EPA/600/R-12/585
August 2012
Trends of Perfluoroalkyl Acid Content in Articles of Commerce
Market Monitoring from 2007 through 2011
Xiaoyu Liu, Zhishi Guo, and Kenneth A. Krebs
U.S. Environmental Protection Agency
Office of Research and Development
National Risk Management Research Laboratory
Air Pollution Prevention and Control Division
Research Triangle Park, NC 27711
and
Robert H. Pope and Nancy F. Roache
ARCADISU.S. Inc.
4915 Prospectus Dr., Suite F
Durham, NC 27709
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Notice
This document has been reviewed internally in accordance with the U.S. Environmental Protection
Agency policy and approved for publication. Mention of trade names or commercial products does
not constitute endorsement or recommendation for use.
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Table of Contents
Notice i
Table of Contents ii
List of Tables iv
List of Figures vi
Abstract viii
Acronyms and Abbreviations ix
Acknowledgments x
1. Introduction 1
2. Conclusions 3
3. Recommendations 4
4. Materials and Methods 5
4.1 Sample Collection 5
4.2 Sample Handling, Storage and Preparation 6
4.3 Sample Extraction and Analysis 6
4.4 Quality Assurance and Quality Control 11
4.4.1 Data Quality Indicators Goals 11
4.4.2 Instrument Calibration 11
4.4.3 Detection Limit 12
4.4.4 Quality Control Samples 12
5. Results 13
5.1 Distribution of AOC Samples 13
5.2 Extractable PFCA Content in AOC Samples 18
5.3 Total PFCAs in AOC Samples 35
5.4 Extractable PFAS Content in AOC Samples 41
5.5 Data Quality 43
5.5.1 LC/MS/MS Calibration 43
5.5.2 Detection Limits 43
5.5.3 Quality Control Samples 43
6. Discussion 48
6.1 Trends of Individual PFCAs 48
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6.2 Trends of Total PFCAs 53
6.3 Domestic versus Imported Articles 54
6.4 Short-Chain versus Long-Chain PFCAs in AOCs 55
6.5 Perfluoroalkyl Sulfonates (PFAS) 55
7. References 57
Appendix A. Summary of PFCAs in AOC Samples 59
m
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List of Tables
Table 4-1. AOCs analyzed for monitoring market trends 5
Table 4-2. Analyte names, chemical formulas, and chemical abstracts service registration
numbers 8
Table 4-3. Operating conditions for the Agilent 1100 HPLC/Applied Biosystem API 3200 9
Table 4-4. Analyte-dependent mass spectra parameters 10
Table 4-5. Data quality indicator goals for critical measurements 11
Table 5-1. AOC samples collected for pre-treated carpeting 13
Table 5-2. AOC samples collected for commercial carpet/fabric-care liquids 14
Table 5-3. AOC samples collected for household carpet/fabric-care liquids and foams 14
Table 5-4. AOC samples collected for treated apparel 15
Table 5-5. AOC samples collected for treated home textile and upholstery 15
Table 5-6. AOC samples collected for treated non-woven medical garments 16
Table 5-7. AOC samples collected for treated floor waxes and stone/wood sealants 16
Table 5-8. AOC samples collected for treated food contact paper 17
Table 5-9. AOC samples collected for membranes for apparel 17
Table 5-10. AOC samples collected for thread-sealant tapes and pastes 17
Table 5-11. Summary of PFAS detected in selected AOCs 42
Table 5-12. LC/MS/MS calibration of PFCAs for the project 44
Table 5-13. LC/MS/MS calibrations of PFAS for the project 45
Table 5-14. IAP results for each calibration 45
Table 5-15. Summary of instrument detection limits (IDL, ng/mL) 46
Table 5-16. Average recoveries of DCCs for the project 47
Table 6-1. Sign test data and p-values for individual PFCAs detected in AOC samples 50
Table 6-2. Sign test results of TPFCA in AOCs 54
Table 6-3. Sign test results of PFCA in AOCs in short-chain-length group versus long-chain-
length group 55
Table A-1. Extractable PFCAs in pre-treated carpeting (ng/g AOC) 60
Table A-2. Extractable PFCAs in commercial carpet-care liquids (ng/g AOC) 60
Table A-3. Extractable PFCAs in household carpet/fabric-care liquids (ng/g AOC) 61
IV
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Table A-4. Extractable PFCAs in treated apparel (ng/g AOC) 62
Table A-5. Extractable PFCAs in treated home textile and upholstery (ng/g AOC) 62
Table A-6. Extractable PFCAs in treated non-woven medical garments (ng/g AOC) 63
Table A-7. Extractable PFCAs in treated floor waxes (ng/g AOC) 63
Table A-8. Extractable PFCAs in treated food contact paper (ng/g AOC) 64
Table A-9. Extractable PFCAs in membranes for apparel (ng/g AOC) 64
Table A-10. Extractable PFCAs in thread sealant tapes (ng/g AOC) 65
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List of Figures
Figure 5-1. Trends of PFCAs detected in nylon carpet 1 (A-l) (Two slightly different
products were purchased on 9/8/2011) 18
Figure 5-2. Trends of PFCAs detected in corn polymer carpet (A-2) 19
Figure 5-3. Trends of PFCAs detected in polypropylene carpet 4 (A-9) 19
Figure 5-4. Trends of PFCAs detected in carpet/upholstery protector concentrate 1 (B-l) 20
Figure 5-5. Trends of PFCAs detected in solvent based fabric protector (B-3) 20
Figure 5-6. Trends of PFCAs detected in carpet/upholstery protector concentrate 2 (B-5) 21
Figure 5-7. Trends of PFCAs detected in ready-to-use carpet protector 1 (B-7) 21
Figure 5-8. Trends of PFCAs detected in carpet shampoo 1 (C-l) 22
Figure 5-9. Trends of PFCAs detected in household carpet protector 1 (C-4) 22
Figure 5-10. Trends of PFCAs detected in household carpet protector 2 (C-5) 23
Figure 5-11. Trends of PFCAs detected in household carpet care 2 (C-8) 23
Figure 5-12. Trends of PFCAs detected in membrane fabric care 1 (C-9) 24
Figure 5-13. Trends of PFCAs detected in girl's uniform shirt (D-3) 24
Figure 5-14. Trends of PFCAs detected in boy's uniform/dress shirt (D-4) 25
Figure 5-15. Trends of PFCAs detected in boy's uniform/dress pant (D-5) 25
Figure 5-16. Trends of PFCAs detected in girl's uniform pant (D-7) 26
Figure 5-17. Trends of PFCAs detected in man's dress pant (D-10) 26
Figure 5-18. Trends of PFCAs detected in mattress pad 1 (E-7) 27
Figure 5-19. Trends of PFCAs detected in mattress pad 2 (E-8) 27
Figure 5-20. Trends of PFCAs detected in surgical gown 1 (F-2) 28
Figure 5-21. Trends of PFCAs detected in surgical gown 2 (F-3) 28
Figure 5-22. Trends of PFCAs detected in surgical gown 3 (F-4) 29
Figure 5-23. Trends of PFCAs detected in household floor wax 1 (G-l) 29
Figure 5-24. Trends of PFCAs detected in household floor wax 2 (G-2) 30
Figure 5-25. Trends of PFCAs detected in commercial floor wax 1 (G-4) 30
Figure 5-26. Trends of PFCAs detected in commercial floor wax 2 (G-6) 31
Figure 5-27. Trends of PFCAs detected in food paper 1 (H-3) 31
Figure 5-28. Trends of PFCAs detected in food paper 2 (H-4) 32
Figure 5-29. Trends of PFCAs detected in food paper 3 (H-5) 32
VI
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Figure 5-30. Trends of PFCAs detected in membrane 1 (1-1) 33
Figure 5-31. Trends of PFCAs detected in membrane 2 (1-5) 33
Figure 5-32. Trends of PFCAs detected in membrane 3 (1-8) 34
Figure 5-33. Trends of PFCAs detected in thread-sealant tape 1 (J-l) 34
Figure 5-34. Trends of PFCAs detected in thread-sealant tape 2 (J-6) 35
Figure 5-35. Trends of TPFCA of C4 to C12 for selected pre-treated carpeting (Two A-l
samples and two A-2 samples were collected on the same day in 2010 and
2011, respectively.) 36
Figure 5-36. Trends of TPFCA of C4 to C12 for selected commercial carpet/fabric-care
liquids (2008 is 5/2008 and 2008-2009 is 11/2008 to 5/2009) 36
Figure 5-37. Trends of TPFCA of C4 to C12 for selected household carpet/fabric-care liquids 37
Figure 5-38. Trends of TPFCA of C4 to C12 for selected treated apparel (2011a is 2/2011
and201 Ibis 8/2011) 37
Figure 5-39. Trends of TPFCA of C4 to C12 for selected treated home textile and upholstery
products 38
Figure 5-40. Trends of TPFCA of C4 to C12 for selected treated non-woven medical
garments 38
Figure 5-41. Trends of TPFCA of C4 to C12 for selected treated floor waxes and stone/wood
sealants 39
Figure 5-42. Trends of TPFCA of C4 to C12 for selected treated food contact paper 39
Figure 5-43. Trends of TPFCA of C4 to C12 for selected membranes for apparel 40
Figure 5-44. Trends of TPFCA of C4 to C12 for selected thread-sealant tapes 40
Figure 5-45. PFAS detected in one membrane for apparel (AOC 1-1-1) 41
Figure 6-1. Relative abundance of PFCA in AOCs from 2007 to 2011 (N is the number of
AOCs monitored) 53
Figure 6-2. Distribution of the AOCs used for market monitoring based on country of origin 54
Figure 6-3. PFAS detected in a carpet shampoo in 2008 and 2011 56
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Abstract
The U.S. Environmental Protection Agency (EPA) has established an ongoing effort to quantify
possible changes in levels of perfluorinated chemicals (PFCs) in articles of commerce (AOCs).
Temporal trends in the concentrations of selected PFCs, including perfluorooctanoic acid (PFOA)
and other perfluorocarboxylic acids (PFCAs), in 35 AOCs were measured from the year of 2007
through 2011. The AOC samples that were collected included carpet, commercial carpet-care
liquids, household carpet/fabric-care liquids, treated apparel, treated home textiles, treated non-
woven medical garments, floor waxes, food-contact paper, membranes for apparel, and thread-
sealant tapes. They were purchased from retail outlets in the United States between March 2007
and September 2011. Two to five AOCs from each of the ten categories were monitored.
Depending on the market availability, products were collected for two to four data points in a span
of four years. The perfluorocarboxylic acid (PFCA) contents in AOCs have shown an overall
downward trend as portion of the fluorochemical industry has reformulated their PFC products.
However, PFOA (C8) could still be detected in many AOCs that we had monitored. No obvious
tendencies for change over the monitored period for short-chain PFCA (sum of C4 to C7) versus
long-chain PFCA (sum of C8 to C12) were observed. A longer and wider range of monitoring will
be required to confirm an observed trend. In addition to monitoring PFCA contents in AOCs,
fourteen AOC samples were analyzed to determine the amounts of perfluoroalkyl sulfonates
(PF AS) they contained. The limited data show the pronounced increase of perfluoro-butane
sulfonate (PFBS-C4), an alternative to perfluorooctanoic sulfonate (PFOS), in the samples.
vm
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Acronyms and Abbreviations
AOC articles of commerce
BDL below detection limit
CAS# chemical abstract service registration number
CFR Code of Federal Regulations
DCC daily calibration check
DQI data quality indicator
EPA Environmental Protection Agency
HPLC high-performance liquid chromatography
TAP internal audit program
DDL instrument detection limit
IS internal standard
LC/MS/MS liquid chromatography/tandem mass spectrometry
MDL method detection limit
NRMRL National Risk Management Research Laboratory
NIST National Institute of Standards and Technology
OPPT Office of Pollution Prevention and Toxics
PFAS perfluoroalkyl sulfonates
PFC perfluorochemical
PFCA perfluorocarboxylic acid
PFOA perfluorooctanoic acid
PFOS perfluorooctane sulfonate
QC quality control
RCS recovery check standard
RSD relative standard deviation
SNURs Significant New Use Rules
TSCA Toxic Substances Control Act
TPFCA total perfluorocarboxylic acids (the concentration sum of C4 to C12, C6 to C12
orC8toC12PFCAs)
TPFAS total perfluoroalkyl sulfonates (the concentration sum of C4, C6, C7, C8, and
CIO PFAS)
IX
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Acknowledgments
We thank Andrew Lindstrom and Mark Strynar of the U. S. EPA for technical consultation and
assistance; Robert Wright of the U.S. EPA for QA support; Russell Logan of ARCADIS for
preparing the samples and Elizabeth Harris of ARCADIS for conducting the sample extraction;
Leonard Stefanski of North Carolina State University and Ross Leadbetter of University of North
Carolina at Chapel Hill for assistance in statistic analysis.
