Document e5NYDa95By8Q75g57ND1xwrK9

Ml Metric Power esearen institute Topics: PCB Chemical analysis Transformers Capacitors PCDF-PCDD Insulating oil e p r i EUEA-5^i3 Volume i Project 2028-7 Final Report October 1987 Analysis of Polychlorinated Dibenzofurans and Polychlorinated Dibenzo-p-Dioxins in Transformers and Capacitors Volume 1: PCDF/PCDD at New York State Health Department Prepared by New York State Department of Health Albany, New York 010953 783764 . Use of the 13C compounds allowed successful separation of the com ponents in several closely eluting pairs of physiologically active PCDF and less-active compounds. Analyses of samples from utility equipment suggested that the PCDF-PCDD present did not result from high-load, high-temperature operation. Volumes 1 and 2 describe several analytic techniques, with the appen dix of Volume 2 including a report on the analysis by the University of Umea in Sweden, as well. Volume 3 summarizes all the laboratory techniques, presents comprehensive statistical analyses, and provides an executive summary. EPRI PERSPECTIVE This research is a landmark in PCDF-PCDD analysis. One important result is the synthesis of new PCDFs for use as spiking compounds in gas chromatography-mass spectrometry analysis. The ability to sepa rate many of the active PCDF compounds from more innocuous materi als is also of great value. The high correlation of results from several laboratories indicates that researchers can exercise great flexibility in selecting techniques and developing facilities. PROJECTS RP2028-7, RP2028-6. RP2028-10 EPRI Project Managers: Gil Addis; Jacques Guertin Electrical Systems Division; Environment Division Contractors: New York State Department of Health; Battelle Columbus Laboratories; Research Triangle Institute For further information on EPRI research programs, call EPRI Technical Information Specialists (415) 855-2411. GENP 010954 783765 Analysis of Polychlorinated Dibenzofurans and Polychlorinated Dibenzo-p-Dioxins in Transformers and Capacitors Volume 1: PCDF/PCDD at New York State Health Department EUEA-5443, Volume 1 Research Project 2028-7 Final Report. October 1987 Prepared by NEW YORK STATE DEPARTMENT OF HEALTH Wadsworth Center for Laboratories and Research Corning Tower The Governor Nelson A Rockefeller Empire State Plaza Albany. New York 12201 Principal Investigators D. R. Hilker G. A Eadon K. M. Aldous R. M. Smith P W. O'Keefe H. Valente S. Connor J. Jurusik Prepared for Electric Power Research Institute 3412 Hillview Avenue Palo Alto. California 94304 EPRI Project Managers G. Addis Transmission Substations Program Electrical Systems Division J. Guertin Land and Water Quality Studies Program Environment Division GETS? 010955 783766  i ORDERING INFORMATION Requests for copies of this report should be directed to Researcn Reports Center (RRC), Box 50490. Palo Alto. CA 94303, (415) 965-4081 There is no charge for reports requested by EPRI member utilities and affiliates. U.S. utility associations. U.S. government agencies (federal, state, and local), media, and foreign organizations with which EPRI has an information exchange agreement. On request. RRC will sena a catalog of EPRI reports Electric Power Researcn institute and EPRI are registered service marks of Electnc Power Researcn Institute me CoDyngnt S 1987 Electric Power Researcn institute. Inc All ngnts reserved NOTICE This report was prepared by the organization(s) named below as an account of work sponsored by the Electric Powr Researcn institute Inc (EPRI). Neither EPRI members of EPRI tne organizations) named below, nor any person acting on behalf of any of them (a) makes any warranty, express or implied, with respect to the use of any information, apparatus, method, or process disclosed in this report or that such use may not infringe privately owned rights: or (b) assumes any liabilities with respect to the use of, or for damages resulting from the use of any information, apparatus, method, or process disclosed m this report Prepared by New York State Department of Health Albany. New York 783767 GENP 010956 ABSTRACT Seven sampLes of in-service utiLity fluids were analyzed for nineteen different polychlorinated dibenzofuran (PCDF) and polychlorinated dibenzo--dioxin (PCDD) compounds. After spiking with five different C-Labeled internal standards, the sampLes were chromatographically simplified (semi-automated). Analyses were conducted with high resolution gas chromatography-mass spectrometry (GC-MS) using a 50-m DB-5 or an OV-225 fused-silica capillary column. Generated calibration plots for eight different individual compounds were linear over four orders of magnitude concentrations. Analyses in triplicate provided some insight on reproducibility of method. Spiked sampLes were analyzed with an average error of 28.9Z, indicating that for the chosen anaLytes in this type of oily matrix, the method was quite reproducibLe and accurate. The reLative standard deviation was less than 30Z for more than 92Z of the analyte determinations. In general, the study showed that the samples of in-service utility fluids have considerably different PCDF-PCDD profiles. Maximum concentrations of tetrachlorodibenzofuran (TCDF) and tetrachlorodibenzo--dioxin (TCDD) were 1.2 and 0.001 mg/kg, respectively. Maximum concentrations of octachlorodibenzofuran (OCDF) and octachlorodibenzo--dioxin (OCDD) were 40 and 0.02 mg/kg, respectively. And two fluids contained barely detectable quantities of any PCDD or PCDF (maximum concentration: 0.003 mg/kg). 783768 ill GENP 010957 ** CONTENTS Section 1 INTRODUCTION 2 METHODS In-Service Fluid Samples PCDD and PCDF Standards Sample Extraction and Extract Preparation High Resolution Capillary Gas Chromatography/Low Resolution Mass Spectrometry (HRGC/LRMS) High Resolution Gas Chromatography/HighResolution Mass Mass Spectrometry (HRGC/HRMS) 3 DISCUSSION Preliminary Baseline Study Data Calibration and Quality Assurance Data Baseline Data In-Service Liquids 4 REFERENCES APPENDIX A IN-SERVICE LIQUIDS BACKGROUND INFORMATION APPENDIX B ANALYTE CALIBRATION CURVES APPENDIX C ANALYTE RESPONSE FACTOR CURVES APPENDIX D TABLES OF RESULTS APPENDIX E BAR GRAPHS OF RESULTS APPENDIX F TABLES OF RECOVERIES, RELATIVERECOVERIES AND DETECTION LIMITS Page 1-1 2-1 2-1 2-1 2-2 2-3 2-4 3-1 3-1 3-2 3-5 3-7 4-1 A-l B-l C-l D-l E-l F-l GENP 010958 v 783769 ILLUSTRATIONS Figure 2- 1Typical MSD Raw Data 3- 1Exact Mass Chromatograms Showing the Retention Time Window for TCDD 3-2 High Resolution Mass Scans & Summaries 3-3 Interference inthe Determination of 2378-TCDD in Spiked Aroclor 1260 3-4 High Resolution Mass Chromatogram of Spiked Aroclor 1260 3-5 High Resolution Mass Data from the 2,3,7,8-TCDD G.C. Peak from the Spiked Aroclor Sample Page 2-4 3-3 3-4 3-10 3-11 3-12 GENP 010959 vii 783770 $ TABLES Table 2-1 H-P 5890 Gas Chromatograph Temperature Program 2-2 Carlo-Erba Gas Chromatograph 4160 Temperature Program Page 2-3 2-5 783771 GENP 010960 ix SUMMARY Much concern has been attached to the occurrence of poLychLorinated dibenzofuran (PCDF) and poLychLorinated dibenzo--dioxin (PCDD) in the environment. SeveraL environmentaL catastrophes were precipitated by the identification and quantita tion of these two cLasses of compounds. 2,3,7,8-tetrachLorodibenzo--dioxin (2,3,7,8-TCDD), one of 2L0 possibLe compounds within these cLasses, is generaLLy regarded as the most toxic man-made compound. Much of the controversy generated at the Love CanaL was a resuLt of finding 2,3,7,8-TCDD. The FederaL government LiteraLly purchased the town of Times Beach, Missouri when 2,3,7,3-TCDD was found wideLy dispersed in the soiL. A transformer fire in the State Office BuiLding in Binghamton, New York, spread high concentrations of PCDF and PCDD throughout the buiLding's eighteen stories. ConsequentLy, the buiLding has been cLosed since February L98L with ongoing cLeanup costs of severaL miLLion doLLars. The Binghamton Office BuiLding disaster heLped to emphasize that PCDF and PCDD contamination is a potentiaL utiLity probLem. This unfortunate event and other research reveaLed that PCDF and PCDD can be found in some transformers as a resuLt of contamination, severe operating conditions, or fire. And hundreds of thousands of AskareL and poLychLorinated biphenyL (PCB)-contaminated mineraL oiL transformers are stiLL in use in the Unites States. An obvious aLternative to repLacing currentLy operating eLectricaL equipment suspected of contamination is to identify the equipment with the greatest environmentaL concentrations of PCDF and PCDD. This wiLL require an understanding of the factors that controL the degree of contamination. It wiLL aLso be necessary to have accurate methods of measurement. EstabLishing accurate measurement methods for PCDF and PCDD in PCB matrices is a goaL of this study. In addition, the study measures compound-specific concentrations of PCDF and PCDD in reLativeLy weLLknown insuLating fLuids from commonLy used eLectricaL equipment. This determines the measurement precision. ALso, this work constitutes part of a Larger interLaboratory study that wiLL provide insight regarding the accuracy and measurement methods for assessing PCDF and PCDD contamination in utiLity equipment. GENP 010961 783772 Seven different pieces of electrical equipment (i.e., load center network trans formers, capacitors, precipitators, distribution transformers, and arc furnace transformers) were analyzed for nineteen PCDF and PCDD compounds. Historical information such as manufacturer, age, use, and maintenance was collected on each piece of equipment. Prior to analysis, the fluid sampLes were chromatographically simplified, concentrating the PCDF and PCDD fractions while eliminating interfering compounds. Each fluid sample was prepared in triplicate and each extract was chemicaLly anaLyzed by gas chromatography-mass spectrometry (GC-MS). In addition, three common insulating fluids (mineral oil, ArocLor 1016, Aroclor 1260) were spiked with known quantities of compounds of interest. Then, these were concentrated and subjected to a similar "cleanup" procedure as used for the samples from the in-service equipment. This latter analytical procedure served as quality control for the analysis of unknown samples. Spiked samples were analyzed with an average error of 28.9Z indicating that for the chosen analytes in this type of matrix, the method was quite reproducible and accurate. The relative standard deviation was less than 30Z for more than 92% of the analyte determinations. In general, the study showed that the samples of inservice utility fluids have considerably different PCDF-PCDD profiles. Maximum concentrations of tetrachlorodibenzofuran (TCDF) and tetrachlorodibenzo--dioxin (TCDD) were 1.2 and 0.001 mg/kg, respectively. Maximum concentrations of octachlorodibenzofuran (OCDF) and octachlorodibenzo--dioxin (OCDD) were 0 and 0.02 mg/kg, respectively. And two fluids contained barely detectable quantities of any PCDD or PCDF (maximum concentration: 0.003 mg/kg). 