Hydrogeochemistry Characteristics and Formation Mechanismof Shallow Groundwater in Yongcheng City, Henan Province
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摘要: 地下水是河南省永城市重要的供水水源，浅层地下水水质污染严重制约了该市经济发展和居民生活质量的提高.在实地调查采样分析的基础上，运用水化学图解法、数理统计法、地球化学模拟法等方法综合分析了永城市浅层地下水的水化学特征和形成机制，探讨了该市浅层地下水污染来源和主要影响因素.结果表明：随含水介质和人类活动影响强度的变化，浅层地下水中K+、Ca2+、NO3-、Cl-、SO42-的浓度和COD（chemical oxygen demand）随深度增加而减少，而Na+、F-、Mg2+、HCO3-的浓度和TDS（total dissolved solids）随深度增加而上升.在煤矿区及煤化工区浅层地下水中SO42-浓度大于250 mg/L，远远高于其他区域的SO42-浓度，而在农业区浅层地下水中NO3-浓度大于30 mg/L，远远高于其他区域的NO3-浓度.综合分析表明：煤矿及其化工业废水和生活污水排放、过量使用化肥农药是永城市浅层地下水污染的主要因素.Abstract: Groundwater is one of the most important water supply resources in Yongcheng City, but the pollution of shallow groundwater seriously restricts the economic development and the improvement of living standards in the city. On the basis of groundwater investigation and sampling, hydrogeochemical diagram method and multivariate statistics method and geochemical simulation method were comprehensively used to analyze the hydrochemical characteristics and formation mechanism, as well as the pollution source and the main affecting factors. With the change of aquifer medium and the intensity of human activities, the concentrations of K+, Ca2+, NO3-, Cl-, SO42- and COD (chemical oxygen demand) gradually decreased, while the concentrations of Na+, F-, Mg2+, HCO3- and TDS (total dissolved solids) gradually increased with the increase of depth, the former comes from human activities, while the latter comes from the original sedimentary environment. The concentration of SO42- in the areas of coal mine and coal chemical industry is higher than 250 mg/L, which is much higher than that in other regions. The concentration of NO3- is higher than 30 mg/L in agricultural areas. Integrated analyses implies that wastewater discharge of coal mine and chemical industry, leakage of household waste leachate and discharge of sewage, excessive application of pesticides and fertilizers are the main factors affecting the water quality of shallow groundwater.
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Key words:
- coal mining city /
- shallow groundwater /
- mathematical statistics /
- geochemical simulation /
- groundwater /
- hydrogeology /
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图 1 研究区浅层地下水水文地质图、地下水流向及采样点位置图
Fig. 1. Contours of water table and sample locations and hydrogeological profile of study area
图 2 浅层地下水三线图及水化学类型分区图
Fig. 2. Piper diagram and hydrochemical type of shallow groundwater
图 4 Na+与Cl-相关性及岩盐饱和指数(SIh)图
Fig. 4. Scatter diagrams of Na+ vs Cl- and (Na+ + Cl-) vs SIh
图 6 [Ca2++Mg2+]/[HCO3-]与[SO42-]/[HCO3-]比值关系图
Fig. 6. Scatter diagram of [Ca2++Mg2+]/[HCO3-] vs.[SO42-]/[HCO3-]
图 7 Ca2+-SO42-与HCO3-、Mg2+与HCO3-相关关系
Fig. 7. Scatter diagrams of Ca2+-SO42- vs. HCO3- and Mg2+ vs. HCO3-
表 1 浅层地下水水化学组分
Table 1. Statistical summary of hydrochemical parameters of shallow groundwater samples
pH K+ Na+ Ca2+ Mg2+ Cl- SO42- HCO3- F- NO3- TDS COD 总硬度 mg/L 浅井水 极小值 7.2 0.28 8.55 25.25 10.69 3.54 24.02 64.18 0.3 0.02 192.24 0.21 138.5 极大值 8.3 49.94 283.6 206.81 105.58 207.74 453.4 655.96 2.6 89.25 1177.9 3.67 893.5 均值 7.538 4.132 77.68 88.628 54.634 54.38 111.955 466.497 1.093 25.585 680.107 0.764 445.92 标准差 0.259 10.011 60.365 44.153 22.034 48.957 90.082 162.078 0.594 32.023 237.28 0.862 148.254 变异系数 0.034 2.423 0.777 0.498 0.403 0.900 0.805 0.347 0.543 1.252 0.349 1.128 0.332 深井水 极小值 7.3 0.43 51.83 32.06 32.93 15.95 47.07 386.87 0.7 0.1 472.57 0.07 277 极大值 8.15 4.92 262.04 108.42 89.67 135.77 271.85 769.46 2.48 103.5 1235.26 0.48 577.86 均值 7.555 1.348 132.364 65.591 55.452 50.799 109.268 576.09 1.508 19.399 739.428 0.193 405.386 标准差 0.278 1.285 73.841 24.036 15.485 36.338 67.94 120.09 0.684 30.798 227.958 0.123 93.598 变异系数 0.037 0.953 0.558 0.366 0.279 0.715 0.622 0.208 0.454 1.588 0.308 0.637 0.231 注：1.浅井水样共25个, 深井水样共10个；2.变异系数无量纲. 
