冲绳海槽唐印热液区中硬石膏的化学及其硫同位素组成

曾志刚, 陈祖兴, 齐海燕, 陈帅. 冲绳海槽唐印热液区中硬石膏的化学及其硫同位素组成[J]. 海洋地质与第四纪地质, 2023, 43(5): 1-16. doi: 10.16562/j.cnki.0256-1492.2023060601
引用本文: 曾志刚, 陈祖兴, 齐海燕, 陈帅. 冲绳海槽唐印热液区中硬石膏的化学及其硫同位素组成[J]. 海洋地质与第四纪地质, 2023, 43(5): 1-16. doi: 10.16562/j.cnki.0256-1492.2023060601
ZENG Zhigang, CHEN Zuxing, QI Haiyan, CHEN Shuai. Chemical and sulfur isotopic compositions of anhydrite from the Tangyin hydrothermal field in the Okinawa Trough[J]. Marine Geology & Quaternary Geology, 2023, 43(5): 1-16. doi: 10.16562/j.cnki.0256-1492.2023060601
Citation: ZENG Zhigang, CHEN Zuxing, QI Haiyan, CHEN Shuai. Chemical and sulfur isotopic compositions of anhydrite from the Tangyin hydrothermal field in the Okinawa Trough[J]. Marine Geology & Quaternary Geology, 2023, 43(5): 1-16. doi: 10.16562/j.cnki.0256-1492.2023060601

冲绳海槽唐印热液区中硬石膏的化学及其硫同位素组成

  • 基金项目: 国家自然科学基金项目“深海界面过程和化能生态系统”(42221005),“西太平洋俯冲体系中岩浆活动及其对热液物质供给的制约”(91958213);中国科学院战略性先导科技专项子课题“热液/冷泉区岩浆物质贡献与流体化学过程”(XDB42020402);国家重点基础研究发展计划(973计划)项目“典型弧后盆地热液活动及其成矿机理”(2013CB429700);泰山学者工程资助项目
详细信息
    作者简介: 曾志刚(1968—),男,博士,研究员,从事海底热液活动及成矿研究,E-mail:zgzeng@qdio.ac.cn
  • 中图分类号: P736.4

Chemical and sulfur isotopic compositions of anhydrite from the Tangyin hydrothermal field in the Okinawa Trough

  • 硬石膏是最早构成热液烟囱体壁的矿物之一,其对于了解流体-海水混合以及海底热液系统中元素的迁移与循环具有重要的意义。为此,对西太平洋冲绳海槽唐印热液区中的硬石膏,进行了微区原位元素以及硫同位素组成分析。根据硬石膏的结晶形态,可以将硬石膏分为两种类型:较早形成的I型硬石膏,其呈半自形或他形晶,似针状、放射状及不规则晶的集合体产出;较晚形成的II型硬石膏,其呈自形晶,以板状及粒状晶的集合体产出。当热液流体初次遇到海水时,将快速沉淀形成I型硬石膏,并构成了热液烟囱体的壁。随后,II型硬石膏经历了一个相对充分的生长阶段。同时,硬石膏中的Ba、Al、Sr、Ni、Fe、Mn和Cr含量明显高于海水,表明产生硬石膏沉淀的热液流体来自于海底面以下,是经历了流体-岩石和/或沉积物相互作用的流体。硬石膏的Mg含量明显分别低于海水和高于喷口流体,表明其是流体-海水混合的结果。I型硬石膏,其Sr含量明显低于II型硬石膏,表明在形成自形、板片状或粒状硬石膏的期间,来自热液流体的Sr,主要进入II型硬石膏中。硬石膏的Fe、As、Sr、Ba和Pb含量,明显高于冲绳海槽喷口流体的,则表明这些来自流体中的元素更容易随着硬石膏的沉淀而进入硬石膏中,并导致硬石膏富集该类元素。硬石膏的稀土元素组成及其配分模式,具正Ce和负Eu异常的特征,其是流体在海底面以下从火山岩和/或沉积物中淋滤出来,并经历了流体-海水混合作用的结果。此外,在流体-海水混合期间,硬石膏中的硫主要来自海水。

  • 加载中
  • 图 1  冲绳海槽唐印热液区中硬石膏样品的位置

    Figure 1. 

