The Application of EPMA in the Textural Characterization of Cryptomelane in the Xialei Manganese Deposit, Southwest Guangxi
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摘要:
八面体分子筛(OMS-2)具有2×2孔道结构，在离子交换、催化剂、能源和环境等方面具有非常重要的应用价值，然而天然OMS-2矿物材料——锰钾矿在典型结构的成分精细表征和成因研究等方面仍然缺乏。环带和核-边结构在锰氧化物矿物的结构中非常具有代表性，明确其矿物种属、探索其成分特征对于探究其成因、开拓锰氧化物的应用具有重要意义。广西锰矿资源储量占中国锰矿资源储量的23%，其中位于桂西南的下雷锰矿是中国最早发现的超大型锰矿床，氧化锰矿石平均品位30%左右。本研究主要利用电子探针(EPMA)定量分析和面扫描等手段针对下雷锰矿中的环带和核-边结构开展研究。结果表明：下雷锰矿产出具有环带结构和核-边结构的锰钾矿，具有环带结构的锰钾矿元素强度按平均强度排序从强至弱依次为Mn、K、Mg、Al、Zn、Ba、P、Fe，具有核-边结构的锰钾矿元素强度按平均强度排序从强至弱依次为Mn、K、Ca、Mg、Zn、Ba、P、Fe，这些元素从内到外的变化反映了其氧化环境的变化。从中间到边部钾含量逐渐升高(质量分数为2.31%~4.17%，单位分子式中原子数为0.38~0.62)，暗示了氧化过程中钾的富集，也反映了锰氧化物逐渐趋于最稳定状态的过程。钾离子和锰离子趋势的变化是导致环带和核-边结构形成的直接原因，氧化环境的变化和锰氧化物逐渐趋于最稳定状态的趋势可能是锰钾矿环带和核-边结构形成的根本原因。
Abstract:BACKGROUND OMS-2 has shown great significance in ion exchange, catalyst, energy and environment, but the research of natural OMS-2 mineral material cryptomelane is still lacking in the detailed characterization of the composition, structure and genetic research. Annulus and core-rim structures are representative in the structure of manganese oxide minerals. It is of great significance to clarify the mineral species and explore its composition characteristics, its origin and develop the application of manganese oxides. The Mn ore resource of Guangxi account for 23% of the manganese ore resource reserves in China. The Xialei Mn deposit located in Southwest Guangxi is the earliest super-large Mn deposit discovered in China, with an average grade of about 30% for the manganese oxide ore.
OBJECTIVES To explore the annulus and core-rim texture and its composition of cryptomelane in the Xialei Mn deposit.
METHODS Quantitative analysis and element mapping of EPMA and microscopy were carried out.
RESULTS The element intensity of the cryptomelane with annulus texture was Mn, K, Mg, Al, Zn, Ba, P, Fe in order of average from strong to weak. The average element intensity of the cryptomelane with core-rim texture was Mn, K, Ca, Mg, Zn, Ba, P, Fe from strong to weak. The K content gradually increased (2.31%-4.17%, 0.38-0.62 atoms per formula unit) from the middle to the rim of the cryptomelane, indicating K enrichment during oxidization and the stable status of Mn oxides.
CONCLUSIONS The change in the trend of K and Mn ions is the direct cause of the formation of the annulus and core-rim texture, reflecting the changes of oxidation environment. Potassium content gradually increases from the inner to outer zone, which may indicate the enrichment of potassium during the oxidation process, and also reflects manganese oxide gradually tending to the most stable state.
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表 1 广西下雷锰矿锰钾矿电子探针定量分析数据
Table 1. Chemical composition of the cryptomelane from the Xialei manganese deposit measured by EPMA
