大溪地黑珍珠的颜色成因研究

Colour Origin of Tahiti Black Pearl

  • 摘要: 珍珠是贝类生物分泌的有机-无机混合物。大溪地黑珍珠以独特的黑色而闻名,养殖过程复杂且周期长。本研究采用红外光谱、紫外-可见吸收光谱、激光拉曼光谱、X荧光光谱、X射线粉末衍射及扫描电子显微镜对大溪地黑珍珠样品的宝石学性质、化学成分和谱学特征进行了测试,旨在分析其颜色成因,为珍珠养殖和鉴定提供新的依据。研究结果显示,大溪地黑珍珠样品的形态各异,颜色从深黑色到灰色不等,直径一般在9.4~11.0 mm,相对密度在2.667~2.749。部分黑珍珠样品带有伴色,长波紫外光下可见暗红色或黄绿色荧光。宝石显微镜下可见螺纹和圆形凹坑等主要瑕疵,以及特征的指纹状纹理。红外光谱分析显示,所有黑珍珠样品在707、879、1 483 cm-1均有一致的吸收峰,分别为文石O-C-O的面内弯曲振动、O-C-O面外弯曲振动以及CO32-离子的反对称伸缩振动所致(图 1)。紫外-可见光谱结果表明,大溪地黑珍珠样品在280、404、493 nm和699 nm处具有特征吸收峰,其中280 nm和699 nm处的吸收峰较为显著(图 2),吸收强度与黑色呈负相关。激光拉曼光谱进一步验证大溪地黑珍珠样品的主要矿物为文石,特征峰1 083 cm-1和703 cm-1各自对应碳酸根离子对称伸缩振动和C-O-C面内弯曲振动引起。有机色素卟啉使黑色变深。能量色散X射线荧光光谱分析显示,大溪地黑珍珠样品富含多种元素,但元素的含量与珍珠的颜色深浅无明显相关。Sr/Ca比值证实大溪地黑珍珠为海水珍珠。基于X射线粉末衍射分析,样品的矿物组成主要由文石和少量方解石组成。扫描电子显微镜观察,黑珍珠样品的横截面显示白色或淡黄褐色的珠核和黑色的珍珠层,且珠核和珍珠质层间的界线非常清晰。珍珠层的颜色均匀,层厚约1 mm, 结构类似砖墙, 平整有序。大溪地黑珍珠表面的梯田式纹理非常明显,文石板片排列紧密,层状规则,大小相似。本研究结论:(1)大溪地黑珍珠颗粒较大,具有典型的珍珠光泽和指纹状纹理;(2)珍珠层的砖墙式结构和珠核的表面特性极其重要地影响珍珠光泽;(3)大溪地黑珍珠的主要矿物为文石,颜色成因与方解石含量和珍珠层的砖墙式结构有关;(4)大溪地黑珍珠的黑色与特定波长的紫外-可见光吸收峰强度负相关,与有机卟啉色素正相关。

     

    Abstract: Pearls are an organic-inorganic mixture secreted by shellfish. Black pearls from Tahiti, whose breeding process is complex and long are known for their unique dark black tone. In this study, the gemmological characteristics, chemical compositions and spectral characteristics of the black pearl samples from Tahiti were studied using infrared spectroscopy, ultraviolet-visible spectroscopy, laser Raman spectroscopy, XRF, XRD, and SEM, in order to clarify their colour causing and provide the pearl cultivation and identification. The research shows that the black pearl samples from Tahiti vary in shape, with body colour ranging from dark black to gray, with the diameter between 9.4 mm and 11.0 mm, and relative density between 2.667 and 2.749. Some black pearl samples from Tahiti are overtone, show darken red or yellow-green fluorescence under long wavelength UV light. Observed under the gem microscope, it is found that defects mainly are threads and circular pits, as well as the fingerprint-like texture. Infrared spectrum result shows that all samples had consistent absorption peaks at 707, 879, 1 483 cm-1, which are in-plane bending vibration of aragonite O-C-O, the out-of-plane bending vibration of O-C-O, and antisymmetric stretching vibration of CO32- ions, respectively (Fig. 1). The UV-Vis spectra of the black pearl samples have characteristic peaks at 280, 404, 493, 699 nm, among which 280, 699 nm are stronger in the peak intenty(Fig. 2) and negatively correlated with black tone. Laser Raman sepectrum result further verifies that the main mineral of black pearl sample is aragonite, with the characteristic peaks at 1 083, 703 cm-1, respectively, corresponding to the symmetric stretching vibration of the carbonate ion and in-plane bending vibration of C-O-C. Organic pigment porphyrins make black pearl samples from Tahiti darker. XRF result shows that the black pearls are rich in various elements, but the contents of elements are not significantly related to pearl's colour. The ratio of Sr/Ca confirms that black pearl samples are seawater cultural pearls. Based on XRD analysis, black pearl is mainly composed of aragonite and a small amount of calcite. The cross section of black pearl reveals white or pale yellowish brown nucleus and black nacreous layer, and boundary between the nucleus and the layer is very clear through scanning electron microscopy. The nacreous layers are uniform colour, approximately 1 mm thick, similar to brick-wall structure, smooth and orderly packed. The terraced texture is very obvious on the surface of the pearl, and the aragonite tablets are closely arranged, regular and almost equal in size. The study led to the following conclusions: (1)black pearl samples from Tahiti are larger in diameter, with typical pearl luster and fingerprint-like texture; (2)the brick-wall structure of nacreous layer and the surface characteristics of nucleus are extremly important to affect the luster of the pearl; (3)the main mineral of black pearl sample from Tahiti is aragonite, and its colour causing is related to the content of calcite and the structure of the nacreous layer; (4)the body colour of black pearl sample from Tahiti is negatively correlated with the intensity of UV-Vis light peaks at specific wavelengths and positively correlated with organic porphyrin pigments.

     

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