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    腾冲热海地热田高温热泉中的硫代砷化物及其地球化学成因

    郭清海 刘明亮 李洁祥

    郭清海, 刘明亮, 李洁祥, 2017. 腾冲热海地热田高温热泉中的硫代砷化物及其地球化学成因. 地球科学, 42(2): 286-297. doi: 10.3799/dqkx.2017.021
    引用本文: 郭清海, 刘明亮, 李洁祥, 2017. 腾冲热海地热田高温热泉中的硫代砷化物及其地球化学成因. 地球科学, 42(2): 286-297. doi: 10.3799/dqkx.2017.021
    Guo Qinghai, Liu Mingliang, Li Jiexiang, 2017. Thioarsenic Species in the High-Temperature Hot Springs from the Rehai Geothermal Field (Tengchong) and Their Geochemical Geneses. Earth Science, 42(2): 286-297. doi: 10.3799/dqkx.2017.021
    Citation: Guo Qinghai, Liu Mingliang, Li Jiexiang, 2017. Thioarsenic Species in the High-Temperature Hot Springs from the Rehai Geothermal Field (Tengchong) and Their Geochemical Geneses. Earth Science, 42(2): 286-297. doi: 10.3799/dqkx.2017.021

    腾冲热海地热田高温热泉中的硫代砷化物及其地球化学成因

    doi: 10.3799/dqkx.2017.021
    基金项目: 

    国家自然科学基金项目 41572335

    生物地质与环境地质国家重点实验室自主研究课题 GBL11505

    详细信息
      作者简介:

      郭清海(1978-),男,教授,博士生导师,主要从事高温地热流体地球化学方面的研究.ORCID:0000-0001-6602-9664. E-mail: qhguo2006@gmail.com

    • 中图分类号: P66

    Thioarsenic Species in the High-Temperature Hot Springs from the Rehai Geothermal Field (Tengchong) and Their Geochemical Geneses

    • 摘要: 以我国大陆范围内典型的岩浆热源型水热系统——云南腾冲热海为研究区,在国内首次对热泉中硫代砷化物含量及其地球化学成因进行了分析.研究采用的在野外对富硫化物水样进行快速冷冻处理、而后在实验室进行砷的形态分离和测试的方法明显优于当前通用的水样砷含量及其形态分析的预处理和测试方法.主要原因为后者在采样现场对水样的酸化处理可使样品中三硫代砷酸盐以非定形态硫砷化合物的形式沉淀,且用常规阴离子交换柱在野外无法实现硫代砷酸盐的完全回收及其与砷酸盐的分离.受岩浆流体输入和热储内高温条件下强烈流体-岩石相互作用的控制,热海水热系统排泄的中性-偏碱性热泉中富集硫化物和砷,为热泉中硫代砷化物的形成提供了必要条件.热海热泉中检出的硫代砷化物包括一硫代砷酸盐、二硫代砷酸盐和三硫代砷酸盐,在总砷中所占比例最高分别可达26.7%、43.3%和33.7%.热海地热田的2个子区(硫磺塘和澡塘河) 的热泉沿不同断裂带出露,地热水升流过程中经历的冷却方式也不同,使硫磺塘热泉具有相对较高的总硫化物含量和总砷含量,并导致其中各类硫代砷酸盐具有更高的含量范围.

       

    • 图  1  热海地热田地质简图及采样位置

      廖志杰和赵平(1999)修改

      Fig.  1.  Simplified geological map of the Rehai geothermal field and sampling locations

      图  2  热泉样品中不同形态砷的含量对比

      Fig.  2.  Comparison of the concentrations of various arsenic species in the hot spring samples

      图  3  热泉样品中硫化物和一、二、三硫代砷酸盐含量的相关分析

      Fig.  3.  Correlation analysis of the concentrations of sulfide with those of mono-, di-and tri-thioarsenates in the hot spring samples

