Analysis of 21 progestagens in various matrices by ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) with diverse sample pretreatment

Abstract

In this study, a highly sensitive and robust method using an ultra-high-performance liquid chromatographytandem mass spectrometry combined with solid-phase extraction and ultrasonic extraction for pretreatment and silica gel purification steps has been developed for determination of 21 natural and synthetic progestagens in river surface water and sediments, and influents, effluents, and sludge from municipal wastewater treatment plants, and flush water and feces from swine farms. For the various matrices considered, the optimized method showed satisfactory performance with recoveries of 70-129 % (except AD, 5α-DHP, DPT, HPC), the limits of quantification below 2.30 ng/L for liquid samples and 2.59 ng/g for solid samples (except AD), and good linearity and reproducibility. This developed method was successfully applied in the analysis of progestagens in environmental samples from Liuxi Reservoir, Xintang municipal wastewater treatment plant, and Shunfeng swine farm in South China. Six analytes were detected at trace levels in surface water, effluent, and sediment samples. Seven analytes (0.7 (HPA)-35.1 ng/L (DGT)) were found in the influent samples and three analytes (5.6 (DGT)-11.8 ng/g (5α-DHP)) in the dewatered sludge samples. Moreover, 13 analytes were detected in swine farm, with high concentrations ranging from 23.8 ng/L (ET) to 5,024 ng/L (P) in flush water, and from 20.0 ng/g (MPA) to 1952 ng/g (P) in feces.

Developmental exposure to progestins causes male bias and precocious puberty in zebrafish (Danio rerio)

“…From these studies, it appears that estrogenic and antiandrogenic chemicals cause delayed gonad maturation in both sexes (Ammann et al, 2014;Baumann et al, 2013;Hutchinson et al, 2006a;Kiparissis et al, 2003;Örn et al, 2006), and that androgenic chemicals cause accelerated gonad maturation, mainly in male fish (Baumann et al, 2013;Hutchinson et al, 2006a;Liu et al, 2014;Morthorst et al, 2010;Orn et al, 2006). Mixtures of organochlorine pesticides, polychlorinated biphenyls and brominated flame retardants have been shown to cause advanced puberty, measured as advanced timing of first spawning (Nourizadeh-Lillabadi et al, 2009).…”

Steroid bioaccumulation profiles in typical freshwater aquaculture environments of South China and their human health risks via fish consumption

“…Ten synthetic steroids were detected in water samples of the aquaculture farms (Table 1). These synthetic ones are used in animal production for the purposes of breeding control and growth promotion (Liu et al, 2012b(Liu et al, , 2014(Liu et al, , 2015c. Previous studies pointed out that synthetic steroids may induce multiple transcriptional responses to brain and gonads of zebrafish embryos or adults at environmental levels (4.8 ng/L for DGT and 2.0 ng/L for 19-NTD) (Zucchi et al, 2012;Zhao et al, 2015b).…”

“…Sample extraction and instrumental analysis were carried out following previously established analytical methods (Liu et al, 2011a(Liu et al, , 2014Zhao et al, 2015a). The detailed method information can be found in the Supplementary materials (Tables S4 and S5).…”

Progestins as endocrine disrupters in aquatic ecosystems: Concentrations, effects and risk assessment

“…These and levonorgestrel were detected together with P4 and metabolites in other rivers in China . Moreover, Liu et al (2014) found P4, megestrol acetate and norethindrone in the range of 0.6-1.7 ng/L as well as up to 9.6 ng/L dydrogesterone in a river downstream of a WTP. In France, Vulliet and Cren-Olivé (2011) found P4, levonorgestrel and norethindrone levels of up to 3.6 ng/L in surface and 4.0 ng/L in groundwater.…”

“…In downstream locations, synthetic progestins were still present. Liu et al (2014) found 9.6 ng/L of dydrogesterone and 2.5 ng/L of P4 downstream of a WTP. Very high levels of norethindrone of up to 188 ng/L were Table 2.…”