Hydrogeochemical characteristics and genesis of Jiusuo geothermal field in southwestern Hainan, China
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摘要:
海南岛地热资源丰富，以往的地热勘查大多停留在生产层面，而对地热水化学成分的来源、水-岩作用、多方法评价热储温度和地热田成因机制等未深入研究。基于前人资料的深入分析，可以加深对成因机制的认识，为地热田开发提供参考。利用离子的比值及相关性、Piper图、F−浓度分布图、硅-焓图解与SiO2混合模型和硅-焓方程法，探讨了九所地热田热水化学组分的来源、阳离子交换、F−成因、热储温度和循环深度，提出了成因概念模型。结果显示：热水化学类型为SO4·HCO3-Na 型；SO42−主要源于安山岩、流纹岩区硫化物氧化；含F矿物溶解、离子交换是F−浓度的控制因素；热储温度99～169℃，冷水混合比例80%～93%，冷、热水混合前蒸汽损失的质量分数约10%；循环深度1.8～3.8 km。概念模型揭示：热水沿构造运移，从花岗岩区流向安山岩、流纹岩区，同时汲取热能，发生矿物溶滤和离子交换，导致F−、SO42−等组分浓度改变，引起水化学类型演化，在水力差和浮力差双重驱动下上升，于地下浅部与孔隙冷水混合存储于沉积盖层之下形成地热田。关于琼西南地热田的热源是否存在幔源热的问题目前没有充分证据，需进一步深入研究。
Abstract:Hainan Island harbors abundant geothermal resources. However, previous geothermal explorations have focused primarily on production, overlooking critical research areas such as the origins of geothermal water chemistry, water-rock interactions, methods for evaluating thermal reservoir temperatures, and mechanisms of geothermal field formation.
Objective This study leverages existing exploration data to deepen our understanding of the genetic mechanism of geothermal fields and to offer valuable insights for their development.
Methods We employed a range of analytical techniques, including major ion ratios and correlations, Piper diagrams, fluoride concentration maps, silicon-enthalpy and SiO2 mixing model graphs, silicon-enthalpy equations, and water
δ D andδ 18O values. Focusing on the geothermal water of Jiusuo, we investigated the sources of chemical components, the cation exchange processes, the origin of F− events, the most likely reservoir temperatures, and the circulation depths of geothermal water, ultimately proposing a conceptual model explaining the genesis of the field.Results The results indicate that the hydrochemistry of geothermal water is mainly characterized by SO4·HCO3-Na type, with Ca2+ and Mg2+ replacing Na+ and K+ in the rock. The primary source of SO42− is the sulfide oxidation of andesite and rhyolite. The fluoride concentration is regulated by the dissolution of minerals such as mica, amphibole, and fluorite, along with ion exchange and alkaline environments. The chemical composition is predominantly shaped by silicate mineral dissolution, ion exchange, and the degree of development of geological strata and structures. Most likely, when mixed with cold groundwater, the temperature range of geothermal water in this area falls to 99℃-169℃, with cold groundwater contributing 80% to 93% of the mix and approximately 10% steam loss prior to mixing. The circulation depth of geothermal water ranges from 1.8 to 3.8 km.
Conclusion The proposed conceptual model suggests that the geothermal water in the Jiusuo geothermal field originates from rainfall recharge and flows under the control of the Furongtian-Wangxia structural belt, Ledong-Xichang structural belt, and Jiusuo-Lingshui deep large fault belt. The water flows from the granite areas to the andesite and rhyolite areas, where it absorbs heat from both radioactive decay in granite and potential minor mantle-derived thermal energy. This process leads to silicate mineral dissolution, cation exchange, and sulfide oxidation, resulting in increased concentrations of fluoride ions (F−), sulfate ions (SO42−), and other chemical components in water. These processes cause an evolution in water chemical types. Owing to the increase in temperature, the density and viscosity of geothermal water decrease, and the pressure increases, generating buoyancy. Driven by both the hydraulic gradient and buoyancy gradient, geothermal water ascends along the Jiusuo-Lingshui deep large fault belt and rock fractures in the subsurface. It then mixes with cold groundwater near the surface before being embedded in the Quaternary and Tertiary sedimentary layers, ultimately forming a geothermal field. While mantle-derived thermal energy's presence in the deep region of geothermal fields in southwestern Hainan remains unconfirmed, it presents an intriguing scientific question meriting further investigation.
