High levels of ammonium from anthropogenic sources threaten the quality of surface waters and groundwaters in some areas worldwide, but elevated ammonium levels of natural sources also have been identified. High levels of ammonium have been detected in both surface water and shallow groundwater of the Jianghan Plain, an alluvial plain of the Yangtze River. This study used N isotopes coupled with ancillary chemistry to identify ammonium in this region. Ammonium in the Tongshun River (up to 10.25 mg L) showed a sharp accumulation in the upstream and gradual attenuation in the downstream. The δN values of ammonium in the TSR were high and ranged narrowly from +12.5 to +15.4‰, suggesting an anthropogenic source that was septic effluent from industrial waste discharge. Sorption and nitrification were likely to respectively serve as the principal processes contributing to ammonium attenuation in different reaches of the downstream TSR. In shallow groundwater, high levels of ammonium (up to 14.10 mg L) occurred in a reducing environment. The narrow δN variation with low values (+2.3 to +4.5‰) in the lower aquifer suggested a natural source that was organic N mineralization. The δN values in the shallow aquitard exhibited a wide range from -1.8 to +9.4‰, owing to various sources. Two types of water in the shallow aquitard could be identified: (1) type-1 water with relatively longer residence time was similar to those in the aquifer where ammonium was mainly sourced from organic N mineralization; (2) type-2 water with shorter residence time was jointly affected by surface input, chemical attenuation and mineralization of organic N. The aquitard prevents prompt ammonium exchange between the surface and aquifer, and the shallower part of the aquitard provides a sufficient reaction time and an active reaction rate for ammonium removal.
It becomes increasingly important and challenging for nitrogen pollution prevention to identify key controls for spatial variability of nitrogen in groundwater that could be affected by multiple factors, including anthropogenic input, groundwater flow, and local geochemistry. This study characterized spatial variability of both nitrate and ammonium in the Pleistocene aquifer of central Yangtze River Basin and assessed the effect of various factors in controlling nitrate and ammonium levels based on multiple statistical approaches (correlation, geostatistics, multiple liner regression). The results indicate that nitrate is mostly influenced by Cl − that represents anthropogenic input, while Eh representing local redox state is a secondary variable influencing nitrate concentrations. The groundwater with elevated nitrate concentrations are estimated to occur mainly in areas with higher-permeability near-surface sediments which can facilitate more anthropogenic nitrate transport and less nitrate removal owing to more oxidized state. Ammonium is mostly correlated to Eh, followed by dissolved organic carbon (DOC), but only DOC improves significantly the accuracy of co-kriging prediction model. The groundwater with elevated ammonium concentrations are estimated to occur mainly in areas with more organic-rich sediments within or around the aquifer which can facilitate more ammonium release owing to natural organic matter consumption accompanying strong reducing conditions. The regional groundwater flow is not a factor significantly controlling nitrate or ammonium levels owing to flat topography and sluggish lateral flow.
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