珍珠的成分特点研究

运用ICP-MS、IC、XRD、IR等分析方法,对我国不同成因、不同产地的珍珠及其贝壳的成分进行了系统的研究,结果表明:淡水养殖珍珠中的P、Mn、Ba的含量相对较高,而海水珍珠中的Sr、Zn、Cr、Ni的含量相对较高;与淡水养殖珍珠相比,海水养殖珍珠中的阴、阳离子种类多,含量高,氨基酸总含量高而稳定;海水养殖珍珠及其贝壳或淡水养殖珍珠及其贝壳在成分上的变化基本一致,而海水养殖珍珠的珍珠层与珍珠核之间差异较大。该结论对于珍珠的鉴定及其理论药理研究具有重要的意义。     

珍珠层有机质及其矿化响应研究

珍珠层中的有机质极其重要,它不仅是生物矿物与纯无机矿物的根本区别,而且具有重要的生物矿化响应效应.但珍珠层中有机质含量极低,约为珍珠层体积的5％,致使研究手段受到了很大限制.选择广西、广东、浙江、江苏等地的海水养殖珍珠、淡水养殖珍珠、育珠贝贝壳中的珍珠层以及现代珊瑚、珊瑚化石作为研究对象,通过日立835-50型高速氨基酸分析仪获得了各样品氨基酸的种类和含量,继而进行相关性分析和聚类分析,得到一些具有特点的氨基酸组合或类,结合对珍珠层进行的TEM、SEM等电镜观察结果,发现这些组合和类很可能分别对应于珍珠层中不同空间位置、不同结构、不同种类和不同形态大小的有机大分子.由此认为有机质的矿化响应十分复杂、多样,并可以通过诱导和控制作用形成多样化、相互演化、复杂的无机矿物及珍珠层独特的微结构.这一结论对于阐释珍珠层有机质复杂多样的矿化响应具有重要意义.     

珍珠层中文石晶体择优取向的XRD极图分析

本文采用XRD极图方法对海水大珠母贝、企鹅珍珠贝及淡水三角帆蚌贝壳珍珠层中文石晶体的结晶学定向进行了研究。根据文石的 ( 0 0 2 )和 ( 0 12 )极图可以推断 ,三种贝壳珍珠层文石的a轴平行珍珠层面 ,c轴垂直珍珠层面。在珍珠层面上 ,二种海水壳珍珠层中文石的a轴亦存在强烈的择优取向现象 ,大珠母珍珠层中文石a轴沿与壳生长纹方向呈 2 0 0°左右的夹角分布 ,企鹅珍珠贝沿近平行壳生长纹的方向分布 ;淡水三角帆蚌珍珠层文石a轴亦平行珍珠层面分布 ,但其择优取向不如海水壳明显 ,在珍珠层面上沿各个角度上均有分布。     

淡水养殖珍珠的矿物组成特征

采用粉末X射线衍射分析及显微激光拉曼光谱对三角帆蚌养殖珍珠的矿物组成进行了研究。结果表明，浙江诸暨产三角帆蚌淡水珍珠的矿物组成主要为文石。在无商业价值的部分珍珠中存在六方碳钙石。其中具珍珠光泽的珍珠层一般呈半透明状，均为文石组成；无珍珠光泽的不透明层有时由文石组成，有时由六方碳钙石组成。三角帆蚌淡水养殖珍珠中不存在方解石，这与海水养殖珍珠中存在方解石明显不同。     

贝壳珍珠层的X射线衍射研究

珍珠层中文石晶体的择优取向是珍珠层具有优异力学性能的重要原因之一，通过对三角帆蚌贝壳珠层的X射线衍射研究，表明珍珠层除存在公认的（002）面网平行珍珠层面的强烈定向文石晶体外，还有强烈的（012）面网平行珍珠层面的亲新定向文石晶体，且在同一贝壳的不同位置，该两种取向的择优取向度变化较大，充分说明了珍珠层结构的不均匀性。     

