| 题名 | 不同产地蛇纹石玉的成分、物相和结构特征 |
| 作者 | 王永亚 |
| 学位类别 | 博士 |
| 答辩日期 | 2013 |
| 授予单位 | 中国科学院上海光学精密机械研究所 |
| 导师 | 干福熹 |
| 关键词 | 蛇纹石玉，无损分析，成矿机理，致色机理 |
| 其他题名 | Characteristics of chemical composition and mineral structure of serpentine jade obtained from different deposits |
| 中文摘要 | 中国玉文化作为中华民族文化的重要标志之一，已有八千年的历史。蛇纹石玉作为中国的四大名玉之一，在中国的古代玉文化，乃至整个古代文化中占有举足轻重的地位。早在距今七千年的新石器时代遗址中已经发现蛇纹石玉器，因此蛇纹石玉的研究对于我国古代玉文化的研究有重要意义。 本论文首先系统的对国内外不同产地的蛇纹石玉石样品进行了化学成分分析，包括主量、次量和微量元素。根据化学成分分析结果对蛇纹石玉和古代蛇纹石玉器的产地及成矿类型进行了分析讨论。其次结合X射线衍射技术(XRD)和样品的化学成分分析了不同产地蛇纹石玉的岩石矿物学特征，探讨了其成矿机理。然后利用漫反射光谱对岫岩玉样品的色度坐标进行计算标定，并结合顺磁共振技术(EPR)和吸收光谱技术(OAS)对岫岩玉样品中的致色机理做了分析。最后，采用共焦拉曼光谱分析技术(LRS)和扫描电镜能谱分析(SEM-EDS)研究了黑绿玉中包裹体的物相及成分，进而探讨其成矿机理。 本论文的主要内容包括以下四个方面： （一）化学成分分析 利用外束质子激发X射线荧光分析技术(PIXE)、便携式X射线荧光分析技术(pXRF)和电感耦合等离子体原子发射光谱分析技术(ICP-AES)对国内外不同产地的37件蛇纹石玉石样品进行了化学成分分析，结果表明蛇纹石玉石样品的主成分基本是一致的，但是由于成矿机理和地质环境的差异，微量元素的含量存在一定的差异，因此微量元素可以作为蛇纹石产地溯源的一个因素。由超基性岩变质作用形成的第二种类型的蛇纹石中Cr, Co, Ni的含量远远超出由白云质大理岩在热液交代作用下形成的第一种类型的蛇纹石中的Cr, Co, Ni的含量，这表明微量元素含量的差异可以作为区分两种成矿类型蛇纹石的标志。通过对不同出土地点的古代蛇纹石质玉器的微量元素的系统分析以及和不同产地蛇纹石玉微量元素的对比认为可以利用微量元素的差异初步判断主要成分为蛇纹石的古代玉器玉料的成矿类型，为其玉料的来源判定提供科学参考。 （二）不同产地蛇纹石玉的岩石矿物学特征 通过对蓝田玉的无损分析，根据其成矿过程将现代蓝田玉分为两类：一类方解石与蛇纹石共存；一类只含蛇纹石，其中又将只含蛇纹石的玉石分为蓝田叶蛇纹石玉和蓝田利蛇纹石玉，本文首次发现了现代蓝田玉中的蓝田利蛇纹石玉。首次对广西陆川蛇纹石玉的岩石矿物学特征进行了系统研究，此外通过激光拉曼光谱鉴定了陆川蛇纹石中两种不同结构的蛇纹石亚种——纤蛇纹石和叶蛇纹石。由于本研究采用的研究方法是无损分析技术，因此这些结论可以为古代玉器的无损分析提供科学依据。 （三）岫岩玉色度学标定及致色机理研究 通过漫反射光谱对岫岩玉样品的色度坐标进行计算，结果表明人眼的感觉颜色类似的样品，其色度坐标和在色空间的位置都有很明显的差异，因此岫岩玉样品颜色的差异可以通过色度坐标定量的区分，这有重要的科学价值和经济价值。通过对比发现铁元素是岫玉的主要致色元素，锰元素对岫玉的绿色有一定影响。电子顺磁共振和吸收光谱的结果表明Fe2+对岫玉的绿色色调起主要作用，而Fe2+和Fe3+的共同作用决定了岫玉的黄色色调，二者的相对强度决定了岫玉的黄绿色，这和前人的认识有一定的差异。 （四）黑绿玉包裹体的物相及成分研究 采用拉曼光谱快速鉴定了黑绿玉的包裹体的物相，主要为透闪石、绿泥石、石英、磁铁矿和针铁矿，并通过SEM-EDS微区成分分析验证了拉曼光谱的结果。拉曼光谱仪的光学显微镜照片显示可以通过包裹体在蛇纹石玉中的面积分布来对玉石的质量做出初步评价。黑绿玉伴生矿物的分析结果表明黑绿玉是超基性岩在中酸性环境下通过变质作用形成的。这些应用拓展了拉曼光谱仪的应用范围，为以后古代玉器包裹体的无损分析的进一步研究奠定了基础。 |
| 英文摘要 | Jade culture is an important symbol of Chinese culture, and has a history of almost eight thousand years. As one of the four most famous jade in China, serpentine jade occupies an important position in the Chinese ancient jade culture, even in the entire ancient culture. Serpentine jade artifacts have been found in the Neolithic site which was as early as seven thousand years, thus, the study of serpentine jade is of great meaning to the research of Chinese ancient jade culture. Firstly, the chemical compositions of serpentine jade samples from different deposits, including the major, secondary and trace elements were systemically analyzed. The sources and metallogenic types of the serpentine jade samples and archaic serpentine jade artifacts were discussed based on the results. Secondly, mineralogy characteristics of serpentine jade samples were analyzed by X-ray diffraction (XRD) and chemical composition analysis, and the metallogenic mechanisms of them were discussed. Thirdly, chromaticity coordinates of Xiuyan jade were calculated according to the diffuse reflectance spectra, and the coloration mechanism was explored based on the results of paramagnetic resonance spectroscopy (EPR) and absorption spectroscopy (OAS). Finally, confocal Raman spectroscopy (LRS) and scanning electron microscope energy spectrum analysis (SEM-EDS) were used to determine the phase and chemical composition of the inclusions of Black-green serpentine jade, then the metallogenic mechanisms was inferred. The main content of this paper includes the following four aspects: (a) Chemical composition analysis Based on the results of major and trace elements