A sensitive, robust method for determining natural and synthetic hormones in surface and wastewaters by continuous solid-phase extraction–gas chromatography–mass spectrometry

• Published in: Environmental science and pollution research international Vol. 29; no. 35; pp. 53619 - 53632
• Main Authors: Chafi, Safae, Ballesteros, Evaristo
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer Berlin Heidelberg 01.07.2022; Springer Nature B.V
• Subjects: 17β-Estradiol; acetone; Androgens; Aquatic Pollution; Atmospheric Protection/Air Quality Control/Air Pollution; chemical species; Chromatography; compliance; derivatization; Detection limits; Dihydrotestosterone; Earth and Environmental Science; Ecotoxicology; Environment; Environmental Chemistry; Environmental Health; Environmental science; Estrogens; Estrogens - analysis; Estrone; Ethinyl Estradiol - analysis; Ethinylestradiol; Gas chromatography; Gas Chromatography-Mass Spectrometry - methods; Green chemistry; Hormones; Low concentrations; Mass spectrometry; Mass spectroscopy; Microwave oven; microwave ovens; Organic solvents; petroleum; Petroleum ether; Progesterone; Progestins - analysis; Reagents; Research Article; rivers; Scientific imaging; Sex hormones; soil; Soil water; solid phase extraction; Solid Phase Extraction - methods; Solid phases; Sorbents; Spectroscopy; Swimming pools; Testosterone; Waste Water Technology; wastewater; Wastewater - chemistry; Water - analysis; Water Management; Water Pollutants, Chemical - analysis; Water Pollution Control; Water resources; Water sampling; Water; Continuous solid-phase extraction; Natural and synthetic hormones; Gas chromatography–mass spectrometry; Microwave-assisted derivatization
• ISSN: 0944-1344; 1614-7499; 1614-7499
• DOI: 10.1007/s11356-022-19577-1

Over recent decades, steroidal estrogens have become an emerging and very serious issue as they pose a serious threat to living organisms, soil, plants, and water resources in general. Estrogens have therefore been the subject of considerable scientific attention in order to develop new methodologies for its determination, being able of detecting them at very low concentrations. Those procedures minimize or eliminate the consumption of organic solvents and reagents that may be incompatible with the environment. In this respect, we developed a sensitive, selective method for the simultaneous determination of thirteen natural and synthetic hormones present at the nanogram-per-liter level in various types of water by using continuous solid-phase extraction in combination with gas chromatography and mass spectrometry (GC–MS). The target analytes were preferentially sorbed on an Oasis HLB sorbent column (80 mg) and eluted with acetone (600 µL) for derivatization with a mixture of 70 µL of N , O - bis (trimethylsilyl) trifluoroacetamide and trimethylchlorosilane and 35 µL of petroleum ether in a household microwave oven at 200 W for 4 min. Under optimum conditions, the ensuing method exhibited good linearity ( r  ≥ 0.998), good precision (RSD ≤ 7%), high recoveries (92–103%), and low detection limits (0.01–0.3 ng L −1 ). The method outperforms existing alternatives in robustness, sensitivity, throughput, flexibility—it allows both estrogens, progestogens, and androgens to be determined simultaneously—and compliance with the principles of Green Chemistry. It was successfully used to analyze various types of water samples (mineral, tap, well, pond, swimming pool, river, and waste) that were found to contain four estrogens (estrone, 17β-estradiol, 17α-ethinylestradiol, and hexestrol), two progestogens (testosterone, dihydrotestosterone), and one progestogen (progesterone) at concentrations ranging from 3.0 to 110 ng L −1 .