Abstract. Compound-specific stable isotope analysis (CSIA) has, in combination with model-assisted interpretation, proven a valuable approach to quantify the extent of organic contaminant degradation in groundwater systems. CSIA data may also provide insights into the origin and transformation of diffuse river pollutants such as pesticides and nitrate at the catchment scale. While CSIA methods for pesticides have increasingly become available, they have not yet been deployed to interpret isotope data of pesticides in surface water. We applied a coupled subsurface-surface reactive transport model (HydroGeoSphere) at the hillslope scale to investigate the usefulness of CSIA in the assessment of pesticide degradation. We simulated the transport and transformation of a pesticide in a hypothetical but realistic two-dimensional hillslope transect. The steady-state model results illustrate a strong increase of isotope ratios at the hillslope outlet, which resulted from degradation and long travel times through the hillslope during average hydrological conditions. In contrast, following an extreme rainfall event that induced overland flow, the simulated isotope ratios dropped to the values of soil water in the pesticide application area. These results suggest that CSIA can help to determine whether pesticides enter the stream via groundwater exfiltration or via surface runoff. Simulations with daily rainfall and evapotranspiration data and one pesticide application per year resulted in small seasonal variations of concentrations and isotope ratios at the hillslope outlet, which fell within the uncertainty range of current CSIA methods. This implies a good reliability of in-stream isotope data in the absence of transport via surface runoff or other fast transport routes, since the time of measurement appears to be of minor importance. The analysis of simulated isotope ratios also allowed quantifying the contribution of two different reaction pathways to the overall degradation, which gave further insight into transport routes in the modelled system. The simulations supported the use of the commonly applied Rayleigh equation for the interpretation of CSIA data, since this led to an underestimation of the real extent of degradation of less than 12% at the hillslope outlet. Overall, the model results emphasize the applicability and usefulness of CSIA in the assessment of diffuse river pollution.
New loading method for high precision Sm isotope analysis of nuclear materials using thermal ionization mass spectrometry