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图 1 九所地热田取样位置和区域地质概况
Figure 1. Sampling location and regional geological overview of the Jiusuo geothermal fields
图 5 F−/Cl−、c（Na+）与ρ（F−）关系图
Figure 5. Plots of F−/Cl− versus F− concentration, and Na+ concentration versus F− concentration
图 6 硅-焓图解与二氧化硅混合模型确定热储温度（D1～D5为点编号）
Figure 6. Geothermal reservoir temperature determined by silicon-enthalpy diagram with silica mixing model
图 7 硅-焓方程计算出的热储温度和冷水混入比例
Figure 7. Geothermal reservoir temperature and cold water mixing ratios calculated by silicon-enthalpy equations
图 8 δD−δ18O关系图（a）及钻孔深度和温度关系图（b）
GMWL. 全球雨水线；LMWL2. 海南岛雨水线；LMWL1. 雷州半岛雨水线
Figure 8. δD−δ18O relationship of gethermal water (a) and relationship between depth and temperature of borehole (b)
图 9 九所地热系统概念模型
剖面线A-B位置见图2b；ZK为钻孔；N+Q为新近系和第四系沉积地层；Kγ为白垩纪花岗岩；F1为九所-陵水断裂带；F2为石门山断裂带；F3为芙蓉田-王下构造带；F5为乐东-西昌断裂带；样点大小表示ρ（F−）大小。
Figure 9. A conceptual model of the Jiusuo geothermal system
表 1 九所及邻近地热田水化学参数表
Table 1. Hydrochemical parameters of geothermal fields in Jiusuo and neighboring areas
地热田 样品编号 K+ Na+ Ca2+ Mg2+ Cl− SO42− CO32− HCO3− NO3− F− ρB/（mg·L−1） 千家 Q-ZK1 3.2 40.1 57.3 11.8 19.4 8.9 0.0 290.0 4.8 0.8 福报 F-ZK2 2.9 25.4 75.4 4.0 15.9 7.3 0.0 296.0 <0.2 0.3 F-ZK4 1.1 28.8 63.4 12.1 28.7 29.3 16.0 207.0 5.0 0.4 崖城 Y-8 3.9 135.0 8.9 0.5 30.2 123.0 16.0 133.0 1.6 11.0 Y-1 3.4 136.0 7.4 0.3 27.2 121.0 11.0 138.0 1.4 11.0 Y-7 3.5 139.0 8.6 0.4 28.7 125.0 16.0 127.0 0.3 11.0 Y-ZK1 3.6 140.0 7.3 0.4 28.2 118.0 15.0 128.0 0.6 18.0 Y-ZK2 6.1 54.2 42.1 4.4 25.1 43.4 9.8 184.0 2.1 4.6 Y-ZK3 5.0 135.0 11.9 0.9 29.5 123.0 20.0 139.0 <0.2 16.0 九所 J-B03 2.9 79.1 9.8 0.9 26.6 6.2 15.0 173.0 2.1 0.7 J-B05 1.4 82.4 5.9 0.6 17.2 <0.2 5.0 198.0 2.7 0.7 J-A04 1.7 134.0 9.3 0.4 26.2 137.0 9.4 110.0 <0.2 12.0 J-ZK1a 1.8 129.0 9.6 0.5 24.6 132.0 14.0 129.0 1.4 8.3 J-ZK1b 2.0 134.0 9.0 0.4 26.2 141.0 19.0 105.0 6.3 12.0 J-ZK2a 2.5 104.0 9.5 0.9 19.7 73.2 14.0 172.0 8.6 0.9 J-ZK2b 2.0 137.0 8.4 0.6 26.2 130.0 19.0 110.0 4.4 12.0 J-ZK2c 3.0 154.0 9.0 0.5 32.8 166.0 14.0 110.0 3.3 19.0 J-ZK3a 2.9 127.0 13.0 0.7 27.9 157.0 9.4 101.0 5.0 9.0 J-ZK3b 2.1 144.0 10.5 0.4 29.5 157.0 14.0 101.0 3.3 19.0 J-ZK3c 3.4 150.0 7.7 0.4 32.8 167.0 14.0 96.7 5.4 19.0 
