Document 5jK9NEG9Dno9daaxNqOv47gz
JO
Katherine E. Reed. Ph.D. Staff Vice President
3M Environmental. Health and Safety Operations
M S 8 6 - & '# ?
900 Bush Avenue. Building 42-2E-26 PO Box 33331 St. Paul. MN 55133-3331 651 778 4331
Certified Mail
August 26, 2005
Y tq - D io s' -0 0 3 7 3
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 n ta in
No
9 4 -4 3 ? NO TSCA CBI
cB l
Re: TSCA Section 8(e) Supplemental Notice: Sulfonate-based and Carboxylic-basgt Fluorochemicals, Docket Nos. 8EHQ-1180-374: 8EHO-Q38 l-0394^H TO ^598-37?:
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 die 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 of previously reported values and/or do not represent "substantial risk"
information
&
If you have any questions, please do not hesitate to contact Dale L. Bacon at (651) 778-4736.
,-n
Sincerely,
0 753 -om
Katherine D. Reed, PhD Staff Vice President Environmental Technology and Safety Services
:'>m
V.O
BEST COPY AVAILABLE
89050000599
8 90 S0 0 0 05 9 9
3M ENVIRONMENTAL LABORATORY PROJECT NO.EOS-0120
NO TSCA CBI
Analytical Report
Revised August 12, 2005
Initial Quantitative Screening of Commercial Lots of Human Serum Obtained in 2004 for Endogenous Ruorochemicals Using Protein Precipitation and Liquid Chromatography/Tandem Mass Spectrometry
Laboratory Request Num ber E05-012Q
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 3331 Saint Paul, MN 55133-3331
Phone:651-778-5405
Testing Facility M anagement 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-09
PO Box 3331 Saint Paul, MN 55133-3331
Phone: 651-778-4736
Page 1 of 18
JL
3M ENVIRONMENTAL LABORATORY PROJECT NO.E0S-0120
3M Environmental Laboratory
Analytical Report
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 designed to provide lower limits o f quantitation (LLOQs) o f approximately 100 - 300 p p t Upon review o f fire data, it was discovered that many o f fire 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 aralytes as low as 19.9 ppt. Therefore, it must be emphasized that much of the da~a 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 of 18
Table t. Summary of Perfluorinated Acid Results
3M ENVIRONMENTAL LABORATORY PROJECT NO.E0S-0120
Mean
3.33 2.84 NR2 0.954 4.61 1.25 NR2 0.623 <LOD
Median High
3.33 2.5 NR2 0.954 4.59 1.09 NR2 0.660 <LOD 7.08 3.56 NR2 1.02 23.0 2.63 : NR2 ' 0.842 <LOD
Low 0.507 2.45 NR2 0.888 0.477 0.337 NR2 0.312 <LOD
Standard Deviation
2.17 0.627 -j NR2: 0:0933 3.64 0.571 NR2 0.208 ND'
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
ND = Not Detected This analyte was not detected in any of the samples.
NR.2= Not Reported. This analyte was detected m one o fthe36 samples but appears to be a contaminant or ~airanDmsiyrifaBrsan#e~will bereanaiyad'aad toe resuitswill be reported in the definilrve study;
Table 2. Summary of Other Perfluorinated.and Highly Fluorinated Analyte R esults
aM'l1'r
Mean
<LOD 0,8770 848< 3.27 16.3
Median -
<LOD: OJD40T 0.0339 ; 3 2 7 16.9
High
LOD 0.199 0.0706 5.80 32.8
Low-
<LOD 0.0311 0.0210 r 0.780 2171
Standard Deviation
ND1 0.0812 0.0122 ' 1.52 6.71
Fraction of Sam ples with Detectable Analyte
0/36 4/36 23/30 `36/36 36/36
ND1- Not Detected. This analyte was not-detectedm any of tibe samples.
<LOD ; 0.0639 <LOD -0.0819 <LOD 0.155' <LOD 0.0480 ND-1 -c Q.0257
0/36 36/36'
Peaks were observed in die chromatograms corresponding to linear and branched ismera >r 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). T he % 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 w ith previously obtained NMR data.
