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西南印度洋中脊龙旂热液区中硫化物的结构和微量元素特征

陈柯安 张慧超 陶春辉 梁锦 杨伟芳 廖时理

陈柯安,张慧超,陶春辉,等. 西南印度洋中脊龙旂热液区中硫化物的结构和微量元素特征−对金赋存形式和沉淀机制的启示[J]. 海洋学报,2023,45(6):93–108 doi: 10.12284/hyxb2023061
引用本文: 陈柯安,张慧超,陶春辉,等. 西南印度洋中脊龙旂热液区中硫化物的结构和微量元素特征−对金赋存形式和沉淀机制的启示[J]. 海洋学报,2023,45(6):93–108 doi: 10.12284/hyxb2023061
Chen Kean,Zhang Huichao,Tao Chunhui, et al. Textural and trace elemental characteristics of sulfide from the Longqi hydrothermal field, Southwest Indian Ridge−Implication for the occurrence and precipitation mechanism of gold[J]. Haiyang Xuebao,2023, 45(6):93–108 doi: 10.12284/hyxb2023061
Citation: Chen Kean,Zhang Huichao,Tao Chunhui, et al. Textural and trace elemental characteristics of sulfide from the Longqi hydrothermal field, Southwest Indian Ridge−Implication for the occurrence and precipitation mechanism of gold[J]. Haiyang Xuebao,2023, 45(6):93–108 doi: 10.12284/hyxb2023061

西南印度洋中脊龙旂热液区中硫化物的结构和微量元素特征对金赋存形式和沉淀机制的启示

doi: 10.12284/hyxb2023061
基金项目: 国家自然科学基金(41802113,42127807);中央高校基本科研业务费(2019B08214);自然资源部第二海洋研究所及中央级公益性研院所基本科研业务费专项资金(SZ2201);中国大洋协会项目(DY135S1-01)。
详细信息
    作者简介:

    陈柯安(1998-),男,河南省商丘市人,主要研究方向为海底热液硫化物中金的成矿作用。E-mail:1187937175@qq.com

    通讯作者:

    张慧超(1990-),男,博士,讲师,硕士生导师,主要研究方向为热液金矿成矿作用。E-mail:zhanghch2012@126.com

  • 中图分类号: P736.4

Textural and trace elemental characteristics of sulfide from the Longqi hydrothermal field, Southwest Indian RidgeImplication for the occurrence and precipitation mechanism of gold

  • 摘要: 相比于快速和中速扩张洋中脊,慢速和超慢速扩张洋中脊热液区通常含有丰富的金属硫化物资源。近年来的研究表明大洋中脊的扩张速率与矿石中金的品位呈明显的负相关,即超慢速扩张洋中脊热液区矿石中金的含量高。前人对龙旂热液区的构造环境以及硫化物组合进行了详细研究,但是对龙旂热液区硫化物中贵金属金的赋存形式和沉淀机制研究较少。本文对西南印度洋龙旂热液区中的硫化物进行了精细的矿物结构和微量元素分析,并探讨了金的赋存形式和沉淀机制。龙旂热液区的硫化物主要以黄铁矿为主,其次是黄铜矿和闪锌矿,黄铜矿普遍出溶等轴古巴矿,此外还观察到了少量的针钠铁矾和自然金等矿物。根据矿物结构和形态,黄铁矿明显被划分为两期,一期黄铁矿(Py1)自形度低,呈细粒状或胶状,内部多孔洞;二期黄铁矿(Py2)自形度高,呈自形−半自形,且粒径较大。Py1往往存在于Py2内部或以包体的形式被Py2所包裹,Py2则与自形−半自形黄铜矿和闪锌矿等矿物共生。自然金主要存在于Py1的内部孔洞之中,少量存在于Py2以及Py2与其他硫化物之间。相比于Py2,Py1含有更高的Ni、Zn、Pb、Ba、Mn、V、Mg、U、Au、Ag、Cd元素含量,更低的Co、Se、As、Sb元素含量。在龙旂热液区的物理化学条件下,热液流体中金的主要存在形式为Au(HS),HS浓度的降低和pH值升高均会促进金的沉淀。龙旂热液区早期热液流体与海水的混合造成热液流体pH值升高,而混合作用导致的热液流体温度降低会促使黄铁矿(Py1)的结晶,从而促使热液流体中HS浓度的降低,热液流体pH值升高和黄铁矿结晶(Py1)引起的硫逸度降低是龙旂热液区自然金沉淀的主要机制。
  • 图  1  西南印度洋龙旂热液区地理位置[29]

