Document zVV3xjLKD1YLeOQLVEEgKoNm
3M ENVIRONMENTAL LABORATORY PROJECT NO E05-0120
iflv l
Analytical Report
Revised August 12, 2005
Initial Quantitative Screening of Commercial Lots of Human Serum Obtained in 2004 for Endogenous Fluorochemicals Using Protein Precipitation and Liquid Chromatography/Tandem Mass Spectrometry
Laboratory Request Number: E05-0120
Testing Laboratory
3M Environmental Health and Safety Operations 3M Environmental Laboratory
3M Environmental Laboratory
Project Lead Mark E. Eliefson Building 2-3E-09
PO Box 3331 Saint Paul, MN 55133-3331
Phone: 651-778-5405
Testing Facility Management William K. Reagen, Ph.D. Building 2-3E-09 PO Box 3331
Saint Paul, MN 55133-3331 Phone: 651-778-6565
Requestor
Dale Bacon Building 2-3E-Q9
PO Box 3331 Saint Paul, MN 55133-3331
Phone: 651-778-4736
Page 1 o f 18
3M Environmental Laboratory
Analytical Report
3M ENVIRONMENTAL LABORATORY PROJECT NO.EG5-0120
Project Number; E05-0120
The following analytical report presents data from commercially available normal pooled human serum that were purchased by the 3M Environmental Laboratory and subsequently screened for endogenous fluorochemicals.
Thirty-six separate lots of pooled normal human serum were extracted using a protein precipitation technique and screened for sixteen different fluorochemicals using liquid ehromatography/tandem mass spectrometry (LC/MS/MS). Serum samples were received from various suppliers between 9/9/04 and 12/2/04. Samples were analyzed between 02/03/05 and 02/09/05.
This range-finding study was designed to provide lower limits o f quantitation (LLOQs) of approximately 100 - 300 ppt. Upon review o f the data, it was discovered that many o f the target analytes were present at concentrations much lower than the 100 - 300 ppt target level. As an interim solution and until a more definitive study can be completed, signal to noise ratios were evaluated .and a limit o f detection (LOD) was defined for each analyte. As a result, calibration curves were extrapolated between the LLOQ and the newly defined LOD, allowing screening quality data to be determined for some analytes as low as 19.9 ppt. Therefore, it must be emphasized that much o f the data presented in this report was derived from extrapolated curves and should be considered as screening quality data only.
Sample results are summarized in Table 1. The average values reported represent samples in which there was detectable analyte. Sample values that were less than the limit of detection were not included in the average value calculations. Please refer to Section 5 for individual sample results.
Page 2 of 18
Table 1. Summary of Perfluorinated Acid Results
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0120
K p f lp il
l l 9 s , .J?
i .':l o g /
S w ii)
Mean
3.33 2.84 NR2 0.954 4.61 1.25 NR2 0.623 <LOD
Median
3.33 2.5 NR2 0.954 4.59 1.09 NRZ 0.660 <LOD
High Low
7.08 3.56 0.507 2.45
NR2 1.02 23.0 2.63 NR2 0.888 0.477 0.337
NR2 0.842 <LOD NR2 0.312 <LOD
Standard Deviation
2.17 0.627 NR2 0.0933 3.64 0.571 NR2 0.208 ND1
Number of Samples with Detectable Analyte
20/36
3/36
0/36
2/36 35/36 34/36
0/36
6/36 0/36
NDl - Not Detected. This analyte was not detected in any of the samples. NR1= Not Reported. This analyte was detected in one of the 36 samples but appears to be a contaminant or an anomaly; the sample will be reanalyzed and the results will be reported in the definitive study.
Table 2. Summary of Other Perfluorinated and Highly Fluorinated Analyte Results
(ng/mL) IgimL] Jjlsj r*rLisiliy
ilSi
Mean
<LOD 0.0776 0.0348 3.27 16.3 <LOD 0.0839
Median
<LOD 0.0401 0.0339 3.27 16.9 <LOD 0.0819
High
<LOD 0.199 0.0706 5.80 32.8 <LOD 0.155
Low <LOD 0.0311 0.0210 0.780 2.71 <LOD 0.0480
Standard Deviation
ND1 0.0812 0.0122 1.52 6.71 ND1 0.0257
Fraction of Samples with Detectable Analyte
0/36 4/36 23/36 36/36 36/36 0/36 36/36
ND1= Not Detected. This analyte was not detected in any of the samples.
