Cited by 373Per- and polyfluoroalkyl substances researchEnvironmental Chemistry and AnalysisToxic Organic Pollutants Impact

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Quantitative Determination of Fluorotelomer Sulfonates in Groundwater by LC MS/MS

Schultz, Melissa M., Barofsky, Douglas F., Field, Jennifer A.·2004·Environmental Science & Technology

DOI 10.1021/es035031j

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Abstract

Aqueous film-forming foams (AFFF) are complex mixtures containing fluorocarbon- and hydrocarbon-based surfactants that are used to fight hydrocarbon-fueled fires. The military is the largest consumer of AFFF in the United States, and fire-training activities conducted at military bases have led to groundwater contamination by unspent fuels and AFFF chemicals. A direct-injection, liquid-chromatography tandem mass spectrometry (LC MS/MS) method was developed to quantify a suite of fluorotelomer sulfonate surfactants in groundwater collected from military bases where fire-training activities were conducted. The 4:2, 6:2, and 8:2 fluorotelomer sulfonates were detected and quantified in groundwater from two of the three military bases. The total fluorotelomer sulfonate concentrations observed at Wurtsmith AFB, MI, and Tyndall AFB, FL, ranged respectively from below quantitation (< or = 0.60) to 182 microg/L and from 1100 to 14,600 microg/L. Analyses of a fluorotelomer-based AFFF concentrate by negative ion fast atom bombardment/mass spectrometry and LC MS/MS analyses indicate that the AFFF concentrate contains only a small amount of fluorotelomer sulfonates and that fluoroalkylthioamido sulfonates are the main anionic fluorosurfactant in the mixtures. More research is needed to determine the fate of fluoroalkylthioamido sulfonates in the environment.

