Search PubMed⌕ Search

Biomedical subjects

M Newville

Publications and source records attributed to M Newville.

15 recordsLinked to original sources

Characterization of Fe plaque and associated metals on the roots of mine-waste impacted aquatic plants.

Iron plaque on aquatic plant roots are ubiquitous and sequester metals in wetland soils; however, the mechanisms of metal sequestration are unresolved. Thus, characterizing the Fe plaque and associated metals will aid in understanding and predicting metal cycling in wetland ecosystems. Accordingly, microscopic and spectroscopic techniques were utilized to identify the spatial distributions, associations, and chemical environments of Fe, Mn, Pb, and Zn on the roots of a common, indigenous wetland plant (Phalaris arundinacea). Iron forms a continuous precipitate on the root surface, which is composed dominantly of ferrihydrite (ca. 63%) with lesser amounts of goethite (32%) and minor levels of siderite (5%). Although Pb is juxtaposed with Fe on the root surface, it is complexed to organic functional groups, consistent with those of bacterial biofilms. In contrast, Mn and Zn exist as discrete, isolated mixed-metal carbonate (rhodochrosite/hydrozincite) nodules on the root surface. Accordingly, the soil-root interface appears to be a complex biochemical environment, containing both reduced and oxidized mineral species, as well as bacterial-induced organic-metal complexes. As such, hydrated iron oxides, bacterial biofilms, and metal carbonates will influence the availability and mobility of metals within the rhizosphere of aquatic plants.

Biological Availability↗

Chromium diffusion and reduction in soil aggregates.

The distribution of metal contaminants such as chromium in soils can be strongly localized by transport limitations and redox gradients within soil aggregates. Measurements of Cr(VI) diffusion and reduction to Cr(III) were obtained in soil columns representing transects into soil aggregates in order to quantify influences of organic carbon (OC) and redox potentials on Cr transport distances and microbial community composition. Shifts in characteristic redox potentials, and the extent of Cr(VI) reduction to Cr(III) were related to OC availability. Depth profiles of Cr(VI, III) obtained with micro X-ray absorption near edge structure (micro-XANES) spectroscopy reflected interdependent effects of diffusion and spatially dependent redox potentials on reduction kinetics and microbial community composition. Shallow diffusion depths (2-10 mm) and very sharply terminated diffusion fronts in columns amended with OC (80 and 800 ppm) reflected rapid increases in Cr reduction kinetics over very short (mm) distances. These results suggest that Cr contamination in soils can be restricted to the outsides of soil aggregates due to localized transport and rapid reduction and that bulk sample characterization is inadequate for understanding the controlling biogeochemical processes.

Chromium↗

EXAFS analysis using FEFF and FEFFIT.

Some of the advanced EXAFS analysis features of FEFF and FEFFIT are described. The scattering path formalism from FEFF and cumulant expansion are used as the basic building blocks of EXAFS analysis, giving a flexible and robust parameterization of most EXAFS problems. The ability to model EXAFS data in terms of generalized physical variables is shown, including the simultaneous refinement of two different polarizations for Co K EXAFS data of CoPt3.

Journal Article↗

A study of the coordination environment in aqueous cadmium-thiol complexes by EXAFS spectroscopy: experimental vs. theoretical standards.

Using EXAFS, we investigated the changes in the local structure of Cd(II) complexes formed with a series of low-molecular-weight thiols at different thiol/cadmium stoichiometries. For dilute solutions, a comparison of theoretical and experimental standards proved the latter approach superior. The number of bound oxygen atoms decreased while the number of sulfur atoms increased as the thiol/cadmium ratios increased, indicating that up to four thiol compounds can bind to cadmium in aqueous solutions. The computer code FEFFIT was modified to employ experimental and theoretical standards with equal facility.

Journal Article↗

IFEFFIT: interactive XAFS analysis and FEFF fitting.

