陕西紫绿玛瑙的环带致色机理研究

Colouration Mechanism of Circular Bands of Purple-Green Agate from Shaanxi Province

  • 摘要: 2015年,陕西省洛南县境内新发现一种特色石英质玉——紫绿玛瑙,以红色、绿色、紫色最为典型,现有文献1-3主要针对“红心绿边”型紫绿玛瑙开展过宝玉石学特征和颜色成因分析,而关于具有橙红-白-绿等多色环带的紫绿玛瑙的宝石学特征以及形成条件的资料较少。本研究选择陕西省洛南县境内麻花沟、十八盘、学沟、朱家洼等矿区产出具有代表性的紫绿玛瑙样品共16块,对其进行常规宝石学观察、偏光显微镜观察以及拉曼光谱、红外光谱、紫外光谱和扫描电子显微镜等测试,对其宝石学特征、矿物组成及其环带致色成因进行了分析。本文紫绿玛瑙样品(图 1)的主要矿物组成为石英,粒度大多约为0.01 mm,含量在90%以上,同时含有少量的粘土矿物、暗色金属矿物以及碳酸盐矿物等。其中,红色杂质矿物呈细小点状或浸染状分布,粒度微细(1~20 μm);绿色杂质矿物呈片状、纤维状分布。红外透射光谱(溴化钾压片法)结果显示,样品显微结构的空隙中还存在不同程度的分子水。红色、紫色、无色样品在3 628 cm-1处基本无结构水特征峰,绿色样品在3 628 cm-1处呈现显著吸收峰,推测其含水矿物所含结构水导致此处吸收。拉曼光谱测试发现极少部分α-石英光谱在508 cm-1处可观察到较弱的斜硅石信号,这与现有文献中紫绿玛瑙中不存在斜硅石的结论不同。在具有橙红-白-绿典型环带结构样品中,橙色中心主要杂质矿物为赤铁矿,还存在大量表面附着赤铁矿的白云石,呈橘红色外观,这一定程度上也造成环带中心区域呈现橙色;中心到边缘过渡的无色环带内存在大量粒度0.01~0.02 mm的锐钛矿;外层绿色部分主要杂质矿物为绿泥石、绢云母,部分样品中还观察到少量钠角闪石;样品QZ-1黄色部分主要成分为白云石。红色、紫红色样品的紫外-可见光谱出现了赤铁矿的特征峰4以及铁离子在740 nm附近的宽范围波谷5。根据一阶导谱峰显示赤铁矿含量越多则峰位越往高波长向偏移,从574 nm偏移向584 nm(图 2)。样品QZ-1黄色部分紫外-可见光谱一阶导数谱在530 nm处出现强度较大的主峰,伴有432 nm处次级峰,二阶导数处理谱图可见位于447 nm的针铁矿特征谷,且强度较高。综合以上结果可确认,紫绿玛瑙的主要成分为石英,红色、绿色、黄色部分为杂质矿物致色,红色主要致色矿物是赤铁矿,且红色的深浅程度与赤铁矿在样品中含量呈正相关;绿泥石、绢云母是绿色的主要致色矿物,黄色部分为针铁矿致色。结合致色矿物的赋存状态,推测紫绿玛瑙的形成环境复杂,绿泥石属于变质成因,低温条件(230~260℃)绿泥石/伊利石比值较低,高温条件(330~350℃)绿泥石/伊利石比值增加,根据该比值可以判断绿泥石形成的温度范围6。锐钛矿的存在指示红色与绿色过渡环带结晶温度范围可能在470~450℃7。橙红中心区域为岩浆热液同期携带的铁质物质,后期缓慢冷却沉积随硅质石英结晶以杂质包裹体的形式留在了燧石中,显微结构表现为环绕石英颗粒的间隙分布着大量红色铁质化合物,并以铁氧化物或氢氧化物的形式包裹碳酸盐胶结物8

     

