Wei Deng , Hanjie Wen , Kunyue Ling , Shengjiang Du , Chongguang Luo , Yang Yang
{"title":"Enrichment mechanisms of Nb, Zr, and REY in the Late Permian coal-bearing strata in western Guizhou, SW China","authors":"Wei Deng , Hanjie Wen , Kunyue Ling , Shengjiang Du , Chongguang Luo , Yang Yang","doi":"10.1016/j.coal.2024.104517","DOIUrl":null,"url":null,"abstract":"<div><p>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 TiO<sub>2</sub> 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 Nb<sup>5+</sup> and Fe<sup>2+</sup>, 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.</p></div>","PeriodicalId":13864,"journal":{"name":"International Journal of Coal Geology","volume":null,"pages":null},"PeriodicalIF":5.6000,"publicationDate":"2024-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"International Journal of Coal Geology","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0166516224000740","RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"ENERGY & FUELS","Score":null,"Total":0}
引用次数: 0
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.
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.