Tungsten Anomaly of the High-Temperature Hot Springs in the Daggyai Hydrothermal Area, Tibet, China
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摘要: 西藏搭格架水热区的热泉含异常高浓度的钨，其钨/钼比也远高于常见天然水.开展了搭格架典型热泉的地球化学研究，发现中性热泉的钨浓度显著高于偏酸性热泉：前者是深部母地热流体经绝热冷却、传导冷却等过程后排出地表而形成，其中的钨主要来自岩浆水的贡献；而后者为中性地热水和蒸汽加热型强酸性水的混合产物，贫钨蒸汽加热型水的稀释使其钨浓度不同程度降低.在地热水中，钨与典型保守组分氯相似，不易自液相沉淀或被热储介质吸附；但地热水含硫化物时，钼则极易以辉钼矿的形式沉淀，导致搭格架热泉的钨/钼比偏高.虽然搭格架地热水中存在硫化物，但钨在水中主要以钨酸盐的形式存在，少量硫代钨酸盐的形成对钨的水文地球化学过程影响不大.Abstract: Extremely high concentrations of tungsten was detected in the hot springs discharged from the Daggyai hydrothermal area, Tibet, and their tungsten to molybdenum ratios are much higher than common natural waters as well. A hydrogeochemical study of typical Daggyai hot springs was carried out, based on which it was found that the tungsten concentrations of the neutral springs are significantly higher than those of the acid springs. The neutral hot springs at Daggyai were formed via the adiabatic cooling or conductive cooling of the parent geothermal fluids ascending from the deep levels to the surface, and the tungsten in these waters is primarily from the contribution of magmatic fluids. In contrast, the slightly acid hot springs are basically a mixture of the steam-heated acid waters and neutral geothermal waters, and the dilution of tungsten-depleted steam-heated waters lowered the tungsten concentrations of these springs to various degrees. In geothermal systems, tungsten behaves generally like chloride, a typical conservative component, and is difficult to precipitate from geothermal water or to be adsorbed by reservoir rocks. However, molybdenum is prone to precipitate from sulfide-rich Daggyai geothermal waters as the form of molybdenite, resulting in the high tungsten to molybdenum ratios of the Daggyai hot springs. Moreover, although sulfide exists in the Daggyai geothermal waters, the major species of tungsten is tungstate instead of thiotungstates. The formation of trace thiotungstates has little effects on the tungsten-involved hydrogeochemical processes.
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Key words:
- hot spring /
- tungsten /
- thiotungstates /
- hydrogeochemical /
- Daggyai /
- Tibet /
- hydrogeology
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图 1 搭格架水热系统的区域大地构造背景
MBT. 主边界断层；ITS. 雅鲁藏布江缝合带；BNS. 班公错-怒江缝合带；JS. 龙木错-金沙江缝合带；据Guo et al.（2019b）修改
Fig. 1. Regional tectonic setting of the Daggyai hydrothermal system
图 2 搭格架水热区地质简图及采样位置
据郑绵平等（1995）修改
