Document Qkx0ka62JGRMEVOOEad4R2r66
3M
K atherine E. R eed, Ph.D. Staff Vice President
3M E nvironm ental, H ealth and Safety O perations
900 Bush Avenue, Building 42-2E-26 PO Box 33331 St. Paul, MN 55133-3331 651 778 4331
A
in A
Certified Mail
J J
--u-Ow
August 26, 2005
& ?-
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NO TSCA CBI
Document Processing Center (Mail Code 7407M)
Room 6428
Attention: TSCA 8(e) Coordinator
Office of Pollution Prevention and Toxics
U.S. Environmental Protection Agency 1201 Constitution Avenue, N. W. Washington, D. C. 20460
Cor>tain Mo cbi
Re: TSCA Section 8(e) Supplemental Notice: Sulfonate-based and Carboxvlic-based Fluorochemicals, Docket Nos. 8EHO-1180-374:/gHQ-0381-0393> 8EHO-Q598-373
Dear Sir:
3M is submitting this notice to supplement its previous submissions on sulfonyl and carboxylic-based fluorochemicals.
3M has recently received the enclosed analytical report which presents data from 36 lots of
commercially available normal pooled human serum that were purchased by the 3M Environmental
Laboratory and subsequently screened for endogenous fluorochemicals. Each sample was analyzed
using a protein precipitation technique and screened for sixteen different fluorochemicals, including
perfluorooctane sulfonate (PFOS) (CgF^SCV) and perfluorooctanoic acid (PFOA) (C7F15COOH),
using liquid chromatography/tandem mass spectrometry (LC/MS/MS). Much of the data presented in
the report was derived from extrapolated curves and should be considered as screening quality data
only and not necessarily representative of the general population levels. Not all of the detected
chemicals are or were produced by 3M. In addition, the levels of fluorochemicals reported are
generally corroborative o f previously reported values and/or do not represent "substantial risk"
information
^rc*zQ>,,
If you have any questions, please do not hesitate to contact Dale L. Bacon at (651) 778-4736. rn o -)
Katherine D. Reed, PhD Staff Vice President Environmental Technology and Safety Services
BEST COPY AVAILABLE
89050000598
0 s0000 5 98
I
3M ENVIRONMENTAL LABORATORY PRO JEC T NO.E05-0120
NO TSCA CBI
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 . EHefson Building 2-3E-09
P O Box 3331 Saint Paul, MN 55133-3331
Phone: 651-778-5405
Testing Facility Management William K. Reagen, Ph.Q. Building 2-3E-09 PO Box 3331
Saint Paul, MN 55133-3331 Phone: 651-778-6565
Requestor
Dale Bacon Building 2-3E-09
PO Box 3331 Saint Paul, MN 55133-3331
Phone: 651-778-4736
Page 1 of 18
JL
3M Environmental Laboratory
Analytical Report
3M ENVIRONMENTAL LABORATORY PRO JEC T NO.E05-0120
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 o f pooled normal human serum were extracted using a protein precipitation technique and screened for sixteen different fluorochemicals 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 analyzed between 02/03/05 and 02/09/05.
This range-finding study was design! to provide lower limits o f quantitation (LLOQs) o f 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 10 - 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 Ofthe 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 o f detection were not included in the average value calculations. Please refer to Section 5 for individual sample results.
