Source Analysis of Sodium of Low-Salinity High-Sodium Geothermal Water in Huangshadong Geothermal Field from East Guangdong
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摘要: 高温地热系统中地热水中Na+含量一般超过300 mg/L，盐度也较大（TDS > 1000 mg/L）.而在中低温地热系统中，低盐度地热水的Na+含量一般小于160 mg/L.但在广东黄沙洞中低温地热系统出露的地热水中Na+高达325.4 mg/L，TDS小于650 mg/L.经典的水文地球化学作用（矿物溶解、离子交换等）很难解释其成因.样品水化学结果表明，地热水水化学类型均为HCO3-Na型，钠含量高（平均值为240.06 mg/L）.氢氧同位素结果表明地热水与浅层地下水均具有相同的大气来源，都是瑶坑山区大气降水补给.水化学地温计和多组分矿物平衡（MME）评估的热储温度为100~130 ℃，地热水循环深度最大为2.43 km.Cl-作为混合比计算指标揭示浅层地下水混入地热水的比例为51%~72%，深部地热水中Na+实际含量应该高达685.2 mg/L.水-岩相互作用模拟结果表明，矿物溶解和离子交换对地热水中Na+富集的贡献较小，也揭示出地热水中存在Na+的额外来源.花岗岩流体包裹体微小但广泛存在于结晶矿物颗粒之间，其中Na+含量平均值为11 758.9 mg/L.在地热水加热情况下，断裂和花岗岩裂隙网络层面及附近的流体包裹体膨胀破裂，流体混入到地热水中，为地热水提供了平均83%的Na+.因此，花岗岩流体包裹体可能是中低温地热系统低盐高钠地热水中Na+的主要来源.Abstract: The Na+ content in the geothermal water in the high-temperature geothermal system generally exceeds 300 mg/L, and the salinity is also large (TDS > 1 000 mg/L). In the medium- and low-temperature geothermal system, the Na+ content of low-salinity geothermal water is generally less than 160 mg/L. However, geothermal water with Na+ as high as 325.4 mg/L and TDS less than 650 mg/L was found in the Huangshadong medium-low temperature geothermal system in Guangdong. It is difficult to explain their formation with typical hydrogeochemical reactions (mineral dissolution, ion exchange, etc.). The water chemistry results show that the chemical types of geothermal water are all HCO3-Na type, with high sodium content (average 240.06 mg/L). The results of hydrogen and oxygen isotopes show that both geothermal water and shallow groundwater have the same atmospheric source which is in the Yaokeng mountainous area. According to the hydrochemical geothermometer and the multicomponent mineral equilibrium (MME), the thermal storage temperature is estimated to be 100-130 ℃ and the maximum circulation depth is 2.43 km. Cl- is used as a mixing ratio calculation indicator to reveal that the proportion of shallow groundwater mixed into geothermal water is 51%-72%, The actual content of Na+ in deep geothermal water should be as high as 685.2 mg/L. The simulation results of water-rock interaction indicate that mineral dissolution and ion exchange make a minor contribution to Na+ enrichment in geothermal water, and also reveal the existence of additional sources of Na+ in geothermal water. Granite fluid inclusions are tiny but widespread among crystalline mineral grains, and its average Na+ content is 11 758.9 mg/L. In the case of geothermal heating, the fluid inclusions at and near the fracture and granite fissure network expand and rupture, and the fluid is mixed into the geothermal water, providing average of 83% of Na+ for the geothermal water. Therefore, granite fluid inclusions may be the main source of Na+ for the low-salinity and high-sodium geothermal water in medium-low temperature geothermal system.
