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Growing attention has been recently paid to safety of food and drinking water, making necessary the adoption of policies for water sources protection and the development of sensitive and rapid analytical methods to identify micropollutants. Endocrine-disrupting compounds (EDCs) have emerged as a major issue as they alter the functioning of the endocrine system. Since ingestion of EDCs via food is considered the major exposure route, there is a growing interest in understanding EDC fate during drinking water treatment and in monitoring potential contamination of surface waters and groundwaters. In this work, a fast liquid chromatography-electrospray ionization-tandem mass spectrometry method was developed for the determination of 4-n-nonylphenol (NP), bisphenol A (BPA), estrone (E1), 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) in drinking waters. In the literature analytical articles seldom provide details regarding fragmentation pathways. In this paper spectra of the five EDCs in negative ESI were interpreted with the support of accurate mass spectra acquired by a quadrupole time-of-flight instrument; fragmentation pathways were also proposed. The chromatographic separation of EDCs was optimized on a Pinnacle DB Biphenylic column with a water-acetonitrile gradient. Quantitative analysis was performed in multiple reaction monitoring (MRM) mode using bisphenol A-d(16) (BPA-d(16)) as internal standard; calibration curves showed good correlation coefficients (0.9989-0.9997). All figures of merit of the method were satisfactory; limits of detection were in the range 0.2-0.4 ng/ml. The method was applied to the determination of the analytes in waters sampled by polar organic chemical integrative samplers in a drinking water treatment plant. Rather low concentration of BPA, NP and E1 were measured in the inlet, while none of the considered EDCs was detected in the outlet.

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Six UV filtersbenzophenone-3 (BP-3), octocrylene (OC), ethylhexyl dimethyl p-aminobenzoate (OD-PABA), ethylhexyl methoxycinnamate (EHMC), ethylhexyl salicylate (EHS) and homosalate (HMS)with endocrine disrupting potential were monitored in different wastewater treatment plants (WWTPs) located in Genoa, Italy. The influent and effluent samples were collected once a month from April to September 2011. The analytes were determined by stir bar sorptive extraction followed by liquid desorption (SBSE-LD) combined with liquid chromatography-tandem mass spectrometry (LC-MS/MS). Quantitative analysis was performed in triggered MRM (tMRM), which allowed improvement of specificity without compromising sensitivity. In the inlet samples four analytes were detected; in particular BP-3, OC, EHMC, and OD-PABA were in the range of 4-163, 12-390, 23-68, and 2-4 ng L À1 , respectively. Measured concentrations indicated variability of UV filter inputs to WWTPs, with higher loads during the warmer months. A highly positive correlation was found between air temperature and the measured concentration of OC and BP-3. Only BP-3 and OC were detected in some effluent samples, with considerably lower concentrations. The removal efficiencies of the plants were in the range of 64 to >99% and 94 to >99% for BP-3 and OC, respectively.

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