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    海南岛罗葵洞斑岩钼矿床地球化学特征及成矿物质来源

    朱昱桦 陈根文 单强 许德如 王历星 何妙玲 兰永文 孙俊

    朱昱桦, 陈根文, 单强, 许德如, 王历星, 何妙玲, 兰永文, 孙俊, 2020. 海南岛罗葵洞斑岩钼矿床地球化学特征及成矿物质来源. 地球科学, 45(4): 1187-1212. doi: 10.3799/dqkx.2019.101
    引用本文: 朱昱桦, 陈根文, 单强, 许德如, 王历星, 何妙玲, 兰永文, 孙俊, 2020. 海南岛罗葵洞斑岩钼矿床地球化学特征及成矿物质来源. 地球科学, 45(4): 1187-1212. doi: 10.3799/dqkx.2019.101
    Zhu Yuhua, Chen Genwen, Shan Qiang, Xu Deru, Wang Lixing, He Miaoling, Lan Yongwen, Sun Jun, 2020. Geochemical Characteristics and Ore-Forming Materials of Luokuidong Molybdenum Ore Deposit in Hainan Island. Earth Science, 45(4): 1187-1212. doi: 10.3799/dqkx.2019.101
    Citation: Zhu Yuhua, Chen Genwen, Shan Qiang, Xu Deru, Wang Lixing, He Miaoling, Lan Yongwen, Sun Jun, 2020. Geochemical Characteristics and Ore-Forming Materials of Luokuidong Molybdenum Ore Deposit in Hainan Island. Earth Science, 45(4): 1187-1212. doi: 10.3799/dqkx.2019.101

    海南岛罗葵洞斑岩钼矿床地球化学特征及成矿物质来源

    doi: 10.3799/dqkx.2019.101
    基金项目: 

    国家重点研发计划深地资源勘查开采重点专项 2016YFC0600401

    国土资源部全国矿产资源潜力评价项目 1212010881625

    详细信息
      作者简介:

      朱昱桦(1989-), 男, 工程师, 矿物学、岩石学、矿床学专业

      通讯作者:

      许德如(1966-), 男, E-mail:xuderu@gig.ac.cn

    • 中图分类号: P611

    Geochemical Characteristics and Ore-Forming Materials of Luokuidong Molybdenum Ore Deposit in Hainan Island

    • 摘要: 为了正确理解海南岛罗葵洞钼矿床赋矿斑岩体的岩石学成因与成矿之间的关系以及成矿物质来源,对矿床中含矿斑状花岗岩进行了全岩主量、微量、Sr-Nd-Pb同位素和金属硫化物S-Pb同位素等测试分析,结果表明:(1)罗葵洞斑状花岗岩具有高SiO2(70.94%~72.59%)、Al2O3(15.11%~16.26%)和低MgO(0.56%~0.68%),高Sr(421×10-6~564×10-6)、低Y(7.50×10-6~14.57×10-6)和Yb(0.76×10-6~1.30×10-6)含量,较弱的负Eu异常(平均0.75),亏损HFSE,富集LREE和LILE,较高的La/Yb(26.1~46.4)与Sr/Y(36.9~67.1)比值特征,表现出与埃达克岩相似的地球化学特征;(2)斑状花岗岩的(87Sr/86Sr)i=0.708 38~0.708 44,(143Nd/144Nd)i=0.512 22~0.512 23,εNdt)=-5.6~-5.5,对应的TDM2模式年龄为1.35~1.36 Ga,表明其可能形成于底侵的增厚玄武质下地壳岩石(中元古代)的重熔;(3)全岩锆饱和温度(平均795±12℃(σ))和锆石Ti温度(平均690±21℃(σ))表明斑状花岗岩岩浆来源于在水近饱和条件下发生的部分熔融;(4)锆石Ce4+/Ce3+比值范围为174~621(平均383),表明其在形成时的岩浆-热液体系的氧逸度较高,有利于Mo等成矿元素在岩浆熔体中富集,成矿潜力较大;(5)金属硫化物δ34S(平均1.7‰)和Pb同位素特征指示成矿物质来源以下地壳为主,同时伴有少量地幔成分的参与;(6)对比年代学、矿物学、地球化学和形成环境等方面后,初步认为该矿床属于Endako型斑岩钼矿床.

