Schofield Eleanor J, Veeramani Harish, Sharp Jonathan O, Suvorova Elena, Bernier-Latmani Rizlan, Mehta Apurva, Stahlman Jonathan, Webb Samuel M, Clark David L, Conradson Steven D, Ilton Eugene S, Bargar John R
Stanford Synchrotron Radiation Laboratory, 2575 Sand Hill Rd., Menlo Park, California 94025, USA.
Environ Sci Technol. 2008 Nov 1;42(21):7898-904. doi: 10.1021/es800579g.
The stability of biogenic uraninite with respect to oxidation is seminal to the success of in situ bioreduction strategies for remediation of subsurface U(VI) contamination. The properties and hence stability of uraninite are dependent on its size, structure, and composition. In this study, the local-, intermediate-, and long-range molecular-scale structure of nanoscale uraninite produced by Shewanella oneidensis strain MR-1 was investigated using EXAFS, SR-based powder diffraction and TEM. The uraninite products were found to be structurally homologous with stoichiometric U02 under all conditions considered. Significantly, there was no evidence for lattice strain of the biogenic uraninite nanoparticles. The fresh nanoparticles were found to exhibit a well-ordered interior core of diameter ca. 1.3 nm and an outer region of thickness ca approximately 0.6 nm in which the structure is locally distorted. The lack of nanoparticle strain and structural homology with stoichiometric U02 suggests that established thermodynamic parameters for the latter material are an appropriate starting point to model the behavior of nanobiogenic uraninite. The detailed structural analysis in this study provides an essential foundation for subsequent investigations of environmental samples.
生物成因晶质铀矿相对于氧化作用的稳定性对于原位生物还原策略修复地下U(VI)污染的成功至关重要。晶质铀矿的性质及其稳定性取决于其尺寸、结构和组成。在本研究中,利用扩展X射线吸收精细结构光谱(EXAFS)、基于同步辐射的粉末衍射和透射电子显微镜(TEM)研究了希瓦氏菌MR-1菌株产生的纳米级晶质铀矿的局域、中间和长程分子尺度结构。在所考虑的所有条件下,发现晶质铀矿产物在结构上与化学计量比的UO₂同源。值得注意的是,没有证据表明生物成因晶质铀矿纳米颗粒存在晶格应变。发现新鲜的纳米颗粒呈现出直径约为1.3 nm的有序内部核心以及厚度约为0.6 nm的外部区域,其中结构局部扭曲。纳米颗粒缺乏应变以及与化学计量比UO₂的结构同源性表明,后者材料已确定的热力学参数是模拟纳米生物成因晶质铀矿行为的合适起点。本研究中的详细结构分析为后续环境样品研究提供了重要基础。