Page 2 o f 18
3M ENVIRON M EN TAL LA BO RA TO RY P R O JE C T NO.E05-0120
Table 1. Summary of Perfluorinated Acid R esults
H 8HjH n IP H
Mean
3.33 2.84 NR2 0.954 4.61 1.25 NR2 0.623 <LOD
Median High Low
Standard Deviation
3.33 7.08 0.507 2.17
2.5 3.56 2.45 0.627 -
NR2 NR2 NR2 NR2
0.954 1.02 0.888 0.0933
4.59 23.0 0.477 3.64
1.09 2.63 0.337 0.571
NR2 :- NR2 ' ` NR2
NR2
0.660 0.842 0.312 0.208
<LOD <LOD <LOD ND1
Number of Sam ples with Detectable Analyte
20/36
3/36 : 0/36
2/36 35/36 34/36
0/36
6/36 0/36
N D 1= N ot D etected. This analyte was not detected in any o f die samples. NR2= N o t Reported. This analyte was detected in one o f the 36 samples but appears to be a contam inant or
Table 2. Summary of Other Perfluorinated.and Highly Fluorinated Analyte R esu lts
i.0 M
. ~,i*r uk
Mean
<LOD 0,6775 0.0348 3.27 16.3 <LOD
Median -
<LO& 0,D40f 6.0339 ? 3.Z7 16.9 <LOD
High
<LOD - 0.199 0.0706 5.80 32.8 <LOD
Low
<LOD 0.0311 0.0210 0.780 2.71 <LOD
Standard Deviation
ND1 0.0812 0.0122 1.52 6.71
ND1 -
Fraction of Sam ples with ' Detectable Analyte
0/36 4/36 23/36 36/36 36/36 0/36
N D 1= N ot Detected. This analyte was not detected in any o f the samples.
0.0839 0.0819 0.155 0.0480 Q.0257
36/36
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, wed-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 wed w ith previously obtained NMR data.
Page 3 of 18
3MENVIRONMENTAL LABORATORY PRO JEC T NO.E05-Q120
Table 3. Summary of PFOA and PFO S Isomer Ratios
Human Serum , average Matrix Spike (QC050203-004)
TCR-123 (99030-030) PFO A Lot 332 (NMR characterized value)
TCR-696 PFO S Lot 171 (NMR characterized value)
6% 23% 22%
`
|f|M
39% 32%
31%
Table 4. Reference Substances
Periluorohexanoic acid
Tridecafluoroheptanoic acid
Perfluorooctanoic acid
Heptadecafluorononanoic acid Nonadecafluorodecanoic acid
Perfluoroundecanoic acid
Perfluorododecanoic acid
Perfluorobutanesulfonamide
Perfluorooctanesulfonande
Perfluorobutane sulfonate
Perfluorohexane sulfonate
Perfluorooctane sulfonate 1H, 1H, 2H, 2H,
perfluorooctanesulfonic acid 1H, 1H, 2H, 2H,
perfluorodecane sulfonate Perfluorooctanoic acid, isotopically labeled
PFHA (C6 Acid) TDHA (C7 Acid) PFOA (C8 Acid)
C9 Acid CIO Acid C l 1 Acid C12 Acid . FBSA
FOSA PFBS PFHS PFOS 1HPFOS THPFDS I3C PFOA
Oakwood Products Aldrich 3M
Oakwood Products Oakwood Products Oakwood Products Oakwood Products
3M 3M 3M 3M 3M SynQuest Labs
TCR-673
97.7%
TCR-267
98.2%
TCR-123 (99030-030) 95.0%
TCR-618 TCR-36
98.0% 98.01%
TCR-619
96.4%
TCR-37 (SD037)
99.65%
TCR-314 (00017-026) unknown
TCR.-280 (99131-038) 98.94%
TCR-282 (99131-040) 97.3%
TCR-83 (SE036)
98.6%
TCR-696
86.4%
TCR-343 (00017-055) 93.5%
Pace/3M
TCR-627
94.7%
Perkin Elmer
TCR-744
>97%
0.997 0.997 0.958 0.998 0.998 0.998 0.998 0.997 0.997 0.885 0.911 0.927 0.998
0.998 0.998
fX
S
Page 4 of 18
3M ENVIRONMENTAL LABORATORY P R O JEC T NO.E05-0120
The samples for this study were prepared as follows:
1. The serum samples were allowed to thaw and warm to room temperature.
2. One m illiliter o f serum (or water in the case o f method blanks) was added to a 15 mL screw-capped polypropylene centrifuge tube.
3. M atrix spikes and method blanks were prepared by spiking the serum (or water) with the analytes o f interest In addition, l3C PFOA was added as a surrogate to all serum samples, calibration standards, matrix blanks, and method blanks at a concentration o f 3.01 g/mL to evaluate extraction method performance
4. Two milliliters Ofacetonitrile 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 ref for 20 minutes to pellet the precipitate.
