Document KJG8Ebv7jeXG6YjZa4o52zB7X

Jean B. Sweeney Vice President 3M Environmental, Health and Safety Operations 3M Center, Building 0 2 2 4 - 0 ^ w i)3 St. Paul, MN 55144-1000 651 737 3569 n Certified Mail March 10,2010 7 3>818-3 Document Processing Center EPA East - Room 6428 Attn: Section 8(e) Office of Pollution Prevention and Toxics, US EPA 1200 Pennsylvania Avenue NW Washington DC 20460-0001 N O C BI Re: TSCA 8(e) Substantial Risk Notice: Supplemental to Docket No. 8EHQ-0598-373; Sulfonate-based and Carboxylate-based Fluorochemicals - Cordova, IL well water sampling To whom it may concern, 3M is submitting this notice to supplement its previous submissions on sulfonyl-based and carboxylate-based fluorochemicals and more specifically, our September 5, 2006 submission on water samples taken from groundwater wells and from the water distribution system at the 3M plant site in Cordova, Illinois. The data contained in the 2006 submission and in this submission have been generated as part of an on-going site-related environmental assessment of fluorochemicals that 3M is performing for its 3M Cordova, Illinois manufacturing facility. As part of this effort, which is being done with the involvement and approval of the Illinois Environmental Protection Agency, 3M has recently received the enclosed well water data taken from various sites on and in the vicinity of the 3M pWlaenstt.waOyff(Csi-t2e)d, aCtaFIar(eC-li3m),itCedFIto(Cfi-v4e),caonmdmCeFrIci(aCl-w5)e.lls3,Mre'fseurrneddertostaansdRinivgerissttohnaet n(Con-el),of this water is used for drinking water purposes. Enclosed please find a map depicting the sampling locations, a data summary table, and a final analytical report (Interim Report #2-Analysis of 3M Cordova Groundwater Samples: December 2009; Analysis of Perfluorobutanoic Acid (PFBA), Perfluorooctanoic Acid (PFOA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Groundwater Using LC/MS/MS for the "3M Fluorochemical (FC) Assessment Work Plan for the 3M Cordova, ELFacility). While 3M does not believe that any of these data taken alone or cumulatively meet the "substantial risk" reporting threshold as defined by the EPA, we nevertheless recognize the on pgolaincigngwothrekseofrtehsuelUts.Sin. tEhPeA8(teo) adsoscekssetflausoaroscuhpepmleimcaelnetxtpoopsruerveiopuasthswubayms.isTsihoenrse.fore, we are C O N T A IN S N O C B I Page 1 o f2 P-2 If you have any questions or would like any additional information, please contact Deanna Luebker at (651) 737-1374 or diluebker@mmm.com. Sincerely, <s. Jean B. Sweeney Staff Vice President, 3M Environmental, Health and Safety Operations Enclosures (3) Page 2 of 2 T able 1 G ro u n d w a te r Sam ple R esu lts: M arch 2008 and D ecem ber 2009 3M -C ordova, IL P-3 W E LL ID Average Sam ple C oncentration (ng/m l, ppb) D ate Sam pled | pfba PLAN T AREA WELLS MW -1-88 Mar 2008 Dec 2009 17.5 158 MW -1-90 Mar 2008 Dec 2009 110 426 MW -2-90 Mar 2008 Dec 2009 53.1 56.9 MW -9-90R Mar 2008 Dec 2009 103 372 M W -1-93 Mar 2008 Dec 2009 22 10.7 M W -3-94 Mar 2008 Dec 2009 734 290 FIELD A R E A W ELLS (SLUDG E INCORPORATION AR E A) MW -1-79 Mar 2008 135 Dec 2009 240 MW -3-79 Mar 2008 Dec 2009 32 81.1 MW -4-79 Mar 2008 Dec 2009 1.22 8.35 MW -5-79 Mar 2008 Dec 2009 0.4 <2.5 M W -2-81 Mar 2008 Dec 2009 2.34 6.04 M W -3-81 Mar 2008 Dec 2009 41.3 48.7 M W -4-81 Mar 2008 Dec 2009 145 155 M W -5-81 Mar 2008 Dec 2009 0.135 0.0891 M W -7-94 Mar 2008 Dec 2009 53.7 63.4 M W -8-94 Mar 2008 Dec 2009 98.4 67.6 M W -9-94 Mar 2008 Dec 2009 14.8 63.5 F orm er A q. W ell (#22580) Dec 2009 5.11 PRODUCTION W ELLS PW -11 Mar 2008 Dec 2009 2.22 2.09 PW -12 Mar 2008 Dec 2009 3.89 4.41 PW -13 Mar 2008 Dec 2009 60.9 57.4 PFOA 0.519 5.85 0.369 5.38 2.36 4.5 1.7 6.09 0.709 0.497 7.61 6.66 6.6 21 2.17 4.1 0.032 0.123 < 0.0298 0.0865 < 0.0298 0.0344 3.56 5.19 12.1 6.26 < 0.0298 <0.0303 2.45 7.23 4 12.2 0.0986 4.8 <0.0303 0.0656 0.118 0.5 1.38 4.16 7.93 PFBS NR 124 5.35 95.8 0.937 7.54 2.87 76.1 0.47 0.217 120 238 2.5 2.57 0.756 19.8 0.025 0.0533 <0.0249 0.0267 0.26 0.87 0.189 0.357 0.829 7.73 <0.0249 <0.0255 0.821 1.9 1.05 1.04 0.199 0.894 0.0604 <0.0249 <0.0255 <0.0249 0.0387 1.82 1.63 PFHS 0.63 6.04 0.628 6.79 2.29 6.5 2.47 4.82 3.78 1.6 11.4 8.97 9.72 14.3 3.95 7.55 0.0339 0.046 <0.0244 <0.0250 <0.0293 <0.0250 4.32 5.4 11.6 6.99 <0.0244 <0.0250 4.98 7.68 NR 15.3 0.763 6.91 <0.0250 0.094 0.111 0.53 1.23 4.84 6.46 PFOS 0.142 41.8 1.25 37 4.46 5.91 27.2 107 4.52 5.75 51.8 76.2 22.2 24.4 3.22 16.9 0.0786 0.174 < 0.0250 0.0548 < 0.0250 0.0538 5.94 7.54 13.7 21.5 < 0.0250 <0.0253 11 20.8 1.34 1.27 0.0878 1.93 <0.0253 0.266 0.278 2.91 11.3 11.4 14.8 L\FOLDERS.O-9\3M-Cordova\FC Assessmenfl2009 Samphng\2010 Sam pling ReportNTabte 1 2009-12-GW Results T able 1 G ro u n d w a te r S am ple R e su lts: M arch 2008 and D ecem ber 2009 3M -C ordova, IL W E LL ID PW -24 PW -37 COM M ERCIAL W ELLS R ive rsto n e (C-1) W estw ay (C-2) CFI (C-3) CFI (C-4) CFI (C-5) D ate S am pled Mar 2008 Dec 2009 Mar 2008 Dec 2009 Dec 2009 Dec 2009 Dec 2009 Dec 2009 Dec 2009 PFBA 2.61 1.45 1.39 1.39 0.788 4.51 0.0767 0.211 0.541 NR - Not reported due to quality control failure. Average Sam ple C oncentration (ng/m l, ppb) PFOA 0.455 0.347 0.449 0.342 PFBS <0.0249 <0.0255 <0.0249 <0.0255 PFHS 0.445 0.408 0.283 0.401 <0.0303 <0.0303 <0.0303 0.0937 0.0357 <0.0255 0.145 <0.0255 <0.0255 <0.0255 <0.0250 <0.0250 <0.0250 <0.0250 <0.0250 P-4 PFOS 3.49 0.727 0.383 0.698 <0.0253 <0.0253 <0.0253 0.0413 <0.0253 L.\FOLDERS.O-9\3M-Cordova\FC Assessment\2009 Samplmg\20t0 Sampling ReportVTable 1 2009-12-GW Results Legend * M o n ito r W ells P ro d u ctio n W e lls O ff-S ite W ells S ite B o u n d a ry N SV 0 1,000 2,000 Feet Figure 5 Groundwater Sampling Locations 3M Cordova Facility Cordova, IL CONFIDENTIAL p.6 Interim Report #2-Analvate of 3M Cordova Groundwater Samples: December 2009 Study Title Analysis o f Perfluorobutanoic Acid (PFBA), Perfluorooctanoic Acid (PFOA), Perfluorobutanesulfonate (PFBS), PsrfluorohexanesuHbnate (PFHS), and Peifluorooctanesuifonate (PFOS) in Groundwater Using LC/MS/MS for the "3M Fluorochemical (FC) Assessment Work Plan for the 3M Cordova, IL Facility Data Requirement EPA TSCA Good Laboratory Practice Standards 40 CFR Part 792 Study Director Jaisim ha Kesari P.E., DEE W eston Solutions, Inc. 1400 W eston Way W est Chester, PA 19380 P hone: 610-701-3701 Author Susan W olf 3M Environm ental Laboratory Report Completion Date Date o f signing Performing Laboratory 3M Environmental Health and Safety Operations Environmental Laboratory 3M Center, Bldg 26O0S-N-17 Maplewood, MN 55144 Project Identification E07-0149 Total Number of Pages 145 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2008 P a g e l o f 145 CONFIDENTIAL This page has been reserved for specific country requirements. p .7 E07-0149; Interim Report #2 3M Cordova Groundwater December 2009 Page 2 of 145 CONFIDENTIAL p .8 GLP C o m p l ia n c e S ta te m e n t Report Title: Interim Report #2 Analysis of 3M Cordova Groundwater Samples: December 2009 Study Tide: Analysis of Perfluorobutanoic Add (PFBA), Perfluorooctanoic Add (PFOA), Perfluonobutanesulforete (PFBS), Perfluorohexanesuffonate (PFHS), and Perfluoroodanesulfonate (PFOS) in Groundwater Using LC/MS/MS for the "3M Fluorochemical (FC) Assessment Work Plan for the 3M Cordova, IL Fadlity". This analytical phase was conducted in compliance with Toxic Substances Control Act (TSCA) Good Laboratory Practice (GLP) Standards, 40 CFR 792. Jaisimha Kesari, P.E., DEE, Study Director Date E07-0149; Interim Report #2 3M Cordova G roundwater* December 2009 Page 3 of 145 CONFIDENTIAL P-9 Q u a l it y A s s u r a n c e S ta t e m e n t R epot Title: Interim Report #2 Analysis o f 3M Cordova Groundwater Samples: December 2009 Study Tide: Analysis o f Perfluorobutanoic Add (PFBA), Perlluorooctanoic Add (PFOA), Perfluorobutenesulfbnate (PFBS), PerfluorohexanesuHbnate (PFHS), and Perfluorooctanesulfbnate (PFOS) in Groundwater Using LC/MS/MS for the *3M Fluorochemical (FC) Assessment Work Plan for the 3M Cordova, IL Facility". This analytical phase was audited by the 3M Environmental Laboratory Qualify Assurance Unit (QAU), as indicated in the following table. The findings were reported to the principal investigator (P.I.), laboratory management and study director. Inspection Dales Phase 1/22/2010,1/25/2010, and 1/28/2010 Data and Report Principal Investigator 1/28/2010 Oats Reported to Testing Facility Mansgantent 2/01/2010 Study Director 2/01/2010 Q - 3 '^ o / h 07-0140; Interim Report #2 3M Cordova Groundwater December 2000 Page 4 of 145 CONFIDENTIAL p. 10 Ta b le of C o n ten ts GLP Compliance Statem ent'...................... ....... ............ ....... .............................. ....... .............. 3 Quality Assurance Statement.......................................... ......................... :.......................... ............... 4 Table o f C ontents................ ................................................................................. ........... ....................5 List o f Tables...................!....... !...... :........................ '............................................................................ 6 1 Study Information............................................................................................................................. 8 2 Summary......... .................. 9 3 Introduction............... ......,.............................................................................................................. 9 4 Test & Control Substances.... ................. ............. ,................................................................ 10 5 Reference Substances..................................................................................................................10 6 Test System ........................................................................... 11 7 Method Sum mary.......................................................................................................................... 11 7.1 M ethods.........................................................................................................................11 7.2 Sample Collection.......................................................................................................... 11 7.3 Sample Preparation....................................................................................................... 11 7.4 Analysis..........................................................................................................................12 8 Analytical R esults.......................................................................................................................... 13 8.1 Calibration...................................................................................................................... 13 8.2 System S uitability.......................................................................................................... 14 8.3 Limit o f Quantitation (LOQ)............................................................................................14 8.4 Continuing Calibration................................................................................................... 14 8.5 Blanks.............................................................................................................................15 8.6 Lab Control Spikes (LC Ss)........................................................................................... 15 8.7 Analytical Method Uncertainty............................ 20 8.8 Sample Results..............................................................................................................20 E07-0149; Interim Report #2 3M Cordova Groundwater December 2006 Page5of 145 CONFIDENTIAL 8.9 Field Matrix Spikes (FMS)........................ 9 Data Summary and Discussion................ ,,.............. 10 Conclusion............................................................... 11 Data/Sample Retention............................................ 12 Attachm ents............................................................. 13 Signatures................................................................ L is t o f Ta b l e s Sample Description Key Code......................................... Table 1. Instrument Parameters..................................... Table 2. Liquid Chromatography Conditions................. Table 3. Mass Transitions.............................................. Table 4. Limit o f Quantitation (LOQ)....................... ..... Tables. Laboratory Control Spike Recovery....... ..... Table 5 continued. Laboratory Control Spike Recovery. Table 5 continued. Laboratory Control Spike Recovery. Tables. Analytical Method Uncertainty......................... Table 7. Sample Concentrations................... .......... Table 8. Field Matrix Spike Concentrations............. ..... Table 9. Lab Matrix Spike Concentrations................ Table 10. COIL-GW-MW-1-88 (Plant Area W ell)..... Table 11. COIL-GW-MW-1-90 (Plant Area W ell)..... Table 12. COIL-GW-MW-2-90 (Plant Area Wall) ........... Table 13. COIL-GW-MW-9-90R (Plant Area W ail)........ Table 14. COIL-GW-MW-1-93 (P la it Area W ell).......... Table 15. COIL-GW-MW-3-94 (Plant Area W ell).......... Table 16. COIL-GW-MW-1-79 (Field W ell)................... E07-0149; Interim Report 2 3M Cordova Groundwater - December 2000 ..22 ..27 ..5 8 .58 ..58 59 11 12 12 13 14 17 .19 .20 .20 .21 .27 .28 .29 .30 .31 .32 .33 .34 .35 Page 6 of CONFIDENTIAL p. 12 Table 17. COIL-GW-MW 3-79 (Field W ell)....................................................................................... 36 Table 18. COIL-GWMW-4-79 (Field W ell)....................................................................................... 37 Table 19. COIL-G W M W 5-79 (Field W ell).......................................................................................38 Table 20. COIL-GW M W 2-81 (Field W ell)........................................................... ......................... 39 Table 21. COIL-GW-MW-3-81 (Field W ell)......................................................................... ..............40 Table 22. COIL-GW-MW4-81 (Field W ell)....................................................................................... 41 Table 23. COIL-GW-MW-5-81 (Field W ell).................... ................................................................ 42 Table 24. COIL-GW-MW7-94 (Field W ^ l)...................................................................... .................43 Table 25. COIL-G W M W 8-94 (Field W ell)......................................................................... ........ ..... 44 Table 26. COIL-GW-MW-9-94 (Field W ell)........................................ ............................................... 45 Table 27. COIL-GWMW2258Q (Field W ell).................................................................................... 46 Table 28. COIL-GW W ell 11 (Production W ell)..................................................................................47 Table 29. COIL-GW W ell 12 (Production W ell).................................................................................48 Table 30. COIL-GW-Well 13 (Production W ell)................. ...............................................................49 Table 31. COlL-GW W ell 24 (Production W ell)................. ............. ......................................... ....... 50 Table 32. COIL-GW-Well 37 (Production W ell).................................................................................51 Table 33. COIL-GW C1 (Commercial W ell)........................................... .......................................... 52 Table 34. COIL-GW C2 (Commercial W ell)..................................................................................... 53 Table 35. COIL-GW C3 (Commercial W ell)............................ ...................................................54 Table 36. COIL-GW C4 (Commercial W ell)..................................................................................... 55 Table 37. COIL-GW C5 (Commercial W ell).......................... ...........................................................56 Table 38. C O ILG W TR IP BLANK................................. .................................................................. 57 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 7 of 145 CONFIDENTIAL r i'1' irr-fq .< 'i ;,I Sponsor 3M Company Sponsor Representative Gary A. Hohenstein Environmental Manager, Special Projects, EHS Operations Bldg 224-5W-03 S t Paul, MN 55144-1000 Phone:(651)737-3570, aahohenstein@mmm.com Study Director Jaisimha Kesari, P.E., DEE Weston Solutions, Inc. West Chester, PA 19380 Phone:(610)701-3761 Fax:(610)701-7401 i.kesari@ westonsolutions.com Study Location Testing Facility 3M EHS Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55106 Study Personnel W illiam K. Reagen, Ph.D., Laboratory M anager. Susan Wolf. Principal Investigator. (stwoH@mmm.comt: phone (6511-733-9851 C liff Jacoby, Ph.D Technical Review Jonathan Steege; analyst Study Dates Study Initiation: 11 April 2007 Interim Analytical Initiation: 08 December 2009 Interim Analytical Completion: 14 January 2010 Interim Report Completion: Date o f Interim Report Signing Location of Archives A ll original raw data and the analytical report have been archived at the 3M Environmental Laboratory according to 40 CFR Part 792. The test substance and analytical reference standard reserve samples are archived at the 3M Environmental Laboratory according to 40 CFR Part 792 EQ7-0149; Interim Report *2 3M Cordova Groundwater - December 2009 Page 8 of 14S CONFIDENTIAL 'i 'i . J The 3M Environmental Laboratory received one hundred forty-seven samples including one set o f trip blanks from the 3M Cordova fe d ity from Wsston personnel on December 1-3,2009 along with their chains o f custody (3M C O C. #15119 -15131). Samples were prepared and analyzed for Perftuorobutanoate (PFBA), Perfluorooctanoate (PFOA), Perfluorobutane sulfonate (PFBS), Perfluorohexane sulfonate (PFHS) and Perfluorooctane sulfonate (PFOS) under 3M Environmental Laboratory project number E07-0149. The objective o f this study was to analyze collected groundwater samples from monitoring and production wells located at the 3M Cordova facility for the selected perfluorocarboxyiate and perfluorosutfbnate analytes. The 3M Environmental Laboratory prepared sample containers (250 mL polyethylene bottles) which were shipped to the 3M Cordova fa d ity prior to field sampling. Sample containers for each sampling location included a field sample, field sample duplicate, and three field matrix spike samples. Each empty container was marked with a "fill to here' Ine to produce a final sample volume o f 200 mL. Containers designated for field matrix spike samples were fortified with an appropriate matrix spike solution containing the analytes o f interest, prior to being sent to the field for sample collection. See section 8.9 o f the report for field matrix spike levels. Samples were prepared and analyzed according to the procedure defined in 3M Environmental Laboratory methods ETS-8-154.3, ` Determination o f Perfluorinated Adds, Alcohols, Amides, and Sulfonates in W ater by Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry' , ETS-3-110.1 "Method of Analysis for the Determination o f Perfluorinated Compounds in Water, Soil and Sediment by LC/MS/MS' , and ETS-8-044.0 "Determination o f Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection Analysis' . Table 7 summarizes the sample results using the analytical methods identified above. All results for quality control samples prepared and analyzed with the samples w ill be reported and discussed elsewhere in this report. ' ' v .<`T E07-0149; Interim Report *2 3M Cordova Groundwater - December 3009 Page 9 of 145 CONFIDENTIAL ?4v Tesi CpntmSubstances ;?V. There was no test substance or control substances fo r this analytical phase in the classic sense. The study was purely analytical in nature. All materials used for this study are listed below and were reference materials as described herein. Reference Subitane* Chemical Name Chemical Formula Identifier Source Expiration Dale Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFBA Perfluorobutanoate C3F7C 0 0 ` Add, CAS # 375-22-4 Sigma 04/1512017 Frozen 11921CH TCR07-0011 Liquid 98.1% PFOA Perfluoroodanoate C7F15COO Ammonium Salt, CAS # 335- 67-1 Oakwood 09/29/2012 Frozen 3440 TCR07-0041 White powder 99.5% PFBS Perfluorobutanesulfonate C4F9SO 3 Potassium Salt, CAS #29420-49-3 3M 01/10/2017 Frozen 101 TCR-121 White powder 96.7% Reference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description PFHS Perfluorohexanesulfonate CgFisSOj Sodium Salt, CAS #3871-99-6 Wellington 04/02/2013 , Frozen LPFHXSAM08 TCR08-0018 Crystalline 98% p ros Perfluorooctane sulfonate G8F17SO3 Potassium Salt, CAS #2795-39-3 Wellington , 10/1812013 Frozen LPFOSKBM06 TCR08-0001 Crystalline 98% ECF-PTOA Perfluoroodanoate CrFtsCOO' Ammonium Salt, CAS # 335-87-1 3M 02/27/2017 Frozen 332 TCR-123 White powder 95% ECF-PFOS Perfluorooctane sulfonate C aF ijS O Potassium Saft, CAS #2795-39-3 3M 12/14/2016 Frozen 171 TCR-896 White powder 86.4 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 10 of 145 CONFIDENTIAL The test system for this study is water samples from the 3M Cordova facility collected December 1-3, 2009 by Weston Solutions, Inc. personnel. Samples for this study are "real world" samples, not dosed with a specific lot of test substance. S am ple D e scrip tio n Key C ode. te in a Number 1 2 3 4 5 Strina Descriptor Q enerelSem pIlng Locador? Sample Type Waff Number S im p le Type , . Sem pUnaDete Example COM." C o n ia v i, Illin o is GW * G round Wafer Example: MW (m onitoring umo O aprim try te m p le D B s d u p tk ii* sample L S o fo fvsp A r* E B ^equipm entrin se bienk 091201 * Decem ber 1,2000 7.1 Methods Alt samples were prepared and analyzed initially by the procedure defined in method ETS-8-110.1 ` Method of Analysis for the Determination o f Perfluorinated Compounds in Water, Soil and Sediment by LC/MS/MS". Samples that could not be reported by ETS-8-110.1 were prepared and analyzed using ETS-8-154.3 ` Determination o f Perttuortnated Ackls;Alcohols, Amides, and Sulfonates In Water by Solid Phase Extractions w xl High Performance Liquid Chromatography/Mass Spectrom etry or ETS-8-044.0 "Determination o f Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection Analysis' . 7.2 Sam ple Collection Samples were collected In 250 mL NalgeneTM (high-density polyethylene) bottles prepared at the 3M Environmental Laboratory. Sample bottles were returned to the laboratory at ambient conditions on December 4,2009. Samples were stored refrigerated at foe laboratory after receipt A set of laboratory prepared Trip Blank and Trip Blank field matrix spikes were sent with each set of collection bottles 7.3 Sam ple Preparation 7.3.1 ETS-8-110.1 Samples were prepared by removing a 1 mL aliquot of foe well mixed sample and diluting it with 9 mL of methanol (dilution factor o f 10). 7.3.2 ETS-8-154.3 Samples with concentrations <1 ppb were prepared by ETS-8-154.3, along with calibration standards, method blanks, and associated quality control samples. Briefly, 40 mL o f sample were loaded onto a pre-conditioned Waters tC18 solid-phase extraction (SPE) cartridge (Sep-Pak, 1.0 g, 6 cc) using a vacuum manifold. The loaded SPE cartridges were then eluted with 5 mL o f methanol. This extraction procedure concentrates foe samples by a factor of eight. (Initial volume = 40 mL, fin d volume = 5 mL). E07-0149; Interim Report #2 3M Cordova Groundwater December 2009 Page 11 of 145 CONFIDENTIAL 7.3.3 ETS4-0444 Samples, along with calibration standards, method blanks, and associated quality control samples, wens prepared by removing an aliquot o f the well mixed sample and placing it in an autovial for analysis. 7.4 Analysis All samples and quality control samples were analyzed for the target analytes listed previously using high performance liquid chromatography/ tandem mass spectrometry (HPLC/MS/MS). Detailed instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the raw data hard copies placed in the finai data packet, and are briefly described below. Table 1. Instrument Parameters. Instrum ent Name A nalytical Mathod/Analysis Datafs) Uauid Chromatograph Guard column A nalytical colum n Inlaction Volume Mass Spectrom eter Ion Source Electrode P o la rity S oftw a re ETS Ginaer ETSS-110.1 - December 11,2009 and January 7.2010 ETS-8-154.3 - December 22.2009 and January 5.2010 Aoent1100 Priam RP (50 mm X 2.1 mm), 5 u Betas! C18 (100 mm X 2.1 mm). 5 u OuL Applied Bbsvstems API 5000 Turbo Spray Z-sorav Negative Analyst 1.45 ETS Jonas ETS-8-044.0 - January 14,2010 Aailent 1100 Betasil C18 (100 mm X 4.6 mm), 5 u Betasll C18 (100 mm X 4.8 mm), 5 u 100 uL Applied Biosvstertn API 5000 Turbo Sorav Z-sorav Neoabve Analyst 1.45 Table 2. Liquid Chromatography Conditions S tep Num ber 0 1 2 3 4 5 0 1 2 3 .4 5 T o ttiT im e (m in) 0 2.0 14.5 15.5 16.5 20.0 0 0.5 11.0 13.5 13.8 17.0 R ow Rata (pU m in) P ercentA (2m M em m onlum etetete) E TS ^-154J and ETS-t-110.1 300 90 300 90 300 10 300 10 300 90 300 0 ETS-3-044.0 1000 1000 1000 1000 1000 1000 97 .97 5.0 5.0 97 97 P e rce n ts (M ethanoi) 10 10 90 90 10 10 3.0 3.0 95 95 3.0 3.0 EQ7-O140; interimReport#2 3M Cordova Groundwater December 2009 Pane 12 of 145 CONFIDENTIAL T able 3. M ass T ra n sitio n s. A e te Mesa T ransition 0 1 /03 ffllffV--f-t-V-- 1 S to rc a n e PFBA 213/199 U n ta r 413/399 PFOA 413019 413/199 U n ta r *\ ' PFBS 29900 29909 L o tta r PFHS 39909 39900 U n ta r 40000 PFOS 49000 U n ta r 400/130 Note: The individual transitions were summed to produces to ta l Ion chromatogram* (TIC), which wee used for quantitation. Dwel Sme was 75 msec. 8.1 Calibration 8.1.1 ET3-8-110.1 Calibration standards were prepared by spiking known amounts of stock solutions containing the analytes of interest into 25 mL o f 90:10 methanol:reverse-osmosis (RO) purified laboratory water. Linear PFOS and PFOA reference standards were used for the stock solutions. A total of fourteen calibration standards ranging from 0.02 ng/mL to 100 ng/mL (nominal) were analyzed. A quadratic, 1/x weighted, calibration curve was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentration using the peak area counts and the resultant calibration curve confirmed aceuracyofeech curve point Each calibration standard included in the final calibration curve met the method calibration accuracy requirement o f 25% (10030% for the lowest curve point). Correlation coefficients (r) were greater than 0.995 for all 8.1.2 ETS-8-154.3 Samples were analyzed against an extracted surrogate-matrix matched external calibration curve prepared in reverse-osmosis (RO) purified laboratory water. Calibration standards were prepared by spiking known amounts of stock solutions Into 40 mL p p water and carried through the solid-phase extraction procedure. Each spiked water standard w asthen extracted in the same manner as the collected samples. A total of twelve spiked standards ranging from 0.025 ng/mL to 25 ng/mL (nominal) were prepared. A quadratic, 1/x weighted, calibration curve was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentration using the peak area counts and the resultant calibration curve confirmed accuracy o f each curve point Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements o f 10025% (10030% for the lowest curve point) were met. The correlation coefficient (r) was greater than 0.995 for all analytes. E07-0149; Interim Report i2 3M Cordova Groundwater - December 2009 Page 13 of 145 CONFIDENTIAL 8.1.3 ETS-8-044.0 Calibration standards were prepared by spiking known amounts of the stock solution containing the target analytes into a laboratory-prepared synthetic groundwater containing calcium and magnesium. A total of twelve spiked standards ranging from 0.025 ng/mL to 25 ng/mL (nominal) were analyzed. The 2.5,10, and 25 ng/mL curve points were disabled for PFBS to meet method criteria. A quadratic, 1/x weighted, calibration curve of the ratio of the standard peak area counts over the internal standard peak area counts was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentrations using the peak area ratios and the resultant calibration curve confirmed accuracy of each curve point. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 100*25% (10030% for the lowest curve point) were met for all analytes included in the calibration curve. The correlation coefficient (r) was greater than 0.995 for PFBS. 8.2 System Suitability Multiple injections o f a calibration standard were analyzed at the beginning o f foe analytical sequence to demonstrate overall system suitability. All compounds met foe acceptance criteria of less than or equal to 5% relative standard deviation (RSD) for peak area and less than or equal to 2% RSD for retention time. 8.3 Lim it o f Quantitation (LOQ) The LOQ for this analysis is the lowest non-zero calibration standard in the curve that meets linearity and accuracy requirements and for which the area counts are at least twice those o f foe appropriate blanks. The nominal LOQ for analytes by analysis date can be found m Table 4. Table 4. Limit of Quantitation (LOQ) Analysis Data 12/11/09 1/7/10 12/22/09 1/5/2010 1/14/10 N A * Not Applicable Analysis M etho d ETS-8-110.1 ETS-8-110.1 ETS-8-154.3 ETS-8-154,3 ETS-8-044.0 Sample Dilution Factor 10 10 1 1 1 8.4 Continuing Calibration LOQ (nolm LI PFBA PFOA PFBS PFHS 2.50 2.50 NA 0.0300 NA 0.505 NA 0.0303 NA NA 1.02 1.02 0.0255 NA 0.0255 0.400 NA 0.0250 NA NA PFOS 0.404 NA 0.0253 NA NA During the course o f each analytical sequence, continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and foe initial calibration curve were still in control. All CCVs met method criteria o f 100% * 25% with foe following exceptions: 12/11/09 analysis - Seventeen CCVs were analyzed during the course o f foe am. One CCV for PFBS bracketed reported sample sets COIL-GW-MW-3-94, COIL-GW-MW-1-79, COIL-GV\AMW-3-79 and COIL-GW-MW4-79, had a recovery o f 141%. 12/22/09 analysis - Eleven CCVs were analyzed during foe course o f foe run. One CCV for PFOA bracketed reported sample sets COIL-GW-C3 (LS and MS), COIL-GW-C4, COIL-GW-C5, Equipment Blanks, and Trip Blanks, had a recovery o f 72.4%. A method deviation has been included in the report. E07-0149; Interim Report 2 3M Cordova Groundwater December 2009 Page 14 or 145 CONFIDENTIAL 8.5 Blanks 8.5.1 ETS-8-110.1 Several solvent blanks o f 90:10 methanol:reverse osmosis purified water were analyzed throughout the analytical sequence and were used to evaluate method performance and to determine the LOQ for each analyte. Fietd/trlfi blanks were also prepared and analyzed with the samples. 8A2 ETS-8-164.3 Three types o f blanks were prepared and analysed with tie samples: method blanks, equipment blanks, and fieldftrip blanks. Each blank result is reviewed and used to evaluate method performance to determine the LOQ for each analyte ' :"r ' r' V 8.5.3 ETS-8-044.0 Two types o f blanks were prepared and analyzed with foe samples: solvent blanks and fieldArip blanks. Solvent blank results were reviewed according to the method and used to evaluate method performance to determine the LOQ for each analyte. <^ 8.6 Lab Control Spikes (LCSs) 8.0.1 ETS-8*110*1 Lab control spikes were prepared in duplicate at two concentration levels (nominal concentrations of 5.0 ng/mL and 50 ng/mL. As the reference materials used for quantitation of PFOA and PFOS are predominantly linear, and the analytes present In the water samples were expected to be comprised of branched isomers, LCS samples of both inear and branched PFOA and PFOS were prepared in triplicate, at two concentrations to evaluate the potential for analytical bias. Method ETS-8-110.1 does not specify the number of required LCS or foe acceptance criteria, however, typical acceptance criteria for LCS is an average recovery within 100% 1 20%, with a RSD 520%. All LCS results met these criteria. , ft&2 E I3 4 -1 M 3 . ,t i l' , Low and high lab control spikes were prepared and analyzed in triplicate. LCSs were prepared by spiring known amounts o f the analytes info 40 mL of,reverse osmosis purified laboratory water to produce the desired concentration. The spiked water samples were then extracted and analyzed in foe same manner as foe samples. Analysis o f triplicate LCSs at the two specified levels cross-validates foe analytical method as used here for any modificatlons/deviations from ETS 8-154.3. The method acceptance criteria states that the average recovery of all LCS be between S0%-120% with a RSD s20%. All LCS samples met method acceptance criteria with the exception PFBA which had an average recovery of 126%. All LCS w ereused in the determination o f analytical uncertainty. A method deviation is filed with foe raw date. As foe reference materials used for quantitation of PFOA and PFOS are predominantly linear, and foe analytes present in foe water samples are 'comprised of branched isomers, LCS samples of branched PFOA and PFOS were prepared In triplicate, at two concentrations to evaluate foe potential for analytical bias. The average recovery for the branched PFOS was outside o f method acceptance criteria with an average recovery o f 126%. A method deviation is filed with foe raw data. E07-0149; Interim Report 2 3M Cordova Groundwater December 2009 Page 15 o f 145 CONFIDENTIAL 8.6.3 ETS-8-044.0 Low and high lab control spikes were prepared and analyzed in triplicate. LCSs were prepared by spiking known amounts of the analytes into laboratory-prepared synthetic groundwater containing calcium and magnesium, to produce the desired concentration. The spiked water samples were then prepared and analyzed in the same manner as the samples. Due to the higher curve being disabled to meet method acceptnace criteria, the high LCS at 5 ng/mL could not be calculated as the area counts for these samples exceeded the calibration range. The method acceptance criteria, average of all LCS should be within 100% 1 20% with an RSD s20%. The average recovery for the low set o f LCS met method acceptance criteria. The following calculations were used to generate data in Table 5 for laboratory control spikes. Calculated Concentration , LCS Percent Recovery Spike Concentration ^ LCS% RSD standard deviation LCS replicates . 