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Online solid phase extraction LC–MS/MS method for the analysis of succinate dehydrogenase inhibitor fungicides and its applicability to surface water samples

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Abstract

A sensitive and selective analytical method, based on online solid phase extraction coupled to LC–MS/MS, was developed and validated to determine traces of several recently introduced fungicides in surface water and wastewater. The list of target analytes included eight succinate dehydrogenase inhibitors (bixafen, boscalid, fluopyram, flutolanil, fluxapyroxad, isopyrazam, penflufen, and penthiopyrad), and two other fungicides with different modes of action, fenpyrazamine and fluopicolide. Detection and quantification limits in various matrices were in the range of 0.1 to 2 and 0.5 to 10 ng/L, respectively. Moderate signal suppression was observed in surface water (≤15 %) and wastewater (≤25 %) and was well compensated by the selected internal standard. The intra- and inter-day precisions were generally <10 and <20 %, respectively. The applicability of the method was demonstrated in a study on the occurrence of fungicides in the river Glatt, Switzerland, that drains a catchment area of 419 km2 with a substantial proportion of agricultural land. Of the studied compounds, only boscalid and fluopicolide were detected in flow-proportional weekly composite samples, generally at low concentrations up to 15 and 5 ng/L, respectively. While fluopicolide was detected in only 30 % of the samples above the LOD of 0.5 ng/L, boscalid was detected in all samples analyzed between March and October 2012.

Concentration of the fungicides boscalid and fluopicolide in flow-proportional weekly-composite watersamples from River Glatt, Switzerland in 2012

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References

  1. Dehne HW, Deising HB, Gisi U, Kuck KH, Russel PE, Lyr H (2011) Modern fungicides and antifungal compounds VI. Lebenshilfe gGmbH, Braunschweig

    Google Scholar 

  2. Keon JPR, White GA, Hargreaves JA (1991) Isolation, characterization and sequence of a gene conferring resistance to the systemic fungicide carboxin from the maize smut pathogen, Ustilago maydis. Curr Genet 19:475–481

    Article  CAS  Google Scholar 

  3. Glättli AG, Grote T, Stammler G (2011) SDH-inhibitors: history, biological performance and molecular mode of action. In: Dehne HW, Deising HB, Gisi U, Kuck KH, Russel PE, Lyr H (eds) Modern fungicides and antifungal compounds VI. Lebenshilfe, gGmbH, Braunschweig, pp 159–169

    Google Scholar 

  4. Avenot HF, Michailides TJ (2010) Progress in understanding molecular mechanisms and evolution of resistance to succinate dehydrogenase inhibiting (SDHI) fungicides in phytopathogenic fungi. Crop Prot 29:643–651

    Article  CAS  Google Scholar 

  5. Walter H (2011) New fungicides and new modes of action. In: Dehne HW, Deising HB, Gisi U, Kuck KH, Russel PE, Lyr H (eds) Modern fungicides and antifungal compounds VI. Lebenshilfe, gGmbH, Braunschweig, pp 47–54

    Google Scholar 

  6. Reilly TJ, Smalling KL, Orlando JL, Kuivila KM (2012) Occurrence of boscalid and other selected fungicides in surface water and groundwater in three targeted use areas in the United States. Chemosphere 89:228–234

    Article  CAS  Google Scholar 

  7. McCall PJ, Swann RL, Laskowski DA, Unger SM, Vrona SA, Dishburger HJ (1980) Estimation of chemical mobility in soil from liquid chromatographic retention times. Bull Environ Contam Toxicol 24:190–195

    Article  CAS  Google Scholar 

  8. Tsuda T, Nakamura T, Inoue A, Tanaka K (2009) Pesticides in water and sediment from littoral area of Lake Biwa. Bull Environ Contam Toxicol 82:683–689

    Article  CAS  Google Scholar 

  9. Tanabe A, Mitobe H, Kawata K, Yasuhara A, Shibamoto T (2001) Seasonal and spatial studies on pesticide residues in surface waters of the Shinano River in Japan. J Agric Food Chem 49:3847–3852

    Article  CAS  Google Scholar 

  10. Anasco N, Uno S, Koyama J, Matsuoka T, Kuwahara N (2010) Assessment of pesticide residues in freshwater areas affected by rice paddy effluents in Southern Japan. Environ Monit Assess 160:371–383

    Article  CAS  Google Scholar 

  11. Anasco NC, Koyama J, Uno S (2010) Pesticide residues in coastal waters affected by rice paddy effluents temporarily stored in a wastewater reservoir in Southern Japan. Arch Environ Contam Toxicol 58:352–360

