Document MNZpErM2a49V89wQeoaMVwy

ANALYTICAL CHEMISTRY OF PCBs Mitchell 0. Erickson BUTTERWORTH PUBLISHERS Boston London Sydney Wellington Durban Toronto An Ann Arbor Science Book HONS 223437 To my sistff, Beverly J. rckson, who was moat interested n my progress with this book, but did not tive to see t completed. HONS 223438 ABOUT THE AUTHOR Mitcneii 0. Erickson i$ a Principal Charms! with Midwest fiesearcn institute m Kansas City, Missouri. He has conducted research m all maior areas of trace organic anetysis m air. water, sod. sediment, biota, nssue. sludge, and hazardous waste; nas developed methods tor determination ot PC8s m a variety of mainces; provided technical assistance to the U S. EPA m permitting PC8 destruction processess: has investigated the formation of chlorinated dibenzofurans and other toxic products trom PC8s and other transformer fluids under fire conditions. He has also studied hatogenated hydrocarbon levels in the environment and human tissues and fluids, and developed methods tor the analysis ot organic materials in dissel exhaust. He has worked extensively in developing analytical techniques using GC, FTIR and GCiFTtfi. Or. Erickson has published *0 government reports. 36 papers in peer review journals and presented 36 papers at scientific meetings. He is a member of the American Chemical Society, the American Society lor Mass Spectrometry, the Society for Applied Spec troscopy, Sigma Xi (Scientific Research Society of North America), and the Cobientz Society. He rectived the A B. in Chemistry <t972) from-Gnnneii College and the Ph D. m Analytical Chemistry (1976) from the University of Iowa. HONS 223439 CONTENTS Uet of Figures Preface Acknowiedgmenta 1. Introduction 2. Physical. Chemical, Commercial, Environmental, and Biological Properties I. introduction li. PCB Nomenclature HI. Physical Properties A. Molecular Weights 8. Physical Constants C. Electrochemical Properties 0, Ultraviolet and Fluorescence Spectra E. Infrared Spectra F. Nuclear Magnetic Resonance (NMR)Spectra tv. Synthesis and Standards V. Production and Use A. Arocior and Related Mixtures 8. Impurities in Commercial Mixtures C. MonochioroOiphenyis 0. Oecachiorobiphenyi E. PCBs as By-products F. PCB Formation Ouring Water Chlorination G. PCB Formation from Thermal Degradation of Other Chlorinated Organics VI. Environmental Occurrence a. General Levels and Distribution B. Major Environmental Contamination VII. Environmental Transport and Fate VHI. Destruction, Degradation, andMetadolism A. Intentional Destruction B. Environmental Degradation C. Microbial Degradation 0. Metabolism by Higher Animals E. Degradation Ouring Usa and Analysis F. Degradation in Fires vii xfl xvil *1* 1 5 5 5 9 9 10 13 13 13 u u 15 IS 17 22 22 22 23 23 24 2* 24 34 36 36 37 37 39 39 40 HONS 223440 vHi Contents IX. Toxicology X. Occupational Exposure ana ItsEffects 3. Analytical Procedures 1. ansi ana a$TM Procedures II EPA Procedure for Oils ill. EPA Procedure lor Spills and incinerators iv. Procedures tor Food V. Procedures for By-productAnalysis 4. Sample Collection and Storage I Water A, Grab Sampling 8. Automatic Composite Samplers C. Solid Adsorbent Sampling 0. CiQuid-LiQUid Extraction Sampling E- Rainwater Sampling F. Water Sample Storage i| Air A. Ambient Air 8. Source Sampling hi. Natural Gas m Pipelines iV. Solids ` V. Surfaces vt. OH, Dielectric Fluids, Etc. 5. Extraction I. General Considerations II. Water A. Liquid-Liquid Extraction 8. Continuous Liquid-Liquid Extraction (CLE) C. Sorbent Column Extraction D. Purge and Trap E. Comparison of Extraction andTechniques in Sewage and Sludge iv. Sediment and Soil A. Solvent Extraction B Collaborative Studies C. Thermal Desorption 0. Comparison of Sediment and Soil Extraction Techniques V. Air A. Polyurethane Foam B. Ftonsil C. XAD*2 0. Dry Deposition Samples VI. Blood A. Environmental Protection Agency 8. Canters (or Oisease Control C. Comparison of Blood ExtractionTechniques VII. Animal and Plant Tissues A. Adipose Tissue 45 5*, 55 55 61 61 62 62 63 63 $4 64 55 67 68 68 71 71 79 64 85 85 88 87 67 88 88 89 90 90 91 91 92 92 93 93 94 . 95 96 96 97 97 97 98 99 100 too 100 HONS 223441 Contents 8. Fish C. Milk D Eggs Other Ammai Organs F Plant Tissue G. Discussion ol Tissue Extraction VIII Paper Products IX. Oils A. Transformer and Related Cits 0. vegetable Ohs X Ancillary Considerations A. Solvent Evaporation B. Sorption onto Glassware C. Sources of Contamination Cleenup 1. Adsorbent Column Chromatography A. General Practices 8- Flonsil C. Silica Gel D Alumma E- Carbon II. High Performance Liquid Chromatography A. Characteristics 8. Applications C. (Detailed Procedure III. Thin-Layer Chromatography IV. Adsorbent Slurry Techniques V. Gel Permeation Chromatography A. Progenies B. Eluting Solvents C. Calibration D Comparison to Other Cleanup Techniques E. Automation f Applications G. Detailed Procedure VI. Uqutd-Liquid Partitioning Vti. Chemical Otgredatton A. Specific Reactione B. Sulfuric Acid C. Chromium Trioxide 0. Bate VIII. Cleanup of OH Samplea IX. Sulfur Removal X. Criteria lor Choice of a Cleanup Ttcnniqut A. Lipids 8. Macromoiecuies C. Organochlonne Pesticides XI. Validation of Cltanup Techniques 7. Determination l. Criteria for Choice of Techniques IX 103 106 107 106 100 109 110 111 111 113 114 114 114 115 117 110 110 119 123 130 134 141 141 143 147 147 140 149 149 149 150 153 153 154 154 154 156 156 156 150 161 162 164 166 167 168 168 168 171 171 HONS 223442 X it Gas Chromaiograpny A Separanon 8 Injection C Oetecnon 0. Perchionnation E. Cafbon SKeieion Chromatograpny ill Thm*Layer Chromaiograpny A. Historical Perspective 9. Comparison to Other Techniques C Current ana Potential Application* iv H(gn Performance Liquio Chromatography A. Literature Citations B. Current and Potential Applications V. Noncnromatographic Methoos A Nuclear Magnetic Resonance (NMR) Spectrometry 8 infrared (|R) Spectrometry C. Radioimmunoassay 0 Other Techniques VI. Confirmation A. Literature Citations B. Current and Potential Applications Vll Screening . A. Screening lor RCBs 8. Screening for interferences VIII. Summary 6. Data Reduction l. Qualitative A. The Importance of Proper Qualitative Data Interpretation 8. Interpretation ol Retention Data C. interpretation of Mass Spectrometric Oata 11 Quantitative A Calibration 8. Quantitation Techniques hi Data Reporting 9. Quality Assurance ' General Considerations 11 Special Considerations m PCB Analyses A. Reference Materials 8. QA in Multiple Laboratory Networks Hi. Previous QC Measures IV. Recommended OA/QC Measures A. Transformer Oi* B. Transformer Fluids ana Waste Ous C. Byproduct PCBs to. Collaborative Studies I Wildlife II Chicken Fai and F*sn Contents ,73 175 ,gg ,97 240 242 242 243 247 247 247 248 254 254 255 255 256 257 257 257 256 259 259 264 264 267 267 267 269 275 276 2 79 281 302 305 305 310 3i0 310 3'4 315 315 3i7 316 319 320 320 HONS 223443 Contents Xl Ml. Paperboard iv. Marine Sediments v Quantitation Techniques ana Milk A Ouantitai<on Techniques B, Milk VI. Paper Mill Effluent VII. Wet Lake Sediment VIM. NatuiaMy Contaminated Ory Sediments IX. Ambient Air X. Ory Pigments Xf. insulating Oils XM. Byproducts from industrial Processes XHI. Byproducts in a Chlorinated Aromatic Waste XiV. Herring XV. Bovine Serum XVI. Lubricating Oils 320 324 324 324 325 335 327 329 329 330 330 331 333 335 335 337 Bibliography 339 Appendix A Nomenclature and Physical Constants of Poiycmonnated Biphenyls 461 Appendix 8 Composition of Some Commercial PC8 Mixtures 469 Appendix C * Mass Spectral Characteristics ofPCBs 477 Appendix 0 PGC/ECD Chromatograms oiArociorMixtures 463 Appendix E * Terms and Abbreviations 46g index SOI HONS 223444 LIST OF FIGURES 2*t Distribution of Chlorine Atoms m the Two Rings of Biphenyl 2-2 Bioaccumulation of PCBs *n the lake Ontario Ecosystem 2-3 Environmental Persistence of Selected Chlorinated Biphenyl isomers 2*4 Common fn Vivo PCB Metabolites 2 5 Polychlorinated O'beruofurans Formed from Thermal Degradation of 2.2`.4,5.5-PentachtoroOiphenyi 2-6 Tetrachlorodibenzofurans Formed from Thermal Combustion of PCBs ana a Tncmorobenzene Mixture 2*7 Summary of PCB Isomers Which induce Cyto chrome P-450 4*1 Passive Water Sampling Device 4- 2 Effect of Storage Conditions on Recovery of Arocfor 1018 from River Water 4.3 Modified Method 5 Tram for Organics Sampling of Slack Gas 5- t Exhaustive Steam*Distiiiation and Solvent* Extraction Apparatus 6*1 Separation of p,p**OOE from Arocior 1254 by Column Chromatography with Different Activities of Silica Gel 6- 2 Apparatus for Pressure-Asaisted Silica Gel Microcolumn Chromatograpmc Separation of Organochlorine Pesticides from PCBs Following Flortsll Cleanup 6-3 Arocior Elution Patterns from Silica Gel Microcotumn with Hexane as Eluting Solvent M PGC/ECD Chromatograms (A) Before and (B) After Alumina Column Chromatographic Cleanup 6-5 Flow Chan of Extraction and Cleanup Using Floristl and Carbon/Foam Column Chromatog raphy to Separate PCBs from Other Organo chlorine Compounds in Sediment Samples 6-6 Chromatograms of PCBs Fractionated According 10 Number of Orrho Chlorines Using a Charcoal Column xti 8 26 38 40 43 44 51 66 70 79 105 t25 128 129 132 tOS 137 HONS 223445 List ot Figures XUI $7 Elution Order ot PCBs from Carbon Column, illustrating Dapendanca on Number of ortho Chlorines ijg 6-8 Enrichment and Frectlonation of PCBs. PCNs, PCDDs, ano PCDFs from Tissue Samples Using Carbon ' ' Column 142 6*9 Preparative Reversed-Phase HPLC Cleanup of Paperboard Extract 144 6*10 Preparative-Scale HPLC Fractionation of Oil iae 6-u QPC Elunon Profiles ot Selected Biogenic Compounds and Environmental Contaminants 151 6-12 QPC Chromatograms of Fat Sample Showing the Separation of Low Molecular Weight Organic Chemicals (LMWO) from Lipids (Top) and Fractionation Ot LMWOs iBottom) 152 6*13 PGC/ECD Chromatograms ot Fish Extract (A) Before and (B) After Treatment with KOH and Chromium Thoxtde to Degrade the p.p -DOE (Peak 1) and p,p'-OOt (Peak 2) i$o 6- u HRGC/ECD Chromatograms illustrating inter. ference by Sulfur m the Early Portion of Chromatogram A 165 7- 1 Temperature-Programmed PGC/ECO Chromatogram of Arocior 1254 131 7-2 PGC/FIO Chromatogram of PCBs and PCTs Using a Bonded Liquid Phase 183 7-3 HPGC/ECO Chromatogram of Arocior 1018, 1254, and 1260 (5:3:2. w/w/w) * 184 7-4 HRGC/E1MS Reconstructed Full Scan ion Chro matogram of PCBs and d.. Anthracene (Internal Standard) 185 7-5 Retention Times of 77 PCB Congeners Relative to d*-3. 3`. 4. 4'-Tetrachlorobiphenyi iRRT of i.OO) 187 7-6 HRGC/ECD Chromatograms of Arocors 1242. 1254, and 1260 on a 0.29 mm ID x 20-m Apiezon L Column 189 7-7 Plot of HRGC Relative Retention Time versus Congener Number tor ait 209 PCBs 193 7-0 Comparison of PGC/ECO (Top) and HRGC/ECO (Bonom) Chromatograms of 29 PCB Congeners 195 7-9 HRGC/ECD Chromatogram of Arocior 1260 Short Capillary illustrating Rapid Separation 196 7-10 Detection Limits and Oynamtc Range for Several instrumental Methods 199 7-11 PGC/ECD Chromatograms of Arocior 1260 (921 pg. Solid Line) and Nine Common Pesticides (38 pg Each. Oashed Line) illustrating the Potential for interference 203 7-12 HRGC/ECD Chromatogram of Process intermedi ate (Bottom) and Arocior 1248 (Top) 204 HONS 223*** xiv List of Figures 713 Plot of HRGC/ECO Relative Response Factor Versus Congener Number for AM 209 PC8s 7-14 Reconstructed ion Current Chromatogram of hAGC/EIMS Analysts ol a Pish Sample from Chesapeake Bay 7-15 Extracted Ion Current Profiles for Tetri-Through HeptachioroDiphenyls in Pish Sample from Chesapeake Bay 7-16 Mass Spectrum of Hexachlorobiphenyl in Fish Sample from Chesapeake Say 7.17 HRGC/EiMS Data for a Chlorinated Aromatic Waste Showing Presence of Octachiorobiphenyls as By-products 7-18 Plot of Average Response Factors Versus PCS Homoiog 7-19 Comparison o> HRGC'NCIMS and HRGC'ElMS (Bottom) Total ion Current Profiles for a Fish Sample 7 20 HRElMS Spectrum of Fish Sample After Sulfuric Acid and Alumina Column Chromatographic Cleanups 7-21 PGC/ECO Chromatograms of Arocior 1254 Before (Top) and After Perchionneoon (Bottom) 7-22 Tie of Aroctors 1221 Through 1268 in Three Systems 723 Two Dimensional TLC ot Arocior 1254 end OOT Analogs on e Silver Nitrate-impregnated Silica Gel Plate 7-24 HPiC Chromatogram of PCBs with UV Detection at Two Wavelengths (205 nm end 254 nm| 725 Reverse Phase HPlCAJV Separation of Arociors 1221, 1016. and 1254 (i:i:t, w/w/wl m Tetrahydrofuran on a u Bonoapak C., Column Monitored at 254 nm 7.26 High Resolution Reversed-Phaee HPLCfUV Chromeiogrem of PCB Mixture Containing 48% Chlorine 7-27 Total Organic HsNde (TOX) Analysis Using a Short Column PGC/H6CD 7-2B TOO Measurements of Arocior 1248 Using Electrolytic Conductivrty 6-t Principal Components Plot of PCB Date 6-2 PGC/6CD Chromatogram ot Arocior 1254 0-3 Ftow Chen for Division of PGC/ECD Chro matograms into Retention Time Regions for Quantitation of Samples With Mixed Arocior Patterns 9-1 Quality Control Chan lor HRGC'ECD Analysts of PCBs and Other OrganocMorme Compounds m Human Milk 208 213 214 215 220 229 235 237 241 245 246 250 251 252 261 262 274 265 266 316 HONS 223447 List of Figures to-t Paired Sample (Youden) Plot tor Two Wot Sediment Samples 10-2 Histogram of Error Contribution by Homologs tor Sample A from CMA Study tO-3 Analysis Flow Scheme for By-product Col laborative Study. Showing Sample Entry Points 10-4 Plot ol Error in By-product Collaborative Study by Sample Type, Showing Contributions of Ihe Analysts Steps XV 328 332 334 335 HONS 223*** PREFACE This book is a comprehensive review of the analytical chemistry of polychlorinated biphenyls (PCBs>. it is pan history, pan annotated bbtography. part comparison and pan guidance, it is nor, however, a cookbook for the neophyte. There are no written step*by*step pro* cedures lor tne analysis of given matrices for PCBs; the field is much loo complex to recommend a finite set ot analytical procedures. Chemists with no experience m PCB analysis should bene'it greatly from this book by gaming an appreciation for the analytical com* piexily and reviewing possible approaches to analytical prop* iem. Experienced analysts may find some guidance on possible improvements 10 thtir currant practices. This project grew out of a literature review that I conducted along with a colleague. John Stanley, in 19B2 for the Office of Toxic Substances of the U.S. Environmental Protection Agency (Erickson and Stanley, 1962). AD of me material from that review has baan substantially revised, updated, ana augmented, in addition me size at me bibliography has more man doubled. The references in me bibliography were obtained by multiple com* puter and manual searches of the published literature and from par* sonai contacts. Every effort has been made to be comprehensive and current in me coverage of articles pertaining to analysis. Never* meiess. t am quite sure mat there are some omissions. | apologize in advance to those authors whose work may have bean slighted and request that they send a reprint so mat any subsequent editions can be properly updated. No attempt was mad# to be comprehensive on the ancillary subjects (environmental occurrence, toxicology, etc.) presented m Chapter 2. The Oook contains tan chapters. Following an introductory chapter, Chapter 2 reviews the physical, chemical, commercial, envi* ronmentai, and oioiogicai properties of PCBe. While these areas art not ail central to analytical concerns, they provide relevant data and a perspective on the properties of PCBs which make them of such great interest to analysts. Chapter 3 discusses the avariaoie written procedures (standard metnodt. etc.) wmch may Dt used directly by analysts. For those desiring more detail or where no written pro* ceoure exists, me next six chapters discuss the discrete steps of analysis: sampling, extraction, cleanup, determination, data reduc tion. and Quality assurance. Chapter 10 discusses collaborative testing, which is the ultimate steo <n a method validation. xvit HONS 223449 xvllt Preface A bibliography is presented An references m the text are in the bibliography; nowever. not ail entries in the bibliography are dis cussed in the text The sheer volume of data overwhelms any attempt to adeguetaty discuss all ot the references, in addition, many references are redundant or outdated. The additional references m the bibliography may help those who need defans m a specific area. Where appropriate, secondary citations to Chemical Abstract have been included to assist those interested w obtaining the reference. The reference callouts m the text use the date of the original citation, not that of the secondary citation. Five appendices present ancillary material on PCB nomenclature end physical proper ties. composition of commerciat mixtures, mast spectra characteristics, and PGC/ECO chromatograms. The final appendix () is a glossary of the specialised terms and abbreviations used throughout this book. As nottO rspestedly throughout this book, the analytical chem istry of PCBs is an evolving science or. in some cases, an evolving art. Much research still needs to be dona to supply methods for the routine analysts of ell of the sample matrices in which PCBs may occur. Many of the current methods suffer trom tack of preci sion or accuracy, or thty do not providt the proper Qualitative infor mation. This book should bring the discipline into better locus and permit analysts to move forward with development of need methods. MHchefi 0. Erickson Midwest Research institute Kentet City. Missouri MOHS 223450 ACKNOWLEDGMENTS I with to thank many colleagues who provided encouragement ana reviewed the book during its gestation. Thay davotad a great daai of time and thought to their reviews and supplied several reterences to augment certain sections and ladles. I also received reviews of in dividual chapters Worn John Craddock. John Going, Daniel Heggem, John Hosenfeid. and John Stanley. . i have received encouragement on this protect from Midwest Research institute's management, particularly John Going. The edi torial staff at Butterwonhs. has been moat helpful in providing assistance and encouragement. Some of the data were tabulated and proofread by Leslie Moody, Jon Onstof. Audrey Sanford. Steve Turner, and P. J. Boone. Technical assistance was provided by the Midwest Research institute Office Services Department, notably the Word Processing Center consisting of Kathy Punk. Cindy Melenson, lanore Moore. Susie Powell, Carol Shaw, and especially Gloria Suitenlk. I would like to thank my family and friends, especially my wife Colleen and my son Adam, for their forbearance over the past two years. They lost many weekends to this project. To ail of you who helped me make this book a reality, thanks! xix HONS 223451 1 INTRODUCTION Polychlorinated biphenyls (PCS s) ire i class of 209 discrete cneimcil compounds, called congeners, in wnich one lo len chlorine atoms ire attached to Diphenyl. //"\\ Cl. Cl n m * n * 1 to 10 Polychlorinated biphenyls (PC8s) were commercially produced is complex mixtures for i variety of uses, including dielectric fluids in capacitors and transformers. The major producer, Monsanto Corporation, marketed PC8s under the trade name Aroclorw from 1930 to 1977. Aroclorsii were marketed for use m transformers. capacitors, printing m*s, paints, de* dusting agents, pesticides, and many other applications (Durfee et al , 1978). Their chemical and pnysical stability ana their electrical insulating properites led to the commer cial util'ty of PCBs. The production and use of PCBs is dis* cussed m detail in Chapter 2. Their chemical and physical stability has also been responsible for tne PCB environmental contamination problem. Since PCBs do not readily degrade in the environment after disposal or dissemination and are lipophilic, they are per sistent and tend to bioaccumulate. In 1966, Jensen (Anon., 1966; Jensen et al., 1969; Jensen, 1972; HuUmger et al.. 1974a) reported PCBs >n eagles, herring, and other Swedish environmenta1 samples. Since then, PCBs have been shown to be nearly ubiQuitous environmental pollutants, occurring in most ngman and animal adipose samples, milk, sediment, and numerous other matrices. 1 HONS 223452 2 Analytical Chemistry of PCBs As early as 1936. occupational exposure as re ported to cause to*' c effects ana .ortplace threshold limn values were subsequently set. Animal studies with Doth com mercial mixtures ana moividua) congener nave s^own a *ar>' ety of enrome toxic ejects (National Research Council. 1979). PC8-contami rated coomg o> ' causea a total of 1.291 "Vusno" patients in 1968 in western Jaoan The clinical man ifestations include various somatic complaints, low omth -eights. chloracne. ana pigmentation (Kuratsune. 1972. Hiquchi. 1976). The animal to*icolog'ca 1 data nave tended to indicate that PCSs are toxic. However, contamination of the commercial PCS mixtures with more toic comoounds suen as polychlorinated d'Denzofurans (PCOFs) confounds tne toxico logical data. For example. 't is ungear wnether the pC8s or other contaminants in the Vjsno oil are responsiple for the observed healtn effects. In addition, it has been snown mat the toxicity of PCBs varies with potn nomolog ana 'somer (Safe et a).. 19B3e). Thus, the toxicology of PCBs remains an area of controversy ana continued research. The discovery of the widespread environmenta1 oc currence. the increased general environmental concern, ana the apparent link to careinogenesis prompted a public outcry which culminated in the United States in 1976 with the regu lation of PC8s by the Toxic Substances Control Act (TSCA), pl 94-469 (U.S. Congress. 1976). Section 6(e) of TSCA specif ically regulates manufacture, processing, distribution in commerce, or use of PCBs. The U S. Environmental Protection Agency (EPA) was charged with rule promulgation and enforce ment. The EPA was also given latitude to grant exemptions to the ban if the manufacture, processing, distribution in com merce. or use is totally enclosed or will not present an un reasonable risk, of injury to health or the environmeM Tne CPA suoseouently promulgated a series of rules on the various aspects of the law Several EPA rules are of concern to analytical chemists, since they require determination of PCBs m various matrices. A rule promulgated on Hay 31, 1979 (EPA. 19790. Velie and Kuntz, 1982. EPA. 1963d) categorized the use. con centration, ana type (liquid or nonliQuio) of PCBs. Portions of this rule were declared invalid Dy a U.S. Court of Appeals ano several rules have stnee been issued to satisfy the court-ordered changes. Certain totally enclosed electrical uses of PCBs are allowed for tne remainder of the useful life of existing equipment (EPA, 1982f, Qtpartment of Transporta tion, 1984). In 1982, a rule on use in closed and controlled manufacturing processes was promulgated (PA, 1982c; Velie and Kuntz. 1982; EPA, 1983d). Tne rule excludes PCBs m pro ducts or wastes Delow the practical limit of quantitation HONS 223453 Introduction 3 (UOQ) from the T$CA can on manufacture, processing, distripu- lion m commerce, ana use, ' e. . pC8s be' o- tn tOQ a^e not regulates. The pract-cai lOQ -as defined as 10 ug/m1 per re solvable gas chromatograomc peak for air, iOO ug/t o*r re solvable gas cnromatograonic peak for -ater, ana 2 ag/g pe' resolvable gas cnromatograoh'C peak for any product or waste, tt snoula De notea that these defined lOQs are mucn higher than those obtainable -ith state-of-the-art instrumentation and -ith low levels of interferences. In this rule, the EPA recommended high resolution (capil'ary) gas Chromatography/ electron impact mass spectrometry (hRGC/ 1M$) as the analyt ical technique ana supplied suggested methods for the three matrices (Erickson et al . 1982) The EPA also recognized that the PCS composition as by-products -ould not resemble mat of commercial products such as Aroclors and Cautioned agamst the use of classic Aroc 1 or-basea analyses methods. TSCA and the PCS rjles promulgated under it were rev'e-ed re cently (Oyer, 198). Trench. 1981; Caims and Siegmund. ]98JO. vel'e ana kunt2 . 1982; Oeoartment of Transportation. 1984} Disposal nas Been a major area of concern since m* restriction of PCS use in me United States and other coun tries. large Quantities of PC0*cnteining products such as transformer oils and capacitors are being removed from ser vice and must be disposed of proDerly In the United States (EPA, l979d), the allowed methods of disposal are keyed Doth to concentretion and to the matrix. If the PCB concentration is 500 ppm or greater, disposal in a nigh efficiency incin erator is stipulated. If the concentration is 50 to 500 pom and the PCBs are in a liquid matrix such as a mineral oil ai* electric fluid, then incinerators. landfills, or nigh effi ciency boilers can be used. In addition, alternate methods of disposal are allowed if they can oe mown to oe eour.alent. To demonst-ate compliance, incinerators must pass an initial test which, among other things, requires mat air emissions oe i 1 mg PCB/kg CB introduced for nonliquid PCBs A full listing of Current U.S. EPA rules on PCBs may be 00* tameo m the current annuli edition of the Code of federal Regulations, 40 CfR 761 (EPA 1903d or Current update). While PCB regulations and disposal reouirements differ from country to country, there is a common analytical interest in determining their oresence m the environment and in potential sources to tne environment. Regardless of the laws and rules, the analytical needs are similar; reliable, practical, sensitive methods which can determine PCBs*-commercial mixtures, byproducts, and destruction residues--in a variety of matrices. HONS 223*5* 4 Analytical Chemistry of PC8$ This boot reviews the puo'ications related to PCS analysis Some of the o;or metnoas may pe merely of histor* 'Cal mterest. but are mc'uded for co*o'eteness and to pro vide the reaoer with a recoro of wnat techniques have been used for soec'f'c applications In addition ang more impor tantly, state-of-tne-art methods are discussed and their rel evance to various applications presented. The analyst moving Into PC8 analysis for the f'rst time or encountering a new PC8*related orooiem will f no the discussions helpful m choosing or designing appropriate methods HONS 223455 2 PHYSICAL, CHEMICAL, COMMERCIAL, ENVIRONMENTAL, AND BIOLOGICAL PROPERTIES 1. INTRODUCTION Tms chapter presents brief overviews of PCB nomen clature. physical ana chemical prooerties, Synthes's, commer cial DroOuct'on ana use, toxicology, metaoolism, degradation ana destruction, environmental occurrence, environmental fate ana transport, ana occupational e^oosure of *CBs. The treat ment of these suDjects is not mtenaea to pe comprehensive but rather to proviae sufficient information to give tne reaaer a oersoective of tire PCB problems which nave lead to the analysis of various samoies. Where possible, monograohs ana review articles have been cited to guide the reader with more than a casual interest in a topical area II. PCS NOMENCLATURE For the purposes of this book, a PCB is one of 209 compounds having the formula C|jH|fi> Cl , where n * 1-10, i e., monocnloroo'pnenyl through oecach?oro0?ohenyl (Tapi* a-I, see Appendix A), with the gene-al structure: The term "PCB1* is used to refer to the entire class or any sublet of one or more comoounds. rtcognue tnat, strictly speaking, "mono' is not "poly," however, the three monochlo* ropipnenyls have been included m this oook since they are members of the chemical class, colloquial usage usually in clude* tne*. ana US. court rulings (Perlman. 1980; McCallum, 1982) have declared them to oe PCBs for PA enforcement pur poses Sipnenvi is not counted as a PCB. although some in vestigators nave used it as a degenerate memoer of tne set 5 RONS 223456 6 Analytical Chemistry of PCBs for chromatographic retention Behavior and other studies (see. for e*ample. Alpro et al . 19 77). Biphenyl includeo n some ohys'cat and chemical property tables in this ork for completeness PC8s are listed m Chemical Abstracts unaer "i.rDipnenyl. chforo aerivs." with a generic tAS^egi stry number of 1336*36*3 However, this CAS number does not yield many Citations m a computerised literature search. Apparently it is not widely used. CAS No. 12767*79*2 is assigned to "Aroc'or" and may be useful m generic PCB literature searches. The synonyms listed By Chemical Abstracts are Biphenyl, chlorinated; chlorinated d'pnenyl, ano dipnenyl, chlorinated. The entire set of 209 PCBs forms a set of congeners (fable 2*11. when PCBs are suboivioeo by degree of cnlorina* hon, the term homo log is used; e g. , the tnchloroBiphenyl homolog. PCBs of a given nomoiog with different chlorine substitution position are called isomers (Taole 2*11. figure 2-1) 2.3.a-tricnlorooiphenyI ano 3.3'.5*trichIorootphenyI are two of the twelve tricnlorooipneny\ isomers. Many researchers have found the full chemical names unwieldy and nave adopted various shorthand nomenclatures, for instance, 3.3 *,4 ,4 *,5,5`-heiachlorobipneny1 has been re* ferred to as 3,3',4,4' ,5.5'*hea or jimoly 3,3`* .4* Recently Ballscnmiter and Zell (1980) arranged the 209 conge* ners in ascending numeric order and assigned wnat are com monly termed "Ballscnmiter" or "luPAC" numbers from 1 to 209. as shown m Table A*I. A minor discrepancy was corrected by Schulte and Haliscn (1983) and has Been incorporated into Table A*l, This shorthand nomenclature has become increas ingly popular and is convenient 'or many uses such as label ing cnromatograms An alternate snorthano numbering system, usmq base 16. can designate each PCS congener py a three digit numoer uiuo. 1983 ) Table 2-1 PCB Nomenclature Categories Category Number of Individual Compounds4 Congener Homo log Isomers/Homol og a Natural isotopic aounoance only 209 10 1-46 HONS 22345? Properties 7 Table MI. Composition of Chlorinated Biphenyl* by Homolog Emc'rica 1 Fonno la Ch1orobiphenyIs Molecular weight4 Average Molecular weight0 Percent Ch1 orine NO of Isomers C l 2h i 0 C,-HaC1 Ci:H*C1; C|,h7C13 Ci2h,.C1, C ! 2 H f, c 1 , CuH.CV, C,2H3C1: C,2H;.Cla CirHd, C| = CT 154 1 188 0 222.0 256.0 289.9 323. 9 3$7 8 391.8 425 8 4$9 7 493. 7 154.2 188. 7 223 1 257.6 292.0 326.4 360 9 395.3 429.8 464.2 498. 7 01 19 3 32 12 41 24 49 4 2 54 46 42 o3 24 66 12 69 3 71 1 a Saseo on --Cl (atomic weight 34.969) ana Ii;C (atomic we>gnt 12.000) and lH (atomic weight 1.0079). Cor responds to the lowest mass in the molecular cluster of the mass spectrum. D "Average" molecular weight; Cased on natural abundance chlorine (atomic weight 35.453), carbon (atomic weight 12 011) and hydrogen (atomic weight 1 0088). HONS 223456 8 Analytical Chemistry of PCBs 3 2 ry 56 6' 5` A0 f ae 1 c 0 * 2 p <3 2? 0a X u 5 0 C^'orln* Afomj on Ring A l 23 a 3 66 3 6 16 16 9 21 36 18 21 16 6 5 1 3 6 6 3 ) figure :*1. D'stnPut>on of Chlorine Atoms m the rwO Rings of Biphenyl Repnnted with permission from Hutxinger et a). (1974a), copyright 1974, CRC Press. Inc . 9oca Raton. Honda HONS 223459 Properties 9 As -ith any complex. symmetric molecule, several nomenclatures may be employed for the same structure. in* molecule inovn nere *ouio Be correctly loenti fied as the O C: Ci 2,2',4.S' conqener. with alternate But less correct designa* lions Of :.4.2`.5'; 2.2'.A', 5, 2.3'.4,6', 2',3,4'.6, etc. Another example >s 8allscnmiter congener No. 98, designated 2.2'.3',a.6. which is listed By Chemical AOstracts as 2.2'. 3.A'.6' ine reader should convince himself tnat these are m fact the same compound ana Be wary of these types of redunoanc > es The complex commercial mixtures marketed as PCBs (see "Commercial Production," below) nave often Been treated as a single chemical entity. Repeatedly, authors have used the term "PCB" to refer specifically to the commercial mix tures (eg.. Aroclors) ratner than the entire compound class. The reader must develop an awareness of the difference and an aoprec'ation of the significance. for instance, many PCS analytical methods focus on only one or more of the commer cial PCS mixtures and could neither detect nor quantitate all PCBs 1J1. SHvsiCAl PROPERTIES The physical properties of PCBs are important to an understanding their analytical oroperties as well as their physlological and environmental properties. The interactions of the various physical properties and their relevance to specific applications can be extremely complex and are not well defined. Many of the references cued in the sections oelow use pnysical properties to derive oioconcentration fac tors (Mackey. 1902b), environmenta1 transport and data (Mackay. 1982a), aqueous movement (Yalkowsky et a 1. , 19B0), and environmental persistence (Neely, 1983> A. Molecular weights Table 2*11 lists the molecular weight, and percent chlorine for the PCB homologs. T*o values of the molecular MQHS 223460 10 Analytical Chamlstry of PC8s weight are presented based on the atomic weight of the most common isotopes (UC. J4C). and lH) and on the average atomic eight of the natural abundance ratios of tne different iso topes the former corresponds to the lowest mass m tne mo lecular cluster of me mass spectrum The letter >s tne av erage molecular weight. The exact masses and relative abun dances of tne major components of the molecular cluster a^e l's ted in Tab le C-1. 8. Physical Constants Table A-J i n Appendix A presents the CAS registry numoer for all 209 PCB Congeners, and the available melt'rg point, and aqueous solubility data. The physical and elec trical orooerties of tne commercial muturit are discussed m the "Production jna Use" section oelow There is growing ev idence that the subcooled liquid prooerties of organic Chem icals control some environmental partitioning processes (Macxay, 19820. Macxay et a I.;. 1982). Thus, melting point data are important m calculating various environmental proo erties of PC8s. Table 2*111 presents the boiling points, vapor pressures and octanol-water partition coefficients (log K ) for several PC8s. The polling point and vapor pressure data from Neely (1983), Ueast and Selby (1967). Cook (1972). Letfer et ai. ( 1983), Bidleman et al. (1983), and Bidleman (1984) may not Ot comparable since different experimental techniques were used in the determinations. Bidleman et al (1983). for example, compared vapor pressures determined by gas saturation, gas chromatography, and from the literature. While most values were in reasonable agreement, some of their determinations differ py more than a factor of two. as can be seen in Table 2-11], the boiling points and vapor pres sures vary not only with the degree of chlorination. put a'so with tne position of subst'tution This >s manifested m m? gas chromatographic e'ution orders, as discussed m Chapter 7 The vapor pressures of Aroclor 1232, 1242. 1248, and 1254 were discussed by Bopo (1983). Additional data on vapor pressures (Vestcott and Bidleman, 1981) and boiling points (Augood et a)., 1963) of individual PCB congeners has been pub!ishd- Th log it and water solubility data (Table a-1) are usefu) in estimating transport and fate througn the en vironment (Mackey, 1962b), as well as analytical properties. Mackay (1982b) has oublished thf octanol-wattr partition co efficients for Aroclor 1016. 1248. 1254, and 1260. Addi tional work, on aqueous solubility (Mackay et al., 1980, StO I If nburg and Andr*n, 1983; Leifer et al., 1983, vaUowuy et al., 1983) and partitioning (Voice et a 1. . 1983; Shaw and HONS 223461 Properties it uP*C HO 2*!!! Soiling Point!, Vapor Pr!tur!, tr>4 Octanol-water Partition Coefficient! (* ) of Selected PCS Congener! 0w Compouno 8oi t mg Point (*CJ (m Hg)"' V400r Pr!!yr* [mm ng 25*C) L *0. - 8'0neny\ 12 23 34 4 2,2' 5 2.3 7 2.4 8 2.4' 9 2.5 11 3,3' 12 3,4 14 3,5 15 4.4' IS 2.2`.S 33 2' .3,4 28 2.*,4' 29 2,4.5 30 2.4.6 31 2.*' .5 37 3.4.4' 40 2.2`.3.3' 44 2.2' .3,5' 47 2.2' .4.4' S2 2.2'.5,5' 53 2.2' ,5.6' 54 2.:'.6.6 61 2.3.4.5 66 2.3' .4,4' 70 2.3' .4' ,5 77 3.3',4.4' 80 3.3'.5.5' et 2.2'.3.4.5 87 2.2',3.4.5' 88 2.2' .3.4.6 99 2.2' .4.4' ,S 101 2.2'.4.5.5' 10$ 2.3,1' .4.4' lit 2.3.4.S.6 255 274 d 28**5fl 291 U2 (30)' ill 415) 322-4r 195*200 (IS) f 166 (10) 315*9 9 5 10*J 8 4 10l* 1.5 10 5* 4 6 * 10.4 1 * 10 J 1.8 x 10 1.4 * 10.4; 6 8 x 10 *e 1.9 > 10 i 9 x 10.` 7. 7 x 10 jn 1.3 * io.*J 8.8 i i.4l 3.0 * 10 * 7.3 i io'B 8 6 10 s 3.7 10 ` 2.1 10 * 4 6 10 * 4 4 i i.: 2.3 10 #1 5.8 > 10 T' 1 6 i 10 ** 2 1 a 10 s* 9.0 a 10.4 6.6 a 10 4* 4 10 4.56 4 72 4 69 5.02 5.15 < 5.32 5 18 5 34 5.26 5.64 6.1* 5, 74 5.77 5.77 5.90 6.67 6. 67 6 44* 6 26 5.94 6 3K 6.67* 6.39 6.52 6.58 6.38* 6 a5o 7.SI 6.65 6.65 HONS 223462 12 IUP*C No Analytical Chemistry of PCBs Tie 1f 2' I II ( COM > nufd) ComeounO 00'1 mg p0'l < *Cg (" Mg)"' viper ' (rnsuri (mm Hg. ;5*C)4 " loo * C * nn< 110 12S 129 13* 130 1*9 153 1SS 156 170 171 100 10S 107 190 202 206 209 2 , 3 ' .4.4' ,5 2.2' .3.3' .4,4' 2,2' ,3,3',4.i 1 9 ' ,3,3' .5,6 :.r ,3,4.4',5' 2.2' .3.4- .S' .6 2,2' .4.4'.5,S' 2,2' .4.4-.6.6' 2,3, 3' .4,4' ,5 2.2' ,3.3'.4,4' .S 2.2' .3.3' .4.4' ,6 2 2' .3.4.4'.S,S' i. * ,3, 4.5. S' .6 2.2' .3.4',S.S' .6 2.2' ,3,3',4.0'.S.S' 2.2' .3.3'.5.S'.6.6* 2.2' .3.3',0.0'.5.S' .6 DfCIChloroe'phfnyl 195**i20 ( 10)' 240-200 (20) 9 0 a io'*# 2 6 i io'*# a 0 a 10'*# 1 1 x 10's* S 2 a 10*-# 1 3 < 10 * l 6 a 10 * 6 3 X 10 '* l 8 a 10 t# 9 7 a 10 ' 2. 3 a 10_`# 7 41 3 26' 3 10' 7 44 7 12 ; 93 0 60 0 42 9 14 9 60 I Nffly (1903). urtlftt othfrvisf nottiT b Valyf* 'n wiouitf prtisurf of mfliurfmfnt if oi(- (frtni from 760 mm Hg. c All leg K iluti from 0rugg*vift it il ( 1902), yriifii oir>*r. >tf rietio d witt ir>d SflOy, 1967 * 0iO>fmin. 1904 viluft orftfntffl 'frf |rf Ivfrages of *.>o H' Dfni*n:.|l y|lol rn or'ginil cuel'Cll'ori ' Cook. 1972. g riUowity tt il . 1.903. r> 0id<cmin it il . 1903. ' Cl)Cu11tfd Oy Nffly (1903). MONS 223463 Properties 13 Connell,- 1904, Rapaport and E'senreich. 1904, Leif>r et *1 1903, 'r1owiky et al , 1983; H TIS. 1904*) has oeen reported ConstderaO1* work has Been aone on measuring *rg calculating the gas'Diase physical constants, especially the Henry's Law constants ana fugac'ties (Hackay et a 1. . 1980, 1983, Hackav. 1902a. 1902b. Murphy et a) , 1903. leifer et *i.. 1903, Bapp. 1983, M*ck*y and Hughes. 1904). The Henry's Law constant is a measure of the eouiliprium attribution co efficient between air ana water (or other gas ana liQuid) Tugaoty 'S a Quantitative measure of the escaping tenaancy of a substance ana is the driving force that causes diffusion anfl partitioning Petween phases (environment*1 compartments). The fugacity m the gas phase is simply the vapor pressure ]n the l*ouifl phase, fugacity is the proauct of the Henry's Law constant and the concentration in solution C. Electrochemical Properties The electrochemical properties of PCBs have not been e'1 studied. Since PC8s are very stable molecules, de termining their oxidation/reduction potential is difficult. However, many of the commercial destruction methods, some metabolic pathways and other routes of degradation, occur via free radical mechanisms. Thus, tneir electrochemical proper ties can be important. A limited study gave the standard po tentials and electron transfer routes of four PCB congeners (Conners et *1., 1985). ` 0. Ultraviolet and fluorescence Spectra The UV spectral properties of PC3s a^e of use not only for HPtC analysis with uv detection, but also for ident ification of synthetic products. The UV spectral properties o' PCBs -ere reviewed Py HuUingtr et *1. (1974a). More re cently, additional data on individual congeners (]ARC, 1978, Appleby. 1976; Brinkman et al., 1976b) and Aroclor mixtures (Bn nkm*n et a 1. . 1976a) have been publ ished. The excitaton. fluorescence, and room temperature phosohorescence maxima for six congeners have oeen reported (wemberger et al.. 1983). The fluorescence soectra of seven congeners in eyclodextnn nave been reported (pemia et al.. 198S). E. Infrared Spectra The IR spectral properties of PCBs were reviewed (HuUinger et al. , 197a). A major component of that review was based on me work of webb and McCall ( 1972 ). Recently, HONS 223*6* 14 Analytical Chemistry of PC8s the diffuse reflectance IR soectra of 16 PCS congeners *ere published (Nyouist et a1 . 1903) In addition to the soec tra. tne group fluencies -ere assigned ana correlations presented which snouid be of use m the identification of other PCS congeners. F. Nuclear Magnetic Resonance (NHR) Spectra Hut2'nger et a* (1974a) presented an extensive re view with 22 references of the proton NHR aata on PCSs. Data on 17 synthetic congeners, the major components of Aroclor 1254. and other data -ere tabulated. Both the 1JC and lH NHR spectra of 10 symmetric PCS congeners -ere investigated by Wilson and Anderson ( 1973) The relationship of structure to shielding and coupling constants -ere discussed. As part of a program to synthe$i:e all 209 congeners, the proton nmr spectral features -ere reported for all tetra- . penta-. he*a-, and heptacn l orooi pheny is (Hu Mm et a'.. 198 A) anp 'or all octa* and nonachloropipheny 1 s (Mullm et a) . 1981) IV. SYNTHESIS ANQ STANQARQS The commercial PCS mixtures -ere synthesized by chlorination of biphenyl -ith chlorine gas (NRC, 1979; Ourfee et al.. 1976). Commercial production is discussed m the following section. Smell quantities (10 to 1,000 mg or di lute solutions) of Aroclors are available for use in scien tific studies from Analabs. North Haven. Connecticut. Ultra Scientific, Hope. Rhode Island, and other suppliers. Routes for synthesis of soeof'c congeners nave Deen revie-ed (Hut2inger et al.. 197a; Roth et al . 1982, Hullin et al . 1901. 1904) Recently. 3.3' .4.4'-tetrecntorobiphenyI was synthesized m gram Quantities (Naxatsu et al. 1902). Although all 209 congeners have oeen synthesized re cently (Hullin tt a).. 1904), only about 00 are commercially available from Ultra Scientific, Hope, Rhode Island, and Analabs. North Haven, Connecticut, in small Quantities (5 to 50 mg or 100~ppm solutions). Various isotopically labeled PCBs hive been synthe sized. 3*Cl-labaled (0-emitter) Aroclors 1240 and 1254 -ere prepared by neutron irradiation of the natural abundance ma terials (Stalling anc Hucfcins, 1971). A uni versa 11y-`Re labeled PCS mixture with 54X chlorine (i.e., Aroclor 1254) has been available from New England Nuclear (Kohli et al. . 1979a). Chlorination of MC*Ubeled biphenyl to 54% chlorine content -as reported by Albro et al. (1904) Tnt'ation of Aroclor 12S4 to yield an Aroclor 1248-like miiture -4S also MOMS 223465 Properties 15 reported by A'Dro et 4'. (1904) Several `C-'abe'ed indi vidual congeners nave oeen vied >n PC0 studies For in stance, MC-2,2' , S , S'- tetracMorooipneny i and 1 *C* 2 ,4 ` .* , 4' . S . S'-ne*acMorot>ioneny 5 -ere used :n oetermm- i ng the t'ssue distribution tn trout and mice (vodcm, 1903). 1 *C 2 . 2' , 4 , 4 ' , S , S'-hencni orooio"ny \ r\4s 4is0 Deen used to study sorption from water to glass surfaces (Pepe and 8yme. 1900; Muidrew et ai . 1931) and was obtained from California Bionuc'ear Corp df, * 3,31 .4.4 1 Tetracn i oropipneny l nas Been available from iCN-kOP Isotopes. Campridge. Massachusetts, and HSO Isotopes. Pointe C'aire-Dorval. Quebec Canada. ! 3C*-4-CM oropipnenyl , 1 3C i j-3.3' . 4 .4 ' - tetracMoro- pipnenyi. ' 3 C, ?-2 . 2 ' . 3.3' ,5.5' .6.6 ' -octacMorob i pneny l . and 13C|2-decacnioropipnenyi -ere synthesized by Roth et a>. (1902) and are available as a miied solution from Oua'ity As surance 0rancn. Environmental Monitoring and Support taoora- tory. u.S. Environmentai Protection Agency. Cincinnati, Ohio, and also from Chemsyn Science . Laboratories. une*a. Kansas. Standard reference materials, usually a solution of an Aroclor, are available 'hese SRms are discussed in Chapter 9 (see Table 9-III). V. PRODUCTION ANQ USE A. Aroclor and Related Mixtures PCBs were commercially produced as complex mixtures beginning in 1929 They are not known to occur *aturai\y. Most producers throughout tne world reduced or stocoea pro duction m tn# 1970s (Brmuman ana Oeno*. i?90). although torn# production continued through at least 1983 (Dersonal communication, Z. Kuntz. uSEPA. Washington. DC, December 1983). Production Oy Monsanto, the major world manufacturer, ceased m 1977. All of the commercial mixtures were synthe* sized by direct chlorination of oioheny) with chlorine gas. The averaga degree of chlorination was controlled by tne re action conditions to yield the desired physical ana chemical properties. The total worldwide production tnrougn i?76 is estimated at about Six 1011 g (1.3 billion pounds. Durfee et a)., 1976). of which about $.7 x )0M g (93%. 1.2S billion pounds) were produced by Monsanto m the United States. Tne total production of PCSs through 1980 is estimated to be about 1.1 * 10,a g (2.4 pillion id; unpublished 0EC0 esti mate. J. 0. Blttchly. PCS Seminar. The Hague. Netherlands. September 1983). The Monsanto PCS mixtures were sold under the registered trade-mark of Aroclor. The Arpc'or (the trademark designation is not used throughout this book) trade-name designated a variety of polychlorinated aromatic HONS 223466 16 Analytical Chemistry of PC8s mixtures. not just PCBs cor instance. Arocior 546Q 'S a Complex mixture of po I yChi or i nated teronenyis. Additional information nas Been presented m a revie* Oy Brmxman ana aeito* (1900) Commercial PC0 mixtures were used in a wide variety of aooi ic*tiQfs. including dielectric fluids n capacitors and transformers, neat transfer fluids, nydraulic fluids, luoncatmg ana cutting oils, and as additives m pesticides, paints, copying oaoer. carbonless cooy ("NCR") paoer, ad hesives. sealants, and plastics. In 1974. caoacitor manufac ture (10 10* g) and transformer manufacture x 10* g) ac counted for a11 of the PCBs sold by Honsanto. An additional 1.0 * 10* g used <n investment casting and 22 x lO7 g used >n soecia>ued neat transfer systems (totaling US of U S sales) were imported. The PCS used m investment casting, unlixe tne other commercial PCBs. was decacMoropipnenyi (Ourfee ei a 1 . 1976). As reviewed by WHO (1976). an Organcation for Economic Cooperation and Development report (1973) divided PCB use ihto three categories: Controllable closed systems. PCBs used as di electrics m transformers and large capacitors have a life equal to that of the eauipment. and with proper de sign leakage does not occur. When the equipment is scrapped the quantity of dielectric is sufficiently Urge to justify regeneration. Uncontrollable c'osed systems. PCBs are used n neat transfer ana nydraulic systems which, altnougn technically closed, permit Uakage. 7he need for fre quent replacement of small ouantities maxes recovery im practical. CBs are very wioe'y dispersed m small :aoacitors, ano there are great difficulties m collecting these items for disposal. Pi ssioative uses. PCBs have been used in the formulation of lubricating and cutting oils, m pesti cides. and as plasticizers in paints, copying paper, ad hesives. sealants, and plastics. In these applications. the PC8s are in direct contact with tne environment, and there is no *ay of recovering them when the product is scrapped. (06C0, 1973; WHO. 1976) It should be noted that one uncontroi UbU closed system, old fluorescent light ballasts, continues to pul PCBs in close contact with humans. When they fail, high indoor air concentration nave been observed (Macieod. 1979). MONS 223467 Properties 17 Since tne vast majority or PC0s of concern to an alytic*' chemists are derived from the commercial sources, tne genera- comoot't'on aro c ha rac te r' > tc s of these mixtures are -eleven "aDl* 2-lv presents a comparison of the com mercial PCBs Tne aoproximate compositions of Aroclor* by nomolog are presented n Table 2-v The composition has been sno*n to vary trom oaten to batch and according to the an alytical procedure As can be seen m Table 2-IV, with the eiceotion of 1016. tne last to digits of the Aroclor series numper correspond to the percent chlorine. A more detailed list of onysicocnemica1 Drooerties of the Aroclor mixtures is presented m Table 2*vl (Srinxman and DeKok, 1900). Similar tables are m tne literature (Hubbard. 1964. Hut2inger et al., 1974a. Ourfee et al.. 1976; NJ05H, 1977c; NfiC, 1979; Huttmger ano Roof, 1980a). Some of these contain other properties of the commercial mixtures. A common PCB-conta m mg product c'ass used in transformers and capacitors is askerel. The caoacitor askarels mcluoe neat Aroclor 1242. 1254, and 1016 and a mixture of ?S% Aroclor 1254 and 25% trichlorobn2ene. The most com mon transformer askarels were 60% Aroclor 1260/40% trichloroben2ene (Type A) and 70% Aroclor 1254/30% tnchloroben2ene (Type 0) The transformer askarels contain other minor com ponents used as free radical scavengers. The ASTM (1978a,o) pub'isned standard specifications for askarels. PCS production and use has been thoroughly reviewed by several authors (Sarofim, 1972. 0EC0. 1573. Hutnnger et al.. 1974a. Ourfee et al.. 1976; whO. 1976; JARC. 1978; NRC. 1979; CEC0. 1979; fir^nxman and OeKQk. 1980. Hiller, 1962) 8. Impurities m Commercial fixtures The impurities m the commercial PCBs are report edly 0.01% (NRC, 1979), a'thougn Tapie 2-v indicates that, m some cases, bipnenyl can be present at well over 1% levels. The presence of polychlorodiben2ofurans (PCOFs) has been documented (Table 2-vlI) at the microcram per gram level ano may account for some of the toxicological Drooerties at tributed to the commercial PCS mixtures (NRC, 1979). PCOFs, polymeric adducts suen as bolychloroouaterpnenyls (PCQs), and other impurities may form during us* and handling. The pres ence and levels of impurities are thought to vary widely from batch to batch. The subject of impurities in the commercial PCBs is presented m more oetail (2itko and Choi, 1971; Anon.. 1972; Nagayama et al., 1975; 8owes et al , 1975a, 1975b; Hiyat* and KasnmotO, 1976; MOSH, 1977c; Mor-it* et al.. 1977; Buser. 1978: Kemps et ml., 1978; Buser et al , 1970a, lARC, 1978; OECD. 1979; NC, 1979; Brinkman and OtKok, 1980; Vucete et al.. 1983; Cull and Oobbs, 1964). MOMS 223468 1 dli 1* 7- IV Cof>jr >*on ol (.oMerc m I I'f 0 Mi < <* N<mes * Nn Cl/ A|i|>rn* A(i|>ro A< ut L 1 tlllltlMI 1'1<< 1 nr l*y i 4 lene Kanechlor 1ent1 nr Mglecule wi \ Cl "Mill WI " \//\ \n? i?*?. 1016 \?*t l?!>4 l?6? I?fi0 12/0 A JU MO Ay > A60 III' 1 y\V% m*s Ill'll ?,noo 1 ,bU0 3,000 ?CK1 300 400 soo 600 1 IS 2\ I'M / 7 )7 11 721 0 7 S 19 >40 J 4? ) 411 4; ?'>> i 4 46 7* 1 9 S -i>4 176 4 66 1 60 166 0 6 e 6/ 369 /H1 / / 6S 419 4 6 / 69 ii 9 9 S >0 401 4 OK 10 M 499 6 4 Monsanto Industrial Chemical! CoApany, USA 6 04yer, GI0. ( C<lfro, 114 ly <1 linfQilmM theon *1 (.n*)tny, Prwlelec , I *ik * t I he two-tfiqit niMrix** sIxhiIU indicate the wt.t Cl, liowever, (hit does no l lit m with the Mnufacturer' i|i*c 11 >t at Wins Source 0rik*4n end OrKoh. 1900 Reproduced with permission. copyright 1990, (Isrvier 0io*edicel Press 9V HONS 223469 Properties Teb'e 2'V. Molecular Composition (wt.X) of Some iroclorj 19 Homo 1og (CMr met > 1221 12 32* Aroc1 Or 1016 1242 1248 1254 1260 0 10 1 SO 26 21 2 35 29 19 13 1 3 4 24 $7 45 2 1 4 1 IS 22 31 49 IS s 10 27 53 12 6 2 26 42 7 4 38 a7 9* a Fve percent unidentified ibiphenyi'). Source: Brsnkm*n end OeKok. 1980. Reproduced with permit* sion. copyright 1980, EHevier Biomedical Press 8V. HOMS 223470 > *1 I !> 1 , 1S>U.H " It,. ll l**M V*t 1 *i * f , i. -.... I i .. w r..t| ** t| O'sl 1 i... *.<p 1*1 I.J Wif'r. *1 1 i. .lr t * > n i ru ***( l*t 1 1 lu* I /SiN 4' /0*f 44 HlflV /S*C *./ 1 ^ (v i/n 1 1* Ml ft i mu 4 It l wu 1 f* H If \ IH %.% iik i / 1 4/4 M*l * 14 IS 1 b/fl Wfc 1i*4 i Mt P 4 | IW I-. l/M 1 > 41 V* 1 4441 l/M ( */ I.1 < t V4 I.W i n* iw 4 *%i .if|. 'a i *i II* I". 1 v% S<|| * .! 4 > fc+tt 1 P ^ t IM oyisl' r lui *>m lv*' | I* Wo* * !*. M4 * ltM <><.i ..(* l ;/\ i/u * a is )>% lA Ml* l/l IS* It i* JA IV* lib 1*0 A *14 it Its IW u. Its *f Mil. IS * JVW n mil IS su 14 to MI -- - - it tint It- ! l**'*< IS**. ))>* 1 /!* /< p It IS/ >1 11 - s 41 1t 41 s* 4* Sg 4 1 41 >' /S *1 v> tv 1 1 |M| /f / 1 1 i 1 <4 s | /!M if / MU \IM n 4 W 1/*// /* 1/ MQll 44 l 1 p l..4| 4/ S 4> 1/4 /> > (Uvl || 4 MONS 223*71 Properties 21 ib' 2-vll. !(>' of COM Co*rci*| PC8* "1 ll/rf In- Iftr*. *"t4- Hf 14- "fpn* f 01A 1 Arof10 ;:8 19891 lr0C'O' i:? A roc > 0 r i:i A'OC(or u] A'OC 1 Or 128* (!?69> A roc 0r ;8* f i?ro i A'OC'or 123* AroC'or '..'84 < 8021 AroC lor :;sa AroC'Or 1280 Aroc lor 1 .'80 119891 AroC 'or ::80 t*0<'Or .< 80 t A 3 > A'OC'or 1018 i 9-'*' 1 C'000*" A80 C'00*0" '84 Bh"OC'or OB-8 'OOP(*f 5010 Unpcn'flr 400 "UiuO'vn1 (uA*al 01 0 08 01 0o Ml 08 0 0? 23 0 28 01 02 0 02 0 08 01 03 01 08 02 N0 1* 03 01 07 8n 4 00 l2 0 03 22 02 02 0< 02 01 36 10 04 09 03 N0 80 1. 73 10 0 0 38 3 30 03 0 003 *0 * 0 91 14 09 0 4-0 8 0 02 19 1 10 08 08 03 N0 22 2 48 ;9 0 07 - 0 83 l 33 0 82 ' Cl 2.0 0 IS *8 l9 1.7 18 08 0.2 86 38 10 22 08 84 54 13 6 20 20 0 10 0 * n 0 *one a\ctd. B *130* HOM' 2 , ) , 7 .8* tir*-CPf. Source ucttl tt <1 . 1903 BtorotfuCta >th Dtnmign, cppyright 1983, (IttVf't Potr *irth lnunut(. MOMS 2234^72 22 Analytical Chemistry of PCBs C. Hpnoc h1 prop(pheny 1 S Monochloropiphenyl (isomer unspecified) was 4 'ow coneentrat 1 on component of several products manufactured py Dow Chemical Company Dowtherm G. a heat transfer fluia oe* signed to replace the Aroc'or-type fluids, is primarily pipheny* pnenyl ether put contemns up to 1.000 ppm monocMorppipnenyi. Manufacture of Do*tnerm G was estimated to produce up to 1 8 * 10s g {<.000 IP) of monochloropiphenyl (Cope'anp. 1979; Perlman, 1980; McCallum. 1982). Current production levels ar* assumed to be negligible, no other instances of monochlorobipnenyl manufacture in commerce are known. D. Decachiorob1 phenyl As can be seen in Table 2-lV. Fenclor On 's teen* meal grade oecacnlorobiphenyl. ]t as imported to me United States and used in investment casting waxes m the middle 1970's (Ourfee et al. . 1976. Brinkman and Cexo*. 1980). Presumably applications in other countries were s>m* ilar. E. PCBs as Byproducts PCBs can be unintentionally produced as by*products in a wide variety of chemical processes. Ths byproduct PCBs are also referred to as incidental PCBs, inadvertently generated PCBs. or unintentionally generated PCBs. Primary concern about these contaminants came about in the united States when the EPA published a rule to implement the t SC A ban on these PCBs (EPA. 1979d; velie and Xuntz, 1962) a rule amendment for PCB processes which are not closed or con trolled set an annua) average uooer limit of 2$ ppm for pro ducts (EPA, 1984b). Closed manufacturing processes ano con trolled waste manufacturing processes are excluded from me T$CA pen if the PCBs are not Quant i f iable; with practical limits of quantitation defined as 10 ug/mVresolvabie chro matographic peak for air; 100 ug/l/resolvable chromatographic peak for water; and 2 ug/g/resolvablt chromatographic pea*, for products and wastes (EPA. 1962c). Thus, current U.S. rules not only control the use of dilute commercial mixtures such as "contaminated11 trans former oils, but also imoinge on any manufacturing process which could manufacture PCBs as a by-product. These pro cesses include, but are not limited to. manufacture of chlor inated benzenes, chlorinated solvents (e.g., chloroform), chlorinated alkanes, chlorobhenylsiloxane adhesives, organosilicone drugs, organic intermediates (e.g., 3.3'-dicMorobenzidine salts), and pigments (e.g., pntha 1 ocyanme green) The PCB composition m these products or their wastes has MONS 223473 Properties 23 Been shown to range from 4 Single congener (e.g., 3,3 -di* cnloropipnenyi in 4 pigment; OCHA. 1962) to comote*. mixtures (e g . Over 60 congener* representing *1] 10 homologs in 4 cnlorirated aromatic production isu. Hanneman, 1982 Hodges t it, 1983). ' Since by-product PCBs ar* not generally looked for in routine production QC analyses, and no organised produc* tion records are kept or reported, estimates of byproduct PC8 production are crude at pest. *ne (U.S.) Chemical Menu* facturers Association (CMA) surveyeo 'ts members on the suOject of oy-product PCB manufacture, processing, distribution, and use (Pittaway et a l , 1961, 2a M eta)., 1982). The pro* duction of byproduct PCBs nas also been estimated by EPA (1982b) and versar, 1982) Based on these surveys, along with data from the Ory Color Manufacturers Association, the total annual By-product PCB product'cn m the United States is estimated at about A S x 10; g (100,000 lb), of which < 5 x 10* g (11,000 IB) is found 'n products and < 4.S * 10s g (1,000 lB) enters the free environment [personal com munication, R. J. Fensterheim, . arrn, and T. Hardy, Kirkland and EUis. Washington, Q.C. , February IS. 1983]. f. PCB Formation Ourinq Water Chlorination A laboratory study (Gaffney. 1977) demonstrated the formation of mono* and dichlorobipnenyls under municipal water chlorination conditions. The lack of other studies in tms area ano the oaucity of data on C3 formation in munici pal water systems would indicate that the incidence of PCBs from this source is small, relative the commercial mix tures already in the environment. G. PCB Formation from Thermal Oeg-idation of Other Chlorinated Organics ---- Mono* through tetrachlorobiphenyls have been found in the pyrolysis (helium atmosphere) and combustion (air at* mosphere) products of chloroalkanes (Bergman et al.. 1964b). Polychlorodedecanes (S9X chlorine and 70% chlorine) were com* busted for 10 to 1.200 sec at temperatures from 300 to 700*C. Several hundred micrograms of the PCB isomers were found under most conditions. Many other comoounds were detected, including other chlorinated organics, and many nonchlorinated organics. St may be speculated that combustion of other chlorinated organics may !e4d to formation of PC8s. HONS 223474 24 Analytical Chemistry of PCBs vt. environmental OCCURRENCE A Central LevE'S ang - ' >trBut 1 Oft PCBs may be consige-ea uoiouitou* pollutants They have been founo in nearly a1' marine plane ana animal speci* mens. fish, mammals, biras Especially fish-eating oiras). Pira eggs, ana. of course, hymens. AM u S. resiotnts have measurable PCBs m their eaiccse tissue (Lucas et a 1. 1983) The occurrence m animals was thoroughly reviewed Oy Wassermann et al (1979) ar>0 is summarized in Table 2*'/M! Generally, the PCB levels inc-eese through the fooa chain, as deoicteo in figure 2*2 ana re.-ewea py EPA (1980d) Selected Evels >n air, water, soil, seoimeni, ano food are summarized in Tables C* 1 x througn 2-XH. Note that the units are not the same all matrices This is a re* flection of the general leve-s of parts per billion m soil, sediment ana food, ana sub*pa-;s per trillion in water The concentrations m ill matrices generally span a large range since everything from highly oolluted to pristine environ ments hat been motutorto. Differences m analytical methoc- ology and elimination of interferences make direct comparison of the data difficult. In adcition, some matrices are poorly defined in the literature, for example, the hign value re ported for birds (14.000 oo) may in fact be selected tissue since tne value was reported 'or an eagle, wmch is not ees* ily analyzed ^_n toto. Dietary exposure tc 3CBs -as reviewed by Corale et al. (1970). Tne environments' occurrence of PCBs nas Deen reviewed in numerous articles ana monographs (toos. 1972. Finklea et al , 1972; Nisbet. lr*2a; Holden. 1973. n<srvey et al., 1974, kutz and Strassmav 1975; Fuller et al . 1976; Risebrough et al.. 1976, QeNarai ana Oesmarais. 1976, Fmlav et a)., 1976; wmO, 1976; NIOSh, 1977c; CoraU et el.. 1978*. I ABC, 1978; Wasserman el al.. 1979; National Research Coun cil, 1979; PA, 1980d; lanangan, 1980b; kimorougn. 1980b, Pavlou, 1980; Hutzmger and Roof, 1980b; Baker et al . . 1960; Eisenrich et al.. 1981a; Murpny et al., 1981; Miller, 1982, Mackey, 1982, Vodicnm, 1983. Hunter, 1983; Eisenreicn et al., 1983a, 1983b; kauss et ml, 1983; Cone etai., 1983; Farrington et al., 1963; lei ft* et al., 1963; Tanabe et al , 1983; NT IS, 1982, 1983a, 1963b. 1984a. 1964b). 8. Major Environmental Cantami net i on Two major contaminations by localized discharge are of note since they nave received so *ucn attention ana nave stimulated analytical research: Yusno and the Hudson River MONS 223475 PfOprtis Table 2*vl11 Occurre-ce of PCBs in Animals 25 Organs" Concentration Range (yg/g) Marine Organisms Zooplankton Shellfish Seals Whales and Oolpnins F > sh fresh Water (USA) Marine . Birds North America Europe Eggs Terrestrial Animals Humans Adipose (general population) Plasma (general population) Plasma (occupational exposure) Adipose (Yusno) Plasma (Yuiho) Mi lit Milk-extracted lipids < 0.003 - 1.0SS < 0.003 - 7 3 * 212 0.012 - 147 Q.l - 15 0.03 - 190 0.1 ' 14.000 0.5 - 9.570 0.1 ' 434 0.01 ' 45 0.3 ' 10.0 0.001 ' 0.029 0.036 - 1.9 0.7 * 75. 5 0.002 - 0.015 0.01 0. 39 0.01 * 18.6 Adapted^ from *assermann et al . ;S79 Reproduced un per* mission, copyright 1979, New one Academy of Science. MOMS 223476 26 Analytical Chamistry of PCBs 'S.OOO figure Z'Z B1oaccu*u)etion of PC8s in the lake Ontario Ecosyste* A>) values art in parts par billion (ng/g). Reprinted, with permission, from Safe ( 1980); copyrignt 1980 by Elsevier Sioeiedical Press 6.V. HONS 223^77 Properties fable 2*1* *etrn iot *t10" ::;jrr*r>ct of C8s Concent 'n ion lno/*1) m Air Source 27 Ambient Hr *nUr(tic Coast Remote Grm i**et Bur* l UrOin Various US* Locations Marine Air Atlantic Ocean Gulf of *e1C0 North Pacific Ocean North Atlantic Ocean *est Pacific Ocean North Atlantic Ocean North Atlantic Ocean tokyo. Japan Matsuyama. Jaoan Sweden 0 06 0 2 0 0? 0 S 01 -S 0.1 - 2 O.S - 30 0.02 - 36 0 OS - 2.0 0. os 0 2-09 0. SB ; 94 o 06 - : ; : 05-02 0 OS - * 6 20 2-S 09- i9 I enabe et a l . 1983 i1 senr*ich t ii.. 19830 t > >enr*lch et a!. . 19830 C'senraicn et a) . 1983b isenf*ticn et a) . 1983b NC. 1979 NRC. 1979 **), 1976 Gia* et ai . 1976 Atlas and Ciam, 1980 TeneOe et a) . 1982 Tanaoe et a). . 1982 8iOlenan et a) . 1976 8oieman et a) , 1981b X'morougn. 1990b Kimbrough, 1980b WHO. 1976 MOMS 223478 28 *i1 r i * Analytical Chemistry of PC8s T|b 1 2I * (cantinuo) IOC Ition CO"C*nt *! t ton (ng/oJ ) Sourct US* u$a, ;.->aoor Conn** initio by ngnt 8i 1 list Burnout USA, Inooor S S .860 19 620 US*. Inaoor Htr $p n 1 S tti U$A, t*nOfit\\ OSA. t'lctnei! Suostitloot USA. Vinjfomifc *inuf ictu'-l'' u$A. So< 1 i $-ti ' 10 - 190 2 18 1 4? 1? S.900 10 - 10,800 Stick CMSCO. i 0or40O. Arkmsll 12.000 - SB.000 RoH (ns, 0r P*rk, toil 9.8 OCCupItipn|I Hiswchumts. PCS Ustr Hints ClDIC'tor Victory 0 1-S 8 10* S* 7 10* vinous Qccuoitiomi nviron*ntS 0.01-10 * 10* WHO. 19?6 Micltoa. 1979 l'ctoo, 19?9 HlcLlOO. 1979 *ICLIO0. 1979 *ICtlOO . 1979 "ictioo. 1979 "ictioo. 1979 Crickson It |1 . 1984| Cnckson it il.. 1984* N10SH, 1977c N]OSH, 1977c KiOrOugn 1980c MOMS 223479 Properties Ublt 2-t 29 Occurrence of PC8 S in Weter Hetn* LOCH 'On Concentretion (ng/t) Source e-terct > c. ie *nl*rctic . Sr>o *ortn Pec' f' c Oceen weii pc*ric Oceen Oeeo Oceen Atlentic terreneen Coest Seoen. River Sweden, Teo USA/Cmeoe. Creel I.1MI Jeoen. Teo u$A. ie*e Micmgen, So' ' 1 S' le uenere 1 jnoo 1 1 uteo R iveri uSA/Ceneoe. Greet lines Generel. Meotreteiy Polluted Rwers Generil. mi only Pol luted Rivers Remote 0 03 0 07 0. 3 - 10 0 3 4.2004 0.2 - 1 1 0 04 - 0 25 0.03 - 0.6 0.3 * 8 13 Tenibe el el , 1983 T|n*be, el el , 1983 8i0le*en et el . 1976 Teneee 6 Tetsukiwe 1980 Tmeoe el el.. 1982 Teneoe et el, 1983 Hirvey 6 Stemneue 1976 eioer, 1976 0.5 033 0 8 31 WHO, 1976 who. 1976 NRC, 1979 1 - 100 100 4S0 WHO, 1976 whO. 1976 < 05 WHO. 1976 < 5 WHO, 1976 < SO WHO, 1976 < 500 WHO. 1976 0. 1 10 Enenrticn et el., 1983b MOMS 223480 30 Analytical Chamistry of PC8s uei M (cootmgca) CoCt"t*`4t l oo ii LCC *t ' O'' log/l) bounce Mjrinc Bu^4 Grt4t HkCV Urblft 0 5 - 10 1 50 10 150 10 250 ' eno*ijn Cl H . 1983b. *t>4l 4 Cl 4N, I960 Hnrt i<n ct <1 . 1983b l' scnr*icrt rill. 1983b >ioot,eft Cl jl . :983b 4 Rf.'t* ftf iVuO'Cl at COIHil cnfl OD*n oct<n s'tts. e no *'gnific4nl cooctotMi'Oft w*r* odwovco n Ototns from 0 to 4*500 n. HONS 223461 Properties. Table 2'<I 31 Occurrence of PCBs in So*) anc Sediment tr t Locat <on Concentration (ug/g) Source So i ] Sediment Sweden Japan - Agricultural Japan * Near l lectncal Component factory USA * 1972 USA - Urban USA * Transformer Manufacturer Spill Site 16 km Oownstream Sweden * Atmospheric Oeposit ton Only Sweden * Potential Industrial Contamination USA USA/Canada * Great Lakes Japan (1,449 sites ) Japan * Polluled Si te 19 < 1.000 510.000 (99.9% < 100) (27X < L00) 17 - 17.8C*. 1,400 * 61,oc: 600 8 - 20 4 * 170 20 * 300* tr - 290 < 1.000 up to 2,700 WHO, 1976 WHO, 1976 WHO. 1976 Kimbrougn, 1960b Kimbrough. 1960b MacLeod, 1979 WHO, 1976 WHO, 1976 NRC, 1979 NftC, 1979 NRC, 1979 NRC, 1979 Kimbrougn, 1960b Kimbrougn, 1960b 3 M*oian-a iues oy state ior 10 ;o 293 samples.itste in nine suits MOMS 223482 32 Analytical Chamiatry of PCBs Table Occurrence of PCBs m Food Matrix Food f i sn F ish Byproducts Cneese Hi 1 k Snell Eggs Location USA USA USA USA USA ' <J7A Concentration (ug/kg) 1,870 1.170 250 2.270 550 The contamination of other ecosystems, including New 8ed'o*-o. HA, Waukegan. Jt. and Bloomington, IN has been reviewed (Weaver. 1984 > 1. Yusho: "Yusho'' w*s a mass food poisoning caused by the ingestion of a commercial brand of rice oil contaminated with PC8$, polychlorinated d'benxofurans (PCOFs), and polychlorinated Quaterphenyls (PCQs). The poi soning occurred in Western Japan in 1968, involving more tnan 1,600 people. The clinical criteria for the Yusho patient included fatigue, ntadacne. joint swelling and pain, bursi tis, inhibition of growth and tootn formation in children, anemia, unusual PC8 patterns in the olooo. reduced neural conduction velocity, acneform eruotions. increased skin pig'mentation, and swelling of tne eyes. PCS concentrations m blood averaged about 7 ppb (range 1*3?) for Yusno patients (Kuratsune. 1980), wnilt a control population of normal per sons had a mean of 3 ppb (range 1*7) and a grouo of PC8 pro* auction workers showing only minor clinictl signs had a mean of 364 opb (range 60*920). This, plus other evidence, indi cated that the PCBs in the rice oil were not solely resoonsible for th clinical mam festations. other, more toxic, chlorinated aromatics have been found in the Yusho oil. in cluding PCDFs and polychlorinated Quaterphenyls Out not ooly* chlorinated dibemodioxins (PCDOs). Table 2-X11J summarizes the PC0F concentrations (Kuratsune, 1980). Polychlorinated Quaterphenyls. along with minor amounts of oolychlorinated terphenyls and polychloroquaterohenyl ethers, were found at concentrations equal to or up to four times that of PCBs in rusho oil, although saponification during cleanuo may have created these compounds as artifacts (Hiyeta et a 1. . 1977. NRC. 1979). Many of the Yusho patients have died and epi demiological studies continue. Yusho was tne suoject of a MOMS 223483 Properties 33 Table 2-XII] Concentrations of PC8s and PCOFs ana Their Radios m Yusho-Reiated Materials Matena t$ PCBs (,ppmb.) PCOFs (ppm0) PC8s/PC0F Kantchlor-400 (unused) Yusho oils* Yusho patientsc Adipose t<ssue Liver 1.000.000 ca. 1.000 13 0.05 ca. 20 5 0.009 0 013 50,000 200 144 4 a Proauced on February 5 or 6. 1968. b On <*r\o>e base. c Two patients *no died m 1969 and one patient who died in 1972 were included. Source: Kuratsune. 1980; reproduced with permission, copy* right 1980 by Elsevier Biomedical Press BV. book (Higuchi. 1976) and was more recently reviewed (Kuratsune, 1960). Other reviews and key articles include Kuratsune (1972); Kuratsune et a). (1972); Nagayama et al. (19?5); Miyata and Kashimoto (1976); Miyata et al. (1977); Honta et al. ( 1977); 8owes et al. (1976); Cordle et al. (1978); Kamps et al. (1978); Urabe et al. (1979); Rappe et al. (1979); Kashimoto et al. (1961a. 1961b); and Masuda et at. (1982) a similar outbreak >n Taiwan affected about 2,000 people Detween 1979 and 1961. This so-called Taiwanese vuiho incident was reported Oy Chen et al. ( 1980. 1981. 1982); Kashimoto et al (1982); Masuda et a) (1962); and Chen and Nites (1983). 2. Hudson River- General Electric manufactured PC8*containing capacitors in two plants at Hudson Falls and Ft. Edward. New fork. Both plants are located immediately adjacent to the Hudson River about S km apart and about 320 km (200 miles) from the river mouth. PCB discharges from these plants have led to massive contamination of the Hudson basin estimated at a total of 6 & 10* g. The problem nas been reviewed by Horn et al. (1979) and Carcich and Tofflemire (1982). Average sediment levels ranged as high as 150 ug/g in some of the river reaches. with occasional samples ex~ ceeding 1,000 pg/g. It- has been estimated that 2.6 * 10* g/year of PC8s flow over the dam 67 km (42 miles) downstream of Ft. Edward and into the estuarian portion of the river. MOMS 223484 34 Analytical Chamiatry of PC8t Thus. "01, only is the ecosystem CO"Uminated. Out th PCBs not controlled end the contami nat i on is spreading. The contamination of the Hudson River Basin ex ceeds. m level end scoot. any other tree found to dtte m the United Stales River sediment concentretions ere et teest an order of magnitude higher then otner contaminated systems (e g. , lake Onterio, lake Michigan; Escambia 8ey, nonoe; end soils from the Monsanto olent). Tne PCS levels et e few other sites (eg., weukegen River. Illinois end Housetomc River. Connecticut) ere comparable. out the sue of the areas contaminated do not aooear to be as greet es the Hudson River Esthetes of the quantity of PCBs in the sedi ments of me Greet lanes (e.g.. lake Onterio. 9 k 10* g; Lake Erie, i & * IQ7 g. and lake Michigan, ? * 10* g) ere consid erably lower men those for the Hudson River (6 * 10* g; Horn et al.. 1979; Cercicn end Tofflemir#. 1982). Between 19$$ end 1974, General Electnc's ft Edward and Hudson fills fa cilities purchased 3 5 * 10` g of PC8s or approximately 1SX of Monsanto's domestic sales during that time. This suggests that General Electric's discharges to the Hudson River Basin might represent close to 15% of the nationwide total dis charges to the environment (Horn et el.. 1979). Vl). environmental transport AND pate Of the 5 7 * 10J1 g (1-25 billion lb) of PCBs esti mated to have been produced in the United States (NRC. 1979, see Section v. aoove. for more details) aoout 5.5 * 1011 g ar thought to be m service, destroyed, or otherwise un available. leaving 0 11 * 1011 g (24 million lo) tn the mo bile environmental reservoir Table 2*xlV presents an esti mate of the PCS distribution (Mackey. 1982a). In 1979, the NRC estimated that $0-801 of the PC8s m the environment had Oeen deposited m the North Atlantic Ocean ana that the major continental sink for PC8 is freshwater sediment. The environmental transport of PCBs is complex and global. PCBs are transported by air, water, fish, birds, and other routes. They are deposited from air oy rain, snow, dry fall-out, and vapor-phase deposition. As noted in Tables 2*IX and 2*X, environmental transport has resulted in fairly uniform global background of PC6s. &y virtue of their high lipid-water partition ratio (see octanol-wattr partition coefficients in Table 2-111). PCBs tend to accumulate in fatty tissues. The long-term dis tribution in tissue is adioose > skin > liver > muscle > blood (Safe, 1980). As with tne wei l-publicued case of 0DT (Carson. 1962). PC8s biomagnify through the food chain (see HOMS 223485 Properties Table 2-XIV 35 Estimated Distribution of P>C8s m 1981 Mass of f>CB (g * 10*) Concentration (g/m3) Atmospnere water Fresn water sediments Fresn water biota Soil - natural Soil * sewage sludge Vegetation Wildlife LivastoCK Humans TOTAL accessible Oceanic water and biota Oceanic sediments Total near oceanic Landfill and storage Other inoustry Electric uti)sties TOTAL INACCESSIBLE TOTAL OEGRAQEO ANQ A0VECTE0 GRANO TOTAL (eaua)s amount produced) 18 20 4.000 15 1.000 4.800 1,000 0.3 0.6 S 10.BS9 6.000 1.000 7.000 175.000 75.000 74.000 324,000 228,000 570.000 1.2 10'* 1.7 10 9.3 x 10 2 30 1. 1 i 10'* > 1.7 * 10 3 0.46 9 3 x 10 3 0.36 Source: Macxay. 1962a. fteoroduceo with permission from aulnor and Ed>$on Electric Institute. Table 2-VJ11 >. A concentration factor of nearly 10* was re ported from Lake Ontario water to herring gulls (Interna* t'onal Joint Commission, 1977). The environmental transport and fate is of great importance since use and disposal practices of existing PC8s must be controlled based on sound predictions of their en vironmental impact. The subject has been reviewed (Nisbet and Sarofim, 1972a, 1972b; Nisbet, 1972b; Ourfee t al., 1976; Sioleman et al., 1976; Risebrougn et al.. 1976; Fuller et al.. 1976. Finlay et al.. 1976; WHO, 1976, N10SH, 1977c, Pomerantz et 11. . 1978; NRC, 1979; Hutzmger and Roof, 1980b; Pavlou, 1980. Miller. 1962; Mackey, 1982a. 1962b; Neely. MOMS 223486 36 Analytical Chemistry of PCSs 1983. Vodicnik, 1983; Moolenaar. 1983; E i snre t ch and Jonnson, 1983. Hunter, 1983; James. 1983. Leifr t *1 , 1983: NT I $, 1984a. 1940; MaCkay and Hughs. 1984 ) a recsn monograph. Physical 8ehavior of PCBs m the Great Lakes (Mackay et el.. 19030). contains U cnapters *n>ch discuss various Aspects of environmenta1 transport and fate viu. OESTSUCTIQH, DEGRADATION. ANQ HgTASOLlSH PCBs ar very stable compounds and do not degrade easily However, under certain conditions, they may be de stroyed By chemical, thermal, and Biochemical processes These may occur intentionally (e.g.. incineration), uninten tionally. or metaoo'icaUy 8ecause of their high tnermooynamic stability, all degradation mechanisms are difficult Intentional degradation generally reouires nigh neat or cat alysis. Environmenta1 and metabolic degradation generally proceeds quite slowly relative to most other compounds A. Intentional Destruction Destruction has generally been limited to incinera tion. although some chemical degradation processes (e.g., de chlorination with metallic sodium) are permitted m the United States and other countries. PC8 destruction is of particular analytical interest since the determination of de struction efficiency requires the analysis of feed stocks, stack gases, and other effluents. In tne United States, incinerators are strictly regulated to assure that PC8s are effectively destroyed. The rules specify for nonliquid PC8s (i.e. . solids containing PCBs. such as caoacitors) that < 0.001 g/kg of the PC8 intro duced may be emitted to air. This 99. 9999% (** s*-9 * s") de struction efficiency has generally been the overall target m the United States for all emissions from all PC8 categories. Most incinerators employ a combination of nigh heat (ca. 1200*C), a long residence time (> 2 sec), an agitation mech anism such as a rotary kiln to mis and move solids through the heated zone, and various pollution control systems (fil ters, precipitators or scrupbers). PC8$ may also be effec tively and legally destroyed in the hign efficiency boilers used by utilities to generate electricity (PA. 1983d; Hunt et al. . 1964). Several nonthermal processes for PCS destruction are being used, investigated, or developed- The chemical techniques include adsorption, chlormolys is. catalytic dehyorochlorination, microwave plasma, ozonation, photolytic. wet air oxidation, reaction with sooium naphthalide. reaction HONS 223487 Properties 37 with molten sodium, and reaction with a sodium salt in an amme solvent. Tie biological orocesses include activated sludge, trickling filters, and special bacterial methods. Tne `object of nontnerma> pCB destruction nas been reviewed (Ackerman et al , 1981. Ackerman et a' . 1983a; fradkin and Bansas, 19B2. Addis and Komai. 198*) Reviews by Erickson and Shah (1983) and Neulicht et al. (198S) contain annotated b'bliographies of major books, articles, rules, and documents on RCB destruction. A book on detoxication of hazaroouS waste (Exner. 1962a) contains two reviews of RCB destruction technology (E*ner, 1982b; Weitzman 1962), a cnapter summarizing the U.S. RC8 regulations (velie and Kuntz. 1902), and four chapters on research into novel destruction technologies (Barton and Arsenault, 1982; Brown et al., 1982, kitchens et al.. 1982. Killer and fox, 19B2). 8. environmental Degradation In the environment, photolysis is the only signif icant chemical degradation process (Nutzmger et al.. 19?2b; WHO, 19?6; NRC, 1979). Several recent publications also dis cuss photochemical degradation (Kalmaz et at.. 1962; Parlar and Mansour. 1962; West et al., 1963; Oilling et al., 1963, Zabik, 1983). Th* atmospheric half-lives for photodegrada tion are dependent on the degree of chlorination. Half-lives of the monocMorobiphenyls r*nge from 0.62 to 1.4 days, while pentacnlorobipneny) had a half-life of 67 days (Oilling et al., 1983). Acid- or base-catalyzed reactions are not likely to degrade RGBs under environmental conditions It should be noted that volati1ization and other transport mechanisms can result m significant removal of PC8s from an environmental compartment without any net loss of RCBs from tne environ ment. Once volatilized, however, the cnances of photolytic degradation are increased- Tne environmentaI degradation of RGBs nas been reviewed (ZeU and BalUcnmiter. 1980; Meely, 29B3; te'fer et al . 1983). C. Microbial Degradation Microbial degradation of RGBs depends on the degree of chlorination and the position of tne chlorine atom on the biphenyl molecule. Lower chlorinated biohenyls ar readily transformed by bacteria, out tne nigner chlorinated compounds are not. as illustrated m Figure 2*3 (Moo'enaar, 1983). In addition, the position of chlorine substitution affects bio degradation; ortnp substitution decreases tne rate- The major products are conjugated and/or free nydroxychlorobiphenyis A furtner degradation product of 4-cniorobiphenyl is 4-cnlorobenzo'C acid (Messier et a).. 1983). MOMS 223488 Hk'j Mp|irinle<( /riHi (1983) HONS 223489 Properties 39 The half*l*ves of tne t h r # e monccn I orob ipheny 15 ** reported to be 2 to 3 days m riv*r ,^r (8ilcy et at.. 1983) wong and Kaiser (1975) sno^eo cc*;'ete metabolic breakdown of Aroc'or 1221 by lake water battena after 1 montn incubation. The products were identif>ec only as "sev eral low molecular weight compounds." fgrukaa et al. (1978) studied the microbial degradation of 31 PCB congeners from mono- tnrougn pentacn1orooipneny1s Tney concluded tnat de* gree of chlorination and extent of ortho substitution af fected degradability, as discussed m me pre.'ous paragraph. In addition, they found that PCBs with a none-;or 1nated ring degraded faster, with preferential fission 0* tne unsubsti* tuted benzene rings. Microbial degradation *a& been reviewed (Menzie. 1978. L980. NftC. 1979. teifer et al . 1983; Peyton 1984). 0. Metabolism by Higher Anma1s The major PC8 metabolites in hig-e<- animals are mono* and aihyaro*ych)orobiDhenyls and tne r conjugates. These compounds are then excreted in the ur--t. figure 2*4 summarizes the uj vivo metapolites (Safe, 1980 Methylthio- ana methy1sulfone derivatives have also been identified in tissues from Yusho victims (Haragucni et al.. 1984) and other environmenta1 matrices, as reviewed by Bergman et al. (1980). Bergman et a) (1960) synthesized and characterized 25 of the methylthio* and 28 of the methy1&u1'cne PC6 deriva tives. The metabolic rates are both isome'* and homolog* dependent. The higner the nomolog, tne siowe' '-~'t metabolism (Safe. 1980) Most of tne studies reported '**e used rats, raobits. and otner nigh level species. It ; assumed that hydroxy)a11 on <s also tne major degradation -oute in otner species Biological degradation ooes not s.pificantly reouce the Lota) env 1 ronmenta 1 burden, eltnougr *t does have a marked influence on the relative concentrations of PCBs (1 e. . chromtographic patterns) passing though the food chain (who. 1976). The metabolism of PC8s has been reviewed (Hammond, 1972; Hutzmger et al.. 1974a; NJOSK 1977; Htnzie, 1976, 1980; JARC, 1976; Matthews et al., 1975: Matthews and teto. 1979; Safe, 1980; Safe et al., 1980; nutzingtr and Roof, 1980b; Safe et al.. 1963b; Hutzinger, 1963a, 1983b; Matthews, 1983; NTIS. 1984b). E. Degradation During Use a0 Analysis Some PC8 uses generate sufficient *eat to degrade commercial PC8 mixtures, forming PCOfs (8usr et el., 1978a, 1978b) and polymeric products (Zitko and Crci. 1971; NRC. 1979). These finding* are of interest, especially to the MOMS 223490 40 Analytical Chemistry of PC8a c ** tttiitn a* "4 twllv*- Figure 2-4 Common ]_n Vivo PC8 Hetabolites Pepriited. with permission, from Sjfe (1980). copyright. 1990 oy Elsevier B'OmeO'Cil PreSS B v .oncologists and epidemiologists studying the health effects of PC3s. since tone contaminants can confound research re sults The classic case of toxic effects caused Dy PC8 con taminants is the Yusho incident discussed in Section VI.8.1, above. A variety of hostile conditions can degrade PC6s Dy oxidation, hydrolysis. alcoholysis. and photochemistry (Pomerjntz et al.. 1978). These conditions are of particular interest to those investigating nontherma! PCS destruction methods. In addition, the analyst must be aware that certain harsn cleanup techmoues can destroy PC8s, especially tne lower chlorinated congeners, This topic is addressed more thoroughly m the acid and base cleanup sections of Chapter 6 (Cleanup). P Degradation -n Fires An extreme case of degradation while in use occurs when PC8*contaimng electrical eauipment is involved m a HONS 223491 Properties it f i re Not Only are PC B S degraded Out they are *1*0 dis persed Sucn an event occurred m 1901 m 0ingn*mton, New York, ner* the 18-st.ory State Office 8\j'icingwtt damaged by rire (vuceta et a) , 1983, EPA, 1984*) leakage from a PC8 transformer was dispersed tnrougnout tne building. The av erage pC8 concentration on exposed horizontal surfaces was 16? ug Aroclor Samples of tne soot were found to contain PCDOs (20 ug/g), pCQFs (700*2,200 ug/g), and ooty- cnlonneted oionenyienes (S4 ug/g). HiUer et al. (1983) analysed samples from tne same fire and found 200 ppm of 2.3,7,8*1 COP and 2 8 oom of 2,3.7.8*TCD0. Similar results at several otner PCB fire sites >ere reported by williams et a) (1983a. 19830. 1985) Tne contaminants from Binghamton and otner ''accident" sites -ere recently reviewed (Vuceta et al.. 1983) lao'e 2-XV presents a summary of the compounds found at these sites Some research nas been conducted to identify the products, expecially the PCDFs. of incomplete PCB combustion (Buser et al.. 1970a.b. Buser and Raooe. 1979; Rappe et al . 1983. Buser and Rappe. 1964. Rappe, 1984. fcncfcson et al 19840. 1984c. 1904e. 1985a. 1988b; Swenson et al.-, 1988). PCOfs were observed to form on heating in sealed ampules con* taining PCB$ (Aroclors or individual congeners) and oxygen (Buser and Rappe. 1979). Even at temperatures as low as 300C. increased levels of PCGFs were observed after 1 wee* (Morua et al., 1978). Figure 2-8 shows the reaction pro* ducts of 2.2' .4.5.5'-pentachlorobipheny 1 The triehlorodi* benjofuran was the major product, with smaller amounts of the four tetr- and a single pentachloro dipentofu'-an (Buser and Raooe. 1979). Using a bench-scale thermal combustion system, E-iCkson et al. (1984b. 1984c. 1984e. l?95a, 1988b, Swanson et al., 1988) found that the optimum conditions 'or PCOF for mation from PC8s are near 67S*C for 0 3 sec or longer, with 9% excess oxygen. Under these conditions, percent levels of PCDFs are formed from mineral oil or silicone oil contami nated with PC8s at 3 ppm or greater. The amount of PCDFs formed from the PC8*containmg materials was directly depen dent on the amount of PC8s fed into the system. As illus trated in Figure 2*6, the composition of the PCDF mixtures formed was mdepenoent of the feed concentration or matrix. PCOFs and PCOOs are formed at mucn lower levels from a tricnloropenzene dielectric fluid used in asfcarels which con tained no detectable PCSs. As illustrated in Figure 2*6, the composition of the PCOF mixture formed from the tricMorobenzene mixture is different from that formed from the PC8 feed HONS 223492 Accident table l*XV SiMiry of Chlorinated Aroaatic Hydrocarbons Ortecled Ouring Different PC6 Accidents* PCOOs P6f$ f*CQs tQf"s RTs PCIPi pepy, ttdi Joronto 5 ppa Norrlalje, Sweden 45*107 pg/g Binghaaton, NY 2.8-19 9 ppa 124-2,163 ppa bb b Stockholm (1981) 43*104 pg/g bb b Skovde, Sweden 0.01*0. 773 pg/a1 bb Yusho, Japan 1-18 ppa b bb Yusho, Taiwan 0.18`l.M ppa b b a Prfls * polychlorinated quaterphenyTs ` ACQCs * polychlorinated quaterphenyl ethers PCf* polychlorinated terphenyls PC8Ps * polychlorinated biphtnylenes PCfYs * polychlorinated pyrenes PCCYs s polychlorinated hrysenes. b Quantification ami conf iriealion not possible doe to lack of standards Source. Vuceta et at , 1983 Reproduced with peraission, copyright 1963, fclectric Power Research Institute. b D b HONS 223493 Properties 43 Figure 2*5. PolyChlorin*td Dibenzofuran* Formed from Thermal Oegraoation of 2,2' .4.5,5'*Pent*chlorooionenyl Mechanis* 1 involves loss of two ortho chlorines; Mechanism 2 involves loss of HCl and a 2,3 chloride shift; Mechanism 3 involves loss of HCl, and Mechanism 4 involves loss of h2. The sample (100 pg) was heated in tne presence of air in a sealed ampule at 600C for 60 sec. Reprinted, with permission, from Buser and Raope (1979), copyright 1979 by Pergamon Press. HONS 223494 44 Analytical Chamlstry of PC8s TETRA COF* 70% Afsclor 1260 30% TficHlorobtnscn* T'<C.K|orbnt*n Figure 2*6. Tetrachlorodibtnzofurans Formed from Thermal Combustion of PCBs ind * Trichlorobeniene Mixture AH mixtures wfr* combusted it 675*C for 0.8 sec witn 8% ex* cess oxygen. The products were tripped on XA0*2, extracted, cleaned up, end inilyzed by HRGC/EIM5. The simples were in* ilyzed under slightly different conditions, accounting for the minor variations in the cMormitogriphic pitterns. Reprinted from Erickson et al. (1984b). HONS 223495 Properties 45 The formation of PCOFs and other compounds from thermal degradation o< CBs has been reviewed (Choudhry and Hutzmger. 1983. Addis and Komai. 1984, Rapoe, 1984. Erickson et a) . 1984b). ix. toxicology The Duoi i c, leg*', and scientific concerns about PC8s arose 'rom the findings that PCBs were toxic and there* fore undesirable as commercial products or environmental con taminants. The evidence for this toxicity was sufficient for special citation by the US. Congress in the Toxic Substances Control Act (see Chapter 1) as well as similar actions by other governments. However, the degree of toxicity and the nature of the effects on man and other organisms has been ana continues to be highly debatable The U.S. National Research Council (1979) conc'udeo, "An analysis of PCB data, leads to the con clusion that PC8s are persistent, and are likely to ac cumulate. PC8s do not appear particularly toxic for short-term exposure, but results are subject to inter pretation (Roberts et al. 1978)." Table 2-XVI presents the NRC1s survey of the chrome effects of PC8s. Table 2-XvII presents a summary of PC8 effects from Reggiam (198?) ana Table ?-xvlII oresents a summary of the pathologic findings from McConnell (1980) Many studies of both occuoat'on*) or environmental exoosure and laboratory exposure are subject to question because of me type ana punty of PC8 useo. All of tne occupational and environmentaI studies ana many other laboratory studies have been conducted with commercial mixtures. Not only are the effects of uo to 70 different PC8 congeners being studied si multaneously. but the possible presence of contaminants such as polychlorinated terpnenyls and ouaterpneny1s and the much ore toxic PCOOs ana PCOFs make assignment of tne observed effect* to PCBs subject to criticism. Some studies, however, have been conducted on in dividual pure congeners. These studies indicate that PC8 toxic'ty is dependent not only on the degree of Chlorination but also on the isomer. For instance, those PC8s which have no ortho-substitution and are heavily substituted at the meti and para positions are capaple of assuming a planar conforma tion wnicn can interact with the same receptor as tCOO. Ex amples include 3,31 ,4,41tetrachlorooioheny 1 (I), 3,3" ,4,4' ,S-0ent4Ch I or obi oheny I (ID, and 3,3` .A.4' ,5,5'" nexacMorob'pnenyl (III). HONS 223496 46 Table 2-HVI Analytical Chamislry of PC8s Summary of Chrome Tone Effects of PC8s rest Ef fects Chronic feeding Aguanc species Terrestrial species Threshold effects m egg hatch* lbility of vertebrates ana m* vertebrates at levels of 2-5 ug/i Embryo to*city evident at SO ug/t Mouse some liver change -un exposure to hign cniorme con* taming products. 2QG-5QQ ug/g Ret * some liver chances, min imal reproductive effects. 100-500 ug/g Monkey ^usho symotoms, al tered reproduction cycles, hyperplastic gastritis and ulceration, 2 5-5 ug/g Chicken * som# morpholoq'C de formity, reproduction dec'me. suPCutaneous edema. 20-50 jo g Mmk oose response relation ship in growth and reproocton, 10 ug/g Pel'can - some hepatoceIlu>ar changes, 100 ug Oogs - reduced growth, some 1iver changes, 100 ug Wildfowl * some reproduction changes, varies with spee'es. 50-200 ug/g MONS 223*97 properties TA8tfc 2~*vi (continued) 47 Test Creels 7eratogeni city Effects seen in avian species. SO*200 ug/g Hutagemoty Oncogenic Uy Chromosomal abnormalities * negat've results Dormant lethal mutations negative results Ames test 1221. A cnloro* D'pnenyl significantly muta* genic Hign chlorinated compounds pro Juced tumors -n rats and mice, relationship with PC8 not always clear Source. Nation*! Research Council (1979); reprinted with permission from the National Academy of Science. HONS 223498 48 ' <C 1 4 1 ! ! J"' f'.. ' . *t t o*". Analytical Chemistry of PCBs (la'H 1 o 1 .1 ' AQ [ 'D0VW4 to pC8v **',:4 c~4y i 4 >* 4*n#c * 0' vorifM .a Q4* ( ? 3*1 .nr -, 0'' \ \k ) ' o o 4 600 . 4 -4 . 1 " Ol'B '^4 '< 4 1 ` ' * 1C ** "vvf; j*1* 11 4 . - 1 ' - . \ s . . ,t *41 I0* .* 1 -c 4'>a '* 4 C ">0 . 1 :j*4if 'c : i ;*-! H 3<> * i -o ' 'v'4 L .'O ioi. > "..f`S4 1 - . ,..l " .A- A' I c 6 ' 0' *< "4 C4S4 4' J* < o . .o*t ,*4t . "0C i o'* 'i- c*v441 if. nn' '4VB'rUry rr4Cl i 'r^r\ I ( J'ornfn I s #40w(t'0'' 5' 14' CfOiC'l. 'fv'f 50 > t 4 1 fn 1 i "4U4004*. ' C i *rj ' * >40cf0 1 J": ' :' . -OiC ->. .c : l '* u 4 ; "f :*oj ! r:r : -or'', i - .4 ' 4> *' 4'QO*0* V 4 0- : r w ti g .40,' HONS 23499 Properties 49 Tab'* xv III. Summary of Patho logic Fmoings Owe 10 the To*city of eC8s Patho logic c i nQing Guinea Rat Mouse Pig Chicken Monkey Human Decreased * Body weight Acne/A1opecia (-) (-) toema (') Lymphoid Atrophy Thymus Spleen Hepatomegaly Hepatomegato* * * * * * cytos i s HuU i nuc 'eated (*> Ciant Cal' Necos i s. Oegeneration fat Bile Quct <) Hypertrophy Porphyria Urinary Bladder (-) (*) Hypertrophy Castropathy Tumor Induction <*) <) * (* ) (*) * * (*) (-) * (*) (*) <- ) (*) (-) * n, r. * * n, r. * () * (> (* ) (*) (-) (*) <) (*) (-) ( ) (*) * (') (') (*) (*) Source. McConneii, I960. Reprinted with Derm- j i Cn . copy* riqnt 1980. C'sev'er Siomeo'ca' P'ess. 6v. HONS 223500 50 Analytical Chemistry of PC8s these are kno*n as cytochrome P--U8 inducers or 3-HC inducers (Goldstein. 1980) or aryl hydrocarbon nydroiy'ate (AHM) in ducers (Sate et al . 1981. 1982) These congeners are not major components (generally much less than l) of the Aroclor mixtures (Alpro and Parker. 19*9. Hucmni et a1 . 1980; Alpro et a< , 1981. Safe et al , l?tl. 1982, 1983d. see Appenoi 8) The other active group of congeners is tne pnenobarbital-type or "PB'type" moucers or cytochrome P-4S0 m* ducers, as snown in Figure 2-7 (Goldstein. 1980). Many con geners exhibit mixed responses or no observable response. Other reviews are available (Hammond, 1972. Kimbrough, 1974; Fisnbein. 1974; Calandra. 1976; Ourfee et a)., 1976; NlOSH, 1977; Matthews et al.. 1978; Kimbrough et al., 1978; IARC, 1978; Department of Health, Education and Welfare. 1978a. 1978b. 1978c; wassermann et al.. 1979; EPA. 1980d; Strik et al., 1980; Golostem, 1980; McConnell, 1980, Baker et al.. 1980; Vos et al., 1980; Brown et al., 1981a, Ecology and Environment, 1982; Caffey, 1983a.b; Friess et a)., 1983: Safe et al., 1982. 19B3a, 1983b. 19B3d. 1983e; and James. 1983. Goodman, 19B3; Sleignt. 1983; Singer, 19B3. Safe. 1984) HONS 223501 properties Cl Cl Cl c .* ! * * Oco oo 5t Cytochrome Peso inducers w?gk wept-inocrive ;i o a ci Cl Cl ;.V6.? J 6 # Cl CI 0-0 LI Cl l i f `io Cl,___C Cl___,C1 :iO"wyci Cl' // c.i * Cl Cl \' / w Cl 2* 2 a V>o J 5 D. figure 2*7. Summary of PCB Isomers Whicr Induce Cytochrome P-450 Reprinted, ith permission, from Goldstein (I9il); copyright 1990 pv Elsevier Biomedical Press B.V x OCCUPATIONAL exposure ANQ its EFFECTS workers in PCS production end use occ.oations were exposed to nign levels of commercial mixtures o* PCBs through both dermal contact and inhalation of vapors ,Table 2IX). Caoacitor plants provided the-highest reportec exposure po tential (Kimbrough, 1980c). The first report :* any effects of occupational exposure was in 1936 (Jones and -Men, 1936), when chloracne was associated with PCBs. Syir;*.oms of nigh PCS exposure include burning of eyes, face, an; skin. Sev eral clinical symptoms are indicative of PCB**elated liver injury, including elevated serum triglycerides nd induction of mixed function oxidases. Although there -is been some evidence of increased incidences of cancer, it s inconclu sive (Kimbrough, 1980c). MONS 223502 52 Analytical Chemistry of PCBs The occupational air levels were Quite mgn rela tive to ambient (see Tab> ?-*II) Table 2-*I* lists a sum mary of some or the PCB levels in workplace air along (th blood levels ano duration or exposure ana clinical e'ects (Kimbrough, 1980c) Several other studies have reported PCB concentrations m workplace air in the 1-10 mg/m^ range (about l million times ampient. NtOSH, 1977c). These expo sures general'y 'nvoiveo tne nanoling of PC8-containng ca pacitors which ere neateo as part of the manufacturing pro cess Table 2**1*. PCB Concentrations m the Occupatioha Environment and m Blood of workers E*poseo to pCBs Druation of PCB Exposure PCB .eve i s E nvlronmentaI ;mg/mJ ) Blood (ppb) Effects Reported hot known 4-8 months < 1-20 years 10 5*7 0. 2-1.6 2 5 year ave. 2.5*18 years Not reported 0.013-0.27 14 months 0. 1 2-23 years 0 32- 1 44 C ZD O s_P years Not reported `1 . . 370. ave. 820, ave. 36-286 - > 200 ?-300 74-1,900 Unbearable imta11 on Chioracne Chloracne. hyperpigmentation, iiver injury Chloracne Irritation, 11 v*r injury Ch loracne . 11 i njury Chloracne. iwer injury Cn loracne . <? > etec triglycerides No effect Source: Kimorougn (1980c) Reprinted -itn permission, copy right 1980, Elsevier Biomedical Press, BV As noted m tn* WHO document (1976), occuoationa) exposure may be widespread among workers handling PCBs m use: mechanics handling lubricating and hydraulic oils, office workers handling carbonless copy paper, analytical laboratory workers, and e'ectncal component handlers. HONS 223503 Properties 53 C n]OSH, HuBbard ( 1978 1. Occupational exposure was thoroughly reviewed 1977c; Kimbrough, 1980c). Other reviews include (1964), who (1976), IA8C (1978). and Cordit *t al. fieviews specifically concentrating on the epideio- logical aspects of PC8 exposure. Both occupational and acci dental (Yusno) include who ( 1976), NI OSH ( 1977 ), and 2 ARC (1978) the seven epidemiologic and three conort mortality studies reported since 1978 were reviewed By Gaffoy (1983a, 1983B 5. HONS 22350* 3 ANALYTICAL PROCEDURES analytical PROCEDURES This chapter focuses on the written analytical pro cedures for the analysis of *C8s in various matrices. These procedures have Been written in sufficient detail that the analyst can implement the* m the laooratory with little or no modifications or development. Most also contain detailed descriptions of the apparatus, instrumentation, supplies and reagents necessary for use of the procedure. Table 3-1 and the sections Below describe the techniques and methoos which comprise some of the procedures, the applicaBle matrices, and the limits of detection, where availaBle. Suoseouent chap ters are devoted to the specific techniques for PC8 analysis ana oresent tnese tecnmques in more detail. The methodology definitions of Taylor (1983), given Below in increasing neirarcnical order, nave generally Been toiioweo throughout this Book. Technique; Scientific principle or specific opera tion (e g" GC/tdt), Flonsi) column cleanup, or Webb and McCall quantitation). Method: A distinct adaptation of a technique for a selected measurement purpose {eg-, a specific GC/ECD operat ing mode for analysis of PC8s, including column specifica tions and sample preparation. Procedure: Th* written directions necessary to use a method or senes of methods and techniques. Protocol. A set of definitive directions that must Be followed without deviation to yield acceptable analytical results. A true analytical protocol m rare, possibly nonMistent, m PCB analysis. 55 MOMS 22350$ 56 Analytical Chamistry ol PCBs Table 3-1 lists the analytical procedures available for PCBs. Severe! are general organic pollutant or chlori nated hydrocarbon procedures which include PCSs along with many other analyte* These include Oevenish, EPA (Ha'ocarbon), EPA (Priority Pollutant). EPA (soil and sediment). EpA (3Q4h), EPA (8100). EPA (S,A.(1}). EPA (5.A.(3]). EPA (608). EPA (626). EPA (SOSO). EPA (6260). EPA (8270). and FDA-PAM. The procedures in Table 3*! address a variety of materials including water, wastewater, soil, sediment, sludge, nr, combustion and incinerator emissions, capacitor askarels. transformer fluid, waste oil. mixtures of chlorinated ben zenes. pigments, food, milk, blood, and adipose tissue Extraction and cleanup techniques are presented 'n Table 3-1 in terms of the materials and reagents required for analysis. Less man naif of the procedures comment on the criteria required to make qualitative determinations for the presence of PCSs m sample extracts. The quantitation tech nique for each of the analysis schemes is presented along with the limit of detection (100). if specified. More man half of me procedures mention quality control (QC) The quality control steps presented include analysis of blanxs, replicates, control samples, spiked additions, and criteria for accuracy, precision, and instrumental performance. Not all of the procedures listed are sanctioned by a sponsoring organization at this point. Hany have interim status and some have been proposed but never endorsed Dy an organiration. 1. ANSI AND ASTM PROCEDURES The ANSI procedures for the isolation and determi nation of PC6s m air. water, soil, sediment, and biological materials are based on techniques that were used by me Mon santo Industrial Chemical Company. Packed column gas cnromatography with electron capture detection (PGC/ECO) is me designated method for quantitation of PCSs as Aroclors in the ANSI procedures. The PC6s are quantitated against an Aroclor standard using the largest peak, or a secondary peak if the largest peak appears to be interfered with. If the PC8 pro* fite is altered with respect to the standard, all major peaks art summed. Mass spectrometry is recommended for confirma tion. The cleanup techniques are required only if interfer ences are noted for the PGC/ECO determination. The Quality control measure in the ANSI procedures emphasize the number of theoretical plates and tailing factor for the packed gas chromatography column. The LOO for the procedure is 2 ppb in air. bated on an instrumental LOO of OS ng. The calculation MONS 223506 M #4 *#'* tot IM I* in 4* i. .*. * 4;> mu< ... IM ||r Ml W . #.*r. *# $., | /% \ * '*>+* m-4.# #*#'! * I (*!..<i IS,.,.. | I*.... I | is *11 iftVm '...I/ sin*# f" HR .(* I V '*! | #.r.# tot****#*'** to# i ru/HI* toi*v U/(< ... i IS ,-l VI /I li |lt*\ HX/M# *<# *. *._* .# V * * >t R4U/*\m **4 r** V IN V0 * -<..# U/H# *#| RU/M| 'V* R#` * IM m Asia mi# IW, |4 * iitor Il##*#% M (M |4*| I * < I # * * <hi m imto** * #M HU %! H*i U| s*# #t ( M 'HI i N"MU * M *M| MM'I m ..... * i.M MM,MAS Kf /M*v '# in ooi mi " 11-* 4*~- IM9 i #ti lMi ift ( , It #| H* l# f4 *! #r.S# M MONS 223507 lK *<*! (ImpimiiI * llll.lHI 1* tf IIP It 1IM IM */ IIIIlM (t/lt/tl '<. (!/ Will |M .III C'ip*m' CPC hP( I*U I ((HllMt) NUr*U1 \m MIM Ml. (mMIIIIIm HMP PU/KI 1*1 <M ir MM <w tot s PU/UMV m V V li* IS* P|i# ll lllli * Ut4 lU Vll* <> M.MIlIPpO <N,U* () <",CI, (Ml, MUM/ in Will III! M tM<M.I P.plM.1 1.*< *4 C,(* o%c IP* I*?' II .PMP.PP. M 1 Ull*l) * lltl MMMW m imi> till III tl Ml' lM Mill II Ip.PP* h W >/ IMP CPC min in HUpiiIH MW ((*,() (IImIiH) him*, mu (<cwyt ci.iiin tti'i* |ii (1 PPM.*!) S<M<IPI<PIIM *M. Imp** (Ml.tllll mcc/i ! / PCC'UKS P/IC Ptt/tlM MCC/I MX P/lt* */( P/*C PCC/IC* IM M ft m to Mi ft* M < M PM fll 1.1.1 |t P. M IPPMMCpU l < i'i ) PC'! 1 *'1 1 (Mill t Imp. Impi r >.SI KU MlfMl PPH*** MPP MMM* fPPII 1 M> P M* (M s */!( U 1*1*1 r* *r 10 SO #Mfc iWlfM f* Ntf* lyv* 1 * \M ). iPN ... li"'f'. 11 pi IP*. pMPp Tit (PI |IP. * 1MI1 ft* t<M UMw, 1**1 M* ip* imp. II* *iU t* Tft Mil . HM ... I'Uii.. n . IMP. IMP. I'low. PM II* (Mil. IMP MONS 223508 * *r f# #M* * H*l * H l I't ( 4S** Ni !,( I I (l*|tHl 0%* >ll I** %IM i . l .. .( lit -. * 0* || 4 / MHH 41 M' IHt ll<4. !'! *<< W*4 lr| * * r. t i II'* MM *' | . - * *1 I AI > PM "S WJ Ml 9 si++s* as : ti*t >' ** Sm^ ii'l M M (0U 10' M .. | ,.t l. <0 4 HiM /Ml m I l<M > , nj /ny *4 0 4I| **/*l HASH |*IJ im4 OSH4* /Mi PW 'MO r#ss *<< MM %<h pmi wh ..I * ! `I <* O'# * n 01 *' M *I0SH (1 / ^ . s M i n i itii $>** |P0*<*l< |l 4 * 0) ***'* IP* (0 > Hill *#.*-* PlN#|t(l*4Hr' 44 *N (N,U * !<*/ ............ I I"i v i | I U. 4H.4H 4 N I t| j< IH r< ir HXHP *</<* **'!( '4 I r |> V I ' > m (II |M|#< ! Hi HV H> HS V Vl IN HH V# H4 M04 M V*4 | (M llt |*M I I * iM lilt tM vnm mi HONS 223509 !< ImnilM Hum' IMI* > KMtlwMI hUMlMIlM HUM mI ImmHiUm NlkN l0* at t<r ... CI llll MM ll> imin -- ! M iNlfMM* {Milt* C,(*^u '< sa*/ <*<( iimi <,( IWWillllln * M*M.II U+J (ill* IM'HIimIH Hill pi t*l'l<*IIW (1 UlilM) JMIlH Kl (IlNllillll'HI ItdMIlM) ltlwt.ll) ><1)1 uvu* IMMIHmKM Hm MC/tt* urn* w/in INC/Mill << */u K*1 MK/IM M '* Ml M a* Ml.l If IM MMI t*r *lm a*i * trl t W mv <e - 1**f#l m IN i in ! ini n |M MM* ll*l MM .1* m II < II 1 Mid m AM . IMH I* IM*. 8 NIU II lM*l . ii4* *n Him t.M<MB IlHllll i!m* wmi |IM(I| (IImI.II hM (M IM Mill m MTHdll M M> a* ilk IMI |l* I'll) I'.Ul . <l* III! 1 (lUiJill) fumt* III Ml* M i mf*t H nu nt w<*ll (IIibImi itm i*hi* po naui <K). <{*,<> 'I I" .!!. Mill "I ll MW ''Mil 1 'pM l|W 1 (HIM/ a (,(!, Ml riiftiM MK/tlM NC/tCI III Ii4 HIM B ta immm i f| I...I > INI* IMH M INI 1 M'HBI^ III MM IN' (Ill* iMlft 1 MB Htnm < !(> MM M NljM'hMI** W. IMI IM i-imm * Mil MM>fi>4 HI Mt|.M ai amiM MC/tM* IM fM MHl n in HI. IMM |l<Nl M 4<>M* *M l*|M I I.|M*M I* MtIMN ' MH'IMI M l)Ml ta IN !<. * *r HI .H llliKMlMBIrlt M twtf*lfl> IHWOlKr HONS 223510 Analytical Procedures 61 procedur* is "01 specified No valifluon flat* ar* given, altnougn general discussions of the applicabi1ity of the techniques are presented. The ASTM procedure 'or atr i$ similar Th-> A$TM ( 1983 ) procedure for mineral insulating oiis util'ze; solvent dilution and a florisil slurry cleanup prior to RGG/ECD determination The procedure assumes that me composition of tn# PCBs present in transformer or capac11or oils closely resemo'es that of the Arodor standaros. It notes that tn* sensitivity of the ECO 's reduced by min eral oil and instructs the analyst to make the amount of oil >n tne stangard and sample eouiva'ent to minimize me effects of me oil interference on the quantitative results. II. PA PROCEDURE C0R OKS Tiv PA procedure for analysis of PCBs in trins* former oils and waste oils (EPA, 1981a; Bellar and Lichtenberg, 1981) provides a generalized approach with re spect to samole preparation, and instrumental analysis. Sev* era) cleanup techniques are provided as optional approaches in this procedure (see Chapter 6). For the instrumental analysis, GC with halogen specific, electron capture, or mass spectrometry detectors are all allowed, provided appropriate limits of detection can be achieved. A strong quality con trol program including control samples, daily quality control check samples, blanks, standard additions, accuracy and pre cision records, and instrumental and chromatographic perfor mance criteria is required to support all oata generated by the method. III. PA PROCEDURES FOR SPILLS AND INCINERATORS The EPA procedures for PC8 spills and incinerators (Beard and Scnaum. 1978) are part of a manual for PCS dis posal, primarily focusing on incineration methods. Although this interim report is badly flawed and incomplete, it has been widely used as the guidance document by the PA Regional Administrators for testing incinerators. The stack gas is sampled using the modified EPA Method 5 technipue developed by Haile and Baladi (1977). PC8s are extracted from the sorbent material in a Soxhlet ex tractor using Both pentane and methanol The GC/MS analysis is taken from a tentative procedure for PC8s m water (Oudenbostel. 1976) Samples may be cnromatograoned on col umns packed with 3% Dexsil 300, Ov-l. or 0V-101 and may be detected using either electron impact or chemical ionization mass spectrometry. MONS 223511 62 Analylical Chemistry of PCBs Tne " Tnui1 vt **moa 'or Testing Polychlori nated Biohenyis (PCBs) h i>ci ' ieo Material" (Attachment a, Bearo ano Schaum. :9'8) directs the analyst to air-ory the sample (main* is not father *Decif'ed). gnnd u, and then extract a 100-g suDsamo'e m a So*niet extractor with hexane- acetone (1 1). The oroceoure theh patches into an unrefer- encefl industrial effluent methoo, which first specifies a PGC/ECD screen If necessary, various cleanup techniques are specif'eo. An acetonitrile partition is used to remove fats and oils. A fiorisil co'umn deanup fractionates out some oesticioes using 6*. 1B, ano SO* ethyl etner/petroleum ether eiuates Two alternate silica gel microcolumn cleanups are presentee, one of which orovioes for sulfur removal 'th mercury. IV PROCEDURES r0 R fQQQ The fOA (1977), AOAC (1980a). jnd Japanese (Tanaoe. 1976) procedures for food are similar. Samples of fooo are ground, extracted with petroleum ether, and me lipids re moved by an acetonitrile partition. Various cleanuo tech niques are utilized prior to determination by PGC/ECD. V. PROCEDURES FOR Bv-PPQOUCT ANALYSIS The orocedures for Oy-oroduct analysis (Dow. 1961. OCMA. 1982. Erickson et al.. 1982. 1983d, Erickson. '.?84a, 1984&. 1964c) all reau're strong QC programs 'he EPa pro cedures (Erickson et al . 198*2. 1983d; Erickson, :??a, 1984b. 1984c) allow a maximum of flexibility in the extrac tion and cleanups to accomodate me ioe range of matr'ces (the product and product waste procedure >s aoplicaoie to liouids. gases, or solias of virtually any composition). In lieu of method control, the procedures rely on me QC, nota bly the measurement of the recovery of four iJC-1abeied PCBs spiked mto each sample as recovery surrogates. MOMS 223512 4 SAMPLE COLLECTION AND STORAGE The first step 'n any successful analysis is the collection of a samo'e The selection of sampling sites, freauency of sampling. number of samples, measurement of physical ang chemical parameters of tne sample, ana the over all statistical design of sampling me mods nave been provided m etens've detail (see for example. Moser and Huioregtse, 1976, EPA. 1976; Mason. 1982; Kelso et al.. 1985). The sam pling design in most cases <s directly related to the objec tives of a specific research program or a regulatory action. PC8s are an inert, non-po'ar class of semivolatile organic compounds As such, they are reasonably well-behaved during samole collection and storage. Consequently, with the exceptions of tne air and water sampling techniques which concentrate the PC8s from the matrix onto an adsorbent, most PC8 sample collections nave utilized tne standard or custom ary methods for semivolati'e organics >n the subject matrix for e*amole. the ASTM procedure (1981b) references general methods for water sampling, sediment and soil sampling, and air sampnng. The reader is referred to general sampling and storage oroceoures m tne absence of a PC8*soecific method. Sampling for chemical analysis nas oeen reviewed (Kratochvil et a) . 1984).I. I. WAT[R water samples may be collected by grab or integra tion techniques Crab sampling has Oeen much more common. The integration techniques include automatic composite sam plers. adsorption onto a solid (xAQ resin, polyurethane foam, etc.), ano iiQuid-1iquid extraction. Since water sampling for PCS analysis may be readily adapted from general water sampling procedures for semivoatile organics, the reader is referred to these procedures for specific guidance. These include E#A s Prior-ty Pollutant Methods 608 and 625 (EPA. 1979a. 1979b. 1984e, l?84f. tongbottom and lichtenoerg, 63 MONS 223513 64 Analytical Chemistry of PCBs 1982), ASTH's (1981b) Method 0 3304; tne EPA Handbook for Sampling and Sample Preparation of water and wastewater (Hoser and Huibregtse, 1976) and an [PA document on Pro cedures for Handling and Chemical Analysis of Sediment ano water Samples (Plumb. 1981). a . Gro Samp 11nq Most water procedures and methods have used simple grab sampling. For eampie. EPA's Method 608 for organo* chlorine pesticides and PC8s in wastewater ([PA. 1979a) stip ulates that grab samples be collected in glass containers a rigorous glassware cleaning method is described m the pro cedure. Samples must be iced or refrigerated from the time of collection until eitraction If samples will be stored for more than 48 hours, the oh is to be adjusted to between 6.0 and 8.0 The Sodman bottle can collect ud to 90 t (Patmor* et al., 1982; Harvey and Stemhauer. 1976). As the sample >s lowered, water flows through a weighted aluminum cylinder At the desired depth, plates at either end are closed and tne sample is retrieved The sample >s transfered to steel drums under nitrogen for storage. A glass sphere which collects a 10*1 sample has the advantage of direct hexane extraction in the sample vessel (Palmork et al.. 1982). Extraction in tne sampling vessel not only reduces the volume of samole to be stored, but also minimises adsorptive losses to the container walls The use and specifications of two large-volume grao samplers were described for sampling seawater (Pavlou et al . 1980). The samplers were designed to be used in conjunction with a filtering system (also described) to collect large volumes of particulate. A gaslift system can collect unlimited water vol umes (Palmork et al.. 1982). water is aspirated through a 3/4 m stainless steel pipe by injecting nitrogen near tne base of the pipe. Marin# water can be collected at 8 to 10 (./min at a depth of 10 m and transferred directly to stain less steel drums to prevent contamination by the shipboard environment. 8. Automatic Composite Samplers An automatic composite sampler generally consists of a pump, tubmg, a timer, and a collection vessel. Typi cally, the timer cycles the pump on for a fraction of every hour, during which water is Dumped into the collection ves* sel. This permits collection of an integrated sample from a flowing water stream over a 1-day period or longer. Th# [PA MOWS 223514 Sample Collection and Storage 65 (19^9*.0) stipulates mat automatic samplers use refrigerated glass containers for the water samol* *ng that the equipment be as free as possible of Tygon tubing and other potential sources of contamination C Solid Adsorbent Sampling A wide variety of solid adsorbent materials have been investigated for use in water sampling. The objective has been to preconcentrate PC8s from a large volume of water onto a small volume of solid adsorbent which may be easily transported, stored, and extracted. In addition to its con* vemence. preconcentration can enhance the method detection limit As discussed below, investigators have reported mi>ed results with adsorbent columns. Background from the sorbent, poor precision, and non-Quantitalive recovery nave all been reported. Thus, investigators must demonstrate that results obtained with these sampling tecnniQuet are valid. RiseOrougn et a) (1976) reviewed early uses of solid adsor bents to sample seawater. 1. Polyurethane foam: The use of polyurethane foam (PUF) to adsorb 0CBs from water samples was reported by Cesser *t al. (1971). They reported 91 to 98X recovery from l-l samples passed through a PUF plug in a glass column. The PCBs were recovered from the sorbent with 20 ml acetone, fol lowed by 100 ml hexane. Seller and Lichtenperg (1975), how ever, noted that this technique was not applicable to river water samoles. since the suspended solids plugged the column. Uthe et al. ( 1974), reported success with PUF coated with DC-200 silicone grease. They used their plugs as indwelling monitors, the plug is submerged in a water system to collect PCBs as they come in contact with the sampler as shown in Figure 4-1 while the simplicity and low cost of this system make U appealing, th authors did not validate the PCB con centrations against an accepted method. Sellar and Lichtenperg (1975) noted that this method led to poorer pre cision and accuracy with dosed river water than with dts* ti lied water An active j_n situ seawater sampler using PUF plugs permits collection of ?C8s from large water volumes (RiseOrougn et al., 1976). The sampler contains five PUF plugs in a 975-cm;5 tube. The sample is lowered to depth and water pumped at 500 mi/min py a vacuum hose connected to the snio. The PCBs are subsequently extracted by successive elu tion with B00 mi each acetone and hexane. The PCB concentra tions obtained from 26 to 79 l samples by this sample compared MONS ZZ3515 66 Analytical Chemistry of PC8s figure 4-1. Passive water Sampling Oev>ce Polyurethane surface. D'ugs ire help just Beneath the water Reprinted. with permission, from Uthe et *1. (1974); cooyngnt 1974 py Marcel Oekker, Inc. favorably with those ootained by methyiehe chloriae extrac* tion and were aoout twice those obtained with hexane extrac tion. Ahling and Jensen (1970) used Puf coated with n-undecane and Carpowax 4000 monostearate to effect a 'reverse onase liauid*Iiquid partitioning " water samples (up to 200 l) were concentrated onto 3 g of soroent and then aesoroed with 5 mt oetroleum etner. Recoveries of 93 to 100% were opserved for 10 ug of Clophen A50 added to 5*1 water samples. 