Document by4ZrJOgbR4jyRRMJNLKKjKZ1

Jean B. Sweeney Vice President S3MafeEtynvOirpoenrmateinotnasl, Health and 3M Center, Building 0224-05Ra/-I)3 St. Paul, MN 55144-1000 651 737 3569 ORIGINAL February 11, 2010 CERTIFIED MAIL 4 ^ Document Processing Center EPA East - Room 6428 Attn: Section 8(e) Office of Pollution Prevention and Toxics, U.S. EPA 1200 Pennsylvania Avenue NW Washington, DC 20460-0001 C,<PfT\cP 'VD>-,\ .0 si3 ... V_ <c. .-C NO CBI *5 Re: TSCA 8(e) Substantial Risk Notice: Sulfonate-based and Carboxylic-based Fluorochemicals, Docket 8EHQ-0598-373 - Results from 2009 Analyses of Fish from the Mississippi River Dear Sir or Madam: 3M is submitting this notice to supplement previous submissions on sulfonyl and carboxyl based fluorochemicals (FCs), and more specifically our June 20, 2006 and November 9, 20g submittals concerning fish data generated by the Minnesota Pollution Control Agency " (MPCA). The November 9, 2009 submittal included an Excel file, provided to 3M by the MPCA, entitled "PFCs MissPool2 Fish all years.xls" and 3M Environmental Laboratory 7T Report No. E09-0372, Fluorochemical Analysis of Fish Fillet Homogenates Collected from the Mississippi River by the Minnesota Pollution Control Agency May 2009 - Phase 1: : PFOS. v.o The aforementioned Excel file included fish fillet data for 297 fish collected from Pool 2 of CD the Mississippi River in 2009 that were analyzed by the MPCA for C4-C12 perfluorocarboxylic acids; C4, C6 and C8 perfluorosulfonates; and perfluorooctanesulfonamide. The 3M Environmental Laboratory Report presented fish tissue analytical results for PFOS for 30 of the 297 fish samples that were split in order to obtain confirmatory data. Enclosed with this correspondence is a second 3M report entitled "3M Environmental Laboratory Report No. E09-0372, Fluorochemical Analysis of Fish Fillet Homogenates Collected from the Mississippi River by the Minnesota Pollution Control Agency May 2009 Phase 2: Perfluorocarboxylic Acids (C4-C12), Perfluorobutane sulfonate (PFBS), Perfluorohexane sulfonate (PFHS) and Perfluorooctanesulfonamide (FOSA). This report presents additional corroborative analytical data for the previously referenced 30 fish for the analytes indicated. As noted in the November 9 correspondence, sample identification nreufmerbeenrcsedinttohceoEmxpcaerlespspreliatdssahmeeptleanrdestuhlets.3M Environmental Laboratory Report can be cross- While 3M does not believe that any of the referenced or submitted data taken alone or cumulatively meet the "substantial risk" reporting threshold, and while 3M was not responsible for the generation of this information (other than the 3M analytical data provided here), we nevertheless recognize the ongoing work by U.S. EPA to assess fluorochemical CONTAINS NO C8I 3 <24 $ 3 ) U.S. EPA Document Processing Center February 11, 2010 Page 2 exposure pathways. Therefore, we are placing these results in the 8(e) docket as a supplement to previous submissions. If you have any questions, please do not hesitate to contact Deanna Luebker at (651) 737-1374 or djluebker@mmm.com. Sincerely, Jean B. Sweeney EVnicveirPornemsiednetnatl, Health and Safety Operations Enclosure / \N: P-3 3M ENVIRONMENTAL LABORATORY REPORT NO. E09372 O sC Final Analytical Report V )* v Perfluorochem ical Analysis of Fish Fillet Hom ogenates Collected from the Mississippi River by the M innesota Pollution Control Agency in M ay 20 09 - Phase II: Perfluorocaryboxylic Acids (C 4-C 12), Perfluorobutane sulfonate (PFB S), Perfluorohexane sulfonate (P H F S ) and Perfluorooctanesulfonam ide (FO S A ) ? Laboratory Request Number: E09-0372 Method Requirement: ETS 8-45.0 Testing Laboratory 3M EHS Operations 3M Environmental Laboratory 3M Center Building 260-5N-17 Maplewood, MN 55144 J. * ! r-C ' i O Requester Gary Hohenstein 3M EHS Operations 3M Center Building 224-5W -03 Maplewood, MN 55144 CCREDITEDI Certificate #2052-01 The testing reported herein meet the requirements of ISO /IEC 17025-2005 "General Requirements for the Competence of Testing and Calibration Laboratories'', in accordance with the A2LA Certificate #2052-01. Testing that complies with this International Standard also operate in accordance with ISO 9001:2000. 3M ENVIRONMENTAL LABORATORY PAGE 1 OF 104 P-4 3MENVIRONMENTAL LABORATORY REPORT NO. E09-Q372 3M Environmental Laboratory 3M Environmental Laboratory Manager: W illiam K. Reagen, Ph.D. 3M Principal Analytical Investigate- and Report Author: Michelle D. Malinsky, Ph.D. Analytical Report E09-0372 Perfluorochemical Analysis of Fish Fillet Homogenates Collected from the Mississippi River by the Minnesota Pollution Control Agency May 2009 - Phase II: Perfluorocarboxylic Acids (PFCAs) C4-C12, PFBS, PFHS, and FOSA Report Date: Upon Signing The Minnesota Pollution Control Agency (M PC A ) submitted thirty fish fillet hom ogenates to the 3M Environmental Laboratory for perfluorochemical analysis under project number E 09-0372. The thirty submitted samples represented an approximate ten percent split of the total samples collected during a May 2009 fish sampling campaign from Pool 2 o f the Mississippi River. Six samples from five different species comprised the sam ple set. The fillet homogenates were extracted and analyzed using method ETS 8-45.0 "Determination o f Fluorochemicals via Protein Precipitation of Fish Tissues (Fillet or W hole Body) and Analysis by High Perform ance Liquid Chromatography with Tandem Mass Spectrometry". The target analytes for this study included perfiuoroalkane carboxylic acids ranging from C4 to C12, perfluoroalkane sulfonates (C 4, C 6, and C 8), and perfluorooctanesulfonamide. Results for PFO S were provided in the Phase I report. This Phase II report provides the results from the other target analytes. T ie foil chemical names, structures, and acronyms for each analyte are provided in Section 2.1. The summarized results h a w been broken out into four separate tables: Table 1: perfluorobutanoic ad d (PFBA), perfluoropentanoic acid (PFPeA ), and perfluorohexanoic acid (PFHxA). Table 2: perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFO A ), and periluorononanoic acid (PFNA ). Table 3: perfluorodecanoic acid (PFD A ), perfluoroundecanoic ad d (PFUnA), and perfluorododecanoic ad d (PFDoA ) Table 4: perfluorobutane sulfonate (PFB S), perfluorohexane sulfonate (P FH S ), and perfluorooctanesulfonamide (FO SA). All results for quality control samples prepared and analyzed with the samples will be reported and discussed elsewhere in this report. The testing reported herein m eet the requirements o f ISO /IEC 17025-2005 "General Requirements for d ie Competence of Testing and Calibration Laboratories", in accordance with the A2LA Certificate #2052-01. Testing that complies with this International Standard also operate in accordance with ISO 9001:2000. C ertificate #2052-01 3M ENVIRONMENTAL LABORATORY PAGE 2 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 T a b le 1. S am p le R e s u lts S u m m ary: P FC A s (C 4 -C 6 ). 3M LIMS ID Sample Description E09-0372-001 E09-0372-001 Dup Axys ID- L12916-14, Client ID - 090191 Axys ID- L12916-14, Client ID - 090191 Dup Species Carp E09-0372-002 E09-0372-002 Dup Axys ID- L12916-24, Client ID - 090054 Axys ID - L12916-24, Client ID - 090054 Dup Carp E09-0372-003 E09-0372-003 Dup Axys ID -112916-26, Client ID- 090056 Axys ID - L12916-26, Client ID - 090056 Dup Carp E09-0372-004 E09-0372-004 D ip Axys ID - L12917-3, CSent ID - 090275 Axys ID - L12917-3, Client ID - 090275 Dup Carp __ E09-0372-005 E09-0372-005 D io Axys ID - L12917-10, Client ID - 090282 Axys ID - L12917-10, Client ID - 090282 Dup Carp E09-0372-006 E09-0372-006 D ip Axys ID- L12917-17, Client ID - 090123 Axys ID- L12917-17, Client ID - 090123 Dup Carp E09-0372-007 E09-0372-007 Dup Axys ID - L12931-6, Client ID - 090173 Axys ID - L12931-6, Client ID- 090173 Dup Smallmouth Bass River Location Extracted Mass (g) <VPFBA Cone (ng/g) Section 3 Section 1 Section 1 Section 4 Section 4 Section 2 Section 3 0.2403 0.2344 Average %RPD 0.2555 0.2613 Average %RPD 0.2468 0.2328 Average %RPD 0.2364 0.2512 Average %RPD 0.2690 0.2604 Average %RPD 0.2638 0.2482 Average %RPD 0.2414 0.2563 Average %RPD <0.275 <0.282 <0.278 NA <0.258 <0.253 <0.255 NA <0.267 <0.284 <0.275 NA 0.299 0.271 0.285 10 0 .9 3 9 0.979 0.959 4.2 <0.250 <0.266 <0.258 NA < 0 .2 7 3 <0.258 <0.265 NA mPFPeA Cone (ng/g) <0.105 <0.108 <0.106 NA 0.124 0.191 0.158 w 43 <0.102 0.147 w 0.147 NA 0.253 0.113 0.183 <4>76 <0.0939 <0.0970 <0.0987 NA <0.0957 <0.102 <0.0987 NA <0.105 <0.0985 <0.102 NA <vPFHxA Cone (ng/g) <0.265 <0.272 <0.269 NA 0.341 <0244 (80.341 NA 0.312 <0.274 <J|0.312 NA <0.270 <0.254 <0.262 NA 1.21 1.05 1.13 14 0.318 0.293 0.306 8.3 <0264 <0.249 <0.256 NA 3M ENVIRONMENTAL LABORATORY PAGE 3 O F 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 1 Continued. 3M LIMS ID Sample Description Species E09-0372-008 EQ9-0372-008 Dup Axys ID - L12931-14, Client ID - 090032 Axvs ID - L12931-14, Client ID- 090032 Dup Smallmouth Bass E09-0372-009 E09-0372-009 Dup Axys ID - L12932-2, Client ID - 090094 Axvs ID - L12932-2, Client ID - 090094 Dup Smallmouth Bass E09-0372-010 E 0 9 -0 37 2 -0 1 0D u p Axys ID - L 12932-4, Client ID - 090096 A xysID - L12932-4,C lient ID -090096D u p Smallmouth Bass E 0 9 -0 37 2 -0 1 1 E09-0372-011 Dup Axys ID - L12932-9, Client ID - 090042 Axvs ID - L12932-9, Client ID - 090042 Dup Smallmouth Bass E09-0372-012 E09-0372-012 Dup Axys ID - L12932-26, Client ID - 090248 Axys ID - L12932-26, Client ID- 090248 Dup Smallmouth Bass E09-0372-013 E09-0372-013 Dup Axys ID - L12933-18, Client ID- 090064 Axvs ID - L12933-18, Client ID - 090064 Dup W hite Bass E09-0372-014 E09-0372-014 Dup Axys ID - L12933-20, Client ID - 090066 Axys ID - L12933-20, Client ID - 090066 Dup W hite Bass River Location Section 1 Section 2 Section 2 Section 1 Section 4 Section 2 Section 2 Extracted Mass (g) 0.2607 0.2507 Average %RPD 0.2375 0.2699 Average %RPD 0.2622 0.2561 Average %RPD 0.2430 0.2548 Average %RPD 0.2646 0.2602 Average %RPD 0.2433 0.2599 Average %RPD 0.2488 0.2424 A verag e %RPD ,VPFBA Cone (ng/g) <0.253 <0.263 <0.258 NA <0.278 <0.245 <0.261 NA <0.252 <0.258 <0255 NA 0,350 0.441 0.395 23 0.891 0.605 0.748 <438 0.538 0.922 0.730 <53 <0265 <0.272 <0.269 NA mPPPeA Cone (ng/g) <0.0969 <0.101 <0.0988 NA <0.106 <0.0936 <0.0999 NA <0.0963 <0.0986 <0.0974 NA 0.217 0.270 0.243 22 0.420 0.175 0.298 83 0.259 0.509 0.384 65 <0.101 <0.104 <0.103 NA ,vPFHxA Cone (ng/g) <0.245 <0254 <0.249 NA <0268 <0236 <0.252 NA <0243 <0.249 <0.246 NA (3|n r NR oN R NA P)NR ^NR P'NR NA mNR oiNR raiNR NA <0.504 <0.518 <0.511 NA 3M ENVIRONMENTAL LABORATORY PAGE 4 O F 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 3M LIMS ID Sample Description E09-0372-015 E09-0372-015 Dup Axys ID- L12933-25, Client ID - 090071 Axys ID - L12933-25, Client ID - 090071 Dup Species W hite Bass E09-0372-016 E09-0372-016 Dup Axys ID - L12934-10, Client ID - 090024 Axys ID - L12934-10, Client ID - 090024 Dup W hite Bass E09-0372-017 E09-0372-017 Dup Axys ID - L12934-12, CBent ID - 090026 Ary in - 117934-12 Client ID - 090026 Dup W hite Bass E09-0372-018 ft n i* \ Axys ID - L12934-18, CBent ID - 090017 Avus in . 117934-18 Client ID - 090017 Dud W hite Bass E09-0372-019 E09-0372-019 Dup Axys ID- L12945-1, Client ID - 090153 Axys ID - L12945-1, CBent ID - 090153 Dup Fresh W ater Drum E09-0372-020 Axys ID - L12945-4, Client ID - 090167 Fresh W ater Drum E09-0372-021 E09-0372-021 Dup Axys ID - L12945-14, Client ID- 090241 Axys ID- L12945-14. Client ID - 090241 Dup Fresh W ater Drum River Location Extracted Mass (g) Section 2 Section 1 Section 1 Section 1 Section 3 Section 3 Section 4 0.2518 0.2492 Average %RPD 0.2570 0.2436 Average %RPD 0.2442 0.2545 Average %RPD 0.2640 0.2433 Average %RPD 0.2568 0.2473 A v e ra g e %RPD 0.2372 0.2509 Average %RPD 0.2375 0.2574 Average %RPD lvPFBA Cone (ng/g) <0.262 <0.265 <0.263 NA <0.257 <0.271 <0.264 NA < 0 .2 7 0 <0.259 <0.265 NA < 0 .2 5 0 <0.271 <0.261 NA <0.257 <0.267 <0.262 NA <0.278 <0.263 <0.271 NA <0.278 <0.256 <0.267 NA n PFPeA Cone (ng/g) <0.100 <0.101 <0.101 NA <0.0982 <0.104 <0.101 NA 0 .1 0 3 <0.0992 0.101 NA 0 .0 9 5 6 0 .1 0 4 <0.0997 NA 0 .0 9 8 3 0.102 <0.100 NA 0 .1 0 6 0.101 0 .1 0 4 NA 0 .1 0 6 <0.0981 0.102 NA wPFHxA Cone (ng/g) 0 .4 9 8 0 .5 0 4 <0.501 NA 0 .4 8 8 0 .5 1 5 0 .5 0 2 NA <0.514 <0.493 0 .5 0 4 NA 0 .4 7 5 0 .5 1 6 0 .4 9 6 NA <0.489 <0.507 <0.498 NA 0 .5 2 9 0 .5 0 0 0 .5 1 5 NA <0.268 0 .2 4 8 <0.258 NA 3M ENVIRONMENTAL LABORATORY PAGE 5 O F 104 3M ENVIRONMENTAL LABORA TORY REPORT NO. E09-0372 Table 1 Continued. 3M UMS ID Sample Description Species E09-0372-022 E09-0372-022 Dup Axys ID - L12945-16, Client ID - 090078 Fresh W ater Drum Axys ID -112945-16, Client ID - 090078 Dup _________ E09-0372-023 E09-0372-023 Dup Axys ID - L12945-19, Client ID - 090081 Axys ID - L12945-19, Client ID - 090081 Dud Fresh W ater Drum E09-0372-024 E09-0372-024 Dup Axys ID - L12945-30, Client ID- 090009 Axys ID - L12945-30, Client ID - 090009 Dup Fresh W ater Drum E09-0372-025 E09-0372-025 Dud Axys ID - L12947-7, Client ID - 090266 Axys ID- L12947-7, Client ID - 090266 Dup Bluegill Sunfish E09-0372-026 E09-0372-026 Dup Axys ID - L12947-8, Client ID - 090267 Axys ID- L12W 7-8, Client ip - 090267D up Bluegill Sunfish __ _____ ___ E09-0372-027 E09-0372-027 Dup Axys ID- L12947-13, Client ID- 090111 Axys ID -L12947-13, Client ID -090111 Dup Bluegill Sunfish E09-0372-028 E09-0372-028 Dup Axys ID - L12947-25, Client ID- 090205 Axys ID- L12947-25, Client ID- 090205 Dup Bluegill Sunfish __... .......... ... River Location Extracted Mass (g) Section 2 0.2468 ____ 0.2657 Average %RPD Section 2 0.2345 0,2537 Average Section 1 Section 3 Section 3 Section 2 Section 4 %RPD 0.2385 0.2430 Average %RPD 0.2338 0.2583 Average %RPD 0.2355 0.2495 Average %RPD 0.2610 0.2581 Average %RPD 0.2455 0.2524 Average %RPD IVPFBA Cone (ng/g) < 0 .2 6 7 <0.248 <0.258 NA <0.281 <0.260 <0.271 NA <0.277 <0.272 <0.274 NA <0.282 <0.256 <0.269 NA < 0 .2 8 0 <0.265 <0.272 NA <0.253 <0.256 <0.254 NA 0.532 0.414 0.473 <25 mPFPeA Cone (ng/g) <0.102 <0.0950 <0.0987 NA <0.108 0.132 <*0.132 NA 0.157 <0.104 **0 .1 5 7 NA <0.108 <0.0978 <0.103 NA 0.124 <0.101 <2,0.124 NA 0.216 0.261 0.238 19 <0.103 <0.100 <0.101 NA mPFHxA Cone (ng/g) <0.258 <0.240 <0.249 NA <0,272 <0251 <0.262 NA <0.267 <0 2 6 2 <0.265 NA <0 7 7 3 <0247 <0.260 NA <0.271 <0.256 <0.263 NA <0.244 <0.247 <0.246 NA <0.260 <0.253 <0.256 NA 3M ENVIRONMENTAL LABORATORY PAGE6 OF1W 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 1 Continued. 3M UMS ID Sample Description Species River Location Extracted Mass (g) (VPFBA Cone (ng/g) mPPPeA Cone (ng/g) lvPFHxA Cone (ng/g) E09-0372-029 E09-0372-029 Dup Axys ID - L12947-26, Client ID - 090206 Axys ID - L12947-26, Client Ip - 090206 Dup Bluegill Sunftsh Section 4 0.2421 0.2479 0.738 0.724 <0.104 < 0.102 <0.263 0.340 Average 0.731 <0.103 '*0 .3 4 0 E09-0372-030 E09-0372-030 Pup Axys ID- L12948-17, Client ID- 090061 Bluegill Sunfish Axys ID - L12948-17. Client ID - 090061 Dup______ ____________ Section 1 %RPD 0.2544 ___ 0.2577 1.9 <0.259 <0.256 NA 0.124 <0.0980 NA <0.251 <0.247 Average <0.258 '*0 .1 2 4 <0.249 %RPD NA NA NA (1) Unless otherwise specified, the recovery of the associated laboratory matrix spice (IM S ) was within 10030% which meets ETS 6 4 5 .0 method acceptance criteriT Sample results are considered accurate to within the overall analytical method uncertainty 10013% (PFBA), 10048% (PFPaA), and 10039% (PFHxA). See Section ASDetBmmMion ofAnalytical Method Uncertainty for more information. Sample results are reported tolhree significant figures and %RPD to two significant figures Addrtxjnal significant figures were used to calculate the average, %RPD, and %recovery. Values in the raw data may vary slightly due to rounding. PFBA and PFPaA results were generated using a solvent (unextracted) curve for quantitation. PFHxA results were quantitated using an extracted cafibration curve prepared in a control matrix of bluegill fillet (2) One sample result was above the limitof quantitation (LOQ) and the other replicate was below the LOQ. The average reflects only the value above the LOQ. A relative percent difference (%RPD) was not calculated. (3) NR = not reported. The percent recovery of the associated laboratory matrix spike did not meet method criteria of 10030% The sanple results are not reported because the accuracy could not be assessed. (4) The %RPD exceeded 20%. 3M ENVIRONMENTAL LABORATORY PAGE 7 O F 101 3M ENVIRONMENTAL LABORA TORY REPORT NO. E09-0372 T ab le 2. S am p le R e s u lts S um m ary: P FC A s (C 7 -C 9 ). E09-0372-001 E09-0372-001 Dup Axys ID - L12916-14, Client ID- 090191 Axys ID - L12916-14, Client ID - 090191 Dup E09-0372-002 Axys ID - L12916-24, Client ID - 090054 E09-0372-002 Dup.... Axys ID- L12916-24, Client ID- 090054 Dup E09-0372-003 E09-0372-003 Dup Axys ID - L12916-26, Client ID - 090056 Axvs ID - L12916-26, Client ID - 090056 Dup E09-Q372-004 E09-0372-004 Dup Axys ID - L12917-3, Client ID - 090275 Axys ID - L12917-3, Client ID - 090275 Dup E09-0372-005 E09-0372-005 Dup Axys ID - L12917-10, Client ID - 090282 Axys ID - L12917-10. Client ID - 090282 Dup E09-0372-006 E09-0372-006 Dup Axys ID - L12917-17, Client ID- 090123 Axvs ID - L12917-17, Client ID - 090123 Dup E09-0372-007 E09-0372-007 Dup Axys ID - L12931-6, Client ID - 090173 Axvs ID - L12931-6, Client ID - 090173 Dup Species Carp Carp Carp Carp Carp Carp Smallmouth Bass River Location Section 3 Section 1 Section 1 Section 4 Section 4 Section 2 Section 3 Extracted Mass (g) 0.2403 0.2344 Average %RPD 0.2555 0.2613 A v e ra g e %RPD 0.2468 0.2328 Average %RPD 0.2364 0.2512 Average %RPD 0.2690 0.2604 Average %RPD 0.2638 0.2482 Average %RPD 0.2414 0.2563 Average %RPD mPFHpA Cone (ng/g) <0.260 <0.267 <0.263 NA <0.245 <0.239 <0.242 NA <0.253 <0.268 <0.261 NA <0.264 <0.249 <0.257 NA <0.232 <0.240 <0.236 NA <0.237 <0.252 <0.244 NA <0.259 <0.244 <0.251 NA '"PFOA Cone (ng/g) <0.273 <0.279 <0.276 NA <0.256 <0.251 <0.254 NA <0.265 <03281 <0.273 NA <0.277 0.262 0 .26 2 NA 1.14 1.20 1.17 4 .9 <0.248 <0.264 <0.256 NA <0271 <0.256 <0.263 NA mPFNA Cone (ng/g) 0.351 0.382 0 .3 6 6 8 .5 <0.256 <0.251 <0.254 NA <0.265 <0,28_|____ <0.273 NA 0.435 0.459 0.447 5 .4 <0.243 <0.252 <0.248 NA <0.248 <0.264 <0.256 NA <0271 ____ < 0256 <0.263 NA p. 10 3M ENVIRONMENTAL LABORATORY PAGE 8 O F 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 2 Continued. 3 M U M S ID E09-0372-008 E9-0372-008 Dijp Sample Description Axys ID - L12931-14, Client ID - 090032 Axys ID- L12931-14, CJient ID - 090032 Dup Smallmouth Bass E09-0372-009 E09-0372-009 Dup Axys ID- L12932-2, Client ID - 090094 Axys ID- L12932-2, Client ID - 090094 Dup Smallmouth Bass E09-0372-010 E09-0372-010 Dup Axys ID- L12932-4, Client ID - 090096 Axys ID - L12932-4, Client ID - 090096 Dup Smallmouth Bass E09-0372-011 E09-0372-011 D ud Axys ID- L12932-9, Client ID - 090042 Axys ID - L12932-9, Client ID - 090042 Dup Smallmouth Bass E09-0372-012 E 0 9 -0 37 2 -0 1 2D u p Axys ID- L12932-26, Client ID- 090248 Smallmouth Bass Axys ID - L12932-26, Client ID - 090248 Dud . E09-0372-013 E09-0372-013 D ud Axys ID - L12933-18, Client ID - 090064 Axys ID- L12933-18, Client ID - 090064 Dup W hite Bass E09-0372-014 E09-0372-014 D ud Axys ID- L12933-20, Client ID - 090066 Axys ID - L12933-20, Client ID - 090066 Dup W hite Bass River Extracted Section 1 Section 2 Section 2 Section 1 Section 4 Section 2 Section 2 0.2607 0.2507 Average %RPD 0.2375 0.2699 Average %RPD 0.2622 0.2561 Average %RPD 0.2430 0.2548 Average %RPD 0.2646 0.2602 Average %RPD 0.2433 0.2599 Average %RPD 0.2488 0.2424 Average %RPD mPFHpA <0.240 <0.249 <0.245 NA <0.263 <0.232 <0.247 NA <0.238 <0.244 <0.241 NA <0.257 <0.245 <0.251 NA < 0 .2 3 6 <0.240 <0.238 NA <0.257 <0.240 <0.249 NA <0.251 <0.258 <0.255 NA lvPFOA <0.251 <0.261 <0.256 NA <0.276 <0.243 <0.259 NA <0.250 <0.256 <0.253 NA <0.270 <0.257 <0.263 NA <0.248 <0.252 <0.250 NA <0.269 <0.252 <0.261 NA <0.263 <0.270 <0.267 NA mPFNA <0.251 <0.261 <0.256 NA <0.276 <0.243 <0.259 NA <0.250 <0.256 <0.253 NA <0.270 <0.257 <0.263 NA <0.248 <0.252 <0.250 NA 0.282 0.296 0.288 4 .8 <0.263 <0.270 <0.267 NA p . 11 3M ENVIRONMENTAL LABORATORY PAGE 9 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 E09-0372-015 E09-0372-015 Dup Axys ID - L12933-25, Client ID - 090071 Axvs ID - L12933-25, Client ID - 090071 Dup E09-0372-016 E09-0372-016 Dup Axys ID - L12934-10, Client ID - 090024 Axvs ID - L12934-10, Client ID - 090024 Dup E09-0372-017 E09-0372-017 Dup Axys ID - L12934-12, Client ID - 090026 Axys ID - L12934-12, Client ID -090026D u p E09-0372-018 Ff>n-037?-018 Dup Axys ID - L12934-18, Client ID- 090017 Axvs ID - L12934-18, Client ID - 090017 Dup E09-0372*019 E09-0372-019 Dup Axys ID - L12945-1, Client ID- 090153 Axys ID - L12945-1, Client ID - 090153 Dup E09-0372-020 FnQ-037?-0?0 D ud Axys ID - L12945-4, Client ID - 090167 Axvs ID - L12945-4, Client ID- 090167 Dup E09-0372-021 E09-0372-021 Dup Axys ID- L12945-14, Client ID - 090241 Axvs ID - L12945-14, Client ID - 090241 Dup River Extracted Mass (a) W hite Bass Section 2 W hite Bass Section 1 W hite Bass Section 1 ______________ W hite Bass Section 1 Fresh W ater Drum Section 3 _____________________ ______________ Fresh W ater Drum Section 3 Fresh W ater Drum Section 4 0,2518 0.2492 Average %RPD 0.2570 0.2436 Average %RPD 0.2442 0.2545 Average %RPD 0.2640 0.2433 Average %RPD 0.2568 0.2473 Average %RPD 0.2372 0,2509 Average %RPD 0.2375 0.2574 Average %RPD mPPHpA Cone fng/g) <0.248 <0.251 <0.250 NA <0.243 ____ <0.257____ <0.250 NA < 0 .2 5 6 ____ <0.246____ <0.251 NA <0.237 <0.257 <0.247 NA <0.243 <0.253 <0.248 NA <0.263 <0.249 <0.256 NA <0.263 <0.243 <0.253 NA ,vPFOA Cone (ng/g) <0.260 <0.263 <0.261 NA <0.255 <0.269 <0.262 NA <0.268 <0.257 <0.263 NA <0.248 <0.269 <0.259 NA <0.255 <0.265 <0.260 NA <0276 <0.261 <0.269 NA <0.276 <0.254 <0.265 NA mPFNA Cone (no/a) 0.387 0.341 0 .3 6 4 13 <0.255 <0.269 <0.262 NA 0.275 0.298 0.287 7 .8 0.504 0.542 0 .5 2 3 7 .2 0.526 0.516 0.521 1.9 0.364 0.337 0 .3 5 0 7 .7 0.617 0.616 0.616 0.17 p. 12 3M ENVIRONMENTAL LABORATORY PAGE 10 O F 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 2 Continued. 