1 average LCS recovery E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 16 oM 45 CONFIDENTIAL Table 5. Laboratory Control Spike Recovery ETS8-110.1 Analyzed 12/11/09 PFBA L in e a rPFQA PFBS PFHS Lab ID LCS-091202-1 LCS-091202-2 LCS-091202-3 LCS-091202-4 LCS-091202-5 LCS-091202-6 S p*red C alculated Spaced C alcolateci C oncentration Concentration Concentration C oncentration (n titn U (n a to li X fo c o w n r (no/m U fn * U 5.00 5.04 101 5.05 5.12 % R ecovery 101 S p *e d C alculated Spaced C alculated Concentiation C oncentration Concentration C oncentration fn g tin (ng *n Q XA acevery (n a tm (ngA rtL) K A k o w v 5.10 5.15 101 5.00 5.09 102 5.00 5.14 103 5.05 5.10 101 5.10 5.15 101 ' 5.00 5.12 102 5.00 5.15 103 5.05 5.14 102 5.10 5.10 99.9 5.00 5.13 103 50.0 SB.9 118 50.5 59.1 117 51.0 43.2 64.6 50.0 43.4 86.9 50.0 65.4 131 50.5 67.3 133 51.0 47.6 93.4 -50.0 46.5 93.0 50.0 66.5 133 50.5 675 134 51.0 48.3 94.7 50.0 47.3 94.6 Average 1 %RSD 113% 13% 115% 1 4 % 95.1% *.7 % 959% 3.7% ETS8-110.1 Analyzed 12/11/09 L in e a rp fO S L a tito LCS-091202-1 LCS-091202-2 LCS-091202-3 LCS-091202-4 LCS091202-5 LCS-091202-6 SpMmd C oncentration (n g tn U 5.05 C oncentration ( n g titij 5.09 5.05 5.05 5.15 5.11 50.5 43.0 50.5 47.2 50.5 47.7 Averaos% R SO 98.2% 1 3.5% XAacevery L a b B 101 LCS-091202-7 102 LCS-091202-8 101 LCS-091202-9 65.1 LCS-091202-10 93.5 LCS-091202-11 94.4 LCS091202-12 Averaoe %RSD BranctiedP FO A S ftik o tt C oncentration (n g tn L ) 5.00 5.00 5.00 50.0 500 500 CafcuArted C o n ce n frK fo n (ngA nL) 5.65 5.66 5.79 61.7 60.5 60.1 115% 3 .5 % X A e co ve ry 113 113 116 123 121 120 BranchedPFO S Spaced Concensation co n ce rm o o n (n o tn L f ( a m t 5.00 5.06 X A e co ve ry 101 5.00 5.00 5.15 5.11 103 102 50.0 55.1 110 50.0 54.6 109 50.0 54.4 109 108% 3Jt% NA - Not Applicable (1) The average recovery did not meet method acceptance criteria o l 100% 20%. (2) No peak was detected in tie sample. Sample was not used in the calculation o f average and RSD. (3) The area count for the sample was greater than the highest curve p o in t A true concentration could not be calculated. p. 22 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 17 o f 145 CONFIDENTIAL Table S continued. Laboratory Control Spike Recovery ETS-8-154.3 Analyzed 12/22/09 and 1/5/2010 PFBA Lab ID LCS-091215-1 LCS-091215-2 LCS-09121S3 LCS-091215-4 LCS091215-5 LCS-091215-6 S piked CM cenflrattM fn g h rfj 0.200 0200 0.200 500 500 500 fn ffh iy 0.223 0259 0296 6.39 6.13 723 Averane %RSO 126 % 9 J X m Lin e a rPFOA PFBS PFHS S piked C alculated C oncentration C oncentration (ng fa iL ) (npA nD % R ecovery S piked fh g ta U 111 0.202 0.215 107 0.204 129 0.202 0208 103 0204 118 0.202 0213 105 0.204 128 5.05 6.11 121 5.10 123 5.05 6.10 121 5,10 145 5.05 6.14 122 5.10 C elculatotd (ng fin L ) 0236 0231 0230 5.72 5.73 5.76 X R ecew nr 115 113 113 112 112 113 S piked 0.200 0200 0.200 5.00 5.00 5.00 C alculated (n a to li 0236 0235 0.227 5.62 5.61 5.59 % A ecovery 118 117 113 112 112 112 113% 8 .0 % 113% 1.0% 114% 2 4 % ETS-8-154.3 Analyzed 12/22/09 U nearPFO S Lab ID LCS-091215-1 LCS-091215-2 LCS-091215-3 LCS-091215-4 LCS-091215-5 LCS-091215-6 S piked C oncentration (n g M i 0.202 0.202 0.202 5.05 5.05 5.05 C alculated Concm ftm Oon (n g to tl) 0226 0218 0222 5.77 5.74 5.78 % R ccovery L a b 112 LCS-091215-7 108 LCS-091215-8 110 LCS-091215-9 114 LCS-091215-10 114 LCS-091215-11 114 LCS-091215-12 Avsraoe %RSD 112% 2.3% A ve rn e %RSD Branched PFOA S piked C oncentration (n g to L } C alculated Conceria aflon (n o m i 0200 0.200 0200 5.00 5.00 5.00 0255 0251 0250 5.89 5.56 5.62 120% 6 .0 % % R ecovery 127 126 125 118 111 112 B ranched PFOS Spced C alculated C ontentadon C oncentration (nnfm U (n a to li %Recovery 0.200 0200 0.200 5.00 5.00 5.00 0251 0.243 0249 6.51 627 6.35 125 122 125 130 125 127 126% Z1% m NA = NotAppfcabte (1) The average recovery did not meel method acceptance criteria of 100% *20% . (2) No peak was detected In the sample. Sample was not used in the calculation o f average and RSD. (3) The area count for the sample was greater than the highest curve point. A true concentration could not be calculated. p. 23 E07-0149; Interim Report *2 3M Cordova Groundwater - December 2009 Page 18 of 145 CONFIDENTIAL Table 5 continued. Laboratory Control Spike Recovery ETS-8-110.1 Analyzed 1/7/2010 PFBA U naarP fO A PFBS PFHS Lab LCS-091228-1 LCS-091228-2 LCS-091228-3 LCS-091228-4 LCS-091228-5 LCS-091228-6 S piked C alculated S piked C alculated S piked C alculated S p ite d C alculated C oncentration C oncentration C oncentration C oncentration C oncentration C oncentration C oncentration C oncentration (ngAnL) (nuAnU K fte c o v ify (meInU (noAnU X R e co w iy (n g lM ) (noA n X A ecovety (noAnL} X flecovery 5.00 5.32 106 5.05 5.46 108 5.10 5.52 108 5.00 5.33 107 5.00 5.14 103 5.05 5.24 104 5.10 5.33 105 5.00 5.18 104 5.00 5.00 100 5.05 5.39 107 5.10 5.35 105 5.00 5.09 102 50.0 68.8 138 50.5 67.2 133 51.0 50.8 99.6 50.0 48.6 97.2 50.0 70.0 140 50.5 c 68.9 136 51.0 51.3 101 50.0 48.0 96.0 50.0 . 7 1 . 1 . _ . 14? : 50,5 68.9. 136 51,0 53.6 105 50.0 49.3 98.7 Averaot %RSD 122% 17 %m ; 121%13%n 104X 13.0% 101% 4.2% ETS-8-110.1 Analyzed 1/7/2010 UnearPFO S Lab LCS-091228-1 LCS-091228-2 LCS-091228-3 LCS-091228-4 LCS-091228-5 LCS-091228-6 S piked C oncentration (ngA nL) 5.05 5.05 5.05 50.5 50.5 50.5 C alculated C oncentration (n o k a U 5.45 5.36 5.31 49.5 50.7 5 1 .8 Average %RSD 103% 3.7% X fle c o iw y la b ID 108 LCS-091228-7 106 LCS-091228-8 . 105 LCS-091228-9 97.9 LCS-091228-10 100 LCS-091228-11 103 LCS-091228-12 Average %RSD B ranched PFOA S p ite d C oncentiatton (noA tiL) 5.00 5.00 5.00 50.0 50.0 50.0 C alculated C oncentration (n g to A i 8.33 6.03 6.11 63.5 62.4 NA 124% 2.2 %m -----B-r-V---K- M---O- *rOTCV3TaM X R e co vo ry 127 121 122 127 125 NA S p ite d CflfcuAritetf C oncentration C oncentration (n o M I fnoA nU 5.00 5.73 5.00 5.62 5.00 5.61 50.0 59.3 5o:o 59.2 50.0 NA % Recovery 115 112 112 119 118 NA 115% 2.0% N A -N o t Applicable (1) The average recovery did not meet method acceptance criteria of 100% 20%. (2) No peak was detected in the sample. Sample wasno* used in Vie calculation o f average and RSD. (3) The area count fo r the sample was greater ttian Ihe highest curve p o in t A true concentration could not be calculated. p. 24 E07-0149; Interim Report 2 3M Cordova Groundwater - December 2009 Page 19 o f 145 CONFIDENTIAL Table 5 continued. Laboratory Control Spike Recovery ETS-8-044.0 Analyzed 1/14/2010 LablO LCS-100113-1 LCS-100113-2 LCS-100113-3 LCS-100113-4 LCS-100113-5 LCS-100113-6 Averaae %RSO PFBS S piked CafcufMad Concentration Concentration (ngfm L) (ngfm L) 0.204 0.204 0.204 5.10 5.10 5.10 0.213 0.209 0.212 N A 13' N A(31 N A '31 103% 2.7% %Recovery 104 102 104 n a(3) n a<3) n a<3! NA = NotApplicable (1) The average recovery did not meet method acceptance criteria o f 100% 20% . (2) No peak was detected In the sample. Sample was not used In the calculation of average and RSD. (3) The area count for the sample was greater than the highest curve point. A true concentration could not be calculated. 8.7 Analytical Method Uncertainty The analytical uncertainty was determined based on historical QC data that is used to evaluate method accuracy and precision. The method uncertainty is calculated following ETS-12-012.2. The analytical uncertainty was determined by the statistical evaluation o f the recoveries for the individual analyte as determined for laboratory control samples. The standard deviation was calculated for the set of recovery results (in %). The expanded uncertainty is calculated by multiplying the standard deviation by a factor of 2, which correspond with a confidence level of 95%, A minimum o f twenty data points is needed to determine method uncertainty by tills method. Table 6. Analytical Method Uncertainty A n a lyte PFBA PFQA PFBS PFHS PFOS PFBA PFQA PFBS PFHS PFOS PFBS A nalytical Method ETS-8-110.1 ETS-8-110.1 ETS-8-110.1 ETS-8-110.1 ETS-8-110.1 ETS-6-154.3 ETS-8-154.3 ETS-8-154.3 ETS-8-154.3 ETS-8-154.3 ETS-8-044.0 Mean Recovery Standard Deviation m 1%) 103 + 15.3 Method Uncertainty (% + 31 117 +10.7 21 942 9.70 19 95.0 10.3 21 104 10.1 20 106 ` 118 V 15.1 1 2 .7 30 25 110 + 7.66 15 109 ; 7.12 14 117 102 , 20 102 11.4 23 8.8 Sample Results Table 7 summarizes the sample results using the analytical methods identified above. All results for quality control samples prepared and analyzed with the samples are reported in section 9 o f the report E07-0149; interim Report #2 3M Cordova Groundwater December 2009 Page 20 of 145 CONFIDENTIAL Table 7. Sample Concentrations Sample Concentration (npftnL) 3M U M 3ID Sample D escription PFBA PFOA PFBS PFHS p ro s P ro d u ctio n W ell E07-0149-118 COIL-GW-MW-1-88-0-091203 158 5.85 124 6.12 41.8 E07-0149-119 COIL-GW-MW-1-88-DB-091203 158 5.84 123 5.95 41.7 Averagr IBB*1' 6.85TM 124TM 6.04TM 41.8TM HRPD SampfWSamprt DupO cntt 0.0 0.17 0.81 2.8 0.24 E07-0149-123 COIL-GW-MW-1 -90-0-091202 420 : 5.26 92.2 6.56 35.6 E07-0149-124 COIL-GW-MW-1 -90-DB-091202 431 5.50 99.4 7.01 38.3 Averapr 426TM , ,, 6.38TM 98.8TM 6.79TM 37.0TM YcftPO Scm ph/Sam ph D u p ik a tt 2 .6 ! 4.6 7.6 6.9 7.3 E07-0149-128 E07-0149-129 C O IL-G W -M W -2-90-0-091202 CO IL-G W -M W -2-90-D B -091202 58.5 57.2 4 -51 4.49 7.81 7.27 - 6.47 6.53 5.80 6.01 E07-0149-133 E07-0149-134 Avwags w f? YtPPD Sam pW Sam pk D uplicate ' 1 J COIL-GW-MW-9-90R-0-091203 . 385 C O IL-G W -M W -9-90R -D B -091203 `` 9 Avaneg* 372n,a 4.60TM 0.44 5.79 ' 6.39 6 .0 9 '"- 7.64TM t:2 77.5. . 74.7 76.1TM 6.60TM 0.92 4.41 5.22 J2TM 5.91TM 3.9 117 96.4 1 0 7 "' YtRPO SampUYSample D uplicate 7.0 A 3.7 17 19 E07-0149-138 E07-0149-139 COIL-GW-MW-1 .-93-0-091202 j,'l \ COIL-GW-MW-1-93-DB-O91202 11.4 0.503 0,211 to.o 0.490 0.222 1.66 1.53 5.95 5.55 Average 10.7TM 0.497TM 0.217TM 1 .6 0 "' 5 .7 6 "' YoRPO Sam pW Stm pI* D upfkato 13 2-6 6.1 8.2 7.0 NA Not Applicable NC > Not Catenated; The sample and sample duplicate produced one result above the IO Q and one result below the LOQ.: The reported average concentration represents or^y the result above the LOQ. A true average was not calculated. (t) Reported sample concentrations w e s te rn method ETS-8-110.1, direct orvoolumn injection of a samples diluted 1:10 with methanol. Method ETS-8-110 is not Included On the 3M Environmental Laboratory's IS 0 17025 scope of aoeredtation. (2) Samples were extracted by solid-phase extraction using method EtS-8-154.3. ETS-8-154 is nduded on the 3M Environmental Laboratory's IS 0 17025 scope of accreditation. (3) Some sample resins may have adjusted analytical uncertainties due to teld matrix spike recoveries. See tables in section 9 ofthe report for additional sample comments. , (4) The retetive percent difference (RPD) did not meet mebtod acceptance criteria o f S20%. (5) Reported samples were from method ETSO-044.0, direct iryecBon analysis. ETS-8-044 Is Included on Ihe 3M Environmental Laboratory's IS 0 17025 scope o l accreditation. E07-0149; Interim Report 2 3M Cordova Groundwater December 2009 Page 21 of 145 CONFIDENTIAL Table 7 continued. Sample Concentrations Sample Concentration (ngfmL) 3M UM SID Sample Description P ro d u ctio n Waffs PFBA PFOA PFBS PFHS p ro s E07-0149-143 COIL-GW-MW-3-94-0-091203 E07-0149-144 COIL-GW-MW-3-94-DB-091203 293 6.80 241 9.17 78.0 288 8.51 234 8.77 74.4 Average 2 9 0 * 6 .6 6 * 238* 8 .9 7 * 7 6 .2 * %PPD Sem ple/Sem ple D uplicate 2.4 4.4 2.9 4.5 4.7 F ie ld W e ll* E07-0148-148 * COIL-GW-MW-1-7904)91202 240 20.5 1.80 13.7 23.7 E07-0149-149 COIL-GW- MW-1-79-D&091202 239 Average 240<W %RPD Sem ple/Sem ple DupHeett 0.42 21.4 2 1 .0 * 4.3 3.34 2 .6 7 * 80* 14.8 1 4 .3 * 7.7 25.1 24.4 6.7 =07-0149-153 COIL-GW-MW-3-79-0-091203 81.3 4.05 19.7 7.40. 18.9 E07-O149-154 COIL-GW- MW-3-79-DB-091203 80.0 4.15 19.9 7.70 16.9 E07-0149-158 Average 1 .1 yt RPD Sem ple/Sem ple D u p lke tt 0A9 COILGWAMW4-79-0-091203 6.97 4.10"* 2.4 0.123 1 9 .8 * 1.0 0.0532 7 .6 8 * 4.0 0.0445 1 6 .9 * 0.0 0.176 E07-0149-159 COIL-GW- MW-4-79-OB-091203 , . 9.72 0.123 0.0533 0.0474 0.172 Average *.s s m 0 .1 2 3 * 0 .0 63 3 * 0.0480* 0.174 %RPD Sem ple/Sem ple D u p lica tt 33 0.0 0.19 6.3 2.3 E07-O149-163 COIL-GW-MW5-79-0-091202 <2.50, 0.0865 0.0273 <0.0250 0.0533 E07-0149-184 COIL-GW MW5-79rDB-091202 <2.50 0.0865 0.0261 <0.0250 0.0562 Average < 2 ,60 * 0.0868* 0.0287' <0.0260 0.0548* %RPD Sem ple/Sem ple D uplicate NA 0.0 4.6 NA 6.3 NA * NotApplicable NC Not Calculated; The sample and sample duplicate produced one result above the LOQ and one result below the LOQ. The reported average concentration represents only the result above the LOQ. A true average was not calculated. (1) Reported sample concentrations were from method ETS-8-110.1. direct on-column Injection of a samples diluted 1:io with methanol. Method ETS-8-110 is not included on the 3M Environmental Laboratory's IS 0 17025 scope of accreditation. (2) Samples were extracted bysolkt-phase extraction using method ETS-8-154.3. ETS-8-154 is included on the 3M Environmental Laboratory's IS 0 17025scope o f accreditation. (3) Some sample results may have adjusted analytical uncertainties due to feld matrix spike recoveries. See tables in section 9 of the report for additional sample comments. (4) The relative percent difference (RPD) did not meet method acceptance criteria of S20%. (5) Reported samples were from method ETS-8-044.0, direct injection analysis. ETS-8-044 is included on the 3M Environmental Laboratory's IS 0 17025scope of accreditation. E07-Q149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 22 of 145 CONFIDENTIAL Table 7 continued. Sample Concentrations Sample Concentration (ng/mL) 3M U M SID Sample Description PFBA PFOA PFBS PFHS PFOS Fielof W ells E07-O149-168 COIL^WMW-2^81-0-091202 6.18 0.0344 0.891 <0.0250 0.0537 E07-0149-169 COIL-GW-MW-2-81-00091202 5.89 0.0343 0.849 <0.0250 0.0538 ,. Average $.04 f- %RPD Sam pt&Srnnple D u p tica ti 4.8 '0:0344 0.29 0.870 <0.0280 0.0638 ;4J8 NA 0.19 E07-0149-173 COIL-GW-MW3-81-0-091202 49.3 5.63 0.352 5.70 7.95 E07-O149-174 COIL-GWMW-3-81 -DB-091202 43.1 A v rtg t 48.7 4 .7 4 ' 8.19 0.361 0.367 5.10 6.40 7.12 7.64 %RPD S tm pW S onph D v p lk ttt 2:6 17 2.8 11 11 E07-0149-178 COIL-GV\FMW4-81-0-091202r ' 155 6.30 7.78 7.08 22.0 E07-0149-17S COIL-GW-MW-4-81-DB-091202 155 i 6.21 7.67 6.89 21 ;o E07-0149-183 E07-0149-184 Averagt %RPO Sampfe'Sampfe D v p iic tte I 55*1' 0.0 CO IL-G W M W O -BI -0091201; 0.0791 COIL-GVV-MW-5-81-D &09120f 0.0991 e.26 1A <0.0303 <0.0303 7.73*1 1.4 <0.0255 <0.0255 6.99 2.7 <0.0250 <0.0250 2 1 .6 "' 4.7 <0.0253 <0.0253 ' Averaga 0.0891 I Y.RPD S m yivS w np th C H ip lica tt 22 <0.0303 <0.0288 <0.0280 NA NA NA <0.0283 NA E07-0149-188 C0IL-GW MW -7-94-0091202 | ' 63.4 ' 7.23 1.54 7.53 21.1 E07-O149-189 XHL-GW NIW -7-940&091202 83.4 7.22 2.26 7.83 20.4 Averag ` 63.4 7.23 1.90 7.68 20.8 - % /W SampfwSampfe Ouptfcatt 0.0 0.14 38 3.9 3.4 NA = Not Applicable . NC * Not Calculated; The sample and sample duplicate produced one result above the LOQ and one result below the LOQ. The reported average concentration represents only the result above the LOQ. A true average was not calculated. (1) Reported sample concentrations were from iheihod ETS-8-110.1, direct on-oolumnInjection of a samples diluted 1:10 with methanol. Method ETS-8-110 is not included on the 3M Environmental Laboratory's IS 0 17025 scope of accreditaton. (2) Reported samples were extracted by solid-phase extractloh using method ETS-8-154.3. ETS-8- 154 is Included on the 3M Environmental Laboratory's IS 0 17025 scope of accreditation. ' (3) Some sample results may have adjusted analytical unoertalntias due to field matrix spike recoveries. See tables in section 9 of the report for additional sample comments. (4) The relative percent difference (RPD) did hofm eet method acceptance criteria of S20%. (5) Reported samples were from method ETS-8O44.0, direct Infection analysis. ETS-8-044 Is included on the 3M Environmental Laboratory's IS 0 17025 scope of accreditation. E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 23 of 145 CONFIDENTIAL Table 7 continued. Sample Concentrations Sample Concentration (ngfmL) 3M U M 3ID Sample Description P fB A PFOA PFBS PFH8 PFOS F ie ld W elle 07-0149-193 COIL-GW-MW-&-94-0-091201 67.3 11.9 1.14 14.0 1.35 E07-0149-193 COIL-GW-MWS-94-DB-091201 67.9 12.5 0.937 18.6 1.18 Aveng 67.61'1 s 12.2 1.04 16.3 1.27 E07-0149-198 y.RPO Sam pla/Sam ph D uplicate 0.89 COII-GW-MW-9-94-O-O01201 64.3 : *> 4.98 , . 20 0.906 17 6.89 13 2.12 EQ7-0149-199 CQIL-GW-MW-9-94-DB-091201 62.7 4.81 0,882 6.92 1.74 A venge 63.6 4.80 0.894 6.91 1 .9 3 "' V.FPD Sem pta/Sam pto D uplicate 2.6 7.7 2.7 0.43 20 E07-G149-203 COIL-GW-MW-22580-0-091203 5.31 <0.0303 <0.0255 <0.0250 <0.0253 E07-0149-204 COIL-GW-MW-2258O-OB-091203 ; 4.91 <0.0303 0.0604 <0.0250 <0.0253 Averaga e . ii(" <0.0303 0.0604 <0.0260 <0.0263 %RPO Sam pW Sam ph D uplicete P ro d u ctio n W elle E07-0149-208 COIL-GW-PVW1-0-091201 7.8 1.97 N A NC NA 0.118 <0.0258 0.111 NA 0.288 E07-0149-209 COIL-GVWW-11-OB-091201 2.20 0.118 <0,0255 0.110 0.268 A venge 2.09 0.118 <0.0265 0.111 0.278 E07-0149-213 yiRPD Sm w M Sam pte D uplicate COiL-GW-PW-12-0-091201 11 4.68 0.0 NA 0.90 1.42 0.0404 1.23 7.2 11.5 E07-0149-214 COIL-GW-PW-12-DB-091201 4.13 1.33 0.0389 1.22 11.1 Avenge 4.41 1.38*" 0.0387**' 1.23 11.3 %RPD Sam pla/Sam ple D uplicate 12 6.6 0.1 0.82 3.6 NA " Not Applicable NC Not CakxMed; The sample and sample duplicate produced one result above the LOQ and one result below the LOQ. The reported average concentration represents only the result above the lO Q . A true average was not calculated. (1) Reported sample concenfadons were from method ETS-8-110.1., direct on-column in|ectton of a samples dUuted 1:10 with methanol. Method ETS-8-110 is not included on the 3M Environmental Laboratory's IS 0 17025 scope of accreditation. (2) Samples were extracted by sold-phase extraction using method ETS-8-154.3. ETS-8-154 is Included on the 3M Environmental Laboratory's IS 0 17025 scope of accreditation. (3) Some sample results may have adjusted analytical uncertainties due to Held matrix spike recoveries. See tables in section 9 of the report for additional sample comments. (4) The relative percent difference (RPD) did not meet method acceptance criteria of 20%. (5) Reported samples were from method ETS-8-Q44.Q, direct injection analysis. ETS-8-044 is included on the 3M Environmental Laboratory's IS 0 17025 scope of accreditation. E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 24 of 145 CONFIDENTIAL Table 7 continued. Sample Concentrations Sample Concentration (119111114 M U M 3 ID Semple D escription PFBA PFOA PFB9 PFHS p ro s P ro d u ctio n W alls E07-0149-218 CIL-GW-PW-13-0-091201 57.9 7.86 1.67 6.49 14.9 0)7-0149219 COIL-GW-PW-13-D9091201 56.9 7.99 1.59 6.43 14.7 Average 7,4 7.93 1.63 6.45 14.8 %PPO Samp/wSampfe D uplicata 1 8 4.9 0.93 1.4 E07-0149-223 COIL-GW-PW-24-0-091201 1.40 0.344 ' <0.0255 0.403 0.729 E07-0149-224 COIL-GW-PW-24-D9091201 1.50 . 0.350 <0.0255 0.412 0.725 Average 1.4 r 0.347 <0.0265 0.408 0.727 y.RRD SrnnpM Sam ple DupUcnH 6.9 1.7 NA 2.2 0.55 E07-0149-228 CdL-GW-PW-37-0-091201 1.41 0.342 <0.0255 0.403 0.709 E07-0149229 CCHLr<3Vm937-D9091201 1.3a 0.342 <0.0255 0.398 0.686 I' (Averagr 1.39. %RPO S m p& S am plB DupUcmO 3.6 C om m ercial W alla . .... E07-0149233 i COIL-GWC1-0-091203 L ;. 0.756 0.342 0.0 <0.0265 NA 0.401 1.2 <0.0303 <0.0255 <0.0260 0.898 3.3 <0.0253 E07-0149234 COIL-GWC1-D9091203 0,819 <0.0303 <0.0255 <0.0250 <0.0263 ; A vantgt 0.788^ <0.0303 <0.0255 <0.0250 <0.0283" %RPD Ssm pla/Sam pl D uplicate : r 8,0 ' NA NA NA NA E07-0149238 COIW3V^C2-9Q91203 " ' 4.32. <0.0303 0.144 <0.0250 <0.0263 E07-0149239 COIL-GW-C2-DB-091203 ' '4 69 <0.0303 0.145 <0.0250 <0.0253 Average '> .5 1 <0.0303 0.146 <0.0250 <0.0253 %RPO Sam pte/Sam pleD yptlcate ' 8.2 NA 0.69 NA NA NA = Not AppBcabte NC = Not Calculatecl; The sample and sample tkjp itcs^ produced orfe result above the LOQ and one result below the LOQ. The reported average concentration represents1only the ri^u lt atidve the LOQ. A true average was not calculated. (D Reported sample concentrations were frbrh rridthbdfet-8-11p.1f 'direct on-odlumn infection of a samples diluted 1:10 with methanol. Method ETS-8-110 is not ln c iu ^ (M #w 3M Enytrortmentafl Laboratory's IS 0 17025 scope of aocredftation. (2) Samples were extracted by sold-phase extraction using method ETS-6-154.3. ETS-8-154 is included on the 3M Environmental Laboratory's IS 0 17025 soope ofaocreditaVori!' (3) Some sample results may have adjusted analytical uncertainties due to #etd matrix spike recoveries. See tables in section 9 of the report for additional sample comments. (4) The relative percent difference (RPD) di(l not meet method acceptanoe criteria of S20%. (5) Reported samples were from method ETS-8-044.0, direct injection analysis. ETS-8-044 is included on the 3M Environmental Laboratory's IS 0 17025 scope of accreditation. E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 25 of 145 CONFIDENTIAL Table 7 continued. Sample Concentrations Sample Concentration (ngfm L) SM U M S ID Sample Description PFBA PFOA PFB8 | . PFHS PFOS C om m ercial W eils E07-0149-243 COIL-GWC3-0-091203 0.0758 <0.0303 <0.0255 <0.0250 <0.0253 E07-0149-244 COIL-GW-C3-D6-O91203 0.0775 <0.0303 <0.0255 <0.0260 <0.0253 Aveng 0.0767l,,, <0.0303 <0.0288 <0.0260 <0.0283 y,RPO Ssm ptafSsm ple D upllcsts 2.2 NA NA NA NA E07-0149-246 COIL-GW-C4-0-091203 0.213 0.0931 <0.0255 <0.0250 0.0420 E07-0149-249 COIL-GW04-D6-091203 0.209 Averags 8,211 0.0943 <0.0255 <0.0250 0.0937 <0.0288 <0.0250 0.0406 0.0413 %RPD Sam pleiSsm ple D uplicate 1.9 1.3 NA NA 3.4 E07-0149-253 COIL-GWC5-0-091203 0.543 0.0361 <0.0255 <0.0250 <0.0253 =07-0149-254 COIL-GW-C5-DB-091203 0.538 0.0353 <0.0255 , <0,0250 <0.0253 QAyerege 0.541 0.0387" ' <0.0258 <0.0280 <0.0253 %RPO Sam pW Sam ple D uplicate 0.93 2.2 NA NA NA NA = Not AppBcabte NC * Not Calculated; The sample and sample duplicate produced one result above the LOQ and one result below the LOQ. The reported average concentration represents only the result above the LOQ A true average was not calculated. (1) Reported sample concentrations were from nnethod ETS-8-110.1, direct ort-cdumn infection of a samples diluted 1:10 with methanol. Method ETS-8-110is not included on ttte 3M Environmental Laboratory's IS 0 17025 scope of accreditation. (2) Samples were extracted by soUd-phase extraction using method ETS-8-154.3. ETS-8-154 is Included on the 3M Environmental Laboratory* IS 0 17025 scope of accreditation. (3) Some sample results may have adjusted analytical uncertainties due to field matrix spike recoveries. See tables in section 9 of the report for additional sample comments. (4) The relative percent difference (RPD) did not meet method acceptance criteria of *20%. (5) Reported sampleswere from method ETS-8-0440, direct^njedion analysis. ETS-8-044 is included on the 3M Environmental Laboratory's IS 0 17025 scope ofacererfitation. E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 26 of 145 CONFIDENTIAL 8.9 Field M atrix Spikes (FMS) Low and high field matrix spikes were collected at each sampling point (with the exception of the rinse blanks) to verily that the analytical method is applicable to the collected matrix. Reid matrix spikes are generated by adding a measured volume of field sample to a container spiked by the laboratory with the target analytes prior to shipping sample containers for sample collection. Field matrix spike recoveries within method acceptance criteria o f 10030% confirm that `unknown' components in the sample matrix do not significantly interfere with the extraction and analysis o f the analytes o f interest Field matrix spikes are presentedin the section 9 of this report. FMS Recovery (SampleConcentration of FMS- Avtrage Concentration :Field Sample & Field Sample Dup.) Spike Concentraton .... lw7o Table 8. Field Matrix Spike Concentrations ' Location Description lx Final Concentration (ng/mL) PFBA, PFOA PFB8 PFHS PFOS MW-1-88, MW-1-93, and MW-3-79 Low Field Matrix Spike Mid Field Matrix Spike y. High Field Matrix Spike 1.00 0.997, ,0.999 1.00 0.999 10.0 9.97 9.99 10.0 . 9.99 50.0 49.9 50.0 50.0 50. MW-1-90, MW-2-90, MW-9- Low Field MatrixSpike 1 1.00 0.997 0.999 100 0.999 90R, MW-1-79, MW-3-81, MW-4-81, MW-7-94, MW-8- Mid Field Matrix Spike r~o 10.0 9.97 9.99 10.0 9.99 94. and PW-13 1- High Field Matrix Spke , 100 101 102 100 101 Low Field Matrix Spike ' ' 10.0 9.97 9.99 10.0 9.99 MW-3-94 Mid Field Mtiix Spike . 100 101 102 1 0 0 101 High Field MatrixSpka , 500 505 510 500 505 MW-4-79, MW-5-79. MW-2- Low Field Matrix Spike B1, MW-5-81, MW-9-94, MW22580l1,1PW-11, PW- Mid Field Matrix Spike 12, PW-24, PW37, and C1(1,-C5 High Field Matrix Spke 0.250 1.00 10.0 0.249 0.997 9.97 0.250 0.999 9.99 0.250 1.00 10.0 0.250 0.999 9.99 Low Field Matrix Spike 0.250 0.249 0.250 0.250 0.250 Trip Blank Mid Field Matrix Spike 10.0 9.97 9.99 10.0 9.99 High Field Matrix Spike 100 101 102 100 101 (1) Sample bottle E07-0149-0206 (CO tL-G m iW -22690-M S) was ovedUed by more then 10% (222 mL). Sample botte E0701494237 (CCXL-GW-C1-HS) was overfilled by more Pan 10% (225mL). The true value ofthese two spikes has been adjusted accordingly. 8.10 Laboratory M atrix Spike (LMS) The high field matrix spike concentration was not sufficient for sample location COIL-GW-MW-1-88 for PFBA and PFBS, for MW-1-90 for PFBA, for MW-9-90R for PFBA, for MW-1-79 for PFBA, and for MW9-94 for PFBA. Laboratory matrix spikes where prepared on the sample prior to analysis by ETS-8110.1. The preparation of a laboratory matrix spike was inadvertnetiy missed for location MW-9-94. A protocol deviation is included in the raw data package. LMS recoveries on this sample are presented on Table 9. Laboratory matrix spikes were prepared on the following samples: E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 27 of 145 CONFIDENTIAL Table 9. Lab M atrix Spike Concentrations. D e ecrtotfon COIL-GWWW-1-88; 100 ppb Lab Matrix Spike COIl-GWWW-1 -90; 500 ppb Lab Matrix Spike COIL-GW-MW-9-0OR; 50 ppb Lab Matrix Spike COIl-GW-MW-1 -79:250 cob Lab Matrix Soike NA * Not Applicable Sample ID E07-0149-118 E7-0149-123 074)149-133 E07-0149-148 Concentration (no/m U PFBA 100 250 500 250 O oncantiation (ng/m L} PFBS 102 NA NA NA LMS Recovery (IM S Sample Concentration-Average Concentration : Sample & Sample P u p .), 10Q% LMS Spike Concentraton The tables below summarize the sample results and field matrix spike recoveries tor the sampling locations as well as the Trip Blanks. Results and average values are rounded to three significant figures according to EPA rounding rules. Because o f rounding, values may vary slightly from those listed in the raw date. Field matrix spikes (FMS) recoveries meeting the method acceptance criteria o f 30%, demonstrate that the method(s) were appropriate for the given matrix and their respective quantitative ranges. In those instances where the most appropriate field matrix spike recoveries did not meet method acceptance criteria, analytical uncertainty has been adjusted accordingly and the date footnoted. COIL-GW-MW-9-90R: The high field matrix spike was not sufficient for PFBA, therefore, a lab matrix spike (LMS) at 500 ppb was prepared. The recovery of the LMS for PFBA was 148%. Since the LMS was the only appropriate spike level as compared to the sample concentration, the analytical uncertainty for PFBA has been adjusted to 100% 48% . ; COIL-GW-MW-1-79: The MS sample for PFHS had a recovery of 139%. The recovery o f the HS for PFHS was 90.8%. Since the MS was the most appropriate spjke level as compared to the sample concentration, the analytical uncertainty for PFHS has beenadjusted to 100% 39%. The high field matrix spike was not sufficient for PFBA, therefore, a lab matrix spike (LMS) at 250 ppb was prepared. The recovery o f the LMS for PFBA was 145%. Since the LMS was the only appropriate spike level as compared to the sample concentration, the analytical uncertainty for PFBA has been adjusted to 100% 45% . COIL43W-MW-3-79: The MS sample for PFOS had a recovery p f 69.1%. The recovery of the HS for PFOS was 79.7%. Since the MS was the most appropriate spike level as compared to the sample concentration, the analytical uncertainty for PFS has been adjusted to 100% 31%. COIL-GW-MW-4-81 : The MS sample for PFBS had a recovery o f 131%. The recovery of the HS for PFBS was 106%. Since the MS was the most appropriate spike level as compared to the sample concentration, the analytical uncertainty for PFBS has been adjusted to 100% 31%. COIL-C1 : The LS sample for PFOS had a recovery o f 66.9%. The recovery o f the MS and HS for PFOS was 80.2% and 85.4%, respectively. Since the LS was the most appropriate spike level as compared to the sample concentration, the analytical uncertainty for PFOS has been adjusted to 100% 33% . E07-014B; Interim Report #2 3M Cordova Groundwater - December 2009 Page 28 of 145 CONFIDENTIAL Table 10. COIL-GW-MW-1-88 (Plant Area W ell) JW U H S /D Description E07-0149-118 COIL-GW-MW-1-88-0-091203 E07-0149-119 E07-0149-120 E07-0149-121 COIL-GW-MW-1-88-DB-091203 C O IL-G W 4/W -1-88-LS-091203 COIL-GW-NMA1-88-MS-091203 E07-0149-122 CaL-(3W-MVV-1 -88-HS-091203 E07-0149-118; 100 DDb LMS CXHL-<3W-WMA1^84W91203 .^ Average Concentration (ng/m L) t %RPD PFBAm P FO /t1" C on cen tratio n C oncentration (no/m U Recovery (nofm U Reeo v e n / 158 NA 5.85 NA 158 NA 5 .8 4 NA NA NA 6.48 NC MA NA 15.3 94.8 MA NA 54.1 . 96.8 251 93.0 NA NA 158n&nLO 0i 5.85 n o M L 1 0.17% 3M U M S ID D escription E07-0149-118 CX1IL-GW-W/V-1-88-0-091203 E07-0149-119 COIL-GW-MW-1-88-DB-091203 B07-0149-120 COIL-GW-MW-1-88-LS-091203 E07-0149-121 COIL-GW-MW-1-88-MS-091203 E07-0149-122 COIL-GW-MW-1-88-HS-091203 E07-0149-118 100ppbLMS C O lL-G W -M W -1-880-091203 - Average Concentration (no/m L) %RPD PFBSn PFHSn ; pFOSm C on cen tratio n C on cen tratio n C o n cen tratio n (n g fo iQ Recovery (ng/m L) Recovery (ngtm L) Recovery 124 NA 6.12 NA 41.8 NA 123 NA 5.95 NA 41.7 NA NA NA 6.77 NC 41.1 NC NA NA 16.1 101 48.6 NC NA NA 57.4 103 87.2 91.0 228 102 NA NA NA NA 124 ng/m L 0.81% 6.04 na/m L Z8% 41.8 noftnL 0.24% N A * NotAppicatto N C * Not Catateted; Endogenous sample concentration is greaterthan 2x spice level. (1) Reported sample concentrations were from m etw dETS8-110.1,direct on-column infection ofasam plesdiuted 1:10v4th methanol Method ETS-8-110 is not included on the 3M Environmental Laboratory's IS 0 17025 scope ot accreditation. (2) Samples were reanalyzed on 1/7/10 with a LMS sample. TheLS. MS. and HS were not analyzed as the spike level was not appropriate as compared to the sample concentration. p. 34 E07-0149; Interim Report #2 3M Cordova Groundwater December 2009 Page 29 o f 145 CONFIDENTIAL Table 11. COIL-GW-MW-1-90 (Plant Area W ell) l j; MUMSID Description E07-0149-123 COtL-GW-MW-1-90-0-091202 E07-0149-124 COIL-GW-MW-1-90-DB-091202 E07-0149-125 COIL-GW-MW-1-90-LS-091202 E07-0149-126 CXJIL-GW-MW-1-90-MS-091202 E07-0149-127 COIL-GW-MW-1-90-HS-091202 E07-0149-123; COIL-GW-MW-1-90-0-091202 250 oob LMS PFBAm PFOAn Concentration (ngtoiL) %Recoverv Con(ncgetnmtrLa)tion %Recoverv 420* NA 5.26 NA 431 NA 5.50 NA NA NA 6.51 NC NA NA 14.8 94.5 NA . NA 104 97.6 722 119 NA NA 426nofmLZ6% S.3nofnA4.S% MIMSID Description E07-0149-123 E07-0149-124 E07-0149-125 E07-0149-126 E07-0149-127 COIL-GW-MW-1-90-0-091202 COIL-GW-MW-1-90-DB-091202 COIL-GW-MW-1-90-LS-091202 COIL-GV\FMW-1-90-MS-091202 COIL-GW-MW-1-90-HS-091202 E07-0149-123; 250 ppb LMS AverageConcentration(nofmL) %RPD PFBSn Concentration (ngAW X A ie o n iy 92.2 NA 99.4 NA 98.9 NC 109 NC 193 95.3 PFHSm PFOS0> Concentration (ngMJ %Recoverv Con(ncgefmntLraJtion ^Recovery 6 56 NA 35.6 NA 7 .0 f NA 38.3 NA 7.66 NC 38.9 NC 16.9 101 48.4 NC 105 98.2 127 89.2 NA NA NA NA NA NA 95.5 nofmL7.5% 6.79mj/mL6.6% 37,0nofmLt7.3% N A *N o t Applicable N C - NotCalculaled; Endogenous sample concentration is greater than 2x spike level. (1) Reported sampte concentrations were from method ETS-8-110.1,<#re<aon-column injection of a samples diuted 1:10 with roethanoL Method ETS-8-110 is not included on the 3M Environmental Laboratory's IS 0 17025 scope of accreditation. (2) Samples were re-anatyzed on 1/7/10 with a LMS sample. The LS, MS, and H Sw eie not analyzed as the spa levelwas not appropriate as compared to the sample concentration. p . 