Development, validation, and application of a new method for the quantitative determination of monohydrogen-substituted perfluoroalkyl carboxylic acids (H–PFCAs) in surface water
Open accessAbstract
Per- and polyfluoroalkyl substances (PFASs) are a large and diverse class of chemicals. While some have been phased out internationally due to concerns over their human and environmental health risks, novel alternative PFASs continue to be manufactured and detected in environmental samples. The occurrence and fate of these alternatives remain poorly understood. The present study investigated the occurrence of an emerging class of PFAS alternative, the monohydrogen-substituted perfluoroalkyl carboxylic acids (H–PFCAs), in conjunction with the more well-known PFCAs. A weak anion exchange solid phase extraction-liquid chromatography tandem mass spectrometry method for quantitative determination of H–PFCAs in surface water was developed, validated, and applied on samples collected from the Netherlands. To improve chromatography, especially for short-chain (H-)PFCAs, an ion-pairing agent, tetrabutylammonium hydrogen sulphate, was used. The method was validated for linearity (R2 > 0.99), instrumental detection limits (0.01–0.09 ng/mL), method detection limits (0.03–0.75 ng/mL), matrix effects (<20%), percent absolute- and relative recovery (57–121%), trueness (130-80%), repeatability (<20%), and within-lab reproducibility (<20%). Eleven out of fourteen PFASs showed acceptable results. Application of the newly validated method to surface water throughout the Netherlands revealed trace levels of H–PFCAs (including two new H–PFCAs) and high concentrations of PFCAs.
The claims and statistics of this paper haven’t been checked yet.
Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
The claims and statistics of this paper haven’t been checked yet.
Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.
Claims other papers make about this one
Each is checked against this paper’s own text: does it say what the citing paper says it does?
Among H-PFCAs, 7H-PFHpA was quantified in one out of eleven surface water samples at 0.3 ng/L, whereas 9H-PFNA was not detected; 4H-PFBA was most frequently detected at 1.4-2.0 ng/L.
“Among these, 7H-PFHpA was quantified in one out of eleven surface water samples at a concentration of 0.3 ng/L, whereas 9H-PFNA was not detected in any of the analyzed samples. The most frequently detected compound was 4H-PFBA, with concentrations ranging between 1.4 and 2.0 ng/L [44].”
From Integrated Targeted and Suspect Screening Workflow for Identifying PFAS of Concern in Urban-Impacted Serbian Rivers (2026) · cites this paper as [44]
Split into 2 atoms — 1 confirmed, 1 partially supported, 0 disputed, 0 misattributed, 0 unverifiable. Expand the claim to see per-atom verdicts.
Experimental — accuracy not yet measuredPrevious research reported the occurrence of H-PFCAs in surface waters from the Netherlands.
“Previous research has reported the occurrence of H–PFCAs in surface waters from the Netherlands [44].”
From Integrated Targeted and Suspect Screening Workflow for Identifying PFAS of Concern in Urban-Impacted Serbian Rivers (2026) · cites this paper as [44]
Recent studies indicate that replacement PFAS may still exhibit considerable environmental persistence and potentially cause equal or even stronger adverse effects than legacy PFAS.
“recent studies have indicated that they may still exhibit considerable environmental persistence and potentially cause equal or even stronger adverse effects than legacy PFAS [44].”
From Integrated Targeted and Suspect Screening Workflow for Identifying PFAS of Concern in Urban-Impacted Serbian Rivers (2026) · cites this paper as [44]
Self-check
Percentages, sums and reported differences re-computed from the paper’s own numbers.
The self-check needs the paper’s full text.