3M LIMS ID E09-0372-022 E09-0372-022 Dup Sample Description Axys ID- L12945-16, Client ID- 090078 Axys ID- L12945-16. Client ID - 090078 Dup Fresh W ater Drum E09-0372-023 E09-0372-023 D ud Axys ID - L12945-19, Client ID - 090081 Axys ID- L12945-19, Client ID - 090081 Dud Fresh W ater Drum E09-0372-024 E09-0372-024 D ud Axys ID- L12945-30, Client ID - 090009 Axys ID - L12945-30, Client ID - 090009 Dud Fresh W ater Drum E09-0372-025 E09-0372-025 D ud Axys ID- L12947-7, Client ID - 090266 Axys ID - L12947-7, Client ID- 090266 Dup Bluegill Sunfish E09-0372-026 E09-0372-026 D ud Axys ID - L12947-8, Client ID - 090267 Axys ID- L12947-8. Client ID- 090267 Dup Bluegill Sunfish E09-0372-027 E09-0372-027 Dup Axys ID - L12947-13, Client ID- 090111 Axys ID- L12947-13, Client ID - 090111 Dup Bluegill Sunfish E09-0372-028 E09-0372-028 D ip Axys ID - L12947-25, Client ID- 090205 Axys ID - L12947-25, Client ID - 090205 Dup Bluegill Sunfish River Extracted Section 2 Section 2 Section 1 Section 3 Section 3 Section 2 Section 4 0.2468 0.2657 Average %RPD 0.2345 0.2537 Average %RPD 0.2385 0.2430 Average %RPD 0.2338 0.2583 Average %RPD 0.2355 0.2495 Average ARPO 0.2610 0.2581 Average %RPD 0.2455 0.2524 Average %RPD mPFHpA Cone (na/a> <0.253 <0.235 <0.244 NA <0.267 <0.246 <0.256 NA <0.262 <0.257 <0.260 NA < 0 .2 6 7 <0.242 <0.255 NA <0.265 <0.251 <0.258 NA <0.239 <0.242 <0.241 NA <0.255 <0.248 <0.251 NA <vPFOA <0.265 <0.247 <0.256 NA <0.279 <0.258 <0.269 NA <0.275 <0.270 <0.272 NA <0.280 <0.254 <0.267 NA <0.278 <0263 <0.270 NA <0.251 <0.254 <0.252 NA <0267 0.291 0 .2 9 1 NA ,VPFNA Cone (na/a) 0.400 0.285 0 .3 4 3 34 0.289 0.265 0 .2 7 7 8.6 <0.275 <0270 <0.272 NA 0.281 <0254 w 0.281 NA <0.278 <0.263 <0.270 NA <0.251 <0.254 <0.252 NA <0267 <0260 <0.263 NA p. 13 3M ENVIRONMENTAL LABORATORY PAGE 11 O F 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Species River Location Extracted Mass (a) mPFHpA Cone (no/g) n PFOA Cone (nq/q) mPFNA Cone (nq/q) E 0 9 -0 37 2 -0 2 9 E 0 9 -0 37 2 -0 2 9D u p Axys ID - L12947-26, Client ID - 090206 Axys ID - L12947-26, Client ID - 090206 Dup Bluegill Sunfish Section 4 0.2421 0.2479 Average <0.258 <0.252 <0.255 <0.271 <0.264 <0.267 <0.271 <0.264 <0.267 %RPD NA NA NA EQ9-0372-030 E09-0372-030 Duo Axys ID - L12948-17, Client ID - 090061 Axys ID- L12948-17, Client ID - 090061 Dup Bluegill Sunfish Section 1 0.2544 0.2577 Average < 0 .2 4 6 <0.243 <0,244 <0.257 <0.254 <0.256 <0.257 <0.254 <0.256 %RPD NA NA NA (1) Unless otherwise specified, the recovery of the associated laboratory matrix sprue (lmoj was wrcnin iw u u /o wnioi meets c i o o -^ .u m euiw uhhb. Sample result are considered accurate to within the overall analytical method uncertainty 10021 % (PFHpA), 10019% (PFOA), and 10022% (PFNA). See Section 4.9 Determination ofAnalytical Method Uncertaintyfor more information. Sample results are reported to three significant figures and %RPD to two significant figures. Additional significant figures were used to calculate the average. %RPD, and %recovery. Values in the raw data may vary slightly due to rounding. PFHpA, PFOA. and PFNA results were generated using an extracted calibration curve prepared in a control matrix of bluegill fillet (2) One sample result was above the limit of quantitation (LOQ) and the other replicate was below the LOQ. The average reflects only the value above the LOQ. A relative percent diference (%RPD) was net calculated. (3) The %RPD exceeded 20%. p. 14 3M ENVIRONMENTAL LABORATORY PAGE 12 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 T ab le 3. S a m p le R e s u lts S um m ary: PFC A s (C 1 0 -C 1 2 ). 3M LIMS ID Sample Description E09-0372-001 E09-0372-001 Dup Axys ID- L12916-14, Client ID- 090191 Axys ID- L12916-14, Client ID - 090191 Dup Species Carp E09-0372-002 E09-0372-002 Dup Axys ID - L12916-24, Client ID - 090054 Axys ID- L12916-24, Client lD - 090054 Dup Carp E09-0372-003 E09-0372-003 Dup Axys ID- L12916-26, Client ID- 090056 Axys ID - L12916-26, Client ID - 090056 Dup Carp E09-0372-004 E09-0372-004 Dup Axys ID - L12917-3, Client ID - 090275 Axys ID- L12917-3, Client ID- 090275 Dup Carp E09-0372-005 E09-0372-005 Dud Axys ID- L12917-10, Client ID - 090282 Axys ID - L12917-10, Client ID - 090282 D ud Carp E09-0372-006 E09-0372-006 Dud Axys ID - L12917-17, Client ID - 090123 Axys ID- L12917-17, Client ID - 090123 D ud Carp E09-0372-007 . E09-0372-007 Dup Axys ID- L12931-6, Client ID - 090173 Axys ID - L12931-6, Client ID- 090173 Dup Smallmouth Bass River Location Extracted Mass (g) n PFDA Cone (ng/g) Section 3 Section 1 Section 1 Section 4 Section 4 Section 2 Section 3 0.2403 0.2344 Average %RPD 0.2555 0.2613 Average %RPD 0.2468 0.2328 Average %RPD 0.2364 0.2512 Average %RPD 0.2690 0.2604 Average %RPD 0.2638 0.2482 Average %RPD 0.2414 0.2563 Average %RPD 1.58 1.70 1.64 7.0 1.55 1.52 1.53 1.6 0.681 0.728 0.704 6.7 2.46 2.46 2.46 0 .2 4 0J267 0.299 0.283 11 1.23 1.58 1.41 25 2.07 2.00 2.04 3.5 (1>PFUnA Cone (ng/g) 0.654 0.659 0.657 0.72 0.889 0.957 0.923 7.3 0.321 0.329 0.325 2.3 1.24 1.09 1.17 12 <0.238 <0.246 <0.242 NA 1.16 1.07 1.11 8.0 1.62 1.48 1.55 8.6 <1>PFDoA Cone (ng/g) 0.361 0.388 0.375 7.3 0.438 0.487 0.463 11 0.497 0.548 0.523 9.6 0.555 0.588 0.572 5.8 <0.239 <0.247 <0.243 NA 0.631 0.728 0.680 14 0.971 1.03 1.00 6.2 p. 15 3M ENVIRONMENTAL LABORATORY PAGE 1 3 0 F 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 3. Continued. 3M UMS ID E09-0372-008 E09-0372-008 Dup Axys ID - L12931-14, Client ID- 090032 Axys ID - L12931-14, Client ID - 090032 Dup Species Smallmouth Bass E09-0372-009 E09-0372-009 Dup Axys ID - L12932-2, Client ID - 090094 Axys ID - L12932-2. Client ID - 090094 Dup Smallmouth Bass E09-0372-010 E 0 9 -0 37 2 -0 1 0D u p Axys ID - L12932-4, Client ID - 090096 Smallmouth Bass Axys lD - L12932-4, Client lD- 090096 D u p ____ E 0 9 -0 3 7 2 -0 1 1 E09-0372-011 Dup Axys ID - L12932-9, Client ID - 090042 Smallmouth Bass Axys ID - L12932-9, Client ID - 090042 Dup____ E09-0372-012 E09-0372-012 Dup Axys ID - L12932-26, Client ID - 090248 Axys ID - L12932-26. Client ID - 090248 Dup Smallmouth Bass E09-0372-013 E09-0372-013 Dup Axys ID - L12933-18, Client ID - 090064 Axys ID - L12933-18, Client ID - 090064 Dup W hite Bass E09-0372-014 E09-0372-014 Dup Axys ID - L12933-20, Client ID - 090066 Axys ID - L12933-20. Client ID - 090066 Dup White Bass River Location Section 1 Section 2 Section 2 Section 1 Section 4 Section 2 Section 2 Extracted Mass (a) 0.2607 0.2507 Average %RPD 0.2375 0.2699 A verag e %RPD 0.2622 0.2561 Average %RPD 0.2430 0.2548 Average %RPD 0.2646 0.2602 Average %RPD 0.2433 0.2599 A v e ra g e %RPD 0.2488 0.2424 A verag e %RPD (,,PFDA Cone (ng/g) 1.12 1.19 1.15 5.6 0.811 1.02 0.915 23 0.912 0.747 0.829 20 1.27 1.22 1.24 3.9 5.55 6.03 5.79 8.4 3.36 3.42 3.39 1.9 3.68 3.47 3.57 5.9 lvPFUnA Cone (ng/g) 0.988 0.973 0.981 1.5 0.813 0.725 0.769 11 0.531 0.572 0.552 7.4 1.32 1.24 1.28 6.3 4.06 4.01 4 .0 3 1.4 1.62 1.78 1.70 9.2 1.75 1.87 1.81 6.5 ,vPFDoA Cone (ng/g) 1.05 1.18 1.11 12 1.21 1.09 1.15 10 0.530 0.554 0.542 4.5 2.10 1.97 2.04 6.2 5.12 5.68 5.40 10 1.26 1.44 1.35 13 1.17 1.14 1.16 1.8 p. 16 3M ENVIRONMENTAL LABORATORY PAGE 14 O F 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-03T2 Table 3 Continued. E09-0372-015 E09-0372-015 Dup E09-0372-016 E09-0372-016 Dup E 0 9 -0 37 2 -0 1 7 E09-0372-017 Dup E09-0372-018 E09-0372-018 Dup E09-0372-019 E09-0372-019 Dup E09-0372-020 E09-0372-020 Dup E09-0372-021 E09-0372-021 Dup Axys ID - L12933-25, Client ID - 090071 Axys ID - L12933-25, Client ID - (0071 Dup W hite Bass Axys ID - L12934-10, Client ID - 090024 Axys ID - L12934-10, Client ID- 090024 Dup W hite Bass Axys ID - L12934-12, Client ID - 090026 Axys ID - L12934-12, Client ID - 090026 Dup W hite Bass Axys ID - L12934-18, Client ID - 090017 Axys ID- L12934-18, Client ID - 090017 Dup - W hite Bass Axys ID - L12945-1, Client ID - 090153 Axys ID - L12945-1, Client ID - 090153 Dup Fresh W ater Drum Axys ID - L12945-4, Client ID - 090167 Axys ID - L12945-4, Client ID - 090167 Dup Fresh W ater Drum Axys ID - L12945-14, Client ID - 090241 Axys ID - L12945-14. Client ID - 090241 Dup Fresh W ater Drum River Location Section 2 Section 1 Section 1 Section 1 Section 3 Section 3 Section 4 Extracted Mass (g) 0.2518 0.2492 Average %RPD 0.2570 0.2436 Average %RPD 0.2442 0.2545 Average %RPD 0.2640 0.2433 Average %RPD 0.2568 0.2473 Average %RPD 0.2372 0.2509 Average %RPD 0.2375 0.2574 A verag e %RPD <VPFDA Cone (ng/g) 3.87 3.11 3.49 <222 2.81 2 .8 .3 2.82 0 .7 5 3.36 3.15 3.26 6.3 3.19 2.55 2.87 m22 4.31 4.51 4.41 4 .4 3.20 3.52 3.36 9.3 (S>3.38 ,S|3.82 1313.60 12 fvPFUnA Cone (na/o) 1.94 1.89 1.91 2.6 1.54 1.68 1.61 9.1 2.01 1.80 1.90 11 1.41 1.29 1.35 8.6 1.29 1.36 1.33 5.3 1.53 1.34 1.43 13 3 .2 9 3 .4 0 3 .3 5 3.1 <vPFDoA Cone (nafa) 1.26 1.44 1.35 14 1.03 0.995 1.01 3.5 1.01 0.919 0.962 8.9 0.716 0.660 0.688 8.2 0.610 0.703 0.656 14 0.763 0.663 0.715 15 2 .5 6 1.96 2.26 *>26 p. 17 3M ENVIRONMENTAL LABORATORY PAGE 15 O F 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E03-0372 Table 3 Continued. 3M UM SID E09-0372-022 E09-0372-022 Oup Samd e Description Axys ID - L12945-16, Client ID - 090078 Axys ID - L12945-16, C lie n tlp -0 9 0 07 8 Dup Species Fresh W ater Drum EQ9-0372-023 E09-0372-023 Pup Axys ID - L12945-19. Client ID - 090081 Axys ID -L12945-19, ClientJD-- 00008.1 Dup Fresh W ater Drum E09-0372-024 E09-0372-024 Dup Axys ID- L12945-30, Client ID - 090009 Axys ID - L12945-30, Client ID - 090009 Dup Fresh W ater Drum E 0 9 -0 3 7 2 -0 2 5 E09-0372-025 Dup Axys ID - L12947-7, Client ID - 090266 Axys ID - L12947-7, Client ID - 090266 Dup Bluegill Sunfish E09-0372-026 Axys ID - L12947-8, Client ID - 090267 E09-0372-026 Dup _ _ Axys ID - L12947-8, Client ID -090267 Dup Bluegill Sunfish E09-0372-027 E09-0372-027 Dup Axys ID - L12947-13, Client ID - 090111 Bluegill Sunfish Axys [D; L12947; 13, Cljent ID- 090111 D u p ___ E 0 9 -0 37 2 -0 2 8 E09-0372-028 Dup Axys ID- L12947-25, Client ID - 090205 Axys ID - L12947-25, Client ID - 090205 Dup Bluegill Sunfish River Location Extracted Section 2 Section 2 Section 1 Section 3 Section 3 Section 2 Section 4 0.2468 0-2657 Average %RPD 0.2345 0.2537 Average %RPD 0.2385 0.2430 Average %RPD 0.2338 0.2583 Average %RPD 0.2355 0.2495 Average %RPD 0.2610 0.2581 Average %RPD 0.2455 0.2524 Average %RPD n PFDA Cone (noAa) 1.65 1.45 1.55 13 1.40 1.41 1.40 0 .9 0 1.65 1.47 1.56 11 2.03 1.73 1.88 16 3.29 2.76 3.02 18 1.91 1.70 1.81 11 228 2.03 2.16 12 tvPFUnA Cone (note) 0.812 0.698 0.755 15 0.732 0.896 0.814 20 0.411 0.486 0.448 17 1.03 0.938 0.985 9.6 1.80 1.88 1.84 4.3 1.59 1.41 1.50 12 1.54 1.65 1.60 7.3 (vPFDoA Cone (na/a) 0.369 0.445 0.407 19 0.420 0.507 0.464 19 <0.269 <0.264 <0267 NA 0.569 0.465 0.517 20 0.727 1.09 0.910 40 0.898 0.867 0.883 3.6 1 .3 0 1 .15 27 p. 18 3M ENVIRONMENTAL LABORATORY PAGE 16 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 3 Continued. 3M LIMS ID Sample Description Species River Location Extracted Mass (q) IVPFDA Cone (nq/q) {vPFUnA Cone (no/q) n PFDoA Cone (nq/q) E09-0372-029 Axys ID -L 1 2947-26, Client ID -090206 Bluegill Sunfish Section 4 0.2421 (3)1.33 1.25 0.719 E09-0372-029 Dup Axys ID - L12947-26, Client ID- 090206 Dup 0.2479 ____ `H 0 5 ____ 0.874 0.764 Average (s>1.19 1.06 0.742 %RPD 24 35 6.2 E09-0372-030 Axys ID - L12948-17, Client ID - 090061 Bluegill Sunfish Section 1 0.2544 1.74 0.879 0.627 E09-0372-030 Dup Axys ID - L12948-17, Client ID - 090061 Dup 0.2577 _____ 1 .5 0 _____ _____ L 0 6 ______ ____ 0 411_____ Average 1.62 0.968 0.519 %RPD 15 18 4 2 (1) Unless otherwise specified, the recovery of the associated laboratory matrix spire (LMS) was within 10030% which meets ETS 8-45.0 method acceptance criteria. Sample results are considered accurate to within the overall analytical method uncertainty 10017% (PFDA), 10021 % (PFUnA), and 10013% (PFDoA). See Section 4.9 Domination ofAnalytical Method Uncertaintyfor more information. Sample resells are reported to three significant figures and %RPD to two significant figures. Additional significant figures were used to calculate the average, %RPD, and % recovery. Values in the raw data may vary slightly due to rounding. PFDA, PFUnA, sad PFDoA results were generated using an extracted calibration curve prepared in a control matrix of bluegill fillet (2) The %RPD exceeded 20%. (3) LMS recovery exceeded 10030%, but was within 100160%. The sample uncertainty has been adjusted to 10060%. p. 19 3M ENVIRONMENTAL LABORATORY PAGE 1 7 0 F 104 3 M ENVIRONMENTAL LABORATORY REPORT NO- E09-0372 T ab le 4 . S am p le R esu lts S u m m ary: P FB S , P FH S , and F O S A . 3M LIMS ID E09-0372-001 E09-0372-001 Dup Samle Description Axys ID - L12916-14, Client ID - 090191 Axys ID- L12916-14, Client ID - 090191 Dup E09-0372-002 E09-0372-002 Dup Axys ID - L12916-24, Client ID - 090054 Axvs ID - L12916-24, Client ID - 090054 Dup E9-Q372-0Q3 Axys ID- L12916-26, Client ID - 090056 E09-0372-003Dup____ Axys ID - L12916-26, Client ID -090056D u p E09-0372-004 Axys ID - L12917-3, Client ID - 090275 E09-0372-004 Dup....... Axys JD- L12917-3, Client [D -090275 Dup,, . E09-0372-005 E09-0372-005 D up Axys ID - L12917-10, Client ID - 090282 Axys ID - L12917-10. Client ID - 090282 Dup E09-0372-006 E09-0372-006 Dup Axys ID -112917-17, Client ID - 090123 Axvs ID - L12917-17, Client ID - 090123 Dup E09-0372-007 Axys ID- L12931-6, Client ID - 090173 E09O372-P07.Dup.___ AxS JD- L12931 -6, Cl it ID ; 090173_Duj> Species Carp Carp Carp Carp Carp Carp Smallmouth Bass River Location Extracted Mass (a) mPFBS Cone (nq/q) (VPFHS Cone (nq/q) lvFOSA Cone (nq/q) Section 3 0.2403 ______________ 0.2344 Average %RPD Section 1 0.2555 0.2613 Average %RPD Section 1 0.2468 0.2328 Average %RPD Section 4 0.2364 0.2512 Average %RPD Section 4 0.2690 0.2604 Average %RPD Section 2 0.2638 0.2482 Average %RPD Section 3 0.2414 0.2563 Average %RPD <0.262 0.479 0.538 ____ < 0.269____ ____ 0.492______ ____ 0.538 <0.265 0.485 0.538 NA 2.7 0.061 <0.247 <0.256 <0.245 <0.241 <0.251 <0.239 <0.244 <0.254 <0.242 NA NA NA <0.255 <0.265 <0.253 <0.271 <0.281 <0.268 <0.263 <0.273 <0.261 NA NA NA <0.266 0.948 0.403 <0.251 0.869 0.447 <0.259 NA 0.908 8.7 0.425 10 < 0 .2 3 4 0.290 0.605 <0.242 0.296 0.603 <0.238 NA 0.293 2.0 0.604 0.35 <0.239 <0248 0.510 <0.254 <0.264 0.591 <0.246 <0.256 0.551 NA NA 15 <0.261 <0.271 0.687 <0.246 <0.256 0.788 <0.253 <0.263 0.737 NA NA 14 p. 20 3M ENVIRONMENTAL LABORATORY PAGE 1 8 0 F 104 3 M ENVIRONMENTAL LABORATORY REPORT NO. EQ9-0372 Table 4 Continued. 3M LIMS ID E09-0372-008 E09-0372-008 Dup E09-0372-009 E09-0372-009 Dup E09-0372-010 E09-0372-010 Dup E09-0372-011 E09-0372-011 Dup E09-0372-012 E09-0372-012 Dup E09-0372-013 E09-0372-013 Dup E09-0372-014 E09-0372-014 D ip Sample Description Axys ID - L12931-14, Client ID - 090032 Axys ID- L12931-14, Client ID - 090032 Dup Axys ID- L12932-2, Client ID - 090094 Axys ID - L12932-2, Client ID - 090094 Dup Axys ID - L12932-4, Client ID- 090096 Axys ID - L12932-4, Client ID - 090096 Dup Axys ID- L12932-9, Client ID - 090042 Axys ID- L12932-9, Client ID - 090042 Dup Axys ID - L12932-26, Client ID - 090248 Axys ID- L12932-26, Client ID - 090248 Dup Axys ID - L12933-18, Client ID- 090064 Axys ID - L12933-18, Client ID - 090064 Dup Axys ID- L12933-20, Client ID - 090066 Axys ID- L12933-20, Client ID- 090066 Dup Species Smallmouth Bass Smallmouth Bass Smallmouth Bass Smallmouth Bass Smallmouth Bass W hite Bass W hite Bass River Location Section 1 Section 2 Section 2 Section 1 Section 4 Section 2 Section 2 Extracted Mass (a) 0.2607 0.2507 Average %RPD 0.2375 0.2699 Average %RPD 0.2622 0.2561 Average %RPD 0.2430 0.2548 Average %RPD 0.2646 0.2602 Average %RPD 0.2433 0.2599 Average %RPD 0.2488 0.2424 Average %RPD (,,PFBS Cone (nq/q) <0.242 <0.251 <0.246 NA <0.265 <0.233 <0.249 NA <0.240 <0.246 <0.243 NA <0.259 <0.247 <0.253 NA <0.238 <0.242 <0.240 NA <0.259 <0.242 <0.251 NA <0.253 <0.260 <0.257 NA mPFHS Cone (nq/q) <0.251 <0.261 <0.256 NA <0.276 <0.243 <0.259 NA <0.250 <0.256 <0.253 NA <0.270 <0.257 <0.263 NA <0.248 <0.252 <0.250 NA <0.269 <0.252 <0.261 NA <0.263 <0.270 <0.267 NA n FOSA Cone (nq/q) 0.512 0.525 0 .5 1 8 2 .4 0.616 0.669 0 .6 4 2 8.2 0.344 0.345 0 .3 4 4 0.11 0.774 0.790 0 .7 8 2 2.1 35.5 35.2 35.3 1.0 1.30 1.24 1.27 5.0 1.41 1.39 140 1.0 p. 21 3M ENVIRONMENTAL LABORATORY PAGE 1 9 0 F 104 3MENVIRONMENTAL LABORATORY REPORT NO. EQ9-0372 Table 4 Continued. 3M LIMS ID E09-0372-015 E09-0372-015 Dup E09-0372-016 E09-0372-016 Dup E09-0372-017 E09-0372-017 Dup E09-0372-018 E09-0372-018 Dup E09-0372-019 E09-0372-019 Duo E09-0372-020 E09-0372-Q20 Dup E09-0372-021 E09-0372-021 Dup Sample Description Axys ID - L12933-25, Client ID - 090071 Axvs ID - L12933-25, Client ID - 090071 Dup Axys ID - L12934-10, Client ID - 090024 Axys ID - L12934-10, Client ID- 090024 Dup Axys ID - L12934-12, Client ID - 090026 Axys ID - L12934-12, Client ID - 090026 Dup Axys ID - L12934-18, Client ID - 090017 Axys ID - L12934-18, Client ID - 090017 Dup Axys ID - L12945-1, Client ID - 090153 Axys ID - L12945-1, Client ID - 090153 Dup Axys ID - L12945-4, Client ID - 090167 Axys ID - L12945-4, Client ID - 090167 Dup Axys ID - L12945-14, Client ID - 090241 Axys ID - L12945-14, Client ID - 090241 Dup Species White Bass W hite Bass White Bass White Bass Fresh W ater Drum Fresh W ater Drum Fresh W ater Dram River Location Section 2 Section 1 Section 1 Section 1 Section 3 Section 3 Section 4 Extracted Mass (q) 0.2518 0.2492 Average %RPD 0.2570 0.2436 Average %RPD 0.2442 0.2545 Average %RPD 0.2640 0.2433 Average %RPD 0.2568 0.2473 Average %RPD 0.2372 0.2509 Average %RPD 0.2375 0.2574 Average %RPD mPFBS Cone (ng/g) <0.250 <0253 <0.252 NA 1 .45 (2)<0.259 ,m ,1.45 NA <0258 <0248 <0.253 NA <0.239 <0.259 <0249 NA <0245 <0.255 <0.250 NA <0.266 <0.251 <0.258 NA <0.265 <0245 <0.255 NA mPFHS Cone (ng/g) <0260 <0263 <0261 NA <0255 <0.269 <0.262 NA <0.268 <0257 <0263 NA <0.248 <0.269 <0259 NA <0255 <0.265 <0.260 NA <0276 <0261 <0.269 NA <0.276 <0254 <0265 NA <"FOSA Cone (ng/g) 1.56 1.81 1.68 15 0.956 1.17 1.06 20 1.73 1.80 1.76 3.8 2.70 2.44 2.57 10 0.653 0.617 0 .6 3 5 5.8 <0.263 0.297 <J)0.297 NA 129 129 1.29 0.23 p. 22 3M ENVIRONMENTAL LABORATORY PAGE 20 O F 104 3M ENVIRONMENTAL LABORATORY REPORT NO. 09-0372 Table 4 Continued. 3M LIMS ID E09-0372-022 ,,10^3724322 pup E09-0372-023 E09-0372-023 Dup E09-0372-024 E09-0372-024 D ip E09-0372-025 E09-0372-025 Dup E09-0372-026 E09-0372-026 Dup E09-0372-027 E09-0372-027 Dup E09-0372-028 E09-0372-028 Dup Species Axys ID - L12945-16, Client ID- 090078 Fresh W ater Drum Axys ID - L12945-16, CJient 0 - 090078 p up _. Axys ID - L12945-19, Client ID - 090081 Axys ID - L12945-19, Client ID - 090081 Dup Fresh W ater Drum Axys ID - L12945-30, Client ID- 090009 Axys ID - L12945-30, Client ID - 090009 Dup Fresh W ater Drum Axys ID- L12947-7, Client ID - 090266 Axys ID- L12947-7, Client ID- 090266 Dup Bluegill Sunfish Axys ID- L12947-8, Client ID - 090267 Axys ID - L12947-8, Client ID - 090267 Dup Bluegill Sunfish Axys ID - L12947-13, Client ID - 090111 Axys ID - L12947-13, Client ID -090111 Dup Bluegill Sunfish Axys ID - L12947-25, Client ID- 090205 Axys ID - L12947-25, Client ID- 090205 Dup Bluegill Sunfish River Location Section 2 Section 2 Section 1 Section 3 Section 3 Section 2 Section 4 Extracted Mass (a) 0.2468 0.2657 Average %RPD 0.2345 0.2537 Average %RPD 0.2385 0.2430 Average %RPD 0.2338 0.2583 Average %RPD 0.2355 0.2495 Average %RPD 0.2610 0.2581 Average %RPD 0.2455 0.2524 Average %RPD ,VPFBS Cone (nq/q) <0255 <0.237 <0.246 NA <0269 <0.248 <0.258 NA <0.264 <0.259 <0.262 NA <0269 <0.244 <0257 NA 0.295 0.260 0.277 13 <0.241 <0.244 <0.243 NA 0.328 0.336 0.332 2.4 mPFHS Cone (nq/q) <0265 <0247 <0.256 NA <0279 <0.258 <0269 NA <0275 <0270 <0272 NA <0.280 <0.254 <0.267 NA <0.278 <0.263 <0.270 NA <0.251 <0.254 <0.252 NA <0267 <0260 <0.263 NA <vFOSA Cone (nq/q) 0.440 0.382 0.411 14 <0267 <0.246 <0256 NA 0.289 <0257 <0.289 NA 0.588 0.609 0 .5 9 8 3 .5 1.00 1.01 1.01 1.2 0.353 0.338 0 .3 4 6 4 .5 2.18 2.71 2.45 w22 p. 23 3M ENVIRONMENTAL LABORATORY PAGE 21 O F 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 4 Continued. 3M LIMS ID Sample Description Species River Location Extracted Mass (al 111PFBS Cone (no/o) mPFHS Cone (no/ct) n FOSA Cone (no/o) E09-0372-029 Axys ID - L12947-26, Client ID - 090206 Bluegill Sunfish Section 4 0.2421 < 0 .2 6 0 <0.271 0.685 E09-0372-029 Pup____ Axys JD- L12%47-26,.CJient |D-_09CB06 Dup............ ....................... 0.2479 <0.254 <0.264 0.544 Average <0.257 <0.267 0 .6 1 4 %RPD NA NA w 23 E09-0372-030 E09-0372-030 Dup Axys ID -L12948-17, Client ID -090061 Axys ID- L12948-17, Client ID - 090061 Dup Bluegill Sunfish Section 1 0.2544 0.2577 <0.248 <0.257 1.46 <0.244____ ____ <0.254_____ _____1.37 ____ A v erag e <0.246 <0.256 1.42 %RPD NA NA 6.8 (1) Unless otherwise specified, the necoveiy of the associated laboratory matrix spike (LMS) was within 100*30% which meets ETS 8-45.0 method acceptance criteria. Sample resuite are considered accurate to within the overall analytical method uncertainty 100*19% (PFBS), 100*27% (PFHS), and 100*20% (FOSA). See Section 4.9 Determination ofAnalytical Method Uncertaintyfor more information. Sample results are reported to three significant figures and %RPD to two significantfigures. Additional significant figures were used to calculate the average, %RPD, and %recovery. Values in the raw data may vary slightly due to rounding. PFBS, PFHS, and FOSA results were generated using an extracted calibration curve prepared in a control matrix of bluegill fillet (2) LMS recovery exceeded 100*30% , but was within 100*50%. The sample uncertainty has been adjusted to 100*50%. (3) One sample result was above the limitof quantitation (LOQ) and the other replicate was below the LOQ. The average reflects only the value above the LOQ. A relative percent difference (%RPD) was not calculated. (4) The %RPD exceeded 20%. p. 24 3M ENVIRONMENTAL LABORATORY PAGE 22 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 2 Study and Sample Information 2.1 Target Analytes. Table 5 below provides pertinent information regarding foe target analytes, internal standards, and surrogate recovery standards investigated in this study. Surrogate recovery standards were separate isotopically labeled compounds spiked into each sam ple aliquot prior to extraction. The recovery of foe surrogate w as used to evaluate the overall extraction process and any potential matrix effects. T ab le 5. T a rg e t A n alyte S um m ary. Compound Name Perfluorobutanoic acid Perfluoropentanoic aad Perfluorohexanoic add Perftuoroheptanoc aad Perfluoroodanac add Synonym or Acronym PFBA (C4 Add) PFPeA (C5 Add) PFHxA (C6Add) PFHpA (C7 Add) PFOA (C8Add) Perfluorononanoic add Perfluorodecanoic add Perfluoroundecanoic acid Perffoorododecanotc add Perfluorobutane sulfonate Perfluorohexane sulfonate PFNA (C9 Add) P F D A (C 1 0 A d d ) PFUnA(C11 Add) F*FDoA(C12 Add) PFBS (C4 Sulfonate) PFHS (C6 Sulfonate) Periluorooctane sulfonate PFOS (C8 Sulfonate) Perffoorooctanesutfonamide FOSA (C8 Sulfonamide) Formula CsFtCOOH C^FgCOOH C5F11COOFI CjF^COOH C7F15COOH CjF .C O O 'N K ,* C*F,tCOOH c f 19c o o h C ,oF21COOH . CnFaCCXJH C^FoSOjlC GsFnSOjNa* CsF^SCMC c , f ,7s o ,ic CsF^SCMMHj Analytical Purpose Reference Standard Source Taget Target Target Target Target Target Target Target Target Taget Target Target Aldrich Alfa Aesar Oakwood Products Aldrich L-PFOA (linear) Wellington Labs ECF PFOA (branched) 3M Production Lot 332 Oakwood Products Oakwood Products Oakwood Products Oakwood Products 3M Production Lot 2 L-PFHS (linear) WeSngton Labs L-PFOS (Snea) Wellington Labs ECF PFOS (branched) 3M Production Lot 217 Target 3M (L-15709) 3M ENVIRONMENTAL LABORATORY PAGE 23 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 5 Continued. Compound Name C 4-Peffluorobiitanok: acid "Cj-Perflixxoheicanoic add nC4-Perfluorooctanac add ,3Cs-Perfkiofononanoic add ,3C2-Perfluaodecanoic add "C^erttuoroundecanojc add '3CrPerfhjorododecancMC acid ,802-Ammoreum Peffluorobutane sulfonate ,8Or Ammonium Perfluorohexane sulfonate nC4-Sodium Pertuoroodane sulfonate '"Oz-Perfluoroodanesulfonanide ,3C2-Perfluoroodanoic add '"OrAmmoraum Perfluoroodane sulfonate Synonym or Acronym [1,2,3,4-13GJPFBA [1 ,2 -13Cj]PFHxA [1,2,3,4-'3C4P F 0 A [1,2,3,4,5-13C5]PFNA [1,2 -13CyPFDA [1l2 - ,3C2[F'FUnA [1,2 -,3CJPFDoA [iaCyPFBS ['"OJPFHS [1,2,3,4-13C4]PFOS fO JFO S A [1,2-,3Cj]PFOA [,aOJPFOS Formula 13CF3(,,CF2fc13COOH CF3(CF3)3( ,:>CF2) '3COOH CF^CFj^ C F ^ 'COOH CF3fC F2)3( '3CF2)4,3COOH CF3(CF2M 13CF2),3COOH C F jfC F ^ C F jp C O O H CF3(CF3)(13CF2)13COOH [Q FsS ^ O jO rN H ," [ ^ ^ " O jO rN H ,* CFj(CF2)3(,3CF2)3,3CF2S03- Na* [CsFtTS^OjNHJ CF3(CF2)5( ,3CF2) ,3COOH [C8F)7S'e0 20 rN H 4* Analytical Purpose IS IS IS IS IS IS IS IS IS IS IS Surrogate Surrogate Reference Standard Wellington Labs Wellington Labs Wellington Labs Wellington Labs Wellington Labs Wellington Labs Wellington Labs RTI International Wellington Labs Wellington LA s RTI International Perlon Elmer RTI International 2.2 Sample Collection and Receipt. On August 6 ,2 0 0 9 , the 3M Environmental Laboratory received the homogenized fillet samples in Nalgene bottles on dry ice. The samples w ere logged into the 3M Environmental Laboratory LIMS system under project E 09-0372 and placed in frozen storage. No information was provided regarding the sampling date. It should be noted that these fish samples have been previously handled and analyzed at another laboratory under contract by the M PCA. It is unknown how these samples have been handled and if the integrity of these samples has been comprised prior to receipt. 