Gemmological and Spectral Characteristics of Ruby from Winza, Tanzania
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摘要:
坦桑尼亚温扎地区产出透明度高、颜色亮度高、色彩饱和度高且常产出粒度大的红宝石，但针对坦桑尼亚温扎红宝石的系统研究较少。利用常规宝石学仪器、激光剥蚀电感耦合等离子体质谱仪、紫外-可见光分光光度计、傅里叶变换红外光谱仪、拉曼光谱仪和三维荧光光谱仪对10颗产自坦桑尼亚温扎的红宝石样品进行系统性的研究与分析。结果显示，坦桑尼亚温扎红宝石含有韭闪石包裹体、气液包裹体、蓝色色区和具有生长间断的负晶包裹体，蓝色色区与较高的Ti元素含量有关，具有产地意义；温扎红宝石具有高Cr和高Fe的特征，两种元素的含量均超过500×10-6，并具有Ti、Mg、V、Ni、Ga等微量元素；紫外-可见光光谱显示清晰的Cr谱，同时也呈现出Fe和Ti的影响；几乎所有样品的红外光谱均可见特征的3 160 cm-1处吸收峰，常伴随着3 240 cm-1和2 420 cm-1吸收峰(称为“3 160组”)，为温扎红宝石的特征峰；拉曼光谱显示散射峰与[AlO6]基团的伸缩、弯曲振动有关，由对称弯曲振动(O-Al-Obend)引起的416 cm-1处吸收峰显示最强的光谱特征；三维荧光光谱中显示4个清晰的荧光峰，以λex=408 nm/λem=694 nm峰为最强。
Abstract:Rubies produced in the Winza region of Tanzania are highly transparent, have high colour brightness, high colour saturation and are often produced in large grain sizes, but few systematic studies have been carried out on the rubies from Winza, Tanzania. Systematic study and analysis of 10 ruby samples from Winza, Tanzania were carried out using conventional gemmological instruments, laser ablation inductively coupled plasma mass spectrometry, ultraviolet-visible spectrophotometer, Fourier transform infrared spectroscopy, Raman spectrometry and 3D fluorescence spectrometer. The results show that the rubies from Winza, Tanzania, contain pargasite inclusions, gas-liquid inclusions, blue colour zones, and negative crystal inclusions. The blue colour zone is associated with higher Ti elemental content and is of provenance significance. Rubies from Winza are characterized by high Cr and high Fe, all of which exceed 500×10-6 and that it also contains trace elements such as Ti, Mg, V, Ni, and Ga. The UV-Vis spectrum shows a clear Cr spectrum and also exhibits the influence of Fe and Ti. The 3 160 cm-1 absorption peak that is visible in almost all samples, is often accompanied by 3 240 cm-1and 2 420 cm-1 absorption peaks, called the "3 160 group". Raman spectra show scattering peaks related to the stretching and bending vibrations of the [AlO6] group, with absorption peak at 416 cm-1 caused by symmetric bending vibrations (O-Al-Obend) showing the strongest spectral features. 3D fluorescence spectra show 4 clear fluorescence peaks and the λex=408 nm/λem=694 nm peak is the strongest one.
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图 2 坦桑尼亚温扎红宝石样品的表面特征：(a)黑色固体物质；(b)黑色固体和黄色浸染物质；(c)生长台阶；(d)平行排列的不规则状凹坑
Figure 2. Surface characteristics of the ruby samples from Winza, Tanzania: (a) black solid material; (b) black solid and yellow impregnated material; (c) growth steps; (d) irregularly shaped pits in parallel rows
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图 3 坦桑尼亚温扎红宝样品中的固体包裹体：(a)大量聚集的固体包裹体；(b)单独分布的灰黑色固体包裹体
Figure 3. Solid inclusions in the ruby samples from Winza, Tanzania: (a) massively aggregated solid inclusions; (b) individually distributed grey-black solid inclusions
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图 4 坦桑尼亚温扎红宝石样品中韭闪石包裹体的拉曼光谱
注：Test为测试包裹体的拉曼光谱；Pargasite为摘自RRUFF数据库的标准拉曼光谱
Figure 4. Raman spectra of pargasite inclusions in ruby samples from Winza, Tanzania
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图 5 坦桑尼亚温扎红宝石样品的内部特征：(a)平行拉长状两相包裹体；(b)大量负晶被气液填充且随愈合裂隙面分布
Figure 5. Internal characteristics of ruby samples from Winza, Tanzania: (a) parallel elongated two-phase inclusions; (b) a large number of negative crystals are filled with gas-liquid and distributed with the healed fracture surface
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图 6 坦桑尼亚温扎红宝石样品中充填在负晶中的H2O的拉曼光谱
Figure 6. Raman spectra of H2O filled in negative crystals in the ruby sample from Winza, Tanzania