2. Macrpreticular resins: The use of macroreticu* lar resins (specifically tn# AmoerHte XA0 series) nas oeen reported by several grouos (Musty ang Nicxless, 1974a; Lawrence and Tosine, 1976; Harvey and Steinhauer, 1976; Osterroht, 1977; Coburn et al., 1977; Picer and Picer, 1980; Palmork et al., 1982; and isenrich et al . 1983a). Musty and Nickless (1974a) reported an overall recovery of 76% after one liter of tap water spiked at the ppp level was ad* sorped onto XA0-4 (a styrene-divinylpentene copolymer), and then eluted with diethyl ether*hexane mixture. Coburn et al. (1977) reborted 78 to 86% recovery of an Aroclor mixture from 2*1 natural water samples collected on xAO-2 (also a sty* rene-divinyIpentene copolymer), and then eluted with ether MONS 223516 Sample Collection ana Storage 67 Recovery of chlorinated hydrocarbons, including PCBs. -as reported lo be low and variable Dy Picer and Picer (1980) in fact, tney noted tnat the results of a collaoora* live study produced results varying by over two orders of magnitude from reo'icate XAD*2 resin cartridges which hag been prepared by one laboratory A column containing 50 ml XA0*2 was used to extract PC8s from 50 to 200 l of seawater which had been collected in a 65*1 sampler (Harvey and Sieinhauer, 1976). The water was bumped through the column at a rate of S bed volumes/mm. The authors noted that the flow rate was critical to selec* tive adsorption of the organochlorines relative to other or ganic matter PCBs were eluted from the column with aceto nitrile. The precision, based on replicate analyses, was within 20V The accuracy based on comparison to solvent extraction of 50*1 aliquots of the same sample was also within 20V Eisenreich et al. (1983a) used XAO-2 to concentrate PCBs from Lake Superior water. The 40*1 sample sue per mitted the authors to quantitate PCBs with average concen trations around 1 ng/l (parts per trillion). The resin was extracted in a Soxhlet extractor using a l: 1 mixture of hex ane and acetone. No validation data were given. 3. Tenax CC: Ltom et al. ( 1976b) reported es* sentSally quantitative recovery of 1.6 ppb of PCBs spiked into 10 L of seacoast water which were concentrated without filtration onio a column packed with a mixture of Celite (di* atomaceous earth), and Tenax GC [poly(2.6"diphenyl*g*pheny1ene oxide)]. The PCBs were eiuted with diethyl ether. They noted that it was often necessary to filter water samples, but did not measure PCB recovery under these conditions. Picer and Picer (I960) reported considerable background from Tenax Columns using a variety of cleanup and desorption sol vents . 0 tiquid-liquid Extraction Sampling Ahnoff and Josefsson (1973. 1974, 1976) reported the use of a continuous 1 iouid* I iqud extractor wnch concen trated PCBs from hundreds of liters of river water into 1D0 to 300 ml of 1 ighter*than-water solvent. The sampler mixed the water and solvent with a stirring bar. Water entered from the top and exited from the bottom. Pumping rates were variable up to about S l/hr Recoveries of chlorinated pest icides were > BOX. PCB concentrations in river water were measured as low as 0.1 ng/l. MOWS 223517 $8 Analytical Chamistry of PCBs . Ramwater Samp) mg Rainwater sampling can employ simple aooaratus For example, stations for continuous collection of ram piu4 dry deposition (Biflleman et at , 1981a) consisted of 22-cm d'ameter stamiess*steei funnels wmcn emptied into 3 8-1 Brown-glas* Jugs The funnels were placed aDout 2 m above a marsh surface and were surrounded with wire spikes to dis courage perching crds. These "continuous'' station* were tended at 2 to 3 week intervals. [vent ram samples were collected &y exposing stamiess*steel bowls during rain storms . More elaborate apparatus designed to either con* centrate the water samole as it is collected or to prevent dry deposition of particulate is used more often. For ex ample. Murpny et al. (1981) used a- sampler which concentrated PCBs onto a sorbeht for them studies of PC8 deposition in the Great takes Pain fell on a 1.5 m* surface, was filtered through glass fiber, and then the PC8s soroed onto polyure thane foam. This approach, however, was suoseouently aban doned in favor of an integrated wet/dry sampler, which simply collected the rainwater in buckets. The sampler had a roof which automatically uncovered a bucket at the start of a rainfall. Two samplers have been described which automatic* ally collect rainwater and concentrate 't onto a resin car tridge (Strachan and Huneault. 1984; Pankow et al , 1984) Both systems sense rainfall and automatically ooen a cover for the collection period. The rjm then falls on a clean surface and flows toward the sorbent cartridge 1'tracnjn anq Huneault used KAO-2 or KAO*? resin. Recoveries from the KAO-2 were mgner than from tne KAO-7 (86% versus 68% for several pesticides). Pankow et al. (1984) used Tenax-GC as the adsorbent. F. Water Sample Storage Most general procedures (eg., the [PA priority pollutant methods) merely specify cold storage, somet'mes in the darn or in amber bottles. Ho special precautions are stipulated for PCBs. The adsorption of PCBs from water onto the con tainer wall has been reported (Peoe and Byrne, 1980; Muldrtw et a)., 1981. Sutcliffe and Nielsen, 1983). If precautions are not made to prevent these adsorptive losses during sam pling and sloraQe, then the extraction technique should inelude extraction of the interior of the sample container. MONS 223518 Sample Collection and Storage 69 The use of formaldehyde r>*j been shown to preserve ater samples for PC8 analysis as shown in figure 4*2 (Better and Lichtenberg, 1975) Aroclor spiked in river water at 1 ug/l decreased steadily over a 15-day study in unpreserved samples, white no tosses were observed when an unspecified amount of formaldehyde had been added. The temperature and light conditions were not specified. The authors noted greater losses with me congeners containing < 3 chlorine atoms Other preservation techmoues were less effective: over the range of 2.7 to 10.5, pH had no effect on storage losses. Both refrigeration ano the absence of light retarded PCB loss relative to storage at ambient temperature in the light, but still showee significant losses, as shown in Fig* ure 4*2. The authors noted that the rate of loss appeared to be affected by the physical, chemical, ano biological char acteristics of the samples. They also documented a faster rate of loss with Teflon than with aluminum cap liners; al* though no PCBs could be recovered by extraction of the Teflon liners Storage temperature (4C versus 24C), pH (2, 7. and 10), and chlorine (0 or 2 ppm NaOCI) did not markedly af fect the recoveries of seven different Aroclors from clean water after storage for 7 days (Millar et al., 1981. 1982). Most of the samples exhibited greater man 90% recovery. Sorption of PC3s to glass and plastic surfaces has been shown to cause significant losses (Peoe and Byrne. 1980; Muidrew et al., 1981; Sutcliffe and Nielsen, 1983), although the first two studies a*e flawed in that the concentration of the 14C*2.2',4,4'.S,S'--e*acn1orobipheny1 .as well in excess of either the water solubility or environmentally significant levels. Nevertheless, sasorption onto the sample container (and me cap) should be considered as a potential source of loss from a sample Under most stc-age conditions, photochemical, chem ical or biological degradation of PCBs in weler samples ap pear unlikely. However, as noted in the two preceeding para* grapns. losses due to pnysical removal nave been observed and can be significant. The sorption of PCBs onto glass, partic ulate, and other surfaces is only to be expected, given their low water solubility and high octanol-water partition coeffi* cients. It may oe mat tie preservation effects of formalde hyde noted Dy Be*>ar arc Licntenperg (1975) above, may nave Been simply the effect :f increasing the solubility of the PCBs in the sample by the addition of a water-miscible or ganic "solvent." Analysts can generally counteract sorptive losses by treating the entire '--tenor of me sample vessel (water, MONS 223519 70 Analytical Chemistry of PCBs Figure 4`2- Effect of Storage Conditions on Recovery of Aroclor 1016 from River Water Samples were dosed it 1 ^g/sample. stored at ampient tempera ture (in light and the dark) under refrigeration, and pre* served with formaldehyde. Reprinted, with permission, from Bel tar and Uchtenberg, 1975; copyright 1975 by American Society for Testing and Materials MONS 223520 Sample Collection ana Storage 71 surface, and cap liner) as part of tn# "sample " ! f the sam* pie container is extracted and combined with the ater ex* tract, the adsorbed PCBs should be recovered. In add!tion, the use of so iked Meld controls ahd/or samples hich are spiked (standard addition) in the field as part of the over* all QC (see Chapter 9} should aid the analyst in assessihg any losses during storage II. MR The general category of air sampling encompasses a wide variety of objectives and techniQues. Ampient (i.e.. breathable) air includes both indoor and outdoor sites, and may be sampled using personal, fixed, and atmospheric depos>* tion sampling techniques. The non*ambient a<r which has been sampled is Stack gas from incinerators, power plants, etc. Regardless of the a<r type or sampling objective, nearly all reported procedures involve some technique of concentrating the PCBs from tne air to a much smaller volume of solid or liquid sorbent; usually with an active pumping mechanism to draw the air through the sorbent medium. The only exceptions to active sampling are the techniques designed to monitor at* mospneric deposition. . Air sampling techniques must quantitatively concen trate the PCBs from the air In addition, the PCBs must be recoverable, tne soroent medium must not generate interfer ences. and the entire process must be shown to accurately re* fleet tne true concentration in air This section presents the techniques used for air sampling and a'so discusses the validation and utility of the techmoues A. Ambient Air 1. Sol id sorbents: Several of the common solid sorbents have been used for collection of PCBs from air- porous polyurethane foam (PUP). florisil. and XAO-2. with all of these sorbents, the PCBs are rather loosely bound and migrate slowly through the medium with the air flow, just as they do through a gas chromatography column. Thus, a major talk in characterizing a sorbent is assessing the break through volume. The more volatile, lower-chlorinated PCBs break through first, so many of the recovery studies show poorer recoveries for these comoounos than for the heavier hoeiologs a. Pplvuretnane foam: PUP plugs have been extensively studied by Bidleman and coworke*s (Bidleman and Olney, 1974; Simon and Bidleman. 1979; Burdick and Bidleman, 19B1; Bidleman and Leonard. 1982: Billings and Bidleman, MONS 223521 72 Analytical Chemistry of PC8* 1980, 1983. 8id'eman et al , 1981b, 1983. 1984), Co*w,er. cially available pUf 'S Cut mto cylindrical plugs ie.g 7 6 cm d'ameter * 7 6 cm truck) The plugs are then traded m a So*niet (8i|:mgs and B'dleman, 1983 ), or Dy r*. oeateo manual comoression (r-ckson et el, 1980a) with or ganic solvents The piuqs are then oried m a vacuum desic cator at 40 to 45C (temoerature is not critical). The move ment of 3,3'-d'chloroo'pneny 1 and 2.4',5-1rich1orob*pneny\ through P{jf has oeen studied (8urd'ck and Sidlemart, 19B1 Bid'eman et al . 1983) They found that the oenetrauon depths of the PCBs depended on the ambient temoerature and volatility of the compound and were linearly related to th* total air volume. < e., tne system Denaves like a gas-solio chromatograph Even for these lighter PCBs, breakthrough volumes for a 15-cm PUP plug at 20C were Over 1,000 m1 Thus, Puf may be used for high-volume air samoling 8idleman`s group has typically collected 600 to 1,500 J of air with PCS concentrations ranging from 0 08 to 100 ng/m>. measured as Aroclor 1016 and 1254. The olanx values for the PUP plugs were m the 5 to 10 ng.<piug range for iresniy cleaned plugs and 10 to 20 ng/plug range for plugs used after 3 months of storage. le^is et al. (1977a.D) reported collection ef ficiencies m the 70 to 85% range for different Aroclors when 200 to 325 m1 of air containing 19 to 153 ng/m> PCBs were sampled through 5-cm diameter x 7.6 cm PUP plugs. The col lection efficiency correlated with the degree of chlorina tion. Using PGC/CCD. they calculated a theoretical detection limit of 0.1 ng/m1. Lewis and Jacuson (1982) reported im proved collecfon efficiencies with a dual sorbent cartridge consisting of a 25 cJ bed of granu'ar sorpent sandwiched be* tween two PUP plugs 15 cm thick upstream and 2 5 cm thick downstream). The granular sorpents tested were Chromosoro 102, Porapak ft. *AD*2, Tenax GC, and rlorisil No specific soroent was recommended. The sampling cartridge was Soxh>etextracted without disassembly The results, shown in Taole 4*1. indicate improved collection for the lighter PCBs (diand trichlorooipnenyls) over PUP alone, lewis and Macieod (1982) reduced the size of the cartridge to 2.2 cm diameter 6 cm for use in personal sampling. At flow rates of 3.8 1/ min and a total sampling volume of 900 l, recoveries of Aro clor 1242. 1254. and 1260 were 96V ?5V and 109V respec tively. An analytical procedure has been prepared, which summarizes the method (lewis. 1982). Oehme and Stray ( 1982) and Oehme and OiUr (1983) used PUP olugt to sample arctic air for extremely low levels of PCBs. They reported a sampling efficiency of 80 to 100% for the first 11-cm diameter t 5 cm plug. The levels HONS 223522 ( Min i>!it|ihf tiy ! I .1.1 ! 1 1 ( i* 1 !><.( i tm 1 11 11 r ri.t i1 * S lil 'Ml Pl'M I s 1 .lit . Air 1 HIM >1 ( lll|/ft ) 1'1 If A 1 uii* X Cutlet t 1 All IT <**t m .it ??'j l / m mi lllf/ - rui 7 *' nif 7~ C III riAMSOl l> III? I'm .|'4t K *A(| / PMf / ' " i'Mi 7 Iijiih* (,(. ( ly vs v 1.V < / >1 .MV </ Vi } ,1 1 < i n / .* it ll> Co /.V .'i Ii < ii / / ii HI. ?.r .'i.'.' i*-i i .i II 7 / M )4 /.?' .A.'./j'-l- nil .t II / 11 1. * <\ 7' . 1 . ` , '< . 'i ' U*d tl. <* / U HI' 0? BO 81 81 >> H4 H/ 'Hi H` H / 'll M'i '(J 80 Hll HH HI 1/ 'll. K4 '>7 ''i H') 111 87 HH 9/ '> 1 >t Avr i itgo o 1 t, ( 1? iffllM ! i.-l l MIMS ------------------- - -- - - - - -- S.iHMf fowls <jii<I .Jjiksou. I`iff? HC||I intel wilfi pf ri vv urn. topyrighl 1907. Aorntpi Chenm*! Sot<ny HONS 223523 74 Analytical Chemistry of PCBs found ift arctC ar using H RC C/ IMS ranged from 0 2 to 4 0 pg/mJ measured as Cl* and Cl? homoiogs *ng from 0 6 lo VO pg/m1 measured as Pnenocnlor DP6. Other investigators re porting successful use of PUF plugs include Erickson et ai (1980a). and Stratton et a< (1978) Although PCBs were not studied, Adams and Caro (I960) puplished an extensive study of the utility of PUF as a soroent for pesticides from atr In a review of available metnods for ambient air, Margeson (1977) recommended the use of PuF for sample collection D. F 1 ori$11: Florisil, a magnesium silicate salt, has been widely used for stack sampling applications, Put 11 s application to sampling PCBs from ambient air nas been rather limited. Small sampling cartridges containing 0.3 g of deactivated Florisil (3% water w/w) and 1 g of an hydrous sodium sulfate were used to samole for ub to 60 nr at 2 to 4 l/min air flow (Giam et a! . 1975). PCB concentra tions were in the 35 to 90 ng/m1 range, losses during sam pling were negligible, even after 5 days of samoling at 2 to 3 l/min air flow. The N10SH (1977 a.b.c) methods for PCBs in air utilize Florisil tubes which are sampled with a personal sam pling pump at 50 to 200 ml/min. The glass tubes are 4 mm 10 * 7 cm long with two sections of 30/*8 mesh deactivated Flor isil containing 100 mg and 50 mg (backup). Glass wool pro ceeds the first section; PUF separates the sections and fol lows the Dackup Florisil. PCBs are so I vent-desorbed and de termined Dy PGC/ECD. * collection efficiency of 100% is re ported for a 50*1 air sample with PCB concentrations of up to 10 mg/m1. This method was recently used to sample for 2,2' .4 .4 ' tetrachlorobiphenyl as a byproduct m 2 .4-d>chiorobenzoyl peroxide manufacture (fiubenstem, 1903) PCB concentrations were in the 100 to 200 ng/m1 range. The Ontario Ministry of the Environment uses Florisil cartridges to samole air in their ambient air sur veys (Singer et *1., 19B3). The cartridge blanks average less than 0.3 ng/m3 PCBs/m1 air. c. XAQ-2: The macrbreticular resin XA0-2 is a styrene*divinylbenzne copolymer with a surface area of 300 to 350 m*/g. The successful use of XAD*2 with a high volume sampler has been reported (Doskey and Andren, 1979). The XAD*2 was held in a resin cabsule with 60*mesh screens. Two 70*g oortions of the resin were sampled in tandem. The resin was cleaned ub by first drying at 60*C overnight, then Soxhlet-extracting with petroleum ether for 72 hr. then dry ing as before. At a flow rate of 0.5 to 0.7 mVmin (total air volume of 700 to 3,100 m1), 90% collection efficiencies were reported for a tetrachlorobiphenyl and Arocior 1221 HONS 223524 Sample Collection and Storage 75 Under similar conditions, 90 to 9SX recoveries of Aroclors 1221. 12<2. and 12S4 have Been reported (Hollod and i s en r*ic n, 1981, Eisenretch et al. 1983b). Only 100-400 m4 of a<r could be sampled before oreakthrough occured. d. Comparison of sorbents. PUP, silicone oil coated on PUP, florin), and XA0-2 were evaluated (Ooskey and Andren, 1979) using ,4C-!abeled 2,2' .5,S'-tetracnlorgpi pnenyl The retention of the PCB spiked (300 ng) onto tne too of the sorbent was tested with flow rates of 3 to 7 l/min and total sample volumes of 7 to 26 m3. XA0-2 and Floruit exhibited essentially quantitative retention of the PCB. while the Pdf exhioited 8OX retention and tne silicone oii coated PUP exhibited S8X retention. The collection effi ciency was then measured. The radiolabeled PCB (ISO ng) was also vaporized into the air stream and then collected by the sorbents The coated PUP was not evaluated due to its poor performance m the previous experiment. At flow rates of S to 16 L/min and total sample volumes of S to 17 m3, the XAD-2 and Ploruil collected the PCB at 99 and 100%, respectively. Tne efficiency of tne P(Jf was measured at SOX. XAD-2 was se* lected over Horisil as the sorbent of choice because it was coarser, had a lower pressure drop, and thus permitted higher air $amol mg rates. Billings and Bfdleman (1983) compared PUP. Tenax GC. and XAD-2 in field studies. Al) three effectively collected Aroclor 1254 on a 10 to 2D-g trap with negligible penetration to a backup trap. In a 24"hr sampling period (500 to 7QQ m3 air) at 2QC. about 1SX of Aroclor 1016 broke through the backup trap with PUP. The breakthrough was less for the other two sorbents. The ambient concentrations found with the three soroents agreed well; generally within 10 to iSX 2. Liquid sorbents: In metnods involving liquid adsorbents, theaTr Ts bupbled through the liquid trapping medium. As reviewed Oy Margeson (1977), a wide variety of glassware geometries and liquids, ranging in volatility from nexant to ethylene glycol, have been used. The latter is used in an i?A (Watts. 1980) method for pesticides and PCBs. Air is bubbled through two impingers in series containing 100 ml of ethylene glycol each, with a glass fiber filter in front to trap particulate matter. The ANSI (1974) procedure for PCBs in air uses tol uene. An unspecified volume of air is drawn through one or more gas scruooers containing toluene. The procedure notes that neither tne capacity nor tne collection efficiency has been evaluated. It further cautions the user to make only comparative measurements with samples collected under equiva lent conditions. MONS 223525 76 Analytical Chemistry of PCBs 3 Sampi >nq apparatus'. The sampling apparatus for PCBs 's no different from that used for other semivoiatMe organics. a typical sampling tram includes a filter, sor bent, pump, and a volume or flowrate measurement device, a filter (e g , glass fiber) often preceeds tne collection me* Oium to f'lter out particulate matter, insects, etc. Tne filter generally contains only i small fraction of the PCBs at normal temperatures. In cold climates, this may not pe true and analysis of the filter should De considered. Air <% drawn through th filter and sorbent as sembly by a pump The size and type of pump depend on tne desired detection limit and portability required. Collection of sufficient sample to detect PCBs at low concentrations re quires either a nigh sampling rate (i.e., b'g Dump), or long sampling periods. Personal sampling reautres small, batterypowered pumps. In addition to tne pump, most samplers in clude a volume or rate measurement device. This may be a dry gas meter or simply a pump cycle counter Regardless, tne system must be calibrated before use. It is important that the exhaust air be vented away from the intake to prevent re* cycling of the same air. a. High volume samplers: A number of inves tigators nave modif Ted the classic "Hi -vol" for PCB sampling by inserting sorbent cartridges in the throat between me B * 10 in. (20 25 cm) filter holder and the motor These sam plers generally operate at flow rates of about 1,000 i/min Among those using these samplers are lisenre'cn et al (1983b), Bidleman and Olney (1974), Billings and Bidieman (1983), and lewis et al. (1977a). A sampler based on tne de signs of lewis and Jackson (1982) is commercially available (model PS-I, General Metals Works Company) . Medium volume samplers. cnckson et a1 (1980a) reoorted tne use of a sampler wmcn collected air at rates up to 250 l/min. . Personal samplers: A personal sampler, capable of sampling up to 4 i/min "for at least 12 hr was de veloped by tne EPA (MacLeod, 1979; lewis and Macieod. 1982) The air was pumped by a OuPont P-4000 constant Mow sampling Dump. PCBs were collected on a small PUF cartridge. Concen trations from < 10 to 10,000 ng/m1 were reported. 4. Atmospheric deposition The measurement of at mospheric deposition is an important link in environmental fate studies involving aerial transport of PCBs Atmospheric deposition may be divided into rainfall (discussed above in the water section) and dry deposition. Dry deposition is generally measured py passively sampling on a flat surface MONS 223526 Sample Collection and Storage 77 The surface may Be dry or .etted with mineral oil (McClure, i9?6. Heesen el al , 1979), glycerin (Chr i stensen el el., 1979 ), 4 muture of dio's ano ater (Murphy t al . 1981a) or other liquids. Bidleman k al (1981a) and Christensen et al ( 1979) collected PCSs on large aluminum caking pans They compared the collection efficiency of dry, water-filled, and water/g!ycerin*coated (50:SO) pans. The wet surfaces collected 1.5 to 3 times more than the dry pans. The use of coated horizontal surfaces appears to be tne only common dry deposition collection technique (Anqren, 1983), although us validity nas not been established and is, in fact, ooen to considerable ouestion (Anqren, 1983). An e*change of com* ments by Murphy et al (1981b) underscores both the theoreti cal and practical differences in the collection mechanisms of wet versus dry surfaces. They also note that the polarity of the wetting agent can affect the collection efficiency 't is possible that wet *urf4Ci collect PCSs not only by depo sition but also by adsorptive scavenging of vapor-phase com ponents which would not normally settle out. An innovative approach to obtaining realistic at mospheric deposition samples is ice coring (Murphy and Schinsky, 1983). Multiple cores (7.6 cm die. * 10 to 80 cm in length) were composited to get representative samples of sufficient volume for detection. A net deposition rate of 2 0 g/km2/mo was measured for Saginaw Bay m Lake Huron 5. Direct sampling: Oirect introduction of an air sample into a mobile mass spectrometer system has been re ported (Thomson et al., 1980; Thomson and Roberts, 1980. 1987). The system allows a 2-min average concentrat'on to be measured at 3- to a-min intervals. The detection limit -as estimated to be in the nanogram per cubic meter range 6. Qiscussion of ampient air sampling techniques. There is no clear mandate for one particular sampling tech nique. The use of solid sorbents is preferable to liQuid sorbents for several reasons. Higher air volumes may be sam pled. The solid sorbent is more portable and more aoaptable to personal monitoring. The apparatus is simpler. Regardless of the sorbent or the apparatus used, background contamination, breakthrough losses, and sample re covery must all be monitored by careful validation and qual ity control. Before sampling, the volume or flow rate device must be calibrated and the system checked for leaks. An interesting observation by Billings and Bidleman (1983) may serve as a good rule of thumb: "Because vapor pressures of pesticides and PCB isomers increase rapidly with temperature, a 5C rise in temperature has nearly the same MOHS 223527 78 Analytical Chemistry of PC8$ effect on temple penetration (into the soroent) at ooupi'ng the air volume " S. Source Sampi mg Stationery source emissions (stack or flue gas) represent the point of entry into the environment for many pollutants, including PCBs which may be in stack gas as a re sult of incomplete compustion during PC8 incineration, or may Be passed through from contaminated fuel. Since stack emis sions of PC0s are control lable, measurement of #*CBs and stack gases is important. In addition, the measurement of PCBs >n the stack gas during trial Burns of pCB incinerators is re quired in the United States to assess the destruction effi ciency ([PA, 1979a; [PA, 1981a, Erickson and Shan. :se3. Ackerman et al , 1983) Stack gas differs from amoient air in several -p- spects The gas is generally hot (70C to 500C), flowing rapidly (S to 20 m/sec), and hostile. The gas can contain large amounts of particulate, is often corrosive, ano is nearly always laden with water. All of these properties must Be considered when collecting stack gas samples. 1. Sampling techniques: Sampling methods for PCBs have Been adaoted from the general stack sampling methods used to measure particulate, acids, and other stack ef fluents. The sampling tram used most often in the u 3 the modified EPA Method S, shown in Figure 4-3. The stack gas is drawn in tnrougn a probe. The samel ing rate is aojusted so that the flow into the probe matches that m the stack (isokinetic sampling) to minimize the flow disturbances which would discriminate the gas samoled accoromg to oarticle size. The filter collects particulate at the same tem perature as the stack. The resin cartrioge (generally *AD-2) is designed to collect PCBs and other semivolatile organics. The impingers collect water and vapors (e.g., HCl) The ge ometry and sequence of tne resin cartridge and impingers differ among investigators. Oifferent lmpmger styles and sequences have Been employed to deal with specific stack sit uations (high temperature, high particulate loading, etc.) The modified Method S tram is generally operated at 1 cfm (2B Lpm) to collect a Z to 10 m* sample. The modified Method 5 uses all glass or glass-lined tuOmg, so corrosion is not generally a problem. The filter for the Modified Method ^ should not Be used to ootain the Method 5 total particulate emissions from the stack in addition to measuring the PCBs. Tne particu lates are measured gravimetrically after the filter nas oeen dried to a constant weight. This drying process can vaporize the PCBs off the filter, resulting in low PCB recoveries. HONS 223528 Sample Collection and Storage 79 Impiwfi I m4 2 CMn <00 ml Wm ImplHfit 3 lmfiwf> 4 Cfm<M 200- J0O C<mi C*> Figure 4*3. Modified Method 5 Train for Organic* Sampling of Stack Gat Reprinted from Haile et al. (1983a). HONS 223529 90 Analytical Chemistry of PCBs Another sampling train used in the United States tne Source Assessment Sampling System (SASS) train (F eairn11er et a I 1976; Lentien et a 1 , 1978) has not been widely used for PCS sampling. Quantitative collection and recovery of PCBs may not be possible with this system. [n addition, the SASS tram has many stainless steel parts, not ably the sorbent module. Corrosion of these components has been noted to be a serious problem, esoecially with high con* centrattons of HC1. such as during PCS incineration (Ackerman et al.. 1983b). A s ide*by*side comparison of the HM5 train with Flonsil sorbent and the SASS train with XA0*2 sorbent at a utility oi 1 * fired boiler was inconclusive (Hunt et a 1. , 1984) No PCBs were detected in tne samples from either tram The SASS tram demonstrated a higher PC8 destruction efficiency solely on the basis of the larger stack gas sample volume. A simple sampling device, consisting of a filter, one condensate trao. and an <A0*2 cartridge **as peoorted by Junk and Richard (1984). Mono- through nexacn lorobipnenyi$ were quantitatively collected from 200C air by the system at tne 10 ng/mJ level with a collection volume of 5 mJ. The PC8 concentrations in a power plant stack were comparable when collected by either this simple sampling train or SASS. Lovett et al. (1983) reported a direct sampling/ analysis system. Stack gas from an incinerator is pumped from an incinerator stack through a 10 urn filter and through a heated transfer line to an atmospheric pressure chemical ionization mass spectrometer (see Chapter 7) mounted in a van. Using this system, the concentration of PCBs in the stack gas could be measured every 3 min with a method de* tection limit of 8 ug/m^. .More detailed discussions or sampling trains and their use are presented elsewhere (Ackerman et al., 1983b; Stanley et al., 1982; Erickson et al., 1982, 1983d; Erickson, 1984b; Haile and Baladi, 1977; Beard and Schaum, 1978; PA, 1977; Johnson and Merrill, 1983). 2. Solid sorbents: The sorbent cartridge of the modified Method S and, presumably, other trains can accomo* date any granular sorbent. Adams et al. (1977) studied the breakthrough of Aroclor 1242 on XA0*2 in a Study of sorbents for use in SASS and modified Method S trains. They found no breakthrough under experimental conditions and projected that XAO-2 would quantitatively trap PCBs under stack sampling conditions MONS 223530 Sample Collection and Storage 81 Hiile and Saladi (1977) recommended Horisil over Tenax GC and X AO-2 for PCS sampling in a modi fled" Method S train because of its lower background and high trapping effi* ciency. In laboratory studies, they found sampling efficien cies of 86 to 92% for Aroclors with Florisi). At flow rates of 17 to 20 L/mm and ambient temperatures, Florist) and Tenax-GC exhibited much better recovery from an adsorption/ desorption experiment as shown in fable 4-11. Subsequent adsorption/desorption experiments at 120C found only 50 to 70% recoveries Tor Florisil while interferences prevented quantitation of the dicnlorobtphenyl from the Tenax. Thus, they recommended cooling the gas before the sorbent to im prove adsorption efficiency. The combined sampling effi ciency and method recovery of the Florisi) in the field sam pling train i shown in Table 4-111. A recovery of 88% for Aroclor 1221 from XA0-2 in the sampling train was also re ported. Hanneman (personal communication, 1982) reported that PCBs were not retained at acceptable levels on common solid adsorbents when the flue gas temperature was greater than 150C or in cases where the air contained an aerosol of a nonpolar material in which PC8s are very soluble. Hanneman reported successful collection of PCBs in these instances us ing PUF plugs coated with liquid polydimethylsiloxane. Sev eral plugs of the coated polyurethane were placed in a watercooled jacket to sample the air at elevated temperatures. A PCS congener was added to the surface of the foam plugs as a surrogate prior to sampling. A second PCB congener was added to the foam plugs after sampling to monitor surrogate recov ery and collection efficiency. More recently, Haile et al. (1983a) examined the PC8 collection recovery efficiency for a modified Method 5 train with XA0*2 as the sorbent. Aroclor 1254 was spiked at two levels (110 and 1,100 ug total) into a simulated flue gas during an 3-hr laboratory test. The recovery was measured by GC/MS as total tri-, tetra-, penta-, and hexachlorobiphenyls. The total recoveries from both the probe rinse and train ex tract ranged from 68 to 99%. While there was no notable trend with homolog in the total recovery, the distribution between the probe rinse and train extract was most illuminat ing. Only the trichlorobiphenyls were volatile enough to collect appreciably in the train (* 30%). The rest of the PCBs apparently adsorbed to the first cooled surface they encountered--the probe. These data suggest that the type of sorbent is not nearly as important as the provision of a cool surface for the PCBs to condense onto. Thus, sample collec tion apparatus geometry and temperature may be of much greater importance than is commonly realized. MONS 223531 82 Analytical Chemistry of PCBs TABLE 4-1! COMPARISON OF A0S0RPTI0N ANO RECOVERY EFFICIENCY OF THREE S0R8ENTS Adsorbent* Florisi1 Tenax XAO-2 Sampling rate (i/min) Recovery (X) 2,2'-Oichlorobipnenyl 2,2'.4,5'*Tetracnlorobiohenyl 2,2'.3,3'.4,4'-Hexacnlorobipneny!1 Mean 17b 71.4 90.5 80_i 80.8 20 20 82.7 92.8 91.0 88. 8 34.0 S9 2 :7 Q SO. 1 a Simi 1 ar volumes or soroent m a 22-TM iQ tuoe sampieo at mbint temperatures. PCBs vaporized in air upstream of sorbent. b Maximum flow rate obtainable. Source: Haile end Baladi (1977). TABLE 4-111 SAMPLING EFFICIENCY OF FL0R1S1L SAMPLING TRAIN PCS Mixture Total Spike (ug) Recovery* (X) Aroclor 1221 Aroclor 1242 Aroclor 12S4 23.8 18.2 11.6 86 : 9 88 10 92 i 3 a Average and standard deviation for six tests. Source: Haile and Baladi (1977). MONS 223532 Sample Collection ana Storage 83 Based on the work by Haile and aaladi~(1977) which was recommended by EPA's interim manual (Beard and Schaum. 1978). Piorisii ''as often been used to trap PCBs from stack gas. for example, it w$ used in the first (October 1979) trial bum at the ENSCO Incinerator in El Dorado, AR (EPA, 1981b), and at two industrial boiler tests (Hall t al.. 1982: Polcyn et a)., 1983). One disadvantage is its rela* tively fine mesh which results in a high pressure drop and lower flow rates during sampling. Another disadvantage is its intolerance of water. In high humidity, florisll will hydrate, cake up, and block the air flow. The use of Florisil in four PCS incineration trial burns was reviewed by Ackerman et al. (1983a) A dual trap system with Florist T followed by XAO-2 was employed at the Rollins Envimomental. Deer Park, Tx (EPA, 1981). second ENSCO, El Oorado, AR (EPA, 1981b), and Vulcanus mT trial burns (Ackerman et al., 1983b). The lack of a consensus on sorbents has'apparently led some sampling teams to use both XAO-2 and Plorisil to ensure the acceDta* bi1ity of the data. A number of studies have employed XAO-2 in the sor bent cartridge in a modified Method 5 tram (Stanley et al., 1982; Haile et al., 1983a,b, 1984). Its use in PC8 incinera tion trial burns has been reviewed by Ackerman et al. (1983b). XAQ-2 was recommended by the EPA for sampling dur ing PCS trial burns (Beard and Schaum, 1978) and also by a standards working group (ASMS, 1984). 3. Liquid sorbents: Oespite some early use, liq uid sorbents have not been extensively used for sampling stack gas. The primary liquid sorbent has been ethylene gly col. liberti et a). (1980) used toluene in two tandem impingerf to sample organochlorine compounds, including PCS $, from an urban incinerator. The subject has been reviewea (Mergeson. 1977; Ackerman et al., 1983a). 4. Samplinq design: The sampling design must meet the objectives of th study. The sample volume, number of sample*, waste feed rates, etc., must all be carefully con sidered beforehand. It is pertlcularly important to under stand alt of the releted variables which impect on the meesurable destruction efficiency. This subject has been pre sented in more deteil (Erickson et a)., 1984a). Another aspect of the study design is distinguishing between PC8 missions and background. A background or baseline run may be an appropriate part of the QC program. Haile et al. (1983b) found that the PCBs emitted from seven coel-Mred utility boilers were higher than the levels in background HONS 223533 64 Analytical Chemistry of PCBs air, but that the two levels .ere generally within one stan dard deviation. Furthermore, the homolog distributions were similar. These two facts indicate that the PCS emissions from these plants may have just passed through the plant witn the combustion air 5. Qiscussion: Stack sampling for PCBs is gener ally done using a complex sampling apparatus designed to sam ple isokinetically and to collect several fractions for a va riety of analytes. In the U.S., the apparatus of choice i$ the modified Method 8 train. Th* exact geometry of the mooified sampling train and the choice of sorbent (XAO-2 or florisil) differ among sampling groups although XAO-2 appear* to have been more preferred in recent years. It appears that the chemical properties of the sorbent may be less important than the physical presence of a cool surface for condensation of the PCBs. Since it has been shown that substantial amounts of PCBs are collected in the probe and other parts or the train olumbing (Haile et a 1. 1983a) it is particularly important to validate the collection and recovery efficiency with the full train under realistic conditions. Better vaiidation techniques are needed to fully assess the collection and recovery efficiency of a sampling system under a given set of sampling conditions. Unless further method validation studies indicate an acceptable alternative, source sampling should utilize a modified Method S train with XAO-2 as the sorbent. The con tents of the entire train (probe, rinse, filter, any uostream impingers. and the sorbent cartridge) must be analyzed for PCBs. As noted above, the modified Method 5 filter should not be used to measure the Method 5 total particulate. Proper experimental design and QC are necessary to discrim inate between unreacted PCBs from the incinerator and PCBs collected from background air. III. NATURAL GAS IN PIPELINES A procedure (Harris et a 1. , 1981) for the sampling and analysis of natural gas for PCBs utilizes the NIOSH Flor isil tubes (HtOSH, 1977a,b.c). The Florisil tube is con nected to a valved port in the line through appropriate fit tings. A Magnahelic, rotometer or dry gas meter downstream monitors the flow rates or volume. HONS 22353* Sample Collection and Storage IV. SOUPS 65 Soil, sediment, biota. and tissue sampling for PCBs all utilize general trace organic sampling techniques. Sam pling equipment and containers must be glass, steel. TFE, or other non-contaminating materials. The samples collected must be representative of the system, and the sample volume must be sufficient for the analyst's needs. Oocuments on sampling hazardous waste streams (devera et a!.. 1980). soil (Mason. 1982), and PCB spill sites (Kelso et a!., 1985) give additional guidance. Using a mobile atmospheric pressure chemical ioni sation mass spectrometer, Lovett et al. (1983) demonstrated a real-time sampling/analysis technique for soil and other sol ids. Air from the surface of a spill, or soil core was pumped through a heated transfer line, "surface sniffing," to the spectrometer. A detection limit of 500 ug/g was reported. V. SUBPACES Solid surfaces may need to be sampled to assess either PC8 contamination or the effectiveness of cleanup after a PC8 spill. These solid surfaces may be smooth and impervious, such as a drum interior, or rough and porous, such as an asphalt driveway. No standard surface sampling technique has been issued by an organization. In an EPA guidance document on PCB spill cleanup, Kelso et al. (1985) recommended that nonporous surfaces be sampled by wiping. Surface wipes are taken with a moistened piece of filter oaoer with toluene, 'sooctane, or other ao~ propnate solvent. The filter paper is held with a pair of stainless steel forceps and used to thoroughly swab a 10 cm x 10 cm area of the surface to be sampled. A template should be used to define the area. The wipe technique should be performed reproducibly. The wipe sample is stored at approx imately 4#C in a precleaned glass jar. Wipe samples are not appropriate for porous surfaces which may absorb the PC8s. These surfaces such as wood, as phalt, and concrete should be sampled by physical removal of a representative portion (Kelso et al., 1985). The sample can be collected by chipping, drilling, coring, chiseling, etc. MONS 223535 86 Analytical Chemistry of PCBs VI. OIL, DIELECTRIC cIUI0S. ETC. A large number of PC8 analyses involve transformer oil. hydraulic Mu'0. askarels, and other similar oils which may be contaminated with PCBs Since these oils are gene'** ally contained in a transformer, drum, tank, etc., obtaining a sample may be as simple as opening a drain valve. The only consideration in samoling <$ representativeness. Especially where the oil is highly contaminated, me PCS content may not be homogeneous. for example, a drum of waste oil may contain several pha$es-*a sludge, a water layer, and an oil layer. The PCB content of the three layers would differ markedly Thus, the sampler must attempt to obtain a representative sample. Small containers may be mixed. with larger con tainers, suosamples from various depths may need to be taken HONS 223536 5 EXTRACTION Reliable trace organic analysis begins with the quantitative extraction or the analytes from the sample ma trix. The general objective of an extraction technique is to separate the analyte (e.g., PCBs) from the sample into a ma trix which is more compatible with the rest of the analytical procedure. The exact separation process is dependent on the complexity of the physical and chemical nature of the matrix the general ormcioies and techniques of extraction for trace organic analysis have been reviewed (Poole and Schuette, 1983) PC8s are readily extracted from matrices such as water, but are difficult to extract from oil and other ma trices in which they are readily soluble. This chapter reviews the literature and discusses licable extraction techniques by matrix. After a discus- of general Dhysicai and chemical considerations, extrac tion techniques for water, sewage and sludge, sediment and soil, air, blood, animal and plant tissue, paper products, and oils are presented. A section at the end of the chapter discusses solvent evaporation, losses of PC8s through sorp tion onto glass containers, and sources of contamination. Many of the extraction techniques discussed in the literature are derived from traditional pesticide analytical methods, and their adaptation to PC9 analysis was made with little or no reported research or validation. Thus, most of the PC8 extraction teehiques discussed in this chapter may be best described as "workable" but not "optimized." I. GENERAL CONSIDERATIONS As noted in Chapter 2, PCBs are nonpolar, semivola tile organics. Thus, they are highly soluble in nonpolar sol vents such as hexane and only slightly soluble in polar sol vents such as water and acetonitrile. This property is ad vantageous for extraction from water samples, since the PCBs will readily partition from the watar to most nonpolar (i.e., immiscible) organic solvents. However, when the PCBs are 87 HONS 22353? 38 Analytical Chemistry of PCBs dissolved in a nonpolar matrix such as oil. the extraction process becomes much more difficult, if not impossible The physical mechanism of the extraction can aiSo be important. The extraction solvent must come into contact with the entire sample to reliably extract the PCBs. With soil, tissue, and other solids, physical mixing or maceration is necessary to assure effective contact. Even more harsn techniques such as ultrasonic disruption or chemical degrada tion (e.g. , saponification with base) may be reou'reo to break up Cells, macromolecules, or other matrix components which could entrain PCBs. The rigor of the technique must be balanced between efficient extraction and degraoation or loss of the analyte. As with any partition scheme between two onuses. PCS extraction relies on a favoraole partition of the PCBs from the sample matrix into the extraction matrix. The more favorable the partition coefficient, the higher the extrac tion efficiency. Efficiency is also imoroved by nepetit'Ous extractions. If. for examole. the partition coefficient, k. is 9, thn 90S of the PCBs will extract from the sample to the solvent in the first extraction (at equilibrium). The second extraction will also yield 90S of the remaining PCBs for a total extraction of 99V After three extractions, the combined extracts should contain 99.9% of the sample, with a lower partition coefficient, more repetitions are required for a similar total extraction. For most matrices, K has been presumed to be high and the traditional number of reptmions is 3. II. WATER Extraction of PCBs fro* water >s generally straightforward, since the solubility $ so 'ow. 4 simole liquid-liquid extraction with any water-immiscible solvent should yield adequate results. As shown in Table 3*1, the standard procedures prescribe hexane, methylene chloride, or mixed solvents for water extraction. The sections below de* scribe considerations for 1 iquid-1iQuid extractions and also present some of the other extraction technioues reported in the literature. A steam distillation technique has been used for extraction of water samples, but was validated primarily for fish samples and is discussed in Section Vll.8.3, below. A. Liquid-liquid Extraction The classic liquid-liquid extraction techniques in volve a simple shaking of the water and solvent in a separa tory funnel. Continuous 1iquid-1iquid extraction is simply MONS 223538 Extraction 89 4n "automation" of the separatory funnel shakeout, "fore eso teric extraction techniques include steam distillation and sorbent column extraction. The latter is particularly ap* pealing for on-site extraction of large volume water samples to achieve very low detection limits. On*$ite water extrac tion was covered under "sampling" (Chapter 4). A study or water extraction solvents and conditions py Miliar et a). (1981; 198?J found no distinctly advanta geous combination of solvent and pH for all PCBs. In the study, a roc 1ors 1016. 1221. 1232, 1242. 1248. 1254. and 12S0 were spiked into unchlonnated well water. The spiked sam ples were then adjusted to pH 2. 7, and 10 and extracted with either dichloromethane/hexane (15:85) or oure dichloromethane. The results were analyzed Dy analysis of variance (ANOVA), For some PCB mixtures either one or the other sol vent was preferable. The effect of pH was similarly con founding; neutral, basic, and "no preference" were statistic ally shown to be the best conditions for various Aroclors. It appears from these data that there is no significant dif ference in these conditions for all PCBs. A liquid*liquid extraction followed by a XOH sapon ification technique has been developed for paper mill efflu ents (Easty and Wabers, 1978; Oelfino and Easty, 1979). Water samples are extracted three times with hexane and then cleaned up on a Florisil column prior to PGC/ECO determina tion. After the hexane extraction, the water sample is fil tered and the isolated paper fibers are refluxed in alcoholic KOH to remove any PCBs. Without the KOH saponification, about 10% of the PCBs remained on the fibers after the hexane extraction. 8. Continuous Liould-Liouid Extraction TCLE) Continuous liquid-liquid extraction (ClE) is a labor-saving technique to replace the common separatory fun nel. In addition CLE is less likely to cause emulsion pro blems with very dirty matrices. A wide variety of apparatus have been described to effect CLE. Most involve refluxing solvent from a flask, which then drips through a water sample and returns to the flask. Godefroot et al. (1982a,b) demonstrated the appli cability of a combined steam distillation/solvent extractor for PC8s. The technique, a micro version of the Nickerson and Likens (1966) apparatus, simultaneously steam distills and gas-phase extracts PCBs and similar organics from 50 mL water into 1-mL pentane. The recovery for Aroclor 1260 av eraged 95%. HONS 223539 90 Analytical Chemistry of PC8a c. Soroent Column Extraction With this technique, a water sample is passed through a sorbent column where the PCBs and other organics are "extracted" onto the soroent. The adsoroed organics are then eluted from the column with an organic solvent. The distinct advantage of sorbent column extraction is the abil ity to extract targe water volumes to ennance the method de tection limit. The soroent column extraction of large water volumes (over two liters) has been emgloyed in the field, as discussed under "Sampling" (Chapter 4). Coburn et at. (197?) reported an XAO-2 column tech nique for extraction of 2*1 samples with subsequent elution with ethyl ether. At the 250-ppt level. 78-86% recoveries were observed for a mixture of Aroclors. A polyurethane foam column technique gave 91-98% recovery at the 20-ppb level from l-i water samples (Gesser et al.. 1971). The PC8$ -ere eluted with acetone and then hexane. Similar results have been shown using XAO-2 or XAO-4 for sea water (Osterroht. 1974) and tap water (Musty and Nlckiess, 1974a). Picer and Picer (1980) compared XAO-2, XAO-4, and Tenax for extraction of PCBs from see and tap water. The Tenax yielded many more peaks at larger intensity, which more closely resembled an Aroclor mixture than the other resins. However, severe PGC/ ECO interferences were noted with all of the sorbents. Leom et al. (1976b) achieved 100% recovery of PCBs at 1.6 ppb in 10-L samples of surface water. The PCBs were collected on a column containing Tenax and Celite and then eluted with three 10-ml portions of ethyl ether. A C -18 reversed phase partitioning cartridge (Sep-Pak, Waters Associates) was used by GaUis et al. (1983) to aosoro PCBs from water samples, me cartridges were pre conditioned with methanol. 0. Purge and Trap A purge and trap technique was demonstrated to yield greater then 90% recoveries for Aroclor 1221, 1248, and 1264 (Colenutt and Thorburn, 1980). Water samples (2.0 l) were purged at room temperature for 4 hr at 1 L/min. The PCBs and other compounds were trapped on S-2S mg activated cerbon. The carbon trap was subsequently desorbed with SO* 1,000 pi of pentane, carbon disulfide, carbon tetrachloride, or diethyl ether. This extract could then be analyzed by PGC/EC0. HONS 223540 Extraction i. Comparison of Extraction Techniques 91 Solvent extraction gave better results than XAO-4, a "partition system'' (Carbowax 4000 monostearate anti n-undecane coated on Chromosorb W) or polyurethane foam (Musty and Nickless, 197$). Recovery of PCBs at the 10*20 ppO level from water un the partition system ranged from 97% to 48%, decreasing with increasing chlorine content of the PCBs. The concentration of PCBs, measured as Aroclor 1260. in a water sample with the solvent extraction (diethyl ether/hexane. 15:85) technique was over twice that found with any of the three sorbent column techniques. Be'lar and lichtenberg (1975) found separatory fun nel 1 iquid*!iquid extraction.to be the most efficient extrac* tion technique for recovery of PCBs from natural waters. The use of polyurethane foam plugs**both in a column-elution mode and where the plug is soaked In the water sample--gave good recoveries with distilled water. With natural waters, how ever. the particulate matter stopped flow through the column. With natural waters, the recoveries from the soaking tech nique had poor precision. In addition, the PUP contributed significant background interferences to the GC/EC0 analysis. A vortex extractor gave lower and less reproducible results, although it was not thoroughly evaluated. III. SEWAGE ANQ SLUDGE These ill-defined matrices range from "dirty weter" to high-organic solids. Thus, many different extraction techniques have been employed. For raw municipal sewage with relatively low organic content, the sample can be extracted using e water technique, such as solvent extraction in a sep aratory funnel More viscous samples can aiso be treated this way by simply diluting the matrix to the desired consistencyat a sacrifice of the method detection limit. The effects of the high levels of organics on ex traction efficiency were illustrated with a sorbent-column technique. Only 23 or 60% of the PCBs spiked into raw sewage were extracted with XAQ-2 or XAQ-4, respectively (Lawrence and Tosine, 197$). Apparently, the sorbent overloaded with this high organic-content matrix. Surprisingly, a column of polyvinyl chloride chips gave the best (73%) adsorption of PCBs and was recommanded by the authors. Four extraction techniques were compared by Rodriguez et a). (I960) in the development of e method for analysis of municipal sewage sludge for PCBs and chlorinated pesticides. The extraction techniques evaluated were; HONS 223541 92 Analytical Chemistry of PC8a (1) Cent**1 1uge Aceton#/di cnloromethane/hexane (2:15:83) mature and then centrifuged to sep arate the emulsified mixture. The upper sol vent layer is removed and the process repeated twice more (2) Column Elution. The sludge (20 g) is mixed ith 80 g annydrous sodium sulfate and then packed into a liquid chromatographic column. The PC8s are then eluted with ISO ml of acetone/hexane (20:80). (3) Soxhlet Extraction. The sludge (20 g) '$ mixed with 180 g anhydrous sodium sulfate and then Soxh*et-extracted with dichloromethane/ hexane (1585) for aoout 40 cycles. (4) Continuous L iouid-tiomd Extraction. Th* sludge w'0 g;, onuteo >th 10 *t water aurtng transfer, was extracted overnight with dtcnloromethane in a modified Soxhlet extractor. The latter technique gave poor (< SOX) recovery, presumably because of poor solvent-sample contact. The first three techniques gave high (> BOX) recoveries. A variety of rea sons including potential interferences, cost, and ease of use, led the authors to recommend the centrifuge technique, which gave 98% recovery of Aroclor 1260 from primary sludge and 80% recovery from digested sludge. IV. SEDIMENT ANO SOIL Sediment and soil diffp- from sewage sludge in their generally lower organic content. As with sewage sludge, the critical component of an extraction technique for either sediment or soil is the contact between the solvent and the matrix. This has generally been accomplished by physical mixing (e.g. , manual shaking) and use of a "wetting" solvent mixture (e.g., hexane and acetone). With soil sam ples, especially, thorough mixing and pulverizing of chunks is an Important preextraction step. A. Solvent Extraction The classic work on extraction of chlorinated in secticides (PC8s were "co-extractives" which could be removed in the chromatographic cleanup) from sediment is by Goerlitz and law (1974). The sediment (SO g) is centrifuged to remove excess water, wetted with 40 ml acetone, extracted with 80 ml hexane, re-wetted with 20 ml acetone, and extracted again HONS ZZ*$hZ Extraction 93 with hexane. Between each solvent addition, the sample is shaken 20 mm on a wrist-action shaker. The extraction should De repeated until at least 75% of the added solvent is recovered. PCS recoveries were 100% after i extractions. This basic approach has been utilized in many other studies, with modifications in the solvent ratio, volume, agitation tine. etc. (Eder, 1976a: Jensen et al., 1977; Chau et al., 1979} Other "wetting" solvents have also been used, such as acetonitrile (ANSI, 1974) or water/ecetonitri1e (ASTM, 1901b). Wetting the soil prior to solvent extraction ap pears to increase the extraction efficiency. A SoxMet ex traction of dry soil with hexane for 10 hr gave 30% recovery of radiolabeled Chlophen A-30 (Seidl and 8alIschmiter, 1976a). while 85% recovery was measured using the same tech niques from wet $0)1. The soil-was wetted with 1 g water per 15 g soil. B. Collaborative Studies Lee and Chau (1981a) conducted an interlaboratory validation for PCBs in wet sediments. Both native and spiked (about 1 ppm) samples were analyzed. The participants were permitted to use analytical methods of their choice for the analysis of the materials. Of the methods used in the ex traction of PCBs from sediment, which included ultrasonic, SoxMet, blender and shaker methods, the ultrasonic was the most popular. In this study, SoxMet extraction did not seem to provide higher recoveries of PCBs in comparison with other extraction techniques. Host participants used a mixture of polar and nonpolar solvents, sucn as 1:1 acetone and hexane, as the extracting solvent, while others used a single polar solvent sucn as acetonitrile or acetone. No oovious rela tionship was observed between the recoveries and the extrac tion procedure. This suggested to the authors that all the extraction methods used in this study were equally efficient for the recovery of PCBs in spiked sediment samples. A sec ond collaborative study (Lee and Chau, 1981b) of PCBs in na turally contaminated dry sediments exhibited too mueh varia bility for the mthort to make Inferences on the differences in analytical techniques. The study is described in more de tail in Chapter 10. C. Thermal Desorption Thermal desorption is commonly used for volatile compounds, such as chloroform, but only rarely employed for semivolatiles such as PCBs. The higher desorption tempera tures and possibly lower desorption efficiencies probably MONS 223543 94 Analytical Chamlatry of PC8a contribute to this lack of popularity. On the other hanc thermal desorption can yield fewer interferences and has tha d'sttnct advantage of introducing the entire sample to the instrument. This provides potentially much better method de tection limits than with solvent extraction where only 1/1000 of the sample is typically injected onto the gas chromato* graph. Lovett et al. (1983) reported the use of both a surface-sniffing and thermal desorption techniques for rapid analysis of PC8s at spill sites. Samples were volatilized and then directly introduced into a mobile atmospheric pres* sure chemical ionization mass spectrometer (see Chapter 7) The surface sniffing technique had a detection limit of 500 pg/g, while thermal desorption could detect 10 pg/g. The thermal desorption technique used mini-core soil samples and nao a total analysis time of 3 min. No details or validation was reported. Thermal desorption has also been used to introduce PCBs to a conventional PGC/EIMS (McMurtrey et al., 1983) Samples were desorbed under a helium stream for 10 sec at 1000C. The desorbed materials were trapped at the head of the cool GC column. PCBs were detectable at the 10 ppm level, although the HOI was not determined, nor was the quantitative reliability of the method presented. The authors mistakenly termed the PCB desorption technique "py rolysis." Thermal desorption of PCBs from hazardous waste samples into a triple quadrupole MS/MS system has also been described (Hunt et al., 198S). The above results indicate that thermal desorption may well be a viable technique for rapid screening analyses Until validation data are presented, the technique cannot be recommended for quantitative analysis. 0. Comparison of Sediment and Soil Extraction Techniques Three techniques were compared for the extraction of PCBs from bottom materials (Bellar et al., 1980); they were: (1) Soxhlet extraction: The Soxhlet extraction was conducted overnight with acetone/hexane (10:90) and the extract concentrated with a Kuderna*0anish evaporator, cleaned up on FlorisU, and then treated with mercury to remove sulfur. MONS 223544 Extraction 95 (2) Somcition: The sonication techniqu# involved a single 5-<nin somcat'on it a power of ISO watts with ISO ml acetone over a 60*90 g sen* pie. The acetone was then decanted, diluted with water, and the organics extracted with hexane/dichloromethane (8S:15). The extract was concentrated and cleaned up as with the Soxnlet extraction. (3) Steam distillation: The steam distillation technique employed the Nielson-krygtr appa* ratus for simultaneous distillation and ex* traction with hexane. Prior to extraction with all three techniques, samples were air-dried, debris (stones, leaves, twigs, etc.) was removed, the sample was mixed, ground in a mortar and pestle and then subsampled. All three extractions gave quantitative recov eries of Aroclor 1254 spiked onto latte bottom samples, how ever. the Soxhlet extraction gave 2S*40% higher results than the other two techniqeus for environmentally contaminated samples. These results emphasize the importance of validat ing methods with real samples, where the PCBs have been thoroughly incorporated into the matrix. 8ellar and lichtenberg (1975) found that Soxhlet extraction of air-dried, 10% water*added bottom materials (muck and sandy muck) with a mixture of acetone/hexane (1090) was the most efficient method for extracting PCBs. The less* efficient techniques included shaking with acetone and then hexane, shaking with an isopropanol/hexane mixture, blending with an acetonitrile/acetone mixture, preparation of a column by mixing with sodium sulfate and then eluting with either hexane or hexane*ecetone, end high freouency dispersion with acetone. All or tne techniques tested were taxen from the literature. Water/methanol/hexane (10:40:50) gave the best re* covery of Aroclor 1242 from dry sediment (Spittler, 1989, 1984) in e single extraction of the sediment for screening purposes. The other solvent systems, which gave poorer re coveries were hexane, water/hexane (50:50), water/ethyl ether/hexanm (33:33:99), water/ethyl ether (50:50), water/ methanol/ethyl ether (33:33:33), and methanol/hexane (50:50). V. AIR PCBs should be readily extracted from the sorbent materials used in air sampling. As discussed In Chapter 4, PCBs are generally "extracted" from the air sample onto a HONS 223545 9e Analytical Chmmistryof PCBs sorbent material during the sampling This sorbent is then returned to th laboratory for analysis. th first step of wnich is a solvent extraction. Chapter 4 presents a detailed discussion of the various sorbents used in air sampling. Thasa include polyurethane foam (PUF). Flonsil. XA0-2 and other macroreticular resins. PCBs are extracted from these sorbent matrices by repeated extraction with a nonpolar solvent such as hexane, benzene, or methylene chloride. Often a continuous extrac tor. such as the Soxhlet extractor, is used to effect the re peated extractions. An important consideration of the at traction technique is contact between tne solvent and aj_l_ of the sorbent. Column elution or other techniques which may develop channeling of the solvent and thus do not ensure com plete contact must be scrutinized carefully to assure Quanti tative extraction of the PCBs. A. Polyurethane Foam PCBs are extractable from PUF plugs using nonpolar or semi-polar solvents. Petroleum ether (e mixture of pen tanes end hexanes, now generally replaced with pesticide res idue grade n-hexane) has been used to Soxhlet-extract PUF plugs (Bidleman and 01 nay, 1974; Bidleman, 1981; Bidleman et al., 1981a; Bidleman and Leonard. 1982). MacLeod (1979) used ethyl ether/hexene (5:95) in a Soxhlet. Erickson et al. (1980a) used toluene, which had been shown to be the most ef ficient for extraction of polychlorinated naphthalenes (Erickson et al.. 1978). Mechanical squeezing was used in stead of Soxhlet extraction to improve the efficiency of ex traction from the middle of the plug. One study (Adams and Caro. 1980) has compared the mechanical extraction techniques for PUF. although PCBs were not tested, similar organochlorine pesticides make the data relevant to this discussion. Soxhlet extraction (S cycles) squeezing (5 times with e metal plunger) end column elution, all using acetone/hexane (50:50) wore compared. The three techniques gave 96 to 101X recoveries with 11 to 18S flSO. Thus, for e series of 11 organochlorine pesticides, these three mechanical extraction techniques appear to be equiva lent. 8. Fiorisll Florisil (trademark, Floridin Company) is a syn thetic magnesium silicate. Most of the authors using Florisil for air sampling have extracted the PCBs with hexane, although one early report (Glam et a)., 1975) used petroleum ether followed by ethyl ether to eluta PCBs from a column MONS 223546 Extraction 97 prepared with the air sampling Florisil. Collin elution has been reported when the amount of Florisil i$ smell (Grm et al., 1975: Hams et al , 1981: Wil 1 iams et al. , 1980). The nIOSH method (1977a.b.c) directs the analyst to simply mix the hexene and Florisil for at least 10 min and then inject an aliquot of the supernatant hexane on the PGC/ECO. Haile and Baladl (1977) used a Soxhlet-extractlon with hexane to desorb PCBs from a 7.5 g Florisil stack sampling cartridge. C. KAQ-2 The extraction of XA0-2 is generally done with a nonpolar solvent such as hexane, benzene (Stanley et al., 1982) or petroleum ether (Eisenreich et al., 1981a) in a Soxhlet extractor The amount of XAQ-2 used (typically 75 g of low-density polymeric resin) makes sample handling more difficult than with the small amounts of Florisil. so the Soxhlet technique has been more popular. 0. Orv Oeoosition Samples Sample collectors (aluminum pans or glycerin-coated pans) are rinsed with solvent to remove the particulate and PCBs. Bidleman et al. (1981a) rinsed their pans with dis tilled water and acetone or dichloromethane and then scraped the surfeee repeatedly with a piece of Teflon* to ensure re moval of adhered material. The combined rinses were then ex tracted with dichloromethane. Eisenreich et al. (1981a,b) washed the PCBs from dry deposition pans with PC8-free water only, which was subsequently extracted by steam distillation into toluene. It is surprising that only a water wash was employed, given the poor solubility of PCBs in water (see Chapter 2). vi. 8LOOP The extraction of blood samples generally entails a simple liquid-liquid partition of whole blood, plasma, or serua with solvent. The techniques differ from those for other aqueous liquids In how the cells and proteins are han dled to assure complete extraction and avoid emulsions. In addition, blood samples are generally small (e.g., 10 ml) relative to water and many other samples, so the mechanical techniques of agitation, etc., are different. Whole blood is essentially the same matrix as ob tained from the body, except for the possible addition of an snticoagulant, such as heparin, to retard clot formation. Plasma is the liquid portion of the blood obtained after MONS 223547 98 Analytical Chemlatryof PCBs physical removal of the cells from whole blood by centring*, tion. Serum is the fluid remaining after the cells ang platelets are allowed to coagulate PC8 analyses have been conducted on all three "blood" matrices. The results may not be comparable, since an unknown portion of the PCBs in whole blood can be removed with the cells or clot. Blood extraction procedures have been issued by two organizations: the U S. Environmental Protection Agency ana the US. Centers for Oisease Control. Host of the references in the primary literature involve one or the other of these procedures. Thus, this section has been divided into subsec* tions describing these two procedures and their validation. A. Envirpnmenta 1 Protection Agency The EPA manual for pesticide residue analysis (Sec tion 5.A.(3),(a), watts, 1980} describes a nexane extraction for serum: "A 2*ml aliquot of serum is extracted with S milliliters of hexane in a round-bottom tube. The extraction is conducted for 2 hours on a s'ow-speed rotating mixer. The formation of emulsion is un likely, but if it should occur, centrifugation may be used to effect separation of the layers. A 5-ml aliquot of the hexane layer is quantitatively transferred to an evaporative concentrator tube to which is affixed a modified micro-Snyder column. The extract is concentrated in a water or steam bath, and the final volume is adjusted to corre spond to the expected concentration of the pesti cide residue. A suitable aliquot is analyzed by electron capture gas chromatography." The method was developed for organochiorine pesticides (Oale et al., 1966) and PC8s are not listed as potential analytes in the method (Watts, 1980). Nevertheless, the technique has been adapted for the determination of PCBs (Curley et al., 1971) and has been routinely used for PC6 analysis (Erickson et al.. 1983e). In the originel form (Oale et al.. 1966), thm extraction entails e vigorous mixing for 3 min on a mini mixer, yielding an emulsion which is then broken by centrifu gation. The EPA modification (Watts, 1980) recommends a gentle mixing for 2 hr on a rack wnich gently rotates the tubes end*for-end. This technique, while much slower, avoids emulsions in most cases and thus saves an additional step. The EPA extraction involves only a single parti tion. In addition, although 6 ml hexane are added, only 5 ml ar recovered, since the hexene-serum interface is indistinct HONS 223548 Extraction 99 4U to * layer of protein. The lack of full solvent recovery i$ compensated in trie calculations by multiplying trie PGC/ECO results by 6/5. 8- Centers for Qisease Control Researchers at the Centers for Oisee.se Control (CDC) have developed methods for determination of PC8s in serum which utilize a triple extraction with ethyl ether/ hexane (50:50) (Needham et a I, 1961: Burse et a 1.. 1963a). Specifically, a mt serum and 2 mi methanol are mixed to dena* ture the protein. The specimen is then extracted with 3 x 5 mt ethyl ether/hexane (50:50). Each extraction is con* ducted for 15 min on a rotary mixer at 50 rpm. The organic and serum layers are separated by centrifugation at 1600 rpm. The combined extracts are concentrated to 0.5 mL, cleaned on silica gel, and determined by PGC/ECO No recovery data were presented; however, the precision of the entire method was x 33% RS0 at 2 ppb Aroclor 1254 and t 12% 8S0 at 46 ppb. Us* ing a similar extraction, McKinney et al. (1964) quantita* tively (90*100%) recovereo Aroclor 1254 except near the de* tection limit (10 ppb), where the recoveries were 77%. The precision was less than zl0% RSO. An earlier publication (Needham et al., 1980) em ployed a similar extraction technique, except the extraction solvent was hexane alone. A recovery of 94 t 5% for Aroclor 1260 spiked into serum at 41 ppb was measured for the entire method. Yet another version employed the ethyl ether/hexane extractions, but added a saponification step (Baker et a)., 1980; Stratton and Geiszler, 1977). The concentrated organic extract was saponified by addition of 2 mi. of a 2% K0H in methanol solution. The mixture was refluxed end concentrated to about 0.3 mL, taken up in 2 mL water/methanol (50:50), end then extracted three times with 2 mL hexane. The combined hexane extracts were then submitted to silica gel chrometog* I'apny. Recoveries of 99 c anq 106 c 7% were reported by two laboratories (Stratton and Geiszler, 1977). Based on these limited results, the choice of hexane or ethyl ether/ hexane dees not appear to have a marked effect on the ex* traction, Hexane was the favored extraction solvent in a col* Uborative study of PC8s in blood sarum (Burst ttal., 1983d). Of tha 25 participants, 12 usad hexane, 8 used athyl ether/haxane; 2 extracted with acatonitrile and than parti tioned into hexane or petroleum ether (see section on extrac tion of adiposa tissue, above); 1 used a mixture of isopropanol/patroleum ether, and 1 adsorbed the blood on a Florlsll column. Nine of tha participants denatured the protein with methanol, while 15 did not. The scatter of the data did not HONS 223549 too Analytical Chemistry of PCBs permit comoarison of tn# efficiency of the traction tech niques. This study is discussed further in Chapter ig C. Comparison of Blood Extraction Techniques The extraction of whole blood with hexane-saturated acetonitrile was found to be quantitative (97*), while e*. traction with hexane alone achieved about 40% recovery (Welborn et a)., 1974). In addition, the hexane extraction was selective, with higher recoveries for early-eluting PCB peaks o'n the PGC/ECO. The hexane extraction involved vigor ous shaking with three aliquots. The combined extracts were dried with sodium sulfate, concentrated, cleaned on alumina, and determined by PGC/ECO. The more efficient technique en tailed vigorous shaking three times with hexane-saturated acetonUri le. The combined extracts were dried with sodium sulfate, diluted with water, and extracted with three por tions of hexane. The combined hexane extracts were concen trated. cleaned on alumina and determined by PGC/ECO. The publication does not explain why both techniques were con ducted on a macro scale. The solvent volumes were SO ml./ xtraction--the volume often used for extraction of 1-L water samples. VII. AN I HAL AND PUNT TISSUES This broad sample matrix category spans a continuum of polarity and extractabi1ity. At the one extreme, adipose tissue can be almost entirely extracted into the organic sol vent. leaving only a small residue of non-extractable matrix. In this case, the matrix has simply been dissolved in the solvent and the PCBs must still be extracted from the lipids. At the other extreme, many plant tissues (food) can be easily extracted with organic solvents, yielding a relatively clean extract. A. Adipose Tissue Adipose tissue, from either humans or animals, con sists of both lipids ("fat") and connective tissue. Spearman (1962) has published detailed review of the properties and biochemistry of adipose tissue. Most extraction techniques first separate the PCBs along with the lipids and any other soluble organics from the connective tissue. The PCBs and other compounds of similar polarity are then separated from the lipids. Host procedures also contain provisions for deter mining "percent fat" by evaporating the solvent from an all'quot of the original extract and then weighing the residue. HONS 223550 Extraction 101 Knowledge of trie fraction of the sample which is extractable is important m comparing tne PCS content of different sam ples. 1. Acetonitrile back-partition: A classic adipose and food extraction procedure developed by Hills et al. (1963) involves first extraction of th# lipids from the con nective tissue with petroleum ether and then extraction of the PCBs and pesticides from the petroleum ether into aceto nitrile. Like many other techniques, it was originally de veloped for organochlorine pesticides and subsequently adapted for PCBs. This MiUj-Onley-Ga'ther ("HOC") procedure has formed the basis of many techniques subsequently re ported. For example, the EPA method (Watts. 1980) for pesti cides in adipose involves: "A 5 g. sample is dry macerated with sand and Na?S04 and the fat is isolated by repetitive extractions with oetroleum ether. Pesticide residues are extracted from the fat with acetonitrile and then partitioned back into petroleum ether by aqueous dilution of the acetoni trile extract. Petroleum ether extract is concentrated to 5 mL by Kuderna-Oanish evaporation and transferred to a Flonsil column for successive elutions with 6% and 15% ethyl ether/ petroleum ether. The respective eluates are both concentrated to suitable volumes in Kuderna-Oanish evaporators and the final extracts are examined by electron capture gas-liquid chromatography." Th PC8s and pesticides are separated in the Florisil step. PC8s are resolved from some co-eluting pesticides by silicic acid chromatography (see Chapter 6). Many users of this method now substitute pesticide residue grade n-hexane for the petroleum ether stipulated in the above procedure. The acetonitrile-hexane (or petroleum ether) partition ing step is reported to be time-consuming (Smrek and Needham, 1982). PC8s may also be lost during this step, since the partition ratio between the two solvents is probably rela tively low. 2. Acid digestion: An alternative approach was presented by Murphy (1972) in which the biological substances were removed from the hexane extract of adipose tissue by shaking the extract with concentrated sulfuric acid. The acid presumably degraded the lipids and other molecules, while leaving the relatively stable PCBs and chlorinated pesticides intact. HONS 223551 102 Analytical Chamistry of PCBs 3. Co 1 umn ch^owtography: Several grouos have in vestigated the use of a column chromatographic step to "X' tract" PCBs from the lipids. Ernst et al. (1974) groung frozen tissue samples with sand and sodium sulfate to form 4 powder which was poured into a glass column. The PC8s were then eluted from the column with acetone/n-hexane (33 67) while the entire system was kept cold. PCB recoveries for the entire procedure, including an alumina cleanup, were 96 99*. A similar elution of a mixture of animal tissue eng sodium sulfate with hexane was judged better than other tech niques (Bowes and Lewis. 1974). Specifically, lower recov eries were obtained for elution of tne column witn 4 methanoI/chloroform mixture (33:67). digestion with a hot perchloric/giacia) acetic acid mixture (40:60), and extrac tion with acetone followed by refluxing with hot isopropanol Smrek and Needham (1982) used a column of 13% silver nitrate on silica gel to retain the lipids, DOT. ana DOT metabolites, while eluting the PCBs with hexane. Recov eries were greater than 90* with standard deviations of less than 3* Prior to the column chromatography, adipose samples were ground with sodium sulfate to macerate the tissue anq adsorb water. The samples were then extracted with petroleum ether three times. Porter and Burke (1973) mixed 8 g fat with 25 g unactivated Horisit, placed the mixture in a col umn. and eluted with 150 ml water/acetonitrile (10:90). The eluate was diluted with water and the PCBs partitioned into petroleum ether, which was further cieened up with a Flonsil column and determined by PGC/EC0. Eighty*five percent of Aroclor 1254 was recovered from corn oil spiked at 100 ppb. Similarly, Swift and Settle (1976) isolated PCBs by distrib uting the fat sample on the top of a column of unactivated Horisil and eluting with water/acetomtri le (10:90). 4. Oisti nation: Sweep codisti nation from animal fat gave extracts which had PGC/EC0 detection limits of 10 ug Aroclor/g fet (Neidert end Saschenbrecker, 1984). with silanized distillation tubes to prevent adsorptive losses, 98* 99* recoveries of Aroclors 1248*1268 were observed. 5. Low temperature precipitation: Low temperature precipitation has also been used to remove lipids (McLeod and Wales, 1972). Samples were extrected by refluxing in acetone/ benzene (95:5) for 1 hr. The extract was then cooled in a dry ice bath for 30 min with a nitrogen stream bubbling through the solution. This caused lipids, waxes, water, and other compounds to precipitate. The supernatant was then separated from the precipitete by vecuum filtration on cellulose. Although not validated for use with PC6s in the original publication, the technique has been applied to PCS analysis of tissue and milk samples (Mes and Campbell. 1976; Mes et a 1. , 1977; Mes and Oavies, 1978. 1979). HONS 223552 Extraction 103 6. Comparison of lipid removal techniques: Sev eral mechanical tecnmques and extraction solvents were com pared m a study by He* and Campbell (1976). A Silverson \*er was found to be slightly more effective at lipid ex traction and easier to use than a Waring Blender or a Virtis Model 23. They also evaluated mn solvents and found a acetone/benzent (95:5) mixture to give the highest PC8 con centrations m unspiked human adipose samples. The other solvents were hexane, acetone/hexane (33:67), methanol/ Oichloromethane (67 33 ano 50:50), dichloromethane, benzene, water-saturated butanol, and diethyl ether/petroleum ether (50:50). F i sh Fish samples can often be extracted by techniques similar to those used for adipose tissue, since fish can con* tain several percent lipids. Fish ar* of interest because of their human consumot'on. indication of pC8 movement through aquatic and marine tropmc levels, ano the ability to stuoy PCB transport by comparison of migratory and nonmigratory species. 1. Solvent extraction: Soxhlet extraction has been used extensively for extraction of fish samples (Zitko, 1971a; Zitko et a!., 1974b; Frank et a)., 1978; KueM et a 1. . 1980a) and Shellfish (Kilikidis et a)., 1981). Average re coveries of 85-90% for PC8s (Frank et a)., 1978), including cleanup and all other analytical steps, indicate that the ex traction is generally adequate. Nevertheless, the lack of mixing cannot assure complete contact of the solvent with the fish tissue. Extraction with hot solvents in a Soxhlet extractor was demonstrated to be more efficient for fish extraction than use of cold solvents in a glass column extraction (Hettula, 1974a). The study involved comparison of four sol vent systems with three different fish (pike, perch and bream). The solvent systems were diethyl ether, diethyl ether/n-pentane (50:50), acetone/diethyl ether/n-hexane/petroleum ether (31:6:14;50), and methanol/chloroform (50:50). In the column extraction technique. 50 ml of the solvent was added to a glass column containing 5 g of loosely packed, ground fish tissue. After 2 hr of unagitated extraction, the solvant was drawn off and the tissue rinsed. Thus, only a single partition was effected. The Soxhlet extractions were carried out for 6 hr. The amount of native PC8s extracted from the fish were consistently higher with the Soxhlet ex tractor. The efficiencies of the different solvents were comparable. The author noted that tne $10 to $20% PSD in the amounts extracted was nigh and cautioned that the extraction step is critical to the overall analytical precision. HONS 223553 104 Analytical Chemlstryof PCB* Blending of the solvent end fish assures good con tact. This technique is employed in the AOAC (1980a) pro cedure for extraction of fish (Method 29.012(e)) jn procedure. 25-50 g of fish are ground with Na2S0, in a riign speed blender to disintegrate the sample and bind any water The sample is then extracted three times with petroleum ether The supernatant solvent is filtered, combined, dr with Na2SO. and concentrated in a K-0 evaporator a portion of the sample is removed for percent fat determination. The AOAC method is widely used, sometimes with minor modifica tions, such as substitution of n-hexane for petroleum ether The collaborative validation was published by Sawyer (L973) 2 Column chromatography: The use of e*tract'on columns has been reported for extraction of PC8s from fi$h (Stalling. 1971; Erney, 1974b; Hattula, 1974a). Fish samo'es are ground with sodium sulfate and sand to yield a dry powder and loosely packed 'nto a column. 'he PCB* are tnen etuteo with solvent. A minor variation reported by Stalling (1971) used dry ice during the grinding step to keep the tissue solid and therefore more amenable to pulverization. Although quantitative recoveries (97 t 3X) have been reported by Stalling (1971), the lack of agitation and possible channel ing of the column may lead to poor or irreproducibte recov eries . 3. Pistillation: A modification of the NielsenKryger steam disTl Ylatlon apparatus was used for extraction of PCBs and other chemicals from fish, water and sediment (Veith and Kiwus. 1977; Qougherty et a 1. , i960) The aooa* ratus (figure 5*1) permits simultaneous steam distillation and solvent extraction. The final extract is amenable to analysis without further cleanuo. A recovery of 92X 'rom 10 g Ohio River catfish diluteo with 2.5 L of water was re ported for a 7-hr extraction. Kuehl et al. (1980b) reported success with a micro version of the extractor for analysis of 0.5 g of tissue. In contrast to the work by Veith ano kiwus, Kuehl et al. added 10X Hz$0, to the distillation flask, pre sumably to "digest" the matrix. 4. Saponification with base: Saponification has also been used to prepare samples of fish, shellfish, and other marine organisms (Castelli et al., 1983). The samples were homogenized with water, refluxed with ethanolic kQH and extracted twice with n-hexane. The hexane was washed with water, dried and concentrated samples were cleaned on Florisi) and analyzed by HRGC/EIHS'SIH. The precision of the en tire method was measured with Aroclor-spiked biological sam ples and found to be between 1.6-19%. depending on the homo log. The injection precision was similar, indicating that the instrumental determination contributed most of tne mea surement error. HONS 223554 Extraction 105 Figure 5-1. Exhaustive Staaa-Oistillation and Solvent' . Extraction Apparatus Reprinted, with permission, froa Veith and Kiwas (1977): copyright 1977 Dy Springer-Verlag. HONS 223555 ioe c. Milk Analytical Chamistry of PCg^ Milk is 4 fatty samo'e, Which can retain PC8S an_ other pollutants. Cow's milk is of interest as a possible source of human consumption. Similarly, human milk i$ concern with respect to consumption by infants. In addition milk can be studied as a non-invasive sample collection proi ccdure to measure body burden (Erickson et el., 1980b) 1. Acetonitrile back-partition: The AOAC (1980a) method for extraction of milk samples (Method 29.012(c)) uses 100 ml of milk. Ethanol (100 ml) and 1 g of sodium oxalate are added. The mixture is extracted three times with ethyl ether/petroleum etner (50:50), separating the layers by cen trifugation. The combined organic layers are then washed with water three times, dried with sodium sulfate, and con centrated by evaporation. The PCBs and related compounds ar separated from the fat by acetonitrile partitioning. McKinney et el (1984) validated a slight modifica tion of the AOAC method, substituting hexane for petroleum ether. Five other solvent systems (all mixtures of a polar, water-miscible and nonpolar solvent) were investigated in lieu of the hexene-ether-ethenol combination. The latter yielded the highest lipid extraction and best reproducibi1ity. At 20 and 40 ppb, PCS recoveries of about 102X with USDs of t 14 to * 24% were reported. The method was applied to both human milk and infant formula samples. PA has utilized two methods for PC8s in human milk (Watts, 1980). The macro method employs an extraction with acetone, followed by hexane. The micro method usas an aceto nitrile extraction, followed by a hexane partition. In the macro method, up to 25 g of milk are extracted three times with acetone and then twice with hexana. The combined ex tracts are washed with water twice to remove water-soluble materials, including tha acetone. The extract is then dried and concentrated. The extract is than partitionad with ace* tonitrila as dascribad for adiposa tissua, abova, and analyzad by PGC/ECO. 2. Saponification with basa: A milk extraction technique similer to the AOAC method was published by Yakushiji et al. (1978). Hovavar, instead of the acetoni trile partition, they employed a reflux in ethanolic KOH to saponify the lipids. The resulting digestate was diluted with water and extracted with hexane. Saponification of milk samples has bean reported by Tuinstra at al. (1980, 1981) and Tuinstra and Traag (1979a, 1979b). HONS 223556 Extraction 107 3. Ac^d digestion: A single extraction of acidi fied milk *ith petroleum etner gave 90-95% recovery for PCBs (Veitrov and Aharonson, I960). The milk was acidified by stowly adding cone. The sample was tnen mixed until the curds redissolved before the extraction. The extract was then cleaned up by addition of sulfuric acid. three times the Quantity needed for decoloration The organic layer was then concentrated and analyzed by PGC/ECO. A. Column chromatography: Savage et al. (1973a,b) published procedures similar to those in Watts (19B0) except a Florisil column cleanup was used instead of the acetoni trile partition. In the micro method. 500 mg of milk are ex tracted three times with acetonitrite. The extraction is per formed in a tissue grinder to effect mixing and the resulting emulsion is broken by centrifugation. The combined extracts are diluted with water and extracted three times with hexane. The PC8*eonta*ning hexane extracts are concentrated, cleaned on a Florisil column, fractionated with a silicic acid column and analyzed by PGC/ECD. A combination extraction/cleanup technique for milk and dairy products used silica gel (Steinwandter, 1982a). Milk wes slurried with silica gel and added to a chromatog raphy column on top of 10% water-deactivated silica gel. The column wes then eluted with dichloromethane/petroleum ether (20:BO), which extracted the PCBs from the milk and cleaned up the eluate on the lower portion of the column. Samples were then analyzed by HRGC/ECO or HRGC/EIMS. 5. Extraction of freeze-dried samples. Freezedried milk samples have been Soxhlet-extracted with hexane (Bush et at., 1983). Recoveries from the entire method, which included a Florisil column cleanup and HRGC/ECO deter mination, were generally 80 to BOX for most congeners. How ever, recoveries in the 26 to 50X range were observed for mono-, di-, and tricnlorobipftenyU, presumably because of volati Hzation losses in the freeze-drying step. The preci sion of the method was t 5% or better for the major individ ual congeners. Bush et at. (1983) noted the poor recovery of the lighter PCS congeners, but judged that the simplicity of the technique made It worth using. 0. Epos Eggs from various species of birds have been ex tracted with hexane after grinding with sodium sulfate. The lipids were removed by chromatograpny on alumina (Zitko. 1976). MOHS 22355? 108 Analytical Chemistry of PCBs A column elution technique (Warden, 197?) compineg the extraction end lipid removal steps Eggs -ere ground with sodium sulfate end then mixed with Cehte 545. ihis mixture -as edded to e glass chromatography column on too or a S-g bed of alumina. The PCBs were then eluted with hexane The eluate was analyzed by GC/ECD without further cleanup Recoveries from 60-80X were observed for four PCB congener E. Other Animal Organs The above sections have described the extraction techniques for fatty organs and samples which generally con tain the highest PCB concentrations and are therefore of the most interest. Other organs also contain PCBs (see Chaoter Z) and are extracted by simitar techniques. The lower ii0,0 content of tnese samples, often allows the analyst to use less stringent PCB/tipid extraction techniques. Quail brains have seen extracted using a column technique after homogenization with Flonsil and sodium sui* fate. The eluent was dichloromethane/petroleum ether (30:70). Whole bald eagle carcasses were homogenized and 20*g aliquots Soxhlet extracted to determine the PCB concen tration in the entire bird (Begley et at. , 1970). Tarradellas et at. (19B2) describe an analytical method for earthworms and their gut contents. The earthworms were digested with a mixture of perchloric acid/glacial ace* tic acid (40:60) for 24 hr over a steam bath. The digestate was then extracted three times with hexane. 5ulfunc acid, mercury, and Florisit cleanup steps prepared the samples for HRGC/ECO analysis. The analysis of earthworms was promoted as a sensitive indicator of the concentration of PC8s in soil, since th earthworms exhibited five to eight times the concentration of the oii. 'wrtnermort, tne earthworms ae* peered to "average" the PC8$ as they migrated through the soil, since the RS0 of earthworm samples was much smaller than the RS0 of the PC8 concentrations of soil samplas taxer from different areas of a plot. F. Plant Tissue Plants, feed, grain, etc., must be ground and thor oughly mixed before extraction. This preparation step may be combined with addition of sodium sulfate to bind water, as with many other matrices. Corn silage has bean extracted in a blendar with isopropanol/haxana (33:67), followed by a sec ond extraction with benzene (Ernst et a)., 1974). The ex tracts were filtered, combined, concentrated, cleaned by Florisi) chromatography, and analyzed by PGC/EC0. HONS 223558 Extraction *09 1. Acetonitrile back-partition: A classic procedure for organochlonne pesticides in nonfatty foods em* ploys an acetonitrile extraction of the chopped sample, fol lowed by a petroleum ether back extraction of the acetoni trile after dilution with water (Hills et al.. 1963; FDA, 1977-Section 212). After blending or chopping, the 100-g sample is blended with 200-ml acetonitrile and 10 g Celite in a blender. The acetonitrile is separated from the solids by filtration. The filtrate is diluted with 600 mi. water. 10 ml saturated NaC 1. and extracted with 100 ml petroleum ether. The organic layer is washed with 2 x 100 mi water and dried with sodium sulfate. The extract is then cleaned with Flori- sil column chromatography and analyzed by gas chromatography. The procedure has not been validated for PCBs, but quantita tive recoveries of several organochlonne pesticides from green vegetables, soups, fruits, and other foods (Mills et al.. 1963) indicate that it would be suitable for PCBs. 2. Column cnromatoqraohv/acid digestion: A column extraction with a bed 57 sulfuric acid/silica gel (40:60. v/v) yielded an extract which was sufficiently clean for sil ica gel cleanup and then PGC/EC0 analysis, without the need for acetonitrile partition. GPC. or other cleanup (Schwart2 and lehmann, 1982). The plant tissue was ground with sodium sulfate and then added to a glass chromatography column on top of the acid/silica gel mixture with a layer of sodium sulfate in between. The PCBs were eluted with nexane. The recoveries of Aroclor 1242 and 1254 were about 75 t 6% at 10 ppb fortification level and about 90 t IX at 250 ppO for tification. This extraction presumably combines matrix deg radation by the sulfuric acid with chromatographic separation in the column elution. G. Discussion of Tissue Extraction Proper extraction of PC6s from animal and plant tissue samples presents a challenge. The matrix must be dis rupted, the PCBs must be removed, and finally the lipids and other co-extractive material must be separated. The tissue can be macerated with a mechanical mixer, as long as the size is appropriate, sufficient maceration is achieved, and no contaminants are introduced from gaskets or other sources. Sodium sulfate and/or sand are often added during this step to adsorb any water and for "grit" to aid in the grinding. The extraction solvent--often added prior to maceration--must not only be a good solvent for PCBs but should also assist in cell disruption. Acetone and alcohols are good solvents for cell lysis, A mixed polar/nonpolar solvent such as acetone/ benzene, ether/hexane, or methanol/chloroform appears to be the best extractant for PCBs. HONS 223559 110 Analytical Chemistry of PC81 The separation of the lipid materiel* he* be#f< achieved by m*ny techniques, as discussed above. If pcs* dPe the sole analyte. a chemical destruction of the lipids may the most straightforward. Sulfuric acid -ill destroy many biological (aliphatic) inttrferents. although losses of the lower-chlorinated PCBs have been reported (see Chapter 6) Saponification with base is also a useful technique for g#. stroying triglycerides and other esters. If additional analytes, such as the chlorinated pesticides, must be preserved, sulfuric acid digestion m*y not be advisable. The silver nitrate column of Smrek and Needham (1982) appears to be an elegant separation technique. The "classic" acttonitrile*he*ane partition (Mills-Qn1eyGaither) may be used, but recoveries from this step must be we 11'documented through validation and appropriate QC mea sures . VIII. PAPER PR00UCTS By virtue of their use in carbonless copy paper and other paper products and the extensive recycling of paper products, analysis for PCBs in paper products has been of considerable interest. A number of simple solvent extrac tions with hexane (Giacin and Gilbert, 1973; Serum et ml., 1973; OeVoogt et a)., 1984), petroleum ether (Shahied et at., 1973), end acetone (Kuratsune and Masuda, 1972) have been re ported. Recoveries of 80*102% were reported by OeVoogt et al. (1984) from a variety of paper products ranging from toilet paper to paperboard. An alcoholic KOH reflux was recommended as the technique for use with routine paper samoles (Young at i 1, 1973) and ultimately adopted as an official method (AOAC. 1980b). While both the KOH saponification and a sulfuric acid digestion gave 96'97% recoveries from fortified paper samples, the latter technique was more tedious. In the KOH procedure, the samples (10 g) are cut up, mixed, and refluxed with 60 al JX KOH in ethanol or methanol for 30 min. The sample Is diluted with water and repeatedly extracted with petroleum ether. The combined extracts are then washed with weter, dried with sodium sulfate, concentrated in a Kuderna* Danish evaporator, claaned on a F Tori si l column, and deter* mined by PGC/ECO. Similar methods have been used by otners (Stanovick et al., 1973; Easty, 1973; Becker and Schulte. 1976; Easty end Wabers, 1977). HONS 223560 Extraction 111 IX. OILS The determination of PCBs in oils has been of in* terest because of the high frequency of contamination of cer tain types of oils. PCBs have many similar chemical, phys ical* and us* properties of mineral oil, silicone oil, *nd other oils. Mixing PCBs with these oils and cross-contamina tion has led to broad-scale contamination of non-PCB fluids nth PCBs at low concentrations, for example, many askarel transformers have been retrofitled with mineral oil or other bielectric fluid to declassify the transformer from "PCB" status. The resulting transformers generally have trace (50* 500 PP") Quantities of residual PCBs and are classified as "PCB-contaminated." In addition, many electrical comoonents *re contaminated from residual PCBs at the manufacturing site. As discussed in Chapter 2, the PCB contamination of these oils determines their dassi f ication, and thus use and disposal rules, in the U.S. PCBs have also contaminated other oils whicn enter the animal or human food sources. A notable, classic example is the Yusho incident (see Chapter 2 for a more detailed dis cussion), in which cooking oil which had been contaminated with PCBs, was distributed in Japan. Many people were con taminated by the PCBs In this oil. As noted above, PCBs and many oils- have similar properties. For this reason, extrac* tion techniques used for polar matrices, such as water, are not appropriate for extraction of oils. Often, the "extrac tion" is simply a dilution of the matrix to lower the viscos ity to make an injection on a GC. Some "extractions" are conducted under cleanup steps, as described in Chapter 6. Transformer and Related Oils 1. Organic oils: Liquid-MQuId partition of PCBs from oils is difficult. The similar polarity of the PCBs and the matrix make unfavorable partition ratios. In addition, the lack of chemical reactivity of the matrix generally pre vents the use of any chemical degradation techniques to con vert the oil to an extractable matrix. Therefore, the most common "extraction" technique for these matrices has been simple dilution. Hexane dilution has been successfully used in the preparation of common PC6*containing oils for analysis by PGC/ECD or PGC/HECD (Sonchik et al., 1904; Levine et a1.t 1903). Samples were diluted either 1:25 or 1:100. Hexane dilution is also recommended for analysis of transformer fluid and waste oils by the U.S. EPA (l9Bla; Bellar and lichtenberg, 19B1). The procedure specifies 1:100 or 1:1000 HONS 223561 112 Analytical Chamistry of PC8a dilution of the oil with pesticide grade hexene The pro cedure recommends screening the sample to determine the ap proximate concentration by X-ray fluorescence, microcoulom* etry, density measurement, or GC screening of a very dilute (1:10,000) sample Samples are then analyzed by PGC/HECO PGC/ECQ, or PGC/EIMS. Several optional cleanup techniques are presented. Several types of matrices are covered by the simple dilution aoproach: a. Transformer pi Is: The most common trans former oil which might be contaminated with PCBs is mineral oil, which contains 20-30% aromatics and the balance hydro* carbons. Polydimethy1 $i1oxane (silicone) fluids, discussed below, are the next most common. Other transformer dielec trics which are used to retrofill PCB transformers are paraf finic hydrocarbons, high temperature esters, tetrachloroethylene (Perc. Wecosol), and non-PCB askarels (chlorinated benzenes). The properties and uses of these matrices are discussed more thoroughly in a review (PEOCo. 1904). 'n addition to these non-PCB dielectric fluids, old transformer oil samples can be PCB askarels. containing up to 70% PCBs, as discussed in Chapter 2. b. Capacitor fluids: Capacitor askarels con tain high levels of PCBs such as Aroclor 1016, as described in Chapter 2. Substitutes which mey be contaminated with PCBs include alkyl phthalate esters, 1.1-phenylxylylethan#, isopropylbiphenyl, and butylated eonochlorodiphenyl ether. c. Hydraulic fluids: Hydraulic fluids may be petroleum based oils, phosphate esters, water glycols, and invert emulsions. These matrices are most often contaminated with Aroclor 1242 in the U.S. (Sonchik et at., 1984). o. waste oils, waste oils can come from many sources and have various compositions, including road oil, automotive crank case oil, and recycled fuel oil. Other oi1s: Water glycol and invert emul sion hydreulic fluids were immiscible with hexane. These ma trices were extracted three times with hexane (Sonchik et al., 1984). A 1iQuid-1iquid partition of transformer oil with acetonitrile/hexane (90:10) has been described (Gordon et al., 1982). Specifically. 1.0 ml of the transformer oil is shaken with 15 ml of the acetonitrile/hexane mixture, cen trifuged. and the oil layer discarded. The acetonitrile is then diluted with 10 ml water and the PCBs extracted into 10 mi hexene. The hexane is concentrated to 1.0 ml and cleaned up with a silica gel cartridge (Sep-Pak) and then determined HONS 223562 Extraction 113 by HflGC/ECO. Recoveries for the total method were 70 to 100% for Aroclor* 125a and 1260 but only 40 to 75% for Aroclor 1242 over a concentration rangt of 5 to 500 ppm. Volatility of the lighter Aroclor 1242 was blamed by the study authors for the low recoveries, although different partition ratios of the lower PCB congeners must also be consioered. 2. Silicone oils: Two extraction techniques have been used for si'Ticone fluids: an acetonitrile partition for subsequent HPlC determination, and a carbon column extraction for PGC/EC0 determination (Xlimisch and Ingebrigtson, 1980). The acetonitrile portion was deemed necessary, since direct injection of the silicone fluid degraded the HPIC column ef* fiC'ency. A 0. 1 g sample was diluted with 2.9 g of clean silicone fluid and extracted with 3 ml of dry (< 0.5% water) acetonitrile. The acetonitrile was then diluted with water to the same composition as the HPlC mobile phase (62% aceto* nitrile). The authors noted that PCBs are only slightly sol* ubte (0*2%) in acetonitrile and that low recoveries would be observed if the PCS concentration in the oil exceeded that concentration. A charcoal extraction technique was used for sam ples in the 25 ppb to 5 ppm range (Klimisch and Ingebrigtson, 1980). A 1*2 g sample was dissolved in acetone/diethyl ether (25:75) and applied to a 1 x 15 cm column of 50-200 mesh activated coconut charcoal. A 75-*l portion of the acetone/ diethyl ether mixture was eluted through th# column. The PCBs were then eluted from the column with 75 ml toluene, which was concentrated, and then determined by PGC/EC0. Aro clor 1248 was quantitatively recovered (91*106%) from the column in the 1-20 ug range. B. Vegetable Oils Vegetable oil and related products have been an alyzed by dilution with ethyl acetate/toluene (75:25), fil tration If necessary, gel permeation chromatography, Florist I chromatography, and determination by PGC/ECD (Young and Kempt, 1982). The method was applied to crude soybean oil and its refinery by-products (soapstock, deoderizer distil late. and clabber stock). Specifically, S.O g of sample was diluted to SO ml with ethyl acetate/hexane (75:25). Viscous or solid samples wero liquified by gentle heating. The sam ple preparation technique was not specifically validated, al though a recovery of 98% for Aroclor 1254 at 3 ppm was mea sured for the entire method. The rice oils implicated in the Yusho incidents (both in Japan and in Taiwan) were prepared for analysis by saponification (Nagayama et al.. 1975. 1976; Chen et al., HONS 22*563 114 Analytical Chemistry of PCBs 1981) The o>l as heated in ethanolic sodium hydroxide 4ft<J extracted with n-ne*ane. Saponification is described jn ITIOr# detail m Section VII.C.2 in this Chapter. X. ANCILLARY CONSIDER! IONS A. Solvent evaporation Concentration of the sample extract by solvent evaporation is common to many of the extraction techniques discussed above for the various matrices. Common evaporative techniques involve either boiling of the solvent or blowing a dry gas stream (usually nitrogen) across the solvent surface The former technique is often accomplished with a reflux col* umn to reduce the chance of solute loss through vaporization or spattering. The most common evaporative apparatus is the Xuderna-Danish (KO) evaporator. Numerous studies nave inves tigated the efficacy or the various concentration teenmoues with a common conclusion that the most important factor m preventing loss of analyte during this Step is operator skill and attention. In short, solvent evaporation techniques are an "art." Caragay and Levins (1979) reported significant losses of Aroclor 1254 during KD concentration of dichloromethane/hexane (15:05). They noted that with proper atten tion to a rapid evaporation, "good recoveries" were obtained 8. Sorption onto Glassware As noted in Chapter 4, significant adsorptive losses onto both glass and plastic surfaces have been docu* mented in water (Pepe and Byrne, 1980; Muldrew et a)., 1981: Sutcliffe ana Nielsen, 1983). SiUmtation appears :o retart the losses (Muldrew et al., 1981; Neidert and Saschenprecker, 1984). While data are available for water and adipose sam ples only, sorptive losses from any matrix or solvent is pos sible. For example, during an evaporative concentration in hexane, it Is entirely possible that significant amounts of PCBs (and other organic analytes) could be deposited on the glass surface as the volume is reduced. Even with hexane and other "good" solvents, the low concentrations of PCBs could easily favor partition to the glass surface. Analysts can guard against sorptive losses through good analytical technique. The entire interior of a sample container (contents, glass surface, and cap liner) should be treated as the "sample." An extract of the container can easily be combined with the samote extract. Furthermore, all sample transfers should be accompanied by a quantitative HONS 223564 Extraction 115 rinse**>ncluding pioets. During the samole concentration steps, the sides of the container should be rinsed where possible end cere should be taken to avoid spattering, if losses are observed or suspected, silanuation may improve reC3vfy finally, proper QC practices will monitor the re covery, so that any PCB losses will be detected (see Chapter 9). C. Sources or Contamination Contamination of samples by PCBs, interfering com pounds. or non-specific interferences can lead to erroneous results and reauire repetition of the analysis, if the pro blem is detected. Interferences may come from solvents, re agents, glassware, the laboratory environment (contaminated air or work areas), or anything else that comes into contact with the sample. Generally, the analysis of laboratory re agent blank is sufficient to demonstrate that the samoles are fret from contam1nants. Preventing contamination of samples requires good general laboratory practice. Glassware must be scrupulously cleaned. It should be rinsed as soon as possible after use to remove gross contaminants from the sample and then sub jected to a strict cleaning protocol. Many standard methods (see Chapter 3) give guidance on glassware cleaning. A good glassware cleanup protocol should reduce carryover from pre vious samples by at least 104 (i.e., only 0.013 of the pre vious sample should remain on the glassware). Nevertheless, a laboratory should segregate glassware and space for low and high level samples to prevent cross contamination of samoles at the nanogram-per-gram level by samples at the percent level. High purity solvents and reagents (e.g.. pesticide residue grade) are generally free from interferences. Never theless. many standard procedures and many laboratories stip ulate that eaeft now lot of a reagent be checked for purity. In addition, most adsorbents used for sampling, extraction, or cleanup are purified prior to use by solvent extraction or thermal desorption. Some of the adsorbents commonly used for sample cleanup have been 'ound to contain interferences, as discussed in Chapter 6. ' Contamination of final extracts can also be a pro blem. Contaminants can leach from the vial cap, cap liner, or the glue that holds the two together. PCB contamination can occur if the syringe used to inject onto a GC is not scrupulously cleaned between injections. Syringes should bo segregated for high and low level work, since cleanup to trace levels is extremely difficult once a syringe has been contaminated. MOHS 223565 HONS 223566 6 CLEANUP The cleanup step In an analytical procedure removes other compounds which may Interfere with the determination of specific analytes such as PCBs. A cleanup takes advantage of ;he difference in physical or chemical prooert'es of PCBs ana interferences to remove the unwanted constituents. The cleanup- process may be expressed in terms of enrichment, where the ratio of PCBs to interferents is increased. Ideally, a cleanup reproducibly achieves 100% recovery of PCBs in one fraction, with the interfering compounds rele* gated to other fractions. The extent of cleanup required is dependent on the requirements of the determination step (see Chapter 7). with a highly selective detector such as mass spectrometry, less cleanup to remove other chlorinated organics would be re* quired than for electron capture detection. On the other hand, low resolution electron impact mass spectrometry re* quires extensive cleanup to remove the oil matrix components prior to determination of trace levels of PCBs, wnfle ECO is lirtually blind to the comoonents of a transformer oil matr'* and little cleanup is required. This chapter discusses the cleanup techniques available for PCBs, including adsorption column chromatog* raphy; high performance liquid chromatography (HPlC); thin layer chromatography (TIC); gel permeation chromatography; and chemical degradation with acid or base. When appropn* ate, adsorption column chromatographic fractionation tech niques which isolate PCBs into different groups are also presented in this chapter. Partition techniques to ramove bulk* matrix interferences were presented in Chapter S (Ex* traction), since these techniques are highly matrix* dependent. Some of these techniques combine extraction and cleanup in one step. 117 HONS 223567 lie Analytical Chemistry of PC8a I. ADSORBENT COLUMN CHROMATOGRAPH* Adsorption column chromitography is the most common sample cleanup. In this technique, a solvent eluted a samole extract through a column containing it least one adsoroent The differences in polarity, solubility and partition cause the PCBs and other compounds to move at different rates Thus, the PCBs can be isolated in an appropriate fraction Common adsorbents include Florist), silica gel, alumina, ana carbon. In addition, a combination of adsorbent materials in one column, a column cleanuo after liquid-liqu'd partition, or a column cleanup after matrix destruction by sulfuric aca or saponification have ail been reported. Adsorption chromatograpny separates compounds by liquid-solid partitioning. The affinity of the PC6s and other components of the samce fo- the adsoroent aeoe^as on their polarity and the surface activity of the adsoroent. The adsorbent can be activated by heat (e g., 130C) or other treatment, which makes more binding sites available. Con versely, adsorbents can be deactivated by tying up the sites. A common deactivation for many of the adsoroents is adding water to hydrate some of the binding sites, thereby making them unavailable for PC8s or other organic samole con stituents. The other aspect of liquid-solid partition is the solubrlity of the sample components in the solvent The sol vent polarity can be precisely controlled to either enhance or retard the elution of the organic components from the col umn. A. General Practices An adsorption commo generally prepared Oy either a slurry-packing or dry-packing technique. The sample is then applied to the top of the column in a small volume. The PC8s and other components are eluted througn the column with an appropriate solvent. Air or nitrogen pressure can be applied to accelerate the elution. The separation is often enhanced by changing the polarity of the solvent during the elution. The PCBs are eluted in a given, predetermined frac tion. This fraction may include nany other organics or may include only a specific subset of the PCBs. Because of the differences in adsorbent activity and packing efficiency, each batch of adsoroent should be tested for the PCB elution volume. This is usually done by passing a PCB mixture through the column and collecting the eluent in smell (eg., 10ml) fractions. The individual fraction* ire then enelyzed to deti-mine where the PCBs elute This permits the analyst to define a routine collection frac tion which will contain all PCBs. Atulene, a blue-colored NONS 223568 Cleanup 119 aromatic compound which is not detected by GC/ECO. hqj betn found to be a useful visual indicator to monitor the elution of each individual Florisil, silica gel. or alumina column (Nowtcki, 1981; Erickson et al.. 1983e). This technique ap pears to greatly reduce the uncertainties in th appropriate volume of the PCS fraction. The position of the blua aiulene pnd serves to mark the location of the end of the first fraction. The cut between fractions is made by the analyst when the atulene band reaches a prescribed point, not when a specified volume of solvent has eluted. Griffin et al. (1980) measured the movement of the azulene down a silica gel column as the fraction of the total column length, ft They found that the best cut point to separate PCBs from g,g'-00E ranged only fron an of 0.32 to 0.38. while the absolute volume ranged from 90'to ISO ml. Clearly, the aaulene in dicator provides a more precise measure of the appropriate elution volume. The authors noted that atglene eluted from a packed 0V-101 column well ahead of the earliest peaks in Aro- clor 1221 .or any other Aroclors and also exhibited a response of 3 * 10 A relative to aldrin. Therefore, atulene should not interfere with PC8 determination by GC/ECO. 8. Florisil 1. Properties: Florisil (trademark, Floridin Co.) is a synthetic magnesium silicate. The Florisil generally used in PCS analyses is 60/100 mesh pesticide residue ("PR") grade. It has typically been activated by heating to 6S0C by the manufacturer. Although cleanup of the reagent with solvent may improve the blank values, most of the standard procedures simoly prescribe heating the Florisil. as re ceived, at 130C until it is to be used (FOA. 1977; AOAC, 1980a; Watts, 1980). TheU.S. EPA (Watts, 1980) specifically recommends storing pre-packed Florisil columns in a 130*C oven at least overnight to ensure column uniformity. It also -commends that the oven used to store sorbents should be re stricted from general use to prevent contamination. While fully activated Florisil has been most widely used, the use of deactivated Florisil has been reported. A 2X deactivated Florisil column cleanup has been used by 8ush et al. (1983. 