海水及淡水养殖珍珠的物质组成

采用偏光显微镜、X射线粉晶衍射仪、傅利叶红外光谱仪、电子顺磁共振谱仪、拉曼光谱仪、原子吸收光谱仪等测定了淡水珍珠、海水珍珠及部分贝壳的矿物及化学组成.研究表明: 珍珠矿物组成单一, 主要由文石构成, 仅含少量球文石或方解石; 淡水珍珠明显富含Mn, 而海水珍珠中明显富含Na、K、Mg、Sr; 这种富集特征与淡水、海水中元素的富集特征相似.此外, 各颜色品种之间化学成分也存在微小的差异, 白色珍珠比有色珍珠更纯净, 所含铁、锰、铬等致色元素更低.紫色珍珠略富含Mg、Mn, 橙色者明显富含Fe, 而黑色海水珍珠的颜色可能与有机组分有关.      

淡水珍珠中文石球粒的发现与成珠机制探讨

长期以来,珍珠的成因理论很少涉及在超显微镜结构研究基础上的具体的珍珠形成机制。珍珠与贝壳珍珠层具有较多的相似性,但也存在很多不同。本文在对AFM下首次观察到的淡水珍珠表面纳米级的六方最紧密堆积文石球粒的研究基础上,结合XRD分析对珍珠内部矿物成分差异的研究,试图在贝壳珍珠层成因理论的基础上探讨淡水珍珠的成珠机制。本文将珍珠的形成过程初步归纳为碳酸钙凝胶的形成,碳酸钙球粒的形成,矿物相的转变和后继生长四个阶段。     

广西合浦海水珍珠变黄机理新议

海水珍珠缓慢变黄的传统解释是无机相文石不稳定向方解石转化这个不可逆过程造成的.然而作者通过肉眼观察、光学显微镜观察、H2O2漂白体系使变黄的海水珍珠重新变白实验及X射线粉晶衍射分析,均表明传统解释可能存在错误,变黄的海水珍珠无机相没有发生明显的相变,故推测珍珠内有机相的变化是珍珠变黄的主要原因.     

珍珠粉和珍珠层粉的差热分析鉴别

珍珠粉和珍珠层粉都是文石-方解石类矿物,但二者在医药上和化妆品上应用的效果有明显差别。利用显微镜观察,电子扫描、化学分析、X射线衍射和红外光谱分析都不可能区别珍珠粉和珍珠层粉。 作者在本文中建议采用差热分析方法鉴定珍珠粉和珍珠层粉。差热分析方法能够得出样品在加热过程中的不同曲线,特别在500℃以下的放热反应曲线。这些特点尤其是对海水产的珍珠粉和珍珠层粉的鉴别有效。 本文设想,珍珠粉和珍珠层粉差热曲线的差别是由于其中的氨基酸含量不同引起的。作者认为氨基酸含量是不同种类的珍珠粉和珍珠层粉的药效不同的原因之一。     

Sinohyliopsis schlegeli珍珠层中Si、Mn、Fe和Sr离子的微生物固定化和环境因素

在日本Ishikawa Prefecture的Kanazawa大学进行了为期8个月的排水池培养实验,利用特征水和营养元素的基本因素对Sinohyliopsis schlegeli贝壳珍珠质所记录的环境变化进行观察。在2007年5月份到11月份之间,每个月向贝壳珍珠质注入四环素作为指示剂。定期测量水质,诸如pH、氧化还原势、电导率、溶解氧以及水温,通过过滤法除掉水中悬浮固体并进行光学显微镜和荧光X射线分析以及扫描电镜 能量色散X射线观察(SEM EDX)。对贝壳珍珠质的X射线荧光化学分析表明那些富含四环素的层对应高含量的Si、Mn、Fe和Sr离子。氧化还原势和溶解氧分析都证明在珍珠质中存在层。排水池中悬浮物质主要由Si、Mn和Fe元素组成,这与2007年夏季贝壳珍珠层的生物固定化中所涉及的元素一致。SEM EDX分析证明离子来自Siderocapsa sp.和Gallionella ferruginea硅藻的胃部。冬季几乎没有发生离子的生物固定化。结果表明在层化的贝壳珍珠质中存在元素的固定化,Sinohyliopsis schlegeli 在夏季以离子为食来生长珍珠质。具有这些生物氧化物的Sinohyliopsis schlegeli可能对自然界水体中重金属的清除有一定的贡献。     