Peaks were observed in the chromatograms corresponding to linear and branched isomers for PFOS and PFOA. Relative branched and linear isomer ratios were determined for both analytes and are presented below (the human serum value represents an average o f % branched isomers for all o f the human serum samples that contained detectable levels o f each analyte). The % branched isomer results for individual samples are presented in Table 12. In addition, well-characterized lots of PFOS (Lot 171) and PFOA (Lot 332) were analyzed together as a matrix spike (QC050203-004) in rabbit serum. Data from that analysis was evaluated for branched and linear isomer distribution and agrees well with previously obtained NMR data.
Page 3 of 18
m ENVIRONMENTAL LABORATORY PROJECT NO.ES-0120
Table 3. Summary of PFOA and PFOS Isomer Ratios
i*. ** ' '* * -* Human Serum, average
Matrix Spike (QC050203-004)
TCR-123 (99030-030) PFOA Lot 332 (NMR characterized value)
TCR-696 PFOS Lot 171 {NMR characterized value)
6% 23%
22%
.2
Pi I It,
39% 32%
31%
1
Table 4. Reference Substances
S
I
I S S -3 SS :
Heptafluorobutyric Acid
PFBA (C4 Acid)
Aldrich
TCR-757
i m t f if e ..
99.2%
0.995
Nonafluoropentaaoic acid NFPA (C5 Acid) '
Aldrich
TCR-333 (00017-045) 96.5%
0.996
Perfluorohexancic acid
PFHA (C6 Acid) Oakwood Products
TCR-673
97.7%
0.997
Tridecafluoroheptanoic 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
Heptadecafluorononanoic acid
C9 Acid
Oakwood Products
TCR-618
98.0%
0.998
Nonadecafluorodecanoic acid
CIO Acid
Oakwood Products
TCR-36
98.01%
0.998
Perfluoroundecanoic 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
Perfluorobutar.esulfonamide
FBSA
3M
TCR-314 (00017-026) unknown
0.997
Pcrfluorooctanesulfonamide
FOSA
3M
TCR-280 (99131-038) 98.94%
0.997
Perfluorobutane sulfonate
PFBS
3M
TCR-282 (99131-040) 97.3%
0.885
Perfluorohexane sulfonate
PFHS
3M
TCR-83 (SE036)
98.6%
0.911
Perfluorooctane sulfonate
IH, 1H, 2H, 211, perfluorooctanesulfonic acid
1H, 1H, 2H, 2H, perfluorodecane sulfonate Perfluorooctanoic acdd,
isotopically labeled
PFOS THPFOS
THPFDS PFOA
3M SynQuest Labs
PaceOM Perkin Elmer
TCR-696 TCR-343 (00017-055)
TCR-627 TCR-744
86.4% 93.5% 94.7% >97%
0.927 0.998 0.998 0,998
Page 4 of 18
3M ENVIRONMENTAL LABORATORY PROJECT NO.E050120
The samples for this study were prepared as follows:
1. The serum samples were allowed to thaw and warm to room temperature.
2. One milliliter o f serum (or water in the case o f method blanks) was added to a 15 mL screw-capped polypropylene centrifuge tube.
3. Matrix spikes and method blanks were prepared by spiking the serum (or water) with the analytes of interest. In addition, 13C PFOA was added as a surrogate to all serum samples, calibration standards, matrix blanks, and method blanks at a concentration o f 3.01 ng/mL to evaluate extraction method performance
4. Two milliliters 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 approximately 3000 re f for 20 minutes to pellet the precipitate.