783773 S-2 GENP 010962 Section 1 INTRODUCTION Considerable interest has been focused on the analysis of various environmental samples for the closely related families of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). This interest originated with the documented occurrence of the most toxic isomer, 2,3,7,8-tetrachloro-dibenzo-pdioxin (2,3,7,8-TCDD). This highly toxic species has been detected in Lake Ontario fish (1_), in human adipose tissue (2.), and turtles (3_) , landfills (4) and municipal incinerators (5.), (6.), (D and the combustion products of askarels and transformer fluids (). Rappe has presented a comprehensive review of the occurrence of 2,3,7,8-TCDD and related isomers (9_). Increased activity in this area stimulated the availability of pure native (12C) and labelled (11C) PCDD and PCDF compounds for use as analytical standards. This development coincided with investigations of improved compound separation techniques and was driven by the known fact that other PCDD and PCDF compounds have significant toxicity (10), ( U ) , (12). (11)- PCDD and PCDF compounds have been detected in Utility Askarel fluids and combusted or pyrolyzed Utility Askarel fluids (8.), (9), (8.). The occurrence of these contaminants in dielectric fluids raises several questions. Fundamental to this work is the question, "What are the predominant isomers and their concentrations in utility fluids in equipment now in use?". Once the specific compounds and their concentrations are known the relative health risk posed by continued use of these fluids can be assessed. To this end seven samples of dielectric fluids from in-service electrical equipment and three baseline samples were analyzed for the presence of 19 different compounds or groups of isomers. The samples were analyzed using five different C-labelled internal standards. In all, 13 different standards were synthesized and used for calibration and quantitation. Fourteen different individual PCDD and PCDF compounds were quantitated along with the total concentration of tetra- through hepta-CDF and tetra-CDD congener classes. The determination of each analyte was replicated three times for each sample in order to generate an average concentration, standard deviation of the concentration, and GENP 010963 783774 percent relative standard deviation (coefficient of variation). Three of the ten fluid samples were spiked with known amounts of individual compounds as a check on the accuracy of this method. Furthermore, the same ten fluid samples were subjected to an interlaboratory round robin analysis. The results of that study will be published elsewhere. Thus, besides providing an initial view of PCDD and PCDF compound concentrations in in-service utility fluids this work represents the most rigorous study of PCDD and PCDF compounds in an environmental matrix. 783775 010964 1-2 m Section 2 METHODS IN-SERVICE FLUID SAMPLES Samples of in-service dielectric fluids were collected by various utilities and shipped to the Battelle Columbus Laboratories. BCL was responsible for accessioning the fluids and developing a catalogue of background information. The type of equipment from which each in-service fluid used in this study was obtained is listed below: 1. 1962 Load Center Network Transformer 2. Load Center Network Transformer 3. Substation Distribution Transformer 4. 1946 Load Center Network Transformer 5. Precipitator 6. 1976 Arc Furnace Transformer 7. Capacitor A listing of accumulated background information on each of these pieces of equipment is given in Appendix A. In addition three typical virgin dielectric fluids were blindly spiked to test the method accuracy. These fluids were: 1. Mineral oil 2. Aroclor 1016 3. Aroclor 1260 PCDD AND PCDF STANDARDS PCDD and PCDF standard compounds including 13JC-labelled standard compounds were synthesized by Radian Corp., Austin. The standards were dissolved in solvent at the various concentration levels and shipped in sealed glass vials. Seven vials were received each containing all of the following compounds: 2.3.7.82.3.7.81.2.3.7.82.3.4.7.8- TCDD TCDF PnCDF PnCDF 2.3.7.8- TCDD-^C.2 2.3.7.8- TCDF-13C12 1.2.3.7.8- PnCDF-13C12 2-1 010965 783776 1, 2, 3, 4, 7, 8-HxCDF 2,3, 4,6,7, 8-HxCDF 1, 2,3,4, 7, 8-HxCDF-13C12 1,2,3,4,6, 7, 8-HpCDF 1,2,3,4,6,7, 8, 9-OCDF 1,2, 3,4, 6, 7, 8, 9-OCDD- C12 Each vial contained all of the native compound3 at one of the following concentration levels: 7.500 ng/ml 2.500 ng/ml 500 ng/ml 150 ng/ml 40 ng/ml 10 ng/ml 2.5 ng/ml Each standard solution contained all of the 1TC-compounds at 500 ng/ml each. SAMPLE EXTRACTION AND EXTRACT PREPARATION Samples of electrical insulating fluids and mineral oil dissolved in hexane were received from Radian Corp. in sealed vials. The volume of a portion of each vial was measured and extracted by adding 25 ml of acetone and mixing thoroughly. Hexane (25 ml) was added and the sample was,stirred and extracted for a minimum of 1 h. To remove PCBs and nonplanar aromatics and isolate one fraction containing all tetra- to octa-CDF and -CDD -the sample extract was chromatographed on acid alumina, PX-21 carbon and neutral alumina. A preprogrammed Hamilton valve control system designed in our lab was used to reproducibly select solvents and chromatographic columns (_.). The recovery of all tetra- to octa-CDFs and -CDDs (as verified with available standards) from an individual chromatographic column is >95Z. The sample extract was applied to an activated acidic alumina column, followed by 30 ml of 3Z CH2C12 in hexane. The CDF/CDD fraction was eluted with 70 ml of 50Z CH2C12 in hexane onto a carbon column followed by 50 ml of 10Z benzene in hexane. The CDF/CDD fraction was eluted in the reverse direction with 30 ml of 50Z xylene in hexane onto a neutral alumina column (replaces xylene with a volatile solvent) followed by 30 ml of 3Z CH2C12 in hexane. The final purified CDF/CDD fraction was eluted with 70 ml of easily volatilized 50Z CH2C12 in hexane and concentrated by heating to 100C and then vacuum evaporating to 4-10 pi (J3j . Prior to GC/MS, extracts were stored in the dark in sealed 150 ul borosilicate capillary tubes. GENP 010966 2-2 783777 HIGH RESOLUTION CAPILLARY GAS CHROMATOGRAPHY/LOW RESOLUTION MASS SPECTROMETRY(HRGC/LRMS) All sample extracts were analyzed with a Hewlett-Packard 5970 Mass Selective Detector. A portion of each extract was injected into the split-split less injection port(250C) and eluted through a 50m(0.25tnm i.d.;0.33ytn film thickness) Hewlett-Packard 5Z phenyl methyl silicone fused silica capillary column. The following temperature program was used: Table 2-1 H -P 5 8 9 0 GAS CHROMATOGRAPH TEMPERATURE PROGRAM Leve 1 1 2 3 4 5 Init ial Temp (C) 190 Initial T ime (min) 1.00 Finai Finai Rate Temp Time (C/Min) (C) (gin) Total T ime (min) 5.0 220 16.00 23.00 5.0 23 5 7 .00 33 .00 5.0 250 18.00 54.00 5.0 270 7 .00 65.00 5.0 300 24.00 95.00 The gas chromatograph was interfaced directly to the source of the mass selective detector and the transfer line and ion source were heated to 275C and 150C, respectively. The mass selective detector was operated in the selective ion monitoring (SIM) mode. The m/z values characteristic of native TCDD, TCDF, PnCDF, HxCDF, OCDF and OCDD and TCDD-13C12> TCDF-13C12, PnCDF-13C12, HxCDF-13C12 and OCDD-^3C^2 were monitored at various times during the 95 minute runsk The time windows used for monitoring the different congener classes (TCDD, TCDF, etc.) were determined by the previous injection of either window standards (TCDD) or a mixture of combusted PCB. Raw data were collected into and processed by an H-P Quicksilver data system. The data system was used to generate electronic copies of reports of retention times and areas at each m/z value monitored (Figure 2-1). Additional custom software was used to identify G.C. peaks and quantitate analyte levels. This software was written by NYSDOH staff (H. Valente) and runs on an IBM PC or XT. The H-P reports are input in ASCII and transferred by using a GENP 010967 2-3 783778 Pet Tine 30.827 32.157 34.550 35.5ZI 35.9'7 35.52! 35.757 37.141 37.794 38.322 38.844 39.1 19 39.562 40.088 40.506 41.446 41 .982 44.696 45.282 Maas 305.90 . Area 107155 22962 7919 44916 8556 129702 80014 508644 151286 96838 38905 38741 73974 2030 220688 83751 12165 3228 11243 Figure 2-1: Typical MSD Raw data. The retention time window for TCDF is shown. The Quicksilver data system automatically integrates the gas chromatographic peaks and labels each with its retention time. The list of retention times for each mass monitored is generated by a separate program. GENP 010968 2-4 783779 customized H-P Pascal operating system (sender) and the. program called Kermit (receiver ). HIGH RESOLUTION GAS CHROMATOGRAPHY/HIGH RESOLUTION MASS SPECTROMETRY(HRGC/HRMS) Some extracts were analyzed with a Kratos MS-50 high resolution GC/MS/DS. In this system, portions of the extracts were injected into the on-column injection port of a Carlo-Erba 4160 high resolution gas chromatograph and eluted through a 50m (0.20mm i.d.;0.33um film thickness) Hewlett-Packard 52 methyl phenyl silicone fused silica capillary column. The oven was temperature programmed as follows: Table 2-2 CARLO-ERBA GAS CHROMATOGRAPH 4 1 6 0 TEMPERATURE PROGRAM Level 1 2 3 Init ia 1 Temp (C) 190 Initial Time (min) 1.0 Rate (C/Min) 5.0 5.0 5.0 F inal Temp -Ll1 220 F inal Time (min) 16.00 235 7 .00 300 50.00 Total Time (min) 23.00 33 .00 86.00 The gas chromatograph was interfaced to the MS-50 through a direct line heated to 250C. The ion source temperature was 250C. The high resolution mass spectrometer was operated in either of two SIM type modes. In normal multiple peak monitoring mode (NMPM), the m/z values of a particular analyte and its corresponding internal standard were observed at 10,000 RP (102 valley) (1J2.) by integrating all the signal detected within 50 ppm of their exact mass values. In high resolution multiple peak monitoring mode (HRMPM) the mass spectrometer is operated at the same high resolving power but the analyte and internal standard exact masses are profiled. The data system adjusts the accelerating and electric sector voltages to focus a mass