Determination of Endocrine Disrupting Chemicals in Water and Wastewater Samples by Liquid Chromatography-Negative Ion Electrospray Ionization-Tandem Mass Spectrometry.

Ghada Aborkhees,Renata Raina-Fulton,Ondiveerapan Thirunavokkarasu

doi:10.3390/molecules25173906

Abstract

A liquid chromatography-negative ion electrospray ionization-tandem mass spectrometry method was developed for the simultaneous analysis of bisphenol A, 4-octylphenol, 4-nonylphenol, diethylstilbestrol, 17β-estradiol, estriol, estrone, 17α-ethinylestradiol, prednisone, and prednisolone. This method used solid-phase extraction with an elution solvent of acetonitrile to improve the stability of the analytes. To maintain the stability of analytes analyses were completed within five days. The recoveries ranged from 84 to 112% and the relative standard deviation of analysis of duplicate samples was <10%. The limits of quantitation were 1–10 ng/L. Surface water and wastewater were obtained from five wastewater treatment plants in Saskatchewan. Matrix effects were moderate to severe. Using standard addition calibration, all analytes except diethylstilbestrol and 17α-ethinyl estradiol were detected. There was a low frequency of detection of the target analytes in upstream and downstream water, indicating good removal efficiency during the wastewater treatment process. Bisphenol A and 4-nonylphenol were the only analytes detected downstream. Bisphenol A was the most frequently detected in raw wastewater (133 to 403 ng/L). Estriol was detected more often in raw wastewater than estrone or 17β-estradiol. This is the first Canadian study with the detection of prednisone and prednisolone with concentrations at 198–350 ng/L in raw wastewater at 60% of the wastewater treatment plants.

Highlights

Endocrine-disrupting chemicals (EDCs) are a group of chemicals or mixtures of chemicals in the environment, food sources, personal care products, and manufactured products that exert hormonal-mimicking effects and interfere with the hormonal regulatory mechanisms of living organisms
Two solid-phase extraction (SPE) sorbents (Oasis HLB and Oasis MAX) were selected from previously published methods for other pharmaceuticals not included in these studies for evaluation [42,43]
The C18 SPE sorbent was selected as an alternative sorbent for the evaluation, as SPE could be completed under neutral pH conditions, which reduced or eliminated the need for additives for pH adjustment of water or elution solvents

Summary

Introduction

Endocrine-disrupting chemicals (EDCs) are a group of chemicals or mixtures of chemicals in the environment (air, soil, or water supply), food sources, personal care products, and manufactured products that exert hormonal-mimicking effects and interfere with the hormonal regulatory mechanisms of living organisms. A variety of methods have been used for targeted analyses of endrocrine-disrupting chemicals (EDCs) in surface and wastewater, and often focus on selective groups or a limited target list of EDCs to address the need to optimize the separation and mass spectrometric detection (MS), and to ensure stability and good recoveries of the EDCs in sample preparation procedures. Selective estrogenic EDCs are included in the watch list for the European Union and the United States Environmental Protection Agency [8,9]. This work focuses on natural estrogens (17β-estradiol, estrone, and estriol), synthetic estrogens (17α-ethinylestradiol, and diethylstilbestrol (not prescribed since 1971 in Canada and United States and was previously prescribed to prevent miscarriage and premature delivery)), xenoestrogens (bisphenol A, 4-octylphenol, and 4-nonylphenol), and two glucocorticoid drugs (prednisolone and prednisone) that are not routinely analyzed. Bisphenol A is used in the manufacturing of plastics, rubber, and flame retardants and is released from plastic and polycarbonate materials into wastewater and surface water [10]

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