Simultaneous Determination of Ten Endocrine Hormone Disrupters in Water Using SPE/LC-(ESI)MS-MS

Abstract

The aim of this study was developed and validated an analytical method based on liquid chromatography and tandem mass spectrometry after solid phase extraction to monitorizing ten endocrine hormone disrupters in Lisbon drinking water system. Natural and synthetic hormones (17-β-estradiol, ethinylestradiol, estriol, estrone, progesterone, mestranol and diethylstilbestrol) and some industrial products (4-n-nonylphenol, 4-tert-octylphenol and bisphenol A) were studied. Mass spectrometer detection parameters were optimized, such as the best conditions for the precursor ion formation, namely cone voltage, when applying negative and positive electrospray ionization, and also collision energy for MRM1 and MRM2 transitions. The best conditions of the solid phase extraction (SPE) using Waters Oasis HLB (6 mL, 200 mg) and Isolute C18 (EC) (6 ml, 1000 mg) were also optimized. The method was validated through the application of several statistical tests and the uncertainty estimation of the analytical assay. This method showed a very good linear range for all the studied analytes with determination coefficients (r 2 ) between 0.9962 and 0.9999 and coefficients of variation lower than 4%. There were no significant differences between recoveries obtained with the studied matrices, like groundwater, surface water and water for human consumption. In these matrices, the recovery values varied between 32 and 95%. The limits of method detection were between 0.28 and 22 ng/L. The validated method was applied for the analysis of water samples from the EPAL (Empresa Portuguesa das Águas Livres, S.A.) water supply system including tap water, spring water, groundwater, and river water. Some target compounds (bisphenol A, progesterone, 4-tert-octylphenol, and 4-n-nonylphenol) were found in trace amounts in analysed waters.

Determination of natural and synthetic oestrogens in surface water using gas chromatography-mass spectrometry

“…The assigned expanded uncertainty with application of a coverage factor of 2 ranged from 24% to 48%, depending on the analyte and was slightly higher than those obtained by LC-MS/MS technique (14).…”

Overview of Sample Preparation and Chromatographic Methods to Analysis Pharmaceutical Active Compounds in Waters Matrices

“…However, most researchers report linear studies based on R 2 and the other parameters are not quantified. Only a few reviews [10,59] write the Mandel test. Usually, the PG and tabulated F values are missing.…”

“…Henriques et al [59] compared the expanded uncertainties that were obtained by bottom-up approach (method 1) and the top-bottom approach (method 2) in the quantification of endocrine disrupters in natural and drinking waters by SPE-LC-MS/MS [238,239]. The estimation of uncertainty by method 1 was between 18% and 26%, while, by method 2, it was between 15% and 30%.…”

“…Owing to the large-scale dilution of these contaminants in water sources (natural waters) or due to the matrix complexity, a preliminary sample preparation technique for concentration or/and clean-up is mandatory, such as liquid-liquid extraction (LLE) [57], solid-phase extraction (SPE) [10,27,[58][59][60], solid-phase microextraction (SPME) [27,28], or stir bar sorptive extraction (SBSE) [61]. Currently, pharmaceuticals are usually extracted from water samples by off-line solid-phase extraction [10,46,61] and on-line solid phase extraction [44,62].…”

Mycoremediation of 17 β‐Estradiol Using Trichoderma citrinoviride Strain AJAC3 along with Enzyme Studies

“…The cartridges rinsed with mixture of methanol: acetone (3:2 v/v) was followed by a wash with methanol and water consecutively. The sample was then added to cartridges and elution was performed with methanol: acetone (3:2 v/v) solution . The eluted constituents were used for HPLC.…”