Fig. 2. Simplified geological map of the Daggyai hydrothermal area and sampling locations
图 4 搭格架热泉样品的钨、钼浓度和钨/钼比
Fig. 4. Concentrations of tungsten and molybdenum as well as their ratios of the Daggyai hot springs
图 5 搭格架热泉样品中硫代钨酸盐占总钨的百分含量与硫化物浓度（a）及pH（b）的关系
Fig. 5. Ratio of thiotungstates to total tungsten vs. sulfide concentration (a) and pH (b) of the Daggyai hot springs
图 6 搭格架热泉样品中一硫代钨酸盐和二硫代钨酸盐占硫代钨酸盐的百分含量与硫化物浓度（a）及pH（b）的关系
Fig. 6. Ratios of mono-thiotungstate and di-thiotungstate to total thiotungstates vs. sulfide concentration (a) and pH (b) of the Daggyai hot springs
图 7 搭格架热泉的δD-δ18O关系
岩浆水氢氧同位素组成引自Giggenbach（1992）；大气降水线引自Tan et al.（2014）；□. 酸性热泉；○. 中性热泉；△. 入渗水；引自Guo et al.（2010）
Fig. 7. δD-δ18O relations of the Daggyai hot springs
图 8 搭格架热泉样品的钨-氯（a）、钨-钠（b）、钨-砷（c）、钨-钼（d）散点图
Fig. 8. Relations of tungsten vs. chloride (a), tungsten vs. sodium (b), tungsten vs. arsenic (c), and tungsten vs. molybdenum (d) in the Daggyai hot springs
表 1 搭格架热泉样品的水文地球化学和同位素地球化学特征
Table 1. Hydrogeochemical and isotopic characteristics of the Daggyai hot springs
样品编号 T(℃) pH EC(µs/cm) EH(V) W(µg/L) Mo(µg/L) W/Mo 硫化物(mg/L) δD(‰ SMOW) δ18O(‰ SMOW) DGJ00 79.3 8.59 1 873 -0.389 899.9 32.20 28 0.15 -153 -20.5 DGJ01 79.5 8.24 1 910 -0.357 868.5 30.20 29 0.09 -153 -20.2 DGJ03 69.1 4.46 386 -0.060 323.1 1.41 230 0.04 -156 -15.3 DGJ04 80.1 7.40 1 912 -0.307 879.2 27.40 32 0.07 -148 -19.3 DGJ05 78.9 8.25 2 004 -0.358 950.1 32.00 30 0.13 -147 -18.8 DGJ06 74.1 6.96 1 916 -0.272 897.6 36.10 25 0.15 n.a. n.a. DGJ07 82.1 6.97 1 872 -0.278 890.4 41.50 21 0.11 -148 -19.7 DGJ08 75.5 6.92 1 994 -0.269 923.1 37.40 25 0.09 n.a. n.a. DGJ09 41.5 6.90 1 678 -0.212 919.9 26.10 35 0.20 n.a. n.a. DGJ10 81.9 7.35 1 914 -0.320 925.6 33.20 28 0.49 -156 -20.0 DGJ11 79.9 6.99 1 966 -0.287 961.2 29.30 33 0.26 n.a. n.a. DGJ12 77.8 7.00 1 805 -0.285 849.3 28.60 30 0.15 -159 -19.7 DGJ13 80.2 6.00 1 502 -0.203 795.7 33.30 24 0.12 -157 -19.4 注：n.a. 未分析；表中水化学数据据 Guo et al. (2019a) .
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表 2 水中钨的不同形态的化学热力学数据
Table 2. Chemical thermodynamic data of various tungsten species in water
钨的形态 化学结构式 化学反应式 log(K) 来源 钨酸盐 HnWO4n-2 (n=0, 1, 2) WO42-+H+=HWO4- 3.60 Smith and Martell(2004) WO42-+2H+=H2WO4 5.80 Smith and Martell(2004) 一硫代钨酸盐 WSO32- WO42-+H2S=WSO32-+H2O 3.08 Mohajerin et al.(2014) 二硫代钨酸盐 WS2O22- WSO32-+H2S=WS2O22-+H2O 3.22 Mohajerin et al.(2014) 三硫代钨酸盐 WS3O2- WS2O22-+H2S=WS3O2-+H2O 2.76 Mohajerin et al.(2014) 四硫代钨酸盐 WS42- WS3O2-+H2S=WS42-+H2O 2.36 Mohajerin et al.(2014) 注：n.a. 未分析；表中水化学数据据 Guo et al. (2019a) .
