PFAS Analysis with Ultrahigh Resolution 21T FT-ICR MS: Suspect and Nontargeted Screening with Unrivaled Mass Resolving Power and Accuracy

Robert B. Young; Nasim E. Pica; Hamidreza Sharifan; Huan Chen; Holly K. Roth; Greg T. Blakney; Thomas Borch; Christopher P. Higgins; John J. Kornuc; Amy M. McKenna; Jens Blotevogel

doi:10.1021/acs.est.1c08143

PFAS Analysis with Ultrahigh Resolution 21T FT-ICR MS: Suspect and Nontargeted Screening with Unrivaled Mass Resolving Power and Accuracy

Robert B. Young, Nasim E. Pica, Hamidreza Sharifan, Huan Chen, Holly K. Roth, Greg T. Blakney, Thomas Borch, Christopher P. Higgins, John J. Kornuc, Amy M. McKenna, Jens Blotevogel

Plant-Soil Interactions

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61 Scopus citations

Abstract

Per- and polyfluoroalkyl substances (PFASs) are a large family of thousands of chemicals, many of which have been identified using nontargeted time-of-flight and Orbitrap mass spectrometry methods. Comprehensive characterization of complex PFAS mixtures is critical to assess their environmental transport, transformation, exposure, and uptake. Because 21 tesla (T) Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) offers the highest available mass resolving power and sub-ppm mass errors across a wide molecular weight range, we developed a nontargeted 21 T FT-ICR MS method to screen for PFASs in an aqueous film-forming foam (AFFF) using suspect screening, a targeted formula database (C, H, Cl, F, N, O, P, S; ≤865 Da), isotopologues, and Kendrick-analogous mass difference networks (KAMDNs). False-positive PFAS identifications in a natural organic matter (NOM) sample, which served as the negative control, suggested that a minimum length of 3 should be imposed when annotating CF₂-homologous series with positive mass defects. We putatively identified 163 known PFASs during suspect screening, as well as 134 novel PFASs during nontargeted screening, including a suspected polyethoxylated perfluoroalkane sulfonamide series. This study shows that 21 T FT-ICR MS analysis can provide unique insights into complex PFAS composition and expand our understanding of PFAS chemistries in impacted matrices.

Original language	English
Pages (from-to)	2455-2465
Number of pages	11
Journal	Environmental Science and Technology
Volume	56
Issue number	4
DOIs	https://doi.org/10.1021/acs.est.1c08143
State	Published - Feb 15 2022

Funding

Financial support for this research was provided by the U.S. Department of Defense’s Strategic Environmental Research and Development Program (SERDP) under Project ER20-1265. Partial support was provided through SERDP Project ER-2718. The Ion Cyclotron Resonance user facility located at the National High Magnetic Field Laboratory in Tallahassee, FL (Florida State University), is supported by the National Science Foundation Division of Chemistry and Division of Materials Research through DMR 16-44779 and the State of Florida. The authors thank Paul Hatzinger (APTIM) for donating the AFFF sample and Boris P. Koch (Alfred Wegener Institute Helmholtz Centre for Polar and Marine Research) for assisting with UltraMassExplorer. Financial support for this research was provided by the U.S. Department of Defense?s Strategic Environmental Research and Development Program (SERDP) under Project ER20-1265. Partial support was provided through SERDP Project ER-2718. The Ion Cyclotron Resonance user facility located at the National High Magnetic Field Laboratory in Tallahassee, FL (Florida State University), is supported by the National Science Foundation Division of Chemistry and Division of Materials Research through DMR 16-44779 and the State of Florida. The authors thank Paul Hatzinger (APTIM) for donating the AFFF sample and Boris P. Koch (Alfred Wegener Institute Helmholtz Centre for Polar and Marine Research) for assisting with UltraMassExplorer.

Keywords

AFFF
KMD
Kendrick mass defect
ion cyclotron resonance
mass spectrometry
network analysis
perfluoroalkyl
polyfluoroalkyl

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10.1021/acs.est.1c08143

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Young, R. B., Pica, N. E., Sharifan, H., Chen, H., Roth, H. K., Blakney, G. T., Borch, T., Higgins, C. P., Kornuc, J. J., McKenna, A. M., & Blotevogel, J. (2022). PFAS Analysis with Ultrahigh Resolution 21T FT-ICR MS: Suspect and Nontargeted Screening with Unrivaled Mass Resolving Power and Accuracy. Environmental Science and Technology, 56(4), 2455-2465. https://doi.org/10.1021/acs.est.1c08143