3M Environmental Laboratory personnel removed the homogenized fish tissue from the sample container by cutting the bottle aw ay from the frozen sample mass using a clean utility knife. The frozen sam ple mass was then rehomogenized before extraction. S ee Section 3.1 for more information. Based on the sam ple consistency in the Nalgene bottles, it appeared that foe sample homogenates had thawed at some point before they arrived at the 3M Environmental Laboratory. (Homogenized tissue had refrozen into a solid m ass that could not be broken up while frozen in foe container.) -A nalytical and Preparatory 3.1 Tissue Preparation Each submitted sam ple and bluegill fillet control tissue (T N 08-0220-1/1) purchased from Osage Catfisheries, Inc. (O sage Beach, M O ) were rehomogenized frozen using dry ice. 3M ENVIRONMENTAL LABORATORY PAGE 24 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO E09-0372 Frozen fish hom ogenate was added to a pre-chilled stainless steel bowl of a Robot Coupe RSI 2Y-1 vertical batch processor and hom ogenized with dry ice until a fine powder consistency was reached. After homogenization, the ground fish tissue was transferred to a polyethylene bag which was placed in the freezer at -20C unsealed overnight to allow file residual carbon dioxide to sublim e. After sublimation, the bag was sealed and hom ogenates w ere kept frozen. 3.2 Sample Extraction A 0.25 g sub-sample of the fish tissue hom ogenate was accurately weighed in a 50 mL polyethylene centrifuge tube. Tissue aliquots w ere then spiked with internal standards (IS s) and surrogates to produce an approximate concentration of 1 ng/g. Sam ples designated as lab matrix spikes or matrixmatched calibration standards w ere additionally spiked with the target and surrogate analytes at appropriate levels to produce the desired tissue concentrations. Sam ples intended few laboratory Q C (laboratory control spikes, LCSs) w ere spiked with surrogates a t 1 ng/g and the other target analytes at approximately 0.5 ng/g, 1.5 ng/g, and 8 ng/g. After sp rin g , the tissue hom ogenates w ere allowed to sit for 30 minutes before 2 .5 mL of acetonitrile was added. The sam ples w ere then thoroughly hom ogenized with the acetonitrile using an Omni Prep multi-place hom ogenizer with disposable plastic probes (15,000 rpm for 2 minutes). The acetonitrile/tissue extracts w ere then placed in a freezer at 20C for at least one hour. Upon removal from the freezer, sam ple extracts w ere centrifuged at a targeted tem perature o f -5C for 20 minutes at 3000 rpm. After centrifugation, 1 mL of clarified supernatant was transferred to a 2 mL autovial spiked with 10 pL of 10% formic acid. Autovials w ere then capped and vortex mixed. Sam ples w ere extracted in three separate batches. For each submitted sample, a sample, sample duplicate, and laboratory matrix spike (LM S ) w ere prepared. Each extraction batch included the following quality control samples: a thirteen point extracted matrix calibration curve using the purchased bluegill fillet control tissue triplicate lab control spikes of the bluegill fillet control tissue at three levels of all target analytes (0 .5 ng/g, 1.5 ng/g, and 8 ng/g) triplicate lab control spikes of 3M electrochemical fluorination (E C F) PFO A and PFO S at 5 ng/g triplicate lab control spikes of PFO S w ily at 100 ng/g duplicate control matrix blanks with and without internal standards and surrogates duplicate method (aqueous) blanks with and without internal standards and surrogates The table below sum m arizes the preparation dates and samples prepared in each batch. T a b le 6 . S a m p le P re p a ra tio n S um m ary. Batch Number Batch 1 Batch 2 Batch 3 Preparation Dates 8 /2 5 /2 0 0 9 -8 /2 6 /2 0 0 9 8/27/2009 - 8/28/2009 8/31/2009 - 9/1/2009 Samples E09-0372-001 to E09D372-010 E09D372-021 to E09D372-030 E09-0372-011 to E09D372-020 3.3 Analysis Analysis for the PFCs listed in Table 5 was performed using high perform ance liquid chromatographytandem mass spectrometry (H P LC /M S/M S ). For this investigation, sam ples w ere analyzed using an Agilent 1100 series (Palo Alto, C A) HPLC system interfaced to either a PE S C IE X API 4000 triple 3M ENVIRONMENTAL LABORATORY PAGE 25 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 q u a d ru p le or S C IE X API 4000 Q-Trap mass spectrometer (Foster City, CA). Both instruments were equipped with a S C IE X Turbo V ion-spray interface operating in the negative ion M S/M S mode using multiple reaction monitoring (M R M ). AnalystTM 1.4.2 software was used for all data collection and reduction. Table 7 lists the M RM transitions monitored for each analyte. A Therm o Scientific PRISM RP guard column (2.1m m * 50 mm; 5p particle size) was placed in-line after the purge valve and before the sam ple injection port to trap any PFC contaminants coming from the HPLC instrument and/or the mobile phases. This sufficiently separated the elution o f the "system" PFC peaks from those present in the sam ple extracts. 3M ENVIRONMENTAL LABORATORY PAGE 26 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO E09-0372 T ab le 7. M R M T ra n s itio n S um m ary. PFBA (C4 Acid) PFPeA (C5 Add) Anatvto Description Target Target PFHxA (C6Add) Target PFHdA (C7 Add) Target PFOA (C8Add) Target PFNA (C9 Add) Target PFDA (C10 Add) Target PFUnA (C11 Acid) Target PFDoA (C12 Acid) PFBS (C4 Sulfonate) PFHS(C6 Sulfonate) Taget Target Target PFOS (C8 Sulfonate) FOSA (C8 Sulfonamide) [1 2 ,3 ,4 -,3C,]PFBA [1 2 -"CzJPFHxA [1 2 ,3 ,4 -,3C ,]PFOA [1 2 ,3 ,4 ,5 -,3Cs]PFNA [1 2 -'3C2[PFDA [1 2 -,3CJPFUnA [12J 3C2]PFDoA r'O JPFB S [" OJPFHS [12,3,4- ,3GJPFOS [" CyFOSA [1 2 - ''CJPFOA [" OjJPFOS Target Target IS for PFBA and PFPeA IS for PFHxA IS for PFHpA and PFOA IS for PFNA IS for PFDA IS for PFUnA IS for PFDoA IS for PFBS IS for PFHS IS for PFOS IS for FOSA Sunogate (Acids) Sunogate(Sulfonates, FOSA) n MRM Transition^) 213>169 263>219 313>269 313>119 363>319 363>169 413>369 413>219 413>169 463>419 463>219 463>169 513>4G9 513>269 513>219 563>519 563>269 563>219 613*569 613>319 613>169 299>80 299>99 399*80 399>99 499>80 499>99 499*130 498>78 217>172 315*270 417*372 468*423 515*470 565*520 615*570 303*84 403*84 503*80 502*82 415*370 503*84 Dwell Time (ms) 100 100 100 100 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 100 100 50 50 50 50 50 50 50 50 50 50 50 3M ENVIRONMENTAL LABORATORY PAGE 27 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Analysis of the short-chain acids (C 4 through C 6) was performed using a Therm o Scientific P R ISM RP column (2.1m m * 50 mm; 5 p particle size) held at 30C with the mobile phase system consisting of 5 mM ammonium acetate with 0.01 % acetic ad d in w ater (A ) and methanol (B). The gradient used to elute foe analytes of interest is presented in Table 8. The flow rate was held at 300 pL/min throughout foe run and a 20 pL injection volume was used. The outlet o f foe analytical column was directed to a column switching valve w here foe first three minutes of foe run w ere diverted to waste. After three minutes, foe valve was switched to direct the effluent to foe mass spectrometer for analysis. The large-chain acids (C 7 through C 12), the sulfonates, and FOSA w ere analyzed using a Thermo 100Scientific BetasilTM C 18 analytical column (2.1m m x mm; 5p particle size) held at 30C with foe mobile phase system consisting of 2 m M ammonium acetate in w ater (A ) and acetonitrile (B). The gradient used is also provided in Table 8. The flow rate was held at 400 pL/min throughout the run and a 25 pL injection volume was used. Sam ples w ere injected onto a W aters (Milford, M A) Oasis HLB on-line extraction column (3.0 mm x 2 0 mm, 25 p particle size) with the outlet directed to a column switching valve where the first five minutes w ere diverted to waste. After five minutes, the valve was switched and foe effluent was directed to foe analytical column for separation of the target analytes and analysis by foe m ass spectrometer. T ab le 8. LC G ra d ie n t P aram eters. Small Acids: C4-C6 Step Total Time (min) %A 0 00 1 3.0 2 3.5 3 9.0 4 15.0 5 15.1 6 19.0 90 90 30 5.0 5.0 90 90 %B 10 10 70 95 95 10 10 A 5 mM ammonium acetate with 0 .01% acetic add (aq) B Methanol Large Acids: C7-C12; Sulfonates, FOSA Step Total Time (min) %A %B 0 0.0 1 3.0 2 35 3 13.5 4 15.5 5 16.0 6 18.0 7 18.3 8 21.0 97 3.0 97 3.0 70 30 40 60 40 60 10 90 10 90 97 3.0 97 3.0 A 2 mM ammonium acetate (aq) B Acetonitrile To m anage foe large num ber of transitions required for the large acids, sulfonates, and FOSA, a multiperiod method was constructed. The `first period (tim e=0 minutes to 11 m inutes) collected the transitions for PFBS, PFHpA, PFO A, [1,2 - ^C JP FO A , PFH S, PFNA and their respective ISs. The second period (tim e=11 min to 21.0 minutes) collected foe transitions for PFDA, PFUnA, PFO S, [ O JP FO S , PFDoA, and FO SA and their respective ISs. For analytes where more than one transition was acquired, a total ion chromatogram (T IC ) which summed foe respective transitions for that analyte was used to quantitate foe results for that analyte. Exact location ofthe period break may vary as individual analytical columns may perform differently or if instrument tubing is charged. 3M ENVIRONMENTAL LABORATORY PAGE 28 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 4 Data Analysis , . v ," " v ' 4.1 Calibration Extracted ` m atrix-matched calibration standards and Q C s w ere prepared by spiking known amounts of target analytes, surrogates, and internal standards into individual 0.25 g aliquots of bluegill fillet control tissue (T N 08-0202-1/1) hom ogenate. Each spiked fish aliquot was then extracted using the procedures outlined in Section 3.2. A total of thirteen spiked standards ranging from 0.25 ng/g to 300 ng/g (nom inal) w ere prepared. Additionally, an unextracted acetonitrile solvent curve ranging from 0.0025 ng/mL to 50 ng/m L was also prepared which is equivalent to 0.025 ng/g to 500 ng/g tissue concentration. AH sam ple results reported here w ere quantitated against the extracted curve except for PFBA and PFPeA . For PFBA, the endogenous concentration present in the bluegill fillet control tissue (historical average = 4.44 ng/g 8.3% for N =6 m easurem ents) was significantly higher than the PFBA levels observed in the study samples. Adjusting the concentration of the extracted calibration standards for the endogenous level would have produced limits of quantitation very dose to the lab matrix spike level rendering the sam ple results generally unreportable. Therefore, the solvent curve was used for reporting the sam ple results. As for PFPeA , the solvent curve was used for quantitation because the response (raw area counts) of the [1,2 ,3 ,4 -13C 4]PFBA surrogate internal standard in the study samples more closely approximated the surrogate internal standard response in the solvent curve than it did in the extracted calibration curve. The average [1,2 ,3 ,4 -13C4]PFBA area counts in the extracted bluegill control matrix was approximately 80% (Batch 1), 56% (Batch 2), and 77% (Batch 3) of the average area counts in the solvent curve. For the study samples, the average ([1,2,3,4- C4]PFBA area counts was 97% (Batch 1), 84% (Batch 2), and 91% (Batch 3 ) of the average area counts in the solvent curve. A quadratic, 1/x weighted calibration curve was used to fit the data for each analyte. Internal standard quantitation was used. The data was not forced through zero during the fitting process. The accuracy erf each curve point was verified by back-calculating the concentration using the area count ratio of the target analyte to the internal standard. Each solvent calibration standard used to generate the final calibration curve m et the method calibration accuracy requirem ent of 10025% (10030% for the LO Q ). The coefficients of determination (r2) w ere greater than 0.990 for all analytes. As required by ETS 8-45, a minimum of six calibration points were used to generate the final calibration curve. For P FH S , PFO S, and PFO A, the reference standard used for calibration and lab control spikes was comprised predominantly of the linear isomer. A separate set of LCSs using an electrochemical fluorination (E C F) source of PFO S and PFO A was also included. *As fish matrix can vary greatly from speaes to speaes, the control matrix used to generate the extracted calibration curve and laboratory control QC samples is considered to be matrix-matched for the biuegi samples only. The laboratory control matrix should be considered as a "surrogate' control matrix tor the other species investigated in this study 4.2 Limit of Quantitation (LOQ) The LOQ as defined in ETS 8-45 is the lowest non-zero calibration standard in the curve in which the area counts of the target analyte are at least twice those of the matrix blank(s). W hen unextracted solvent quantitation w as used, the area counts o f the extracted aqueous method blanks w as used to assess the LOQ. 4.3 System Suitability Three replicate injections of a solvent calibration standard w ere analyzed at the beginning of the analytical sequence to demonstrate overall system suitability. Method criteria states that system suitability injections shall produce a R SD of less than 7% for the ratio of target analyte area counts to 3M ENVIRONMENTAL LABORATORY PAGE 29 OF 104 3M ENVIRONMENTAL LABORA TORY REPORT NO E09-0372 internal standard area counts and an R SD of less than 2% for the retention tim e. All analytes m et method acceptance criteria for system suitability with the following exceptions: Extraction Batch 1: Area Count R S D s - P F N A (13% ), P FD A {10% ), P FU n A (13% ) f1 2 - 213C ]PFO A (8.1% ), PFBS (9.1% ), and PFHS (8.3% ) Extraction Batch 2: Area Count RSDs - PFN A (7.5% ), PFUnA (11% ), PFBS (17% ), and PFHS (12% ). Additionally, no system suitability injections w ere analyzed for the short adds (PFBA, PFPeA, and PFHxA). Extraction Batch 3: Area Count RSDs - PFO A (10% ) A method deviation has been issued and is included in the data package. The overall impact to the sam ple results is considered minimal. An increase in variability in the area count precision is often observed with an increased num ber of M RM transitions collected within a given period of the data acquisition method. W ith a large num ber of M RM s, few er scans across the chromatographic peak are collected and overall peak shape can vary more from injection to injection. However, the calibration curve, QCs, and samples all experience the sam e conditions. Any increased variability observed in the system suitability injections would also be observed in the LCS data which is used to determine overall method uncertainty. Thus, the variability is accounted for in the assigned method uncertainty reported with the sample results. 4.4 Continuing Calibration During the course of the analytical sequence, several continuing calibration verification samples (C C Vs) w ere analyzed to confirm that the instrument response from initial calibration curve was still in control. For PFCAs (C 7-C 12), PFBS, PFH S, FOSA, [1,2 -13C2]PFOA, and [^O JP F O S all C CV injections (extracted curve) produced recoveries within 100% 25% , which m et method criteria. For PFBA, and PFPeA , no solvent curve C CVs were analyzed in the second batch (s090831a) as the solvent curve vials w ere inadvertently not placed on the autosampler tray until the end o f the analysis. However, the extracted curve C CVs analyzed throughout the run w ere compliant except for one injection of PFPeA (74.1% ). This indicated that the overall instrument response was stable throughout the run. In the third batch, one C C V injection did not m eet method acceptance criteria for PFBA (139% ) and PFHxA (198% ). The samples prior to this injection were LCSs. These LCSs were included in the method uncertainty determination and any noncompliant recoveries essentially increased the overall uncertainty. The sample results after this injection were not reported for PFHxA due to non-compliant LMS recoveries. A method deviation has been issued and is included in the data package. 4.5 Blanks Five types of blanks w ere prepared and analyzed with the samples: matrix blanks of bluegill fillet control tissue (two with IS and surrogate, two without IS and surrogate), aqueous method blanks (two with IS and surrogate, two without IS and surrogate), acidified acetonitrile solvent blanks, acetonitrile blanks with internal standards and surrogates, and acetonitrile solvent blanks (unmodified). Each blank result was reviewed and used to evaluate method performance to determ ine the LOQ for each analyte. Surrogate recoveries of spiked blanks are provided in the Supplemental Information Section 10.3 4.6 Lab Control Spikes (LCSs) Triplicate lab control spikes of the purchased bluegill fillet control matrix at three different levels for all analytes were prepared each extraction day to determ ine analytical method uncertainty (See Section 4.9). For PFH S, PFO S, and PFO A, the standard reference material used for the LCS spikes was the linear isomer, which was the sam e used for the calibration curves. Additional triplicate PFO S LCSs at 3M ENVIRONMENTAL LABORATORY PAGE 30 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 100 ng/g w ere prepared as most of the study sam ple concentrations w ere anticipated to be around this concentration level. Separate technical grade (3M electrochemical fluorination) spikes of branched/linear isomer standards of PFO S and PFO A w ere prepared to evaluate any potential bias from quantitation against a linear standard. Lab control spikes w ere prepared to evaluate method accuracy and precision and w ere used to determ ine analytical method uncertainty (S ee Section 4.9). The [1,2 -13C2]PFOA and [18O dP FO S surrogate w ere spiked at a consistent 1 ng/g (0.1 ng/mL) for all LCS samples. Lab control spike recoveries are provided in the Supplem ental Information (Section 10.1). For ETS 8-45.0, method acceptance criteria for LCS recoveries is 10030% with RSD <20% . 4.7 Sample Concentration Calculation The extracted calibration curve or solvent calibration curve used for quantitation provided extract concentration in unite of ng/mL. The following equation w as used to convert the extract concentration to sam ple tissue concentration in unite of ng/g. Extract Concentration * ExtractionVolume(mL) Tissue C o n c e n t r a t i o n ^ ----------------------- Extracted Massfc) Extraction Volume = 2.5 mL Extracted Mass -0.25 g 4.8 Lab Matrix Spikes (LMSs) For each submitted sam ple, a separate laboratory matrix spike was prepared by extracting a separate aliquot of the fillet tissue that was spiked with the target analytes. For each LM S, all target analytes w ere spiked at a nominal concentration of 5 ng/g except PFO S, which was spiked at a concentration of approximately 110 ng/g. The recovery of the LMS was calculated using the following equation. ^Extract Cone. ( - ^ - ) * ExtractionVolume(mL) j - 1Average Sample C o n c j ^ j * LMS Sample Mass (g)j LMS %Recovery ----------------------- ------------------------------------ Spike Amount (ng) * Although ETS 8-45.0 does not provide specific criteria for the lab matrix spike concentrations, the 3M Environmental Laboratory uses a general guideline that lab matrix spike concentration should be at least half the endogenous concentration before the spike is considered "appropriate" for the given matrix. For PFO S, the LM S was 27.6 ng (-1 1 0 ng/g.tissue concentration) except far sample E 090372-012 w here the LMS w as 128 ng (-5 1 0 ng/g tissue concentration). The FOSA LMS for this sam ple was also increased to -1 1 0 ng/g tissue concentration. The [1 ,2 -1 C JP FO A and [ O JP FO S surrogate was spiked at 0.261 ng (-1 ng/g tissue concentration). 4.9 Analytical Uncertainty ETS 8-45.0 states that the analytical method uncertainty will be determ ined by statistical evaluation of the individual analyte recoveries in LCSs. Current project Q C results, as well as histoncal values, are used in the evaluation until a maximum of fifty points (minimum of twenty, if possible) are included. For ETS 8-45.0, the historical LCSs are categorized by tissue type: whole-body or fillet unless there is strong evidence suggesting that a species-specific matrix effect is present and that results from these species should be considered separately. The standard deviation of the collective recovery results (in % ) is calculated. The expanded uncertainty is then calculated by multiplying the standard deviation by a factor of two, which corresponds to the 95% confidence limit. Table 9 below provides the analytical uncertainty fa -the target analytes. 3M ENVIRONMENTAL LABORATORY PAGE 31 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 T a b le 9. A n a ly tic a l M etho d U n certain ty Average %Recovery Standard Deviation 2*Standard Deviation Analytical Uncertainty rvPFBA 99.2 6.56 13.1 50 13% mPFPeA PFHxA 97.9 24.0 47.9 27 48% 103 19.6 39.1 50 39% PFHpA 91.9 10.7 21.3 50 21% PFOA 101 9.68 19.4 50 19 PFNA 101 11.1 22.2 50 22 PFDA 97.5 8.65 17.3 50 17 PFUnA PFDoA PFBS PFHS FOSA [1,2-13CJPFOA f*OJPFOS Average %Recovery 101 96.6 96.9 99.1 101 105 Standard Deviation 10.5 6.34 9.55 13.3 10.2 9.63 2'Standard Deviation P)N 21.1 50 12.7 19.1 26.6 50 50 50 20.5 50 19.3 50 Analytical Uncertainty 21 13 19% 27% 20% 19 (1) All LCS recoveries for PFBA and PFPeA used to determine uncertainty were calculated using a solvent curve The PFPeA LCSs from this study only were used for (he analytical method uncertainty determination (2) For N>27, some of the historical LCSs were prepared in walleye fillet 106 8.73 17.5 50 18% 5 Data Summary and Discussion 5.1 All Samples The tables below provide the results for the sample, sam ple duplicate, and lab matrix spikes for the target analytes and the two surrogates. Except for PFBA and PFPeA, all sam ple results were reported from foe extracted calibration curve prepared in bluegill fillet control matrix. In general, most samples produced lab matrix spike and surrogate spike recoveries within method acceptance criteria of 10030% with R PDs less than 20% between foe sam ple and sam ple duplicate. Exceptions have been flagged appropriately in each data table. The recoveries of the 3M PFO A EC F LCSs prepared with each extraction batch (N =9 for foe study) ranged from 82.3% to 113% with a calculated average of 98.0 (11% R SD ). S ee Section 10 1 Similiariy, the recoveries of foe 3M PFO S E C F LCSs (E 09-0372 Phase I Report) ranged from 98.9% to 114% with a calculated average of 107% (4.7% R SD ). The results of foe ECF Q C spikes demonstrated that there is no discernible bias when PFO A and/or PFO S ECF isomers are quantitated against the predominantly linear reference standard. Therefore, the reported PFO A and PFO S values are considered accurate to within the stated method uncertainty regardless of the degree of branched isomers present in the sam ple extracts. 