       

    • 图  1  海南岛位置简图(a)和海南岛地层、构造及相关钼矿床位置地质简图(b)

      均据Xu et al.(2016)修改. 1.中生代-新生代地层;2.新生代玄武岩;3.白垩纪盆地;4.古生代地层;5.晚中元古-新元古代石碌群和上覆石灰顶组;6.古-中元古代抱板群;7.新太古代杂岩(?);8.晚中生代花岗质岩类;9.白垩纪火山岩;10.晚古生代-早古生代花岗质岩类;11.变基性岩和相关沉积岩;12.地质界线;13.钼(多金属)矿床(矿化点),包括①红门岭、②红岭、③报告村、④文且、⑤石门山、⑥新村、⑦罗葵洞、⑧龙门岭、⑨高通岭、⑩梅岭

      Fig.  1.  Location map of Hainan Island (a); geological sketch map showing major stratigraphic and magmatic units, structures and molybdenum (Mo)-related ore deposits or occurrences on Hainan Island (b)

      图  2  罗葵洞钼矿区及邻区地质简图

      朱昱桦等(2018)修改. 1.第四系含砂粘土、砂砾石;2.白垩系六罗村组中-酸性火山碎屑岩、火山岩类;3.白垩纪石英二长(斑)岩、石英正长岩;4.白垩纪斑状花岗岩(主);5.白垩纪花岗闪长岩;6.侏罗纪(白垩纪?)中-粗粒花岗岩;7.英安斑岩;8.安山玢岩;9.辉绿岩;10.含钼强硅蚀变带;11.含钼硅钾蚀变带;12.含钼硅化蚀变带;13.遥感环形影像;14.实测(F1)与推测(物探WF1/遥感YF1)断层;15.7’号剖面线;16.斑状花岗岩采样位置;17.矿石样采样位置;18.钻孔位置及编号

      Fig.  2.  Simplified geological map showing the Luokuidong mining district and its adjacent areas

      图  3  罗葵洞钼矿床矿区7’号线地质剖面图

      据辽宁省有色地质局勘查总院(2008)海南省保亭县罗葵洞矿区钼矿详查地质报告.1.第四系残坡积层;2.白垩系六罗村组中-酸性火山碎屑岩、火山岩类;3.白垩纪花岗质岩石;4.工业矿体(0.040%≤Mo≤0.170%,平均0.058%);5.低品位矿体(0.020%≤Mo < 0.040%,平均0.025%);6.矿化体;7.层序界线;8.钻孔位置及编号

      Fig.  3.  Geological section map of the No. 7' prospecting line in the Luokuidong molybdenum ore deposit

      图  4  斑状花岗岩标本截面(a);斑状花岗岩正交偏光显微镜下特征(b~c);斑状花岗岩上见少量浸染状辉钼矿(d);石英-辉钼矿阶段中的金属硫化物(e~f)

      Bt.黑云母;Ccp.黄铜矿;Chl.绿泥石;Kfs.钾长石;Mo.辉钼矿;Pl.斜长石;Py.黄铁矿;Qz.石英

      Fig.  4.  The section of porphyritic granite (a); photographs from orthogonal polarizing microscope of porphyritic granite (b-c); A small amount of molybdenite in porphyritic granite (d); Metal sulfide from quartz-molybdenite stage (e-f)

      图  5  岩浆岩TAS图解(a);硅-钾图(b);球粒陨石标准化稀土元素分布模式(c);原始地幔标准化微量元素蛛网图(d);Sr/Y-Y图解(e);(La/Yb)N-YbN图解(f)

