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3M EtWIRONMENTAL LABORATORY PROJECT NO.E05-O442
Analytical Report
Definitive Study: Quantitative Screening of Commercial Lots of Human Serum Obtained in 2004 for Endogenous Fluorochemicals Using Solid Phase Extraction and Liquid Chromatography/Tandem Mass Spectrometry
Laboratory Request Num ber E05-0442
Testing Laboratory
3M Environmental Health and Safety Operations 3M Environmental Laboratory
3M Environmental Laboratory
Project Lead Mark E. Ellefson Building 2-3E-09 PO Box 33331 Saint Paul, MN 55133-3331 Phone: 651-778-5405
Testing Facility Management William K. Reagen, Ph.D. Building 2-3E-09 PO Box 33331
Saint Paul, MN 55133-3331 Phone: 651-778-6565
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Requestor
Dale Bacon Building 2-3E-09 PO Box 33331 Saint Paul, MN 55133-3331 Phone: 651-778-4736
Page 1 of 19
3M ENVIRONMENTAL LABORATORY PROJECT NO.EQS-0442
3M Environmental Laboratory
Analytical Report Project Number: E05-0442
1 Introduction / Summary
The following analytical report presents data from com m ercially available normal pooled human serum that ware purchased by the 3M Environmental Laboratory and subsequently screened for endogenous fluorochemicals. Thirty-six separate lots o f pooled normal human serum were extracted using a solid phase extraction technique and screened for sixteen different fluorochem icals using liquid chromatography/tandem mass spectrometry (LC/MS/MS). Serum samples were received from various suppliers between 9/9/04 and 12/2/04. Samples were extracted on 5/11 /2005 and analyzed 5/23/2005. H eptafluorobutyric acid (PFBA) was included in the original list o f sixteen target analytes. However, due to instability in the methanol extract, analytical data for PFBA w ill not be included in this report. Instead, a separate study w ill be conducted including the re-extraction o f the thirty-six lots o f commercial serum w ith acetonitrile and analysis using a newly developed method that provides isomer resolution. Those results w ill be reported in a separate report. Sample results are summarized in Tables 1 and 2. The average values reported represent samples in w hich there was detectable analyte. Sample values that were less than the lim it o f quantitation were not included in the average value calculations. Please refer to Section 5 for individual sample results.
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3M ENVIRONMENTAL LABORATORY PROJECT NO.05-0442
Tab! 1. Summary of Perfluorinated Acid Results
Analyte
Mean
Median High Low
Standard Deviation Number of Samples with
Detectable Analyte
NFPA PFHA TDHA PFOA (ng/mL) (ng/mL) (ng/mL) (ng/mL)
C9 Acid (ng/mL)
CIO ACID (ng/mL)
C11 ACID
ing/niy
C12 ACID (ng/mL)
1.04 '0:01 tV 0.151' 2.98 0.813
0.282 0.185 0.0246
1.05 2.11 0.327 0.378
0.00838 0.0323 0.00633 0.00822
0.118 0.474 0.0232 0.111
321 5.72 0.359 1.27
0.737 1.97 0.0950 0.445
0.281 0.599 0.0274 0.137
0,134 0.734 0.0152 0.176
0.0197 0.0833 0.0108 0.0149
36/36 9/36 33/36 36/36 j 36/36
36/36 36/36 30m
Table 2. Summary of Other Perfluorinated and Highly Fluorinated Analyte Results
Analyte
Mean Median
High Low
Standard Deviation
Number of Samples with Detectable Analyte
FBSA (ng/mL)
NA1 NA' 0.00542 0.00542
NA1
FOSA (ng/mL)
0.149 0.124 0.446
0.0378
0.0876
1/36 36/36
PFBS (ng/mL) 0.0165 0.0101
0.0840
0.00545
PFHS PFOS THPFOS THPFDS (ng/mL) in g im L ) (ng/mL) (ng/mL)
2.55
14.9 i NA3
0.0442
2.85 15.5 NA3 0.0366
4 18 27.0
NA3 0.126
0.606 2.03
NA2 0.00772
0.0169 1.07 5.94
NA2 0.0227
33/36 36/38 36/36 0/36 38/36
NA2 = Not Applicable because this analyte w as not detected in any of the sam ples.