Cites
Buck, R. C., Franklin, J., Berger, U., Conder, J. M., Cousins, I. T., de Voogt, P., Jensen, A. A., Kannan, K., Mabury, S. A., & van Leeuwen, S. P. (2011) · Integrated Environmental Assessment and Management · doi:10.1002/ieam.258 · Cited by 4,641 · see citing works
An overview of the uses of per- and polyfluoroalkyl substances (PFAS)
Glüge, J., Scheringer, M., Cousins, I. T., DeWitt, J. C., Goldenman, G., Herzke, D., Lohmann, R., Ng, C. A., Trier, X., & Wang, Z. (2020) · Environmental Science: Processes & Impacts · doi:10.1039/d0em00291g · Cited by 2,466 · see citing works
Risk to human health related to the presence of perfluoroalkyl substances in food
Panel), E. P. O. C. I. T. F. C. (. C., Schrenk, D., Bignami, M., Bodin, L., Chipman, J. K., del Mazo, J., Grasl‐Kraupp, B., Hogstrand, C., Hoogenboom, L. (., Leblanc, J., et al. (2020) · EFSA Journal · doi:10.2903/j.efsa.2020.6223 · Cited by 989 · see citing works
Li, F., Duan, J., Tian, S., Ji, H., Zhu, Y., Wei, Z., & Zhao, D. (2020) · Chemical Engineering Journal · doi:10.1016/j.cej.2019.122506 · Cited by 707 · see citing works
Xiao, F. (2017) · Water Research · doi:10.1016/j.watres.2017.07.024 · Cited by 634 · see citing works
Gebbink, W. A., van Asseldonk, L., & van Leeuwen, S. P. J. (2017) · Environmental Science & Technology · doi:10.1021/acs.est.7b02488 · Cited by 438 · see citing works
Self-citationGaballah, S., Swank, A., Sobus, J. R., Howey, X. M., Schmid, J., Catron, T., McCord, J., Hines, E., Strynar, M., & Tal, T. (2020) · Environmental Health Perspectives · doi:10.1289/ehp5843 · Cited by 437 · see citing works
Toxicological Effects of Perfluoroalkyl and Polyfluoroalkyl Substances
(2015) · Molecular and Integrative Toxicology · doi:10.1007/978-3-319-15518-0 · Cited by 360 · see citing works
Sheng, N., Cui, R., Wang, J., Guo, Y., Wang, J., & Dai, J. (2018) · Archives of Toxicology · doi:10.1007/s00204-017-2055-1 · Cited by 295 · see citing works
Wang, Y., Yu, N., Zhu, X., Guo, H., Jiang, J., Wang, X., Shi, W. F., Wu, J., Yu, H., & Wei, S. (2018) · Environmental Science & Technology · doi:10.1021/acs.est.8b03030 · Cited by 219 · see citing works
Newton, S., McMahen, R., Stoeckel, J. A., Chislock, M., Lindstrom, A., & Strynar, M. (2017) · Environmental Science & Technology · doi:10.1021/acs.est.6b05330 · Cited by 217 · see citing works
Liu, Y., Pereira, A. D. S., & Martin, J. W. (2015) · Analytical Chemistry · doi:10.1021/acs.analchem.5b00039 · Cited by 209 · see citing works
Zhang, C., Hopkins, Z. R., McCord, J., Strynar, M. J., & Knappe, D. R. U. (2019) · Environmental Science & Technology Letters · doi:10.1021/acs.estlett.9b00525 · Cited by 202 · see citing works
Song, X., Vestergren, R., Shi, Y., Huang, J. G., & Cai, Y. (2018) · Environmental Science & Technology · doi:10.1021/acs.est.7b06657 · Cited by 200 · see citing works
Li, Y., Yu, N., Du, L., Shi, W. F., Yu, H., Song, M., & Wei, S. (2020) · Environmental Science & Technology · doi:10.1021/acs.est.9b06505 · Cited by 143 · see citing works
Krippner, J., Falk, S., Brunn, H., Georgii, S., Schubert, S., & Stahl, T. (2015) · Journal of Agricultural and Food Chemistry · doi:10.1021/acs.jafc.5b00012 · Cited by 143 · see citing works
Fromme, H., Wöckner, M., Roscher, E., & Völkel, W. (2017) · International Journal of Hygiene and Environmental Health · doi:10.1016/j.ijheh.2016.12.014 · Cited by 104 · see citing works