35 l 5 o E07-0149; Interim Report *2 3M Cordova Groundwater December 2009 Page 30 of 145 CONFIDENTIAL Table 12. COIL-GW -MW -2-90 (Plant Area W ell) ' PFBAm PFOA m 3M L M S ID D escription ` E07-0149-128 E07-0149-129 E07-0149-130 E07-0149-131 E07-049-132 COIL-GW-MW-2-90-0-091202 COIL-GW-MW-2-9G-OB091202 COIL-GW-MW-2-90-LS091202 COIL-GW-MW-2-90-MS091202 COIL-GVIAMW-2-90-HS091202 ~ Averaoe Concentration (notm U t %RPD C o n cen tratio n (ng/m U S6.5 57.2 56.1 65.0 151 % Recovery NA NA NC NC 94.2 C o n cen tratio n (ng/m L) % Recaveiy 4.51 NA 4.49 NA 5.62 NC 14.4 99.3 107 101 & .9n o > m L t1.2% 4.50 natm Lt 0.44% - . - -. - , 3ULMSID Description E07-0149-128 COIL-GW-MW-2-90-0-091202 _ E07-0149-129 COIL-GW-MW-2-90-DB091202 E07-0149-130 COIL-GW-MW-2-90-LS091202 E07-0149-131 CXDIL-GW-MW-2-90-MS091202 E07-0149-132 COIL-GW-MW-2-90-HS091202 AverageConcentration(ng/mL) %RPD : PFBSm PFHSm Concentration Concentration %Recovery (ngtotlj XRMowy ' 7.81 NA 6.47 NA 7.27 NA 6.53 NA 8.83 NC 7.67 NC 7.9 104 16.1 96.0 102 92.6 107 101 7.54n<JmL 7.2% 6.50ng/mLt0.92% f PFOSm (ngAnL) Xiwcow y 5.80 NA 6.01 NA 7.45 NC 149 90.0 91.2 84.5 5.91ngimLi3.6% | NA = NotApplicable NC = No!Calculated; Endogenous sample concentration greater than 2x spke level. (1) Reported sampte concentrations were from melhodETS-6-110.1, direct on-oolumniryection o fa samples diuled 1.10 with methanol. Mefrod ETS-8-110 is not included on frieSM Environmental Laboratory's IS 0 17025 scope of accreditation. p. 36 E07-0149; Interim Report *2 3M Cordova Groundwater - December 2009 Page 31 o f 145 CONFIDENTIAL Table 13. COIL-GW-MW-9-90R (Plant Area W ell) 3U L M S ID Description E07-0149-133 COIL-GW-WIW-9-90R-0-091203 E07-0149-134 CX5IL-GW-MW-9-90R-DB-091203 E07-0149-135 COIL-GW-MW-9-90R-LS-091203 E07-0149-136 COIL-GW-MW-9-90R-MS-091203 E07-G149-137 C O IL-G W M W -9-90R -H S -091203 E07-0149-133 COIL-GW-MW-9-90R-0-091203 500 ppb LMS Average Concentration (nofmL) i %RPD PFBAni PFOA (1 Concentration Concentration (ngtmL) %Recovery (ngfmL) %Recoverv 385 NA 5.79 NA 359 NA 6.39 NA na NA 6.95 NC NA NA 16.5 104 NA NA 100 93.0 1110 148 NA NA 372no/htU7.W f9 6.09 notmLt 93% 3MUMSID -. Description E07-0149-133 E07-O149-134 COIL-GW-MW-3-90R-0-091203 COIL-G W -M W -9-90R -D B -091203 E07-0149-135 EO7-0149-136 COIL-GW-M/V-9-90R-LS-091203 CCML-GWAAW-9-90R-MS-091203 E07-0149-137 COIL-GW4i4V\A9-90R-HS-091203 Average Concentration (no/mL) t %RPD PFBS(,> PFHS () PFOSm Concentration Concentration Concentration (ngfinL) %Recovery (nofatU %Recoverv (ngM .) %Recovery 77.5 NA 4.41 NA 117 - NA 74.7 NA 5 22 NA. 96,4 NA 74.8 NC 5.99 NC 100 NC 86.4 NC 16.3 .. 115 110 NC 174 96.0 95.7 90.9 199 91.4 76.1 ngtml3.7% 4.82 nq/m L 17% 107 mj/mL 19% NA = Not Appicable NC = Not Caldfated; Endogenous sample concentration greater than 2x spike level (1) Reported sample atncenfratioos were to m method ETS-6-110.1, diredon-colunwi Injection of a samples dialed 1:10 w ttu n e fta n o t Method ETS-&-110 is not included on the 3M Environmental Laboratory's IS 0 17025scope o l accreditation. (2) Samples were re-anjriyzed on 1/7/10 with a LMS sample. The LS.MS, and HS vrere not analyzed as the spite level was not appropriate as compared to the sample concentration. (3) The lab matrix spike did not meet method acceptance criteria oHOO % 30%. (4) The analytical uncertainly has been adjusted fairPFBA to 100% 48%. p. 37 07-0149; Interim Report #2 3M Condova Groundwater - December 2009 Page 32 o f 145 CONFIDENTIAL Table 14. COlL-GW-MW-1-93 (Plant Area W ell) 3M U M SID Description E07-0149-138 COIl-GW-MIAM-03-0-091202 E07-0149-139 CX)IL-GW-MW-1-93-DB-091202 E07-0149-140 CGIL-GW-MW-1-93-LS-091202 E07-0149-141 COIL-GW4A/V-1-93-MSO91202 E07-0149-142 CIL-(3W4^1,93+ISO91202 Average Concentration(na/mL)%RPD PFBA,X> PFOA Concentration Concentration (ngAnL) %Recovetv (rigtriU X A ecow y 11.4: NA 0.503 NA 10.0 NA 0.490 NA 11.4 NC 1.43 93.6 20.4 97.0 9.78 m 93.1 56.7 92.0 45.8 90.9 10.7jKtitnL 1 13% 0.497 n o tn L t 2.6% - " -J PFBS PFHS m t*FOSn 3M U M SID Description E07-0149-138 COIL-GWMW-1-934W91202 E07-0149-139 COIL-GW-MW-1-93-DB-091202 E07-0149-140 COIL-GW-MW-1-93-LS-091202 E07-0149-141 CC4L-GW-MW-1-93-MS-091202 E07-0149-142 COIL-GW44W-1-93+1S-091202 Average Concentration (ngfmU %RPD Conctihtntjon Concentration Concentration (noAnl) %Recovetv ' ("9*U %Recoverv ( * * & K A tc o iw y 0.211 9 X. \ !__0.222. NA-- 1 NA 1.66 .. - _ NA ... . _ . 5.95_ 1.53 NA .5,55 ..... NA . NA 1.39 1,17 2.41 81.5 6.28 NC 9.70 01 94.9 11.1 95.1 14.5 87.6 45.2 90.1 49.0 94.8 47.3 83.2 0.217 n g M -t 5.1% 1.00 ntf/mLt 8.2% 5.75 nq/mL 7.0% NA = NotApplicable NC * NotCalculated; Endogenous sample concentration greater than 2x spike towel (1) Reported sarrplecxirKXrtrations were fiom method ETS-tM 10.1, d ire d o rw x *jm injection o f a samples <*uted 1:10 w*h methanol Method ETS-8-110 is not indudod on tie 3M Environmental Laboratory's IS 0 17025 scope o f aocreritation. (2) Reported sample uxicenOations were from method ETS-8-154.3. sofcf-phase extraction. Method ETS-8-15* is included on the 3M Environmental Laboratory's ISO 17025 scope of accreditation. p. 38 E07-0149; Interim Report 2 3M Cordova Groundwater - December 2009 Page 33 o f 145 CONFIDENTIAL Table 15. COIL-GW-MW-3-94 (Plant Area Well) 3U LUIS ID D escription E07-0149-143 COIL-GW-MWG-94-0-091203 E07-0149-144 COIL-GW-MW-3-94-DB-091203 E07-0149-145 COIL-GVtf-MWG-94-LS-091203 E07-0149-146 E07-0149-147 CXML-GW-MW-3-94-MS-091203 COIL-GW-MW-3-94-HS-091203 Average Concentration (n o titi) i. %RPD PFBAm PFOA C oncentration Concentration (no/mL) YaRecoverv (n o titi) 293 NA 6.80 286 NA 6.51 296 NC 16.5 378 NC 102 725 87.1 448 %Recoverv NA NA 98.7 94.4 87.4 290 no/mL i 2.4% 6.66 no/mL4.4% 3MLUIS ID ^. D escription E07-0149-143 COIL-GW-MW-3-94-OO91203 E07-0149-144 QOIL-GW-MW-3-94-DB-091203 E07-0149-145 COIL-GV\AMW-3-94-LS-091203 E07-0149-146 COIL-GWLMW-3-84-MS-Q91203 E07-0149-147 COIL-GW-MW-3-94-HS-091203 Average Concentration (n o tili) %RPD PFBSm PFHS m p ro s TM C oncentration (no/mL) %Recoverv 241 NA 234 NA 240 NC C oncentration (no/m L) 9.17 8.77 18.9 C oncentration %Recoveiv (n a ta ti) %Retxwery NA 78.0 NA NA 74.4 NA 99.3 84.0 NC 314 NC 103 94.0 162 85.0 671 85.0 441 86.4 493 82.5 238 n o titi. 29% 8.97 no/mL 4.5% 76.2 n o titi. 1 4.7% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater tia n 2 x spike level (1) Reported sample conoentralions were from method ETS^110,1, direct orKxAjnininjecbon of a samples dtUed 1:10 wthmethanoL Method ETB-8-110 is not included on the 3M Environmental Laboratory's tS 0 17025 scope o f accreditation. p. 39 E07-0149; Interim Report 2 3M Cordova Groundwater - December 2009 Page 34 o f 145 CONFIDENTIAL Table 16. COIL-GW -MW -1-79 (Field W ell) PFBATM PFO A m 3M UM SU) Description C oncentration C oncentration (n o M J % Recovery (ngfatL) % R ecam y E07-0149-148 COIL-GW-MW-1-79-0-091202 240 NA 20.5 NA E07-0149-149 COIL-GW-MW-1-79-OB-091202 239 NA 2 1 .4 NA E07-0149-150 E07-0149-151 CXJIL-GW-MW-1-79-LS-091202 COIL-GW A1W -1-7 9-M S -091202 NA NA NA NA 20.3 28.8 NC 78.7 E07-0149-152 . QOIL-GWMW-1-79-HS-O91202 . $ I i E07-0149-148:250 ppbtM S NA 6Q1 . NA 145 117 NA 95.1 NA . Average Concentration (ng/rnL) % R PD ' 240n o/m l. 10A 2% n 21.0 notmL 4.3% '* ' N- -yP tB S m pm s* ; PFOS m 3M U M S ID A--' -' >. \ D escription E07-0149-148 COIL-GW-MW-1-79-0-0912Q2 E07-0149-149 COIL-GW-KAW-1-79-OB-091202 E07-0149-150 COIL-GW-MW-1-79-LS-091202 E07-0149-151 COIL-GW-MW-1-79-MS-091202 E07-0149-152 COIL-GW-MW-1-79-HS-091202 E07-0149-148; 250 ppb LMS COIL-GW-MW-1-79-0-091202 Average Concentration (no/m U %RPO C o n cen tratio n C oncentration . Concentration ::-y (ngtm L) % Recevery (ngtm Q ^R ecovery (n g *) 1.80 NA 13.7 NA 23.7 3.34 NA 14.8. NA 25.1 3.17 NC 16.8 NC 26.8 14.2 116 28.1 139 36.7 98.5 9 4 .0 105 90.8 109 NA NA NA NA NA %R ecovery NA NA NC 123 83.8 NA 2 .s rn g 4 n L W % m 1 4 .3 n q ftn L i 7.7% n 24AngM LSJ% NA NotApplcable NC = Not Calculated; Endogenous sample concentaSon Is greater than 2x spite level (1) Reported sample ooooeniraioTOwere ftram m effiodETS-S-llO .I.dined ofvcolum nirvectionofasam ptesdftitad LlOvviffirnelhanol. M eihodTS-8-110lsrtlnduttedonthe3M Environmental Laboratory's IS 0 17025 scope of accreditation. (2) Samples were re-analyzed on 1/7/10 with a LMS sample. The LS, MS, and HS were not analyzed as the spike level was not appropriate as compared to Ihe sample concentration. (3) The fiekttab matrix spike did not meet method acceptance criteria of 100% 30% . (4) The analytical uncertarty has been adjusted lor PFBA to 100 % 45% and forPFHS to 100 % 39%. (5) The relative percent difference (RPD) did not meet method acceptance criteria of 20% p. 40 E07-0149; Interim Report 2 3M Cordova Groundwater - December 2009 Page 35 of 145 CONFIDENTIAL Table 17. CCXL-GW-MW-3-79 (Field W ell) 3 M U U S ID D e s c rip tio n E07-0149-153 E07-0149-154 C XH L-G W -M W -3-7M -091203 COIL-G W -M W -3-79-DB-091203 E 0 7 -0 14 9 -1 5 5 E07-0149-156 E07-0149-157 C 0IL-G W -M W -3-79-LS-091203 CO IL-G W -M W -3-79-M S-091203 COIL-G W -M W -3-79-HS-091203 A ve ra g e C o n ce n tra tio n (n g fln U t % RPD P F B A a> PFOAm C o n c e n tra tio n C o n c e n tra tio n (n g /m L ) W fa co ve /y (n o /m U % R ecovery 8 1 .3 N A 4 .0 5 N A 8 0 .9 NA 4 ,1 5 NA 7 2 .7 NC 4 .3 6 NC 8 9 .4 NC 1 3 .0 8 9 .3 123 8 3 .8 5 2 .0 96.1 81.1 n g /m L 0.49% 4 .1 0 n o M L tZ 4 % 3 M U M S ID D e s c rip tio n E07-0149-153 E07-0149-154 C01L43W -M W -3-79-0-091203 COIL-G W -M W -3-79-DB-091203 E07-0149-155 COIL-G W -M W -3-79-LS-091203 E07-0149-156 E07-0149-157 C 0IL-G W -M W -3-79-M S 091203 C O IL-G W -M W -379-H S-091203 A ve ra g e C o n ce n tra tio n ( n o M J t % RPD PFBSm PFHS m PFOS Iti C o n c e n tra tio n C o n ce n tra tio n (n o fa n U % R e c w e n t (ng tm L ) % R ecoverv 1 9 .7 N A 7 .4 0 NA 19.9 N A 7.70 N A 172 2 8 .3 NC 85.1 7 .7 4 1 6 .5 NC 8 9 .5 6 3 .7 8 7 .9 5 7 .2 9 9 .3 19.8no/m L 1 1.0% 7.55 n o fa tL 4 .0 % C o n ce n tra tio n (n s tm j 1 6 .9 1 6 .9 1 4 .7 2 3 .8 5 6 .7 X R ecoverv NA NA NC 69.1 m 7 9 .7 1 6 S n a 4 n L 0 .0 % lv NA = Not Applicable NC= Not Calculated; Endogenous sample concentration is greater than 2x spike level (1) Reported sample concentrators were from method ETS-8-110.1. direct orw jokjm nirjecton o f a samples (fluted 1:10 with methanol. Method ET&6-110 is not included on tre 3M Environmental Laboratory's IS 0 17025 soope of accreditation. (2) The field matrix spike dki not meet method acceptance criteria of 100 % 30%. (3) The analytical uncertainty has been adjusted for PFOS to 100 % 31%. IV 'd E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 36 o f 145 CONFIDENTIAL Table 18. COIL-GW-MW-4-79 (Field W ell) 3 M U M S ID E07-0149-158 E07-0149-159 E07-0149-160 E07-0149-161 C O IL-G W -M W 4-79-0-091203 CXH L-G W -M W 4-79-DB-091203 C O IL-G W 44W 4-79-LS -091203 C O IL-G W -M W 4-79-M S -091203 E07-0149-162 C O IL-G W W W -4-79-H S-091203 A veram Concentration (no/m U tM R P D PFBA m P fO A C on cen tratio n C oncentration `A R eco very (*# *) 6 .9 7 NA 0 .1 2 3 % Raeoverv NA 9 .7 2 NA 0 .1 2 3 NA 8 .6 7 NC 0 .3 5 5 93.1 9 .7 4 NC 1 .0 6 94.0 1 8 .0 9 6 .6 1 0 .5 , 104 1 L 3 S n o fo lL t3 3 % a 0 .1 2 3 K M . *0 .0 % ' p f Ds PFHS PFOS 3M L M S ID ,, D escription <C on cen tratio n C oncentration C oncentration (ngtoiL) % Racoverv (n g M ) % Recovery inoAnU X R e c o m y E07-0149-158 E07-0149-159 E07-0149-160 E07-0149-161 E07-0149-162 COtL-GW-MW-4^79-0-091203 ^ r 0.8 5 3 ? , COIL-GW-MW-4-79 -0 B-091203 0.0533 .. COIL-GW-MW-4-79-LS-091203 0 .3 5 4 COIL-GW-MW-4-79-MS-091203 1 .2 8 C O IL-O W M W -4-79-H SO 91203 1 0 .7 NA. ". NA 120 123 107 0 .0 4 4 5 0 .0 4 7 4 0.331 1 .2 3 -1 0 .5 ' NA , NA 114 118 105 0 .1 7 6 6 .1 7 2 0.421 1 .2 6 9.45 NA NA 98.9 109 92.9 Average Concentration (no/m L) i %RPD 0.0S33 ng/m L 0.19% 0.0400 nofmL 6.3% 0.174 K tA n L *Z 3 % NA*NotAppicat>fe NC= Not Calculated; Endogenous sample concentration Is greater than 2 * spike level. (1) Reported sam pteaxxafriralons were from nrethod ETS-8-110.1,diredon-oolurnnirqec6on of a samples dHuted 1:10 with medianol. Method ETS-8-110 is no! included on the 3M Environmental Laboratory's IS 0 17025 scope of accreditation. (2) Reported sample concentrator were from method ETS-8-154.3, solid-phase extraction. Method ETS4M 54 is rrtu d e d on the 3M Environmental Laboratory's IS O 17025 scope of accredtation. (3) The relative percent difference (RPD) (fid not meet method acceptance criteria of 20% . p. 42 E07-O149; Interim Report *2 3M Cordova Groundwater - December 2009 Page 37 of 145 CONFIDENTIAL Table 19. COIL-GW-MW-5-79 (Field W ell) M U M S ID D e s c rip tio n E07-0149-163 C O IL-G W -M W -5-79-M 91202 E07-0149-164 C01L-G W -M W -5-79-DB-091202 E07-0149-165 CO IL-G W -M W -5-79-LS-091202 E07-O149-166 CO IL-G W -M W -5-79-M S-091202 E07-0149-167 CO IL-G W -M W -5-79-HS-091202 A ve ra g e C o n c e n tra tio n (n g /m L ) % R PD PFB A ft) PFOAm C o n c e n tra tio n C o n c e n tra tio n (n g /m L ) `/ R eco ve ry (n g /m L ) < 2.50 NA 0 .0865 < 2.50 NA 0 .0865 < 2.50 NC 0 .3 14 < 2.50 NC 1.01 10.8 108 9 .8 5 % R ocoverv NA NA 9 1 .3 9 2 .6 9 7 .9 < 2.50 n g /m L 0.0865 n a /m L 0.0% 3 M U M S ID D e s c rip tio n E G 7-0149-163 E 0 7 -0 14 9 -1 6 4 E07-0149-165 E07-0149-166 E07-0149-167 COIL-GVV-MW -5-79-CK1202 COIL-GW -M VV-5-79-DB-091202 CO IL-G W -M W -5-79-LS-091202 C O IL-G W -M W 6-79-M S -091202 CO IL-G W -M W -5-79-H S-091202 A ve ra g e C o n c e n tra tio n (n g /m U t % RPD PFBS m PFHS m PROS m C o n c e n tra tio n C o n c e n tra tio n C o n ce n tra tio n (n g fa L ) % R ecovery (ng /m L ) X R ecovery (n o /tn U % R ecovery 0 .0 27 3 N A < 0.0250 NA 0 .0 53 3 NA 0.0261 NA <0.0250 N A 0 .0562 NA 0 .340 125 0 .2 96 118 0 .2 8 5 9 2 .2 1.20 . 117 1 .1 6 116 1 .1 0 . 105 - 9 .9 5 9 9 .3 10.3 103 8 .9 0 8 8 .5 0.02S 7 n g /m L 1 4.5% <0.0250 n g fin L 0j0548 n q /n tL L S .3 % N A= Not Applicable (1) R e p o rt sampiocorxsentrations were to rn rnetfiodETS-8-110.1, direct on-cofcimn injection ot a samples cButed 1:10 with methanol Method ETS-8-110 is not included on the 3M Environmental Laboratory's IS 0 17025 scope of aocreditaSon. (2) Reported sample concentrations were from method ETS-8-154.3. soid-phase extraction. Method ETS-8-154 is included on the 3M Environmental Laboratory's IS 0 17025 scope of accreditation. p. 43 E07-0149; Interim Report 2 3M Cordova Groundwater - December 2009 Page 38 o f 145 CONFIDENTIAL Table 20. COIl-GW -M W -2-81 (Field W ell) 3M U M S ID D escription E07-0149-168 E07-0149-169 E07-0149-170 COIL-GW-MW-2-81-0-091202 COIL-GW-MW-2-81-DB-091202 COIL-GW-MW-2-81-LS-091202 E07-O149-171 E07-0149-172 COIL-GW-MW-2-81-MS-091202 COIL-GW-MW-2-81-HS-091202 Average Concentration (ng/m L) %RPD mPFBA PFO A m C on cen tratio n C oncentration (ng/m L) ^R ecovery (ng/m L) 6.18 NA 0.0344 5.89 NA 0.0343 5.41 NC 0.263 7.98 NC 0.996 15.9 98.7 9.92 % Recovery NA NA 91.7 96.5 99.2 6.04ng6nL 4,8% 0.0344 n g M . 0.29% M U M S ID , D escription E07-0149-168 COiL-GW-M\Af-2-81-0-091202 E07-0149-169 COIL-GW-MV^2-81-OB<)9T2Q2 E07-0149-170 COIL-GW-MW-2-81-LS-091202 E07-0149-171 COIL-GW-MW-2-81-MS-091202 E07-0149-172 COIL-GW-MW-2-81-H&O91202 Average Concentration (ng/m U %RPD PFBS a PFHSa PFOS C oncentration C o n cen tratio n (n g M L ) K fb c o ra y (nq/m U 0.891 , NA <0.0?50. % Recoverv NA C oncentration (n g M i W hcovery 04537 NA 0 .8 4 9 NA <0.0250 ,NA - 0.0538 , NA 1.15 2.09 10.1 112 122 92.4 0.299 1.23 O 10.0 120 123 100 0 .3 0 2 1.14 6.81 99.4 109 8 7 .7 0.870n a M -t 48% <0.0250 ngfrnL 0.0538 ng/m L 0.19% NA NotApplicable NC = Not Calculated: Endogenous sample concentration is greater than 2x spke level (1) Reported sample concentrator were from meBtodETC-tM 10-l.<flrectoiHiolum niNection o f a samples (fluted 1:10 w itfi methanol. Method ETS-8-110 is not included on the 3M EiMronmental Laboratory's IS 0 17025soope o f accreditation. (2) Reported sample concentrations were from melhod ETS-8-154.3, sofid-phase extraction. Method ETS-S-154 is included on the 3M Environmental Laboratory's ISO 17025soopeof accreditation. p. 44 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 39 o f 145 CONFIDENTIAL Table 21. COIL-GW-MW-3-81 (Field W ell) 3M U M S ID D escription E07-0149-173 E07-0149-174 E07-0149-175 E07-0149-176 E07-0149-177 CCHL-GW-MW-3-81-0-091202 COIL-GW-MW-3-61-DB-091202 CXML-<3VV4ylV-81-LS-091202 CO IL-G W -M W ^-81-M S-091202 COIL-GW-MW-3-81-+1S-091202 Average Concentration (no/m L) 1 %RPD PFBA (i) PFO A m C oncentration C o n cen tratio n (no/m L) %Aecovery (ng/m L) % Recoverv 49.3 NA 5.63 NA 48.1 NA 4.74 NA 5 1 4 NC 5.68 NC 56.3 NC 14.6 94.4 144 95.3 106 100 4 8 .7 n g M . Z 5 % 5.19 no/m L 17% M U M S ID D escrip tion E07-0149-173 COIL-<3WMVV^-81-CO91202 E07-0149-174 COIL-GW-MW'3-81-DB-O91202 E07-0149-175 CCML-GW-MW-3-81-LS-091202 E07-0149-176 CCHL-GW-MW3-81-MS091202 E07-0149-177 COIL-GW-MW-3-81-HS-091202 Averaae Concentration (no/m L) %RPD PFBS m is n PPOS m C oncentration C oncentration C oncentration (nofm U %Recoverv (no/m L) % ftecoverv (rigfinL) % Recoverv 0.352<2> NA 5.70 NA - . 7.95 NA 0.361 NA 5.10 NA 7.12 NA 1.35 99.4 5.93 NC 7.99 NC 9.07 87.2 14.6 92.0 15.5 79.7 95,2 93.0 100 94.6 94.5 86.1 0.357 no/m L 1 2.5% S .40no/m L11% 7.54 no/m L 1 11% NA=N ot Applicable NC = Not Calculated: Endogenous sample concentration is greater than 2x spike level. (1) Reported sample concentrations were from method ETS-8-110.1, directo rK xrkjm injection of a samples dfcjted 1:10 with methanol. Method ETS-8-110 is not included on the 3M ErMronmerrtal Laboratory's IS 0 17025 scope of accredtation. (2) Reported sample concentrations were from method ETS-8-044.0, direct Section analysis. Method ET5-0-044 is included on the 3M Environmental Laboratory's IS 0 17025 scape of accreditation. p. 45 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 40 o f 14S CONFIDENTIAL Table 22. COIL-GW-MW-4-81 (Field W ell) 3M U M S ID D escription E07-0149-178 COIL-GW-MW-4-81-0-091202 E07-0149-179 COIL-GW-MW-4-81-DB-091202 E07-0149-180 COIL-GW-MW-4-81-LS-091202 E07-0149-181 COIL-GW-MW-4-81-MS-091202 E07-0149-182 COII-GW -MW -4-81-HS-091202 Average Concentration (n a /m L it %RPD PFBA m PFO A m C on cen tratio n C oncentration (rxj/m U Recovery (na/m L) % Recoverv 155 NA 6.30 NA 155 155 , 197 264 NA NC NC 109 6.21 7.13 17.6 103 NA NC 114 95.8 155 ng/m L 0.0% 6.26 ng/m L i 1.4% 3M U M S ID D escription E07-0149-178 C O IL-G m /IW -4-81-0091202 E07-0149-179 E07-0149-180 E07-0149-181 E07-0149-182 COIL-GW-MW-4-81-DB-091202 C O IL-G W -M W 4-81-LS-091202 COIL-G W -M W -4-81-M S-091202 C O IL-G W -M W -4-81-H S -0 9 1202 Average Concentration (ng/m L) t %RPD PFBS tV PFHS m PROS m C on cen tratio n C oncentration (no/m U Recovery (noAnU 7.78 NA 7.08 7.67 . NA 6.89 8.81 NC 8.29 20.8 131 19.1 116 106 104 % Reccvety NA NA NC 121 97.0 C o n cen tratio n (ng/m L) %Recovery 2 2 .0 NA 2 1 .0 NA 22.6 NC 34.0 NC 112 89.6 7 .7 3 r& m L lj% < * 6.99 ng/m L 2.7% 2 f.5 n g M L t4 .7 X N A >N o tA p p tce U e NC = Not Calculated; Endogenous sample concentration is greater than 2 spike level. (1) Reported sairqjteconGereationswere frommethod ETS-0-110.1, direct orvoolumninjection ofa samplesdUed 1:10 with methanol. Method ETS-8-110 is not indudedan the3M EnvironmentalLaboratory's IS 0 17025 scope of accreditation. (2) The field mabix spike did not meet method acceptance criteria of 100 % 30%. (3) The analytical uncertainty has been adjusted far PFBS to 100% 31% . p. 46 E07-O149; Interim Report 2 3M Cordova Groundwater - December 2009 Page 41 of14S CONFIDENTIAL Table 23. COIL-GW-MW-5-81 (Field W ell) 3 M IM S U ) D escription E07-0149-183 E07-0149-184 E07-0149-185 COIL-GW-MW-5-81-0-091201 COIL-GW-MW-5-81-DB-091201 COIL-GW-MW-5-81-LS-091201 E07-0149-186 COIL-GW-MW-5-81-MS-091201 E07-0149-187 COIL-GW-MW-5-81-HS-091201 .Average Concentration (no/m L) t %RPD PFBA ti) PFO A m C oncentration C o n cen tratio n (ngAnL) XRecovery (no/m L) 0.0791 NA <0.0303 0.0991 NA <0.0303 0.415 130 0.264 1.34 125 0.907 9 .8 7 97.8 9 . ) % Recoverv NA NA 106 91.0 95.3 0.0891 mymL 22% <0.0303 no/m L 3M U M S ID D escription E07-0149-183 E07-0149-184 COIL-GW-MW-5-81-O-O91201 C O IL-G W -M W ^81-D B -091201 E07-0149-185 COIL-GW-MW-5-81-LS-091201 E07-0149-186 COIL-GM7MW5-81-Wfj091201 E07-0149-187 COIL-GW-MW6-81-HS-091201 Averaoe Concentration (no/m L) t %RPD PFBS m PFHS m PFOS m C oncentration C on cen tratio n (n a /triU %Recovery (n g h n li <0.0255 NA <0.0250 1 < 0 0255 NA <0.0250 0.316 127 0.294 % Recom v NA NA 118 C o n cen tratio n (n g fim li ^R ecovery <0.0253 NA <0.0253 NA 0.256 103 1.21 9 .7 4 121 97.5 1.13 9 .8 8 113 9 8 .8 0.951 8.56 95.2 85.7 <0.0255 no/m L <0.0250no/m L <9.0253 ngfaiL NA = NotApp*cable (1) Reported sample concentrafions were from method ETS-8-154.3, solid-phase extraction. Method ETS-8-154 it included on the 3M Environmental Laboratory's IS 0 17(05 scope of accreditation. (2) Reported sample concertrafions were ftom method ETS-8-110.1, direct on-column ^ecSonota samples cHuted 1:10 with methanol. Method ETS-8-110 is not included on the 3M Environmental Laboratory's IS 0 17025 scope of accrediation. (3) The relative percent difference (RPD) did not meet method acceptance criteria of 2 0 % . p. 47 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 42 o f 145 CONFIDENTIAL Table 24. COIL-GW-MW-7-94 (Field W ell) 3M U M S ID D escription E07-0149-188 CO IL-GW-MW-7-94-0-091202 E07-0149-189 COIL-GW -M W -7-94-DB-091202 E07-0149-190 E07-0149-191 E07-0149-192 COIL-GW -M W -7-94-LS-091202 COIL-GW -M W -7-94-M S-091202 COIL-GW -MW -7-94-H S -091202 A vetaoe C oncentrationinotm L) 1 %RPO PFBA to PFOA to C oncentration C oncentration (ngrinL) % Recovery (natm U 63.4 NA 7.23 63.4 NA 7.22 63.0 NC 8.55 % Recoverv NA NA NC 69.5. 160 NC 96.6 17.1 109 99.0 101 63A nafimL 0.0% 7.23 n a rin L i 0.14% 3M U M S ID D escription E07-0149-188 COIL-GW -M W -7-94-0-091202 E07-0149-189 COIL-GW -M W -7-94-DB-091202 E07-0149-190 COIL-GW -MW -7-94-LS-091202 E07-0149-191 E07-0149-192 COIL-GW -M W -7-94-M S-091202 COIL-GW -MW -7-04-HS-O91202 Average Concentration (ng/m U %RPD PFBS to PFHS m PFOS to C oncentration C on cen tratio n (ngrinU % /tecoverv (ngfaiL) 1 .5 4 " NA 7.53 2.26 NA 7.83 Concentration % Kecovery (n o tn U X flK o m y NA 21.1 NA NA 20.4 NA 2.76 86.1 8.56 10.8 891 17.4 102 98.1 101 NC 97.2 9 3 .3 20.8 29.1 109 NC NC 87.4 1.90 no/m L 38% w 7.6 i nq/m L 3.9% 20.B n o h rd .i3A % N A * NotAppfcaMe NC = No! Calculated; Endogenous sample conoentralon is greater than 2x spike level (1) Reported sample concertraflons were from method ETSA-110.1, direct otvcolunun InjacBon of a samples dauted 1:10 with melhanol. Method ETS-8-110 is not ndudedon the 3M Environmental Laboratory's BO 17025 scope o f accredHaflon. (2) The relative percent cMetence(RPD) did not meet method acceptance criteria of 20%. p. 48 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 43 o f 145 CONFIDENTIAL Table 25. COIL-GW -MW -8-94 (Field W ell) 3 M L M S ID D e s c rip tio n 8)7-0149-193 CO IL-G W -M W 6-94-O O 91201 8)7-0149-194 CO IL-G W -M W -8-94-O B-091201 8)7-0149-195 CO IL-G W -M W -6-94-LS-091201 8)7-0149-196 CO IL-G W -M W -8-94-M S-091201 8)7-0149-197 CX)IL-GW -M W -8-94-HS-091201 A ve ra g e C o n c e n tra tio n ( n o tm li t % RPD PFBA m P fO A C o n c e n tra tio n C o n ce n tra tio n In g frriU ` R e co ve ry (n g h n L ) 6 7 .3 N A 11.9 % R ecoverv NA 6 7 .9 N A 12.5 NA 6 9 .2 7 7 .9 161 NC NC 9 3 .4 1 3 .5 2 2 .7 116 NC 105 103 6 7.5nq/m L 0.89% 12.2 n o /m L 4.9% M U M S ID D escription 8 )7 -0 1 4 9 -1 9 3 8 )7 -0 1 4 9 -1 9 4 CXM L-GW -M W -6W -0-091201 CO IL-G W -M W -8-94-DB-091201 E07-0149-195 CO IL-G W -M W -8-94-LS-091201 E07-0149-196 CO IL-G W -M W -8-94-M S-091201 8 )7 -0 1 4 9 -1 9 7 CO IL-G W -M W -8-94-HS-091201 Average Concentration irm /m U %RPD PFSS PFHS m PFOS a C oncentration C oncentration (n g to L ) 9{Recovery <& >*-) 1.14 N A 14.0 ' 0 ,937 NA 1 6 .6 225 121 17.1 X R aco tw y NA NA NC C oncentration (n g h r*J 1 .3 5 1 .1 9 2 .2 8 % Recovery NA NA 101 1 0 .7 9 6 .7 2 6 .5 112 9 .1 7 79.1 93.1 9 0 .3 109 9 3 .7 8 3 .8 8 1 .7 1M 4ngAnL20% 15.3n o /m L 17% 1.27 no/rnL 13% NA = Not Applicable NC= Not CaloJated; Endogenous sample concentration is greater than 2x spite level. (1) Reported sanf^conoenratlorevw tB to m m e d E T 5 ^1 10.1,direcl on-column injection ofa samples (fluted 1:10 with methanoL Method ETS-8-110 is not included on the 3M Environmental Laboratory's IS 0 17025 scope o f accreditation. (2) Reported sample concentrations were from method ETS8-154.3, soSd-phase extraction. M etiod ETS-8-154 is included on the 3M Environmental Laboratory's IS 0 17025 scope of accreditation. p. 49 E07-0149, Interim Report *2 3M Cordova Groundwater - December 2009 Page 44 o f 145 CONFIDENTIAL Table 26. COIL-GW -MW -9-94 (Field W ell) PFBAft* PFO A n M IM S ID D escription C oncentration C oncentration (ngAnL) K R tcovanr (nq/m L) % Recovery E07-0149-198 E07-0149-199 E07-0149-200 E07-0149-2Q1 E07-0149-202 COIL-GW-MW-9-94-0-091201 COIL-GW-MW-9-94-OBO91201 COIL-GWV-MW-S-94-LS-091201 COIL-GW-MW-9-94-MS-091201 CaL-<3m W V-9-94-H^091201 64.3 NA 4.98 62.7 NA 4.61 59.6 NC 4.27 63.7 NC 5.10 72.0 NC 15.7 NA NA NC NC 109 ~ Averaae Concentratton fooftaLj t '/iR P D ~ ~ SSJS noftntrt 2.5% 4.60 n o /m L t 7.7% > . ' . S' 3M L M S ID D escrip tion . EQ7-0149-198 COIL-<3W 44W *W W ?81201 ' E07-0149-199 E07-0149-200 CCHL-GW-MW-9-94-0BO91201 COIL-GW-MW-9-94-LS-091201 E07-0149-201 C C a-G W -M W ^94-M S-091201 B07-01492Q2 COIL-GW-MW-9-94-HS-091201 Average Concentration (no/m U % R P O ____ 1 . PFBS PFHSm PFOS m C o n cen tratio n C oncentration C on cen tratio n (ngM Lt ^Recovery (ngfm L) % Recovery (n afinU XW acowry " - 0.906(^ 0.882. , N.AU' NA ~ 6.8? 6.92 - -2 .1 2 - NA NA 1.74 NA NA<4) NA141 6.08 NC 2.19 . NC 1.88?1 98.7 7.14 NC 2.75 82.1 10.7*1' 9 8 .2 19.0 121 10.4 84.8 0.894 n p /h tL i 2.7% 6.91 n o /h tL 0ri3% 1.93 npfmL 1 20% NA = NotApplicable NC - Noi Calculated; Endogenous sample concentration is greater than 2x spike level. (1) Reported eampte concentrations vwre from method ETS-8-110.l.diredotY oolijnr Injection of a samples (fluted 1:10 with melhanol. Method ETS-8-110 is not included on the 3M Environmental Laboratory's IS 0 17025 scope o l accreditation. (2) The high Held matrix s p te at 10 ngfrnL was not appropriate as compared to the sample concentrcrfon (or PFBA. A laboratory m alm spite was not prepared on this sample. This is a deviation from the protocol. (3) Repotted sample concentrations were from method ETS-8-044.0, direct injection analysis. Method ETS-8-044 Is frdudd on the 3M Environmental Laboratory's IS 0 17025 scope of accreditation. (4) Sample not analyzed by ETS-8-044.0, since the spike levelwas not appioppate as compared to the expected sample concentration. p. 50 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 45 o f 145 CONFIDENTIAL Table 27. COIL-GW-MW-22580 (Field W ell) 3M UM SID Description E07-0149-203 COIL-GWWW-2258GO-091203 E07-0149-204 CX3IL-GW-MW-22580-DB-091203 E07-0149-205 COIL-GW-MVV-22580AS-091203 E07-014&-206 CCHL-GW-fiAAA22580-MS-091203 E07-0149-207 COIL-GW-MW-22580-HS-091203 Average Concentration fno/mLJ 1 %RPD PFBA to PFOAm Concentration Concentration %Recoverv ^R ecovery 5.31 NA <0.0303 NA 4.91 NA <0.0303 NA 4.63 NC 0.238 95.5 5.56 NC 0.841 93.6 14.4 92.9 10.6 106 5.11 n g /M L t 7.9% <0.0303 n o M . 3 M IM S ID Description E07-0149-203 COIL^5W-MW-22580-O-091203 E07-0149-204 COIL-GW-MW-22580-DB-091203 E07-0149-205 COIL-GW-MW-22580-LS-091203 E07-0149-206'3' COIL-GW-MW-22580-MS-091203 07-0149-207 COIL-GW-MW-22580-HS-O91203 Average Concentration (ng/mL) %RPD PFBS to PFHSm PROS <9 Concentration Concentration Concentration (nq/m U %Rccoveiy <ngtmL) ^Recovery (ngthtQ %Recow ry <0.0255 NA <0.0250 NA <0.0253 NA 0.0604 NA <0.0250 NA <0.0253 NA 0.299 95.5 0.272 109 0.236 94.5 1.11 117 1.02 113 0.959 ; 107 9.73 96.8 11.0 110 8.75 87.6 <0.0255ngfmL <OJt2SO ngtnti. <0.0253 ng/mL NA - NotAppfcable NC = NolCalateted; Endogenous sample concentration is greater than 2xspke level (1) Reported sampleconcentraSorts were from m etiod ETS-8-110.1. diedon-cx>lumn injection Ola samples diluted 1:10 with methanol. MeSiod ETS-8-110 is not Included on the 3M Environmental Laboratory's IS 0 17025scope of accreditation. (2) Reported sample concentrations were from m etiod ETS-&-1543, sofid-ptiase extraction. Method ETS-8-154 is included on the 3M Environmental Laboratory's IS 0 17025 scope of accredtabon. (3) Sample bottle was overdled by more than 10% (222 mL). The field matrix spfce true value was acjusled accordingly. p. 51 E07-0149: Interim Report 2 3M Cordova Groundwater December 2009 Page 46 ot 145 CONFIDENTIAL Table 28. COIL-GW -W ell 11 (Production W ell) 3M U M SID Description E07-0149-208 C O Il-G W -PW -11-0-091201 E07-0149-209 COIL-GW -PW -11-OB-091201 E07-0149-210 COIL-GW -PW -11-LS-091201 E07-0149-211 COIL-GW -PW -11-M S-091201 E07-0149-212 COIL-GW -PW -11-HS-091201 Average Concentration (n&mU t %RPO PFBAn PFOA Concentration Concentration (ngtnU '/Recovery (ngtmL) %Recovery 1.97 NA 0.118 NA 220 NA 0.118 NA 2 .4 9 NC 0.343 90.3 3.10 102 0.984 86.9 11.6 95.2 9.83 97.4 2Q9notmL 11% 0.119 noML 0.0% -- ; . - . - 3M U M SID ' Dscitron . E07-0149-208 COIL-GW -PW -11-6-091201 E07-0149-209 COIL-GW -PW -11-DB-091201 E07-0149-210 COIL-GW -PW -11-LS-091201 E07-0149-211 COIL-GW -PW -11-M S-091201 E07-0149-212 COIL-GW -PW -11-HS-091201 Average Concentration (no/mU i %RPD PF8S$ PFHS n PFOSm Concentration (ngfaiLt %Recovery ; <0c0255- NA <0.0255 NA Concentration (ng/mU 0.111 "0.110 ; %Recovery NA NA Concentration (ngAntj 0296 0:268 HRecovety NA NA 0.293 117 0.386 110 0.491 85.3 1.10 110 1.18 107 1.19 91.3 9.44 94.5 9.88 97.7 8.34 80.7 <0.0255ng/mL 0.111 ng/mL 0.90% 0278 ng/mL A 7.2% N A * Not Applicable NC - Not Calculated; Endogenous sample concentration is greater than 2x spfce level. (1) Reported sample concenfcaio n e were from m eltxxt ETS-8-1S4.3, sotid-phase extraction. Method ETS-8-154 s included on the 3M Environmental Laboratory's IS 0 17025 scope of accreditatio n (2) Reported sample concentrafcms were tram method ETS-8-110.1, direct otMxrlunw Injection of a samples (fluted 1:10 with methanol Method ETS-8-110 is not induded on the 3M Environmental Laboratory's IS 0 17025 scope o f accredtation. p. 52 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 47 o f 14S CONFIDENTIAL Table 29. COIL-GW-Well 12 (Production W ell) 3M U M S ID D escription E07-0149-213 E07-0149-214 E07-0149-215 E07-O149-216 E07-0149-217 COIL-GW-PW-12-0-091201 COIL-GW-PW-12-DB-091201 COIL-GW-FW-12-LS-091201 COIL-GW-PW-12-MS-091201 COIL-GW-PW-12-HS-091201 Average Concentration (n g M L i i %RPD P FB A 0> PFOA n> C on cen tratio n C oncentration (nttfm Li X R ecoverr (nq/m L) % R ecovery 4.68 NA 1.42 NA 4.13 NA 1.33 NA 5.30 NC 1.71 NC 6.43 NC 2.50 113 15.5 111 11.6 103 4A 1ngA nU 12% 1.39 nq/m L 6.596 3M U M S ID D escription E07-0149-213 COIL-GW-PW-12-0-031201 E07-0149-214 CO1L-GWPW-12-OB-091Z)1 E07-0149--215 COIL-GW-PW-12-LS-091201 E07-0149-216 COIL<W-FW42-MS-091201 E07-0149-217 COIL-GW4>W-12-HS-091201 Average Concentration (norinU %RPD P FB S ** PFHS m PFO Sn C oncentration {na/m U % Recoverv 0.0404 NA 0.0368 NA 0.324 114 1.11 107 10.1<1) 101 C o n cen tratio n (n tt/m U 1.23 1.22 1.48 2.35 11.7 X R eco very NA NA NC 113 105 C oncentration (n o tin L ) 11.5 11.1 11.7 12.4 . 19.9 % Recoverv NA NA NC NC 86.1 0.0337 n o/m L i 3.1% 1.23 noTmU. 0.82% 11.3 no/m U t 3.5% NA-NatApplcaM e NC = Not Calculated; Endogenous sample concentration is greaterthan 2x spike level. (1) Reportedsampteconrantratiore were from method ETS4M 10.1,direct orvcolum nirqectionofasarTvtesdluted 1:10 with methanol. Method ETTS8-110 is not inducted on the 3M EnvironmentalLaboratory's IS 0 17025 scope Ofaccreditation (2) Reported sample concentrations were from method ETS-8-154.3. soid-phase extraction. Method ETS-8-154 is inducted on the 3M Environmental Laboratory's IS 0 17025 scope of accreditation. p. 53 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 40 o f 145 CONFIDENTIAL Table 30. CO!L-GW-Well 13 (Production W ell) PFBAn PFO A m M U M S ID D escription E07-0149-218 COIL-GW-PW-13-0-091201 E07-0149-219 COIL-GW- PW -13-08-091201 E07-0149-220 COIL-GW- PW-13-LS-091201 07-0149-221 COIL-GW- PW-13-MS-091201 E07-0149-222 COIL-GW-PW-13-HSO91201r. A veraaeC oncentrationtno/rnU % R PD C oncentration C o n cen tratio n (ngftnL) % Recovery (ng/m L) % Recovery 57.9 NA 7.86 NA 56.9 NA 7.98 NA 57,8 NC 8.33 NC 66.1 NC 17.5 96.1 151 93.6 107 98.1 -------S t.4n o M L 1.7% 7.S2 ng/m L 1.5% *" -- M U M S ID .. D escription- E07-0149-218 COH.