Document g2ejNzDM22LDGxjO7bZXR5JvL

Monsanto S6EH/ESC Ito.7D? ;/Rpr. TlocrtTon) Analysis^ (Type of ReportJ REPORT NO.: HSL-S61S ESC-UAG-86-32 JOB/PROJECT NO.: 6216 DATE: April 22, 1986 sa TITLE: ANALYSIS OF TOTAL PCB CONGENERS IN KRUMHRICH SOIL SAMPLES AUTHORS: B.M. Hughes, D. McKenzie, and C. Trang ABSTRACT: Krumarlch Plant soil samples were analyzed for total 5 PCB congener concentrations using capillary GC/EC analysis techniques. All samples contained total PCB congeners at levels less than SO vg/g. ?g Ii TECHNICAL APPROVAL: Environmental Sciences Center Senior Research 6roup Leader APPROVED BY: Environmental Sciences Center Quality Assurance Specialist APPROVAL DATE: HONS 0239 74 COMPANY CONFIDENTIAL This document is the property of Monsanto Company and the recipient is responsible for its safekeeping and disposition. H contains CONFIDENTIAL INFORMATION which must not be reproduced, revealed to unauthorized persons or sent outside the Company without proper authorization. DISTRIBUTION! COPY NUMBER 1. J. Gloeckner - 1740 2. B.M. Hughes - U4E 3. D. McKenzie - U4F 4. C. Trang - U4F 5. P.l. Sherwn - U1F 6. W.H. Mees - U4D 7-9 Report* tlbrery - RPC 10. Chesterfield Intonation Center - AA3A ABSTRACT ONLY H.A. Woltermann - U4E COMPANY CONFIDENTIAL This report has been assigned to you. When it is no longer needed, you are responsible lor reluming it to: II you trensler it to anyone else, please let your librarian know, so the records can be changed. iMstcnatv i/ioi MOWS 023975 Time Scamp <860422.10l3> ANALYSIS REPORT DATE: April 22, 1966 LOC NUMBER: U-86-04-08-01 PROJECT NO: 760.28-6216 TO: Jim Cloacknar/Krummrleh Plane FROM: Environmental Sclancaa Cantar KonaanCo Company 800 N. Lindbergh Blvd. St. Louie, Mo. 63167 Phono No: (314) 694-1464 Title: Analyela of Total PCB Congeners In Kruamrleh Soil Samples. ABSTRACT Kruamrleh Plant soil eaaplee vara analysed for total PCB congener concentrations using capillary CC/EC analysis techniques. All samples contained total PCB congeners at levels less than 50 ug/g. IBTRODOCTIOH Ten soil samples vers analyzed for total PCB congener concentrations. These analyses are required as a pert of the Kruamrleh Plane cleanup of an area where chemicals had previously been stored. SUMMARY Table 1 summarizes the results of capillary GC/EC analyses of 10 soil ex tracts. Note that all samples contained a total PCB concentration less than 50 ug/g. Table 1 also summarises quality control experiments conducted on one blank aoll sample. Table 2 summarises results from qusllty control native spiking studies for blank soil and sample IB-3. See PCEX21 and PCEX03 for the details of how the samples were extracted and cleaned up prior to CC/SC analy sis. Refer to Standard Analysis Method ECAN02 for the details of hev the cleaned up extracts vere analyzed. This information is Included in a later section of this report. The patterns of PCB eongeners found In these soil samples vere similar to the Aroclor 1262 pattern. However they vere not identical. In a previous project for the Krummrlch Plant (Project Number 760.28-6204), similar results vere ob tained for soil samples which were analyzed using GC/EC and GC/MS extract analysis methods. In that study, the PCB congener patterns vere also net Identical to Aroclor 1262. Therefore ve have chosen to report data based upon this less expensive, yet technically equivalent, GC/EC analysis method for this present study. 'continued) HONS 023976 Page 2, A21618 (cont'd) QC RESULTS Quality control raaulta ora shown In Tablaa 1 and 2. Thate tablaa show good recoveries of surrogate compounds which wr* added to each saaple before extraction. Thle Inforaetlon Indicate# hov well each soil saaple was extracted. Duplicate analyses of IB-2 and IB-3 are also shown In Table 1. Table 2 suaaarlzes recoveries of Aroclor 1254 which was added to Blank Soil saaplee, and IB-3. These data show that good PCB congener recoveries would be expected using these Methods for the enelysls of soils froa the Rruanrlch Plant. DETAILS Standard Saapllng Method No(s): Saaples supplied by the Kruaarich Plant. Standard Extraction Method No(s): PCEX03 and PCEX21 (See PCFS03 and PCFS21 for flow sheets describing these Methods) Standard Analysis Method No<s): ECAN02 Final Report File Mo<a): A21618 Table File No(s): B21618, C21618 Also Included In this report are: 1) Suanarles of Standard Extraction and Analysis Methods used for this project. 2) Cheln-of-eustody Inforaetlon. 3) Analysis Request Inforaetlon recorded at saaple login. 