5.2 Sample E09-0372-012 (Client ID 090064, Smallmouth Bass River Section 4) Sam ple E 09-0372-012 exhibited the highest concentration of PFCs collectively: PFO S (570 ng/g Phase I report), FOSA (35.3 ng/g), PFDA (5.79 ng/g), PFDoA (5.40 ng/g), PFUnA (4.03 ng/g), PFBA (0.748 ng/g), and PFPeA (0.298 ng/g). PFH xA was detected in this sample, but quantitative concentrations could not be reported due to Q C failures. For this smallmouth bass sample only (River Section 4 ), branched isomers of PFUnA and PFDoA w ere present in the fillet extract. Isomers of PFDA were present, but at a significantly less amount than the PFUnA and PFDoA isomers. 3M ENVIRONMENTAL LABORATORY PAGE 32 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Figure 1 (PFUnA) and Figure 2 (PFD oA ) display the total ion chromatograms for both E 09-0372-012 and a 15 ng/g extracted calibration standard prepared in the bluegill fillet control matrix using predominantly linear reference standards for comparison. Based on raw area counts, the PFUnA branched isomers in E 09-0372-012 comprise approximately 15% of foe total PFUnA signal and PFDoA branched isomers comprise approximately 29% of the total PFDoA signal. For comparison, Figure 3 displays the sam e chromatograms for PFDA. The PFDA isomer signature accounts for approximately 1% of the total PFD A signal. Figure 4 straws the individual M R M transitions of PFUnA and PFDoA in E 09-0372-012 confirming that sm aller peaks preceding foe linear isomer are structural equivalents of PFUnA and PFDoA and not unidentified co-extracted matox components. Representative 3M PFO S production lots have trace levels of PFDA (0 0005% w t), PFUnA (0.0002% wt), and PFDoA (0.0004% w t) with significant degrees of branched isomers: PFD A (51% ), PFUnA (46% ), and PFDoA (33% ). Figure 5 displays a representative chromatogram of foe PFDA, PFUnA, and PFDoA impurities present in a 10 pg/mL solvent standard of 3M EC F PFO A and PFO S. For E09-0372-G 12, the branching profile observed for PFUnA and PFDoA is consistent with the branching profile of PFC A impurities in 3M EC F production PFO S. The small presence of PFD A isomers in this sam ple is not consistent with 3M ECF production P FO S. In this study, no other fish tissue samples with m easurable PFDA, PFUnA, or PFDoA showed foe presence of branched isomers. All study samples had levels of PFDA, PFUnA, and PFDoA above the approximate LOQ of 0.25 ng/g with foe following exceptions: E 09-0372-005 (Carp Section 4): PFD A = 0.283 ng/g (near foe LO Q ), PFUnA <0.242 ng/g, and PFDoA <0.243 ng/g E 09-0372-024 (Freshwater Drum Section 1): PFDA = 1.56 ng/g, PFUnA = 0.448 ng/g a id PFDoA <0.267 ng/g. Assuming that foe branched isomer response factors are equivalent to that of the linear isomer, the estim ated branched isomer LOQ as a percentage of foe linear isomer detected is provided in Table 15 for each sample. The average branching LOQs w ere 17% (PFD A ), 25% (PFUnA ), and 34% (PFDoA). Additionally, foe PFUnA and PFDoA total ion chromatograms for sam ple E09-0372-021 (Fresh w ater drum, Section 4 ) are displayed in Figure 6. This sam ple represents foe second highest detected concentrations of both PFUnA (3.35 ng/g) and PFDoA (2 .2 6 ng/g) for this project; however, the branched isomer signature in E 09-0372-021 is not detected at approximately 7.5% and 11% of foe linear isomer for PFUnA and PFDoA, respectively. Therefore this sam ple is not consistent with the branching profile of PFC A impurities in 3M ECF production PFO S. The PFO S concentration of this sam ple was 23.6 ng/g (Phase I report). Additional samples from river sections 1 ,2 , and 3, with m easurable levels o f PFD A /PFU nA/PFD oA , could not be quantitatively assessed for isomer profiles due to limitations of branched isomer LOQs. 5.3 Specificity The M RM s of 399>80 and 399>99 (P F H S ) and 499>80 (P FO S ) have been documented as potential matrix interferences in some biological tissues arising from the presence of 5-pregnan-3,20-dio!-3sulfate isomers and taurodeoxycholate isomers (bile salt), respectively. To verify that foe reported quantitation was free from significant unknown matrix interferences, foe raw area count ratios of 399>80 to 399>99 and 499>80 to 499>99 w ere evaluated for each sam ple extract and compared to the average area count ratios observed in foe solvent calibration standards and bluegill fillet control matrix extracted calibration curve and LCSs. 1WiSam K Reagen et al , "Characterization at 3M ECF PFCA Byproducts in PFO and PFOS Production Lots', Milwaukee SETAC North America 28*12Annual Meeting (2007). 2 Bensktn, J.P., Bataineh, M, Martin, J.W., Anal. Chem 2007,79,6455-6464 3M ENVIRONMENTAL LABORATORY PAGE 33 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 16 displays the area count ratio of the 499>80 to 499>99 M RM transitions for each sample replicate. The area count ratio for each sam ple replicate was within 25% of foe corresponding instrument batch average for foe solvent calibration calibration curve. The average ratio varied between foe two instruments used (API 4000 Q-trap and A PI 400 0 ) in this study and is likely due to differences in tuning param eters. Only three samples produced PFH S concentrations greater than foe stated LOQ: E 09-0372-001, -004, and -005. The area count ratio of 399>80 to 399>99 (data not shown, but is provided in foe data package) for each replicate of these three samples was also within 25% of the average ratio for foe solvent calibration curve. 3M ENVIRONMENTAL LABORATORY PAGE 34 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 10. Sample Results Summary with QC fo r PFCAs: C 4-C6. 3M LIMS ID E09-0372-001 E09-0372-001 Dup E09-0372-001 LMS E09-0372-002 E09-0372-002 Dup E09-0372-003 E09-0372-003 Dup E09-0372-003 LMS E09-0372-004 E09-0372-004 Dup E09-0372-004 LMS E09-0372-005 E09-0372-005 Dup E09-0372-005 LMS mPFBA Sample Description ,, Species River Location Extracted Mass (g) (fn g?/gf :) %Rec Axys ID-L12916-14, Client ID - 090191 Axys ID- L12916-14, Client ID- 090191 Dup Axys ID- L12916-14, Client ID- 090191 LMS Carp Section 3 .. 0.2403 0.2344 0 2584 Average <0.275 <0.282 4.77 <0.278 %RPD NA Axys ID-L12916-24, Client ID - 090054 Axys ID-L12916-24, Client ID - 090054 Dup Carp Section 1 0.2555 0.2613 <0.258 <0.253 4.98 Average <0.255 %RPD NA Axys ID- L12916-26, Client ID- 090056 Carp Section 1 0.2468 Axys ID- L12916-26, Client ID- 090056 Dup 0.2328 Axys ICF U 2916:26. C!ient ip - 090056 LMS____________ __ _______ ____ ___________P.-2508.-Average <0.267 <0.284 4.98 <0.275 %RPD NA Axys ID- L12917-3, Client ID- 090275 Axys ID- L12917-3, Client ID- 090275 Dup Axys ID -L 1 2917-3, Client ID -090275 LMS Carp Section 4 0.2364 0 2512 02633 Average 0.299 0.271 4.87 0.285 %RPD 10 Axys ID- L12917-10, Client ID- 090282 Carp Axys ID-L12917-10, C lie n tID -090282 Dup Axys ID- L12917-10, Client ID- 090282 LMS________________ Section 4 0.2690 0.2604 ----------------------------- 0 2632 Average 0.939 0.979 5.59 0.959 %RPD 4.2 NA NA 93.4 NA NA 93.4 NA NA 94.7 NA NA 91.5 NA NA 92.4 (,,PFPeA <' on?\ (ng/g) %Rec <0.105 <0.108 4.90 <0.106 NA 0.124 0.191 5.29 0.158 `43 <0.102 0.147 5.40 (fl0.147 NA 0.253 0.113 5.04 0.183 (76 <0.0939 <0.0970 4.88 <0.0954 NA NA NA 98.8 NA NA 99.3 NA NA 103 NA NA 99.9 NA NA 82.4 (i,PFHxA 9(ngn/tg\) yRec <0.265 <0.272 4.66 <0.269 NA 0.341 <0.244 5.34 a,0.341 NA 0.312 <0.274 5.49 0.312 NA <0.270 <0.254 4.92 <0.262 NA 1.21 1.05 5.64 1.13 14 NA NA 96.4 NA NA 99.0 NA NA 104 NA NA 104 NA NA 95.1 p. 37 3M ENVIRONMENTAL LABORATORY PAGE 35 O F 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 10 Continued. 3M U M S ID Sample Description E09-0372-006 E09-0372-006 Dup E09-0372-006 LMS Axys ID- L12917-17, Client ID- 090123 Axys ID- L12917-17, Client ID- 090123 Dup Axys ID- L12917-1 T. Client lD-; 090123 LMS E09-0372-007 E09-0372-007 Dup E09-0372-007 LMS Axys ID- L12931-6, Client ID -090173 Axys ID- L12931-6, Client ID -0 0 )1 7 3 Dup ___ Axys ID- L12931-6, Client ID -090173 LMS E09-0372-008 E09-0372-008 Dup E09-0372-008 LMS Axys ID- L12931-14, Client ID- 090032 Axys ID- L12931-14. Client ID- 090032 Dup Axys ID- L12931-14, Client ID- 090032 LMS E09-0372-009 E09-0372-009 Dup E09-0372-009 LMS Axys ID- L12932-2, Client ID- 090094 Axys ID- L12932-2, Client ID- 090094 Di*> Axys ID- L12932-2, Client ID- 090094 LMS E09-0372-010 E09-0372-010 Dup E09-0372-010 LMS Axys ID- L12932-4, Client ID- 090096 Axys ID- L12932-4, Client ID- 090096 Dup Axys ID- L12932-4, Client ID- 090096 LMS mPFBA ,vPFPeA mPFHxA Spedes River Location Extracted Cone. Mass (g) (ng/g) %Rec Cone. (ng/g) %Rec Cone. (ng/g) %Rec Carp ____ ________ Smalknouth Bass Smallmouth Bass Smallmouth Bass Smallmouth Bass ............. ............ Section 2 Section 3 Section 1 Section 2 Section 2 0.2638 0.2482 0.2594 Average %RPD 0.2414 0.2563 0.2689 Average %RPD 0.2607 0.2507 0.2601 Average %RPD 0.2375 0,2699 0.2688 Average %RPD 0.2622 0.2561 0.2434 Average %RPD <0.250 <0.266 4.73 <0.258 NA <0.273 <0.258 4.51 <0.265 NA <0.253 <0.263 4.66 <0.258 NA <0.278 <1.245 4.69 <0.261 NA <0.252 <0.258 5.24 <0.255 NA NA NA 93.0 NA NA 91,9 NA NA 91.9 NA NA 95.5 NA NA 96.6 <0.0957 <0.102 4.91 <0.0987 NA <0.105 <0.0985 5.14 <0.0988 NA <0.0969 <0,101 5 33 <0.0999 NA <0.106 <0.0936 5.07 <0.0999 NA <0.0963 <0.0986 5.69 <0.0974 NA NA NA 99.4 NA NA 108 NA NA 108 NA NA 106 NA NA 108 0.318 0.293 5.20 0.306 8.3 <0.264 <0.249 4.62 <0.256 NA <0.245 <0.254 g -ffi <0.249 NA <0.268 <0.236 4 57 <0.252 NA <0.243 <0.249 4.99 <0.246 NA NA NA 102 NA NA 99.4 NA NA NA NA 98 2 NA NA 97.2 p. 38 3M ENVIRONMENTAL LABORATORY PAGE 36 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 3M L IM S ID E09-0372-011 E09-0372-011 Dup E09-ryi7J>J111l M S E09-0372-012 E09-0372-012 Dup E09-Q372-013 E09-0372-013 Dup E09-0372-014 E09-0372-014 Dup E09-0372-014 LMS EQ9-0372-015 E09-0372-015 Dup E09-0372-015 LM S mPFBA Sample Description Species River Location Extracted C o hc. Mass(g) (ng/g) y jfa c Axys ID- L12932-9, Client ID- 090042 Axys ID- L12932-9, Client ID- 090042 Dup Axys ID- M 2932-9. Client ID- 090042 LMS A xys ID -L 1 2932-26, Client ID -090248 Axys ID -L 1 2932-26, Client ID - 090248 Dup Smallmouth Bass Smallmouth Bass Section 1 Section 4 0.243 0.2548 0.2483 Average %RPD 0.2646 0.2602 Axys ID -L 1 2933-18, Client ID -090064 Axys ID- L12933-18, Client ID- 090064 Dup White Bass Section 2 Average %RPD 0.2433 0.2599 Average %RPD Axys ID- L12933-20, Client ID- 090066 White Bass Section 2 0.2488 Axys ID- L12933-20, Client ID- 090066 Dup 0 2424 Axys ID- L12933-20. Client ID- 090066 LMS . ------------- -- Average Axys ID-L12933-25, Client ID -090071 White Bass Section 2 %RPD 0.2518 Axys ID- L12933-25, Client ID- 090071 Dup 0.2492 Axys l l > y 2933:25,C lientlD -q90p71 LMS______________________________________ P.?4! Average %RPD 0.350 0.441 4.68 0.395 <423 NA NA 80.6 0.891 0.605 4.89 NA NA 83.7 0.748 <38 0.538 0.922 4.96 NA NA 81.5 0.730 53 <0.265 NA <0.272 NA 4 .8 8 ____ 98.5 <0.269 NA <0.262 <0.265 5.16 <0.263 NA NA NA 96.2 <1,PFPeA mPFHxA Cone. (ng/g) %Rgc Cone. y jte c (ng/g) 0.217 0.270 4.67 0.243 (4 22 0.420 0.175 4.33 0.298 <83 0.259 0.509 4.66 0.384 65 <0.101 <0.104 4.44 <0.103 NA <0.100 <0.101 4.65 <0.101 NA NA NA 85.9 `' 'NR P!NR 0)N R >1 NA NA 84.0 NA NA 85.1 NA NA 92.4 NA NA 89.5 ^'NR PIN R " VlR PINR NA `' 'NR PIN R '' 'NR P,NR NA <0.504 0 .5 1 8 4.40 0 .5 1 1 NA 0 .4 9 8 0 .5 0 4 4.87 <0.501 NA NA NA NR NA NA NR NA NA NR NA NA 93.8 NA NA 95.8 p. 39 3M ENVIRONMENTAL LABORATORY PAGE 37 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 10 Continued. 3M L IM S ID ___________ E09-0372-016 E09-0372-016 Dup E09-0372-016 LMS Sample Description Axys ID -L 1 2934-10, Client ID -090024 Axys ID -L 1 2934-10, Client ID -090024 Dup Axys ID- L12934-10, Client ID- 090024 LMS Spades White Bass ------------------------------------ -- ------------------------------------------------------------------------ E09-0372-017 Axys ID-L12934-12, Client ID -090026 E09-0372-017 Dup Axys ID- L12934-12, Client ID- 090026 Dup E09-0372-017 LM S____Axys ID- L I2934-12, Client lD- 090026 LMS White Bass -------------------------------------------------------------------------------------------------------------- E09-0372-018 Axys ID-L12934-18, Client ID -090017 E09-0372-018 Dup Axys ID-L12934-18, Client ID -090017 Dup . E09-0372-018 LMS Axys ID- L12934-18, Client ID- 090017 LMS White Bass --------------------------------------- ------------------------------- ------------------------------------------ E090372-019 Axys ID- L12945-1, Client ID- 090153 Fresh Water Drum E09-0372-019 Dup Axys ID- L12945-1, Client ID- 090153 Dup E09-0372-019 LMS Axys ID- L12945-1, Client ID- 090153 LMS ________________________________ ______________________________________ E09 0372-020 E09-0372-020 Dup Axys ID -L 1 2945-4, Client ID -090167 Axys ID- L12945-4, Client ID- 090167 Dup Fresh Water Drum . E ^ M Z i ^ p L M S ........_ ^ ^ 1 D :_ L 1 2 9 4 M j Cfent lD: 090167 LMS -- mPFBA mPFPeA mPFHxA River Extracted Cone. Location Mass (g) (ng/g) %Rec fng%) Section 1 0.257 0.2436 0 2R33 Section 1 Average %RPD 0.2442 0.2545 0.2528 Section 1 Average %RPD 0.2640 0.2433 n 2540 Section 3 Average %RPD 0.2568 0.2473 n 2478 Section 3 Average %RPD 0.2372 0.2509 n 7R1R Average %RPD <0.257 <0.271 NA NA 4.70 93.8 <0.264 NA <0.270 <0.259 NA NA 4.9 3 ____ 94.5 <0.265 NA <0.250 <0.271 5.08 NA NA 98.1 <0.261 NA <0.257 NA <0.267 NA 5.16____ 96.8 <0.262 NA <0.278 <0.263 4.76 NA NA 94.3 <0.271 NA <0.0982 <0.104 4.28 <0.101 NA <0.103 <0.0992 4.98 <0.101 NA <0.0956 <0.104 4 81 <0.0997 NA <0.0983 <0.102 4.84 <0.100 NA <0.106 <0.101 4.31 <0.104 NA Cone. %Rec (ng/g) NA NA 881 NA NA 98.4 NA NA 95 7 NA NA 93.8 NA NA 88.1 <0.488 <0.515 A <0.502 NA <0.514 <0.493 4.70 <0.504 NA <0.475 <0.516 <0.496 NA <0.489 <0.507 4.67 <0.498 NA <0.529 <0.500 4.47 <0.515 NA %Rec NA NA Q** f) NA NA 95.0 NA NA NA NA 92.6 NA NA 93.6 p. 40 3M ENVIRONMENTAL LABORATORY PAGE 38 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 10 Continued. 3MLIMSID E09-0372-021 E09-0372-021 Dup E09-0372-021 LMS Sample Description Axys ID- L12945-14, Client ID- 090241 Axys ID- L12945-14, CBent ID- 090241 Dup Axys ID- L12945-14, Client ID- 090241 LMS E09-0372-022 E09-0372-022 Dup E09-0372-022 LMS Axys ID- L12945-16, Client ID- 090078 Axys ID- L12945-16, Client ID- 090078 Dup Axys ID- L12945-16, Client ID- 090078 LMS E09-0372-023 E09-0372-023 Dup E09-0372-023 LMS Axys ID- L12945-19, Client ID- 090081 Axys ID- L12945-19, Client ID- 090081 Dup Axys ID -L12945-19,C B entlD -090081 LMS E09-0372-024 E09-0372-024 Dup E09-0372-024 LMS Axys ID- L12945-30, Client ID- 090009 Axys ID- L12945-30. Client ID- 090009 Dup Axys ID- L12945-30, Client ID- 090009 LMS E09-0372-025 E09-0372-025 Dup E09-0372-025 LMS Axys ID- L12947-7, Client ID- 090266 Axys ID- L12947-7, Client ID- 090266 Dup . .Axys ID- L I2947:7^ Client ID- 090266 LMS __ mPFBA (1>PFPeA mPFHxA Species River Location Extracted Cone. Mass (g) (ng/g) %Rec Cone. (ng/g) %Rec Cone. %Rec (nglg) Fresh Water Drum Fresh Water Drum Fresh Water Drum Fresh Water Drum Bluegill Sunftsh Section 4 Section 2 Section 2 Section 1 Section 3 0.2375 0.2574 0.2341 Average %RPD 0.2468 0.2657 0.2533 Average %RPD 0.2345 0.2537 0.2528 Average %RPD 0.2385 0.2430 0.2470 Average %RPD 0.2338 0.2583 0.2576 Average %RPD <0.278 <0.256 5.39 <0.267 NA <0.267 <0.248 4.89 <0.258 NA <0.281 <0.260 5.01 <0.271 NA <0.277 <0.272 5.04 <0.274 NA <0.282 <0.256 5.67 <0.269 NA NA NA 95.6 NA NA 93.9 NA NA 96.0 NA NA 94.3 NA NA 111 <0.106 <0.0981 5.71 <0.102 NA <0.102 <0.0950 5.28 <0.0987 NA <0.108 0.132 5.17 <*0.132 NA 0.157 <0.104 5.37 <*0.157 NA <0.108 <0.0978 5.74 <0.103 NA NA NA 104 NA NA 104 NA NA 99.5 NA NA 101 NA NA 115 <0.268 <0.248 5.16 <0.258 NA <0.258 <0.240 4.48 <0.249 NA <0.272 <0.251 4.95 <0.262 NA <0.267 <0.262 4.57 0 .2 6 5 NA 0 .2 7 3 0 .2 4 7 4.44 <0.260 NA NA NA 96.6 NA NA 90.8 NA NA 100 NA NA 90.4 NA NA 91.6 IV 'd 3M ENVIRONMENTAL LABORATORY PAGE 3 9 0 F 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 10 Continued. mPFBA ^ PFPeA mPFHxA 3M LIMS ID Sample Description Species River Location 1Extractad Conc. Mass (g) (ng/g) %Rec Conc. (ng/g) %Rec Conc. (ng/g) %Rec E09-0372-026 E09-0372-026 Dup E09-0372-026 LMS Axys ID- L12947-8, Client ID- 090267 Axys ID- L12947-8, Client ID- 090267 Dup Axys ID- L12947-8, Client ID- 090267 LMS Bluegill Sunfish Section 3 0.2355 0.2495 0.2502 Average %RPD <0.280 <0.265 4.77 q 272 NA NA NA 90.3 0.124 <0.101 5.55 `* 0 .1 2 4 NA NA <0.271 NA NA <0.256 NA 106 4.87 97.4 <0.263 NA E09-0372-027 E09-Q372-027 Dup E09-0372-027 LMS Axys ID- L12947-13, Client ID- 090111 Axys ID- L12947-13, Client ID- 090111 Dup Axys ID- L12947-13, Client ID- 090111 LMS Bluegill Sunfish Section 2 0.2610 0.2581 0.2691 Average %RPD <0.253 <0.256 4.81 <0.254 NA NA NA 98.1 0.216 0.261 5.86 0.238 19 NA <0.244 NA NA <0.247 NA 118 4.03 86.8 <0.246 NA E09-0372-028 E09-0372-028 Dup E09-0372-028 LMS Axys ID- L12947-25, Client ID- 090205 Axys ID- L12947-25, Client ID- 090205 Dup Axys ID- L12947-25, Client ID- 090205 LMS Bluegill Sunfish Section 4 0.2455 0.2524 0.2488 Average %RPD 0.538 0.420 5.38 0.479 (,,25 NA NA 92.6 <0.103 <0.100 5.57 <0.101 NA NA <0.260 NA NA <0.253 NA 108 4.66 92.8 <0.256 NA E09-0372-029 E09-0372-029 Dup E09-0372-029 LMS Axys ID- L12947-26, Client ID -090206 Axys ID- L12947-26, Client ID- 090206 Dup Axys ID- L12947-26, Client ID- 090206 LMS E09-0372-030 E09-0372-030 Dup E09-0372-030 LMS Axys ID- L12948-17, Client ID -090061 Axys ID- L12948-17, Client ID- 090061 Dup Axys ID- L12948-17, Client ID- 090061 LMS Bluegill Sunfish Bluegill Sunfish Section 4 0.2421 0.738 NA <0.104 NA <0.263 NA 0.2479 0.724 NA <0.102 NA 0.340 NA 0.2397 5.65 89.4 6.14 115 5.19 93.1 Average 0.731 <0.103 0.340 %RPD 1.9 NA NA Section 1 0.2544 <0.259 NA 0.124 NA <0.251 NA 0.2577 <0.256 NA <0.0980 NA <0.247 NA 0.2350 5.70 102 5.90 106 4.94 92.8 Average <0.258 `*0 .1 2 4 <0.249 %RPD NA NA NA (1) Unless otherwise specified, the recovery of the associated laboratory matrix spike (LMS) was within 10030% which meets ETS 8-45.0 method acceptance criteria. Sample results are considered accurate to within the overall analytical method uncertainty 10013% (PFBA), 10048% (PFPeA), and 10039% (PFHxA). See Section 4.9 Determination ofAnalytical Method Uncertaintyfor more information. Sample results are reported to three significant figures and %RPD to two significant figures. Additional significant figures were used to calculate the average, %RPD, and %recovery. Values In the raw data may vary sightly due to rounding. PFBA and PFPeA p. 42 3M ENVIRONMENTAL LABORATORY PAGE 40 O F 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 results were generated using a solvent (unextracted) curve for quantitation- PFHxA results were quantitated using an extracted calibration curve prepared in a control matrix of bluegill fillet (2) One sample resultwas above the limit of quantitation (LOQ) and the other replicate was below the LOQ. The average reflects only the value above the LOQ. A relative percent difference (%RPD) was not calculated. (3) NR = not reported. The percent recovery of the associated laboratory matrix spke did not meet method criteria of 10030%. The sample results are not reported because the accuracy oould not be assessed. (4) The %RPD exceeded 20%. p. 43 3M ENVIRONMENTAL LABORATORY PAGE 41 O F 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 T ab le 11. S am p le R e s u lts S u m m ary w ith Q C fo r P FC A s: C 7-C 9. 3M LIMS ID Sample Description E09-0372-001 E09-0372-001 Dup E09-0372-001 LMS Axys ID- L12916-14, Client ID- 090191 Axys ID- L12916-14, Client ID- 090191 Dup _Axys ID- L12916-14, Client ID -090191 LMS E09-0372-002 EQ9-0372-002 Dup E09-0372-002 LMS Axys ID- L12916-24, Client ID- 090054 Axys ID- L12916-24, Client ID- 090054 Dup Axys ID- L12916-24, Client ID- 090054 LMS E09-0372-003 E09-0372-003 Dup E09-0372-003 LMS Axys ID- L12916-26, Client ID- 090056 Axys ID- L12916-26, Client ID- 090056 Dup Axys ID- L12916-26, Client ID- 090056 LMS E09-0372-004 E09-0372-004 Dup E09-0372-004 LMS Axys ID- L12917-3, Client ID- 090275 Axys ID- L12917-3, Client ID- 090275 Dup Axys ID- L12917-3, Client ID- 090275 LMS E09-0372-005 E09-0372-005 Dup E09-0372-005 LMS Axys ID- L12917-10, Client ID- 090282 Axys ID- L12917-10, CllentID- 090282 Dup Axys ID- L12917-10, Client ID- 090282 LMS Species Carp Carp Carp Carp Carp River Extracted Location Mass (g) <1>PFHpA Cone (ng/g) LMS %Rec wPFOA Cone (ng/g) LMS %Rec n PFNA Cone LMS (ng/g) %Rec Section 3 Section 1 Section 1 Section 4 Section 4 0.2403 0.2344 0.2584 Average %RPD 0.2555 0.2613 0.2475 Average %RPD 0.2468 0.2328 0.2508 Average %RPD 0.2364 0.2512 0.2633 Average %RPD 0.2690 0.2604 0.2632 Average %RPD <0.260 <0.267 4.39 <0.263 NA <0.245 <0.239 4.61 <0.242 NA <0.253 <0.268 4.50 <0.261 NA <0.264 <0.249 4.23 <0.257 NA <0.232 <0.240 4.26 <0.236 NA NA NA 92.3 NA NA 92.7 NA NA 91.7 NA NA 90.7 NA NA 91.1 <0.273 <0.279 5.07 <0.276 NA <0.256 <0.251 5.59 <0.254 NA <0.265 <0.281 5.57 <0.273 NA <0.277 0.262 5.55 e,0.262 NA 1.14 1.20 6.06 1.17 4.9 NA NA 102 NA NA 107 NA NA 108 NA NA 108 NA NA 99.7 0.351 0.382 5.17 0.366 8.5 <0.256 <0.251 4.75 <0.254 NA <0.265 <0.281 5.38 <0.273 NA 0.435 0.459 4.70 0.447 5.4 <0.243 <0,252 4.99 <0.248 NA NA NA 96.2 NA NA 91.1 NA NA 105 NA NA 86.8 NA NA 102 p. 44 3M ENVIRONMENTAL LABORATORY PAGE 42 O F 104 3M ENVIRONMENTAL LABORA TORY REPORT NO. EOS-0372 Table 11 Continued. 3MLIMSID E09-0372-006 E09-0372-006 Dup E09-0372-006 LMS E09-0372-007 E09-0372-007 Dup E09-0372-007 LMS E09-0372-008 E09-0372-008 Dup E09-0372-008 LMS E09-0372-009 E09-0372-009 Dup E09-0372-009 LMS E09-0372-010 E09-0372-010 Dup E09-0372-010 LMS Sample Description Axys ID- L12917-17, Client ID- 090123 Axys ID- L12917-17, Client ID- 090123 Dup Axys ID- L12917-17, Client ID- 090123 LMS Axys ID- L12931-6, Client ID -090173 Axys ID- L12931-6, Client ID- 090173 Dup Axys ID- L12931-6, Client ID- 090173 LMS Axys ID- L12931-14, Client ID- 090032 Axys ID- L12931-14, Client ID- 090032 Dup Axys ID- L12931-14, Client ID- 090032 LMS Axys ID- L12932-2, Client ID- 090094 Axys ID- L12932-2, Client ID- 090094 Dup Axys ID- L12932-2, Client ID- 090094 LMS Axys ID- L12932-4, Client ID- 090096 Axys ID- L12932-4, Client ID- 090096 Dup Axys ID- L12932-4, Client ID- 090096 LMS Species Carp Smallmouth Bass Smallmouth Bass Smallmouth Bass Smallmouth Bass River Extracted Location Mass (g) Section 2 Section 3 Section 1 Section 2 Section 2 0.2638 0.2482 0.2594 Average %RPD 0.2414 0.2563 0.2689 Average %RPD 0.2607 0.2507 0.2601 Average %RPD 0.2375 0.2699 0.2688 Average %RPD 02622 0.2561 0.2434 Average %RPD <1>PFHpA Cone (ng/g) LMS %Rec lvPFOA Cone (ng/g) LMS %Rec <0.237 <0.252 4.20 <0.244 NA <0.259 <0.244 3.82 <0.251 NA <0.240 <0.249 4.25 <0.245 NA <0.263 <0.232 4.01 <0.247 NA <0.238 <0.244 4.38 <0.241 NA NA NA 88 6 NA NA 83.5 NA NA 89.8 NA NA 87.6 NA NA 86.6 <0.248 <0.264 __ 5 .5 4 ___ <0.256 NA <0.271 <0.256 5.16 <0.263 NA <0.251 <0.261 4.96 <0.256 NA <0.276 <0.243 5.71 <0.259 NA <0.250 <0.256 5.76 <0.253 NA NA NA 111 NA NA 108 NA NA 100 NA NA 119 NA NA 109 n PFNA Cone LMS (ng/g) %Rec <0.248 <0.264 4 ,6 2 __ <0.256 NA <0.271 <0.256 4.87 <0.263 NA <0.251 <0.261 4.86 <0.256 NA <0.276 <0.243 4.40 <0.259 NA <0.250 <0.256 5.09 <0.253 NA NA NA 92.8 NA NA 102 NA NA 98.1 NA NA 91.7 NA NA 96.1 3M ENVIRONMENTAL LABORATORY PAGE 43 O F 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 11 Continued. 