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

Abstract

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.

Sensitivity Enhancement for Separation-Based Analytical Techniques Utilizing Solid-Phase Enrichment Approaches and Analyte Derivatization for Trace Analysis in Various Matrices

“…The simultaneous determination of natural and synthetic estrogens, progestogens, and androgens in environmental water samples at very low quantities using a quick and sensitive analytical approach has been described utilizing the GC technique [67]. An analytical GC approach incorporating a one-way SPE has been used to analyze geosmin and its metabolite, 2-methylisoborneol, for drinking water [68].…”

Establishment of a graphene quantum dot (GQD) based steroid binding assay for the nuclear progesterone receptor (pgr)

“…The assay has also been used to determine the progestagenic activities of anabolic androgenic steroids used in sports doping [ 39 ], a wide variety of compounds [ 40 ], and as a pseudo-immunoassay for the detection of progestins [ 41 , 42 ]. Recently, several advanced analytical techniques have been developed for the detection of EDCs [ [43] , [44] , [45] ]. These are mainly monitored by in vitro reporter gene bioassays based on human Pgr.…”

Novel biosensor for high-throughput detection of progesterone receptor-interacting endocrine disruptors

“…Multiple highly sensitive analytical methods for detection of these EDCs have been developed recently 43 , 44 . Although these methods are sensitive, they are expensive, time-consuming and for the most part not suitable for high-throughput screening of environmental samples.…”