Trace element geochemistry of pyrite from the Jinzhuzhou gold deposit in the Dayaoshan district, Qin-Hang Metallogenic Belt (South China): Implications for the metallogenesis
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摘要:
研究目的 作为钦杭成矿带的重要组成部分，广西大瑶山地区发育众多金矿床，但由于成矿的精细过程、成矿物质来源等方面缺乏有效的制约，其矿床成因一直存在争议。本次以大瑶山金竹洲金矿床为研究对象，为区域金矿床成因提供约束。
研究方法 黄铁矿是热液矿床中常见的蚀变矿物，其微量元素特征能够在反演物理化学条件、制约成矿精细过程、限制矿床成因等方面发挥重要作用。通过野外地质调查，在成矿过程精细解剖的基础上，借助扫描电镜、电子探针、激光剥蚀等离子质谱仪等测试技术，开展金竹洲黄铁矿内部结构和原位微量元素研究。
研究结果 大瑶山中部的金竹洲金矿床是区内典型金矿床之一，以发育近南北向的含金石英脉为特征，其成矿过程可划分为3个阶段：(Ⅰ)石英-绢云母-黄铁矿-毒砂阶段；(Ⅱ)石英-自然金-多金属硫化物阶段；(Ⅲ)石英-方解石-绿泥石阶段。系统的背散射图像观察发现，Ⅰ阶段黄铁矿(Py1)发育明显的核-幔-边结构，Ⅱ阶段多孔状和富硫化物包裹体的黄铁矿(Py2)明显交代Ⅰ阶段黄铁矿幔部(Py1b)。原位微区微量元素分析显示，Py1核部(Py1a)Co、Ni、Se、Bi等元素含量较高；幔部(Py1b)富集As和Au；边部(Py1c)元素含量普遍偏低；Py2呈现出亏损Au、As的特征。从Py1a、Py1b到Py1c，Co、Ni两种微量元素含量呈下降趋势，反映温度逐渐降低，这可能是导致Ⅰ阶段黄铁矿出现核-幔-边结构的主要因素；孔洞状且富含包裹体(如方铅矿、辉银矿)的Py2与Py1b的交代界线呈尖锐、突变接触，同时Py2中As、Au等微量元素显著低于Py1b，说明Py2可能是Py1b经过溶解-再沉淀形成的，该作用导致Py1b中的Au发生活化并在Ⅱ阶段富集沉淀形成自然金。
结论 金竹洲黄铁矿明显富集亲岩浆元素Se(3.76×10−6 ~ 73.3×10−6，平均值16.5×10−6)，结合大瑶山地区普遍发育岩浆热液成因的金矿床及深部存在巨大隐伏岩体的可能，推测金竹洲金矿床可能为岩浆热液成因。
Abstract:Objective As an important part of the Qin−Hang Metallogenic Belt, the Dayaoshan district develops abundant gold deposits. However, due to the lack of effective constraints on the ore−forming process ore source the genesis of these deposits has always been controversial. The aim of this study is to provide constraints on the deposit genesis of regional gold deposits by taking the Jinzhuzhou gold deposit in the Dayaoshan district as the study object.
Methods Pyrite is a common mineral in hydrothermal deposits, and its trace element geochemistry can play an important role in constraints on physicochemical conditions, ore−forming process and origin of deposits. In this paper, the internal structure and in situ trace element studies of Jinzhuzhou pyrite are carried out through field geological investigations, on the basis of fine dissection of the metallogenic process, and with the help of SEM, EPMA, LA−ICP−MS and other testing techniques.
Results The Jinzhuzhou gold deposit is one of the typical gold deposits in this district, and characterized by the NS−trending ore−bearing quartz veins. Its mineralization can be divided into three stages: (Ⅰ) Quartz−sericite−pyrite−arsenopyrite stage; (Ⅱ) Quartz−native gold−polymetallic sulfide stage; (Ⅲ) Quartz−calcite−chlorite stage. Systematic back−scattering imaging observations revealed that the Stage Ⅰ pyrite (Py1) has developed a distinct core−mantle−rim texture, while the porous Stage Ⅱ pyrite (Py2) trapping some sulfide inclusions commonly replaces the mantle zone (Py1b) of Py1. In−situ LA−ICP−MS trace element analysis showed that the core zone (Py1c) of Py1 is enriched in Co, Ni, Se, and Bi. Py1b is commonly enriched in As and Au, while the rim zone of (Py1c) of Py1 is commonly depleted in trace elements. Generally, Py2 is characterized by the depletion of Au−As. Notably, the Co−Ni concentrations declines from Py1a, through Py1b, to Py1c, suggesting a gradual decreasing temperature, which may have been responsible for the core−mantle−rim texture of Py1. Moreover, the sharp and irregular contact boundary between Py2 and Py1b, abundant porosities and mineral inclusion of Py2, and the lower Au−As concentrations of Py2 than Py1b, indicate that Py2 may have been formed via dissolution and precipitation of Py1b. This process results in the remobilization of gold solid solution within Py1b and the further precipitation of visible gold in Stage Ⅱ.
