Metasomatized Lithospheric Mantle and Gold Mineralization
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摘要: 交代岩石圈地幔与大型金矿床之间的成因联系受到越来越多的关注.研究成矿金属在地幔源区的富集程度和幔源岩浆中的金含量，以及金从地幔源区释放、迁移并大规模富集成矿的机制和过程可以帮助我们更好地认识交代岩石圈地幔对金富集成矿的重要作用.金是高度亲铜元素，同时还具有流体活动性，在地幔岩浆作用、岩浆热液演化和富集成矿等诸多过程中的行为较为复杂.主要从金的地球化学行为出发，通过梳理金在各类地幔岩石和幔源岩浆中的分布，以及岩浆热液中金的主要行为及其受控因素，探讨交代岩石圈地幔对巨量金成矿的关键控制机制.主要认识包括：（1）交代岩石圈地幔可能是形成大规模热液型金矿床的重要源区，但金在源区的异常富集可能并不是成矿的必要条件；（2）地幔交代组分（特别是挥发分）有助于金从地幔源区中有效释放、并通过跨岩石圈尺度的深大断裂迁移富集；（3）富挥发分的岩浆热液中金的富集沉淀过程远比一个富金的地幔源区对大规模金成矿作用的贡献更大.因此，深刻理解岩石圈地幔长期演化过程中金在地幔交代和岩浆-热液演化过程中的行为与富集机制是解析大型金矿床成因的关键.Abstract: Metasomatized lithospheric mantle has been considered to play a key control on the formation of giant gold (Au) deposits. Investigating the extent of Au enrichment in the metasomatized lithospheric mantle source and Au contents of mantle-derived magmas, as well as the mechanisms that promote the transportation and enrichment of Au from mantle source to large Au mineralization, could help us to understand the major controls responsible for the formation of giant hydrothermal Au deposits. Gold is one of the highly chalcophile elements and is also mobile in fluids. The behavior of Au in many processes such as mantle melting/metasomatism, magmatic-hydrothermal evolution, and mineralization is complicated. In this study, it compiles Au contents of mantle rocks and their derivative mafic magmas, and attempts to clarify key factors that control the behavior of Au from mantle, magmatic-hydrothermal processes to gold mineralization. It suggests that the metasomatized lithospheric mantle is an important source for giant hydrothermal Au deposits, but the remarkable Au enrichment of such mantle source is not necessarily required. Metasomatic components, especially volatiles, enable efficient release of Au from the mantle source to hydrous magmas and promote subsequent transportation and enrichment during magmatic-hydrothermal processes through trans-lithospheric fault systems. It thus emphasizes the main role of the metasomatized lithospheric mantle as the source of giant Au deposits and highlight the importance of metasomatic volatiles and related magmatic-hydrothermal processes in Au enrichment rather than anomalously pre-enriched sources or primary magmas. Therefore, understanding the behavior of Au in mantle metasomatism and magmatic-hydrothermal processes during the long-term evolution of the lithospheric mantle is the key to decode the genesis of giant hydrothermal Au deposits.
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Key words:
- lithospheric mantle /
- metasomatism /
- gold mineralization /
- chalcophile element /
- volatile /
- geochemistry
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图 1 俯冲循环和地幔交代控制的金成矿构造模式
不同类型(富)金矿床的形成均与汇聚板块边缘俯冲相关的构造体制和交代岩石圈地幔部分熔融形成的岩浆/流体有关, 修改自Groves et al.(2021)
Fig. 1. Schematic diagram of gold mineralization controlled by subduction structure and mantle metasomatism