4) A copy of the ESC/UAC Cood Laboratory Practices Manual. ANALYST(S): B. Mason Hughes, David McKenzie and Chi Trang ANALYST APPROVAL: HONS 02397? TABLE 1. Summary of FCB Concentrations In Soil Semples Determin'd using KEX21 end FCEX03 Extraction Methods end ECAN02 Analytical Method. ESC Project Mo; 760.29 - 6216 Date: April 21, 1916 Semple I.D. Surrogate Recoverles(tRecovery) PCB(a) CL5-benzene 2,4,6-CL3-blphenyl Concentration (ug/g) Method Blank IB-1 IB-2 (Dur) IB-3 (DUP) IB-4 IB-5 34 49 SB 95 80 * 49 49 56 73 65 82 86 61 68 71 Total ND(b) - 8.9 10.6 3.1 3.1 ND(b) * IB-6 72 103 IB-7 52 74 IB-8 72 97 0B-30 64 96 OB-32 60 97 8.1 ND(b) Footnotes: a. b. Aroclor 1256 end Aroclor 1262 standard formulations were used to calibrate the capillary GC/EC response for PCB congeners. Mow* ever the pattern of congeners in these soil samples were not identical to these formulations. See text for more details. NIK None Detected (<1.0 ug/g) TABLE FILE NO: 021619:MH HONS 023978 TAILS 2. Suaunary of Aroclor 1254 Spiking Concentration! and Recoveries In Quality Control Experlnents for Soil Saaplaa. ESC Project Ho: 7(0.2S - <21< Data: April 21. lt< Sample l.D. Surrogate Racovarlaa (IRecovery) Aroclor 1254 CL5*benzene 2,4,6-CL3-Biphenyl Soli Blank(L. Splk*) (H. Splk*) 34 44 48 84 IB-3 (L. Splk*) (H. Spike) 22 99 77 84 Anount Added Recovery (Ug/g) <%> 1.00 10.00 110 103 1.00 10.00 109 79 TABLE FILE NO: C2071S:MH HONS 023979 Th following pi|l deicrlba Standard Sampling, Extraction, and/or Analytic Mathoda usad for thla projaet. MOMS 023980 ISC Standard Extraction Kathod (SEM) TITLE: tCU in Non*EC Activ* Matrices ESC Standard Extraction Method MoFCEX21 MATRI(X),(CES): Solis end other non-EC active solids end solvents TYPICAL SAMPLE SIZE (*) TYPICAL EXTRACT VOLUME <!) 0.5 - 5.0 10 TYPICAL ANALYTES: Aroclore 1232, 1242, 1248, 12S4, 1260, 1262, trlchloro blphenyl isoaers through octachloro* biphenyl leoaere ESC Standard Analysis Method Not: ECAN01, ECAN02 INTERFERENCES: Any electron capturing epeelee In the retention tlas region of trlchloroblphenyl leoaere through octechloroblphenyl leoaere that le non acid hydrolytabla TYPICAL SURROGATES TYPICAL RECOVERIES () pentachlorobenxene 2,4,6-trlchloto- blphenyl 50 - 120 50 - 120 APPARATUS AMD MATERIALS: Eurdick and Jackson benzene or haxana for saaple extraction or dilution. Pierce vials. Sulfuric acid at varying concentrations. Ultrasonic bath. Disposable glassware. (See flow sheet for this extraction aethod in PCFS21.) LIMITATIONS: Method applies only to aatrlees which do not contain Interfering electron capturing species in the trlchloroblphenyl through octachlorobiphenyl laoaer retention tine region. SAFETY PRECAUTIONS: See PCS handling protocola In laboratory eafaty aanual. DATES OF METHOD CREATION AND UPDATES: 12/17/84 MOHS 023991 FLOW SHEET FCFS21 FOR ESC EXTRACTION METHOD FCEX21 SAMPLE ID: EXTRACTION DATE and TIME: ... SAMPLE COLOR AND DESCRIPTION MRC EXTRACT LOC NO: WEIGH OUT SAMPLE INTO A 14 OR 40 aL PIERCE VIAL [) . SAMPLE WEIGHT SURROGATE SPIKE OF SAMPLE . [] ADD 10.0 bL BENZENE TO SAMPLE. . [] ULTRASONICATE SAMPLE FOR 1/2 HOUR IN A SOUND BATH. () . . PLACE 2 aLOF THE EXTRACT INTO A 7 aL VIAL * ADD 2 aL ............ SULFURIC ACID AND SHAKE . [] . . (] . . ALLOW PHASES TO SEPARATE REMOVE 1 aL FOR ANALYSIS. . [1 EXTRACT NO: ............... DATE/TIME COMPUTED ANALYST: ..................... ESC JOB NO: 10.0 aL FINAL VOLUME .............................. MONS 023982 ESC Standard Extraction Mathod (SEM) TITLE: PCBs In Non-EC Active Matrices ESC Standard Extraction Method Mo: PCEX03 KATRI(X),(CCS): Soils and othtr non-EC active solida.solvants and oils. TYPICAL SAMPLE SIZE (g) TYPICAL EXTRACT VOLUME <1) TYPICAL ANALYTES: Aroclora 1232. 1242, 1248, 1254, 1260. 1262. trlehloro* blphanyl lsomsra through octachloro* blphanyl isoaara 0.5 - 5.0 10 ESC Standard Analysis Mathod Nos: ECAN01, ECAN02 INTERFERENCES: Any alactron capturing spsciss in tha ratantlon tima rsgion of trlchloroblphanyl Isomer* through octaehloroblphanyl isoaers which ir not ramovad by tho thraa*phasa silica* gsl column. TYPICAL SURROGATES TYPICAL RECOVERIES (%) pantachlorobanzana 2,4,6-trlchloro* blphanyl SO 120 SO 120 APPARATUS ADD MATERIALS: Burdick and Jackaon haxana for staple axtractlon or dilution. Sodluai aulfata for drying tha aanpla Matrix. Silica gal colunne lnpregneted with potaaslun parnanganata, sulfuric acid. and potasaluM hydroxide. Nitrogen for extract volujee reduction. Dlsposeble glaaswara. (Sea flow sheet for this axtractlon Method In PCFS03.) LIMITATIONS: Mathod applies only to aatrlcaa which do not contain lnterfarrlng electron capturing species In the trlchloroblphenyl through octaehlorobiphenyl laoner retention tine region when electron capture analytical Methods are used. This llnlcation does not apply to naas spectronetrle Methods.. SAFETY PRECAUTIONS: See PCS handling protocols In laboratory safety Manual. DATES OF METHOD CREATION AND UPDATES: 2/13/84. 9/2S/S4 HONS 023983 FLOW SHEET FCFS03 FOR ESC EXTRACTION METHOD FCEX03 SAMPLE ID: .............................................................