6. After removal from the centrifuge, the supernatant was transferred to an autovial for analysis.
Quantification was accomplished by high performance liquid chromatography tandem mass spectrometry. The following parameters were used:
Liquid C hrom atograph: Hewlett-Packard Series 1100 Liquid Chromatograph system Analytical column: Keystone BetasilTM Cig 2x100mm, 5pm particle size Column temperature: 30 C Stop Time: 20.0 m inutes Flow rate: 300 pL/min Injection volume: 5 pL Mobile phase components: Solvent A: 2.0 mM ammonium acetate in ASTM Type I water Solvent B: KPLC Grade Methanol Solvent Gradient:
Time 0.00 1.00 14.50 15.50 16.50 20.00
%i 20% 20% 90% 90% 20% 20%
PageS of 18
3M ENVIRONMENTAL LABORATORY PROJECT NO,05 0120
Mass Spectrometer: MDX Sciex API 4000 Q-Trap Mass Spectrometer Detector Software: AnalystTM Version 1.4 Ionization Mode: Electrospray Negative Temperature: 450 C GS1: 35 GS2: 45 Entrance Potential: 10 Analysis Type: Multiple Reaction Monitoring (MRM)
Table S. Acquisition Parameters
g lliijfiS lI M PFBA (C4acid) NFPACsAcid PFHA (CBacid) TDHA (C7 Acid) PFOA (Cs Acid) Cs Add C10Acid Ct1 Add Q 2Acid FBSA FOSA PFBS PFHS PFOS THPFOS THPFDS PFOA [1>2-13C]
iM 213.0 262.9 313.0 362.9 413.0 463.0 512.9 563.0 613.0 2S7.S 497.9 298.9 398.9 498.9 426.9 526.9 414.9
ras .I S _'hb' * ft!' MM? f t?ir
168.9 219.0 268.7,118.9 318.7,168.8,118.9 368.9,219.0,169.0 418.7,268.9,218.9 468.8,218.9,269.1 518.7,268.9,218.8 568.7,168.9,318.7 78.0 77.9 98.9,79.9 98.9,80.0 80.0,99.2,130.0 406.8,80.9 506.7,81.0 369.8
* ] Ppfaria{-. ,,
-30 -30 -45 -35 -40 ; -50 -100 -45 -50 -55 -90 -65 -95 -80 -70 -70 -40
When multiple transitions were monitored, the total ion current (TIC) was used to quantify each analyte, thereby providing greater sensitivity than individual Q3 ion measurements.
4.1 Calibration 4.1 J 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 fluorochemicals and diluted in methanol (except PFBA, which was prepared in Milli-Q water to prevent esterification from occurring). Samples were quantified versus an 8-point extracted calibration curve. The regression analysis was performed using a quadratic curve fit weighted 1/x.
Page 6 o f 18
3M ENVIRONMENTAL LABORATORY PROJECT NQ.E05-0120
Calibration standards were within 20% (25% for the Lower Limit o f Quantitation (LLOQ)) with a coefficient o f determination >0.995. Low-level calibration standards, which were not within 25%, were not included in the calibration curve. Calibration standards that were not greater than twice the method blanks were not included in the calibration curve. 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: Several individual transitions monitored for the Cio Acid failed the retention time system suitability criteria. However, the data reported was derived from the quantitation o f the TIC, which passed system suitability requirements. All o f the system suitability sets for FBSA area counts failed. The %RSDs were 6.2%, 7.5% and 8.4%. However, no samples had area counts above the LLOQ for this analyte therefore the data was accepted. 41.4 Lower Limit of Quantitation (LLOQ) The LLOQ for each analyte was equal to the lowest standard in the calibration curve that met accuracy requirements o f 75% -125%. 41.5 Limit of Detection (LOD) The LOD for each analyte was equal to the area counts (converted to a concentration) that w ere 2-3 tim es above the m ethod blank. 41.6 Blanks Method Blanks All of the method blanks in this study had area counts < 50% o f the LLOQ. Matrix Blanks Two matrix blanks were prepared in rabbit serum and analyzed with the samples. One matrix blank contained endogenous levels o f PFOS that were above the LLOQ. An average endogenous value for PFOS was determined by substituting a number equal to % the LLOQ for BLK050203-003.
Page 7 of 18
3/W ENVIRONMENTAL LABORATORY PROJECT NO.E05-0120
Table 6. Average Endogenous PFOS Value Determination
LLOQ (ng/mL)
ju l..#*...**.. .
0.306
rOEJ M
Blk050203-003
< LLOQ
Blk050203-004
0.477
Average:
0.315
The average endogenous PFOS value was used to correct the matrix spike
response for endogenous levels o f PFOS in rabbit serum.
41.7 Solvent Blanks
Acetonitrile blanks were analyzed throughout the analytical run. Analyte response was less than lA the LLOQ in all cases.
41.8 Surrogate
13C PFOA was added as a surrogate to all serum samples, calibration standards, matrix blanks, and method blanks at a concentration o f 3.01 ng/mL to evaluate the extraction method performance, All surrogate recoveries were within 20%.
4.2 Laboratory Control Spikes (LCS)
Six Laboratory Control Spikes (LCS) were prepared in rabbit serum and analyzed with the samples. Results were corrected for endogenous levels o f analyte in the matrix (where appropriate), and are presented below.
