Discovery of C 5 –C 17 Poly- and Perfluoroalkyl Substances in Water by In-Line SPE-HPLC-Orbitrap with In-Source Fragmentation Flagging
Abstract
The presence of unknown organofluorine compounds in environmental samples has prompted the development of nontargeted analytical methods capable of detecting new perfluoroalkyl and polyfluoroalkyl substances (PFASs). By combining high volume injection with high performance liquid chromatography (HPLC) and ultrahigh resolution Orbitrap mass spectrometry, a sensitive (0.003-0.2 ng F/mL for model mass-labeled PFASs) untargeted workflow was developed for discovery and characterization of novel PFASs in water. In the first step, up to 5 mL of water is injected to in-line solid phase extraction, chromatographed by HPLC, and detected by electrospray ionization with mass spectral acquisition in parallel modes cycling back and forth: (i) full scan with ultrahigh resolving power (RP = 120,000, mass accuracy ≤3 ppm), and (ii) in-source fragmentation flagging scans designed to yield marker fragment ions including [C2F5](-) (m/z 118.992), [C3F7](-) (m/z 168.988), [SO4H](-) (m/z 96.959), and [Cl](-) (m/z 34.9). For flagged PFASs, plausible empirical formulas were generated from accurate masses, isotopic patterns, and fragment ions. In the second step, another injection is made to collect high resolution MS/MS spectra of suspect PFAS ions, allowing further confirmation of empirical formulas while also enabling preliminary structural characterization. The method was validated by applying it to an industrial wastewater, and 36 new PFASs were discovered. Of these, 26 were confidently assigned to 3 new PFAS classes that have not previously been reported in the environment: polyfluorinated sulfates (CnFn+3Hn-2SO4(-); n = 5, 7, 9, 11, 13, and 15), chlorine substituted perfluorocarboxylates (ClCnF2nCO2(-); n = 4-11), and hydro substituted perfluorocarboxylates (HCnF2nCO2(-); n = 5-16). Application of the technique to environmental water samples is now warranted.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
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?
Pairing HPLC to on-line SPE had multiple benefits including high speed, high recovery, minimizing contamination, and high sensitivity by allowing large volumes to be extracted and immediately directed to the HPLC-HRMS instrument.
“This had multiple related benefits, including high speed, high recovery, minimizing contamination, and high sensitivity by allowing large volumes to be extracted and immediately directed (up to 5 mL) to the HPLC-HRMS instrument [34].”
TOF, Orbitrap, and FTICR are three HRMS technologies already proven as useful tools in PFAS discovery.
“TOF [29e32,35,39e41], Orbitrap [34,37,38,42] and Fouriertransform ion cyclotron resonance (FTICR) [30] are three HRMS technologies already proven as useful tools in PFAS discovery.”
Several studies have reported replacement PFASs in manufacturing wastewater or in river water downstream of manufacturing sites, with concentrations estimated in the microgram per liter range.
“several studies have reported on the presence of replacement PFASs in wastewater from manufacturing sites or in river water collected downstream from them, with concentrations estimated in the μg/L range.7−10”
From Presence of Emerging Per- and Polyfluoroalkyl Substances (PFASs) in River and Drinking Water near a Fluorochemical Production Plant in the Netherlands (2017) · cites this paper as [10]
Emerging PFASs reported in those studies include perfluoroalkyl ether carboxylic acids such as GenX, polyfluoroalkyl carboxylic acids of the C2nH2nF2nO2 class, and polyfluorinated alkanesulfonates and sulfates.
“Emerging PFASs detected in these studies included perfluoroalkyl (mono and poly) ether carboxylic acids including GenX (also named PFPrOPrA or HFPO–DA), polyfluoroalkyl carboxylic acids (C2nH2nF2nO2 homologues), and polyfluorinated alkanesulfonates and sulfates”
From Presence of Emerging Per- and Polyfluoroalkyl Substances (PFASs) in River and Drinking Water near a Fluorochemical Production Plant in the Netherlands (2017) · cites this paper as [10]
6:2 Cl-PFESA is a principal component of F-53B, has been used in the Chinese chrome-plating industry for about 30 years, and has been detected in wastewater, fish, human serum, and human placenta.
“This compound, which is a principal component of F-53B, has been used in the Chinese chrome-plating industry for about 30 years 63 and has been detected in wastewater, 64 fish, 65 human serum, 66 and even human placenta.”