-............... MRC EXTRACT 0 ............................................................................... LOG NO: ............ EXTRACTION DATE And TIME: WEIGH OUT SAMPLE INTO A 16 aL VIAL [] SURROGATE SPIKE OF SAMPLE . (] FINAL WEIGHT INITIAL WEIGHT SAMPLE WEIGHT DRY SAMPLE IF NEEDED BY . ADDING ABOUT 0.1 ( {1 Na SO TO VIAL . 24 . .(] RINSE COLUMN WITH 2 X 20 bL HEXANE DILUTE SAMPLE IN VIAL WITH HEXANE AND PUCE ONTO CLEAN-UP COLUMN. [] . . QUANTITATIVELY RINSE VIAL ONTO COLUMN WITH 4 X 1 at RINSES. . [] . ELUTE SAMPLE INTO 50 aL . CENTRIFUGE TUBE WITH [ ] 40 aL HEXANE. . NITROGEN BLOW DOWN TO . ___ ________________ aL [1 EXTRACT NO: .............. DATE/TIME COMPLETED ANALYST: ..................... ESC JOB NO: ............ CLEAN-UP COLUMN DESCRIPTION 25 aL DISPO PIPET 1 ea Na SO 24 4 ea It POTASSIUM PERMANGANATE SILICA CEL 1 ea SILICA CEL 4 ea ACID SILICA CEL 1 ea SILICA GEL 4 c BASE SILICA GEL \/ \/ GLASS WOOL MOHS 0239* ESC Stanford Analyali Method (SAM) TITLE: Aroelor Porsulatlene In Solventa ESC Standard Analyale Hathod Ho: ECAN02 ANALYTICAL INSTRUMENT AND MODE OF OPERATION: HP-5880 Capillary CC/EC Inter faced to an HP-3357-LAS Laboratory Data Syatco TYPICAL ANALYTE TYPICAL INSTRUMENT LEVEL OF DETECTION (LOD) (ug/sl) Aroelor foraulatlona 1232, 1202, 1208, 1250, 1260, and 1262 0.1 TYPICA1. PRECISION 8 10X LOD <> 30 TYPICAL ACCURACY 8 10X LOD <) 30 INTERFERENCES AND LIMITATIONS: Any alactron capturing apocloa In tho reten tion tlae region of trlchloroblphenyl through oetachloroblphonyl leoaero aro potential lnterforencoe. Exact retention claoo of Boat likely PCS laoaere can bo obtained fro* the analyala of Aroelor 1208, Aroelor 1250 or Aroelor 1260 fonulatlona. CHROKATOCRAPH1C COLUMN: 30-seter fuaad alllca J&U DB-S (0.25 uM) with vide bora (0.32aa). COLUMN TEMPERATURE PROGRAM: 130(11/0/300 INJECTION TYPE: Splltlaoa CALIBRATION AND STANDARDIZATION: Uee Internal atanford quantitation technique and calibrate lnatrusont reaponae factora froa authentic Aroelor forsulatlon atandarda. Uaa a wlnlaus of 10 PCB laosera for the foterwlnatlon of fore lation Identity and quantity. CALCULATIONS: Forsulatlon concentration (looser RRF)(looser area/internal atandard area) where: RRF la the relative reaponae factor for the appropriate PCB looser In a given forsuletion. Forsuletlon concentretlon la obtained fros the average of at leaat 10 euch cal culation. SAFETY PRECAUTIONS: Sao PCB handling protocola In laboratory aafacy annual. DATE OF METHOD CREATION: 10/25/83, 2/3/84 Tine Stasp - <860422.0936> HONS 023985 Th. following p>g .how chsln-of-custody Inform.tIon for thl( proj.ct. HONS 023986 Monsanto MONSANTO INOUSTOmi CHEMICALS OO. MllnoU CftOl (ij tri-teas CHAIN OF CUSTODY SAMPLING RECORD Sampling Identification: Log Number: Date: tf.J.U 3 t&-t *-,z ' V-/ S4 T0-Z. t-tjK.' d-t.ttlZ-3 -j.i.it a-t 7/t:,wj Analyses Required: V-/JK ts-i yf-nft d.i-nt J&-1 0 .//4' f-i-m jb \ ja-u' S-3-Jt 4 a ?*-///, /-J-ti ti -td 3*-.,,< Sanpla Takao By: 7/004 d/tf.z*11 <- Data: LABORATORY RECORD keeclvad By: /tt4 0fi6.aTtt.rz. Data: V- /.ft Data H r=2k Comments ________ REPORT OP AWALTSES Data dh/jk Report No. rnj-st/s Author INSTRUCTIONS Th person taking the sample completes the Information In the Sampling Record area. Each person to vhoa the sample la relinquished should algn the form and forvard as necessary. Analyses performed should be listed uith comments. When all analyses are complete, the original should return to the "Received By" signature. HONS 023997 Tha follovlnf pi|l daacrlbe Analytical Raquaat InforHtion ganaratad for thla projaet. HONS 023988 Tin* Stanp - <860422.0920> MONSANTO COMPANY/ENVIRONMENTAL SCIENCES CENTER ANALYSIS REQUEST DATE: 4-8-86 LOG NO: U-86-04-08-01 REQUESTER: Kruamrlch PROJECT NO: 6216 REPORT RESULTS TO: F1LES/MEES, Hugh**, Sharaan, McKanzla, Trang ANALYSIS REQUESTS SENT TO: FILES, Mesa, Sher.en, Hughe*. McKenzie SAMPLE PICKUP BY: McKenzie SAMPLE LOCATION: U-420 SAMPLE DESCRIPTION FOR 10 SAMPLES ESC SAMPLE IDENTIFICATION NUMBER OF BOTTLES NUMBER(S) Blank oil (METHOD BLANK) Blank aoll a LS Blank aoll a HS IB-l, 3-31-86, 6-12' IB-2, 4-1-86, 0-13 1/2' IB-}, 4-1-86, 0-17 1/2* 1 x 4 OS 1 x 4 os 1 x 4 os IB-4, 4-1-86, 7 1/2-19 1/2' IB-5. 