    图 2  冲绳海槽唐印热液区中硬石膏样品的手标本(a)、单偏光(b)和正交偏光(c,d)显微镜下照片

    Figure 2. 

    图 3  冲绳海槽唐印热液区中硬石膏(a,b,c)与硫化物(d)的扫描电镜背散射电子图像

    Figure 3. 

    图 4  冲绳海槽唐印热液区中硬石膏与硅质物的扫描电镜能谱面扫描图像

    Figure 4. 

    图 5  冲绳海槽唐印热液区中硬石膏的电子探针背散射电子图像

    Figure 5. 

    图 6  冲绳海槽唐印热液区中硬石膏样品的主量元素组成

    Figure 6. 

    图 7  冲绳海槽唐印热液区中硬石膏样品的微量元素组成

    Figure 7. 

    图 8  冲绳海槽唐印热液区中硬石膏样品的稀土元素球粒陨石标准化配分模式图

    Figure 8. 

    图 9  冲绳海槽唐印热液区硬石膏中Ag与Bi的相关关系

    Figure 9. 

    表 1  唐印热液区样品R11-H2中硬石膏的电子探针分析结果和化学式

    Table 1.  Electron microprobe analyses of the anhydrite in sample R11-H2 from the Tangyin hydrothermal field and their atoms per formula unit for elements %