    Article  CAS  Google Scholar 

  12. Oh YJ, Jung YJ, Kang J-W, Yoo YS (2007) Investigation of the estrogenic activities of pesticides from Pal-dang reservoir by in vitro assay. Sci Total Environ 388:8–15

    Article  CAS  Google Scholar 

  13. Moreno-González R, Campillo JA, García V, León VM (2013) Seasonal input of regulated and emerging organic pollutants through surface watercourses to a Mediterranean coastal lagoon. Chemosphere 92:247–257

    Article  Google Scholar 

  14. Rasmussen JJ, McKnight US, Loinaz MC, Thomsen NI, Olsson ME, Bjerg PL, Binning PJ, Kronvang B (2013) A catchment scale evaluation of multiple stressor effects in headwater streams. Sci Total Environ 442:420–431

    Article  CAS  Google Scholar 

  15. Smalling KL, Kuivila KM, Orlando JL, Phillips BM, Anderson BS, Siegler K, Hunt JW, Hamilton M (2013) Environmental fate of fungicides and other current-use pesticides in a central California estuary. Mar Pollut Bull 73:144–153

    Article  CAS  Google Scholar 

  16. Garcia-Ac A, Segura PA, Viglino L, Furtos A, Gagnon C, Prevost M, Sauve S (2009) On-line solid-phase extraction of large-volume injections coupled to liquid chromatography-tandem mass spectrometry for the quantitation and confirmation of 14 selected trace organic contaminants in drinking and surface water. J Chromatogr A 1216:8518–8527

    Article  CAS  Google Scholar 

  17. Huntscha S, Singer HP, McArdell CS, Frank CE, Hollender J (2012) Multiresidue analysis of 88 polar organic micropollutants in ground, surface and wastewater using online mixed-bed multilayer solid-phase extraction coupled to high performance liquid chromatography-tandem mass spectrometry. J Chromatogr A 1268:74–83

    Article  CAS  Google Scholar 

  18. The Swiss Federal Statistical Office (SFSO), Swiss statistics web site, Arealstatitstik 2004/2009.

  19. Buerge IJ, Buser H-R, Kahle M, Müller MD, Poiger T (2009) Ubiquitous occurrence of the artificial sweetener acesulfame in the aquatic environment: an ideal chemical marker of domestic wastewater in groundwater. Environ Sci Technol 43:4381–4385

    Article  CAS  Google Scholar 

  20. Buerge IJ, Kahle M, Buser H-R, Müller MD, Poiger T (2008) Nicotine derivatives in wastewater and surface waters: application as chemical markers for domestic wastewater. Environ Sci Technol 42:6354–6360

    Article  CAS  Google Scholar 

  21. Kahle M, Buerge IJ, Hauser A, Müller MD, Poiger T (2008) Azole fungicides: occurrence and fate in wastewater and surface waters. Environ Sci Technol 42:7193–7200

    Article  CAS  Google Scholar 

  22. Reemtsma T, Alder L, Banasiak U (2013) Emerging pesticide metabolites in groundwater and surface water as determined by the application of a multimethod for 150 pesticide metabolites. Water Res 47:5535–5545

    Article  CAS  Google Scholar 

  23. Federal Office of Consumer Protection and Food Safety (BVL) 2011, Report on domestic sales and export of plant protection products in 2011 (in German). Available online:http://www.bvl.bund.de/SharedDocs/Downloads/04_Pflanzenschutzmittel/meld_par_19_2011_EN.pdf?__blob=publicationFile&v=2

  24. Federal Office of Consumer Protection and Food Safety (BVL) 2012, Report on domestic sales and export on plant protection products in 2012 (in German). Available online: http://www.bvl.bund.de/SharedDocs/Downloads/04_Pflanzenschutzmittel/meld_par_19_2012.pdf?__blob=publicationFile&v=3

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Acknowledgments

We thank Thorsten Behsen from LKC Switzerland Ltd. for providing a penthiopyrad analytical standard and the Office of Waste, Water, Energy and Air of the Canton of Zurich (AWEL) for conducting the sampling on River Glatt.

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Correspondence to Thomas Poiger.

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Gulkowska, A., Buerge, I.J. & Poiger, T. Online solid phase extraction LC–MS/MS method for the analysis of succinate dehydrogenase inhibitor fungicides and its applicability to surface water samples. Anal Bioanal Chem 406, 6419–6427 (2014). https://doi.org/10.1007/s00216-014-8073-4

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  • DOI: https://doi.org/10.1007/s00216-014-8073-4

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