-GW-PW-13-0;0912Q1 E07-0149-219 E07-0149-220 COIL-GW- PW-13-DB-091201 COIL-GW- PW-13-LS-Q91201 E07-0149-221 E07-0149-222 COIL-GW- PW-13-MS-091201 COIL-GW- PW-13-HS-091201 Average Concentration (ngtm U %RPD ~ PFBSm P FH $m PFO Sm C o n cen tratio n / C o n cen tratio n r C oncentration (nqfinL) M b c o r a y {n g M J % Reeovery (ng/m L) X fleco very ^ 1,67 1 .5 9 -'. NA ' - na = NA - 6.43 NA 14.9 14.7 NA NA 2.43 ^ 80.1 7.27 NC 15.1 NC 11.2 95.8 15.9 94.4 22.5 77.1 9 7 .8 94.3 101 94.5 94.4 78.8 1 6 3 ng/m L i 4.0% 6.46 ng/m L 1 0.93% 14.8 ng/m L 1 1.4% N A -N o t Applicable NC = Not Calculated; Endogenous sample concentration Is greater than 2x spike level. (1) Reported senate concentrations were from method ETS-8-110.1, diredon-oolumn injection of a samples diluted 1:10 with methanol. Method ETS-8-110 is not included on the 3M Environmental Laboratory's S O 17025 scope o faccredBatioa p. 54 E07-0149; Interim Report #2 3M Cordova Groundwater December 2009 Page 49 o f 145 CONFIDENTIAL Table 31. COIL-GW-Well 24 (Production W ell) M U M S tD D escrip tion E07-0149-223 E07-0149224 E07-0149-225 E07-0149-226 E07-0149-277 COIL-GW-PW-24-0-091201 COIL-GW-PW-24-DB-091201 COIL-GW-PW24-LS-091201 CX)IL-GW-PW-24-MS-091201 COIL-GW-PW-24-HS-091201 Average Concentration (no/rnU %RPD PFBAn PFO A m C oncentration C oncentration (ng/m L) H R ecovery (ng/m L) % R ecm m rv 1.40 NA 0.344 NA 1.50 NA 0.350 NA 1.64 2.41 NC 96.0 0.585 1.21 95.5 86.6 1 1 .2 ' 97.5 10.6 103 1.45 n tfM L i 6.9% 0 .347m rfn L i 1.7% 3M U M S ID D escription E07-0149-223 COIL-GW-PW-24-0-091201 E07-0149-224 COIL-GW-PW-24-DB-091201 E07-0149-225 C01L-GW-PW-24-LS-091201 E07-0149-226 COM.-GW-PW-24-MS-091201 E07-0149-277 COIL-GW-PW-24-HS-091201 Average Concentration (no/m U %RPD PFBSm PFHS TM PFO Sm C oncentration C oncentration (ng/m L) % Recovery (ngfm Q <0.0255 NA 0.403 <0.0255 NA 0.412 0.305 122 0.697 1.10 110 1.50 1 0 .0 100 10.9 C o n cen tratio n % R ecn/etv (ng/m L) %Recoverv NA 0.729 NA NA 0.725 NA 116 0.936 NC 109 1.66 93.4 105 9.45 87.3 <00255 nofoiL 0.406 no/m L Z2% 0.727 no/m L 0.55% NA = NotApplicable NC * NotCalculated; Endogenous sample concentration is greater than 2x spite level (1) Reported sample concentrations were from method ETS-a-154.3, soBd-phase extraction. Method ETS-8-154 is included on tte 3M Erwnonmertal Laboratory's IS O 17025 scope o f accreditation. (2) Reported sampte concentrations were from method ETS-ft-110.1, direct orvcoUmn injection ofa samples (fluted 1:10 with methanoL Method ETS-8-110 is not included on the 3M EnvironmentalLaboratory's IS 0 17025 scope of accrecKation. p. 55 E07-0149; Interim Report *2 3M Cordova Groundwater December 2009 Page SO o f 145 CONFIDENTIAL Table 32. COIL-GW-Well 37 (Production W ell) m u m to D escription E07-0149-228 COIL-GW-PW-37-0-091201 E07-0149-229 COIL-GW-PW-37-DB-09121 E07-0149230 COIL-GW-PW-37-LS-091201 E07-0149231 COIL-GW-PW-37-MS-091201 E07-0149-232 COIL-GW-PW-37-HS-091201 A venoe Concentration (n q /m L it% R P D PFBAn PFO A m C oncentration C on cen tratio n (ng/m L) % Recoverv (ngrinL) H Recoverv 1.41 NA 0.342 NA 1.36 NA 0.342 NA 1.69 NC 0;561 87.9 2.48 110 1.22 88.1 11.2 98.2 10.6 103 1.3S th g /iM lX 6% 0 3 4 2 n&m L 1 0.0% ~..r- " \ . * ^ 3H 4UU SID ' D escription - E07-0149-228 E07-0149-229 E07-014 9 2 3 0 C O IU 4 3 V I ^ 7 -^ 1 2 0 1 . COIL-GW-PW-37-DB-091201 COIL-GW-PW-37-LS-091201 E07-0149231 E07-0149232 COH.-GW fW 37-M S-091201 COIL-GW-PW-37-HS-091201 Average Concentration (na/m U % RPD . i<PPB Sm . PFHSm ,v p ro s m C oncentration C oncentration ! in o /m - % Recovwy (n g M J XR ecoverv ! <0:0255 NA 0 .4 0 3 NA . ' <0.0255 NA 6.398 7 NA 0.301 121 0.680 112 1.13 113 1.50 110 9 .9 1 99.2 11.0 106 <0.0255na/m L 0 M 1 no/m L 1 1.2% C on cen tratio n (n g tin U 0.709 0.686 0.917 1.67 9 .1 9 % Pecoverv NA NA NC 97.3 8 5 .0 0.6S S m j/m L3.3% NA=Not Applicable NC = Not Calculated; Endogenous sample concentration is greater than 2x spfca level. (1) Reported sample concentrato r ware from method ETS-8-154.3. sotd-phase extraction. Method ETFS-8-154 is included on the 3M Enviroomental Laboratory's IS 0 17025 scope of accredilaiion. (2) Reportedsamptecofxjentrattons were from method ETS4M 10.1,ded on-column injection of asam ptoerfiuted 1:10 with methanol Method ETS-8-110 is not included on the 3M Environmental Laboratory's IS 0 17025 scope o f accreditation. p. 56 E07-0149; Interim Report 2 3M Cordova Groundwater - December 2009 Page 51 of 14S CONFIDENTIAL Table 33. COIL-GW-C1 (Commercial W ell) 3M IM S ID D escription E07-0149-233 COIL-GW-C1-0-091203 E07-0149-234 COIL-GW-C1-DB-091203 E07-0149-235 COIL-GW-C1-LS-091203 E07-0149-236 COIL-GW-C1-MS-091203 E07-014&-237 COIL-GW-C1-HS-091203 Average Concentration (ng/m L) t %RPD PFBA m PFO A w C on cen tratio n C on cen tratio n (ngAnLi % Recoverv (ngfaiL) 0.756 NA <0.0303 % Recoverv NA 0.819 0.961 1.85 NA <0.0303 NA NC 0.217 87.1 106 0.846 8 4 .9 9 .5 4 98.5 8.97 101 0.788 ng/m L 8.0% <0.0303 ng/m L PFBSTM PFHSm PFO Sm M U M S ID D escription E07-0149-233 E07-0149-234 COIL-GW-C1-0-091203 COIL-GW-C1-OB-091203 E07-0149-235 COIL-GW-C1-LS-091203 E07-0149-236 COIL-GW-C1-MS-091203 E07-0149-237tS| COIL-GWC1-HS-91203 Average Concentration (ng/m L) % RPD C o n cen tratio n C on cen tratio n (ng/m L) % ttitcovwy (ng/m L) <0.0255 NA <0.0250 <0.0255 NA <>.0250 0.267 107 0.253 1.09 109 1.02 8.79 9 9 0 9.29 ^R e c o v e ry NA NA 101 102 105 C o n cen tratio n (ngfinL) % Recoverv <0.0253 NA <0.0253 NA 0.167 66.9 0.801 80.2 7.58 85.4 <0.0255 ng/m L <0.0250 ng/m L <0.0253 nofoiLm NA = Not Applicable NC = Not Calculated; Endogenous sample conoentraion is greater an 2x spike level. (1) Reported sample concentraions were from m etiod ETS-&-154.3, sofid-phase extraction. Method ETS4M54 is included on the 3M Environmental Laboratory's IS 0 17025 scope o f accreditation. (2) Reported sanylecancertoations were from method ETS-8-110.1, direct on-column injection o l a samples dfcitedU O with methanol. Met)x>dETS-&-110 is riot inducted on the 3M Environmental Laboratory's IS 0 17025 scope of accreditation. (3) The field matrix spike did not meet method acceptance criteria of K X nt 30%. (4) The analytical uncertainty tor PFOS had been adjusted to 100% 33%. (5) Sample bottle was overfilled by more than 10% (225 mL). The field matrix spire *u e value w asadjjsted according^. p. 57 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 52 of 145 CONFIDENTIAL Table 34. COIL-GW-C2 (Com m ercial W ell) 3M U M S ID D escription E07-0149-238 COIL-GW-C2-0-091203 E07-0149-239 COIL-GW-C2-OB-091203 E07-0149-240 COIL-GW-C2-LS-091203 E07-0149-241 COIL-GW-C2-MS-091203 E07-0149-242 COIL-GW-C2-HS-091203 Average Concentration (ng/m L) * %RPD PFB n PFO A m Concentration Concentration (ng/m L) % Recovery (ngtinU % Recovery 4.32 NA <0.0303 NA 4 .6 9 4 .8 2 5.76 NA <0.0303 NA NC 0.224 88.7 NC 0.872 87.5 15.3 108 9.83(n 98.6 4 .S 1 n g A n L t.i% <0.0303 ngfmL 3N U M S ID ' Description E07-0149-238 COIL-GW-C2-CL091203 E07-0149-239 E07-0149-240 COIL-GW-C2-DB-091203 COIL-GW-C2-LS-091203 EQ7-0149-241 E07-0149-242 COIL-GW-C2-MS-091203 COIL-G W C 2-H S091203 Averaoe Concentration (no/m U %RPO RF8S 0 PFHS 0 PFOS 0 Concentration C oncentration Concentration (n o ttiU % Recoverv (ngfm L) ^R e c o v e ry (no/m L) R ecovery 0 .1 4 4 NA <0.025<y NA <0.0253 NA 0.145 0.400 1.21 9 .8 6 (1) NA .... 100 107 97.3 <0.0250 0.245 1.04 9 .9 9 (" NA 98.0 104 9 9 .9 <0.0253 0.205 0.930 8.29{,) NA 81.2 93.1 83.0 0.143 nq/m L 1 0.69% <0.0250 n o M . <0.0253 no/mL N A= Not Applicable NC = Nat C alaialed; Endogenous sample concentration is greater than 2x spike level. (1) Reported sample concentrations were from method ETS-8-110.1. direct orvoolumniniecSon of a samples dtirled 1:10 with methanol. Method ETS-8-110 is not Included on lhe3M Environmental Laboratory's IS 0 17025 scope of accreditation. (2) Reported sample concentrations were from method ETS-8-154.3, solid-phase extraction. Method ETS-ft-154 is included on the 3M Environmental Laboratory's IS 0 17025 scope o f accreditation. p. 58 E07-0149; Interim Report 2 3M Cordova Groundwater December 2009 Page S3 o f 145 CONFIDENTIAL Table 35. COIL-GW-C3 (Commercial W ell) 3M L M S IO D escription E07-0149-243 CCML-GW-C3-0-091203 E07-0149-244 COIL-GW-C3-DB-091203 E07-0149-245 COIL-GW-C3-LS-091203 E07-0149-246 COIL-GW-C3-MS-091203 E07-014S-247 C0IL-GW-C3-HS-091203 Average Concentration (ng/m L) %RPD PFBA n PFO A m C on cen tratio n C on cen tratio n (nofniU % Recoverv (ngfm L) 0.0758 NA <0.0303 0 .0 7 7 5 NA <0.0303 % P ocw etv NA NA 0.427 1.37 10.2 140 129 101 0.208 0.819 10.1 82.4 82.1 101 0.0787 ngfmL 2.2%n 0 .0 3 0 3 ngfm L 3M L M S ID D escription EQ7-0149-243 E07-0149-244 E07-0149-245 C O IL-G W C 3-0-091203 CCML-GWC3-DB-091203 COIL-GW-C3-LS-091203 E07-0149-246 COIL-GWC3-MS-091203 E07-0149-247 CCML-GW-C3-HS-091203 Average Concentration (ncmL) %RPD PFBS ru PFHS m p ro s n C oncentration C oncentration C on cen tratio n (n g /M .) %RecoYery (ngfm L) % Recovarv (ngfm L) X ftecoverv <0.0255 NA <0.0250 . : NA . <0.0253 NA <0.0255 NA <0,0250 NA <0.0253 . NA 0.264 104 . 0.240 96.0 0.210 83.2 1.04 104 _ 0.987 98.7 0,862 86.3 9 .7 4 9 7.5 10.2 - 102 8 .3 0 83.1 <0.0255 ngfm L ........ <OJO250ng/mL <0.0253 no/mL NA = Klol Appicabte NC= Not Calculated; Endogenous sample concentration is neater than 2x spfce level. (1) Reported sample concentrations were from method ETS-6-154.3, solid-phase extraction. Method ETS-ft-154 is included on (tie 3M Environmental Laboratory's IS 0 17025 soope of accreditation. (2) Reported sample conc^ntrafiorrs were from mettwd ETS-8-110.1. direct orvcotumn injection of a samples diuled 1:10 w rit methanol. Method ETS-8-110 is not included on the 3M Environmental Laboratory's IS 0 17025scope ofacaedSation. (3) The field matrix spite did not meet method acceptance criteria o f 100% 30%. (4) The analytical uncertainty for PFBA had been adjusted to 100% 40%. E07-0149; Interim Report *2 3M Cordova Groundwater - December 2009 Page 54 o t 14S p O<>l CONFIDENTIAL Table 36. COIL-GW-C4 (Comm ercial W ell) 3M U M S ID D escription E07-0149-248 E07-0149-249 E07-0149-250 E07-0149-251 E07-0149-252 COIL-GW-C4-0-091203 C O IL-G W C 4-D B -091203 CCHL-GW-C4-LS-091203 C O IL-G W C 4-M S-091203 . C0IL-GW C4-HS-091203 Average Concentration (ng/m U i %RPD PFBA w PFOA m Concentration Concentration (n g to l) ^R ecovery (ngfm Q 0.213 NA 0.0931 %Rocovery NA 0.209 0.564 1.41 NA 141 120 0.0943 0 .2 9 6 0 .9 2 5 NA 80.1 83.4 12.1 . . . -119 9 .7 1 96.5 0.211 nq/m L 0.0937 ng/m L A 1.394 M U M S ID D escription E07-0149-248 E07-0149-249 E07-0149-250 E07-0149-251 E07-0149-252 CCML-GW04-0-091203 COIL-GW-C4-DB-091203 COIL-GW-C4-LS-091203 C O IL-G W -C 4-M S -091203 COIL-GW C4-HS-091203 * Average Concentration ino/m L} A %RPD PFBS m PFHS n PFOS m C oncentration Concentration (no/m U . V Jtecoven (no/m U -- <0.0255 NA <0.0250 <0.0255 NA <0.0250 0.289 113 . 0.257 1.09 109 1.04 10.0 100 10.1 % Recovaty NA NA 103 104 101 C o n cen tratio n (n g tw % Recoverv 0.0420 NA 0.0406 NA 0.233 75.9 0.924 8 8 .4 8 .3 6 8 3 .3 <0Jt25SnoM L <0.0250nofm L 0.0413 n a /tiiL t 3.4% N A -N o tA p p tca b le NC * No! Calculated; Endogenous sample concentration is greaterthan 2x spite towel (1) Reported sample concentrations were from method ETS-8-1543, so6d-phase extraction Method ETS-8-154 is included on the 3M Environmental Laboratory's IS 0 17025 scope of acgedi aBoft (2} Reported sample concentrations were from method ETS-8-110.1, direct ofxnlum n injection o f a samples cButed 1:10 with methanol Method ETS-8-110 is not included on the 3M Environmental Laboratory's ISO 17Q2S scope o f accreditation. (3) The fekJ matrix sp&e did not meet method aooaptanoa criteria of 100% 30%. (4) The analytical uncertainty for PFBA had been adjusted to 100% 41% . p. 60 E07-O149; Interim Report #2 3M Cordova Groundwater December 2009 Page SS o f 145 CONFIDENTIAL Table 37. COIL-GW-C5 (Comm ercial W ell) m um ) D escription E07-0149-253 E07-0149-254 E07-O149-255 COtL-GW-C5-0-091203 COIL-GW-C5-DB-091203 COIL-GW-C5-LS-091203 E07-0149-256 E07-0149-257 COIL-GW-C5-MS-091203 CCHL-GWV-C5-HS-091203 Average Concentration (ngfrriL) 1 %RPD PFBA m PFOAm C o n cen tratio n C oncentration (m j/m L) % Recovery (ng/m U 0.543 NA 0.0361 0.538 NA 0.0353 0.856 NC 0.247 1 6 9 115 0.925 9.59 9 0 .5 9 .8 0 % Recoverv NA NA 83.7 89.2 97.9 0.541 n gfynL t0.93% 0.0357ng/m L 2.2% m um ) D escription 0)7-0149-253 0)7-0149-254 COIL-GW-C5-0-091203 COIL-GW-C5-DB-091203 0)7-0149-255 E07-0149-256 COIL-GW-C5-LS-091203 COIL-GW-C5-MS-091203 E07-0149-257 CCML-GW-C5-HS-091203 Avereoe Concentration (n a/tn U % R P D PFBS ro PFHS m p ro s i C o n cen tratio n C o n cen tratio n %Recovery (ngfm Q <0.0255 NA <0.0250 <0.0255 NA <0.0250 0.283 111 0.259 1.09 9 .2 9 109. 93.0 1.05 10.4 C oncentration % Recoverv . (hg/m L) % Recovery NA <0.0253 NA NA <0.0253 NA 104 0.233 92.3 105 0.952 95.3 104 8 .2 9 83.0 < 0 .0 2 5 5 no/m L <0.0250notm L <0.0253 no/mL N A - Not Applcabte NC = Not Calculated; Endogenous sample concentration is greaterthan 2x spite lavai (1) Reported sample coocerftations were from method ETS-8-154.3. sold-phase extraction. Method ETS-8-154 is induded on the 3M Environmental Laboratory's IS 0 17025 scope of accreditation. (2) Reported sample carKsrttafons were from rne&iodETS-8-110.1, direct orv<x>lumn injection o f a samples rffluled 1:10 with methanol Method ETS-8-110 is not induded on the 3M Environmental Laboratory's IS 0 17025 scope o f accreditation. p. 61 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 56 o f 145 CONFIDENTIAL Table 38. COIL-GW -TRIP BLANK M U M S ID D esolation E07-0149-258*11 COIL-GW -MW -3-94-EB E o z -o i'ts -^ a *'' COIL-GW-MW-1 -88-EB E07-0149-264(,) CCML-GW-MW-22580-EB E07-0149-268,,) COIL-GW -TRIP01-0 E07-0149-269*'> COIL-GW -TRIP01-LS E07-0149-270 COIL-GW -TRIP01-MS E07-0149-270<2' - COIL-GW -TRIP01-MS E07-0149-27 CIL-GW -TRIP01-HS 3M U M S ID E07-0149-258*1' E07-0149-263(1) E07-0149-264(1> E07-0149-268(" E07-0149-26901 E 0 7 -0 1 4 9 -2 7 0 '1' E07-O149-270<2' E 0 7 -0 1 4 9 -2 7 1 ----- D escription COIL-GW -MW -3-94-EB COIL-GW -M W -1-88-E8 COIL-GW -M W -22580-E8 COIL-GW -TRIP01-0 COIL-GW -TRIP01-LS COIL-GW -TRIP01 -MS COIL-GW -TRIP01-MS COIL-GW -TRIP01-HS PFBA PFOA Concentration (n g fa W Kftecowt n <0.0300 NA <0.0300 NA <0.0300 NA <0.0300 NA 0.323 129 8.43 8 4 .3 10.2 - 102 _ 94.8 !- 9 4 .6 C o n cen tratio n (ngfm L) <0.0303 <0.0303 <0.0303 <0.0303 0.250 8.13 _ 10.3 102 I -. Y tR oco vw NA NA NA NA 100 81.5 103 . 101 J ; PPBS PFHS PFOS Concentration Concentration, C oncentration (n g /rit) ^Recovery {ngtm L) %Jfccovery A ttim L i ^Recovery <0.0255 NA <0.0250 NA <0.0253 NA <0.0255 NA <0.0250 NA <0.0253 NA <0.0255 NA <0.0250 NA <0.0253 NA <0.0255 NA <0.0250 NA <0.0253 NA 0.280 112 0.280 112 0 .2 6 5 106 10.8 108 10.9 109 10.8 108 9.94 9 9 .5 10.8 108 9 .3 4 93.5 93.9 92.1 93.7 93.7 8 6 .6 85.7 NA = Not Applicable (1) Reported sample concentrations were tram method ETS-8-154.3, so6d-phase extraction. Method ETS4-154is included on the 3M Environmental Laboratory's ISO 1702S scope of accreditation (2) Reported s a n ^ concentrations were from method ETS-8-110.1, direct oo-ookjmn injection ot a samples fllluted 1:10 with methanol. Method ETS-8-110 is not included art the 3M Environmental Laboratory's IS 0 17025 scope ot accreditation. p. 62 E07-0149; Interim Report *2 3M Cordova Groundwater - December 2009 Page 57 o t 145 CONFIDENTIAL l';T Laboratory control spikes and field matrix spikes were used to determine the analytical method accuracy and precision lo r all analytes. Analysis was successfully completed following 3M Environmental Laboratory methods described herein. Ail remaining samples and associated project data (hardcopy and electronic) w ill be archived according to 3M Environmental Laboratory standard operating procedures. Attachment A: Test Protocol Attachment B: Test Protocol Amendment Attachment C: Analytical Method Attachment D: Representative Chromatograms and Calibration Curves Attachment E: Method/Protocd Deviations ,' . Jt::<?. ryS v1 E07-O149; Interim Report #2 3M Cordova Groundwater - December 2009 Page S8 of 145 CONFIDENTIAL r ><vfw?i; r t. is * r . . ^ ! i k . ..V n>*2 mil, Ti frii I-- n _A --SiA" E07-0149; Interim Report 2 3M Cordova Groundwater - December 2008 Page 69 of 145 CONFIDENTIAL Attachment A: T est Protocol E07-014B; Interim Report * 2 3M Cordova Groundwater - December 2008 Page 60 o f 145 3M E N V IR O N M E N T A L L A B O R A T O R Y CONFIDENTIAL Lab Request Number: E07-0149 ANALYTICAL STUDY PROTOCOL Study Title Analysis of Perfluorobutanoic Acid <PFBA), Perfluorooctanolc Add (PFOA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Groundwater Using LC/MS/MS for the "3M Fluorochemical (FC) Assessment Work Plan for the 3M Cordova, IL Facility". Data Requirement GLP Date: April 11,2007 Performing Laboratory 3M Environmental, Health, and Safety Operations 3M Environmental Laboratory 3M Center, Bldg 260-5N-17 St. Paul, MN 55144 Laboratory Project Identification E07-0149 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 1 o f 10 Page 61 of 145 3M ENVIRONMENTAL LABORATORY CONFIDENTIAL Lab Request Number: E07-0149 Study Identification Analysis of Perfluorobutanoic Acid (PFBA), Perfluorooctanoic Acid (PFOA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Groundwater Using LC/MS/MS for the "3M Fluorochemical (FC) Assessment Work Plan for the 3M Cordova, IL Facility". Test Substance Sponsor Sponsor Representative Study Director The test materials are perfluorobutanoic acid (PFBA), perfluorooctanoic acid (PFOA), perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS), and perfluorooctanesulfonate (PFOS). 3M Corporation St. Paul, MN 55144 Gary Hohenstein 3M Environmental Health and Safety Operations Bldg 42-02-E-27 St. Paul, MN 55144 Phone: (651) 778-5150 Fax (651) 778-7203 gahohenstein@mmm.com Jai Kesari Weston Solutions 1400 Weston Way West Chester, PA 19380 Phone: (610) 701-3761 Fax: (610-701-7401 j.kesari@westonsolutions.com E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 2 o f 10 Page 62 ot 145 3M ENVIRONM ENTAL LABORATORY CONFIDENTIAL Lab Request Number: E07-0149 Principal Analytical Investigator (PAi) Susan Wolf 3M Environmental Health and Safety Operations 3M Center, Bldg. 260-05-N-17 St. Paul, MN 55144 Phone: (651)733-9851 Fax (651) 733-4687 stwolf@mmm.com Study Location(s) Testing Facility 3M Environmental, Health, and Safety Operations 3M Environmental Laboratory 3M Center, Bldg 260-5N-17 St, Paul, MN 55144 Proposed Study Timetable Experimental Start Date y, - :Sample Receipt: Early April, 2007 Experimental Termination Date :j May 31, 2007 n:- - . .. > '-i -r, E07-0149; Interim Report #2 3M Cordova Groundwater December 2009 Page 3 o f 10 Page 63 of 145 3M ENVIRONMENTAL LABORATORY CONFIDENTIAL Lab Request Number: E07-0149 1. S t u d y Analysis of Perfluorobutanoic Acid (PFBA), Perfluorooctanoic Acid (PFOA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Groundwater Using LC/MS/MS for the "3M Fluorochemical (FC) Assessment Work Plan for the 3M Cordova, IL Facility". 2. P u r po se The purpose of this study is to analyze groundwater samples from seventeen monitoring wells and five production wells from the 3M Cordova facility, for perfluorobutanoic acid (PFBA), perfluorooctanoic acid (PFOA), (PFBS), perfluorohexanesulfonate (PFHS), and perfluorooctanesulfonate (PFOS). The samples will be prepared and analyzed using the current version 3M Environmental Laboratory analytical method ETS-8-154: "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". The targeted limit of quantitation will be 0.025ng/mL (ppb) for all compounds of interest. 3. R e g u l a t o r y C o m p l ia n c e The analytical portion will be conducted in accordance with the United States Environmental Protection Agency Good Laboratory Practice Regulations for Non-dinical Laboratory Studies, 40 CFR 792. 4. Q u a lity A s s u r a n c e The 3M Environmental Laboratory Quality Assurance Unit will audit the study conduct, raw data, and final report to determine compliance with Good Laboratory Practice Regulations, this protocol, and 3M Environmental Laboratory Standard Operating Procedures. 5 . Te s t S u b s t a n c e s Test Substance Chemical Name PFBA Perfluorobutanoic Add Chemical Formula CsFrCOO' Identifier Acid CAS# 375-22-4 PFOA Perfluorooctanoic Acid C 7F 1 &COO' Ammonium Salt CAS# 3825-26-1 PFBS Perfluorobutane sulfonate CiFsSOa Potassium Salt CAS# 29420-49-3 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 4 o f 10 Page 64 o f H 5 3 M ENVIRONM ENTAL LABORATORY CONFIDENTIAL Lab Request Number: E07-0149 Test Substance Chemical Name Chemical Formula Identifier PFHS Perfluorohexane sulfonate C tFuS O j' Potassium Salt CAS# 3871-99-6 PFOS Perfluorooctane sulfonate CnFirSOa' Potassium Salt CAS# 2795-30-3 Samples for this study are "real world" samples, not dosed with a specific lot of test substance, at any particular rate. Therefore only the analytical phase of this study will be performed under the GLP standards. - The test substances for this study are not test substances in the classic sense, The known source, expiration date, storage conditions, chemical lot number, TCR number, physical description, and purity of the test-substances that are being monitored inthe test system are not known as they wouldbe known for the reference substances. E07-0149; Interim Report #2 3M Cordova Groundwater December 2009 Page 5 o f 10 Page 65 of 145 3M E N V IR O N M E N TA L L A B O R A T O R Y Lab Request N um ber E07-0149 6. R efe r e n c e S u b s ta n c e s Reference Substance Chemical Name Chemical Formula Identifier <nSource E xp iratio n Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity ^ 'Solubility PFBA Perfluorobutanoic Acid C jF jC O O Acid CAS# 375-22-4 Aldrich 02/16/2017 Frozen 09713EC T C R -7 5 7 Liquid, room temp. 98.7% No information available PFOA Perfluorooctanoic Acid C rF .sC O O Ammonium Salt CAS# 3825-26-1 3M 02/27/2017 Frozen 332 T C R -1 2 3 White powder ; 95% >2 0 % PFBS Periluorobutanesulionate C 4F9S O 3 Potassium SaR CAS# 29420-49-3 3M 0 1 /1 8 /2 0 1 7 Frozen 2 T C R -2 8 2 Good/white crystals 6 7 .3 % - 54.400 ppm PFHS Perfluorohexanesulfonate CsF jjSOj' Potassium SaR CAS# 3871-99-6 3M 02/12/2017 Frozen NB 120067-69 T C R -0 8 3 White powder 98.6% No,information available PFOS Perfluorooctanesulfonate CaFtrSOs Potassium San CAS# 2795-39-3 3M 08/31/2016 Frozen 217 T C R -1 1 6 6 White powder 8 6 .6 % 680 ppm (1) Documentation regarding synthse o f the le st substances is located at the source ~ - (2) Samples w ill be analyzed against solutions prepared from these reference substances, arid these solutions w ill be assigned expiration dates according to SOP ETS-4-027. (3) A l test substances are believed to be soluble in water at the leveis to be investigated. During tire course o f the study, if mere is any inctication that the substances are not soluble at the levels tested (visible prcipittes), soiubtirty win be further investigated and discussed in the report. CONFIDENTIAL E07-0149; Interim Report #2. 3M Cordova Groundwater - December 2009 Page 66 of 145 Page 6 of 10 p 3M ENVIRONM ENTAL LABORATORY CONFIDENTIAL Lab Request Number. E07-0149 7. Te s t S y s te m The test system is groundwater. Additional sources may be added as requested. Sections 40 CFR 792.120 (6), (9). (10) and (11) are not applicable as only the analytical phase of this study is under the Good Laboratory Practices. The test systems were chosen to access the impact of the reference substances in the 3M Cordova, Illinois facility, and are defined in the work plan. The samples will be collected by Weston Solutions and shipped to the testing facility. The control samples will be prepared by the testing facility. Prior to collection, each sample bottle sent to the testing location will be identified with a laboratory sample reference number. This reference number will be unique and will distinguish each laboratory sample that is carried through the analytical procedure. Chromatographic data will be identified by the laboratory sample reference number. 8. S p e c im e n R e c e ip t The groundwater samples will be collected from seventeen monitoring wells and five production wells from the 3M Cordova facility; Water samples will be collected by Weston Solutions personnel and shipped to the 3M Environmental Lab on ice. Samples will be kept refrigerated at 2*C- 8C from the time of sample receipt until analysis. * 9 . E x p e r im e n ta l D e s ig n ! 9.1 Preparatory and Analytical Method Samples will be prepared and analyzed, usingETS-8-154: "Determination of Perfluorinated Adds, Alcohols, Amides' and. Sulfonates In Water By Solid Phase Extraction and High Performance Liquid Chfomatography/Mass Spectrometry". Extracted calibration standards will be prepared in a similar matrix (Mill! Q or matrix matched water) to be determined along with;the QC samples. i`! All containers used for water sample collection wilt be shipped to the sample location. A field duplicate and at least two levels of field;spikes of each sample will be collected. Some sites may have additional field spikesta bracket the possible concentration ranges of analytes in a location. The field spikes will contain PFBA, PFOA, PFBS, PFHS and PFOS. The field spikes will be used1to determine the precision and accuracy of the method for each site sampled. Laboratory spikes and laboratory duplicates will not be a component of this study but, if necessary, can be done with approval or by request of the study director. Recoveries of field matrix spikes (FMS) are anticipated to be between 70% and 130% of the fortified levels. If the recoveries of the field spikes fall outside the acceptable range, the sample result will be reported as "NR" (not reported due to QC failures). E07-0149; Interim Report #2 3M Cordova Groundwater December 2009 Page 7 o f 10 P a ge67of145 3M ENVIRONMENTAL LABORATORY CONFIDENTIAL Lab Request Number: E07-0149 For each extraction batch at least three method blanks will be prepared. In addition, triplicate lab control spikes at a minimum of two different concentrations are to be performed with each extraction batch. 9.2 Methods for Control of Bins Control of bias is accomplished using laboratory control samples (as indicators of method accuracy and precision) and blanks. Laboratory control samples are used to determine the overall data uncertainty for each batch. Milli Q or matrix matched water will be used to prepare the laboratory control samples. Triplicate laboratory control samples at a minimum of two different concentrations are to be performed with each extraction batch. The relative standard deviation of the pooled recoveries must be less than or equal to 20% and the average recovery must be 80-120%. Low lab control spikes will be prepared at concentrations approximately five to ten times higher than the targeted LOQ and high laboratory control spikes will be prepared at concentrations near the mid-point of the calibration curve. For each analytical batch of samples, solvent and method blanks will be analyzed. Method blanks must be done with each extraction batch. A range of three to seven method blanks must be prepared interspersed throughout the extraction batch and analyzed throughout the analytical sequence. The mean area count for each analyte in the method blanks must be less than 50% of the area count of the LOQ standard. If the mean area counts of the method blanks exceed 50% of the LOQ standard, then the LOQ must be raised to the first standard level in thecurve that meets criteria. Alternatively, the method blanks could be evaluated statistically to determine outliers or technical justification toeliminate a blank may be made when determining the LOQ. The criteria are then applied again to evaluate method blank compliance. If any method blanks are removed from the LOQ determination,, document in the report or the raw data as appropriate. 10 . D a t a Q u a l it y O b j e c t iv e s Method performance criteria will be demonstrated for; each analytical batch in accordance with ETS-8-154. The appropriate laboratory control samples prepared with each set of samples should verify the method's accuracy is 100% 20%, and the method's precision is within 20% relative standard deviation. 11. S ta tistic a l A n a ly s is Averages and standard deviations will be calculated. Additional calculations are provided in ETS-8-43. 12. Repo rt A report of the results of the study will be prepared by 3M Environmental Laboratory. The report will include, but not be limited to, the following, when applicable: 12.1 Name and address of the facility performing the study, EO7-O140; Interim Report #2 3M Cordova Groundwater December 2009 Page 8 o f 10 Page 68 of 145 3M ENVIRONM ENTAL LABORATORY CONFIDENTIAL Lab Request Number: E07-Q149 1 2 .2 Dates upon which the study was initiated and completed. 12.$ A statement of compliance by the Study Director addressing any exceptions to Good Laboratory Practice Standards. 12.4 Objectives and procedures as stated in the approved protocol, including any amendments to the original protocol. 12.5 The test substance identification by name, chemical abstracts number or code number, strength, purity, and composition or other appropriate characteristics, if provided by the Sponsor; , . 12.6 Stability and the solubility of the test substances under the conditions of , administration, if provided by. the Sponsor. 12.7 A description of the methods;used toconduct the test(s). 12.8 A description of thetest system.' 12.9 A description of any-circumstances that may have affected the quality or the- integrity of the data. . ^ v -- v 'v,., 1 2 .1 0 The name of the Study Director and the names ofiotber scientists, ,. professionals, and supervisory personnel involved in the study. 12.11 A description of the transformations; calculations, or operations performed on the data, a summary and analysis;of the analytical chemistry data, anda t. statement of the conclusions drawn from the analyses. 12.12 Statistical methods used to evaluate the data, if applicable. b.. 1 2 .1 3 The signed and dated reports of each of the individual'scientists or other professionals involved irrthe study, if applicable. , ,, 1 2.14 The location where raw data;andthe final report are to be stored, r 1 2 .1 5 A statement prepared bythe Qualityassurance unit listing the dates that study inspections ahd auditswere madeand the dates of any findings reported to the Study Director and Management. 1 2 .1 6 If it is necessary to mdke corrections or additions to a final report after it has been accepted, the changes will be made in the form of an amendment issued by the Study Director. The amendment will clearly identify the part of the final report that is being amended, the reasons for the amendment, and will be signed by the Study Director. 13. L o c a t io n o f R a w D a t a , R e c o r d s , a ^i d F in a l R e p o r t Original data or copies thereof, \$IJ,be:available at 3M Environmental Laboratory to facilitate audits of the study during;its progress,.and before acceptance of the final report. When the final report is completed, all original paper data, including those items listed belowwill be retained in the permanent record archives of 3M Environmental Laboratory following signing of the report 13.1 The following raw data and records will be retained in the study folder in the archives according to 3M Environmental Laboratory Standard Operating Procedures. 13.1.1 Approved protocol and amendments 1 3 .1 .2 Study correspondence 1 3 .1 .3 Shipping records 1 3 .1 .4 Raw data 1 3 .1 .5 Approved final report (original signed copy) EO7-0149; interim Report *2 3M Cordova Groundwater - December 2009 Page 9 o f 10 Page 69 of 146 3M ENVIRO NM ENTAL LABORATORY CONFIDENTIAL Lab Request N um ber E07-0149 13.1.6 Electronic copies of data 13.2 The following supporting records will be retained separately from the study folder in the archives according to 3M Environmental Laboratory Standard Operating Procedures: 1 13.2.1 Training records 1 3 .2 .2 Calibration records 13.2.3 Instrument maintenance logs 13.2.4 Standard Operating Procedures, Equipment Procedures, and Methods 1 3 .2 .5 Appropriate specimens 14. D a t a / S a m p l e R e te n tio n A portion of the test substance used in this study will be retained for a period not less than 10 years following the application of the final test rule. The extracts will only be retained so long as their quality affords evaluation. 15. P r o to c o l A m e n d m e n t s a n d d e v ia tio n s Planned changes to the protocol will be inthe form of written amendments signed by the Study Director and the Sponsor's Representative. Amendments will be considered as part of the protocol and will be attached to the final protocol. Any other changes (unplanned) will be in the form ofwritten deviations, signed by the Study Director and filed with the raw data. All changes tp the protocol and the reason for the changes will be indicated in the final report. 