Exploring the hydrogeochemical processes of karst groundwater has significant meaning for protecting local groundwater systems in semi-arid areas. Taking a typical semi-arid karst groundwater system—the Liulin spring area—as the research region, hydrogeochemical processes from rainfall infiltration to formation of higher total dissolved solids (TDS) water were studied, applying a mass balance model and the prediction of water chemical components in the focus area was explored. The results showed that hydrogeochemical processes dominating chemical components of karst groundwater included lixiviation, cation exchange and mixture. Calcite dissolved during rainfall infiltration processes in recharge area and saturated, then precipitated along the whole flow path. CO₂ dissolved significantly along with rainfall infiltration process and outgassed in discharge area and stagnant area. The dissolution of dolomite, gypsum and halite accompanied entire flow path and maximum dissolution load occurred in stagnant area. Mg-Na or Ca-Na exchange prevailed along flow path but exchange types depended on ionic concentration. The mixture between surface water and karst groundwater took place in surface water leakage belt in recharge and discharge area and mixture ratio for surface water ranged from 40% to 70%. TDS of the Liulin springs will increase with decreasing surface water leakage. Conversely, TDS of karst groundwater near Henggou area will decrease accompanied by the continuous discharge of the Henggou artesian well.

The comprehensive geological, hydrogeological and hydrogeochemical model of the Liulin karstic spring area in the eastern limb of the Ordos syncline was established by a combination of chemical thermodynamics, chemical kinetics and hydrogeology. The study area was divided into four zones based on the saturation indices of calcite, dolomite and gypsum, which were computed by the groundwater-chemical simulation software PHREEQC (a computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations), with consideration of the geological and hydrogeological conditions and hydro-geochemical reactions. The weight and volume modulus of carbonate rocks and sulphate rocks in each zone were calculated by the method of correlation analysis to evaluate the dissolution law of karst groundwater. The results showed that in the zone I (saturation index of calcite βc ≤ 1) the dissolution of calcite was the major geochemical reaction, the weight modulus of calcite was higher than that of dolomite and gypsum, and the pore space generated by the dissolution of calcite was one order of magnitude larger than that of dolomite and gypsum. In zone II (saturation index of calcite βc > 1 to saturation index of dolomite βd ≤ 1) the corrosion moduli were all smaller than that in zone I, the solubility of dolomite and gypsum increased, and calcite reached saturation. The space occupied by the calcite sediment was less than that dissolved by dolomite and gypsum. In zone III (saturation index of dolomite βd > 1 to saturation index of gypsum βg ≤ 1), calcite and dolomite had reached saturation, accompanied by dedolomitization, and the amount of gypsum dissolution increased obviously. The conclusions indicate that the hydrogeochemical environment plays an important role in mineral dissolution.