1984) for cleanup of milk and blood samples, and by Bush and Barnard (1982) for cleanup of fish eggs, rat brain, and aquatic macroinvertebrates. Specifically, flor isil was activated at 450*C. deactivated by addition of 2X water (v/w), and equilibrated by shaking for at least 0.6 hr. Columns (1 cm 1.0.) were dry-packed with 10 g sorbent and the PC8s eluted with 40 ml hexane. Hirex, photomirex, g,g'*006. o.g'*00, hexachlorobenzene. and octachlorostyrene eluted with the PC8s. Other pesticides were eluted with ethyl ether/hexane (10:90). HONS 223569 120 Analytical Chomistry of PC8s 2. Evaluation of activity: A$ with othr Jor. btnt$, tht adsorption characteristics of Florisil can vary significantly from * ot to lot. Thus, it has often been rec ommended that each 'ot be evaluated. An evaluation of the quality of Florisil nas been described in detail in Section 3,0of EPA's pesticide residue analysis manual (watts. 1980) A representative sample of Florisil Is thoroughly mixed ang packed into columns. A standard solution of pesticides (PC8s could also be added if they are to be an analyte) is then eluted through the column and the appropriate fractions col' lected. The elution pattern is then measured and the accept' ability of the batch determined. Acceptable total recovery of organochlorine pesticides from all fractions is 90 to 10SX (Watts. 1980; Sherma. 1981) No provision is made by Watts (1980) for adjusting me volume or composition of the elution l solvents to optimize recovery. However. F0A (1977) permits the analyst to adjust the amount of sorbent in the column from the normal *-n. depth to compensate for "over* retentive" or "under-*etentive" Florisil A lauric acid adsorption technique has also been widely used to estimate the adsorptive capacity of Florisil (Hills, 1968; FDA, 1977). An excess of lauric acid in hexane is added to a weighed amount of Florisil and the amount not adsorbed is measured by titration with sodium hydroxide. A "lauric acid value" is then calculated as the milligrams lauric acid adsorbed per gram Florisil. From this laur>c acid value, the amount of Florisil in the column is adjusted from the normal 20-g column. The elution characteristics of the batch are then verified by elution of a standard mixture of pesticides (F0A, 1977), similar to that described for the EPA procedure in the previous paragraph. The elution of each column can also be visually monitored with azulene. This technique is discussed in Sec* tion l,A, above. 3. HI 11s-QnleyGaither technique: The Florisil column cleanup in a classic pesticide analysis method (Hills et al., 1963) was the basis for many of the standard PC8 pro cedures presented in Chapter 3. These include food (FOA, 1977; AOAC. 1980a); adipose (Watts, 1980); soil and bottom sediment (EPA. 1982d): and paper and paperboard (AOAC, 19800). Specifically, the "Mills-Onley-Gaither" (M0G) method used a large column (10 x 2.5 cm) of activated Florisil to clean up extracts of ICO-g samples of fruits and vegetables. The elution solvents were ethyl ether/petroleum ether (6:94; Fraction 1). ethyl ether/petroleum ether (15:85; Fraction II), and ethyl ether/petroleum ether (50:50; Fraction 111). The method was adopted for PCB analysis. Seven Aroclor mix tures (1221 through 1262) were shown to elute in Fraction I, HONS 223570 Cleanup 121 "the 6* fraction" (McMahon and Burke. 1978: Watts, 1980; pillar et al., 1981. 1982). This fraction is often submitted to further cleanup, as discussed in the section on silica gel (Section I.C. below), since many organochlorine pesticides (e g-. OOE. 00T, heptachlor) also elute in this fraction and interfere with PGC/ECO determination. The HOG Florisil cleanup has been widely used to clean up fish (Erney, 1974; Sawyer, 1973), animal and human adipose (Sawyer. 1973. Erickson et al., 1983e); wastewater (Hillar et al.. 1981. 1982) and other matrices in addition to the food matrices for which it was originally validated. 4. E1utina solvent: It has been noted (Watts. 1980. Section 3, b, VIII, 2) that the polarity of the solvent dramatical1y affects the elution characteristics of many pes* ticides on a Florisil column. The standard elution charac teristics have been obtained with ethanol/diethyl ether (2:98). The solvent comoosition should be tightly controlled to ensure reproouciole resuits. Ethyl ether/petroleum ether (6:94) or ethyl ether/ hexane (6:94) is the classic solvent mixture used to elute PC8s and many organochlorine pesticides from Florisil (Hills et al., 1963; see Section 1.8-3, above). A substitution of dichloroaethane/hexane (20:80 to elute PCBs) has also been shown to be effective (Seidl and 8a1Ischmiter, 1976b). PC8 recoveries of > 90S from up to 1 g fat were observed. Methanol/hexane (2:98) has also been found effective for elu tion of PC8s and 00E from Florisil columns (McKinney et al., 1984). Hexane has been found to be a satisfactory eluent for PC8s, in a cleanup of adipose (Erickson et al., 1983e), fish and shellfish (Castelli et at.. 1983). milk and blood (8usn et al., 1984, 1984). and eggs, brain, and aquatic in* vertebrates (Bush and Barnard. 1982). Oichtoromethane was used to elute PCIs from a Ftorisil column to clean up phthal* ocyanine blue, phthalocyanine green, and diarylide yellow pigments (OCHA, 1982). 5. Cartridges: A rapid cleanup using commercially prepared Florisi1 cartridges (Sep-Pak, Waters Associates, MiWord. HA) was demonstrated to yield quantitative PCS re coveries from fish samples (HcKone and Oaub. 1983). In addi* tion, the Sep-Pak and conventional column Florisil cleanups were compared using eight fish samples with Aroclor 1260 con* contrition ranging from 2 to 178 ppm. The results from the two techniques compared within 10%. In the Sep-Pak cleanup a S-el petroleum ether extract of fish was flushed through the cartridge. The eluate, plus an additional 2-ml of petroleum HONS 223571 122 Analytical Chemistry of PCBs ether. was collected. diluted to a known volume and anaiyi(J by PGC/ECO. Repetition with a second cartridge was required to effectively remove the lipids from samoles containing *0Pt than 4% fat. The use of the cartridges gave equivalent per formance and was much faster and easier to perform. 6 Appiications: In addition to the applications noted above. Florist 1 has been used to remove gross interfer ences from sample extracts from air. water, wastewater, tis sue. dairy products, oil pigments, paper, paperboard, jno paper mill effluent (AOAC. 1980; Adams et at.. 1979. Oe l f i r0 and Easty. 1979; Easty, 1973; EPA. 1979a; EPA, 1979b. EP*. 1978; EPA, 1980; Sonchik et a)., 1984; Kamps et ml. 1979[ Kuehl et al., 1980; Modi et at., 1976. Price and Welch, 197j[ Reynolds. 1969. 1971; Robbins and willhite, 1979; Rodriguei et al., 1980; Stijve et al.. 1974; Swift and Settle. 19?6; Tessari and Savage, 1980; Yakushiji et al.. 1978; Bagley et al.. 1970; Bagley and Cromartie, 1973; Sellar and tichtenberg, 1975; Chau and Babjak, 1979). Flonsii has also been used to provide additional separation of samole extracts following initial deanuo of matrices by low temperature precipitation, acetonitrile par titioning, oxidation, sulfuric acid digestion, alumina chro matography, or gel permeation chromatography (Eder, 1976a Ernst et al., 1974; Kohli et al., 1979; Hes et al.. 1977a, Mes et al., 1977b; Mulhern et al., 197?; Stanovick et al.. 1973; Swift and Settle, 1976; Tessari and Savage, I960; Trotter, 1974; Uk et al.. 1972: Bagley et al.. 1970; Bagley and Cromartie, 1973; Copeland and Gohmann, 1982). 7. Oetailed procedure: As an example of the Florisil column cleanup technique, the appropriate section of the Bellar and lichtenberg (1981) procedure for PCBs in trans former oils is given below. 1. Variations among batches of Florisil (PR grade or equivalent) may affect the elution volume of the various PCBs. For this reason, the volume of solvent required to completely elute all PCBs must be verified by the analyst. The weight of Florisil can then be adjusted accord ingly. 2. Place1 a 20-g charge of Florisil, activated overnight at 130*0. into a Chromaflex column. Settle tne Florisil by tapping the column. Add about 1 cm of anhydrous sodium sulfate to the top of the Florisil. Pre-eiute the column with 70 to B0 ml of hexane. Just before the expo sure of the sodium sulfate layer to air, stop the flow. Oiscard the eluate. HONS 223572 Cleanup 3. Add the sample extract to the column 123 4. Carefully wash down the inner wall of the coiumn with S ml of hexane. 5. Add 200 ml of ethyl ether/hexane (6.94) and set the flow to about S ml./min. 6. Collect 200 mi of eluate in a Kuderna-Oani$h flask. All the PCBs should be in this frac tion. Concentrate to an appropriate volume 7. Analyte the sample. 1. Properties: Silica gel is a granular form of silicic acid (HjSiOj). It is widely used as an adsorbent for organic molecules in both gas ana 'iquio phases. It has oeen used both for primary sample cleanup and for fractionation of PCBs from similar organics after another cleanup. Z. Contaminants; Contaminated silica gel can pre sent blank problems. Up* to 160 ng PCBs/g silica gel were found in liquid-chromatographic grade silica gels from sev eral manufacturers (Bergman et al . , 1984a). The authors at tributed the contamination to either the final cleanup or ad sorption of PCBs from ambient air during storage. The PCBs were extracted from the silica gel by eluting a column with dichloromethane. This cleanup step was recommended by the authors as a satisfactory cleanup technique. Huckins et a). (1976) also reported contaminants, including bis-2-ethy1hexy1 phthqlate, and PCBs. The occasional presence of H2S04 in the soroent may have produced other contaminants which interfered <th PGC/EC0 analysis. A purification of the silica gei cy extraction with acetonitri le/dichloromethane (40:60) and then drying at 160*C for at least 48 hr was recommended. 3. Eluting solvent: The composition of the elu tion solvent can have marked effects on the elution of PCBs (and other organics) through silica gel. Zitko (1971b) demonstreted that the benzene content of different pesticide grade hexanes could markedly affect tha elution of Aroclor 1254. Only 1BX of the PCBs eluted with 10 al of hexane con taining 210 ppm benzene, while 56X of the PCBs eluted when the hexane Contained 800 ppm benzene. Even higher recoveries were observed when more benzene was intentionally added. The benzene content of hexane has also been shown to decrease the resolution of PCBs from p,p'-00E on silica gel (Griffin et at. . 1980). HONS 223573 124 Analytical Chemistry of Peg* 4 Elution characteristics a. Activated s>1ica pel The source anQ activity of the silica gel are important factors in the elu tion of PCBs ana other compounds. Griffin et a!. (1900) com pared several batches of silica gel and demonstrated a wiae variation in their activity. The best cut point to separate Aroclor 1254 and g.gl-00E ranged from 20 to 150 ml of hexane for different brands of fully activated silica gel m4ilinckrodt No 2847 ( 100 mesh, relieved to 100 mesh), which had the highest cut point, was judged best since it gave the best resolution of the PCBs from the g,g`-0DE. Davidson No 923 was also judged acceptable; Oavidson No. 950. fair, Davidson No. 50. poor; and Merck Silica Gel 60, poor the latter two adsorbents exhibited very low adsorbent activity With the Ma11inckrodt No. 2847, lot-to-lot variation did not affect the cut point, relative to an azulene visual indi cator. although the absolute elution volumes did vary 5. Deactivated si iica gel: Intentional de activation with distilled water is a common practice to speed up the elution of PCBs through a silica gel column. As il lustrated in Figure 6*1, a less active sorbent (i.e., more water) will exhibit a shorter PCS retention, but will have poorer resolution (Griffin et a!., 1960). Similar results were obtained by Armour and Burke ( 1970). The choice of the activity depends on the objective of the cleanup. If a gross cleanup of polar materials such as lipids is desired, a de activated adsorbent may be practical, while a fractionation of PCBs from g,g'-Q0E and other pesticides would be most ef fectively done with a fully activated adsorbent. The elution volumes of PCBs and 50 pesticides on silica gel have been tabulated (leoni, 1971). PC9s and several nonpolar pesticides such as hexachlorobenzene. si* drin, heptacnlor, and several 00T analogs were eluteo ith n-hexane. The more polar pesticides required correspondingly more polar solvents. Oavison 950 silica gel was activated for 2 hr at 130*C and then deactivated with 5% water. c. Modi fled silica gel: An early application of silica gel to clean up samples for PC8 analysis utilized an 80:20 mixture of 3%-activated silica gel/celite (Amour and Burke, 1970). A 25-g portion of the mixture was slurrypacked into a chromatographic column. PCBs were eluted with 250-ml petroleum ether, using air pressure to accelerate the elution. Fish extracts were first cleaned up on a florisil column and the PCB fraction further cleaned up with the sil* ica gel. The recoveries for Aroclor 1254 and 1260 were 95 to lOOt at tn# 40-pg level in solvent. Recoveries of 100X and 76% were observed for the same PCS mixtures at a similar col umn loading when spiked into trout extract. MONS 223574 Cleanup 125 Figure 6*1. Separation of p.g'-OOE fro* Aroclor 1254 by Column Chromatography With Oifferent Activities of Silica Gel A - 1% Water-deactivated; 8 * 0,5% water-deactivated; and C * 0% water-deactivated, either activated in column (____) or bullc-deactivated and then cooled before packing (---), Col* umns were eluted with UV-grade hexane with 100 pg Aroclor 1254 or 10 pg g,g'-00E, Reprinted, with permission, from Griffin et al. (1980); copy right 1960 by Association of Official Analytical Chemists. Inc. MONS 223575 126 Analytical Chemistry of PC8% SiNr nitrate has been used to alter th properties of a silica gel column (Needham et al., I9gn* irevisam, 1980). The AgNQ-j (10%) acts as a "trap" for OQt and related comoounds, according to the authors who oriQ1. nated the technique lor cleanup of fish samples for tcod analysis (Lamparskt et al.. 1979). d. Alumina and silica gel in series: Silica gel columns were used to separate PC8s and pesticides into groups after an initial cleanup with alumina (Holden aft<J Harsoen, 1969; Musial et al., 1974, ZUko, 1971a). PC8 ODE, DOT and several other pesticides eluted with 10-ml h#i ane, while the BHCs. dieldrin, endrin, and heptachlor epoxide eluted with 10-ml ethyl ether/hexane (10:90) (Holden Harosen, 1969). A careful cut of the nexane eluent couid separate the PCBs and 006 (6-8 ml hexane) from the p.p'-OQT (14*16 ml hexane) (Musial et al., 1974). A similar separa* tion scheme, using alumina and silica gel columns in series as used to seoarate ohthalate esters. PCBs, pesticides *na other compounds into appropriate fractions for analysis (Russell and McQuffie, 1983). The phthalate esters must be determined separately because they interfere with the GC/ECO detection of the PC8s and other chlorinated organics. 5. Column site; The site of the silica gel column should be scaled to the amount of material in the sample to be cleaned up. Steinwandter (1963) demonstrated that micro silica gel columns could effectively remove fat, while pro viding quantitative recovery of PCBs and pesticides when eluted with dichloromethane/petroleum ether (20:80). Columns containing 2, 3, and 4 g of silica gel retained 90, 140 and 190 mg fat with elution volumes of 20, 25, and 30 ml. respec tively. The adsorbent was prepared by activating the silica gel at 450*C for 3 hr and then deactivating with 10% dis tilled water. Similarly, Ernev (1974a) demonstrated Quanti tative elution of Aroclor mixtures from a 5*g silica gel col umn with 35 ml of petroleum ether. g.g'-DOE coeluted with the PCBs, while other common pesticides (e.g., 00T) eluted in a more polar fraction. Silica gel "as received" (i.e.. no activetion) was used for the validation studies after it was found that the "as received" materia) gave separations equal to or better than activated silica gel. This cleanup, fol lowing a FlorisH cleanup, was used in a procedure for fish Analysis (Erney, 1974b). The procedure geve comparable re sults, was faster, and used smaller amount of reagents than those in FOA's (1977) Pesticide Analytical Manual (PAM) stan dard procedure. 6. Applicatlons: The ASTM (1981a) standard pro cedure for PCBs in water utiliits the silica gel microcolumn cleanup technique shown in Figure 6-2 after an initial HONS 223576 Cleanup 127 cleanup using florisil me PCBs in the 6% fraction (ethyl ethpr/petroleum ether; 6:94) from the Florun column ere separated from the other organochlorin* compounds by elution with n-nexane. The pesticides can be eluted with ethyl ethtr/benzen* (0.5:99.5). The amount of solvent needed to elute the PC8s is determined by collecting l-ml fractions of tne eluate of standard solutions of PCBs and pesticides. Figure 6*3 presents the Aroclor elution patterns given by aSTH. It is interesting to not* that the more hignly chlor inated mixtures (eg., Aroclor 1260) elute before the less chlorinated mixtures (t.g. . Aroclor 1242). Silica gel column cleanup has been aoplied to the determination of PC8s in a variety of matrices, including fish (Armour and Burke, L970; Erney, L974b; Stalling, 1971, HuCkins et a!., 1976), adipose (Sawyer, 1973. Swift and Settle, 1976; Mes and Campbel1. 1977), blood (Needham et a I., 1980; Stratton and Geiszler, 1977), milk (watts, 1980; Musial, 1974; Steinwandter, 1982a), food (Tanabe, 1976, FDA, 1977; Leoni et jl., 1973; Nose, 1973; Vannuchi et si , 1976; Trevisam, 1980), biological matrices (Kveseth and Srevik, 1979). sewage sludge (Erickson and Pellizzari, 1977, 1979; Ballinger, 1978), soils (EPA, l982d*. Nose, 1973), sediment (Sellar and lichtenberg, 197$), air and stack gas (Bidleman et al., 1978; levins et al., 1979; Macteod, 1979), water (EPA, 1978; ASTH, 1981a; Erickson et al,, 1982, 1983d; Nose, 1973; United Kingdom Department of Environment, 1979; Oerenish and Harling*8owman, 1980), paper (Serum et a'., 1973), transformer oils (Seller and lichtenberg, 1981; GorOon et al., 1962; Ogata et al., 1980; Steicnen et al.. 1982; 8alya and farrah, 1980) and industrial products and wastes (Erickson et al., 1982. 1983d, 1964d). 7. Oetailed procedure: As an example of the sJ* ica gel cleanup technique, the appropriate section of th Seller and lichtenberg (1981) orocedure for PCBs m trans former oils is given below. 1. Activate silica oel (Oavison Grade 950 or equivalent) at 135*C overnight. 2. Variations between batches of silica gel may affect the elution volume of the various PC8s. For this reason, the volume of solvent required to completed elute all of the PCBs must be ver ified by tne analyst. The weight of silica gel can then be adjusted accordingly. HONS 223577 128 Analytical Chamlatry of PC8* Organochlorine Pesticides from PCBs following florisil Cleanup The sample is added to the top of the column and the 15 mi reservoir filled with sufficient hexane to elute the ?C8s. The flow is adjusted to 1 mt/min using the air pressure. Reprinted, with permission, from ASTM (1981a); copyright 198L by American Society for Testing and Materials. MONS 223578 Cleanup 1__________ utmox 1 1 l 44C 1 I 1 or 129 t H u ti or to itt. Figure 6-3. Aroclor Elution Patterns fro* $ "ica Cel Microcolumn with Hexene as Eluting Solvent See Figure 6*2 for column specifications. Reprinted, with permission, from ASTH (1981*); erryright 1981 oy American Society for Testing and Materials. 3. Place a 25-g charge of activated silica gal into a Chromaflex column. Settle the silica gel by tapoing the column. Add acrut l cm of anhydrous sodium sulfate to the top of the sil ica gel. 4. Pre-elut* the column with 70 to 80 mi of hex ane. Oiscard the eluate. Just befc-e exposing the sodium sulfate layer to air, stc: the flow. 5. Add the sample extract to the columr 6. W*sh down the inner wall of the column with 5 ml of hexane. MONS 223579 130 Anilyticat Chemistry of Pcag 7. 1utc the PC8s with 195 n of diethyl ether/ hexene (10:90; v:v), B. Collect 200 ml of the eluate in o KuderneOenish flask. All of the PCBs should be in this fraction, Concentrate to en appropriate volume. 9. Analyze the sample. 0 Alumina 1. Properties: Alumina (Ai39}) is a common in organic sorbent with a typical surface area of 100 to 400 mJ/g (Stanl, 1969). It is typically activated by heating to remove water (anywhere from 120*C tc 800*C has been re ported). The activated material is then often deactivated with water to varying degrees, sometimes referred to s Brockmann Activity 1 through V, Activty 1 is most active (i e., OX water) and Activity v (15X -j-.er) is least acti.* (p. 203 in Stahl, 1969). Intermediate activities are n (j% water). III (6% water) and IV (10* water). 2. lipid removal; A classic alumina cleanup, de veloped for organocMorlftt pesticides, (Holden and Marsoen, 1969), has been successfully used to remove lipids fro* fish (ZIiko, 1971a) and milk (MusU! et al., 1979) for PC8 analy sis. Columns were prepared by dry packing 2 g of 5% waterdeactivated. alumina. PCBs, as well as many organochlorine pesticides, eluted in 20ml hexane. 'he sample was then chromatographed on a silica gel column of the same site to separate the pesticides and PC8s into g-oups. A 2*g column or alumina has a capacity for SO mg lipid (Hutzinger et al.. 1974a), while at least 100 mg of fat a-e removed with both the silica and alumina columns (Holden a-o Harsdtn, 1969). A combination of alumina and silica ;ei i.* one column was useo to simultaneously dean up fat and egg samples and concur rently separate PCBs p,p'*006 from (Oesetn and Srevik, 1979). Hexane was used to elute the anlytes from the col umns which were packed with 2 g alumira on top and 4 g of fully activated silica gel on the botton. Quantitative re coveries were observed. PCBs were quantitatively recovered in the first fraction of hexane eluted from a coluri of SX-deactivated neutral alumina (Teichman et al., 1976). Many pesticides such as 00, 00T, aldrin, and heptachlor were also recovered in this fraction. The technique was usea for the cleanup of soi), sediment, and oyster samples. HONS 223580 C!nup 131 Telling et at. 0977) used two alumina columns for the cleanup of oly extracts from fish and fatty foods. The smaller column, 4 g alumina (activity II), had a caoacity for 4t least 200 mg oil, with 100% recovery of PCBs in 5 ml hex* ane. * larger column with 22 g activity IV alumina could quantitatively elute PCBs in 10 ml hexane with SCO mg oil present. Some fractionation from the pesticides was thieved. The major co*eluting pesticides wereg,g'*00 and #,g'-OQT Millar et al. (19B1, 1982) demonstrated that the larger column gave quantitative recoveries for seven common Aroclor mixtures from wastewater (Millar et al., 1981, 1982). This and a Florisi) cleanup (Mills et al., 1963) gave similar results, exceptthe alumina column spread Chlordane, toxa* phene, and some other pesticides over a broad band, often in two or three fractions. The PCBs eluted quantitatively in the first 40 ml hexane. 3. Cleanup of air samples: Alumina column chroeatography has oeen used to clean up extracts of air samoies collected on poiyuretnane roam (lewis et al., 1977; Macieod. 1979; Lewis, 1982). The cleanup reduced interferences to < 1 pg/mJ air (lewis et al., 1977). A 1-ml concentrated ex* tract was applied to a column of basic alumina (8rockan Activity IV) and eluted with 15 ml hexane. Recoveries of BB to 107% were observed for five individual di* through hexa* chlorobiphenyls. figure 6*4 illustrates the extent of the cleanup achieved. Clearly, the cleanup removes many ECO* active interferences. 4. Separation of PCOfs and PCODs from PCBs: Col umn chromatography using alumina has been used to separate PCDFs and PCDOs from commercial PCBs and Yusho oil (Nagayama et al., 1975, 1976). After saponification of the Yusho oil (see Chapter 2) and an initial cleanup on silica gal, an alumina fractionation .as performed. The alumina column was eluted with four solvents: (a) 20 ml n-hexane, (b) 120 ml carbon tetrachloride/n-htxane (20:80), 7c) 10 ml n-hexane, and (d) dichloromethane/n-nexane (20:80). The P?DFs and PCOOs were recovered in the final fraction, A second frac tionation was required in some cases to adequately remove the PCBs, A smaller column and smaller solvent volumes were used for the repetition of the alumina fractionation. A recovery of 90S was obtained for an unspecified PCOf. 5. Other applications: Alumina has been used for column chromatographic cleanup of wide variety of matrices, including fish (litko, 1971a; Ofstad et a!., 1878), human and animal adipose (Oonkin et al., 1977); eggs (Wardall, 1977; litko, 1976), blood (Welborn et a)., 1974), milk (Musial et al., 1972; Siyali, 1973; Tuinstra and Traag, 1919a), biolog ical matrices (Keveseth and Brevik, 1979; Tuinstra and HONS 223581 132 Analytical Chamiatry 0< Pcat figure 6-4. PGC/ECO Chromatograms (A) Before end (9) After Alumina Column Chromatographic Cleanup The sample is e personal eir monitoring sample collected at Inez, Horth Caroline. Peprinted from Mecleod (1979). MOWS 223582 Cl#anup 133 Traege. 1979*; Tuinstra et *1.. 1981, Teichmen et *1., 1978), sediment (Goerlitz and Law, 1974, Teichman et *1., 1978), soil (Tuinstra end Traag, 1979a; Teichman et a 1. , 1978), air (Lewis et 41. , 1977; MacLeod, 1979; Lewis, 1982), water (United Kingdom Department of Environment, 1979; Devenish end Harling-8owen, 1980), end oil (Kohli et el., 1979; Nagayama #t el., 1975, 1976; Telling et el., 1977; Sonchik et el.. 1984). 6. Oetei led procedure; As en exempte of the alum* ine cleanup technique, the eppropriete section of the Seller end lichtenberg (1981) procedure for PC8s in transformer oils is given below. 1. Adjust the activity of the alumina (Fisher AS40 or equivalent) by heating to 200C for at least 2 hr. When cool, add 3% water (wt:wt) end mix until uniform. Allow the deactivated alumina to equilibrate at least 1/2 hr before use. Store m a tightly sealed bottle. 2. Variations between batches of alumina may af* feet the elution volume of the various PCBs. For this reason, the volume of solvent required to completely elute all of the PC8s must be verified by the analyst. The weight of alumina can then be adjusted accordingly. 3. Place a 50*g charge of alumina into a Chroma* flex column. Settle the alumina by tapping. Add about 1 cm of anhydrous sodium sulfate. Pre*e1ute the column with 70 to 80 mL of hex* ane. Just before exoosure if the sodium sul* fete layer to air, stop the flow. Oiscard the eluate. 4. Add the sample extract to the column. 5. Carefully wash down the inner wall of the col* umn with 5 ml of hexane. 6. Add 295 ml of hexane to the column. 7. Oiscard the first 50 mL. 8. Collect 250 mL of the hexene in a KuderneOanish flask. All of the PC8s should be in this fraction. Concentrate to an appropriate vo 1 ume. MONS 223583 134 Analytical Chemistry of PCas 9. An1yz the sample. i. Carbon Carbon (or charcoal) has long been used to Oecoi0r reaction mixtures and otherwise dean up organic solutions The chemical properties of the graphitic lattice mane carbon not only a strong, but also a selective adsorbent. Thus carbon can be used to both clean up samples and also fracdonate PC8s and other organics according to their structural properties. The carbon column techniques exhibit excellent se lectivity, but poor capacity. Thus, they are generally used as a second cleanup after major interferences have been re moved by another technique. Oougherty et al. (1980) used gel permeation chromtography (see Section v, below) to remove the lipids and other major interferences from fish extracts be fore aoplying a carbon/foam cleanuo. Smith et i (10841 used a senes of silica-oased soroents prior to tne esreon, fiber column, as described later in this section. 1. Separation of PC8s from other compounds: Chau and aakj'ak (197?) use^a carbon/foam mixture to separate PCBs from chlorinated pesticides. Following a general cleanup on FlorisU column, mirex, photomirex, heptachlor and aldrin were quantitatively separated from PCBs and certain other organochlorines by elution of the carbon/foam column with cy clohexane. The Cleanup scheme is shown in Figure 6-5. Greater than 95% of the target chlorinated compounds, in cluding PC8s, were recovered in their respective fractions The columns were prepared by chopping pesticide quality poly urethane foam (Analabs) in chloroform and slurrying with car bon (Norit C*170: four parts carbon per six parts foam, by weight). The mixture was then dried, drv-oacked into s 5 mm ID column to a depth of S cm (about 0.2 g), and toooed with 1 cm Na2S0. A charcoal column has also been used to separate PCBs from several pesticides which co-eluted from an alumina column (Teichman et a)., 1978). The column, 140 x 6 mm 10 was slurry-packed to a height of 90 mm with 50-200 mesh char coal (Fisher No. 5-690). Aldrin, heptachlor, g.g'-DDE, p.g'00T, g,p' -000, lindane, and chlordane eluted in a first frac tion of 90 ml acetone/diethyl ether (25:75). Recoveries ranged from 81 to 112% at a fortification level of 1 to 4 ppb in soil. The PCBs eluted in a second fraction of 60 ml ben zene. Recoveries of 100% were reported for Aroclor 1254 at a forti f ication level of 7 ppb in soil. MONS 223584 Cleanup 135 Sdim* nt i Exfroef I Floriiil Column i Petroleum Fraction Conjoining Heorocnlor a -8HC, p.p'-OOE, Aldrin, Mir#*, Phofomirax, PC8 :i Focion Containing 13 Orgonochiorin| i Chorcool-Foom Column ( Cvdohnon* Fraction Mi rax, Phofomirax. Hptochtor. Aldrin 1 Banian* fraction PCBi, a-BHC. ,jT-DDE Figura 6*5. Flow Chart of Extraction and Claanup Using Florisil and Carbon/Foaa Column Chromatography to Separata PC8s front Other OrganocMorina Compounds in Sediment Samples Reprinted, with permission, from Chau and Sabjak (1979); copy right 1979 by Association of Official Analytical Chemists, Inc. HONS 223585 136 Analytical Chemistry of PC83 2. Separation of PCSs by structural featuresbon has a high se'activity for those""i}CBs which can assume * planar conformation. These PC8s contain no ortho-chlorines As tne degree of ortno-substitution increases (up to four chlorines in o.o' positions), the retention decreases. tkus a PCS -ith four ortho-chlorines would elute from a caroon column before other PCSs. This selectivity is useful for fract ionat ion of PCSs The degree of ortho-substi tution 4f. fects the toxicity of PCSs (see Chapter 2 for a more detailed discussion and references). Therefore, isolation and char acterization of different fractions from commence) sutures has been of interest. Jensen and Sundstrcjm ( 1974) used a caroon column to seoarate PCSs according to the number of o.o'-chlorines. By combining this procedure with high resolution gas chromatog raphy, better separation and identification of individual PCB congeners was achieved. As illustrated in Figure 6-6. nearly 60 PCS congeners were identified in the technical mixtures of Clopnen A50 and A60. This cnarcoal column (1.5 x 20 cm) as a modification of that reported by Berg et a 1. ( 1972) to sep arate DOT, 000, and 00E from PCSs. The Jensen and Sundstrom (1974) modification of the procedure consisted of using Oarco G*60 activated charcoal mixed with equal weight of Celite 545. The column was eluted with tetrahydrofuran and then benzene. PCSs with four ortho-chlorines eluted essentially with the dead volume of the column (10 ml tetrahydrofuran; Fraction l; Tract 8 in Figure 6*6) and those with three ortho-chlorines eluted with an additional 20 ml of tetrahydrofuran (Fraction 2; Trace C in Figure 6*6). However, the compounds with only one or two ortho-chlorines required at least 100 mi of benz ene for elution. The substitution pattern of additional chlorina atoms in the non-ortho positions of the PCS molecule did not noticeably affect the order of elution. The carbon column cleanup was applied to the analy sis of human adipose tissues following removal of 000, 00T, 00E and metabolites by hydrolysis and oxidation (Jensen and Sundstrdm, 1974). Most of the PCSs present in the pooled adipose extracts contained one to three ortho-chlorines. The only PCS with four ortho-chlorines that was positively iden tified in these samples was decachlorobiphenyl. Jensen and SundstrB* (1974) suggested that the co planarity of the phenyl rings might be affected by the number of chlorine atoms ortho to the biphenyl bridge. This differ ence in molecular conformation could explain the separation properties of activated charcoal based on the interactions between the graphite structure and aromatic character of the PCBs. The authors also suggested that this mechanism might explain the elution of o.g'-QOT and its metabolites before MONS 223586 Cleanup 137 Figure 6*6. Chromatograms of PCBs Fractionated According to Number of Ortho Chlorines Using a Charcoal Column The number of ortho chlorines is indicated above the peaks m (A) Chlophen a55 starting material; (B) Fraction 1, contain* log PCBs with A ortho chlorines, eluted with 10 ml tetrahy* drofuran; (C) Fraction 2, containing PCBs with 3 ortho chlo* rines, eluted with 20 mi tetrahydrofuran. and (0) Fraction 3. containing PCBs with 2 and 1 ortho chlorines, eluted with 100 mL-benzene. PGC/ECD chromatograms were obtained on a 5.2 m glass column packed with AX Apiezon l on Chromosorb W, op* rated isothermally at 2$0*C. Reprinted, with permission, from Jensen and Sundstrom ( 1974) copyright 1974 by the Royal Swedish Academy of Science. Stockholm, Sweden. MONS 223587 138 Analytical Chamiatryof PC8a the Corresponding E . E ' isomers Jensen and Sundstrom ( 1974) noted several considerations for working with activated carOon systems: (1) additional effort is reouired to analy** more than one fraction of an extract containing PC8s (thr** injections versus one); (2) and the elution profiles of each batch of activated carbon adsorbent must be established. Stalling t at. (1978. 1979a,b) and Huckins et al. (1980) have used activated cnarcoal dispersed on either poly urethane foa or, more recently, on glass fibers (Smith et a 1 , 1984), to separate structurally similar components 0f Aroclor mixtures in structyre*toxicity correlation studies The results presented by Stalling et 1. (1978) corroborated the previous work by Jensen and Sundstrom (1974). Those PCBs With more Chlorines in the ortho positions eluted first from a column of 1.7S g of activated carbon (Amoco PX*21) as shown in figure 6-7. In addition, within each of the six possible o,o'`chlorine substitution groups shown in Figure 6*7, elu tion volumes generally increased -ith additional chlorine substitution. This conrlicts with the findings or Jensen ana Sundstrom (1974) and may be a function of solubility. Using the activated charcoal cleanup procedure, separation and de tection of Aroclor 1248 and 1254 components lacking o,o'- chlorine substitution was feasible at concentrations "less than 1 pg/g Aroclor using high resolution gas chromatography/ election capture detection. Huckins et al. (1980) determined the concentration of non ortho-ortho1-substituted PC8s in several Aroclor mix tures (fable 6-1) and fish. The non ortho-ortho'-substituted PCBs are of interest because of the higher toxicological ac tivity of these compounds relative to other PCS congeners. Carbon-14-labeled 3,3' ,4,4'-tetrachlorobiphenyl, added to the Aroclor mixtures, averaged 89* recovery from the carbon/foam column. As indicated Table 6-1. the highest concentra tion* of the 3,3',4,4'-tetrachlorobiphenyl were found in Aro- clors 1248 end 1242 which correlated well with the higher toxicity of these mixtures to fish (Huckins et al. 1980). In addition, 3,3` ,4,4'-tetrachlorobiphenyl was isolated and identified as a major constituent of the non ortho-ortho'- substituted PCB fraction from composite ffsh samples. Huckins et al. (1978) and Stalling et al. (1978) have also used the carbon/foam chromatographic procedure to isolate other planer polychlorinated aromatics such as dibemo-g- dioxins (PCDOs) and dibenzofurans (PCOFs) in formulations of the Herbicide Agent Orange, Aroclors, and as trace environ* mental contaminants in fish tissues. MONS 223588 Cleanup 139 tlIIIH'II tMKMMf ** Figure 6*7. Elution Order of PC0S from Carbon Column, Illustrating Dependence on Number of ortho Chlorines Two 10 cm x l cm 10 columns containing 1.75 g PX-Z1 carbon (> 325 mesh) were eluted in series with a steo gradient of 60*mt. portions of toluene/cyclohexane (2:96 and 100:0). Reprinted, with permission, from Stalling et el. (I979)s copyright 1979 by New York Academy of Sciences. HONS 223589 6*1. Concentretion oi Non*o,o*Chlorlne Substituted PCtt ionyeuers u\ Aroclor Htstures4 Aroclor _M4* -inC8 found, N t<g/g std dev M\44- *l*treC6 Found, N j.y/g Std. dev. iiilci.?' PenteCS found, * i'9/9 3.3' .4.4* .b.V-he.eCB f uutul. ug/g 1016 3342 1240 12S4 1260 3 13,200 3 16,600 S 6.100 3 300 3 b? 1,700 3,100 1.200 40 ? N0L 3 2,400 S 3,400 3 210 NO 200 330 12 NO NO NO NO NO NO NO * "Aroclor teapl* site ranged fro* SO to 10) ag end separations were aaue by using coluansd ca ID 10 ca) of Amco M-21 carbon dispersed *n f oaa (IS* /w. carbon/foaa). N * nueber oi taaplet b NO * None delected; alniaua detection Unit wet 0.4 p9/g for eapufiaental conditions described in aelhodt section, also see a*tbods for recovery veiues. c Plus sign indicates that J, J'.4,4',S'PenteCS was present in concentrations < 2S0 pg/g. lock of standard* of known concentre!ions prevented exact aeesureaents No 3.3',4,4'.S.S'-HenCB was detected in eny of the five Aroclort. Source: rtuckins *t el., i960, reproduced with peraisslon of the Association of Official Analytical Cheaists, Copyright 1900. MONS 223590 Cleanup 141 The caroon/foam columns suffered from breakdown of the foam during use and a carbon/glass fiber system nas been adopted. Tn# most recent version of this system utilized th# carbon/glass fiber column in series with other columns to ex tract. clean uo and fractionate tissue samples in a two-part continuous process (Stalling et a I. . 1982; Smith et a I. . 1984). The serial columns are connected by tubing and valves to provide semiautomated operation with gravity flow. In part I (Figure 6*6) the santQle, in a mixture with sodium sul fate. is extracted with dichloromethane/beniene (SO;SO) and the extract is, in the same process, passed through the sor bent columns. Specifically, the extract passes through silica-based adsorbents in the following order: potassium silicate, silica gel, cesium silicate, and finally silica gel. The residues of interest (PCOFs, PCDOs, specific PCS isomers, PCNs, as well as other aromatic chemical classes) are retained on tne carbon/fiber adsorbent and are subseouently recovered by reverse elution with toluene. In pert II (Figure S-i), following a change of solvent to hexane, the sample is epplitd to a second series of adsorbents contained in two columns. The first column contains small amounts of cesium silicate and sulfuric acid-impregnated silica gel. The effluent from this column flows directly onto an activ ated alumina column on which several classes of residues are fractionated. Following reduction of sample volume, GC/ECO or GC/MS analyses are carried out. A similar system has been automated, using pressurized flow, solenoid values, and mi crocomputer control (O'Keefe et a!., 1985). II. HIGH PERFORMANCE LIOUIO CHROMATOGRAPHY A. Characteristics High performance liquid chromatography (HPlC) can be used either as a cleanup technique, as discussed here, or as a final determination technique, as discussed in Chapter 7. As a cleanup technique, HPlC follows the same chromato graphic principles as the open column adsorption column tech niques discussed above. Molecules are selectively retarded by their adsorptive interections with the solid phase. Under the proper conditions, PC8s {re separated from interferences. If an appropriate fraction is collected, the PCS content may be subsequently determined by GC or other techniques. The advantages of HPLC over the open column tech niques are resolution, speed, reproducibi1ity, and the abil ity to monitor the effluent. HPlC, as the name implies, has much better resolution than open column systems oecause the sorbent particles are smaller, more uniform, and more tightly HONS 223591 142 *n i umcito*. --< AQiomtON CAMON |*l**a (C*"|*/CM,CI, I .1 fdHiwi (>0<l WIk* 0*1 (|J <* l`**l S1H<* 0*1 U) lH I <*< **4 >**' **l k*9*adi (a***^ M># l*#Wi .. I.mao*- < KD&i *m4 PCM. i*M> C***-!**,) Oiw P>W. nihim t*l*1* NlipiU* *4 PC00* KDfi on* >** MU It >c?>ON*now ri *omahc nto4i.< ^C..tw* l.lUw. MjVO,/il* Cat (< *?|) *1 iiiMmi MIH A fating t.*t )%CMIC4/ctM14 PCI*. KM -*. J- * CMyCi)/C^u KM.. KM. F<gur 8*8. Enrichment and frectfonation of PC8s, PCNs, PCOOs, and PCOFs from Tissue Samples using Carbon Column Reprinted, with permission. from Smith et el. (1984); copyright 1984 by American Chemical Society. MOMS 223592 Cieanuo 143 packed. HPLC can be faster because the solvent flow is con trolled Oy 4 hign pressure pump, instead of gravity. Because the same column is used repeatedly, the separations are re* producible. The UV detector normally associated with an HPtC system provides a real-time indication of the compounds elut ing from the column, which allows the analyst to make precise fraction cuts. The disadvantages of HPlC are low capacity and high cost. In general, HPlC has less capacity for very dirty sam ples (e.g., fat extracts) than an open column system using the same sorbent. In addition to the substantial cost of the instrumentation and accessories, the per-sample cost may be higher, since only one HPlC system is generally operated at a time. In contrast, 8*12 open columns are typically monitored by one analyst. 8. Pop!ications 1. Tissue: Ocspite the aforementioned capacity problems, HPlC has been successfully useo to clean up animal and plant samples for PCS and pesticide analysis (RoMender et a!., 1976). PCS* and organochlorine pesticides from a silica column with n-hexane and the triglycerides eluted with acetone. Recoveries of about 95% were noted. 2. Paper: figure 6*9 presents an example of an HPLC cleanup of a paperboard extract (Dark and Crossman, 1973). The composition of the large pea* after the PCB re* gion was not identified. The sample was extracted with ace* tonitrile in a blender, filtered, and concentrated. The HPlC conditions are given on the figure. The authors noted that the PCS retention time wes roughly proportional to the number of chlorines, with dichlorobiphenyls eluting in the 2*5 min region and trichlorobiphenyls eluting in tne 6*10 min region. Aitzetmuller (1975) used e 10-ym silica column with petroleum ether as the solvent to clean up cardboard extracts for sub* sequant PCB determination by PCC/ECO. large amounts of wax present in the sample required additional cleanup. The we* was saponified and the resulting wax aleohols removed by Florisil column chromatography. Without the Florlsil step, the alcohols overloaded the HPlC column. DOE and OQT were separated from Aroclors 1254 and 1260, indicating that, with proper fraction collection, this HPlC system could be useful for separation of 0D, 00T, and other interfering pesticides from PCBs. Krull (1977) reviewed this and similar previous work on HPlC fractionation. HONS 223593 144 Analytical Chemistry of PC8 EXTRACT OF Figure 6*9, Preparative Reversed-Phase HPlC Cleanup of Paperboard Extract A Bondapak C,,/Cora*iI column was eluted with acetonitrile water Reprinted, with permission, from Dark and Crossman (1973); copyright 1973 by Waters Associates. MONS 223594 Cleanup 145 3. Oil: Oil samples have also oeen cleaned up by HPLC for subsequent HRGC/EC0 analyse (Ches)er et el., 1979, 1981; Parris et al. . 1984). The presentive aminosi1 an* col umn (see figure 6*10) removed more CCD interferences then solvent extraction, sulfuric ecid treatment, or open column chromatography. In addition, the HPtC cleanup was more rapid. A total analysis time of 70 min was required for the HPlC cleanup and HRGC/ECO determination as compared to 8 hr for a procedure which employed solvent extraction, column chromatography, and sulfuric acid partitioning prior to the gas chromatographic analysis. The latter procedure did not clean up the sample sufficiently to yield an identifiable chromatogram of Aroclor 1254, which had been spiked into waste crankcase oil at 10 ppm* The HPlC cleanup of Chester et al. (1979, 1981; Parris et a!., 1984) was used in my laboratory to clean up transformer c11 samoles after chemical C8 destruction. The resultant oil -*$ clean enough for GC/ CD determination, but did not rme-' sufficient mineral oil for HRGC/EIMS determination. An HPlC cleanup for oils removed 96X of the oil background which was sufficient for analysis of PCBs by HRGC/ EIMS at the 100 ppb level (Nero ano Hudson, 1984). The NO?bonded column (Nucleosil 5 NQa; l-(4-nitrophenyl)propyl bonded to silica) was eluted with ah isooctane/tetrahydrofuran gradient. 4. Commercial PCS mixture: Preparative HPlC has been used to characterize commercial PC8 mixtures (Krupcik et al., 1977). A 42* chlorine PCS mixture was first frac tionated into 70 fractions by vacuum distillation. Pour of these fractions ware further fractionated into 10-14 subfrac'.:ons on a 25 cm x 8.0 nm 10 column sacked with 5 um silica gel. Tht PCBs were eluted with n-pentane at a flow rate of 400 ml/hr. These subfractions ware then analyzed by HPLC and HRGC/FI0. Individual congeners ware identified by comparison with authentic standards. 5. Separation of PCOQs f-on PC8s: PCBs are sepa rable fro* PCDOs on an alumina HPlC-column (Oolphin and Will- nott, 1976). Using a 10 pm Alox T column (250 x 4.$ mm 10). n-hexane at 1.8 ml/min, and UV detection at 270 nm, Aroclor 1268 eluted with the solvent at about 2 min. PCOOs eluted from 2.9 to 4.0 min. Separations of PCBs and other chlor inated organics on silica columns we**e also presented. HONS 223595 146 Analytical Chemistry of PC8s figure 4-10, Preparative-Scale HPLC Fractionation of Oil Conditions: Column, preparative-scale aainosUane, 7.9 mm ID x 30 ca; nod He phase, pesticide grade hexane; Mow rate, 4 nl/ain; detection, ultraviolet adsorption, 254 n; sample injected, 100 uL. Reprinted, with permission, froa Chester ct al. (1961) and Parris et al. (1984). HONS 223596 Cleanup 147 C. detailed Procedure As an example of the HPLC c'eanup technique, the *pproori*te section of the BeUer and Lichtenberg (1981) pro cedure for PCBs in transformer oils is given below. L. Quantitatively transfer the concentrated ex tract into the sample loop or the barrel of a syringe. Rinse the vial with several small por tions of solvent. It may be necessary to in ject saveral fractions. 2. Inject the extract and washes onto the amine column (Waters pSondepak 3.9 x 300 mm or equiv alent) and elute the PC0s with 1.0 ml/min hex ane. Tne IIV at 254 nm or lower should be mon itored. 3. Collect the eluent from 3 min to 9.5 min as it exits UV cell. The elution time snould be ver ified using PC8 standards covering a range from mono- to decachlorobiphenyls. 4. After collection, wash the column by eluting with methylene chloride until the absorbance attains a stable minimum. Return the system to hexane. 5. Concentrate the hexane eluate under a gentle stream of purified nitrogen to an appropriate volume and a*jlyze. III. THIN-LAfER CHROMATOGRAPHY As mPLC, L.V.n layer c.-.romatograpny (TIC) can be used either as a cleanup technique or as a final deter mination technique, as discussed in Chapter 7. The chemical separation mechanisms of TLC are also discussed in Chapter 7. Silica gel (Kieselgel G) TLC plates were used to clean up fish axtraets for PC8 and organoehtorine pesticide analysis by GC/ECO (Hattule, 1974b). The technique was a useful supplement to the routine sulfuric acid cleanup for confirming the concentrations of dieldrin, endrin, and the OOT-type compounds. Up to 15-mg fish fat could ba applied per spot. The TLC cleanup involved a two-stage elution, first with dichloromethene to half of the plate height and second with n-heptene. Plates were sprayed with diphenylamine reagent'and developed under UV light for 3 min to yield colored spots. PC8s were light violet. PC8s, aldrin, and HONS 223597 143 Analytic*! Chemistry of PCBs g.g-OOE co-eluted in an upoer spot, while g.g'-OOT, o.p'-00T g.g'-OOO. dieldrin, end endrin were separated into"* spot. Tn fat renamed much lower on the plate. The Tm technique gave PCB recoveries comparable to Doth 5lj|furi(. acid cleanup and an alumina column cleanup. Nevertheless tne TlC technique was recommended for routine use only f0fl samples with very low fat content (less than 10 mg) suen *s plankton, bottom invertebrates, and water plants. Silica gel TLC has also been used to clean up extracts of bird egg* (Koeniger et al. ; 1975.) and bald eagle carcasses (Begley *t ai., 1970) for PCS determination. Animal feed extracts were cleaned up on alumina Tic plates using nheptane as the developing solvent (Vestoo ar>0 Noren, 1970)." The PCBs, along with g,g'O0E, o.g'-QQE, **d o.g'-DDT were contained in on# area of th# plate, -nicn .*$ scraped from the plate and extracted. The extract couio tnn Oe analyzed by GC or further cleaned up to remove p.p'-OOC Cy oxidation with chromium trioxide or by saponification sodium hydroxide to remove o.g'-DOT. A reversed phase TLC system was used to separate PCB mixtures into seven fractions for GC determination (Oe Vos and Peet, 1971). Paraffin-impregnated silica gel plates were developed with a solvent mixture of acetonitriI#/ acetone/methanol/water (40:18:40:2). Silver nitrate and Uv light were used to visualize the spots. For preparative work, a small part of the plate was visualized and tne rmaining, unvisualized portions of the bands were scraped off the plates. IV. AOSOR8ENT SLURRY TECHNIQUES Adsorbent materials can be used in a simple slurry with the sample to effect a cleanup. As noted above, caroon has been used to decolor chemical -taction mixtures n * slurry, although the technique has not been reported for PC8 analysis. The only adsorbent slurry technique commonly used for PCB analysis is the flonsil slurry for cleanup of trans former oil and similar matrices (EPA, 1981a, Bellar and Lichtentoerg, 1901; A$TM, 1963). Although no articles have been published showing either the extent of cleanup or PCB recovery, this technique appears to oe in common application. It may be speculated that the Florisil slurry removes ECO active oxidation products formed during transformer oil use and also the onenolic and epoxide antioxidants which are added to askarels, mineral oil dielectric fluid, and other oil matrices. HONS 223598 Cltanup 149 As an example of the Morisil slurry cleanup techniou. the appropriate section of the BelUr end Uchtenberg (1961) procedure for PCBs in transformer oils >s given below. 1. Piece the semple extrect into e 20-ml narrowmouth screw-cep conteiner. Add 0.25 g of Florisll (PR grede or equivelent). Seel with e Teflon-lined screw cep end shake for 1 min. 2. Allow the Florisil to settle; then decent the treeted solution into e second conteiner with rinsing. Concentrete the sample to en appro* priate volume. Anetyze the semple. V. GEL PERMEATION CHROMATOGRAPHY A. Properties Gel permeetion chromatography (GPC), also called size-exclusion chromatogrepny. separates molecules primarily by size. Large molecules ere not well retained by the solid phese and elute early, while smell molecules elute later. The stationery phese is a hydrophobic gel which is swollen with the elution solvent. Smeller molecules permeate into the gel particles, are retarded, and elute later than larger molecules. In addition to the separation based on molecular dimensions, adsorption phenomena in the GPC column can also separate compounds of similar molecular weight but different polarity. Thus, GPC cannot be regarded as solely a size sep aration technique. Common GPC packing materials are copoly mers of styrene and divinylbenzene, often modified with dif ferent functional groups (e.g., Styrage!, Bio-Beads); and polydextran (Sephadex). A more detailed description of GPC is available In genera! chromatography monographs (e.g., Zweig and Shema, 1972). Gel permeation chromatography (GPC) is a popular cleanup technique for complex matrices, especially those con taining macromoleeular intarferents. Examples include bio logical materials containing high levels of lipid materials or oils with molecular weights in the range of $00 to 1500 emu. GPC has been fully automated to accommodate Urge num ber of sample extracts. B. Eluting Solvents The use of GPC to clean up biogenic extracts for PCS analysis was introduced by Stalling et al. (1971, 1972), using Biobeads $X-2 with cyclohexane as the solvent. Re coveries of PCBs as well as endrin, methoxychlor, lindane, HOMS 223599 150 Analytical Chemistry of PCBs ditldrin, malathion, parathion, 00C. 000 end OOT were rt. ported to be > 95X for samples containing up to 500 mg lipid materials. Stalling at a). (1971) recommended thet lipid materia) should not exceed S00 mg for a single analysis with this size column. A mixed dichloromethane/cyclohexane solvent wes used to elute yoler compounds such as chioropnenols along with the PCBs and organochlorine pesticides (Kuenl mg Leonard, 1978). Retention volumes end recovery studies for the polar and nonpolar compounds were measured on Bio-Rad SX-2 column using the following mixtures of dichloromethme/ hexene: (a) 100:0, (b) 10:90, (c) S0:S0, and (e) 7S: 2S. The 50:SO mixture was the best compromise between high recoveries and compound separation. Figure 6*11 is en example of the resolution with the 50:50 mixture on a similar column (R'bick et a). . 1982). . Oichloromtthant alone was used as a raoid ana effi cient eluent for the bulk separation of lipids from low no* lecular weight organic compounds, while the dichlorometnane/ hexene (50:50) solvent system was usad to fractionata low molecular weight organics Into polar and nonpolar solvtnts. Figurt 6*12 is an txamplt of the two-step cleanup. The upper trace (100X methylene chloride) represents bulk lipid separa tion for a fish extract and the lower trace (SOX methylene Chloride) is the fractionation Into polar and nonpolar constitutnts. Fractions 1 and 2 from the second cleanup con tained PCBs end chlorobenzene, while fractions 1 through 10 contatntd phenols, anisole, and hetarocyclic aromatics. Kuehl et a). (1980a,b) usad the combination of GPC and negativt chemical ionization mess spectrometry to analyze fish tissues for PCBs, organochlorine pesticides end a number of polar compounds- A micro-GPC system consisting of e column of Bio* Bed SX-2 beads (500 n x 10 an) using dichloromethsne/cyclo* hexene (50:50) as eluent was described by Kuehl et el. (1980b) for the cleanup of S to SO mg of human adipost tis sue. Larger sample masses overloaded the column end the PCBs were net resolved from the fat. Steinwandter (1982b) re ported e similar GPC cleanup with dichloromethane as the elu tion solvent for e Bio-Beads SX-3 column. C, CalIbration A variety of substances have been used to calibrate the elution of sample components on GPC. A traditional call* brant is corn oil. Tht PCBs art collected in the fraction that elutes after the corn oil (Haile and lopez-Avila, 1984). HONS 223600 GPC cn SX"3 Bk>>Bo<is 60 CRRnS ? 6X48 Cn nwnN r<.Hi?/CH?tL? so/sn MBS' >* wa/r(,<* itl'O *'< *<'<* < < J B*'*** IiuIMiMN . ii*4 t ' *o "' IdtgwuniMtirit I >*<*..** , t, | k uO* i >4 -- I n*H*n ucim*-*** i '***< >* nn *1 . rtUDS mm iyiHH>N i <!> > % [Mild HjUBlMItt *11100(1 |niM iin* # tMMIC I0 t Mt Figurt 6*11. GPC Elution Profiles of Selected Biogenic Compounds and Environmental Contaminants Conditions: 60 g SX*3 SioBeads, 2.5 cm x 48 cm column, cydohexane/dichloromethane (1:1), 6 ml/min. Ki'printtd, with permission, from Ribicfc at al. (19821; copyright WQ? Uy American Chemical boc iety. HONS 223601 IM* I2S ISO 175 200 225 250 Elution Volume (ml) Figure 6-12. GPC Chrometograms of Fit Sample Showing the Separation of low Molecular Weight Organic Chemicals (IMWO) fro* lipids (Top) and Fractionation of IMWOs (Bottom) In the first step (Chromatogram A), the IMWO fraction is collected, eliminating most of th* lipids, which elute first. In the second step (Chromatogram B), 10 fractions were collected for PGC/ICD analysis. PCBs were in Fractions 1-4 Reprinted, with permission, from Kuehi and Leonard <|9//). copyrtgnt 19// by American Cnemlcal Society. HONS 223602 Cl^up 753 A more elegant calibration uses Vitamin acatate and Vitamin Xj to bracket the PCB window (Pellizzari at al., 1983a) Th vitamins are detected in the column effluent by a UV detector at 254 nm. Degradation of the vitamins has been observed, so solutions should be fresh and their duality monitored (unpub lished results, J. Stanley, Midwest Research Institute, Kansas City, Missouri). 0. Comparison to Other Cleanup Techniques Griffitt and Craun (1974) compared GPC cleanup *ith acetonitrile partitioning for the analysis of PCBs and or* ganochlorine pesticides in fat~containing food. In most cases 98% of the fat or oil eluted from the column before the pesticides or PCBs. Cleanup efficiency was better than mat obtained with ecetonitrile partitioning. Recoveries of Aroclor 1254 from milk ft were generally better with GPC (92 100%) then with a combined acetonitrile partitioning and Monti! column cleanup (77%). Since a GPC column is generally used repetitively, Griffith and Craun (1974) investigated the potential for an alyte carryover. High concentrations (500 ug each) of heptachlor epoxide, malathion, end Aroclor 1242 were loaded in al ternate sample loops with the intermediate loops containing cyclohexane only as blanks. The analysis of the "planks" showed that carryover was less than 0.10% (0.5 ug) for each of the spikes. The study authors concluded that this carry over was insignificant at the residue levels encountered in oils end fats. The use of automated GPC was shown by Tessari at ai. (1980) to be fester end more economical than the classic Mills'Onley-Gaither acetonitrile partioning and Floristl col umn chromatographic techniques (Mills at el.. 1963; Watts, 1980) for cleanup of human adioose samolas. Comparable re sults for PCBs end 19 orgenochlorine pesticides were obtained by me two techniques for 21 aoipose *amp*. . Automation Tindle and Stalling (1972) reported an automated apparatus for GPC cleanup in residue analysis with specific applications for fish lipids. The automated system allowed continuous operation with capability to process up to 23 sam ples, in sequence, Recoveries were reproducible (< 5% RSD) end cross-contamination from one sample to another was less than 1%. Since the introduction of the automated apparatus, gel permeation chromatography has been successfully used as e cleanup for high molecular weight matrices and has provided e cost-affective approach cleanup of large numbers of samples MONS 223603 154 Analytical Chemistry of PCBt (Albro. 1979; Caragay and levins. 1979: Gnffitt and CreUA 1974; Hail* and lopez-Avila, 1984, Hopper and Mugnes 197c' Kohli at al , 1979; Kuthl et al., 1980a, 1980b; Rodrigue? I* a I. 1980; Stalling, 1971, 1976; Stalling at al., 197? ia7 restart, 1980). * f. App I ications Tht use of GPC cleanup in PCS analysis has bttn re viewed (Krull. 1977). In addition to the applications cited in the paragraphs abovt, GPC has bean used to claan up fun (Kloeofer, 1982; Kuehl at al., 1980a: Ooughtrty at al., 1980 Stalling at al., 1972; Stalling, 1971, 1976; Tuinstra at al ' 1983); adiposa (Egestad at al., 1982; Tessari at al., 1980> oil (Kohli at a 1 . 1979; Young and Kamps, 1982); mi)i| (Egastad at al., 1982); fatty foods (Griffitt and Craun 1974); blood (Needham at al., 1981); sludge (Rodriguez at al., 1980; EPA, 1979a); and wasttwater (Caragay and levin* 1979). ' G. Qatailtd Procedure As an examole of tht GPC cleanuo tecnniaue. the 10propriata section of the Sellar and llcntenetrg (1981) pro cedure for PCBs in transformer oils is given below. 1. Sat up and calibrate the gal permeation chro matograph with an SX*3 column according to tht Autoprap instruction manual. Ust methylene chloride/cyclohexane (15:85, v:v) as tht mobile phase. 2. Inject 5.0ml of the sample extract into tht instrument. Collect the fraction containing the PCBs (sea Autoprap operator's manual) in Kuderna-Oanish flask equipped with a 10-ml ampul. 3. Concentrate tne i>C8 traction to an appropriate volume. 4. Analyte the staple. VI. LIQUIO-llQUIO PARTITIONING UQuid*iiquid partitioning is ustd in both cleanup and extraction (see Chapter 5) steps. Partitioning is gen erally ustd to remove polar inttrftrtnce wnich have muen dif ferent partition coefficients from PC8s. As described in Chapter 5, an acetonitrile-hexane partition is ofttn ustd to MONS 229604 Cleanup 155 remove bulk lipids from hexene extracts of fatty samples. These include adipose (watts, I960; Swift and Settle, 19?6; Porter and Burke. 1973), food (Mills et al., 1963; Leoni et al., 1973; AOAC, 1980a; FOA, 1977; Tanade. 1976; Leoni et al., 19^3), milk (Watts, 1980; fessari. 1977; Tessan and Savage, 1980). blood (Welborn et al., 1974) and eggs (Muthern et al.. 1972). Acetonitrile partition has also been used as part of the extraction cleanuo for both mineral oil (Gordon et el., 1982) and silicone oil (Ktimisch and Ingebrigtson, 1980) transformer dielectric fluids, as described in Chapter 5. Either a hexane-dimethylformamide (OMF) partition or a Florisil column c>eanup were recommended as cleanups for determination of lighter PCS mixtures such as Clophen A-30 and Aroclor 1242 (Seidl and Bal1schmiter, 1976b). Both tech* niques gave > 90% recovery of Clophen A-30 from olive oil ith only 5-10% of the matrix carried into the extract. These deanuos were judged adequate for GC/EC0 determination. In the partition cteanuo. 5-10 g oil were dissolved in SO mi. nexane, ana extracted times with 15 ml OMF. The combined OMF extracts were diluted with 100 ml water and back* extracted with 2 x 20 ml hexane. The hexane layers were com bined, dried, concentrated and then determined by HRGC/ECQ. Two other cleanup techniques gave inferior recoveries: hex ane/acetonitrile partition (45-60% recovery) and saponifica tion/sulfuric acid extraction (80% recovtry). As an example of a liquid-liquid partition cleanup technique, the acetonitrile partition section of the Bellar and lichtenberg (1981) procedurt for PCBs in transformer oils is given below. 1. Place the sample extract into a 125-ml sepa ratory funnel with enough hexane to bring the final volume to IS ml. Extract the sample four times by snaking vigorously for 1 min with 30-ml portions of hexana-saturated acetoni trile. Retain hexane layer for combination with other hexane extracts in stap 3. 2. Combine and transfer the acetonitrile phases to a 1-L separatory funnel and add 650 ml of dis tilled water and 40 ml of saturated sodium chloride solution. Mix thoroughly for about 30 sec. Extract with two 100-ml portions of hex ane by vigorously shaking about IS sec. 3. Combine the hexane extracts in a 1-L separatory funntl and wash with two 100-ml portions of HONS 223605 156 Analytical Chemistry of PC8| distilled water. Discard the water Uytr 4nd pour the hexane layer through an 8- to lo-rf anhydrous sodium sulfate column into .a 500*? Kuderna-Oemsh flask equipped with a 10*mi re ceiver. flinse the separatory funnel and coty*,, with three 10-ml portions of hexane. 4. Concentrate the extracts to an appropriate vol ume 5. Analyze the sample. vtt. CHEHlCfcl OEGBAQATION Host of the cleanup techniques discussed tn thi4 chapter involve physical separation of the PCBs from inter ferences. In this section, however, selective chemical deg radation of the matrix is discussed as a technique for re moving interferences. Chemical degradation techniques must be used with caution to ensure that PCBs are not destroyed along with the interferences. A. Specific Reactions Specific chemical reactions can be used to destroy the matrix or interferents if they are already known, for example, technical-grade products can be selectively degraded during by-product PCB analyses (Erickson et a!., 1982, 1983e, 1984d; Erickson, 1984a). Senzoyl chloride has been hydro lyzed using l H NaOH, with a small amount of hexane present to extract any PCBs. After the hydrolysis, the aqueous layer was extracted three times with hexene and the combined hexane extracts back-extracted with 0.1 M NaOH to remove eny resid ual benzoic acid. The hexane extract was dried and concen trated to an appropriate level for HRGC/E1HS determination. Methyl esters and anhydrides have been similarly treated (un published data, Mitchell 0. Erickson, Midwest Research tute, Kansas City, Missouri). B. Sulfuric Acid This cleanup usually involves a simple shaking of the sample extract with concentrated sulfuric acid for a short time. 'he sulfuric acid oxidizes both potential GC interferents and organic macromolecules. An organic-water partition is sometimes used after the sulfuric acid treatment to remove residual acid and also any polar materials which did not fully partition into the acid. The techniaue has the advantage of both speed and ease relative to most column cleanups. MONS 223606 Cleanup 157 The technique validates for the more acid* susceptible monochlorobiphenyts (Haile and Saladi, 1977). Specifically, 10$ to 10771 recoveries were observed for 2*-and 4-chJorobipheny! in $ ml hexane after shaking for 1 min with S ml concentrated sulfuric acid. Additional cleanup with Florisil column chromatography was recommended. On the other hand, losses of mono- through trichlorobiphenyI $ were re ported when pigment samples were heated with sulfuric acid for at least 1$ min at 40-50C to dissolve the matrix (OCMA, 1982). A related technique utilized mixtures of sulfuric and nitric acids. Various reports prior to 1970. reviewed by linear (1973), conflicted on whether or not PCBs were lost by nitration. The use of sulfuric and nitric acid mixtures has not been reported since that time. Sulfuric acid treatment is often used to cleanup transformer and other oil samples for PCS analysis (Sellar and lichtcnberg, 1981; Sonchik et a). 1984). It was recom mended as the best cleanup for PC8 fluid (askarel) and min eral oil; while column cnromatograpnic deanuos were recom mended for waste oil, hydraulic fluids, and capacitor fluids (Sonchik et a 1., 1984). A sulfuric acid cleanup was found to be sufficient for PGC/ECD analysis and PGC/EIMS confirmation of PCSs in oil samples (Vcierov and Aharonson, 1980). Unlike most other sul furic acid cleanups, in which the sample and acid are simply shaken together, the sulfuric acid was eluted through the or ganic phase. Specifically, the sample was placed in a chro matographic column and concentrated sulfuric acid added dropwise. The heavier acid phase was drawn off occasionally and discarded. Acid was passed through the sample until twice the amount needed for the acid to emerge colorless had been added. This usually required about 10 ml acid/g fat. For cleanup of large samples, an alternating acid treatmentsaapie aodition scr.ame -as used. A ;mai" aliquot :f sample was first dissolved in the solvent and acid-treated, then another aliquot of sample was added to the solvent and treated, and so on. This method allowed cleanup of up to 200 g fat in one day with no need for solvent evaporation, and with lipid carryover of only 0.02%. Greater than 8S% re coveries were measured for soybean and safflower oil samples spiked with Aroelor 1254. Another alternate configuration for sulfuric acid cleanup is to elute the sample through a column of acidtreated silica gel (Lamparski and Nestrick, 1980). At least 40% HaSO can be loaded onto a silica gel column. This tech nique has been found to be efficient and considerably less MONS 223607 158 Analytical Chemistry of PC8s $sy than the traditional shakeout. especially foe. Ijrq*. volume samples (unpublished data. Mitchell 0. Erickson, ne west Research Institute, Kansas City, Missouri). Sulfuric acid has been used to clean up fish (Hattula, 1974b; Ofstad et al., 1978); adipose (United Kingdom et at.. 1972); biological materials (Murphy, 1972) oil (Kohti et at., 1979a; Sonchik et al., 1984; Levine ec al., 1983; Veierov and Aharonson, 1980); stack gas (Haile ana Beladi, 1977); paper products (Serum et at., 1973; Becker and Schulte, 1976). Fuming sulfuric (7\) has been used to clean up sewage sludge samples (Mattsson and Nygren. 1976). As an example of the acid cleanup technique, the appropriate section of the Sellar and lichtenberg (1981) pro cedure for PCS $ in transformer oils is given below. 1. Place S ml of concentrated sulfuric acid into a 40-ml narrow-mouth screw-cap bottle. Add the samole extract. Seal the bottle with a Teflonlined screw cap and Shane for 1 mm. 2. Allow the phases to separate, transfer the sampie (upper phase) with three rinses of 1*2 mi solvent to a clean container. 3. Back-extract the sample extract with 5 to 10 drops of distilled water. Pass through a snort column of anhydrous sodium sulfate and concen trate to an appropriate volume. 4. Analyze the saeiple. 5. If the sample is highly contaminated, a second or third acid cleanup may be employed. C. Chromium Trioxide The presence of g.g'-ODE, usually at a much higher concentration, can interfere with the determination of PCSs by PGC/ECO, since the d.d'-DDE peak elutes with pentachloroblphenyls (Webb and McCall, 1974). Because of the chemical and phyticel similarity of g.g'-ODE and PC8s, most column cleanups yield both analytes in the same fraction. Often, analysts have simply quantitated the g.p'-OOE peak and ig nored interference by co-eluting PCBs. Tn addition, the PC8 quantitation is affected since some PCBs are buried under the large g,g`-ODE peak. g,g'-DO can be chemically degraded to g.g'-dicMo* robenzophenone, which can then be readily fractionated with a MOMS 223606 Cltanup 159 column chromatographic cleanup. A chromium trioxide (Cr03, chromic add) degradation, followed by a silica gel column chromatography has been shown to remove the g.g'-OOE with 91% PCS rtcovtry (Underwood. 1979). Specifically, the Florijil column eluate of fatty food samole (AOAC. 1980b) was shaken with a solution of 8% Cr03 m glacial acetic acid. The chro mium trioxide layer was back-extracted with hexane and dis carded. The comoinad hexane fractions were back-extracted with water and then analyzed. The PCS peak at the retention time of 2,g'-DDE was quantitated and subtracted from the g.g'-OOE value obtained before the chromium trioxide treat ment to yield a "true" value for g,p'-00E. The extract can also be further cleaned up using silica gel column. It was noted that high lipid content of some extracts would inter fere with the g.g'-OOE degradation. Therefore, for such samples. GPC or another efficient lipid removal cleanup was recommended prior to the Chromium trioxide cleanup. Chromtum trioxide oxidation was also used to remove g.g'-OOE from pel ican egg samples for TLC determination (Mulhern et a 1. . 1972). g.g'-OOE had the same Rf as Aroclor 1254, while the dichlorobenzophenone product was well separated from the PCBs. In a related technique, Hizutani and Matsumoto (1973) prepared liquid chromatographic column using chromium trioxide and acetic add on a silica gel support, which quan titatively degraded OOE to dichlorobenzophenone to remove the O0E interference from the PCB chromatogram. Chlorinated naphthalenes (PCNs) can be selectively oxidized by chromium trioxioe to permit reliable determina tion of PCBs (Holmes and Walen. 1972). The PCNs, which occur in environmental samples as complex mixtures similar to PCBs, were oxidized by chromium trioxide in a boiling water bath for 20 min. No validation data were presented. Losses of PCBs. especially the lower chlorinated homologs, during chromium trioxide cleanup nave oten reporteo (Szelewski #t al., 1979). For the oxidation step, recoveries from spiked fish extracts ranged from 30 to 90% for eight replicates each of Aroclor 1016 and 12S4, while no Aroclor 1221 vat recovered. The lower PCBs may have been lost by ox idation, by volatilization due to tho highly exothermic na ture of the oxidative process, or a combination of the two. Similar losses and potential causes were observed by Trotter (1975). A similar but more elaborate procedure separated DOT and its analogs from PCBs, as shown in Figure 6-13 (Trotter, 1975). The PCB-Containing fraction from a Florisil HONS 223609 P G C /E C D Respoi 160 Analytical Chemistry of PC3$ Figure 6*13, PGC/ECD Chromatograms of Fish Extract (A) Before end (B) After Treatment with ROM and Chromium Trioxide to Oegrade the .'-00E (Peak 1) and .'"OOT (Peek 2) The sample, Lake Michigan chub, contained 1.3 Ppmg.g'-OOE and 2.2 ppm p.p'-ODT as measured in Chromatogram A and 2.3 ppm PCBs, calculated as Aroclor 1254, from Chromatogram B. Reprinted, with permission, from Trotter (1975); copyright 1975 by Association of Official Analytical Chemists, Inc. HONS 229610 Cleanup 161 column cleanup of fish extracts was first treated with #thanolic KOH (see below) to dehydrochlorinate DDT and related compounds to their respective olefins. The 00T products, ODE. and other olefins were then oxidized with chromium tri oxide to dichioroDen:oonenone. The PCfis were eluted in a pe troleum ether fraction from a micro Florisil column. Recov eries for Aroclors 1254 and 1260 were > SOX in the ppm range, but were poorer for lower chlorinated Aroclors and for lower concentrations. 0. Base Treatment of a sample with strong base can selec tively degrade many interferences without affecting the PCfis. The most common reaction is saponification of fats to their corresponding glycerols and carboxylates. These products are water-soluble and can be back-extracted. Another common re action is dehydrochiorination of organochlorine pesticides. In addition, and generally unreported, are a variety of other reductive degradations which remove both chromatographable and nonchromatographable interferences along with the fats or organochlorine pesticides. As noted below, losses of the lower chlorinated PCfis have been reported, so analysts must exercise both caution and appropriate QC when using base treatment to clean up samples. Saponification of fat-containing samples with base is a commonly used technique to eliminate the lipids, as dis cussed in Chapter 5. For instance, ailk fat can be sapon ified by refluxing in ethanolic KOH. The digestate can then be diluted with water and the PCBt extracted with hexane (Yakushiji et at., 1970; Tuinttra et a1.. 1900, 1901; Tuinstra and Traag, 1979*.b). A similar technique was ap plied to soil and tissue (Tatsukawa and Vakimoto, 1972). Many of the standard procedures (Chapters) utilize sapon ification of sediment, soil, water, food and adipose matri ces. Another application of bate to sample cleanup is dehydrochiorination of organochlorine pesticide* (Young and Burke, 1972; Trotter, 1975). In conjunction with several other cleanup techniques, Trotter used ethenolic KOH to de grade DOT and similar compounds to their corresponding ole fins, which were then oxidized with CrO* to their corre sponding dibenzophenones, as described above. Specifically, the PCB fraction from a floriai) column was concentrated to 2 ml and 1 ml of 2% ethanol ic KOH was added. The aixture was refluxed for 15 min or until the volume reached 0.2 ml. The PCBs and other organics were then extracted from the residue with hexane. The dehydrochiorination reaction can also be used to confirm the identity of pesticides by observing the changes in the chromatograms (Young and Burkt, 1972). HONS 223611 162 Analytical Chemistry of PCBs As an example of the base cWanuo technique, the approonate section of the Sellar and Uchtenoerg (L981)'procedure for PC8s in transformer oils is given below. 1. Quantitatively transfer the concentrated ex tract to a I25*mi extraction flask with the aid of several small portions of solvent. 2- Evaporate the extract just to dryness with a gentle stream of dry filtered nitrogen, and add 2S ml of 2.5X alcoholic KOH. 3. Add a boiling chip, put a water condenser in glace, and allow the solution to reflux on j hot plate for 45 min. 4. After cooling, transfer the solution to a 250*mi separatory funnel with 25 ml of distiI led water. 5. Rinse the extraction flask with 25 ml of hexane and add it to the separatory funnel. 6. Stopper the separatory funnel and shake vigor* ously for at least 1 min. Allow the layers to separate, and transfer the lower aqueous phase to a second separatory funnel. 7. Extract the saponification solution with a sec* ond 25-ml portion of hexane. After the layers have separated, add the first hexane extract to the second separatory funnel and transfer the aqueous alcohol layer to the original separa* tory funnel. 8. Repeet the extraction with a third 25-ml por tion of hexane. Discard the saponification so* lution, and comoine the hexane extracts. 9. Concentrate the hexane layer to an appropriate volume, and analyze the sample. VIII. ClEAWP Of OH SAMPLES Determining the extent of RC8 contamination in oil has been a major analytical application. While many labors* tories nave prescribed procedures for cleanup of specific matrices, few studies have been published recommending a given cleanup for these matrices. Table 6*11 presents the cleanup techniques recommended by Sonchik et al. (1984) for a HONS 223612 Cleanup Table 6-11. Reconmnded Sample Preparation Procedures for GC/ECD Ana lysis 163 Oil Type Procedure waste oi1 Florisil column chromatography Hydraulic fluid (excluding water glyco1s) Alumina column Chromatography Water glycol hydraulic fluids Hexane extraction Capacitor fluids (excluding PCS fluid) Alumina column chromatography PCS fluid Dilution; sulfuric acid wash Transformer oi1 Sulfuric acid wash Source: Sonchik et el., 1984; reproduced from J. Chrom. Sci. with permission of Preston Publications, Inc., Copyrignt 1984. variety of oil inetrices. For some matrices different clean ups were coaoared, but many of the recommendations eppeer to be based on experience and subjective evidence. A simple Florisil slurry cleanup (see Section IV) is recommended by ASTM (1983) to remove interferences from mineral insulating oils for PGC/ECO determination. Prior to the cleanup, the sample is diluted with hexane or isooctane. Florisil (0.25 g) is then added, the mixture shaken, and the supernatant solution oecanteo to another .ial *cr ;nstruenta) analysis. Shaking with concentrated sulfuric acid and a Florisil microcolumn cleanup are given in the procedure as alternative cleanup techniques. The Florisil slurry cleanup was preferred because it is safer to use and dispose of than the sulfuric acid and simpler than the adsorbent column cleanup. ASTM (1983) also notes that a combination of th Florisil slurry and acid treatment may be beneficial in some cases. MONS 223613 194 Analytical Chemistry of PC8s IX. SULFUR REwqval Elemental sulfur frequently occurs in sediment, sewage sludge, and similar matrices. As seen in figure 6*14] sulfur can significantly interfere with the early portion of a GC/ECD nromatogram. Several chemical treatments have been reoorted `or sulfur removal, including mercury (Sellar and LiChtenOerg, 1975. 1980; Goerlitz ano Law, 1971, 1974, Rodriguez et al . 1980); tetrabutylammonium sulfite (Jensen et al.. 1977; Sellar and Lichtenberg, 1980); cyanide (Hattsson and Nygren. 1976): ana barium hydroxide (Hattsson and Nygren. 1976) Treatment with mercury appears to be the most widely used sulfur removal. A simple shaking for at least 1 mm with 0.1 to 0.2 ml mercury removes sulfur (Goerlitz and law. 1971. 1974). If the mercury darkens or causes precipitation, the sample is filtered with glass wool and the treatment repeated. In contrast. Rodriguez et al. ;1980) found u aovisaole to snaxe siucce samples -ith 0 ; ^ mercury for 2 hr. The tetrabutylammonium sulfite reagent 1$ prepared by saturating a 0.1 molar aqueous solution of tetrabutylam* moniua hydrogen sulfate with sodium sulfite (Jensen et a)., 1977). The reagent (1 ml) and 2 ml isopropanol are added to a 2*ml sample extract in isooctane and shaken for at least 1 min. Additional sodium sulfite is added, if necessary, until a solid residue persists. When the treatment is complete, 5 ml water is added, the mixture shaken, and the organic phase removed. Greater than 935* recoveries of PC8s were observed for both mercury and tetrabutylammonium sulfite treatment, and the techniques judged equivalent (Sellar and lichtenberg, 1980). The C/amae treatment illustrated >n Figure o*i4 was used by Hattsson and Nygren (1976), since mercury did not remove all of the sulfur. However, the cyanide degraded the hexachlorocyclohexane insecticides (8HCs) and a milder barium hydroxide treatment was recommended. Specifically. 1.5 ml of 0.1 H aqueous barium hydroxide is added to a 1*2 ml sample in hexane. Acetone (3 mL) is added dropwise and the solution will turn yellow-brown if sulfur is present. A second 3*ml aliquot of acetope is added and, upon shaking, a light green color appears. After 2 min the green color should disappear; if not, the treatment is repeated- when the color has disap peared, 10 mL water is added and the hexane phase separated and injected onto a gas chromatograph. HONS 223614 Cleanup 165 0 10 20 X 40 50 60 70 50 t (min) Figure 6*14. HRGC/ECO Chroeietogrems IHustreting Interference by Sulfur in the Eerly Portion of Chro*eto9r*m A A stwege sludge staple wes extracted end the lipids removed by shelling with 7% fuming sulfuric <cic (Chrometogrem A). The sulfur wes then removed by eddition of potessium cyenide (Chrometogrem 6). The semples were enelyied on e 50-m SF 96 gless cepHlery column et 18S*C isotherael. Reprinted, with permission, from Hettsson end Nygren (1976); copyright 1976 by Elsevier Science Publishers, 8.V. HONS 223615 166 Analytical Chemistry of PC0j x. criteria fob CHOICE op a CLEANUP TECHNIQUE . This chapter has presented a review of the cleanu0 techniques used for removing m*ny different interfering chem icals from a variety of matrices. The confusing ana even conflicting data often maxes the choice of cleanup technique difficult. This section discusses the criteria for choosing a sample cleanuo where possible, one of the standard procedures dis cussed in Chapter 3 should be used. However, many analytical problems do not fit within the confines of any of the stan dard procedures. Thus, the analyst is often forced to adact a cleanup to the proplem at hand. The criteria for choice of a cleanup include: 1. Reported success at removing the interferences C Reported success at retaining jny ?CSs m *1* sample extract. 3. Appropriate capacity for the sample sue to be used. 4. Previous experience in the laboratory. 5. Cost of sttup and execution relative to other candidate cleanups. If the analyst has previous experience witn the cleanup, the setup and validation time will be shorter and it will require less practice to gam proficiency witn the tech nique. Often a Cleanup requires more tnan one stage First, major interferences (eg., lipids in adipose tissue) are removed. This is often done in the extraction step, as discussed in Chapter 5. liquid-1iquid partitioning and macro columns are widely used for this step. Second, a general cleanup will separate the PC8s from other trace level inter ferences, such as organochlorine pesticides. Since these in terferences are usually chemically and physically similar to PCSs, the cleanup must involve a well-defined cut between the interference and PCS fractions. Adsorbent column chromatog raphy is most often employed for this step. The third stage of a cleanup is fractionation of the PC8$ by structural cate gory. Since many analyses reouire only determination of to tal PCS content, this stage is not usually employed. Carbon columns and other spec'aliied chromatographic techniques are generally used for fractionation of PCBs. HOMS 2236X6 Cleanup 167 The choice of a cleanup technique is also dependent 0n the degree of purification required. In some cases, tne concentration of the interferences is a million or more signer than the PCB concentration. In tnese cases, tne c'eanup and determination steps must effect a 10* concentra tion of the PC8s relative to th# interferences. This will reouire a very efficient removal of th# interferences with very little loss of the PC8s. Often a combination of tech niques is used. Tor example, a chemical degradataion may cnange the bulk of tne interferences into polar compounds -men are easily removed in a solvent partition. An adsor bent column can then be used to remove the remaining inter ferences. Unfortunate 1y. there is insufficient agreement among the research reviewed in the preceeding sections to make specific recommendations for cleanup of individual ma trices. Nevertheless, there is a general consensus on some of the more general approaches for specific interferences. These are discussed in the following paragraphs. A. Lipids Lipids and other polar, relatively fragile biolog ical molecules have been most often removed by acetonitrile partition (see Chapter 5). As noted in Section V.O, above, the acetonitrile partitioning does not yield quantitative re coveries, so other techniques should be considered. Other candidate primary cleanups are gel permeation chromatography. Flonsil column chromatography, and saponification with alco holic KOH. Regardless of the primary cleanup, an adsorbent column cleanup will probably be necessary to fully remove the l>ptds. Removal of a wide variety of less-stable interfer ences may be done with a chemical degradation cleanup (sul furic acid, a>conoiic xOH, or cnromium tnoxiot;. In the literature, these cleanups are generally targeted at a spe cific interference, such as lipids or 006; however, in real'ty, m*ny other interferences are often removed. This is Quite often expressed by an instruction to repeat the treat ment until all color is gone. Analysts should seriously con sider the use of the chemical degradation cleanups (sulfuric acid, base, etc.) with PCB samples. Unlike many other or ganic analytes, PC8s are generally resistant to attack by these reagents and thus survive the cleanup. Since most ali phatic and many aromatic compounds are degraded, these chem ical cleanups can be quite effective at removing Mini in terferences. As long as the chemical degradation is shown to not affect the PC9s, these techniques should be considered for cleanup of most samples. HONS 223617 168 B. Macromolecules Analytical Chamlatry of PCBs Macromolecules can be efficiently removed by CPC Applicable matrices include sediment, sludge, and biota of all kinds. The macromolecules may be cellulose, sugars, pro teins. or even synthetic polymers. The major impediment to use of CPC appears to be the cost and effort of the initial setup. If GPC cannot be justified, most of the adsorbent column techniques -ill efficiently remove macromelecules. al though they may suffer from capacity problems. In addition, the adsorbent columns will probably not be reusable. ' C. Qrganochiprint Pesticides fractionation of PCBs from similar compounds sucn as organocMorme pesticides usually requires one of the ad* sorbent columns. Florisil is the classic adsorbent for this purpose and is still widely used. Silica gel ana alumina nave also been extensive1/ used. Arguments can be made `or the use or any one of these. Both silica gel and alumina can be deactivated with water to alter the adsorbent properties and control the elution volumes. On the other hand, "bad batches" of alumina seem to be reported more often than with the other adsorbents. Any of the three adsorbents will work adequately for most cleanups, provided that the column and solvent volumes are scaled to the sample size and the elution volumes are carefully validated. A visual indicator such as azulene can be effective in monitoring the elution character istics of individual columns. xi. validation op cleanup techniques Even when a we! l*documented technique is bei^o used, it must be validated *or use by each laboratory ana for eacn sample type. Subtle differences in execution, reagents (especially adsorbent activity), solvent composition, matrix, and PCS composition can affect the ef fectiveness of a cleanup. A thorough validation would include assessment of the PCS recovery (accuracy), reproducibility (precision), and enrichment factors. As noted in Chapter 9, these arc all part of good general quality control. Ongoing QC measures constitute a reassurance that the cleanup remains valid. With adsorbent column cleanups, the sorbent must be properly activated and characterized (Edwards. 1974; Zitko, 1972). The levels of interferences are assessed by eluting a blank column with each sample set. In addition, deactivation of the sorbent by the sample, column overloading, and impure solvents can adversely affect the performance (Edwards. HOMS 223618 Cleanup 169 l9?7). Particular care must be taken with cleanups nicn ose columns only once. The coIumn-to*CO1umn variability can often change the elution volume by several percent (Enckson et a I.. 1983e) The elution vo1ume must allow for the vari aD'l'ty to assure full recovery of aM PCS congeners in the PCS fraction. Alternatively, a visual indicator such as aiulene can be used to check the elution pattern for each in dividual column as discussed m Section 1.A. of this chapter (Griffin et a 1. . 1980; Nowicni, 1981; Erickson et a)-. 1989*). HONS 223619 7 DETERMINATION All analytical methods art designed to answer ' <$ the analyte present?", "how much analytt is in tnt sample'", or both questions. The dtntification and Quantitation is gtntrally accomplished in the samt stto. This determination sttp <S the foundation of any method around which all other steps (cleanup, data reduction. QC, etc.} art centered witn PC0s, a chromatographic separation nas almost always Ottn an integral part of the determination technique. This chapter presents :he three major separation techniques, gas chroma tography (GC>, thin layer enromatograpny (TIC). anq hign per formance liquid chromatography (HBlC). The CC section con tains subsections on separation, where Doth packed column (PGC) and high resolution (capillary) (HRGC) techniques are discussed, and detection, where electron capture (ECO), Hal I electrolytic conductivity (HECO), mass spectrometry (MS), and other detectors are discussed. Other, non-chromatographic. techniques are presented separately. Confirmation and screening represent the two ex tremes of analysis; the former striving for the maximum con fidence in the results and the other sacrificing confidence for speed and/or simoler apparatus. These two topics are discussed, where appropriate, along with the determination techniques. Separate subsections at the end of this chapter discuss the techniques dtvoteo specifically to aither confir mation or screening, Although often integral to the determination step, the reduction of data (interpretation of chromatograms and qutntitation) is presented separately in Chapter B. I. CRITERIA FOB CHOICE Of TECHNIQUES Most of the determination techniques used for PCBs employ a chromatographic separation coupled to a detector. The choice of technique depends upon: t71 HONS 223620 172 Analytical Chamistry of Peg, L. anticipated PCS concentration (limit of 0el, . t' On required). 2. anticipated number, level, and type of 1fner_ ferences, 3 resolution needed (congener-specific Or fQfl) PCS). 4. qualitative discrimination power (are fa)$* positives acceptable?), 5. Quantitative accuracy and precision, $. availability of lnstrumentation, and 7 analysis time and cost. C'eariy, no one tecnmque is the oest for all jnai/ses, ur else the plethora of tecnniques discussed below would not ex ist. Needless to say. the extraction, cleanup, and determi nation techniques are all interrelated and must be appropri ately mated in a method design. In an analysis where "total PCS" is the desired output, packed column GC, TIC, or HPIC may provide sufficient resolution. On the other hand, if congener-specific analysis is required for a metabolism study, HRGC would be the tech nique of choice. The qualitative discrimination power of a detector is a major factor in selection of a determination technique. This is especially relevant when considering the variety of C8 mixtures diving r*$e to comolex chromatooraohic saltern*. If the concentrations are high enougn (t.g., percent itveij and the interferences are minimal (e.g,. transformer A$kartU), * "universal" detector such as low resolution (packed column) GC/FIO or GC/TCO may be appropriate. If ad ditional discrimination is required, GC/CCO may be appropri ate if there are few other non-electron capturing compounds (i.e., non-halogenated) in the matrix. In these cases, PCS mixtures which fit the classic Aroclor patterns are identi fied by visual pattern recognition. When visual pattern recognition cannot be used, where interferences are too com plex, or where higher qualitative confidence i$ required, a more discriminating technique such as hRGC/MS must be em ployed. Another aspect of the qualitative discrimination power of a technique is the acceptability of false positives or negatives, a false positive may be acceptable m a survey of transformers for PCS contamination, if the false positive would simply result in the added expense of unnecessary HOMS 223621 Determination 173 changing 0/ the transformer die'ectric fluid. On the other hand, 'al$e positives m human m)k samples collected near a pC8 incinerator wou'd cause undue puplic concern and would therefore oe highly undesiraole. A false negative may arise from se'ecuon of a technique which has insufficient sensi tivity *or the anticipated concentrations (eg., GC/EIHS analysis of blood samples as described above) False nega tives may also arise from visual pattern recognition of GC/ ECO Chromatograms in which the PC8 pattern is skewed from that of the standard due to weathering, retention time snifts. or other factors. High quantitative accuracy and precision can, in theory, oe met py most of the common techniques, provided that appropriate calibration, chromatographic separation, and data reduction steps are employed. One exception is HC, which is generally regarded as "semiquantitative." Calibra tion using individual congeners is mor# difficult with ECO than EI MS because the ECO response can vary by an order of magnitude for different isomers of one homolog. Instrument aval labi 1 i ty is oovtously a major `actor m cr.qica of teen* mque. A laboratory with GC/EIMS capabilities is much more likely to choose this technique than one which must Purchase instrumentation or employ an outside laboratory. The analysis time and cost are also factors to be considered. TLC is quick, inexpensive, and requires no major capital equipment expenditures- At the other extreme, some HRGC/C1HS analyses can take well over an hour per sample, not counting the time required to set up and calibrate the in strument. 7ime-con$u*ing analyses such as HRGC can be made more cost-effective by automation of the sample introduction and data reduction steps so that the instrumentation can be used beyond the customary 6-hr work day. il. GAS CHROMATOGRAPHY Gas chromatography (GC), also called gas-'iquid chromatography, has been a workhorse technique in most an alytical laboratories for over 20 years. The function of a GC is to separate complex mixtures and detect the components. The -instrumentation consists of a pressurized gas (generally purified nitrogen, helium, or hydrogen) source, an injector, the separation column, and a detector. A very small (gener ally 1-10 Ml) amount of sample is injected at the head of the column with a microsyringe. where it is vaporized. The va pors are swept by the carrier gas onto the column, where the components are separated, and then to the detector, where they are detected. The detection output consists of a series of peaks with time. The intensity of the peaks is generally HOMS 223622 174 Analytical Chemistry of PCBs proooruopt* 1 to the amount of compound present. The separanon is effected by the interaction of the compounds with th* gas and liquid phases. The more soluble the compound >n liquid phase, the more time it ilt spend dissolved in ^ liquid phase and the later it will elute. In addition * analyses use elevated temoeratures or a programmed temor|. ture range to enhance separation, so compound volatility also affects the retention time. PC8s generally elute in oroer of cnlorination: Cl2H9Cl first. C,-Cl,0 last; althougn the<-f ^ considerable overlap in the middle homologs. Many UnutQ phases are available with different separating powers baseo on polarity, solubility, and other factors. The liquid phases are usually high molecular weight, low viscosity oils gums, or waxes, which may be coated on the inside wa'l of * long, thin tube ("column") or they may Be coated on an inert granular solid which is then packed into a column. In tn* former case, the columns are usually 0.2'O.S mm ID and 10. 100 m long and may De made of steel, glass, or, more r. cently, fused silica ("Quartz"). GC using these "caoillary" columns gives >erv high resolution ino is therefore :ai!<j high resolution gas chromatography (HRGC). Other terms for the same technique include capillary GC (CGC), glass capil lary GC ((GC)2], and fused silica capillary GC (PSCGC). The second alternative, packed column GC (PGC), utilizes columns which are usually 2*4 mn 10 and 1*3 m long. PGC exhibits less resolution than HRGC, so more peaks tend to overlap, but is simpler to use and was preferred in the United States un til the mid 1970's. Common GC detectors include flame ionization (FID), which detects anything which burns and is therefore a ''uni versal" detector, electron capture (ECO), which is selective for halogenated organics and a few other compounds, and mass spectrometry (MS), which detects all compounds and provides a characteristic spectrum for identificat ion. Many other de;eciors are avaiiaole, some or wmen are discussed oeiow. The separated peaks exit ("elute") from the GC col umn and are detected at different times- Measurement of the time required to elute through a given column yields a reten tion time (RT) which is reproducible for a given compound. To enhance the measurement precision. RT$ are often measured relative to an internal standard to compensate for fluctua tions in temperature or carrier gas flow rate. The relative retention time. RRT, can be used to identify components by comparison to RRTs of an authentic standard. Selective de tectors provide an added dimension to the identification of PC8s. GC is discussed in detail in most analytical chemistry texts and in many monographs. Examples include McNair and Bonnelli (1969) and Jennings (1980). HONS 223623 Determination 175 Gas Chromatography ,, m combination with various de actons, has Been by far the most popular and useful analyt* ,cal procedure for PCSs In recent years. HRGC has been used me1"*** ' n9' y > although many analysts still use PGC. The poo* ulanty of GC for PCS analysis lies in its resolution and speed (most PGC analyses take less than 30 min) and the sen* 4itivity (ECO), selectivity (ECO. nCO), and specificity (MS) 0f the available detectors. This section is divided into s*paration, which is subdivided by PGC and HRGC techniques, and detection, which is subdivided By the various detectors A. Separation As noted above, the separation of a complex mixture not only provides an identification of PCfls By their reten tion times, but also effects an wj situ cleanub. The reten tion time of each component is generaHy measured relative to a standard run on the same system under the same conditions, preferably on the same day. This is not generally possible due to the large number of PCS congeners and their lack of avai1abi1ity. Several investigators have tabulated retention times or related parameters of individual congeners, as shown in Table 7*1. These data, especially the half-retention in dices (Table 7*U) reported by Albro et al. ( 1977 ), may be useful to analysts who need to identify individual congeners. The analyst must exercise caution in using literature data without validating the reproduci&i1 i ty with selected authen tic standards. Since many analysts center on identification of components of commercial mixtures, Table 7-111 summarizes the literature references to peak identifications in these commercial mixtures. 1. Packed column GC (PGC): Packed column gas chromatography (PGC). has been the most widely used analyt ical separation technique for PC8s. The vast majority of the literature references have used PGC in a routine manner with a common liquid phase. The quality of ?CT ;.--o.,?jtsg-2DPy (resolution and tailing) is adequate for low resolution sepa ration of Aroclor~derived samples into "fingerprints" for identification or quantitation. as snown in Appendix 0 and Figure 7-1, Since the Aroclor mixtures are too complex for resolution into peaks containing single congeners by PGC. little or no emohasis was placed on Improving resolution. The most common PGC detector has been C0. C0 has histor ically required isothermal GC operation (not so with modern instruments) HONS 2*3624 *'V'- I I Hto. .0 I'll ft" 1 ' > i* in.,. ...j* .. .. | Mll* '* I'll 1 l-l K..H- ,,*............ Si 4>-i < i tf 1. 4 /1 h Ml *" >-l 1 '' ,, Si HI ' 1 *l>,........... s| 1*. .... $)| <1 II 1" * * . -M Mm* 11 / _ , , ' 1 HI II 1 1 it ft V ) *1,*< 1 1W 1 **.............. IHI I* M , .1* 0 J Mft t Hi hi * ' M* . * t V. M > V, Afil * tun N i\ /IV i*w ?M IVi . r IM no ie * w HO'IWI I k ItH. /#V. /It '1 lit * l 1 iv>m * id IwO/tU t 1 1 Ml 1 l . ) 1 III *1 II I !l tl SI- /|MH 1 '* 1 ,, -- , V* * 'O-lhl t IV. 1 IO-//H V 1 iiw-m * i Ml til *ll*,.*v IM,| / II I V H >i algru |,l^lnr | IKK n *1.,tl, . Mm << rl*l* HW n *lti <1 *11 tHVt J. 1.1 4 4 1*1 I1M411 &'**> 1 1.3 tuMn If lf .? 1 **W * ti *t HM4^A 1 tl* !<* U* f 4* *'* tf A*|lM Ui 1 4, ft hit >iti |tll I.ft4 lM S 1 ( >! *> * ll . | * 1 | w*i,k i(t Hi ( i 1 111/ * Ifel U lttf !** I" I1*'/* tmt Vu*Ji|,, lt/ *>!>< *i , If" *1 l |k < i ltf| tv* | y*t l > ll *, <*r 1*10 *< |4t/ lx *1 *1 . |'l If 1 > it l> i 11 I**? f* M . 1 l* i *| t 1 init k SM>t|t *| *1 IS.I 1 1* *1 *1 (kR| list *1 ipHnI iiih iiwlri II .. i* *ii i > >* 1*1 lu tM|#lH| |l|M^|l^ llvlr.l ii rvt#*1'ft* 1 tftft *A tlAMU> 6 t(H< #! 6U 'f s* 0* lul 1 yi Afif<mm ( iriwlril lt>t t>A\<| | ( wl inA im Ifti# t tiq o* /.', MM 1 tO*N )>* fcvt) 1 AMftA) ! % I,., tii . 1 > b0 i 4 It ttl4 | J * < M(if4 *h .Jl Iriml . itiarnt int. a| ! r- I II kfc * .1. tiki.*4 HONS 223625 177 I il>l i>a 1 11 1 1 1 I ) *4lW lf M III.) (1/; 1(1 1 i 'i `/ N * ll, 1 1 1/ 1 V hlir > .4 .J S .4 .4 > . * . IS tS .1 4 4 .1 S 1. 'll 111 nil MB ( , rt.il /* '4*B4 III/ 1 1 HI.1 ... 1 Hl* 1 . I/H 1.11/ 1 . U II 1 HI It 1 n 14 Mil mill 'M. l 'l/.i >1/ 1*S *l| <111 1*4 '*'V* 1 0|H 1 11/1, 1 ll/ii 1 II'**. 1 <!/, I I IH \ M / 1 .<**. III.M I II! 1 IMS 1 |NB I I, 1 1M. 1 1*4 I/ll 1 . *<* *1 1 . Ii * I. in i BID *SH 1 .mi 1 4 .`B** i ii n II 14 1 IIS 1 IW> i //i ')> 4/1 // n/ 1 ,*o 1.1/14 ).H i.i* H 1 U/S 1.04/ I.OOS Kill l.HS 1.14/ I./V4 1 KM 1 1*1 1.1/4 1 U)|l i.m 1.1/4 1 1 ,/nt 1)11 1/4* IIS 1./// 1 , Ml 1 4I*S i m 1 US ). /1/ l .>. >./>* 1. IS* * 4*14 1 . IB 1 1 ,/4|. l . ss 0// 1 *4.-4 1 .!* 1 11`M, 1 It,4 ii Ii) 1 1*1 1 1 lim 1. 1.11 1 l.'M *14 1 MSS 1 l* 1 U* 1 IBB 1.4/S 114* ).?S1 I./*I4 1 l '* l.l/< l./l/ 1 /** l // I.//S 1 . /'IS l/'l.' l MU 1 ! 1 *111 1 ./Sl 1.1 /' 1 MS l./us 1 nr* III* l./Ss 1 ....... 1 *'M 1 . I**1 l ISI 1 I'M. 1 4*11 1 4 /> 1 4M 1 / '* i 4m* 1 l 1 .* 1 VI* 1 4.11 i mb, * Wi 1 /V 1 / I./S4 1 . MS 1 >// 1 III/ 1 /* 1 S/S I <41 1 4 IB 1 1-tll 1 S14 1 *l*> 1 Mi* 1 S*m 1II r,t> ssu i*/ 14 1 U/S 1 01* 1 . 1/51 l ls 1 in 1 Ins 1 14.. 1 .'UK 1/ It. 1 ,'tif 1 U.* 1 /III 1 / t 1 US', 1 // 1 /*s 1 /,' I./OS III/) 1 ISI 1 41t* 1 *s* 1 ISI 1 Bill 1 *8* 1 . IS* 1 S*>H 1 li. > 1 \ >n "/ Nflft m.M 1BII *B* 1 01' 1 1**4 1 i.*4 1111 1 IN/ 1 1)11 1 1*1 1 US l./M l /' ..... 1 /<. 1 Vi II I.' II . II*. I HOMS 223626 WpsI n*i l'4{< * ii// n m 1 41* 1* / II it... 1 .M* <1} *, n/ i 4 X t. 1 4 10 II 1/ 11 1 t * ./< 1 | .i* 1 i**/ 1 IK* 1 .'1/ 1 )i.n \ 1 r. I K'll 1 ii* 1 4 Mil 1 /UN XI *4 / I| 1 in 1 i i*'i 1 X11 1. 1X4 ./* 1 V. 1 ISM 1 Ml I **l I 411* 1 *! i i. X.l. / 1.' / 1.' *l**i 1 I* i. * * 1 .1.4*1 l.l/ 1X41 1 fc.'ll l.x/l. 1 UN 1 IK} 1 *811 1 /-*. i'*i 444 ). 114 1 11 1 I <MI 14/1 l XIV 1 V*/ I ,/lk I ll 1 /Ml 1 4',|l 1 .Ml. 1 *1-1 1 .'i1 1.441 | X 1'. 1.14/ 1 . II*/ ./'I 4 l> V /4 ' V . ii .Ml/ 1 1 ** 1 141 1 ...... 1 4 11 1 . V*. I* Vi I.*/ II'/ XU/ >11 1 VH l <7 1 ) Xtt) 1 >4 / 1 VX4 | 4N 1 <*rt> 1 in/ I.4VI 1 MR / H1 4 1.. ns* IK* 1 . 11 * 1 Mi 1. 4*lr*aiH Ik* Ufh.l il'ui |.4l1l nn ***h 1 .1 !** . Iptl * 1 If* luffs 11 Is* >1**u|*l *4tr <** 4N 41M |K*a |aQ4tr*i |i | liiMIAif4 | ii 11***| i>.|M l 11.N 1K4 f a*. ti i*i < *** f t NiaMll'i ill. J 0 < ar 1 X IVM> 1 1 f * 1 1 llV Ill* |ll*l ... II 1 l. a.. ... 1. W tw Unt 4 M . M y*. **. > Ml >u hmi * || 1 k> .,isnl MW* /K, 1* . l.X *,.* I'll 1 .-I. i W Av 4 ini tiv /|M. M> 1 *** a. U Wi ll .*nl t X III i IIV 1. Ill l.'H a. f l. is I M> / 1. I'll rv 1 |*| * *Mir > *||HM | / ll'l |W f\ 1** |.`J< mm- * lilt 1 M / * X M U>| |*l l/'l a ll Ik t> it* Ml* 1 , >111 4 M lllll ** IIMI 4 'f . ll* / Illli 4 If / 1 l" i< Ml |H| l| ,m,t 1 1 **lll* * 1*1 U 1 I**-. 1 . *4 ! Iim g H.'Ml IlHI ' 11 M till. * II (*<< ft 1 1**11 s.4>p i* >i*.u, * ,'* 1 '.v l 1 >i \>*i w U i. , i . ; /** H * I II lip. 1 4 1 i * i*. *4 i< A. .1 < .* lx U' .'*0 .*hl ,'lfif /utl /HI HI | **v ...... . II* i . .I.*- I'l X.*** i * 1 >1 1 I|M Jf//. 1*, 1 1, -*.. - ... * . **~ * '<1 X 4 . 1 * 1 ill nl rn> - 4.4 if * .tw * l h OftrfilKj p ** . i, r t'M 1 .IKIX X . 9 1 ' \ < 4**ft , f .K ri . ...I*.. p.| kill. |>* a 1 x 1 </l 1 4 11 1 1*1* 1 III 1 *// 1 X/l HONS 223627 179 III I . / III I . k> >i| i | r 41 I in> ii I **V B 1 iimft*l.r i HuL' l ( iinl|r..rl \ N l.l*--l II ini Ifli4l>1 H..I..I ................. I.'*' I /l* l.'l.lt l..i l.ll I mu. I,.. |,'411 I.-.4 (/l.ll ..........ill l.YI 1.1/ i/; | .'4H i/'.4 l III liil I . I himi U'. i/kii in. i.n mm/ I.1'.*/ I . Ml 1/ I I.l I 'Ii II It'll M I I | >1 I l.ll III 11 .) 4.-1.11 .1 `-HI. I'l > II................. i . I.|i. m i.i s mIii .I III. HI iWl.l l III I'l.l I III l c.... i.-r ...l 4 . 4111 I*4*111 II V f 4ln! II If*. I.l r*\ iKM.i < i n iiu/M ims ml Ih'mI | ti-MKl4l|l-. III*.......... . li~l.n .1 11.1..I.IU II *'.ll *1.41 IlHi.l II II ..I lllllii III II .........(Is fA (III )/* 44 y 1.1 t* III Hi /' l ;/ /S ./ *1 l I'. I `l 1.1 '|4 Mi *ii Hu s Hi I 4 I ................ . |i,,. I . |M| ..M-1 I .1 . 11 i It ' I I II IMu., .ml l,.l,, *1 *14.... ,1 4 urn <>Mi *iv .i iii 11'/ i (. *> yi#/ I'WI **I I I// * r| 4 I 111 (4 II HOI I I. .. I II 41 JI I I'H HONS 223628 180 *..... . 4l l.lr / III (toim I| R.Alirj I#I ( iiiipjfiim t \ IlMAI I I )f4 .< sip - r|oi I jn* ir'rl phi r M.ll I fl A Ml I I. Iiniln n A Mi Ill AM, l,,. 11*1 I Jp IIII lull *lf MM l-l- . p..... .... llloillll, 14I*I"'I , .ill III .iIppI | V IPtriJ I III ...III i .ill. I . Imii.) 11111,1IlM.-l | I |l , | |N . ..,l pm il i. I nppj.pl 'I i.( I l|l II..J l.l 'Ms St l{ tl / /II j? I. I ,/ t/ 0/ I/ / // n *1 4IHIillHIl.i ->l /r j i. nnn 4Si hill If >,,l Hf I i II I,, ItB* 0IS I A Uilinlr 4*i, I III lift.I in,I I Sr l >* Ifi.fl.r IS/* 4 II ll <M l fl pl.l lul, IiMp i kll , l| ... Iril ppIiIIip >*|ru|lfp II : IFlrnl'Pln lilf I 4I.? RF4*p Ilk 111 l I IF.I Ip 'API i <||,|`,<P ||||*PI f Klin II# ||. Imp i-pi p. l|, l I I ip lul POM *4p 0 4llmlr rll|4il |lk|ll >.mi.| I ||p-sp i.M-Hl l l |r,I 01.1, flf H*||iM, >,.ljll>* p# t lp*l.|l'l> l|lpr<l In Ilf* i4lri#llivp HOMS 223629 Qetefminaiion RROCLOR 1254 161 Figure 7-1. Tamotratura'Programmao PGC/ECD Chromatogram of Aroclor 12$4 A 0 2 cm ID * 180 cm glass column, oackad with 1.5% SP-2250/ 1.95% SP-2401 on 100/120 mash Suoalcooort was Orogrammad from 150C to 250#C at 10C/mm. Tha mtrogan carrar gas flow rata wat 30 mi/mm. HONS 223630 182 Analytical Chemistry of pcq, fly 19? 1 Sufficient worn m PCB analyS'S by PCC h been comoifted to *er,t a '*! (Reynolds. 197]) 40 follortfl Oy $evfr*l othfr reviews (fishbem, 19?2. HumJ*' et 1 , 197*a, fu;ir tft di . 1976. kfull. 1977, Margesoft* 1977. ana CMA. 1981) On* review by Sherma (1975) wjs a . voteo to PCC aniiys'S of PCBs ana related cnionnateo a*0! *etic pollutants PCC is trie recommended analytical seoar*. tion technique in most Of the Standard procedures Hsteo in Table 3-1, a testimony to its reliability and popularity Aibro et a< (1977) evaluated 13 packed co'umn., ranging m polarity from Apiezon t to OV-22S (Table 7*ij; The numoer of observed theoretical plates ranged from a9i / 3.833 None of the columns could successfully resolve *m PC8s. It as calculated that of the 21.945 theoretically possible pairs Of PCB congeners. 465 would be 1noiStinguiin. able using the best column tested. The researchers discussed the use of multiple columns for resolving indistinguishable pairs and concludeo mat five columns were necessary to re solve all isomers. Thus, using this scheme, each sa*oi would have to be analyzed once on each of five PCC columns to resolve all congeners. Aibro and Parker (1979) applied this technique to the identification of the components in Aroclor 1016 and 1242. The identity of 44 congeners was reported, a report by Jensen and Sundstrom (1974) oresents what nay oe the highest resolution PGC chromatogram of PCBs (Figure 6*6) Even though it was ooerated isothermal ly, this 5.2-m Apie-or l column resolved S9 peaks in a Chlopnen mixture A recent development, bonded phases, gives more rugged and stable columns. The lighter loading of 'iqu-.o phase also reportedly reduces the analysis time in tne amole shown in Figure 7*2. l*hr PGC ana'ys'S was reoucee to IB min using the bonded liquid phase (Driscoll ano nryi' 1983). 