应用元素分析-电子顺磁共振能谱研究不同颜色青海软玉致色元素
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摘要
颜色是软玉价值的重要体现,青海软玉颜色丰富,而致色方面的研究较为滞后。近年来青海软玉致色研究多为翠青玉和烟青玉,认为Cr~(3+)和Mn~(2+)分别为翠青玉和烟青玉致色元素。青海软玉的颜色非单一色彩,如青白色、翠绿色、灰紫色等,因此青海软玉致色应包含多种致色元素。本文在前人研究的基础上,利用X射线荧光光谱法(XRF)、化学滴定法、电感耦合等离子体质谱法(ICP-MS)和电子顺磁共振能谱(EPR)测试数据,根据分析数据与色调变化之间的关系揭示了8种颜色青海软玉的致色元素。结果表明:白玉致色元素为Fe~(3+);青白玉和碧玉致色元素为Fe~(2+)和Fe~(3+);青玉致色元素为Fe~(2+)、Fe~(3+)和高价态的Mn;翠青玉致色元素为Fe~(2+)、Fe~(3+)、Cr~(3+);黄玉和糖玉致色元素为Fe~(3+)和高价态的Mn;烟青玉致色元素为Fe~(3+)和Ti~(4+)。研究认为青海软玉中绿色调与Fe~(2+)有关,黄色调与Fe~(3+)和高价态的Mn有关,而蓝紫色调与Fe~(3+)和Ti~(4+)有关。本研究基本确定了不同颜色青海软玉的致色元素,为青海软玉致色机制的研究提供了理论依据。
BACKGROUND: Color is the important manifestation of nephrite value. Qinghai nephrite has different colors, but there is a lack of research on coloration. In recent years, the study on the coloration of nephrite in Qinghai mainly focused on azure-green and blue-violet, and it was considered that Cr~(3+) and Mn~(2+) were respective coloration elements of azure-green and blue-violet. The color of Qinghai nephrite is not a simple color, such as white-green, azure-green, and blue-violet. Therefore, Qinghai nephrite should contain a variety of color-causing elements.OBJECTIVES: To reveal the color-causing elements of eight colors of nephrite from Qinghai based on the relationship between analysis data and hue changes.METHODS: X-ray Fluorescence Spectrometry(XRF), Chemical Titration, Inductively Coupled Plasma-Mass Spectrometry(ICP-MS) and Electron Paramagnetic Resonance Spectroscopy(EPR) were used to study the color-causing elements of nephrite.RESULTS: The color-causing element of white Qinghai nephrite was Fe~(3+). The color-causing elements of white-green and azure-green Qinghai nephrite were Fe~(2+) and Fe~(3+), respectively. The chromogenic elements of green Qinghai nephrite were Fe~(2+), Fe~(3+) and Mn in high valence. The color-causing elements of azure-green Qinghai nephrite were Fe~(2+), Fe~(3+) and Cr~(3+). The chromogenic elements of yellow and brown Qinghai nephrite were Fe~(3+) and high-valence Mn. Fe~(3+) and Ti~(4+) were the color-causing elements of blue-purple Qinghai nephrite.CONCLUSIONS: This study determined the color-causing elements of different colors of Qinghai nephrite, which provided a theoretical basis for the study of the coloration mechanism of Qinghai nephrite.
