Isotopic and Hydrogeochemical Studies on Abnormally High Ammonium of Natural Origin in A Coastal Aquifer-aquitard System

Excessive nitrogen concentration in water bodies is regarded as an environmental contamination because of its possible harm to human bodies and significant ecological effects. Previous studies commonly concerned on elevated nitrogen in water of anthropogenic origins, such as agricultural, domestic, sewage and industrial discharges, because people realize that it is necessary to manage negative influences of human being to the natural environment. Understanding contamination sources of nitrogen is crucial for both waste discharge management and pollutants cleanup. This study was aimed to 1) understand the spatial distribution of abnormally high ammonium groundwater in the Quaternary basalt aquifer in the Pearl River Delta (PRD), China; 2) to distinguish sources of recharge to the basalt aquifer; and 3) to identify the origin of the ammonium in the aquitard and aquifer system. Total 40 boreholes were drilled, and approximately 1000 deposit samples from the aquitard and over 200 groundwater samples from the Quaternary basalt aquifer were collected. A cluster of 7 piezometers was installed in Minzhong Town to study the hydraulic relationships between the aquitard and the basalt aquifer. The results demonstrated that the greater groundwater ammonium concentrations were preserved in the aquifer buried deeper. The ammonium concentration up to 390 mg/L was observed in the basalt sand and gravel Pleistocene aquifer of 20-50m deep, and this is the greatest concentration ever reported for natural groundwater globally. The Quaternary aquitard, which contained abundant sedimentary organic matter and was mainly composed of silt and clay, provided a strict anaerobic environment for sedimentary organic matter mineralization and ammonium preservation. Ammonium concentrations in the aquifer were predominantly controlled by the aquitard ammonium content. This naturally occurring abnormally high ammonium in the Quaternary sediments is areally extensive (over 1600 km2). Great groundwater salinity originated from a marine source redounded to the release of adsorbed ammonium to groundwater via ion exchange processes. This naturally originated high ammonium groundwater may find its way to the river channels and estuary. The flow paths are likely shortened by sand dredging activities Literature shows that no particular studies have been developed for ammonium research in delta aquitards and aquifers. The geological settings of fine texture of delta sediments containing abundant sedimentary organic matter are not unique to the PRD, and this “geological” ammonium may not be an uncommon source of nitrogen and may present as a large and hitherto unappreciated source of nitrogen for surface water bodies.