黄绿色葡萄石的谱学特征及颜色成因

doi:10.3964/j.issn.1000-0593(2024)09-2538-07

摘要
参考文献
相关文章 (3)

全文: PDF (11834 KB)
输出: BibTeX | EndNote (RIS)

摘要：颜色是宝石重要的光学性质之一，也是影响宝石品质及价格的重要参数。黄绿色葡萄石作为一种常见的玉石品种，其结构、致色离子的种类、价态及配位的复杂性，导致前人关于其致色成因存在较大的争议。采用傅里叶红外吸收光谱（FTIR）、紫外-可见光分光光谱（UV-Vis）、激光剥蚀-等离子体质谱（LA-ICP-MS）及穆斯堡尔谱（Mössbauer）等现代分析测试手段，对2个典型的黄绿色葡萄石样品（浅黄绿色样品LYG和深黄绿色样品DYG）的主要致色离子种类、价态及配位状态进行了深入研究，为黄绿色葡萄石的致色成因提供科学的解释。UV-Vis分析结果表明，样品LYG和样品DYG均出现明显的~425和~585 nm处的吸收带，分别与Fe³⁺_oct的电子跃迁和Fe²⁺_ch-Fe³⁺_oct的电荷转移有关。Mössbauer超精细参数分析结果显示，样品LYG和样品DYG中Fe³⁺的IS均为0.34 mm·s^-1，QS值分别为0.22和0.35 mm·s^-1，均符合葡萄石八面体配位中Fe³⁺的特征。样品LYG（IS=1.08 mm·s^-1）和样品DYG（IS=1.07 mm·s^-1）的Fe²⁺具有相近的IS值，均符合八面体配位中Fe²⁺的特征。然而，样品DYG中Fe²⁺的QS值（QS=2.78 mm·s^-1）明显高于样品LYG（QS=1.12 mm·s^-1），说明前者结构中Fe²⁺处于畸变的八面体中。样品DYG结构中Fe的含量和Fe²⁺的比例（4.02 wt%；11.88%）均高于样品LYG（3.55 wt%；5.27%），表明黄绿色葡萄石的颜色可能与Fe的含量和Fe²⁺的比例有关。样品LYG和样品DYG中V的含量分别为633和1 810 μg·g^-1，指示V可能对黄绿色葡萄石的颜色有贡献，但含量明显低于Fe，所以V对颜色的贡献远低于Fe³⁺和Fe²⁺。该研究不仅查明了黄绿色葡萄石的主要致色离子种类（Fe），而且确定了致色离子的价态（Fe³⁺和Fe²⁺）和配位状态（八面体配位），为黄绿色葡萄石颜色的定量研究提供了有益的基础素材。

关键词：离子种类、价态；配位状态；致色机理

Abstract：Color is one of the important optical properties of gemstones, and it is also an important parameter affecting their quality and price. As a common jade variety, the complex structure, color ions, valence states and coordination of yellow-green prehnite have led to great controversy about its color genesis. In this paper, the species, valence, and coordination state of the main chromogenic ions of two typical yellow-green prehnite samples (light yellow-green sample LYG and dark yellow-green sample DYG) were investigated using modern analytical methods such as Fourier infrared absorption spectroscopy (FTIR), ultraviolet-visible spectroscopy (UV-Vis), laser-exfoliation-plasma mass spectrometry (LA-ICP-MS) and Mössbauer spectroscopy, which provides a scientific explanation for the color genesis of yellow-green prehnite. UV-Vis analysis indicates that both sample LYG and sample DYG showed obvious absorption bands at ~425 and ~585 nm, which were related to the electron leap of Fe³⁺_oct and the charge transfer of Fe²⁺_ch-Fe³⁺_oct, respectively. Ultrafine parameter analysis of Mössbauer shows that the IS of Fe³⁺ in both sample LYG and sample DYG is 0.34 mm·s^-1, and the QS values are 0.22 and 0.35 mm·s^-1, respectively, both consistent with the characterization of Fe³⁺ in the octahedral ligand of prehnite. Sample LYG (IS=1.08 mm·s^-1) and sample DYG (IS=1.07 mm·s^-1) have similar IS values for Fe²⁺, both of which are consistent with the characterization of Fe²⁺ in octahedral coordination. However, the QS value of Fe³⁺ in sample DYG (QS=2.78 mm·s^-1) is significantly higher than that of the light yellow-green sample LYG (QS=1.12 mm·s^-1), suggesting that Fe²⁺ is in the distorted octahedron in the former structure. The content of Fe and the proportion of Fe²⁺ in sample DYG (4.04 wt%; 11.88%) are higher than those of the light yellow-green sample LYG (3.55 wt%; 5.27%), suggesting that the yellow-green color of prehnite may be related to the content of Fe and the proportion of Fe²⁺. The contents of V in sample LYG and the dark yellow-green sample DYG are 633 and 1 810 μg·g^-1, respectively, indicating that V may contribute to the yellow-green color of prehnite. Still, its content is significantly lower than Fe, so the contribution to the color is much lower than Fe³⁺ and Fe²⁺. The present study not only identified the main chromogenic ion species (Fe) of yellow-green prehnite, but also determined the valence states (Fe³⁺ and Fe²⁺) and coordination states (octahedral coordination) of the chromogenic ions, which provides a solid theoretical basis for the quantitative study of the color of yellow-green prehnite.

