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滇东南南秧田钨矿床白钨矿原位Sr同位素对成矿的指示

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王忠强, 李超, 张定才, 江小均, 周利敏, 严清高. 滇东南南秧田钨矿床白钨矿原位Sr同位素对成矿的指示[J]. 岩矿测试, 2020, 39(2): 285-299. doi: 10.15898/j.cnki.11-2131/td.201907310117
引用本文: 王忠强, 李超, 张定才, 江小均, 周利敏, 严清高. 滇东南南秧田钨矿床白钨矿原位Sr同位素对成矿的指示[J]. 岩矿测试, 2020, 39(2): 285-299. doi: 10.15898/j.cnki.11-2131/td.201907310117
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Zhong-qiang WANG, Chao LI, Ding-cai ZHANG, Xiao-jun JIANG, Li-min ZHOU, Qing-gao YAN. Implication of in situ Sr Isotope of Scheelite for Tungsten Mineralization: A Case Study of the Nanyangtian Scheelite Deposit, Southeast Yunnan, China[J]. Rock and Mineral Analysis, 2020, 39(2): 285-299. doi: 10.15898/j.cnki.11-2131/td.201907310117
Citation: Zhong-qiang WANG, Chao LI, Ding-cai ZHANG, Xiao-jun JIANG, Li-min ZHOU, Qing-gao YAN. Implication of in situ Sr Isotope of Scheelite for Tungsten Mineralization: A Case Study of the Nanyangtian Scheelite Deposit, Southeast Yunnan, China[J]. Rock and Mineral Analysis, 2020, 39(2): 285-299. doi: 10.15898/j.cnki.11-2131/td.201907310117
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滇东南南秧田钨矿床白钨矿原位Sr同位素对成矿的指示

  • 1.

    昆明理工大学国土资源工程学院, 云南 昆明 650093

  • 2.

    国家地质实验测试中心, 北京 100037

  • 3.

    中国地质科学院Re-Os同位素地球化学重点实验室, 北京 100037

  • 4.

    文山麻栗坡紫金钨业集团有限公司, 云南 文山 663600

  • 基金项目:
    国家自然科学基金项目（41673060，41873065）
详细信息
    作者简介: 王忠强, 硕士研究生, 从事矿物学、地球化学研究。E-mail:kmustwzq@126.com
    通讯作者: 李超, 博士, 副研究员, 从事同位素地球化学研究。E-mail:Re-Os@163.com

  • 中图分类号: O628

Implication of in situ Sr Isotope of Scheelite for Tungsten Mineralization: A Case Study of the Nanyangtian Scheelite Deposit, Southeast Yunnan, China

  • 1.

    Faculty of Land Resource Engineering, Kunming University of Science and Technology, Kunming 650093, China

  • 2.

    National Research Center for Geoanalysis, Beijing 100037, China

  • 3.

    Key Laboratory of Re-Os Isotope Geochemistry, Chinese Academy of Geological Sciences, Beijing 100037, China

  • 4.