16. S ig n a tu r e s Jai Kesari, Study Director Date Gary A. Hohenstein, Sponsor Representative Date / i ifrilliam K, Reagen, 3M Environmental Laboratory Management Date E07-0149; Interim Report #2 3M Cordova G roundwater. December 2009 Page 10 o f 10 Page 70 o f 145 3M ENVIRONMENTAL LABORATORY CONFIDENTIAL Lab Request Number. E07-0149 13.1.6 Electronic copies of data 13.2 The following supporting recordswill be retained separatelyfromthe study folder inthe archives according to 3M Environmental Laboratory Standard Operating Procedures: 13.2.1 Training records 13.2.2 Calibration records 13.2.3 Instrument maintenance logs 13.2.4 Standard Operating Procedures, Equipment Procedures, and Methods 13.2.5 Appropriate specimens 14. D a t a / S a m p l e R e t e n t io n A portion ofthe test substance used in,this studywill be retained for a period not less than 10 years following die applicatidhpfthe final test rule. The extractswill onlybe retained so long as their qualityaffords evaluation. 15. P r o t o c o l A m e n d m e n t s a n d d e v ia t io n s Planned changes tothe protocol will b'einthe form of written amendments signed by the Study Director and the Spon^or'bRepresentative. Amendments will be considered as part ofthe protocol and will be attached to thefinal protocol. Any other changes (unplanned) will be in the formof written deViatfofos, signed bythe Study Director and filed with the rawdata. All changes to the protocol and the reason for thechanges will be indicated in the final report. 16. Sig natures Jai Kesari, Study Director ' i m A -H H /h fa n GaryA/ Hohenstein, Sponsor Representative Date M 17 , 2 0 0 1 I Date William K, Reagan, 3M Environmental Laboratory Management . Date E07-014B; Interim Report #2 3M Cordova Groundwater December 2009 Page 10 o f 10 Page 71 of 145 CONFIDENTIAL Attachment B: T est Protocol Amendment E07-0149; Interim Report #2 3M Cordova Groundwater December 2009 Page 72 of CONFIDENTIAL #23 M Protocol E 0 7 -0 1 49 Amendment Study Title Analysis o f Perfluorobutanolc Acid (PFBA), Perfluorooctanolc A d d (PFOA), Perftuorobutanesulfbnate (PFBS). Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Groundwater Using LC/MS/MS fo r the *3M Ftuorochemical (FC) Assessm ent W ork Plan fo r the 3M Cordova, IL Facility" PROTOCOL AMENDMENT NO. 2 Amendment Date: November 19,2008 Performing Laboratory 3M Environmental, Health, and Safety Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55144-1000 Laboratory Project Identification E07-0149 E07-0149; Interim Report #2 3M Cordova Groundwater December 2009 Page 1 of 4 Page 73 of 145 CONFIDENTIAL #23 M Protocol E 0 7 -0 1 4 9 Amendment This am endm ent m odifies the following portion of protocol: Analysis o f Perfluorobutanoic Acid (PFBA), Perfluorooctanoic A dd (PFOA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Groundwater Using LC/MS/M5 for the "3M Fiuorochemical (FC) Assessm ent W ork Plan fo r the 3M Cordova, IL F ad lity" PROTOCOL READS: 6. REFERENCE SUBSTANCE Reference Substance Chemical Name , Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description P u rity S o lu b ility PFBA Perfluorobutanoic Acid CjFrCOO Acid CAS# 375-22-4 Aldrich 02/16/2017 Frorein 09713EC TCR-757 Liquid, room temp 98.7% No inform ation available PFOA Perfluorooctanoic A dd c 7f ,, c o o Ammonium S ail CAS# 3625-26-1 3M 02/27/2017 Frozen 332 TCR-123 W hite powder 95% >20% PFBS Perfluorobutanesulfonate CF|SO) Potassium Sait CAS# 29420-49-3 3M 01/18/2017 Frozen 2 TCR-282 Good/white crystals 97.3% 54.400 ppm Reference S ub ita n e a Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity S o lu b ility PFHS Perfluoronexanesurfonate C *F,,SO , Potassium Salt CAS# 3671-99-6 3M 02/12/2017 Frozen NB 120067-69 TCR-083 , White powder 98.6% No information available PFOS Perfluorooctanesulfonate CF,tSOj' Potassium Salt CAS# 2795-39-3 3M 08/31/2016 Frozen 217 TCR-1166 W hite powder 86.9% 680 ppm E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 2 of 4 Page 74 o f 145 CONFIDENTIAL 3M Protocol E07-0149 Amendment #2 AMEND TO R EAD: 6. REFERENCE SUBSTANCE Reference Subetanee Chemical Name PFBA Perfluorobutanoic Acid - PFOA(,) Periluorooctanoic Add PFBS Peffluorobutanesutfonate Reference Substance Chemical Name PFHS PFOS`1) Perfluorohexanesutfonate Periluorooctanesulfonate (1) Two reference substances will be used tor PFOA and PFOS, one containing primarily1linear isomers, and the second containing branched isomers. REASON: To allow fo r the use o f reference substance* that may be Identified by TCR num ber or lot num ber other that those stated in the protocol. PROTOCOL READS: 9.1. Preparatory and Analytical method Sam ples w ill be prepared and analyzed'using ETS-8-154: "Determ ination o f Perfluorinated Acids, Alcohols, Am ides, and Sulfonates In Water: By Solid Phase Extraction and High Performance Liquid Chrom atography/M ass Spectrometry". AMEND TO READ: 9.1. Preparatory and Analytical method Samples w ill be prepared and analyzed by LC/MS/MS follow ing ETS 8*154.3 "Determ ination o f Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance, Liquid Chromatography/Mass Spectrometry*. Alternately, samples m ay be analyzed by ETS-8-044.0 "Determ ination o f Perfluorinated Compounds In W ater by High Performance liq u id Chrom atography/M ass Spectrometry Direct Injection Analysis" or ETS-8-110.1 "Method o f Analysis fo r the Determ ination o f Perfluorinated Compounds in W ater, S oil and Sedim ent by LC/MS/MS". REASON; Method ETS-8-154 is typically used for samples that contain perfluorinated compounds In the concentration range from 0.025 ng/m L to 25 n g/m L Previous analysis o f groundwater samples from the Cordova area (Interim reporL#1)'produced sample results at levels that were greeter than 25 ng/m L. The reason for this amendment is to allow fo r foe use of methods ETS-8-110 and ETS-8-044, which are better suited for foe analysis o f samples o f varying concentrations. E07-0149; Interim Report #2 3M Cordova G roundwater. December 2009 Page 3 of 4 Page 75 oM 45 CONFIDENTIAL Amendment Approval 3M Protocol E07-0149 A m endm ents -- -- __________________________________/ / A s * i / < a c 0 ? 07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 P ag e4o f4 Page 76 of 145 CONFIDENTIAL A t t a c h m e n t C : E x t r a c t io n a n d A n a l y t ic a l M e t h o d s E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 77 of CONFIDENTIAL Document may be used, if current for ;4 days: from 02/ 8 M B n i i w i n a t i ta l L fllm iM iif y Method Analysis of Ftuorochemicals in Extracts Using HPLC-Electrospray/Mass Spectrometry/Mass Spectrometry Method Number: ETS-8-110.01 Adoption Date: 08 Sept 1999 Revision Date; Upon signing Effective Date: j0f(3 h i Approved By: W illiam K. Reagen Manager Date Analysis of FluorocheEmTicSa-l8s-i1n1E0.x0t1racts Using LC/MS/MS EO7-O140; Interim Report #2 3M Cordova Groundwater * December 2009 Page 1 of 10 Page 78 o f 145 p. 84 CONFIDENTIAL O o c u Y 'tn t r-.v-i b e i se e ' -i u . r ^ t fo Fror--: Q 2i(:V2Q 1 Scope and Application The method describes the analysis of fluorochemicals (typically perfluoronated adds, alcohols, amides, and sulfonates) using HPLC-mass spectrometry/mass spectrometry. Specific analytes, ions (parent and daughter) matrices, solvents, solutions, quality controls, internal standards(s), and other parameters w ill be defined in the protocol or the sample preparation w o rksh e e t^). , Applicable Compounds: EJectrospray ionizable fluorochemicals. Matrices: To include, but not limited to, water, aqueous solutions, organic solvents, soils, tissues, and serum. The matrix will be defined b the ^srotocbl or sample preparation worksheets). 2 Method Summ ary < v- \ This method describes the analysis of electropray ioriizable fluorochemicals using HPLC-electrospray tandem mass spectrometry (HPLC-ES/M^/MS). The analysis is performed by following the mass selection of a single ion characteristic of a particular fluorochemical, such as the perfluorooctanesulfonate (PFOS) anion, m /z - 499 or perfluorooctanoate (PFOA), m/z = 413. A compound specific product ion is created through high-energy collisions, and the creation of the product Ion is quantitatively monitored. For example, the transition from 499 > 99 (characteristic o f FSQ r) is monitored for PFOS and the 413 >119 (characteristic of C2F5-) transition is monitored for PFOA. This selectivity afforded by this technique reduces background interferences and enhances analytical sensitivity. 3 Definitions 3.1 Atm ospheric Pressure Ionization (API): Commercially available LC/MS and LC/MS/MS systems allow for various methods o f ionization by utilizing a variety of sources, probes, and interfaces. These include but are not limited to: Electrospray Ionization (ESI), Atmospheric Pressure chemical Ionization (APcI). The ionization in these processes occurs at atmospheric pressure (i.e., not under a vacuum). 3.2 Electrospray Ionization (ES, ESI): A method of ionization performed at atmospheric pressure, whereby ions in solution are transferred to the gas phase via tiny charged droplets. These droplets are produced by the application of a strong electrical field. Typically, this is for the analysis of fluorochemicals. 3.3 Mass Spectrom eter (MS) or Tandem Mass Spectrom eter (MS/MS): Single mass spectrometer QMS) or Tandem mass spectrometers (MS/MS) systems are equipped with quadrupofe mass selective detectors. Ions are selectively discriminated by mass to charge ratio (m/z) and subsequently detected. A single MS may be employed for ion detection or tandem MS (MS/MS) may be employed to obtain specific fragmentation information. 4 W arnings and Cautions 4.1 Health and Safety Always wear appropriate personal protective equipments such as protective gloves, eye protection, and appropriate clothing when working with biological matrices, solvents, chemicals E T S -8 -1 10.01 Analysis o f Fluorochem icals in Extracts Using LC/MS/MS E07-0149: Interim Report *2 3M Cordova' Groundwater - December 2009 Page 2 o f 10 Page 79 of 145 p. 85 CONFIDENTIAL Document may be used, if current, for 14 oay* (roti! 02*02; and instrumentation. For potential hazard information refer to material safety data sheets, packing material, the 3M Environmental Laboratory's Chemical Hazard Review, tire 3M Guide to Laboratory Practices or other information as appropriate. 4.2 Cautions The analyst must be familiar with the laboratory equipment and potential hazards inducting, but not limited to, the use o f biological materials, solvente, high temperatures, pressurized gas and solvent lines, high voltage, and vacuum systems. Refer to the appropriate equipment procedure or operator manual for additional information and cautions. 5 Interferences To minimize interferences when analyzing samples, use containers and instruments parts that will not contaminate the sample(s) or extracts). Co-extracted matrix components may enhance or suppress the measured analyte signal in the mass spectrometer. These effects are minimized using an 8 PE technique, but the.precision and accuracy of spike results must be evaluated for possible effects of coextracted matrix interferences that may be present. 6 Instrum entation, Supplies, and Materials_______ ______ .______ 6.1 Instrum entation Equipment listed below may be modified in order to optimize the system. Document the actual configuration in the raw data and in the Analytical Equipment Systems documentation or other equivalent documentation system. Agilent HPLC1100 system: Pump: Quaternary Pump, Agilent, Model G1311; or Binary Pump, Agilent, Model 1312 or equivalent. Solvent Degasser, Agilent, Mode) G1322A or equivalent. Autosampler, Agilent, Model G1313A, or Thermostated Autosampler, Agilent, Model G1329A or equivalent. Autosampler thermostat (used with the ThermostatedAutosamplar), Agilent, Model G133QA or equivalent Column Compartment (Temperature Controlled), Agilent, Model G1316A or equivalent. Diode Array Detector, (DAD) Agilent, Model # G1315A or equivalent. Controller, Hand Held, Agilent, Model # G1323A or equivalent UltimaTM, Tandem MS, Micromass, or Quattro II, Tandem MS, Micromass, or equivalent Capillary Pump, Waters, Model CAPLC, or equivalent Capillary Autosampler, Spark-Holland, Model SPF, or equivalent. Computer Hard Drive, Compaq AP200 or better, or equivalent System control/data analysis software: MassLynxTM, Version 3.4 or better, or equivalent. Other instrumentation as needed, document as appropriate. Analysis of FluorochemETicSa-ls8-i1n1E0.x0t1racts Using LC/MS/MS E07-0148; Interim Report #2 3M Cordova Groundwater - December 2009 Page 3 o f 10 Page 80 ot 145 p. 86 CONFIDENTIAL Document may be used, if ouiY.-'n fo> "4 days fror, 0?A13-'20*:C 9.2 Supplies Tubing: PEEK, stainless steel, etc. Ferrules and other connective parts. Autovials and caps : 6.3 M aterials High purity grade nitrogen gas regulated to approximately 100 psi (or other suitable gas system). High purity grade collision gas, argon. HPLC analytical columns. Guard Columns. > Crimpers '-.-0 '"1 : 'S . 7 Reagents and Standards : D. B , 7.1 Reagents Methanol, HPLC grade.or equivalent. . l' ASTM Type I W ater or equivalent. All water used in this method should be ASTM Type I or equivalent, and may be provided by a M ili-Q TOC Plus System or by another system or vendor, provided there is adequate documentation o f the s o u r c e , , .... ., Ammonium Acetate, reagent grade or equivalent When preparing cffferent amounts than those listed, adjust accordingly. 2.0 mmol/L ammonium acetate solution. Weigh approximately 0.300 g of ammonium acetate tc a 2 L volumetric flask. Add water to the mark and. mix until all solids are dissolved. Store at room temperature. Other solvents and solutions may be used as stated in the protocol or in the sample preparation worksheets). Document all solvents and solutions used in the appropriate logs or media. 7.2 Calibration Standards Typically, a minimum of 6 standards a re analyzed with each group of samples. 8 Sam ple Handling / tr . , - i Standards, sample extracts, and prepared samples may be stored in capped autovials, capped 15m L centrifuge tube, or other suitable containers ^ f Analysis. If analysis will be delayed, standard^,'sample extracts; and prepared samples may be refrigerated at approximately 4*C until the analysis can be performed. Appropriate sample storage conditions w ill be evaluated on a case-by-case basis, and will be addressed in the protocol o r by the analyst in the raw data and/or prep worksheets. ; r. \ > 9 Q uality Control The following quality control is recommended for this method. If an approved protocol or extraction procedure is used for the samples, any quality procedures described therein takes precedence over the quality control in this method. For non-GLP studies without protocols or Analysis of FluorochemETicSa-l8s-i1n1E0.x0t1racts Using LC/MS/MS E07-0149: Interim Report *2 3M Cordova Groundwater - December 2009 Page 4 of 10 Page 81 of 145 p. 87 extraction methods, document the chosen quality control on the sample preparation worksheets and or the final report 9.1 Blanks 9.1.1 Solvent Blank Solvent blanks are not extracted. They are.analyzed with each sample set to determine contamination or carryover. The solvent used should* in some approximation, represent the solvent used for the standard curve and/or the sample extracts. Solvent blank area counts should be less than 50% o f the area count of the lowest calibration standard. Solvent blanks should be analyzed prior to each calibration curve, if carryover is a problem consecutive solvent blanks may be necessary. Solvent blank area counts should be less than 50% o f the area count o f the lowest calibration standard prior to the injection o f unknown samples. 9.1.2 Method Blank Method blanks are extracted and analyzed with each group of samples, consisting of water or another commercially available solvent: The protocol or project lead will define the number and frequency o f these samples. Method blanks should have area counts less than 50% o f the area count of the lowest calibration standard. 9.1.3 Matrix Blank Matrix blanks are extracted and analyzed with each group of samples. These groups would include tissue and sera samples. Endogenous levels o f target analytes contained in the sample matrix are evaluated by taking an aliquot o f blank (unexposed) matrix and carrying it through the entire extraction process alongside the samples. The protocol or project lead will define the number and frequency o f these samples. Matrix blanks should have area counts less than 50% of the area count of the lowest calibration standard. If this is not possible in cases where there are detectable levels of endogenous target analyte present in the matrix, then the endogenous levels should be taken into account when evaluating sample data and discussed in the raw data. 9.2 Surrogate A surrogate standard may be used for quality control. The surrogate is used to qualitatively evaluate the entire analytical procedure including sample preparation and analysis. The surrogate should be spiked at the beginning of the sample preparation and should tell within the low to mid-range o f the calibration curve. 9.3 Post-Extraction Control Sample Post-extraction control samples may be prepared for each set o f extracted samples (if applicable to the study) and analyzed to determine extraction stability. The samples are prepared by adding additional target analyte to the final extract, and after any dilution. Post-extraction control sample duplicates may be prepared periodically to measure the precision associated with the analysis. These samples should be analyzed in the same run as the unsplked sample. Post-extraction control sample concentrations should fall in the mid-range of tie initial calibration curve or should be prepared at 1.5-5 times the endogenous concentration of the analyte. Spike concentrations should fall in the law-range of the Initial calibration curve if extremely low levels are expected Analysis of FluorochemETicSa-l8s-i1n1E0.x0t1racts Using LC/MS/MS E07-0149; Interim Report #2 3M Cordova Groundwater December 2Q09 Page 5 o f 10 Page 82 of 145 p. 88 CONFIDENTIAL Document may be used. :f current, for 14 days from 02/03/20 -0 10 Calibration and Standardization 10.1 Instrum ent Calibration Analyze the standard curves prior to each set of samples. The standard curve may be plotted by linear regression (y = mx + b) or quadratic tit (y * ax2+ b x + C); weighted 1/x or unweighted, using MassLynxTM or other suitable software. The calibration curves may include but should not be forced through zero. The mathematical method used to calculate the calibration curve should be applied consistently throughout a study. Any change should be thoroughly documented in the raw data. If the calibration curve does not meet adceptanoe criteria perform routine maintenance or prepare a new standard curve (if necessary>and reanalyze:' For purposes of accuracy when quantitating low levels o f analyte, it may be necessary to use the low end of the calibration curve rather than the full range. Example: when attempting to quantitate approximately 10 ppb o f analyte, generate a calibration curve consisting o f the standards from 5 ppb to 100 ppb rather than the full range of the curve (5 ppb to 1000 ppb). This w ill reduce inaccuracy attributed to linear regression weighting o f high concentration standards. High and/or low points may be excluded from the calibration curves to provide a better fit over the linear range appropriate to the data or because they dkl notm eet the predeterm ined acceptance criteria. Low-level curve points should also be excluded if their area counts are not at least twice that o f the method blanks. Any curve point may be rejected due to a bad injection or if a possible prep error can be deduced by the raw data. Justification for exclusion of calibration curve points will be noted In the raw data. '. i 'U! J - i A minimum o f 6 points will be used to constructthe calibration curve. 10.2 Internal Standard ,, An internal standard (IS) may be used to quantify the target analytes by establishing a relationship between the ratio o f analyte response fo is response a id a known concentration of the analyte of interest. The IS should be spiked at aparnount that w il foil within the mid-range of the calibration curve. The IS should be added after tlte,^(tiactfon process and before analysis 10.3 Continuing Calibration Vrification (CCV) Continuing calibration verifications (CCV) are analyzed to verify the continued accuracy o f the calibration curve. i; . i i ' - Analyze a mid-range calibration stantiard(at a'minimum) after every tenth sample, not including solvent blanks, with a minimum of one per sarfipteset. Calibration verification injections must be within 25% to be considered acceptable. The calibration curve and the last passing CCV will then bracket acceptable samples. Multiple CCV levels may be used. The CCVs used should be documented in th e . raw data 11 Procedures For instrument set-up, refer to th manual that pertains to the specific instrum ent Actual parameters w ill be recorded on the instrument printouts/ The procedures that follow are from Micromass9 instruments using MassLynxTM. Conditions may be adjusted, provided adequate QC is used. Analysis of FluorochemETicSa-l8s-i1n1E0.x0t1racts Using LC/MS/MS E07-014B; Interim Report #2 3M Cordova Groundwater December 2009 P age0 o f 10 Page 83 of 145 CONFIDENTIAL Document may be used r currem for 14 days vm 0?/0 11.1 Tune Page The Tune Page controls many o f the MS system parameters. Open up the Tune Page and review the parameters, change if necessary. Selected parameters and their recommended initial settings are as follows: Tune Page Initial Conditions: Sot. ice Setting Anslyze' Sen ng Capillary 2 LM Res 1 15 Cone 20 H M R e sI 15 Source Block Temp 160 (on Energy ((energy) 1 2 Desolvation Temp 250 LM Res 2 14 Analyze' Sot:ipg HM Res 2 14 M ultiplier 650 Ion Energy (lenergy) 2 2 Ensure that the instrument is operating and that the appropriate gases are on. 11.2 Inlet Editor The Inlet Editor contains all of the parameters for the LC. Open the Inlet Editor, use the existing method or load a different method. Review the parameters and change if necessary. Selected parameters and their recommended initial settings are as follows: LC Pump Initial Conditions: Parameter Setting Gradient Initial Conditions: Solvent A 90 S olvents 10 Flow Rate (mL/min) 0.300 Stop Time (mins) 10 Max Pressure (bar) 400 Oven Temp Left (C) 30 Oven Temp Right <C) 30 L.___-- Ime 0.00 1.00 5.50 7.50 8.00 C'% 10% 10% 95% 95% 10% Analysis of FluorochemETicSa-l8s-i1n1E0.x0t1racts Using LC/MS/MS E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 7 of 10 Page 84 of 145 CONFIDENTIAL rovurrer t :o.?y b?v j ' ..ure1'! for -4 days from 02. Autosampler Initial Conditions: 3r3!i pt " NRlinr: Draw Speed ' 200.0 Eject Speed (uL/min) 200 Draw Position (mm) 0.00 Stop Time (mins) .1 .. Injection Volvm e(uL) 10.00 10.0 It is recommended, for consistency, that the aqueous solution is in Pump A and the organic solvent is always in Pump B. ^,. Save the method with an appropriate method name. Check the solvent levels In the reservoirs and refill if necessary. Load the method and turn cm the solvent flow. 11.3 Function list editor Create a MS acquisition method appropriate for the data needed. See the Micromass* MassLynxTM "Guide To Data Acquisition" for additional jnforrnation. Selected parameters and their recommended initial settings follow. Ion information is not listed due to the numerous possible ions o f interest and their daughter ions. MS Initial Conditions: , Solvent Delay Mode ., Interchannel Delay (Secs) Span (Dltons) St^rt Time (Mins)1 End Tim (M ins) ' Repeats 0.00 ESP- 0.07 0.00 0.00 10.0 1 12 Data Analysis and Calculations Calculations (including, but not limited to): , -4 Calculate matrix spike percent recoveries using the flo w in g equation: % R eco very = bserved Re.^ L ~ Background Re s u it. 1QQ Expected Result Calculate percent difference using the following equation: %Difference - ^ alculatecl Concentration - Expected Concentration , ^ Expected Concentration Analysis of FluorochemETicSa-l8s-i1n1E0.x0t1racts Using LC/MS/MS E07-0149; Interim Report 2 3M Cordova Groundwater - December 2009 Page 8 of 10 Page 85 of 145 CONFIDENTIAL Document may be used, if current, for 14 days from 02/0 13 Method Perform ance Criteria listed in a protocol will supercede this method. Document any changes from the method in the protocol, raw data and/or the report. If criteria listed in this method performance section are not met, maintenance may be performed on the system and samples reanalyzed o r other actions as determined by the analyst Document all actions in the raw data. If data is to be reported when performance criteria have not been met, the data must be footnoted on tables and discussed in the text of the report. 13.1 System Suitability A minimum of three system suitability samples m il be injected at the beginning o f each analytical run. Typically these samples are run prior to the calibration durve. The system suitability injections must have area counts with an RSD of 5% and a retention time RSD o f s2%. 13.2 Q uantitation The coefficient o f determination (r2) value for the calibration curve must be greater than or equal to 0.990. Each point in the curve must be within 25% of the theoretical concentration with the exception of the LLOQ, which may be within 30%. 13.3 Lower Lim it of Q uantitation The Lower Limit o f Quantitation (LLOQ) is analyte and matrix specific. For most analytes, the LLOQ concentration is selected as the lowest acceptable non-zero standard in the calibration curve. Solvent, matrix and method blank area counts must be < % that o f the lowest standard used in the calibration curve. This is not always possible for matrix blanks, where there may be detectable levels of target analytes. The endogenous levels, if any should be taken into account when evaluating sample data and discussed in the raw data. 14 Pollution Prevention and W aste Management Sample extract waste and flammable solvent is disposed in high BTU containers, and glass pipette waste is disposed in broken glass containers located in the laboratory. 15 Records Record data per the laboratory's standard operating procedures. 16 Attachm ents None. 17 References ETS-9-024, "Operation and Maintenance of Micromass Triple Quadrupole Mass Spectrometers fitted with Atmospheric Pressure Ionization Source'. Analysis of FluorochemETicSa-l8s-i1n1E0.x0t1racts Using LC/MS/MS E07-0149; Interim Report #2 3M Cordova Groundwater December: 2009 Page 9 o f 10 Page 86 of 145 CONFIDENTIAL 0 , . c r ^ n in?y be u$ec .. i i'>< 14 days from 'V.-vO-ir 18 Affected Documents None. 19 Revisions R evision Number 1 .. Summary o f Changes Updated to the new form at. Changed the title to allow fo r m ore types o f matrices to be tested. Revised the m ethod to include the new requirem ents of the new form at. Removed or m odified the.definitions,In Section 3. ! Analysis of FluorochEmTicSa-l8s-i1n1E0.x0t1racts Using LC/MS/MS E07-0149; Interim Report #2 3M Cordova Groundwater December 2009 Page 10 o f 10 Page 87 of US Document may be used, !' current, for 14 days ficm D2/03/201 CONFIDENTIAL 3M Environm ental Laboratory Method Determination of PerfluorinatedAcids, Alcohols, Amides, and Sulfonates In Water By Solid Phase Extraction andHigh Performance Liquid Chromatography/Mass Spectrometry MethodNumber: ETS-8-154.3 Adoption Date: 28Apr 2000 Revision Date: Upon Signing Effective Date: 0 % [ z H /o l Approved By: William K. Reagen Manager Date DePtehramsineaEtixotnraocftiPoenraflunodriHniagthedPeArcfEoidrTmsS,aA-n8lcc-1oeh5Lo4iql.s3u,iAdmCihdreosm, aantodgSrauplfhoyn/aMteasssInSWpeaPcttearogrmbeye1tSroyofli2d0 E07-0149; Interim Report #2 3M Cordova Groundwater December 2009 Page 88 ot 148 p. 94 Document may be used, <: cuneni for 14 days from 02/03/201C CONFIDENTIAL 1 Scope and Application This method describes the extraction o f target analytes from water matrices using solid phase extraction (SPE) followed by separation, identification, and quantitation using high-performance liquid chromatography mass spectrometry (HPIC/M S) or tandem mass spectrometry (HPLC/MS/MS). This method has been validated for periluorooctane sulfonate (PFOS), perfluorooctane sulfonytamide (FOSA), and perfluorooctanoate (PFOA) in groundwater, surface water, and drinking water samptes. This method is considered a perform ance-based method and may be applied to the determination of other perfluorinated adds, alcohols, amides, and sulfonates in similar matrices, as long as the defined QC elements are satisfied and with the understanding that the method Is not validated for compounds outside the scope of the original protocol. ...... , This method is based in part on the 3M Environmental Laboratory report E01-0454, ` Method o f Analysis for the Determination of Pedluofooctpne sulfonate (PFOS), Perfluorooctane sulfonytamide (PFOSA), and Perfluorooctanoate (PQAA) in Water", as developed and validated by Exygen Research (formerly Centre Ang^tical Laboratories, Inc.). This method was originally validated using a 40 mL sample aliquot for extraction and a final elution volume o f 5 mL. These volumes may be changed on a per prqject basis to meet the data quality objectives set forth by the prqject lead. Acceptable recoveries o f laboratory quality control samples w ill demonstrate that the extraction and elution volumes do not impact the validity of the method. Sample collection is n o t covered under this analytical procedure. 2 Method Sum m ary Water samples are collected from a site o f interest and shipped to the analytical facility. Perfluorinated acids, alcohols, amides, and sulfonates are extracted from aliquots of the water samples using solid phase extraction (SPE) cartridges. The compounds are eluted from the SPE cartridge, using methanol. Separation, identification, and measurement are accomplished by high-performance liquid chromatography/ tandem mass spectrometry (HPLC/MS/MS) analysis, high-performance liquid chromatography/mass spectrometry (HPLC/MS) may be used if the defined QC elements are satisfied and meets the data quality objectives outlined in the general project outline for the given project. The concentration of each identified component is measured by comparing the MS response of the quantitation ion (or summed total o f multiple ions) produced by that compound to the MS response o f the quantitation ion (or summed total o f multiple ions) produced by the same compound in an extracted calibration standard (external standard). 3 Definitions 3.1 SPE cartridge A column containing an open solvent reservoir, retaining frit, sorbent bed, retaining frit, and luer tip. The sorbent bed is bonded silica which is designed to selectively retain o r elute the compounds o f interest depending on the solvent conditions. The compounds o f interest can be separated from the water matrices and introduced into an appropriate solvent for analysis. 3.2 Analytical Sam ple A portion o f an extracted laboratory sample prepared for analysis. DePtehramsineaEtixotnraocftiPoneraflunodrHiniagthedPeArdfEodrTmsS,aA-n8lcc-1oeh5Lo4iql.s3u,iAdmCihdreosm, aantodgSrauplfhoyn/aMteasssInSWpeaPcttaerogrmbeye2tSroyofli2d0 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2000 Page 89 of 145 CONFIDENTIAL 3.3 Calibration Standard An aqueous solution prepared by spiking a known volume o f the Working Standard (WS) into a predetermined amount of ASTM type I water, HPLC grade reagent water, or other suitable water (Le. matrix water), and extracting the solution according to this method- The calibration standard solutions are used to calibrate the instrument response with respect to analyte concentration. ; 3.4 Laboratory Duplicate Sample (LDS) A laboratory duplkatq,sample is a separate aliquot o f a sample, taken in the analytical laboratory that is extracted ancl analyzed Separately with identical procedures. Analysis of LDSs compared to that of the first aliquot give a measure o f the precision associated with laboratory procedures, but not with sample collection, preservation, or storage procedures. 3.5 Field Blank (FB)/Trip Blank ASTM Type I water, HPLC grade reagent water, or other suitable water, is placed in a sample container in the laboratory and treated as a sample in all respects, inducing exposure to sampling site conditions, storage, preservation and all analytical procedures. The purpose of the F B isto determine if test substances or other interferences are present in the field environment.' This sample is also'refenred to as a Trip Blank. 3.6 Field Duplicate Sam ple (FDS) A sample collected in duplicate at the same time from the same location as the sample. The FDS is placed under identical drcumstances and treated exactly the same throughout field and laboratory procedures. Analysis o f the FDS compared to that o f the first sample gives a measure of the predsion assodated with sample collection, preservation and storage, as well as with laboratory procedures. 