锂铍络合物稳定性与花岗伟晶岩中锂铍“差异跃迁”耦合关联

doi:10.13745/j.esf.sf.2023.5.3

地学前缘 ›› 2023, Vol. 30 ›› Issue (5): 93-105.DOI: 10.13745/j.esf.sf.2023.5.3

锂铍络合物稳定性与花岗伟晶岩中锂铍“差异跃迁”耦合关联

洪涛¹^,²(), 翟明国³^,⁴^,⁵^,^*(), 王岳军¹^,², 刘星成⁵^,⁶, 徐兴旺³^,⁴^,⁵, 高俊³^,⁴^,⁵, 胡明曦¹^,², 马靖¹^,²

1.中山大学地球科学与工程学院广东省地球动力作用与地质灾害重点实验室, 广东广州 510275
2.南方海洋科学与工程广东省实验室(珠海), 广东珠海 519082
3.中国科学院大学, 北京 100049
4.中国科学院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, 北京 100029
5.中国科学院地球科学研究院, 北京 100029
6.中国科学院广州地球化学研究所同位素地球化学国家重点实验室, 广东广州 510640

收稿日期:2022-12-15 修回日期:2023-01-31 出版日期:2023-09-25 发布日期:2023-10-20
通信作者: *翟明国(1947—),男,中国科学院院士,主要从事变质岩石学、前寒武纪地质和地球化学、火成岩岩石学研究工作以及战略性关键金属超常富集机理研究工作。E-mail: mgzhai@mail.iggcas.ac.cn
作者简介:洪涛(1989—),男,副教授,主要从事稀有金属伟晶岩成矿过程解析、战略性关键矿产集成与科普、锂铍金属熔体/残留相实验岩石学研究工作。E-mail: hongt5@mail.sysu.edu.cn
基金资助:
国家自然科学基金原创探索项目(42250202);国家自然科学基金重大研究计划集成课题(92162323);广东省引进人才创新创业团队项目“大数据-数学地球科学与极端地质事件”;国家自然科学基金面上项目(42272075);广东省自然科学基金面上项目(2022A1515010003)

Coupling relationship between the stability of Li/Be complexes and Li/Be differential enrichment in granitic pegmatites—an experimental study

HONG Tao¹^,²(), ZHAI Mingguo³^,⁴^,⁵^,^*(), WANG Yuejun¹^,², LIU Xingcheng⁵^,⁶, XU Xingwang³^,⁴^,⁵, GAO Jun³^,⁴^,⁵, HU Mingxi¹^,², MA Jing¹^,²

1. Guangdong Provincial Key Laboratory of Geodynamics and Geohazards, School of Earth Sciences and Engineering, Sun Yat-sen University, Guangzhou 510275, China
2. Guangdong Southern Marine Science and Engineering Laboratory (Zhuhai), Zhuhai 519082, China
3. University of Chinese Academy of Sciences, Beijing 100049, China
4. CAS Key Laboratory of Mineral Resources, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
5. Innovation Academy for Earth Science, Chinese Academy of Sciences, Beijing 100029, China
6. State Key Laboratory of Isotope Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China

Received:2022-12-15 Revised:2023-01-31 Online:2023-09-25 Published:2023-10-20

摘要/Abstract

摘要：

伟晶岩型锂铍矿床是国家紧缺的战略性金属锂铍的重要供给矿床类型。但伟晶岩成因中深熔作用产生熔体量少、萃取锂铍效率低;岩浆结晶分异能否高度富集和高效萃取锂铍也存在争议;随着富锂铍的硅酸盐熔体、熔体-热液不混溶作用的发现,岩浆不混溶作用可能也是新的成因机制。近年来,针对伟晶岩型锂铍矿床的熔体至热液阶段成矿过程的研究主要集中在:花岗伟晶岩全岩地球化学特征解析;造岩矿物(云母、石英、长石等)与矿石矿物(绿柱石等)的精细微区元素地球化学变化规律的总结;造岩矿物、矿石矿物及副矿物(石榴石等)中熔体-热液包裹体矿物学-地球化学特征解析。但伟晶岩矿床中熔体、流体包裹体类型复杂,且与矿床形成时代也没有明显关联性。

锂铍在熔体-热液相间的分配行为和分配过程,以及运移锂铍的络合物稳定性差异是深入认识锂铍超常富集机制的关键。然而,对锂铍在熔体-热液相间分配行为的研究仍然相对薄弱,针对运移锂铍的络合物的稳定性也未开展研究。我们设计了不同矿化溶液的pH值、不同钙和铝含量影响下锂铍络合物结晶锂铍的实验,发现锂铍元素在以上3种不同条件下存在明显的差异性结晶沉淀行为:(1)pH对铍络合物的稳定性控制比锂络合物更明显;(2)在pH值不变的条件下,铝的加入促进了铍的沉淀,却影响锂的沉淀;(3)钙的加入对锂沉淀的影响没有对铍沉淀的影响大。后续将从实验地球化学角度(高温高压实验模拟)剖析锂铍各自络合物的类型、稳定性受控因素,以期建立“锂、铍络合物失稳-成矿”新机制。