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1. Introduction
Perfluoroalkyl acids (PFAAs) came to the attention of researchers and risk managers because of
their persistence, developmental toxicity and other health effects in laboratory animals [1'2] and
their ubiquitous presence in humans, wildlife, and environmental media. [3"10] To fully understand
the health and environmental risks associated with PFCAs and related chemicals, EPA's Office of
Pollution Prevention and Toxics (OPPT) was interested in investigating the role that articles of
commerce (AOC) containing or having been treated with fluoropolymers and fluorotelomers have
in human exposure in the microenvironments of homes and offices and as a source of
environmental exposure once released to the outside world.
A project to test the perfluorocarboxylic acid (PFCA) content of various AOCs began in late 2006
in response to OPPT's need for data for use in assessing the risk of human exposures to
perfluorooctanoic acid (PFOA) and other PFCAs. In March 2007, in Phase 1 of the project, EPA's
National Risk Management Research Laboratory (NRMRL) initiated the collection of AOC
samples in determining the PFCA content in new AOCs, and the analyses of all the samples were
completed in May 2008. [3'11] In that phase of the project, 13 categories of articles containing 131
consumer articles produced in 19 countries were collected. These articles were believed to have
been treated with fluorinated chemicals and were analyzed to determine their content of five to
twelve carbons (C5 to C12) PFCAs. We analyzed 116 of the 131 samples successfully and found
that their total PFCA concentrations (i.e., the sum of C5 through C12) ranged from non-detectable
to 47,100 ng/g, whereas their PFOA concentrations ranged from non-detectable to 6,750 ng/g. One
of the major findings in Phase 1 was that, among the 13 article categories, commercial carpet-care
liquids, mill-treated carpeting, treated floor waxes and sealants, and treated home textile and
upholstery were potentially the largest PFCA sources in non-occupational indoor environments.
The results of Phase 1 provided a snapshot of the transition period during which the use of
fluorotelomer and fluoropolymer products in consumer products was changing rapidly. The limited
data from the Phase 1 study suggested that some fluorinated surface-modifying agents had been
reformulated to lower the PFCA content. The trends were uneven and many articles with high
PFOA content could still be found on the market.
In May 2000, 3M, the primary American producer of perfluorooctane sulfonate (PFOS),
announced the phase-out of its production of PFOS. However, there may still be other producers of
PFOS-related compounds around the world.
In 2006, eight major companies in the PFC industry and the EPA jointly launched the PFOA
Stewardship Program. Under this cooperative program, the goal is to reduce facility emissions to
all media of PFOA, precursor chemicals that can break down to PFOA, and related higher
homologue chemicals and product content levels of these chemicals by 95 percent by 2010, and to
work toward the elimination of these chemicals from emissions and products by 2015. [12] Also,
EPA promulgated three Significant New Use Rules (SNURs) under the Toxic Substances Control
Act (TSCA) to limit any future manufacture or importation of 271 perfluoroalkyl sulfonates
(PFAS)[13]. Thus, as portion of the fluorochemical industry reformulates its products, it is
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anticipated that the overall content of PFOA and other PFCAs in articles of commerce will show a
downward trend. However, it will take a long time (i.e., several years) and extensive sampling to
verify if this indeed is a significant trend.
The project to test for PFCAs in AOCs was extended into a second phase to assess the market
trends between 2007 and 2011. The objectives were to determine how the levels of PFCAs in
AOCs changed over the monitoring period and which AOCs were potentially major PFCA sources
in microenvironments. This market trend monitoring study provided a means to conduct
independent assessment of the degree of success of the PFOA Stewardship Program. Priority was
given to monitoring the market trends of the AOC categories established in Phase 1 that had the
highest exposure potential, so samples with the highest PFCA content were selected. The results of
the PFCA analyses were compared with the results acquired in Phase 1. In addition to seeking a
general understanding of the market trends, this study also was intended to determine whether
short-chain, fluorinated compounds are being used as alternatives and whether PFOS-related
substances were still being used in AOCs.
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2. Conclusions
To the best of the authors' knowledge, this is the first time that the temporal market trends of C4 to
C12 PFCA contents in a wide variety of AOCs have been reported. In conclusion, large reduction
of PFOA was observed in each of the AOC categories with the exception of one product in the
home textile and upholstery category and two thread-sealant tape products, for which increased
PFOA concentrations were detected. It was observed that the PFBA-C4 content increased in 19 of
the 35 AOCs monitored, with all floor wax products showing significant increases in the amount of
PFBA-C4. The latest monitoring data suggest that commercial carpet-care liquids, treated floor
waxes, treated food contact paper, and thread-seal ant tapes are likely the most significant sources
of the nine PFCAs, including PFOA, among the 10 article categories that were studied. The data
presented here indicate that the concentrations of PFCAs in the AOCs have decreased rapidly in
recent years. The observed trends of the relative increase of PFBA-C4 and PFBS-C4S confirm that
perfluorinated substances that have shorter chain are being used as alternatives to long-chain
PFCAs. However, no significant difference in trends was observed for short-chain PFCA (sum of
C4 to C7) versus long-chain PFCA (sum of C8 to C12) over the monitored period. Our limited data
show that the PFOA Stewardship Program has produced the following measurable results: (1) the
availability of consumer articles that have been treated with fluorinated chemicals is declining; (2)
PFCA content has declined significantly for most of the AOCs, although the PFCA content of a
few samples still remains high; and (3) PFOS is still being used in the market, and PFBS-C4 is
being used as an alternative for PFOS for some products. Global collaboration is needed to further
reduce the PFCA content in consumer articles. The results of this study can help inform risk
management decisions on the changing market for PFCAs as well as provide insight for designing
future research work.
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3. Recommendations
This study demonstrated the importance of monitoring over time the use and variations in
emergence of environmental pollutants in products and the marketplace. Also demonstrated was
the efficacy of the measures taken to reduce the release and subsequent exposure associated with
their use. However, the data presented here provide only a limited assessment of the usage trends
for PFCAs in AOCs over time due to the limited number of samples, the relatively short duration
of data collection, the inability to obtain the same products on the market, and the statistical
uncertainties associated with limited quantities of data. Related research is recommended to: (1)
extend the market monitoring period for the AOCs studied, including new products that are likely
to contain PFCAs; (2) monitor perfluorinated telomeric substances and polyfluorochemicals in
AOCs because some of them are known to be precursors of PFCAs; (3) monitor PFAS in the
market; and (4) study the mechanisms that lead to the transfer of PFCAs from sources to indoor air,
dust, and surfaces, especially during the use of consumer products.
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4. Materials and Methods
4.1 Sample Collection
The first step of the long-term market monitoring effort was the purchase of AOCs between 2007
and 2011 for ten of the thirteen categories identified in Phase 1. Three product categories (i.e., non-
stick cookware, dental floss, and miscellaneous) were not monitored due to low PFC content or
low market availability. The ten AOC categories and the numbers of AOCs purchased for each
category are presented in Table 4-1.
A total of 95 samples from 35 AOCs were collected and analyzed over the four-year period.
Whenever possible, the exact product was purchased based on the product barcode information
recorded for the original samples. This has proven to be a very limiting factor for the monitoring
because of the ever-changing markets, especially for clothing (apparel and membranes) and carpet
products. With the exception of school uniforms, exact duplicate products for apparel were
impossible to purchase. The school uniforms retained the barcode identity, but some of the new
products had different countries of origin. Carpets proved to be the most challenging. Carpets are
manufactured in runs using the same dye and yarn formulations over the production life of a
particular style. Some styles are in production for years, while others are replaced with newer
fibers and manufacturing technologies more rapidly. The carpet-care solutions in both the
commercial and household categories retained product continuity, as did the food contact products
and non-woven medical garments. If it became necessary to replace products with similar products,
the following three criteria were considered: (1) same manufacturer, (2) similar stain-resistant
properties, and (3) similar formulations as indicated on the product label.
Table 4-1. AOCs analyzed for monitoring market trends
Category ID
A
B
C
D
E
F
G
H
I
J
Category name
Pre-treated carpet
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
Total
Purchase Year
2007-2008 [a]
o
J
4
6
5
2
3
4
o
J
3
2
35
2009 w
0
4
1
4
0
o
J
0
0
0
0
12
2010
4
0
o
J
0
2
0
0
o
J
o
J
2
17
2011
2
4
3
6
2
3
4
3
2
2
31
1 Purchase dates were from 2007 to early 2008;[b] Purchase dates were from late 2008 to 2009.
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4.2 Sample Handling, Storage and Preparation
The market-trend monitoring project followed specific methods for handling, storing, extracting,
and analyzing the samples, as well as the QA measures and criteria that were established during
Phase I[3].
AOCs were purchased from local retailers and online stores. Samples were kept in their original
packaging and transported to the EPA laboratory, where they were photographed and the product
information was logged into the AOC record notebook. Product name, vendor name, manufacturer,
purchase date, price, quantity, information indicating possible use of fluorinated compounds, and
other descriptive details were documented.
After being logged into the database, small samples of solid AOCs, such as fabrics or carpets, were
cut from the primary sample in a set often 5 x 5 cm coupon samples and ten 10 x 10 cm samples
using a 60-mm rotary cutter and scissors. The subdivided sets were triple wrapped in aluminum
foil, placed in appropriately-labeled plastic bags and stored in a refrigerator. The rest of the
primary sample and any additional pieces of the same AOC were wrapped in three layers of
aluminum foil, placed in labeled plastic storage bags, and stored in an air-conditioned storage
facility.
Multiple 5 x 5 cm subsample coupons were selected from each AOC to achieve the desired sample
weight for extraction. The weight necessary for extraction and analysis was determined during
Phase 1. Triplicate subsample sets were prepared for each AOC and placed in a desiccator
overnight, after which, the samples were removed from the desiccator, weighed, and placed in
labeled 50-mL polypropylene vials. Then the samples were transferred to the laboratory for
extraction.
Liquid samples were logged into the database and then subdivided into 30-mL polyethylene vials.
The vials were wrapped in three layers of aluminum foil, placed in labeled plastic storage bags, and
stored in a refrigerator. The subsamples were transferred to the laboratory for extraction. The
remaining primary liquid and any additional bottles of the same AOC were wrapped in three layers
of aluminum foil and placed in labeled plastic storage bags.
4.3 Sample Extraction and Analysis
Sample coupons of solid AOCs were extracted with 45 mL of methanol and 100 |aL of 2 ng/|iL
recovery check standard (RCS) in the 50-mL polyethylene centrifuge vials ( BD Falcon ) by
using a Nutating Mixer (Model VSN-5, PRO Scientific, Inc., CT, USA) at a speed setting of
two for 24 ฑ 2 hours. After extraction, the methanol extract was transferred to a 170-mL
borosilicate-glass concentration tube with stem (LabConco, MO, USA). The extraction vials
were rinsed three times with approximately 3 mL of methanol. The glass concentration tubes
were placed in a RapidVap N2 Evaporation System (Model 791000, LabConco, MO, USA) that
was custom-made without tetrafluoroethylene parts and coatings. The volume of the extract was
reduced to approximately 1.5 mL, which were transferred into a 3-mL syringe with a 0.1 |im
Anotop 25 filter attached and filtered into a clean 10-mL volumetric flask. The concentration
tube was rinsed five times with approximately 1.5 mL of solution consisting of 60% (v/v)
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methanol and 40% (v/v) 2 mN ammonium acetate aqueous solution (hereafter referred to as the
60:40 solution). Each 10-mL flask received 100 jiL of 0.5 ng/|iL internal standard (IS) and was
brought to volume with the 60:40 solution. The volumetric flasks were placed in a sonication
bath for 10 minutes, and the contents were transferred to a 15-mL polypropylene storage vial
with appropriate label. The samples were stored at 4 ฐC in the refrigerator in the laboratory and
were analyzed within 30 days.
