采用HRMS结合13C-同位素比值技术探究水环境中新兴污染物的归趋和转化机制
Migration and transformation mechanism of emerging contaminants in the aquatic environments by HRMS coupled with 13C-isotope labeling
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摘要: 新兴污染物（ECs）释放到水体中能够对野生物种和人群健康构成潜在隐患.天然有机质（NOM）含有羟基、氨基、羧基和醌基等活性官能团，可参与水体中天然酶介导的酶催化氧化腐殖化反应（ECOHRs），并通过自由基耦合机制与ECs形成共价结合产物.该过程不仅降低了ECs的生态毒性，也增加了水体中有机碳、氮储备.然而，如何分析和鉴定ECOHRs中ECs和NOM分子之间形成的共价结合产物已经成为限制研究者阐明ECs在天然水体中迁移和转化机理的瓶颈.本文综述了天然水体中ECs的来源、污染现状、分布特征和生态毒理学效应，明确了ECOHRs对ECs生物有效性和转化行为的影响，重点利用高分辨质谱（HRMS）结合13C-同位素比值技术分析和鉴定了ECs和NOM分子之间形成的共价结合产物.该方法主要通过精确的分子量、同位素标记差值和相对强度比值，从水环境中筛选出ECs和NOM分子之间所有可能存在的共价结合产物，为深入阐明ECs在天然酶介导ECOHRs中的归趋和转化机理提供了理论支持和技术保障.Abstract: Emerging contaminants (ECs, such as endocrine disrupting chemicals, antibiotics, pharmaceuticals, and personal care products, etc.) are released into the aquatic environments from multiple sources including effluents from municipal and industrial wastewater treatment plants, which pose potential threat to the wild species and human health. Natural organic matter (NOM) is rich in various functional groups such as carboxyl, amino, hydroxyl, and quinone groups, which play a vital role in the aquatic environments during natural enzyme-catalyzed oxidative humification reactions (ECOHRs). In particular, NOM radicals can couple ECs radicals to form the cross-coupling products via the covalent binding mechanism during ECOHRs, which can alter the migration ECs in the natural aquatic environments. It is noted that the formation of cross-coupling products effectively reduces the toxicity of ECs and improves the conservation of organic C and N. The information is however limited regarding the analysis and identification of covalent binding products between NOM and ECs molecules during ECOHRs. Aiming at the problems, this paper reviews the sources, pollution situations, distribution characteristics, and environmental effects of ECs, and the influence of ECOHRs on the bioavailability and transport of ECs is also investigated. More importantly, a method combining high-resolution mass spectrometry (HRMS) and 13C-isotope ratio is systematically estimated for the identification of cross-coupling products between NOM and ECs molecules. The analytical method is mainly based on the following four rules:(1) The isotope labeling in combination with the extremely high accuracy of the HRMS; (2) The exact difference in molecular weight (MW) between monoisotopic m/z peak and its corresponding isotope peak (ΔMW=1.0033n, n is an integer and n > 0); (3) The relative intensity ratios between product peaks and their isotope-labeled counterparts (1:1 for one isotope-labeled counterpart, 1:2:1 for two isotope-labeled counterparts, and 1:3:3:1 for three isotope-labeled counterparts, etc.); (4) The MW of the covalent binding product is greater than ECs, and does not appear in the control samples. The combination of HRMS and isotope labeling is of great importance to screening all of cross-coupling products between NOM and ECs molecules, and to illuminating the fate and transformation of ECs in the complex aquatic environments.
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