In the arid area of northern Chile, groundwater resources in the Andean formations are essential for native populations, ecological services, mining, and other human activities. Validated conceptual hydrogeological models are required for current and future water and land management. This work aims to explain the processes controlling the origin and distribution of recharge and groundwater composition in the Andean Precordillera and Altiplano of the Tarapacá Region of northern Chile, using major solutes in spring, river, and well water, and the stable and radioactive isotopes of water oxygen, hydrogen, and dissolved inorganic carbon. The waters are mainly of the Na-Ca-SO4 type. Processes controlling the chemical evolution of waters are atmospheric dust contribution, evapo-concentration, and enhanced volcanic rock weathering, as well as halite dissolution in some locations. The isotopic composition of Precordillera eastern flank water samples follows an evaporation line, while those in the western flank, in the Altiplano, follow a line that is parallel to the local meteoric line, suggesting unsaturated zone evaporation processes of infiltrated rainfall. δ13CDIC contents (-2 to -27‰) indicate mixing processes, volcanic CO2 in the Altiplano, and calcite dissolution in some sectors. In the western depression, the only recharge is due to water infiltration in creek channels. In the highland areas, 5–25% of precipitation produces recharge. The estimated groundwater renewal time in the Precordillera was 3–14 kyr. The piezometric elevation in the Precordillera due to low-permeability intrusive rocks and local recharge prevents the east-west groundwater transfer from the Altiplano to the western depression and explains why the volcanic CO2 in the Altiplano basins is not observed on the western flank. These results provide new insights for the evolution of water quality in volcanic aquifers in arid environments and provide considerations for estimating groundwater residence times using radiocarbon in areas influenced by volcanic CO2.
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