From Non-Target and Suspect Screening of Per- and Polyfluoroalkyl Substances in Airborne Particulate Matter in China (2018) · cites this paper as [64]
Most non-target PFAS screening studies have focused on PFAS sources such as AFFF and wastewater, and on contaminated samples.
“Most studies on the non-target screening of PFASs are concerned with the PFAS source (e.g., AFFF [20][21][22][23] and wastewater 24 ) and contaminated samples (water affected by AFFF or wastewater 20,25 ).”
From Non-Target and Suspect Screening of Per- and Polyfluoroalkyl Substances in Airborne Particulate Matter in China (2018) · cites this paper as [24]
Cites
Global Distribution of Perfluorooctane Sulfonate in Wildlife
Giesy, J. P., & Kannan, K. (2001) · Environmental Science & Technology · doi:10.1021/es001834k · Cited by 2,750 · see citing works
Wang, Z., Cousins, I. T., Scheringer, M., & Hungerbühler, K. (2013) · Environment International · doi:10.1016/j.envint.2013.08.021 · Cited by 924 · see citing works
Backe, W. J., Day, T. C., & Field, J. A. (2013) · Environmental Science & Technology · doi:10.1021/es3034999 · Cited by 611 · see citing works
Martin, J. W., Asher, B. J., Beesoon, S., Benskin, J. P., & Ross, M. S. (2010) · Journal of Environmental Monitoring · doi:10.1039/c0em00295j · Cited by 311 · see citing works
Self-citationMyers, A. L., Jobst, K. J., Mabury, S. A., & Reiner, E. J. (2014) · Journal of Mass Spectrometry · doi:10.1002/jms.3340 · Cited by 103 · see citing works
Flagged first, then by citations
Cited by
Sorted by citations
Barzen-Hanson, K. A., Roberts, S. C., Choyke, S., Oetjen, K., McAlees, A., Riddell, N., McCrindle, R., Ferguson, P. L., Higgins, C. P., & Field, J. A. (2017) · Environmental Science & Technology · doi:10.1021/acs.est.6b05843 · Cited by 873 · 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
“Liu et al.(10) reported on the presence of chemicals with these masses in 294”
BackgroundInfluentialLiu, Y., D'Agostino, L. A., Qu, G., Jiang, G., & Martin, J. W. (2019) · TrAC Trends in Analytical Chemistry · doi:10.1016/j.trac.2019.02.021 · Cited by 344 · see citing works
Self-citationNewton, 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
Yu, N., Guo, H., Yang, J., Jin, L., Wang, X., Shi, W., Zhang, X., Yu, H., & Wei, S. (2018) · Environmental Science & Technology · doi:10.1021/acs.est.8b02492 · Cited by 200 · see citing works
McCord, J., & Strynar, M. (2019) · Environmental Science & Technology · doi:10.1021/acs.est.8b06017 · Cited by 183 · see citing works
Wang, X., Yu, N., Qian, Y., Shi, W., Zhang, X., Geng, J., Yu, H., & Wei, S. (2020) · Water Research · doi:10.1016/j.watres.2020.115989 · Cited by 179 · see citing works
Hall, S. M., Zhang, S., Hoffman, K., Miranda, M. L., & Stapleton, H. M. (2022) · Chemosphere · doi:10.1016/j.chemosphere.2022.133873 · Cited by 144 · see citing works
Discovery of a Novel Polyfluoroalkyl Benzenesulfonic Acid around Oilfields in Northern China
Xu, L., Shi, Y., Li, C., Song, X., Qin, Z., Cao, D., & Cai, Y. (2017) · Environmental Science & Technology · doi:10.1021/acs.est.7b04332 · Cited by 148 · see citing works
Analysis of emerging per- and polyfluoroalkyl substances: Progress and current issues
Pan, Y., Wang, J., Yeung, L. W. Y., Wei, S., & Dai, J. (2020) · TrAC Trends in Analytical Chemistry · doi:10.1016/j.trac.2019.04.013 · Cited by 133 · see citing works
Munoz, G., Ray, P., Mejia-Avendaño, S., Vo Duy, S., Tien Do, D., Liu, J., & Sauvé, S. (2018) · Analytica Chimica Acta · doi:10.1016/j.aca.2018.06.046 · Cited by 103 · see citing works
