Document BrYx5m2Gr3zg1mgJ0kG2ZyNk
jean B. Sw. Staff Vice F' es
3M Environmental, Health and Safety Operations
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December 15, 2008
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RE: TSCA 8(e) ADDITIONAL INFORMATION SUBMISSION for Sulfonate-based and Carboxylic-based Fluorochemicals: Docket No. 8EHQ-1180-373
To whom it may concern:
Enclosed please find the presentation Analysis o f the Homologus Series ofPerfluorocarboxylates - Perfluorobutanoate (C4) through Perfluorododecanoate (Cl2)from American Red Cross Adult Blood Donors, 2006, by Geary Olsen, Mark Ellefson, and William Reagen. This presentation was prepared for the SETAC North American 29thannual meeting and presented on November 19, 2008.
The data provided in the presentation focus on plasma C4 - C12 perfluorocarboxylate levels in
samples collected in 2006 from donors in six different US locations. Comparisons are made to a
similar set of data from samples collected in 2000. Declines were previously noted from 2000 -
2006 for perfluorooctanesulfonate (PFOS) and perfluoroooctanoate (PFOA) (see Olsen et al.
ES&T 2008; 42:4989-4995). In the presentation submitted herein, plasma concentrations for
perfluorononanoate (PFNA), perfluorodecanoate (PFDA), and perfluoroundecanoate (PFUnDA),
appeared to have increased. Strong correlations were also observed between higher chain lengths
and weak correlations were observed between higher and lower chain lengths. Perfluorobutyrate
(PFBA) was also measured and appeared to have declined between 2000 and 2006.
'
Please note that 3M historically did not manufacture, and does not currently produce, the higjher homologs or their precursors. 3M does not believe that any of these data taken alone or cumulatively meet the "substantial risk" reporting threshold as defined by EPA., We nevertheless recognize the on-going work of the U.S. EPA to assess fluorochemical exposure pathways. Therefore, we are placing these results in the 8(e) docket as a supplement to previous submissions.
If you have any questions or would like any additional information, please contact Deanna Luebker at (651) 737-1374 or diluebker@mmm.com.
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COW W ISNOC
Jean B. Sweeney Staff Vice President, 3M Environmental, Health and Safety Operations
TSCA CONFIDENTIAL BUSINESS INFORMATION DOES NOT CONTAIN NATIONAL SECURITY INFORMATION (E.D. 12065)
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Analysis of the Homologous Series of
Periluorocarboxylates - Perfluorobutanoate
(C4) through Perfluorododecanoate (C12)
from American Red Cross Adult Blood
Donors, 2006
-
r2 C'J
setac North America 29thAnnual Meeting Tampa Bay, Florida November 19, 2008
CD
Geary Olsen1 Mark Ellefson2 William Reagen2
123M Company,1Medical Department, Environmental Laboratory
Acknowledgements
3M - John Butenhoff - Sue Chang - Larry Zobel
American Red Cross - David Mair - Theresa Boyd - Ross Herron - Zahra Medhdizadehkashi - John Nobiletti - Jorge Rios
University of Minnesota - Tim Church
Methods
(Olsen et al. ES&T 2008;42:4989-4995
Study design
- Total of 600 plasma samples collected
100 plasma samples were collected between May and July 2006 in each of six locations
- Boston, MA; Charlotte, NC; Hagerstown, MD; Los Angeles, CA; MpIs-St.Paul, MN; Portland, OR.
- 10 samples per each sex and age group >20-29 > 30-39 >40-49 > 50-59 > 60-69
Methods
Analytical
- PFOS (perfluorooctanesulfonate, c 8f 17s o 3-) - PFOA (perfluorooctanoate, C7F15C 0 2) - PFHS (perfluorooctanehexanesulfonate c 6f 13s o 3-) - PFBS (perfluorobutanesulfonate, C4F9S 0 3) - Me-PFOSA-AcOH
(N-methyl perfluorooctanesulfonamidoacetate,
C8F17S 02N(CH3)CH2C 0 0 )
- Et-PFOSA-AcOH (N-ethyl perfluorooctanesulfonamidoacetate, C8F17S 0 2N(CH2CH3)CH2C 0 0 )
N a of adults
Distribution of PFOS Concentrations (ng/mL), American Red Cross Blood Donors, 2000 - 2006
PFOS (ng/mL)
No. of adults
Distribution of PFOA Concentrations (ng/mi_), American Red Cross Blood Donors, 2000 - 2006
PFOA (ng/mL)
Geometric Mean (95% Cl) Concentrations CDC NHANES
9>
Q.