    Fig.  1  Geographical location of Longqi hydrothermal field in Southwest Indian Ocean[29]

    图  2  西南印度洋龙旂热液区代表性硫化物样品

    Fig.  2  Representative sulfide samples from the Longqi hydrothermal field in Southwest Indian Ocean

    图  3  龙旂热液区黄铁矿显微照片(I)

    a−b:存在于自形黄铁矿内部的细粒黄铁矿;c−e:细粒黄铁矿包体;f:细粒黄铁矿被自形黄铁矿包围;Py1:一期黄铁矿,Py2:二期黄铁矿,Sp:闪锌矿,Ccp:黄铜矿

    Fig.  3  Photomicrograph of pyrite in Longqi hydrothermal field(I)

    a−b: Fine-grained pyrite found in the euhedral pyrite; c−e: fine-grained pyrite inclusions; f: fine-grained pyrite is surrounded by euhedral pyrite; Py1: pyrite I, Py2: pyrite II, Sp: sphalerite, Ccp: chalcopyrite

    图  4  龙旂热液区黄铁矿显微照片(II)

    a−c,f:黄铜矿和闪锌矿填充黄铁矿内部的孔洞;d−e:闪锌矿内部含有黄铜矿;Py1:一期黄铁矿,Py2:二期黄铁矿,Sp:闪锌矿,Ccp:黄铜矿

    Fig.  4  Photomicrograph of pyrite in Longqi hydrothermal field(II)

    a−c, f: Chalcopyrite and sphalerite fill the pores of pyrite; d−e: the sphalerite contains chalcopyrite; Py1: pyrite I, Py2: pyrite II, Sp: sphalerite, Ccp: chalcopyrite

    图  5  龙旂热液区黄铜矿显微照片

    a−b:以环状集合体形式出现的黄铜矿;c:黄铜矿出溶等轴古巴矿;d−f:和闪锌矿共生的黄铜矿;Py1:一期黄铁矿,Py2:二期黄铁矿,Sp:闪锌矿,Ccp:黄铜矿,Iso:等轴古巴矿

    Fig.  5  Photomicrograph of chalcopyrite in Longqi hydrothermal field

    a−b: Chalcopyrite occurs as annular aggregate; c: exsolution texture of isocubanite; d−f: coexistence of chalcopyrite and sphalerite symbiosis; Py1: pyrite I, Py2: pyrite II, Sp: sphalerite, Ccp: chalcopyrite, Iso: isocubanite

    图  6  龙旂热液区闪锌矿及针钠铁矾矿显微照片

    a:闪锌矿大块集合体;b−d:与黄铜矿共生的闪锌矿;e−f:存在于黄铁矿和闪锌矿附近的针钠铁矾;Py1:一期黄铁矿,Py2:二期黄铁矿,Sp:闪锌矿,Ccp:黄铜矿,Iso:等轴古巴矿,Frt:针钠铁矾

    Fig.  6  Photomicrograph of sphalerite and ferronatrite in Longqi hydrothermal field

    a: Large aggregate of sphalerite; b−d: symbiosis of sphalerite and chalcopyrite; e−f: ferronatrite found near pyrite and sphalerite; Py1: pyrite I, Py2: pyrite II, Sp: sphalerite, Ccp: chalcopyrite, Iso: isocubanite, Frt: ferronatrite