3.7 Field M atrix Spike (FMS) A sample to which known quantities of th target analytes are added to the sample bottle in the field or in the laboratory before the bottles are sent to the field. A known, spedfic volume o f sample must be added to the sample container without rinsing. This may be accomplished by making a "fill to this level" line on the outside o f the sample container. The FMS should be spiked at approximately 0.5-10 times the expected analyte concentration in the sample. If the expected range of analyte concentrations is unknown, multiple spikes at varying levels may be prepared to increase the likelihood that a spike at pn appropriate level is made. Typically a low and a high spike re prepared for each sampling location. The FMS is analyzed to ascertain if matrix effects or sample holding time contributes bias to the analytical results. 3.8 Field Spike Control Sample (FSCS)/Trip Blank M atrix Spike An aliquot o f ASTM Type I water (HPLC grad reagent water or other suitable water may used) to which known quantities of foe target analytes are added in the field at foe time of sample collection (at an appropriate concentration to be determined by foe project lead) or in the laboratory prior to foe shipment o f the collection bottles. The FSCS is extracted and analyzed exactly like a sample to determine whether a loss of analyte could be attributed to holding time, sample storage and/or shipment issues. A lo w and high FSCS may be appropriate when expected sample concentrations are not known. This sample may also be referred to as Trip Blank Matrix Spfte. 3.9 Laboratory Control Sample (LCS) An aliquot o f ASTM Type I water (HPLC grade reagent water or other suitable water may used) to which known quantities o f the target analytes are added in foe laboratory at foe time o f sample extraction. At least two levels are included, one generally at the low end o f foe calibration curve ETS-8-154.3 Page 3 of 20 Determination o f Perfluorinated Adds, Alcohols, Amides, and Sulfonates In Water By solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 90 o f 145 p. 96 Occ.irper; may he v>secl. if ru"sn< 'or 14 csyr- Trr. CONFIDENTIAL C V sO V .. and one near the mid to upper range o f the curve. The LCSs are extracted and analyzed exactly like a laboratory sample to determine whether die method is in control. LCSs should be prepared each day'samples are extracted. ;1 3.10 LaboratoryM atrlx Spike(LM S) A laboratory matrix spike is an aliquot o f a sample to which known quantities o f target analytes are added in the laboratory. The LMS is extracted and analyzed exactly like a laboratory sample to determlne.wheth^r.the.sample matrix contributes Was to the analytical results. The endogenous concentrations of die analytes in the sample matrix must be determined in a separate afiquot and the m easuredvaluesinthe L^S con re ^dfortfiese co nce ntra tion s. 3.11 Laboratory Sample A portion or aliquot of a sample received from the field for testing. :3.12 L lib it6 fQ u ^ n tlta tio n (L 9 Q lj' ^ V / The lower lim it o f quantitation (LLOQ) for a dataset is the lowest concentration that can be reliably quarttftated within the specified limits of precision and accuracy during routine operating * conditions. To simplify data reporting, the LLOQ is generally selected as the lowest non-zero standard in the calibration curve that meets method criteria. Sample LLOQs are matrix- dependent. * The upper limit o f quatitation (ULOQ)for a dataset is the highest concentration that can be reliably quantitatied within the specified lim its o f precision and accuracy during routine operating conditions. The highest standard in the calibration curve that meets method criteria is defined as th eU L O Q . v x. 3.13 Method Blank An aliquot o f ASTM Type I water (HPLC grade reagent water or other suitable water may used) that is treated exactly like a laboratory sample including exposure to all glassware, equipment, solvents, and reagents that are used With other laboratory samples. The method blank is used to determine if test substances or otherlnterferences are present in the laboratory environment, the reagents, or the apparatus. ' t " i- 3.14 Sam ple : A sample is a small portion Collected fre m a i^ g e r quantity o f material intended to represent the original source material. .7 "7 3.15 Stock Standard Solution (SSS) A concentrated solution o f a,single analyte,j)i;eparpd in the laboratory with an assayed reference compound. '... ; 3.16 Surrogate ! 77. A compound similar to the target anatytefs) in chemical composition and behavior that is not normally found in the sample(s). A 'surrogate compound typically a target analyte with at least one atom containing an isotopically labeled substitution. If used, surrogate^) are added to all samples and quality control samples (except solvent blanks and half of the prepared method blanks). Surrogate^) are added to quantitatively evaluate the entire analytical procedure inducting sample collection, extraction, and analysis. Indusion of a surrogate analyte is an optional quality control measure and is NOT required. The project lead should indicate in the general project outllne/protoCol whether or not a surrogate compound will be part of the analysis. DePtehramsineaEtixotnraocftiPoenraflunodriHniagthedPeArcfEoidrTmsS,aA-n8lcc-o1eh5Lo4iql.s3u,iAdmCihdreosm, aantodgSrauplfhoyn/aMteasssInSWpeaPctatergormeby4etbroyofn2d0 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 91 of 145 Duairreni may be i sed CONFIDENTIAL p. 97 for U o<iyz fr-:*r: 02 3.17 W orking Standard (WS) A solution of several analytes prepared in the laboratory from SSSs and diluted as needed to prepare calibration standards and other required analyte solutions. 4 W arnings and Cautions . '.______ ' 4.1 Health and Safety The acute and chronic toxicity o f the standards for this method have not been precisely determined; however, each should be boated as a potential health hazard. Unknown samples may contain high concentrations of volatile toxic compounds. Sample containers should be opened in a hood and handled with gloves to prevent ejgjosure. The laboratory is responsible for maintaining a sate work environment and a current awareness of local regulations regarding the handling of the chemicals used in this method. A reference file o f material safety data sheets (MSDS) should be available to all personnel involved in these analyses. 4.2 Cautions The analyst must be familiar with the laboratory equipment and potential hazards including, but not limited too, the use of solvents, pressurized gas and solvent lines, high voltage, and vacuum systems. Refer to fee appropriate equipment procedure or operator manual for addfflonal information and cautions. S interferences During extraction and analysis, be aware o f potential contaminant sources from reagents and solid phase extraction devices. u All materials used in the analyses shall be demonstrated to be te e from interferences under conditions o f analysis by running method blanks. Parts and supplies that contain Teflon should be avoided or minimized due to the possibility of interference and/or contamination. These may include^ but are not limited to: wash bottles, Teflon lined caps, autovial caps, HPLC parts, etc. The use o f disposable micropipettes or pipettes to aliquot standard solutions is recommended to make caKbration standards and matrix spikes. 6 Instrum entation, Supplies, and M aterials Note: Brand names, suppliers, and part numbers are for illustrative purposes only. Equivalent performance may be achieved using apparatus and materials other than those specified here. Demonstration o f equivalent performance (quality control samples meeting method acceptance criteria) is fee responsibility o f the laboratory performing the analysis. 6.1 Instrum entation Balance, analytical (display at least 0.0001 g), MetHer HPLC/MS/MS or HPLC/MS system, as described in Section 10. 6.2 Supplies and M aterials. DePtehramsienaEtixotnraocftioPneraflunodrHinaigthedPeArdfoEdrTmsS,aA-8nlcc-1oe5hL4oiql.s3u,iAdmCihdreosm, aantodgSrauplfhoyn/aMteasssInSWpeaPctaetrogrmtetye5stroyoflid20 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 92 o f 145 L 'ii' ' ;IT t * : i rt^ y ir,j CONFIDENTIAL p. 98 Sample collection bottles--LDPE (e.g., NalgeneTM) narrow-mouth bottles with screw cap. Note: Do not use Teflon bottles or Teflon lined caps. Coders or boxes for sample shipm ent AutoTrace automated SPE workstation, Caliper Life Sciences. A manual SPE manifold with vacuum pump may be used if desired. Supplies for the manual SPE manifold are included below.) Vacuum pump, BOchi. Visiprep vacuum manifold, Supek. 15mL disposable polypropylene centrifuge tubes, VWFL 50mL disposable polypropylene centrifuge tubes! VWR Sep Pak Vac 6cc (ig ) tC18 cartridges.,(part # WAT 036795), Wiaters. (Cartridges with other amount or types o f sorbent material m ay be used depending On the data quality objectives o f the project'.) \ . 15 m l disposable culture tubes (17 x 100 mm), VWR (C at No. 60818-626). Disposable micropipettes (50-1 OOpL, 100-200pL), Drummond. Class A pipettes and volumetric flasks, various. LDPE narrow-mouth bottles, Nalgene (volumes may vary depending on analytical needs). 2 mL dear HPLC via lkit (cat# 5181-3400), Xgilerit/He\Mett Packard. Standard lab equipment (graduated cyinders, disposable tubes, etc.), various. 7 Reagents and Standards ______________________________ Note: Suppliers and catalog numbers are for illustrative purposes only. Equivalent performance may be achieved using chemicals obtained from other suppliers. Do not use a lesser grade of chemical than those listed. 7.1 Chem icals Methanol (MeOH), HPLC grade, JT Baker, Catalog No. JT9093-2. Ammonium Acetate, Reagent grade, Sigma-Aldrich, Catalog No. A-7330. ASTM Type I Water, prepared in-house (HPLC grade reagent water or other suitable water may also be used) Sodium Thiosulfate, Reagent grade, JT B akers 7.2 Standards ;f PFBA, Heptafluorobutyric Add, (C< Perfluorinated Acid) NFPA, Nonafluoropentanoic Add(C*Perfluonnated Add) PFHA, Perfluorohexanoic Add (Ce Perfluorinated Add) TDHA, Tridecafluoroheptanoic Acid, (C7Perfluorinated Add) PFOA, Ammonium perfluorooctanoate, (Ce Perfluorinated Add) Ce Add, Heptadecafluorononanoic Add PFDA, Nonadecafluorodecanoic Add (Cio Perfluorinated Add) DePtehramsienaEtixotnraocftioPneraflundoriHnaigthedPeArdfoEdrTmsS,aA-8nlcc-1oe5hL4oiql.s3u,iAdmCihdreosm, aantodgSrauplfhoyn/aMteasssInSWpeaPctaetrgormbey6estroyoflid20 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 93 of 145 p. 99 ccutr-'( may be :.'&r 'current, for 14 ays from 02/03/2010 CONFIDENTIAL Cn Add, Perfluoroundecanoic Add C12Add, Perfiuorododecanoic Acid FBSA, PertuorobUtanesulfonamide FOSA, Perfluorooctanesulfonylamide PFBS, Potassium Perfluorobutanesutfbnate PFHS, Perfluorohexanesulfonate PFQS, Potassium perfluorooctanesullbnate r THPFOS, 1H, 1H( 2H, 2H-perfluorooctanesulfonic Acid THPFDS. IH, IH, 2H, 2H-perfluorodecanesulfonic Acid PFOA [1,2-13C], 13C isotopically labeled perfluorooctanoic acid, Perkin Elmer PFOS ["O d , " 0 2isotopically labeled Ammonium Perfluoroocatanesulfbnate Others as required. 7.3 Reagent Preparation 250 mg/mL sodium thiosulfate solution -- Dissolve 25g of sodium thiosulfate in 100 mL reagent water. 2 mM ammonium acetate solution (Analysis)--w eigh 0.3 g of ammonium acetate and dissolve in 2.0 L of reagent water. Note: Alternative volumes may be prepared as long as the ratios of the solvent to solute ratios are maintained. 7.4 Stock Standard Solution (SSS) and W orking Standard Solution Preparation The following standard preparation procedure serves as an example. Weighed amounts and final volumes may be changed to suit the needs of a particular study. For example, pL volumes may be spiked into volumetric flasks when diluting stock solutions to appropriate levels. 100 pg/m L ta rg e t analyte SSSs--Weigh out 10 mg of analytical standard (corrected fo r percent s a lt a nd p u rity and dilute to 10QmL with methanol or other suitable solvent, in a 100mL volumetric flask. Transfer to a 125mL LDPE bottle or other suitable container. Prepare a separate solution for each analyte. Expiration dates and storage conditions of stock solutions should be assigned in accordance with laboratory standard operating procedure. An example of purity and salt correction is given below for PFOS. sa,,lt correc.t.ion ,fac.tor = --m o-le--c--u--la--r--w---e-i=g-h--t--o--f-a---nionm oclecular weight o f salt 499 PFOS (K +)salt correction factor * ---- = 0.9275 538 10 mg CbFitSGj'IO with purity 90% * 8.35mg C8F17S03~(10 mg*0.90*0.9275=8.35 mg) 1 pg/m L (1000 ng/m L) m ixed w orking standard--Add 1.OmL each of the 100pg/mL SSSs to a 10OmL volumetric flask and bring up to volume with solvent. 0.1 pg/m L (100 ng/m L) m ixed w orking standard--Add 10.0m l o f the 1.0pg/mL-mixed working standard solution to a 10OmL volumetric flask and bring up to volume with solvent. DePtehramsienaEtixotnraocftioPneraflnudorHiniagthsdPeArdfEodrTmsS,aA-8nlc-c1oe5hL4oiql.s3u,iAdmCidhreosm, aantodgSrauplfhoyn/aMteasssInSWpeaPctaetrogrmBeye7Stroyoflid20 E07-0149; Interim Report #2 3M Cordova Groundwater December 2009 Page 94 of 145 `'eciren: rryy i>s .`SC-rJ, CONFIDENTIAL p. 100 for 14 days frc-yi 02/0 V? 0.01 pg/m L (10 ng/m L) m ixed standard--Add 10.OmL o f the 0.1 pg/m l-m ixed working standard solution to a 100mL volumetric flask and bring up to volume wrfth solvent Storage C onditions-- Store all SSSs and working standards in accordance with laboratory standard operating procedure or in a refrigerator at 42*C for a maximum period of 6 months from the date o f preparation. 7.5 Calibration Standards Using the working standards described above, prepare calibration solutions in ASTNI Type I water, or other suitable water, using the following table as a guideline. Nate:: Volumes o f water and working standards may be adjusted to m e t the data quality objectives addressed in the general project outline. Calibration levels other than those listed below can be prepared as needed. Concentration o f WS, ng/m L V olum aofW S , F in a l Volunta o f C alibration S tandard (mL ofA S TM Type 1Water, or o ttta rs u ita b la watar) F ina l Concentration of C alibration Standard, ng/m L (ppb) In ASTM T>pe 1 Watar, o r o tita r auHabla w atar 100 10 40 0.025 100 20 40 ' 0.050 100 40 40 0.100 100 100 40 0.250 1000 20 40 0.500 1000 40 40 1.00 1000 10000 100 20 40 40 2.50 5.00 10000 40 40 10.0 10000 100 r . - 0 25.0 The calibration standards ere processed through the entire extraction procedure (Section 11), identical to the laboratory samples. The concentration of the calibration standard in the final extract depends on the volume extracted nd th final elution volume, Final sample concentration factor = Volume .extracted (mLyElution Volume (mL) Storage Conditions-- Store all extracted calibration standards in 1SmL polypropylene tubes or in labeled autovials at 4*2C. After analysis, archiv a l extracted standards with the sample extracts in accordance with laboratory standard operating procdures. 8 Sam ple Collection Bottfe Preparation For most projects, sample collection bottles are prepared by 3M Environmental Laboratory personnel before they are shipped to foe collection site. Typically, four separate collection bottles are associated with a angle colection site; sample, field duplicate sample, low field matrix spike, and high field matrix spike. Depending oh the scope o f the project, additional replicates of the field sample and field matrix spikes may be added. Also, it is not uncommon for additional mid level field matrix spikes to pe collected if the expected sample concentrations are truly unknown or could span a large concentration range. Low-density polyethylene (LOPE) wide-mouth Nalgene bottles are used for the sample collection containers. (Volumes of the bottles may vary depending on how much sample is required to meet DePtehrmasineaEtixotnraocftiPoneraflunodriHnaigthedPeArdfEodrTmsS,aA-8nlcc-1oe5hLo4iql.s3u,iAdmCihdreosm, aantbdgSrauplfhoyn/aMteasssInSWpeaPctaetrogrmbeye8btroyofn2a0 E07-0149; Interim Report 2 3M Cordova Groundwater December 2008 Page 95 of 145 tfi'? . fiiy v CONFIDENTIAL ci."^nt. h ' 14 p. 101 Out data quality objectives.) The interiors o f the Nalgene bottles may be rinsed multiple times with acetone and methanol and allowed to dry before adding the appropriate spikes. Note: rinsing o f the bottles is optional and is not required. The project lead will communicate what the final collection volume w ill be and a corresponding "fill to here' line is drawn on the exterior of the bottle using a permanent marker. Typically, placement o f the `fjtl to here' line is done by using a marker template. Alternatively, bottles with pre-marked volume indicators may be purchased. For the sample bottles designated for matrix spikes, an appropriate volume o f matrix spiking solution is added to the empty bottle. The volume o f spike solution added should produce the desired final concentration of target analytes once the bottle is filled with sample to the 'fill to here line*. (If a surrogate is included for the project, the surrogate compound should also be added to the matrix spikes). The matrix spiking solution should be prepared in a suitable solvent and contains all of the target (and surrogate if applicable) analytes; however, multiple spike solutions m ay be used if an appropriate mixed component standard is not available. The matrix spiking solution is often the same as the working standards used to create the calibration standards. An example of a bottle spike is given below. "Fill to here' volume = 450 m l (A 500 mL Nalgene bottle is used) Desired Field Spike Concentration = 0.1 ng/mL 45pL of a 1 pg/mL spiking solution (containing the target analytes) is added to the bottle and the bottle cap promptly sealed If analysis o f a surrogate analyte Is included in the project objectives, the preparatory analyst should also add an appropriate volume of surrogate standard solution to all the bottles designated as samples or field duplicate samples. All bottles should be clearly labeled to indicate its intended use as a sample/fiekf sample duplicate, low spike, or high spike. If each location has different designated spike levels, toe label should also clearly indicate the sample location designation. Generally, a set o f bottles for a given collection site are then grouped together in plastic bags for Organizational purposes. For each collection event, at least one set of top blank and top blank matrix spikes are prepared. The number o f top blank sets required for a given project will be communicated by the project lead. For the top blank, the surrogate spike is added to the bottle (if included) and then ASTM Type I water (HPLC grade reagent water or other suitable water may used) is added to toe "fill to here' line. The bottle cap is replaced and tape may be placed around the outer edge o f the cap. Trip blank matrix spikes are prepared by adding the appropriate volume of matrix spiking solution, filling the bottle to the desired volume with the appropriate water and replacing and sealing toe cap. The preparatory analyst should document bottle preparation in a Note to File or on a sample preparation worksheet The Note to File should induce the following information: date prepared, total number o f bottles prepared, number o f sample sites, the standard identification numbers and spike volumes used to prepare spiked bottles, toe "till to here' volume, and any other pertinent information needed for reconsiructibility of the data. The Note to File w ill be included in toe final data package for the project. DePtehramsienaEtixotnraocftiPoneraflunodriHnaigthedPeArdfoEdrTmsS,aA-n8lcc-1oe5hLo4iql.s3u,iAdmCihdreosm, aantodgSrauplfhoyn/MateasssInSWpeaPctaetrogrmBeye9Btroyofn2o0 E07-0149; Interim R e p o rt 3M Cordova Groundwater - December 2009 Page 96 of 145 may c-e CONFIDENTIAL p. 102 for I 4 c:3'/.- ?- v \ < M:.' 9 Q uality Control and Data Q uality Objectives Analyticalresults o f the FB, FMS, LMS.FD, and F$CS should be evaluated at the conclusion o f the study to help interpret the quality of sample data. Analytical results for these controt/duplicate samples must be reported with the sample data. ; :-!|.V ,1,:' ' -'il . . ! "j .1 9.1 Solvent Blanks : - SdverXbtenksare analyzed with,each sample set.to determine contamination or carryover. In general, solvent blanks shoyld have area counts that, are less than 50% o f th ar count o f the towestcafibnationstandard, ..... t S o lvlt blanks should be analyzed prior to 'arid following each calibration curve, each set o f system suitabffity sariiples,'and after nOtriore than 10unknown sample extracts, ^instrum ent carryover Is a problem, consecutive solvent blanks may be necessary. In this case the area counts o f the solvent blanks should return to <50% o f the lowest calibration standard prior to the injection o f further standards or samples. ' '1 9.2 Meth od Blanks i' .'i1!,,' o ' '' 1 ' r- 'i'. A method blank consists o f an aliquot of ASTM Type I water (HPLC grade reagent water, or other suitable water may be used) equal in volume to the samples, and extracted in the same manner as the samples. At least five method brahks sHduld be prepared and analyzed each day that extractions are performed for a particular studyref'project Method blanks must be interspersed throughout the extraction batch and analyzed interspersed throughout the analytical sequence. The average area counts for each finalyte mtistbeTeSSthan 50% o f the area count of toe LOQ standard. The standard deviation o fth e area counts should be calculated. A specific %RSD acceptance criteria is not spedfied bgt is assessed cH a batch basis. If the mean area counts of toe method blank exceed 50% of the LOQ stehdaW.th&n the LOQ must be raised to toe first standard level in toe curve that meets eriteria. ;Method blanks may be .eliminated if technical justification can be provided (e.g. toe method blank was analyzed after an unexpectedly high level sample). If any method blanksare removed from the LOQ determination, document in toe raw data and report as appropriate. r '- 'r-i >^ - . o- 9.3 Laboratory Sam ple Replicates / Field Duplicate Sam ple Depending on toe scope o fth e projct, it or Seleed samples m aybe extracted at least in duplicate, and In triplicate if cfifficulties were encountered in the sampling and/or holding conditions o f the samples. If field sample repdcatessre collected, duplicate and triplicate extractions o f an individual sample may notJ required: rThereiativepercent difference (RPD) o f duplicate samples or relative stendate deviation (RSD)should beiess than 20%.for toe precision o f sample preparation and analysis to be.consktetad in control. Replicate samples not meeting the 20% method criteria w ill be reviewed and evaluated on a case by case basis. 9.4 Laboratory M atrix Spikes (LMSs) LMSs are performed if FMSs have previously been performed for toe sample matrix. Alternatively, LMSs are performed for a sample matrix if the FMS levels were not appropriate for determining spike recoveries relative to endogenous levels. Generaly, each sample location represents a different sample and sample matrix. LMSs are prepared for each sample and analyzed to determine the matrix effect on spike recovery efficiency of each target analyte. Lab matrix spike recoveries should fall within 30% o f expected values. LMS concentrations should be prepared at approximately 0.5-10 times the endogenous concentration or approximately 4-10 times the LOQ concentration o f each analyte. DePtehramsienaEtixotnraocftioPneraflunodriHnaigthedPAerdfEodrTmsS,aA-Snlcc-1oe5hL4oiql.s3u,iAdmCidhreosm, aantodgSrauplfhoyn/aMteasssInSWpeaPctaetrogrmBeye1St0ryoolidf20 E07-0149; Interim Report #2 3M Cordova Groundwater December 2009 Page 97 of 145 p. 103 Document may be used, if current, frv 14 o's.ys from 02/G3 CONFIDENTIAL 9.5 Laboratory Control Spike (LCS) Lab control spikes are prepared for each extraction batch to determine method accuracy and precision. LCSs should be prepared at a minimum o f two levels and in triplicate. Low lab control spikes should be prepared at a concentration in the range of approximately four to ten times higher than die targeted LOQ and the high lab control spikes should be prepared at a , concentration near the mid-point of the calibration curve. For each target analyte, the percent relative standard deviation (method precision) o f the pooled control spikes must be less than or equal to 20% and the average recovery (method accuracy) must be 80-120% Sample data for target analytes outside of the laboratory control spike acceptance criteria are not reportable' 9.6 Field Matrix Spikes (FMSs) FMSs are prepared for each sample and analyzed to determine the matrix effect and sample holding time on spike recovery efficiency of each target analyte. Generally, each sample location represents a different sample and sample matrix. FMS samples are a sample to which known quantities of the target analytes are added to the sample bottle in the field or in the laboratory before the bottles are sent to the field. Typically a low and a high FMS are prepared for each sampling location. The ratio o f endogenous analyte to field spike concentration that is appropriate to assess accuracy Is defined as approximately 0.5 to 10 times the expected sample concentration;''For example, if the endogenous level of analyte in the sample is expected to be 1.0 ng/mL, the appropriate range for FMS used to assess accuracy of results would be approximately 0.5 ng/mL to 10 ng/mL. For samples that are expected to have endogenous analytes present at or below foe targeted LOQ, the appropriate range for FMS would be approximately 4 to 10 times foe LOQ concentration. For example, if the analyte LOQ is 0.025 ng/m L the appropriate range for low level FMS would be 0.1 ng/mL to 0.25 ng/mL. If foe expected range o f analyte concentrations is unknown, multiple spikes at varying levels may be prepared to increase the likelihood that a spike at an appropriate level is made. Field matrix spike method acceptance criteria are recoveries within 30% o f the expected value. If FMS recovery is outside of 30% o f the expected value o f could not be assessed because the FMS was spiked at an inappropriate leybl, foe sample result is reported as NR, where NR is defined as "Not Reportable*. For dat reportabiirty, a sample may be re-extracted and re analyzed o r an alternate analytical method may be applied to the sample. Alternatively, resampling and reanalysis o f a new sample may be completed. If re-extraction, resampling, and re-analysis fail to meet the FMS acceptance criteria, the sample result w it be reported as ` NR* (not reported due to noncompliant QC results). Exceptions to the 30% FMS acceptance criteria for data reportability are as follows: 1. ) If FMS recovery could not be assessed because FMS's ware at an inappropriate level, then Laboratory Matrix Spikes (LMS) may be substituted. If LMS recoveries are within 30% the data are reportable but flagged as not meeting the FMS method acceptance criteria. 2. ) If multiple FMS's were prepared on a sample and foe dosest FMS level to foe reported sample meets foe 30% acceptance criteria but additional FMS's are outside the 30% acceptance range, foe data are reportable but flagged with an expanded uncertainty and as not meeting FMS method acceptance criteria. 3. ) If tire FMS recoveries are outside o f the 30% acceptance range but at least 20 acceptable historical reportable FMS sample results are available, the data may be reported but flagged with an expanded uncertainty and as not meeting FMS criteria. 10 Calibration and Standardization DePtehramsienaEtixotnraocftioPneraflundoriHnaigthedPeArdfoEdrTmsS,aA-n8lcc-1oe5hL4oiql.s3u,iAdmCidhreosm, aantodgSrauplfhoyn/aMteasssInSWpeaPctaterogrmbeye1St1ryoolidf 20 EQ7-0149; Interim Report #2 3M.Cordova Groundwater - December 2009 Page 98 ot 145 0-r>:';i.;-*rer-t may be ,t. CONFIDENTIAL p. 104 fro ;v 10.1 Instrum ent Setup Note: In this example, an Applied Blosystems Sdex API 4000 Tandem Mass Spectrometer (LC/MS/MS) is used. Other-brands of LC/MS/MSs as well as single quadnjpole mass spectrometers (LC/MS) may be used as long as the method criteria are met. Brand names, suppliers, part numbers, and models are for illustrative purposes only. Equivalent performance ' may be achieved using apparatus and materials other than those specified here, but demonstration o f equivalent perforrrtancethat meets the requirements o f this method is the responsibility o f the laboratory. The operator must optimize and document the equipment and settings used. Establish the LC/MS/MS system and operating conditions equivalent to the following: Mass Spec: Applied Biosystems API 4000 Ion Source: Turbo Ion Spray (ABS) - , ; Mode: Electrospray Negative - Scan Type: MRM (Multiple Reaction Monitoring) Harvard infusion pump (Harvard Instruments), for tuning .. - Computer DellDHM J' ; 1/ Software: \Mndows 2000 or Windows ^CP, Analyst 1 4.1 HPLC: Agilent Series 1100 Agilent Quaternary Pump < Agilent Vacuum DegasSer - Agilent Autosampler Agilent Column Oven ': Note: One dr mdre C.18. HPLC (?.1 m m x100m m ,5um or 2.1 mm x SO mm, 5pm) may be attached on-line after the purge valve and before the sample injection port to retard HPLC Column: Betasil C 1 8 , 2.1mm x ;1O0mm, 5pm (ThermoElectron Corporation) '..lev " v : ! Column Temperature: 35*^ . Injection Volume. 5pL r- Mobile Phase (A): 2mM Ammonium Acetate in ASTM Type I water (See 7.3) - Mobile Phase (B): Methanol v' n' . i. r : : " ' /i . : .1 DePtehramsineaEtixotnraocftiPoneraflunodriHnaigthedPeArdfoEdrTmsS,aA-8nlcc-1oe5hL4oiq.ls3u,iAdmCihdreosm, aantodgSrauplfhoyn/aMteasssInSWpeaPctaetrgormBeye1St2ryoolidf 20 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 99 ot 145 Dccuiryir.f wyy l'.-' CONFIDENTIAL p. 105 if :xrfcn!. for 14 days f'O.n 02/03' Liquid Chromatography Gradient Program. Step Number Total Tim (mty FlowRat (fi/mln) 00 1. .1 .0 2 14.5 3 15.5 4 16.5 5 20.0 300 300 300 300 300 300 PmxptA (2mM ammoniumacetate) 80.0 80.0 10.0 10.0 80.0 ' 80.0 flfothanoO 20.0 200 00.0 S0.0 20.0 ' 20.0 Note: Other HPLC gradients may be used as long as the method criteria and project data quality objectives are met. It may be necessary to adjust the HPLC gradient in order to optimize instalment performance. Columns with different dimensions (e.g. 2.1 mm x 30mm) and columns from different manufacturers (Keystone Betas!) C18 etc.) may be used. Mesa Transitions Monitored. Anafyla Mae* Transition Q1 (turni) PFBAiC, A ddi 213.0 ! NFPA <CsA ddi 262.9 PFH AfC iAdd) 313.0 TDHA (Cr A ddi 362.9 l i 413.0 Ct Add 463.0 ______ Maas Transition 03 (m u l 169.0 219.0 268.7.118.9 318.7.168.8.118.9 368.9.219.0.169.0 416.7,168.9,218.9 ' D o clu ste rtn g PotanUaH -30 -30 45 35 -45 45. CAdd CAdd Cio Add FBSA FOSA PFBS PFHS PFOS THPFOS THPFDS PFO Ai1.2,3C1 p fo s r "o>i 512.9 563.0 613.0 297.7 497.9 2989 398.9 498.9 428.9 526.9 414.9 503.0 468.8,218.9,269.1 518.7.288.9.218.8 568.7.168.9.318.7 78.0 779 98.8.79.9 9 6 9 .8 0 .0 80.0.98.8,130,0 46.8.B0.9 506.7.81.0 369.8 103.0.84.0 -35 45 -50 -55 -90 65 1 ' ' -95 ' -120 . -70 -70 -40 -100 ETS-8-154.3 Page 13 of 20 Determination o f Perfluorinated Acids, Alcohols, Amides, and Sulfonates in W ater By solid Phase Extraction and High Performance Liquid Chromatography,Mass Spectrometry E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 100 ot 145 Document may be CONFIDENTIAL p. 106 foi d<-.-/s f.'orn Multiple transitions for monitoring the analytes is an option as summing multiple transitions may provide quantitation of isomers that more closely matches NMR data and may have the added benefit of increased analyte signal. The use of one daughter ion is acceptable if method sensitivity is achieved, provided that retention tim e criteria are met to assure adequate specificity. VWiile the daughter ions may be chosen at the discretion of the analyst, mass transition 99 is suggested for PFOS. Quantitation may be performed using the total ion chromatogram (TIC) for a given analyte. For example, the PFOA TIC would sum ail three of the monitored transitions. Use of the suggested primary ion is recommended. Retention times may vary slightly, on a dayto-day basis, dependng on the batch of mobile phase and the gradient, column, guard ooiumrKs) used etc. Drift in retention times is acceptable within an analytical run, as long as the drift continues through the entire analysis and the standards are interspersed throughout the analytical run. . i . ` '* ^ '. + ` 1 10.2 Method Acquisition Param eters The following values are provided as an example o f method acquisition parameters for a single period, single experiment method using the SdexinstrUmentatiori. A c ^ values may vary from instrument to instrum ent Also, these values maybe changed from'time to time in order to optimize for greatest sensitivity. If a multiple period is used, each period may have different gas, temperature, and ion spray voltages. Curtain Gas (C IR ) CoOslon Gas (CAD) lonSoray Vottaoe (IS) Temperature (TEM) Gas 1 (Nebulized GS1 Gas 2 (Turbo Gas) GS2 Entrance PotenBal (BP) 1 5 .0 '. wgh` -1500 . 