关键词: 锂铍矿床, 熔体-热液, 锂铍络合物稳定性, 差异成矿

Abstract:

Pegmatite lithium (Li)-beryllium (Be) deposits are an important type of strategic Li-Be deposit. However, anatexis, on one hand, only produces a small amount of pegmatite-forming melts while Li/Be extraction efficiency for anatectic pegmatites is low; on the other hand, it is still controversial whether magmatic fractional crystallization results in high Li/Be enrichment in pegmatites and increased extraction efficiency. With the observation of fluid immiscibility in Li/Be-rich silica melt, it suggested that melt-fluid immiscibility may also lead to pegmatite formation. Current studies on the pegmatite Li-Be mineralization processes during the melt-fluid phase mainly focus on the whole-rock geochemical characteristics of granitic pegmatites, the in-situ geochemical changes of the rock-forming minerals (mica, quartz, feldspar, etc.) and ore minerals (beryl, etc.), and the mineralogical and geochemical characteristics of melt/fluid inclusions in petrogenic minerals, ore minerals, and accessory minerals (garnet, etc.). So far no obvious correlation has been found between the depositional age and the types of melt/fluid inclusions. To understand the mechanism of abnormal Li/Be enrichments in pegmatites it is key to study the distribution and stability of Li/Be complexes during the melt-fluid phase, however, the former study is scarce and the latter non-existent. In this study we investigated the effects of pH and calcium/aluminum additions on the stability of Li/Be complexes. We found that (1) the stability of Be complex was more affected by pH compared to Li complex; (2) under constant pH, the addition of aluminum promoted Be but hindered Li precipitations; and (3) the addition of calcium had less effect on Li than on Be precipitations. Future high-temperature, high-pressure experimental simulation studies should further enhance our understanding of the Li/Be enrichment processes and provide a geochemical basis for new Li/Be mineralization models based on the stability of Li/Be complexes.

Key words: Li-Be deposits, melt/fluid inclusions, stability of Li/Be complexes, episodic metallogenic process

中图分类号:

P571

洪涛, 翟明国, 王岳军, 刘星成, 徐兴旺, 高俊, 胡明曦, 马靖. 锂铍络合物稳定性与花岗伟晶岩中锂铍“差异跃迁”耦合关联[J]. 地学前缘, 2023, 30(5): 93-105.

HONG Tao, ZHAI Mingguo, WANG Yuejun, LIU Xingcheng, XU Xingwang, GAO Jun, HU Mingxi, MA Jing. Coupling relationship between the stability of Li/Be complexes and Li/Be differential enrichment in granitic pegmatites—an experimental study[J]. Earth Science Frontiers, 2023, 30(5): 93-105.