    图  7  龙旂热液区自然金显微照片

    a−c:存在于细粒黄铁矿和其他矿物溶蚀孔洞之中的自然金;d−e: 包裹于自形黄铁矿中的自然金;f:存在于黄铁矿和其他矿物之间的自然金;Py1:一期黄铁矿,Py2:二期黄铁矿,Sp:闪锌矿,Ccp:黄铜矿,Au:自然金

    Fig.  7  Photomicrograph of Native gold in Longqi hydrothermal field

    a−c: Native gold found in pores of fine-pyrite and other minerals; d−e: native gold occurs in euhedral pyrite f: native gold found between pyrite and other mineral; Py1: pyrite I, Py2: pyrite II, Sp: sphalerite, Ccp: chalcopyrite, Au: gold

    图  8  黄铁矿、闪锌矿、黄铜矿中部分主微量元素的时间分辨LA-ICP-MS深度剖面

    Fig.  8  Time-resolved LA-ICP-MS depth profiles of pyrite,sphalerite and chalcopyrite

    图  9  两期黄铁矿中微量元素含量对比

    Py1:一期黄铁矿,Py2:二期黄铁矿

    Fig.  9  Comparison of trace elements in pyrite of two types

    Py1: pyrite I, Py2: pyrite II

    表  1  黄铁矿、黄铜矿、闪锌矿的LA-ICP-MS分析结果

    Tab.  1  LA-ICP-MS analysis results of pyrite、chalcopyrite and sphalerite

    类型样品编号含量/10−6
    Cu(1σ)Zn(1σ)V(1σ)Mn(1σ)Co(1σ)Ni(1σ)As(1σ)Se(1σ)Mo(1σ)Ag(1σ)Sn(1σ)Sb(1σ)Ba(1σ)Au(1σ)Pb(1σ)U(1σ)
    一期黄铁矿19II-S7-TVG4-2-1173(6.76)4.55(1.33)0.45(0.04)124(7.63)0.43(0.10)138(5.11)0.25(0.29)7.15(0.95)8.23(0.71)1.34(0.11)5.43(0.27)0.05(0.03)1.68(0.19)76.0(7.21)0.01(0.00)
    19II-S7-TVG4-2-2138(4.70)10.8(0.84)0.52(0.04)0.88(0.11)12.4(2.27)1.20(0.12)19.5(2.31)0.86(0.24)22.3(0.49)14.4(0.58)1.48(0.08)1.91(0.17)2.77(0.11)226(6.00)
    19II-S7-TVG4-7-1669(24.8)745(30.8)0.88(0.06)283(6.64)10.8(0.68)1.67(0.18)34.5(1.09)2.16(0.31)26.8(0.82)115(3.21)5.57(0.20)2.80(0.11)0.18(0.05)2.60(0.11)93.4(1.67)0.03(0.01)
    19II-S7-TVG4-7-2365(16.6)181(10.0)0.62(0.04)174(7.51)282(16.2)0.81(0.12)39.8(1.22)3.79(0.50)15.4(0.70)57.8(2.39)3.86(0.18)2.38(0.13)0.12(0.03)1.58(0.10)63.2(2.15)0.01(0.00)
    19II-S7-TVG4-7-3853(31.1)2497(80.8)1.05(0.12)647(21.2)2.38(0.12)0.87(0.11)29.0(0.91)2.79(0.43)16.8(0.62)143(6.14)4.47(0.18)3.96(0.24)0.34(0.07)1.79(0.09)117(3.94)0.02(0.00)
    19II-S7-TVG4-7-41030(36.6)795(38.6)0.60(0.04)113(3.24)10.8(0.67)2.02(0.17)29.5(0.57)2.98(0.30)49.2(1.57)158(6.58)4.71(0.16)4.50(0.17)0.14(0.03)3.01(0.13)130(2.86)0.15(0.10)
    19II-S7-TVG4-7-5414(15.7)4742(165)0.56(0.04)12.8(0.43)1.52(0.20)0.93(0.11)6.18(0.36)1.01(0.25)12.0(0.33)9.78(0.38)1.42(0.08)1.47(0.11)2.02(0.10)130(2.01)0.02(0.00)
