Document xzpQw2z5rjR8e3RE7q87Zr63E
Jean B. Sweeney Staff Vise President
3M Environmental, Health and Safety Operations
o r r '
p. 1
900 Bush Avenue, Building 42-2E-26 P0 Box 33331 St. Paul, MN 55133-3331 651 778 5488
CERTIFIED MAIL
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April 9, 2009
NO CBI
Document Processing Center EOPffAiceEaosftP-oRlluotoimon6P4r2e8veAntttino:nSaencdtiTonox8i(ces), U.S. EPA 1200 Pennsylvania Avenue NW Washington, DC 20460-0001
1||1I11I1!1I:; IIIt M11 l|l| j. IilI:1I1I IIIl|l|'1l1l JI|j ' ' " " iC H 11
Re: TSCA 8(e) Substantial Risk Notice: Supplemental to Docket No. 8EHQ-0598-373; Sulfonate-based and Carboxylate-based Fluorochemicals
To whom it may concern:
3M is submitting this notice to supplement its previous submissions on sulfonate and carboxylate-based fluorochemicals.
3M recently conducted fluorochemical (FC) analysis of 33 fish fillet tissues of walleye, northern pike, sauger, bluegill, smallmouth bass, and black crappie as split samples collected by the Minnesota Pollution Control Agency (MPCA) from the Mississippi River.
Levels of PFOS quantified in all tissues were comparable to those reported by the MPCA (March 2009, http://www.pca.state.mn.us/publications/c-pfc 1-01 .pdf) and ranged from 28.5 to 382 ng/g. In addition, levels of perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), and perfluorododecanoic acid (PFDoA) were quantified in most of the samples. PFDA levels ranged from 0.581-10.2 ng/g, PFUnA levels ranged from 0.288-5.81 ng/g, and PFDoA levels ranged from 0.271-3.38 ng/g.
The PFOS data have been finalized and are provided in the enclosed report. Data for the other analytes are currently being finalized, and will be forwarded to EPA upon completion of the reports.
While 3M does not believe that any of these data taken alone or cumulatively meet the "EsPuAbsttoanatsiasel srsisFkC" reexppoorstuinrge tphartehswhoalyds,. wTehnereevfeorrteh,ewleessarreecpolganciiznegtthheesoengreosiunlgtswinortkheby8(Ue).S. docket as a supplement to previous submissions.
If you have any questions or would like any additional information, please contact Deanna ~ Luebker at (651) 737-1374 or diluebker@mmm.com.
Sincerely,
Jean B. Sweeney Staff Vice President, 3M Environmental, Health and Safety Operations
Enclosure eM* m ciiC0NTAINSN0CBi
jy i $ $ o3
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3M ENVIRONMENTAL LABORATORY REPORT NO. 0 9 -0 0 5 3
Final Analytical Report
Perfluorochemical Analysis of Fish Fillet Homogenates collected from the Mississippi River by the Minnesota Pollution
Control Agency Phase I: PFOS
Laboratory Request Number: E09-0053 Method Requirement: ETS 8-45.0
Testing Laboratory 3M EHS Operations 3M Environmental Laboratory
3M Center Building 260-5N-17 Maplewood, MN 55144
Requester
Gary Hohenstein 3M EHS Operations
3M Center Building 224-5W -03 Maplewood, MN 55144
laccHepiTEPl
The testing reported herein meet the requirements of ISO/1EC17025-2005 "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.
Certificate #2052-01
3M ENVIRONMENTAL LABORATORY
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3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0053
3M Environmental Laboratory 3M Environmental Laboratory Manager: William K. Reagen, Ph.D. 3M Principal Analytical Investigator and Report Author Michelle D. Malinsky, Ph.D.
Analytical Report E09-0053 Phase I
Perfluorochemical Analysis of Fish Fillet Homogenates collected from the Mississippi River by the Minnesota Pollution Control Agency Phase I: PFOS
Aprii 1,2009
The Minnesota Pollution Control Agency (MPCA) submitted thirty-three fish fillet homogenates to the 3M Environmental Laboratory for perfluorochemical analysis under project number E09-0053. The samples were extracted and analyzed using method ETS 8-45.0 "Determination of Fluorochemicals via Protein Precipitation of Fish Tissues (Fillet or Whole Body) and Analysis by High Performance Liquid Chromatography with Tandem Mass Spectrometry''. The target analytes for this study included perfluoroalkane carboxylic acids ranging from C4 to C12, perfluoroalkane sulfonates (C4, C6, and C8), and perfluorooctanesulfonamide. This phase I report summarizes the results for perfluorooctane sulfonate (PFOS) only. The results for the other target analytes will be issued in a phase II report.
The 3M Environmental Laboratory maintains A2LA accreditation to ISO/IEC 17025 for the specific tests/calibrations listed in A2LA Certificate #2052-01 and meets the relevant quality systems requirements of ISO 9001:1994. ETS 8-45.0 falls under the laboratory's current scope of accreditation. The data and final report were audited for compliance to laboratory's ISO/IEC17025 quality system.
A key for the sample descriptions is provided in Section 2.2.
Table 1 below summarizes the PFOS results. 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 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.
Certificate #2052-01
3M ENVIRONMENTAL LABORATORY
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3MENVIRONMENTAL LABORATORY REPORT NO. E09-0053
T a b le ! Sample Results Summary: PFOS
3M UM SID E09-0053-001 E09-0053-001 Dup
E09-0053-002 E09-0053-002 Dup
E09-0053-003 E09-0053-003 Dup
E09-0053-004 E09-0053-004 Dup
E09-0053-005 E09-0053-005 Dup
E09-0053-006 E09-0053-006 Dup
E09-0053-007 E09-0053-007 Dup
E09-0053-008 E09-0053-008 Dup
E09-0053-009 E09-0053-009 Dup
E09-0053-010 E09-0053-010 Dup
PFOS
Sample Description
mConc. (ng/g)
MissR_pool2_WE_1
Average %RPD MissR_pool2_WE_2
Average %RPD MissR_pool2_WE_3
Average %RPD MissR_pool2_WE .4
Average %RPD MissR_pool2_SAG_1
Average %RPD MissR_pool2_SAG_2
Average %RPD MissR_pool2_SMB_1
Average %RPD MissR_pool2_SMB_2
Average %RPD
28.7 28.4 28.5 1.0 45.9 43.4 44.7 5.8 84,3 81.9 83.1 Z9 51.0 43.C 47.0
17 41.1 ............ 38.6 ..... . 39.8 6.3 43.7 43.4 43.5 0.68 57.5 50.4 54.0
13 l2l379 384 382
1.4
MissR_pool2_SMB_3
Average %RPD MissR_poo!2_SMB_4
............................... . ............
Average %RPD
111 123 117 10 131 122 127 7.1
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Table 1 Continued.
3 M U M S ID E09-0053-011 E09-0053-011 Dup
E09-0053-012 E09-0053-012 Dup
E09-0053-013 E09-0053-013 Dup
E09-0053-014 E09-0053-014 Dup
E09-0053-015 E09-0053-015 Dup
E09-0053-016 E09-0053-016 Dup
E09-0053-017 E09-0053-017 Dup
E09-0053-018 E09-0053-018 Dup
E09-0053-019 E09-0053-019 Dup
E09-0053-020 E09-0053-020 Dup
E09-0053-021 E09-0053-021 Dup
Sample Description MissR_pool2_SMB_5
Average %RPD MissR_pool2_BKS_1
Average %RPD NlissR_pool2_BGS_1
Average %RPD MissR_pool2_BGS_2
Average %RPD MissR_pool2_BGS_3
Average %RPD MissR_pool2_BGS_4
Average %RPD MissR_pool2_BGS_5
Average %RPD MissR_pool3_WE_1
Average %RPD MissR_pool3_WE_2
Average %RPD MissR_pool3_WE_3
Average VoRPD MissR_pool3_WE_4
Average %RPD
9
oX
j
PFOS
n Conc. (ng/g) 141 150 146 6.2 55.5 54.5 55.0
1.8
155 168 161 7.8 110 100 105 9.4 188 167 177 11 ^331
e)336 2.7 123 120 122 2.0 97.4 95.5 96.4 2.0 78.3 78.6 78.5 0.37 97.4
................ 82.3...... . 89.9 17 49.4 52.3 50.8 5.7
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3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0053
PAGE 4 OF 31
Table 1 Continued.
