褐帘石的谱学特征
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摘要
本文研究了6个来自不同产状、不同地区的含褐帘石样品,包括4个伟晶岩(M1663来自内蒙集宁益元兴、M7673来自内蒙集宁察汗营地区、M4960来自美国Amherst County Virginia地区、M4976来自挪威Liksviken地区)、2个矽卡岩(M1697产自河北地区、M1679产自湖南郴县地区)。通过对这6个不同产状褐帘石的电子探针主量、稀土和微量元素分析及拉曼、红外光谱学的研究来揭示褐帘石晶体化学特征。结果表明,褐帘石成分均匀,晶体内发育微裂隙,局部有脉体充填,但不同产状的褐帘石样品在主量元素如Fe O、Ca O、Al_2O_3以及REE如Ce_2O_3、Nd_2O_3、La_2O_3的含量具有明显的差别。其系统的光谱学数据表明褐帘石晶体的特征峰强度和峰位的偏移均与其组分有关,并分析指派了部分光谱峰位的归属,揭示了褐帘石中特殊谱峰位置的迁移与其元素含量、晶体结构之间的关系。拉曼光谱揭示了褐帘石单晶有20组拉曼活性谱峰(ν1～ν20),其中ν2～ν4、ν5～ν8、ν16～ν19谱峰的迁移与A位上的Ca与稀土元素之间置换作用有关;ν10～ν12谱峰是O-Si-O弯曲振动引起,其拉曼谱峰的偏移可能与Si含量有关;ν13～ν14谱峰的迁移则可能是多种元素变化共同作用的结果。褐帘石单晶红外光谱展示了13组红外活性谱峰(a-m),h-k谱峰的偏移与在M1或M3位上Fe~(3+)和Al相互替代而导致的; b-g谱峰的偏移是与硅氧四面体中Si-O非对称伸缩振动有关; OH(l-m)双峰的出现可能与M1、M3位上Fe~(3+)的含量有关。研究结果表明伟晶岩类岩石中褐帘石晶体结构中Fe~(3+)与Al~(3+)间的置换作用强于矽卡岩类岩石中的褐帘石;而矽卡岩类岩石中褐帘石晶体结构中在A位上稀土元素与Ca置换作用则大于伟晶岩类岩石中的褐帘石。
Six allanite-bearing samples from different occurrences and locations including four pegmatites and two skarns are studied. The pegmatites are from the Yiyuanxing( M1663) and the Chahanying( M7673) in the Tsining of Inner Mongolia,the Amherst County Virginia of America( M4960),the Liksviken of Norway( M4976). The skarns are from Hebei Province( M1697) and the Chen County of Hunan Province( M1679). The chemical features of six allanite samples are revealed by analysis of the major and trace elements of Electron Probe Microanalysis( EPMA),Raman,Infrared spectroscopy. The results show that compositions of allanite grains are homogeneous. The allanite grains have cracks with vein filled. However,the contents of major element including Fe O,Ca O and Al_2O_3 and Rare Earth Element( REE) such as Ce_2O_3,Nd_2O_3 and La_2O_3 are different in the allanites. The systematic spectroscopic data of the allanites show that the characteristic peak intensity and their shift are related to their components,and assigning,discussing the relationship between special peak shift of allanite,the component of element and its crystal structure. The systematic research of Raman,Infrared spectroscopy and its constituent not only can reveal characteristics of the crystal structure,but also can discuss the difference between its structure and forming environment. Raman spectroscopy reveals that there are 20 Raman peaks of the allanites( ν1 ～ ν20). The peaks shift of ν2 ～ ν4,ν5 ～ ν8 and ν16 ～ ν19 are related to the substitution between Ca and REE. The ν10 ～ ν12 are attributed to the O-Si-O bending vibration modes and their peak shift are related to Si content. The shifts of ν13 ～ ν14 maybe result of the combined action of multi-element changes. Infrared spectroscopy shows 13 infrared peaks( a-m) of the allanites. The peak shifts of h-k are described as substitution between Fe~(3+)and Al on the M1 or M3. The shifts of b-g are attributed to Si-O asymmetric stretching modes on the Si-O tetrahedron. The occurrence of OH double peaks of stretching( l-m) may be related to the content of Fe~(3+)at the M1 and M3. Our results show that substitution between Fe~(3+)and Al~(3+)of the allanite of the pegmatites is more than the allanite of the skarns. However,substitution between REE and Ca on the A of the allanite of the pegmatites is less than those of the skarns.