BACKGROUND: Color is the important manifestation of nephrite value. Qinghai nephrite has different colors, but there is a lack of research on coloration. In recent years, the study on the coloration of nephrite in Qinghai mainly focused on azure-green and blue-violet, and it was considered that Cr~(3+) and Mn~(2+) were respective coloration elements of azure-green and blue-violet. The color of Qinghai nephrite is not a simple color, such as white-green, azure-green, and blue-violet. Therefore, Qinghai nephrite should contain a variety of color-causing elements.OBJECTIVES: To reveal the color-causing elements of eight colors of nephrite from Qinghai based on the relationship between analysis data and hue changes.METHODS: X-ray Fluorescence Spectrometry(XRF), Chemical Titration, Inductively Coupled Plasma-Mass Spectrometry(ICP-MS) and Electron Paramagnetic Resonance Spectroscopy(EPR) were used to study the color-causing elements of nephrite.RESULTS: The color-causing element of white Qinghai nephrite was Fe~(3+). The color-causing elements of white-green and azure-green Qinghai nephrite were Fe~(2+) and Fe~(3+), respectively. The chromogenic elements of green Qinghai nephrite were Fe~(2+), Fe~(3+) and Mn in high valence. The color-causing elements of azure-green Qinghai nephrite were Fe~(2+), Fe~(3+) and Cr~(3+). The chromogenic elements of yellow and brown Qinghai nephrite were Fe~(3+) and high-valence Mn. Fe~(3+) and Ti~(4+) were the color-causing elements of blue-purple Qinghai nephrite.CONCLUSIONS: This study determined the color-causing elements of different colors of Qinghai nephrite, which provided a theoretical basis for the study of the coloration mechanism of Qinghai nephrite.
引文
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[18] Balan E.Structural Fe3+ in natural kaolinites:New insights from electron paramagnetic resonance spectra fitting at X and Q-band frequencies[J].Clays & Clay Minerals,1999,47(5):605-616.
[19] Gaite J M,Izotov V V,Nikitin S I,et al.EPR and optical spectroscopy of impurities in two synthetic beryls[J].Applied Magnetic Resonance,2001,20(3):307-315.
[20] Ollier N,Fuchs Y,Cavani O,et al.Influence of impurities on Cr3+ luminescence properties in Brazilian emerald and alexandrite[J].European Journal of Mineralogy,2015,27(6):783-792.
[21] Zheng W C,Zhou Q,Wu X X,et al.Theoretical investigations of the EPR parameters of Ti3+ in beryl crystal[J].Zeitschrift Für Naturforschung A,2006,61(5-6):286-288.
[22] Yuan Z,Wu X X,Lü H,et al.EPR parameters and defect structures of the off-center Ti3+ ion on the Sr2+ site in neutron-irradiated SrTiO3 crystal[J].Journal of Physics & Chemistry of Solids,2007,68(9):1652-1655.
[23] 赵敏光.晶体场和电子顺磁共振理论[M].北京:科学出版社,1991:204-216.Zhao M G.Theory on Crystal Field and Electron Paramagnetic Resonance[M].Beijing:Science Press,1991:204-216.
[2] 那宝成,冷莹莹,李祥虎.软玉致色元素的研究[J].超硬材料工程,2008,20(3):55-58.Na B C,Leng Y Y,Li X H.Research on coloring element of nephrite[J].Uperhard Material Engineering,2008,20(3):55-58.
[3] Wang Y Y,Gan F X.Coloration mechanism and chromaticity of Xiuyan jade of China[J].Spectroscopy and Spectral Analysis,2012,32(9):2305-2310.
[4] 冯晓燕,陆太进,张辉,等.拉曼光谱分析在软玉颜色评价中的应用[J].矿物岩石,2015,35(1):1-6.Feng X Y,Lu T J,Zhang H,et al.Application of Raman spectroscopic technique to investigation on nephrite color[J].Journal of Mineralogy and Petrology,2015,35(1):1-6.
[5] 韩文,洪汉烈,吴钰,等.和田玉糖玉的致色机理研究[J].光谱学与光谱分析,2013,33(6):1446-1450.Han W,Hong H L,Wu Y,et al.Color genesis of brown jade from Hetian nephrite[J].Spectroscopy and Spectral Analysis,2013,33(6):1446-1450.
[6] 周征宇,陈盈,廖宗廷,等.溧阳软玉的岩石矿物学研究[J].岩石矿物学杂志,2009,28(5):490-494.Zhou Z Y,Chen Y,Liao Z T,et al.A petrological and mineralogical study of Liyang nephrite[J].Acta Petrologica et Mineralogica,2009,28(5):490-494.
[7] 卢保奇.四川石棉软玉猫眼和蛇纹石猫眼的宝石矿物学及其谱学研究[D].上海:上海大学,2005.Lu B Q.The Gemological Mineralogy and Spectroscopy of Nephrite Cat’s Eye and Serpentine Cat’s Eye from Shimian,Sichuan Province,Southwest of China[D]:Shanghai:Shanghai University,2005.
