新疆大红柳滩伟晶岩型锂矿床中磷铁锂矿地球化学特征及其对伟晶岩演化的指示意义
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摘要
新疆大红柳滩伟晶岩型锂矿床近年来找矿取得了新进展。我们在该地区典型锂矿脉(90-1号)首次鉴定出磷铁锂矿,其在伟晶岩中呈树枝状、团簇状集合体分布岩脉的边缘带和中部。边缘带尤为富集磷铁锂矿,含量可达10%～15%。本文系统地开展了磷铁锂矿的岩相学和矿物学研究。利用电子探针和激光剥蚀等离子质谱测定了脉体边缘带和中间粗粒锂辉石-白云母-石英带磷铁锂矿的主微量元素含量。结果表明,磷铁锂矿除含有主要元素P、Fe、Mn及Li外,还含有较高的Mg、Ca和Zn,几乎不含高场强元素、稀土元素。综合电子探针和LA-ICP-MS分析结果,认为伟晶岩脉中部分磷铁锂矿已被氧化,成分向铁磷锂锰矿过渡。从脉体的边缘带往中间带,磷铁锂矿中Mg和Zn平均含量下降,而Mn/(Mn+Fe)比值由0.388升至0.409,显示逐渐富Mn特点,与前人关于花岗伟晶岩熔体演化过程中Fe-Mn的分离趋势一致,也与该伟晶岩脉中铌钽铁矿早期演化阶段Mn/(Mn+Fe)比值变化趋势相同;磷铁锂矿被晚期氟磷灰石部分交代,反映伟晶岩演化至热液阶段F、Ca活度增加。表明该矿物可以很好的记录伟晶岩岩浆及热液阶段的演化。
This contribution presents a detailed petrographic and mineralogical study of triphylite from the wall zone and coarse-grained spodumene-muscovite-quartz zone(intermediate zone) of No. 90-1 spodumene pegmatite at Dahongliutan, Xinjiang. Triphylite occurs as dendritic or rounded aggregates in the pegmatite. Electron probe micro-analyzer(EPMA) and laser ablation-inductively coupled plasma-mass spectrometer(LA-ICP-MS) were used to determine the concentrations of major and trace elements in triphylite. Our results show that, besides major elements P, Fe, Mn, and Li, the triphylite contains subordinate Mg, Ca, and Zn. Moreover, HFSE and REE concentrations of the triphylite are extremely low. Integrating the EPMA and LA-ICP-MS data, our study indicates that the triphylite has been partially oxidized and that its composition has evolved towards ferrisicklerite. From the wall zone towards the intermediate zone, the triphylite shows decreased Mg and Zn contents but becomes relatively Mn-enriched as the Mn/(Mn+Fe) ratios of triphylite increase from 0.388 to 0.409. Such a compositional evolutionary trend is consistent with the typical Mn-Fe fractionation trend in many pegmatites according to the literature. Similarly, the columbite-group minerals in the same pegmatite show increasing Mn/(Mn+Fe) ratios at early stages. In addition, the triphylite is partially replaced by fluorapatite, which suggests that the activities of Ca and F increased at the late hydrothermal stage. This suggests that triphylite has potential to document magmatic and hydrothermal evolution of pegmatites.
This contribution presents a detailed petrographic and mineralogical study of triphylite from the wall zone and coarse-grained spodumene-muscovite-quartz zone(intermediate zone) of No. 90-1 spodumene pegmatite at Dahongliutan, Xinjiang. Triphylite occurs as dendritic or rounded aggregates in the pegmatite. Electron probe micro-analyzer(EPMA) and laser ablation-inductively coupled plasma-mass spectrometer(LA-ICP-MS) were used to determine the concentrations of major and trace elements in triphylite. Our results show that, besides major elements P, Fe, Mn, and Li, the triphylite contains subordinate Mg, Ca, and Zn. Moreover, HFSE and REE concentrations of the triphylite are extremely low. Integrating the EPMA and LA-ICP-MS data, our study indicates that the triphylite has been partially oxidized and that its composition has evolved towards ferrisicklerite. From the wall zone towards the intermediate zone, the triphylite shows decreased Mg and Zn contents but becomes relatively Mn-enriched as the Mn/(Mn+Fe) ratios of triphylite increase from 0.388 to 0.409. Such a compositional evolutionary trend is consistent with the typical Mn-Fe fractionation trend in many pegmatites according to the literature. Similarly, the columbite-group minerals in the same pegmatite show increasing Mn/(Mn+Fe) ratios at early stages. In addition, the triphylite is partially replaced by fluorapatite, which suggests that the activities of Ca and F increased at the late hydrothermal stage. This suggests that triphylite has potential to document magmatic and hydrothermal evolution of pegmatites.
