Hydrochemical Evolution Processes of Karst Groundwater in Guiyang City: Evidences from Hydrochemistry and 87Sr/86Sr Ratios
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摘要: 岩溶地下水的水化学特征及其水岩作用过程研究对岩溶地下水合理开发利用和污染防治具有重要意义.综合利用水化学分析、主要离子比值、锶含量和87Sr/86Sr比值分析和反向水文地球化学模拟，深入分析了贵阳市地下水和地表水不同季节的水化学特征变化和水文地球化学演化过程.水化学特征分析表明，贵阳市地下水以HCO3·SO4-Ca型和HCO3-Ca·Mg型为主，水化学组成在季节和空间分布上存在一定的规律性变化，地表水与地下水的直接混合对地下水化学组成有一定的影响.锶同位素比值和水文地球化学反向模拟表明，地下水水化学组分主要受岩石风化作用的控制，以方解石和白云石为主的碳酸盐的溶解－沉淀作用以及硫酸盐和岩盐的溶解是控制研究区地下水水化学特征的重要过程，并受上覆孔隙含水层硅酸盐矿物水解的影响.Abstract: Study on hydrochemical characteristics and water-rock interaction is of great significance to ascertain the causes of groundwater pollution and the sustainable use of karst water. Hydrochemical components and types, ion ratios, strontium content, 87Sr/86Sr ratio and inverse hydrogeochemical modelling were employed to identify hydrochemical evolutional processes of karst groundwater in Guiyang City. The results show that the hydrochemical types of groundwater are mainly HCO3·SO4-Ca and HCO3-Ca·Mg, and the hydrochemical compositions of groundwater varied with time and space due to the dissolution/precipitation of different minerals. The mixing of surface water and groundwater has a certain influence on the hydrochemical characteristics of groundwater. Strontium isotope analysis and inverse hydrogeochemical modeling indicate that the hydrochemical characteristics of groundwater are mainly controlled by rock weathering. The dissolution-precipitation of carbonate dominated by calcite and dolomite as well as the dissolution of sulfate and halite are important processes to control the hydrochemical characteristics of groundwater in the study area, and are also affected by the hydrolysis of silicate minerals in the overlying porous aquifer.
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图 1 贵阳市水文地质图及采样点分布
Fig. 1. Hydrogeological map and the sampling location of the study area
图 2 枯水期和丰水期地下水中各组分的平均浓度（a）、枯水期与丰水期不同溶质平均浓度比（b）以及地下水与地表水中不同溶质平均浓度比（c）
Fig. 2. The average concentration of different solutes in groundwater samples during the rainy and dry seasons (a), ratios of the average solute concentration for rainy season to dry seasons (b), and ratios of the average solute concentration for groundwater to surface water samples (c)
图 3 研究区地下水水化学类型分布
Fig. 3. The distribution of groundwater hydrochemical type in the study area
图 4 地下水不同矿物饱和指数与TDS的关系（a）及不同水文地质单元地下水的方解石饱和指数与HCO3-含量的关系（b）
Fig. 4. Relationship between mineral saturation index and TDS content in groundwater (a) and relationship between SIcalcite and HCO3- content in groundwater from different hydrogeological units (b)
图 5 贵阳市地下水和地表水Piper图
Fig. 5. Piper diagram of major ionic compositions of the water samples in Guiyang City