Page 3 of 18
3M ENVIRONMENTAL LABORATORY PROJECT NO.E0S-0120
Table 3. Summary of PFOA and PFOS isomer Ratios
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)
23% 22%
32% 31%
Table 4. Reference Substances
Heptafluorobutyric Add
Nonafluoropentanoic acid
Perfluorohexanoic add
Tridecafluoroheptanoie acid
Perfluorooctanoic acid
Heptadecafiuorononanok acid Nonadecafluorodecanoic acid
Perfiuoroundecanoic acid
Perfluorododecanoic acid
PerSuorobutanesulfonamide
Perfluorooctanesulfonamide
Perfiuorobutane sulfonate
PerfluoTohexane sulfonate
PerQuorooctane sulfonate 1H, 1H, 2H, 2H,
pcrfluorooctancsulfonic acid 1H, 1H.2H.2H,
pcrfluorodecane sulfonate Perfluorooctanoic acid,
isotopically labeled
PFBA (C4 Add) NFPA (C5 Add) PFHA(C6 Acid) TDHA (C7 Acid) PFOA (C8 Acid)
C9 Acid CIO Acid C ll Acid C12 Acid
FBS FOSA PFBS PFHS PFOS THPFOS
THPFDS 3C PFOA
Aldrich Aldrich Oakwood Products Aldrich
3M Oakwood Products Oakwood Products Oakwood Products Oakwood Products
3M 3M 3M 3M 3M SynQuest Labs
TCR-757
99.2%
TCR-333 (00017-045) 96.5%
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%
TOR-83 (SE036)
98.6%
TCR-696
86.4%
TCR-343 (00017-055) 93.5%
Pace/3M
TCR-627
94.7%
Peridn Elmer
TCR-744
>97%
0.995 0.996 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
Page 4 of 18
S
3M ENVIRONMENTAL LABORATORY PROJECT 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. Matrix spikes and method blanks were prepared by spiking the serum (or water) with die analytes o f ihterestrht addition, 13C PFOA was added as a surrogate to all seram samples* caiibradon standards, matrix blanks, and method blanks at a concentration o f 3.01 ngftnL to evaluate extraction method performance
4. Two milliliters o f acetonitrile were added to the serum and die 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 SromJhe centrifuge, die 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 colum n Keystone* BetasiiTM Cu 2xl00mm, 5pm particle size-
Column temperature: 30 Stop Time; 20.0 minutes How rate: 300 pIAnin Injection volume: S pL
Mobile phase components:
Solvent A: 2.0 mM ammonium acetate in ASTM Type I water
Solvent Bt HPLC Gradb M ttbanot 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 PROJECT NO. E05-012Q
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 5. Acquisition Parameters
'w . .
>
PFBA (C4add) NFPACs Arid PFHA (C*add) TDHA (C7 Arid) PFOA (C*Arid)
CArid C10Arid Ci, Arid C12 Arid FBSA FOSA PFBS PFHS PFOS
THPFOS THPFDS PFOA[1,2-,sq
:iSuuiUiiji
J1
213.0
168.9
-30
262.9
219.0
-30
313.0
268.7,118.9
362.9
318.7,168.8,118.9
-35
413.0
368.9,219.0,169.0
-40
463.0
418.7,268.9,218.9
-50
512.9
4686,218.9,269.1 | -100
563.0
518.7,268.9,218.8 I
-45
613.0
568.7,168.9,318.7
-50
297.9
78.0
-55
497.9
77.9
-90
298.9
98.9,79.9
-65
398.9
98.9,80.0
-95
498.9
80.0,992,130.0
-80
426.9
406.8,80.9
-70
526.9
506.7,81.0
-70
414.9
369.8
40
When multiple transitions were monitored, tine 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 of 18
1
3M ENVIRONMENTAL LABORATORY PROJECT NO. EOS-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. 4.1J 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. 4.1.4 L o w v lM irfQ im iitio n O u L O Q The LLOQ for each analyte was eqiial to the lowest standard in dm calibration curve ' that m e taccuracy 4 .1 5 L im it o fD etection (LOD) The LOD for each analyte was equal to the area counts (converted to a concentration) that were 2-3 times above the method blank. 4.1.6 Blanks Method Blanks All o f the method blanks in this 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 % the LLOQ for BLK050203-003.
f Page 7 o f 18
3M ENVIRONMENTAL LABORATORY PROJECT NO.E0S-0120
Table 6. Average Endogenous PFOS Value Determination
LLOQ (ng/mL)
0.306
Blk050203-003
< LLOQ
Bik050203-004
0.477
Average:
0.315
The average endogenous PFOS value was used to correct die 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 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 wore 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
- Ht
PFBA(C4add) LOO * 0.426 ng/mL LLOQ" 3.00 ng/mL
NFPA (C5 add) LOD * 4.53 ng/mL LLOQ 13.3 ng/mL
NA = Not Applicable
g
y l.