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3M ENVIRONMENTAL LABORATORY PROJECT NQ.E05-0442
2 Reference Substances
Table 3. Reference Substances
Name Nonafluoropentancic acid
Synonym or Acronym
NFPA (C5 Acid)
Standard Source Material
Vendor
Traceability Number
Purity *
Aldrich
TCR-333 (00017-045) 96.5%
Additional Correction Factor (K* salt or H*}
0.996
Periluorohexanoic acid
PFHA (C6 Acid) Oakwood Products
TCR-673
97.7%
0.997
Tridecafiuoroheptanoic acid TDHA (C7 Acid)
Aldrich
TCR-267
98.2%
0.997
Perfluorooctanoic acid
PFOA (C8 Acid)
3M
TCR-123 (99030-030) 95.0%
0.958
Hcptadecafluorononanoic acid
CO Acid
Oakwood Products
TCR-618
98.0%
0.998
Nonadecafluorodecanoic acid
CIO Acid
Oakwood Products
TCR-36
98.01%
0.998
Periluorouitdecanoic acid
Cl 1Acid
Oakwood Products
TCR-619
96.4%
0.998
Perfluorododecanoic acid
Cl 2 Acid
Oakwood Products
TCR-37 (SD037)
99.65%
0.998
Perfluorobutancsulfonamide
FBSA
3M
TCR-314 (00017-026) unknown
None
Perfluorooctanesulfonamide
FOSA
3M
TCR-280 (99131-038) 98.94%
None
Perfluorobatane sulfonate
PFBS
3M
TCR-l 16 (99030-023) 96.7%
0.8844
Pcrftuorohcxane sulfonate
PFHS
3M
TCR-83 (SE036)
98.6%
0.911
Perfluorooctane sulfonate
PFOS
3M
TCR-696
86.4%
1H, 1H, 211,2H, pcrfluorooctanesulfcnic acid
THPFOS
SynQuest Labs TCR-343 (00017-055) 93.5%
IK, 1H, 2H, 2H, perfluorodecane sulfonate
THPFDS
Paee/3M
TCR-627
94.7%
Perfluorooctanoic acid, isotopically labeled
PFOA [l,2-'JC)
Perkin F.lmer
TCR-744
>97%
Perfluorooctane sulfonate, ammonium salt, isotopically
labeled
PFOS ["OtJ
RTI Internationa]
TCR-756
100 ug/mL Standard
* Reference substance purities have not been corrected for impurities due to shorter chain hornotogoes which cannot be
distinguished by NMR analysis.
0.927 0.998 0.998 None
None .
NMR results indicate that the PFOS reference substance consists o f 30.8% branched isomer, and the PFOA reference substance consists o f 22.1% branched isomer. These values were used for the determ ination o f the isomer ratios in the serum samples (presented in Table 10).
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3M ENVIRONMENTAL LABORATORY PROJECT NO. E06-0442
3 Sample Preparation
The samples for this study were prepared as follows:
1. The serum samples were allowed to thaw and warm to room tem perature.
2. Four m illiliters o f serum (or w ater in the case o f method blanks) w ere added to a 15 mL screw-capped polypropylene centrifuge tube.
3. M atrix spikes and method blanks were prepared by spiking the serum (or w ater) w ith the analytes o f interest. In addition, l3C PFOA and 18Q j PFOS were added as surrogates to all serum samples, calibration standards, m atrix blanks, and method blanks at concentrations o f 1.04 and 0.950 ng/m L serum respectively to evaluate extraction method performance.
4. Ten m illiliters o f acetonitrile were added to the serum and the centrifuge tubes were capped and vortex mixed, allowing the serum proteins to precipitate.
5. The tubes were centrifuged at approxim ately 3500 rpm for 20 m inutes to pellet the precipitate.
6. A fter rem oval from the centrifuge, the supernatant was transferred to a bottle containing 70 mL o f water.
7. Th sam ples were passed through a preconditioned SPE cartridge and eluted w ith 2 mL o f methanol.
Q uantitation was accomplished using high performance liquid chromatography tandem mass spectrom etry. The following param eters ware used:
L iquid C h rom atograph: Hewlett-Packard Series 1100 Liquid Chromatograph
s y ste m
Analytical column: Keystone BetasilTM Cu 2.1x100mm, 5pm particle size Column tem perature: 30 "C Stop Time: 20.0 m inutes Flow rate: 300 pL/min Injection volume: 5 pL M obile phase components: Solvent A: 2.0 mM ammonium acetate in ASTM Type I w ater Solvent B: HPLC Grade M ethanol Solvent Gradient:
Urns
0.00 1.00
14.50
15.50 16.50
20.00
20% 20% 90% 90% 20% 20%
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3M ENVIRONMENTAL LABORATORY PROJECT NO.05-0442
M ass Spectrom eter: MDX Sciex API 4000 Q-Trap Mass Spectrom eter D etector Software: A nalyst TMVersion 1.4 Ionization M ode: Electrospray Negative Temperature: 450 C GS1: 35 GS2: 45 Entrance Potential: -10 Analysis Type: M ultiple Reaction M onitoring (MRM)
Table 4. Acquisition Parameters
Comoound
NFPA (Cs Acid) PFHA (Ce Acid) TDHA(CrAcid) PFOA (CeAcid)
Ce Acid C10Add Cn Acid C12Add
FBSA FOSA PFBS PFHS PFOS THPFOS THPFDS P F 0A [1 2-iaC] PFos ro d
Q1 Mass (amu)
262.9 313.0 362.9 413.0 463.0 5129 563.0 613.0 297.9 497.9 298.9 398.9 498.9 426.9 526.9 414.9 503.0
Q3 Mass (annul
219.0 268.7,118.9 318.7,168.8,118.9 360.9,219.0,169.C 418.7,168.9,218.9 468.8, 218.9,269.1 518.7,268.9,218S 568.7,168.9,318.7
78.0 77.9 98.9,79.9 98.9,80.0 80.0,98.9,130.0 40&8.80.9 50a7,81.0 369.8 103.0, 84.0
Declusterina Potential
-30 -45 -35 -45 45 -35 -45 -50 -55 -90 -65 -95 -120 -70 -70 -40 -100
W hen m ultiple transitions were monitored, the total ion current (TIC) was used to quantify each analyte, thereby providing greater sensitivity than individual Q3 ion m easurem ents.