3M UM SID E09-0053-022 E09-0053-022 Dup
E090053-023 E09-0053-023 Dup
E09-0053-024 E09-0053-024 Dup
E09-0053-025 E09-0053-025 Dup
E09-0053-026 E09-0053-026 Dup
E09-0053-027 E09-0053-027 Dup
E09-0053-028 E09-0053-028 Dup
E09-0053-029 E09-0053-029 Dup
E09-0053-030 E09-0053-030 Dup
E09-0053-031 E090053-031 Dup
E09-0053-032 E09-0053-032 Dup
Sample Description MissR_pool3_WE_5
Average %RPD MissR_pool3_NOP_1
Average %RPD MissR_pool3_SMB_1
Average %RPD MissR_pool3_SMB_2
Average %RPD MissR_pool3_SMB_3
Average %RPD MissR_pool3_SMB_4
Average %RPD MissR_pool3_SMB_5
Average %RPD MissR_pool3_BGS_1
Average %RPD MissR_pool3_BGS_2
Average %RPD MissR_pool3_BGS_3
Average %RPD
MissR_pool3_BGS_4
Average %RPD
PFOS mConc. (ng/g)
64.2 68.1
66.2
5.8 49 8 512 50.5 28 29.5 29.9 29.7 1.1 103 108 105 4.9 48.8 48.3 48.5
1.0 63.0 66.9 64.9 6.0 55 0 53.3 54.2 3.1 76.7 72.8 74.7 5.3 160 165 163 2.6 138 128 133 7.6 223 219 221 1.7
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3M ENVIRONMENTAL LABORATORY REPORT NO. 0 9 -0 0 5 3
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3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0053
Table 1 Continued.
PFOS
3 M U M S ID
Sample Description
E09-0053-033 E09-0053-033 Dup
MissR_pool3_BGS_5
126 133
Average
129
%RPD
5.7
(1) Unless otherwise specified, the recovery of associated laboratory matrix spike (LMS) was within 10030% which meets
ETS 8-45.0 method acceptance critena. Sample results are considered accurate to within the overall analytical method
uncertainty 10015% (PFOS), 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.
(2) Sample results were repotted from a 1:10 post-extraction dilution.
;?
2.1 Target Analytes.
Table 2 below provides pertinent information regarding the target analytes, internal standards, and surrogate compounds investigated in this study.
Table 2. Target Analyte Summary.
Compound Name
Perfluorobutanoic acid Perfluoropentanoic acid Perfluorohexanoic acid Perfluoroheptanoic acid
Synonym or Acronym
PFBA (C4 Add) PFPeA (C5 Add) PFHxA (C6 Acid) PFHpA (C7 Acid)
Analytical Purpose
Target Target Target Target
Perfluorooctanoic acid
PFOA (C8 Acid)
Target
Perfluorononanoic acid Perfluorodecanoic acid Perfluoroundecanoic add Perfluorododecanoic add Perfluorobutane sulfonate Perftuorohexane sulfonate
PFNA (C9 Add) PFDA (C10 Acid) PFUnA(C11 Acid) PFDoA (C12 Acid) PFBS (C4 Sulfonate) PFHS (C6 Sulfonate)
Target Target Target Target Target Target
Perftuorooctane sulfonate
PFOS (C8 Sulfonate)
Target
L.
Formula
C 3F7C O O H C,,FbCOOH c 6f ,, c o o h CoFtjCOOH CrF ,5C O O H [C7F15C 001[N H 4*] C bF,tC O O H c 9f ,9c o o h C ,oF2,C O O H C 11F23C O O H [C4F8S 0 31[K*] [CjFuSOsHNa*] [C,F,tSO ,1IC] [CsF17SO,1[K*]
Reference Standard Source
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)Wellington Labs L-PFOS (linear)Wellington Labs ECF PFOS (branched) 3M Production Lot 217
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3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0053
Table 2 Continued.
Compound Name
Synonym or Acronym
Analytical Purpose
Formula
Reference Standard Source
Perfluorooctanesulfonamide
FOSA (C8 Sulfonamide)
Target
C ,,F ,,S 0 2 N H 2
3M (L-15709)
'' GrPerfluorobutanoic acid
" Cz-Perfluorohexanoic acid
13C4-Perfluorooctanoic acid
13C5-Perfluorononanoic acid
,3Cj-Perfluorodecanoic add
13Cz-Perfluoroundecanoic add l3CrPerfluorododecanoic add '"Or-Ammonium Perfluorobutane sulfonate ,sOrAmmonium Perfluorohexane sulfonate 13C<-Sodium Perfluorooctane sulfonate
,3CrPerfluorooctanoic add
18OrAmmonium Perfluorooctane sulfonate
[1,2,3,4-nC,]PFBA [1 ,2 -13C 2]PFHxA
[1,2,3,4-'3C4]PFOA [1,2,3,4,5-,3C$]PFNA
[1 ,2 -'3CyPFDA [1.2 "CaJPFUnA [1,2 -''CzJPFDoA
['"OJPFBS [ '"O J P F H S [1 .2 ,3 ,4 -, 3C ,]P F O S [1,2-13CJPFOA ['"OJPFOS
IS IS IS IS IS IS IS IS IS IS Surrogate Surrogate
,3C F 3( '3C F 2)2,3C O O H C F ,(C F 2)j(13C F2)' 3C O O H C F j(C F2)3(13C F2)j13C O O H C F j(C F 2)3(' 3C F2)4' 3C O O H CF3(CF2M ,3CF2),3COOH C F 3(C F 2) ,( 13C F 2)13C O O H C F 3(C F 2)3(13C F 2)' 3C O O H
[C4FS'i 0 20J [N H 4l [CeFnS^OjOKNH*] [CF3{CF2)3(,3CF2)3'3CF2S0 3^[Na,] C F3(CF2)5('3CF2) 13COOH [CeF,,S,s0 201[NH4*]
Wellington Labs Wellington Labs Wellington Labs Wellington Labs Welington Labs Wellington Labs Wellington Labs RTI International Wellington Labs Wellington Labs
Perkin Elmer RTI International
2.2 Sample Descriptions.
The table below summarizes the abbreviations provided by the MPCA used to identify the fish species collected for this study. No information was provided regarding the location of sample collection within Pool 2 or Pool 3 of the Mississippi River.
Table 3. Sample Description Key.
Species Blueqill Walleye Black Crappie Sauger Smallmouth Bass Northern Pike
Abbreviation BGS WE BKS SAG SMB NOP
2.3 Sample Collection and Receipt.
The chain of custody provided by the MPCA indicated that the samples were collected on June 5 and June 9, 2008. On January 27, 2009, the 3M Environmental Laboratory received the homogenized fillet samples in Nalgene bottles on dry ice. The samples were logged into the 3M Environmental Laboratory LIMS system under project E09-0053 and placed in frozen storage. Information provided by the MPCA indicated that the samples were homogenized with the skin on and scales removed; however, no specifics regarding the homogenization procedure were given.
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3M ENVIRONMENTAL LABORATORY REPORT NO. 09-0053
It should be noted that these fish samples have been previously handled and analyzed at another laboratory under contract by the MPCA. It Is unknown how these samples have been handled during analysis and storage. It is possible that some, or all, of these samples may possibly have been compromised during the previous handling, analysis and storage. No assumptions are being made to the integrity of these samples.
3M Environmental Laboratory personnel removed the homogenized fish tissue from the sample container by cutting the bottle away from the frozen sample mass using a clean utility knife, i he frozen sample mass was then placed in a plastic bag and returned to frozen storage before the tissue was homogenized before extraction. Based on the sample consistency in the Nalgene bottles, it appeared that the sample homogenates had thawed at some point before they arrived at the 3M Environmental Laboratory. (Homogenized tissue had refrozen into a solid mass that could not be broken up while frozen in the container.)
i x ii/lethods - Analytical and
'V
3.1 Tissue Preparation
Each submitted sample and bluegill fillet control tissue (TN08-0220-1/1) purchased from Osage Catfisheries, Inc. (Osage Beach, MO) were homogenized frozen using dry ice.
Depending on the sample size, frozen fish tissue was added to a pre-chilled stainless steel bowl of either a Robot Coupe RSI 2Y-1 or a RSI 23B vertical batch processor and homogenized 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 the residual carbon dioxide to sublime After sublimation, the bag was sealed and homogenates were kept frozen.
3.2 Sample Extraction
Polyethylene centrifuge tubes (50 mL) were chilled in a cooler with dry Ice for approximately thirty minutes prior to weighing homogenate aliquots to prevent the tissue powder from thawing and congealing during the weighing process. A 0.5 g sub-sample of the fish tissue homogenate was accurately weighed in a pre-chilled 50 mL polyethylene centrifuge tube. Tissue aliquots were then spiked with internal standard (IS) and surrogates to produce an approximate concentration of 1 ng/g Samples designated as lab matrix spikes or matrix-matched calibration standards were additionally spiked with the target and surrogate analytes at appropriate levels to produce the desired tissue concentrations. Samples intended for laboratory QC (matrix blanks and laboratory control matrix spikes) were spiked with surrogates at 1 ng/g and the other target analytes at appropriate levels. After spiking, the tissue homogenates were allowed to sit for 30 minutes before 5 mL of acetonitrile was added.' The samples were then thoroughly homogenized with the acetonitrile using an Omni Prep multi-place homogenizer with disposable plastic probes (15,000 rpm for 2 minutes). The acetonitrile/tissue extracts were then placed in a freezer at -20C for at least one hour. Upon removal from the freezer, sample extracts were centrifuged at a targeted temperature of -5C for 20 minutes at 3000 rpm. If any delays occurred, samples were returned to the -20C freezer and then re-centrifuged.
