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 (ΔδC  = 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 (ΔδN=-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.

Understanding the fate of copper (Cu) fungicides in vineyard soils and catchments is a prerequisite to limit the off-site impact of Cu. Using Cu stable isotopes, Cu retention in soils and runoff transport was investigated in relation to the use of Cu fungicides and the hydrological conditions in a vineyard catchment (Rouffach, Haut-Rhin, France; mean slope: 15%). The δ(65)Cu values of the bulk vineyard soil varied moderately through the depth of the soil profiles (-0.12 to 0.24‰±0.08‰). The values were in the range of those of the fungicides (-0.21 to 0.11‰) and included the geogenic δ(65)Cu value of the untreated soil (0.08‰). However, δ(65)Cu values significantly differed between particle-size soil fractions (-0.37±0.10‰ in fine clays and 0.23±0.07‰ in silt). Together with the soil mineralogy, the results suggested Cu isotope fractionation primarily associated with the clay and fine clay fractions that include both SOM and mineral phases. The vegetation did not affect the Cu isotope patterns in the vineyard soils. Cu export by runoff from the catchment accounted for 1% of the applied Cu mass from 11th May to 20(th) July 2011, covering most of the Cu use period. 84% of the exported Cu mass was Cu bound to suspended particulate matter (SPM). The runoff displayed δ(65)Cu values from 0.52 to 1.35‰ in the dissolved phase (<0.45μm) compared to -0.34 to -0.02‰ in the SPM phase, indicating that clay and fine clay fractions were the main vectors of SPM-bound Cu in runoff. Overall, this study shows that Cu stable isotopes may allow identifying the Cu distribution in the soil fractions and their contribution to Cu export in runoff from Cu-contaminated catchments.