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TIean B. S weeney Staff Vice Resident
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JSetaanffBV.icSewPereenseiydent, 3M Environmental, Health and Safety Operations
Analysis of the Homologous Series of
Periluorocarboxylates - Periluorobutanoate
(C4) through Perfluorododecanoate (C12)
from American Red Cross Adult Blood
Donors, 2006
SETAC
North America 29thAnnual Meeting Tampa Bay, Florida November 19, 2008
CmcD;
~
i 3
Geary Olsen1 Mark Ellefson2 William Reagen2
1i23M Company, 1Medical Department, 2Environmental 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, C8Fi 7S 0 3') - PFOA (perfluorooctanoate, - PFHS (perfluorooctanehexanesulfonate C6Fi 3S 0 3') - PFBS (perfluorobutanesulfonate, C4F9S 0 3') - Me-PFOSA-AcOH
(N-methyl perfluorooctanesulfonamidoacetate,
C8F17S02N(CH3)CH2C 0 0 )
- Et-PFOSA-AcOH (N-ethyl perfluorooctanesulfonamidoacetate, C8F17S 0 2N(CH2CH3)CH2C 0 0 )
Distribution of PFOS Concentrations (ng/mL), American Red Cross Blood Donors, 2000 - 2006
300
250 2006
2000 200
150
No. of adults
100
50
II
5588S88S
i t "i-- T--** i i TMi i i S>8?88888S88
PFOS (ng/mL)
si I
Distribution of PFOA Concentrations (ng/mL), American Red Cross Blood Donors, 2000 - 2006
150
, 2006 2000
100
50
0 N ' t t O C O O ^ C rM ^r - r C rO CN O ON N ON )
PFOA (ng/mL)
< LOQ(1.92)
Geometric Mean (95% Cl) Concentrations CDC NHANES
and American Red Cross Studies, 1999-2006
Calafat et al. ES&T 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
40.0
35.0
Concentration (ng/mL)
30.0 25.0 20.0
NHANES (1999-2000) Am Red Cross (2000-2001) NHANES (2003-2004) Am Red Cross (2006)
15.0
10.0
5.0
0.0
PFOS
PFOA
PFHS
Me-PFOSAAcOH
Et-PFOSAAcOH
95th Percentile (upper bound), CDC NHANES and American Red Cross Studies, 1999-2006
110.0
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
CDC NHANES (1999-2000) Am Red Cross (2000-2001) CDC NHANES (2003-2004) Am Red Cross (2006)
ntration (ng/mL)
PFOS
I
PFOA
PFHS
Me-PFOSAAcOH
Et-PFOSAAcOH
Age- and Sex-Adjusted PFOS Concentrations (ng/mL), American Red Cross Blood Donors, 2000 - 2006, by Six Geographical Locations
CM C
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CL
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Boston 2000 Boston 2006 Charlotte 2000 Charlotte 2006 Hagerstown 2000 Hagerstown 2006 Los Angeles 2000 Los Angeles 2006 Mpls-St. Paul 2000 Mpls-St. Paul 2006 Portland 2000 Portland 2006
o- .o r ooPcFOoAo-(nPg/om^L )c on *_o o^ i oc o
H----- 1------1------1----- 1------1------1----- 1------1------1----- !------1----- 1----- 1-----
-- -----X
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Age- and Sex-Adjusted PFOA Concentrations (ng/mL) American Red Cross Blood Donors, 2000 - 2006, by Six Geographical Locations
Methods
Current Analysis
Target Analytes
- PFBA (perfluorobutanoate, C3F7C 0 2`) - PFPeA (perfluoropentanoate, C4F9C 0 2') - PFHA (perfluorohexanoate CgF^CO f) - PFHpA (perfluoroheptanoate, CF13^02') - PFOA (perfluorooctanoate, C7Fi 5C0 2') - PFNA (perfluorononanoate, c 8f 17c o 2-) - PFDA (perfluorodecanoate, C9F19^^2 ) - PFUnA (perfluoroundecanoate, C 10F21CO2`) - PFDoA (perfluorododecanoate, ^ n F ^ C O ^ )
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
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
Ranae 0.04 - 8.63 0 .0 3 -0 .9 6 0 .0 4 -1 .5 3 0.02 - 2.030 0.78 - 53.70 0 .1 2 -5 .1 0 0.05-5.270 0 .0 2 -3 .1 7 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
<0.3 (LOD)
0.09 (0.08-0.09)
PFOA
3.9 (3 .6 -4 .3 )
3.44 (3.30-3.59)
PFNA
1.0 (0 .8 -1 .1 )
0.97 (0.93-1.05)
PFDA
<0.3 (LOD)
0.34 (0.33-0.35)
PFUnA
<0.3 (LOD)
0.18 (0.17-0.19)
PFDoA
<1.0 (LOD)
*Calafat et al. EHP 2007
0.03 (0.03-0.04)
> |
Multivariate Scatterplot Matrix
PFBA
y.
