Document 4vm04zQdBmjZRaDnxROOk9a4R
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Katherine E. Reed, Ph.D. Staff Vice President
3M Environmental, Health and Safety Operations
M sla6 - 3 W
900 Bush Avenue, Building 42-2E-26 PO Box 33331 St. Paul, MN 55133-3331 651 778 4331
it
3M
Certified M ail
Cil! - - u - . j d
August 26,2005
9 .< 2 ,4 * `l s f
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
c ntair> N O C B l
Re: TSCA Section 8(e) Supplemental Notice: Sulfonate-based and Carboxvlic-based Fluorochemicals, Docket Nos. 8EHO-1180-374:/gglTO-0381-035fo 8EHO-0598-373
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) (CgFnSCV) 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
rO O
If you have any questions, please do not hesitate to contact Dale L. Bacon at (651) 778-4736. ^ rn 0 - 0
Katherine D. Reed, PhD Staff Vice President Environmental Technology and Safety Services
B ES T CO PY AVAILABLE:
89050000598 9 0 s 000 0 5 9 8
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 ENVIRONMENTAL LABORATORY P R O JEC T NO.E05-0120
Table 1. Sum m ary of Perfluorinated Acid Results
H Hn II n V HR
9B
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 NR2 3.56 NR2 2.45 NR2 0.627 - 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 35/36-1 34/36
0/36
6/36 0/36
ND1= N ot Detected. 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 contaminant or
Table 2. Sum m ary of OtherPerfluorinated.and Highly Fluorinated Analyte R esults
P H i l .0
Mean
<LOD 0,6775 0.0348 3.27 16.3
Median -
<LOD 0,D40f 6.0339 ? 3.Z7 16.9
High
<LOD 0.199 0.0706 5.80 32.8
Low <LO 0.0311 0.0210 0.780 2.71
Standard Deviation
ND1 - 0.0812 0.0122 1.52 6.71
Fraction of Sam ples with ' Detectable Analyte
0/36 4/36 23/36 36/36 36/36 _____ i
ND1= N ot Detected. This analyte was not detected in any o f the samples.
<LOD <LOD <LOD <LOD ND1 -
0.0639 0.0819 0.155 0.0480 Q.0257
0/36 .
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 well w ith previously obtained NMR data.
Page 3 o f 18
3MENVIRONMENTAL LABORATORY PRO JEC T NO.E05-Q120
Table 3. Sum m ary of PFOA and PFO S Isomer Ratios
jss.
-r .vf
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%
`
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
Pace/3M Perkin Elmer
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%
TCR-627
94.7%
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 PFOAwas 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 ref for 20 minutes to pellet the precipitate.
6. After removal from ihe 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 Cj* 2x100mm, 5pm particle size
Column temperature: 30
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:
Tim e 0.00 1.00 14J0 15.50 16.50 20.00
%B 20% 20% 90% 90% 20% 20%
Page 5 o f 18
G
3M ENVIRONMENTAL LABORATORY PRO JEC T NO.E05-0120
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
llljB B E S fli
PFBA (C4add) NFPACs Arid PFHA (Cb add) TDHA (C7Arid) PFOA (Cg Arid)
Ce Acid C 10Arid Cu Arid C i2Add
FBSA FOSA PFBS PFHS PFOS THPFOS THPFDS PFO A [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 4689,218.9,269.1 518.7,268.9,218.8 568.7,168.9,318.7 78.0 77.9 98.9,79.9 98.9,80.0 8 0 .0 ,9 9 9 ,1 3 0 .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
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 maimer 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
3M ENVIRONMENTAL LABORATORY PRO JEC T NO.E05-Q120
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 25% 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 fee data was accepted. 4.1.4 I^wer 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%. 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. 4X 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
Blk050203-0Q3
< 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 14die 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. M atrix Spike Recoveries in Rabbit Serum
PFBA (C4 add) LOO = 0.426 ng/mL LLOQ -3 .0 0 ng/mL
QC050203-001 :
3.00
QC050203-002
3.00
QC050203-003
' 3.00
QC050203-004
75.6
QC050203-005
75.6
QCO50203-006
75.6
' ' " ...
.