Key words：Ion species; Valence;Coordination state;Chromogenic mechanism

收稿日期: 2023-09-18 修订日期: 2024-05-08

中图分类号:

P571

基金资助: 横向课题（6602424717），山东省艺术科学重点课题（ZD202008219），国家自然科学基金项目（42072056）资助

通讯作者: 殷科，郑海蓉 E-mail: yinke1984@qq.com；1295593632@qq.com

作者简介: 李灿，女，1990年生，青岛农业大学艺术学院讲师 e-mail: 906919847@qq.com

引用本文:

李灿，陈江军，王文杰，殷科，郑海蓉，陆卓，刘振东，王一铭，杨云淇，韩文，王朝文. 黄绿色葡萄石的谱学特征及颜色成因[J]. 光谱学与光谱分析, 2024, 44(09): 2538-2544.
LI Can, CHEN Jiang-jun, WANG Wen-jie, YIN Ke, ZHENG Hai-rong, LU Zhuo, LIU Zhen-dong, WANG Yi-ming, YANG Yun-qi, HAN Wen, WANG Chao-wen. Spectral Characteristics and Color Genesis of Yellow-Green Prehnite. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2024, 44(09): 2538-2544.

链接本文:

https://www.gpxygpfx.com/CN/10.3964/j.issn.1000-0593(2024)09-2538-07 或 https://www.gpxygpfx.com/CN/Y2024/V44/I09/2538

[1] PENG Zhi-zhong, ZHOU Gong-du, TANG You-qi(彭志忠，周公度，唐有祺). Acta Chimica Sinica(化学学报), 1959, 25(1): 56.
[2] Deer W A, Howie R A, Zussman J. An Introduction to the Rock-Forming Minerals. London: The Mineralogical Society, 2013.
[3] Nagashima M, Iwasa K, Akasaka M. Mineralogy and Petrology, 2018, 112: 173.
[4] Ross N L, Detrie T A, Liu Z. Minerals, 2020, 10(4): 312.
[5] Papike J J, Zoltai T. American Mineralogist, 1967, 52: 974.
[6] QIN Shan, GU Ting-ting, WU Xiang(秦善，顾婷婷，巫翔). Acta Petrologica Sinica(岩石学报), 2019, 35(1): 146.
[7] Detrie T A, Ross N L, Angel R J, et al. Mineralogical Magazine, 2008, 72(6): 1163.
[8] White A J R, Laukamp C, Stokes M A, et al. Geochemistry: Exploration, Environment, Analysis, 2017, 17(4): 315.
[9] Akizuki M. Canadian Mineralogist, 1987, 25: 707.
[10] Baur W, Joswig W, Kassner D, et al. Journal of Solid State Chemistry, 1990, 86: 330.
[11] Kano K, Satoh H, Bunno M. Journal of the Japanese Association of Mineralogists Petrologists & Economic Geologists, 1986, 81: 51.
[12] Reddy N C G, Fayazyddin S M, Reddy R R S, et al. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2005, 62: 71.
[13] Pan Y, Mao M, Lin J. The Canadian Mineralogist, 2009, 47(4): 933.
[14] Malatesta C, Crispini L, Ildefonse B, et al. Journal of Structural Geology, 2021, 147: 104350.
[15] WANG Qian-qian, GUO Qing-feng, GE Xiao(王倩倩，郭庆丰，葛笑). Journal of Synthetic Crystals(人工晶体学报), 2022, 51(4): 723.
[16] Elburg M A，Cairncross B. South African Journal of Geology, 2022, 125: 113.
[17] Kumar A, Singh M R, Sarma P R, et al. Journal of Physics D: Applied Physics, 1989, 22: 465.
[18] ZHANG Fu-liang, YI Fan, CHEN Yi-long, et al(张富良，易凡，陈义龙, 等). Wuhan University Journal of Natural Sciences[武汉大学学报(自然科学版)], 1997, 43(3): 348.
[19] WANG Qiu-xia, PING Xian-quan, DAI Hong-kun, et al(王秋霞，平先权，戴宏坤, 等). Earth Science(地球科学), 2023, 48(3): 1217.
[20] Wang Q, Guo Q, Li N, et al. RSC Advances, 2022, 12: 3044.
[21] Dyar M D, Agresti D G, Schaefer M W, et al. Annual Review of Earth and Planetary Sciences, 2006, 34: 83.
[22] Nazarova G S, Ostashchenko B A, Mitrofanov V Y, et al. Journal of Applied Spectroscopy, 1990, 53(2): 305.
[23] Farmer V C. Infrared Spectra of Minerals. Mineralogical Society, 1974.