    类型 测试点 K2O SO3 CaO BaO TiO2 Na2O Al2O3 SrO MgO SiO2 NiO FeO MnO Cr2O3 总计 化学式
    类型I 6-6 n.d. 58.02 41.95 0.09 n.d. 0.02 n.d. 0.14 0.02 n.d. n.d. 0.03 n.d. 0.03 100.29 Ca1.58S0.71O3.71
    6-8 n.d. 57.45 41.03 0.11 n.d. n.d. n.d. 0.11 0.86 0.74 n.d. n.d. n.d. n.d. 100.31 Ca1.55Mg0.02Si0.01S0.71O3.71
    6-10 n.d. 56.84 42.68 n.d. n.d. 0.03 n.d. 0.19 0.04 n.d. n.d. n.d. n.d. 0.03 99.81 Ca1.60S0.70O3.70
    6-11 n.d. 55.64 44.29 n.d. n.d. 0.06 n.d. 0.19 0.16 n.d. n.d. n.d. n.d. 0.08 100.43 Ca1.65S0.67O3.67
    6-12 n.d. 55.43 45.47 0.06 n.d. 0.03 0.02 0.15 0.07 n.d. 0.04 n.d. n.d. n.d. 101.26 Ca1.67S0.66O3.66
    6-13 n.d. 56.29 42.67 n.d. 0.04 0.06 n.d. 0.22 0.19 n.d. n.d. n.d. n.d. 0.07 99.53 Ca1.61S0.69O3.69
    6-15 n.d. 57.19 42.29 n.d. n.d. 0.08 n.d. 0.20 0.04 n.d. n.d. n.d. n.d. n.d. 99.80 Ca1.59S0.70O3.70
    6-16 n.d. 56.28 42.27 n.d. 0.05 0.05 n.d. 0.14 0.07 n.d. 0.04 0.10 n.d. n.d. 99.00 Ca1.60S0.70O3.69
    6-17 n.d. 57.25 42.76 n.d. n.d. 0.02 n.d. 0.19 0.03 n.d. n.d. n.d. 0.05 n.d. 100.29 Ca1.60S0.70O3.70
    6-24 n.d. 57.74 42.59 n.d. n.d. n.d. n.d. 0.18 0.03 n.d. n.d. 0.03 0.04 n.d. 100.59 Ca1.59S0.70O3.70
    类型II 4-1-1 n.d. 56.72 43.84 n.d. n.d. 0.07 0.02 0.31 n.d. n.d. n.d. n.d. n.d. 0.09 101.05 Ca1.62S0.68O3.68
    4-1-2 n.d. 58.23 42.41 n.d. n.d. 0.05 n.d. 0.29 0.02 n.d. n.d. 0.04 n.d. n.d. 101.03 Ca1.58S0.71O3.71
    4-1-3 n.d. 56.38 42.89 0.08 n.d. 0.04 n.d. 0.62 0.02 n.d. n.d. n.d. n.d. 0.04 100.07 Ca1.61Sr0.01S0.69O3.69
    4-1-4 n.d. 57.63 42.96 n.d. n.d. 0.02 n.d. 0.22 n.d. n.d. n.d. n.d. n.d. 0.05 100.89 Ca1.60S0.70O3.70
    4-1-5 n.d. 57.31 44.11 0.07 n.d. n.d. n.d. 0.19 0.06 n.d. n.d. n.d. n.d. n.d. 101.73 Ca1.62S0.69O3.69
    4-1-6 n.d. 58.12 42.71 n.d. n.d. n.d. 0.04 0.20 0.04 n.d. n.d. n.d. n.d. n.d. 101.10 Ca1.59S0.70O3.70
    4-1-7 n.d. 57.87 42.18 n.d. n.d. 0.03 n.d. 0.28 0.06 n.d. 0.04 n.d. 0.05 n.d. 100.50 Ca1.58S0.71O3.71
    6-1-1 n.d. 58.17 41.78 n.d. n.d. 0.04 n.d. 0.25 n.d. n.d. n.d. n.d. n.d. n.d. 100.23 Ca1.57S0.71O3.71
    4-14 n.d. 58.92 42.00 0.08 n.d. n.d. 0.02 0.52 0.07 n.d. n.d. 0.03 n.d. n.d. 101.64 Ca1.56S0.71O3.71
    4-16 n.d. 57.92 43.33 n.d. n.d. 0.03 n.d. 0.28 0.04 n.d. 0.07 0.03 0.05 n.d. 101.75 Ca1.60S0.70O3.70
    4-17 n.d. 56.52 42.94 n.d. n.d. 0.03 0.02 0.23 n.d. n.d. n.d. 0.04 n.d. n.d. 99.78 Ca1.61S0.69O3.69
    4-18 n.d. 56.70 44.63 0.07 n.d. 0.02 n.d. 0.24 0.08 n.d. n.d. 0.03 0.04 0.05 101.85 Ca1.64S0.68O3.68
    检测限 K2O SO3 CaO BaO TiO2 Na2O Al2O3 SrO MgO SiO2 NiO FeO MnO Cr2O3
    0.02 0.03 0.02 0.05 0.03 0.02 0.02 0.03 0.01 0.03 0.03 0.03 0.03 0.03
    注:n.d表示无数据。
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    表 2  使用LA-ICP-MS分析唐印热液区样品R11-H2中硬石膏的微量元素含量

    Table 2.  Trace element concentrations of the anhydrite in sample R11-H2 from the Tangyin hydrothermal field determined via LA-ICP-MS μg/g

