EPA/600/R-09/033
March 2009
Perfluorocarboxylic Acid Content
in 116 Articles of Commerce
Zhishi Guo, Xiaoyu Liu, and Kenneth A. Krebs
U.S. Environmental Protection Agency, Office of Research and Development
National Risk Management Research Laboratory, Research Triangle Park, NC 27711
and
Nancy F. Roache
ARCADIS, 4915 Prospectus Dr., Suite F, Durham, NC 27713
National Risk Management Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
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Notice
This report has been subjected to the Agency's peer and administrative review
and has been approved for publication as an EPA document. Mention of trade names or
commercial products does not constitute endorsement or recommendation for use.
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Contents
Notice ii
Contents iii
Abstract iv
Acronyms and Abbreviations v
Acknowledgments vi
1. Introduction 1
2. Conclusions 3
3. Recommendations 4
4. Materials and methods 5
4.1 Sample collection 5
4.2 Verifying the presence of fluorine 5
4.3 Sample preparation, handling, and storage 6
4.4 Sample extraction and analysis 6
4.5 Quality assurance and quality control 8
5. Re suits 9
5.1 Statistics of AOC samples 9
5.2 Data quality of the analytical results 9
5.3 Extractable PFCA content in AOC samples 10
5.4 Statistics by sample category 31
6. Discussion 38
6.1 Source strengths 38
6.2 Comparison with literature values 40
6.3 Relative abundance of PFCAs 40
6.4 Domestic versus imported articles 43
6.5 Market trends 43
7. References 45
Appendix 48
in
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Abstract
Several recent studies have found elevated levels of perfluorocarboxylic
acids (PFCAs) in house dust, suggesting strongly the presence of indoor sources
of these compounds. The main goal of this study was to identify and rank
potentially important indoor sources by determining the PFCA content in articles
of commerce (AOCs). We analyzed 116 AOC samples purchased from retail
outlets in the United States between March 2007 and May 2008 by using a newly
developed extraction/analytical method. For these 116 samples, the content of
perfluorooctanoic acid (PFOA-C8) ranged from non-detectable to 6750 ng/g,
whereas the content of total PFCAs (the sum of C5 to C12 acids) ranged from
non-detectable to 47100 ng/g. Given the quantities of articles found in typical
homes, it is clear that professional carpet-care liquids, pre-treated carpeting,
treated floor waxes and sealants, and treated home textile products and upholstery
are likely the most important PFCA sources in non-occupational indoor
environments. The perfluorochemical-containing AOC market has been in a
transition period. Limited data suggest that the PFCA content in AOCs has shown
a downward trend overall. However, definitive confirmation of such a trend will
require long-term monitoring. More studies are needed to better understand PFCA
transport, exposure routes, and ways to reduce exposures in indoor environments.
IV
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Acronyms and Abbreviations
AOC articles of commerce
CAS# chemical abstract service registration number
HPLC high-performance liquid chromatography
TAP internal audit program
LC/MS/MS liquid chromatography / tandem mass spectrometry
PFC perfluorochemical
PFCA perfluorocarboxylic acid
PFOA perfluoroocanoic acid
PTFE polytetrafluoroethylene
RCS recovery check standard
RSD relative standard deviation
TPFCA total perfluorocarbonyl acids (the sum of C5 to C12 PFC As)
WD wavelength dispersive
XRF X-ray fluorescence
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Acknowledgments
We thank Andrew Lindstrom, Mark Strynar, Shoji Nakayama, and Ed Heithmar
of the U.S. EPA and Timothy Begley of the U.S. FDA for technical consultation and
assistance; Robert Wright of the U.S. EPA for QA support; Shirley Wasson (retired) and
Dean Smith of the U.S. EPA and David Natschke of Arcadis for operating the X-ray
fluorescence spectrometer; and Ivan Dolgov of the U.S. EPA for laboratory support.
VI
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1. Introduction
Although man-made perfluorochemicals (PFCs) have been widely used for
several decades, their potential impacts on human health and the global environment did
not draw much attention until the turn of the century when evidence of their widespread
presence in various environmental media, wildlife, and human tissue became clear [1"3].
Toxicological studies indicate that perfluorooctanesulfonic acid (PFOS) and
perfluorooctanoic acid (PFOA) - the two most extensively studied perfluorinated
compounds so far - can cause developmental and systemic toxicity in laboratory animals.
Reviews of the existing toxicological data can be found in references 4-6. The potential
health risks associated with perfluorocarboxylic acids (PFCAs) have promoted intensive
research on the sources, transport, transformation, and distribution of these chemicals and
their precursors in environmental media, as well as research related to ways to reduce the
health risks. Despite the significant progress that has been made so far, researchers are
yet to reach a consensus on what are the most important routes by which the general
population is exposed to these chemicals. In particular, there are different opinions on
whether PFCA-containing AOCs are significant contributors to the total exposure. For
instance, a study conducted by Washburn, et al. in 2005 concluded that exposures to
PFOA during consumer use of the articles evaluated in their study were not expected to
cause adverse health effects in infants, children, adolescents, and adults, nor result in
quantifiable levels of PFOA in human serum [7]. A more recent study by Fromme, et al.
used the data from indoor measurements in Canada and Norway and estimated that, for
the general population in Western countries, the inhalation of house dust contributed only
0.6% of the mean PFOA daily intake and 8.2% of the high PFOA daily intake [8]. By
contrast, Tittlemier, et al. identified treated carpeting as the second most important source
of exposure for PFOA after ingestion of food [9]. A study by Trudel, et al. found that the
consumption of contaminated food is the most important pathway causing exposure to
PFOA, followed by ingestion of dust and inhalation of air in low- and intermediate-
exposure scenarios. Their study also found that direct, product-related exposure is
dominant in high-exposure scenarios, in which consumers regularly use PFC-containing
products, such as impregnation sprays, or have treated carpets in their homes [10]. Trudel
and his co-workers also observed that product-related exposure tends to be more
important for PFOA than for PFOS, most likely because PFOS is no longer used in
consumer products. It is, therefore, apparent that the paucity of indoor source and
exposure data contributes to the significant uncertainty and differences of opinion about
the most prevalent exposure routes for these compounds.
The fact that elevated levels of PFCAs have been detected in house dust in Japan
[11], Canada [12], and the United States [13] strongly suggests the presence of indoor sources.
It is well known that fluorotelomer and fluoropolymer products are sources of PFCAs
and that PFCAs may exist in fluorotelomer products as unwanted by-products and in
fluoropolymer products as residuals [14]. Because a broad range of AOCs either contain or
are treated with fluorotelomer and fluoropolymer products [15-16\ they can be potential
sources of PFCAs. Given that AOCs are often used in close proximity to humans, it is
1
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hypothesized that they can contribute to human exposure to PFCAs either directly (e.g.,
by dermal contact and hand-to-mouth transfer) or indirectly (e.g., inhalation of suspended
particles from treated carpet and other interior surfaces).
There have been several studies of the PFCA content in AOCs, but most of them
report a single compound - PFOA. In 2005, Washburn and his colleagues reported the
PFOA content in 14 article groups based on theoretical calculations and analytical
measurements. Of these groups, pre-treated carpeting and carpeting treated with carpet-
care solution had the highest PFOA loadings: 0.2 to 0.6 and 0.2 to 2 mg of PFOA per kg
of article, respectively [7]. Studies by other researchers reported PFOA content in non-
stick cookware, food contact paper, thread sealant tape, and dental floss [17"20]. Data for
other PFCAs in AOCs are rather scarce. One study by Sinclair, et al. reported the C5 to
C12 PFCA content in three brands of popcorn packaging paper [20].
The main goal of this study was to identify the major PFCA sources in non-
occupational, indoor environments by determining the content of these chemicals in a
variety of AOCs and rank them in terms of source strengths. Policy-makers and
manufacturers can use the data for risk management purposes. The results also provide a
snapshot of the current uses of PFCAs on the market and may serve as baseline data for
future, long-term monitoring.
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2. Conclusions
We analyzed 116 AOC samples purchased from retail outlets in the United States
between March 2008 and May 2008 to determine the extractable content of C5 to C12
PFCAs using a newly developed extraction/analytical method. To the authors' best
knowledge, this is the first time that the C5 to C12 PFCA contents in a wide variety of
AOCs are been reported. The PFCA contents in these samples cover a broad range, from
nondetectable to as high as 6750 ng/g for PFOA and from non-detectable to 47100 ng/g
for total PFCAs (i.e., the sum of C5 to C12). In typical American homes with carpeted
floors, pre-treated carpet and commercial carpet-care liquids are likely the most
significant PFCA sources among the 13 article categories studied. For homes without
carpeting, floor waxes and stone/tile/wood sealants that contain fluorotelomers products
are important sources of PFCAs. Other potentially important indoor sources include
treated home textile, upholstery and apparel, and household carpet/fabric care liquids and
foams. The data presented in this report may help explain why PFCAs are frequently
detected in house dust. While the exact mechanisms by which PFCAs are transferred
from sources to dust are not well characterized, existing data strongly suggest that AOCs
may contribute to indoor human exposures to PFCAs either directly (dermal contact and
hand-to-mouth activities) or indirectly (inhalation of dust).
