Groundwater pollution mechanisms in karst critical zone of western mountain of the Jinci Spring area
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摘要:
岩溶地下水资源是我国重要供水水源。在全球气候变化和采煤等强烈人类活动的叠加作用下，晋祠泉域地下水水质恶化。探明水环境问题，识别泉域岩溶关键带地下水污染机制对于泉域岩溶地下水保护具有重要意义。采用熵权法水质指数对泉域地下水进行水质评价。基于水质评价结果，采用水化学耦合地下水硫酸盐硫氧和硝酸盐氮氧同位素进行地下水污染溯源。通过地下水无机碳同位素、锶同位素和硫同位素进一步识别出岩溶地下水污染途径。结果表明，岩溶水中硫酸盐均值为582.07 mg/L，孔隙水硝酸盐质量浓度高达424.72 mg/L，研究区地下水受到明显硫酸盐、硝酸盐污染。污染岩溶水中硫酸盐硫同位素显著偏负，硝酸盐污染岩溶水锶同位素和碳同位素特征与深部孔隙水相似。地下水中过量硫酸盐的主要来源是硫化物氧化和石膏溶解，污水排放和粪肥输入是地下水受硝酸盐污染的重要原因。岩溶含水层的主要污染途径为孔隙水的反向补给和上层老窑水的串层补给。研究成果为晋祠泉域岩溶地下水污染治理及岩溶水资源的合理开发利用提供了重要科学依据。
Abstract:Objective Karst groundwater resources are vital water sources in China. Due to the combined effects of global climate change and intense human activities, such as coal mining, groundwater quality in the Jinci Spring area has deteriorated. Identifying water environmental issues and understanding the groundwater pollution mechanisms in the karst critical zone of this area are crucial for the protection of karst groundwater resources.
Methods The groundwater quality in the spring area was evaluated using the entropy weight method and water quality index. Based on the water quality assessment, isotopic tracing of sulfate oxygen and nitrate nitrogen in groundwater was further performed to trace pollution sources. Additionally, the pollution pathways in karst groundwater were identified through the analysis of inorganic carbon isotopes, strontium isotopes, and sulfur isotopes.
Results The results showed that the average sulfate concentration in karst groundwater was 572.07 mg/L, while the nitrate concentration in pore water reached 424.72 mg/L, indicating obvious sulfate and nitrate pollution in the groundwater from the study area. Sulfur isotopes in the polluted karst water exhibited a remarkable negative deviation, and the strontium and carbon isotopic characteristics of nitrate-polluted karst water resemble to those of deep pore water.
Conclusion The primary source of excessive sulfate in groundwater is sulfide oxidation and gypsum dissolution, while sewage discharge and manure input are the important sources of nitrate contamination. The main pollution pathways in karst aquifers include reverse recharge from pore water and cascade recharge from upper-layer goaf water. This study provides important scientific evidence for the control of karst groundwater pollution and the rational development and utilization of karst water resources in the Jinci Spring area.
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图 1 晋祠泉域西边山岩溶关键带地质综合图
a. 主要地层年代略图；b. 研究区地质剖面图（A-A'-A"）；c. 采样点位置图
Figure 1. Comprehensive geological map of the karst critical zone of the Jinci Spring
图 2 地下水水样EWQI值堆积柱状图（TH为总硬度）
Figure 2. Stacking histogram of EWQI values of groundwater samples
图 4 地下水污染组分(a) TDS, (b) Na+, (c) ${\mathrm{NO}}_3^{-} $和(d) ${\mathrm{SO}}_4^{2-} $空间分布图
