Hydrochemical Characteristics and Formation Causes of Karst Water in Jinan Spring Catchment
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摘要: 济南泉域水质逐年变差，查明其污染来源和影响因素，对岩溶水资源开发利用及生态环境保护具有十分重要的意义，而对包含补给径流区的全区岩溶水系统分析尚未见报道.综合运用水化学(Piper三线图、离子比例系数、相关分析)和多元统计(因子分析、聚类分析)方法分析地下水水化学特征，探讨了不同区域水质影响因素及影响强度.因子分析反映了灰岩水岩作用、工业和生活污染、白云岩水岩作用、农牧业和生活污染对水化学组分的影响，贡献率依次为33.1%、28.4%、12.0%和11.8%.分析结果表明：研究区岩溶水水质受水岩作用和人类活动的双重影响；南部补给区、西郊及其以西排泄区水质优良，主要受碳酸盐岩溶解的影响；直接补给径流区部分岩溶水受农牧业和农村生活污染的影响，NO3-含量较高；东郊排泄区、城区及近郊开采区受工业及城镇生活污染的影响，水质较差，少数地段SO42-、NO3-、TDS和总硬度超标.Abstract: Water quality of Jinan spring catchment is getting worse year by year. It is of great significance to find out the pollution sources and influence factors for exploitation of the karst water and ecological environment protection. However, analysis of the whole karst water system including the recharge and runoff area has not been reported yet. Hydrochemical method (piper diagram, ion ratio, correlation analysis) and multivariate statistical method (factor analysis and cluster analysis) were comprehensively used to analyze the hydrochemical characteristics of groundwater, as well as the factors affecting water quality and relevant impact strength in different areas in this study. Factor analysis indicates the effects of water-rock interaction between limestone and groundwater, industrial and domestic pollution, water-rock interaction between dolomite and groundwater, and agriculture, husbandry and domestic pollution. Their contribution rates to groundwater quality are 33.1%, 28.4%, 12.0%, and 11.8%, respectively. Combined with hydrochemical and cluster analyses, the results indicate that groundwater quality in the study area is controlled by both water-rock interaction and anthropogenic activities. Groundwater with high quality in the southern recharge area and western discharge area is mainly affected by the dissolution of carbonate minerals. Some parts of the recharge-runoff area are influenced by agriculture, husbandry and rural domestic pollution with higher content of nitrate in the groundwater. Industrial and urban domestic pollution severely impacts the eastern suburb, urban and suburban exploitation area with poor groundwater quality and excessive levels of SO42-, NO3-, TDS and total hardness in a few sections.
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Key words:
- Jinan spring catchment /
- karst water /
- hydrochemistry /
- multivariate statistics /
- cluster analysis /
- formation cause /
- hydrogeology
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图 3 济南岩溶地下水水化学类型分布
Fig. 3. The spatial distribution of hydrochemical types of karst groundwater in Jinan
图 4 TDS与矿物饱和指数关系
Sic.方解石饱和指数；Sid.白云石饱和指数；Sig.石膏饱和指数；SIh.岩盐饱和指数
Fig. 4. Relationships between TDS and the saturation indexes of minerals
图 5 离子比值关系
图a, b中，mEq/L=mmol/L×原子价
Fig. 5. Relationships between the ratios of the selected ions
图 6 研究区地下水水化学样品聚类树状图
Fig. 6. Cluster dendrogram of groundwater hydrochemical samples in the study area
图 7 水化学样品系统聚类空间分布
Fig. 7. Spatial distribution of the hydrochemical sample clusters from HCA
表 1 济南岩溶水水化学分析结果统计
Table 1. Results of the hydrochemical analysis of karst water in Jinan
参数 单位 极小值 极大值 均值 标准差 变异系数 T ℃ 10.3 17.0 16.6 1.22 0.07 pH / 7.7 8.5 8.1 0.17 0.02 K++Na+ mg/L 3.0 170.6 18.9 24.15 1.28 Ca2+ mg/L 66.3 197.0 105.4 26.54 0.25 Mg2+ mg/L 10.4 36.6 20.5 5.48 0.27 Cl- mg/L 7.6 247.7 35.7 38.12 1.07 SO42- mg/L 30.6 287.5 91.2 43.42 0.48 HCO3- mg/L 144.3 348.3 251.6 41.51 0.17 NO3- mg/L 5.6 100.3 37.8 22.92 0.61 F- mg/L 0.1 0.4 0.2 0.07 0.35 TDS mg/L 270.3 1125 449.9 134.67 0.30 总硬度 mg/L 228.4 607.4 347.7 75.57 0.22 COD mg/L 0.2 1.8 0.6 0.33 0.54 注：变异系数无量纲. 
