PFOS or PreFOS? Are perfluorooctane sulfonate precursors (PreFOS) important determinants of human and environmental perfluorooctane sulfonate (PFOS) exposure?
Abstract
The extent to which perfluorooctanesulfonate precursors (PreFOS) play a role in human or environmental exposure to perfluorooctanesulfonate (PFOS) is not well characterized. The diversity of manufactured PreFOS and its degradation products (e.g. C(8)F(17)SO(2)R and C(8)F(17)SO(2)NR'R'', where R is H or F, and R' and R'' are various) has made it difficult to track their fate. Temporal trends of PFOS in both humans and wildlife are discrepant, thus it is difficult to predict future exposure, and hypotheses about the role of PreFOS have been raised. Although abiotic degradation of commercially important PreFOS materials requires further research, current data suggest that the yield of PFOS is negligible or minor. On the other hand, in vivo biotransformation of PreFOS yields PFOS as the major metabolite, and >32% yields have been observed. In Canadians, exposure to PreFOS was equivalent or greater than direct PFOS exposure prior to 2002. In most ocean water, PFOS is dominant to PreFOS, but in the oceans east of Greenland there may be more PreFOS than PFOS, consistent with the fact that whales and humans in this region also show evidence of substantial PreFOS exposure. Quantitative assessments of PFOS body-burdens coming from PreFOS are complicated by the fact that PreFOS partitions to the cellular fraction of blood, thus biomonitoring in serum under predicts PreFOS relative to PFOS. Many unknowns exist that prevent accurate modelling, thus analytical methods that can distinguish directly manufactured PFOS, from PFOS that has been biotransformed from PreFOS, should be applied in future human and environmental monitoring. Two new source tracking principles are presented and applied to human serum.
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PFSAs and their precursors have been manufactured almost exclusively by ECF, which produced a mixture of linear (70%) and many branched (total 30%) isomers.
“PFSAs and their precursors have been manufactured almost exclusively by ECF which produced a mixture of linear (70%) and many branched (total 30%) isomers [32].”
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Self-citationDistribution of perfluorinated compounds in surface seawaters between Asia and Antarctica
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“These N-alkyl FASEs are analogous to FTOHs.”
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“However, determining isomer patterns have been of particular interest for exploring sources of exposure (Martin et al., 2010; Miralles-Marco and Harrad, 2015).”
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“Martin et al. (2010); Zhao et al. (2018) New studies on the toxicity of PFOA and PFOS (also referred as “legacy PFAS”), along with replacement PFAS (also referred to as “alternative PFAS”) based on animal and cell studies, epidemiological studies in humans, and computational models, continue to…”
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“The less proportion of linear PFOS in serum might be used as a biomaker of exposure to PFOS-precursors (Martin et al., 2010).”
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“Martin et al. (2010) recommended more precise analytical methods might distinguish directly manufactured PFOS from that biotransformed from PFOSprecursors.”
BackgroundObservation of emerging per- and polyfluoroalkyl substances (PFASs) in Greenland marine mammals
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“…acid (PFOS) and its precursors were phased out in 2002 by 3 M, and emissions of long chain PFCAs and their precursors are to be eliminated by 2015 (Martin et al., 2010; US EPA, 2006), manufacturing of other PFASs has gone unnoticed (De Silva et al., 2011; Wang et al., 2013a).”
BackgroundLevels of Perfluorinated Compounds in Food and Dietary Intake of PFOS and PFOA in The Netherlands
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Self-citationHelsingør Statement on poly- and perfluorinated alkyl substances (PFASs)
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“…et al., 2012; Gawor et al., 2013; Wang et al., 2013; Zareitalabad et al., 2013), wildlife (Giesy and Kannan, 2002; Houde et al., 2011), and human tissue (Giesy and Kannan, 2002; Kannan et al., 2004; Martin et al., 2010; Kato et al., 2011; Loi et al., 2013; Yeung et al., 2013a,b) all over the globe.”
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“PFSAs and their precursors have been manufactured almost exclusively by ECF which produced a mixture of linear (70%) and many branched (total 30%) isomers [32].”
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Temporal Trends of Perfluoroalkyl Concentrations in American Red Cross Adult Blood Donors, 2000–2010
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“Nonetheless, PFOS and its precursors continue to be manufactured by other companies in Asia (Martin et al. 2010).”