of 37 serpentine jade samples from different deposits determined by PIXE, XRF and ICP-AES, the major chemical composition of serpentine jade is basically the same. However, as the effect of metallogenic mechanism and geological environment, the trace element contents are different, and the trace element contents can be an indicator for the source of serpentine jade. Type I formed by contact metasomatism between dolomitic marble and intermediate acidic intrusive nearly has no Cr, Co and little Ni, however there is much Cr, Co and Ni in Type II which is formed by metasomatism of ultramafic rocks and low-medium temperature hydrotherm. Thus this could be used to distinguish the two kinds of serpentine jade formed by different mechanisms. By the comparison of trace element of archaic serpentine jade artifacts and that of serpentine jade from different deposits, it was found that trace element can be used to infer the original source of raw material of archaic serpentine jade artifacts, which can provide some references to the archaeology. (b) Petrological and mineralogical characteristics of serpentine jade Jade samples from Lantian can be classified into two types according to their mineralogy. The predominant mineral of the first type is serpentine, whereas, the second type contains both calcite and serpentine. The first type can be further subdivided into Lantian antigorite jade and Lantian lizardite jade, and Lantian lizardite jade was found for the first time in Lantian jade. As to Luchuan serpentine jade, the major mineral is antigorite and chrysotile. And laser Raman spectroscopy was used to identify chrysotile and antigorite of the serpentine minerals in Luchuan jade. As nondestructive analysis methods were carried out in the research, these inclusions can provide useful data to the nondestructive analysis of archaic serpentine jade artifacts. (c) Chromaticity and coloration mechanism of Xiuyan jade Chromaticity coordinates of Xiuyan jade were calculated according to the result of diffuse reflectance spectra. The results indicate the difference of colors for Xiuyan jade can be quantitatively distinguished by standard chromaticity coordinate, which can pay a scientific reference to the evaluation of the value of Xiuyan jade. The transition metal element analysis demonstrates Fe is the main color-causing element of Xiuyan Jade. The Fe2+ ions determine the green color while the absorption of Fe3+ and Fe2+ ions together introduce the yellow color of Xiuyan Jade. (d) The phase and composition of the inclusions of Black-green jade The Raman results indicated that the inclusions of black-green serpentine jade were actinolite, chlorite, calcite, quartz, magnetite and goethite. SEM-EDS results verify the coexistence of the five kinds of minerals found in the Raman spectra. The jade quality was preliminarily evaluated based on the area ratio of antigorite to the inclusions by optical microscopy. Moreover, black-green serpentine jade formation was inferred to occur by the metasomatism of ultramafic rocks, which was a new application of Raman spectrum in mineralogy, and laid the foundation for further studies on the nondestructive analysis of the inclusions of ancient jade artifacts. |
| 语种 | 中文 |
| 内容类型 | 学位论文 |
| 源URL | [http://ir.siom.ac.cn/handle/181231/15724]  |
| 专题 | 上海光学精密机械研究所_学位论文 |
| 推荐引用方式 GB/T 7714 | 王永亚. 不同产地蛇纹石玉的成分、物相和结构特征[D]. 中国科学院上海光学精密机械研究所. 2013. |
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