6. After removal from jhe 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:
L iquid C hrom atograph: Hewlett-Packard* Series 1100 Liquid Chromatograph
system
'
Analytical column: Keystone BetasilTM Cm2x100mm, 5pm particle size
Column temperature: 30 `C
Stop Time; 20.0 minutes
Flow rate: 300 pL/min
Injection volume: 5 pL
M obile phase components:
Solvent A: 2.0 mM ammonium acetate in ASTM Type I water
Solvent B: HPLG Grade Methanol
Solvent Gradient:
Time 0.00 1.00 14.50 15.50 16.50 20.00
%B 20% 20% 90% 90% 20% 20%
Page 5 o f 18 6
3M ENVIRONMENTAL LABORATORY PRO JEC T NO.E05-012Q
Mass Spectrom eter: 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 5. Acquisition Param eters
PFBA (C4add) NFPACs Arid
PFHA (Ce add) TDHA (Qy Arid) PFOA (Cg Arid)
Ce Acid C 10Arid Cu Arid C i2Acid
FBSA FOSA PFBS PFHS PFOS THPFOS THPFDS PFOA[1,2-13C]
213.0 262.9 313.0 362.9 413.0 463.0 512.9 563.0 613.0 297.9 497.9 298.9 398.9 498.9 426.9 526.9 414.9
:
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 4686,218.9,269.1 518.7,268.9,218.8 568.7,168.9,318.7 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
-30 -30 -45 -35 -40 -50 -100 -45 -50 -55 -90 -65 -95 -80 -70 -70 -40
Up Sills
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 4.1.1 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 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
1
m ENVIRONMENTAL LABORATORY P RO JEC T NO.E05-0120
Calibration standards were within 20% (25% for the Lower Limit of Quantitation (LLOQ)) with a coefficient of 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. 4.12 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 125% for all analytes. 4.13 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 felled. The %RSDs were 6.2%, 7.5% and 8.4%. However, no samples had area counts above the LLOQ for this analyte therefore tiie data was accepted. 4.1.4 Ix>wer Omit 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%. 4.15 Limit ofDefection (LQD) The LOD for each analyte was equal to the area counts (converted to a concentration) that were 2-3 times above the method blank. 4J..6 Blanks Method Blanks All o f the method blanks in tins study had area counts <50% o f the LLOQ. M atrix 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 Vi the LLOQ for BLK050203-003.
f Page 7 o f 18
3M ENVIRONMENTAL LABORATORY PRO JEC T NO.E0S-0120
Table 6. Average Endogenous PFO S Value Determination
LLO Q (ng/mL)
0.306
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 ofPFOS in rabbit serum.
4.1.7 Solvent Blanks
Acetonitrile blanks were analyzed throughout the analytical run. Analyte response was less than 14the LLOQ in all cases.
4.1.8 Surrogate
13C PFOA was added as a surrogate to all senrm 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 of analyte in the matrix (where appropriate), and are presented below.
Table 7. Matrix Spike Recoveries in Rabbit Serum
PFBA (C4 add) LOO =0.426 ng/mL
LLOQ 3.00 ng/mL
IP
QC050203-001
3.00
QC05203-002'
3.00
QC050203-003
' 3.00
QC050203-04
75.6
QC050203-005
75.6
QCO50203-006
75.6
' ' "....
.
N FPA (CSacid) LOD * 4.53 ng/mL LLOQ * 15.3 ng/mL
NA = N ot Applicable
QC05Q203-001 QC050203-002 QC050203-003 QCQ502Q3-004 QC050203-005 QC050203-006
"" 3.06 3.06 3.06 77.7 77.7 77.7
< LLO Q .... < LLOQ < LLOQ
70 71.3 70.2
< lloq < LLOQ < LLOQ 68.00 80.50 97.20
-
NA NA NA 93% 94% 93%
P
M NA
1.0%
NA NA NA 88% 104% 125%
.|
NA 17.9%
Page 8 of 18
<1
Table 7. Matrix Spike Recoveries in Rabbit Serum (continued)
3M ENVIRONMENTAL LABORATORY P R O JEC T NO.EOS-0120
PFHA (06 add) U-OQ = 15.1 ng/mL
QC050203-001 QC050203-0Q2 QC050203-003 QC050203-004 QC050203-005 QC050203-006
i >* _ :rib.