After centrifugation, 1 mL of clarified supernatant was transferred to a 2 mL autovial spiked with 10 pL of 10% formic acid. Autovlals were then capped and vortex mixed.
Samples were extracted in three separate batches For each submitted sample, a sample, sample duplicate, and laboratory matrix spike (LMS) were prepared. Two samples were re-extracted in a fourth batch as the associated LMSs prepared the first time were not high enough for resultant endogenous concentration. Each preparation batch consisted of the following calibration and quality
control elements:
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3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0053
a nine 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 (0.05 ng/g, 1.5 ng/g, and 8 ng/g)
triplicate lab control spikes of 3M electrochemical fluorination (ECF) PFOA and PFOS at 5 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 summarizes the preparation dates and samples prepared in each batch.
Table 4. Sample Preparation Summary.
Batch Number Batch 1 Batch 2 Batch 3 Batch 4
Preparation Dates 2/18/2009-2/20/2009 2/19/2009 - 2/23/2009 2/24/2009 - 2/25/2009 3/5/2009 - 3/6/2009
Samples E09-0053-001 - E09-0053-011 E09-0053-012 - E09-0053-022 E09-0053-023 - E09-0053-033 E09-0053-008 & E09-0053-016 (reprep)
3.3 Analysis
Analysis for the suite of PFCs listed above was performed using high performance liquid chromatography-tandem mass spectrometry (HPLC/MS/MS). For this investigation, samples were analyzed using an Agilent 1100 series (Palo Alto, CA) HPLC system interfaced to either a PE SCIEX API 4000 triple quad ru p le or SCIEX API 4000 Q-Trap mass spectrometer (Foster City, CA). Both instruments were equipped with a SCIEX Turbo V ion-spray interface operating in the negative ion M S/M S mode using multiple reaction monitoring (MRM). AnalystTM 1.4.2 software was used for all data collection and reduction. Table 5 lists the MRM transitions monitored for each analyte. A Thermo
Scientific PRISM RP guard column (2.1mm x 50 mm; 5p particle size) was placed in-line after the purge valve and before the sample injection port to trap any PFC contaminants coming from the HPLC instrument and/or the mobile phases. This sufficiently separated the elution of the "system" PFC peaks from those present in the sample extracts.
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3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0053
Table 5, MRM Transition Summary.
Compound PFPeA (C5 Acid) PFHxA (C6 Acid) PFHpA [C7 Acid)
Analyte Description Target Target
Taraet
Target
PFNA iC9 Acidl
Target Target
PFl InA fC11 Acid)
Target
p f o s fC8 Sulfonate) FD.SA (C8 Sulfonamide) [1,2,3,4 -,JC,]PFBA [1 2 ."CJPFHxA
I1,2,3,4-'3C 4Ff o a [1,2,3,4,5-130 s]PFNA [1,2 -"CJPFDA [1,2 -13C2]PFUnA [1,2 -nC2]PFDoA ['"OzJPFBS ['' OzJPFHS [1,2,3,4- ,3C<]PFOS [1,2 -''3C2]PFOA ["OdPFOS
Target Target IS for PFBA and PFPeA IS for PFHxA IS for PFHpA and PFOA IS for PFNA IS for PFDA IS foi PFUnA IS for PFDoA IS for PFBS IS for PFHS IS for PFOS, FOSA Surrogate (Acids) Surrogate(Sulfonates FOSA.)
mMRM Transition(s)
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>469 513>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*34
403*84
503*80
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
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3M ENVIRONMENTAL LABORATORY REPORT NO. 0 9-0053
(1) Individual transitions were summed for each analyte to produce a "total ion chromatogram" (TIC). The TICs were used for quantitation.
Analysis of the small acids (C4 through C6) was performed using a Thermo Scientific PRISM RP column (2.1mm * 50 mm; 5 p particle size) held at 30C with the mobile phase system consisting of 5 mM ammonium acetate with 0.01 % acetic acid in water (A) and methanol (B). The gradient used to elute the analytes of interest is presented in Table 6. The flow rate was held at 300 pL/min throughout the run and a 20 pL injection volume was used. The outlet of the analytical column was directed to a column switching valve where the first three minutes of the run were diverted to waste. After three minutes, the valve was switched to direct the effluent to the mass spectrometer for analysis.
The large acids (C7 through C12), the sulfonates, and FOSA were analyzed using a Thermo Scientific BetasilTM C18 analytical column (2.1mm * 100 mm; 5p particle size) held at 30C with the mobile phase system consisting of 2 mM ammonium acetate in water (A) and acetonitrile (B). The gradient used is also provided in Table 6. The flow rate was held at 400 pL/min throughout the run and a 25 pL injection volume was used. Samples were injected onto a Waters (Milford, MA) Oasis HLB on-line extraction column (20 mm * 3.0 mm, 25 p particle size) with the outlet directed to a column switching valve where the first five minutes were diverted to waste. After five minutes, the valve was switched and the effluent was directed to the analytical column for separation of the target analytes and analysis by the mass spectrometer.
Table 6. LC Gradient Parameters.
Small Acids: C4-C6
Large Acids: C 7-C 2; Sulfonates, FOSA
Step 0 1 2 3 4 5 6
A B
Total Time (min) 0.0 30 3.5 9.0 15.0 15.1 19.0
%A
90 90 30 5.0 5.0 90 90
%B
10 10 70 95 95 10 10
5 mM ammonium acetate with 0.01% acetic acid (aq) Methanol
Step 0 1 2 3 4 5 6 7 8
A
B
Total Time (min) 0.0 3.0 3.5 13.5 15.5 16.0 18.0 18.3 21.0
%A 97 97 70 40 40 10 10 97 97
2 mM ammonium acetate (aq)
Acetonitrile
%B 3.0 3.0 30 60 60 90 90 30 3.0
To manage the large number of transitions required for the large acids, sulfonates, and FOSA, a multiperiod method was constructed. The first period (tim e-0 minutes to 10.6 minutes) collected the transitions for PFBS, PFHpA, PFOA, [1,2 - 13C2]PFOA, PFHS, PFNA and their respective ISs. The second period (time=10.5 min to 21.0 minutes) collected the transitions for PFDA, PFUnA, PFOS, [180 2]PFOS, PFDoA, and FOSA and their respective ISs. For analytes where more than one transition was acquired, a total ion chromatogram (TIC) which summed the respective transitions for that analyte was used to analyze the data.
JET*?7--'
4.1 Calibration
Extracted ` matrix-matched calibration standards and QCs were prepared by spiking known amounts of target analytes, surrogates, and internal standards into individual 0.5 g aliquots of bluegill fillet control
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3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0053
tissue (TN08-0202-1/1) homogenate. Each spiked fish aliquot was then extracted using the procedures outlined in Section 3.2. A total of nine spiked standards ranging from 0.25 ng/g to 25 ng/g (nominal) were prepared. Additionally, an unextracted acetonitrile solvent curve ranging from 0.025 ng/mL to 50 ng/mL was also prepared. All sample results for PFOS and [1B0 2]P F 0S were quantitated against the solvent curve as sample extract concentrations for PFOS exceeded the upper calibration range of the extracted curve. To demonstrate equivalency, the extracted curve and the laboratory control QC samples were quantitated using the solvent curve. Once the concentrations were corrected for the endogenous level of PFOS in the control tissue, PFOS recoveries of the calibration curve points were within 10014%. The recoveries of the extracted curve points quantitated against the solvent curve points are provided in the Supplemental Information Section 11.1.
A quadratic, 1/x or 1/x2weighted calibration curve was used to fit the data for PFOS and [180 2]PFOS. Internal standard quantitation was used. The data was not forced through zero during the fitting process. The accuracy of each curve point was verified by 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 met the method calibration accuracy requirement of 10025%, except the LOQ standard (10030%). The coefficients of determination (r2) were 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 PFHS, PFOS, and PFOA, the reference standard used for calibration and lab control spikes was comprised predominantly of the linear isomer.
It is noted that the purchased control bluegill tissue matrix differs in composition from the study bluegill samples in that the purchased bluegill fillet homogenate does not contain the skin of the fillet, only the "meat".
*As fish matrix can vary greatly from species to species, the control matrix used to generate the extracted calibration curve and laboratory control QC samples is considered to be matrix-matched for the bluegill samples only. The laboratory control matrix should be considered as a "surrogate" control matrix for 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). Since the solvent curve was used for quantitation, the aqueous method blanks were used to establish the LOQ so that the curve could be used to quantitate the endogenous levels of PFOS in the control matrix. The limit of quantitation for PFOS varied from extraction date and instrument batch. The PFOS LOQ ranged from 0.00251 ng/mL to 0.00995 ng/mL which corresponds to approximately 0.025 ng/g to 0.1 ng/g in fish tissue once the conversion is made.
4.3 System Suitability
Four replicate injections of the solvent calibration standard were analyzed at the beginning of the analytical sequence to demonstrate overall system suitability. Method criteria states that system suitability injections shall produce a RSD of less than 7% for the ratio of target analyte area counts to internal standard area counts and an RSD of less than 2% for the retention time. Method acceptance criteria were met for both PFOS and [180 2]PF0S.
