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致色机理是彩色宝石精准鉴定和颜色优化基础。为深入揭示蓝绿色电气石致色机理，本文对巴西蓝绿色电气石开展宝石学常规测试，X射线衍射、红外光谱、紫外-可见分光光谱、X射线-电子能谱等一系列谱学研究。结果表明，该电气石为锂电气石，相对密度为3.08,No=1.640,Ne=1.619；该电气石在红区718 nm处形成对称性良好的宽大吸收带，在蓝区和绿区透射良好，因此呈现其特有的明亮蓝绿色。基于光谱数据与晶体化学环境分析，本文推断718 nm处吸收系由Fe2+-Fe3+的电荷转移引起，其中，Fe2+和Fe3+可能分别占据晶格中的Y位和Z位，质量百分比为42.1%和57.9%。另外发现Mn3+，推测占据晶格Z位，但Mn3+未引起可见光选择性吸收。上述研究深入揭示了彩色电气石中致色离子的化学状态，为电气石的精准鉴定、改色优化等提供了可靠依据。对于离子占位的精确指认，未来可借助X射线单晶衍射精修晶体结构等更直接的表征技术予以进一步验证。
Abstract：The coloration mechanism is fundamental to the accurate identification and color optimization of colored gemstones. To gain deeper insights into the coloration mechanism of blue-green tourmaline,this study conducted a series of spectroscopic investigations on blue-green tourmaline mined from Brazil,including routine gemological testing,XRD analysis,FTIR analysis,UV-Vis spectral analysis,and XPS analysis. The results indicated that the tourmaline was lithium tourmaline,with a relative density of 3. 08,No=1. 640,and Ne=1. 619. A broad,wellsymmetric absorption was found at 718 nm in the red region,whereas good transmission was detected in the blue and green regions,which produced the tourmaline's unique color of bright blue-green. Based on spectral data and analysis of the crystal chemical environment,we infered that the absorption at 718 nm may be caused by Fe2+-Fe3+ charge transfer,wherein Fe2+ and Fe3+ may occupy the Y and Z sites within the crystal lattice,respectively,with mass percentages of 42. 1% and 57. 9%. Additionally,Mn3+ was found,inferred to occupy the Z site within the lattice,but it did not cause selective absorption of visible light. The above research provides in-depth revelation of the chemical states of chromogenic ions in colored tourmaline,offering a reliable basis for the accurate identification and color improvement optimization of tourmaline. For the precise assignment of ion occupancy,future studies could employ more direct characterization techniques such as single-crystal X-ray diffraction refinement of the crystal structure for further verification.
[1]张蓓莉.系统宝石学[M].北京：地质出版社，2008:308-309.ZHANG Beili. Systematic gemmology[M]. Beijing:Geological Publishing House,2008:308-309.
[2]HAWTHORNE F C,HENRYS D J. Classification of the minerals of the tourmaline group[J]. European Journal of Mineralogy,1999,11(2):201-216.
[3]PEZZOTTA F,LAURS B M. Tourmaline:the kaleidoscopic gemstone[J]. Elements,2011,7(5):333-338.
[4]王雅涵，王丹，申婷婷，等.电气石成分及同位素特征在示踪成矿流体来源方面的应用[J].岩石矿物学杂志，2025,44(5):1193-1216.WANG Yahan,WANG Dan,SHEN Tingting,et al.Application of tourmaline composition and isotope characteristics in tracing the source of ore-forming fluids[J]. Acta Petrologica et Mineralogica,2025,44(5):1193-1216.
[5]郭伟康，董随亮，张松浩，等.西藏嘎波伟晶岩型锂矿中电气石组成、硼同位素特征及其地质意义[J].岩石学报，2025,41(3):804-819.GUO Weikang,DONG Suiliang,ZHANG Songhao,et al.Characteristics of tourmaline composition and boron isotope from the Gabo pegmatite-type lithium deposit in Xizang and their geological significance[J]. Acta Petrologica Sinica,2025,41(3):804-819.
[6]周起凤，秦克章，刘宇超，等.喜马拉雅东段库曲伟晶岩铁电气石-锂电气石-钙锂电气石系列及其指示意义[J].岩石学报，2025,41(3):837-858.ZHOU Qifeng,QIN Kezhang,LIU Yuchao,et al.Tourmaline of the schorl-elbaite-liddicoatite series from the Kuqu pegmatite in the East Himalaya,Tibet,and its implication[J]. Acta Petrologica Sinica,2025,41(3):837-858.