4 Analysis
4.1 C alibration
4.1.1 Calibration Curve An extracted calibration curve was formed by spiking rabbit serum at prescribed levels and extracting the curve in the same manner as the samples. Stock solutions were individually prepared from neat flucrrochemicals and diluted in methanol. Samples were quantified versus a 15-point extracted calibration curve.
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3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0442
The regression analysis was performed using a quadratic curve fit weighted 1/x. Calibration standards were within 25% {30% for the Lower Limit o f Quantitation (LLOQ)) with a coefficient o f determination >0.990. Low-level calibration standards which were not within 30% were not included in the calibration curve. Calibration standards that were not greater than 2x the method blanks were not included in the calibration curve, except where noted.
4.1.2 Continuing Calibration Verification (CCV)
A Continuing Calibration Verification (CCV) was run at least once every 10 samples, bracketing the samples with the calibration curve. The CCV recovery was within 25% for all analytes.
4.1.3 System Suitability
Five system suitability standards were analyzed before the initial calibration curve and after the last CCV. These samples had area counts with a %RSD o f <5% and a retention time %RSD o f<2% when evaluated independently except for the following instances:
The system suitability samples for each o f the perfluorinated acids and FOSA failed. In each case the %RSD o f the retention times was well within tolerance limits, but the area counts varied by as much as 20.3%. The; failure o f every perfluorinated acid tested suggests the presence o f a systematic effect on that class o f analytes. This should be kept in mind when evaluating the data presented in this report.
4.1A Lower Lim it o f Quantitation (LLOQ)
The LLOQ for each analyte was equal to the nominal concentration o f the lowest standard in the calibration curve that met accuracy requirements o f 70% -130% and that had at least twice as many area counts as the method blanks.
4.2 Blanks
4.2.1 M ethod Blanks
M ethod blanks consisted o f aliquots o f Milli-Q water extracted in the same manner as foe samples. All o f foe method blanks in this study had area counts < 50% o f die LLOQ for their respective analytes with the following exceptions:
PFHA: Two out o f three method blanks was greater than 50% o f the LLOQ; none were above the LLOQ.
C7 Acid: One o f three method blanks had area counts greater than 50% o f the LLOQ; none were above the LLOQ.
C l 1 Acid: One o f three method blanks had area counts greater than 50% o f the LLOQ; none were above the LLOQ
FOSA* Two out o f three method blanks were greater than 50% o f the LLOQ; none were above the LLOQ.
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3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0442
PFBS: Two method blanks had area counts greater than 50% o f the LLOQ; one showed anomalous contamination and was above the LLQQ.
4 2 2 M atrix Blanks
Matrix blanks consisted o f aliquots o f blank rabbit serum extracted in the same manner as the samples. Three matrix blanks were prepared and analyzed with the samples. Matrix blanks containing endogenous levels o f analyte that were above the LLOQ are detailed below.
Table 5. Endogenous Analyte in Rabbit Serum
Sample ID
TDHA
C11 ACID
PFBS
THPFOS
THPFDS
LLOQ (ng/mL)
0.00504
0.00992
0.00506
0.00520
0.00503
MxBIk 050511-1
0.0065
0.0196
0.00941
0.0260*
0.0146
MxBIk 050511-2
0,00252*
0.0138
0.00729
0.0260*
0.0131
MxBlk_050511-3
0.0102
0.0169
0.00774
0.0249
0.0137
Average
0.00641
0.0188
0.00815
0.0256
0.0138
"Please refer to the note to file included in the raw data describing the calculation o f the endogenous levels.
The average endogenous values were used to correct the matrix spike response.
4 1 3 Solvent Blanks
Methanol blanks were analyzed throughout the analytical run. Analyte response was less than Vt the LLOQ in all cases.
Surrogate
PFOA [1,2-13C] and PFOS [18Oz] were added as surrogates to all serum samples, calibration standards, m atrix blanks, and method blanks to evaluate the extraction m ethod perform ance. A ll PFOA [ 1JL- 3C] surrogate recoveries w ere w ithin 30%, but two o f the PFOS [ 1802] recoveries were outside 30%, extending the surrogate
reco v ery ran g e to + /-34% . S pecific surrogate reco v ery d ata is p resen ted belo w .