3.03 <LLOQ
3.03 <LLOQ
3.03 < LLOQ
76.8 -
62.4 .
76.8 '
772
76.8 94.2
NA NA
NA 81% :. 401% 123%
NA 20.4%
TDHA (C7 add) LLOQ 3.03 ng/mL
QC050203-001 QC050203-002 QC050203-003 QC050203-004 QC050203-005 0005020^006
3.03 3.03 3.03 76.5 . 76.5 . 76.5
<LL0Q < LLOQ < LLOQ
66.9 80.1 95.4
NA NA NA 87% 105% ,. 125%
NA 17.7%
C1ACID LLOQ 3.12 ng/mL.
QC050203-001 QC050203-002 QC050203-003 QC050203-004 QC050203-005
QC050203-006
3.12 3.12 3.12 78.6
78.6 78.6
< LLOQ <LLOQ < LLOQ
65.4
71.9
83.1
..
C 1 1 A C ID LLOQ * 0297 ng/mL
....
00056203-001 ' 2.97
QCQ5203-002
297
00050203-003 3. 2 9 7 .
QC050203-004 75.3
QC050203-005 hi- 75.3 -- :
QC050203-006
752. .
298 271 295. 752 . - 78.3 _ .. 782
......... ..... -
QC050203-001 I" 3.0b : L- 3.04-
QC050203-02
3.06 '
3.13
C12ACID.............. : QC050203-003 i - 3.00 i~ . 3.28
LLOQ *0.747 ng/mL
QC05203-OQ4 - ........ 75.6 .
QC050203-005
.. 75.6 -
762 822-
QC050203-006
75.6
78.3
N A = N ot A pplicable
NA NA NA. 83% 91% 106%
-T 100% 91% 99% 101% 104% 104%
101% 104% 109% 101% 109% 104%
NA
12% ---
' 5.1%
1.8% ! 3.8%
'3.9%
I 1
Page 9 o f 18
/?
Table 7. Matrix Spike Recoveries in Rabbit Serum (continued)
3M ENVIRONMENTAL LABORATORY PRO JEC T NO.E0S-0120
M B B S H p E f T W irP iT
" c PFOA
C9 Acid LLOQ =0.303 ng/mL
QC050203-001 QC050203-02 QC050203-003 QC05203-Q04 QC050203-005 QC050203-006
.- :
QC050202-001 QC050202-002 QC050202-003 QC050202-004 QC050202-005 QC050202-006
3.1
3.01 3.01 3,01 3.01 .
3.01
-
.................................
3.03
. 3,03 ... .................. 3.03 .
75,4 75:4 :
75.4;
PFOA LLOQ * 0J298 ng/mL
QC050202-001 QC050202-002 QC050202-003 QC050202-004 QC050202-005 QC050202-006
2 .9 8 ;:. 2.98
2.96 . 75,6 75,6 75.6
: QC050203-001
FBSA
QC050203-002 QC050203-003 .
LLOQ =0.303 ng/mL QC050203-Q04 QC050203-005
QC050203-006
FOSA LLOQ *0.300 ng/mL
QC050203-001 QC050203-002 QC050203-003
QC050203-004 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
2.81 3.06 2.94 2.68 2.91 2.75 .
3.23 3.04 ' 2.95 77.4 . 75.8 69.9
..