2. High resolution oas chromatography: HPGC has not been as popular as p5c, aitnougn its use nas increased dramatically in the past few years. This increase m poou* larity can be traced primarily to the advent of f)e*<bi* fused silica capillary columns, which are easier to use. longer*las ting, and yield better enromatograpny than the glass end metal columns used previously. Tne Quality of me HftGC separation currently acnievapie is illustrated in Figure 7-3 (Safe et al., 1963a). white tms e*emole represents me state of the art, a more "routine" enromatogram is presented in figure 7-4 (Erickson and Stanley. 1982). Even the routine HftGC chromatogram provides substantially more resolution and information than a PGC chromatogram As noted below, tnis can have both oositive and negative ramifications Generally speaking, any analysis wnich may be done oy PGC may also oe HONS 223631 Dal&rnvnation 183 Figure 7*2. PGC/F1D Chromatogram of PC8s and PCT* Using a Bonded uquuJ Phase A Pe'-maDond methv) silicone column was programmed from ]40C at :3#:/nn to J50CPeprmted. with permission, from Driscoll and Krul) (1983), copyrignt 1983 Oy Internetiona 1 Scientific Communications, Inc. HOMS 223632 *I 1260 10 16 OAD. J I igure /') 1 III ill! t 1 lru Imin I MRGC/ICO Uh omatograai ol Aroclor 1016. 1264, and 1260 (6 3 2, w/w/w) A so-* (used iilica capillary coaled wilh SE54 was prnga*wed fro* 100#C at 1 C/*m to Numbers above peaks refer l I'CB (onqener. Ihe PC8 congeners are mmfcered according to tUHsilmiier and /et t U9) I In* m \ aclOoronephtlielene internal standard >s denoted by OlN ...letl, -HU i.r.-missnni, ' * WH- * -I 4 I ".t.l IWI My fh.ic*.~"in HONS 223633 Determination ;**.'ij* 2*o 2J0e/**.i i X) 0D*^/1*I. '*1 185 20 00 25:00 20 00 3 5:00 *0-00 500 .'0 00 25 00 im| Figure 7-4 hrgc/EIH$ Reconstructed Full Scan [on Chromatogram of PCBs and dl0-Anthracene (Internal Standard) The number of chlorines is denoted above each peak. Instru mental oaraneters: column IS , DB*5, fused silica, column temperature * B0*C for 2 min, 8#C/min to 300C, helium car rier at 2.S ps i; 1 uL injected on J&W on-column injector. Reprinted, with permission, from Erickson and Stanley (19B2) and Haile et al (1983b). HONS 223634 1W Analytical Chemistry of Pcs* achieved by hRGC. although the converse may not always h true. for nstance. congener* soec i Me analysts of comDie* PCB mixtures requires hRGC. ' figure 7*6 shows the relative retention times of 77 congeners ustng a OB'S bonded phase column (Erickson et ai 19B2. Stanley et al , 19B3). This figure illustrates the overlap of the homologs. There is no way to separate con* geners into homolog groups based so'ely on retention Relative retention times (RRT) for 77 PCB congeners as 11 as a mixture of Arodors (1016. 1242, 1260) were determtftea with respect to the internal standard. 3. 3`, 4.4' - tetracni0f.0. bipheny 1 -d*. to establish relative retention windows that are required for identification of specific PC8 homologs. in* RRT data can also be used in selecting standard isomers mch elute in the middle of the range as -ell as establishing proper retention windows for HRGC-EIMS data acquisition *0r particular PCB homologs. . HRGC as bnef'y cited (five references) in one re view (Sherma. 1975). An Aroclor hRGC/ECD enromatogram -as included m a HRGC monograph (Jennings, 19B0) as an applica tion of HRGC. One of the standard methods in Table 3-1 recom mends hRGC. specifically a support coated open tubular (SCOT) column coaled with FFAP (free fatty acid phase) for analysis of PCBs in capacitor Askarels. ERA Method 625 (EPA, 1979&) recommends PGC or if desired, capillary or SCOT columns may be used. High resolution gas chromatography is also allowed, if desired, for the analysis of PCBs in transformer fluids or waste oils (EPA. 1981a). HRGC/EIMS is the technique used for analysis of PCBs. PCDDs, ana PCDFs in stack gas during incinerator tests (Ackerman et a' . 19B3a. naile et al 1983a, 1983b. 1984a. 1984b). The resolution and column specifications for hRGC analysis of PCBs span a wide range Althougn me resolution was poor by today's standards. Biros et al. (1970) used hRGC/ EI MS to determine PCBs in human adipose in 1970- Sissons and welti (1971) published an early article which character':eo many of the PCB isomers in Aroclor 12S4. Using an Apiezon 1 packed column, 23 peaks were resolved, while me same pnase on a SCOT column (24,000 to 27.000 plates) separated 65 peaks. M*ny investigators have used Apition a purified hydrocarbon grease, as an hRGC liquid phase (Alpro el al . 1981; Stalling et a I. 19B0; Bush and Barnard. 1982; Bush et al., 1983; Jensen and SundStrom. 1974; Nakamura and Kashi* mato. 1977; united Kingdom Department of Environment. 1979) Apiezon l has been reported by several groups to be the most selective phase for PCB congeners after comparison with other HONS 223635 c Wc,'0 C ]?ll,ci9 C |2H2C,8 C,2M3CI; C 12 * *4 ^ * 6 C c1?m6u4 ReJotive Kclcnlion Timet of PCI Congeneit by Homolog Veiitn 3.3',4,4' Telfochlofobiphenyl-d^ me m me 7o to?no in *e << !*! in mi 1S ISf J|l5lM)l4l>>f i?eiy -on ijhbi \it uw io) ti*e nun s to <* If 10 X 1) lIXil *ut< t* PC3 Homoiogt <-12"Al3 00 -4 cI2mOc,2 > > ?to tm tI )ll !17K *. 0.40 0.50 0.60 0,70 0.80 0.90 l. 00 1 10 (.20 1.30 Rdolivt Relem Ion Time I iyure 7 t>. Welentinn limes Of 77 PCB Congeners Relative to d,.* 3 . i' .4.4' * Telraclilorobipheny I (HR 1 of 1.00) 1.40 Ihe nimhi'i s reler lo llie IIM'AC sequence number (or each congener Relaltve retention limes were iielermmetj un a JAW 1)0*5. 1S (used side* column to 4 l ttiutyan 4023 CC/llMS system Icmperatmo program: 110C for 2 min, then lOC/min lu J2'jC Ni'pt iiileil, with permission, from fcnekson et a) (1962) and Stanley et al (198i) MOMS 223636 188 Analytical Chemistry of PC0j phases (Sissons and Welti, 19?1; AI&ro et ai . ;9?7 8usn .. al , 1982. 1983. 1984; *ll.::an. 1981. pe"-:;ar> n 4." 1981. 1983b)c<gu-e 7*6 oresents e*ampi*s o' pc3 seo<jrd. tions on an Apiezon L capillary column (Bush et ai . 1987) Krupci* et a' (1976) evaluated metal -a'l-coated open tubular (WCOT) columns coated With Apiezon i, or 0v*iq^ and found them unsuitable. Hpwever, OV*101 on a glass wCOT column gave good results. Krupcik et al (1982) have reoorted the optimization of experimental conoit'ons ror analysis of comole* mixtures by capillary gas chromatog<-a0ny The optimization procedure for complex materials -as demon strated with a roc lor 1242 porty PCBs were ifoai-a\.eo at 170C using a 40 m CarDowa* 20H glass capillary column con nected to a ?6 m Apiezon t glass capil'ary column Using a SO-m Oexsi I MO glass capillar;.. At&r0 e. a). (1901) achieved 175,000 effective theoretical oiates for 2,2' ,3,3' ,S,V* nexachlorob i phenyl Resolution : Aroc ior 1260. which reoyired an isothermal chromatogram o l n. ge*. erated 110 peaks, of which only 4 were unioentif'eo Even at this resolution, the Oexsil 410 did not resolve a>' congener pa*rs- Less efficient columns coated with Siiar $c, Aoiezon L, and OV-25 were used to provide different separations which resolved the congener pairs not previously resolved Mullin and co-workers nave achieved mpressive resolution by temperature-programmed hRGC/ECD on C*5? co'umns (Mullm ano Filkins, 1981; Mullin et al . 1981) ano SE-j-i columns (Safe et al., 19B3a; Mullin et al . 1983, 1904) rne retention times on an SE*>4 column of al' 209 ccngen*-* are listed in Table 7-!V(Mullin et a' . 1984) F>gu*e r-7 <* lustrates tne general trend of increas'ng r^^ent'on time *u,n chlorine content. For isomeric PC9s tsame degree ot :nior<* nation), the retention time s dependent on ,tructure Mullin et al. (1984) noted a general increase m retention time as the chlorines are placed further from tne orioge Be* tween the two benzene rings (i.t.. decreasing ortno-cnioro substitution and increasing para-chloro substitution. ?or the monochlorobipheny 1 s, the elution order is 2- ' 3* ' 4- For tne dichlorobipnenyls with chlorines all on one -'ng. tne elution order is 2,6* < 2,5* < 2,4* < 2,3- - 2.S- < 3,4* The limited data on boiling points (Table 2*111) indicate that the more non-planer PCBs have lower coil mg points, which is consistent with the observed retention times. In addition, it may be that those congeners which can more r*ao- ily assume a planar conformation are more soluble the ;'Q- uid phase and are therefore retained longer m :e column. HONS 223637 Determination 189 figure 7-6. MRGC/ECO Chromatogram* or Aroclor* 1242, 1254. and 1260, on a 0 29 mm 10 x 2Q- Apiezon t Column Th# column temperature was 70*C, programmed at 10C/min to 130*C, than at 4*C/min to 230C. with a 10-min nold. Samples (? mI) were injected using splitless injection. Reprinted, with permission, from Bush et al. (1982). copy right 1982 Dy Association of Office' Analytical Chemists, Inc. HONS 223630 190 Analytical Chemistry q( P^Bj '<&'* ; : v f 1<l 1 v *lnlion T |**J <r>0 (CO or 209 PCI Congener/ f#clorj IVlPjkC No. 7 / Sfiooni.# ftclor^ JUPgC NO. *l*Uvo PfltnilOf f'** el|i.,, *oonv* doctor* 0 0 0997 C 0251 1 0 1544 0 039) 2 0 3937 0 04* 3 0 1975 0 019) 4 0 ::5 0 0374 5 0 :'B5 0 119 6 0 7709 0 38 7 0 :566 0 69 B 0 2783 0. 206 9 0 257 0 366 10 0 rr*3 0 262 11 0 3:36 0.0*49 1? 0 3?9fl 13 0 3315 0 179 02* 1* 0 3973 0.3047 15 0 2387 0.107 16 0 3625 0 447 1? 0 3396 0 *12 IB 0 3376 0 313 19 0 30*5 0 3037 20 0.417 0.7231 a 0 *135 1.0596 22 0 *267 1 0935 2i 0 377 0 $* 24 0 3506 0 793 0 3937 0.5* 26 0 3911 0 603 27 0 2523 0.495 :a 0 4031 0 654 29 0 362 0 6)39 JO : : 165 0 3202 n 0 4024 0 562 3? 0 2636 0 276 33 0 4163 0. *47 34 0 1782 0.6092 35 0 4 736 0 3746 36 0 4375 0.29*6 37 0 4866 0 56 36 0 4593 0 *696 39 0 *466 0. 3*7 40 0 5102 0.722 41 0 *99 0 5*69 4? 0 467 0. -'92 43 0 *567 44 0 *0)2 *5 0 *33* 46 0 <5 47 0 *639 *6 0 *651 9 0 *61 50 0 *007 51 0 *2*2 52 0 4557 53 0 4107 6* 0 36 55 0 5562 56 0 5676 67 0 5155 56 0 5267 69 0 *66 60 0 5676 61 0.5331 62 0 *665 63 0 529 6* 0 *999 65 0 *671 66 0 5**7 67 0.521* 66 0.50* 69 0 *51 70 0 5*07 71 0 4909 72 0 498* 73 0 4554 7* 0 511 ?5 0 4641 76 0 5*08 77 0 6295 76 0 602* 79 0.569* 80 0 5*64 61 0 61*9 62 0 6*53 63 0 6029 6* 0 57*4 65 0 622* 0 503 0 524 0 5* 0 <68 0 6*4 0 556 0 6*8 00 664* a 0 <18 0 3606 0 164) 0 829 0 429 0 6* 0 609 0 6* 1 0164 1 222 7 1.1478 0 728 0.607 0 8408 0 646 0 6* 0. 726 0 8024 0 658 0 *68 0 5515 0 S805 C 671 0 6*61 0.5795 0 3812 1 1151 0 881 0 7278 0 7159 0 7 7) 0 6339 0 386 C 7396 HONS 223639 petermtnatton lUPgC MO 66 0? 88 89 90 91 9? 93 9* 95 96 9? 90 99 100 101 102 103 10* 109 106 10? 106 109 no 111 112 113 n* 115 116 11? 110 119 120 ::i 122 123 12* 125 126 12? 121 129 130 Rf'4( 1 *f ion Umt' 0 6105 0 61?5 0 5*66 0 5??9 0 501* 0 55*9 0 S?*2 0 5*3? 0 5)31 3 5*6* 0 505? 0 6] 0 5*15 0 506 0 5212 0 5016 0 5*31 0 51*2 0 *?5? 0 ?0*9 0 666 0 6626 0 6626 0 6016 0.631* 0 6163 0 5966 0 5662 0 6626 0 6W1 0 6132 0 615 0 669) 0 5966 0 6256 2 5516 0 66?1 0 6656 0 656* 0 61*2 0 7512 0 70?6 0.7761 0.7501 0 ?26* f4bl* ?'IV *' l'. 8**00"! c 4Cl0" 0 ?966 1 021 0 6692 0 561 0 611 0 5?1 0 5375 0 6676 0 *51* 0 **3 0 *306 0 6)1 0 62*6 0 613 0 5871 0 666 0.4561 0 6066 0 *561 0 9* 1 00*6 0 6163 1 065* 0.9675 0 65* 0 6601 0 6266 0 60* 1 0261 1 1326 1 296? 0 A696 0 8? 0 8239 U 744* 3 .'659 0 ?2*7 0 66*5 0 6*6 0 556 0 *757 0 563* 1. 166 0 99? 0 952 191 .rsc '41'it ion 131 132 133 13* 135 136 13? 136 139 1*0 1*1 1*2 1*3 1** 1*5 1*6 1*7 1*6 1*9 150 151 152 153 IS* 155 156 157 156 159 160 161 162 163 16* 265 166 167 166 169 2'0 1?1 172 1?3 1?* .75 0 666) 0 7035 0 6671 0 6796 0 6563 0 6257 3 7129 0 ?*03 0 670? 0 670? 0 ?203 0 66*6 . 0 709 0 5563 0 61*9 0 6955 0 6606 0 62*3 0.66?2 0 5969 0 6*99 0.6062 0 ?0)6 0.63*9 0 5666 0 6105 0 016* 0 ?<29 0 7655 0 7 396 0 5966 0 7?3? 3 .'296 1 * '00 3 692 : '572 0 7014 0 7066 0 3625 0 8?* 0 6069 0 2?0 0 615? 3 7965 0 ?6U R* *001* *4Clor 0 8*92 0.?303 1 1*6 0 7331 0 7031 0 *4* 1.112 0 62? 0 ?219 0 6732 1 352 1 216 0 7006 0 676* 0 6789 0.770 0 6* 0.554 0 572 0 5676 0. 70S 0.5235 0.600 0.57 0 500 1 309 1 1965 1 132 0 993* 1. 191* 0 9672 1 0322 0 99 76 0 90*6 1 0777 1 0*21 1.0656 0 6375 0 6355 0. 75 1 1712 1.172 2 0* 0 806 0 361 HONS 223**0 192 *111 > e etet1 a1 1 e Analytical Chemisiry of f *D' IV (cone I uOtd) 6*' 411e f*"! '4C tOf :r*c *141' e *eientio l '**1 fi*soonje 1 4tl#r* 176 0 'JOS 1 OS09 177 0 8031 1 009 170 0 7S3? 0 6? 1 179 0 7205 0 0237 180 0 836? 1 ?9S 101 0 7968 1 6046 18? 0. 765J 1 1?7? 183 0 772 0 976 184 0 ?016 1 0046 10s 0 7040 1 *37 186 0 7416 1 :?36 187 0 7654 1 1?2 188 0 69? 0 7337 109 0 914? 1 `091 190 0 074 1 31 191 0 844 7 1 4 741 19? 0 0?69 1. S?9 193 0 0397 194 OH? 19S 0 93?1 196 0.0938 197 0 8?9! 190 0 0045 199 0 0494 ?00 0 0197 ?01 0.0075 0 369 0 803 ?0? 0 0009 ?03 0 8930 ?04 0. 6?1 7 1 165 1 6?9 0 8034 ?os 0 9670 1 06 ?06 1 0103 1 67j ?07 0 94?1 ?O0 0 93? ?09 1 0496 1 3257 1 1 ?S6 1 139 4 fne mgn* resolution ciciliry g#s cnroaitogrepny es eeror*tg or* 4 ,<r. iin Moat 1 3700 ges enro*etograpn tau'ppto >th ***> electron ctoturt ddltctor. A 50* fuito *ilC4 cepillery cd1i*a (0.? m 10) coeteo .urt Si'S* (Htw'tU'ftcktra) wes ut to teperete me PCI 1 sobers ma con gener* 7n oven ItaptPOlurt 4S progrianta it * 'it* of 1.0*C m'i fro* 100 to 240*C. Trt* injector ine atltctor tepertures were 270 *a J30*C, respectively Staple volume. 6.0 ul. * injected Pv using *0 iuloiMl'C stapler witn splitting m tne injector (10:1 v01 t rt,a vented fro* 0.75 to 1.75 **n).. The nyorogen corner ge* * neio ji 4 cgnstont pressure of 2.?S tg c* ; to give tne optienjed imeer veioei;, (u) 4t 100*C of ts c* s 1 b BilUcnaiten tno 7*11. 1900 c Attention i'*e* (AT) o' me PC0s were expressed reietive to m* oc.*- enlorontonimlene (AT * l?e 9 m) s'eneero 4 Aesoonst '*ttors (ty wt>gnt) for tne >CE expressed relol'e 10 sc;*- cnloronoonmolene tA( 1 0 for 1 ng of OCN) by u$mg mlegrtteo ftn e `sliMiea reitiwe resoonse 'ector oosed on otner isomeric PC0s Source: *uilin *1 *1 . 1 ?6*. reproduced <tn o*nision. copyright ;98< by teencen Cne*<cil Society. HONS 2236*1 Determination 193 Figure 7*7. Plot of HRGC Relative Retention Time versus Congener Number for all 209 PCBs See Table 7-1V for more detailed data ana chromatographic conditions. Reprinted, with permission, from Mullin et a' (1984), copy* right 1984 by American Chemical Society. Recently, bonded liQuid pnases `ave seen made available on capillary GC columns. These exnipit 'o bleed and background and have long lifetimes. Figure 7*3 presents a HRCC/EIMS chromatogram of a PC8 standard on a 08*: column. Narrow-bore capillary columns produce both high resolution and fast analyses, although the capacity is reduced since less liquid phase is present. For example, an 8-min chr omatogram of Aroclor 1260 has been reported using a short (4.1 si) capillary column operated isothermally at 222C (Schutjes et al. , 1984). A resolution of 70.000 theoretical plates was obtained with the SS-ym 10 fused silica column coated with 0V-1. Similarly, Onuska (1984) demonstrated nearly double the resolution with about half the analysis time (36 versus 60 min) for a mixture of Aroclor 1242. 1254. and 1260 with a 25 m x 104 u" 10 column relative to a 50 m x 300 um 10 column. Both columns were coated wtn 0v-l, pre pared in a similar way. HONS 223642 194 Analytical Chemlstryof PC8$ Oespite tne advances >n column technology, no Qr metnoo reported or oredicted will separate a'l 209 PCS con geners. As an example of the overlap problem, Mulhn et (1904) noted that 11 pairs of congeners coelute on an $E*5a column. Using their conditions, as shown in Taple 7-]v, con gener numoers 94/61, 70/76, 96/80, 60/56, 145/81, 144/ps 140/139. 133/122, 163/160. 202/171, and 203/196 exhibited similar or identical retention times. In addition to tn* prooiem of congener separation, interferences may coelute wmle EI MS c.an readily discriminate against non-PCBs. co eluting major components may affect the mass spectral r,. sponse of PC8s ' 3. Comparison of PGC and HRGC: The relative mer its of PGC and hRGC are weH-known (Jennings. 1980) and aopiy to the separation of PC6s. As seen in Figure 7-0 (Bush al., 1982), hRGC provides better resolution, and thus high**Qualitative reliability. PGC yields a simple chromatogrlm (less data reduction), permits higher sample loading (jno therefore possibly lower limits of Quantitation), and <s gen erally considered easier to use. The inherent low resolution of PGC has been further hindered since PGC analyses traditionally nave been done iso* thermally due to requirements of the ECO (see below) Thu has not only degraded the resolution pf later-eluting peaks (see Figures 7-1 and 7-8) but also lengthened the analysis time. On the other hand, HRGC chromatograms are generally temperature-programmed, which yields similar resolution throughout the chromatogram. Until recently, the empnasis with hRGC has been "ultimate" resolution, achieved oy slow temperature program rates, low earner gas flow rates, ana. especially, long (> 50 m) capillary columns Thts nas suited in very long chromatograms (see Figure 7*3) relative to PGC (see Figure 7-1). Hn extreme example is the 5-nr chromatogram published by Albro et al. (1981). In tne past few years the trend nas shifted toward practical applications of HRGC. Using shorter columns and faster temperature pro gram rates, at the sacrifice of some resolution, chromatog* rapners nave produced rapid hRGC separations (Figure 7-9). Properly utilized, HRGC transmits more of the sam ple injected to the detector than PGC. with less surface area, there are fewer active sites and less chance for ad sorptive losses or catalytic degradation. This advantages translates into lower detection limits. In direct comparison of PGC and hRGC, no signif icant difference was observed in tne results for tne analysis of PC8s in oils at tne 30-500oom levels (Levine et al . 1983) The PGC analyses were done on a 180 cm x 2 mm 10 HONS 2236*3 Qetarmmation 195 Figure 7-8, Coeioarison of PGC/ECO (Top) and HRGC/ECO (8ottoa) Chromatograms of 29 PC8 Congeners The PGC/ECD chromatogram was obtained on a 5.2 Apieion l column operated isothermally at 2S0C, as described by Jensen and Sundstrom (1974). The HRGC/ECO chromatogram was obtained on a 20 a i 0.29 mm ID glass capillary coated with Apewon t and operated at an initial temperature of 70*C, programmed at 10#C/min to 130*C. then at 4C/in to 230*C. Reprinted, with permission, from 8uSh et a). (1982); copy* right 1982 by Association of Official Analytical Chemists. Inc. HONS 223644 196 Analytical Chemistry of Pces F igure 7-9 hRGC/ECD Chromatogram of Aroclor 1260 Short CpH)ry Illustrating Rapid Separation The 4.1 m * 55 u ID fused silica column was coated with ov- and operated isotherma)ly at 222*C. Reprinted, with permission, from Onuska (1584); copynynt 1984 py Elsevier Science Publishers 8V. glass column packed with 3% QV*1. operated isothermally. The hRGC analyses were done on a 3Q*m fused silica capillary coated with SE-54. A Grob injector was used and the column was programmed from 50*250C at 10C/min. Both ECD and HECD were used as detectors. B. Injection The injector is an integral and important part of the chromatographic process. While often overlooked and not even reported, the type of injector can affect resolution, discriminations, and sensitivity. In PGC, most modern in* struments have "on-column" injectors, while earlier work fa vored injection mto a chamber, with the analytes being swept onto the column after vaporization. This latter tecnniQue is the basis of hRGC's split and splitless injectors. Recently, on-column injectors have become available for hRGC and pro vide generally superior chromatography. One detriment of on-column injectors is that, with dirty matrices, inorganics. HONS 223645 Determination 197 polymeric materials, etc., stay on the front of the column, degrading performance ana 'ncreasmg the oacxqrouno. ihe common solution is to orea* off the front portion of the col umn periodically C. De tec t 'on The CC detector 'S a transducer, concerting a chem ical signal (molecules in a gas stream) to an electrical sig nal Some detectors te.g. , HD) destroy the comoounds in the detection process, while others (e.g., ECD) are non-destruc tive. CC detectors are discussed in more detail m several monograph* ana reviews (David. 1974; Severn, 1976; Adlara, 1978. McNair and Bonnelli. 1969). GC detectors may be categorized as either universal or selective. The ECD ana Hall electrolytic conouct'vity oe* lector (hECD) are selective toward halogenated comoounos This selectivity, coupled with its extreme sensitivity, has made ECD very popular for analysis of trace levels (residues) of pesticides and PC8s and has. in fact, had a significant role in regulatory actions on these classes of compounds. HD is the most common GC detector and is an universal detec tor, giving similar responses for most organic compounds Thus, f(0 would be unsuitable for detection of PCBs in a com plex matrix. Mass spectrometry and Courier transform infrared spectrometry (F T1R) are in essence both universal and selec tive GC detectors. By focusing on a spectral property char acteristic of a compound or class of compounds. these detec tors can be Quite specific. However, by using the full spec tral range, any comoounfl eluting from the GC will pe detected Due to the much higher information content of mass and infra red soectra. iflentifications made by GC/MS or GC/FT|r gener ally have much greater certainty than those made by other oetectors. The analysis of PCBs generally requires selectivity and sensitivity. Even after cleanup. PCBs are usually a minor component of the sample; mixed in with other halocar- bons (e.g., DDE), hydrocarbons. lipids. etc. Thus, tne oelector often must selectively detect PCS* >n tne presence of otner compounds present at orders of magnitude higher con centration. Furthermore, the levels typically observed in food, biota, tissue, soil, and other matrices of interest are in the parts per billion range. These levels strain the cap abilities of even the most sensitive detection device such as ECD. resulting m a large number of "not detected" values m many reports HONS 223646 196 Analytical Chemistry of PQ8s The choice of detector oft*n depends upon the ]e ^ of analytes. Low concentrations demand a detector capable of detecting low amounts (Mgh sensitivity). figure 7-)0 DP#. sent* tne typical rang* and detection limits for most of the GC detectors used in analysis for PCBs. The detection limn of,, tn* HtCO is 10 11 g with a Imear rang* uo to about 10 2 g. as measured for 1 i ndan# (Anderson and Hall, 1960) As can oe seen. ECO exhibits the lowest limit of detection UDD). The reported LOO for PCBs m a variety of metric** are listed m Tati* 7*v. Comparison of the reported lODs i* difficult because no standard definition of LOO was uses Glaser et al. (1981) followed a rigorous definition and ex perimental ly determined the LOO with a fair degree of confi dence. while other investigators clearly approximated tn* LOD. Th* issue is further clouded by inconsistency in pre senting the lOD as a measure of the instrumental determina tion or th* entire procedure. Some LODs ar* reported for standard solutions, while others take into account the in terferences in tne matrix which raise the detection limit considerably. Every review article (Risebrough, 1971; Reynolds. 1971; fishpein. 1972; lincer, 1973; Hutzmger et al. 1974a, Sherme. 1975; Puller *t al.. 1976; Margeson. 1977; Krull] 1977; Safe. 1976) has covered th* subject of ECD detection of GC effluents. fishpein (1972), Sherma (1975). and Hytzinger et a) (1974a) all reviewed the use of electrolytic conduc tivity detectors for PC8 determination Safe (1976) ana Hutzmger et al. ( 1974a) discussed the use of Mam* ioniza tion detection (FID), mostly with r*$p*ct to calibration of ECD or establishing CCD response factor* Hutzing*r et al. (1974a) noted that for th* mono- and dichlorobiphenyis FID and ECD sensitivities ar* comparable. As noted in Table 3-1, most of the standard methods specify ECD as either the detector or on* of the option* FID is the detector prescribed m the American Society for Testing and Materials (1980) procedure for determining PCBs in capacitor Askareis. In this case, the matrix is well* characterized and generally contains no other compounds in the PCS retention window. hCD is permitted as an alternate detector in three procedures (EPA. 1978; EPA. 1981a; FDA. 1977). 1. Electron capture detection Th* electron caotur* detector (ECO) detects tn# drop in current caused by tn# absorption of electrons by the sample compound. A radioac tive source emits 8 particles (electrons) which ar* swept toward the anode by an applied voltage across the electrodes HONS 22364*7 Qiikim iiiNHMiy G<m*i rhtimti c*f|r Afirtyui Phoi*nUliait CtflKI* 'iin Sptctiaaimr -- CUciiaa iMfMi j$ Mvitifti l*a On N| ChiMktf Ua. fivaintm** fl>m laaiiMwa ThomtlCaMvcimir FT/IK '/V 10'1 * lO'" 10`" IO'1* I0`* JO'4 10 >0** t0`* 10"* TO'1 i0`* i fjqine /* 10. Detection tiit> end Oyneaic ftonqe for Several InvlruMHia> Methods Reprinted, with permission. > roa PelMnorl (1981); copyright 1984 by 8uttei*worth Publishers HONS 223648 200 t.llll.fftfl.l W/IUI r>i / it >t i.( /in in 1.1 / I t*\ IMI IH> Nf|M.tt *<J UNI / v Iri-urlrii t iaitt nl U*(r.ii>.n (* vt8- t i4***9 * 1 *00' >u> Kt t,pr M 1 f i r flf. .... <1 ,.<|/l II b M4i fc '> H* Ml 1*4. 1 II | ,y.|i/ 1 >iari U S H* 1 t*l< 0 *> IN* 0 * l|/l 1 if/#` 0 ) m</a* 1 l"l't 1 w* III |*4. in**. M ! 1* <l IKII'S II llllb'i II II'. II INI | II InMil H t II It > It tHXIb M* <i mu l i. .! I> tt( llul Ini 1 71/ *< <W l. lilllllrs A r nt Inr % 11'Mm U< III! l Utl vet lilil NrtMa tnrtni VvrChl*rlnltf hrrll(l tiff UiMi iiKllI l/lm tft umin i/M liMlli )/> *l M III! t/M II..1 * ##li>r l . .vM iw Hi tk Vr|vt U'U > . f >> Ur*r> 1 tr..<| Ult Oh. (it tvtiM !#< ftlr *ll HI.M..I .r<<* ti.fVI.IS Mill Sri i* A * ItUMt t\ * rnt\ ft t` INNOf l* > >nm il 11 t'l <N **'* J*| ) J t f.|f 1 lll ..1.......... r . >1 f i 1 III 1 .**<, | | 0 .Chf t Iff f| l 1101 lltyf *A0 >> > ISAU tl'IUll ft < n/i IMttl* <1 l tHItt. I f 11 *1 fl IH It *>>.. *1 * 1 CHNM 111/ M I 1 nnf y ft 4 1 Nt 1 tnnfy f l l I1NI |10 Itol fl 4* * nrr / A s ............... 1 *| Ml \n < H. |H|'i U III U / i-l' 1 1 l< W tllll ll IIH. h -i| o 1 1 I'-I'U in m-*> 1 II Hi IK till % *. IK til* t."t l |N ll l/>* i-rnttf iwiniriiri s< A* iV v mi >-. ..If. Ii>. 1 ftn lintel.I . > ! .f|ilf 1 > . 1 t ft tM M| f( Mpifr ir | f|rt<* 1*r i \ |tti( .ll 1..,1 r .l |. 1 , > V ft 1 IB 1 ft 1 .t Cl.itri >1 fi 1101 l.n.Uii nC Mln.nufi 118.1 ,t(t< ..1 If l .1 fn.l l, llrt.'f 0 HMI I Mi * w ft f l 1 In H ij'i- ft t 1 n'N HONS 223**9 Inst.il**"! tr|uolvU HM ile l-v ((vm i.ntr.ii (gnr(Ml i on1 " IH> rta in* MmI. * 11 ** w m ins III 1 It tl tt'l II III 0H 0 0001 Mono- In ('lit' IIOWI S H*** lu ,h-( t ItOWII OS'* MS vrtlriunq ri *1 w#.(.b#rij rt 4| isgi t.nl roo Dm I'lohr I m<ii ii tmi MV tiuloij it it r i i i * Oouqnrriy rt > isnii N< |HS tt( It w II tM |i|ia It 1 'H It H'J IMJ tl f Kl| 1 l"l II II 04 Anti lor AOK tr At M tor At o(lor Arm Ai m lr 4 (IimI I" .: "aasttt imil n t tl lK|rMi |irr gr (pt I \ fri It NA .i..l ill l| * Nr.- / IVI 'n* .nMM *'. .1 lit* f 4 1 I 1 It NS 'wit ll I Mr| AiII(h.m> Mi it An.oil t'ttot MS An IB4 1 (itliil MS 11 him) istuainq 1 at lutS |lt't >0. t`|l| S.*#v ft i< . IWl. Or vos in Pttt iq/t till". 1414 Mnlltn. n *| , 1 | -| > I lsV4tt "<) ^.rinff (*|M l q M*"* i f HOMS 223650 202 Analytical Chemistry of PC8s (10-50 v) Tm$ electron migration produces a current ap. pronmately 10 * amperes H a molecule or >on_capabe of aosoromg an electron enters :ne detector, H * e (Me'] , energy. The aosorption or capture Of electron^ Oy M will f*. ouce tne current, since tne species [Me ] ""grates more slowly than an electron. ]n older ECDs tne prop *n turret yielded the detector response. Most ECDs now sold use puis- mg circuitry to maintain a constant current. The freauenc, of the pulses reauired to maintain the constant current s the oetector response Pulsed ECDs exhipit a greater linear, i ty range than the old constant current models Because of its extreme sensitivity and selectivity toward halogenated compounds, ECO has seen the most common oetector for CC analysis of PCBs. wnile it is cons'derea a selective detector, it does detect many non-PC8 comoognos (halogenated pesticides, PCNs, cnloroaromatics, pntnaUte ano adioate esters, and otner compounds) which may oe differenti ated from PCBs onty on the Basis of retention time figure ?*11 illustrates tne potential interferences from cntonnated pesticides, figure 7-12 illustrates the actual interferences ooserved in a chlorinated organic process intermediate (Hanneman, 1982). Clearly, ECO was not a suitable detector for this sample. In addition to ECD'actwe compounds such as na'o* genated organics and phthalate esters, there are other inter* Terences wmch do not give discrete peaks s mentioned in Chapter 6, elemental sulfur can interfere with C8 analyses m sediment and other samples whicn h#vt seen suojectea to anaerobic degradation conditions Anotner nor-soecif'c |ri* terference is mineral oil (ASTM. 1983) l"ne,a' c'i a com plex mixture of hydrocarbons, often contains 3CSs as a `esult of cross-contamination of transformer oils. A typical analy sis of mineral oil for PCBs entails simole dilution with n*ane to reduce the viscosity ano also acmeve a concentration in the linear range of the ECD. Tne mineral oil in the di luted sample reduces the ECD response (ASTM. 1983). in order to minimize the effects of the mineral oil interference on the quantitation, ASTM (1983) recommends that tne sample and standard contain the same amount of mineral oil A major disadvantage of ECD is the range of re sponse factors (Tables 7-Jv. 7-VI, 7-vII, and /-fill ano fig ure 7-13) wmch different PC8 congeners exhibit Tne earlier PGC/ECD work (Table 7-VI) has a response factor range of about 7000, while recent hRGC/ECD work (Table 7-vtJ) ^as a rjnge of only apout 100. Data sets similar to that m Table 7-v] were publisned Oy Zitko et al (1971) ana Hatton et al MONS 223651 Determination 203 00 ( 'loi-Oo >M >00< Figure 7*11. PGC/ECO Chromatograms of Aroclor 1260 (921 pg. Solid line) and Nine Common Pesticides (36 og Eacn. Oasned Line) Illustrating the Potential for Interference A 163 x 0.4 cm 10 glass column packed with 3* SE*30 as od* erated at 19S*C, isothermal *th a nitrogen Mow of IS mi/ min. Reprinted, with permission, from Needham *t al (I960), cooyright 1980 By American Chemical Society. HOMS 223652 204 Analytical Chemistry of PCB$ -t (-. figUr 7*12. MftGC/ECD Chromatogram of Process Intermediate (Bottom) and Aroclor 1248 (Too) The sample contained mono* ana O'cnlorobipnenyis ana over 500 ECO*responsive interferences. A 60*m 08*1 (Donaeo polyp'* metnylsiloxane) fused silica capillary column as programmed from 100C to 290C at 2 min. Reprinted, with permission, from Hanneman (1982), copyright 1982 By 0o Corning Corporation. HONS 223653 Determination 205 Tifi'e 7*vJ PeUt've *oi|r RfiDo^ifS of Electron CepUr* f <*no 1 lom/it'On Del*C 10 r J to Soe C f ' orop i pneny 1 J Chiorop'onenyi Relative "o'er Aejpon** ['CUon C40ture tom hi von (* 3* 42.2' *<3> 2 4-a* 2.6*<J' 3.4*01 4.4'-di 2,4,4'*tn 2.2' .4.4 2.2'.6.6 tlr4 3.3-.4-4 'tetri 3.3'.9.9 ''tetri 2.3.4.9-'tetri 2.3.9.6*'tetre 2.2' .4.4 ' ,6.6'*he*4 3.3' .4.4 ' .9.9'*h*i 2,2`.3,3 ' .4.4'.6,6''OC14 2.2'.3.3 ' .9.9'.9.6'*ct deci 1 00 0 2Q 1 10 9 16 17 7 12 0 6 10 19 2 9 97 139 106 20 6 396 320 367 299 347 726 1.180 1.190 1.410 1 00 0 92 0 67 0.99 0 86 0 91 0 94 0 86 0 81 0 ?6 0 67 0 90 0 8? 0 89 0 87 0. n H M4n 90 990 [X) 21 16 310 0 86 436 0 07 140 3 3 Source *uumger et 4) . '.9744. reproOuceo 11h permission. copyright 1974 By CRC *rei, iric . 9oC4 Aiton. 'or>04. MOMS 223654 206 ?40l ? * v | I *o*elog No 0 > I104W r% Analytical Chemistry of PCBs St**ry 0f (CO 6lti** |MI' ft 41 . 1964) *" so SO f XI fCtorv4 Hi<Mouo V* lu* "**v 1i 1 0 1 ? 3 5 6 J S 9 10 1 0 0751 3 0 0)79 0 0119 u 0.7412 0 1875 74 0 (ill 0.7787 *2 0 6750 0 1997 i 0 U71 0.211$ *2 0 0550 0 284 7 2 1 1579 0 1705 12 1 3720 0 452 3 1 1914 0 2551 1 139 * tgNMnjtO fro* TiOlt >*1V 14 ?5 41 10 29 10 17 42 16 * 0 0193 0 0374 0 113 0 4106 0 444 0 161 ) 169 1 1756 * 0 04 0 49 ; 09is * 1 )98> l 169 ; 044 1 366 1 67] MOMS 223655 207 Uiii>' ' v I | I I l'| It ( Mtlip'.W. l h.C/Kll HestKfl.Vf t 4t I ... i 1M>)I.y U.Ht>4( f 4f.r 4|<.> |> ! 4t `00 l-t/At J 1 1 4*H.I 4) O. J NiiMip. 4 s (, H.-i. 0 11) t bllli 4..{>li^.iy 1 1.1' lllllllui ill. I.I.pMy 1 / . 4 ' t * H f. till ifli 1 / . / ' , 4 . 4 - 1. f I .it il.il>.|.ftt-My 1 /.)' .4.S' .1. I*f.l4lhli.>0|.ttpyl / , 7" .).)'. b . ' Mym. 1.Ii.f ybi)ilirn|i I 7.7' . 1.4.'. .S' , A hf (! . fltwily 1 } . 7 ' . t. )' , . 4 ' . ' .S' ' fit * 4 hlolt>l>py t 7.7' . t, l' . 1.4' , s ` . i. Maim. 1.1 ifl. .............. i 7.7' . 1, 1' .4 4* ' .ii.li tt**> *i ....................iiti.'i.y l u 0H4)S It AM))S .1 009191) .1 owk/s u UOSk/O u fllt?kS II H0SS4S II IM*>4S iKM.ns .1 )ttl4/(N> ou1 \ t is 0 19 u / 0 II 0 17 ft os> 0 00/ A u*n II Uttb 1 >Mt II `fl <) II 1 IS 0 1 HI 0 ll'l (1 14) II IM./S It II4M II ma-is tl 1'.l.4 I n> fl //. II (Mi S u uni it u)/ U OB) 0 0/i 0 07k II 1117 0 <1 Xl. I on /)4fc 0 CtASfl n itA'l u nssB 0 osss 0 074S 0 0/4.0 11 04|| II 11 ]/b 1 11.1 .1 l>(IS >1 0S4 u USA 0 U// u U0 0 MIS 11 IM t I. li74 1. l'/ 1 .1.1 ) 1 >4*4 0 11 0 O tS 0 fl/4 0 HO 0 04 1 0 fl)B U MSA 0 04'l 1 '. >b D I.H It ll 0 1^9 0 ids 001/ 0 11'A 0 1 in 4 0 oik H 49 4/ S4 47 A st> Sf St ltl*yMl*'*f ...Uh' 11>> 1 \ t1i` \4i f 7 4) 77 *l U it HO 40 III 0 //'IB 1) 1./ IS Mf...tPl .iMy.l / . 11 1 .i. ill* ..il.l'.i y 1 u 04 4 il 11/4) IS 11 U4/I 11 OI.S4 A Miyly . m.mImc 1 pi) .r, y.|i t of a i m rim ................................ |i)im. ) m*.-. 1 > Mil.... Ilir >yv|MH.sr l ,*<! .il f 4l >.|4) ion ul IN* Oiy tl.lur H4.11.i4l t < pi' ' l 4>|ih 41 v *! l'n.1 11. 1 1'. ........'if... 1 > IMI *) 1 l6P4tf>> in ir.4ly.pi) IlNM fl. ll.l luftV A|> yli* A(]t 41 1 If m04 sI.4hii.iIh * t*s < ml him II.) ) 4 1 LI * 1 If I*... 11. p |.P44 1.4 1 (iii 1 In* yll.fi 1 ft....... .y > B.WI > 1 4.'.r.NTI*l.al.1 Ml f.l'.l1 Im'MjIiI *. mi ..trnM .i.<vlv ) I.ip ll 1 >*<,.> ) (In. |I V '.41' 11.14 * . . l.i'il I.. llv 1 ................... 41 ill*............... Ml. il ltt It.. I.ll....... ..... 1 .. - 1 1.1 Wi> .<,>!< M.II ).|| m >|. I..t l>l.| . |>| ll.l 1 M .1 W. 4 MM| . I.Mf.' All 1.. I.IP '! . .1 ' .1 1 .1 1a'l f(H| IMffA.t./l1 1 III / . I.lm <fl< .fdH'My 1 ilii m ih- 1 In .111-. Il t4fl>. ill If . tMtf.' l.ll 1.1 ...*<! 1).1n*..y 1 il. Imimii lid l > 11. '4t<- llv <> >1 !.' Mm 11 * I'.l . 1 r .1 . . 1............. ..1 'niHii'i III HA I'HI.*. < v|l 1/ih'i /!' < . Iiy It. y lulu. M.nwl.l lul'M' MOMS 223656 208 2-r Analytical Chemistry of PCBs 0 tl 0 Congener Ng/rfcer 209 figure 7-13. Plot of HRGC/ECO Relative Response factor Versus Congener Number for All 209 PC8s See Table 7-1V for more detailed data and cnromatographic conditions. Reorinted. with permission, fro* Mullin et al. (1984), :oo>* rignt 1984 by American Chemical Society (1981) with response factors ranges about 540 ana 9000. re* soectively. The opposite trend m response factors m Taoie 7-v111. relative to the other tables, presumably results from differences in the equations used (i e.. whether tne RC8 re sponse is in the denominator or numerator) Boe and Egaas (1979). Onuska et al. (1983) and Singer et al. (1983) nave also published ECO response factors. Tne range of response factors seriously inhibits reliable quantitation. The difference in response factors noted above may be a function of the differences in detector design and CC column throughput. In addition, the hRGC is temperature* programed, while PGC data were presumably obtained isotnerally. Despite these differences, all four tables clearly illustrate that, even within a homo log. tne RSD is very large and would result in poor accuracy if Quantitation involves extraoo1 ation from one isomer to another. for example, tne ECO relative response factors for all 12 octachloropipnenyls snowed a range from 1.007 to 2.644 (range of 2-6 K) with a RSO of 35% (Mullin et al.. 1981). A more recent tabulation (Table 7-iv and 7-vlI) of tne respons# factors for tnese same HONS 223657 Determination 209 confounds Oy same authors (Hgllm et al , 1994) yielded mucn different results wm) tne values would pe expected to differ Oy virtue of changing tne internal standard ( 2. 2' 4 * ' * S' *ne*acnl oroo 1 pneny I in t ne former publication and octacM oronaontna lee m tne latter), the trend* jmong tne sets of resoonse factors -ere not similar (ve., tne mgnest in one set was not tne nignest in tne other). This illustrates tne importance of calibration of instruments at tne time of tne analysis The ECD resoonse factors for a solution of one isomer of each homolog ere comoared for six laboratories as part of a co11aborative validation of tne Ory Color Manufac turers Association method for by-product PCBs in pigments (OCMA, 1982: see Cnaoter 10 for furtner discussion). Tn* laboratories reported a mean value for tne resoonse factor ( RF ) and the range of the RFs ODtained Dy analysis of four dilutions of tne stock solution ranging from one order of magnitude in concentration. As shown at the bottom of Tapie 7-vlIl, the intraiaPoratory range was Quite large. The study authors attnputed tne wide range to the nonlinearity of 6CD detectors and lack of amplifiers with 1 meander* in older instruments. They noted that samples should Pe concentrated or diluted to within * 25% of the standard to get reliable results. The results presented in Table 7-viH were recal culated from the driginal data to normalize the response factors. These normalized Rfs permit direct comparison of the data from the different 1 aboratones. The subject of ECO response factor variability is also discussed m the Quanti tation section df Chapter 9. To further complicate its quantitative use, ECD has notoriously variable sensitivity. On tne same aay, an in strument's response can drift enough to dramatically affect the Quantitation of PCSS. The sensitivity i' e. . limit of detection) of GC/ECO is affected by the brand, -ndwidual in strument, daily instrumental response, attenuation, injection volume, and detector temperature (Rust, 1984). Aue and Kapila (1978) presented a novel dual GC where selected Peaks from the first ECO were 'heart-cut" routed to a second PGC column, and detected 0y a second ECD. The chemical degradation of PC8$ in the first detector yielded new electron-capturing species and provided confirma tory evidence of PC8s. The system probably >s not suited to routine application. PGC/ECO is generally tne metnod of choice for anal ysis of transformer oils, nydraulic oils, askarels, mineral oil dielectric fluid, and otner similar matrices wnich must MOMS 223658 210 Analytical Chemistry of pcq, be assayed for pC8 content prior to incineration or other de struction (Coo'and end Gohmann. 1982). Tn PC8s general]' resemble Arocior standards. halogenated interferences are al most none* i s ten t, GC/ECO is highly selective against the nv. orocaroon matrix, and the technique is relatively mexpensi to operate. v* A f>eid'oortabie PGC/ECO was used to obtain r4D,a measurements of pC8s m sediment and soil (Spittier, 198*). The sample preparation consisted of a single solvent extraction and the PCBs were eluted within 9 mm. In a 6-nr period. *0 soils end 10 QC samples were analyzed, with con centrations ranging from 02 to 2*.000 ppm. Tne use of field analysis permits rapid decisions in a cleanup operation ang reouces the need for either return visits to a site py a cleanup crw or excessive excavation of uncontaminated $o'i$ Similar portable systems nave been reported (Colby et al 1983; Picker and Colby. 198*). The only novel aspects of most articles deals with Qualitative or quantitative aspects of the detector and are discussed in Chapter 8. Two studies comparing ECO with the electrolytic conductivity detector ar# discussed below. 2. Electrolytic conductivity: The Mall electro lytic conductivity detector (HftC) measures the change m conductivity of a solution containing MCI or Mfir wnicn is formed by pyrolysis of halogenated organic CC effluents. th* column eluent is oxidized in a microcombustion furnace m * Quartz tube. The reaction products are absorbed into the liquid electrolyte >n the gas-liquid contactor and the elec trolytic conductivity of the liautd measured between the to electrodes. The reaction products of non-nalogenated or ganics are CO;, h:o. h2, and SO;- The SO,. is scruobed out with CaO and the other components give little or no response, leaving HC), Hfir. and the other hydrogen haiides as the oetected species- The hC0 exhibits 10s*10* selectivity for halogenated compounds over other comoounos. It also gives a linear response over at least a 10-* rang*, it i$ much less suDject to interference from nonnalogenated compounds than ECO and the retoonte is proportional to tne number of chlo rines. The nigh limit of quantitation and difficulty of ooeration are the disadvantages of this oetector. Webb and McCall (1973) and Sawyer (1978a) used HC0 in the characterization of Aroclor standards. Serum et al. (1973) used hECO, ECO, and electron impact mass soectrometry as PGC detectors in analysis of paper products for PCBs and other compounds. Hofstaoer et al. (1974) determined that HONS 223659 Determination 211 sulfur compounds m Certain petroleum Oils gave positive in terferences m PCC/ECO determinations of PCBs. flame photoMtnc, *'c rocow 'o*tr ic, and Hell detectors *ere used to characterize me PCBs end i nterferences. cnesier et a*. 11981 > cnerectenjeo oil oroducts m the preparation of Na tional Bureau of Steward* stenderd reference materials for PCBs >n oil. Tney used doth CCO end hC0 as hRGC detectors, me ECO as found to p more sensitive then the HC0 by Wo orders of magnitude end tester to maintain in e noncontemineted stele However, ECO response fectors veried for dif<*r*nt PC8 i sobers. rule the molar response to chlorine which is obtemed from the HC0 eppeered to be constant. The hCD exhibited a >oer linearity range and was more selective as it responded only to nelogenated compounds. Butler (1981) demonstreted the application of HE CD coupled to both packed end HRGC columns m sfverel matrices; milk. fish, trensformer oil, and water Detection of 1 ng of Aroclor 1254 es shown. An interesting, though tangential, use of HC0 wes presented by Oolan et ai. (1972), Oolen and Hall (1973). end Su and Price (1973). By adjusting the HC0 operating param eters they selectively detected organochlorint pesticides in the presence of PCB interferences. HC0 and ECO were compered for their use in detect' mg PCBs m waste oil, nydraulic fluid, capacitor fluid, and transformer oil (Soncmk et el., 19B4). They found both de tectors acceptable, but noted that the hC0 gave higher re sults with less precision than the CCO. The method detection limits ranged from 3-12 ppm for HECO end 2-4 opm for ECO. Greater tnen IOCS recovery of spikes analyzeo by the HECO in dicated a non-specific response to non-PCB components, smce extraneous peaks were not observed. Nevertheless, tne authors recommended nECO for general applications, because simple dilution may oe employed for the sample preparation. They noted, however, that injection of such large amounts of oil was injurious to both the column and the reactor tube in the detector. It was especially difficult to analyze Duty)ated monochlorodiphenyl ether and phlhalate ester dielectrics without sample pretreatment. They alto noted that ECD is easier to operate, maintain, and troubleshoot than the HECO. . Another comparison of HECO and ECO for the analysis of PCSt in oils at the 30-500 ppm levels found that the type of detector made no significant difference in the r*sults (Levine et al., 1983). The authors noted that higher accur acy had been expected from the more specific HECO. They postulated that tn* cleanup procedures (Ftorisil, alumina, and sulfuric acid) all had effectively removed the non-PCB species which would nave caused interferences in tn* ECO and degraded its accuracy HOMS 223660 212 Analytical Chemistry of pcb* } Hist spectrometry: Mass Spectrometer* K#y only recently come mto common use as CC detectors, aitn0uo* they have Dttn widely used for decides in other trees spectrometers contain three mejor components t region ,,ri*!S >ons re genertted (source), a mess analyzer (megnet or quI? rupole). end tn ion detector Molecules introduced to t *4i spectr-vjneter vie e CC ere generelly ionized by $ t*am 6j nigh*energy electrons ("electron impect") or By reection ionized molecules such es methene ("chemical ionization" The ionized molecule end/or its fragments ere then swept (0 the analyzer section In e megnetic sector instrument. t.h strength of the applied magnetic field controls the ntsv (actually masS'to'Charge ratio, m/z) of the tons -men car pass through the curved flight path, a quedrupoie anaiy;e, has a flight path down the center of four rods. Oscillating ftf and OC fields of opposing polarities are applied to ;-,e rods Only those tons of the desired mass pass througn tn* Quedrupoie. the others oscillat* out of the path and st-ii* the rods. Ions passing through either type of analyzer jr* focused on an electron multiplier for detection. The polar ity of the aopMed voltages determine whether oositwe ions (usually) or negative ions are transmitted and detected Associated electronics control all of the components and rap idly change the mass analyzer conditions to scan a mass range. A GC/MS produces a chromatogram consisting of oat* points at about 1-sec intervals, which are actually full mass spectra. The data are stored by a dedicated computer and mv be retrieved in a variety of ways. The data file contains information on the amount of comoound (signal intensity;, mo lecular weight ("parent" ion), and chemical composition (fragmentation patterns and isotopic clusters). a recon structed ion chromatogram (ftlC or total ion current profile; is the sum of all measured ions and is analogous to the re sponse of a flame ionization detector (see Figures 7-a no 7-1A). extracted ion current profiles (UCPs) or ion plots are chromatograms of only selected portions of the data, usually a Single ion. As illustrated m figure 7-15, the ElCPs for PCBs allow comparison of the isotopic ratios ano also exhibit characteristic patterns for commercially derivea PCBt. finally, the individual spectra may be used to iden tify compounds. The spectrum in figure 7-16 is typical of a hexachloroo'phenyl. More complete descriptions of GC/MS in strumentation, principles, and data interpretation are availaple from many monographs ana analytical text ooofcs. One ex ample is Mctefferty (I960). MS is particularly smted to detection of PCBs De cause of their intense molecular ion and tne cnaracter'st >c HONS 223661 N> W figure /* II. Reconstructed Ion Current Chroaetogrea of IIRCC/IIMS Analysis of e Fish Seaple frua Chesepeeke Biy Ihe ereo where Die telre* through heplechlorobiphenyts would elute is aerked on the chiometogrea. Ihe PC8v iu the staple ere not epperenl in this figure beceuse of the higher levels of ini e i f t *ni rs !)** li.lt v.is >al t >ir l <i) with hra.inu .mil iIimiumI n|t with |i* I iierai'.it ton I *| .p.lty Mu' In OM.tt .|i w,i>, *il*l >i I n'.| mii * Ilia 11(1 'j |.llWll, with I i>ni| i rtl Ml I tor 2 am, prOijreMied et lUC/am to 4U)*C. full seen, low resolution election lapeel (/(j eV) dele were collected tor aesset froa m/i Mi to SI/ Unpubl isneil dele, MitctieM D. Erickson end Stephen fc. Swenson, April 2, 1984, Midwest Research Institute, Senses City, Missouri. MOMS 223662 38.6 232 J I*lrcht>b<phin)ilt Jit, ...4. JU,, . jl 603. 231.912 l 0.900 hW.Un 32i re. 2 ** J Penlochlorobiphanyl* . X, >li. uJ, 1 l lexotMofobiphanyli 1564. 325.962 * 1.500 1192. 359.892 t 0.500 ::;7i Hplochlbiphenyl| 1- -.................................... .................... -------------------1, . . It. ,U - < , ,1 fM UsW iM ;0:W lfl lltOO 116* Ji:00 UK 23:80 1290 24:00 1239 25:00 1299 26:90 308. 333.382 * 0.500 1350 3COM 22:00 TIME figure 7-15 Extracted Ion Current Profilet for Tetra* Tit rough deptachforob'pheny i \ m fish Staple fro* Chesapeake Bay See \ Mjnre 7-14 for analysis detail*. Shaded peaks are PCBs Unshaded peaks are either not PCfls or fragments of higher chlorinated hooologt. for exaapte, the peaks at Scan no: USS. 1180, and 1211 in the m/i 2HZ I CP are fragments (H*70) of heachlorobiphenyis tlitfniO 11 shed data. HI ti l*e I I I) 11 ri i * .mil Stephen f S*ai*n. A|>i 1 2. 1984 . Midwet ( Heteareh Institute. Kansas City, Misvuui t HONS 223663 215 Mgur 7*16. Mass Spectnia ot Hexachlorobipheny) in fish Saaple troa Chesapeake 8ay bpectnia No 1100 in Hi|iires 7-14 and 7*15, see figure 7-14 for details on analysis unpublished data. Mitchell 0. Irtckson and Stephen t Swanson, April 2. 1984, Midwest Research Institute, Kansas City, Missouri HONS 223664 216 Analytical Chamistry of PCBs Chlorine cluster ^Chlorine has two naturally occurring ij0. tOpfS. Jsd and 3?Cl. *nicn occur in rim of 100 3} Thus, a fiolcu' *ith on chlorine atom will have a parent ion. M, and an m*2 pa at nS relative intensity witn t0 chlorine atoms, **2 has an intensity of 66% and M*. i\x Append'* C gives acre detailed presentations of the isotope ratios. Mass spectrometry may De subdivided Dy the type of ionization and polarity of ions detected (electron impact ionization/posit>ve ion detection, 1; chemical ionization/ positive ion detection. Cl; ano chemical iomzation/negati ion detection, NCI) or by the resolution, low (able to sep arate at least unit masses, i e.. m/z 321 from m/z 322) or high (able to separate ions of the same unit mass, but on* ferent molecular formulae, i e . C,jCljM, m/z 319 8529-*a pcb fragment--fro* C,jH0;C'. m/z 319.8967--TC00. The differ ences and relative applicabilities to toxic comoounas . eluding PCBs. have been reviewed (Oougherty. 1980) m*** different modes of operation are discussed separately m the subsections below. Because of its expense, complexity of data, and lack of sensitivity, GC/MS has not been used as extensively as other detectors (particularly GC/ECD), despite its in herently higher information content. As the aoove factors have improved. GC/MS has become much more popular for anaiy* sis of PCBs. and will probably continue to increase m mportance. for example, the sensitivity of GC/M$ has steadily improved over the years. As noted in Taple *-v and F'gur* 7-10. GC/EIMS is still best characterized as a mooe-ateiy sensitive techniQue. Several factors including tn intro duction of "routine" instruments without costly accessories, decreases in data system costs, and mass-marketing teenniques, have combined to keep the costs of GC/MS down wmi* prices of other instruments have risen steadily. Neverthe less, a GC/MS is still considerably mere expensive tnn GC/ECD (MO.000 and uo versus S10.000-S20.000). with larger data systems and more versatile and "user-frienoiy" software, the large amount of data is more easily handled. However, data reduction of a GC/MS enromatogram still reouires sub stantially more time than for a GC/ECD chromatogram. CC/E1MS has found increasing use in trace analysis of PCBs es pollutants, including human mtU (YakuShiji et a)., 1976), municipal sewage sludge (Erickson and Pellizzart. 1979), and stack gas from incinerators and power plants (levins et a).. 1979; Hail* et ai. , 1983a.b. 1984). One area whr GC/EIMS (or possiDly other MS mooes) is mdispens>ble as the primary analytical technique is for samples whicn con tain large amounts of other cnlorinated organics. In these HONS 223665 Determination 217 samo'es. chlorin*sDci 1 tc detectors (C0 or wECO) cannot discriminate between PCBs and mterferents. An e*amole 's the analysts of cniormateo organic products and astes m which the PCBs are generated as py-prooucts GC/tlMS has been recommended as the technique of choice 'or these types of samples (CMA, 1981, rckson and Stanley, 1982) a. Electron impact mass spectrometry dec* tron impact mass spectrometry ( IMS) ranks secono on ly to ECO in popularity as a GC detector for PCBs. Electron impact has been and continues to be tn most widely used MS ionization technique. While the chemical ionization (CI) and negative chemical ionization (NCI) techniques are often more sensitive (Table 7-V, Figure 7-10). their operation ts more complicated and the spectral patterns and response factors are mucn less reproducible. EJMS has been applied to PCB determination us ing Doth direct probe and gas chromatography for sample in troduction. Early work generally emoloyed the then-e*otic technique for confi rmation of GC/ECQ results. In recent years, as GC/EIHS has become more routine, analysts have in creasingly chosen GC/E1MS as the primary technique. As listed in Table 3*1, several standard procedures use GC/EIHS. either as the primary analytical tecftnioue or as the con firmatory technique. The application of E1 MS to analysis for PCBs has been reviewed by Fishpein (1972), Oswald el a). (1974b). Hutlinger et al. (197aa). Safe (1976), and Stan (1981). Among the pioneers, Biros et al (1970) used HRGC/E1HS to determine PCBs in hueien adipose tissue. 8g)ey et al. (1970) determined PCBs in paid eagles by DGC/]MS. anq Sonelli (1972a.b) presented PGC/ElMS oata for an Ar0ctor 1254/chlorinated pesticide mixture. In addition. Sissons ana welts (1971). webb and HcCall (1972. 1973). Ugawa et al. (1973). Ouinker and Hillebrand (1963) and Tuinstra and Traag (1983) employed GC/EIHS in characterization of commercial PCB mixture. Using both electron impact and chemical ionization mass spectrometry. Oswald et al. (1974a) were able to differ entiate seme isomers in complex mixtures from their spectra. While full spectra provide the most ouaiita* tive information, the use of selected ion monitoring ennances both instrument sensitivity and selectivity and simplifies data interpretation. Examples of tnis technique nave been presented by BegQs and Banks (1976), Eichelberger et al (1974), Tressl 4nd Wessely (1976), Martelli et 4>. (1981), Collard end Irvin (19824,0. 1983), end Erickson and Pellizzeri (1977, 1979). Eichelberger et el (1974) gave 'on selection criteria which were based on tn*ir intensity and HONS 223666 218 Analytical Chemistry of PCBs the probability of interference fro* higher homologs or other compounds. 'ie 7-1X presents a set of SIM ions approen4te for PC6s originally published by Rote ano Morris (1973) jn<j expanded upon py Enckson et el. (1962, 1963d). Generally only the ratio of the primary to secondary ions is necessary for qualitative identification. The tertiary ion is u^0 only when the other data are Questionable. The analyst must also include ions for the internal standards and recovery surrogates added to the sample. A compromise between full scan and SIM tech* niQues is mass chromatography, alsp called extracted ion cur* rent profiles, full spectra are collected and then ion in. tensity versus file position plots are extracted from the data by the computer Thus, mass chromatograpny has the ease of interpretation of SIM put higher (.OQs since full spectra are collected. These full spectra are available for Quali tative us* if needed. Canada and Regmer ( 1976 ) presented a techniQue which used mass chromatography to monitor tne ion ratios in the PCB isotopic clusters. Another compromise techniQue. limited mass scanning (IMS), involves scanning the spectrometer only over the mass range of interest (e.g., molecular ion cluster) This permits the spectrometer to spend more time on the ions of interest and thus achieve better sensitivity than the full scan mode. Figure 7*1? presents an example of an LM$ analy sis (Erickson et a!., 19830). The lower portion of the fig ure. the "reconstructed ion chromatogram" (RlC), is a sum of all of the ranges scanned. The plots of the individual >ons for the octacnlorobipnenyi and ,JC*octachlorobiphenyl clearly show fewer peaks and thus, less complexity than the 3IC Tindall and Wininger (1960), Erickson et a! (1962. 1963a,D.d) and westerberg et al. (196*) utilized l*$ in their GC/E1MS analysis of commercial products for by product PCBs. Table 7-X presents a set of suggested IMS ranges, develooed Dy Tindall and wininger (i960) and modified by Erickson et al. (1962). The analyst must adjust these ranges or add new mass ranges to cover internal standards and recovery surrogates. The mass ranges cover at least the ions for SIM analysis (Table 7-VllI) and also include the two masses below the parent ion. These ions are included both to monitor the background, since M-l and M-? losses arc uncom mon, and also to permit the system to settle down electron ically before it is measuring a mass wnich would be used for Quantitation. A similar approacn was used Py Westerperg et al. (1964). MOMS 223667 Determination 219 Table 7* IX. Characteristic SIM Ion* for PCS* Homolog Ion (Relative Int.ensn.vl Primary Secondary Tert i ary c,2h9ci 186 (100) 190 (33) - C,2HBC1: C|2H7C13 C,aHCl, CI=HSC1S C12H4^ 1 * cI2H2C17 222 (100) 256 (100) 292 (100) 326 (100) 360 (100) 394 (100) 224 (66) 2S8 (99) 290 (76) 328 (66) 362 (82) 396 (98) 226 (ID 260 03) 294 (49) 324 (6) ) 364 (36) 398 (S4) Ci2H2CI 430 (100) 432 (66) 426 (87) C|2^C19 464 (100) 466 (76) 462 (76) CUC1 io C|0Hfcla CI208Cl/ 496 (100) 2$A (100) 298 (100) 500 (87) - 300 (49) 496 <6B) - 296 ( 76) c i a 0 r 2a 13C6'^C6^C1 D 'K.jH.ci,0 '3Cl2H,Cl|b 240 (100) 194 (100) 304 (100) 442 (100) .96 (33) 206 (49) 444 (65) 302 ( 76) 440 (87) 13Cl2Cl!0 510 (100) 512 (87) 508 (68) Interna) stanoero* added to sample before hkuc/IIMS analy*i* b Recovery surrogates added to sample before extrac* Uon. Source: Erickson et al. 1985c. MOMS 223668 220 Analytical Chamistry of PCBs ANALYSIS OP CHLORINATEO AROMATIC WASTE .or no ' *M i v i . Ml Mr o C 3o''0"% C - C. K1 Figure 7*17. HRGC/E1MS Oata for a Chlorinated Aromatic Waste Showing Presence of Octacnlorooipheny 1 s at Byproduct* Extracted ion currant profiles (upper) of octacMoropioheny' congeners identified <42$, 430 Qaltons), the 1 ^C-octachlore* Diphenyl surrogate (442 Oaltons), and portion of recon* structed ion chromatogram. Reprinted, with permission, from Erickson et al. (1983b). copyright 1983 by Battelle Press. HONS 223*69 Determination Tab'e ?*x limited Mass Scanning (LM$) Ranges Tor PC8s 221 Comoound Mass Range ( 2 ) c,2h,ci, `H6'-'csh,ci3 Ci2 H,Ct, c,2h7ci3 c12h6ci, * Cu06CUb * ,3Ci:H#C1/ 186*198 220*226 254*260 288-no C,2H$t 1 S 322*328 CtJH,Cls 356*362 Ci2HjC17 390-396 Ci2h2c1j 426*434 cI2 HC 1 9 460*468 Cj2Clio CiyH,Ib ^I!2^ 496*502 254 240 i:1Cl2H;,Cl,a UC12C1P,,4 44Q-446 508*514 a Recovery surrogates added to semole before extrac tion, b Internal standards added to sample before hrqc/EIMS analysis Source* Erickson et al., 1985c. HONS 223670 222 Analytical Chemistry of PCq, In contrast to ECO. the responses of the p,fi congeners are relatively we 11-benaved. As seen \t\ t 4l) , 7* 1 v, ?*v], 7-vIi. and 7-V11I. the ECO response factors Ca^ range over at least two orders of magnitude and can even *ar widely among isomers of one homolog. The CiMS aata 0f Martel) i et al. (1981) are presented m Table 7-xj. ihej response factors are somewhat confusing, in that the response for each homolog uas set at 1 000. Thus, there no way to compare the responses of the different homoiogS a more complete set of response factors (Rfs) is presented m Table 7-xtI (Erickson et al., 1982, 19B3b Stanley et al . 1983). Comparison of the data (Table 7*<nj ana figure ?*18) indicated that there was a statistically significant difference in the RF values from the Quadruoolf and magnetic instruments for all but the mono-, tetra*. ^nd pentacniorooiphenyl homologs. Differences between instrument types were expected due to differences in mass discrimination and hence sensitivity between the quadruoole and magnetic sector instruments. Further comparison of the data showed no significant difference in the variance of the RF within each homo log. Based on the consistency of the RF data, standards were selected for calibration and quantitation of all PCS isomers for each homolog (Table 7-XIV). The RF values indi cate that HRGC/EIMS should provide more accurate Quantitation of PCBs than can be obtained by other instrumental methods. b. Positive chemical ionization mass spec* trometry, Positive chemical ionization (Cl) mass spectromery (ciws) is one of the "soft" ionisation tecnniQues wmch teno to produce fewer fragments. Thus, the spectra are simple ano the molecular ion is generally one of the most intense oeaxs However, with PC8$. the electron impact spectra generally ex hibit good molecular ions, reducing the advantages of Cl Another problem with Cl is that the ionisation process de pends on a reagent gas introduced with me sample into me source. Slight changes in gas pressure, source temperature, and electronic conditions can affect the reaction conditions and thus the spectrum (both fragmentatioo patterns and over all intensity). Thus, Cl is not as reproducible as electron impact, either qua 1itatively or Quantitatively. Several researchers have utilized GC/CIMS for determination of PC8s. Oswald et a). (1974a), Sawyer (1976a), and Cairns and Siegmund (1961a) character!zed stan dard solutions. Oswald et a<. ( 1974b), 1 ida and Kasnigi (1975), Stalling (1976). Cairns and Jacobsen (1977), and !-da t al. (1983) applied GC/C1HS to PCS metaoolites, environ mental samples, and food samples. HONS 223671 Determination Tael* 7'*I Molecular Ion Response of PCB* Congenr$ to E1MS* Compound Response Mean SO, n * 4 223 MonochIorobiphenyl $ 4 3 2Menc Oichlorooipntny1t 2.2'' 2.6 2.3 3,4 2.5 2.4 4,4' 3,5* 3.3' 2.4*Man Tr ch 1 prob i pheny 1 s 2.5.2'* 2.3.4 2.4,6 2.3.6' 3.4.2 2.4.4' 2.5.3* 2.4.6 2.5.4'Mean Tetreeh1orobipheny1s 2.3.2' .3' 2.3.2* ,5' 2,4.2* .4' 3,4.3' .4*2.4,2* .5'2,5.2'.S'2.4.3' .4* 2,6.2' ,6' 2.5.3' .4' 2.3.4.5 2.3.5,6Mean 1.000 0 004 1.060 0.015 1.090 0.015 1.050 0.046 (4 4) 1.000 0.078 1.505 6 0. 148 1.669 0.021 1.738 0.016 1.821 0.023 1.851 0.021 1.666 0.033 1.909 1 O. 140 1.922 0.062 2.062 t 0.035 1.736 t 0.30 (17.2) 1.000 t 0. 066 1.273 0.064 1.2B6 1 0. 087 1.315 0. 122 1.319 0.079 1.356 0 143 1. 356 0.103 1.474 0.097 1.627 0.061 1.334 t 0.221 (16 4) 1.000 0.039 1.253 0.094 1.315 * 0.092 1.418 0.146 1.478 1 0.090 1.536 i 0.086 1. 749 1 0.097 1. 766 4 0.045 1 826 * 0.133 1.854 1 0.206 2.146 0.092 1.577 0.32 (20.7) HONS 223672 224 Analytical Chamijtry of PC8s Table 7**1 (concluded) ComoOund Relative Response "ean SO, N * 4 PentaCh 1 orob'phehy1s 2.4,5.2',3'* 2.4.5,2'.5'* 2.3,4,2'.5'Mean Hexacnlorobipheny)S 2.3.5,6.2'.S'2,3,4.5.2',S' 2.3.4,2'.3'.42,3,4,2'.4' .S'2.3.6.2',3'.6'* 2.4.6.2' .4' .6'2,4.5,2' ,4' .S'* Mean OctacMorobipheny Is 2.3.4.5,2'.3'.4'.5'2.3.5,6.2'.3',5' .6'- 1.000 0. 041 1.001 0.072 1.013 O. 047 1.005 0 007 (0. 7 ) 1.000 0 077 1.092 0.100 1.100 0.047 1.107 4 0 071 1. 184 4 0.038 1.265 4 0.022 1.321 s 0.103 1.153 4 0.13 (10.8) 1.000 0.056 1.359 0.034 graph low resolution mass spectrometer oper ated in the U mode with selected 'on moni toring acquisition, equipped with an LKQ~?130 computer for data acquisition and calculation The GC conditions were as follows: glass column, 2 m x 2 mm (0. packed with 3 0V* 1 on Gas Chrom Q (100*120 mesh); helium flow, 25 mt/min J; electron energy, 70 eV; trap current. 100 pA; ion temperature. 250C; separator temperature, 250*C. b Relative to the isomer with the lowest respdnse, for each homolog. c Mean * standard deviation (relative standard deviation) of the responses for the con geners in the homolog. Source; Martelli et al., 1981. reproduced un permission, copyright 1981 by John Wiley and Sons, Ltd. HONS 223673 225 t u '< '*11 llviii *> IfilniMiiii, 1 1 1 I S/ // 1? ta 11 tt li; > / is / it 1 /i ; 1 /a 1 /a 1 /o I* I 1 II 1 v M / so / M M <4 I I. .fc i.-a '*'* i <! lUnA'iias (no,,, i,, li>* ....... t*i; (* wimHwiii*1 i.i.-- i i. i... -- f*fl77 .,i itxtliM l\ y,* 4 ^|IM ) " *<' I . r, 4 4 11/ 1 / O'. 1 / 0*4 l I.1 'I'.O / non / H4'. / 1 IK l MHO 1 / 1 I / IMM 1 OIIO 1 1*1* i sa* 1 M ( M* ti sa/ IT/ 1 S11/1l.. 1 IM SI/ II >u I .>/ 0 >l| II IS/ .. 11/ u r*i II I'.M 1> 1 1I ua II |)S* u /* II nnn i> (/IS t /> 0 / 1 tl on t 0/1 o ait at* at* a ui? a ait a on a an a a/a a t<a a a*) a */ a an o an to*/ t asi 0 tit * .' 11 ii 11 tia null I i.l ' J* lift# U1/ '' II 10 *1 ' i > * ' 1' ' I ** *' 11 II *I *> I ff `* i I* / as s* // /* IS in ii I| l * M I / /Ml* * gif in i MS : is/ 1 i*1* * / /a* / ai l to* > !/ l I l*S I M* I 'So I I*W i *ao i *si I /! n sos it ts M (j o<| * urn o "i ii i it i. --i l *.* | | I) > S 16 . , ,, /hi ,, i in i i /if i / , iSfl / i/u is< i /> I til U 4/1 | , 0 Ul I /i/ i /O' ISM i /so i /< l ??( 1/ >N> 'Ml I Ut' a a in v h '* * <1 HI MOMS 223674 226 ly If /S li HI m * ir iM MM lai |M MS IM> * i;i 1 *N I ri 1 1* or (M 111 l*t 1 Ml IS IV* MS IS4 Id tat in t*s Mil*. t 1 . % s S S , v 1. a k * t> h 1. k k k k k k r i i / At* MM i.'fi*.*.n'* ..** <<> \4I*mSismssrasK(1v^t*r< bxtiiM >tmi >*1 < m iMM.ititll* * I %<! n*<ur**ni I l ! ii imi l !. 1 !<. .1. 1 I'll M './ y Ml f> Ifl <>'. 1 >* i. < i a*. i ii 1 <./ H MB i. I n ii i| ij* . U Ml .1*11 II h.` it t-r u . Hi 4 III g st* >1 Ml ii '.*< i Si-i i it. i. lial M IW. * Ik. u tnn MM * M*l * MS* l MX tar1. at* MB Ml mt U* */k Nil *11 mt Mfl tmf. * mM *!fc a mat ii.'k * talk ID t IM ! )> *4* v Mir MU* MlM <s t . | 1 < | i. / tr || HI us Ik 1 i. '1 >I ti .'1 1I > a . Ik ii i /4 lu ft ii ft | 1 uk ' 1 I IS 11* n m in , .i .1 '/; k SO 0 M <) III H kSa I. M|k ii/ .. ars .. r.% .. in l M t / 1 %* I .' I *tl 1 k1 *SS a 4M 0 W .1 u 1 U */ 1 U Ml . /S MS 114 air I \*4 9V*M II |^| II 1|f i v i; i >* *i i i ii ii U 411 0 Mt w * in ' M> 1 \m w *** U M/ U M4 .1 ff .1 M ll Mlf 1 s/t Ski tf S/ Ml M k<1 0 /* U /I M w <kk l> S*l n > i l< MS MOMS 223675 l IMMfTOtl ......................... (MO( <A*I 1 lilt / III I'fnc lug'll l|.i nit Hfrfllr | Rf4turrmi 11*''1 '4r <|r *4 l.lt tr Rrt|iuntr 1 41 tui Of4ltlff> (!*<* ul *' tl 110 \\\ bA 1 t tttf 1 r Sr|(wt I S t -f 1 r III Its l /w /tl/ /lit H n P< H II ll .71 ,'! 1 H II U'l 11 ,'Su 1 //* 0 OUI 0 1/01 0 no/ 0 (Ml/ u#/ II h 1/ / ' /4 1 1/ 1 iSH I !*> ll |ll I /so ll ;/ 11/1/ |, \>> It 41/ 0 tit 1, t 1 l> S'S u M /lib /II/ /r>n I 1 I 111 1 , i / M ."I 0 UOI 0 0 mu 1/ is 11 II Ol 11 / in I //Ml \J l* tl S l Ip Slh rfoo < 11 l* ll 1 1 l< hh. ('- >* l> *4t 4* \\\ t, )' . 1 trim Itl.tt tai'liftf-a 1 CalluUtril 4' 11*-- 4'ii4ir 1 IHH 1 4ft 1 > 1 4<r 44mk 'm 1 a n l*tf 'iw 4iy I tdoiinlt \rw4> i\r.l 0* 4 0 fl) mm Id l`j a UR S I It /> |ia I t I I lutrt I ti 1 t|n l li , iiliw I4 Si ini) 111< I at Ih i'l t iam >*! i<m iim r< . u > niia* ,, ,i 1 >v.i 1 i(i a I 1 0 ,.t 1*444-4 1 iuMi In- i.il<aii irRir'iliHt mi |tri<i)><a*il I'M I III |r i/y*C ji (* <(.* i,t l>l > a lk iimiif aith 4 Itrnslrt 11II- (fir'altil 11 fMl'l ll I I an I 40 In,'I Quoitt ifat I r M4i'. Sltai 11 natt-l*' hi th - I fit'an * *!>* >.m , - |.r 11 im*I 4 m .1 It * // f, SVI 11 h a | >< I y< l I , an 11 'rtf I Hi `an . imm f I ra*` tlxir ol /BO* I /0 ** |l|i|im rttri III, / / lifi (II`M ItHM * milt |'t <rt ft| 404 , fail III ` I/I m r rap'''im* It 1*11 r ">4 4.. i|tri 11 aia-t r> i I all :if If or I o< ||HH| If I lyu'fvt I "lr I 4 ll ti > to" I I . I HR/ > la ii 1 l |`< HltW 111 t I `t > 1 I imi (.< 4>r a-- 1 i% I'fH'tn 1 a.tiM .in Ilr iff* 1I49 (Hr ffi h 1 utitfrttrr a S"-|l <>> -it !. rfi It t nifTtaf > . *11 <Jfl < h* !< I rtf imi 4 t tafia 1/4/ I *> '!I'nlt ol I n<j ut 111 . rli . uliiilt Itiir ilfy la 4*r 44' 1 fat a 4 1 igi> Ml |) f'i|i'l n \nlst 4tt tff I ihmIii iia ,l.<i,ni. taartl iti-iiriift iff iwiiiwih mi m artarti ti < */ 'M 't't rt|int<f<ll `4*1* !<> 4 I / tfl I n If I IM- '4in(l tun at lmj **> t raia> 41 o' ul /M"! . It rl ilnn >in ran ir. 1/ Ml mitt ton <411 ml, 4ntf 141*0 V aal I 1 wM 4fr ............... liiilum rl 4I I I'M/ , I HR If I, stanlff ft * (IbOII, *nt af*n*t l tltf4 04*4. Rtfaftl I|>t4nli 1'itl`lulr t'tt { t|*. Ml Haiti t MOMS 223676 228 Ittiffr 1 9'| 1 , t Mrtt.it >I I I ,m> ir , f ItfM /f (MS l >. | , i Uif > <111 Unt il .|(|||1 t frtv.i.. Ill N ` >V,i. si) SO l* UiiKI'i Hti|H (1 #>m **(! l fi'^fiwi 1 . *f ft so so \ IfMiifl II Sf< | i Hf an so SO 1 11 C I. 1 1 HI . Hit it i f 1 it t< < ni // H . >*: / .1 1. I.v ,I IS > 1 l.'l t kk 1 II Iff u //* s 11 1 1, f 1 Ml .. HI /i i 1 SfV 0 /9t If 1 1 'O' / /l / !> If f. 1 II l`> ( t 0 Mh >i im /o u U 101 (1 1 10 1 / i; It 1 l . tl (0 1 o /if 0 IHI II 0 SI 1 1 IS 0 1 II 11 Il l 1 Ir ma is i tt Viill II ll'Hi If ( 0 ktM II l/t 11 l fit 11. i ' II Ifcl U tl. t ..... t0 11 ' u Mm //# u u/s M mt II 0 1/ I II *11 (I h | 11 UhO 1. .i/| / 0 IS II. M 4 Ml II I'll M0 0 lio* It ir III 10 / 0 u < lus // s LI,.. i W 'll U Iff U Sk # III ('ll, | I 1` f ' If | m Mm ufeiptirny I iff (ml<K>lft > Iflfllft tl.itoMnl Iitixlt.i* i*1 f| il'ill/. I '! t*a). Slfitlff ft tl ( IfO 11 rntl Ift'tf t I Hi M< tti'H' 1 I fir If I t|| (fl rrffnffMlI I ul|t I > * sMil tltu. titKnl Irttritt Itvti tttilt MOMS 2236?? Determination 229 Pigu* 7-18. Plot of Average Response Factors versus RCB Homolog Response fetors were determined relative to 0^-3 .3 ' ,4 .4 ' * tetrachloror*ohenyl for 77 congeners on a single oav to unriaiit mjtr.-ental effects. See Table 7-x 11 for instrumental conditions. Reprinted. *th permission, from Erickson et at. t!982, 1903b) and Stanley et al. (1983) MOMS 223678 230 Analytical Chemtatry 0t Pqq, *401* 7*<IV. *tirmg of *1yl* And CAl'brAlion Congener* tQr Noio9-Spec11 >c GC/JI^S 0*l*t)n*iion of PCB ___________________*n*iyt .0 t.ong*n#r No to*OOvnd C* 1 'pr<tion StAndA'O4 Conqonor NO Co*0unfl 1 Cu"*c: 17 < IS 16- 39 C.jH.CIj Ci;*,C'3 7 7. 10 7.4.6 40-01 ^1, so 7.7' .<.6 07*177 ::a-i69 170-193 C uKC U C|>HaCI- 97 7.7` .3' ,.5 IO 7.7'.3.. 5. 6 183 7.2-,y * * S' .6 194*^05 C,jH,Cl, 702 7.2' .3.3'.5.5',6.S' m*?0B C.2HC1, 707 7.2' .3.3'.5,6.6' 709 Ciiclia 709 C|*C1|Q i In* cong*n*rv or* pr*p*r*d 'n 4 titur* long in i*u*rn*i ttn> dordt And wv*d to g*nrt* in* netpont* fctor| for th* *n*lytrj in tn* I4M row. 0 0o)lciwu*r od Jill, i960 goitre* EncMOn *t 1 , 198$C MOMS 223679 Determination 231 Tht fragmentation patterns of nyarogen C! mass spectra are i somer-aepenaent for trie >oer homologs (C' ana 'o-er) anfl may Of useful >n identificat'on of C6 'somers (Harnson et al., 1981) The higher nomoiogs a>a not frag* mens enough to be of Qualitative value Dougherty et al. <1973) reported the use of direct probe positive ana negative C1MS for the analysis of numan adipose tissues for PCBs. Stalling et al (1980b) re* ported an hplC/M$ tecnmoue for PC8s which is presume to use tne Cl mofle This preliminary report SDfCulatfO that HPtC/MS could oe useful as a screening technique for environmental samples. a related (Put often defined as seoarate) technique, atmospheric pressure chemical ionization (APCI) has been reported for PC8 determination. Ozidic et al. ( 1975 ) reported subprogram detection of 2.3 .4.5,6*penta* cniorooiphenyl. An instrument in a van has been used 'or m si tu detection of PCS s m clay and sol (Thomson et al"" 19B0; Thomson and Roberts 1980, 1982; Lovett et al.. 1983 ) It has been used for direct samoling and analysis of mono* through hexachlorobiphenyls in stack gas (Lovett et al.. 1983) and ambient air (Thomson et al., 1980). Data were available about 2 mm after the sample was collected. A oe* tection limit for total PC8s of B ug/m3 was reported. c. Negative chemical ionization mass spectrom etry: Negative chemical ionization (NCI) mass spectrometry (NCiHS) is similar to both CIMS and ECO. The basic oifference Between negative and positive Cl is the polarity of the various voltage potentials in tne spectrometer ana tne a*- tector. Many of the Chemical reactiohs in the NCI source ana tne CD are tne same. NCI and C0 exhibit similar detection limits and se1ectivities toward chlorinated compounos. thus tne interest in NCI. The reproducibi1ity problems of Cl are also present in NCI. The range of response factors found with ECO are also founo with NCI (see Table "**v) ncims. only recently available, is still considered to be a research technique. The ma^or reasons for use of nCIms for PCS analysis are its sensitivity ana selectivity. Tne sensitiv ity is highly dependent on tne degree of chlorination. As shown in Table 7-xvl, the sensitivity of NCIMS is much worse than E1MS for the lower nomplogs and up to AO times oetter for the higher homologs (westerberg et al.. 1984) Neverthe less. the lower MOL for the higher homologs can oe a oecioea advantage for trace worn. It should De noted mat tne mag nitude of the homolog di scnmmation may be dependent on con ditions or instrument configuration. MOMS 223680 23? Analytical Chemistry of PCBs 0' I 7-iv >< for MIGC/HCIHS Ooloction of *Clt (/I JS> *or Hoao'ooout 4ri of ( HkO'0 of ItMO'l 'oii'blO HO Of c lifWM "oor* **** t so 1 ISO 1C t ] ] 0 SS-l 71/ .'(1 i; 1C' 2 1 1 MWt 111 7 0 UHO Ml *ct *1 16 0 102` 267 SCI *6 1? 0 44S-I 2)6 6C1 42 16 0 169*| 440 7CI ; 1) 0 2M* l 1J Cl \l 0 lit Cl i 10(1 l J 0 066-0. S6S l. a *>> <luo r r* l*ii * to 9CKCtMoro<**pfithlM Source *fH>ntr< t l . jMJb 0 ! t 0 s >41 1 6 17 2 12i t > 64 7 os t i o; 0 MS ( 0 V 0 17 1 0 21 0 >01 t 0 o Vi t 0 24 0]$ l 0 26 0 *11 1 M I2S SO 1) 16 4) <6 7J HONS 223681 Determination 233 T *0 * * ' I*C 10*' Vi< t * 0' DtltCl'O" 'Of pCtl n-- + Ot* I 900} -Cl Ot* (900. / ttoMttn la'Oe 'Ofttny > 1U 1 3 10 t 777 > 1 10 1 * 1 f i ( M#f 00 i#J\ny 1 in 7 4 to }.}' ..* 710 : o . to i. j- i 17 1 7 to i7 lii 17* 1 9 10 i.r i y . 4 4 -M.#<M*r*oio*yl 7.7 j.) *' ~ot'i>0''00>B*y' 7.7 .1 1 ; ; 3.3 * * i 5'-0ct#'>lof*6<"*'yl lit [ 3 M 7 117 7 : 411 1 7 3i tt 0 14 0 09 : .3.3 . .'.4.1 fc**on#Ch'*r6iB*"y1 *40 t i 0 13 :.: j 1 * i i 4W t 1 0 to 4 HQt - jwou'ti ..f" :s"rtao*et ! oo* i<e* tt <',9r " i >9 iy*yl 400v *** ,oPt iMiwi ft |I . i9H. f>po>K*o uh o*r>vion. tooyf'qM Or Ouo 1 1 l*fM . I v MOMS 223682 234 . Analytical Chemistry of PC8j 'he selectivity of NCIMS was illustrated oy ,uenl et al ( 1900a). who used Both KflGC/EIMS ano HflGC.'NClH$ *.o analyse fish samples for a variety of cn l oro* orgam c s. in cluding PC8s. The electron impact spectra -ere used 'or pri mary 'dentif i cat ion, although the NCI spectra were also of great value, figure 7-19 presents the NCI and electron im pact RICs for comparison. Tne NCI is much more selective toward the halogenated compounds, eliminating tne broad humo hch i$ presumably a complex fixture of lipids and oi's fr0(B the fish main*. Other investigators have aDbiied GC/ncihs to analysis for PC8s m Lake Ontario sediment (kammsky and Hites. 1982) and marine sediments (Lewis and Jamieson, 1983) The group led by Dougherty has published ex tensively on the methods and application of (oirect probe) sC]MS (Dougherty, 1980. 1981a.b; Dougherty et al , i97]. 1980; kuehl et al., 1980b). Tne techmoue is described as rapid ahd highly selective toward halogenated compouncs Tne latter advantage reduces the need for cleanup and, according to Qougnerty (1981a), permits the analysis without the cus tomary GC separation. HRGC/NC1MS proved much more sensitive than hRCC/EIMS for PCBs in the analysis of ambient air samples collected during a demonstration of PCS destruction at the ENSCO incinerator in El Ooraoo. AR (Erickson et al.. 1980a> Extracts of the polyurethane foam arr sampling sorbent con tained no detectable PCBs when analyzed by hRGC/EIHS, whereas t*e analysis of the same extracts by HRGC/NCIMS found mono;r>w0ugh hexacnlorobiDheny I s in most of me samples at con centrations uP to 91 ng/m-/homolog The HRGC/NCIMS instrumental operating oarameters have been characterized (Pellwzari et al . 1981. 1963a, 1983b). The choice of reagent gas and us pressure markedly affect the relative intensities of tne major peaks (m/2 35 and 37, molecular ion. etc.). The response factors -or several PCB congeners are summarized in Table 7*xv iPellizzari et al., 1983b) As witn ECO. tne range of the -esponse factors is broad. Thus quantitation by extrapola tion from a single calibration isomer presents similar proo'ms. They have comoared the quantitatipn of single con geners obtained by hRGC/ ECO and HRGC/NCIHS (Peiiizzan et al., 1983b). In both cases, mere was a one-to-one corre spondence between tne calibration and analyte congeners, for unt congeners in serum and 36 in aoipose. the analyses gen erally correlated well. For some congeners, however, there as a distinct bias toward one or tn# other technique, wnich may have been due to discrepancies in calibration. They also note that the HRGC/ECO is more sensitive than hRGC/nCImS; 109 versus 50 peaks were quantitated by me two techniques, respectively HONS 223683 Determination ^0*Tiwt ,i I I '( II 1 'ONi;*TION 235 ooe r:cc $oc"'jm Ngr-ser .!"ON ir :3 ' I i! ti i, I^V, 4'..1 .. 1 -/ ' "-1 .a,'** see SO:rum .-toe Figure 7-19. Comparison of HRCC/NCIHS (Top) and hRGC/EIHS (Bottom) Tot*) Ion Current Profile* for Fish Sample The fi*h sample was extracted with dichloromethane/ne*ane (50:50), cleaned up by Florisil column chromatography and further cleaned up by gel permeation chromatography. The sample.was injected via a Grob injector onto a 30 m * 0 25 mm glass capillary column coated with SE-30 which was programmed from 100*C to 22SC at *C/min with a 30-min notd. A Finnigan 4000 guadrupole mass spectrometer was operated at 70 ev 'oniiation energy for the IMS mode and with 0.5 torr metnane for the NICMS mode. Reprinted, with permission, from Kuehl et al. (1960a), copy right 1960 Py Association of Official Analytical Cnemists. Inc. MONS 223664 236 Analytical Chemistry of PCBs while not directly used for PCB determination, HRGC/atmosphenc pressure negative chemical ionization mass spectrometry was shown to Pe both sensitive and selective for PCDOs in the presence of PC6s (Mitchum et a!.. 1982). with proper selection of masses and ioniration conditions. tm$ technique may be highly selective for PCBs. d. High resolution electron impact mass spec trometry: HREIMS is capable of obtaining precise and accurat: mass measurements of a peak. As reviewed by Safe (1976), HRE1MS is particularly useful for chlorinated com pounds because the chlorine mass defect clearly distinguishes a halocsrbon from a molecule containing only carbon, hydro gen, nitrogen, and oxygen. Safe (1976) and Safe et al. (1975) have reported the application of direct probe hreims to the analysis of crude goat urine extracts and other bi ological samples for PCB and polychloroterphenyl metabolites. The reported 10-ppP detection limit and the rapid analysis time (no GC separation is used) would appear to make mis technique a suitable technique for rapid screening of samples for the presence of PCBs. Figure 7*20 illustrates the need for HREIMS to separate interferences if they are not chromatographically separated. The direct probe mass spectrum in Figure 7-20 shows that ODE, TC00, and PCB would have given one peak under low resolution conditions (Saughman and Meseison, 1973) Similar spectra have been published by Hass and Friesen (1979) and Oougherty (1960). HRGC/HRE1MS has been applied to the analysis of fat and blood samples for PCBs (Voyksner et al.. 19B3). As discussed in the next section, the technique proved more reliable than direct probe MS/MS analysis. Several factors have inhibited me wide usage of GC/HREIMS for routine analytical work. Instrumentation i$ more expensive, more difficult to use, and much less avail* able. Nevertheless, HREIMS does provide much higher qualita* tive confidence than most other detectors and should be con sidered as jn excellent candidate for confirmation, when re* qulred. e. Mass spectrometry/mass spectrometry (M$/ MS): MS/MS couples two or more mass analyzers m one instru* ment so that a fragment of a molecule (eg., M-70 for a PCB) may pe selected out of the entire spectrum, further frag* merited and, in a subsequent analyzer, its fragments analyzed. MS/MS may be operated in several different modes to produce different Outputs from this multidimensional ion map. The technique has been reviewed (Kondrat and Cooks. 1978. Yost HONS 223665 Determination 237 372,000 321.900 321.800 a/C figure 7-20. HREIMS Spectrum of Fish Samole After Sulfuric Acid and Alumina Column Chromatographic Cleanups Th CH*C17 /hexane (20:80) fraction was analyzed after pree'ution with A CC)4/hexane (20:80) or B - CH2C12/hexane (1:99). Reprinted, with permission. f rom Baughman and Heselson ( 1973). HONS 223666 238 Analytical Chemistry of RGBs and Enke, 1979). A triple quadrupole was used to analyse ma rine sediments (Bonner, 1963) By normal GC/EIMS analysis, PCBs were indistinguisnab'e from the hydrocarbon background! wmle GC/MS/HS was able to detect (but not quantitate) tetrathrough heptacnIorobipheny1s with little interference. for each homolog, the first quadrupole filtered only tne Ci*Mn3SCl(0.rt (i. e. . the lowest ion in the molecular cluster) ion. The second quadrupole, the collision chamber, generated daughter ions, and the third^ quadruple scanned the spectrum of the daughter ions (H-Cl . M-HC1 , M-Clj , etc.). The major advantage cited was the ability to use the instrument to filter out interferences, reducing or eliminating the often lengthy sample preparation. Voyksner et a). (1983) also found MS/MS useful in analyzing complex samples for PCBs; however, they noted that interferences caused the PCB quantitation to be errone ously high In the first stage of the ms/ms analysis, [mj ions (e.g., 358 for hexachiorobiphenyl) were passed by the magnetic sector. The electrostatic analyzer was tnen scanned to observe the loss of one and two chlorines. Samples were introduced by direct probe. The valuts by MS/MS were 2 to 10 times larger than the GC/HREIMS values, The results obtained by direct probe HREIMS on the blood samples were higher than those obtained by GC/HREIMS. These results suggest that the direct probe HREIMS and MS/MS techniques are detecting more interferences, possibly dua to ajiphatics (cholesterol, etc.) in blood and fat (large [M-CH3] present) or from higher PCB homologs. The GC/HREIMS was presumed to be the more accurate method since it gave lower quantitative results, wnich indi cated less influence from the matrix. The accuracy of the analyses could not be checked since the true levels m the samples were not known a priprj. The advantages of soeed and less sample preparation were, in Voyksner's opinion, out weighed by the fact that tht results were consistently and unpredictably high and did not agree with other techniques. They further noted that GC introduction reduces the probabil ity of encountering interferences compared to direct probe techniques. 4. Flame ionization detection; The flame ioniza tion detector (FID) measures the change in electrical con ductivity of a flam* which is proportional to the number of charged particles in the flame. The GC column effluent enters the base of a hydrogen/air microburner and is burned. An electrode at the base and one at the top measure the cur rent. FID is the most commonly used GC detector because of its sensitivity and universality. Although some investiga tors navt used F10 for determination of PCB* in samples, it has generally been used only for calibration of response factors, to check purity of standards, or other method devel opment worn. HONS 223687 Ottefminaiion 239 HO has bee" used for determination of PCBs m en vironmental samples (Mirutam and Matsumoto. 1972; Modi et a) . 1976; Lao et al. . 1976. Onuska and Comba. 1980). Biros (1971) split the GC exigent to MO for quantitation and EIHS for identification Cook et al. (1978) and Zimmerli (1974) used TI0 to oetect &;pnenyi following dehydrocnlorination of PC8s. a technique termed carbon skeleton chromatography. Host of the HO applications have been in estab lishing response factors, cnarac ter t z i ng Aroclors. or other method development areas (weob and McCall. 1972. Aipro and pishbein, 1972a. ugawa et al., 1973, Oexter and Pavlou. 1976. 8oe and Egaas. 1979. Pavlou et al.. 1980; Aipro and Parker. 1980; Albro et a I., 1981; Stalling et al.. 1982). An example of the use of MO is presented in Table 7-v, where the molar responses of no and ECO were compared (Hutzmger et al.. 1974a. Safe. 1976). F10 is not selective enough for general application to PCB problems. 5. Photoipnization: The photoionization detector (PIO) uses a high intensity UV source to ionize molecules m the GC effluent. The ions are then detected at an electrode. The energy of the UV source (measured in electron volts) de termines the selectivity of the PIO. GC/PID was studied for possible application as a portable PCB monitor (Bostick et al., 1983; Oenton et al.. 1981) PID was found to be about 40 times more sensitive thin FID. However, using the standard 10.2 ev lamp, the PIO was not selective for PCBs in hydrocarbon matrices Better selectivity as obtained with an experimental 8 3 ev lamp. The lack of selectivity and problems with portability made the technioue impractical. Therefore, the approach *as not pursued further. 6. Thermal conductivity (TCP): Hirwe et al. (1974) used TCD to Characterize Aroctor mixtures. This ap plication is similar to many of the FID appl ications. GC/TCD was used to determine PCBs in ethylene glycol impingers used to collect the gaseous effluent from a bench-scale plasma arc destruction test (Barton and Arsenault, 1982). A 10 pg/10 ul detection limit for Aroclor 1254 was reported, which as ade quate to demonstrate > 99* destruction efficiency. Since TCD is neither selective nor sensitive, 't is not generally considered a detector of choice for PCB analy sis. HONS 223688 240 Analytical Chemistry of PCBs 0- Perch I On nat i 0n Perchlormation methods ere based on the exhaustive chlorination of the Diphenyl ring of the PCB congener*. Th major disadvantage of the perchlorination reactions is that Diphenyl can also be perchiormated. thus, the presence of biphenyl can lead to erroneously nigh levels of quantitation Quantitative analysis is typically accompli shed by GC/ECD (Figure 7-21) although GC/M$ iaentificat ion has been used in some instances. Perchlorination reactions are reportedly troublesome Because of contamination of reagents with dtca- ChIoropipheny1 or Orominated compounds (Trotter and Young 1975). Percnlormation reaction methods were first studied using antimony pentachI orige (Berg et a l. . 1972, Masumoto. 1972; Armour, 1973) and thionyl chloride in the presence of aluminum chloride (Nose. 1972) Armour (1973) reported greater than 90% recovery of PCBs by perchlormation and found the technique comparable to PGC/ECD comparison with Aroclor standards. Nose (1972) reported approximately 100% conversion of tn-, tetra-, and hexacMorobiphenyls to deca- chlorobiphenyI with the thionyl chloride system. Antimony Dtntachloride is apparently the most frequently used reagent. Hutiinger et al. (1973) studied trichlorosulfur tetrachloro- aluminate to quantitatively convert Aroclor 1254 to decacnio- robipherryl. A rapid perchlorination technique, which uti lizes an iron catalyst, has also been rtoorted (Steinwangter and Bruene, 1982; Stemwandter, 1984). Complete percMonna* t*on was reported in 10 min after addition of 10 mg iron pow der and 0.2 m(. SbClj and heating to 205C. One of the major disadvantages of perchlormation arises from plank problems (Trotter and Young, 1975). This has resulted in the need to carefully characterize perchlorination reagents prior to reaction (Huckins et al., 1974), The other major disadvantage of perchlormation is the con version of biphenyl to decachlorobiphenyl. Ch1orine*37 la beled perchlorination reagents have been studied as a means to clarify this problem and at tha same time distinguish the contribution of various PCB homo logs to the final decacnlorobiphenyl by computer assisted isotope dilution interpretation (Burkhard and Armstrong, 1981). This technique, although unique in approach, requires optimum reaction and MS condi tions for successful analysis. A recent study claimed that the perchlorination yield is constant regardless of the de~ gree of chlorination of the starting material and that a con stant factor (0.9X) could be used to convert the gecacnlorobiphenyl mass back to the original commercial mixture (Takamiya, 1983). This method was reported to be an accurate MONS 223689 N) / 21. '(it/tCD Chromatograms of Arotlur 1?64 Heltue (tuii) <tij Alter Perchloriualiott (Bottom) 1 lie sample was chromatographed on a 6 (L H im glass column coniaining 4% St * 30 on acid*washed Clirumusurb W 60*80 mesh al 26U*C with a nitrogen carrier gas at 60 *l/*in Hrpn tiled, with permission, from Hullinger et al. (19/4,i), copyright 19/4 tiy CRC Press, [m. , Hoc * Halmt, i lurida HONS 223690 242 Analytical Chemistry of PCBs and rapid screen for PC8$. PercMorination has been uied successfully for numerous studies in recent years ({.eoni et al., 1976a; Vannucchi et al., 1976; Crist andMoseman, 1977; Haile and Baladi, 1977; Margeson, 1977, Hes et al., 1977 Brinkman et al., 1978; Stratton et al., 1978a,b, 1979; kohl I et a 1. , 1979a; Hes and Davies, 1979, Robbins and Hilltute, 1979; Albro et al., 1979; Trevisani, 1980; Sherma, 1981) l. Carbon Skeleton Chromatography Carbon skeleton chromatography is based on the de chlorination of PC6s to biphenyl. Catalysts for the dechlor ination are typically platinum or palladium. The disadvant* age of carbon skeleton chromatography is that background levels of biphenyl in the sample extract will yield errone* ously high concentration* of total PC8* a* noted for perchlorination. Also, since the product of dechlorination is biphenyl, mass spectrometry must be used to reliably identify the compound, especially in extracts from complex matrices. Quantitative carbon skeleton chromatography by catalytic decomposition of the PCBs over platinum or pal la* dium to biphenyl has been discussed in three articles (Berg et al., 1972; Zimerli, 1974; Cooke et al., 1978). Zimerli (1974) and Cooke et al. (1978) studied conversion of PCBs as well as halogenated terphenyls, naptha lents, dioxins, furans, and DOT. Effective catalysts were found to be effective as 3% palladium at 305C and 5X platinum at 180C. Reaction products for the various compounds were identified by GC/HS. III. THINHAYER CHROMATOGRAPHY Thin-layer chromatography employs a liquid as the mobile phase and a thin layer (e.g., 100*250 pm) of solid ad* sorbent as the solid phase. The thin layer is generally ad* hared to a glass plate for mechanical stability. The TIC plate is spotted with the mixture solution near one end. The plate is then placed vertically, spot down, in a developing tank containing a smell amount of the mobile phase in the bottom. . The mobile phase climbs the plate by capillary ac* tion and draws components of the mixture upward. Since the components interact with the mobile phase and adsorbent dif* ferently, they migrate at different rates, thereby effecting the seperetion. The different components of the mixture are subsequently detected as spots either visually or with an optical scanner. Occasionally derivatizlng reagents are used to enhance visualization. Compounds are identified by com parison of the height they climb the plata (Rf) with the R^ of authentic standards, preferably run on the same plate. Quantitation is generally only approximate and is done t>y HONS 223691 Determination 243 comparison of the '"tensity of the color with that of a stan dard. TCC is discussed in more detail in most analytical chemistry texts and many monographs. One example is Stahl (1969). In addition to its use as a cleanup technique (Chapter 6), TIC has been used as a determination technique TIC was used extensively in early work (latter 1960$, early 1970s) because h(>{,C was not readily available and the GC techniques were not wel 1 -developed. Host of the early TLC reports were normal phase (silica gel) and included elaborate cleanup steps to remove interferents (e.g., oxidation of DOE to a benzophenone derivative). In the mid-1970s when packed column gas-liquid chromatography/electron capture detection (PGC/ECD) became the method of choice, emphasis on TLC meth ods dwindled. Several articles have been published which take advantage of modern TLC. techniques: high performance TLC, two-dimensional TLC, reverse phase TLC, and new detec tion methods. TLC has been shown to be an effective tech nique for determination of (Aroclor) PC8s in a wide variety of matrices. The advantages included its ease of use and the simplicity of the apparatus. The disadvantages include lack of resolution, moderate sensitivity, and low specificity. A. Historical Perspective TLC analysis of PC8s was reviewed by Fishbein (1972). TLC is included as an alternate technique for "semi quantitation" analysis of PC8s in human adipose tissue in EPA manuals (Watts, 1960; Sherma, 1961). It is also included in the Association of Official Analytical Chemists methods for confirmation of identity (AOAC, 1980a,0). TLC is mentioned by the Food and Orug Administration (1977) as a technique which they fael may also be useful. The TLC properties of commercial polychlorinated terphenyls have also been investi gated (Oe Kok et al., 1982). Since the publication of a TLC method for PC8s by Mulhern (1968) and Mulhern et al. (1971), several researchers have used a similar method for analysis of PCBs in food (Stijve and Cardinale, 1974), animal feeds (Westdti and Horen, 1970), food packaging (Zimmerli et al., 1973), bald eagles (Begley et al., 1970), Aroclor mixtures (Willis and Addison, 1972), animal tissue (Collins at a)., 1972: koeniger et a 1., 1976; Bush and Lo, 1973; Hattula, 1974b; Mes et al., 1977), human adipose tissue (Price and Welch, 1972; Lucas et al., 1980), human milk (Savage et al., 1973a, 1973b; Mes and Oavies, 1979), soil (Piechalak, 1984), and oil (Stahr, 1984). Many of those researchers employed TLC in conjunction with other techniques such as GC/EC0, Often, TLC has been used as a qualitative confirmation technique. MONS 223692 244 Analytical Chemistry of PCBs Bruggeman et at. (1982) used reverse phase TLC (Cl8 bonded phase) to study the relationship between PCS retention and hydrophobicity (water solubility and octanol-water parti tion coefficients) Anomalous behavior was observed for ortho-s ubstituted PC8s relative to other PCBs, chloroben zenes, a'kyIbenzenes, and polynuclear aromatic hydrocarbons The authors attributed the results to the non-planarity of the ortho-substituted PCBs, which apparently reduces the ability of the solute molecule to interact with the sta tionary phase Several developments have improved the technique Circular TLC reportedly improves sensitivity by an order of magnitude with a PCB limit of detection of about 0.05 pg (Koch, 1979). Fused glass TLC has been reported as yielding longer plate life (Qkumura et a 1. , 1973). Proper selection of the solid phase and eluting solvent permit separation of Aroclor components into discrete bands, as shown in Figure 7*22 (Brinkman et al. , 1976a). Reverse phase (Figure 7-22) gives better resolution, but norma) phase is more convenient and less time*consuming. Reverse phase TlC has been reported to yield better separation of PCBs from interferences (OeVos and Peet, 1971; OeVos, 1972; Stalling and Huckins, 1973: Brinkman et al., 1976a). An impregnated silica gel plate has been reported (Bergman et al., 1976) which improves selectiv ity apparently on the basis of ion-pairing. The use of sur factant micellar solutions as the mobile phase is certainty novel and reportedly has potential for separation of chlor inated aromatics, including decachlorobiphenyl (Armstrong and Terrill, 1979). Improvements in detection have included an AgH03 spray followed by UV irradiation (OeVos and Peet, 1971, DeVos, 1972; Kawabata, 1974) and fluorescence (Kan et ml, 1973; Ueta et al., 1974; Stahr, 1904). A two-dimensional TlC method was developed which barely separated the DDT analogs from PCBs, as shown in Figure 7*23 (Fehringer and Westfall, 1971), This last reference points to one of the major problem* with TLC determination of PCBs. Many common inter ferences (e.g. , DDE in biological tissues) have similar elu tion characteristics and are not easily resolved. One common technique for remove) of ODE prior to TLC is oxidation of the DOE to dichlorobenzophenone with chromium trioxide or other oxidant (Biro* et al., 1972; Sherma, 1901; Watts, 1900; Collins et al., 1972). Thielemann (1976) reported separation of PC0s from ODE on paraffin-impregnated Kieselguhr 9 plates. Quantitation can be improved with the use of a densitometer (Stahr, 19B4). Aever$e*phaa TLC was performed on C,a plates with methanol/water (95:5) as the eluting sol vent. A limit of detection of 10 ng was reported, with St repeatability in the linear quantitation range of 1'4 pg. HONS 223693 Determination 'O (=3 C=3 E3 G3 ao E3 Ii7t iIM t?? '?*! <?V '7*0 CD CCD |----- ) m c=3 c=3 r--i CZ) a =3 <=> 245 0 fl fOflO 4* 737 '7*7 >7* '?V 7*0 \?M 17V I70 17*1 Tigor* 7*22. TIC of Aroclors 1221 Through 1268 in Thr** Systems (a) Silica gel/n*h#xane; (b) Kieselguhr impregnated with par* affin oi1/acetonitrlle*m*thano1*wat*r (8:9:3), (c) Kieselguhr impregnated with paraffin oil/acetonitrile-methanol-acetonewater (20:20:9:1) Reprinted, with permission, from Brinkman *t a). (1976a); copyright 1976 by Elsevier Science Publishers, 8.V. MOWS 223694 246 Analytical Chemistry of PCBs AP`*00 * rv S* ?i. 0< i DDT ?S f* *- o 8* ti ! I l i 1 1 W'l % l J- . I _J____ aroc for DOT AnOJOQS AP'-OOe o.o' OOr p.p' DO1 p.p-* roe Keitno"* Figure 7-23. Two Dimension*] HC of Aroclor 1254 and OCT Analogs on a Silver Ntrate*Impregnated Silica Gel Plate The samole was spotted at the intersection of the two oasneo lines and several standards along the top third of the vert ical dasned line. The plate was then developed (from ngnt to left in this figure) with n-heotane until the solvent front had reached 10 cm, as denoted by the double vertical line. The plate was then turned 90* to the orientation shown, additional standards spotted along the bottom dashed line, and the plate developed with acetone/n*heptane (2 981 to the horizontal doudle solid line. The Aroclor 12b4 from the sample is within the dashed oval. The DDT analogs from the sample are in a diagonal line to me right and oelow me Aroclor 1254. Reprinted, with permission, from Fehringer and Westfall (1971); copyright 1971 by Elsevier Science Publishers. 8.v. MOMS 223695 Determination 247 8. Comparison to Other Techniques Two studies (Bush et a l. 1975. Collins et al . 1972) compared HC and GC/ECD In Doth studies the PCB val ues oDtained were comparable, although m the study Dy Busn et al , the HC results were generally lower than GC/ECD. Lucas et al. (19B0) reported a statistical analysis of semiguantitative determinations of PCBs in numan adipose tissue generated Dy tne EPA's National Human Monitoring Pro gram (Kutz and Strassman. 1976) during Ft 1972 to 1976 Re sults were reported only as ranges (not determined, < 1, 1 to 3, and > 3 Dpm) for 5.25 9 samples. The EPA T lC tecnmoue (Watts, 1980; Sherma, 1901) was used m this study through November 1974 and a GC/ECO technique involving a single PCB peak quantitation was used thereafter. A total of 3.802 HC results and 1.457 PGC/ECO results were comoared and found to be not significantly different. Reverse-phase TIC compared favorably with GC/ECD for the analysis of PCBs in transformer oil in the 4-65 ppm range (Stahr, 1984). The difference in the results of the two methods averaged i 20X. C. Current and Potential Applications TIC lacks the congener resolution of GC, so it is not apolicable to detailed analysis for individual PCBs However, the low setup and per*analysi$ costs (no capital eouipment) and rapid analysis make *t ideal for screening samoles wnere a simple "yes'' or "no" answer for total PCBs is sufficient. Examples could include screening of industrial products for by-product PCBs and screening of soil or haz ardous waste samples for PCB contamination. In samples where PCBs are uoiouitous. sucn as human adipose, TLC may be of less utility, since more detailed Qualitative and Quantita tive information is generally sougnt. However, it should be noted that tne LOOs Quoted for TLC are not as sensitive as loose for other techniques, so it will be less applicable where trace level analysis is reQuired. IV. HIGH PERFORMANCE LIQUID CHROMATOGRAPHY High performance liquid chromatograohy. also called high p'ressure or nigh speed liquid Chromatography (HPiC). is essentially an instrumental version of the common open column chromatographic techniques used for sample cleanuo (see Chapters). The instrumentation consists of a pumping sys tem, injector, separation column, and a detector. All com ponents are linked by tubing, so the separation and detection MONS 223696 246 Analytic*! Chemistry of PC0$ are done in One continuous operation. the separation may based on lQuid*solid partitioning ( g . hexane on get). t iQuid-1 iQuid parti Honing (e g. , bonded alkane column* such as Ci,). sue exclusion (gel permeation). or chemice' functionality interactions (eg., amine columns) LQuio- soiid and 1 lQuid-1'Quid chromatography ere collectively kno-r* as adsorption chromatography, since the interaction with the stationary phase occurs at the surface. Separation of an- alyt*s by adsorotion cnromatography may be effected usmq either of two modes of operation controlled by tne nature o' the mobile phase: normal or reverse pnase. In normal phase adsorption chromatograpny, the mobile phase or solvent (e g . hexane, methylene chloride, benzene) is less polar than the stationary phase (a.g.. silica or alumina). Reverse phase chromatograpny utilizes a more polar solvent (eg . ater. acetonitrile, methanol) relative to tne stationary phase (e. g. . chemca i ly bonded C* or Cn* silica gel). Common detectors include ultraviolet (not very leclive), fluorescence (somewhat selective), and electrochem ical (selective, depending on compound classes). Several other detectors are employed less commonly, including mass spectrometry. Compounds are identified by their retention time (RT) when compared to that of a standard and by detec* tion with a selective detector. The intensity (height or area) of the peak is used for Quantitation by comparison to the response obtained from a standard. HPlC is discussed in detail >n most analytical chemistry teats and in many monographs. Two examples ar? Vost et a). (1980) and Snyder and Kirkland (1979) A. titerature Citations High performance liQuid chromatography (HPLC), with ultraviolet and other detectors, has been reported in the cheracterization of commercial PC0S, as a cleanup tecnmoue. and as a determination technique. Despue its general ap* plicabillty in analytical cnemistry, HPLC has not been as popular as gat chromatography for PCB analysis. The major reason 1$ that CC detectors, especially those selective to* ward halogens, exhibit much lower limits of detection. Since HPLC is basically an instrumental version of the column chromatographic cleanup technioues. described m Chapter 6, it is applicable both as a cleanup and a determi nation techniaue. Some researchers have exploited this and combined cleanup and determination into one step with HPLC (Hanai and Walton, 1977; Van Vliet et a).. 1979). HONS 22369? Determination 249 Krull (19?') discussed HPlC ano its utility as a cleanup technique, especially for removing similar chlori nated hydrocarbons s-cn as the 00T family. Lawrence ano Turton (1978) reviewed tne hPiC data on pesticides anc PCBs The>r review provides a useful taOulation of hPlc cn<-omaio* graphic systems (column packings, dimensions, moDile pnases. detectors) and elution volumes for 166 pesticides and PCBs Although hPlc has oeen used for measurement cf PCBs from a variety of matrices discussed below, this tecnniQue has not been used with any of tne standard procedures centi* f ied m Chapter 3. 1. Characterization of commercial mixtures Sev eral authors (TrTn*man e"t a I. 1976a,b; vei th ana sti, 1976; Albro and Parser, 1979; Brinkman and Oe Vries. 1979) nave used HPLC in cnaracteruation of commercial PCB products or estaolishing the cremical behavior of PCBs Krupc*< et al. (1977) used hPLC/Uv and hRGC/FID to characterize frac* tions obtained by vacuum distillation of an Arodor 1C-C mix* ture. The hplC separation was performed on silica ge <th n-pentane as the elution solvent. Figure 7*24 illustrates the chromatography and also the effect of different uv wave* lengths on sensitivity. About 20 congeners were identified in this and other fractions by comparison of retention times to. those of authentic standards. Brinkman et al. (1976a.b) used a similar system to characterize Arodors and listed re* tention times and UV oata for SI congeners. Kaminsky anc Pasco (1978) used reverse pnase (RP) HPtC/UV to characterize Arodor 1221. 1016. and 12S4 Tne retention times on a uBondapak Cia column with a -ater/ acetonitrile gradient ano relative response at 2S4 nr reported for 48 congener* Figure 7* 25 illustrates tne separation power of S? hPLC. Clearly the reverse orase *s mucn better at resoi.mg PCBs than normal phase d'gure 7-24). Issaq et al. (1984) also used a C,B bonoed co'-nn to obtain an RP HPLC/UV seoaration of Arodor 1254 into IS oeaks. Brinkman and Oe Vries (1979) used silica ge and alumina columns with n-nexane as the eluent to characte-'ze a variety of ha)earoat"ics. including PC8s, relating cnr^mato* graphic behavior to structure. Planarity and linear'ty of the molecule were founo to affect adsorption on alumina, but not silica gel. The presence of substituents ortho to each otner or the central C-C bond promotes retention on both ad sorbents. Veith and Austin (1976) found that the HPtC reten* tion tine on a Ct$ column with methanol/water eluent was pro* portional to the octanol/water partition coefficient MONS 223698 250 Analytical Chemistry of PCB$ mifl F>gure 7-24. mPlC Chromatogram of PCBs with uv Detection at Two wavelengths (205 nm and 254 m) The sample was th last fraction (No. 70) from fl'iUl'liUon of Aroclor 1242. A 25 cm x 4 7 mm 10 glass column was picked with 5 spherical silica get. The solvent -as n*pentane at 40 *i/min. Reprinted, with permission, from Krupcik *t at. (1977), copy* right 1977 by Elsevier Science Publishers B.v. HONS 223699 Determination 251 ui -j ioo cr H-- z Ho-- UJ 90 60 4 12 20 28 36 MINUTES Figure 7*25. Reverse Phase HPiC/UV Separation of Aroclors 1221. 1016. ana 1254 (1.1.1. w/w/w) m Te;rahydrofuran on a uBondapak C,* Column Monitorec at 234 nm Initial conditions. 40* ater-aceton < tn ' (9:1) ana 60S water-acetom tn le (1:9); final condit'c-is. 100S wateracetonitrile (1:9); gradient time, 40 min, flow rate, 2 *1/ min; injection volume, 10 uL; amount injected, SO ug total. Reprinted, with permission, from Kaminsky and Fasco (1978); copyright 1978 by 1stvier Science Publishers B.v. Recently, high resolution HPlC .s<ng capillary or micropacked columns has revol utioni zed the *eso1ving power of HPlC. The pioneers in this field, lshii a^d Takeuchi (1983) have illustrated the high resolution RP HPlC of PCBs. as Shown in Figure 7-26. This is by far the "ighest resolution HPlC chromatogram of those in tne literat.re reviewed. The high resolution, however, is achieved only it a cost in tune. The analysis in Figure 7-26 took about B ~r to elute all of the PCBs. HONS 223700 252 Analytical Chemistry of PCBs figure 7*26. High Resolution Reversed-Phase HPiC/UV Chromatogram of PC0 Mixture Containing 48t Chlorine The column was a 1 S m x 0 26 mm ID fused silica capillary packed th 5 urn silica 00S SC-01. Acetonitri ie/water (85:25. v/v) was pumped at 0.6 yl/min. The sample -as St PC0 >n acetonitrile; 0 2 pi was injected. The UV Oetactor wave length was 254 nm. Reprinted. with permission, fro* Ishii and TakeuChi (1983); copyright 1983 by Elsevier Science Publishers B.v. De Kofc at ai (1982b) used HPIC to characterize com mercial polychlorinated terpnenyls (PCTs). Hernangez and Walton (1982) reported the retention volumes of polychlori nated btphenylols by RP HPlC/UV using a C;* column and methanol/water as the eluent. HPLC has been used as a cleanup technique prior to gas cnromatograpnic determination (Aiuetmul l*r. 197S; Dark and Crossman. 1973. Rohleder et al . 1976; krupcik et a'., 1977; Oolphin and willmott. 1978). More recently it has been HONS 223701 Determination 253 utd on a oreoaratwe scale to clean uo waste nd transformer oils prior to hRGC/ECD de termi nat i on (Anonymous. 1982a; Chester et a 1. 1961). In tne course of these investiga tions. the researchers noted tnat the HRCC/ECD limit of de* tect'on as aoout 100 times ioer than the hPlC/UV limit of detection. 2 Trace ana)ysis As HPLC Became increasingly pooular in the early 1970s. Eisenoeiss and Sieper (1973) oer* formed preliminary investigations of the use of hplC for oes* node (and PCB) residue analysis. They concluded that mPlC can be regaroed as "an alternative or supplementary method to conventional methods suen as gas chromatograony," and also would Be applicable as a confirmatory analysis. Electron capture detection of HPtC effluents has been described (Willmo11 and Oolphm, 1974) for the analysis of PC8$. The lOQ of HPLC.'ECO was reported to be abogt 10 times higher tnan for GC/ECO in a study of decachlorobiphenyl following per* chlorination (Brinkman et al., 1978). Room temperature phosphorescence in liguid solu* tions (RTPl) was used as a RP HPlC detector for PC8s (Oonkerbroek et a)., 1982. 1983). Detection limits were re* ported for nine congeners ranging fro* 0.21*5.6 ng. Orthosubstituted PC8s are poorly detected, so the technique may be useful for qualitative identification of compounds when used in conjunction with UV detection. Stalling et al. (1980b) gave a preliminary description of an HPlC/MS (presumably the chemical ionization MS mode) system for rapid screening for PCBs . Hanai and Walton (1977) developed an HPiC/UV method for determining PC8s in water. No LOO was determined, but good recoveries were obtained for 250 yg/i of Aroclor 1232 spiked into distilled water. The water was oumped directly through the HPLC system and the PCBs subsequently eluted by gradient elution. A similar application (Van Vliet et a).. 1979) used an HPIC precolumn to concentrate PCBs from water and then elute them onto the analytical column for separation and determination. The example presented was for 20 ug/ 16.5 ml of water or 1,200 ug/l. SeMiardo et al. (1979) developed a RP HPLC/UV pro cedure for PCBs in oil and compared it with a PGC/ECO methodThe HPiC method was judged suitaole to approximate, but not quantitate, the PCB content. Compared with GC/ECO methods, the RP WPlC/UV was termed rapid, convenient, and aoplicable to routine analysis. Klimisch and Ingeprigtson (1980) re ported a RP hPlC/UV method for determination of PC8s in polyQimethy1si1oxane (silicone) fluids. PC8s were extracted with HONS 223702 2S4 Analytical Chemistry of PC0j acetonitrile and then injected on a C,, column with acetom. trile/water eluent. A method detection limit (HOl) or iqq ppb and repeatability of less than * 4% at the Q.1-3% level were reported. A PGC/ECO metnod had an MOl of 25 ppb ana was judged to be preferable for low level analyses ana for r0g. tine screening where a single dilution is the only prepara tion reoui red. For PCB levels over IX, hPLC was recomenaed for Quantitative work since the serial dilutions required to get within tne PGC/ECQ linearity are wore time-consumi r>g Seidl and Ballschmiter (1979) used silica gel hplc/ UV to detect biphenyl after denydrochlorination of PCBs m soil and olive oil. A detection limit of 100 ng absolute was reported, which translates to about 0.05*0.5 yg/g depending on sample sue and other factors. A simple, rapid method for Quantitation of PCBs re moves interferences by the 00T family by oxidation to dichlorobenzophenone and then determination by normal phase HPlC/UV (Chiosi et al., 1982). The PCB detection limit (as Aroclor 1242) was reported as 2.57 ng. The precision of the hplc step was in the range of t 2%. The method was applied to snails and tuna with no observed interferences. B. Current and Potential Applications HPLC has found little use in analysis for trace PCBs in environmental samples. With the shift toward analy sis of commercial products and assessment of transformer anq other fluids for PCB contamination (often at the high ppm to percent levels), HPLC should be more useful. The poor inher ent sensitivity of most HPLC detectors is partially compen sated for by the large injection volumes (often more than 100 uL). Another drawback of HPLC is that the specific detectors available for GC (eg., ECO and MS) are not as widely applied to HPLC. Thus, most applications have utilized the UV detec tion, which is not very selective. Perhaps the greatest po tential advantage of HPLC is when it can be used as a onestep cleanup/determination technique. This could be easily automated to provide PCB analysis with virtually no labor costs. Sample matrices which are much different from PCBs, such as water, would be particularly amenable to tnis ap proach. V. nonchbohatogbaphic hethoos This section presents a variety of aiscel1aneous methods reported for the determination of PCBs. Some of the MS techniques (notably hREIMS and MS/MS) are used either as GC detectors, or as stand-alone techniques with direct probe HONS 223703 Determination 255 sample introduction. Both appi ications ir discussed in in* respective subsections above. While many of the nonchromato* graphic techniques are of greet use in characterwing PCBs, few of them nave the reouireo specificity ana sensitivity for trace determinations. A. Nuclear Magnetic Resonance (NMR) Spectrometry Wilson and Anderson ( 1973) used both 1 *C and 1M nuclear magent'C resonance (NMR) to characterize the cnemi stry of selected PCBs. No attempt at analysis of real sam ples was made. Levy and Hewitt (1977) reported the analysis of PCB mixtures by l3C NMR, but noted that the technique was not as useful for higher homologs. Hutzmger el al. (1974a) included a discussion of the NMR characteristics of PCBs m their review book. Synthetic congeners have been character ized by proton NMR (Hullin et al., 1981, 1984). 