    19II-S7-TVG4-7-61563(86.3)2619(68.7)0.72(0.06)57.1(3.16)584(32.2)1.00(0.13)28.4(1.41)2.56(0.44)14.8(0.80)257(13.1)19.5(0.94)8.63(0.52)0.28(0.07)4.67(0.29)219(10.6)0.01(0.00)
    19II-S7-TVG4-7-71685(66.7)2129(49.8)0.45(0.04)49.9(2.60)640(29.7)0.64(0.10)38.5(1.34)2.77(0.37)13.9(0.60)254(9.78)19.6(0.63)8.08(0.29)0.11(0.04)4.71(0.20)225(7.79)0.01(0.00)
    19II-S7-TVG4-7-81217(68.3)387(13.1)0.71(0.05)313(10.5)856(32.1)1.39(0.13)28.7(0.73)4.69(0.48)37.2(1.79)131(5.84)8.91(0.34)4.04(0.22)0.11(0.03)3.57(0.19)138(5.25)0.02(0.00)
    19II-S7-TVG4-7-9727(27.2)918(56.1)0.78(0.05)440(10.6)253(12.9)2.27(0.17)26.3(0.65)4.00(0.38)59.3(2.98)113(4.64)3.26(0.15)2.93(0.14)0.16(0.04)2.21(0.11)104(3.02)0.05(0.00)
    19II-S7-TVG4-7-10465(15.1)212(13.1)0.45(0.04)236(8.80)1200(57.3)0.48(0.70)36.9(0.98)6.98(0.50)14.9(0.65)75.8(2.46)3.87(0.14)2.38(0.11)0.09(0.03)1.49(0.08)79.6(2.61)
    19II-S7-TVG4-7-11602(21.9)784(32.7)0.72(0.05)420(14.1)31.2(2.40)0.95(0.10)25.5(0.74)3.87(0.38)25.8(0.98)88.6(3.33)3.74(0.18)2.87(0.16)0.14(0.04)1.61(0.10)94.6(3.50)0.02(0.00)
    最大值168547421.0564712002.271386.9859.325719.68.630.344.712260.15
    最小值1384.550.450.881.520.436.180.257.158.231.341.470.051.4963.20.01
    平均值78213850.672293471.1641.73.0625.51136.844.10.162.661320.04
    二期黄铁矿19II-S7-TVG4-2-374.3(3.29)3.38(0.48)0.35(0.04)0.40(0.11)931(62.0)0.26(0.07)162(9.64)0.42(0.29)5.57(0.38)5.54(0.27)0.55(0.09)4.87(0.29)0.02(0.02)1.53(0.09)87.6(4.67)
    19II-S7-TVG4-2-462.6(1.68)66.5(7.19)0.34(0.03)0.78(0.14)120(23.0)0.48(0.08)46.4(3.60)0.36(0.22)11.5(0.65)4.89(0.21)0.50(0.05)1.61(0.11)1.05(0.06)179(4.24)
    二期黄铁矿19II-S7-TVG4-2-566.0(3.82)7.15(1.53)0.30(0.03)0.38(0.09)1113(79.1)0.16(0.06)307(8.36)0.47(0.26)1.92(0.13)2.41(0.15)0.65(0.07)5.63(0.20)0.79(0.08)94.8(1.62)
    19II-S7-TVG4-2-675.4(2.30)138(19.1)0.44(0.03)1.49(0.10)0.82(0.05)0.73(0.10)4.10(0.41)1.18(0.24)17.8(0.46)3.16(0.19)0.31(0.05)0.63(0.05)1.13(0.08)221(6.84)
    19II-S7-TVG4-2-7181(5.51)4046(246)0.47(0.03)2.05(0.12)37.1(4.46)1.21(0.11)42.0(3.25)0.39(0.26)22.0(0.91)4.64(0.25)0.59(0.06)1.40(0.12)1.01(0.06)198(6.24)
    19II-S7-TVG4-6-143.0(2.41)1.47(0.37)0.13(0.02)0.70(0.67)0.28(0.20)370(6.45)0.6(0.20)0.50(0.06)0.94(0.09)0.17(0.06)10.5(0.31)0.03(0.03)0.13(0.02)3.03(0.27)
