Genesis of Mesoproterozoic Gaoyuzhuang Formation Manganese Ore in Qinjiayu, East Hebei: Constraints from Mineralogical and Geochemical Evidences
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摘要:
冀东秦家峪锰矿赋存于中元古界蓟县系高于庄组二段底部含锰岩系内，其成因尚不明确. 以秦家峪锰矿ZK58-2钻孔样品为研究对象，通过显微薄片观察、电子探针分析及全岩地球化学分析等方法，探讨了高于庄组锰矿的锰质来源和沉积环境对成矿的贡献. 显微薄片观察、电子探针分析表明，原生矿带中含锰矿物主要为菱锰矿、铁镁菱锰矿、钙菱锰矿、锰方解石等含锰碳酸盐矿物. 主量元素分析显示，相对于底板样品，锰矿层样品(Mn>8%)的TiO2、SiO2、Al2O3、K2O、Na2O含量较低，Mn含量与Al2O3呈负相关. 锰矿层样品和底板样品微量元素相对于上地壳(UCC)未表现出特别富集的特征，富集系数显示仅Th、U轻微富集. Th/U及自生Th/U比值具有相似的地层变化趋势，与较低的Fe/Mn比值共同指示沉积水体以次氧化环境为主. UCC标准化的稀土元素配分曲线较为平坦，不存在显著的Ce异常(Ce/Ce*=1.00±0.02，n=39)，具有较低的Y/Ho比值. 初始87Sr/86Sr比值介于0.713 383~0.725 378之间，平均值为0.720 180，与Al2O3含量呈负相关. 秦家峪锰矿矿物学及地球化学特征表明，高于庄组含锰岩系的锰质来源于热液与陆源风化双重输入，其与裂谷盆地演化、古海洋氧化以及海平面变化等多种因素共同制约着高于庄组锰矿的形成.
Abstract:The Qinjiayu manganese ore in East Hebei occur mainly in manganese-bearing rock series at the bottom of the second member of the Mesoproterozoic Gaoyuzhuang Formation, however, the cause of manganese ore is unclear. In this paper, it uses microscopic observation, electronic microprobe analysis and whole rock geochemical analysis based on the drilling core ZK58-2 samples to provide information on the manganese sources and sedimentary environments which contribute to manganese mineralization. Microscopic examination and electronic microprobe analysis show that manganese-bearing minerals of primary ore belt samples are dominated by rhodochrosite, Fe-Mg rhodochrosite, Ca rhodochrosite and Mn calcite. Compared with based samples, the major elements of the manganese ore belt samples show low TiO2, SiO2, Al2O3, K2O and Na2O contents. Besides, all samples show negative correlation between manganese and Al2O3 contents. The trace elements of all samples show no enrichment relative to the upper crust content (UCC), except Th and U. Th/U ratios and authigenic Th/U ratios have similar stratigraphical tendency, with low Fe/Mn ratios, indicating that paleo-ocean environment was dominated by oxic-suboxic conditions. UCC-normalized REE+Y patterns are flat, showing no Ce anomaly (Ce/Ce*=1.00±0.02, n=39) and low Y/Ho ratios. Initial 87Sr/86Sr ratios of Mn ore belt are between 0.713 383 and 0.725 378, having an average value of 0.720 180, showing a negative correlation with Al2O3 contents. Comprehensive sedimentary and geochemical analyses show that Mn sourced from both hydrothermal fluids and continental weathering input. Manganese sources, combined with paleo-ocean oxidation and sea level fluctuations, controlled the Gaoyuzhuang manganese ore.