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图 1 广东黄沙洞地热田水文地质简图及采样位置
Fig. 1. The simplified hydrogeological map and sampling location in Huangshadong geothermal field, Guangdong
图 2 黄沙洞地下水piper三线图
Fig. 2. Piper diagrams of thermal groundwater from Huangshadong geothermal field
图 3 广东黄沙洞地热田地热水和常温地下水氢氧同位素关系
Fig. 3. Plot of δD vs. δ18O compositions for thermal groundwater and non-thermal groundwater sampled from Huangshadong geothermal field, Guangdong
图 4 热井水(ZK8、ZK4、ZK1、ZK2和ZK3)的多种矿物的饱和指数(SI)与温度关系
Fig. 4. The diagrams of saturation index (SI) vs. temperature of various minerals in thermal well water (ZK8, ZK4, ZK1, ZK2 and ZK3)
图 5 地热水出露温度下各种矿物饱和指数(SI)
Fig. 5. Saturation index (SI) of various minerals at measured temperature
图 6 热井水(ZK8、ZK4、ZK1、ZK2和ZK3)校正后的多种矿物的饱和指数(SI)与温度关系
Fig. 6. The diagrams of saturation index (SI) vs. temperature of various minerals after correction in thermal well water (ZK8, ZK4, ZK1, ZK2 and ZK3)
图 7 黄沙洞地热田中地下水的Na-K-Mg三角图
Fig. 7. The Na-K-Mg triangular diagram for the groundwater from Huangshadong geothermal field
图 8 研究区地下水离子毫克当量比值图
Fig. 8. Diagram of ionic milligram equivalent ratio of groundwater in the study area
图 9 研究区地下水氯碱指数(CAI)图
Fig. 9. The chloro-alkaline indices (CAI) of groundwater in the study area
图 10 广东黄沙洞地热田低盐高钠地热水成因概念模型
Fig. 10. Conceptual model of formation of low-salinity and high-sodium geothermal water in Huangshadong geothermal field, Guangdong
表 1 广东黄沙洞地热田样品水化学和同位素组成(水化学组分单位：mg/L)
Table 1. Hydrochemical and stable isotopic characteristics of the sampled waters from Huangshadong geothermal field in Guangdong (mg/L)
样品编号 类型 井深(m) 温度(℃) pH TDS HCO3‒ F‒ Cl‒ SO42‒ K+ Na+ Ca2+ Mg2+ SiO2 Li Al B Sr δD
(‰)δ18O
(‰)ZK8 热井水 591.5 89 7.54 638.6 631.4 15.585 57.240 112.893 26.090 325.40 12.41 0.403 142.000 1.215 0.066 0.600 0.256 ‒44.1 ‒6.8 ZK4 热井水 380 52 7.16 503.4 596.5 6.222 60.027 48.722 18.780 209.20 44.52 3.899 56.432 0.878 0.027 0.439 0.407 ‒40.8 ‒6.4 ZK1 热井水 100 58 7.80 301.1 285.6 15.244 14.429 36.006 7.207 131.80 12.41 0.260 95.173 0.255 0.041 0.073 0.301 ‒46.1 ‒7.2 ZK2 热井水 360 50 7.12 608.1 682.2 8.506 41.330 77.908 22.86 273.60 39.38 1.966 74.893 1.094 0.089 0.540 0.393 ‒44.2 ‒7.1 ZK3 热井水 310 47 7.69 614.6 666.3 9.084 34.621 69.798 21.950 260.30 35.86 1.919 65.481 1.060 0.015 0.535 0.420 ‒43.3 ‒6.9 泉10 泉水 22 5.64 17.2 25.4 0.066 2.942 3.983 0.302 0.69 1.61 0.926 10.538 ‒ 0.022 0.007 0.004 ‒43.9 ‒7.2 泉3 泉水 23 5.29 32.0 38.1 0.099 9.399 3.469 3.653 5.30 6.07 0.458 12.016 ‒ 0.107 0.007 0.017 ‒43.6 ‒7.4 泉2 泉水 22.5 6.11 54.3 50.8 0.218 8.757 5.953 2.230 5.53 15.00 1.042 8.617 ‒ 0.053 0.012 0.027 ‒40.5 ‒5.8 泉1 泉水 23 5.37 24.7 6.3 0.131 3.681 4.048 1.141 2.41 1.06 0.129 8.311 ‒ 0.086 0.006 0.003 ‒46.2 ‒7.5 CK2 井水 10.2 25 6.64 95.3 120.6 1.557 6.514 6.831 4.196 21.01 13.45 5.184 43.939 0.062 0.063 0.024 0.079 ‒35.2 ‒5.1 CK22 井水 9.6 26 6.58 134.6 88.8 0.616 4.512 5.162 2.042 8.39 16.19 6.400 36.195 ‒ 0.020 0.005 0.082 ‒41.3 ‒6.7 CK23 井水 11 26 7.73 128.4 158.6 0.910 5.052 13.527 1.909 3.81 51.29 3.209 21.018 ‒ 0.027 0.007 0.077 ‒46.0 ‒6.8 