N F P A (C Sacid) LOD 4.53 ng/mL LLOQ 15.3 ng/mL
NA = N ot Applicable
QC05Q203-001 QC050203-002 QC050203-003 QC050203-004 QC050203-005 QC050203-006
"" 3.06 3.06 3.06 77.7 77.7 77.7
< LLOQ... < LLOQ < LLOQ
70 71.3 70.2
I S S S lfl llP lj ll -
NA NA NA NA 93% 94% 1.0%
93%
< LLOQ < LLOQ < LLOQ 68.00 80.50 97.20
-
NA NA NA
NA . 1
88% 104%
17.9%
125%
Page 8 of 18
Table 7. Matrix Spike Recoveries in Rabbit Srum (continued)
3M ENVIRONMENTAL LABORATORY P R O JEC T NO.EOS-0120
IIm B p I
PFHA (C6 ad d ) LLOQ = 15.1 ng/mL
QC050203-001 QC050203-0Q2 QC050203-003 QC050203-004 QC050203-005 QC050203-006
3.03 3.03 3.03 76.8 76.8 ' 76.8
<LLOQ <LLOQ <LLOQ
62.4 . 772 94.2
TDHA (C7 ad d ) LLOQ * 3.03 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
<LLOQ < LLOQ < LLOQ
66.9 80.1 95.4
CIO ACID 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 ., 78.8
< LLOQ < LLOQ < LLOQ
65.4
71.9
83.1
C11ACID LLOQ * 0297 ng/mL
QCQ56203-00-1 QC05203-002 00050203-003 QC050203-004 QC050203-005 QC050203-006
- 2.9X
2.97
a. 227
75.3 -
.
- 75.3---:' -
752. .. .....
. .......
.
2.98 2.71 2.95752 78.3 782
.
.
_
C12ACID............ LLOQ *0.747 ng/mL
NA = N ot Applicable
QC050203-001
3.05 -
QC050203-02
3.06 "
- QC050203-003 3.00 h -.
QC050203-004 - ...... 75.6 . .
QC050203-005 .. 75.6 -
QC050203-006
75.6
3.043.13 3.28 :
762 82278.3
NA NA NA 81%:. 401% 123%
NA NA NA ' 87% 105% 125%
NA NA NA. 83% 91% 106%
100% 91% 99% 101% 104% 104%
101% 104% 109% 101% 109% 104%
NA 20.4%
NA 17.7%
NA 12%
5.1% 1.8% 3.8% 3.9%
Page 9 o f 18
/?
Table 7. Matrix Spike Recoveries in Rabbit Serum (continued)
-" " ft. ,"W
if? .. f j a t e ,
" 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
3.01
3.01
3.01
3.01 .
3.01
...
............................................
3.03
. 3,03 ... ...............3.03
75.4 75:4 : 75.4;
PFOA LLOQ* 0.298 ng/mL
QC050202-001 QC050202-002 QC050202-003 QC050202-004 QC050202-005 QC050202-006
2.98 1 2.98
2.98 . 75,6 75,6 75.6
: QC050203-001
FBSA
QC050203-002 QC050203-003
LLOQ = 0.303 ng/mL QC050203-004 QC050203-005
QC050203-006
FOSA LLOQ *0.300 ng/mL
QC50203-001 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
3M ENVIRONMENTAL LABORATORY PRO JEC T NO.EQS-0120
-1 f
3.06 2.94 2.68 2.91 2.75 .
3.23 3.04 ' 2.95 77.4 . 75.8 69.9
93% 102% 98% 89% 97% 91%
107% 100% 97% 103% 101% 93%
I
2.93 98%
2.58 87%
2.65 89%
; 75.2
99%
76,4 - ; 101%
77.6 103%
2.96 98% 2.92 96% 2.95 97% 75.9 99% 77.9 102% 77.7 102%
2.78 93% 2.74 91% 2.74 91% 76.6 101% 77.1 102% 76.0 100%
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.E05-O120
Table 7. M atrix Spike Recoveries in Rabbit Serum (continued)
--"i Sr* tr
PFBS
4 t-'
-(
'j `i t 'l l ;
1 QC050203-001 QC050203-002 QC050203-003
,
3.03 . - ' 3.03" ` "
....... 3.03 ;
-356 3.00 3.01
;ii
-M 1 , 101%
i 99% H 99%
LLOQ = 0.303 nfl/mL
QC050203-004
76.8
QC05203-05'
: 7 6 .8 .......
QC05203-006 ' ' ...........7 6 a ' ......... ........... ; -
75.8 '. ! 99%
78.3 102%
77a '
101%
"~
' PFHS
LLOQ = 0.315 ng/mL
QC0502Q3-001 "" ..... 00050203=002 QC050203-003 QC0502034)04 QC050203-005 QC050203-006
i t s ':........ 3.15.: 3.15: 79:8 79.8 79.8 7
354 3.08 3.04 78.2 79.9 78.6
THPFOS
QC050203-001 QC050203-002 00050203^03
3.2 3.12... 3 .t2 -: ..