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Biomonitoring of perfluorochemicals and toxicity to the downstream fish community of Etobicoke Creek following deployment of aqueous film-forming foam
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Sonochemical degradation of perfluorinated chemicals in aqueous film-forming foams
Rodríguez-Freire, L., Abad-Fernández, N., Sierra‐Álvarez, R., Hoppe‐Jones, C., Peng, H., Giesy, J. P., Snyder, S. A., & Keswani, M. (2016) · Journal of Hazardous Materials · doi:10.1016/j.jhazmat.2016.05.078 · Cited by 78
Exploring the Prospects and Challenges of Fluorine-Free Firefighting Foams (F3) as Alternatives to Aqueous Film-Forming Foams (AFFF): A Review
Jahura, F. T., Mazumder, N., Hossain, M. T., Kasebi, A., Girase, A., & Ormond, R. B. (2024) · ACS Omega · doi:10.1021/acsomega.4c03673 · Cited by 81
Geographical Distribution of Perfluorinated Compounds in Fish from Minnesota Lakes and Rivers
Delinsky, A. D., Strynar, M. J., McCann, P. J., Varns, J. L., McMillan, L., Nakayama, S. F., & Lindstrom, A. B. (2010) · Environmental Science & Technology · doi:10.1021/es903777s · Cited by 77
Contribution of selected perfluoroalkyl and polyfluoroalkyl substances to the adsorbable organically bound fluorine in German rivers and in a highly contaminated groundwater
Willach, S., Brauch, H.-J., & Lange, F. T. (2016) · Chemosphere · doi:10.1016/j.chemosphere.2015.11.113 · Cited by 71
Removing emerging perfluoroalkyl ether acids and fluorotelomer sulfonates from water by nanofiltration membranes: Insights into performance and underlying mechanisms
Zhi, Y., Zhao, X., Qian, S., de Faria, A. F., Lu, X., Wang, X., Li, W., Han, L., Tao, Z., He, Q., et al. (2022) · Separation and Purification Technology · doi:10.1016/j.seppur.2022.121648 · Cited by 77
Perfluorinated compounds (PFCs) in groundwater and aqueous soil extracts: using inline SPE-LC-MS/MS for screening and sorption characterisation of perfluorooctane sulphonate and related compounds
Enevoldsen, R., & Juhler, R. K. (2010) · Analytical and Bioanalytical Chemistry · doi:10.1007/s00216-010-4066-0 · Cited by 76
Evaluation and Management Strategies for Per- and Polyfluoroalkyl Substances (PFASs) in Drinking Water Aquifers: Perspectives from Impacted U.S. Northeast Communities
Guelfo, J. L., Marlow, T., Klein, D. M., Savitz, D. A., Frickel, S., Crimi, M., & Suuberg, E. M. (2018) · Environmental Health Perspectives · doi:10.1289/ehp2727 · Cited by 73
“…past 20 y in utilizing liquid chromatography tandem mass spectrometry (LC-MS/MS) techniques (and gas chromatographic techniques for volatile PFASs such as fluorotelomer alcohols) for PFAS analysis (e.g., Mahmoud et al. 2009; Moody et al. 2001; Schultz et al. 2004), significant challenges remain.”
BackgroundMethod
Evaluating the sub-lethal toxicity of PFOS and PFOA using rotifer Brachionus calyciflorus
Zhang, L., Niu, J., Li, Y., Wang, Y., & Sun, D. (2013) · Environmental Pollution · doi:10.1016/j.envpol.2013.04.031 · Cited by 78
Determination of polyfluoroalkyl compounds in water and suspended particulate matter in the river Elbe and North Sea, Germany
Ahrens, L., Plassmann, M. M., Xie, Z., & Ebinghaus, R. (2009) · 中国环境科学与工程前沿：英文版 · doi:10.1007/s11783-009-0021-8 · Cited by 73
“The source of 6:2 FTS could be aqueous film-forming foams (AFFF) used to fight hydrocarbon-fueled fire [29].”
Background
Investigating sources and pathways of perfluoroalkyl acids (PFAAs) in aquifers in Tokyo using multiple tracers
Kuroda, K., Murakami, M., Oguma, K., Takada, H., & Takizawa, S. (2014) · The Science of The Total Environment · doi:10.1016/j.scitotenv.2014.04.066 · Cited by 75
Sorption of per- and polyfluoroalkyl substances (PFASs) on filter media: Implications for phase partitioning studies
Chandramouli, B., Benskin, J. P., Hamilton, M. C., & Cosgrove, J. R. (2014) · Environmental Toxicology and Chemistry · doi:10.1002/etc.2751 · Cited by 72
“These substances have been detected at elevated concentrations in groundwater near airports and military bases [22] and can transform into PFCAs [23].”
Background
Aerobic biotransformation of 6:2 fluorotelomer sulfonate in soils from two aqueous film-forming foam (AFFF)-impacted sites
Yan, P.-F., Dong, S., Manz, K. E., Woodcock, M. J., Liu, C., Mezzari, M. P., Abriola, L. M., Pennell, K. D., & Cápiro, N. L. (2023) · Water Research · doi:10.1016/j.watres.2023.120941 · Cited by 73
Bioconcentration of Aqueous Film-Forming Foam (AFFF) in Juvenile Rainbow Trout (Oncorhyncus mykiss)
Yeung, L. W. Y., & Mabury, S. A. (2013) · Environmental Science & Technology · doi:10.1021/es403170f · Cited by 71
Trace analysis of environmental matrices by large-volume injection and liquid chromatography–mass spectrometry
Busetti, F., Backe, W. J., Bendixen, N., Maier, U., Place, B. J., Giger, W., & Field, J. A. (2011) · Analytical and Bioanalytical Chemistry · doi:10.1007/s00216-011-5290-y · Cited by 70
Impact of Long-Term Perfluorooctanoic Acid (PFOA) Exposure on Activated Sludge Process