Table 7. Matrix Spike Recoveries in Rabbit Serum
--TH
PFBA{C4 ad d ) LOD = 0.426 ng/m L LLOQ = 3.00 ng/m L
Q C 050203-001 QC050203-002 QC050203-003 QC050203-004 Q C 050203-005 QC050203-006
NFPA {CS acid) LOD * 4.53 ng/mL LLOQ -1 5 .3 ng/m L
NA = Not Applicable
QCO50203-001 QC050203-002 QC050203-003 QC050203-QQ4 QC050203-Q5 QC0502Q3-006
3.00 3.00 3.00 75.6 75.6 75.6
3.06 3.06 3.06 77.7 77.7 77.7
<LLQQ <LLOQ <LLOQ
70 71.3 70.2
<LLOQ <LLOQ <LLOQ 68.00
80.50
97.20
NA NA NA
NA
93% 94%
1.0%
93%
NA
NA NA
NA________________
88%
104%
17.9%
125%________________
Page 8 of 18
Table 7, Matrix Spike Recoveries in Rabbit Seium (continued)
3M ENVIRONMENTAL LABORATORY PROJECT NO.E0S-0120
mm
PFHA {C6 acid) L LO a=1S.1 ng/mL
P i 9 ^ H P
QC050203-001 Q C 050203-002 QC050203-003 QC050203-004 QC050203-005 Q C 050203-006
3.03 3.03 3.03 76.8 76.8 76.8
W
<LLOQ <LLOQ
<LLOQ
62.4 77.2
94.2
NA NA NA 81% 101% 123%
NA 20.4%
TDHA{C7 acid) LLOQ = 3.03 ng/mL
QC050203-001 Q C 050203-002 QC05203-003 Q C 050203-004 Q C 050203-005 Q C 050203-006
3.03 3.03 3.03 76.5 76.5 76.5
< LLOQ < LLOQ < LLOQ
66.9 80.1 95.4
NA NA NA 87% 105% 125%
NA 17.7%
CIO ACID LLOQ = 3.12 ng/m L
QC050203-001 QC050203-Q02 QC050203-C03 QC0502Q3-04 Q C 050203-005
Q C 050203-006
C11 ACID LLOQ = 0.297 ng/m L
-_ C12ACID
LLOQ = 0.747 ng/m L
NA = Not Applicable
QC05Q203-1 Q C 050203-002 Q C 050203-003 QCQ502Q3-Q04 QC050203-005 QCO5O2O3-OO0
QC050203-001 QC050203*002 QCO50203-003 QC050203-004 Q C 050203-005 Q C 050203-006
3.12 < LLOQ
NA
3.12 < LLOQ
NA
3.12 < LLOQ
NA
78.6 65,4 83%
78.6 71 g 91%
78.6 83.1 106%
NA 12%
2.97 2.98 100%
J
2.97 2.71
91% 5.1%
2.97 2.95 99%
75.3 75.8 101%
75.3
78.3
104%
1.8%
75.3 78.2 104%
.....................................................................................................1 3.00 3.04 101%
3.00
3.13
104%
3,8%
3.00 3.28 109%
75.6 78.2 101%
75.6
82.2
109%
3.9%
75.6 78.3 104%
Page 9 o f 18
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0120
Table 7. Matrix Spike Recoveries in Rabbit Serum (continued)
if - iS w iiiif B
I B g a b i 5 N om inal C o n e..
SSS
r ; 1!'*!-
IS i
m ir r f l;!
QC05C203-001
3.01
QC050203-002
3.01
" c PFOA
QC050203-03
3.01
Q C 050203-004
3.01
QG050203-005
3.01
QC050203-006
3.01
2.81 3.06 2.94 2.68 2.S1 2.75
r -----------------
-.M e : --iWBST ' i &
93% 102% 98% 89% 97% 91%
4.8%
C9 Acid LLOQ = 0.303 ng/m L
QC050202-001 QC05202-002 Q C 050202-003 QC050202-004 QC050202-005 QC050202-006
PFOA L L O O -0.298 ng/m L
QC050202-001 QC050202-002 Q C 050202-003 Q C 050202-004 Q C 050202-005 Q C 050202-006
3.03 3.03 3.03 75.4 75.4 75.4
2.98 2.98 2.98 75.6 75.6 75.6
3.23 107%
3.04
100%
4.7%
2.95 97%
77.4 103%
75.8
101%
5.3%
69.9 93%
2.93 98%
2.58 87% 8.8%
2.65 89%
75.2 99%
76.4
101%
1.6%
77.6 103%
FBSA LLOQ = 0.303 ng/mL
QC05Q203-001 QC050203-002 QC050203-03 Q C 050203-004 QC05O2O3-O5 Q C 050203-006
FOSA LLOQ* 0.300 ng/m l.
