Evidence for the effect of sorption enantioselectivity on the availability of chiral pesticide enantiomers in soil

Abstract

Although enantioselective sorption to soil particles has been proposed as a mechanism that can potentially influence the availability of individual chiral pesticide enantiomers in the environment, environmental fate studies generally overlook this possibility and assume that only biotic processes can be enantioselective, whereas abiotic processes, such as sorption, are non-enantioselective. In this work, we present direct evidence for the effect of the enantioselective sorption of a chiral pesticide in a natural soil on the availability of the single pesticide enantiomers for transport. Batch sorption experiments, with direct determination of the sorbed amounts, combined with column leaching tests confirmed previous observations that from non-racemic aqueous solutions the sorption of the chiral fungicide metalaxyl on the soil appeared to be enantioselective, and further demonstrated that the enantiomer that was sorbed to a greater extent (R-metalaxyl, Kd = 1.73 L/kg) exhibited retarded leaching compared to its optical isomer (S-metalaxyl, Kd = 1.15 L/kg). Interconversion and degradation of the pesticide enantiomers, which are potential experimental artifacts that can lead to erroneous estimates of sorption and its enantioselectivity, were discarded as possible causes of the observed enantioselective behavior. The results presented here may have very important implications for a correct assessment of the environmental fate of chiral pesticides that are incorporated into the environment as non-racemic mixtures, and also of aged chiral pesticide residues that have been transformed from racemic to non-racemic by biologically-mediated processes.