Yu, X., Nishimura, F., & Hidaka, T. (2018) · Water Air & Soil Pollution · doi:10.1007/s11270-018-3760-y · Cited by 71
Poly- and Perfluoroalkyl Substances in Runoff Water and Wastewater Sampled at a Firefighter Training Area
Dauchy, X., Boiteux, V., Colin, A., Bach, C., Rosin, C., & Munoz, J.-F. (2019) · Archives of Environmental Contamination and Toxicology · doi:10.1007/s00244-018-0585-z · Cited by 69
Determination of Perfluorinated Compounds in Packaging Materials and Textiles Using Pressurized Liquid Extraction with Gas Chromatography-Mass Spectrometry
Lv, G., Wang, L., Liu, S., & Li, S. (2009) · Analytical Sciences · doi:10.2116/analsci.25.425 · Cited by 67
Experimental investigations of Per- and Poly-fluoroalkyl substances (PFAS) degradation by non-thermal plasma in aqueous solutions
Alam, D., Lee, S., Hong, J., Fletcher, D. F., McClure, D. D., Cook, D., Cullen, P. J., & Kavanagh, J. M. (2023) · Journal of environmental chemical engineering · doi:10.1016/j.jece.2023.111588 · Cited by 67
“The use of Aqueous Film Forming Foam (AFFFs), which historically contained PFAS, has also contributed to extensive environmental pollution as these were commonly used to extinguish hydrocarbon-fuel fires at military bases, airports and firefighting training facilities worldwide [11].”
Relationship Between Industrial Discharges and Contamination of Raw Water Resources by Perfluorinated Compounds. Part I: Case Study of a Fluoropolymer Manufacturing Plant
Dauchy, X., Boiteux, V., Rosin, C., & Munoz, J.-F. (2012) · Bulletin of Environmental Contamination and Toxicology · doi:10.1007/s00128-012-0704-x · Cited by 66
“They may also be directly released during manufacture, application, use, and disposal (Lin et al. 2009; Ruan et al. 2010; Schultz et al. 2004; Skutlarek et al. 2006; Yoo et al. 2010).”
Background
Spatio-temporal dynamics of per and polyfluoroalkyl substances (PFASs) and transfer to periphytic biofilm in an urban river: case-study on the River Seine
Munoz, G., Fechner, L. C., Geneste, E., Pardon, P., Budzinski, H., & Labadie, P. (2018) · Environmental Science and Pollution Research · doi:10.1007/s11356-016-8051-9 · Cited by 64
“6:2 FTSA is often associated with industrial sites or areas impacted by firefighting trainings (Schultz et al. 2004; Backe et al. 2013; Ahrens et al. 2015; Munoz et al. 2015), and may biodegrade to short-chain PFCAs (Liu and Mejia Avendaño 2013).”
Background
Toxic effect of perfluorooctane sulfonate on plants in vertical-flow constructed wetlands
Li, R., Tang, T., Qiao, W., & Huang, J. G. (2020) · Journal of Environmental Sciences · doi:10.1016/j.jes.2020.02.018 · Cited by 66
Quantification of pharmaceuticals, personal care products, and perfluoroalkyl substances in the marine sediments of Puget Sound, Washington, USA
Long, E. R., Dutch, M., Weakland, S., Chandramouli, B., & Benskin, J. P. (2013) · Environmental Toxicology and Chemistry · doi:10.1002/etc.2281 · Cited by 68
“In the United States, highly elevated levels of PFOS have been reported in groundwater near Naval Air Station Fallon (up to 380 mg/L), Tyndall Air Force Base (up to 2300 mg/L) and Wurtsmith Air Force Base (up to 110 mg/L) [50,51].”
Background
Towards deployable electrochemical sensors for per- and polyfluoroalkyl substances (PFAS)
Clark, R. B., & Dick, J. E. (2021) · Chemical Communications · doi:10.1039/d1cc02641k · Cited by 65
Sorption of Perfluoroalkyl Acids to Fresh and Aged Nanoscale Zerovalent Iron Particles
Zhang, Y., Zhi, Y., Liu, J., & Ghoshal, S. (2018) · Environmental Science & Technology · doi:10.1021/acs.est.8b00487 · Cited by 62
Removing per- and polyfluoroalkyl substances (PFAS) in water by foam fractionation
Wang, Y., Ji, Y., Tishchenko, V., & Huang, Q. (2022) · Chemosphere · doi:10.1016/j.chemosphere.2022.137004 · Cited by 64
Performance and mechanisms for removal of perfluorooctanoate (PFOA) from aqueous solution by activated carbon fiber
Wang, Y., Niu, J., Li, Y., Zheng, T., Xu, Y., & Liu, Y. (2015) · RSC Advances · doi:10.1039/c5ra15853b · Cited by 63
Effects of water matrix on per- and poly-fluoroalkyl substances (PFAS) treatment: Physical-separation and degradation processes – A review
Zeidabadi, F. A., Esfahani, E. B., & Mohseni, M. (2023) · Journal of Hazardous Materials Advances · doi:10.1016/j.hazadv.2023.100322 · Cited by 61
Per- and Polyfluoroalkyl Substances, Epigenetic Age and DNA Methylation: A Cross-Sectional Study of Firefighters
Goodrich, J. M., Calkins, M. M., Caban-Martinez, A. J., Stueckle, T. A., Grant, C. C., Calafat, A. M., Nematollahi, A., Jung, A. M., Graber, J. M., Jenkins, T. G., et al. (2021) · Epigenomics · doi:10.2217/epi-2021-0225 · Cited by 62
Determination of perfluorooctanesulfonate and perfluorooctanoic acid in sewage sludge samples using liquid chromatography/quadrupole time-of-flight mass spectrometry
GUO, R., Zhou, Q., Cai, Y., & JIANG, G. (2008) · Talanta · doi:10.1016/j.talanta.2008.01.052 · Cited by 61