For the extraction of liquid samples, a target amount of the samples (typically 1 g) was weighed
and transferred from the 30-mL polyethylene storage vial to a 25-mL volumetric flask with 100
jiL of 2 ng/|iL RCS and brought to volume with the 60:40 solution. Then the flasks were
sonicated for 10 minutes. After vacuum filtration via a 0.22-|im of Corning filter, 9.9 mL of the
filtrate were transferred to a 10-mL volumetric flask with 100 jiL of the 0.5 ng/|iL internal
standard. The Corning filter and flask were not rinsed during this time. It was necessary to filter
some of the liquid samples again through a 0. l-|im Anotop filter by syringe (Micro-Mateฎ,
Sigma-Aldrich). Then, each flask was sonicated for 10 minutes. The sample contents were
transferred to a 15-mL polypropylene storage vial, after which the vial was labeled appropriately
and stored at 4ฐC in a refrigerator. The samples were analyzed within 30 days.
Sample quantification was conducted using an Agilent 1100 HPLC equipped with an Applied
Biosystem API 3200 Triple Quadrupole Mass Spectrometer (LC/MS/MS) with a Turbo V ion-
spray interface. The analytes included nine PFCAs (C4 to C12) and five sulfonates, which are
listed in Table 4-2. The PFCAs and sulfonates were calibrated separately. An isotopically-labeled
PFCA (perfluoro-n-[l, 2-13C2] decanoic acid) was used as the extraction recovery check standard
for PFOA and its homologues. An isotopically-labeled sulfonate standard (sodium perfluoro-1-
hexane [18C>2] sulfonate) was used for PFOS and its homologues. The internal standards were
perfluoro-n-[l, 2, 3, 4-13C/t] octanoic acid for PFCAs and sodium perfluoro-l-[l, 2, 3, 4-13C/t]
octanesulfonate for PFAS analysis. Each batch was analyzed along with its corresponding QC
samples. The conditions of the instrument are presented in Table 4-3 and Table 4-4.
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Table 4-2. Analyte names, chemical formulas, and chemical abstracts service registration
numbers
Analyte name
perfluorobutyric acid
perfluoropentanoic acid
perfluorohexanoic acid
perfluoroheptanoic acid
perfluorooctanoic acid
perfluorononanoic acid
perfluorodecanoic acid
perfluoroundecanoic acid
perfluorododecanoic acid
perfluoro-n-[l,2,3,4-13C4] octanoic acid (IS)
perfluoro-n-[l,2-13C2] decanoic acid (RCS)
potassium perfluoro-1-butanesulfonate
sodium perfluoro-1-hexanesulfonate
sodium perfluoro-1-heptanesulfonate
sodium perfluoro-1-octanesulfonate
sodium perfluoro-1-decanesulfonate
sodium perfluoro-l-[l,2,3,4-13C4]octanesulfonate (IS)
sodium perfluoro-l-hexane[18O2]sulfonate (RCS)
Short name
PFBA-C4
PFPeA-C5
PFHxA-C6
PFHpA-C7
PFOA-C8
PFNA-C9
PFDA-C10
PFUnDA-Cll
PFDoDA-C12
PFOA-C8-13C4
PFDA-C10-13C2
PFBS-C4
PFHxS-C6
PFHpS-C7
PFOS-C8
PFDS-C10
PFOS-C8-13C4
PFHxS-C6-18O2
Chemical formula
C4HF7O2
C5HF9O2
C6HFn02
C7HF1302
C8HF1502
C9HF17O2
CioHFi9O2
CnHF2102
C12HF2302
13C412C4HF1502
13C212C8HF1502
C4F9SO3K
C6F13SO3Na
C7F15SO3Na
C8F17SO3Na
C10F21S03Na
13C412C4F17SO3Na
C6F13S18O216ONa
CAS#
375-22-4
2706-90-3
307-24-4
375-85-9
335-67-1
375-95-1
335-76-2
2058-94-8
307-55-1
~
~
29420-49-3
108427-53-8
~
1763-23-1
~
~
~
-------
Table 4-3. Operating conditions for the Agilent 1100 HPLC/Applied Biosystem API 3200
triple quadrupole mass spectrometer for the analysis of PFCAs and PFAS
LC Parameters
Column
Guard column
Oven temperature
Injection volume
Mobile phase
Flow rate
Gradient
Mass Spectrometric Parameters
Ion source
Curtain gas (CUR)
Collision gas (CAD)
Ion spray voltage (IS)
Temperature (TEM)
Ion source gas (GS1)
Ion source gas (GS2)
Interface heater (ihe)
Scan type
Polarity
Resolution Ql
Resolution Q2
Settings
Agilent Zorbax Eclipse XDB-C18, 2. 1 x
Agilent Eclipse XDB-C18, 2.1 x 15 mm,
50 mm, 3.5 um
3.5 um
50 ฐC
20 uL
2 mM ammonium acetate -H2O (A), MeOH (B)
250 uL/min
Steps
0
1
2
3
4
Time (min) %A
4 35
5 20
7 20
12 10
12.5 35
%B
65
80
80
90
65
Turbo spray
10 arbitrary unit (setting)
3 arbitrary unit (setting)
- 4500 V
425 ฐC
14 arbitrary unit (setting)
4 arbitrary unit (setting)
On
MRM
Negative
Unit
Unit
-------
Table 4-4. Analyte-dependent mass spectra parameters
Analyte
Ql Mass (amu)
Q3 Mass (amu)
Time (ms)
DP(V)
EP(V)
CE(V)
CXP(V)
PFC-Acids
PFBA-C4
PFPeA-C5
PFHxA-C6
PFHpA-C7
PFOA-C8
PFOA-C8-13C4
PFNA-C9
PFDA-C10
PFDA-C10-13C2
PFUnDA-Cll
PFDoDA-C12
213
263
313
363
413
417
463
513
515
563
613
169
219
269
319
369
372
419
469
470
519
569
125
125
125
125
125
125
125
125
125
125
125
-20
-10
-15
-15
-15
-15
-15
-12
-10
-15
-10
-4.5
-3
-4
-4.5
-4.5
-4.5
-5
-4.5
-6
-7
-9
-12
-12
-12
-12
-14
-14
-12
-8
-10
-6
-18
-4
-4
-4
-6
-6
-6
-6
-8
-38
-8
-10
PFC-Sulfonates
PFBS-C4
PFHxS-C6
PFHxS-C6-18O2
PFHpS-C7
PFOS-C8
PFOS-C8-13C4
PFDS-C10
299
399
403
449
499
503
599
99
99
103
99
99
99
99
125
125
125
125
125
125
125
-45
-55
-55
-50
-75
-70
-80
-5.5
-9.5
-9
-7
-8
-6
-12
-38
-52
-52
-85
-66
-118
-74
-2
-2
0
-9
-2
-56
-2
10
-------
4.4 Quality Assurance and Quality Control
Quality assurance (QA) and quality control (QC) procedures were implemented in this project by
following the guidelines and procedures detailed in the approved Category II Quality Assurance
Project Plan (QAPP).
4.4.1 Data Quality Indicators Goals
The QA measures and criteria remained the same as those for Phase 1. Data quality indicator
(DQI) goals for the measurement parameters and validation methods are listed in Table 4-5.
Table 4-5. Data quality indicator goals for critical measurements
Measurement
Quantification by the
LC/MS/MS method
Solvent extraction
Weight of AOC samples
Parameters
Instalment detection limit
Accuracy
Precision
Calibration
Accuracy
Precision
System blank
Accuracy
Objective
<0.2 ng/mL
85-115%
ฑ20%
0.99
80-120%
ฑ20%
-------
4.4.3 Detection Limit
The method detection limit (MDL) was not investigated for the project. After each calibration, the
instrument detection limit (IDL) was determined by analyzing the lowest calibration standard
seven times and then calculating three standard deviations from the measured concentrations of the
standard.
4.4.4 Quality Control Samples
Quality control samples consisted of field blanks, solvent blanks, duplicates or triplicates, daily
calibration checks and recovery check standards.
With each daily batch of extractions, a set of five QC samples was prepared and analyzed. Each set
consisted of one field blank, one solvent blank, and three blanks for the recovery check standards.
The field blank was taken through the entire extraction process similar to the corresponding AOC
samples. The solvent blank was prepared in a clean, 10-mL flask with 9.9 mL of 60:40 solution
and 100 jiL of the internal standard. The three RCS blanks were prepared with 9.8 mL of 60:40
solution, 100 jiL of IS, and 100 jiL of RCS in a 10-mL flask. These five flasks were sonicated for
10 minutes and transferred to labeled polypropylene vials. The QC samples were stored in the
refrigerator with each batch of samples to be analyzed. Samples were analyzed in batches,
including AOC samples in duplicate or triplicate, quality control samples, and two daily
calibration check standards analyzed at the beginning and the end of the analysis sequence.
12
-------
5. Results
5.1 Distribution of AOC Samples
Ninety-five samples from 35 types of AOCs were obtained between 2007 and 2011 (Table 4-1).
The dates the samples were manufactured were unknown, because the product labels did not
include that information. The purchase data and sample descriptions are presented in Tables 5-1
through 5-10. The AOC ID numbers were kept consistent with those used in Phase 1. For example,
A-1-0 refers to the AOC in category A, product 1, and the first purchase, which was measured
during Phase 1 of the project. A-l-1 is the same AOC in category A, product 1, second purchase.
No AOC samples were collected under categories of cookware, dental floss, and miscellaneous.
Table 5-1. AOC samples collected for pre-treated carpeting
AOC ID
A- 1-0
A-l-1
A-1-2W
A- 1-3 [a]
Purchase Date
03/09/2007
05/18/2010
09/08/2011
09/08/2011
Description
Nylon carpet 1
Nylon carpet 2
Nylon carpet 3
Nylon carpet 4
Country of Origin
USA
USA
USA
USA
A-2-0
A-2-1 [a]
A-2-2 [a]
03/12/2007
05/18/2010
05/18/2010
Corn polymer carpet 1
Corn polymer carpet 2
Corn polymer carpet 3
USA
USA
USA
A-9-0
A-9-1
02/4/2008
05/18/2010
Polypropylene carpet 1
Polypropylene carpet 2
USA
USA
1 The AOCs were not exactly the same products even though they were purchased on the same day.
13
-------
Table 5-2. AOC samples collected for commercial carpet/fabric-care liquids
AOC ID
B-l-0
B-l-1
B-l-2
Purchase Date
04/19/2007
05/26/2009
02/23/2011
Description
Carpet/upholstery protector concentrate 1
Carpet/upholstery protector concentrate 1
Carpet/upholstery protector concentrate 1
Country of Origin
USA
USA
USA
B-3-0
B-3-1
B-3-2
04/19/2007
11/24/2008
02/23/2011
Solvent-based fabric protector
Solvent-based fabric protector
Solvent-based fabric protector
USA
USA
USA
B-5-0
B-5-1
B-5-2
04/19/2007
11/24/2008
02/23/2011
Carpet/upholstery protector concentrate 2
Carpet/upholstery protector concentrate 2
Carpet/upholstery protector concentrate 2
USA
USA
USA
B-7-0
B-7-1
B-7-2
04/19/2007
05/1/2008
02/23/2011
Ready-to-use carpet protector 1
Ready-to-use carpet protector 1
Ready-to-use carpet protector 1
USA
USA
USA
Table 5-3. AOC samples collected for household carpet/fabric-care liquids and foams
AOC ID
C-l-0
C-l-1
C-l-2
Purchase Date
04/19/2007
11/06/2008
03/28/2011
Description
Carpet Shampoo 1
Carpet Shampoo 1
Carpet Shampoo 1
Country of Origin
USA
USA
USA
C-2-0
C-2-1
05/10/2007
02/23/2011
Household carpet care 1
Household carpet care 1
USA
USA
C-4-0
C-4-1
C-5-0
C-5-1
05/16/2007
02/22/2010
05/16/2007
02/23/2011
Household carpet protector 1
Household carpet protector 1
Household carpet protector 2
Household carpet protector 2
USA
USA
USA
USA
C-8-0
C-8-1
06/06/2007
03/26/2010
Household carpet care 2
Household carpet care 2
USA
USA
C-9-0
C-9-1
09/29/2007
03/01/2010
Membrane fabric care 1
Membrane fabric care 1
England
England
14
-------
Table 5-4. AOC samples collected for treated apparel
AOC ID
D-3-0
D-3-1
D-3-2
D-3-3
Purchase Date
05/10/2007
11/12/2008
02/24/2011
08/16/2011
Description
Girl's uniform shirt
Girl's uniform shirt
Girl's uniform shirt
Girl's uniform shirt
Country of Origin
Vietnam
Vietnam
China
China
D-4-0
D-4-1
D-4-2
D-4-3
05/10/2007
11/24/2008
02/24/2011
08/16/2011
Boy's uniform/dress shirt
Boy's uniform/dress shirt
Boy's uniform/dress shirt
Boy's uniform/dress shirt
Thailand
El Salvador
El Salvador
Bangladesh
D-5-0
D-5-1
D-5-2[a]