450X1 3510 : ,, 45.0 ON ' -10 11 i|t 10.3 Calibration Curve Analyze the standard curve prior to each set o f samples. The validated method specifies mat the standard curve should be plotted ustqg a linsarfit, weighted 1/x or unweighted. However, the standard curve may also be plotted by ,quadratic fit (y * ax* + bx + c), weighted 1/x or unweighted, using suitable software. The calibration citfves may include but should not be forced through zero. The mathematical method used k /ta lc u la te the calibration curve should be applied consistently throughout a study. Any chariige should be thoroughly documented in the raw data. If the calibration curve does not meet acceptance criteria, perform routine maintenance or prepare a new standard curve (if necessary) and reanalyze. For purposes o f accuracy when quantitating low levels o f analyte, it may be necessary to use the low end o f the calibration curve rather than the full range. For example, when attempting to quantitate approximately 0.05 ng/mL of analyte, generate a calibration curve consisting o f the standards from 0.025 ng/mL to 10.0 ng/mL rather than the full range of the curve (0.025 ng/mL to 25.00 ng/mL). This w ill reduce inaccuracy attributed to linear regression weighting of high concentration standards. High and/or low points may be excluded from the calibration curves to provide a better fit over the range appropriate to the data or because they did not meet the pre-determined acceptance criteria. Low-level curve points should also be excluded if their area counts are not at least twice that of the method and/or solvent blanks. Any curve point may be rejected due to a bad injection DePtehramsienaEtixotnraocftiPoneraflunodrHiniagthedPeArdfoEdrTmsS,aA-n8lcc-1oe5hL4oiql.s3u,iAdmCihdreosm, aantodgSrauplfhoyn/aMteasssInSWpePactaetrgoremBy1e4Stryoolifd20 E07-O149; Interim Report #2 3M Cordova Groundwater December 2009 Page 101 or 145 .'.:<T*nt, nvv !;*? < iJr'K* CONFIDENTIAL p. 107 or failing to meet accuracy requirements o f 25% (and 30% for the LLOQ). Justification for exclusion o f calibration curve points will be noted in the raw data. A minimum o f 6 points will be used to construct the calibration curve. No more than 25% of the total extracted calibration standards should be excluded. This does not pertain to low and high levels that may needto be disabled to achieve an accurate curve in the concentration range of the samples, rather, this is intended to apply to mid curve points only. 10.4 Continuing Calibration Verification (CCV) Continuing calbration verifications (CCV) are analyzed to verify the accuracy of the calibration curve. Analyze a mid-range calibration standard, one o f the same standards used to construct the calibration curve, at a minimum after every tenth sample, not including solvent blanks, with a minimum of one per sample set. Calibration verification injections must be within 25% to be considered acceptable. The calibration curve and the last passing CCV will then bracket, acceptable samples. Multiple CCV levels may be used. 10.5 System Suitability A minimum o f three system suitability samples will be injected at the beginning o f each analytical run, prior to the analysis o f the calibration curve; Typically these samples are at a concentration riar the mid-level of the calibration curve are repeated injections from one autosampler vial. The system suitablity injections must have area counts with an RSD o f 5% and a retention time RSD o f 2% to be compliant 11 Procedures 11.1 Extraction Scheme The following steps represent a typ ica l extraction scheme. Sample extraction volumes and final elution volumes may be adjusted to meet data quality objectives. Allow samples to equilibrate to room temperature. Thoroughly mix samples by gently inverting the sample bottle. Measure a 40mL representative aliquot o f the well-mixed sample into a 50mL polypropylene centrifuge tubes (Spike the lab matrix spites as required*, replace lid and mix well). Alternate volumes may be used depending on the scope o f the project. Use a consistent sample volume for all extractions and document on the sample prep sheet Add 40pL o f 250 mg/mL sodium thiosulfate solution to 40mL of sample. Adjust the amount of sodium thiosulfate solution added if alternate sample volumes are used. Thoroughly mix sample. Note: * Samples may need to be prescreened to determine an appropriate matrix spike level (typicaly approximately 0.5 to 10 times the sample concentration). Alternatively the samples could be spiked at more than one level, allowing for the inappropriate spike level to be eliminated. Condition the C18 SPE cartridges (1g, 6mL) by passing approximately 10mL methanol (at a minimum) followed by approximately 50mL (at a minimum) ASTM Type I water. Do not let column run dry. If column does run dry, recondition. SPE cartridges cannot be over conditioned. Load the analytical sample onto the C18 SPE cartridge. Once the entire sample has loaded onto the cartridge, isolate the cartridge from the vacuum and wait until all samples on the vacuum manifold have been loaded. Discard eluate. Open manifold valves and pull a vacuum on the SPE cartridges for approximately 3 minutes to remove residual water from the SPE cartridge. Elute with exactly 5 mL of 100% methanol. Collect eluate into graduated 15mL polypropylene centrifuge tubes. This is the target elution fraction (final volume approximately 4.5 mL as not all of the solvent w ill leave the SPE column. This will not affect the calculations in any way since the ETS-8-154.3 Page 15 of 20 Determination of Perfluorinated Adds, Alcohols, Amides, and Sulfonates In Water By bond Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Pape 102 of 145 Dixu.r.ef'l may <)? CONFIDENTIAL p. 108 V2M . for 14 5 `i i 'O"' -*f* curve is also extracted). Note: the elution volume may be altered to meet project needs. The same elution volume' needs to be used for aH samples, calibration standards, and QC samples. Intersperse the method blanks throughout the extraction batch. Transfer well-mixed aliquots of the final extract to labeled autovials. i, Analyze a portion o f the target elution fraction eluent using negative electrospray HPLC/MS/MS or HPLC/MS. Note: Samples are concentrated by a factor of eight during the extraction; Initial Vol = 40mL -> Final V o l.-5 m L 11.2 Sam ple Analysis Set up analysis Sample queue.M ethod blanks must be interspersed throughout the analytical sequence. Inject the same volume (between 5-25pL) o f each standard, analytical sample end blank into the instrument (unless an on-instrument sample dilution is desired). All sample extracts with a concentration >. JLOO must be diluted and reanalyzed, if dilution of the final extract fails to produce acceptable, results (e.g. poor MS recoveries) dilute the original sample and re-extract r,; 12 Data Analysis and Calculations The chromatography analysis softw atew ill typically calculate the amount o f target analyte in the sample extracts using the established calibration curve. Calculate the percent recovery of the LCS using the following equation: (" .^ > - J; \ . ; LCS Concentration (--- ) L C S % r e c o v e r y -S--p--i-k-e;--Concent,rat,i--on ^(---^*-1) 0 0 % Calculate the percent recovery o f theFSCS?using the following equation: ... ` O -' , 0.' 'Vi -v " ' FSCS Concentration (-- ) FSCS% recovery * 100% : . JSpjfc^Concemmtion(^7-) Calculate the percent recovery dfthe-FM S using the following equation: FMS% recovery = FMS Concentration (--m--L)_-_A__v_e_r_ag__e_C_o_n_c_e_n_t_r_a_ti_o_n_o__f_S_a_m__p_le_/_S_a;_m_p_l_e_D__u_p_li_c_a_te__(--mL ) . 100% Spike Concentration (--mngL-) ETS-8-154.3 Page 16 o f 20 Determination of Perfhjorinated Acids, Alcohols, Amides, and Sulfonates In Water By solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 103 o f 145 p. 109 Dcc-u^ehl rnay be e^oC. CONFIDENTIAL sni. for 14 asys from C-2:2 ' i ':.'0 1C; 13 Method Perform ance Any method performance parameters that are not achieved m is t be considered in th evaluation of the data. Nonconformance to any specified parameters must be described and discussed if the project lead chooses to report the data. If criteria listed in this method performance section are not met, maintenance may be performed on the system and samples reanalyzed, or other actions taken as determined by the analyst/project lead. Document all actions in the raw data. If data are to be reported when performance criteria have not been met, the data must be footnoted on tables and discussed in the text o f the report. 13.1 System Suitability A minimum o f three system suitability samples w ill be injected at the beginning o f each analytical run. These samples are run prior to the calibration curve..The system suitability injections must have area counts with an RSD of 5% and a retention time RSD o f 2% to be compliant. 13.2 Q uantitation C alibration C urve: Th coefficient of determination (r2) value for the calibration curve must be greater than or equal to 0.990. Each point in the curve must be within 25% o f the theoretical concentration with the exception o f the LLOQ, which may be within 30%. D em onstration o f S p ecificity: Specificity is demonstrated by chromatographic retention time (within 3% of standard) and the mass spectr'a.lmre?,sp"onse1oJL;f unique ions. 13.3 Sensitivity Solvent Blanks and M ethod B lanks: Solvent and method blank area counts must be < 50% that of the lowest standard used in the calibration'curV. Solvent blanks analyzed a ft ' high level samples or calibration standards may have area counts greater than 50% ofthe lowest standard from instrument carryover as long as subsequent solvent blanks analyzed before the next sample/QC sample demonstrate that foe instrument carryover is decreasing back to expected levels. Lim its o f Q uantitation (LOQ): The lower LOQ (LLOQ) is foe lowest non-zero active standard in the calibration curve; the peak area of the LLOQ must be a t least 2X that of the method blank(s). By definition, the measured vaiue of the LLOQ must be within 30% of foe theoretical value. 13.4 Accuracy CCV Perform ance: Calibration verification injections must be within 25% to be considered acceptable. The calibration curve and foe last paissirig CCV will then bracket acceptable samples. Multiple CCV levels may be used. LCS recoveries should be within 25% to be considered acceptable and to verity that the method is in control on a given day. Lab C ontrol S pikes: The average recovery of the pooled LCSs for each target analyte should be within 80-120% and the percent relative standard deviation of foe recoveries must be less than or equal to 20%. ........ 13.5 Precision R eproducibility: Reproducibility erf foe method is defined by the results of duplicate or triplicate analysis of samples. A RPD or RSD of s 20% will be considered acceptable for replicate lab control spikes. Because field sample duplicates account for variability in sample location (as well as variability in the extraction procedure), RPD or RSD values may be higher. Report foe RPD or ETS-8-154.3 Page 17 o f 20 Determination of Perfluorinated Adds, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry E07-Q149; Interim Report #2 > 3M Cordova Groundwater December 2009 P 8ge104of145 p. 110 i'.JO";. l-r'-.i -Tifcy u* ,,i>` . >\ "felli V r I * o CONFIDENTIAL `-Th Cl-'. RSD of sample/fietd duplicates and discuss in the report if greater than 20% and the impact on field matrix spike recoveries, if any. 13.6 A nalytical Method. Uncertainty / Data Acceptability Analytical method uncertainty d a y be defined and reported in one o f two ways. The first approach uses historical LCS data that is control charted and is used to evaluate method ' accuracy and precision, based on procedures defined in ETS-12r012. in ETS-12-012, a detailed estimation of uncertainty measurements was performed on ETS-8-231.2, ` Solid Phase Extraction and Analysis o f Perfluorinated Adds, Alcohol, Amides, Sulfonates and other Fluorinated Compounds by High Performance Liquid Chromatography/Mass Spectrometry*. The procedure outlined in this m thodutilizs the same preparation and analysis steps as'those identified in ETS-B-2312. In that evaluation it wasdeterm iried mat the use of control charts was an acceptable approach to determining analytical method uncertainty. At least twenty data points are required when using this method for determining analytical uncertainty. Th method uncertainty is defined as 2x the standard deviation o f the percent recoveries of the pooled lab control spikes.. While an LCS data points are control chartd, only the most recent fifty data points are used for determining the method uncertainty. When less than twenty LCS data points have been generated for a given analyte, the batch LCS and FMS QC determine the data acceptability. If FMSs meet the 30% recovery criteria at a level appropriate to the endogenous level, and the LCS meet the 20% recovery criteria, then the uncertainty o f the data is deemed accurate to within 10020%. If FMS do not meet the 30% recovery criteria, and historical FMS data does not exist, the analytical uncertainty is evaluated on a case-by-case basis and a discussion included in the final analytical report. 14 Pollution Prevention and W aste Managem ent Sample extract waste and flammable solvent is discarded in high BTU containers, and glass pipette waste is.discarded in broken glass containers Ideated in the laboratory. 15 Records Each data package generated for a study must include all supporting information for reconstructibility of the data. Information for the data package must indude, but is not limited to the following items; study or project number, sample and standard prep sheets/records, instrument run log (instrument batch records, instrument acquisition method, summary pages), instrument results files, chromatograms, calibration curves, and data calculations. 16 Attachm ents None. 17 References "Method o f Analysis for the Determination o f Perfluorooctane sulfonate (PFOS), Perfluorooctane sulfonylamide (PFOSA). and Perfluorooctanoate (POAA) in w ater" , E. Wickremesinhe and J. Flaherty. Study Number 023-002, Centre Analytical Laboratories, Inc., State College, Pennsylvania, Januaiy 2000. ' E01-0454; Validation report for the ` Method o f Analysis for the Determination o f Perfluorooctane sulfonate (PFOS), Perfluorooctane sulfonylamide (PFOSA), arid Perfluorooctanoate (POAA) in DePtehramsienatxiotrnaoctfioPneraflunodriHnaigthedPAerdfEodrTmsS,aA-8nlcc-1oe5hL4oiql.s3u,iAdmCihdreosm, aatiodgSrauplfhoyn/aMteasssInSWpeaPctaetrgorBmeye1Bt8ryoolidf 20 E07-014B; Interim Report #2 3M Cordova Groundwater - December 2009 Page 105 o f 145 p. 111 Document may te used, r currant, for 14 days from 02/03/20 CONFIDENTIAL Water", E. Wickremesinhe and J. Flaherty, Study Number 023-002, Centre Analytical Laboratories, Inc., State College, Pennsylvania. 18 Affected Documents None. 19 Revisions R evision Number Summary of Changes 1 Updated to the new format. Changed Title. Section 1: States the validation o f 3 analytes, rem oves reference id'EPA document that's no longer applicable. Section 2: Provided for the extractbn o f more than the 3 validated analytes, allows the use o f a LC /M S system, not only the LS/M S/M S previously mentioned. Section 3: Revised definitions for held matrix spike, field control spike, LLOQ, m ethod blank, and MDL. , Section 5: Reworded the interferences, added recommendation to use disposable pipettes. Section 6: Re-categorized and pared down. Section 7: Changed storage time to 6 months. Added more calibration points to the table. Section 8:Added statem ent addressing labeling requirements and spiking procedures. Expanded section 8.8. Section 9: N ew Section Section 10: Changed some o f the param eters in the tables. Allowed for use of different instnrmentation. Added information from section 12 o fprevious version, extensively revised. Section 11 (section 9 in previous version): Clarification o f wash step, stated exact volume o f eluate is 5 mL, revised standardization process, rem oved requirement to use LC/M S/M S. Section 12 (section 13 in previous version: no changes Section 13 (section 14 in previous version): Extensively rewritten. Section 14 (section 15 in previous version): no changes Section 15 (section 16 in previous version): M inor changes to recording requirem ents. Section 16 (section 17 in previous version): Rem oved attachment. Section 17 (section 18 in previous version): Rem oved reference to EPA document that no longer applied to this SOP. Section 18: N ew section. 2 Section 1: Added emphasis that the method is a perform ance-based method. Added statem ent that this method does not cover sample collection. Section 2: Rem oved statem ent that samples are shipped cold as this is no longer the practice. Rem oved reference to specific C 18 SPE cartridge. Added statement that other extraction and elution volumes m ayb e used. Section 3. M inor edits/clarifications to severe/ definitions. Added surrogate and S PE cartridge as a definition. Rem oved references to LOD and MDL as this ETS-8-154.3 Page 19 of 20 Determination of Perfluorinated Adds, Alcohols, Amides, and Sulfonates In W ater By solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry EQ7-0148; Interim Report #2 3M Cordova Groundwater - December 2009 Page 106 of 145 in re -'l iiv w CONFIDENTIAL p. 112 laboratory does not report LCD and/or MDL values. Section 6. Added reference to autom ated S PE workstatton. OSectlon 7. A dded additional analytes and updated standard preparation exam ples. S ection8. Rem oved verbiage that pertained to sam ple collection as the 3M Environmental Lab personnel typically do not collect samples. Addressed sample bottle preparation. Section 9. Changed m ethod blank criteria, LM S and FM S acceptance criteria from 10025% to 10030% , and LCS criteria where pooled recoveries are used to determ ine acceptance. Section 10. Updated all example Instalm ent conditions for Sciex Instrumentation rem oved Micromass references Section 11. Clarified extraction procedure - rem oved inclusion o f a 40% methanol wash step. Section 12. M inor edits. Section 13. Added section,on determination o f analytical uncertainty and changed perform ance criteria as appropriate. 3 Section 11.1. A dded use o f sodium thiosulfate ETS-8-154.3 Page 20 o f 20 Determination o f Perfiuorinated Adds, Alcohols, Amides, and Sulfonates In Water By solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry E07-0149; Interim Report #2 3M Cordova Groundwater December 2009 Pape 107 of 145 p . 113 Dcaimenl may be used, ' current for 14 days from 02^03/20 CONFIDENTIAL 3 M E n v ir o n m e n ta l U y w w t o iy Method Method ofAnalysis for the Determination of Perfiuorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Method Number: ETS-8-044.0 Adoption Date: (Jpon Signing Effective Date: Q y fo * ] Approved By: ` '' W illiam K. Reagen, Laboratory Manager // /o y Date E T S -8 -0 4 4 .0 P ag e 1 of 11 Method of Analysis for the Determination of Perfiuorinated Compounds in W ater by LC/MS/MS; Direct 3M Cordova Groundwater - December 2009 Page 108 of 145 CONFIDENTIAL p. 114 1., *03/201 1 Scopo and Application This method is to be used to quantify Perfludrobutanoic Add (PFBA), Perfluoropentanoic Add (PFPeA), Perfluorohexanoic A dd (PFHA), Perfluoroheptanoic A dd (PFHpA), PerfluoroqctanoicAdd (PFOA), Perfluorononanoic A dd (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Add (PFUnA), Peffluorododecandc A dd (PFDoA), Perfluorobutanesuifonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) by High Performance Liquid Chromatography coupled to a tandem Mass SpectrometriC Detector (LC/MS/MS) in clean water samples. W ater samples containing heavy particulate may require preparation by an alternate method such as ETS-8-154 "Determination of Perfluorinated Adds, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Perteimarxte U qdd avonrtetei^aphy/MisS>S^ectrometry*. . This method Is considered a perform ance-based method. Data Is considered acceptable as long as the defined QC elements are satisfied. ' , v ' Sample collection Is not covered under this analytical procedure. 2 Method Summ ary ____ _____ Clean aqueous samples are analyzed by direct injection using LC/MS/MS. Samples containing heavy particulate may not be suitable for analysis by this method. Samples containing suspended particulate should be centrifuge prior to removing a sample aliquot, or filtered. This is a performance-based method. Method accuracy is determined for each sample set using multiple laboratory control spikes at multiple concentrations. This method also requires that the precision and accuracy for each sample be determined using field matrix spikes to verify that the method is applicable to each sample matrix. Sample results for spikes outside o f 70% to 130%, may be flagged as such (with expanded accuracy statements), or will not be reported due to non-compliant quality control samples. Fortification levels for Held matrix spikes and for laboratory matrix spikes should be at least 50% of the endogenous level and less than 10 times the endogenous level to be used to determine the statement of accuracy for analytical results. 3 Definitions 3.1 Calibration Standard A solution prepared by spiking a known volume o f the Working Standard (WS) into a predetermined amount o f ASTM Type I, HPLC grade water, or other suitable water, and analyzed according to this method. Calibration standards are used to calibrate the instrument response with respect to analyte concentration. 3.2 Laboratory Duplicate Sam ple (LDS, or Lab Dup) A laboratory duplicate sample is a separate aliquot of a sample taken in the analytical laboratory that is analyzed separately with identical procedures. Analysis o f LDSs compared to that o f the first aliquot give a measure o f the precision associated with laboratory procedures, but not with sample collection, preservation, or storage procedures. 3.3 Field Blank (FB)/Trip Blank ASTM Type I, HPLC grade water, or other suitable water, placed in a sample container in the laboratory and treated as a sample in alt respects, including exposure to sampling site conditions, storage, preservation and all analytical procedures. The purpose o f the FB is to determine if test substances or other interferences are present in the field environment. This sample is also referred to as a Trip Blank. ETS-8-044.0 Page 2 o f 11 M ethod o f Analysis for the Determ ination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct injection Analysis E07-0149; Interim Report #2 Page 109 of 145 3M Cordova Groundwater - December 2009 p. 115 Oocurne.Tt may be used. i!curent. for 14 days from CONFIDENTIAL 3.4 Field Duplicate Sam ple (FDS, Field Dup) A sample collected In duplicate at the same time from the same location as the sample. The FDS is handed under identical circumstances and treated exactly the same throughout field and laboratory procedures. Analysis of the FDS compared to that of the first sample gives a measure of the precision associated with sample collection, preservation and storage, as well as with laboratory procedures. 3.5 Field Matrix Spike (FMS) A sample to which known quantities o f the target analytes are added to the sample bottle in die laboratory before the bottles are sent to die field for collection of aqueous samples. A known, specific volume o f sample must be added to the sample container without rinsing. This may be accomplished by making a Till to this level' line on the outside of the sample container. The FMS should be spited between approximately 50% and 10 times the expected analyte concentration in the sample, if the expected range o f analyte concentrations is unknown, multiple Spikes at varying levels may be prepared to increase the likelihood that a spike at an appropriate level is made. The FMS is analyzed to ascertain if any matrix effects, interferences, or stability issues may complicate the interpretation of the sample analysis. 3.6 Trip Blank Spike (Field Spike Control Sample, FSCS) An a iq u o to f ASTM Type I, HPLC grade water, o r other suitable water, to which known quantities of the target analytes are added in the laboratory prior to the shipment o f the collection bottles. The FSCS is extracted and analyzed exactly like a study sample to help determine if the method is in control and whether a loss o f analyte could be attributed to holding time, sample storage and/or shipment issues. A low and high FSCS are appropriate when expected sample concentrations are not known or may vary. At least one separate, un-spiked sample must be taken at the same time and place as each FMS. 3.7 Laboratory Control Sam ple (LCS) . An aliquot of control matrix to which known quantities of the target analytes are added in the.laboratory at the time of sample extraction. At least two levels are included, one generally at the low end o f ttie calibration curve and one near the mid to upper range of the curve. The LCSs are extracted and analyzed exactly like a laboratory sample to determine whether the method is in control. LCSs should be prepared each day samples are extracted. 3.8 Laboratory Matrix Spike (LMS) A laboratory matrix spite is an aliquot o f a sample to which known quantities o f target analytes are added in the laboratory. The LMS is analyzed exactly like a laboratory sample to determine whether the sample matrix contributes bias to the analytical results. The endogenous concentrations o f the analytes in the sample matrix must be determined in a separate aliquot and the measured values in the LMS corrected for these concentrations. LMSs are optional for analysis ofaqueous sampies. 3.9 Laboratory Sample A portion or aliquot o f a sample received from the field tor testing. 3.10 Lim it o f Q uantitation (LOQ) The lower limit o f quantitation (LLOQ) for a dataset is ttie lowest concentration that can be reliably quantitated within the specified limits o f precision and accuracy during routine operating conditions. To simplify date reporting, the LLOQ is generally selected as the lowest non-zero standard in the calibration curve that meets method criteria. Sample LLOQs are matrix-dependent. The upper lim it o f quantitation (ULOQ) for a dataset is the highest concentration that can be reliably quantitated within the specified limits of precision and accuracy during routine operating conditions. The highest standard in the calibration curve that meets method criteria is defined as the ULOQ. ETS-8-044.0 Page 3 o f 11 Injection AnalysisMethod o f Analysis for the Determination o f Perfluorinated Compounds in W ater by LC/MS/MS; Direct E07-0149; Interim Report #2 Page 110 o f 145 3M Cordova Groundwater - December 2009 C e ''.'mi?' i f-v y 'e CONFIDENTIAL v< p. 116 . , 1 4 CJ C< ^ 1O . . 4. 3.11 Method Blank An aliquot of control matrix that is treated exactly like a laboratory sample including exposure to all glassware, equipment, solvents! and reagents that are used with other laboratory saniples. The method blank is used to determine if test substances or other interferences are present in Hie laboratory environment, the reagents, or the apparatus. ' 3.12 Sam ple '! <f A sample is dn aliquot removed from;a larger quantity o f material intended to represent the original source 'm aterial. .. 3.13 % c k t d f r t ih ^ S d lu ^ (SSS) ; !' A concentrated solution ofasingle-anatyte prepared in the laboratory w ith an assayed reference compound * . ... .>r, - 3.14 Surrogate A compound similar In chemical compositirxi arid behavior to the target analyte(s), but iS not normally found in the samplefs). A surrogate compound:is typically,a target apalyte with at least one atom containing an isotopically-labeled substitution. If used, surrogatefsj are added Jp all samples and quality control samples. Surrogate^) are added to quantitatively evaluate the entire analytical procedure including sample collection, preparation, and analysis. Inclusion o f a surrogate analyte is an optional quality control measure arfo is NOT reqiared:. ' (( 3.15 W orking Standard (WS) A solution of several analytes prepared in the laboratory from SSSs and diluted as needed to prepare calibration standards and other required analyte solutions. ,, 4 W arnings and Cautions V : ! ; '/ ! f ____________ 4.1 Health and Safety ., The acute and chronic toxicity of the standards for this method have not been precisely determined; however, each should be treated as'a'pdferitlal Health hazard.; The analyst should wear gloves, a lab coat, and safety glasses to preveht exFK ^re tdcherriktels that might be present. The laboratory is responsible for maintaining p safe work environment and a current awareness of local regulations regarding the handling of.the chenrvqals used in this m ethod A reference file of material safety data sheets (MSDS) should be available to all personnel involved in these analyses. 4.2 Cautions The analyst must be fam iliar with the laboratory equipment and potential hazards including, but not limited to, tire use o f solvents, pressurized gas and solvent lines, hjgh voltage, and vacuum systems. Refer to tire appropriate equipment procedure or operator manual for additional information and cautions. 5 Interferences During sample preparation and analysis, major potential contaminant sources are reagents and glassware. All materials used in ijre analyses shall be demonstrated to be free from interferences under conditions o f analysis by running m ethod blanks. ETS-8-044.0 Page 4 o f 11 Injection AnalysisMethod o f Analysis for the Determination of Perfluorinated Compounds in W ater by IC/M S/M S; Direct E07-0148; Interim Report #2 Page 111 o f 145 3M Cordova Groundwater - December 2009 p. 117 curne'U may be used, if currant, for 14 days from 02/03/2010 CONFIDENTIAL Parts and supplies that contain Teflon should be avoided or minimized due to fie possibility of interference and/or contamination. These may include, but are not limited to: wash bottles, Teflon* lined caps, autovial caps, HPLC parts, etc. The use of disposable micropipettes or pipettes to aliquot standard solutions is recommended to make calibration standards and matrix spikes. 6 Instrum entation, Supplies, and Equipm ent 6.1 Instrum entation and Equipm ent A high performance liquid chromatograph capable o f pumping up to two solvents and equipped with a variable volume injector capable o f injecting 5*100 uL Connected to a tandem Mass Spectrometer (LC/MS/MS). I ` L; Analytical balance capable o f reading to 0.0001g , , A device to collect raw data for peak integration and:quantitation 15-mL and 50-mL disposable polypropylene centrifuge tubes. Gas tight syringes, 25pL,50pL, 100pL, 250pL, 500pL> 1000pL 1 mL plastic HPLC autovial. Disposable pipettes, polypropylene or glass as appropriate Centrifuge capable of spinning 15-mL and 50-mL polypropylene tubes at SOOOrpm. 6.2 Chrom atographic System Guard Column: Prism RP, 4.6 mm x 50 mm, 5 pm Analytical Column: Betasil C18,4.6 mm x 100 mm, 5 pm Temperature: 10C ' 1: Mobile Phase (A): 2 mM Ammonium Acetate in Water Mobile Phase (B): Methanol Gradient Program: > Time /m int 0.0 0.5 11.0 13.5 13.6 17.0 %A ' 07 , 97 5 5 97 97 %B 3 3 95 95 3 3 Flow Rate (m U m in) 1L0 1.0 1.0 1.0 1.0 1.0 Injection Volume: 100 p L Quantitation: Peak Area - quadratic curve fit, 1/x weighted. RunTime: ~ 1 7 minutes. The previous inform ation is Intended as a guide; alternate conditions and equipment may be used provided that data quality objectives are met. ETS-8-044.0 Page 5 of 11 Injection AnalysisMethod o f Analysis fo r the Determination o f Perfluorinated Compounds in W ater by LC/MS/MS; Direct E07-0149; Interim Report #2 Page 112 of 145 3M Cordova Groundwater - December 2009 p. 118 Desumerti may be n CONFIDENTIAL f C U Tl'ttf: fe r 1 Cf-.-'S f.-OTi O tV 03/^01 6.3 M S/MS System 6.3.1 Mode: Electrospray Negative ion, MRM mode, monitoring the following transitions: A n a ly te Transition M onitored PFBA 213 - 169 PFPeA 263 ->219 PFHA 3 1 3 - 2 6 9 and 313 - 119 PFHpA 363 - 319.363 - 169 and 363 -> 119 PFOA 4 1 3 - 3 6 9 ,4 1 3 - 219 and 4 1 3 - 169 PFNA 463 - 419.463 - 169 and 463 -. 219 PFDA , 513 - 469. 513 - 219 and.513 - * 269, PFUnA 563 - 519. 563 - 269 and 563 - 219 PFDoA 613 - 569.613 - 169 and 613 - 319 PFBS 2 9 9 - 8 0 and 2 9 9 - 9 9 PFHS 399 - 60 antf.399 - * 9 9 PFOS 499 - 80. 