Source and evolution of sulfate in the multi-layer groundwater system in an abandoned mine-Insight from stable...

The source and evolution of sulfate (SO₄^2-) in groundwater from abandoned mines are widely concerned environmental issues. Herein, major dissolved ions, multi-isotopes (δ³⁴S, δ¹⁸O_sulfate, δ²H and δ¹⁸O_water), machine learning (Self-organizing maps) and Bayesian isotope mixing model were used to identify the source and evolution of SO₄^2- in an abandoned mine (Fengfeng mine, northern China) with a multi-layer groundwater system. Groundwater in the study area was mainly divided into three clusters (Cluster I, Cluster II and Cluster III), dominated by Na-SO₄, Ca-SO₄ and Ca-HCO₃ types, respectively. According to δ²H and δ¹⁸O_water, groundwater in the study area mainly originated from atmospheric precipitation. δ³⁴S, δ¹⁸O_sulfate and SO₄^2- suggested that bacterial sulfate reduction did not affect the SO₄^2- isotopic composition. Dual SO₄^2- isotopes, and MixSIAR model revealed that the main source of SO₄^2- in the study area was pyrite oxidation/gypsum dissolution, accounting for an average of 57.4 % (gypsum), 71.24 % (pyrite oxidation) and 52.93 % (pyrite oxidation) of SO₄^2- in the samples of Clusters I-III, respectively. Combined with the hydrochemical diagrams, the evolution of SO₄^2- in different clusters of samples was derived. Cluster I was mainly gypsum dissolution; In contrast, Clusters II and III were mainly pyrite oxidation accompanied by carbonate dissolution, and Cluster II was also influenced by cation exchange. These findings will help in developing management strategies for protecting groundwater quality, which will provide a reference for the study of solute sources and S cycling in abandoned mines.