Development of analytical methods for speciation analysis of copper and zinc-based antifouling agents in surface water
Final Report Abstract
Surfaces in direct contact with the aquatic environment are subjected to strong chemical and mechanical encroachments. Moreover, so called bio-fouling takes place. During bio-fouling, microorganisms (e.g. bacteria, algae) and in the further course e.g., sea squirts and barnacles attach to e.g., ships´ hull. Bio-fouling results in enhanced fuel consumption as well as greenhouse gas emissions in consequence of strongly enhanced friction. Additionally, it is supposed that attached invasive species can enter aquatic ecosystems leading to incalculable ecological consequences. Given the fact that more than 90% of global trade is transacted via shipping, large economic effects are supposed. Hence, strategies were developed to reduce/prevent bio-fouling - in particular anti-fouling biocides are in use to prevent bio-fouling. Current anti-fouling biocides are based on metal-based complexes. However, analytical methods to detect these substances in surface waters are lacking; furthermore, knowledge on potential degradation routes as well as “target” elemental species are missing. Hence, the focal points of this project were: PI) The development of selective as well as sensitive complementary analytical methods allowing for the (1) separation, (2) sensitive quantification and (3) selective identification/structure elucidation. PII) Lab-scale leaching experiments with increasing of the matrix complexity for the identification of potential target elemental species. PIII) Sampling campaign of potentially polluted marinas/harbors to mirror the status quo of pollution. Within this project a capillary electrophoresis (CE) based method coupled on-line with complementary mass spectrometry (MS; ESI-QToF-MS, ICP-MS) for species identification as well as species-unspecific quantification was successfully developed (PI)). Lab-scale leaching experiments were conducted and by means of the CE/MS based method potentially relevant degradation products were identified (PII)). Due to insufficient sensitivity of the developed CE/MS methods as well as high metalbackground concentrations in sediment samples, PIII) was topically shifted: A challenge in environmental analysis is the distinction between “anthropogenic” as well as “natural” elemental species and tracing of species in complex matrices. Thus, CE was coupled on-line to multicollector-ICP-MS (CE/MC-ICP-MS) - by means of CE/MC-ICP-MS species specific isotope ratios are obtained; within a first successful proof-of-concept study (including also a potential stable degradation product of the anti-fouling agents) different source-dependent isotope ratios of the species were obtained. Except from PIII) all work packages have been successfully completed. As mentioned, the topic shift in PIII) and obtained CE/MC-ICP-MS results are highly promising and inspired us to start a further DFG granted project in the research area of life-sciences.
Publications
- Antifoulingmittel im Wasser, Nachrichten aus der Chemie 2019, Band 67, 56-58
Faßbender S., Meermann B.
(See online at https://doi.org/10.1002/nadc.20194088793) - Development of complementary CE-MS methods for speciation analysis of pyrithione-based antifouling agents, Anal. Bioanal. Chem. 2019, 411, 7261-7272
Faßbender S., Döring A.-K., Meermann B.
(See online at https://doi.org/10.1007/s00216-019-02094-5) - Method development for on-line species-specific sulfur isotopic analysis by means of capillary electrophoresis/multicollector ICP-mass spectrometry, Anal. Bioanal. Chem. 2020, 412, 5637-5646
Faßbender S., Rodiouchkina K., Vanhaecke F., Meermann B.
(See online at https://doi.org/10.1007/s00216-020-02781-8) - Species-specific Isotope Dilution analysis of Monomethylmercury in Sediment using GC/ICP-ToF-MS and comparison with ICP-Q-MS and ICP-SF-MS, Anal Bioanal Chem 2021, 413, 5279-5289
Faßbender S., von der Au M., Koenig M., Pelzer J., Piechotta C., Vogl J., Meermann B.
(See online at https://doi.org/10.1007/s00216-021-03497-z)
