Origins of groundwater nitrate in a typical alluvial-pluvial plain of North China plain: New insights from groundwater age-dating and isotopic fingerprinting

Identifying nitrate sources and their temporal evolution in different land use is important for the sustainable management of groundwater resources. In this study, groundwater dating (3H-3He and time series of 3H) was combined with chemical and stable isotope analyses to resolve the evolution of nitrate sources and the driving mechanism of nitrate contamination. Approximately 75% of the groundwater samples (collected in 2014 and 2018) had nitrate concentrations exceeding World Health Organization's guideline for drinking water (50 mg/L), and 44% exceeded the groundwater quality standard of China (88.6 mg/L), indicating severe nitrate pollution. The shift of nitrate sources in different land use was identified using stable isotope composition of nitrate and groundwater age. The decreasing median value of 815N from 10.6%o to 7.5%o of dated groundwater in farmland irrigated by clean water indicated the shift of nitrate sources from manure toward the mixing of fertilizer and manure due to the increased application of chemical fertilizers from intensive plant farming since 1980s. Comparably, the trend of increasing 815N (the median value from 7%o to 12%o) in farmland irrigated by wastewater might be attributed to the decreasing proportion of industrial wastewater since 2000s. The prevailing sources of nitrate in residential area were manure and sewage, and showed no obvious change along the recharge time. Driven by rapid urbanization, the nitrate sources of land use change area exhibited a marked shift from inorganic fertilizers toward manure and sewage. Principal component analysis (PCA) on nitrate concentrations with multiple parameters indicated nitrogen input in agricultural development and urbanization were the main controlling factors of nitrate contamination in the study area. The study results are a good reference for groundwater management in regions with nitrate source change during the process of rapid urbanization and agricultural intensification. The coupling of chemical, isotopic analyses and groundwater dating proved to be invaluable and should be applied in similar studies of nitrate contamination.