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安大略省地表水和废水排放中有机磷阻燃剂的液相色谱-串联质谱直接进样分析

Liquid chromatography-tandem mass spectrometry direct injection analysis of organophosphorus flame retardants in Ontario surface water and wastewater effluent.

作者信息

Hao Chunyan, Helm Paul A, Morse David, Reiner Eric J

机构信息

Laboratory Services Branch, Ontario Ministry of the Environment and Climate Change, 125 Resources Road, Etobicoke, Ontario, M9P 3V6, Canada.

Environmental Monitoring and Reporting Branch, Ontario Ministry of the Environment and Climate Change, 125 Resources Road, Etobicoke, Ontario, M9P 3V6, Canada.

出版信息

Chemosphere. 2018 Jan;191:288-295. doi: 10.1016/j.chemosphere.2017.10.060. Epub 2017 Oct 10.

DOI:10.1016/j.chemosphere.2017.10.060
PMID:29040943
Abstract

Organophosphorus flame retardants (OPFRs) started to be used in plastics, electronics and furnishings back in the 1960s and became popular again last decade. They are now widely present in the environment and regarded as "new" emerging organic pollutants. An effective liquid chromatography-tandem mass spectrometry (LC-MS/MS) direct injection analysis (DIA) method was developed to monitor OPFR levels in aquatic environment. The removal of sample extraction and concentration steps not only improved operation efficiency, but also reduced the potential contamination commonly observed during the sample preparation process before. Positive background signals from the analytical instrument were eliminated by employing a "trap" column in front of the sample injector while an ACE C18 and an ACE C18-PFP column were compared for the separation of OPFRs. Nineteen OPFR related compounds were evaluated and rapid signal drops were observed for seven of them including TOTP, TMTP, TPTP, TEHP, T35DMPP, T2iPPP and EHDP, due to their low water solubility. The other twelve compounds, TMP, TEP, TPrP, TiPP, TBP, TCEP, TCPP, TDCPP, TPP, TBEP, BDCP and BEHP, were included for the measurement of OPFRs in drinking water, surface water, ground water and wastewater effluent samples. The instrumental detection limits of these twelve OPFRs at signal-to-noise ≥3 were in the 1.5-30 ng/L range. The method was applied for the determination of OPFRs in surface water and wastewater samples in Ontario, Canada, and BEHP, TBEP, TBP, TCEP, TCPP, TDCPP, and TEP were commonly detected.

摘要

有机磷阻燃剂(OPFRs)早在20世纪60年代就开始用于塑料、电子产品和家具中,并且在过去十年中再度流行起来。它们如今广泛存在于环境中,被视为“新型”新兴有机污染物。开发了一种有效的液相色谱 - 串联质谱(LC-MS/MS)直接进样分析(DIA)方法来监测水生环境中的OPFRs水平。省去样品萃取和浓缩步骤不仅提高了操作效率,还减少了之前样品制备过程中常见的潜在污染。通过在样品进样器前使用一个“捕集”柱消除了分析仪器的正背景信号,同时比较了ACE C18和ACE C18-PFP柱对OPFRs的分离效果。评估了19种与OPFR相关的化合物,其中7种包括三(2-氯乙基)磷酸酯(TOTP)、三(2-甲基-1-氯丙基)磷酸酯(TMTP)、三(2,3-二氯丙基)磷酸酯(TPTP)、三(2-乙基己基)磷酸酯(TEHP)、三(5-氯-2-甲基苯基)磷酸酯(T35DMPP)、三(2-异丙基苯基)磷酸酯(T2iPPP)和2-乙基己基二苯基磷酸酯(EHDP),由于它们的低水溶性,观察到快速的信号下降。另外12种化合物,即磷酸三甲苯酯(TMP)、磷酸三乙酯(TEP)、磷酸三丙酯(TPrP)、磷酸三异丁酯(TiPP)、磷酸三丁酯(TBP)、磷酸三(2-氯乙基)酯(TCEP)、磷酸三(2-氯丙基)酯(TCPP)、磷酸三(2,3-二氯丙基)酯(TDCPP)、磷酸三苯酯(TPP)、磷酸三(2-丁氧基乙基)酯(TBEP)、双(2-氯乙基)磷酸酯(BDCP)和双(2-乙基己基)磷酸酯(BEHP),用于测量饮用水、地表水、地下水和废水排放样品中的OPFRs。这12种OPFRs在信噪比≥3时的仪器检测限在1.5 - 30 ng/L范围内。该方法应用于加拿大安大略省地表水和废水样品中OPFRs的测定,常见的检测到的有BEHP、TBEP、TBP、TCEP、TCPP、TDCPP和TEP。

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