Impact of the atmospheric deposition of major acid rain components, especially NH4, on carbonate weathering during recharge in typical karst areas of the Lijiang River basin, southwest China

We analysed precipitation and river water samples from the Lijiang River basin with the aim of understanding the important role of acid rain components, especially NH4, in chemical weathering of karst areas. First, analysis of the hydrochemical characteristics revealed the following: In the precipitation samples, the volume-weighted mean pH was 4.91, and the acid rain rate was 65%. The major ion composition was characterized by a dominance of NH4, Ca, SO4 and NO3, accounting for 40.0%, 35.3%, 46.3% and 30.5%, respectively, of the total cation and anion concentrations. In the river water samples, the pH ranged from 6.75 to 9.16, with an average of 7.55. The major hydrogeochemical species in the river water samples were Ca–HCO3 and Mg–HCO3. Second, by employing chloride-normalized ratios of the other major ions in precipitation, we estimated that the contributions of SO4 and NO3 from the atmosphere to the river were53.6% and 35.0%, respectively. Third, combining the hydrochemical index with the value of δ13CDIC and using the hydrochemical composition method showed that the proportion of carbonate weathered (R) by NH4, H2SO4 and HNO3 from acid rain accounted for 9.3%, 9.4% and 3.1% of the total weathering rate, respectively, and the proportions in the upper reaches were significantly higher than those in the lower reaches of the river. The average values of the carbonate weathering proportion (R) and the carbonate weathering rate (CWR) due to acid rain were approximately 22.0% and 2.1 t/km2/yr, respectively. Taken together, our results revealed that carbonate weathering by acid rain can significantly increase the carbonate weathering rate, which is essential information for accurate estimation of the carbon cycle (namely, inorganic carbon sources and sinks). [Display omitted] •Analysis of hydrochemical characteristics of precipitation and river water.•NH4(H), H2SO4 and HNO3 may provide the required protons for weathering reactions.•Carbonate weathering by acid rain can significantly increase weathering rate.