Are (fluorinated) Ionic Liquids Relevant Environmental Contaminants? High-resolution Mass Spectrometric Screening for Per- and Polyfluoroalkyl Substances in Environmental Water Samples Led to the Detection of a Fluorinated Ionic Liquid

Overview

Journal Anal Bioanal Chem

Specialty Chemistry

Date 2020 Apr 3

PMID 32236657

Citations 4

Authors

Isabelle J Neuwald

Daniel Zahn

Thomas P Knepper

Affiliations

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Abstract

Fragmentation flagging (FF), a high-resolution mass spectrometric screening variant that utilizes intentionally produced indicative in-source fragments, was used to screen for per- and polyfluoroalkyl substances (PFASs) in surface waters. Besides expected legacy PFAS, FF enabled the detection of some rarely investigated representatives, such as trifluoromethanesulfonic acid (TFMSA). Additionally, a novel PFAS was detected and identified as tris(pentafluoroethyl)trifluorophosphate (FAP) via MS/MS experiments and confirmed with a reference standard. The first monitoring of FAP in 20 different surface waters revealed a localized contamination affecting three connected rivers with peak concentrations of up to 3.4 μg/L. To the best of our knowledge, this is the first time FAP has been detected in environmental water samples. The detection of FAP, which is exclusively used as a constituent of ionic liquids (ILs), raises questions about the environmental relevance of ILs in general and particularly fluorinated ILs. A following comprehensive literature search revealed that ILs have already been intensely discussed as potential environmental contaminants, but findings reporting ILs in environmental (water) samples are almost non-existent. Furthermore, we address the relevance of ILs in the context of persistent, mobile, and toxic chemicals, which are at present gaining increasing scientific and regulatory interest, and as part of the PFAS "dark matter" that represents the gap between the amount of fluorine originating from known PFAS and the total adsorbable organically bound fluorine. Graphical abstract.

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References

Backe W, Day T, Field J . Zwitterionic, cationic, and anionic fluorinated chemicals in aqueous film forming foam formulations and groundwater from U.S. military bases by nonaqueous large-volume injection HPLC-MS/MS. Environ Sci Technol. 2013; 47(10):5226-34. DOI: 10.1021/es3034999. View

Rotander A, Karrman A, Toms L, Kay M, Mueller J, Ramos M . Novel fluorinated surfactants tentatively identified in firefighters using liquid chromatography quadrupole time-of-flight tandem mass spectrometry and a case-control approach. Environ Sci Technol. 2015; 49(4):2434-42. DOI: 10.1021/es503653n. View

Becanova J, Melymuk L, Vojta S, Komprdova K, Klanova J . Screening for perfluoroalkyl acids in consumer products, building materials and wastes. Chemosphere. 2016; 164:322-329. DOI: 10.1016/j.chemosphere.2016.08.112. View

Ahrens L . Polyfluoroalkyl compounds in the aquatic environment: a review of their occurrence and fate. J Environ Monit. 2010; 13(1):20-31. DOI: 10.1039/c0em00373e. View

Cai M, Yang H, Xie Z, Zhao Z, Wang F, Lu Z . Per- and polyfluoroalkyl substances in snow, lake, surface runoff water and coastal seawater in Fildes Peninsula, King George Island, Antarctica. J Hazard Mater. 2012; 209-210:335-42. DOI: 10.1016/j.jhazmat.2012.01.030. View

Taniyasu S, Yamashita N, Moon H, Kwok K, Lam P, Horii Y . Does wet precipitation represent local and regional atmospheric transportation by perfluorinated alkyl substances?. Environ Int. 2013; 55:25-32. DOI: 10.1016/j.envint.2013.02.005. View

Franco A, Hauschild M, Jolliet O, Trapp S . Atmospheric fate of non-volatile and ionizable compounds. Chemosphere. 2011; 85(8):1353-9. DOI: 10.1016/j.chemosphere.2011.07.056. View