    19II-S7-TVG4-6-2122(5.80)44.7(5.41)0.24(0.02)0.09(0.08)0.29(0.05)0.16(0.10)65.2(2.18)0.31(0.05)6.58(0.36)0.67(0.06)16.3(0.60)0.34(0.03)5.16(0.23)
    19II-S7-TVG4-6-3107(4.27)184(6.94)0.18(0.02)0.21(0.07)0.03(0.01)0.01(0.02)151(6.97)0.14(0.03)4.70(0.34)0.56(0.06)14.4(0.40)0.02(0.02)0.38(0.03)4.32(0.17)
    19II-S7-TVG4-7-1254.1(3.98)16.5(1.74)0.18(0.02)2702(84.5)342(8.81)22.6(0.88)0.22(0.04)2.02(0.17)0.37(0.05)5.52(0.21)0.15(0.02)6.67(0.36)
    19II-S7-TVG4-7-1331.6(1.38)1512(68)0.17(0.02)3269(83.0)0.04(0.03)327(5.84)24.7(1.33)0.20(0.04)1.69(0.11)0.09(0.04)5.77(0.17)0.06(0.01)1.12(0.06)
    19II-S7-TVG4-7-1462.7(5.43)17.0(1.80)0.17(0.03)0.17(0.08)2556(145)327(3.72)29.2(1.98)0.79(0.13)3.21(0.19)0.40(0.07)4.77(0.17)0.11(0.02)13.1(0.45)
    19II-S7-TVG4-7-1525.2(0.99)9.73(1.58)0.16(0.02)5534(267)0.02(0.03)326(7.54)45.6(1.94)0.35(0.05)0.80(0.07)0.04(0.05)6.94(0.22)0.09(0.02)1.91(0.22)
    19II-S7-TVG4-7-1621.5(1.00)13.5(1.43)0.17(0.03)0.08(0.07)5848(313)1.65(1.67)334(7.68)48.2(1.90)0.28(0.05)0.38(0.05)0.16(0.04)6.92(0.22)0.01(0.01)0.04(0.01)0.47(0.05)
    最大值18140460.472.0558481.6537048.2226.580.6716.30.031.53221
    最小值21.51.470.130.080.030.014.10.360.140.380.040.630.010.040.47
    平均值75.36740.260.7118640.5121617.15.583.190.386.810.020.5669.2
    闪锌矿19II-S7-TVG4-2-8335842(6262)287(9.97)0.09(0.04)4.83(0.34)44.3(1.10)0.36(0.15)70.6(4.02)61.8(1.84)6.23(0.29)0.03(0.02)0.24(0.06)0.02(0.01)
    19II-S7-TVG4-2-9336661(6154)175(6.25)0.03(0.04)3.35(0.35)43.5(0.97)0.23(0.12)42.9(2.43)0.02(0.04)62.8(1.85)4.95(0.30)0.04(0.08)0.07(0.04)0.11(0.05)
    19II-S7-TVG4-2-10324280(5933)153(4.93)0.14(0.05)3.36(0.32)44.5(1.42)0.41(0.15)1.43(0.37)45.7(2.19)61.1(1.79)4.18(0.28)0.22(0.04)0.03(0.04)
    19II-S7-TVG4-2-11345651(8092)526(12.8)6.58(0.31)52.9(1.35)39.4(2.16)0.03(0.04)52.2(1.73)4.18(0.22)0.19(0.06)0.04(0.03)0.23(0.05)
    闪锌矿19II-S7-TVG4-2-12330451(5126)1054(23.1)0.11(0.04)7.88(0.34)59.4(1.39)0.27(0.13)34.6(2.07)52.1(1.32)4.91(0.24)0.09(0.06)0.13(0.03)0.05(0.04)
    19II-S7-TVG4-2-13336351(5833)479(10.0)0.05(0.03)6.15(0.32)53.1(1.24)0.47(0.11)1.12(0.40)44.3(2.29)48.3(1.09)4.03(0.22)0.29(0.07)0.01(0.01)0.18(0.04)0.22(0.04)
