Biomedical subjects

Matthew Newville

Publications and source records attributed to Matthew Newville.

4 recordsLinked to original sources

PubMed2004

Hexavalent uranium diffusion into soils from concentrated acidic and alkaline solutions.

Uranium contamination of soils and sediments often originates from acidic or alkaline waste sources, with diffusion being a major transport mechanism. Measurements of U(VI) diffusion from initially pH 2 and pH 11 solutions into a slightly alkaline Altamont soil and a neutral Oak Ridge soil were obtained through monitoring uptake from boundary reservoirs and from U concentration profiles within soil columns. The soils provided pH buffering, resulting in diffusion at nearly constant pH. Micro X-ray absorption near edge structure spectra confirmed that U remained in U(VI) forms in all soils. Time trends of U(VI) depletion from reservoirs and U(VI) concentration profiles within soil columns yielded Kdvalues consistent with those determined in batch tests at similar concentrations (approximately 1 mM) and much lower than values for sorption at much lower concentrations (nM to microM). These results show that U(VI) transport at high concentrations can be relatively fast at non-neutral pH, with negligible surface diffusion, because of weak sorption.

Adsorption↗

PubMed2004

The formation of sp3 bonding in compressed BN.

Attributed to their specific atomic bonding, the soft, graphite-like, hexagonal boron nitride (h-BN) and its superhard, diamond-like, cubic polymorph (c-BN) are important technological materials with a wide range of applications. At high pressure and temperature, h-BN can directly transform to a hexagonal close-packed polymorph (w-BN) that can be partially quenched after releasing pressure. Previous theoretical calculations and experimental measurements (primarily on quenched samples) provided substantial information on the transition, but left unsettled questions due to the lack of in situ characterization at high pressures. Using inelastic X-ray scattering to probe the boron and nitrogen near K-edge spectroscopy, here we report the first observation of the conversion process of boron and nitrogen sp(2)- and p-bonding to sp(3) and the directional nature of the sp(3) bonding. In combination with in situ X-ray diffraction probe, we have further clarified the structure transformation mechanism. The present archetypal example opens two enormous, element-specific, research areas on high-pressure bonding evolutions of boron and nitrogen; each of the two elements and their respective compounds have displayed a wealth of intriguing pressure-induced phenomena that result from bonding changes, including metallization, superconductivity, semiconductivity, polymerization and superhardness.

Boron Compounds↗

PubMed2003

Bonding changes in compressed superhard graphite.

Compressed under ambient temperature, graphite undergoes a transition at approximately 17 gigapascals. The near K-edge spectroscopy of carbon using synchrotron x-ray inelastic scattering reveals that half of the pi-bonds between graphite layers convert to sigma-bonds, whereas the other half remain as pi-bonds in the high-pressure form. The x-ray diffraction pattern of the high-pressure form is consistent with a distorted graphite structure in which bridging carbon atoms between graphite layers pair and form sigma-bonds, whereas the nonbridging carbon atoms remain unpaired with pi-bonds. The high-pressure form is superhard, capable of indenting cubic-diamond single crystals.

Journal Article↗

PubMedDate not supplied

Distribution of chromium contamination and microbial activity in soil aggregates.

Biogeochemical transformations of redox-sensitive chemicals in soils can be strongly transport-controlled and localized. This was tested through experiments on chromium diffusion and reduction in soil aggregates that were exposed to chromate solutions. Reduction of soluble Cr(VI) to insoluble Cr(II) occurred only within the surface layer of aggregates with higher available organic carbon and higher microbial respiration. Sharply terminated Cr diffusion fronts develop when the reduction rate increases rapidly with depth. The final state of such aggregates consists of a Cr-contaminated exterior, and an uncontaminated core, each having different microbial community compositions and activity. Microbial activity was significantly higher in the more reducing soils, while total microbial biomass was similar in all of the soils. The small fraction of Cr(VI) remaining unreduced resides along external surfaces of aggregates, leaving it potentially available to future transport down the soil profile. Using the Thiele modulus, Cr(VI) reduction in soil aggregates is shown to be diffusion rate- and reaction rate-limited in anaerobic and aerobic aggregates, respectively. Thus, spatially resolved chemical and microbiological measurements are necessary within anaerobic soil aggregates to characterize and predict the fate of Cr contamination. Typical methods of soil sampling and analyses that average over redox gradients within aggregates can erase important biogeochemical spatial relations necessary for understanding these environments.

Bacteria, Aerobic↗