2.93 2.58
2.65 ; 75.2
76.4 77.6
2.96 2.92 2.95 75.9 77.9 77.7
2.78 2.74 2.74 76.6 77.1 76.0
93% 102% 98% 89% 97% 91%
107% 100% 97% 103% 101% 93%
98% 87% 89% 99% 101% 103%
98% 96% 97% 99% 102% 102%
93% 91% 91% 101% 102% 100%
4.8%
4.7% 5.3%
6.8%
-
1.6%
0.7% 1.4%
0.8% 0.7%
Page 10 of 18
3M ENVIRONMENTAL LABORATORY PRO JEC T NO.EOS-0120
Table 7. Matrix Spike Recoveries in Rabbit Serum (continued)
~
PFBS LLOQ = 0.303 ng/mL
1 QC050203-001
3.03 . - '
QC050203-002
3.03"" " -
QC050203-003
......... 3.03
QC050203-004
76.8
QC050203-05"
: 7 6 .8 .........
QC05203-006 ' ' ............. 76.8 ........... -- .........; -
PFHS LLOQ =>0.315 ng/mL
QC0502Q3-001 00050203*002 QC050203-003 00050203-4)04 QC050203-005 QC050203-006
...... ..
3.15 .......... 3 tg /
3.1$ 79:8 79.8 79.8 ;
-3.06 3.00 3.01
75.8 78.3 77.2 ' -r "
H
! 101% 99% 99% 99% 102%
101% -
3.04 3.08 3.04 78.2 79.9 78.6
''
97% 98% 97% 98% 100% 98%
I
1.1% 1.6%
0.8% 1. 1%
THPFOS LLOQ = 0.780 ng/mL
QC050203-O0T QC050203-002 00050203*903 QC050203-004 QC050203-005
3 .f2 3.12-
...: 3 .2 -: 78:9 78.9
3.02 2.63 2.83 . . . 6e;o 80.0
97% " 91%
- 91% . 84%
101%
QC050203-006 '!
r' '
78.9
l -':'
g a s / / - . " 122%
\:
QCQ5Q2Q3*0Q1_ .
THPFOS
_ 00050203902. . 00050203*003___
LLOQ 0.303 ng/mL L . QC050203-004.. J QC050203-005 !
-3.03 -- .
2.96
3.03 '____ ' . . 3.00
..... 3 X S - ........- : 3.12
7 6 ------ ~ - 77.6
76.
79.8
98% 99% 103% 102% . 104%
QC050203-006
76:
782 102%
i
3.8% 19%
2.8% 1.3%
Page 11 o f 18 I fi"
3M ENVIRONMENTAL LABORATORY PRO JEC T NO.EQS-0120
Table 8. PFO S Matrix Spike Recovery in Rabbit Serum, Corrected for Endogenous Levels
4.3 Accuracy The accuracy for each analyte reported was calculated by taking the average o f die matrix spike recoveries for that analyte. The results are presented below.
Table 9. Method A ccuracy for Individual Analytes
j^ A cteiraibjis fjjih^k^ -Anal.yte '.'I.-J.'.
PFBA *
7%
C 1 2 A cid
5%
N FPA *
6%
FBSA
..1%
PFH A *
2%
FO SA
4%
C 7 A cid *
6%
PFBS
1%
PFO A
4%
PFH S
2%
C 9 A cid
1%
PFO S
5%
C 1 0 A cid *
7%
TH PFO S
2%
C 1 1 A cid
1%
TH PFDS
1%
T he % A ccuracy reported for this analyte is based on the high concentration spike recovery data only because the low concentration
spike recoveries were less than the ULOQ.
4 .4 Sample Related Comments
The extraction and analysis o f the samples was performed utilizing a non-validated method. The matrix spike results, l3C PFOA surrogate recoveries, and the extrapolated calibration curve (between the LLOQ and LOD) should be considered when evaluating the accuracy and precision of the sample results.
Tables 10 and 11 summarize individual sample data.
3M ENVIRONMENTAL LABORATORY P R O JEC T NQ.E05-0120
Table 10. Perfluorinated Acid R esults
`
;
.
,.......
-,
e*<a;r-/> ' ',
'_j "' f - i "
T ` r ("""l
*<
* . "?
>?* -31.1 S+
,
-1 if
^ " 1 J-.-- -.-"if
i ` 1'
^ ~ -**1*** _A^'
j " ` 1 'T*!