Barrett, H., Du, X., Houde, M., Lair, S., Verreault, J., & Peng, H. (2021) · Environmental Science & Technology · doi:10.1021/acs.est.0c05957 · Cited by 96 · see citing works
Esparza, X., Moyano, E., de Boer, J., Galcerán, M. T., & van Leeuwen, S. P. J. (2011) · Talanta · doi:10.1016/j.talanta.2011.09.024 · Cited by 69 · see citing works
Washington, J. W., Jenkins, T. M., & Weber, E. J. (2015) · Environmental Science & Technology · doi:10.1021/acs.est.5b03379 · Cited by 50 · see citing works
Hensema, T. J., Berendsen, B. J. A., & van Leeuwen, S. P. J. (2020) · Chemosphere · doi:10.1016/j.chemosphere.2020.128599 · Cited by 45 · see citing works
Self-citationLiu, J., Li, C., Qu, R., Wang, L., Feng, J., & Wang, Z. (2018) · Chemical Engineering Journal · doi:10.1016/j.cej.2018.05.055 · Cited by 39 · see citing works
The analysis of perfluoroalkyl substances at ppt level in milk and egg using UHPLC-MS/MS
Berendsen, B. J. A., Lakraoui, F., Leenders, L., & van Leeuwen, S. P. J. (2020) · Food Additives & Contaminants Part A · doi:10.1080/19440049.2020.1794053 · Cited by 32 · see citing works
Self-citation
Flagged first, then by citations
Research works printed but not linked: 1
- EU, 2002, 2002/657/EC: commission Decision of 12 August 2002 implementing Council Directive 96/23/EC concerning the performance of analytical methods and the interpretation of results, Official Journal of the European Communities
Cited by
Sorted by citations
Harris, K. J., Munoz, G., Woo, V. H. K., Sauvé, S., & Rand, A. A. (2022) · Environmental Science & Technology · doi:10.1021/acs.est.2c02660 · Cited by 106 · see citing works
Recent progress in per- and polyfluoroalkyl substances (PFAS) sensing: A critical mini-review
Thompson, D., Zolfigol, N., Xia, Z., & Lei, Y. (2024) · Sensors and Actuators Reports · doi:10.1016/j.snr.2024.100189 · Cited by 69 · see citing works
Wang, D., Liu, X., Guo, Z., Shan, W., Yang, Z., Chen, Y., Ju, F., & Zhang, Y. (2024) · Environmental Science & Technology · doi:10.1021/acs.est.4c05913 · Cited by 60 · see citing works
Ogunbiyi, O. D., Ajiboye, T. O., Omotola, E. O., Oladoye, P. O., Olanrewaju, C. A., & Quinete, N. (2023) · Environmental Pollution · doi:10.1016/j.envpol.2023.121705 · Cited by 44 · see citing works
Koronaiou, L.-A., Nannou, C. I., Xanthopoulou, N. J., Seretoudi, G., Bikiaris, D. Ν., & Lambropoulou, D. A. (2022) · Microchemical Journal · doi:10.1016/j.microc.2022.107457 · Cited by 42 · see citing works
Ismail, U. M., Elnakar, H., & Khan, M. F. (2023) · Toxics · doi:10.3390/toxics11040335 · Cited by 40 · see citing works
Analytical methodologies and occurrence of per- and polyfluorinated alkyl substances – A review
Jiménez-Skrzypek, G., González‐Sálamo, J., & Hernández‐Borges, J. (2023) · Journal of Chromatography Open · doi:10.1016/j.jcoa.2023.100089 · Cited by 32 · see citing works
Per- and Poly-Fluoroalkyl Substances in Portuguese Rivers: Spatial-Temporal Monitoring
Barbosa, M. O., Ratola, N., Homem, V., Pereira, M. F. R., Silva, A. M. T., Ribeiro, A. R. L., Llorca, M., & Farré, M. (2023) · Molecules · doi:10.3390/molecules28031209 · Cited by 26 · see citing works
“The second class (in green) presents centroids at slightly higher levels and groups the studies of France, Spain, Italy, The Netherlands and some results from Sweden and Austria.”
