Enrichment mechanisms of Nb, Zr, and REY in the Late Permian coal-bearing strata in western Guizhou, SW China

IF 5.6 2区 工程技术 Q2 ENERGY & FUELS International Journal of Coal Geology Pub Date : 2024-04-22 DOI:10.1016/j.coal.2024.104517
Wei Deng , Hanjie Wen , Kunyue Ling , Shengjiang Du , Chongguang Luo , Yang Yang
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Abstract

Niobium, Zr, REE, and Y are widely enriched in the Upper Permian coal-bearing strata in southwestern China and are regarded as a substantial resource. To better understand the occurrence modes and enrichment mechanisms of these rare metals, comprehensive heavy-mineral separation, Micro-Raman spectroscopy, EPMA, and LA-ICP-MS analyses of primary and secondary metal minerals were conducted in the polymetallic beds in western Guizhou. In addition, the XRD, XRF, and ICP-MS analyses of bulk rocks were carried out. Our results suggest that Nb is primarily hosted in secondary TiO2 polymorphs which converted from primary Nb-rich rutile, and occurs as minor ilmenorutile and columbite-(Fe). The Zr is sequestered in both detrital zircon and secondary microcrystalline zircon. REE and Y (REY) are mainly incorporated into secondary florencite-(Ce), rhabdophane-(Ce), churchite-(Y), and zircon, also partially adsorbed by clay minerals. The assemblage of detrital zircon, Nb-rich rutile, and discrete Nb minerals reveals that rare metals are preconcentrated during the waning-stage Emeishan alkaline magmatisms. Complex zonings in rutile crystals may result from the diffusion of Nb5+ and Fe2+, and these grains are further overprinted by magmatic-hydrothermal and enveloped by ilmenorutile and columbite-(Fe). Furthermore, magmatic rutile is commonly converted into anatase, brookite, and leucoxene under supergene conditions, and then persisted as stable phases. Authigenic REY-rich (Al)-phosphates and zircon are sourced from the leaching, even decomposition of primary REY-phosphates and zircons. Their colloidal aggregates are precipitated from the acidic and oxidizing low-temperature fluids, which are superposed onto clay matrix. The mineralogical and geochemical features suggest that the polymetallic beds are enriched by both alkaline magmatic-hydrothermal processes in source rocks and supergene fluid alterations in sediments. This study gives new insights into the enrichment processes and conditions, and further extraction of critical metals in the coeval coal-bearing strata in southwestern China.

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中国西南部贵州西部晚二叠世含煤地层中 Nb、Zr 和 REY 的富集机制
铌、锆、稀土和钇在中国西南地区上二叠统含煤地层中广泛富集,被认为是一种可观的资源。为了更好地了解这些稀有金属的发生模式和富集机制,对贵州西部多金属床中的原生和次生金属矿物进行了全面的重矿物分离、显微拉曼光谱、EPMA和LA-ICP-MS分析。此外,还对块状岩石进行了 XRD、XRF 和 ICP-MS 分析。研究结果表明,铌主要赋存于由原生富铌金红石转化而来的次生二氧化钛多晶体中,并以少量钛金红石和铌铁矿(铁)的形式存在。锆被封存在锆英石和次生微晶锆石中。REE和Y(REY)主要掺入次生萤石(Ce)、斜长石(Ce)、教堂石(Y)和锆石中,也有部分被粘土矿物吸附。碎屑锆石、富铌金红石和离散铌矿物的组合揭示了稀有金属在峨眉山碱性岩浆活动的减弱阶段被预先富集。金红石晶体中的复杂分带可能是 Nb5+ 和 Fe2+ 扩散的结果,这些晶粒进一步被岩浆-热液覆盖,并被钛金红石和铌铁矿(铁)包裹。此外,岩浆金红石在超成岩条件下通常会转化为锐钛矿、褐铁矿和白钨矿,然后作为稳定相持续存在。原生富REY(Al)-磷酸盐和锆石来源于原生REY-磷酸盐和锆石的浸出甚至分解。它们的胶体聚集体从酸性和氧化性低温流体中析出,叠加在粘土基质上。矿物学和地球化学特征表明,多金属矿床是在源岩的碱性岩浆-热液过程和沉积物的超生流体蚀变作用下富集而成的。这项研究对中国西南部共生含煤地层的富集过程和条件,以及临界金属的进一步提取提出了新的见解。
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来源期刊
International Journal of Coal Geology
International Journal of Coal Geology 工程技术-地球科学综合
CiteScore
11.00
自引率
14.30%
发文量
145
审稿时长
38 days
期刊介绍: The International Journal of Coal Geology deals with fundamental and applied aspects of the geology and petrology of coal, oil/gas source rocks and shale gas resources. The journal aims to advance the exploration, exploitation and utilization of these resources, and to stimulate environmental awareness as well as advancement of engineering for effective resource management.
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