No 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.

One recent trend in Analytical Chemistry is to develop economical, fast green methods using minimal amounts of solvents to determine a variety of analytes spanning a wide range of physicochemical properties. In this work, 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 and eluted with acetone for derivatization with a mixture of N,O-bis(trimethylsilyl) trifluoroacetamide and trimethylchlorosilane 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.

Food safety can be severely compromised by the presence of chemical contaminants. This has raised a pressing need to develop efficient analytical methods for their determination at very low levels in complex food matrices. In this manuscript, we developed a simple, sensitive, fast, green analytical method for the determination of thirteen natural and synthetic hormones from different families including progestogens, estrogens and androgens in meat and fish products. The method involves direct extraction with a (9:1) acetonitrile−water mixture and subsequent purification of the extract by semi-automated solid-phase extraction on a sorbent column (hydrophilic−lipophilic copolymer of N-vinylpyrrolidone and divinylbenzene). This treatment enriches samples with the target compounds while removing proteins, lipids and other potential interferences from their matrix for the accurate determination of the analytes by gas chromatography−mass spectrometry, all within 15 min. The proposed method exhibits good linearity (r ≥ 0.996), low limits of detection (0.4–15 ng/kg), acceptable recoveries (90–105%) and relative standard deviations (≤7%); in addition, it is scarcely subject to matrix effects (1–20%). The method was successfully used to determine natural and synthetic hormones in meat and fish products from Spain, Portugal, Italy, Germany, Greece, Norway, Morocco and the USA. The analytes were found at especially high levels (30−1900 ng/kg) in mussels, beef and pork.