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地热田 样品编号 温度/°C pH TDS SiO2 修正SiO2 δ18OV-SMOW/‰ δDV-SMOW/‰ 水化学类型 ρB/（mg·L−1） 千家 Q-ZK1 42 8.21 354 — — — — HCO3-Ca·Na 福报[17] F-ZK2 47 7.56 502 — — — — HCO3-Ca F-ZK4 35 8.39 440 — — — — HCO3-Ca 崖城[7] Y-8 55 7.00 466 — — — — SO4·HCO3-Na Y-1 50 8.10 457 — — — — SO4·HCO3-Na Y-7 57 8.09 465 — — — — SO4·HCO3-Na Y-ZK1 58 8.46 470 — — — — SO4·HCO3-Na Y-ZK2 34 8.35 315 — — — — SO4·HCO3-Na Y-ZK3 46 8.14 477 — — — — SO4·HCO3-Na 九所 J-B03 35 8.43 252 21.6 — — — HCO3-Na J-B05 36 8.96 234 18.8 — — — HCO3-Na J-A04 44 8.72 420 34.2 29.7 −7.84 −53.5 SO4·HCO3-Na J-ZK1a 45 8.72 415 27.5 23.6 −7.84 −52.8 SO4·HCO3-Na J-ZK1b 45 8.81 444 35.7 29.9 −7.86 −53.2 SO4·HCO3-Na J-ZK2a 39 8.85 359 30.6 — −7.50 −51.6 HCO3·SO4-Na J-ZK2b 40 8.85 422 24.3 20.5 −7.94 −53.0 SO4·HCO3-Na J-ZK2c 41 8.73 507 49.3 43.1 −8.09 −52.8 SO4·HCO3-Na J-ZK3a 42 8.68 443 29.4 — −7.94 −53.9 SO4·HCO3-Na J-ZK3b 42 8.71 476 45.4 39.7 −8.10 −53.3 SO4·HCO3-Na J-ZK3c 38 8.75 509 57.5 50.5 −8.11 −52.2 SO4·HCO3-Na J-A06（望楼河） 28 7.01 131 45.2 — −3.71 −25.8 — 雨水 — — — — — −6.33 −38.9 — 注：J-ZK1a、J-ZK1b，J-ZK2a、J-ZK2b、J-ZK2c，J-ZK2c、J-ZK3a、J-ZK3b、J-ZK3c分别为钻孔ZK1、ZK2和ZK3不同深度水样
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表 2 硅-焓图解与二氧化硅混合模型绘图数据
Table 2. Mapping data for silicon-enthalpy diagram with silica mixing model
ρ（SiO2）/
（mg·L−1）[37]焓/
（J·g−1）[37]T/°C 100°C下蒸气足量
损失的焓/（J·g−1）点编号 修正后焓/
（J·g−1）修正后ρ（SiO2）/
（mg·L−1）13.5 209.3 56.3 234.4 A 115.0 37.9 26.6 314.0 78.8 330.7 D1 419.0 127.5 48.0 419.1 100.9 423.3 D2 607.0 127.5 80.0 525.0 122.5 514.4 D3 607.0 115.0 125.0 632.2 143.5 604.3 D4 419.0 68.0 185.0 741.1 163.9 693.0 D5 485.0 68.0 265.0 852.4 184.4 780.9 — — — 365.0 966.7 204.3 870.4 — — — 486.0 1085.2 223.7 962.0 — — — 614.0 1210.0 240.7 1042.0 — — —
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表 3 不同方法计算的热储温度
Table 3. Temperature of geothermal reservoir calculated by different methods
样品编号 硅-焓方程法热储
温度/℃冷水混入比例
（硅-焓方程）硅-焓图解与SiO2混合
模型热储温度/℃冷水混入比例
（混合模型）最可能的热储
温度均值/℃冷水混入
比例均值J-ZK2c 123 0.87 116 0.85 120 0.86 J-ZK3b 99 0.80 98 0.79 99 0.80 J-ZK3c 194 0.94 144 0.91 169 0.93 均值 139 0.87 119 0.85 129 0.86
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