4.4 Continuing Calibration
During the course of the analytical sequence, several continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response from initial calibration curve was still in control. CCV injections produced recoveries of PFOS and [180 2]P F 0S within 100%25%, which met method criteria.
3M ENVIRONMEhiTAL LABORATORY
PAGE 12 OF 31
p. 14
3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0053
4.5 Blanks
Five types of blanks were prepared and analyzed with the samples: matrix blanks (bluegill filet 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 determine the LOQ for each analyte. Surrogate recoveries of spiked blanks are provided in the Supplemental Information Section 11.2.
4.6 Lab Control Spikes (LCSs)
Triplicate lab control spikes of the purchased bluegill fillet control matrix at three different levels were prepared each extraction day to determine analytical method uncertainty (See Section 4.9). For PFHS, PFOS, and PFOA, the standard reference material used for the LCS spikes was the linear isomer, which was the same used for the calibration curves. Separate 3M electrochemical fluorination (ECF) spikes of branched PFOS and PFOA were prepared to evaluate any potential bias from quantitation against a linear standard. Lab control spikes were prepared to evaluate method accuracy and precision and were used to determine analytical method uncertainty (See Section 4.9). The [180 2]P F 0 S surrogate was spiked at a consistent 1 ng/g (0.1 ng/mL) for all LCS samples. For PFOS, the spiked concentration was corrected for the average PFOS concentration determined for the control matrix in the same extraction batch. Lab control spike recoveries are provided in the Supplemental Information (Section 11.3). For both PFOS and [102)P F0S, all replicates (N=48) except one, produced recoveries within method acceptance criteria 100%25%.
4.7 Sample Concentration Calculation
The solvent calibration curve used for quantitation provided extract concentration in units of ng/mL. The following equation was used to convert the extract concentration to sample tissue concentration in units of ng/g.
Extract Concentration (-^-)*ExtractionVolum e(m L) Tissue Concentration (-- ) = ---------------- ------------------ -- ---------------------------------------
g Extracted Mass (g)
Extraction Volume = 5 mL Extracted Mass -0 .5 g
4.8 Lab Matrix Spikes (LMSs)
For each submitted sample, 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 LMS, all target analytes were spiked at a nominal concentration of 2 ng/g except PFOS, which was spiked at a total concentration of approximately 150 ng/g. The recovery of the LMS was calculated using the following equation.
j jExtract Cone. ( - ^ - ) ' ExtractionVolume(mL) J - ^Average Sample C o n c |-- * LMS Sample Mass (g)
LMS%Recovery =
Spike Amount (ng)
100%
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 PFOS, the LMS was 76.0 ng (-1 5 0 ng/g tissue concentration) except for samples E090053-008 and -016 where the LMS was 250 ng (-5 0 0 ng/g tissue concentration). The [,80 2]P F 0S surrogate was spiked at 0.502 ng (-1 ng/g tissue concentration).
3M ENVIRONMENTAL LABORATORY
PAGE 13 OF 31
3M ENVIRONMENTAL LABORATORY REPORT NO. EC9-0053
4.9 Analytical Uncertainty
ETS 8-45.0 states that the analytical method uncertainty will be determined by statistical evaluation of the individual analyte recovery in LCSs. Current project QC results, as well as historical 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 7 below provides the analytical uncertainty for PFOS and the [180 2]P F 0S surrogate.
Table 7. Analytical Method Uncertainty
Average % Recovery Standard Deviation 2*Standard Deviation N
Analytical Uncertainty
PFOS
105 7.6 15 50 (2 Rainbow Trout fillets, 48 Bluegill fillets) 15%
C' OJPFOS Surrogate 108 7.1 14
48 (Bluegill fillet only)
14%
> . ;Vj 1
'
Table 8 below provides the sample and lab matrix spike results for PFOS and the [180 2]P F0S sumogate quantitated using an unextracted, solvent curve. The extracted curve prepared in bluegiH fillet control matrix was demonstrated to be equivalent to the solvent curve for both PFOS and the [180 2]P F 0S surrogate over the approximate range of 0.25 ng/g to 25 ng/g. (See Supplemental information Section 11.1 for additional information.) As most of the study samples were greater than 25 ng/g for PFOS, the solvent curve, which went up to 50 ng/mL or -5 0 0 ng/g was used for quantitation. All samples produced PFOS LMS recoveries within method acceptance criteria of 19030%. E09-0053-008 and -016 were re-prepared in a separate extraction batch with a LMS of 250 ng (-5 0 0 ng/g). The initial analyses for these two samples indicated that the original LMS concentration of -1 5 0 ng/g was less than half the endogenous concentration and therefore was not considered an appropriate level for assessing sample quantitation accuracy. Results for these two samples from the initial analysis were not reported. Instances of the surrogate recovery exceeding 10030% have been flagged in Table 8; however, ETS 8-45 0 specifies no acceptance criteria for surrogate recoveries as the intent of the surrogate is to evaluate systematic biases or interferences that may be present As the PFOS LMS recoveries were all within 100+30% and the overall number of surrogate recoveries exceeding 10030% were few, all results were considered reportable and accurate to within the stated analytical method uncertainty of 10015%.
The recoveries of the 3M ECF LCSs prepared with each extraction batch (N=12 for the study) ranged from 97.5% to 130% with a calculated average of 110% (8.4% RSD). The results of the ECF QC spikes demonstrated that there is no discernible bias when PFOS ECF isomers are quantitated against the predominantly linear reference standard. Therefore, the reported PFOS values are considered accurate to within the stated method uncertainty regardless of the degree of branched PFOS isomers present in the sample extracts.
The PFOS sample concentrations presented in Table 1 and Table 8 were reported from the total ion chromatogram (TIC) where the instrument software summed the three individual transitions (499>80,
3M ENVIRONMENTAL LABORATORY
PAGE. 14 OF 3 !
3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0053
499>99, 499>130). As the 499>80 transition has been well documented to produce PFOS matrix interferences in biological tissue studies[1], the three individual transitons were evaluated separately, to verify that the area ratios observed in the standards were conserved in the samples. For Batches 1, 2, and 3, the combined average area percentages of 499>80,499>99, and 499>130 in the solvent calibration curve points were 76.5% (3.4% RSD), 21.1% (13% RSD), and 2.36% (42%RSD), respectively. The 499>99 and 499>130 transitions are significantly weaker in intensity when compared to the 499>80 transition. The higher variabilities observed for these two transitions in the solvent curve was largely due to very weak signals in the calibration standards less than 0.5 ng/mL in concentration. Calibration standards of 0.5 ng/mL and higher produced %RSD of approximately 8% for these two transitions. Figure 1 and Figure 2 display the average area percentages observed for each transition in the study samples. Flere, the plotted average and %RSD is the statistical calculations for sample, sample duplicate, and associated LMS. For viewing simplicity, the % RSD for 499>130 was excluded from the graphs as it was often larger than the area average and produced error bars that extended into the negative y-axis region making the graph difficult to read. From the figures, it is clear that the overall transition ratios observed in the solvent standard are conserved in the extracted samples and QC.
3M ENVIRONMENTAL LABORATORY
PAGE 15 OF 31
3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0053
Table 8. Sample and Lab Matrix Spike Results: PFOS and [iaOJPFOS surrogate.
3M UM SID
Sample Description Mass(g)
Cone. (ng/mL)
E09-0053-001 E09-0053-001 Dup E09-0053-001 LMS
MissR_pool2_WE_1
0.4799 0.4884 0.5032 Average
2.75 2.77 19.9
%RPD
E09-0053-002 E09-0053-002 Dup E09-0053-002 LMS
MissR_pool2_WE_2
0.5049 0 5212 0.5008 Average %RPD
4.64 4.52 18.9
E09-0053-003 E09-0053-003 Dup E09-0053-003 LMS
MissR_pool2_WE_3
0.5202 0.5056 0.5159 Average
8.77 828 24.4
%RPD
E09-0053-004 E09-0053-004 Dup E09 0053-004 LMS
MissR_pool2_WE_4
0.4822 0.4974 0.5163 Average
4.92 4.28 20.5
%RPD
E09-0053-005 E09-0053-005 Dup E09-0053-005 LMS
MissR_pool2_SAG_1
0.4871 0.4954 0.4781 Average
4.00 3.82 18.4
%RPD
E09-0053-006 E09-0053-006 Dup E09-0053-006 LMS
MissR_pool2_SAG_2
0.4808 0.5129 0.4891....... Average
4.20 4.45 183
%RPD
E09-0053-007 E09-0053-007 Dup E09-0053-007 LMS
MissR_pool2_SMB_1
0.5287 0.5257 0.4943 Average
. 6.08 5.30 22.9
%RPD
E09-0053-008 E09-0053-C08 Dup E09-0053-008 LMS
MissR_pool2_SMB_2
i S--------------------------------
0.4785 0.5163 0.5012 Average %RPD
p)36.3 p?39.7
PFOS
<1,Conc.
