Simultaneous determination of human pharmaceuticals in water samples by solid phase extraction and HPLC with UV-fluorescence detection

The presence of pharmaceutical active products (PPs) in the aquatic environment is principally due to insufficient removal at wastewater treatment plants (WWTPs). Although PPs and their metabolites are often found in waters at trace levels, they can maintain a high biological activity with potential adverse effects on biotic communities. The development of accurate and sensitive methods is therefore necessary for their detection in aquatic ecosystems. In this context, the aim of this study was to validate a simple and reliable analytical procedure for determining selected pharmaceuticals in wastewaters and surface waters by applying solid phase extraction (SPE) using polymeric Strata X extraction cartridges and HPLC with simultaneous UV and fluorescence detection. Nine selected PPs belonging to different therapeutic classes (carbamazepine, gemfibrozil, clofibric acid, fenofibrate, fenoprofen, ibuprofen, naproxen, ketoprofen, and diclofenac) and three steroid hormones (17β-estradiol, 17α-ethinylestradiol, and estrone) were considered. The method, validated on spiked real water samples (river water, influent and effluent from a WWTP), showed satisfactory accuracy and sensitivity, with average recoveries in the 65–104% range and relative standard deviations (RSD) ≤ 16%. The limits of quantification (LOQs) ranged from 10 to 1100 ng/L for all spiked matrices. The optimized method has been successfully applied to the detection of the selected compounds in environmental waters, such as two contaminated sites along the urban stretch of the River Tiber in the city of Rome (Italy) and from both the influent and effluent from a municipal WWTP close to Rome. The method developed is proposed for routine analysis of PPs in polluted waters as it is a useful and affordable alternative when more sophisticated techniques are not available.

► Pharmaceuticals are emerging contaminants in waters not yet regulated at EU level.
► Incomplete removal of PPs in WWTPs is the main source of water contamination.
► Accurate and sensitive methods are necessary for PPs detection in water samples.
► We validated a simple and reliable analytical method based on SPE and HPLC-UV-FL.
► The optimized method has been successfully applied to polluted waters.