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表 2 广东黄沙洞地热田地热水热储温度评估
Table 2. Calculated temperatures using geochemical geothermometers and multicomponent mineral equilibrium method
样品编号 测量温度
(℃)玉髓地温计 校正SiO2 Na-K- Ca-Mg Na-
KK-
MgNa-
K-Ca多矿物组分平衡法 循环深度(km) ZK8 89 130.1 161.3 149.4 186.7 136.2 184.7 130 2.43 ZK4 52 78.9 108.6 132.3 198.1 93.0 171.4 100 1.75 ZK1 58 106.2 136.1 119.9 151.9 103.8 149.8 128 2.39 ZK2 50 93.2 122.9 136.2 190.8 107.8 173.4 110 2.27 ZK3 47 86.3 115.9 136.3 191.7 107.0 173.8 105 1.87
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表 3 广东黄沙洞地热水中矿物溶解化学反应方程式
Table 3. Chemical reaction equation of mineral dissolution in thermal groundwater of Huangshadong geothermal field, Guangdong
矿物名称 溶解反应方程式 角闪石 $ 2\mathrm{N}\mathrm{a}\mathrm{C}{\mathrm{a}}_{2}\mathrm{F}{\mathrm{e}}_{5}\left[\mathrm{S}{\mathrm{i}}_{7}\mathrm{A}\mathrm{l}{\mathrm{O}}_{22}\right]{\left(\mathrm{O}\mathrm{H}\right)}_{2}+3\mathrm{C}{\mathrm{O}}_{2}+39{\mathrm{H}}_{2}\mathrm{O}=\mathrm{A}{\mathrm{l}}_{2}\mathrm{S}\mathrm{i}{\mathrm{O}}_{5}{\left(\mathrm{O}\mathrm{H}\right)}_{4}+30\mathrm{H}\mathrm{C}{{\mathrm{O}}_{3}}^{-}+2\mathrm{N}{\mathrm{a}}^{+}+4\mathrm{C}{\mathrm{a}}^{2+}+10\mathrm{F}{\mathrm{e}}^{2+}+12{\mathrm{H}}_{4}\mathrm{S}\mathrm{i}{\mathrm{O}}_{4} $ 钾长石 $ 2\mathrm{K}\mathrm{A}\mathrm{l}\mathrm{S}{\mathrm{i}}_{3}{\mathrm{O}}_{8}+2{\mathrm{H}}_{2}\mathrm{C}{\mathrm{O}}_{3}+9{\mathrm{H}}_{2}\mathrm{O}=2{\mathrm{K}}^{+}+5{\mathrm{H}}_{2}\mathrm{S}\mathrm{i}{\mathrm{O}}_{4}+2\mathrm{H}\mathrm{C}{{\mathrm{O}}_{3}}^{-}+\mathrm{A}{\mathrm{l}}_{2}\mathrm{S}\mathrm{i}\mathrm{O}{}_{5}({\mathrm{O}\mathrm{H})}_{4}\left(\mathrm{高}\mathrm{岭}\mathrm{石}\right) $ 岩盐矿物 $ \mathrm{N}\mathrm{a}\mathrm{C}\mathrm{l}=\mathrm{N}{\mathrm{a}}^{+}+\mathrm{C}{\mathrm{l}}^{-} $ 方解石 $ \mathrm{C}\mathrm{a}\mathrm{C}{\mathrm{O}}_{3}+{\mathrm{H}}_{2}\mathrm{O}=\mathrm{C}{\mathrm{a}}^{2+}+\mathrm{H}\mathrm{C}{{\mathrm{O}}_{3}}^{-}+\mathrm{O}{\mathrm{H}}^{-} $ 白云石 $ \mathrm{C}\mathrm{a}\mathrm{M}\mathrm{g}(\mathrm{C}{\mathrm{O}}_{3}{)}_{2}+2{\mathrm{H}}_{2}\mathrm{O}=\mathrm{C}{\mathrm{a}}^{2+}+\mathrm{M}{\mathrm{g}}^{2+}+2\mathrm{H}\mathrm{C}{{\mathrm{O}}_{3}}^{-}+2\mathrm{O}{\mathrm{H}}^{-} $ 石膏 $ \mathrm{C}\mathrm{a}\mathrm{S}{\mathrm{O}}_{4}\cdot 2{\mathrm{H}}_{2}\mathrm{O}=\mathrm{C}{\mathrm{a}}^{2+}+\mathrm{S}{{\mathrm{O}}_{4}}^{2-}+2{\mathrm{H}}_{2}\mathrm{O} $
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表 4 黄沙洞地热田中模拟的地热水组分(mg/L)