(ng/g)
28.7 28.4 198 28.5 1.0 45.9 43.4 189 44.7 5.8 84.3 81.9 236 83.1 2.9 51.0 43.0 199 47.0
17 41.1 38.6 192 39.8 6.3 43.7 43.4 187.... 43.5 0.68 57.5 50.4 232 54.0
13 pl379 p)384 p;8S4 a'382
1.4
[1sOJPFOS
Cone. %Rec (ng/mL)
Cone.
(ng/g)
NA 0.102
1.06
NA 0.108
1.11
112 0.126
1.25
Average %Recovery
%RSD
NA NA 95.0
0.107
1.06
0.104
1.00
0.122
1.22
Average %Recovery
%RSD
NA 0.108
1.04
NA 0.112
1.11
104 0.133
1.29
Average %Recovery
%RSD
NA 0.114
1.18
NA 0.105
1.06
103 0.115
1.11
Average %Recovery
%RSD
NA NA 96.1
NA NA 92.4
0.101
1.04
0.106
1.07
0.107
1.12
Average %Recovery
%RSD
0.0999
1.04
0.114
1.11
. 0 .11.1 . ....1.13 Average %Recovery
%RSD
NA NA 116
NA NA B)96.6
0.105
0.99
. 0.109
1.04
0.116
1 17
Average %Recovery
%RSD
p,0 130 p)0 .121
P)1.36 p)1.17
p,0.143
P,1 43
Average %Recovery
%RSD
%Rec
102 108 126 112 11 '.07 104 122 111 8.7 108 112
117 11 114 105 115 111 4.9 101 106 107 104 3.1 100 114 .... 111___ 108 6.9 105 109 116 110 5.1 ^130 121 142 50131 8.4
3M ENVIRONMENTAL LABORATORY
PAGE 16 OF 31
3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0053
Table 8 Continued.
3M UM SID E09-0053-009 E09-0053-009 Dup E09-0053-009 LMS
E09-0053-010 E09-0053-010 Dup E09-0053-010 LMS
E09-0053-011 E09-0053-011 Dup E09-0053-011 LMS
E09-C053-012 E09-0053-012 Dup E090053-012 LMS
E09-0053-013 E09-0053-013 Dup E09-0053-013 LMS
E09-0053-014 E09-0053-014 Dup E09-0053-014 LMS
E09-0053-015 E09-0053-015 Dup E09-0053-015 LMS
E09-0053-016 E09-0053-016 Dup E09-0053-016 LMS
Sample Description MissR_pool2_SMB_3 MissR_pool2_SMB_4 MissR_pool2_SMB_5 MissR_pool2_BKS_1 MissR_pool2_BGS_1 MissR_poo/2_BGS_2 MissR_pool2_BGS_3 MissR_pool2_BGS_4
Mass(g) 0.4963 0.4975 0.4784 Average %RPD 0.5107 0.4952 0.4839
Average YcRPD C 4926 0.4861 0 5148
Average %RPD 0.4749 05146 0.5028
Average %RPD 0.5058 04887 0.5147
Average %RPD 0.5237 0 4809 0 5201
Average %RPD 0.5118 0.5022 05098
Average %RPD 0.5024 0.5096 0.5124 Average %RPD
Cone. (ngfinQ
11.0 12.2 26.8
13.4 12.1 26.6
13.9 14.6 27.6
5.27 5 61 225
15.7 16.4 35.3
11.5 9.61 26.0
19.2 16.8 37.4
p>33,3 pl34.7 Pl83.7
i1
PFOS
<1>Conc.
111 123 280 117 10 131 122 275 127 7.1 141 150 268 140
6.2
55.5 54.5 224 55.0 1.8 155 168 343 161 7.8 110 100 250 105 9.4 188 167 367 177 11 p>331 p>340 *817 m336 2.7
NA NA 103
NA NA 94.4
NA NA 83.0
NA NA 112
NA NA 123
NA NA 99.3
NA NA 127
NA NA P)98.5
[iaOJPFOS
Cone. (ng/mL)
Cone.
(ng/g)
0.106
1.07
0.116
1.17
0.116
1.21
Average %Recovery
%RSD
0.119
1.17
0.102
1.03
0.124
1.28
Average `/Recover/
%RSD
0.114
1.16
0.120
1.23
0.122
1.18
Average "ARecovery
%RSD
0.0995
1.05
0.105
1.02
0.116
1.15
Average "/Recovery
%RSD
0.110
1.09
0.105
1.07
0.108
1.05
Average "ARecovery
%RSD
0.123
1.17
0.109
1.13
0.113
1.09
Average "ARecovery
%RSD
0.108
1.06
0.112
1.12
0.117
1.15
Average "ARecovery
%RSD
pl0.122
p,1.21
" O.H 8
p,1.16
P)0.163
P)1.59
Average "/Recovery
"ARSO
"/Ree 106 116 116 112 5.1 119 102 124 115 10 114 120 122 118 3.5 99.1 105 116 106 7.9 110 105 108 107 2.3 123 109 113 115 6.3 108 112 117 112 4.0 122 118
162 *134
19
3M ENVIRONMENTAL LABORATORY
PAGE 17 OF 31
3MENVIRONMENTAL LABORATORY REPORT NO. E09-0053
Table 8 Continued.
3M U M S I0 E09-0053-017 E09-0053-017 Dup E09-0053-017 LMS
Sample Description MissR_pool2_BGS_5
E09-0053-018 E09-0053-018 Dup E09-0053-018 LMS
MissR_pool3_WE_1
E09-0053-019 E09-0053-019 Dup E09-0053-019 LMS
MissR_pool3_WE_2
E09-0053-020 E09-0053-020 Dup E09-0053-020 LMS
MissR__pool3_WE_3
E09-0053-021 E09-0053-021 Dup E09-0053-021 LMS
MissR_pool3_.WE_4
E09-0053-022 E09-0053-022 Dup E 09-0053-022 LMS
MissR_pool3_WE_5
E09-0053-023 E 09-0053-023 Dup E09-0053-023 LMS
MissR_pool3._NOP_1
E09-0053-024 E09-0053-024 Dup E09-0053-024 LMS
MissR_pool3_SMB_1
Mess (g) 0.5005 0.5146 0.5052 Average %RPD 0.5021 0.5091 0.5168 Average %RPD 0.5233 0.5150 0.4892 Average %RPD 0.5075 0.5040 0.5172 Average %RPD 0.5093 0.5144 0.5168 Average %RPD 0.5152 0.4847 0.4779 Average %RPD 0.4741 0.5087 0.5024 Average %RPD 0 4791 0 5276 0.5115 Average %RPD
PFOS
[ `O J P F O S
Cone. (ngfmL)
<1>Conc. (ngigj
Cone. %Rec (ng/mL)
Cone. (n&9)
12.3
123
NA 0.116
1.16
12.4 120 NA 0.104 1.01
28.0
277
103 0.118
1.17
122 Average "/Recovery
2.0 %RSD
9.78 9.72 27.1
8.20 8.10 24.9
97,4 95.5 262 964 2.0 78.3 78.6 254 78.5 0.37
NA 0.102
1.02
NA 0.102
1.00
113 0 117
1.13
Average "/Recovery
%RSD
NA 0.115
1.10
NA 0.105
1.02
113 0.119
1.22
Average "/Recovery
%RSD
9.89 8.30 28.7
97.4 82.3 277 89.9
17
NA 0.130
1.28
NA 0.106
1.05
128 0.122... .........1.13 .....
Average %Recovery
%RSD
5.03
49.4
5.38 52.3
21.0 _____ 203
50.8
5.7
NA NA __104__
0110
1 08
0.100
0.972
0.105
1.02
Average "ARecovery
"ARSO
6.62 6.60 23.7
64.2 68.1 248 66.2 5.8
NA 0.100
0.970
NA 0.105
1.08
114 0.123
1.29
Average %Recovery
"ARSO
4.72 5.21 _ 217
49.8 51.2 216 50.5 2.8
NA NA ........ 109
0.108
1,14
0.108
1.06
01 32 __ 1.31
Average "/Recovery
"ARSO
2.83 3.15 18.2
29.5 29.9 178 29.7 1.1
NA 0.110
1.15
NA 0.102
0 967
100 0.114
1.11
Average "ARecovery
"ARSD
"/Ree
116 104 118 112 6.7 102 102 117 107 8.1 115 105 119 113 6.4 130 106 122 119 10 110 100 105 105 4.8 100 105 123 109
11 108 108 )3? 116 12 110 102 114 108 5.6
3M ENVIRONMENTAL LABORATORY
PAGE 18 OF 31
3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0053
Table 8 Continued.