05/10/2007
08/16/2011
02/24/2011
Boy's uniform/dress pant
Boy's uniform/dress pant
Boy's uniform pant
Dominican Republic
Dominican Republic
Dominican Republic
D-7-0
D-7-1
D-7-2
05/10/2007
11/12/2008
08/16/2011
Girl's uniform pant
Girl's uniform pant
Girl's uniform pant
China
Vietnam
China
D-10-0
D-10-1
08/17/2007
11/24/2008
Man's dress pant
Man's dress pant
Malaysia
Malaysia
1 For PFAS only.
Table 5-5. AOC samples collected for treated home textile and upholstery
AOC ID
E-7-0
E-7-1
E-7-2
Purchase Date
07/10/2007
02/22/2010
03/30/2011
Description
Mattress pad 1
Mattress pad 1
Mattress pad 1
Country of Origin
USA
USA
USA
E-8-0
E-8-1
E-8-2
07/10/2009
03/30/2010
03/30/2011
Mattress pad 2
Mattress pad 2
Mattress pad 2
USA
USA
USA
15
-------
Table 5-6. AOC samples collected for treated non-woven medical garments
AOC ID
F-2-0
F-2-1
F-2-2
Purchase Date
01/30/2008
05/05/2009
03/28/2011
Description
Surgical gown 1
Surgical gown 1
Surgical gown 1
Country of Origin
Assembled in China with U.S. materials
China
China
F-3-0
F-3-1
F-3-2
01/30/2008
05/05/2009
03/28/2011
Surgical gown 2
Surgical gown 2
Surgical gown 2
China
China
China
F-4-0
F-4-1
F-4-2
01/30/2008
05/05/2009
03/28/2011
Surgical gown 3
Surgical gown 3
Surgical gown 3
Assembled in China with U.S. materials
China
China
Table 5-7. AOC samples collected for treated floor waxes and stone/wood sealants
AOC ID
G-l-0
G-l-1
G-l-2
Purchase Date
07/10/2007
02/23/2011
02/23/2011
Description
Household floor wax 1
Household floor wax 1
Household floor wax 1
Country of Origin
USA
USA
USA
G-2-0
G-2-1
07/10/2007
03/30/2011
Household floor wax 2
Household floor wax 2
USA
USA
G-4-0
G-4-1
07/10/2007
03/31/2011
Commercial floor wax 1
Commercial floor wax 1
USA
USA
G-6-0
G-6-1
07/10/2007
03/31/2011
Commercial floor wax 2
Commercial floor wax 2
USA
USA
16
-------
Table 5-8. AOC samples collected for treated food contact paper
AOC ID
H-3-0
H-3-1
H-3-2
Purchase Date
10/15/2007
02/22/2010
09/07/2011
Description
Food paper 1
Food paper 1
Food paper 1
Country of Origin
USA
USA
USA
H-4-0
H-4-1
H-4-2
10/15/2007
02/22/2010
09/07/2011
Food paper 2
Food paper 2
Food paper 2
USA
USA
USA
H-5-0
H-5-1
H-5-2
10/30/2007
02/22/2010
09/12/2011
Food paper 3
Food paper 3
Food paper 3
USA
USA
USA
Table 5-9. AOC samples collected for membranes for apparel
AOC ID
1-1-0
1-1-2
Purchase Date
05/16/2007
03/30/2010
Description
Membrane 1
Membrane 1
Country of Origin
China
Vietnam
1-5-0
1-5-1
1-5-2
05/16/2007
03/30/2010
03/31/2011
Membrane 2
Membrane 2
Membrane 2
China
China
Indonesia
1-8-0
1-8-1
1-8-2
08/17/2007
03/30/2010
03/31/2011
Membrane 3
Membrane 3
Membrane 3
China
China
China
Table 5-10. AOC samples collected for thread-sealant tapes and pastes
AOC ID
J-l-0
J-l-1
J-l-2
Purchase Date
04/06/2007
03/28/2010
03/31/2011
Description
Thread-sealant tape 1
Thread-sealant tape 1
Thread-sealant tape 1
Country of Origin
Malaysia
China
China
J-6-0
J-6-1
J-6-2
08/17/2007
03/28/2010
03/31/2011
Thread-sealant tape 2
Thread-sealant tape 2
Thread-sealant tape 2
China
China
China
17
-------
5.2 Extractable PFCA Content in AOC Samples
Figures 5-1 through 5-34 present PFCA contents detected in AOC samples. The data do not
include values that were below the lowest calibration concentration or the value that did not meet
QA criteria. All PFCA concentrations in one of the AOCs in the household carpet-care category,
C-2, were below the lowest calibration concentration. Therefore, the data are not presented in the
figures. The complete data of PFCA concentrations, including percentage of recovery check
standards (%RCS) and the number of samples analyzed for each of the AOCs (N) are summarized
in the Appendix A (Tables A-l through A-10).
1 en
PFCA Content (ng/g)
l-> h
ฃ* 00 NJ C
3 o o o e
I I I
A-l
Jhfl
,# ^ ,<ฃ ,<^
n n
ml r-, n JH
3/9/2007
5/18/2010
D 9/8/2011
9/8/2011
.Or >^*^ jJfr* >Jfr* >Jfr*
^^ X^ <*v O O
PFCAs
Figure 5-1. Trends of PFCAs detected in nylon carpet 1 (A-l) (Two slightly different
products were purchased on 9/8/2011)
18
-------
c
*> fin
1
5
O_ **"
0_
^
*
A-2
'////////
PFCAs
D 3/12/2007
5/18/2010
D 5/18/2010
Figure 5-2. Trends of PFCAs detected in corn polymer carpet (A-2)
280
D 2/4/2008
5/18/2010
PFCAs
Figure 5-3. Trends of PFCAs detected in polypropylene carpet 4 (A-9)
19
-------
16,000 n
^ 12,000 -
M
c
ฃ 8,000 -
8
(j
u_ /i nnn
o_ *i,uuu
B-l
n n
^ ^ฐ ^
-
~
*
4
---
...
f ^
P 4*
,
*
<
"I
x
fl
&
4
\-
^<
-
?
3
...
p
^
4
JL
D 4/19/2007
5/26/2009
>*
p
\ %
PFCAs
Figure 5-4. Trends of PFCAs detected in carpet/upholstery protector concentrate 1 (B-l)
100
PFCAs
D4/19/2007
11/24/2008
D 2/23/2011
Figure 5-5. Trends of PFCAs detected in solvent based fabric protector (B-3)
20
-------
160
B-5
<- 120 -f
oo
_
c
01 on
+- 80 +
O
u D4/19/2007
40 -\-m-l \ 11/24/2008
,.., ,...n .n, n D"
PFCAs
Figure 5-6. Trends of PFCAs detected in carpet/upholstery protector concentrate 2 (B-5)
BT
s= 2,250 +-
oo
| 1,500 -f-
D4/19/2007
750 +- --[>- 5/1/2008
, n II II II II II II n D2/23/20n
PFCAs
Figure 5-7. Trends of PFCAs detected in ready-to-use carpet protector 1 (B-7)
21
-------
100
D4/19/2007
11/06/2008
D 3/28/2011
PFCAs
Figure 5-8. Trends of PFCAs detected in carpet shampoo 1 (C-l)
800
M 600
00
8
400 4
200 -(
C-4
Ik
D 5/16/2007
2/22/2010
PFCAs
Figure 5-9. Trends of PFCAs detected in household carpet protector 1 (C-4)
22
-------
200
C-5
.- 150 -f-
oo
4-ป
ฃ 100 + -
o
u
5 50 I--.-- B D5/16/2007
| 2/23/2011
0 I II,
_tofc to* .to* ^* .^* v^
ป Cr -J5 *.O^ ^1 ^v
*O s*$^ ^V^ ^t^ ^^r~
PFCAs
Figure 5-10. Trends of PFCAs detected in household carpet protector 2 (C-5)
" C-8
S 30
oS
c
_
4-ป
c
S 20 +---
8
5 I D6/6/2007
U. J_Q _ . .
3/26/2010
0
rk r<* r A A tfy tf\
\Ji ^J s^V ^^V ^^V
ฃ t>* ^ ^ ^
PFCAs
Figure 5-11. Trends of PFCAs detected in household carpet care 2 (C-8)
23
-------
Figure 5-12. Trends of PFCAs detected in membrane fabric care 1 (C-9)
Figure 5-13. Trends of PFCAs detected in girl's uniform shirt (D-3)
24
-------
oo
240
180 -
S 120
o
u
60
D-4
I
D 5/10/2007
11/24/2008
D 2/24/2011
8/16/2011
PFCAs
Figure 5-14. Trends of PFCAs detected in boy's uniform/dress shirt (D-4)
^ 30
oB
ฃ 20
8
$
D-5
10
n
.
.
D 5/10/2007
8/16/2011
PFCAs
Figure 5-15. Trends of PFCAs detected in boy's uniform/dress pant (D-5)
25
-------
Figure 5-16. Trends of PFCAs detected in girl's uniform pant (D-7)
Figure 5-17. Trends of PFCAs detected in man's dress pant (D-10)
26
-------
400
E-7
300 4- H--
"
ฃ 200 +-
D 7/10/2007
100 +--D--- r-| 2/22/2010
11 L n n D 3/30/2011
n n I L ILIinlLnlmlLIL-i
h^^ ซ**r Cr Cr C!r
ป ซXป f*h^ t*k *K^
PFCAs
Figure 5-18. Trends of PFCAs detected in mattress pad 1 (E-7)
80
rll -, 03/30/2011
PFCAs
Figure 5-19. Trends of PFCAs detected in mattress pad 2 (E-8)
27
-------
100
00
c
01
4-ป
c
o
u
F-2
I
IL
n
D1/30/2008
5/5/2009
D 3/28/2011
PFCAs
Figure 5-20. Trends of PFCAs detected in surgical gown 1 (F-2)
80
60 --
ฃ 40 +
I
5
ฃ 20 +
F-3
EL
m
D1/30/2008
5/5/2009
D 3/28/2011
PFCAs
Figure 5-21. Trends of PFCAs detected in surgical gown 2 (F-3)
28
-------
y*nn
is
c
c
8
5
ฃ 200 -
-
F-4
1-1
1-1
0.
fr & & & & &
V^ V^
-------
24
;3 18
M
PFCA Con
G-2
D 7/10/2007
3/30/2011
PFCAs
Figure 5-24. Trends of PFCAs detected in household floor wax 2 (G-2)
40 nnn -,
*rซ ac nnn
bB
c
+j
c
-------
240
oB
ฃ 120
8
ฃ 60 +---
G-6
nn n.
D 7/10/2007
3/31/2011
PFCAs
Figure 5-26. Trends of PFCAs detected in commercial floor wax 2 (G-6)
17-
53
ฃ
~ 6 -
3
(j
LL. a
0. 3
0_
^
^
-
t
ซ
*V
1
1
'/"
H-3
n
t*k^ t*h^ CA Cx' Cr
PFCAs
D 10/15/2007
2/22/2010
D 9/7/2011
Figure 5-27. Trends of PFCAs detected in food paper 1 (H-3)
31
-------
Figure 5-28. Trends of PFCAs detected in food paper 2 (H-4)
Figure 5-29. Trends of PFCAs detected in food paper 3 (H-5)
32
-------
80
60 -
r 40 -
01
4-ป
S -
LL.