图/表 10

参考文献 90

[1]	翟明国, 吴福元, 胡瑞忠, 等. 战略性关键金属矿产资源: 现状与问题[J]. 中国科学基金, 2019, 33(2): 106-111.
[2]	侯增谦, 陈骏, 翟明国. 战略性关键矿产研究现状与科学前沿[J]. 科学通报, 2020, 65(33): 3651-3652.
[3]	李娜, 张振芳, 王靓靓, 等. 战略性新兴产业若干关键矿产开发应用与展望[M]. 北京: 地质出版社, 2020: 1-185.
[4]	ČERNÝ P. Rare-element granitic pegmatites, part I: anatomy and internal evolution of pegmatitic deposits[J]. Geoscience Canada, 1991, 18(2): 49-67.
[5]	BENSON T R, COBLE M A, RYTUBA J J, et al. Lithium enrichment in intracontinental rhyolite magmas leads to Li deposits in caldera basins[J]. Nature Communications, 2017, 8: 270. DOI PMID
[6]	LINNEN R L, VAN LICHTERVELDE M, CERNY P. Granitic pegmatites as sources of strategic metals[J]. Elements, 2012, 8(4): 275-280. DOI URL
[7]	王登红, 王成辉, 孙艳, 等. 我国锂铍钽矿床调查研究进展及相关问题简述[J]. 中国地质调查, 2017, 4(5): 1-8.
[8]	许志琴, 王汝成, 赵中宝, 等. 试论中国大陆“硬岩型”大型锂矿带的构造背景[J]. 地质学报, 2018, 92(6): 1091-1106.
[9]	郑范博, 王国光, 倪培. 花岗伟晶岩型稀有金属矿床流体成矿机制研究进展[J]. 地质力学学报, 2021, 27(4): 596-613.
[10]	张辉, 吕正航, 唐勇. 新疆阿尔泰造山带中伟晶岩型稀有金属矿床成矿规律、找矿模型及其找矿方向[J]. 矿床地质, 2019, 38(4): 792-814.
[11]	蒋少涌, 王春龙, 张璐, 等. 伟晶岩型锂矿中矿物原位微区元素和同位素示踪与定年研究进展[J]. 地质学报, 2021, 95(10): 3017-3038.
[12]	MÜLLER A, KEYSER W, SIMMONS W B, et al. Quartz chemistry of granitic pegmatites: implications for classification, genesis and exploration[J]. Chemical Geology, 2021, 584: 120507. DOI URL
[13]	WEBSTER J D, THOMAS R, RHEDE D, et al. Melt inclusions in quartz from an evolved peraluminous pegmatite: geochemical evidence for strong tin enrichment in fluorine-rich and phosphorus-rich residual liquids[J]. Geochimica et Cosmochimica Acta, 1997, 61(13): 2589-2604. DOI URL
[14]	CERNY P, LONDON D, NOVAK M. Granitic pegmatites as reflections of their sources[J]. Elements, 2012, 8(4): 289-294. DOI URL
[15]	LONDON D, MORGAN G B. The pegmatite puzzle[J]. Elements, 2012, 8(4): 263-268. DOI URL
[16]	李杭, 洪涛, 杨智全, 等. 稀有金属花岗伟晶岩锆石、锡石与铌钽铁矿U-Pb和白云母⁴⁰Ar/³⁹Ar测年对比研究: 以阿尔金中段吐格曼北锂铍矿床为例[J]. 岩石学报, 2020, 36(9): 2869-2892.
[17]	LONDON D. Ore-forming processes within granitic pegmatites[J]. Ore Geology Reviews, 2018, 101: 349-383. DOI URL
[18]	HULSBOSCH N, BOIRON M C, THOMAS R, et al. Evaluation of the petrogenetic significance of melt inclusions in pegmatitic schorl-dravite from graphic tourmaline-quartz assemblages: application of LA-ICP-QMS analyses and volume ratio calculations[J]. Geochimica et Cosmochimica Acta, 2019, 244: 308-335. DOI URL
[19]	MCCAULEY A, BRADLEY D C. The global age distribution of granitic pegmatites[J]. The Canadian Mineralogist, 2014, 52(2): 183-190. DOI URL
[20]	王汝成, 邬斌, 谢磊, 等. 稀有金属成矿全球时空分布与大陆演化[J]. 地质学报, 2021, 95(1): 182-193.
[21]	舒良树, 朱文斌, 许志琴. 华南花岗岩型锂矿地质背景与成矿条件[J]. 地质学报, 2021, 95(10): 3099-3114.
[22]	CUNEY M, MARIGNAC C, WEISBROD A. The Beauvoir topaz-lepidolite albite granite (Massif Central, France): the disseminated magmatic Sn-Li-Ta-Nb-Be mineralization[J]. Economic Geology, 1992, 87(7): 1766-1794. DOI URL
[23]	熊欣, 李建康, 王登红, 等. 川西甲基卡花岗伟晶岩型锂矿床中熔体、流体包裹体固相物质研究[J]. 岩石矿物学杂志, 2019, 38(2): 241-253.
[24]	THOMAS R, WEBSTER J D, HEINRICH W. Melt inclusions in pegmatite quartz: complete miscibility between silicate melts and hydrous fluids at low pressure[J]. Contributions to Mineralogy and Petrology, 2000, 139(4): 394-401. DOI URL
[25]	CAO M J, ZHOU Q F, QIN K Z, et al. The tetrad effect and geochemistry of apatite from the Altay Koktokay No. 3 pegmatite, Xinjiang, China: implications for pegmatite petrogenesis[J]. Mineralogy and Petrology, 2013, 107(6): 985-1005. DOI URL
[26]	KAETER D, BARROS R, MENUGE J F, et al. The magmatic-hydrothermal transition in rare-element pegmatites from Southeast Ireland: LA-ICP-MS chemical mapping of muscovite and columbite-tantalite[J]. Geochimica et Cosmochimica Acta, 2018, 240: 98-130. DOI URL
[27]	陈欢, 冯梦, 康志强, 等. 桂东北茅安塘伟晶岩中石榴子石的特征及对岩浆演化的指示意义[J]. 地球科学, 2020, 45(6): 2059-2076.
[28]	王汝成, 谢磊, 诸泽颖, 等. 云母: 花岗岩-伟晶岩稀有金属成矿作用的重要标志矿物[J]. 岩石学报, 2019, 35(1): 69-75.
[29]	BREITER K M. Evolution of rare-metal granitic magmas documented by quartz chemistry[J]. European Journal of Mineralogy, 2009, 21(2): 335-346. DOI URL
[30]	OYARZÁBAL J, GALLISKI M Ã, PERINO E. Geochemistry of K-feldspar and muscovite in rare-element pegmatites and granites from the totoral pegmatite field, San Luis, Argentina[J]. Resource Geology, 2009, 59(4): 315-329. DOI URL
[31]	徐兴旺, 洪涛, 李杭, 等. 初论高温花岗岩-伟晶岩锂铍成矿系统: 以阿尔金中段地区为例[J]. 岩石学报, 2020, 36(12): 3572-3592.
[32]	CHAROY B. Beryllium speciation in evolved granitic magmas: phosphates versus silicates[J]. European Journal of Mineralogy, 1999, 11(1): 135-148. DOI URL
[33]	FRANZ G, MORTEANI G. The system BeO-Al₂O₃-SiO₂-H₂O: hydrothermal investigation of the stability of beryl and euclase in the range from 1 to 6 kb and 400 to 800 ℃[J]. Neues Jahrbuch für Mineralogie Abhandlungen, 1981, 140(3): 273-299.
