雪宝顶白钨矿的谱学特征及主微量元素分析

doi:10.3964/j.issn.1000-0593(2024)06-1689-08

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摘要：白钨矿是一种稀有宝石，具粒状、块状构造，颜色为白-浅黄色，油脂光泽，荧光性明显。四川平武雪宝顶白钨矿矿床为围岩蚀变较弱的脉状热液巨晶宝石级矿床，产出白钨矿颜色饱和度较高，具完美晶型且色泽纯正，与绿柱石、锡石和白云母共生。该研究选取雪宝顶近无色-橘黄色调白钨矿为研究对象，使用X射线粉晶衍射（XRD）、傅里叶变换红外光谱分析仪、紫外-可见分光光度计、激光拉曼光谱仪、电子探针、激光剥蚀电感耦合等离子体质谱仪（LA-ICP-MS）的综合分析，结合矿物学、谱学与主微量元素特征，确定近无色-橘黄色调白钨矿的矿物成分、晶体结构、特征鉴别谱带、致色离子以及主微量、稀土等化学组分含量，探讨白钨矿稀土元素含量与颜色成因关系，为雪宝顶近无色-橘黄色调白钨矿提供诊断性鉴别依据。研究结果表明，白钨矿结晶程度较好，化学成分均匀，无明显间断，矿物成分含量相对集中，共生矿物多为白云母和伊利石。样品具典型的白钨矿红外特征峰440、809和870 cm^-1及与Ca²⁺有关的448 cm^-1特征峰，谱峰显示色调越深者吸收度越高；拉曼特征峰909 cm^-1和Ca—O晶格振动峰207 cm^-1，随色调加深强度加深；紫外吸收峰表现为橙黄区强吸收，尖峰在383、570、584和804 nm附近，近无色调者仅具383 nm尖峰，黄色调较浅者近紫外区Fe³⁺吸收度较低，黄色调较深者蓝紫区Fe³⁺强吸收且其橘黄色调由Nd³⁺所致；白钨矿化学组分WO₃和CaO质量比接近甚至超过理想值，近无色者含量相对集中；微量元素中Fe元素与色调呈正相关，黄色调越深者，含量越高；稀土总量变化范围大，轻稀土更为富集，具明显的Eu负异常，Ce异常不明显。浅黄色调受微量元素Si、Fe元素及Fe³⁺的d—d电子跃迁影响，黄色调受微量元素Mn、Fe元素及Fe³⁺的电子跃迁所致，橘黄色调受稀土Nd和Sm元素影响较大。

关键词：雪宝顶；白钨矿；近无色-橘黄色调；谱学特征；原位微区主微量元素特征

Abstract：Scheelite is a rare gemstone with a massive granular structure, exhibiting a white to light yellow coloration, greasy luster, and obvious fluorescence. The scheelite deposit at Xuebaoding in the Pingwu region of Sichuan Province is a vein-like hydrothermal-type deposit with weak alteration of host rocks. Scheelite produced has a high color saturation, perfect crystal form, and pure color, associated with beryl, cassite and muscovite. The nearly colorless to orange tone scheelite from Xuebaoding was taken as the research object in this study. Comprehensive analysis was conducted using X-ray powder diffraction (XRD), Fourier infrared spectrum analysis, ultraviolet-visible spectrophotometer, laser Raman spectrometer, electron probe, and laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS). The mineral composition, crystal structure, characteristic identification spectral bands, color-causing ions, as well as the contents of the main and trace elements, rare earth and other chemical components of the nearly colorless to orange tone scheelite were determined by combining mineralogy, spectroscopy and main and trace elements characteristics. The relationship between rare earth element content and color genesis was also discussed. All have to provide the diagnostic basis for identification of nearly colorless to orange tone scheelite from Xuebaoding. The research results demonstrate that scheelite exhibits good crystallinity, displaying a uniform chemical composition without obvious discontinuity. The mineral composition is relatively concentrated, and the accessory minerals are mostly muscovite and illite. Significantly, scheelite's typical infrared characteristic peaks were observed at 440, 809 and 870 cm^-1, along with a peak at 448 cm^-1 related to Ca²⁺. The spectral peak exhibits higher absorption for deeper color tones. In the same way, the Raman characteristic peak is at 909 cm^-1, and the Ca—O lattice vibration peak is at 207 cm^-1, with increasing intensity as the color tone deepens. Additionally, the ultraviolet absorption peaks show strong absorption in the orange-yellow region, with peaks around 383, 570, 584 and 804 nm. The nearly colorles scheelite samples only exhibit a peak at 383 nm, while the scheelite sample with a lighter yellow tone demonstrates weak absorption of Fe³⁺ in the near ultraviolet region. Conversely, the scheelite samples with a deeper yellow tone display strong absorption of Fe³⁺ in the blue-purple region and the orange tone due to Nd³⁺. Moreover, the chemical components of scheelite reveal a WO₃/CaO mass ratio that approaches or exceeds the ideal value, while the content of the nearly colorless scheelite sample is relatively concentrated. The trace element Fe demonstrates a positive correlation with color tone, whereby the content increases as the yellow tone becomes darker. Nevertheless, the total amount of rare earths varies widely, with an enrichment of light rare earths, significant negative Eu anomalies, and insignificant Ce anomalies. The light yellow tone is influenced by trace elements Si and Fe and the d-d electronic transition of Fe³⁺. Similarly, the yellow tone is affected by trace elements Mn and Fe, along with the electronic transition of Fe³⁺. In contrast, the orange tone is significantly impacted by rare earth elements Nd and Sm.