引文
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?erny P,Meintzer R E,Anderson A J.1985.Extreme fractionation in rare-element granitic pegmatites;selected examples of data and mechanisms.The Canadian Mineralogist,23(3):381～421.
?erny,Ercit T S.2005.The classification of granitic pegmatites revisited.Canadian Mineralogist,43:2005～2026.
?ernyP,London D,Novak M.2012.Granitic pegmatites as reflections of their sources.Elements,8:289～294.
Deng Wanming.1995.The geologic characteristics of the ophiolites in the Karakoram-West Kunlun region and their tectonic significance.Acta Petrol.Sin.,11:98～111.
Dong Yongguan,Guo Kunyi,Xiao Huiliang,Zhang Chuanlin,Wang Aiguo,Zhao Yu.2003.Ore prospects of the West Kunlun area in western China.Geology in China,30(2):173～178.(in Chinese with English abstract).
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Fransolet AM,Keller P,Fontan F.1986.The phoshate mineral associations of the Tsaobismund pegmatite,Namibia.Contrib.Mineral.Petrol.,92:502～517.
Fransolet A M,Hatert F,Fontan F.2004.Petrographic evidence for primary hagendorfite in an unusual assemblage of phosphate minerals,Kibingo granitic pegmatite,Rwanda.The Canadian Mineralogist,42(3):697～704.
Fransolet A M,Martins T,Vieira R.2007.Phosphate associations in the granitic pegmatites:the relevant significance of these accessory minerals.Granitic Pegmatites:the State of the Art,8:7～8.
Hatert F.2004.The crystal chemistry of lithium in the alluaudite structure:a study of the (Na1-xLix) 1.5Mn1.5Fe1.5(PO4)3 solid solution (x=0 to 1).Mineralogy and Petrology,81(3-4):205～217.
Hatert F,Ottolini L,Schmid-Beurmann P.2011.Experimental investigation of the alluaudite+ triphylite assemblage,and development of the Na-in-triphylite geothermometer:applications to natural pegmatite phosphates.Contributions to Mineralogy and Petrology,161(4):531～546.
Hatert F,Roda-Robles E,Ottolini L,Schmid-Beurmann P,Baijot M,Dal Bo F.2016.Triphylite-Sarcopside Miscibility Gap In the FeO-MnO-Li2O-P2O5-H2O System:Experimental Investigation and Thermometric Application To Granitic Pegmatites.The Canadian Mineralogist,54(4):827～845.
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Hu Jun,Wang He,Mu Shenglu,Wang Min,Hou Xuewen.2017.Geochemistry and Hf Isotopic Compositions of Early Paleozoic Granites in Nanpingxueshan from the Tianshuihai Terrane,West Kunlun:Crust-Mantle Magmatism.Acta Geologica Sinica,91(6):1192～1207.(in Chinese with English abstract).
Huminicki D M,Hawthorne F C.2002.The crystal chemistry of the phosphate minerals.Reviews in Mineralogy and Geochemistry,48(1):123～253.
Keller P,Knorring O.1989.Pegmatites at the Okatjimukuju farm,Karibib,Namibia Part I:Phosphate mineral associations of the Clementine II pegmatite.European Journal of Mineralogy,1:567～594.
Keller P,Fontan F,Fransolet A M.1994.Intercrystalline cation partitioning between minerals of the triplite-zwieselite-magniotriplite and the triphylite-lithiophilite series in granitic pegmatites.Contributions to Mineralogy and Petrology,118(3):239～248.
Li Sanzhong,Jahn B,Zhao Shujuan,Dai Liming,Li Xiyao,Suo Yanhui,Guo Lingli,Wang Yongming,Liu Xiaochun,Lan Haoyuan,Zhou Zaizheng,Zheng Qiliang,Wang Pengcheng.2017.Triassic southeastward subduction of North China Block to South China Block:Insights from new geological,geophysical and geochemical data.Earth-Science Reviews,166:270～285.
London D.2008.Pegmatites:the canadian mineralogist special publication 10.Mineralogical Association of Canada,Quebec,Canada,p.347.