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3. Recommendations
Further research is needed in the following areas to better understand the effect of
PFCA-containing AOCs on human exposure: (1) PFCA transfer from sources to indoor
air and surfaces; (2) the relationship between AOCs and inhalation exposure; (3) the
significance of dermal exposure; (4) risk management measures for reducing PFCA
levels in polluted homes; and (5) monitoring of the market transition on a global scale
over an extended period of time.
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4. Materials and Methods
4.1 Sample Collection
AOC samples were purchased from retail outlets in the United States. Before
collecting samples, a survey was conducted to determine the availability of AOCs that
contained or were treated with fluorinated chemicals. Sample candidates were identified
based on one of the following claims by the vendors: (a) the article contains fluorinated
chemicals identifiable by their trade names (e.g., Scotchgard, GoreTex, and Teflon); (b)
the article contains fluorinated chemicals identifiable by the chemical names (e.g.,
polytetrafluoroethylene or PTFE); or (c) the article was identified as having certain
properties that are common for articles treated with fluorinated chemicals (e.g., stain
resistant, water repellent, and anti-grease). Sample candidates were purchased from local
stores in the Raleigh and Durham areas of North Carolina, in Atlanta and New York City,
and from on-line stores. While it was not the goal of this study to obtain statistically
representative samples for the entire U.S. market, efforts were made to maximize the
representativeness of the samples by considering the following factors whenever
applicable: article category, trade name of the fluoropolymer or fluorotelomer product,
brand name of the article, price range (high, medium, and low), store type (chain stores,
high-end stores, low-end stores, and specialty stores), and country of origin.
4.2 Verifying the Presence of Fluorine
Sample articles obtained from the market were first screened for the presence of
fluorine to exclude those with false claims and those that achieved certain surface
properties (e.g., anti-grease) without using fluorinated chemicals. Sample articles
containing less than 0.01% fluorine by weight were discarded. Typically, 0.05 to 0.5% of
the fluorochemical by weight of the article is used to ensure durable repellency [15]. For
articles made of polytetrafluoroethylene (PTFE), such as thread sealant tape and some
dental floss, the fluorine content can be greater than 70%. Thus, the 0.01% cut-off
provided an adequate safe margin to ensure that all sample articles treated with
fluorinated chemicals were included for further analysis. The fluorine content was
determined by wavelength dispersive (WD) X-ray fluorescence (XRF) spectrometry.
Instrument and operating parameters are provided in Table 4-1.
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Table 4-1. Analytical instrument and operating parameters for screen-testing AOC
samples for the presence of fluorine by the XRF method a
Instrument
Software
Power of X-ray tube
Measurement atmosphere
Scan method
Panalytical PW2404 Wavelength Dispersive (WD) X-ray
Fluorescence (XRF) Spectrometer equipped with the
PW2540 Sample Changer
SuperQ (Panalytical) for instrument control
IQ+ (Panalytical) for calibration and quantification
4000 watts
Vacuum (<10 mb) or under helium atmosphere
A continuous scan mode followed by fluorine-specific data
collection at the peak fluorine wavelength for an additional
10 second measurement.
a Liquid samples were tested on filters by wetting a 47-mm paper filter (Whatman) with
approximately 0.5 mL sample, and then air drying the filter under an aluminum foil cover.
4.3 Sample Preparation, Handling and Storage
Upon receipt, solid articles (except cookware) were cut into smaller subsections
for storage or extraction. Each AOC was divided into at least three subsections with a 60-
mm, tungsten carbide steel, rotary cutter and stainless steel scissors. These subsections
were used to cut specific-sized coupons (e.g., 4 x4, 6x6, and 10*10 cm, depending on
sample weight per unit area) as needed for extractions. Subsections for extraction were
placed in a desiccator for a minimum of eight hours and then weighed prior to extraction.
Non-stick cookware remained in its original package until extraction.
Liquid samples in bottles were subdivided into at least three 30-mL
polypropylene vials. For aerosol cans, the liquids were shaken and then collected in a 50-
mL beaker by gently pressing the release button. The liquids were then divided into
aliquots and stored in polypropylene vials. Samples for extraction were stored in the
refrigerator until needed for analysis.
All archived samples were individually wrapped in three layers of aluminum foil,
placed in a sealed plastic bag, and stored in a climate-controlled room.
4.4 Sample Extraction and Analysis
Coupons of solid samples (approximately 1 g) were weighed and placed in a 50-
mL, polyethylene, centrifuge vial with 45 mL of HPLC-grade methanol spiked with 100
jiL of recovery check standard (RCS, 2 ng/|iL perfluoro-w-[l, 2-13C2] decanoic acid} and
then extracted for 24 hours with a Nutating Mixer (Model VSN-5, PRO Scientific, Inc.,
CT, USA). The extract was transferred to a 170-mL borosilicate glass tube and
concentrated to approximately 1 mL under a nitrogen atmosphere by using a RapidVap
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N2 Evaporation System (Model 791000, LabConco, MO, USA), which was modified at
the factory to remove all Teflon parts and coatings. The blow-down sample was
transferred from the tube to a 10-mL volumetric flask through a 0.1 um Anotop syringe
filter (Whatman International, Madestone, England); the tube was rinsed five times with a
solution consisting of 60% (v/v) methanol and 40% (v/v) 2 mN ammonium acetate
aqueous solution (hereafter referred to as the 60:40 solution). The rinse liquids were
filtered and combined with the blow-down sample. After adding 100 jiL of the internal
standard (0.5 ng/jiL perfluoro-w-[l, 2, 3, 4-13C4] octanoic acid}, the sample was brought
tolO-mL with the 60:40 solution and sonicated for 10 minutes before LC/MS/MS
analysis.
A different extraction procedure was used for cookware, because the interior
coatings were difficult to remove from the metal base. Cookware was extracted by
covering the entire cooking surface with 100 to 150 mL of methanol spiked with 100 jiL
of the recovery check standard to a depth of approximately 0.3 mm. To minimize solvent
evaporation during extraction, the opening of the cookware was tightly sealed with
aluminum foil by compressing the foil to the inside and outside walls of the cookware
edge to a depth of approximately 0.5 cm. The static extraction was conducted at room
temperature. After 24 hours, the extract was collected from the cookware and
concentrated to 1 mL by the procedure described above.
All solid AOC samples were extracted by a single-step, 24-hour extraction, and
the extraction efficiency, as determined by consecutive extractions, ranged from 70% to
100% except for non-stick cookware, which had an extraction efficiency of 46% for
PFOA. The analytical results were reported as "extractable PFCAs."
For liquid samples, approximately 1 mL of sample were weighed, spiked with 100
jiL of 2 ng/|iL of the recovery check standard, and diluted to 25 mL with the 60:40
solution. The diluted samples were sonicated for 10 minutes and then filtered with a 50-
mL tube-top filter (Corning, Inc., NY, USA; 0.22-|im pore size). Ten milliliters (10 mL)
of the filtrate were transferred into a 10-mL volumetric flask and spiked with 100 jiL of
the internal standard. The final solution was sonicated for 10 minutes before LC/MS/MS
analysis. For samples with high levels of PFCAs, a second dilution was needed before
adding the recovery check standard.
Sample quantification was conducted using an Agilent 1100 HPLC equipped with
an Applied Biosystem API 3200 Triple Quadrupole Mass Spectrometer with a Turbo V
ion-spray interface. The instrument was calibrated for eight PFCA homologues (Table 4-
2) plus the recovery check standard at eight concentration levels in the concentration
range of 0.3 to 100 ng/mL with triplicate injections. The instrument detection limits for
individual PFCAs in the injection sample were <0.05 ng/mL. The method detection limits
were 1.0 to 3.9 ng/g for solid AOCs and 1.1 to 6.8 ng/g for liquid AOCs. The practical
quantification limit for the injection sample was 0.3 ng/mL, which is equivalent to 3 ng/g
for solid AOCs and 7.5 ng/g for liquid AOCs.
7
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The extraction and analytical methods described above have been evaluated and
are reported elsewhere [21].
