Origin of sulphate in the unsaturated zone and groundwater of a loess aquifer

The use of the sulphate mass balance (SMB) between precipitation and soil water as a supplementary method to estimate the diffuse recharge rate assumes that the sulphate in soil water originated entirely from atmospheric deposition; however, the origin of sulphate in soil and groundwater is often unclear, especially in loess aquifers. This study analysed the sulphur (delta S-34-SO4) and oxygen (delta O-18-SO4) isotopes of sulphate in precipitation, water-extractable soil water, and shallow groundwater samples and used these data along with hydrochemical data to determine the sources of sulphate in the thick unsaturated zone and groundwater of a loess aquifer. The results suggest that sulphate in groundwater mainly originated from old precipitation. When precipitation percolates through the unsaturated zone to recharge groundwater, sulphates were rarely dissolved due to the formation of CaCO3 film on the surface of sulphate minerals. The water-extractable sulphate in the deep unsaturated zone (>10 m) was mainly derived from the dissolution of evaporite minerals and there was no oxidation of sulphide minerals during the extraction of soil water by elutriating soil samples with deionized water. The water-extractable concentration of SO4 was not representative of the actual SO4 concentration in mobile soil water. Therefore, the recharge rate cannot be estimated by the SMB method using the water-extractable concentration of SO4 in the loess areas. This study is important for identifying sulphate sources and clarifying the proper method for estimating the recharge rate in loess aquifers.

Automated summary

This study identified the sources of sulphate in a loess aquifer by analyzing isotopes and hydrochemical data, finding that sulphate in groundwater mainly comes from old precipitation and extractable sulphate originates mainly from evaporite minerals. The method of using extractable SO4 concentration for SMB estimation was deemed inappropriate for recharge rate estimation in loess areas.