Application of EMPA-XRD-SEM to Study the Mineralogical Characteristics of Turquoise from Xichuan, Henan Province
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摘要: 河南省淅川县位于我国重要绿松石产区——秦岭东部绿松石矿区东延部分，与淅川毗邻的许多早期考古遗址中出土了大量的绿松石制品，因此淅川绿松石的矿料流布受到许多考古学者的关注。研究淅川绿松石的矿物学特征有助于完善我国不同矿区绿松石矿物学研究，为追溯我国早期绿松石文物的矿料来源提供重要的数据支撑。本文利用偏光显微镜观察、扫描电镜、粉晶X射线衍射等技术对淅川绿松石进行结构研究，辅以电子探针、背散射电子图像观察等方法研究了淅川绿松石的矿物组合。结果表明：淅川绿松石主要由细小的鳞片状、短柱状、板片状微晶集合体组成，可见环带状、结核状、碎斑碎粒状结构；通过对比不同样品的微晶结构，可知其微晶的大小、晶型和分布状态会影响淅川绿松石集合体的致密程度和颜色；淅川绿松石集合体中常见石英、玉髓和铁氧化物，部分样品含有硫磷铝锶矿。通过对比其他矿区绿松石矿物组合，发现淅川绿松石与湖北地区的绿松石矿物组成相近，主要杂质为石英、褐铁矿，明显区别于安徽地区以高岭石为主要杂质矿物的绿松石。Abstract:
BACKGROUNDThe Xichuan turquoise mining area in Henan Province belongs to the east extension of the turquoise metallogenic belt in the junction of Hubei and Shaanxi Provinces. A lot of turquoise artifacts have been excavated in many early archaeological sites near Xichuan. Therefore, the distribution of the Xichuan turquoises has attracted wide attention of many archaeologists. OBJECTIVESTo study mineralogical characteristics of Xichuan turquoise in order to improve the mineralogical study of turquoise in different mining areas in China and provide important data support for tracing the mineral resources of early turquoise artifacts in China. METHODSTechnologies including polarizing micro-scope, scanning electron microscope, X-ray diffraction were applied to study the texture and structure of turquoise. Electron probe microanalysis and back scattered electron imaging were applied to study the mineral assemblage of Xichuan turquoise. RESULTSXichuan turquoise, ring-like, nodular and patchy granular was primarily composed of fine scaly, short columnar and lamellar microcrystalline aggregates. By comparing the microcrystalline structures of different samples, it was noted that the sizes, shapes and distributions could affect the densification and color of Xichuan turquoise. Quartz, chalcedony and iron oxide were common in the Xichuan turquoise aggregate. Svanbergite could also be observed in some samples. CONCLUSIONSBy comparing the mineral assemblages of turquoise in other mining areas, it was found that Xichuan turquoise was similar to the turquoise in Hubei Province with quartz and limonite as main mineral impurities, different from the turquoise in Anhui Province with kaolinite as main mineral impurities. -
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表 1 河南淅川绿松石样品的特征
Table 1. Regular gemological characteristics of turquoise from Xichuan area of Henan Province
样品编号 外观特征 DSQ-1 浅蓝色、蓝色；土状光泽；绿松石为结核状；围岩为层状页岩，黄褐色，靠近松石的边缘处为深褐色 DSQ-2 蓝色；玻璃光泽；绿松石为致密块状；表面可见不规则网状分布的黑色杂质，俗称“铁线” DSQ-3 浅蓝色；玻璃光泽；边缘为浅白色风化层；绿松石为致密块状; 围岩为黑色 DSQ-4 浅蓝色、蓝白色、表面有白色风化层；土状光泽；绿松石呈镶嵌状；围岩为褐黄色 DSQ-5 深蓝色；玻璃光泽；绿松石为结核状；围岩为褐黄色，紧紧包裹着绿松石 DSQ-6 蓝色；玻璃光泽；绿松石为结核状、脉状；围岩为褐黄色 
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表 2 河南淅川绿松石电子探针分析结果
Table 2. EMPA analysis of turquoise from Xichuan area of Henan Province
成分 绿松石 硫磷铝锶矿
(图 3b-B区)石英 褐铁矿 Tur(图 3a) Tur(图 3b-A区) Qz-1(图 3a) Qz-2(图 3a) Lm-1(图 3a) Lm-2(图 3a) SiO2 0.478 0.519 1.237 89.262 97.162 0.604 7.731 FeO 0.158 0.137 0.088 0.017 0.105 55.402 69.386 SO3 0.379 0.393 4.519 0.005 0.205 0.143 0.117 Al2O3 39.716 40.66 32.639 0.019 0.408 4.406 1.088 CuO 6.61 5.973 0.449 - 0.224 0.209 0.382 P2O5 33.86 35.124 20.185 - 0.121 1.306 0.314 SrO 0.428 0.741 7.542 - - 0.011 - V2O3 - 0.14 0.685 - 0.027 8.125 3.173 CaO 0.55 0.983 7.728 0.042 0.034 0.356 0.382 MgO 0.042 0.037 0.071 0.032 - 0.047 0.071 ZnO 1.34 1.188 - - - 2.029 - BaO 0.085 0.07 1.324 0.002 - 0.078 0.215 MnO 0.051 0.029 0.015 0.033 0.038 0.035 0.093 K2O 0.08 0.1 0.412 0.048 0.035 0.137 0.108 TiO2 0.073 - 0.064 0.025 - 0.263 0.339 PbO - - 0.032 - - - - 总量 83.85 86.094 76.99 89.485 98.359 73.151 83.399 注：①由于绿松石中含水，故测试结果总和低于100。②“-”表示低于电子探针检测限。
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表 3 河南淅川绿松石样品DSQ-5B粉晶X射线衍射数据和硫磷铝锶矿标准卡片对比
Table 3. X-ray powder diffraction data of sample DSQ-5B area and the standard card of Svanbergite
PDF#39-1361 Svanbergite标准卡片 样品DSQ-5B 2θ d(nm) 2θ d(nm) 15.602 0.5675 15.7 0.56398 25.524 0.3487 25.49 0.34916 30.032 0.2973 30.049 0.29714 30.283 0.2949 30.38 0.29398 36.789 0.2441 36.87 0.24358 40.341 0.22339 40.91 0.22041 46.235 0.19619 47.979 0.18946 52.444 0.17433 52.279 0.17484 63.965 0.14543 63.021 0.14738 65.743 0.14192 65.664 0.14207 68.52 0.13683 68.543 0.13679 69.611 0.13495 69.183 0.13568 73.854 0.12821 73.618 0.12856 80.148 0.11965 80.04 0.11978
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