    Wenshan Malipo Zijin Tungsten Group Co., LTD. Wenshan 663600, China

More Information

    摘要
  • 南秧田钨矿床位于滇东南老君山W-Sn矿集区，地处扬子地块和印支地块的结合部位，地质背景复杂并遭受了多期岩浆活动和区域变质事件，其成矿时代和成因一直存在争议。本文对矽卡岩型和长石-石英脉型白钨矿开展了年代学、原位微量元素、Sr同位素研究，分析了两类白钨矿年龄、成因以及物质来源的差异。结果表明，长石-石英脉内与白钨矿共生辉钼矿的Re-Os同位素等时线年龄为151.0±1.3Ma，明显晚于矽卡岩矿体年龄，属于后期成矿事件。矽卡岩型白钨矿的轻稀土富集、重稀土强烈亏损，Eu呈明显负异常（δEu=0.46），∑REE平均含量为65.60μg/g，Mo平均含量为240.16μg/g，Sr平均含量为883.43μg/g；长石-石英脉型白钨矿稀土呈Eu正异常（δEu=2.8）的平坦型，∑REE平均含量为194.40μg/g，Mo平均含量为16.01μg/g，Sr平均含量为129.26μg/g。以上两者微量、稀土元素含量的差别显示它们具有性质明显不同的流体来源，Eu异常指示矽卡岩型白钨矿形成于氧逸度较高的环境，长石-石英脉型白钨矿形成于还原性环境。矽卡岩白钨矿87Sr/86Sr值相对较低，并且比较均一，介于0.71319~0.71491之间，表明成矿流体主要来自岩浆热液；长石-石英脉型白钨矿87Sr/86Sr值较高且变化范围大，介于0.71537~0.72803之间，平均0.72079，呈现出变质流体特征。两种不同类型白钨矿Sr同位素都具有二元混合的特征，显示长石-石英脉型白钨矿对矽卡岩型白钨矿有叠加改造作用，成矿流体与围岩的强烈交代作用是白钨矿形成的关键。
    BACKGROUNDThe Nanyangtian scheelite deposit is an important skarn scheelite deposit in Yunnan Province, which is located in Laojunshan W-Sn deposit area, Southeast Yunnan. Due to its complex geological background and multi-stage metallogenic characteristics, its mineralization age and genesis remain controversial. OBJECTIVESTo explore the metallogenic age, genesis and material origins of two types of scheelite deposits in order to explore formation patterns. METHODSMolybdenum Re-Os isotope dating was used to constrain the age, whereas in situ trace element and in situ Sr isotopes of scheelite were used to determine the composition of trace elements and Sr isotopes in scheelite. RESULTSThe Re-Os isochron age of molybdenite associated with scheelite in the feldspar-quartz mineral vein of Nanyantian was 151.0±1.3Ma, younger than the age of skarn mineralization, indicating a later mineralization event. The skarn-type scheelite was enriched in light rare earth elements with negative Eu anomaly (δEu=0.46). The average content of ∑REE, Mo and Sr in skarn scheelite were 65.60, 240.16 and 883.43μg/g, respectively. Feldspar-quartz vein-type scheelite showed a flat rare earth pattern with positive Eu anomaly (δEu=2.8) and average content of ∑REE, Mo and Sr were 194.40, 16.01 and 129.26μg/g, respectively. respectively. The skarn scheelite had a relatively low and uniform 87Sr/86Sr value of 0.71319 to 0.71491, indicating that the ore-forming fluids were mainly magmatic-hydrothermal in origin, whereas feldspar-quartz vein type scheelite had a wide 87Sr/86Sr range of 0.71537 to 0.72803, with an average of 0.72079, characteristic of metamorphic fluids. CONCLUSIONSThe differences in trace and rare earth element contents between two types of mineralization indicate that they have different fluid sources. The negative Eu anomaly of the skarn-type scheelite indicates a high oxygen fugacity environment, whereas the feldspar-quartz vein-type scheelite is formed in a reductive environment in terms of positive Eu anomaly. Sr isotopes of two different types of scheelite display a feature of binary mixing, indicating that feldspar-quartz vein-type scheelite has a superimposed transformation effect on skarn-type scheelite, and the strong metasomatism of ore-forming fluids and surrounding rocks is the key to the formation of scheelite.
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  • 图 1  南秧田钨矿床地质图(据冯佳睿等[16]、李建康等[17]修改)

    Figure 1. 

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    图 2  南秧田钨矿床样品特征

    Figure 2. 

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    图 3  长石-石英矿脉中辉钼矿等时线年龄图

    Figure 3. 

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    图 4  白钨矿稀土、微量元素以及Sr同位素比值特征(含矿矽卡岩稀土数据来源文献[22])

    Figure 4. 

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    表 1  长石-石英脉中辉钼矿Re-Os同位素分析结果

    Table 1.  Re-Os isotope analytical results of molybdate in feldspar-quartz veins

    样品编号 样品质量
    (g)    		 Re(μg/g) 普Os(ng/g) 187Re(μg/g) 187Os(ng/g) 模式年龄(Ma)
    测定值 2σ 测定值 2σ 测定值 2σ 测定值 2σ 测定值 2σ
    NYTS-16-1 0.00304 60.93 0.460 0.0309 0.0024 38.29 0.289 95.71 0.59 149.8 2.1
    NYTS-16-2 0.02081 197.6 1.723 0.5608 0.0454 124.2 3.768 313.7 2.1 151.4 2.3
    NYTS-16-3 0.01190 235.0 2.141 0.5961 0.0178 147.7 1.346 373.6 2.3 151.7 2.2
    NYTS-16-4 0.00309 213.1 1.678 0.1013 0.0077 133.9 1.055 333.9 2.0 149.4 2.1
    NYTS-16-5 0.00313 246.2 2.146 0.1744 0.0076 154.8 1.349 390.0 2.8 151.1 2.3
    下载: 导出CSV

