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利用双示踪剂(二辛基和单辛基磺基琥珀酸酯)监测海水中的溢油分散剂:来自科瑞希特 EC9500A 的油基分散剂。

Improved oil spill dispersant monitoring in seawater using dual tracers: Dioctyl and monoctyl sulfosuccinates sourced from corexit EC9500A.

机构信息

Pacific and Yukon Laboratory for Environmental Testing, Science and Technology Branch, Pacific Environmental Science Centre, Environment & Climate Change Canada, North Vancouver, British Columbia, Canada.

Pacific and Yukon Laboratory for Environmental Testing, Science and Technology Branch, Pacific Environmental Science Centre, Environment & Climate Change Canada, North Vancouver, British Columbia, Canada.

出版信息

J Chromatogr A. 2019 Aug 2;1598:113-121. doi: 10.1016/j.chroma.2019.03.049. Epub 2019 Apr 7.

DOI:10.1016/j.chroma.2019.03.049
PMID:30987784
Abstract

A high resolution mass spectrometry method was developed for the environmental impact monitoring of oil spill dispersants. Previously reported instability of dioctyl sulfosuccinate (DOSS) dispersant tracer was addressed by the new procedure. The method monitors both DOSS and its degradation product, monooctyl sulfosuccinate (MOSS), by liquid chromatography time-of-flight mass spectrometry. The related isomer, 4-(2-ethylhexyl) 2-sulfobutanedioate, was chromatographically resolved from MOSS but was not a product of DOSS degradation. Using this direct injection method (10 μL), the practical lower limit of quantitation was 0.5 nM for each analyte, a concentration equivalent to 0.22 ng mL, or 0.30 ng mL including initial dilution factor with acetonitrile. The method was shown applicable to analysis of the dispersants Corexit® EC9500 A, Finasol OSR 52, Slickgone NS, and Slickgone EW for which DOSS is an active ingredient. A marine microcosm study of Corexit EC9500A, together with diluted bitumen (dilbit), at 15 ± 1 °C, provided evidence of the stoichiometric conversion of DOSS to MOSS under conditions reflecting a western Canadian marine environment. The advantage of the developed method is in its ability to extend environmental seawater sample collection time from 4 days for DOSS alone, to 14 days when both DOSS and MOSS are simultaneously analysed and results combined. The collection time is likely extended beyond the 14 day period with cooler temperatures. Preservation of collected seawater samples using sodium hydroxide, converting DOSS into MOSS in situ, was rejected due to stability issues. Addition of disodium ethylenediaminetetraacetic acid did not improve hold times, thus eliminating the theory of cation induced micelle effects causing DOSS loss.

摘要

建立了一种高分辨质谱方法,用于监测溢油分散剂的环境影响。通过新方法解决了先前报道的二辛基琥珀酸磺酸钠(DOSS)分散剂示踪剂不稳定的问题。该方法通过液相色谱飞行时间质谱法监测 DOSS 及其降解产物单辛基琥珀酸磺酸钠(MOSS)。相关的异构体 4-(2-乙基己基)2-磺基丁二酸酯在色谱上与 MOSS 分离,但不是 DOSS 降解的产物。使用这种直接进样方法(10μL),每个分析物的实际定量下限为 0.5nM,浓度相当于 0.22ng·mL-1,或包括与乙腈初始稀释因子在内的 0.30ng·mL-1。该方法适用于分析含有 DOSS 作为有效成分的分散剂 Corexit®EC9500A、Finasol OSR 52、Slickgone NS 和 Slickgone EW。在 15±1°C 的条件下,对 Corexit EC9500A 与稀释沥青(dilbit)进行的海洋微宇宙研究提供了证据,表明在反映加拿大西部海洋环境的条件下,DOSS 与 MOSS 发生了化学计量转化。所开发方法的优点在于能够将单独分析 DOSS 时的环境海水样品采集时间从 4 天延长至同时分析 DOSS 和 MOSS 并将结果结合使用时的 14 天。在温度较低的情况下,采集时间可能会延长至超过 14 天。由于稳定性问题,使用氢氧化钠保存采集的海水样品,将 DOSS 就地转化为 MOSS 的方法被拒绝。添加乙二胺四乙酸二钠并没有提高保留时间,因此排除了阳离子诱导胶束效应导致 DOSS 损失的理论。

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