Joint interpretation of enantiomer and stable isotope fractionation for chiral pesticides degradation

Abstract

Chiral pesticides are important contaminants affecting the health and functioning of aquatic systems. The combination of stable isotope and enantiomer analysis techniques has been recently proposed to better characterize the fate of these contaminants in natural and engineered settings. We introduce a modeling approach with the aim of unifying and integrating the interpretation of isotopic and enantiomeric fractionation. The model is based on the definition of enantiomer-specific isotopologues and jointly predicts the evolution of concentration, enantiomer fractionation, as well as changes in stable isotope ratios of different elements. The method allows evaluating different transformation pathways and was applied to investigate enzymatic degradation of dichlorprop (DCPP), enzymatic degradation of mecoprop methyl ester (MCPPM), and microbial degradation of α-hexachlorocyclohexane (α-HCH) by different bacterial strains and under different redox conditions. The model accurately reproduces the isotopic and enantiomeric data observed in previous experimental studies and precisely captures the dual-dimensional trends characterizing different reaction pathways. Furthermore, the model allows testing possible combinations of enantiomer analysis (EA), compound specific isotope analysis (CSIA), and enantiomer specific isotope analysis (ESIA) to identify and assess isotope and enantiomer selective reaction mechanisms.