QC050203-001 Q C 050203-002 QCQ50203-Q03 Q C 050203-004 QC050203-005 QC050203-006
3.03 3.03 3.03 76.5 76.5 76.5
3.00 3.00 3.00 75.9 75.9 75.9
2.96 98% 2.92 96% 0.7%
2.95 97%
75.9 99%
77.9
102%
1.4%
77.7 102%
2.78 93% 2.74 91% 0.8%
2.74 91%
76.6 101%
77.1
102%
0.7%
76.0 100%
Page 10 of 18
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0120
Table 7. Matrix Spike Recoveries in Rabbit Serum (continued)
ta lly T ia g g a w iM
fp a!.C n ci.t> !.
m l S S fe a - y % \;-H
O bserved | , nn/m ll-
PFBS LLOQ = 0.303 ng/mL
QC050203-001 QC050203-Q02 QC050203-003 QC050203-004 QC050203-005 QC050203-006
3.03 3.03 3.03 76.8 76.8 76.8
3.06 3.00 3.01 75.8 78.3 77.2
101% 99% 99% 99% 102% 101%
PFHS LLOQ = 0.315 ng/mL
QC050203-001 00050203-002 Q C 050203-003 QC050203-004 QC050203-005 QC050203-006
3.1S 3.15 3.15 79.8 79.8 79.8
3.04 97% 3.08 98% 3.04 97% 78.2 98% 79.9 100% 78.6 98%
THPFOS LLOQ 0.780 ng/mL
QC050203-001 QC050203-002 QC050203-003 QC050203-004 QC050203-005 QC050203-005
3.12 3.12 3.12 78.9 78.9 78,9
3.02 97% 2.83 91% 2.83 91% 66.0 84% 80.0 101% 96.5 122%
THPFOS LLOQ = 0.303 ng/mL
QC050203-001 QC050203-002 QC0502C3-003 QC050203-004 QC050203-005 QC0502G3-0Q6
3.03 3.03 3.03
76.5 76.5 76.5
2.96 98% 3.00 99% 3.12 103% 77.9 102% 79.8 104% 78.2 102%
FEU
1.1% 1.6% 0.8% 1.1% 3.8% 19% 2.8% 1.3%
Page 11 of 18
3M ENVIRONMENTAL LABORATORY PROJECT NO.E5-Q120
Table 8. PFOS Matrix Spike Recovery in Rabbit Serum, Corrected for Endogenous Levels
W if
4.3 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 below.
Table 9. Method Accuracy for Individual Analytes
Analyte ^A ccuracy
Analyte ' "/Accuracy
PFBA*
+ 7%
C12 Acid
5%
NFPA* PFHA* C7 Acid*
8%
2% 6%
FBSA FOSA PFBS
= 1% 4%
1%
PFOA
4%
PFHS
2%
C9 Acid
1%
PFOS
5%
C10 Acid*
7%
THPFOS
2%
C11 Acid
1%
THPFDS
1%
'T h e % Accuracy reported for this analyte is based on the high concentration spike recovery data only because the low concentration
spike recoveries were less than the LLOQ.
4.4 Sample Related Comments
The extraction and analysis of the samples was performed utilizing a non-validated method. The matrix spike results, 13C PFOA surrogate recoveries, and the extrapolated calibration curve (between the LLOQ and LOD) should be considered when evaluating the accuracy and precision o f the sample results.
Tables 10 and 11 summarize individual sample data.
Page 12 o f IS
Table 10. Perfiuorinated Acid Results
ill!... PFHA
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0120
C9 Acid
TNA 6340 TNA 6843 TNA6847 TNA 6934 TNA 6935 TNA 6944 TNA 6959 TNA 6960 TNA 6967 TNA 6973 TNA 6975
5.19 0.990* 0.507* <LOD 1.17*
7.08 4.91 3.32 4.09 6.73 2.95*
2.50 cLOD <LOD <LOD cLOD CLOD <LOD <LOD <LOD 3.56 cLOD
<LOD <LOD <LOD <LOD <LOD <LOD cLOD <LOD cLOD cLOD cLOD
<LOD cLOD cLOD cLOD cLOD cLOD cLOD cLOD <LOD 0.888* cLOD
i
5.48 I 0.581 4.61
7.69 5.19 7.38 ! 3.13 4.59 5.30 5.51 5.52
Xi:-: iVAiSf as.Ts<is>*-.