Six allanite-bearing samples from different occurrences and locations including four pegmatites and two skarns are studied. The pegmatites are from the Yiyuanxing( M1663) and the Chahanying( M7673) in the Tsining of Inner Mongolia,the Amherst County Virginia of America( M4960),the Liksviken of Norway( M4976). The skarns are from Hebei Province( M1697) and the Chen County of Hunan Province( M1679). The chemical features of six allanite samples are revealed by analysis of the major and trace elements of Electron Probe Microanalysis( EPMA),Raman,Infrared spectroscopy. The results show that compositions of allanite grains are homogeneous. The allanite grains have cracks with vein filled. However,the contents of major element including Fe O,Ca O and Al_2O_3 and Rare Earth Element( REE) such as Ce_2O_3,Nd_2O_3 and La_2O_3 are different in the allanites. The systematic spectroscopic data of the allanites show that the characteristic peak intensity and their shift are related to their components,and assigning,discussing the relationship between special peak shift of allanite,the component of element and its crystal structure. The systematic research of Raman,Infrared spectroscopy and its constituent not only can reveal characteristics of the crystal structure,but also can discuss the difference between its structure and forming environment. Raman spectroscopy reveals that there are 20 Raman peaks of the allanites( ν1 ～ ν20). The peaks shift of ν2 ～ ν4,ν5 ～ ν8 and ν16 ～ ν19 are related to the substitution between Ca and REE. The ν10 ～ ν12 are attributed to the O-Si-O bending vibration modes and their peak shift are related to Si content. The shifts of ν13 ～ ν14 maybe result of the combined action of multi-element changes. Infrared spectroscopy shows 13 infrared peaks( a-m) of the allanites. The peak shifts of h-k are described as substitution between Fe~(3+)and Al on the M1 or M3. The shifts of b-g are attributed to Si-O asymmetric stretching modes on the Si-O tetrahedron. The occurrence of OH double peaks of stretching( l-m) may be related to the content of Fe~(3+)at the M1 and M3. Our results show that substitution between Fe~(3+)and Al~(3+)of the allanite of the pegmatites is more than the allanite of the skarns. However,substitution between REE and Ca on the A of the allanite of the pegmatites is less than those of the skarns.
引文
Anenburg M,Katzir Y,Rhede D,J9ns N and Bach W.2015.Rare earth element evolution and migration in plagiogranites:A record preserved in epidote and allanite of the Troodos ophiolite.Contributions to Mineralogy and Petrology,169(3):25
Boundy TM,Donohue CL,Essene EJ,Mezger K and Austrheim H.2002.Discovery of eclogite facies carbonate rocks from the Linds Nappe,Caledonides,Western Norway.Journal of Metamorphic Geology,20(7):649-667
Bradbury SE and Williams Q.2003.Contrasting bonding behavior of two hydroxyl-bearing metamorphic minerals under pressure:Clinozoisite and topaz.American Mineralogist,88(10):1460-1470
Cui TS.1995.Research on high REE allanite and its prospecting significance.Journal of Guilin Institute of Technology,15(2):137-141(in Chinese with English abstract)
Della Ventura G,Mottana A,Parodi GC and Griffin WL.1996.FTIRspectroscopy in the OH-stretching region of monoclinic epidotes from Praborna(St.Marcel,Aosta Valley,Italy).European Journal of Mineralogy,8(4):655-666
