Determination of endocrine‐disrupting compounds in drinking waters by fast liquid chromatography–tandem mass spectrometry

Abstract

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.

Multiple Reaction Monitoring for Direct Quantitation of Intact Proteins Using a Triple Quadrupole Mass Spectrometer

“…One of the MRM transitions was used for quantitation while the other was used for confirmation (termed a qualifier ion). This strategy is in accordance with common practice for MRM-based quantitation on a triple quadrupole and helps ensure specificity [33]. If an interfering matrix ion has the same m/z ratio as the analyte of interest and produces a fragment at the same m/z ratio as the first product ion, confirming the absence of the qualifier ion aids the assignment of this signal as an interference.…”

Assessment of source water contamination by estrogenic disrupting compounds in China

“…Pharmaceuticals, waste water plant effluents, agricultural fertilizers and fish farming wastes are important man-made sources of these environmental pollutants (Yamazaki, 1983;Desbrow et al, 1998;Tashiro et al, 2003). Moreover, they are not completely removed by many conventional water treatment processes, such as chlorination, coagulation, and sedimentation (Kuch and Ballschmiter, 2001;Magi et al, 2010). Estrogenic activity has been detected in effluents of drinking water treatment plants (DWTP) in China, resulting in increased risks to human health (Rao et al, 2004;Wang et al, 2005;Luo et al, 2006).…”

Fungal transformation of 17α-ethinylestradiol in the presence of various concentrations of sodium chloride

“…MS/MS detection was carried out in an MRM negative ionization mode. Optimized MRM pairs for EE2 were: 295.1e145.1 m/z (CE ¼ 41) e quantifier ion, 295.1e159.2 (CE ¼ 19) e qualifier ion as it was previously described by Magi et al (2010). The other optimized parameters of the detector were: CUR: 25.00; TEM: 600.00; GS1:50.00; GS2: 60.00; interface heater: ON; IS: 5500.00; CAD: Medium; DP: 56.00; EP: 6.50; CEP: 16.00; CXP: 3.00.…”

“…The conventional wastewater treatment plants designed for the common effluent treatment have been reported as not being able to efficiently remove the estrogenic contaminations (Magi et al, 2010;Aris et al, 2014;Pessoa et al, 2014). Therefore, EE2 is commonly detected in seawater or in marine sediments but its amounts vary in different geographic regions (Beck et al, 2005;Braga et al, 2005;Pinto et al, 2005;.…”