3*
QC0502034I01
3.00 .
QC05203-002-
3.00
QC050203-003
' 3:00
QC050203-004
75.5
QC050203-005
75.6 .
QC050203-006
75.5
'- .......
!
QC05Q203-001 QC050203-002 QC050203-003 QC050203-004 QC050203-005 QC050203-006
" 3.06 3.06 3.06 77.7 77.7 77.7
iiis :
.;.-y --a*-"
- ..f.i
<LLOQ
<txoa
< LLOQ 70 7f.3
70.2
NA NA NA 33% 94% 93%
NA 1.0%
< LLOQ < LLOQ < LLOQ 68.00 80.50 97.20
- I.
NA NA NA 88% 104% 125%
NA 17.9%
3M ENVIRONMENTAL LABORATORY PRO JECT NO.E0SO120
Table 7. M atrix Spike Recoveries in Rabbit Serum (continued)
` V- -te; i ;
- ;~If*',` v - i - rVi-'
H
./
R
-;v ; 1.
QC050203001
3.03
PFHA (C6 acid)
QC05203-002 QC050203-003
3.03 3.03
LLOQ 15.1 ng/mL
QC050203-004
76.8
QC050203-005
76.8 '
QC050203-006
76.8
Sr Abiii ,, . < lloq lloq < LLOQ 62.4 778
948
il;.
-V & SSL NA NA
!*?.- T t * r J& 2
NA
NA
81%. 101%
20.4%
123% j
TDHA(C7 add) LLOQ 3.03 ngftnL
CIO ACC LLOQ 3.12 ng/mL
L- - C11 ACC
LLOQ 0.297 ng/mL -
C12ACC . . LLOQ-0.747 ng/mi. NA = N ot Applicable
QC050203-001
3.03
Q0S0203-002
3.03
QC050203-003
3.03
QC050203-004
76.5
QC50203-005
. 76.5 .
QC050203-006 b--___ 76.5
<LLOO <LLOQ <LL0Q
66.9 80.1 95.4
NA NA NA 87% 105% 125%
QC0S0203-001 QC0S0203-002 QC050203-003 000502034)04
000502034)05 QC050203-006
3.12 3.12 3.12 78.6
78.6 ,.
78.8
CLLOQ <LLOQ <LLOQ
65.4 71.9
83.1
NA NA NA 83%
91%
106%
- -.. QCQ5B203-6Q4 -
... 2.92
000508034)02.
2.97
00050203003 i y287
000502034)04 75.3 . ..
,
000502034)05 -
75.3-- . -
000502034)06 a 7 5 8 .> h. .
...... .
000502034)01-: 000502034)02
3.00- - - 3.00- 1
; QC0502034X'
3.00- r
000502(84)04. 00050203485 QC0502034506
. 75.6 . !. . . 75.fr . ! 75.0
- .... 2.98 Z71 295758 . 78.3 . .
788 .
3.043.13 388 782 82878.3
-
100% 91% 99% 101% 104% 104%
101% 104% 109% 101% . 109% 104%
NA
17.7% i
NA *
12% - _
5.1%
1.8%
3.8%
3.9%
j
Page 9 of 18
\o
Table 7. Matrix Spike Recoveries in Rabbit Serum (continued)
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-O20
flEBSSte-.'^rTT.1vTBIti -a ''CPFOA
C9 Add LLOQ 0.303 ng/mL
QC050203-001 QC050203-002 QC050203-003 QC050203-004 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 3.01
....
35 1 3.01 _ 3,03 754 ' 75;4 : 75.4
PFOA LLOQ 0.298 ng/mL
QC050202-001 QC050202-002 QC050202-003 QC050202-004 QC050202-OOS QC050202-006
2.38 , 2.98 2.96
75,8 75.6 75.6.
: QC050203-001
FBSA
QC050203-002 QC050203-003
LLOQ 0.303 ng/mL QC050203-004 QC0502Q3-005
QC050203-006
FOSA LLOQ" 0.300 ng/mL
QC0S0203-001 QC050203-002 QC050203-003 QCC50203-004 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
B S.s-;:sHB6S cHfnimtti"v-`je
T
2.81 93%
3.06 102%
2.94 96% 4.8% 2.68 89%
2.91 97%
2.75 91%
3.23 3.04 ' 195 77.4 . 75.8 69.9
..