Table 4. The water chemical composition (mg/L) of simulated geothermal water from Huangshadong geothermal field
样品 HCO3‒ F‒ Cl‒ SO42‒ K+ Na+ Ca2+ Mg2+ SiO2 ZK8 379.91 5.45 111.01 74.73 5.03 71.16 45.16 0.83 135.42 ZK4 571.45 6.32 151.76 72.69 4.01 96.81 89.72 1.81 61.68 ZK1 125.17 5.95 28.90 65.46 4.70 17.91 63.32 1.14 96.18 ZK2 152.74 5.97 80.30 94.41 4.29 51.01 83.52 1.60 78.60 ZK3 175.25 6.19 66.14 70.55 4.15 41.91 80.32 1.57 70.02
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表 5 华南黄沙洞地热田中不同地下水的钠含量(mg/L)及混合比
Table 5. The sodium content (mg/L) in different groundwaters and mixing ratio in geothemal water from Huangshadong geothermal field, South China
样品 混合比(Cl‒)
(%)混合比(Na+)
(%)矿物溶解平衡后地热水的Na+ 真实深部地热水的Na+ 矿物溶解平衡后地热水的Cl‒ 真实深部地热水的Cl‒ ZK8 53 ‒361 71.2 685.2 111.0 111.0 ZK4 64 ‒123 96.8 578.7 151.8 152.9 ZK1 72 ‒920 17.9 454.6 28.9 41.8 ZK2 51 ‒458 51.0 551.3 80.3 77.4 ZK3 53 ‒1045 41.9 546.3 66.1 63.8
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表 6 地热水离子(mg/L)交换作用结果
Table 6. The ion (mg/L) exchange results of geothermal water
样品编号 混合后的地热水的Ca2+(热井水) 矿物溶解平衡后地热水的Ca2+ 混合前的地热水的Ca2+ 离子交换作用的Ca2+含量 离子交换作用的Na+含量 ZK8 12.41 45.16 18.15 27.01 54.02 ZK4 44.52 89.72 84.00 5.72 11.44 ZK1 12.41 63.32 23.42 39.90 79.81 ZK2 39.38 83.52 74.30 9.22 18.44 ZK3 35.86 80.32 67.66 12.66 25.32
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表 7 石英矿物中单个流体包裹体的化学成分(10‒6)
Table 7. Chemical compositions (10‒6) of individual fluid inclusion trapped by quartz
Spot Li7 Na23 Mg24 Al27 K39 Sc45 Ti49 Mn55 Fe57 Cu63 Zn66 1 3 993 14 949 < LOD 12 517 < LOD 450.3 < LOD < LOD < LOD 1 192 < LOD 2 376 14 949 < LOD < LOD < LOD 48 < LOD < LOD < LOD 138 < LOD 3 3 330 14 949 < LOD 3 635 < LOD < LOD < LOD < LOD < LOD 1 721.5 < LOD 4 < LOD 11 022 1 243 839 2 678 < LOD < LOD 25 438 122 424 < LOD 1 891 5 9 194 14 949 < LOD < LOD < LOD 2 278.4 < LOD < LOD < LOD 3 344 < LOD 6 16 045 14 949 < LOD < LOD < LOD 2 640.4 < LOD < LOD < LOD 7 541 < LOD 7 2 836 1 562 < LOD < LOD 22 768 540 < LOD < LOD < LOD 1 425 < LOD 8 < LOD 13 958 52.1 < LOD 1 518 3.3 79.2 47 < LOD 6.9 6.7 9 < LOD 6 624 4 400 6 775 < LOD < LOD 4 416 62 549 271 070 < LOD 4 113.3 10 2 001 1 260 < LOD < LOD 23 282 293.2 < LOD < LOD < LOD 933 < LOD 11 < LOD 13 482 < LOD 9 239 2 489 < LOD 67.9 < LOD < LOD < LOD < LOD 12 < LOD 12 184 1 461 2 616 < LOD < LOD 5 180 13 791 114 088 < LOD 2 207.5 13 < LOD 10 423 2 392 2 757 < LOD < LOD 5 025 25 452 167 508 < LOD 2 446.9 14 < LOD 14 519 227 545 < LOD < LOD 218 1 889 12 639 < LOD 267.3 15 < LOD 11 540 1 802 4 107 < LOD < LOD 1 036 15 814 111 855 < LOD 1 745 16 < LOD 13 938 534 3 001 < LOD < LOD 752 6 487 55 285 < LOD 536.6 17 < LOD 14 644 161 262 < LOD < LOD 145.5 1 113 10 948 < LOD 224.1 注：据 Yang et al., 2019 ； < LOD表示低于检测限.
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