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

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


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


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 



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)


  1. 1.
    Dafforn KA, Lewis JA, Johnston EL. Antifouling strategies: history and regulation, ecological impacts and mitigation. Mar Pollut Bull. 2011;62:453–65.CrossRefGoogle Scholar
  2. 2.
    Dormon JM, Cottrell CM, Allen DG, Ackerman JD, Spelt JK. Copper and copper-nickel alloys as zebra mussel antifoulants. J Environ Eng. 1996;122:276–83.CrossRefGoogle Scholar
  3. 3.
    Schultz MP. Effects of coating roughness and biofouling on ship resistance and powering. Biofouling. 2007;23:331–41.CrossRefGoogle Scholar
  4. 4.
    Voulvoulis N, Scrimshaw MD, Lester JN. Alternative antifouling biocides. Appl Organomet Chem. 1999;13:135–43.CrossRefGoogle Scholar
  5. 5.
    Voulvoulis N, Scrimshaw MD, Lester JN. Analytical methods for the determination of 9 antifouling paint booster biocides in estuarine water samples. Chemosphere. 1999;38:3503–16.CrossRefGoogle Scholar
  6. 6.
    Amara I, Miled W, Slama RB, Ladhari N. Antifouling processes and toxicity effects of antifouling paints on marine environment. A review. Environ Toxicol Pharmacol. 2018;57:115–30.CrossRefGoogle Scholar
  7. 7.
    Sánchez-Rodríguez A, Sosa-Ferrera Z, Santana-Rodríguez J. Analytical methods for the determination of common booster biocides in marine samples. Cent Eur J Chem. 2012;10:521–33.Google Scholar
  8. 8.
    Grunnet KS, Dahllöf I. Environmental fate of the antifouling compound zinc pyrithione in seawater. Environ Toxicol Chem. 2005;24:3001–6.CrossRefGoogle Scholar
  9. 9.
    Neihof RA, Bailey CA, Patouillet C, Hannan PJ. Photodegradation of mercaptopyridine-N-oxide biocides. Arch Environ Contam Toxicol. 1979;8:355–68.CrossRefGoogle Scholar
  10. 10.
    Okamura H, Kobayashi N, Miyanaga M, Nogami Y. Toxicity reduction of metal pyrithiones by near ultraviolet irradiation. Environ Toxicol. 2006;21:305–9.CrossRefGoogle Scholar
  11. 11.
    Onduka T, Mochida K, Harino H, Ito K, Kakuno A, Fujii K. Toxicity of metal pyrithione photodegradation products to marine organisms with indirect evidence for their presence in seawater. Arch Environ Contam Toxicol. 2010;58:991–7.CrossRefGoogle Scholar
  12. 12.
    Sakkas VA, Shibata K, Yamaguchi Y, Sugasawa S, Albanis T. Aqueous phototransformation of zinc pyrithione degradation kinetics and byproduct identification by liquid chromatography--atmospheric pressure chemical ionisation mass spectrometry. J Chromatogr A. 2007;1144:175–82.CrossRefGoogle Scholar
  13. 13.
    Thomas KV. The environmental fate and behaviour of antifouling paint booster biocides: a review. Biofouling. 2001;17:73–86.CrossRefGoogle Scholar
  14. 14.
    Turley PA, Fenn RJ, Ritter JC, Callow ME. Pyrithiones as antifoulants: environmental fate and loss of toxicity. Biofouling. 2005;21:31–40.CrossRefGoogle Scholar
  15. 15.
    Fenn RJ, Alexander MT. Determination of zinc pyrithione in hair care products by normal phase liquid chromatography. J Liq Chromatogr. 1988;11:3403–13.CrossRefGoogle Scholar
  16. 16.
    Nakajima K, Yasuda T, Nakazawa H. High-performance liquid chromatographic determination of zinc pyrithione in antidandruff preparations based on copper chelate formation. J Chromatogr. 1990;502:379–84.CrossRefGoogle Scholar
  17. 17.
    Nakajima K, Ohta M, Yazaki H, Nakazawa H. High-performance liquid chromatographic determination of zinc pyrithione in antidandruff shampoos using on-line copper chelate formation. J Liq Chromatogr. 1993;16:487–96.CrossRefGoogle Scholar
  18. 18.
    Ferioli V, Rustichelli C, Vezzalini F, Gamberini G. Analysis of pyrithiones by reversed-phase high-performance liquid-chromatography. Chromatographia. 1995;40:669–73.CrossRefGoogle Scholar
  19. 19.
    Thomas KV. Determination of the antifouling agent zinc pyrithione in water samples by copper chelate formation and high-performance liquid chromatography-atmospheric pressure chemical ionisation mass spectrometry. J Chromatogr A. 1999;833:105–9.CrossRefGoogle Scholar
  20. 20.
    Doose CA, Ranke J, Stock F, Bottin-Weber U, Jastorff B. Structure–activity relationships of pyrithiones – IPC-81 toxicity tests with the antifouling biocide zinc pyrithione and structural analogs. Green Chem. 2004;6:259–66.CrossRefGoogle Scholar
  21. 21.
    Kobayashi N, Okamura H. Effects of new antifouling compounds on the development of sea urchin. Mar Pollut Bull. 2002;44:748–51.CrossRefGoogle Scholar
  22. 22.
    Okamura H, Togosmaa L, Sawamoto T, Fukushi K, Nishida T, Beppu T. Effects of metal pyrithione antifoulants on freshwater macrophyte Lemna gibba G3 determined by image analysis. Ecotoxicology. 2012;21:1102–11.CrossRefGoogle Scholar