    元素 4-1-1 4-1-2 4-1-3 4-1-4 4-1-5 4-1-6 4-1-7 6-1-1 最小值 最大值 平均值 检测限 SRM610平均值 SRM610参考值 RE%
    Sc n.d. 1.56 1.46 n.d. n.d. n.d. n.d. n.d. 1.46 1.56 1.51 0.721 441.20 441.00 0.05
    Ti 66.7 30.0 84.1 33.4 4.57 12.3 34.1 164 4.57 164 53.7 0.891 439.66 434.00 1.31
    V 1.55 0.837 2.44 0.501 0.199 0.424 0.509 2.40 0.199 2.44 1.11 0.134 442.09 442.00 0.02
    Cr 8.06 57.9 2.36 34.7 417 2.80 16.7 11.9 2.36 417 68.9 1.797 405.81 405.00 0.20
    Fe 707 551 776 160 484 n.d. 388 1760 160 1760 689 134.53 473.45 458.00 3.37
    Mn 107 78.6 234 96.7 108 75.1 159 122 75.1 234 123 0.417 485.27 485.00 0.06
    Co n.d. 0.218 0.217 n.d. 0.085 n.d. n.d. 0.716 0.085 0.716 0.309 0.079 405.07 405.00 0.02
    Ni 2.67 0.658 2.74 n.d. 0.357 1.31 1.25 5.28 0.357 5.28 2.04 0.314 458.80 458.70 0.02
    Cu 58.8 54.8 84.0 41.3 98.0 47.8 56.7 92.8 41.3 98.0 66.8 0.614 430.15 430.00 0.04
    Zn 107 164 464 9.25 82.6 100 328 411 9.25 464 208 2.979 456.02 456.00 0.01
    Ga 1.02 0.396 1.65 0.612 n.d. 0.160 0.261 1.81 0.160 1.81 0.843 0.115 438.07 438.00 0.02
    Ge n.d. 0.987 3.73 n.d. n.d. 1.67 n.d. 1.24 0.987 3.73 1.91 0.347 426.05 426.00 0.01
    As n.d. 9.25 27.0 2.55 5.85 2.68 12.6 10.3 2.55 27.0 10.0 0.991 317.06 317.00 0.02
    Rb 9.61 4.17 13.6 4.09 0.607 1.69 4.44 19.5 0.607 19.5 7.22 0.101 425.77 425.70 0.02
    Sr 1785 1919 1372 1661 1708 1569 1778 1580 1372 1919 1671 0.048 515.58 515.50 0.02
    Y 1.22 0.341 1.67 0.455 0.108 0.237 0.448 2.66 0.108 2.66 0.893 0.016 450.10 450.00 0.02
    Mo 0.137 0.050 0.087 n.d. 0.034 0.117 0.109 0.120 0.034 0.137 0.093 0.027 410.00 410.00 0.00
    Ag 0.755 1.15 1.17 0.679 1.77 0.403 1.08 4.26 0.403 4.26 1.41 0.166 239.06 239.00 0.02
    Cd 1.05 n.d. 0.640 0.152 0.208 0.706 0.913 1.85 0.152 1.85 0.789 0.105 259.22 259.00 0.08
    In 0.020 n.d. n.d. n.d. n.d. n.d. 0.046 0.317 0.020 0.317 0.128 0.018 441.02 441.00 0.01
    Sn n.d. n.d. 2.85 1.76 2.90 2.26 4.92 4.58 1.76 4.92 3.21 0.797 396.01 396.00 0.00
    Sb 3.28 14.3 24.3 12.4 33.5 14.5 17.5 6.65 3.28 33.5 15.8 0.063 369.05 369.00 0.01
    Ba 164 97.1 136 149 193 76.6 123 177 76.6 193 139 0.219 435.01 435.00 0.00
    La 2.90 1.51 4.17 1.44 0.701 0.731 1.64 6.31 0.701 6.31 2.43 0.009 457.02 457.00 0.00
    Ce 8.67 4.12 12.4 4.48 0.968 1.75 4.60 18.8 0.968 18.8 6.97 0.007 448.02 448.00 0.01
    Pr 0.420 0.281 0.610 0.218 0.078 0.101 0.340 0.946 0.078 0.946 0.374 0.004 430.07 430.00 0.02
    Nd 1.11 0.933 2.65 0.816 0.258 0.510 0.868 3.45 0.258 3.45 1.32 0.022 431.01 431.00 0.00