3.02 2.83 2.83
LLOQ = 0.780 ng/mL
QC050203-004
QC050203-005 -
QC050203-006 ,A "V,
r' '
78.9
78a
1
. 66.0 80.0
gas
00050203=001 -
. 3.03 -- .
2:96
THPFOS
_ 00050203-002. 00050203=003__
....... 3.03 '___ ' .... 3X 3.. ...... -
. 3.00 : 3.12
LLOQ 0.303 ng/mL
QC050203-004.. ... QC050203-005
7 6 a '------- .. - 77a
76.5
79.8
QC050203-006
7 sa
78.2
97% 98% 97% 98% 100% 98%
' 'I 97% 91%
- 91% 84% 101%
": 122%
-i.. :
98% 99% 103% 102% 104% ^ 102%
1.1% 1.6%
0.8% 1.1%
3.8% 19%
2.8% 1.3%
Page 11 o f 18
3M ENVIRONMENTAL LABORATORY PRO JEC T NO.E0S-0120
Table 8. PFO S M atrix Spike Recovery in Rabbit Serum , Corrected for Endogenous L e v e ls
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
y ' ._j ,
PFBA*
7%
A n a lyte '
k . '.'I.- J.'.
C12 Acid
5%
NFPA* PFHA*
6%
2%
FBSA FOSA
..1% 4%
C7 Acid*
6%
PFBS
1%
PFOA
4%
PFHS
2%
C9 Acid
1%
PFOS
5%
C10 Add*
7%
THPFOS
2%
C11 Acid
1%
THPFDS
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, 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 18
3M ENVIRONMENTAL LABORATORY P R O JEC T NO.E05-0120
Table 10. Perfluorinated Acid Results
1,, r i i.: i
n1 , -, *<
W - : 4' Jt r ' J?
j
ri,
f ' ' "**
r .- r
i'
1 Ui - *1 1iP
t
TNA6840 TNA6843 TNA6847 TNA6934 TNA6935 TNA6944 TNA6959 TNAB960 TNA6967 TNA6973 TMA697S
.M M 5.19 0.990* 0.507* <LOD 1.17* 7.08 4.91 3.32 4.09 6.73 2.95*
i i i i 1!..atiLaaa:!2.L -s t Va.>tU,*i*S* 2.50 " CLOD CLOD 5.48 ' ' j <LOD CLOD CLOD 0.581 CLOD CLOD CLOD . 4.61 : CLOD CLOD cLOD 7.69 CLOD <LOD~ CLOD 19 CLOD cLOD cLOD 7.38' CLOD CLOD cLOD 3.13 CLOD CLOD cLOD 4.59 <LOD CLOD cLOD 5.30 3.56 CLOD 0.888* 5.51 CLOD CLOD CLOD 5.52
1.52 0.574 0.976 2.26 1.63 1.45 2.45 1.11 1.62 1.64 1.31
il L~J
J j j j .d p i
It * &/
*- V.' .
J J* j ItS - i t |
CLOD CLOD CLOD CLOD CLOD CLOD cLOD cLOD CLOD CLOD CLOD
CLOD cLOD CLOD CLOD 0.451 CLOD 0.700 CLOD cLOD CLOD CLOD
CLOD cLOD CLOD cLOD cLOD CLOD cLOD cLOD CLOD CLOD CLOD
Page 13 of 18
/f
3M ENVIRONMENTAL LABORATORY PRO JEC T NO.EQS-0120
Table 10. Perfluorinated Acid Results (continued)