Dollase WA.1968.Refinement and comparison of the structures of zoisite and clinozoisite.American Mineralogist,53(11-12):1882-1898
Fu Y,Sun XM,Li DF,Lin H and Lai C.2017.LA-ICP-MS U-Th-Pb dating and trace element geochemistry of allanite:Implications on the different skarn metallogenesis between the giant Beiya Au and Machangqing Cu-Mo-(Au)deposits in Yunnan,SW China.Minerals,7(12):251
GieréR and Sorensen SS.2004.Allanite and other REE-rich epidotegroup minerals.Reviews in Mineralogy and Geochemistry,56(1):431-493
Gregory CJ,Rubatto D,Hermann J,Berger A and Engi M.2012.Allanite behaviour during incipient melting in the southern Central Alps.Geochimica et Cosmochimica Acta,84:433-458
Gu XP.1989.Characteristics of the rare earth composition of allanite and their geological implications in Xinfeng granite.Mineral Resources and Geology,(3):47-50(in Chinese with English abstract)
Gu XP.1995.Research of metagenetic allanite with IR.Mineral Resources and Geology,9(48):275-279(in Chinese)
Guastoni A,Nestola F and Schiazza M.2017.Post-magmatic solid solutions of CaCeAl2(Fe3+2/3-1/3)[Si2O7][SiO4]O(OH),allanite-(Ce)and REE-bearing epidote in miarolitic pegmatites of Permian Baveno granite(Verbania,central-southern alps,Italy).Mineralogy and Petrology,111(3):315-323
Guo HH,Xiao YL,Gu XP,Huang J,Hou ZH and Liu HY.2014.LA-ICP-MS Allanite U-Th-Pb Geochronology study on Guangdong Xinfeng REE-rich granite.Acta Geologica Sinica,88(6):1025-1037(in Chinese with English abstract)
Guo HH,Xiao YL,Xu LJ,Sun H,Huang J and Hou ZH.2017.Origin of allanite in gneiss and granite in the Dabie orogenic belt,Central East China.Journal of Asian Earth Sciences,135:243-256
Hermann J.2002.Allanite:Thorium and light rare earth element carrier in subducted crust.Chemical Geology,192(3-4):289-306
Hoschek G.2016.Phase relations of the REE minerals florencite,allanite and monazite in quartzitic garnet-kyanite schist of the eclogite zone,Tauern Window,Austria.European Journal of Mineralogy,28(4):735-750
Hoshino M,Kimata M,Arakawa Y,Shimizu M,Nishida N and Nskai S.2007.Allanite-(Ce)as an indicator of the origin of granitic rocks in Japan:Importance of Sr-Nd isotopic and chemical composition.Canadian Mineralogist,45(6):1329-1336
Langer K and Raith M.1974.Infrared spectra of Al-Fe(Ⅲ)-epidotes and zoisites,Ca2(Al1-pFe3+p)Al2O(OH)[(Si2O7][SiO4].American Mineralogist,59(11-12):1249-1258
Liebscher A.2004.Spectroscopy of epidote minerals.Reviews in Mineralogy and Geochemistry,56(1):125-170
Liebscher A and Gottschalk M.2004.The T-X dependence of the isosymmetric displacive phase transition in synthetic Fe3+-Al zoisite:A temperature-dependent infrared spectroscopy study.American Mineralogist,89(1):31-38
Liu CL.1959.Allanite in skarn.Chinese Science Bulletin,(10):132(in Chinese)
Liu XC,Dong SW,Xue HM and Zhou JX.1999.Significance of Allanite-(Ce)in granitic gneisses from the ultrahigh-pressure metamorphic terrane,Dabie Shan,central China.Mineralogical Magazine,63(4):579-586
López A and Frost RL.2015.Identification of allanite(Ce,Ca,Y)2(Al,Fe3+)3(SiO4)3OH found in marble from Chillagoe,Queensland using Raman spectroscopy.Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,138:229-233