slightly below the mass of interest. The computer then triggers a 0.3 s analog scan through a 300 ppm section of the mass range which includes the exact mass of the ion of interest (IX)* In both ion monitoring modes, the raw data were acquired and processed by the Kratos DS-55 data system. Quantitation was done manually by calculating concentrations using peak areas obtained from the DS-55 output. G E N P 010969 2 -5 783780 Section 3 DISCUSSION PRELIMINARY BASELINE STUDY DATA In an initial phase of this project, five fluids were analyzed. These five fluids included the Aroclors 1016, 1242, 1260, tri- and tetrachlorobenzenes, and mineral oil. Each of these fluids was spiked with four C-labelled internal standards, i.e. 2,3,7,8-TCDF-13C 12, 1,2,3,7,8-PnCDF-13C12, 2,3,7,8-TCDD-1 3 2, OCDD-13C12Native 1,2,3,4,7,8-HxCDF and 1,2,3,4,6,7,8-HpCDF were also added since the R e labelled version of these compounds was not available at the time the samples were prepared. Additionally, one of the fluids, aged mineral oil, was spiked with "blind" levels of certain native PCDD and PCDF compounds and approximately 500 ppm each of Aroclor 1260 and tri- and tetrachlorobenzene and 100 ppb each of 1,2,3,4,7,9-HxCDF, 2,3,4,7,8-PnCDF, 1,2,3,4,8-PnCDF and 2,3,4,8-TCDF. The results of these preliminary analyses are given in Appendix D Tables D-l and D-2. The levels of PCDD and PCDF compounds added as a blind spike to the aged mineral oil sample were quantitated with reasonable accuracy. Three of the four compounds spiked were the same compounds as the internal standards used for quantitation. 2.3.7.8- TCDD, 2,3,7,8-TCDF and 1,2,3,7,8-PnCDF were quantitated by comparing the areas for these isomers with 2,3,7,8-TCDD-Rc^2, 2,3,7,8-TCDF-Rc^2, and 1.2.3.7.8- PnCDF-13JC^2 respectively. The percentage error in the determination of the levels of these native isomers was 7.5Z, 70Z and 0Z respectively. Although the level of 1,2,3,7,8-PnCDF is reported as 140 ppb, this includes 100 ppb of 1.2.3.4.8-PnCDF, which had been added. These two isomers were not separated on the SP2330 fused silica capillary column with the conditions that were used. 2.3.4.8- TCDF was added to the mineral oil sample but was not specifically determined. It was detected as part of the total TCDF that was reported (Total TCDF120 ppb). Thus the percentage error in the determination of Total TCDF(2,3,7,8- and 2,3,4,8-TCDF) is 21Z. The determination of 1,2,3,4,7,8-HxCDF (as Total HxCDF) is grossly in error. The total HxCDF added was 220 ppb and 1100 ppb was detected. The HxCDF added by the addition of 500 ppm of Aroclor 1260 and the chlorobenzenes is neglible and does not account for this discrepancy. The GENP 010970 3-1 7 8 3 7 ft1 exact cause of this error is unknown but similar errors have been recorded whenever a compound is determined using an internal standard not of the same congener class. Total PnCDF and total HpCDF were not determined and OCDF was inadvertently destroyed in the clean-up. The spiked Nujol which represents a purified aliphatic hydrocarbon matrix was prepared in this laboratory and provides an additional check on the accuracy of the determinations. All of the compounds added to the aged mineral oil were added to the Nujol. In terms of accuracy the results were similar. In all cases except total HxCDF, the absolute value of the ratio of the difference between the spiked level and the measured level was .90 or less. As before total PnCDF and OCDF levels were not determined. The results quoted for the Aroclor and chlorobenzene mixtures agree with later determinations of these mixtures (see section on In-service liquids). In general the detection limits for all these results were <1 ppb. The data in these preliminary experiments were acquired at high resolution using the HRMPM mode of ion monitoring. Typical data are shown in Figures 3-1 and 3-2. The area of the mass peak shown in Figure 3-2 is used to calculate the amount of 2,3,7,8-TCDD. Although least susceptible to interferences, this instrumental technique addresses the largest amount of data and is least automated. CALIBRATION AND QUALITY ASSURANCE DATA A calibration curve for each of eight of the analytes of interest was constructed from HRGC/LRMS data. The curve for 2,3,7, 8-TCDD is shown in Appendix B Figure 1. The log of the ratio of the area of native 2,3,7,8-TCDD to 13C-labelled TCDD is plotted versus the log of the concentration of native 2,3,7,8-TCDD. Seven solutions containing concentrations of native 2,3,7,8-TCDD of 2.5, 10, 40, 150, 500, 2500 and 7500 pg/yl and a constant 13C-labelled 2,3,7, 8-TCDD concentration of 500 pg/pl were used to construct this curve. The same concentrations of the other analytes and internal standards were used in other curves (Appendix B Figures 2-8). These curves demonstrate a linearity of response of almost four orders of magnitude. The percentage fit (100 x (correlation coefficient)^) of the least squares line in each of the curves constructed with low resolution mass spectrometry data is: 783782 3-2 GENP 010971 2.3.7.8- TCDD - 99.7398 2',3,7,8-TCDF - 99.7614 1.2.3.7.8- PnCDF - 99.6357 23,4,7,8-PnCDF - 99.0483 1.2.3.4.7.8- HxCDF - 99.7262 2.3.4.6.7.8- HxCDF - 99.3756 1.2.3.4.6.7.8- HpCDF - 99.5848 OCDF - 99.7685 DS65 K1CH RESOLUTION NPN RUNNflME 45344 BATE 2/ 6 /'S5 TINE 22i36 RETN Figure 3-1: Exacc Haas Chromatograms showing the retention time window for TCDD. Three 100 mmu. mass windows were monitored one each centered on m/z 321.8936 and m/z 319.8965 respectively for native TCDD and one centered on m/z 333.9338 for i-}C12-labelled-237 8-TCDD. GENP 010972 3-3 783783 SSt MICM IttOLUTtO* A M RCAk SUnnQTION REPORT RlMKflAE 46344 |BTE 2 ' 6 'S S is:M S S 319.6*46 i\ifrtH .i!#.KS SCAM UMCtS 133- 146 STRMMIS Mill frctor o 1.4UU or 7.2 TOT BASCLlHC 6 7 463 itch atea T in e 2 2:3 6 449. 27626176. a. ifr.Hsr SSSS H16H RESOLUTION A M F E B I SUHRBTION REPORT RUMMBRC 45344 B S T t 2 ' 6 '6 S BBSS 321 .6936 $CPN WIDTH 3 6 6 PPA 6CBH TIRE 6 . 3 SECS SCAN NUHICRS 1 3 3 - 14 ITBNDBRS 6.6666 FACTOR 6 I.4UL or 7.2 TOT tOSELlNE Sana 463 ITCH AREA TOTRL 1 2 3 37616366. 4666. 34336726. 126. TIRE 2 2 :3 e Figure 3-2: High Resolution Mass Scans & Summaries. This figure shows che sum of the mass scans which were taken during the elution of the 2378-TCDD peaks shown in Figure 3-1. E N P 010973 3-4 783784 Each curve also shows the 99X confidence interval for the slope and intercept of the least squares regression line. These calculations were based on equations given in a recently published book on statistics for chemists Cl2). Calibration curves derived from high resolution mass spectrometric dataCHRGC/HRMS) for some of the analytes are drawn in Appendix B Figures 9-13. The curves were constructed using the same solutions as described above. They also demonstrate linearity over approximately four orders of magnitude. The percentage fit of the least squares line in each of the curves constructed with high resolution mass spectrometry data is: 2.3.7.8- TCDD - 99.5395 2.3.7.8- TCDF - 99.4736 1.2.3.7.8- PnCDF - 97.0347 1.2.3.4.7.8- HxCDF - 99.949 1.2.3.4.6.7.8- HpCDF - 99.1012 Response factors were calculated daily from data collected from the injection of a portion of one of the standard solutions. The response factors (RF) are used in the following equation to calculate the concentration of analyte in the sample: CA = (An /Ai s )(RF)(Cis) (3-1) where, CA * concentration of analyte in the sample ^IS a concentration of internal standard added to the sample before the clean-up procedure Ajj 3area counts of the signal due to the analyte Ajs *Area counts of the signal due to the.internal standard RF 3 Response factor 3 SIS/SN SjS 3Area counts per unit mass of the internal standard 3 Area counts per unit mass of the native compound Ideally, for greatest precision, the response factors should not vary from analysis to analysis. The day-to-day variation in response factorCexpressed as area ratio) can be demonstrated by comparing the daily area.ratios to the area ratios generated for the calibration curve. In Appendix C Figure 14, the area ratios for the 2,3,7,8-TCDD, in the standard injection analyzed on each day of the project are plotted on the calibration curve. The area ratios for other analytes are-plotted in Figures 15 through 21 Appendix C. For 2,3,7,8-TCDD only one area ratio fell outside the 99Z confidence interval. Since no criteria had been 3-5 783785  specifically established, this area ratio (and consequently, response factor) was adjusted based upon the average of area ratios generated by injections on the previous and following days. Errant ratios obtained for other analytes were treated in this same fashion. This was considered acceptable because it was observed that the area ratios fluctuated only rarely and randomly. These large apparently random changes in the area ratios constituted the greatest factor responsible for any large relative standard deviations in the sample determinations. At the time of analysis no mechanism had been established to efficiently check the daily response factors of so many analytes. In future work, daily checks of the response factors could be made by incorporating more currently available automation into the methodology. Instrument manufacturers are continually developing software and one could expect that among the developments would be an efficient and reliable check of the response factors. We can envision a relatively easy method of checking the response factors against the calibration curve using the relatively general and widely available Lotus 1-2-3 software package. When many response factors can be easily checked, a criteria for the reproducibility of response factors could be included as an analytical specification before analysis commences. Likely criteria could be typical confidence intervals such as the 90, 95 or 992 confidence interval or a percentage of the average response factor calculated from the responses generated during the construction of the calibration curve. Analysis of blank samples is a final quality assurance point requiring some discussion. A laboratory blank was generated by carrying a sample of the solvents used in the analysis through the clean-up procedure. This sample was spiked with the appropriate internal standards. The internal standards were detected with reasonable recoveries. None of the analytes of interest were detected. The three baseline fluids, which constituted three of the ten samples in the project, were analyzed to quantify any of the PCDD and PCDF analytes which might be present before the blind spiking levels