Sources of ammonium enriched in groundwater in the central Yangtze River Basin: Anthropogenic or geogenic?

The occurrence of excessive ammonium in groundwater threatens human and aquatic ecosystem health across many places worldwide. As the fate of ammonium in groundwater systems is often affected by a complex mixture of transport and biogeochemical transformation processes, identifying the sources of groundwater ammonium is an important prerequisite for planning effective mitigation strategies. Elevated ammonium was found in both a shallow and an underlying deep groundwater system in an alluvial aquifer system beneath an agricultural area in the central Yangtze River Basin, China. In this study we develop and apply a novel, indirect approach, which couples the random forest classification (RFC) of machine learning method and fluorescence excitation-emission matrices with parallel factor analysis (EEM-PARAFAC), to distinguish multiple sources of ammonium in a multi-layer aquifer. EEM-PARAFAC was applied to provide insights into potential ammonium sources as well as the carbon and nitrogen cycling processes affecting ammonium fate. Specifically, RFC was used to unravel the different key factors controlling the high levels of ammonium prevailing in the shallow and deep aquifer sections, respectively. Our results reveal that high concentrations of ammonium in the shallow groundwater system primarily originate from anthropogenic sources, before being modulated by intensive microbially mediated nitrogen transformation processes such as nitrification, denitrification and dissimilatory nitrate reduction to ammonium (DNRA). By contrast, the linkage between high concentrations of ammonium and decomposition of soil organic matter, which ubiquitously contained nitrogen, suggested that mineralization of soil organic nitrogen compounds is the primary mechanism for the enrichment of ammonium in deeper groundwaters.

Hydrogeological controls on ammonium enrichment in shallow groundwater in the central Yangtze River Basin.

The controlling processes of excessive ammonium in surface water and groundwater in the central Yangtze River Basin remain unclear. In this study, monitoring of water levels and temporal-spatial distributions of major N compounds were implemented at the large Jiangshan plain and at the local site scale in the central Yangtze River Basin. The results indicate that the recharge, movement and transformation of ammonium were controlled by hydrogeological conditions. Manure and sewage from anthropogenic activities were identified as the main source of nitrogen compounds. The nitrogen loading into aquifers were governed by water table and groundwater flow. After entering subsurface soils, nitrification and dissimilatory nitrate reduction to ammonium (DNRA) were proposed as the ammonium consumption and production mechanisms, respectively, by combining the concentrations of ammonium­nitrogen and nitrate­nitrogen with the corresponding isotopic compositions. These microbially mediated processes controlling transport and transformation of nitrogen compounds were influenced by the seasonally varying groundwater flow regime that changed the redox conditions in the aquifers. In the subsurface environments, ammonium was converted to nitrate when sufficient oxygen supply was available, and this process was reversed under anoxic conditions along the groundwater flow path. A conceptual model for the reactive transport of nitrogen compounds jointly controlled by the vertical groundwater flows and biogeochemical processes was proposed, which provides new insights into the genesis of high ammonium groundwater.