| 题名 | 不同产地软玉玉石的主成分、微量元素、矿相结构和产地特征研究 |
| 作者 | 张朱武 |
| 学位类别 | 博士 |
| 答辩日期 | 2011 |
| 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 | 无损分析，软玉，PIXE，产地，包裹体 |
| 其他题名 | The major compositions, trace elements, mineralogical structure and origin characters of nephrite minerals obtained from different deposits |
| 中文摘要 | 中国最早的软玉型玉器出土于辽宁省的查海遗址，距今8000多年。从新石器时代开始，越来越多的软玉型玉器从墓葬和遗址中出土，如辽宁的红山文化（4000-3000 B.C.）和浙江的良渚文化（位于太湖地区，包括浙江北部、上海和江苏南部，3300-2300 B.C.)。但是，这些大量的古代玉器的玉料来源问题一直没有解决，因为大多数古代玉器没有进行无损的成分分析，特别是微量元素分析，而且也没有对不同产地软玉玉石进行系统的分析。 本研究通过外束质子激发X荧光分析技术（PIXE）对国内外不同产地的51个软玉玉石进行了成分析，发现由于成矿机理和地质环境的差异，由花岗闪长岩侵入体和白云石大理岩在应力条件下交代作用生成的D型软玉主要矿物成分大部分偏向于透闪石，Fe元素的含量一般较低，但少数样品受地质环境影响Fe含量会增加；由镁橄榄石与中-低温热液交代作用形成的蛇纹石，此蛇纹石再与围岩(大理石或白云石)接触交代蚀变形成的S型软玉主要矿物成分更偏向于阳起石，Fe元素的含量普遍较高，因此不能仅仅依据Fe元素含量的高低判定软玉的成矿类型。但S型软玉微量元素中Cr、Co、Ni的含量明显高于D型软玉，通过对微量元素进行因子分析可以很好的区分两种类型的软玉。同时，由于软玉矿床的围岩条件不同，会使某些微量元素的含量偏高，可以作为其产地特征的重要参考，如小梅岭软玉较高的Sr含量（306-498 μg/g）和汶川软玉的高Mn/Fe比值（3.298-3.512）。外束PIXE作为一种无损分析方法可以运用于古代玉器的分析，良渚文化的软玉型玉器PIXE测试表明大部分为D型软玉，且Sr含量为<1-30 μg/g，明显少于小梅岭软玉，因此以前的观点（良渚文化软玉玉器的玉料来源于小梅岭）应该值得再商榷。所以软玉玉石微量元素含量上的差异可以帮助判断古代玉器玉料的成矿类型，为其玉料的溯源问题提供科学的参考依据。 利用等离子体激发光谱分析仪(ICP-AES)和中子活化仪器分析(INAA)对其中的部分软玉样品进行了微量元素分析，并与外束PIXE的分析结果进行比对，发现3种方法测试的软玉玉石微量元素含量在总体分布趋势上是一致的，由于不同分析方法的系统误差等方面存在差异对于含量较低的元素测量结果存在较大偏差。而且通过对ICP-AES和INAA的微量元素数据进行因子分析，显示都可以较好的区分两种类型软玉，且ICP-AES测试显示小梅岭软玉有较高的Sr含量，与PIXE分析结果一致。同时INAA对软玉玉石的稀土元素也进行了初步的分析。 通过扫描电镜能谱仪（SEM-EDS）和激光拉曼光谱仪（LRS）分析台湾（HL-1）、玛纳斯（MNS-1、MNS-2）和新西兰（XXL-2）的S型软玉中铬铁矿包裹体。SEM-EDS测试显示台湾软玉除了Zn明显高于其它2个产地，MgO和Al2O3的含量明显低于其它2个产地的软玉。而且台湾软玉的铬铁矿标准化学式显示Fe3+含量也明显偏高。台湾软玉的铬铁矿包裹体中Mg/(Mg+Fe2+)比值较低，说明其铬铁矿晶粒在软玉成矿过程中的形成时间较晚。LRS分析显示，与玛纳斯和新西兰的软玉相比，受离子替代影响台湾软玉中铬铁矿包裹体的A1g、Eg和F2g(1)模式振动峰向低波数方向偏移20 cm-1左右。实验还对新疆且末的2个D型软玉中石墨包裹进行了详细的成分和拉曼谱线特征分析。与SEM-EDS相比，LRS可以更方便的运用于分析古玉中的包裹体，并与软玉玉石分析结果进行比对，可以为古玉的玉料溯源提供有效的无损分析方法。 运用X射线衍射分析（XRD）对软玉玉石进行了矿相分析，并对块体样品XRD测试中由于样品的测试表面与仪器的测试平面存在高度差造成的谱线整体偏移进行了定量分析，对不同颗粒度的软玉粉末样品进行测试，分析XRD谱线择优取向问题。同时利用扫描电镜（SEM）对不同产地的软玉微观形貌进行分析，发现不同产地软玉在纤维化程度、纤维的几何尺寸以及组合形态等方面存在有不同程度的差别。 |
| 英文摘要 | According to the nephrite artifacts excavated from Chahai ruins (in Liaoning province, China), nephrite, as a symbolic materials used for ancient ornaments and ritual objects, can be traced back to 8000 years ago in China. Commencing in the late Neolithic period, more and more ancient nephrite artifacts were excavated from tombs and ruins such as Hongshan culture (in Liaoning province, China, 4000 to 3000 B.C.) and Liangzhu culture (in Lake Tai region, including northern Zhejiang province, western Shanghai and southern Jiangsu province, China, 3300 to 2300 B.C.). However, the provenience of raw materials of those abundant ancient nephrite artifacts has never been solved, because chemical compositions, especially trace elements, of most nephrite artifacts have not been studied by non-destructive methods. Moreover, systematic analyses of nephrite minerals from different deposits also have never been carried out. External-beam proton-induced X-ray emission (PIXE) has been used to non-destructively analyse chemical compositions of 51 nephrite minerals. Depending on different mineralization mechanism and geological environment, the major compositions of D-type nephrite minerals, formed by contact metasomatism between intermediate-acidic intrusive rocks (e.g. granodiorite) and dolomitic marble, are tremolite and have lower content of Fe, but the Fe content of few samples may increase because of influenced by geological environment; the major compositions of S-type nephrite minerals, formed by contact metasomatism between serpentine (which is formed by metasomatism between olivine and low-medium temperature hydrotherm) and wall rock, are close to actinolite and have higher content of Fe. Therefore, it is not correct to judge the types of nephrite minerals just according to the content of Fe. However, contents of