LAUSR

Understanding interface structures, nano-precipitates, vacancies, impurities, and adsorbed atoms on mineral surfaces are important to elucidate formation mechanism and reactions of minerals in the earth environments. Aberration-corrected Z-contrast imaging can provide chemical images with sub-Å resolution. Z-contrast images are HAADF images with atomic resolution. Multiple diffraction effects that appear in high-resolution transmission electron microscopic (HRTEM) images can be eliminated or minimized in Z-contrast images, because Z-contrast imaging uses non-coherent elastically scattered electrons at high scattering angle. We can obtain positions of atoms directly over a large range of thickness, with Z-contrast to help distinguish columns of different atoms and their occupancies along the beam direction. Interface structures and crystal structures of nano-minerals and nano-precipitates can be solved by combining the Z-contrast imaging and ab-initio calculation using density functional theory (DFT) methods. Vacancies, impurities, adsorbed heavy atoms can be also revealed directly [1-2]. Zcontrast images of the Fe-oxyhydroxides show ordered FeOOH proto-goethite nano-domains intergrown with nanophase goethite. The FeOOH nanophase is a precursor to the goethite. DFT calculations indicate that goethite is more stable than proto-goethite. Our results suggest that ordering between Fe and vacancies in octahedral sites result in the transformation from feroxyhyte to goethite through a proto-goethite intermediate phase. Combining Z-contrast images and TEM-EDS reveals that arsenate (AsO43-) tetrahedra are preferentially adsorbed on the proto-goethite (001) surface (Fig.1). Vacancy ordering in Fe-bearing forsterite olivine was observed. The phenomenon may explain observed highly anisotropic diffusion in some Fe-bearing olivine minerals and more ordered structure analyzed at high-temperature in air. In a Sibearing magnetite, Si replaces Fe3+ in tetrahedral sites of the magnetite structure and vacancies are introduced in the octahedral Fe2+ sites (Fig. 2). Nano-precipitates of Si-magnetite with composition of (□0.5 Fe2+0.5)VI(Fe3+)VISiIVO4 or γ-Fe1.5SiO4 occur in the magnetite [4].