[7]侯一俊，洪汉烈，薛惠娟，等.巴西Minas Gerais彩色电气石的宝石矿物学特征[J].宝石和宝石学杂志，2008,10(3):8-11,22,53.HOU Yijun,HONG Hanlie,XUE Huijuan,et al.Gemmological and mineralogical characteristics of coloured tourmaline from Minas Gerais state,Brazil[J]. Journal of Gems&Gemmology,2008,10(3):8-11,22,53.
[8]王元龙，康旭，等.新疆阿尔泰彩色电气石的颜色成因研究[J].矿产与地质，1996,10(3):172-178.WANG Yuanlong,KANG Xu,et al. Study of color tourmalines for their color genesis from Altay,Xinjiang[J]. Mineral Resources and Geology,1996,10(3):172-178.
[9]岳素伟，剡晓旭，林佳淇，等.热处理棕褐色电气石光谱学特征与颜色成因初探[J].光谱学与光谱分析，2021,41(8):2524-2529.YUE Suwei,YAN Xiaoxu,LIN Jiaqi,et al.Spectroscopic characteristics and coloring mechanism of brown tourmaline under heating treatment[J].Spectroscopy and Spectral Analysis,2021,41(8):2524-2529.
[10]王进军，陶晓风，王武军.新疆绿色电气石颜色成因研究[J].岩石矿物学杂志，2005,24(4):319-323.WANG Jinjun,TAO Xiaofeng,WANG Wujun.Color characteristics of green tourmaline from Xinjiang[J]. Acta Petrologica et Mineralogica,2005,24(4):319-323.
[11]刘国彬，郭九皋.新疆色带电气石的生长过程及颜色起因研究[J].矿物学报，1985,5(3):199-207,289.LIU Guobin,GUO Jiugao. Growth process and origin of colour-banding tourmaline from Xinjiang[J].Acta Mineralogica Sinica,1985,5(3):199-207,289.
[12]HENN U,BANK H,BANK F H,et al. Transparent bright blue Cu-bearing tourmalines from Paraiba,Brazil[J]. Mineralogical Magazine,1990,54(377):553-557.
[13]范建良，冯锡淇，郭守国，等.电气石晶体的光学吸收谱[J].硅酸盐学报，2009,37(4):523-530.FAN Jianliang,FENG Xiqi,GUO Shouguo,et al.Optical absorption spectra of tourmaline crystals[J].Journal of the Chinese Ceramic Society,2009,37(4):523-530.
[14]仲佩佩，沈锡田.赞比亚墨绿色电气石的颜色成因初探[J].宝石和宝石学杂志，2017,19(6):7-14.ZHONG Peipei,SHEN Xitian. Colour origin of dark green tourmaline from Zambia[J]. Journal of Gems&Gemmology,2017,19(6):7-14.
[15]WILKINS R W T,FARRELL E F,NAIMAN C S.The crystal field spectra and dichroism of tourmaline[J].Journal of Physics and Chemistry of Solids,1969,30(1):43-56.
[16]MATTSON S M,ROSSMAN G R. Fe2+-Fe3+interactions in tourmaline[J]. Physics and Chemistry of Minerals,1987,14(2):163-171.
[17]李明，洪汉烈.阿富汗浅绿色电气石宝石学及谱学特征[J].光谱学与光谱分析，2023,43(7):2195-2201.LI Ming,HONG Hanlie. Gemological and spectro graphic characteristics of light-green tourmaline of Afghanistan[J]. Spectroscopy and Spectral Analysis,2023,43(7):2195-2201.
[18]洪汉烈，李晶，杜登文，等.彩色电气石致色离子的化学状态研究[J].宝石和宝石学杂志，2011,13(2):6-12.HONG Hanlie,LI Jing,DU Dengwen,et al.Chemical states of colour-induced cations in colourful tourmaline[J]. Journal of Gems&Gemmology,2011,13(2):6-12.
[19]LI M. Characterization of blue tourmaline from Madagascar for exploring its color origin[J]. Advances in Condensed Matter Physics,2022,2022:7167793. DOI:10. 1155/2022/7167793.
[20]MATTSON S M,ROSSMAN G R. Ferric iron in tourmaline[J]. Physics and Chemistry of Minerals,1984,11(5):225-234.
[21]彭文世，刘高魁.矿物红外光谱图集[M].北京：科学出版社，1982:350-351.PENG Wenshi,LIU Gaokui. Mineral infrared spectrum atlas[M]. Beijing:Science Press,1982:350-351.