0. Infrared (IR) Spectrometry Hutzinger et al. (1974a) discussed the infrared (IR) spectral properties of PCBs. w*pb and McCall (1972) used IR and other techniques to identify 24 PCS congeners m Aroclor 1221. The spectra of 14 pentachlorobiphenyls and two trichlorobiphenyls were studied in detail by Nyquist et al. (1983). Spectra were obtained on a Fourier transform infra red spectrometer (FUR) using the diffuse reflectance tech nique. In addition to spectra, major peaks were assigned to the various bending and stretching modes and the group fre quency contributions presented. The authors noted that this data base should be useful in the identification of other congeners. Chen and Gardner (1983) used the higher sensitivity and data manipulation capabilities of FTIR to identify and quantitate the individual congeners in mixtures. The metnod was applied to fractions collected from a gas chromatograph Up to three components were accurately identified and Quanti tated. FTIR has been used as an on-line GC detector (Erick son, 1979J and could probably be applied to PC8 analyses, where the concentrations are sufficient and the identity of individual congeners is needed. This technique would be es pecially applicable as a confirmatory technique. FTIR has been studied as a field-usable instru mental technique for rapidly determining PCBs in transformer oil. (Nordstrom, 1983; Nordstrom and McIntosh, 1981). For regulatory purposes (EPA, 1979d), transformer oils must be categorized as "clean" (< SO ppm), "contaminated" (SQ-SOO ppm), or "PCB-containing" (> 500 ppm). Transmittance spectra HONS 223704 258 Analytical Chemistry of PCBs are collected and the concentration determined by a leastsquares fit of the absorbance to a standard curve. In order to clean up the sample sufficiently for reliable measurement in the 50*500 ppm concentration range, an automated dimethyl formamide extraction and concentration apparatus is attached to the FTIR spectrometer. The entire procedure can analyze a sample in 10 min with t 10* accuracy in the 50*500 ppm range. The technique was judged impractical and further research dis continued (Hinganori, 19B4). A filter ]R instrument has been studied for use as a portable field monitor (Oenton et a 1. . 1981; Bostick et a 1., 1983; Denton and walker, 1983). The authors selected IR because of its ability to detect PCBs in the presence of min eral oil. In fact, mineral oil is the well-known Nujol used to mull solid samples in classic infrared spectroscopy. The authors found the 8.5 pm (1,180 cm >) and 9.2 pm (1,090 cm*1) bands selective for Aroclor 1260 in the presence of mineral oil or trichlorobenzene (a common component of transformer askarels). The major limitation of the technique was the high limit of detection-*500*l,000 pg/g. The authors also used IR to detect PC8s in soil. The PC8s were extracted from the soil matrix with a volatile solvent (eg., acetonitrile) and then spotted onto the window of a multiple internal re* flectance (MlR) cell. After the solvent had evaporated, the absorbance was measured. The authors were able to detect a "few dozen micrograms" of Aroclor 1260. C. Radioimmunoassay AlDro and coworkers reported preliminary results in the development of a radioimmunoassay (RIA) method for PCSs (Albro et al., 1979; KohH et al. , 1979a; Luster et al.. 1979, 1981). The evidence indicated the feasibility of em* ploying radioimmunoassays for determining the Aroclor number and concentration in environmental samples (Luster et al., 1979). The assay required an antistrum for each isomer but was termed fairly specific. A radioimmunoassay was developed capable of deter* mining Aroclor 1260 in milk at levels of from 20 to 80 ppb and in blood from 2 to 16 ppb (Newsome and Shields, 1981). The values obtained by radioimmunoassay correlated well with those determined by gas*Hquid chromatography but were up to 25* lower. Antiserum was produced in rabbits and was see* cific for 2,2'.4,4',5,5'*hexachlorobiphenyl. It cross- reacted with congeners and isomers in Aroclor 1254 and 1260 to the extent that a 20* decrease in binding was observed with 0,1 ng of either mixture. The method required prelim* inary cleanup of the extract on alumina. HONS 223705 Determination 257 0 Other Techniques Interrupted-sweep voltametry has been applied to the identification of PCSs, yielding positive identifications (Farwell et al., 1975). Plasma Chromatography has been re ported to give characteristic Qualitative data for PCBs (Karasek, 1971). One report utilized neutron activation analysis for the determination of PCBs in dosed rats (Manri et al., 1971). Low temperature luminescence has been pro* posed as a simplified method for the identification and ouan* titation of PCBs (EPA, 1972; Brownrigg and Hornig, 1974, 1976). The limit of detection was reported to be as low as 0.01 ppm. VI. CONFIRMATION Confirmatory techniques have been used frequently in PCB analysis. The term confirmation may be loosely de~ fined as any operation performed to increase the confidence of the results beyond the primary analysis. Qualitative con* formation is much more often reported than quantitative con* firmation. Confirmatory techniques involve variation of the same technique (PGC/ECO on two dissimilar columns), confirms* non by a lesser technique (PGC/ECO with TIC confirmation), or confirmation by a more advanced technique (PGC/ECO with PGC/6IMS confirmation). A review on confirmatory tests pre* sents a general overview of confirmation as it relates to pesticides (Lawrence. 1981). A. Literature Citations Hutzinger et al. (1974a) reviewed confirmation. While mass spectrometry was briefly mentioned, most of the discussion centered on perchlorination. Table 3*1 lists all of the standard methods and notes the type of confirmation suggested. All of these confirmations are optional and qual* native. >s early as 1969. the need for confirmation of PCB findings was discussed (Reynolds, 1969). An exchange of com* ments following a presentation by Risebrough (1971) led to a proposal for confirmation, covering mass spectrometry, de* chlorination, and perchlorination. Price and Welch (1972) are typical of many early investigators who backed up their PGC/ECO analysis with a TLC confirmation (see also the stan* dard methods; AOAC, 1980a; FDA, 1977). Hannan et al. (1973) utilized a cumbersome ultraviolet irradiation method to con* firm PGC/ECO results. A dual GC to heart-cut a chromatogram and separate the decomposition products from the first ECO has been proposed as a confirmation technique for pesticides HONS 223706 258 Analytical Chemistry of PCBa and PCBs (Aue ana $huoh*r>d*r, 1978). A nPLC/room temperatur* phosphorescence system has oeen reported whicn not only pf0. videt a second detection m addition to UV, out also aids in cent!f'cation of isomers, since ortho*substiluted PC8s jr* ot detected by the phosphorescence technique (Oonkerproek > al . 1982. 1983). i ized a <variety of tech;:on in the ana lys >$ of ad'oose end mtU samples (Hes et at . , 1977, I960, Hes and Cavies. 1979). The methods include two q>s simi1 a r GC col umns . percMorinetion, and GC/EIM$. et al. (1972) anq tut: results . GC/E IMS Coninnat'on hat also been reported ( iaile and Balao i . 1977 . 'fichman et al.. 1978; Musial et a . . 1974;; Lucas et a i , '.980; Pastel et al.. 1960: Rodrigue; et al. . 1980; En Ckson et al.. 1983e) hREIMS nas been ret orted as a conirirmatorv technique (Safe et al., 197$. Safe., 1976; Husia 1 et al , 1974). Kueht et al. (1980b) used HRGC/NCIMS to qualitatively confirm their HRGC/EIMS PC6 identifications in fish. Hass and Friesen (1979), placing particular emphasis on polychlo* -mated dibenzodioxins, reviewed the advanced mass spectrometric techniques for bpth high sensitivity and high reli ability analysts; HREIMS and NC1HS. 8. Current and Potential Applications The choice of a confirmation technique deoenqs on ;:) the information content from the primary technique, (2) *.ne PCB and interferent concentrations, (3) the level of conlaence needed, and (4) availability of instrumentation Clearly, the confirmation technique must increase knowledge about the sample. Confirmation by GC/ECO after a successful analysis by GC/EIMS therefore maxes little sense, while te -everse may often make sense. The analytical technique must be sufficiently sensitive for the level of PCBs in the sam ple. This frequently means that GC/EIHS cannot be used to confirm residue levels in trace environmental samples. The higher the level of interferences, the more selective the confirmation technique must be. Even with the high selec tivity of MS, high levels of dissimilar compounds (e.g., an oil matrix) can totally obscure PC8s at the part-per-mi11 ion level in a GC/EIMS confirmation. The level of analytical confidence required can often be a political or financial de cision. In addition, it depends on the prior knowledge of tne sample. Oetection of PCBs at 10 ug/g in human adipose ov GC/ECO would not normally require confirmation, since this >s a typical level and tney are ubiquitous (Lucas et a) , 1982) HONS 22370? Determination 259 On tne other fiend, conf i rmat 1 on would most certainly be reai>irea if an Aroc) or-1 ike pattern were observed m e CC/ECO 'ftrometogre* of e commercial product sample -men should not be contaminated end had e negative essey for cniorme. With CCD detection of either GC or HRGC, second* column confirmations ere often <oorooriAte. All of the more eavenced ms techniques (nc|n$, h*EJm$. ms/ms), with direct probe or preferebly es GC semole introduction, ere useful confirmetion techniques. Quantitative confirmetion nes rereiy been noted m the litereture. Confirmetion of the auentitetion is elmost as imoortent es the confirmetion of the identity of the en* alyte. Not only cen mterferences mask or augment the oeak identified es e PCB. but calibration by e second technique is often sufficiently different to minimize systemetic bies Quentitettve confirmation cen be viewed es e oortion of e good QC program since it verifies tne reported values. VII SCREENING A. Screening for PCBs Screening techniques sacrifice the confidence in tne analysis for soeed end/or simplicity of eooeretus. Often a screening analysis orow ides only qualitative or semiquenti* tative information. Samples should be screened where immedi ate analysis >s needed, such as during an incinerator trial burn to mate sure that the RGBs are being destroyed, or nere most of the samples should contain no PCBs aoove the detec tion I'mit of either the screening or primary analytical technique and may oe efficiently eliminated oy tne screen 1. Chromatographic screening: As discussed ear lier. TlC, HPL?^ ana uC ail have application for screening samoles. In addition, the oerchlorination and caroon skele ton chromatography techniques can serve for screening sam ples Finally, abbreviated analytical procedures can be used to Quickly screen samples. An example is a PGC/ECO analysis of fish tissue with a Quick extract>on/cleanuo using minia ture chromatographic columns (erney. 1974a). Another aspect of screening is simole range finding. If there is a poss'Oility of an extremely high concentration sample, such as in transformer oil samoles or in hazardous waste samoles. very dilute or very small volume injections can orevent a catastrophic overloading of tne analytical system. MONS 223708 2eo Analytical Chemistry of PCBs 2. Total organic haiide: An increasingly popular screening technique 's total organic halide <TOX) or total organic chlorine (T0C1 or RCU. TOC1 values are reouired for incinerator testing for PCBs (EPA, 1979d). While TOX is one of tne 'east selective techniques since it detects "all" or ganic halides, it is Quite sensitive and can oe useful when there are low levels of other chlorinated compound* relative to the PCBs. TOX nave been monitored using a very short column (2.5 cm long) PGC/HECD method, shown in Figure 7-27 (Stanley et a I. 1982; Haile et a 1. . 1983a; Nulton et a!.. 1984), or extractioh/GC/EIMS metnod (Beard and Scnaum. 1978). Both emoioy a Soxhlet extraction of the XAD-2 resin from the modified Metnod 5 tram (EPA, 1977; Haile and Baladi, 1977). Tne TOX values for stack gas and fly ash from a power plant and an incinerator obtained by HRGC/EIMS averaged about 14% higher than the values obtained by the snort column GC/HECO technique (Nulton et at., 1984). It should be noted that these methods do not in fact measure total chlorinated organ ics. but rather semivolatile. gas cnromatographablt, chlori nated organics. The GC/HECD TOX measurement was applied to background air oarticulate, stack gas oarticulate. and ash samples from a municipal incinerator and a co-fired oower plant (Haile et al., 1983a,b; Nulton et al., 1984). values ranged from 0.9 to 46,000 ng/g. In water samples they ranged from 100 to 1,000 ng/L. Two techniques for total chlorinated organics in volve concentration of the organic halides on a sorbent trap, and reduction to HC1 at 9S0*C. In one system the MCI gas is detected by electrolytic conductivity (Model 610 Total Or ganic Halogen Analyzer, 0.1. Corporation, College Station, Texas). In tne other system, the HC1 gas is detected by microcoulcmetry (Mode) OX-20 Total Organic Halide Analyzer, Oohrmann Xertex, Santa Clara, California). Both techniques nve tne advantage over previously used methods in that vol atile, semivolatile, and non-volatile organic chlorides can ba detected. The extrection/GC methods detect only the semi volati le Organic chlorides. The electrolytic conductivity technique wes characterized by Bernard and Russell (1983). As shown in Figure 7-28, the analyses with the electrolytic conductivity technique are quite rapid and reproducible. Tn response is linear with concentration. The coefficients of variation at both PCS levels were less then ZX and about 2.6% for the blank. This technique features en optional dedicated data system. The microcoulometrlc technique was character ized by Berger (1984). 3. Chemical determination of total chloride: The classic organic reduction of organochlorine to free" chloride ion with metallic sodium has Paan used to develoo screening techniques for PCBs. The free chloride ion can De datacted by a chloride ion-specific electrode or colorimetrically. HONS 223709 Determination 261 figure 7-27 Total Organic Halide <T0>t) Analysis Using a Short Column PGC/HECO Th* staple IS-20 wt) is injected onto a 1-m column containing 2.S cm of 10% 5P-2100 on Ultrabond packing with a helium flow rate of 60 mi/min. The column temoerature -as 60*C for 3 min, then programmed at 40*C/min to 230C. The total area under the chromatogram is integrated and compared to the re* sponse for monochlorobiphenyl. Reprinted, with permission, from Nulton et al. (1964); copy* right 1984 py American Chemical Society. MONS 2237X0 262 Analytical Chamiatry of PCs* Tim*. Minutet Figure *-28. TOC 1 *eesure<eents of Aroclor 1248 using Electrolytic Conductivity tight tenc * injections (5 ut) ere shown. Reormteo >th permission, from Bernard end Russell ( 1983). HONS 223711 DtteriTi<nit*on 263 Using the C0i0ri*tric detection princio'e, in inPipensive. rapid, if ) 1 conte' nea tit Mt been Ofve'ooed for 1 ie Id* test mg irins'ort^r o') nmoles (Fisher et il.. 198*) tne ooject is to otifrmme wnemer the oil is "contaminated" ($0*500 opm). *ith PCBs and therefore requires soecial hin* olmg nq OiSDOSai m the United itates {ERA. ]979d). The tit (Chlor-N0i1$), developed for the Electric Power Research Institute ind merketea oy 0esil Corporation, it oased on the quantitative convert'on of the chlorine atom on PCBS to chlonOe >ons hiqn m turn are extracted into an aqueous to* lution and measured colorimetncal ly. Chlorine is converted io cnloriqe <ons Dy sodium salts formed by naonthalene to gether with the dimethyl ether of diethylene glycol ("digiyme") as stabi)i:mg ligand. The chloride ions are ex tracted mto an aoueous buffer solution and reacted witn a carefully controlled amount of dissolved mercuric nitrate Diohehy karoazone s added Reaction of any excess mercuric ion with the oiphenylcaroazone will form a vivid o>ue com plex. If the chloride ion content exceeds that taxen uo oy the available mercuric ion, the complex is not formed and the reaction mixture remain$ colorless to pale yellow The re actions are carried out in soft plastic test tubes containing premeasured reagents in breakable glass ampules Proper con trol of the samole sue and of the quantity of mercuric ni trate allows the plue-coiorlets response level in the mineral transformer oiV to be set at levels from a few oom to several thousand oom The lowest ratio of chlorine to PCB found in an as- kare) u 0 (Aroclor 1242). Therefore, an oil sample con taining lest man H opm cnlorme cannot contain more man $0 pom PCB A color response level set at 21 opm chlorine 'or me xit should assure that no contaminated oil (i e.. 50- $00 opm) gives blue responses Samples giving colorless re sponses can be cnecked by gas chromatography to determine nether they actually contain more than SO pom PCB. It has been estimated mat the use of a colorimetric test kit can reouce the number of GC/ECO analyses reduced to determine whether or not a transformer oil is contaminated by $0-60% (Walsh, 1983), `his would result in a significant reduction in cost of a monitoring orogram. . The test was validated Dy <0 utilities with a total of B24 samples tested. Using a 50-pom regulator cutoff. 27% of the samples yielded false positives and only 2.3% were false negatives when comoartd to GC/CC0 results, which were assumed to De accurate (Tahiliani. 1984). Minor manges m the kit and instructions promise to improve the accuracy o' the test. MONS 223712 264 Analytical Chemistry of 4 fluorescence x-ray fluorescence (*Sf nas been studied at a pCB screening technique wn*n #n .. ! like cn'orme it pomoerqed with **rays. electront a--e a,* lodged t rom nn*r o'-oua's, creating "hotti." These noi* are *aoidiy oy electrons fro* outer orpitals f!' energy difference Detween an inner and outer orouaT result* m the emission of a tecondary a-rjy *nen a no)e is f'lieo' This secondary *-ray it measured by xRf. McQuase (198?i snowed that XRF could accurately detect and Quantitate cnior. me down to a concentration equivalent to about 10 dd* or Arodor The tecnniQue cannot differentiate between RCBs *nC other cnlorme soecies (including inorganic chlorides) ih> total analysis time is about 5 min/ samo'e and tne instrument it small enougn (40 kg) for field use. The oouaoie en*iy2*T was used to test transformer oils at electrical substation* (Scnwaib and Marouez. 1982) Tne mam objective was to cate gorize the oils as "clean'' (< SO po*). "contaminated" (50-SCO ppm), or "PCe*containmg" (> 500 Ob*) for ERA regulatory 0ur. poses (ERA, 19790). Tne xRF results compared well witn those ootamed off-site by GC, although there were occasional fai** negatives. B. Screening for Interferences Samples may also be screened to assess the effec tiveness of cleanup before submission to a final determina tion tecnniQue such as GC.'CIMS. Tne oojective is to assets me overall level of chromatograpnable compounds, not to spe cifically detect PCBs. Background screening for sample* which .ill oe analyzed by a gas cnromatograonic technique <s best accomplished using wl.flame ionization detection (P.cn MO ' s a universal" detector and thus provides a relatives uniform response to all e'uting comoonents of the mixture Sntarferenca screening is esoecially apoi'cab'e for unfamiliar samples, when T>ajor interferences may contaminate tne analytical instrumentation. Indications for screening include: nighly colored samples or extracts; evidence of c>eanuo tecnniQue overloading; orecioitation on solvent evap oration; sample history (eg., solid hazardous waste of un< known composition); and matrices wmcn nave similar physical properties to PCBs (eg., oils). vlll. summary As discussed <n this chaote-, a wide variety of mstrumental techniques are available to determine the RGB con tent of a sample. The choice of the technique deoends on i numoer of factors, as presented in "Criteria for Choice of Techniques" at tne oeomnmg of tnis cnaoter For routine ,-ONS 223713 Dettmvnation 265 ana'yS'*. GC/1C0. GC/MECD, or GC/U*$ would prooat / oe most aOPfOOr>*t The selection of *GC Of H#GC deDe*0S On the nc*d f Or '$0<Mf soec'fiC'ty and, 10 $0*t etent, 'dividual preference Several screening techniques ay 0* aoolicable , f the orooao' 11 ty of *CB occurrence is low and tie natMx compo*' t'on permit their use TlC. TQX, CC/MO, snd GC/ECD are a*) candidate screening techniques under the 'ight cir cumstances Confirmation g*nerai'y involves eitne* reanaly- $is on a second colutin using tne same detector, steoomg up * n instrumental sophistication to mpr^.a the c.alitatwe reliability of the analysis. Thu*, 1 MS, HRElMS, "S/MS, and HCIMS *p often considered confirmatory techniques HONS 223714 8 DATA REDUCTION CUt* reauction is a key element in nmole analysis in tms steo, me analyst converts tne instrumental outout into information for tne user. Specifically, any PCBl pres ent in tne sa0es are identified and Quantitated. Depending on tne oetection ana outout system, data may oe oresented to tne analyst as analog chromatograms, numerical tabulations. MS extracted ion current olots, etc. Computers and integra tors can reduce tne analyst's worn in data acouisition and reduction: however, tne judgement of a Qualified analyst is critical to reiiaole data reduction. Tne imoortance of data reduction cannot be over emphasized. esoecially with PCBs. In a col laoorative study. Delfmo and Casty (1979) reoorted an RSO of IS.6% for Di rect injection of an Arocior 1242. They "Oted tnat the PCC/ ECO analysis aooeared to orovidt tne principal source of var iation in tne overall determination. Similarly, Enckson et al. (1903c) noted tnat data reduction constituted about oneinird of tne error associated 'tn a hSGC/EIMS oroceoure for by*oroduct PCB analysis. Set Cnaoter 10 for more detail* on Doth studies. Tn first task in data reduction is to Qualita tively identify the analyte, answering tne Question "is tne analyte oresent?" Quantitation can oe attended only after a coaoound has been identified, although the retired level of confidence in the identification can vary widely, as dis cussed below. I. QUALITATIVE A. The Importance of Proper Qualitative Oata Interpre tation The Qualitative asoects of the analysis are ail too often overlooked. Esoec'ally with complex mixtures of PCBs. aiffertnces m tne Qualitative assessment of a sample can 267 MONS 223715 268 Analytical Chemistry of PCBs dramaticaI 1y affect tne number o' peaks OuantUated Ou<litat've assessment 0' results depenOS to a Urge extent on semel* lye* for samples wnere the presence oi PCBs nas been we"*estebiished (e 9 . human or expose tissue) tne ouaiitj* tive buroen is not nearly so greet as for samples m hicn PCBs are not expected. The cleanup and determination techniques used to generate the data also o'etete the level and type of oata as* sessmnt needed. PCS-spec 1 f 1 c methods reduce the oropabiiitv of interference and ease the qualitative burden in som cases, tne cleanup involves a rather specific i'ou>d chro matographic separation which separates PCBs from most o^gano* chlorine pesticides and other potential interferences in addition, the u*e of specific CC detectors (C0, hCD) re duces tne probability 0' interferences and increases conn, dence >n tne identification. Better still. MS brovides soectra o' the eluant which mey be compared with those 0' autnntic comoounds to give higher confioence in the 'oentifica* tions. The retention time of the unknown should match that of a standard or at least be within a PCB window, hrqc gives much more precise retention times than PGC and increases Qualitative confidence. In the case of samples contaminated by commercial mixtures (eg, Aroclor), the pattern of enromatograohic beaks often resembles the pattern of a standard Tnis visual pattern recognition has been a common ouai'tatw* technique in residue analyses, especially when PGC/ECu '$ tne analytical procedure. For many analyses, Qualitative >dent1''cat'on 0' PCBs <s trivial. For examole. human adioose samo'es most assureoiy have a cnaractenstic PCS pattern n samoie after samole. In cases where the presence of PCBs is less likely, tne qualitative criteria should be established before the analysis, generally as part of the QA plan. To some ex* tent. Qualitative criteria are controlled by external 'ac tors: economics, politics, orgamrational oolicy. etc. For example, a regulated industry ny set relatively >ow Quali tative criteria, so that samples even suspected of containing PCBs win be properly disposed of. Also, if confirmation of suspected PCBs m a waste is more expensive than disposal, then furtner analysis is clearly not warranted, tne waste 'S simply labeled "PCB*contemmated" and shipped o'f for dis posal. hot only should the Qualitative criteria estaplisn limits (retention time windows, ion ratios, etc). Out mey should direct the analyst to alternate courses of action (consult supervisor, confirm oy alternate teenmoue. analyse Dy standard addition, etc.). MQNS 223716 Data Reduction 269 In addition to tne various gas chrm4t0gr jdmc njenl' 'Cation techniques discussad here, tmn-layr chroma* tograpfiy and nign performance liquid chromatography y'a'd oua.ntativa information, as discussad m Chapter 7. Mora exotic tacrfniQuas Sucn as specialised mass soectro*etrc techniques, fOuria r transform infrarad Spectro*etry , nd nu clear magnetic rasonanca spectroscopy ara not usad routinely for PC8 analysis and were discussad m Chapter 7. 8- lnterpretation of Retention Qata Regardless of the detector used, the retention time oata fro* a gas chromatogram provides the first dimension of information used to identify PC8s. Tne peaks must pa within tna PCS window oafora any of the other Qualitative criteria are applied, with ECO and hECO oati, the detector seiecuv* ily reduces, Out does not eliminate, the prooaoiiity tnal non*PC8 peaks will interfere with tna qualitative mtarprata* cion. with mass soeciromtric detection, the mass spectrum provides a second qualitative dimension, as discussed m Sec* t>on I C, below Only a few of the references using ECO or other analog detectors have mentioned the Qualitative criteria used in identification of PCBs. In PGC/ECO procedures, visual pattern recognition is normally the Qualitative technique Often two GC columns of different polarity are used to en* nance the confidence of the ioentificat'on. with hRGC data, individual congeners may oe identified oy use of retention time or retention mdex tables or oy comoanson to a cnar* acic'-ued commercial mixture Increasingly, formal computer ized oattern recognition routines are used to compare the PCS comoosu>on of samples. i. tow resolution Chromatograms. Ihf low reso'u* tion chromatograms generated oy frcc/fcb or PGC/mECO can oe comoared to the retention windows estaolsned witn standards (e'tntr congener mixtures, or commercial mixtures) Tne only other Qualitative assessment which can be made is comparison of the pattern with that of a commercial mixture. a repre* sentative qualitative criterion in tne literature that the chromatogram exhibit a "typical Aroc'or pattern" (Gordon el al.. J982; Giam et !.. 19?2; Ofstad *t al., i9?8; K'rshen, 1981a_b). for many purposes, visual pattern recognition is entirely satisfactory, However, the C8 mixtures m many samples do not resemole a single Aroc'oc mixture, so denti* fication is difficult Computerized pattern recognition nas oeen applied to the relatively Simple las* of identifying mcn Aroc'dr is MONS 223717 270 Analytical Chtmistry of PCfis present m transformer oi's and related samples (Coipy an P'Cker. 1983 ). The goal -as to mnmje both the anau*?0 time and operator ntervention with an automated fi*)0 'yrer (Coiby et a1 . 1983. Picker and Colby. 1983). An ,i. gontnm was wr>tten for tne dedicated microprocessor wh,Cfl identified PGC/ECO peaks m tne Aroclor retention windows ana tnen converted tne retention t im* miens i ty data pair* 1nl an n-dimens iona l vector The cosine of the angle of tni s vector m n-space -as calculated and compared ->tn tne cosine of tne angle for the various Aroclor standards Pur* ariQ major-component Aroclors m a sample were readily disting uished. Tne a'goritnm was unreliable for components oi than 20% re'at've to tne total amount of Aroclor. Tne au thors noted tnat visual interpretation was also jnreiiaou at this level lerman et a) (198?) developed an algorithm *c, analysis of eC8s >n transformer oils vmcn ca'cuiates concentration Of an unknown against standard Aroclors 1254, and 1260 us>ng potn the total area and a mean of f>* key oeaks for each An error factor is calculated and an "error score" reoorted. Tne analyst can then review tne oata and decide whicn Aroclor best fits the unknown The article does not present the routine in detail. Another routine (tea et a I. . 1983) to identify Aroclors 1242, 1254, and 1260 is designed to De used with common chromatographic data Systems (e g., varin Vista 401) and integrators (e g . Vinin CDS111). Peaks are identified by retention time and tnen <nte* grated. Tne peak areas are compared to those m tne stanoarg Aroclors by a ratio technique. Tne relative stanoaro devia tion of these ratios indicates how well the unknown matches tne standard. Statistical tests ("Q test') are also 'nco1-oorated to test for outliers, which can tnen be ei'mmateo from the calculation A novel data reduction approach is to treat a pGC/ CO chromatogram as a spectrum and use infrared spectral sub traction software to match the unknown to a standard(s) in an interactive mode. Gossman (1983) presented this conceot as applied to PCB-contammated wastes. Tne ability to reject peaks which did not fit with an Aroclor standard was used to fit "only the good data." Tne concept, used with discretion, has particular appeal in analysis of mixed or degraded Aro clors, After a subtraction of one Aroclor, tne residuai peak* are observable on a screen and the analyst can visually assess the data. 2 Hiqn resolution gas chromatograms a. Use of retention times and retention in dices: Several -esearcne'-s nave comoa'-eo retention t'* (RTs) or relative retention times (RRTs) between tne sample HONS 223718 Data Reduction 271 4nO an Aroc'or standard for PCS ' dent i f icai 1 on (webb 4nd McCall. 1972, Qnsuka and Comoa. 19*8, Erickson et at , I962t. p*iiw:ari t a' . 1983a.b. Tumstra etal.. 1980). Another ,denti f 'cat i on technique invouts use f one of the retention index (91) sch**s (e g , Kovats) Several publications con* taowUt'Ons of Rls of PC8 congeners as snown in table 7* I (S'ssons and Welti. 1971, Zell et at., 1978, Sal Ischmtter and ZtH, i960, Atbro et a) , 1981, Albro and Pishbem. 1972a.0, Hanneman, 1982). Since all 209 PCB congeners are not readily available, a scheme of predicting Bis has been developed based on the n*if-R1 values (see Table 7-11) for the various chlorination oositons on one of the oenzene pmQS Sissons and Welti (1971) first proposed this System, wmen was expanded upon and further validated by Albro and fishbfin (1972a) and Albro et a>. (1977). The use of half Bis permits the analyst to Qualitatively identify all 209 PCBs on the basis of their retention time, although the level of confidence m this identification has not been determined, us'ng state-of* the*art enromatograpfty. Ri measurement preci* s ion of i 0 052 h*s been reported for PCBs (Neu et a 1 , 1978), and w'th full optimization, precision of D 012 has been predicted (Neu and Zinpurg, 1979). b. Individual congener identification: Sev eral publications, dating back to the landmark1 -or* of Sissons and Welti (1971), concentrated on tne identification of PC8 congeners in commercial mixtures such as Aroclor or Chlophen (Tas and de Vos, 1971; Tas and kleipool. 1972. Armour, 1972, Willis and Addison, 1972; Paasivirta and Pitkanen, 1975; Jensen and Sundstrqm, 1974*. Neu et al . 197B, Zell et a) , 1978; Ballscnmiter and Zell, 1980, Pel)ixzan et al., 1981; Tu'nstra et al., 1981; Bush et al.. 1982, Ou'nker end HiMebrand. 1983 ) The objective of most of these papers -as to characterize the commercial mixture as an aid to Quan- tuation in ehvironmehta I samples cr for toxicological infor- nation The recent work by Bush et al (1982) exoaoed on previous work and assigned 72 peaks in a mixture of Aroc'ors 1221, 1016, 1254, and 1260 (2 yg/mt each). Where there were ambiguities *n previous work which they could not resolve, only the homo log is listed (eg.. Clj). They note that the confidence of the oeak identities differs, debenoing on availability of standards, number of isomers eluting in tne samm region, etc. They also note that the confidence m the assignments will increase with t'e as more standards become available and further work is done to corroborate the assign* mints Using the feur-Aroclor calibration mixture and tne peak tables. Bush et al. (1982) can identify all of me major and most of tne minor PCS oeaks found m environmental sam ples from the northeast United States. They state mat MOHS 223719 272 Analytical Chtmistry of PCBs " although chromatographic matching of tention parameters floes not necessarily constitute perfect authentication of peak assignment, several authors are reaching a consensus on the structure of compounos separatee on Apieion t (MuMm et al 1961. fiaMschanrer anfl ZeU, i960) and other phases (A1Dro et a). . 1981) we consider that the strut* tunes of the major peaks are now well enough estaolisned to warrant reporting the* ouantitative'y as descnoed here. This will enable the task of determining the toxicological significance of *-es*dues of PCB to oe started, a hopeless task wnen r.. suits are expressed m terms of Aroclor mixtures has been toe practice hitherto." For environmental'y flenvefl samples where specification of congeners is useful and where PC8 concentrations are verv low, this HfiGC/C0 method holds great promise Zell and Ballscnmiter (1960) interpreted any deviation of an environmental PCS pattern from the pattern of como)netions of commercial mixtures as the result of degra dation or weathering. These authors established mcn con geners are indicative of metabolism, or other degradation process for different types of environmental samples Th's method allows tne analyst to focus attention on those com ponents of interesfei ther because of their constancy from matn* to matrix, or because of their change with environ mental conditions. c Cgmcanson pf retention times on two hpqc columns Singer et al. (1983) used two HflGC ^oiumns (Gv-l and SE-S4) with ECO detection for both qualitative and Quan titative analysis The data from the two analyses were cor related and the following criteria supplied using a program written on the chromatograhpic data system: "1. The retention time of the peek must nave been within limits (usually s O.IX) pf the expected retention time, otherwise the peat was rejected. 2. If the peak for a given PCB was identified on both columns and the Quantities were within lim its (usually t 203). the average wes calculated and printed followed by the word 'confirmed.' 3. If the peak for a given PCB was identified on both columns, but the quantities were not within given limits, then the lower value was taken as tne result, followed by word 'interference' (we assumed HONS 223720 Data Reduction 273 that tn* ign<r vjlue was caused by an <mourity co* el ut mg wi th tne PCS) A. If th* pea* for a given PCB -as iOtntiffl on on* column only, the value was rejected and l dent i f i ffl by the words not PCS.' 5. Although th* capillary columns have very nigh r*soiv'ng power. so* PCBs could not b* re solved At all or could be resolved on one column only If thu h*pp#n*o. tnen the determined Quan tities of unresolved PCBs on one or ooth columns wer* summed up eng evaluated under identical cri teria. " d. Pattern recoqni tion: As noted *t th* Be ginning of this section, "oc/Scd data nave traditionally been evaluated by visual pattern recognition, in tn* bast f*w years some analysts nave used computerized pattern recogni tion. Bush et *1(1963) nave used a rather simple teenmoue to study differential concentrations of PCB congeners in ma ternal and fetal cprd blood. They used histograms of tne frequency of detection at different concentration intervals to compare the two matrices. They were able to detect sev eral congeners which are differentiated by the placenta. Gassiot et al. (1982) compared the Zobel and simplex comouter algorithms for the identification and quantitation of uo to three Aroclors in fish sample. The simplex routine -as judged easier and more flexible to use Ounn et el (1982) nave used a comouitr<:eg pattern recognition teenmoue to evaluate hPGC.'ECO oata on PC8s. hRGC/ECO data for 6S congeners m about ?00 samples of sediment, suspended sediment, benthos, and f*sn -ere examined using the Simple Classification py Analogy (S1MCA) principal components modeling technique. SIHCA performs a vector anal ysts of al) of the relationships (e.g., concentration of a congener m water) and derives a set of artificial coordi nates which best separate the data into classes. Tne two di mensional eigenvector plots of the data readily indicated samples that were (a) either incorrectly assigned to a class, i.e.. fish instead of water, or (b) those that were experi mentally abnormal. S1HCA proved to be especially valuable for identifing outlier samples for reanalysis and also pro vided a basis for defining "trace" concentration levels. Ounn et al. (19$A) also comoared SIMCA. *nearest neignpor (KNN) and partial least squares (PlS) techmgues to cate gorize HflGC/fCQ data py Arocior. A transformer oil from a dump sit* was found to contain predominantly Arocior 1260 witn about 8% Arocior 1254 (Figure 8-1). Pattern recognition apoears to pc a most promising tecnnique for interpretation of large numoers of PCB determinations. HONS 223721 27 < Analytical Chamistry of PCBs figure 6>l. Principal Components Plot of RC8 Oata Thf data for four Aroclors. a transformer oil, and a 1: 1 .1.1 aiuuri of the Aroclors snowing tnet the transformer oils are similar, but not equivalent, to Arocior 1260. The axes a* noted t, and t3. are arbitrary, unities* scales depicting tne relationship of the data in n-dimensional space. Reprinted, with permission, from Qunn et al ngnt 1964 by American Chemical Society. (198*). copy HONS 223722 Data Reduction 275 3. Recommenced qualitative techniques for GC data where "total pcTT or r>mi i*r genera! ioentification is oe* s>red, simple pattern recognition (visual or computerised) of tne PCBs r)ativ to Aroc'or stanoards nay oe appropriate However, as noteo apove. many types of samples can oe weath ered or metaooiweo to sne tne Aroc'or patterns. In tMse cases, more advanceo >oanti Mcation techniques are necessary. The precise relative retention times on MflGC columns repre* sent a high 'eve* of confidence in tne iotntUy of tne peaks Use of a dual co'umn analysis and correlation of tne oata provide additional confidence Automated data Quality assessment is becoming in creasingly popular as olo strip cnart recorders and inte grators are replaced by cnromatograpnic oata systems. which are becoming increasingly soonisticated. Retention time windows, peak height ratios, and other criteria art- already m use. More sopnisticated statistical techniques, correla tion and pattern recognition, will become more popular as tne programs become more available and cnemists become familiar with their utility. Automated injectors, better instrumenta tion control, and possibly lmorovtd columns can all be uti* tiled to improve tne retention time precision. As the pre cision improves, tne time window for an identification can oe narrowed, reducing the possibility of other compounds being identified as PCBs. C. Interpretation of Hass Soectrometric Oata 1 General when a mass spectrometer *s used as me GC detector. > second qualitative dimension <s avaiiaoie m addition to the retention time. The mass soectra of PCBs are distinctive Owe to tne cluster of masses generated by tne presence of two cnlorine isotooes m nature (see Appendu C) If sufficient material is oresent to obtain full mass spec tra. an unknown can be reliably identified by comparison with soectra of authentic standards or from spectra) compilations (Stenhagen et a> . 1974; Mass Soectrometry Oata Centre. 1970: Heller and Hilne. 1978). As mentioned above, tne natural isotopic abundance ratios yield a Characteristic pattern (Aooendi* C). The ra tios* nave been taou'ated for PCBs (Appendix C, Erickson et al. , 1983d: Rote and Morns, 1973). The use of these ratios m selected ion monitoring can provide Qualitative informa tion when full miss spectra are not ootained (Canada and Regnir. 1976. [r eason and PeMijjari. 1977, 1979; Erickson et al.. 1982). ;v*n though the natural isotoo'C aounoance ratios are constant, i n$tru<*tnta \ variances and interferences can affect the observed ratio. rhus. ratios observed with HONS 223723 278 Analytical Chemistry ol PCB| standards may be more aoorooriate than the natural rjt<0 f comparison to an untno*n (Ericsson et el . 1983D) or l. Spec ' r i c extern Tindall end win.nQtl. (1980). 'n a method designed to determine PC8$ even if ^ ere not "Aroc l o r* oer < ved." established Qualitative criteni* Each peak in tne chromatogram is evaluated to determine if >t <s a PCB peak. Peaks must meet these criteria to oe labeled PCB peaks 'or Quant5. tation: (1) tne peaks or the characteristic <ons must maximize at the same retention time. (2) the peak must Pc in tne proper retention time moo and (3) tne relative peak intensities of tne mo* 'eCular ions must be within * 15% or the theoret ical ratio. This tolerance is arbitrary ano can oe made larger for very low concentrations or PC8s where statistical variations m peak intensity come large. Work y CoUard and Irwin (1982a.b. 1983) ano Do* (1981) established similar Qualitative criteria; Identify the chlorinated biphenyl homologs by their mass ion response, relative retention time, and ion intensity ratio (s 20% relative). Secon* Gary confirmation of trichloro- through decacnlorbiphenyl may rely upon the M-70* ion response. The procedure developed for EPA's enforcement of by-product PC0s m cnemical products and wastes (Erickson et a) . 1962. 1983d: Erickson. 1984a) includes similar Qualitative C'Uhj for data collected under full scan, selected >on monitoring (SIM), or limited mass scan (IMS) conditions, for full scan data "1. The peak must elute within the retention time windows set for that homolog. 2. The unknown spectrum should be compared to that of an authentic PC8. Th# intensity of the three largest ions in the molecular cluster (two largest for monochlorobiohenyls) must match tne ra tio observed for a standard within * 20%. Fragment clusters with proper intensity ratios should also be present. System noise at low concentration or interferences may skew the ion ratio beyond tne 20% criteria. If the analyst's best judgement >s that a peak, which does not meet tne oualitative criteria, is a PCS. the oeak may be included m tne calculation, with a footnote explaining tne data and the reason for relaxing tne criteria. HONS 223724 pata Reduction 277 3 Alternatively. SpeCtr*! search may p used to automatically <-*dwCf the data. The cri teria fgp acceotablf 'dent'f'C4t>on include 4 high > noe* of i >mi 1an ty. " Th* criteria for selected ion monitoring end limited mess scanning data 4re similar, but 4dd the soecific requirement tnet the analyst searcn rtigner mess windows, in particular M*?0 to prevent misioentificetion of a PC8 fragment ion clus* ter 4s the parent. If there is reasonaole ooubt as to the identity of 4 peak as a ?C0. "the analyst must either iden* tify the peak as a PCB or proceed to a conf*rmetional analy sis," This approach for marginal data reflects regulatory constraints to err on the high s'de of the true value. These three works (Tindall and Winmger, 1980; Colljrd and Irwin, 1963 ; and trickson et a 1. 1983d) suggest a new awareness tnat qualitative criteria must be stipulated in any method if tne results are to nave any significance. A novel use of GC/MS data in identifying the rela tive concentrations of different Aroclors was described by Liu et a). (1983). A multiple regression algorithm identi fied the oercent of each Aroclor (1242. 1248. 1254. or 1260) contributing to each of 40 GC Peaks. This data base was then used to comoare unknowns and identify the relative concentra tions of the different Aroclors. The authors noted that lower correlations were obtained with samples which had Deen subjected to degradation. 3. Recommended qualitative techniques for GC/MS data- The aual 1 tat 1 ve criteria of Tindall ano wmmger (1980), CoUard and Irwin (1963), and Erickson et a). (1983d) are the most complete guidance on mass soectral identifica tion of PC0s. These criteria cannot cover ail cases. At low levels, or witn interferences, the ?C8 dusters can become stewed. In addition, data massaging techniques (summing spectra, background subtract, etc.) can be used (and misused) to bring a peak ratio which had been out of the proper ion intensity ratio requirement (eg., i 205 relative) within the requirement. Rules for data manipulation nave not been welldefined for general GC/MS analysis a well as for PC8s. Bet ter guidance for data acceptance are needed. future software packages will undoubtedly permit automated identification of PCBs basto on isotopic abundance ratios. Although the technology is available, nigh precision retention times with GC/MS. have hot been widely used. As noted above. HRGC/ECO can give fairly high confidence ident ifications of over 70 congeners, based solely on relative re tention times, with the added dimension of the mass spec trum, data of very high qualitative confidence can easily be generated- HONS 223725 278 II quantitative Analytical Chtrmstryof Pcga Quant> tat>on (or (is accurately, ouan t'f iCai, 0n is the final step m a chemical analysis sequence. Some Sure of signal intensity (peak height, or peat area) is eon" verted into concentration for most detectors used in analysis, the mass of analyte m a peak. M , is prooort\nai to me signal for the analyte, *4 4 Ma * * Aa Id 6*1 The resoonse factor, RF. is a constant which accounts for tr. strunent attenuation, response of the compound, and other factors RFs are derived by injection of a standard of uno-n h and pack-calculating Equation 6*1. Quantitation can 'Iproved oy injection of several standards of different m >>0 give a plot of response versus amount (or concent ,$n j Then RF can be read off the response Curve at the orec's# area for the unknown. Since there can be I nstrumenta 1 -jr,. ation from run to run (different injection volumes, instru mental drift, etc.) additional precision can usually be oo- tamed with the internal standard (IS) method a mown amount of an internal standard. M. is added to each >ancle Then the equation becomes , M. M * RF x A x a a *is :a t*' For this equation, the RF <s derived u$mg the '"te'"ii stan dard areas, and would not have the same value as m -ouaticn 8*1. Once the mass of the analyte in the oea* >s ncn -,* concehtratioh m the extract, . can be derived H rm A : - o-i where V. is th volume injected onto the instrument Trie concentration in the extract may be converted to concentra tion in the original sample. C, by C Eq. 9-4 s where M is the mass of the sample (volume may be used for water aAd air samples). V . the volume of the extract, 's often 1.0 ml and care must* be taken to ensure that prober units are used tb prevent mi scaUulation by a factor of 1.000. since v. is often l pi HONS 223726 0i Reduction 279 Equation* 0*3 and 0*4 are oUn combined with either Equation* 8*1 or 8*2 so that trie calculation vs qone m on* pQuat'on C OF A sa v _e Eq 0*S M S If * a 11 of the values for the terns m Equation 9*8 ere known, me only error m quantitation could oe a mistake m calculation or transcrvot'on. Unfortunately, deriving the a>ue for Hf (me calibration steo) and * (the determination step) fro* the re*, data can easily induct significant errors in in* overall analysis Thi* s particularly true for PCBs, as discussed Below. With most organic compounds, quantitation is re'a* tively Straigntforward The instrumental response is cali brated using standard solutions of tne csmoOund, The amount of unknown is measured by companion of the signal 't gen erates with the calibration factor or curve. Quantitation of PC0s 's not nearly so simple since tre analyte is not a single compound Put rather a complex mixture of 209 possible congeners. in addition, standards of all 209 congeners are not readily available for calibration. Given these problems, analysts have devised alternate quantitation methods, often based on the similarity of the sample PCB mixture to a com mercial product (eg.. Aroctor). Aroc1or-based Quantitation schemes may be appropriate if the sample and standard "fingeronnts1* are similar. As the similarity diverges, me quantitative confidence diminishes. A Ca1ipration thr** calibration techniques *e available ex ternal standard, internal standard response factors, anq in ternal standard multipoint calibration. i. External standard calibration: Calibration of the analysis system versus an external standard and then quantitation using the absolute intens'ties of me oeaks lacks precision (Maefelfinger. 1901) ao is not generally recommended for gas chromatographic analysis. Often, a major source of imprecision Is tne reproducibi1ity of injection volume. Nevertheless, many PCB analyses, especially those using PGC/ECD. nave successfully used external standard cal ibration. 2. Internal standard calibration: In this tech nique. internal standard(s) are added to tne sample extract immediately prior to tne instrumental determination, and tne analytes are quantitated using tne ratio of me analyte and HONS 22372? 200 Analytical Chemistry of PCBs internal standard responses A previously determines ... soonse 'actor (essentially a one-pomt calibration cUrv# *>th an assumed intercept at the origin) n used m verting tne response ratio to the mass for t>C8$. which can span a large retention time range, three or four internal standards which span tne PC8 winoow may improve tne precision of tne response 'actors, ano therefore tne final ouantHat ion. Response factor precision is related to now dose tne analyte peak ano internal stan* oara e*ute (Haeft1finger, 19B1; 8<Ckford et a I. 19801 Other factors to oe considered in tne selection of 'nterr>a, standards are cnronatographic resolution from analytes n<j interferences. different mass soectral orooerties to asswr* identificat ion m CC/m$ analysis, cnemical similarity l0 analyte (to minimise effects of cnanges >n system selectiv ity), very 10w probability Of occurrance in samples, ana chemical stability. Candidates for internal standards <n analysis include RC8 congeners known not to oe present m tne matrix, other halobiphenyls (eg., tribromobioneny l), related haloaromatics (eg., chloronaontnalenes), and isotopicat<y labeled compounds (eg., dc*3,3'.4.4'-tetrachlorobipnenyl or d,2*cnrysene). Since the internal standard technique 'S a onepoint calibration, the response factor must be determined at a concantration dose to that of the analyte. Differences of more than one order of magnitude may induce significant er ror . 3. Internal standard multipoint calibration Tru* tecnmque is essentially the same as the resoonse 'actor teenmoue, aoove, except multiple calibration points (typ ically three, spanning up to two oroers of magnitude) are used to establish a calibration curve. This nas the poten tial for greater precision, but requires much more time and several standard solutions. In cases where detector sensi tivity (signal response versus amount or concentration) is either nonlinear or the Curve does not intercept close to tne origin, a multipoint curve is especially aovisaDle. 4. Selection of compounds for calibration: Since PC8s consist of 209 separate congeners, most of~wniCh are not readily available, a subset must generally be employed 'or calibration. This subset must be judiciously selected, since Quantitation based on a calibration factor obtained for another congener introduces an error. The options for se lection of compounds to be used in calibration are 1. Establish end use relative r**Qont* for at 1 209 congeners. MONS 22372 Data Reduction 281 2. Establish and use responses for several congener* and extrapolate me responses (or me other congeners. 3 Characterize a secondary standard oreoared from commercial mixtures to span the range f con* geners. 4. Calibrate against one or more Aroclor mu* lures 5. Calibrate (or only a few selected avail* able congeners. Option 1 is the ultimate technique: however, all 209 con* geners are not readily available. Option 2 is a compromise. Option 3 would utilize a e11'characterized mixed Aroclor or similar mixture. This has the advantages of lo cost (once the Characterization h*s been completed) and uniformity. One disadvantage' is that the concentrations of the congeners range over two or more orders of magnitude, so calibration of the instrument would be difficult. Another problem i$ mat non*Aroclor constituents cannot be quantitated. Option a has been utilized extensively, especially with PGC/ECO analysis As discussed elsewhere, this approach is valid only if the standard and the unknown "fingerprmts" are similar. Option S will not yield a "total PCS" value, but may be the most ac* propnate approach for many applications where information about selected congeners m Sufficient 6. Quantitation Techniques It is obvious tnat PCBs were ouahtitated m most references m the pibl iography. since Quantitative data rf presented. However, many authors neglected to mention now me detector signal was converted into a concentration value Many other articles only made a brief mention of "integra* tipn" or ''comparison with Aroclor 1260 standard" with resoect to the quantitation. As shown in Table 3~1, all standard procedures give at least Cursory instructions on quantitation. At one e* treme, tne general purpose stmivolatile organic procedures (CPA, 1976, 1979a.b; Ballinger, 1976) contain vague direction to "integrate the aree under the peak." Much more complete Quantitation guidelines are given in E PA`s (Sellar and lichtenberg, 1981. PA, 1981a) procedure for analysis of pC8s n transformer fluids and waste oils. MOMS 2237*9 282 Analytical Chemistry of PC8$ tore detection 4. WPPMcC411 The "OSL prominent RGC/CCO Quantitation technique was originated py wepo and ^cC4li (1973) The weiqnt percent and homolog identification (pelj. live proportions where more then ore homolog *4$ oresent) were determined R&C/E1MS for several Aroclorj, end retention times reletive to g. p_ ' *00E were specified. An example iS presented in Teoie 8*1 4nd Figure 8*2 The gener*| oroceour* is is follows'. 1. Chrometogreoh known amounts 0f tne standards md measure the area for each oeai 2. using me tapies of data determine the response factor for each peak 3. Chromatograph the sample and measure the area of each peak. 4. Multiply the area of each peak py the response factor for that peak. 5. Add the nanograms of PC8 found m each peak to optain the total nanograms of present. 6. Samples containing one or more Amc'ors can pc Quantitated Py comparison itn appropriate standards. Regarding the *ast point, wePP ano *cCai' de* vised the chromatogram division scheme shown in figure 6*3 This scheme accounts for the cnromatograohic overlap of the three comon Aroclors. Their article presents a detailed ex* planation of the rationale for this flowchart, validation of the multi*Aroclor Quantitation with nine known mixtures 'ouno recoveries ranging from 96 to 107V Following an interIaboratory survey. Chau ana Sampson ( 1975) recommended that the veDD*McCall techniQue Pe adoottd as the uniform quantitation technique. They cued th# general applicabi1ity. elimination of mixed standards, the more realistic results, and simplicity of the method as reasons for their recommendations. Another interlaPoratory study (ice and Chau. 1981a) also found wePP*HcCa 11 guant'ta* tion preferable. *aW of the 14 participants used weoo* McCall, while tne others used either selected peaks or a sum* mation of all peaks. The mean of tne results Py the weob* McCall Quantitation ws only IX higher than the design value, wnile the otner Quantitations averaged 22% higher. MONS 223730 Data Reduction 283 Exact replication of the webb-McCaH quantita* nor* *cauirs e'tner 'eorofluC'the cnromatographic pattern using me sane lot of Arocior itanoaros as weoo ana McCall used or determining tne compos'tion of tnt peaks ootamed with O'ffertnt chromatograph'c conditions or Aroclor lots. These stringent requirements have lea mast researchers to characterise tne>r ouantitation practice as a meoif'eo webbMcCaM (Sawyer, 1978a. Kreiss et al.. 1981; Harris et a'., 1981. Stephen et al.. 1982, Erickson et al.. 1983e) These users have not replicated the webo*McCall chromatography or Aroclor >ot number, out have decided that the chromatograonic patterns are similar enough to use Webb*McCa 11 ` s data taP'es. The error induced by this practice is probably not sgmfi* cant, since participants in the interlaboratory studies d>s* cussed in the previous paragraph reported a variety of chro* matograohic conditions and undoubtedly used several lots of Aroclors Ugawa et at. ( 1973) devised a Quantitation tech* maue similar to weoP*McCali which as based on nanecniors. the Jaoanese commercial PCB mixtures. A scheme similar to webb-HcCall (Dexter and Pavlou. 1976. Pavlou et a> . 1980) used PCC/FI0 to charactenje the Aroclor mixtures. tn anal* yS'S of samples by PGC/ECO Several standard procedures have adopted the Webb*HcCall Quantitation techmoue for analysis of PCBs in a variety of matrices as summarized in TaPle 3*1 (NIOSH. 1977b. 1977c; Beard and Schaum. 1978; EPA. 1978. 1981a; Sellar and L>chtenperg. 1981; Harris et a).. 1981). The calculations reauired with the w#bb*McCel) technique can be easily automated using common GC integrators or data systems (Needham et al.. 1981; *>rshen. 1901a.P. Neton and laski, 1983, Erickson et a) . I983e t Newton and Last) (1983) reported a Computer routine for Ouant'tation of Aroclor 12*2. 125*. and 1260 and their combinations The routine, essentially an automation of tne weoo and McCan (1973) procedure using BASIC, compared `avoraply with manual calculation by peak height or peak area. About 5 minutes of ooerator time is reQuired per analysis. One apparent Maw of the routine, in addition to the assumption that the analyte PC6s are unmodified Aroclors. is that it does not consider the chromatographic overlap of the Aroclors. The three Aro* dors are segregated into non*over)aDDing time windows b. Total areas; Several researchers (Collins et a).. 1972; Sellar and uchtenberg, 1975) ana standard methods (AOAC. 1980*.b; A$TH, 1981a.b) advocate comparison of the total areas undr the "Aroclor region" in the sample and standard chromatograms. This is a simple approach nd has Peen recommended by Sawyer (1973) as the most reliable method for obtaining interiaeoratory precision In a later cot lap* orative study (Sawyer, 1978b), the individual peak height. HONS 223731 284 Analytical Chemistry of PCBs T|bl* 8*1. Comoos ' f On Of ArociOr 1254 AcCOrflinq to -ebb md Celi (1973) PUT* Mean we ignt Percent Relative Std. Oev D fo or Ch!ertn$ 47 54 58 70 84 98 104 125 M6 160 174 203 232 Total 62 2.9 14 13 2 17 3 75 13 6 15 0 10.4 1. 3 8.4 1-8 1.0 100.0 3. 7 26 28 27 19 53 38 2.4 2. 7 0.4 5. 5 18.6 26.1 a 4 4 4 (2SX) 5 ( 7 SX) 5 5 5 5 (70t) 6 (30*) 5 (30*) 6 (70*) 6 6 6 7 a Retention time relative io_d7d *006 * 100. Meesureo fro* first abbearance of solvent. b Standard oivituon of si* f*sv'U as a percentage of tie mem of tne results c From GC/H$ data. Peans containing mixtures of 'somers are brc*ettd. Source: webb and McCall (1973). reprinted ->tn oermiss>on. copyright 1973 py Preston Publications. Inc. HONS 223732 Data Reduction 285 Figure 8*2. PCC/ECD Zhroaetogrem of Aroclor 1254 Th sample as chrometogree*ed on $E*30 with a Ni-63 detector operated >n the DC mode. The peek ident' f icetion numbers correspond to the retention time relative to g.g'*00E = 100 See Table 6*1 for peak companions. Reor'nted. with permission. f*om Webb and McCall (1973), copyright 1973 by Preston ?oi >cations . lr>c. HONS 223733 286 Analytical Chemistry of pcq# figure 8*3 flow C^art ter Oi ''on of CC-'ECD Chromatogram* Into Retention T>m* Regions for Quantitat'on of SaiftD'es witn MU*a Ar:cior Patterns Reor'nted. ith permission, ''-on weoo and McCall (1973). cooyrigftt 1973 by Preston Publ cations. Inc. HONS 229734 Data Reduction 287 ton I peak height ang total peak area methods were all com* cared ana gave similar results, although the individual peak method (wePD and McCall. 1973. $ayan. 1976a), was judged 511 gnt t y battar On mu oasis, AOAC ( 1900a.d) permits either individual oaak (weOb*McCal1) or total araa Quanti* tation of PCBs. Baiiar and Itchtenperg (1975) used either me total oaak. f>a'ght (or samples closely resembling Aroclors or waob*McCall for patterns "not representing a single Arodor " Transformer oils must often De ana'yied to como'y win regulations regarding their use and disposal The objective m me United States nas bean to classify tne oil as "PCB*contanmg" if t contains over 500 pom KB* and "KB contaminated" if it contains 50 to 500 ppm KBs. Thus. Quantitation nas focuieo on deriving a "total PCS" concentra* tion Transformer oil analysis s relatively simple, tne sample matrices are relatively consistent and unmodified Aroc lor patterns are almost always observed. Thus, sophisti* cated analytical tecnniQues have not generally Peen neces* $ary. In addition, raotd results from on*site laboratories nave often peen desired. The PA (Sellar and Lichtenberg, 1981. PA, 1981a) nas issued an analytical method for PCS* in trans* former fluid and waste oils. If the parent Aroclor is identifiable, it may be used as the standard for quantita* t'on "The concentration of the KBs m tne samole is calculated by comparing tne sum of the responses for each PCS in the standard to the sum of all of the KBs >n me samoie. This is oarticularly important as sample con* eenmations approach within 20% of 50 mg/kg or my other PA*re9ulated concentration. If calculations are based upon a single PCS peak or upon a small percentage of the total PCB peaks, serious errors may result. Peaks com* prising less than 50% of the total can oe dis* regarded only if (a) interference proplems oersut after cleanup; (b) the source of PCBs is obvious; or (c) the concentret'on of PCBs are not w'thin s 20% of an PA*contrpUed value such as 50 mg/kg." The method directs me anj'ysl to use me following formula to calculate me concentration of PCBs >n the sample. B v "Coneenfat' on (mg/kg) * ^ a. 8*6 HONS 223735 288 Analytical Chamistry of PC8* here . .. Sun of Sunoco Peak Heights (Areas! ; ' ng of Sljnojro Injected * TM*m/ 0 Sum of Sample Peak Hfignts (Arm) . ML injecteo ' dilution volume of temple >n milliliters. ana W eight of the sample in grams." If the parent Arodor is not apparent, the analyst '$ ai. rectee to calculate the concentration accoromg to me pr0. cedure of Webb and McCall (1973). The concentration of the PC8s m each peak is determined individually these concen trations are then addeo together to determine me total pcs content of the sample Each PCS identified n me sample must be included in these calculat ions. Specific instruc tions are given 2. High resolution gas cnromatooraphy/e ecmon capture detection a. Single congener Quantitation: The appli* cation of HflGC to PCS determination coeiplicates an aireaey difficult Quantitation problem: more beaks are present Since the beaks are presumably single congeners '"stead of the mixtures obtained by PGC. Quantitation of single con* geners has been emphasized by many authors Boe and Egaas (1979) devised a calibration factor system that oermits me analyst to calculate the ECO response factor (of a given con* gener, once its structure is mown. More recently, me ECD response factors for all 209 congeners were measured (Myi'nn et a 1. , 1984; Tables 7-1v and 7-vll). As oncussea m Chapter 7 the ranges over homoiogs and within a nomoiog 'ngicate that calibration with each congener would be necessary for accurate results. b. Calibration with commercial mixtures: One ootion for calibration is to use a commercial mixture (>.e., Aroclor) as a secondary standard, as mentioned* in Section II.A.4. This is the aooroach taken with the Webb and McCall (1973) Quantitation for PGC/ECO data (see Section 11.8.1 a. above), with hRGC/ECO data, similar approaches can pe used, although identification and ouantitation of all of the com* ponents in tne Arpclor mixture >s much more tedious. The various publications wnich characterize commercial PCS mix* tures are reviewed m Table 7* 111 and Appendix 6. Among me more recant and complete tabulations. Albro et a). (1981) de* termmed the relative molar percentages of tne individual HONS 223736 Data Reduction 269 CODOn*nts of about 100 different PCS COng*r^*rj >n Aroclors 1248. 1254. and 1280 They recommend using the Aroclor ma tures 44 secondary standards to determine hRCC/ECO response factors Schulte and Haliscn (1984) have published similar loproacn eased on me xnown compos't ton of Chioohen *50 This approach has been further refined by Sush et al. (1982, 1983) and the mass 'or ?2 peaks in four common Aroclors de* termmed (Tao*e 8*11) Tne accuracy was assessed by compari son of the gravimetric versus GC-caiculated concentrations. The total amount calculated by the chromatographic data sys* ten was 12% higher than the gravimetric value. The orecs>on, based on replicate injections of a mixture of 27 au thentic congeners, ranged from * 1.17% USD to * 8.26% RSO for individual peaks, with a precision on the total of * 2.25% PSD A nenu*driven computer program as recently reoorted which gives congener-soec>fic Quantitation of over 100 components of Aroclors 1242, 1248, 1254, and 1260 (Schwartz et a)., 1984 ). The data may be presented >n sev eral ways, such as by congener, by homolog, or by number of ortho chlorines. The data may also be fed into a pattern recognition program for additional Qualitative studies (Dunn et a). . 1964 ). The use of a wel l-characterired secondary standard has several advantages. The preparation of stan dards >s relatively simple and cheap. All of me congeners likely to occur in environmental samples will be calibrated and will be m roughly similar proportions m me samples and standards A disadvantage is that, like the webb`*cCeli ouantitauon. it presupposes that ail PC8s are derived f'-om the commercial mixtures and does not Quantitate aJJ PC8s This can be detrimental m analysis of true unknowns, es- cecially where by-product PCBs or partially destroyed PC8s may be present. c. Statistical evaluation of hBGC/ECD data: A rigorous statistical Quantitation as described (kafaoar and Ebtrnardt, 1983) for the certification of tne N8$ stan dard reference material of Aroclors in oil (Uriano. 1982). The linear statistical mode) recognized that tne data for tne individual beaks determined by hRGC/ECD were not independent. Each of four SAMs were analyzed six times as described by Chester et a). (1981) ana Parris et al. (1984). yielding 10 PCS peaks and 3 internal standard areas. The statistical analysis yielded the certified concentrations snown in Table 8-111. peaks. d. Quantitation using selected diagnostic Zell ana dallscnmiter (1980) presented a simplified HONS 223737 290 Analytical Chemistry of PCBs ia *'*. am *l*l* l.l.l.l Ml itv't *** $*4*rtt 4r*lf HUtwr* Uri*trt lift H/*C ran--iair(*2 9 iuflai/ai ') i7B it* *t ftrat loM 1 33 ft 1ft 1 10 1 21 ft 3ft ft ft< ft 2ft 10 11 10 1 11 Oft 11 37 11 3 11 13 11 11 ftl 11 IS 12 12 12. S7 17 *0 11 07 11 <7 VI SO 11 14 U IS 3) 17 l* 17 IS 0) IS IS 11*4 11.0) 11 11 11 14 1ft M i IS 17 37 17 44 17 7 11 11 7 72 4 71 2 73 7.3 7 .4 * 1.2" ,V 2 2'.* 2.2-.3' 3.2' 2'.*.* 4 4' :: r i ,j.i 2.3.1- Cl. C, 2.3.4' 73.)' ' 2'.ft.*' 2' ,J*,4 2,7' .VV 7.7'.1.S' 7.7'.2.1' 7.7*.4.4- C'. 7.7' .1.1' C>, Cl. C' 7.7'.3.3'.' 7.3'.4'.S 1.3'.4,ft7' .4.47.7'.3.3-.1.4' 7.7',4-,J.S' 2 7' ft.4- S' 7 7\1'.*'.S 2.7' .3,1' 2 7'-l'.S.S'.4' 7.2'.3.3'.S'.*' y3.1'.3. S' 0 7ftft 0 112 0 421 0 02t 0 03S 0 947 0 042 0 373 0 714 0 024 0 Oft* 0 074 0 111 3 Oil 0 040 0 031 0 071 0 07S 0 1*2 0.717 ft 140 0 73) 0m 0 114 0.047 6 0S* 0 44ft 0.9 SO o.uo 0 14S 0 MS 0 114 9 447 9.0S3 0 4M 0. til 0 070 , wOu ft 111 0. lift 0 112 0 02ft 0 704 1 744 0 111 0 400 0 Oil 0 03J 0 041 0 ON 0 713 r T r 0 104 t 1 T f r T T T T I T 0 0*4 0 000 ooot 0 114 0 021 0 144 0 IIS 0 04S 0 094 0 0S7 0 044 J OIS 0 032 0 014 0 017 0 021 0 lift 0 7M 0 177 o.us 0 111 0. 10S 0.047 0.9M 0 OJft 0 04} 0 107 9 ID 0 047 0 047 0 Oil 00 000 oil 0 OIS 0 0S7 o ns 0 071 0 10S 0 037 0 01ft 0 041 0 1J4 0 04ft 0. lit 0 70ft 0 037 0 017 0 Ml 0 124 0 041 00 103 ost 0 3> 0 073 0 140 J Oil 0 037 0 144 0 771 9 117 9 7M 9 til 9.17ft 0. Ml 9 047 9 9SO 0 114 0 Ml 0 IN 0 07S 9 193 0 013 9 OM o on 0 930 0 074 0 0S4 9. Oft 7 0 077 0 7M 0 9M ft 07} "ttAPtCM 0 074 9 >71 0 Olft 0 110 0 007 0 174 00 071 us 0.013 0 779 HONS 229738 Data Reduction 291 1>*. am Struct**-* '*m i-n (CAClu0) C i* **t IrM tar <2 0 U0/4L/ 1771 nrrr i7l* 12M Su o' 4'SCl|< l SO 21.72 ji >4 22 1) 22 73 1) 2) 22 23 13 2* 22 2* S3 24 M 2* JJ 2 90 2S 44 23 27 C\ .3..) 3 4i .1' . 1 1 .3 .3 t'* 2.3, 3 S' c* C>, 2.2 ,3 .5 2.2'. 3' .4 S' S 2.7' ,3' *.S ,3 .S' CH 2 2' J 3' . 4 * . . a . J 3' S S 4 ' 2.2'..3..1 4 .4 4 2.J\ ' .3 ,3' 2.2' r .3-.4.4' 2' .3 .3' ,4 . .S' 2.2V .3' .S.S' 2,2` ,r ,4.4' s.s 2.2',.3. J' . .',s 2.2' .,3. r .4, S.s .*' Cl, 2.2' .3. j- ,i SO' 2.2' ,3' S.S',4' 2.2`, 3. 2` .4 s * 2' ,3 .3' .4.$' Tftfl 0 014 0 OH o oso 0 13S 0 032 0 Oil 0 042 0 344 #023 0 043 0 2*4 0 OSS 0 930 0 u 0.033 J 141 0 044 0M 0 021 0 #47 0 024 0 270 0 120 0 044 9 933 9 91S 0 0*2 0 033 9 90S im 2 244 2.9*4 0 Oil 9 913 0 OIS 0 170 0 OSS 0 07* 0 000 0 127 0 013 0 021 0 1J9 0 03S 0 004 9 040 0 027 J Oil 9 000 0 004 9 0)3 0 003 0 077 Q 020 T 1 r T r 2 341 1 007 1.0*4 0 017 0 90S 0 eu * 021 0 143 9 021 0 MO 0 127 1 1 70 ' J40 9 947 0 Oil 9 014 0 021 9 2SO 9 192 0 0S4 0 020 0 032 0 ON 9 ON 9 0*2 2 334 0 D MS 0 0 021 0 0 29S 0 0 1J4 0 040 on 0 S2 021 0 277 0 122 0 0 035 0 OH 0 043 0 Ml 4 22i I 1 *" Tr*f surrt Out* ft *1 . 1402. 0<fieii *)rt>tf) ChM<tit wtth cWrr'fAt 1407 *y MONS 223739 292 ro) 8*111 Analytical Chamlstry of PC83 t 0 8Qwnliut<on o "OS St*n r t*f*r*nc* M4t*n*) Polycnlr>fl*l*a 8 ic^ony)* in 0>l Aroclor Typo Crt-f >09 Concontr,IS0" (vl/1) Concimr|t<oA k>0/fle Coftf 'OfflCf UftlU Motor o<1 "Otor o' 1 1 r*o* fpr**r oi) Tr|ftfor*r O'> 1202 1260 1202 1260 t100 1 t100 2 100 : 1 100 : 3 100.07 100.89 100.)9 100.07 98 68, ltl 8 9*. 70, 102 >4 99 It, 101 62 9t 65. 101 4* 4 >'o* u'in0 , .962 3 Veftjmly <i 01 lh# 9 5*. ce'"3*C* lf*t> *.tta*rc :'om ng (pornorot. >98}. MOWS 223740 Data Reduction 293 approach to Quantitation us>ng "diagnostic oeaks." The *t* fonai* for selection of these diagnostic Deans is discussed in Section 1.8.2b. aDove Althougn subject to some e^sr. the authors consider the inherent error steal I relative to total PCS quantitation at the parts oar billion range, they also assert that the small, unresolved peaks are more likely to be (or contain) nonPCB components such as polychioro- terpenes (toaaphene) The validity of the approach nas not been reported. Tuinstra et a>. (1963) presented an extension of tne above approach. for regulatory analyses, where the full quantitation of samples below the regulatory cut-off level is of no interest, they selected sa PCS congeners (Table 8-IV) for use in Quantitation. The six are present >n at least one Aroclor mixture, tend to accumulate in biolog ical samples, are commercially available, and are chromatographtcaily resolved from other congeners. Tnis approach may be especially useful >n large sample screening programs. *nere the Aroclor-aer:veo ?CB patterns are similar ana :cmpliance with a regulatory cut-off is the primary concern Simplistic quantitatipn routines are still used with HRGC, even though most analysts choose it over PGC for the increased information content. Gordon t el. (1982) used only three peaks from each Aroclor standard to duantitate PCBs in transformer oil by HRGC/ECO. White PCBs do not weather extensively in transformer oil and are thus more likely to resemble the parent Aroclor, this method utilizes only a small portion of the available information. Schulte et a!. (1976) recommended Quantitation of HRGC/ECO enromatograms based on two selected characteristic peaks m food ex tracts. 3. Comparison of Quantitation bv PGC/ECO and H8GC/ ECO: woiff et al. (1982a; used one tr>*. penta*. ano ne*achTorobiphenyl as standards for HRGC/ECO quantitation of tri- tnrough heotachlorootphenyls in plasma and adipose samples of occupationaIly exposed people. Quantitation by this sum of individual peaks gave comparable results to the Webb-McCall method using PGC/ECO. Both methods gave lower values than the sum of peak areas method using PGC/ECO data. A col'aborst iy# study of PCBs ano organocnlorine pesticides in open ocean waters come to an emphatic conclu sion that PC8 concentrations in seawater should not be re ported in terms of Aroclor 1254 (Palmork et a>.. 1932) Al most all of the literature nad previously reported seawater concentrations as an Aroclor 1254 equivalent. The study snowed that the measured amounts of individual PCB congeners RONS 223741 294 Analytical Chemistry of PC3s It '<>* I'lv i' i *Cli utfd i*>'*< tu'ptttr WK M 0t' . < *l'CIM*9t <1 '*1'xtt` *t*i*e*` *!# <*0'0I , ' 1 * 1 ; ; .s * i*'*# ;.2 : ; 3 * * .l >. lorot '*")"' 32 j i.r 3 .. 1. S' ttttxit't* *** 1 21 10 Ox *i>*c'*r 12*23 12 (lx *>< lr 121l 101 1 {lx ftr*c >' 121*) 3* .0 I |x *'< It' >2*01 1)3 10 (|X Afttl*' 12MI 100 12 (lx '*c>tr 1240 > 01 32 9 01 01 01 4 0*r#O "# ' Mmr wt ' 'ft' rxc* *1 S '*<1 * i i>m citti iit # tt<**-c*i *'*<>' !>> m t**'* StM'CI ft ll (10031 'Il'MMtl t* e#t''0t vt'MM IM I'lMX *wtl't*'t Lid It !<' i 1M3 NOMS 2237*2 Data Reduction 295 In a single sample varied fro* the equivalent of 0 Q ^57 ng/L Aroclor 1254 inflicating severe flijtortion of the AroclQr pattern. Th# study authors recommended that congener- specif'c PC0 measurement Mas the only valid method 'or deter* *ming PC8s m open ocean water. The PCS concentrat ions in air samples were measured by PGC/CCO. HBGC/ECO on three different columns, and by duel column HRGC/ECO. as shown in Table 8*V (Singer et ai . 1913). The dual column approach involved simultaneous injection of the sample onto two columns in one GC oven. The Quantitative results decreased about one order of magnitude for each of the levels of increased analytical sophistication. The HftCC analyses on the different single columns agree fairly mcM and are roughly an order of magnitude less than the PGC data and an order of magnitude greater than the dual column hAGC data. Singer et a) believe that the higher values result from erroneous Quantitation of interferences along uith the PC8s and speculata that most of the data for PCS concentra tions m ambient air may be biased hign. This conclusion should be verified by indeoendent confirmatory techniques. It is unclear from cne article wnetner tne dual coiumn HftGC approach is eliminating only interferences, as the authors Claim, or applying overly*stringent identification criteria (see Section 1.8.2.c. above). 4 Gas chromatoqraphy/electron impact 'onitation mass spectrometry: The ability of tlHS to"easily sort PCBs by nomoiog has led to a tendency among GC/EIMS users to Quan titate by homolog (i.e., summing all beaks for each homolog). Another major difference from ECO U the ability to Quanti tate using either a single PC8*specific m/z peak or the total ion current. The latter corresponds to an analog detector output. The first reported GC/6IHS quantitation of PC8s was a nmole translation of classical CC/EC9 auantitat;on -qmpanson of "the area under one or more of the eight PC8 peaks to the area of a known amount of a standard" (8on!li. 1972a.b). Eichelberger et al. (197a) cnose what they termed "the convention*! approach" and assumed that the PC8 mixture was one of the commercial mixtures. The total peak area for each selected ion monitoring (SIM) mass in the sample and standard were compared using an internal standard to normal ize the peak areas, williams and Senoit ( 1979) used tne sum med total integrated area for six to eight selected peaks for Quantitation of PC8s in several household products. A multiple regression statistical analysis orogram quantitated H8GC/EIMS data for sediment samples using stan dard areas for 40 peaks in Aroclors 1242. 1248, 12S4 and 1260 HONS 229743 296 Analytical Chamlstry of PC8s 'lOle I*' Ca*o<r<on f C ConctAtfUant in lir by ICC. -ICC m Oul Coia "*CC* S*ai Ca* iictae imfll* !*'1 *' c (6*2100 0v-1 illt'ncnio 3vl' CO *n ovmTTTT*" l *# 61*12*16 2 **61* 12- M ) HW^Sl-12-it 4 SA-Sl* ul 16 6 SAl* SI*UI- It 66 14 Jl 61 62 42 10 22 * *2 1 *! 6 SUO-Sl-Sl-lt 62 J 5(J0* SI Si* 17 61 1 'l 6uO*61*6l*4 uO*si*$i*i *7 *6 3 9* 10 5AI-S1-WMJ 116 3 *b u SAI-Sl-Ul-17 If J 'b 12 H(U 6 l -U- 4 u HttA'Sl-U-l i T0*S1-UI-1 13 M 317 uj 2t U-J is r0A* Sl-ul ? 16 70l*Sl*vi* It 2 It 6 21 0 l> "M-SI-U2-16 It I6*6l-J4*I6 If -l-il u4- 1? 11 6' .1 3 b 2 *5 : 79 20 *1 * >1U4* 1 21 "Art-6l-U2*4 22 *IS*Sl-tf4-l6 16 121 If * b 2 *1 1 t 23 HA*Sl'W2*lt i* NAt*$l*V*6 26 4 4b 62 t 7" a LON* 61* SI It 16 11 b 26 SAt*61*V*2 2 HAM*S1*U*1S 21 NIS*51*U1*J 1.616 6t * u* 61 2> 26 61 32 21 2f 1t 1f 17 33 62 n 10 16 66 2) 1 ; ** 2i 3t 26 22 0.7 f4 43 6t 2f 14 30 12 43 10 2l 20 26 1l 14 23 4l 70 10 >6 *t iJ 11 ;i i6 30 23 1.6 16 f1 66 f7 3l 04 07 00 06 0 02 0 ft 00 03 oa C6 02 14 33 5 63 l6 o; 93 j; 01 09 13 l 02 02 63 2l l1 06 SabOlBt allylBO BA RmiU'NCUM 6D40A r 6M0A " in *o 'Hilt 'A* JBCI'B" tM CCD NIKKI* r** licit! iCBlwNft *41 f * I/O" aa SI IKUt '!* IS DiIttl 400 An*cnr* Q Tab ciBilla'v eo,>^ii .** ill 2S i 02 m at *o 7tl/iJ i1 * e A pearly 'l*olM i pretant royM 1IT * 26 *><*. men wit ar q *411, cgil'MMI It *tt In tmt tat 1 4414 t*4 BI4* l* au iuao Sawwca S<*> at <i (Itt)l. ni'HKM w*lh . ap*- f*t 1913 By luttlrvirilil atlifAn (AM Arftn $C<B*<B) HONS 223744 Data Reduction 297 (Liu et at., 1984) to yield in "Aroctor" concentration. un-- eathered Aroclor matures yielded very low deviations from the expected value. wnile weathered PCBs extracted from field sediment samples gave less reliable Quantitations. A single isomer for each homolog has been used to calibrate HRGC/EIrtS for Quantitation of PCBs in sludge (Erickson and Peliizzari, 1977, 1979) and stack gases (Haile et at., 1983a,b, 1984). Stack gas samples from the N/T Vuicanus I were analyzed by HRGC/NREIMS (Ackerman et a!., 1983b). The analytical system was calibrated using a suite of three isomers for each homolog (except C,2Cljo)> as shown in Table 8-VJ. An average response factor for the three iso mers was used to quantitate the unknown isomers for that homolog. 2.3.6-Tribromobiphenyl was added to the sample be* fore extraction or cleanup to monitor recovery and du-cnrysene was coinjected with each sample as an internal standard. Instrumental detection limits were either 25 pg/pl or 100 pq/uL for each homo log In one of the few papers addressing analysis of noncommercial PCBs, Tindall and Wininger (1980), established homolog response ratios using an unspecified number of iso* mers per homolog. The highest and lowest response factors for a homolog were averaged to give the average response fac* tor relative to tribromopiphenyl. Collard and Irwin (1982a,b, 1983) and Oow (1981) used 22 congeners to establish response factors, for hoaologs with more than one isomer in the standard, a summed Intensity was used. A daily caliora* non plot at three concentrations was used for comparison of the summed peak heights for one homolog. Martelli et al. (1981) reported the EIMS relative response factors for 45 PC8 congeners (Table 7-xl). The rel ative standard deviation per homolog ranged from 0.72 (3 of 48 possioie isomers measured to 2L2 (11 of 42 isomers mea sured). They proposed using these average response factors on CC/EIMS Quantitation of PC8$ by homolog. The relative response fectors (RRf) for 77 PCB con geners (Tablet 7-Xll and 7-Xlll and figure 7-15), obtained by both quadrupole and magnetic sector instruments, were used to determine the average RRfs by homolog (Erickson et a)., 1982, 1903b; Stanley et a).. 1983). A subset of 11 congeners hav ing average RRFs and RRTs (Table 7-XIV) were recommended for us* as calibrants in a method for analysis of by-product PC8$ m product and product waste samples (Erickson et al.. 1982, 1983b). Th approach, similar to those discussed above, uti lizes the most complete set of EIMS response factors avail* aol. MOMS 229745 HMOkoft 1 tOlt 0*V! K1 Coo^OMf* Uwd Vo Otti-rtint ftctpontt Udsri Slutk Solj/lion 1 i MOAOChlofO DkMoro frtvMoro ItlncMOro frniochloro >!* (Cht oro ltr|>t -at It tut Odithltru NO(wChtoro Uet ochloro 2 2.2' 2' . M 2.2' .4.V 2.2' .U,*' 2.2'J`.4.4* t ,4,'j. v > 2.2 ,3.r .4.S.4.4* ?,r).r.4.b(y .fc.b* 2.2.1.1* .4.4* ,*, .*>' } 2.4 2.*.h ).)*.4.4* ? , J ,4 ,4' .4 2./\4,4\4.4` 2.2' . *.4.4`,i.4 2.2` , *. J ` .4,4- .VV >.? . 1. .4.4* .4.V .< 4 ?.t> ?,4,4' 2.2`.4.41 ?.).) ,b.6 ?.?.l.VV .0 >.J1 .J.J* .4.4' 0 ?.?* 6.4' J7',J.),,4.r .V6.6' Wurtt Atkef*io p| 41 (rti)l't) MONS 223746 Data Reduction 299 5. Hi setlteneous Cairn* and Jacobson ( 1977) ad vocated PCS quantitation by PGC/CIHS because of the reduction in interferences by other halogenated compounds such as OOE relative to GC/ECD. however They did not compare CIMS with EIMS. A$ discussed m Chapter 7, perch ton nation and de* nydrochionnation. followed by PGC/ECD end PGC/flQ deterennations. respectively, have been proposed as PCS quantitation techniques which eliminate many of the problems arising from multiple congeners An advantage of these techniques is that the area of a single peak is being measured, so there is less potential for error. A disadvantage is that the derivatiza* tion step introduces its own source of error In addition Qualitative information about the PCS congener distnpution i$ lost. Safe (1976) suggested that percnlorination would be more consistently accurate than Quantitation of the complex chromatogram of the original PCB mixtures because of the var iability in ECO response factors (see Table 7-vI). TIC and hPlC have a<so been emoloyeo is auantita* tive techniques. TIC spots can only be semiQuantitated with visual interpretation. Probably order-of-magnitude estima tions of concentration are possible. With a densitometer, TLC spots can be quantitated with more precision. MPLC quan titation is at least as precise as most GC quantitations. However, problems of quantitating multiple peaks, insuffi* cient standards, coelution of homologs, etc., afflict HPlC in much the same way as GC. The absorption maxima and extinc* tion coefficients for Z7 congeners (Hutzinger et al.. 1974a; see Chapter 2) indicate considerable variability cm be ex pected in the of HPLC/UV response factors. 6. Automated quantitation: for many analyses, quentitation of Jtds i $ the most labor-intensiv step. Even with electronic integration of all of the peaks in a chro* maiogram, me analyst often races a long cast. or Eliminating nonPCB peeks and totaling the areas. Thus, it is only log ical that analysts have increasingly sought to automate the date reduction. The eutometed dete reduction techniques which have been reported can be categorized as either simple integration routines or pattern recognition routines. Pat* tern recognition routines were discussed above under quali* tative data reduction. The simplest automated integration routine sums the eree.of all peaks within a given retention window. The total area is then comoered to the tornesoonoing area for a stan dard (usually an Arodor) and the concentrat ion reported. A more complex variation involves individual peak Quantitation by comparison of the peeks to those in en Arodor cockteil. MONS 223747 300 Analytical Chemistry of PCQs flush et al. (1982; 1983) hdvc automated such a system iv dividual resoonj* factors -ere used for quantitation of'?? peaks in unknowns. 2obel (1974) devised a computer fit routine for PQ data which matched the sample chromatogram with various "co* added" Aroc'or chromatograms to obtain a best fit. "Sounously large or small peak heights, causeo by interfering cam* pounds or metabolism, are automatical ly sorted and rejected ' The method reports results in terms of the different Arodors and can be modified to generate an estimate of "premetabo1ism" PCS content. Several authors nave reported computerized quanta tation techniques for PCBs in transformer oils (Newton ana laski. 1983; Colby et a 1. . 1983; Colby and Picker, logj Cossman, 1983, lea et a)., 1983; Picker and Colby, 1?83) while automation of mis time-consuming steo is aooealing for economic reasons, trained analysts must both validate the quantitation witn real samples and audit the results curing routine application for QC purposes. In an intralaboratory comparison of several matrix/ cleanuo/GC column/detector/quantitation combinations, Levine et al. (1983) found some significant differences m quantita tion results. For instance, the PGC/HECQ/area quantitation results for n ISO ppm Aroclor 1254 in waste road oil were about twice as high as those obtained by PGC/HECO/oeak heights, PGC/ECO/area. PGC/ECD/peak height, or a similar set of four HRGC/detector/quantitation combinations. Tne authors concluded that a computerized data system did not yield more accurate results than either a low-cost printer/plotter inte grator or a ruler (for peak heights). 7. Measurement of PCS recovery with surrogates: Recovery surrogates are added prior to any sample treatment and are used to assess the recovery of the native PCBs through the extraction and cleanup, like the native PCBs. surrogates may also be quantitated against the internal stan dard. Since th* amount added is known, the surrogate recov ery can bo calculated. The criteria for selection of recov ery surrogates are similar to those for internal standards discussed above. ,3C-labe1ed PCB congeners have been used as recovery surrogates in byproduct PCS analysis (Erickson et al.. 1982. 1983b. 1983d; Erickson. 1984a. 1984b. 1984c. 1384d). Knowledge of the percent recovery is useful m mon itoring extraction/cleanuo performance. The final reported concentration may be corrected for recovery if desired, or the value found and percent recovery reported separately. It should be noted that if the recovery surrogates and analytes MONS 229748 Data Reduction 301 are not, in fct. eouaiiy recovered, then the reported recov try is meaningless This can haooen if the surrogates are not fully incorporated into the matrix. 8. Piscuss>on The applicabi1>ty of the different Quantitation techniques depends on the analytical technique, tne PCB concentrations, consistency of the PCB pattern within a sample set, and analytical oDjectives. HRGC permits identtfication and quantitation of individual congeners, while PGC is generally limited to either reporting an '*AroclorM concen tration, or "total PCB" concentration. If MS is used as the detector, the different homologs are readily discernaole. and concentration by homolog i$ often reported. If the PCB pat* tern is consistent itn that of a commerical mixture (eg . transformer askare's). Quantitation of GC/ECO data against a Known quantity of Aroclor may be appropriate and can yield satisfactory data. This approach must be utilited with in creasing caution as the cnromatographic pattern diverges from mat of the stanoard. 7he objectives of the data user also affect the appropriateness of the quantitation tecnmques. A study of selective degradation of congeners in an Aroclor mixture would require Quantitation of individual peaks, while analysis of a waste to determine dispose) requirements mey only require a total PCB quantitation. The analyst employing PGC/ECO for trace environ* mental samples will probably obtain the best results using the Webb-McCall technique. The best techrtique for quantita* tion of environmental samples using HRGC/ECO is not as clearly defined. "Total PCB" values mey be obtained by inte* gration of all of the peaks, using response factors generated from an Aroclor cocktail (see Bush at al.. 1982). The ap proach. used by 2ell and Ballscnmitar (1980). of ouantitatmg only a selected few "diagnostic peaks" may be appropriate for jvme implications, provioeo *.ne PCB patterns i-e similar jnd provided that the approach Is thoroughly validated, for reg ulatory cutoff analyses, the approach used by Tginstra et al. (19B3) which uses six specific, diagnostic congeners appears to be both reasonable and expedient. If the PCB pattern closely resembles that of the commercial mixtures (eg., transformer oils), quantitation against an Aroclor standard, either by total area, or by tne area of selected peaks may be appropriate. These analysts are often automated to reduce the labor costs. 7ne analyst must review the dete and employ appropriate QC measures to monitor the data Quality When the PCBs are present at sufficient levels, when there are significant levels of chlorinated interfer ences. or when the situation demands additional Qualitative MOMS 223749 302 Analytical Chemistry of PC8s confidence. EI MS should be used as the CC detector w,th mess spectral data. PCBs are most often duantitated by h0mo- log. generally .tn only one calibration isomer per nomoloa The added information of congener-specific Quantitation may be obtained the same ay as with hRGC/ECO data, i.e.. the re sponse factors and retention times for each congener of in terest are obtained with authentic standards. Regardless of the Quantitation techniQue employed it snould be described m detail or adequately referenced in tne analysis report or publication. As noted repeatedly m this boox, tne data reduction can be a significant or even major source of analytical error. Thus, the analyst must document this step with the same detail as is customary for instrufflentation and procedure 1 1 1 DATA REPORTING The data report must be formatted to fulfill the analytical objectives. If individual congener concentrations are needed, the report will be complex, wnile if "total PCB" is sufficient, the data report may consist of a single value The report must specify the reporting units. Units such as micrograms per gram (solids), micrograms per liter (water), and micrograms per cubic meter (air) are recommended. Parts per million and parts per billion can be confusing, not only is there international disagreement on the term "bill ion" (10* m American System; I0U in British System), but also it may be unclear in some matrices whether tne measure is weight/ weight or weight/volume. for high density liquid samples (eg., a halogenated solvent), the difference can be signifi cant. The analyst should include on the data report some measure of the qualitative confidence. This is often done in the text, or as a footnote. The d*te report should include mention of any re covery correction employed and the correction factor. Re* covery correction has not been customary practice in residue analysis. Often the error associated with the recovery mea surement is larger than the error associated with the PCS quantitation, so a recovery correction may add to rather than reduce uncertainty of the reported value. The analyst must treat values near the detection limit approoriately. "Zero'* should never be reported, only "not detected." "trace,** or other expression of the limit of detection (LOO) or the limit of quantitation (IQQ). if sam ples or congeners are reported as "not detected," "trace," NONS 223750 Data Beduction 303 "not quanti tatable etc., the numerical value or estimate of the LOO or lOQ should be stated in the data reoort A^di* lional guidance is available (Keith et al., 1983, Crummett, 1979. MacDougall et al., 1980; Glaser etal., 1981. long and Winefordner. 19831 finally, as a QC measure, the data report should include sufficient information to trace the data. In addi* tion to the customer's sample number, an internal sample cod*, data file code, notebook number, analyst identifier, etc. . nay be aporopnatf HONS 223751 9 QUALITY ASSURANCE I. GENERAL CONSIDERATIONS Emphasis on quality assurance (QA) in chemical analysis has increased dramatically m the past few years with the realization that data of unknown quality are vir* tually useless. In previous chapters. QA considerations have occasionally been mentioned with "e^ards t: soecific :ecn* niQues This cnapter focuses on ootn general QA considera* tions and specific quality control (QC) measures applied to RCBs. The terms "quality assurance" and "quality control" have often been inappropriately used- QA 1$ generally de* fined as the program or structure within an organization which plans, designs, and monitors the QC procedures and af* firms the data duality in reports. The elements of a QA program plan for the Office of Toxic Substances in the USERA (ERA, 1983c) are listed in Table 9*1. The specific require* ments for other QA plans can vary from this list, but the general content should be similar. QC is the term used to describe the activities in he QA oropra* which control er*ir srrf Tjta dual ity. Some of the potential QC elements or activities are listed in Table 9*11. few QC programs, if any, will imple* ment all of these measures. The selection of measures and the degree to which they are applied (e g., f-eouency of cal* ibration) are dependent on the analytical objectives of the program and on the procedures, people, and equipment being used. A third term, quality assessment, describes the data verification process, for more details on quality assurance the reader is referred to more detailed reviews on the sub* ject (Keith et al., 1983; HacOougafl et at., 1980; ERA, 1979c,f. 1980a.b. 1983c; Cardone. 1983a.b; Cairns and Rogers. 1983; Morwitz. 1983; nateman and Rijpers. 1981; nirchmer. 1983; Sherrna. 1981; Watts, 1980). 305 MONS 223752 300 Analytical Chemistry of PCBs Table 9-1. Suggested Teblt of Content* for QA Project Plan 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0 Title page Table of contents . Project description and objectives Project organization and management Personnel qualification* Facilities, equipment, consumables, and services 6.1 Facilities and equipment 6.1.1 Evaluation 6.1.2 Inspection and maintenance 6.1.3 Calibration procedures and reference materials 6.2 Consumables 6.3 Services Oata generation 7.1 Experimental design 7.2 Sample collection 7.3 Sample custody 7.4 Laboratory analysis procedures 7.5 Interna] quality control checks 7.6 Performance and system audits Oata processing 8.1 Collection 8.2 Validation 83 Storage 8.4 Transfer 0.5 Reduction 9.5 Analysis Oata quality assessment 9.1 Precision 9.2 Accuracy 9.3 Representativeness 9.4 Comparability 9.5 Completeness Corrective action Documentation and reporting 11.1 Documentation 11.2 Document control 11.3 Quality assurance reports to management `11.4 Report design Source: EpA, f983c. "~ MOMS 223753 Quality Assurance Table 9*11. Quality Control Consideration* in PC8 Analysis 307 METHOD VALIDATION * Analyze blanks Analyze spikes * Analyze standard addition samples Analyze replicates (precision) * Assess potential interferences * Conduct a ruggedness test - Compare to other methods (accuracy) * Select and validate PCS* to Oe used for instrumental calibration Assess transferabUity to other analysts * cscaolish instrumental performance criteria (e.g., sensitivity, resolution) Determine instrumental limit of detection - Determine instrumental limit of Quantitation * Determine method limit of detection/quantitation * Determine range of quantitation * Oecide on treatment of questionable identifications * Oecide on treatment of trace data * Conduct a collaborative study SAMPLING * Use field controls (eg.. 10%) to assess losses * Use field blanks (e.g.. 10%) to assess contamination Use a well-designed sampling scheme to fit study objectives * Evaluate representativeness of sampling schema * Use a valioated sample preservation and storage orocedure * Use clear, unambiguous, informative, permanent labels HETHOO EXECUTION * Monitor instrumental performance (e.g., sensitivity, resolution) Calibrate instrumentation - Calibrate apparatus (e.g., 1-mt, volume marks on sample vials) Verify reagent end standard purity - Verify reagent end standard identity * Verify reagent end standard concentration * Periodically check stability of standard solutions Control glassware contamination * Monitor glassware contamination with blanks ' Use either sample traceebility (not legally defensible) or chain of custody (legally defensible) HONS 221754 306 Analytical Chemistry of Pces Table 9-II (continued) SAMPLE PREPARATION ANO ANALYSIS - Include bUnits (e.g., 10%) with Mch siaplt set Include replicates (eg, 10%) with eech sample set Include spikes (eg., 10%) with eech sample set - Include cneck samples (e.g., 10%) with each sample set Include blind check samples on a regular basis - Repeat analyses on a regular basis - Use Surrogates to measure method recovery on eech samoi* Use internal standards for quantitation Determine LOO, LOO, MOL. or MQL for each analysis aav or semoU set - Monitor retention times for PC6 identification QATA REDUCTION ANO REPORTING Validate eouetions, algorithms, or orograms Checc selected identifications by a econo analyst q 10%) ' Check selected quantitations by a second analyst (e q 10%) ' Label and annotate all chromatograms end other output Include sample number, date of analysis, notebook refer ence, or other information in analysis report so that data may be traced Cite method end document all deviations in the analysis report Report date in uniform, unambiguous units Report analytical uncertainty Report any blank on recovery corrections Report results of QC samples Footnote any questionable identifications or quantitations Oo not reoort any quantitation below the '.DO Report the LOO, LOO, MOL. or MQL end when it was determmeo Report results only to the appropriate number of signifi cant figures Review data with another analyst Repeat questionable analyses CONFIRMATION ' Analyte sample using an alternate technique (eg., addiLionel column cleanup) * Use a confirmatory technique (e.g.. alternate GC co'umns. more specific detector) Send to another laboratory for repeat analysis HONS 223755 Quality Assurance Table 9*11 (concluded) 309 networks of multiple laboratories Oesignate a QA laboratory Use the same procedure Use consistent reporting format Use aliquots of the seae standard solution n<j critic*' reagents Use similar pprtus and instrumentation Provide assistance to the analysts fro* both QA lb end others in network Conduct periodic informal site visits for information exchange Conduct periodic fomel systeas eudits Conduct periodic informal QC check se*ple enelyses Conduct periodic formal performance eudits Use e centre! s**p?e tracking, coding, scheduling, end distribution syste* Incorporate blind duplicates, blanks, end spikes into the sample set Have olind duplicates analyzed by different laboratories Have a central date review organization Conduct periodic confirmatory analyses The QA program for a given laboratory, if already in place end operational, should need little adjustment for analysis of samples for PCBs. The QC* however, oust be tail* or*d not only to the general considerations discussed in this paragraph, but also to the analytical peculierities of PCBs discussed in the following sections and in other chapters of this book. The first step in planning a QC program is to es* tabiish the data quality needed by the end user. At this point, the analyst and user must agree (or at least compro* 'i$el nn the lata ouality objectives: specifically the deqree of qualitative confidence, limit of detection, cate confi dence level (i.e., precision and accuracy), validity of the method, end the amount of QC needed. Next, the analyst must design the QC program to fit these needs in the context of the analytical program, finally, the analytical program is conducted. During this last phase, it is critical that ell of the plans for QC be executed. The analyst must insert ap propriate blanks end replicates. The QA staff must conduct audits. Management must insist on timely QA/QC reports so that corrective action can be taken. Last, and most im portantly, the QC data and a data quality assessment should accompany the analytical report so that the user will know the date quality. The vast majority of the PCS publications omit the last step, forcing the reader to speculate on the data qua)ity. HONS 223756 310 Analytical Chemlstrv of pQgs n. SPECIAL CONSIDERATIONS IN PCS ABUSES Sine* PCB* generally occur as complex mixtures of analytes. soecial QC measures must be considered- The PCBs used for calibration of the analytical instrument my be mixture (e.g.. Aroclor 12&A) similar to that found in th* samples or group of inoividuel congeners. Any realistic option is a compromise from cal ibretion >th all 209 con geners. Thus, an estimate of the error sauced by the com promise should accompany the data. The selection of cel ibre tion mixtures was discussed in Chapter 8 Because of the complexity of the data, special pre cautions should be taken to assure both the qualitative no quantitative aspects. Many quantitation techniques involve summing the calculated response or concentration for many ,in dividual PCB peaks to yield a total'PCB value. Any system atic error replicated through severe) quantitations could re sult in a magnified error in the 'eoorted result, "he com plexity of the calculations also increases the chance of cal culation and transcription mistakes. A. Reference Materials A major component of a good QC program is the in clusion of reference materials as QC check samples. These may be routine daily accuracy checks, or may be part of a performance audit. Regardless of their use, reference ma terials must be validated prior to use. While in-house prep aration may be appropriate in many cases, the use of refer ence materials certified by an external organization lends much more credence to the results. Table 9-III lists some reference materials. The availability of standards of neet PCB mixtures and individual congeners was discussed in Chopiar 2. B. QA in Multiple Laboratory Networks When data from more than one laboratory are to be compared. special measures must be taken to assure data com parability. In a formal multi-laboratory network, it is ad visable that on# organization function as a QA laboratory. Tht QA laboratory must ensure that all laboratories in the network: Use the same procedure. * Execute these procedures without significant variation. HONS 223757 table VIII. Ief*r*c* Material* far PCI Analytic Melrla Ml iHImi IrtM iMtamt PCI Caaaaalt iim PCI Ceaceatrattea racier I2M/I2u0 (1 11 racier 12S4/I2M (I I) |m ?^ Mater it Metar || Ireatferwr all 1re*ferer all Mrthaaal* Metheaal* NeUeaei* Mrlheaet* Matbeaet* MatMaai* MlliMir NiMal' Pcrteae* Itaactaaa Uaactaaa Ueactaaa Ueacteae Caaactter all (aaacitar ail Pradar 1242 Pradar 12*4 Praclar l)({ pradar I2M Praclar i|| Praclar 12S4 Pradar IJH Praclar till Praclar 12M Praclar mi Praclar 1/21 Prat lar 17*2 Pradar I ft* Pradar |||| Praclar 1742 Praclar I2*4 Praclar 12*4 Praclar Hi* radar 1142 1" Mf/| >10 f/ m M/| S.MO i>f/at VMO **/. S.MI **/. S.OM ao/ot S.4M af/at S.MO */ S.MO ho/at S.ooo ao/ai 2.Mb 'Vat I.MO HO/P I.MO HO/P i.mo ao/at I.MO / 1 tare It* 1 lerai* I I Crbe SM IMt ( 104 t IM ( 107 I IM ( IM I 111 t 121 i no I ill ( us ( 132 t ns t 121 reliability tefrace Harlaa Analytical Cdabtttry StaMara* Prayrab Ptlaatlc lataarch Labaratary Matlaaal leteerch Cawncil 1411 la far# Street Mail fat. Naa Scatla IM 121 Chau at *1 . tv* Chaa aa it*. ISM U S Matlaaal laraav f tfaaPlaftaa. 0C 2UM Urlaaa iM) QA Ireach lost * Ciac iMett US. (PA Ciac iMett. OH 4%2iO (PP. IMlb HONS 221750 312 loOl# 1-|ll front ii.uod) HlUli PCI (.uapotH'on PCI CoACOotrotton Code AeoiUblltly Copotitor oil tApocitor oil MyOrowttc oi1 ttyorooltt oil HyOrowlit oil HyOrowlic oil lr**kluio*r ml t4i>v(r* oii IroAiiorwr ol 1 lr*ufor*r oil t tvh t Ivh I Vkh Sodtoont Vd>Mt Aroclor l?il Aroclor mo Aroclor iQtt Aroclor i;? Aroclor Aroctor IttO Aroclor 1014 Aroc tor via: Aroclor l?S Aroctor mo Aroclor i?? Aroclor I/S4 Aroctor l?A0 Aroclor 1 ?? Arocior IIV* 3 #*olk* 3 lo.otk* 3 loooU* 3 lf*olk* 3 ioooi*i 3 10*0 Ik* 3 1 o*o1k? 3 Io*o1* 1 io*our 1 to**tk? ? to*oIk* ? lovott* ? 10*0 Ik* 3 l0*0lk? 3 t o*ot k* lor kolkloQ tor to p >p*r otor chock ktaplo for prior Iky i'Ollutoni or other *tyk*% U levolt noi kpodHoO t <oito|. totoro HONS 223759 Quality Assurance 313 Obtain similar performance (i.e. . precision aod accuracy). * .Report results in a consistent format. It is advisable that all network members use aliquots of the sane standard solutions, use commonly obtained reagents where critical (e g., Horisii for column cleanup), and use similar apparatus and instrumentation. The QA measures specifically applicable to multiple laboratory analysis networks are Iisted in Table 9*11. As an example of ,ch a network, the U S. ERA has operated a network of laboratories for pesticide analysis in a variety of sample matrices (blood, adipose, milk, urine, soil, water, air, wildlife, and others) since the late 1960s As part of this network, an EPA laboratory (the QA Section of the Health Effects Research laboratory, 0R0, EPA, Research Triangle Park, NC, until 1982; now Environmental Monitoring and Suoport Laboratory. 0R0. EPA, Las Vegas. NV)) functions as a centra) QA laboratory. Analysis of composites, oeveiop* ment of methods, revision of the methods manual, supply of special reagents and standards, maintenance of instruments, site visits, analyst assistance, assessment of method execu* tion, and conduct of a periodic QC check sample program are among this groups duties. The check sample program consists of issuing a standard pesticide reference material (eg., fat spiked with pesticides and .PCBs), receiving results, and evaluating laboratory performance. The results from the 10* 20 participating laboratories are tabulated and each labora* tory given a numerical performance score based on both quel* native and quantitative results. Results for three fat samples spiked with PC8s at 0.5*1.5 ppm levels averaged be* tween 93% and 105% of the formulated concentration, with rel* ative standard deviations between 12 and 34% (Personal com* ".unications. R. R. Walts. 'J.S. EPA, Research Trianqle Park, NC, 1980*1981). However, several participants**SO% in one east**did not report PCBs in these samples. It is not known whether participants "missed" the PCBs or simply chose not to report their findings. Oespite the relatively good perfor* mances noted above, at least one participant was found (lucat et a!., 1980) to be short-cutting the prescribed analytical method (Watts, I960). The participating laboratory had elim* inated a liquid chromatographic fractionation and was quanti* tating only a single heptachlorobiphenyl peak against an Aroclor 1260 standard. HONS 223760 314 III. PREVIOUS QC MEASURES Analytical Chemistry of Pcas The U.S. ERA has taken steps to implement strong nr programs in various standard Methods of analysis and as oart of long-term project goals (EPA, 1979c, 1980a,b, 1981j Sellar and lientenberg, 1981). Table 3-1 listed the standard procedures that acknowledge the need to follow some type 0f QC program. QC measures have also been cited in several col laborative studies (OCKA, 1982; Sawyer, 1973, 19786; Oelfino and Easty, 1979; Oevenish and Herling-Bowen, I960; Pittaway and Horner, 1982). These and other collaborative studies are also discussed in Chapter 10. The QC program for the Ory Color Manufacturers As sociation (DCKA, 1982) collaborative study included instru ment calibration specifications, performance evaluation 0f the gas chromatography column with a standard mixture of PCBs. and measurement of sensitivity for PCSs by serial di lution of the standard, method blanks, specification of quan titation procedures and validation of sample preparation pro cedure. The validation of samole extraction, cleanup and analysis included workup of phnd and known spike samples. The results of the OCHA study indicate that variance in re ported PCB levels between laboratories was significantly re duced when a commercially prepared quantitation standard was used by all participating laboratories. Oata from the OCMA report indicated relative standard deviations of 3.1 to 9. IX within a laboratory, 2.4 to 40% between laboratories, and 7.3 to 41X for the total reproducibility for analysis of three different pigments. The Chemical Manufacturers Association sponsored a collaborative study of PCB concentrations in five different byproduct PCB samples (Pittaway and Horner, 19B2). Eight different laboratories participated in the study. In con trast to the OCMA study, no defined protocol or QC programs were specified for analysis of the matrices. Each laboratory was allowed to choosa the method of eitraction, cleanup, in strumental determination and quantitation, and QC program it desired. This study indicated that there are many sources of potential error in the quantitative analysis of PCBs. The lack of agreement of the measurements between laboratories indicated a true need for a strong QC program to produce com parable data. In a study of emissions from a municipal inciner ator and a co-fired (refuse*derived fuel plus coal) power plant, Haile et al. (1983a) used three laboratories to an alyze the different samples. Sets of spiked fly ash were sent periodically to the laboratories to serve as QC check HONS 223761 Quality Assurance 315 simples. Recovery of decachlorobiphenyl spikd at the 500?.S00 ng/g level ringed over an order or magnitude Oupiicote analyses within 4 libortory differed by is much s 4 factor of 3. Bush et }. (1983) hive illustrated 4 good quality control technique for single laboratory analyses. In routine analyses of environmental samples for PCBs by automated NRGC/ ECO. they utilized a quality control chart (figure (9*1) to monitor th instrumental response. The standard was run after every sixth sample. The chart in figure 9-1 also il lustrates the additive effects of random errors. While the fluctuation of the plots for the individual congeners is small, much larger fluctuations are seen for the "Total PCB" plot. IV. RECOMMENDED QA/QC MEASURES A good working QA program requires a set 01 written standard operating procedures for instrumental operation, routine laboratory operations, data review, reporting, and all other aspects of data generation. More importantly, the QA program must have support from all levels in the organiza tion. The goal must be to assure that data of known quality are being reported while minimizing interference with the analysis process. Once a working QA program is in place, the specific QC aspects pertaining to RGBs are relatively simole to imple ment. The QC will differ from organization to organization, and indeed, according to the individual project. The QC should be discussed with the data user (i.e., tne client) to reach agreement on the desired precision and accuracy. Summaries of the QC recommendations from three analytical procedures are presented in this section as ex* amples of thorough QC programs. A, Transformer Qi1 (Jung, 1981) In a review of analytical methods for PCB analysis in transformer oil, Jung (1981) recommended several QC mea sures: 1. Analyze a quality check sample daily to assess accuracy. Z. Analyze 102 of all samples in duplicate, se lected at random, to assess the precision. HONS 221762 316 COMKDUNO Analytical Chemistry of PCBs QUAUTY COnUOL CHAAf 20-2123 March 2130 21 22 23-24J3 20-2f figure 9*1, Quality Control Chart for HRGC/ECO Analysis of PCBt and Othtr Organoehlorina Compounds in Human HI 1k A "quasiilk" QC saaplt, containing individual PCS congantrs and insacticidas at known concantrations, was analyzad aftar avary sixth silk sanpla. Tha rasultt, plottad abova, indi* cata iamadiataly whathar tha pravious analysas ara within tha QC toiarancas. Raprlnted, with pamission, from Bush at al. (1983); copy* right 1983 by Association of Official Analytical Chamists. Inc. HONS 223763 Quality Assurance 317 3. Maintain a i0g 0f precision and accuracy data. 4. Maintain a record of the retention times of un known PC8s Analyze a certified sample, if available, at least quarterly. 8. Transformer fluids and Waste Oils (Seller and Lichtenberg, 1981) The elements of a section entitled "Precision and Accuracy" include: 1. A formal QC program must be operational. 2. The laboratory must demonstrate its capability with check samples on a periodic basis. 3- The analyst must dtmonstrate precision and ac curacy by analyzing at least four replicate standard addition samples- The recovery and standard deviation must meet EPA performance criteria (these were to be established at a later date). 