4-2-86, 10-19' IB-6, 4-2-86, 7 1/2-17 1/2* IB-7, 4-2-86, 0-14 1/2' IB-8, 4-3-86, 7 1/2-20' OB-30,, 4-3-86, 7-14 1/2' OB-32 , 4-3-86, 20-22 1/2' 1 x 4 os 1 x 4 os 1 X 4 OS 1 x 4 os 1 x 4 os 1 x 4 os 1 x 4 os PCB-1582 FCB-1S83-LS PCB-1584-HS PCB-1585 PCB-15S6, PCB-1587-DUP PCB-1599-NS PCB-1588, PCB-15B9-DUP PCB-1590-LS, PCB-1591-HS PCB-1600 PCB-1592 PCB-1593 PCB-1594 PCB-1595 PCB-1596 PCB-139? PCB-1598 Not*- DUP t*f*r* to duplicate analyala, LS r*f*ra to * low l*v*l natlvt aplka, HS rafara to a high l*vl nativa aplka, and NS rafara to no alaulatad aplka, which waa dona to dotarwlna If any of th* aurrogat* coapounda war* In th* aaaplaa alnca thla waa auggaacad by low racovary of th* pantachlorobonzan* aurrogat*. It waa detaralnad that th* aaaiplaa did contain aaaaurabla quantltla* of both pantachlorobonzan* (aurrogat* aplklng compound) and haxachlorobanzan* (lntarnal atandard), *o an axtarnal atandard aethod wax uaad for quantitation. RECORDED BY: McKanzla REQUIRED ANALYSES: PCBa ANALYTICAL TECHNIQUES: TECHNIQUE (EN) DATE COMPLETED TECHNIQUE(EN) DATE COMPLETED x CC/EC (18) 4/22/86 QUALITATIVE: x SEMIQUANTITAT1VE: QUANTITATIVE: X HONS 023989 REQUIRED QA/QC: SEE GOOD LABORATORY PRACTICES MANUAL COMPLETION DATE REQUESTED: COMMENTS: Verbal taaulca reported to Gloacknor on April 21. SAMPLE DISPOSITION: HOLD FOR 30 DAYS SAFETY PRECAUTIONS: SEE SAFE LABORATORY PRACTICES MANUAL ANALYSIS REQUEST FILE NAME: AA216:LI HONS 0239^0 ANALYSIS REQUEST |WTl |LOG NO. MONSANTO COMPANY DAYTON LABORATORY REQUESTER- SAMPLE DESCRIPTION NUMBER Of BOTIIB. .' CHAItGI mr MJMBER Of SAMPLES " - 1 '' / ; ' ' 1 -. n ; -7 * ' ` - - . . /; . .' \/ * '/ " * * * ' 7 REQUIRED ANALYSIS** P'f. . RECORDED BY: ^ . REPORT NISULTI TO* ANALYSIS MOUfSI W nus * n' SAMPLES FOR: h . -- SAMftt LOCATHM KNOWN HEALTH HAZARD PRESENTED IY SAMPLE: REFERENCE TO PREVIOUS WORK (REQUEST I. JOURNAL.ETC.) COMPLETION DATE........................... .......... TIME ALIOTED FOR ANALYSES ANALYST HOURS INST. TIME ANALYTICAL TECHNIQUE ** GAS CHROMATOGRAPHY Q NMR ULTRAVIOLET O HPIC VISIBLE XRD INFRARED ICP EMISSION A10MIC ABSORPTION EDAX XRF D MICROSCOPY MASS SPEC O GCJMS O OTHER _ 0 AUTOANALYZER QUAL__ SEMIQUANT_________ QUANT. _ REQUIRED QAJQC AJTLMNPORT COAPlflt D DISCARD RC1URN HOLD FOR D 30 DAYS UtOOAYS _ - THIS INFORMATION MUST IE SUPPLIED IY ANALYSIS REQUEST ORIGINATOR MONS 023991 OTHER Th following 1 copy of thft ESC/OAC Cood Laboratory Practical Manual. HONS 023992 Copy Number: GOOD LABORATORY PRACTICES MANUAL A Guide to Quality Control/Quality Anurinci Ultratrace Analydp Group March 1984 oaaoR J. Rro Croup Leader, Ultratrace Analytic ____ _______ R. A. Woltemann Manager, Envlronaental Sclancaa Canter leaued to: Data: _ JR3/JOB A Envirotmntal Sclaocta Center Dayton Laboratory Dayton, Ohio 45407 HONS 023993 TABLE or CONTENTS I Objective* II Scop* 111 Analyal* A. Method* 1. QA/QC Frograa 1. Staple Preparation QA/QC *. Method Blank* b. R*pllc*te* c. Spike* 2. lottruaental Analyala QA/QC *. In*truaent*tlon b. Blank* c. Quntlt*tlon Internal Standard d. Standarda C. Degree* of Quantitation 1. Qualitative Analyal* a. Tentative b. Confined 2. Seal-Quantitative Analyal* 3. Quantitative Analyal* D. Quality Criteria and Beaedlal Action 1. Quality Criteria a. Blank* b. Bacovarla* c. Precision d. Llalt of Detection e. Accuracy 2. Beaedlal Action IV Data V Staple Dlapoaal FIGURES lit!"* 1 Exaapl*.of GC/MS Logbook page 2 Exaapl* of CC/EC Logbook page 3 Exaapl* of Dlec/Tape Logbook page !str I l t j 2 2 2 2 2 3 3 ^ A 4 4 ; 7 7 7 7 g g g g g ) 9 y y 10 ISE 3 6 11 HONS 023*9* I. Objectives Th* Min objectives of cbt Ultratroet Analysis Croup quality sssurence/quallty control profraa art: 1) to aaaura that our laboratory generates high quality raaulta; and 2) to Mlntaln the otcaaaary rtcorda that docunant laboratory perfonsnee. II. Scope The ecopa of this manual tncludaa araaa of CLP not epeelflcally addraaaad In the ESC eectlon manual and expands upon certain araaa where QA/QC practlcea differ from thoac deacrlbcd In the eectlon menual. It la Intended to be need along with the eectlon manual to provide a complete picture of the CLP within the Dltratrace Analytic Croup. III. Analytic The generetlon of analytical reaulta within the Dltratrace Anelyala Croup routinely lnvolvee two proceaaeai eample preparation and lnatrumental aoalyala. Sample preparation Involves one or more of a variety of techniques Including extraction, dilution, aeld/baee waahea, column chroMtography, concentration and numerous other techniques to render the eample la a suitable condition for lnatrumental analyala. Instrumental analysis takes the suitably prepared sample and lntroducea It Into an analytical Inatnaent to measure the desired parameter(a), loth of these processes can be described by clearly defined and separable methods called sample preparation methods (SPMa) and lnatrwencal analyala methods (IAMs). SPMa and lAMs My be combined In numerous ways (depending upon the Mture of the samples and the needs of the customer) to produce a auccaasful analytical protocol. For example, aevaral different SPMa My be used to product samples that are suitable for analysis by a single LAM. The sesaurea Incorporated Into each of these experimental processes to ensure that an sssesaMnt of the quality of the results can be made constitute the QA/QC program for a project. The following subsections describe the elements of the analyala proceaa: A. Methods Methods are