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Predicting runoff hot spots and hot‐moments within a headwater crop‐catchment is of the utmost importance to reduce adverse effects on aquatic ecosystems by adapting land use management to control runoff. Reliable predictions of runoff patterns during a crop growing season remain challenging. This is mainly due to the large spatial and temporal variations of topsoil hydraulic properties controlled by complex interactions between weather, growing vegetation, and cropping operations. This interaction can significantly modify runoff patterns and few process‐based models can integrate this evolution of topsoil properties during a crop growing season at the catchment scale. Therefore, the purpose of this study was to better constrain the event‐based hydrological model Limburg Soil Erosion Model by incorporating temporal constraints for input topsoil properties during a crop growing season (LISEM). The results of the temporal constraint strategy (TCS) were compared with a classical event per event calibration strategy (EES) using multi‐scale runoff information (from plot to catchment). The EES and TCS approaches were applied in a loess catchment of 47 ha located 30 km northeast of Strasbourg (Alsace, France). A slight decrease of the Nash–Sutcliffe efficiency criterion on runoff discharge for TCS compared to EES was counterbalanced by a clear improvement of the spatial runoff patterns within the catchment. This study showed that limited agronomical and climatic information added during the calibration step improved the spatial runoff predictions of an event‐based model. Reliable prediction of runoff source, connectivity, and dynamics can then be derived and discussed with stakeholders to identify runoff hot spots and hot‐moments for subsequent land use and crop management modifications.

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Abstract. Compound-specific stable isotope analysis (CSIA) has proven beneficial in the characterization of contaminant degradation in groundwater, but it has never been used to assess pesticide transformation on catchment scale. This study presents concentration and carbon CSIA data of the herbicides S-metolachlor and acetochlor from three locations (plot, drain, and catchment outlets) in a 47 ha agricultural catchment (Bas-Rhin, France). Herbicide concentrations at the catchment outlet were highest (62 µg L −1 ) in response to an intense rainfall event following herbicide application. Increasing δ 13 C values of S-metolachlor and acetochlor by more than 2 ‰ during the study period indicated herbicide degradation. To assist the interpretation of these data, discharge, concentrations, and δ 13 C values of S-metolachlor were modelled with a conceptual mathematical model using the transport formulation by travel-time distributions. Testing of different model setups supported the assumption that degradation half-lives (DT50) increase with increasing soil depth, which can be straightforwardly implemented in conceptual models using travel-time distributions. Moreover, model calibration yielded an estimate of a field-integrated isotopic enrichment factor as opposed to laboratory-based assessments of enrichment factors in closed systems. Thirdly, the Rayleigh equation commonly applied in groundwater studies was tested by our model for its potential to quantify degradation on catchment scale. It provided conservative estimates on the extent of degradation as occurred in stream samples. However, largely exceeding the simulated degradation within the entire catchment, these estimates were not representative of overall degradation on catchment scale. The conceptual modelling approach thus enabled us to upscale sample-based CSIA information on degradation to the catchment scale. Overall, this study demonstrates the benefit of combining monitoring and conceptual modelling of concentration and CSIA data and advocates the use of traveltime distributions for assessing pesticide fate and transport on catchment scale.

Surface runoff and erosion during the course of rainfall events are major processes of pesticides transport from agricultural land to aquatic ecosystem. These processes are generally evaluated either at the plot or the catchment scale. Here, we compared at both scales the transport and partitioning in runoff water of two widely used fungicides, i.e., kresoxim-methyl (KM) and cyazofamid (CY). The objective was to evaluate the relationship between fungicides runoff from the plot and from the vineyard catchment. The results show that seasonal exports for KM and CY at the catchment were larger than those obtained at the plot. This underlines that non-target areas within the catchment largely contribute to the overall load of runoff-associated fungicides. Estimations show that 85 and 62 % of the loads observed for KM and CY at the catchment outlet cannot be explained by the vineyard plots. However, the partitioning of KM and CY between three fractions, i.e., the suspended solids (>0.7 μm) and two dissolved fractions (i.e., between 0.22 and 0.7 µm and <0.22 µm) in runoff water was similar at both scales. KM was predominantly detected below 0.22 μm, whereas CY was mainly detected in the fraction between 0.22 and 0.7 μm. Although KM and CY have similar physicochemical properties and are expected to behave similarly, our results show that their partitioning between two fractions of the dissolved phase differs largely. It is concluded that combined observations of pesticide runoff at both the catchment and the plot scales enable to evaluate the sources areas of pesticide off-site transport.

Evaluating pesticide degradation and transport in the soil-surface water continuum remains challenging at the catchment scale. Here we investigated the dissipation of the chiral herbicide S-metolachlor (SM) in soil in relation to its transport in runoff. Analyses of SM, transformation products (TPs, i.e., MESA and MOXA), and enantiomers were combined to determine SM degradation at plot and catchment scales. Assisted by modeling, we found that the main dissipation pathways of SM at the plot scale were degradation (71%), volatilization (5%), leaching (8%) and runoff (3%), while 13% of SM persisted in topsoil. This highlights the relevance of degradation processes. TPs could trace the different discharge contributions: MOXA prevailed in runoff water, whereas MESA was associated with slower flowpaths. At the catchment outlet, 11% of SM applied was exported in dissolved or particulate phases or as TPs (in SM mass equivalent). A single event 1 week after application exported 96% of SM, which underlined the potential importance of severe rainfall on seasonal SM export. Enantioselective degradation enriched SM in the R-enantiomer over longer periods and may be associated with slower flowpaths. Altogether, combining observation scales and analytical approaches enabled to quantify SM degradation and to identify how degradation controls SM export at the catchment scale.

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