    表 2  白钨矿中稀土元素含量测定结果

    Table 2.  Anaytical results of rare earth elements in scheelite

    白钨矿类型 样品编号 元素含量(μg/g) δEu
    Mo Sr Y La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu ∑REE
    矽卡岩型 NYTX-5-01 300.1 1202 0.15 8.21 28.80 5.73 24.13 1.18 0.07 0.73 0.03 0.05 0.01 0.03 < LOD < LOD 0.01 68.98 0.24
    NYTX-5-02 295.2 1332 0.24 18.60 52.48 8.57 36.18 2.20 0.15 0.85 0.04 0.07 < LOD < LOD 0.01 0.04 < LOD 119.18 0.36
    NYTX-5-03 283.7 1197 0.02 6.54 25.21 4.97 22.30 1.56 0.15 0.45 0.06 < LOD < LOD 0.06 < LOD 0.01 < LOD 61.30 0.60
    NYTX-5-04 237.8 1167 0.34 5.71 24.43 5.11 30.62 2.65 0.21 1.33 0.10 0.47 0.03 0.04 < LOD 0.01 < LOD 70.72 0.38
    NYTX-5-05 248.8 1167 0.52 8.33 28.80 4.95 23.28 1.73 0.12 0.68 0.03 0.15 0.03 0.09 < LOD < LOD < LOD 68.20 0.37
    NYTX-5-06 231.6 1191 1.20 7.33 27.39 5.61 32.38 3.49 0.25 1.90 0.18 0.48 0.10 0.23 0.00 0.07 < LOD 79.41 0.33
    NYTX-12-01 246.3 672.1 4.23 4.25 15.53 2.96 18.02 4.17 0.77 3.73 0.38 1.96 0.29 0.62 0.04 0.20 0.02 52.95 0.66
    NYTX-12-02 231.3 607.0 3.24 3.96 15.51 3.32 20.00 4.21 0.48 3.07 0.29 1.73 0.17 0.40 0.06 0.07 0.03 53.30 0.45
    NYTX-12-03 223.5 588.1 4.43 4.66 17.57 3.47 19.00 4.24 0.68 3.80 0.37 1.67 0.29 0.52 0.04 0.20 0.04 56.55 0.58
    NYTX-12-04 191.8 547.5 4.72 4.70 17.99 3.00 15.74 3.04 0.48 2.41 0.18 1.11 0.24 0.46 0.06 0.47 0.03 49.91 0.60
    NYTX-12-05 207.9 520.8 4.87 3.25 14.63 3.31 17.82 4.71 0.65 4.42 0.47 2.36 0.37 0.84 0.07 0.11 0.02 53.05 0.49
    NYTX-12-06 183.8 407.1 4.57 2.68 14.17 3.34 19.77 5.25 0.55 3.82 0.42 2.26 0.37 0.73 0.06 0.16 0.02 53.60 0.42
    长石-石英脉型 NYTS-1-01 19.0 136.0 174.20 7.83 30.75 6.59 41.23 15.67 6.61 16.33 3.50 26.85 5.92 19.34 2.64 15.93 2.16 201.35 1.41
    NYTS-1-02 19.4 106.4 52.82 3.31 8.45 1.54 8.32 3.58 1.59 4.26 1.16 6.40 1.96 5.89 0.77 4.71 0.94 52.87 1.39
    NYTS-1-03 17.8 150.4 91.45 4.75 23.19 5.68 29.20 8.41 7.19 8.28 1.42 10.27 2.66 7.95 1.38 8.33 1.29 119.98 2.94
    NYTS-1-04 21.5 149.9 299.92 41.05 86.35 12.79 62.13 15.88 9.40 17.89 3.64 28.31 7.14 22.83 4.72 34.81 4.72 351.65 1.90
    NYTS-1-05 25.4 147.4 115.65 5.13 29.22 6.12 34.18 9.97 9.09 10.18 1.79 12.52 3.31 8.66 1.66 10.33 1.42 143.58 3.08
    NYTS-1-06 18.5 156.0 78.63 6.28 29.29 6.54 34.74 8.53 8.80 8.56 1.43 8.57 2.19 6.05 0.91 4.96 0.86 127.71 3.51
