Microstructure and Trace Elements of Pyrite from Sanshandao Gold Deposit in Jiaodong District: Implications for Mechanism of Gold Enrichment
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摘要:
三山岛金矿床是位于胶东金矿集区西北部的超大型破碎带蚀变岩型金矿床. 该矿床细致的矿相学及元素地球化学研究尚有不足，限制了对其金富集机制及过程的理解. 基于野外地质调查和室内矿相学研究将该矿床划分为4个成矿阶段：石英-绢云母-黄铁矿阶段(Ⅰ)、石英-金-黄铁矿阶段(Ⅱ)、石英-金-多金属硫化物阶段(Ⅲ)和碳酸盐-石英阶段(Ⅳ). 黄铁矿是该矿床主要载金矿物，其中第Ⅰ阶段黄铁矿(Py1)呈自形且基本无变形，As、Au含量较低；第Ⅱ阶段黄铁矿(Py2)可分为未变形或弱变形的Py2a和强烈变形的Py2b两种类型，Au和As在Py2a中含量高，而在Py2b中含量降低；第Ⅲ阶段黄铁矿(Py3)分为与石英共生的细粒黄铁矿Py3a和与多金属硫化物共生的Py3b两个亚世代，均变形较弱，Au、As含量中等. 黄铁矿原位微量元素分析指示Co、Ni和Ag以固溶体形式进入黄铁矿晶格，而Pb、Zn、Cu主要以硫化物包裹体形式存在. 黄铁矿裂隙和粒间发育大量以银金矿为主的可见金，是该矿床中金的主要赋存状态. 不可见金主要为黄铁矿中晶格金，且其与As关系密切：As-替代黄铁矿内的S-使得黄铁矿晶格发生畸变，并促使Au+进入到黄铁矿晶格中. 第Ⅱ阶段成矿流体减压沸腾导致金沉淀并以包体金、晶隙金的形式与Py2a共生. 受成矿期构造活动影响，第Ⅱ阶段Py2b发生的位错蠕变、晶格旋转等应变行为可促进晶内形成一种“快速通路”，通过晶内扩散或流体介导将黄铁矿内不可见金活化，并在黄铁矿颗粒的微裂缝或晶隙中再富集为可见金.
Abstract:The Sanshandao gold deposit, located in the northwest of Jiaodong district, is a super-large altered-rock type gold deposit. The lack of detailed studies of mineralogy and element geochemistry in this deposit limits the understanding of Au enrichment mechanism and process. Based on field work and mineralogical observation in the deposit, the Au mineralization is divided into four stages: the quartz-sericite-pyrite stage (Ⅰ), quartz-gold-pyrite stage (Ⅱ), quartz-gold-polymetallic sulfide stage (Ⅲ) and carbonate-quartz stage (Ⅳ). The main gold-bearing mineral is pyrite. Py1 in stage Ⅰ is characterized by euhedral grains with no deformation and low contents of As and Au. In stage Ⅱ, the Py2 can be divided into two sub-generations: coarse Py2a with no deformation and Py2b with massive plastic and brittle deformation. The contents of Au and As are high in Py2a and low in Py2b.In stage Ⅲ, the Py3 includes fine-grained euhedral Py3a coexisting with quartz and Py3b coexisting with polymetallic sulfide, both with weak deformation and medium Au and As contents. In-situ trace element analysis of pyrite indicates Co, Ni and Ag entering pyrite lattice by forming solid solution, whereas Pb, Zn and Cu mainly presenting as sulfide inclusions. The main occurrence state of gold is visible Au that occurs in the cracks and intergranular space of pyrite as electrum. The invisible Au in pyrite is lattice gold, and its enrichment is closely related to As. To be specific, As- replacing S- entered into pyrite, resulting in lattice distortion of pyrite, which prompted the Au+ into the pyrite lattice. The decompression boiling of ore-forming fluids in stage Ⅱ resulted in Au precipitation and intergrowth with Py2a as visible inclusions and intergranular gold. The plastic deformation of Py2b in stage Ⅱ induced by syn-activation of ore-controlling fault, such as dislocation creep, lattice rotation, promoted the formation of intracrystalline "fast pathways", and further remobilized invisible Au through intragrain diffusion or fluid-mediated liberation. The remobilized Au re-concentrated as visible gold in microfractures and boundaries of pyrite grains, which contributes to the formation of high-grade gold ores in Sanshandao.
