Groundwater hydrochemical signatures, nitrate sources, and potential health risks in a typical karst catchment of North China using hydrochemistry and multiple stable isotopes

Nitrate pollution in aquatic ecosystems has received growing concern, particularly in fragile karst basins. In this study, hydrochemical compositions, multiple stable isotopes (δ²H-H₂O, δ¹⁸Ο-Η₂Ο, δ¹⁵Ν-ΝΟ₃^-, and δ¹⁸Ο-ΝΟ₃^-), and Bayesian stable isotope mixing model (MixSIAR) were applied to elucidate nitrate pollution sources in groundwater of the Yangzhuang Basin. The Durov diagram identified the dominant groundwater chemical face as Ca-HCO₃ type. The NO₃^- concentration ranged from 10.89 to 90.45 mg/L (average 47.34 mg/L), showing an increasing trend from the upstream forest and grassland to the downstream agricultural dominant area. It is worth noting that 47.2% of groundwater samples exceeded the NO₃^- threshold value of 50 mg/L for drinking water recommended by the World Health Organization. The relationship between NO₃^-/Cl^- and Cl^- ratios suggested that most groundwater samples were located in nitrate mixed endmember from agricultural input, soil organic nitrogen, and manure & sewage. The Self-Organizing Map (SOM) and Pearson correlations analysis further indicated that the application of calcium fertilizer, sodium fertilizer, and livestock and poultry excrement in farmland elevated NO₃^- level in groundwater. The output results of the MixSIAR model showed that the primary sources of NO₃^- in groundwater were soil organic nitrogen (55.3%), followed by chemical fertilizers (28.5%), sewage & manure (12.7%), and atmospheric deposition (3.4%). Microbial nitrification was a dominant nitrogen conversion pathway elevating NO₃^- levels in groundwater, while the denitrification can be neglectable across the study area. The human health risk assessment (HHRA) model identified that about 88.9%, 77.8%, 72.2%, and 50.0% of groundwater samples posing nitrate's non-carcinogenic health hazards (HQ > 1) through oral intake for infants, children, females, and males, respectively. The findings of this study can offer useful biogeochemical information on nitrogen pollution in karst groundwater to support sustainable groundwater management in similar human-affected karst regions.