Indication of Hydrochemistry and δ34S-SO42‒ on Sulfate Pollution of Groundwater in Daye Mining Area
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摘要: 铜铁矿区周边地下水硫酸盐污染是生态环境研究关注的热点问题，精确识别硫酸盐来源及迁移途径对于矿区周边地下水污染防控和供水安全至关重要.利用水化学与硫同位素耦合分析，结合矿区水文地质条件和潜在污染源分布，探讨了区内地下水硫酸盐污染特征、来源及迁移途径.区域内地下水包括松散岩类孔隙水、碳酸盐岩裂隙岩溶水及岩浆岩风化裂隙水，水化学类型主要为HCO3∙SO4-Ca型，水化学组分主要来源于硅酸岩、碳酸盐岩和硫酸盐矿物的溶解以及硫化物氧化；地下水中SO42‒含量范围为44.4~2 089.0 mg/L，高值区主要分布在洪山溪尾矿库、矿渣堆存处及矿业生产区附近；地下水中δ34S-SO42‒在2.6‰~31.5‰之间，反映其SO42‒具有多源性.地下水中SO42‒的主要来源包括含水层中石膏矿物的溶解和黄铁矿等含硫矿物氧化输入，高含量的SO42‒主要来源于黄铁矿氧化的贡献；矿坑排水、尾矿渗漏、选矿粉尘沉降淋滤下渗以及废水渗漏是地下水硫酸盐污染的主要途径.Abstract: Sulfate pollution of groundwater around copper and iron mining areas is a hot issue in ecological environment research. It is very important to identify the sources and migration routes of sulfate in the groundwater system for the prevention of groundwater pollution and the safety of water supply in the mining area. Combined with the hydrogeological setting and the distribution of potential pollutant sources in the mining area, the coupled analysis of hydrochemistry and δ34S-SO42‒ was carried to explore the characteristics, sources and migration pathways of groundwater sulfate pollution in the area. The results show that the groundwater in the area included the pore water in the sedimentary aquifers, the karst water of carbonatite and the fissure water of igneous rocks. The main hydrochemical type was HCO3·SO4-Ca. The formation of hydrochemical components mainly included the dissolution of silicate, carbonate and sulfate minerals, as well as the oxidation of sulfide. The content of SO42‒ ranged between 44.4 mg/L and 2 089.0 mg/L. The groundwater with elevated SO42‒ concentration occurred near the Hongshan River tailings reservoir, the slag heap and the industrial areas. The value of δ34S in regional groundwater ranged between 2.6‰ and 31.5‰, indicating that SO42‒ came from multiple sources. The sources of sulfate in groundwater included the dissolution of gypsum, the oxidation of sulfide such as pyrite. The maximum of SO42‒ attributed to the oxidization of pyrite. Mine drainage, tailing leakage, the settling of dust and wastewater infiltration were the main pathways of groundwater pollution.
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Key words:
- Daye mining area /
- hydrogeochemistry /
- source of sulfate /
- sulfur isotope /
- groundwater /
- environmental engineering
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图 1 研究区水文地质及采样点分布
Fig. 1. Hydrogeological map of the study area and distribution of the sampling sites
图 3 研究区地表水和地下水Durov图
Fig. 3. Durov diagram of groundwater and surface water samples in the study area
图 4 研究区水样SO42‒含量分布
Fig. 4. Distribution of SO42‒ concentrations in water samples of the study area
图 7 地下水不同矿物饱和指数与TDS关系
Fig. 7. Relationship between mineral saturation index and TDS in groundwater
图 8 研究区地下水δ34S-SO42‒与SO42‒关系
Fig. 8. Relationship between δ34S-SO42‒ and SO42‒ in the groundwater samples from the study area
图 9 大冶矿区地下水硫酸盐污染概念模型
Fig. 9. Conceptual model diagram of groundwater sulfate pollution in Daye mining area
表 1 地下水及地表水主要水化学指标统计特征
Table 1. Hydrochemical parameters of groundwater and surface water samples
类型 项目 pH TDS 硬度 Na+ K+ Ca2+ Mg2+ Cl‒ SO42‒ HCO3‒ Fe Mn 地表水
n=3最大值 8.70 1 338.00 951.00 43.72 22.21 290.70 74.78 57.10 884.00 148.00 0.094 0.796 最小值 7.64 918.60 624.80 21.85 6.31 199.10 30.50 13.50 613.00 67.83 0.005 0.003 平均值 8.12 1 190.00 810.40 29.68 13.64 248.60 45.33 28.20 772.30 104.80 0.037 0.268 CV 0.05 0.16 0.17 0.34 0.48 0.15 0.46 0.72 0.15 0.31 1.078 1.394 地下水
n=22最大值 8.65 3 184.00 2 437.00 163.00 46.98 422.80 331.20 41.30 2 089.00 528.00 6.820 2.970 最小值 7.20 121.20 92.75 0.89 0.14 27.31 4.27 2.96 44.40 55.50 < 0.050 < 0.050 平均值 7.82 708.80 523.00 32.16 7.57 140.19 37.18 16.64 340.20 254.00 0.770 0.220 CV 0.05 0.96 0.95 1.31 1.51 0.72 2.14 0.59 1.41 0.50 2.020 2.900 注：CV为变异系数；除pH外，其他指标单位均为mg/L. 
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表 2 研究区地下水中δ34S-SO42-分析结果
Table 2. Analytical results of δ34S-SO42- of groundwater in the study area
样品编号 调查点类型 水位埋深
（m）地下水类型 δ34S-SO42‒
（‰）DJ11 井水 0.70 松散岩类孔隙水 5.0 DJ12 井水 1.10 松散岩类孔隙水 2.6 DJ21 井水 1.80 松散岩类孔隙水 5.4 DQ01 泉水 / 岩浆岩风化裂隙水 4.3 DQ05 泉水 / 碳酸盐岩岩溶水 4.7 DQ04 泉水 / 碳酸盐岩岩溶水 5.5 DQ03 泉水 / 岩浆岩风化裂隙水 5.4 D01 井水 4.36 碳酸盐岩岩溶水 31.5 D02 井水 2.26 碳酸盐岩岩溶水 8.4 D03 井水 7.83 碳酸盐岩岩溶水 5.9 D05 井水 15.57 碳酸盐岩岩溶水 4.6 D07 井水 18.65 碳酸盐岩岩溶水 9.7
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