Q.
1-1
D 5/16/2007
3/30/2010
PFCAs
Figure 5-30. Trends of PFCAs detected in membrane 1 (1-1)
200
.M 150 -
_c_
4-ป
ฃ 100 -
o
u
5
K- 50 4
1-5
n
E
n
D 5/16/2007
3/30/2010
D 3/31/2011
PFCAs
Figure 5-31. Trends of PFCAs detected in membrane 2 (1-5)
33
-------
100
1-8
1 75
01 JQ
^ D8/17/2007
3
S- 25 +- ---- -- h- -- h- " B3/30/2010
D 3/31/2011
_n_ linn n n ,-, n 11
0
f v* f^5 f^ f * f^P
_i^ ^K _ป^^ ^^ ^^^ V^
* j^r* jj5c^ ^?^ ^r^ cr^
PFCAs
Figure 5-32. Trends of PFCAs detected in membrane 3 (1-8)
12
J-l
1 9'
_
c
v 6
Q
D4/6/2007
3 +- - -- -- 3/28/2010
D 3/31/2011
0
ซ$* Jfr* .^* Jfr* >ซ!& v^* fc^* fc^* fc^*
PFCAs
Figure 5-33. Trends of PFCAs detected in thread-sealant tape 1 (J-l)
34
-------
> /!/->/->
PFCA Content (ng/g)
_J-> _J-> _ฃ
O TvJ ^0 "j
O O O C
3 o o o e
n _ n .
PI
-
J-6
^/A-VVVV*
PFCAs
D 8/17/2007
3/28/2010
D 3/31/2011
Figure 5-34. Trends of PFCAs detected in thread-sealant tape 2 (J-6)
5.3 Total PFCAs in AOC Samples
The total perfluorocarboxylic acids (TPFCA) is defined as the sum of the concentrations of C4 to
C12, C6 to C12 or C8 to C12 PFCAs. The TPFCA of C4 to C12 values are presented in Figures 5-
35 to 5-44. In the figures, the sample collection dates were represented by years. All of the data are
provided in Appendix A (Tables A-l to A-10).
35
-------
1,200
12007
I 2008
2010
I 2010
i 2011
2011
A-l
Figure 5-35. Trends of TPFCA of C4 to C12 for selected pre-treated carpeting (Two A-l
samples and two A-2 samples were collected on the same day in 2010 and 2011,
respectively.)
48,000
I 2007
I 2008
2008-2009
I 2011
B-l
B-3
AOCs
B-7
Figure 5-36. Trends of TPFCA of C4 to C12 for selected commercial carpet/fabric-care
liquids (2008 is 5/2008 and 2008-2009 is 11/2008 to 5/2009)
36
-------
1,200
12007
12008
2010
2011
C-l
C-2
AOCs
C-9
Figure 5-37. Trends of TPFCA of C4 to C12 for selected household carpet/fabric-care
liquids
1,000
I 2007
I 2003
2011a
I 2011b
D-3
D-10
Figure 5-38. Trends of TPFCA of C4 to C12 for selected treated apparel (2011a is 2/2011
and 201 Ibis 8/2011)
37
-------
1,000
12007
12010
2011
E-7
AOCs
E-8
Figure 5-39. Trends of TPFCA of C4 to C12 for selected treated home textile and
upholstery products
4,000
3,000 -
5
2,000
1,000
2008
12009
2011
F-4
Figure 5-40. Trends of TPFCA of C4 to C12 for selected treated non-woven medical
garments
38
-------
4,000
12007
12011
G-l
G-2
G-4
AOCs
G-6
Figure 5-41. Trends of TPFCA of C4 to C12 for selected treated floor waxes and
stone/wood sealants
16,000
H-3
H-5
12007
12010
2011
Figure 5-42. Trends of TPFCA of C4 to C12 for selected treated food contact paper
39
-------
400
12007
12010
2011
1-1
Figure 5-43. Trends of TPFCA of C4 to C12 for selected membranes for apparel
2,800
12007
12010
2011
J-l
AOCs
Figure 5-44. Trends of TPFCA of C4 to C12 for selected thread-sealant tapes
40
-------
5.4 Extractable PFAS Content in AOC Samples
During the market monitoring of PFCA in AOCs, some perfluoroalkyl sulfonates were detected in
the AOCs. Thus, the instrument was calibrated for PFAS, and samples that were identified as
having PFAS content were reanalyzed for PFAS. The results are presented in Table 5-11. Figure 5-
45 is a chromatogram that shows the detectable PFAS.
/iflflnn
^nnnn
OtlUUU
01
10
0
a
01
ef onnnn
11 ZUUUU
01
ro
01
tc
H nnnn
1UUUU
PF
PF
(
HxA
3A^J
)
'FBS
RC
PFOA
1
PFOS
-U-""
nlL's
fit
2 4
.S
1
6 8 10 12 1
Retention Time (min)
4
Figure 5-45. PFAS detected in one membrane for apparel (AOC 1-1-1)
41
-------
Table 5-11. Summary of PFAS detected in selected AOCs
AOCID
B-l-1
B-5-1
C-l-1
C-l-2
C-5-1
C-9-1
D-7-1
D-5-2
E-7-1
E-8-1
G-l-2
1-1-2
J-l-1
J-6-1
Purchase date
05/26/2009
11/24/2008
11/06/2008
03/28/2011
02/23/2011
03/1/2010
11/12/2008
11/12/2008
02/22/2010
03/30/2010
02/23/2011
03/30/2010
03/28/2010
03/28/2010
PFBS-C4S
45.8
89.6
25.7
911
161
BDL
2.00
BDL
BDL
BDL
143
30.7
BDL
BDL
PFHxS-C6S
194
BDL
88.8
155
BDL
BDL
BDL
1.70
BDL
12.1
BDL
7.10
BDL
60.3
PFHpS-C7S
190
BDL
45.1
352
BDL
BDL
BDL
BDL
BDL
BDL
BDL
8.20
BDL
BDL
PFOS-C8S
585
BDL
361
257
BDL
BDL
BDL
BDL
BDL
BDL
12.0
8.60
BDL
BDL
PFDS-C10S
19.6
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
%RCS [al
80.4
102
88.0
92.2
83.3
108
109
91.3
119
88.4
87.0
80.6
112
82.7
TPFAS [bl
1030
89.6
521
1670
161
BDL
2.00
1.70
BDL
12.1
155
54.7
112
60.3
NW
2
2
2
2
2
2
3
3
3
2
2
2
3
3
Percent recovery of recovery check standards.[b] Total perfluoroalkyl sulfonates.[c] Number of samples analyzed for of the each AOCs.
42
-------
5.5 Data Quality
5.5.1 LC/MS/MS Calibration
Tables 5-12 and 5-13 summarize all LC/MS/MS calibrations conducted for the project, including
the lowest and the highest calibration concentrations. The linear coefficient of determination (r2)
for the calibration curve was equal to or greater than 0.991, meets the DQI goal.
The TAP results are listed in Table 5-14. The recovery percentage of TAP standards ranged from
91% tol 15% and %RSD of triplicate injections ranged from 0.4% to 9.5%. They all meet the
criteria for IAP analysis, which were 100 ฑ 15% recoveries and % RSD of triplicate analyses within
15%.
5.5.2 Detection Limits
The instrument detection limits were determined by three times of standard deviation of seven
injections of the lowest calibration standards after each calibration. The detection limits are
summarized in Table 5-15. As shown in the table, not all the instrument detection limits for
LC/MS/MS met the DQI goal.
5.5.3 Quality Control Samples
The quality control samples consisted of field blanks, solvent blanks, duplicates or triplicates, daily
calibration checks and recovery check standards. If the content of the analyte in the solvent blank
was above the lowest calibration concentration, it was subtracted from all samples and field blanks.
The data presented were not adjusted for recovery of RCS.
The RCS recoveries for individual samples are available in Appendix A and Table 5-11. More than
95 AOC samples were analyzed for the project, but only 95 samples were analyzed successfully.
The data for samples that failed to meet the data quality requirements after three or more trials
were discarded. The common causes of the failures were low recovery (i.e., < 80%) for the
recovery check standard and poor precision of duplicate or triplicate samples (%RSD > 20%).
Table 5-16 summarizes the average recovery of DCCs for the tests. The recoveries were in a range
that met the criterion for acceptable LC/MS/MS instrument performance, i.e., 85 to 115%
recovery.
43
-------
Table 5-12. LC/MS/MS calibration of PFCAs for the project
Date
06/15/2011
07/18/2011
09/13/2011
10/13/2011
11/07/2011
Analyte
r2[a]
Low cal (ng/mL) [b]
High cal (ng/mL) [c]
r2
Low cal (ng/mL)
High cal (ng/mL)
r2
Low cal (ng/mL)
High cal (ng/mL)
r2
Low cal (ng/mL)
High cal (ng/mL)
o
r
Low cal (ng/mL)
High cal (ng/mL)
C4
0.9966
0.3
80
0.9964
0.3
100
0.9929
0.3
100
0.9944
0.3
160
0.9952
0.3
160
C5
0.9973
0.5
80
0.9962
0.3
100
0.9974
0.3
100
0.9944
0.3
160
0.9952
0.3
160
C6
0.9985
0.5
80
0.9985
0.3
100
0.9988
0.3
100
0.9971
0.3
160
0.9920
0.3
160
C7
0.9995
0.3
80
0.9988
0.3
100
0.9945
0.3
100
0.9931
0.3
160
0.9931
0.3
160
C8
0.9983
0.3
80
0.999
0.3
100
0.9972
0.3
100
0.9933
0.3
160
0.9930
0.3
160
C9
0.9982
0.5
80
0.9979
0.3
100
0.9993
0.3
100
0.9935
0.3
160
0.9965
0.3
160
CIO
0.9994
0.5
80
0.9994
0.3
100
0.999
0.3
100
0.9923
0.3
160
0.9908
0.3
160
Cll
0.9995
0.3
80
0.9989
0.3
100
0.9978
0.3
100
0.9939
0.3
160
0.9937
0.3
160
C12
0.9992
0.3
80
0.9987
0.3
100
0.9951
0.3
100
0.9921
0.3
160
0.9910
0.3
160
C10-13C2
0.9992
0.5
80
0.9985
0.3
100
0.998
0.3
100
0.992
0.3
160
0.9944
0.3
160
r is linear coefficient of determination.l J Low cal is the lowest calibration concentration. LCJ High cal is the highest calibration concentration.
44
-------
Table 5-13. LC/MS/MS calibrations of PFAS for the project
Date
Analyte
PFBS-C4
PFHxS-C6
PFHxS-C6-18O2
PFHpS-C7
PFOS-C8
PFDS-C10
j2W
10/05/2011
0.9977
0.9980
0.9997
0.9989
0.9969
0.9984
11/07/2011
0.9936
0.9915
0.9951
0.9960
0.9969
0.9921
Calibration Range
Low cal (ng/mL)[bl
0.30
0.30
0.30
0.30
0.30
0.30
High cal (ng/mL)[cl
100
100
100
100
100
100
[a] r2 is linear coefficient of determination.[b] Low cal is the lowest calibration concentration.[c] High cal is the highest
calibration concentration.
