The Occurrence State of Metal Sulfides and Its Relationship with Uranium Mineralization in Diantou-Shuanglong Area, Ordos Basin
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摘要:
在砂岩型铀矿勘查中，除了黄铁矿以外还识别出其他种类丰富的金属硫化物，但目前对于其复杂的矿物种类、微观形态、赋存特征以及和铀矿物关系缺少系统性研究。本文以店头-双龙地区中侏罗世直罗组赋矿岩层为研究对象，利用光学显微镜、扫描电镜以及配备的能谱仪和全反射X射线荧光光谱等方法识别出大量金属硫化物，以黄铁矿、闪锌矿、黄铜矿和方铅矿为主；并在含矿砂岩的过渡带发现金属硫化物呈现出残留的氧化痕迹并被铀矿物所取代。通过对古层间氧化带不同分带中金属硫化物的含量进行统计，由高到低依次为过渡带的含矿砂岩>还原带的灰色不含矿砂岩>二次还原的绿色砂岩≥氧化的红色砂岩；不同类型硫化物含量由高到底依次为黄铁矿>闪锌矿>黄铜矿≥方铅矿。氧化带酸性或偏酸性的地下水以及存在的Fe3+为金属硫化物的氧化提供有利条件。铀酰离子伴随着金属硫化物氧化形成的离子络合物随氧化流体在铀储层砂体中运移，随着还原介质占主导地位，金属离子在过渡带重新富集沉淀形成成矿期金属硫化物。与此同时，过渡带的金属硫化物氧化形成的$ {\text{SO}}_{\text{4}}^{{2-}} $可被还原为H2S，而H2S对铀酰离子具有很强的还原能力。因此，金属硫化物和铀矿物紧密伴生，说明除了黄铁矿以外，其他类型的金属硫化物也可充当还原剂来参与铀的富集沉淀，这对其他砂岩型铀矿床无机还原介质的研究提供一定的借鉴。
Abstract:In the exploration of sandstone-hosted uranium deposits, besides pyrite, other types of metal sulfides have been identified. Nevertheless, there is currently a lack of systematic investigation and research into the metal sulfides about their complex mineral types, microstructure, occurrence characteristics, and relationship with uranium minerals. Therefore, this paper takes the ore-bearing rock strata of the Middle Jurassic Zhiluo Formation in the Diantou-Shuanglong area as the research object. By utilizing optical microscopes, scanning electron microscopes, energy spectrometer, and synchrotron X-ray fluorescence, a large number of metal sulfides were identified, mainly including pyrite, sphalerite, chalcopyrite, and galena. Furthermore, in the transition zone of ore-bearing sandstone, the four principal metal sulfides manifest residual oxidation traces and are replaced by uranium minerals. Through the statistical analysis of the content of metal sulfides, the distribution of various metal sulfides in different zones of the ancient interlayer oxidation zone is as follows, ranked from highest to lowest content: ore-bearing sandstone in the transition zone>gray ore-free sandstone in the reduction zone>green sandstone in the secondary reduction zone≥oxidized red sandstone. The order of different types of metal sulfides content from high to low is pyrite>sphalerite>chalcopyrite ≥ galena. Comprehensive analysis indicates that the acidic or weakly acidic groundwater and the presence of Fe3+ in the oxidation zone can provide favorable conditions for the oxidation of metal sulfides. Uranyl ions accompanied by ion complexes formed by oxidation of metal sulfides migrate in the uranium reservoir with the oxidizing fluid. As reducing media dominates, the migrated metal ions are re-enriched and precipitated in the transition zone to form mineralization stage metal sulfides. Meanwhile, $ {\text{SO}}_{\text{4}}^{{2-}} $ formed by oxidation of metal sulfides in the transition zone can be reduced to H2S, which has a strong reducing ability for uranyl ions. Therefore, metal sulfides are closely associated with uranium minerals, indicating that beyond the well-known pyrite, other metal sulfides can also serve as reducing agents, actively participating in the enrichment and precipitation of uranium. This discovery offers valuable insights for the study of inorganic reducing media in other sandstone-hosted uranium deposits.
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Key words:
- metal sulfides /
- uranium mineralization /
- Zhiluo Formation /
- metallogenic model /
- Diantou-Shuanglong area /
- Ordos Basin
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表 1 研究区金属硫化物在探针片中所占比例
Table 1. The proportion of metal sulfides in the thin sections of the study area
岩性 样品号 金属硫化物占比（%） 总占比（%） 闪锌矿 黄铁矿 黄铜矿 方铅矿 红色+黄色砂岩（n=6） ZK319-05-8 / 0.034 0.0024 0.0061 0.0425 ZK2402-6 / / 0.049 / 0.049 ZK127-09-2 / 0.063 / / 0.063 ZK319-05-5 / / / / / ZK257-01-1 / / / / / ZK175-03-5 0.60 0.20 0.02 0.014 0.834 总占比（%） 0.60 0.297 0.0714 0.02 0.99 平均值（%） 0.1 0.05 0.012 0.003 0.17 绿色砂岩（n=5） ZK127-07-2 / 0.001 / / 0.001 ZK31-08-2 / 0.058 / / 0.058 ZK127-07-5 / 0.232 / / 0.232 ZK127-07-1 / 0.336 0.172 0.002 0.51 ZK31-08-5 / 0.12 / / 0.12 总占比（%） / 0.747 0.172 0.002 0.92 平均值（%） / 0.15 0.034 0.0004 0.18 灰色不含矿砂岩（n=8） ZK159-09-1 0.31 3.73 0.02 / 4.06 ZK323-01-3 0.23 3.4 0.01 0.013 3.65 ZK323-01-1 0.24 0.9 / 0.026 1.17 ZK159-14-2 / 2.11 / / 2.11 ZK003-32 / 2.03 / / 2.03 ZK143-02-3 0.22 1.23 / / 1.45 ZK143-02-6 0.1 1.98 0.02 / 1.982 ZK159-09-2 0.32 1.36 / / 1.68 总占比（%） 1.42 16.74 0.05 0.039 18.13 平均值（%） 0.18 2.09 0.006 0.005 2.28 含矿砂岩（n=8） ZK159-09-4 2.95 0.54 0.003 0.036 3.53 ZK159-09-5 0.05 5.22 无 0.163 5.43 ZK159-09-7 3.82 7.91 0.04 0.005 11.78 ZK159-09-8 2.79 4.18 0.009 0.008 6.99 ZKZ159-09-9 3.83 2.85 无 0.036 6.72 ZK175-03-1 5.2 3.0 0.02 0.09 8.31 ZK175-03-2 2.58 1.56 0.03 0.004 4.17 ZK175-03-6 2.35 2.95 0.003 0.029 5.33 总占比（%） 23.57 28.21 0.105 0.371 52.26 平均值（%） 2.95 3.53 0.01 0.05 6.54 注：/代表百分比小于0.001，可忽略不计. 
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