Abiotic transformation of synthetic progestins in representative soil mineral suspensions

Abstract

Altrenogest (ALT), drospirenone (DRO), and melengestrol acetate (MLA) are three highly potent synthetic progestins that can be released into agricultural soils, while their fate in soil minerals remains unclear. This study explored the transformation of these progestins in MnO₂, SiO₂, and ferrihydrite suspensions and identified their transformation products (TPs) via high resolution mass spectrometry and density functional theory calculations. Transformations were only observed for DRO and MLA in SiO₂ suspension and ALT in MnO₂ suspension (half-lives = 0.86 min - 9.90 day). ALT transformation was facilitated at higher MnO₂ loadings, while DRO and MLA transformations were inhibited at higher SiO₂ loadings. These data indicated that hydrophobic partitioning interaction was dominant at higher SiO₂ loadings rather than specific interaction, which limited subsequent surface-catalyzed transformation. ALT transformation rate decreased with increasing pH because MnO₂ reduction requires proton participation. In contrast, relatively high pH facilitated MLA and DRO transformation, indicating that base-catalyzed hydrolysis occurred in SiO₂ suspension. The clustermap demonstrated the formation of abundant TPs. Lactone ring and acetoxy group hydrolysis was the major transformation pathway for DRO and MLA, with estimated yields of 57.7% and 173.2% at 6 day, respectively. ALT experienced C12 hydroxylation and formed the major TP 326g (yield of 15.4% at 8 hr). ALT also experienced allyl group oxidation and subsequent C5 hydroxylation, forming the major TP 344a (yield of 14.1% at 8 hr). This study demonstrates that TPs of metastable progestins are likely the main species in soils and that TP identification is a particular priority for risk assessment.

Keywords: Altrenogest; Drospirenone; Hydrolysis; Melengestrol acetate; Oxidation; Transformation products.