Sources and fate of excessive ammonium in the Quaternary sediments on the Dongting Plain, China.

Excessive ammonia-nitrogen (N) in aquifers has caused groundwater pollution on the Dongting Plain (DTP), which seriously threatens the safety of drinking water. It is urgent and necessary to determine the sources and enrichment mechanisms of ammonia-N in groundwater. Carrying out water and soil collaborative research on a three-dimensional scale can more comprehensively analyze the sources of N, including natural and anthropogenic sources. In this study, surface and groundwater quality characteristics were examined from a total of 77 sites on the DTP. Two subsequent boreholes were drilled in the high ammonia concentration area and normal groundwater area, respectively, to compare the effects of anthropogenic activities. Indicators from hydrogeochemical and pedogeochemical analyses, as well as various isotopes, including δN-NH, δN-TON, δN-NO, δO-NO, δO-HO, δD-HO, and δC-TOC were used to identify ammonium sources and transformation mechanisms in the strata. We found that the sediments were contaminated by manure and sewage in the aquifers, and part of the shallow groundwater was additionally contaminated by nitrogen fertilizers. Excessive ammonium-N was also detected in the deep aquitards and sediments, which were mainly dominated by mineralization. Ammonia oxidation (with weak hydroxylamine oxidation) is an important biogeochemical process in which ammonia and nitrate do not accumulate in oxidizing groundwater environments. However, heterotrophic nitrification (HN) and anaerobic ammonium oxidation (ANAMMOX) are the release mechanisms for excessive ammonium-N under reducing conditions. In addition, organic matter (OM) on the DTP had a wide range of biogeochemical proxies generated by phytoplankton within a lake, and the comparatively resilient terrestrial organic residues washed in from the surrounding terrestrial area. This study breaks through the conventional mechanisms for the release of excessive ammonium from sediments to aquifers, which provides new ideas for research on ammonium in sediments and ammonia in groundwater.