Effect of intensive seasonal pumping and recharge on sulfur biogeochemistry in groundwater of agricultural riparian zones.

ABSTRACT

Physico-chemical characteristics of groundwater are often impacted by agricultural practices such as land use, fertilizer types, and groundwater pumping. This study aimed to identify contaminant sources and redox processes controlling the hydrogeochemistry of groundwater in riparian zones influenced by intensive agricultural activities, focusing on sulfur species. Groundwater samples were collected bimonthly from March 2014 to March 2015 from groundwater wells in two zones in South Korea with different agricultural systems. The water isotopic compositions of the groundwater indicated that all groundwater originated from the same meteoric water. Groundwater samples affected by periodic groundwater pumping exhibited wide variations in Mn2+ (47.8 ± 18.2 µM) and Fe2+ (123 ± 61.0 µM) and elevated SO42-, while NO3- was below the detection limit. Groundwater chemistry was affected by fertilizer and manure, and denitrification. The oxidation of reduced sulfur compounds by oxygen and nitrate did not fully account for the elevated SO42- concentrations and isotopic composition of sulfate (δ34S and δ18O) in the investigated aquifers. Therefore, we postulate that water level change due to periodic groundwater pumping and recharge enabled oxidants (MnO2 and Fe3+) to also contribute to oxidation of reduced sulfur. Additionally, fertilizers with distinct δ34S values and bacterial sulfate reduction (BSR) affected groundwater chemistry and its sulfur species, including δ34SSO4 and δ18OSO4. Removal of sulfate from the aquifer during pumping limited BSR. Consequently, the agricultural practices may further increase sulfate concentrations in the groundwater. This environmental impact should be thoroughly managed because high sulfate concentrations in drinking water cause ingestion problems in humans.