    Abstract: In 2015, the characteristic quartz jade-purple-green agate, was discovered in the territory of Luonan county, Shaanxi Province, whose typical colour is red, green, and purple.The existing literature mainly focused on the gemmological characteristics and colour genesis of the "red core and green belt" type of purple-green agates1-3. However, there are still fewer studies on the gemmological characteristics and formation conditions of the purple-green agate with a multicoloured band of orange-white-green. There are still fewer studies on the gemmological characteristics and formation conditions of purple-green agate.In this study, a total of 16 representative samples from the mining areas of Mahuagou, Shibapan, Xuegou, and Zhujiawa in Luonan county, Shaanxi Province, were selected. The gemmological characteristics, mineral compositions, coloration genesis of the ring-banding of the purple-green agate samples were studied using conventional gemmological tests, polarizing microscope, Raman spectrometer, infrared spectrometer, ultraviolet spectrometer, and scanning electron microscope.The main mineral composition of purple-green agate (Fig. 1) is quartz with the particle size about 0.01 mm, and the quartz content is more than 90 %, as well as a small amount of clay minerals, dark metallic minerals and carbonate minerals. Among them, the red impurity minerals are distributed in the form of fine dots or dipping, with fine particle size (1-20 μm); and the green impurity minerals are distributed in the form of flakes and fibres. The results of infrared transmission spectroscopy (potassium bromide tabletting method) showed that there are different degrees of molecular water in the void of the agate samples' microstructure. The red, purple, and colourless agate samples have basically no characteristic peak of structural water at 3 628 cm-1; the green samples show a significant absorption peak at 3 628 cm-1, and it is speculated that the structural water contained in the water-bearing minerals causes absorption here. Raman spectroscopy tests revealed a very small fraction of α-quartz spectra with a weak plagioclase signal observed at 508 cm-1, which is different from the existing literature that concludes that plagioclase is not present in purple-green agates. In the samples with the typical orange-red-white-green ring-banding structure, the main impurity mineral in the orange central area is hematite, and there are also a large amount of dolomite with hematite attached to the surface, showing the orange-red appearance, which contribute to the orange colouration of the central area of the ring-banding; there are a large amount of anatase with a grain size of 0.01-0.02 mm in the colourless ring-banding from the centre area to the edge area.The main impurity minerals in the green edge area are chlorite, sericite, and a small amount of sodium-hornblende is also observed in some samples; the yellow area of sample QZ-1 is mainly composed of dolomite. The UV-Vis spectra of the red and purplish red samples show characteristic peaks of hematite4 and a wide range of troughs of iron ions around 740 nm5. According to the first-order derivative spectrum peaks show that the more the hematite content is, the more the peak position is shifted to higher wavelengths, from 574 nm to 584 nm (Fig. 2). The first-order derivative spectrum of the yellow area of the UV-Vis spectrum of sample QZ-1 shows the main peak at 530 nm with a larger intensity, accompanied by a secondary peak at 432 nm.The second-order derivative processed spectrum shows the characteristic valley 447 nm of goethite, with a high intensity.Based on the above results, it can be confirmed that the main component of purple-green agate is quartz, and the red, green and yellow area are coloured by impurity minerals.The main red colouring mineral is hematite, and the depth of red is positively correlated with the content of hematite; the chlorite and sericite are the main green colouring minerals, and the yellow area is coloured by goethite. Combined with the occurrence state of the chromogenic minerals, it is speculated that the formation environment of purple-green agate is complex, and chlorite belongs to the metamorphic genesis.The chlorite/illite ratio is low at low temperature (230-260 ℃), and the ratio increases at high temperature (330-350 ℃) According to this chlorite/illite ratio, the temperature range of chlorite formation can be judged6. The presence of anatase indicates that the crystallization temperature range of red and green transition ring zone may be 470-450 ℃7. The orange-red central area is the iron material carried by the magmatic hydrothermal fluids during the same period, and the later slow cooling deposition stayed in the flint in the form of impurity inclusions along with the siliceous quartz crystals.The microstructure exhibits that a large number of red iron compounds are distributed in the interstices surrounding the quartz grains and wrapped around the carbonate collodion in the form of iron oxides or hydroxides8.

     

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