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“The human and environmental toxicological response to such exposure is not known, but could include, among others, endocrine disruption (Clarke and Smith, 2011; Martin et al., 2010).”
BackgroundJha, G., Kankarla, V., Mclennon, E., Pal, S., Sihi, D., Dari, B., Diaz, D., & Nocco, M. A. (2021) · International Journal of Environmental Research and Public Health · doi:10.3390/ijerph182312550 · Cited by 160 · see citing works
“In fact, PFAS were added to the Persistent Organic Pollutant (POPs) list under the Stockholm Convention in 2009 for their persistence and subsequent negative environmental and health impacts [32].”
BackgroundEvidence for the trophic transfer of perfluoroalkylated substances in a temperate macrotidal estuary
Munoz, G., Budzinski, H., Babut, M., Drouineau, H., Lauzent, M., Menach, K. L., Lobry, J., Selleslagh, J., Simonnet-Laprade, C., & Labadie, P. (2017) · Environmental Science & Technology · doi:10.1021/acs.est.7b02399 · Cited by 165 · see citing works
“60 Galatius et al. reported a high degree of variability of FOSA to PFOS ratios across marine mammal species.”
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“The most studied compounds to date are perfluoroalkyl carboxylic acids (PFCAs), like perfluorooctanoate (PFOA) and perfluoroalkyl sulfonic acids (PFSAs), like perfluorooctane sulfonate (PFOS) (D'eon andMabury, 2011; Martin et al., 2010).”
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“Some of these compounds are persistent in the environment, whereas others degrade to more environmentally stable compounds such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), which can make determining exposures and concentrations in organisms difficult (Dinglasan et al., 2004; Martin et al., 2…”
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“Recently however, new approaches (discussed further below) have been have been suggested as biomarkers of exposure and applied in efforts to differentiate between direct exposure to PFOS and PFOSprecursor exposure (Benskin et al., 2009; Martin et al., 2010).”
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“Frequently cited precursors include N-ethyl perfluorooctane sulfonamide (EtFOSA) and FOSA (Benskin et al., 2009; Martin et al., 2010; Tomy et al., 2004; Yeung et al., 2009).”
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Polyfluorinated Compounds in Serum Linked to Indoor Air in Office Environments
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“This could have resulted in decreased environmental concentrations of PFOS precursors, or “PreFOS” as has been coined by Martin et al. (2010), which refers to the complexity of fluorinated precursors that can degrade and give rise to PFOS.”
BackgroundAdult Dose-dependent Behavioral and Cognitive Disturbances after a Single Neonatal PFHxS Dose
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Perfluoroalkyl acids and their precursors in indoor air sampled in children's bedrooms
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“For the second ionic PFAS fraction (i.e. PFSAs and PFCAs), the collection bottles were changed and the SIPs were extracted with acetonitrile.”
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“PFSAs and their precursors have been manufactured almost exclusively by ECF which produced a mixture of linear (70%) and many branched (total 30%) isomers [32].”
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“Migration of N-EtFOSE based chemicals from carpet cleaning products and food packaging materials and subsequent transformation to PFOS may explain these results [10, 11].”
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Systematic developmental toxicity assessment of a structurally diverse library of PFAS in zebrafish
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“FOSA, an intermediate metabolite of longer-chain PFOS precursors (Martin et al., 2010), has been identified in previous studies as particularly bioactive compared to other PFAS in zebrafish (Dasgupta et al.”
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Treatment of perfluorooctane sulfonic acid (PFOS) using a large-scale sonochemical reactor
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Self-citationPer- and polyfluoroalkyl substances (PFAS) and total fluorine in fire station dust
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“For TMFs, the ratio of themaximum to minimum reported values is not so great, but it reaches about 20 for the most intensely studied PFASs (PFOA and PFOS).”