,.q>. . .. ... j l-r .. i . . . M*m I____ **, n , J
T" :
"
. ' t i' rA '"
,,'i I r r
1' \
' ..r...
.
^
-
r;.v1.i. -Ui.i .t... 1*P i
..i
jjf- A L JJ
iif 12
^
/ A
' ' l i m m i: ' i
IS a J .*
TNA6840
5.19
Z50 " <LOD < L00
5.48 ' ' : 1.52
<L00
<LOD
<LOD
TNA6843
0.990* <LOD <LOD < .0 0 ! 0.581
0.574
<LOO
<-OD
UOD
TNA6847
0.507* <LOD <-OD <LOD
4.61 : 0.976
<LOD
<LOD
<LOD
TNA6934
<LOD
<L0D <LOD <LOD 1 7.69 : 2.26
<LOD
<LOD
<LOD
TNA6935
1.17*
<LOD <loct <LOD " 5TW ' 1.63
<LOD
0.451
<LOD
TNA6944
7.08 <tOD <LOD <LOD ! 7.38'
1.45
<L0D
<LOD
<LOD
TNA6959
4.91
<UOD <L0D <LOD
3.13
2.45
<LOO
0.700
<UOD
TNA6960
3.32
<LOD <LOD <L0D
4.59
1.11
<L0D
<LOD
<LOD
TNA6967
4.09
<LOD <LOD <LOD
5.30
1.62
<L0D
<LOD
<LOD
TNA6973
6.73
3.56 <L0D 0.888* 5.51
1.64
<LOD
<LOD
<LOD
TNA6975
2.95*
<LOD <LOD <.OD
5.52
1.31
<L0D
<LOD
<LOD
Page 13 of 18
/f
Table 10. Perfluorinated Acid Results (continued)
3M EN VIRON M EN TAL LA BO RATO RY P R O JE C T N0.EQS-0120
BSeHEP P H w m m . 111911S f s i
TNA 6977** 5.04
<LOD cLOD CLOD 0.477 CLOD
TNA6981 6.76
Z45 <LOD CLOD 4.12
1.28
TNA 6992 0.690* <LOD CLOD CLOD 4.76 0.912
TNA 6994 <LOD <LOD CLOD <LOD 1.15 0.337
TNA6995 1.98* <LOD
i
1.02*
3.58 ' 2.63
TNA6997 3.90
cLOD CLOD <LOD
3.46
2.52
TNA7000 3.34
<LOD CLOD CLOD
23.0;
T08
TNA7006 3.19
<LOD CLOD , CLOD
4.18
1.09.
TNA6938 <LOD <LOD. CLOD CLOD 5.00 0.979
TNA6939 <LOD <LOD - CLOD <LOD 2.32 0.941
TNA6941 3.56 <LOD CLOD CLOD 5.82
1.69
TNA 6950 <LOD <LOD CLOD CLOD 3.87 0.723
TNA6953 0.621* <LOD CLOD CLOD 5.49 0.725
TNA6955 <LOD <LOD CLOD CLOD 2.54 0.562
TNA 6962 <LOD <LOD CLOD CLOD 4:68 0.941
TNA6964 <LOD <LOD CLOD <LOD
5.61:
1.58
TNA 6966 <LOD <LOD CLOD. CLOD
4.73
1.35
TNA 6970 <LOD <LOD CLOD <LOD 6.00
1.42
TNA6972 <LOD <LOD CLOD CLOD
3.40
1.09
TNA 6978** ! <LOD <LOD CLOD CLOD cLO D <LOD
TNA 6979 <LOD <LOD CLOD CLOD 3.32 0.981
TNA 6982 <LOD <LOD CLOD <LOD 1.48 0.664
TNA 6984 <LOD <LOD CLOD CLOD 2.84 0.955
TNA 6986 0.530* <LOO CLOD <LOD . 2.08
0.645
TNA 6988 <LOD <LOD CLOD CLOD 2.57 0.881
Moan
3.33 2.84
NA j 0.954* 4.61
125
Median 3.33 2.50
NA 0.954* 4.59
1.09
High
7.08 3.56
NA
1.02*
230
2.63
Low ] 0.507* 2.45
NA 0.888* 0.477 0.337