4. Using the recovery end standard deviation from slope, control charts are to be constructed to serve as per formance criteria. 5. At least 10% of all samples or one sample per month, whichever is greater, must be analyzed by standard ad dition tecnniQues to monitor spike recoveries. S. Each time a set of samples is analyzed or there is a Change in reagents, a laboratory reagent blank should be processed. 7. Additional QC measures should be considered by each laboratory. These may include field duplicates to mon itor sampling precision, qualitative confirmation with a dis similar GC column, halogen-specific detector or MS. 8. A standard sample of KBs in a typical oi 1 ma trix must be analyzed daily before any samples are analyzed. The results of this analysis serve as instrument status checks, calibretion curve validation, and long-term precision measures. 9. An PA QC sample must be analyzed on a quart erly basis. Results within 15% of the true value are ac ceptable. If the results are unacceptable, the analyst must resolve the problem. MONS 223764 318 Analytical Chemistry of PCBs C. Byproduct PCSs (Erickson t at., 1983d) are. The elements of the QA section of this document 1. A formal QA plan is required. 1. A formal QC program must be in operation, in* eluding recordkeeping, certification, and performance checks. 3. Procedural QC measures include: a. GC performance criteria. b. H$ performance criteria. c. Confirmation of at least 10% of all qual itative identifications by a second analyst. d. Confirmation of at least 10% of all cal culations by a second analyst. 4. Sample QC measures Include: a. Acceptable recoveries of ,3C-labeled sur rogates (e.g., 50-150%). b. Spectral data quality must be evaluated. The chlorine isotope intensities must be of the proper ratios (e.g.. within t 20% of the ratios observed for standards). c. Internal standard areas must be within t 20% from injection to injection. d. For small (1-10) sample sets, 1 method blank, 1 duplicate (triplicate preferred), and 1 standard addition sample aust accompany the set. e. For intermediate (10*100) sample sets, the number of method blanks, replicates, and stenderd addition samples must comprise at least 10% each. f. With large (> 100) sample sets, alternate QC measures may be proposed. For example, if contamination has never been observed in blanks, the frequency of method blanks may be reduced. 5. Additional QC, specific to each organization and analytical problem, should be considered- HONS 2237*5 10 COLLABORATIVE STUDIES A collaborative study is tha validation of an an alytical method by several laboratories. Collaborative stud ies are generally considered the ultimate in Mthod valida tion and are required by most organizations before a method is accepted as "official," "final," etc. Collaborative stud ies ire i i so termed i nteriaboratory studies, round robins, etc. Guidelines for a collaborative test are available (Youden end Steiner, 1975; AOAC, 1982) although many studies differ markedly in both objectives and execution. Ideally, each participating laboratory receives the same sample set, performs the analysis according to a written protocol and re ports the results to a coordinator for evaluation. Two areas of fundamental disagreement are the degree of control over the participants and the data evaluation. The objective of a true collaborative study is to evaluate a given protocol, so all variables are held as constant as possible. Many stud ies, however, have permitted the participants to use any method they choose. These studies, then, evaluate either the "current state of the art" or the laboratories. The other point i: lisagreemert i$ the data evaluation. In a true col laborative study, whore the objective is to evaluate the method performance, the statistical evaluation summarizes the precision, accuracy, and any other performance measures and then attempts to evaluate potential sources of error (random, systematic, and laboratory-specific). Many studies, however, have been used to also evaluate the participant's perfor mance. Labs are rated by how closely they meet target val ues. This chapter discusses several PC8 collaborative studies in some detail because they (a) demonstrate the qual ity of the data obtainable for many procedures, (b) emphasize those few out of the myriad methods discussed in earlier chapters which have been subjected to this level of valida tion, (c) illustrate the different approaches to the eonduet of collaborative studies, and (d) permit direct comparison of some of the techniques for those studies whieh allowed the participants to select various techniques. 319 HONS 223766 320 Analytical Chpmistry of PCBj I. wiLOUre (HOLDEN, 1973) I'm study used three test samples containing kfl0^ amounts of organocnlorme pesticides, PC8s. or mercury, 5^,. teen of the 26 participants reported values for both a hexane solution of Chiophen A-60 and a cormorant homogenate sample (Table 10*1). The average accuracy */as 99* and the precision was about * 13% for the hexane solution and t 22% for the cormorant samp'e The participants were avowed to use the>r customary m-house procedures, which covered the rang# of ex traction, cleanup. GC column, and quantitation techniques All participants apparently used PGC/ECO. II. CHICKEN FAT ANO FISH (SAWYER, 1973) Nine laboratories collaborated an the analysis of PCBs in hexane, chicken fat, and fish. Existing AOAC multi* pesticide methods with PGC/ECO or PGC/ha'oqen specific oe* lector (HECD or microcoulometric) quantilitron -ere xmployea. The results shown in Table 10*1 indicate excellent perfor mance of the method for direct injection GC/ECO analysis with peak height quantitation. With the chicken fat which re* quired laboratory preparation, the precision was poorer, but the accuracy was very near 100%. The accuracy for the fish was much lower (n 75%). Similar results were obtained for all three matrices using PGC/ECO or PGC/halogen specific de tector with total area quantitation. III. PAPER80AR0 (FINSTERWALOER, 1974) Eleven laboratories participated in this AOAC study to validate a method for PCBs (Aroclor 1242 and 1254) in paperboard. The metnod involves alcoholic KOH extraction f-loristi coiumri Cleanup, ana PGC/ECO determination. The re* suits, shown in Table 10*1, indicate an average precision of about t 20% relative standard deviation (RSO) and an average accuracy of about 85%. In addition to tabulation of the data ana discussing potential outliers, the study author ranked the laboratories for each sample with a "1" for the highest reported concentration, a "2" for the next highest, etc. The sum of a laboratory's rank for each sample yielded a col* laborativa score. This technique is useful for identifying systematic errors which make a participant consistently either high or low. Laboratory ranking is discussed in more detail by Youdan and Steiner (1975). HONS 223767 ( l R|m KI <*MMi IWikM #< (#>.,Mji \*cu* *u fi 4 **l l ( (*lirW> ill J l*<*a* , AM f*4'<<9. << ixtt/ixti fH ifmm* t b In* 1111 I*m lai ii-, * */! t .|* f. IM ' xn H* > IV *'! I" *N'M V M M (* ii-- ! Hi IX II t1 IX t 11 t *t 1 ,w,}. , \ 4 M'M* l*.( ****** |tlt '**< X# tl MM t> l*tl t.a. la* I)** !. It |l*t ** r* IfM *>< ix*x / V !** 1 *.* <1 1 M* *** lt ( >- 1 to* It > ** ' N* V * ** xt > it t it r a t' it M1 4* % It I 1 '*l***laai *< Mm* tO <M*t*<l<>* in ** \9 MK <*U/U*I wm ui m 1 M ** ( <1 M* kl> *t'* 1 It BM I IS M* Mt It IX 1 # it IiiIm M Na in**' lt>tt W 1***4 t i( Cfl(t M1IIN l)*l 1 * *' 1 * N/M It t 1.. uro I I HlN Nl>m l.*i*|XttOC ImlM 1nt it 1 n lilt IMt ri * I m Imimi*M'H IW * 1 .M * >!> i||B N-< -- X 1* *'l ' l l i-* ' It |. * K% N~.|a. M,.* .tltl.M* < * | l > 1' N'.l it I'M | *>. I* M*a HiN *l/St'tt.-* 1 III wN It > t/ A *ilM't|XM > .< ** It i Mt )< 1* )m >li*t Mi tX */*> ' II t n * i * IN 1 a** J \\ WmitiH t* <** X V* 1-tX* Xt t M t >* In i*Im > Ht<* Xt X u><< I.V i*iMi>i(>rl t*i a*tU***-M*a*l (,,,(!, > 1 ,,,(> !*> > (,,,(>. )>> t,, ' *,(* MNP* t,,*<!, l|,,l>. IlMNI C,,t.Clv 1 (,,,tl. UMII tt *) <> l ***. >/ M* >1 t M*1 M ** M 1 *M* t > HH* It 1 IX t II II XI *i K*t iti/ A't |*4x|>l a MfM ***** In* 1 I **>< t t a*-*1 xt l<4'Ma. |tt| HONS 22376a 4t' I* I laaaal l~4l ** >a>a it (ak-tl1 (. 1` 11 IS* **' 9 laaalCI HI* I* WUlt ////% kSMJ iMI'taiv. mu im'tiM tllM >/ < S a s* a i Ik 4t k m Ik* s# a w at t m m M M t ii * i> i* i it aS ia.4 lk/ 4 II Itl t4 >aiai iiilMta > aM I (aw* ii'* la. rink* k I <4/a 4S l.tttai .< i it4 lla* *(*> a/ ta *M'`'tt mini a>-ai IIM mmtf It IS /* S **/! A >4/ 1 I **/< M tl !< 14*1 ttlaakaaa lit) tkl.M*aa* MiaaM Ik Hla< llla kk (aaapaal | It > ** m "Htai mm ttaaaa tnavia .a (tlanaaiaa u W>*< Ik *< < '9* kal\4 1441. a. . Mm* k> '1 Ittl N> t.aa. a akiaala4<'t N> Malta.. Ik akaax|i*a /l laauaiij > k tM* II aM IS iiimi *i iiakaiu miii ik aawiliak I> lit ** If Mina >i vataiu<. <k HaaniaaN (,,*,1' I M '- a* > mi>-- 14 la tl *1laiMiaiaiauauaa ama laianwaai aaaaau aaala I* Ikl a aa.i aaatatf Mat** 14 III (ailuitiiUMaataa tut* 14 iia it M|C*l4llaul*k MMau *!* k 4 4 4 4 ttai uu `<Uan\ tl ."N ti w >n 1 lw a* a W/an IItalail /<4k lalliiail It I P<4f it I ",/m II ,*/aa tkt ,.*/" *4* utV n a ,*/ta it it M Itl l ai mu Ml 'tf aal WI'IU ail ktaaak IMM Malat .>M /> tt/m U um ltwint'Mitut tint* I 4 I tt '* ittk* Ik kk Mk* I 14 af/tf I tl atilt 1) Mk Ik ti Mk at It II t Ml ' tl I II Ilk I MS 4 *>al aat via*. Ik I tutl4 <1 al Ikkl* HONS 223769 323 !#* It I KM '-J.il *M > . &.V lm ' tMM IM'II I MM '`(III** l WI l.l.*. .* Itl *><a.* lM*ll*llaf #< 4 UHl* HIM HIM *1H* It Ml Ulmt M l/U HIM IMII'HI a Ml *'M IMrtlMrl .Ml lUKIKMtl SK 'H* I -Mm* ' I n M MM Mm* M* IM<.M t% \ll S S* tt Ht I4i l IM **<* iaa I* M SI M ' M II Si III >1 l* I Itl 'iji i .*m ' -- ** > ii*4 11*^1.- anl Wivt M ..... *a. << im I'M I>'M hf IM MNIM IMMMIIW *|t'll MlllM. t KM "Mil 4m mutwi..' ml** iM >M im'ii taWi Mr* "M*a at HK.H i Una, ih< w lammaa in* '>!< iitalia laa #aaia* aij i.iiaH' > t*'i idlaaM Mai* mi dull M a"KI laavatiM M <M It *'111 >M t MIHliai a>'M *<.< I'M >* Kami iiIim aliMW *.*>*<>* auM/a.U, Ml'l'M \if*( tHl<4IUI IMlIlK M Mil tail ilaa *** iMMa IHHIia ralalll ** >*4 I lM| 40 1 tI H #H *4 >| 4M* iinriiiai tMiaia (il ) Minil ! >aa ii.ihi >m>< ImM IMII Cl,* MM a *la <* !* tm al U IIHIIIII la* * <l*l <M i.w*. al t,,a.ta *M a 'aaaait ml l,.a,ai, Mtai iua> MM** a* Immii a* MMtaa m iviiuaaM m Ml aiMr IM* m>* *t*a Vila la m<>ii a>im la aw m aa*ai<<*aa* mi Ma ai#*4 laaa all *.** .a im Mill#* Ml l*a ia Mm la <* |*M lni< at <* ana Miavt a. i'** iMMannt ..** *1 la. i|n. .iai* iMaraiaiaa *i im a*a "* Kl 1*1 aaalfi** ia..^> IM a*M Mill" l<a*M *M'*a< * iii'wa i* aiaaawi m . /*a m*U<mi Ml M' ** II .|| Ml **'. * * m tr* a <M HONS 223770 324 Analytical Chemistry of PC8s IV. MARINE SEOlHENTS (PAVIOU AND HOM, 1976) Ten participints were asked to analyze a sediment sample to assess the reliability of chlorinated hydrocarbon measurements. A)) participants presented values for total PC8s, seven presented a sum of 00T metabolites, *nd one auntitated dieldrin, cis-chlordane, end trens-cMordene. As can be seen in Table 10*1. the RSO of tnt PC8 values for all of tne laboratories was i 22V The participants used a variety of techniques for all steps of the analysis. The reporter concentration was slightly dependent on whether the sediment was dried and on the weight of sediment used; the authors recommended drying the sediment before extraction. The ouan* titation technique also affected the results. "Total PCB" and "Aroclor1' Quantitations both led to much less accurate results then a Webb and McCall (1973) type approach, which the authors incorrectly termed a homolog quantitation. They recommended the latter approach. V. QUANTITATION TECHNIQUES AND MILK (SAWYER, 1978b) Ten collaborators quantitated a synthetic mixture of one tri-, two tetra-, and one pentachlorobiphenyl; one tri* and two tetrechlorobiphenyls; and another mixture of two Aroclor 1254-fortiffed milk samples; one milk sample contain ing bioincurred PCBSi and one chicken fat sample containing bioincurred Aroclor 1242. The study was conducted by the AOAC to evaluate (a) different PGC/ECO quantitation tech* niques and (b) the applicability of the AOAC multiresidue pesticide method to milk. A. Quantitation Techniques Each collaborator was asked to analyze the two syn thetic PCB mixtures and the chicken fat sample by direct injection onto a PGC/ECO system wftfch met certain specifics* tions. The data were to be quantitated against standard Aro clor solutions supplied by the coordinator. Three quantita tion techniques were to be used: (a) summation of the height of peak matching the retention time of peaks in the Aroclor standard, (b) summation of the area of peaks matching the re tention time of peaks in the Aroclor standard, and (c) the individual peak comparison of Webb and McCall (1973). The first two techniques were those recommended in Section 29.018 of the AOAC method (1980a). The Webb-McCaU technique was being considered for inclusion in the method as an alternate Quantitation technique. HONS 223*71 Collaborative Studies 325 Based on the results summarized in Table 10-ii. the study author concluded that the Webb'McCall technique was generally an improvement over the other two techniques. The author also recommended that AOAC adopt the Webb-McCall tech* mque as the technique of choice when residues do not exhibit a PCB pattern similar to that of an Aroclor standard. 0. Milk The two milk samples were extracted, cleaned up, and determined by PGC/ECD using the AOAC method for quanti* tating PCB residues. The 05% average recovery and RSDs rang* ing from t 14% to t 17* (see Table 10*i) were considered ade* quate and consistent with previous results for PCBs in fatty foods (Sawyer, 1973). The author recommended that the AOAC method be modified to include milk and other fatty dairy pro* ducts as applicable matrices. VI. PAPER MILL EFFLUENT (DEIFINO AND EASTY. 1979) The collaborative study reported by Oelfino and Easty (1979) focused on the analysis of PC8s in paper mill effluents. The study consisted of two phases. The first phase was used to determine the comparability of PCB meth odologies between six different laboratories and the abil ities of the participating analysts to perform the basic op erations required for PCB analysis. These factors were de termined by direct injection of a performance standard and also the simple extraction and analysis of a spiked aqueous solution. The second phase required analysis of both known and blind samples by a single method. A modified EPA waste water analysis procedure (EPA, 1973) was followed by all participating laboratories, which involved liquid*liquid ex traction. a Florisil column cleanup, and PGC/ECO determina tion. The silica gei mtcrocoiumn step for ^pd<at>on 'C3s from pesticides was deleted for this study, since pesticides were judged to be unlikely constituents of paper mill efflu ents. The results of the first phase, extraction from distilled water, yielded an average recovery of 95 6% with a relative standard deviation of 14.7*. The relative standard deviation for direct injection of a standard solution was 1S.6X. The results for paper mill effluent yielded similar results with 93-6* average recovery with a 16.0* relative *OW$ 223772 326 fabl* IU II SiMfta'y < r.llattwatliat I. .I *1 kt* QwaM >1 l >Vn lailuitwcs ft.*U l v 1 1 |4 I^M 1<>> mm tar ViaiM-jni u CQV* ft tayalnl CiW">*l *wft (fftM tn| * mmi 1 mil '*< ii >* t *s0> .1. %*!* tin<*. tm1 <* W ft * V ft * m ft ft ft I'M ft A 4 *4 ft H ft M 4 n Ml A ft- HI A MM i/k 1/4* u** u*a U** l i*a m U* W* u* u*r w*a it*t u*a uu ua i/s* US* I/S4 US* us* US* ws US* US* /./ s i r s.s' /, . .S if * S.S141.1 (l>* 1*1.1 1)1 la*.1 ill la*** <1* *1 1*1 *.* *** Arac*wr ]f*f IIMlw U* irftltr *J4| *tw<lf l}*l Atacliir UU *il U4? AfMla. US* ArMla. US* AiNlti 1/S* liH'tr US* At-ktl* US* Atwltr m< Arktlwr US* A. Ml> US* Atwtlu* 1/S4 U tv .M*/w1 k S) 1*9/1* SS ftft/ftl U Ilf W|/ai 1 / Wwl 1 / a*/Ml * /* \M 1 1* ftM 1 M **/w( I 1 Ik MM l 1* Iftfft 1 1* MM / U MM l >1 MM i.U M " 0 U>ta t|/|.l *)* .*/( S If .Vvl lit "t/|A l 1* i*/** 1 /I "t'vi 1 It "t/yl 1 SI* w^'yl 1 S4 n*/wl 1 * "tM SUM* S M MM S * MM S */ mm S 11 I# 1 14 MM > l MM 1 1* MM i It MM > 1* PlM / IS KIM 1 1* i*ft S* *>* 1 IS iaM 1/ l Id t *0 * IS ns it \ S) IS 4 ; * ss li s ss ;; 41 ia IS *1 1 IS / II I M1 IB f lu 11 I* 4 04 1 *4 S * l IIS s ill s III* * a/ as a* * as i a/ i 4* 4 w < T if5rvt 4)ia, 111 lUI |Mt ft*i*M t>k Ai*S*r MiAtt'4. * * > 1*4*1 . NMM Sr\t tlMftMt* k tiiuKf *\ * (Wknllttllii Inimt litlikil lay ll~ yr*y*rt4 < imm i lh* kulvH k it* tM MA/tCIf 4 mi mlidkMi !*.**t. furkt i.f ,*.S,S'I t *il turn mmin ' iwn t*ifKarr*il kfkkkTM CMl*lrll* awl Wl*rft*hU- S**m1* MMlyti* by MMC aaltirktiftww ulrKliM. c !-*<*. <> Wit lirii ( istftkt, *na ii*1m! ** wi*. im<> <w r>'" '* <l * >."' ><>. niM>k .m-- (t> > <> 4aaltl< <*#. t MOHS 223773 Collaborative Studies 327 standard deviation, and indicated that the method was satis* factory for paper mill effluents. The similarity of the pre cision and accuracy of direct injection, a distilled water sample, and th* papermill samples indicated that the PCC/ECD analysis (including quantitation) was the principal source of error. VII. WT LAKE SEDIMENT (LEE AND CHAU, 1981a) Fourteen laboratories were given one isooctane so* lution and three sediment samples for analysis by the method of their choice. One sediment sample contained the native PC0s and the other two were aliquots of the first to which 1.01 and 1.22 ppm of a 1:1 mixture of Aroclor 1254 and 1260 had been added. the participants used a variety of tech* niquts, with the only common denominator being PGC/ECO for the instrumental determination, The results for the unspiked sample of Lake Ontario sediment were generally low, trace or not detected and were not summarized by the authors. The re* suits for the spiked samoies were summarized *n terms or the percent recovery of the spike. The mean percent recoveries were 93 and 99%, with R$0s of t 18 and t 19V respectively. The fourth sample, 1.00 ng/pl of a 1:1 mixture of Aroclor 1254 and 1260, wasanalyzed by direct injection onto the GC. The 112% recovery with an RS0 of t 19% was surprisingly poorer than the results for the samples whichwent through the entire method. The authorsused a Youden plot (Youden and Steiner, 1975) to compare the results for the two spiked sediment samples (Figure 10*1). The 45 diagonal line repre* sents the true ratio of the PC6 content in the two samples. As can be seen in Figure 10*1. the plot easily distinguishes the systematic error (distance along the 45 line from the design value) from random error (distance from the 45 line). The value reported by Laboratory No. 4 for Sample No. 3 was rejected as an outlier. lee and Cheu presented some discussion of the rela* tive merits of the various extraction, cleanup, and notably, quantitation techniques employed. Eight participants used the Webb and McCall (1973) quantitation technique and had a mean accuracy of 103% with a BSD of t 4.5% for the sample of Aroclors in Isooctane for direct injection. The other eight participants used a variety of multiple*peak quantitation techniques and had a mean accuracy of 122% with a ffSO of t 23%. Clearly, for these laboratories and this sample, the Webb and McCall technique was both more accurate and more precise. The authors concluded that tne RS0 for these sam ples was i 20%, the method detection limit was between 0 01 MOMS 223774 LAB RESULT ON SAMPLE 3 (ppm PCB) 328 Analytical Chemistry of PCBj LAB RESULT ON SAMPLE 2 (ppm PCB) Figure 10-1. Pet red Semple (Youden) Plot for Two Wet Sediment Semples Numbers in circles ere the participant's identification numbers. Reprinted, with permission, from lee and Chau (1981a). NONS 223775 Collaborative Studies 329 and 0 02 ppm, the various extraction and cleanup methods ap pear to Be equally efficient, and quant 1 tat-;n was a major source of error. VIII. NATURALLY CONTAMINATE!) QRY S0lHNT$ (fcE ANO CHAU. 19816) a companion to the wet lake sediment study (Lee and Chau, 1981a) discussed above, this study required 15 partici pants to analyze four samples (actually two duplicate ali quots) of naturally contaminated dry sediment, a cleaned up extract of one of the sediments, and a 600 p$ yL mixture of Aroclor 1242, 1254, and 1260 (1:1; 1). As cjn be seen in Table 10-1, the results for the Aroclor mixtu-e had accuracy and precision similar to the other studies. The precision for the sediment samples, however, was about t 2$%, even after rejection of outliers. Furthermore, the intralabora trietory precision fflSO of values reporteo *'ar the blind duplicate samples) ranged from less than IX to over 100X. Typically, the results were in fair agreement ;e.g., 1.4 and 1.7 pg/g for an RS0 of 14X). The participants used a variety of techniques for all stages of the analysis. One participant used HRGC/EC0; the rest, PGC/ECD. The authors attributed the poor perfor mance of the participants in this study relative to that in the wet sediment study to the fact that this study utilized real samples. They recommended the use of these sediment reference materials for both internal and inte-laboratory QC studies to improve the data quality. IX. AHeiENT AIR (8I0LEKAH, 1981) High-volume air samples from Boston, Massachusetts. and Columbia, South Carolina, were collected or. a glass fiber fi lter-polyurethane foam sorbent trap. Alfqusts of the or ganic extracts were sent to nine laboratories. The labora tories were permitted to use any procedure in the analysis. Host groups used either Horisil or silica gel :olumn chroma tography in the cleanup. Several used a chemical degradation (sulfuric acid, base, br chromium trioxide) as an additional cleanup step. Host of the participants used P1C/ECD for the sample analysis. Two laboratories used HRGC/EC3 and one used GC/EIMS. The precision for the PCB measurements (t 26% to t 39%, see Table 10-0 was comparable to that observed for most pesticides; however, the precision for t-e polychloroterpenes (toxaphene) was t 116%. Bidleman (1961) recommended that the validity of sample collection also be studied in a collaborative study. NONS 223776 330 Analytical Chemistry of PC8$ X. QRT PIGMENTS (OCHA. 1982) The Ory Color Manufacturers Association (OCHA) veloped a method for the analysis of pigments using PGC/ECD The method has two sample preparation options, hexane/ sulfuric acid partition for phthalocyanine blue pigments Jnd a methylene chloride extraction/Horisi l column cleans tor diarylide yellow, phthalocyanine blue, and phthalocyanin* green pigments. The 10 participants of a col laborati ve conducted by OCHA were all OCMA member companies. They *er asked to analyze five samples (one yellow, two blue, end t-o green pigments). The two blue pigment samples were analyzeo by both cleanup options. Several of the participants did not adhere to the method and their data were not included m the summaries presented in Table 10*1. The average fiSD for tn^ seven values in Tjpie 10*1 was about t 19%. The participants reported their repeatability on four different days, which permitted an evaluation of the within* and between-laboratory components of the $S0. for aiaryim* yellow (first sample in Table 10*1), the quantitation of the 3,3'-dUMorobipheny] in the sample had similar within* ano between*laboratory error components. The source of error in the quantitation of the decacftlorobiphenyl in the two phthal ocyanine green samples could not be deduced. The toetwtenlaboratory error contribution accounted for almost 80% of the total error for the four analyses of phthalocyanine blue, which contained several pente* and hexachlorobiphenyl con geners. The higher RSOs for these samples was attributed to the greater number of congeners and also to the large number of interferences. JU. INSULATING OILS (ROUSE. 1982) This study was conducted to test the precision of a proposed American Society for Testing Materials (ASTH) method (Method 0 4059) for the analysis of PC8$ in mineral insulat ing oils by GC/ECD. In# study was conducted by ASTH Com mittee 027 * Electical Insulating liquids and Oils. Ten par ticipants reported results for six transformer oil samples containing Aroclor 1242, 12S4. 1260. or mixtures thereof. As shows in Table 10*1, the average recovery was 98% and the average RSQ was 1S%. MOMS 22377? Collaborative Studies 331 XII. BV* PRODUCTS FROM INDUSTRIAL PROCESSES (PITTAWAY ANO HORNER. 1982; HGQCES ET Al. . 1982; WESTER8ERG V hi 1984) ' This study was conducted by the Chemical Menu* lecturer's Association (CMA) to evaluate th available an* atytica) methodologies for analysis of commerc-al products and wastes. The eight participants were mostly industrial laboratories experienced in the analysis of by-product PC8s in industrial matrices. The study was designed to "simulate the situation in which a company independently attempts to determine the number and quantity of incidentally generated chlorobiphenyls in its process and/or waste streams" (Pitt* away and Horner, 1982). The participants were asked to an alyze a set of five samples: a chlorinated benzene waste, two mixtures of chlorinated benzenes, a chlorinated aliphatic waste stream sample, and a chlorinated aromatic sample. The samples were chosen to typify process stream matrices that were regulated by ERA. The coordinators made no attempt at controlling sample preparation, analysis, quantitation, re porting format, or QA. Most participants useo either direct injection or a simple dilution for sample preparation. Most participants used GC/EIMS, although one participant used PGC/ ECO and one used PGC/FIO. The latter's results were 100 to 1000 times higher than the average and were excluded from the data analysis (Pittaway and Horner, 1982). As can be seen from the results In Table 10-1. the precision ranged from i 34% to t 92% RSD. The accuracy for one sample, which was a spike of another sample, was found to be 75%. Since the data were tabulated by homolog, the error contribution by homolog was assessed. As shown in figure 10-2 for one of the samples, the lower homologs tended to contribute more of the error. This may be a function of the techniques used, but is more likely a function of the matrix interferences, which were chlorinated benzenes and chlori nates alipnatic*. in aodition to the differences in tech niques, the reporting units were often vague or unspecified. Some of the overall error may have been caused by differences in data reporting, since it is unknown whether the all of the respondents corrected for density in their reporting of "ppm." Pittaway and Horner (1962) concluded that, under uncontrolled conditions, one cannot expect to receive PC8 an alytical results which are sufficiently reliable for regula tory decision-making. It should be noted that the complexi ty of the PCS mixtures and the matrices in this study were much greater than those in studies involving Aroclor-derived PC8s in environmental matrices. NONS 223778 68% figure 10-2. Histogram of Crror Contribution l>y Homologs for Sample A from CMA Study Reprinted from Mo.ujes el at. ( 1083). MONS 223779 Collaborative Studies 333 XIII. BY-PRODUCTS I* A CHLORINATED AROMATIC WASTE fFRTrxtfMI T Al.. 1983c) Th>$ stufly -as conducted to assess a method for the analysis of incidentally generated chlorinated biphenyls in commercial products and product wastes (Erickson et al., 19B2). Four participant* received calibration solutions at known concentrations, instructions for analysis and data re* porting, and a set of samples. The sample set included paired samples of (a) additional ampules of the calibration solution of 11 PCS congeners at unknown and slightly differ ing concentrations which required only GC/E1MS determination (samples 7 and 8), (b) a chlorinated aromatic waste which re quired only GC/ElMS determination (samples 9 and 10), and (c) the same chlorinated aromatic waste which required both la boratory preparation (Florisil column cleanup) and GC/EIM5 determination (samples 11 and 12). An additional sample, again the chlorinated aromatic waste, was supplied in the form of a magnetic tape (sample 14). This last sample re quired only data interpretation by the participants. Figure 10-i presents 3 schematic of the entry points into the sample analysis scheme. The results are summarized in Table 10-1. The overall errors ranged from t 12 to t 182%. The two RSDs over 100% were inflated by one participant who appeared to be an outlier. The first two samples were dilutions of the cali bration solution. Since the concentrations were known, the accuracy could be assessed as shown in Table 10-1. A compar ison of the Youden pair samples (samples differing only in concentration by about 10%; Youden and Steiner. 1975) were compared using a Student's t-test. At the 95% confidence level none of the participants correctly differentiated among the samples. This indicates that the method precision is > 10%. One or tne samples consistea simpiy of a magnetic tape containing a calibration analysts and an analysis of the same original sample used for four of the other samples in this study. The interpretation of this magnetic tape pro vided a direct assessment of the data reduction error The qualitative analyses identified from 55-109 peaks as PCBs al though the participant reporting the highest number clearly did not evaluate the data since they reported 14 monochlorobiphenyls. Two of the three reporting participants calcu lated equivalent response factors from the standard run, while one participant reported response factors two tines higher. The t 25% R$0 for this sample was the largest indi vidual contribution to the total error, as shown >n Figure 10*4. AONS 223760 334 Analytical Chemistry of PC8s Samples 11 and 12 Samples 7, 8. 9, and 10 Sample 14 Figure 10-3. Analysis Flow Scheme tor Byproduct Collaborative Study. Showing Sample Entry Points Reprinted, with permission, from Erickson et al. i1983c HONS 223781 Collaborative Studies 335 70 40 JO 'H. '12 > ioU S i JO '7 'I 'V. '10 -l|% 7>oa>-o" -17% iurv*a*al ti'or 20 M* -2*% Figure 10*4. Plot of Error in By-product Collaborative Study by Semple Type, Showing Contributions of the Anelysis Steps Reprinted, with permission, from Erickson et el. (lBB3c). HONS 223782 336 Analytical Chemistry of PC6s The data indicate that the overall method variation appears to be t 60% RSQ. This is shown in figure 10-4 (out liers excluded). There is about t 25% variation associated with the data interpretation step. About t 17% variation pears to be associated with instrumental error and t 18% var iation is associated with sample preparation. The results of this study indicate that the precision and accuracy of this method are lower than for many other methods. This collabor ative study, however, was operating at the lower limit of in strumental sensitivity (selected ion monitoring mode) where precision is poor and also employed samples containing about 80 PC8 congeners in a matrix containing many other chlori nated compounds. Thus, this was an extremely tough challenge to the method. A second study of the method using more col laborators. simpler PCS mixtures, and higher concentrations is currently being conducted. Preliminary results indicate that the precision, accuracy, and surrogate recovery are bet ter at higher PCS concentrations (8>shop and Gebhart, 1984). XIV. HERRING tMUSIAl ANO UTHE. 1983) In this international study, 23 participants re ported results for PC8s in unspiked and spiked (1,00 mg/kg Aroctor 1254 in oil) samples of herring oil. Each partici pant was free to choose the analytical method, although Aroclor 1254 standard solutions were provided for use as a quan titation standard. The overall precision of the higher level (spiked) sample was substantially better than the precision for the lower level sample. There was no significant differ ence in the quantitation based on four calculations*, either the participant's usual method or the sue of three prominent Aroclor 1254 peaks compared to either the participant's own standards or a standard solution of Aroclor 1254 supplied by the coordinators. Also, no significant difference was found when the GC column efficiencies were compared. There did. however, appear to be e dependence of the results on the type of liquid phase in the GC column; the euthors recommended the use of high grade silicone stationary phases. They also noted that the in-house calibration standards were as much as 6% different than that supplied by the coordinators. The authors also observed significantly higher velues for parti cipants who used Florisil cleanup as opposed to those who used alumina. A lengthy discussion of the ceuses was incon clusive. XV. 80VIHE SERUH (8URSE ET At., 1983b) Twenty-five laboratories which are engaged in rou tine analysis of blood samples for PCBs and other chlorinated MONS 223783 Collaborative Studies 337 hydrocarbons collaborated in this study coordinated by the Centers for Disease Control (CDC). The participants were free to choose the analyticel method and employed a wide va* nety of techniques. Only 12 participants which reported the prescribed duplicate analyses on a low- and high-level sample were included by the study authors in the statistical analy ses presented in Table 10-1. The total precision of t 37.0% and t 30.7% for the two samples (Tab)t 10'1) was further broken down. The intra-laboratory variance was t 16.8% and 11%. while the inter*laboratory variance was t 33.0% and t 28.6% for the low and high level samples, respectively. The accuracy reported in Table 10-1 is highly mis* leading. The prepared value used for comparison with the participants' values is actually a COC analysis of the sam* pies which were prepared from in vivo-bound PCBs (8urse et a!.. 1983a). There is no data on ' the accuracy of the in house analysis. Nevertheless, the two samples were dilutions of the same pool, so it may be reasonable to assume that the relative ratios are reasonably correct. Thus, the collabora tive oate show that there is a higher bias at lower concen trations (239% recovery for the lower concentration sample versus 165% for the higher). The authors attributed most of the accuracy error (i.e., high values by the collaborators) to two sources: high reagent blanks and failure to com* pletely separate PCBs from OOT and its metabolites. They noted that the three participants which were within t 3 stan dard deviations of the COC mean either used a small volume of solvent to minimize the background or oxidized the OOT ana logs . XVI. IU8RICATINC OILS (BECXER. 1984) This study was part of a cooperative program be* tween the U. S. National Bureau of Standards and the American Society for Testing and Materials to develop an accurate ano relative simple aothod for determining PCBs in used and re* refined lubricating oils. Eleven samples were prepared, some containing knptm amount of Aroclors in clean oil, and some containing industrially incurred PCBs as shown in Table 10-1. Two duplicates and a blank were included in the sample set. In addition, one sample contained only an oil additive pack* age which was suspected of causing interferences with some PCS analyses. The samples were analyzed using the partici* pants' in-house procedures. The 19 participants all used GC/ ECO, some packed and some capillary column. All laboratories used external standard calibration and quantitated the PCSs as individual Aroclors. A variety of cleanup techniques were reported, although a combination of Florist) and sulfuric <eid was most widely used. HONS 2237* 308 Analytical Chemistry of PCBs As noted in Table 10*l. most of the resu'*- were very close to the prepared concentrations, i.e.. the ^curaCy was high. However, the AO to 60% relative standard deviation on most of the samples indicates that the precision was not nearly as good. An examination of the data by decker (1984), including Youden plots of the duplicate samples, indicated that most of the error was systematic. The intralaboratory precision was generally good. Becker inferred that problems with standardization and/or quantitation caused the bias in some of the participants' results. HONS 223785 BIBLIOGRAPHY Aaronson, M. J. , J. 0. Tessari and S. M. 8ergin. "PC8s in Transformer Oils." Bull. Environ. Contam. Toxicol. 28:584-591 (1982). Acker, i. and F. Schulte. "Occurrence of He*achlorobenzene and Polychlorinated 8ipheny)enes Besides Chlorinated Insecti cides in Human Fat Tissues and Mil*.," Ernaehrunosforschuno 16(4): 559-67 ( 1972), Chem, Abst. 78:805S2c71OT).----------------- Atkerman, 0. C. . L. 1. Scinto. P. S. Sakshi. 9. G. Oelumyea. 9. J. Johnson, G. Richard and A. M. Takata. "Guidelines for the Oisposal of PC8s and PC8 Items by Thermal Destruction," USEPA, IERl, Research Triangle Park, NC, EPA-600/ 2*81*022, February 1981, 317 pp. Ackerman, 0. G. , L. 1. Scinto, P. S. Sakshi, R. G. Oelumyea, R. J. Johnson, G. Richard, A. M. Takata and E. M, Sworzyn. "Destruction and Oisposal of PC8s by Thermal and Non-Thermal Methods," TRW, Inc., Redondo Beach, CA, Noyes Oata Corpora tion, Park Ridge, New Jersey, 1983a, 417 pp. Ackerman, 0. G.. J. f. McGaughty and 0. i. Wagoner. "At-Sea Incineration of PC8-Containing Wastes Onboard the M/T Vulcanus," TRW Inc., Redondo Beach, CA, for the U.S. Environmen tal Protection Agency, Office of Research and Developercnt, Contract .'lo. 53-02-3174, Work Assignment No. 103 (April 1963b), 273 pp. Adams, J. 0. and J. M. Caro. "Polyurethane Foam as Trapping Agent for Airborne Pesticides, Analytical Method Develop ment,1' Environmental Research Laboratory, office of Research and Development, U.S. Environmental Protection Agency, Athens, GA. EPA-600/4-80-008 (January 1980). Adams, J., K. Menzies and P. Levins. "Selection and Evalua tion of Sorbent Resins for the Collection of Organic Com pounds," U.S. Environmental Protection Agency, Research Triangle Park, NC. EPA-600/7-77-044 (April 1977). 339 MONS 223786 340 Bibliography Adam*, T. T. , N. J. Williams, ft. J. McElhaney and ft. 4 Viator. "Analysis for Polychlorinated Biphenyls in Environ mental Samples," Union Carbide report prepared for the u s Department of Energy, Contract No. W 7405 eng 26 (June 1979) Addis, C. and ft. Y. Komai, Eds. "Proceedings: 1983 PCB Sem inar,' Electric Power Research Institute, Palo Alto ca EPRI-EL-3581, June 1984. ' Addis, G. and J. Marks, Eds. "Proceedings: 1981 PC8 Sem inar." Electric Power Research Inst., PaloAlto, CA. epqj. El-2572. CONF-01126O (NTIS No. 0EB29O6457), September 1962 296 pp. ' Addison, J. 8. and M. E. Nearing. "An Approach to the Prpa. ration of Standard ReferenceMaterial for the Analysis 0f Polychlorinated Biphenyls in Marine Sediments." Intern, j Environ. Anal. Chem. 11:9-16 (1902). Ad lard, rapny." (1978). E. ft. "A Review of Octectors for Gas Chromatog* :n CRC Critical Reviews >n Analytical Chemistry Afghan. 8. K. and 0. Mackay (Eds.). Hydrocarbons and Halogenated Hydrocarbons in the Aquatic Environment, Pfenum Pub7 llshing Corporation, New York. Proceedings of International Symposium on the Analysis of Hydrocarbons and Halogenated Hy drocarbons in the Aquatic Environment, Ontario. Canada. 1978 (I960). Ahling, B. and S. Jensen. "Reversed liquid-liquid Partition in Determination of Polychlorinated Biphenyl (PCB) and Chiorinated Pesticides in Water," Anal. Chem. 42(13):1483-1406 (1970). Ahnoff, M.. G. Eklund and B. Josefsson. "Analysis of PCB in Water from the Sweoisn West Coast,' Acta Hyorocnim. Hyprobiol. 7(2):171-178 (1979). Ahnoff, M. and 6. Josefsson. "Confirmation Studies on Poly chlorinated Biphenyls (PCB) from River Waters Using Mass fragmentography," Anal. Lett. 6(12):1083*1093 (1973). Ahnoff, M. and 6. Josefsson, "Simple Apparatus for On-Site Continuous liquid-liquid Extraction of Organic Compounds from Natural Waters," Anal. Chem, 46(6): 658-663 (1974). Ahnoff, M. and B. Josefsson. "Clean Up Procedures for PCB Analysis on River Water Extracts, Bull. Environ, Contain Toxicol. 13(2):159*166 (1975). MONS 223787 Bibliography 341 Ahnoff. M. and 8. Josefsson. "Apparatus for in Situ Solent Extraction of Nonpolar Organic Compounds in~lea and River water." Anal. Chem 40(0):1260-1270 (1976) Aitzetmuller, K. "Adsorption Liquid Chromatography of ODT end Polychlorinated Biphenyls," J. Chromatogr. 107:411*415 (1975). Alben. K. end E. Shpirt. "Distribution Profiles of Chloro form, Weak Organic Acids, and PC8s on Granular Activated Car bon Columns from Waterford, New fork." Environ. Sc 1 - Technol. 17(4):187*192 (1983). -------------------------------------------- Albro. P. W. "Problems in Analytic Methodology: Sample Han dling, Extraction, and Cleanup," Ann. N.f. Acad. Sci. 320: 19*27 (1979). Albro, P. W. "Validation of Extraction and Cleanup Pro cedures for Environeiental Analysis," Chapter 0 in Environ mental Health Chemistry, The Chemistry of Environmental Agents as Potential Human Hazards, 3. 0. McKinney, Ed. (Ann Arbor, Ml^ Ann Arbor Science Publishers, Inc., 1980), pp, 163-175. Albro, P. W. and l. Fishbein. "Quantitative and Qualitative Analysis of Polychlorinated Biphenyls by Gas-liquid Chroma tography and Flame Ionization Oetection, I. One to Three Chlorine Atoms," J, Chromatogr, 69:273-283 (1972a). Albro, P. W. and L. Fishbein. "Intestinal Absorption of Polychlorinated Biphenyls in Rats," Bull. Environ. Contam. Toxicol. 8(1):26-31 (1972b). Albro, P. W., J. K. Haseman, T. A. Clemmer and 0. J. Corbett. "Identification of the Individual Polychlorinated Biphenyls in a Mixture oy Ges*Liquid Chromatography," C, Chrc-ausr. 136:147-153 (1977). Errata published in J. Chromatogr. 139T 404 (1977). Albro, P. w. and 6. J. Corbett. "Extraction and Clean*up of Animal Tissues for Subsequent Determination of Mixtures of Chlorinated 0ibenzo*o-dioxins and Oibtnzofurans." Chemosphert 7:381-385 (1977). Albro, P. W., J. R. Hass and W. 6. Crummett. "Summary of the Workshop on Recent Advances in Analytical Techniques for Halogenated Aromatic Compounds," Ann. N.Y. Acad. Sci. 320: 125-130 (1979). MONS 223788 342 Bibliography Albro, P. W. and C. E. Parker. "Comparison of the Composi tions of Aroclor 1242 and Aroclor 1016," J. Chromatnnr iso. 161*166 (1979). Albro, P. W. and C. E. Parker. "General Approach to the fractionation and Class Determination of Complex Mixtures of Chlorinated Aromatic Compounds," J. Chromatoor. 197 (1980). Albro, P. W. , J. T. Corbett and J. 1. Schroeder. "Quantita tive Characterization of Polychlorinated Biphenyl Mixtures (Aroclors 1246, 1254 and 1260) by Gas Chromatography Using Capillary Columns." J. Chromatoor, 205:103*111 (1981). Albro, P. W.. J. S. Schroeder, 0. J. Harvan. and 0. j Corbett. "Characteristics of an Extraction and Purification Procedure for Chlorinated 0ibenzo(g]dioxins and 0ibenzofurans in Soil and Liver." J. Chromatoor. 312:165-182 (1984). American National Standards Institute, Inc. "American Na tional Standard Guidelines for Hanoiinq and Qisoosal of Capicator- and Transformer-Grade As kart Is Containing Poly chlorinated Biphenyls, ANSI C107.1*1974 New York. NY (1974). American Society of Mechanical Engineers. "Test Protocol: Sampling for the Determination of Chlorinated Organic Com pounds in Stack Emissions" (1964). Unpublished report from Environmental Standards Workshop. American Society for Testing and Materials. "Standard Speci* fications for Chlorinated Aromatic Hydrocarbons (Askare)s) for Capacitors, ANSI/ASTM 0 2233-7*" in Annual Book of ASTH Standards Part 40, Philadelphia, Pennsylvania (1978a), p. 647-649. American society .or Tasting .iu Macanais. 'Standard Speci fications for Chlorinated Aromatic Hydrocarbons (Askarels) for Transformers, ANSI/ASTM 0 2283-75," in Annual Book of ASTH Standards. Part 40, Philadelphia, Pennsylvania (1978b)7 p. 650*658. American Society for Testing and Materials. "Standard Method for Rapid Gas Chromatographic Estimation of High Boiling Homologues of Chlorinated Biphenyls for Capacitor Askarels, ANSI/ASTM D 3303-74 (Reapproved 1979)." in Annual Book of ASTM Standards, Part 40, Philadelphia, Pennsylvania (19$&a)~ pp. 670-876. American Society for Testing and Materials. "Standard Prac* tice for Sampling Water, ASTM 0 3370," in Annual Book of ASTM Standards, Part 31, Philadelphia, Pennsylvania. MONS 223789 Bibliography. 343 American Society for Testing and Materials. "Standard Method for PoJych Jorinated 8'phenyJs (PC8s) in Water, AN5I/S7M D 3534*80," in Annual Book of ASTM Standards Part 31, Philadelphia, Pennsylvania (1981a), pp. 816-033. American Society for Testing and Materials. "Standard Method for Analysis of Environmental Materials for Polychlorinated Biphenyls, A$NI/A$TM 0 3304*77," in Annual Book cf ASTM Standards Part 31, Philadelphia, Pennsylvania (1981b), pp. 877*885. American Society for Testing and Materials. "Standard Method for Analysis of Polychlorinated Biphenyls in Mineral Insulat* ing Oils by Gas Chromatography," ANSI/ASTM 0 4059*63," in Annual Book of ASTM Standards. Part 40, Philadelphia, Pennsylvania (1983), pp. 542*550. Anderson, ft. J. and ft. C. Hall. "Hall Bipolar Pulse. Differ ential Electrolytic Conductivity Qetector for GC," Amer. Lab. 106*124 (February I960). Anderson, T. "The Pole of Legislature in the Peculation of Toxic Materials," in PCBs: Human and Environmental Hazards, f. M. O'ltri and M. T! Kamrin, Eds. (Boston; Butter-worth Publishers, 1983), pp. 375*382, Andren, A. W. "Processes Determining the Flux of PC6$ Across Air/Water Interfaces," in Physical Behavior of PCBs in the Great Lakes, 0. Mackay, S. Paterson, T 7! feisenreich and M. S. Timmons, Eds. (Ann Arbor, MI: Ann Arbor Science Pub lishers, Inc., 1963), 442pp. Anonymous. Mew Scientist. 612 (1966). Anonymous. "Toxic Impurities in Polychlorinated Biphenyls Environmental Impact," in Environ, ftet. 5:308-312 (1972). AnonyaK>us. "Extraction of PCBs from Transformer OH for GCEC0 Analysis with 'Baker* Disposable Extraction Column Octyl(Ca) (7087-6)," Application Mote SS-AN017 (J. T. Baker Chemical Co. Phi 11ipsburg, NJ), November 1981. Anonymous. PC8s in (1982a). "M8S Oevelops Improved Technique for Measuring Oils," J. Assoc. Offic. Anal. Chem. 65(4): 1033 Anonymous. "Method Improves PC8 Measurements in Oil," Chem. Ehq. News 19, March 1, 1982b. Appleby, A. "Atmospheric Freons and Halogenated Compounds," U.S. Environmental Protection Agency, Office of Research and Development, EPA-600/3-76-108 (November 1976). MONS 223790 Biography Araki. Y. and K. Tanak*. ''Simple Screening Method for [Hepatic] Enjyme-inducing Agents of Polychlorinated Biphenv) (PCB) Type." Pukuoka-lqaku-2asshi 6S<1);47-52 (1974)- chem Abst. 81: 146433n ( 1974). -------- Armour, J. a. "Gas Chromatographic Data for Polychlorinated Biphenyl Components in Six ArodorsB." J. Chromatoar. 7Mu. 2B2 (1972). ---------------------- Armour, J. A.. "Quantitative Perchlorination of Polychlor inated Biphenyls as a Method for Confirmatory Residue Mea surement and Identification." J. Assoc. Offic. Anal. Ch* 56(4): 988-993 (1973). '------------ Armour, J. A. and J. A. Burke. "Method for Separating Poly chlorinated Biphenyls from DOT and Its Analogs," J. Assoc Offic. Anal. Chew. 53(4): 761-768 (1970). ----------------- Armour, J. A. and J. A. Burke. "Behavior of Chlorinated Naphthalenes in Analytical Methods for Organochlorine Pesti cides and Polychlorinated Bionenyls." J. Assoc. Offic. Anal Chew. 54:175-177 (1971). " Armstrong, 0. E. and D. L. Swackhamer. "PCB Accumulation in Southern Lake Michigan Sediments: Evaluation from Core Analysis," in Physical Behavior of PCBs in the Great Lakes. 0. Mackey, S. Paterson, $. J. Eisenreich, M. T. iimmons, Eds! (Ann Arbor, MI: Ann Arbor Science Publishers, Inc., 1983). 442 pp. ' Armstrong, D. w. and R. Q. Terrill. "Thin Layer Chromato graphic Separation of Pesticides, Decechlorobiphenyl, and Nucleosides with Micellar Solutions." Anal. Chem. 51H3): 2160-2163 (1979). Arnoux. A.. J. L. Monod, and T. Schembri. "Cas-Chromatngrephic and Gas Chromatographic/Mass Spectrometric Identifi cation of PCBs, Linear Saturated Hydrocarbons, Polynuclear Aromatic Hydrocarbons and Phthalates in Oeep Sediments from the Western Mediterranean Sea," Journ. Etud. Pollut. Mar. Hediterr.. 6:469*474 (1983); Chem. Abstf. 16171770661 (199*). Arpino, P. J., B. G. Dawkins and F, W. McLefferty. "A Liquid Chromatography/Mass Spectrometry System Providing Continuous Monitoring with Nanooram Sensitivity," J. Chromatoar. Sci 12:574*578 (1974). Association of Official Analytical Chemists. "General Method for Organochlorine and Organophosphorus Pesticides, Method 29.001," Official Methods of Analysis of the Association of Official Analytical Chemists, w. Horwitz, ET ^ 13th ed"T Washington, OC 1980a), pp. 466-474. HONS 223791 Bibliography 345 Association or Official Analytical Chemists. "PC6 m Paper and Paperboard. Method 29.029." Official Methods of Analysis of the Association of Official Analytical Chemists. * W. Horvitz". Ed. (13th od. , Washington, OC 1900b). p. 475-476. Association of Official Analytical Chemists. AQAC Members (5th Edition. 1962). 109 pp. Handbook for Adas, E. , and C. S. Giam. "Global Transport of Organic Pol lutants: Ambient Concentrations in the Remote Marine Atmo sphereScience. 211:163-165 (1981). Aue. w. A. and $. Kapila. "The Electron Capture Oetector-- Controversies, Comments, and ChromatoaramsJ. Chromatoar Sci. 11:255-263 (1973). ----------------------X" Aue, w. A. and S. Kapila. "Use of Electron Capture*Induced Products for Confirmation of Identity in Pesticide Residue Analysis," Anal. Chem. 50:536*538 (1978). Augood, 0. R. . D- H. Hey, and G. H. Williams. "Homolytic Aromatic Substitution. Part III. Ratio of isomerioes formed in the Phenylation of Chlorobenzene. Competitive Experiments on the Phenylation of g-Dichlorobenzene and 1.3.5-Trichloro benzene. Partial Rate factors for Chlorobenzene." J. Chem. Soc. (London) pp. 44-50 (1953). Ayer. f. A. (Ed.). "National Conference on Polychlorinated Biphenyls (November 19*21, 1975, Chicago, Illinois)," Report of proceedings prepared for the U.S. Environmental Protection Agency, Office of Toxic Substances, Report No. EPA-560/6-75004, HTIS No. P8-253 248 (March 1976), 471 pp. Babkina, E. I., T. P. Fanaskova and T. v. Shpotova. "Deter mination of Orgenochlorine Pesticides and Polychlorinated Bi phenyls in the Ground and the Water," Gidropiol. 2h, 18(3): 86-91 (1982); Chem. Abstr. 97:06006f (19ffT"^ Begley, G. E., W. 1. Reichel and E. Cromartic. "Identifica tion of Polychlorinated 0iphenyls in Two Bald Eagles by Com bined Ges-Liguid Chromatography-Mass Spectrometry," J. Assoc. Offfc. Ana). Chem, 53(2):251-261 (1970). Bagley, G. E. and E. Cromartic. "Elimination Pattern of Aroclor 1254 Components in the Bobwhite," J. Chromatogr, 75:219* 226 (1973). 6ailey, R. E. , S. J. Gonsior and W. L. Rhinehart. "Biodegra dation of the MonocMorobipheny I s and Biphenyl in River Water," Environ. Sci. Tcchnol, 17(10):617-621 (1983). MON$ 223792 W6 . Biography Baird, W. H. J. "C-*sponding to Public Concern Over Environ* mental Pollution Hazards." in PC8s: Human and Envi rontwnt. i Hazards, F. H. D'ltri and H. A* iTamnn, Eds. TSoTtoiv Butterworth Publishers, 1983), pp. 91*100. Baker, E. 1., P. J. Landrigan, C. J. Glueck, H. M. Zack. jr. J. A. Liddle, V. w. 8urse, w. J. Housworth and L. Needham' ''Metabolic Consequences of Exposure to Polychorinated Bi phenyls (PCB) >n Sewage Sludge." Amer. J. Eoidemiol. n?/av 553-563 (1980). Ballinger, 0- G. "Test Procedures Tor Priority Organics in Municipal Wastewater and Sludges," US. Environmental Protec tion Agency, Cincinnati, Ohio, Oecember 11, 1978. 8al1schrniter. K. "High Resolution Gas Chromatography in En vironmental Analysis," in Reviews in Analytical Chem, 4 139 156 (1983a); Chem, Abstr. 99:63564b (1983). BalIscnmiter, K. "Sample Treatment Techniques for Organic Trace Analysis," Pure Appl. Chem. $$(12):1943-1956 ( 1983b) Chem. Abstr. 100:9579Id (1964). Ballschmiter, K. and M. Zell. "Analysis of Polychlorinated Biphenyls (PCB) by Glass Capillary Gas Chromatography. Com position of Technical Aroclor- and C1ophen-PC6 Mixtures," Fresenius* Z. Anal. Chem. 302:20-31 (1980). 6a I lschmi ter, K. , Ch. Unglert and H. J. Neu "Abbau Von Chlorierten Aromaten: Mikrobiologischer Abbau Oer Polychlorierten Biphenyle (PCS). HI: Chloriert# Benzoesauren als Metabolite Der. PCB," Chemosphere 6(1):51-56 (1977). Balya, D. R. and G. H. Farrah. "Column Chromatographic Pro cedure for the Determination of Pplycnlonnateo Bipnenyls m Certain Industrial Oils," Anal. Lett. 13(B8):655-671 (1980). Bartla, K. 0. "Identification of Polychlorobiphenyls by High Resolution Proton Magnetic Resonance," J. Assoc. Offic. Anal. Chem. 55(5): 1101-1103 (1972). Barton, T. G. and G. P. Arsenault. "Ultimata Oisposai of Polychlorinated Biphenyls," Chapter 10 in Detoxication of Hazardous Waste. J. H. Exner, Ed. (Ann Arbor, mT: Ann Arbor Science Publishers, Inc., 1982), pp. 185-199. Bauer, u.. "Combination of Thin-layer and Gas Chromatography for Identifying Halogenated Hydrocarbons," Vom Wasser 38:49 62 (1971); Chem. Abstr. 76:136672* (1972). MONS 223793 Bibliography 347 Baughman. R. and H. MeseUon. "An Analytical Method for De tecting TCDO (Dioxin): Levels of TCDO in Semples from Vietnam," Environ. Health Perspect. 5:27-35 (1973). -Sear*. J. K. . Ill and J. Schaum. "Sampling Methods and Ana lytical Procedures Manual for PC6 Disposal: Interim Report, Revision 0," Office of Solid waste, U. $. Environmental Pro tection Agency, Washington, QC (February 10, 1978). Becker, 0. A. "Analysis for PCBs in Oil: The NBS/ASTM Round Robin," in National Bureau of Standards Special Publication 674. Proceedings, Conference on Measurements and Standards for Recycled Oil. - Iv, Gaithersburg, Maryland, pp. 33-41 (1984). Becker, 0. A. "Used Lube Oil: Hazardous waste vs. Valuable Resource," Trace Subst. Environ. Health 16:22-27 (1982); Chem, Abstr, 99:160990v (1983). Becker, G. and E- Schulte. "Presence of PCS in Packaging Ma terials," Mltteilunqsbl. GQCh-Fachqruppe Lebensmittelcham. uancntl. Chem. 30(6): 101- LOS \ 1976)Chem.' Abstr.~85: lQ7S64u (TWT Beezhoid, F. L. and V. F. Stout. "The Use and Effect of Mixed Standards on the Quantitation of Polychlorinated Siphenyls," Bull, Environ. Contam. Toxicol. 1D(1):10-15 (1973). Beggs, D. P. and 0. 6. Banks. by GC/MS," Application- Note Avondale, Pennsylvania (1976). "Qualitative Analysis of PCS AN 176-20. Hewlett-Packard, Sellar, T. A. and J. J. Lichtenberg. "Some Factors Affecting the Recovery of Polychlorinated Biphenyls (PCB's) from Water and Bottom Samples," in Special Technical Publication 573. American Society for Testing and Materials, Philadelphia, Pennsylvania (1975), PP. 206*219. Sellar, T, A., J. J. Lichtenberg and S. C. Lonneman. "Recov ery of Organic Compounds from Environmentally Contaminated Bottom Materials," Chapter 4 in Contaminants and Sediments. Vo). 2, R. A. Baker, Ed. (Ann Arbor, MI; Ann Arbor Science Publishers, Inc., I960). Sellar, T. A. and J. J. Lichtenberg. "The Determination of Polychlorinated Biphenyls in Transformer Fluid and Waste Oils," Prepared for U.S. Environmental Protection Agency, EPA-6OO/4-01-O4S (1901). HONS 223794 Bibliography Seller. T. A. and 6. Froning. "Application ef Methods 606 and 606 for Analysis of PCBs Organochlorine Pesticides end Phthelete Esters Conteined in Lendfill leachates," II S En vironmental Protection Agency, Cincinnati, OH 'EPA-600/4" B2-044, NT 1S No. P682 227463 (1982). 16 pp. ' Bellierdo, F., E. Gionchiglie end G. H. Neno. "Analysis of Polychlorinated Biphenyl Residues in Waste Oils by High* Performance liquid Chromatography," J. liq. Chromatoor. 2(1): 77-83 ( 1979), -------------------- - Benville, P. E. end R. C. Tindle. "Dry Ice Homogenisation Procedure for Fish Semples in Pesticide Residue Analysis " J. Aqr. Food Chem. 18<5):940-949 (1970). Bercovici. 8, M. Wessermenn. S. Cucos, M. Ron, 0. Wessermen and A. Pines. "Serum levels of Polychlorinated Biphenyls end Some Orgenochlorine Insecticides in Women with Recent end Former Missed Abortions," Environ, Res. 30:169*174 (1983). Berg, 0. w. . p l. Dlosady and G. A. v. Rees. "Column Chro* metogrephic Separation of Polychlorinated Biphenyls from Chlorinated Hydrocarbon Pesticides, end their Subsequent Gas Chromatographic Quantitation in Terms of Derivatives." Bui I. Environ. Confm. Toxicol. 7(6)*. 338*347 (1972). Berger, 0. L. "Screening Procedure for Total Organic Halo- genAnal. Chem. 56:2271*2272 (1984). Bergman, A., R. Gdthe and C. A. Wechtmeister. "Impregnation of Silica Gel with Tetraalkylaamnnium Salts in Adsorption Chromatography of Neutral Aromatic Compounds," J. Chrpmatoqr. 123: 231*236 (1976). Bergman, A., 8. Jansson, and I. Bamford. "MethyUhio* and Methy1su)fony1polychlorobi0henyl$' Svnth#si Ctu-ies *i> Correlations detween Structure and Fragmentation Pattern on Electron Impact," Biomedical Mass Spectrometry. 7(1):20-27 (1980). Bergman, A., L. Reutegardh, and H. Ahlman, "Determination of Polychlorinated Biphenyls in Commercial Silica Gel by Capil lary Gas Chromatography," J. Chrpmatoqr. 291:392*397 (1984a). 9 Bergman, A. , A, Hagman, S. Jacobsson, B. Jansson. and M. Ahlman. "Thermal Degradation of Polychlorinated Alkanes." Chemosphere. 13(2):237-2S0 (1984b). MONS 223795 Bibliography 349 Bernard, B 8 and 8. 0. Russell. "Rapid Oeternination of PCBs in insulating Fluids." unpublished report, 0. I. Cor* poration, College Station, TX (1983), S pp. Bezot, P., C. Hesse-Bezot and 6. Quentrec. "Transmission of Light and local Order in viscous liquids. IV. Angular Oe* ptndence of OepolarUed Spectra," Mol, Phys, 43(6):1407*1418 (1981); Chem. Abstr, 96;?6686p (1982). Bezot, P. , C. Hesse*8ezot. "Fabry*Perot Study of Polarized and Oepolarized Spectra of liquid Pentachlorobiphenyl from *54 to lS0oC,*` Can. J, Phys. 60(11): 1709-1715 (1982). Bickford, 8., J. Bursey, l. Michael, E. Pellizzari, R. Porch, 0. Rosenthal, L. Sheldon, C. Sparacino, K. Tomer, R. Wiseman, S. Yung, J. Gebhart, L. Rando, 0. Perry and J. Ryan. "Pre* limrnary Oraft Report, Master Scheme for the Analysis of Or ganic Compounds in Water, Part III: Experimental Development and Results.'' EPA Contract No. 68-03*2704 (March 1900). Bidleman, T. F. "Interlaboratory Analysis of High Molecular Weight Organochlorines in Ambient Air," Atmos. Environ. IS. 519-624 (1981). Bidleman, T. F. "Estimation of Vapor Pressures for Nonpolar Oraanic Comoounds by Capillary Gas Chromatocraphy." Anal. Chem,, 56:2490*2496 (1904). Bidleman, T. F. and C. E. Olney. "High-volume Collection of Atmospheric Polychlorinated Biphenyls," Bull. Environ. Contarn. Toxicol. 11(5):442~450 (1974). Bidleman, T. F. , C. P. Rice, and C. E. Olney. "High Molecu lar weight Chlorinated Hydrocarbons in the Air and Sea: Rates and Mechanisms of Air/Sts Tronsftr," in Morin* Pol lutant Transfer. "H, l. Windom and R. A. Ouce, Eds. (Lexington, MA: Lexington Books, 1976), pp. 323-351. sioieman, f. r., J. R. Matthews, C. i. Olney and C. P. Rice. "Separation of Polychlorinated Biphenyls, Chlordane, and p,p'-00T from Toxaphene by Silicic Acid Column Chromatog raphy," J, Assoc. Qffic. Anal. Chem. 61(4):B2O-02B (1978). Bidleman, T. f. , W. N. Billings and C. G. Simon. "Evaluation of Solid Adsorbents for Collecting Atmospheric Chlorinated Hydrocarbons," EPA 600/2-80-167 (19B0). HONS 223796 350 Bibliography Bidieman, T. F. , E. J. Christensen and H. w. Harder, "Aeriji Oepositlon of Organochlormes in Urban and Coastal South Carolina," Chapter 24 in Atmospheric Pollutants in Waters. S. J. Eisenreich, d~ (Ann Arbor, HI; Ann Arbor ScP ence Publishers, Inc.. 1981a), pp. 481-508. Bidieman, T. F. , E. J. Christensen, w. N, Billings and R. Leonard. "Atmospheric Transport of Organochlorines in the North Atlantic Gyre," J. Marine Res. 39(3):443*464 (1981b). Bidieman, T. F. and R. Leonard. "Aerial Transport of Pesti cides over the Northern Indian Ocean and Adjacent Seas " Atmos. Environ. 16:1099-1107 (1982). ' Bidieman, T. F., N. F. Burdick. J. W. Westcott and W. n. Billings. "Influence of Volatility on the Collection of Air borne PCS and Pesticides with Filter-Solid Adsorbent Sam plers." Chapter 2 in Physical Behavior of PCB* in the Great Lakes. 0. Mackay, S. Paterson. S. J. Eisenreich and M. S, Simmons, Eds. (Ann Arbor, MI: Ann Arbor Science Puolisners Inc.. 1983), pp. 15-48. ' Bidieman, T. F. , C. G. Simon, N. F. Burdick, and F. You. "Theoretical Plate Measurements and Collection Efficiences for High-Volume Air Samplers Using Polyurethane Foam," J. ChromatOQr. 301:440-453 (1904). Billings, W. N. , and T. F. Bidieman, "Field Comparison of Polyurethane Foam and Tenax-GC Resin for High-Volume Air Sam pling of Chlorinated Hydrocarbons," Environ. Sci. Techno!. 14(6): 679-683 (I960). Billings, W. N. and T. F. Bidieman. "High Volume Collection of Chlorinated Hydrocarbons in Urban Air Using Three Solid Adsorbents." Atmos. Environ. 17:383-391 (1983). Biocca, M., J. A. Moore, B. N. Gupta and J. D. McKinney. "Toxicology of Selected Symmetrical Hexachlorobiphenyl Isomers: I. Biological Responses in Chicks and Mice," Conf, Proc, - Natl. Conf. Polychlorinated Biphenyls pp. 67-72 (1976): Chem. Abstr. 85;73086x (1976). Biocca, M., B. N. Gupta, K. Chae, J. 0. McKinney and J. A. Moore. "Toxicity of Selected Symmetrica) Hexachlorobiphenyl Isomers, in the Mouse." Toxicol. Appl. Pharmacol. 58(3):461474 (1981). MONS ZZ3797 Bibliography 351 Biros, F. J. "An Integrated Gas Chromatograph-FUme Ionisa tion Oetector-Mass Spectrometer System for Pesticide Residue Analysis,1' Pestic. Chem. Proc. Int. IUPAC Conor. Pestic Cham. 2nd 4:149-169 (1971). Biros, F. J. . A. C. walker and A. Medbery. "Polychlorinated Biphenyls In Human Adipose Tissue," Bull. Environ. Contain. Toiicol. S(4):317-323 (1970). Biros. F. J. . H. F. Enos, A. C. Walker and J. F. Thompson. "Analytical Aspects of Polychlorinated Biphenyl Oetermina* tions in Human and Animal Adipose Tissue," Prepr. Pap. Natl. Meet. (Hew York); Oiv. Water, Air and Waste Chem.; Amer. Chew. Soc. 12:61-66 (I97?)l~ Chew. Abstr. 81:384c (1972). Bishop. T. A., and J. E. Gebhart. "Method validation for in cidental Generation of Polychlorinated Biphenyls in Products and Waste Streams,'* Final Report, Task 66. EPA Contract No. 68-01-6721. Office of Toxic Substances, U.S. Environmental Protection Agency, Washington, 0C (1964). Soe, B. and E. Egaas. "Qualitative and Quantitative Analyses of Polychlorinated Biphenyls by Gas-Liquid Chromatograpny, ' J. Chromatoqr, 180:127-132 (1979). Bonelli, E. J.. "GC/MS Techniques for the Determination of Interferences in Pesticide Analysis." Inst. Environ. Sci. Proc. 18:251-254 (1972a). Bonelli, E. J. "Gas Chrometograph/Mass Spectrometer Tech niques for Determination of Interferences in Pesticide Analy sis," An*1- Chem. 44(3): 603*606 (1972b). Boniforti, L.. G. Cittl and G. laguzzi. "Identification and Quantitative Determination of Polychlorinated Biphenyls and Polynuclear Aromatic Hydrocarbons in Fly Ash from Municipal Incinerators by Gas Chromatography with Electron-Capture de tection ana Gas Chromatograpny-Mass ipoctrosetry," amChem. Svmo. Ser. -- 7:219-225 (1981): Chem. Abstr. ---------------------------- 96:90803v Bonner, R. F. "Environmental Analysis with a Triple Quedru* pol*" Int. J. Mass Spectrometry Ion Phys. 48:311-314 (1983). 8opp, R. F., "Revised Parameters for Modeling the Transport of PC8 Components Across an Air Water Interface," J. Geophys ical Research. 88(C4):2521-2529 (1983). Bostick, W. 0., M. S. Oenton and S. R. Dinsmore. "Develop ment of a Portable Field Monitor for PCBs," Prepared for Electric Power Research Institute, Palo Alto, CA, EPRI CS2828 (1983); NT IS No. 0E83 007425. MONS 223798 3^ . 8'bliography Bourke, J. 8. "PCS'* and Pesticides," N.Y, State Assoc m> 1l and Food Sanitarians. Ann, Reot- 46:41*43 ( 1972). ~ "-- Bowes, G- W. and J. A. lewis. "Extraction of Polychlorinated Biphenyls: Evaluation of A Column Technique Applied to Polar Bear and Seal Tissue." J. Assoc. Qffic Anal. Chem. 67m. 118*164 (1974). "" Bowes, G. W. , M. J. Mulvihill, M. R. OeCamp and A. $ Kende "Gas Chromatographic Characteristics of Authentic Chlorinated Oibenzofurans; Identification of Two Isomers in American anq Japanese Polychlorinated Biphenyls," J. Aqmc. Pood Chen 23(6):1222*1223 (1975a). ~ Bowes, G. W. , H. J. Hulvlhlll, B. R. T. Simoneit. A. t. Burlingame and R. W. Rlseprough. "Identification of Chlor inated Oibenzofurans in American Polychlorinated Biphenyl Nature 256:305-307 (1975b). ' 3owes, G. , H. J. Mulvihill, 3. R. T. jimone\t. A t. Burlingame and R. W. Risebrough. "Isolation and Identifica tion of Chlorinated Oibenzofurans from Polychlorinated Bi phenyls (PCB) and from Vusho Rice Oil Containing PCB," Chapter 8 in 01ox1n--Tox1colog1cal and Chemical Aspects, f. Cattabeni, A. Cavaharo and G. Galli, Eds7 (New York, NY: SP Medical and Scientific Books, 1978), pp. 79-98. 9remer, 4. E. "Oeellng with Multi-Agency and Multi-State Regulation of Polychlorinated Biphenyls," in PCBs: Human and Environmental Hazards, F, M. O'ltri and M. A. Kamrin, Eds. (Boston: Butterworth Publishers, 1963). pp. 367-374. Brinkman, U. A, Th:, A. Oe Kok, G. Oe Vries and H. G. M. Reymer, "High-speed Liquid end Thin-layer Chromatography of Polychlorinaited Biphenyls," J. Chromatopr. 128:101-110 ;1976mj. Brinkman, (J. A. Th. , J. W. F, L. Seetz and H. G. M. Reymer. "High-speed Liquid Chrometogrephy of Polychlorinated Bi phenyls and Related Compounds," J. Chromatoqr. 116:353-363 (1976b). Brinkman, U, A. Th., G. Oe Vries, A. Oe Kok and A. L. Oe Jonge. "Discrimination Between Polychlorinated Naphtha lenes end Polychlorinated Biphenyls," J. Chromatoqr. 152: 97-104 (1978). Brinkman, U. A. Th. and G. Oe Vries. "Relationship Between Structure and Retention of Polyhelogenated Aromatics in Two Adsorption Chromatographic Systems," J. Chromatogr. 169: 167-1B2 (1979). HONS 22S799 Bibliography 353 Brinkman, U. A. Th. and A. Oe Kok. "Ha logenated Biphenyls, Ttrphenyls, Naphthalenes, Oibenzodioxins and Related Prod ucts. Production, Properties and Usage." Chapter-1.- R. o. Kimbrough, Ed. (New York: NY: Elsevier/North-Holland Bio medical Press, 1980), pp. 1-40. Broto-Puig, f, M. Gassiot-Matas, R. Martlnez-Fonrodona. "Application of an On-Line Potassium Hydroxide Microreactor to the Resolution of Interferences Between PCBs and OOTs in the Gas Chromatography of High-Molecular-Weight Organochlorinated Contaminants." Journ. Etud. Pollut. Mar. Mediterr, 6:449-454 (1983); Chem. Abst. 101:l$>346w (1984). Brown, 0. P. and M. Jones. "Mortality and Industrial Hygiene Study of Workers Exposed to Polychlorinated Biphenyls," Archives of Environmental Health 36(3):120-129 (1981). Brown, J. f. Jr. , J. T. Coe and H. 0. Pocock Jr. "Human Health Effects of Electrical-Grade PCB's," Corporate Health and Safety Operation, General Electric Company, Fairfield, CT (August 1961a). Brown, J. F. Jr,, M. . Lynch, J. C. Carnahan, and J. Singleton. "Chemical Destruction of PCBs in Transformer Oil," General Electric Company, Schenectady, NY, Technical Information Series. 81CRQ2S7 (November 1961b). Brown, J. F. Jr., M. . lynch, J. C. Carnahan and J. Singleton. "Chemical Destruction of Polychlorinated Bi phenyls in Transformer Oil," Chapter 11 in Oetoxication of Hazardous Waste. J. H. Exner, Ed. (Ann Arbor, Ml: Ann Arbor Science Publishers. Inc., 1982), pp.201-214. Brown J. F. , Jr. , and R. W. Lawton. "Polychlorinated Bi phenyl (PC6) Partitioning Between Adipose Tissue and Serum," Bull. Environ. Contem. Toxicol. 33:277-2B0 (1984). 3rownrigg, J. T. and A. W. Hornig. "Estimation of Polychlor inated Biphenyls In the Presence of OOT-Type Compounds," Pre pared for the U.S. Environmental Protection Agency, NT IS Pub lication No. PS-233 599 (June 1974). Brownrigg, J. T. and A. W. Hornig. "Identification of PCB's in the Presence of OOT-Type Compounds Using Low Temperature Luminescence," Arch. Environ. Contam, Toxicol. 4:175-182 (1976). MONS 223800 3** Bibliography Bruggeman, w. A . J. van der Steen and 0. Hutzinger "fieversea-Phas* TMn-uyer Chromatography of Polynuclear Aro matic Hydrocarbons and Chlorinated Biphenyls. Relationship -ith Hydrophoetoty as Measured by Aoueous Solubility and Gctanol-Water Partition Coefficient/' J. Chromatoor. 23B(?V 335-346 (1982). -----------------------' Brugger, J E , J. j. Ytzzi Jr., I. Wilder, F. J. Freestone. R. A. Miller and C. Pfrommer, Jr. "The EPA-ORO Mobile In cineration System: Present Status.'' Proceedings in- 1982 Hazardous Material Spills Conference Paper No. 167 (April igzZ, 1982). Brune"e, 0. J. "Reaction of Polychlorinated Biphenyls with Mercaptans tn Non-polar Media: Formation of PolycMoroDtphenyl Sulfides," Cnemosphere 12(2). 167-181 (1983). BruneMe. 0. J. and 0. A. Singleton. "Oestruction/Removal of Polycniortnated Biphenyls from Non--oiar Media. Reaction or PCB with Polyethylene Glycol )A0H." Chemosohere 12(2):183196 (1983). Brunn, H. "Quantitative Gat Chromatographic Oetection of Residues of Polychlorinated Biphenyls in Raw and Processed Foods of Animal Orioin." Arch. Lebensmittelhya 33(5): 116-122 ( 1982); Chem. Abttr. 98:33l35z (1993). Burdick. N. F. and T. F. Bidleman. "Frontal Movement of Hexacnloroptnzene and Polychlorinated Biphenyl Vapors through Polyurethane Foam." Anal. Chew. 53(12):1926-1929 (1981). Burke, J. A. "Report on Chlorinated Insecticides," J. Assoc. Offic. Anal. Chem. 58(2):233-235 (1975). Burke, J. A. "Report on Chlorinated Pestictoes Offic. Anal. Chw. 59(2):338-340 (1976). Burkhard, L. P. and 0. E. Armstrong. "Labeled Perchlorination Reagent for Determination of Polychlorinated Biphenyls." Ana). Chem. 53(3):523-52B (1981). Bums, J. E. "Pesticides in People: Orgenochlorine Pesti cide and Polychlorinated Biphenyl Residues in Siopsied Human Adipose Tissue--Texas 1969-1972." Prepared for the U.S. En vironmental Protection Agency, NT IS No. PB-2B0 613/1. 5 pp. (1974). Burse. V. w. . R. F. Moseman, G. w. Sovocool and E. C. Villanueva. "PCB Metabolism in Rats Following Prolonged Ex posure to Aroclor 1242 and Aroclor 1016," Bull. Environ. Contarn. Toxicol. 15(1): 122-128 (1976). MONS 223601 Bibliography 355 Burse, v. w. . i. i. Needham, j. a. liddle, 0. 0. Bayse and H. A. Price. "Inter 1 abo^atory Companion for Results of Analy ses for Pol yen 1 or<mated Btpnenyls tn Human Se^t*." J. Anal Toxicol. 4:22-26 (1980). Burse, V. w. ,i. i. Neednam, M. P. Korver, C. R lapeza Jr., J. A. liddleand 0 0. Bayse.Gas*Uquid Chromatographic De termination of Polychlorinated Biphenyls and a Selected Num ber of Chlorinated Hydrocarbons in Serum." J Assoc. Off Anal. Chem. 66( 1).32-39 ( 1983a). Burse, V. W. ,i. i. Neednam, M. P. Korver, C. R lapeza Jr. . J. A. ilddleand 0. 0. Bayse. "Assessment of Metnods to De termine PCB levels tn Blood Serum: Interlaboratory Study," J. Assoc. Off Anal. Chem, 66(l):40-45 (1983b). Buser. H. R. "Analysts of TCDOs by Gas Chromatsgraphy-Hass Spectrometry Using Glass Capillary Columns.' Chapter 4 in Dioxin--Toicoloqical anq Chemical Aspects. F Cattaoem. A. Cavailaro ano u. Jaili. ids. ;New .orx, ny: Heoical and Scientific Books, 1978), pp. 27-41. Buser, H. R. , H. P. Bosshardt and C. Rappe. cormetton of Polychlorinated Oibenzofurans (PCDFs) From the Pyrolysis of PCBsChemosphere 7:109-119 (1978a). Buser, H. R. , H. P. Bosshardt, C. Rappe and R. Lindahl. "Identification of Polychlorinated Dlbenzofuran Isomers in Fly Ash and PCB Pyrolyles," Chemospntre 7(S):419--29 (1976b). Buser, H. R. and C- Rappe. "Formation of Polychlorinated Oi benzofurans (PCOFs) from the Pyrolysis of Inoividua! PCB Isomers," Chemospnere 8(3):157-174 (1979). Buser, H. R. and C. Rappe. "Isomer-Specific Separation of 2373-iuwSt;tutd ^oiycniurmatto Cvoenzd-g-uto*<-s oy HignResolution Gas Chromatography/Mass Spectrometry,1 Anal. Chem. 56;442*448 (1984). Bush, B. and F.-c. lo. "Thin-layer Chromatograofy for Quan titative Polychlorinated Biphenyl Analysis," J. Chrpmatoqr. 77: 377-388 (1973). Bush, 8., F. Baker. R. Dell'Acaua. C. l. Houck a-d F.-C. Lo. "Analytical Response of Polychlorinated Biphenyl Homologues and Isomers in Thin-layer and Gas Chromatographv," J. Chroaaatoqr. 109:287-295 (1975). HONS 223802 356 Bibliography Bush, 6. ana E. i. Barnard. Oetirmmation of Nonpolar Chlorinated Hydrocaroons and ?C3 in Microsamples '' Anal Lett 1S(A20):1643-1640 (1902). ------- - Bush, B. , S. Connor and J. Snow 'Class Capillary Gas Chro matography for Sensitive, Accurate Polychlorinated Biphenyl Analysis.M J Assoc. Off Anal >*. 65(3): 555-566 (1902) 8uih B. , J. T. Snow, and S. Connor, "Hign Resolution Gas Chromatographic Analysis of Nonpoiar Chlorinated Hydrocaroons in Human Milk," J. As#0c. Off. Anal. Chem. 66(2) 240- (1983). ---------------------------------------------------- Bush. B., J. Snow, and R. Koblinti, "Polychlorobiphenyl (RCB) Congeners, g,g*00E, and Hexachlo*coenzene >n Maternal and Fe tal Cord Blood from Mothers in upstate New York," Arch, Env Cont. Tqx, 13{5):517-527 ( 1984) -----------------" Sutler, J. "Analysis of Divers* -amoie Matrices `or 3oiv* cniormateo Bipnenyls using the /GOA Hail Electrolytic Con* ductivity Detector," 1961 Pittsburgh Confirence, Abstract No 041. Cairns, T and R. A, Jacobson. "New Approaches to FOA Analyt ical Problems." J. Chem. Infor. Como. Sct. 17(2):105*109 (1977). ------------ Cairns, T. and E. G, Siegmund. 'Determination of Polychlor inated Biphenyls by Chemical Ionization Mass Spectrometry," Anal. Chem. 53(11):1599*1603 (1961a). Cairns, T. and E. G. Siegmund. "PCBs; and Analytical Problems." Anal Chem. (1981b). ---------------------- Regulatory History 53(11): 1183A-U93A Cairns, T. and w. H. Rogers. "Acceptable Analytical Oata for Trace Analysts," Anal. Chem. SSU):S4A*S7A (1983). Calandra, J. C. "Summary of Toxicological Studies on Commer* cia) PCBs," in National Conference on Polychlorinated Si* phenyls. Franklin A. Ayer, Ed, U.S. Environmental Protection Agency, Office of Toxic Substances. EPA*560/6*75*004, nT1S No. PB*2S3 248, pp. 35*42 (1976). Call, 0. J. , Y. A, Greichus and J. J. Woman. "A Gas Chro* matographic*mass Spectrometric Comparison of Polychlorinated Biphenyl Residues in the Japanese Quail Brain to an Aroclor Standard," Bull. Environ. Contain, Toxicol. 11(4 ): 333*336 (1974). HONS 223803 Bibliography 357 Canada. 0. C- and F. E. Regnier. "Isotope Ratios as a Char* acteristic Selection Technique Tor Mass Chromatography " J. Chromatoqr Sci I4.U9-IS4 ( 1976). Cantlon, J. E. "Th* PCB Problem: An Overview," in PCBs: Human and Environmental Hazards. F. M. O'ltri and M. a. KarnTtn, Tds. (Boston: Butterworth Publishers. 1983), pp. 5* 10. Caragay, A. B. and P L. Levins. "Evaluation of Protocols for Pesticides and PCB's in Raw Wastewater," Final Report, Arthur 0- Little. Inc.. Contract No. 68*01*38S7, Office of Research and Development, Environmenta I Protection Agency, Report No EPA*600/2*79-166 (Novemoer 1979). Carcich, I. G. , and T. J. Tofflemire. "Distribution and Con centration of PCB in the Hudson River and Associated Manage* ment Problems," Environmental International 7:73*85 (1982). Cardone, T J. Detection and Determination or Error :n Analytical Methodology. Part I. In the Method verification Program," J. Assoc. Off. Anal. Chem. 66(5):1257*1282 (1983a). Cardone, M. J. "Detection and Determination of Error in An alytical Methodology. Part II. Correction for Corrigible Systematic Error in the Course of Real Sample Analysis," J. Assoc. Off Anal. Chem, 66(2): 1283*1294 ( 1983b). Carey, A. E. and J. A. Cowen. "PC8's in Agricultural and Urban Soil." In: Procttdinds of tha National Conferenct on PC8s, po. 195-198, EPA UO/B^-OOA 0976). Carson, L. J. "Inter laboratory Study of the Hall 700A Halo gen Electrolytic Conductivity Gas Chromatographic Oetector," J. Assoc. Off Anal Chem. 66(6): 1335-134* (1983). Carson. R. Silent Spring. (Greenwich, CT: Fawcett Publica tions, Inc.. 1962), 304 pp. Caste!li, M. G. , G. P. Martelli, C. Spagone. L. Cappellini and R. Panel)i. "Quantitative Determination of Polychlori nated Biphenyls (PCB) in Marina Organisms Analyzed by HighRetolution Gat Chromatography Selected Ion Monitoring," Chemosphere 12(3): 291-298 (1983). Chau. A. S. Y. and C. J. Sampson. fchromatograpnic Methodology for tne chlorinated Biphenyls: Survey and Lett. 8(2):89** 101 (1975). "Electron Capture Gas Quantitation of Poly Compromise," Environ. MONS 223804 3* . Bibliography Chau. A. S. Y. and l. J Babjak. "Column Chromatographic Of* termination of Hirt*. Pnotomirex. and Polychlorinated Siphenyls in take Sediments." J Assoc. Off Anal Chem fi;m 107-113 (1979). Chau. A. S. Y.. J. Carron and H.-8. lee. "Analytical Refer* ence Materials. II. Preparation and Sample Integrity of Homogeneous fortified wet Sediment for Polychlorinated Bi phenyl Quality Control Studies," J. Assoc. Off Anal. Ch*m 62(6):1312-1314 (1979). Chau. A. S. Y. and H.-B. lee. "Analytical Reference Materi als. Ul. Preparation ano Homogeneity Test of large Quanti ties of Wet and Ory Sediment Reference Materials for Long Term Polychlorinated Biphenyl Quality Control Studies J Assoc. Off Anal. Chem. 63:947*951 (1980). Chemical Manufacturers Association, "the Analysis of Chlori nated 8ipnenyis,'' suomittaa to the environmental 3"otec*. on Agency, August 21. 1981. in reference to 0PTS-62017. Chen, J-Y. T. and A. M. Gardner. "Multicomponent Analyses of PC8s by fTIR Spectroscopy," Amer. lab, pp. 26-33 ( 1983). Chen. K. "The Reclamation of PCB-Contaminated Transformer Oils by The SunPhlo PC8X Process," Interim Report, TVA/OP/ E0T--82/45. NT1S Mo. 0E82 906112, 49 pp. (1982). Chen, K. "Evaluation of the Sunohio PC8X Process for Recla mation of Transformer Oils Containing P8Cs." IEEE Trans. Power Aooar. Syst. PAS-102(12):3893*3898 (1983); Chem. Abstr IWriQfij79f (1984). Chen. H . J. M. Gaw. C <. Vono and C. J. Chen 'levels and Gas Chromatographic Patterns of Polycnlonnateo Sipneny s in the Blood of Patients After PC8 Poisoning in Taiwan," Bull. Environ. Contam. Toxicol. 2S:325-329 (1980). Chen, P. M. , K. T. Chang and Y. 0. lu. "Polychlorinated Bi* ohenyls and Polychlorinated Oibenzofurens in the Toxic RiceBran Oil that Caused PCS Poisoning in Taichung," 8ul 1 . Environ. Contam. Toxicol. 26:489-495 (1981). Chen, P. H., M. l. luo, C. K. Wong and C. J. Chen. "Compara tive Rates of Elimination of Some Individual Polychlorinated Biphenyls from the 81ood of PC8-Poisoned Patients in Taiwan," food Chem. Toxicol. 20:417*425 (1982). Chn, P. H. and R. A. Hites. ''Polychlorinated Biphenyls and Oibeniofurjns Retained m toe Tissues of a Oeceased Patient with Yucheng in Taiwan," Chemosphere 12(11-12):1507*1516 (1983). MOMS 223805 Bibliography 359 Chesl#r, S. N. . W. . Hay. P A. Whit*, R, M. Parris and F. R. Guenther "Determination or Polychlorinated Biphenyls in waste and lubricating Oils.' National Sureau of Standards Special Publication 504, Proceedings of Joint Conference on Measur*ments and Standaras for Recycled Qil/Svstems Perfor mance and Ourabi1ity, Gaithersburg, MO. October 23-26^ 1979, pp. 295-29), N0S. Tissued November 1980). Chester, S. N. , F. R. Guenther, w. . Hay and R. H. Parris. "SRM's for Accurate Analyses of PC8s m Oil," Abstract, Center for Analytical Chemistry, National Bureau of Stan dards, Washington, DC, 20234 (1981). Chiosi, S.. A. Evident*. G. Randazzo and 0. Scalorbi. "Anal ysis of a Mixture of Polychlorinated Biphenyls, 00T and Its Analogues by High-Performance liquid ChromatographyJ liq uid Chromatoqr. S(9): 1653-1663 (1982) Chittim, 8. G. , 8. S. Clegg, S. H, Safe and 0. Hutzinger. "Chlorinated Oibenzofurans and 0benzo-g`dioxins: Oetection and Quantitation in Electrical Equipment and Their Formation During the Incineration of PC3s,' preoared under Contract No.: 0SS78-00067 for Fisheries and Environment Canada (September 1979) 79 pp. Choudhry, G. G. *nd 0. Hutzinger, Eds. Mechanistic Aspects of the Thermal Formation of Haloqenated Organic Compounds Including Polychlorinated Qibenzo-p-dioxins (New York: Gordon and Breach Science Publishers, 1983), 194 pp. Christensen, E. j., C. E. Olney and T. F. Bidleman. "Compar ison of Ory and Wet Surfaces for Collecting Organochlorine Qry Deposition." dull. Environ. Contam. Toxicol. 23:196-202 (1979). Claeys, R. R. "Analysis of PCBs in Pulp Mill Effluent," Spe cial Report-NCASI (National Council of the Paper Industry for .r no Stream improvement;, No. /7*04, pp. 46-49 (1977). Coburn, J. A., I. A. Valdmanis and A. S. Y. Chau. "Evalua tion of XA0-2 for Multiresidue Extraction of Organochlorine Pesticides and Polychlorinated Biphenyls from Natural Waters," J. Assoc. Off. Anal. Chem. 60(1):224-228 (1977). Colby, 8. N. and J. E. Picker. "Automated Recognition of Aroclor GC Patterns," Abstract No. 574, 1983 Pittsburgh Con ference and Exposition on Analytical Chemistry and Applied Spectroscopy (1983). MOMS 223806 360 Bibliography Colby, 8. N. . E. A. Burns and P. 1. lagus. "The S-Cubed PC0A 101. an Automated Fie'd Analyzer for PCBs," Abstract Ho. 731 1983 Pittsburgh Conference ana Exposition on Analytical Chem istry and Applied Spectroscopy (1983) Coleman. W. . and A. C. Tardiff. "Contaminant levels in An imal feeds Used for Toxicity Studies." Arch. Environ. Contain Toxicol. 8:693-702 (1979) ' Colenutt, 8. A. and S. Thorburn. Stripping Concentration Technique Pollutants." Intern. J. Environ. (1980). "Optimisation of a Gas for Tract Organic water Anal. Chem. 7;231-?44 Collard, R. 5. and M. H. Irvin, Jr. "GC/MS Determination of Chlorinated Biphenyls in Complex Chlorinated Hydrocarbon Pro cess and waste Streams," The Oow Chemical Company (1962a) Collard, R. S. and M. H. Irvin, Jr. "Determination of Chlor* mated Bipnenys (Incidental PC8s) m Chlorinated Hydrocaroon Process and Waste Streams." Abstract. 164th Annual American Chemical Society National Meeting, September 12*17, 1962b. Collard, R. S and H. M. Irvin. "GC/MS Determination of In cidental PC8s in Complex Chlorinated-Hydrocarbon Process and wtste Streams." Talanta 30(11):8U-818 (1983). Collins, G. 6.. 0. C. Holmes and f. J. Jackson. "The Estima tion of Polychlorobiphenyls," J. Chromatoqr. 71:443-449 (1972). Cone, M. V., M. F. Baldauf. 0. M. Opresko and M. S. Uxiel. "Chemicals Identified in Human Breast Milk, A Literature Searcn," U.S. Environmental Protection Agency, Office of Pesticides and Toxic Substances, wasnmoton. 0C. SPA e,50/ i-33-009; nTIS No. P884-U8538 (October 1983), 125 pp. Connors, T. F.. J. F. Rusling, and A. Owlia. "Determination of Standard Potentials and Electron-Transfer Rates for Halobiphenyls from ElectrocataIvtic Oita." Anal. Chem. 57:170-174 (1985). Cook, W. J. "Some Chemical Aspects of Polychlorinated Siphenyls (PCI*)," Environ. Health Perspec. 1:3-13 (1972). Cooke, M. , G. Nickless, A. M. Prescott and 0. J. Roberts. "Analysis of Polychlorinated Naphthalenes, Polycnlorinated Biphenyls and Polychlorinated Terphenyls via Carbon Skeleton Gas-liquid Chromatography," J. Chromatoor. 156:293-299 (1978). HONS 223*0* Bibliography 361 Copeland, R. A. Letter to U S. Environmental Protection Agency, Office of Toxic Substances, Re. Manufacturing Ban Exemption Petition (TS-794), from Honochlorobiphenyl Task Force. 0ow Chemical USA., July 31, 1979. Copland, G. B. ana C S. Gohmann. "Improved Method for Poly chlorinated Biphenyl Determination in Complex Matrices," En viron, Sci Ttchnol. 16.121-124 (1982). Cordle, F., P. CorneIius sen, C. Jelinek, 6. Hack ley, R. Lehman, J. McLaughlin, R. Rhoden and R. Shapiro. "Human Exposure to Polychlorinated Biphenyls and Polybrommated 61' phenyls," Environ. Health Perspec. 24:157-172 (1978). Cordle, F., R. Locke and J. Soringer. "Risk Assessment in a Federal Regulatory Agency: An Assessment of Risk Associated with the Human Consumption of Some Soecies of Fish Contami nated with Polychlorinated Biphenyls (PCBs)." Environ. Health Perspec. 45:171-182 (1982). Corneliussen, P. . "Report on Multiresidue Methods (Inter laboratory Studies)." J. Assoc. Off Anal. Chew, 58(2>:238- 239 (197S). Crist, H. L. and R. F. Moseman. "Simplified Micro Perchlorination Method for Polychlorinated Biphenyls in Biological Samples," J. Assoc. Off. Anal. Chem. 60(6):1277-1281 (1977). Crummett, W. 6. "The Problem of Measurements Near the Limit of Detection," Ann. N. Y, Acad. Sci. 320:43-47 (1979). Cull, M. R. , and A. J. Oobbs, "Analysis of Polychlorobiphenyls from Used Transformers for Polychlorodibenzofurans," Chemosohere 13(9): 1085-1089 (1984). Curley, A., V. W. Burse, M. E. Grim, R. W. Jennings and R. E. Linder. "Polychlorinated Biphenyls: Distribution and Stor age *n Body cluids 3nd Tissues if Sherman Rats." Environ. Res. 4:481-495 (1971). Oale, W. E., A. Curley and C. Cueto, Jr. "Hexane Extractable Chlorinated Insecticides in Human Blood," Life Sci. 5:47-54 (1968). Dark, W, A. and L. W. Crossman, Jr. lights ' Polychlorinated Biphenyls." Milford, Massachusetts. AH-324 (1973). "Applications High waters Associates, HONS 223808 362 Bibliography Oas, K. G. and P S. Kulkarm "Gas-liquia Chroma tograoy," Chapter 2 in Pesticide Analysis. < C. Oas. Ed. (Nw , NY: Marcel Oekker, Inc. 1981), pp 45-90. Qavenport. R. J. end 8. K. Bernard (Eds.). Advances n ft* posure, Health and Environmental Effects Studies of PCBs " Symposium Proceedings. Office of Toxic Substances, u S. n- vironmental Protection Agency, Washington, OC, LSI-TR-S071378, NT IS No. P884- 135771 (Oecemoer 1983) 365 pp. Oavid. 0. J. "Gas Chromatographic Oetectors," Corporation (New York. NY: wi ley-Interscience Publication, 1974). deAlencastro, 1. F., V. Prelax. and J. TarradeMas. "Contamination of Silos in Switzerland by PCB Residues m Ccatings," Bull. Environ, Contain. Tpmcol. 33:270*276 (1984 ) De Kanei, J. , S.-y. Tang and R; C. Dougherty. "CapiHary GC/'MS Profiling of Xenooiotic Ch'emicjiS in 3 i o YI u i d s - ; ana NCI Moats,'' American Society for Mass Spectrometry. 30th Annual Conference on Mass Spectrometry and Allied Topics, ao* stract, June 6-11, pp. 197 (1962). De Kok, A., R. 8. Geerdink, R. W. Frei and U. A. Th. Brink* man. "The Use of Dechlorination in the Analysis of Poly* chlorinated Biphenyls and Related Classes of Compounds." Intern, J. Environ. Anal. Chew. 9:301*318 (1981). De Kok, A., R. 6. Geerdink, R. W. Frei and U. A. Th. Brink man. "limitations in the Use of Perchlorination as a Teen* nique for the Quantitative Analysis of Polychlorinated Bi phenyls," Intern. J, Environ. Anal. Chem. 11:17-41 (1982a). De Kok, A., R. B. Geerdink, G. De Vries and U. A. Th. Brink- *jn. "\.i :. 4`t-aiion ;f Ch.-omatogripnic Metnocs 'ar -..*e Analysis of Polychlorinated Terphenyls in Environmental Sam ples," Intern.J. Environ. Anal. Chem. 12:99-122 (1982b). De Kok, A. , R. 8.Geerdink and U. A. Th. Srinkmen. "Th# De termination of Polychlorinated Naphthalenes in Soil Samples by Means of Various Gas and Liquid Chromatographic Methods," Chromatoor. Sioche*. . Med. Environ. Res.. 1. A. friaeno. Ed. niU>. 5p- 26i-iie! --------------------------- Oelfino, J. J. "Toxic Substances in the Great Lakes." En viron. Sci. Ttchnol. 13(12):1462-1468 (1979). Oelfino, J. J. (Ed.). Methods for Analysis of Organic Com pounds in the Great Lakes. Proceedings of an Invitational Workshop, Apri1 1-2, 1980, University of Wisconsin Grtat Lakes Research Facility, Milwaukee. Wisconsin, WIS-SG-80-236 (1980). HONS 223809 Bibliograpny 363 Oelfino. J. J. and 0. B. Easty. "Interlaboratory Study o' the 0eter*n nation of Polychlorinated Biphenyls in a Pape' Mill Effluent.'1 Anal. C*tm. 51(13):223S-2239 ( 1979 ). Dennis. 0. S. "Polychlorinated Biphenyls in the Surface waters and Bottom Sediments of the Major Oramage Basins o' the United States." Prepared for the U.S. Environmental Pro tection Agency. Office of Pesticide Programs, NT IS No. PS276 313/4 (1974), 12 pp. Denton. M. S. "Portable f'eld Monitor for PCBs," Abstract No. 629. 1983 Pittsburgh Conference and Exposition on An alytical Chemistry and Applied Spectroscopy, March 7-12. 1983. Qenton, M S.. S. R. Oinsmore and W. D. 8ostiCk. "Portable field Monitor for PC8s." in Proceedings: 1981 PC8 Seminar. G. Addis and J. Marks, Eds. Peoort No. tPRI-El-2572 (Palo Alto. CA: Electric Power Research Institute. 1982). op. 3*3 to 3-21. Denton, M S. , ano M. H. walker. "Portaole Infrared F>eic Monitor for PC8s: Phase II." in Proceedings: 1983 PCS Sem inar, G. Addis and R. v. Komai EdT Report No. EPRI-Et-358*. (Palo Alto. CA: Electric Power Research Institute, 1984). Department of Health, Education and Welfare, "final Report of the Subcommittee on the Health Effects of Polychlorinated Bi phenyls and Polybrominated B'phenyls of the OHEW Committee t: Coordinate Toxicology and Related Programs." Env. Health Persp. 24:129-208 (1978a). Department of Health, Education and Welfare. "OHEW Subcom mittee on Health Effects of PC8s and PBBs, General Recommen dations," Env. Health Perso, 24:107-189 (1978b). Department of Health. Education and Welfare. "OHEW Subcom mittee on Health Effects of PC8s. General Summary and Con clusions," Env. Health Persp. 24:191-198 (1978c). Department of Transportation. "Polychlorinated Biphenyls (PCBs) in Transit System Electrical Equipment." Final Report. Urban Mass Transportation Administration, Office of Technical Assistance, Washington, 0C, UMTA-MA-06-0098-84-1; NT IS No. P684-222207 (1984) 104 pp. Oequidt, J. , F. Erb, C. Van Aerde and P. Colein. "Determina tion of Polychlorinated 8ionenyls in Biological Media," 8u1I. Soc. Pharm. Lille 31(2-3):149-155 (1975); Chem. Abst.. 84:3939ln (1976). HONS 223810 364 Bibliography OeRoos, f. 1. , M. Cooke. J E. Gebhart, L. E. Slivon, and P J. Mondron. "An uodate on Analytical Methods for Rolycnlonnated Biphenyls (PCS). Polychlorinated Oibento- furans (PCDf) and Polycnlorinated Dibenjo-g'dioxins (PCOO)." in Proceedings: 1983 PC9 Seminar, G. Addis and J. Mams Eds.. Report No, EPRI*El*3581. (Palo Alto, CA, Electric Power Research Institute. 1904). Oevemsh, I W. and L. Har 1ng-Bowen, "The Examination ang Estimation of the Performance Characteristics of a Standard Method for Organo-Chlorme Insecticides and PCB," in Hydro* carbons ang Haloqenated Hydrocarppns in the Aouitic Environ* ment~! r *" Afghan and 0. Macjcay", EdT. (New 'vortx,: Plenum Press. 1900). OP. 231*253. deVera, E. R. , B. P. Simmons, R. 0. Stephens and 0. 1. Storm. 'Samoiers ina $*moi'no Procedures for Hazardous Waste Streams." Municipal Environmental Researcn laooratory, j.j. Environmental Protection Agency. Cincinnati, OH. EPA-60O/2* 00*018 (January 1900). 0e Voogt, P.. J. C. Ktamer and U. A. T. Brinkman. "Identifi* cation and Quantificatidn of Polychlorinated Siphenyls in Paper Board Using Fused Silica Capillary Gas Chromatography," Bull. Environ. Contam. Toxicol. 32(l):45-52 (1904) 0e Vos, R. H. "Analytical Techniques in Relation to the Con* lamination of the Fauna." TNQ-nieuws 2 7;615* 622 ( 1972). 0e Vos. R. H. and E. W. Peet. "Thin-layer Chromatograohy of Polychlorinated Biphenyls." Bull. Environ. Contam. Toxicol. 6(2):164*170 (1971). Oexter, R. N. and S. P. Pavlou. "Characterization of Poly chlorinated Biphenyl Distribution in the Marine Environment." Bull. Environ, Contam. Toxicol 16(4):477-482 (1976). 0'ltri, F. M. and M. A. Kamrin, Eds. PCBs: Human and En vironmental Hazards (Boston; Butterwortn Publishers, 1903) Wpp. Oniing, w. i. , G. E. Miracle and G. u Boggs. "Organic Photochemistry. XVIII. Tropospheric Phototransformat ion Rates of Z~ , 3". and 4-ChlorobiphenylPreprints, Oivision Of Environmental Chemistry, American Chemical Society Na tional Meeting, Washington, 0C, pp. 34J-346 (August 1983). OiNardi, S. R. and A. M, Oesmarais. "Polychlorinated Bi phenyls in the Environment," Chemistry. 49(4>:14-17 (1976). MONS 223611 Bibliography 365 0 Toro, 0. M. and i. M. Horzemoa. "Reversible ana Resistant Component Model of Hexacnlorobionenyl Adsorot jon-0esorpt-ion Resusoension and Oilution," Chaoter 6 in Physical 8ehavior PCBs m the Great lakes, C. Mac*ay, S. Paterson, S. J. Cisenreicn and M. 5. Simmons, Eds. (Ann Arbor, Ml: Ann Arbor Science Publishers, Inc., 1983), po 89*113. Qi Toro, 0. M. , l. M Horzemoa and M. C. Casey. "Adsorption and Oesorption of Hexacnlorooipnenyl. A. Experimental Re* suits and Oiscussions- 6. Analysis of Exchangeable and Nonexcnangeab'e Components." EPA-600/3`83-088, PB83-261677 (September 1983), 322 pp Ooguchi, M. and S. Fukano. "Residue Levels of Polychlori nated Terphenyls. Polychlorinated Biphenyls and 00T in Human Blood," Bull. Environ Contam. Toxicol. 13:57-63 (1975). Qolan. J. w and R. C. Hall. "Enhancement of the Sensitivity and Selectivity of trie Coulson Electrolytic Conductivity OeLector to Chlorinated Hydrocaroon Pesticides." Anal. Chem. -SU3) 2193-2204(1973). Oo'an. J. W. , R. C. Hall and T. M. Todd. "Selective Oeteclion of Chlorinated Insecticides in the Presence of Poly* chlorinated Biphenyls," J. Assoc. Off. Anal. Chem. 55(3): S37-538 (1972). Oolphin, R. J. and f. W, Willmott. "Separation of Chlori nated 0ibenzo*p*dioxins from Chlorinated Congeners." J. Chromatoor. 149:161*160 (1978). Conkerbroek, J. J. , n. J. R. van Eikema Homes, C. Gooijer, n h. Veithorst and R. W. Frel. "Sensitized Room*Temperature Phosphorescence for Detection in Continuous Flow and Chro matographic Systems." Chromatoorapnia 15(4):218*222 (1982). ....eroroet, J. ... ... J. R. van eikema nommes, C. Gooijer, N. H. Veithorst and 8. W. Frei. "Phosphorescence Oetection of Polychloronaphthalanes and Polychlorobiphenyls in liquid Chromatography," J. Chromatoor. 255:581*590 (1983). Oonkin, P. , S. V. Mann and E. I. Hamilton. "Microcoulomatric Determination of Total Organochlorine Pesticide and Poly chlorinated Biphenyl Residues in Grey Seal (Maiichoerus qrypua) Blubber," Anal. Chim, Acta 88:289-301 (1977). Ooskey, P. V. and A. W. Andren. "High-Volume Sampling of Afrborne PolychlorobipnenyIs with Amberlite KAO-2 Resin," Anal. Chim. Acta 110:129-137 (1979). HONS 223812 Bibliography Oougherty, R C. "Toxic Residues and Pollutants," Chaoter 32A in Biochemical Applications of Mass SpectroWtrv. f:p, Supplemental volume, G. R. wal ler and 0. C. Oermer, (N*w Yorx, NY: PP. 951-960. wi ley-[nterscence Publication i^ani ' Oougherty, R. C. "Negative Chemical Ionization Mass Soectrometry: Apolications in Environmental Analytical Chem istry," B'omeo Mass Spectrom. 0(7)203-291 (1981a). Oougherty, R. C. Fields can Cause 11:71-84 (1901b). "Chemical Asymmetric Geometrodynamics: Physical Synthesis." Origins of ' Oougherty, R. C. . J. 0. Roberts. H. P. Tannenbaum, and F j Biros, "Positive and Negative Chemical Ionization Mass Soec* tra of Polychlorinated Pesticides," in Mass Spectrometry ^nq `<MR Spectroscopy Pestic'de Chemistry, R. -iaoue and y~ . Biros (Eds ), New Yorx-tondon U973 ). pp. 33-4 7 Oougherty, R. C., M. J, Whitaker, L. M. Smith, 0. 1. Stalling and 0. W. Kuehl, "Negative Chemical Ionization Studies of Hu man and Food Chain Contamination with xenooiotic Chemicals 1 Environ. Health Persp., 36:103-110 (1900). Oougherty, R. C., M, J. Whitaker, S.-Y, Tang, R. Bottcher, m. Keller, and 0. W. Kuehl, "Sperm Oensity and Toxic Substances: A Potential Key to Environmental Health Hazards," Chapter n in Environmental Health Chemistry, The Chemistry of Environ mental Agents as Potential Human HazardT! J. 0. McKinney (Ed. ), Ann Arbor Science Publishers, [nc., Ann Aroor. Michigan (1981). pp. 263-270. Cow Chemical Company, "determination of Chlorinated Siohenyi-, in the Presence of Chlorinated Benzenes," Midland Ml, July 1, 1901. Driscoll, J. N. and l. S, Krull. "Improved GC Separations with Chemically Bonded Supports," Amer. Lao, pp. 42-52 (May 1983). Ory Color Manufacturers Association, "An Analytical Procedure for the Determination of Polychlorinated Biphenyls in Ory Phthalocyanine Blue, Phthalocyanine Green, and Oiarylide Yel low Pigments," Arlington, VA (1982). Oudenoostel, B, F. "Tentat ive Method of Test for Polycnlon* nated diphenyls in Water," Attachment B in "Sampling Methods and Analytical Procedures Manual for PCS Disposal: Interim Report," J. H, Beard, III and J. Schaum. Office of Solid Waste, U-S. Environmental Protection Agency, Washington, 0C (February 10, 1970). HONS 223813 BibMograpny 367 Oufefc, P. , V. Pacaxova ano K. Zivny. ''Gas Chromatographic Behaviour of Mono- and O'hydroxybiphenyls on various Silicon* Phases," J. Chromatoqr 11.ISO-154 (1981). Ouinner, J. C. and M. T. j. Hillebrand. "Characterization of PC8 Components m Cloonen Formulations by Caoillary GC-MS and GC-ECO Techniques," Environ Sci, Ttchnpl. 17:449-456 (1983). Ounn, W. 0., 1. Johannson, 0. L. Stalling, T. R. Schwlrtz, 8. R. Marlow, J. 0 Petty, and J. 0. Hogan, 'Apoiication of SI MCA to the Characterization of PCB Residue Profiles in Sed iment, Water, and Aquatic B'ota," Abstract, 134th Annual Chemical Society National Meeting, September 12-17, 1982- Ounn, W. J. , MI. 0. L. Stalling, T. R. Schwartz. J. W. Hogan J. 0 Petty, E Johansson, and S. Wold. "Pattern Recognition for Class'fication and Determination of Polychlorinated Bi phenyls in Environmental SamolesAna l. Chem. 56:1308-1313 ( 1904). 0urf*e. R. L. . G. Contos. F. C. Whitmore, J. 0. Barden, i. i. Hacxman, 111 and R. A. Westm. "PC8$ ;n the United States Industrial Use and Environmental Distributions," Prepared for the U.S, Environmental Protection Agency, Office of Tone Substances, Report No. EPA 560/6-76-005 (NT IS No. PB-252 012), 488 pp. (1976). Ouvall. D. S. and W. A. Rubey. "Laboratory Evaluation of Htgh-Temperatur Destruction of Polychlorinated Biphenyls and Related Compounds." U.S. Environmental Protection Agency, EPA-600/2-77-228; NT IS No. P8 279 139 (December 1977). Oyer, N. "PCBs * The Federal View." in Proceedings: 1981 PCB Seminar. G. Addis and J. Mark*, Eds. (Palo Alto, CA: Electric Power Research Institute, 1981), pp. 1-1 to 1-10. Dyment, P G. . L. M. Hebertson. E. 0. Gomes. J. S. Wiseman ano R. w. Homabrook. "Absence of Polycnionnated Btpnenyis in Hyman Milk and Serum from Texas and Human Milk from New Guinea," Bull. Environ. Contam. Toxicol. 6(6):532-534 (1971). Oztdic, 1., 0. 1. Carroll. R. N. Stillwell and E. C. Horning. "Atmospheric Pressure Ionization (API) Mass Spectrometry: Formation of Phenoxide Ions from Chlorinated Aromatic Com pound*," Anal. Chem, 47(8):1308-1312 (1975). Eadie, B. J. . C. P. Rice and w. A. Frez. "The Role of the Benthic Boundary in the Cycling of PCBs in the Great Lakes," Chapter 12 in Physical Behavior of PCBa in the Great Lakes, 0. Maekay, S. Paterson, i. J. Eisenreich-end'M. ~S. Simmons, Eds. (Ann Arbor, MI: Ann Arbor Science Publishers, Inc., 1983) 442 pp. MONS 223014 368 Bibliography Easty, 0. Biphenyls fiber," ( 1973 ). 8. "Quantitation of Mixtures of Polychlorinated Isolated from Paperboard Containing Recycled Tech. Assoc. Pulp and Paper Ind. 56(5)131-134 Easty, 0. B. and 8. A Waoers. "Determination of Polychlor inated Biphenyls in Paper M1)l Effluents and Process Streams," Analytical letters, l0(ll):857-867 (1977). Easty, 0. 8. and 8. A. Wabers. "Determination of Polychlor inated Biphenyls in Paper Mill Effluents," Tech. Assoc. Pulp and Paper Ind. 61(10);71-74 (1978). Ecology and Environment, Incorporated. "Summary of the Heaith Effects or PCBs," Report Supmittea to U.S. Environ mental Protection Agency and Admitted as Part of the "Offi cial Rulemaking Record PC8 Regulations for Closed and Con trolled waste Manufacturing Processes," Fed. Reg. 47:46993-5 (1982). Eder, G. "Polychlorinated Biphenyls and Compounds of the DOT Group in Sediments of the Central North Sea and the Norwegian Depression," Chemosphere 5(2):101-106 (1976a). Eder, G. "Evaluation of Environmental Polychlorobiphenyls and DOE in Terms of Mixtures of Commercial Preparations from Peak Heights of Packed-Column Gas Chromatograms Using a Pro grammable Calculator," J, Chrpmatoqr. 121:269-277 (1976b). Edison Electric Institute, and The National Rural Electric Cooperative Association. "Comments and Studies on the Use of Polychlorinated Biphenyls in Response to an Order of the United States Court of Appeals for the Oistrict of Columbia Circuit, Vol. Ill, Report of the Study of PCBs in Equipment Owned by the Electric Utility Industry," submitted to the U.S. Environmental Protection Agency, Washington, 0-C. (February 12, 1982). Edwards, R. "Some Factors in the Separation of Polychlorobiphenyls (PCBs) from Organochlorine Pesticides by Column Chro matography Combined with Gas-liquid Chromatography," Pestle, Sci. 5:293-304 (1974). Egestad, B., T. Curstedt and J. Sjtivall. "Simple Procedures for Enrichment of Chlorinated Aromatic Pollutants from Fat, Weter and Milk for Subsequent Analysis by High-Resolution Methods," Anal, Lett. 15(A3):293-307 (1982). Eichelberger, J. W,, l. E. Harris and W. 1. Budde. "Applica tion of Gas Chromatography-Mass Spectrometry with Computer Controlled Repetitive Oata Acquisition from Selected Specific Ions." Anal. Chem. 46(2):227-232 (1974). MOMS 2238X5 Bibliography 369 EisenDeiss, F. ana h. Sieper. "The Potential Use of High- Performance Liquid Chromatography on Residue Analysis " J. Chromatoqr, 83:439-446 (1973). ' Eisenreich, S. J.t G. J. Ho Mod and T. C. Johnson. "Atmo spheric Concentrations and Deposition of Polychlorinated Bi phenyls to Lake Superior," Chapter 21 in AtmosoheHc Pol lutants in Natural Waters. S. J. Eisenreich, Ed. (Ann Arbor, M]: Ann Arbor Science Publisher*, Inc., 1981a) pp. 425-444. Eisenreich, $. J., B. B. Looney and J. 0. Thornton. "Air borne Organic Contaminants in the Great lakes Ecosystem," Environmentat Science and Technology 15:30-38 (1981b)- c isenreicn. S. J. and T. C. Johnson. Lakes: Sources, Sinks, Burdens," in vironmental Hazards, F. M. O'ltri and (Boston: Butterworth Publishers, 1983), "PCBs in the Great PCBs: Human and En W. JT Kamrin, Eds7 pp. 49-76. Eisenreich, S. J. . P. 0. Capel and B. B. Looney. "PCB Dy namics in Lake Superior Water.'* Chapter 11 in Physical Be havior of PCSs in the Great Lakes. D. Mackay, S. Paterson, S. J. Eisenreich and H. S. Simmons, Eds. (Ann Arbor, Ml: Ann Arbor Science Publishers, Inc., 1983a), 442 pp, Eisenreich, S. J., B. B, Looney and G. J. Hollod. "PCBs in the Lake Superior Atmosphere 1978-1980," Chapter 7 in Phys ical Behavior of PCBs in the Great Lakes. 0. Mackay, S.Paterson, S. J7 Eisenreich and M. 5. Simmons, Eds. (Ann Arbor, MI: J42 pp. Ann Arbor Science Publishers. Inc., 1983b). Eisenreich, S. J. and 8. 8. Looney. "Evidence for the At mospheric Flux of Polychlorinated Biphenyls to Lake Superior," Chapter 9 in Physical Behavior of PCBs in the Great Lakes. 0. Mackay. S. Paterson. $. J. Eisenreich and M, $. Simmons, Eds. (Ann Arbor, Ml: Ann Arbor Scienco Pub lishers, Inc., 1983), 442 pp. Elder, 0. "PCBs in N.W. Mediterranean Coastal Waters," Marine Pollution Bulletin. 7(4):63-64 (1976). Elder, V. A,, B. I, Proctor and R. A. Kites. "Organic Com pounds Near Oumpsites in Niagara Falls, New York." Biomedical Mass Spectrometry 8:409-415 (1981). Environmental Oefense Fund. Natural Resources Oefense Coun cil, and Chemical Manufacturers Association. "Recommendation of the Parties for a Final EPA Rule on Inadvertent Generation of PCBs," Submitted to Oon R. Clay. Acting Assistant Admin istrator, Environmental Protection Agency, Office of Toxic Substances, Washington, OC. April 13, 1983. MOMS 223SX* 370 Bibliography Environmental Protection Agency. "Identification of Poly chlorinated Biphenyls m the Presence of ODT-Type Compounds," Office of Research and Monitoring, Washington, O.C., epa-r?. 72-064 (NTl$ No. P0-213 900) (October 1972), ' Environmental Protection Agency "Sample Collection Manual, Ecological Monitoring Branch," Office of Pesticides Programs^ Benefits and Field Studies Oivision, Washington, O.C. (1976) Environmental Protection Agency, "40 CFfl Part 60 - Standards of Performance for New Stationary Sources," Fed, fteo. 4?41754-417B9 (August 10, 1977). Environmental Protection Agency. "Methods for Benzidin*, Chlorinated Organic Compounds. Pentachlorophenoi and Pesti cides in Water and Wastewater." Interim Report. EnvironmentaI Monitoring and Support Laboratory. Cincinnati. OH. September 1978. Environmental Protection Agency. and PCBs-- Method 608," Fed. Peg 1979a). "Qrganochlonne Pesticides 44:69501-69509 (December 3. Environmental Protection Agency. "Bast/Neutrals, Acids, and Pesticides-'Method 625," Fed. Peg. 44:69540-69552 (Oecember 3, 1979b). Environmental Protection Agency. "Appendix III - Example Quality Assurance and Quality Control Procedures for Organic Priority Pollutants," Fed. Peg. 44:69553-69559 (Oecemoer 3, 1979c). Environmental Protection Agency. "40 CFR 761, Polychlori nated Biphenyls (PCBs) in Manufacturing, Processino. Dis tribution in Commerce, ano use Promo11ions, final Rule,' Fed. Reg. 44:31514-31568 (1979d). Environmental Protection Agency. "Analytical Protocol Screening Publicly Owned Treatment Works (PON) Sludges Organic Priority Pollutants," Environmental Monitoring Support Laboratory, Cincinnati. OH (Septemoer 1979e). for for and Environmental Protection Agency. "Handbook for Analytical Quality Control in Water and Wastewater Laboratories." En vironmental Monitoring and Support Laboratory, Cincinnati. OH (March 19790. Environmental Protection Agency. "Interim Guidelines and Specifications for Preparing Quality Assurance Project Plans." Office of Monitoring Systems and Quality Assurance, Washington, O.C.. QAMS-Q0S/8Q, Oecember 27, 1980a. MOMS 2238X7 Bibliography 371 Environmental Protection Agency. ''Quality Assurance Program Plan for the Office of Toxic Substances, Office of Pesticides and Toxic Substances," wasnmgton, O.C. Octacer 19800. Environmental Protection Agency. "Test Methods for Evaluat ing Solid Waste - Physical-Chemical Methods,' Office of water and Waste Management, -asnmgton. O.C.. $w-846 ( 1980c). Environmental Protection Agency "Ambient water Quality Cri teria for: Polychlorinated Biphenyls (PCBs)," Report for Office of Water Regulations and Standards. Criteria and Stan dards Oivision. Washington, D.C.. EPA 440'5-80*068 NT IS No. PB81-117798), October 19804. Environmental Protection Agency. "The Analysis of Polychlor inated Biphenyls in Transformer fluid and Waste Oils." Office of Research and Development, Environments1 Monitoring and Support laboratory, Cincinnati. OH (February 1981a) Environmental Protection Agency. "PC8 Oisoosa! by Thermal Destruction," Report by Solid Waste Branch, Air and Hazardous Materials Oivision. U S. E^vironmental Protection Agency, Re gion p, Oailas, TX, EPA-ZQu/ 9-81-001 (.NT IS Ho. ?B82 HI 260), 606 pp. (1981b). Environmental Protection Agency. "Interim Methods for the Sampling and Analysis of Priority Pollutants in Sediments and Fish Tissue," Report by Physical and Chemical Methods Branch, Environmental Monitoring and Support laboratory, Cincinnati, OH, EPA 600/4-81-055 (1981c). Environmental Protection Agency. "Toxic Substances Control Act Inspection Manual; Volume 1, TSCA Base Manual; Volume 11, PCS Inspection ManualU.S. Environmental P-otection Agency. Pesticides and Toxic Substances Enforcement Oivision, Washington, OC (March 1981d). r-ivi ronmental P-ntection Agencv. "40 CfR art 761. Poly chlorinated Biphenyls (PC8s) Manufacturing, Processing, Dis tribution in Commerce, and Use Prohibitions; Recodification." fed. Reo. 47; 19526-19527 (May 6. 1982a). Environmental Protection Agancy. "40 CFR Part 761, Poly chlorinated Biphenyls (PCBs); Manufacture, Processing, Dis tribution, and Use ih Closed and Controlled Waste Manufac turing Processes," fed. Reg. 47:24976-2498? (June B. 1982b). Environmental Protaction Agancy. "40 CPR Part 761, Poly chlorinated Biphenyls (PCBs); Manufacturing, Processing, Dis tribution in Commerce, ana Use Prohibitions; Use in Closed and Controlled waste Manufacturing Processes," fed. Reg. 47:46980*46986 (October 21. 19B2c). MONS 223818 372 Bibliography Environmental Protection Agency. "Analysis of Pesticides Phthaiates. and Polychlorinated Biphenyls in Soils and Bottom Sediments," HWl Sample Management Office, Alexandria, VA, un punished method (November 4, 1982d). 12 pp. Environmental Protection Agency. "Test Methods for Evaluat ing Solid waste-Physlcal/Chemica1 Methods, SW-846, 2nd Edi tion, '* Office of Solid waste and Emergency Response, Washington, OC (July 1982e). ' Environmental Protection Agency. "40 CRF Part 761, Polycnlonnateo Biphenyls (PCBs) Manufacturing, Processing, Dis tribution in Commerce and Use Prohibitions; Use in Electrical Eouipment," Fed, fteo. 47:37342-34360 (August 25. 1982f) Environmental Protection -gency. "40 CFR art '61. Pro cedural Amendment of the Approval Authority for PCS Disposal Facilities and Guidance for Obtaining Approval," Fed. Rea 48:13181-13186 (1983a). Environmental Protection Agency. "Quality Assurance News letter," Vol. 5, No. 3. Environmental Monitoring and Support laboratory, Cincinnati, ON (April 1983b). Environmental Protection Agency. "Quality Assuranca Program Plan for the Office of Toxic Substances. Office of Pesticides and Toxic Substances," Washington, O.C. (September 30, 1983c). Environmental Protection Agency. "40 CFR Part 761, Poly chlorinated Biphenyls (PCBs); Manufacturing, Processing, 0's- tnoution in Commerce, ano use Promoi tions, ' m loqe o* Peg- era) Regulations, Title 40. Part 425 to End (Revised as of July 1, 1983d), U.S. Government Printing Office, Washington, OC (1983d) pp. 530-566. Environmental Protaction Agancy. "40 CFR Part 761. Poly chlorinated Biphenyls (PCBs); Manufacture. Processing. Ois- tribution in Coeimerce and Use Prohibitions; Use in Electrical Transformers, Advanced Notice of Proposed Rgleeiaking," Fed- Red. 49:11070*11083 (March 23. 1984a). Environmental Protaction Agancy. "40 CFR Part 761. Poly chlorinated Biphanyls (PCBs); Manufacturing, Processing. Dis tribution in Coemrce and Use Prohibitions; Response to In dividual and Class Petitions for Exemptions; Exclusions. Exemptions, and Use Authorizations. Final Rule," Fed. Reg. 49 2B154-28209 (July 10. 1984b). HONS 223819 Bibliography 373 Environmental Protection Agency. '40 CFR Part 761, o'ychlorinated Biphenyls (PC8s); Manufacture, Processing. Dis tribution in Commerce and Use Prohibitions: Use in Electrical Trans formers," Pea, Peg 49:39966*39989 (Octooer 11. 1984c). Environmental Protection Agency. "Hass Spectrometric Identi* f'cation and Measurement of Polychlorinated Biphenyls as Isomer Groups." Oraft Report by Physical and Chemical Methods Branch. Office of Research and Development. Cincinnati, OH (Octooer 1984d) Environmental Protection Agency, "Organochlorme Pesticides and PC8s"Method 608." Fed. Rea. 49(2091:89-104 (October 26. 1984e). Environmental Protection Agency. "Base/Neutrals. Acids, and Pesticides**Method 625," Fed. Red.. 49(209):153*174 (Octooer 26, I984f) Erickson, M. 0. "Gas Chromatoqraphy/Fourier Transform Infrareo Spectroscopy Applications." Appl. Soectrosc. Jev 15(2): 261-325 (1979). Erickson, M. 0. "Review of the Report 'Statistical Analysis of Oata from a Round Robin Experiment on PCS Samples,"1 Letter Report, U.S. EPA Contract No. 68-01-5915, Task 06, February 1982. Erickson. M. 0. "Analytical Method: The Analysis of By Product Chlorinated 8iphenyls in Commercial Products and Product Wastes. Revision 2," U.S. Environmental Protection Agency. Office of Toxic Substances, Washington, OC, EPA 560/ 5-85-010 (1984a). Erickson, M. 0. "Analytical Method: The Analysis of By- roduct Chlorinated Biohenyls in Air. Revision 2." U.S. En vironmental Protection Agency, Office of Toxic Suostances. Washington, 0C, EPA 560/5-85-011 (1984b). Erickson, M. 0. "Analytical Method: The Analysis of By Product Chlorinated 8iphenyls in Water, Revision 2," U.S. Environmental Protection Agency, Office of Toxic Substances, Washington, 0C. EPA 560/S-8S-012 (1984c). Erickson, M. 0. and C. D. Pallizzari. "Identification and Analysis of Polychlorinated Biphenyls and Other Related Chem icals in Municipal Sewage Sludge Samples," U.S. Environmental Prottction Agency, Office of Toxic Substances, Washington, 0.C,. EPA-560/6-77*021 (August 1977), HONS 223820 374 Bibliography Erickson, M. 0. and E. 0. Estes. 'Evaluation of Chlorinated Hydroca roon Catalytic Reduction technology" U.S. Environ* mental Protection Agency. Office of Research and Development, Washington, 0- C. , EPA-60G/2*78*059 (Marcn 1978). Erickson, M. 0., L. C. Michael, R. A. Zweidinger and E. 0 PelUzzarl. "Development of Metnoos for Sampling and Analy sis of Polychlorinated Naphthalan** in Ambient Air." Environ Sci. Ttcftnol., 12:927*931 (1978). ' Erickson, M. 0. and E. 0. Pellizzari. "Analysis of Municipal Sewage Sludge Samples by GC/H$/Computer for Polychlorinated diphenyls and Other Chlorinated Organics." Bull Environ Con* tarn. Toxicol. 22.688*694 (1979). ~ Erickson, M. 0.. C. M. Soaracino. E. 0. Pellizzari and k. 8. Tomer. "Point Source Ambient Monitoring to Determine Imoact or ENSC0 incinerator located at V dorado, Arnansas." Draft Report submitted to Phillip Schwindt, U.S. Environmental Pro* tection Agency. Region 6, Sampling and Analysis Division. Oallas. TX, EPA Contract No, 68*01*4141, Task 29, October 1980a, 135 pp. Erickson, M. 0., 8. S. H. Harris, E. 0. Pellizzari, k. 8. Tomer, R. 0. Waddell end 0. A. Whitaker, "Acquisition and Chemical Analysis of Mother's Mrlk for Selected Toxic Sub* stances,11 Office of Toxic Substances, U.S. Environmental Pro* tection Agency. Washington, O.C., EPA 560/13*80*029, 1980b. Erickson, M. 0. and John $. Stanley. "Methods of Analysis for By-Product PC8**-literature Review and Preliminary Recom mendations," Interim Report No. 1. Office of Toxic Sub* stances, U.S. Environmental Protection Aaencv, Vashinoton. O.C. . c?A-56u/5-b2-u05, NfIS No. 135 pp. PB83 126 573 (1982). Erickson, M. 0., J. $. Stanley, k. Turman, G. Radolovicn, K. Bauer, J. Onstot, 0. Rose and M. Wickham. "Analytical Methods for 8yProduct PC8*--Preliminary Validation and In terim Methods," Interim Report No. 4, Office of Toxic Sub stances, U.S. Environments! Protection Agency, Washington, 0. C. , EPA-560/582*006, NTIS No. P883 127 696 (1982), 243 pp. Erickson, M. 0. and R. V. Shah. "Guidelines for PCS Destruc tion Permit Applications and Demonstration Test Plans," Oraft Interim Report No. 5, Revision 1, EPA Contract No. 68-01* 5915, Tesk 51. May 17, 1983, 80 pp. HONS 223921 Bibliography 375 Erickson, M. 0., J. S. Stanley, J. K. Turman, G. Radolovich, J. Onstot, M. Wicxham an<j J Going. "Determination of Inci dental 1 y Generated PCBs m Commerical Products and wastes By Capillary GC/EIMS." Abstract from 1983 Pittsburgh Conference and Exposition on Analytical Chemistry and Applied Spec* troscopy, Marcn 1983a. Erickson, M. 0., J. S. Stanley, J. K. Turman. J. E. Going and 0. P Redford. "Methods for Analysis of Complex Mixtures in Complex, Vanaole Matrices**Ch1orinated Biphenyls in Commer cial Products and wastes,1' in Polynuclear Aromatic Hydrocar* bons: formation, HetaDolism and Measurement, m. Cooke and A. J. Senni's. Eds! (Columbus. OH: 8atte11 e Press, 1983b), pp. 483*492, Erickson, M. 0., K. M. 8auer, F. J. Bergman, "Analytical Methods for By-Product and Destruction Oerived PCBs'-lnterlaboratory Validation A," Oraft Interim Report No. 6, Task SI, EPA Contract No. 68*01*5915, August 23. 