Figure 4. Spatial distribution of contaminant (a) TDS, (b) Na+, (c) ${\mathrm{NO}}_3^{-} $, and (d) ${\mathrm{SO}}_4^{2-} $ concentrations in groundwater
图 5 地下水硫酸盐δ18O-δ32S散点图(a)以及地下水硫酸盐$ \delta^{18}{\mathrm{S}}\text{-}{\mathrm{SO}}_4^{2-} $散点图(b)
Figure 5. Scatter plot of δ18O-δ32S in groundwater sulfate (a), and scatter plot of $\delta^{18}{\mathrm{S}}\text{-}{\mathrm{SO}}_4^{2-} $ in groundwater sulfate (b)
图 6 地下水$c({\mathrm{NO}}_3^{-}) $/c(Cl−)与c(Cl−)变化图(a)以及地下水硝酸盐δ15N-δ18O散点图(b)
Figure 6. Variation of ${\mathrm{NO}}_3^{-} $/Cl− molar ratios and Cl− concentrations in groundwater (a) and Scatter plot of δ15N-δ18O nitrate (b) in groundwater
图 7 δ13C与$ {\mathrm{NO}}_3^{-} $/(Ca2++Mg2+)摩尔比散点图(a)以及δ13C与$ {\mathrm{NO}}_3^{-}/{\mathrm{HCO}}_3^{-} $摩尔比散点图(b)
Figure 7. Scatter plot of δ13C versus ${\mathrm{NO}}_3^{-} $/(Ca2++Mg2+) molar ratios in groundwater (a), and scatter plot of δ13C versus ${\mathrm{NO}}_3^{-}/{\mathrm{HCO}}_3^{-} $ molar ratios in groundwater (b)
图 8 地下水87Sr/86Sr与1/Sr散点图
Figure 8. Scatter plot of 87Sr/86Sr versus 1/Sr in groundwater
图 9 地下水硫酸盐$ {\mathrm{SO}}_4^{2-}\text{-}\delta^{34}{\mathrm{S}} $散点图
Figure 9. Scatter plot of ${\mathrm{SO}}_4^{2-}\text{-}\delta^{34}{\mathrm{S}} $ in groundwater sulfate
表 1 EWQI等级分类
Table 1. Grade classification of EWQI
EWQI 等级 水质描述 EWQI≤25 Ⅰ 优秀 25<EWQI≤50 Ⅱ 良好 50<EWQI≤100 Ⅲ 中等 100<EWQI≤150 Ⅳ 较差 150<EWQI Ⅴ 极差 
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表 2 研究区水化学参数统计表
Table 2. Statistical table of hydrochemical parameters in the study area
样品 项目 pH Ca2+ Mg2+ Na+ K+ ${\mathrm{NO}}_3^{-} $ Cl− ${\mathrm{SO}}_4^{2-} $ ${\mathrm{HCO}}_3^{-} $ F TDS ρB/(mg·L−1) 岩
溶
水最小值 6.59 23.85 2.27 20.61 0.00 0.00 10.45 94.68 83.54 0.00 449.70 最大值 7.66 456.09 123.93 253.73 36.68 80.73 124.50 1558.64 664.25 1.22 2645.86 平均值 7.18 229.00 61.14 70.40 8.78 17.14 29.06 582.07 290.00 0.46 1145.16 变异系数 0.19 0.60 0.62 1.01 1.24 1.52 0.92 0.72 0.41 0.83 0.54 孔
隙
水最小值 6.75 46.36 0.00 27.83 0.00 0.00 20.92 67.12 65.33 0.00 377.58 最大值 9.49 718.63 151.36 183.52 42.68 424.72 172.47 1489.07 640.50 0.65 2595.51 平均值 7.47 214.94 51.13 82.56 5.57 77.32 70.50 430.25 352.70 0.14 1111.23 变异系数 0.64 0.80 0.76 0.51 1.66 1.56 0.69 0.85 0.39 1.59 0.55 裂
隙
水最小值 7.42 19.35 2.11 21.85 0.25 5.05 6.78 60.68 166.07 0.00 252.30 最大值 8.39 114.59 36.50 83.56 5.43 210.19 105.3 245.97 296.95 0.57 770.71 平均值 8.01 65.76 19.87 55.66 3.99 45.43 23.1 119.98 233.76 0.21 451.38 变异系数 0.04 0.41 0.57 0.43 0.40 1.41 31.3 0.47 0.17 0.97 0.37 地
表
水最小值 7.66 40.80 17.20 35.25 3.07 0.00 13.10 132.84 154.41 0.00 431.65 最大值 8.56 225.63 76.49 125.41 8.45 41.10 69.01 820.16 326.64 1.87 1200.15 平均值 8.03 102.14 34.26 65.46 4.56 14.09 31.33 324.72 240.19 0.58 697.31 变异系数 0.04 0.70 0.64 0.44 0.35 0.87 0.57 0.76 0.23 1.00 301.78 注：pH无量纲，其他指标单位均为mg/L，TDS为总溶解性固体，下同
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