Table 5-14. IAP results for each calibration
Calibration
06/15/2011
07/18/2011
09/13/2011
10/05/2011
10/13/2011
11/07/2011
11/07/2011
Analyte
PFHxA-C7
PFOA-C8
PFDA-C10
PFHxA-C7
PFOA-C8
PFDA-C10
PFHxA-C7
PFOA-C8
PFDA-C10
PFBS-C4
PFHxS-C6
PFOS-C8
PFHxA-C7
PFOA-C8
PFDA-C10
PFBS-C4
PFHxS-C6
PFOS-C8
PFHxA-C7
PFOA-C8
PFDA-C10
IAP Concentration (ng/mL)
11.8
5.55
8.09
11.8
5.55
8.09
9.87
7.26
9.31
10.2
7.87
9.13
9.87
7.26
9.31
10.2
7.87
9.13
9.87
7.26
9.31
Avg. % Recovery
113
101
107
97.9
95.1
93.3
94.2
93.3
105
98.3
98.9
115
112
110
110
91.2
100
97.7
112
95.8
93.1
%RSD (n = 3)
4.5
5.5
6.3
0.4
2.9
2.7
9.5
5.7
7.9
5.2
3.2
4.6
6.5
3.6
7.5
6.2
6.5
9.4
3.3
4.8
8.6
45
-------
Table 5-15. Summary of instrument detection limits (IDL, ng/mL)
Analytes
PFBA-C4
PFPeA-C5
PFHxA-C6
PFHpA-C7
PFOA-C8
PFNA-C9
PFDA-C10
PFUnDA-Cll
PFDoDA-C12
PFDA-C10-13C2
06/15/2011
0.16
0.38
0.35
0.23
0.19
0.37
0.33
0.28
0.23
0.32
07/18/2011
0.22
0.27
0.18
0.29
0.27
0.29
0.20
0.18
0.12
0.26
09/13/2011
0.14
0.18
0.25
0.17
0.25
0.22
0.09
0.11
0.13
0.13
10/13/2011
0.22
0.28
0.29
0.28
0.27
0.24
0.06
0.09
0.13
0.11
11/07/2011
0.27
0.29
0.28
0.28
0.18
0.18
0.09
0.15
0.27
0.17
Analytes
PFBS-C4
PFHxS-C6
PFHxS-C6-18O2
PFHpS-C7
PFOS-C8
PFDS-C10
-
-
-
10/05/2011
0.12
0.07
0.14
0.05
0.06
0.11
-
-
-
-
11/07/2011
0.16
0.22
0.21
0.24
0.15
0.22
-
-
-
-
46
-------
Table 5-16. Average recoveries of DCCs for the project
Analytes
PFBA-C4
PFPeA-C5
PFHxA-C6
PFHpA-C7
PFOA-C8
PFNA-C9
PFDA-C10
PFUnDA-Cll
PFDoDA-C12
PFDA-C10-13C2
PFBS-C4
PFHxS-C6
PFHxS-C6-18O2
PFHpS-C7
PFOS-C8
PFDS-C10
Avg. % Recovery
92.7
98.7
96.4
94.4
98.4
102
104
104
98.7
101
103
112
107
111
101
91.5
Std. Dev[a]
0.08
0.08
0.09
0.07
0.05
0.07
0.07
0.08
0.08
0.08
0.02
0.03
0.06
0.02
0.04
0.05
%RSDM
8.4
8.3
9.0
7.7
4.9
6.7
6.4
7.4
7.6
7.8
2.1
2.7
5.7
2.1
3.6
5.3
Nw
40
40
40
40
40
40
40
40
40
40
6
6
6
6
6
6
LaJ Std. Dev. is standard deviation.
[b] %RSD is percentage relative standard deviation.
[c] N is the number of DCCs analyzed.
47
-------
6. Discussion
6 1 Trends of Individual PFCAs
Two to five AOCs from each of the ten categories were monitored for C4 to C12 PFCAs from
2007 through 2011. Depending on their market availability, products may only have been collected
for two to four data points in a span of four years.
As mentioned in Section 4.1, due to the difficulty of collecting carpet samples, it was not possible
to compare the PFCA concentrations between similar products. The reduction trend for PFCAs in
similar products was not clear. There was still a fair amount of PFCAs in the products purchased in
2010 and 2011 relative to those purchased in 2007 to 2008.
Different temporal trends were observed for concentrations of the various PFCAs in the AOC
samples. In general, the market monitoring data suggested that reduction occurred in the PFCA
content in AOCs from 2007 to 2011, especially for commercial carpet/fabric-care products, treated
apparel, treated non-woven medical garments, and membranes for apparel products. Significant
reductions of PFOA were observed in all AOC categories except for one home textile and
upholstery product and two thread-sealant tape products, in which increased PFOA concentrations
were detected. It was observed that the amount of PFBA-C4 had increased in 19 of the 35 AOCs
monitored, with all floor wax products showing significant increases in the amount of PFBA-C4.
The results are consistent with the fact that short-chain perfluorinated compounds have become the
alternatives for various uses [2'16].
The monitoring data also showed a significant increase for most of the PFCAs in two of the treated
apparel and two of the three food contact paper samples acquired in 2010 compared with those
acquired in 2007 to 2008 and then followed by a decrease in samples acquired in 2011.
A non-parametric statistical method, the sign test[15], was performed using percent reduction as the
null hypothesis. The sign test allocates a sign, either positive (+) or negative (-), to each
observation according to whether it is greater or less than some hypothesized value [15]. The percent
reduction of PFCA concentrations was calculated as:
/ PFCA concentration \
Reduction (%) = 11 x 100
\ Initiai PFCA concentration measured in 2007 2008 /
The results are summarized in Table 6-1. In the table, the null hypothesis is that the percent
reduction has a "+" sign when the data meet one of the following three criteria: (1) the percent
reduction is greater than zero; (2) all measurements were below the detection limit; or (3) the initial
concentration was not reported, but the concentrations afterwards were below the detection limit.
-------
The "-" sign was used when the PFCA concentration was greater than its initial concentration. The
table does not include pre-treated carpet products. P-values, calculated using SAS 9.2 (SAS
Institute Inc., Gary, NC) were also presented in the table. A p-value < 0.05 is considered to be
statistically significant, although the smaller the p-value, the stronger the evidence of a difference.
The observation that there is more N+ than N- in the table and that most of the p-values are small
(many less than 0.0001) provide strong evidence that the concentrations of PFCAs in AOCs have
decreased. PFBA-C4 has the largest number of N- and also the largest p-value (0.14) indicating
little evidence of a change in the usage of PFBA-C4, which implies the increasing relatively
portion of PFBA-C4 in AOCs.
The relative abundance of each PFCA in each monitor year was calculated by:
(Sum of individual PFCA in all AOCs\
Relative abundance (%) = ^f AH our A AH *nr x 10ฐ
V Sum of All PFCAs in All AOCs )
The relative abundances of PFCAs on the market for different years are summarized in Figure 6-1.
The figure shows that PFCA C6 to C9 is predominant with PFOA (C8) being still the most
abundant PFCA species on the market. It is also evident that PFBA-C4 and PFPeA-C5 had
increases in the 2011 data.
49
-------
Table 6-1. Sign test data and p-values for individual PFCAs detected in AOC samples
AOC ID
B-l-1
B-l-2
B-3-1
B-3-2
B-5-1
B-5-2
B-7-1
B-7-2
C-l-1
C-l-2
C-2-1
C-4-1
C-5-1
C-8-1
C-9-1
D-3-1
D-3-2
D-3-3
D-4-1
D-4-2
D-4-3
D-5-1
D-7-1
D-7-2
D-10-1
Purchase date
05/26/2009
02/23/2011
11/24/2008
2/23/2011
11/24/2008
02/23/2011
05/01/2008
02/23/2011
11/06/2008
03/28/2011
02/23/2011
2/22/2010
02/23/2011
03/26/2010
03/01/2010
11/12/2008
02/24/2011
08/16/2011
11/24/2008
02/24/2011
08/16/2011
08/16/2011
11/12/2008
08/16/2011
11/24/2008
C4
+
+
+
+
+
+
+
+
NR
-
+
+
NR
NR
-
-
+
+
-
-
+
+
+
+
+
C5
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
C6
+
+
+
+
+
-
+
+
NR
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
C7
+
+
+
+
+
+
+
+
-
-
+
+
+
+
-
+
+
NR
-
+
+
NR
-
+
+
C8
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
-
+
+
+
-
+
+
C9
+
+
+
+
+
+
+
+
-
+
+
+
+
+
+
+
+
+
-
+
+
+
-
+
+
CIO
+
+
-
+
+
+
+
+
-
-
+
+
+
+
+
+
+
+
-
+
+
+
-
+
+
Cll
+
+
+
+
+
+
+
+
-
-
+
+
+
+
+
+
+
+
-
+
+
+
-
+
+
C12
+
NR[a]
+
+
+
+
+
+
NR
-
+
+
+
+
+
+
+
+
-
+
+
+
-
+
+
50
-------
Table 6-1. Sign test value for individual PFCAs detected in AOC samples (continued)
AOC ID
E-7-1
E-7-2
E-8-1
E-8-2
F-2-1
F-2-2
F-3-1
F-3-2
F-4-1
F-4-2
G-l-1
G-2-1
G-4-1
G-6-1
H-3-1
H-3-2
H-4-1
H-4-2
H-5-1
H-5-2
1-1-1
1-5-1
1-5-2
1-8-1
1-8-2
Purchase date
02/22/2010
03/30/2011
03/30/2010
03/30/2011
05/05/2009
03/28/2011
05/05/2009
03/28/2011
05/05/2009
03/28/2011
02/23/2011
03/30/2011
03/31/2011
03/31/2011
02/22/2010
09/07/2011
02/22/2010
09/07/2011
02/22/2010
09/12/2011
03/30/2010
03/30/2010
03/31/2011
03/30/2010
03/31/2011
C4
+
-
NR
NR
+
+
NR
+
NR
+
-
-
-
-
-
-
-
-
+
+
-
+
+
+
-
C5
+
+
+
+
+
+
NR
+
NR
+
-
+
+
-
+
+
-
+
+
+
-
+
+
+
+
C6
+
NR
+
-
+
+
NR
+
NR
+
+
+
+
+
+
+
NR
+
+
+
+
+
+
+
+
C7
+
+
NR
NR
+
+
+
+
NR
+
+
+
+
+
-
+
NR
+
+
+
+
+
+
+
+
C8
+
+
-
-
+
+
+
+
+
+
+
+
-
+
+
-
-
+
+
+
+
+
+
+
+
C9
+
+
-
+
+
+
+
+
NR
+
+
+
-
-
+
+
-
+
-
-
-
+
+
+
+
CIO
+
+
-
-
+
+
+
+
+
+
NR
-
NR
+
+
+
NR
+
+
+
-
+
NR
+
+
Cll
+
+
NR
NR
+
+
NR
+
+
+
+
+
-
-
+
+
-
+
+
+
+
NR
+
+
+
C12
+
+
NR
NR
+
+
+
+
+
+
+
+
NR
+
+
+
+
+
+
+
+
+
+
+
+
51
-------
Table 6-1. Sign test value for individual PFCAs detected in AOC samples (continued)
AOC ID
J-l-1
J-l-2
J-6-1
J-6-2
Statistics
Purchase date
03/28/2010
03/31/2011
03/28/2010
03/31/2011
N+M
N.w
NR
P-value
C4
+
+
-
-
29
18
7
0.1439
C5
+
+
+
-
47
5
2
0.0001
C6
+
+
NR
NR
45
3
6
0.0001
C7
+
+
NR
NR
40
6
8
0.0001
C8
-
-
NR
-
43
10
1
0.0001
C9
+
+
+
+
43
10
1
0.0001
CIO
+
+
+
-
40
10
4
0.0001
Cll
+
+
+
+
43
7
4
0.0001
C12
+
+
+
+
46
3
5
0.0001
Not reported due to QA failure.
[b] N+ is the total number of "+" sign.
[c] N- is the total number of"-" sign.
52
-------
0)
u
ฃ
(D
-a
E
3
.a
0)
32
24 --
16 1-
8 -
I 2007-2008 (N=35)
I 2008-2009 (N=12)
2010(N=17)
I2011(N=31)
Figure 6-1. Relative abundance of PFCA in AOCs from 2007 to 2011 (N is the number of
AOCs monitored)
6.2 Trends of Total PFCAs
The sign test results for the total PFCA (TPFCA) for C4 to C12, C6 to C12, and C8 to C12 for all
monitored AOCs are presented in Table 6-2. The p-value of 0.0005 provides strong evidence that
TPFCA has been reduced in a majority of the AOCs in recent years. The data presented in the
tables in Appendix A also show that, among the ten categories of AOCs, commercial carpet-care
liquids, treated floor waxes, treated food contact paper, and thread-sealant tapes are the most
significant sources of PFCAs.