图 2 Au在硅酸盐溶体中的溶解度以及在不同物相间的分配系数
a.高温高压实验结果表明硅酸盐熔体中的Au主要受控于还原性S含量.当氧逸度过高时, S将转化为硫酸盐而失去对Au的控制作用; 数据引自Botcharnikov et al.(2011); Jégo and Pichavant(2012); Zajacz et al.(2013); Botcharnikov et al.(2013); Li et al.(2019a); b.天然样品及实验测定的Au在不同物相间的分配系数, 由于温度、压力、氧逸度以及熔/流体成分等条件的变化, Au在各相之间的分配系数变化非常大.数据引自Ulrich et al.(1999); Simon et al.(2005); Williams-Jones and Heinrich(2005); Simon et al.(2007); Seo et al.(2009); Botcharnikov et al.(2011); Frank et al.(2011); Botcharnikov et al.(2013); Li and Audétat(2013); Zajacz et al.(2013); Li et al.(2019a)
Fig. 2. The solubility of Au in silicate melts and partition coefficients of Au between different phases
图 3 热液中Au的主要络合状态示意
a.图中显示在特定造山型变质流体中Au的主要络合形式(黄铁矿-磁黄铁矿-磁铁矿矿物缓冲对, 3% NaCl, pH: 5~6条件下), 该图主要用于指示热液中溶解的Au主要和还原性S络合, 在高温热液体系中Au还会与Cl络合.需要注意的是, S、Cl和Au的络合状态以及Au溶解度会随温度、压力、氧逸度或含S或Cl相浓度的改变而显著变化.该图修改自Pokrovski et al.(2015); b.热液体系中Au的不同络合物的示意图, Au主要受控于还原性S, 而硫酸根(SO42-)对金没有控制作用.Au可与Cl和OH有一定程度的络合
Fig. 3. Schematic diagram of speciation of gold in hydrothermal fluids
图 4 地幔橄榄岩、幔源熔体(a)以及地幔硫化物(b)中亲铜元素含量的典型分布
上地幔主要以饱满的二辉橄榄岩为主, 具有与原始地幔类似的亲铜元素特征.由于部分熔融作用, 不相容的亲铜元素会进入到岩浆中, 造成方辉橄榄岩以及残余的硫化物中相对亏损这些不相容亲铜元素(如Pd、Au和S等); 相反, 地幔来源的熔体及结晶产物(如辉石岩和洋中脊玄武岩)以及熔体交代形成的粒间硫化物则表现出相对富集不相容亲铜元素的特征.地幔橄榄岩、地幔辉石岩以及洋中脊玄武岩数据引自Fischer-Gödde et al.(2011), Wang and Becker(2015), 硫化物数据引自Tassara et al.(2018)
Fig. 4. Typical patterns of chalcophile element contents in mantle peridotites, magmas (a) and sulfides (b)
图 5 岩浆演化过程中岩浆岩Au元素含量(a)和Au/Pd(N)比值(b)随MgO降低的变化趋势
岩浆达到硫化物饱和会造成残余熔体的Au含量下降, 但由于Au相对于Pd在硫化物中更不相容, 残余熔体的Au/Pd比值会逐渐升高.科马提岩数据引用自Brügmann et al.(1987), Hofmann et al.(2017); 岛弧玄武质岩浆岩数据引用自Park et al.(2013, 2015); 洋中脊玄武岩数据引自Jenner and O’Neill(2012).图b黑色虚线代表原始地幔Au/Pd(N)比值据McDonough and Sun(1995)
Fig. 5. The variations of Au contents (a) and Au/Pd(N) ratios (b) of magmas with decreasing MgO content during magmatic differentiation
图 6 全球地幔岩的Au含量(a)和Au/Pd(N)比值(b)箱型图
图中显示全球地幔岩石及幔源岩浆的Au含量普遍在1~2 ng/g, 引用数据见正文参考文献.所有数据均剔除了Au含量大于100 ng/g的极端异常值; 箱内显示出平均值(叉线)和中值(横线)
Fig. 6. The Au contents (a) and Au/Pd(N) ratios (b) of global mantle rocks and magmas
图 7 全球地幔岩石及幔源岩浆的Au含量频率分布直方图
箭头指示引用数据的最大值, 数据来源与图 6一致
Fig. 7. The frequency distribution histograms of Au contents in global mantle rocks and magmas
图 8 全球地幔岩石Au含量和Au/Pd(N)比值与Al2O3含量(a, b)和Ba/Nb比值(c, d)
地幔橄榄岩的Au含量理论上与地幔的饱满程度相关(Al2O3), 但地幔岩石的Au含量和Au/Pd比值总体上并没有随着Al2O3和Ba/Nb的升高而显著升高, 暗示地幔交代过程中Au的加入非常有限.数据来源和图 6一致, 其中原始地幔值来源于McDonough and Sun(1995)
Fig. 8. The Al2O3 (a, b), Ba/Nb (c, d) vs. Au and Au/Pd(N) ratios for global mantle rocks
图 9 地幔部分熔融程度与硅酸盐熔体Au含量的模拟结果
Au在地幔部分熔融过程中主要受控于岩浆硫化物饱和时的S含量(SCSS), 随着氧逸度和水含量升高, 硅酸盐熔体的SCSS会升高(假设为1 200、1 600和2 300 μg/g), 同时Au在硫化物与硅酸岩熔体中的分配系数则显著降低(假设为1 000和200)(Botcharnikov et al., 2011).模拟假设地幔源区的Au含量为0.5, 1和1.5 ng/g, S含量为180 μg/g, 地幔硫化物含量为0.06%, 部分熔融模型引自Lee et al.(2012).其中Au在地幔初始部分熔融时, 主要表现为轻微不相容性, 而当地幔硫化物完全耗尽时, 主要表现为强不相容性.部分熔融模拟显示地幔在相对氧化和富水的条件下, 即使源区不富集Au(0.5~1.5 ng/g), 也能够形成富Au的岩浆(~1~16 ng/g), 该图修改自Wang et al. (2022)
