As part of a study of the effect of particle size on reactivity of hematite to aqueous metal ions, the sorption of Zn(II) on hematite nanoparticles and microparticles was examined over a wide range of Zn(II) concentrations using Zn K-edge EXAFS. When reacted with nanoparticles at pH 5.5 and low Zn(II) sorption densities (0.04 {le} {Lambda} < 2.76 imol/m{sup 2}), Zn(II) formed five-coordinated or a mixture of four- and six-coordinated surface complexes with an average Zn-O distance of 2.04({+-}0.02){angstrom}. At pH 5.5 and high Zn(II) sorption densities (2.76 {ge} {Lambda} {le} 3.70 mol/m{sup 2}), formation of surface precipitates is suggested based on the presence of second-shell Zn and multiple scattering features in the Fourier transform (FT) of the EXAFS spectra. EXAFS fitting of these high {Lambda} samples yielded an average first-shell Zn-O distance of 2.10({+-}0.02){angstrom}, with second-shell Zn-Fe and Zn-Zn distances of 3.23({+-}0.03){angstrom} and 3.31({+-}0.03){angstrom}, respectively. Qualitative comparison between the EXAFS spectra of these sorption samples and that of amorphous zinc hydroxide and Zn-bearing hydrotalcite indicates the development of surface precipitates with increasing {Lambda}. EXAFS spectra of Zn(II) sorbed on hematite microparticles under similar experimental conditions showed no evidence for surface precipitates even at the highest Zn surface coverage ({Lambda} …

Gold is a highly valuable metal that can concentrate in iron-rich exogenetic horizons such as laterites. An improved knowledge of the retention mechanisms of gold onto highly reactive soil components such as iron oxyhydroxides is therefore needed to better understand and predict the geochemical behavior of this element. In this study, we use EXAFS information and titration experiments to provide a realistic thermochemical description of the sorption of trivalent gold onto iron oxy-hydroxides. Analysis of Au L{sub III}-edge XAFS spectra shows that aqueous Au(III) adsorbs from chloride solutions onto goethite surfaces as inner-sphere square-planar complexes (Au(III)(OH,Cl){sub 4}), with dominantly OH ligands at pH > 6 and mixed OH/Cl ligands at lower pH values. In combination with these spectroscopic results, Reverse Monte Carlo simulations were used to constraint the possible sorption sites on the surface of goethite. Based on this structural information, we calculated sorption isotherms of Au(III) on Fe oxy-hydroxides surfaces, using the CD-MUSIC (Charge Distribution--Multi Site Complexation) model. The various Au(III)-sorbed species were identified as a function of pH, and the results of these EXAFS+CD-MUSIC models are compared with titration experiments. The overall good agreement between the predicted and measured structural models shows the potential of this combined approach …

XAFS and {mu}-XAFS spectra were collected at the Cu K-edge for seven chrysocolla samples (Peru, USA, and Congo). The results suggest that the local structure around Cu is similar to that in Cu(OH){sub 2} (spertiniite). Cu-L{sub 3} STXM imaging and spectroscopy confirm that the chrysocolla samples examined here consist of mesoscopic Cu(II)-rich domains surrounded by Si-rich domains (in agreement with results from infra-red spectroscopy). Hence, we suggest that chrysocolla, which is generally considered to be orthorhombic with composition (Cu,Al){sub 2}H{sub 2}Si{sub 2}O{sub 5}(OH){sub 4} {center_dot} nH{sub 2}O, is in actually a mesoscopic assemblage composed dominantly of spertiniite (Cu(OH){sub 2}), water and amorphous silica (SiO{sub 2}).

Analyses of archaeological materials aim to rediscover the know-how of Prehistoric people by determining the nature of the painting matter, its preparation mode, and the geographic origin of its raw materials. This study deals with identification of manganese oxides in black pigments by micro-XANES (X-ray absorption near-edge structure) based on previous TEM (transmission electron microscopy) studies. Complex mixtures of the manganese oxides studied are present in some of mankind's oldest known paintings, namely those from the caves of Lascaux (Dordogne, France) and Ekain (Basque country, Spain). Scarce manganese oxide minerals, including groutite, hausmannite, and manganite, were found for the first time in Paleolithic art at these archaeological sites. Because there are no known deposits of such minerals in these areas, more distant origins and trade routes are inferred. The closest known Mn-rich geological province for Lascaux is the central Pyrenees, which is {approx} 250 km from the Dordogne area.

Many in situ XAFS studies have shown that zinc incorporated in layered minerals is a major form of zinc in Zn-contaminated soils. Quantitative information on the local structural environment(s) and ordering of Zn in these minerals is required to better understand its behavior in soils. In this study, EXAFS spectroscopy was used to assess the structural environment of zinc incorporated at trace levels (40 ppm to 4,000 ppm) within the octahedral sheets of various natural and synthetic layered minerals. Results indicate that EXAFS data analyzed using ab initio FEFF calculations (FEFF 8.10) can unambiguously distinguish between zinc incorporation within the octahedral sheet of dioctahedral versus trioctahedral layered minerals and can determine the distribution (random or ordered) of zinc cations within the octahedral sheets of these minerals.

