Quantitative identification of groundwater contamination sources by combining isotope tracer technique with PMF model in an arid area of northwestern China.

Nowadays, groundwater quality has deteriorated because of intensive human activities. It is important to accurately identify the pollution source for controlling the deterioration of groundwater quality. However, the accuracy of the current source analysis method needs to be improved. In this study, we combined hydrochemical method, isotope tracing technique and PMF model, for the first time, to trace the source of groundwater pollution in Beichuan River basin, Qinghai Province, China. According to the results, there were 35.8% of Fe, 34.1% of total hardness, 24.3% of SO42- and 8.09% of NO3- samples exceeded the Grade III standards for Groundwater quality in China, which indicated that the groundwater in the study area has been significantly affected by human activities. Hydrochemical method suggested that the chemical component originated from rock weathering, cation exchange and mineral dissolution. Based on isotope tracing technique (δ15N-NO3-, δ18O-NO3-, δ34S-SO42- and δ18O-SO42-), the primary sources of nitrate and sulfate in groundwater were soil nitrogen and oxidation of sulfide minerals in the forest area, domestic sewage and oxidation of sulfide minerals in the urban and industrial area, and mixed sources in the village and agricultural area. Finally, the pollution source of groundwater was distinguished by combining the PMF model, isotope tracing technique and hydrochemical method. Results showed that the main pollutant of groundwater is domestic sewage in the urban, village and industrial area. The contribution rates to groundwater pollution were 60.7%, 60.8% and 57.8%, respectively. However, in the forest and agricultural area, the main source changed to water-rock interaction and chemical fertilizer, and the contribution rates to groundwater quality were 53.5% and 61.0%, respectively. Our results suggested that the coupling tracing methodology can improve the accuracy of source resolution in the water environment and it can be applied to other areas of the world.

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 δ15N from 10.6‰ to 7.5‰ 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 δ15N (the median value from 7‰ to 12‰) 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.

[Hydrochemical and Isotopic Evidence for Groundwater Conversion of Surface Water in Alpine Arid Areas: A Case Study of the Datong River Basin].

Global warming and regional extreme climates will lead to unbalanced rainfall, melting glaciers, and permafrost degradation in alpine and arid mountain plains, thereby changing the regional hydrological cycle. The relationship between surface water and groundwater conversion is one of the important scientific issues of hydrological cycle climate response in alpine arid areas. Taking the Datong River Basin at the southern foot of the Qilian Mountains as the study area, based on 119 sets of basic hydrochemical parameters and deuterium-oxygen isotope data, using multivariate statistical analysis and isotopic techniques, the hydrochemical characteristics of surface water and groundwater in the basin and their mutual transformation process were studied. The results showed that the surface water was HCO3-Mg·Ca type, which was mainly controlled by rock weathering, whereas the groundwater was HCO3-Mg·Ca type and Cl·SO4-Na type, which was controlled by rock weathering and evaporation concentration. There was a small amount of calcium and magnesium feldspar dissolved in the upstream groundwater, and the chemical components of the midstream groundwater were mainly the weathering and dissolution of carbonate rocks. The contribution rates of weathering filtration, anthropogenic activities, native sedimentary environment, alternating adsorption of cations, and other factors to the chemical components of surface water and groundwater in the study area were 39.1%, 15.0%, 12.6%, 13.8%, and 19.5%, respectively. The deuterium and oxygen isotope contents of Datong River water showed a trend of enrichment to depletion along the groundwater flow direction. The δD and δ18O isotope test results showed that the deuterium and oxygen isotope content in the Datong River along the groundwater flow showed a trend of enrichment to depletion. The upper and middle reaches of the Datong River were mainly recharged by atmospheric precipitation, whereas the lower reaches were affected by geological structure and influenced by hydrogeological conditions, which was mainly due to diving and spring water overflow to supply river water, as the discharge area of groundwater.

Distributions, origins, and health-risk assessment of nitrate in groundwater in typical alluvial-pluvial fans, North China Plain.

High concentration of nitrate (NO3-) in groundwater is a major concern because of its complex origin and harmful effects on human health. This study aims to investigate the distributions of nitrate in various aquifers and in areas with different land use types in alluvial-pluvial fans in North China Plain, to identify dominant sources and factors using hydrochemical data and principal component analysis, and to conduct health-risk assessment of groundwater nitrate using the models recommended by USEPA. Results show that approximately 76.1% groundwater in fissured aquifers showed high-NO3- (> 50 mg/L), and was 2.7 times of that in granular aquifers. In fissured aquifers, the proportion of high-NO3- groundwater (PHNG-WHO) in peri-urban areas was more than 1.3 times of those in other areas. Similarly, in shallow granular aquifers, the PHNG-WHO in peri-urban areas was also higher than that in other areas. By contrast, in deep granular aquifers, the PHNG-WHO in urbanized areas was 2.8 and 5.2 times of that in peri-urban areas and farmland, respectively. High NO3- levels in both granular and fissured aquifers originated mainly from domestic sewage and animal waste, and fertilizers are also important sources of NO3- in fissured aquifers. Intensive groundwater exploitation aggravated nitrate contamination because more thickness of vadose zones resulting from over-exploitation is in favor of nitrification. Risk assessment of groundwater nitrate indicated about 43.3%, 45.6%, and 54.2% of the groundwater samples showed unacceptable non-carcinogenic risk to adult males, adult females, and children, respectively. The proportion of samples with health risks had a significant positive correlation with the urbanization level. Our study indicates that several effective measures for pollution prevention, such as strengthening sewage treatment and prohibiting groundwater over-exploitation, must be adopted so as to ensure the sustainable management of groundwater and the safety of drinking water.

Groundwater quality assessment and pollution source apportionment in an intensely exploited region of northern China.

Deterioration in groundwater quality has attracted wide social interest in China. In this study, groundwater quality was monitored during December 2014 at 115 sites in the Hutuo River alluvial-pluvial fan region of northern China. Results showed that 21.7% of NO3- and 51.3% of total hardness samples exceeded grade III of the national quality standards for Chinese groundwater. In addition, results of gray relationship analysis (GRA) show that 64.3, 10.4, 21.7, and 3.6% of samples were within the I, II, IV, and V grades of groundwater in the Hutuo River region, respectively. The poor water quality in the study region is due to intense anthropogenic activities as well as aquifer vulnerability to contamination. Results of principal component analysis (PCA) revealed three major factors: (1) domestic wastewater and agricultural runoff pollution (anthropogenic activities), (2) water-rock interactions (natural processes), and (3) industrial wastewater pollution (anthropogenic activities). Using PCA and absolute principal component scores-multivariate linear regression (APCS-MLR), results show that domestic wastewater and agricultural runoff are the main sources of groundwater pollution in the Hutuo River alluvial-pluvial fan area. Thus, the most appropriate methods to prevent groundwater quality degradation are to improve capacities for wastewater treatment and to optimize fertilization strategies.