3M UM S/D E09-0053-025 E 09-0053-025 Dup E09-0053-025 LMS
E09-0053-026 E09-0053-026 Dup E09-0053-026 LMS
E09-0053-027 E09-0053-027 Dup E09-0053-027 LMS
E09-0053-028 E09-0053-028 Dup E09-0053-028 LMS
E09-0053-029 E09-0053-029 Dup E09-0053-029 LMS
E09-0053-030 E09-0053-030 Dup E 09-0053-030 LMS
E09-0053-031 E09-0053-031 Dup E09-0053-031 LMS
E09-0053-032 E09-0053-032 Dup E09 0053-032 LMS
Sample Description MissR_pool3_SMB_2 MissR_pool3_SMB_3 MissR_pool3_SMB_4 MissR_pool3_SMB_5 MissR_pool3_BGS_1 MissR_pool3_BGS_2 MissR_pool3_BGS_3 MissR_pool3_BGS_4
Massfy)
0.4868 0.5146 0.5212 Average %RPD 0.5004 0.4942 0.4928 Average %RPD 0.4802 0.4978 0.5202 Average %RPD 0.5170 0.5016 0.5015 Average "ARPO 0.4922 U.5236 0.5289 Average %RPD 0.5234 0.5010 0.4780 Average %RPD 0.4868 0.5055 0.4815 Average %RPD 0.5164 0.4841 0.5015 Average %RPD
PFOS
Conc. (ngrinL)
10.0 11.1 25.9
f1>Conc. (ng/g)
103 108 248 105 4.9
4.88 4.77 200
6.05 666 20.2
48.8 48.3 203 48.5 1.0 63.0 66.9 194 64.9
6.0
5.69 5.35 20.6
7.55 762 21.3
55.0 53.3 205 54.2 3.1 76.7 72.8 201 74.7
5.3
16.8 16.5 283
160 165 296 163
13.4 12.9 258
26 138 128 268 133 7.6
23.0 21 2 34.5
223 219 344 221
1.7
%Rec NA NA 98.2
NA NA 100
NA NA 86.5
NA NA 100
NA NA 88.2
NA NA 840
NA NA 85.8
NA NA 81 3
fOJPFOS
Conc. (ngrinL)
Conc. (ng/g)
0.105
1.08
0.125
1.21
0.122
1.17
Average "/Recovery
"ARSD
0.108 0.105 0.12
1.08 1.06 1.22
Average "/Recovery ARSD
0.112
1.17
0.115
1.16
0.118
1.13
Average "/Recovery
%RSD
0.108 0.114
1.04 1.14
0.12
1.20
Average "ARecovery
"ARSD
0.113
1.15
0.0988
0.943
0.112
1.06
Average "ARecovery
"ARSD
0.104
0.994
0.115
1.15
0.122
1.28
Average %Recovery
`ARSO
0.119
1.22
0105
1.04
0.122
1.27
Average "ARecovery
"ARSD
0.105
1.02
0.115
1.19
0.124
1.24
Average "ARecovery
"ARSD
"ARec
105 125 122 117 9.2 108 105 120 111 7.2 112 115 118 115 2.6 108 114 120 114 5.3 113 98.4 112 108 7.3 104 115 122 113 8.0 119 105 122 115 7.9 105 115 124 114 8.3
3M ENVIRONMENTAL LABORATORY
PAGE 19 OF 31
3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0053
Table 8 Continued.
PFOS
f1BOJPFOS
3M UMS ID
Sample Description
Cone. Mass (g) (ng/mL)
!1>Conc. (ng/g)
Cone. %Rec (ng/mL)
Cone. (ng/g)
%Rec
E09-0053-033
MissR_pool3_BGS_5 0.5092
E09-0053-033 Dup
0.5071
E09-0053-033 LMS ..... ...... ............ .................. 0 4998
Average
12.8 13.5 26.0
126 NA 0 1 1 7 1.15 117
133 NA 0.121 1.19 121
260
86.0
0.120
1.20
120
129
Average "ARecovery
119
%RPD
5.7
%RSD
1.7
7 n Unless otherwise specified, the recovery of 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 10015% (PFOS). See Section 4.9 Determination o fAnalytical 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. (2) Surrogate recovery exceeded 10030% (3) Reported concentrations for these samples are from a 1:10 post-extraction dilution of the final extract. These two
samples were re-prepared and analyzed in Batch 4 with a ~500 ng/g LMS. The results from the original analysis were
not reported as the LMS concentration (-150 ng/g) was less than half the endogenous sample concentration and
consequently, the accuracy of the sample concentrations could not be assessed.
Figure 1. Area Percentages of Individual PFOS Transitions: Samples -001 through -018.
90.00
% 499> 130 % 499>99 % 499>80
3M ENVIRONMENTAL LABORATORY
PAGE 20 OF 31
3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0053
Figure 2. Area Percentages of Individual PFOS Transitions: Samples -019 through -033.
11 II r i m
11 11 m u
11 11 m u
o>
3 s 3 3 3 3 3mo i 3 3 390o3
LU
8 m9CO 8 do> LU
0r~4
mo 90OLU3
So i oCmoO 0OLU3
C0O4 9CnooO do> LU
COM' i9CfO)
o LU
i0n4 m9CO 0OU3J
C0O4 i9CoonO doLU>
ChM m9coo 90OLU3
C0O4
m ? 8LU
0CM3 ioo0OLnU3i
8 mo o LU
CO ion oLU
CCOMO Cmo^3 90o3 UJ
CCOO
m ?0o3 LU
CO
n(5X < 0) 3
o
ca>>
o
(/>
B499>130 499>99 499>80
The PFOS sample results presented In Table 1 and Table 8 are considered accurate within the overall method uncertainty of 10015%. When compared to the solvent standards used for quanitation, area count ratios of the individual PFOS transitions (499>80, 499>99, and 499>130) were conserved in extracted samples. The accuracy (% recovery) and precision (% RSD) of 3M EOF (branched) PFOS laboratory control spikes quantitated against the predominantly linear reference standard demonstrated that the isomers produce no discernable quantitative bias.
Results for remaining target analytes will be in a phase II report.
[1] J. P. Benskin, M. Bataineh, J.W. Martin, Simultaneous Characterization of Perfluoroalkyl Carboxylate, Sulfonate, and Sulfonamide Isomers by Liquid Chrom atography-Tandem Mass Spectrometry, Anal. Chem. 79 (2007) 6455-6464.
3M ENVIRONMENTAL LABORATORY
PAGE 21 OF 31
3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0053
All remaining sample and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures
9.1 3M Environmental Laboratory
Michelle D. Malinsky, Ph.D
Research Specialist
9.2 Pace Lab Ops
Jonathan Steege Lab Analyst II
3M ENVIRONMENTAL LABORATORY
PAGE P.2 OF 31
I
p. 24
3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0053
--.-..i*..*....
icialist, Principal Analytical Investigator Date
William K. Reagen, Ph.D,, Environmental Laboratory Management
Date
Cliffton a. Jaooby
M Technical Reviewer
/ & j 2*7^9
Date
The 3M Environmental Laboratory's Quality Assuranoe Unit has audited the data and report for this project.
QAI R epresenive
9 - / - ><7
Date
3M ENVIRONMENTAL LABORATORY
PAGE 23 OF 31
3M ENVIRONMENTAL LABORATORY REPORT NO. 0 9-00 53
11.1 Solvent/Matrix-Matched Extracted Calibration Curve Equivalency
Extracted Matrix Curve. Preo Batch 1. Analysis Date: 02/207009
Sample ID
Sample Decriphon
Extracted Mass (g)
mCorrected Standard Cone. (ng/mL)
PFOS
Calc. Cone. (ng/mL)
% Recovery
Standard Cone. (ng/mL)
090220 BG fillet Extracted Curve Point 1
0.25 ng/g curve point
0.4903
0.0829
0.0720
86.9
0.0253
090220 BG fillet Extracted Curve Point 2
0.35 ng/g curve point
0.4918
0.0929
0.0926
100
0.0353
090220 BG.fillet Extracted Curve Point 3
0.5 ng/g curve point
0.5022
0.111
0.106
95.6
0.0522
090220 BG fillet Extracted Curve Point 4
1 ng/g curve point
0.5201
0.161
0.154
958
0.100
090220 BG fillet Extracted Curve Point 5
2.5 ng/g curve point
0.5024
0.310
0.319
103
0.253
090220 BG fillet Extracted Curve Point 6
5 ng/g curve point
0.5039
0576
0.605
105
0.522
090220 BG fillet Extracted Curve Point 7
10 ng'g curve point
0.5088
1.05
1.16
110
1.00
090220 BG fillet Extracted Curve Point 8
15 ng/g curve point
0.4853
1.57
1.60
102
1.53
090220 BG fillet Extracted Curve Point 9
25 ng/g curve point
0.4873
2.57
2.71
106 2 5 3
(1) Average endogenous concentration as determined by quantitation of the matrix blanks using solvent curve quantitation = 0.589 ng/g (RPD= 0.57%).
