Mass balance of emerging contaminants in the water cycle of a highly urbanized and industrialized area of Italy.

The occurrence of several classes of emerging contaminants (ECs) was assessed in the River Lambro basin, one of the most urbanized and industrialized areas of Italy. The study aims were to identify the main sources of ECs, quantify their amounts circulating in the water cycle, and study their fate in the aquatic environment. More than 80 ECs were selected among pharmaceuticals (PHARM), personal care products (PCPs), disinfectants (DIS), illicit drugs (IDs), perfluorinated compounds (PERF), alkylphenols and bisphenol A (Alk-BPA), and anthropogenic markers (AM). Specific analytical methods were developed for quantitative analysis based on solid phase extraction and liquid chromatography tandem mass spectrometry. ECs were measured in rivers upstream and downstream of the main city (Milan), and in untreated and treated wastewater from Milan to assess the contribution to river contamination, and in superficial and deep groundwater in the city area to study the relationship between river and groundwater contamination. Samples were collected in a two-year monitoring campaign. Almost all ECs were ubiquitous in untreated wastewater, at concentrations up to the μg/L range, and the most abundant classes were PHARM and AM. Removals during different wastewater treatment processes were studied and the most stable substances were PHARM, PCPs and PERF. The mass loads increased for all the classes of ECs along the River Lambro basin. A mass balance was done in the river basin and allowed to identify the main sources of contamination, which were domestic, from treated or untreated wastewater, for PHARM, PCPs and IDs, mainly industrial for PERF, and both industrial and domestic for Alk-BPA. The study of AM helped to identify direct discharges of untreated wastewater. A substantial contribution of surface water to groundwater contamination was observed. This study improves the knowledge on occurrence, sources and fate of multiple classes of ECs in a highly urbanized area providing useful information to help the establishment of EU regulations for ECs.