Tebuconazol und Penconazol – Bestimmung von TEB-OH, TEB-COOH, PEN-OH und PEN-COOH in Urin mittels LC-MS/MS

Biomonitoring-Methode

Elisa Polledri¹ (Methodenentwicklung)
Rosa Mercadante¹ (Methodenentwicklung)
Silvia Fustinoni¹ (Methodenentwicklung)
Laura Kuhlmann² (Methodenprüfung)
  Thomas Göen² (Methodenprüfung; Leitung der Arbeitsgruppe „Analysen in biologischem Material“ der Ständigen Senatskommission zur Prüfung gesundheitsschädlicher Arbeitsstoffe, Deutsche Forschungsgemeinschaft)
  Andrea Hartwig³ (Vorsitz der Ständigen Senatskommission zur Prüfung gesundheitsschädlicher Arbeitsstoffe, Deutsche Forschungsgemeinschaft)
  MAK Commission<sup>4

1</sup> Laboratory of Environmental and Occupational Toxicology, Department of Clinical Sciences and Community Health, University of Milano and Fondazione IRCCS Ca Granda Ospedale Maggiore Policlinico, Via Francesco Sforza 35, 20122 Mailand, Italien
² Friedrich-Alexander-Universität Erlangen-Nürnberg, Institut und Poliklinik für Arbeits-, Sozial- und Umweltmedizin, Henkestraße 9–11, 91054 Erlangen, Deutschland
³ Institut für Angewandte Biowissenschaften, Abteilung Lebensmittelchemie und Toxikologie, Karlsruher Institut für Technologie (KIT), Adenauerring 20a, Geb. 50.41, 76131 Karlsruhe, Deutschland
⁴ Ständige Senatskommission zur Prüfung gesundheitsschädlicher Arbeitsstoffe, Deutsche Forschungsgemeinschaft, Kennedyallee 40, 53175 Bonn, Deutschland

Abstract

The working group “Analyses in Biological Materials” of the German Senate Commission for the Investigation of Health Hazards of Chemical Compounds in the Work Area (MAK Commission) developed and verified this biomonitoring method for the measurement of the most important urinary metabolites of the triazole fungicides tebuconazole and penconazole. Specifically, this method determines (RS)-5‑(4‑chlorophenyl)-2,2‑dimethyl-3‑(1H‑1,2,4‑triazol-1‑ylmethyl)-1,3‑pentanediol (TEB‑OH) and (RS)-5‑(4‑chlorophenyl)-2,2‑dimethyl-3‑(1H‑1,2,4‑triazol-1‑ylmethyl)-3‑olpentanoic acid (TEB‑COOH) as well as 4‑(2,4‑dichlorophenyl)-5‑[1,2,4]‑triazol-1‑ylpentanol (PEN‑OH) and 4‑(2,4‑dichlorophenyl)-5‑[1,2,4]‑triazol-1‑ylpentanoic acid (PEN‑COOH) in urine. After adding isotope-labelled internal standards, the samples are enzymatically hydrolysed to release the analytes from the glucuronide and sulfate conjugates. After online purification, the analytes are separated by liquid chromatography and analysed using tandem mass spectrometry. Calibration is performed using calibration standards prepared in pooled urine and processed analogously to the samples to be analysed. The method provides reliable and accurate analytical results, as shown by the good precision data with standard deviations in the range of 0.1–10.7%. Good accuracy data were obtained with mean relative recoveries in the range of 100–107%. The method is selective, sensitive, and provides quantitation limits of 0.3 μg/l for TEB-OH and TEB-COOH and of 1.0 μg/l for PEN-OH and PEN-COOH.

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