Conclusions Generally, the Jinzhuzhou pyrite is obviously enriched in Se (3.76 ~ 73.3×10−6, with an average of 16.5×10−6). Combining with the widespread development of magmatic−hydrothermal gold deposits, and the possible concealed magmatic pluton in the Dayaoshan district, it is inferred that the Jinzhuzhou gold deposit may have been magmatic hydrothermal origin.
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Key words:
- pyrite /
- trace element /
- ore-forming process /
- Jinzhuzhou gold deposit /
- Dayaoshan district /
- Guangxi
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图 2 金竹洲金矿床矿区地质图(a)和00号勘探线设计剖面图(b)(据广西昭平县金竹洲金矿勘查（变更）实施方案，2017修改)
Figure 2.
表 1 金竹洲金矿床手标本特征
Table 1. Hand specimen characteristics of the Jinzhuzhou gold deposit
序号 样品号 主要矿物组合 手标本特征 成矿阶段 1 J1-7 石英-黄铁矿 石英脉，脉中含黄铁矿细脉 Ⅰ阶段 2 J4-2 石英-黄铁矿 石英脉，脉中含少量黄铁矿 Ⅰ阶段 3 J5-3 石英-黄铁矿 石英脉，脉中含黄铁矿细脉 Ⅰ阶段 4 J6-4 石英-黄铁矿 石英脉边部蚀变晕 Ⅰ阶段 5 J1-5a 石英-黄铁矿-毒砂-方铅矿-闪锌矿 石英脉及两侧蚀变带，脉中含大量硫化物 Ⅱ阶段 6 J1-5b 石英-黄铁矿-毒砂-方铅矿-闪锌矿 石英脉及两侧蚀变带，脉中含大量硫化物 Ⅱ阶段 7 J5-1a 石英-黄铁矿-毒砂-方铅矿-闪锌矿 石英脉，脉中黄铁矿等多金属硫化物呈细脉状 Ⅱ阶段 8 J5-1b 石英-黄铁矿-毒砂-方铅矿-闪锌矿 石英脉，脉中黄铁矿等多金属硫化物呈细脉状 Ⅱ阶段 9 J7-1 石英-黄铁矿-毒砂-方铅矿-闪锌矿 石英硫化物脉，脉中含大量硫化物 Ⅱ阶段 10 J7-2 石英-黄铁矿-毒砂-方铅矿-闪锌矿 石英脉，脉中含少量硫化物 Ⅱ阶段 
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表 2 金竹洲金矿床黄铁矿电子探针分析结果
Table 2. Electron microprobe analyses of pyrite from the Jinzhuzhou gold deposit
% 样品 黄铁矿类型 S Fe As Co Ni Cu Pb Sb Ag Au 总量 J1-7 Py1a 53.77 46.14 0.23 - - - - - - 0.02 100.17 J1-7 Py1a 53.69 46.20 0.25 - - - - - - 0.04 100.18 J1-7 Py1a 53.84 46.37 0.02 - 0.07 - 0.02 - - - 100.32 J5-1b Py1a 53.84 46.23 0.96 - - - - - - - 101.04 J5-1b Py1a 53.62 46.40 0.64 - - - - - - - 100.66 J1-7 Py1b 53.12 46.13 1.48 - - 0.01 - - - - 100.74 J1-7 Py1b 52.87 45.80 1.50 - - - 0.04 - - 0.02 100.23 J5-1b Py1b 52.10 45.84 2.27 - - 0.02 - - - - 100.22 J5-1b Py1b 53.11 46.09 1.45 - - 0.01 - - - - 100.67 J5-1b Py1b 53.49 46.26 1.31 - - - 0.03 - - - 101.06 J1-7 Py1c 54.23 46.33 - - - - - - - 0.03 100.60 J1-7 Py1c 53.49 46.23 - - 0.01 - - - - - 99.74 J1-7 Py1c 54.06 46.24 - - - - - - - 0.05 100.36 J1-7 Py1c 52.80 46.00 - - - 0.02 - - 0.01 0.02 98.86 J1-7 Py1c 53.76 46.05 - - - - - - - 0.05 99.86 J5-1b Py2 54.49 46.50 - - - - - - - - 101.00 J5-1b Py2 54.33 46.44 - - - 0.03 0.02 - - - 100.83 J5-1b Py2 54.20 46.58 - - - 0.01 0.09 - - 0.02 100.89 J5-1b Py2 53.99 46.52 - - - - - - - - 100.51 J5-1b Py2 54.11 46.52 0.05 - 0.01 - 0.03 - - - 100.73 注：“-”表示低于检出限