图 6 研究区地下水及地表水87Sr/86Sr与Mg2+/Ca2+关系（a）和Mg2+/Ca2+与Sr2+/Ca2+关系（b）
Mg2+/Ca2+、Sr2+/Ca2+均为摩尔比值
Fig. 6. 87Sr/86Sr vs. Mg2+/Ca2+ (a) and Mg2+/Ca2+ vs. Sr2+/Ca2+ (b) of groundwater and surface water samples in the study area
表 1 地下水TDS与离子含量相关性矩阵
Table 1. Correlation matrices of hydrochemical parameters of groundwater
K+ Na+ Ca2+ Mg2+ Cl- SO42- HCO3- TDS 枯水期
（n=41）K+ 1 Na+ 0.766 1 Ca2+ 0.108 0.277 1 Mg2+ 0.146 0.345 -0.329 1 Cl- 0.570 0.910 0.442 0.347 1 SO42- 0.375 0.635 0.573 0.343 0.791 1 HCO3- 0.153 0.374 0.150 0.651 0.361 0.269 1 TDS 0.382 0.707 0.651 0.415 0.842 0.928 0.547 1 丰水期
（n=34）K+ 1 Na+ 0.650 1 Ca2+ 0.267 0.511 1 Mg2+ 0.227 0.346 -0.174 1 Cl- 0.535 0.958 0.564 0.322 1 SO42- 0.559 0.776 0.580 0.423 0.762 1 HCO3- 0.138 0.267 0.438 0.508 0.283 0.202 1 TDS 0.539 0.832 0.764 0.431 0.847 0.890 0.552 1 
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表 2 研究区地下水及地表水锶含量、87Sr/86Sr及不同来源贡献率
Table 2. Statistical results of Sr2+ concentration and 87Sr/86Sr ratios of groundwater and surface water in the study area and contribution rate of different rock sources
样品 类型 Sr2+(mg/L) 87Sr /86Sr 不同来源贡献率（%） 硅酸盐岩 石灰岩 白云岩 GZ075 碳酸盐岩 1.00 0.707 8 0.0 50.0 50.0 GZ004 0.55 0.708 2 0.0 48.0 52.0 GZ046 0.34 0.708 1 0.0 44.0 56.0 GZ021 0.94 0.707 7 2.0 98.0 0.0 GZ015 0.44 0.709 2 14.0 86.0 0.0 GZ054 0.34 0.708 9 9.0 74.0 17.0 GZ053 0.52 0.708 0 3.0 92.0 5.0 GZ008 0.80 0.710 3 19.0 60.0 21.0 GZ003 碳酸盐岩
夹碎屑岩0.58 0.708 2 0.0 55.0 45.0 GZ001 1.02 0.708 1 0.0 52.0 48.0 GZ047 1.59 0.708 0 0.0 46.0 54.0 GZ044 0.30 0.708 1 0.0 50.0 50.0 GZ043 0.59 0.710 6 22.0 53.0 25.0 GZ052 0.78 0.708 1 0.0 59.0 41.0 GZ055 碎屑岩 0.05 0.710 7 26.0 74.0 0.0 GZ005 地表水 0.63 0.708 0 0.0 72.0 28.0 GZ108 0.49 0.710 3 21.0 65.0 14.0
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表 3 模拟地下水流路径的水样分析统计（mg/L）
Table 3. Hydrochemical data of groundwater samples along the flow path
水样 pH值 Na++K+ Ca2+ Mg2+ Cl- SO42- HCO3- 路径1 GZ044 7.07 8.6 91.8 25.3 13.6 50.6 298.0 GZ044→GZ001 GZ001 7.16 16.9 118.4 32.5 27.2 170.8 355.7 GZ001→GZ003 GZ003 6.69 24.5 123.1 33.3 39.2 203.9 342.9 路径2 GZ042 7.21 16.0 101.0 19.4 17.7 89.4 349.3 GZ042→GZ006 GZ006 6.84 29.2 116.9 25.9 31.8 145.4 334.9
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表 4 反向模拟结果
Table 4. Results of the inverse hydrogeochemical modeling
路径 矿物相 转化量（mol） 化学式 GZ044→GZ001 GZ001→GZ003 路径1 方解石 -5.017×10-4 -3.095×10-4 CaCO3 白云石 3.391×10-4 3.301×10-5 CaMg(CO3)2 石膏 1.120×10-3 3.846×10-4 CaSO4·2H2O 岩盐 3.697×10-4 2.961×10-4 NaCl CO2 (g) 1.169×10-3 3.345×10-5 CO2 路径2 方解石 -9.618×10-4 CaCO3 白云石 2.677×10-4 CaMg(CO3)2 石膏 6.218×10-4 CaSO4·2H2O 岩盐 3.969×10-4 NaCl CO2 (g) 1.904×10-4 CO2 CaX2 4.378×10-4 CaX2 NaX -8.756×10-4 NaX
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