Environmental Fate of the Azole Fungicide Fluconazole and Its Persistent and Mobile Transformation Product 1,2,4-Triazole

Fluconazole is a persistent and mobile pharmaceutical azole fungicide observed in natural waters globally. It does not significantly degrade via traditional wastewater treatment, resulting in likely environmental and human exposure and environmental-origin azole fungicide resistance. Indirect photochemistry is known to degrade many recalcitrant contaminants in natural waters but has not been tested for fluconazole. We systematically measured rates and identified products of the indirect photodegradation of fluconazole in genuine and synthetic surface waters with varying nitrate, bicarbonate, and dissolved organic matter using high resolution mass spectrometry. Degradation half-lives of fluconazole ranged from 2 weeks to a year, indicating indirect photochemistry is slow but competitive with other loss processes. The transformation products 1,2,4-triazole and 1,2,4-triazole-1-acetic acid were produced in 30 to 100% yield during fluconazole degradation. These products are far more resistant to indirect photochemistry than fluconazole, with half-lives for 1,2,4-triazole in the environment of between 1 and 3 years when measurable with our methods. These "very persistent very mobile" contaminants are likely formed by most pharmaceutical and agrochemical azole fungicides, are regularly detected in the US and Denmark in monitoring programs and our exposure modeling demonstrates high potential for human exposure through drinking water with uncertain health implications.