Hydrochemical and Isotopic Characteristics of Water in Mamian Pyrite Mining Area and Their Environmental Indication Significance
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摘要: 酸性矿坑水（acid mine drainage，AMD）会导致受纳水体水质恶化，加速碳酸盐岩溶解而释放CO2，危害甚广.结合水文地质条件，采用水化学和同位素手段，探讨桂林马面矿区地表水和地下水中污染物来源及迁移机制.流域水体化学组分主要来源于碳酸盐岩和硅酸盐岩的风化以及硫化物的氧化，水化学类型以Ca-HCO3为主，部分采样点受人类活动影响转为Ca-HCO3·SO4和Ca·（K+Na）-HCO3型.硫氧同位素揭示硫化物氧化、雨水和污水是流域地表水和地下水SO42-的主要来源.从水化学和同位素组成变化表明，AMD对地表水和地下水的影响沿流程增加而逐渐降低，分别影响至下游约13.5 km和1.5 km.此研究不仅揭示了AMD和人类活动对研究区水体的负面影响，为马面矿区水资源保护治理提供了基础数据；同时证实了同位素和水化学相结合是研究矿区污染物迁移转化的有效手段，为其他矿区污染物的研究提供了新思路.Abstract: Acid mine drainage (AMD) can contribute to deterioration of the receiving water quality, accelerate the dissolution of carbonate rocks, leading to the release of CO2, which poses a wide range of hazards. Combined with the hydrogeological setting, hydrochemical and isotopic methods are employed to investigate the sources and migration mechanisms of pollutants in surface and groundwater of the Mamian mining area in Guilin, China. Results show that: (1) the chemical composition of surface water and groundwater mainly came from the weathering of carbonate and silicate rock, as well as the oxidation of sulfide, and Ca-HCO3 was the main water type in the study area, while some sites affected by AMD and domestic sewage wastewater changed to Ca-HCO3·SO4 and Ca·(K+Na)-HCO3 types; (2) sulfur and oxygen isotopes indicate that sulfide, rainwater and sewage were the three main SO42- sources for sampled surface-ground waters; and (3) changes in hydrochemical and isotopic composition indicate that the influence of AMD on surface water and groundwater gradually decreased along the flow directions, affecting to approximately 13.5 km and 1.5 km downstream, respectively. This study not only revealed the negative impact of AMD and human activities on the waters, provided basic data for the protection of water resources for the studied mine area. At the same time, the combination of isotope and water chemistry is proved to be an effective means to study the migration and transformation of pollutants in mining area, which provides a new idea for the study of pollutants in other mining areas.
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Key words:
- hydrochemistry /
- sulfur and oxygen isotopes /
- acid mine drainage /
- sulfate /
- karst /
- hydrogeology
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图 1 研究区（a）地理位置，（b）水文地质概况和采样点分布和（c）A-A'水文地质剖面
Fig. 1. Location of the study watershed (a), details of the hydrogeology and sampling sites (b) and hydrological cross-section (c)(line A-A')
图 2 研究区不同水体水化学Piper图
Fig. 2. Piper diagram for the different waters within the study area
图 3 研究区不同水体Gibbs图
Fig. 3. Gibbs diagram for the different waters within the study area
图 4 研究区不同水体Ca2+/Na+与Mg2+/Na+（a）, Ca2++Mg2+与HCO3-（b）, Ca2++Mg2+与HCO3-+SO42-（c）, 和Mg2+/Ca2+与SO42-的关系（d）
Fig. 4. Plots of Ca2+/Na+ vs. Mg2+/Na+ (a), Ca2++Mg2+ vs. HCO3- (b), Ca2++Mg2+ vs. HCO3-+SO42- (c), and Mg2+/Ca2+ vs. SO42- (d) for the different waters within the study area
图 5 研究区不同水体Cl-与TIN的关系图
图中对应范围修改自Panno et al.（2006a，2006b），Zhang et al.（2014）和Ren et al.（2022）
Fig. 5. Cl- vs. TIN plot for the different waters within the study area
图 6 研究区不同水体（a）1/SO42-与δ18O-SO4和（b）δ34S-SO4与δ18O-SO4的关系
图6b中边界斜率0.26和0.48来源于Gammons et al.（2013）
Fig. 6. Plots of 1/SO42- vs. δ18O-SO4 (a) and δ34S-SO4 vs. δ18O-SO4 (b) for the different waters within the study area
图 7 研究区不同水体δ18O-H2O与δ18O-SO4关系
Fig. 7. The δ18O-H2O vs. δ18O-SO4 plot for the different waters within the study area
图 8 采样点中SO42-（a）和δ34S-SO4与δ18O-SO4（b）沿流程变化
Fig. 8. Changes in SO42- concentration (a) and δ34S-SO4 and δ18O-SO4 values (b) at sampling points along the water flow path
图 9 各输入端贡献比例沿流程变化（a）和Cl-与δ34S-SO4的关系（b）
Fig. 9. Changes in contribution ratios of each input along the flow path (a) and the relationship between Cl- and δ34S-SO4 (b)
表 1 研究区不同水体理化性质、化学成分和同位素组成变化范围
Table 1. Ranges of physicochemical, chemical parameters and stable isotope ratios for the different waters within the study area
水体 时间/范围 pH EC DO Ca2+ Mg2+ K+ Na+ TFe Cl- SO42- HCO3- NO3- NO2- NH4+ δ18O-H2O δ34S-SO4 δ18O-SO4 （μS/cm） (mg/L) （‰） 老窑水（n=3) 2023年9月 4.4 7 030 5.4 439 810.0 2.4 0.5 638.90 2.8 6 263 0 0.4 bdl 11.38 -5.9 -10.5 1.3 2023年2月 3.8 12 060 6.0 432 2 164.4 3.3 2.6 1 532.50 4.6 12 038 0 2.9 bdl 246.25 -5.8 2022年7月 5.5 4 630 5.7 498 450.7 4.4 1.0 342.40 2.7 3 680 6 0.9 bdl 40.21 -6.8 -13.2 3.1 地表水（n=7) 最小值 7.4 350 3.3 39 5.8 1.0 1.0 0.44 2.9 15.4 58 0.7 bdl bdl -6.6 -11.6 3.7 最大值 9.0 779 12.0 110 37.7 13.7 4.1 1.29 9.1 199 249 10.6 0.52 bdl -5.0 5.5 9.2 平均值 7.8 446 7.3 69 11.5 4.1 3.0 0.70 6.6 60.2 189 5.4 0.36 -5.7 -1.9 7.1 标准偏差 0.6 152 3.0 22 11.6 4.3 1.1 0.29 2.0 68.1 62 3.9 0.26 0.6 6.8 1.9 地下水（n=15) 最小值 6.9 298 3.4 53 4.6 0.3 0.4 0.40 1.1 11.2 165 0.1 bdl bdl -6.3 -13.2 3.1 最大值 7.7 2, 170 11.8 381 120.6 44.4 9.8 3.99 14.4 1 184 299 54.3 8.85 0.75 -5.2 4.2 8.0 平均值 7.2 676 5.7 112 20.4 7.4 2.1 1.13 5.9 147.9 256 14.1 1.39 0.45 -5.8 -5.3 5.4 标准偏差 0.2 463 2.5 80 31.6 13.5 2.5 0.85 4.0 307.3 36 17.7 2.87 0.38 0.3 4.4 1.7 污水（n=4） 2023年2月 38.14 48.37 26.56 25.93 2022年7月 7.69 23.16 6.62 11.79 注：dbl为低于仪器检测限. 
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