Mattern F,Schneider W.2000.Suturing of the Proto- and Paleo-Tethys oceans in the Western Kunlun (Xijiang,China).J.Asian Earth Sci.,18:637～650.
Moore P B.1973.Pegmatite phosphates:descriptive mineralogy and crystal chemistry.Mineral.Record,4:103～130.
Roda-Robles E,Pesquera A,García De Madinabeitia S,Gil Ibarguchi J I,Nizamoff J,Simmons W,Falster A,Galliski M A.2014.On the geochemical character of primary Fe-Mn phosphates belonging to the triphylite-lithiophilite,graftonite-beusite,and triplite-zwieselite series:first results and implications for pegmatite petrogenesis.The Canadian Mineralogist,52(2):321～335.
Schmid-Beurmann P,Moavenian M,Hatert F.2004.Phase stability of triphylite,LiFePO4,and the phases of the Mason-Quensel sequence.Ber Deut Min Ges,Bei Eur J Mineral,16:126.
Schmid-Beurmann P,Hatert F.2005.Experimental Fe2+-oxidation in triphylite,LiFePO4:possible formation of ferrisicklerite and heterosite.Ber Deut Min Ges,Bei Eur J Mineral,17:118.
Schmid-Beurmann P,Ottolini L,Hatert F,Geisler T,Huyskens M,Kahlenberg V.2013.Topotactic formation of ferrisicklerite from natural triphylite under hydrothermal conditions.Mineralogy and Petrology,107(4):501～515.
Qiao Gengbiao,Zhang Hande,Wu Yuezhong,JinMoushun,Du Wei,Zhao Xiaojian,Chen Denghui.2015.Petrogenesis of the Dahongliutan monzogranite in western Kunlun:Constraints from SHRIMP zircon U-Pb geochronology and geochemical characteristics.Acta Geol.Sin.,89:1180～1194.(in Chinese with English abstract).
Vignola,P.,Diella,V.,Oppizzi,P.,Tiepolo,M.,& Weiss,S.2008.Phosphate assemblages from the Brissago granitic pegmatite,western Southern Alps,Switzerland.The Canadian Mineralogist,46(3):635～650.
Wang Hui,Qin Xuwen,Fan Yuhai,Yang Jinzhong,Jin Moushun,Zhang Shaopeng,Liao Youyun,Yang Chen,Cui Sheng,He Xiaolong,Kuang Jingshui,Guo Pengcheng.2018.The application of high resolution remote sensing technology to ore-prospecting in Dahongliutan-Fulugou area of West Kunlun Mountains.Geology in China,45(6):1289～1301.(in Chinese with English abstract).
Wei Xiaopeng,Wang He,Hu Jun,Mu Shenglu,QiuZengwang,Yan Qinghe,Li Pei.2017.Geochemistry and geochronology of the Dahongliutan two-mica granite pluton in western Kunlun orogen:Geotectonic implications.Geochimica,46:66～80.(in Chinese with English abstract).
Xiao Wenjiao,Han Fanglin,Windley,BF,Yuan Chao,Zhou Hui,Li,Jiliang.2003.Multiple accretionary orogenesis and episodic growth of continents:Insights from the western Kunlun Range,Central Asia.Int.Geol.Rev.,45:303～328.
Xiao Wenjiao,Windley,BF,Liu D.Y.,Jian Ping,Liu Chuanzhou,Yuan Chao,Sun Mengru.2005.Accretionary tectonics of the Western Kunlun orogen,China:A Paleozoic-Early Mesozoic,long lived active continental margin with implications for the growth of southern Eurasia.J.Geol.,113:687～705.
Yan Qinghe,QiuZengwang,Wang He,WangMin,Wei Xiaopeng,Li Pei,Zhang Rongqing,Li Congying,Liu Jianping.2016.Age of the Dahongliutan rare metal pegmatite deposit,West Kunlun,Xinjiang (NW China):Constraints from LA-ICP-MS U-Pb dating of columbite-(Fe) and cassiterite.Ore Geol.Rev.DOI:10.1016/j.oregeorev.2016.11.010.
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Zhang Rubo.1981b.Discovery of gahnite and lithiophilite in Altai pegmatites.Geological Review,27(1):1～7.(in Chinese with English abstract).
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?erny,Ercit T S.2005.The classification of granitic pegmatites revisited.Canadian Mineralogist,43:2005～2026.