Fig. 9. Fractional mantle melting models: primary melt Au contents as a function of degree of melting and SCSS in melts
图 10 交代岩石圈地幔控制大规模金成矿的模式
长期的地幔交代会使一部分Au以及大量挥发分进入亏损的岩石圈地幔(< 0.5 ng/g), 但这并不会造成地幔Au的异常富集(< 0.5~2 ng/g).在交代地幔部分熔融条件下, 幔源富水岩浆能够有效迁移源区的易熔组分, 促使Au和挥发分(H2O、S、Cl、C等)在岩浆中的初步富集.富含挥发分的幔源岩浆沿着跨岩石圈尺度的深大薄弱构造向上迁移, Au随着出溶的挥发分进入岩浆热液中.这些成矿热液携带着幔源Au和挥发分沿着次级断裂进一步迁移, 并由于流体不混溶、沸腾脱气等作用而发生Au的高效沉淀, 最终形成大规模、高品位的金矿床
Fig. 10. The schematic cartoon of large-scale gold mineralization controlled by metasomatized lithospheric mantle
图 11 巴布亚新几内亚利希尔岛Ladolam大型金矿床(> 1300 t)的区域构造背景(a)和成矿热液的钻孔取样示意(b)
该图修改自McInnes et al.(1999); Simmons and Brown(2006).该金矿的成矿流体具有和下部交代岩石圈地幔一致的Os同位素组成, 指示成矿金属和流体主要来自交代的岩石圈地幔源区(McInnes et al., 1999).然而, 强烈交代的地幔橄榄岩包体和矿体下部1 km处成矿流体钻孔样品显示, 其下伏的交代岩石圈地幔源区(< 1 ng/g)以及成矿岩浆热液(~ 16 ng/g)并不异常富集金(McInnes et al., 1999; Simmons and Brown, 2006).这意味着Au在交代岩石圈地幔源区以及成矿热液中的显著富集并不是形成大规模金矿床的必要条件, 而Au在热液中的高效迁移和沉淀可能更为关键.巨大的交代地幔源区保证了充足的Au和热液.其中橘黄色椭球体代表Ladolam金矿集区.b图为全球不同地区地热流体钻孔样品Au含量.这些热液金含量整体与Ladolam大型金矿成矿热液的Au含量相当, 数据来源于Chambefort and Stefánsson (2020)
Fig. 11. Schematic diagram of geological settings (a) and down-hole sampling of geothermal fluids (b) of the Ladolam gold deposits, Lihir Island, Papua New Guinea
表 1 Au在硅酸盐熔体中的含量和与硫化物之间的分配系数
Table 1. Experiment-determined Au contents in silicate melts and the partition coefficients between sulfide melts/monosulfide solid solution and silicate melts
实验熔体成分 温度(℃) 压力(GPa) 氧逸度ΔFMQ 硫逸度logf$ {}_{{\mathrm{S}}_{2}} $ 硅酸盐熔体S含量(10-6) 硅酸盐熔体Au含量(10-6) 硫化物熔体/硅酸盐熔体(DAu) 单硫化物固溶体/硅酸盐熔体(DAu) 参考文献 含水玄武质熔体 1 175~1 300 1.5~2.5 -3.1~0.9 -2.4~2.0 1 500~14 400 0.02~1.08 790~4 070 60~360 Li and Audétat, 2012 含水玄武质熔体 1 200 1.5 -2.1~1.6 -1.1~2.1 < 100~15 900 0.6~15.4 7 522~15 339 50~72 Li and Audétat, 2013 玄武质安山岩-流纹岩 950~1 050 0.5~3.0 -1.7~2.7 -2.17~2.08 48~5 536 0.012~55.300 10~14 194 Li et al., 2019a 玄武质-安山质熔体 1 050 0.2 -0.70~3.16 -0.69 ~1.97 390~6 020 0.23~7.97 110~278 Botcharnikov et al., 2013 玄武质熔体 1 050~1 200 0.2 0.1~1.3 1 200~6 110 0.22~13.04 ~2 205 ~170 Botcharnikov et al., 2011 玄武质-流纹质熔体 800~1 030 0.2 0 -3.03~-1.74 115~670 0.06~4.30 Zajacz et al., 2013 闪长岩-英安岩熔体 1 000~1 090 0.4 -1.0~3.2 1.00~2.03 548~957 1.21~4.25 Jégo et al., 2010 闪长岩-英安岩熔体 995~1 000 0.4 -0.6~4.1 -3.76~3.16 256~2 442 0.25~5.16 Jégo and Pichavant, 2012 闪长岩-英安岩熔体 950~1 000 0.9~1.4 0~0.8 0.55~3.84 261~3 865 0.07~47 Jégo et al., 2016 
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表 2 Au在流体-气相-硅酸盐熔体之间的分配系数
Table 2. Partition coefficients of Au between silicate melts-fluids-vapors
实验初始物质 温度(℃) 压力(MPa) 气相/流体 气相/熔体 流体/熔体 参考文献 DAu 花岗质熔体 323~492 9~48 0.28~14 Seo et al., 2009 花岗质熔体 710 110~145 0.14~0.72 8~72 56~100 Simon et al., 2005 花岗质熔体 800 100 0.07~0.58 70~160 20~2 400 Frank et al., 2011 花岗质熔体 800 120 6~50 Simon et al., 2007 花岗质熔体 375~680 1~37 Williams-Jones and Heinrich, 2005
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