Endocrine disruption effects of long-term exposure to perfluorodecanoic acid (PFDA) and perfluorotridecanoic acid (PFTrDA) in zebrafish (Danio rerio) and related mechanisms
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“However, since PFAAs can be occurring often at mg L 1 levels in waters near industrial point sources (Schultz et al., 2004), and are persistent in aquatic environment, their long-term effects at lower water concentrations should not be ignored.”
Background
Genomic and proteomic characterization of gordonia sp. NB4-1Y in relation to 6: 2 fluorotelomer sulfonate biodegradation
Van Hamme, J. D., Bottos, E. M., Bilbey, N. J., & Brewer, S. E. (2013) · Microbiology · doi:10.1099/mic.0.068932-0 · Cited by 66
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Background
Human placental transfer of perfluoroalkyl acid precursors: Levels and profiles in paired maternal and cord serum
Yang, L., Wang, Z., Shi, Y., Li, J., Wang, Y., Zhao, Y., Wu, Y., & Cai, Z. (2015) · Chemosphere · doi:10.1016/j.chemosphere.2015.10.063 · Cited by 61
Density Functional Theory Calculations Decipher Complex Reaction Pathways of 6:2 Fluorotelomer Sulfonate to Perfluoroalkyl Carboxylates Initiated by Hydroxyl Radical
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Removal of PFAS from aqueous solution using PbO2 from lead-acid battery
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Per- and polyfluoroalkyl substances (PFASs) in contaminated coastal marine waters of the Saudi Arabian Red Sea: a baseline study
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Occurrence and fate of legacy and novel per- and polyfluoroalkyl substances (PFASs) in freshwater after an industrial fire of unknown chemical stockpiles
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Fluence-based photo-reductive decomposition of PFAS using vacuum UV (VUV) irradiation: Effects of key parameters and decomposition mechanism
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Removal of perfluorooctane sulfonates from water by a hybrid coagulation–nanofiltration process
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“3 mg/L due to the use of aqueous film-forming foams [15].”
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Perfluorooctane sulfonate (PFOS) removal with Pd0/nFe0 nanoparticles: Adsorption or aqueous Fe-complexation, not transformation?
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Is the phase-out of long-chain PFASs measurable as fingerprint in a defined area? Comparison of global PFAS concentrations and a monitoring study performed in Hesse, Germany from 2014 to 2018
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Temporal Trends (1981–2013) of Per- and Polyfluoroalkyl Substances and Total Fluorine in Baltic cod ( Gadus morhua )
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Contribution of Nonaqueous-Phase Liquids to the Retention and Transport of Per and Polyfluoroalkyl Substances (PFAS) in Porous Media
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Fate and Transformation of 6:2 Fluorotelomer Sulfonic Acid Affected by Plant, Nutrient, Bioaugmentation, and Soil Microbiome Interactions
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Authors: Schultz, M. M., Barofsky, D. F., & Field, J. A.
Affiliations: Oregon State University (US)
Corresponding author: Field, Jennifer A.
ORCID: Barofsky, Douglas F.
Field, Jennifer A.
Venue: Environmental Science & Technology
Publisher: American Chemical Society (ACS)
Published: 2004-02-04
Volume: 38
Issue: 6
Pages: 1828-1835
ISSN: 0013-936X (ISSN-L)
1520-5851
DOI: 10.1021/es035031j
OpenAlex: W2067287961
Semantic Scholar: 53d890af0ea89834be554f0b6ff22bea4293c383
Cited by: 373
References: 13
Citations by year: 2026: 18 · 2025: 24 · 2024: 21 · 2023: 30 · 2022: 28 · 2021: 26 · 2020: 24 · 2019: 14 · 2018: 15 · 2017: 22 · 2016: 17 · 2015: 18 · 2014: 15 · 2013: 21 · 2012: 7
FWCI: 6.69
Type: journal article
Language: en
Open access: closed
Locations: Environmental Science & Technology (publishedVersion)
PubMed (publishedVersion)
Funders: Oregon State University
National Institutes of Health (5p30es000210-46)
National Institute of Environmental Health Sciences (#P30-ES00210)
Topics: Physical Sciences › Environmental Science › Environmental Chemistry › Per- and polyfluoroalkyl substances research
Physical Sciences › Environmental Science › Environmental Chemistry › Environmental Chemistry and Analysis
Physical Sciences › Environmental Science › Health, Toxicology and Mutagenesis › Toxic Organic Pollutants Impact
Keywords: fluorotelomer sulfonates, aqueous film-forming foam, groundwater contamination, military installations, fire training, fluorosurfactants, Tyndall Air Force Base
MeSH terms: Alkanesulfonates, Environmental Monitoring, Fluorocarbons, Mass Spectrometry, Surface-Active Agents

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Quantitative Determination of Fluorotelomer Sulfonates in Groundwater by LC MS/MS

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