      图a据Martin(1993);图b据Peccerillo and Taylor(1976)Middlemost(1985);图c据Sun et al.(1989),其中海南屯昌埃达克质岩贾小辉等(2010)Wang et al.(2012),六罗村组流纹岩周云等(2015)Zhou et al.(2015);图d据Sun et al.(1989);图e据Defant and Drummond(1990)Defant et al.(2002);图f据Martin(1993).1.橄榄辉长岩;2a.碱性辉长岩;2b.亚碱性辉长岩;3.辉长闪长岩;4.闪长岩;5.花岗闪长岩;6.花岗岩;7.硅英岩;8.二长辉长岩;9.二长闪长岩;10.二长岩;11.石英二长岩;12.正长岩;13.副长石辉长岩;14.副长石二长闪长岩;15.副长石二长正长岩;16.副长石正长岩;17.副长石深成岩;18.霓方钠岩/磷霞岩/粗白榴岩;Ir分界线上方为碱性系列,下方为亚碱性系列岩石

      Fig.  5.  Diagrams of TAS (a); SiO2-K2O (b); the chondrite-normalized rare earth elements (REE) (c); The primitive mantle-normalized multi-element diagrams(d); Sr/Y vs. Y (f) and (La/Yb)N vs.YbN(e)

      图  6  La-La/Yb、Th-Rb、Rb/V-Rb和Rb/V-1/V图解

      Schiano et al.(2010)

      Fig.  6.  La-La/Yb, Th-Rb, Rb/V-Rb and Rb/V-1/V diagrams

      图  7  罗葵洞钼矿区斑状花岗岩εNd(t)-(87Sr/86Sr)i图解(a);SiO2-MgO图解(b)

      图a中华南下地壳数据周云等(2015)及其参考文献,六罗村组火山岩数据周云等(2015)Zhou et al.(2015),屯昌早白垩世埃达克质侵入岩及镁铁质包体数据贾小辉等(2010)Wang et al. (2012)及其中的参考文献.图b据Wang et al.(2006, 2007)侯增谦等(2007)及其中的参考文献

      Fig.  7.  εNd(t)-(87Sr/86Sr)i diagram for the Luokuidong magmatic rocks (a) and MgO vs. SiO2 diagram for the Luokuidong(b)

      图  8  罗葵洞钼矿区Pb同位素图解

      Zartman and Doe(1981). UC.上地壳;OR.造山带;M.地幔;LC.下地壳

      Fig.  8.  Diagrams showing lead isotopic compositions of the Luokuidong

      图  9  构造背景示意图(a);成岩成矿过程示意图(b~c)

      图a据Xu et al.(2016)修改

      Fig.  9.  Tectonic setting(a) and rock formation and mineralization of Luokuidong(b-c)

      图  10  斑岩型钼矿床分类特征

      Fig.  10.  Characteristic of porphyry molybdenum deposit

      表  1  罗葵洞斑状花岗岩主量(%)、微量(10-6)元素测试结果

      Table  1.   Major (%) and trace elements (106) compositions from Luokuidong porphyritic granite