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3M ENVIRONMENTAL LABORATORY PROJECT NO.EOS-0442
Table 6. Surrogate Recovery
Sample ID
PFOA [1,2-13C] PFOS [1*OJ Recovery, % Recovery, %
MxBlk_050511-1 MxBlk_050511-2 MdBlk_OS0511-1 MdBlk_05C511-2 LS_Q505115-1 LS_Q505115-2 ISJD5C5115-3 HS_0505115-1 HS_C505115-2 HS_0505115-3
TN-A-6840 TN-A-6843 TN-A-6847 TN-A-6934 TN-A-6935 TN-A-6944 TN-A-5959 TN-A-6960 TN-A-69S7 TN-A-6973 TN-A-6975 TN-A-6977 TN-A-6981
110% 102% 80% 99% 114% 109% 98% 85% 120% 90% 80% 93% 78% 102% 89% 80% 85% 78% 91% 76% 84% 82% 83%
m% 98% 112% 103% 103% 94% 98% 95% 98% 88% 87% 82% 79% 72% 82% 79% 80% 66% 85% 76% 82% 73% 67%
Sample ID
PFOA [1,2-1*CJ Recovery, %
PFOS [18OJ Recovery, %
TN-A-6992 TN-A-6994 TN-A-6995 TN-A-6997 TN-A-7000 TN-A-7006 TN-A-6938 TN-A-S939 TN-A-6941 TN-A-8950 TN-A-8953 TN-A-6955 TN-A-8962 TN-A-S964 TN-A-6966 TN-A-8970 TN-A-8972 TN-A-6978 TN-A-6979 TN-A-6982 TN-A-8984 TN-A-6988 TN-A-6988
\
1 :
94% 87% 83% 84% 78% 91% 92% 78% 88% 96% 78% 85% 84% 89% 83% 84% 73% 74% 92% 113% 86% 81% 85%
83% 77% 74% 75% 72% 84% 76% 88% 82% 85% 81% 81% 85% 88% 75% 84% 75% 80% 78% 87% 86% 83% 83%
4 .4 L aboratory C ontrol Spikes (LCS)
Six Laboratory Control Spikes (LCS) were prepared in rabbit serum and analyzed w ith the samples. Results were corrected for endogenous levels o f analyte in the m atrix (where appropriate), and are presented below.
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3M ENVIRONMENTAL LABORATORY PROJECT NO.EOS-0442
Table 7. Matrix Spike Recoveries
A nalyte NFPA
Sam ple ID
Nominal
O bserved
Cone., ng/mL Cone., ng/mL
Recovery, %
LS 0505115-1 LS 0505115-2 LS 0505115-3 HS 0605115-1 HS 0505115-2 HS 0505115-3
0.306 0.306 0.309 3.06 3.06 3.06
0.517 0.373 0.336 2.89 3.48 3.55
169% 122% 109% 94% 114% 116%
% RSD 23% 11%
PFHA
LS 0505115-1 LS 0505115-2 LS 0505115-3 HS 0505115-1 HS 0505115-2 HS 0505115-3
0.303 0.303 0.303 3.03 3.03 3.03
0.699 0.261 0.224 3.43 2.79 3.09
231% 93% 74% 113% 92% 102%
65% 10%
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3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0442
Table 7. Matrix Spike Recoveries (continued)
PFOA
LS 0505115-1 LS 0505115-2 LS 0505115-3 HS 0505115.1 HS...0505115-2 HSJJ505115-3
0.297 0.297 0.297 2.97 2.97 2.97
0.235 0.129 0.136 2.46 2.82 2.7
C9 Acid
LS 0505115-1 LS 0505115-2 LS_0505115-3 HS_.Q5C5115-1 HS 0505115-2 HS_D505115-3
0.300 0.300 0.300 3.00 3.00 3.00
0.285 0.237 0.31 2.14 3.03 3.04
C10ACID
LS 0505115-1 LS 0605115-2 LS 0505115-3 HS 0505115-1
HS 0505115-2 HS_0505115-3
0.311 0.311 0.311 3.11
3.11 3.11
0.291 0.323 0.323 3.30
3.16 3.06
C12ACI0
LS 0505115-1 LS 0505115-2 LS 0505115-3 HS 0505115-1 HS 0505115-2 HS 0505115-3
0.30 0.30 0.30 2.99 2.99 2.99
0.323 0.371 0.341 2.91 3.65 3.56
FBSA
LS 0505115-1 LS 0905115-2 LS 0505115-3 HS 0505115-1 HS 0505115-2
HS 0505115-3
0.300 0.300 0.300
3.00 3.00
3.00
0.305 0.354 0.318 3.00 3.25
3.51
70% 43% 48% 83% 95% 91%
95% 79% 103% 71% 101% 101%
94% 104% 104% 106% 102% 98%
108% 124% 114% 97% 122% 119%
102% 118% 106% 100% 108% 117%
38% 5.9%
13% 19%
5.9% 3.8%
7.0% 12% 7.8% 7.8%
Page 11 of 19
Table 7. Matrix Spike Recoveries (continued)
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0442
A nalyte FOSA PFHS PFOS
Sam ple ID
IS 0505115-1 LS 0505115-2 LS 0505115-3 HS 0505115-1 HS .0505115-2 HS 0505115-3