      图  4  热泉样品的总砷含量(ICP-MS) 和各种形态砷的含量之和(IC-ICP-MS) 的对比

      Fig.  4.  Comparison of total arsenic (determined by ICP-MS) and the sum of all arsenic species (determined by IC-ICP-MS) in the hot spring samples

      图  5  热泉样品的砷的形态分析结果的对比

      Fig.  5.  Comparison of the measurements of arsenic species in the hot spring samples

      表  1  热泉采集情况及现场测试指标

      Table  1.   Sampling information of the hot springs and their in-situ parameters

      样品编号 子区 采样位置 采样温度(℃) pH EC(μs/cm) TDS(mg/L) Eh(Mv)
      TQL 硫磺塘 听泉楼 81.3 7.96 3 413 1 680 -292
      YJQ-L 硫磺塘 眼镜泉-左 91.0 8.88 3 485 1 708 -390
      GMQ 硫磺塘 鼓鸣泉 91.5 8.12 3 331 1 632 -371
      HTJ-L 硫磺塘 怀胎井-左 91.2 7.40 3 181 1 559 -364
      HTJ-R 硫磺塘 怀胎井-右 82.5 6.88 2 450 1 201 -311
      DGG 硫磺塘 大滚锅 96.0 7.45 4 042 1 981 -267
      XKT-L 澡塘河 霞客亭-左 75.0 7.46 2 050 1 005 -165
      XKT-R 澡塘河 霞客亭-右 95.0 7.53 2 137 1 048 -363
      ZTH 澡塘河 澡塘河热泉 85.0 7.13 2 239 1 098 -256
      HMZP-R 澡塘河 蛤蟆嘴坡-右 91.0 9.96 2 493 1 222 -326
      下载: 导出CSV

      表  2  热泉水化学组成(mg/L)

      Table  2.   Hydrochemical compositions of the hot springs (mg/L)

      样品编号 碱度 SO4 Cl F Na K Ca Mg Li Rb Cs Al Fe B Si 总硫化物
      TQL 830 31.1 597.1 14.6 699.0 113.1 0.99 0.07 6.56 1.68 1.02 0.06 0.01 9.08 99.6 2.60
      YJQ-L 960 33.1 594.0 15.3 771.0 133.8 1.20 0.10 7.50 1.62 0.83 0.08 0.01 9.73 124.1 5.90
      GMQ 848 32.2 593.9 14.5 716.2 127.9 1.28 0.09 6.84 1.95 1.03 0.05 0.02 9.18 113.9 5.20
      HTJ-L 795 33.3 560.7 13.8 692.6 124.5 1.02 0.08 6.90 1.50 0.78 0.03 0.02 8.89 102.6 4.20
      HTJ-R 640 44.5 464.6 11.5 547.6 100.1 1.42 0.10 5.78 1.27 0.63 0.13 0.02 7.23 99.5 2.10
      DGG 1 030 40.3 715.9 19.2 893.4 153.6 0.95 0.13 8.50 1.79 0.90 0.20 0.04 11.3 156.3 0.24
      XKT-L 520 64.3 311.2 7.6 430.3 78.3 4.46 0.32 4.40 0.98 0.50 0.11 0.01 5.09 63.4 0.17
      XKT-R 600 37.3 335.6 8.0 456.1 81.4 2.19 0.07 4.64 0.98 0.51 0.08 0.02 5.34 66.5 0.71
      ZTH 580 43.9 337.6 8.0 449.7 81.9 2.31 0.18 4.61 1.00 0.52 0.11 0.06 5.33 66.3 0.60
      HMZP-R 580 52.5 339.5 9.1 469.0 81.0 5.11 0.40 4.67 1.00 0.52 0.10 0.13 5.44 67.0 0.43
      下载: 导出CSV

      表  3  热泉中砷及其不同形态的测试结果(μg/L)

      Table  3.   Arsenic and its speciation in the hot springs (μg/L)