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Key words:
- Qinjiayu /
- Gaoyuzhuang Formation /
- manganese ore /
- paleoenvironment /
- geochemistry
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图 1 燕辽坳拉槽高于庄期岩相古地理图
Fig. 1. Lithofacies paleogeographic map of the northern Yanliao aulacogen in the Gaoyuzhuang period
图 2 秦家峪ZK58-2钻孔岩性柱状图
Fig. 2. Lithological column of drilling core ZK58-2 in Qinjiayu area, Qianxi County, Hebei Province
图 3 ZK58-2钻孔岩石薄片照片(a~c)及电子探针背散射照片(d~f)
Q. 石英；Rds.菱锰矿；Cbn.碳酸盐矿物；Py.黄铁矿；Kfs.钾长石
Fig. 3. Optical (a‒c) and BSE (d‒f) micrographs of drilling core ZK58-2
图 4 ZK58-2钻孔样品碳酸盐矿物电子探针分析结果，(Mg+Fe)CO3-CaCO3-MnCO3三角图展示了碳酸盐岩矿物组成
Fig. 4. EMPA results of drilling core ZK58-2 carbonates minerals, (Mg+Fe)CO3-CaCO3-MnCO3 ternary diagram showing the component of carbonate minerals
图 5 ZK58-2钻孔主量元素相关性二元图
红色表示锰矿层样品，黑色表示底板样品
Fig. 5. Cross-plots of major elements of drilling core ZK58-2
图 6 ZK58-2钻孔样品UCC标准化的微量元素蛛网图(a)及富集系数蛛网图(b)
红色表示锰矿层样品，黑色表示底板样品
Fig. 6. UCC-normalized trace element distribution pattern(a)and enrichmemt factor distribution pattern (b)of drilling core ZK58-2 samples
图 7 ZK58-2钻孔UCC标准化的稀土元素配分模式
红色表示锰矿层样品，黑色表示底板样品
Fig. 7. UCC-normalized REE+Y distribution pattern of drilling core ZK58-2 samples
图 8 ZK58-2钻孔Mn、总稀土含量、Ce/Ce*、Th/U比值、自生Th/U比值变化趋势
红色表示锰矿层样品，黑色表示底板样品
Fig. 8. Mn, REE+Y, Ce/Ce*, Th/U ratio and authigenic Th/U ratio variation tendency of drilling core ZK58-2 samples
图 9 ZK58-2钻孔锰矿层初始87Sr/86Sr比值与Al含量相关性
Fig. 9. Initial 87Sr/86Sr vs. Al diagram of drilling core ZK58-2 manganese ore samples
表 1 秦家峪锰矿ZK58⁃2钻孔电子探针分析结果
Table 1. EMPA results of drilling core ZK58-2 in the Qinjiayu manganese ore deposit
点号 1 2 4 5 6 7 9 12 13 14 15 16 17 20 21 25 28 30 31 33 CaO 3.817 13.332 24.904 8.446 13.65 2.908 21.909 54.062 6.65 5.739 5.026 5.942 4.776 28.518 53.828 6.825 5.079 26.963 2.608 5.287 MgO 12.822 8.749 4.466 3.991 6.754 13.014 10.374 0.021 2.322 2.522 2.845 1.957 3.575 9.809 0.019 1.603 7.208 5.612 3.798 2.504 MnO 23.417 21.404 10.033 33.037 25.337 24.371 17.735 0.075 36.847 37.206 36.224 39.249 37.927 10.548 0.21 41.16 34.974 14.711 43.395 38.944 FeO 6.727 4.025 14.502 2.657 3.200 7.223 3.839 0.153 9.715 9.140 9.787 6.559 7.249 8.084 0.294 3.457 8.768 5.612 3.614 6.331 CO2 35.635 35.751 42.221 33.101 35.757 36.026 41.864 42.580 36.556 35.930 35.510 35.159 35.613 44.575 42.564 53.045 38.915 39.842 35.321 34.913 总计 82.418 83.261 96.126 81.232 84.698 83.542 95.721 96.891 92.090 90.537 89.392 88.866 89.140 101.534 96.915 87.796 94.944 92.740 88.736 87.979 CaCO3 8.4 29.3 46.3 20.0 30.0 6.3 41.1 99.6 14.3 12.5 11.1 13.3 10.5 50.2 99.2 15.4 10.2 53.1 5.8 11.9 MgCO3 39.3 26.7 25.9 13.2 20.6 39.4 27.0 0.1 6.9 7.7 8.7 6.1 11.0 24.0 0.0 5.0 20.2 15.4 11.7 7.8 MnCO3 40.8 37.1 21.3 61.9 43.9 42.0 26.3 0.1 62.5 64.2 63.3 69.2 66.1 14.7 0.3 73.5 55.7 22.9 76.2 69.2 FeCO3 11.6 6.9 6.5 4.9 5.5 12.3 5.6 0.2 16.3 15.6 16.9 11.4 12.5 11.1 0.4 6.1 13.8 8.6 6.3 11.1 注：CaCO3、MgCO3、MnCO3、FeCO3的单位为mol%，其他元素含量的单位为%. 
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