the written documentation that describe the enalytlcal process. They contain sufficient detail such that a competent scientist or technician can readily perform the required analyses. The usual practice la to have methods that describe the sample preparation process (SPMa) and nethods that describe the instru mental analyala process (IAMs). Each method developed within the Ultratrace Analysis Groups la assigned a method number as described In the ISC Section Manual. Met hoda are obtained from various sources Including ln-bouse develop ment, modification/adaptation of literature Mthods, or specific protocol methods dictated by government agencies. Methods may be tonally validated by a aeries of experiments that describe a claaalcal validation protocol or My be less vigorously proven ovlng to factors such as frequency or use, custooer needs and 1 HONS 023995 coet/tlalng restrictions. In any eaaa a QA/QC prograa la applied to tha analyele proceaa to provide a aaaaura of tha quality of tha reeulta. Unless a QA/QC prograa la preecrlbed by a required protocol (e.g., IfA Dioxin In Soil protocol), certain nlnlnun QA/QC aaaauraa (depending upon tha analyele type) ara Incorporated Into all Ultratrace Analyele projeete. The following aubaactlon daaerlbaa tha Ultratraca QA/QC prograa: QA/QC Program An effective QA/QC progran lneorporatea axptrlnenta that provide Information relative to each of tha following queetlonei (1) Are there any lmpurltlee, background or contamination that will Influence tha reeulta? (2) How reproducible are tha raaulta? (1) How well can the analyte be recovered from tha eample matrix? (A) What la the limit of detection for the analyele? (5) What la tha dynamic range of the analyele? (6) What le the accuracy of the analyele? All of thaaa queetlone ara addraaaed by properly aelectlng/applylng the uae of blanke, replicator, eplkee and etandarda In a QA/QC prograa. The dlacuaalon of tha uae of thaae QA/QC tecbnlquee aa they apply to Ultratrace Analyele Croup actlvltlea la beet done by considering tha aaaple preparation and lnetrumentel analyele proceeeea aeparately. 1. Sample Preparation QA/QC a. Method blenke - kepreeentatlve glaeevare, aolventa and reagente ara need with eample aetrlcee which arc elmllar to thoee for which reeulta are being reported, yat do not contain the analytee of lntareat. Method blanka are analyaad at a frequency equal to 10X of tha analyzed eamplae for aaaple acta which are aultlplee of 10. At leant one method blank la analyzed for aaaple acta containing between 1 and 9 aaaplea. b. lepllcataa - If aufflclent aaaple amounts have been aubalttcd for analyele, replicate frequency la the aaae aa tha method blank frequency. If at all poeelble, replicator rhould be obtained froa the acme aaaple bottle In order to alolalae eample inhomogeneity problaae due to aaaplea being taken at ellghtly different tlaee. c. Splkea - If aufflclent eample la available for each aaaple type, the aaaple la epllt and aplkad at two levela with 2 HONS 023996 the native (unlebeled) enalyte(s). Th levels ere typically 2x (low) and 20x (high) the anticipated detection Halt and eerve as a technique (or esti mating the Halt of detection far each aatrlx. These low and high spikes are conducted at a frequency equal to the Method Blank frequency. Obviously spiking with the native analyte cannot be done for wldescan analysis since this presupposes knowledge of the Identity of the anslyte(s) In the eaaple. Other spiking techniques are used to evaluete the extrac tion/recovery efficiencies for the analyte(s) of Interest. Ideally extrectlon/recovery efficiencies are determined for each saaple, since. In principle, each seaple nay represent a different matrix. Thle can be done very easily when the detection technique Is aasa spectroaetry If an leotoplcally labeled version of the analyte(e) Is avalleble. Docuacntetlon of extraction/recovery efficiencies Is not required for each saaple If the seaple matrix for a set of saaples Is constant. However, for a eaaple set for which the similarity of saaples Is not known, end for which adequate eaaple la available, each saaple Bust be epllt end spiked with a known aaount of the aaalyte(s) of Interest to determine extraction efficiency. If adequate eaaple alee le sot available or the Identity of tha analyte(s) la sot known before the fact (l.e., wldescan analysis), surrogate spiking compounds aey be used to assese extraction efficiencies In each seaple without actually spiking each seaple with the aoalyte(s) of Interest. The choice of the surrogate spiking compound Is tailored for each analyte. This aurrogate must be chosen so that It la either ehealcally Identical to the analyte of Interest (for axaaple using leotoplcally labeled analogues of the aoalytes), or Is closely elallar la terms of llquld/llquld