Abstract

Various environmental factors could induce groundwater hydrochemical evolution, which should be considered when addressing groundwater environmental issues. However, the complex interactions among the environmental controls remain unknown for a groundwater flow system spanning multiple geological units. To fill this gap, we conducted a study on the groundwater hydrochemical evolution in the fluvial corridor of the Fen River, Northern China, utilizing a combination of hydrogeochemical and multiple isotope methods. Results reveal that the groundwater in the corridor has significantly degraded due to high concentrations of SO42-\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext{SO}}_{4}^{2 - }$$\\end{document}, NO3-\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext{NO}}_{3}^{ - }$$\\end{document}, Cl−, or F−. We find an unordered evolution of the hydrochemical composition of groundwater along this corridor. These evolutions are driven by mineral dissolution/precipitation, dedolomitization, and cation exchange processes. Human activities play a significant role, with notable contributions including NO3-\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext{NO}}_{3}^{ - }$$\\end{document} fluxes from agricultural fertilizers, manure, and sewage, as well as SO42-\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext{SO}}_{4}^{2 - }$$\\end{document} fluxes arising from coal mining activities. The combination between karst spring areas and faults/uplifts, between coal-bearing strata and mining activities fosters the mixing of karst water/mine water with shallow groundwater, promoting dramatic hydrochemical evolution of groundwater. The flat terrain and the natural blockage formed by mountains significantly enhance water–rock interactions and groundwater evaporation by slowing groundwater flow. The contribution of evaporation on groundwater salinity ranges from ~ 0.2% to 4.8%, highlighting its importance in the groundwater hydrochemical evolution. This study unravels the multifaceted nature of groundwater hydrochemical evolution. It emphasizes the four types of environmental controls, including hydrogeochemical processes, climate factors, human activities, and variations in geological settings, can be equally important, which is usually ignored. The findings enrich our understanding of groundwater evolution and highlight the challenges encountered in regions composed of diverse geological units.

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