Hydrogeochemical zonation and its implication for arsenic mobilization in deep groundwaters near alluvial fans in the Hetao Basin, Inner Mongolia

• It is the first investigation of geochemistry of deep groundwaters in the Hetao Basin.
• Three zones are delineated with different reduction stage, hydrogeological setting and As concentration.
• Low As deep groundwaters near alluvial fans, and high As ones in flat plain.
• Reductions of Fe minerals and SO42- are the major factors controlling groundwater As.

SummaryHigh As groundwater has been found in shallow aquifers of the flat plain of the Hetao basin, but little is known about As concentration in deep groundwaters around piedmont areas, which are the major drinking water resources. One hundred and three groundwater samples from wells with depths >50 m and seven samples from one multi-level monitoring well (89 m in depth) were analyzed for chemical compositions and 18O and D isotopes to examine the geochemical processes controlling As mobilization. According to hydrogeological setting, chemical and isotopic characteristics of deep groundwater, three distinguished hydrogeochemical zones are delineated, including Recharge-Oxic Zone (Zone I), Groundwater Flow-Moderate Reducing Zone (Zone II), and Groundwater Flow-Reducing Zone (Zone III). Zone I is located in proximal fans in the recharge area with oxic conditions, where low As groundwater generally occurs. In Zone II, located in the intermediate between the fans and the flat plain with Fe-reduction predominated, groundwater As is moderate. Zone III lies in the flat plain with the occurrence of SO42- reduction, where high As groundwater is mostly found. This indicates that release of As to groundwater is primarily determined by reduction sequences. Arsenic is immobilized in O2/NO3- reduction stage in Zone I and released in Fe-reducing conditions of Zone II, and displays a significant elevated concentration in SO4-reducing stage in Zone III. Dissolution of carbonate minerals occurs in Zone I, while Ca2+ and Mg2+ are expected to precipitate in Zone II and Zone III. In the multi-level monitoring well, both chemical and isotopic compositions are dependent of sampling depths, with the similar trend to the hydrogeochemical zonation along the flow path. The apparent increases in δD and δ18O values in Zone III reveal the possibility of high As shallow groundwater recharge to deep groundwater. It indicates that deep groundwaters in proximal fans have low As concentrations and are considered as safe drinking water resources in the Hetao basin. However, high As concentration is frequently observed in deep groundwater in the flat plain, which should be routinely monitored in order to avoid chronic As poisoning.