Nominal Cone., ng/mL
O bserved Cone., ng/mL
Recovery, %
0.299 0.299 0.299 2.99 2.99 2.99
0.370 0.274 0.251 2.79 3.45 2.36
124% 92% 84% 93% 115% 79%
LS 0505115-1 LS 0505115-2 LS 0505115-3 HS 0505115-1 HS 0505115-2 HS 0505115-3
0.315 0.315 0.315 3.15 3.15 3.15
0.305
0.302 0.317 3.12 2.85 2.90
97% 96% 101% 99% 90% 92%
QC050202-001 QCC50202-002
QC050202-003 C050202-004 QC050202-005 QC050202-006
0.308 0.308 0.308 3.08 3.08 3.08
0.195 0.160 0.230 3.07 3.08 2.52
63% 52%
75% 100% 100% 82%
% RSD . 21% 19%
2.6% 4.9%
18% 11%
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3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0442
Tabla 7. Matrix Spike Recoveries (continued and corrected for endogenous target analytes)
Analyte
Sample ID
TDHA
LS_0505115-1 LS 0505115-2 LS 0505115-3 HS 0505115-1 HS 0505115-2 HS. 0505115-3
C11 ACID
LS 0505115-1 LS 0505116-2 LS 0505115-3 HS 0505115-1 HS 0505115-2 HS 0505115-3
Nominal
Cone., ng/mL
Observed
Cone., ng/mL
Endogenous
Level in Matrix, ng/mL
Observed Cone.,
Corrected for Endogenous Level, ng/mL
Recovery, %
0.302 0.302 0.302 3.02 3.02 3.02
'
0.297 0.297 0.297 2.97 2.S7 2.97
0.392 0.354 0.334 2.93 2.84 2.74 .
0.355 0.292 0.310 2.89 2.82 2.69
0.00641 0.00641 0.00641 0.00641 0.00641 0.00641
0.0168 0.0168 0.0168 0.0168 0.0168 0.0168
0.39 0.35 0.33 2.9 2.8 2.7
0.338 0.275 0.293 2.87 2.80 2.67
128% 115% 108% 97% 94% 91%
114% 93% 99% 97% 94% 90%
% RSD 8% 3%
11% 3.6%
PFBS
LS 0505115-1 LS 0505115-2 LS._0505115-3 HS 0505115-1 HS 0505115-2 HS 0505115-3
0.304 0.304 0.304 3.04 3.04 3.04
10.8 0.314 0.342 297 3.10 3.14
0.00815 0.00615 0.00615 0.00815 0.00815 0.00815
10.8* 0.306 0.334 2.96 3.09 3.13
3550%* 101% 110% 97% 102% 103%
6.2% 2.9%
THPFOS
LS 0505115-1 LS 0505115-2 LS 0505115-3 HS 0505115-1 HS 0505115-2 HS 0505115-3
0.312 0.312 0.312 3.12 3.12 3.12
NR NR 0.589 2.94 3.06 2.44
0.0256 0.0256 0.0256 0.0256 0.0258 0.0256
NR NR NR NR NR
0.56 181% Z9 93% 3.0 97% 12%
2.4 77%
THPFDS
LS 0505115-1 LS 0505115-2 LS 0505115-3 HS 0505115-1 HS 0505115-2 HS 0505115-3
0.302 0.302 0.302 3.02 3.02 3.02
0.330 0.306 0.302 2.94 2.85 Z94
0.0138 0.0138 0.0138 0.0138 0.0138 0.0138
0.316 0.292 0.288 Z93 Z84 293
105% 97% ! 95% 97% 94% 97%
5.1% 1.8%
*This value can be eliminated as an outlier at the 99% confidence level and will be excluded in all further calculations. NR = Not Reported because measurable amounts o f target analyte were not observed.
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3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0442
4 .5 Accuracy The accuracy for each analyte reported was calculated by taking the average o f the matrix spike recoveries for that analyte. The results are presented in Table 8.
Table 8. Method Accuracy for Individual Analytes
Analyte
NFPA PFHA TDHA PFOA C9 Acid C10 Acid C11 Acid C12 Acid
% Accuracy
21% 17% 5% 27%
8% 1%
2%
14%
Analyte
FBSA FOSA PFBS PFHS PFOS THPFOS THPFDS
% Accuracy
8%
2% 3%
4%
21%
12%
3%
4 .6 Sam ple R elated Com m ents
The extraction and analysis o f the samples was performed utilizing a non-validated method. The m atrix spike results, PFOA [1,2-13C] and PFOS [l8C>2] surrogate recoveries, and the calibration curve should be considered when evaluating the accuracy and precision o f the sample results.