IFEFFIT, an interactive program and scriptable library of XAFS algorithms is presented. The core algorithms of AUTOBK and FEFFIT have been combined with general data manipulation and interactive graphics into a single package. IFEFFIT comes with a command-line program that can be run either interactively or in batch-mode. It also provides a library of functions that can be used easily from C or Fortran, as well as high level scripting languages such as Tcl, Perl and Python. Using this library, a Graphical User Interface for rapid 'online' data analysis is demonstrated. IFEFFIT is freely available with an Open Source license. Outside use, development, and contributions are encouraged.

Journal Article↗

Growth induced magnetic and chemical anisotropy in CoPt3 alloy films.

We report the results of polarized Co EXAFS experiments on a series of CoPt3 films grown by molecular beam epitaxy on (100) MgO singe crystal substrates over a range of temperatures from 473 K to 1073 K. These samples exhibit substantial perpendicular magnetic anisotropy that is strongly dependent on the substrate growth temperature Tg. We measure a preference for in-plane Co-Co pairs that is correlated with the magnetic properties.

Journal Article↗

Structure of the hydrated alpha-Al(2)O(3) (0001) surface

The physical and chemical properties of the hydrated alpha-Al(2)O(3) (0001) surface are important for understanding the reactivity of natural and synthetic aluminum-containing oxides. The structure of this surface was determined in the presence of water vapor at 300 kelvin by crystal truncation rod diffraction at a third-generation synchrotron x-ray source. The fully hydrated surface is oxygen terminated, with a 53% contracted double Al layer directly below. The structure is an intermediate between alpha-Al(2)O(3) and gamma-Al(OH)(3), a fully hydroxylated form of alumina. A semiordered oxygen layer about 2.3 angstroms above the terminal oxygen layer is interpreted as adsorbed water. The clean alpha-Al(2)O(3) (0001) surface, in contrast, is Al terminated and significantly relaxed relative to the bulk structure. These differences explain the different reactivities of the clean and hydroxylated surfaces.

Journal Article↗

X-Ray Absorption Spectroscopy of Strontium(II) Coordination.

Detailed analyses of crystalline, hydrated, and precipitated strontium compounds and an aqueous strontium solution by synchrotron extended X-ray absorption fine structure (EXAFS) were used to quantify local thermal and static disorder and to characterize strontium coordination in a variety of oxygen-ligated bonding environments. Analysis of anharmonic vibrational disorder (i.e., significant contribution from a third cumulant term (C(3)) in the EXAFS phase-shift function) in compounds with low and high static disorder around strontium showed that first-shell anharmonic contributions were generally not significant above experimental error in the EXAFS fits (R+/-0.02 Å with and without C(3)). The only case in which a significant apparent decrease in Sr-O distance was observed with increasing temperature, and for which a third cumulant term was significant, was for dilute strontium in aqueous solution. Empirical parameterization of Debye-Waller factor (sigma(2)) for strontium compounds as a function of backscatterer atomic number (Z), interatomic Sr-Z distance, and temperature of spectral data collection showed systematic increases in sigma(2) as a function of increasing temperature and Sr-Z bond length. At values of sigma(2) greater than approximately 0.025 Å(2) (for N<12 and R(Sr)-Z>3 Å), backscattering was generally not significant above noise levels in spectra of compounds of known crystal structure. Comparison of the EXAFS spectra of freshly precipitated SrCO(3) (spectra collected wet) to that of dry, powdered strontianite (SrCO(3)(s)) indicated no significant differences in the local atomic structure around strontium. Analysis of partially hydrated strontium in natural Ca-zeolite (heulandite) showed that strontium is substituted only in the calcium (Ca2) site. Backscattering from aluminum and silicon atoms in the zeolite framework were apparent in the EXAFS spectra at low and room temperature at distances from central strontium of <4.2 Å. Comparison of strontium structural coordination determined in this and previous studies suggests that previous EXAFS determinations of hydrated strontium may have underestimated first-shell interatomic distances and coordination numbers because minor contributions to the EXAFS phase-shift and amplitude functions were not accounted for, either theoretically or empirically. Copyright 2000 Academic Press.

Journal Article↗