光谱学与光谱分析, 2019, 39 (9): 2746, 网络出版: 2019-09-28  

白色-浅灰色高山石与昌化石产地鉴别谱学初探

Preliminary Study on Origin Identification of White-Light Gray Gaoshan Stone and Changhua Stone
作者单位
中国地质大学珠宝学院, 湖北 武汉 430074
摘要
我国印章石文化源远流长。 寿山石和昌化石是我国著名的印章石品种, 但是其价格存在一定的差异。 高山石是寿山石中的主要品种, 市场占有率高。 为了有效进行产地鉴别的初步研究, 选择白色-浅灰色高山石与昌化石, 以避免致色矿物或致色元素对产地鉴别的干扰。 采用傅里叶变模红外光谱(FTIR)、 拉曼光谱(LRM)、 和激光剥蚀-等离子体质谱(LA-ICP-MS)分析白色-浅灰色的高山石和昌化石的矿物组成和痕量化学成分, 并结合两者的物理性质, 探究两个产地的印章石的异同和鉴别方法。 白色-浅灰色高山石颜色较昌化石均一, 高山石透明度整体上较好, 两者密度和折射率非常相近。 根据红外光谱指纹区谱峰, 可以确定白色-浅灰色的高山石和昌化石的基质均以高岭石族矿物为主要成分。 高岭石族矿物中羟基在结构中的占位不同, 因此在红外光谱中羟基伸缩振动吸收峰的数目与形态各不相同。 根据红外光谱中官能团区的羟基峰形态和数目的测试结果, 可知高山石的主要矿物成分为有序地开石, 而昌化石样品中的主要矿物成分为无序地开石, 两者均可含有少量高岭石。 利用拉曼光谱对两者的砂钉状及棉点状杂质矿物成分进行了研究, 发现高山石中杂质矿物成分较简单, 暗色砂钉为黄铁矿, 透明砂钉为石英; 而昌化石中的杂质矿物成分较复杂, 含有赤铁矿、 金红石、 锐钛矿、 石英和重晶石。 对比两者中地开石的LA-ICP-MS数据发现, 高山石中Ge元素含量较高, 而昌化石中V和Zn元素含量较高。 根据Ge/Zn元素含量比值, 高山石基本大于02, 昌化石基本小于02; 而根据Ge/V元素含量比值, 昌化石大部分小于01, 而高山石分布在0~10之间。 两个产地Ge/V—Ge/Zn散点分布不同, 区分度可达90%以上。 白色-浅灰色的高山石和昌化石的颜色、 密度和折射率等物理性质均相近, 仅通过外观特征和物理性质较难准确将两个产地的白色-浅灰色印章石区分开。 但是两者的杂质矿物种类和含量不同, 杂质矿物成分的和分析可以作为两者产地的鉴别依据之一。 另外, 两者的痕量元素化学成分不同, 根据它们的Ge/V—Ge/Zn散点图可以有效进行产地鉴别。
Abstract
China has a long history enjoying in the Seal Stones. Both Shoushan Stone and Changhua Stone are famous Seal Stones in China. But their prices are different. Gaoshan Stone is a main variety of Shoushan Stones, which has high market share. In order to preliminarily study the origin identification of Seal Stone, this paper chooses white-light gray Gaoshan Stone and Changhua Stone as study objects that can avoid disturbance of color minerals and color elements to the identification of origin. Infrared spectrum (FTIR), Raman spectrum (LRM) and laser ablation-plasma mass spectrum (LA-ICP-MS) were used to study mineral compositions and trace chemical compositions of white-light gray Gaoshan Stone and Changhua Stone. Combined with physical properties of them, differences and identification methods have been discussed in the two origins. The color of white-light gray Gaoshan Stone is more uniform than that of Changhua Stone. The transparency of Gaoshan Stone is better. They have similar density and refractive index. According to the absorbance peaks of IR in the fingerprint area, the main mineral compositions of white-light gray Gaoshan Stone and Changhua Stone are kaolin-group minerals. Because the different occupied site of hydroxyl in kaolin-group minerals, the forms and amounts of absorbance peaks of stretching vibration of hydroxyl are different. According to the results of the forms and amounts of absorbance peaks of functional area in IR spectrum, the main mineral composition of Gaoshan Stone is ordered dickite, but Changhua Stone has disordered dickite. However, both of them can contain a minor amount of kaolinite. Raman spectrum was used to study impurity minerals on the site of pricker- and soft-spot areas. It is found that Gaoshan Stone has simple impurity minerals. The dark pricker-spot is pyrite, and the soft-spot is quartz. However, Changhua stone has relative complex impurity minerals, such as hematite, rutile, anatase, quartz and barite. Comparing the LA-ICP-MS data of dickite, we found that Gaoshan Stone contains relative high Ge element, while Changhua Stone contains relative higher V and Zn. According to the value of Ge/Zn, which is larger than 02 for Gaoshan Stone, but is smaller than 02 for Changhua Stone. And according to the value of Ge/V, which is smaller than 01 for most of Changhua stone, but which is between 0~10 for Gaoshan Stone. The distributions of splashes of Ge/V-Ge/Zn values of the two origins are different. The distinction degree can be larger than 90%. Color, density and refractive index are similar for white-light gray Gaoshan Stone and Changhua Stone. It is difficult to distinguish them only by the appearance characters and physical properties. However, their varieties and contents are different. The test and analysis can be used to identify their origins. On the other hand, they are different in the amount of trace elements, which also can be used to identify the origin by Ge/V-Ge/Zn scatter diagram.

陈涛, 陈梦瑶, 邓雨晴. 白色-浅灰色高山石与昌化石产地鉴别谱学初探[J]. 光谱学与光谱分析, 2019, 39(9): 2746. CHEN Tao, CHEN Meng-yao, DENG Yu-qing. Preliminary Study on Origin Identification of White-Light Gray Gaoshan Stone and Changhua Stone[J]. Spectroscopy and Spectral Analysis, 2019, 39(9): 2746.

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