Coupling hydrochemistry and stable isotopes to identify the major factors affecting groundwater geochemical evolution in the Heilongdong Spring Basin, North China

Understanding the interference of natural processes and anthropogenic activities in geochemical evolution of groundwater is vital for groundwater sustainable management in water-stressed regions. This study is devoted to the identification of the main factors controlling the evolution of groundwater chemistry by the combined use of hydrogeochemical indicators along with isotope tracers in the Heilongdong Spring Basin, North China. Thirty-nine groundwater samples and twelve surface water samples were collected, and major ions and stable isotopes were measured during the two campaigns (December 2017 and August 2018). The isotope approach indicates that the groundwater is recharged by precipitation infiltration after evaporation, and interacts with surface water along preferential flow paths in fault zones and karst conduits. Currently, the main chemical facies of groundwater evolve from Ca-HCO₃ and Ca-Mg-HCO₃ types with low TDS, through Ca-Mg-HCO₃-SO₄ and Ca-HCO₃-SO₄ types with moderate TDS, to Ca-SO₄, Ca-SO₄-Cl and Ca–Cl types with high TDS. Apart from natural processes (involving dissolution/precipitation of minerals, cation exchange, and evaporation) regulating the groundwater quality, the stagnant zones also play a crucial role in the formation of severe localized nitrate contamination. The deterioration in groundwater quality can be attributed to anthropogenic factors (including the change in groundwater exploitation, the leaching of solid waste, and the overuse of agricultural fertilizers). The high loads of agricultural fertilizers in irrigation return flows are likely to be the main contributor of the dissolved nitrate in groundwater. The findings of this work not only have important implications for groundwater sustainable utilization, but also could serve as a template for other rapidly industrialized and water-stressed regions.