CLOD CLOD <LOD CLOD <LOD CLOD <LOD CLOD <LOD <LOD <LOD 14.0*** <LOD <LOD CLOD <LOD <LOD <LOD CLOD cLOO cLOD CLOD CLOD CLOD CLOD
NA NA NA NA
warn CLOD CLOD CLOD CLOD 0.815 0.842 CLOD CLOD cLOD 0.312 0.620 | CLOD CLOD CLOD CLOD CLOD <LOD cLOD CLOD cLOD CLOD cLOD CLOD c LOD <LOD 0,623 0.660 0.642 0.312
CLOD CLOD cLOD CLOD cLOD CLOD CLOD CLOD CLOD cLOD cLOD CLOD CLOD CLOD CLOD cLOD CLOD cLOD CLOD CLOD cLOD CLOD cLOD CLOD CLOD
NA NA NA NA
Standard Deviation
# OF HITS
2.17 20
0.627 3
NA 0.0933 3.64 0.571 0 2 35 34
NA 0
0.208 6
NA 0
NA = N ot A pplicable A nalyte concentration was below the LLOQ and above the LOD. T N -A -6977 and TN -A -6978 are from die sam e lo t o f pooled serum . A n alyte w as detected in one o f die 36 sam ples but appears to be a contam inant or an anom aly; the
sam ple w ill b e reanalyzed and the results w ill be reported in the definitive study. Based on 15C PFOA surrogate recovery, the overall m ethod uncertainty is + /- 20%.
Page 14 of 18
.BfcJiI
3M ENVIRON M EN TAL LA BO RATO RY P R O JE C T NO.E05-0120
Table 11. Sam ple Results for Additional Perfluorinated and Highly Fluorinated Analytes
TNA 6840 TNA 6843 TNA 6847 TNA 6934 TNA 6935 TNA6944 TNA6959 TNA6960 TNA6967 TNA 6973 TNA 6975 TNA 6977TNA 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 6978TNA 6979 TNA 6982 TNA 6984 TNA 6986
.
COD COD COD COD COD COD COD COD COD COD COD COD COD COD COD COD COO COD COD COD COD COO COD COD COD COD COD COD COD COD COD COD COD COD COD
k;
COD COD 0.0458* COD COD COD COD COD 0.199* COD COD COD 0.0311* COD COD COD COD COD COO COD COD COO COD COD COD COD COD COD COD COD COD 0.0344* COD COD COD
COD 0.0228* COD 0.0304* 0.0433* 0.0706* COD 0.0292* Q.0358* COD Q.0393* 00339* 0.0313* 0.0429* COD 0.0366* 0.0479* oases* 0.04,12* 0.0226* COD 0.0224* COD 6.0226* COD 0.0312* 0.0374* 0.0229* COD 0.0349* 0.0210* 0;0228* COD COD COD
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
i1t 4.06
6:945
2.31 1.26 1.73 1.41
23.0 3.42
23.7 32.8 16.2 20.4 1.4.8 19.6 21.3 20.5 19.4 3.01 17.4 19.8 3.50 15.1 15.2 22.9 202! 15.6 6.23 23.4 14.3 22.1 10.1 19.8 .2 1 .7 17.5 17.0 12.7 2.71 16.7 9.37 15.8
11.3.
