A new on-line SPE LC-HRMS method for the analysis of Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) in PM2.5 and its application for screening atmospheric particulates from Dublin and Enniscorthy, Ireland

Ivan Kourtchev; Stig Hellebust; Eimear Heffernan; John Wenger; Sam Towers; Evangelia Diapouli; Konstantinos Eleftheriadis

doi:10.1016/j.scitotenv.2022.155496

A new on-line SPE LC-HRMS method for the analysis of Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) in PM_2.5 and its application for screening atmospheric particulates from Dublin and Enniscorthy, Ireland

Sci Total Environ. 2022 Aug 20:835:155496. doi: 10.1016/j.scitotenv.2022.155496. Epub 2022 Apr 26.

Authors

Ivan Kourtchev¹, Stig Hellebust², Eimear Heffernan², John Wenger², Sam Towers³, Evangelia Diapouli⁴, Konstantinos Eleftheriadis⁴

Affiliations

¹ Centre for Agroecology Water and Resilience (CAWR), Coventry University, Wolston Lane, Ryton on Dunsmore CV8 3LG, UK. Electronic address: ivan.kourtchev@coventry.ac.uk.
² School of Chemistry and Environmental Research Institute, University College Cork, Cork, Ireland.
³ Centre for Agroecology Water and Resilience (CAWR), Coventry University, Wolston Lane, Ryton on Dunsmore CV8 3LG, UK.
⁴ ERL, Institute of Nuclear and Radiological Science & Technology, Energy & Safety, NCSR Demokritos, 15310 Athens, Greece.

PMID: 35483471
DOI: 10.1016/j.scitotenv.2022.155496

Abstract

A sensitive analytical method has been developed and validated for the determination of 16 polyfluorinated alkyl substances (PFAS) in fine airborne particulate matter (PM_2.5) using on-line solid phase extraction (SPE) coupled with liquid chromatography (LC) - negative electrospray ionisation high resolution mass spectrometry (-) ESI-HRMS. On-line SPE allows simultaneous sample clean-up from interfering matrices and lower limits of detection (LODs) by injecting a large volume of sample into the LC system without compromising chromatographic efficiency and resolution. The method provides LODs in the range 0.08-0.5 pg/mL of sample extract allowing detection of selected PFAS in aerosol particles at low fg/m³ level and showed good tolerance to the considered PM matrix. The validated method was applied for analysis of PFAS in ambient PM_2.5 samples collected at two urban locations in Ireland, i.e., Enniscorthy and Dublin. Several PFAS were observed above the detection limit, including perfluorobutyrate (PFBA), perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), perfluorobutanesulfonic acid (L-PFBS) and perfluorononanoic acid (PFNA), as well as fluorotelomer sulfonates: 4:2 FTS, 6:2 FTS and 8:2 FTS. The results indicate that some toxic PFAS, such as PFOS and PFOA, are still detected in the environment despite being phased out from production and subject to restricted use in the EU and USA for more than two decades. Observation of fluorotelomer sulfonates (4:2 FTS, 6:2 FTS and 8:2 FTS, which are used as alternatives for legacy PFOA and PFOS) in ambient PM_2.5 samples raises a concern about their persistence in the atmosphere and impact on human health considering emerging evidence that they could have similar health endpoints as PFOA and PFOS. To our knowledge, this is the first study to identify PFAS in ambient PM_2.5 at urban locations in Ireland and also the first study to detect 4:2 and 8:2 fluorotelomer sulfonates in atmospheric aerosol particles.

Keywords: 6:2 FTS; 8:2 FTS; Aerosol; Fluorotelomer sulfonates; PFOA; PFOS.

MeSH terms

Alkanesulfonic Acids* / analysis
Chromatography, Liquid / methods
Dust / analysis
Fluorocarbons* / analysis
Humans
Ireland
Particulate Matter / analysis
Solid Phase Extraction
Spectrometry, Mass, Electrospray Ionization

Substances

Alkanesulfonic Acids
Dust
Fluorocarbons
Particulate Matter