      样品号 16LK-21 16LK-22 16LK-23 16LK-24 16LK-25 16LK-26 16LK-27 17LK-01 17LK-02
      SiO2 72.41 71.94 71.50 72.07 72.59 71.66 70.94 72.16 72.34
      TiO2 0.29 0.33 0.33 0.27 0.30 0.32 0.33 0.30 0.31
      Al2O3 15.41 15.64 16.26 15.51 15.48 15.92 15.77 15.11 15.71
      MnO 0.04 0.05 0.05 0.04 0.05 0.06 0.04 0.05 0.05
      TFe2O3 2.01 2.23 1.79 1.83 2.25 1.99 2.73 1.97 1.80
      MgO 0.62 0.68 0.68 0.56 0.59 0.63 0.62 0.64 0.58
      CaO 0.84 1.44 1.53 1.32 1.05 1.47 1.68 1.97 1.17
      Na2O 3.23 3.20 3.36 2.94 2.65 3.45 3.44 3.69 2.72
      K2O 5.08 4.40 4.43 5.39 4.99 4.46 4.38 4.03 5.28
      P2O5 0.07 0.09 0.09 0.07 0.05 0.05 0.07 0.09 0.04
      Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00
      LOI 1.41 1.60 1.62 1.25 1.73 1.27 1.19 0.56 1.43
      Alk 8.31 7.59 7.78 8.32 7.64 7.91 7.82 7.72 8.00
      δ 2.35 1.99 2.13 2.38 1.97 2.18 2.19 2.04 2.18
      A/CNK 1.25 1.24 1.24 1.19 1.33 1.21 1.17 1.08 1.27
      A/NK 1.42 1.56 1.57 1.45 1.58 1.51 1.51 1.45 1.54
      Mg# 0.34 0.34 0.39 0.34 0.31 0.35 0.28 0.35 0.35
      K2O/Na2O 1.58 1.38 1.32 1.83 1.88 1.29 1.27 1.09 1.94
      TZr 799 799 799 783 801 801 812 772 790
      Sc 4.04 3.44 3.42 3.72 3.98 4.16 4.56 4.26 3.51
      Ti 1 658 1 940 1 948 1 621 1 809 1 851 1 935 1 836 1 721
      V 19.1 20.2 19.0 17.9 20.4 21.3 26.1 24.2 19.0
      Cr 17.2 13.0 10.9 12.7 14.2 11.2 12.7 13.9 13.0
      Mn 308 365 318 302 328 417 321 393 345
      Co 1.32 3.12 2.11 3.00 1.43 2.05 2.53 1.41 1.46
      Ni 5.24 2.62 2.14 2.46 3.60 2.36 2.97 2.30 2.70
      Cu 84.9 61.9 44.6 99.4 66.5 52.0 13.5 56.0 92.8
      Zn 51.9 43.0 50.8 49.5 76.7 181.9 58.5 175.8 49.6
      Ga 19.0 20.3 20.7 19.6 19.9 20.4 20.8 20.5 20.0
      Ge 1.38 1.55 1.32 1.27 1.42 1.35 1.52 1.48 1.30
      Rb 199 183 182 207 208 202 162 189 196
      Sr 436 487 533 503 421 519 537 564 438
      Y 10.4 10.0 8.0 7.5 8.1 11.0 14.6 14.5 8.0
      Zr 153 156 157 135 147 165 194 133 136
      Nb 8.1 8.3 7.9 8.2 8.9 9.1 9.6 9.3 7.8
      Cs 3.45 3.34 3.40 3.05 3.03 3.62 2.59 3.34 3.39
      Ba 995 708 904 1127 742 805 873 686 946
      La 35.3 41.9 28.3 30.9 36.0 27.8 39.4 40.5 30.5
      Ce 62.9 73.0 52.3 55.5 66.5 51.8 69.4 72.7 60.9
      Pr 6.70 8.21 5.78 5.75 7.10 5.37 7.74 7.89 6.31
      Nd 22.5 27.8 20.5 19.4 24.4 18.5 25.9 26.8 21.8
      Sm 3.48 4.17 3.22 2.95 3.56 2.69 3.75 3.93 3.23
      Eu 0.76 0.92 0.78 0.70 0.74 0.61 0.86 0.82 0.71
      Gd 2.69 3.06 2.42 2.19 2.64 2.24 3.02 3.13 2.46
      Tb 0.34 0.37 0.29 0.28 0.32 0.29 0.38 0.42 0.30
      Dy 1.78 1.83 1.51 1.40 1.60 1.64 2.04 2.27 1.57
      Ho 0.35 0.34 0.28 0.27 0.30 0.35 0.43 0.46 0.30
      Er 0.96 0.91 0.75 0.72 0.80 1.01 1.15 1.26 0.82
      Tm 0.15 0.14 0.11 0.11 0.12 0.15 0.18 0.20 0.12
      Yb 1.01 0.90 0.78 0.76 0.81 1.07 1.12 1.30 0.82
      Lu 0.15 0.14 0.12 0.12 0.12 0.17 0.19 0.20 0.13
      Hf 4.73 4.50 4.36 4.30 4.19 4.75 5.58 3.95 4.04
      Ta 0.78 0.61 0.58 0.73 0.63 0.69 0.75 0.67 0.61
      Pb 13.7 12.9 13.0 15.0 15.3 12.5 14.0 13.2 14.9
      Th 16.3 14.0 12.9 15.0 14.5 14.2 15.1 17.1 9.1
      U 2.25 1.83 1.68 2.10 2.25 3.39 2.44 2.69 2.02
      ∑REE 139 164 117 121 145 114 156 162 130
      δEu 0.73 0.75 0.82 0.80 0.70 0.73 0.75 0.69 0.75
      (La/Yb)N 25.2 33.3 26.1 29.2 31.9 18.7 25.4 22.4 26.6
      La/Yb 35.1 46.4 36.4 40.7 44.4 26.0 35.4 31.2 37.1
      Sr/Y 42.1 48.5 66.6 67.1 52.1 47.2 36.9 39.0 54.7
      Th/Ta 20.9 23.0 22.4 20.5 23.3 20.4 20.3 25.7 14.9
      Th/Nb 2.0 1.7 1.6 1.8 1.6 1.6 1.6 1.8 1.2
      注:LOI.烧失量;碱度Alk=Na2O+K2O;里特曼指数δ=(Na2O+K2O)2/(SiO2-43)(ωB,%);A/CNK=Al2O3/(CaO+K2O+Na2O),分子数比值;A/NK=Al2O3/(K2O+Na2O),分子数比值;Mg#=Mg2+/(Mg2++Fe2+)的摩尔数比值;TZr为全岩锆饱和温度计.
      下载: 导出CSV