?ernyP,London D,Novak M.2012.Granitic pegmatites as reflections of their sources.Elements,8:289～294.
Deng Wanming.1995.The geologic characteristics of the ophiolites in the Karakoram-West Kunlun region and their tectonic significance.Acta Petrol.Sin.,11:98～111.
Dong Yongguan,Guo Kunyi,Xiao Huiliang,Zhang Chuanlin,Wang Aiguo,Zhao Yu.2003.Ore prospects of the West Kunlun area in western China.Geology in China,30(2):173～178.(in Chinese with English abstract).
Feng Yonggang,Liang Ting,YangXiuqing,Zhang Ze,Wang Yiqian.2019.Chemical evolution of Nb-Ta oxides and cassiterite in phosphorus-rich albite-spodumene pegmatites in the Kangxiwa-Dahongliutan pegmatite field,Western Kunlun Orogen,China.Minerals 2019,9(3),166,doi.org/10.3390/min9030166.
Fransolet AM,Keller P,Fontan F.1986.The phoshate mineral associations of the Tsaobismund pegmatite,Namibia.Contrib.Mineral.Petrol.,92:502～517.
Fransolet A M,Hatert F,Fontan F.2004.Petrographic evidence for primary hagendorfite in an unusual assemblage of phosphate minerals,Kibingo granitic pegmatite,Rwanda.The Canadian Mineralogist,42(3):697～704.
Fransolet A M,Martins T,Vieira R.2007.Phosphate associations in the granitic pegmatites:the relevant significance of these accessory minerals.Granitic Pegmatites:the State of the Art,8:7～8.
Hatert F.2004.The crystal chemistry of lithium in the alluaudite structure:a study of the (Na1-xLix) 1.5Mn1.5Fe1.5(PO4)3 solid solution (x=0 to 1).Mineralogy and Petrology,81(3-4):205～217.
Hatert F,Ottolini L,Schmid-Beurmann P.2011.Experimental investigation of the alluaudite+ triphylite assemblage,and development of the Na-in-triphylite geothermometer:applications to natural pegmatite phosphates.Contributions to Mineralogy and Petrology,161(4):531～546.
Hatert F,Roda-Robles E,Ottolini L,Schmid-Beurmann P,Baijot M,Dal Bo F.2016.Triphylite-Sarcopside Miscibility Gap In the FeO-MnO-Li2O-P2O5-H2O System:Experimental Investigation and Thermometric Application To Granitic Pegmatites.The Canadian Mineralogist,54(4):827～845.
Hu Jun,Wang He,Huang Chaoyang,Tong Laixi,Mu Shenglu,Qiu Zengwang.2015.Geological characteristics and age of the Dahongliutan Fe-ore deposit in the Western Kunlun orogenic belt,Xinjiang,northwestern China.J.Asian Earth Sci.,116:1～25.
Hu Jun,Wang He,Mu Shenglu,Wang Min,Hou Xuewen.2017.Geochemistry and Hf Isotopic Compositions of Early Paleozoic Granites in Nanpingxueshan from the Tianshuihai Terrane,West Kunlun:Crust-Mantle Magmatism.Acta Geologica Sinica,91(6):1192～1207.(in Chinese with English abstract).
Huminicki D M,Hawthorne F C.2002.The crystal chemistry of the phosphate minerals.Reviews in Mineralogy and Geochemistry,48(1):123～253.
Keller P,Knorring O.1989.Pegmatites at the Okatjimukuju farm,Karibib,Namibia Part I:Phosphate mineral associations of the Clementine II pegmatite.European Journal of Mineralogy,1:567～594.
Keller P,Fontan F,Fransolet A M.1994.Intercrystalline cation partitioning between minerals of the triplite-zwieselite-magniotriplite and the triphylite-lithiophilite series in granitic pegmatites.Contributions to Mineralogy and Petrology,118(3):239～248.
Li Sanzhong,Jahn B,Zhao Shujuan,Dai Liming,Li Xiyao,Suo Yanhui,Guo Lingli,Wang Yongming,Liu Xiaochun,Lan Haoyuan,Zhou Zaizheng,Zheng Qiliang,Wang Pengcheng.2017.Triassic southeastward subduction of North China Block to South China Block:Insights from new geological,geophysical and geochemical data.Earth-Science Reviews,166:270～285.
London D.2008.Pegmatites:the canadian mineralogist special publication 10.Mineralogical Association of Canada,Quebec,Canada,p.347.