Table 4-2. Analyte names, chemicals formulas, and chemical abstracts service
registration numbers (CAS#)
Analyte name
perfluoropentanoic acid
perfluorohexanoic acid
perfluoroheptanoic acid
perfluorooctanoic acid
perfluorononanoic acid
perfluorodecanoic acid
perfluoroundecanoic acid
perfluorododecanoic acid
Chemical formula
CsFnCOOH
C6Fi3COOH
CyFisCOOH
C8Fi7COOH
C9Fi9COOH
Ci0F2iCOOH
CnF23COOH
Ci2F25COOH
CAS#
2706-90-3
307-24-4
375-85-9
335-67-1
375-95-1
335-76-2
2058-94-8
307-55-1
4.5 Quality Assurance and Quality Control
A quality assurance project plan (QAPP) was developed before the start of the
project. The acceptance criterion for the calibration curve was that the coefficient of
determination (r2) be no less than 0.99. The internal audit program (LAP) standard, which
contains at least four of the calibrated PFCAs using a different chemical source, was
prepared by someone other than the person who prepared the calibration standards. The
analyst who conducted the calibration received the TAP standard without knowing the
concentrations. TAP standards were analyzed after each calibration as a measurement of
calibration verification. The criterion for acceptance was that the calculated concentration
and measured TAP standard using the calibration had to be within 15% of each other.
Daily calibration check (DCC) standards, approximately 5 ng/mL for each analyte, were
analyzed to evaluate the LC/MS/MS performance. Analytical results of a sample batch
were considered acceptable only if the percent recovery of the DCC was within 100 ±
15% and the percent relative standard deviation (%RSD) of DCCs was within ± 15%. All
samples and standards were injected in triplicate.
Solvents, glassware, gloves, and the FtPLC system were routinely checked for
PFCA contamination. A solvent blank was prepared with each set of standards and
samples to assess the solvent and the FIPLC system.
Each AOC sample was extracted in duplicate for LC/MS/MS analysis. The
analytical results were considered acceptable when the measured concentrations were in
the calibration range, the RSD for duplicates was within 20%, and the recovery of the
recovery check standard was within 100 ± 20%.
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5. Results
5.1 Statistics of AOC Samples
A total of 130 AOC samples containing at least 0.01% (w/w) fluorine were
obtained between March 2007 and May 2008. The dates the samples were manufactured
were unknown, because the product labels did not include that information. Breakdowns
of these samples by article category are given in Table 5-1. Sample descriptions and
conversion factors are presented in the Appendix (Table A-l).
Table 5-1. Sample breakdowns by article category
Category ID
A
B
C
D
E
F
G
H
I
J
K
L
M
Category name
Pre-treated carpeting
Commercial carpet-care liquids
Household carpet/fabric-care liquids and foams
Treated apparel
Treated home textile and upholstery
Treated non-woven medical garments
Treated floor waxes and stone/wood sealants
Treated food contact paper
Membranes for apparel
Thread sealant tapes and pastes
Non-stick cookware
Dental floss and plaque removers
Miscellaneous"
a Includes four car-care products, two boat-care products, one deck
sack for outdoor
use.
Samples
9
9
12
16
14
5
11
5
10
10
14
8
7
cleaner, and one dry
The samples were divided approximately equally between domestic and imported
products: United States - 58, China - 35, Thailand - 5, Dominican Republic - 3, France
- 3, Malaysia - 3, Mexico - 3, Bangladesh - 2, Canada - 2, Indonesia - 2, Ireland - 2,
Sri Lanka - 2, Vietnam - 2, Brazil - 1, Colombia - 1, England - 1, Italy - 1, Nicaragua
- 1, and Pakistan - 1. The origins of two samples could not be identified. According to
the product labels, six imported articles used materials or contain components made in
the United States, and one domestic product used imported material.
5.2 Data Quality
Samples were analyzed in batches. Each batch included four to seven AOC samples in
duplicate, one solvent blank, one field blank, and two daily calibration check standards.
For individual analytes, the relative standard deviation for duplicate samples had to be
9
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within 20% to be accepted. The estimated precision of the results was 100 ± 20% based
on duplicate samples, and the accuracy was 100 ± 20% based on the recovery of RCS.
The data presented were not adjusted for recovery of RCS. The RCS recoveries for
individual samples are available in the last column in Tables 5-2 through 5-14. Of the 130
AOC samples, 116 were analyzed successfully. For the 116 sets of valid data, the average
percent recovery of RCS was 97.9%. The results of the remaining 14 samples failed to
meet the data quality requirements after three or more trials, and the data were discarded.
Low recovery (i.e., <80%) for the recovery check standard was the common cause of the
failures. These samples are identified in the footnotes of Tables 5-2 through 5-14. They
belong to eight article categories, and no obvious trends could be identified.
5.3 Extractable PFCA Content in AOC Samples
Complete data for PFCA content in individual samples is presented in Tables 5-2
through 5-14, in which the following abbreviations and fonts are used:
BDL = result below instrument detection limit,
NR = not reported (i.e., the result does not meet data quality requirements),
RCS = recovery check standard; RCS percent recovery is the average of duplicate
or triplicate samples, and
Italics = result below practical quantification limit.
Figure 5-1 shows the distribution of the total amount of PFCAs (TPFCA, the sum of C5
to C12 PFCAs) for the 116 samples. Note that, for data comparability, the results for non-
stick cookware have been converted from (ng/cm2) to (ng/g) by assuming an average
coating thickness of 50 um and a PTFE density of 2.2 g/cm3 [17].
10
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Table 5-2. Extractable PFCAs in pre-treated carpeting (ng/g fiber)a
Sample
ID
A-l
A-2
A-3
A-4
A-5b
A-6C
A-8b
A-9
C5
NR
BDL
BDL
BDL
NR
BDL
2.16xl02
l.lSxlO1
C6
3.98X101
BDL
BDL
BDL
NR
NR
2.42xl02
1.92X101
C7
1.41X101
NR
NR
BDL
7.46X101
NR
5.16xl02
4.30X101
C8
1.04X101
BDL
8.39x10°
BDL
4.62xl02
5.77x10°
2.98xl02
1.99X101
C9
6.31x10°
BDL
NR
BDL
7.26X101
6.56x10°
2.92xl02
2.07X101
CIO
5.29x10°
BDL
7.26x10°
BDL
8.84X101
BDL
1.46xl02
1.84X101
Cll
2.34x10°
6. 1 7x1 ff1
NR
6.59X10'1
2.01X101
3.64x10°
5.22X101
1.23X101
C12 RCS
Recovery (%)
BDL
BDL
5.19x10°
BDL
NR
2.10x10°
6.35X101
4.20X101
81.7
91.4
84.3
90.8
81.9
84.6
92.4
84.7
a Results for sample A-7 failed to meet data quality requirements;
b This sample was extracted in triplicate;
c According to the vendor, sample A-6 is a replacement of A-5.