BackgroundKang, D., Yun, D., Cho, K. H., Baek, S., & Jeon, J. (2024) · Chemosphere · doi:10.1016/j.chemosphere.2024.141402 · Cited by 27 · see citing works
Shanbhag, M. M., Shetti, N. P., Daouli, A., Nadagouda, M. N., Badawi, M., & Aminabhavi, T. M. (2024) · Langmuir · doi:10.1021/acs.langmuir.3c03666 · Cited by 25 · see citing works
Zango, Z. U., Ethiraj, B., Al‐Mubaddel, F. S., Alam, M. M., Lawal, M. A., Kadir, H. A., Khoo, K. S., Garba, Z. N., Usman, F., Zango, M. U., et al. (2023) · Environmental Research · doi:10.1016/j.envres.2023.116102 · Cited by 25 · see citing works
Haque, F., Soerensen, A. L., Sköld, M., Awad, R., Spaan, K. M., Lauria, M. Z., Plassmann, M. M., & Benskin, J. P. (2023) · Environmental Science Processes & Impacts · doi:10.1039/d3em00141e · Cited by 22 · see citing works
“Hydrogen-substituted PFAAs have been previously reported in surface water, 77,78 sediment, 17 human blood 79 and biota, 33 but the dominant congener has varied depending on matrix ( e.g. H-PFDA and H-PFDoDA were dominant in blood, 79 while H-PFHxA was dominant in sediment 17 ).”
Self-citationChokwe, T. B., Themba, N., Mahlambi, P. N., Mngadi, S. V., & Sibali, L. L. (2024) · Environmental Science and Pollution Research · doi:10.1007/s11356-024-35727-z · Cited by 17 · see citing works
Dalmijn, J., Shafer, J. J., Benskin, J. P., Salter, M. E., Johansson, J. H., & Cousins, I. T. (2025) · Environmental Science & Technology · doi:10.1021/acs.est.4c13943 · Cited by 17 · see citing works
Self-citationSun, J., Liu, Y., Yao, L.-L., Guo, Y., Ma, C., Xiang, T., Cheng, Z., Deng, Y., Xie, X., Qu, G., et al. (2025) · Environmental Science & Technology · doi:10.1021/acs.est.4c09020 · Cited by 16 · see citing works
Quan, H., Ji, F., Zhong, Z., Li, R., & Lü, H. (2025) · Journal of Hazardous Materials · doi:10.1016/j.jhazmat.2025.140184 · Cited by 13 · see citing works
Li, S., Wang, Q., Lyu, L., & Leng, J. (2025) · Microchemical Journal · doi:10.1016/j.microc.2025.113789 · Cited by 12 · see citing works
Per- and polyfluorinated substances: An environmental update
Falandysz, J., Jiménez, B., & Taniyasu, S. (2021) · Chemosphere · doi:10.1016/j.chemosphere.2021.132876 · Cited by 12 · see citing works
Barola, C., Bucaletti, E., Moretti, S., Buiarelli, F., Simonetti, G., Lucarelli, F., Goracci, L., Lorenzetti, S., Filippo, P. D., Pomata, D., et al. (2023) · Separations · doi:10.3390/separations10110547 · Cited by 12 · see citing works
Engelhardt, J. A., Plassmann, M. M., & Weiss, J. M. (2024) · Environment International · doi:10.1016/j.envint.2024.109214 · Cited by 8 · see citing works
Boragave, V. A., Khouqeer, G. A., Sreenivasulu, M., AbdelAll, N., Alodhayb, A. N., & Shetti, N. P. (2025) · Electrochimica Acta · doi:10.1016/j.electacta.2025.147343 · Cited by 7 · see citing works
Antić, I., Buljovčić, M., Cochran, R. E., Živančev, J., Llorca, M., Farré, M., Rakić, D., Tautenhahn, R., & Đurišić-Mladenović, N. (2026) · Toxics · doi:10.3390/toxics14010078 · Cited by 3 · see citing works
“Although these substitutes were developed with the intention of being less bioaccumulative and toxic, recent studies have indicated that they may still exhibit considerable environmental persistence and potentially cause equal or even stronger adverse effects than legacy PFAS [44].”