107% 100% 97% 103% 101% 93%
4.7% 5.3%
2.93 2.58 2.65 75.2 78,4. 77.6
98% 87% 89% 99% 101% 103%
6.8%
-
1.6%
2.96 96% 2.92 96% 0.7%
2 5 5 97%
75.9 99%
77.9
102%
1.4%
77.7 102%.
2.78 2.74 2.74
76.6 ' 77,1
76.0
93% 91% 91%
101% 102% 100%
0.8% 0.7%
Page 10 of 18
iW *
3M ENVIRONMENTAL LABORATORY PROJECT NQ .E0S4120
Table 7. Matrix Spike Recovaras in Rabbit Serum (continued)
-- - ~ r ft?*.
-.-
\ `h ' - 4
PFBS
LLOQa 0.303 ng/mL
QC050203-001
3.03 -
QC050203-002
3.03- - -
QC05Q203-003
" 3.03
QC050203-004
" 76.8
QCOS0203-O(i5'
'76.8
QC05C203-006 ' ~ 76.8 :
- -y;-'- '
; . `"ii
-396 ' 3.00 3.01 75.8 78.3 775'
iff' .
101% 99% 99% 99% 102%
101%
PFHS LLOQ> 0.315 ng/mL
THPFOS
l
U.OQ a o.780 ng/mL
THPFOS
LLOQ- 0.303 ng/mL . 1 1
QC050203-001 00050203=002 QC050203-003 QC050203<004 QC050203005 QC050203-006
~ .....
t s ..... " ' 3.1&: 3.13 79;8 79.8 73.8 ;
394 3.08 3.04 785 79.9 78.8
97% . 98%
97% 98% 100% 98%
QC05C203-001
. 3.fa -
3.02 97%
QC050203-002
3.12-
2.83 91%
00050203^003
Z .f l
aa .. 91%
QC050203-004
m ;.
____86.0
: 84%
QC050203-005
78.9
80.0 101%
QC0502QW06 .v1^.
TBS ; xi-.'-
96.5,. ` 122% l.
00050203=001 ...
..-ios." -- . ... 2.9
98%
QC0502Q3002. . ........... 3.03 . _ - 3.00
99%
QC050203003 --
- . 3.- . ----- : 3.12
103%
0 0 0 5 0 2 0 3 -0 0 4 .. OC0S0203-00S
7 6 3 ____ - ' - 77.9
78.5 .
. 7.9.8
102% 104%
QC0502Q3-006
78
785 102%
1.1% 1.6%
0.8% 1.1%
3.8% 19%
2.8% 1.3%
Page 11 o f 18
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0120
Table 8. PFOS Matrix Spike Recovery in Rabbit Serum, Corrected for Endogenous Levels
III i
n
! QC0502Q2-001
pros
QC0502Q2-0G2 QCO50202-003
U-00*0.303 ng/mL QC050202-004 QC050202-005
QC050202-006
H
3.06 3.17 3.06 3.03 3X6 3.1 77.4 77.4 77.4 77.6 77.4 76.1
n gj
0.31S . 0.315
0.31S . 0.315
0.315 0.31S'
I
; 2.86
202
79 77.1 -
77.3
75.8
93% 89% 91% 100% 100% 98%
2.5% 1.1%
4.3 Accuracy The accuracy for each analyte reported was calculated by taking fee average o f fee matrix spike recoveries for feat analyte. The results are presented below.
Table 9. Method Accuracy for Individual Analytes
k - . *-ns*
PFBA*
7%
C12 Acid
5%
NFPA*
6%
FBSA
1%
PFHA*
2%
FOSA
. 4%
C7Acid*
6%
PFBS
1%
PFOA
4%
PFHS
2%
C9 Acid
1%
PFOS
5%
C10 Add*
7%
THPFOS
2%
C11 Add
1%
THPFDS
1%
The / Accuracy icponcd for this analyte ii based on the high concentration spike recovery data only became the low concentrstian
spike recoveries were less then the LLOQ.
4.4 Sample Related Comments
The extraction and analysis o f fee samples was performed utilizing a non-validated method. The matrix spike results, l3C PFOA surrogate recoveries, and the extrapolated calibration curve (between fee LLOQ and LOD) should be considered when evaluating fee accuracy and precision o f fee sample results.