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Key words:
- pyrite /
- trace element /
- Sanshandao gold deposit /
- EBSD /
- mineral deposit
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图 1 华北克拉通(a)和胶东金矿区(b)地质简图(据Li et al., 2018修改)
Fig. 1. Simplified geological maps of the North China Craton (a) and Jiaodong gold province (b) (modified from Li et al., 2018)
图 2 三山岛矿床地质特征
a.三山岛断裂地质特征(据邓军等，2010)；b.三山岛金矿床地质简图(据Hu et al. 2013修改)
Fig. 2. The geologic map of Sanshandao gold deposit
图 3 三山岛金矿床蚀变特征及矿化阶段
a.钾化，残留花岗质原岩；b.黄铁绢英岩化及残留早期的硅化团块；c. 三山岛断裂主断面被构造定向的黄铁绢英岩，上盘弱矿化蚀变，残留钾化花岗岩；d.浸染状黄铁绢英岩矿石被Ⅲ阶段烟灰色石英脉穿插；e. Ⅱ阶段石英‒黄铁矿脉被Ⅲ阶段多金属硫化物脉穿插；f. Ⅳ阶段石英‒碳酸盐脉
Fig. 3. The hydrothermal alteration and mineralization stage in the Sanshandao gold deposit
图 4 三山岛金矿床矿石矿相学特征
a. Ⅰ阶段石英(Qz)+绢云母(Ser)+黄铁矿(Py1)组合，少量热液金红石(Rt)；b. Ⅱ阶段未变形的粗粒黄铁矿(Py2a)和晶隙金(Au)；c. Ⅱ阶段黄铁矿(Py2a、Py2b)及包体金和裂隙金(Au)；d. Ⅱ阶段黄铁矿(Py2b)呈碎裂结构，充填了黄铜矿(Ccp)、闪锌矿(Sp)等硫化物和银金矿(El)；e、f. Ⅲ阶段石英‒多金属硫化物脉内黄铁矿(Py3a、Py3b)与闪锌矿(Sp)和石英(Qz)共生，共同切割Ⅱ阶段石英‒黄铁矿脉
Fig. 4. The mineralography characteristics of the ores in the Sanshandao gold deposit
图 6 三山岛金矿黄铁矿的多世代特点
a. 零星状自形细粒Py1；b、c. 中粗粒Py2a与碎裂化细粒Py2b，Py2b常见于Py2a周缘，Py2a的BSE图象(图c)明暗度整体变化不大，但Py2b呈现较大变化；d、e. 碎裂的Py2b，BSE图象(图e)明暗不一现象明显；f. 与闪锌矿共生的细粒Py3
Fig. 6. The multi-generational characteristics of pyrite in the Sanshandao gold deposit
图 7 各世代黄铁矿EBSD测试结果
a. Py1反射光照片；b. Py1的AE图，暗蓝色区域被标定为一个颗粒；c. Py1的TC图，整个晶体不显晶体取向差异；d. 边部弱变形的Py2a反射光照片；e. Py2a晶体AE图，绿色部分为一个颗粒；f. Py2a晶体TC图，取向差边部(4°~6°)较大，颗粒周围2°~10°部分作为Py2b；g. Py2b反射光照片；h. Py2b的AE图，主体为一个颗粒，少数欧拉角变化较大；i. Py2b的TC+BC图，取向差连续变化(0°~12°)，箭头给出了图k的剖面线；j. 图i中颗粒的极图，箭头给出了旋转方向，a0和b0为旋转轴；k. 图i中线段的取向差剖面；l. Py3b反射光照片；m. Py3b的TC图，显示 < 2°的晶内取向差异
Fig. 7. The EBSD results for pyrite in different generations
图 8 三山岛金矿各世代黄铁矿的微量元素LA-ICP-MS剥蚀曲线
Fig. 8. Representative time-resolved depth profiles by LA-ICP-MS for pyrite grains of different generations in the Sanshandao gold deposit
图 9 三山岛金矿各世代黄铁矿微量元素含量变化
Fig. 9. The changes of trace elements in different generation pyrites in the Sanshaodao gold deposit
图 10 三山岛金矿黄铁矿微量元素相关性
Fig. 10. Correlation of pyrite trace elements in the Sanshandao gold deposit
图 11 黄铁矿结构与成矿构造‒流体演化模式
Fig. 11. The texture of pyrite and model of structure-fluid evolution during mineralization
表 1 三山岛金矿黄铁矿LA⁃ICP⁃MS微量元素分析结果
Table 1. The LA-ICP-MS data of pyrite from the Sanshandao gold deposit