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Gebbink, W. A., Glynn, A. W., & Berger, U. (2015) · Environmental Pollution · doi:10.1016/j.envpol.2015.01.024 · Cited by 93 · see citing works
“The manufacturing of PFOS and its precursors resulted in a mixture of linear and branched isomers (Martin et al., 2010), and production was phased out by the main manufacturer”
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“When using a biotransformation factor determined in a study with rats (20% biotransformation of precursors to PFOS (Martin et al., 2010)) the total dietary intakes of PFOS (precursor intakes converted to PFOS on a molar basis) were”
BackgroundMethodWidening the Lens on PFASs: Direct Human Exposure to Perfluoroalkyl Acid Precursors (pre-PFAAs)
McDonough, C. A., Li, W., Bischel, H. N., Silva, A. O. D., & DeWitt, J. C. (2022) · Environmental Science & Technology · doi:10.1021/acs.est.2c00254 · Cited by 86 · see citing works
Recent developments in trace analysis of poly- and perfluoroalkyl substances
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“The role of neutral precursor PFASs in bioaccumulation and human exposure is a controversial issue that is currently debated [41].”
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“Perfluorooctane sulfonamide (FOSA) is the most commonly detected precursor that is degraded to PFOS [33].”
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Riverine inputs and source tracing of perfluoroalkyl substances (PFASs) in Taihu Lake, China
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Gewurtz, S. B., Backus, S. M., Silva, A. O. D., Ahrens, L., Armellin, A., Evans, M. S., Fraser, S., Gledhill, M., Guerra, P., Harner, T., et al. (2013) · Environment International · doi:10.1016/j.envint.2013.05.008 · Cited by 78 · see citing works
“…Harbour, Toronto Harbour, Lake Ontario, and the St. Lawrence River, the PFAA profile was similar and typical of abiotic and food web studies e.g., (Ahrens et al., 2010; Furdui et al., 2008a; Kelly et al., 2009; Kwadijk et al., 2010; Labadie and Chevreuil, 2011; Martin et al., 2003a, 2003b, 2004).”
MethodLetcher, R. J., Chu, S., McKinney, M. A., Tomy, G. T., Sonne, C., & Dietz, R. (2014) · Chemosphere · doi:10.1016/j.chemosphere.2014.04.022 · Cited by 76 · see citing works
“In particular, the degradation of PFOS precursors (or ‘‘PreFOS’’) is largely unknown, which refers to the complexity of fluorinated precursors that can degrade and give rise to PFOS in exposed biota (Parsons et al., 2008; Martin et al., 2010; Liu and Avendaño, 2013; Wang et al., 2013).”
BackgroundMethodResultSun, Y., Angelotti, B., Brooks, M., Dowbiggin, B., Evans, P. J., Devins, B., & Wang, Z.-W. (2018) · Chemosphere · doi:10.1016/j.chemosphere.2018.06.162 · Cited by 76 · see citing works
- Authors
- Martin, J. W., Asher, B. J., Beesoon, S., Benskin, J. P., & Ross, M. S.
- Affiliations
- University of Alberta (CA)
- Corresponding author
- Martin, Jonathan W.
- Venue
- Journal of Environmental Monitoring
- Publisher
- Royal Society of Chemistry (RSC)
- Published
- 2010
- Volume
- 12
- Issue
- 11
- Pages
- 1979
- ISSN
- 1464-0325 (ISSN-L)
- 1464-0333
- OpenAlex
- W2088093177
- Cited by
- 311
- References
- 169
- Citations by year
- 2026: 21 · 2025: 21 · 2024: 18 · 2023: 22 · 2022: 24 · 2021: 19 · 2020: 21 · 2019: 9 · 2018: 22 · 2017: 17 · 2016: 10 · 2015: 19 · 2014: 23 · 2013: 19 · 2012: 27
- FWCI
- 2.61
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Journal of Environmental Monitoring (publishedVersion)
- PubMed (publishedVersion)
- Topics
- Physical Sciences › Environmental Science › Environmental Chemistry › Per- and polyfluoroalkyl substances research
- Physical Sciences › Environmental Science › Health, Toxicology and Mutagenesis › Toxic Organic Pollutants Impact
- Life Sciences › Pharmacology, Toxicology and Pharmaceutics › Pharmaceutical Science › Fluorine in Organic Chemistry
- Keywords
- PFOS, human exposure, environmental exposure, serum biomonitoring, body burden, source tracking, whales, abiotic degradation, temporal trends
- MeSH terms
- Animals, Biotransformation, Environmental Exposure, Environmental Monitoring, Environmental Pollutants, Fluorocarbons, Food Analysis, Humans, Alkanesulfonic Acids
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