1983c. Erickson, M. 0., J. S. Stanley, G. Radolovich and R. 8. 8lair. "Analytical Method; The Analysis of 8y*Product Chlorinated Bionenyls m Commercial Products mo Product Wastes," Revision 1, Prepared by Midwest Research Institute for Office of Toxic 5ubstances, U.S. EnvironmentaI Protection Agency, Washington, 0C, under Subcontract No. A*1044(8149)* 271. Work Assignment No. 17 to Sattelle, Washington, 0C August* 15, 1983d. Erickson, M. 0., J. P. Goforth, M. A. Jones, M. C. Saylor, K. 8. Tomer, and E. 0. PelHzzari, 8. T. Cook. M. Franken* berry, J. J. Breen and F. W. Kutz. "Analysis of Blood and Adipose Tissue Samples from GSA Workers for Polychlorinated Biphenyls (PCBs) Phase I: Packed Column GC/EC0 and GC/MS Analyses," Interim Report, Contract No. 68*01-3849, Task 4, U.S. Environmental Protection Agency (1983e). Erickson, M. 0., P. G. Gorman, and 0. T. Heggem. "Relation- snip or Destruction Parameters to the Oestruction/Removal Ef ficiency (ORE) of PCBs," Journal of the Air Pollution Control Association, in press (1984a). """ Erickson, M. D., C. J. Cole, J. 0. Flora, Jr., P. G. Gorman, C. 1. Haile, G. 0. Hinshaw, F. C. Hopkins, and S. . Swanson. "Thermal Degradation Products from Olelectric Fluids," U.S. Environmental Protection Agency, Washington, 0C. EPA 560/ 5-84-009; NT IS No. P8 85/38535 (1984b). .Erickson, M. 0., C. J. Cole, J. 0. Flora, Jr., P. G. Gorman, C. l. Haile, G. 0. Hinshaw, F. C. Hopkins, S. E. Swanson, and 0. T. Heggem, "PC0F Formation from PC8s Under Fire Condi tions," Chemosphere (submitted) (1984c). HONS 223822 370 Bibliography Erickson. M. 0 , J. S. Stanley, J. K. Turman. J E- Going 0. P. Redford, and 0. T. Heggem. "Determination of By Product PC8s in Commercial Products and Wastes oy High R#jo- lution GC/EIMS," Anal. Ch*m. (submitted) (1984d). Erickson, M. 0., C. 4. Cola, J. 0. Flora, 4r., P. G. Gorman, C. 1. Hail*, G. 0. Hinshaw, F. C. Hopkins, S. E. Swanson, and 0. T. H*gg*m. "Formation of PCOFs Under 'Optimized' Combus tion Conditions from iow-i*v*l PC8 Oielectric Fluids," Prsented at EPRl PC0F Workshop, Palo Alto, California (1984*). Erickson, M. 0., C. J. Cole, J. 0. Flora, 4r., P. G. Gorman, C. 1. Haile, G. 0. Hinshaw, F. C. Hopkins. S. E. Swanson, and 0. T. Heggem. "Formation of PCOFs Under 'Optimized' Combus tion Conditons from low-level PCS Oielectric Fluids," in pro ceedings: 1984 EPRI PCDf Workshop, G. Addis and R. Komai, Eds., Electric Power Research Institute. (1985a) m press. Erickson, C. J. Cole, J. 0. Flora, P. G. Gorman, C. 1. Haile, G. 0. Hinshaw. F C. Hopkins, $. E. Swanson, and 0- T Heggem. "Thermal Degradation Products from Oielectric Fluids," Presented at 189th ACS National Meeting, Miami Beach, Florida (May 1985b). Erickson, M. D. , 4. $. Stanley, J. K. Turman, and G. Radolovich. "Analytical Method: The Analysis of Chlorinated Biphenyls in liquids and Solids," U.S. Environmental Protec tion Agency, Office of Toxic Substances, Washington, 0C, EPA560/5-85-023 (February 1985c). Erney, 0. R. "A Feasibility Study of Miniature Silica Gel Columns for the Separation of Some Polychlorinated Biphenyls, OOT, and Analogs." Bull. Environ. Contam. Toxicol. 12(6):710716 (19?4a;. Erney, 0. R. "Rapid Screening Method for Analysis of Chlori nated Pesticide and Polychlorinated Biphenyl Residues in Fish," J, Assoc. Offic. Anal. Chem, 57(3):576-579 (1974b). Ernst, W., R. G. Schaefer, H. Goerke and G. Eder, "Aufarbeitung von Meerestieren fiir die 8estimmung von PC8, OOT, 001. 000. y-HCH und HCB," Z. Anal. Chem. 272:358-363 (1974). Exnmr, J. H. (Ed.). Oetoiication of Hazardous Waste. Ann Arbor Science, Ann Arbor, Ml (1952a), 362 pp. Exner, J. H. "Summary of Polychlorinated Biphenyl Treatment Alternatives," Chapter 6 in Oetoiication of Hazardous waste, J. H. Exner, Ed. (Ann Arbor, MI: Ann Arbor Science Pub lishers. Inc., 1982b), pp. 119-120. HONS 223023 Bibliography 377 Farrington. J. V#. , E. 0. Goldberg, R W. Risebrougn, J. H. Martin and V. T. Bowen. "U.S. 'Mussel Watch* 1976-1978: An Overview of tht Trace-Metal. ODE. PCB, Hydrocarbon, and ArtT- ficial Radionuclide Oata." Environ. Sc i. Techno) 17.490-496 (1983) ' Far-well. S. 0., F A. Seland and R. 0. Geer. '* InterruptedSweep Voltammetry for tht Identification of Polychlorinated Biphenyls and Naphthalenes, Anal. Chem. 47(6);895-902 (Mav 1975). ftairheller. w. , P. J. Warn, 0. M. Harris and 0. l. Harris. "Technical Manual for Process Sampling Strategies for Organic Materials," Prepared for the U.S, Environmental Protection Agency, Office of Research and Development, Washington, 0. C., Report No. EPA-600/2-76-122 (Apri1 1976). Fehringer, N. v. and J. E. Westfall. "Separation and Identi fication of 00T Analogs in the Presence of Polycnlormeted Biphenyl Compounds by Two-Dimensional Thin-layer Chromatograohy," J, Chromatoor 57-397-405 (1971). Femia, R. A., $. Scypinski, and L. J. Cline love. "Fluores cence Characteristics of Polychlorinated Biphenyl Isomers in Cyclodextrin Media," Environ. Sci, fechnol.. 19(2):155-159 (1985). Finklea, J. 0., 1. . Priester, J. P. Creason. T. Mauser, T, Hinners and 0, I. Hammer, "Polychlorinated Biphenyl Res idues in Human Plasma Expose a Major Urban Pollution Pro blem," Amer. J, Putol, Health 62:645-6*1 (19"). Finlay, 0. J. , F. H, $iff and V. J. OeCarlo. "Review of PCS levels in the Environment," EPA-560/7-76-001; NTIS no. P8-2S3 735 (1976), Finstervalder. C. E. "Industrial Chemicals: Collaborative Study of the Oettrminetion of Polychlorinated Bipncnyis in Paperboard," J. Assoc. Off. Anal. Chem, 57(3):518-521 (1974), flshbtin, l. "Chromatographic and Biological Aspects of Polychlorinated Biphenyls," J. Chromatoqr 68:345-426 (1972). Flshbetn, l. "Toxicity of Chlorinated Biphenyls," Ann. Rev, Pharmacol. 14:139-156 (1974). Fishbtin, i. (Ed.). Potantial Industrial Carcinogens and Mutagens. (Amsterdam; Elsevier, 1979). _ HONS 223824 370 Bibliography Fisher, 0. J., T. 0. Rouse. ana T. * Lynn, "Field Oetermma- ton of PCB in fran$formr Oil 'ClOR-N-011 Kit1,'' in Pro* ceedinqs: 1983 PCB Seminar. G. Addis and R. Y. Komat fiT* Report No. EPRI-El-3581 (Palo Alto, CA; Electric Power Re search Institute. 1984). Food and Orug Administration. "Pesticide Analytical Manual 11 Vol. I, August 1, 1977. ' Fradkin, L. and S. Barisas. "Technologies for Treatment, Pa use, and Oisposa) of Polycnormated Siphanyl Wastes," Argonna National LaDoratory, Argonna. IL. Report No. ANl/EES-TM-168 (NT1S No. 0E 02013715]. 51 pp. (1982). Frank, R. , M. Holdrinet, H. E. Braun, 0. P. Oodga and G. E. Spranglar. "Residues of Organocnlorine Insecticides and olycnlonnateo Sionenyis in risn from tanas Huron -ino Superior, Canada. 1968-76," Pastic. Monit. J. 12(21:69-80 (197B). Frank, R. , R. 1. Thoeias, M. Holdrinat, A. L. W. Kemp, H. E. Braun and R. Oawson. "Organochlorint Insecticides and PCS in the Sediments of lake Huron (1969) and Georgian Bay and North Channel (1973).M Sci. Total Environ. 13:101-117 (1979). Frias, G. F. "Polychlorinated Biphenyl Residues in Milk of Environmentally end Experimentally Contaminated Cows," En viron. Health Perspec. 1(1):55-62 (April 1972). Friess, S. 1., V. A. Drill, H. W. Hays, T. A. Loomis and C. B. Schaffer. "Potential Health Effects from Exposure to Polychlorinated Biphenyls; laboratory Studies," in Advances in exposure, neaith and Environmental effects Stuoies or ^8s: Symposium Proceedings. T J. Davenport and 5. K. Bernard (tds. ), Office of Toxic Substances, U.S. Environ mental Protection Agency, Washington, 0. C., Report No. LSITR-S07-137B. NT IS No. P8S4-135771 (Oecemder 1983). op. 212 228. Frimmel, F. "01 fferentiation of Polychlorinated Biphenyls from Pesticides with Combined Gas Chromatography-Hass Spec trometry," Z. Watser Abwasser Forsch 6(4):113-116 (1973). 'Fufcano, S. and H. Ooguchi. "PCT, PCB and Pesticide Residues in Humen Fat and Blood," Bull. Environ. Contam. Toxicol. 17(5): 613-617 (1977). Fuller, 0. , J. Gordon and M. Kornreich. "Environmental As sessment of PCBs in the Atmosphere." U.S. Environmental Pro tection Agency, Washington, 0. C., EPA-450/3-77-045 (April 1976). HONS 223*25 Bibliography 379 furukawa. X. , K Tonomura and A. Kamipayashi. "Effect-of Chlorine Substi tut ion on the B todegradabi I i ty or Polychlori nated Biphenyl*," Appl Environ MicroD'o! 35(?1 ?23-??7 ( 19781. ---------- Gaffey, w. R. "The Epidemioloqy of PCBs." in PCS*: Human and Environmental Hazard*. F M. D'ltri and H. A. namrin, IdT iBoston- Sutterworth Publisher*, 1983a), pp. 279-298. Gaffey. W. R. "Recent EpidemioIogic Studies of PCBs," in Ad vances in Exposure. Health and Environmental Effect* Studies of PC8$: Symposium Proceeding*, r! j" Qavenport and 8 it. Bernard (Ed*.), Office of Toxic Substances, U. S. Environ mental Protection Agency, wasnington, 0. C. , Report No. ISI- TR-507-137B. HTIS No. PB84-135771 (Oecember 1983b). pp. 189 201. Gaffney, P. E. "Chlorobiphenyls and PCBs: Formation During Chlorination." Journal Water Pollution Control federation 49(3) 401-404 (Marcn 19?7) ' ------ ------- Galli*, 0.. A. Defner-Hallowel, J. C. White and J. Weber. "Optimization of a Reversed Phase Partitioning Technique for the Analysis of Polychlorinated Biphenyls in Aqueous Samples by Gas Chromatography/Mass Spectrometry." Bull. Environ, Contarn. Toxicol. 31(3);285-291; Chen. Abstr. "$9:145823: (19B3). Garcia-Gutierrez, A., A. E. Hcintyre, J. N. Lester and R. Perry. "Determination of Drgenochlorine Compounds in Waste Water Samples by Gas Chromatography and Gas Chromatography-Mass Spectrometry Using Capillary Columns," Environ, Technol. Lett- 4:129-140: Chem. Abstr. 98:204072h (1983). Garty. J.. A. $. Perry and J. Mozel. "Accumulation of Poly chlorinated Sipnenyl* (PC8s) in the Transplanted L;men Rama line Duriaei in Air Quality Biomonitoring Experiments," Nord. J. Bot. 2(6):583-586 (19833: Chem. Abstr. 98;14B790b (1$*3). Gassiot, M. , X. Tomis, F. Broto, L. G. Sabattf and G. Codinas. "Algorithms for the Quantitative Determination of PCBs in Chromatograms of Organocniorinated Contaminants: Application to Samples of Sediments and Marine Organisms." Analytical Techniques in Environmental Chemistry 2. J. Alpaiges, Ed. (Nw Tom. NY: Pergamon Press, 1982) pp. 249-258. Gast, R. "Studies into Quantitative PCS Determination," Muench. Btitr, Apwasser, Fisch.-Flussbiol. 30:215*225 (1978); Chem. Abst. 90: U5924e ( 1979). MOWS 229826 360 Bibliography General Accounting Office. "PA Slow \n Controlling PC3s " GAO/CED-82-21, 39 pages. Oecemoer 30. 1981. ' Gesser. H. 0.. A. Chow and F. C. Oavis. "The Extraction ana Recovery of Polychlorinated Biphenyls (PCB) Using Porous Polyurethane Foam." Anal, letters 4(12) 083*086 (1971) Giacin, J. R, and S. G. Gilbert. "Analysis of Polychlori nated Biphenyl $ in Packaging Materials," m Technical *a* vances in Packaging with Flexible Barrier Materials, ASTM stp 548, 10*19 (1973) Giam, C. S., A. R. Hanks, R. 1. Richardson, v. M. Sackett ana M. K. Wong. "00T, ODE. and Polychlorinated Biphenyls in Biota from the Gulf of Mexico and Caribbean Sea 1971 " Pesuc. Honlt. Jj. 6(3): 139*143 (1972). Giam, C S. , h. S Chan and G. S. Neff "''aoio md !-*oensive Metnoa for Oetection of Poiycnlormateo Stpnenyis ano Phthalates in Air," Anal. Chem. 47(13):2319*2320 (137S) Giam. C. S., H. $. Chan, and G- S. Neff. "Concentrations and Fluxes of Phthalates, DOTs, and PCBs to the Gulf of Mexico." in Karine Pollutant Transfer, H. l. Windom and R. A. Ouce. Eds. (Lexington. MA: Lexington Books. 1976) po. 375*386. Giger, W. , M. Reinhard, C. Schaffner and F. Ziircher. "Analy ses of Organic Constituents in Water by High-Resolution Gas Chromatography in Combination With Specific Oetection and Computer*Assisted Mass Spectrometry," Chapter 26 in identi fication and Analysis of Organic Pollutants in Water, i. h Iteith Ed! (Ann Arbor, Ml; Ann Arbor Science Pub)isners. Inc., 1976), pp. 433*452. Gilman, A. P. "Monitoring for PCBs in Fish; The Human Health Perspective," in PCBs: Human and Environmental Haz ards. F. M. 0'ltri and M. A. Kaarin. Eds. (Boston: Butter* worth Publishers, 1993). pp. 115*122. Glaser, J. A., 0. 1. Foerst. G. O. McKee, S. A. Quave and w. L. Budde. "Trace Analyses for wastewaters." Environ. Sci. Techno). 15;1426-1435 (1981). Godefroot, M.. M. Stechele, P. Sandra and M. verzele. "A New Method for the Quantitative Analysis of Organochlorine Pesti cides and Polychlorinated Biphenyls," J, High Resol. Chrom, and Chrom. Comm. 5:75-79 (1982a). MON$ 22982? Bibliography 381 Godefroot, M. ; M. SteChele, P. Sandra and H. venele. "a New Method for the Quantitative Analysis of Organochlorine Pesti cides and PolycnJorinated Biphenyls." Comm. Ejt, Communities. [Rep.] EUR 1982, EUR 7623 . Anal. OrQ. Microooilut water 16 23; Chew. Abstr. 97 13 3257p (1982b). Goer I i U, 0. f. , and L. M. Law. "Note on Removal of Sulfur Interferences from Sediment Extracts for Pesticide Analysis." Bull. Environ. Contam. Toxicol. 6:9*10 (1971) Goerl'U, 0. f and L. H. Law. "Determination of Chlorinated Insecticides in Suspended Sediment and Bottom Material," J. Assoc, Off. Anal Chem. S7<1):176-181 (1974). Goldstein. J. A. "3tructure*Activity Relationships for the Biochemical Effects and the Relationship to Toxicity," Chapter 4 in Ha loqenated Biphenv \ s. Terphenyls. Naphthalenes, Qitienro-dioxins and Related Products7 r! 5" KtmOrougn, Ed7 (New"fork. nT! ElsevTer/North*Hol land Biomedical Press. 1980), pp. 151*190. Goldstein, J. A., J. 0. McKinney. Z. W. LuC'er. 3 Hickman. H. Bergman and J. A. Moore. "Toxicological Assessment of Hexachlorobiohtnyl Isomers and 2.3,7,B-Tetrachlorodiben2ofuran in Chicks," Toxicol. App|. Pharmacol. 36(1):81*92 (1976). Goodman, J. [. `'Concepts in Toxicology and Carcinogenesis: A Basis for Oiscussing the Potential Environmental Hazard Posed by PCBs." in PCBs: Human and Environmental Hazards. F M. O'ltri and M. Kamrin, Eds. (Boston: Butterworth Pub* lishers. 1983). pp. 179*186. Gordon, R. j.. j. Szita and . J. Faeder. "Determination of Polychlorinated Biphenyls in Transformer Oils by Capillary Gas ChromatographyAnal, Chew. 54:478-481 (1982). Gorski, T. 4nd T. Syrowatka. "Simplified Method for the Sep aration and Determination of Residues of Organochlorine Pest* icides and Polychlorinated Biphenyls In Human Fatty Tissue." Chen, Abst. 91:88SW (1979). Gossaan, 0. G. "Oata Processing as an Alternative to Exten sive Sample Cleanup in the Gas Chromatographic Determination of PCBs," Abstract from the 1983 Pittsburgh Conference and Exposition on Analytical Chemistry and Applied Spectroscopy, March 7*12, 1983. Gothe, R. "Oxidation with Tetrabutylammonium Permanganate for Quantitation of DOT Residues in GLC Determination of Chlorinated Hydrocarbons," Bull, of Environ. Contam. Toxicol. 11(5):4S1-4S5 (1974). MOMS 223828 382 Bibliography Grant. 0. L. "Regulation of PCBs in Canada." in PCBs and Environmental Hazards. F. M. O'Itn and M.-a" RamrTfT Eds. (Boston1 Sutterworth Publisher*. 1983), pp. 383*392 Creichus, r. A. , J. J. woman. H. A. Pearson *nd D. J. Cal! "Analysts of Polychlorinated Biphenyls in Bird Tissues and Aroclor Standards with Gas Chromatography and Hass Spectrom* etry," ( 1974). Bull, of Environ. Contain, Toxicol. Ilf?)m-??n Griffin, 0. A. . A. 8. Marin and M. L. Deinzer. ''Optimization of Chromatographic Conditions for th* Separation of g,j)`*0DE from Aroclor 1254 on Silica, Using Aju1ee as Indicator " J. Assoc- Off Anal. Chem. 63(5):9S9-964 (1980). ' Griffitt. K. R. and J. C. Craun. "Gel Permeation Chromato graphic System: An Eva luation." J-. Assoc. Off. Anal. Chem :?(1) 168-1 72 ( 1974 ) ' Gross. H. L. . J. 0. Lay. Jr.. D. A. Lyon. 0. Lippstreu, N. Kangas, R. L. Harless, S. E. Taylor and A. E. Oupuy. Jr "2,3,7.8-Tetrach)orodibenzo-g-dio*in Levels in Adipose Tissue of Vietnam Veterans," Environ, Res. 33(l):261-268 (1984); Chem. Abstr. 100:108498r (1984). Gu, T. and M. Hanes. "Adsorptive Displacement from Activated Carpon: Recovery of 4,4'-Dichlorobipheny1Environ, Sci Techno). 18:55-57 (1984). Gutierrez. A. G. . A. E. McIntyre. J. N. Lester and R. Perry. "Comparison of Gas Chromatograpny and Gas Chromatography/Hass Soectrometry for the Analysis of Polychlorinated Biohenyis and Organochlorine Insecticides in Sewage Sludges." Enyiron ecnnoi. Lett. 4(12):521*528 (1983). Chem. Apsir iG0.5cj57* (1984). Hadorn. h. and K. Zuercher. "Contamination of Food with Polychlorinated Biphenyls (PCS) by Packaging Material and En vironmental Pollution," Gordian 73(12):458-462 (1973). Raefelfinger, P. "Limits of the internal Standard Technique in Chromatography," J. Chromatoqr. 218:73-81 (1901). Rahn, G. . and C. A. Ward. "The Determination of PCSs in Human Blood," Presented at the FACSS 10th Annual Meeting. September 25*30, 1983. Haile, C. L. and E. Baladi. "Methods for Determining the Total Polychlorinattd Biphenyl Emissions From incineration and Capacitor and Transformer Filling Plants," U. S. Environ mental Protection Agency, EPA-600/4-77-048, NTtS No. P8-276 745/7G1 (November 1977), 90 pp. HONS 223829 Bibliography 383 Haile, C. , J Stanley. R. H. Lucas. 0. Helroy. C. Nulton and w Gauger, Jr. "Comprehensive Assessment of Soecific Com* pounds Present 'n Combustion Processes. Vol. 1-Pilot Study of Combustion Emissions variability," Office of foaic Sub stance. U.$. Environmental Protection Agency, Washington. O.C. , EPA-560/ 5-83-004 (June 1963a). Haile. C. 1. . J. S. Stanley, T. walker. G. R. Cobb and 6. A. Boomer. "Comprehenstve Assessment of the Specific Compounds Present in Combustion Processes, Volume 3, National Survey of Organic Emissions from Coal Fired Utility Boiler Plants,'* Office of Pesticides and Toaic Substances, US- Environmental Protection Agency, Washington. O.C., EPA-560/5-03-006 (1963b). Haile, C. L.. and V. lopez-Avila. "Development of Analytical Test Procedures for the Measurement of Organic Priority Pollutants-'Project Summary," U.S. Environmental Protection Agency. Environmental Monitoring and Support Laboratory. Cincinnati. Ohio. EPA-600/S4-84-001; (Full Report available 4S NT IS No. ?6 84-129 048) (1?84). Haile, C. L.. J. S. Stanley. A. H. Magin, R. V. Northcutt and O. P. Radford. "Emissions of Organic Pollutants from Coal- Fired Utility Boiler Plants,- in Identiffcation and Analysis of Organic Pollutants in Air. i. Keith, (Boston*. Butterworth Publishers, 1984a), pp. 443-458. Haile, C. L., R\ B. Blair. T. Walker, and R. m. Lucas. "As sessment of Emissions of Specific Compounds from a Resource Recovery Municipal Refuse Incinerator," U.S, Environmental Protection Agency, EPA 600/5-84-002, (June 1984b). Hall, J., F. Record, P. Wolf, G. Hunt, $. Zelenski, P. Fennelly, A. Fisher, A. Garvick, T. Hockmen. w. Kilgore and 0. Koenig. "Evaluation of PCS Destruction Efficiency in an Industrial Soiier,' Report by GCn/Tecr.nsicgy division, Bedford, HA, to Oavid C. Sanches, USEPA, Office of Research and Development, (ERL, Research Triangle Park. NC, EPA-600/281-OSSa and b (NTIS Nos. P6 82-224 940 and PB 61-187 270), 172 pp. (1962). Hammer, 0. I., J. F. Finklee, l. E. Priester, J. E. Keil, S. H. Sandifer and K. Bridbord. "Polychlorinated Biphenyl Resi dues fn the Plasma and Hair of Refuse workers,- Environ. Health Pertpec. 1(1):83 (1972). Hammond, P. 6. "Biological Effects in Polychlorinated Biphenyls - Environmental Impact," Environ. Res. 5:312-338 (1972). MQN$ 228880 384 . Bibliography Hanai, T. and H F. Walton, "Chromatography of Ch)oririat*d Biphenyl* o> 4n lon-Eichanoe Resin." Ana). Chem 4^/Al 7sj. 766 (1977) Hanks, A. R. and 8. H. Colvin. "High-Performance Liquid Chromatography." Chapter 3 in Pesticide Analysis. K. C. 04$. d. (New fork. NY: Marcel Dekner. fncT! 1981). pp 99-174 Hannan, . J. and 0. 0. 8'II*. "Seoaration of Aldrsn from Aroclor 1254." 8u)l Environ Contam To<icol.. 8(6)-327-3?r (1972). H4nn4n, E. J. , 0. 0. 01)1$ and J. L. Herring. '`Analysis of Polychlorinated Biphenyls by Gas Chromatography and ultravio let Irradiation." J. Agr. Food Chem, 21(l):87-90 (1973) Hanneman, l. F. '`The New PCB Issue - Analysis of Soecific Congeners ^roouceo bv Unintentional 3v*3roduct Chemistry." Presented at Capillary Chromatography 82--An International Symposium. Tarrytown. NY. October 4-6. 1982. Hague, R. . 0. W. Schmedding and V. H. Freed. "Aqueous Solu bility. Adsorption, and Vapor Behavior of Polychlorinated Bi phenyl Aroclor 1254," Environ. Scl. Tech. 8(2):139-142 (1974). Haque, R. and 0. Schmedding. "A Method of Measuring the Water Solubility of Hydrophobic Chemicals; Solubility of Five Polychlorinated Biphenyls," Bull. Environ. Contain, Toicol. 14(1); 13-18 (1975). Haque, R. and 0. Schmedding. "Studies on the Adsorption of Selected Polychlorinated Biphenyl Isomers on Several Sur faces,* j. environ, ici. rieaiin 611(21.-23-127 ( 1975). Haraguchi, H. , M. Kuroki, Y. Masuda, and N. Shigematsu. ''De termination of Methylthio' and Methylsulfone Polychlorinated Biphenyls n Tissues of Patients with 'Yusho'," Food Chem. Toiicol. 22(4):282-288 (1984). Harris, J. C., 0. J. Larsen, C. E. Rechsteiner and K. E. Thnm, "Sampling and Analysis Methods for Hazardous waste Incineration (First Edition)," Report to Larry 0. Johnson. U.S. Environmental Protection Agency, 1ERL, Research Triangle Park, NC, EPA Contract No. 68-02-3111, Technical Oirective No. 124, February 1982, 400 pp. Harris, R. W. , C. F. Grainger and W. J. Mitchell. "Valida tion of a Method for Measuring Polychlorinated Biphenyls in Natural Gas Pipelines." EPA 600/4-81-048: NTIS No. PB82207556 (1981). MOMS 223831 Bibliography 385 Harrison, A. G. , F I Qnuska, and C. W. Tseng. "Chemical Ionization Mass Spectrometry of Specific Polychlorinated Bi phenyl Isomers," Anal. Chem. . 53:1183*1186 ( 1981). Harvey, G R. , h p Mieias. v. T Bowen and w G. 5te*n- hauer. "Observations in the Distribution of Chlorinated Hydrocarbons in Atlantic Ocean Organisms," J. Marine Res 32:103*118 (1974) -------------------------- Harvey, G. R. , and w. G. Steinhauer. "Transport Pathways of Polychlorinated Biphenyls in Atlantic Water." J. Marine Res 34:561-575 ( 1976). -------------------------- Harvey. J. . Jr., G. Zeig, R. Cannizzaro, H. Oishburger and J. Sherma (Ed.), "Pesticide Analytical Methodology," ACS Sym posium Series 136 (Washington, 0. C.: Amer. Chem. Soc. 1980). Harz, A., of Mirex Gericntl. (155?7. and u. Muelder. "Gas Chromatographic Determination and Polycnlorinated Biphenyls," lebensmittelchem. Chem. 37(6): 146-174 ( 1983); Chem. Abst. l6l:$S94k Hass, J. R. and M. 0. Friesen. "Qualitative and Quantitative Methods for Oioxin Analysis." Ann. N.Y. Acad. Sci. 320:28*42 (1979). Hass, J. R., M. 0. Friesen and M. K. Hoffman. "Recent Mass Spectrometric Techniques for the Analysts of Environmental Contaminants," Chapter 11 in EnvironmentaI Health Chemistry, The Chemistry of Envirorwnental~Aqents as Potential Human Hazards. J. 0. McKinney, Ed. (Ann Arbor, Mf! Ann Arbor Science Publishers, Inc., 1981), pp. 219*243. Hattori, Y. , Y. Kuge and M. Nakamoto. "The Correlation Be tween the Electron-Capture Oetector Response and the Chemical Itructure for Polychlorinated 9iohenyls." Bull Chem. Soc. Jpn. S4(9);2807-2810; Chem. Abstr. 96:34427s (1981). Hattula, M. L. "Some Aspects of the Recovery of Chlorinated Residues (OOT-Type Compounds and PC8) From Fish Tissue by Using Different Extraction Methods," Bull, Environ. Contam. Toxicol. 12(3):301-307 (1974a). Hattula, M. 1. "Simultaneous Clean Up of Fish Fat Containing low levels of Residues and Separation of PCB From Chlorinated Pesticides by Thin-layer Chromatography," Bull. Environ. Contam. Toxicol. 12(3):331-337 (1974b). Hattula, M. l. and 0. Karlog. "Adsorption of Polychlorinated Biphenyls (PCB) on Glass Surfaces," Pan, Tidsskr. Fane. 45(7): 259-261 (1971), HONS 223832 0i bhoQraotiy Heeg, F. J. , R. Zinburg, H. J. Neu and K. Ballschimter '`Re. tention Index Calculation Based on a Nonlinear Relation%no Between Net Retention Tine and Caroon Number of n*AUanes Chroma-tooraphia 12(7).451-458 (1979) ' Heesen. T. c. , and 0. R. Young. "Precision of CMonnateo Hydrocarbon Measurements,'' in Southern California Coastal Water Research Project Annual Report for the Year Enoeo June 30. 1977. p. 69-74 (1977) (NT1$ No. PB274 463/9C1). Heesen, T. C.. 0. R. Young, and 0. McOermott-Ehrlicn. "Eval uation of a Techniaue for Measuring Ory Atnosohenc Oeoosi- tion Rates of 00T and PCB Residues." Atmospheric Environment 13:1677* 1680 (1979). ' Heller, $ R, , j. m. McGuire and w. i. Budde. "Trace Qr- janics 0v GC.MS.' Environ. Sc*. rechnol 9(3).210-213 (Marcn 1975). Heller. S. R. and G. w. A. Milne. "1978 Indices to EPA/nih Mass Spectral Qata Bast," U.S. G.P.O., Washington. 0 C (1978). p. 25409. Henderson, J. E. and W. H. Glaze. "GC/MS Analysis of XA0-2 Extracts of Superchlorinated Septaoe." water Res. 16:211-219 (1982). Hernandez, A. and H. f. Walton, "liquid Chromatograohy of Chlorinated Biphtnylols," J. Chromatoqr. 242:346*348 (1982). Herzel, F. "Polychlorinated Biphenyls and Their Oiscrimina tion from Oroanochlorine Insecticides." Vom wasser 36:71-80 11971). Hesse 1 berg, R. J, and J. 1. Johnson. "Column Extraction of Pesticides from Fish, Fish Food and Mud," Bull. Environ. Con* tam. Tokico 1. 7`.U5-120 (1972). HlguChl, K. (Ed.). PC6 Poisoning and Pollution. (New York. NY* Academic Press. 1976). ---- Hllker, 0. R. , K. M. Aldous, R. M. Smith, P. W. O'Keefe and J. Jurusik. "Comparison of Methods for the Determination of PCOOs and PCOFs in Transformer Oil and Transformer Oil Soot." Presented at the American Society for Mass Spectrometry. Thirty-First Annual Conference on Mass Spectrometry and Allied Topics, Boston, MA, May 8*13, 1983. Hlngorani, N. G., "PCB Technical Report from EPRl, No. 9." EPR1 Technical Newsletter. Electrical Power Reserch Insti tute, Pal oAi to, California (Novemoer 28. 1984). HONS 22333 Bibliography 387 Hirota. K. , Y. Takata. Y. Arikawa, T. Yoshihara. H. Akrmori and S. Ganno. "Preparation and Application of Class Capil lary Columns." Bunsexi Ragaku 23(10);1194- 1201 ( 1974). Hirv, S. N. , R. E. Sorchard, 1. G. Hantan and R. L Hetcalf. "Gas-LiQuid Chromatography Hass Spectrometric Characterua* tion of Aroclor 1242 and 1254 Componants 8u 11 Environ. Contain, Toxicol. 12(2): 138-144 <1974). --------------------------- Hodgas, K. 1. , T. A. Robinson, C. J. Hentler, R. S. Raley, H. Caspars, F Eald and A. R. Pittaway. "Exposure Studies Relating to Industrial Processes Containing Incidental PCS," in Advances <n Exposure, Health and EnvironmentaI Effects Studies of PC8s. Symposium Proceedings* R" j" Oavenport and iT Bernard (Tbs) Office of Toxic Substances. U S. En vironmental Protection Agency, Washington, O.C., Report No. LSI-TR-507-1378. NTIS No. PB84-135771 (Oecemoer 1983). pp. 137-181. ' Hoeting, A. l. "EOA Regulation jr` C8 in Fooo.'' ;n PC8s: Human and Environmental Hazards, F. M. O'ltri and M. a. Ramrm, Eds. (Boston: Sutterworth Publishers. 1983), pp. 393-408. Hofstader, R. A., C. A. Bache and 0. J. lisk. "Interference in the Electron-Capture Technique for Determination of Poly chlorinated Biphenyls by Sulfur-Containing Compounds in Pe troleum Products," Bull. Environ. Contam. Toxicol. 11(2):136* 138 (1974). Holden, A. V. "The Analysis of Pish for Organochlorine Resi dues." International Symposium on Identification and Measure ment of Environmental Pollutants, Ottawa, Ontario, Canada (June 1971). Holden, A. v. "Internationa I Cooperative atuoy or Organo chlorine and Mercury Residues in Wildlife, 1969-71," Pestic. Honit. J. 7(1): 37-52 (1973). Holden, A. V. "Report on the Fourth ICES Organochlorine In tercalibration Exercise," International Council for the Ex ploration of the Sea. Copenhagen, Denmark, CM 1980/E: 40 (1980). Holden, A. V. and K. Marsden. "Single-Stage Clean-Up of Ani mal Tissue Extracts for Organochlorine Residue Analysis," Journal of Chromatography. 44:481-492 (1969). Holdrlnet, M. V. H. "Preliminary Results of an Interlabora tory PCB Check Sample Program," Environ, Qua!, Safety Suppl. 3 (Pesticides):51-56 (1975). HONS 223834 386 Bibliography Holdrinet. M, V M. "Confirmation of Mire* *nd cis- and trans*CMoroan in the Presence of Other Organochlorme In secticides and Polychlorinated 8iphenyl$," Bull. Environ Contam Toxicol 21 46-52 (1979). 1------ Hollod, C. J. and S. J. E'senreich. "Collection of Atmo spheric Polychlorinated Sipnenyls on Amberllte XA0*2 Resins Anal. Chim. Acta 124:31*38 (1981). ` Holmes. 0. C. and M. Wallen. "A Simple Differentiation of Polychlorobiphenyls from Chlorinated NaphthalenesJ Chromatoor. 71:562*563 (1972). Hopper. M. 1. and 0. 0. Hyghes. "An Improved CPC System for Pesticides m Fats." Laboratory Information Bulletin No 1958, FS8/EOPO, U.S. Food and Drug Administration, Kansas City, MO. p. 50*55 (July 1976). Horn. 3,, ... J. Hetling and 7. J. Tofflemire. 'The Pro* blem of PC8s in the Hudson River System," Ann. N, y Acad Sci. 320:591*609 (1979). Hornig, A., and H. Masters. "Destruction of PC8*Contaminated Soils with a High-Temperature Fluid-wall (HTFW) Reactor." Municipal Environmental Research taboratory-Cincinnati. OH. Office of Research and Development, EPA-600/0-84-072 1198*) Horwitz, w. "Evaluation of Analytical Methods Used for Regu* lation of Foods and Orugs," Anal. Chem. 54(1):67A*76A (1982) Horwitz, w. "Today's Chemical Realities," J. Assoc. Off Anal. Chem. 66(5):1295-1301 (1983). Horremoa. L. M and 0. M. Of Torse. "Extent of Reversibility or Polychlorinated 8ipheny\ Adsorption," Water Research 17: 851-859 (1983). Hubbard, H. l. "Chlorinated Biphenyl and Related Compounds," in Encvclooedi* of Chemical Technology, 2nd Ed. (Hew fork, NY: Kirk-Qthmer, Publishers - Wiley and Sons Interscience, 1864). Vol. 5 pp. 289-297. Muck ins, J. N. , J. E. Swanson and 0. 1. Stalling. "Perchlorination of Polychlorinated Biphenyls," J. Assoc. Off Anal. Chem, 57(2);416-417 (1974). Huekins, J. n. , 0. 1. Stalling and J. 1. Johnson. "Silicic Acid Chromatographic Separation of Polychlorinated Biphenyls and Pesticides: Some Contaminants and Limitations," J. Assoc. Off. Anal. Chem. 59(S):975-9B1 (1976). HONS 223635 Bibliography 389 Huckins. J. N. . 0. L. Stalling jng W. a. Smith. '`Foam* Charcoal Chromatograpny for Analysis of Polycnlonnated Qi- benzodionns in Herbicide Orange." J. Assoc. Off Anal Chem 61:32-33 ( 1970). ' Huckins, J N , 0. L. Stalling and J. 0. Petty. "Carbon-Foam Chromatographic Separation of Non-o,o'-Chlorine Substituted PC0S from Arodor Mixtures." j""^ssoc. Off Anal. Cheat. 63(4): 7SO-7SS (1980). ' Humphrey. H. 6. 8. "Population Studies of PCBs in Michigan Residents." in PC8s: Human and Environmental Hazards. F. M. O'ltri and M. A. Kamrm, ds. (Boston: 8utter*orth Pub lishers. 1983), pp. 299-310. Hunt. 0. f. , j. Schabanowitz. T. M. Harvey, and M. Coates. "Scheme for the Oirect Analysis of Organics in the Environ ment by Tandem Mass Spectrometry." Anal. Chetn. . S7:52S'$37 (1905). Hunt. G. r. , P. Wolf and P. F. Fnn#|ly. "Incineration of Polychlorinated Biphenyls in High-Efficiency Boilers: A vi able OiSDOsal Ootion." Environ. Sci. Technol. 18:171-179 (1904). Hunter, R. G. "Environmental Effects of Polychlorinated Bi phenyls. Important Ecological Aspects." in Advances in Ex posure . Health and Environmental Effects Studies of PCBs: Symposium Proceedings. JC, " Qavenport and 8. iC Sernard (Eds.), Office of Toxic Substances, U.S. Environmental Pro tection Agency, Washington, O.C.. Report No. ISI-TR-S07-1378, NT IS No. P884-135771 (Oecember 1983), pp. 265-291. Hutzinger. 0. (1983a). "PC8 Symposium," Chempsphere 12( 7/8): N39-N43 Hutzinger, 0. "Summary of Recent Advances in Exposure, Health and Environmental Effects Studies of PCBs." in Ad vances in Exposure. Health and Environmental Effects Studies of PCBs: Symposium Proceedings." R, J, 6avenport and 8. K. Bernard (Ed*.), Office to Toxic Substances, U.S. Environ mental Protection Agency, Washington, O.C., Report No. ISITR-507-U7B, NT1S No. PB04-135771 (Oecemoer 1983b). pb. 340 345. Hutzinger, 0., S. Safe, and V. Zitko, "Analysis of Chlori nated Aromatic Hydrocarbons by Exhaustive Chlorination: Qualitative and Structural Aspects of the PerchloroOerivatives of Biphenyl, Naphthalene, Terphenyl. Qibenzofuran, 0-benzodtoxin and 00E," Intern. J. Environ. Anal. Cham., 2. 95*106 (1972a). MONS 223836 390 Bibliography Hutzinger. 0.. S. Safe ana V. Z11ko. '`Photochemical Degrada tion of ChlorooiohenvI s (PC8s)," Environ Health persn#c 1(1): 1S-20 ( 1972b). ---------- - Hutzinger, 0. . w C. Jamieson. S. Safe and V. Zitko. haustive Chlorination as a Techmaue in the Analysis of Aro matic HydrocarbonsJ assoc. Off. ana). Chem. 56(4):982-qRr (1973). Hutzinger, 0 , S Safe, and V. Zitko. The Chemistry of PCB*\ (CRC Press: Cleveland. Ohio. 1974a) 269 pp. Hutzinger, 0.. S. Safe and V. Zitko. "Preparation, Gas Chro matographic Behavior, and Spectroscopic Properties of Hy- droiylated Chlorobiphenyl $ J. Assoc. 0ff. Anal. Chem 57(5): 1061-1067 ( 1974b). ---------- Hutzinger. 0. . R. A. Heacock and S. Safe. "'Thin-Layer Chromatograpnv jnd Colour factions of Some Hydroxy Iated Chlorobiphenyls.'' J. Chromatoqr. 97.233-247 ( 197cj. Hutzinger. 0. and A. A. M. Roof. "Polychlorinated 9ipneny)j and Related Halogenated Compounds." in Analytical Techniques in Environmental Chemistry. J. Albaiges.^d. (New York, NY* Fergamon Press, 1980a), pp. 167-184. Hutzinger, 0. and A. A. M. Roof. "Hydrocarbons and Halo genated Hydrocarbons in the Aquatic Environment: The Thoughts on the Philosophy and Practice of Environmental Analytical Chemistry.' Environ. Sci. Res. 16:9-20 (1980b). lida. Y. and T Kashiwagi. "Analysis of Polychlorinated 81phenyls by Gas Chromatography-Chemical Ionization Mass Spec trometry,'' Seikei Oaiqaku Koqakubu koqaku Hokpku 19:1461*1462 (1975). lida, Y. . S. Oaishine and T. kashiwagi. "Determination of Polycnloropiphenyls by Chemical Ionization Mass Spectrom etry," Bunseki kaqaku 32(2):80-86; Chem. Abstr. 98:154737f (1983). International Agency for Research on Cancer. "[ARC Mono graphs on the Evaluation of the Carcinogenic Risk of Chem icals to Humans--Po!ycn!orinated Biphenyls and Polybrominjted Biphenyls." Volume 12 (Lyon, Prance, 1978). pp. 43-103. International Joint Commission. "Great Lakes Water Quality Appendix E. Status Report on the Persistent Toxic Pollutants in the Lake Ontario Basin." IJC (1977). HONS 223837 Bibliography jgt lshi, 0. and r Tdkeucht "High-Performance L'duid Chro matography using Flexible Fjsed*$i l ica Micro-Packeo Columns M J. Chromatoqr 255:J58 (1983) I sun 11, R. J. and F L- 8onner. "New. Improved Thin Layer Chromatoqrapny for Polychlorinated Biphenyls, Toxaphene. and Cnlordane Components." J. Assoc. Off Anal. Chem 57CS1:10261032 (197*). lss*q, H. J. , J. Most, and G. M Muschik. "Separation of Polychlorinated Biphenyls (Aroclor 125*) by High Performance Liquid Chromatography," J, Chromatoor, 302; 159-165 (198*). IT Corporation. "Initial Report for Destruction of Poly chlorinated Biphenyls in a Mobile Incineration System at EPA Region (I Facility. Edison, NJ. Vol ume I," U.S. EnvironmentaI Protection Agency. Municipal Environmental Research Laboratory-Ci, Oil and Hazardous Material Spills Branch, Edison, NJ, September 18, 1981. 16 PP. IT Corporation. "Trial Burn Plan for the U.S. EnvironmentaI Protection Agency Nobile Incineration System at EPA Region II Facility. Edison. NJ." o*eoared for: U.S. Environmental Pro tection Agency. Municipal tnvironmentai Research LaooratoryCi. Oil and Hazardous Material Spills Branch, Edison, NJ, February 26, 1982a. 1*8 pp. IT Corporation. "USEPA Mobile Incineration System SPCC Plan," Prepared for U.S. Environmental Protection Agency, Municipal Environmental Reseircn Laboratory, Solid and Haz ardous Waste Research Oivision, Oil and Hazardous Material Spills Branch, Edison, NJ, July 16. 1962b. IT Corporation. "USEPA Mobile Incineration System, Phase II Interim Trial Burn Results." Prepared for: U.S. Environ mental Protection Agency, Municipal Environmental Research Laboratory, Solid and Hazardous Waste Researcn Division. Oil and Hazardous Materials Spills Branch. Edison, NJ, December 10. 1992c. -C rp. IT Corporation. "Mobile Incineration System Trial Burn Qual ity Assurance Project Plan EERU/QA-2," Prepared for: U.S. En vironmental Protection Agency. Municipal Environmental Re search Laboratory, Solid and Hazardous Waste Research Oivision, Oil and Hazardous Spills Branch. Edison, NJ. Otcember 30, 19S2d. Jacobson, S. w. , J. L. Jacobson, P. M. Schwartz and G. G. Fein. "Intrauterine Exposure of Human Newborns to PCBs; -Measures of Exposure." in PCBs: Human and Environmenta! Hazards, F. M. 0'ltri and M,, A. Kamrin, Eds. (Boston: Jut" terworth Publishers, 1963). PP- 311-344. MONS 223838 392 Slbiiograohy James, R. C. and R 0. Harbison. "Assessment of the Human Risks to PCBs Associated with the Expected Environmental lx. posures." in Advances in Exposure. Ha)th and nv1ronmtntji Effects Studies of PCBs: Symposium Proceedings. R. J. flavanT port and B. K. Bernard (Eds.). Office of Toxic Substances U.S. Environmental Protection Agency. Washington, O.C. Re port No. LSI-TR-507-1376. NTIS No. P884-135771 (Oecember 1983), pp. 300-336. Jennings, w. "Gas Chromatography with Glass Capillary Col umns." 2nd Edition (New York. NY: Academic Press, 1980) Jensen. S. Ambio 1:123 ( 1972). Jensen, $., A. G. Johnels, M. Olsson, and G. Qlterimd. 00T and PCS in Marine Animals from Swedish Waters." Nature 274 247-250 (1969). Jensen. $., i. Renperg and R. var. "Problems in the Quantif ication of PCB in Biological Material." Committee Proceeding PCS 2nd Conference. Wenner-Gren Center. 1972. 7*14 (1973) Jensen. S. and G. Sundstrom. "Structures and Levels of Most Chlorobiphenyls in Two Technical PCB Products and in Human Adipose Tissue." Amp ip 3(2):70*76 (1974). Jensen, $., L. Renberg and R. Vai. "Methods for Analysis of 00T and PC8 in Environmental Samples Using Chromatographic Methods." FA0 Fisheries Technical Paper, Rome. FIRI/T137 (1975). pp. 229-236. Jensen. $. , L. Renberg and L. Reutergardh. "Residue Analysis of Sediment and Sewage Sludge for Organochlorines in the Priance of Elemental Sulfur," Anal. Chem. 49(2) 216-212 (19771 Jiang, K. , Z. Kang and Y. Btan. "Quantitative Analysis of Polychlorinated Biphenyl Residues in Environmental Samples by GC-MS," Huanjing Kexue Xuebao 2(l):85-89; Chem, Abstr, 96: 194988d (1962a). Jiang, K., R. Chen, J. Wang, Z, Kang and Y. Sian. "Environ mental Analysis of Polychlorinated Biphenyls by Gas Chroma tography and Mass Spactroscopy * Use of Chinese Commercial Products as References," Fenxi Huaxue 10(12):711-715 (1962b); Cham. Abstr. 98:185022y (T55TT Jiang, K. . Z. Kang and Y. Sian. "Determination of Poly chlorinated Biphenyl Residues in tha Environment Dy GC-MS with Multiion Detection," Huanjing Heuxue 1(4); 274-280 (1982c); Chem. Abst. 96:29072j (1983). HONS 223639 Bibliography 393 Jiang, K. , l. Kang, and y. Bian. "Determination of Poly* chlorinated 8iphenyl Residues in the Environment by Quanti tative GC/MS Ane)ysis*-o,p'-00E Internal Standard Mthoa." Huanjing Huaue 3(3): 71-75 (1984); Cham. Abst 101:150579p (1984). Johnson. t. 0. and ft. G. Merrill, "Stack Sampling for 0rqanic Emissions. Toxicol. Environ, Chen. 6:109-126 (1983). Jones. J W and H $ Alden. "An Acneform Oermatergosis." Arch. Dermatol. Svphilol 33:1022-1034 (1936). ' Jung, J. 0. "A Review of Methods for PCS Analysis of Trans former Oil." Proc. Oectr./Electron. Inu). Conf 15th. 231 236 (1981); Chem. Abst. 9^ 163356 (1982). Junk, G. A and J. J. ganic Compounds." in Pollutants in Air, l. Pup)isners. 1984 ). pp. Richard. "Vapor-Phase Sampling of Or Identification and Analysts of Organic IT Keitn, cf (Boston: Butterwortn 61-78. Kafaaar. K. ana K. R. cbernarot. 'Statistical Analysis ot Some Gas Chromatography Measurements." J. Res Nat. Bur. Stand. 88(1): 37-46 ( 1983). Xelmez. E. V., R. 8. Craig and G. w. Zimmerman. "Kinetics Model and Simulation of Concentration Variations of Species of Polychlorinated diphenyls Involved in Photochemical Trans formation," Chapter 14 in Oetoxication of Hazardous waste. J. H. Exner, Ed. (Ann Arbor"! HTi Ann Arbor Science Pub lishers, Inc., 1982), pp. 233-240. Kaminsky, L. S. and M. J. Pasco. "High-Performance Liquid Chromatoqraphy of Polychlorinated 8ioheny1s," J. Chromatoar 155:363-370 ( 1978). Kaminsky. 9. snd 9. A Hites. "Analysis if Ccmoounas from Niagara Palls Oump Sites Using NCI GC/MS." Abstract from 30th Annual Conference on Mass Spectrometry and Allied Topics, American Society for Mass Spectrometry, June 6-11, 1982. Kemps, L. R., w. J. Trotter, S. J. Young, l. J. Carson, J. A. G. Roach, J. A. Sphon, J. T. Tanner and 8. McMahon. "Poly chlorinated Quaterphenyls Identified in Rice Oil Associated with Japanese 'Yusho' Poisoning," Suit. Environ. Contain, Toxicol. 20:589-591 (1978). MONS 223840 394 Bibliography Kemps. 1. R., W. J. Trotter. S. J. Young. A. C. Smith, J. A C. Roach and S W. Page. "Separation and Quantitation of 3.3'.4.4'-Tetrachlorobipheny1 and 3.3',4,4' ,5.5'-Hexachlo- rooiphenyl in Aroclors Using Flonsil Column Chromatography and Gas-liQuid Chromatography.* Bull. Environ. Contam. Tn*. iCQI 23; 51-56 ( 1979). "------- Kan. T. . K. K*mjta, T Ueta, R. Yamatoe and T Totam "Fluorescence Reactions or Organohalogen Compounds. i fluorometry or Polychlorinated Biphenyls (PCS) with Oiphenyiamme on Thin-Layer Chromatograms." Tokyo Toritsu Eisei Kenku usho Kenky Nempo 24 137* 145 ( 1973); Chemr'Abst" bu: iiS77u' (1974). Kapila. S and W. A. Aue. "Chemical Degradation of Single. Gas Chromatograpnic Peaks for Confirmation of Pesticide Resiaue Identity.' J. >romatoar Sci. i.5;559-B72 (1977) Karasek. F. W. "Plasma Chromatography of the Polychlorinated Biphenyls," Anal. Chem. 43(14):1982-1986 (1971). Karppanen, E. and L. Kolho. "The Concentration of PC8 in Hu man Blood and Adipose Tissue in Three Different Research Groups." PCS Conference II, 1972, Stockholm. Natl. Swedish Environ. Protection Board. Publication No. 1973:4E. 124-B (1973). Kashimoto, T. . H. Miyata. S. Kunita. T.-C. Tung, S.-T. Hsu. K. -J. Chang, S.-Y Tang. G. Ohi, J. Nakagawa and S -[. Yamamoto. "Role of Polychlorinated Oibenzofuran in Yusho (PCS Poisoning)," Archives of Environmental Health 36(6): 321-326 (1981a). Kashimoto. T. , h. Miyata and N. Kunita. "The Presence or Polychlorinated Quaterphenyls in the Tissues of Yusho vic tims," Food Cosmet. Toxicol. 19:335-340 (1981b). Kashimoto, T., H. Miyata. S. Fukushima, N. Kunita, T. C. Tung, S. T. Hsu, C. J. Chang, S. Y. Tang, G. Ohi and S. Yamamoto. "Chlorinated Compounds in Taiwanese 'Yusho' Patients' Stood," Abstract from 30th Annual Conference on Mass Spectromttry and Allied Topics, American Society for Mass Spectrometry. June 6*11. 1982. pp. 198-199. Kateman, G. and F. w. Pijpers (Eds.). Qua!ity Control <n Analytical Chemistry (John Wiley and Sons; wTTey- Interscience Publishers. 1981). HONS 223841 Bibliography 395 Kauss. P. 8.. K. Sun* and A. F. Johnson. Montiroing of^PCSs in Water. Sediments and Biota of the Great lakes - Some Re* cent Examples." Chaoter 20 in Physical Behavior of PC8s in The Great Lakes, D. Mackay. S. Paterson, S. J. Euenreicn and M. S. Simmons. Ed (Ann Arbor, Ml: Ann Arbor Science Pub lishers, Inc., 1983), pp. 385-409. Xawabata, J. "Simple Method for the Determination of PC8s [Polychlorinated Biphenyls] by a Combination of Thin-Layer Chromatography and UV Absorption,'* Koqai To Taisaku 10(10): 1112-1116 ( 1974); Chem, Abst. 83: 20165Tb' ( 1975). Kawaguchi. T. , $. Hiratsuka. T. Yoneshima and Y. Nagao. "A Method of Analysis for Polychlorobipheny) Gas Chromatograms Tokyo-Toritsu Koqyo Gijutsu Sent* Kenkvu Hokoku (1975); Chem. Abst. 86:e3287y (1977). 5:57-60 Keith. L. H. , W. Crummett, J. Oeegan Jr.. R. A. Libby. J K. Taylor and G. Wentler. "Principles of environmental Analy sis," Anal. Chem. 55:2210-2218 (1983). Kelso. G. L. , M. 0. Erickson, 8. A. Boomer. $ E. Swanson, D. C. Cox, and 8. 0. Schultz. "Cleanup of PCS Spills from Capacitors and Trans formers Oreft Interim Report No. 1. Work Assignment Task 37, EPA Contract No. 68-02-3938. U S- Environmental Protection Agency, Office of Toxic Substances. Washington, 0C (January 1985). Kennedy, P. A., 0- J. Roberts and M. Cooke. "Determination of Polychlorinated Naphthalenes in the Presence of Polychlor inated Biphenyls by Capillary Gas Chromatography." J. Chromatoqr. 249:257-265 (1982). Xerkhoff, M. A. T. A. 0e Vries, R. C. C. Wegman and A. w. M. Hofstee. "Analysis of PC8s in Sediments by Glass Caoillary Gas Chronatograohy," Chemosohere 11(2): 165-174 (1982). Khan, M. A. , A. F. Novak and R. M. Rao. "Comparative Evalua tion of Polychlorinated Biphenyl Solutions," 8uH Environ. Contam. Toxicol, 16(3): 360-367 ( 1976). Xilikidis, S. 0., J. E. Psomas, A. P. Kamarianos and A. G. Panetsot. "Monitoring of OOT, PCBs, and Other Organochlorine Compounds in Marine Organisms from the North Aegean Sea," Bull. Environ. Contam. Toxicol. 26:496-501 (1981). Kimbrough, R. 0. "The Toxicity of Polychlorinated Polycyclic Compounds and Related Chemicals." CRC Crit. Rev. Toxicol. 2: 445-498 (1974). HONS 223842 396 Bibliography Kimbrough. R. 0.. (Ed. ) Haloqenated Biphenyls, TerphenyU Naphthalenes, Qibenzoaioxirn ana Rt>ateq Croquets ^New raritf Elsevier/North-Hol Una BTomedTcTi Press, 1955*). 406 pp. Kimbrough, R. 0. "Environmental Pollution of Air. Water ang Soil," Chapter 3 in Haloqenated Biphenyls, Terphenyls. Naph thalenes, Qibenzodioxins and Related Products. ~ R. o' Kimbrough. Ed! (New York. NY: Elsevier/North-Holland 8io- medical Press. 1980b), pp. 77-80. Kimbrough. R. 0. "Occupational Exposure," Chapter 9 in Halogenated Biphenyls, Terpnenyis, Napththalenes, Oibenzodioxms and Related Compounds. R. D, Ktmbrouon. Ed. (New rorT. ny Elsevier/North-Holland Biomedical Press, 1980c), pp. 333*398. Kimbrough, R. , J. Buckley, l. Fishbein, 0. Flamm, t. Kasza, w. Marcus. S. Shibko and R. Teske. "Animal Toxicology," En viron. Health Pe-so. 24: 173-184 (1978). Kirchmer, C. J. "Quality Control in Water Analyses." En viron. Sci. Techno). 17(4):174A-181A (1983). Kirshen, N. A. "PCBs in Transformer Fluids," Varian Instrum. Appl, 15(2): 1-10; Cheei. Abst. 94(26):219095j (1981a). Kirshen. N. A. "PC8s in Transformer Fluids." Amor. Lab. 6S69 (December 1981b). Kitchens, J- F. , W, . Jones. Ill, G. 1. Anspach and 0. C. Schubert. "Light-Activated Reduction of Chemicals for De struction of Polychlorinated Biphenyls in Oil and Soil," Oetoxication of Hazardous Waste. J. H. Exnef. Ed. (Ann Arbor, mT! Ann Arbor Science Publishers, Inc., 1982), pp. 215-226. KUaisch, H. M. and 0. N. lngebrigtson. "Determination or Polychlorinated Biphenyls in Silicone Fluids." Anal. Chem. 52:1675-1678 (1980). Kloepftr, R. 0. "Preparation of Fish Tissue for Extractable Organics Analysis." Method No. EE01STR, US. Environmental Protaction Agency, Region VII, Kansas City, MO (October 19, 1983), 3 pp. Koch, R. "Circular Thin-Layer Chromatography as a Rapid Method for a Qualitative Detection of Organochiorine Com pounds." Acta Hydrochim. Hydrobiol 7(3):355-356 ( 1979); Chem. Abst^TT: 101674"(791$). Kodama, H. , N, Kawamura and H. Ota. "A Simple Method for the Determination of PC8 in Human Milk and 8lood Using an Im proved Essential Oil 0isti)latorNippon Eiseioaku 2asshi 31(6): 644-651 (1977), Chem. Abst. 87:96dS3a (1*777* HONS 223643 Bibliography 397 Kodama, H. and 0. Hideo. "Transfer of Polychlorinated 8i- pheny1 $ to Infants From Their Mothers," Arch. Environ .Health 35(2):95-100 (1980), " Koeniger, M. , P. Wallnoeer and G. Engelhardt. "Residue Oe- termination of Polychlorinated Biphenysi (PC8s) in the Pres ence of Chlorinated Hydrocaroon Pesticides in Eggs of Wild Birds." Nachrichtenbl. Otsch, Pflamenschutidienstes 17(9): 131-135 ( 197$); Chew. Abst. 64:gS5Bv (1376).---------------- Kohli, K. K. , P. w, Albro and J. 0. McKinney. "Radioisotope Oilution Assay (RI0A) for the Estimation of Polychlorinated Biphenyls (PC8s)." J. Anal. Toxicol. 3:125-128 (1979a). Kohli, P., w. Aloro and J. 0. McKinney. "Radioisotope Oilu tion Assay (RI0A) for the Estimation of Polychlorinated Bi phenyls (PCBs)," Environ. Health Perso. 33:347 (1979b). Kolbye. A. C.. Jr. "Regulatory Considerations Regarding limiting Human Exposures to PC8$," in PC8s: Human and En vironmental Hazards. C. M. 0`ltri and ^ V xamrm. ids. (Boston: Butterworth Publishers, 1983), pp. 77*90. Kondrat. R. w. and R. G. Cooks. "Oirect Analysis of Mixtures by Mass Spectrometry," Anal, Chen. 50(1):81A-92A (1978). Kovits, von E. "Gas-Chromatographische Charakterisierung Organischer Verftindungen. Teil 1: Retentionsindices Aliphatischer Halogenide, Alkohole, Aldehyde und Ketone," Helv. Chin. Acta 41:1915-1932 (1958). Kratochvil, 8., 0. Wallace and J. K. Taylor. "Sampling for Chemical Analysis," Anal. Cham. S6:113*-129* (1984). Kraul, I, and 0. Karlog. "Persistent Organochlorinated Com pounds in Human Organs Collected in Oenmark 1972-73," Acta afcsrmacoi ?9:39*48 (1975) Kreiss, K., M. M. Zack, R. 0. Kimbrough, l. 1. Needham, A. 1. Smrek and B. T. Jones. "Association of Blood Pressure and Polychlorinated Biphenyl levels," J. Amer. Med. Assoc. 245(24):2505-2509 (1981). Kmll, t. S. "Recent Advances in PCS Analysis," in Residue Reviews. F. A. Gunther and J. 0. Gunther (Eds.). 66. New York 0977T " -Krupcik, J., P. A. leclercq, A. Simova, P. Suchanek, M. Collak and J. Hrivnek. "Possibilities and limitations of Capillary Gas Chromatography and Mass Spectrometry in the Analysis of Polychlorinated Biphenyls," J. Chromatoqr. 119:217-283 (1976). MONS 223044 396 Bibliography Krupcik, J. . J- *rw. 0- Prusova. P. Suchanek and 2. Irv*nka "Analysis of Polychlorinated 8 i phny l s by High-Per*-.rmance liguid Chromatograpny and Capillary Cas-Uqutd Cr-'-.natography,'1 J, Chromatoqr 142:797*807 ( 1977). Krupcik. J.. P. A. leclercq. J. Garaj and A. Simova. Analy sis of Alkylated futures of Polychlorinated 0iphe*/ls by Capillary Gas Chromatography-Mass Spectrometry." J >roma- toqr. 191:207*220 ( 1980). ---------------- - Krupcik. J. . J. Hocak. A. Simova. J. Garaj and G. o. ochon "Optimization of Experimental Conditions for the Ana'/sis of Complex Mixtures bv Gas Chromatography.1* J. Chromate:* 23ft 1*12 (1982). Kuehl. 0. w. and E N. Leonard. "Isolation of x*-:piotic Chemicals from Tissue Samples by Gel Permeation C!":matography," Anal, Chew. S0(1):182*185 (1978). Kuehl. 0. W. , E. N. Leonard, K. J. Welch and G. Z veith "Identification of Hazardous Organic Chemicals in f m from the Ashtabula River, Ohio, and Wabash River, Indiana. J. Assoc. Off. Anal. Chew. 63(6):1238-1244 (1980a). Kuehl, 0. w., M. J. Whitaker and R. C. Oougherty. Micro methods for Toxic Residue Screening by Negative Chema:al Ion ization Mass SpectrometryAnal. Chem. 52:935*940 1980b). KuQe, Y. "Pollution Analysis and Examples of Meas.'ement," Kankyo Gijutsu 12( 10): 659-665 (1983); Chem. Abst* 100: >9161t (1984). Kuratsune. M. "An Abstract Results of Laboratory !*amina- tions of Patients with Yusho and of Animal Expe*nents," environ, weann rerspec. 1.123*136 ^ 1372). Kuratsune. M. "Yusho," Chapter 981 in Haloqenated S.nenyls, Terphenyls, Naphthalenes. Oibenzodioxins and Rejatec :roducts. R. 0. Kimbrough. Ed. (New York, NT: ElsevievNorthHoTTand Biomedical Press. 1980). pp. 287-302. Kuratsune. M. and Y. Kasuda. "Polychlorinated 8ip-jnyls in Non-Carbon Copy Paper," Env. Health Persp.. 1:61*62 (1972). Kuratsune, M. , T. Yoshimura. J. Matsuzaka and A. u-aguchi. "Epidemiologic Study on Yusho, A Poisoning Caused Inges tion of Riee Oil Contaminated with a Coneerical rand of Polychlorinatad Biphenyls," Environ. Health Perspec 1:119* 128 (1972). MOHS 223645 Bibliography . 399 Kuroki, H. n Y. Masuda. "Determination of Polychlorinated Oibenzofuran isomers Retained in Patients with Yujho " Cwemo- sphere 7(10):771^777 (1978) ----------- Kutz. F. w. and S. C. Strassman. "Residues of Polychlori nated Biphenyls m the General Population of the United States," in Proceedings of the National Conference on Poly- mental Protection Agency, Washington, O.C., EPA-560/6-75-004, NT IS No. P8 253 248 (March 1976), pp. 139-143. Kutz, F. W, , S. C. Strassman and J. F. Sperling. "Survey of Selected Organochlorine Pesticides in the General Population of the United States Fiscal Years 1970-1975." Ann. N. Y. Acad. Sci. 320:60-68 (1979). ------------------ Kveseth, N. J. and E. M. 0revik. "Column Chromatographic Method for Cleaning Up Extracts from Biological Material and Simultaneous Separation of PCBs and 00E." Bull. Environ. Contain. Toxicol. 21:213-218 (1979) laBrosse, J. and R. J. Anderegg. "Using the Mass Spectrom eter as a Chlorine-Selective Oetector," Abstract from 30th Annual Conference on Mass Spectrometry and Allied Topics, American Society for Mass Spectrometry, June 6-11, 1982. laitem, l. and P. Caspar. "A T.l.C. Procedure for Identifi cation of OOT and Its Metabolites in Presence of PCB," Bull. Environ. Contam. Toxicol. 19:264*265 (1978). Lam. N, K. , and H. Kopanica, "Determination of Trichlorobiphenyl by Adsorptive Stripping Voltammetry," Anal. Chim, Acta 161:315-324 (1984). Lamoarski, L. L. . T. J. Nestrick, and R. H. Stahl. "Deter mination of Pari-per-iri 1 lion Concentrations ur 2.J./.6Tetrachlorodibenzo-p-dioxin in Fish," Analytical Chemistry. 51(9): 1453-1458 (1979). Laaparski, l. L., and T. J. Nestrick, "Micro Chlorination Procedure for Synthesis of Higher Chlorinated Oibenzo-gdioxins from C,JC]-2.3,7,8- Tetrachlorodibenzo-p-dioxin," Anal. Chtm,. 54:402-406 (1982). Landrigan, P. J, "General Population Exposure to Environmen tal Concentrations of Halogenated Biphenyls," Chapter 9A in Halogenated Biphenyls. Terphenyls, Naphthalenes. Olbenzodioxlns and Related Products, ft. D. Kimbrough, Ed. (New York, NY: tlTevier/North-Holland Biomedical Press, 1980), pp. 267-286. MQNS 223846 400 Bibliography 1*0, R. C. , R. $. Thomas, and J l. Monkman. "Aoplication of Computerized Gas Chromatography-Mass Spectrometry to the Analysis of Polychlorinated Biphenyls." Oynamic Mass Snr- trom.. 4: 107-131 ( 1976). ---------------x--- Lawrence, J. F. "Confirmatory Tests," Chapter 10 in Pesti- ciqe Analysis. K, G. Oas. Ed. (New York, NY: Marcel Oekker Inc. , 1961), pp 425-460. ' Lawrence, J. , and H. M. Tosine, "Adsorption of Polychlori nated Biphenyls from Aqueous Solutions and Sewage." Environ Scl. Techno 1, . 10(4): 361-383 ( 1976). --------------" Lawrence. J. F. and 0. Turton, "High-Performance Liquid Chro- matoqraphic Data for 166 Pesticides." J Chromatoor isr 207-266 (1978). Lea. Robert E., R. Bramston-Cook and J. Tschida. "Pattern Recognition 'or Identification and Quantitation of Comole* Mixtures in Chromatography," Anal. Chem. SSratS-o*? (.333) Lech, J. J. and R. E. Peterson. "Biotransformation and Per sistence of Polychlorinated Biphenyls (PCBs) in Fish," in PCBs: Human and Environmental Hazards. F. M. O'ltri ana M. A. Aamrin. Eds. (Boston: ButUrworth Publishars, 1983) pp. 187-202. L'ederman, T. C. and G-Y. Rhee. "Bioconcentration of a Hexachlorobiphenyl in Great Lakes Planktonic Algae," Canadian j of Fisheries and Aquatic Sci. 39:380-387 (1982). Lee, H. B. and A. $, Y, Chau. "National Intar laboratory Quality Control Study No. 25. PC8s in Wet Sediments," Rep. Ser. - Inland Waters 01r. (Can.) Report Series No. 71:12 pp. (l?8ia); Them. ibst. 97~~?22S36d fl982) Lee, H. 8. and A. S. Y. Chau. "National Interlaboratory Quality Control Study No. 27. PCBs in Naturally Contaminated Ory Sediments," Rep, Ser, - Inland Waters Qir. (Can.) Report Series No. 72, ISpp. (1981b): Chem. Abst. 97:22263 ( 1982). leiP, A. J., and 0. 0. Bills, "Influenca of Storage Tempera ture of Florist) on Analysis of Polychlorinated Biphenyls." Bull. Environ. Contam. Toxicol.. 12(3):328-330 (1974). leifer. A., R. H. 8rink, G. C. Thom, and K. G. Partymilier. "Environmental Transport and Transformation of Polychlori nated diphenyls," U.S. Environmental Protection Agency, Office of Pesticides and Toxic Substances, Washington, D.C.. EPA-560/S-83-025. NTIS No. P884-142579 (1983). MQNS 22364? 8ibtiography 401 Ltntztn, 0. E. . 0. E. Wagoner, . 0. Estes and w. F. Gutknecnt. "IERL-RTP Procedures Manual: level 1 Environ mental Assessment (Second Edition)," Prepared for US. En vironmental Protection Agency, Office of Reseercn and Devel opment. EPA-600/7-70-201, October 1970. leoni, V., "The Separation of Fifty Pesticides and Related Compounds and Polychiorobiphenyis into Four Croups by Silica Gel Microcolumn Chromatooraohy." J. Chromatoor. . 62:63*71 (1971). ----------------------*" Leoni. v., E. o'AI lesiandro de luce and A. m. Simeone. "Techniques of Qualitative and Quantitative Analysis of Poly chlorinated Biphenyls in Food Products and Packing Materi als." Rass. Chim. 25(2):99-111 (1973); Chem. Abst. 79:77061j (1973). --------------------- leoni, V., M. Biocca and E. d'A1lessandro de Luca. "I Poli* clorodifenili Nei Tessuti Adiposi liman i: Accertamento Sperimentale E Possible Sionificato laienico." II farmeco 31(2): 57*79 (1976a). leoni, V., G. Puccetti, R. J. Colombo and A. M. d'Ovidio "The use of Tenax for the Extraction of Pesticides and Poly chlorinated Biphenyls from Water. II. Tests with Artifi cially Polluted and Natural Waters." J. Chromatoor. 125: 399*407 (1976b). leoni, V. and C. Vannueehi. "Analytical Methods for water. 6. Determination of Polychlorinated Biphenyls and Polychlor inated Terphenyls in Wastewater." Quad. - 1st. Ric. Acoue 11: 41 pp. (1981); Chem. Abst. 97:115203T7T552TT lermen, S. I. and J. P. Hendricks. "Determination of Poly chlorinated Biphenyls in Transformer Oil." Chromatoor. Newsl. 9(l):5-6 (1961); Chem, Abst, 95(7):55674r (lMl). lerman, S. 1. , H. Gordon and J. P. Hendricks. "A Study in laboratory Automation - Analysis of PCBs in Transformer Otis." Amor, lab. 14(2):176*181 (February 1982). Levine. $. P., M. T. Homsher and J. A. Sullivan. "Comparison of Methods of Analysis of Polychlorinated Biphenyls in Oils," J. Chromatoor. 257:255-266 (1983). levins. P. 1.. C. E. Rechsteiner and J. 1. Stauffer. "Mea surement of PCS Emissions from Combustion Sources." U.S. En vironmental Protection Agency. Report No. EPA-600/7-79-047 (February 1979), MONS 223848 402 Bibliography Levins, P. L., C. E. Rechsteiner, Jr. and J. 1. Stauffer. "A New Procedure for the Meesurement of Polychlorinated 8i* phenyls (PCBs) in Combustion Sources," AIChE Svm. Seni 76(196):33Q-337 (1980), ----------------- .Levy, G. C. and J. M. Hewitt. "Analysis of Polychlorinated Biphenyls by Carbon-13 Nuclear Magnetic Resonance Spectros* copy," J. Assoc. Offic. Anel. Chem. 60(1);241^242 (1977). Lewis, . and w. 0. Jamieson. "Use of Negative Chemical Ion ization GC/MS to Study Polychlorinated Biphenyls in Marine Sediments," Int. J. Mass Soectrom. Ion Physics 48:301-306 (1903). --------------------------- --------- Lewis, R. G. "Procedures for Sampling and Analysis of Poly chlorinated Biohenyls in the Vicinities of Hazardous Waste Disposal Sites." U. S. Environmental Protection Agency. Research Triangle Park, North* Carolina, Marcn 16, 19B2, 14 PP- Lewis, R. G. , A. R. Brown and M. 0. Jackson. "Evaluation of Polyurethane Foam for Sampling of Pesticides, Polychlorinated Biphenyls end Polychlorinated Naphthalenes in Ambient Air,'* Ana). Chem. 49(12):1688-1672 (1977a). Lewis, R. G.. A. R. Brown and M. 0. Jackson. "Sampling for Low Levels of Airborne Pesticides, Polychlorinated Biohenyls. and Polychlorinated NaphthalenesPaper No. 78, 173rd Na tional Meeting, American Chemical Society, New Orleans, Louisiana (1977b). Lewis, R. G. and M. 0- Jackson. "Modification and Evaluation of a High-Volume Air Sampler for Pesticides and Semivolatile Industrial Organic Chemicals," Anal. Chem. 54:592-594 (1982). Lewis, R. G. and K. 6. MacLeod. "Portable Sampler for Pesti cides and Semivolatile Industrial Organic Chemicals in Air," Ana), Chem. 54:310-315 (1902). Liberti, A., 0. Brocco, V. Oi Palo end M. Possanzini. "Eval uation of Qrganochlorine Compounds in the Emissions of Urban Incinerators," in Analytical Techniques in Environmental Chemistry. J. Albaiges* Ed. (New York, NY: Pergamon Press, 1980),pp. 157-166. Liddle, J. A. "Method Standardization and Interlaboratory Compatibility of Serum Polychlorinated Biphenyl Analysis," Abstract, 184th Annual Chemical Society National Meeting, September 12-17, 1982. HOMS 2230*9 Bibliography 403 Lincer, J. L. "Polychlorinated Biphenyls: Their Potential Interference with Pesticide Residue Analysis end Present An alytical Status," Proqr, Anal, Chew. 5:109-131 (1973). liu, R. H., S. Ranesn and J. r. Liu. "Qualitative and Quan titative (Determinations of Aroclor Formulations," Abstract from the Thirty-First Annual Conference on Mass Spectrometry and Allied Topics, American Society for Mass Spectrometry, May 8-13. pp. 213 (1983). Liu, R. H. , S. Ranesh, J. Y. Liu, and S. Kim. 'Qualitative and Quantitative Analyses of Commercial Polychlorinated Bi phenyl Formulation Mixtures by Single Ion Monitoring GasLiquid Chromatography/Mass Spectrometry and Multiple Regres sion." Anal, Chem. H: 1808-1812 (19B4). Long, G. L. and J. D. Winefordner. "Limit of Detection - A Closer Look at the lUPAC Definition," Anal. Chem. $S(7): 712A-724A (1983). Longanbach, J. R. and W. H. Mink. "Development of a Process 'or PCB Removal from Triaryl Phosonate Hyoraul-.c :'iuids by Vacuum Distillation," Environ. Sci. Techno). 17(5):305-307 (19B3). Longbottom, J. E. and J. J, Lichtenberg, Eds. "Methods for Organic Chemical Analysis of Municipal and Industrial Waste water." U. S. Environmental Protection Agency, Report No. EPA-800/4-82-057 (July 1982). Lovell, R, J. , ft. A. Mfller, C. Pfommer, Jr., J. E. Brugger, and J. J. Yexzi, Jr, "Trial Burn Testing of the EPA-ORO Mo bile Incineration System/' Enviroscienee, Inc., Knoxville, TN, EPA-600/0*84*054, NTIS No. P884-17SS20 (1984. Lovett, A, M., $. Nacson, N, H. Hijazi, and ft. Chan. "Real Time Ambient Air Measurements for Toxic Cnemical." in Procteair.qs: A Specialty Conference on: Measurement and Mon itoring of Non-Criteria (Toxic) Contaminants in Air. E^ ft. Frederick, id., the Air Pollution Control Association, Pittsburgh, PA (1983), pp, 113*125. Incas, ft, M., M. 0, Erickson, P. V. Plserchia and S. R. Williams, "PC8 Residue Levels in Human Adipose Tissue, A Stetistical Evaluation by Racial Grouping," Office of Toxic Substances, U.S. Environmental Protection Agency, Washington, 0:C., EPA-6S0/13-79-01S (November 1980). MONS 223850 <04 Bibliography Lucas. R. M. . V. G. lannacchione and K. 0. Melroy. "Poly chlorinated Biphenyls in Human Adipose Tissue and Mother's Milk," Office of To*ic Substances. US. EnvironmentaI Pro tection Agency. Washington, D.C., EPA-560/5-83-011 NT IS no P883-25J179 (1982). luckas. 8. , h. Pscheidl and 0. Haberland. "Determination of Chlorinated Pesticides and Polychlorinated Biphenyls by Oe- nvatuation Gas ChromatoqraphvJ. Chromatoar. 147 41-Af, (1978). --------------------- Lunde. G. and E. 8. Ofstad. "Determination of Fat-Soluble Chlorinatad Compounds in Pish," Z. Anal. Chem. 282,3Q5*199 (1976). Luster, M. 1., P. w. Albro. G. Clark, K. Chae. S. x Chaudhary, l. 0. Lawson, J. T. Corbett and J. 0. McKinney. 'Proauction ana Characterization of Antisera Soeofic for Chlorinated Biphenyl Species: Initiation of a Saco immuno assay for Aroclors," Toxicol. Appl. Pharmacol. 50:147-15^ (1979). Luster, M. 1., P. w. Albro, K. Chae, S. K. Chaudhary and J. 0. McKinney "Development of Radioimmunoassays for Chlori nated Aromatic Hydrocarbons," Chapter 14 in Environmental Health Chemistry, The Chemistry of Environmental'Agents as Potential Human Hazards. X O. McKinney Ed. fAnn Arbor, MI: Ann Arbor Science Publishers, Inc., 1981), pp. 279*297. MacOougall, 0. et a). "Guidelines for Data Acquisition and Data Quality Evaluation in Environmental Chemistry," Anal Chem. 52:2242-2249 (1980). Macxay, u. c-i* - renmenta i 3t*iways if elych1orinated Bi- phenyIs," in Comments and Studies on the Use of Polycnori* nated Biphenyls in Response to an Order o7 the United States Court of Appeals for the district of Columbia CircuiT, voT fV. Submitted by The Utility Solid waste Activities Group. The Edison Electric Institute and The National Rural Electric Cooperetive Association to The U. S. Environmental Protection Agency, February 12, 1982a, 61 pp. Mackay, 0. "Correlation of Sioconcentration Factors," Environ. Sci. Techno). 16(5):274*278 (1982b). Mackay, 0., R. Mascarenhes, w. v. $hiu, S. C. Valvam, and S. H. Yelkowsky. "Aqueous Solubility of Po lychlorinated Bi* phenyls," Chemosphere 9.257*264 (1980). Mackay, D. , A. 8obra. D. w. Chan, and W. r. Shiu. `vaoor Pressure Correlations for Low-volatility Environmental Che** icals," Environ. Sci. Technpt. 16:645*649 (1982). HONS 223851 Bibliography 405 Mackay, 0. and S. Paterson. "Fugacity Mode-s of Indoor Expo sure to volatile Chemicals," Chemosohere 12(21 14V164 (1983). Hackay, 0., S. Paterson, $ J. Eisenreich, and M. S Simmons. Physical Behavior of PC8s in the Great takes. Ann Arbor Sci ence. Ann Arbor, HI, (1983a), 442 pp. Hackay, 0., w. Y Shiu, J. Billington and G. t. Huang. "Physical Chemical Prooerties of Polychlorinated Biphenyls," Chapter 4 in Physical Behavior of PCBs in the Great lakes. 0. Mackay, S. Paterson, S. J. Eisenreich and M. S. S immons\_Eds. (Ann Arbor, HI: Ann Arbor Science Publishers, Inc.. 1983b), pp 59-69. Hackay, 0., and A. 1. Hughes. "Three-Parameter Eauation De scribing the Uotake of Organic Compounds by Fish." Environ. Sci. Techno 1. 10(6):439-444 (1984). " MacLeod, K. E "Sources of Emissions of Polychlorinated Bi phenyls into the Amoient Atmosphere and Indoor Air," U-S. En vironmental Protection Agency, Reoort Ho. EPA-600/4-79-022 (Marcn 1979). MacNeil, J. 0., S. Safe and 0, Hutzinger, "The Ultraviolet Absorption Spectra of Some Chorinated Biphenyls.'* Bui 1. Environ. Contain. Toxicol. 1S( 1); 66-77 (1976). Manri, T. , Y. Shinbori, S. Murakawa and Y. Mochizuki. "De termination of Chlorobiphanyl in Rat Adipose Tissues by Neu tron Activation Analysis." Radioisotopes 20(B):371-375 (1971); Chem. Abst. 76:11738s (1072). Marchand, M., 0. Vas, and . K. Duursma. "Levels of PCBs and DOTs in Mussels from the N.W. Mediterranean." Marine Pollut. Bull. 7(4):65'69 (1976). M4rgeson, J. H. "Methoooiogy -or Measurement of Poiycntorinated Biphenyls in Ambient Air and Stationary Sources - A Re view," U.S, Environmental Protection Agency, Report No. EPA600/4-77-021 (April 1977). Marfcovec, l. N. , and R. J. Magee. "Identification of Major Perphloroaromatlc Compounds in waste Products from the Pro duction of Carbon Tetrachloride and Tetrachloroethylene," Analyst. 109(4):497-501 (1984). MarteUi, G. P. M. G. Caste! li and R. Fane 11 i. "Analytical Response of Single Polychlorinated Biphenyls Analysed by Se lected Ion Monitoring." Biomed. Mass Scectrom. 8(8),347-350 (1981). HONS 223852 406 Bibliography Mason, B. J. "Preparation of Soil Sampling Protocol: Tech niques and Strategies." ETHURA, McLean, Virginia, under sub contract to Environmental Research. Center, university of Nevada. Cooperative Agreement No. CR808529-01-2. for US. En vironmental Protection Agency, Las Vegas (October 1982). Mass Spectrometry Oata Centre, in collaboration with 1CI Ltd. Eiqht Peak Index of Mass Spectra. 2nd ed. , Vol. 1*3. AWRE, AldermastonT Reading RG 7/4PR, united Kingdom (1970). Masuda, y. and H. Shiokawa. "Experimental Pile. 42. Chro matography. Three Experiments," Kaqaku No Jikken 23(7) .669 671 (1972); Chem. Abst. 77:87143k (197?) Masuda, h. Kuroki, T. Yamaryo, K. Haraguchi , M. Kuratsune ina S. T. Hsu. "Comoanson of Causa) Agents in Tjiwan Pukuoka PCB Poisonings," Chemosphere 11(2).199-206 (1982). Masuda, Y., KH. Kuroki. and J. Nagayama. "Polychlorinated Oibenzofurans in the Tissues of Patients with Yusho and Their Enzyme-Inducing Activities on Aryl Hydrocarbon Hydroxylase," Chlorinated Dioxins Oibenzofurans Total Environ, (1963): Chew. Abst, 10fl:152fclp (13841, 375-384 Masui, T. , M. Yamamoto and S. Kimura. "Problems in Poly chlorinated Biphenyl Analysis," Shizuoka-ken Ejsei Kenkyusho Hokoku 19:59-64 (1976); Chem, Abst. 90:109442e (1979). Masumoto, H. T. "Study of the Silicic Acid Procedure of Armour and Burke for the Separation of Polychlorinated Bi phenyls from ODT and Its Analogs," J. Assoc. Qffic. Anal. Chem, 3S(5).iG92'il00 ( 1972). Masumoto, H. T. "Total Polychlorinated Biphenyl Quantitation bv Reduction." EORO SARAP Res. Tech. Rep. l:Paper 20-73, 30 pp. (1976); Chem, Abst. 66:73094k (1976). Mathar, W. , and H. Beck. "Simple Use of Fat-Containing Foods for the Determination of PCB Residues by Oistillation with Steam," Lebensmittelchem. Gerichtl. Chem., 37(6):147*148 (1983); Chem. Abst. ~l00:173236t (1984)~ Matthews, H. 8. "Metabolism of PCBs in Mammals: Routes of Entry, Storage, and Excretion," in PCBs: Human and Environ mental Hazards. F, M. 0'ltri and M. A. Kamrm, Eds. (Boston: Butterworth Publishers, 1983), pp. 203-214. Matthews, stein. y. icity of (1978). H. , G. Fries, A. Gardner, l. Garthoff, J. Gold Ku and J, Moore "Metabolism and Biochemical Tox PCBs and P66s," Env. Health Persp, 24:147-155 MOMS 223653 Bibliography 407 Matthews. h. 8. and S. Kato. "The Metabolism and Disposition of HaloQnated Aromatics." Ann. h y Acad. Sci. 320-131- 137 ( 1979). ' ' ------- Hattsson, P . and S. Nygren 'las Chromatographic Deter mination of Poiycn lorinated Biphenyls and Some Chlorinated Pesticides in Sewage Sludge Using i Glass Capillary Column " J. Chromatodr 124265-275 (1976) McCallum, R. 1. "Order Dismissing Interlocutory Appeal," Before the Admi m strator U.S. Environmental Protection Agency, Washington, DC. In the Hatter of: The Oow Chemical Company, Appellant. Docket No. 7SCA (16(a))-l, July 28 1982. McClure, V. i. "Transport of Heavy Chlorinated Hydrocarbons in the Atmosphere." Environ. Sc * Technol. 10(131:1223-1229 (1976). McConnell, E. E. "Acute and Chronic Toxicity, Carcinogenesis, Reproduction, Teratogenesis and Mutagenesis in Animals,1' Chapter 5 in Haloqenated Biphenyls, Terphenyls, Naphthalenes. QiQentcoioxins jno ^elateo ^rooucts. ~ V. J. kimorougn. Ed. (New York, nv": E1sevier/North-Ho!land Biomedical Press, 1980). pp. 109-1S0. McConnell, E. E-. J. R. Hass, N. Altman, J. A. Moore. "A spontaneous Outbreak of Polychlorinated Biphenyl (PCS) Tox icity in Rhesus Monkeys (Macaca Mulatta): Toxtcopathology Lab. Anim, Sci. 29(5):666-673 (1979). McCracken, W. E. "Edible Tissue Sampling for Pish Contami nant Analysis." in PCSs; Human and Environmental Hazards. F. M. O'ltri and M. A* Kamrin, Eds. (Boston: Butterworth Pub* Ushers, 1983). pp. 123-140. Mclnnes, R. G. "Technical Assistance in Support of Permit ting Activities for the Thermal Destruction of PC8s." USEPA, vffiue ui xesearcn ano ueveiopment, iERl, Research Triangle Park, NC, EPA 600/2-81-240 (NTIS No. PB62 231 32S), 70 pp. (1982). Mclnnvs, R. G. and R. J. Johnson. "Provision of Technical Assistance to Support Regional Office Implementation of the PCS Rtgulations'-East and west." Oraft Project Summary Report by GCA Corporation, New Bedford, MA. and TRW, Inc., Redondo Beach, CA, on EPA Contract No. 68-02-3168, Work Assignment No. 45. and Contract No. 68-02-3174. Work Assignment No. 68, for Oavid C. Sanchez, USEPA. Office of Research and Develop ment. 1 ERL, Research Triangle Park. NC, 186 pp. (1982). HONS 223654 406 Bibliography McKinney. J. 0 . K Chae. B. N. Gupta. J. A. Moore, and J A Goldstein. "Toxicological Assessment of Htxacnlorooipnenyl Isomers and 2,3,7.8*Tetracnlorodibenrofuran in Chicks. 1 Relationship of Chemical Parameters." To*. and Aool Pharma . 36;65-BO ( 1976) -------------------"------------------- McKinney. J. D. "Environmental Health Chemistry-Oef ini lions and Interrelationships: A Case in Point," Chapter 1 in En vironmental Health Chemistry. The Chemistry of Environmental Agents as Potential Human Health Hazards. J. 0. McKinney. Ed. (Ann Aroor. Ml": Ann Arbor Science Publishers, Inc.. 1981). pp. 3-15. McKinney. J. 0., 1. Moore. A. Prokopetz and 0. B. Walters"Validated Extraction and Cleanup Procedures for Polychlori nated Biphenyls and DDE in Human Body fluids and Infant for mula," J. Assoc- Off. Anal. Chem. 67( 1):122-129 ( 1984 ) HcKone, H. T. ano A. OauO. 'A Rapid ana Efficient C'eanuO Technique for the Quantitative Determination of Polychlori nated Biphenyls in fish," Chromatoqr, Mass Spectrpm, Biomeo. SC.K 2.497-503 (1983). ~ McLafferty, F. W. Interpretation of Hass Spectra, 3rd Edi tion, (Mil) valley, CA; University Science Books. 1980) Mclafferty, F. W. , R. Knutti, R. Venkataraghavan, P. J. Arpino and 8. G. Dawkins. "Continuous Mass Spectrometnc Monitoring of a Liquid Chromatograph with Subnanogram Sensi tivity Usino an On-Line Computer." Anal. Chem. 47(9):15031505 (1975). McLeod. H. A. and P. J. Wales. "A Low Temperature Cleanup Procedure for Pesticides snd Their Metabolites ;n Biological samples." J. Aqr. Food Chem. 2Q(3):624-627 (1972). McMahon B. and J. A. Burke. "Analytical Behavior Data for Chemicals Determined Using AOAC Multiresidue Methodology for Pesticide Residues in Foods," J. Assoc. Off. Anal. Chem,. 81(3):640-652 (1978). McMurtrey, K. D., N. J. Wildman and H. Tai. "Pyrolysis Gas Chromatography*Mass Spectrometry of Polychlorinated Biphenyls on Sediment." Bull. Environ. Conta*. Toxicol. 31(6):734-737 (1983). McNair, H. M. and E. J. Bonelli. Basic Gas Chromatography. Sth Edition. (Walnut Creek. CA, Varian Aerograph, March 1969. ) HONS 2238$$ Bibliography 409 McQuade, J. *. 'PCB Analysis by X-Ray Fluorescence," in Pro codings: 1981 PCS Seminar. G. Addis and J. Marks, Eds. .""le7 port No. EPRI:EL-2572" (PaloAlto. CA: Electric Power Re search Institute, 1982), pp. 2-9. ~ Menzie, C. Oeoartment Washington, 212 (1978). "Metabolism of Pesticides - uodate II," u. S. of Interior, Fish and Wildlife Service, 0 C. Special Scientific Report - wildlife No Menjie, C. M. "Metabolism of Pesticides update III," US. Department of the Interior, Fish and Wildlife Service, Washington, O.C.. Special Scientific Report--wiId!ife 232, NTIS No. P883-17S349 (1980). Mes, J. and 0. S. Campbell, "Extraction Efficiency of Poly chlorinated Biphenyl. Organochlorme Pesticides, and Phthalate Esters from Human Adipose Tissue." Bull. Environ. Contam. Toxicol. 16(1);S3*60 (1976). Mes, J. , 0. S. Campbell, R. N. "Robinson and 0. J. A. Oavies. "Polychlorinated 8iohenyl and Organochlorme Pesticide Res cues in Adipose Tissue of Canadians," Bull, environ. Contain Toxicol. 17(2):196-203 (1977). Mes, J. and 0 J. Oavies. "Variation in the Polychlorinated Biphenyl and Organochlorine Pesticide Residues Curing Human Breastfeeding and Its Oiurnal Pattern," Cnemosphere 7(9): 699-706 (1978). Mes, J. and 0. J. Oavies. "Presence of Polychlorinated Bi phenyl and Organochlorine Pesticide Residues and the Absence of Polychlorinated Terphenyls in Canadian Human Milk Sam* pies," Bull. Environ. Contam. Toxicol. 21:381-387 (1979). Mes, J. , 0. Oavies and J. Truelove. "The Determination of Polychlorinated Biphenyl in Small Samples of Monkey Milk and Tissues- I..M Intern. ). Erv<*on. nal '>*. :39*?5 (1980). Mes, J. and P. V. Lau. "Distribution of Polychlorinated 8i* phenyl Congeners in Human Milk and Blood During Lactation," Bull. Environ. Contam. Toxicol. 31(6):639-643 (1983). Mes, J., J. A. Ooyle, 8. R. Adams, 0. J. Oavies, and 0. Turton. "Polychlorinated Biphenyls and Organochlorine Pesticides in Milk and Blood of Canadian Women Ourmg Lacta tion," Arch. Environ, Contam. Toxicol. 13(2):217-223 (1984): Chem. Abst. 100;T52123r (1984). MOHS 223*56 410 Bibliography Messier, F M-f. Levesque ana R. Masse. "Metaooitsm of 4-Chlorooiph#ny] by tne Acnromooacter Strain 8*218 and Bacillus Srevts Strain 0-257." Abstract fro* The Thirty-First Annual Conference on Mass Spectrometry ana Allied Topics. American Society for Mass Spectrometry, May 8-13 la3 p. 225. ' "' Mestres. R . C Chevallier and M Pagnon. "Mass Sptctrometric Confirmation of tne Identity and Content of Pesticide and Chlorinated Biphenyl Residues in the Sediments of the Mediterranean Sea," Tray. Soc. Pharm. Montpellier 36(2) 151 160 (1976). Chew. AftstT~85:73422d (1976). Mestres, ft. and C. Chevallier. "XXXII. Method of Research and Determination of PC8 and Phthalate Pesticide Residues m Water," Ann. Fa Is i f Expert. Chi*. 70( 750):101- 11 1 ( 1977 ) Che*. Abst.~87: 79446c ( 1977 ). Mestres. R. , C. ChevaiHer. J. Espinoza ano fi. Cornet. Ap plication of Coupled Cas ChromatograpnyMass Spectrometry m Methods for tne Study and Determination of Pesticide Residues and Organic Micropollutants in Environmental and Food Materi als," Ann, falsif. Expert. CM*. 70(751): 177-188 ( 1977), Chem. Abst. 87:63535v (1977). Metcalf, ft. 1. "Screening Compounds for Early Warnings About Environmental Pollution," in Trace Substances in Environ mental Health - VIII, 0. 0. Hemoh?11 (d.), Proceedings of Unrversity of Missouri's 8th Annual Conference on Trace Sub stances in Environmental Health," Columbia, Missouri. June 11-13, 1974. pp. 213*217. Meuser, J. M, and w. C. Weimer. "Amine-Enhanced Photodegra dation of polvchlorinated B^renyU." `'or*.-- west Labs, Richland, WA, Report No. EPRI-CS-2S13 (NMS No. OE02 021378), 57 pp. (July 1982). Middleditch, 8. S., S. R. Missler and H. 8. Hines. Mass Spectrometry of Priority Pollutants. Plenum Press, n#w ror* (1981). Mieure, J. P., 0. Hicks. R. G. Kaley and v. w. Saeger. "Characterization of Polychlorinated Biphenyls," in National Conference on Polychlorinated Biphenyls (November 19-21, 197^. Chicago, Illinois). F. A. Ayer (Ed.). prepared for U.S. Environmental Protection Agency, Report No. EPA-560/6-75-004; NTIS No. PB2S3 248 (March 1976). Mlki, T. "PCBs (Polychlorinated Biphenyls] and Organochio- rine Pesticide Residues in Sugars," Seito Gijutsu Kenkvukaishi 25: 32-38 (1975); Chew. Abst. 83;14945ft (19^5) HONS 223857 Bibliography 411 Millar, J. 0. . R E Thomas and H. J. Schattenberg, III. 'Determination of Organocnlorme Pesticides and Polychlori nated Sionenyis m water by Gas Chromatography " Anal Chem 53.214-219(1981). -------------------- ' Millar, J. 0., 9. E. Thomas and 0. E. Johnson. "Oetermina- tion of Pesticides ana PC8$ in Industrial and Municipal wastewaters." U.S. Environmenta 1 Protection Agency, Contract No. 68*03*2606. Report No EPA-600/4-82-023 (NTlS No. P882 214222) (March 1982). Millar, J. 0., R E. Thomas, and H. J. Schattenberg. "EPA Method Study 18. Method 608-*0rganochlorine Pesticides and PCS' S, *' Envt ronmenta 1 Protection Agency, Envi ronmental Mon itoring and Suooort Laboratory. Cincinnati. Ohio, EPA-600/ 4-84-061; NT IS No. PB84 211358 (1984) 197 pp. Miller, R.A. and R. 0. Fox."Catalyzed wet Oxidation of Hazardous Wastes," Chapter 13 in Oetoxication of Hazardous waste. J H E*ner. Ed. (Ann Arbor 'll: ;nn Aroor science PuO'isners, inc., 1982), pp. 227-232. Miller. S. "The Persistent PC8 Problem," Environ. Sci. Technpl, 16(2):98A-99A (1982). Mills, P. A., J. H. Onley and R. A. Gaither. "Rapid Method for Chlorinated Pesticide Residues in Nonfatty Poods," J. Ass. Qffic. Anal. Chew. 46(2):186*191 (1963). Mills, P. A. "Variation of flonsil Activity: Simple Method for Measuring Adsorbent Capacity and Its Use in Standardizing Florisil Columns." J. Assoc. Qffic. Anal. Chem. 51(1):29*32 ( 1968). Mitchum, R. K. , w. A. Korfmacher and G. F. Moler. `'Capillary 'Tas '`hmmatogr.'ony/ atmospheric Pressure `legative Chemicai ionization Mass Spectrometry of the 22 Isomeric TetracMoro* dibenzo**dixin$," Anal. Chem. 54:719*722 (1982). Miyata, H. and T. Kashimoto. "The Finding of Polychlorodi* benzofurans in Commercial PCBs (Aroclor, Phenoclor and Clophen)," Shpkuhin Eiseiqaku Zasahi 17(6):434-437 (1976). Miyata, H. , T. Kashimoto and N. Kunfta. "Oetection and 0e* termination of Polychlorodibenzofurnas in Normal Human Tis* suet and Kanemi Rice Oils Caused 'Kanemi Yusho1 ," J. Food Hyp. Soc. 18(3):260*265 (1977). Mizushima, Y. and H. Mukai. "Study of Cleanup Operations in PC8 Analysis," Niiqata*ken Koqai Kenkvusho Kenkyu Hokoku 6: 110-11* (1982): Chem. Abst. 98:I0864x (1983). HONS 223656 . Bibliography Mizutani, T. and M. Matsumoto "Determination of Polychlor- Inatad Biphanyls by an Exhaustive Chlorination Method " Shokuhin Siseioanu Zasshi 13(5):398*404 ( 1972); Chao flbst 78:66666* (1973). ------------------- * Mizutani, T. and M Matsumoto. "Separation and Oatermmation of Polychlorinated Biphenyls and 00E by Oxidation in a Solid Support." i$1 Keqaku 19(5): 287-292 (1973); Che*. Apst. SO 116961b (1974). -------------------- Modi, G. , M. Piccimni and S. 8onciani. "Study of Pesticide Contamination m Soma Tuscany Winas," Soil. Chim. Union* I.tal. Lab. Prov. 2( 3) 133-147 (1976); Cham." Abst. 84:141276* rw------------------ --------------------- Moain. G. J. "Study of the Distribution and Fata of PoUcnlormateo Sipnanyis and Benzenes After Spill or Transformer Fluid," Report No. EPA 904/9*76*014, NTIS No. P82B8484 (1976). Moolenaar, 8. J. "Distribution and Fate of Chlorobiphenyls in the Environment," in Advances in Exposure, Health and n* vironmental Effects Studies of PC8s: Symposiumi Proceedings. R. J. Davenport and 8. X. Bernard (Ed*.), Office of Tone Substances, tl.S, Environmental Protection Agency, Washington 0.C, , Report No. 15I-TR-507-1378, NTIS No. P884-135771 (December 1963), pp. 67*96. Morita, M. , J. NakagawS. K. Akiyama, S. Mimura and N. [sono. "Oetailed Examination of Polychlorinated Oibenzofurans in PC8 Preparations and kanemi Yusho Oil," Bull. Environ. Contam. Toico 1 :S(l):57-'3 (1977). Morita, M. , J. Nakagawa, and C. Raooe. "Polychlorinated Oi* benzofuran (PCOF) Formation From PCS Mixture by Heat and 0*y* gen," Bull. Environ. Contam. Toxicol. 19:665-670 (1978). Moseley, M. A. and E- 0. Pellizzari. "Development and Eval* uatien of Wall Coated Open*Tu6uler Columns for GC Analysis of Individual Polychlorinated Biphenyl Isomers," J, High Res. ChromatPdf. and Chromatoor. Common. 5:404*412 (1982). Moser, J. H. and K. R. Huibregtse. "Handbook for Sampling and Sample Preservation of Water and Wastewater," EPA-600/ 4*76*049 (NTIS No. PS-259 946) (1976). Meye, H. A. "High Speed llouid Chromatography of Pesti* cides," J. Chromatogr. 5ci. 13:268*278 (1975). HONS 223659 Bibliography 413 Muldre*, 0. H,, Q i Worobey and G. R. 8. Webster. "Sorp tion of [l4C] 2,4 ,5.2' .4',5'-H*Kacnlorobipheny to Glass and Plastic Surfacesp>*oc. Annu. workshop Pst)c. Residua Anal. (Watt. Can ), 16th. 0. C. G. Muir. d. , pp. 98-100 (1981); Chem. Abstr ~96~1S20d ( 1982). Mulnern, B. M. "An Improved Method for the Separation and Removal of Qrganocnlorme Insecticides front Thin-layer Plates.M J Chromatogr 34;SS6-SS8 (1968). Mulhern. B. M. , . Cromartie, W. l. Reicnei and A. Bel isle "Semiquantitat>ve Determination of Polychlorinated 6iphenyls in Tissue Samples by Thin LayerChromatooraDny.*' J Assoc. Qffic. Anal. Chem. 54(3) 548"550 (1971). Mullin, M. 0. and J C. Fiikins. "Analysis of Polychlori nated Biphenyls by Glass Capillary and Packed*Column Chro matography ," Chapter 11 in Advances m the [denti f ication and Analyse of Organic Pollutants in water, i. h. Keith Ed. , `/ol. . (Ann Aroor, "11: Ann Aroor science FuOiisners inc, 1981). pp. 107-196. MuMin. M. , G. Sawka, i, Safe. S. McCrindle and S. Safe. "Synthesis of the Octa- and Nonachlorobipheny) Isomers and Congeners and Their Quantitation in Commercial Polychlori nated Biphenyls and Identification in Human Sreast Milk," J. Ana). Toxicol. 5:130-142 (1901). Mullin, M, 0.. C. M. Pochini, S. H. Safe and L. m. Safe. "Analysis of PCBs Using Specific Isomer High-Resolution Capillary Gas Chromatography," Chapter 12 in PCBs: Human and environmental Haiards, f. m. O'ltri and M. A. Kamrin, Eds". (Boston: 0utten*orth Publishers. 1983), pp. 165-176; Chem- Abstr, 100:79164* (1904). Mullin, M. 0., C. M. Pochini, S. McCrindle, M. Romkes, S. H. Safe and l. M. Safe. "High-Resolution PCB Analysis; Synthe sis and Chromatographic Properties of All 209 PC0 Congeners," Environ. Sci. Techno! 10:460-476 ( 1904). Murphy, P. G. "Sulfuric Acid for the Cleanup of Animal Tis sues for Analysis of Acid-Stable Chlorinated Hydrocarbon Res idues/ J. Assoc. Qffic. Anal. Chem. SS(6);1360-1362 (1972). Murphy, T, J,, A, Schinsky, G. Paolucci and C. P. Riesiutko. "inputs of Polychlorinated Biphenyls from the Atmosphere to Lakes Huron and Michigan," Chapter 22 in Atmospheric Pol>utants in Natural Waters. S. J. Eisenreich, Ed. (Ann Aroor, Ml; Ann Arbor Science Publishers. Inc., 1901a). pp. 44J-450. HONS 223860 414 Bibliography Murphy, T. J., T C. Heesen, and 0. R. Young. "Exchange or Comments: Evaluation or a Technique ror Measuring Qry Aerial Deposition Rates or 00T and PCB Residues." Atmos. Environ 15.206-200 (1901b). Murphy, T. J. , and A. w. Schmsky. "Met Atmospheric Inputs or PC0s to the Ice Cover on lake Huron," J. Great Lakes Res 9(1): 92-96 ( 1903).----------------------------------- - Murphy, T. J., J. C. Pokojowczyk and M, 0. Hu 11 i n. "Vapor Exhange of PC0s with Lax# Michigan; The Atmosphere as a Sin* ror PC8s," Chapter 3 in Physical Behavior of PC0s m the Great Lakes. 0. Mackay, S. Paterson. S. J. E i senre i cn ino M" r Simmons. Eds. (Ann Arbor, Ml: Ann Arbor Science Puo- lishers, Inc., 1903), pp 49-50. Musia), C. J., 0. Hutzinger, V. Zitka and J. Crocker. "Pres ence of PCB. 00E and OOT in Human Milk in the Provinces of New Brunswick and Nova Scotia. Canada." 3ull Environ '^ij* "ixirci ::c) :53-:67 cs74). Musial. C. J. and J. F. Uthe. "Interlaboratory Calibration Results of Polychlorinated Biphenyl Analyses m Herring," J. Assoc. Off. Anal. Chew, 66(1);22-31 (1983). Musty, P. R. and G. Nickless. "Use of Amberlite XAD-4 for Extraction and Recovery of Chlorinated Insecticides and Poly chlorinated Biphenyls from Water," J. Chromatogr, 89:135-190 (1974a). Musty. P. R. and G. Nickless. "The Extraction and Recovery of Chlorinated Insecticides and Polychlorinated Biphenyls from Water Using Porous Polyurethane Foams." J. Chromatogr 100(1): 03-94 (1974b). ,#ust>, r. k. and G. Nickless. "Extractants for Organocnlo* rine Insecticides and Polychlorinated Biphenyls from water." J. Chromatoor. 120:369-378 (1976). Myers, 0. S. , S. 0. Myers and J. J. Kelly. "PCB White Paper. Part II." Natl. Ena. 86(91:26-32; Chem. Abstr 94;194024a (1982). Nagayama, J. , Y. Masuda and M. Kuratsune. "Chlorinated Qi* benzofurans in Kanechlors and Rice Oils Used by Patients with Yusho." Fukuoka Ioanu Zasshi 66(10):593-599 (1975) Nagayama. J. . M. Kuratsune and Y. Masuda. "Determination of Chlorinated Oibenzofurans in Kanechlors and `Yusho Oil'." Bull Environ, Contam, TqkIcqI. 15(1).9-13 (1976). HONS 223861 Bibliography 415 Nakagawa. M. . M Kayama and E. Ariyojhi "Measurements of Polychlorinated Biphenyl (PCB) in Water. Sediments. and Or ganisms or Two Rivers in Hiroshima PrefectureJ. fac. Fish Amm Husp NirosMua Univ. 14 ( 2). 253-259 ( 197TT! Pup 11 c Hea 11r> Apst- 62(6).34268 (1976). Nakagawa. J-. M. Morita and y. Higuchi. "Analysis of Poly chlorinated Oibenzofurans by Gas Chromatography Using Glass Capillary Columns,1' Tokyo-tor i tsu Eisei Kenkvusho Kenkyu Nampo 30-1 260-264 (3979); Cham, AQst. 93:360694c (3900). Nakamura, A. and T. Kashimato. "Studies on a Calculation Method ror Polychlorinated Biphenyl (PC8) Isomars. Analysis Usinq an Apiezon i, Column." Shokuhin Ei$eiqa*u Zasshl 18(3); 1-12 (1977). Cham. AQst. 87;6}$2*r (19??). Nakatsu. K. . J. f Brian, h. TauD, w. J. Racz and G. S Warns. "Gram Quantity Syntnasis and Chromatographic Assess ment of 3.3' .4 ,41 -TetracMorobiphany IJ Chromatoar. 239 97-106 ( 1982). Namovicz, R. M. (Ed.). Environ. Health Parsoac.. Experi mental Issua Number One. National Institute (Environmental Health Sciences. Research Triangle Park. nC, 181pp. (April 1972). Napier. J. M. , H. A. Travaglini, E. G. Laggis and M. A. Makerewicz. "Evaluation and Oevelopment of Polychlorinated Biphenyl Removal Processes." Oak Ridge Y-12 Plant. Oak Ridge. TN. Report No. Y/0Z*1, February 5. 1982. National Bureau of Standards. "Standard Reference Material 1581. Polychlorinated 8iphenyls in Oil," U.$. Department of Commerce, Washington. O.C.. Summer 1982. 1 pp. National Institute for Occupational Safety and Health. NIOSH Manual or Analytical Metnoqs. Second Edition, 5rt 1, NlQSH Monitoring Methods,-VoT'.' l7 "Polychlorinated Biphenyls (PCB) in Air, Analytical Method P4CM4 244," U.S. Department of Health. Education, and Welfare, Cincinnati, Ohio. April 1977a. National Institute for Occupational Safety and Health. NIOSH Manual of Analytical Methods. Second Edition, Part I, NIOSH Monitoring methods, vol. 3, "Polychlorinated Biphenyls (PCS) in Air, Analytical Method P4CAM 253," U.S. Department of Health, Education, and Welfare, Cincinnati, Ohio, April 1977b. (RONS 223062 416 Bibliography National Institute for Occupational Safety and Health. ''Cri teria for a Recommended Standard....Occuoational Exposure to Polychlorinated Biphenyls (PCBs)." U.S. Oepartment of Health, Education, and welfare, (Public H*a1th Service, Center f0)l Disease Control, and National Institute for Occupational Safety and Health), QHW (NlQSH) Publication No. 77-22S, 224 pp. (September 1977c). ' National Research Counci1 Polychlorinated Biphenyls, Na tional Academy of Sciences. Wasnmgton. Q.C., 182 PP. ( 1979). National Technical Information Service. "Polychlorinated Bi phenyls in the Environment. 1980-September, 1981." PB82303867, 70 pp. (1082). National Technical Information Service. "Polychlorinated Si- phenyls m the Environment. 1977-January, 1983,'* P883 859322, 199 pp (1983a). National Tecnntcai Information Service. "Polycnlormateo Siphenyls in the Environment. September 1900-February 1983,'* PB83-804716. 154 pp. (1983b). National Technical Information Service. "Polychlorinated Bi phenyls: Occurrence in Sediments and Soils. 1977-January 1984 (Citations from the Selected water Resource Abstracts Oata Base)." P884-B60790, 124 pp. (1984a). National Technical Information Service. "Polychlorinated Bi phenyls: Occurrence and Treatemnt in Municipal and Indus trial Wastes. 1977-1983. (Citations from the Selected Water Resource Abstracts Oata Base)," PB84-06O949 (1984b). National Technical Information Service. "Polychlorinated Bionenvls in the c-*shwater Environment. '.977-January '.984 (Ci tations from the Selected water Resources Abstracts Oata Base)." P884-8573S8, 118 pp. (1984c). National Technical Information Service. "Polychlorinated Bi phenyls in the Environment, September 1980-Apnl 1984 (Cita tions from the NTIS Oata Base)," P684-865724, 188pp. U964d). Ntdham, l. l., A. l. Smrek, S. l. Head. v. w. Burse and J. A. Liddle. "Column Chromatography Separation of Polychlo rinated Biphenyls from Oichlorodiphenyltrichloroethane and Metabolites," Anal, Chem, 52:2227-2229 (1980). Needham. 1. L., v. w. 8urse and H. A. Price. "Temperature' Programmed Gas Chromatographic Determination of Polychlori nated And Polybrominated Biphenyls in Serum,'* J. Assoc. Off. Anal. Chem. 64(5):1131-1137 (1981). HONS 223863 Bibliography 417 Neely, w 8. 'Reactivity and Envtronmental Persistence or PCB Isomers," Chapter % in Physical Behavor of PCBs m the Great Lakes. 0. Mackay, S. Paterson, s. Eisenre'ch- and H S. Simmons. Eds. (Ann Arbor. Ml: Ann ~bor Science Pub* lishers. Inc.. 1903) pp 71-00. Neidert, E. . and P. w Saschenprecker, improved Storherr Tube for Assisted and Seep Co-Oisti I lation Cleanup of Pesti cides. Polychlorinated B'phenyls, and Pentachloropnenol from Animal Fats.'1 J Assoc Off. Anal. Chem . 67(4). 773*775 (1984). Nelson. N. "Comments on Research Needs.' Environ Health Perspec- 1:181-185 ( 1972 ). Nero, V P , and R. 0. Hudson. "Liquis Chromatographic Cleanup Prior to Determination of Polychlorinated Biphenyls in Oil by Gas Chromatography/Mass Spectrometry," Anal. Chem. 56; 1041*1043 (1904). Neu, H. J , M. Zell anc K. 8a 11 scnmi ter. ' Identi f 11 lerung /on 'nte'komoonenten in kompiexen jemiscnen ourcn Retentions*Index*vergleich nach Caoi1lar-Gis-Chromatographie mit Elektroneneinfangdetektor (C0)." Fresenius" l. Anal. Chem. 293: 193*200 (1978). Neu, H. J. and R. Zinburg. "Are We Using tie Full Resolving Power of Capillary GC?" J. High Rescl. Chromatoqr, 4 Chromatoqr. Commun. , 2:395*399 Neulicht, R. M., M. 0. Erickson, and R. V. Shah. "Guidelines for PC8 Destruction Permit Applications ino Demonstration Test Plans," Work Assignment No. 6, Oraft Interim Report No. 1, Revision No. 2, ERA Contract No. 68-02*3938. U S. Environ mental Protection Agency, Office of 7;*ic Substances, Washington, DC (March 1965). newsome, . n. and j. a. imeias. Raaioi'^unoassay or ?C0s in Milk and Blood," Intern. J. Environ. Anal. Chem. 10:295 304 (1981). Newton, 0. A. and R. R. Laski. "A Computer Routine for the Rapid Quantitation of Combinations of Aroclors 1242, 12M 4nd 1260,* J. Chromatoqr. Scl. 21:161*165 (1393). Nicholson, w. J. and J. A. Moore (Eds.). "Health Effects of Halogenated Aromatic Hydrocarbons," Ann, s Y, Acad. ScL. .Vol. 320 (1979). Nickerson G. 8. and S. T. Liken*. "Quantitative Analysis of Organochlorine Pesticides and PCB's," J. C^rpmatogr. 21:1*5 (1966). MOMS 223*6+ 418 Bibliography Nisbet. I C T "Environmental Occurrence and Hymen E*do* sure m Polycnlorineced Siphenyls * Environmental Impact," Environ Pes. 5:287-308 (1972a). ' Nisbet. I. C. T. "Transport Models and Monitoring Schemes for PC8s in Polychlorinated Biphenyls EnvironmentaI Im pact," Environ. Res 5 348*352 (1972b). Nisbet, C. T. and A ? Sarofim. "Rates and Routes of Trans port of PC6s m tne Environment," Environ, Health Persoec 1:21-36 (1972a). " Nisbet, 1. C. T. ano a f. Sarofim. "Transport ana Transfor mation in the Environment in Polychlorinated Biphenyl* Environmental Impact," Environ. Res. 5:213*287 (1972b). Nordstrom, R. J. "(Detection of PCBs by Infrared Seectros:ooy.' in Proceedings: 1983 Seminar. G. Addis and R t Komai, Eds.^ fleport No.tP&l-cl'jool ;Palo Alto, CA. elec tric Power Research Institute), 1984. Nordstrom, R. J. and 8. McIntosh. "Infrared Spectroscopy for Field Measurements of PCBs," in Proceedings'. 1961 PCB Sem inar. G. Addis and J. Marks, Eds., Report No. ^PRl-Ei*2i7j (Palo Alto, CA; Electric Power Research Institute), 1982, Norstrom, R. J, , R. W. Risebrough and 0. J. Cartwright. "Elimination of Chlorinated Oibenzofurans Associated with Polychlorinated Biphenyls Fed to Mallards (Anas platyrnynchos).1' Toxicol. App), Pharmacol. 37:217-228 ( 1976)! Nose, A. "Oecachlonnation of Polychlorinated Biphenyls and Its Application to Soil and Rice Analyses." Nippon Npgei Txfrrr.v.asaku 'jijhi 16(12). 579-581 (1972); Chem. Abst. 78: I*^633r --------- ---------------- Nose, K. "Assay of Residual PCS [Polychlorinated Biphenyl) in water, Soil, and Agricultural Products," NQyaku Se'san Gijutsu 30;23-36 (1973); Chem. Abst. 79:10l5lTf U973). Nose, K. "Determination of PC8 (Polychlorinated Biphenyls)," Yukaqaku 25(101:638-644 (1976); Chem. Abst. , 86:2656Sp TT5777T Nowicki, H. G. "Application of Azulent as Visual Aid to Mon itor Column Chromatographic Fractionation of Samples for Pesticide and Polycnlorinated Biphenyl Determination," J. Assoc. Offlc. Anal. Chem. 64(1):16-18 (1981). MONS 223865 Bibliography 419 Nulton, C. P. , C. 1. Haile, and 0. P. Redford. "Oetermina* lion of Total Organic Halogen in EnvironmentaI Extracts by Gas Chromatography with Hall Oetection." Anal. Chem. 56 - 598- S99 ( 1984 ) ---------------------- Nygren, S. and P. E. Mattsson. "Flow Programming in Glass Capillary Column-Electron Capture Gas Chromatograpy by Using the Valve in the Splitter Line." J. Chromatoor 123:101*100 (1976). ---------------------^ Nyquist, R. A , C. l. PuUig and 0. P. Peterson. "Identifi cation of Pentachiorobiphenyl Isomers by Application of Oif* fuse Reflectance Fourier Transform infrared Spectroscopy,'* Appl. Spectrosc. 37(2):140*153 (1903). Qehme. M. , and h. Stray, "Quantitative Oetermination of Ultra-Traces of Chlorinated Compounds in High-vo'ume Air Samples from the Arctic Using Polyurethane Foam as Collection Medium.*' Frsnius' l. Anal. Cham. . 311:66S-6?3 ( 1902). Oehm*. H and 9. Ottar "Toxie Organic Air Pol lut.mts in the Arctic," in Proceedings: A Speciality Conference On: Mea surement and Monitoring of Non-Criteria (Toxic) Contaminants in Air, . R. Frederick (Ed. ), The Air Pollution Control As sociation, Pittsburgh, PA, pp. 60-67 (1903). Ofstad, E, 0. , G. I unde, and K. Martinsen, "Chlorinated Aro matic Hydrocarbons in Pish from an Area Polluted by Indus trial Effluents," Sci Total Environ.. 10:219-230 (1970). Ogata, J. N. , J. 0. Okun, J. W. Hylin, and A. Sevenue, "Gas Chromatographic Method for the Analysis of Polychlorinated Biphenyls in Transformer Oil," J. Chromatoqr, . 189:425*427 (1900). O'Keefe, P. W. , R. M. Smith, 0. R. Hilker, K. M. Aldous, and V. Gilday "1 Semi automated Cleanup Method 'nr 3^lyrhlonnated Oibenzo-g-dioxins and Polychlorinated Oibenzofurans in Environmental Samples," in Chlorinated Oioxins and Oibentofurans in the Total Environeynt, II. 1. H, Keith, C. Rappe. and (T Choudhary, ds"! (Boston: Suttervorth Publishers, 1985) pp. 111-124. Okumura, T. , T. Kadono, and M. Nakatani, "Thin-layer Chroma tography on Precoated Adsorbents Fixed with Fused Glass, v. Thin-layer Chromatography on Kieselguhr Sintered Plate," Yakuooku Zasshi 93(1);79*06 (1973); Chem. Abst. 70:105744j 1973). O'Hara, T. and 6. Mage). "Sample Analysis for Neal's land fill Case," unpublished memorandum, U.S. Environmenta1 Pro tection Agency Region V, Chicago. It. October 27. 1982. HONS 223866 420 Bibliography OnuSka, F I. and M. Comb*, " Identification and Quant*t*tive Analysis of Polychlorinated Biphenyls on wCOT Glass Capillary Columns," in Hydrocarpons and Haloqenated Hydrocarbons -n me Aquatic Environment, T K. Afghan ana 0. Mackay. Zci~ (New fork: Plenum Press, 1980) pp. 285*302. Onuska, F. I., R. J. Koainar and K. A. Terry, "Identifica tion and Determination of Polycnlorinated Bipnenyis by High* Resolution Gas Chromatography." J. Chromatoqr 279:111-118 ( 1983). --------------------- Onuska. F. I. "N*rrow-8ore Wall-Coated Open-'ubuiar Columns for Fast High-Resolution Gas Chromatographic Separations of Toxicants of E.nvironment*I Concern." Journal of Chromatoq* raphy. 289:207-221 (1984) Organization for Economic Cooperation ana Oeve>ooment 'l~> I chlorinated Biphenyls. Their Use and Control, Environmental Directorate. Parist1973). Organization for Economic Cooperation and Development. 0C0 Report on Protection of the Environment by Control of Poly chlorinated Biphenyls, Pans (1979). ~~ Osterroht, C. , "Development of a Method for the Extraction and Determination of Non-polar. Dissolved Organic Substances in Sea Water," J. Chroeiatoqr, 101;289-298 (1974). Osterroht, C. , "OissoWed PC8's and Chlorinated Hydrocarbon Pesticides in the Baltic, Determined by Two Different Sam pling Procedures." Marine Chem. 5:113*121 (1977). uSwaid, l. u. , w. uvy, o. v. C-rpett, . "Oi fferentiation and Characterization of Isomeric Polychlori nated Biphenyls by Gas-Liquid Chromatography Coupled with Electron impact and Chemical Ionization Mass Spectrometry J, Chromatoqr. 93:63-90 (1974a). Oswald. E. 0., P. W. Albro, and J. 0. McKinney, "Uti1ization of Gas-liquid Chromatography Coupled with Chemical Ionization and Electron Impact Mass Spectrometry for tne Investigation of Potentially Hazardous Environmental Agents and Their Me tabolites," J, Chromatoqr. 98:363-448 (1974b). Ouw, H. K. , G. R. Simpson, and 0. S. Siyali, "Use and Health Effects of Aroclor 1242, a Polychlorinated Biphenyl, m an Electrical Industry." Arch. Environ. Health. 31:189-194 (1976). Paasivirta, J. and M. Pitkinen. "Structure Analysis of the Main Components in PCB Mixture Clophen A 60," Finn. Chem. Lett. 89-93 (1975). HONS 229667 Bibliograpfiy 421 Pacco. J. M. and A K. Mukherji. "Determination of Polychlo rinated BipntnyU in a Polymer Matrix by Gel Permeation thro- matograony using Micro-Styrag*1J Columns," J Cbromatoor 144: 1:3- 11 7 ( 1977 ). --------------------- Palmork. k. h. , J. C Ouinker, A. H. Knap, and J. P. Villeneuve. "Organochlonnesin Scientific Report of the Intercalibration Exercise. Intergovernmental Oceanograpnic Commission Technical Senes. Report No. 22. UNESCO, Paris (ISSN 92-3-102077-3) (1982) pp. 60-83. Pankow, J. P., t. M. Isabelle, and w. E. Asher. "Trice Or ganic Compounds in Rain. 1. Sampler Oesign and Analysis by Adsorption/Thermal Oesorption (ATO)," Environ. Sci, Techno I. 18.310*318 (1984), Errata puolished in Environ. Sci. technol. 18:987 (1984). Parker, c. E., P. w. Albro, M. J. Sobenrieth. T. w. Cochran and J. 0. Robinson. "Quantitation of Haiogenated Aromatic Comoounos by Gas Chromatography-Mass Soectrometry." J. Chromatoor. 278(1).1-il (1983). Parkinson, A., R. Cockerline, and S. Safe, "Polychlorinated 8ipnenyl Isomers and Congeners as Inducers of 8oth 3-Methylcholanthrene* and Phenobarbitone*Type Microsomal Enzyme Activity," Chtm.-8iol. Interactions. 29:277*289 (1980a). Parkinson, A., i. Robertson, L. Safe, and S, Safe. "Poly chlorinated Biphenyls as Inducers of Hepatic Microsomal Inrymes: Structure-Activity Rules," Chew.-8iol Interactions. 30:271-285 (1980b). ParUr, h. and M. Mansour. "Gaschromatograpnic Determination of Several Cyclodiene Insecticides in the Presence of Poly chlorinated Biphenyls by Photoisomerisation Reactions," in Analytical Techniques Environmental Chemistry 2. J. ATbaigesT Ed. (New fork: Pergemon Press, 1982), pp. 241 247. Parns, R. M. , f, R. Guenther, w. . May. and S. N. Chetler. "Analysis of PCBs in Oil: Technique and SRM Development." in National Bureau of Standards Special Publication 674) Proceedings, Conference on Measurements and Standards for Re cycled Oil - IV. field at N8S,Gaithenourg, Maryland (July wRFpp. 27-32. Pastel, M. , 8. flush and J. S. Kim. "Accumulaton of Poly chlorinated Biphenyls in American Shad Ouring Their Migration in the Hudson River, Spring 1977," Pestic. Mpnit. J. 14(1): 11-22 (1980). MOMS 22S668 422 Bibliography Pavlou, S. P. "Environmental Oynaimcs of Trace Organics Con taminants in Estuarine and Coastal Zone Ecosystems." m An alytical Technique* in nvi r-pnmental Chemistry. j. AlbaigeT" Ed. (New York; Pergamon Press. 1980),"op. 387-399. ' Pavlou. S. P. and W Horn. "Interlaboratory Calibration Re sults from Chlorinated Hydrocaroon Analyses in Marine Sedi ments." Hanne Chem. 4 155*163 ( 1976). Pavlou. S. P. , R. N. Dexter and w. Horn. "Characterization of Chlorinated Hydrocarbons in the Marine Environment: Sampling and Analytical Aspects," in Analytical Techniques in Environ mental Chemistry , J AI beiges, Ed" (Mew~rort: Pergamon Press, 1980)._DP- 185-196. Pearson. C. R. "Halogenated Aromatics." in The Handbook of nvirpnmenta 1 Chemistry, 0. Hutzmger. Ed. (New iorx, Soringer-verlao. 1982). DP 89*116. PEDCo Environmental, Inc. "Substitutes for PCS's for use in Indoor Electrical Transformers." Contract No. 68-01-3935, Work Assignment 1-16, PN 3607-6. Office of Pesticides anq Toxic Substances, U.S. Environmental Protection Agency, Washington, O.C. (January 6, 1984). Pellizzari. E. 0. "Electron Capture Detection in Gas Chroma tography," J. Chromatoor, 98:323*361 ( 1974), Pellizzari, E. 0. "State-of-the-Art Instrumental Organic Analysis in Environmental Chemistry," Chapter 10 in Environ mental Health Chemistry. J. 0. McKinney, Ed. (Ann Arbor, MI: Ann Arbor Science Publishers, Inc., 1981), pp. 195-218. Pellizzari E 0. "Analysis of Adioose and 9!ood Se*a c.jmples for Individual PCS Isomers," MR I Subcontract No. 82 4900-21, EPA Contract No. 68-01-5915, Monthly Tech. Prog. Re port No. 2, March 1, 1982. Pellizzari, E. 0., K. 8. Tomtr and M. A. Moseley. "HighResolution Gat Chromatography and Negative Ion Chemical Ioni zation Mass Sptctromotry of Polychlorinated Biphenyls," Chapter 12 in Advances in thm Identification and Analysis of Organic Pollutants in Water, T FT Keith, Ed., vol. 1 (Ann Armor. Ml: Ann Areor Science Publishers, Inc., 1981), pp. 197-218. Pellizzari, E. 0., S. 0. Cooper, T. 0. Hartwell and 0. A. Whitehurst. "Analysis of Adipose and Stood Sera Samples for Individual PCS Isomers." Pinal Report, Midwest Research Institute, Kansas City, M0, Prepared for Office of Pesticides and Toxic Substances, U.S. Environmental Protection Agency, Contract No. 68-01-5915, Task 46 (1983a). MONS 229669 Bibliography 423 Ptllizzari, E. 0., M A. Moseley, S. 0. Cooper, J. V. Harry 8. A. Oeeutn and M. 0. Mull in. "fitctnt Advances in tne Anal* ysis of Polycnormated 8'phenyls in Environmental and Biolog ical Media," m Advances =n Exposure, Health and Environ mental Effects Studies^ of PC8s: Symposium Proceedings, R. J. Oavenport and B. iT Bernard (TdV), Office of Toxic Sub stances. US. Environmental Protection Agency. Washington, 0-C. . Report No. tSI-TR-507- 1379. S No. P884-135771 (Oecemper 1903b). pp. 4-60. Pepe, M. G. and J. J. Byrne "Adhesion-Binging of 2,2'.4,4',S,S'*He<acnioroOipnenyl to Glass and Plastic: A Posible Source of Error for PCB Analysis." Bull. Environ. Contain. Tpxicol 25:936-940 (1980). Perlman, h. l. "Accelerated Oecision.'* US. Env i ronmenta I Protection Agency, Before the Administrator, in re: Oow Chemical Company, Respondent. Oocket No. T$CA (I6(a))-1, September 22. 1980. Perry, T W , 3. J Everson, \. S. Henor**, ?. C. Peterson and F. R. Robinson. "Placental Transfer of Ingested Aroclor 1254 in the Bovine." in Trace Substances in Environmental Health 16:326-330 (1982). Peterman, P. H. , J. J. Oelfino, 0. J. Oube. T. A. Gibson and F. J. Priznar. "Chloro-organic Compounds in tne Lower Fox River, Wisconsin." in Hydrocarbons and Halogenated Hydrocar bons in the Aquatic Environment. B. K. Afghan and 0. Mackay, Eds. (New York: Plenum Publishing Corporation. 1980), pp. 145-160. Peyton, T. 0. "Biological Disposal of Hazardous Waste." En zyme Microb. Technol, 6(4);146-154 (1904). Picer, M. and M Ahet. "Seoaration of Polychlorinated Bi phenyls from GOT ano its Analogues on a miniature ji'uca j*i Column," J. Chromatoor, 150:119-127 (1978). Picer, N. and M. Picer. "Evaluation of Macroreticular Resins for the Determination of Low Conctntratons of Chlorinated Hy drocarbons in Sea Water and Tap Water." J. Chromatoor. 193: 357-369 (1990). Pickor, J. E. . and 8. N. Colby. "Field Determination of Aroclors Using an Automated Electron Capture Qetector Gas Chro matograph," in Proceedings: 1983 PCS Seminar. G. Addis and R. Y. Komai. EdsT^ Report Ho. EPR1`El-3581 (Palo Alto. CA: Electric Power Research Institute). 1964. HONS 223*10 424 Bibliography Piechalak, 8. "The Semiquantitative Cetection of Polycnlor i n a ted 8iptttnyl$ (ftC8s) m Contaminated Soils by Thin-Layer Chromatography," m Proceedings, 1383 PC8 Seminar. C. Ao<jiS and R t. Komai, Eds.. Report no. EPRI-El-3581 (Palo Alto CA. Electric Power Research Institute), 1984. ' Pittaway, A. R. , R. S. O'Connor and E. J. Heiden. "A Report of a Survey on the Incidental Manufacture, Processing, Dis tribution, and Use of Polycnlormated Biphenyl at Concentra tions 8elow SO ppm," Report prepared for Chemical Manufac turers Association by Regulatory Research Service (Novemoer 1981). Pittaway. A. R. and T. w. Homer. "Statistical Analysis Oala from a Round Robin Experiment on PCS Samples," Report prepared for Chemical Manufacturers Association, Washington O.C. (Marcn 18. 1982). ' P1 umo. "i., / "P-ocedures 'or -land I i ng jnu Chemical Analysis of Sediment and water Samples,'' Prepared for u.$ Environmental Protection Agency/Corps of Engineers Technical Committee on Criteria for Dredged and fill Material, Contract No. EPA-4805572010, NTIS No. AO A103788 (May 1981). Polcyn, A. J. , S, A. Whitlock and T. E, Siedhoff. "PC0 Waste Destruction Study: High Efficiency Boiler," in Proceedings A Specialty Conference on: Measurement and Monitoring of Non-Criteria (Toxic) Contaminants in Air, E, IT Frederick. Ed. .T^ittsburgh, PA^ The Air Pollution Control Association, 1983), pp. 361-373. Polishuk. 2. W. , M. Ron, M. Wassermann, $ Cucos. 0. Wassermann and C. Lemescn. "Pesticides in People. Organochlorm* Comoounds in Human Blood Plasma and Milk." Pesnc Mpmt J iCH**;. ui- U'i <1377). Pomeranta, I. J. 0urk 0. firestone, J. McKinney, J. Roacn and W. Trotter. "Chemistry of PC8s and PB0S," Environ. Health Perspec. 24:133-1*6 (1978). Poole, C. F. and $. A. Schuette, "Isolation and Concentra tion Techniques for Capillary Column Gas Chromatographic Analysis," J. Chromatoor, pp. 526-5*9 (1903). Porter, M. L. , and J. A. 8urke. "An Isolation and Cleanuo Procedure for Low Levels of Organochlorinc Pesticide Residues in fats and Oils," J Assoc. Offlc. Anal- Chem. 56:733-738 (1973). MONS 223871 Bibliography 425 Pressley, T A. and J . longbottom. "The Determination of Organon*I ia Pest'ooes ana PCBs in Industrial and Municipal wastewater Method 617," u.S. Environmental Protection Agency, Report no. EPA-600/4-82-006, 35 po. . NT[S PB82-156001 (1982). Price, h. a., and R. Welch. "Occurrence of Polychlori nated Biphenyls in Humans," EnvironmentaI wea'th Perspec tives. 1:73-78 (1972). ~" Pyysalo, H. , K. Wickstrom, and R. litmanen. "A Baseline Study on the Concentrations or Chlordane-. PC8- and DOTComoounds in Finnish Pish Samples in the fear 1982." Chempsphere. 12(6):837-842 (1983). Cue Hee, S. S. , J. A. Ward, M. w. Tabor and R. R. Suskind. "Screening Method for Aroclor 1254 in Whole Blood,'1 Anal. Chem. 55:157-160 (1983). Rapaoort, R. A. ana S. J. Eisenreich. "Chromatograohic De termination of Octanoi-water Partition Coefficients (A 'S) for 58 Polychlorinated iipnenyi lonqeners," Environ.0^!. Techno 1. 18:163-170 ( 1904). Rappe, C. "Analysis of Polycnlorinated Oioxms and Purans," Environ Sci. Techno). 18(3):78A-90A (1984). Raooe, C. , H. R. 8user, H. Kuroki, and Y. Masuda. "Identifi cation of Polycnlorinated Oibenzofurans (PCOFs) Retained in Patients with Yusho," Chemosphert B(4);259"266 (1979). Rappe, C. and H. R. 8user. "Chemical Properties and Analyt ical Methods," Chapter 2 in Haloqenated Biphenyls, Terphenyls, Naphthalenes, Dibenzodioxins and Related PTooucts^ R 'D Aimbrougn, d. (New York" NY: Elsevier/North-Holland Biomedical Press, 1980), pp. 41-76. lappe, C. . i. Marxiuno. P.-A. 8ergqvist jna M nansson. "Polychlorinated Oibenzo*"dioxins, Dibenzofurans and Other Polynuclear Aromatics Formed Ouring incineration and Poly chlorinated Bfphenyl Fires," in Chlorineted Qixoins and 01benzofurant in the Total Environment. 0. Choudhary, l. H. Aeith, C. Rappe (Eds.) (Xnn Arbor Science Book: Buttervorth Publishers, 1903), pp. 99-124. Reggiani, G. " Toxicology of TC00 and Related Compounds: 0bservations in Man," in Chlorinated Dioxins and Related Compounds. 0. Hut* inger, R. w. frei, t. Herian ana f. Pocchian, Eds. (New York , NY: Pergamon Press, 1902), op. 463-493. HONS 426 Bibliography Reynolds. L, M. "Polychlorobiphenyls (PCB's) end Their In terference ith Pesticide Residue Analysis/* Bull. Envirn Contam. Toxicol. 4(3) 128-143 ( 1969). '-- Reynolds, L. M. , and T Cooper. "Analysis of Organocnlonn# Residues m Fish," Water Quality Parameters. A$TM sTP $73( American Society for testing and Materia Is, pp. 196*205 (1975). Ribick, M. A.. G. R. Oubay. J. 0. Petty, 0. 1. Stalling, 4no C. J. Schmitt. "Toxaphent Residues in Fish: Identificat ion. Quant 1fication. and Confirmation at Part per Billion Levels/* Environ, Sci. techno I, 16:310"318 (19B2). Rice. C, P. and W. A, Frez. `Aoolication of Capillary Chro matography to the Study of the Cycling of PCBs on Suspended Particles." Final Report Prepared for the Great Lakes En vironmental Research Laboratory The National Oceanograpmc ind Atmosoheric Administration. Oeoartment or Commerce /ant NA79RA0GQQG6, NUS No. PB82-245903 (1981). Rice, C. P. , P. A. Meyers and G. S. Brown. "Role of Surface MtcroUytrs m the Air-Water Exhange of PCBs," Chapter 10 in Physical Behavior of PCBs in the Great Lakes. 0. Mackay, S. Paterson, S. J. E isenreich and M~S Simmons, Eds. (Ann Arbor, MI: Ann Arbor Science Publishers, inc., 1983), OP. 157-179. Rice, C. P. , 8. J. Eadie, and K. M. Erstfeld. ''Enrichment of PCBs in Lake Michigan Surface Films," J. of Great Lakes Re search. 8(2):265-270 (1982). Richardson, W. 1,, v. t. Smith and R. wethington. "Oynamic Mass Balance of PCB and Suspended Solids in Saginaw 8ay--A Case Study/' Ihaoter 13 " :hysicai leiuvmr ji ACs* .0 ~nt Great Lakes. 0. Mackay, S. Paterson, l.J, Eisenretcn and mTT 57*5ons, Eds. (Ann Arbor, Ml: Ann Arpor Science Pub lishers, Inc., 1903), pp. 329-366. Ringer, R. K, "Toxicology of PCBs in Mink and Ferrets," in PCBs: Human and Environmental Hazards, F. M. 0'ltri and M. A. Kamn n, Eds. (Boston: Butterworth Publishers, 1983). pp, 227-240. Risebrough, R. W. "Determination of Polychlorinated Bi phenyls in Environmental Samples," Presented at the Interna tional Symposium on Identification and Measurement of En vironmental Pollutants, Ottawa. Ontario. Canada, June W-17. 1971. HONS 223873 Bibliography 427 Riseorough. R w. . 8 w de tappe, and y. Walker J], "Trans fer of Higher Moltcular weignt Chlorinated Mydrocarpony to the Marine Env i ronment," in Marine Pollutant Transfe-. h. l. winaom, R. A 0-ce. Eds (Lexington, MA- .Txmgton Books 1976). po. 261-321. Riva. M. , A. Cartsano and A. Caghetta. "Rapid GLC-ECO [Gas- Liquid Chromatograohy*Electron Caoture Qetector] Otter>na* tion of CMoroorgamc Pesticide and Po lycMorooipheny 1 (PC8*s) Residues m Animal Foods. General Considerations about Ecological Contamination." Riv. Ital Sostan;e Grasse 50( 12): 434-442 ( 1973 ), Chem. Aost. STm^cTittlj Roooins, A. L. and c. R. wilihite. 