Mixing calculations have been widely applied to identify sources of groundwater recharge, but these calculations have assumed that the concentrations of end-members are well known. However, the end-members of water remain unclear and are not easily available in practical applications. To better determine end-members and mixing ratios, an end-member mixing analysis combining multivariate statistical methods was used on a large, complex water chemistry dataset collected from the Shashandao gold mine in China. Multivariate statistical methods, including principal component analysis (PCA) and hierarchical cluster analysis (HCA), were applied to determine the specific end-members (these two methods verified each other). On the basis of the identified end-members, a maximum likelihood method was then used to estimate the mixing ratios of the water sources. The combined method proposed in this study can help to identify more accurate end-members and deal with uncertainty in end-member concentrations, and it can also adjust the concentrations until the optimal mixing ratios for the calculation are obtained. This method can be a powerful tool for groundwater management and in predicting water inrush in mining operations.

The Sanshandao gold mine, which is the largest coastal mine in China, is under threat from seawater intrusion and water inrush. The objective of this study is to determine the water end-members (seawater, freshwater, and brine) of the seepage water in the mine and quantify the proportion of end-members. Non-conservative ions and ion exchange were identified by using hydrogeochemical analysis. Then, the principal component analysis (PCA) was used to identify the end-members of mine water. Three end-members were identified, so a ternary mixture model was applied to compute the mixing ratios. The potential water flow channels and the prevailing supply patterns were inferred by combining the results of mixing ratios with the tectonic and engineering geological conditions. The results indicate that the proportion of seawater in mine water is about 57%, the freshwater is about 16% and the brine is about 27% for the entire mine area, the prevailing supply pattern of seawater was lateral recharge, the water samples which were located in −510 m sublevel or in the northeast of prospecting line 2260 had high proportions of seawater, the freshwater supplied the groundwater mainly through the secondary fractures developed area in a vertical recharge and the influence depth was about −500 m, and F3 was the largest tensile-shear fault in the study area and it was both a watercourse for seawater and fresh water.

The natural discharge of geothermal water containing harmful components affects the water quality of the surrounding environment and brings security risks to drinking water safety. The geothermal water in Tibet is characterized by high boron content, but the water pollution caused by the discharge of this high boron geothermal water is not clear. In this study, we collected geothermal water and surface water from the Zhaxikang geothermal system in southern Tibet to investigate the causes of high boron geothermal water and the water pollution of water quality by its discharge. The results indicate that the hydrochemical type of geothermal water was HCO₃-Cl-Na, while that of cold spring water, mine water, river water, and lake water was SO₄-HCO₃-Ca-Mg. Hydrogen and oxygen isotopes show that the recharge source of cold groundwater was mainly snow-melting water and meteoric water, while in addition to that, there is magmatic water for hot springs. The boron content of geothermal water in the study area is as high as 42.36 mg/L, far exceeding the World Health Organization limit for drinking water (0.5 mg/L). The analysis of ion components and PHREEQC modeling indicated that the dissolution of silicate minerals and cation exchange controlled the composition of groundwater, and the boron in groundwater mainly came from the volatilization of magmatic components and the leaching of shallow sediments. The entropy weight water quality index was used to evaluate the water quality of the study area; about 42.9% of the groundwater samples are of good quality and can be used for drinking, mainly cold water that has not been mixed with geothermal water in the upstream. With the discharge of geothermal water into the river (with a mix ratio of ~20%), the downstream water quality gradually deteriorated. The health risk assessment of drinking water in the study area showed that the hazard index (HI) of drinking water in the mixed area was higher than 1 (with an average of 1.594 for children and 1.366 for adults), indicating that children are at a higher health risk than adults. Geothermal water with high boron content has been found all over the world, and the adverse effects of its natural drainage cannot be ignored.