Tables 10 and 11 summarize individual sample data.
13
Page 12 o f 18
Table 10. Perfluorinated Acid Results
3M ENVIRONMENTAL LABORATORY PROJECT NO.E0S-0120
1
TNAS840 TNA 6843 TNAS847 TNA 6934 TNA6935 TNA6944 TNA6958 TMA6960 TNA 8967 TNA 6973 TNA6975
|
1||
g
5.19 0.990* 0.507* <LOD 1.17* 7.08 4.91 3.32 4.09 6.73 2.95*
2.50 <LOD < .00 < .0 0 < .0 0 < .00 <00 <00 <00 3.56 <00
1 ' <00 <00
<OD < 0 0 <00 < 00 <00 i <00
<ocr < 00
<00 I <00 <00 <00 < 00 <0D <00 <00 < 0 0 Q.888* <00 ! <00
5.48 0.581 , 4.81 7.69 519 7.38' 3,13 4.59 5.30 5.51 5.52
: 1 .5 2 ^ 0.574 0.978 2.28
. ' 1.63 . : 1.45 2.45 1.11 1.62 1.64 1.31
<00 <00 <00 <00 <00 <00 <00 <00 <00 <00 <00
p Rl
<00 <00 <00 <0D 0.451 <00 0.700 <00 <00 <OD <OD
<LOD <00 <00 <LOD <0D <00 <LOO <00 <00 <00 <0D
Page 13 of 18
/f
Table 10. PerRuorinated Acid Results (continued)
3M ENVIRONMENTAL LABORATORY PROJECT NO.EQ5-0120
TNA6977** TNA6981 TNA6992 TNA6994 TNAS995 TNA6997 TNA7000 TNA7006 TNA6938 TNA6939 TNA6941 TNA6950. TNA6953
5.M 6.76 0.690 <LOD 1.98* 3.90 3.34 3.19 <LOD <LOD 3.56 <LOD 0.621*
<LOO Z45 <LOO <LOD <LOO <LOO <LOD 4 .0 0 <LOD <LOO 4 .0 0 4 .0 0 4 .0 0
4 .0 0 <LOD <00 <00 ia.4-- <00 <OD
<oo
<OD <OD <00 <OD <00
<00
<00
<00
<00
1.02
<oo <oo
<00 <00
<oo
<00
<00
<0D
0.477 4.12 4.78 1.15. 3.58 ' 3.46 23.0; 4.18 5.00 2.32 5.82 3.87 5.49
4430 1.28 0.912 0.337 2.63 2.52
r.oa
1.09. 0.979 0.941 1.69 0.723 0.725
<00 <OD <00 <OD <00 <00 <00
<oo
<00 <OD <00 . 14.0** <OD
<LOD
<0D
<oo
<00 0.615 0.642
<oo
<00 <OD 0.312 0.620 <OD <00
<OD <00 <0D <00 <0D <00 <00 <OD <00 <OD <00 <00 <OD
TNA6955 <LOD 4 .0 0 < 0 0 < 0 0 2.54 0.562
TNA6962. <LOD 4 .0 0 < 0 0 < 0 0
4:68 0.941
TNA6964 <LOD 4 .0 0 <oo < 0 0 5.61 1.58
TNA6966 <LOD TNA6970 <LOD
4 .0 0
4.00
<L00
<oo
<00
<oo
4.73 6.00
1.35 1.42
<OD
<OD
<00
<oo <oo
<0D <00 <00 <00 <00
<00
<0D <00 <OD
<oo
TNA6S72 TNA6978** TNA6979 TWA6982 TNA69B4 TNA6986
<LOD <LOD <LOD <OD <LOD 0.530*
4 .0 0
4.00
4 .0 0
4 .0 0 4 .0 0
4 .0 0
<0D <OD
<OD
<oo
<00 <OD
<00
<oo
<00
<00
<oo <oo
3.40 < LOO 3.32 1.48 2.84 2.08
1.09 < LOD 0.981 0.664 0.955 0.645
<00
<oo <oo <oo
<OD
<oo
<00 <OD
<00 <OD
<00
<00
<OD <OD
<00
<OD
<OD <LOD
TNA6988 Maafl
Madian High Low
< .0 0 3.33 3.33 7.08 0.507*
4 .0 0 2.84 2.50 3.56 2.45
<00 NA NA NA NA
<0D 0.954* 0.954* 1.02* 0.886*
2.57 4.61 4.59 23.0 0.477
0.881 1.25 1.09 2.63 0.337
<OD NA NA NA NA
<00 0.623 0.660 0.842 0.312
<00 NA NA NA NA
Standard Deviation
2.17
0.627
NA 0.0938 3.64 0.571
NA
0.208
NA
# OF HITS 20
3
0
2 35 34
0. 6
0
NA = Not Applicable *Analyte concentration was below the LLOQ and above the LOD. **TN-A-6977 and TN-A-i978 are flora the same lot o f pooled serum.
