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Development of complementary CE-MS methods for speciation analysis of pyrithione-based antifouling agents

  • Sebastian Faßbender
  • Ann-Katrin Döring
  • Björn MeermannEmail author
Research Paper

Abstract

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 μM (HPT) and between 0.062 and 0.59 μM ((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

Keywords

Capillary electrophoresis–mass spectrometry (CE-MS) Electrospray ionization–mass spectrometry (ESI-MS) Inductively coupled plasma–mass spectrometry (ICP-MS) Complementary MS Environmental speciation Cu/Zn pyrithione antifouling biocides 

Notes

Acknowledgments

The Department Aquatic Chemistry of the Federal Institute of Hydrology, Koblenz, Germany, is gratefully acknowledged for instrumental, consumables, and laboratory space support.

Funding information

The German Research Foundation (DFG—Deutsche Forschungsgemeinschaft; reference number ME 3685/3-1, project number 321800101) is gratfully acknowledged for funding.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no competing interests.

Supplementary material

216_2019_2094_MOESM1_ESM.pdf (1.3 mb)
ESM 1 (PDF 1.29 mb)

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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Division 1.1 – Inorganic Trace AnalysisFederal Institute for Materials Research and TestingBerlinGermany
  2. 2.Department G2 – Aquatic ChemistryFederal Institute of HydrologyKoblenzGermany

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