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表 3 搭格架热泉中钨酸盐和硫代钨酸盐的浓度(mol/L)
Table 3. Concentrations of tungstate and thiotungstate in the Daggyai hot springs (mol/L)
样品编号 钨酸盐 一硫代钨酸盐 二硫代钨酸盐 三硫代钨酸盐 四硫代钨酸盐 WO42- HWO4- H2WO4 WSO32- WS2O22- WS3O2- WS42- DGJ00 4.90×10-6 3.08×10-11 1.06×10-17 3.40×10-12 3.26×10-18 1.08×10-24 1.43×10-31 DGJ01 4.73×10-6 6.68×10-11 5.16×10-17 3.16×10-12 2.92×10-18 9.33×10-25 1.19×10-31 DGJ03 2.83×10-7 3.06×10-8 1.55×10-10 3.09×10-10 4.68×10-13 2.45×10-16 5.11×10-20 DGJ04 4.79×10-6 4.67×10-10 2.50×10-15 2.64×10-11 2.01×10-16 5.32×10-22 5.59×10-28 DGJ05 5.18×10-6 7.06×10-11 5.30×10-17 5.86×10-12 9.14×10-18 4.95×10-24 1.07×10-30 DGJ06 4.89×10-6 1.33×10-9 1.96×10-14 1.84×10-10 9.51×10-15 1.71×10-19 1.22×10-24 DGJ07 4.85×10-6 1.27×10-9 1.82×10-14 8.16×10-11 1.89×10-15 1.52×10-20 4.88×10-26 DGJ08 5.03×10-6 1.50×10-9 2.42×10-14 1.40×10-10 5.36×10-15 7.12×10-20 3.77×10-25 DGJ09 5.01×10-6 1.63×10-9 2.80×10-14 4.70×10-10 6.09×10-14 2.74×10-18 4.90×10-23 DGJ10 5.04×10-6 5.50×10-10 3.29×10-15 2.04×10-10 1.14×10-14 2.20×10-19 1.70×10-24 DGJ11 5.24×10-6 1.31×10-9 1.80×10-14 2.50×10-10 1.64×10-14 3.75×10-19 3.41×10-24 DGJ12 4.63×10-6 1.16×10-9 1.57×10-14 3.15×10-10 2.96×10-14 9.65×10-19 1.25×10-23 DGJ13 4.32×10-6 1.12×10-8 1.54×10-12 9.79×10-10 3.06×10-13 3.32×10-17 1.43×10-21 注：n.a. 未分析；表中水化学数据据 Guo et al. (2019a) .
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表 4 搭格架热泉样品相对于常见含钼矿物的饱和指数
Table 4. Saturation indices of the Daggyai hot springs with respect to common molybdenum-bearing minerals
样品编号 辉钼矿 硒钼矿 钼钙矿 钼铁矿 钼镁矿 钼镍矿 钼华 DGJ00 5.77 -26.04 -1.75 -29.99 -10.85 -10.40 -11.88 DGJ01 6.21 -24.62 -1.75 -28.67 -10.86 -9.80 -11.21 DGJ03 18.83 n.a. -3.24 -24.30 -12.16 -8.64 -5.09 DGJ04 9.41 -21.27 -1.67 -26.72 -10.78 -9.19 -9.57 DGJ05 6.79 n.a. -1.81 -28.45 -11.15 -10.01 -11.21 DGJ06 12.78 n.a. -1.74 -26.07 -10.89 -8.14 -8.57 DGJ07 11.09 6.88 -1.74 -25.32 -10.94 -8.24 -8.53 DGJ08 12.39 -19.48 -2.29 -26.91 -11.43 -8.31 -8.47 DGJ09 17.99 11.37 -1.91 -26.59 -11.14 -8.00 -8.57 DGJ10 11.31 n.a. -1.69 -26.63 -10.80 -8.87 -9.39 DGJ11 12.18 -19.84 -2.08 -26.69 -11.39 -8.61 -8.72 DGJ12 12.77 -19.85 -2.45 -28.50 -11.56 -8.91 -8.74 DGJ13 15.10 n.a. -2.36 -24.46 -11.54 -7.80 -6.82 注：n.a. 由于样品中硒未检出，未计算样品相对于硒钼矿的饱和指数.
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