测点编号 各成分含量(%) Al2O3 SiO2 CaO P2O5 BaO ZrO2 PbO TiO2 FeO Cr2O3 NiO CuO Na2O MgO ZnO MnO2 K2O SrO SO3 总计 环带1-1 0.04 0.08 0.64 0.47 0.02 0.02 0.02 0.04 0.15 0.05 0.00 0.08 0.12 0.06 0.14 96.04 3.41 0.16 0.01 101.52 环带1-2 0.02 0.06 0.67 0.46 0.00 0.00 0.05 0.00 0.05 0.00 0.00 0.06 0.05 0.03 0.09 95.46 3.44 0.15 0.01 100.60 环带1-3 0.15 0.12 0.66 0.26 0.00 0.02 0.00 0.09 0.04 0.00 0.00 0.06 0.02 0.06 0.10 93.71 3.74 0.13 0.17 99.34 环带1-4 0.16 0.10 0.67 0.24 0.00 0.01 0.02 0.05 0.06 0.02 0.00 0.11 0.06 0.09 0.12 93.72 3.77 0.21 0.13 99.53 环带1-5 0.13 0.07 0.63 0.28 0.00 0.06 0.00 0.00 0.04 0.00 0.00 0.06 0.06 0.07 0.10 94.09 3.94 0.22 0.04 99.78 环带1-6 0.04 0.06 0.50 0.57 0.00 0.00 0.05 0.02 0.01 0.06 0.05 0.08 0.11 0.03 0.11 95.62 4.17 0.12 0.02 101.62 环带2-1 0.01 0.02 0.03 0.08 0.11 0.00 0.00 0.00 0.04 0.06 0.14 0.01 0.02 0.03 0.08 94.76 3.38 0.11 0.02 98.71 环带2-2 0.00 0.05 0.00 0.00 0.13 0.02 0.05 0.02 0.04 0.03 0.14 0.00 0.05 0.00 0.00 94.54 3.33 0.09 0.00 98.39 环带2-3 0.00 0.00 0.00 0.06 0.11 0.04 0.13 0.00 0.08 0.05 0.19 0.00 0.00 0.00 0.06 91.84 3.70 0.13 0.08 96.41 环带2-4 0.01 0.00 0.00 0.01 0.12 0.05 0.17 0.00 0.08 0.06 0.19 0.01 0.00 0.00 0.01 92.04 3.70 0.18 0.07 96.66 环带2-5 0.00 0.01 0.00 0.00 0.09 0.07 0.16 0.08 0.07 0.08 0.13 0.00 0.01 0.00 0.00 91.85 3.73 0.14 0.11 96.50 环带2-6 0.01 0.00 0.00 0.00 0.06 0.03 0.07 0.01 0.03 0.06 0.17 0.01 0.00 0.00 0.00 93.13 3.87 0.15 0.05 97.64 核1-1 0.12 0.04 1.45 0.00 0.15 0.00 0.01 0.00 0.06 0.00 0.00 0.00 0.09 1.98 0.00 85.40 2.31 0.07 0.01 91.68 核1-2 0.11 0.00 1.37 0.00 0.14 0.00 0.00 0.00 0.12 0.02 0.00 0.01 0.06 1.96 0.02 86.61 2.33 0.04 0.01 92.81 核1-3 0.17 0.04 1.21 0.15 0.08 0.00 0.02 0.12 0.04 0.02 0.00 0.07 0.06 1.02 0.14 89.00 3.02 0.17 0.02 95.33 边1-4 0.15 0.06 0.47 0.72 0.02 0.01 0.02 0.00 0.05 0.02 0.00 0.00 0.09 0.00 0.18 94.20 4.02 0.19 0.01 100.21 边1-5 0.14 0.04 0.64 0.66 0.02 0.01 0.00 0.03 0.12 0.00 0.00 0.00 0.06 0.05 0.00 94.94 3.97 0.11 0.02 100.81 边1-6 0.13 0.06 0.46 0.72 0.00 0.02 0.03 0.07 0.11 0.04 0.03 0.03 0.09 0.04 0.16 95.49 4.07 0.18 0.00 101.72 核2-1 0.04 0.10 1.13 0.16 0.07 0.00 0.04 0.00 0.16 0.00 0.09 0.01 0.09 1.16 0.13 88.21 2.97 0.10 0.03 92.98 核2-2 0.04 0.07 1.11 0.30 0.00 0.00 0.04 0.04 0.14 0.00 0.13 0.05 0.14 0.46 0.12 91.09 3.39 0.16 0.01 95.75 核2-3 0.04 0.07 1.22 0.23 0.06 0.00 0.00 0.02 0.19 0.03 0.10 0.00 0.06 0.85 0.25 89.01 3.12 0.13 0.00 93.74 边2-4 0.11 0.07 0.43 0.53 0.00 0.01 0.00 0.00 0.04 0.01 0.05 0.04 0.00 0.03 0.13 94.20 3.84 0.12 0.01 98.47 边2-5 0.12 0.06 0.45 0.74 0.00 0.00 0.02 0.00 0.08 0.01 0.04 0.02 0.05 0.03 0.27 94.37 3.77 0.12 0.01 98.79 边2-6 0.10 0.05 0.44 0.59 0.01 0.00 0.01 0.03 0.12 0.06 0.00 0.01 0.08 0.01 0.11 94.36 3.86 0.11 0.02 98.78 最大值 0.37 0.12 1.45 0.74 0.15 0.06 0.05 0.12 0.19 0.07 0.17 0.11 0.14 1.98 0.27 96.04 4.17 0.22 0.17 - 最小值 0.02 0.00 0.43 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 85.40 2.31 0.04 0.00 - 平均值 0.11 0.06 0.78 0.39 0.03 0.01 0.01 0.03 0.10 0.02 0.05 0.03 0.07 0.38 0.13 92.39 3.48 0.13 0.03 - 单位分子中阳离子数 测点编号 Al2O3 SiO2 CaO P2O5 BaO ZrO2 PbO TiO2 FeO Cr2O3 NiO CuO Na2O MgO ZnO MnO2 K2O SrO SO3 环带1-1 0.005 0.009 0.080 0.046 0.001 0.001 - 0.003 0.014 0.005 - 0.011 0.009 0.003 0.012 7.718 0.506 0.010 