Trace Analysis of Five Androgens in Environmental Waters by Optimization of Enzymolysis and Solid-Phase Extraction Ultra-Performance Liquid Chromatography-Mass Spectrometry and its Risk Assessment.

Steroid hormones (SHs) have received widespread attention in recent years. However, current studies of SHs have primarily focused on estrogenic substances, with androgen-related studies being quite limited. We optimized the solid-phase extraction (SPE) pretreatment method, as well as the enzymolysis conditions of five androgens (androstenedione, boldenone, methandienone, nandrolone, and testosterone), to simultaneously determine their concentrations in the effluent from wastewater treatment plants and surface water samples. Then we evaluated the ecological risks of the five androgens in the effluent and Pearl River basin of Guangzhou (PR China) using the risk quotient method. The recovery rates of the targets were 90% to 99% in water samples when digested with ß-glucosidase for 90 min before solid-phase extraction, extracted with a Poly-Sery HLB column, and washed with 15% methanol aqueous solution and 2% ammonia. The established instrument's limit of detection was between 0.02 and 0.39 µg/L, and the limit of quantification was between 0.05 and 1.29 µg/L. Androstenedione, boldenone, methandienone, nandrolone, and testosterone were detected in all samples from the 2018 and 2022 wastewater influent and the 2018 surface water, with concentrations of 3.06 × 101 ng/L to 1.33 × 103 ng/L, 1.03-8.15 × 102 ng/L, and 0.93 × 101 ng/L to 5.50 × 102 ng/L, respectively. The ecological risks of androgens in wastewater influent and surface water were medium to high and low to medium, respectively. Moreover, the biotoxicity of androgens was predicted by the Ecological Structure Activity Relationships model, with methandienone and androstenedione having the highest and lowest acute and chronic toxicities, respectively. These results suggest that the risk of environmental androgens should not be ignored and that further research should be carried out. Environ Toxicol Chem 2024;43:915-925. © 2023 SETAC.

Assessment of the excretion of oxidative stress biomarkers and anabolic steroids based on sewage: A case study of college students and the general population.

The use of wastewater-based epidemiology to evaluate the health and lifestyle of the population is a novel research interest. However, studies concerning the excretion of endogenous metabolites due to oxidative stress and the consumption of anabolic steroids have rarely been involved. In this study, we compared the effects of events such as final examination and sports meeting on the levels of four oxidative stress biomarkers (8-isoPGF2α, HNE-MA, 8-OHdG, and HCY) and four prohibited anabolic steroids (Testosterone, Androstenedione, Boldenone, and Metandienone) in sewage, using university students and urban populations as studying target. It was found that the per capita mass load of the four oxidative stress biomarkers 8-isoPGF2α, HNE-MA, 8-OHdG, and HCY in the sewage of Guangzhou urban area and university town were 256.6 ± 76.1, 9.4 ± 3.8, 1.1 ± 0.5, and 0.9 ± 0.4 mg/d/1000, respectively. The mean mass load of 8-isoPGF2α was significantly higher than that before the COVID-19 pandemic (74.9 ± 29.6 mg/d/1000 people, P < 0.05). The per capita load levels of oxidative stress biomarkers were significantly higher (P < 0.05) during the 2022 exam week relative to the pre-exam period, indicating that the exams caused transient stress to students. The per capita mass load of androgenic steroids was 77.7 mg/d/1000 people. There was an increase in the per capita load level of androgenic steroids during the provincial sports meeting. In this study, we quantified the concentration of oxidative stress biomarkers and androgenic steroids in the sewage and better realized the application of WBE on the health level and lifestyle of the population during special events.