    NYTS-2-01 17.1 165.3 120.68 16.43 39.71 7.26 42.71 13.38 11.60 16.78 3.98 28.50 6.19 18.28 2.33 11.63 1.44 220.20 2.64
    NYTS-2-02 15.8 181.8 82.32 5.44 26.48 5.87 30.35 8.32 8.43 7.77 1.62 12.49 3.11 10.01 1.50 9.37 1.31 132.06 3.58
    NYTS-2-03 18.2 138.9 195.53 11.58 36.86 8.00 42.80 10.24 11.37 10.68 2.56 18.15 4.43 17.55 3.84 35.18 5.12 218.36 3.71
    NYTS-2-04 17.4 139.1 331.40 50.60 232.17 16.05 63.10 14.95 12.72 14.35 2.84 23.03 6.50 26.72 5.35 54.33 7.82 530.55 2.96
    NYTS-2-05 24.2 229.1 379.33 59.31 137.24 19.31 72.11 15.77 9.86 17.64 3.78 33.46 8.80 35.80 6.48 50.59 6.27 476.44 2.02
    NYTS-2-06 36.6 233.8 30.11 0.57 2.57 0.71 4.22 3.23 0.83 4.28 0.98 6.18 1.51 4.45 0.62 3.56 0.46 34.16 0.77
    NYTS-16-A01 7.2 80.9 104.49 15.83 64.67 9.43 44.49 9.55 8.90 10.71 1.74 12.00 2.89 8.07 0.89 4.63 0.71 194.51 3.00
    NYTS-16-A02 9.9 78.8 84.31 24.08 49.34 8.61 40.72 9.13 10.06 8.91 1.57 10.65 2.45 6.68 0.75 3.72 0.54 177.21 3.80
    NYTS-16-A03 8.0 75.5 216.48 17.77 78.41 11.97 60.53 17.28 10.48 20.42 3.80 27.34 6.30 17.84 2.13 11.33 1.80 287.41 1.90
    NYTS-16-A04 8.5 74.2 117.84 20.31 100.61 18.61 78.68 15.98 10.67 14.52 2.58 16.47 3.58 9.60 1.11 5.74 0.71 299.17 2.39
    NYTS-16-A05 9.1 69.0 93.65 22.56 68.14 10.58 46.13 15.18 10.49 9.47 1.57 10.35 2.69 6.78 0.87 3.83 0.62 209.26 2.99
    NYTS-16-A06 9.3 69.1 164.20 58.80 122.66 17.72 73.98 14.31 13.80 13.55 2.26 15.54 3.49 10.22 1.16 6.81 1.05 355.37 3.38
    NYTS-16-B01 14.7 115.9 39.49 1.42 6.00 1.16 7.47 2.46 6.46 3.25 0.67 5.20 1.21 4.01 0.60 4.23 0.72 44.87 7.79
    NYTS-16-B02 12.9 139.4 58.82 3.64 13.09 2.72 18.22 6.37 5.01 8.18 1.53 10.89 2.43 7.31 0.90 5.19 0.72 86.22 2.37
    NYTS-16-B03 13.5 133.5 44.99 2.01 8.90 1.98 14.00 4.96 5.60 6.88 1.30 8.96 2.05 5.56 0.71 4.33 0.66 67.90 3.27
    NYTS-16-B04 11.8 115.6 79.60 5.51 20.36 4.57 34.26 10.83 4.33 12.07 1.88 12.31 2.82 7.75 0.99 6.86 1.11 125.64 1.29
    NYTS-16-B05 12.9 106.3 57.57 4.57 17.56 3.47 25.36 7.21 4.69 8.98 1.53 9.00 2.03 5.58 0.71 4.44 0.79 95.90 1.99
    NYTS-16-B06 15.4 110.0 50.36 14.57 30.26 4.50 26.18 6.14 5.79 6.50 0.97 6.32 1.48 4.32 0.63 4.62 0.85 113.13 3.13
    注：“ < LOD”表示低于检出限。
    下载: 导出CSV

