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一种新的在线 SPE LC-HRMS 方法,用于分析 PM 中的全氟烷基和多氟烷基物质 (PFAS),及其在爱尔兰都柏林和恩尼斯的大气颗粒物筛选中的应用。

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

机构信息

Centre for Agroecology Water and Resilience (CAWR), Coventry University, Wolston Lane, Ryton on Dunsmore CV8 3LG, UK.

School of Chemistry and Environmental Research Institute, University College Cork, Cork, Ireland.

出版信息

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

DOI:10.1016/j.scitotenv.2022.155496
PMID:35483471
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) 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/m level and showed good tolerance to the considered PM matrix. The validated method was applied for analysis of PFAS in ambient PM 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 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 at urban locations in Ireland and also the first study to detect 4:2 and 8:2 fluorotelomer sulfonates in atmospheric aerosol particles.

摘要

已经开发并验证了一种灵敏的分析方法,用于使用在线固相萃取(SPE)与液相色谱(LC)-负离子电喷雾高分辨质谱(-)ESI-HRMS 联用,测定细颗粒物(PM)中 16 种全氟烷基物质(PFAS)。在线 SPE 允许通过将大量样品注入 LC 系统,同时从干扰基质中进行样品净化,并降低检测限(LOD),而不会影响色谱效率和分辨率。该方法提供的检测限在 0.08-0.5 pg/mL 样品提取物范围内,允许在 fg/m 级别的低水平下检测气溶胶颗粒中的选定 PFAS,并对所考虑的 PM 基质具有良好的耐受性。该验证方法应用于在爱尔兰两个城市地点(恩尼斯和都柏林)收集的环境 PM 样品中 PFAS 的分析。在检测限以上观察到几种 PFAS,包括全氟丁烷磺酸(PFBA)、全氟辛酸(PFOA)、全氟辛烷磺酸(PFOS)、全氟丁烷磺酸(L-PFBS)和全氟壬酸(PFNA),以及氟代醇磺酸盐:4:2 FTS、6:2 FTS 和 8:2 FTS。结果表明,尽管 PFOS 和 PFOA 等一些有毒 PFAS 已从生产中淘汰并在欧盟和美国受到限制使用超过二十年,但它们仍在环境中被检测到。在环境 PM 样品中观察到氟代醇磺酸盐(4:2 FTS、6:2 FTS 和 8:2 FTS,它们被用作传统 PFOA 和 PFOS 的替代品),这引起了人们对它们在大气中持久性及其对人类健康影响的关注,因为新兴证据表明它们可能与 PFOA 和 PFOS 具有相似的健康终点。据我们所知,这是首次在爱尔兰城市地区的环境 PM 中识别 PFAS 的研究,也是首次在大气气溶胶颗粒中检测到 4:2 和 8:2 氟代醇磺酸盐的研究。

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