[8] 杨林.贵州罗甸玉矿物岩石学特征及成因机理研究[D].成都:成都理工大学,2013.Yang L.Study on Petro-mineral Features and Genetic Mechanism of Luodian Jade,Guizhou Province[D].Chengdu:Chengdu University of Technology,2013.
[9] 刘虹靓,杨明星,杨天翔,等.青海翠青玉的宝石学特征及颜色研究[J].宝石和宝石学杂志,2013,15(1):7-14.Liu H L,Yang M X,Yang T X,et al.Study on colour and gemological characteristics of viridis nephrite from Qinghai Province[J].Journal of Gems & Gemmology,2013,15(1):7-14.
[10] 罗泽敏,沈锡田,杨明星.青海三岔河灰紫色软玉颜色定量表达与紫色成因研究[J].光谱学与光谱分析,2017,37(3):822-828.Luo Z M,Shen X T,Yang M X.Study on color quantitative expression,replication and color origin of gray-purple nephrite from Qinghai,China based on spectroscopy methods[J].Pectroscopy and Spectral Analysis,2017,37(3):822-828.
[11] Manoogian A.The electron spin resonance of Mn2+ in tremolite[J].Canadian Journal of Physics,2011,46(2):129-133.
[12] Manoogian A.Intensity of allowed and forbidden electron spin resonance lines of Mn2+ in tremolite[J].Canadian Journal of Physics,2011,46(9):1029-1033.
[13] Mcgavin D G,Palmer R A,Tennant W C,et al.Use of ultrasonically modulated electron resonance to study S-state ions in mineral crystals:Mn2+,Fe3+ in tremolite[J].Physics & Chemistry of Minerals,1982,8(5):200-205.
[14] Vinokurov V M,Zaripov M M,Stepanov V G.Paramagnetic resonance of Mn2+ions in diopside[J].Solid State Communications,1964,2(5):Ⅲ-Ⅳ.
[15] Pan Y,Nilges M J.Electron paramagnetic resonance spectroscopy:Basic principles,experimental techniques and applications to earth and planetary sciences[J].Reviews in Mineralogy & Geochemistry,2014,78(1):655-690.
[16] Vasyukov V N,Shapovalov V V,Schwarz S A,et al.Temperature-induced changes in the EPR spectrum of the magnetic center in kaolin[J].Journal of Magnetic Resonance,2002,154(1):15-21.
[17] Pan Y,Mao M,Lin J.Single-crystal EPR study of Fe3+ and VO2+ in prehnite from the Jeffrey mine,Asbestos,Quebec[J].Canadian Mineralogist,2009,47(4):933-945.
[18] Balan E.Structural Fe3+ in natural kaolinites:New insights from electron paramagnetic resonance spectra fitting at X and Q-band frequencies[J].Clays & Clay Minerals,1999,47(5):605-616.
[19] Gaite J M,Izotov V V,Nikitin S I,et al.EPR and optical spectroscopy of impurities in two synthetic beryls[J].Applied Magnetic Resonance,2001,20(3):307-315.
[20] Ollier N,Fuchs Y,Cavani O,et al.Influence of impurities on Cr3+ luminescence properties in Brazilian emerald and alexandrite[J].European Journal of Mineralogy,2015,27(6):783-792.
[21] Zheng W C,Zhou Q,Wu X X,et al.Theoretical investigations of the EPR parameters of Ti3+ in beryl crystal[J].Zeitschrift Für Naturforschung A,2006,61(5-6):286-288.
[22] Yuan Z,Wu X X,Lü H,et al.EPR parameters and defect structures of the off-center Ti3+ ion on the Sr2+ site in neutron-irradiated SrTiO3 crystal[J].Journal of Physics & Chemistry of Solids,2007,68(9):1652-1655.
[23] 赵敏光.晶体场和电子顺磁共振理论[M].北京:科学出版社,1991:204-216.Zhao M G.Theory on Crystal Field and Electron Paramagnetic Resonance[M].Beijing:Science Press,1991:204-216.
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