5 Individual Sample Data
Tables 9 and 10 summarize individual sample data. Table 9. Perfluorinated Acid Results
Sam ple ID
NFPA PFHA (ng/mL) (ng/mL)
TDHA ina/m L)
PFOA (ng/m L)
C9 Acid (na/m L)
C10 ACID (ng/mL)
C11 ACID (ng/m L)
LLOQ (ng/m L)
0.102 0.00505 0.00504 0.0991 0.0150
0.0259
0.00992
TNA6340 0.445 < LLOQ < LLOQ 3.89 0.656
0.198
0.0968
TNA6843 TNA6847 TNA6934
1.51 1.56 0.866
< LLOQ 0.0133 0.00633
0.0752 0.118 0.0232
0.509 3.55 5.72
0.127 0.756 1.19
0.0768 0.309 0.450
0.0259 0.141 0.188
TNA6935 1.04 0.00838 0.0964 3.48
1.17
TNA6944 1.43 <LLOa 0.290 5.67 1.18
TNA6959 0.795 0.00964 0.195 2.52 1.96
TNA6960 0.932 0.00889 0.210 2.91 0.611
TNA6967 0.450 < LLOQ 0.270 3.68 0.531
TNA 6973 0.680 0.00652 0.352
3.60 0.940
TNA 6075 0.682 0.00779 0.398
4.02 0.906
0.551 0.584 0.193 0.300 0.209 0.391 0.402
0.384 0.196 0.734 0.121 0.1OS 0.124 0.149
The uncertainty o f these results (based on isotopically labeled surrogate recovery) is +/- 34%.
C12 ACID (ng/mL)
0.00997
0.0282 0.0212 0.0207 0.0264 0.0833 0.0465 0.0370 0.0190 0.0198 0.0328 0.0295
Page 14 of 19
3M ENVIRONMENTAL LABORATORY PROJECT NO.EOS-0442
Table 9. Perfluorinatod Acid Results (continued)
Sampie ID
NFPA ng/niL)
PFHA (ng/mL)
TDHA (ng/mL)
PFOA (ng/mL)
C9 Acid (ng/mL)
C o ACID (ng/mL)
C11 ACID (ng/mL)
C12ACID (ng/mL)
LLOQ (ng/mL)
0.102 0.00505 0.00504 0.0991 041150
0.0259
0.00992 0.00997
TNA 6977* 1.23 < LLOQ 0.0442 0.406 0.0950 0.0374
0.0152
LLOQ
TNA 6981 0.327 < LLOQ 0.0555 226 0.423
0.147
0.0708
LLOQ
TNA6992 1.09 < LLOQ 0.239 3.32 0.842
0.319
0.158
0.0124
TNA 6994 1.75 0.00694 0.0750 0.770 0.206
0.0830
0.142
0.0223
TNA 6995 1.06 < LLOQ 0.198 2.00
1.41
0.169
0.688
0.0147
TNA 6997 1.32 LLOQ 0.179 2.33
1.97
0.202
0.637
0.0185
TNA 7000 1.08 < LLOQ 0.174 3.92 0.717
0.332
0.112
0.0240
TNA 7006 0.818 <U-OQ 0.166 3.32 0.686
0.306
0.0946
0.0128
TNA 6938 1.09 LLOQ 0.474 4.36
1.20
0.421
0.165
0.0150
TNA $939 0.615 0.0323 0.0826 2.01
1.09
0.344
0.28
0.0302
TNA 6941
1.02 LLOQ 0.0608 4.07
1.61
0.599
0.424
0.0527
TNA 6950 11 < LLOQ 0.0925 320 0.792
0.229
0.116
0.0115
TNA 6953 1.27 <LLOQ 0.0442 3.08 0.785
0.249
0.0753
0.0150
TNA 6955 1.26 LLOQ 0.H1 2.20 0.603
0.341
0.196
0.0309
TNA 6962 1.09 < LLOQ LLOQ 3.51 0.690
0.311
0.111
0.0183
TNA 6964 1.28 <U-OQ 0.259 4.00 0.933
0.386
0.117
0.0176
TNA $966 0.665 < LLOQ LLOQ 2.81 0.562
0.249
0.0916
0.0195
TNA 6970 0.781 < LLOQ 0.159 4.17 0.917
0.322
0,148
0.0119
TNA 6972 1.19 < LLOQ 0.123 3.79 0.761
0257
0.126
0.0192
TNA 6978* 1.36 U-OQ 0.0481 0.359 0.114
0.0Z74
0.0152
LLOQ
TNA 6979 1.11 LLOQ 0.126 3.21 0.568
0.304
0.156
0.0161
TNA6982 0.751 LLOQ 0.0660 2.16 0.653
0.173
0.0547
LLOQ
TNA 6984 0.899 LLOQ 0.0636 2.19 0.558
0261
0.184
0.0108
TNA 6986 0.500 LLOQ 0.0549 2.31 0;480
0.179
0.03S4
LLOQ
TNA 6988 0.916 LLOQ 0.0443 1.93 0.610
0239
0.164
LLOQ
Mean
1.04 0.0111 0.151 2.98 0.813
0282
0.185
0.0246
Median Hlgh
1.05 0.00838 0.118 3.21 0.737
2.11 0.0323 0.474 5.72
1.97
0281 0.599
0.134 0.734
0.0197 0.0833
Lew
0.3Z7 0.00833 0.0232 0.359 0.095
0.0274
0.0152
0.0108
Standard Devlation 0.378 0.00822 0.111 1.27 0.445
0.137
0.176
0.0149
# OF HITS 36 9 33 36 36
36
36
30
` TN-A-69?? and -6978 are from die same lot of pooled serum.
