60 research outputs found

    Surface Structure of Protonated R-Sapphire (11̅02) Studied by Sum-Frequency Vibrational Spectroscopy

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    Sum frequency vibrational spectroscopy was used to study the protonated R-plane (1{bar 1}02 ) sapphire surface. The OH stretch vibrational spectra show that the surface is terminated with three hydroxyl moieties, two from AlOH{sub 2} and one from Al{sub 2}OH functional groups. The observed polarization dependence allows determination of the orientations of the three OH species. The results suggest that the protonated sapphire (1{bar 1}02 ) surface differs from an ideal stoichimetric termination in a manner consistent with previous X-ray surface diffraction (crystal truncation rod) studies. However, in order to best explain the observed hydrogenbonding arrangement, surface oxygen spacing determined from the X-ray diffraction study requires modification

    Precipitation pathways for ferrihydrite formation in acidic solutions

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    Iron oxides and oxyhydroxides form via Fe hydrolysis and polymerization in many aqueous environments, but the pathway from Fe monomers to oligomers and then to solid phase nuclei is unknown. In this work, using combined X-ray, UV-vis, and Mössbauer spectroscopic approaches, we were able to identify and quantify the long-time sought ferric speciation over time during ferric oxyhydroxide formation in partially-neutralized ferric nitrate solutions ([Fe ]=0.2M, 1.

    Analysis and Simulation of the Structure of Nanoparticles That Undergo a Surface-Driven Structural Transformation

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    This report addresses the analysis and simulation of the structure of nanoparticles that undergo a surface-driven structural transformation

    Wintertime phytoplankton bloom in the subarctic Pacific supported by continental margin iron

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    Author Posting. © American Geophysical Union, 2006. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 20 (2006): GB1006, doi:10.1029/2005GB002557.Heightened biological activity was observed in February 1996 in the high-nutrient low-chlorophyll (HNLC) subarctic North Pacific Ocean, a region that is thought to be iron-limited. Here we provide evidence supporting the hypothesis that Ocean Station Papa (OSP) in the subarctic Pacific received a lateral supply of particulate iron from the continental margin off the Aleutian Islands in the winter, coincident with the observed biological bloom. Synchrotron X-ray analysis was used to describe the physical form, chemistry, and depth distributions of iron in size fractionated particulate matter samples. The analysis reveals that discrete micron-sized iron-rich hot spots are ubiquitous in the upper 200 m at OSP, more than 900 km from the closest coast. The specifics of the chemistry and depth profiles of the Fe hot spots trace them to the continental margins. We thus hypothesize that iron hot spots are a marker for the delivery of iron from the continental margin. We confirm the delivery of continental margin iron to the open ocean using an ocean general circulation model with an iron-like tracer source at the continental margin. We suggest that iron from the continental margin stimulated a wintertime phytoplankton bloom, partially relieving the HNLC condition.This work was supported by the U.S. Department of Energy, Office of Science, Office of Biological and Environmental Research (KP1202030) to J. K. B and by NSFATM-9987457 to I. F. The Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, Division of Materials Sciences and Division of Chemical Sciences, Geosciences, and Biosciences of the U.S. Department of Energy at Lawrence Berkeley National Laboratory under contract DE-AC03-76SF00098

    Special phase transformation and crystal growth pathways observed in nanoparticles†

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    Phase transformation and crystal growth in nanoparticles may happen via mechanisms distinct from those in bulk materials. We combine experimental studies of as-synthesized and hydrothermally coarsened titania (TiO(2)) and zinc sulfide (ZnS) with thermodynamic analysis, kinetic modeling and molecular dynamics (MD) simulations. The samples were characterized by transmission electron microscopy, X-ray diffraction, synchrotron X-ray absorption and scattering, and UV-vis spectroscopy. At low temperatures, phase transformation in titania nanoparticles occurs predominantly via interface nucleation at particle–particle contacts. Coarsening and crystal growth of titania nanoparticles can be described using the Smoluchowski equation. Oriented attachment-based crystal growth was common in both hydrothermal solutions and under dry conditions. MD simulations predict large structural perturbations within very fine particles, and are consistent with experimental results showing that ligand binding and change in aggregation state can cause phase transformation without particle coarsening. Such phenomena affect surface reactivity, thus may have important roles in geochemical cycling
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