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Table 5-3. Extractable PFCAs in commercial carpet-care liquids (ng/g)
Sample
ID
B-l
B-2
B-3
B-4a
B-5
B-6
B-7b
B-8a
B-9b
a Samples
b Samples
C5
C6
C7
C8
C9
CIO
Cll
C12
RCS
Recovery (v/o)
1.73xl03
1.61X101
2.19x10'
1.23xl02
1.14x10'
1.94xl03
3.63xl02
3.77xl02
NR
B-4 and B-8
B-7 and B-9
5.20xl03
1.75xl02
4.48X101
l.OOxlO3
3.09X101
5.25xl03
9.28xl02
1.84xl03
2.20X101
are of same
are of same
1.41x10
5.18x10
4.95x10
7.47x10
1.98x10
1.3xl04
2.56x10
1.48x10
4
1
1
1
1
3
3
1.42x10'
brand, but
brand, but
6.75xl03
5.96xl02
S.OlxlO1
5.99xl02
1.91X101
S.OlxlO3
1.84xl03
1.72xl03
2.55X101
were purchased
were purchased
8.86xl03
NR
5.61X101
NR
6.38x10°
8.46xl03
NR
1.30xl03
1.75X101
1 year apart;
1 year apart;
4
1
2
1
8
2
.38xl03
.67xl02
NR
NR
BDL
.93xl03
.33xl03
.41xl02
.lOxlO1
4.00xl03
2.80x10'
NR
NR
NR
3.05xl03
8.44xl02
5. 07x1 02
1.62X101
2.15xl03
NR
NR
NR
NR
9.57xl02
NR
4.43 xlO2
8.52x10°
100
84.1
100
106
99.9
90.8
101
96.3
101
18
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Table 5-4. Extractable PFCAs in household carpet/fabric care liquids and foams (ng/g)
Sample
ID
C-l
C-2
C-3
C-4
C-5
C-6
C-7
C-8
C-9
C-10
C-ll
C-12
C5
BDL
BDL
1.40xl02
NR
NR
NR
NR
NR
BDL
BDL
1.84X101
NR
C6
BDL
BDL
1.09xl03
T.SSxlO1
1.95xl02
3.90X101
BDL
BDL
1.73xl02
4.18X101
5.61X101
BDL
C7
1.14X101
BDL
2.50xl03
NR
BDL
BDL
BDL
BDL
BDL
BDL
1.21X101
BDL
C8
6.97x10°
BDL
l.lSxlO3
6.66xl02
BDL
1.09X101
BDL
BDL
7.07xl02
8.79X101
1.37xl02
6.64X101
C9
3.09x10°
1. 63x10*
1.71xl03
NR
BDL
BDL
BDL
BDL
1.99X101
2.15x10*
5. 70x10°
NR
CIO
1.14x10°
3.25x10*
6.76xl02
1.04xl02
BDL
BDL
BDL
BDL
2.89xl02
3.36X101
4.00X101
1.86X101
Cll
BDL
4.29x10*
S.OlxlO2
BDL
BDL
BDL
BDL
BDL
4.51x10*
1.21x10*
BDL
BDL
C12 RCS
Recovery (%)
NR
BDL
3.28xl02
BDL
BDL
BDL
BDL
BDL
BDL
1.69x10*
7.91x10°
BDL
120
105
103
98.3
93.4
103
97.6
81.0
94.6
105
86.3
108
19
-------
Table 5-5. Extractable PFCAs in treated apparel (ng/g)a
Sample
ID
D-lb
D-2
D-3
D-4
D-5
D-6
D-7
D-8
D-10
D-ll
D-12
D-13
D-14
D-15
C5
7.26X101
5.41 xlff2
1.64X101
NR
NR
1.08x10°
3.94x10°
6.77x10°
NR
NR
BDL
1.75x10°
4.26x10°
3.55x10°
C6
1.53xl02
1.43x10°
4.32X101
2.70X101
2.72X101
2.71x10°
3.83X101
2.91X101
6.37X101
2.83X101
4.21x10°
1.40X101
2.61X101
4.61x10°
C7
2.21xl02
1.08x10°
6.49X101
8.96x10°
NR
3.11x10°
8.05x10°
1.27X101
1.87X101
4.92x10°
4.73x10°
4.66x10°
7.12x10°
8.58x10°
C8
1.14xl02
NR
i.eixio2
S.SOxlO1
3.20X101
5.44x10°
S.SSxlO1
S.SSxlO1
1.09xl02
4.43X101
2.76X101
6.93X101
NR
l.SlxlO1
C9
7.72X101
2. 86x1 ff1
2.35xl02
3.85x10°
5.97x10°
2.59x10°
4.13x10°
8.73x10°
1.36X101
3.55x10°
6.54X101
6.28x10°
NR
5.86x10°
CIO
5.37X101
NR
6.92X101
2.20X101
l.SSxlO1
3.26x10°
2.83X101
3.93X101
4.68X101
2.39X101
1.66X101
2.32X101
2.30X101
8.06x10°
Cll
3.94X101
5.04 xlff1
6.15X101
1.39x10°
3.60x10°
NR
1.94x10°
3.61x10°
5.17x10°
1.81x10°
2.14X101
2.00x10°
2.03x10°
1.38x10°
C12 RCS
Recovery (%)
4.10X101
4.27 xlff1
2.12X101
1.45X101
8.04x10°
NR
l.SOxlO1
6.47x10°
NR
9.42x10°
NR
5.36x10°
NR
3.67x10°
102
101
88.9
99.9
99.3
108
103
103
96.0
80.0
113
89.3
96.0
86.7
a Results for samples D-9 and D-16 failed to meet data quality requirements;
b This sample was extracted in triplicate.
20
-------
Table 5-6. Extractable PFCAs in treated home textile and upholstery (ng/g)
Sample
ID
E-l
E-2
E-3
E-4
E-5
E-6
E-7
E-8
E-9a
E-10
E-ll
E-12
E-13
E-14
C5
BDL
BDL
3.09X101
BDL
BDL
BDL
2.16X101
BDL
9.47X101
BDL
BDL
BDL
1.43x10°
BDL
C6
BDL
1.19x10°
6.22X101
BDL
BDL
2.96x10°
6.80X101
l.OSxlO1
2.38xl02
BDL
8.56x10°
BDL
3.87x10°
1.59x10°
C7
NR
1.22x10°
9.46X101
1.80x10°
4.09xlff'
1.76x10°
9.66X101
NR
5.15xl02
1.11x10°
3.14x10°
7.96X101
6.03x10°
1.23x10°
C8
5.83x10°
3.26x10°
2.93xl02
3.49x10°
6.12x10''
2.18x10°
3.30xl02
l.SSxlO1
4.38xl02
NR
2.75X101
S.SOxlO1
UTxlO1
3.83x10°
C9
BDL
1.36x10°
3.18xl02
2.01x10°
3.96x10''
NR
2.13xl02
7.15x10°
4.37xl02
NR
3.95x10°
3.41x10'
4.37x10°
1.78x10°
CIO
2.66x10°
BDL
l.SOExlO2
BDL
BDL
2.20x10°
1.25xl02
8.99x10°
2.47xl02
2.42x10°
8.37x10°
BDL
6.55x10°
2.29x10°
Cll
NR
BDL
9.80X101
BDL
BDL
6.80x10''
4.57X101
NR
1.86xl02
BDL
BDL
BDL
5.63X10'1
1.09x10°
C12 RCS
Recovery (%)
NR
NR
NR
NR
BDL
7. 78x10''
4.30X101
NR
LlOxlO2
9.34xlff'
BDL
3.73x10'
NR
1.13x10°
111
108
97.3
91.1
89.2
102
100
106
110
99.0
97.2
97.9
103
104
a This sample was extracted in triplicate.
21
-------
Table 5-7. Extractable PFCAs in treated non-woven medical garments (ng/g)
Sample
ID
F-l
F-2
F-3
F-4
F-5
C5
4.31x10°
4.26x10°
BDL
7.86xl02
6.02x10°
C6
1.45X101
NR
NR
5.98xl02
1.43X101
C7
2.05X101
1.84X101
9.03x10°
5.06xl02
2.24X101
C8
4.62X101
4.71X101
6.07X101
3.69xl02
8.42X101
C9
7.82X101
8.21X101
6.33x10°
3.34xl02
l.OSxlO2
CIO
2.90X101
2.00X101
1.74X101
2.18xl02
6.42X101
Cll
2.74X101
2.48X101
NR
1.73xl02
4.17X101
C12 RCS
Recovery (%)
l.OSxlO1
8.72x10°
5.30x10°
8.89X101
2.69X101
85.8
86.9
80.4
101
101
22
-------
Table 5-8. Extractable PFCAs in floor waxes and stone/tile/wood sealants (ng/g)a
Sample
ID
G-l
G-2b
G-3b
G-4b
G-6
G-7
G-8
G-9
G-10
G-ll
C5
NR
7.19x10°
8.19x10°
8.62x10°
BDL
NR
1.12xl02
BDL
3.15xl02
3.73xl02
C6
4.83X101
l.SSxlO1
1.41X101
1.91X101
4.07X101
1.17xl03
7.72xl02
BDL
5.38xl03
1.16xl03
C7
6.39X101
2.14X101
2.75X101
2.73X101
6.25X101
l.OSxlO2
3.13xl02
BDL
5.46xl02
1.56xl03
C8
4.48X101
7.50x10°
1.32X101
1.56X101
3.69X101
S.OSxlO2
4.77xl02
4.35x10'
3.72xl03
1.21xl03
C9
5.04X101
4.19x10°
1.23X101
l.lTxlO1
4.76X101
3.31X101
l.SSxlO2
3.30x10'
2.60xl02
9.39xl02
CIO
1.91x10'
3.56x10°
5.32x10°
NR
2.38x10'
3.30xl02
2.65xl02
3.44x10'
l.SSxlO3
6.32xl02
Cll
2.21x10'
1.65x10°
2.12x10°
2.10x10°
2.22x10'
BDL
BDL
BDL
4.15x10'
3.75xl02
C12 RCS
Recovery (%)
1.41x10'
2.97x10°
3.33x10°
NR
2.37x10'
BDL
NR
BDL
4.70xl02
2.84xl02
98.2
95.4
109
116
101
90.2
94.4
99.8
92.3
110
a Results for sample G-5 failed to meet data quality requirements;
b Samples G-2, G-3, and G-4 could not be filtered after dilution. They were applied on aluminum foil
cover. The dry films were then extracted as solid samples. The potential PFCA loss during the curing
expected to be insignificant.
as a thin layer and dried under
period was not evaluated but is
23
-------
Table 5-9. Extractable PFCAs in food contact paper (ng/g)a
Sample
ID
H-2
H-3
H-4
H-5
C5
BDL
BDL
BDL
2.21xl02
C6
BDL
l.lTxlO1
NR
4.43xl03
C7
BDL
BDL
BDL
2.85xl03
C8
BDL
BDL
1.04xl02
4.64xl03
C9
2.25x10°
BDL
BDL
1. 53x10*
CIO
BDL
BDL
7.02X101
BDL
Cll
BDL
BDL
BDL
BDL
C12
BDL
BDL
5.40X101
BDL
RCS
Recovery (%)
106
86.9
105
103
'Results for sample H-l failed to meet data quality requirements.
