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Linking biogeochemical processes to water flow paths and solute travel times is important for understanding internal catchment functioning and control of water quality. Base cation weathering is a process closely linked to key factors affecting catchment functioning, including water pathways, soil contact time, and catchment characteristics, particularly in silicate-dominated areas. However, common process-based weathering models are often calibrated and applied for individual soil profiles, which can cause problems when trying to extrapolate results to catchment scale and assess consequences for stream water and groundwater quality. Therefore, in this work, base cation export was instead modelled using a fully calibrated 3D hydrological model (Mike SHE) of a boreal catchment, which was expanded by adding a relatively simple but still reasonably flexible and versatile weathering module including the base cations Na, K, Mg, and Ca. The results were evaluated using a comprehensive dataset of water chemistry from groundwater and stream water in 14 nested sub-catchments, representing different catchment sizes and catchment characteristics. The strongest correlations with annual and seasonal observations were found for Ca (r = 0.89-0.93, p < 0.05), Mg (r = 0.90-0.95, p < 0.05), and Na (r = 0.80-0.89, p < 0.05). These strong correlations suggest that catchment hydrology and landscape properties primarily control weathering rates and stream dynamics of these solutes. Furthermore, catchment export of Mg, Ca, and K was strongly connected to travel times of discharging stream water (r = 0.78-0.83). Conversely, increasing Na export was linked to a reduced areal proportion of mires (r = -0.79). The results suggest that a significant part (~45%) of the catchment stream export came from deep-soil weathering sources (>2.5 m). These results have implications for terrestrial and aquatic water quality assessments. If deep soils are present, focusing mainly on the shallow soil could lead to misrepresentation of base cation availability and the acidification sensitivity of groundwater and water recipients such as streams and lakes., Competing Interests: Declaration of competing interest The authors declare that they have no conflict of interest., (Copyright © 2021 The Author(s). Published by Elsevier B.V. All rights reserved.)

A groundwater plume containing high concentrations of pharmaceutical compounds, mainly sulfonamides, barbiturates, and ethyl urethane, in addition to chlorinated ethenes and benzene was investigated. The contamination originating from a former pharmaceutical industry discharges into a multilayered aquifer system and a downgradient stream. In this study, geological and hydrogeological data were integrated into a numerical flow model to examine identified trends using statistical approaches, including principal component analysis and hierarchal cluster analysis. A joint interpretation of the groundwater flow paths and contaminant concentrations in the different compartments (i.e., groundwater and hyporheic zone) provided insight on the transport processes of the different contaminant plumes to the stream. The analysis of historical groundwater concentrations of pharmaceutical compounds at the site suggested these compounds are slowly degrading. The pharmaceutical compounds migrate in both a deep semiconfined aquifer, as well as in the shallow unconfined aquifer, and enter the stream along a 2-km stretch. This contrasted with the chlorinated ethenes, which mainly discharge to the stream as a focused plume from the unconfined aquifer. The integrated approach developed here, combining groundwater flow modeling and statistical analyses of the contaminant concentration data collected in groundwater and the hyporheic zone, lead to an improved understanding of the observed distribution of contaminants in the unconfined and semiconfined aquifers, and thus to their discharge to the stream. This approach is particularly relevant for large and long-lasting contaminant sources and plumes, such as abandoned landfills and industrial production sites, where field investigations may be very expensive., (© 2019, National Ground Water Association.)

An analytical solution to describe dilution and volatilization of a continuous groundwater contaminant plume into streams is developed for risk assessment. The location of groundwater plume discharge into the stream (discharge through the side versus bottom of the stream) and different distributions of the contaminant plume concentration (Gaussian, homogeneous or heterogeneous distribution) are considered. The model considering the plume discharged through the bank of the river, with a uniform concentration distribution was the most appropriate for risk assessment due to its simplicity and limited data requirements. The dilution and volatilization model is able to predict the entire concentration field, and thus the mixing zone, maximum concentration and fully mixed concentration in the stream. It can also be used to identify groundwater discharge zones from in-stream concentration measurement. The solution was successfully applied to published field data obtained in a large and a small Danish stream and provided valuable information on the risk posed by the groundwater contaminant plumes. The results provided by the dilution and volatilization model are very different to those obtained with existing point source models, with a distributed source leading to a larger mixing length and different concentration field. The dilution model can also provide recommendations for sampling locations and the size of impact zones in streams. This is of interest for regulators, for example when developing guidelines for the implementation of the European Water Framework Directive., (Copyright © 2014 Elsevier B.V. All rights reserved.)