[34]	EVENSEN J M, LONDON D, WENDLANDT R F. Solubility and stability of beryl in granitic melts[J]. American Mineralogist, 1999, 84(5/6): 733-745. DOI URL
[35]	LONDON D, EVENSEN J M. Beryllium in silicic magmas and the origin of beryl-bearing pegmatites[J]. Reviews in Mineralogy and Geochemistry, 2002, 50(1): 445-486. DOI URL
[36]	Ryan J G, Langmuir C H. The systematics of lithium abundances in young volcanic rocks[J]. Geochimica et Cosmochimica Acta, 1987, 51(6): 1727-1741. DOI URL
[37]	BRENAN J M, NERODA E, LUNDSTROM C C, et al. Behaviour of boron, beryllium, and lithium during melting and crystallization: constraints from mineral-melt partitioning experiments[J]. Geochimica et Cosmochimica Acta, 1998, 62(12): 2129-2141. DOI URL
[38]	BARTELS A, BEHRENS H, HOLTZ F, et al. The effect of lithium on the viscosity of pegmatite forming liquids[J]. Chemical Geology, 2015, 410: 1-11. DOI URL
[39]	MULJA T, WILLIAMS-JONES A E. The physical and chemical evolution of fluids in rare-element granitic pegmatites associated with the Lacorne pluton, Québec, Canada[J]. Chemical Geology, 2018, 493: 281-297. DOI URL
[40]	LONDON D. The origin of primary textures in granitic pegmatites[J]. The Canadian Mineralogist, 2009, 47(4): 697-724. DOI URL
[41]	THOMAS R, WEBSTER J D, DAVIDSON P. Be-daughter minerals in fluid and melt inclusions: implications for the enrichment of Be in granite-pegmatite systems[J]. Contributions to Mineralogy and Petrology, 2011, 161(3): 483-495. DOI URL
[42]	MANETA V, BAKER D R, MINARIK W. Evidence for lithium-aluminosilicate supersaturation of pegmatite-forming melts[J]. Contributions to Mineralogy and Petrology, 2015, 170(1): 1-16. DOI URL
[43]	WEBSTER J, THOMAS R, FÖRSTER H J, et al. Geochemical evolution of halogen-enriched granite magmas and mineralizing fluids of the Zinnwald tin-tungsten mining district, Erzgebirge, Germany[J]. Mineralium Deposita, 2004, 39(4): 452-472.
[44]	ZAJACZ Z, HALTER W E, PETTKE T, et al. Determination of fluid/melt partition coefficients by LA-ICPMS analysis of co-existing fluid and silicate melt inclusions: controls on element partitioning[J]. Geochimica et Cosmochimica Acta, 2008, 72(8): 2169-2197. DOI URL
[45]	丁欣, 李建康. 新疆阿斯喀尔特铍矿床的流体和熔体包裹体特征成矿机制研究[J]. 矿物学报, 2015, 35(增刊1): 573-574.
[46]	LI J K, CHOU I M. Homogenization experiments of crystal-rich inclusions in spodumene from jiajika lithium deposit, China, under elevated external pressures in a hydrothermal diamond-anvil cell[J]. Geofluids, 2017, 2017: 1-12.
[47]	ICENHOWER J, LONDON D. An experimental study of element partitioning among biotite, muscovite, and coexisting peraluminous silicic melt at 200 MPa (H₂O)[J]. American Mineralogist, 1995, 80(11/12): 1229-1251. DOI URL
[48]	ACOSTA-VIGIL A, BUICK I, CESARE B, et al. The extent of equilibration between melt and residuum during regional anatexis and its implications for differentiation of the continental crust: a study of partially melted metapelitic enclaves[J]. Journal of Petrology, 2012, 53(7): 1319-1356. DOI URL
[49]	LINNEN R L. The solubility of Nb-Ta-Zr-Hf-W in granitic melts with Li and Li+F; constraints for mineralization in rare metal granites and pegmatites[J]. Economic Geology, 1998, 93(7): 1013-1025. DOI URL
[50]	LONDON D, MORGAN G B. Experimental crystallization of the macusani obsidian, with applications to lithium-rich granitic pegmatites[J]. Journal of Petrology, 2017, 58(5): 1005-1030. DOI URL
[51]	徐兴旺, 翟明国, 洪涛, 等. 大陆地壳锂铍迁移-循环过程与富集-成矿机制[J]. 岩石学报, 2023, 39(3): 639-658.
[52]	BADANINA E V, VEKSLER I V, THOMAS R, et al. Magmatic evolution of Li-F, rare-metal granites: a case study of melt inclusions in the Khangilay complex, Eastern Transbaikalia (Russia)[J]. Chemical Geology, 2004, 210(1/2/3/4): 113-133. DOI URL
[53]	THOMAS R, DAVIDSON P. Revisiting complete miscibility between silicate melts and hydrous fluids, and the extreme enrichment of some elements in the supercritical state: consequences for the formation of pegmatites and ore deposits[J]. Ore Geology Reviews, 2016, 72: 1088-1101. DOI URL
[54]	赵博, 张德会, 张荣臻, 等. 富F熔体-溶液流体体系的地球化学性状及成矿效应研究进展[J]. 地质科学, 2015, 50(1): 222-240.
[55]	WOOD S A. Theoretical prediction of speciation and solubility of beryllium in hydrothermal solution to 300℃ at saturated vapor pressure: application to bertrandite/phenakite deposits[J]. Ore Geology Reviews, 1992, 7(4): 249-278. DOI URL
[56]	MIGDISOV A A, WILLIAMS-JONES A E, WAGNER T. An experimental study of the solubility and speciation of the Rare Earth Elements (III) in fluoride- and chloride-bearing aqueous solutions at temperatures up to 300 ℃[J]. Geochimica et Cosmochimica Acta, 2009, 73(23): 7087-7109. DOI URL