Availability modeling of the proposed International Linear Collider (ILC) predicts unacceptably low uptime with current electronics systems designs. High Availability (HA) analysis is being used as a guideline for all major machine systems including sources, utilities, cryogenics, magnets, power supplies, instrumentation and controls. R&D teams are seeking to achieve total machine high availability with nominal impact on system cost. The focus of this paper is the investigation of commercial standard HA architectures and packaging for Accelerator Controls and Instrumentation. Application of HA design principles to power systems and detector instrumentation are also discussed.

The National Ignition Facility (NIF) is currently the largest and most energetic laser system in the world. The main amplifiers are driven by the Injection Laser System comprised of the master oscillators, optical preamplifiers, temporal pulse shaping and spatial beam formatting elements and injection diagnostics. Starting with two fiber oscillators separated by up to a few angstroms, the pulse is phase modulated to suppress SBS and enhance spatial smoothing, amplified, split into 48 individual fibers, and then temporally shaped by an arbitrary waveform generator. Residual amplitude modulation induced in the preamplifiers from the phase modulation is also precompensated in the fiber portion of the system before it is injected into the 48 pre-amplifier modules (PAMs). Each of the PAMs amplifies the light from the 1 nJ fiber injection up to the multi-joule level in two stages. Between the two stages the pre-pulse is suppressed by 60 dB and the beam is spatially formatted to a square aperture with precompensation for the nonuniform gain profile of the main laser. The input sensor package is used to align the output of each PAM to the main laser and acquire energy, power, and spatial profiles for all shots. The beam transport sections split …

The local structure around Th, U, Ce and Nd in leached silicate glasses was examined using XAFS spectroscopy at their L3 edges and also at the K edge of Fe, Co, Ni, Zr and Mo. Pellets of inactive borosilicate glasses with a simplified or a complex composition were leached statically at 90 C, at pH buffered to 0 or 6 for 28 days (surface/volume, S/V, ratios of 0.1 cm{sup -1}). These glasses are compared to another SON68 sample (denoted ''SP1'' in this paper) that was statically leached for 12 years under similar conditions, except for a higher S/V of 12 cm{sup -1} and a higher unconstrained pH of 9.6. The speciation of Fe, Co, Ni, Zr and Mo in the simple and the complex unleached are similar. In the statically leached glasses, the speciation of these transition metals is mostly identical to in the unleached glasses, except in the gels formed at the surface of the glasses leached at low pH, where large speciation differences are observed. Surface precipitates, especially for Fe (as ferrihydrite), Mo (possibly sidwillite) and Th (as ThO{sub 2}) were detected. Finally, the drying of the gels considerably affects the metal speciation by enhancing metal polymerization.

The ninth-order weighted essentially non-oscillatory (WENO) shock-capturing method is used to investigate the physics of reshock and mixing in two-dimensional single-mode Richtmyer-Meshkov instability to late times. The initial conditions and computational domain were adapted from the Mach 1.21 air(acetone)/SF{sub 6} shock tube experiment of Collins and Jacobs [J. Fluid Mech. 464, 113 (2002)]: the growth of the bubble and spike perturbation amplitudes from fifth- and ninth-order WENO simulations of this experiment were compared to the predictions of amplitude growth models, and were shown to be in very good agreement with the experimental data prior to reshock [Latini, Schilling and Don, Phys. Fluids (2007), in press]. In the present investigation, the density, vorticity, baroclinic vorticity production, and simulated density Schlieren fields are first presented to qualitatively describe reshock. The baroclinic circulation deposition on the interface is shown to agree with the predictions of the Samtaney and Zabusky [J. Fluid Mech. 269, 45 (1994)] model and linear instability theory. The time-evolution of the positive and negative circulation on the interface is considered before and after reshock: it is shown that the circulations are equal before, as well as after reshock, until the interaction of the reflected rarefaction with the layer leads to …

Se K-edge XAFS spectra were collected for various model compounds of Se as well as for 3 biofilm samples from bioreactors used for Se-contaminated wastewater treatment. In the biofilm samples, Se is dominantly as Se(0) despite Se K-edge XANES spectroscopy cannot easily distinguish between elemental Se and Se(-I)-bearing selenides. EXAFS spectra indicate that Se is located within aperiodic domains, markedly different to these known in monoclinic red selenium. However, Se can well occur within nanodivided domains related to monoclinic red Se, as this form was optically observed at the rim of some sludges. Aqueous selenate is then efficiently bioreduced, under sulfate reducing and methanogenic conditions.