'A Rapid Method for the Analysis of Polychlorinated Biphenyls in Milk," 2uH En* virpn. Contam, Toxicol 21:428-431 (1979). RoDerts, J. R. . 0. W. Rodgers. J R. Salley and M *. Rorkt. "Polycnormated Biphenyls: Biological Criteria for an As sessment of Their Effects on Environmental Quality.' Asso ciate Committee on Scientific Criteria 'or Enyironmtnta I Quality. Ottawa, Canada: National Research Council of Canada ( 1978). Rodgers. R. W. "Model Simulation of PCB Oynamics in Lake Michigan," Chapter 17 in Physical Behavior of PC8s in the Great Lakes, 0. Mackay, S. Paterson. S, J. Eisenreicn and M. S. Simmons, Eds. (Ann Arbor. MI: Ann Arbor Science Pub lishers, Inc., 19B3), po. 311-327. Rodriguez. C. F. , W. A, McMahon and R. E. Thomas. "Method Development for Determination of Polychlorinated Hydrocarbons in Municipal Sludge," Final Report, Contract No. 65*03-2606, Environmental Protection Agency, EPA-600/2*80-029. NTlS No, P8 82-234 071 (March 1980). Rogan, w. J. , 8. C. Giaoen, J. 0. McKinney, no P. nloro. "Chromatographic Evidence of Polychlorinated Biphenyl Expo sure from a Spill," J. Amer. Med. Assoc. 249(8):1057*1058 ( 1983). Rohleder, H.. H. Steudacher and W. Suemmermann. "Highpressure Liquid Chromatography for the Separation of lipo philic OrgenocMorine Xenooiotics from Triglycerides in Trace Analysis." Fresenius' 2. Anal. Chem. 279(2):152*153 (1976); Chem. Abst. 847l60197g (1976). Ross, P. F., 0. 1. Osheim and H. A. Nelson. "PCB Residues in Feedlot Steers," Bull. Environ. Contam. Toxicol. 25485-488 (1981) HONS 223874 428 Bibliography Roust, T. 0., "PCS Round Robin Analysis," in Proceedings 1981 PC8 Seminar. C. Addis and J. Marks, Eds , Reoort HoEPRl-El*2572 (Palo Alto. CA: Electric Power Research In$11tute). 1982- Rote, J. w. and w J Morns. "Use of Isotopic Abundance Ra* tios in Identification of Polychlorinated Bipnenyls by Mass Spectrometry." ( 1973). J. Assoc. Offic. Anal. Chem. 56( 1): 188* 19< Roth, R. w. , j. R. Heys, 0. H. r. Chten, G. A. Rotert, J. h. Saugier and M. 0. Erickson. "Methods of Analysis for inci* dentally Generated PCBs "Synthes i s of l3C-PC8 Surrogates ." Oraft Interim Report No. 3, Revision No. 1, EPA Contract no. 60*01-5915, Task 51., prepared by Midwest Research institute, Kansas City, MO, for Office of Toxic Substances, US. En vironmental Protection Agency, Washington, O.C.. Novemoer 22. 1982. 91 op. Rubenstein. H. M. "Polychlorinated Biphenyls: Single Isomer Formation from 2,4*0ich1orobenzoyl Peroxide," Abstract No 614, 1983 Pittsburgh Conference and Exposition on Analytical Chemistry and Applied Spectroscopy, March 7-12. 1983. Russell, 0. J. and 6. McOuffie. "Analysis for Phthalate Esters in Environmental Samples: Separation from PCB's and Pesticides Using Oual Column liquid Chromatography," Int. J rvmr.Environ. Anal, Chem. 15(31:165*183; Chem, Abstr. 99:iS1456v ------------------- ----------------- Rust, S. w. "Study of Errors Generated in the Chemical Analysis of Environmental Samples." Final Report, Task 67, Contract No. 68-01-6721, U.S. Environmental Protection Agency, Office of Toxic Substances. Washington. 0C (198*) Ruzo, 1. 0., H. J. Zabik and R. 0. Schuetz. "Polychlorinated diphenyls; Photolysis of 3.4,3'.4'-TetrachlorobiphenyI and 4,4* *0ichIorobiphenyl in Solution," flu 11. Environ. Contam. Toxicol. 8(4);217-218 (1972). Ryn, J. J., P-Y lau, J. C, Pilon. 0. lewis. H. A. McLeod, end A. Gervals. "Incidence and Levels of 2,3,7,8-Tetrachlorodibenzo-p-didxln in Lake Ontario Commerciel Fish," Environ, Sci. Techno!. . 18:719-721 (1984). Ryan, R. M. , 0. R. Pendleton and J. M. Jenks. "Coastal Im pacts of PC8 Incineration Operations in the Gulf of Mexico." in Proceedings: A SpecieIty Conference on: Measurement and Monitoring of Non-criteria noxic) Contaminants in Air, E. R. Frederick, Ed. (Pittsourgn: The Air Pollution^Control Asso ciation, 1983). pp. 351-360. HONS 223875 Bibiiograpny 429 Sabate. L. G. . X. Tom**, M. A, Colom and i Carcia-CarriIlo. "Oua^ttation of PCS - Chesbysnav' s HfthCa " Comout Add! lab 1C). 146; Chew. A&$tr 99:224441b (i;:2) " Saeiu. , A Tsutsu: . K. Ogun, H. ro$hi-ura and M. Hamana. "Isolation and Structure Elucidation of t*e Ammo Component of KC-400 (Chloroo iphenyIs)," PuAuoka* Icatu-Zasshi 62(11 21*24 ( 1971). Chew Abst. 74: I4624y7l97i; Safe. S. '`Overview of Analytical Identi f < tit ion and Soectro* scopic Properties." tn National Conference on Polychlorinated Biphen.1s (November l9*Tl, 19?5. Chicago. I Hino1s). P. A. Ayer. id. . EPA*S60/6*7S*004; NT IS No. PB 252-248. March 1976. Safe. S. "Metabolism. Uptake, Storage an: Bioaccumulation.'* Chaote- 4 m Haipgenated Biphenyls, Terphe*vls. Naoothalenes, 0iber:2d'Oins and Related Products. R. j. kimorougn, Ed. (New -or*, NT; Elsev1er/NortrrHo 11 and 5ioedical Press. 19B0). 30 81-107. Safe. S. "Polychlorinated Biphenyls (PC*s) and Polybrom*nateo iipnenyis vPBBs;. 3 iocnemi s try. Tox-coiogy, ind Mech anism ofAction," CRC Crit. Rev Toxicol. -3.319- 395 (19B4). Safe, S. ,N. Platonow, 0. Hutzingeran; w. 0. Jamieson. "Analysis of Organochlorine Metabolites in Crude Extracts by High Resolution photdplate Mass Spectrometry." Biomed. Hass Spectrpm. 2:201*203 (1975). Safe. S. . C. Wyndham, A. Parkinson, R. Pure./ and A. Crawford. "Halogmated Biphenyl Metaool ism,'* in Hyg*;caroons and Halo* genated Hydrocarbons in the Aquatic Enviro-*ent. B. K. Afghan and 0 Mackay, Eds. ( New rork, NY: Plenum Press, I960), op. 517-544. Safe, S. and R. K. Boyd, "Pesticide Anal,ii$ by Mass Spec* trometrv." in Pesticide Analysis Conf Pr;c . *. G. Das, Ed. (New orx: Ofkktr, i.981), pp. J29"i6e. Chew. Ap$t. 95: 110007b (19B1). , Safe, 3., A. Parkinson, t. Robertson, R. Ccckerline, l. Safe, S. Bandiera and A. Okey. "PCBs as AHH [r.aucers," in Chlor inated Oioxine and Related Compounds, 0. ruttinger, fi. w. Frei, t. Merian and F. Pocchiari , feds. (New York: Pergamon Press, 1981), pp. 383-392. Safe, 3., 1. W. Robertson, L. Safe, A. Pammson, S. Bandiera, T. Sawyer, and M. A, Campbell. "Halogenated Biphenyls; Mo lecular Toxicology," Can J. Physiol. Pharwa;ol.. 60:1057*1064 (1982). HONS 22387^ *30 Bibliography Safa, S. , M. Muilin, L. Safe, C. PocMni, S. McCrinole arid m Romkes. "High Resolution PCB Analysis," Chaoter 1 in Phvs. J 'cal Behavior of PCBs in The Great lakes. 0. Mackay. -- S. Paterson, S ' J. Eisenrei"ch and M. $. Simmons, Eds. (Ann Arbor. Ann Arbor Science Publishers. ]nc 19B3ai OP. 1-13 '' Safe, S, , l. Robertson, T. Sawyer, A, Parkinson, $. Bandiera l. Safe and M. Campbell "PCOOs and Related Compounds: Me* / tabolism and Biochemi stry in Human and Environmental Risks of Chlorinated O'omns anp Related Compounds, T T igcxer a"! C Young and A. P. Gray, l6i. (Hew fork, NY: Plenum Press, 19830), po. 393-403. Safe, S. , M. Muilin. l. Safe. C. Pochini and S. McCrinate 'Hign Resolution PCS (Polychlorinated Biohenyls) snalvSK." Environmental Research Laboratory, u$. Environmental Pro tection Agency. Ouluth. MN. EPA-600/0-03-095; NTIS No. P883* 246124; Chem. ftbstr 100:61153g (l?83c). Safe, $., A. Parkinson, L. Robertson, T. Sawyer and S. Sandiera. "PCBs (Polychlorinated Biphenyls): Structurey Activity Relationships," Environmental Research laboratory, U.S. Environmental Protection Agency, Washington, Q.C.. Epa600/063-096, NTIS No. PB03-247466 (1963d). Safe, S., A. Parkinson, L. Robertson, T. Sawyer, S. Bandiera. t. Safe, M. A. Campbell end H. Muilin. "PCBs: StructureActivity Relationships," in Advances in Exposure, Health and Environmental Effects of PCBs: "^ymoosTum Proceedings. 5" 7" davenport and 8. iT Bernard < Eds. ). ifTTce of fox-ic Sub- jtances, J.Z. Z.iv \ rcns-.en:-; '-Ttac-.-Tn iie"cv v^shinotan O.C., Report No. ISI-TR-S07-137B; NTIS No. PB-84-135771 (Oecemper 1963e), pp. 229-248. Sans, W, W. ''Multiple Insecticide Residue Determination us ing Column Chromatography, Chemical Conversion, and Gasliquid Chromatography," J Aqr, food Chem. 15-192-198 (1967). Saperstein, M. 0., R. J. Gordon and E. J. Faeder. "PCS Con tamination in Distribution Trans formers," J. Environ Sci. Health AU(2):241-2S1 (1902). Sarofim, A, F. "Properties. Production, and Uses in Poly chlorinated Biphenyls - Environmental Impact," Environ. Res. 5;258*273 (1972a). Sarofim, A. F. "Analytical Methods in Polychlorinated BiOhenyls - Environmental Imoact," Environ. Res. $330-340 (1972b). HONS 223877 Bibliography 431 Sarro, r. L. . 0. R Moore and 0. C. Ackerman. "Emissions Testing Ourmg Incineration of PCBs at Energy System*. Igm- pany, El Dorado. Arkansas,' Oraft Report py T9w, i-c., Redondo Beacn. CA. to Philip C. Scnwmqt. u.S. Env i ronmenta 1 Protection Agency. Region vI , Dallas, TX, EPA Contract ko. 6B-02-217A, work Assignment 56 (Septemoer 198 la), 171 pp. Sarro, T. l.. D. R. Moore and 0. G. Ackerman. "Emissions Testing Our mg incineration of PCBs atRollins Env 1 ronme*- i91 Services, Inc.. Oeer Park, Tx," Oraft Report Oy TRW, I-:., Redondo Beach, CA, to Philip C. Schwindt, U.S. Environmental Protection Agency. Region vl. Dallas, TX, EPA Contract ho. 68-02-3174, work Assignment 56 (Septemoer I9B10), 128 op. Sauter, A. 0.. P. E. Mills, W. 1. fitch and R. Dyer. "Inter laboratory GC/MS Response Factor Precision." J. High Resol, Chromatoqr, & Chromatoqr Common, 5:27-30 (1982). Savage. E. P , J. 0 Tessari. J. w. MalOerg, h w. Wheeler and J. R. BagOy. "A Search for Polychlorinated Biphenyls in Human Milk m Rural Colorado.'* Bull r-viron Contam. "*- icq 1 3(4): 222-226 U973aj. Savage, E. P. , J. 0. Tessari, J. W. MalOerg, H. w. Whee'er and J. R. Bagby "Organochlorine Pesticide Residues *nd Polychlorinated Biphenyls in Human Milk, Colorado-- 1971-72," Pestic. Monit. J. 7(1):1-3 (1973b). Sawyer, L. 0. "Collaborativt Study of the Recovery and Gas Chromatographic Quantitation of Polychlorinated Biphenyls -n Chicken Fat and Polychlorinated Biphenyl-00T Combinations in Fish," J. Assoc. OfMc. Anal. Chem. 56(4): 1015-1023 (1973). Sawyer, 1. 0. "Quantitation of Polycnlorinated Biphenyl Rsibues Oy Electron Capture Gas-Liquid Chromatograpny: Refe-- ence Material Characterization and Preliminary Study," Assoc, nfc Anal Chem 81(2):272-2S1 ('.978a). Sawyer, L. 0. "Quantitation of Polychlorinated Biphenyl Res idues by Electron Capture Gas-liQuid Chromatography: Collab orative Study," J. Assoc. Offic. Anal. Chem. 61(2):282-231 (19780). Schneider, J. F, S Bourne, and A. S. Boparai. "Parallel Capillary Column Gas Chromatography in the Oetarmmation :f Chlorinated Pesticides and PCBs," Journal of Chromatograph*z Science. 22 C1984) Schulte, i. and l. Acker. "Identifizitrung und Metaoolisie-barkeit von polychlorierten Qiphtnylen," Naturwissenschaften 61:79-80 (1974a). MONS 223878 Bibliography Schulte, Z ar,Q t. Acker. "Gas*Chromatographie <i,t dacap'IUren Dei Temperaturen bis iu 320C und ihre Anwendung 2ur Trennung von Polych1oPbipheny len." Fresenujs' Z Ana 1 Cha. 268(4) 2SO-2&7; Chaw. Abst. 81:1153771" ( 1974b): Schulte. E. . h. P. Thier and L. Acker 'Residual Analysts 0f PolychIorinatec 8'0henyIs in Foods of Animal Qng>n; E*pariancas and Proposals for Standardization," Otscn. Lebensm Rundsch. 72(7) 229-232 ( 1976), Cham. Abst. B5:'lJiB94h (l$7$)' Schulte. E. and R. Malisch. "Berecnnung der wahran Peg * Gehalte in UfTreitDroben l. Ermntlung d#r Zusammensetzung Zwatar Techmscnar PC8*Gemi sent," Fresemus' Z. Ana*. Cham 314:545-551 (1983) ' Schulta, E.. and R. Malisch. "Calculation of tna Real r3 Content -n nv>ronmantai Samples 11. las Chromatcgrapnic Jtermination of tna PCS Concentration in Human Milk nd Sui ter," Fnestnius' Z. Anal. Cham. 319:54-59 (1904). Schutjas, C. P. M. , E. A. Vermeer, G. J. Scherpenjeel. R. W Bally, and C. A. Cramers. "Practical Aspects of Fast Gas Chromatography on 50 [.0. Capillary Columns: Combination >th Electron-Capture Detection," Journal of Chromatography 28$: IS7-162 (1984). Scltwalb. A. L. and A. Marquez. "Salt River Project's Experi ence with the Horiba Sulfur/CMonne-in-on Analyzer," in Proceedings: 1981 PCB Seminar. G. Addis and J. Marks, Eds Report No. E^RI-El-2572 (alo Alto, CA: Electric Power Re search Institute. 1982), pp. 2*23. lenwart:. ?. M. , .. *. Jacooson, J. ram, J. L. Jacooson ano H. A. Price. "Lake Michigan fish Consumption as a Source of Polychlorinated Biphenyls in Human Cord Serum. Maternal Strum, and Milk," Am, J, Public Health 73(3):293-296 (1983). Schwartz, T. R, and R. G. Lehmann. "Determination of Poly chlorinated Biphenyls in Plant Tissue," Bull Environ. Contarn. Toaicol. 28:723-727 (1982). Schwartz. T. R., J. D. Petty, 0. L. Stalling. J. w. Hogan, M. X. Marlow. R. 0. Campbell and R. 1. Little, "a mump? (OSH-U) Oersved Data Base for Congener Specific PCB Analysis Leading to Pattern Recognition Studies." Abstract, 104th Annual Chemical Society National Meeting, September 12*17. 1962. Schwartz, T R. , J. 0. Petty and 6. M. Kaiser. "Preparation of n-Alkyl Trichloroacatatts and Their Use 4s Retention Index Standards in Cas Chromatography," Ana*. Cham. 55:1839*1840 (1983). MQNS 223879 Bibliography 433 Schwartz. T. R. , R. 0. Campbell. 0. 1. Stalling, R. Little, J. 0. Petty, J W Hogan and E. M. Kaiser. "laboratory Data 8ase for I$omer-$pctfic Determination of Polychlorinated Bi* Dheny's," Anai Cnem 56 1303*1308 (1984) Scinto. L. L. , p. A. Painter, A. M. fakata and T J. Hen* ntngs. '`Preliminary Operations Plan and Guidelines for the At-sea Incineration of Liquid PCS wastes/' Office of Research and Development, U.S. Environmental Protection Agency, Re* search Triangle Park, NC, EPA-6Q0f2-82*06B, NTIS No. PB83181834 (1982). Seiber, J. N. "Reversed*Phase Liquid Chromatograpny of Some Pesticides and Related Compounds. SolubIityRetent ion Re* lationships." J. CHromatoqr. 94:151*157 (1974). Seidl. G. and K. Ballscnmiter. "Isolation of PCB's from Soil. Recovery Rates Using Qifferent Solvent Systems/' Chemosphere 5:373*376 (1976a). Seidl, G. and K. Ba11scnmiter. Isolation of PCB's from vegetable Oils: Recovery and Efficiency of "Clean Up* Methods," Chemosohere 5:363-366 (1976b). Seidl, G. and K. BeUschmiter. "Quantitation of Polychlori nated Biphenyl (PC8)-Re$idues after Hydrodecnlorination to Biphenyl Using Liquid Chromatography with UV-0etect'on/` Fresenius' Z. Anal. Chem. 296:281-264 (1979). Serum. J. W. , S. C. Tong, L. E. St. John Jr.. C. A. 8ache, 0. R. Mertens and 0. J. Usk. "Electron-Capturing Compounds and Selected Elements in Paper," Bull. Environ Contem. Tox icol. 10(2):88-96 (1973). Sevcik, J "Oetectors in Gas Cnrematograpny/' J. Chromatogr. I i brarv Vol. 4 f New vork. ny- c/ Sc* ent*. *'r. Pub- lisntrs, 1976). Sexton, f. W. and 0. E. Lentzen. "Audit of tne vuicanus In cineration Ship Prior to tne August 1982 PC8 Burn. Mobile, Alabama," U.S. Environmental Protection Agency, Office of Re search and Development, Industrial Environmental Research Laboratory. Research Triangle Park, NC, Report No. EPA-600/ 7-83-023; NUS No. P883-193698 (April 1983). Shahied, S. 1., R. P. Stanovick, 0. 1. Mclnturff and E. Missagni. "Determination of Polychlorinated Biphenyl (PCB's) Residues in Grades of Pulp, Paper and Paperboard," Bull. Environ. Contem. Toxicol. 10(2):8Q*87 (1973). MONS 223880 434 Qibiiograony Shaw. 0. G. "0scrtmination 8et*een PCB and 00T Residues Cy a Gas Chromatograpnic-Mass Spectrometry Technique," 9uu Environ Contam. rpicol 8(4).208-211 (1972). ` Shaw. G. R. , h. C. Chapman and G. W Roache. "Determination of Organochlonne Pesticide* and Polycniormated Biphenyls Sediment Samoies Containing Oil Residues.'1 Residue (Melbourne 3( 2 ).2-8 ( 1976); Chem. ftbst. 88:1362y (19781" -------------------------- - Shaw, G. R. and 0. W. Connell. "Physiochemical Prooerties Controlling Polychlorinated Bioheny) (PCB) Concentrations m Aouatic Organisms," Environ $ci. Technpl 18:18-23 (1984) Sherma. J. "Gas-Chromatography Analysis of Polychlorinated 8iphenyis and Other Nonpesticide Organic Pollutants.' Chapter 5 in Advances in Chromatography, J. C. Giddings, . Crusnka. R. A. Keller and-T Cazes. Eds. (New York, ny- Marcel Oekker. Inc.. '.?75i, pp. 141*175 Sherma. J. Manual of Analytical Quality Control for Pesti cides and Related Comoounds m Human and n i ronmental lamplesT &PA-6M/j*ffI-0BT7 nTIS no. minimi (Aon l 1981) Shirai, F. "Qetection of Polychlorinated Terphenyls on Food Wrappers by Reversed'Phase Partition Thin-Layer Chromatog raphy," Eisei Kaqeku 20(5): 282*286 (1974); Chem. Abst. 82: 84S59t (1$75). Skrentny, R. F. , R. W. Hemken and H. w. Dorough. 'Silo Seal ants as a Source of Polycnloropiphenyl (PCS) Contamination of Animal feed." Bull Environ, Contam. Toxicol 6(S):4Q9-416 (1971). Simon C. ri *nd r c. 9irt)r"r. "Timoling ti-ior-* j- cnionnatefl Biohenyls with Polyurethane Foam--Chro*atograonic Approach to Oetermininq Retention Efficiencies." Anal. Chem. Sl(8);1110-1113 (1979). Singer. E., T. Jarv and M. Sage. "Survey of Polychlorinated Biphenyls in Ambient Air Across tne Province of Ontario," Chapter 19 in Physical Behavior of PCBs in the Great Lakes. 0. Mackey, S. Paterson. $. J. Eisenreich and M, V. Simmons, Eds. (Ann Arbor, HI: Ann Arbor Science Publishers. Inc., 1983), pp 367-383. Sissons, 0. and 0. Welti. "Structural Identification of Polycnlorinated Biphenyls in Commercial Mixtures by GasLiquid Chromatography, Nuclear Magnetic Resonance and Mass Spectrometry," J. Chromatoqr. 60:15*32 (1971). MONS 223881 Bibliography 435 Siyjli. 0. $ "Polychlorinated Biphenyls, HexachloroDeniene and Other Crganocnlorine Pesticides in Hyman Milk " Med J Aust. 2.015-818 ( 1973). --------- Sleignt, S. Q. "Pathologic Effects of PCBs in Mammals." in PCBs: Nyman and Environmental Hazards. F M. D'ltri and M. A Kamrm, Eds. (Boston: 8utterworth Publishers, 1983), pp. 215-226. Smith, A. 8., J. Schloemer, i. K. Lowry, A. w. Smallwood. R. N. Ligo, $. Tanaka, w. Stringer, M. Jones, R. Hervin and C. J. Giuec*. "Metaoolic and Health Conseauences of Occupa tional Exposure to Polychlorinated Biphenyls." 0r. J. Ind. Hed. 39:361-369 ( 1982). Smith. G. C. , G. A. Gauger and R. M. Frey "Using Capillary Gas Chromatograohy to Oetermine Polychlorinated Biphenyls (PC8s) in Electrical Insulating Liquids," IEEE Trans Power Appar Svst. PAS-10K 7):2260*2267 (1982). Chem Abstr. 97: 229462c (1982) Smith. J. "Quanty Assurance Plan ror Measurment or Inciden tally Generated Chlorinated Biphenyls (PCBs)," Unpublished Memorandum, u.$. Environmental Protection Agency. Office of Toxic Substances, Washington, 0C, April 6, 1982. Smith, l. M. , 0. L. Stalling, and J. L. Johnson. "Determina tion of Part-per-Tri11 ion Levels of Polychlorinated Qibenzofurans and Oioxins in Environmental Samples," Anal. Chem. 56: 1830-1842 (1984). Smodlake, N. "Unidentified Compounds in Seewater Chromatographically Similar to PC8s." Marine Pollut. Bull. 5:84*86 (1974); Chem. Abstr. 83:12063d (1975). Smrek. A. l. and L. L. Needham. "Simplified Cleanup Proce* lures 'or Adioose T>ssue Containing oclvchlortnated Bi phenyls. 00T, ana DOT Metabolites," flu)). Environ, Contan. Toxicol. 28:718-722 (1982). Snyder, 0. and R. Reinert. "Rapid Separation of Polychlori nated 8 i phony Is from 00T and Its Analogues on Silica Gel," Bull. Environ. Contam. Toxicol. 6(5):385*390 (1971). Snyder, l. R. and J. J. Kirkland. Introduction to Modern liouid Chromatography, 2nd Ed. (Hew York, N'T; Wi ley- Interscience, 1979), 863 pp. Sonchik, S., 0. Madeleine, P. Macek and J. Longbottom. "Evaluation of Sample Preparation Techniques for tne Analysis of PCBs in Oil," J. Chromatoor. Sci. 22:265-271 (1904). MONS 223882 436 Bibliography $p*w, $ H. , 0. R. Pendleton ana J. M. Jenks. "Environmental Sampling and Analysts of Airborne Contaminants Identified as Skin Irritants: Ceer Park, Texas." in Proceedmos: A sne- cialty Conference on: Heasurement and Monitoring pf son- ' cr~iter^a (Toxic) Contaminants > -I Air] . (T~ Frederic*. d (Pi t tsDurgh: i fie Air Pollution Control Association 1303 ) pp. 156*167. ' Spearman. fl. I. C. " 6ocfiemi i try of Adipose Tissue and its Regulation," in Trie Physiology and Pathophysiology of tne Skin (London. New rorx: Academic Press, 198?), pp. 2233 2175; Chem. Apstr 98: W6S4& (1962). Spies. 0. N. "Rapid Field Extraction Technique for Oeter* mining Extent of PCB Contaminated Sediments." in Hazardous Materials Spills. Conference Proceedings. J. Ludwigson Ud } pp. 435*437 7198277 Cnem. Apst. 97760688t (1982) ' Spittier, T. M. Fieid Measurement or PC8's m Son ano >eo- iment Using a Portaple Gas Chromatograph." Natl. Conf. uanaoe Uncontrolled Hazard, waste Sites, pp. 105-IoT (1983), t^cm ' Abst. 100:220890p (1904). * Spittler, T. M. "Field Measurement of Polychlorinated 8i* phenyls in Soil and Sediment Using a Portable Gas Chromato* graph," in Environmental Sampling for Hazardous wastes. G. E. Schweitzer and J. A. Santolucito, Eds.. ACS Symposium Senes 267 (Washington, 0C, American Chemical Society, 1984) pp. 37* 42. Stahl. E., Ed. Thin-Layer Chromatography: A Laboratory Handbook (New York: Springer-Verlag, 1969) ~ Stahr, H M. "Analysis Of C2s Ov Th n-ivn*apny," J. Liq. Chromtogr, 7( 7): 1393*1402 (1904). Stalling, 0. 1. "Analysis of Organochlorine Residues in Fish: Current Research at the Fish-Pestlcide Research Labors atory," in Pestic. Chew., Proc. Inti. IUPAC Conqr, Pest. Chem.. 2nd 4:413*li& (1571). Stalling, 0. L. "Application of Analytical Methods Research to Monitoring Organic Residues in fish," The Institute of Electrical and Electronics Engineers, Inc., Annals No. 75CH1004-I 7*5 (1976). Stalling, 0. L. and J. N. Hucktn*. "Gas-Liquid Chromatog raphy-Mass Spectrometry Characterization of Polychlorinated 0iphenyls (Aroclors) and 36CI'Labeling of Aroclors 1240 and 1254." J, Assoc. Offic. Anal. Chem. S4(4):801*807 (1971). MONS 223883 Bibliography 437 Stalling,'0. 1. . * C T-ndleandJ. L. Johnson. "Cleanup of Pesticide and Po'yeniorinated Biohenyi Residues in Fish Ex tracts by Gel Permeation Chromatography" j Assoc Offic Anal Chem 550.3708 (1972). ' --------------------------------------------------- Stalling, 0. 1. and J. N, Huckins ''Reverse Phase Thin Layer Chromatography of Some Aroctors, Halo*a*es, and Pesticides." J. Assoc. Qffic. Anal. Chem. 56(2):367-372 (1973). Stalling, 0. L. . J. Johnson and J. N. Huckins. "Automated Gel Permeation-'Caroon Chromatographic Cleanup of Dioxins, PCBs, Pesticides, and Industrial Chemicals," in Environmental Quality and Safety, Supplement Vol. III. Pesticides lectures of WlUPAC, Third International Congress of Pesticide Chem istry, Helsinki. July 1974, F Coulson and F korte, Eds. (Stuttgart, Germany: G. Thieme Publishing, 1975), pp. 12-18. Stalling, 0. L., J. N Huckins. J, 0. Petty, J. 1. Johnson and H. 0. Sanders. "An Expanded Approacn to the Study and Measurement of PCBs and Selected Planar Halogenated Aromatic Environmenta1 Pollutants," Ann. N Y. Acad. Sci. 320:48-59 ( 1979a). Stalling, 0. L., L. M. Smith and J. 0. Petty. "Approaches to Comprehensive Analyses of Persistent Halogenated Environ mental Contaminantsin Measurement of Organic Pollutants in Water and Wastewater, ASTM STP686. C. E van Hall,' Ed. (American Society for'testing and Materials, 1979tt>, pp. 302 323. Stalling, 0. L, , J. N. Huckins and J. 0. Petty. "Presence and Potential Significance of o-o'-Unsubstituted PC8 Isomers and Trace Aroclon# 1248 and 1253 Impurities," in Hydrocarbons and Halogenated Hydrocarbons in the Aouatic Environment, ST Afghan and fi. Mackay, Eds. (New York: Plenum Press 1980a), pp. 131-139. Stallino, 0. L. . J. 0. Petty, G. R. Oubay and R. A. Smith. Application or lC/MS to uhromatograpmc reparation or Aro matics Using Carbon as the Stationary Phase," J. Chromotogr. Sci. 18:107*106 (1980b). Stalling, 0. L. , J. 0. Petty, L. M. Smith and G. R. Oubay. "Contaminant Enrichment Modules and Approaches to Automation of Sample Extract Cleanup." Chapter 9 in Environmental Health Chemistry. The Chemistry of Environmental Agents as Potential Human Hazards, J, Q. McKinney, Edi (Ann Arbor, Ml: Ann Arbor Science^ubi ishers, Inc., 1981), pp. 177-193. HONS 223884 *3 . Bibliography Stalling, 0. 1. . J. 0. Petty. 1. M Smith. C. flaooe. ana H R Buser "Isolation ana Analysis or Polycnionnateo Furans in Aauatic Samples," in Chlorinated Qioxms ang Pe. lated Compounds: Impact on the EnyTronment. 0- HutT'"nger- R. w Fret, . Henan. F Pescnan. Eds. (Pergamon P**ess 1982) ' Stan. H.-J. "Combined Gas Chromatography-Hass Spectrometry,1' Chapter 9 in Pesticide Analysis. K. G. Das. Ed. (New tor*Marcel Dekker. {nc.. 1981). pp. 369-423. Stanley, J.. C. Hail*. A. Small and E. Olson. "Sampling ano Analysis Procedures for Assessing Organic Emissions from Sta tionary Combustion Sources for E*ooSure Evaluation Division Studies Methods Manual," U.S. Environmental Protection Agency, EPA-560/5-82-014 (1982). Stanley, J. $., M. 0. Erickson. J. K. Turman. G. Radolov'ri <. jnstot, <., 3auer ana J. c. Going. Relative Response fac tors ana Relative Retention Times of PCBs Obtained oy Caoii- lary GC/ElMS." Abstract No. 801 presented at the 1993 PittsPurgn Conference and Exposition on Analytical Chemistry and Applied Spectroscopy, March 7-12, 1983. Stanley, J. S., C. 1. Haile, A. M. Magin. 8. V. Northcutt and 0. P. Bedford. "Quality Assurance Program for Compustion Source Studies," in Identification and Analysis of Qroamc Pollutants in Air, l. H. Keith, EcT (Boston: Sutterwortn Publishers, 1984), pp. 459-473. Stanovick, R. P., S. Shahitd and E. Missagni. "Determination of Polychlorinated Biphenyl (Aroclor 1242) Migration Into Food Types." Bull, Environ. Contam. Toxicol. 10(2):101*107 (1973). Steichen, R. J., R. G. Tucker and E. Mechon. "Standaroi:a* tion of Aroclor Lots for Individual-Poak Gas Chromatograpnic Calibration," J. Chromatoor, 236:113-126 (1982). Steinwandttr, H. "Contributions to Silica Gel Application m Pesticide Residue Analysis," Presents' 2. Anal. Chem. 312'. 342*345 (1982a). SUinwandttr, H. "Contributions to the Application of Gel Chromatography in Residue Analysis," Freseniut' 2. Anal Chen. 313:536-538 (1982b). Steinuandter, H. "Contributions to Silica Gel Application >n Residue Analysis. v. Simple Micro Method for Liquid Chro matographic Separation of Chlorinated Hydrocarbon Pesticides and Polychlorinated Sipnenyls (PCS's), Presents' 2. Anal Chem 316(5):493-494 (1983). MOMS 223885 Bibliography 439 Steinwandter, h. "Chlorination of Organic Compounds.* II. Kinetics of PC3 Perch lor mat ion," Presents' l -Aal Chem 317:869-871 ( 1984) ---------------------------------------------- "" Steinwandter. H and H. Bruent. ''Chlorination cr Organic Compounds. I. A Simple 10 Min Perchlorination Tecnnioue for the Quantitative Determination of Polychlorinates Biphenyls (PCS's)," Presents' l. Ana) Chem, 314(2).160 (1933). Stenhagen, E , S. APrahamsson and F. w. Mctaffert/ Rrgistry of Hass Spectra I Qata Vo). 1*4, Wiley, New fort ( 1974) Stijve. T. and E. Cardinal*. "Rapid Determination of Chlor inated Pesticides, Polychlorinated Biphenyls, and a `lumper of Phosphated Insecticides m fatty foods," Hitt. Gao lebensmittelonters. hvq. 65(1):131-150 (1974); Chem -dst. 32: 137862v (1975). StoUenpurg, T R. and A. w. Andr^n, "Oeterminat' :n of the Aoueous Solubility of 4-chiorooiohenvI." Anal !*;-n. Acta 151(1).271*274 ( 1983). ' Strachan, w. m. J. , H. Huneault, w. M. Schertter, and F. C. Elder. "Organochlorines in Precipitetion in the Great Lakes Region," in Hydrocarpons and Haloqenated Hydrocarbons in the Aquatic Environment, 8^ Afghan and 0. Mac*ay. :ds. (New York: Plenum Press, 1980), pp. 387-396. Strachan, w. M. J. , and H. Huneault. "Automated Ram Sampler for Trace Organic Substances," Environ, Sc>. Tecnnpl, i&; 127-130 (1984). Stratton, C. L. and P. C. Geisjler. ''Analysis of p:lycMormated Biphenyl (PCB) in Human Blood Serum Samples. Report prepared for u.S. EnvironmentaI Protection Agency. E;4-56Q/6's*co7. *:r:s 'io "2-:?: .:5a/s Cc.cscr Stratton, C. L. . K. L. Tuttle arid J. H. Allan. Environ mental Assessment of Polychlorinated Bfohenyts (POSs) near New Bedford, HA Municipal Landfill," Report prepareo ror u.S, Environmental Protection Agency, Report No. EPA 560/9-78-006 (May 1978a). Stratton, C. L. , S. A. Whitlock and J. M. Allan. 'a Method for the Sampling and Analysis of Polychlorinated Biphenyl (PCI) in Air," Report prepared for U.S. Environmental Pro tection Agency, Report No. EPA-600/4-78-048, NT IS No. P8 268 410/4 (August 1976b). HONS 223886 440 Bibliography Stratton. C. L. , J. M. Allan and S. A. Whitlock. "Advances in the Application of the Perenlorination Technique for the Ouantitation and Confirmation of Polychlorinated 8ipneny)$ (PCBs)," Bull Environ Contain roico' 21:230*237 (1979) Strauo, C. P. and J. m. Sprafka. "Environmental Levels or PCB in Great Lakes Pish," Environmental Research Laboratory, U.S. Environmental Protection Agency. Oututn, MN, EPA-500/ 8*83*094. NT1S No. PB83-264481 (1983). Strlk, J. J. T, w. A., F, M. H. Debets and G. Koss. "Chem ical Porpnyri a.Chapter 7 in Haloqenated Biphenyls. rrphenyls. Naphtha lenes. Oibenzodioxms and Related Products, R. 0. Kimprougn, Eo. (N*w rorn: 61 sevier/Nortn-oI Iano Bio medical Press, 1980). pp. 191-240. $u, G. C. C. and H. A. Price. "Element Specific Gas Chro matographic Analyses of Grganocnlonne Pesticides m the 5r*sence or ?C2' by Cvecf/e ;,ncei iation or Interfering Peaks." Aqr, Pood Chem, 21;1099*1102 (1973). Sundaram, X. M. S and P. G. Oavis. "Analysis of OOT Residues in Animal Tissues and Soils Collected from Oifft rent Regions of Canada," File Rep. * Chem. Control Res, Inst. . Ottawa 3: 63 pp. ( 1974)rCheffi. Abst. 82:939521 (19757 ^ Sundstrdm, G. and C. A. Wachtmeister. "Synthesis of `Re labelled and Unlabelled PCS Compounds." in PCS Conference 11. National Swedish Environment Protection Board, Stocknolm, Publications 1973:4 (1972), pp. 73*86. Suftdstrom. G.. 0. HutZinger, F W. Karasek and J. Micnnowicz. "Environmental Chemistry of SuPstitutes for Polycniorinated Biphenyls. I. Comoosition and Prooerties of an AUvlchlor*>wipneny. r roouct. * *ssoc- 3rfic. *nat. them 59(5) 982-?58 (1976). Suoelco, Chromatography Supplies Catalog 20. p. 26. Sutcliffe, C. R. and S. 0. Nielson. "Adsorption of Poly chlorinated Biphenyls on Glass Surfaces," Presented at FACSS 10th Annual Meeting, September 25*30, 1983. Swain, W. R. "An Overview of the Scientific Basis for Con* cern with Polychlorinated Biphenyls in the Great lakes." *n PCBs: Human and Environmental Hazards. F. M. 0`ltri and M. A. Kamrin, ds. (Boston: Buttervorth"Publishers, 1983). pp. 11* 48. HONS 22398? Bibliography 44 \ Sw#nsort, $ . , m 0 '>c*son, and l. Hooe. "Products of Thermal Degradation of 0-e'ectnc Fluids." - j Env i r-onmenta I Protection Agency. Office of Toxic Suosta-;*? Report No EPA-560/5-25-022 (1985) 23 pp. Swift, R and H. Settle. "A Procedure for *.* Determination of Polychlorinated Biohenyls in Fat Sadies." Residue (Melbourne > 3(2): 9* 12 (1976 ); Chew. Abst. 67 99289a Swonyn, E M. and 0 G. Ackerman. "Inter-* Guidelines for the 01sposa l/Oestrue11on of PCBs and PCS Ite** oy Non-tnermal Methods," Environmental Protection Agency. i:ntract No. 68 02-3174. Task 41. Report no. EPA-600/2-82-069 (1981) Sworjyn, E. M. and 0. G Ackerman, "Inter-* Guidelines for the 0i sposa1/Destruction of PC8s and PCB Ite'-? oy Non-thermal Hetnods." Office of Research and Development. u.S. Environ mental Protection Agency. Research Triangle *srk. NC EPA* 600/2-32*069; NT 1S No. P882-217 490. 177 pp. 1982). SreiewsKi, J , 2. R. Min. S. J. Spiege1 --o t. t. Tifft, Jr. "Loss of Polychlorinated 8iphenyi Hc-jlogues during Chromium Trioxide Extraction of Fish Tissue.1' Anal. Chem S1( 14):240S-2407 ( 1979). Tahiliani, V. H. . "CLOR-N-OIL Field Test P-:gram," in Pro ceed! nos; 1983 PCB Seminar. G. Addis and R f. Komai, Eds. Report No. PRI*6L-3S61 (Palo Alto. CA: Electric Power Re* search Institute), 1904. Tai, H. , M. T. Williams and K. 0. McMurtrey "Separation of Polychlorinated Biphenyls from Toxaphen* by S icic Acid Col* umn Chromatoaraohv." Bull Environ. Contam. Tcjicol 29:64*67 (1982). Takamiya, K. "Perchlormation Reaction Aopl*: to tne Rapid Determination or PC0S, suit. Environ. Cunta* *uxico<._ 30; 600*605 (1983). Takei, G. H. . $. M. Kauanikaua and G. H. Leone. "Analysis of Human Milk Semples Collected in Hawaii for Residues of Or* genochlorfne Pesticides and Polychlorobiphen;. s." Bull. En viron. Contam. Toxicol. 30:606*613 (1983). Takeshita. R. and T. Yameshita. ''Reversed':iase Partition Thin-Layer Chromatography of Chlorinated Ptstv:ides and Poly chlorinated Biphenyls,'' Eisei Kadlku 18(6): :ES*392 ( 1972); 'Chew, Abst. 78:144191w (1973T ' MONS 223888 442 Bibliography Talhelm. 0. R. "Economic Jmoacts of PC8 Regulations in Foca and Fisn." in PCBs Human and Environmenta1 Hazards, f. h Q'ltri and M. A. kamnn. Eds. (Boston; 8ult#rwOrm Puolisners. 1983), pp. *09*422. Tanabe, H "Methods of Analysis of PCS (Polychlorinated Bi phenyls) in Edible Oil and Fat," Yukagaku 22(1):3S-40 (1973) Chem. Apst. 78:11978Jn (1973). ' TanaPe. H. "PC8 Microana1ysiS ," in PC8 Poisoning and Pollu tion, x. Higucni. Ea. (Tokyo: Kodansna,~iLtd; New torn: 5caT deenc Press 1976), pp. 127-146. Tanabe. S . and R. Tatsukawa. "Chlorinated Hydrocaroons n the North Pacific and Indian Oceans." Journal of the Qceanp* qrapmcal Society of Japan 36.217-226 (1980). ' Tanabe, S. , M. Kawano, and R. Tatsuxawa. "Chlorinated Hydro carbons m the Antarctic, Western Pjc'.fic. and Eastern lie-in Oceans," Transactions of the Tokyo University of Fisner's S. 97-109 (1982). Tanabe, S. and R. Tatsukawa. "Vertical Transport and Resi dence lime of Chlorinated Hydrocarbons in the Open Ocean Water Column," Journal of the Oceanographical Society of Japan 39:S3-62 (1983). Tanabe, S. , H. Hidaka and R. Tatsukawa. "P8$ and Chlori nated Hydrocarbon Pesticides in Antarctic Atmosphere and Hy drosphere.' Chemosphere 12(2):277-263 (1983). Tanner, H. A. "Regulation of PC8s in Michigan," in PC9s Human and Environmental Hazards, f M. O'ltn and M Kamnn, q$. (8oston: 8utterworth Publishers, 1983). A ;d. :*7'-2. Tarradellas, J. , P. Oiercxsens and H. 8, Souche. "Methods of Extraction and Analysis of PC8s from EarthwormsIntern, j. Environ, Anal, them. 13;55*67 (1982). Tas, A. C. and R. H. de Vos. "Character!tation of Four Major Components in a Technical Polychlorinated Biphenyl Mixture," Environ. Sci. Ttcftnol. 5(12); 1218-1218 (1971). Tasv A. C, and R. J. C. Kleipool. "Characterization of the Components of Technically Polychlorinated 8iphenyl Mixtures' ll, " Bui). Environ. Contam. Toxical. 8(1):32*36 (1972). Tatsukawa. R. and T. Wakimoto. "Pollution Analysis. Deter mination of Polycnlorinated Sipheny) in Soil," Kooai Bunsexi Shishin 6:45*56 (1972), Chem. Abst. S2.U793e (197?) MONS 223B9 Bibliography 440 Tauten, M. . C- Stenl'k and H Wihiidal. "Analyse vonOrgano* cnlorpestizid-und PCB-Ruckstjnaen >n fischen mittels Kapil1 argaschromatoqrapnie/Massen$Decktrometrie," Chromatooraoha 14(7);403-410 (1981) Baylor, j. k. "validation of Analytical Methods." Anal. Chem. 55(6): 600A-608A (1983). Teichman, J. , A Bevenue and J. W. Mylin. '"Separation of Polychlorooipheny1s from Chlorinated Pesticides in Sediment and Oyster Samples for Analysis hy Gas Chromatography,'* J Chromatoqr, 151:155-161 (1973). ' Telling, G. M. and 0 J. Sissons. "Determination of Organo* cnlorme Insecticide Residues in Patty Poodstuffs using a Clean-up Technique Based on a Single Column of Activated Alumina." Journal of Chromatoqrapny. 137.405-423 ( 1977). Tenzner. R. 8. Ford, Jr., w. Mattox, and J. E. Brugger. "Mo bile System for the Detoxification/Incineration of Cleanup Residuals from Hazardous Material SoiUs." in Qisoosal -if Qil ano Oepns Resulting from a Spill Cleanup OperatTonTASTM TT? 703, J. s. Farlow and C. Swanson, Eds.", American Society for Testing and Materials (1980) pp. 118-136. Tessari, J. 0. "Analytical Methods for PCBs in Human Milk," Env Chem: Human A Animal Health 5:227-229 (1977). Tessari, J. 0. and E. P. Savage. "Gas-Liquid Chromatographic Oetarmination of Organochlorme Pesticides and Polychlori nated Biphenyls in Human Milk." J. Assoc. Offic. Anal. Chem. 63(4): 736*741 (1980). Tessari. J. 0.. l. Griffin and M. J. Aaronson. "Comparison of Two Cleanup Procedures (Mills, Onley, Gaither vs Automated Gel Permeation) for Residues of Organochtorine Pesticides and Pn1venlor'n*ted Bioh^vis u,"*Mn Adipose ';`jue." ull Environ, Contain. Tokico! . 25:59-64 (1980). Thielemann, H. "OUnnscMcht-chromatographi sche Auftrennung und Identifizierung eines Gemisches von polychlorierten Bi phenyl en (PC8) und p.p'-OOE an parraffinimpragnierten Kieselgur G-Schichten." fresenius1 Z. Anal. Chem. 282:144 (1976). Thielemann, H. "Ounnschichtchromatographische Nachweisgrenzen (semiquantitative Bestimmung) von polychloriertem Biphenyl (Chlophen Aso$) sowie Identifizierung des Insektizids Thiodan (Endosulfan)l. Chem, 18:147-148 (1978). MONS 223090 U4 Bibliography Thiel tminn, h. "Separation ana Ident Meat ion of Polychlor inated Biphenyls ana p,p''00E in Paraff1n*Impregnatea Com mercial Sheets by Repeated Thin-Layer Chromatograony," 2. Gesamte Hvg Ihre Grenjqeo. 26(6).463-464 (1980). Chem aort *4:2QZZ0fia U981). ' Thoeiann, R. v. and J. P Connolly. "Age Oeoendent model of PCB in a Lake Michigan Pood Cham." U S. Environmenta' Pro tection Agency, Report no. EPA-60Q/3-84*Q26. hTI$ P86A-\SS993 (1984). 122 PP. Thomann, R V and J. A. Mueller. "Steady State Modeling of Tox 1 c Chemica l* Theory and Application to PCS s m the Great lakes and Saginaw Bay." Chapter 16 in Physical Behavior of PC8s m the Great Lakes, 0. Mackay. S. Paterson? S. J. Eisenreicft and M. S. Simmons. Eds. (Ann Arbor. MI Ann Arbor Sci ence Publishers, Inc., 1983), pp 283*309. Thomas, R. L. and R. Prank. "PC8s in Sediment and Fluvial Suspended Solias in the Great Lakes," Chapter 14 in Phys cal Behavior of PC8s in the Great Lakes, 0. Mackay, S. Paterson, S. J. E'senre'Ch and M. $. Simmons, Eds. (Ann Arbor, Ml: Ann Arbor Science Publishers, Inc., 1983), pp 2^5-267. Thomson, B. A. and J. 8. Roberts. "The Development of an Analytical Technique for the Rapid in si tu Detection of PCBs and Trichlorobenzene in Clay," in A*Tase Study of A Spill pf Industrial Chemicals*Polychiorinated frToneny ;V anp CMpr;nated Benzenes, National Research Council ot Canaoa. Associ ate CommTttee on Scientific Criteria for Environmental Qual ity (NRCC No. 17586), Section vlI (Apoenai* 2 ) ( 1980) 22 PO. Thomson. 8. A . T. $akue. J. Fulford, 0. a Lane. n. m Reid, and J. 8. French. "Fasj. l_n S i tu Measureisent of PC8 levels in Ambient Air to ng M - Levels Using a Mobil Atmo* spheric Pressure Chemical Ionization Mass Soectrometer Sys tem," in Advances in Mass Spectrometry, vol. 88, a. Quayle. Ed., (Heyaen and Son Ltd. . London, 1980) pp. 1422-1428. Thomson, 8. A. Rapid Analysis Siphenyls," (1982). and J. 8. Roberts. "A New Technioue for the of Soil for the Presence of Polychlorinated Intern. J. Environ. Anal. Che*. 11;129*1S1 MONS 223891 Bibliography 445 Tiernn. T 0.. M L. Taylor. J G Solch. G. f Vanness, J. h. Garrett and M. 0 Porter. "Incineration or Chemical wastes Containing Polychlorinated Sip^enyls Assessment of 1 ests Conducteo at Rollins Environmental Services. Oeer Park. Te*as. and Energy Systems Company. El Ooraao. Arkansas." Chapter 9 in Oetoncation of Hazardous waste. J H E^ner, Ed. (Ann Aroor. Ml: Ann Arbor Science Publishers. Inc , 1982). pp 143- 183. Tindall, G. w. and P. E. winingtr. "Gas Chromatography-Mass Spectrometry Method for identifying and Determining Polychlo rinated Biphenyls." J. Chromatoor 196:109*119 (1980). Tindle, R. C. and 0. 1. Stalling. "Apparatus for Automated Gel Permeation Cleanup for Pesticide Residue Analysis. Ap* plications to Pish Lipids." Anal. Chem. 44( U). 1768-1773 ( 1972). Tofflemire. T. J. . T. T. Shen and E. H. Suckley "volatili zation of PC8 from Sediment and Water-. Experimental and field Oata." Chapter 21 in Physical Behavior of PC8s in the Great Lakes. 0. Mackay, S. Paterson, $. j. Eisenreicn and M. S. Simmons, Eds. (Ann Arbor, Ml: Ann Arbor Science Pub lishers, Inc., 1983), pp *11**22. Tpng. H. Y.. 0. L. Shore, and F. W. Karasek. "Identification of Organic Compounds Obtained from Incineration of Municipal Waste by High-Performance Liquid Chromatographic fractiona tion and Gas Chromatograpny-Mass Spectrometry," Journal of Chromatography, 285:423*441 (1984). Trench, w. C. "New PC8 Rulemaking * A Repeat of History or final Conclusions?" in Proceedings: 1981 PC8 Seminar. G. Addis and J. Marks, Ids.", Report no. EPRI-El-2S72 (Palo Alto, CA: Electric Power Researcn Institute, 1981). Section 1. PP. 11-34. Tress I. G. and K wessely. "Analysis of Chloropesticioes and PCS'* in Cheese by C14Ss Capillary GC/MS Using the Selected Ion Monitoring Technique," Application Note an 176-22, Hewlett-Packard Company, Avondale, Pennsylvania (1976). Trevisani, G. R. "Simultaneous Studies on Chlorinated Pesti cides, Polychlorinated Biphenyls, Polychlorinated TriDhenyls, and Polychlorinated Naphthalenes in fatty foods of Various Types," Soil. Chim unione Ital. tab. Prov . &arte Sc; 6(2): *17-142 (1$80); Chem. Abst 93:202765j (1980). Trotter. W. J. "Removing the Interference of 00T and Its Analogs in the Analysis for Residues of Polychlorinated Bi phenyls," J assoc. Qffic. Anal, Chem. 58(3):461*465 (1975). HONS 223892 Bibliography Trotter. w J. and S. J v Young. "limitation on the use of Antimony Pen t acn I Of 1 de f0r Pe rch 1 ori na 11 on of Po 1 ych) or i n*teO 6'onenyis." J A$$0C OffiC. Anal. Chffl 58(3) 4&fi-4fiA {1975) '' Trotter, w J. . S J. V. Young, J. I,. Casterline. Jr. , J. a &r*gl*w eno i. 8. Kamos "Industrial Cnemcals: induction of Aryl Hydrocarbon Hydroxylase Activity in Cell Cultures by Aroclors, Residues from YUsno Oil Samples, and Polycnlon- natefl B'enenyi Residues from fisn Samples." J. Assoc Off Anal, Chem 6S(4);838-841 ( 1982). ' Tjuthimoto. C.. S. Asano. J. E. TroskO and C-C. Chang, "In* rnbition of Intercellular Communications by Various Congeners of Polyorommated Biphenyl and Polycnlorinated Siohenyl." in PCBs~ *uman and Environmental Hazards. f M. O'ltn ana M. a Kamrin, Eos. (Boston- Butterworth Publishers. 19B3) DD. 241-252. Tuinstra. 1. G. M, Th. and w. A. Traag. "Automated Glass Caoillary Gas Chromatograoic Analysis of KB ano OrganocMorine Pesticide Residues in Agricultural Products." J. High Resol Chromatoor. i Chromatoor, Common. 2: 723-72B U979a). Tuinstra. i. G. m. Th. and w. A. Traag. "Automated <GC)' Analysis of PC8 and Organochlorine Pesticide Residues :n Agricultural Products." Med. faC. lanflOouww. Rijksun'v. Gent 44(2) 885-893 (1979b). Tuinstra. l. G. M. Th , w. A. Traag and h J. Keuken*. "Quantitative Oetermination of Individual Chlorinated Bi- onenyls in Milk fat, by Sblit'ess Glass Capillary Gas Chroma- tograpny,'' J Assoc. Qffic, Anal. Chem. 63( 5):952-958 ( 1980) Tuinstra. 1. G. M. Th. , w. A. Traag and A. J. van Munsteren. "Determination of Individual Chlorinated Biphenyls in Agri cultural Products by Automated Capillary Gas Chromatograony Determination in Cattle feed and Its Relation to Milk Resi dues." J. Chromatoor, 204:413-419 (1981). Tuinstra. L. G. M. Th. and w. A. Traag. "Capillary Gas Chro matographic-Mass Spectrometnc Determination of Individual ChioroDiphenyls in Technical Aroclors." J. Assoc. Off Anal. Chem. 66(3):708-717 (1983). Tuinstra. L. G. M. Th. . J. J. M. Driessen. h J Keukens. T. J. Van Munsteren, A. H. Roos and W. A. Traag. "Quantita tive Determination of Soecifieo Ch1orooioheny1s in Pish witn Capillary Gas Chromatograony and Its Use for Monitoring and Tolerance Purposes." Intern. J. Environ, Anal, Chem. 14.147 157 (1983) MOWS 223093 Bibliography 447 UCl. T.. K. Kamela, T Kan, H KaZama and T. Totam. "fluo rescence Reactions for Organic Halogen Comoounds. II. ]n Si lu Huorometry of Polychlorinated Biphenyls arQ Their Iso mers on Thin-ciyer Chromatograms using Oipheny l ami n*. Tokyo Tontsu Etsci Kentyusno Kenicyu h*mpo 25:111-118 <1974). Chem Aost 83 21?Tlc~ ( 1975 ) " ---------- Ugawa. M. Nakamura ana T Kashimoto. "Calculation Method for Po lycn)nrinaied Biphenyl (PC8) Isomers m Gas Chromaio* graphic Oc v. mnati on," Shokunin Eiseioaku Zassn 14<SV.41S- 424 (1973). Ch<m. Abst. 8Q:909S5u <1974). Ugawa. M. , a. Nakamura and T. Kashimoto. "Studies on a Cal culation Method for Po lycn lori nated Biphenyl Isomers (PCBs)." 'n New Methods in EnvironmentaI Chemistry and Toxicology. Collection of Papers Presented "at tn# Research Conference on New Methodology in Ecological Chemistry, Susono, Japan"' Novemoer ,13 25, ~19fr3. Couiston. f. korte. and M* Golo Uds.), ` .rmational Academic Printing Co., ltd., Tokyo (1973). ^ 253-267. Uk. C. M. Himel ana T. Dirks. "Hass Spectrometric iden tification of Mirex Residues in Crude Extracts and in the Presence of Polychlorinated Biphenyls." Bull Environ. Contarn. Toxicol. 8<2);97-104 (1972). United kingdom Oeoartment of the Environment. "Organochlo- rine- Insecticides and Polychlorinated Biphenyls in waters 197B; Tentative Method. Methods for the Examination of waters and Associated Materials," Qrqanochlonne Instctic. Polychlorinated Biphenyls waters 20 ppi ( 1979). ; United States Congress. Toxic Substances Control Act. Public law 94-469. October 11. 1976. Underwood. J. C. "Separation of Polychlorinated Biphenyls from QOT *nd Its Analogs Using Chromic Acid ano Silica Gel." Bull. Environ. Contam, Tpiicol. 21.707-790 (1979). urabe. H.. H. Koda and M. Asahi. "Present State of Yusho Pa tients." Ann. N, Y. Acad. Sci. 320:273-2B3 ( 1979). Uriano. G. A. "National Bureau of Standards Certificate of Analysis. Standard Reference Material 1501 - Polycnlorinated Biphenyls in Oils," wasnington, OC, June 25, 1982. Uthe. J. f., J. Rink* and H, O'Brodovich. "field Studies on the Use of Coated Porous Polyurethane Plugs as Indwelling Monitors of Organocnlorm* Pesticides ano Polycnlonnated 0ipnenyl Contents of Streams." Environ. l*tt. 6(2).103-115 (1974). HONS 223894 448 Bibliography Uthe. j F. and C J. Musial. Report of the Fifth ICES Intrc*liDration Study of PCBs in Biological Material." Inter national Council for the Exploration of the Sea. Copenhagen, Oenmarn, ICES CM 1980/E-8, Marine Environmental Quality Commif.ee (1980) Utility Solid waste Activities Group. Edison Electric Insti tute. and National Rural Electric Cooperative Association "Comments and Studies on the Use of Polycnormated Biphenyls in Response to an Order of the United States Court of Appeals for the Oistritt of ColumPia Circuit." U.S. EnvironmentaI Protection Agency. f0ru4ry 12. 1982, volumes I-lv Uyeta. M. . S. Taue. k. Chikasawa and M. Mazaki. "Photoforma tion of PolycnlormateO Biphenyls fro* Chlorinated Benzenes " Nature 264:583*584 ( 1976). vannuccni. C., R. Salvador), R. Nottoli, G. Ghimenti and G. Taooneco. "Identification and Quantification of Aromatic Polychlorinated Hydrocarbon Residues in the Environment," Riv. Sci. Tecnol. Alimenti Nutr, U*. 6(2):101-114 (1976); Chew. Apst. 85:175663a (197(T). Vannuccni, C. and m. Berlincioni. "Sa*ol'ng and Analytical Method to Oetermine PCB Concentrations in the Air of me working Areas of an Electrical Industry." a* (no. hvo Assoc J 41:352-360 (1980). van fiavn$w4*y, g, 0. "The Science*Policy Interface *n fteoulatory Oecis>on-Making," n PCBs; Human and Env1ronmentaI Hanaro*, f M. O'ltn ano M. A. kamrm. Eds. (Boston. 9ut* tervorth Publishers. 1903). pp. 353-366. van viiet. h. P. m., Th. C. Boots*an. R. w. Frei and u. a. Th. 8rin,man. "On-Line Trace Enrichment m High-Performance Liouid Chromatography Using a Pre-Column." J, Chromatoor 185:483-495 (1979). Veierov, 0. and N. Aharonson. "Economic Method for Analysis of Fluid Mil* for Organochlorine Residues at the 10 opo level." J. Assoc. Qffic. Anal. Chem. 63(3):532-535 (1980). Veierov. 0. and N. Aharonson. "Improved Cleanuo of Large lipid Samples for Electron Capture Gas Chromatographic Quan titation and Gas Chromatograonic-Mass Soectrometnc Confirma tion of Organochlorine Residues," J. Assoc. Offic. Anal Chem. 63(2). 202-207 (1980). Veith, G. 0. "Basel me Concentrations of Polychlorinated Bi phenyl* and 00T in lake Michigan Fish. 1971." Pest'C. Monit J. 9(1):21-29 (1975). MOMS 223695 Bibliography 449 Veith. G. 0 and N M. Austin. "Detection ana Isolation or 8toaccumuable Chemicals m Complex Effluents," Chapter 20 in lOent 1 1 i cat ipn ang AnalyS'S of Organic poMutants water, L. h xeun, ta. (Ann Ar00r_ mi. Ann Arbor Science Pub lishers. Inc . 1976), OD 297* 302 veith, G 0. ana l. M Kiwus. "An Exhaustive Steam- Distillation ana Sol vent-Extraction unit for Pesticiaes and Industrial Chemicals." Bull Environ Contam Toxicol. 17: 631-636 (1977) "~ Veith. G. 0 . D. w. Authi, 6. N. Leonara. K. welch ana G. Pratt. "Polychlorinated Biphenyls and Other Organic Chem ical Residues m Pish from Major united States watersheds Near the Great Lanes. 1978." Pestic Mpnit J IS 1-8 (1981). Veith. G 0. ana P. Kosien. "Estimating Bioconcentration Po tential from Octanol/Water Partition Coefficients." Chapter IS in Physical Behavior of PCBs m the Great Lanes. 0. Macnay. S ^aterson^ S. J. Eisenreich and M. S. Siweons, Eds. (Ann Arbor. Mj; Ann Arpor Science Publishers. Inc.. 1963). dp 269-282. Velie. M. and G. Kunti. "Pederal Polychlorinated Biphenyl Regulations," Chapter 7 in Oetoxication of Hazardous waste. J. H. Exner, Ed. (Ann Arbor. Ml: Ann Aroor Science Pub lishers, Inc., 1982), pp. 121-130. Ver Ouin, c. "The Commtncal fishermen's view of the PCBs Problem in the Great Lakes." m PCBs: Human and Environ mental Hazards. F. M O'ltn and M. A. kamrin, Eds. (Boston: Butterworth Publisners. 1903), pp. 109-112. Versar. Inc. "Revised Materials Balance for Inadvertently Produced PCBs." Report to u.S. Environmenta1 Protection Agency. Washington. OC (April 22. 1982). villeneuve. J P. " Intercal 'oration of Organocn'orme Stan dard Solutions," in Scientific Report of the Intercalipration Exerc i se. Intergovernmental Oceanograpmc Commission Tech nical Series Report No. 22. UNESCO. Paris (ISBN 92-3 102077-3), (1982) DO. 04-91. Vodicnik, M. J. "Factors Affecting the Bioaccumulation and Persistence of Polychlorinated Biphenyls." in Advances in Ex posure, Health ano Environmental Effects Studies 'o~f~pfgr-- Symposium Proceedings. R. J. Davenoort and B. k. Bernard (TdTT Office of Toxic Substances, U.S. Environmenta 1 Pro tection Agency, Washington, Q.C., Report No. lSI-TR-507-1378; NT1S No. P004-13S771 (Oecemoer 1903). pp. 97-127. HONS 223896 450 BlOiiograpny Vogel. C. . K. Brooxs. 1. frankel. $. hus and w, JacoOsen "Guidance Manual for Evaluating Permit Applications for tn* Operation of Incinerator units,'' Report by The Mitre Corpora tion, Mctean. vA, to U S Environmental Protection Agency. Contract No 63-01-6092. December 31. I960, 221 pp. voice. T. c. . C. P Rice ana w. J. weber. Jr. "Effect of Solids Concentration on the Sorptive Partitioning of Hydro- ohobic Pollutants in Aouatic Systems." Environ Sci recnnoi 17(9):513-510 (1983). ~ Vos. J. G. . J. h. Koeman. H. L. van der Maas, m C. ten Noever de Brauw and R. H. de Vos. "Identi f ication and Tocologica) Evaluation of Chlorinated Oibenzofuran and Chlori nated Naphthalene in T,,o Commence) Polychlorinated Bi phenyls," rood Cosmet. Tpnicol. 8:625-633 (1970). vos. J. G-, R. . rath and M. I. Luster. "Immune Altera tions," Chaoter S in HaloqenattO Biphenyls, Terpnenyis, Naphthalenes, Oibenxpoio>n$ ang Relateo Products. R. u Kimbrough, Ed. (New fork, n7! Elsevier/Nortn-Molland Bio medical Press, 1980). p. 241-266. Voyksner, R. 0., J. R. Hass, G. W. Sovocoo) and M. M. Bursey. "Comparison of Gas Chromatogrepfty/High-Resolution Mass Soectrometry and Mass Spectrometry/Mess Spectrometry Oetection of Polychlorinated Biphenyls and Tetrachlorodibehidfuran," Ana 1 Chem, 55:744-749 (1983). Vuceta, J. , J. R. Marsh, S. Kennedy, l Hilpemann and S. Wiley. "State-of the-Art Review: PCDOs and PCOfs tn Utility PCB Fluid," C5-3308. Research Project 1263-11, final Reoort. Electric Power Research Institute, Palo Alto. CA (Novemoer 1983). wammoto, T. , R. Tatsukawa and V Ogawa. Koqai to Taisaku 7:517 (1971); fish Res. Bd Can. Translation no. 2185. Wakimoto. T., M. fukushima. R. TatSukawa and T. Ogawa. "Sep aration of PCBs (Polychlorinated Biphenyls) from o.p'-DOE ano Other Orgenochlorine Pesticides by a Newly Oeveioped Silica Gel," Nippon Hopei Kaoaku Ka'shi 49< 10)-.499-503 (1975). Chem, Abst. 84:U6448r (1976). Welsh, E. J. "Interpretation of PCB field Testing Kits." m Proceedings: 19B3 PCB Seminar, G. Addis and R. t Komai. Eds. Report No. EPRI-tL-3581 (Palo Alto. CA: Electnc Power Research Institute), 1984. HONS 223897 Bibliography 451 ward. R. S. ana a PeHer "The Analysis 0f Mutuns of Closely Related Ka ture i ly-occum ng Organic Comoou-id* Using High Performance L'Qu'd Chromatoqraphy," J Chroma'aor Set 12:S70-S?4 (1974) ------------------------------------- warden. G. i "M*t.hod 'or tne Extraction of OrganocMonne Compounds from Quail Eggs," Analyst 102.54-55 ( 1977). Warsfia**, ft., a. Piscnpe'n. J. Thornton, A. Hiller ana I. J. Selikoff "Decrease >n v<tal Capacity in PC8-Exposa Workers m a Capacitor Manufacturing facility.'* Ann. N t Acad. Sci 320: 2 77- 2B3 ( 1979) Washington, T i. "Tne Environmenta 1 ist s view o* the PCBs Problem tn the Great lakes." in PCBs: Human ar; Environ mental Hazaras. e. H. O'ltn ana M. ~A. Kamrin, Eos (Boston: 8utter*orth Puol'shers. 1983), pp. 101-108. wassermann, m , 0. wassermann, S. Cucos and m . Hiller. "World PCBs Hao: Storage ana Effects in Han ana Hi; Biologic Environment m the 1970s," Ann. N t, Acad. So. :20'69-124 (1979). wassermann, M,, m. fton. 8. Sercovici. 0. Wassermann. S. Cucos ana A. Pines. "Premature Oelivery and Organocftlcrine Com pounds: Polycnlonnated Biphenyls and Some OrganocMonne Insecticides," Environ. Res, 20:106-112 (1902). watanabe. I.. T. rakushiji. K. Kuwaoara. S. toshiaa. a. Koyama, I. nara ana N. Kunite. "Studies on Pt'ycMorinated Sipnenyl (PCS) Isomers in Blood of Orflinsr. Persons. Oil Sickness Patients, ana Occuoationally Exposec workers. 2 Aoieion i Column Analysis." Osaka-furusu x:snu Eisei Kenkvusno kennvu nokoku. Shpkuhin Eisei wen 8 Si-El (1977)-. Chem,~Apst. d8: 163989p (1978). watanaoe. I.. T. vakusniji and N. Kunita. Distribution Differences Between Polychlorinated Terphenyls ana 5olycMor- mated 8*phenyls in Human Tissues." Buil. nv>ro~ Contam. TokicoI. 25:810-015 <1980). watts. R. R. <Ed.). Analysis of Pesticide Residue* m Human and Environmental Samples. A Compslation of nethoot ielectefl for use in PeYticioe HohitorinQ Programs, U.S. Env-praienta 1 Protection Agency. Research Triangle Park. NC. EPA-50O/8-8O- 038 <Jun I960). Weast. ft. C. and S. H. Selby (Eds.). CRC Hanooook ;f Chemii stry and Physics 40th Ed. (Cleveland. OH: The Chemical Rubber Co.. 1967 ). MOWS 223696 452 Bibliography Weaver, G. "PCB Contamination m and Around Nw Bedford Ha$$." Environ Sc < Technol L8(1): 22A-2?A (19B4). ' woo. R C. and A C. McCall "Identities of Polycnlorinat^o Bipnnyi Isomers >n Aroc'ors," J Assoc. Offic. Anal Chem 55(4). 746-752 (1972) " Webb. R. C. . and a. c. McCall. "Quantitative PCB Standards for Electron Caoture Gas Cnromatoqrapny J. Cnromstoor Sr, 11:366- 373 ( 1973) `' Weinberger, 8.. P. rarmcftuH and L- J. Cline love. "MicelleStabilized Room Temperature Pnospnorescence and fluorescence of Polychlorinated and olyDrominated 8'ohenyls." Abstract No. 295 from tne 1983 Pittsburgh Conference and Exposition on Analytical Chemistry ana Applied Spectroscopy. March 7-12 1963 Weminger. 0., 0- E. Armstrong and 0. 1. Swacfchamer. "Appli cation of a Sediment Dynamics Model for Estimation of Verti cal Burial Rates of PCBs in Southern lake Michigan." Chapter 22 in Physical Behavior of PCBs in the Greet lakes. D. Mackey. T Paterson. sT"1 j" ETsenfeTcrT"and"M S. Simmons, Eds. (Ann Aroor, Ml: Ann Arbor Science Publishers, (nc., 1983). po. 423-439- weitzman, l. "Treatment and Destruction of Polychlorinated Biphenyls and Polychlorinated Biphenyl-Contaminated Materi als." Chapters in Oetomcation of Hazardous waste. J h E*ner, Ed. (Ann Arbor. Ml: Ann Arbor Science Publishers, Inc. . 1902). pp. 131-142. "elborn, M . R. Borcnara. i. C. Hansen ana R. I Met calf "Extraction and Analysis of Arocior 1254 Comoonents m Blood." J Assoc. Offic. Anal. Chem. 57(6):1240-1252 (1974) wells. 0. E. and A. A- Cowan. "Use of Gas Chromatography Mass Spectrometry in the Environmental Analysis of Industrial Pollutants," in Recent Advances in Chromatooraohy-Mass Spec trometry (Anal. ProcT M?pV 242-246 ( 1982). welsch, F. "Effects of Polychlorinated Biohenyls on the Ex pression of Emcryotoxicity Caused By Model Teratogens." in r ' 'PCBs: Human and Environmental Hazards. F. m. O'ltn and m. A. Kamrin, Eds. (Boston: Butttrvorth Publishers. 1983). pp. 253-276. Welti. 0 and D- Sissons. "The Proton Chemical Shifts of Polychlorinated Biohpnyls." Organic Magnetic Resonance 4 309-319 (1972). MOMS 223399 Bibliography 453 West. P R . S. k Chaudhary and R. M *'tCheH 'Photode chlorination of Polychlorinated Bioheny'i Induced by Hygro- Quinone *i Basic Media." Extended Apstra:*.S. Qivision of En vironmental Chemistry, American Chemical society, wasnmgton, 0 C. , pp. 284*187 (Seotemoer 1983). westcott. J w , ang T. F. flidltman. "Determinat ion of Poly* chlorinated flionenyi vaoor Pressures by Caoillary Gas Chro matography." J Chromatoor 210:331-336 (1?81). Westerberg, fl. 0., s L. Alibrando an; F J. van Lenten. "Determination of Polychlorinated Bionenyls Using Limited Mass Scan Gas Chromatography Mass Spectrometry,'' J. Cnromatoqr 294(2):4a7*456 ( 1984). westin, R. A. "Polychlorinated Bion#nyi 1929-1979," Office of Tome Substances, U.S. Environmental Protection Agency, Washington, O.C., EPA-560/6-79/004; n*;$ No. P8-2965591/B ( 1979). Westdfi, . and K. Noren. "Oettrminaticr of Organocnlorme Pesticides and Polychlorinated Bipnenyis in Animal Poods," Acta Cham Scand. 24(5):1639-1644 (1970). Whitmore, F. C, "Destruction of Polychlorinated Bipnenyis in Sewage Sludge Ouring Incineration,'' Report by Versar, Inc., Springfield,VA, to U.S. Environmental Protection Agency, Washington, OC. EPA Contract No. 60-O1-1ES7 (NTIS No PB-258 162) 73 cp. (1976). wmtmore. F. C. and J. 0. Barden. "A Stjdy of PCB Destruc tion Efficiency and Performance for a Coal-Fired Utility Boiler; toiume 1. Test ana Evaluation, `j. S. Env i ronmenta 1 Protection Agency. Office of Rtsearc* and Oeveloom*nt, Researcn Triangle Park. NC. EPA-600/2-S2-101a (NT Is no. P884-110147) 79 pp. (Octooer 19B3a). Whitmore. F. C. and J. 0. Barden. "A Study of PCS Destruc tion Efficiency and Performance for a Coal-Fired Utility Boiler', Volume 2, Test Protocol." U.S, Environmental Pro tection Agency. Office of Researcn ana Development. Research Triangle Park. NC. EPA-600/2-83-101b (NTJS No. PB04- 110154) 69 pp. (1983b). Williams. C. H.. C. l. Prescott. P. 6. Stewart and G. Choudnary. "Formation of Polychlorinated Oibenzofurans and Other Potentially Toxic Chlorinated ryroiysis ProOucts in PCB Fires," Extended Abstract, Oivisian of Environmental Chewistrj, American Chemical Society, Washington, O.C. , pp. 265-266 (Septemoer 1903). MOWS 223900 *54 Bibliography W'llims, C. H Jr . L Prescott, ana i. 0. Carretson, "Detection of Polychlorinated Qibenjofur*ns jno Oth#r Chlor. nated Pyrolysis Products m tn* Soot formed m PCB f t <-es ' Proceedings1983 PCB Seminar, G Addis and ft, y \omi Eds. Report no. EPRI-Ei*3S01 (Palo Alto, CA. Electric Power Pesearcn Institute. 1984). williams, C. h., jr , c. L- Prescott, p.B. Stewart, ano G `Choudhary. "formation of Polychlorinated 0>0en:ofurans ano Other Potentially Toic Chlorinated Pyrolysis Products m Peg fires." in Chlorinated Qioins and Oibengofurans 'n the Total Environment 11. L. h. *eitn, C. Rappe, ano G._ Chouonary^ Eds., (Boston: Butterworth Publishers, 198S) pp. AS7-4&8 williams, 0. T. and 8. J. Blanchfield. "Thin layer Cnromato* graonic Separation of Two Cnlorooibenio-g-oio*tns 'rom Some Polycnlonnated Biphenyl and Organocnlorine Pesticides.1' J Assoc. Qffic Ana). Chem, S4(6):1429*1431 (IS71). ~ williams, 0. T. and B, J. Blanchlield. "Screening Method for the Oetection of Chlorodibenzo-g-dioxin* in tne Presence of Chlorobipheny 1 s, CMoronaohthalehes, and CMorodibenzofurans," J. Assoc. Qfflc. Anal. Chew. $5(1):93*9$ (1972) Williams, 0. T and f M. Benoit. "Tnt Determination of Polychlorinated Biphenyls in Selected Household Products." Bull. Environ. Contain. Toxicol. 21:179-184 ( 1979). Williams, 0. T.. G. 1. LeBel and T furmancryk. `Polychlor inated Biphenyl Contamination of Laboratory Air," Chemosonere 9 4S-S0 (1980). Willis, 0, E. and R f. Addison "Identification ana Estima tion of th# Major Components of a Commercial Polycnlonnated Biphenyl Mittur#, Aroclor 1221." J. fish, ties Board Can 29(5): 592-595 (1972). wiUmott, F. W. and R. J. Oolphin. "A Novel Combination of liQuid Chromatography and Electron Capture Oetecton m the Analysis of PestiCl0*S," J. Chromatopr, Sci. 12:69S-700 (1974). Wilson. N, K. and M. Anderson. "Carpon-13 and Proton Mag netic Resonance Studies of Chlorinated Biphenyls," *n Mass Spectrometry and mmR Spectroscopy in Pesticide Chemistry, R. Hague ano f. T! Slros, Eds. (New iorx, NT: p lenum ?ress. 1973), pp. 197-218. wingender, R. J. and R. M. williams. "Evidence for tne longOistance Atmosonenc Transport of Polychlorinated Teronenyi," Environ Sci. Technol , 1B:S2S-62B (19B4). HONS 223901 Bibliography 455 Winslow, S G. a*0 H. 0 Gerstner (Ed*. >. Polychlorinated fiipnenyls, Pp 1 vprpm! nj t fg Biphenyls, and Ther Contaminants: A literature Compilation 1965-1977, Oak ftioge National laboratory, Oat Riage, Tnnss \197S) wolbach, C. 0 . w f. f`tch, M- Flynn and B. Markoja. "An alytical Results of a PCB Test Incineration." in Second Sym posium on Process Measurements for Environmental Assessment (fe&ru^y 1980, Atlanta). T C~. hams (Id. ), TnvTronmenta 1 Protection Agency, Report No, EPA-600/9-81-018 (1981), Wolff. M. S. , J. Thornton.A. FisChPein, ft Lilis and 1. J. Se1> kof f. 'Qisoosition of Polychlorinated Qiphtnyl Congeners in Occupationally Exposed Persons," Toxicol Aop' Pharmacol 62:294* 306 (1982*). ' WoHf, H. S. , A F\scn&e>n, J, Thornton, C Rice, R. Lahs and 1 J. SeliAoff. "Body Burden of Polycnlormated Biphenyls Among Persons Employed m Capacitor Manufacturing,** lot. Aren Occup Environ Health 49.199*203 (1982D) wolff, M. S. , m. A. Anderson, I, J. Selikoff. "Human Tissue Burdens of Halogenated Aromatic Chemicals m Michigan," J. Am. Med. Assoc. 247(15): 2112*2116 (1982c). Wong, P. T. S. ana A. L. 6. Raiser. "Bacterial Degradation of Polychlorinated Biphenyls II. Rate Studies." Bull. En viron, Contain. Toxicol. 13(2): 249-255 ( 1975). world Health Organization. "Polychlorinated Biohenyls and Teronenyls. Envi rorwienta 1 Health Criteria 2." world Health Organization (1976) S5 po. Geneva: Taxushiji, T . I. watanape, K. Kuwabara and S Yoshida "Identification of Low Chlorinated Bionenyts in Human Milk, ey Gas ChromatograpnyMass Spectrometry," J Chromatoor, 154: 203*210 (1978). YakusnijS, T.. 1. watanaoe. S tosMoa. R. Tanaka. T. Kashimo to and N. kumta. "Analytical Methods for Organochiorine Compounds in Human Milk," Osaka*furitsu Koshu E;sei Kenkvusho Kenkvu HokOku, Shokuhin Eise'i Hen 11.87-91 (1980); Chernl* Abstr 96: 137221Z (1982). Yakushiji, T.. I. Vetanaoe, k. Kuwaoara. R. Tanaka, T. Kashimoto, N. Kumta. and I. Hra. "Rate of Oecrease and Half'life of Polychlorinated Biphenyls (PCBs) in tne 8!ood of Mothers and Their Children Occupationally Exposed to PCBs," Aren. Environ. Contam. Toxicol. 13(3).341-345 (1984); Chem. A&stT 101:42B&7w (1984). HONS 223902 *66 Bibliography rjIkowsxy, S. h . s C. vilvim, and 0. MCky. "Estimation of tne Aoutous Solubility of Some Aromatic Compounds ` 9esi. due Btvitws 0S:43-SS ( 1983). `---------- Yarbrougn. J 0. 4na H R Well* "Vertebrate Insecticide Resistance: The j_n vitro Enonn Effect on Succinic Oenyorogenase Act>vty on Endnn-Resistant and Susceptible Mosouitofish," 3ul> Environ Contam Toxicol 6(2)171-176 (1971). **21. J. , J. Brugger. 1. wilder, f. Freestone, R. Hitler. C. Pfrorwner, and R. Lovett. "Results of the Initial Trial Burn of the &PA-QR0 Mobile Incineration System." Environ mental Protection Agency, Municipal Environmental Research Lat>oratory--Cincinnati, OH, EPA-600/0-84-000 ( 1984) Yobs, A. R. "Leva's of Polychlorinated Sionenyls in Aoioose Tissue of the General Population of the Nation," Environ Health Persoec 1.79-01 ( 1972). ------------- -- Yoshimura, H. . N. Ozawa. and S. Saeki. "Inductive Effect of Polychlorinated Biphenyls Mixture and Individual Isomers on the Heoatic Microsomal Entvmes." Chem, Phana. Bull.. 26:1216 1221 (1978). Yoshimura, H., S. Yoshihara. N, Ozawa and M. Mini. "Possible Correlation Between Induction Modes of Hepatic Enzymes by PCBs and Their Toxicity in Rats.** Ann. N. y Acad. Sci 320 179-192 (1979) Yost, R. a. and C- G. Enke. "Triple Ouadruoo'e Mass Spec* trometry for Oirect Mixture Analysis and Structure E]uc'Ga* tion," Anal.Chem 51(12): 12S1A-12MA ( 1979) rost. R. w , i. s, ttre and R. 0. Conlon (Eds). Pract1cai liquid Chromatooraphy * An Introduction (Norwa1k~ GT P#rkin-timer. 19SQ). _ Youden, w. J. and E. h. Steiner. Statistical Manual of the Association of Official Analytical Chemists (Arlington, vA: Association of Official Analytical Chemists, 1975), 68 pp, Young. S. ment for Cleanup." (1972). J. v. and J. a. Burke. "Micro Scale Alkali Treat use in Pesticide Residue Confirmation and Samole Bull. Environ. Contam. Toxicol. 7(2/3):160-167 Young, S. J. , C. Finsterwalder and J. A. Burke. "Extraction and Cleanup for Determination of Polychlorinated Biphenyls in Paoer ano Paperboard," J. Assoc. Off Anal. Chem 56:957-961 ( 1973). MONS 223903 Bibliography 457 Young, $ J. v and i. R Kamos. Gas-L'Qu'd Chromatographic Determination of Nonpolar Organocn I on n* Pesticide Residues >n a Crude vegetable Oil and Its Refinery By-ProductsJ. Assoc 3ff ftnal Che* 65(4) 916-920 (198?) Toung, $ , m Closer, jr , j a. G. Roach. Method for Oe- terminmation or Organona logon Pesticide Residues in vege table OH Ref in*ry By-Products." J. Assoc Off. Ana). Guam. 67(1): 95-106 (1984). ' Zabik. H. J. "The Photochemistry of PCBs." m PCBs; Human and EnirpnmantaI Hazaras, F. M. O'ltn and M. A. Kinrin, Eds. (Boston: Buttarworth PuOlisnars. 1983), pp. 141-164. Zelenski, S. C. , J. Tasmro and L. R. Worthen. 'A Gas Chro matographic nathod of Quantitating 00T in tha Presence of Intarfarnng Polychlorinated Biphanyl." J. Chromatoor. 84: 67-73 (1973). ----------------------- Zelenski, S. G. . J. Mall and S. E. Haupt. "Applying for a Parmit to Oastroy PCB wasta Oil; vol. I Summary." u. S. En vironmental Protact-ion Agancy, Office of Rasaarch and Oavalopmant, Rasaarch Triangla Park, NC. EPA-600/2-8l-033a; NT1S No. PBB1-173 346, B5 pp. (March 19Bla). Zalanski, S. G. , J. Hal) and $. E, Hauot. "Applying for a Parmit to Oastroy PCB wasta Oil; Vo!. 11. Oocumantation," U.S. Environmental Protection Agancy, Offica of Rasaarch and Oavelopmant. Rasaarch Triangla Park, NC, EPA-600/2-Sl-033b: NTIS no. PBB1-234B74, 220 pp. (March 19Blb) Zell, M. , h. J. Neu and K. Bal 1schmitar. " IdantifiIierung dar PCS-komoonantan durch Ratantionsinda*vrg)a'cn nach Kapil I ar-Gascnromatograonia,' Chtmosohara 6:69-76 (1977). Zall. M. , h. J. Neu and K, Ballsch*>ter. "Single Component Analysis of Polycnlorinattd Biphenyl (PCB)- and Chlorinated Pesticide Residues in Manna Fish Samples," crasamus' Z. Anal. Cham, 292:97-107 (1978). Zall, M. and K. Ballscnmitar. "Baseline Study of the Global Pollution. III. Trace Analysis of Polychlorinated Biohenyls (PCS) Py ECO Glass Capillary Gas Chromatography in Environ mental Samples of'Oifferent Trophic Levels," Presents' 2 Anal. Cham. 304:337-349 (1980). Zhang, T. , T. Gu, and X. Xu, "Determination of Polychlori nated Biphenyls m $t4w4ter,'* HaiyanQ Tu Hothao 14(4). 353-356 (1983); Cham. Apst. 101:11919m (1984). MONS 223904 *56 ` Bibliography Zimm*r ] i , 9 "Be'trag lur Bestimmung von Umweltkontemm*,,. ti*n M111*ls der Hyflritr#non Peakt lonsgaschromatograon** J_ Chrpmatogr 88 6b- ?S (1974) 1 2'mm*rli, 0. , 0. H*rfk and M Suiter "Determination 0f Chlorinated Bionenyis *no Chlorio* Pesticides," Mitt Cr> L*b*nUtcluntr$ vg. 64( 1): 70-79 ( 1973). Chem Tpst Tv* 12*762* (1973). ---------------------- 2 i t ko, V "Polychlorinated Biohenyl* and Organochlon** Pesticioes m Some Freshwater no Ninnt Fishes." Boll En viron Contam Tq>cq1 6(5):464-470 ( 1971*). _ Zitko. V. "Effects of Pesticide-grao* Hexanes en th* Silicic Acid Chromatography of Polychlorinated Biphenyls *nd Org*nocMonn* PettlOdes," J ChrQmatOQr. 69:444-4*5 (1971b) Zitko, V "ProP1*ms in the 0*termin*tion of PolyChI or'n*t#o Biphenyls," Inttm. J. Environ. An*). Chem. 1 221*231 ( 1972). Zitko, V. "Chrpmatography of Chlorinated Paraffins on Alumin* *nd Siliea Columns," J. Chromatpqr 81:152-155 (1973). Zitko, V. "Th* Oetection of Aromatic nd Chlorinated Hydro carbons m Marine Lipids," J. Am, Oil Chemists' Soc. 52:121A U97S). Zitko, V. "levels of Chlorinated Hydrocarbons in Eggs of Oouble-Crested Cormorants from 1971 to 1975," Su)1 Environ Cont*m. T oico i 16(4):399-405 ( 1976). Zitko, v "Th* interference of Aromatic Hydrocarbons in th# Determination of PCB's," m Proceedings of the Joint Conf*- net on Sensing of Environmental Pollutants. *tn. h*w Orleans (19^7) po. 757-760 Zitko, V. `"Shorthand' Numbering of Chlorooionenyls." Chemosphere 12(6):835*836 (1983). Zitko, V. end P. M. K. Choi. "PCS and Other Industrial Halo* geneted Hydrocaroons in tn Environment" Technical Reoort No. 272. St. Andrews, New Brunswick, Canada. Fisheries Re search Board of Canaoa (1971). Zitko. V.. 0. Hutzinger and S. Safe. `Retention Times and Electron-Capture 0eteetor Responses of Some Individual Chio* robiphenyls Bull Environ. Contam. T oco1. 6(2)160-163 (1971). Zitko. V. and P M. K, Choi. "PCB and g,g`*00 in Eggs of Cormorants. Gulls, and Oucks from the Bay of Fundy, Canao*." Bull. Environ, Contam. Toxicol. 7(1>:63-64 (1972). HONS 223905 Bibliography 459 Z'tko. v . 0 Mutzmger, and P H K. Choi. 'determination of PentacMoroonenci i no Chlorooionenylols in Biological Sam ples," Bull E nv i 'pn CoMam ToiCol 12(6) 649-653 (1974*). Iitkc. v P M K Choi. 0 J. Wildish, C- f. Mon*gh*n *no N 4 lister "Omnoution of PCS angg.g-DOE Residues m Atlantic Herring (C'upe* h*rengus harenQus) *nfl Yellow Perch (Perea f I avescen* ) i n Eastern Canada* 19/2." Pestic Hon. J. . 0(T) I0f-109 (1974b) Zobel, m. C. R. "Quant* tativ# Determination of Polychlori nated Biphenyl*--* Computer Approacn," J. Asspc. Qffic. Ana) Chem. 57(4 ) 791* 795 ( 1974 ). 2o 11. 0. f , G. v. Cox, R. J. fensterhaim and l w. warren. "CoMtents in Response to Proposed Rule on Manufacture, Pro cessing, distribution and use of Polychlorinated Sionenyl* in Closed and Controlled waste Manufacturing Processes.'' Sub mitted to tne u S Environmental Protection Agency by tn* Chemical Manufacturers Association Soecial Program Panel on PCBs, EPA Oocnet No. DPTS-62D17A, July 8. 1982. 80 pp. Zwtig, G. and J. Shenea. CRC Handbook of Cnrowatooraphy. (Cleveland. DH: CRC Press. 197TT MOMS 223906 APPENDIX A NOMENCLATURE AND PHYSICAL CONSTANTS OP POLYCHLORINATED BIPHENYLS 461 HONS 223907 462 Appendix A Tab)* 4-1 No**"clature and Physical Constants of Polycnlormatafl fliohnyls lUPAr NO. Coaoouno 8ioh*nyl MonochloroDionany1 12 23 34 OichloroOipheny) 4 2.2' s 2.3 6 2.3' 7 2.4 8 2.4' 9 2.5 10 2.6 11 3.3' 12 3.4 13 3.4' 14 3.5 15 4.4' TrichlorODionanyl 16 2.2' .3 17 2.2' .4 18 2.2' .5 19 2.2' .6 20 2.3.3' 21 2.3.4 22 2.3.4' 23 2.3.5 24 2.3,6 25 2.3*.4 26 2.3' .5 27 2.3* .6 28 2.4,4' 29 2.4.5 30 2,4.6 31 2.4' ,5 CAS No. Halting Point (aC) Solubl!, ' n M;0 ( OQA 1 92-52-4 27323-18-8 2051-60-7 2051-61-8 2051-62-9 25512-42-9 13029-08-8 16605-91-7 25569-80-6 33284-50-3 34883-43-7 34883-39-1 33146-45-1 2050-67-1 2974-92-7 2974-90-5 34883-41-5 2050-68-2 25323-68-6 38444-78-9 37680-66-3 37680-65-2 38444-73-4 38444-84-7 65702-46-0 38444-85-8 55720-44-0 58702-45-9 55712-37-3 38444-81-4 38444-76-7 7012-37-5 15862-07-4 35693-92-6 16606-02-3 71C 34 16.5 77. 7 60.5 27.7-28.2 01 1 24.1*24.4 46 22-23? 35-36 29 49-50 01 \ 31-32 148-149 28.1-28.8 43-44 101-102 73-73.2 41 40-40.5 57-58 78-79 62.5 67 7 59 36 1 19 1.50 1.40 1.88. 0 59a 0 08 0 14a 0 085 0.092 MOMS 223908 Nomenclature ana Physical Constants 'D 1 e A-! (Continued) 463 UPAC NO 3 Conoouna 32 :.4- .6 33 2' .3.4 34 :.3,5 35 3.3' .4 36 3.3' ,5 37 3.4.4' 38 3.4.5 39 3.4' .5 TetrichloroDloneny1 40 2.2' .3.3' 41 2.2' .3.4 42 2.2' .3.4' 43 2.2' .3.5 44 2.2',3.5' 45 2.2' .3,6 46 2.2',3 ,6` 47 2.2'.4.4' 48 2.2' .4.5 49 2.2'.4.5' SO 2,2' .4.6 51 2.2'.4,6' S2 2.2* .5.5* 53 2.2'.5.6' S4 2.2',6.6* SS 2.3.3' .4 S6 2.3.3' .4' S 7 2.3.3' .5 58 2.3.3*.5' 59 2.3,3* ,6 60 2.3.4.4' 61 2.3,4.5 62 2.3,4.6 63 2,3,4*.5 64 2,3.4' .6 65 2,3,5.6 66 2.3'.4.4' 67 2,3' ,4,5 68 2.3',4.5' 69 2,3' ,4,6 70 2.3'.4* ,5 71 2.3' .4' ,6 CAS No. Me 111ng Point (cr So1uD \ \ m Hj< (PD* 38444*77*8 38444*86-9 37600*60*5 37680*69*6 38444-07-0 30444-90*5 53555-66-1 30444*00*1 26914*33*0 38444-93-8 52663-59-9 36559*22*5 70362-46-0 41464-39-5 70362*45*7 41464-47-5 2437-79-0 70362-47*9 41464-40*8 62796*65*0 65194-04-7 35693-99*3 41464-41-9 15960-05-5 74330*24-2 41464-43-1 70424-67-0 41464-49-7 74472-33-6 33025-41*1 33204*53*6 54230*23*7 74472-35*0 52663*58*8 33204-54-7 32590*10-0 73575*53*0 73575-52*7 60233-24*1 32598*11*1 41464*46*4 60 58 86.8*87.8 88 119.5*121.S 68-70 46.5-47 125.5-127 41. 83 64-66 87-89 103-104.5 198 96-97 127.5-129 142 92-92.5 104 79 124 104 0.078 0 . 015C 0. 034 0.170 0.068 0.046 0.058 0.0191 0.058 0,041 MONS 229909 464 Appendix A laole A*I (Continued) lUPAC NO. Compound CAS No. Melting Point (*C) So 1uo i ] n 'n (pp*)& 72 2.3',5.5' 71 2.3' .S' .6 74 2.4,4' ,5 75 2.4.4' ,6 76 2' .3.4,5 77 3.3',4.4' 78 3.3',*,5 79 3.3',4,5' 80 3.3',5.5' 81 3.4,4' .5 Pentechlorooiphenyl 82 2.2'.3.:'.4 81 2.2',3.3' ,5 84 2,2' ,3,3' ,6 85 2,2',3,4,4' 86 2 ,2',3,4.5 87 2.2',3,4,5' 88 2.2*.3.4,6 89 2,2' .3,4,6' 90 2.2'.3,4'.5 91 2.2',3.4',6 92 2,2'.3.5,5' 93 2.2'.3,5,6 94 2.2'.3.5,6' 95 2.2'.3,5' .6 96 2.2',3.6,6' 97 2,2'.3'.4,5 98 2,2',3',4,6 99 2,2',4,4* ,5 100 2,2',4,4' ,6 101 2,2'.4,5,5' 102 2.2*.4.5,6' 10) 2,2'.4,5'.6 104 2,2*.4,6,6' 105 2,3,3',4,4* 106 2,3.3'.4,5 107 2,3.3'.4' ,5 108 2,3.3',4,5' 109 2.3.3'.4.6 no 2.3.3'.4' ,6 111 2.3.3'.5.5' 41464-42-0 74338- 23*1 32690-93*0 32598-12-2 70362*48*0 32590-13-3 70362-49*1 41464-40-6 33204-52-5 70362-50-4 105.5-106.5 125 173 119-120 164 25429-29-2 52663-62-4 60145-20-2 52663-60-2 65510-45-4 55312-69-1 38380-02-8 55215-17-3 73575-57-2 68194-07-0 58194-05-8 52663-61-3 73575-56-1 73575-55-0 38379-99-6 73575-54-9 41464-51-1 60233-25-2 38380-01-7 39405-83-1 37680-73-2 68194-06-9 60145-21-3 56558-16-8 32590-14-4 70424-69-0 70424-60-9 70362-41-3 74472-35-8 38380-03-9 39635-32-0 119-120.5 111.5-113 98.5-100 81-92 76,5-77.5 101-105 0 175 0 0098' 0 022. 0.012 0.031 MONS 223910 Nomenclature an<3 Physical Constants Tap1e A-1 (Continued ) 465 1UPAC No ComDOuno nr 2.3.3' .5.6 113 2.3.3'.S' ,6 114 2.3.4.4- .5 ns 2.3.4.4- .6 116 2.3.4.S.6 117 2.3.4' ,5.6 118 2.3'.4,4' .5 119 2,3' .4.4' .6 120 2.3'.4,5.5' 121 2.3',4,5'.6 122 2' .3.3'.4,5 123 2'.3,4,4' .5 124 2* .3,4.5.5' 12S 2' .3.4,5.6' 126 3.3'.4,4' .5 127 3,3'.4,5.5' HexAchloroDipheny1 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 >46 147 148 149 ISO 1S1 2.2' .3.3'.4 .4' 2.2* .3.3'.4.5 2.2'.3.3'.4,S' 2.2' .3.3'.4,6 2.2'.3.3'.4,6' 2.2'.3.3'.5.5' 2.2' .3.3' .5.6 2.2'.3,3'.5,6' 2.2' .3.3',6.6' 2.2' .3.4.4' .5 2.2'.3.4,4- .5' 2.2'.3,4.4- .6 2.2' .3.4.4' .6' 2.2'.3.4.5.5' 2,2'.3,4.5.6 2,2',3,4,5.6' 2,2' .3,4.5' .6 2.2'.3,4.6.6' 2.2',3,4'.5.5' 2.2', 3.4',5.6 2.2'.3.4',5.6' 2.2* .3.4',5' .6 2,2' ,3,4' ,6.6' 2.2' .3.5.5' ,6 CAS No Mf Hing . Po*ni (#C)D Solubi1ity in H;0h (PP*) 74472-36-9 68194-10-S 74472- 37-0 74472-38- 1 18259-05-7 68194-11-6 31508-00-6 S6558-17-9 68194-12-7 56558*18-0 76842-07-4 65510-44-j 70424-70-3 74472-39-2 57465-28-8 39635-33-1 26601-64-9 38380-07-3 55215-18-4 52663-66-8 61798-70-7 38380-05-1 35694-04-3 52704-70-8 52744-H-S 38411-22-2 35694-06-5 35065-28-2 56030-S6-9 59291-64-4 52712-04-6 41411-61-4 68194-15-0 68194-14-9 744 72-40-5 51908-16-8 68194-13-8 74472-42-7 38380-04-0 68194-08-1 52663-63-5 98-99 123 105-107 1455-146,6 128-129 114-114.5 77-70 78.5-80 69.5-71 134-137 01 1 100-101 0.0068 0.00044*5 0.00085 0.00091 HONS 223911 466 Appendix A TjO'e A* I ( Cont i nue<3) NO. * Compound 152 1,2' .3,5.6.6' 153 2.2'.4.4'.6,5' 154 2,2'.4,4-,5.6' 155 2,2'.4.4'.6.6' 156 2.3.3' .4.4' ,5 157 2.3.3' .4.4',5' 158 2.3.3' .4.4' ,6 159 2.3.3'.4,5.5' 160 2.3.3' .4,5.6 161 2.3.3'.4.5'.6 162 2.3.3' .4',5.5' 163 2.3.3'.4'.5.6 164 2.3,3'.4'.5'.6 165 2.3.3'.5.5' .6 166 2.3.4.4'.5,6 167 2.3'.4.4'.5,5' 168 2.3' ,4,4'.5' .6 169 3.3' .4,4',5.5' HeptacMoroDiOfttny 1 170 2.2' .3,3',4,4` .5 171 2.2' .3,3',4.4' ,6 172 2.2'.3.3',4,5.5 173 2.2' .3.3' .4.5,6 174 2.2'.3.3'.4.5.6' 175 2.2'.3.3',4.5'.6 176 2.2' .3.3'.4.6.6' 177 2.2'.3.3',4' .5.6 178 2.2'.3,3'.5.5'.6 179 2.2*.3.3'.5.6.6' 180 2.2*.3.4,4',5,5' 181 2.2*.3.4,4' ,5.6 182 2.2'.3,4,4',5,6' 183 2.2' .3.4,4' .5' .6 184 2.2'.3.4.4* .6.6' 185 2.2'.3,4.5.5' .6 186 2.2',3.4,5.6.6* 187 2.2* .3.4'.5,5' .6 188 2.2'.3.4',5,6,6' 189 2.3.3'.4,4',S,5' 190 2.3.3',4.4',5.6 191 2.3.3'.4,4' ,5' .6 CA5 No. )t'ng Po^nt (#C) So 1UO \ ! , ^ m;o 1 (00*)^ 68194*09-2 35065-27-1 60145-22-4 33979-03-2 38380-08-4 69782-90*7 74472-42-7 39635-35-3 41411-62-5 74472-43-8 39635-34-2 74472-44-9 74472-45-0 74472-46-1 41411-63-6 52663-72-6 59291-65-5 32774-16-6 28655- 71-2 35065-30-6 52663-71-5 52663-74-8 68194-16-1 38411-25-5 40186-70-7 52663-65-7 52663-70-4 52663-67-9 52663-64-6 35065-29-3 74472-47-2 60145-23-5 52663-69*1 74472-48-3 52712-05-7 74472-49-4 52663-68-0 74487-85-7 39635-31-9 41411-64-7 74472-50-7 103-104 01 1 112.5 97-100 160-165 110-111 201-202 134.5-135 130.5-130. 109-110 152-153 147-150 162-163 116-118 0.0013 0 0009l3 0.00046' MOMS 223912 Nomenclature ano Physical Constants 'aDIe a-I (Cont i ^uea ) 467 MJPAC NO. Compound CAS No He 111ng Point (C) So 1 upi1 i ty in HjO. (ppm ) 192 193 194 19S 196 197 198 199 200 201 202 203 204 205 206 207 208 209 2 . 3. 31 . 4 . S, S ' , 6 2,3,3' ,4' ,5,S' .6 Octacnlorobipnenyl 2,2' ,3,3',4.4-.5.5' 2,2'.3.3',4,4' ,5.6 2.2' ,3.3' ,4.4` ,5.6' 2.2' ,3.3' ,4,4' .6,6' 2.2',3,3'.4,S,S' ,6 2,2',3.3'.4.5,5',6'9 2.2' ,3.3'.4,5,6.6'' 2.2' .3.3'.4,5', 6 , G' 9 2,2'.3.3',S,S'.6.6' 2.2' .3.4,4',5.5' .6 2.2' .3,4,4',5.6.6' 2.3.3'.4,4',5,5' .6 Nonacnloropiohenyl 2.2'.3.3'.4,4' ,5.S'.6 2.2' ,3,3' ,4,4',5.6.6' 2.2'.3.3'.4.5.5',6.6' OecacnlorobiphenyI 2,2'.3.3' ,4,4' ,5.5',6,6 74472-51*3 69782*91-8 31472'83-0f 35694-08-7 52663-78-2 42740-50-1 33091-17-7 68194-17-2 52663* 75-9 52663-73-7 40186-71*8 2136-99-4 52663* 76-0 74472-52-9 74472-53-0 53742-07-7 40186-72-9 52663-79-3 52663-77-l 2051-24-3 2051-24-3 156-157 132 161 204.5-206.5 305-306 0.0014 0.00018 0.00011 0.00049 a Bailscnmiter, k . ano H Zell (1980) 0 All melting point and water solubility data from Hutzinger, et a). (1974a) unless otherwise noteo. Otn#r eaoenmental values were often reported; where major discrepancies exist, extreme values are separated by a comma. The otner references report conflict* ing values for many of the congeners. Oo not compare values from different citations without consulting primary reference, c CSC Handbook of Chemistry and Physics (S7tn ed. ) d . Yalkowssy et al. (1983). e Mackay et il. (1980). f four chlorines on eacn ring at unsoecified locations, g Revised numbering seQuence as noted by Schulte and Malisch (1983). HONS 223913 APPENDIX 8 COMPOSITION OF SOME COMMERCIAL PCB MIXTURES 469 MOMS 223914 470 ItDlt B-I l)nt 111 *l > ve tnd Percool Ch)uio(>ipl>enyl jnd B lphetty I Compos 11tony of CommotcuI PCB Pttptrtliont II < lainrirlat I'mmmxm ilup mhiHi III! 1111 in nil mi itll III HU mi lit IM IIM im im m IM IM im im im 0% 1 I) n Ml II a IS a Ml Ml ) It li ft Is a a tl a 1m 1 IS >s m ft a > 1 tl M ill a < 1 M ti aa # * * ft 11 t a II 1 a a < 11 11 ft a M 1< it >1 a II a S tl Ha a * ft IS 11 II 1 St s a III \ ft III 1 It 11 1 aa 1II ti < 1II IIS lit II 1 111 III ns 1s 1< s 111 11 ti tt ti ti aa a aa tt a a a a II S a IS 11 1a 1 < 1 11 a 1 II s a m II It a am 1a a ft m ft * ft it 11 ni ) Ml Ml 1s 1 II 11 11 < 11 a M a (0 II a m 1 Ml B-l (Continued) MOMS 223915 471 leb>e 8*l (Continued) imi imi im imi mi; (in mi; >> 11 )* 111 M I I> i > i) i ii II < il i I 11 Ili il II i <; 11) r > ll i >l < }M II I n < Ml IH II * Ml n> ni II i >i i Ml Iin11 i tr i >l III ) ni 11 111 in iJM ih; imi uii mm mi i;ii m mm m* il i i <** m M M HONS 223916 472 mu iin Mil Ilf I Iflf lilt uu 11 tt mi Iftt lilt im ini ifw irw m tm i~nT7^~ m m m% nu no ii o ii i Mil J Ml 1111 1i m *> I 14 II > u ki MMI lint ff HI Mill I II* * ii III Mill M< l Mill M M ii III I i III Mill Ml M Mill If H I M III If III fII I I MMI Mill MMI If II I M III fllll fllll fl 1 II fI l M Ml II III l I I II I I ) Ml tl HI / * * I HONS 223917 473 l4b> 0-> (Continued) tin un mi (fii iim mi imi uJ im im tr im im mi im im nu m m m% l ' i ii in IIMI (I n i j 11 * i M"1 Mill Mill IIMI II Ml m mi M r III mill Inin II > I 4 I n itiv If III! Ml II I MIMI II II II II IM I II Hit it I ii Mini III it t min a ii it I I It! I MMII M r it Mint inru iriMi II IM v Mini ii nit II |I4| II M r MOMS 223918 474 l*bi 6*1 (Continutd) it)i it 11 M tV n 11 tt m 11 tt iiini tMttt IM4 ti UHlt mitt II M II I lit nun mum II Mil II | III Mtt tt II |4I It ii ntt t il nttl IIIHtt mint . il tint n it ttt i >t Hi II M It ii mu it M ti it M HI ii it it i >1 II lit 11Ml\t II I <1 IV mlllluttttl ii nnt i m i tit M n tt i ii ttt limit ii mitt n ttt tt t II II 411 t II I I 4ttt III IM Mil MM MM M4| Mil 111! UM IM m- IIM ifM tM MM IM MM ~i# ~~rn w* Ml It 11 tl HONS 223919 IIIMII nmn ll M i t( >' 11 II t II IMII M <1)tt >111 k i i II i i \ * II lt t > \ i II IIMU I ll MU It lit >|| (I < n lftl I (I t IV 1 T<*blt 8' I (Cone 1 tided) mi mi n;i mi mi itit m> > 1 l 11 V v t 1 > l lilts II l mvi 11 1 1 V \ 1 i; i 1 M it /1 < ) t s i t II II tv ss nil i sit IMI MS it Hit M \S 4 /l l It (( (VI < I curl* .1 ! < ! ll C ini im ihi mi us* iis* iisi isa us* U44 >> IU 01 i * ft i It <), h i ll 41 s m J. hh m m M m mm <| < I. it t ft * f i I Note;-Qualitatively major'peaks = M, minor peaks 8 m, ambiguous identities = ?, quantitatively, percentages rounded a Nagayan* et ai ( IM/G) t> Albro, P.W. , NlMIS, ttesearcli Triangle Park, North Carolina, written communication (November ><m). t Willis and Addison (I'J/?) d Sissons and Welti <19/1). e .leosen and Slindstrbm (1974). ( las and deVos (1971). Source: N10SH (1977c). 475 HONS 223920 appendix c MASS SPECTRAL CHARACTERISTICS OF PCBs 477 MONS 223921 478 c ]2H 10 ^12h8C1: Appendix q C i2H9Ci, 14 il; n Tin 186 <92 Ci2H?C13 222 226 C12m6C,4 256 260 C12H5CI5 290 296 Mgure C*l. Mess Specirel Patterns of PC8s a Mono- Through PentachloroDOhenyls The molecular ion clusters were calculated using natural apunoance ratios of caroon, nyorogen, and chlorine. MOMS 223922 Mass Spectral Characteristics of PCBs 479 Ci2H3CI? Figure C*1 (concluded). Me** Soectrel Pattern* of PCB* Mexa* Through DecacMorobiphenyl The molecular ion cluster* were calculated using natural abundance ratios of carbon, hydrogen, and chlorine. HONS 223923 480 Appendix c * *< C>e# >-- i t i kM.lir I ................t -rr---------------- -rrr,---------------- (, 1 l*t 4(l *'1 imr------------t..i'.i, I>MI *>1> ,* WT---------------< 1., * K . 1 .( *>( *(. it* I'll l/l t*M iM IW* *04 04'* - iM Im ;M M ni im >9* * III lilt 144 44 ! Ml 11 H Ml III* ii / m in* ii * Mn in in h i 14 If* M*> if* Ml) i M I'M 144 44 > M 10 44 m *ii* i*i fit* / *M 144 44 II > .ii *ii ' .4 i IM * f/t H*> 144 44 m im IM M ,'40 4*04 *1 U >11 1>* > .*> m II '1 *m i; if Ml t)M i/ ** .m *m n 10 i '/ ill Mf 1u HI fit) 1M ns ilia * '4 i im % 1.1 *MI * >i 11* M*t ** *1 >44 4* 44 *1 '> 4414 /* MM (44 44 i /> IM l*M III MM 104 04 H *| 104 000' 161 **' 10 44 HI MM :< 0440 II M * 4? in mm >}( 444 l II II 4 44 111 * 4 \ 1,-) Ml* i' ii .Ml **>' i ii Itl 1*1* 10 00 IK */' > 01 .44 44 :n 4444 >M M HI IM* IM M 111 t**' '> *41 4110 1* \> 1*' Ml' It *h KM IVM >i It* Mil :: *i !1 |4ifl 1 4i *04 0440 i >> Ml MM i 'l HI IM* I 04 it' MM MM 111 l/M M f* H IlM WH l'l llll H* H11 iM 44 111 */M it0 44 II* IlM IM M l'l l/l' 100 00 ; w m //t *i i> m MM )U III* i: a hi *h* It 4' hi im * w HI Ml nn 111 11*1 Ml I l/l *w m im ii m M * * !'* Ill* tn HI MM HI >M* 1*1 HM t M t* M M *1 M 1' M II* 'IM HI 'IM Ml 'IM l'l 'Ml >') MM > i* *44 44 * ii W *1 ( ' 44 fl MM It "*l n *m /* <*M n hi* 1 M 104 04 HU > ) 1 * 00 #* IM 1 0J (0|t M I'M 1) I'M II I'M > 44 100 00 01 i / * It 11 IM **M ii m lit lM ua M '*! ; *4)t * II '* 1* Ml '111 > ii Il '/! 1' S n *000 <44 44 10) '*44 100 44 It* ll*l *04 04 1 MM ii nr* H 0* H/t > 4 *i mi *t * lt llll 1) V4I > *$ M4* * j HI MM . > ii M' Mi* .K 4* * *4 i >.**> ei r.v* >* >* <1 `If. .* t < .i 04 It / iii te * kM ** */* 444 4 '4* t/l *lfl > it HONS 223924 Mf55 Spectra Chtrectenstics of PC8s 481 4M ' i <v ' *( lit ^ k. U *| *'4 l ) ff"" "" .% 1 tm% Iii| 9 i>/ Mil '1i Mil IM lt 19 9ft* >1oft N91 10 9$ 1 M ., * m.* no hi> ..**'11114' f 9Iff* M 11>M M II (Oft ftft 1 '1M '< i . ;>i im IM M ;ii mi iN M <1H M ; ,'1 11i `f mi mi ** fH *[< *' 'M ' 91 1 4i ' *> * i ' Iftt | k .11 4 141MW iPv M ** l*> M <1im iii* II 94 111 6;i n/i :P MM II k 4 1j III H)l > V m u>t 9i 91 111*11 I'll I'M .m4 m11 1U' >J *1111 * ; i i ll ft' HI Mil l> Ml .'k11 *i 9M * 11. ll KM wM in mi M i>' i?t* im a* l`k IM IM M 1 111m km I> * H> II'* K -V u i" iim !' MM HI W'k i; i 11I* .ft t 1*1 HM '1 'M* 1 ) MM m 'mi HI >>M 1M * M M W II >1 M 1' U MM 111>M * 4 11 tMft <>> 'in ilk >M <1 1* 11IM M < itn *k *i ft `11 1 111 11 V'VM 11/I lilt *11 Hit 11 *1IN HM ) It M IM M M *kl 'kM mi 'Mk nn tr ik IM M tk k> Ml OM n ii mi in* ii w '1* k ' Ik M " 'IM II it mi 1*19ft I l>)t Ml ' IM M 9>9 J 1J .( 9*M*I UCh ' Mi*( k i9smmix l* |Mt 55------------------TTW T-------------- f.'SV'.M k'Hi flftftl *M Ml||l '1 MM mmhi ll< Mkl 1>I MM 1" Mil IK Mil 14* M i; ii tftft ftft <1) >1 >i M Mil mmj.'ft ftftn it 1*1 MM III Mlt lit ftft* >1 *1 *1Ik II II titi iH IM* ill till HI kill >* till *\'ll *1411l .11 1Ml Mil *> l 'll till .'< Mil .".1Ml Mil Mil m m*i Ml 'll **111*11 ;ik M>i .'11 Mil .11 Mil IM M MM 1 >1i: ii (Oft ftft 44 *I1f .'11 M tl >0*1 M M 1 ' 111It' * III 1111 ..._____ H' "! jot ftMft 1M llkl MM 1 11 ft ft 1 tft <ftt < HONS 223925 APPENDIX D PGC/ECD CHROMATOGRAMS OP AROCLOR MIXTURES Hexane solutions were chromatographed on a 160 x 0.2 cm 10 glass column, packed with 1.5X SP 2260/1.95X SP 2401 on 100/120 mesh Supelcoport. The nitrogen carrier gas Mow rate was 30 i/min. The injector and detector tempera' tures were 250*C and 300C, respectively. The column temper* atures are noted on each figure. 463 HONS 223926 464 RROCLOR 1016 Appendix 0 RROCLOR 1232 RROCLOR 1248 Figure 0-1. Isothermal Chromatograms of Aroclors 1016, 1232. mo 1248 The column temperature was 1B0*C HONS 223927 PGC/CO Cftromafograms o 1 Aroctor Mixtures RROCLOR 1248 485 Figure 0-2. Isothermal Chromatograms of Aroclors 1248, 1254, ana 1260 The column temperature was 200*C. HONS 223928 486 RROCLOR 1016 Appendix 0 RROCLCR 1232 Figure 0-3. Temperature-Programmed Chromatogram of Aroctors 1016, 1232, ana 1248 The column temperature *as programed from 150C to 250C at 10#C/mm HONS 223929 PGC/ECD Chromatograms of Arocior Mixturas RROCLOR 1240 487 RROCLOR 1254 RROCLOR 1260 Figure 0*4. Temperature-Programmed Chromatogram of Arocior* 1248, 1254and 1260 The column temperature wa programmed from 1S0*C to 2S0C at 10#C/nn. MONS 223930 APPENDIX E TERMS AND ABBREVIATIONS 469 HONS 223931 490 Table E-l. Glossary of Terms Appendix Accuracy: Closeness of the analytical result to the "true" value. Analysis: The ascertainment of th# identity ana/or the con centration of the constituents or components of a sam ple. Analysis is often used incorrectly >n place of de termination. Only samples can ot analyzed: constituents or components are determined (see below). Examples of correct usage are: Analysis of fish for KBs. determi nation of KBs in fish.] Analyte; Chemical comoound or element which is the subject of an analysis. Aroc lor: Trade name (Monsanto) for a senes of commercial PCB and polychlorinated terpnenyl mixtures marketed in the Uni ted States. Askarel; A general term fpr a group of nonflammable syn thetic chlorinated aromatic hydrocarbons used as elec trical insulating media. See ASTM 197Ba, b. BrocMiann Activity; Amount of water added to alumina to control its adsorbent activity (Activity 1 * OX water; Activity V * 15X water). By-product KBs: PCBs unintentionally generated as impur ities m synthesis of other products (as opposeo to com mercial PCBs). CAS Registry Numoer: Unique number assigned by Chemical Abstracts Service to each chemical compound (see Ap pendix A). Chlophen; Trade name (Bayer, GFR) for a series of PCB mixtures. Congener: One of 209 PCBs or other group of compounds, not necessarily the same homolog. Destruction and removal efficiency (ORE); A measure of an incinerator's (or alternative method of destruction) performance in removing or destroying PCBs (or another compound). ORE is expressed as percent efficiency; ****in - mass out x 10 0 "#*sin MOMS 223932 Terms and Abbreviations ' ao l* E* 1 (Conn nued) 491 Determination: ascerta i nmen t of the ouantity or con centration of a specific substance m a samp]# See analyses. Electron imo*ct 'nass spectrometry (E IMS ): Low resolution mass spectrometry operated m the electron impact ion* wation mooe Equivalent method: Any method, certified against the primary method, whicn can be used for routine analysis of sam* pies External standard: Standards for calibration *rnch are not added to the sample extract. M or i s 11: Trade name (Flondin Company) for a synthetic magnesium silicate used for liQuid chromatographic cleanup and also for air sampling. High resolution gas-liquid chromatography: Gas chromatog raphy with a capillary column including WCOT. SCOT, fused silica, glass, and metal. Homolog: One of the 10 degrees of chlorination of PC8s (C,2H9C! through Cl2Clv0) or other group of compounds varying by systematic addition of a suostituent. Internal standard: Standards used expressly for quantitation adaed to samote extract immediately prior to the analyt ical determination. Isomer' Any PC8 or other cmpound which has the same molecu lar formula, out different positional suostitutions. 2.2'-Oichlorooipheny1 and 2,3-dichlorootpheny1 are iso meric; 4-chlorooipheny! and 2.2.4-tncntorobiphtny 1 art not. limit of detection (also MOD: Lowest concentration at which an analyte can be identified as present m the semple at a stated statistical confidence level- lower limit of Quantitation: lowest concentration to which a value can oe assigned at a staled statistical confi dence level MONS 223933 492 Appendix lab'e -1 (Continued) Mean. Arithmetic mean. Method: A series of techniques which for* specific, welldefined sampling or chemcei analysis for a specified compound( s )/matri x(ces) comomation. A distinct adapta tion of a tecnmque for a selected measurement purpose (e. g. , a specific GC/ECO opera11ng mode for analysis of pC6s. including column specifications and sample prepa ration Method detection limit: See limit of detection. Mineral oil: Liquid mixture of hydrocarbons obtained from petroleum. Packed column gas chromatography (PGC): Gas'liquid chroma tography performed using a column, typically ISO cm long i 2 m ID, packed with a liquid phase on a granular solid support materiel. Part per million (ppm): One part in 10*. For gaseous mix tures. a volume/volume (v/v) basis is typically used and: 1 ppm * mg/ml x RT ww where RT 22.A L/g-mole at 0C and \ atm * 24.5 i/g-mole at 25*C ana l atm and MW * molecular weight of compound, i .e. . g/g-moie for low concentration aqueous samples, a weight/volume (w/v) basis is most commonly used and 1 ppm * 1 mg/L ( l mg/kg for liquids with density * i). for nonaqueous liquids and solid materials, a weight/weight (w/w) basis is most commonly used and 1 ppm * 1 g/kg. Polychlorinatad biphenyl (PCS): On# of 209 individual com pounds having the molecular formula Ct2h Clt0fl, where n * 0-9. 4-Chlorobiphtnyl and 3,4.3',4'-tetrechlorooiphenyi are examples. This definition includes monochlorobiphenyl$, but not biphenyl. Polychlorinated dibento-g-dioxin (PCOO): One of 75 indi vidual compounds having the molecular formula C,*H Cl* 0-, where n 0-7 This definition includes monochloroflibtoidioxins. HONS 223934 Terms and Abbreviations Table E'l (Continued) 493 Ro lycn l or 1 nated a l be ^ o < uran (RCDP). One of 125 individual compounds having the molecular formula C,?H Clj 0. wnere n 0-7 ims definition includes mohoch lorodi * benzofurans. Procedure: The written directions necessary to us* a method or series of metnoos and tecnmques. Protocol, a sampling or analysis crocedu*e which is highly specific and from which few or no deviations are *1lowed Qualitative: Having to do with establishing the presence or identity of a compound. Quantitative: Having to do with measuring the amount or concentration of a compound m a sample Relative retention time; Retention time of a compound on a chromatographic system, relative to an internal stan dard; unitless number. Response factor; Instrumental response of an analyte mea sured against an interna) standard. Retention index; Systematic, unitless measure of a com pound's chromatographic retention as comoared to an homologous senes of standards, usually the n-alkanes. Retention time; Time ottween injection and detection of a compound on a chromatographic system under specified conditions, expressed m seconds or minutes. Saponification: Chemical reaction of a fat with strong base to form a glycerol and an acid salt. Sensitivity*. The slope of instrument response with respect to the amount of analyte. Also used colloquially in reference to lowest detectable amount of analyte. Silica gel: Granular form of silicic acid (H2Si03). Standard operating procedure: A written QA document which describes the way an organization typically conducts a routine activity. May address instrumental operation, instrumental maintenance, application of a laboratory technique, data review, or management oversight. HONS 223935 494 Appenai* E Table *1 (Continued) Surrogate-. Nonanalytt comeounes added to the samel* prior to any analytical man 1ou1 ations for the exoress purpose of measuring recovery tnrougn extraction, cleanup, etc. Technique: Scientific principle or specific operation (eg.. GC/ECO. Floristl column cleanup, or Webb and Hctall Quantitation). Yusno: A mass food poisoning incident caused by ingestion of a commercial rice oil contaminated with PC8s and otner haloaromatics HONS 223936 Terms and Abbreviations Table -2. L > St of Abbreviations 495 ASM ANSI AOAC ASTM 9HC Cl C IMS ClE OCHA 00E OOT ECO El EICP IMS EPA EPP1 FOA FFAP FID FTIR GC GC/MS American Society of Mechanical Engineers American National Standards Institute Association of Official Analytical Chemists American Society for Testing and Materials Benzene hexachloride (hexacnlorocyclohexane); several possible isomers Chemical ionization (mass spectrometry) Positive cnemical ionization mass spectrometry Continuous Iiquid-1iqgid extraction Ory Color Manufacturer's Association 1.1*0icnloro*2,2*bis(g"chloropneny1)etny1ene 1.1,l*Tricnloro-r,2-bi$(g-cnloropnenylJethane Electron capture detector Electron impact ionization (mass spectrometry) Extracted ion current plot Electron impact ionization mass spectrometry (US.) Environmenta1 Protection Agency Electric Power Researcn Institute (U.S.) Food and Orug Administration Free fatty acid phase Flam# ionization detector Fourier transform infrared spectrometry Ges*liQuid chromatography (column type unspecified) Gas*liQuid chromatography/mass spectrometry (ionization mode unspecified) MONS 223937 496 GPC HECO HPIC HRE1MS HRGC 10 IR IUPAC K K0 KOH IMS LOO LOQ M MOL MOG MS/MS Table E*2 (Continued) Appendix Gel permeation chromatography Hall electrolytic conouctivity detector (other similar detectors such as the Coulson are me I uded) High performance liquid chromatography High resolution electron impact mass spectrometry High resolution ga$"1iquid chromatography Inside diameter Infrared spectrometry International Union of Pure and Applied Chemistry Partition coefficient Octano1-water partition coefficient Kudtma-Oani$n evaporator Potassium hydroxide Limited mass scanning (mass spectrometry) Limit of detection. Lowest concentration at which an analyte can pc identified as present in the sample at a stated statistical confidance level Limit of quantitation. Parent m/i ion in a mass spectrum (equivalent to molecular weight) Method detection limit Mi 11s'Onley"Gaither procedure for analysis of fatty foooi and related matrices (Mills et al. , 1963) Mass spectrometry/mass spectrometry co n. HONS 223938 firms and Abbreviations Table E*2 (Continued) 497 m/z NAA H8S NCI NCI MS NIOSH NMR NRC NTlS OECD PAM PBS PC8 PCBP PCCY PCOO PCOF PCH PCPY PCQ PCQE PCT PCC Mass*to*charge ratio m mass soectrometry; m/e. amu. and dalton also oescnoe the mass units in mass spectrometry Neutron activation analysis (US ) National Bureau of Standards Negative cnemical ionization (mass spectrom etry) Negative chemical ionization mass spectrometry (US.) National Institute for Occupational Safety and Health Nuclear magnetic resonance spectrometry National Research Council (U.S.) National Technical Information Service Organization for Economic Cooperation and De velopment Pesticide Analytical Manual (PDA) Polyoroninated Diphenyl Polychlorinated biphenyl Polychlorinated Dipnenylene Polychlorinated chrysene Polycnlorinated dibenzo-g-dionin Polychlorinated dlbenzofuran Polychlorinated naphthalene Polychlorinated pyrenes Polychlorinated queterpnenyl Polychlorinated quaterphenyl ether Polychlorinated terpnenyl Packed column gas-liquid chromatography HONS 223939 496 p 10 ODD DO* Precision PUP QA QC "f RF RI ft IA R1C RK(t RP RRF RRT RSD RT SASS SCOT Table 2 (Continued) Appendix E Photo'onwenon oetector P*rts per billion (10 *; American system) Parts par mi 11 ion (10 *) Reproduob'lity of an analysis, measured by SO of replicates Polyurethane foam Quality assurance. An organization's program for assuring the integrity of data it produces or uses Quality control. The specific activities and procedures designed and imolemented to measure and control the Quality of data being produced Movement of a UC spot, measured as a fraction of the solvent front. Also used with column chromatography to measure the fraction of the total column length a band moves. Response factor Retention index Radioimmunoassay or radioisotope o'lution assay Reconstructed ion chromatogram (in GC/MS) Relative molar response Reverse phase (liquid chromatography) Relative response factor Relative retention time Percent relative standard deviation (SO/maan % 100) Retention time Source Assessment Sampling System Support coated open tubular (HRGC column) HONS 223940 Terms and Abbreviations Table E*2 (Continued) 499 SIM SiMCA T CO TCDO TCOF TIC TIC TOC 1 TOM T SCA USWAG uv WHO XAO-2 XRF Selected ion monitoring (also multiple ion de lection, *10. on mass fragmentography; in GC/HS) SIMple Classification by Analogy (principal components modeling technigue) Thermal conductivity detector Tetracnlorodibenzo-g*dioxin TetracnioroQibenrofuran Total >on current cnromatogram (in GC/MS) Thin-layer chromatograpny Total organic cnlorme Total organic halogen Toxic Substances Control Act, PI 94-469 (1976) Utilities Solid Waste Activities Group of the Edison Electric Institute Ultraviolet (spectroscopy) world Health Organization Poiystyrene*div>nylbenzene copolymer; also marketed with different numerical suffices. Trade mark. Rome and Haas x-ray fluorescence HONS 223941 INDEX Acetonitrile back-partition. 50-60. 62. 101. 106. 109. 122. 154*156. 167 (also see Hduid*1>quid partition) Acid digestion. 101. 107. 109. 156*158. 167 (also see sulfuric acid) Adipose tissue (also see animal tissues, humans, and \ipids) Analysis of. 56. 59. 99*103. 106. 12Q. 121. 12S. 127. Ul. 136. 143. 150. 152. 153. 155, 157. 161. 166. 186, 313. 326 Occurrence in. 24. 25, 33, 34. 258 Adsorptive losses. 68*69. 71. 114. ll5 Air (also see source sampling) Analysis of. 56-59. 95-97. 122. 127, 131*133. 321. 329 Contamination by, 115. 123 Occurrence in. 24. 27. 28, 35, 51*53 Sampl mg of. 63, 71*84 Alcoholic K0H (see Base, cleanup) Alumina, 100. 102. 107, 108, 118, 119. 122. 126. 130-134, 141, 145. 148, 163. 168 Animal tissue (also see adipose tissue. Blood, eggs, food, humans, mi Ik) Analysis of. 100-108, 119. 121. 122. 127. 131. 141-143. 161. 166 Occurrence in. 24*26. 32. 35 Apiezon l, 176. 182. 186. 188. 189. 19S Aqueous solubility. 10. 461*467 Arodor composition. 17*19, 136*138, 140. 145. 175, 179-180, 290. 469-475 Aroclor. 1, 15. 16. 490 (also see Aroclor composition) Askarel. 17, 490 Automated quantitation, 299*300 Azulent. 118-120. 124, 169 Sallscnmiter numbers (see iUPAC numbers) Base, cleanup. 57-60, 89. 99. 104. 106, 110. 131. 161, 162. 165 8ioconceotration. 9. 24. 26. 34 Biological properties, 37-40, 45-51 Biphenyl, 5. 177. 190, 242. 462 Birds (also see animal tissue) Analysis of. 108. 146. 320*322 (also see food) Occurrence in. 24-26 Blood (also see animal tissue, and humans) Analysis of. 56. 59. 87, 97-100. 119. 121. 127. 131, 154, 155. 313. 322. 336 Occurrence in. 24, 25, 51-53 Bodman bottle. 64 Boiling points, 10-12 Brockmann activity. 130. 490 By-product PCBs, 3. 490 (also see pigments) Analysis of. 60-62. ?4. 121, 156, 314. 318. 331-336 Sources and regulations, 22-23 501 moms 223942 502 index Calibration (GC). 230. 279*281 (also see response factors) Caoacuor fluids. 60. 112. 157, 162- 163. 211. 311-312 (also see oi1) Capillary GC. 174 (also see nign resolution gas chromatography) Carbon (adsorbent). 113, 118, 131. 134-142. CAS registry number, 6, 461-467. 490 Celite, 60. 67. 90. 124. 136 Charcoal (sat carbon) 148. 166 Chemical ionization mass spectrometry, 61, 77. 85 222 231. 299. 495 ' Chemical properties. 14-23, 36*44 (also see physical properties) Chlor-N-Oi1 . 263 Chlorinated benzenes, 17. 60 Chromic acid (see enromium trioxide) Chromium tnoxide, 148, 158-161, 167 CI MS (see cnemical ionization mass spectrometery) Coeluting congeners. 188-194 Collaborative studies. 6?. 93, 99. 267. 293. 319-337 Colorimetric detection, 260. 263 Commercial mixture properties. 15-22 Commercial use. IS-17, 22 Computerized Quantitation (see autometed Quantitation) Confirmation, 161. 257-259. 308. 317. 318 Congener, 6. 490 Continuous liquid-liquid extraction, 63, 67, 88. 89. 91. 92 Cooiting oil (see Yusho) Cyanide. 164-165 ODE, 119. 121. 123-126, 130, 131, 134, 136. 148. 150. 158-161. 167. 197. 236, 243, 244. 496 00T. 34. 102, 121. 124, 126. 130, 131, 134, 126. 147. 148. 150, 160, 161. 242, 244, 246. 249, 254, 495 Decachlorobipnenyl, 5, 12, 15. 16, 22. 240-242. 467 Degradation, 36-45, 156. 159 Oetection limn (general), 61. 65, 89-91, 194. 209, 248, 259, 302, 307-309 (also see limit of detection and method detection limit) Diagnostic pea**, 272, 289. 293-294 Oisposel, 3. 35-37 Disti)lation, 89, 102. 145 (also see steam distillation) Oowther* 6, 22 Dry deposition, 68, 76. 77, 97 Duel column GC. 257-258, 295-296 Earthworms, 108 Eggs (also see birds, animal tissue) Analysis of, 107, U9, 121, 130, 131. 148. 155 Occurrence in. 24. 25, 32 ElMS (see electron impact mass spectrometry) HOMS 223943 Indax 503 Electrochemical properties. 13 Electrolytic conduct!vity detector, 210*211. 260*262, 26 5 Electron capture detection (see high resolution gas chromatograpny and packed column gas chromatography) Electron impact mass spectrometry, 217*230, 275*277, 295, 297 (also see hign resolution gas chromatography, packed column gas chromatography. ana response factors) Environmental persistence, 37*39 (also see weathering) Environmental transport, 34*36 (also see weathering) Eat (see adipose tissue) feed (animal), 108, 148 (also see food, analysis of) F enc1 or OK. 22 Pish (also see shellfish) Analysis of. 103*105. 121. 124, 126. 127. 130, 131. 134, 138, 141, 147, ISO. 154. 1S8. 160. 161, 320*322. 336 (also see food, analysis of) Occurrence in, 1, 24*26. 32 Flor 1 si 1, 491 Air sampling, 58, 59. .*7S, 80*84, 96-97 Column cleanup. 55, 57*60, 62. 99. 119*124, 126-128. 131. 134, 135. 143. 153. 1S5, 157, 1S9, 161, 167, 168. 337. 330 Slurry cleanup. 61. 148*149. 163 Fluorescence spectra. 13 Fluorescent light ballasts, 16. 28 Food (also see animal tissue, feed, fish, milk, oil, plant tissue, and shellfish) . Analysis of. 56. 60. 62. 100*110. 113-114, 120. 127. 131. 153, 155, 1S9. 161 Occurrence m, 24, 32 Formation. 23 Fourier transform infrared spectrometry (see infrared spectrometry) Freeze-oned samoles. 107 FTIR (see infrared soectrometry) Fugacity, 13 Fuming sulfuric acid, 158. 185 (also see sulfuric acid and acid digestion) Fused silica capillary GC (see high resolution gas chromatography) GC (unspecified). 57*60. 171*243. 255, 275, 495 (also see high resolution gas chromatography and packed column gas chromatography) GC/MS (unspecified), 57, 58. 60, 240. 2*2, 277-280. 284, 495 (also see high resolution gas chromatograony and packed column gas Chromatography) Gel permeation chromatography, 149*154, 167 Glass capillary GC (see high resolution gas chromatography) Glass fiber filter, 76. 78*80 HONS 223944 504 index Grtn, 108 (also see feed no food, analysis of) Half-lives, 37-39 Half-retention indices, 175, 177-179, 271 (also see rettntiOn m0*x) Hal) detector (see electrolyte conductivity detector) Henry s Law constants, 13 Hi-Vo) sampler, 76 High performance liquid chromatography, 1*1-147, 247-254, 299, 496 High resolution electron impact mass spectrometry, 200 236-237, 254. 258-259, 265 ' High resolution gat chromatograony, 174, 182, 186-188, 270-273, 491 (also see packed column gas chromatograohy) Electron capture detection, 184, 188-196, 204. 273 288-296, 301-302. 329 Electron impact mass soectrometry, 3, 44. 57-60, 186. 212-230. 258, 275-277. 295-98, 315-316, 322, 331. 333 (alto see electron impact mats spectrometry) Marne ionization detection, 249 Negative chemical ionization mass spectrometry, 201. 231-234, 258 (also see NCIMS) Homo log, 6, 491 HftGC (see high resolution gat chromatography) Humans (also see adipose tissue, blood, milk) Analysis of, 56, 59, 97-103. 121, 313 Occurrence in, 1, 24-32 Hydraulic fluids, 16. 112, 157, 163, 209, 211. 312 Ice coring, 77 Impingert, 75, 83 (alto see Modified Method 5) Inadvertently generated PCBs (see by-product PCBs) Incidental PCBs (see by-product PCBs) Incineration, 3. 36, 56, 59. 78-84, 314-315 Infrared spectra, 13, 14 Infrared spectrometry, 197, 255-256 Injection (GO, 196-197 Interlaboratory studies (see collaborative studies) Ion-tpcific electrode, 260 Isomer, 6, 491 iUPAC numoers. 6, 461-467 Laurie acid, 120 Limit of detection (instrumental), 56, 198, 199, 211. 233, 239, 253, 254. 256, 257, 297. 492 (also tee dttection limit and method detection limit) Lipids. 100-103. 106-110, 122, 124, 130, 134, 149-155. 159, 161, 165-166 (alto tea adipote tissue, acetonitrile back-partitioning, Morisil, food, milk, and gel permeation chromatography) Liquid-liquid partition, 154-156, 159 (alto see aceto nitrile back-partition) Low temperature luminescence, 257 Low temperature precipitation, 102 HONS 223945 Index 505 Mamma's {'occurence m), 2*-26 < 4) so sec imnils, humans) Mass spectra, 215*216, 2?5*277, 478*481 Mess spectrometry, 212*238, 295*299 {also see nigh resolution gas chromatography, mess soectre, end Decked column chromatography) Hess, eiect, 10. 480*481 (elso see molecular weight) Melting oomt. 10, 481*467 Mercury, 164 Method (Selection limit, 55*60, 72, 77, 80, 85, 94, 102 138, 198, 200, 201, 231, 236, 244, 247. 254, 327, 492 (elso see detection limit end limit of detection) Microcoulometry, 260 Milk Analysis of, 56, 59, 102, 106, 107, 119, 121. 122, 127. 256, 313, 315-316, 321. 324*326 (also see food, analysis of) Occurrence in, 1, 24, 25, 32 MiUs*0niy*Geither (see Florisil) Mineral oil (see oil, mineral) Motile mess spectrometer, 75, 85, 231 (also see portable instrueient) . Modified Method 5 sampling train, 61, 78*84 (elso see source sampling) Molecular weight, ?, 9, 10 (also see mass, exact) Monochlorobiphtnyl, 5, 22, 39, 462 MS/MS, 94, 236*238. 254, 259. 265, 496 Nature) gas, 56, 59, 84 NCJMS, 231*236, 258, 259, 265. 497 (also see high resolution gas chromatography) Neutron activation analysis, 257 Nuclear magnetic resonance spectrometry, 14, 255 0ctanol*water partition coefficient, 10*13, 244 Oil, 85, 122. 133, 153. 1S4, 157, 253 (also see caoacitor fluids, hydraulic fluids-) Cooking (see Yusho) Insulating, 322, 330 lubricating. 323. 337-338 Mineral, 60. 77. 111*112, 145. 148. 155. 202. 209-211, 256, 330. 492 (also see transformer oil) Motor, 292. 311 Dice, 32*33 (also see Yusho) Silicone, 75, 111. 113, 155, 253 Transformer. 60, 61, 85, 111*113. 117. 122, 127. 133. 145*148, 154, 155, 158, 162, 163, 186, 202, 209-211, 247, 253, 255*256. 259, 263, 264, 270. 273, 274, 281, 287, 292, 293. 300, 301, 311-312, 315, 317, 330 Vegetable, 113-114, 155. 157 Waste, 60, 61. 85. 112, 157. 163, 186, 211, 281, 287, 300, 317 MONS 223946 906 inddx Picked column gas chroMtography (1so see high resolution ges chroMtography) Oectron cepture detection. 56*60, 74. 200, 203, 247 254 268*270. 282-288. 293, 295, 296, 301*302, 320*331,`337 * 483-488 * electron impact mss spectrometry, 59*61, 200, 295 (also see electron impact mss spectromectrometry) F)m ionizetion. 205, 238*239 Hell electrolytic conductivity detection, 200, 210*211. 269. 320 Photoionization detection, 329 ThenMl conductivity detection, 239 Peper end peper products, 56, 60, 110, 120, 122, 127, 143. 144, 158, 320, 321, 325, 327 Partition coefficients, 10, 13, 88 (also see octenol* water partition cofficients) Pattern recognition. 268*270, 273*274 PC8 nomenclature, 5, 6 PC8s as dy-products (see dy-product PC8s) Percent chlorine in PCBs, 7, 18 Perchlorination, 240*242, 253, 257 PGC (see packed column gas chromatography) Phosphorescence, 13, 2S3, 258 Photolysis, 37 Physical progenies, 9*14, 461*467, 480, 481 (also see chemical properties) Pigments. 22. 23. 56. 60, 121. 123, 157. 207. 314, 321. 330 Plant tissue, 24, 35, 108*109, 143, 148 (also see feed. food, and grain) Plasma chroMtography. 257 Polychlorinated biphenylenes, 41, 42, 481, 497 Polychlorinated dibenzo*p*d1oiins, 32, 41, 42. 126. 131. 138, 141, 142. 145. 186. 236, 237. 480, 492, 497 Polychlorinated dibenzofurans, 2, 17, 21, 32, 33, 39. 41, 42. 45. 131, 138, 141, 142, 14$, 186. 480. 493, 497 Polychlorinated naphthalenes, 141, 142, 159, 480, 497 Polychlorinated quaterphenyls, 17, 42 Polychlorinated terpnenyls, 16, 42, 183 Polyurethane foam Air sampling. 71*75. 96. 131 Column cleanup (with carton). 134, 135. 138, 140, 141 water sampling. 63, 65*68, 68 Portaole instrument. 7S, 85, 210, 231 `Preservation (see sample storage) Prppertle* (see chemical properties, commercial mixture properties, and physical properties) Purge and trip, 90 Quality assurance, 305*318, 49B Quality control, 56*61, 30S, 307*310, 314*318. 498 Radioimmunoassay, 256 HONS 22394? Indtx 507 Rainwater. 29. 68 (also see dry disposition) RC1 (see total organic na'>de) Reference materials (see standards) Registry numoer (see CAS registry number) Regulatory analyses. 292-29* (a'so see diagnostic oeefcs) Relative retention times (see retention time) Response factors, 278*27?, *93. *98 (also see cal iteration) eco. lee, 190-192, :;2. :o5. :o9 MO, 205 HMS, 222-229 NCIMS, 231. 232 Retention index. 175, 179-180. 270-271, *93. *98 (also see na)f-retention moe and retention time) Retention time, 174, 175, 176, 179. 186. 187, 190-19*. 268-273, 276, *93, *96 (also see retention index) Rice oil (see oil, rice) Samole storage, 68-71 Saponification, 493 (see oast, cleanup) SASS train, 60 (also see source settling) Screening for interferences, 26* Screening for PCBs, 2*0-22, 259-26* Sediment, 311-312 Analysis of, 56-58, 92-5, 120, 130, 133, 135, 161, 16*. 168. 321, 32*. 327-329 Occurrence in, 2*. 31, 33-35 Settling of, 85 Sewage sludge (see sludge) Shellfish and other macroinvertabrates (also see fish), 119, 121, 130, 1*8 Silica gel. 57-60, 62. 119, 123-130, 1*3, 1*5, 1*7, 1*8, 157-158. 2*5, 2*6. 2*9. 250, 252. 325, 329. *13 Silicone oil (see oil, silicone) S1HCA, 273-274, *99 (also see oattern recognition) Size-exclusion chrometog-aphy (see gel permeation cnromatograpny) Sludge, 33. 37. 56-68, 91-92. 127, 15*. 158. 16*. 165, 168 Soao, 113 Soi 1 Analysis of, 56-58 , 92-95. 120, 127, 130, 133, 134, 161, 313 Occurrence in, 2*. 31, 35 Settling of, 85 Solid waste, 58 Sorbents (set alumina, caroon, florisil, polyurethane foam, Tenax, and XAO) Source sampling, 58, 59, 61, 62, 78-84, 96-97, 127, 158. 186. 260-261 Spills. 61 Stack gas (see source templing) Standards, 14-15, 289. 292, 310-312 HONS 223948 506 Indox SUM disti llation, 66, 96, 104, 10$ (also see distillation) Sulfuric *Cid, 57-60. 101. 109. 110, 122. Ml. 147. I4g, 166*166, 163, 167 (also see acid digestion) ' Surface sapl, 41, 86 Surrogate, 300*101, 494 Synthesis, 14-16 Ten** Air stapling, 72. 73, 75. 61 Utter stapling, 67. 68. 90 Thtratl desorption. 93-94 Thin-layer chromatography, 59. 147*148, 242*247, 259 26$, 269, 299 ' TOC I (set tottl orgtnic htI id#) Tot*) trees (quantitation), 57*60. 281. 287*288, 324*327 Tot*) orgtnic chlorine (set tottl orgtnic htlidt) Tot*) orgtnic htlidt. 260*262 T0X (see tot*) orgtnic htlidt) Toxic Subtances Control Act, 2, 45, 499 Trtnsforatr oil (set oil, transformer) Ultraviolet spectra, 13, 299 Unintentionally generated RC8s (see by-product 9CBs) Vapor pressures, 10*13, 77*78 Vegetable oi) (see oil, vegetable) Veltametry, 257 (also see electrocheaical properties) Waste oil (see oil, waste) water Analysis of, 56, 57. 61, 88*90, 121, 122, 127, 131. 133. 154, 161, 293, 294, 321-322, 325-327 Occurrence in. 24, 29*30. 35 Samp I ing of, 63*71 (also see rainwater stapling) Water solubility, 10. 461*468 Weathering, 272. 293*295 (also see environaentat persistence and environmental transport) Webb-HcCall, 57-60, 282*286, 293, 324*327 wipe samples (see surface staples) X-Ray fluorescence, 264 XA0 Air stapling, 71*75. 78. 80*84, 96, 97 weter sMMng, 63. 66*68. 90*91 Yusho, 2, 2$, 32*33. 39, 40. 42. 46. 48, 111, 113*114, 131, 494 MOMS 223949