f'O J P F O S
Calc. Cone. (ng/mL)
0.0195 0.0365 0.0551 0.107 0.256 0.591
1.18 1.69 2.53
% Recovery
771 103 106 107 101 113 118 111 99.9
Extracted Matrix Curve. Prep Batch 2, Analysis Date: 02/23/2009
Sample ID
Sample Decriphon
Extracted Mass (g)
<r`Corrected Standard Cone. (ng/mL)
PFOS
Calc. Cone. (ng/mL)
% Recovery
Standard Cone. (ng/mL)
090223 BG filler Extracted Curve Poini 1
0.25 ng/g curve point
0.4791
0.0744
0.0830
112
0.0253
090223 BG fillet Extracted Curve Point 2
0.35 ng/g curve point
0.4878
0.0852
C 0894
105
0.0353
090223 BG fillet Extracted Curve Point 3
0.5 ng/g curve point
0.5148
0.105
0.105
100 0.0522
090223 BG fillet Extracted Curve Point 4
1 ng/g curve point
0.5036
0.151
0.152
100
0.100
090223 BG fillet Extracted Curve Point 5
2.5 ng/g curve point
0.5135
0.304
0.297
97.7
0253
090223 BG fillet Extracted Curve Point 6
5 ng/g curve point
0.4782
0.566
0.622
110
0.522
090223 BG fillet Extracted Curve Point 7
10 ng/g curve point
0.5116
1,05
1.15
110
1.00
090223 BG fillet Extracted Curve Point 8
15 ng/g curve point
0.4986
1.56
1.75
112
1.53
090223 BG fillet Extracted Curve Point 9
25 ng/g curve point
0.5233
2.56
2.79
109
2.53
f1) Average endogenous concentration as determined by quantitation of the matrix blanks by solvent curve quantitation = 0.515 ng/g (RPD - 1.7%).
f 'OJPFOS
Calc. Cone. (ng/mL)
0.0238 0.0359 0.0487 0.0952 0.237 0.568
1.00 1 59 2.37
% Recovery
94.0 102 93.2 95.2 93.6 109 100 104 93.6
3M ENVIRONMENTAL LABORATORY
PAGE 24 OF 31
p. 25
3M ENVIRONMENTAL LABORATORY REPORT NO. E09-0053
Extracted Matrix Curve. Preo Batch 3. Analysis Date: 02/25/2009
PFOS
Sample ID
Sample Decription
Extracted Mass (g)
mCorrected Spike Cone.
(ng/mU
Calc. Cone. (ng/mL)
% Recovery
Spike Cone. (v W
090225 BG fillet Extracted Curve Point 1 0.25 ng/g curve point
0.5253
0.0847
0.0817
96.5
0.0253
090225 BG fillet Extracted Curve Point 2 0 35 ng/g curve point
0.5141
0.0933
0.102
109 0.0353
090225 BG fillet Extracted Curve Point 3
0.5 ng/g curve point
0.4962
0.108
0.113
105 0.0522
090225 BG fillet Extracted Curve Point 4
1 ng/g curve point
0.5119
0.158
0.159
101
0.100
090225 BG fillet Extracted Curve Point 5
2.5 ng/g curve point
0.5159
0.309
0.332
107
0.253
090225 BG fillet Extracted Curve Point 6
5 ng/g curve point
0.5231
0.576
0.608
106
0522
090225 BG fillet Extracted Curve Point 7
10 ng/g cuive point
0.5265
1.05
1.14
108
1.00
090225 BG fillet Extracted Curve Point 8
15 ng/g curve point
0.4783
1.56
1.78
114
1.53
090225 BG fillet Extracted Curve Point 9
25 ng/g curve point
0.4785
2.56
2.90
113
2.53
(1) Average endogenous concentration as determined by quantitation of the matrix blanks by solvent curve quantitation = 0 567 ng/g (RPD = 2.8%)
f'O J P F O S
Calc. Cone. (ng/mL)
0.0216 0.0348 00557 0.106 0.267 0 583
1.00 1.60 2.41
% Recovery
85.2 98.6 107 106 105 112 100 105 95.1
Extracted Matrix Curve, Prep Batch 4, Analysis Date: 03/06/2009
PFOS
f'O J P F O S
Sample ID
Sample Decription
Extracted Mass(g)
mCorrected Spike Cone.
(ng/mL)
Calc. Cone (ng/mL)
% Recovery
Spike Cone. (ng/mL)
Calc. Cone. (ng/mL)
% Recovery
090306 BG fillet Extracted Curve Point 1 0.25 ng/g curve point
0.5067
0.0807
0.0859
106
0.0253
0.0223
88.3
090306 BG fillet Extracted Curve Point 2 0.35 ng/g curve point
0.4898
0.0887
00905
102
0.0353
0.0326
92.3
090306 BG fillet Extracted Curve Point 3 0.5 ng/g curve point
0.4852
0.105
0.111
106
0.0522
0.0587
112
090306 BG fillet Extracted Curve Point 4 1 ng/g curve point
0.5124
0.156
0.152
97.6
0.100
0.100
100
090306 BG fillet Extracted Curve Point 5 2.5 ng/g curve point
0.4998
0.306
0.298
97.4
0.253
0.257
102
090306 BG fillet Extracted Curve Point 6 5 ng/g curve point
0.4934
0.571
0.66
116
0.522
0.575
110
090306 BG fillet Extracted Curve Point 7 10 ng/g curve point
0.4948
1.05
1.13
108
1.00
1.02
102
090306 BG fillet Extracted Curve Point 8 15 ng/g curve point
0.5037
1.57
1.74
111
1.53 1.64
107
090306 BG fillet Extracted Curve Point 9 25 ng/g curve point
0.5182
2.57
2.87
112
2.53
2.67
106
(1) Average endogenous concentration as determined by quantitation of the matrix blanks by solvent curve quantitation = 0.548 ng/g (RPD =
5.0%).
3M ENVIRONMENTAL LABORATORY
PAGE 25 OF 31
U ro o>
3M ENVIRONMENTAL LABORA TORY REPORT NO. 0 9-00 53
11.2 Surrogate Recoveries in Spiked Blanks.
Table 9. Surrogate Recoveries in Spiked Blanks.
Prep Batch 1, Analysis Date: 02/20/2009
Sample ID
Matrix Blank-1 (with IS/surr) 090220 Matrix Blank-2 (with IS/surr) 090220 Aqueous Blank-1 (with IS/surr) 090220 Aqueous Blank-2 (with IS/surr) 090220 ACN Blank with IS/surr ACN Blank with IS/sun Prep Batch 2. Analysis Date: 02/23/2009
Sample Description
Method Blank (BG fillet) Method Blank (BG fillet) Aqueous Blank Aqueous Blank (1>08 007-62 <1>08 007-62
Sample ID
Matrix Blank-1 (with IS/surr) 090223 Matrix Blank-2 (with IS/surr) 090223 Aqueous Blank-1 (with IS/surr) 090223 Aqueous Blank-2 (with IS/surr) 090223 ACN Blank -with IS/surr ACN Blank with IS/surr Prep Batch 3, Analysis Date: 02/25/2009
Sample Description
Method Blank (BG fillet) Method Blank (BG fillet) Aqueous Blank Aqueous Blank (1,08 007-62 l1)08 007-62
Sample ID Matrix Blank-1 (with IS/surr) 090225 Matrix Blank-2 (with IS/surr) 090225 Aqueous Blank-1 (with IS/surr) 090225
j| Aqueous Blank-2 (with IS/surT) 090225 ACN Blank with lS/sun | ACN Blank 'with IS/surr
Sample Description
Method Blank (BG fillet) Method Blank (BG fille*) Aqueous Blank Aqueous Blank '"08 007-62 (1)08 007-62
Area Counts 66130 62887 69115 64501 158329 147907
Area Counts 68808 69717 67533 56872 135129 135207
Area Counts 71175 73840 65016 64033 153699 151127
f'O J P F O S
Spike Cone. (ng/mL)
Calc. Cone. (ng/mL)
0.100 0.100 0.100 0.100
NA NA
0.109 0.107 0.116 0.0991
N/A NA
( " OJPFOS
Spike Cone. (ng/mL}
Calc. Cone. (ng/mL)
0.100 0.100 0.100 0.100
0.100 0.103 0.116 0.0908
NA N/A NA NA
t'O J P F O S
Spike Cone. (ng/mL)
Calc. Cone. (ng/mL)
0.100
0.113
0.100 0.100
0.109 0107
0.100 NA
0.102 NA
NA NA
%Rec 109 107 116 99.1 NA NA
%Rec 100 103 116 90.8 NA NA
%Rec 113 109 107 102 NA NA
p. 27
3M ENVIRONMENTAL LABORATORY
PAGE 26 OF 31
3M ENVIRONMENTAL LABORA TORY REPORT NO. E9-0053
Table 9 Continued.
