Stable isotope geochemistry of dissolved chloride in relation to hydrogeology of the strongly exploited Quaternary aquifers, North China Plain

Deep Quaternary groundwater is the main source for industrial, domestic, and agricultural water supply in the North China Plain (NCP). There is currently a regional decline of groundwater levels, deterioration of water quality and environmental geological problems induced by increasing exploitation of the NCP Quaternary aquifer system. To trace sources and transport processes of dissolved Cl− in a regional aquifer system and to reveal hydrogeological characteristics of Quaternary complexes, δ37Cl, δ18O and δD, and chemical compositions (including F−, Cl−, Br−) of the deep groundwater sampled from the northern flow system of the NCP were measured along the west–east groundwater flow paths. The measured δ37Cl values decreased from 0.39‰ to −2.22‰ (SMOC) along the groundwater flow direction, with increasing Cl− concentrations. Marine aerosol input via rainfall is the main source of Cl− in the deep groundwater near the recharge areas, and subsequent evaporation/evapotranspiration appears to be responsible for Cl− accumulation. Mixing of recharge water with water of high-Cl− and low-δ37Cl accounts for the pattern of δ37Cl and Cl− concentration observed in Aquifer-3 along the west–east transect. The water with high-Cl and low-δ37Cl is likely from pore water released from compacted clays induced by over-exploitation of deep groundwater, suggesting that clay is a dominant subsurface source of Cl− for groundwater where a regional depression cone is present in the Quaternary aquifers. The groundwater of Aquifer-4 in the Huang-Hua depression is potentially mixed with an upward flux of Cl− from the Neogene aquifer through subvertical faults. Diffusion and ion filtration are two mechanisms invoked to explain the highly negative δ37Cl data for groundwater of Aquifer-4 in the Yanshan–Haixing areas, which provides new insight into solute migration and the hydraulic relationship in the strongly exploited groundwater system. This study using the conservative solute Cl− provides additional important information for further investigations of the geochemistry of a wide range of reactive solutes in the Quaternary aquifer system, so guiding water resource management.

► Decrease in δ37Cl with increase in Cl was observed along groundwater flow direction.
► Released pore water from compacted clay by over-exploitation accounted for increasing Cl.
► Upward flux of Cl from the Tertiary aquifer could occur at the fault areas.
► Cl isotope fractionation mechanisms indicated solutes migration and hydraulic connection between aquifers.