were added. None of the analytes were detected in the mineral oil or Aroclor 1016. However, the recovery of internal standards spiked into these samples was low. Some of the analytes were detected in Aroclor 1260. The results of these analyses are tabulated in Appendix D Tables 3, 4 and 5 and are used in conjunction with the results of the spiked Baseline fluids to determine the accuracy of the analysis. BASELINE DATA The actual project consisted of the analysis of ten samples of various utility fluids. Of these ten samples, six were dielectric fluids taken from in-service 3-6 783786 electrical equipment. Three of the samples were mineral oil, Aroclor 1U16, and Aroclor 1260 that were spiked before analysis with both the internal standards and blind levels of various native FCDD-PCDF analytes. The results of these analytes are tabulated in Appendix D Tables 3-5. The average percent error is 28.9%. In two cases, an analyte was measured where none had been spiked. In the spiked Aroclor 1016, 1,2,3,4,7,8-HxCDF was detected even though it had not been spiked. In spiked Aroclor 1260, 1,2,3,7,8,9-HxCDF was detected but not spiked. It is impossible to determine with these results if these compounds were present in the unspiked fluids since the detection limit in the unspiked fluids is greater than the level detected in the spiked fluids. The % error for the determination of OCDF in the spiked Aroclor 1260 was not included in the 28.9% average percent error calculation. The spike level was so low relative to the native amount of OCDF in Aroclor 1260 that the comparison of the spiked to measured level was not a reasonable indication of accuracy. -The % ' error figure was eliminated from the average based upon the similarity in magnitude of the spiked level and the standard deviation for the triplicate determination (compare the OCDF values in Table D-15). The average % error in each matrix is listed at the bottom of Tables D-L, D-2 and 0-3. The % error in the OCDF determination in Aroclor 1260 (Table D--3) was not included in the local average as explained above. The large average % error in the case of Aroclor 1260 is due to the large error in the determination of ,4,6,7,8-HxCDF and 1,2,3,4,6,7,8-HpCDF. This large error could be accounted for by a low recovery of these compounds in the blank Aroclor 1260. Recovery, as measured in this report, refers to the recovery of the internal standard used to quantitate a particular analyte and not to the recovery of the actual analyte. For these two compounds the internal standard was 1,2,3,4,7,8-HxCDF. This isomer may be different enough that slight differences in the performance of the chromatographic system will cause large differences in recovery. This phenomenon may account for many of the large relative standard deviations observed in this study. IN-SERVICE LIQUIDS The results of the triplicate analysis of each of the seven in-service dielectric fluids are tabulated in Appendix D, Tables D-6 to D-15. These results are 783787 graphically displayed in Appendix E, Figures 1 through 10. In each table the result for each replicate for each analyte is listed along with the average of the three replicates, the standard deviation and the percent relative standard deviation (coefficient of variation). Analytes that were not detected are indicated by the detection limit enclosed in parentheses. In all ten samples, the concentrations range from 0.15 ppb of 2,3,7, 8-TCDF in the Substation Distribution Transformer (Appendix D, Table D-ll) to 39,600 ppb of OCDF in the Load Center Network Transformer (Appendix D, Table D-6 ). For all the analytes in all the samples, only 15 average values (out of 180) had percent relative standard deviations over 302. None of these analyses involved the more toxic compounds namely 2,3,7,8-TCDD or 2,3,7,8-TCDF. The largest relative standard deviations (RSD) occurred in the analysis for Total TCDF or an isomer in one of the higher chlorinated congener classes. Some had percent relative standard deviations as low as 12. Six of the analyzes with greater than 302 RSD were determinations of total congener concentrations, two were determinations of closely eluting PnCDF isomers and seven were determinations quantitated at < 10 ppb. The detection limits and recoveries are tabulated in Appendix F Table 1 through 10. Tables 11 through 20 list 2 recovery versus 2, 3, 7, 8-TCDD-^C^2 The detection limits were calculated based upon a background response of 1000 counts in the diluted sample extract. Thus the following equation was used: Detection Limit - (1000/Ajg) (RF) (100) (3-2) where, Ajc area counts due to the internal standard RF Sjg/SN response factor Sis area counts per unit mass of internal standard Sjj area counts per unit mass of native compound A background area count of 1000 was chosen because this size peak was typical for G.C. peaks which are just distinguishable from background by the detector and computer combined. Smaller noise peaks are distinguishable in the detector output but these are not generally integrated by the computer and its integration algorithm. Furthermore 1000 counts is a conservative general estimate of the area noise observed just prior to the elution of the internal standards based upon the 2.5 pg/ml standard solution used for the calibration curves. GENP 010977 3-8 783788 Some apparent discrepancies may arise when comparing these detection limit values with the results (and detection limits) listed in Appendix D Tables D-6 through D15. However, the basis for any particular calculation in these two groups of tables may be different. The detection limit calculations in Appendix F Tables 1 through 10 are based on the previous equation for detection limits which includes the area count observed for each internal standard in a diluted extract. Most of the sample extracts were diluted because most contained one or two analytes which were highly concentrated relative to the other analytes. Many of the values listed in Appendix D Tables 4 through 13 were generated from data collected on the concentrated extracts before they were diluted. In one sample, spiked Aroclor 1260, the replicate analysis of 2378-TCDD generated the following values: 61.7, 65.5 and 32.0 ppb. A possible reason for the discrepancy between the first two determinations and the third is an interference in the 2,3,7,8-TCDD- I T . internal standard peak eluting at 42.194 minutes (see figure 3-3). To check for the occurrence of an interferant and generate the most accurate quantitation, the third extract was reanalyzed by high resolution G.C./high resolution M.S.(see Figure 3-4). The mass profile of the scans acquired during the elution of the 2,3,7,8-TCDD- Cj^ internal standard shows the presence of an interferant (see Figure 3-5). The small peak in the profile was used with a typical response factor to quantitate 2,3,7,8-TCDD at a level of 106 ppb. GENP 010978 3-9 783789 !2Q` 1000' 600- Ion 322.00 amu. S P IK E D AROCHLOR 1200 4 600- 400* 2001 2378-TC00 36 36 4Q 42 44 4g Time (min.i 3000- Ion 334.00 amu. IN T E R N A L STANDARD 2000- IN T E R F E R E N C E u IV -o c3 -a * 1000- ! la 36 1L J_ A 1 __________ ,_____ ! 36 40 42 44 4 Ti me ( m m . l Figure 3-3. Interference in the determination of 2378-TCDD in spiked Aroclor 1260. The internal standard G.C. peak appears to have a coeluting interference which would cause the determination of 2,3,7,8-TCDD to be too low. GENP 010979 3-10 783790 RETENTION TIME (minutes seconds) 00:30 _____ 1________________ i___ 03:30 1 MC Ml 319.8964 M2 321.8935 06:30 i Ai Dl AA A 09:30 i ]_______ 12:30 a_ /I100% = 3901091 /U 100% - 3901091 ( 1 1 ' t 100% = 3901091 i i M3 331.9367 - - A a __ /V 100% = 3901091 j AJ M4 333.9335 1 57 -- J\A _ A. . t-- 113 169 SCAN NUMBER 100% = 3901091 A- 225 ! 281 Figure 3-4. High resolution Mass Chromatogram of spiked Aroclor 1260. Notice the same pattern of G.C. peaks as in the law resolution data. This allows, in a sense, the analysis of isobaric components of the internal standard G.C. peak in the law resolution mass data. E N P 010980 3-11 783791 MASS 321.8935 SWEEP 3000 (PPM) SCANTIME 0.3 (SECS) SCANS 116-123 100% INTENSITY 91565 MASS 333.9335 SWEEP 300 (PPM) SCANTIME 0.3 (SECS) SCANS 116-123 100% INTENSITY 281879 Figure 3-5. High resolution mass data from the 2,3,7,8-TCDD G.C. peak from the spiked Aroclor sample. The mass scan of the internal standard ion shows a coeluting interference responsible for the low determination of 2,3,7,8-TCDD. GENP 010981 783792 Section 4 REFERENCES 0 \0 9 ^ 783793 $& 40 1. P.W. O'Keefe; C. Meyer; D.R. Hilker; K. Aldous; B. Jelus-Tyror; K. Dillon; R. Donnelly; E. Horn and R. Sloan. "Analysis of 2,3,7,8-Tetrachlorodibenzo-p-dioxin in Greac Lakes Fish." Chemosphere 12, 1983, p. 325 2. P.W. Albro and et al. "Methods for the Quantitative Determination of Multiple, Specific Polychlorinated Dibenzo-p-dioxin and Dibenzofuran Isomers in Human Adipose Tissue in the Parts-per-TriIlion Range." Analytical Chemistry. November 1985, p. 2717. 3. J.J. Ryan; B. P.-Y. Lau; J.A. Hardy; W.B. Stone; P. O'Keefe and J.F. Gierthy. "2,3,7,8-Tetrachlorodibenzo-p-dioxin and Related Dioxins and Furans in Snapping Turtle (Chelvdra Serpentina) Tissues from the Upper St. Lawrence River." Chemosphere, Vol. 15 1986, p. 537. 4. R.M. Smith; P.W. O'Keefe; K.M. Aldous; D.R. Hilker and J.E. O'Brien. "2,3,7,8-Tetrachlorodibenzo-p-dioxin in Sediment Samples from Love Canal Storm Sewers and Creeks." Environ. Sci. Tech.. Vol. 17 1983, p. 6. 5. K. Olie; P.L. Venneulen and 0. Hutzinger. "Chlorodibenzo-p-dioxins and Chlorodibenzofurans Are Trace Components of Fly Ash and Flue Gas of Some Municipal Incinerators in the Netherlands." Chemosphere. Vol. 6 1977, p. 455. 6. H.R. Buser; H-P. Bosshardt and C. Rappe. "Formation of Polychlorinated Dibenzofurans (PCDFs) from the Pyrolysis of PCBs." Chemosphere. Vol. 7 1978, p. 109. 7. H.R. Buser; H-P. Bosshardt; C. Rappe and R. Lindahl. "Identification of Polychlorinated Dibenzofuran Isomers in Fly A$h and PCB Pyrolyses." Chemosphere. Vol. 7 1978, p. 419. 8. R.M. Smith; P.W. O'Keefe; D.R. Hilker; B. Jelus-Tyror and K.M. Aldous. "Analysis for 2,3,7,8-Tetrachlorodibenzofuran and 2,3,7,8-Tetrachlorodibenzo-p-dioxin in a Soot Sample from a Transformer Explosion in Binghamton, New York." Chemosphere. Vol. 11 1982, p. 715. 9. C. Rappe. "Analysis of Polychlorinated Dioxins and Furans." Chemosphere. Vol. 18 No. 3 1984, p. 78A. 10. A. Poland; E. Glover and A.S. Kende. "Stereospecific, High Affinity Binding of 2,3,7,8-Tetrachlorodibenzo-p-dioxin by Hepatic Cytosol." J. Biol. Chem.. August 25, 1976, p. 4936, 11. E.E. McConnell; J.A. Moore; J.K. Haseran and M.W. Harris. "Toxicological Assessment of Hexachlorobiphenyl Isomers and 2,3,7,8-Tetrachlorodibenzo furan in Chicks." Toxicol. Appl, Pharmacol.. April 1976, p. 65. 