Preo Batch 4. Analysis Data: 03/06/2009
f ' OJPFOS
Sample ID
Matrix Blank-1 (with IS/surT) 090306 Matrix Blank-2 (with IS/surr) 090306 Aqueous Blank-1 (with IS/surr) 090306 Aqueous Blank-2 (with IS/surr) 090306 ACN Blank with IS/surr ACN Blank with IS/surr
Sample Description
Method Blank (BG fillet) Method Blank (BG fillet) Aqueous Blank Aqueous Blank <'>08 007-62 o>08 007-62
Area Counts
93301 93408 90119 87716 198454 190408
Spike Cone. <nq/mL)
0.100 0.100 0.100 0.100
NA NA
Calc. Cone. (ng*"L) _
0.101 0.108 0.105 0.102
NA NA
%Rec
101 108 105 102 NA NA
I t ) Standard 0 8-007-62 was prepared using the sam e acetonitrile used for extraction procedure; however, the IS/surrogate w as mispnepared. Essentially, the surrogate w as spiked twice, and the IS was not spiked. Therefore, no concentrations and recoveries could be calculated.
p. 28
3M ENVIRONMENTAL LABORATORY
PAGE 27 OF 31
3MENVIRONMENTAL LABORATORY REPORT NO. E09-0053
11.3 Lab Control Spike Results.
Table 10. LCS Results Prep Batch 1
Preo Batch 1, Analysis Date: 02/20/2009
PFOS
("OJPFOS
Sample ID
Sample Decryption
Extracted Mass (g)
<vCorrected Spike Cone.
(ng/mL)
Calc. Cone. (ng/mL)
Spike Cone.
% Recovery
(ng/mL)
Calc. Cone. (ng/mL)
% Recovery
090220 LCS Low 1
0.5 ng/g LCS
0.4851
0.109
0.108
99.2
0.100
0.114
114
090220 LCS Low 2
0.5 ng/g LCS
0.4893
0.109
0.105
960
0.100
0.108
108
090220 LCS Low 3
0.5 ng/g LCS
0.4981
0,110
0.106
96 0
0.100
0.106
106
090220 LCS Mid 1
1.5 ng/g LCS
0.4791
0.207
0.200
96.4
0.100
0.105
105
090220 LCS Mid 2
1.5 ng/g LCS
0.5101
0.211
0.220
104
0.100
0 104
104
0S0220 LCS Mid 3
1.5 ng/g L.CS
0.5028
0.210
0 205
97.5
0.100
0.108
108
090220 LCS High 1 090220 LCS High 2
8 ng/g LCS 8 ng/g LCS
0.5202 0.4921
0.857 0.854
0.831 0.832
96.9 97 4
0.100 0.100
0.103 0.0906
103 90.6
090220 LCS High 3
8 ng/g LCS
0.4811
0.853
0.940
110
0.100
0.116
116
ECF LCS High 1
5 ng/g ECF LCS
0.4748
0.554
0.556
100
0.100
0.101
101
ECF LCS High 2
5 ng/g ECF LCS
0.5239
0.560
0.546
97,5
0.0974
97 4
ECF LCS High 3
5 ng/g ECF LCS
0.5132
0.558
0.728
130
0.100
0.116
116
Average %RSD
102%10%
106%7.1%
(1) Spiked sample concentration corrected for the average endogenous concentration as determined by quarritaSon of the batch's matrix blanks using solvent cuive quantitation.
Endogenous PFOS = 0.589 ng/g (RPD= 0.57%).
p. 29
o o d
3M ENVIRONMENTAL LABORATORY
PAGE 28 OF 31
3M ENVIRONMENTAL LABORATORY REPORT NO. 09-0053
Table 11. LCS Results Prep Batch 2
Preo Batch 2 Analysis Date: 02/23/2009
Sample ID
Sample Decryption
090223 LCS Low 1
0.5 ng/g LCS
090223 LCS Low 2
0.5 ng/g LCS
090223 LCS Low 3
0.5 ng/g LCS
090223 LCS Mid 1
1.5 ng/g LCS
090223 LCS Mid 2
1.5 ng/g LCS
090223 LCS Mid 3
1.5 ng/g L.CS
090223 l CS High 1
8 ng/g LCS
090223 LCS High 2
8 ng/g LCS
090223 LCS High 3
8 ng/g LCS
ECF LCS High 1
5 ng/g ECF LCS
ECF LCS High 2
5 ng/g ECF LCS
ECF LCS High 3
5 nq/g ECF LCS
Average 1 %RSD
1( ) Endogenous PFOS = 0.515 ng/g (RPD= 1.7%).
Extracted Mass (g)
0.5299 0.5109 0.5079 04975 0.5199 0.5044 0.4844 0.5215 05188 0.5019 0.5017 0.5009
01Corrected Spike Cone.
(ng/mL)
0.105 0.103 0.103 0.201 0.204 0.202 0.845 0.849 0.848 0.549 0.549 0.549
PFOS
Calc. Cone (ng/mL)
0.106 0.116 0.103 0.212 0.217 0.213 0.806 0.833 0.895 0.558 0.553 0.635 104%5.6%
% Recovery
101 112 99.9 105 107 105 95.4 98.1 105 102 101 116
Spike Cone. (ng/mL)
0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100
OJPFOS
Calc. Cone. (ng/mL)
% Recovery
0.0948 0.113 0.102 0.113 0111 0.108 0.0953 0.103 0.0986 0.105 0.0985 0.110 104%6.4%
94.8 113 102 113 111 108 95.3 103 98.6 105 98.5 110
p. 30
3M ENVIRONMENTAL LABORATORY
PAGE 29 OF 31
3M ENVIRONMENTAL LABORA TORY REPORT NO. 09-0053
Table 12. LOS Results Prep Batch 3
Prep Batch 3. Analysis Date: 02/25/2009
Sample ID
090225 LCS Low I 090225 LCS Low 2 090225 LCS Low 3 090225 LCS Mid 1 090225 LCS Mid 2 090225 LCS Mid 3 090225 LCS High 1 090225 LCS High 2 090225 LCS High 3 ECF LCS High 1 F.CF IC S High 2 ECF LCS High 3
Sample Decryption
0.5 ng/g LCS 0.5 ng/g LCS 0 5 ng/g LCS 1.5 ng/g LCS 1.5 ng/g LCS 1.5 ng/g LCS 8 ng/g LCS 8 ng/g LCS 8 ng/g LCS 5 ng/g ECF LCS 5 ng/g ECF LCS 5 ng/g ECF LCS Average %RSD
Extracted Mass (g)
0.5271 0.4908 0.4871 0.4926 0.5105 0.4982 0.4814 0.5146 0.5257 0.4944 0.5284 0.5157
(vCorrected Spike Cone.
(ng/mL)
0.111 0.107 0.107 0.207 0.209 0.207 0.851 0.854 0.856 0.554 0 558 0.556
PFOS
Calc. Cone. (ng/mL)
0.114 0.113 0.105 0.238 0.251 0.210 0.842 0.928 0.871 0.635 0.601 0 599 107%6.5%
% Recovery
102 105 98.2 115 120 101 99.0 109 102 115 108 108
Spike Cone. (ng/mL)
0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0100
C'OJPFOS
Calc. Cone. (ng/mL)
0.112 0.106 0.110 0.134 0.115 0.111 0100 0.114 0.105 0. 14 0.104 0.112 111%7.6%
% Recovery
112 106 110 134 115 111 100 114 105 114 104 112
(1) Spiked sample concentration corrected for the average endogenous concentration as determined by quantitation of the batch's matrix blanks using solvent curve quantitation Endogenous PFOS = 0.567 ng/g (RPD= 2.8%).
p. 31
3M ENVIRONMENTAL LABORATORY
PAGE 30 OF 31
3M ENVIRONMENTAL LABORATORY REPORT NO. 09-0053
Table 13. LCS Results Prep Batch 4.
Prep Batch 4, Analysis Date: 03/06/2009
Sample ID
Sample Decryption
090306 LCS Low 1 090306 LCS Low 2 090306 LCS Low 3 090306 LCS Mid 1 090306 LCS Mid 2 090306 LCS Mid 3 090306 LCS High 1 090306 LCS High 2 090306 LCS High 3 ECF LCS High 1 ECF LCS High 2 ECF LCS High 3
0.5 ng/g LCS 0.5 ng/g LCS 0.5 ng/g LCS 1.5 ng/g LCS 1.5 ng/g LCS 1.5 ng/g LCS 8 ng/g LCS 8 ng/g LCS 8 ng/g LCS 5 ng/g ECF LCS 5 ng/g ECF LCS 5 nq/g ECF LCS Average i %RSD
Extracted Mass (g)
0.5095 0.4898 0.5065 0.5000 0.5211 0.5079 0.5028 0.4853 . 0.5079 0.5028 0.5189 0.5299
n Corrected Spike Cone.
(ng/mL)
0108 0.105 0.107 0.206 0.208 0.207 0.851 0.849 0.852 0.553 0.555 0.556
PFOS
Calc. Cone. (ng/mL)
0110 0.105 0.104 0.217 0 223 0.205 0.910 0956 0.943 0.636 0,636 0.627 107%5.9%
% Recovery
102 100 97.0 105 107 99.2 107 113 111 115 115 113.
Spike Cone. (ng/mL)
0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0 .1.00 0.100
("OJPFOS
Cale. Conc. (ng/mL)
0.106 0.109 0.106 0.110 0.109 0.108 0.113 : 0.111 0.104 0,113 0.109 0.111 109%Z5%
% Recovery
106 109 106 110 109 108 113 114 104 113 109 111
aVera9C end09en USconoentration ^ determined by quantitation of the batch's matrix blanks using solvent curve quantitation.
p. 32
3M ENVIRONMENTAL LABORATORY
PAGE 31 OF 31