    Sm n.d. 0.070 0.824 n.d. 0.076 0.114 0.310 0.591 0.070 0.824 0.331 0.009 451.16 451.00 0.04
    Eu 0.091 0.019 0.068 n.d. 0.088 0.046 0.048 0.115 0.019 0.115 0.068 0.018 461.03 461.00 0.01
    Gd 0.246 0.210 0.432 0.157 0.021 0.049 0.113 0.434 0.021 0.434 0.208 0.010 444.01 444.00 0.00
    Tb 0.025 n.d. 0.028 0.023 0.010 n.d. 0.006 0.084 0.006 0.084 0.029 0.006 443.02 443.00 0.00
    Dy 0.224 0.200 0.427 0.134 0.039 0.044 0.023 0.438 0.023 0.438 0.191 0.012 427.01 427.00 0.00
    Ho 0.082 0.018 0.058 n.d. 0.010 n.d. 0.029 0.078 0.010 0.082 0.046 0.006 449.00 449.00 0.00
    Er 0.104 0.025 0.135 0.105 0.018 0.051 0.063 0.183 0.018 0.183 0.085 0.016 426.04 426.00 0.01
    Tm n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.040 0.040 0.040 0.040 0.035 420.02 420.00 0.00
    Yb n.d. 0.077 0.191 0.081 n.d. 0.016 n.d. 0.138 0.016 0.191 0.101 0.010 445.05 445.00 0.01
    Lu 0.040 n.d. 0.023 n.d. n.d. n.d. 0.021 n.d. 0.021 0.040 0.028 0.006 435.08 435.00 0.02
    Au 0.036 0.066 n.d. 0.042 n.d. n.d. n.d. n.d. 0.036 0.066 0.048 0.025 23.01 23.00 0.04
    Tl 0.134 0.098 0.133 n.d. n.d. n.d. 0.116 n.d. 0.098 0.134 0.121 0.086 61.01 61.00 0.02
    Pb 145 318 505 136 375 278 401 340 136 505 312 0.120 426.00 426.00 0.00
    Bi 0.043 n.d. 0.098 n.d. 0.010 0.021 n.d. 0.141 0.010 0.141 0.063 0.010 358.02 358.00 0.01
    Th 0.657 0.291 1.01 0.332 0.045 0.101 0.301 1.23 0.045 1.23 0.496 0.011 457.21 457.20 0.00
    U 0.231 0.367 0.983 0.145 0.079 0.071 0.452 0.623 0.071 0.983 0.369 0.003 461.55 461.50 0.01
    ∑REEs 13.9 7.46 22.0 7.46 2.27 3.41 8.06 31.6 2.27 31.6 12.0
    LREE/HREE 18.3 13.1 16.0 13.9 22.1 20.4 30.7 21.7 13.1 30.7 19.5
    LaCN/LuCN 7.80 n.d. 19.8 n.d. n.d. n.d. 8.34 n.d. 7.80 19.8 12.0
    (Eu/Eu*)CN 2.62 0.443 0.314 n.d. 5.08 1.62 0.638 0.661 0.314 5.08 1.62
    (Ce/Ce*)CN 1.70 1.44 1.69 1.75 0.837 1.38 1.43 1.68 0.837 1.75 1.49
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    表 3  使用LA-MC-ICP-MS分析唐印热液区样品R11-H2中硬石膏的硫同位素组成

    Table 3.  Sulfur isotopic compositions of the anhydrite crystals in sample R11-H2 from the Tangyin hydrothermal field determined by LA-MC-ICP-MS

    测试点 矿物 δ34Sv-CDT/‰ 2SE
    4-1-1 硬石膏 20.08 0.31
    4-1-2 硬石膏 18.32 0.82
    4-1-3 硬石膏 20.26 0.42
    4-1-4 硬石膏 19.82 0.28
    标准物质
    PSPT-3
    闪锌矿 26.36 0.29
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收稿日期:  2023-06-06
修回日期:  2023-07-27
刊出日期:  2023-10-28

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