499 -*-9 9 and 499 - 130 M ultiple transitions fo r m onitoring the analytes Is an option, as Summing m ultiple transitions may provide quantitation o f isom ers that more closely matches NMR data and may have the added benefit of increased sensitivity. The use of one daughter ion is acceptable if method sensitivity is achieved, provided that retention tim e criteria are met to assure adequate specificity. , ..o . The previous information is intended, as a guide, alternate instruments and equipment may be used. 7 Reagents and Standards 7.1 Chem icals W ater - Milli-Q, HPLC grade, or other suitably appropriate sources Methanol - H P IC grade \ Ammonium A cetate-A .C .S . Reagent Grade 7.2 Standards PerfluorobutanoicAcid (P F B A - C4 add);,Oalcwood P roduqtsjnc Perfluoropentanoic A dd (PFPeA - C5 acid, also known as NFPA, nonafluoropentanoic add); Alfa Aesar Perfluorohexanoic Add (PFHA - C6 add); -Oakwood Products, Inc Perfiuoroheptanoic Add (PFHpA - C7 add, alS'khOwn as TDHA, tridecafluoroheptanoicadd); Oakwood Products, Inc Perfluorooctanoic A dd (PFOA - C8 add); 3M Perfluorononanoic A dd (PFNA - C9 add); Oakwood Products, Inc Perfluorodecanoic A dd (PFDA - C10 add); Oakwood Products, Inc Perfluoroundecanoic Add (P FU nA -C 11 add); Oakwood Products, Inc Perfluorododecanoic A dd (P F D oA - C12 add); Oakwood Products, Inc Perfluorobutanesulfonate (PFBS - C4 sulfonate); 3M Perfluorohexanesulfonate (PFHS - C6 sulfonate); 3M Perfluorooctanesulfonate (PFOS - C8 sulfonate); 3M ETS-8-044.0 Page 6 o f 11 M ethod o f Analysis for the Determ ination o f Perfluorinated Compounds in W ater by LC/MS/MS; Direct injection A n a ly s is E07-0149; Interim Report #2 Page 113 of U S 3M Cordova Groundwater - December 2009 p. 119 i -.ume-v. may t - v s i r c>. : f y '<scav <- CONFIDENTIAL The previous inform ation is intended as a guide. Reagents and standards from alternate sources may be used. 7.3 Reagent Preparation 2 mM Ammonium acetate solution (Analysis)--Weigh 0.3 g of Ammonium acetate and dissolve in 2.0 L o f reagent water. Note: Alternative volumes may be prepared as long as the ratios o f the solvent to solute ratios are maintained. 7.4 Stock Standard Solution (SSS) and W orking Standard Solution Preparation The following standard preparation procedure serves as an example. Weighed amounts and final volumes may be changed to suit the needs of a particular study. For example, pL volumes may be spiked into volumetric flasks when diluting stock solutions to appropriate levels. 100 pg/m L ta rg et analyte SSSs--Weigh out 10 mg of analytical standard (corrected fo rp e rc e n t s p it and p u rity) and dilute to 100mL with methanol or other suitable solvent, in a 100mL volumetric flask. Transfer to a 125mL LOPE bottle or other suitable container. Prepare a separate solution for each analyte! Expiration dates and storage conditions of stock solutions should be assigned in accordance with laboratory standard operating procedure. An example of purity and salt correction is given below for PFOS. salt correction factor m olecular weight o f anion m oclecular weight of salt PFOS (K +)salt correction factor = ---- ,0.9275 538 10 mg CbF17S03K * with purity 90% = 8.35mg CF17S 0 f (10 mg*0.90*0.9275=8.35 mg) $ pg/m L (5000 ng/m L) m ixed w orking standard--Add 0.5mL each of the lOOpgrmL SSSs to a 10mL volumetric flask and bring up to volume with solvent. 250 ng/m L m ixed w orking standard--Add 1 25mL of the 5 pg/mL -mixed working standard solution to a 25mL volumetric flask and bring up to volume with solvent 125 ng/m L m ixed standard--Add 625pL o f the 5 pg/m l-m ixed working standard solution to a 25mL volumetric flask and bring up to volume with solvent. Storage C onditions-- Store all SSSs and working standards in accordance with laboratory standard operating procedure or in a refrigerator at 4<>20C fo ra maximum period of 6 months from the date of preparation. ETS-8-044.0 Page 7 o f 11 AnalysisMethod of Analysis for the Determination o f Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection E07-O149; Interim Report #2 Page 114 of 145 3M Cordova Groundwater - December,2009 p. 120 Dv;:urr'i.-.t r.>av .v v-er4 current, for 14 o/s hr--; 02/0/T:C; CONFIDENTIAL 7.5 Calibration Standards Using the working standards described above, prepare calibration solutions in ASTM Type I water, HPLC water, or other suitable water, using the following table as a guideline. Note: Volumes o f water and working standards may be adjusted to meet the date quality objectives addressed in the general project outline. Calibration levels other than those listed below can be prepared as needed. C oncentration o f WS, ng/m L p -- r~ r-- , tj Volum e o f WS, pL P in ti Volum e o f C alib ra tion S tandard (m l ; o f ASTM ty p e f W ater; o r : o th e r auttabfe water) P inal C oncentration o f C alibration Standard, ng/m L (p p b )ln ASTM ty p e / W ater, o r o th e r su ita b le w ater 125-, 125 v . 15 > I 1:n. ,!> 'Q r 50 < .' 0.025 0.0375 125 20 ; . .. ' fiO . . > 0.050 125 30 f - . :V : ::j 'gQ H' L '. V IC" ' 0.075 250 20. , . . . ; . :. ,, 0.100 250 50 , ! . :;50'.- 0.250 250 100 . 50 , 0.500 250 5000 200 25 50 1.00 2.50 5000 5000 50 100 50 50 5.00 10.0 8 Sam ple Handling 8.1 W ater Sam ple Preparation This method is applicable to dean water samples. Samples containing heavy particulate may not be suitable for analysis by this method. Samples containing Suspended particulate should be centrifuge prior to removing a sample aliquot, or Altered. Thoroughly mix sample before removing1analiquot and pladng in a labeled plastic autovial. Plastic is preferred over the use of gfassautovials, to prevent the possibly o f fluorochemical sticking to the glass. Dilute sample, if necessary, w ith ASTM Type I, HPLC water, or other suitable water. Prepare method QC samples and multiple method blanks and aliquot into labeled plastic autovials. Prepare at least five method blanks. 9 Sample Analysis - LC/MS/MS . Analyze the standard curve prior to each set o f samples. The standard curve may be plotted using a linear fit, weighted 1/x or unweighted, or by quadratic fit (y = ax2+ bx c), weighted 1/x or unweighted, using suitable software. The calibration curves may indude but should not be forced through zero. The mathematical method used to calculate the caSbration curve should be applied consistently throughout a study. Any change should be thoroughly documented in the raw data. High and/or low points may be exduded from the calibration curves to provide a better fit over the range appropriate to the date or because they did not meet the predeterm ined acceptance criteria. Low-level curve points should also be exduded if their area counts are not at least twice that of the method and/or solvent blanks. The coefficient of determination (t2) value for the calibration curve must be greater than o r equal to 0.990. Each point in the curve must be within 25% o f the theoretical concentration with the exception of the LLOQ, which may ETS-8-044.0 Page 8 of 11 M ethod o f Analysis for the Determ ination o f Perfluorinated Compounds in W ater by LC/MS/MS; D irect Injection A n a lysis E07-0149; Interim Report #2 Page 115 of 145 SMCordova G roundwater* December 2009 p. 121 Document may be used. arreni, for H oa/s from 02/03/2 CONFIDENTIAL be within 30%. Justification for exclusion o f calibration curve points will be noted in the raw data. A minimum o f 6 points w ill be used to construct the calibration curve. If the calibration curve does not meet acceptance criteria, perform routine maintenance 6r prepare a new standard curve (if necessary) and reanalyze. Continuing calibration verifications (CCV) are analyzed to verify the accuracy o f the calibration curve. Analyze a mid-range calibration standard, one of the same standards usd to construct th calibration curve, at a minimum after every tenth sample, not Including solvent blanks, with a minimum o f one per sample set. Calibration verification injections must be within 25% to be considered acceptable. The calibration curve and the last passing CCV will then bracket acceptable samples. Multiple CCV levels may be used. Samples containing analytes that are quantitated above the concentration o f the highest standard in the curve should be further diluted and reanalyzed. 10 Q uality Control 10.1 Data Q uality Objectives This method and required quality control samples is designed to generate data accurate to 30% with a targeted LOQ of 0.025 ng/m L Any deviations from the quality control measures spelled out below will be documented in the raw data and footnoted in the final report. 10.2 Method Blanks Method blanks must be prepared with each analysis batch. A t least five method blanks must be prepared. Method blanks may be injected multiple times, but no more than 3 injections should be removed from a single method blank. A t a minimum, method blanks are analyzed prior to instrument calibration, prior to the analysis of CCV samples, and at the end o f the analytical run. The mean area count for each analyte in the method blanks must be less than 50% of the area count of the LOQ standard. The standard deviation of the area counts o f these method blanks should be calculated and reported. If the mean area counts o f the method blanks exceed 50% o f the LOQ standard, then the LOQ must be raised to the first standard level in the curve that meets Criteria, o r alternatively, the method blanks must be evaluated statistically to determine outliers, or technical justification to eliminate one or more results should be made. . 10.3 Sam ple Replicates Samples duplicates are collected in the field. The relative percent difference, RPD, should be repotted. RPD results greater than 20% win be flagged in the report, but will not be excluded from reporting. The requirement for replicates excludes field blanks. 10.4 Surrogate Spikes Surrogate spikes are not required but may be used on project specific requirements. 10.5 Lab Control Sample Triplicate lab control spikes at a minimum of two different concentrations are to be prepared with each preparation batch. Low lab control spikes should be prepared at concentrations in the range of five to ten times higher than the targeted LOQ and high lab control spikes should be prepared at concentrations near the mid-point of the curve. The relative standard deviation o f the control spikes evaluated independently at each concentration level must be less than or equal to 20% and the average recovery must be 80-120%. If the above criteria are not met, the entire set o f samples should be re-injected or re-prepared as appropriate. ETS-8-044.0 Page 9 of 11 AnalysisMethod o f Analysis for the Determination of Perfiuorinated Compounds in W ater by LC/MS/MS; D irect Injection E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 116 of 145 p. 122 Ir,eumeni may be ueed, >fcurrent, for U days from 02'03/2010 CONFIDENTIAL 10.6 Field M atrix Spikes / Lab M atrix Spikes Recoveries of field matrix spikes and laboratory m atrix spikes are anticipated to be between 70% and 130% o f the fortified levels. Sample results for spikes outside o f 70% to 130%, may be flagged as such (with expanded accuracy statements), or win not be reported due to non-compliant quality control samples. The targeted fortification leveteshould be at least 50% o f the endogenous level and less than 10 times the endogenous level to tie used w ithoutjustification,to determine the statement of accuracy for analytical results. The average of Hie sam pleand the Held duplicate should be used to calculate the recovery. 11 Data Analysis.and C alculations. Use the following equation to calculate the amount o f analyte found (In ng/mL, based on peak area) using the standard cu n (linear regression parameters) generated by an appropriate software program: (Peak Area - Intercept) ^ Analyte found (ng/mL) Slope DF = factor by which the final volume was diluted, if necessary. For samples fortified with known amounts of analyte prior to extraction, use the following equation to calculate the percent recovery. Total analyte found (ng/mL) - Average analyte found In sample (ng/mL) )c _Q Recovery Analyte added (ng/mL) 12 Methpd Perform ance . , , , _________ Any method performance param etersfoat are not achieved must be considered in the evaluation of the data. Nonconformance to any specified parameters must,be described and discussed if the Technical Manager (nonGLP study) or Study Director (GLP study) chooses to report the data. If criteria listed in this method performance section are not met, maintenance may be performed on the system and samples reanalyzed, or other actions taken as appropriate. Document all actions in the raw data. If data are to be reported when performance criteria have not been met, the data must be footnoted on tables and discussed in the text o f the report. ' u 12.1 System Suitability System Suitability standards are not a required component o f this method. If required by protocol or by foe technical manager, d minimum o f fore^ systenVsuitability samples are injected at'the beginning of each analytical run prior to foe calibration curve. Typically these samples are at a concentration near foe mid level o f foe calibration curve and are repeated injections from one autosampler vial. The system suitability injections must have area counts with an RSD of s 6% and a retention time RSD o f s2% to be compliant. 12.2 Quantitation ! .,' C alibration C urve: The coefficient o f determination (r2) value for foe calibration curve must be greater than or equal to 0.990. Each point in the curve must be within 25% of foe theoretical concentration with the exception of the LLOQ, which may be within 30%. CCV Perform ance: The calibration standards that are interspersed throughout foe analytical sequence are evaluated as continuing calibration verifications in addition to being part o f the calibration curve. The accuracy of each curve point must be within 25% o f foe theoretical value (within 30% for lowest curve point). Samples that are bracketed by CCVs not meeting these criteria must be reanalyzed. ETS-8-044.0 Page 10 o f 11 M ethod o f Analysis fo r the Determ ination o f Perfluorinated Compounds in W ater by LC/MS/MS; D irect Injection A n a ly s is E07-0149; Interim Report #2 Page 117 of 145 3M Cordova Groundwater December 2009 'jo.'utT ir-n m a y i; CONFIDENTIAL p. 123 14 cays iVotj C?/G3:?3 D em onstration o f S p ecificity: Specificity is demonstrated by chromatographic retention time (within 4% of standard) and the mass spectral response o f unique ions. 12.3 Sensitivity The targeted limit of quantitation for all analytes is 0.025 ng/mL. The LOQ for any specific analyte may vary depending on the evaluation of appropriate blanks and the accuracy of the low-level calibration curve points. Refer to Section 10 for additional details. 12.4 Accuracy This method and required quality control samples are designed to generate data that are accurate to +1-20%. Section 10 contains additional information regarding the required accuracy o f laboratory control spikes, field matrix spikes and laboratory matrix spikes. 12.5 Precision Samples should be collected in duplicate in the field. The relative percent difference, RPD, should be reported. RPD results greater than 20% will be flagged in the report, but w ll not be excluded from reporting. The requirement for replicates exdudes field blanks or rinse blanks. Section 10 contains additional information regarding the required precision o f laboratory control spikes. 13 Pollution Prevention and W aste Management Waste generated whan performing this method w ill be disposed of appropriately. The original samples will be archived at the 3M Environmental Laboratory in accordance with internal procedures. 14 Records Each data package generated for a study must indude all supporting information for reconstruction o f the data. Information for the data package must include, but is not limited to the following items: study or projed number, sample and standard prep sheets/reoords, instrument run log (instalment batch records, instrument acquisition method, summary pages), instrument results files, chromatograms, calibration curves, and data calculations. 15 Affected Documents None. 16 Revisions R e visio n Number Summary o f Changes ETS-8-044.0 Page 11 o f 11 AnalysisMethod o f Analysis fo r the Determination o f Perfluorinated Compounds in W ater by LC/MS/MS; D irect Injection E07-0149; Interim Report #2 Page 116 of 145 3M Cordova Groundwater - December 2009 p. 124 CONFIDENTIAL Atta c h m e n t D: S a m p l e C h r o m a to g r a m s a n d C a lib r a tio n C urves E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 119 of 14S *** Ginger AGQ13J0S09 UrWUlaW 0CMlWhAWIHw.a~:V-pOffvcPA*d-rc!d!rfw)i&iobtooinuMcWr `rrrtitin ~ li*ll lltMX; :i SM(1 Typa: tAM tfd 1.08 C aidviatad Cvnsi t . l l t nyt ml AC, t o l* : \tt u /i " t aaoe AC. T i M ; tM R w tiflM i h c . A lgorithm Mj<*. I k Haight Hi. ? ** Hjdthi Ih M C liitf Hjdtftl IT Hi SAM: Cxj'*'lad AT: VS A a U tlir ftT; Mu Irrs eD iC - iQ4 rt PA T>3 0. 0 * sac 6 puints iO .fl sac t.o e alis Ha 900 aoeo 00 lC. typ*. VaiJay ItN I ,T ie *. l.OA in w u ro HalghC: 1 . ! ! ' } cps l t * i t T i**c i.T l n (i>3 T i 4: 1 ..*t nn 4000 MOO 3 u *ft tg^i^iaynpfc-yi CPtwtkwNWmwX:TOWl-OWMtaW3M40*t2A1I*VflrtMcrSJt>aaMr K * f H p l t !ndh; 15 C M pI* Ty|: C om c*t/'in: It/K C l I c a U l M Cc.nc? M i . o fla i AC. t * t i : As. T |* j tHl i / U / $ 1:4<;*5 AT U iM tav! fctp<cti At: US till! v AT: .>9. l.M s sac to Jut. tys*. Manual Aaw a lle r, *r*h* t in -2 3?*2>P- in mini t . U v M i rps *:se Tt* i.00 in ' **-A Tl*i 1 2 in CONFIDENTIAL Results Name: g091211a.rdb SM1* IM*X: #1 t/> t% ac O h r.tftlU iiM ! S .*0 h ^ /U ( M l t t a * Cm W> i l i * / l AAec., PtkAaW*:! W1:9M1:U01W SM A t tfiMev< Exparta AT: V ia B alativa M i Yea )M l.fti Ha 8tc > 4iM?0 i j cawc#itco>i isaiTss^iyu.iiy S o a p l* Im tox; t t a f i M TyT*: m Unknuwn H/A C t l c a l i t a d Carter 0 . ' i T *Qi Ac. U t t t U fli/W * Ac:. T ia a i 10; J * s M FM AT WiMAows it p C f 4 A?j '.m A a U t lv a M i ,0 .0 t.o o Ha 84C in t u t - Typ* K l t t i t t i t n Tistar A rt*; H eight: S ta n Tie: CM T lM I *unal Y -t sift IA ` J3 n * ; .W W er* 0.04 1 41 In TMw.flHn p . 125 Data worked up by STW Printing Time: 11:32:14 AH Printing Date: Thursday, January 28, 2010 E07-0149; Interim Report *2 3M Cordova Groundwater - December 2009 Page 1 of 5 Page 120 o f 145 Ginger AG01330509 CONFIDENTIAL Results Name: g091211a.rdb p. 126 Printing Date: Thursday, January 28, 2010 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 1 2 t Of 145 Ginger AG01330509 CONFIDENTIAL Results Name:.g091211a.rdb p. 127 Printing Date-. Thursday. January 28. 2010 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 122 of145 Ginger AG01330509 CONFIDENTIAL Results Name: g09l2lia.rdb p. 128 Printing Time: 11:32:14 AM Printing Date: Thursday, January 28. 2010 07-01*9; Interm Report *2 3M Cordova Groundwater - December 2009 Page 123 erf 145 Singer AG0U30S09 CONFIDENTIAL Results Name: g091Zlla.rdb p. 129 Printing Date: Thursday, January 2 6 , 2010 E07-0149. Interim Report #2 3M Cordova Groundwater - December 2009 Page 124 Of 145 Ginger AG01330509 CONFIDENTIAL S g09121 la .ttf (PFBA): ' Q uadratic" R egression (" 1 / x* w eighting)?y = -41 xA2 + 8.27e+004 x 4.54e+003 (r = 0.9999) 1.19e7 1.15e7 1.10e7 Results Name: g091211a.rdb illliliii 11 | 1 1 1 1 1 1 1 1 1 I p. 130 0 IO 20 30 40 50 60 70 80 90 100 110 120 130 140 150 ______ _______________________________________________________________ C oncentration. ng/m L_______________________________________________________________________ Data worked up by s u Printing Ti: 11:32:38 AM Page 1 of .1 Printing Date: Thursday, January 28, 2010 EO7-0149; In te rn i Report #2 3M Cordova Groundwater * December 2009 Page 125 o f 145 Ginger AG01330f>09 CONFIDENTIAL Resuits Name: g0912Ila.rdb p. 131 Printing Dace: Thursday, January 28, 2010 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 126 o f 145 *** Ginger AG01330509 CONFIDENTIAL Results Name: g09121la.rdb p. 132 Printing Time: 11:33:10 AM Printing Date: Thursday, January 29. 2010 - E07-0149; Interim R eport#2 3M Coidova Groundwater - December 2009 Page 127 Of 145 *** Ginger AG01330509 CONFIDENTIAL Results Name: g09121la.rdb g091211a.rdb (PFHS): "Q uadratic" R egression ("1 / x" w eighting): y = -1.1e+003 xA2 5.37e+005 x + 4.32e+003 (r = 0.9996) p . 133 10 20 30 40 50 60 70 80 ____________________________________________________________ C oncentration. ng/m L 90 Data worked up by STVf Printing Time: 11:33:28 AM Printing Date: Thursday, January 28, 2010 07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 100 110 120 130 140 150 Page 1 of 1 Page i2 8 o i4 5 Ginger AG01330S09 CONFIDENTIAL Pesiti ts N am e: g091213a.rdb g091211a.rdb (PFOS). "Quadratic" Regression ("1 / x" weighting): y = -1.78e+003 x*2 + 6.73e+005 x 1.3e+004 (r = 0.9999) 7.0e7 -t 6 .5 e7 - O 6 .0 e7 - 5 .5 e 7 - S.0e7 4.5e7 4.0e7 A rea, counts 3 .5 e 7 - 3.0e7 2 .5 e7 - 2 .0 e 7 - 1.Se7 1.0e7 S.0e6 - o.o 0 10 S> 30 4 0 SO 60 70 80 90 100 110 120 130 140 150 C oncentration. ng/m L _________________________________________________________ Data worked up by STW Printing Time: 11:33:44 AM Page 1 of l Printing Date: Thursday January 28 2010 07-0149; Interim Report #2 Page 129 b! 145 3M Cordova Groundwater - December 2009 p . 134 Ginger AG01330509 CONFIDENTIAL Results Name: glOQlOba.rdb p . 135 Data worked up by STW Printing Time: 11:38:58 AM Printing Date: Thursday- January 28, 2010 E07-0149: Interim Report 2 3M Cordova Groundwater - December 2009 Page 1 of 1- .. Page 130 o f 145 " * Ginger AG0J330509 i i Mfi^SiStaw*'t'iioofa*iiriz.zm..aM...mi.r....`i.a.m..{.aI.IImIIB,>mecm4aijmt2jat_smooornw*w ?*fizB S 3F ia a p l* Irdeiir 2 ) ip !t T /te: Stendatd i> M *ftirM t-o: '.'ttivlarw d '..w. : I . #2 1.40 n/*}. n ^/iL M il Ac*. Oita: J2/2T/2 4 Ait- T la e i PK I M S M M Ifiw fe AT M in s -. tap .-** *TUs* f t I* t iv 9 PT ?* is t.t 54. 1 >*< ate SM 30*8 In . Type: Manual K a lin in s Ti = 10.i am > 12 )0 founts j.T 2 * * W S cpa S t* ft Tie*: .9 am tr.4 -am: :0.e am 1M temni 4*6 us i f 14*6 * 1*4 1M 1 2 bS 13h6 SOM IM 0*4 XOaa 04 0.9021? nj/ttL 13/2S/H 19 . U J T : 1 AM lo t . Typti ft*l*M i9 r. Tiff A r*i K arw ai 74J:i .2 r. Data worked up by STO Printing Time: 11:36:48 AM Printing Date: Thursday, January 28, 2010 CONFIDENTIAL Results Name: g09122Za.rdb I *<*>:rmamo ----- ---ft. I CiWMif.t jw ttK M ICr NMMMi'* S *a f>l* Jadea : IT **>1 * T,*p! i2C lfn: C * 5 t a i i ' *d Lur.. i.itt i.2 ta */*>i. tW | A c*. Cat*> Acq. T la ei U rli/M D t s: 14:52 PH H V 74*4* AT H if tiv r , E*fk-tt*4 AT: C<* H a la t U a AT >0-0 td .l * 74M ;j U t . Typ*: Aaie&tior. T in *: H O -jr-t! S tart Tin*: C M Tlln* t Manual to .2 IIK < M IR U #. *09 4 cpa M J thin 10.1 a: a MM SOM ISM SOM ! * I SOM 3SM 10M ISM ZOM-j t jS *4 ; 14M u 1 is 1 Sanpl* Saaj/U Tyv*j C o n cn tfiti*> ! C a le a l it a a Cone; A*. l t i A*. T l**: ni ynlftvwn M/A a . i 2: uf/m i. 1 2 /1 4 /2 4 9 ! : ; 4 : i 4 AH AT Uifidov: l a r i e t ! STi !i s . t a la r i AT: T il > *. 14. 1 It MCale In?. Trp*: S t*n tjw r. TIM M Staff 7U #t Cn4 7 l e * i tumtaal at A J*?4 W* S,0T**442 cp* t . i t ain 14.1 am so n 900 400 $ 360 s 1 300 2S0 300 ISO - - 1 .' 100 so 0 Page 1 of,.A E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 131 of 145 p. 136 Ginger AG0330509 CONFIDENTIAL Results Name: g091222a.rdb p. 137 Printing Time: 11:36:48 AM Printing Date: Thursday, January 23, 2010 E07-0149; Interim Report 2 3M Cordova Groundwater December 2009 Page 132 o f 146 Ginger AG013305O9 c o n f id e n t ia l Results Name.- g09i222a.rcJt' p. 138 (tinting Date: Thursday, January 28, 2010 E07-0149; Interim Report #2 3M Cordova Groundwater - Oecember 2009 Page 133 Of 145 Ginger AG01330509 w o r Ww n )'W u An iii'MUwM<twhaU> j*>wyj ooafnoonw r M* Hi<wtnvl i p t c t * K?: e t* ftelatkfe t t ; A t**: l i e n Ti*; IM tlM i k-)CII1.2!*111U22...2i c*o unriftiiin*nns UiS SM I S*S I 1M Ifla S 2M ia e p ie *nrtk! i * y l * Type; Bertram ra t in ; tile u liiM ft. O il : Ae\C T ie ; * Onnuwe KM i.m ji tn /ii 1 2 /2 J /2 ** l i ? * : 1 M N M itU ri; T Window. L tp tc tM *T : Bie (telai IV * St Urn is .* ij.i Rj me ` irv t*:n ;io n T|*. St: * 19* 1 ' H at* ri-** EMl t l r N iiV iil 12.1 1# li t * *HI|U l . i T * . '/ ) . rpa ie .i in 12. in 700 400 1300 1100 ^ 1000 1- 00 700 00 900 , 400 200 200 00 0 Data worked up by STW Printing Time: 11:36:4$ AM Printing Date: Thursday, January 26# 2010 CONFIDENTIAL Results Name: gG91222a.rdb PtthMwn,*WQT Staple liM : S tap le Typ * i iivAkVUl tm%.1uus C a U u le ra d r.-wAc Ac*. fu te i hot. T IM I 2 ' OC .3 4 * . 232 np/rrO. 12/ 22/ 200% it ti hi r r viM inai b * j lW IT : V a Ite 1a t i r e R? Ve 1A.A 1 2 .4 to sec in t a t . type; Manuel T i : 12. a.ir. re*: I M I5 e o 'w u 2 . d,1*PCS fip * S t a r t Tia>*: U .> In CM tie.ei U .4 in ZOeS IM 1M IM Ifie t IM 14eS iM S I fptma.*itJietmfcL:i'-rWfoUr BnbuWm1i:b49a8p.abam&*Wm.f*takJaimiao' mWouaWwoozxzommtet/ SuCB*pmtenm1*M. 'MC c!m .-G m1*c1w A n w ta to n ' 3***lo 1{y i ,., filf>uu S M n i> m t( n ! MM CAA*4le..atiTM*lt*t***s:4 Can-;:1{2:2)24;/2*4i* n^/tiL M M } t !<*- ST Window: IV^tp* *ck `a.U-3t iRvTAt RT: !A t. Tv?*! A *i a t|0 til*; *r**i >t*x t:! tn-i r iM - IK*M*n* E07-0149; In te rn i Report #2 3M Cordova Groundwater - December 2009 12 4 f Page 4 of 4 7t 0 10 11 12 t t 14 IS IS Page 134 o f 145 p. 139 ** Ginger AG01330509 CONFIDENTIAL Results Name: gl00105a.rdb p. 140 Printing Date: Thursday. January 38, 2010 E07-0149; Interim R eport#2 3M Cordova Groundwater - December 2009 F>age 135Of 145 * Ginger AG01330S09 CONFIDENTIAL Results Name: g091222a.rdb p. 141 Printing Date: Thursday. January 28, 2010 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 1 3 6 of 145 Ginger AG01330SQ9 CONFIDENTIAL Resuits Name: g09l222a.rdb p. 142 Printing Date: Thursday, January 28, 2010 E07-0149. Interim R e p o rt 3M Cordova Groundwater - December 2009 P age137of145 **' Ginger AGQU30509 CONFIDENTIAL Results Name: g09l222a.rdb K g091222a.rdb (PFHS): 'Q ua d ra tic" R egression ("1 / x" w eighting): y = -5.94e+004 xA2 + 4e+006 x + 2.6e+003 (r = 0.9991) 6 .5 e 7 - 6.0e7 5.5e7 5.0e7 4 .5 e 7 4 .0 e 7 - Sc 3,5e7 3 3.0e7 I 2 .5 e 7 - 2.0e7 1.5e7 1.0e7 p . 143 5 .0 e 6 - / 0.0 - 1 Data worked up by STW Printing Time: 11:35:36 AM Printing.Date: Thursday* January 28, 2010 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 ____________ C oncentration. ng/roL________ ______________________________________________________________ Page 1 of 1 E07-0149; Interim Report *2 3M Cordova Groundwater - December 2009 Page 138 o f 145 *** Ginger AG01330509 CONFIDENTIAL Results Name: g091222a.rdb A rea, counts p. 144 Printing Time: 11:35:51 AH Printing Date: Thursday, January 28, 2010 E07-0149; Interim R eport#2 3M Cordova Groundwater - December 2009 P aae1 3 9 of1 4 5 Ginger AG01130S09 CONFIDENTIAL Results Nane: jlOOlHa rdb p . 145 Data worked up by 5TW Printing Time: 11:42:08 AM Printing Date:. Thursday, .January 28, 2010 E07-0149; Interim Report *2 3M Cordova Groundwater." December 2009 Page l o f i Page 140 of 145 ** Ginger AG01330509 CONFIDENTIAL Results Name: jlOOllra.rdb J100114a.rdb (PFBS): "Q uadratic" R egression ("1 / x" w eighting): y = -1 .1 1e+006 x*2 + 1.22e+007 x + 3.82e+004 (r = 0.9988) p. 146 ___________________________________________________________ _______________________C oncentration, n g /m L _________ Data worked up by STW Printing Time: 11:40:40 AM Printing Bate: Thursday, January ZB, 2010 E07-0149: Interim R eport#2 3M Cordova Groundwater - December 2009 Page 1 o f 1 Page 141 Of 145 CONFIDENTIAL Atta c hm en t E: P r o to c o l a n d M etho d D eviations p. 147 E07-0149; Interim Report #2 3M Cordova Groundwater - December 2009 Page 142 of 145 p. 148 3M Confidential Record of Deviation^onconformance I. Identification Study / Project No. E07-0149 - Interim Report #2 Date(s) o f Occurrence: Document Number: Sequence g091222a and gl00105a ETS-8-154.3 Deviation type SOP Equipment Procedure El Method (Check one) Protocol Q GPO O th e r____________ II. Description (attach extra pages as needed) Method Requirements: 1. CCV recovery within 1 25% of true value (section 10.4). 2. IC S average recovery of 100% 20% . 3. FMS recoveries within 30% (section 9.6). Actual procedure/process: (1 ) Sequence g091222a - One of the eleven CCVs for PFOA had a recovery of 72.4% . (2 ) LCS of branched PFOS and PFBA both had an average recovery of 126%. (3 ) PFOS FMS LS recovery for location C0IL-GW -C1 was 66.9% III. Actions Taken (such as amendment issued, SOP revision, etc.) Corrective Action ( Yes 0 No) Reference: Acceptability of the nonconforming work: 1) Eleven CCVs were analyzed during the course of the run with one CCV for PFOA recovering at 72.4% . Curve criteria, LCS criteria, and FMS recovery criteria were all met for PFOA. Samples bracketed by the CCV will be noted in the report. 2) The branched PFOS when quantitated against calibration curve point prepared from linear PFOS have been quantitating around 15-20% higher. The average recovery of 126% for both PFOS and PFBA were within the acceptance criteria of 30% for FMS samples. 3) The other two FM S samples for PFOS for location C O Il-G W -C I met method acceptance criteria with recoveries of 60.2% and 85.4% . Since the low spike was the most appropriate as compared to the sample concentration, the analytical uncertainty will be adjusted accordingly. Actions: O Halting o f W ork C lient N otification W ork Recall W ithholding o f Report El O th e r D eviations w ill be noted in final report. Project Lead/PAI Approval: Susan Wolf p ^ Date-, , Study Director (if GLP): Q SponsorApproval (for GLP p ro toco l deviatio ns): NA lllS Itb Ds% ltz llO Date: NA Technical Reviewer (optional): Date: Laboratory Department ManagerApproval: Date: P9 IV. Authorization to Resume Work Where halting o f work occurred, resumption o f work must first be approved by Laboratory Management LaboratoryDepartment ManagerApproval: NA Date: NA Deviation No. f (assigned b y S tudy D ire ctor o r Teem L e a d e r at the end ot study o r p roject) Attachm ent A Documentation of DeviSflr9ET^Sh-iJ4f-00i50?8i.B7Ktff^onconfomriing Testing Page 1 o f 1 Page 143 of 145 3M Cordova Groundwater December 2009 p . 149 3M Confidential R e c o r d o f D e v ia tio n W ^ n c o n f o r m a n c e I. Identification Study / Project No. E07-0149 - Interim Report #2 Date(s) o f Occurrence:, ' Document Number; Sequence g091211a and glOOlOTa ETS-8-110.1 Deviation type SOP Equipment Procedure 0 M ethod (Check one) Protocol GPO ' Other: //. Description (attach extra pages asneeded) Method Requirements: 1. CCV recovery within 2 5 % of true value (section 10.3) ,,, - Actual procedure/process: (1 ) One of the seventeen CCVs for PFSA and PFBS did not meet method acceptance criteria with recoveries 163% and 141%, respectively. III. Actions Taken (such as amendmentissued, SOP revision, etc.) Corrective Action ( Yes 0 N o) Reference: Acceptability of the nonconforming work: . s. 1) QC criteria were reviewed and met method acceptance criteria: curve accuracy. LCS and sample FMS recoveries. Semples bracketed by the PFBA and PFBS CCV not meeting method acceptance criteria, will be noted in the report. Actions: Hatting o f W ork O Client N otification W ork Recall W ithholding of Report El Other: CCV deviation will be noted in final report. Project Lead/PAI Approval: Susan Wolf Study Director {if GLP): SponsorApproval (for GLP protocol deviations): NA Technical Reviewer (optional): / / WDate / Date: t i fillio Date: NA Date: Laboratory Department Manager Approval: Date: IV. Authorization to Resume Work Where halting o f work occurred, resumption o f work must first be approved by Laboratory Management LaboratoryDepartment ManagerApproval: NA Date; NA Deviation No. 2 (assigned b y S tudy D ire ctor o r Teem Leader a t th e end o f study orp roject) Attachm ent A ETS-4-008.7 Page 1 o f 1 D o c u m e n ta tio n o f D e v iiftriy W l n e c m fiia P e f N b n c o n fo rm in g T e s tin g 3M Cordova Groundwater - December 2009 Page 144 of 145 p. 150 3M Confidential RECORD OP DEVIAffoN^ONCONFORMANCE /. Identification Study / Project No. E07-0149 - Interim Report #2 Date(s) o f Occurrence: Document Number: S equenceg0912l1aandg100107a ETS-8-110.1 Deviation type SOP Equipment Procedure M ethod (Check one) El Protocol GPO Other. II. Description (attach extra pages as needed) Method Requirements: 1. Field matrix spikes (section 9.1 of Protocol). Actual procedure/process: (1 ) Location COlL-GW -M W -9-94 did not have fit matrix apike level appropriate for P F8A . Several other locations also did not have an appropriate field matrix strike level for PFBA. In those instances, a laboratory matrix spike was prepared a t an appropriate level. This sample (C O Il-G W -M W -9-94) was Inadvertent!y missed when preparing laboratory matrix strikes. III. Actions Taken (such as amendment fesuedf SOP rvision, efc.) Corrective Action ( Yes 0 N o) Reference: Acceptability of the nonconforming work: 1) Data will be flagged in the report as not having an appropriate matrix s p ik e .; Actions: Halting o f W ork C lient N otification W ork Recall W ithholding o f Report 0 Other: Deviation will be noted in final report. Project Lead/PAI Approval: Sus< Study Director (if GLP): Sponsor Approval (for GLP protocol deviations): Technical Reviewer (optional): $. D a te ; /O . p i/io D a t e : ^ Y ^ /i D ate: Laboratory Department Manager Approval: Date: IV. Authorization to Resume Work Where halting o f work occurred, resumption o f work must H itt be approved by Laboratory Management Laboratory Department Manager Approval: N A Date: NA Deviation No. y (a s s ig n a i b y S tudy D ire c to r o r Team L e a d e r a t th e end o f study o r pro je ct) Attachm ent A Documentation of D eyiil5itE^TSi(-!4|t-00f0th8ff.e7i<8ff?onconforming Testine ofPage 1 o f 1 Page 145 145 3M Cordova Groundwater December 2009