    表 3  白钨矿原位Sr同位素分析结果

    Table 3.  in situ Sr isotope analytical results of scheelite

    白钨矿类型 样品编号 85Rb信号强度(V) 88Sr信号强度(V) 87Rb/86Sr 2 σ 87Sr/86Sr 2 σ
    矽卡岩型 NYTX-5-01 0.0003 10.34 0.00009 0.00004 0.71383 0.00008
    NYTX-5-02 0.0000 10.48 0.00001 0.00001 0.71352 0.00007
    NYTX-5-03 0.0001 9.74 0.00004 0.00004 0.71359 0.00007
    NYTX-5-04 0.0003 9.58 0.00009 0.00005 0.71351 0.00007
    NYTX-5-05 0.0007 10.26 0.00021 0.00004 0.71353 0.00006
    NYTX-5-06 0.0072 11.08 0.00227 0.00041 0.71364 0.00008
    NYTX-5-07 0.0000 11.32 0.00000 0.00001 0.71356 0.00006
    NYTX-5-08 0.0000 11.25 0.00001 0.00001 0.71356 0.00007
    NYTX-5-09 0.0001 11.23 0.00002 0.00001 0.71351 0.00007
    NYTX-5-10 0.0002 7.25 0.00009 0.00001 0.71359 0.00007
    NYTX-5-11 0.0000 10.88 0.00000 0.00001 0.71354 0.00006
    NYTX-5-12 0.0003 10.44 0.00008 0.00003 0.71358 0.00007
    NYTX-5-13 0.0006 9.95 0.00021 0.00005 0.71359 0.00007
    NYTX-5-14 0.0098 8.76 0.00393 0.00060 0.71384 0.00010
    NYTX-5-15 0.0014 9.61 0.00048 0.00006 0.71354 0.00008
    NYTX-12-01 0.0002 3.32 0.00021 0.00004 0.71491 0.00011
    NYTX-12-02 0.0002 6.12 0.00011 0.00002 0.71339 0.00007
    NYTX-12-03 0.0004 6.43 0.00019 0.00003 0.71336 0.00007
    NYTX-12-04 0.0001 5.28 0.00008 0.00002 0.71354 0.00008
    NYTX-12-05 0.0003 3.02 0.00036 0.00004 0.71429 0.00011
    NYTX-12-06 0.0003 4.85 0.00021 0.00003 0.71349 0.00010
    NYTX-12-07 0.0001 5.53 0.00008 0.00001 0.71319 0.00010
    NYTX-12-08 0.0002 5.13 0.00013 0.00002 0.71349 0.00011
    NYTX-12-09 0.0002 2.57 0.00032 0.00003 0.71478 0.00015
    NYTX-12-10 0.0005 4.17 0.00044 0.00013 0.71374 0.00013
    NYTX-12-11 0.0003 3.39 0.00034 0.00006 0.71385 0.00012
    NYTX-12-12 0.0929 3.59 0.08473 0.01206 0.71401 0.00014
    NYTX-12-13 0.0003 5.54 0.00020 0.00003 0.71357 0.00010
    NYTX-12-14 0.0007 4.42 0.00051 0.00011 0.71389 0.00011
    NYTX-12-15 0.0007 5.15 0.00044 0.00003 0.71353 0.00009
    长石-石英脉型 NYTS-1-A01 0.0026 1.41 0.00589 0.00039 0.72027 0.00021
    NYTS-1-A02 0.0033 1.33 0.00804 0.00071 0.72014 0.00027
    NYTS-1-A03 0.0025 0.90 0.00968 0.00198 0.72135 0.00035
    NYTS-1-A04 0.0050 1.18 0.01394 0.00101 0.72072 0.00032
    NYTS-1-A05 0.0046 1.34 0.01109 0.00094 0.72043 0.00023
    NYTS-1-A06 0.0014 1.29 0.00369 0.00028 0.72094 0.00022
    NYTS-1-A07 0.0019 1.24 0.00506 0.00036 0.72106 0.00025
    NYTS-1-A08 0.0014 1.18 0.00409 0.00032 0.72061 0.00026
    NYTS-1-A09 0.0038 1.09 0.01114 0.00090 0.72085 0.00030
    NYTS-1-A10 0.0017 1.11 0.00518 0.00020 0.72104 0.00031
