Processes of Enrichment of Trace Metals for High-Tech Applications in Hydrothermal Veins of the Ruhr Basin and the Rhenish Massif, Germany

S. Henning, T. Graupner, Thomas Krassmann, H. Gäbler, S. Goldmann, J. Kus, Peter Onuk
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Abstract

The increasing demand for high-tech trace elements supports the need for systematic investigations of their primary occurrences. Mineralogy and trace element characteristics of hydrothermal base-metal veins from the Ruhr Basin (Ruhrgebiet) and the Rhenish Massif (Bergisches Land) in Germany were studied by energy-dispersive X-ray fluorescence mapping, laser ablation-ICP-mass spectrometry, and electron microprobe analyses. Quantitative trace element analysis proves elevated concentrations of Ge and Ga in sphalerite from the Ruhrgebiet. In addition to about 6 Mt of sphalerite-dominated ore, a potential of about 10 t of Ge is indicated to be concentrated in the Auguste Victoria and Graf-Moltke base-metal deposits in the Ruhrgebiet. Assessments on physicochemical fluid properties and metal sources using vitrinite reflectance analysis and host rock investigation indicate a genetic link between the Carboniferous carbonaceous rocks (hosting a number of coal seams) and significant trace metal enrichment in the veins. Gallium enrichment, outlining primary growth zones in ore stage 1 sphalerite, is facilitated by the alteration of Al-bearing minerals in adjacent host rocks due to intense fluid/rock interaction. Reduced Ga and very low In concentrations in ore stage 2 may reflect sealed fluid pathways or changes in the fluid properties. The high level of organic matter in the system probably supported enrichment of Ge in the hydrothermal fluids. The constantly high levels of fixation of Ge in sector zoning patterns of the sphalerite during both ore stages indicate a continuous supply. Elevated contents of Sb together with Cu, As, and Pb in sectors of the sphalerite grains point to a local enrichment of nanometer-scale inclusions of sulfosalt-like phases. Sphalerite of both districts and even of the two ore stages in the Ruhrgebiet shows variations in δ34S isotope compositions due to varying sulfur sources. Both the host rock composition and the presence of organic matter contributed to the trace metal enrichment in the Ruhrgebiet base-metal sulfides as compared to the low contents typical of base-metal ore from the Bergisches Land.
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德国鲁尔盆地和莱茵地块热液脉中用于高科技应用的微量金属富集过程
对高科技微量元素日益增长的需求支持了对其主要出现点进行系统调查的需要。采用能量色散x射线荧光成像、激光烧蚀- icp -质谱和电子探针分析等方法研究了德国鲁尔盆地(Ruhrgebiet)和莱茵地块(Bergisches Land)热液基本金属矿脉的矿物学和微量元素特征。微量元素定量分析表明,鲁尔盖特闪锌矿中锗和镓含量升高。除了约600万吨闪锌矿为主的矿石外,在Ruhrgebiet的Auguste Victoria和grafmoltke贱金属矿床中还发现了约10吨的锗。利用镜质组反射率分析和寄主岩石调查对物化流体性质和金属来源进行评价,表明石炭系碳质岩石(寄存大量煤层)与矿脉中显著的微量金属富集之间存在成因联系。由于强烈的流体/岩石相互作用,邻近寄主岩石中的含铝矿物发生了蚀变,从而促进了镓的富集,描绘了矿期1闪锌矿的原生生长带。矿石阶段2中Ga的减少和非常低的In浓度可能反映了封闭的流体通道或流体性质的变化。该体系中有机质含量高,可能支持了热液中Ge的富集。在两个矿石阶段,闪锌矿的扇形分区模式中,锗的固定水平一直很高,这表明有持续的供应。闪锌矿颗粒部分中Sb、Cu、As和Pb含量升高,表明局部富集了纳米级的类硫代盐相包裹体。由于硫源的不同,鲁尔盖盖特两区甚至两矿期闪锌矿的δ34S同位素组成也发生了变化。与Bergisches地的低含量贱金属矿石相比,宿主岩石组成和有机质的存在都有助于Ruhrgebiet贱金属硫化物中微量金属的富集。
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