Cr, Co and Ni of S-type nephrite minerals are obviously higher than that of D-type, and the two types of nephrite minerals can be more accurately distinguished through factor analysis of trace elements. According to the content of Sr (306-498 μg/g) and Mn/Fe value (3.298-3.512) nephrite minerals from Xiaomeiling and Wenchuan deposit can be distinguished with others also from D-type, respectively. External-beam PIXE also can be used to non-destructively analyse ancient nephrite artifacts. Moreover, depending on the Sr content (<1-30 μg/g) detected by PIXE, clear evidence was given to prove that the raw materials of ancient nephrite artifacts from Liangzhu culture ruins are not from Xiaomeiling nephrite deposit. Therefore, the difference of trace elements of nephrite minerals can provide scientific basis for seeking the provenance of raw materials of ancient nephrite artifacts. In this work based on some nephrite minerals, it shows that the distribution of trace elements of nephrite samples in inductively coupled plasma-atomic emission spectroscopy (ICP-AES), instrumental neutron activation analysis (INAA) and PIXE data are generally consistent, although large differences exist in some elements. According to the trace elements detected by INAA and ICP-AES, the two types of nephrite minerals also can be distinguished using factor analysis, respectively. Moreover, depending on the ICP-AES data, Sr can be regarded as fingerprint element of Xiaomeiling nephrite minerals, which is consistent with the result by PIXE. The contents of rare earth elements of nephrite minerals also were analysis by INAA. Scanning electron microscopy with energy dispersive spectrometer (SEM-EDS) and laser Raman spectroscopy (LRS) were used to analyse the chromite inclusions found in four samples of the mineral nephrite that were obtained from Taiwan (HL-1), Manasi in China (MNS-1, MNS-2) and New Zealand (XXL-2). The chromite inclusions found in sample HL-1 (Taiwan) contain low contents of MgO and Al2O3, as well as a characteristically high Zn content. According to the chemical formulas, Fe3+ content of chromite inclusions found in Taiwan nephrite are obviously high. In general, where the chromite has a high ratio of Mg/(Mg + Fe2+), it implies that the chromite inclusions formed early on the sequence of crystallisation. This finding suggests that the chromite inclusions in HL-1 formed later than MNS-1, MNS-2 and XXL-2 during the mineralisation of the nephrite. The most significant finding, however, was that HL-1 could also be distinguished from the other samples by the lower wavenumbers (about 20 cm-1) of the positions of the peaks that belong to the A1g, F2g(1) and Eg modes. Moreover, graphite inclusions found in two samples from Qiemo were also analysed using SEM-EDS and LRS. Compared with SEM-EDS, LRS, as a effectively non-destructive method, can more easily be used to analyse inclusions found in ancient nephrite artifacts to compare with nephrite minerals. X-ray diffraction (XRD) was used to analysis mineral structure of nephrite samples. The quantitative analysis of shift degree of XRD spectrum induced by the difference in height between surface of sample and testing plane of instrument was carried out. Nephrite mineral was pulverized to powder with different particle sizes to analysis preferred orientation of XRD spectrum. According to microstructure analysis of nephrite minerals, it is shows that degree of fibrosis, size of fibers and style of fiber combination found in samples exist difference in varying degree. |
| 语种 | 中文 |
| 内容类型 | 学位论文 |
| 源URL | [http://ir.siom.ac.cn/handle/181231/15662]  |
| 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 | 张朱武. 不同产地软玉玉石的主成分、微量元素、矿相结构和产地特征研究[D]. 中国科学院上海光学精密机械研究所. 2011. |
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