InfluentialXie, H., Gu, S., Cui, Y., Dong, J., Wang, H., & Fu, G. (2025) · Journal of Environmental Sciences · doi:10.1016/j.jes.2025.06.021 · Cited by 3 · see citing works
Analysis of needs for enforcement of PFAS in articles and chemical products
Krause, M., Stoesser, J., de Carvalho, A. R., Hanozin, E., Jacobs, G., Voorspoels, S., & Polcher, A. (2024) · TemaNord · doi:10.6027/temanord2024-510 · Cited by 3 · see citing works
Liu, X., Zhao, L., Hong, A.-B., Zhuang, L., Lu, Q., Wang, B., Min, W., & Chen, D. (2023) · Chinese Science Bulletin (Chinese Version) · doi:10.1360/tb-2023-0129 · Cited by 2 · see citing works
Akhtar, N., Iqbal, A., Javid, A., & Tayyab, M. (2025) · International Journal of Environmental Research · doi:10.1007/s41742-025-00843-2
“Hydrogen substituted perfluoroalkyl carboxylic acids abbreviated as H–PFCAs are emerging PFAS substitutes in the natural environment.”
Současný stav sledování vybraných PFAS v povrchových vodách v České republice
Marešová, D., Očenášková, V., Mičaník, T., Pospíchalová, D., Juranová, E., Bohadlová, E., & Chrastina, D. (2025) · Vodohospodářské technicko-ekonomické informace · doi:10.46555/vtei.2025.09.004
Lei, S., Shang, M., Dong, J., Wen, W., Xie, H., Cui, Y., & Wu, C. (2026) · Journal of Environmental Sciences · doi:10.1016/j.jes.2026.03.050
- Authors
- Awchi, M., Gebbink, W. A., Berendsen, B. J. A., Benskin, J. P., & van Leeuwen, S. P. J.
- Affiliations
- Wageningen University & Research (NL)
- Stockholm University (SE)
- Venue
- Chemosphere
- Publisher
- Elsevier BV
- Published
- 2022-01
- Volume
- 287
- Issue
- Pt 2
- Pages
- 132143
- ISSN
- 0045-6535 (ISSN-L)
- OpenAlex
- W3196408600
- Semantic Scholar
- a91fe0d3be499066cfcd47c0cb3ad6eb225891a8
- Cited by
- 28
- References
- 23
- Citations by year
- 2026: 2 · 2025: 8 · 2024: 7 · 2023: 8 · 2022: 2 · 2021: 1
- FWCI
- 1.70
- Type
- journal article
- Language
- en
- Open access
- hybrid
- doi.org
- Licence
- Locations
- Chemosphere (publishedVersion, cc-by)
- PubMed (publishedVersion)
- Socio-Environmental Systems Modeling (acceptedVersion, cc-by)
- Data Archiving and Networked Services (DANS) (submittedVersion, cc-by)
- Topics
- Physical Sciences › Environmental Science › Environmental Chemistry › Per- and polyfluoroalkyl substances research
- Life Sciences › Pharmacology, Toxicology and Pharmaceutics › Pharmaceutical Science › Fluorine in Organic Chemistry
- Physical Sciences › Environmental Science › Environmental Chemistry › Environmental Chemistry and Analysis
- Keywords
- per- and polyfluoroalkyl substances, PFAS alternatives, surface water contamination, ion-pairing agents, short-chain PFASs, emerging contaminants, method validation
- MeSH terms
- Carboxylic Acids, Environmental Monitoring, Fluorocarbons, Humans, Water, Water Pollutants, Chemical, Reproducibility of Results
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review