Hu X, Andrews D, Lindstrom A, Bruton T, Schaider L, Grandjean P . Detection of Poly- and Perfluoroalkyl Substances (PFASs) in U.S. Drinking Water Linked to Industrial Sites, Military Fire Training Areas, and Wastewater Treatment Plants. Environ Sci Technol Lett. 2016; 3(10):344-350. PMC: 5062567. DOI: 10.1021/acs.estlett.6b00260. View

Rahman M, Peldszus S, Anderson W . Behaviour and fate of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in drinking water treatment: a review. Water Res. 2013; 50:318-40. DOI: 10.1016/j.watres.2013.10.045. View

10.

Valsecchi S, Rusconi M, Polesello S . Determination of perfluorinated compounds in aquatic organisms: a review. Anal Bioanal Chem. 2012; 405(1):143-57. DOI: 10.1007/s00216-012-6492-7. View

11.

Shi Y, Vestergren R, Nost T, Zhou Z, Cai Y . Probing the Differential Tissue Distribution and Bioaccumulation Behavior of Per- and Polyfluoroalkyl Substances of Varying Chain-Lengths, Isomeric Structures and Functional Groups in Crucian Carp. Environ Sci Technol. 2018; 52(8):4592-4600. DOI: 10.1021/acs.est.7b06128. View

12.

Felizeter S, McLachlan M, de Voogt P . Uptake of perfluorinated alkyl acids by hydroponically grown lettuce (Lactuca sativa). Environ Sci Technol. 2012; 46(21):11735-43. DOI: 10.1021/es302398u. View

13.

Ghisi R, Vamerali T, Manzetti S . Accumulation of perfluorinated alkyl substances (PFAS) in agricultural plants: A review. Environ Res. 2018; 169:326-341. DOI: 10.1016/j.envres.2018.10.023. View

14.

Fromme H, Wockner M, Roscher E, Volkel W . ADONA and perfluoroalkylated substances in plasma samples of German blood donors living in South Germany. Int J Hyg Environ Health. 2017; 220(2 Pt B):455-460. DOI: 10.1016/j.ijheh.2016.12.014. View

15.

Ballesteros V, Costa O, Iniguez C, Fletcher T, Ballester F, Lopez-Espinosa M . Exposure to perfluoroalkyl substances and thyroid function in pregnant women and children: A systematic review of epidemiologic studies. Environ Int. 2016; 99:15-28. DOI: 10.1016/j.envint.2016.10.015. View

16.

Shi Y, Vestergren R, Xu L, Zhou Z, Li C, Liang Y . Human Exposure and Elimination Kinetics of Chlorinated Polyfluoroalkyl Ether Sulfonic Acids (Cl-PFESAs). Environ Sci Technol. 2016; 50(5):2396-404. DOI: 10.1021/acs.est.5b05849. View

17.

Domingo J . Health risks of dietary exposure to perfluorinated compounds. Environ Int. 2011; 40:187-195. DOI: 10.1016/j.envint.2011.08.001. View

18.

Ritscher A, Wang Z, Scheringer M, Boucher J, Ahrens L, Berger U . Zürich Statement on Future Actions on Per- and Polyfluoroalkyl Substances (PFASs). Environ Health Perspect. 2018; 126(8):84502. PMC: 6375385. DOI: 10.1289/EHP4158. View

19.

Willach S, Brauch H, Lange F . Contribution of selected perfluoroalkyl and polyfluoroalkyl substances to the adsorbable organically bound fluorine in German rivers and in a highly contaminated groundwater. Chemosphere. 2015; 145:342-50. DOI: 10.1016/j.chemosphere.2015.11.113. View

20.

Koke N, Zahn D, Knepper T, Fromel T . Multi-layer solid-phase extraction and evaporation-enrichment methods for polar organic chemicals from aqueous matrices. Anal Bioanal Chem. 2018; 410(9):2403-2411. DOI: 10.1007/s00216-018-0921-1. View