1.52 cLOD
0.574
CLOD
0.976
cLOD
2.26 CLOD
: 1.63
CLOD
! 1.45
CLOD
! 2.45
cLOD
1.11 cLOD
1.62 <LOD
1.64 CLOD
1.31 CLOD
cLOD <LOD <LOD cLOD 0.451 CLOD 0.700 cLOD CLOD cLOD cLOD
||
cLOD cLOD <LOD cLOD cLOD cLOD cLOD cLOD CLOD cLOD cLOD
Page 13 of 18
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-120
Table 10. Perfluorinated Acid Results (continued)
^ flB l (n g /m U
PFOA im iftiB
m m Ip J'.-j. * i a ma j - . i i a ! w s k
1
TNA6977" TNA 6981 TNA 6992 TNA6994 TNA 6995 TNA 6997 TNA 7000 TNA 7006 TNA6938 TNA 6939 TNA 6941 TNA6950 TNA 6953 TNA 6955 TNA 6962 TNA 6964 TNA 6966 TNA6970 TNA6972 TNA6978** TNA 6979 TNA 6982 TNA6984 TNA698B TNA6988
M ean M edlan
High Low
5.04 6.76 0.690* <LOD 1.98* 3.90 3.34 3.19 <LOD LOD 3.56 LOO 0.621* LOD <LOD <LOD <LOD <LOD LOD <LOO <LOD <LOO <LOD 0.530* LOD 3.33 3.33 7.08 0.507*
<LOD 2.45 LOD <LOD LOD <LOD <LOD LOD <LOD <10D <LOD LOD <LOD <LOD <LOD LOD <LOD <LOD LOD LOD <LOD <LOD LOD LOD LOD 2.84 2.50 3.56 2.45
<LOD <LOD LOD <LOD 16.4*** LOD <LOD <LOD LOD LOD LOD LOD <LOD LOD <LOD LOD <LOD <LOD <LOD LOD <LOD <LOD LOD <LOD LOD NA
NA NA NA
LOD <LOD LOD LOD 1.02* LOD <LOD LOD LOD LOD LOD LOD <LOD LOD LOD <l o d LOD <LOD <LOD LOD <LOD <LOD <LOD LOD LOD 0.954* 0.954* 1.02* 0.888*
0.477 4.12 4.76 1.15 3.58 3.46 23.0 4.18 5.00 2.32 5.82 3.87 5.49 2.54 4.68
Shi/.U 4
4.73 8.00 3.40 < LOD 3.32 1.48 2.84 2.08 2.57 4.61 4.59 23.0 0.477
l 'W H I
&
o ;3 o r< & life- $
"
a
w
jja
ss
'i
<LOD
<LOD
1.28 <LOD
0.912
LOD
0.337
LOD
2.63 LOD
2.52 LOD
1.08 <LOD
1.09 LOD
0.979
LOD
0.941
LOD
1.69 LOD
0.723
14.0***
0.725
LOD
0.562
LOD
0.941
LOD
1.58 <LOD
1.35 <LOD
1.42 <LOD
1.09 <LOD
< LOD
LOD
0.981
<LOD
0.664
LOD
0.955
LOD
0.645
<LOD
0.881
<LOD
1.25 NA
1.09 NA
2,63 NA
0.337
NA
LOD <LOD LOD <LOD 0.815 0.642 <LOD <LOD LOD 0.312 0.620 LOD <LOD <LOD LOD <LOD LOD LOD <LOD <LOD LOD <LOD <LOD <LOD <LOD 0.623 0.660 0.842 0.312
LOD LOD LOD LOD LOD LOD LOD LOD LOD LOD LOD LOD LOD LOD LOD LOD LOD LOD LOD LOD LOD LOD ! LOD | LOD LOD ! NA ~ NA NA NA
S ta n d a rd D eviation
2.17
0.627
NA
0.0933
3.64
0.571
NA
0.208
NA
# O F HITS
20
3
0
2 35 34
0
6
NA = Not Applicable Analyte coocentraticm was below the 1.LOQ and above the LOD. TN-A-6977 and TN-A-6978 are from the same lot o f pooled scrum.
