Changes in dissolved inorganic carbon in river water due to urbanization revealed by hydrochemistry and carbon isotope in the Pearl River Delta, China

Under natural conditions, the dissolved inorganic carbon (DIC) in river water is dominantly derived from carbonate or silicate dissolution by carbonic acid. However, sulfuric and nitric acids produced by human activities provide additional acidity for chemical weathering, which would affect the DIC flux and change its isotopic composition. To identify the natural and anthropogenic impacts on DIC, the major ion concentrations and stable carbon isotopes of the DIC (δ13C-DIC) of river waters were measured in the Pearl River Delta (PRD) region, which is one of the most developed and populated areas in China. The mass balance calculations for DIC-apportionment showed that carbonate dissolution by carbonic acid was the dominant origin of DIC in the Beijiang (BJ) River (67%) and Xijiang (XJ) River (78%) and silicate dissolution by carbonic acid was the dominant origin of DIC in the Guangzhou (GZ) Channel (37%) and Dongjiang (DJ) River (50%), which was related to the lithology of the catchment. The contribution of carbonate dissolution by sulfuric and nitric acids, which represented the contribution of human activities to the total DIC concentrations in river water, showed high proportions in the GZ Channel and DJ River, with averages of 42% and 34%, respectively, which were associated with a high degree of urbanization. Evidence of hydrochemical parameters and δ13C-DIC signatures indicated that human activities had impacts on the DIC pool. Carbonate dissolution by sulfuric and nitric acids caused by human activities changed DIC apportionments rather than the DIC flux, and this part of DIC would ultimately become a source of CO2 to the atmosphere on the geological timescale and affects the CO2 budget. An increase in nutrient concentration due to increased sewage discharge in the urbanized area could promote phytoplankton photosynthesis, which could change the DIC pool and increase the δ13C-DIC value. This study quantitatively highlights the influence of human activities on DIC apportionment in river water, suggesting that anthropogenic impacts should be seriously considered when evaluating the evolution of DIC.