3M LIMS ID E09-0372-011 E09-0372-011 Dup E09-0372-011 LMS E09-0372-012 E09-0372-012 Dup E09-0372-012 LMS -0372-013 E09-0372-013 Dup E9-0372-013 LMS E09-0372-014 E09-0372-014 Dup E09-0372-014 LMS E09-0372-015 E09-0372-015 Dup E09-0372-015 LMS Sample Description Axys ID- L12932-9, Client ID- 090042 Axys ID- L12932-9, Client ID- 090042 Dup Axys ID- L12932-9, Client ID- 090042 LMS Axys ID- L12932-26, Client ID- 090248 Axys ID- L12932-26, Client ID- 090248 Dup Axys ID- L12932-26, Client ID- 090248 LMS Axys ID- L12933-18, Client ID- 090064 Axys ID- L12933-18, Client ID- 090064 Dup Axys ID- L12933-18, Client ID- 090064 LMS Axys ID- L12933-20, Client ID- 090066 Axys ID- L12933-20, Client ID- 090066 Dup Axys ID- L12933-20, Client ID- 090066 LMS Axys ID- L12933-25, Client ID- 090071 Axys ID- L12933-25, Client ID- 090071 Dup Axys ID- L12933-25, Client ID- 090071 LMS Species Smallmouth Bass Smallmouth Bass White Bass White Bass White Bass River Extracted Location Mass (g) <f>PFHpA Cone (ng/g) LMS %Rec <1)PFOA Cone (ng/g) LMS %Rec (VPFNA Cone LMS (ng/g) %Rec Section 1 Section 4 Section 2 Section 2 Section 2 0.2430 0.2548 0.2483 Average %RPD 0.2646 0.2602 0.2667 Average %RPD 0.2433 0.2599 0.2547 Average %RPD 0.2488 0.2424 0.2666 Average %RPD 0.2518 0.2492 0.2461 Average %RPD <0.257 NA <0.245 NA 3.89 78.5 <0.251 NA <0.236 NA <0.240 NA 3.92 ......85,0 <0.238 NA <0.257 NA <0.240 NA 4.37 90.4 <0.249 NA <0.251 NA <0.258 NA 4.41 95.5 <0,255 NA <0.248 NA <0.251 NA 4.98 99.6 <0.250 NA <0.270 <0.257 4.95 <0.263 NA <0.248 <0.252 4.68 <0.250 NA <0.269 <0752 4.80 <0.261 NA <0.263 <0.270 4.65 <0.267 NA <0.260 <0.263 5.74 <0.261 NA NA NA 95.3 NA NA 96.7 NA NA 94.8 NA NA 96.1 NA NA 109 <0.270 <0.257 5.03 <0.263 NA <0.248 <0.252 5.14 <0.250 NA 0.282 0795 5.17 0.288 4.8 <0.263 <0.270 4.89 <0.267 NA 0.387 0.341 5.16 0.364 13 NA NA 96.9 NA NA 106 NA NA 96.4 NA NA 101 NA NA 91.5 p. 46 3M ENVIRONMENTAL LABORATORY PAGE 44 O F 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 3M LIMS10 E09-0372-016 E09-0372-016 Dup E09-0372-016 LMS E09-0372-017 E09-0372-017 Dup E09-0372-017 LMS E09-0372-018 E09-0372-018 Dup E09-0372-018LMS E09-0372-019 E09-0372-019Dup E09-0372-019 LMS E09-0372-020 E09-0372-020 Dup E09-0372-020 LMS Sample Description Axys ID- L12934-10, Client ID- 090024 Axys ID- L12934-10, Client ID- 090024 Dup Axys ID- L12934-10, Client ID- 090024 LMS Axys ID- L12934-12, Client ID- 090026 Axys ID- L12934-12, Client ID- 090026 Dup Axys ID- L12934-12, Client ID- 090026 LMS Axys ID- L12934-18, Client ID- 090017 Axys ID- L12934-18, Client ID- 090017 Dup Axys ID- L12934-18, CSent ID- 090017 LMS Axys ID- L12945-1, Client ID- 090153 Axys ID- L12945-1, Client ID- 090153 Dup Axys ID- L12945-1, Client ID- 090153 LMS Axys ID- L12945-4, Client ID -090167 Axys ID- L12945-4, Client ID- 090167 Dup Axys ID- L12945-4, Client ID- 090167 LMS Species White Bass White Bass White Bass Fresh Water Drum Fresh Water Drum River Extracted Location Mass (g) Section 1 Section 1 Section 1 Section 3 Section 3 0.2570 0.2436 0.2633 Average %RPD 0.2442 0.2545 0.2528 Average %RPD 0.2640 0.2433 0.2549 Average %RPD 0.2568 0.2473 0.2478 Average %RPD 0.2372 0.2509 0.2618 Average %RPD <1lPFHpA Cone (ng/g) LMS %Rec <0.243 NA <0.257 NA 4.33 927 <0.250 NA <0.256 NA <0.246 NA 4.80 98.6 <0.251 NA <0.237 NA <0257 NA 4.67 96.7 <0.247 NA <0.243 NA <0.253 NA 5.06 102 <0.248 NA <0263 NA <0249 NA 4.15____ 88.4 <0.256 NA <nPFOA Cone (ng/g) LMS %Rec ,1>PFNA Cone LMS (ng/g) %Rec <0.255 <0.269 4.68 <0.262 NA <0.268 <0.257 5.27 <0.263 NA <0.248 <0269 5.02 <0.259 NA <0.255 <0.265 4.95 <0260 NA <0276 <0.261 4.69 <0.269 NA NA NA 95.5 NA NA 103 NA NA 992 NA NA 95.2 NA NA 95.2 <0.255 <0.269 4.72 <0.262 NA 0.275 0.298 5.30 0.287 7.8 0.504 0.542 5.38 0.523 7.2 0.526 0.516 5.73 0.521 1.9 0.364 0.337 5.00 0.350 7.7 NA NA 96.3 NA NA 98-3 NA NA 96.1 NA NA 100 NA NA 94.4 p. 47 3M ENVIRONMENTAL LABORATORY PAGE 45 O F 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 11 Continued. 3M LIMS ID Sample Description E09-0372-021 EQ9-0372-021 Dup E09-0372-021 LMS Axys ID- L12945-14, Client ID- 090241 Axys ID- L12945-14, Client ID- 090241 Dup Axys ID- L12945-14, Client ID- 090241 LMS E09-0372-022 Axys ID- L12945-16, Client ID- 090078 E09-0372-022 Dup Axys ID- L12945-16, Client ID- 090078 Dup E09-0372-022LMS . AxysID- L12945-16, Client ID - 090078 LMS E09-0372-023 E09-0372-023 Dup E09-0372-023 LMS Axys ID- L12945-19, Client ID- 090081 Axys ID- L12945-19. Client ID- 090081 Dup Axys ID- L12945-19, Client ID- 090081 LMS E09-0372-024 E09-0372-024 Dup E09-0372-024 LMS Axys ID- L12945-30, Client ID- 090009 Axys ID- L12945-30, Client ID- 090009 Dup Axys ID- L12945-30, Client ID- 090009 LMS E09-0372-025 E09-0372-025 Dup E09-0372-025 LMS Axys ID- L12947-7, Client ID- 090266 Axys ID- L12947-7, Client ID- 090266 Dup Axys ID- L12947-7, Client ID- 090266 LMS Species Fresh Water Drum Fresh Water Drum Fresh Water Drum Fresh Water Drum Bluegill Sunfish River Extracted Location Mass (g) <vPFHpA Cone (ng/g) LMS %Rec Section 4 Section 2 Section 2 Section 1 Section 3 0.2375 0.2574 0.2341 Average %RPD 0.2468 0.2657 0.2533 Average %RPD 0.2345 0.2537 0,2528 Average %RPD 0.2385 0.2430 0.2470 Average %RPD 0.2338 0.2583 0.2576 Average %RPD <0.263 <0.243 4.72 <0.253 NA <0.253 <0.235 4.35 <0.244 NA <0.267 <0.246 4.04 <0.256 NA <0.262 <0.257 4.87 <0.260 NA <0,267 <0.242 4.17 <0.255 NA NA NA 89.8 NA NA 89.6 NA NA 83.1 NA NA 97.8 NA NA 87.4 mPFOA Cone (ng/g) LMS %Rec <VPFNA Cerne (ng/g) LMS %Rec <0.276 <0.254 5.84 <0.265 NA <0.265 <0.247 5,27 <0.256 NA <0.279 <0.258 4.73 <0.269 NA <0.275 <0.270 5,83 <0.272 NA <0.280 <0.254 4.54 <0.267 NA NA NA 106 NA NA 103 NA NA 92.6 NA NA 112 NA NA 90.7 0.617 0.616 6.00 0.616 0.17 0.400 0.285 5.49 0.343 34 0289 0265 4.91 0.277 8.6 <0.275 <0.270 4.90 <0.272 NA 0.281 <0.254 5.64 Pl0.281 NA NA NA 97.7 NA NA 101 NA NA 90.7 NA NA 93.8 NA NA 107 p. 48 3M ENVIRONMENTAL LABORATORY PAGE 46 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 3M LIMS ID Sample Description Species River Extracted Location Mass (g) <nPFHpA Cone (ng/g) LMS %Rec tnPFOA Cone (ng/g) LMS %Rec ,1>PFNA Cone LMS (ng/g) %Rec E09-0372-026 E09-0372-026 Dup E09-0372-026 LMS Axys ID- L12947-8, Client ID- 090267 Axys I D L12947-8, Client ID- 090267 Dup Axys ID- L12947-8, Client ID- 090267 LMS Bluegill Sunfish Section 3 0.2355 0.2495 0.2502 Average <0.265 <0.251 3.83 <0.258 NA NA 77.8 <0.278 <0.263 4.39 <0.270 NA NA 85.1 <0.278 <0.263 5.20 <0.270 NA NA 101 %RPD NA NA NA E09-0372-027 Axys I D L12947-13, Client ID- 090111 E09-0372-027 Dup Axys I D L12947-13, Client ID - 090111 Dup E09-0372-027 LMS ___ Axys I D L12947-13, Client I D 090111 LMS Bluegill Sunfish __ Section 2 0.2610 0.2581 0.2691 Average <0.239 <0.242 4.37 <0.241 NA NA 95.5 <0.251 <0.254 A.72 <0.252 NA NA 98.4 <0.251 <0.254 5.04 <0.252 NA NA 105 %RPD NA NA NA E09-0372-028 E09-0372-028 Dup E09-0372-028 LMS Axys I D 112947-25, Client I D 090205 Axys I D L12947-25, Client I D 090205 Dup Axys ID- L12947-25. client I D 090205 LMS Bluegill Sunfish Section 4 0.2455 0.2524 0.2488 Average %RPD <0.255 <0.248 371 ... <0.251 NA NA NA 75-P <0.267 0.291 4.38 <s>0.291 NA NA NA 78.9 <0.267 <0.260 4.69 <0.263 NA NA NA 90.5 E09-0372-029 E09-0372-029 Dup E09-0372-029 LMS Axys I D L12947-26, Client ID 090206 Axys I D L12947-26, Client I D 090206 Dup Axys I D L12947-26, Client I D 090206 LMS Bluegill Sunfish Section 4 0.2421 0.2479 0.2397 Average <0.258 <0.252 3 84 <0.255 NA NA 74.8 <0.271 <0.264 3.93 <0.267 NA NA 73.1 <0.271 <0.264 5.15 <0.267 NA NA 95.7 %RPD NA NA NA E09-0372-030 Axys I D L12948-17, Client I D 090061 Bluegill Sunfish E09-0372-030 Dup Axys I D L12948-17, Client I D 090061 Dup E09-0372-030 LMS ___ Axys I D L12948-17, Client I D 090061 L M S ____ Section 1 0.2544 0.2577 0.2350 Average <0.246 <0.243 4.74 <0.244 NA NA 90.7 <0.257 <0.254 5.37 <0.256 NA NA 97.9 <0.257 <0.254 5.89 <0.256 NA NA 107 %RPD NA NA NA (D unlessomerwisespecmea, me recovery or me associated laooiaiuiy maui*syuvo vao m m iw w u n -- -------- Sample results are considered accurate to within the overall analytical method uncertainty 100421 % (PFHpA), 10Q19% (PFOA), and 10022% (PFNA). See Section 4.9 Determination ofAnalytical Method Uncertaintyfor more information. Sample results are reported to three significant figures and %RPD to two significantfigures. Additional significant ffcures were used to calculate the average, %RPD, and %recovety. Values in the raw data may vary slightly due to rounding. PFHpA PFO A and PFNA results were generated using an extracted calibration curve prepared in a control matrix of bluegill fillet. 3M ENVIRONMENTAL LABORATORY PAGE 4T OF 104 p. 49 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 (2) The %RPD exceeded 20%. (3) One sample resultwas above the limit of quantitation (LOQ) and the other replicate was below the LOQ. The average reflects only the value above the LOQ A relative percent diference (%RPD) was not calculated. p. 50 3M ENVIRONMENTAL LABORATORY PAGE 48 O F 104 3MENVIRONMENTAL LABORATORY REPORT NO. 09-0372 T able 12. S am p le R esu lts S um m ary w ith Q C fo r P FC A s: C 10-C 12. mPFDA <nPFUnA (vPFDoA 3U LIUS ID Sample Description Species River Location Extracted Cone LMS Mass (g) (ng/g) %Rec Cone (ng/g) LMS %Rec Cone LMS E09-Q372-001 E09-0372-001 Dup E09-0372-001 LMS Axys ID-L12916-14, Client ID - 090191 Axys ID- L12916-14, Client ID- 090191 Dup Axys ID- L12916-14, Client ID- 090191 LMS Carp Section 3 0.2403 0J2344 02584 ------------------------- ---------------------------------------------------- E09-0372-002 Axys ID- L12916-24, Client ID- 090054 E09-0372-002 Dup Axys ID- L12916-24, Client ID- 090054 Dup E09-0372-002 LMS Axys ID- L12916-24, Client ID- 090054 LMS Carp Section 1 Average %RPD 0.2555 02613 0 2475 -------------- ---------------------------------------- -------------------------------- E09-0372-003 Axys ID- L12916-26, Client ID- 090056 E09-0372-003 Dup Axys ID- L12916-26, Client ID- 090056 Dup E09-0372-003 LMS Axys ID- L12916-26, Client ID- 090056 LMS Carp Section 1 Average %RPD 0.2468 0.2328 0.2508 ____________________________________ _____ ___________ E09-0372-Q04 Axys ID -L 1 2917-3, Client ID -090275 E09-0372-004 Dup Axys ID- L12917-3, Client ID- 090275 Dup . E0SMJ372-004 LMS Axys ID- L12917-3, Client ID- 090275 LMS Carp Section 4 Average %RPD 0.2364 02512 n o fiii ----- ------------------------------------------------------------------ ----------- E09-0372-005 Axys ID- L12917-10, Client ID- 090282 E09-0372-005 Dup Axys ID-L12917-10, Client ID - 090282 Dup E09-0372-005 LMS Axys ID- L12917-10, Client ID- 090282 LMS Carp Section 4 Average %RPD 0.2690 02604 0 2632 Average ------------------------------------------------------------------------------------------------ ---------------------------------------------------------------------%RPD 1.58 NA 1.70 NA 6.58 103 1.64 7.0 1.55 NA 1.52 NA 6.72 103 1.53 1.6 0.681 0.728 NA NA 6.21 111 0.704 6.7 2.46 NA 2.46 NA 7.16 99.8 2.46 0.24 0.267 0.299 NA NA 5.15____ 103 0.283 11 0.654 NA 0.659 NA 4.98 88.7 0.657 0.72 0.889 NA 0.957 5.73 NA 94.4 0.923 7.3 0.321 NA 0.329 NA 4.99 929 0.325 2.3 124 NA 1.09 NA 5.84 97.7 1.17 12 <0.238 NA <0246 NA ,, . 4 7 1 . _____ 98.4 <0.242 NA 0.361 NA 0.388 NA ,, 4 7 5 . ____ 8 9 7 0.375 7.3 0.438 NA 0.487 NA 5.28 94.7 0.463 11 0.497 NA 0.548 NA 5 2 5 ____ 9 4 2 0.523 9.6 0.555 NA 0.588 NA 5 .2 8 ____ 98.4 0.572 5.8 <0.239 NA <0247 NA 4 .6 1 ____ 9 6 2 <0.243 NA p. 51 3M ENVIRONMENTAL LABORATORY PAGE 49 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 mPFDA 3M UMS ID Sample Description Species River Location Extracted Cone Mass (g) <ng/g) LMS %Rec E09-0372-006 E09-0372-006 Dup pnQ-f79-nnR i m s E09-0372-007 E09-0372-007 Dup E09-0372-007 LMS E09-0372-008 E09-0372-008 Dup pno.rw7?-nnft i m s E09-0372-009 E09-0372-009 Dup PfVQ.m77-AnQ I MS E09-0372-010 E09-0372-010 Dup E09-0372-010 LMS Axys ID- L12917-17, Client ID- 090123 Axys ID- L12917-17, Client ID- 090123 Dup Axvs ID- L12917-17, Client ID- 090123 LMS Carp Section 2 0.2638 0.2482 0.2594 Average %RPD Axys ID- L12931-6, Client ID- 090173 Smallmouth Bass Axys ID- L12931-6, Client ID- 090173 Dup A m ID- L12931-6, Client ID -090173 L M S ____ ......... ........................... Section 3 ................. ........ 0.2414 0.2563 0.2689 Average %RPD Axys ID- L12931-14, Client ID- 090032 Axys ID- L12931-14, Client ID- 090032 Dup A m I D L12931-14, Client ID- 090032 LMS Smallmouth Bass Section 1 0.2607 0.2507 0.2601 Average %RPD Axys ID- L12932-2, Client ID- 090094 Axys ID- L12932-2, Client ID 090094 Dup Axys I D L12 9 ,2-2 , Client I D 090094 LMS Smallmouth Bass Section 2 0.2375 0.2699 0,2688 Average %RPD Axys I D L12932-4, Client ID- 090096 Axys I D L12932-4, Client I D 090096 Dup A m I D L12932-4, Client ID 090096 LMS Smallmouth Bass Section 2 ____________________ ........................... 0.2622 0.2561 0.2434 Average %RPD 1.23 1.58 6.02 1.41 25 2.07 2.00 5.43 2.04 3.5 1.12 1.19 5.62 1.15 5.6 0.811 1.02 4.58 0.915 23 0.912 0.747 4.67 0.829 20 NA NA 96.6 NA NA 73.6 NA NA 93.7 NA NA 79.4 NA NA 75,5 mPFUnA Cone (ng/g) LMS %Rec 1.16 1.07 5.21 1.11 8.0 1.62 1.48 5.65 1.55 8.6 0.988 0.973 5.58 0.981 1.5 0.813 0.725 5,35 0.769 11 0.531 0.572 5.13___ 0.552 7.4 NA NA 84.4 NA NA 87.6 NA NA 95.0 NA NA 97.7 NA NA 88.4 1,1PFDoA Cone LMS (ng/g) %Rec 0.631 0.728 5.44 NA NA 97.9 0.680 14 0.971 1.03 5.07 NA NA 86.7 1.00 62! 1.05 1.18 5.79 NA NA 96.5 1.11 12 1.21 1.09 5.39 NA NA 90.3 1.15 10 0.530 NA 0.554 NA 6.30 __ 111___ 0.542 4.5 p. 52 3M ENVIRONMENTAL LABORATORY PAGE 50 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 12 Continued. 3M LIMS ID Sample Description Species River Location Extracted Mass (g) E09-0372-011 Dup E09-0372-011 LMS Axys ID- L12932-9, Client ID- 090042 Axys ID- L12932-9, Client ID- 090042 Dup Axys ID- L12932-9, Client ID- 090042 LMS Smallmouth Bass Section 1 -------------------- ----------------------- ----------------------------------- ---------------------------------------------------------------- E09-0372-012 E09-0372-012 Dup Axys ID- L12932-26, Client ID- 090248 Axys ID- L12932-26, Client ID- 090248 Dup Smallmouth Bass Section 4 E09-0372-012 LMS Axys ID- L12932-26, Client ID- 090248 LMS E09-0372-013 E09-0372-013 Dup E09-0372-013 LMS Axys ID- L12933-18, Client ID- 090064 Axys ID- L12933-18, Client ID- 090064 Dup Axys ID- L12933-18, Client ID- 090064 LMS White Bass Section 2 E09-0372-014 E09-0372-014 Dup E09-0372-014 LMS Axys ID- L12933-20, Client ID- 090066 Axys ID- L12933-20, Client ID- 090066 Dup Axys ID- L12933-20. Client ID- 090066 LMS White Bass Section 2 E09-0372-015 E09-0372-015 Dup E09-0372-015 LMS Axys ID- L12933-25, Client ID- 090071 Axys ID- L12933-25, Client ID- 090071 Dup Axys ID -L 1 2933-25, Client ID - 090071 LMS White Bass Section 2 ........... .. . . ______ 0.2430 0.2548 0.2483 Average YoRPD 0.2646 0.2602 0.2667 Average %RPD 0.2433 0.2599 0.2547 Average %RPD 0.2488 0.2424 0.2666 Average %RPD 0.2518 0.2492 0.2461 Average %RPD PFDA Cone (ng/g) LMS %Rec 1.27 1.22 5.69 1.24 3.9 5.55 6.03 9 84 5.79 8.4 3.36 3.42 8.19 3.39 1.9 3.68 3.47 8.92 3.69 5.9 3.87 3.11 8.10 3.49 22 NA 89.1 NA NA 87.2 NA NA 98.5 NA NA 115 NA NA 91.4 PFUnA Cone (ng/g) LMS %Rec 1.32 1.24 6.40 1.28 6.3 4.06 4.01 8.49 4.03 1.4 1.62 1.78 6.20 1.70 9.2 1.75 1.87 7.18 1.81 6.5 1.94 1.89 7.68 1.91 2.6 NA 101 NA NA 94.4 NA NA 91.0 NA NA 114 NA NA 113 PFDoA Cone LMS (ng/g) %Rec 1.97 6.41 2.04 ft ? 5.12 5.68 9.47 5.40 10 1.26 1.44 5 68 1.35 13 1.17 1.14 5.68 1.16 1.8 1.26 1.44 5.91 1.35 14 NA 86 3 NA NA 86.1 NA NA 86 9 NA NA 95.8 NA NA 89.1 p. 53 3M ENVIRONMENTAL LABORATORY PAGE 51 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 mPFDA 3M UMS ID Sample Description Species River Location Extracted Cone Mass (g) (ng/g) LMS %Rec E09-0372-016 E09-0372-016 Dup I MS E09-0372-017 E09-0372-017 Dup E09-0372-017 LMS E09-0372-018 E09-0372018 Dup Pn0.m794l1fi I MS E09-0372-019 E09-0372-019 Dup E09-0372-019 LMS E09-0372-020 E09-0372-020 Dup E09-0372-020 LMS Axys ID- L12934-10, Client ID- 090024 Axys ID- L12934-10, Client ID- 090024 Dup Axvs ID- L12934-10. Client ID- 090024 LMS White Bass Section 1 0.2570 0.2436 0.2633 Average %RPD Axys ID- L12934-12, Client ID- 090026 Axys ID- L12934-12, Client ID- 090026 Dup Axvs ID- L12934-12, Client ID- 090026 LMS White Bass Section 1 ...... .. 0.2442 0.2545 0.2528 Average %RPD Axys ID- L12934-18, Client ID- 090017 Axys ID- L12934-18, Client ID- 090017 Dup Axvs ID- L12934-18, Client ID- 090017 LMS White Bass Section 1 0.2640 0.2433 0.2549 Average %RPD Axys ID- L12945-1, Client ID- 090153 Axys ID- L12945-1, Client ID- 090153 Dup Axvs ID- L12945-1. Client ID- 090153 LMS Fresh Water Drum Section 3 0.2568 0.2473 0.2478 Average %RPD Axys ID- L12945-4, Client ID- 090167 Axys ID- L12945-4, Client ID- 090167 Dup Axvs ID- L12945-4, Client ID- 090167 LMS Fresh Water Drum Section 3 . . . _______________ ............. ..... 0.2372 0.2509 0.2618 Average %RPD 2.81 NA 2.83 7.07 NA 90.3 2.82 0.75 3.36 3.15 NA NA 8.50 ___ 107 3.26 6.3 3.19 NA 2.55 NA 6.88 82.3 287 22 4.31 NA 4,51 9.19 NA 95.5 441 4.4 3.20 NA 3.52 NA 8.07 99.4 3.36 9.3 mPFUnA Cone (ng/g) LMS %Rec 1.54 NA 1.68 5.37 NA 78.7 1.61 9.1 2.01 1.80 NA NA 6.87 99.7 1.90 11 1.41 NA 1.29 NA 6.74 109 1.35 8.6 1.29 NA 1.36 NA 6 .2 7 ____ 97.1 1.33 5.3 1.53 1.34 NA NA 6.65 108 1.43 13 mPFDoA Cone (ng/g) LMS %Rec 1.03 0.995 5.10 1.01 3.5 1.01 0.919 5.47 0.962 8.9 0.716 0.660 6.11 0.688 8.2 0.610 0.703 5.31 0.656 14 0.768 0.663 5.06 0.715 15 NA NA 85.4 NA NA 90.4 NA NA 110 NA NA 91.5 NA NA 90.3 p. 54 3M ENVIRONMENTAL LABORATORY PAGE 52 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 12 Continued. 3M U M S ID E09-0372-021 E09-0372-021 Dup E09-0372-021 IM S Sample Description Species Axys ID- L12945-14, Client ID- 090241 Axys ID- L12945-14, Client ID- 090241 Dup Axys ID- L12945-14, Client ID- 090241 LMS Fresh Water Drum E09-0372-022 E09-0372-022 Dup E09-0372-022 LMS Axys ID- L12945-16, Client ID- 090078 Axys ID- L12945-16, Client ID- 090078 Dup Axys ID- L12945-16, Client ID- 090078 LMS Fresh Water Drum E09-0372-023 E09-0372-023 Dup E09-0372-O23 LMS Axys ID- L12945-19, Client ID- 090081 Axys ID- L12945-19, CtientID- 090081 Dup Axys ID-L12945-19, Client ID - 090081 LMS Fresh W ater Drum E09-0372-024 E09-0372-024 Dup E09-0372-024 LMS Axys ID- L12945-30, Client ID- 090009 Axys ID- L12945-30, Client ID- 090009 Dup Axys ID- L12945-30. Client ID- 090009 L M S _ Fresh Water Drum E09-0372-025 E09-0372-025 Dup E09-0372-025 LMS Axys ID- L12947-7, Client ID- 090266 Axys ID- L12947-7, Client ID- 090266 Dup Axys ID- L12947-7, Client ID- 090266 LMS Bluegill Sunfish River Location Extracted Mass (g) <VPFDA Cone LMS (ng/g) %Rec Section 4 Section 2 Section 2 Section 1 Section 3 0.2375 0.2574 0.2341 Average %RPD 0.2468 0.2657 0.2533 Average %RPD 0.2345 0.2537 0.2528 Average %RPD 0.2385 0.2430 0.2470 Average %RPD 0.2338 0.2583 0.2576 Average %RPD <J|3.38 (s3.82 11.4 3.60 12 1.65 1.45 6.60 1.55 13 1.40 1.41 5.86 1.40 0.90 1.65 1.47 7.35 1.56 11 2.03 1.73 7.40 1.88 16 NA NA 148 NA NA 103 NA NA 91.0 NA NA 115 NA NA 115 mPFUnA Cone (ng/g) LMS %Rec 3.29 3.40 7.90 3.35 3.1 0.812 0.698 5.59 0.755 15 0.732 0.896 5.07 0.814 20 0.411 0.486 6.07 0.448 17 1.03 0.938 5.38 0.985 9.6 NA NA 84.6 NA NA 97.1 NA NA 85.5 NA NA 110 NA NA 89.8 mPFDoA Cone (ng/g) LMS %Rec 2.56 1.96 7.36 2.26 26 0.369 0.445 5.14 0.407 19 0.420 0.507 5.02 0.464 19 <0.269 <0.264 4.62 <0.267 NA 0.569 0.465 4.81 0.517 20 NA NA 94.7 NA NA 95.2 NA NA 91.5 NA NA 90.5 NA NA 87.8 p. 55 3M ENVIRONMENTAL LABORATORY PAGE 53 O F 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 3M UMS ID Sample Description Species River Location mPFDA Extracted Cone LMS Mass (g) (ng/g) %Rec 1,1PFUnA Cone (ng/g) LMS %Rec mPFDoA Cone (ng/g) LMS %Rec E09-0372-026 E09-0372-026 Dup E09-0372-026 LMS Axys ID- L12947-8, Client ID- 090267 Axys ID- L12947-8, Client ID- 090267 Dup Axvs ID- L12947-8, Client ID- 090267 LMS Bluegill Sunfish Section 3 0.2355 0.2495 0.2502 Average 3.29 276 __ 7.94 3.02 NA NA 99.3 1.80 1.88 ....7 .8 8 ........ 1.84 NA NA 120 . 0.727 1.09 5.17 0.910 %RPD 18 4.3 40 E09-0372-027 E09-0372-027 Dup E09-0372-027 LMS Axys ID- L12947-13, Client ID- 090111 Axys ID- L12947-13, Client ID- 090111 Dup Axvs ID- L12947-13, Client ID- 090111 LMS Bluegill Sunfish Section 2 0.2610 0.2581 0.2691 Average 1.91 1.70 6.77 1.81 NA NA 108 1 . 1.41 5.62 1.50 NA NA 88.0 0.898 0.867 5.33 0.883 %RPD 11 12 3.6 E09-0372-028 E09-0372-028 Dup E09-0372-028 LMS Axys ID- L12947-25, Client ID- 090205 Axys ID- L12947-25, Client ID- 090205 Dup Axys ID- L12947-25, Client ID- 090205 LMS Bluegill Sunfish Section 4 0.2455 0.2524 0.2488 Average 228 2.03 __ 6.48 216 NA NA 86.8 1.54 1.65 8.12 1.60 NA 1 .30 NA 0,990 129 4.64 1.15 %RPD 12 7.3 27 E09-0372-029 E09-0372-029 Dup E09-0372-029 LMS Axys ID- L12947-26, Client ID- 090206 Axys ID- L12947-26, Client ID- 090206 Dup Axvs ID- L12947-26, Client ID- 090206 LMS Bluegill Sunfish Section 4 ________ 0.2421 0.2479 0.2397 Average 1.33 1.05 9.11 1.19 NA NA 153 1.25 0.874 5.16 1.06 NA NA 78.0 0.719 0.764 624 0.742 %RPD 24 35 6.2 E09-0372-030 E09-0372-030 Dup E09-0372-030 LMS Axys ID- L12948-17, Client ID- 090061 Axys ID- L12948-17, Client ID- 090061 Dup Axys ID- L12948-17, Client ID- 090061 LMS Bluegill Sunfish Section 1 02544 0.2577 02350 Average 1.74 NA 0.879 1.50 NA 1.06 7.30 108 5.86 1.62 0.968 NA NA 91.3 0.627 0.411 4.44 0.519 %RPD 15 18 42 (1) Sample suite are considered accurate to within the overall analytical method uncertainty 10017% (PFDA), 10021% (PFUnA), and 10013% (PFDoA). See Section 4 9 Determination ofAnalytical Method Uncertainty for more information. Sample results are reported to three significant figures and %RPD to two significant figures. Additional significant figures were used to calculate the average, %RPD, and "/recovery. Values in the raw data may vary slightly due to rounding. PFDA PFUnA and PFDoA results were generated using an extracted calibration curve prepared in a control matrix of bluegill fillet NA NA 84.5 NA NA 95.0 NA NA 69,0 NA NA 105 NA NA 73.1 3M ENVIRONMENTAL LABORATORY PAGE 54 O F 104 p. 56 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 (2) The %RPD exceeded 20%. (3) IM S reooveiy exceeded 10030%, but was within 10060%. The sample uncertainty has been adjusted to 10060%. p. 57 3M ENVIRONMENTAL LABORATORY PAGE 55 O F 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 T a b le 13. S am p le R e s u lts S u m m ary w ith Q C fo r P FB S , P FH S , an d F O S A . 3 M U M S ID E09-0372-001 E09-0372-001 Dup E09-0372-001 LMS Sample Description Species Axys ID- L12916-14, Client ID- 090191 Axys ID- L12916-14, Client ID- 090191 Dup Axys ID- L12916-14, Client ID- 090191 LMS Carp E09-0372-002 E09-0372-002 Dup E09-0372-002 LMS Axys ID- L12916-24, Client ID- 090054 Axys ID- L12916-24, Client ID- 090054 Dup Axys ID- L12916-24, Client ID- 090054 LMS Carp E09-0372-003 E09-0372-003 Dup E09-0372-003 LMS Axys ID- L12916-26, Client ID- 090056 Axys ID- L12916-26, Client ID- 090056 Dup Axvs ID- L12916-26, Client ID- 090056 LMS Carp E09-0372-004 E09-0372-004 Dup E09-0372-004 LMS Axys ID- L12917-3, Client ID- 090275 Axys ID- L12917-3, Client ID- 090275 Dup Axvs ID- L12917-3, Client I D 090275 LMS Carp E09-0372-005 E09-0372-005 Dup Fni)-0372-005 LMS Axys ID- L12917-10, Client I D 090282 Axys ID- L12917-10, Client I D 090282 Dup Carp River Location Extracted Mass (g) ,1>PFBS Cone (ng/g) LMS %Rec Section 3 Section 1 Section 1 Section 4 Section 4 0.2403 0.2344 0.2584 Average %RPD 0.2555 0.2613 0.2475 Average %RPD 0.2468 0.2328 0.2508 Average %RPD 0.2364 0.2512 0.2633 Average %RPD 0.2690 0.2604 0.2632 Average %RPD <0.262 <0.269 4.39 <0.265 NA <0.247 <0.241 4.46 <0.244 NA <0.255 <0.271 4.40 <0,263 NA <0.266 <0.251 4.39 <0.259 NA <0.234 <0.242 3.79 <0.238 NA NA NA 91.5 NA NA 89.1 NA NA 88.9 NA NA 93.1 NA NA 80.4 mPFHS Cone (ng/g) LMS %Rec 0.479 0.492 5.64 0.485 2.7 <0.256 <0.251 5.43 <0.254 NA <0.265 <0.281 4.85 <0.273 NA 0.948 0.869 5.47 0.908 8.7 0.290 0.296 4.36 0.293 2.0 NA NA 103 NA NA 104 NA NA 94.4 NA NA 93.1 NA NA 83.0 ^FOSA Cone (ng/g) LMS %Rec 0.538 0.538 5.46 0.538 0.061 <0.245 <0.239 5.24 <0.242 NA <0.253 <0.268 5.06 <0.261 NA 0.403 0.447 5.37 0.425 10 0.605 0.603 5.32 0.604 0.35 NA NA 103 NA NA 105 NA NA 103 NA NA 106 NA NA 101 p. 58 3M ENVIRONMENTAL LABORATORY PAGE 56 O F 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 13 Continued. 