  23. 23.
    Ohji M, Harino H. Comparison of toxicities of metal pyrithiones including their degradation compounds and organotin antifouling biocides to the Japanese killifish Oryzias latipes. Arch Environ Contam Toxicol. 2017;73:285–93.CrossRefGoogle Scholar
  24. 24.
    Marcheselli M, Rustichelli C, Mauri M. Novel antifouling agent zinc pyrithione: determination, acute toxicity, and bioaccumulation in marine mussels (Mytilus galloprovincialis). Environ Toxicol Chem. 2010;29:2583–92.CrossRefGoogle Scholar
  25. 25.
    Bones J, Thomas KV, Paull B. Improved method for the determination of zinc pyrithione in environmental water samples incorporating on-line extraction and preconcentration coupled with liquid chromatography atmospheric pressure chemical ionisation mass spectrometry. J Chromatogr A. 2006;1132:157–64.CrossRefGoogle Scholar
  26. 26.
    Doose CA, Szaleniec M, Behrend P, Müller A, Jastorff B. Chromatographic behavior of pyrithiones. J Chromatogr A. 2004;1052:103–10.CrossRefGoogle Scholar
  27. 27.
    Dabek-Zlotorzynska E, Lai EPC, Timerbaev AR. Capillary electrophoresis: the state-of-the-art in metal speciation studies. Anal Chim Acta. 1998;359:1–26.CrossRefGoogle Scholar
  28. 28.
    Peña-Méndez EM, Havel J, Maleček J. High-performance capillary electrophoresis determination of pyrithione in antidandruff preparations and shampoos. J Capillary Electrophor. 1997;4:269–72.Google Scholar
  29. 29.
    Timerbaev AR. Element speciation analysis using capillary electrophoresis: twenty years of development and applications. Chem Rev. 2013;113:778–812.CrossRefGoogle Scholar
  30. 30.
    Meermann B, Bartel M, Scheffer A, Trumpler S, Karst U. Capillary electrophoresis with inductively coupled plasma-mass spectrometric and electrospray time of flight mass spectrometric detection for the determination of arsenic species in fish samples. Electrophoresis. 2008;29:2731–7.CrossRefGoogle Scholar
  31. 31.
    De Wolf K, Balcaen L, Van De Walle E, Cuyckens F, Vanhaecke F. A comparison between HPLC-dynamic reaction cell-ICP-MS and HPLC-sector field-ICP-MS for the detection of glutathione-trapped reactive drug metabolites using clozapine as a model compound. J Anal At Spectrom. 2010;25:419–25.CrossRefGoogle Scholar
  32. 32.
    Corcoran O, Nicholson JK, Lenz EM, Abou-Shakra F, Castro-Perez J, Sage AB, et al. Directly coupled liquid chromatography with inductively coupled plasma mass spectrometry and orthogonal acceleration time-of-flight mass spectrometry for the identification of drug metabolites in urine: application to diclofenac using chlorine and sulfur detection. Rapid Commun Mass Spectrom. 2000;14:2377–84.CrossRefGoogle Scholar
  33. 33.
    Meermann B, Sperling M. Hyphenated techniques as tools for speciation analysis of metal-based pharmaceuticals: developments and applications. Anal Bioanal Chem. 2012;403:1501–22.CrossRefGoogle Scholar
  34. 34.
    Kroepfl N, Marschall TA, Francesconi KA, Schwerdtle T, Kuehnelt D. Quantitative determination of the sulfur-containing antioxidant ergothioneine by HPLC/ICP-QQQ-MS. J Anal At Spectrom. 2017;32:1571–81.CrossRefGoogle Scholar
  35. 35.
    Paints and varnishes - Determination of release rate of biocides from antifouling paints - Part 1: General method for extraction of biocides, ISO 15181-1, 2007.Google Scholar
  36. 36.
    Foret F, Thompson TJ, Vouros P, Karger BL, Gebauer P, Boček P. Liquid sheath effects on the separation of proteins in capillary electrophoresis/electrospray mass spectrometry. Anal Chem. 1994;66:4450–8.CrossRefGoogle Scholar
  37. 37.
    Huhn C, Ramautar R, Wuhrer M, Somsen GW. Relevance and use of capillary coatings in capillary electrophoresis-mass spectrometry. Anal Bioanal Chem. 2010;396:297–314.CrossRefGoogle Scholar
  38. 38.
    Katayama H, Ishihama Y, Asakawa N. Stable cationic capillary coating with successive multiple ionic polymer layers for capillary electrophoresis. Anal Chem. 1998;70:5272–7.CrossRefGoogle Scholar
  39. 39.
    Soga T, Igarashi K, Ito C, Mizobuchi K, Zimmermann HP, Tomita M. Metabolomic profiling of anionic metabolites by capillary electrophoresis mass spectrometry. Anal Chem. 2009;81:6165–74.CrossRefGoogle Scholar
  40. 40.
    Turley PA, Fenn RJ, Ritter JC. Pyrithiones as antifoulants: environmental chemistry and preliminary risk assessment. Biofouling. 2000;15:175–82.CrossRefGoogle Scholar
  41. 41.
    Chemical analysis - Decision limit, detection limit and determination limit under repeatability conditions - Terms, methods, evaluation, DIN 32645, 2008.Google Scholar

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

Personalised recommendations