Preliminary Study on the Enrichment Mechanism of Strategic Metals and Their Resource Prospects in Global Modern Seafloor Massive Sulfide Deposits
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摘要: 海底块状硫化物(SMS)蕴藏有丰富的Cu、Cd、Au、Fe、Ag、Co等战略性金属，是未来可供人类开发利用的战略资源.本文搜集了全球3 946组SMS化学成分数据，根据构造环境可将其分成4类(快速、中速、慢速、超慢速扩张)洋中脊型和2类(弧后扩张中心和弧火山)岛弧型SMS矿床.利用多元统计方法分析了SMS战略性金属的分布特征和主控因素，探讨了其资源前景.结果表明：洋中脊型SMS矿床富集Cu+Fe+Co±Mo，而岛弧型普遍富集Zn+Pb+Cd+Sb+Ag±Au等关键元素.分析表明，成矿温度、成矿物质来源、酸碱度和氧化还原条件是战略性金属富集的主要影响因素，其中流体温度主要受水深条件控制，成矿物质来源主要受控于构造地质环境，酸碱度和氧化还原性主要受控于围岩类型.Cu+Au+Fe+Co在水深超过约2 650 m的慢速—超慢速扩张脊非转换不连续带和拆离断层带等区域具较好的勘查前景；而Cu+Au+Cd+Ag在水深约1 080~2 160 m的弧后扩张中心区域具较好的勘查前景.Abstract: Seafloor massive sulfides (SMS), which are rich in strategic metals such as Cu, Cd, Au, Fe, Ag, and Co, are strategic resources available for human development and utilization in the future. We collected the geochemical composition data of 3 946 SMS samples in global hydrothermal systems. They were classified into six types according to the tectonic setting: fast-spreading ridge type, medium-spreading ridge type, slow-spreading ridge type, ultra-slow spreading ridge type, back-arc spreading center type, and arc volcano type, respectively. The distribution and main controlling factors of SMS strategic metals are analyzed by multivariate statistical method, and then the resource prospects of SMS strategic metals are discussed. It is found that the strategic metals in SMS deposits of different tectonic environments are quite different. The SMS deposits at mid-ocean ridge tend to be enriched in Cu+Fe+Co±Mo, while the SMS deposits in the back-arc spreading center and arc volcano tend to be enriched in Zn+Pb+Cd+Sb+Ag±Au. The main controlling factors of SMS strategic metals are metallogenic temperature, ore-forming source, pH and redox conditions, respectively. The fluid temperature is mainly controlled by the water depth. The sources of ore-forming materials are mainly controlled by the structural geological environment. The pH and redox properties are mainly controlled by the type of wall rock. We propose that the back-arc spreading center with water depth of 1 080-2 160 m could be key targets for strategic metals such as Cu, Au, Cd and Ag, while the regions such as non-transform discontinuous and detachment fault extensional shear zone of slow- and ultraslow-spreading ridges with water depth greater than 2 650 m could be key targets for Cu, Au, Fe, Co, etc.
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图 1 全球108个SMS矿床分布
海底扩张速率参考DeMets et al.(2010).单位矿石价值估值：按照美国联邦地质调查局2020年公布的金属价格和所选元素在各矿床的中值作为品位估算，据U.S. Geological Survey(2020).底图数据来自GEBCO Compilation Group (2020) GEBCO 2020 Grid (https://doi.org/10.5285/a29c5465-b138-234d-e053-6c86abc040b9)，采用Goode等积投影
Fig. 1. Global distribution of 108 SMS deposits