Makreski P,Jovanovski G,Kaitner B,Gajovi c'A and Biljan T.2007.Minerals from Macedonia XVIII.Vibrational spectra of some sorosilicates.Vibrational Spectroscopy,44(1):162-170
Mitchell RS and Redline GE.1980.Minerals of a weathered allanite pegmatite:Amherst County,Virginia.Rocks&Minerals,55(6)245-249
Petrusenko S,Taran MN,Platonov AN and Gavorkyan SV.1992.Optical and infrared spectoscopic studies of epidote group minerals from the Rhodope region.The Review of Bulgarian Geological Society,53:1-9(in Russian)
Qin F,Wu X,Wang Y,Fan DW,Qin S,Yang K,Townsend JP and Jacobsen SD.2016.High-pressure behavior of natural single-crystal epidote and clinozoisite up to 40GPa.Physics and Chemistry of Minerals,43(9):649-659
Shaw DM.1956.Geochemistry of pelitic rocks,Part III:Major elements and general geochemistry.GSA Bulletin,67(7):919-934
Winkler B,Langer K and Johannsen PG.1989.The influence of pressure on the OH-valence vibration of zoisite:An infrared spectroscopic study.Physics and Chemistry of Minerals,16(7):668-671
崔天顺.1995.高稀土褐帘石的特征研究.桂林工学院学报,15(2):137-141
谷湘平.1989.广东新丰稀土花岗岩中褐帘石的稀土组成特点及其地质意义.矿产与地质,(3):47-50
谷湘平.1995.变生褐帘石的红外光谱研究.矿产与地质,9(48):275-279
郭海浩,肖益林,古湘平,黄建,侯振辉,刘海洋.2014.广东新丰稀土花岗岩中褐帘石LA-ICP-MS的U-Th-Pb定年研究.地质学报,88(6):1025-1037
刘长龄.1959.矽卡岩中褐帘石的发现.科学通报,10:132
Boundy TM,Donohue CL,Essene EJ,Mezger K and Austrheim H.2002.Discovery of eclogite facies carbonate rocks from the Linds Nappe,Caledonides,Western Norway.Journal of Metamorphic Geology,20(7):649-667
Bradbury SE and Williams Q.2003.Contrasting bonding behavior of two hydroxyl-bearing metamorphic minerals under pressure:Clinozoisite and topaz.American Mineralogist,88(10):1460-1470
Cui TS.1995.Research on high REE allanite and its prospecting significance.Journal of Guilin Institute of Technology,15(2):137-141(in Chinese with English abstract)
Della Ventura G,Mottana A,Parodi GC and Griffin WL.1996.FTIRspectroscopy in the OH-stretching region of monoclinic epidotes from Praborna(St.Marcel,Aosta Valley,Italy).European Journal of Mineralogy,8(4):655-666
Dollase WA.1968.Refinement and comparison of the structures of zoisite and clinozoisite.American Mineralogist,53(11-12):1882-1898
Fu Y,Sun XM,Li DF,Lin H and Lai C.2017.LA-ICP-MS U-Th-Pb dating and trace element geochemistry of allanite:Implications on the different skarn metallogenesis between the giant Beiya Au and Machangqing Cu-Mo-(Au)deposits in Yunnan,SW China.Minerals,7(12):251
GieréR and Sorensen SS.2004.Allanite and other REE-rich epidotegroup minerals.Reviews in Mineralogy and Geochemistry,56(1):431-493
Gregory CJ,Rubatto D,Hermann J,Berger A and Engi M.2012.Allanite behaviour during incipient melting in the southern Central Alps.Geochimica et Cosmochimica Acta,84:433-458
Gu XP.1989.Characteristics of the rare earth composition of allanite and their geological implications in Xinfeng granite.Mineral Resources and Geology,(3):47-50(in Chinese with English abstract)
Gu XP.1995.Research of metagenetic allanite with IR.Mineral Resources and Geology,9(48):275-279(in Chinese)
Guastoni A,Nestola F and Schiazza M.2017.Post-magmatic solid solutions of CaCeAl2(Fe3+2/3-1/3)[Si2O7][SiO4]O(OH),allanite-(Ce)and REE-bearing epidote in miarolitic pegmatites of Permian Baveno granite(Verbania,central-southern alps,Italy).Mineralogy and Petrology,111(3):315-323