The uncertainty o f these results (based on isotopicaJly labeled surrogate recovery) is -*/- 34%.
Page 15 o f 19
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0442
Table 9. Sample Results for Additional Perfluorinated and Highly Fluorinated Analytes
Sample ID
FBSA FOSA PFBS PFHS PFOS THPFOS THPFDS (ng/mL) (ng/mL) (ng/mL) (ng/mL) (ng/mL) (ng/mL) (ng/mL)
LLOQ (ng/mL) 0.00501 0.00498 0.00508 0.0158 0.103 ti.00520 0.00503
TNA 6840
< LLOQ 0.356 0.00795 3.07
21.9
TNA6843 TNA 6847
< LLOQ 0.124 0.OQB54 < LLOQ 0.0694 0.00854
0.606 1.62
278 22.4
TNA 6934 TNA 6935
< LLOQ 0.314 0.0112 1.95 27.0 < LLOQ 0.133 0.0101 1.75 14.5
TNA 6944
< LLOQ 0.0786 0.00969 3.66
16.9
TNA6959
< LLOQ 0.232 0.00979 2.85
12.4
TNA 6960
< LLOQ 0.166 0.0107 3.27 14.6
TNA 6967
0.00542 0.446 0.0238
3.04
19.7
TNA 6973 TNA 6975
<LL0Q 0.156 0.0172 LLOQ 0.127 0.00858
3.94 3.97
16.9 18.0
TNA 6977*
LLOQ 0.118 0.0840 0.662 2.03
TNA 6981
< LLOQ 0.122 < LLOQ 1.17
12.5
TNA 6992 TNA 6994
< LLOQ 0.159 0.0103
3.66
16.6
< LLOQ 0/116 0.0211 1.37 2.78
TNA 6995
< LLOQ 0.248 0.0160
288
11.6
TNA 6997
< LLOQ 0.224 0.00942 292
12.0
TNA 7000
< LLOQ 0.0906 0.0148
3.97
17.5
TNA 7006
< LLOQ 0.202 0.00989 3.43
19.2
TNA 6938
< LLOQ 0.0446 0.00711 238
16,3
TNA6939
< LLOQ 0.0967 0.0202 1.65 6.43
TNA6941
< LLOQ 0.130 0.00991 290
21.8
TNA 6950
< LLOQ 0.0378 0.00545 284
14.9
TNA 6953
LLOQ 0.0459 0.00804 4.08
21.9
TNA 6955
< LLOQ 0.0981 0.00588 273
9.62
TNA6962
< LLOQ 0.162 0.0122
3.64
17.8
TNA 6964
TN A 6366
< LLOQ < LLOQ
0.187
0.135
0.0218 0.00802
4.18
3.10
20.1 15.2
TNA 6970
< LLOQ 0.238 0.00737 3.22
18.3
TNA 6972
< LLOQ 0.124 0.0557
282
14.4
TNA 6978*
< LLOQ 0.109 0.00577 0.640 2.21
TNA 6979
< LLOQ 0.121 0.0127 1.97 19.0
TNA 6982
< LLOQ 0.0903 0.0144 1.53 14.7
TNA 6984
< LLOQ 0.108 < LLOQ 1.32
14.2
TNA 6986
< LLOQ 0.0712 0.0567 1.57 14.1
The uncertainty o f these results (basal on isotopically labeled surrogate recovery) is +/- 34%.
