Development of complementary CE-MS methods for speciation analysis of pyrithione-based antifouling agents
Development of complementary CE-MS methods for speciation analysis of pyrithione-based antifouling agents
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DOI：
10.1007/s00216-019-02094-5
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发表时间：
2019-11-01
影响因子：
4.3
通讯作者：
Meermann, Bjoern
中科院分区：
文献类型：
--
作者：
Fassbender, Sebastian;Doering, Ann-Katrin;Meermann, Bjoern
近十年来，金属吡啶配合物已成为重要的船舶杀菌剂。金属吡啶并咪唑络合物及其降解产物/物种在环境样品中的分析是具有挑战性的，因为它们表现出快速的UV降解，transmetalation和配体取代，并且已知易于在色谱系统内自发物种转化。梨形目物种的环境特性，例如，对目标生物和非目标生物的毒性有很大的不同，因此不可避免地要分别对所有物种进行识别和量化。为了科普分析过程中金属吡啶类化合物的分离问题，建立了一种基于毛细管电泳（CE）的方法。CE与选择性电喷雾离子化和电感耦合等离子体质谱（ESI-，ICP-MS）的联用提供了互补的分子和元素信息，用于鉴定和定量的吡蚜酮物种。为研究吡啶硫酮的形态分布，对几种市售含吡啶硫酮锌的油漆在超纯水和河水中的浸出行为进行了研究。在浸提介质中只发现了两种物质----嘧啶（HPT）和双嘧啶（（PT）（2）），浓度在0.086和2.4 μ M之间（HPT）和0.062和0.59 μ M之间（（PT）（2）），取决于油漆和浸提介质。检测限为20 nM（HPT）和10 nM（（PT）（2））。结果表明，互补CE-MS是关于物种转化的机制研究的合适工具（例如，降解）和鉴定金属吡啶络合物在真实的地表水基质中的目标物种，为未来的环境研究奠定了基础。图形摘要CE与ESI-和ICP-MS联用提供了互补的分子和元素信息。在超纯水和河水基质中，可以识别和量化从商业油漆中释放的金属吡啶类物质
In the recent decade, metal pyrithione complexes have become important biocides for antifouling purposes in shipping. The analysis of metal pyrithione complexes and their degradation products/species in environmental samples is challenging because they exhibit fast UV degradation, transmetalation, and ligand substitution and are known to be prone to spontaneous species transformation within a chromatographic system. The environmental properties of the pyrithione species, e.g., toxicity to target and non-target organisms, are differing strongly, and it is therefore inevitable to identify as well as quantify all species separately. To cope with the separation of metal pyrithione species with minimum species transformation during analysis, a capillary electrophoresis (CE)-based method was developed. The hyphenation of CE with selective electrospray ionization- and inductively coupled plasma-mass spectrometry (ESI-, ICP-MS) provided complementary molecular and elemental information for the identification and quantification of pyrithione species. To study speciation of pyrithiones, a leaching experiment of several commercial antifouling paints containing zinc pyrithione in ultrapure and river water was conducted. Only the two species pyrithione (HPT) and dipyrithione ((PT)(2)) were found in the leaching media, in concentrations between 0.086 and 2.4 mu M (HPT) and between 0.062 and 0.59 mu M ((PT)(2)), depending on the paint and leaching medium. The limits of detection were 20 nM (HPT) and 10 nM ((PT)(2)). The results show that complementary CE-MS is a suitable tool for mechanistical studies concerning species transformation (e.g., degradation) and the identification of target species of metal pyrithione complexes in real surface water matrices, laying the ground for future environmental studies.Graphical abstract Hyphenation of CE with ESI- and ICP-MS provided complementary molecular and elemental information. Metal pyrithione species released from commercial antifouling paints could be identified and quantified in ultrapure and river water matrices