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Development of analytical methods for speciation analysis of copper and zinc-based antifouling agents in surface water

地表水中铜基和锌基防污剂形态分析方法的开发

基本信息

批准号：
321800101
负责人：
Dr. Björn Meermann
金额：
--
依托单位：
Fachbereich 1.1: Anorganische Spurenanalytik
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2016
资助国家：
德国
起止时间：
2015-12-31 至 2020-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/321800101?language=en
关键词：
Development analytical methods speciation analysis

项目摘要

Surfaces in contact with the aquatic environment (e.g., ship´s fuselage, constructions in hydraulic engineering) are subjected to incrustation of fouling matter, so called bio-fouling. Bio-fouling leads to strong impairment with regard to, e.g., increase of ship´s water-friction, interference of operational capability of constructions in hydraulic engineering. Thus, today anti-fouling biocides on the basis of copper- and zinc-complexes are being used (e.g., pyrithiones). The environmental behavior of these metal-complexes is not fully unraveled yet, due to the fact that appropriate analytical tools for direct detection and speciation analysis are missing. Furthermore, transmetalation with further bivalent metal-cations is likely, thus influence the bioavailability and mobility of metal ions in the aquatic environment. However, investigations on this aspect are missing.Consequently, the main objectives of this project are:I) The development of appropriate complementary analytical methods for speciation analysis of metal-based anti-fouling biocides. Given the fact that ionic or at least polar substances are under investigation, method development is based on on-line coupling of capillary electrophoresis (CE) with high resolution molecular- as well as complementary elemental-mass spectrometry (CE/ESI-Q-ToF-MS <=> CE/ICP-SFMS). CE/ESI-Q-ToF-MS allows for an unambiguous species-identification on basis of exact molecular masses as well as MS/MS experiments and characteristic fragmentation pattern. Though, ESI-MS exhibits a species-specific detector response. Therefore, complementary CE/ICP-SFMS coupling will be deployed for species quantification on basis of a species-independent response. Furthermore, the determination of isotope ratios enables the application of enriched stabile isotopes (e.g., 65Cu, 67Zn) for tracing and quantification purposes.II) Upon method development lab-scale leaching-experiments will be conducted and complexity of the matrix will be increased during the course of experiments. On basis of these experiments the speciation and transmetalation behavior of metal-based anti-fouling biocides will be elucidated. Owing to the experience gained during the lab-scale experiments selective and invariant target species will be identified (acting as indicators of the formerly pristine metal-complexes).III) Based on the target species identified, analysis of real surface water samples collected from marinas/harbors will be conducted to assess the input as well as environmental pollution of antifouling biocides into the aquatic environment. Finally, the developed methods will be simplified to be widely applicable and transferable to other laboratories.Complete abandonment of anti-fouling substances is (currently) impossible, as environmentally justifiable alternative approaches are at present not robust enough. Thus, analytical methods are needed to end up with a more targeted and efficient use of anti-fouling substances.

与水生环境接触的表面（例如，船舶的机身，水利工程中的建筑物）受到污垢物质的结壳，所谓的生物污垢。生物结垢导致关于以下方面的强烈损害，例如，增加船舶水摩擦力，干扰水利工程施工作业能力。因此，目前正在使用基于铜和锌络合物的防污杀生物剂（例如，吡啶硫酮）。这些金属配合物的环境行为尚未完全解开，由于缺乏直接检测和形态分析的适当分析工具。此外，可能与其他二价金属阳离子发生金属交换，从而影响金属离子在水环境中的生物利用度和流动性。因此，本项目的主要目标是：（一）开发合适的补充分析方法，用于金属基防污杀菌剂的形态分析。考虑到离子或至少是极性物质正在研究中，方法开发基于毛细管电泳（CE）与高分辨率分子以及互补元素质谱（CE/ESI-Q-ToF-MS <=> CE/ICP-SFMS）的在线耦合。CE/ESI-Q-ToF-MS允许基于精确分子量以及MS/MS实验和特征裂解模式进行明确的物种鉴定。尽管如此，ESI-MS表现出物种特异性检测器响应。因此，将采用互补CE/ICP-SFMS耦合，根据种属非依赖性响应进行种属定量。此外，同位素比的确定使得能够应用富集的稳定同位素（例如，65 Cu，67 Zn）用于追踪和量化目的。II）在方法开发后，将进行实验室规模的浸出实验，并且在实验过程中将增加基质的复杂性。在这些实验的基础上，将阐明金属基防污杀菌剂的形态和金属转移行为。由于在实验室规模的实验中获得的经验，选择性和不变的目标物种将被确定（作为以前的原始金属络合物的指示剂）。III）根据所确定的目标物种，从码头/港口收集的真实的地表水样品的分析将进行评估输入以及环境污染的杀虫剂进入水生环境。最后，将简化所开发的方法，使其能够广泛适用并可转移到其他实验室。（目前）完全放弃防污物质是不可能的，因为环境上合理的替代方法目前还不够稳健。因此，需要分析方法，以更有针对性和更有效地使用防污物质。