53
-------
Table 6-2. Sign test results of TPFCA in AOCs
AOC Category
ID
B
C
D
E
F
G
H
I
J
Total
C4 to C12
N+M
7
4
8
2
6
1
4
5
1
39
N_[bl
1
3
2
2
0
3
2
0
3
15
C6 to C12
N+M
8
6
8
2
6
1
4
5
1
41
N_[bl
0
1
2
2
0
o
J
2
0
o
J
13
C8 to C12
N+M
8
6
8
2
6
1
4
5
1
41
N_[b]
0
1
2
2
0
3
2
0
3
13
Number of samples with reduced TPFCA (+).L J Number of samples with increased TPFCA (-).
6.3 Domestic versus Imported Articles
It was our intention to collect domestic and imported products equally. However, since some of the
imported products that we collected in Phase 1 were no longer available in the marketplace, we
collected more domestic AOCs than foreign AOCs. The geographical distribution of the AOCs is
presented in Figure 6-2.
I USA - 60%
I England-2%
I Vietnam -4%
I China-23%
I Thailand -1%
(Bangladesh -1%
Dominican Republic - 2%
Malaysia - 3%
El Salvador - 2%
Indonesia -1%
Figure 6-2. Distribution of the AOCs used for market monitoring based on country of
origin
54
-------
As shown in Tables 5-1 to 5-10, among the 10 article categories, all pre-treated carpet, commercial
carpet-care, treated home textile and upholstery, treated floor wax, treated food contact paper, and
11 of 13 AOCs of household carpet/fabric-care products were manufactured in the United States,
while treated apparel, non-woven medical garments, membranes for apparel, and thread sealant-
tape products were imported. The data showed no obvious tendencies for high PFCA contents in
domestic vs. imported articles.
6.4 Short-Chain versus Long-Chain PFCAs in AOCs
PFCA-C4 to C7 was grouped as short-chain PFCAs and PFCA-C8 to PFCA-C12 was grouped as
long-chain PFCAs. The results of the sign test in Table 6-3 showed no significant difference in
trends between the two groups over the monitoring period. There was not much difference between
short-chain and long-chain PFCAs in AOCs in terms of N+, number of samples with reduced
PFCA (+), and N-, number of samples with increased PFCA(-).
Table 6-3. Sign test results of PFCA in AOCs in short-chain group versus long-chain group
Sign Test
N+[a]
N.M
NR[C]
P-value
Short-Chain
161
32
23
O.0001
Long-Chain
215
40
15
O.0001
[a] Number of samples with reduced PFCA (+).[b] Number of samples with increased PFCA(-).
[c] Not reported due to QA failure.
6.5 Perfluoroalkyl Sulfonates (PFAS)
Following the voluntary phase out of PFOS by 3M between 2000 and 2002, EPA took prompt
regulatory action in 2002 to limit any future manufacture or importation of the 88 PFAS chemicals
that were specifically included in the phase-out list.[13] No measurements of PFAS were conducted
in Phase 1 of the project. However, we did observe PFAS during the PFCAs market monitoring
study. Several AOC samples were selected for analysis to determine their PFAS C4, C6, C7, C8,
and CIO. Among the samples that were analyzed, carpet/upholstery protector concentrate 1,
purchased in 2008, and carpet shampoo 1, purchased in 2009 and 2011, had most PFAS. The
carpet shampoo product showed an increased amount of PFAS (Figure 6-3) in the products
purchased in 2011 compared to the same products purchased in 2008.
It has been reported that a short-chain sulfonate (i.e., PFBS-C4), which has no bioaccumulative or
toxic effects, has been developed by 3M as an alternative to PFOS.[16] The pronounced increase of
PFBS-C4 in the AOC in Figure 6-3 indicates that PFBS-C4 is being used as an alternative to
PFOS.
55
-------
1000
D11/06/2008
3/28/2011
PFBS-C4S PFHxS-C6S PFHpS-C7S PFOS-C8S PFDS-C10S
PFAS
Figure 6-3. PFAS detected in a carpet shampoo in 2008 and 2011
56
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7. References
[1] Lao, C., Anitole, K., Hodes, C., Lai, D., Pfahles-Hutchens, A., and Seed. J. Perfluoroalkyl
acids: a review of monitoring and toxicological findings. lexicological Sciences, 99: 366-
394, (2007).
[2] Lindstrom, A. B., Strynar, M. J. and Libelo, E. L. Polyfluorinated compounds: past, present,
and future. Environmental Science & Technology, 45: 7954-7961, (2011).
[3] Guo, Z., Liu, X., Krebs, K. A. and Roache, F. N. Perfluorocarboxylic acid content in 116
articles of commerce, U.S. EPA, EPA/600/R-09/033 (2009).
http://www.epa.gov/nrmrl/pubs/600r09033/600r09033.html
[4] Haug, L. S., Thomsen, C. and Becher, G. Time trends and the influence of age and gender
on serum concentrations of perfluorinated compounds in archived human samples,
Environmental Science & Technology, 43: 2131-2136, (2009).
[5] Kato, K., Calafat, A. M. and Needham, L. L. Polyfluoroalkyl chemicals in house dust,
Environmental Research, 109: 518-523, (2009).
[6] Butt, C. M., Berger, U., Bossi, R. and Tomy, G. T. Levels and trends of poly- and
perfluorinated compounds in the arctic environment, Science of Total Environment, 408:
2936-2965, (2010).
[7] Fiedler, S., Pfister, G. and Schramm, K. Poly- and perfluorinated compounds in household
consumer products, Toxicological & Environmental Chemistry, 92: 1801-1811, (2010).
[8] Haug, L. S., Huber, S., Becher, G. and Thomsen, C. Characterisation of human exposure
pathways to perfluorinated compounds - comparing exposure estimates with biomarker of
exposure, Environment International, 37: 687-693, (2011).
[9] Houde, M., De Silva, A. O., Muir, D. C. G, Letcher, R. J. Monitoring of perfluorinated
compounds in aquatic biota: an updated review. Environmental Science & Technology, 45:
7962-7972, (2011).
[10] Shoeib, M., Harner, T., Webster, G. M. and Lee, S. C. Indoor sources of poly- and
perfluorinated compounds (PFCS) in Vancouver, Canada: implications for human exposure,
Environmental Science & Technology, 45: 7999-8005, (2011).
[11] Liu, X., Krebs, K. A., Guo, Z. and Roache, F. N. Method development for liquid
chromatography/triple quadrupole mass spectrometer analysis of trace level
perfluorocarboxylic acids in articles of commerce. Journal of Chromatography A, 1216:
3910-3918, (2009).
57
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[12] U.S. EPA. 2010/2015 PFOA Stewardship Program, U.S. EPA, Office of Pollution
Prevention and Toxics (2010). http://www.epa.gov/oppt/pfoa/pubs/stewardship/index.htm
[13] U.S. EPA. EPA Action on PFAS Compounds, U.S. EPA, Office of Pollution Prevention and
Toxics (2010), http://www.epa.gov/oppt/pfoa/pubs/pfas.html#snurs
[14] 40 CFR 136 Appendix B (1986), Code of Federal Regulations Part 136, Appendix B,
Definition and Procedure for the Determination of the Method Detection Limit Revision
1.11.
[15] Whitley, E. and Ball, J. Statistics review 6: Nonparametric methods, Critical Care. 6: 509-
513, (2002). http://www.ncbi.nlm.nih.gov/pmc/articles/PMC153434/.
[16] Swedish Chemical Agency, Perfluorinated substances and their uses in Sweden, KEMI
Report No. 7, ISSN: 0284-1185, (2006).
http ://www.kemi. se/Documents/Publikati oner/Try cksaker/Rapporter/Report7_06.pdf
58
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Appendix A. Summary of PFCAs in AOC Samples
The PFCA concentrations in AOC samples are summarized in Tables A-l through A-l 1. The
following abbreviations and fonts are used:
BDL = result below the detection limit;
NR = not reported (i.e., the result does not meet data quality requirements);
NA = not available, when PFBA-C4, PFPeA-C5 and perfluoroalkyl sulfonates were not calibrated
in Phase 1;
RCS = recovery check standard; RCS percent recovery is the average of duplicate or triplicate
samples; and
Bold Italics = result above highest calibration concentration.
TPFCA does not include data below the lowest calibration concentration or data that do not meet
data quality requirements.
59
-------
Table A-l. Extractable PFCAs in pre-treated carpet (ng/g AOC)
AOC ID
A- 1-0
A-l-1
A- 1-2
A- 1-3
A-2-0
A-2-1
A-2-2
A-9-0
A-9-1
Purchase Date
03/09/2007
05/18/2010
09/08/2011
09/08/2011
03/12/2007
05/18/2010
05/18/2010
02/04/2008
05/18/2010
C4
4.10
65.1
14.6
131
BDL
107
BDL
BDL
34.0
C5
NR
BDL
BDL
BDL
BDL
BDL
BDL
11.5
22.6
C6
39.8
3.70
14.7
8.70
BDL
5.80
BDL
19.2
40.1
C7
14.1
BDL
39.3
BDL
BDL
BDL
BDL
43.0
146
C8
10.4
5.50
52.9
3.50
BDL
BDL
BDL
19.9
226
C9
6.30
BDL
35.7
BDL
BDL
BDL
BDL
20.7
236
CIO
5.30
5.20
27.5
BDL
BDL
BDL
BDL
18.4
179
Cll
2.30
BDL
3.30
BDL
BDL
BDL
BDL
12.3
160
C12
BDL
3.40
6.50
BDL
BDL
BDL
BDL
42.0
129
%RCS[a]
81.7
120
111
107
91.4
116
83.6
84.7
89.7
TPFCA[b]
82.3
82.9
195
143
BDL
113
BDL
187
1172
N[c]
2
3
3
3
2
2
3
2
3
1 Percent recovery of recovery check standards.[b] Total perfluorocarboxylic acids.[c] Number of samples analyzed for each AOC.
Table A-2. Extractable PFCAs in commercial carpet-care liquids (ng/g AOC)
AOC ID
B-l-0
B-l-1
B-l-2
B-3-0
B-3-1
B-3-2
B-5-0
B-5-1
B-5-2
B-7-0
B-7-1
B-7-2
Purchase Date
04/19/2007
05/26/2009
02/23/2011
04/19/2007
11/24/2008
02/23/2011
04/19/2007
11/24/2008
02/23/2011
04/19/2007
05/01/2008
02/23/2011
C4
440
67.7
186.
85.4
BDL
BDL
131
26.9
55.7
NA
BDL
BDL
C5
1725
BDL
28.3
BDL
BDL
BDL
BDL
BDL
BDL
363
BDL
BDL
C6
5197
61.5
BDL
44.8
BDL
BDL
30.9
8.27
52.9
928
22.0
17.1
C7
14051
118
BDL
49.5
8.69
BDL
19.8
BDL
BDL
2564
BDL
BDL
C8
6748
192
58.1
50.1
38.3
BDL
19.1
9.67
BDL
1838
25.5
BDL
C9
8856
311
86.7
56.2
44.8
BDL
BDL
BDL
BDL
2693
17.5
BDL
CIO
4376
117
BDL
BDL
12.5
BDL
BDL
BDL
BDL
1330
21.0
BDL
Cll
3999
109
BDL
35.0
7.74
BDL
BDL
BDL
BDL
844
16.2
BDL
C12
2151
61.8
NR
37.6
BDL
BDL
19.8
BDL
BDL
300
BDL
BDL
%RCS[a]
101
87.5
116
100
85.6
82.8
99.9
112
113
101
101
82.1
TPFCA[b]
47552
1038
359
359
112
BDL
220
44.8
109
10859
102
17.1
Nw
2
2
2
2
2
2
2
2
2
2
2
2
Percent recovery of recovery check standards.[b] Total perfluorocarboxylic acids.[c] Number of samples analyzed for each AOC.