黄铁矿世代 样品号 Au As Ag Co Ni Cu Zn Pb Sb Te Bi 0.015[1] 0.412[1] 0.048[1] 0.012[1] 0.136[1] 0.414[1] 1.045[1] 0.061[1] 0.024[1] 0.233[1] 0.010[1] Py1 SSD‒2‒1 001 0.12 98.43 4.01 0.17 73.58 1 007.98 354.42 290.90 0.35 2.54 15.71 SSD‒2‒1 002 0.13 54.76 13.60 0.17 120.98 4.71 ‒ 105.83 1.67 4.92 9.65 SSD‒2‒1 003 0.06 14.66 8.60 0.06 8.02 1 341.78 35.20 10.59 0.37 0.62 3.80 SSD‒2‒1 004 nd 107.14 nd 0.16 13.13 0.85 ‒ 0.13 nd 0.86 0.02 SSD‒2‒1 006 0.04 198.16 8.17 ‒ 0.47 329.50 18.29 568.60 0.37 1.13 13.76 Py2a SSD‒5‒4 001 0.34 3 451.28 17.01 nd 1.39 257.37 5.93 26.49 3.23 0.24 0.58 SSD‒5‒4 003 0.39 594.35 38.05 0.60 2.12 259.54 966.86 493.20 53.69 1.33 21.20 SSD‒5‒4 006 0.52 2 539.66 8.37 0.03 0.34 20.05 2.09 85.54 8.97 0.46 1.64 SSD‒5‒4 010 0.81 2 203.63 54.69 0.65 2.86 101.81 77.96 1 138.10 86.25 1.35 20.24 SSD‒5‒4 011 0.34 3 049.76 6.46 0.04 0.85 9.92 2.39 54.40 5.75 0.40 0.71 SSD‒5‒4 014 0.61 3 799.72 ‒ nd 0.56 ‒ ‒ nd ‒ ‒ nd SSD‒8‒1 004 0.65 1 772.29 89.37 0.02 2.43 95.52 22.39 28 257.00 25.65 ‒ 202.20 SSD‒9‒1 002 0.58 1 264.51 36.50 0.05 0.54 73.82 3.58 7 424.10 45.10 nd 35.89 SSD‒9‒1 005 0.35 1 447.80 32.02 0.27 2.01 94.57 ‒ 681.60 45.69 ‒ 10.59 Py2b SSD‒5‒4 002 0.13 198.08 6.59 1.71 2.48 14.26 3.37 29.58 5.39 0.62 1.30 SSD‒5‒4 004 0.14 1 577.08 18.00 0.11 2.62 16.38 5500.46 7616.00 9.29 0.35 12.26 SSD‒5‒4 005 0.34 740.94 8.63 0.03 0.99 60.74 6.10 162.30 8.44 0.47 1.70 SSD‒5‒4 012 0.05 1 067.39 1.02 0.02 0.96 2.21 ‒ 6.90 0.94 ‒ 0.15 SSD‒5‒4 015 0.13 1 646.47 22.57 ‒ 0.19 19.90 ‒ 32.31 5.23 nd 0.49 SSD‒8‒1 001 0.12 2 264.75 1.33 0.66 36.60 3.13 ‒ 14.06 2.17 ‒ 0.62 SSD‒8‒1 002 0.18 1 081.45 21.29 1.20 32.24 2 539.03 8.55 3 768.50 7.26 ‒ 24.45 SSD‒8‒1 003 0.09 996.71 1.77 44.35 280.75 3.12 ‒ 51.36 3.00 ‒ 4.35 SSD‒9‒1 001 0.19 583.87 12.11 0.01 ‒ 436.15 51.49 1 766.11 3.75 nd 8.21 SSD‒9‒1 003 0.51 1 177.90 10.45 nd nd 1 039.79 18.84 1 451.70 6.83 ‒ 14.31 SSD‒9‒1 004 0.12 1 995.83 4.11 0.08 0.43 9.05 ‒ 35.85 9.08 ‒ 0.90 SSD‒9‒1 006 0.21 1 899.42 6.23 0.02 0.15 19.92 ‒ 117.53 11.42 nd 2.06 Py3 SSD‒5‒4 007 0.17 412.84 9.43 ‒ 0.70 326.07 7.94 908.21 3.10 ‒ 4.66 SSD‒5‒4 008 0.20 2 478.58 3.34 ‒ ‒ 5.93 ‒ 17.95 2.15 ‒ 0.42 SSD‒5‒4 009 0.40 2 765.01 84.74 ‒ 1.41 25.78 ‒ 57 992.00 13.54 0.37 123.68 SSD‒5‒4 016 0.19 213.13 5.14 ‒ 1.51 8.34 ‒ 17.54 2.81 ‒ 0.96 SSD‒5‒4 017 0.18 2 261.84 3.44 ‒ 0.14 4.76 ‒ 13.78 1.75 ‒ 0.32 SSD‒5‒4 018 0.38 2 729.76 83.88 ‒ 1.11 25.38 ‒ 57 010.65 14.19 0.35 122.77 注：nd表示未测出，“‒”表示可检出但低于检出限，元素含量单位为10‒6.数据[1]表示元素检出限. 
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