partition properties, chaalcal reaction properties, eoluan elution propertlee or other aatrlx 1eola tion properties which are seed to Isolate the aaalyte(a) from the saaple aatrlx. another property of the aurrogate eplklng compound Is that It not ha present In the saaple being analysed Instriaantal analysis QA/QC The final step In obtaining analytical results Involves the use of an appropriate Instrumental technique to produce the analytical data feveral QA/QC practices must be Incorporated In this process to ensure validity of the data. a. Instrumentation Careful docwcntatlon of Instrument usage, calibration, and maintenance la essential for the generation of high quality results. Iach major Instrument within the Oltratrace Analysis Croup will be the assigned responsibility of a professional eaployae designated as the Instrxment steward. The Instalment Scewerd IS rssponslbls for making aura that logbooks are avail able and properly completed by lnetriment users. It Is the 3 HONS 023997 responsibility of o*ch Individual ualn| tha equipment to xocotd *11 tha pertinent data required in tha logbook. An example of a page fro* a CC/MS logbook 1* glvtn In Figure 1 and that of a GC/EC logbook la given In Figure 2. Instruments vlll b* callbtatad according to the lnstruant aanufacturara' specifleatIona or according to tha method being uaad with the lnatrument. A log of lnatrument calibration vlll be maintained with tha Instrument. Tha Inatrumant Stavard vlll b* responsible for anaurlng that preventative and corractlva maintenance prograna are carried out on all lnatnaeenta under hla/har responsibility. If a specific problem la noted by an inatrumant near, It ahould be noted In the logbook and tha Inatrumant Stavard notified ao that appropriate corractlva action can be taken. b. llanka A solvent blank vlll bt analyaad at a frequency equal to tha method blank. Tha method blank can serve a* the solvent blank provided It la clean In tha area of tha analyta(a) af lntareat. This practlea eliminate* tha possibility of background Instru mental contamination. c. Quantitation Internal Standard A quantitation Internal standard vlll be added to each sample follovlng sample preparation but prior to lnstriaeutal analysis. This compound vlll serve for determining relative response factor* and for correcting for variation* In sample Injection voliasea and evaporation of solvent*. d. Standards Standards ara solution* of the analyte(a) of Interest used to determine the response of the detector over the rang* of analyte concentration* found In the samples. For Quantitative analytes, sufficient standards and replication of standard* vlll be run to demonstrate linearity and precision of tha detector reeponse over the range of analyte concentrations. Should sample concen tration* fall outalde the demonstrated linear range, either additional standard* *r* prepared to anpand the raoge, or appropriate dllutlon/concentratlon of the sample la don* to place It In the proper range. Degrees of Quantitation The Information provided for any particular analysis Is tailored to the needs of the customer. In actual practice the** need* vary across the broad continuum from the grossly qualitative to the precisely quantitative. It la informative to examine vhat is Involved in providing the varying degrees of quantitation required by our customer*. HONS 02399 4 HM IMNIWI bmi_ ___ -. HP 5985A *m_ . - M*<NtcaiiMaai _ *_ _ Iff IMN ncwtt I. Uwflt ( CC/NK U|tok HI1* HONS 0239 toiitcf____ ... __ ... . ht see gc/cc. . ftH______ . . taitw -- - Mulatto!HIM* ft IN .... . . _ m utm HONS 024000 1. Qualitative Analyala Qualitative analytic implied no quantitation at all but rathar aeeka only tha Identity ef tba eonpound<e) priotne. GC/HS it particularly applleabla to thle type oi analyale problem. Tun typta of ldantlflcatlona can be aade: a. Tentative A tentetive identification la node on the baala of tha aoelyet'a judgement of a natch between the aaaa apectrt* fion the aanpla and a aaaa epectrta fioa a reference library. Thla la often done for the large nuaber of coapounde found in a videocan organic analyala. b. Confined A confined Identification required that the ehroaatographic retantloo tlaa and the aaaa apectrua of the unknown conpound natch thoee of a known etaodard of the tentatively identified coapound. Thla la often dona in videacan analyaea when atandarda can be obtained for tentatively identified coapounde that are of concern. Tha normal QA/QC requireaenta for qualitative analyale are (1) analyala of a blank, (2) analyala of duplicate aaaplea and (3) uae of a calibration compound (uaually Decafluorotriphenylphoepblne, omr) to aaaure that the aeaa apectroaeter will produce aaaa apectra that can be coaparad with library apeetra. 