[57]	CARROLL M R, WEBSTER J D. Chapter 7. solubilities of sulfur, noble gases, nitrogen, chlorine, and fluorine in magmas[M]//Volatiles in magmas. Berlin: De Gruyter, 1994: 231-280.
[58]	KEPPLER H. Partitioning of phosphorus between melt and fluid in the system haplogranite-H₂O-P₂O₅[J]. Chemical Geology, 1994, 117(1/2/3/4): 345-353. DOI URL
[59]	马绍良. LiAlO₂ 添加对Na₃AlF₆Al₂O₃熔体初晶温度, Al₂O₃溶解度的影响[C]// 中国科协. 第十五届中国科协年会第15分会场:全国铝冶金技术研讨会论文集. 贵阳: 工程科技Ⅰ辑, 2013: 340-346.
[60]	贾晓林, 郭晓伟, 封鉴秋, 等. 溶胶-凝胶法制备Li-β-Al₂O₃纳米粉体[J]. 硅酸盐通报, 2008, 27(1): 38-41.
[61]	孙仁安, 刘永东, 王长生. SiOM(M=Li, Be, B, Na, Mg, Al)分子结构的DFT研究[J]. 高等学校化学学报, 2000, 21(12): 1870-1874.
[62]	AHRLAND S, CHATT J, DAVIES N R. The relative affinities of ligand atoms for acceptor molecules and ions[J]. Quarterly Reviews, Chemical Society, 1958, 12(3): 265-276. DOI URL
[63]	BAES J C F, MESMER R E. Thermodynamics of cation hydrolysis[J]. American Journal of Science, 1981, 281(7): 935-962. DOI URL
[64]	王玉荣. 高温高压下络合物研究的地球化学意义与实验方法[J]. 科学通报, 1978, 11: 682-686.
[65]	何俊杰, 丁兴, 王玉荣, 等. 沉淀-陈化-返溶作用和压力对热液中氟钛络合物高温水解的影响及地质意义[J]. 岩石学报, 2015, 31(7): 1870-1878.
[66]	熊小林, 侯通, 王小林. 实验矿床学的发展现状和前景展望[J]. 地球科学, 2022, 47(8): 2701-2713.
[67]	朱笑青, 王中刚. 纳米粒子-胶体溶液-吸附作用: 对某些金属矿床成因的探讨[J]. 中国地质, 2002, 29(1): 82-85.
[68]	马生凤, 温宏利, 李冰, 等. 微波消解-耐氢氟酸系统电感耦合等离子体发射光谱法测定铌钽矿中的铌和钽[J]. 岩矿测试, 2016, 35(3): 271-275.
[69]	FEDOSEYEV A D. Synthesis of chrysoberyl and investigation of its suitability as a refractory[J]. Refractories, 1961, 2(5): 230-235. DOI URL
[70]	DAILEY S R, CHRISTIANSEN E H, DORAIS M J, et al. Origin of the fluorine- and beryllium-rich rhyolites of the spor mountain formation, western Utah[J]. American Mineralogist, 2018, 103(8): 1228-1252. DOI URL
[71]	LONDON D. Granitic pegmatites: an assessment of current concepts and directions for the future[J]. Lithos, 2005, 80(1/2/3/4): 281-303. DOI URL
[72]	司幼东, 黄舜华. 铍矿化交代作用的地球化学实验研究[J]. 地质科学, 1963, 4(4): 169-176.
[73]	何畅通, 秦克章, 李金祥, 等. 喜马拉雅东段错那洞钨-锡-铍矿床中铍的赋存状态及成因机制初探[J]. 岩石学报, 2020, 36(12): 3593-3606.
[74]	CHRISTIANSEN E H, BIKUN J, SHERIDAN M, et al. Geochemical evolution of topaz rhyolites from the Thomas Range and Spor Mountain, Utah[J]. American Mineralogist, 1984, 69(3/4), 223-236.
[75]	SOUFI M. Origin and physical-chemical control of topaz crystallization in felsic igneous rocks: contrasted effect of temperature on its OH-F substitution[J]. Earth-Science Reviews, 2021, 213: 103467. DOI URL
[76]	衣龙升, 范宏瑞, 翟明国, 等. 新疆白杨河铍铀矿床萤石Sm-Nd和沥青铀矿U-Pb年代学及其地质意义[J]. 岩石学报, 2016, 32(7): 2099-2110.
[77]	KUNZ B E, WARREN C J, JENNER F E, et al. Critical metal enrichment in crustal melts: the role of metamorphic mica[J]. Geology, 2022, 50(11): 1219-1223. DOI URL
[78]	WEBSTER J D, MANDEVILLE C W. Fluid immiscibility in volcanic environments[J]. Reviews in Mineralogy and Geochemistry, 2007, 65(1): 313-362. DOI URL
[79]	唐勇, 覃山县, 赵景宇, 等. 稀有金属矿物溶解度对花岗伟晶岩成矿作用的制约[J]. 地学前缘, 2022, 29(1): 81-92. DOI
[80]	CANDELA P A. A review of shallow, ore-related granites: textures, volatiles, and ore metals[J]. Journal of Petrology, 1997, 38(12): 1619-1633. DOI URL
[81]	HARRIS A C, KAMENETSKY V S, WHITE N C, et al. Volatile phase separation in silicic magmas at Bajo de la Alumbrera porphyry Cu-Au deposit, NW Argentina[J]. Resource Geology, 2004, 54(3): 341-356. DOI URL
[82]	ZHANG H J, TIAN S H, WANG D H, et al. Lithium isotope behavior during magmatic differentiation and fluid exsolution in the Jiajika granite-pegmatite deposit, Sichuan, China[J]. Ore Geology Reviews, 2021, 134: 104139. DOI URL
[83]	JAHNS R H, BURNHAM C W. Experimental studies of pegmatite genesis: 1, a model for the derivation and crystallization of granitic pegmatites[J]. Economic Geology, 1969, 64(8): 843-864. DOI URL
[84]	SIMMONS W B, PEZZOTTA F, SHIGLEY J E, et al. Granitic pegmatites as sources of colored gemstones[J]. Elements, 2012, 8(4): 281-287. DOI URL
[85]	LENTZ D, FOWLER A. A dynamic model for quartz-feldspar graphic intergrowths from granitic pegmatites in the southwestern Grenville Province[J]. The Canadian Mineralogist, 1992, 30(3), 571-585.
[86]	ČERNÝ P. Rare-element granitic pegmatites, part II: regional to global environments and petrogenesis[J]. Geoscience Canada, 1991, 18(2), 68-81.
[87]	TAYLOR R P, STRONG D F. Recent advances in the geology of granite-related mineral deposits[C]. Montreal: Canadian Institute of Mining and Metallurgy, 1988, S( 39): 50-71.
[88]	张玲, 梁磊. 伟晶岩与细晶岩的成因: 以广西栗木稀有金属花岗岩地区为例[J]. 桂林理工大学学报, 2018, 38(2): 175-188.
[89]	付小方, 黄韬, 邹付戈, 等. 甲基卡式锂矿田控矿作用与深部找矿方向[J]. 地质学报, 2021, 95(3): 791-808.
[90]	朱金初, 李人科, 周凤英, 等. 广西栗木水溪庙不对称层状伟晶岩-细晶岩岩脉的成因讨论[J]. 地球化学, 1996, 25(1): 1-9.