      表  2  罗葵洞斑状花岗岩Sr-Nd同位素组成

      Table  2.   Sr-Nd isotopic compositions of the Luokuidong porphyritic granite

      样品编号 Rb(10-6 Sr(10-6 87Rb/86Sr 87Sr/86Srs (87Sr/86Sr)i Sm(10-6 Nd(10-6 147Sm/144Nd 143Nd/144Nd (143Nd/144Nd)i εNd(0) εNd(t) TDM2(Ma)
      16LK-22 183 487 1.09 0.709 963 0.000 020 0.708 38 4.17 27.8 0.090 655 0.512 281 0.000 010 0.512 22 -6.97 -5.6 1 354
      16LK-23 182 533 0.99 0.709 855 0.000 016 0.708 43 3.22 20.5 0.094 797 0.512 282 0.000 011 0.512 22 -6.95 -5.6 1 357
      17LK-01 189 564 0.97 0.709 839 0.000 020 0.708 44 3.93 26.8 0.088 580 0.512 284 0.000 011 0.512 23 -6.91 -5.5 1 347
      下载: 导出CSV

      表  3  罗葵洞斑状花岗岩Pb同位素组成

      Table  3.   Pb isotopic compositions of the Luokuidong porphyritic granite

      样品
      编号
      U
      (10-6
      Th
      (10-6
      Pb
      (10-6
      206Pb/
      204Pb
      207Pb/
      204Pb
      208Pb/
      204Pb
      (206Pb/
      204Pb)i
      (207Pb/
      204Pb)i
      (208Pb/
      204Pb)i
      μ ω
      16LK-22 1.83 14.0 12.9 18.941 0.000 8 15.635 0.000 8 38.991 0.002 3 18.795 15.628 38.626 9.48 36.23
      16LK-23 1.68 12.9 13.0 18.894 0.000 9 15.635 0.000 9 38.940 0.002 7 18.762 15.629 38.606 9.49 36.28
      17LK-01 2.69 17.1 13.2 19.042 0.000 9 15.647 0.000 8 39.040 0.002 2 18.832 15.637 38.603 9.50 36.02
      注:μ=238U/204Pb,ω=232Th/204Pb.
      下载: 导出CSV