* PFPeA
t , .4 - . - m .
% t
k 'L
. k.
.i
.k . t , .
.i . . L
.
fakfllMIpVh" a L , . H r< . ' L , . .
PFHA * 99
.k -
k . -------- .
. PFHpA
h~
>* k - .i
k>_. 9 mm m
i ft'. -
fe a r'--
fc - - U
L
: PFOA = * :
J P -:PFNA
% m^T
t
.fe i
b n "- - fe - .
, ` PFDA
. a-" -
f r
. '
K h U ..
fe. . -f e - ' , - m - . M r * -
PFUnA
* A lfe . , - L iw . - I f -
1 2 3 4 .1 .3 .5 .7 .9
-
fc -.:
* 9%m* a. " A%'
-^ "
*
* . * PFDoA
10 20 30 1 2 3 4 5 1 2 3 4 5 .51 2 3 .1 .2 .3 .4
Multivariate
1-iScatterplot Matrix -14 -34 -1o--jj
-2 2
-Z -.
---023i4-44j
o4
2- - .
-432-44j
i4
01.55o4-4. --01..55-]E
i4
--2o1i4444
-3 -2 -1 0 1 -3 -2 -1 0 - 3 -2 -1 0 -4 -3 -2 -1 0 0 1 2 3 -1.5 0 .5 1.5-2 -1 0 1 -3 -2 -1 0 1 -4 -3 -2 -1
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 PFDoA 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
2000 American Red Cross Serum Samples (N = 645) Compared to 2000 QC Reanalyzed w/ 2006 (N - 78):
Geometric Means (95% Cl)
o> 2000 Am Red Cross
0
1c
112000 Am Red Cross QC Samples
8
OO
PFOS
PFOA
rf*! PFHxS
rrrr^ l
Et-PFOSAAcOH
1 T1
MePFOSA-
AcOH
2000 American Red Cross QC Serum Samples (N = 78) vs 2006 Plasma Samples (N = 600): Geometric Mean (95% Cl)
8.0 7.0 6.0 5.0 4.0 3.0
Concentration (ng/mL)
2006 American Red Cross Plasma Samples (N = 600) by Location: Geometric Means
5.0
Boston Charlotte Hagerstown Los Angeles Mpls-St. Paul Portland
Concentration (ng/mL)
0 oX
0
4C
2000 American Red Cross QC Serum Samples (N = 78) vs. 2006 Plasma Samples (N = 600):
PFOS
PFOA
2006 American Red Cross Plasma Samples (N = 600): Percent Branched PFOS, by Location
2006 American Red Cross Plasma Samples (N = 600): Percent Branched PFOA, by Location
<r
Serum Elimination Half-lives in Humans
Geo Mean
Compound Half-life
95% Cl
PFBA
2.7 days 1 .9 - 3 .8
PFOA
3.5 yrs
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 etal. 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
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
PFOA
Summary (continued)
- 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
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 perfluorocarboxylates
PFOA/PFNA PFNA/PFDA PFDA/PFUnA PFUnA/PFDoA
Summary (continued)
Weak Correlations - Observed between higher chain and lower
chain perfluorocarboxylates