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表 3 金竹洲金矿床黄铁矿微量元素含量
Table 3. Electron microprobe analyses of pyrite from the Jinzhuzhou gold deposit
10−6 类型 点号 Co Ni Cu Zn Ge As Se Mo Ag Sb Te Au Tl Pb Bi Py1a J1-7-PY1 - 3.24 0.500 - 3.98 3356 - - - - - - - 0.061 - Py1a J1-7-PY5 0.624 0.913 6.46 0.934 3.29 9587 - - 1.05 5.84 - 4.11 0.367 18.1 0.234 Py1a J1-7-PY9 0.104 210 5865 739 3.54 8233 - - 26.5 6.11 - 0.261 0.053 31.2 0.554 Py1a J1-7-PY11 0.250 38.9 1.99 7.67 2.69 10068 6.82 - 0.383 1.17 - 1.52 0.024 13.9 0.162 Py1a J1-7-PY14 0.122 1.33 450 9.06 2.61 19613 9.04 - 13.9 45.1 - 14.0 0.430 201 0.300 Py1a J1-7-PY19 2.66 1513 105292 8354 2.62 2639 - - 269 21.7 - 1.53 0.171 111 0.970 Py1a J4-2PY21 11.5 47.6 326 42.4 3.19 23884 - - 17.8 46.1 - 2.24 0.234 89.9 0.567 Py1a J4-2PY22 4.51 - 11.1 6.17 2.91 2828 33.9 - 3.98 37.7 - - 0.203 73.9 0.482 Py1a J5-1aPY25 2.29 2.44 26.2 9.60 2.62 19190 11.7 0.060 1.85 9.61 - 2.65 0.160 68.2 - Py1a J7-1PY31 0.157 0.804 10.0 1.47 3.00 15304 4.74 - 21.4 28.3 - 2.70 0.238 20987 0.287 Py1a J7-1PY37 0.080 0.944 84.5 3.18 3.54 28278 38.9 - 65.5 117 - 12.1 0.324 52573 4.79 Py1a J1-5bPY48 - - 10.2 - 1.23 20381 15.3 0.043 0.269 0.512 - 6.18 0.052 5.85 - Py1a J1-5bPY49 76.0 110 9.69 2.61 3.80 25608 23.8 0.444 5.02 4.94 - 4.96 0.159 9545 0.186 Py1a J1-5bPY54 - 2.66 2.93 1.07 2.58 735 - - 4.67 5.86 - 0.321 0.054 13.1 - Py1a J1-5bPY57 - - 5.23 0.950 2.60 7676 - - 8.23 13.4 - 0.303 0.136 72.2 - Py1b J1-7-PY4 - - 60.8 - 3.49 32623 - - 1.42 2.36 - 7.53 0.044 16.4 0.026 Py1b J1-7-PY12 0.143 0.715 88.6 1.50 2.95 18949 - - 14.5 119 - 4.26 1.11 435 0.175 Py1b J1-7-PY16 0.776 10.8 347 14.2 2.89 20160 16.2 - 8.55 23.2 - 36.8 0.599 60.2 0.070 类型 点号 Co Ni Cu Zn Ge As Se Mo Ag Sb Te Au Tl Pb Bi Py1b J7-1PY27 0.313 - 101 0.770 3.75 23947 - - 78.3 305 - 8.50 0.525 1947 - Py1b J7-1PY29 - - 131 0.699 2.88 23449 - 0.097 109 429 - 9.06 0.799 2539 - Py1b J7-1PY33 1.33 1.19 81.8 1.14 3.37 57128 4.82 - 69.2 301 - 3.78 0.732 1665 - Py1b J7-1PY38 0.167 2.08 63.7 - 3.14 18728 73.3 - 186 268 1.41 4.96 0.671 587923 51.6 Py1b J5-1bPY41 2.72 20.6 48.6 1.57 2.79 24325 6.96 0.192 7.08 24.5 - 3.69 0.200 161 0.008 Py1b J5-1bPY42 0.057 1.90 345 1.76 3.32 23656 6.95 0.071 16.5 72.0 - 10.8 0.430 665 0.184 Py1b J5-1bPY45 - - 82.3 1.96 3.18 35368 9.71 0.042 3.71 31.8 - 13.5 0.075 208 0.042 Py1b J5-1bPY46 0.089 - 139 39.1 3.30 26071 10.0 1.23 12.8 35.6 - 