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Pesticide metabolites are frequently detected in groundwater, often exceeding the concentrations of their parent pesticides. Ceasing the application of certain pesticides has often not led to the expected decrease in metabolite concentrations in groundwater, which is potentially caused by residues in soil. Whereas pesticide residues in soils are well-documented, there are only few studies about metabolite residues. We investigated if the soil/unsaturated zone can act as a long-term source for metabolites in groundwater by combining soil analysis, groundwater analysis and numerical modelling. The field study focused on the herbicide chloridazon (CLZ) and its frequently detected metabolites desphenyl-chloridazon (DPC) and methyl-desphenyl-chloridazon (MDPC) while in the model additional pesticides and metabolites were considered. In soil samples from an agricultural area, where the last CLZ application was 5 to 10 years ago, we observed 10 times (DPC: 0.22 - 7.4 µg kg -1 ) and 6 times (MDPC: 0.12 - 3.1 µg kg -1 ) higher metabolite concentrations compared to CLZ (< 0.050 - 1.0 µg kg -1 ). Calculations suggested that the majority of the metabolites (DPC: 63 - 96%, MDPC: 74 - 97%) were sorbed despite their lower sorption tendency. The metabolite retention was in particular related to the organic carbon content. The calculated pore water concentrations were highest in the deepest part of the soil profile (75 - 100 cm) with median concentrations of 3.6 and 1.7 µg L -1 for DPC and MDPC, respectively. The groundwater concentrations of DPC and MDPC were 3 to 3.5 times higher in monitoring wells downgradient from the agricultural zone than upgradient of it. This increase highlights the potential of soil and unsaturated zone as a long-term metabolite source after the application stop of pesticides, consistent with the calculated elevated pore water concentrations. Numerical flow and transport model simulations suggested that this input from soil and unsaturated zone can cause elevated metabolite concentrations (> 0.1 µg L -1 ) in groundwater over more than one decade. The study highlights that soil and unsaturated zone can act as a long-term source of pesticide metabolites even if they have much higher mobility than the parent compound., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Daniel Hunkeler reports financial support was provided by Federal Office for the Environment. Daniel Hunkeler reports financial support was provided by Swiss Gas and Water Industry Association (SGWA). Daniel Hunkeler reports financial support was provided by Canton of Zürich., (Copyright © 2024. Published by Elsevier Ltd.)

This study investigates how catchment properties influence low-flow dynamics. With 496 synthetic models composed of a bedrock and an alluvial aquifer, we systematically assess the impact of the hydraulic conductivity of both lithologies, of the hillslope and of the river slope on catchment dynamics. The physically based hydrogeological simulator HydroGeoSphere is employed, which allows obtaining a range of low-flow indicators. The hydraulic conductivity of the bedrock K bedrock , a proxy for transmissivity, is the only catchment property exerting an overall control on low flows and explains 60% of the variance of Q95/Q50. The difference in dynamics of catchments with same K bedrock depends on hillslope gradients and the alluvial aquifer properties. The buffering capacity of the bedrock is mainly related to K bedrock and the hillslope gradient. We thus propose the dimensionless bedrock productivity index (BPI) that combines these characteristics with the mean net precipitation. For bedrock only models, the BPI explains 82% of the variance of the ratio of Q95 to mean net precipitation. The alluvial aquifer can significantly influence low flows when the bedrock productivity is limited. Although our synthetic catchment setup is simple, it is far more complex than the available analytical approaches or conceptual hydrological models. The direct application of the results to existing catchments requires nevertheless careful consideration of the local geological topographic and climatic conditions. This study provides quantitative insight into the complex interrelations between geology, topography and low-flow dynamics and challenges previous studies which neglect or oversimplify geological characteristics in the assessment of low flows., (© 2018, National Ground Water Association.)

The potential impact of climate change on water resources has been intensively studied for different regions and climates across the world. In regions where winter processes such as snowfall and melting play a significant role, anticipated changes in temperature might significantly affect hydrological systems. To address this impact, modifications have been made to the fully integrated surface-subsurface flow model HydroGeoSphere (HGS) to allow the simulation of snow accumulation and melting. The modified HGS model was used to assess the potential impact of climate change on surface and subsurface flow in the Saint-Charles River catchment, Quebec (Canada) for the period 2070 to 2100. The model was first developed and calibrated to reproduce observed streamflow and hydraulic heads for current climate conditions. The calibrated model was then used with three different climate scenarios to simulate surface flow and groundwater dynamics for the 2070 to 2100 period. Winter stream discharges are predicted to increase by about 80, 120, and 150% for the three scenarios due to warmer winters, leading to more liquid precipitation and more snowmelt. Conversely, the summer stream discharges are predicted to fall by about 10, 15, and 20% due to an increase in evapotranspiration. However, the annual mean stream discharge should remain stable (±0.1 m 3 /s). The predicted increase in hydraulic heads in winter may reach 15 m and the maximum decrease in summer may reach 3 m. Simulations show that winter processes play a key role in the seasonal modifications anticipated for surface and subsurface flow dynamics., (© 2018, National Ground Water Association.)

Recent models that couple three-dimensional subsurface flow with two-dimensional overland flow are valuable tools for quantifying complex groundwater/stream interactions and for evaluating their influence on watershed processes. For the modeler who is used to defining streams as a boundary condition, the representation of channels in integrated models raises a number of conceptual and technical issues. These models are far more sensitive to channel topography than conventional groundwater models. On all spatial scales, both the topography of a channel and its connection with the floodplain are important. For example, the geometry of river banks influences bank storage and overbank flooding; the slope of the river is a primary control on the behavior of a catchment; and at the finer scale bedform characteristics affect hyporheic exchange. Accurate data on streambed topography, however, are seldom available, and the spatial resolution of digital elevation models is typically too coarse in river environments, resulting in unrealistic or undulating streambeds. Modelers therefore perform some kind of manual yet often cumbersome correction to the available topography. In this context, the paper identifies some common pitfalls, and provides guidance to overcome these. Both aspects of topographic representation and mesh discretization are addressed. Additionally, two tutorials are provided to illustrate: (1) the interpolation of channel cross-sectional data and (2) the refinement of a mesh along a stream in areas of high topographic variability., (© 2014, National Ground Water Association.)