3 M U M S ID E09-0372-006 E09-0372-006 Dup E09-0372-006 LMS Sample Description Species Axys ID- L12917-17, Client ID- 090123 Axys ID- L12917-17, Client ID- 090123 Dup Axvs ID- L12917-17. Client ID- 090123 LMS Carp E09-0372-007 E09-0372-007 Dup E09-0372-007 LMS Axys ID- L12931-6, Client ID- 090173 Axys ID- L12931-6, Client ID- 090173 Dup Axys ID- L12931-6. Client ID- 090173 LMS Smallmouth Bass E09-0372-008 E09-0372-008 Dup E09-0372-008 LMS Axys ID- L12931-14, Client ID- 090032 Axys ID- L12931-14, Client ID- 090032 Dup Axys ID- L12931-14, Client ID- 090032 LMS Small mouth Bass E09-0372-009 E09-0372-009 Dup E09-0372-009 LMS Axys ID- L12932-2, Client ID- 090094 Axys ID- L12932-2, Client ID- 090094 Dup Axys ID- L12932-2, Client ID- 090094 LMS Smallmouth Bass E09-0372-010 E09-0372-010 Dup E09-0372-010 LMS Axys ID- L12932-4, Client ID- 090096 Axys ID- L12932-4, Client ID- 090096 Dup Axys ID- L12932-4, Client ID- 090096 LMS Smallmouth Bass River Location Extracted Mass (g) (,,PFBS Cone (ng/g) LMS %Rec Section 2 Section 3 Section 1 Section 2 Section 2 0.2638 0.2482 0.2594 Average %RPD 0.2414 0.2563 0.2689 Average %RPD 0.2607 0.2507 0.2601 Average %RPD 0.2375 0.2699 02688 Average %RPO 0.2622 0.2561 0.2434 Average %RPD <0239 <0.254 4.73 <0.246 NA <0.261 <0.246 4.39 <0.253 NA <0.242 <0.251 4.68 <0.246 NA <0.265 <0.233 3.96 <0.249 NA <0.240 <0.246 4.37 <0.243 NA NA NA 99.0 NA NA 95.2 NA NA 98.2 NA NA 85.9 NA NA 85.7 mPFHS Cone LMS %Rec <0.248 <0.264 4.92 <0.256 NA <0.271 <0.256 4.82 <0.263 NA <0.251 <0.261 4.81 <0.256 NA <0.276 <0.243 4.59 <0.259 NA <0.250 <0.256 6.12 <0.253 NA NA NA 99.0 NA NA 100 NA NA 96.9 NA NA 95.7 NA NA 116 mFO S A Cone (ng/g) LMS %Rec 0.510 0.591 4.77 0.551 15 0.687 0.788 4.91 0.737 14 0.512 0.525 4.92 0.518 2.4 0.616 0.669 5.20 0.642 8.2 0.344 0.345 4.88 0.344 0.11 NA NA 89 0 NA NA 91.2 NA NA 93.1 NA NA 99.6 NA NA 89.7 3M ENVIRONMENTAL LABORATORY PAGE 57 O F 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 3 M U M S ID E09-0372-011 E09-0372-011 Dup E09-0372-011 LMS E09-0372-012 E09-0372-012 Dup RKU1377-012 LMS E09-0372-013 E09-0372-013 Dup pns-na7?-0i3 LMS E09-0372-014 E09-0372-014 Dup E09-0372-014 LMS E09-0372-015 E09-0372-015 Dup E09-0372-015 LMS Sample Description Species River Location Extracted Mass (g) (1>PFBS Cone (ng/g) LMS %Rec Axys ID- L12932-9, Client ID- 090042 Axys ID- L12932-9, Client ID- 090042 Dup Axvs ID- L12932-9, Client ID- 090042 LMS Smallmouth Bass Section 1 ... ........... 0.2430 0.2548 0.2483 Average %RPD Axys ID- L12932-26, Client ID- 090248 Axys ID- L12932-26, Client ID- 090248 Dup Axvs ID- L12932-26, Client ID- 090248 LMS Smallmouth Bass Section 4 0.2646 0,2602 0.2667 Average %RPD Axys ID- L12933-18, Client ID- 090064 Axys ID- L12933-18, Client ID- 090064 Dup Axvs ID- L12933-18, Client ID- 090064 LMS White Bass Section 2 0.2433 0.2599 0.2547 Average %RPD Axys ID- L12933-20, Client ID- 090066 Axys ID- L12933-20, Client ID- 090066 Dup Axys ID- L12933-20, Client ID - 090066 IM S White Bass Section 2 0.2488 0.2424 ............................ _____.......--__ 0.2666 Average %RPD Axys ID- L12933-25, Client ID- 090071 Axys ID- L12933-25, Client ID- 090071 Dup Axvs ID- L12933-25, Client ID- 090071 LMS White Bass Section 2 0.2518 0.2492 0.2461 Average %RPD <0.259 <0.247 4.38 <0.253 NA <0.238 <0.242 4.59 <0.240 NA <0.259 <0.242 4.81 <0.251 NA <0.253 <0.260 4.59 <0.257 NA <0.250 <0.253 5.31 <0.252 NA NA NA 87.7 NA NA 98.8 NA NA 98.8 NA NA 98.8 NA NA 105 mPFHS Cone (ng/g) LMS %Rec <0.270 NA <0.257 NA 4 .9 0 ...... 94.4 <0.263 NA <0.248 NA <0.252 NA 4.65 ,96.1 <0.250 NA <0.269 NA <0.252 NA 4,78 94.4 <0.261 NA <0,263 <0.270 NA NA 4.50 93.0 <0.267 NA <0.260 NA <0.263 NA 5.87 112 <0.261 NA mFOSA Cone (ng/g) LMS %Rec 0.774 NA 0.790 NA 5.39 93.0 0.782 2.1 35.5 35.2 NA NA 142 35.3 101. 1.0 1.30 NA 1.24 NA 5.73 92.3 1.27 5.0 1.41 NA 1.39 NA 5.96___ 98.9,, 1.40 1.0 1.56 NA 1.81 6.03 NA 87.1 1.68 15 p. 60 3M ENVIRONMENTAL LABORATORY PAGE 58 O F 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 13 Continued. 3M U M S ID E09-0372-016 E09-0372-016 Dup E09-0372-016 LMS Sample Description Species Axys ID- L12934-10, Client ID- 090024 Axys ID- L12934-10. Client ID- 090024 Dup Axys ID- L12934-10, Client ID- 090024 LMS White Bass E09-0372-017 E09-0372-017 Dup E09-0372-017 LMS Axys ID- L12934-12, Client ID- 090026 Axys ID- L12934-12, Cient ID- 090026 Dup Axys ID- L I2934-12, Client ID- 090026 LMS White Bass E09-0372-018 E09-0372-018 Dup E09-0372-018 LMS Axys ID- L12934-18, Client ID- 090017 Axys ID- L12934-18, Client ID- 090017 Dup Axys ID- L12934-18, Client ID- 090017 LMS White Bass . E09-0372-019 E09-0372-019 Dup E09-0372-019 LMS Axys ID- L12945-1, Client ID- 090153 Axys ID- L12945-1, Client ID- 090153 Dup Axys ID- L12945-1, Client ID- 090153 LMS Fresh Water Drum E09-0372-020 E09-0372-020 Dup E09-0372-020 LMS Axys ID- L12945-4, Cyent ID- 090167 Axys ID- L12945-4, Client ID- 090167 Dup Axys ID- L12945-4, Client ID- 090167 LMS Fresh Water Drum River Location Extracted Mass (g) mPFBS Cone (ng/g) LMS %Rec Section 1 Section 1 Section 1 Section 3 Section 3 0.2570 0.2436 0.2633 Average %RPO 0.2442 0.2545 0.2528 Average %RPD 0.2640 0.2433 0.2549 Average %RPD 0.2568 0.2473 0.2478 Average %RPD 0.2372 0.2509 0.2618 Average %RPD 1.45 P)<0.259 4.68 m 1.45 NA <0.258 <0.248 5.12 <0.253 NA <0.239 <0.259 4.90 <0.249 NA <0.245 <0.255 5.13 <0.250 NA <0.266 <0.251 4.59 <0.258 NA NA NA 68.6 NA NA 104 NA NA 101 NA NA 102 NA NA 97.0 <VPFHS Cone (ng/g) LMS %Rec mFOSA Cone (ng/g) LMS %Rec <0.255 <0.269 4.52 <0.262 NA <0.268 <0.257 4.78 <0.263 NA <0.248 <0.269 4.98 <0.259 NA <0.255 <0.265 5.03 <0.260 NA <0.276 <0.261 4.70 <0.269 NA NA NA 92.2 NA NA 93.6 NA NA 98.4 NA NA 96.7 NA NA 95.3 0.956 1.17 5.35 1.06 20 1.73 1.80 6 r30 1.76 3.8 2.70 2.44 6.99 2.57 10 0.653 0.617 5.22 0.635 5.8 <0.263 0.297 4.86 Pl0.297 NA NA NA 91.7 NA NA 93.2 NA NA 91.7 NA NA 92.3 NA NA 97.1 p. 61 3M ENVIRONMENTAL LABORATORY PAGE 59 O F 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 13 Continued. 3M U M S ID E09-0372-021 E09-0372-021 Dup E09-0372-021 LMS Sample Description Species Axys ID- L12945-14, Client ID- 090241 Axys ID- L12945-14, Client ID- 090241 Dup Axvs ID- L12945-14, Client ID- 090241 LMS Fresh Water Drum E09-0372-022 E09-0372-022 Dup E09-0372-022 LMS Axys ID- L12945-16, Client ID- 090078 Axys ID- L12945-16, Client ID- 090078 Dup Axys ID- L12945-16, Client ID- 090078 LMS Fresh Water Drum E09-0372-023 E09-0372-023 Dup Fno-n379-n?3 i m s Axys ID- L12945-19, Client ID- 090081 Axys ID- L12945-19, Client ID- 090081 Dup Axys ID- L12945-19, Client ID- 090081 LMS Fresh Water Drum E09-0372-024 E09-0372-024 Dup E09-0372-024 LMS Axys ID- L12945-30, Client ID- 090009 Axys ID- L12945-30, Client ID- 090009 Dup Axvs ID- L12945-30, Client ID- 090009 LMS Fresh Water Drum E09-0372-025 E09-0372-025 Dup E09-0372-025 LMS Axys ID- L12947-7, Client ID- 090266 Axys ID- L12947-7, Client ID- 090266 Dup Axvs ID- L12947-7, Client ID- 090266 LMS Bluegill Sunfish River Location Section 4 Section 2 Section 2 Section 1 Section 3 Extracted Mass (a) 0.2375 0.2574 0.2341 Average %RPD 0.2468 0.2657 0.2533 Average %RPD 0.2345 0.2537 0.2528 Average %RPD 0.2385 0.2430 0.2470 Average %RPD 0.2338 0.2583 0.2576 Average %RPD ,VPFBS Cone LMS %Rec <0.265 <0.245 5.43 <0.255 NA <0.255 <0.237 6.16 <0.246 NA <0.269 <0.248 6.05 <0.258 NA <0.264 <0.259 5.57 <0.262 NA <0.269 <0.244 4.92 <0.257 NA NA NA 102 NA NA 126 NA NA 123 NA NA 111 NA NA 102 mPFHS Cone LMS %Rec <0.276 <0.254 6.61 <0.265 NA <0.265 <0.247 4.55 <0.256 NA <0.279 <0.258 5.19 <0.269 NA <0775 <0.270 5.58 <0.272 NA <0.280 <0.254 6.05 <0.267 NA NA NA 120 NA NA 89.3 NA NA 102 NA NA 107 NA NA 121 mFOSA Cone (ng/g) LMS %Rec 1.29 1.29 6.44 1.29 0.23 0.440 0.382 4.00 0.411 14 <0.267 <0.246 4.04 <0.256 NA 0.289 <0.257 4.77 O,0.289 NA 0.588 0.609 5.21 0.598 3.5 NA NA 97.9 NA NA 73.9 NA NA B3.1 NA NA 89.9 NA NA 96.6 p. 62 3M ENVIRONMENTAL LABORATORY PAGE 60 O F 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 13 Continued. 3M U M S ID Sample Description Species River Location Extracted Mass (g) <VPFBS Cone (ngtg) LMS %Rec mPFHS Cone (ng/g) LMS %Rec mFOSA Cone (ng/g) LMS %Rec E09-0372-026 E09-0372-026 Dup E09-0372-026 LMS Axys ID- L12947-8, Client ID- 090267 Axys ID- L12947-8, Client ID- 090267 Dup Axys ID- L12947-8, Client ID- 090267 LMS Bluegill Sunfish Section 3 0.2355 0.2495 0.2502 Average %RPD 0.295 0.260 4.86 0.277 13 NA NA 92.4 <0.278 <0.263 5.36 <0.270 NA NA NA 104 1.00 1.01 5.80 1.01 1.2 E09-0372-027 E09-0372-027 Dup E09-0372-027 LMS Axys ID- L12947-13, Client ID- 090111 Axys ID- L12947-13, Client ID- 090111 Dup Axys ID- L12947-13, Client ID - 090111 LMS Bluegill Sunfish Section 2 0.2610 0.2581 0.2691 Average %RPD <0.241 <0.244 4.03 <0.243 NA NA NA 87.5 <0.251 <0.254 4.56 <0.252 NA NA NA 95.2 0.353 0.338 5.01 0.346 4.5 E09-0372-028 E09-0372-028 Dup E09-0372-028 LMS Axys ID- L12947-25, Client ID- 090205 Axys ID- L12947-25, Client ID- 090205 Dup Axys ID- L12947-25, Client ID- 090205 LMS Bluegill Sunfish Section 4 0.2455 0.2524 0.2488 Average %RPD 0.328 0.336 5.28 0.332 2.4 NA NA 99.2 <0.267 <0.260 4.58 <0.263 NA NA NA 88.4 2.18 2.71 6.70 2.45 m22 E09-0372-029 E09-0372-029 Dup E09-0372-029 LMS Axys ID- L12947-26, Client ID- 090206 Axys ID- L12947-26, Client ID- 090206 Dup Axys ID- L12947-26, Client ID- 090206 LMS Bluegill Sunfish Section 4 0.2421 <0.260 NA <0.271 NA 0.2479 <0.254 NA <0264 NA 0.2397 5.68 110 5.98 111 Average <0.257 <0.267 %RPD NA NA 0.685 0.544 5.47 0.614 <4>23 E09-0372-030 E09-0372-030 Dup E09-0372-030 LMS Axys ID- L12948-17, Client ID- 090061 Axys ID- L12948-17, Client ID- 090061 Dup Axys ID- L12948-17, Client ID- 090061 LMS Bluegill Sunfish Section 1 0.2544 0.2577 0.2350 <0.248 <0.244 4.74 NA NA 89.9 <0.257 <0.254 6.68 NA NA 122 1.46 1.37 6.32 Average <0.246 <0.256 1.42 %RPO NA NA 6.8 (D Sample results are considered accurate to within the overall analytical method uncertainty 10019% (PFBS), 10027% (PFHS), and 10020% (FOSA). See Section 4.9 Determination ofAnalytical Method Uncertaintyfor more information. Sample results are reported to three significant figures and %RPD to two significant figures. Additional significant figures were used to calculate the average, %RPD, and "/recovery. Values to the raw data may vary slightly due to rounding. PFBS, PFHS, and FOSA resultswere generated using an extracted calbration curve prepared in a control matrix of bluegill fillet NA NA 97.4 NA NA 102 NA NA 86.1 NA NA 94.5 NA NA 93.7 p. 63 3M ENVIRONMENTAL LABORATORY PAGE 61 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 (2) LMS recovery exceeded 10030%, but was within 10050%, The sample uncertainty has been adjusted to 10050%, (3) One sample result was above the limit of quantitation (LOQ) and the other replicate was below the LOQ. The average reflects only the value above the LOQ. A relative percent difference (%RPD) was not calculated. (4) The %RPD exceeded 20%. p. 64 3M ENVIRONMENTAL LABORATORY PAGE 62 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. EOS-0372 Table 14. Summary Results for Surrogate Recovery Standards. 3M LIMS ID 09-03724)01 E09-0372-001 Dup E09-0372-001 LMS Sample Description Axys ID- L12916-14, Client ID- 090191 Axys ID- L12916-14, Client ID- 090191 Dup Axys ID- L12916-14, Client ID- 090191 LMS E09-0372-002 E09-0372-002 Dup E09-0372-002 LMS Axys ID- L12916-24, Client ID- 090054 Axys ID- L12916-24, Client ID- 090054 Dup Axys ID- L12916-24, Client ID- 090054 LMS E09-0372-003 E09-0372-003 Dup E09-0372-003 LMS Axys ID- L12916-26, Client ID- 090056 Axys ID- L12916-26, Client ID- 090056 Dup Axys ID- L12916-26, Client ID- 090056 LMS E09-0372-004 E09-0372-004 Dup E09-0372-004 LMS Axys ID- L12917-3, Client ID- 090275 Axys ID- L12917-3, Client ID- 090275 Dup Axys ID- L12917-3, Client ID- 090275 LMS E09-0372-005 E09-0372-005 Dup E09-0372-005LMS Axys ID- L12917-10, Client ID- 090282 Axys ID- L12917-10, Client ID- 090282 Dup Axys ID- L12917-10, Client ID- 090282 LMS Species Carp Carp Carp Carp Carp River Location Section 3 Section 1 Section 1 Section 4 Section 4 Extracted Mass (g) Surrogate %Recovery <1l[1,2-13CJPFOA y 'O J P F O S 0.2403 0.2344 0.2584 Average %RSD 0.2555 0.2613 0.2475 Average %RSD 0.2468 0.2328 0.2508 Average %RSD 0.2364 0.2512 0.2633 Average %RSD 0.2690 0.2604 0.2632 Average %RSD 105 105 100 103 2.7 111 105 111 109 3.1 112 111 106 109 2.8 104 99.0 112 105 6.0 113 110 108 110 2.7 96.2 90.1 99.0 95.1 4.8 105 87.1 99.0 97.0 9.3 96.0 107 103 102 5.4 97.1 96.2 103 98.7 3.7 95.8 94.5 96.2 95.5 0.90 3M ENVIRONMENTAL LABORATORY PAGE 63 O F 104 U 0> Ol Table 14 Continued. 3M LIMS ID E09-0372-006 E09-0372-006 Dup E09-0372-006 LMS Sample Description Axys ID- L12917-17, Client ID- 090123 Axys ID- L12917-17, Client ID- 090123 Dup Axys ID- L12917-17, Client ID - 090123 LMS E09-0372-007 E09-0372-007 Dup E09-0372-007 LMS Axys ID- L12931-6, Client ID- 090173 Axys ID- L12931-6, Client ID- 090173 Dup Axys ID- L12931-6, Client ID- 090173 LMS E09-0372-008 E09-0372-008 Dup E09-0372-008 LMS Axys ID- L12931-14, Client ID- 090032 Axys ID- L12931-14, Client ID- 090032 Dup Axys ID- L12931-14, Client ID- 090032 LMS E09-0372-009 E09-0372-009 Dup E09-0372-009 LMS Axys ID- L12932-2, Client ID- 090094 Axys ID- L12932-2, Client ID- 090094 Dup Axys ID- L12932-2, Client ID- 090094 LMS E09-0372-010 E09-0372-010 Dup E09-0372-010 LMS Axys ID- L12932-4, Client ID- 090096 Axys ID- L12932-4, Client ID- 090096 Dup Axys ID- L12932-4, Client ID- 090096 LMS 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Species Carp Smallmouth Bass Smallmouth Bass Smallmouth Bass Smallmouth Bass River Location Section 2 Section 3 Section 1 Section 2 Section 2 Extracted Mass (g) 0.2638 0.2482 0.2594 Average %RSD 0.2414 0.2563 0.2689 Average %RSD 02607 0.2507 0.2601 Average %RSD 02375 0.2699 0.2688 Average %RSD 0.2622 0.2561 0.2434 Average %RSD Surrogate %Recovery m[1,2-13CJPFOA ^ t ' OJPFOS 112 114 101 109 6.5 108 108 113 109 2.5 119 121 102 114 9.3 127 114 123 121 5.3 109 Pl135 121 121 11 96.2 832! 90.2 89.8 7.2 88.9 88.5 91.7 89.7 2.0 98.1 118 101 106 10 90.9 101 99.0 97.0 5.5 104 106 107 105 1.4 p. 66 3M ENVIRONMENTAL LABORATORY PAGE 64 O F 104 Table 14 Continued. 3M LIMS ID E09-0372-011 E09-0372-011 Dup E09-0372-011 LMS Sample Description Axys ID- L12932-9, Client ID- 090042 Axys ID- L12932-9, Client ID- 090042 Dup Axys ID- L12932-9, Client ID- 090042 LMS E09-0372-012 E09-0372-012 Dup E09-0372-012 LMS Axys ID- L12932-26. Client ID- 090248 Axys ID- L12932-26, Client ID- 090248 Dup Axys ID- L12932-26, Client ID- 090248 LMS E09-0372-013 E09-0372-013 Dup E09-0372-013 LMS Axys ID- L12933-18, Client ID- 090064 Axys ID- L12933-18, Client ID- 090064 Dup Axys ID- L12933-18, Client ID- 090064 LMS E09-0372-014 E09-0372-014 Dup E09-0372-014 LMS Axys ID- L12933-20, Client ID- 090066 Axys ID- L12933-20, Client ID- 090066 Dup Axys ID- L12933-20, Client ID- 090066 LMS E09-0372-015 E09-0372-015 Dup E09-0372-015 LMS Axys ID- L12933-25, Client ID- 090071 Axys ID- L12933-25, Client ID- 090071 Dup Axys ID- L12933-25, Client ID- 090071 LMS 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Species Smallmouth Bass Smallmouth Bass White Bass White Bass White Bass River Location Section 1 Section 4 Section 2 Section 2 Section 2 Extracted Mass (g) 0.2430 0.2548 0.2483 Average %RSD 0.2646 0.2602 0.2667 Average %RSD 0.2433 0.2599 0.2547 Average %RSD 0.2488 0.2424 0.2666 Average %RSD 0.2518 0.2492 0.2461 Average %RSD Surrogate %Recovery (n[1,2-*CJPFOA ''f ' OJPFOS 104 105 95.3 101 5.2 94.9 99.0 97.1 97.0 2.1 101 102 110 104 4.6 96.2 125 122 114 14 108 98.1 107 104 5.1 101 116 112 110 7.2 P)114 '" 106 <3|107 P'109 4.4 117 118 111 115 3.6 103 107 113 108 5.0 112 109 107 109 2.2 3M ENVIRONMENTAL LABORATORY PAGE 65 O F 104 Table 14 Continued. 3M LIUS ID E09-0372-016 E09-0372-016 Dup E09-0372-016 LMS Sample Description Axys ID- L12934-10, Client ID- 090024 Axys ID- L12934-10, Client ID- 090024 Dup Axvs ID- L12934-10. Client ID- 090024 LMS E09-0372-017 E09-0372-Q17 Dup E09-0372-017 LMS Axys ID- L12934-12, Client ID- 090026 Axys ID- L12934-12, Client ID- 090026 Dup Axys ID- L12934-12, Client ID- 090026 LMS E09-0372-018 E09-0372-018 Dup E09-0372-018 LMS Axys ID- L12934-18, Client ID- 090017 Axys ID- L12934-18, Client ID- 090017 Dup Axys ID- L12934-18, Client ID- 090017 LMS E09-0372-019 E09-Q372-Q19 Dup E09-0372-019 LMS Axys ID- L12945-1, Client ID- 090153 Axys ID- L12945-1, Client ID- 090153 Dup Axys ID- L12945-1, Client ID- 090153 LMS E09-0372-020 E09-0372-020 Dup E09-0372-020 LMS Axys ID- L12945-4, Client ID- 090167 Axys ID- L12945-4, Client ID- 090167 Dup Axys ID- L12945-4, Client ID- 090167 LMS 3M ENVIRONMENTAL LABORA TORY REPORT NO. E09-0372 Species White Bass White Bass White Bass Fresh Water Drum Fresh Water Drum River Location Section 1 Section 1 Section 1 Section 3 Section 3 Extracted Mass (g) 02570 0.2436 02633 Average %RSD 0.2442 0.2545 0.2528 Average %RSD 0.2640 0.2433 0.2549 Average %RSD 0.2568 0.2473 0.2478 Average %RSD 0.2372 0.2509 0.2618 Average %RSD Surrogate %Recovery (v[1,2-' 3CJPFOA " Y 'ojpfo s 108 98.1 107 104 5.1 104 113 110 109 4.1 104 100 103 102 2.0 98.1 103 105 102 3.4 99.0 104 109 104 4.6 97.1 117 113 109 9.8 114 112 124 117 5.6 120 102 124 115 10 121 110 126 119 7.1 115 112 113 113 1.8 p. 68 3M ENVIRONMENTAL LABORATORY PAGE 66 O F 104 Table 14 Continued. 3M LIMS ID E09-0372-021 E09-0372-021 Dup E09-0372-021 LMS Sample Description Axys ID- L12945-14, Client ID- 090241 Axys ID- L12945-14, Client ID- 090241 Dup Axys ID- L12945-14, Client ID- 090241 LMS E09-0372-022 E09-0372-022 Dup E09-0372-022 LMS Axys ID- L12945-16, Client ID- 090078 Axys ID- L12945-16, Client ID- 090078 Dup Axys ID- L12945-16, Client ID- 090078 LMS E09-0372-023 E09-0372-023 Dup E09-0372-023 LMS Axys ID- L12946-19, a ie n t ID- 090081 Axys ID- L12945-19, a ie n t ID- 090081 Dup Axys ID- L12945-19, Client ID- 090081 LMS E09-0372-024 E09-0372-024 Dup E09-0372-024 LMS Axys ID- L12945-30, Client ID- 090009 Axys ID- L12945-30, Client ID- 090009 Dup Axys ID- L12945-30, Client ID- 090009 LMS E09-0372-025 E09-0372-025 Dup E09-0372-025 LMS Axys ID- L12947-7, Client ID- 090266 Axys ID- L12947-7, Client ID- 090266 Dup Axys ID- L12947-7, Client ID- 090266 LMS 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Species Fresh W ater Drum Fresh Water Drum Fresh Water Drum Fresh Water Drum Bluegill Sunfrsh River Location Section 4 Section 2 Section 2 Section 1 Section 3 Extracted Mass (g) 0.2375 0.2574 02341 Average %RPD 0.2468 0.2657 0.2533 Average %RPD 0.2345 0.2537 02528 Average %RPD 02385 0.2430 02470 Average %RPD 02338 02583 0.2576 Average %RPD Surrogate %Recovery m[1,2-'3CJPFOA mf ` OJPFOS 122 118 109 116 6.0 125 115 111 117 6.3 100 115 130 115 13 89.5 118 111 105 13 107 112 102 107 4.5 98.1 104 127 110 14 92.8 120 108 107 13 105 104 98.1 102 3.6 102 108 110 106 3.8 100 113 119 111 8.8 3M ENVIRONMENTAL LABORATORY PAGE 67 O F 104 3M ENVIRONMENTAL LABORATORY REPORT NO. EOS-0372 Table 14 Continued. 3M LIMS ID Sample Description Species River Location Extracted Mass (g) Surrogate %Recovery ('>[1,2-'3CJPFOA y O J P F O S E09-0372-026 E09-0372-026 Dup E09-0372-026 LMS Axys ID- L12947-8, Client ID- 090267 Axys ID- L12947-8, Client ID- 090267 Dup Axys ID- L12947-8, Client ID- 090267 LMS Bluegill Surfisti Section 3 0.2355 0.2495 0.2502 120 126 92.7 107 112 105 Average 113 108 %RPD 16 3.2 E09-0372-027 E09-0372-027 Dup E09-0372-027 LMS Axys ID- L12947-13, Client ID- 090111 Axys ID- L12947-13, Client ID- 090111 Dup Axys ID- L12947-13, Client ID- 090111 LMS Bluegill Sunfish Section 2 0.2610 0.2581 0.2691 p>136 87.8 101 111 96.1 114 Average 108 107 %RPD w 23 9.1 E09-0372-028 E09-0372-028 Dup E09-0372-028 LMS Axys ID- L12947-25, Client ID- 090205 Axys ID- L12947-25, Client ID- 090205 Dup Axys ID- L12947-25, Client ID- 090205 LMS Bluegill Sunfish Section 4 0.2455 0.2524 0.2488 103 p)145 106 99,0 103 107 Average 118 103 %RPD 20 3.7 E09-0372-029 E09-0372-029 Dup E09-0372-029 LMS Axys ID- L12947-26, Client ID- 090206 Axys ID- L12947-26, Client ID- 090206 Dup Axys ID- L12947-26, Client ID- 090206 LMS Bluegill Sunfish Section 4 0.2421 0.2479 0.2397 90.7 115 108 a!136 ei138 130 Average 105 134 %RPD 12 3.0 E09-0372-030 E09-0372-030 Dup E09-0372-030 LMS Axys ID- L12948-17, Client ID- 090061 Axys ID- L12948-17, Client ID- 090061 Dup Axys ID- L12948-17, Client ID- 090061 LMS Bluegill Sunfish Section 1 0.2544 0.2577 0.2350 138 122 98.1 116 133 101 Average 120 117 %RSD 17 14 (1) Unless otherwise specified, the recovery of the associated laboratory matrix spike (LMS) was within 10030% which meets ETS 8-45.0 method acceptance criteria. Sample results are considered accurate to within the overall analytical method uncertainty 10Q19% f l l ^ - ' CJPFOA) and 10018% (''OJPFOS). See Section 4.9 Determination ofAnalytical Method Uncertaintyfor more information. Sample results are reported to three significantfigures and %RPD to two signitcant figures. Additional significant figures were used to calculate the average, %RPD, and %recovery. Values in the raw data may vary slightlydue to rounding. [1,2-,3Cj]PFOA and pQJPFOS resultswere generated using an extracted calibration curve prepared in a control matrix of bluegill fillet p. 70 3M ENVIRONMENTAL LABORATORY PAGE 68 O F 104 3M ENVIRONMENTAL LABORA TORY REPORT NO. E09-0372 (?) Recovery exceeded method criteria of 10030%. (?) Results reported from a 1:100 dilution of the sample extract that was respiked with surrogates post dilution. PFOS endogenous levels greater than 500 note biased the f,eQ>PFOS signal in the undiluted extract (4) %RSD>20%. p. 71 3M ENVIRONMENTAL LABORATORY PAGE 69 O F 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Figure 1. (A) E09-Q372-012 PFUnA Total Ion Chromatogram (sum of 563>519, 563>269, and 563>219). Average PFUnA calculated sample concentration = 4.03 ng/g. Inset displays a baseline zoom of the branched isomer region. (B) PFUnA Total Ion Chromatogram of an extracted bluegill fillet calibration standard spiked at 15 ng/g with a predominantly-linear reference standard. 3M ENVIRONMENTAL LABORATORY PAGE 70 OF 104 3M ENVIRONMENTAL LABORA TORY REPORT NO. E09-0372 Figure 2, (A) E09-0372-012 PFDoA Total Ion Chromatogram (sum of 613>569, 613>169, and 613>319). Average PFDoA calculated sample concentration = 5,40 ng/g. Inset displays a baseline zoom of the branched isomer region. (B) PFDoA Total Ion Chromatogram of an extracted bluegill fillet calibration standard spiked at 15 ng/g with a predominantly-linear reference standard. 3M ENVIRONMENTAL LABORATORY PAGE 71 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Figure 3. (A) E09-0372-012 PFDA Total Ion Chromatogram (sum of 513>469, 513>269, and 513>269). Average PFDA calculated sample concentration = 5.79 ng/g. Inset displays a baseline zoom of the branched isomer region. (B) PFDA Total Ion Chromatogram of an extracted bluegill fillet calibration standard spiked at 15 ng/g with a predominantly-linear reference standard. 3M ENVIRONMENTAL LABORATORY PAGE 72 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 A 563>519 ! NJ '.9.5 if.i ' * 0 3 6 -v 2B C Branched PFUnA a n i3 4 1? 1 2 i Linear ! 1 PFUnA ; '( is <13 o 4 'n it <i* " , ! 563>269,,, nsn 1 A 1 jjc; i\ 7/ 1 '1 /, j\ ll*< 1' U .0 u u t i . t u a ii.it 1 4 u 'i 1 3 4 ` j f i -.jv <i,3 Ul<9K30>>. <KU0 5 6 3 > 2 1 9 l '58 ?" 2SZZ il i; 'T ' ! ' \ |<9 1 1 N 9.4j4'.Vi B <>l 1 soi "I ilJ 612> 569 B ra n c h e d ,,t P FD o A '!