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title = "PFAS Analysis with Ultrahigh Resolution 21T FT-ICR MS: Suspect and Nontargeted Screening with Unrivaled Mass Resolving Power and Accuracy",

abstract = "Per- and polyfluoroalkyl substances (PFASs) are a large family of thousands of chemicals, many of which have been identified using nontargeted time-of-flight and Orbitrap mass spectrometry methods. Comprehensive characterization of complex PFAS mixtures is critical to assess their environmental transport, transformation, exposure, and uptake. Because 21 tesla (T) Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) offers the highest available mass resolving power and sub-ppm mass errors across a wide molecular weight range, we developed a nontargeted 21 T FT-ICR MS method to screen for PFASs in an aqueous film-forming foam (AFFF) using suspect screening, a targeted formula database (C, H, Cl, F, N, O, P, S; ≤865 Da), isotopologues, and Kendrick-analogous mass difference networks (KAMDNs). False-positive PFAS identifications in a natural organic matter (NOM) sample, which served as the negative control, suggested that a minimum length of 3 should be imposed when annotating CF2-homologous series with positive mass defects. We putatively identified 163 known PFASs during suspect screening, as well as 134 novel PFASs during nontargeted screening, including a suspected polyethoxylated perfluoroalkane sulfonamide series. This study shows that 21 T FT-ICR MS analysis can provide unique insights into complex PFAS composition and expand our understanding of PFAS chemistries in impacted matrices.",

keywords = "AFFF, KMD, Kendrick mass defect, ion cyclotron resonance, mass spectrometry, network analysis, perfluoroalkyl, polyfluoroalkyl",

author = "Young, \{Robert B.\} and Pica, \{Nasim E.\} and Hamidreza Sharifan and Huan Chen and Roth, \{Holly K.\} and Blakney, \{Greg T.\} and Thomas Borch and Higgins, \{Christopher P.\} and Kornuc, \{John J.\} and McKenna, \{Amy M.\} and Jens Blotevogel",

note = "Publisher Copyright: {\textcopyright} 2022 American Chemical Society",

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doi = "10.1021/acs.est.1c08143",

language = "English",

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Young, RB, Pica, NE, Sharifan, H, Chen, H, Roth, HK, Blakney, GT, Borch, T, Higgins, CP, Kornuc, JJ, McKenna, AM & Blotevogel, J 2022, 'PFAS Analysis with Ultrahigh Resolution 21T FT-ICR MS: Suspect and Nontargeted Screening with Unrivaled Mass Resolving Power and Accuracy', Environmental Science and Technology, vol. 56, no. 4, pp. 2455-2465. https://doi.org/10.1021/acs.est.1c08143

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T2 - Suspect and Nontargeted Screening with Unrivaled Mass Resolving Power and Accuracy

AU - Young, Robert B.

AU - Pica, Nasim E.

AU - Sharifan, Hamidreza

AU - Chen, Huan

AU - Roth, Holly K.

AU - Blakney, Greg T.

AU - Borch, Thomas

AU - Higgins, Christopher P.

AU - Kornuc, John J.

AU - McKenna, Amy M.

AU - Blotevogel, Jens

PY - 2022/2/15

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N2 - Per- and polyfluoroalkyl substances (PFASs) are a large family of thousands of chemicals, many of which have been identified using nontargeted time-of-flight and Orbitrap mass spectrometry methods. Comprehensive characterization of complex PFAS mixtures is critical to assess their environmental transport, transformation, exposure, and uptake. Because 21 tesla (T) Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) offers the highest available mass resolving power and sub-ppm mass errors across a wide molecular weight range, we developed a nontargeted 21 T FT-ICR MS method to screen for PFASs in an aqueous film-forming foam (AFFF) using suspect screening, a targeted formula database (C, H, Cl, F, N, O, P, S; ≤865 Da), isotopologues, and Kendrick-analogous mass difference networks (KAMDNs). False-positive PFAS identifications in a natural organic matter (NOM) sample, which served as the negative control, suggested that a minimum length of 3 should be imposed when annotating CF2-homologous series with positive mass defects. We putatively identified 163 known PFASs during suspect screening, as well as 134 novel PFASs during nontargeted screening, including a suspected polyethoxylated perfluoroalkane sulfonamide series. This study shows that 21 T FT-ICR MS analysis can provide unique insights into complex PFAS composition and expand our understanding of PFAS chemistries in impacted matrices.

AB - Per- and polyfluoroalkyl substances (PFASs) are a large family of thousands of chemicals, many of which have been identified using nontargeted time-of-flight and Orbitrap mass spectrometry methods. Comprehensive characterization of complex PFAS mixtures is critical to assess their environmental transport, transformation, exposure, and uptake. Because 21 tesla (T) Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) offers the highest available mass resolving power and sub-ppm mass errors across a wide molecular weight range, we developed a nontargeted 21 T FT-ICR MS method to screen for PFASs in an aqueous film-forming foam (AFFF) using suspect screening, a targeted formula database (C, H, Cl, F, N, O, P, S; ≤865 Da), isotopologues, and Kendrick-analogous mass difference networks (KAMDNs). False-positive PFAS identifications in a natural organic matter (NOM) sample, which served as the negative control, suggested that a minimum length of 3 should be imposed when annotating CF2-homologous series with positive mass defects. We putatively identified 163 known PFASs during suspect screening, as well as 134 novel PFASs during nontargeted screening, including a suspected polyethoxylated perfluoroalkane sulfonamide series. This study shows that 21 T FT-ICR MS analysis can provide unique insights into complex PFAS composition and expand our understanding of PFAS chemistries in impacted matrices.

KW - AFFF

KW - KMD

KW - Kendrick mass defect

KW - ion cyclotron resonance

KW - mass spectrometry

KW - network analysis

KW - perfluoroalkyl

KW - polyfluoroalkyl

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JO - Environmental Science and Technology

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IS - 4

ER -

PFAS Analysis with Ultrahigh Resolution 21T FT-ICR MS: Suspect and Nontargeted Screening with Unrivaled Mass Resolving Power and Accuracy

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