COD COD COD COD COD COD COD COD COD COD COD COD COD COD COD COD COO COD COO COD COS COD COD COD COD CO S' COD COD COD COD COD COD COD COD COD
0.124* 0.155* 0.145* 0.0531* 0.0820* 0.0860* 0.0649* 0.0819* 0.0857* 0.0618* 0.0622* 0.0916* 0.103* 0.0826* 0.0616* 0.0853* o .0 7 o r 0.0638* 0.0667* 6.0601* 0.0625* 0.0577* 0.0909* 0.0480* 0.0493* 0.0705* 0. 101* 0.0620* 0.137* 0.0653* 0.0998* 0. 102* 0.0790* 0.0911* 0.0683*
Page 15 o f 18
16
3M ENVIRONMENTAL LABORATORY PRO JEC T NO.E05-0120
Table 11. Sample R esults for Additional Perfluortnated and Highly Fluorinated Analytes (continued)
TNA6988 Mean
- Median High Low
<LOP NA NA NA NA
<LOO
0.0776* 0.0401* 0.199* 0.0311*
<LOD 0.0348* 0.033910.0706* 0. 0210*
1.79 3.27 3.27 5.80 0.780
16.5 16.3 16.9 32.8 2.71
Standard Deviation NA 0.0812 0.0122 1.52 6.71
# OF HITS
23 36 36
NA = N ot A pplicable
...........'
A nalyte conceatraticin was below the LLOQ and above die LOD.
TN -A -6977 and -6 9 7 8 are from the same lot o f pooled serum .
B ased on llC PFOA surrogate recovery, die overall method uncertainty is + /- 20% .
<LOD NA NA NA NA
NA
0
0.0979* 0.0839* 0.0819* 0.155* 0.048*
0.0257
36
Table 12. isom er Ratios for Individual Samples
TNA 6840 TNA6843 tN A6847 TNA6934 TNA6935 TNA6944 TNA6859 TNA6960 TNA6967 TNA6973 TNA6975 TNA 6977** TNA6981 TNA 6992 TNA 6994 TNA 6995 TNA 6997 TNA 7000 TNA 7006 TNA 6938 TNA 6939 TNA 6941
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
11% 13% 4.1% 0.8% 12% 3.4% 4.3% 4.5% ' 9.5% 4.3% 4.0% < LLOQ* 3.7% 4.2% 4.0% 6.0% 4.0% 17% 6.3% 2.7% 4.0% 3.0%
(7
40% 40% 43% 45% 37% 35% 40% 38% 43% 42% 42% 39% 43% 40% 39% 41% 41% 41% 41% 44% 35% 36%
Page 16 of 18
3M ENVIRONMENTAL LABORATORY PRO JEC T NO.E05-0120
Table 12. Isomer Ratios for individual Sam ples (continued)
TNA6950 TNA69S3 TNA6955 TNIA6962 TNA6964 TNA6966 TNA6970 TNA6972 TNA6976TNA6979 TNA6982 TNA6964 TNA6986 TNA6988
Michigan Michigan Michigan Virginia Virginia Virginia i :: Maryland , Maryland Massachusetts Massachusetts
Texas Txs Texas Texas
0.3%
10%
3.0% 6.8% 5.4% 7.9% 6.7% 5.1% <U-OCr 7.6% 6.0% 1.3% 0.1% 4.5%
Average;
S tandard D eviation
Sample value was < LLQQ
**T N -A -697f and TN -A -6978 are from the same lot o f pooled serum.
6%
3%
39% 39% 35% 41% 42% 40% 39%
38%
41% 30% 41% 31% 43% 33%
39% 3%
A ll original raw data arid 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 pap: data will be retained in the archives o f 3M Environmental Laboratory for a period o f at least 10 years following report signing.
Under the conditions o f 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. I3C PFOA surrogate recoveries were all within 20%.
Page 17 of 18
IS
3M ENVIRONMENTAL LABORATORY PRO JEC T NO.E05-0120
The 3M Environmental Laboratory's Quality Assurance Unit has audited the data and report for this project
Q uality Assurance R ep resen tative
D ate
jjjjjj AAUG. 12. 2005 5:' 1PM -QUALITY ASSOCIATES W 01
8 . S jE g a^o m
NO. 074" P. I/'
SUEUVmONU&iTAL LABORATORY PR O JE C T N C JSO & ^t20
Tbe3M Baw ronm entilIjboattory,sQ u a% Aasoxanca Unit has audited fee data and
RECEIVED TIME AUG. 12. 4:48PM
?*ee is of is
PRINT TIME AUG, 12. 4:49PM