and American Red Cross Studies, 1999-2006
Calafat et al. ES&T 2007;41:2237-2242 Olsen etal. EHP 2003;111:1892-1901 Calafat et al. EHP 2007;115:1596-1602 Olsen et al. ES&T 2008;42:4989-4995
40.0
INHANES (1999-2000) IAm Red Cross (2000-2001) INHANES (2003-2004) IAm Red Cross (2006)
Concentration (ng/mL)
PFOS
PFOA
PFHS
Me-PFOSAAcOH
Et-PFOSAAcOH
95th Percentile (upper bound), CDC NHANES and American Red Cross Studies, 1999-2006
Calafat et al. EST 2007;41:2237-2242 Olsen et al. EHP 2003;111:1892-1901 Calafat et al. EHP 2007;115:1596-1602 Olsen et al. ES&T 2008;42:4989-4995
ion (ng/mL)
p. 10
PFOS
PFOA
PFHS
M e-P F O S A AcOH
Et-PFOSAAcOH
Age- and Sex-Adjusted PFOS Concentrations (ng/mL) American Red Cross Blood Donors, 2000 - 2006, by Six Geographical Locations
PFOS (ng/mL)
o Ol o o o
A to Is) 04 to cn o Ol O Ol o
oooo
Ol Ol o> Ol o Ol o
oooo
__ i__ __ i__ __ i__ __ i__
__ __ __ __ i__ __ __
Boston 2000
Boston 2006 Charlotte 2000
IT*
-- 4 ^ ------- X
Charlotte 2006
V
Hagerstown 2000
Hagerstown 2006
Los Angeles 2000
Los Angeles 2006
Mpls-St. Paul 2000 Mpls-St. Paul 2006
Portland 2000 Portland 2006
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Age- and Sex-Adjusted PFOA Concentrations (ng/mL) American Red Cross Blood Donors, 2000 - 2006, by Six Geographical Locations
PFOA (ng/mL)
oo o-- oN ao c oo - i o^ mc-- on mO o' J oO 'o
Portland 2006
p. 13
Methods
Current Analysis
Target Analytes
- PFBA (perfluorobutanoate, C3F7C 0 2') - PFPeA (perfluoropentanoate, C4F9C 0 2") - PFHA (periluorohexanoate CgF^CO^) - PFHpA (perfluoroheptanoate, c 6f 13c o 2-) - PFOA (perfluorooctanoate, ^7^15^02') - PFNA (perfluorononanoate, C8Fi 7C 0 2') - PFDA (perfluorodecanoate, ^9^ igC02') - PFUnA (perfluoroundecanoate, C 10F21CO2 ) - PFDoA (perfluorododecanoate, C h F23C02')
Methods
Analytical
- Target analytes extracted by protein precipitation in acetonitrile
- Perfluoro-n-[1,2,3,413C]octanoic acid spiked into all samples and the matrix-matched fetal bovine serum calibration curve prior to extraction for use as an internal standard
-Quantitation accomplished by HPLC/MS/MS using Applied Biosystems MDS Sciex API 5000 triple quadrupole mass spectrometer
p. 15
Methods
Analytical
