Rare earth elements (REEs) have been used as tracers to reveal the hydrochemical sources and processes in groundwater systems that are usually modified by anthropogenic inputs. However, the REE behaviors in groundwater affected by mining activities have yet to be fully understood. In combination of REE geochemistry with general hydrochemical and isotopic (δH and δO) methods, this study investigated the concentration and fractionation of REEs in alkaline groundwater from two coal mines with similar aquifer lithology but different mining histories in the Northern Ordos Basin. One of the coal mines started mining in March 2009 (Ningtiaota coal mine, NTT), while the other started mining in December 2018 (Caojiatan coal mine, CJT). Results show that the primary hydrochemical type is HCO-Ca in NTT groundwater with pH value ranging between 7.68 and 8.60, while CJT groundwater was dominated by the HCO-Na type with higher pH of 9.09-10.00. The average values of ΣREEs were lower, and the NASC-normalized pattern reflected more intense fractionation in NTT groundwater than those in CJT groundwater. The evident differences are caused by the distinctions in water-rock interaction, complexation of inorganic species, and adsorption of REEs in NTT and CJT groundwater. Furthermore, these processes were closely related to the pH of groundwater that was different in two coal mines, which is likely linked to the different durations of coal mining activities that led to differences in development of rock fractures and pyrite oxidation. It is expected that REEs, combined with other indicators such as pH, can be used to trace and help better understand the hydrochemical changes in groundwater caused by mining.
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