Material characterization of biomieneralization in marine animals and hydrothermal events in the deep sea

通过对相模湾大豆盖生菌（Calyptogenasoyae）和海泥藻（Vestimentiferasp.）中硫的化学状态分析，揭示了深海热液矿床中物质的动力学特征。在Photon Factory，KEK，Tsukuba的光束线8B处测量这些动物的S K-XAFS光谱。光谱与标准样品的比较表明，这两种动物都含有元素硫，Vestimentifera sp.在它们的体内含有额外的四价或六价硫。用红外光谱分析硫的化学形态是不成功的，这种信息只能通过XANES分析来揭示。SEM-EDX分析揭示了样品中存在元素硫小球。结果表明，烟囱产物由无定形二氧化硅组成。Iheya的溢流物质含有Si、Mn、Ca、Fe、Cl和S ;方解石和kutnohorite被鉴定为矿物; Izena的溢流物质含有Si、Ba、S、Fe、Zn、Cl和B ;鉴定的矿物为重晶石和α-硫。由于海水中氯离子的严重干扰，EXAFS振荡的定量分析比较困难。由于许多生物矿物中含有Si和P的非晶相，我们开始将固体NMR技术引入到生物矿化的研究中。我们还研究了日本刺肋鱼（Acanthopleurajaponica）牙齿的生物矿化作用，揭示了物种间生物矿化作用的差异。通过对鳗鱼耳石中微量元素的分析，揭示了鳗鱼的洄游特征。

Chemical state analysis sulfur in Calyptogena soyae (Shirourigai) from Sagami Bay and Vestimentifera sp. (Haorimushi) has been carried out to reveal dynamics of materials in deep sea hydrothermal deposits. S K-XAFS spectra of these animals were measured at beam line 8B of Photon Factory, KEK, Tsukuba. A comparison of the spectra with standard specimens shows that both animals contain elemental sulfur, and Vestimentifera sp. Contains additional tetravalent or hexavalent sulfur in their bodies. The analysis of chemical forms of sulfur by infrared spectra was unsuccessful and such information could be revealed only by XANES analysis. SEM-EDX analysis has disclosed existence of spherules of elemental sulfur in the samples. It is found that chimney products are composed of amorphous silica. The effusive materials at Iheya contain Si, Mn, Ca, Fe, Cl and S ; calcite and kutnohorite are identified as minerals, while those at Izena contain Si, Ba, S, Fe, Zn, Cl and B ; minerals identified are barite and α-sulfur. Quantitative analyses of EXAFS oscillation were difficult to do because of the serious interference from chlorine ion, whose origin was sea water. We have started to introduce solid NMR technique into our research of biomineralization, because many biominerals contain Si and P as amorphous phases. We have also studied biomineralization of the teeth of Chiton, Acanthopleura Japonica and revealed the existence of difference in biomineralization among the species. The analysis of the trace elements in otolith of eels revealed the migration characteristics of the eels.