- Quality control elements for each batch of samples extracted
Spiked control human plasma at two levels
Spiked control bovine serum at three levels
MPFBA, MPFDA, and MPFDoA spiked into each sample pre-extraction to determine extraction efficiency
MPFOA spiked into each sample pre-extraction as an Internal Standard
Matrix-matched calibration curve and solvent calibration curve prepared with each batch
Methods
Analytical
-Q uality assurance
Split samples (n = 60) Reanalysis of 2000 Am Red Cross serum
samples (n = 78) using 2006 methods
American Red Cross 2006 Plasma Samples (N = 600), Percent Above (blue) and Below (red) LOQs
PFBA PFPeA PFHA PFHpA PFOA PFNA PFDA PFUnA PFDoA
American Red Cross 2006 (N = 600), Measures of Central Tendency in Plasma Concentrations
(ng/mL)
PFBA PFPeA PFHA PFHpA PFOA PFNA PFDA PFUnA PFDoA
Arithmetic Mean 0.80 0.07 0.07 0.14 4.40 1.04 0.36 0.22 0.04
Geometric Mean 0.33 0.06 0.06 0.09 3.44 0.97 0.34 0.18 0.03
Range 0.04 - 8.63 0.03 - 0.96 0.04-1.53 0.02 - 2.030 0.78 - 53.70 0.12-5.10 0.05 - 5.270 0.02-3.17 0.04 - 0.44
Comparison of CDC NHANES 2003-2004 (Serum) and American Red Cross 2006 Plasma Concentrations (ng/mL)
Geometric Means with 95% Cl (or Median when LOD)
Compound_______ CDC* Am Red Cross (95% Cl)
PFHpA PFOA PFNA PFDA
<0.3 (LOD) 3.9 (3 .6 -4 .3 )
1.0 (0.8-1.1)
<0.3 (LOD)
0.09 (0.08-0.09) 3.44 (3.30-3.59) 0.97 (0.93-1.05) 0.34 (0.33-0.35)
PFUnA
<0.3 (LOD)
PFDoA
<1.0 (LOD)
*Calafat et al. EHP 2007
0.18 (0.17-0.19) 0.03 to.03-0.04)
Multivariate
Scatterplot Matrix
4- , *
3-j
2-|
1-j PFBA i4
t - . i.
-7i
0.4^
sa
0.1=1
-
PFPeA
#
b- '
:L
4V S i*.,. . k -
# %
k -i
" L , . . . i
i4
m i4
m
j
20 4
i-..
- PFHA % #
r ... .
-
*
fc - PFHpA
f t - -- -
.1
fe e - - -
5- j
3-I
fc -51
L
||k :
PFOA
i
L:
a
PFNA
$
*
L .t
-
.1 .
.L
.
a"
* / fc -s q
-fe .
1 t
lc-. fe *-*-*
PFDA
J
3
fe --
- b . . - fe -'-.' K - .
PFUnA
0.3-f
v>
0.1-1
1
12 3
kfcr-r. TTin'ii
-v--ri
l
"
-1111"
.
r
. 1...........
4 .1 .3 .5 .7 .9
1
*L
% # . *
am
a
% A*
*
: , * - *1i n r | T " T ' ; ii i it tttt r " | " i |' i q 'T rrr
*
10 20 30 1 2 3 4 5 1 2 3 4 5 .51
2
PFDoA 3 .1 .2 .3 .4
p. 20
Multivariate Scatterplot Matrix
i L is ta k i ' *
!* a
p. 21
In PFBA
In PFPeA
)'
i
!k
\
-
-S '
1
s
A-
AA
fe .