图 3 全球不同构造环境中SMS矿床的浅表层硫化物样品组成箱线图
图上的数字表示有数据的样品数量
Fig. 3. Whisker-and-box-plot of shallow samples collected from seafloor massive sulfide deposits in different tectonic settings
图 4 SMS斯皮尔曼秩相关系数矩阵
圆的大小和颜色表示相关系数的大小，圆上数值是显著性 > 0.05时的显著性值(显著性 < 0.05时表明显著相关，故未标出)；下三角矩阵显示的是相关系数的值
Fig. 4. Seafloor massive sulfide Spearman's rank correlation coefficients matrix
图 5 经中心对数比变换后的SMS化学数据因子分析双标图：F1 vs. F2(a、b、c)；F1 vs. F3(d、e、f)
Fig. 5. Biplots for distribution of the factor analysis of centered log-ratio (clr) transformed SMS geochemistry data: F1 vs. F2 (a, b, c); F1 vs. F3 (d, e, f)
图 6 现代SMS矿床结构简图
a. TAG矿床，据Lehrmann et al.(2018)；b. Bent Hill矿床，据Zierenberg et al.(1998)；c. Pacmanus/Roman Ruins矿床，据Petersen et al.(2005)；d. Solwara 12矿床，据Lipton et al.(2018)
Fig. 6. Schematic cross sections of the modern SMS deposits
图 7 F1与热液流体温度(a)、SMS矿床的水深(b)和样品中Ag (c)、Co (d)含量相关图
Fig. 7. The scatter plots of approximations to the F1 vs. temperature (a) of hydrothermal fluids, the water depth (b) of the SMS deposit and the content of Ag (c), Co (d) in SMS
图 8 SMS样品Co-Sb-Au×10相对质量分数
形状和颜色代表了不同的构造环境
Fig. 8. Relative contents for Co-Sb-Au×10 in samples of SMS deposits
图 9 F3与热液流体pH(a)、lgfO2 (b)和SMS中Cu (c)、Au (d)相关关系
热液流体数据见附录B
Fig. 9. The scatter plots of approximations to the F3 vs. pH (a), lgfO2 (b) of hydrothermal fluids and the content of Cu (c), Au (d) in SMS
图 10 SMS矿床品位‒吨位关系
VMS矿床数据来自Mosier et al. (2009)；SMS矿床数据同表 3
Fig. 10. Relation of grade-tonnage of SMS deposits
图 11 全球各SMS矿床战略性金属含量中值频率累积曲线
灰色虚线分别表示10%、50%、90%的位置.黑色实线表示最低工业品位，引自矿业行业标准DZ/T0214- 2002，其中Cd、Mo和Sb为Zn-Pb伴生矿的最低工业品位
Fig. 11. Cumulative frequency of strategic metals median content of 108 SMS deposits
图 12 全球各SMS矿床战略性金属含量中值与水深散点图
水深与各SMS矿床Cu (a)、Fe (b)、Co (c)、Au (d)、Cd (e)、Ag (f)含量中值散点图，浅粉红色表示慢速‒超慢速扩张洋脊型SMS矿床较高潜力的水深范围，浅青色代表弧后扩张中心型SMS矿床较高潜力的水深范围.因为洋中脊型和到岛弧型SMS矿床中Au的中值趋势差异较大，所以对其分别与水深进行拟合
Fig. 12. Scatter plot of median strategic metals content and water depth of global SMS deposits
表 1 我国可能的及现代海底潜在的战略性金属对比
Table 1. List of possible "strategic metals" in China and the potential strategic metals on the seafloor
类别 战略性金属1 现代海底 多金属结核2 富钴结壳3 块状硫化物4 稀有金属 Li, Be, Nb, Ta, Rb, Sr, Zr, Hf, Cs Li, Zr Zr, Nb Sr 稀土金属 REE REE REE - 稀散金属 Ga, Ge, In, Tl, Cd, Se, Te, Re Tl Te, Tl Cd, Ga, Ge, In, Se, Te, Tl 稀贵金属 Os, Ir, Ru, Rh, Pd, Pt, Au, Ag Ru, Rh, Pd, Pt, Au, Ag Os, Ir, Ru, Rh, Pd, Pt, Au, Ag Au, Ag 能源金属 U - - - 其他 Fe, Cu, Al, Mn, Cr, V, Ti, Mg, Ni, Co, W, Sn, Bi, Mo, Sb, Hg, Se Fe, Mn, Ni, Cu, Co, Mo, W Fe, Mn, Co, Mo,
Bi, WCu, Fe, Bi, Hg, Co, Mo, Ti, Sb, Hg, Se 
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表 2 不同构造环境海底块状硫化物矿床浅表层样品战略性金属含量统计结果
Table 2. Element content of shallow samples collected from seafloor massive sulfide deposits located in different tectonic settings