***Analyte was detected in one of the 36 samples but appears to be a contaminant or an anomaly; the sample will be reanalyzed and the results willbe reported in the definitive study.
Based on " C PFOA surrogate recovery, the overall method uncertainty is +/- 20%.
0
Page 14 of 18
3M ENVIRONMENTAL LABORATORY PROJECT NO.EOS-0120
Table 11. Sample Results for Additional Perfiuorlnated and Highly Fluorlnated Analytes
TMA6640 TNA6843 TNA 6847 TNA 6934 TNA 6935 TNA 6944 TNA 6959 TNA 6960 TNA 6967 TNA 6973 TNA 6975 TNA 6977** TNA 6981 TNA 6992 TNA 6994 TNA 6995 TNA 6997 TNA 7000 TNA 7006 TNA 6938 TNA 6939 TNA 6941 TNA 6950 TNA 6953 TNA 6955 TNA 6962 TNA 6964 TNA 6966 TNA 6970 TNA 6972 TNA 6978*' TNA 6979 TNA 6982 TNA 6984 TNA 6986
[ 1PFHS,; PFOS (nj^niL) (n g M it) ;TMgP/mL?
<100 <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOO <LOD <LOO <LOD <LOD <LOD <LOD <LOD <l o d <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LQD <LOD
<L0D
<LOD <LOO <LOD <LOD <LOD cLOD <LOD
s S S i 5.0 1 9 9
<LOO
<LOD
<LOD 0.0228*
00458* <LOD
<LOD 0.0304*
<LOO 0.0433*
<LO0 0.0706*
<LOD
<LOD
<LOD 0.0292*
0.199* 0.0358*
<LQD
<LOD
<L0D 0.0393*
<LOD 0.Q339*
0.0311* 0.0313*
<LOD 0.0429*
<LOD
<LOD
<LOD 0.0366*
<lO D 0.0479*
cLQD 0.0568*
< O D 0.0412*
<LOD 0.0226*
<LOD
<LOD
<LOD 0.0224*
<LOD
<LOD
<LOD 0.0226*
<LOD
<LOD
<LOD 0.0312*
<LOD 0 0374*
<LOD 0.0229*
<LOD
<LOD
<L.OD 0.0345*
<LOD 0.0210*
0.0344* 0.0228'
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
.* '
4.39 0.780 2.05 2.41 2.14 4.73 3.75 4.52 4.27 5.18 4.98 0.844 1.77 4.45 1.71 3.79 3.81 5.68 4.90 2.78 1.79 3.06 3.24 5.24 3.29 5.22 5.80 4.62 4.06 3.09 0.945 2.31 1.26 1.73 1.41
23.0 3.42 23.7 32.8 16.2 20.4 14.8 19.6 21.3 20.5 19.4 3.01 17.4 19.8 3.50 15.1 15.2 22.9 20.2 15.6 6.23 23.4 14.3 22.1 10.1 19.8 21.7 17.5 17.0 12.7 2.71 16.7 9.37 15.8 11.3
<LOD <LOD CLOD <LOD CLOD CLOD <LOD <LOD <LOD <LOD CLOD <LOD <LOD CLOD <LOD CLOD <LOD CLOD CLOD <LOD <LOD <LOD <LOD cLOD cLOD <LOD CLOD <LOD CLOD cLOD <LOD cLOD cLOD cLOD <LOD
0.124* 0.155* 0.145* 0.0531* 0.0820* 0.0860* 0.0649* 0.0819* 0.0857* 0.0818' 0.0622* 0.0916* 0.103* 0.0826* 0.0616* 0.0853* 0.0707* 0.0638* 0.0667* 0.0601* 0.0625* 0.0577* 0.0909* 0.0400* 0.0493* 0.0705* 0.101* 0.0620* 0.137* 0.0653* 0.0998* 0.102* 0.0790* 0.0911* 0.0683*
Page 15 of 18
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-020
Table 11. Sample Results for Additional Perfluorinated and Highly Fluorinated Analytes (continued)
k b t Td
iF"y/Or%
TNA 6988 Mean M edian High Low
ir" -f '
<LOD NA NA NA NA
- Q .3 ( j
<LOO 0.0776' 0.0401* 0.199' 0.0311*
<LOD 0.0348* 0.0339* 0.0706* 0.0210'
0 .0 0 2 6 1 1.79 3.27 3.27 5.80 0.780
1S.5 16.3 16.9 32.8 2.71
S tandard D eviation NA
0.0812 0.0122
1.52
6.71
# OF HITS
0 4 23 36 36
NA = Not Applicable Analyte concentration was below the LLOQ and above the LOD. TN-A-6977 and -6978 are from (he sanie lot o f pooled semiti. Based on n C PFOA surrogate recovery, the overall method uncertainty is +/- 20%.