0.001 环带1-2 0.003 0.007 0.084 0.046 - - 0.002 - 0.005 - - 0.009 0.004 0.002 0.008 7.739 0.514 0.010 0.001 环带1-3 0.022 0.015 0.084 0.026 - 0.001 - 0.008 0.004 - - 0.008 0.002 0.003 0.009 7.700 0.568 0.009 0.015 环带1-4 0.023 0.012 0.085 0.024 - - 0.001 0.004 0.006 0.002 - 0.016 0.004 0.005 0.010 7.697 0.572 0.014 0.012 环带1-5 0.019 0.008 0.080 0.028 - 0.003 - - 0.003 - - 0.009 0.004 0.004 0.009 7.718 0.597 0.015 0.004 环带1-6 0.006 0.007 0.062 0.056 - - 0.002 0.002 0.001 0.005 0.005 0.011 0.008 0.002 0.009 7.697 0.620 0.008 0.002 环带2-1 0.006 0.004 0.075 0.047 0.001 0.001 0.001 0.007 0.011 - - - 0.003 0.003 0.012 7.734 0.510 0.007 0.001 环带2-2 0.008 0.002 0.085 0.048 - 0.003 - - 0.013 0.002 0.004 0.003 0.003 0.002 0.012 7.735 0.503 0.006 - 环带2-3 0.053 0.013 0.090 0.039 - - - 0.006 0.011 0.004 0.012 - 0.006 0.003 0.017 7.658 0.570 0.009 0.007 环带2-4 0.030 0.012 0.081 0.030 0.001 - - 0.001 0.012 0.005 0.016 - 0.006 0.003 0.017 7.692 0.571 0.012 0.007 环带2-5 0.014 0.007 0.085 0.032 - 0.001 - - 0.009 0.007 0.016 0.011 0.005 0.004 0.012 7.695 0.578 0.010 0.010 环带2-6 0.009 0.008 0.090 0.030 - - - - 0.006 0.003 0.007 0.002 0.002 0.004 0.015 7.719 0.593 0.010 0.005 核1-1 0.018 0.005 0.199 - 0.008 - - - 0.007 - - - 0.006 0.102 - 7.580 0.379 0.005 0.001 核1-2 0.017 - 0.187 - 0.007 - - - 0.012 0.002 - 0.001 0.004 0.102 0.002 7.594 0.377 0.003 0.001 核1-3 0.024 0.005 0.160 0.015 0.004 - 0.001 0.011 0.004 0.002 - 0.010 0.004 0.055 0.012 7.623 0.478 0.012 0.001 边1-4 0.021 0.007 0.059 0.072 0.001 - 0.001 - 0.005 0.002 - - 0.007 - 0.016 7.680 0.606 0.013 0.001 边1-5 0.019 0.005 0.080 0.066 0.001 0.001 - 0.002 0.011 - - - 0.004 0.003 - 7.687 0.594 0.008 0.002 边1-6 0.017 0.007 0.058 0.071 - 0.001 0.001 0.006 0.011 0.004 0.003 0.004 0.006 0.002 0.014 7.671 0.603 0.012 - 核2-1 0.006 0.012 0.151 0.017 0.003 - 0.001 - 0.016 - 0.009 0.002 0.006 0.061 0.012 7.625 0.474 0.007 0.003 核2-2 0.005 0.009 0.145 0.031 - - 0.001 0.003 0.014 - 0.013 0.007 0.010 0.025 0.010 7.661 0.527 0.011 0.001 核2-3 0.006 0.008 0.162 0.024 0.003 - - 0.002 0.019 0.003 0.010 - 0.004 0.045 0.023 7.635 0.494 0.009 - 边2-4 0.015 0.008 0.055 0.054 - - - - 0.004 0.001 0.005 0.006 - 0.002 0.011 7.718 0.581 0.008 0.001 边2-5 0.017 0.007 0.057 0.074 - - 0.001 - 0.007 0.001 0.004 0.003 0.004 0.001 0.024 7.686 0.567 0.008 0.001 边2-6 0.014 0.005 0.056 0.059 - - - 0.002 0.011 0.006 - 0.001 0.006 0.001 0.010 7.706 0.583 0.008 0.002 最大值 0.053 0.015 0.199 0.074 0.008 0.003 0.002 0.011 0.019 0.007 0.016 0.016 0.010 0.102 0.024 7.739 0.620 0.015 0.015 最小值 0.003 - 0.055 - - - - - 0.001 - - - - - - 7.580 0.377 0.003 - 平均值 0.016 0.007 0.101 0.039 0.001 - - 0.003 0.010 0.002 0.005 0.004 0.005 0.020 0.012 7.679 0.532 0.009 0.003 注：环带1-1至1-6指对下雷锰矿具有环带结构的锰钾矿中从中间依次向边部进行电子探针分析，分析位置见图 3a；环带2-1至2-6用于数据验证(选取另一采自下雷锰矿具有环带结构的锰钾矿中从中间依次向边部进行电子探针分析)。核-边1-6指对下雷锰矿具有核-边结构的锰钾矿进行电子探针分析，核1-1至1-3为核部，边1-4至1-6为边部，分析位置见图 3c；核-边2-1至2-6用于数据验证(选取另一采自下雷锰矿具有核边结构的锰钾矿，核2-1至2-3为核部电子探针数据，边2-4到6为边部电子探针数据)。
表中变价元素Mn以+4价计算。0.00表示低于检测限。
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