60
-------
Table A-3. Extractable PFCAs in household carpet/fabric-care liquids (ng/g AOC)
AOC ID
C-l-0
C-l-1
C-l-2
C-2-0
C-2-1
C-4-0
C-4-1
C-5-0
C-5-1
C-8-0
C-8-1
C-9-0
C-9-1
Purchase Date
04/19/2007
11/06/2008
03/28/2011
05/10/2007
02/23/2011
05/16/2007
02/22/2010
05/16/2007
02/23/2011
06/06/2007
03/26/2010
09/29/2007
03/01/2010
C4
BDL
NR
94.6
BDL
BDL
NA
BDL
NA
52.8
NA
29.8
BDL
14.8
C5
BDL
BDL
BDL
BDL
BDL
NA
BDL
NA
BDL
NA
BDL
BDL
BDL
C6
BDL
NR
BDL
BDL
BDL
75.5
18.9
195
76.6
BDL
BDL
173
25.9
C7
11.4
13.7
19.5
BDL
BDL
NR
BDL
BDL
BDL
BDL
BDL
BDL
10.6
C8
6.97
BDL
BDL
BDL
BDL
666
74.6
BDL
BDL
BDL
BDL
707
10.9
C9
3.09
37.3
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
CIO
BDL
9.27
15.5
BDL
BDL
104
24.9
BDL
BDL
BDL
BDL
289
BDL
Cll
BDL
16.5
48.0
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
C12
BDL
NR
28.6
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
%RCS[a]
120
109
120
105
84.0
98.3
96.4
93.4
106
81.0
81.4
94.6
107
TPFCA[b]
21.5
76.7
206
BDL
BDL
846
118
195
129
BDL/NA
29.8
1169
62.3
Nw
2
2
2
2
2
2
2
2
2
2
2
2
2
Percent recovery of recovery check standards.l J Total perfluorocarboxylic acids. LCJ Number of samples analyzed for each AOC
61
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Table A-4. Extractable PFCAs in treated apparel (ng/g AOC)
AOC ID
D-3-0
D-3-1
D-3-2
D-3-3
D-4-0
D-4-1
D-4-2
D-4-3
D-5-0
D-5-1
D-7-0
D-7-1
D-7-2
D-10-0
D-10-1
Purchase Date
05/10/2007
11/12/2008
02/24/2011
08/16/2011
05/10/2007
11/24/2008
02/24/2011
08/16/2011
05/10/2007
08/16/2011
05/10/2007
11/12/2008
08/16/2011
08/17/2007
11/24/2008
C4
7.38
36.6
BDL
BDL
6.50
16.8
29.9
BDL
5.58
BDL
8.00
5.18
BDL
5.11
BDL
C5
16.4
BDL
BDL
BDL
NR
BDL
BDL
BDL
NR
BDL
3.94
3.51
BDL
NR
BDL
C6
43.2
12.4
BDL
6.20
27.0
19.1
BDL
8.80
27.2
4.62
38.3
28.2
BDL
63.7
BDL
C7
64.9
12.5
BDL
NR
8.96
38.8
BDL
BDL
NR
2.48
8.05
37.7
BDL
18.7
BDL
C8
160.5
15.7
BDL
5.09
38.0
235
BDL
2.86
32.0
4.80
55.5
269
BDL
109
BDL
C9
235
22.3
BDL
BDL
3.85
164
BDL
BDL
5.97
2.64
4.13
199
BDL
13.6
BDL
CIO
69.2
8.56
BDL
3.38
22.0
154
BDL
BDL
13.5
8.36
28.3
246
BDL
46.8
BDL
Cll
61.5
4.86
BDL
BDL
1.39
47.2
BDL
BDL
3.60
3.18
1.94
98.2
BDL
5.17
BDL
C12
21.2
2.77
BDL
BDL
14.5
79.6
BDL
BDL
8.04
6.08
13.0
87.7
BDL
NR
BDL
%RCS[a]
88.9
119
93.3
90.6
99.9
95.3
98.7
99.1
99.3
119
103
120
107
96.0
81.1
TPFCA[b]
678.91
115.59
BDL
14.67
122.18
755.23
29.88
11.66
95.93
32.16
161.21
973.75
BDL
261.66
BDL
Nw
2
3
o
5
2
2
2
o
5
2
2
2
2
o
3
2
2
2
Percent recovery of recovery check standards.l J Total perfluorocarboxylic acids. LCJ Number of samples analyzed for each AOC
Table A-5. Extractable PFCAs in treated home textile and upholstery (ng/g AOC)
AOC ID
E-7-0
E-7-1
E-7-2
E-8-0
E-8-1
E-8-2
Purchase Date
07/10/2007
02/22/2010
03/30/2011
07/10/2007
03/30/2010
03/30/2011
C4
17.7
8.80
116
NR
18.3
3.48
C5
21.6
BDL
16.44
BDL
BDL
BDL
C6
68.0
6.47
NR
10.5
4.52
10.6
C7
96.6
7.41
8.44
NR
3.56
4.97
C8
330
33.3
16.9
18.8
72.4
38.1
C9
213
14.7
8.70
7.15
8.05
3.80
CIO
125
21.0
21.3
8.99
52.2
17.8
Cll
45.7
7.11
6.62
NR
3.96
2.73
C12
43.0
9.78
13.5
NR
30.2
7.24
%RCS[a]
100
116
113
106
84.1
93.6
TPFCA[b]
961
109
208
45.5
193
88.8
Nw
2
o
J
3
2
2
2
Percent recovery of recovery check standards.l J Total perfluorocarboxylic acids. LCJ Number of samples analyzed for each AOC
62
-------
Table A-6. Extractable PFCAs in treated non-woven medical garments (ng/g AOC)
AOC ID
F-2-0
F-2-1
F-2-2
F-3-0
F-3-1
F-3-2
F-4-0
F-4-1
F-4-2
Purchase Date
01/30/2008
05/05/2009
03/28/2011
01/30/2008
05/05/2009
03/28/2011
01/30/2008
05/05/2009
03/28/2011
C4
BDL
BDL
BDL
4.87
NR
BDL
515
NR
BDL
C5
4.26
BDL
BDL
BDL
NR
BDL
786
NR
BDL
C6
NR
BDL
BDL
NR
NR
BDL
598
NR
BDL
C7
18.4
BDL
BDL
9.03
8.15
BDL
506
NR
BDL
C8
47.1
7.37
BDL
60.7
37.3
43.5
369
18.4
BDL
C9
82.1
6.14
BDL
6.33
4.35
BDL
334
NR
BDL
CIO
20.0
4.75
BDL
17.4
9.17
16.6
218
9.27
BDL
Cll
24.8
3.02
BDL
BDL
NR
BDL
173
7.55
BDL
C12
8.72
BDL
BDL
5.30
1.58
BDL
88.9
6.14
BDL
%RCS[a]
86.9
82.5
112
80.4
82.0
94.0
101
94.0
106
TPFCA[b]
205
21.3
BDL
104
60.6
60.1
3588
41.4
BDL
NW
2
3
2
2
2
3
2
2
2
1 Percent recovery of recovery check standards.[b] Total perfluorocarboxylic acids.[c] Number of samples analyzed for each AOC.
Table A-7. Extractable PFCAs in treated floor waxes (ng/g AOC)
AOC ID
G-l-0
G-l-1
G-2-0
G-2-1
G-4-0
G-4-1
G-6-0
G-6-1
Purchase Date
07/10/2007
02/23/2011
07/10/2007
03/30/2011
07/10/2007
03/31/2011
07/10/2007
03/31/2011
C4
BDL
45.9
3.50
12.7
BDL
131
BDL
219
C5
BDL
1542
7.19
BDL
8.62
BDL
BDL
39.0
C6
48.3
21.4
15.3
BDL
19.1
BDL
40.7
BDL
C7
63.9
51.8
21.4
BDL
27.3
13.5
62.5
BDL
C8
44.8
BDL
7.50
BDL
15.6
59.7
36.9
13.6
C9
50.4
26.7
4.19
BDL
11.8
2737
47.6
155.6
CIO
BDL
NR
3.56
8.18
NR
18.4
BDL
BDL
Cll
BDL
BDL
1.65
BDL
BDL
461
BDL
22.6
C12
BDL
BDL
2.97
BDL
NR
BDL
BDL
BDL
%RCS[a]
98.2
119
95.4
106
116
98.7
101
87.2
TPFCA[b]
207
1688
67.3
20.9
82.3
3421
187.7
450
Nw
2
2
2
2
2
2
2
2
Percent recovery of recovery check standards.[b] Total perfluorocarboxylic acids.[c] Number of samples analyzed for each AOC .
63
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Table A-8. Extractable PFCAs in treated food contact paper (ng/g AOC)
AOC ID
H-3-0
H-3-1
H-3-2
H-4-0
H-4-1
H-4-2
H-5-0
H-5-1
H-5-2
Purchase Date
10/15/2007
02/22/2010
09/07/2011
10/15/2007
02/22/2010
09/07/2011
10/30/2007
02/22/2010
09/12/2011
C4
BDL
6.55
5.16
BDL
24.1
15.2
166
59.0
48.7
C5
BDL
BDL
BDL
BDL
30.8
BDL
221
142
50.9
C6
11.7
5.32
BDL
NR
65.2
BDL
4427
1298
1903
C7
BDL
8.29
BDL
NR
87.
BDL
2854
874
1469
C8
BDL
BDL
1.83
104
137
10.6
4642
1186
2498
C9
BDL
BDL
BDL
BDL
212
BDL
BDL
5.27
8.74
CIO
BDL
BDL
BDL
70.2
NR
BDL
BDL
BDL
BDL
Cll
BDL
BDL
BDL
BDL
105
BDL
BDL
BDL
BDL
C12
BDL
BDL
BDL
54.0
23.1
BDL
BDL
BDL
BDL
%RCS[a]
86.9
119
98.8
105
100
92.8
103
93.1
116
TPFCA[b]
11.7
20.2
6.99
228
685
25.9
12310
3564
5978
Nw
2
3
o
6
2
o
5
3
2
3
3
1 Percent recovery of recovery check standards.[b] Total perfluorocarboxylic acids.[c] Number of samples analyzed for each AOC.
Table A-9. Extractable PFCAs in membranes for apparel (ng/g AOC)
AOC ID
1-1-0
1-1-1
1-5-0
1-5-1
1-5-2
1-8-0
1-8-1
1-8-2
Purchase Date
05/16/2007
03/30/2010
05/16/2007
03/30/2010
03/31/2011
08/17/2007
03/30/2010
03/31/2011
C4
2.94
4.17
22.0
13.4
BDL
3.86
BDL
7.49
C5
BDL
3.48
8.23
BDL
BDL
3.33
BDL
BDL
C6
17.2
9.25
50.9
4.22
3.20
30.3
BDL
6.74
C7
11.5
3.34
12.1
BDL
BDL
5.46
BDL
2.01
C8
77.0
34.3
163
10.6
6.33
82.6
BDL
5.31
C9
5.95
8.71
12.8
4.65
BDL
5.97
BDL
4.80
CIO
24.3
37.8
72.2
14.0
NR
27.7
BDL
7.60
Cll
3.24
2.35
NR
1.98
BDL
2.02
BDL
1.57
C12
18.7
8.91
23.6
3.11
BDL
10.3
BDL
2.56
%RCS[a]
109
103
113
109
120
87.7
101
104
TPFCA[b]
161
112
364
51.9
9.54
172
BDL
38.1
Nw
2
o
6
2
2
2
2
3
o
5
Percent recovery of recovery check standards.[b] Total perfluorocarboxylic acids.[c] Number of samples analyzed for each AOC.
64
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Table A-10. Extractable PFCAs in Thread sealant tapes (ng/g AOC)
AOC ID
J-l-0
J-l-1
J-l-2
J-6-0
J-6-1
J-6-2
Purchase Date
04/06/2007
03/28/2010
03/31/2011
08/17/2007
03/28/2010
03/31/2011
C4
BDL
BDL
BDL
BDL
2.81
88.6
C5
BDL
BDL
BDL
BDL
BDL
23.8
C6
BDL
BDL
BDL
NR
NR
335
C7
BDL
BDL
BDL
NR
3.35
37.4
C8
BDL
8.00
11.2
1440
NR
2130
C9
BDL
BDL
BDL
BDL
BDL
BDL
CIO
BDL
BDL
BDL
BDL
BDL
4.74
Cll
BDL
BDL
BDL
BDL
BDL
BDL
C12
BDL
BDL
BDL
BDL
BDL
BDL
%RCS[a]
99.2
81.4
95.9
105
107
89.4
TPFCA[b]
BDL
BDL
11.2
1440
6.17
2620
Nw
2
2
3
2
2
3
Percent recovery of recovery check standards.l J Total perfluorocarboxylic acids. LCJ Number of samples analyzed for each AOC
65
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