Guo HH,Xiao YL,Gu XP,Huang J,Hou ZH and Liu HY.2014.LA-ICP-MS Allanite U-Th-Pb Geochronology study on Guangdong Xinfeng REE-rich granite.Acta Geologica Sinica,88(6):1025-1037(in Chinese with English abstract)
Guo HH,Xiao YL,Xu LJ,Sun H,Huang J and Hou ZH.2017.Origin of allanite in gneiss and granite in the Dabie orogenic belt,Central East China.Journal of Asian Earth Sciences,135:243-256
Hermann J.2002.Allanite:Thorium and light rare earth element carrier in subducted crust.Chemical Geology,192(3-4):289-306
Hoschek G.2016.Phase relations of the REE minerals florencite,allanite and monazite in quartzitic garnet-kyanite schist of the eclogite zone,Tauern Window,Austria.European Journal of Mineralogy,28(4):735-750
Hoshino M,Kimata M,Arakawa Y,Shimizu M,Nishida N and Nskai S.2007.Allanite-(Ce)as an indicator of the origin of granitic rocks in Japan:Importance of Sr-Nd isotopic and chemical composition.Canadian Mineralogist,45(6):1329-1336
Langer K and Raith M.1974.Infrared spectra of Al-Fe(Ⅲ)-epidotes and zoisites,Ca2(Al1-pFe3+p)Al2O(OH)[(Si2O7][SiO4].American Mineralogist,59(11-12):1249-1258
Liebscher A.2004.Spectroscopy of epidote minerals.Reviews in Mineralogy and Geochemistry,56(1):125-170
Liebscher A and Gottschalk M.2004.The T-X dependence of the isosymmetric displacive phase transition in synthetic Fe3+-Al zoisite:A temperature-dependent infrared spectroscopy study.American Mineralogist,89(1):31-38
Liu CL.1959.Allanite in skarn.Chinese Science Bulletin,(10):132(in Chinese)
Liu XC,Dong SW,Xue HM and Zhou JX.1999.Significance of Allanite-(Ce)in granitic gneisses from the ultrahigh-pressure metamorphic terrane,Dabie Shan,central China.Mineralogical Magazine,63(4):579-586
López A and Frost RL.2015.Identification of allanite(Ce,Ca,Y)2(Al,Fe3+)3(SiO4)3OH found in marble from Chillagoe,Queensland using Raman spectroscopy.Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,138:229-233
Makreski P,Jovanovski G,Kaitner B,Gajovi c'A and Biljan T.2007.Minerals from Macedonia XVIII.Vibrational spectra of some sorosilicates.Vibrational Spectroscopy,44(1):162-170
Mitchell RS and Redline GE.1980.Minerals of a weathered allanite pegmatite:Amherst County,Virginia.Rocks&Minerals,55(6)245-249
Petrusenko S,Taran MN,Platonov AN and Gavorkyan SV.1992.Optical and infrared spectoscopic studies of epidote group minerals from the Rhodope region.The Review of Bulgarian Geological Society,53:1-9(in Russian)
Qin F,Wu X,Wang Y,Fan DW,Qin S,Yang K,Townsend JP and Jacobsen SD.2016.High-pressure behavior of natural single-crystal epidote and clinozoisite up to 40GPa.Physics and Chemistry of Minerals,43(9):649-659
Shaw DM.1956.Geochemistry of pelitic rocks,Part III:Major elements and general geochemistry.GSA Bulletin,67(7):919-934
Winkler B,Langer K and Johannsen PG.1989.The influence of pressure on the OH-valence vibration of zoisite:An infrared spectroscopic study.Physics and Chemistry of Minerals,16(7):668-671
崔天顺.1995.高稀土褐帘石的特征研究.桂林工学院学报,15(2):137-141
谷湘平.1989.广东新丰稀土花岗岩中褐帘石的稀土组成特点及其地质意义.矿产与地质,(3):47-50
谷湘平.1995.变生褐帘石的红外光谱研究.矿产与地质,9(48):275-279
郭海浩,肖益林,古湘平,黄建,侯振辉,刘海洋.2014.广东新丰稀土花岗岩中褐帘石LA-ICP-MS的U-Th-Pb定年研究.地质学报,88(6):1025-1037
刘长龄.1959.矽卡岩中褐帘石的发现.科学通报,10:132