24
-------
Table 5-10. Extractable PFCAs in membranes for apparel (ng/g)a
Sample
ID
1-1
1-2
1-4
1-5
1-7
1-8
1-9 b
1-10
C5
BDL
BDL
BDL
8.23x10°
BDL
3.33x10°
BDL
BDL
C6
1.72X101
NR
NR
5.09X101
NR
3.03X101
NR
2.05X101
C7
l.lSxlO1
3.23x10°
NR
1.21X101
1.09X101
5.46x10°
4.66x10°
5.02x10°
C8
7.70X101
9.15x10°
2.96X101
1.63xl02
4.35X101
8.26X101
1.04xl02
7.30X101
C9
5.95x10°
1.84x10°
1.06X101
1.28X101
8.08x10°
5.97x10°
5.37x10°
5.95x10°
CIO
2.43X101
4.33x10°
7.59x10°
7.22X101
l.SSxlO1
2.77X101
4.19X101
2.92X101
Cll
3.24x10°
1.10x10°
6.01x10°
NR
NR
2.02x10°
3.41x10°
3.03x10°
C12 RCS
Recovery (%)
NR
3.26x10°
NR
2.36X101
6.29x10°
NR
8.59x10°
9.82x10°
109
108
108
113
82.4
87.7
111
112
a Results for sample 1-3 and 1-6 failed to meet data quality requirements.
b This sample was extracted in triplicate.
25
-------
Table 5-11. Extractable PFCAs in thread seal tapes and pastes (ng/g)a
Sample
ID
J-l
J-2
J-3
J-4
J-5
J-6
J-7
J-9
J-10
C5
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
9.50X101
C6
BDL
BDL
BDL
BDL
BDL
NR
1.97X101
BDL
3.26X101
C7
2.85x10°
BDL
7.32X10'1
NR
NR
NR
2.87X101
BDL
3.24X101
C8
4.43x10°
5.35x10°
NR
NR
2.30X101
1.44xl03
3.49xl03
BDL
3.89X101
C9
2.82x10°
2.31x10°
NR
NR
2.28x10°
2.80x10°
4.56x10°
1.67x10'
4.06X101
CIO
BDL
BDL
NR
NR
BDL
BDL
BDL
BDL
3.62X101
Cll
1.69x10°
1.42x10
BDL
BDL
1.38x10°
BDL
BDL
9.86x10°
4.06X101
C12 RCS
Recovery (%)
NR
NR
NR
NR
2.14x10°
BDL
BDL
1.25X101
3.75X101
99.2
102
82.9
92.0
96.1
105
109
93.0
87.0
a Results for sample J-8 failed to meet data quality requirements.
26
-------
Table 5-12. Extractable PFCAs in non-stick cookware (ng/cm2 coated surface)21
Sample
ID
K-l
K-3
K-4
K-5
K-6
K-7
K-8
K-9
K-10
K-ll
K-12
K-13
K-14
C5
BDL
l.SOxlO'2
NR
NR
BDL
BDL
BDL
BDL
NR
BDL
BDL
1.87xlO'2
NR
C6
BDL
BDL
NR
NR
BDL
BDL
3.71xlO'3
BDL
BDL
BDL
BDL
l.SlxlO'2
7.02xlO'3
C7
BDL
1.55 xlff3
NR
NR
BDL
BDL
BDL
2.55xlff3
4.01 xlff3
NR
8.69xlO'3
1.72xlO'2
9.00xlO'3
C8
BDL
NR
2.09xlO'2
4.74xlO'2
BDL
BDL
BDL
4.02 xlff3
BDL
7.57xlO'3
BDL
1.21xlO'2
1.25xlO'2
C9
4.89xlff3
2.47 xlff3
NR
NR
BDL
BDL
BDL
4.31 xlff3
8.50xlff3
5.66xlO'3
BDL
9.85xlO'3
2.67X10'3
CIO
BDL
BDL
NR
NR
BDL
BDL
BDL
BDL
BDL
BDL
BDL
9. 56 xlff3
BDL
Cll
2.89 xlff3
1.48 xlff3
NR
NR
BDL
BDL
BDL
2. 55 xlff3
3.89 xlff3
3.12xlO'3
BDL
9.95xlO'3
2.60xlO-3
C12 RCS
Recovery (%)
3. 70 xlff3
1.88xlff3
NR
NR
1.37xlO'2
1.07 xlff2
3.63xlO'3
3.23xlff3
4.81xlff3
3.96xlO'3
8.57xlO'3
1.85xlO'2
9.06xlO'3
103
96.9
92.0
99.4
98.2
94.5
96.4
98.3
99.5
95.6
92.2
95.5
114
a Results for sample K-2 failed to meet data quality requirements.
27
-------
Table 5-13. Extractable PFCAs in dental floss and plaque removers (ng/g)a
Sample
ID
L-l
L-2
L-4
L-5
L-7
L-8
C5
BDL
2.50x10°
BDL
BDL
BDL
BDL
C6
BDL
NR
BDL
BDL
BDL
BDL
C7
BDL
6.30x10°
6. 20x1 ff1
BDL
3.99x10°
1.71x10°
C8
NR
5.48x10°
NR
9.67X101
BDL
4.58X101
C9
9.39X10'1
NR
7.02 xlff1
BDL
5.81x10°
2.25x10°
CIO
BDL
BDL
BDL
BDL
BDL
BDL
Cll
BDL
2.87x10°
BDL
BDL
3.43x10°
1.33x10°
C12 RCS
Recovery (%)
NR
NR
1.43x10°
BDL
4.40x10°
1.69x10°
102
81.4
118
112
102
106
a Results for sample L-3 and L-6 failed to meet data quality requirements.
28
-------
Table 5-14. Extractable PFCAs in miscellaneous AOC samples (ng/g)a
Sample
ID
M-l
M-2
M-3
M-5
C5
l.OSxlO1
BDL
BDL
BDL
C6
2.09X101
BDL
1.73xl02
BDL
C7
e.oixio1
BDL
2.05xl02
2.98x10°
C8
2.49X101
BDL
1.25xl02
BDL
C9
3.28X101
8. 26x1 01
6.95x10'
BDL
CIO
1.44X101
BDL
BDL
BDL
Cll
1.47X101
BDL
BDL
BDL
C12
1.09X101
BDL
BDL
2.97x10°
RCS
Recovery (%)
84.9
93.0
89.7
80.7
'Results for sample M-4, M-6 and L-7 failed to meet data quality requirements.
29
-------
(U
.a
E
50
40
30
cu
o. 20
E
CO
w 10
0
>104 103-104 102-103 101-102
TPFCA Range (ng/g)
<10
Figure 5-1. Distribution of total extractable PFCAs for 116 AOC samples.
30
-------
5.4 Statistics by sample category
The ranges, arithmetic means, and medians of PFCA content for individual article
categories are presented in Figures 5-2 through 5-14. The overall TPFCA range is from
non-detectable to 47100 ng/g; the range for PFOA is from non-detectable to 6750 ng/g.
For most article categories, the means were greater than the medians in most cases,
indicating that the PFCA content in a small number of samples was significantly higher
than in the rest of samples.
<~IWW
500
3
0) 400
c
"£ 300
0)
§ 200
0
100
0
i
.
4
>
^^— Range
k
t
:
A Mean
x Median
i
I , ,
t X 1 Xvvvv-
5 6 7 8 9 10 11 12
PFCA Carbon Number
Figure 5-2. Ranges, arithmetic means, and medians for PFCAs in the fiber of pre-treated
carpeting (N = 8).
-------
3 12000
O)
c
•£ 8000
0
c
<§ 4000
0
x
5
I
i
,
'
^— Range
A Mean
i
i
x :
X Median
: x x x
f '.» T T T T T
6 7 8 9 10 11 12
PFCA Carbon Number
Figure 5-3. Ra
liquids (N = 9)
3000 -,
2500
O)
"5, 2000
+T 1500
0)
= 1000
o
O
500
0
nges, arithmetic means, and medians for PFCAs in commercial carpet-care
A
• :
'
V
' !