12.9 0.309 414 0.077 Py1b J1-5bPY52 - - 13.9 - 3.37 23581 - 0.086 0.132 0.435 - 2.21 - 8.20 - Py1b J1-5bPY56 - - 124 0.791 2.76 33410 - 0.057 6.79 27.4 - 7.69 0.030 130 - Py1b J1-5bPY58 - - 245 0.825 3.15 50595 - 0.045 4.12 5.88 0.058 14.7 0.041 21.1 - Py1b J7-1@50 16.5 423 162 11.3 - 35921 - - 146 532 - 9.74 0.863 2743 0.178 Py1c J1-7-PY2 - - 71.5 - 3.51 8218 - - 1.08 9.30 - 0.937 0.042 9.05 - Py1c J1-7-PY3 - - 24.1 0.696 4.35 - - - 2.13 15.1 - - 0.766 6.00 - Py1c J1-7-PY7 - - 28.0 - 4.31 206 - - 2.63 7.72 - - 0.068 1.93 - Py1c J1-7-PY8 - - 1583 5.63 4.34 10649 - 0.063 17.6 32.9 - 3.06 1.46 69.3 0.040 Py1c J1-7-PY10 - - 56.8 - 3.16 16912 - 0.044 0.945 8.31 - 1.06 0.124 11.4 - Py1c J1-7-PY15 - - 46.7 - 3.26 237 - - 3.80 16.5 - 0.188 0.585 2.00 - Py1c J1-7-PY18 - - 710 27.2 3.11 579 - - 9.08 34.4 - 0.824 5.70 42.4 0.019 Py1c J7-1PY26 - - 36.3 17.0 1.32 13206 - 0.030 32.8 109 - 5.35 0.228 686 - 类型 点号 Co Ni Cu Zn Ge As Se Mo Ag Sb Te Au Tl Pb Bi Py1c J7-1PY34 0.161 - 3.47 2.84 2.72 8316 - - 1.55 0.942 - 3.62 0.010 16.4 - Py1c J7-1PY36 - - 8.27 1.08 3.26 21571 - - 1.50 4.91 - 3.43 - 33.4 - Py1c J7-1PY39 - 1.97 31.3 2.10 2.82 12356 - - 19.8 70.9 - 5.69 0.173 821 0.086 Py1c J1-5bPY51 - - 1.10 1.60 3.37 7206 - - - - - 0.159 - 0.701 - Py1c J1-5bPY55 1.94 - 34.9 7.66 3.34 56854 - - 9.68 12.1 - 2.39 0.079 60.8 - Py1c J1-5a@14 - - 3.13 - - 7312 - - 2.45 5.72 - 0.320 0.034 19.4 - Py1c J1-5a@15 - - 5.49 - - 19224 - - - - - 0.650 - 0.390 - Py2 J1-7-PY6 0.690 0.799 2612 81.4 3.69 4443 - 0.051 63.9 146 - 1.06 9.86 646 0.066 Py2 J1-7-PY13 - - 2797 875 3.63 1849 - - 84.3 218 - 0.242 1.63 1487 0.112 Py2 J5-1aPY23 1.06 24.6 655 126 2.92 894 - 0.501 127 130 - 0.487 1.32 2550 0.558 Py2 J5-1aPY24 - - 657 103 2.93 10590 11.6 - 82.3 223 - 0.592 0.693 11498 0.030 Py2 J7-1PY40 - 0.768 16.9 1.23 3.06 3191 - - 20.0 61.2 - 0.067 0.375 4496 0.049 Py2 J5-1bPY43 7.02 6.81 1740 9.01 3.29 6204 9.57 0.179 21.9 9.70 - 0.592 0.099 245 0.077 Py2 J5-1bPY44 - - 783 818 3.44 250 3.76 0.643 41.5 46.3 - 0.233 0.636 1354 - Py2 J1-5bPY47 0.345 6.01 167 162 3.51 7572 - - 495 138 - 0.879 1.25 1038 0.354 Py2 J1-5bPY50 - - 113 154 2.97 1568 - - 2.18 4.33 - 0.081 - 84.4 0.027 Py2 J1-5bPY53 - - 914 36.1 2.56 8.77 - - 12.8 6.80 - - 0.006 58.4 0.028 元素平均检出限 0.098 0.806 0.827 1.43 0.696 1.56 5.97 0.125 0.049 0.238 0.510 0.051 0.008 0.071 0.016 注：“-”表示低于检出限
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