三角帆蚌贝壳珍珠层中类胡萝卜素的激光拉曼光谱研究

三角帆蚌贝壳珍珠层及养殖珍珠的拉曼光谱中除由文石矿物引起的拉曼峰外，还可观察到明显的由全反式结构的类胡萝卜素引起的1132cm^-1(C-C单键的伸缩振动）和1527cm^-1(C=C双键的伸缩振动）两个拉曼峰，根据类胡萝卜素的拉曼光谱特征推断其分子中的C＝C双键的数目为10。珍珠层中类胡萝卜素的相对浓度与珍珠层的颜色密切相关，在同一贝壳中从壳后端至壳顶，其相对浓度逐渐变小。对贝壳珍珠层中类胡萝卜素的研究可为珍珠漂白及在食品、化妆品等领域的应用提供科学的依据。     

珍珠显微结构及纳米矿物的电镜分析

采用SEM(扫描电子显微镜)和HRTEM(高分辨透射电子显微镜)技术,系统地研究了珍珠层及其微结构.发现珍珠质层是由有机质胶结的文石组成片状晶层,文石大量为六边形、不规则多边形和近圆形,并与有机质层交互平行叠置.在棱柱层的柱状晶体周围也有纤维状、胶状有机质.同时,在棱柱状和片状文石晶体的截面上,含有大量纳米级的圆形、椭圆形等形状的有机质、气液包裹体或孔洞.其中许多部位的有机基质中不同程度地显现出晶格条纹像,均为纳米矿物所致.以上结果均表明珍珠层具有有序、精细、多层次、整体性好等优良的结构特点.这一结论对于探讨珍珠的成因、机械强度及医药保健性能等方面均具有重要的意义.     

A novel multiproxy approach to reconstruct the paleoecology of extinct cephalopods

Reconstructing marine paleoenvironments from the skeletal hardparts of nektic organisms is often hampered by their unknown migrational pathways involving different water masses and their corresponding physico-chemical parameters. Despite significant progress over the last years, the reconstruction of migration patterns of extinct ammonoids is difficult because both, vertical and horizontal ones lead to an intricate combination of reconstructed seawater temperatures. Paleonvironmental data retrieved from exceptionally well-preserved lower Albian (Douvilleiceras mammillatum ammonite zone, uppermost CC8a nannofossil zone, 110.5–111.0 Ma) cephalopod shells from Madagascar (Mahajanga Basin, 40–42° southern latitude) are reconstructed based on a novel multi-proxy approach. Here we combine and contrast: (i) nacre tablet-paleobathymetry, (ii) Westermann Morphospace, and (iii) shell isotope geochemistry analysis. Results obtained allow for a robust reconstruction of habitat depth, paleo-seawater temperatures, and paleoecology of extinct cephalopod taxa. The discocone nautiloid Cymatoceras is regarded as vertical migrant with a maximum habitat depth of 250 m and a mean habitat water temperature of 20–21 °C. All three ammonoid taxa (Cleoniceras, Desmoceras, and Eogaudryceras) share a platycone to planorbicone shell shape suggesting a demersal life habit at maximal water depths of 450–500 m and temperatures of 19–21 °C for Cleoniceras and Desmoceras, and the deepest (525 m) and coolest (14 °C) habitat for Eogaudryceras. Circumstantial evidence from benthic mollusk shells from the same stratigraphic interval as well as sedimentological and paleopathological data provide further support for habitat reconstructions. Reconstructed paleotemperatures shown here provide well-constrained evidence for the thermal structure of past oceanic water masses and have significance for Cretaceous paleoceanography in general.     

