Hydrochemical research and identification of nitrate contamination are of great significant for the endorheic basin, and the Northern Huangqihai Basin (a typical endorheic basin) was comprehensively researched. The results showed that the main hydrochemical facies were HCO₃–Mg·Ca and HCO₃–Ca·Mg. Spatial variation coefficients of most indices were greater than 60%, which was probably caused by human activities. The hydrochemical evolution was mainly affected by rock weathering and also by cation exchange. The D–¹⁸O relationship of groundwater was δD = 5.93δ¹⁸O − 19.18, and the d–excess range was −1.60–+6.01‰, indicating that groundwater was mainly derived from precipitation and that contaminants were very likely to enter groundwater along with precipitation infiltration. The NO₃(N) contents in groundwater exceeded the standard. Hydrochemical analyses indicated that precipitation, industrial activities and synthetic NO₃ were unlikely to be the main sources of nitrate contamination in the study area. No obvious denitrification occurred in the transformation process of nitrate. The δ¹⁵N(NO₃) values ranged from +0.29‰ to +14.39‰, and the δ¹⁸O(NO₃) values ranged from −6.47‰ to +1.24‰. Based on the δ¹⁵N(NO₃) – δ¹⁸O(NO₃) dual isotope technique and hydrochemical methods, manure, sewage and NH₄ fertilizers were identified to be the main sources of nitrate contamination. This study highlights the effectiveness of the integration of hydrochemical and isotopic data for nitrate source identification, and is significant for fully understanding groundwater hydrochemistry in endorheic basins and scientifically managing and protecting groundwater.

Groundwater is the main clean water resource in northern China, and its quality is critical for both human health and social sustainable development. Due to complex anthropogenic and/or geogenic processes, the sources of groundwater contaminants are not easy to determine. The Tabu River Basin, located in northern China, is an agriculture and pasture interlaced area in which phreatic groundwater is the predominant water resource for domestic and agricultural purposes. Groundwater with abnormally high levels of NO₃⁻, F⁻, and TDS was observed here based on 87 groundwater samples collected from the phreatic aquifer in 2022. In this study, hydrogeochemical and isotopic methods were used to trace groundwater contaminants in the phreatic aquifer, and a risk assessment was conducted to analyze their threat to human health. The results indicated that NO₃⁻ in the phreatic groundwater primarily originated from manure, the high concentration of TDS was highly associated with irrigation, and the enrichment of F⁻ was mainly controlled by geogenic factors, including alkaline condition, competitive adsorption, the dissolution of fluorine-bearing minerals, and cation exchange. A principal component analysis (PCA) showed that both anthropogenic (PC1, 50.7%) and geogenic (PC2, 19.9%) factors determined the quality of the phreatic groundwater in the study area. The human health risk assessment demonstrated that 98.9%, 92.0%, and 80.5% of the groundwater samples exceeded the permissible limit of the total noncarcinogenic risk for children, adult females, and adult males, respectively. The monitoring results from 2022 to 2023 suggested that phreatic groundwater contamination could not be mitigated through natural attenuation under the existing external pressures. Measures need to be taken to decrease the contamination of phreatic groundwater and enhance the groundwater sustainability in the Tabu River Basin. The findings of this study can provide a reference for sustainable groundwater development in the Tabu River Basin and other arid and semi-arid regions worldwide.