*' ! \ N *. " " J '' / A '> ' ,J * U * 3` 1 L in e a r 1 '^ / P F D o A .4, 4* H ' " '*1PJ3<VT 11 v X 612> 169 a* I TM 7010 1 onK i .*|; ^ ,j 1 .A \ A i --C - V / : . t<m flftVt & <0 -- 61 2 > 3 1 9 "' ' :1 11 y r. J .:n rxi: i <P, ;- ^ v v ,1 V. ;4 F ig u re d Individual MRM transitions of E09-0372-012. (A) PFUnA. (B). PFDoA. 3M ENVIRONMENTAL LABORATORY PAGE 73 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Figure 5. Representative Total Ion Chromatograms of (A) PFDA. (B) PFUnA, and (C) PFDoA Impurities in a 10 pg/mL solvent standard of technical grade {3M ECF) PFOA and PFOS. 3M ENVIRONMENTAL LABORATORY PAGE 74 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Figure 6. Total Ion Chromatograms of E09-0372-021. (A) PFUnA - average calculated sample concentration 3.35 ng/g. (B) PFDoA - average calculated sample concentration 2.26 ng/g. 3M ENVIRONMENTAL LABORATORY PAGE 75 OF 104 3 M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 15. Branched Isomer Summary for PFDA, PFUnA, and PFDoA. 3M LIMS ID E09-0372-001 E09-0372-002 E09-0372-003 E09-0372-004 E09-0372-005 E09-0372-006 E09-0372-007 E09-0372-008 E09-0372-009 E09-0372-010 E09-0372-011 E09-0372-012 E09-0372-013 E09-0372-014 E09-0372-015 E09-0372-016 E09-0372-017 E09-0372-018 E09-0372-019 E09-0372-020 E09-0372-021 E09-0372-022 E09-0372-023 E09-0372-024 E09-0372-025 E09-0372-026 E09-0372-027 E09-0372-028 E09-0372-029 E09-0372-030 Species Carp Carp Carp Carp Carp Carp Smallmouth Bass Smallmoufh Bass Smallmouth Bass Smallmouth Bass Smallmouth Bass Smallmouth Bass W rite Bass White Bass White Bass White Bass White Bass White Bass Fresh Water Drum Fresh Water Drum Fresh Water Drum Fresh Water Drum Fresh Water Drum Fresh Water Drum Bluegill Sunfish Bluegill Sunfish Bluegill Sunfish Bluegill Sunfish Bluegill Sunfish Blueqill Sunfish River Location Section 3 Section 1 Section 1 Section 4 Section 4 Section 2 Section 3 Section 1 Section 2 Section 2 Section 1 Section 4 Section 2 Section 2 Section 2 Section 1 Section 1 Section 1 Section 3 Section 3 Section 4 Section 2 Section 2 Section 1 Section 3 Section 3 Section 2 Section 4 Section 4 Section 1 "'Estimated Branching (as % of Linear Detected) PFDA <15 <16 <36 <10 <88 <18 <12 <22 <27 <30 <20 (,,1% of total <7.4 <7.0 <7.2 <8.9 <7.7 <8.7 <5.7 <7.4 <6.9 <16 <18 <16 <13 <8.3 <14 <12 <21 <15 PFUnA <38 <27 <77 <21 NA <23 <16 <25 <33 <45 <20 M15% of total <15 <14 <13 <16 <13 <19 <19 <17 <7.5 <33 <31 <56 <25 <14 <17 <16 <24 <26 PFDoA <67 <54 <48 <44 NA <37 <25 <23 <22 <46 <12 P)29% of total <19 <22 <19 <25 <26 <36 <38 <35 <11 <61 <54 NA <48 <27 <28 <22 <34 <48 (1) Branching LOQs estimated using the approximate linear LOQ for PFDA. PFUnA, and PFDoA (0.25 ng/g) (2) Branched isomers detected in this sample Reported value represents the percentage of the total PFUnA and PFDoA quantitated. 3M ENVIRONMENTAL LABORATORY PAGE 76 OF 104 3 M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 16. PFOS sample specificity: Comparison of Area Count Ratio of 499>80 to 499>99. Instrument Batch o090826a (API 4000 0-trap) Solvent Standards (0.025 ng/mL - 50 ng/mL) Bluegill Fillet Control Tissue (Extracted Curve and LCSs) Average Area Count Ratio 499>80:499>99 3.13 3.32 Sample ID E09-0372-001 E09-0372-001 Dup E09-0372-002 E09-0372-002 Dup E09-0372-003 E09-0372-003 Dup E09-0372-004 E09-0372-004 Dup E09-0372-005 E09-0372-005 Dup E09-0372-006 E09-0372-006 Dup E09-0372-007 E09-0372-007 Dup E09-0372-008 E09-0372-008 Dup E09-0372-009 E09-0372-009 Dup E09-0372-010 E09-0372-010 Dup Sample Description Axys ID- L12916-14, Client ID- 090191 Axys ID- L12916-14. Client ID- 090191 Dup Axys ID- L12916-24, Client ID- 090054 Axys ID- L12916-24. Client ID- 090054 Dup Axys ID- L12916-26, Client ID- 090056 Axys ID- L12916-26. Client ID- 090056 Dud Axys ID- L12917-3, Client ID- 090275 Axys ID- L12917-3. Client ID- 090275 Dud Axys ID- L12917-10, Client ID- 090282 Axys ID- L12917-10, Client ID- 090282 Dud Axys ID- L12917-17, Client ID- 090123 Axys ID- L12917-17, Client ID- 090123 Dup Axys ID- L12931-6, Client ID- 090173 Axys ID- L12931-6, Client ID- 090173 Dup Axys ID- L12931-14, Client ID- 090032 Axys ID- L12931-14. Client ID- 090032 Dup Axys ID- L12932-2, Client ID- 090094 Axys ID- L12932-2, Client ID- 090094 Dud Axys ID- L12932-4, Client ID- 090096 Axys ID- L12932-4, Client ID- 090096 Dup Species Carp Carp Carp Carp Carp Carp Smallmouth Bass Smallmouth Bass Smallmouth Bass Smallmouth Bass Location Section 3 Section 1 Section 1 Section 4 Section 4 Section 2 Section 3 Section 1 Section 2 Section 2 %RSD 6.5 8.8 499>80:499>99 Area Count Ratio 3.36 3.46 3.43 3.45 3.58 3.20 3.08 3.37 3.31 3.50 3.37 3.48 3.42 323 292 3.18 3.08 3.10 322 2.93 3M ENVIRONMENTAL LABORATORY PAGE 77 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 16 Continued. Instrument Batch s090909a (API 4000) Solvent Stds (0.02S ng/mL - SO ng/mL) Bluegill Fillet Control Tissue (Extracted Curve and LCSs) Average Area Count Rado 499>80:499>99 1.48 1.48 Sample ID E09-0372-011 E09-0372-011 Dup E09-0372-012 E09-0372-012 Dup E09-0372-013 E09-0372-013 Dup E09-0372-014 E09-0372-014 Dup E09-0372-015 E09-0372-015 Dup E09-0372-016 E09-0372-016 Dup E09-0372-017 E09-0372-017 Dup E09-0372-018 E09-0372-018 Dup E09-0372-019 E09-0372-019 Dup E09-0372-020 E09-0372-020 Dup Sample Description Axys ID- L12932-9, Client ID- 090042 Axys ID- L12932-9, Client ID- 090042 Dup Axys ID- L12932-26, Client ID- 090248 Axys ID- L12932-26. Client ID- 090248 Dup Axys ID- L12933-18, Client ID- 090064 Axys ID- L12933-18, Client ID- 090064 Dup Axys ID- L12933-20, Client ID- 090066 Axys ID- L12933-20, Client ID- 090066 Dup Axys ID- L12933-25, Client ID- 090071 Axys ID- L12933-25, Client ID- 090071 Dup Axys ID- L12934-10, Client ID- 090024 Axys ID- L12934-10, Client ID- 090024 Dup Axys ID- L12934-12, Client ID- 090026 Axys ID- L12934-12, Client ID- 090026 Dup Axys ID- L12934-18, Client ID- 090017 Axys ID- L12934-18, Client ID- 090017 Dup Axys ID- L12945-1, Client ID- 090153 Axys ID- L12945-1, Client ID- 090153 Dup Axys ID- L12945-4, Client ID- 090167 Axys ID- L12945-4, Client ID- 090167 Dup Species Smallmouth Bass Smallmouth Bass White Bass White Bass White Bass White Bass White Bass White Bass Fresh Water Drum Fresh Water Drum Location Section 1 Section 4 Section 2 Section 2 Section 2 Section 1 Section 1 Section 1 Section 3 Section 3 %RSD 3.7 8.9 499>80:499>9 9 Area Count Ratio 1.44 1.49 1.50 1.47 1 46 1.44 1.50 1.54 1.51 1.44 1.49 1.50 1.51 1 43 1.49 1.45 1.44 1.45 1.46 1.43 3M ENVIRONMENTAL LABORATORY PAGE 78 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 16 continued. Instrument Batch o090828a (API 4000 O-trap) Solvent Stds (0.025 ng/mL - 50 ng/mL) Bluegill Fillet Control Tissue (Extracted Curve and LCSs) Sample ID E09-0372-021 E09-0372-021 Dup E09-0372-022 E09-0372-022 Dup E09-0372-023 E09-0372-023 Dup E09-0372-024 E09-0372-024 Dup E09-0372-025 E09-0372-025 Dup E09-0372-026 E09-0372-026 Dup E09-0372-027 E09-0372-027 Dup E09-0372-028 E09-0372-028 Dup E09-0372-029 E09-0372-029 Dup E09-0372-030 E09-0372-030 Dup Sample Description Axys ID- L12945-14, Client ID- 090241 Axys ID- L12945-14. Client ID- 090241 Dup Axys ID- L12945-16, Client ID- 090078 Axys ID- L12945-16, Client ID- 090078 Dup Axys ID- L12945-19, Client ID- 090081 Axys ID- L12945-19, Client ID- 090081 Dup Axys ID- L12945-30, Client ID- 090009 Axys ID- L12945-30, Client ID- 090009 Dup Axys ID- L12947-7, Client ID- 090266 Axys ID- L12947-7, Client ID- 090266 Dup Axys ID- L12947-8, Client ID- 090267 Axys ID- L12947-8, Client ID- 090267 Dup Axys ID- L12947-13, Client ID- 090111 Axys ID- L12947-13, Client ID- 090111 Dup Axys ID- L12947-25, Client ID- 090205 Axys ID- L12947-25, Client ID- 090205 Dup Axys ID- L12947-26, Client ID- 090206 Axys ID- L12947-26, Client ID- 090206 Dup Axys ID- L12948-17, Client ID- 090061 Axys ID- L12948-17. Client ID- 090061 Dup Average Area Count Ratio 499>80:499>99 3.19 2.97 Species Fresh Water Drum Location Section 4 Fresh Water Drum Section 2 Fresh Water Drum Section 2 Fresh Water Drum Section 1 Bluegill SunFish Section 3 Bluegill Sunfish Section 3 Bluegill Sunfish Section 2 Bluegill Sunfish Section 4 Bluegill Sunfish Section 4 Bluegill Sunfish Section 1 %RSD 8.0 11 499>80:499>99 Area Count Ratio 2.95 2.83 3.19 3.36 3.01 264 322 2.82 297 3.07 3.02 3.12 2 87 3.11 3 16 2.99 2.93 2.98 3.03 3.12 3M ENVIRONMENTAL LABORATORY PAGE 79 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 6 Conclusions Sam ple results presented in Tables 1-4 and Tables 1 0 -1 4 are considered accurate within the stated overall method uncertainty for each analyte. The accuracy {% recovery) and precision (% R S D ) of 3M ECF (branched) PFO A and PFO S laboratory control spikes quantitated against the predominantly linear reference standard demonstrated that the isomers produce no discernable quantitative bias. Area count ratios for 399>80:399>99 and 499>80:499>99 for each sam ple extract w ere within 25% of the average area count ratio observed for the solvent calibration curve analyzed within the given instrument batch thus verifying that the reported quantitation was free from significant matrix interferences. 7 .. Data/Sample Retention All remaining sam ple and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures. 8 Analytical Personnel 8.1 3M Environmental Laboratory Michelle D. Malinsky, Ph.D Research Specialist 8.2 Pace Lab Ops Jonathan Steege 3M ENVIRONMENTAL LABORATORY PAGE 80 OF 104 9 Signatures 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 / // / a y ? Ipedalist, Principal Analytical Investigator Date W illiam K. Reagen, Ph.D., Environmental Laboratory M anagem ent D a te / `J X MV D ate The 3M Environmental Laboratory's Quality Assurance Unit has audited the data and report for this project. 3M ENVIRONMENTAL LABORATORY PAGE 81 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 10 Supplemental Information ; 10.1 Lab Control Spike Recoveries by Extracted Matrix-Matched Calibration with IS Quantitation. Table 17. LCS Recoveries for Extraction Batch 1 Using Extracted Matrix-Matched Calibration: (PFBA, PFPeA, PFHxA). PFBA extracted curve quant) PFPeA (extracted curve quant) PFHxA (extracted curve quant) '' 'Corrected Spike Cone. (na/mL) Calc. Cone. (ng/mL) % Recovery Std. Cone. (no/mL) Calc. Cone. (ng/mL) % Recovery Std. Cone. (ng/mL) Calc. Cone. (ng/mL) % Recovery 090826 BGF LCS Low 1 0.504 0.520 103 0.0528 0.0594 113 0.0502 0.0431 85.9 090826 BGF LCS Low 2 0.493 0.514 104 0.0528 0.0617 117 0.0502 0.0425 84.6 090826 BGF LCS Low 3 0.493 0.513 104 0.0528 0.0606 115 0.0502 0.0460 91.6 090826 BGF LCS Mid 1 0.613 0.609 99.4 0.159 0.172 108 0.151 0.156 103 090826 BGF LCS Mid 2 0.587 0.606 103 0.159 0.180 113 0.151 0.161 106 0826 BGF LCS Mid 3 0.593 0.577 97.2 0.159 0.174 110 0.151 0.145 96.1 0826 BGF LCS High 1 1.29 1.35 105 0.838 0.969 116 0.797 0.870 109 090826 BGF LCS High 2 1.28 1.28 100 0.838 0.892 106 0.797 0.762 95.7 090826 BGF LCS High 3 1.29 1.34 104 0.838 0.975 116 0.797 0.862 108 Average 102 113 97.8 %RSD 2.6 3.4 9.5 (1) Spike level of PFBA corrected for endogenous concentration of the bluegill fillet control matrix as determined by method of standard addition (PFBA Cone = 4.25 ng/g). p. 84 3M ENVIRONMENTAL LABORATORY PAGE 82 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 18. LCS Recoveries for Extraction Batch 2 Using Extracted Matrix-Matched Calibration: PFBA, PFPeA, and PFHxA. Sample ID 090828 BGF LCS Low 1 090828 BGF LCS Low 2 090828 BGF LCS Low 3 090828 BGF LCS Mid 1 090828 BGF LCS Mid 2 090828 BGF LCS Mid 3 090828 BGF LCS High 1 090828 BGF LCS High 2 090828 BGF LCS Hiah 3 Average %RSD PFBA (extracted curve quant) ' Corrected Spike Cone. (ng/mL) Calc. Cone. (ng/mL) % Recovery 0.560 0.581 0.540 0.681 0.672 0.686 1.34 1.36 1.35 0.530 0.562 0.499 0.632 0.771 0.674 1.36 1.41 1.24 94.6 96.8 92.3 92.9 115 98.2 101 103 91.8 98.5 7.4 PFPeA (extracted curve quant) Std. Cone. (ng/mL) 0.0510 0.0510 0.0510 0.154 0.154 0.154 0.810 0.810 0.810 Calc. Cone. (ng/mL) 0.0481 0.0429 0.0440 0.137 0.276 0.141 0.759 0.805 0.703 % Recovery 94.3 84.2 86.2 88.8 Sl179 91.3 93.7 99.3 86.8 100 30 PFHxA (extracted curve quant) Std. Cone. (ng/mL) 0.0502 0.0502 0.0502 0.151 0.151 0.151 0.797 0.797 0.797 Calc. Cone. (ng/mL) 0.0476 0.0393 0.0506 0.142 0.151 0.138 0.813 0.814 0.745 % Recovery 94.8 78.4 101 93.8 100 91.1 102 102 93.5 95.2 7.9 (1) Spike level of PFBA corrected for endogenous concentration of the bluegill fillet control matrix as determined by method of standard addition (PFBA Cone = 5.00 ng&). (2) LCS recovery exceeded 10030%. (3) RSD exceeds method acceptance of <20% for all LCSs considered collectively. p. 85 3M ENVIRONMENTAL LABORATORY PAGE 83 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 19. LCS Recoveries for Extraction Batch 3 Using Extracted Matrix-Matched Calibration: PFBA, PFPeA, and PFHxA. Sample ID 090901 BGF LCS Low 1 090901 BGF LCS Low 2 090901 BGF LCS Low 3 090901 BGF LCS Mid 1 090901 BGF LCS Mid 2 090901 BGF LCS Mid 3 090901 BGF LCS High 1 090901 BGF LCS High 2 090901 BGF LCS High 3 Average %RSD PFBA (extracted quant) (1)Corrected Spike Cone. (nq/mL) 0.433 0.459 0.467 0.573 0.551 0.562 1.26 1.25 1.24 Calc. Cone. (nq/mL) 0.408 0.461 0.428 0.604 0.548 0.572 1.25 1.29 1.16 % Recovery 94.3 101 91.7 105 100 102 100 103 93.4 98.9 4.8 PFPeA (extracted curve quant) Std. Cone. (nq/mL) 0.0671 0.0682 0.0686 0.171 0.170 0.171 0.826 0.826 0.825 Cala Cone. (nq/mL) 0.0585 0.0593 0.0559 0.154 0.161 0.164 0.754 0.806 0.730 % Recovery 872 86.9 81.5 89.9 94.5 95.7 91 -2 97.6 88.5 90.3 5.6 PFHxA (extracted curve quant) Std. Cone. (nq/mL) 0.0502 0.0502 0.0502 0.151 0.151 0.151 0.797 0.797 0.797 Calc, Cone. (nq/mL) 0.0579 0.0878 0.0722 0.179 0.221 0.220 0.819 0.875 0.851 % Recovery 115 175 e>144 118 Bi146 8>146 103 110 107 129 19 (1) Spike level of PFBA corrected for endogenous concentration of the Wueglll fillet control matrix as determined by method of standard addition (PFBA Cone = 3.92 ng/g). (2) LCS recovery exceeded 100*30%. p. 86 3M ENVIRONMENTAL LABORATORY PAGE 84 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 20. LCS Recoveries for Extraction Batch 1 Using Extracted Matrix-Matched Calibration: PFCAs (C7-C12) e IP 090826 BGF LCS Low 1 090826 BGF LCS Low 2 090826 BGF LCS Low 3 090826 BGF LCS Mid 1 090826 BGF LCS Mid 2 090826 BGF LCS Mid 3 090826 BGF LCS High 1 090826 BGF LCS High 2 090826 BGF LCS High 3 090826 BGF E C F L C S 1 090826 BGF EC FLC S 2 090826 BGF ECF LCS 3 Average %RSD Sample ID 090826 BGF LCS Low 1 090826 BGF LCS Low 2 090826 BGF LCS Low 3 090826 BGF LCS Mid 1 090826 BGF LCS Mid 2 090826 BGF LCS Mid 3 090826 BGF LCS High 1 090826 BGF LCS High 2 090826 BGF LCS High 3 Average %RSD Spike Cone. Jng /m ^ 0.0492 0.0492 0.0492 0.148 0.148 0.148 0.781 0.781 0.781 PFHpA Calc. Cone. J n g /m y ^ 0.0509 0.0546 0.0492 0.144 0.166 0.145 0.781 0.720 0.705 % Recovery 104 111 100 97.4 112 98.2 100 92.1 90.3 Spike Cone. (ng/mL) 0.0497 0.0497 0.0497 0.150 0.150 0.150 0.789 0.789 0.789 PFDA Calc. Cone. (ng/mL) 0.0455 0.0471 0.0452 0.151 0.159 0.168 0.871 0.773 0.856 101 7.4 % Recovery 91.5 94.8 91.0 101 106 112 110 98.0 108 101 7.9 Spike Cone. 0.0516 0.0516 0.0516 0.156 0.156 0.156 0.819 0.819 0.819 0.520 0.520 0.520 Spike Cone. (ng/mL) 0.0503 0.0503 0.0503 0.152 0.152 0.152 0.799 0.799 0.799 PFOA Calc. Cone. 0.0460 0.0548 0.0535 0.162 0.180 0.159 0.880 0.787 0.763 0.558 0.570 0.587 PFUnA Calc. Cone. (ng/mL) 0.0476 0.0472 0.0509 0.146 0.139 0.142 0.819 0.693 0.779 89.2 106 104 104 115 102 107 96.0 93.1 107 110 113 102 7.7 % Recovery 94.7 93.9 101 95.9 91.3 93.4 102 86.7 97.5 95.2 5.0 Spike Cone. JngM jL^ 0.0515 0.0515 0.0515 0.155 0.155 0.155 0.818 0.818 0.818 Spike Cone. (ng/mL) 0.0506 0.0506 0.0506 0.152 0.152 0.152 0.802 0.802 0.802 PFNA Cate. Cone. 0.0486 0.0472 0.0469 0.147 0.162 0.149 0.880 0.794 0.792 % Recovery 94.4 91.7 91.1 94.9 104 96.1 108 97.1 96.8 PFDoA 97.1 5.7 Calc. Cone. (ng/mL) 0.0496 0.0449 0.0494 0.157 0.162 0.150 0.780 0.775 0.785 % Recovery 98.1 88.8 97.7 103 107 98.5 97.2 96.6 97.8 98.3 5.0 p. 87 3M ENVIRONMENTAL LABORATORY PAGE 85 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 21. LCS Recoveries for Extraction Batch 2 Using Extracted Matrix-Matched Calibration: PFCAs (C7-C12). e ID 090828 BGF LCS Low 1 090828 BGF LCS Low 2 090828 BGF LCS Low 3 090828 BGF LCS M id i 090828 BGF LCS Mid 2 090828 BGF LCS Mid 3 090828 BGF LCS High 1 090828 BGF LCS High 2 090828 BGF LCS High 3 090828 BGF ECFLCS 1 090828 BGF ECFLCS 2 090828 BGF ECF LCS 3 Average %RSD Spike Cone. 0.0492 0.0492 0.0492 0.148 0.148 0.148 0,781 0.781 0.781 Sample ID Spike Cone. (na/mL) 090828 BGF LCS Low 1 0.0497 090828 BGF LCS Low 2 0.0497 090828 BGF LCS Low 3 0.0497 090828 BGF LCS Mid 1 0.150 090828 BGF LCS Mid 2 0.150 090828 BGF LCS Mid 3 0.150 090828 BGF LCS High 1 0.789 090828 BGF LCS High 2 0.789 090828 BGF LCS Hiah 3 0.789 Average %RSD (1) LCS recovery exceeded 10030%. PFHp A Calc. Cone. 0.0457 0.0314 0.0349 0.124 0.156 0.115 0.807 0.820 0.624 ^^R ecover^ 92.9 l,)63.8 71.0 83.7 105 78.0 103 105 79.9 PFDA Calc. Cone. (na/mL) 0.0428 0.0513 0.0407 0.154 0.166 0.155 0.963 0.834 0.796 86.9 18 % Recovery 86.1 103 81.8 103 111 103 122 106 101 102 12 Spike Cone. 0.0516 0.0516 0.0516 0.156 0,156 0.156 0,819 0.819 0.819 0.520 0.520 0.520 Spike Cone. (na/mL) 0.0503 0.0503 0.0503 0.152 0.152 0.152 0.799 0.799 0.799 PFOA Calc. Cone. ^Jng/m L) 0.0644 0.0502 0.0457 0.136 0,183 0.153 1.07 0.925 0.813 0.460 0.428 0.550 PFUnA ^ ^ R ec o v e r^ 125 97.3 88.5 87.2 117 98.2 (,)131 113 99.2 88.4 82.3 106 106 15 Calc. Cone. 0.0568 0.0690 0.0676 0.125 0.161 0.146 0.770 0.913 0.719 % Recovery 113 !,,137 ,1)134 82.0 106 96.2 96.4 114 90.0 108 18 Spike Cone. ig/m U 0.0515 0.0515 0.0515 0.155 0.155 0.155 0.818 0.818 0.818 Spike Cone. (na/mL) 0.0506 0.0506 0.0506 0.152 0.152 0.152 0.802 0.802 0.802 PFNA Calc. Cone. 0.0475 0.0478 0.0565 0.150 0.162 0.160 0.822 0.769 0.780 ^^R ecover^ 92.1 92.9 110 97.0 104 103 101 94.1 95,4 PFDoA 98.8 6.1 Calc. Cone. (ng/mL) 0.0511 0.0463 0.0484 0.149 0.130 0.159 0.826 0.760 0.742 % Recovery 101 91.6 95.6 97.8 85.8 105 103 94.7 92.5 96.3 6.3 p. 88 3M ENVIRONMENTAL LABORATORY PAGE 86 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 22. LCS Recoveries for Extraction Batch 3 Using Extracted Matrix-Matched Calibration: PFCAs (C7-C12). ie ID 090901 BGF LCS Low 1 090901 BGF LCS Low 2 090901 BGF LCS Low 3 090901 BGF LCS Mid 1 090901 BGF LCS Mid 2 090901 BGF LCS Mid 3 090901 BGF LCS High 1 090901 BGF LCS High 2 090901 BGF LCS High 3 090901 BGF EC FLC S 1 090901 BGF ECF LCS 2 090901 BGF ECF LCS 3 Average %RSD Spike Cone. isaasLL 0.0492 0.0492 0.0492 0.148 0.148 0.148 0.781 0.781 0.781 PFHpA Calc. Cone. (n9/mL) 0.0439 0.0341 0.0396 0.117 0.128 0.116 0.595 0.693 0.604 PFDA J^ecovei^ 89.2 `"69.4 80.4 79.1 86.7 78.3 76.2 88.7 77.4 80.6 8.1 Spike Cone. JngAn^ 0.0516 0.0516 0.0516 0.156 0.156 0.156 0.819 0.819 0.819 0.520 0.520 0.520 PFOA Calc. Cone. (ng/mL) 0.0490 0.0482 0.0561 0.143 0.153 0.150 0.827 0.934 0.755 0.492 0.501 0.506 PFUnA ^ ^ e c o v e ro 95.0 93.4 109 91.9 97.9 96.0 101 114 92.1 94.7 96.4 97.3 98.9 7.9 Spike Cone. n g /rn ^ 0.0515 0.0515 0.0515 0.155 0.155 0.155 0.818 0.818 0.818 PFNA Calc. Cone. ^ J n g /m L ^ 0.0520 0.0474 0.0523 0.146 0.170 0.158 0.890 0.906 0.775 PFDoA Sample ID Spike Cone. (ng/mL) Calc. Cone. (ng/mL) % Recovery Spike Cone. (ng/mL) Calc. Cone. (ng/mL) % Recovery Spike Cone. Calc. Cone. (ng/mL) 090901 BGF LCS Low 1 0.0497 090901 BGF LCS Low 2 0.0497 090901 BGF LCS Low 3 0.0497 090901 BGF LCS Mid 1 0.150 090901 BGF LCS Mid 2 0.150 090901 BGF LCS Mid 3 0.150 090901 BGF LCS High 1 0.789 090901 BGF LCS High 2 0.789 090901 BGF LCS High 3 0.789 Average %RSD (1) LCS recovery exceeded 10030%. 0.0534 0.0527 0.0420 0.137 0.133 0.145 0.808 0.741 0.787 108 106 84.5 91.5 88.6 96.8 102 93.9 99.7 96.8 8.2 0.0503 0.0503 0.0503 0.152 0.152 0.152 0.799 0.799 0.799 0.0552 0.0503 0.0556 0.135 0.158 0.150 0.905 0.884 0.880 110 99.9 110 89.1 104 98.7 113 111 110 105 7.5 0.0506 0.0506 0.0506 0.152 0.152 0.152 0.802 0.802 0.802 0.0498 0.0519 0.0510 0.152 0.161 0.154 0.656 0.810 0.762 % Recovery 101 92.0 102 94.5 110 102 109 111 94.8 102 7.0 % Recovery 98.4 103 101 100 106 101 81.8 101 95.1 98.6 7.1 p. 89 3M ENVIRONMENTAL LABORATORY PAGE 87 O F 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 23. LCS Recoveries for Extraction Batch 1 Using Extracted Matrix-Matched Calibration: PFBS, PFHS, and FOSA. Sample IO 090826 BGF LCS Low 1 090826 BGF LCS Low 2 090826 BGF LCS Low 3 090826 BGF LCS Mid 1 090826 BGF LCS Mid 2 090826 BGF LCS Mid 3 090826 BGF LCS High 1 090826 BGF LCS High 2 090826 BGF LCS High 3 Average %RSD Spike Cone. Infl/mL) 0.0496 0.0496 0.0496 0.150 0.150 0.150 0.788 0.788 0.788 PFBS Calc. Cone. (ng/mL) 0.0518 0.0581 0.0473 0.122 0.142 0.140 0.805 0.711 0.781 % Recovery 104 117 95.4 81.0 94.8 93.4 102 90.3 99.2 97.5 10 Spike Cone. (ng/mL) 0.0516 0.0516 0.0516 0.156 0.156 0.156 0.819 0.819 0.819 PFHS Calc. Conc. (ng/mL) 0.0472 0.0559 0.0519 0.151 0.167 0.144 0.819 0.708 0.852 % Recovery 91.5 108 101 96.6 107 92.4 100 86.5 104 98.6 7.5 Spike Conc. 0.0492 0.0492 0.0492 0.148 0.148 0.148 0.781 0.781 0.781 FOSA Cale. Conc. (ng/mL) 0.0473 0.0496 0.0469 0.141 0.158 0.139 0.756 0.782 0.777 % Recovery 96.1 101 95.3 95.1 107 94.2 96.8 100 99.5 98.3 4.1 Table 24. LCS Recoveries for Extraction Batch 2 Using Extracted Matrix-Matched Calibration: PFBS, PFHS, and FOSA. Sample ID 090828 BGF LCS Low 1 090828 BGF LCS Low 2 090828 BGF LCS Low 3 090828 BGF LCS Mid 1 090828 BGF LCS Mid 2 090828 BGF LCS Mid 3 090828 BGF LCS High 1 090828 BGF LCS High 2 090828 BGF LCS High 3 Spike Conc. (ng/mL) 0.0496 0.0496 0.0496 0.150 0.150 0.150 0.788 0.788 0.788 PFBS Cale. Conc. (ng/mL) 0.0477 0.0474 0.0390 0.147 0.162 0.156 0,823 0.713 0.809 % Recovery 96.2 95.6 78.6 97.7 108 104 104 90.5 103 97.5 9.1 Spike Conc. (ng/mL) 0.0516 0.0516 0.0518 0.156 0.156 0.156 0.819 0.819 0.819 PFHS Cale. Conc. (ng/mL) 0.0438 0.0469 0.0541 0.139 0.148 0.183 0.873 0.925 0.860 % Recovery 84.9 90.8 105 89.1 94.6 117 107 113 105 101 11 Spike Conc. (ng/mL) 0.0492 0.0492 0.0492 0.148 0.148 0.148 0.781 0.781 0.781 FOSA Cale. Conc. (ng/mL) 0.0558 0.0573 0.0582 0.119 0.147 0.159 0.987 1.00 0.750 % Recovery 113 116 118 80.4 99.3 107 126 128 96.0 109 14 p. 90 3M ENVIRONMENTAL LABORATORY PAGE 88 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 25. LCS Recoveries for Extraction Batch 3 Using Extracted Matrix-Matched Calibration: PFBS, PFHS, and FOSA. Sample ID Spike Cone. (ng/mL) 090901 BGF LCS Low 1 0.0496 090901 BGF LCS Low 2 0.0496 090901 BGF LCS Low 3 0.0496 090901 BGF LCS Mid 1 0.150 090901 BGF LCS Mid 2 0.150 090901 BGF LCS Mid 3 0.150 090901 BGF LCS High 1 0.788 090901 BGF LCS High 2 0.788 090901 BGF LCS High 3 0.788 Average %RSO (1) LCS recovery exceeded 10030%. PFBS Calc. Cone. (ng/mL) 0.0468 0.0588 0.0386 0.154 0.172 0.172 0.807 0.833 0.771 94.3 119 77.7 103 115 115 102 106 97.8 103 12 Spike Cone. (ng/mL) 0.0516 0.0516 0.0516 0.156 0.156 0.156 0.819 0.819 0.819 PFHS Calc. Cone. (ng/mL) 0.0400 0.0289 0.0342 0.144 0.138 0.132 0.835 0.773 0.891 % Recovery 77.6 (1)56.1 (1>66.2 92.0 88.5 84.8 102 94.4 109 85.6 20 Spike Cone. (ng/mL) 0.0492 0.0492 0.0492 0.148 0.148 0.148 0.781 0.781 0.781 FOSA Calc. Cone. (ng/mL) 0.0580 0.0506 0.0519 0.136 0.157 0.139 0.835 0.922 0.846 % Recovery 118 103 105 92.1 106 93.6 107 118 108 106 8.5 p. 91 3M ENVIRONMENTAL LABORATORY PAGE 89 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 26. LCS Recoveries for Extraction Batch 1 Using Extracted Matrix-Matched Calibration: Surrogates. Sample ID 090826 BGF LCS Low 1 090826 BGF LCS Low 2 090826 BGF LCS Low 3 090826 BGF LCS Mid 1 090826 BGF LCS Mid 2 090826 BGF LCS