12. J.A. Moore; E.E. McConnell; D.W. Dalgard and M.W. Harris. "Comparative Toxicity of Three Halogenated Dibenzofurans in Guinea Pigs, Mice and Rhesus Monkeys." Ann. N.Y. Acad. Sci.. Vol. 320 1979, p. 151. 13. J.E. Huff; J.A. Moore; R. Saracci and L. Tomatis. "Long-Term Hazards of Polychlorinated Dibenzodioxins and Polychlorinated Dibenzofurans." Environ. Health Perspect.. November 1980, p. 221. GENP 010983 *.2 783794 #* cf 14. State-of-the-Art Review: PCDDs and PCDFs in Utility Fluid. Palo Alto, Calif.: Electric Power Research Institute, November 1983. CS-3308-FR. 15. P.W. O'Keefe; R.M. Smith; D.R. Hilker; K.M. Aldous and W. Gilday. "A Semiautomated Cleanup Method for Polychlorinated Dibenzo-p-dioxins and Polychlorinated Dibenzofurans in Environmental Samples." In Chlorinated Dioxins and Dibenzofurans in the Total Environment II, L. Keith, C.Rappe and G. Choudhary, Eds., 1985, pp. 111-124. 16. J.H. Beynon. Mass Spectrometry and Its Application to Organic Chemistry. Amsterdam: Elsevier Publishing Co., 1960, pp. 51-54. 17. D.R. Hilker; K.M. Aldous; R.M. Smith; P.W. O'Keefe; J.F. Gierthy; J. Jurusik S.W. Hibbins; D. Spink and R.J. Parillo. "Detection of Sulfur Analog of 2,3,7,8-TCDD in the Environment." Chemosphere, Vol. 14 1985, p. 1275. 18. R. Caulcutt and R. Boddy. Statistics for Analytical Chemists. New York: Chapman and Hall, 1983, p. 54. 783795 4-3 GENP 010984 Appendix A IN-SERVICE LIQUIDS BACKGROUND INFORMATION Type of equipment: Load Center Network Transformer BCL Laboratory Code: ISL-02-A Voltage Rating: *750 KVA 12 KV to 480/277 V Liquid Volume: 2650 lbs. Year: 1962 PCB/Askarel Type: Aroclor 1260 29Z - T3CB 29Z - T4CB 2Z PCB Levels (for Oil Filled): Additional Equipment Identification: 65C max. rise Length of Actual Service: 20 yrs. Major Maintenance: Recorded Failure in Service: Was Fluid Changed at Failure: Any Record of Temperature Excursions: Are Maintenance Records Available: Any Other Pertinent Information: Type of equipment: Load Center Network Transformer BCL Laboratory Code: ISL-03-A Voltage Rating: 500 KVA 13 KV to 213 V Liquid Volume: ? Year: 1953 PCB/Askarel Type: Aroclor 1260 70Z - T3CB 29Z - T4CB 1Z PCB Levels (for Oil Filled): Additional Equipment Identification: Length of Actual Service: 31 yrs. Major Maintenance: Recorded Failure in Service: Was Fluid Changed at Failure: A-l 783 ? 9 6 Any Record or Temperature Excursions: Are Maintenance Records Available: Any Other Pertinent Information: Type of equipment: Substation Distribution Transformer BCL Laboratory Code: ISL-04-0 Voltage Rating: Liquid Volume: 200 gal. Year: PCB/Askarel Type: PCB Levels (for Oil Filled): 100 ppm Additional Equipment Identification: 65 C max. rise Length of Actual Service: 20 yrs. Major Maintenance: Recorded Failure in Service: Major arcing and in-service failure Was Fluid Changed at Failure: Any Record of Temperature Excursions: Are Maintenance Records Available: Any Other Pertinent Information: Type of equipment: Load Center Network Transformer BCL Laboratory Code: ISL-08-A Voltage Rating: 500 KVA 12 KVA to 213 V Liquid Volume: 3175 lbs. Year: 1946 PCB/Askarel Type: Aroclor 1260 about 672 - T3CB 302 - T4CB 22 PCB Levels (for Oil Filled): Additional Equipment Identification: 55 C max. rise Length of Actual Service: 28 yrs. Major Maintenance: None Noted Recorded Failure in Service: Was Fluid Changed at Failure: Any Record of Temperature Excursions: Are Maintenance Records Available: Any Other Pertinent Information: Carbon present throughout the Askarel Type of equipment: Precipitator BCL Laboratory Code: ISL-17-A 783797 A-2 G & s O ' 9 8 6 Voltage Racing: 480 to 53,500 V Liquid Volume: 143 gal. Year: PCB/Askarel Type: PCB Levels (for Oil Filled): Additional Equipment Identification: Serial No. TH 5875, 50 KVA Length of Actual Service: 1947 - 1974 (27 yra.) Major Maintenance: Recorded Failure in Service: Any Record of Temperature Excursions: Are Maintenance Records Available: Any Other Pertinent Information: Full load rise of 45C. Type of equipment: Arc Furnace Transformer BCL Laboratory Code: ISL-23-0 Voltage Rating: 12470/280 Liquid Volume: 4500 Year: 1976 PCB/Askarel Type: Mineral Oil PCB Levels (for Oil Filled): 150 ppm Additional Equipment Identification: 7500/8750 KVA, 4.72 imp., No-load Secondary tap changer, FOA, 65C rise insulation. Length of Actual Service: 8 yrs. Major Maintenance: Top cover of transformer and tap changer removed each year for internal visual inspection and check of connections. Recorded Failure in Service: None Was Fluid Changed at Failure: Any Record of Temperature Excursions: None occurred Are Maintenance Records Available: Yes Any Other Pertinent Information: Oil chemical test and gas chromatography tests run yearly. Type of equipment: Capacitor BCL Laboratory Code: ISL-27-? Voltage Rating: 7200 KVAR 100 Liquid Volume: 4" x 13.5" x 22" Year: PCB/Askarel Type: PCB Levels (for Oil Filled): A-3 783798 Additional Equipment Identification: Length of Actual Service: ? Major Maintenance: Recorded Failure in Service: Was Fluid Changed at Failure: Any Record of Temperature Excursions: Are Maintenance Records Available: Any Other Pertinent Information: GENP 783799 A-4 Appendix B ANALYTE CALIBRATION CURVES Figures B-l through B-8. Calibration curves constructed with data obtained from the low resolution mass selective detector. Along with the least squares line the 992 confidence interval is also plotted. Figures B-9 through B--13. Calibration curves constructed with data obtained from the high resolution mass spectrometer. 783800 B-l FIGURE B--1:EPR I BASELINE PROJECT 2378-TC D D CALIBRATION CURVE co NI> GENP 010990 STANDARD SOL'NS LOG(CONC in p g a /u l or p p b ) -------- LST SQS &L 99% CON FIGURE B --2: EPRI BASELINE PROJECT 2 3 7 8 --TCDF CALIBRATION CURVE GENP 010991 B-3 783802 STANDARD SOL'NS LOG(CONC in p q a /u l or p p b ) -------- LST SQS Sc 99% CON FIGURE B -3 : EPRI BASELINE PROJECT 12378 --PnCDE CALIBRATION CURVE co IIS O 03 O VO VO to STANDARD SOL'NS LOG(CONC in p g a /u l or p p b ) -------- LST SQS Sc 99% CON FIGURE B--4: EPRI BASELINE PROJECT 23478 --PnCDF CALIBRATION CURVE O l-- * O vo LO CO eIn ~ nI 00 CO 00 O STANDARD SOL'NS L0G(C0NC in p g a /u l or ppb) LST SQS &c 99% CON FIGURE B - 5 : EPRI BASELINE PROJECT 1 2 3 4 7 8 --HxCDF CALIBRATION CURVE 9Q GJ oo Oo V O 1 VO STANDARD SOL'NS L0G(C0NC in pg a/u l or ppb) -------- LST SQS & 99% CON FIGURE B --6: EPRI BASELINE PROJECT 2 3 4 6 7 8 --HxCDF CALIBRATION CURVE O H -* O VMOD KJ\ ta 'l-j 00 co 00 O a> STANDARD SOL'NS L 0 G (C 0 N C in p g s /u l) --------- LST SQS 8c 9 9 % CON FIGURE B --7: EPRI BASELINE PROJECT 1 2 3 4 6 7 8 --HpCDF CALIBRATION CURVE DII CD O I-- * OVVOO D STANDARD SOL'NS LOG(CONC in pgs/ul or -------- ppb) LST SQS Sc 99% CON cv FIGRE B--8: EPRI BASELINE PROJECT STANDARD SOL'NS LOG(CONC in p gs/ul or ppb) -------- LST SQS <3t 99% CON Figure B-9i COLI BROT ION CURVE FOR 2 , 3 , 7 , 8-TCDB fe " GENP 010998 00 A M T (C0NC .)RATIO CO 00 o CO GENP 010999 Figure B-10; CALIBRATION CURVE FOR Least squares curve fit 2 , 3 , ? ,8-TCDF W I 00 00 00 o A M T . iC H C .)R A T 10 F i q u re B-llsCfiLI BRAT ION C U R V E FR 1 , 2 , 3 , 7 ,8-PnCDF Least sauares curve fit AMT. (C H C .)R A T 10 GENP 011000 Q w Figure B-12: CALIBRATION CURVE FOR 1 ,2,3,4,7,8-HxCDF oO Least squares curve tit v RESPONSE RATIO -o4q A M T . (C O N C .)RAT 10 co co . to C~ .-- i 1y ! fc- I 1 v 1 O l Li i c u X GENP 011002 et8E8Z AMT.COHC.)RATIO Appendix C ANALYTE RESPONSE FACTOR CURVES Figures C-l through C-8. Area ratios from daily response factor determinations plotted onto the calibration curves. G B^ 0 lI0 0 3 783814 FIGURE C --1:EPRI BASELINE PROJECT 2 3 7 8 -T C D D DAILY RESP. FACTORS 0 1 NJ O O' 4^ O X DAILY RESP. FACTORS 8cLOG(CONC in pgs/ul) -------- LST SOS 99% CON O X DAILY RESP. FACTORS SeLOG(CONC in pgs/ul or ppb) LST SQS 99% CON FIGURE C --3:EPRI BASELINE PROJECT 1 2 3 7 8 --PnCDF DAILY RES. FACTORS 0 1 O rn o O O LST SQS Sc 99% CON LOG(CONC in p g s /u l or p p b ) V X DAILY RES. FACTOR ON FIGURE C--4: EPRI BASELINE PROJECT 2 3 4 7 0 --PnCDF DAILY RESPONSE FACTORS <*> O iIn 00 00 OD 00 LOG(CONC in p g s /u l or ppb) Sc DAILY RESP. FACTORS -------- LST SQS 99% CON FIGURE C--5: EPRI BASELINE PROJECT 1 2 3 4 7 a -H x C D F DAILY RESPONSE FACTORS 0 1 O' O O 8cCO + DAILY RESP. FACTORS LOG(CONC in p g a /u l or p p b ) --------- LST SQS 99% CON FIGURE C - 6 : EPRI BASELINE PROJECT 2 3 4 6 7 B --HxCDF DAILY RESPONSE FACTORS 0'1J -co4 co croo o + DAILY RESP. FACTORS SeLOG(CONC in pgs/ul or ppb) LST SOS 99% CON FIGURE C--7: EPRI BASELINE PROJECT 1 2 3 4 6 7 8 -H p C D F DAILY RESP. FACTORS . 0 1 CD o W % orid o o X DAILY RESP. FACTORS LOG(CONC in p g s /u l or ppb) LST SQS Sc 99% CON  X DAILY RESP. FACTORS LOG(CONC in pg a/u l or ppb) LST SOS Sc 99% CON Appendix D TABLES OF RESULTS TABLE D-l BASELINE SAMPLES PRELIMINARY RESULTS OF SPECIFIC COMPOUND ANALYSIS SAMPLES CONC. 237 8-TCDD ppb (D.L.) RET. CONC. TIME RATIO 2378-TCDF (min.) (2) ppb (D.L.) RET. CONC. TIME 123 78-PCDF (min.) ppb (D.L.) RET. TIME (min.) Aroclor 1016 E-729-09-01 -- 0.14(0.12) 22.34 0.40(0.08) 23.41 Aroclor 1016 0.51(0.19) 17.63 E729-09-01 77 0.34(0.08) 22.48 0.32(0.24) 23.48 ND1 ND1 Aroclor 1242 0.45(0.03) E729-10-01 106 150(1.6) 22.3 4 1000(25) 62(1.4)2 23 .03 Aroclor 1260 7.3(0.72) 17.35 E729-11-0 79 190(1.7) 22.15 220(5) 23 .20 Tri/Tetra Cl Benz E729-12-01 0.46(0.13) 17.29 44 0.43(0.05) 22.27 0.63(0.09) 23 .24 Aged Mineral 43(0.01) Oil E729-08-01 17.55 80 34(0.27) 22.44 140* 23.52 Blind Spike 40 Levels 20 40 Blank 0.93(0.06) 17.58 83 0.14(0.051 22.53 N.D.(0.41) 23.55 Nujol Spike 10(0.08) 17.58 91 12(0.58) 22.45 24(0.3 4) 23.48 *Sum of 1,2,3,7,8-PnCDF and 1, 2,3, 4, 8-PnCDF X.) ND " Not Detected in a second analysis 2.) The results of an alternative interpretation of the high resolution mass data. GENP 011012 D-l 783823  5 TABLE D-2 EPRt BASELIKE STUDY PRELIMINARY TOTAL CONGENER GROUP RESULTS SAMPLE TOTAL TCDD Ppb (D.L.) TOTAL TCDF ppb (D.L.) TOTAL PENTA CDF ppb (D.L.) TOTAL HEXA CDF ppb (D.L.) TOTAL HEPtA ppb (D.L.) OCDF -ppb (D.L.) Aroclor 1016 E729-09-01 N.D .(0 .6) 0.42 7.3 3 50 92 N.D.(12) Aroclor 1242 E729-10-01 N.D.(0.2) 1900 584 140 130 2300 Aroclor 1260 E729-11-0 N.D.(1.0) 940 932 5500 2970 NA Chlorobenzenes N.D.(0.2) 3.0 12.5 1000 91 NA E729-12-0i Aged Mineral Oil 42 95 -- 1100 -- NA E7 29-0 8-01 Blind Spike Levels 40 20 40 120 0 0 Total-Spiked 40 120 240 220 0 160 Blank N.D.