    19II-S7-TVG4-2-14330208(5120)133(3.77)5.01(0.26)52.6(1.27)61.9(2.82)59.3(1.39)7.01(0.32)0.06(0.06)0.02(0.03)0.26(0.04)0.13(0.04)
    19II-S7-TVG4-2-15333972(5083)137(4.73)0.14(0.04)5.01(0.29)45.3(0.96)0.29(0.13)69.7(2.91)65.5(1.66)7.66(0.30)0.16(0.04)
    19II-S7-TVG4-2-16343704(4923)144(4.58)0.02(0.03)5.13(0.31)47.7(0.97)0.15(0.13)0.74(0.36)59.6(2.84)0.06(0.03)61.1(1.34)5.04(0.28)0.06(0.06)0.20(0.04)0.09(0.04)0.01(0.00)
    最大值34565110540.147.8859.40.471.4370.60.0665.57.660.290.070.260.220.02
    最小值3242801330.023.3543.50.150.7434.60.0248.34.030.040.010.130.030.01
    平均值3351863890.085.3249.70.311.0952.20.04585.440.130.040.20.110.02
    黄铜矿19II-S7-TVG4-7-175793(97.9)643760(10220)56.8(1.20)8.32(0.25)0.03(0.01)9.44(0.39)1.66(0.37)388(5.60)4.08(0.16)4.80(0.22)0.37(0.03)553(8.40)
    19II-S7-TVG4-7-183996(98.0)644943(10652)38.9(0.92)8.97(0.20)0.03(0.02)6.85(0.29)1.31(0.34)382(11.4)8.52(0.24)3.51(0.13)0.83(0.05)407(11.0)
    19II-S7-TVG4-7-193452(58.8)639219(10078)30.4(0.56)9.63(0.23)0.04(0.03)7.72(0.27)1.33(0.30)209(4.56)11.7(0.21)3.08(0.11)0.01(0.01)0.45(0.04)209(4.58)
    19II-S7-TVG4-7-205574(128)640315(10063)0.04(0.02)65.1(1.51)8.90(0.20)8.3(0.30)460(5.07)4.13(0.20)11.3(0.50)0.70(0.04)439(3.88)
    19II-S7-TVG4-7-214005(100)625020(9235)0.07(0.02)56.6(1.19)0.43(0.06)0.06(0.04)0.49(0.16)1.16(0.28)1680(53.0)653(16.9)90.9(1.84)0.02(0.01)0.91(0.05)188(5.98)
    19II-S7-TVG4-7-224416(57.8)618220(10031)37.6(0.56)18.3(0.28)5.77(0.30)1.02(0.30)158(3.03)39.2(0.63)11.1(0.22)0.01(0.01)0.18(0.02)59.9(4.46)
    19II-S7-TVG4-7-236117(103)639676(10343)0.02(0.01)36.6(0.73)9.65(0.26)0.05(0.03)8.79(0.30)1.81(0.30)418(8.79)73.6(1.03)20.4(0.47)0.50(0.04)268(7.03)
    19II-S7-TVG4-7-244927(67.3)643376(10009)0.04(0.02)32.8(0.72)9.24(0.26)0.09(0.03)6.56(0.29)0.48(0.31)0.01(0.01)452(7.19)33.5(0.92)8.52(0.28)0.53(0.04)159(4.38)
    最大值61176449430.0765.118.30.099.441.810.01168065390.90.020.91553
    最小值34526182200.0230.40.430.030.490.480.011584.083.080.010.1859.9
    平均值47856357690.04459.220.056.391.230.01599148.524.80.010.56290
    注:“—”代表含量在仪器检测限之下;1σ 为一倍标准偏差。
    下载: 导出CSV
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  • 收稿日期:  2022-07-29
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