      表  4  罗葵洞金属硫化物S-Pb同位素组成

      Table  4.   S and Pb istopic compositions for Luokuidong metal sulfides

      矿物 δSV-CDT34(‰) 206Pb/204Pb 平均 207Pb/204Pb 平均 208Pb/204Pb 平均 μ 平均 平均 ω 平均 平均 Th/U
      辉钼矿 3.3 18.692(0.011) 18.635 15.660(0.009) 15.628 38.811(0.024) 38.674 9.55 9.50 9.50 37.06 36.52 36.47 3.76
      1.6 18.679(0.001) 15.621(0.001) 38.674(0.003) 9.48 36.23 3.70
      2.5 18.658(0.004) 15.685(0.004) 38.901(0.007) 9.61 37.84 3.81
      2.9 18.744(0.006) 15.645(0.006) 38.777(0.018) 9.52 36.52 3.71
      2.4 18.543(0.004) 15.577(0.003) 38.406(0.007) 9.41 35.47 3.65
      3.7 18.492(0.002) 15.578(0.002) 38.472(0.004) 9.41 36.01 3.70
      黄铁矿 2.1 18.654(0.002) 18.687 15.646(0.002) 15.632 38.809(0.004) 38.708 9.53 9.50 37.13 36.42 3.77
      1.6 18.714(0.002) 15.652(0.002) 38.768(0.005) 9.54 36.70 3.72
      2.2 18.653(0.003) 15.620(0.002) 38.643(0.006) 9.48 36.23 3.70
      -4.7 18.698(0.003) 15.643(0.003) 38.724(0.009) 9.52 36.53 3.71
      1 18.658(0.002) 15.604(0.002) 38.610(0.004) 9.45 35.93 3.68
      2.1 18.744(0.002) 15.626(0.002) 38.695(0.004) 9.48 36.02 3.68
      注:μ=238U/204Pb,ω=232Th/204Pb.
      下载: 导出CSV

      表  5  罗葵洞斑状花岗岩(16LK-22)锆石Ce4+/Ce3+比值计算值

      Table  5.   Calculated Ce4+/Ce3+ ratios of zircons in the Luokuidong granite sample 16LK-22

      锆石编号 锆石Ce4+/
      Ce3+
      熔体Ce4+/Ce3+ D(Ce4+ D(Ce3+ D(Ce锆石/熔体
      16LK-22-2 174 0.000 890 810.113 738 0.004 148 0.725 508
      16LK-22-4 500 0.000 913 896.461 715 0.001 636 0.819 900
      16LK-22-5 198 0.000 927 782.932 100 0.003 661 0.729 655
      16LK-22-6 209 0.000 654 753.944 164 0.002 366 0.495 818
      16LK-22-7 544 0.000 878 801.997 038 0.001 295 0.705 816
      16LK-22-8 621 0.000 675 686.383 176 0.000 747 0.463 996
      16LK-22-11 347 0.000 810 770.383 170 0.001 798 0.625 953
      16LK-22-13 577 0.000 637 748.363 413 0.000 827 0.477 231
      16LK-22-16 384 0.000 750 706.709 990 0.001 382 0.531 316
      16LK-22-18 306 0.000 900 718.052 331 0.002 115 0.648 074
      16LK-22-19 188 0.000 918 724.125 709 0.003 541 0.668 523
      16LK-22-20 304 0.001 012 719.665 184 0.002 396 0.731 012
      16LK-22-21 375 0.000 934 717.837 055 0.001 787 0.672 084
      16LK-22-23 465 0.000 803 766.278 035 0.001 323 0.616 388
      16LK-22-27 213 0.001 121 829.556 966 0.004 381 0.934 451
      16LK-22-28 571 0.000 873 739.250 902 0.001 132 0.646 488
      16LK-22-29 533 0.001 093 699.556 320 0.001 437 0.766 053
      16LK-22-30 295 0.001 064 726.850 626 0.002 623 0.776 350
      16LK-22-35 467 0.000 960 691.609 170 0.001 422 0.665 422
      下载: 导出CSV
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