(0.4) 0.75 -- 28 -- NA Nujol 11 (10)* 22 (10)* -- 420 (10)* 19 (10)* NA * Spike Level NA - Not Available 783824 D-2 GENP 011013 TABLE D-3 EPRI BASELINE PROJECT: ANALYSIS OF AGES MINERAL OIL TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD BLANK AGED MINERAL OIL (in ppb) (0.61) (1.03) (102.3) (164) (58.3) (0.93) (58.3) SPIKED MIN OIL (in ppb) 178 282 400 3 56 3.37 18.8 (2.1) SPIKED LEVEL TERROR (in ppb) 200 11.0 300 6.0 475 15.8 400 11.0 NS NA 25 24.8 -NS NA 2,3,7, 8-TCDD (0.93) 18.8 25 24.8 2,3,7, 8-TCDF (0.61) 178 200 11.0 2,3,4, 8-TCDF (0.61) 91.3 100 8.7 1,2,3,7,8-PnCDF (1.03) 135 150 10.0 1,2,3, 4, 8-PnCDF (1.03) (0.06) . NS NA 2,3,4, 7, 8-PnCDF (1.03) 141 150 6.0 1,2,3,4, 7, 8-HxCDF (102) 227 250 9.2 1,2,3,4, 7, 9-HxCDF (102) (0.22) NS NA 1,2,3,7, 8, 9-HxCDF (102) (0.22) NS NA 1,2,3,6,7, 8-HxCDF (102) 41.5 50 17.0 2,3, 4,6,7, 8-HxCDF (120) 160 175 8.6 1, 2,3,4, 6,7, 8-HpCDF (164) 354 400 11.5 ATE. X ERR 12.5 1. ) Numbers in parentheses indicate detection limits in ppb 2. ) Average detection limit of three determinations 3. ) NS - not spiked; NA - not applicable 4. ) 2,3,7,8-TCDF value is the sum of 2,3,7! 8- and 2,3,4, 8-TCDF concentrations. GENP 011014 D-3 783825 TABLE D-4 EFRI BASELINE PROJECT: ANALYSIS OF AROCLOR 1016 TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD BL AROCLOR SPIKED 1016 AROCL 1016 (in ppb) (in ppb) SPIKED LEVEL (in ppb) Z ERROR (0.41)1 (0.50) (22.2) (36) (7.9) (0.58) (16) 63 312 212 627 120 48.2 (2.I)2 53 316 185 526 13 2 53 NS3 -18.9 1.3 -14.6 -19.2 9.1 9.1 NA3 2f3, 7, 8-TCDD (0.58) 2,3,7, 8-TCDF (0.41) 2,3,4, 8-TCDF (0.41) 1,2,3, 7, 8-PnCDF (0.50) 1, 2,3,4, 8-PnCDF (0.50) 2,3,4, 7, 8-PnCDF (0.52) 1,2,3,4, 7,8-HxCDF (22) 1,2,3,4, 7, 9-HxCDF (22) 1,2,3,7, 8, 9-HxCDF (22) 1,2,3,6,7,8-HxCDF (22) 2,3,4,6, 7, 8-HxCDF (26) 1,2,3,4,6, 7, 8-HpCDF (36) 48.2 53 62.3 53 (0.71)2 NS 159 158 (0.38)2 NS 148 158 3.98 NS (0.26)2 NS (0.26)2 NS 56.5 53 151 132 625 526 AVE Z ERR 9.1 -17.5 NA -0.6 NA 6.3 NA NA NA --6.6 -14.4 -18.8 11 1. ) Numbers in parentheses indicate detection limits 2. ) Average detection limit of- three determinations 3. ) NS * not spiked; NA - not applicable 783826 O B N P o ilo n TABLE D-5 EPRI BASELINE PROJECT SAMPLE: ANALYSIS OF AROCLOR 1260 TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD SPIKED AROCL 1260 (in ppb) 1613 1320 2473 2390 5037 i6f (4.78)1 '2 SPIKEDBLANK (in ppb) 1093 412 1253 732 403 NAJ SPIKED LEVEL (in ppb) 1137 222 834 111 222 NSJ % ERROR 3 `? NA;? NA^ NA A -81.54 42.3 NA3 2,3,7,8-TCDD 2,3,7,8-TCDF 2,3,4, 8-TCDF 1,2,3,7,8-PnCDF 1,2,3,4,8-PnCDF 2,3,4,7,8-PnCDF 1,2,3,4,7,8-HxCDF 1,2,3,4,7,9-HxCDF 1,2,3,7,8, 9-HxCDF 1,2,3,6,7,8-HxCDF 2,3,4,6,7,8-HxCDF 1,2,3,4,6,7,8-HpCDF 64 1210 436 205 140 294 (0.5)1 2 38 336 297 845 64 111 1033 1027 NA 194 L27 111 61 NS 119 111 647 500 NA NS 38 NS 336 27 8 260 56 358 111 AVE Z ERR 42.3 -0.6 NA -14.4 NA -7.2 -29.4 NA NA -20.9 -364.34 -222.54 75 1. ) Numbers in parentheses indicate detection limits 2. ) Average detection limit of three determinations 3. ) NS not spiked; NA * not applicable 4. ) These values are discussed in the text GENP 011016 D-5 783827 TABLE D-6 EPRI BASELINE PROJECT SAMPLE 1953 LOAD CENTER NETWORK TRANSFORMER TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 232 1930 6840 10100 39000 (1.32) 11.8 10 DET. 2 121 1690 6570 8610 37700 (62.2) 9 10.4 DET. 3 337 1760 6520 8880 42100 (2.76) 14.3 17 AVE. 230 1793 6643 9196 39600 12 SD 108.1 123.4 172.1 7 93.9 2234 3 cv 47 6528....6569 25 2,3,7,8-TCDD (1.32) 2,3,7,8-TCDF 48.9 2,3,4,8-TCDF 16.5 1,2,3,7,8-PnCDF 19.2 1,2,3,4,8-PnCDF 919 2,3,4,7,8-PnCDF 101 1,2,3,4,7,8-HxCDF 4790 1,2,3,4,7,9-HxCDF (2.34) 1,2,3,7,8,9-HxCDF (2.34) 1,2,3,6,7,8-HxCDF 360 2,3,4,6,7,8-HxCDF 51.2 1,2,3,4,6,7,8-HpCDF 3890 (62.2) 42.9 29.4 705 107 4610 (4.14) (4.14) 367 42.4 3280 1.) Average of six (6) results (2.76) 67.7 53.17 15.6 772 105 4620 (5) (5) 362 40.6 3990 21.4 798.7 104.3 4673 363 44.7 3720 12.94 24.3 7.16 33 109.5 13.7 3.06 2.9 101.2 2.2 3.61 1 5.67 12.7 384.3 10.3 783828 GENP 011017 D-6 TOTAL TCDF TOTAL PnCDF TOTAL KxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD TABLE D-7 EFRI BASELINE PROJECT SAMPLE: LOAD CENTER NETWORK TRANSFORMER DET. 1 228 430 983 2400 6800 (0.35) (27.4) DET. 2 182 303 897 1940 8000 (0.43) (26.6) DET. 3 518 435 938 1850 7010 (7.1) (27.1) AVE. 309.3 3 89.3 939.3 2063 7270 SD 182.2 74.8 43 295 640.9 cv 58.9 19.2 4.6 148..38 2,3,7,8-TCDD 2,3,7,8-TCDF 2,3,4,8-TCDF 1,2,3,7,8-PnCDF 1,2,3,4,8-FnCDF 2,3,4,7,8-PnCDF 2,3,4,7,8-HxCDF 1,2,3,4,7,9-HxCDF 1,2,3,7,8,9-HxCDF 1,2,3,6,7,8-HxCDF 2,3,4,6,7,8-HxCDF 1,2,3,4,6,7,8-HpCDF (0.05) 68.6 29.4 88.8 60.6 619 1.5 37.9 33.9 43 15.2 662 (0.12) 61.1 6.95 30.7 38.1 39.6 596 1.54 17.7 22.2 44.6 9.1 545 (2) 90.9 73.5 15.5 21.1 28.9 72.3 59.4 610 1.8 36.1 31.5 42.3 12.3 631 29.7 66.4 53.2 608.3 1.6 29.9 0.93 3.13 25.9 39 11.8 22.2 11.6 1.9 0.16 10 7. 25 43.3 1.18 12.2 3.05 612.7 60.6 2.7 25 . GENP 011018 783829 TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD TABLE D-8 EPRI BASELINE PROJECT SAMPLE: CAPACITOR DET.'l 686 368 39.7 3.3 13 .4 (0.16) (x.i) DET. 2 700 351 51.9 12.5 15.3 (0.39) (0.38) DET.3 942 346 42 9.51 16.6 (0.83) (0.29) AVE. 776 355 44.5 10.1 15.1 SD 144 11.5 6.48 2.16 1.60 CV 15 3.3 15 21 11 2.3.7.8- TCDD 2.3.7.8-TCDF 2,3,4, 8-TCDF 1,2,3,7,8-PnCDF 1,2,3,4,8-PnCDF 2,3,4,7,8-PnCDF 1,2,3,4,7,8-HxCDF 1,2,3,4,7,9-HxCDF 1,2,3,7,8,9-HxCDF 1,2,3,6,7,8-HxCDF 2,3,4,6,7,8-HxCDF 1,2,3,4,6,7,8-HpCDF (0.16) 197 8.3 11.5 61.3 16.5 0.3 0.19 3.4 1.7 3.4 (0.39) 226 44.1 9.6 7.7 61.5 21.5 0.36 0.36 4.36 2 ` 4.8 (0.83) 273 8.37 8.7 71.1 15.8 0.38 0.24 3.94 1.75 3.38 232 3 8.40 8.757 9.3 64.63 13.53 0.35 0.263 3.9 1.817 3.86 0.73 1.97 5.60 4.55 0.04 0.09 0.48 0.16 0.81 7 8.4 21 8.7 34 12 33 12 8.9 21 GETSn? 011019 D-8 783830 TABLE D-9 EPRI BASELINE PROJECT SAMPLE : PRECIPITATOR TRANSFORMER TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 DET. 2 1500 10500 953 10200 10500 10900 2000 2020 190 187 (0.05) - 1.04 0.42 0.98 DET. 3 1100 10800 10700 2100 181 0.98 1.01 AVE. 1184 10500 10700 2040 186 SD 283.1 300 200 52.9 4.6 1.01 0.03 CV 23.9 2.9 1.9 2.6 2.5 3 2,3,7,8-TCDD 2,3,7, 8-TCDF 2,3, 4, 8-TCDF 1,2,3, 7, 8-PnCDF 1,2,3,4, 8-PnCDF 2,3,4, 7, 8-PnCDF 1,2,3,4, 7, 8-HxCDF 1,2,3,4, 7, 9-HxCDF 1,2,3, 7, 8, 9-HxCDF 1,2,3,6,7, 8-HxCDF 2,3,4,6,7, 8-HxCDF 1, 2,3,4,6, 7, 8-HpCDF (0.05) 480 799 307 1930 43 90 22.5 162 1030 366 690 ( 0 .02) 349 101 796 256 1920 4410 21.6 177 1030 404 678 (0.09) 395 818 317 1970 4360 22 175 1000 398 700 408 66.5 16.3 804.3 293 .3 1940 43 87 22 171.3 1020 389.3 689.3 11.9 32.7 26.5 25.2 0.45 8.2 17.3 20.4 11 1.5 11.2 1.4 0.6 2.1 4.8 1.7 5.2 1.6 GENP 011020 D-9 783831 TABLE D-10 EPRI BASELINE PROJECT SAMPLE: 1976 ARC FURNACE TRANSFORMER TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 0.53 1.72 1.78 0.51 0.46 CO.09) 3.02 DET. 2 0.38 1.94 1.14 0.23 0.3 (0.08) 3.3 8 DET.3 0.31 2.14 2.43 0.19 0.24 (20) 3.8 AVE. 0.41 1.93 1.78 0.31 0.33 3.4 SD 0.11 0.21 0.64 0.17 0.11 0.39 CV 28 11 36 56 34 11 2,3,7,8-TCDD 2,3,7,8-TCDF 2,3,4, 8-TCDF 1,2,3,7,8-PnCDF 1,2,3,4, 8-PnCDF 2,3,4,7,8-PnCDF 1,2,3,4,7,8-HxCDF 1,2,3,4,7,9-HxCDF 1,2,3,7,8, 9-HxCDF 1,2,3,6,7,8-HxCDF 2,3,4,6,7, 8-HxCDF 1,2,3,4,6,7,8-HpCDF (0.09) 0.2 0.21 (0.16) 0.45 1.08 (0.2) 0.22 0.25 (0.21) (0.28) (0.08) 0.24 (0.54) 0.26 (0.13) 0.51 0.54 (0.06) 0.11 0.13 (0.14) (0.08) (20) 0.23 0.223 0.23 (0.08) 0.41 1.13 (0.03) 0.28 0.27 (0.07) (0.09) 0.23 0.46 0.917 0.203 0.217 0.02 9.3 0.03 11 0.05 0.33 11 36 0.09 0.08 42 35 783832 GENP 011021 D-10 TABLE D-1L EPRI BASELINE PROJECT SAMPLE: SUBSTATION DISTRIBUTION TRANSFORMER TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. I 0.15 (0.34) 0.56 (0.65) (0.63) (0.61) 20.8 DET. 2 0.18 (0.6) 0.52 (0.23) (2.4) 0.19 16.8 DET.3 0.23 (0.53) 0.71 (0.21) (3.8) 0.1 17.1 AVE. 0.19 0.6 18.2 SD 0.04 0.1 2.23 CV 22 16.7 12 2,3,7,8-TCDD 2,3,7,8-TCDF 2,3,4,8-TCDF 1,2,3,7,8-PnCDF 1,2,3,4,8-PnCDF 2,3,4,7,8-PnCDF 1,2,3,4,7,8-HxCDF 1,2,3,4,7,9-HxCDF 1,2,3,7,8,9-HxCDF 1,2,3,6,7,8-HxCDF 2,3,4,6,7,8-HxCDF 1,2,3,4,6,7,8-HpCDF (0.6) 0.15 (0.34) (0.34) (0.34) 0.56 (0.21) (0.21) (0.21) (0.32) 0.65 (0.12) 0.18 (0.09) (0.09) 0.09 0.52 (0.19) (0.19) (0.19) (0.2) (0.23) (0.09) 0.13 (1.5) (0.07) (0.07) 0.11 0.53 (0.16) (0.16) (0.16) (0.18) (0.21) 0.15 0.54 0.025 0.02 16 3.7 GENP 011022 783833 TABLE D-12 EPRI BASELINE PROJECT SAMPLE: 1962 LOAD CENTER NETWORK TRANSFORMER TOTAL TCDF TOTAL PtlCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 553 1170 1760 1780 3 960 (1.16) 18.7 DET. 2 552 1130 17 80 1580 4410 (0.82) 24.2 DET. 3 512 1100 1820 1610 4730 (0.71) 28.4 AVE. 53 9 1133 1790 1657 4366 SD 23.4 35.1 30.5 107.8 3 87.7 23.8 4.9 CV 4.3 3.1 1.7 6.5 8.9 20.6 2.3.7.8-TCDD 2.3.7.8-TCDF 2.3.4.8- TCDF 1.2.3.7.8- PnCDF 1.2.3.4.8- PnCDF 2.3.4.7.8- PnCDF 1.2.3.4.7.8- HxCDF 1.2.3.4.7.9- HxCDF 1.2.3.7.8.9- HxCDF 1.2.3.6.7.8- HxCDF 2.3.4.6.7.8-HxCDF 1.2.3.4.6.7.8- (1.16) 195 59.4 230 170 1000 (0.89) (0.89) 64.9 70 HpCDF815 (0.82) 184 42.4 60.8 216 151 1030 (0.86) (0.86) 65.2 58 761 (0.71) 182 187 61.4 206 173 1110 (0.59) (0.59) 61.7 56 784 60.5 217 164.6 1047 63.9 61 787 7 1 12 11.9 56.9 1.9 7.6 27 3.7 1.7 5.5 7.2 5.4 3 12 3.4 783834 g Btf Ol' 0 2 3 D-12 TABLE D-13 EPRI BASELINE PROJECT SAMPLE: SPIKED AGED MINERAL OIL TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 145 251 396 354 3.49 17 (5.09) DET. 2 195 312 455 341 3.55 21.3 (0.49) DET.3 194 283' 350 372 3.06 18.2 (0.67) AVE. 178 282 400 356 3.37 18.8 SD 28.6 30.5 52.6 15.6 0.27 2.219 CV 16.1 10.8 13.2 4.4 7.9 12 2,3,7,8-TCDD 2,3,7,8-TCDF 2,3,4, 8-TCDF 1,2,3,7,8-PnCDF 1,2,3,4,8-PnCDF 2,3,4,7,8-PnCDF 1,2,3,4,7,8-HxCDF 1,2,3,4,7,9-HxCDF 1,2,3,7,8,9-HxCDF 1,2,3,6,7,8-HxCDF 2,3,4,6,7,8-HxCDF 1,2,3,4,6,7,8-HpCDF 17 146 121 (0.04) 127 224 (0.53) (0.53) 42.1 150 351 21.3 195 91.3 153 (0.07) 158 259 (0.07) (0.07) 47.4 161 341 18.2 18.8 2.219 12 192 177.7 27.5 15.5 132 (0.07) 138 199 (0.05) (0.05) 35.1 170 369 135 141 227 41.5 160 353.7 16.3 15.7 30.1 6.2 10 14.2 12.1 11.1 13.3 14.9 6.3 4 GENP 011024 D-13 783835 TABLE D-14 EPRI BASELINE PROJECT SAMPLE: SPIKED AROCLOR 1016 TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 60.8 276 201 578 133 39.6 (1.44) DET. 2 62.7 336 209 712 107 50.4 (0.41) DET.3 AVE. 65.5 63 324 312 225 212 591 627 121 120.3 54.S 48.2 (4.52) SD 2.4 31.7 12.2 73.9 13 7.7 CV 3.8 10.1 5.8 11.8 10.8 15.9 2,3,7,8-TCDD 2,3,7,8-TCDF 2,3,4,8-TCDF 1,2,3,7,8-PnCDF 1,2,3,4,8-PnCDF 2,3,4,7,8-PnCDF 1,2,3,4,7,8-HxCDF 1,2,3,4,7,9-HxCDF 1,2,3,7,8,9-HxCDF 1,2,3,6,7,8-HxCDF 2,3,4,6,7,8-HxCDF 1,2,3,4,6,7,8-HpCDF 39.6 60.8 13 8 (0.30) 122 2.56 (0.21) (0.21) 58.5 140 575 50.4 60.5 (0.72) 171 (0.09) 159 3.8 (0.05) (0.05) 54.6 150 709 54.5 48.2 65.5 62.3 16 8 159 (0.75) 163 148 5.6 3.98 (0.52) (0.52) 56.5 6.5 162 150.7 592 625 7.7 15.9 2.8 4.5 18.2 11.4 22.6 15.3 1.52 38 2 3.5 11 7.3 73 11 GENP 011025 D-14 783836  I TABLE D-15 EPRI BASELINE PROJECT SAMPLE : SPIKED AROCLOR 1260 TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 1630 1330 2490 2470 4850 65.1 (3.73) DET. 2 1620 1290 23 80 2300 5090 65.5 (0.72) DET. 3 1590 1340 2550 2400 5170 106 (9.89) AVE. 1613 1320 2473 23 90 5037 79.9 SD 20.82 26.46 86.2 85.4 166.5 23 CV 1.3 2 3.5 3.6 3.3 30 2,3,7,8-TCDD 2,3,7,8-TCDF 2,3,4, 8-TCDF 1,2,3,7,8-PnCDF 1,2,3,4,8-PnCDF 2,3,4,7,S-PnCDF 1,2,3,4,7,8-HxCDF 1,2,3,4,7,9-HxCDF 1,2,3,7,8,9-HxCDF 1,2,3,6,7,8-HxCDF 2,3,4,6,7,8-HxCDF 1,2,3,4,6,7,8-HpCDF 65.1 1210 207 139 304 1228 (0.41) 37.8 339 313 865 65.5 1220 436 203 139 288 1209 (0.09) 35.8 321 286 805 1061 79.9 1200 1210 23 30 10 0.83 206 142 291 1284 (0.99) 39.9 347 291 865 205 140 294.3 1240 2.08 1.73 8.5 38.99 37.8 336 297 845 2.05 13.32 14.36 34.64 1 1.2 2.9 3.1 5.5 4 4.9 4.1 1.) Analyzed by high resolution m.s. GENP 011026 D-15 783837 Appendix E BAR GRAPHS OF RESULTS Figures E-l through E-10. Bar plots of the results. The numbers listed along the analyte axis in each of these figures represent the following isomers or groups of isomers: 1. Total TCDF 2. Total PnCDF 3. Total HxCDF 4. Total HpCDF 5. OCDF 6. Total TCDD 7. OCDD 8. 