产地	主矿物	子晶矿物组合	Be和Li₂O的质量分数/10^-6	文献来源
Beauvoir, France	花岗岩全岩		303±58(Be)	Charoy^[32]
实验室合成	无堇青石花岗岩		130(Be)	London和Evensen^[35]
Ehrenfriedersdorf, Germany	熔体包裹体		9 600(Be)	Webster等^[13]
Zinnwald, Germany	熔体包裹体		670(Be)	Webster等^[43]
Mt. Malosa	伟晶状石英中熔体包裹体		570±150(Be)	Zajacz等^[44]
Ehrenfriedersdorf, Erzgebirge, Germany	伟晶状石英中熔体包裹体	锂磷铝石+磷铍钙石+ 磷酸钠铍石+硼铍石	1 450(Be)	Thomas等^[41]
富Ta(Ta质量分数为2 000×10^-6~ 4 000×10^-6)细晶岩	实验熔体		10 000(Li₂O )	Linnen^[49]

产地	主矿物	子晶矿物组合	Be和Li₂O的质量分数/10^-6	文献来源
Beauvoir, France	花岗岩全岩		303±58(Be)	Charoy^[32]
实验室合成	无堇青石花岗岩		130(Be)	London和Evensen^[35]
Ehrenfriedersdorf, Germany	熔体包裹体		9 600(Be)	Webster等^[13]
Zinnwald, Germany	熔体包裹体		670(Be)	Webster等^[43]
Mt. Malosa	伟晶状石英中熔体包裹体		570±150(Be)	Zajacz等^[44]
Ehrenfriedersdorf, Erzgebirge, Germany	伟晶状石英中熔体包裹体	锂磷铝石+磷铍钙石+ 磷酸钠铍石+硼铍石	1 450(Be)	Thomas等^[41]
富Ta(Ta质量分数为2 000×10^-6~ 4 000×10^-6)细晶岩	实验熔体		10 000(Li₂O )	Linnen^[49]

