Silicate weathering contributed to arsenic enrichment in geotherm-affected groundwater in Pliocene aquifers of the Guide basin, China

Abstract

High arsenic (As) groundwater in reduced shallow Holocene and Pleistocene aquifers has been intensively investigated, but the occurrence and the genesis mechanisms of high As groundwater in deep Pliocene aquifers affected by geothermal activity still remain unclear. To address these issues, geochemical characteristics of groundwater and aquifer sediments in both middle-Pliocene aquifers and Quaternary aquifers of the Guide basin were investigated to clarify groundwater-sediments interaction and the causes of As enrichment in groundwater from middle-Pliocene aquifer. Higher As and Na+ concentrations were observed in groundwater from middle-Pliocene aquifer (GPA) than those in groundwater from Quaternary aquifer (GQA), while GPA had lower Ca2+ concentrations than GQA. Results showed that middle-Pliocene aquifer sediments had low contents of carbonate minerals, and water-soluble Ca-bearing minerals relative to Quaternary aquifer sediments, which explain higher concentration of Ca2+ in GQA than in GPA. Na+ from weathering of silicates (i.e. (Na+)*), being calculated based on mass balance, accounted for high proportion of dissolved Na+ (up to 68%) in GPA. Weathering of silicates was related to As accumulation in GPA, which was proved by a positive correlation between As and (Na+)* in GPA, and high proportion of As bound to unweathered silicates (up to 65.7%) in middle-Pliocene aquifer sediments. The weathering of silicate minerals directly released As bound to silicates into GPA, and indirectly led to As desorption from solid surfaces by increasing pH, HCO3– and CO32–. Both (Na+)* and As in groundwater increased with the increasing groundwater temperature, showing that high temperature was conducive to weathering of silicates and As enrichment. This paper establishes a bridge between high groundwater temperature and high As concentration with weathering of silicates in aquifers.