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图 7 坦桑尼亚温扎红宝石样品中平行规律排列且有生长间断的负晶包裹体
Figure 7. Parallel regularly arranged negative crystal inclusions with growth discontinuities in the ruby sample from Winza, Tanzania
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图 8 坦桑尼亚温扎红宝石样品中被CO2充填的特殊形态的包裹体(a)及其3个点位的拉曼光谱(b)
Figure 8. The CO2-filled inclusions (a) and Raman spectra of the 3 testing points in ruby sample from Winza, Tanzania (b)
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图 9 坦桑尼亚温扎红宝石样品的片状蓝色色区
Figure 9. Flaky blue coloured zone in ruby samples from Winza, Tanzania
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图 10 坦桑尼亚温扎红宝石P-1样品蓝色色区和化学成分测试点
Figure 10. Blue colour zone and chemical composition test points of ruby sample P-1 from Winza, Tanzania
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图 11 坦桑尼亚温扎红宝石样品的紫外-可见光光谱: (a)O组样品；(b)P组样品；(c)PR组样品；(d)样品PR-1
Figure 11. UV-Vis spectra of ruby samples from Winza, Tanzania: (a) Group O; (b) Group P; (c) Group PR; (d) sample RP-1
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图 12 坦桑尼亚温扎红宝石样品的红外透射光谱
Figure 12. Infrared transmission spectra of ruby samples from Winza, Tanzania
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图 14 坦桑尼亚温扎红宝石样品的指纹区红外光谱
Figure 14. Infrared spectra of the fingerprint region of ruby samples from Winza, Tanzania
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图 16 坦桑尼亚温扎红宝石样品O-2的三维荧光光谱
Figure 16. 3D fluorescence spectrum of the ruby sample O-2 from Winza, Tanzania
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图 17 坦桑尼亚温扎红宝石样品的激发光谱
Figure 17. Excitation spectra of ruby sample from Winza, Tanzania
表 1 坦桑尼亚温扎红宝石样品的常规宝石学特征
Table 1 Conventional gemmological characteristics of ruby samples from Winza, Tanzania
样品号 颜色 光泽 透明度 折射率 相对密度 紫外荧光 二色性 长波 短波 O-1 橙粉色 亮玻璃光泽 半透明 1.760~1.768 3.89 中等红色 惰性 强黄色/粉色 O-2 橙粉色 亮玻璃光泽 透明 1.761~1.769 3.96 强红色 惰性 弱浅黄色/浅粉色 O-3 橙粉色 亮玻璃光泽 透明 1.760~1.768 3.81 强红色 惰性 强黄色/粉色 P-1 浅粉色 亮玻璃光泽 透明 1.760~1.768 3.80 中等红色 惰性 弱粉色/浅粉色 P-2 浅粉色 亮玻璃光泽 透明 1.760~1.768 4.00 中等红色 惰性 弱粉色/浅粉色 P-3 浅粉色 亮玻璃光泽 透明 1.758~1.766 3.90 中等红色 惰性 弱橙粉色/浅粉色 PR-1 紫红色 亮玻璃光泽 透明 1.760~1.768 4.00 中等红色 惰性 中等黄色/粉色 PR-2 紫红色 亮玻璃光泽 透明 1.760~1.768 4.00 中等红色 惰性 强浅粉色/紫红色 PR-3 紫红色 亮玻璃光泽 半透明 1.760~1.768 3.92 中等红色 惰性 强淡黄色/紫红色 PR-4 紫红色 亮玻璃光泽 半透明 1.761~1.769 4.02 中等红色 惰性 强橙黄色/紫红色 
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表 2 坦桑尼亚温扎红宝石样品的颜色与LA-ICP-MS测试结果
Table 2 The colours and testing results of LA-ICP-MS of ruby samples from Winza, Tanzania
样品号 颜色描述 MgO/% Al2O3/% SiO2/% P2O5/% TiO2/% FeO/% V/10-6 Cr/10-6 Ni/10-6 Ga/10-6 O-1 橙粉色 0.006 4 98.6 0.73 0.024 0.004 0 0.49 1.86 831 - 34.7 O-2 橙粉色 0.009 2 98.5 0.87 0.017 0.005 6 0.48 1.47 751 - 36.7 O-3 橙粉色 0.005 5 98.7 0.85 0.015 0.002 9 0.31 1.03 963 - 23.5 P-1 浅粉色 0.006 8 98.8 0.69 0.026 0.001 4 0.41 0.96 603 2.51 23.0 P-2 浅粉色 0.008 8 98.6 0.83 0.020 0.009 0 0.45 1.86 582 7.04 34.6 P-3 浅粉色 0.010 0 98.6 0.71 0.019 0.004 2 0.50 2.35 624 0.34 33.9 PR-1 紫红色 0.007 8 98.5 0.81 0.015 0.004 3 0.36 1.44 2028 0.91 24.2 PR-2 紫红色 0.009 6 98.7 0.71 0.030 0.004 8 0.30 7.45 1634 - 41.9 PR-3 紫红色 0.002 3 98.6 0.87 0.010 0.010 8 0.30 2.03 874 2.75 32.4 PR-4 紫红色 0.015 1 98.4 0.84 0.019 0.015 0 0.45 5.62 1674 6.44 29.9 注：-表示低于检测限。
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表 3 坦桑尼亚温扎红宝石样品中不同色区微量元素的种类与含量
Table 3 Types and contents of ruby trace elements in different colour zones of ruby samples from Winza, Tanzania /10-6
测试点位 Mg Ti Fe Cr V Ni Ga P-1-01 0.86 26.15 2 763 400 0.97 2.69 21 P-1-02 40.65 8.58 3 202 603 0.96 2.51 23
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