铍质量的变化			锂质量的变化
控制沉淀时的pH值	制备K₃BeF₄溶液,换算出其中Be质量。 m₁(Be)/mg	沉淀物以Be(OH)₃为主,换算出其中Be质量。 m₂(Be)/mg	控制沉淀时的pH值	制备LiF溶液,换算出其中Li质量。 m₁(Li)/mg	沉淀物以Li₂CO₃为主,换算出其中Li质量。 m₂(Li)/mg
7	69	0	7	80	0
8	69	2.5	8	80	1.22
9	69	3.95	9	80	2.35
10	69	30.23	10	80	2.47
12	69	63.56	12	80	2.53

铍质量的变化			锂质量的变化
控制沉淀时的pH值	制备K₃BeF₄溶液,换算出其中Be质量。 m₁(Be)/mg	沉淀物以Be(OH)₃为主,换算出其中Be质量。 m₂(Be)/mg	控制沉淀时的pH值	制备LiF溶液,换算出其中Li质量。 m₁(Li)/mg	沉淀物以Li₂CO₃为主,换算出其中Li质量。 m₂(Li)/mg
7	69	0	7	80	0
8	69	2.5	8	80	1.22
9	69	3.95	9	80	2.35
10	69	30.23	10	80	2.47
12	69	63.56	12	80	2.53

铍质量的变化						锂质量的变化
制备K₃BeF₄溶液,换算出其中Be质量。 m₁(Be)/mg	加入不同量的CaCl₂,换算出其中Ca质量。 m₁(Ca)/mg	沉淀时的pH值	从K₃BeF₄及不同量的CaCl₂混合溶液中沉淀物以Be(OH)₂为主,换算出其中Be质量。 m₂(Be)/mg	从上列混合溶液中,沉淀出CaF₂,换算出其中Ca质量。 m₂(Ca)/mg		制备1 mol (锂辉石) LiAl(SiO₃)₂/ Li₂O·Al₂O₃·4SiO₂,换算出其中Li 质量。 m₁(Li)/mg		加入不同量的CaCO₃,换算出其中Ca质量。 m₃(Ca)/mg		沉淀时的pH值		从锂辉石及不同量的CaCO₃混合溶液中沉淀物以铝酸锂(LiAlO₂) 和硅酸钙为主,换算出其中Li 质量。 m₂(Li)/mg		从上列混合溶液中,沉淀出硅酸钙,换算出其中Ca质量。 m₄(Ca)/mg
69	35.7	7	2.7	31.23	20.8		32		7		11.1		30.2
69	71.4	7	4.68	64.01	20.8		73.2		7		13.5		60.1
69	107.1	7	7.92	102.24	20.8		103.2		7		28.2		100.2
69	142.8	7	9.9	136.02	20.8		144.2		7		37.9		116.2
69	178	7	14.78	170.8	20.8		166.5		7		44.3		144.2

锂铍络合物稳定性与花岗伟晶岩中锂铍“差异跃迁”耦合关联

Coupling relationship between the stability of Li/Be complexes and Li/Be differential enrichment in granitic pegmatites—an experimental study