      样品编号 用ICP-MS测定 计算值 用IC-ICP-MS测定
      总砷 三价砷 五价砷 各形态砷的总和 亚砷酸盐 砷酸盐 一硫代砷酸盐 二硫代砷酸盐 三硫代砷酸盐
      TQL 751 78.8 398.8 1 139.9 81.8 401.3 304.8 169.6 182.5
      YJQ-L 897 31.6 574.8 1 348.3 74.6 309.9 247.8 324.1 391.9
      GMQ 837 50.7 346.9 842.7 57.4 172.7 151.6 214.3 246.6
      HTJ-L 802 127.9 461.4 807.8 91.6 88.8 117.6 349.4 160.5
      HTJ-R 593 403.6 151.3 791.8 416.0 44.0 15.9 148.3 167.7
      DGG 1 059 940.6 104.6 1 288.6 755.3 84.7 54.0 229.5 165.2
      XKT-L 305 21.3 262.0 272.1 31.2 239.8 1.1 0.0 0.0
      XKT-R 257 79.4 146.7 272.4 26.9 38.5 17.8 97.3 91.9
      ZTH 255 123.2 124.7 283.0 142.7 71.7 24.5 24.6 19.5
      HMZP-R 264 153.0 102.1 295.4 155.9 74.9 15.4 27.6 21.6
      下载: 导出CSV

      表  4  热泉中砷及其不同形态的测试结果的相对标准偏差(R.S.D.)

      Table  4.   Relative standard deviations (R.S.D.) of the analytical results of total arsenic and its species in the hot springs

      样品编号 总砷 三价砷 五价砷 亚砷酸盐 砷酸盐 一硫代砷酸盐 二硫代砷酸盐 三硫代砷酸盐
      TQL 2.0% 9.9% 3.1% 2.8% 2.1% 1.7% 5.8% 0.3%
      YJQ-L 2.5% 7.3% 0.8% 3.8% 1.4% 3.8% 2.5% 2.7%
      GMQ 1.5% 10.2% 4.1% 9.6% 1.3% 4.9% 2.0% 1.7%
      HTJ-L 0.5% 9.4% 1.0% 2.3% 1.8% 6.4% 1.6% 5.8%
      HTJ-R 1.5% 2.1% 6.0% 1.1% 5.5% 5.3% 4.2% 3.7%
      DGG 2.1% 2.5% 7.0% 0.3% 7.3% 2.4% 2.2% 1.5%
      XKT-L 1.5% 10.0% 2.9% 3.2% 4.5% 12.9% 0.0% 0.0%
      XKT-R 4.2% 4.4% 6.2% 11.6% 1.5% 5.6% 0.9% 4.0%
      ZTH 1.9% 5.3% 1.2% 4.8% 4.3% 17.3% 2.9% 6.5%
      HMZP-R 2.5% 2.9% 7.2% 3.9% 4.5% 2.8% 4.1% 2.0%
      下载: 导出CSV

      表  5  热储温度计算结果(℃)

      Table  5.   Calculated reservoir temperatures (℃)

      样品编号 样品所在子区 采样温度 Na-K温度 K-Mg温度 石英温度
      TQL 硫磺塘 81.3 274 230 185
      YJQ-L 硫磺塘 91.0 281 231 201
      GMQ 硫磺塘 91.5 283 233 195
      HTJ-L 硫磺塘 91.2 284 232 187
      HTJ-R 硫磺塘 82.5 286 218 185
      DGG 硫磺塘 96.0 280 231 219
      XKT-L 澡塘河 75.0 285 181 155
      XKT-R 澡塘河 95.0 283 216 158
      ZTH 澡塘河 85.0 285 195 158
      HMZP-R 澡塘河 91.0 280 178 158
      注:硫磺塘样品的Na-K温度平均值为281 ℃,K-Mg温度平均值为229 ℃,石英温度平均值为195 ℃;澡塘河样品的Na-K温度平均值为283 ℃,K-Mg温度平均值为192 ℃,石英温度平均值为157 ℃.计算Na-K温度和K-Mg温度的地热温标引自Giggenbach (1988),计算石英温度的地热温标引自Verma and Santoyo (1997).
      下载: 导出CSV
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