SPE-LC-MS/MS Analysis of Chiral and Achiral Fungicides in Drinking Water

Fungicide contamination is an increasing global environmental concern, due to the harm they may pose to non-target organisms, their contribution to antimicrobial resistance, and the potential risks to human health when drinking water (DW) sources are impacted. Many fungicides used in agriculture are chiral and may exist as racemates, or a combination of diastereoisomers and/or enantiomers. Since enantiomers can differ in environmental fate, distribution, and toxicity, enantioselective analysis of chiral fungicides is crucial. The aim of this study was to develop and validate an analytical method for the determination of azole chiral and achiral fungicides in DW using solid-phase extraction followed by liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS). Chromatographic separation of one achiral fungicide and five chiral fungicides was achieved using a polysaccharide chromatographic column under reverse elution mode. The validated method demonstrated high sensitivity with method detection limits (MDL) below 0.86 ng L−1 and was successfully applied to 13 DW samples collected from various supply networks across Portugal. Seven out of the 15 targeted analytes were found at trace concentrations (>MDL). Fluconazole was the most frequently detected (~87% of the samples). The hazard quotients (HQs) for individual compounds for each individual fungicide (sum of the enantiomers for those chiral) and the hazard index (HI, sum of the individual HQ values) were calculated in each DW sample, indicating no significant health risks to consumers, since it is well below 0.1 for all compounds.