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Phase relationships in the system ZnS-CuInS2: Insights from a nanoscale study of indium-bearing sphalerite

文献类型：期刊论文

作者Xu, Jing1,3; Ciobanu, Cristiana L.1; Cook, Nigel J.1; Slattery, Ashley5; Li, Xiaofeng2,3,4; Kontonikas-Charos, Alkiviadis1
刊名AMERICAN MINERALOGIST
出版日期2021-02-01
卷号106期号:2页码:192-205
关键词Sphalerite indium system ZnS-CuInS2 HAADF STEM
ISSN号0003-004X
DOI10.2138/am-2020-7488
英文摘要Micrometer- to submicrometer-scale indium-rich domains are preserved within sphalerite included in hornfels-hosted pyrrhotite from the Dulong polymetallic skarn, Yunnan, China. The nano-mineralogy of the ZnS-bearing blebs was investigated using scanning transmission electron microscopy on thinned foils extracted in situ from pyrrhotite. Indium incorporation in sphalerite occurs via the coupled substitution 2Zn(2+) <-> Cu+ + In3+; the results thus allow insights into phase relationships in the system ZnS-CuInS2 in which solubility limits are debated with respect to a cubic to tetragonal phase transition. The highest concentrations of In are measured in basket-weave domains from the smallest ZnS blebs or from un-patterned areas in coarser, irregular ZnS inclusions in pyrrhotite. Indium-rich domains contain 17-49 mol% CuInS2, whereas In-poor sphalerite contains <5 mol% CuInS2. Atomic-scale metal ordering observed in In-(Cu)-rich ZnS domains was modeled as mixed sites in a cubic structure with P<(4)over bar>3m symmetry and empirical formula [(Cu,In,Zn)(3)(Zn0.5Fe0.5)](4)S-4. This sphalerite modification is distinct from the cubic-tetragonal phase transition reported elsewhere for analogous, synthetic phases with abundant planar defects. The Zn1.5Fe0.5CuInS4 nanophase described here potentially represents a Fe-bearing polymorph of Zn2CuInS4, considered as an end-member in the sakuraiite solid-solution series. At <= 50 mol% CuInS2 in the ZnS-CuInS2 system, incorporation of In via coupled In+Cu substitution is promoted within a cubic ZnS phase with lower symmetry than sphalerite rather than into the spatially coexisting chalcopyrite of tetragonal symmetry. Solid-state diffusion accounts for phase re-equilibration resulting in the basket-weave textures typical of In-(Cu)-rich domains in the smallest blebs, whereas fluid percolation assists grain coarsening in the irregular inclusions. The results show evidence for the existence of a more complex phase transition than previously recognized from experimental studies, and, intriguingly, also to a potential eutectic in the system ZnS-CuInS2. Pyrrhotite-bearing hornfels in skarns may concentrate In and other critical metals hosted in sphalerite and related sulfides due to the efficient scavenging from fluid by these minerals and the subsequent preservation of those included phases by sealing within the pyrrhotite matrix.
WOS关键词CRYSTAL-CHEMISTRY ; MINOR ELEMENTS ; TRACE-ELEMENTS ; ZNS MINERALS ; STANNITE ; DEPOSIT ; TRANSITION ; MECHANISM ; DISORDER ; FILMS
资助项目National Key RandD Program of China[2017YFC0602500] ; Key Laboratory of Mineral Resources[KLMR2017-13] ; China Postdoctoral Science Foundation ; China Scholarship Council
WOS研究方向Geochemistry & Geophysics ; Mineralogy
语种英语
WOS记录号WOS:000613919300004
出版者MINERALOGICAL SOC AMER
资助机构National Key RandD Program of China ; National Key RandD Program of China ; National Key RandD Program of China ; National Key RandD Program of China ; Key Laboratory of Mineral Resources ; Key Laboratory of Mineral Resources ; Key Laboratory of Mineral Resources ; Key Laboratory of Mineral Resources ; China Postdoctoral Science Foundation ; China Postdoctoral Science Foundation ; China Postdoctoral Science Foundation ; China Postdoctoral Science Foundation ; China Scholarship Council ; China Scholarship Council ; China Scholarship Council ; China Scholarship Council ; National Key RandD Program of China ; National Key RandD Program of China ; National Key RandD Program of China ; National Key RandD Program of China ; Key Laboratory of Mineral Resources ; Key Laboratory of Mineral Resources ; Key Laboratory of Mineral Resources ; Key Laboratory of Mineral Resources ; China Postdoctoral Science Foundation ; China Postdoctoral Science Foundation ; China Postdoctoral Science Foundation ; China Postdoctoral Science Foundation ; China Scholarship Council ; China Scholarship Council ; China Scholarship Council ; China Scholarship Council ; National Key RandD Program of China ; National Key RandD Program of China ; National Key RandD Program of China ; National Key RandD Program of China ; Key Laboratory of Mineral Resources ; Key Laboratory of Mineral Resources ; Key Laboratory of Mineral Resources ; Key Laboratory of Mineral Resources ; China Postdoctoral Science Foundation ; China Postdoctoral Science Foundation ; China Postdoctoral Science Foundation ; China Postdoctoral Science Foundation ; China Scholarship Council ; China Scholarship Council ; China Scholarship Council ; China Scholarship Council ; National Key RandD Program of China ; National Key RandD Program of China ; National Key RandD Program of China ; National Key RandD Program of China ; Key Laboratory of Mineral Resources ; Key Laboratory of Mineral Resources ; Key Laboratory of Mineral Resources ; Key Laboratory of Mineral Resources ; China Postdoctoral Science Foundation ; China Postdoctoral Science Foundation ; China Postdoctoral Science Foundation ; China Postdoctoral Science Foundation ; China Scholarship Council ; China Scholarship Council ; China Scholarship Council ; China Scholarship Council
源URL[http://ir.iggcas.ac.cn/handle/132A11/100124]  
专题地质与地球物理研究所_中国科学院矿产资源研究重点实验室
通讯作者Xu, Jing
作者单位1.Univ Adelaide, Sch Chem Engn & Adv Mat, Adelaide, SA 5005, Australia
2.Univ Chinese Acad Sci, Coll Earth & Planetary Sci, Beijing 100049, Peoples R China
3.Chinese Acad Sci, Inst Geol & Geophys, Key Lab Mineral Resources, Beijing 100029, Peoples R China
4.Chinese Acad Sci, Inst Earth Sci, Beijing 100029, Peoples R China
5.Univ Adelaide, Adelaide Microscopy, Adelaide, SA 5005, Australia
推荐引用方式
GB/T 7714		 Xu, Jing,Ciobanu, Cristiana L.,Cook, Nigel J.,et al. Phase relationships in the system ZnS-CuInS2: Insights from a nanoscale study of indium-bearing sphalerite[J]. AMERICAN MINERALOGIST,2021,106(2):192-205.
APA Xu, Jing,Ciobanu, Cristiana L.,Cook, Nigel J.,Slattery, Ashley,Li, Xiaofeng,&Kontonikas-Charos, Alkiviadis.(2021).Phase relationships in the system ZnS-CuInS2: Insights from a nanoscale study of indium-bearing sphalerite.AMERICAN MINERALOGIST,106(2),192-205.
MLA Xu, Jing,et al."Phase relationships in the system ZnS-CuInS2: Insights from a nanoscale study of indium-bearing sphalerite".AMERICAN MINERALOGIST 106.2(2021):192-205.

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来源：地质与地球物理研究所

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