An online solid-phase extraction and liquid chromatography in combination with tandem mass spectrometry method was developed for the simultaneous determination of 31 antibiotics in drinking water, surface water and reclaimed waters. The developed methodology requires small sample volume (10 mL), very little sample preparation and total sample run time was 20 min. An Ion Max API heated electrospray ionization source operated in the positive mode with two selected reaction monitoring transitions was used per antibiotic for positive identity and quantification performed by the internal standard approach, to correct for matrix effects and any losses in the online extraction step. Method detection limits were in the range of 1.2-9.7, 2.2-15, 5.5-63 ng/L in drinking water, surface water and reclaimed waters, respectively. The method accuracy in matrix spiked samples ranged from 50-150% for the studied antibiotics. The applicability of the method was demonstrated using various environmental and reclaimed water matrices. Erythromycin was detected in more than 85% of the samples in all matrices (28-414, n.d.-199, n.d.-66 ng/L in reclaimed, river and drinking waters respectively). The other frequently detected antibiotics in reclaimed waters were nalidixic acid, clarithromycin, azithromycin, trimethoprim, and sulfamethoxazole.
The photochemical fate of seven sulfonamides was investigated in matrices representative of natural water bodies under various light sources. Fundamental photolysis parameters such as molar absorption coefficient, quantum yield (QY) and first-order rate constants were determined. The photolysis decay rate was dependent on the protonation state of the molecule, pH of the water sample and dissolved organic matter. Natural organic matter was the most significant factor in the indirect photolysis of sulfonamides. Half-lives were in the range of minutes at 254 nm to days under natural sunlight. Under natural sunlight, all sulfonamides showed higher removal rates in natural waters implying that indirect photolysis is the predominant mechanism.
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