Abstract
A sensitive and reliable liquid chromatographic–tandem mass spectrometric method for enantiomeric determination of five chiral azole antifungals (econazole, ketoconazole, miconazole, tebuconazole, and propiconazole) in wastewater and sludge has been established and validated. An isotope-labeled internal standard was used for quantification. Recovery of the individual enantiomers was usually in the range of 77–102 % for wastewater and 71–95 % for sludge, with relative standard deviations within 20 %. No significant difference (p > 0.05) was observed between recovery of pairs of enantiomers of the chiral azole antifungals except for those of tebuconazole. Method quantification limits for individual enantiomers were 0.3–10 ng L−1 and 3–29 ng g−1 dry weight for wastewater and sludge, respectively. The method was used to investigate the enantiomeric composition of the azole pharmaceuticals in wastewater and sludge samples from a sewage treatment plant in China. Enantiomers of miconazole, ketoconazole, and econazole were widely detected. The results showed that the azole antifungals in wastewater and sludge were generally racemic or marginally non-racemic. The method is a useful tool for investigation of the enantiomeric occurrence, behavior, and fate of the chiral azole antifungals in the environment.
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MRM chromatograms (black) and simulated chromatograms by PeakFit (red) for the chiral azole antifungals in standard solution and samples. MQL, method quantification limit
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Acknowledgements
This work was financially supported by the NSFC program (no. 40972221, no. 41172319) and the Innovative Program of the CAS (no. KZCX2-EW-108). We thank Mr He Jiazhuo of the SKLOG for his help with LC–MS–MS. The personnel of the studied STP are thanked for their help with sampling. This is contribution No. 1472 from GIGCAS.
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Huang, Q., Zhang, K., Wang, Z. et al. Enantiomeric determination of azole antifungals in wastewater and sludge by liquid chromatography–tandem mass spectrometry. Anal Bioanal Chem 403, 1751–1760 (2012). https://doi.org/10.1007/s00216-012-5976-9
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DOI: https://doi.org/10.1007/s00216-012-5976-9