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 90

相关文章 15

编辑推荐

Metrics

本文评价

铍质量的变化						锂质量的变化
制备K₃BeF₄溶液,换算出其中Be质量。 m₁(Be)/mg	加入不同量的AlCl₃,换算出其中Al质量。 m₁(Al)/mg	沉淀时的pH值	从K₃BeF₄及不同量的AlCl₃混合溶液中沉淀物以Be(OH)₂为主,换算出其中Be质量。 m₂(Be)/mg	从上列混合溶液中,沉淀出Al(OH)₃,换算出其中Al质量。 m₂(Al)/mg		制备1 mol (锂辉石) LiAl(SiO₃)₂/ Li₂O·Al₂O₃·4SiO₂,换算出其中Li 质量。 m₁(Li)/mg		加入不同量的AlCl₃,换算出其中Al质量。 m₃(Al)/mg		沉淀时的pH值(同量的碳酸钙)		从锂辉石及不同量的CaCO₃混合溶液中沉淀物以铝酸锂(LiAlO₂) 和硅酸钙为主, 换算出其中Li 质量。 m₂(Li)/mg		从上列混合溶液中,沉淀出铝酸锂(LiAlO₂),换算出其中Al质量。 m₄(Al)/mg
69	33.1	7	2	9.4	20.8		40.1		7		12.3		11.1
69	66.2	7	3.1	12	20.8		50.2		7		9.5		12.3
69	99.3	7	—	—	20.8		70.3		7		8.6		9.4
69	132.4	7	6.05	39.5	20.8		80.6		7		6.37		19.5
69	165.5	7	13.55	85.53	20.8		133.2		7		3.22		25.3

[1]	陈国超, 张晓飞, 裴先治, 裴磊, 李佐臣, 刘成军, 李瑞保. 雅鲁藏布江中段日喀则地区却顶布—路曲地幔橄榄岩岩石地球化学特征、成因及其地质意义[J]. 地学前缘, 2024, 31(3): 1-19.
[2]	聂潇, 陈雷, 郭现轻, 于涛, 王宗起. 南秦岭中段宁陕地区绿柱石-铌铁矿型伟晶岩中磷灰石和铌铁矿族矿物的矿物地球化学研究[J]. 地学前缘, 2023, 30(5): 115-133.
[3]	杜佰松, 朱光有, 刘舒飞, 王业晗, 于炳松, 徐渴鑫. 浅析影响方解石生长和溶解的动力学因素及机制[J]. 地学前缘, 2023, 30(4): 335-351.
[4]	肖雪薇, 陈红汉, 刘秀岩, 彭中勤, 李培军, 王保忠. 湘西吉首斜坡带下寒武统牛蹄塘组页岩气成气过程的流体包裹体证据:以湘吉地1井为例[J]. 地学前缘, 2023, 30(3): 181-194.
[5]	申俊峰, 闫国英, 张萌萌, 王昭静, 徐渴鑫, 孟文祥. 白云鄂博矿床稀土富集过程:来自成因矿物学的证据[J]. 地学前缘, 2023, 30(2): 370-383.
[6]	崔晓亮, 苏尚国, 张雅南, 陈学根, 司晓博, 霍晓燕. 河北太行山南段符山杂岩体岩浆作用深部过程及其大地构造意义[J]. 地学前缘, 2022, 29(1): 342-363.
[7]	樊馥, 侯献华, 郑绵平, 孟凡巍, 杨振京, 苗青. 柴达木盆地大浪滩梁ZK02孔早—中更新世石盐纯液相流体包裹体均一温度及其对钾盐成矿的约束[J]. 地学前缘, 2021, 28(6): 105-114.
[8]	倪艳华, 李明慧, 方小敏, 孟凡巍, 颜茂都, 刘迎新. 柴达木盆地西部中更新世气候转型期的古水温:来自SG-1钻孔石盐流体包裹体的证据[J]. 地学前缘, 2021, 28(6): 115-124.
[9]	李胜荣, 申俊峰, 李林, 张华锋. 基于大数据的成因矿物学研究思考[J]. 地学前缘, 2021, 28(3): 76-86.
[10]	龙政宇, 余晓艳, 郑育宇, 郭碧君. 云南大丫口祖母绿矿床中电气石的地球化学特征及其对成矿的指示意义[J]. 地学前缘, 2021, 28(2): 333-347.
[11]	李瑞鹏, 崔晓亮, 苏尚国, 张雅南, 梁存涛, 陈学根. 河北武安地区隐爆角砾岩特征及成因探讨[J]. 地学前缘, 2021, 28(1): 353-362.
[12]	鲁安怀, 李艳, 丁竑瑞, 王长秋, 许晓明, 刘菲菲, 刘雨薇, 朱莹, 黎晏彰. 天然矿物光电效应:矿物非经典光合作用[J]. 地学前缘, 2020, 27(5): 179-194.
[13]	张聚全, 梁贤, 闫丽娜, 李胜荣, 申俊峰, 卢静, 吴伟哲, 李清. 岩浆作用过程的矿物记录:以邯邢地区中生代侵入岩为例[J]. 地学前缘, 2020, 27(5): 70-87.
[14]	罗照华. 四川攀西地区层状侵入体中堆晶岩成因的矿物学约束[J]. 地学前缘, 2020, 27(5): 61-69.
[15]	孟繁聪, 白盛锦, Alexander B. MAKEYEV, Ksenia V. KULIKOVA. 俄罗斯极地乌拉尔硬玉岩成因矿物学研究[J]. 地学前缘, 2020, 27(5): 88-98.