Determination of Commonly Used Azole Antifungals in Various Waters and Sewage Sludge Using Ultra-high Performance Liquid Chromatography-tandem Mass Spectrometry

Sensitive and reliable methods have been developed and validated for determination of commonly consumed azole antifungal pharmaceuticals (clotrimazole, econazole, ketoconazole, and miconazole) and biocides (propiconazole and tebuconazole) in various waters and sewage sludge. Solid phase extraction (SPE) combined with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was used to determine the azole antifungals in waters. Azole antifungals in sewage sludge were extracted with ultrasonic-assisted extraction, followed by SPE cleanup and UHPLC-MS/MS detection. Quantification was performed by internal standard calibration in multiple reaction monitoring mode. Recoveries were mostly in the range of 52-110% with relative standard deviations generally within 20%. Method quantification limits were 0.5-6 ng L(-1) in waters and 3-9 ng g(-1) dry weight (dw) in sewage sludge, respectively. The methods were applied to determine the azole antifungals in wastewater, river water, sediment, and sewage sludge sampled from the Pearl River Delta, China. Clotrimazole, ketoconazole, and miconazole were widely detected at low ng L(-1) in waters, low ng g(-1) dw in river sediment, and low microg g(-1) dw in sewage sludge. The methods can provide valuable tools for investigating occurrence and fate of the azole antifungals in the environment.