Mid 3 090826 BGF LCS High 1 090826 BGF LCS High 2 090826 BGF LCS High 3 090826 BGF ECF LCS 1 090826 BGF ECF LCS 2 090826 BGF ECF LCS 3 090826 BGF PFOS LCS 1 @ 100 ng/g 090826 BGF PFOS LCS 2 @ 100 ng/g 090826 BGF PFOS LCS 3 @ 100 ng/g Average %RSD [1,2-1>C JPFO A Spike Cone. (ng/mL) 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0,104 0.104 0.104 0.104 0.104 0.104 Calc. Conc. (ng/m U 0.102 0.113 0.102 0.113 0.111 0.107 0.115 0.111 0.106 0.126 0.125 0.124 0.111 0.106 0.116 % Recovery 97.8 109 98.1 109 107 103 110 106 101 121 120 119 107 102 111 108 6.8 Spike Conc. (ng/mL) 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 [" OJPFOS Cale. Conc. (ng/mL) 0.101 0.109 0.124 0.117 0.105 0.100 0.097 0.0968 0.106 0.110 0.112 0.109 0.0914 0,104 0.108 % Recovery 97.5 104 119 113 101 96.2 93.3 93.1 101 106 107 105 87.9 99.6 104 102 7.8 p. 92 3M ENVIRONMENTAL LABORATORY PAGE 90 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 27. LCS Recoveries for Extraction Batch 2 Using Extracted Matrix-Matched Calibration: Surrogates. SamDle ID 090828 BGF LCS Low 1 090828 BGF LCS Low 2 090828 BGF LCS Low 3 090828 BGF LCS Mid 1 090828 BGF LCS Mid 2 090828 BGF LCS Mid 3 090828 BGF LCS High 1 090828 BGF LCS High 2 090828 BGF LCS High 3 090828 BGF ECF LCS 1 090828 BGF ECF LCS 2 090828 BGF ECF LCS 3 090828 BGF PFOS LCS 1 @ 100 ng/g 090828 BGF PFOS LCS 2 @ 100 ng/g 090828 BGF PFOS LCS 3 @ 100 ng/g Average %RSD Spike Cone. (ng/mL) 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 rU-^CdPFO A Calc. Cone. In a/m L I 0.127 0.0918 0.127 0.0936 0.115 0.0969 0.128 0.124 0.111 0.0961 0.0866 0.112 0.108 0.117 0.118 % Recovery 122 88.2 123 90.0 111 93.2 123 119 107 92.4 83.2 108 104 112 113 106 13 Spike Cone. (ng/mL) 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 f'O JPFO S Calc. Cone. (ng/mL) 0.111 0.113 0.119 0.106 0.102 0.0975 0.106 0.112 0.111 0.122 0.115 0.126 0.119 0.111 0.122 % Recovery 106 109 114 102 98.5 93.7 102 107 107 118 110 121 114 107 117 108 7.0 p. 93 3M ENVIRONMENTAL LABORATORY PAGE 91 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 28. LCS Recoveries for Extraction Batch 3 Using Extracted Matrix-Matched Calibration: Surrogates. Sample ID 090901 BGF LCS Low 1 090901 BGF LCS Low 2 090901 BGF LCS Low 3 090901 BGF LCS Mid 1 090901 BGF LCS Mid 2 090901 BGF LCS Mid 3 090901 BGF LCS High 1 090901 BGF LCS High 2 090901 BGF LCS High 3 090901 BGF ECF LCS 1 090901 BGF ECF LCS 2 090901 BGF ECF LCS 3 090901 BGF PFOS LCS 1 @ 100 ng/g 090901 BGF PFOS LCS 2 @ 100 ng/g 090901 BGF PFOS LCS 3 @ 100 ng/g Average %RSD Spike Cone. (ng/mL) 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0,104 0.104 0.104 0.104 [1 ,2 -1sC i] P F O A Calc. Cone. (nq/mL) 0.109 0.114 0.115 0.106 0.113 0.103 0.105 0.125 0.0970 0.119 0.112 0.105 0.104 0.105 0.114 % Recovery 105 110 111 102 109 98.8 101 120 93.3 115 108 101 100 101 110 106 6.6 Spike Cone. (ng/mL) 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0,104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 [1*Oj]PFOS Calc. Cone. (ng/mL) 0.0946 0.116 0.118 0.126 0.124 0.105 0.115 0.106 0.112 0.102 0.123 0.104 0.128 0.116 0,113 % Recovery 91.0 112 114 121 120 101 110 102 107 98.0 118 99.8 123 112 109 109 8.6 p. 94 3M ENVIRONMENTAL LABORATORY PAGE 92 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. EQ9-0372 10.2 Lab Control Spike Recoveries by Unextracted Acetonitrile Calibration using IS Quantitation. Table 29. LCS Recoveries for Extraction Batch 1 Using Unextracted Acetonitrile Calibration: PFBA, PFPeA, PFHxA. PFBA (solvent curve quant) PFPeA (solvent curve quant) PFHxA (solvent curve quant) Sample ID (1)Corrected Spike Cone. (nq/mL) Calc. Cone. (nq/mL) % Recovery '^Corrected Spike Cone. (ng/mL) Calc. Cone. (ng/mL) % Recovery Std. Cone. (ng/mL) Calc. Cone. (ng/mL) % Recovery 090826 BGF LCS Low 1 0.544 0.554 102 0.0686 0.0821 120 0.0502 0.0502 100 090826 BGF LCS Low 2 0.531 0.549 103 0.0682 0.0848 124 0.0502 0.0496 98.8 090826 BGF LCS Low 3 0.532 0.548 103 0.0682 0.0835 122 0.0502 0.0529 105 090826 BGF LCS Mid 1 0.653 0.636 97.4 0.175 0.211 121 0.151 0.158 105 090826 BGF LCS Mid 2 0.625 0.632 101 0.174 0.220 126 0.151 0.163 108 090826 BGF LCS Mid 3 0.631 0.606 96.1 0.175 0.214 123 0.151 0.148 97.9 090826 BGF LCS High 1 1.33 1.34 101 0.854 1.13 0I132 0.797 0.810 102 090826 BGF LCS High 2 1.32 1.27 96.6 0.853 1.04 122 0.797 0.715 89.7 090826 BGF LCS Hklh 3 1.33 1.32 99.0 0.854 1.13 <" 132 0.797 0.803 101 Average 100 125 101 %RSD 2.7 3.8 5.3 (1) Spke level of PFBA corrected for endogenous concentration of the bluegill fillet control matrix as determined by quantitation of the matrix blanks by the using the unextracted acetonitrile calforation (PFBA Cone = 4.61 ng/g). (2) Spike level of PFPeA corrected for endogenous concentration of the bluegill filletcontrol matrix as determined by quantitation of the matrix blanks by the using the unextracted acetonitrile calferation (PFPeA Cone = 0.148 ng/g). (3) LCS recovery exceeded 10030%. p. 95 3M ENVIRONMENTAL LABORATORY PAGE 93 O F 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 30. LCS Recoveries for Extraction Batch 2 Using Unextracted Acetonitrile Calibration: PFBA, PFPeA, PFHxA. PFBA (solvent curve auant) PFPeA (solvent curve auant) PFHxA (solvent curve guant) Samle ID ,1'Corrected Spike Cone. (ng/mL) Calc. Cone. (nglmL) % Recovery (2|Corrected Spike Cone. (ng/mL) Calc. Cone. (ng/mL) % Recovery Std. Cone. (ng/mL) Calc. Cone. (ng/mL) % Recovery 090828 BGF LCS Low 1 0.521 0.498 95.6 0.128 0.106 83.1 0.0502 0.0609 121 090828 BGF LCS Low 2 0.540 0.528 97.8 0.128 0.0974 76.4 0.0502 0.0525 105 090828 BGF LCS Low 3 0.503 0.468 93.1 0.128 0.0990 77.6 0.0502 0.0640 127 090828 BGF LCS Mid 1 0.640 0.595 92.9 0,385 0.249 w64.7 0.151 0.156 103 090828 BGF LCS Mid 2 0.633 0.727 115 0.385 0.473 123 0.151 0.166 110 090828 BGF LCS Mid 3 0.646 0.635 98.4 0.385 0.256 m66.5 0.151 0.152 101 090828 BGF LCS High 1 1.30 1.28 98.2 2.03 1.24 w61.2 0.797 0.791 99.3 090828 BGF LCS High 2 1.32 1.32 99.7 2.03 1.31 " 64.7 0.797 0.792 99.4 090828 BGF LCS High 3 1.31 1.16 88.3 2.03 1.15 " 56.8 0.797 0.731 91.7 Average 97.6 74.9 106 %RSD 7.6 <4|27 11 ( i j Spike level of PFBA corrected for endogenous concentration of the bluegill fillet control matrix as determined by quantitation erfthe matrix blanks by the using the unextracted acetonitrile calibration (PFBA Cone = 4.61 ng/g). (2) Spike level of PFPeA corrected for endogenous concentration ofthe bluegill fillet control matrix as determined by quantitation of the matrix blanks by the using the unextracted acetonitrile calibration (PFPeA Cone = 0.275 ng/g). (3) LCS recovery exceeded 10030%. (4) %RSD exceeded 20%. p. 96 3M ENVIRONMENTAL LABORATORY PAGE 94 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 31. LCS Recoveries for Extraction Batch 3 Using Unextracted Acetonitrile Calibration: PFBA, PFPeA, PFHxA. PFBA (solvent curve quant) PFPeA (solvent curve quant) PFHxA (solvent curve quant) Sample ID (1'Corrected Spike Cone. (ng/mL) Calc. Cone. (ng/mL) % Recovery '''Corrected Spike Cone. (ng/mL) Calc. Cone. (ng/mL) % Recovery '' 'Corrected Spike Cone. (ng/mL) Calc. Cone. (ng/mL) % Recovery 090901 BGF LCS Low 1 090901 BGF LCS Low 2 090901 BGF LCS Low 3 0.528 0.561 0.571 0.486 0.542 0.507 92.0 96.6 88.8 0.0635 0.0644 0.0646 0.0566 0.0574 0.0538 89.1 89.2 83.2 0.0549 0.0644 0.0646 0.0566 0.0574 0.0538 103 89.2 83.2 090901 BGF LCS Mid 1 0.677 0.691 102 0.168 0.158 94.3 0.168 0.158 94.3 090901 BGF LCS Mid 2 0.649 0.633 97.5 0.167 0.165 98.9 0.167 0.165 98.9 090901 BGF LCS Mid 3 0.663 0.657 99.1 0.167 0.169 101 0.167 0.169 101 090901 BGF LCS High 1 1.36 1.34 98.3 0.824 0.792 96.1 0.824 0.792 96.1 090901 BGF LCS High 2 1.35 1.38 102 0.824 0.847 103 0.824 0.847 103 090901 BGF LCS High 3 1.35 1.26 93.7 0.823 0.767 93.2 0.823 0.767 93.2 Average 96.7 94.2 95.8 %RSD 4.6 6.7 6.9 (1) Spke level of PFBA corrected for endogenous concentration of the bluegill fillet control matrix as determined by quantitation of the matrix blanks by the using the unextracted aoetonitrile calfcration (PFBA Cone=4.91 ng/g). (2) Spice level of PFPeA corrected for endogenous concentration of the bluegill fillet control matrix as determined by quantitation of the matrix blanks by the using the unextracted acetonitrile calfcration (PFPeA Cone = 0.129 ng/g). (3) Spice level of PFHxA corrected for endogenous concentration of the bluegill fillet control matrix as determined by quantitation of the matrix blanks by the using the unextracted acetonitrile calfcration (PFHxA Cone = 0.0482 ng/g). p. 97 3M ENVIRONMENTAL LABORATORY PAGE 95 O F 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 32. LCS Recoveries for Extraction Batch 1 Using Unextracted Acetonitrile Calibration: PFCAs (C7-C12) PFHpA PFOA PFNA Sample ID Spike Cone. (ng/mL) Calc. Cone. (ng/mL) % Recovery Spike Cone. (ng/mL) Calc. Cone. (ng/mL) % Recovery Spike Cone. (ng/mL) Calc. Cone. (ng/mL) 090826 BGF LCS Low 1 090826 BGF LCS Low 2 090826 BGF LCS Low 3 090826 BGF LCS Mid 1 090826 BGF LCS Mid 2 090826 BGF LCS Mid 3 090826 BGF LCS High 1 090826 BGF LCS High 2 090826 BGF LCS High 3 090826 BGF ECF LCS 1 090826 BGF ECF LCS 2 Average %RSD 0.0492 0.0492 0.0492 0.148 0.148 0.148 0.781 0.781 0.781 0.0502 0.0540 0.0485 0.146 0.169 0.147 0,797 0.735 0.720 PFDA 102 110 98.6 98.8 114 99.6 102 94.1 92.3 101 6.9 0.0516 0.0516 0.0516 0.156 0.156 0.156 0.819 0.819 0.819 0.520 0.520 0.520 0.0455 0.0536 0.0524 0.153 0.170 0.150 0.815 0.730 0.708 0.520 0.531 0.546 PFUnA 88.1 104 102 98.2 109 96.2 100 89.1 86.4 99.9 102 105 97.0 8.0 0.0515 0.0515 0.0515 0.155 0.155 0.155 0.818 0.818 0.818 0.0455 0.0440 0.0437 0.148 0.163 0.150 0.906 0.818 0.816 PFDoA Sample ID Spike Cone. (ng/mL) Calc. Cone. (ng/mL) % Recovery Spike Cone. (ng/mL) Calc. Cone. (ng/mL) % Recovery Spike Conc. (ng/mL) Cale. Conc. (ng/mL) 090826 BGF LCS Low 1 090826 BGF LCS Low 2 090826 BGF LCS Low 3 090826 BGF LCS M id 1 090826 BGF LCS Mid 2 090826 BGF LCS Mid 3 090826 BGF LCS High 1 090826 BGF LCS High 2 090826 BGF LCS High 3 Average %RSD 0.0497 0.0497 0.0497 0.150 0.150 0.150 0.789 0.789 0.789 0.0437 0.0452 0.0435 0,142 0.149 0.157 0.817 0.724 0.803 87.9 90.9 87.5 94.4 99.1 104 104 91.8 102 95.7 7.0 0.0503 0.0503 0.0503 0.152 0.152 0.152 0.799 0.799 0.799 0.0554 0.0549 0.0587 0.156 0.149 0.152 0.844 0.716 0.804 110 109 117 103 97.8 100 106 89.6 101 104 7.7 0.0506 0.0506 0.0506 0.152 0.152 0.152 0.802 0.802 0.802 0.0485 0.0438 0.0483 0.155 0.160 0.148 0.774 0.769 0.779 % Recovery 88,3 85.5 84.8 95.2 105 96.5 111 100 99.7 96.2 9.2 % Recovery 95.8 86.6 95.4 102 105 97.2 96.5 95.9 97.1 96.8 5.2 p. 98 3M ENVIRONMENTAL LABORATORY PAGE 96 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 33. LCS Recoveries for Extraction Batch 2 Using linextracted Acetonitrile Calibration: PFCAs (C7-C12) Sample ID 090828 BGF LCS Low 1 090828 BGF LCS Low 2 090828 BGF LCS Low 3 090828 BGF LCS Mid 1 090828 BGF LCS Mid 2 090828 BGF LCS Mid 3 090828 BGF LCS High 1 090828 BGF LCS High 2 090828 BGF LCS High 3 090828 BGF ECF LCS 1 090828 BGF ECF LCS 2 090828 BGF ECF LCS 3 Average %RSD Spike Cone. (ng/m L ) 0.0492 0.0492 0.0492 0.148 0.148 0.148 0.781 0.781 0.781 Samgle ID Spike Cone. Jn g /m L ^ 090828 BGF LCS Low 1 0.0492 090828 BGF LCS Low 2 0.0492 090828 BGF LCS Low 3 0.0492 090828 BGF LCS Mid 1 0.148 090828 BGF LCS Mid 2 0.148 090828 BGF LCS Mid 3 0.148 090828 BGF LCS High 1 0.781 090828 BGF LCS High 2 0.781 090828 BGF LCS High 3 0.781 Average %RSD (1) LCS Recovery exceeded 10030%. PFHpA Calc. Cone. ^ n g /m L ^ 0.0494 0.0344 0.0381 0.131 0.165 0.123 0.844 0.858 0.654 PFDA Calc. Cone. ^ J n g /m ^ _ 0.0494 0.0344 0.0381 0.131 0.165 0.123 0.844 0.858 0.654 ^^Jecovery 100 <"69.9 77.4 88.8 112 82.8 108 110 83.7 92.5 17 J ij^e c o v e r^ 100 69.9 77.4 88.8 112 82.8 108 110 83.7 92.5 17 Spike Cone, (no 0.0516 0.0516 0.0516 0.156 0.156 0.156 0.819 0.819 0.819 0.520 0.520 0.520 Spike Cone. Jng/m L^ 0.0503 0.0503 0.0503 0.152 0.152 0.152 0.799 0.799 0.799 PFOA Cala Cone. 0.0785 0.0664 0.0562 0.134 0.182 0.149 0.941 0.814 0.718 0.414 0.387 0.492 PFUnA Calc. Cone. ^ J n g /m ^ _ 0.0617 0.0749 0.0734 0.135 0.174 0.158 0.833 0.987 0.779 '"152 129 109 86.1 116 95.7 115 99.4 87.7 79.6 74.4 94.5 110 19 % Recovery 123 <"149 <"146 88.9 115 104 104 124 97.4 117 18 Spike Cone. Jng/m L^ 0.0515 0.0515 0.0515 0.155 0.155 0.155 0.818 0.818 0.818 PFNA Calc. Cone. ^ n g /m ^ _ 0.0429 0.0433 0.0525 0.153 0.165 0.163 0.871 0.814 0.826 Spike Cone. (ng/mL) 0.0506 0.0506 0.0506 0.152 0.152 0.152 0.802 0.802 0.802 PFDoA Calc. Cone. (n9/mL) 0.0532 0.0480 0.0502 0.160 0.140 0.171 0.907 0.833 0.813 J^ecovei^ 83.2 84.0 102 98.7 106 105 106 99.5 101 98.4 8.9 J ^ e c o v e rj^ 105 94.9 99.3 105 91.8 113 113 104 101 103 7.0 p. 99 3M ENVIRONMENTAL LABORATORY PAGE 97 O F 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 34. LCS Recoveries for Extraction Batch 2 Using Unextracted Acetonitrile Calibration: PFCAs (C7-C12), Sample ID Spike Cone. (n g /m L ^ PFHpA Calc. Cone. (ng/mL) % Recovery Spike Cone. (ng/mL) PFOA Calc. Cone. (ng/mL) % Recover^ Spike Cone. J n g /m L |_ PFNA Calc. Cone. ^ J n g /m ^ ^ 090901 BGF LCS Low 1 090901 BGF LCS Low 2 090901 BGF LCS Low 3 090901 BGF LCS Mid 1 090901 BGF LCS Mid 2 090901 BGF LCS Mid 3 090901 BGF LCS High 1 090901 BGF LCS High 2 090901 BGF LCS High 3 090901 BGF ECF LCS 1 090901 BGF ECF LCS 2 090901 BGF ECF LCS 3 Average %RSD 0.0492 0.0492 0.0492 0.148 0.148 0.148 0.781 0.781 0.781 0.0387 0.0296 0.0347 0.107 0.118 0.106 0.553 0.644 0.562 PFDA 78.8 (,)60 2 70.5 72.6 79.7 71.7 70.8 82.5 72.0 73.2 9.0 0.0516 0.0516 0.0516 0.156 0.156 0.156 0.819 0.819 0.819 0.520 0,520 0.520 0.0489 0.0481 0.0557 0.139 0.148 0.145 0.786 0.886 0.718 0.470 0.479 0.483 PFUnA 94.8 93,3 108 89.0 94.8 92.9 96.0 108 87.6 90.4 92.0 92.9 96.0 7.6 0.0515 0.0515 0.0515 0.155 0.155 0.155 0.818 0.818 0.818 0.0515 0.0469 0.0518 0.146 0.169 0.157 0.888 0.904 0.773 PFDoA Sample IP Spike Cone. Jng/m L^ 090901 BGF LCS Low 1 090901 BGF LCS Low 2 090901 BGF LCS Low 3 090901 BGF LCS Mid 1 090901 BGF LCS Mid 2 090901 BGF LCS Mid 3 090901 BGF LCS High 1 090901 BGF LCS High 2 090901 BGF LCS High 3 0.0497 0.0497 0.0497 0.150 0.150 0.150 0.789 0.789 0.789 Average %RSD (1) LCS recovery exceeded 10030% . Calc. Cone. 0.0543 0.0535 0.0424 0.141 0.137 0.149 0.839 0.769 0.816 ^^Recove^ 109 108 85.4 94.0 91.0 99.5 106 97.4 103 99.3 8.1 Spike Cone. (ng/mL) 0.0503 0.0503 0.0503 0.152 0.152 0.152 0.799 0.799 0.799 Calc. Cone. (ng/mL) 0.0591 0.0545 0.0594 0.133 0.153 0.146 0.845 0.825 0.822 % Recove^ 117 108 118 87.3 101 96.1 106 103 103 104 9.2 Spike Cone. m arnsL 0.0506 0.0506 0.0506 0.152 0.152 0.152 0.802 0.802 0.802 Calc. Cone. ^ n g /m L J ^ 0.0496 0.0520 0.0510 0.167 0.178 0.169 0,746 0.923 0.868 ^^Recover^ 100 91.0 101 94.0 109 101 109 111 94.5 101 7.2 % Recovery 98.1 103 101 110 117 111 93.1 115 108 106 7.5 p. 100 3M ENVIRONMENTAL LABORATORY PAGE 98 O F 104 3M ENVIRONMENTAL LABORA TORY REPORT NO. E09-0372 Table 35. LCS Recoveries for Extraction Batch 1 Using Unextracted Acetonitrile Calibration: PFBS, PFHS, and FOSA. PFBS PFHS FOSA Sample IO 090826 BGF LCS Low 1 090826 BGF LCS Low 2 090826 BGF LCS Low 3 090826 BGF LCS Mid 1 090826 BGF LCS Mid 2 090826 BGF LCS Mid 3 090826 BGF LCS High 1 090826 BGF LCS High 2 090826 BGF LCS High 3 Average %RSD Spike Cone. (n a /m U 0.0496 0.0496 0.0496 0.150 0.150 0.150 0.788 0.788 0.788 Calc. Cone. (ng/mL) 0.0408 0.0473 0.0362 0.112 0.134 0.131 0.813 0.717 0.788 % Recovery 82.2 95.3 73.0 75.0 89.1 87.6 103 90.9 100 88.5 12 Spike Cone. (ng/mL) 0.0516 0.0516 0.0516 0.156 0.156 0.156 0.819 0.819 0.819 Calc. Cone. (ng/mL) 0.0437 0.0529 0.0486 0.153 0.171 0.146 0.859 0.743 0.894 % Recovery 84.7 103 942 98.2 109 93.7 105 90.7 109 98.6 8.6 Spike Cone. (ng/mL) 0.0492 0.0492 0.0492 0.148 0.148 0.148 0.781 0.781 0.781 Calc. Cone. (ng/mL) 0.0455 0.0478 0.0451 0.140 0.157 0.139 0.764 0.790 0.785 % Recovery 92.4 97.2 91.7 94.6 106 93.7 97.8 101 101 97.3 4.9 Table 36. LCS Recoveries for Extraction Batch 2 Using Unextracted A cetonitrile Calibration: PFBS, PFHS, and FOSA. Sample 10 Spike Cone. (ng/mL) PFBS Calc. Cone. % Recovery Spike Cone. (ng/mL) PFHS C ala Cone. (ng/mL) % Recovery Spike Cone. (ng/mL) FOSA Calc. Cone. (ng/mL) 090828 BGF LCS Low 1 090828 BGF LCS Low 2 090828 BGF LCS Low 3 090828 BGF LCS Mid 1 090828 BGF LCS Mid 2 090828 BGF LCS Mid 3 090828 BGF LCS High 1 090828 BGF LCS High 2 090828 BGF LCS Hiqh 3 0.0496 0.0496 0.0496 0.150 0.150 0.150 0.788 0.788 0.788 (1) LCS recovery exceeded 10030%. 0.0390 0.0387 0.0310 0.128 0.143 0.137 0.745 0.645 0.732 78.5 78.0 (% 2.5 85.6 95.0 91.4 94.6 81.8 92.9 84.5 13 0.0516 0.0516 0.0516 0.156 0.156 0.156 0.819 0.819 0.819 0.0398 0.0425 0.0488 0.123 0.131 0.162 0.777 0.825 0.766 77.2 82.3 94.5 78.9 83.7 104 94.9 101 93.5 90.0 11 0.0492 0.0492 0.0492 0.148 0.148 0.148 0.781 0.781 0.781 0.0632 0.0649 0.0658 0.133 0.164 0.176 1.09 1.11 0.828 129 ('>132 (1,134 89.7 111 119 '" 140 m142 106 123 14 p. 101 3M ENVIRONMENTAL LABORATORY PAGE 99 O F 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 37. LCS Recoveries for Extraction Batch 3 Using Unextracted Acetonitrile Calibration: PFBS, PFHS, and FOSA. Sample ID 090901 BGF LCS Low 1 090901 BGF LCS Low 2 090901 BGF LCS Low 3 090901 BGF LCS Mid 1 090901 BGF LCS Mid 2 090901 BGF LCS Mid 3 090901 BGF LCS High 1 090901 BGF LCS High 2 090901 BGF LCS High 3 Spike Cone. (nq/mL) 0.0496 0.0496 0.0496 0.150 0.150 0.150 0.788 0.788 0.788 PFBS Calc. Cone. (ng/mL) 0.0412 0.0530 0,0331 0.146 0.164 0.164 0.787 0.813 0.752 (1) Recovery not calculated. Sample result was below the LOQ. (2) LCS recovery exceeded 10030%. (3) %RSD exceeded 20%. % Recovery 83.0 107 ,2166.7 97.6 109 110 99.9 103 95.4 96.8 14 Spike Cone. (ng/mL) 0.0516 0.0516 0.0516 0.156 0.156 0.156 0.819 0.819 0.819 PFHS Calc. Cone. (ng/mL) <0.0102 <0.0102 <0.0102 0.104 0.0986 0.0925 0.815 0.751 0.872 % Recovery (1,N/A (,)N/A <'>N/A <2|66.8 <a6 3 .2 w59.3 99.5 91.7 107 81.3 m2S Spike Cone. (ng/mL) 0.0492 0.0492 0.0492 0.148 0.148 0.148 0.781 0.781 0.781 FOSA Calc. Cone. (ng/mL) 0.0538 0.0465 0.0478 0.131 0.151 0.133 0.818 0.904 0.829 % Recovery 109 94.5 97.1 88.2 102 89.8 105 116 106 101 9.1 p. 102 3M ENVIRONMENTAL LABORATORY PAGE 100 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 38. LCS Recoveries for Extraction Batch 1 Using Unextracted Acetonitrile Calibration: Surrogates. Sample ID 090826 BGF LCS Low 1 090826 BGF LCS Low 2 090826 BGF LCS Low 3 090826 BGF LCS Mid 1 090826 BGF LCS Mid 2 090826 BGF LCS Mid 3 090826 BGF LCS High 1 090826 BGF LCS High 2 090826 BGF LCS High 3 090826 BGF ECF LCS 1 090826 BGF ECF LCS 2 090826 BGF ECF LCS 3 090826 BGF PFOS LCS 1 @ 100 ng/g 090826 BGF PFOS LCS 2 @ 100 ng/g 090826 BGF PFOS LCS 3 @ 100 ng/g Average %RSD Spike Cone. (ng/mL) 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 [1,2 -1lC J P F O A Calc. Cone. (ng/mL) 0.0947 0.105 0.095 0.106 0.103 0.1 0.107 0.103 0.0982 0.117 0.116 0.116 0.103 0.0991 0.108 % Recovery 91.1 101 91.3 102 99.2 96.1 103 99.1 94.4 113 112 111 99.2 95.2 104 101 6.9 Spike Cone. (ng/mL) 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 [1*O J P F O S Calc. Cone. (ng/mL) 0.104 0.112 0.128 0.121 0.108 0.103 0.0997 0.0995 0.109 0.114 0.115 0.112 0.0938 0.107 0.112 % Recovery 100 108 123 117 104 99 95 9 95.7 105 110 111 108 90.2 103 107 10S 8.1 p. 103 3M ENVIRONMENTAL LABORATORY PAGE 101 OF 104 3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 39. LCS Recoveries for Extraction Batch 2 Using Unextracted Acetonitrile Calibration: Surrogates. [1,2-" Cj]PFOA ("O J P F O S Samle ID 090828 BGF LCS Low 1 090828 BGF LCS Low 2 090828 BGF LCS Low 3 090828 BGF LCS Mid 1 090828 BGF LCS Mid 2 090828 BGF LCS Mid 3 090828 BGF LCS High 1 090828 BGF LCS High 2 090828 BGF LCS High 3 090828 BGF ECF LCS 1 090828 BGF ECF LCS 2 090828 BGF ECF LCS 3 090828 BGF PFOS LCS 1 090828 BGF PFOS LCS 2 090828 BGF PFOS LCS 3 Average %RSD Spike Cone. (ng/mL) 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 1.104 2.104 3.104 Calc. Cone. (ng/mL) 0.121 0.0878 0.121 0.0895 0.110 0.0926 0.121 0.118 0.106 0.0918 0.0830 0.107 0.103 0.111 0.112 % Recovery 116 84.4 116 86.1 106 89.0 117 113 102 88.3 79.8 116 84.4 116 86.1 100 15 Spike Cone. (ng/mL) 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 Calc. Cone. (ng/mL) 0.0984 0.101 0.106 0.0944 0.0907 0.0860 0.0940 0.0992 0.099 0.109 0.102 0.113 0.106 0.0987 0.109 % Recovery 94.6 96.9 102 90.7 87.2 82.7 90.4 95.4 95.2 105 98.2 109 102 94.9 105 96.6 7.4 p. 104 3M ENVIRONMENTAL LABORATORY PAGE 102 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. E09-0372 Table 40. LCS Recoveries for Extraction Batch 3 Using Unextracted Acetonitrile Calibration: Surrogates. Sample ID 090901 BGF LCS Low 1 090901 BGF LCS Low 2 090901 BGF LCS Low 3 090901 BGF LCS Mid 1 090901 BGF LCS Mid 2 090901 BGF LCS Mid 3 090901 BGF LCS High 1 090901 BGF LCS High 2 090901 BGF LCS High 3 090901 BGF ECF LCS 1 090901 BGF ECF LCS 2 090901 BGF ECF LCS 3 090901 BGF PFOS LCS 1 090901 BGF PFOS LCS 2 090901 BGF PFOS LCS 3 Average %RSD Spike Cone. (ngimL) 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 [ 1 ,2 -1sC j]P F O A Calc. Cone. (ng/mL) 0.104 0.109 0.109 0.101 0.107 0.0981 0.101 0.119 0.0929 0.113 0.106 0.0999 0.0988 0.100 0.108 % Recovery 99.9 105 105 97.2 103 94.4 96.8 114 89.3 109 102 96.0 95.0 962 104 100 6.4 Spike Cone. (ng/mL) 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 0.104 ["QdPFOS Calc. Cone. (ng/mL) 0.0906 0.111 0.114 0.121 0.120 0.100 0.110 0.102 0.107 0.0977 0.118 0.0995 0.123 0.111 0.108 % Recovery 87.1 107 109 116 115 96.6 106 97.9 103 94 113 95.7 118 107 104 105 8.6 p. 105 3M ENVIRONMENTAL LABORATORY PAGE 103 OF 104 3MENVIRONMENTAL LABORATORY REPORT NO. EQ9-0372 10.3 Surrogate Recoveries in Spiked Blanks (Extracted Curve Calibration). Extraction Batch 1 Sample ID Sample Description Spike Cone. (ng/mL) [1,2-13C j]P F O A Calc. Cone. (ng/mL) %Rec 090826 BGF Matrix Blank-1 090826 BGF Matrix Blank-2 090826 Aqueous Blank-1 090826 Aqueous Blank-2 Acetonitrile Blank with IS & Surr Acetonitrile Blank with IS & Surr (with IS/surr) (with IS/surr) (with IS/surr) (with IS/surr) 08 007-145 08 007-145 0.104 0.104 0.104 0.104 0.0998 0.0998 0.113 0.112 0.0980 0.113 0.104 0.125 109 108 94.2 109 104 125 Extraction Batch 2 Sample ID 090828 BGF Matrix Blank-1 090828 BGF Matrix Blank-2 090828 Aqueous Blank-1 090828 Aqueous Blank-2 Acetonitrile Blank with IS & Surr. Acetonitrile Blank with IS & Surr. Semple Description (with IS/surr) (with IS/surr) (with IS/surr) (with IS/surr) 08 007-145 08 007-145 Spike Cone. (ng/mL) [1,2 -1,C j]P F O A Calc. Cone. (ng/mL) 0.104 0.104 0.104 0.104 0.0998 0.0998 0.114 0.103 0.103 0.102 0.0929 0.0793 %Rec 110 99.0 99.0 98.1 93.1 79.5 Extraction Batch 3 Sample ID Sample Description 090901 BGF Matrix Blank-1 (with IS/surr) 090901 BGF Matrix Blank-2 (with IS/surr) 090901 Aqueous Blank-1 (with IS/surr) 090901 Aqueous Blank-2 (with IS/surr) Acetonitrile Blank with IS & Surrogate 08 007-145 Acetonitrile Blank with IS & Surrogate 08 007-145 (1 ) Surrogate recovery exceeded 10030% . [1,2-i3C*JPFOA Spike Cone. (ng/mL) 0.104 0.104 0.104 0.104 0.0998 0.0998 Calc. Cone. (ng/mL) 0.102 0.0990 0.108 0.108 0.107 0.110 %Rec 98.1 95.2 104 104 107 110 Spike Cone. (ng/mL) 0.104 0.104 0.104 0.104 0.0956 0.0956 ["cyp F O S Calc. Cone. (ng/mL) 0.112 0.121 0.0810 0.110 0.0995 0.0948 Spike Cone. (ng/mL) 0.104 0.104 0.104 0.104 0,0956 0.0956 [1*OiJPFOS Calc. Cone. (ng/mL) 0.101 0.107 0.0998 0.118 0.109 0.125 Spike Cone. (ng/mL) 0.104 0.104 0.104 0.104 0.0956 0.0956 [" OJPFOS Calc. Cone. (ng/mL) 0.105 0.107 0.107 0.104 0.101 0.106 %Rec 108 116 77.9 106 104 99.2 %Rec 97.1 103 96.0 113 114 (,,131 %Rec 101 103 103 100 106 111 p. 106 3M ENVIRONMENTAL LABORATORY PAGE 104 OF 104