Analyte was detected in one of die 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.
Based an llC PFOA surrogate recovery, the overall method uncertainty is +/- 20%.
Page 14 o f 18
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0120
Table 11. Sample Results for Additional Periluorinated and Highly Fluorinated Analytes
.: - V ' . ' V 1 : ' : -
x ' - ' '
i? "
TNA6840 TNA6843 TNA 6847 TNA 6934 TNA 3 5 TNA 6944 TNA8959 TNA6960 TNAS967 TNA 7 3 TNA 7 5 TNA 6977** TNAS981 TNA6992 TNA 6984 TNA 6995 TNA688P TNA 700 TNAiTOO*^ TNA 6938 TNA 3 9 TNA 4 1 TNA 5 0 TNA 6953 TNA 6955 TNA 6962 TNA 6 4 TNA 6966 TNA 7 0 TNA72 TNA 7 8 TNA 6979 TNA 6962 TNA 6964 TNA 6966
; ik .
<00 <00 <Q 0 <00 <00 <00
<OD
<00 <00 <00 <00 <00 <00 <00 <00 <00
<oo
<00
" a rm
<00 <00 <00 <00 <00 <00 <00
<oo
<00 <00 <00 <00 <00 <0D <00 <00
...
\f* 1
...
-..< r
. 5! ;^ .
. a U y ff."
'
:j .O i :T_" : - . ' : h l i `.
< 0 0 ' < 0 0 - 4 ^ 9 .: 23.0
<00
0.124*
< 0 0 0.0228* 0.760 3.42 1 < 0 0
0.155*
0.0456* < 0 0
2.05
23.7 < 0 0
0.145*
<00
0.0304* ' 41
32.8
<OD
0.0531*
< 0 0 0.0433* 2.14 ' 182 < O D 0.0820*
< 0 0 0;0708* ` " 4.73
20.4 < 0 0 0.0860*
<00
<00
75, 1 1,4.8
<00
0.0649*
<00
0.0282* ' 4.52 .1 19.6
<00
0.0819*
0.199* 0.0358*
4.27
21.3 < 0 0 0.0857*
<00
< 0 0 5.18 I 20.5
<00
Q.0818*
< 0 0 0.0393* ' 4.98 - 19.4
< 0 0 ! 0.0622*
< 0 D 00339* 0344 3.01 <OD 0.M16*
0.0311* 0.0313* . 1 . 7 7
17.4 < 0 0 0.103*
< 0 0 0.0429* ; 4.45
19.8 < 0 0 0.0826*
<oo
<00
.1.71
3.50 <O D 0.0616*
< 0 0 0.0366* " ' 3 . 7 9
15.1 <OD 0.0853*
: < 0 0 .; 0.0478* . 3J1
12 <O D 0.0707*
; <oo
a a a r"
5.68
22.9 ; < 0 0 ' 0.0638*
< 0 0 0 d 4 ir U <96 , 20J!