2. Seal-Quantitative Analyala Seal-Quantitative Analyala extenda tha information provided by a qualitative analyala to include aoae eetlaate of the amount of analyte(a) prevent. The method of aeal-quantltatlon Involved the eoaparlaon of detector reepooee of tha analyta(a) with that of an Internal etandard. The aatimated concentration la obtained by aeewing a unit reepooee faccor between the analyte(e) and the Internal atandard(o). An Indication of recovery from the eampla matrix la obtained from the recovery of the eurrogote Internal atandard(a). j. Quantitative Analyale Quantitative Analyala provided for the accurate aaaeaaaent of the amount of analyte(a) preaent in a aaaple. To be able to do quanti tative analyale one aunt know the Identity of the analyte ao that atandarda can be prepared for apiklng and for the generation of calibration curvea. The nethod of quantitation la baaed on a three-point calibration curve uelng atandarda of the analyte(a) of lotereat over the range of coocentratlone in the aamplea. A onepoint calibration nethod can be uaed (ae with the laboratory data 7 HONS 024001 tjtttm) provided that linearity boo boon dcaonatrated ovtr (ho concentration rant* of the oaaplec using standards of tk* analyte(s) at tbraa cooceotratlooa to tha rang*. Thla calibration carva la than aaad to provide concantratlona of.tha analyte(e) In tha eaaplee via an akternal atandarda aatbod or aora preferably via an Internal atandarda aatbod. for tha Internal atandarda aethod. the quantita tion internal atandard la added to each of tha atandarda (Just aa with tha aaaplaa) prior to lnatruaaotal analysis and relative reaponoe factota ara dataralnad. for quantitative analysis tha aaaa apactroaatar la operated aa a gaa chroaatographlc detector. Tha MS la therefore tuned and operated In a aanner epeclfled In the approved aethod rather than vein* a calibra tion coapound aa required for qualitative analyses. Quality Criteria and keaedlal Action Tha lnclualon of QA/QC aeaaurea into an analyala prograa haa little aeanlag unleaa tbe reaulta are Interpreted and approprlata action la taken vhen necaaaary. The ability to do tbla aaauaea aoae aet of criteria that will trigger a reaponaa or reaedlal action. Tha following aubaectlona daacrlbe the critarle that are need in the Ultretrace Analyala Croup to evaluate when quality control data Indicate a need for corrective aeaaurea and what reaedlal action will be taken. 1. Quality Criteria The overriding quality criterion above all ethera lai Do the redults aeet tha needa of the cuatoaer. Thla deteralnatlon will be Bade jointly between the cuatoaer and the analyat. The aaalyat Boat axerclae caution In not allowing the cuatoaer to overatate. alalnterprat or unintentionally alerepretent the data. In addition to thla prlae quality criterion, the following condltlono auet be aet: a. (lanke - In tha event that a blank producer a poeltlve value. It aay not be uaed aa a valid blank If It axcaeda 10X of any reported value for a aaaple. b. tecoverlee - lecovcrlea for all aurrogate and native aplkea aunt lie In the range of SO!<Xecovery<l$OX. c. Praclelon - Praclalon will be calculated baaed on the recoveries of aurrogate Internal atandarda. Average recoverlea will be calculated with 1 atanderd deviation for each aaaple aet. lepllcate anelyaea and low and high native apike tecoverlee aay aleo be uaed to provide additional lnforaatlon/lnelght Into the praclalon of the analyala. HONS 02*00* 4. Halt of Detection - Th* limit of detection (LOO) will nornally ba stated as % th* value of tht low laval oatlv* spike if it la tocovorod and quantifloblo. Should th* low lv*l aatlw* splk* not b* recovered, th* LOO will b* *t*t*d a* *i th* wain of th* hl|h level native aplk* If It 1* recovered and quantifiable. Should neither aplk* b* recovered, a daclalon Boat b* aad* rsrdln( th* advisability of raprocaaalns th* aaapla. Should all aanplaa contain auch lere quantities of th* aaalyta(a) that th* level* of th* low and high aplk** *r* insignificant (<10t) bp conparlaon, th* valu* of th* LOD becowet 1*** inporcant and 1* alaplp Stated a* th* LOD for th* lnstriaantal analysis proc*** d*trnin*d by th* analysis of standard* and the ability to recover th* aurrosat* aplk**. a. Accuracy - Th* accuracy of th* analyaa* la baat datarnlnad by analyalas none aanpla which contain* th* analyta at sows pradatarnlnad level (a.f., an MIS atandardltad aanpla). If thl* type of atandard la not available than th* low laval and hlsh laval aplk** can b* uaad aa a nassura of tha accaracy of th* analyaa*. taaulta auat fall within a tans* of 7SZ to 1202 of th* axcaptad valua for th* analyaa* to ba conaldared valid. If th* abova quality criteria ar* not not th* analyat will lwedlataly aaaaa* th* naad for and extant of ranadlal action that nay b* nacaaaary. 