In situ Raman spectroscopic investigation of the hydrothermal speciation of tungsten: Implications for the ore-forming process

doi:10.1016/j.chemgeo.2019.119299

CORC > 深海科学与工程研究所 > 中国科学院深海科学与工程研究所 > 深海科学研究部 > 深海极端环境模拟研究实验室

	In situ Raman spectroscopic investigation of the hydrothermal speciation of tungsten: Implications for the ore-forming process
	Wang, Xiaolin 3,6; Qiu, Ye 6; Lu, Jianjun 6; Chou, I-Ming 4; Zhang, Wenlan 6; Li, Guanglai 1; Hu, Wenxuan 6; Li, Zhen 2; Zhong, Richen 5
刊名	CHEMICAL GEOLOGY
	2020-01-20
卷号	532 页码:14
关键词	In situ observation Raman spectroscopy Hydrothermal fluids Tungsten speciation CO2 Ore-forming process
ISSN号	0009-2541
DOI	10.1016/j.chemgeo.2019.119299
英文摘要	Knowledge on hydrothermal tungsten (W) species is vital towards a better understanding of tungsten transport and mineralization mechanisms. In this study, in situ Raman spectra of a 0.005 - 0.1 mol/kg (m) K2WO4 solution containing CO2, HCl, and NaHCO3 were collected at 50-400 degrees C and 20-60 MPa. The spectra for the symmetric stretching vibration mode of the W=O bond, nu(1) (W=O), were analyzed to investigate the hydrothermal rung-state species. Results showed that carbonate/bicarbonate do not associate with tungstate to form carbonic tungstate species. Nevertheless, the presence of CO2 can increase the fluid acidity, which favors the formation of polymeric tungstate species at < 300 degrees C. Above about 300 degrees C, monomeric tungstates (e.g., WO42-, HWO4-, H2WO4 and alkali tungstate ion pairs) are responsible for the hydrothermal transport of tungsten, and the nu(1) (W=O) modes of these species are centered at similar to 930 cm(-1) and similar to 950 cm(-1). Based on the above observations, we simulated the mineralization process in the context of fluid-rock interactions using tungstate and alkali tungstate ion pairs as the only aqueous W species. The thermodynamic simulations showed that (a) the timing of mineralization mainly depends on the W concentration in the initial mineralizing fluid and the availability of Ca2+, Fe2+ and Mn2+, with higher W concentrations generally favoring higher temperature mineralization; (b) highly W-enriched fluid is not essential for W mineralization, while extremely low contents of Fe, Mn and Ca in the magma are useful to maintain the mobility of aqueous W until favorable host rocks are encountered; and (c) a "hydrogen reservoir" effect was identified for dissolved CO2. The presence of CO2 can promote the extraction of Fe(II) from the pelitic host rocks, thereby facilitating a high-grade vein-type W mineralization. At < similar to 300 degrees C, polytungstate species, whose nu(1) (W=O) modes are centered at similar to 965 - 995 cm(-1), are important hydrothermal W species along with monomeric tungstates. Therefore, polymeric tungstate species should be considered in future thermodynamic modeling of W transport and mineralization at < 300 degrees C. An increase in fluid pH induced by CO2-escape and/or fluid-rock interactions will destabilize the polymeric rungstates to form WO42- and other monomeric tungstate, which interacts with metal cations to form wolframite and/or scheelite.
资助项目	National Natural Science Foundation of China[41830428] ; National Natural Science Foundation of China[41922023] ; National Natural Science Foundation of China[41862004] ; National Natural Science Foundation of China[41573054] ; Fundamental Research Funds for the Central Universities[020614380056] ; Fundamental Research Funds for the Central Universities[020614380078] ; Key Frontier Science Program of the Chinese Academy of Sciences[QYZDY-SSW-DQC008]
WOS关键词	INITIO MOLECULAR-DYNAMICS ; LIQUID PHASE-SEPARATION ; W-SN DEPOSITS ; FLUID-INCLUSION ; AQUEOUS-SOLUTIONS ; STABLE-ISOTOPE ; DEGREES-C ; THERMODYNAMIC PROPERTIES ; CHINA IMPLICATIONS ; COEXISTING QUARTZ
WOS研究方向	Geochemistry & Geophysics
语种	英语
出版者	ELSEVIER
WOS记录号	WOS:000513868400015
资助机构	National Natural Science Foundation of China ; Fundamental Research Funds for the Central Universities ; Key Frontier Science Program of the Chinese Academy of Sciences
内容类型	期刊论文
源URL	[http://ir.idsse.ac.cn/handle/183446/7486]
专题	深海科学研究部_深海极端环境模拟研究实验室
通讯作者	Wang, Xiaolin; Zhong, Richen
作者单位	1.East China Inst Technol, State Key Lab Breeding Base Nucl Resources & Envi, Nanchang 330013, Jiangxi, Peoples R China 2.Curtin Univ, Fac Sci & Engn, John de Laeter Ctr, GPO Box U1987, Perth, WA 6485, Australia 3.Shandong Univ Sci & Technol, Shandong Prov Key Lab Deposit Mineralizat & Sedim, Qingdao 266590, Shandong, Peoples R China 4.Chinese Acad Sci, Inst Deep Sea Sci & Engn, CAS Key Lab Expt Study Deep Sea Extreme Condit, Sanya 572000, Hainan, Peoples R China 5.Univ Sci & Technol Beijing, Civil & Resource Engn Sch, Room 903,Civil Bldg,30 Xueyuan Rd, Beijing 100083, Peoples R China 6.Nanjing Univ, Sch Earth Sci & Engn, State Key Lab Mineral Deposits Res, Nanjing 210023, Jiangsu, Peoples R China
推荐引用方式 GB/T 7714	Wang, Xiaolin,Qiu, Ye,Lu, Jianjun,et al. In situ Raman spectroscopic investigation of the hydrothermal speciation of tungsten: Implications for the ore-forming process[J]. CHEMICAL GEOLOGY,2020,532:14.
APA	Wang, Xiaolin.,Qiu, Ye.,Lu, Jianjun.,Chou, I-Ming.,Zhang, Wenlan.,...&Zhong, Richen.(2020).In situ Raman spectroscopic investigation of the hydrothermal speciation of tungsten: Implications for the ore-forming process.CHEMICAL GEOLOGY,532,14.
MLA	Wang, Xiaolin,et al."In situ Raman spectroscopic investigation of the hydrothermal speciation of tungsten: Implications for the ore-forming process".CHEMICAL GEOLOGY 532(2020):14.