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表 2 岩溶水各水化学组分间的相关系数
Table 2. Correlation coefficient of hydrochemical composition of karst groundwater
项目 K++Na+ Ca2+ Mg2+ Cl- SO42- HCO3- NO3- F- pH TDS 总硬度 COD K++Na+ 1.00 0.55* 0.28* 0.94* 0.68* 0.31* -0.11 0.14 -0.37* 0.82* 0.57* 0.55* Ca2+ 1.00 0.27* 0.65* 0.69* 0.70* 0.47* 0.11 -0.62* 0.91* 0.96* 0.10 Mg2+ 1.00 0.26 0.44* 0.51* 0.11 0.06 -0.23 0.46* 0.54* 0.05 Cl- 1.00 0.61* 0.35* -0.01 0.14 -0.46* 0.84* 0.65* 0.46* SO42- 1.00 0.30* -0.01 0.06 -0.29* 0.82* 0.74* 0.40* HCO3- 1.00 0.40* -0.01 -0.68* 0.63* 0.77* -0.16 NO3- 1.00 0.35* -0.21 0.31* 0.44* -0.25 F- 1.00 0.10 0.18 0.12 0.11 pH 1.00 -0.55* -0.61* 0.03 TDS 1.00 0.93* 0.31* 总硬度 1.00 0.10 COD 1.00 注：*表示通过α=0.05显著性检验.
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表 3 旋转因子载荷矩阵
Table 3. Matrix of rotated factor loadings
水化学指标 F1 F2 F3 F4 K++Na+ 0.313 0.885* 0.103 -0.007 Ca2+ 0.844* 0.385 0.116 0.217 Mg2+ 0.201 0.111 0.941* 0.021 Cl- 0.438 0.824* 0.030 0.031 SO42- 0.337 0.688* 0.409 0.017 HCO3- 0.832* -0.033 0.367 0.029 NO3- 0.510 -0.292 0.008 0.691* F- -0.120 0.174 0.031 0.885* pH- 0.831* -0.128 0.027 0.180 TDS 0.677* 0.642* 0.283 0.191 总硬度 0.800* 0.371 0.382 0.197 COD -0.238 0.798* -0.029 0.009 贡献率(%) 33.067 28.440 12.007 11.820 累积贡献率(%) 33.067 61.507 73.514 85.334 注：*表示较高的因子载荷.
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表 4 系统聚类水化学参数平均含量
Table 4. Average contents of hydrochemical parameters in the clusters determined from HCA
Cluster n K++Na+ Ca2+ Mg2+ Cl- SO42- HCO3- NO3- F- pH TDS 总硬度 COD 1 16 10.9 86.6 18.9 21.4 65.8 239.3 24.9 0.2 8.1 361.0 294.3 0.4 2 11 14.6 84.9 17.3 22.5 87.6 200.2 23.3 0.3 8.3 366.0 283.2 0.9 3 18 15.4 114.3 20.2 31.7 85.2 268.8 53.0 0.2 8.1 468.8 368.6 0.5 4 9 28.4 135.9 27.1 61.6 130.9 293.5 50.7 0.2 8.0 597.8 451.0 0.6 5 1 170.6 197.0 28.0 247.7 287.5 326.3 12.5 0.2 7.7 1125 607.4 1.8 注：n表示各类所包含的样品数量，各指标(除pH)单位均为mg/L.
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