2,3,7,8-TCDD 9. 2,3,7,8-TCDF 10. 2,3,4,8-TCDF 11. 1,2,3,7,8-PnCDF 12. 1,2,3,4,8-PnCDF 13. 2,3,4,7,8-PnCDF 14. 1,2,3,4,7,8-HxCDF 15. 1,2,3,4,7,9-HxCDF 16. 1,2,3,7,8,9-KxCDF 17. 1,2,3,6,7,8-HxCDF 18. 2,3,4,6,7,8-HxCDF 19. 1,2,3,4,6,7,8-HpCDF In the Figures a bracket is used to indicate that most of the individual isomer determinations were multiplied by a factor of 10 before they were plotted. Thus, for example the concentration of 123 47 8-HxCDF in the-first figure is 4.7 x 10J ppb. G B N p o i, 027 E-l 78383 FIG E--1 : LOAD CENTER NETW. TRANSFORMER AVERAGE ANALYTE CONC.S cm 0- 0- o fi> Pi rIo U3 Zo Of t o 's! 00 CO 00 CO CD O 0K 0) [771 AVERAGE CONO. [ m STANDARD DEV. FIG E--2: LOAD CNTR NETWORK TRANSFORMER GENP 011029 _____ C7~7I AVERAGE CONC. ANALYTE____ I V V l STANDARD DEV. FIG E--3: CAPACITOR AVERAGE ANALYTE CONC.S GENP011030 ( Z 7 1 AVERAGE CONC. ANALYTE _ i X \ l STANDARD DEV. FIG E--4: PRECIPITATOR TRANSFORMER IZ7I AVERAGE CONC. ANALYTE \ 7 \ 1 STANDARD DEV. FIG E - 5 : ARC FURNACE TRANSFORMER AVERAGE ANALYTE CONC.S & 783843 GENP 011032 _{ / / \ AVERAGE CONC, ANALYTE_____ STANDARD DEV. FIG E--6: SUBSTATION DISTRIBUTION TRANSF 21 20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 ^LHxCDF Tt> 0 ______ _____ AVERAGE ANALYTE CONC.S -QCOO-------------------------------------- N S 7 / / / / / / / / / / / / / / / / / / / / / I 6 X10 1 2 3 4 7 8 --HxCDF / / / T ~ * -- I-- 1-- r r t / / A '" i r 9 10 11 12 13 14 "T-- ' I 1 I 15 16 17 T 18 19 IZ71 AVERAGE CONC. ANALYTE r v X l STANDARD DEV. GENP 011034 FIG E--7: LOAD CNTR NETWORK TRANSFORMER AVERAGE ANALYTE CONC.S * FIGURE E--8: SPIKED MINERAL OIL AVERAGE ANALYTE AND SPIKE CONC.S GENP 011035 td *I0 -4 00 CO 2 05 \ / / \ AVERAGE CONC. ANALYTE SPIKED CONC. Z777X STAND. DEV. FIGURE E--9: SPIKED AR0CL0R 1 0 1 6 AVERAGE ANALYTE AND SPIKE CONC.S l ->l oo CO 00 '"'J GENP 011036 8 o U) M I FIGURE E--10: SPIKED AROCLOR 1260 AVERAGE ANALYTE AND SPIKE CONC.S GO GO 00 O0 I X X I AVERAGE CONC. ANALYTE K X ) SPIKED CONC. ZP77X STAND. DEV. Appendix F TABLES OF RECOVERIES, RELATIVE RECOVERIES AND DETECTION LIMITS O EN P 011038 783849 TABLE 1 RECOVERIES AND DETECTION LIMITS EFRI BASELINE PROJECT SAMPLE: 1953 LOAD CENTER NETWORK TRANSFORMER TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 XREC DET LIM. (.in ppb) 43 2.1 47 2.1 55 2.1 55 2.9 24 10.2 43 3.0 24 20.3 DET. 2 ZREC DET LIM. (in ppb) 16 4.3 19 4.0 24 3.7 24 3.7 8 23.5 16 6.3 8 46.9 DET. 3 ZREC DET LIM. (in ppb) 3 15.1 10 5.2 14 4.5 14 6.1 7 19.0 1 47.4 7 38.1 2f3 ,7,8-TCDD 43 2,3,7,8-TCDF 43 2,3,4,8-TCDF NA 1,2,3,7,8-PnCDF 47 1,2,3,4,8-PnCDF 47 2,3,4,7,8-PnCDF 47 1,2,3,4,7,8-HxCDF 55 1,2,3,4,7,9-HxCDF 55 1,2,3,7,8,9-HxCDF 55 1,2,3,6,7,8-HxCDF 55 2,3,4,6,7,8-HxCDF 55 1,2,3,4,6,7,8-HpCDF 55 1.) NA " not applicable 3.0 2.1 NA 2.1 2.1 2.2 2.1 2.1 2.1 2.1 2.5 2.9 16 6.3 16 4.3 16 0.1 19 4.0 19 4.0 19 4.2 24 3.7 24 3.7 24 3.7 24 3.7 24 4.4 24 5.1 w 1. 3 NA 10 10 10 14 14 14 14 14 14 47.4 15.1 NA 5.2 5.2 5.5 4.5 4.5 4.5 4.5 5.3 6.1 783850 GENP 011039 TABLE 2 RECOVERIES AND DETECTION LIMITS EFRI BASELINE PROJECT SAMPLE: 1946 LOAD CENTER NETWORK TRANSFORMER TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 ZREC DET LIM. (in ppb) 29 1.2 28 1.5 31 1.5 31 2.0 22 5.6 35 1.6 22 10.9 DET. 2 %REC DET LIM. (in ppb) 18 2.1 17 2.5 18 2.7 18 3.5 7 17.9 18 3.2 7 34.6 DET. 3 ZREC DET LIM. (in ppb) 10 2.9 27 1.3 30 1.3 30 1.7 18 5.9 4 19.0 18 11.4 2,3,7,8-TCDD 35 2,3,7,8-TCDF 29 2,3,4,8-TCDF NA 1,2,3,7,8-PnCDF 28 1,2,3,4,8-PnCDF 28 2,3,4,7,8-PnCDF 28 1,2,3,4,7,8-HxCDF 31 1,2,3,4,7,9-HxCDF 31 1,2,3,7,8,9-HxCDF 31 1,2,3,6,7,8-HxCDF 31 2,3,4,6,7,8-HxCDF 31 1,2,3,4,6,7,8-HpCDF 31 1.) NA not applicable 1.6 1.2 NA 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.7 2.0 18 3.2 18 2.1 18 0.2 17 2.5 17 2.5 17 . 2.5 18 2.7 18 2.7 18 2.7 18 2.7 18 3.0 18 3.5 4 10 NA 27 27 27 30 30 30 30 30 30 19.0 2.9 NA 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.5 1.7 GENP 011040 783851 TABLE 3 RECOVERIES AND DETECTION LIMITS EFRI BASELINE PROJECT SAMPLE: CAPACITOR TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 IREC DET LIM. (in ppb) 35 0.1 34 0.2 38 0.2 38 0.2 35 0.7 61 0.1 35 1.4 DET. 2 2REC DET LIM. (in ppb) 17 0.2 16 0.2 19 0.2 19 0.2 23 0.3 18 0.2 23 0.6 DET. 3 2REC DET LIM. (in ppb) 2 1.3 55 o . i 63 0.1 63 0.1 59 0.1 5 0.9 59 0.3 2,3,7,8-TCDD 61 2,3,7,8-TCDF 35 2,3,4,8-TCDF NA 1,2,3,7,8-FnCDF 34 1,-2,3,4,8-PnCDF 34 2,3,4,7,8-PnCDF 34 1,2,3,4,7,8-HxCDF 38 1*2,3,4,7,9-HxCDF 38 1,2,3,7,8,9-HxCDF 38 1,2,3,6,7,8-HxCDF 38 2,3,4,6,7,8-HxCDF .38 1,2,3,4,6,7,8-HpCDF 38 1.) NA noe applicable 0.1 0.1 NA 0.2 . 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 18 17 17 16 16 16 19 19 19 19 19 19 0.2 0.2 0.3 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 5 0.9 2 1.3 NA NA 55 0.1 55 0.1 55 0.1 63 0.1 63 0.1 63 0.1 63 0.1 63 0.1 63 .0.1 783852 GENP 011041 TABLE 4 RECOVERIES AND DETECTION LIMITS EPRI BASELINE PROJECT SAMPLE: PRECIPITATOR TRANSFORMER TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. I ZREC DET LIM. (in ppb) 16 4*2 17 4.3 19 4.4 19 5.7 14 15.0 16 6.5 14 30.6 DET. 2 ZREC DET LIM. (in ppb) 24 1.5 28 1.5 29 1.6 29 2.1 17 7.1 26 2.3 17 14.5 DET. 3 ZREC DET LIM. (in ppb) 21 2.2 32 1.6 34 1.7 34 2.3 24 6.2 56 3.3 24 12.7 2,3,7,8-TCDD 16 2,3,7,8-TCDF 16 2,3,4,8-TCDF NA 1,2,3,7,8-FnCDF 17 1,2,3,4,8-PnCDF 17 2,3,4,7,8-PnCDF 17 1,2,3,4,7,8-HxCDF 19 1,2,3,4,7,9-HxCDF 19 1,2,3,7,8,9-HxCDF 19 1.2,3,6,7,8-HxCDF 19 2,3,4,6,7,8-HxCDF 19 1,2,3,4,6,7,8-HpCDF 19 1.) NA not applicable 6.5 4.2 NA 4.3 4.3 4.3 4.4 4.4 4.4 4.4 4.7 5.7 26 2.3 24 1.5 24 0.2 28 1.5 28 1.5 28 1.5 29 1.6 29 1.6 29 1.6 29 1.6 29 1.7 29 2.1 56 3.3 21 2.2 NA NA 32 1.6 32 1.6 32 1.6 34 1.7 34 1.7 34 1.7 34 1.7 34 1.9 34 2.3 GENP 011042 F-5 783853 TABLE 5 RECOVERIES AND DETECTION LIMITS EFRI BASELINE PROJECT SAMPLE: 1976 ARC FURNACE TRANSFORMER TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 ZREC DET LIM. Cin ppb) 67 0.1 81 0.1 82 0.1 82 0.2 63 0.5 74 0.1 63 1.0 DET. 2 ZREC DET LIM. (in ppb) 37 0.1 51 0.1 51 0.0 51 0.1 24 0.4 45 0.1 24 0.8 DET. 3 ZREC DET LIM. (in ppb) 78 0.05 128 0.03 123 0.04 123 0.05 119 0.11 0.4 28.12 119 0.19 2,3,7,8-TCDD 74 2,3,7,8-TCDF 67 2,3,4,8-TCDF NA 1,2,3,7,8-PnCDF 81 1,2,3,4,8-PnCDF 81 2,3,4,7,8-PnCDF 81 1,2,3,4,7,8-HxCDF 82 1,2,3,4,7,9-HxCDF 82 1,2,3,7,8,9-HxCDF 82 1,2,3,6,7,8-HxCDF 82 2,3,4,6,7,8-HxCDF 82 1,2,3,4,6,7,8-HpCDF 82 1.) NA not applicable 0.1 0.1 NA 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.2 45 0.1 0.4 28.12 37 0.1 78 0.05 37 0.7 NA NA 51 0.1 128 0.03 51 0.1 128 0.03 51 0.1 128 0.04 51 0.0 123 0.04 51 0.0 123 0.04 51 0.0 123 0.04 51 0.0 123 0.04 51 0.1 123 0.04 51 0.1 123 0.05 783854 F-6 GENP 011043 TABLE 6 RECOVERIES AND DETECTION LIMITS EFRI BASELINE PROJECT SAMPLE: SUBSTATION DISTRIBUTION TRANSFORMER TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 ZREC DET LIM. (in ppb) 36 0.2 48 0.2 60 0.1 60 0.2 66 0.1 38 0.3 66 1.0 DET. 2 ZREC DET LIM. (in ppb) 69 0.04 80 0.04 36 0.09 36 0.12 4 2,14 80 0.05 4 21.61 D E T .3 ZREC DET LIM. (in ppb) 76 0.04 66 0.05 33 0.11 33 0.13 7 1.33 73 0.07 7 2.54 2,3,7,8-TCDD 38 2,3,7,8-TCDF 36 2,3,4,8-TCDF NA 1,2,3,7,8-PnCDF 48 1,2,3,4,8-PnCDF 48 2,3,4,7,8-PnCDF 48 1,2,3,4,7,8-HxCDF 60 1,2,3,4,7,9-HxCDF 60 1,2,3,7,8,9-HxCDF 60 1,2,3,6,7,8-HxCDF 60 2,3,4,6,7, d-HxCDF 60 1,2,3,4,6,7,8-HpCDF 60 1.) NA " not applicable 0.3 0.2 NA 0.2 0.2 0.2 0.1 0.1 0.1 0.1 0.2 0.2 80 0.05 69 0.04 69 0.04 80 0.04 80 0.04 80 0.04 36 0.09 36 0.09 36 0.09 36 0.09 36 0.10 36 0.12 73 0.07 76 0.04 NA NA 66- 0.05 66 0.05 66 0.05 33 0.11 33 0.11 33 0.11 33 0.11 33 0.11 33 0.13 GENP 011044 783855 TABLE 7 RECOVERIES AND DETECTION LIMITS EFRI BASELINE PROJECT SAMPLE: 1962 LOAD CENTER NETWORK TRANSFORMER TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 ZREC DET L1H. (in ppb) 42 2.0 51 2.0 51 2.3 51 3.3 30 8.6 46 2.8 30 19.4 DET. 2 ZREC DET L1M. (in ppb) 45 1.4 47 1.6 40 2.2 40 3.1 29 26.7 50 2.0 29 124.7 DET. 3 ZREC DET LIM. (in ppb) 55 1.2 62 1.3 60 1.5 60 2.2 26 7.7 59 1.7 26 17.3 2,3,7,8-TCDD 46 2,3,7,8-TCDF 42 2,3,4,8-TCDF NA 1,2,3,7,8-PnCDF 51 1,2,3,4,8-PnCDF 51 2,3,4,7,8-PnCDF 51 1,2,3,4,7,8-HxCDF 51 1,2,3,4,7,9-HxCDF 51 1,2,3,7,8,9-HxCDF 51 1,2,3,6,7,8-HxCDF 51 2,3,4,6,7,8-HxCDF 51 1,2,3,4,6,7,8-HpCDF 51 1.) NA not applicable 2.8 2.0 NA 2.0 2.0 1.8 2.3 2.3 2.3 2.3 2.6 3.3 50 45 45 47 47 ' 47 40 40 40 40 40 40 2.0 1.4 0.2 1.6 1.6 1.5 2.2 2.2 2.2 2.2 2.5 3.1 M 59 55 NA 62 62 62 60 60 60 60 60 60 1.7 1.2 NA 1.3 1.3 1.1 1.5 1.5 1.5 1.5 1.7 2.2 783856 O B W 011045 * TABLE 8 RECOVERIES AND DETECTION LIMITS EFRI BASELINE PROJECT SAMPLE: SPIKED AGED MINERAL OIL TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 ZREC DET LIM, (in ppb) 50 0.5 55 0.6 55 0.7 55 1.1 49 3.6 54 0.8 49 6.3 DET. 2 ZREC DET LIM. (in ppb) 45 2.7 44 3.2 43 3.7 43 4.8 33 13.1 47 4.0 33 123.6 DET. 3 ZREC DET LIM. (in ppb) 39 0.1 43 0.1 40 0.1 40 0.1 27 0.5 40 0.1 27 0.9 2,3,7,8-TCDD 54 2,3,7,8-TCDF 50 2,3,4,8-TCDF NA 1,2,3,7,8-PnCDF 55 1,2,3,4,8-PnCDF 55 2,3,4,7,8-PnCDF 55 1,2,3,4,7,8-HxCDF 55 1,2,3,4,7,9-fixCDF 55 1,2,3,7,8,9-HxCDF 55 1,2,3,6,7,8-HxCDF 55 2,3,4,6,7,8-HxCDF 55 1,2,3,4,6,7,8-HpCDF 55 1.) NA - not applicable 0.8 0.5 NA 0.6 0.6 0.6 0.7 0.7 0.7 0.7 0.8 1.1 47 4.0 45 2.7 45 0.2 44 3.2 44 3.2 44 3.2 43 3.7 43 3.7 43 3.7 43 3.7 43 4.1 43 4.8 40 39 NA 43 43 43 40 40 40 40 40 40 0.1 0.1 NA 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 OEI^P 011046 783857 TABLE 9 RECOVERIES AND DETECTION LIMITS EFRI BASELINE PROJECT SAMPLE: SPIKED AROCLOR 1016 TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 ZREC DET LIM. (in ppb) 52 0.3 68 0.2 77 0.2 77 0.4 103 0.5 57 0.4 103 1.4 DET. 2 ZREC DET LIM. (in ppb) 32 2.2 37 2.0 36 2.4 36 4.0 37 7.0 34 3.1 37 100.7 DET. 3 ZREC DET LIM. (in ppb) 30 0.9 44 0.8 42 1.0 42 1.4 40 2.2 42 1.1 40 5.0 2,3,7,8-TCDD 57 2,3,7,8-TCDF 52 2,3,4,8-TCDF NA 'l|2,3,7,8-PnCDF 68 1,2,3,4,8-PnCDF 68 2,3,4,7,8-PnCDF 68 1,2,3,4,7,8-HxCDF 77 1,2,3,4,7,9-HxCDF 77 1,2,3,7,8,9-HxCDF 77 1,2,3,6,7,8-HxCDF 77 2,3,4,6,7,8-HxCDF 77 1,2,3,4,6,7,8-HpCDF 77 1.) NA not applicable 0.4 0.3 NA 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.3 0.4 34 3.1 32 2.2 32 2.3 37 2.0 37 2.0 37 2.1 36 2.4 36 2.4 36 2.4 36 2.4 36 3.2 36 4.0 42 1.1 30 0.9 NA NA 44 0.8 44 0.8 44 0,7 42 1.0 42 1.0 42 1.0 42 1.0 42 1.1 42 1.4 783858 OENP 011047 TABLE 10 RECOVERIES AND DETECTION LIMITS EPRI BASELINE PROJECT SAMPLE: SPIKED AROCLOR 1260 TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 ZREC DET LIM. (in ppb) 52 0.5 5S 0.6 64 0.6 64 0.8 57 1.8 161 0.3 57 3.1 DET. 2 DET. 3 ZREC DET LIM. ZREC DET LIM. (in ppb) (in ppb) 75 2.4 63 4.6 80 2.7 60 6.0 91 2.8 61 6.8 91 3.8 61 9.4 72 9.4 45 24.8 112 2.5 98 4.8 72 74.6 45 42.3 2,3,7,8-TCDD 161 0.3 112 2.5 2,3,7,8-TCDF 52 0.5 75 2.4 2,3,4,8-TCDF NA NA 75 1.0 1,2,3,7,8-PnCDF 58 0.6 80 2.7 1,2,3,4,8-PnCDF 58 0.6 80 2.7 2,3,4,7,8-PnCDF 58 0.6 80 2.7 1,2,3,4,7,8-HxCDF 64 0.6 91 2.8 1,2,3,4,7,9-HxCDF 64 0.6 91 2.8 1,2,3,7,8,9-HxCDF 64 . 