[22]ERTL A. Mn-bearing"oxy-rossmanite"with tetrahedrally coordinated Al and B from Austria:structure,chemistry,and infrared and optical spectroscopic study[J]. American Mineralogist,2005,90(2/3):481-487.
[23]李雯雯，吴瑞华，董颖.电气石红外光谱和红外辐射特性的研究[J].高校地质学报，2008,14(3):426-432.LI Wenwen,WU Ruihua,DONG Ying. Study on infrared spectra and infrared radiation characteri stics of tourmaline[J]. Geological Journal of China Universities,2008,14(3):426-432.
[24]赵春芳，尹正勇，李波. α型氧化铝的微观结构对红外光谱图的影响[J].光谱实验室，2007,24(3):341-344.ZHAO Chunfang,YIN Zhengyong,LI Bo. Effect of alpha type alumina microstructure on infrared spectra[J].Chinese Journal of Spectroscopy Laboratory,2007,24(3):341-344.
[25]LI K,YUE S W. Mechanisms of thermal color change in brown elbaite-fluorelbaite tourmaline:insights from trace elements and spectral signatures[J]. Minerals,2025,15(10):1032. DOI:10. 3390/min15101032.
[26]ERTL A,HUGHES J M,PROWATKE S,et al.Tetrahedrally coordinated boron in tourmalines from the liddicoatite-elbaite series from Madagascar:structure,chemistry,and infrared spectroscopic studies[J].American Mineralogist,2006,91(11/12):1847-1856.
[27]PASETTI L,FORNASINI L,MANTOVANI L,et al.Study of Mg-Fe content in tourmalines from the draviteschorl series by Raman spectroscopy[J]. Journal of Raman Spectroscopy,2024,55(2):276-286.
[28]BOSI F,CELATA B,SKOGBY H,et al. Mn-bearing purplish-red tourmaline from the Anjanabonoina pegmatite,Madagascar[J]. Mineralogical Magazine,2021,85(2):242-253.
[29]CASTA??EDA C,OLIVEIRA E F,GOMES N,et al.Infrared study of OH sites in tourmaline from the elbaiteschorl series[J]. American Mineralogist,2000,85(10):1503-1507.
[30]NASSAU K. The origins of color in minerals[J].American Mineralogist,1978,63(3/4):219-229.
[31]SKOGBY H,BOSI F,LAZOR P. Short-range order in tourmaline:a vibrational spectroscopic approach to elbaite[J]. Physics and Chemistry of Minerals,2012,39(10):811-816.
[32]MANNING P G. On the origin of colour and pleochroism of astrophyllite and brown clintonite[J]. The Canadian Mineralogist,1969,9(5):663-677.
[33]周琳，张伟，周磊，等.铁镁电气石Y位阳离子主导的构效关系[J].硅酸盐学报，2024,52(10):3192-3204.ZHOU Lin,ZHANG Wei,ZHOU Lei,et al. Structurefunction relationship of Fe-Mg tourmaline dominated by positive ion in Y site[J]. Journal of the Chinese Ceramic Society,2024,52(10):3192-3204.
[34]王亚军.激光拉曼光谱测试和田玉中的石墨[J].中国无机分析化学，2024,14(12):1698-1704.WANG Yajun. Determination of graphite in Hetian jade by laser Raman spectroscopy[J]. Chinese Jorunal of Inorganic Analytical Chemistry,2024,14(12):1698-1704.
[35]薛景源，董发勤，周琳，等.电气石晶体内微结构对其压电性的影响及机制研究[J].矿物学报，2024,44(6):835-844.XUE Jingyuan,DONG Faqin,ZHOU Lin,et al. A study on the influence and mechanism of the microstructure of tourmaline crystal on its piezoelectricity[J].Acta Mineralogica Sinica,2024,44(6):835-844.
基本信息:
DOI：10.20236/j.CJIAC.2026.02.006
中图分类号:TS933.2;O657.3
引用信息:
[1]陈令霞,李明,王亚军,等.综合光谱技术深度分析蓝绿色电气石致色机理[J].中国无机分析化学,2026,16(02):228-235.DOI:10.20236/j.CJIAC.2026.02.006.
基金信息:
国家自然科学基金面上项目(42572402); 广东省教育科学规划课题(高等教育专项)(2024GXJK024); 广州市高校科研项目(2024312302)~~
2025-11-10
2025-11-10
2025-11-10