|, [d v P f -- - '-"ffc*. 2
sijj *
5. - *-*x T* ' ip t '-!! _->H t <> -
t it _
_i _
TNA 6977** TNA6981 TNA6992
5.04 6.76 0.690*
<LOD 245 cLOD
--* r it >-2 iti
cLOD <LOD <LOD
<LOD <LOD <LOD
r a il fofrHiAitn
0.477 4.12 4.76
CLOD 1.28 0.912
CLOD CLOD cLOD
n
I CLOD CLOD CLOD
SR
CLOD CLOD cLOD
TNA 6994 TNA6995
<LOD 1.98*
<LOD <LOD
t ed
<LOD
<LOD 1.02*
1.15 0.337 3.58 ' 263
CLOD CLOD
CLOD 0.815
CLOD cLOD
TNA6997 TNA7000 TNA7006
3.90 3.34 3.19
<LOD <LOD <LOD
<LOD cLOD <LOD ,
CLOD CLOD CLOD
3.46 23.0; 4.18
252 T08 1.09.
CLOD CLOD CLOD
0.842 CLOD CLOD
cLOD CLOD cLOD
TNA6938 <LOD <LOD. <LOD CLOD 5.00
0.979
CLOD
cLOD
CLOD
TNA6939 TNA 6941 TNA6950
<LOD 3.56 <LOD
<LOD . <LOD <LOD <LOD <LOD <LOD
CLOD CLOD CLOD
2.32 5.82 3.87
0.941 1.69 0.723
CLOD CLOD 14.0***
0.312 0.620 CLOD
cLOD cLOD CLOD
TNA6953 0.621* <LOD <LOD CLOD 5.49 0.725
CLOD
CLOD
CLOD
TNA6955 <LOD <LOD <LOD CLOD 254
0.562
CLOD . CLOD
CLOD
TNA6962 <LOD <LOD cLOD CLOD 4168 0.941
CLOD
CLOD
CLOD
TNA6964 <LOD <LOD <LOD CLOD 5.61:
1.58
cLOD
CLOD
CLOD
TNA 6966 <LOD <LOD <LOD CLOD 4.73 1.35 cLOD TNA 6970 <LOO <LOD <LOD CLOD 6.00 1.42 CLOD
CLOD cLOD
CLOD CLOD
TNA6972 <LOD TNA 6978** <LOD
<LOD <LOD
<LOD <LOD
CLOD CLOD
3.40 cLOD
1.09 CLOD
CLOD cLOO
CLOD cLOD
CLOD CLOD
TNA 6979 TNA 6982 TNA 6984 TNA 6986 TNA 6988
Moan Median
<LOD <LOD <LOD 0.530.* <LQD 3.33 3.33
<LOD <LOD CLOD <LOD cLOD CLOD <LOD <LOD CLOD <LOO ! <LOD CLOD . <LOD <LOD CLOD 2.84 NA . 0.954* 2.50 NA 0.954*
3.32 1.48 2.84 2.08 257 4.61 4.59
0.981 0.664 0.955 0.645 0.881 1.25 1.09
cLOD CLOD CLOD CLOD CLOD
NA NA
CLOD cLOD CLOD cLOD ' CLOD 0,623 0.660
CLOD CLOD CLOD CLOD CLOD
NA NA
High Low
7.08 0.507*
3.56 2.45
NA 1.02* 230 263 NA 0.888* 0.477 0.337
NA NA
0.842 0.312
NA NA
Standard Deviation
2.17
0.627
NA 0.0933 3.64 0.571
NA
0:208
NA
# OF HITS , 20
3
0
2 35 34
0
6
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 fio ra file sam e lo t o f pooled serum . A nalyte was detected in one o f die 36 samples but appears to be a contaminant or an anomaly; the
sample w ill be reanalyzed and fee results w ill be reported in fee definitive study. Based on 15C PFOA surrogate recovery, the overall m ethod uncertainty is + /- 20%.
Page 14 of 18
3M ENVIRONMENTAL LABORATORY PRO JEC T NO.E05-0120
Table 11. Sample Results for Additional Perfluorinated and Highly Fluorinated Analytes
'
-
V
*
r: ,lJ /,
wl
?
f
Vc
!i
TNA 6840 TNA 6843 TNA 6847 TNA 6934 TNA 6935 TNA6944 TNA5959 TNA6960 TNAB967 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 TNA6962 TNA 6964 TNA 6966 TNA 6970 TNA.6972 TNA 6978" TNA 6979 TNA 6962 TNA 6984 TNA 6986
.
