Impact of anthropogenic sulfate deposition via precipitation on carbonate weathering in a typical industrial city in a karst basin of southwest China: A case study in Liuzhou

An analysis was performed of the hydrochemical characteristics of precipitation and river water samples collected from the Liujiang River Basin from June 2014 to May 2015, SW China to determine the carbon source and sink of carbonate weathering by anthropogenic sulfate deposition via precipitation in a typical Karst industrial city. Our findings revealed that (1) the pH of the precipitation samples has a volume-weighted mean (VWM) of 5.78 and that the acid rain rate is 12%. The enrichment factor (EF), sea salt fraction (SSF), crustal fraction (CF) and anthropogenic fraction (AF) were calculated, and the results indicated that precipitation was characterized by high concentrations of SO4, NH4, Ca and NO3. Na and Cl, Ca and NH4, and SO4 (98.2%) and NO3 (99.8%) were mainly derived from sea salt, earth crust, and anthropogenic activities, respectively. Combined with the air mass trajectory (HYSPLIT (Hybrid Single-Particle Lagrangian Integrated Trajectory)) and the concentration of non-sea salt (NSS) SO4 and δ34S–SO4nss, the δ34S–SO4sam ranged from −2.6–12.6‰ and atmospheric sulfate was mainly associated with local coal combustion, fossil fuels and the transmission distance of pollution sources from the northwest and southwest in the interior of the continents. (2) An analysis of the river hydrochemical characteristics showed that the cations are mainly Ca and Mg, and they accounted for approximately 90% of the total cations. The anions were mainly HCO3 and SO4, and the hydrochemical composition of the river was mainly controlled by the weathering of carbonate minerals in the river basin. An analysis of the correlation between the changes in the chemical equivalence concentration of [Ca + Mg]/[HCO3+SO4] showed that the ratio of most river water samples was approximately 1, indicating that Ca and Mg in the river need HCO3 and SO4 for chemical equilibrium and that SO4 in the river may be involved in the dissolution of carbonate minerals. (3) Corrections were performed based on the chloride-normalized ratios and the contribution of each terminal element was calculated to estimate the major ions of precipitation input; the results showed that the average contribution ratio of SO4 transported to the river by anthropogenic sulfuric acid in precipitation reached 85.57%. (4) According to the proportional relationships, carbonate weathering accounts for 31.73% of the anthropogenic sulfuric acid via precipitation and would cause an approximate 6.27% increase in carbonate