构造环境 Ⅰ.快速扩张洋脊 Ⅱ.中速扩张洋脊 Ⅲ.慢速扩张洋脊 Ⅳ.超慢速扩张洋脊 Ⅴ.弧后扩张中心 Ⅵ.弧火山 全部 Cu (%) 中值 1.65 1.04 2.97 0.77 1.25 0.29 1.21 均值 5.43 3.42 9.85 1.94 5.06 2.84 5.20 75% 6.75 2.30 12.98 1.75 4.93 1.76 4.80 25% 0.34 0.31 0.55 0.32 0.38 0.07 0.32 N 478 813 645 276 1 270 256 3 738 Fe (%) 中值 28.3 23.9 29.3 18.7 10.4 10.0 19.8 均值 27.0 23.8 28.1 21.4 13.8 13.6 20.7 75% 36.6 33.1 37.9 31.2 21.1 19.1 31.3 25% 16.80 13.50 18.40 9.90 3.73 2.60 8.00 N 512 828 637 274 1 261 272 3 784 Zn (%) 中值 1.54 4.60 0.54 2.84 11.70 3.39 4.17 均值 8.74 11.30 6.81 7.08 17.10 8.18 11.60 75% 11.50 20.70 6.58 9.12 30.50 12.40 19.70 25% 0.16 0.43 0.10 0.23 1.45 0.25 0.31 N 485 831 669 276 1 291 267 3 819 Pb (%) 中值 0.03 0.07 0.02 0.03 0.17 0.50 0.06 均值 0.17 0.37 0.04 0.18 2.46 2.49 1.17 75% 0.07 0.20 0.05 0.15 0.70 3.47 0.26 25% 0.02 0.02 0.01 0.01 0.04 0.05 0.02 N 409 750 495 262 1 158 249 3 323 Cd (10‒6) 中值 133 347 40 115 420 144 209 均值 338 532 259 309 668 430 493 75% 557 913 297 328 1 115 575 804 25% 33.00 35.50 8.82 9.86 48.00 20.80 23.00 N 336 567 427 242 1 085 235 2 892 Co (10‒6) 中值 190.0 21.0 147.0 98.0 9.0 10.8 37.0 均值 565.0 152.0 925.0 142.0 63.6 36.4 365.0 75% 529.0 87.8 615.0 194.0 37.0 29.0 218.0 25% 30.00 3.85 24.00 11.30 2.00 4.00 6.00 N 390 626 579 245 560 140 2 540 Mo (10‒6) 中值 85.0 61.0 41.0 19.8 35.5 53.5 48.0 均值 108.0 90.6 67.0 54.2 92.1 82.2 87.2 75% 139 123 73 43 97 99 106 25% 38.0 24.0 20.0 11.0 15.0 19.6 19.0 N 278 606 330 112 718 208 2 252 Sb (10‒6) 中值 6.5 17.0 5.0 14.4 110.0 222.0 31.0 均值 14.1 153.0 27.5 79.1 852.0 1 387.0 474.0 75% 15.0 71.5 25.0 52.5 469.0 898.0 150.0 25% 2.55 6.33 2.09 3.83 34.40 70.00 7.10 N 267 680 312 207 907 240 2 613 Ag (10‒6) 中值 33.9 52.0 30.0 66.0 105.0 100.0 62.0 均值 63.1 145.0 133.0 149.0 300.0 206.0 193.0 75% 83.5 121.0 100.0 122.0 240.0 272.0 163.0 25% 13.5 17.3 10.2 19.6 36.6 41.0 20.0 N 403 730 462 243 1 146 235 3 219 Au (10‒9) 中值 200 170 1 100 1 965 3 370 1 685 970 均值 641 844 4 110 4 639 7 163 6 294 4 054 75% 506 770 3 662 3 770 8 250 4 765 3 738 25% 66.8 70.0 430.0 705.0 1 200.0 471.0 178.0 N 320 687 439 198 856 222 2 722 注：N为分析的样品数，表中元素含量未统计其样品的大小.
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表 3 全球已钻探SMS矿床的品位和吨位
Table 3. The grade and tonnage of SMS deposits in world's oceans obtained by drilling
矿床 区域 钻孔数(个) 总长(m) 吨位(Mt) Cu (%) Zn (%) Pb (%) Ag (g/t) Au (g/t) Bent Hill1 胡安德富卡脊 7 1 918 10~15 1.65 1.29 0.008 3 4.48 0.05 TAG2 北大西洋脊 5 304 3.9 2.83 0.42 0.006 5 14.0 0.534 Izena3 冲绳海槽 176 3 785 7.4 0.41 5.75 1.44 95.6 1.45 Hakurei3 伊豆小笠原岛弧 41 405 0.1 0.82 15.84 1.30 294.2 8.63 Solwara 14 帕克马努斯海盆 247 2 779 2.6 7.74 0.7 ‒ 29.59 5.84 Solwara 124 帕克马努斯海盆 28 329 0.2 7.3 3.6 ‒ 56 3.6 注：1 Fouquet et al.(1998) 、Zierenberg et al.(1998) ；2Hannington et al.(1998) ；3 JOGMEC官网(海底热液矿床开发计划综合评价报告书)；4Lipton et al.(2018) .
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