- . -----
in PFHA ;
*I k/ -
v" A - &
In PFHpA J j-
g;
li
w t 1
%1
fe -
#
m m
il-
In PFOA
#
#
.J K -
o
In PFNA /
S -
f
.A
IT
*
>
In PFDA #
i* '
j^ F ? :--
f
w* ^----
1] >
t
#-
\ m . f e r i - | \y - . :
*
0
# -O
*
In PFUnA if
#
In PFDoA
Multivariate
Correlations
In PFBA In PFPeA In PFHA In PFHpA In PFOA In PFNA In PFDA In PFUnA In PFDoA
In PFBA 1.0000 0.2648 -0.0239 0.0701 0.0781 0.0887 0.0450 0.0116 0.0660
In PFPeA 0.2648 1.0000 0.0715 -0.1117 -0.1463 -0.1941 -0.2156 -0.1129 -0.1709
In PFHA In PFHpA -0.0239 0.0701 0.0715 -0.1117
1.0000 0.0431 0.0431 1.0000 0.0222 0.4406 -0.0026 0.3773 0.0249 0.3635 0.0689 0.1451 0.0702 0.1780
In PFOA 0.0781 -0.1463 0.0222 0.4406 1.0000 0.6805 0.5580 0.2884 0.2605
In PFNA 0.0887 -0.1941 -0.0026 0.3773 0.6805 1.0000 0.8538 0.6334 0.5563
In PFDA In PFUnA In PFDo/> 0.0450 0.0116 0.0660 -0.2156 -0.1129 -0.1709 0.0249 0.0689 0.0702 0.3635 0.1451 0.1780 0.5580 0.2884 0.2605 0.8538 0.6334 0.5563 1.0000 0.7281 0.7164 0.7281 1.0000 0.8250 0.7164 0.8250 1.0000
-
p. 22
2000 American Red Cross Serum Samples (N = 645) Compared to 2000 QC Reanalyzed w/2006 (N = 78):
50 45 40 ^ 35 1 30
Geometric Means (95% Cl)
10
5
0
PFOS
PFOA
PFHxS
Et-PFOSAAcOH
MePFOSAAcOH
2000 American Red Cross QC Serum Samples (N = 78) vs 2006 Plasma Samples (N = 600): Geometric Mean (95% Cl)
Concentration (ng/mL)
p. 24
2006 American Red Cross Plasma Samples (N = 600) by Location: Geometric Means
Boston Charlotte Hagerstown Los Angeles Mpls-St. Paul Portland
Concentration (ng/mL)
2000 American Red Cross QC Serum Samples (N = 78) vs. 2006 Plasma Samples (N = 600):
Percent Branched PFOS & PFOA
Percent Branched
PFOS
PFOA
2006 American Red Cross Plasma Samples
,(N = 600): Percent Branched PFOS, by Location
60
2006 American Red Cross Plasma Samples (N = 600): Percent Branched PFOA, by Location
10
8
c6
p. 28
p. 29
Serum Elimination Half-lives in Humans
Geo Mean
ComDound Half-life
95% Cl
PFBA PFOA
2.7 days 3.5 yrs
1 .9 -3 .8 3.0-4.1
Reference
Chang et al. Tox Sei 2008 Olsen et al. EHP2007
PFBS PFHxS PFOS
25.8 days 7.3 yrs 4.8 vrs
16.6-40.2 5 .8 -9 .2 4 .0 -5 .8
Olsen etal. Toxicol 2008 Olsen et al. EHP 2007 Olsen et al. EHP 2007
PFOS
Summary American Red Cross Studies
2000 - 2006
- Approximate 60 percent decline in PFOS serum concentrations between 2000 and 2006. No change in ratio of linear to branched isomers from 2000 to 2006
- Comparable percentage declines across age, sex, and locations
- Consistent with serum elimination half-life of PFOS and phase-out time period
* Long half-like likely due to saturable renal resorption
CO
Q.
Summary (continued)
PFBA
- Average plasma concentrations of 2 ng/mL in 2000; 85% reduction by 2006
PFPeA
- majority of 2006 values < LLOQ
PFHA
- majority of 2006 values < LLOQ
PFHpA
- 34% reduction in average concentration from 2000 to 2006; 1/3 values < LOQ in 2006
Summary (continued)
PFOA
- Decline in PFOA concentrations was also observed but lower percentage than PFOS.
- 2000 samples had an average of 5.3% branched PFOA while samples from 2006 contained 3.2% branched PFOA isomers.
- Suggests PFOA can not be solely attributed to POSF-based production activities despite the strong correlations between PFOS and PFOA Half-life of PFOA is less than PFOS
p. 33
Summary (continued)
PFNA
- 100% increase in average concentration from 2000 to 2006. Consistent with CDC findings.
PFDA
- 100% increase in average concentration from 2000 to 2006
PFUnDA
- 80 % increase in average concentration from 2000 to 2006
PFDoA
- Majority of 2006 values < LLOQ
Summary (continued)
Strong Correlations
- Observed between higher chain pe rfIuo roca rboxy Iates
PFOA/PFNA PFNA/PFDA PFDA/PFUnA PFUnA/PFDoA
p. 35
Summary (continued)
Weak Correlations
- Observed between higher chain and lower chain periluorocarboxylates