-SBtf*
<LOD NA NA NA NA
\o 2 9 1 0.0979* 0,0839* 0.0819* 0.155* 0.048*
NA 0.0257
o 36
Table 12. Isomer Ratios for Individual Samples
m w m S p lits-*
t ?: 4 yw r-
TNA 6840 TNA 6843 TNA 6847 TNA 6934 TNA 6935 TNA 6944 TNA 6959 TNA 6960 TNA 6967 TNA 6973 TNA 6975 TNA 6977** TNA 6981 TNA 6992 TNA 6994 TNA 6995 TNA 6997 TNA 7000 TNA 7006 TNA 6938 TNA 6939 TNA 6941
l'ISelSrSSSIM ?m
P Branched
Isorne!;:'
California
11%
Missouri
13%
Pennsylvania
4.1%
Pennsylvania
0.8%
New York
12%
Michigan
3.4%
Virginia
4.3%
Virginia
4.5%
Maryland
9.5%
Montreal, Quebec
4.3%
Montreal, Quebec
4.0%
M assachusetts
< LLOQ*
Texas
3.7%
California
4.2%
California
4.0%
California
6.0%
California
4.0%
California
17%
California
8.3%
New York
2.7%
New York
4.0%
New York
3.0%
40% 40% 43% 45% 37% 35% 40% 38% 43% 42% 42% 39% 43% 40% 39% 41% 41% 41% 41% 44% 35% 36%
jj _
Page 16 of 18
3M ENVIRONMENTAL LABORATORY PROJECT NO.E050120
Table 12. Isomer Ratios for Individual Samples (continued)
iH
TNA 6950 TNA 6953 TNA 6955 TNA 6982 TNA 6964 TNA 6966 TNA 6970 TNA 6972 TNA 6976** TNA 6979 TNA 6982 TNA 6984 TNA 6986 TNA 6988
v t! v
Michigan Michigan Michigan Virginia Virginia Virginia Maryland Maryland M assachusetts M assachusetts
Texas Texas Texas Texas
fTM
0.3% 10% 3.0% 8.8% 5.4% 7.9% 6.7% 5.1% < LLOQ* 7.6% 6.0% 1.3% 0.1% 4.5%
A verage:
S tandard D eviation
*Sample value was < LLOQ **TN-A-6977 and TN-A-6978 are from the same lot of pooled serum.
6% 3%
PFOS % 1 B ran ch ed
39% 39% 35% 41% 42% 40% 39% 38% 41% 30% 41% 31% 43% 33%
39% 3%
mi
All original raw data and the analytical report have been archived at the 3M Environmental Laboratory. The test materials and analytical reference standard reserve samples, as well as the samples pertaining to this project are archived at the 3M Environmental Laboratory.
Reserve samples, digital copies o f original data and all original paper data will be retained in the archives of 3M Environmental Laboratory for a period o f at least 10 years following report signing.
Under the conditions of the study, endogenous fluorochemicals were found to be present in all samples. PFHS, PFOS, and THPFDS were detected in every lot o f serum while PFOA was present in detectable levels in all but one sample. Conversely, FBSA, THPFOS, and the C12 acid were not detected in any o f the samples using the present methodology. 13C PFOA surrogate recoveries were all within 20%.
Page 17 of 18
3M ENVIRONMENTAL LABORATORY PROJECT NO,E05-C120
William Reagen, Laboratory Manager
Date
The 3M Environmental Laboratory's Quality Assurance Unit has audited the data and report for this project.
Quality Assurance Representative
Date
Page 18 of J8
AAUfi. 12.2C05 5; `1PM ^QUALITY ASSOCIATES U1
p. ir
SMENVinOmENTAL UdCftATORY PROJECTNQlBC&WSO
Wiliam Reagen, Laboratory Manager
Date
The JM EavirOBmentei Laboratoiy's Quality Assurance U nit la s audited foe data and report for this project.
RECEIVED TIME AM. 12. 4;48PM
Pace IS of IS
PRINT TIME AM. 12, 4:49PM