Chemical compositions of mussels and clams from the Tangyin and Yonaguni Knoll IV hydrothermal fields in the southwestern Okinawa Trough

Studies of the chemical characteristics of mussels and clams in seafloor hydrothermal fields are important for understanding mass fluxes and elemental partitioning from hydrothermal vents into the biosphere, metal bioaccumulation of seafloor hydrothermal ecosystems, and the sources and sinks of biogeochemical and fluid cycles. We are the first to measure the mineral, major, trace and rare earth element, and carbon and oxygen isotope compositions of mussels (Bathymodiolus platifrons) and clams (Conchocele bisecta) from the Tangyin and Yonaguni Knoll IV hydrothermal fields in the southwestern Okinawa Trough. Mineralogical analysis shows that the carbonate shells of the mussel and clam samples are mainly composed of calcite and aragonite. Metal elements exhibit linear correlations in the shells (e.g., V and U) and tissues (e.g., Li and Rb) of the mussels and clams, suggesting that not all positive correlations of elements in tissues are inherited by the shells. V/As, Ca/Sr, and Fe/Cr ratios in the mussels and clams are close to those in the seawater, indicating that element ratios of seawater might be inherited by the mussels and clams. In addition, the Fe/Cr ratio of the shells of both mussels and clams can be used to trace the local seawater composition.The total LREE concentrations of mussel and clam tissue samples are higher than those of the mussel and clam shell samples, are similar to the hydrothermal fluids, exhibit LREE enrichment (La_CN/Nd_CN ratios = 1.86-32.1), and no or only slightly negative Eu anomalies, indicating that benthic animals are a sink of LREEs from hydrothermal fluids, and that the Eu/Eu* ratios of fluids change when fluids are incorporated into the tissues of the mussels and clams. In addition, the δ¹³C values of mussel shell samples are heavier than those of the clam shell samples in the hydrothermal field, indicating that more than one carbon source may be involved in defining the δ¹³C compositions of the shells. The majority of the δ¹⁸O values of clam shell samples fall in the range of δ¹⁸O values of the mussel shell samples, and are close to the hydrothermal fluid δ¹⁸O_H2O values, implying that the δ¹⁸O values of mussel and clam shell carbonate is influenced by the hydrothermal environment (magmatic water and fluid dilution with seawater).     

A stable isotope record from freshwater lake shells of the eastern Tibetan Plateau, China, during the past two centuries

Lake Xingcuo is a small, closed, hardwater lake situated in the eastern Tibetan Plateau. Stable isotope data (δ¹⁸O and δ¹³C) from the freshwater snail Gyraulus sibirica (Dunker) in a 34-cm-long, radioactive isotope-dated sediment core represent the past 200 years of Lake Xingcuo environmental history. Carbon and oxygen isotope ratios in the shells of the snail yield information on the isotopic composition of the water in which the shell was formed, which in turn relates to climatic conditions prevailing during the snail's life-span. Living and fossil shells from Lake Xingcuo were collected. δ¹⁸O values in the living shells from Lake Xingcuo are in equilibrium with ambient waters, while δ¹³C values may trace snail dietary carbon. On comparing δ¹⁸O and δ¹³C in the shell of Gyraulus sibirica with monitored data for the period 1954-1995, we found that the δ¹⁸O composition in the shell is an efficient proxy revealing air temperature during the warmer months from April to September. There is a positive correlation between the δ¹⁸O in the shells of Gyraulus sibirica and the running average temperature of the warmer months. Climatic variability in the eastern Tibetan Plateau for the past two centuries has been inferred from the δ¹⁸O record from the freshwater snails in the sediments of Lake Xingcuo. As such, the last 200 years' palaeoclimatic record for this region can be separated into three periods representing oscillations between warm and cool conditions consistent with the Guliya ice record in the Tibetan Plateau.