2. kaaadlal Action Th* flrat court* of action will b* for th* analyst and/or group laadar to contact tha cuatoner and dlacuaa tba raaulta pointing out the llaltatlon* of tha data Indicated by th* quality control raaulta. At thla point th* overtIdlnt quality crlttrlon of cuatonar needs will b* addressed first. It could b* that tha euatonar's needs ar* act without naatlns on* or nor* of tha other criteria. In such n caaa no ranadlal action is nacaaaary. It could also b* that th* cnatoaar has such a danand for cl|htn*aa In th* result* that hla naad* era not act even though th* other quality criteria ar*. Thl* would trigger further analyses with tl|htar quality control designed around th* result* obtained (a.g., replications of positives to batter establish praclaloo or splkas of aoo-d*t*ct*d aanpla* to batter establish th* Halt of detection). In consultation with th* cuatonar additional axparlnants will be designed Including th* appropriate quality control to ultlnataly provide tha result* of sufficient quality to neat tb* cuatonar'* naad*. IV. fist* This section deal* with tha subject of data and how they ar* obtained, recorded and reduced so as to ba usaabl* In a report and yat readily available for referral and Inspection. HONS 024003 4 The pit* will t> labeled wltb lo| nunbar <t aenpla login according to tlx procedure described in tbn CSC Section CLP Manual. Vh*n ItllwtTod to th* responsible tochnlcnl parson, th sanplaa any then rccolvo iddltlonol labeling as deened necestry. This additional labeling will be doewented In a laboratory logbook aad/or notebook. Tbeae logbooka and notebooka will ba uaed by the analyata to record all portleant work and roaulta obtained tram the sanplea. The laboratory notebooka will be filled out In accordance with Mootanto Unlfotn notebook Procedures. All raw data generated for a given project, which cannot be conveniently placed In the laboratory notebook (e.g., chronatograaa, conputer output, ate.), will be filed under none prescribed order (l.a., log nuober) In a central file under the aupervlaoo of the Project leader and/or QA Speciallet. Moat of the data generated by the Ultratrace Analyale Croup are conputer data etored on nagnetlc dlaca. In order to archive theae data the apedflc file none and dlec ntvbar eaaoclated with the analyala will be written down In the laboratory notabook and/or lnatrunent logbook. When th* dlac la cenpletely full of data an entire unedited dlac Inage or copy of th* file* on the dlac will be traneferred to nagnetlc tape. A logbook will be kept for recording the dlac ntaber, none and prafln aaeoclated with It, along with the aeeodated tape and file nunbar to which th* dlac uae tranafatrad. An exanple of auch a logbook la given In Figure 3. When th* data ar* traneferred a verification prograo 1* need to check all traneferred record* for correctneaa. When tape* ara filled (they typically held seven to ten dlac laagea) they should be stored In fireproof vault. All calculations of the result* of th* data will be apeelfled In the wethed used. These calculations will be entered la th* analysts laboratory notebook unless they ore conputer generated. In thla case, a copy of th* conputer output will he filed with th* raw data. Th* Project Leader will be responsible for cheeking th* correctneaa of the data. V. Sanple Plapoaal Sanplea will be disposed of In accordance with the Instruction* on th* Analyala laquast torn. Th* only exception to this would result when th* analyst* reveals a problan which requires sanple disposal In a wanner other than that originally specified. If th* Project leader notes fron the result* of th* analysis that a potentially toxic product was present In th* sanple* then th* sanple* will be disposed of In a nannar decned safe by th* Safety Departnent. Th* date of sanple disposal and the nanner should be noted on th* request torn stored with th* raw data conpletlng th* ehaln of custody of th* aanple. MONS 024004 10 (kUI-Orlvt toriM MU CM kllputlm) kw4 Cmm Hnod kt* Tm4 'WM -T* I (MU |) /*> 'Ai fcnft i> i p& itfu . ri-L- <5wv) . /3> fw) I I />/ -4r *jk *&> (&0 xattiiyZZ filZ' affe i>5 w* -Ak3 " (.At*) C/iiO IMH LiK tyi i*** oJ sn 3'n-o#HL or (**) cin ` -u-t> 2K. / - mw *s cwjy)<i - <v*o* C*>Wr) i. V/r* Gt>6tCr) GPW7) &*(*) >/`Y*/`0 S/n*l) 1 <jt>K>) ;v,% m y*in $T>7/0) //i (^i /N OKW) X/K3 il 5t>?/ ?/(*) os (ftfttsHvQ ISO (*!#) C /V/ ^A2<V) fyffc Hi- OMo>) /y> ft#**) (V/ //**) ?M j6K SM , 3/>yfc3 >$< ft#/ sfc <*2> S> i-3 5/l^ti Hailt* fyi/to tMi> GWM 6) n<s) dblA (t) <o3>*W(7> P73V) > C?/ /V? I'AfcS) -2> /*< f/W') /V7 /**<>?) /VI /ff (?**) /st> 0/) i* tWj 3trs>fiy*+VC &) /Si <At*)(he3 *7v?/b a q*ihs s~& U>tks JB iu>w 32 t/j-Vu O +*5 i< n/Hlti <SM3 Q/ (iil'/L- C*) W> v (3) rj>- U 62>7<. W 63,-p.lCA 6&1* <1) <f *- <**> i | /O //!* ^ J .T/n/b " oOK m I r i ft ncuu 3. bpl< of DIfiC/TfO Logbook Ml*HONS 024005 11