< 0 0 : 0.0687*
< o o 0.0226*" 2.78 ' - 15.6 / i < 0 O
0.0661*
<oo
<00
79 ' 6J23 i < 0 6
0.0625*
<OD 0.0224*
3.08 :; 23.4
< 0 O " 0.0577*
<00
< o o . : .. 324
' 14.3
<60
0.0909*
< 0 0 0.0226* &24
22.1
<00
0.0480*
< 0 0 < 0 0 l ~ ; ;'.3;29" 10.1 < O 0 0.0493*
< 0 D 0.0312* ,-.-&22- " , '19.6
< 0 0 ' ; 0.0705*
< 0 0 0.0374*
. . 21.7
< 0 0 ! 0.101*
<00
0.022T ' \ - 4.62 ' I ' 17.5
<00
0.0620*
<qp"
< ' 4.06 ' r 17.0
<00
0.137*
<OD 0345*
3 . L 12.7
< 0 0 i 0.0653*
< o o 0.0210* ; * 0:945 2.71 < 0 0 ; 0.0998*
0.0344* 0.0228* ' 31 : . 16.7
<00
0.102*
<00
<00
"1.26 ' 9.37
<00
0.0790*
<00
<00
1 .n
15.8' < 0 0
0.M11*
<oo
<00
1.41
11.3 < 0 0 0,0683*
Page 15 of 18
6
3M ENVIRONMENTAL LABORATORY PROJECT NO.EQ5-0120
Table 11. Sample Results for Additional Perfluormated and Highly Fluorinated Analytes (continued)
JMfrr-iafSsfmFi
TNA6988 Mean
- Madian High Low
<LOD NA NA NA NA
<1.00 0.0776* 0.0401* 0.199* 0.0311*
<LOD I 0.0346* 0.0339* 0.0706* , 0.0210*
1.79 327 327 5.80 0.780
16.5 J 162 16.9 32.8 2.71
<LOD NA NA NA NA
Standard Deviation NA
0.0812 0.0122 . 1.52
6,71
NA
# OF HITS
0 j 4 23
36 36
NA " Not Applicable Analyte concentration v u below die LLOQ and above the LOD. **TN-A-<>9T7 and -6978 re from the same lot o f pooled serum. Based on I3C PFOA surrogate recovery, the overall method uncertainty is +/- 20%.
0
0.0979* 0.0839* 0.0819* 0.155* 0.048*
0.0257
36
Table 12. Isomer Ratios for Individual Samples
TNA6840 TNA6843 TNA6847 TNA6934 TNA6935 TNA6944 TNA69S9 TNA8960 TNA6967 TNAK73 TNA6975 TNA6977** TNA6981 TNA6992 TNA6994 TNA6995 TNA6997 TNA7000 TNA7006 TNA6933 TNA6939 TNA6941
. ..... :! ;' ' '.. .
CaBfomia
11%
Missouri
13%
Pennsylvania
4.1%
Pennsylvania
0.8%
New York
12%
Michigan
3.4%
Virginia
4.3%
Virginia
4.5%
Maryland
92%
Montreal, Quebec
4.3%
Montreal, Quebec
4.0%
Massachusetts
< LLOQ*
Texas
3.7%
CaSfbmta
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%
*..i:>*
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 PROJECT NO.05-0120
Table 12. Isomer Ratios for Individual Samples (continued)
. -b -, .
1
tfei.nH
1
,:s;
*' ' - ...
TNAS950
j.:E lL: ..... J L l t S ^ 6 l^ : .: J E ^ J _- ' ' I j .
Michigan
0.3%
38%
TNA6953
Mtehigan
10% 39%
TNA6955
Mfchlgan
3.0%
35%
TNA6962
Virginia
6.6%
41%
TNA6964
Virginia
5.4%
42%
TNA6966
Virginia
7.9%
40%
TNA6970
: Maryland ,
6.7%
39%
TNA6972
Maryland
5.1%
38%
TNAS978**
Massachusetts
U.OQ*
41%
TNA6S79
Massachusetts
7.6%
30%
TNA6962
Texas
6.0%
41%
TNA6964
Texas
1.3%
31%
TNA6986
Texas
0.1%
43%
TNA6988
Texas
..
4.5%
33%
Average:
6% 39%
Standard Deviation
3%
3%
"Sample value was < LLQQ **TN-A-6977 and TN-A-6978 are from die same lot o f pooled sen n a
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 axe 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 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 of serum while PFOA was present in detectable levels in all but one sample. Conversely, FBSA, THPFOS, and the C n acid ware not detected in any of the samples using the present methodology. I3C PFOA surrogate recoveries were all within 20%.
Page 17 o f 18
\t
3M ENVIRONMENTAL LABORATORY PROJECT NO.E05-0120
The 3M Environmental Laboratory's Quality Assurance Unit has audited the data and report for this project
Quality Assurance Representative
D ate
Page 18 o f 18
14
jjj ^ UG' 12,2665 5: '1PM DUALITY ASSOCIATES l* l
NO. 074J P. 1/'
MOMONuenrALlABO^ATOfy
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T h a P rP*n'nTxwTl Ta hii|ytnyy'c Q uality AflgnrmvTfiptItay aodttsdthO d s t& w l
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