Coupled processes involving ammonium inputs, microbial nitrification, and calcite dissolution control riverine nitrate pollution in the piedmont zone (Qingshui River, China)

Rivers in agricultural countries widely suffer from diffuse nitrate (NO3−) pollution. Although pollution sources and fates of riverine NO3− have been reported worldwide, the driving mechanisms of riverine NO3− pollution associated with mineral dissolution in piedmont zones remain unclear. This study combined hydrogeochemical compositions, stable isotopes (δ18O–NO3−, δ15N–NO3−, δ18O–H2O, and δ2H–H2O), and molecular bioinformation to determine the pollution sources, biogeochemical evolution, and natural attenuation of riverine NO3− in a typical piedmont zone (Qingshui River). High NO3− concentration (37.5 ± 9.44 mg/L) was mainly observed in the agricultural reaches of the river, with ~15.38 % of the samples exceeding the acceptable limit for drinking purpose (44 mg/L as NO3−) set by the World Health Organization. Ammonium inputs, microbial nitrification, and HNO3-induced calcite dissolution were the dominant driving factors that control riverine NO3− contamination in the piedmont zone. Approximately 99.4 % of riverine NO3− contents were derived from NH4+-containing pollutants, consisted of manure & domestic sewage (74.0 % ± 13.0 %), NH4+-synthetic fertilizer (16.1 % ± 8.99 %), and soil organic nitrogen (9.35 % ± 4.49 %). These NH4+-containing pollutants were converted to HNO3 (37.2 ± 9.38 mg/L) by nitrifying bacteria, and then the produced HNO3 preferentially participated in the carbonate (mainly calcite) dissolution, which accounted for 40.0 % ± 12.1 % of the total riverine Ca2+ + Mg2+, also resulting in the rapid release of NO3− into the river water. Thus, microbial nitrification could be a new and non-negligible contributor of riverine NO3− pollution, whereas the involvement of HNO3 in calcite dissolution acted as an accelerator of riverine NO3− pollution. However, denitrification had lesser contribution to natural attenuation for high NO3− pollution. The obtained results indicated that the mitigation of riverine NO3− pollution should focus on the management of ammonium discharges, and the HNO3-induced carbonate dissolution needs to be considered in comprehensively understanding riverine NO3− pollution in piedmont zones. [Display omitted] •NH4+-containing pollutants are the primary NO3− source in river water.•Microbial nitrification facilitates the conversion of NH4+ to HNO3 in the piedmont zone.•Involvement of HNO3 in calcite dissolution results in the rapid release of NO3− into river.