0.6 91 2.8 1,2,3,6,7,8-HxCDF 64 0.6 91 2.8 2,3,4,6,7,8-HxCDF 64 0.6 91 2.9 1,2,3,4,6,7,8-HpCDF 64 0.8 91 3.8 1.) NA not applicable 98 4.8 63 4.6 NA NA 60 6.0 60 6.0 60 5.8 61 6.8 61 6.8 61 6.8 61 6.8 61 7.1 61 9.4 GENP 011048 783859 TABLE 11 RECOVERIES RELATIVE TO 2378-TCDD-13C12 EPRI BASELIKE PROJECT SAMPLE: 1953 LOAD CENTER NETWORK TRANSFORMER TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 ZREC ZREC vs 13C-TCDD 43 100 47 109 55 128 55 128 24 56 43 100 24 56 DET . 2 ZREC ZREC vs 13C-TCDD 16 100 19 119 24 150 24 150 8 50 16 100 8 50 DET . 3 ZREC ZREC vs 13C-TCDD 3 300 10 1000 14 1400 14 1400 7 700 1 100 7 700 2,3,7,8-TCDD 43 2,3,7,8-TCDF 43 2,3,4,8-TCDF NA 1,2,3,7,8-PnCDF 47 1,2,3,4,8-FnCDF 47 2,3,4,7,8-FnCDF 47 1,2,3,4,7,8-HxCDF 55 1,2,3,4,7,9-HxCDF 55 1,2,3,7,8,9-HxCDF 55 1,2,3,6,7,8-HxCDF 55 2,3,4,6,7,8-HxCDF 55 1,2,3,4,6,7,8-HpCDF 55 1.) NA not applicable 100 100 NA 109 109 109 128 128 128 128 128 128 16 100 16 100 16 100 19 119 19 119 19 119 24 150 24 150 24 150 24 150 24 150 24 150 f-12 1 100 3 300 NA NA 10 1000 10 1000 10 1000 14 1400 14 1400 14 1400 14 1400 14 1400 14 1400 783860 GENP 011049 TABLE 12 RECOVERIES RELATIVE TO 2378-TCDD-13C12 EPRI BASELINE PROJECT SAMPLE: 1946 LOAD CENTER NETWORK TRANSFORMER TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 ZREC ZREC vs 13Cl-TCDD 29 83 28 80 31 89 31 89 22 63 35 100 22 63 DET. 2 ZREC ZREC vs 13C -TCDD 18 100 17 94 18 100 18 100 7 39 18 100 7 39 DET. 3 ZREC ZREC vs 13 C-TCDD 10 1000 27 2700 30 3000 30 3000 18 1800 1 100 18 1800 2,3,7,8-TCDD 35 2,3,7,8-TCDF 29 2,3,4,8-TCDF NA 1,2,3,7,8-PnCDF 28 1,2,3,4,8-PnCLF 28 2,3,4,7,8-PnCDF 28 1,2,3,4,7,8-HxCDF 31 1,2,3,4,7,9-HxCDF 31 1,2,3,7,8,9-HxCDF 31 1,2,3,6,7,8-HxCDF 31 2,3,4,6,7,8-HxCDF 31 1,2,3,4,6,7,8-HpCDF 31 1.) NA " not applicable 100 83 NA 80 80 80 89 89 89 89 89 89 18 100 1 100 18 100 10 1000 18 100 NA NA 17 94 . 27 2700 17 94 27 2700 17 94 27 ' 2700 18 100 30 3000 18 100 30 3000 18 100 30 * 3000 18 100 30 3000 18 100 30 3000 18 100 30 3000 G o tto so F-13 783867 TABLE 13 RECOVERIES RELATIVE TO 2378-TCDD-13C12 EPRI BASELINE PROJECT SAMPLE: CAPACITOR TOTAL TCDF TOTAL PnCDF TOTAL KxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 ZREC ZREC vs 13C-TCDD 35 57 34 56 38 62 38 62 35 57 61 100 35 57 DET . 2 ZREC :ZREC vs 13C -TCDD 17 94 16 89 19 106 19 106 23 128 18 100 23 128 DET. 3 ZREC ZREC vs 13C-TCDD 2 40 55 1100 63 1260 63 1260 59 1180 5 100 59 1180 2,3,7,8-TCDD 61 2,3,7, 8-TCDF 35 2,3,4, 8-TCDF NA 1,2,3,7,8-PuCDF 34 1,2,3,4, 8-PnCDF 34 2,3,4,7,8-PnCDF 34 1,2,3,4,7, 8-HxCDF 38 1,2,3,4,7,9-HxCDF 33 1,2,3,7,8,9-HxCDF 38 1,2,3,6,7, 8-HxCDF 38 2,3,4,6,7, 8-HxCDF 38 1,2,3,4,6,7, 8-HpCDF 38 1.) NA * not applicable 100 57 NA 56 56 56 62 62 62 62 62 62 18 100 i7 94 17 94 16 89 16 89 16 89 19 106 19 106 19 106 19 106 19 106 19 106 5 100 2 40 NA NA 55 1100 55 1100 55 1100 63 1260 63 1260 63 1260 63 1260 63 1260 63 1260 783862 GENP 011051 TABLE 14 RECOVERIES RELATIVE TO 237 8-TCDD-13C12 EFRI BASELINE PROJECT SAMPLE: PRECIPITATOR TRANSFORMER TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 XREC XREC vs 13C-TCDD 16 100 17 106 19 119 19 119 14 88 16 100 14 88 DET. 2 XREC XREC vs 13C-TCDD 24 92 28 108 29 112 29 112 17 65 26 100 17 65 DET. 3 XREC XREC vs 13C-TCDD 21 38 32 57 34 61 34 61 24 43 56 100 24 4 2,3,7,8-TCDD 16 2,3,7, 8-TCDF 16 2,3,4, 8-TCDF NA 1,2,3,7,8-PnCDF 17 1,2,3,4, 8-PnCDF 17 2,3,4,7, 8-PnCDF 17 1,2,3,4,7, 8-HxCDF 19 1,2,3,4,7,9-HxCDF 19 1,2,3,7, 8, 9-HxCDF 19 1,2,3,6,7,8-HxCDF 19 2,3,4,6,7,8-HxCDF 19 1,2,3,4,6,7, 8-HpCDF 19 1.) NA * not applicable * 100 100 NA 106 106 106 119 119 119 119 119 119 26 100 24 92 24 92 28 108 28 108 28 108 29 112 29 112 29 112 29 112 29 112 29 112 56 100 21 38 NA NA 32 57 32 57 32 57 34 61 34 61 34 61 34 61 34 61 34 61 GENP 011052 F 1S 783863 TABLE 15 RECOVERIES RELATIVE TO 237 8-TCDD-13C12 ETRI BASELINE PROJECT SAMPLE: 1976 ARC FURNACE TRANSFORMER TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 ZREC ZREC vs 13C-TCDD DET. 2 ZREC ZREC vs 13C-TCDD 67 91 37 82 81 109 51 113 82 111 51 113 82 111 51 113 63 85 24 53 74 100 45 100 63 85 ,, 24 53 DET. 3 XREC %REC vs 13C-TCDD 78 19500 128 32000 123 30750 123 307 50 119 297 50 0.4 100 119 29750 2,3,7,8-TCDD 74 100 2,3,7,8-TCDF 67 91 2,3,4,8-TCDF NA NA 1,2,3,7, 8-PnCDF 81 109 1,2,3,4, 8-PnCDF 81 109 2,3,4,7,8-PnCDF 81 . 109 1,2,3,4,7, 8-HxCDF 82 111 1,2,3,4,7,9-HxCDF 82 111 1,2,3,7,8,9-HxCDF 82 111 1,2,3,6,7,8-HxCDF 82 111 2,3,4,6,7,8-HxCDF 82 111 1,2,3,4,6,7, 8-HpCDF 82 111 1.) NA not applicable 45 100 0.4 100 37 82 78 19500 37 82 NA NA 51 113' 128 32000 51 113 128 32000 51 113 128 32000 51 113 123 30750 51 113 123 307 50 51 113 123 307 50 51 113 123 307 50 51 113 123 30750 51 113 123 30750 783864 GENP 011053 f t - , ' a, " TABLE 16 RECOVERIES RELATIVE TO 237 8-TCDD-13C12 EPRI BASELINE PROJECT SAMPLE: SUBSTATION DISTRIBUTION TRANSFORMER TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 1 ZREC ZREC vs I 13C-TCDD 36 95 48 126 60 158 60 158 66 174 38 100 66 174 DET. 2 ZREC ZREC vs 13C-TCDD 69 86 80 100 36 45 36 45 45 80 100 45 DET. 3 ZREC ZREC vs 13C-TCDD 76 104 66 90 33 45 33 45 7 10 73 100 7 10 2,3,7, 8-TCDD 38 2,3,7,8-TCDF 36 2,3,4, 8-TCDF NA 1,2,3,7,8-PnCDF 48 1,2,3,4,8-PnCDF 48 2,3,4,7,8-PuCDF 48 1,2,3,4,7, 8-HxCD ? 60 1,2,3,4,7,9-HxCDF | 1,2,3,7, 8, 9-HxCDF 60 60 1,2,3,6,7,8-HxCDF 60 2,3,4,6,7,8-HxCDF 60 1,2,3,4,6,7, 8-HpCDF 60 1.) NA not applicable 100 95 NA 126 126 126 158 158 158 158 158 158 80 100 69 86 69 86 80 100 80 100 80 100 36 45 36 45 36 45 36 45 36 45 36 45 73 100 76 104 NA NA 66 90 66 90 66 90 33 45 33 45 33 45 33 45 33 45 33 45 O B ^ o u OS4 F-17 783865 TABLE 17 RECOVERIES RELATIVE TO 237 8-TCDD-13C12 EPRI BASELINE PROJECT SAMPLE: 196 2 LOAD CENTER NETWORK TRANSFORMER TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 ZREC ZREC vs 13C-TCDD 42 91 51 111 51 111 51 111 30 65 46 100 30 65 DET. 2 ZREC ZREC vs 13C-TCDD 45 90 47 94 40 80 40 80 29 59 50 100 29 59 DET. 3 ZREC ZREC vs 13C-TCDD 55 93 62 105 60 102 60 102 26 44 59 100 26 44 2,3,7,8-TCDD 46 2,3,7,8-TCDF 42 2,3,4, 8-TCDF NA 1,2,3,7,8-PnCDF 51 1,2,3,4, 8-PnCDF 51 2,3,4,7,8-PnCDF 51 1,2,3,4,7, 8-HxCDF 51 1,2,3,4,7,9-HxCDF 51 1,2,3,7, 8, 9-HxCDF 51 1,2,3,6,7,8-HxCDF 51 2,3,4,6,7,8-HxCDF 51 1,2,3,4,6,7,8-HpCDF 51 1.) NA not applicable 100 91 NA 111 111 111 i'll 111 111 111 111 111 50 100 45 90 45 90 47 94 47 94 47 94 40 80 40 80 40 80 40 80 40 80 40 80 59 100 55 93 NA NA 62 105 62 105 62 105 60 102 60 102 60 102 60 102 60 102 60 102 783866 GENP 011055 TABLE 18 RECOVERIES RELATIVE TO 2378-TCDD-13C12 EFRI BASELINE PROJECT SAMPLE: SPIKED AGED MINERAL OIL TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 ZREC ZREC vs 13C -TCDD DET. 2 ZREC ZREC vs 13C -TCDD DET. 3 ZREC ZREC vs 13C-TCDD 50 93 55 102 55 102 55 102 49 91 54 100 49 91 45 96 44 94 43 91 43 91 33 70 47 100 33 70 39 98 43 108 40 100 40 100 27 68 40 100 27 68 2,3,7,8-TCDD 54 2,3,7,8-TCDF 50 2,3,4, 8-TCDF NA 1,2,3,7,8-PnCDF 55 1,2,3,4, 8-PnCDF 55 2,3,4,7, 8-PnCDF 55 1,2,3,4,7, 8-HxCDF 55 1,2,3,4,7,9-HxCDF 55 1,2,3,7,8, 9-HxCDF 55 1,2,3,6,7, 8-HxCDF 55 2,3,4,6,7,8-HxCDF 55 1,2,3,4,6,7,8-HpCDF 55 1.) NA * noc applicable 100 93 NA 102 102 102 102 102 102 102 102 102 47 100 45 96 45 96 44 94 44 94 44 94 43 91 43 91 43 91 43 91 43 91 43 91 40 100 39 98 NA NA 43 108 43 108 43 108 40 100 40 100 40 100 40 100 40 100 40 100 GENP 011056 ?-19 783867 TABLE 19 RECOVERIES RELATIVE TO 2378-TCDD-13C12 EPRI BASELINE PROJECT SAMPLE: SPIKED AROCLOR 1016 TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDD OCDD DET. 1 ZREC z r e c vs 13C-TCDD 52 91 68 119 77 135 77 135 103 181 57 100 103 181 DET. 2 ZREC ZREC vs 13C -TCDD 32 94 37 109 36 106 36 106 37 109 34 100 37 109 DET. 3 ZREC ZREC vs 13C -TCDD 30 7144 105 42 100 42 100 40 95 42 100 40 95 2,3,7;8-TCDD 57 2,3,7.8-TCDF 52 2,3,4, 8-TCDF NA 1,2,3,7,8-PnCDF 68 1,2,3,4, 8-PnCDF 68 2,3,4,7,8-PnCDF 68 1,2,3,4,7, 8-HxCDF 77 1.2,3,4,7,9-HxCDF 77 1,2,3,*7, 8, 9-HxCDF 77 1,2,3,6,7.8-HxCDF 77 2,3,4,6,7, 8-HxCDF 77 1,2,3,4,6,7,8-HpCDF 77 1.) NA not applicable 100 91 NA 119 119 119 135 135 135 135 135 135 34 100 32 94 32 94 37 109 37 109 37 109 36 106 36 106 36 106 36 106 36 106 36 106 F-20 42 100 30 71 NA NA 44 105 44 105 44 105 42 100 42 100 42 100 42 100 42 100 42 100 783868 GENP 011057 TABLE 20 RECOVERIES RELATIVE TO 237 8-TCDD-I3CI2 EFRI BASELINE PROJECT SAMPLE: SPIKED AROCLOR 1260 TOTAL TCDF TOTAL PnCDF TOTAL HxCDF TOTAL HpCDF OCDF TOTAL TCDDOCDD DET. 1 m e m e vs 13C-TCDD 52 32 58 36 64 40 64 40 57 35 161 100 57 35 DET. 2 ZREC m e vs 13C-TCDD 75 67 80 71 91 81 91 81 72 64 112 100 72 64 DET. 3 ZREC ZREC vs 13C-TCDD 63 64 60 61 61 62 61 62 45 46 98 100 45 46 2,3,7,8-TCDD 161 100 112 100 2,3,7, 8-TCDF 52 32 75 67 2,3,4, 8-TCDF NA NA 75 67 1,2,3,7.8-PnCDF 58 36 80 71 1,2,3,4, 8-PnCDF 58 36 80 71 2,3,4,7,8-PnCDF 58 36 80 71 1,2,3,4,7, 8-HxCDF 64 40 91 81 1,2,3,4,7,9-HxCDF 64 40 91 81 1,2,3,7,8,9-HxCDF 64 40 91 81 1,2,3,6,7,8-HxCDF 64 40 91 81 2,3,4,6,7, 8-HxCDF 64 40 91 81 1,2,3,4,6,7, 8-HpCDF 64 40 91 81 1.) NA not applicable 98 100 63 64 NA NA 60 61 60 61 60 61 61 62 61 62 61 62 61 62 61 62 61 62 OBNP01 oss F-21 "783869