    NYTS-1-A11 0.0008 1.10 0.00244 0.00013 0.72186 0.00029
    NYTS-1-A12 0.0044 1.13 0.01254 0.00145 0.72168 0.00034
    NYTS-1-A13 0.0013 1.30 0.00348 0.00037 0.72079 0.00024
    NYTS-1-A14 0.0006 1.39 0.00149 0.00026 0.71923 0.00028
    NYTS-1-A15 0.0017 1.24 0.00420 0.00039 0.72066 0.00022
    NYTS-1-B01 0.0022 2.35 0.00338 0.00125 0.71604 0.00014
    NYTS-1-B02 0.0014 2.17 0.00213 0.00021 0.71584 0.00016
    NYTS-1-B03 0.0033 2.14 0.00510 0.00031 0.71613 0.00015
    NYTS-1-B04 0.0039 2.40 0.00530 0.00042 0.71693 0.00014
    NYTS-1-B05 0.0019 2.23 0.00272 0.00010 0.71618 0.00015
    NYTS-1-B06 0.0021 2.49 0.00293 0.00036 0.71649 0.00016
    NYTS-1-B07 0.0028 2.28 0.00394 0.00038 0.71666 0.00015
    NYTS-1-B08 0.0028 2.15 0.00449 0.00093 0.71622 0.00015
    NYTS-1-B09 0.0013 2.37 0.00174 0.00009 0.71537 0.00013
    NYTS-1-B10 0.0010 2.47 0.00138 0.00016 0.71589 0.00017
    NYTS-1-B11 0.0007 2.67 0.00084 0.00007 0.71588 0.00011
    NYTS-1-B12 0.0030 2.74 0.00355 0.00031 0.71601 0.00011
    NYTS-1-B13 0.0018 2.82 0.00231 0.00026 0.71636 0.00023
    NYTS-1-B14 0.0039 1.29 0.00978 0.00060 0.71716 0.00023
    NYTS-1-B15 0.0065 1.72 0.01303 0.00185 0.71724 0.00018
    NYTS-2-01 0.0018 1.45 0.00402 0.00025 0.72024 0.00018
    NYTS-2-02 0.0005 1.45 0.00120 0.00019 0.72020 0.00018
    NYTS-2-03 0.0005 1.48 0.00108 0.00007 0.71906 0.00019
    NYTS-2-04 0.0006 1.47 0.00126 0.00011 0.71918 0.00020
    NYTS-2-05 0.0004 1.27 0.00108 0.00007 0.72151 0.00023
    NYTS-2-06 0.0007 1.27 0.00170 0.00014 0.72158 0.00021
    NYTS-2-07 0.0016 1.29 0.00412 0.00022 0.72105 0.00021
    NYTS-2-08 0.0016 1.30 0.00404 0.00061 0.72108 0.00023
    NYTS-2-09 0.0008 1.39 0.00192 0.00020 0.72372 0.00022
    NYTS-2-10 0.0015 1.45 0.00351 0.00031 0.72230 0.00019
    NYTS-13-01 0.0004 1.05 0.00125 0.00009 0.72803 0.00029
    NYTS-13-02 0.0009 0.94 0.00312 0.00031 0.72764 0.00032
    NYTS-13-03 0.0001 0.97 0.00039 0.00008 0.72694 0.00026
    NYTS-13-04 0.0001 1.02 0.00034 0.00007 0.72614 0.00028
    NYTS-13-05 0.0003 0.95 0.00119 0.00007 0.72705 0.00024
    NYTS-13-06 0.0003 0.87 0.00096 0.00008 0.72757 0.00028
    NYTS-13-07 0.0001 0.82 0.00055 0.00008 0.72719 0.00030
    NYTS-13-08 0.0032 0.91 0.01163 0.00189 0.72769 0.00033
    NYTS-13-09 0.0007 0.78 0.00271 0.00018 0.72774 0.00036
    NYTS-13-10 0.0005 0.75 0.00204 0.00037 0.72756 0.00034
    标准样品 XJSSTD(n=8) 0.0000 6.48 0.00001 0.00002 0.72086 0.00015
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