Key words：Xuebaoding;Scheelite;Nearly colorless to orange tone;Spectral characteristics;Characteristics of main and trace elements in in-situ micro areas

收稿日期: 2023-07-15 修订日期: 2024-03-05

中图分类号:

P575.4

基金资助: 国家自然科学基金项目（42002156），河北省自然科学基金项目（D2021403015），河北省高等学校科学技术研究项目（QN2021027），河北地质大学国家预研项目（KY2024YB01），河北省研究生创新项目（CXZZSS2023134和CXZZSS2024107）资助

通讯作者: 史淼 E-mail: miaoer727@126.com

作者简介: 曹沁元，1996年生，河北地质大学地球科学学院硕士研究生 e-mail: maxcaoqinyuan@163.com

引用本文:

曹沁元，史淼，马世玉. 雪宝顶白钨矿的谱学特征及主微量元素分析[J]. 光谱学与光谱分析, 2024, 44(06): 1689-1696.
CAO Qin-yuan, SHI Miao, MA Shi-yu. Spectral Characteristics and Analysis of Main and Trace Elements of Scheelite From Xuebaoding. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2024, 44(06): 1689-1696.

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[1] LI Sheng-rong(李胜荣). Crystallography and Mineralogy(结晶学与矿物学). Beijing: Geological Press(北京: 地质出版社), 2008. 284.
[2] SONG Guo-xue, XIONG Yu-xin(宋国学, 熊玉新). Shandong Land and Resources(山东国土资源), 2021, 37(2): 1.
[3] LIU Yan(刘琰). Acta Petrologica et Mineralogica(岩石矿物学杂志), 2017, 36(4): 549.
[4] WU Da-wei, LI Bao-hua, DU Xiao-fei, et al(吴大伟, 李葆华, 杜晓飞, 等). Mineral Deposits(矿床地质), 2015, 34(4): 745.
[5] LIU Yan, DENG Jun, LI Chao-feng, et al(刘琰, 邓军, 李潮峰, 等). Chinese Science Bulletin(科学通报), 2007, 52(16): 1923.
[6] ZHU Xin-xiang, LIU Yan(朱鑫祥, 刘琰). Rock and Mineral Analysis(岩矿测试), 2021, 40(2): 296.
[7] LIU Xian-yu, YANG Jiu-chang, TU Cai, et al(刘衔宇, 杨九昌, 涂彩, 等). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2023, 43(8): 2550.
[8] LIU Yan, DENG Jun, XING Yan-yan, et al(刘琰, 邓军, 邢延炎, 等). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2008，28(1): 121.
[9] AN Na, GUO Qing-feng, LIAO Li-bing(安娜, 郭庆丰, 廖立兵). National Gemstone Testing Center, Proceedings of the China International Jewelry and Jewelry Academic Exchange Conference(国家珠宝玉石质量监督检验中心，中国国际珠宝首饰学术交流会论文集), 2019: 174.
[10] LI Jian-kang, LIU Shan-bao, WANG Deng-hong, et al(李建康, 刘善宝, 王登红, 等). Mineral Deposits(矿床地质), 2007, 26(5): 557.
[11] YAN Dan-ping, LI Shu-bing, CAO Wen-tao, et al(颜丹平, 李书兵, 曹文涛, 等). Earth Science Frontiers [China University of Geosciences (Beijing); Peking University][地学前缘(中国地质大学（北京）；北京大学)], 2010, 17(5): 106.
[12] LIU He, YAN Dan-ping, WEI Guo-qing(刘鹤, 颜丹平, 魏国庆). Acta Geologica Sinica(地质学报), 2008, 82(4): 464.
[13] Zhu Xinxiang, Raschke M B, Liu Yan. Minerals, 2020, 10(5): 438.
[14] CAO Zhi-min, REN Jian-guo, LI You-guo, et al(曹志敏, 任建国, 李佑国, 等). Science in China (Series D)[中国科学(D辑：地球科学)], 2002, 32(1): 64.
[15] Liu Yan, Deng Jun, Li Chaofeng, et al. Chinese Science Bulletin, 2007, 52(18): 2543.
[16] ZHAO Yu-ting, LI Zi-ying, LIU Jun-gang, et al(赵宇霆，李子颖，刘军港，等). World Nuclear Geoscience(世界核地质科学), 2021, 38(2): 144.
[17] WEN Lu(闻辂). Mineral Infrared Spectroscopy(矿物红外光谱学). Chongqing: Chongqing Univesity Press(重庆: 重庆大学出版社), 1989.
[18] ZHOU Pei-ling(周佩玲). Journal of East China Institute of Geosciences(华东地质学院学报), 1983，(2): 12.
[19] De La Pierre M, Noel Y, Mustapha S, et al. American Mineralogist, 2013, 98(5-6): 966.
[20] LUO Yue-ping, CHEN Jing-jing(罗跃平, 陈晶晶). Journal of Gems & Gemology[宝石和宝石学杂志(中英文)], 2020, 22(5): 39.
[21] SU Yu-zhi, YANG Chun, LUO Yuan(苏雨峙, 杨春, 罗源). Journal of Gems and Gemology(宝石和宝石学杂志), 2015, 17(6): 25.
[22] CHEN Tao, LIU Yun-gui, YIN Zuo-wei, et al(陈涛, 刘云贵, 尹作为, 等). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2013, 33(11): 2964.
[23] WU Rui-hua, ZHU Feng-fu, BAI Feng(吴瑞华，朱凤福，白峰). Geological Review(地质论评), 2001, 47(3): 255.
[24] Crane M, Frost R L, Williams P A, et al. Journal of Raman Spectroscopy, 2002, 33(1): 62.
[25] LI Mei-rong, WANG Hong-ling, LI Bo, et al(李美荣, 王洪岭, 李波, 等). Acta Mineralogica Sinica(矿物学报), 2022, 42(2): 213.
[26] Sun S S, McDonough W F. Geological Society, London, Special Publications, 1989, 42(1): 313.