is
l
,t
' <
.'<*-
V E-"-
~P ' , 1 fr-
<; \
i
z m .m i
<L0D COD
COD , COD
COD' 0.0228*
J : : ' 7 : i: .1 - . i :>*'" . -vUir.sa / . V.vri
4.39 23.0
0.780 1 3;42
COD COD
0.124* 0.155*
COD COD COD COD
0.0458* COD COD COD
COD 2.05 23.7
0.0304*
2,41 - 32.8
0.0433*
Z14 162
0.0706* " " 4.73 " 20.4
; COD COD COD COD
0.145* 0.0531* 0.0820* 0.0860*
COD COD COD
COD COD 0.199*
COD 0.0292* Q.0358*
3~75
4.52
V 427
14.8
/ 19.6
21.3
COD COD COD
0.0649* 0.0819* 0.0857*
COD COD COD 5.18 20.5 COD 0.0818*
COD
COD Q.0393*
4.98
19.4 C od 0.8622*
COD COD 00339* 0,844 3.01 C O D ' 0.0916*
COD 0.0311* 0.0313* . 1.77 ` 17.4
COD
0.103*
COO COO 0-0429* : 4.45
19.8 COD 0.0826*
COD COD COD 7.1.71
3.50 COD 0.0616*
COD COD 0.0366* ' 3.79
15.1 COD 0.0853*
C O D COD 0.0479* 3.81
15.2 COD 0.0707*
C O O , COD 00568*
5.68
22.9 COD "! 0.0638*
COD COO
COO COD
0.04,12* 4.90 7 20.2
8.0226* :
- - 15.6
COD .066r COD 0.0601*
COD COD COD' ' 1.79 '6 .2 3
COD 0.0625*
CO
COO 0.0224*
3.06 23.4
CD ~ 0.0577*
COD
COD
COD
3.24
14.3 C od 0.0909*
COD
COD 0.0226* ; 524 :: 22.1
cod
0.0480*
COD COD
COD COD
.COD"
32 9 7 10.1
0.0312* ic ic 5 Z 2 \ 7 19.8
COD 0.0493* C O D ' : 0.0705*
COD COD 0,0374*
. 21.7 ' COD ; 0.101*
COD COD 0.0229* ; 4.62 ` ' 17.5
COD
0.0620*
COD CQD C O D ' '4 .0 6 r 17.0
COD
0.T37*
COD
COD " 0.0345*
3.09 . 12.7
COD
0.0653*
COD COD 0.0210* ' 0.945 2.71 COD 0.0998*
COD 0.0344* 00226* 2.31
16.7 COD 0.102*
COD
COD
c o d : t 126
9.37 'C O D
0.0790*
COD
COD
COD
1.73
15.8 COD 0.0911*
COD
COD
COD
1.41
11.3 . . -COD 0,0683*
Page 15 o f 18
\6
3M ENVIRONMENTAL LABORATORY PRO JEC T NO.E05-0120
Table 11. Sample Results for Additional Perfluortnated and Highly Fluorinated Analytes (continued)
TNA 6988 Mean
- Median High Low
TM <LOD NA NA NA NA
<LOD 0.0776* 0.0401* 0.199* 0.0311*
<LOD 0.0348* 0.0339*; 0.0706* 0.0210*
1.79 327 327 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 0 4 23 '36- 36
NA = N ot Applicable
...........'
A nalyte conceatraticin was below the LLOQ and above die LOD.
**TN-A-6977 and -6 9 7 8 are from the sam e lo t o f pooled serum .
B ased on llC PFOA surrogate recovery, die overall m ethod 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
TNA6840 TNA6843 TNA6847 TNA6934 INA 6935 TNA6944 TNA6959 TNA6960 TNA6967 TNA6973 TNA6975 TNA 6977** TNA6981 TN 6992 TNA 6994 TNA6995 TNA 6997 TNA 7000 TNA 7006 TNA 6938 TNA 6939 TNA 6941
aKi^i.yr^saBawtaniraiiig1T.JmiiJT11iJcieianBTS!iYnrTriuaaitnM
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%
Massachusetts
< LLOQ*
Texas
3.7%
California
42%
California
4.0%
California
6.0%
California
4.0%
California
17%
California
6.3%
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%
Page 16 of 18
(7
3M ENVIRONMENTAL LABORATORY PRO JEC T NO.E05-0120
Table 12. Isomer Ratios for individual Samples (continued)
TNA6950 TNA69S3 TNA6955 TNIA6962 TNA6964 TNA6966 TNA6970 TNA6972 TNA6978TNA6979 TNA6982 TNA6964 TNA6986 TNA6988
Michigan Michigan Michigan Virginia Virginia Virginia l : Maryland , Maryland M assachusetts M assachusetts Texas Texas Texas Texas
0.3%
10%
3.0% 6.8% 5.4% 7.9% 6.7% 5.1% <LLOCr 7.6% 6.0% 1.3% 0.1% 4.5%
Average: Standard Deviation
Sam ple value was < LLQQ TN -A -6977 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 papa: 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 o f 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
Quality A ssurance Representative
Date
AAUG. 12, 2005 5 : '1PM -QUALITY ASSOCIATES 2* !1 8 . S ig o g to m
NO. Q74i J P. I / '
3MBJVHVMUENTAL LABORATORY PROJECTNCJ505-0t20
4 r I*
---------- -------------------------------- -----WMtaffl Reagan. Laboratory Manager
Oat
The 3M Bxviroomeniai Labonaray's Q ua% Assurance Unit has audited the dot*,and
RECEIVED TIME AUG. 12. 4:48PM
pee is of is
PRINT TIME AUG, 12. 4:49PM