< LLOQ LLOQ < LLOQ < LLOQ < LLOQ < LLOQ < LLOQ < LLOQ < LLOQ < LLOQ LLOQ LLOQ < LLOQ LLOQ < LLOQ < LLOQ < LLOQ <U.OQ <LLOQ < LLOQ < LLOQ < LLOQ < LLOQ LLOQ LLOQ LLOQ LLOQ LLOQ LLOQ LLOQ LLOQ LLOQ LLOQ LLOQ < LLOQ
0.0562 0.106 0.126 0.00772 0.0457 0.048 0.0311 0.0365 0.0425 0.0353 0.0366 0.0413 0.0351 0.0417 0.0249 0.028 0.0273 0.034 0.0358 0.0259 0.0349 0.0279 0.0753 0.0273 0.0287 0.0345 0.0461
0.0281
0.0466 0.0319 0.0485 0.0799 0.0581 0.0529 0.0459
Page 16 of 19
!v
3M ENVIRONMENTAL LABORATORY PROJECT NO.EOS-0442
Table 9. Sample Results for Additional Perfluorinated and Highly Fluorinated Analytes (continued)
Sample ID
LLOQ (ng/mL) TNA6988 Mean Median High Low
FBSA FOSA PFBS (ng/mL) (ng/mL) (ng/mL)
0.00601 0.00498 0.00506
< LLOQ
NA NA 0 00542 0.00542
0.101
0.149 Q.124 0.448 0.0378
< LLOQ
0.01845
0.0101
0.084 0.0055
PFHS PFOS THPFOS THPFDS (ng/mL) (ng/mL) (ng/mL) (ng/mL)
0.0158 0.103 0.00520 0.00503
1.45 2.55 2.85 4.18 0.606
15.7 < LLOQ 0.0586 14.9 NA 0.0442 15.5 NA 0.0386 27 NA 0.126 2.03 NA 0.00772
Standard Deviation NA
0.0878 0.0169
1.07
5.94
#OF HITS
1 36 33 36 36
TN-A-6977 and -6978 are from lbe same tol o f pooled serum. The uncertainty o f these results (based on isotopically labeled surrogate recovery) is +/- 34%.
NA 0.0227 0 36
Table 10. Isomer Ratios for Individual Samples
Sample ID
TNA6840 TNA6843 TNA6847 TNA6934 TNA6935 TNA6944 TNA 6959 TNA6960 TNA6967 TNA6973 TNA 6975 TNA 8977** TNA 6981 TNA 6992 TNA 6994 TNA 6995 TNA 6997 TNA 7000 TNA 7006 TNA 6938 TNA 6939 TNA 8941 TNA 8950 TNA 6953
Sample Origin
California Missouri Pennsylvania Pennsylvania New York Michigan Virginia Virginia Maryland Montreal, Quebec Montreal, Quebec Massachusetts Texas California California California California California California New York New York New York Michigan Michigan
PFOA% Branched
Isomer
LLOQ* LLOQ*
3.2% 1.3% 6.8% 2.7% 3.9% 2.3% LLOQ* 2.3% 2.3% LLOQ* LLOQ* LLOQ* 3.1% 4.2% 3.9% 2.2% LLOQ* 2.3% 1,1% 0.7% 1.6% 0.8%
PFOS % Branched
Isomer
37% 35% 42% 46% 34% 33% 37% 36% 40% 39% 40% 35% 40% 36% 38% 39% 39% 40% 39% 40% 33% 35% 37% 39%
Page 17 of 19
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0442
TNA 6955 TNA6962 TNA 6964 TNA 6966 TNA 6970 TNA 6972 TNA 6978** TNA 6979 TNA 6982 TNA 6984 TNA 6986 TNA69B8
Michigan Virginia Virginia Virginia Maryland Maryland Massachusetts Massachusetts Texas Texas Texas Texas
1.6% <LLOQ* <LLOQ* <LUOQ* <LLOQ*
Z1% <lloq*
3.5% 0.8%
<LLOQ* <LLOQ* <LLOQ*
34% 39% 39% 37% 38% 36% 36% 30% 41% 30% 41% 33%
Average:
2.5%"*
37%
Standard Deviation
1,4%"*
3.3%
*The branched isomer in the sample was < LLOQ **TN-A-6977 and -6978 are from the same lot o f ptxiled serum. ***The average and standard deviation represent only those samples with isomer values above the LLOQ.
6 Data/Sample Retention
All original raw data and the analytical report have been archived at the 3M Environm ental Laboratory. The test materials and analytical reference standard reserve samples, as w ell as the samples pertaining to this project are archived at the 3M Environm ental Laboratory.
Reserve samples, digital copies o f original data and all original paper data w ill be retained in the archives o f 3M Environmental Laboratory for a period o f at least 10 years following report signing.
7 Conclusion
Under the conditions o f the study, endogenous fluorochemicals were found to be present in all samples. NFPA, PFOA, C9Acid, Cio Acid, C | i A cid, FOSA, PFHS, PFOS and THPFDS w ere detected in every lot o f serum. TDHA and PFBS were detected in all but three samples, and the C u Acid was detected in 30 o f 36 samples. Conversely, PFHA was only detected in 9 o f 36 samples, and FBSA was only detected in 1 o f 36 samples. THPFOS was not detected in any o f the samples using the present methodology. PFOA [1,2-13C] surrogate recoveries w ere all w ithin 30% w hile PFOS ['*02] surrogate recoveries were all within +/- 34%. M ethod accuracy for individual analytes ranged from + /-1% to +/- 27% w hile overall method uncertainty (based on. isotopically labeled surrogate recovery) was +/- 34%.
Page 18 of 19
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0442
The 3M Environmental Laboratory's Quality Assurance U nit has audited the data and report for this project.
QualityAssurance Representative
Date
Page 19 of 19
