Multi-proxy approach (2H/H, 18O/16O, 13C/12C and 87Sr/86Sr) for the evolution of carbonate-rich groundwater in basalt dominated aquifer of Axum area, northern Ethiopia

The δ2H and δ18O values of all solutions clearly indicate meteoric origin. Shifts from the local meteoric water line are attributed to evaporation of surface and spring water, and to strong water-rock interaction. The δ13CDIC values of shallow groundwater between −12 and −7‰ (VPDB) display the uptake of CO2 from local soil horizons, whereas δ13CDIC of deep groundwater ranges from −5 to +1‰. Considering open system conditions with respect to gaseous CO2, δ13CDIC = +1‰ of the deep groundwater with highest PCO2 = 10−0.9 atm yields δ13CCO2(gas) ≈ −5‰, which is close to the stable carbon isotopic composition of magmatic CO2. Accordingly, stable carbon isotope ratios within the above range are referred to individual proportions of CO2 from soil and magmatic origin. The uptake of magmatic CO2 results in elevated cations and Si(OH)4 concentrations. Weathering of local basalts is documented by 87Sr/86Sr ratios of the groundwater from 0.7038 to 0.7059. Highest values indicate Sr release from the basement rocks. Besides weathering of silicates, neoformation of solids has to be considered, which results in the formation of, e.g., kaolinite and montmorillonite. In several solutions supersaturation with respect to calcite is reached by outgassing of CO2 from the solution leading to secondary calcite formation.