Development of a Multi-Residue Method for Monitoring 44 Pharmaceuticals in Slovene Surface Water by SPE-LC-MS/MS

摘要

The article describes a novel analytical method based on solid-phase extraction and LC-MS/MS for detection of a high number (n = 44) of selected pharmaceuticals in surface waters. The validated method showed suitable accuracy, precision, and linearity. The extraction efficiency for pharmaceuticals was mostly above 90% and the determined LOQs were generally below 5 ng/L and even down to 0.03 ng/L. The matrix effect was successfully minimized with isotopically labeled internal standards. Six river and lake samples from Slovene regions were afterwards analyzed. Forty-two of the 44 target pharmaceuticals were detected in at least two water samples; 66% of them were detected in all samples. Three analytes were present above the LOQ in all samples: caffeine (1.1-3.1 ng/L), irbesartan (0.2-9.3 ng/L), and valsartan (0.8-47 ng/L). The highest concentration was measured for valsartan. Comprehensive comparison with the literature data showed that the found concentrations of pharmaceuticals were notably lower in our study and that a number of the pharmaceuticals had not been reported previously. Comparison of the measured and predicted (calculated) environmental concentrations of pharmaceuticals in surface waters showed high discrepancy between the two approaches, clearly indicating the need for comprehensive analytical methods for routine monitoring of these newly emerging pollutants. In conclusion, our method was proven to be adequately sensitive to reliably quantify the majority of pharmaceutical contaminants even though they were found in notably lower concentrations in Slovenian surface waters than it was predicted from their consumption and from the literature.