Investigating sources and evolution of groundwater in the Black Volta River basin is vital for understanding aquifer chemical configuration. Though resettlement has made groundwater in the region an important water supply source, its hydrochemical origin is poorly understood. Therefore, hydrochemistry was coupled with stable isotope (δ2H and δ18O) techniques to improve knowledge for effective groundwater resource management. For this purpose, 23 boreholes were sampled in the Black Volta River basin of Ghana. Major ion dominance is in the order: Na+ > Ca2+ > Mg2+ >K+ and HCO3− > Cl− > SO42− > NO3− respectively. Hydrochemical facies indicates the presence of soluble silicate minerals within aquifer. Hierarchical cluster analysis showed higher ionic concentration within aquifers which decreases towards discharge areas. This is attributed to longer residence time at lower elevations leading to interaction of water with silicate and accessory minerals. Oxygen-18 spatial plot shows recharge occurs along subsurface fractured zones which is confirmed by the water table contour of the study area. Natural geochemical processes, anthropogenic influences and the dissolution of silicate/albite components were extracted using Principal component analysis/factor analysis. These two components which explains the hydrochemistry constituted 79.5% of the total variance in the hydrochemical data and have eigen values > 1. Isotopic composition of groundwater indicates is of meteoric origin and the aquifers were recharged by precipitation. The outcome of this study provides theoretical support for the monitoring and management of groundwater, and its implication on the migration of people in arid/semi-arid regions.
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