Ruan, T., & Jiang, G. (2017) · TrAC Trends in Analytical Chemistry · doi:10.1016/j.trac.2017.07.024 · Cited by 94 · see citing works
Jeong, Y., Da Silva, K. M., Iturrospe, E., Fuiji, Y., Boogaerts, T., van Nuijs, A. L. N., Koelmel, J., & Covaci, A. (2022) · Journal of Hazardous Materials · doi:10.1016/j.jhazmat.2022.129378 · Cited by 76 · see citing works
Guo, R., Megson, D., Myers, A. L., Helm, P. A., Marvin, C., Crozier, P., Mabury, S., Bhavsar, S. P., Tomy, G., Simcik, M., et al. (2016) · Chemosphere · doi:10.1016/j.chemosphere.2016.08.126 · Cited by 58 · see citing works
Janousek, R. M., Mayer, J., & Knepper, T. P. (2019) · TrAC Trends in Analytical Chemistry · doi:10.1016/j.trac.2019.01.017 · Cited by 56 · see citing works
Aly, N. A., Luo, Y.-S., Liu, Y., Casillas, G., McDonald, T. J., Kaihatu, J. M., Jun, M., Ellis, N., Gossett, S., Dodds, J. N., et al. (2020) · Environmental Pollution · doi:10.1016/j.envpol.2020.115009 · Cited by 52 · see citing works
Self-citationJiang, L., Yao, J., Ren, G., Sheng, N., Guo, Y., Dai, J., & Pan, Y. (2023) · Science of The Total Environment · doi:10.1016/j.scitotenv.2022.159638 · Cited by 51 · see citing works
OECD (2018) · OECD Series on Risk Management of Chemicals · doi:10.1787/1a14ad6c-en · Cited by 50 · see citing works
Comprehensive Emerging Chemical Discovery: Novel Polyfluorinated Compounds in Lake Michigan Trout
Fakouri Baygi, S., Crimmins, B. S., Hopke, P. K., & Holsen, T. M. (2016) · Environmental Science & Technology · doi:10.1021/acs.est.6b01349 · Cited by 49 · see citing works
Mumtaz, M., Bao, Y., Li, W., Kong, L., Huang, J., & Yu, G. (2019) · Frontiers of Environmental Science & Engineering · doi:10.1007/s11783-019-1145-0 · Cited by 45 · see citing works
Rehnstam, S., Czeschka, M.-B., & Ahrens, L. (2023) · Chemosphere · doi:10.1016/j.chemosphere.2023.138925 · Cited by 36 · see citing works
Awchi, M., Gebbink, W. A., Berendsen, B. J. A., Benskin, J. P., & van Leeuwen, S. P. J. (2022) · Chemosphere · doi:10.1016/j.chemosphere.2021.132143 · Cited by 28 · see citing works
- Authors
- Liu, Y., Pereira, A. D. S., & Martin, J. W.
- Affiliations
- University of Alberta (CA)
- Corresponding author
- Martin, Jonathan W.
- Venue
- Analytical Chemistry
- Publisher
- American Chemical Society (ACS)
- Published
- 2015-04-09
- Volume
- 87
- Issue
- 8
- Pages
- 4260-4268
- ISSN
- 0003-2700 (ISSN-L)
- 1520-6882
- OpenAlex
- W1979435857
- Semantic Scholar
- b3316fd63d24503c904f2044937a9d16b49a05cf
- Cited by
- 209
- References
- 5
- Citations by year
- 2026: 14 · 2025: 24 · 2024: 17 · 2023: 26 · 2022: 34 · 2021: 21 · 2020: 22 · 2019: 19 · 2018: 9 · 2017: 11 · 2016: 11 · 2015: 1
- FWCI
- 7.86
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Analytical Chemistry (publishedVersion)
- PubMed (publishedVersion)
- Funders
- Ministry of Health and Wellness, Government of Alberta
- China Scholarship Council
- Natural Sciences and Engineering Research Council of Canada
- Topics
- Physical Sciences › Environmental Science › Environmental Chemistry › Per- and polyfluoroalkyl substances research
- Physical Sciences › Chemistry › Spectroscopy › Mass Spectrometry Techniques and Applications
- Life Sciences › Pharmacology, Toxicology and Pharmaceutics › Pharmaceutical Science › Fluorine in Organic Chemistry
- Keywords
- perfluorinated compounds, polyfluoroalkyl substances, non-targeted analysis, water analysis, industrial wastewater, organofluorine compounds, empirical formula determination
- MeSH terms
- Chromatography, High Pressure Liquid, Fluorocarbons, Water Pollutants, Chemical, Solid Phase Extraction
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