^— Range
A Mean
X Median
1 1
III
f V \/ \/
5 6 7 8 9 10 11 12
PFCA Carbon Number
Figure 5-4. Ranges, arithmetic means, and medians for PFCAs in household carpet /
fabric care liquids and foams (N = 12)
32
-------
ouu
250
"55
0) 200
c
+T 150
S 100
O
0
50
0
^^— Range
=
x
: \
1
'
x
1
A Mean
x Median
r x 1 1
x 1 0 x
I T I ',•» T
5 6 7 8 9 10 11 12
PFCACarbon Number
Figure 5-5. Ranges, arithmetic means, and medians for PFCAs in treated apparel (N = 14)
500
TO
0) 400
•£ 300
, '> '> ^\ ^N
5 6 7 8 9 10 11 12
PFCA Carbon Number
Figure 5-6. Ranges, arithmetic means, and medians for PFCAs in treated home textile
products and upholstery (N = 14).
33
-------
^ 800
*U>
S 60°
"c
aj 400
c
O
° 200
0
t
i
k
>
k
)
^^^ Range
A Mean
X Median
In,
/ x I v X 1
< 1 X X y
ii i
5 6 7 8 9 10 11 12
PFCACarbon Number
Figure 5-7. Ranges, arithmetic means, and medians for PFCAs in non-woven medical
garments (N = 5)
5000
o
0, 4000
c
*T 3000
0)
c 2000
O
o
1000
0
i
i
I
f V V
Range
A Mean
x Median
! I A i
5 6 7 8 9 10 11 12
PFCA Carbon Number
Figure 5-8. Ranges, arithmetic means, and medians for PFCAs in floor waxes and
stone/tile/wood sealants (N = 10).
34
-------
^ 4000
o
? 3000
"c
« 2000
o
° 1000
0
i
XX
i
f V
j
V
^^~ Range
A Mean
X Median
f \^ \^ \^ \^
5 6 7 8 9 10 11 12
PFCACarbon Number
Figure 5-9. Ranges, arithmetic means, and medians for PFCAs in food contact paper (N
4)
200
O) 15°
c
+r 100
0)
3 50
0
PFCA Carbon Number
Figure 5-10. Ranges, arithmetic means, and medians for PFCAs in the membranes for
apparel (N = 9). Note that the means are invisible because they are superimposed by the
medians.
5
)
X
I *
^— Range
A Mean
X Median
; i
X
* 1 x
T i i
6 7 8 9 10 11
X
1
12
35
-------
3 sooo
+T 2000
0)
c
<§ 1000
0
J
^^^ Range
A Mean
X Median
i
A A A A A A A
5 6 7 8 9 10 11 12
PFCA Carbon Number
Figure 5-11. Ranges, arithmetic means, and medians for PFCAs in thread seal tape and
pastes (N = 9)
0.06
^ 0.05
CM
E
o 0.04
^ 0.03
| 0.02
O
o 0.01
0
i
x
—T—
X
—T—
6 7 8 9 10 11
PFCA Carbon Number
I
12
Figure 5-12. Ranges, arithmetic means, and medians for PFCAs in non-stick cookware
(N=13)
36
-------
120
100
O) 80
c^
+T 60
0)
c
o
o
40
20
0
i
v v X
A Mean
X Median
:
V v «i V
5 6 7 8 9 10 11 12
PFCACarbon Number
Figure 5-13. Ranges, arithmetic means, and medians for PFCAs in dental floss and
plaque removers made from PTFE (N = 6)
240
•g 120
60
0
X
X
X
-f-
X
u_5_
6 7 8 9 10 11
PFCA Carbon Number
x
12
Figure 5-14. Ranges, arithmetic means, and medians for PFCAs in miscellaneous articles
(N = 4)
37
-------
6. Discussion
6.1 Source Strengths
A recent study by Strynar, et al. [13] reported that the house dust samples collected
from 102 home and 10 day care centers in the United States showed higher PFOA content
and greater prevalence compared to samples collected from Japan [11] and Canada [12].
These authors also find that 96.4% of their samples have quantifiable levels of PFOA,
suggesting widespread PFCA contamination in American homes. In simplified terms, the
strength of a PFCA source can be expressed as the product of the PFCA content in unit
weight (or area) and the quantity of the article in a given microenvironment. Table 6-1
compares the source strengths by using the arithmetic means for different AOC
categories and the estimated quantities of articles in a hypothetical "typical" American
home. Among the 13 article categories, professional carpet-care liquids, pre-treated
carpeting, floor waxes and stone/tile/wood sealers and household textiles and upholstery
are likely the largest PFCA sources in American homes.
38
-------
Table 6-1. Comparison of source strengths for total amount of PFCA (TPFCA) in a hypothetical, "typical" American home a
Group ID
A
B
C
D
E
F
G
H
I
J
K
L
M
Article category
Pre-treated carpeting c
Commercial carpet-care liquids
Household carpet/fabric-care liquids and foams
Treated apparel
Treated home textile and upholstery
Treated non-woven medical garments
Treated floor waxes and stone/tile/wood sealants
Treated food contact paper
Membranes for apparel
Thread seal tapes and pastes
Non-stick cookware
Dental floss and plaque removers
Miscellaneous
TPFCA
in article
48.4 ng/cm2
12000 ng/g
953 ng/g
198 ng/g
336 ng/g
795 ng/g
2430 ng/g
3 100 ng/g
124 ng/g
603 ng/g
0.028 ng/cm2
3 1.3 ng/g
69.5 ng/g
Article
quantity b
150m2
6kgd
1kg
2kg
5kg
Okg
1kg
0.01 kg
1kg
0.02 kg
1m2
0.005 kg
0
TPFCA in
home (mg)
72.6
71.8
0.95
0.40
1.68
0
2.42
0.03
0.12
0.01
0.0003
0.0002
0
aThe average, single-family home size in the U.S. in 2004 was 2330 ft2 (http://www.nahb.org/).b The quantities of articles are rough
estimates.c Assuming 70% of floor area is carpet; conversion factors for total PFCA are given in supporting information. d For one
application; dilution factor is considered.
39
-------
6.2 Comparison with literature values
Comparison between the results of this study and those of other reported studies
can be made only for PFOA, because data are unavailable in the literature for other
PFCAs. As shown in Table 6-2, which compares the ranges of PFOA content in different
article categories, the results from this study appear significantly higher than the literature
values for treated non-woven medical garments, stone/tile/wood sealants, membranes for
apparel, food contact paper, and dental floss/tape. The opposite appears true for treated
apparel and treated home textiles. Washburn, et al. did not detect PFOA in any treated
medical garments samples [7], but PFOA was detected at relatively high levels in all five
samples in this study (Table 5-7 and Figure 5-7). Further statistical comparisons are
impossible due to the lack of details about the literature values.
Table 6-2. Comparison of PFOA content ranges between this study and literature values
(in ng PFOA/g sample, unless indicated otherwise)
Article category Literature a This study a
Pre-treated carpeting 200 to 600 b ND (<1.5) to 462
Carpet-care liquid treated carpeting 200 to 2000b 0.6 to 224 c
Treated apparel ND (<20) to!400b 5.4tol61
Treated uphol stery ND (<3 4) b 0.6 to 293
Treated home textiles ND (<20) to 1400b 3.8 to 438
Treated non-woven medical garments ND(<34)b 46 to 369
Industrial floor wax and wax removers 0.5 to 60 b 7.5 to 44.8
Stone, tile, and wood sealants ND (< 100)b 477 to 3720
Membranes for apparel 0.008 to 0.07 ng/cm2 b 0.1 to 2.5 ng/cm2
Food contact paper 6 to 290 d ND (<1.5) to 4640
Dental floss/tape 3 to 4 d ND (<1.5) to 96.7
Thread sealant tape 1800d ND (<1.5) to 3490
PTFE cookware 4 to 75 d ND (<1.5) to 4.3
a ND: not detected (detection limit in parentheses). Data source: ref 7 (based on
theoretical calculations).c Calculated by using the recommended coverage and assuming
the area density of the carpet is 0.25 g/cm2. d Data source: ref 17.