Mattern F,Schneider W.2000.Suturing of the Proto- and Paleo-Tethys oceans in the Western Kunlun (Xijiang,China).J.Asian Earth Sci.,18:637～650.
Moore P B.1973.Pegmatite phosphates:descriptive mineralogy and crystal chemistry.Mineral.Record,4:103～130.
Roda-Robles E,Pesquera A,García De Madinabeitia S,Gil Ibarguchi J I,Nizamoff J,Simmons W,Falster A,Galliski M A.2014.On the geochemical character of primary Fe-Mn phosphates belonging to the triphylite-lithiophilite,graftonite-beusite,and triplite-zwieselite series:first results and implications for pegmatite petrogenesis.The Canadian Mineralogist,52(2):321～335.
Schmid-Beurmann P,Moavenian M,Hatert F.2004.Phase stability of triphylite,LiFePO4,and the phases of the Mason-Quensel sequence.Ber Deut Min Ges,Bei Eur J Mineral,16:126.
Schmid-Beurmann P,Hatert F.2005.Experimental Fe2+-oxidation in triphylite,LiFePO4:possible formation of ferrisicklerite and heterosite.Ber Deut Min Ges,Bei Eur J Mineral,17:118.
Schmid-Beurmann P,Ottolini L,Hatert F,Geisler T,Huyskens M,Kahlenberg V.2013.Topotactic formation of ferrisicklerite from natural triphylite under hydrothermal conditions.Mineralogy and Petrology,107(4):501～515.
Qiao Gengbiao,Zhang Hande,Wu Yuezhong,JinMoushun,Du Wei,Zhao Xiaojian,Chen Denghui.2015.Petrogenesis of the Dahongliutan monzogranite in western Kunlun:Constraints from SHRIMP zircon U-Pb geochronology and geochemical characteristics.Acta Geol.Sin.,89:1180～1194.(in Chinese with English abstract).
Vignola,P.,Diella,V.,Oppizzi,P.,Tiepolo,M.,& Weiss,S.2008.Phosphate assemblages from the Brissago granitic pegmatite,western Southern Alps,Switzerland.The Canadian Mineralogist,46(3):635～650.
Wang Hui,Qin Xuwen,Fan Yuhai,Yang Jinzhong,Jin Moushun,Zhang Shaopeng,Liao Youyun,Yang Chen,Cui Sheng,He Xiaolong,Kuang Jingshui,Guo Pengcheng.2018.The application of high resolution remote sensing technology to ore-prospecting in Dahongliutan-Fulugou area of West Kunlun Mountains.Geology in China,45(6):1289～1301.(in Chinese with English abstract).
Wei Xiaopeng,Wang He,Hu Jun,Mu Shenglu,QiuZengwang,Yan Qinghe,Li Pei.2017.Geochemistry and geochronology of the Dahongliutan two-mica granite pluton in western Kunlun orogen:Geotectonic implications.Geochimica,46:66～80.(in Chinese with English abstract).
Xiao Wenjiao,Han Fanglin,Windley,BF,Yuan Chao,Zhou Hui,Li,Jiliang.2003.Multiple accretionary orogenesis and episodic growth of continents:Insights from the western Kunlun Range,Central Asia.Int.Geol.Rev.,45:303～328.
Xiao Wenjiao,Windley,BF,Liu D.Y.,Jian Ping,Liu Chuanzhou,Yuan Chao,Sun Mengru.2005.Accretionary tectonics of the Western Kunlun orogen,China:A Paleozoic-Early Mesozoic,long lived active continental margin with implications for the growth of southern Eurasia.J.Geol.,113:687～705.
Yan Qinghe,QiuZengwang,Wang He,WangMin,Wei Xiaopeng,Li Pei,Zhang Rongqing,Li Congying,Liu Jianping.2016.Age of the Dahongliutan rare metal pegmatite deposit,West Kunlun,Xinjiang (NW China):Constraints from LA-ICP-MS U-Pb dating of columbite-(Fe) and cassiterite.Ore Geol.Rev.DOI:10.1016/j.oregeorev.2016.11.010.
Yang Yueqing,Wang Wenying,Ni Yunxiang,Chen Chenghu,Zhu Jinhuang.1994.Phosphate minerals and their Geochemical evolution of granitic pegmatite in Nanping,Fujian Province.Fujian Geology,4:215～226.(in Chinese with English abstract).
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