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表 2 浅层地下水离子间Pearson相关系数
Table 2. Pearson correlation coefficient matrix of shallow groundwater samples
K+ Na+ Ca2+ Mg2+ Cl- SO42- HCO3- NO3- F- 总硬度 COD TDS pH H2SiO3 浅
井
水K+ 1 0.764** -0.32 0.044 0.140 0.203 0.409* -0.086 -0.175 -0.211 0.071 0.417* 0.693** 0.495* Na+ 1 -0.240 0.369 0.375 0.365 0.570** 0.212 -0.038 0.048 0.058 0.709** 0.621** 0.465** Ca2+ 1 0.081 0.530** 0.489* 0.023 0.043 -0.437* 0.793** -0.215 0.431* -0.602** -0.141 Mg2+ 1 0.614** 0.493* 0.361 0.107 0.397* 0.672** 0.118 0.660** 0.134 -0.121 Cl- 1 0.652** 0.215 0.312 -0.102 0.769** 0.121 0.801** -0.041 -0.004 SO42- 1 0.165 -0.133 0.042 0.664** -0.111 0.752** 0.163 -0.093 HCO3- 1 0.106 -0.076 0.238 -0.011 0.552** 0.210 0.286 NO3- 1 -0.106 0.097 0.376 0.210 -0.004 0.005 F- 1 -0.082 -0.177 -0.131 -0.058 -0.326 总硬度 1 -0.087 0.724** -0.365 -0.179 COD 1 -0.002 -0.013 -0.010 TDS 1 0.186 0.229 PH 1 0.311 H2SiO3 1 深
井
水K+ 1 0.660 -0.019 0.822** 0.797** 0.842** 0.649* -0.210 -0.142 0.525 -0.074 0.797** -0.135 0.453 Na+ 1 -0.511 0.800** 0.669* 0.882** 0.911** -0.116 0.339 0.042 0.595 0.924** -0.179 -0.067 Ca2+ 1 -0.295 0.215 -0.150 0.478 0.218 0.867** 0.611 -0.316 -0.186 -0.326 0.425 Mg2+ 1 0.661* 0.880** 0.852** -0.078 0.174 0.459 0.276 0.885** -0.273 0.326 Cl- 1 0.903** 0.516 -0.024 -0.193 0.481 0.252 0.853** -0.253 0.402 SO42- 1 0.798** -0.114 0.097 0.399 0.389 0.974** -0.293 0.293 HCO3- 1 -0.255 0.206 0.204 0.517 0.857** -0.356 0.151 NO3- 1 -0.057 0.034 0.154 0.008 -0.150 -0.019 F- 1 -0.641* 0.257 0.073 0.394 -0.567 总硬度 1 -0.084 0.369 -0.542 0.733* COD 1 0.492 -0.384 0.096 TDS 1 -0.355 0.286 pH 1 -0.419 H2SiO3 1 注：*0.05水平上(双侧)显著相关；**0.01水平上(双侧)显著相关；单位：mg/L.
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表 3 浅井水旋转成分载荷矩阵
Table 3. Matrix of rotated factor loadings of groundwater in shallow wells
成分 F1 F2 F3 F4 K+ -0.004 0.912 -0.023 -0.050 Na+ -0.299 0.882 -0.108 0.148 Ca2+ 0.674 -0.381 -0.571 -0.165 Mg2+ 0.734 0.106 0.499 0.179 Cl- 0.865 0.114 -0.062 0.242 HCO3- 0.336 0.557 -0.045 0.078 SO42- 0.806 0.173 -0.086 -0.252 F- -0.008 -0.121 0.928 -0.136 NO3- 0.128 0.017 -0.066 0.820 H2SiO3 -0.139 0.683 -0.390 -0.023 总硬度 0.950 -0.218 -0.119 -0.013 TDS 0.864 0.476 -0.069 0.081 PH -0.141 0.749 0.501 -0.053 COD -0.175 0.031 -0.001 0.810 贡献率(%) 30.73 24.55 13.49 68.77 累积贡献率(%) 30.73 55.28 11.21 79.98
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表 4 深井水旋转成分载荷矩阵
Table 4. Matrix of rotated factor loadings of groundwater in deep wells
成分 F1 F2 F3 K+ 0.853 0.312 -0.350 Na+ 0.930 -0.277 0.166 Ca2+ -0.309 0.891 0.038 Mg2+ 0.931 0.051 -0.010 Cl- 0.797 0.365 -0.010 HCO3- 0.902 -0.166 0.147 SO42- 0.970 0.099 0.036 F- 0.159 -0.901 -0.006 NO3- -0.198 0.117 0.596 H2SiO3 0.294 0.731 0.077 总硬度 0.345 0.855 0.022 TDS 0.966 0.072 0.184 PH -0.259 -0.486 -0.625 COD 0.402 -0.265 0.773 贡献率(%) 45.53 25.31 11.13 累积贡献率(%) 45.53 70.84 81.97
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