6.3 Relative Abundance of PFCAs
For fluorotelomer-treated articles (categories A to H in Table 5-1), three patterns
are recognizable: (a) the distribution of the relative abundances resembles, to a certain
degree, a log-normal distribution (Figure 6-1); (b) PFCAs with even numbers of carbons
are predominant (Figure 6-2); and (c) PFCAs with odd numbers of carbons are
predominant (Figure 6-3). The frequencies of occurrence for the three patterns are (a) >
(b) > (c). Case c is rare. Depending on the article categories, the relative abundance of
PFOA (C8) ranges from 15% to 38% (Figure 6-4). The large value for category H (food
40
-------
contact paper) was the result of a single sample that had the highest PFCA content. The
previous study on popcorn packaging paper gave the PFOA abundance of 34% in total
(C5 to C12) PFCAs [20]. For articles containing or made from fluoropolymers
(categories I to L), PFOA (C8) was the most abundant PFCA species. Its relative
abundance ranged from 38% to 93%.
30
^ 25
at
1 20
•a
§ 15
.a
1 1°
Jo 5
at
* 0
7 8 9 10
PFCA Carbon Number
11
12
Figure 6-1. Relative abundance of PFCA in floor wax G-l 1.
41
-------
40
2 30
c
ro
| 20
> 10
+->
"oJ
* 0
7 8 9 10
PFCA Carbon Number
11
12
Figure 6-2. PFCA relative abundance in sample D-7 (treated apparel).
35
Sso
o>
£ 25
ro
•o 20
3
-Q 15
« 10
^ 5
o>
06 0
7 8 9 10
PFCA Carbon Number
11
12
Figure 6-3. PFCA relative abundance in sample B-l (commercial carpet-care liquid).
42
-------
^ 50
0) 40
O
C
•S 30
-Q 20
O 10
LJ_
Q.
B
D
H
AOC Category
Figure 6-4. Relative abundance of PFOA (C8) in fluorotelomer-treated AOC samples (i.e.,
article categories A to H in Table 3-1).
6.4 Domestic versus Imported Articles
Side-by-side comparison between U.S. domestic products and imported products
was difficult because they were unevenly distributed among the 13 article categories
studied. For instance, pre-treated carpeting, carpet-care liquid, and floor wax categories
are dominated by domestic products. On the other hand, treated apparel, treated home
textile and upholstery, treated non-woven medical garments, and membranes for apparel
categories are dominated by imported products. The articles with the highest PFCA
content in each category were divided approximately evenly between domestic and
imported products. Domestic products have the highest PFCA content in categories A, B,
C, G, H, and M, while imports have the highest PFCA content in categories D, E, F, I, K,
and L. The sample with the highest PFCA content treated non-woven medical garments
(category F) was an imported product using materials made in the U.S. Because of the
globalization of the world economy, it is obvious that international collaboration will be
necessary to reduce further the PFCA content in consumer articles in the world market.
6.5 Market Trends
In recent years, government agencies, chemical companies, the research
community, and environmental groups have been working to reduce the production of
PFCAs and the use of PFCAs and their precursor chemicals in fluorotelomer and
fluoropolymer products. For example, the U.S. Environmental Protection Agency
initiated the PFOA Stewardship Program in 2006, in which the eight major companies in
the industry committed voluntarily to reduce facility emissions and product content of
43
-------
PFOA and related chemicals on a global basis by 95 percent no later than 2010 and to
work toward eliminating emissions and product content of these chemicals by 2015
(http://www.epa.gov/oppt/pfoa/pubs/pfoastewardship.htm). During the process of
collecting samples for this study, the application of fluorinated chemicals in AOCs had
been undergoing a transition aimed at reducing the PFCA content. The availability of
treated AOCs in certain categories, such as treated apparel and food contact paper, had
been reduced. The limited data from this study seem to suggest that some fluorinated
surface-modifying agents have been re-formulated to lower the PFCA content. The first
two cases in Table 6-3 show such changes. The trends are uneven, however, and
significant numbers of articles with high PFOA content are still on the market. In one
case, the PFOA content even increased significantly (the third case in Table 6-3). The
data in Table 3-3 are very limited in scope and the two sampling times are only one year
apart. It takes a much longer period of time (e.g., several years) and a much wider range
of sampling to confirm any trends.
Table 6-3. Changes in PFOA content for three AOC samples
Product
Pre-treated carpet
Commercial carpet protector
Commercial carpet protector
PFOA content (ng/g)a
Apr-May 2007
462 ±51.6
1838 ±92.7
599 ±65.1
May 2008
5. 88 ±0.444
24.5 ± 1.21
1722 ±89.2
- p-Valueb
<0.001
O.OOOl
<0.001
a Mean and standard deviation for duplicate extractions; For one-sided student test.
44
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7. References
[1] Renner, R. Growing concern over perfluorinated chemicals.
Environmental Science & Technology 35: 154A-160A (2001).
[2] Giesy, J. P., and K. Kannan. Perfluorochemical surfactants in the environment.
Environmental Science & Technology 36: 146A-152A (2002).
[3] Kannan, K., J. Newsted, R. S. Halbrook and J. P. Giesy. Perfluorooctanesulfonate
and related fluorinated hydrocarbons in mink and river otters from the United
States. Environmental Science & Technology 36: 2566-2571 (2002).
[4] Kennedy Jr., J. L., J. L. Butenhoff, G. W. Olsen, J. C. O'Connor, A. M. Seacat, R.
G. Perkins, L. B. Biegel, S. R. Murphy and D. G. Farrar. The toxicology of
perfluorooctanoate. Critical Review of Toxicology 34, 351-384 (2004).
[5] Lau, C., J. L. Butenhoff and J. M. Rogers. The developmental toxicity of
perfluoroalkyl acids and their derivatives, Toxicology and Applied Pharmacology.
198:231-241 (2004).
[6] U. S. EPA. Draft risk assessment of the potential human health effects associated
with exposure to perfluorooctanoic acid and salts., U.S. EPA, Office of Pollution
Prevention and Toxics, http://www.epa.gov/oppt/pfoa/pubs/pfoarisk.pdf (2005).
[7] Washburn, S. T., T. S. Bingman, S. K. Braithwaite, R. C. Buck, L. M. Buxton, H.
J. Clewell, L. A. Haroun, J. E. Kester, R. W. Rickard and A. M. Shipp. Exposure
assessment and risk characterization for perfluorooctanoate in selected consumer
articles. Environmental Sciences & Technology 39: 3904-3910 (2005).
[8] Fromme, H., S. A. Tittlemier, W. Volkel, M. Wilhelm and D. Twardella,
Perfluorinated compounds - exposure assessment for the general population in
western countries. InternationalJournal of Hygiene and Environmental Health
(in press).
[9] Tittlemier, S. A., K. Pepper, C. Seymour, J. Moisey, R. Bronson, X. L. Cao and R.
W. Dabeka. Dietary exposure of Canadians to perfluorinated carboxylates and
perfluorooctane sulfonate via consumption of meat, fish, fast foods, and food
items prepared in their packaging. Journal of Agricultural and Food Chemistry 55:
3203-3210 (2007).
[10] Trudel, D., L. Horowitz, M. Wormuth, M. Scheringer, I. T. Cousins, and K.
Hungerbiihler. Estimating consumer exposure to PFOS and PFOA. Risk Analysis
28:251-269(2008).
45
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[11] Moriwaki, H., Y. Takatah, and R. Arakawa. Concentrations of perfluorooctane
sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in vacuum cleaner dust
collected in Japanese homes, Journal of Environmental Monitor ing 5: 753-757
(2003).
[12] Kubwabo, C., B. Stewart, J. Zhu and L. Marro. Occurrence of perfluorosulfonates
and other perfluorochemicals in dust from selected homes in the city of Ottawa.
Journal of Environmental Monitoring 1: 1074-1078 (2005).
[13] Strynar M. J., and A. B. Lindstrom. Perfluorinated compounds in house dust from
Ohio and North Carolina, Environmental Science & Technology 42: 3751-3756
(2008).
[14] Prevedouros, K., I. T. Cousins, R. C. Buck and S. H. Korzeniowski. Sources, fate
and transport of perfluorocarboxylates. Environmental Science & Technology 40:
32-44 (2006).
[15] Rao, N. S., and B. E. Baker. "Textile Finishes and Fluorosurfactants." In
Orgaofluorine Chemistry, ed. R. E. Banks, B. E. Smart and J. C. Tatlow, Plenum
Press, New York and London, 1994.
[16] Kissa, E. Fluorinated Surfactants and Repellents, 2nd ed. Marcel Dekker Inc. New
York and Basel, 2001.
[17] Begley, T. H., K. White, P. Honigfort, M. L.Twarski, R. Neches, R. and R. A.
Walker. Perfluorochemicals: potential sources of and migration from food
packaging. Food Additives and Contaminants 22: 1023-1031 (2005).
[18] Powley, C. R., M. J. Michalczyk, M. A. Kaiser and L. W. Buxton. Determination
of perfluorooctanoic acid (PFOA) extractable from the surface of commercial
cookware under simulated cooking conditions by LC/MS/MS. Analyst 130: 1299-
1302 (2005).
