Pesticide degradation and export losses at the catchment scale: Insights from compound-specific isotope analysis...

Although pesticides undergo degradation tests prior to use, determining their export, degradation and persistence under field conditions remains a challenge for water resource management. Compound specific isotope analysis (CSIA) can provide evidence of contaminant degradation extent, as it is generally independent of non-destructive dissipation (e.g., dilution, sorption, volatilization) regulating environmental concentrations. While this approach has been successfully implemented in subsurface environments, its application to pesticides in near-surface hydrological contexts at catchment scale is lacking. This study demonstrates the applicability of CSIA to track pesticide degradation and export at catchment scale and identify pesticide source areas contributing to changes in stable isotope signature in stream discharge under dynamic hydrological contexts. Based on maximum shifts in carbon stable isotope signatures (Δδ¹³C  = 4.6 ± 0.5‰) of S-metolachlor (S-met), a widely used herbicide, we estimate maximum degradation to have reached 96 ± 3% two months after first application. Maximum shifts in nitrogen isotope signatures were small and inverse (Δδ¹⁵N=-1.3±0.6‰) indicating potential secondary isotope effects during degradation. In combination with a mass balance approach including S-met main degradation products, total catchment non-destructive dissipation was estimated to have reached 8 ± 7% of the applied product. Our results show that CSIA can be applied to evaluate natural attenuation of pesticides at catchment scale. By providing a more detailed account of pesticide dissipation and persistence under field conditions we anticipate the contribution of pesticide CSIA to the improvement of regulatory and monitoring strategies.