[19] Bononi, M. and F. Tateo. Identification of perfluorooctanoic acid release from
commercial coated cooking pans by liquid chromatograpgy coupled to electospray
ionization tandem mass spectrometry, American Journal of Agricultural &
Biological Science. 2: 191-194 (2007).
[20] Sinclair, E., S. K. Kim, H. B. Akinleye and K. Kannan, Quantitation of gas-phase
perfluoroalkyl surfactants and flurotelomer alcohols released from nonstick
cookware and microwave popcorn bags, Environmental Sciences & Technology.
41: 1170-1175(2007).
[21] Liu, X., K. Krebs, Z. Guo and N. Roache. Method development for liquid
chromatography/triple quadrupole mass spectrometer analysis of trace level
46
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perfluorocarboxylic acids in articles of commerce. Journal of Chromatography A
(in press).
47
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Appendix
Description of AOC Samples
Table A-l. Sample description and conversion factora
Sample
ID
Description
Conversion Factor
Units
Value
A. Pre-treated carpeting
A-l
A-2
A-3
A-4
A-5
A-6
A-7
A-8
A-9
Nylon Carpet 1
Renewably sourced polymer
Polyester carpet
Berber 94% Olefin/6%Nylon carpet
Nylon Carpet 2
Frieze nylon carpet
Nylon Carpet 3
Textured carpet
Nylon Carpet 4
g of fiber/cm2
g of fiber/cm2
g of fiber/cm2
g of fiber/cm2
g of fiber/cm2
g of fiber/cm2
g of fiber/cm2
g of fiber/cm2
g of fiber/cm2
1.41X10'1
8.57xlO'2
9.33xlO'2
l.lSxlO'1
l.SlxlO'1
7.15xlO'2
6.61xlO'2
1.45X10'1
7.44xlO'2
B. Commercial carpet/fabric care liquids (not applicable)
B-l
B-2
B-3
B-4
B-5
B-6
B-7
B-8
B-9
Carpet and upholstery protector
Carpet protector concentrate 1
Fabric protector solvent based
Carpet protector concentrate 2
Carpet/upholstery protector concentrate
Carpet protector concentrate 3
RTU Carpet protector
Carpet protector
RTU Carpet protector
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
C. Carpet/fabric care liquids for spot treatment
C-l
C-2
C-3
C-4
C-5
C-6
C-7
C-8
C-9
C-10
C-ll
C-12
Household carpet shampoo
Carpet spot and stain remover
Spot removal kit
Fabric protector 1
Fabric protector 2
Household carpet protector
Household carpet/upholstery cleaner
Household spot & stain remover
Wash-in waterproofing
Spray-on water repellent
Wash-in waterproofing
Spray-on water repellent
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
a N/A = not applicable.
48
-------
Table A-l. Sample description and conversion factor (cont.)
Sample
ID
Description
Conversion Factor
Units
Value
D. Treated apparel
D-l
D-2
D-3
D-4
D-5
D-6
D-7
D-8
D-9
D-10
D-ll
D-12
D-13
D-14
D-15
D-16
Man's pant
Man's short pant
Girl's uniform shirt
Boy's dress shirt 1
Boy's dress pant 2
Lady's dress pant
Girl's uniform pant
Woman's hiking shoe
Woman's knee pant
Man's dress pant
Man's polo shirt
Man's nylon shirt
Man's dress shirt 1
Man's dress pant 2
Man's dress pant 3
Lab coat
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
2.06xlO'2
2.50xlO'2
2.28xlO'2
1.60xlO'2
2.61xlO'2
2.35xlO'2
2.30xlO'2
2.35xlO'2
1.23xlO'2
2.93xlO'2
2.18xlO'2
LlOxlO'2
1.14xlO'2
2.78xlO'2
2.65xlO'2
1.68xlO'2
E. Treated home textile and upholstery
E-l
E-2
E-3
E-4
E-5
E-6
E-7
E-8
E-9
E-10
E-ll
E-12
E-13
E-14
Microfiber fabric 1
Microfiber fabric 2
Loveseat slip cover 100% cotton
Loveseat slip cover 100% polyester
Loveseat slip cover 60% cotton/40%
polyester
Loveseat slip cover 100% polyester
Mattress pad 1
Mattress pad 2
Mattress pad 3
Table cloth
Ironing board cover
Table cloth
Upholstery fabric, 57% cotton/43% polyester
100% Cotton throw
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
2.43xlO'2
2.45xlO'2
l.SOxlO'2
2.49xlO'2
2.00xlO'2
1.40xlO'2
1.35xlO'2
1.95xlO'2
1.38xlO'2
1.60xlO'2
l.lSxlO'2
2.19xlO'2
4.75xlO'2
2.20xlO'2
F. Treated non-woven medical garments
F-l
F-2
F-3
F-4
F-5
Lab coat
Surgical gown 1
Surgical gown 2
Surgical gown 3
Reuseable pillow
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
6.00xlO'3
e.ooxio'3
S.OOxlO'3
7.50xlO'3
LlOxlO'2
49
-------
Table A-l. Sample description and conversion factor (cont.)
Sample
ID
Description
Conversion Factor
Units
Value
G. Treated floor waxes and stone/tile/wood sealants
G-l
G-2
G-3
G-4
G-5
G-6
G-7
G-8
G-9
G-10
G-ll
Household floor wax 1
Household floor wax 2
Commercial spray and buff
Commercial floor sealer 1
Commercial floor sealer 2
Commercial floor sealer 3
Stone & tile sealer
Granite sealer
Household floor polish
Marble & granite sealer
Stone, tile & wood sealant
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
H. Treated food contact paper
H-l
H-2
H-3
H-4
H-5
French fry bag
French fry carton
Popcorn bucket
Popcorn bag
Microwave cooking bag
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
3.25xlO'3
2.41xlO'2
1.99xlO'2
3.87xlO'3
8.60xlO'3
/. Membranes for apparel
1-1
1-2
1-3
1-4
1-5
1-6
1-7
1-8
1-9
1-10
Women's rain jacket
Men's rain jacket
Men's jacket
Women's insulated pant
Men's parka
Woman's rain jacket
Sombrero (hat) 1
Sombrero (hat) 2
Man's rain parka
Ball cap
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
9.83xlO'3
9.39xlO'3
8.64xlO'3
1.59xlO'2
1.82xlO'2
1.90xlO'2
l.SOxlO'2
1.40xlO'2
9.00xlO'3
1.83xlO'2
J. Thread seal tapes and pastes
J-l
J-2
J-3
J-4
J-5
J-6
J-7
J-8
J-9
1/2" Tape 1
1/2" Tape 2
1/2" Tape 3
1/2" Tape 4
1/2" Tape 5
1/2" Tape 6
1/2" Tape 7
Pipe thread sealant 1
Pipe thread sealant 2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
g/cm2
N/A
N/A
2.97xlO'3
2.86xlO'3
2.66xlO'3
2.71xlO'3
2.89xlO'3
l.OlxlO'3
9.49xlO'3
N/A
N/A
50
-------
Table A-l. Sample description and conversion factor (cont.)
Sample
ID
Description
Conversion Factor
Units
Value
J. Thread seal tapes and pastes (cont.)
MO
Pipe thread sealant 3
N/A
N/A
K. Non-stick cookware
K-l
K-2
K-3
K-4
K-5
K-6
K-7
K-8
K-9
K-10
K-ll
K-12
K-13
K-14
10" Fry pan
10"Frypanw/lid
5 qt Sautesse w/lid
12"Frypanw/lid
14" Untility pan w/lid
10" Camp fry pan
Child's mess kit
Cookie sheet
11" Skillet
2 qt Sauce pan
22-cm Fry pan
10" Skillet
10" Skillet
4qt 10.5" Sauteusepan
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
L. Dental floss and plaque removers
L-l
L-2
L-3
L-4
L-5
L-6
L-7
L-8
Unflavored floss
Mint floss
Satin floss
Satin tape
Flosser
Deep clean floss
Micro-mint flosser
Angle flosser
g/m
g/m
g/m
g/m
g/m
g/m
g/m
g/m
1.75E-01
1.30E-01
9.91E-02
1.21E-01
4.67E-02
1.42E-01
4.67E-02
1.53E-01
M. Miscellaneous
M-l
M-2
M-3
M-4
M-5
M-6
M-7
Tire shine
Car spray wax
Car wheel cleaner
Dry sack
Deck cleaner
Boat polish 1
Boat polish 2
N/A
N/A
N/A
g/cm
N/A
N/A
N/A
N/A
N/A
N/A
l.OOE-02
N/A
N/A
N/A
51
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