Fenton's reagent, a solution of hydrogen peroxide and ferrous iron catalyst, is used for an in-situ chemical oxidation of organic contaminants. Sulfuric acid is commonly used to create an acidic condition needed for catalytic oxidation. Fenton's reaction often involves pressure buildup and precipitation of reaction products, which can cause safety hazards and diminish efficiency. We selected citric acid, a food-grade substance, as an acidifying agent to evaluate its efficiencies for organic contaminant removal in Fenton's reaction, and examined the impacts of using citric acid on the unwanted reaction products. A series of batch and column experiments were performed with varying H{sub 2}O{sub 2} concentrations to decompose selected chlorinated ethylenes. Either dissolved iron from soil or iron sulfate salt was added to provide the iron catalyst in the batch tests. Batch experiments revealed that both citric and sulfuric acid systems achieved over 90% contaminant removal rates, and the presence of iron catalyst was essential for effective decontamination. Batch tests with citric acid showed no signs of pressure accumulation and solid precipitations, however the results suggested that an excessive usage of H{sub 2}O{sub 2} relative to iron catalysts (Fe{sup 2+}/H{sub 2}O{sub 2} < 1/330) would result in lowering the efficiency of contaminant …

Where Martian rocks have been exposed to liquid water, chemistry versus depth profiles could elucidate both Martian climate history and potential for life. The persistence of primary minerals in weathered profiles constrains the exposure time to liquid water: on Earth, mineral persistence times range from {approx}10 ka (olivine) to {approx}250 ka (glass) to {approx}1Ma (pyroxene) to {approx}5Ma (plagioclase). Such persistence times suggest mineral persistence minima on Mars. However, Martian solutions may have been more acidic than on Earth. Relative mineral weathering rates observed for basalt in Svalbard (Norway) and Costa Rica demonstrate that laboratory pH trends can be used to estimate exposure to liquid water both qualitatively (mineral absence or presence) and quantitatively (using reactive transport models). Qualitatively, if the Martian solution pH > {approx}2, glass should persist longer than olivine; therefore, persistence of glass may be a pH-indicator. With evidence for the pH of weathering, the reactive transport code CrunchFlow can quantitatively calculate the minimum duration of exposure to liquid water consistent with a chemical profile. For the profile measured on the surface of Humphrey in Gusev Crater, the minimum exposure time is 22 ka. If correct, this estimate is consistent with short-term, episodic alteration accompanied by ongoing surface …

Soils contain the largest inventory of organic carbon on the Earth's surface. Therefore, it is important to understand how soil organic carbon (SOC) is distributed in soils. This study directly measured SOC distributions within soil microaggregates and its associations with major soil elements from three soil groups (Phaeozem, Cambisol, and Ultisol), using scanning transmission X-ray microscopy (STXM) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy at a spatial resolution of 30 nm. Unlike previous studies, small intact soil microaggregates were examined directly in order to avoid preparatory procedures that might alter C speciation. We found that SOC exists as distinct particles (tens to hundreds of nm) and as ubiquitous thin coatings on clay minerals and iron-oxides coatings. The distinct SOC particles have higher fractions of aromatic C than the coatings. NEXAFS spectra of the C coatings within individual microaggregates were relatively similar. In the Phaeozem soil, the pervasive spectral features were those of phenolic and carboxylic C, while in the Cambisol soil the most common spectral feature was the carboxyl peak. The Ultisol soil displayed a diffuse distribution of aromatic, phenolic, and carboxylic C peaks over all surfaces. In general, a wide range of C functional groups coexist within individual …

Operons are a major feature of all prokaryotic genomes, buthow and why operon structures vary is not well understood. To elucidatethe life-cycle of operons, we compared gene order between Escherichiacoli K12 and its relatives and identified the recently formed anddestroyed operons in E. coli. This allowed us to determine how operonsform, how they become closely spaced, and how they die. Our findingssuggest that operon evolution may be driven by selection on geneexpression patterns. First, both operon creation and operon destructionlead to large changes in gene expression patterns. For example, theremoval of lysA and ruvA from ancestral operons that contained essentialgenes allowed their expression to respond to lysine levels and DNAdamage, respectively. Second, some operons have undergone acceleratedevolution, with multiple new genes being added during a brief period.Third, although genes within operons are usually closely spaced becauseof a neutral bias toward deletion and because of selection against largeoverlaps, genes in highly expressed operons tend to be widely spacedbecause of regulatory fine-tuning by intervening sequences. Althoughoperon evolution may be adaptive, it need not be optimal: new operonsoften comprise functionally unrelated genes that were already inproximity before the operon formed.

The linearized approximation to the semiclassical initial value representation (LSC-IVR) is used to calculate time correlation functions relevant to the incoherent dynamic structure factor for inelastic neutron scattering from liquid para-hydrogen at 14 K. Various time correlations functions were used which, if evaluated exactly, would give identical results, but they do not because the LSC-IVR is approximate. Some of the correlation functions involve only linear operators, and others involve non-linear operators. The consistency of the results obtained with the various time correlation functions thus provides a useful test of the accuracy of the LSC-IVR approximation and its ability to treat correlation functions involving both linear and nonlinear operators in realistic anharmonic systems. The good agreement of the results obtained from different correlation functions, their excellent behavior in the spectral moment tests based on the exact moment constraints, and their semi-quantitative agreement with the inelastic neutron scattering experimental data all suggest that the LSC-IVR is indeed a good short-time approximation for quantum mechanical correlation functions.

This report describes a screening and ranking framework(SRF) developed to evaluate potential geologic carbon dioxide (CO2)storage sites on the basis of health, safety, and environmental (HSE)risk arising from possible CO2 leakage. The approach is based on theassumption that HSE risk due to CO2 leakage is dependent on three basiccharacteristics of a geologic CO2 storage site: (1) the potential forprimary containment by the target formation, (2) the potential forsecondary containment if the primary formation leaks, and (3) thepotential for attenuation and dispersion of leaking CO2 if the primaryformation leaks and secondary containment fails. The framework isimplemented in a spreadsheet in which users enter numerical scoresrepresenting expert opinions or general information available frompublished materials along with estimates of uncertainty to evaluate thethree basic characteristics in order to screen and rank candidate sites.Application of the framework to the Rio Vista Gas Field, Ventura OilField, and Mammoth Mountain demonstrates the approach. Refinements andextensions are possible through the use of more detailed data or modelresults in place of property proxies. Revisions and extensions to improvethe approach are anticipated in the near future as it is used and testedby colleagues and collaborators.

X-ray magnetic circular dichroism (XMCD) is utilized to explore the temperature dependence of the interface moments in Co{sub 2}MnSi (CMS) thin films capped with aluminium. By increasing the thickness of the capping layer we demonstrate enhanced interface sensitivity of the measurements and the existence of a thin Mn oxide layer at the CMS/Al interface even when a thick capping layer is used. We show that for well ordered L2{sub 1} CMS films there is no significant variation in either the Co or Mn interface moments as a function of temperature. However, a dramatic reduction in the interface moments at low temperature is observed in a disordered CMS film that is likely to be caused by increased Mn-Mn antiferromagnetic coupling. It is suggested that for ordered L2{sub 1} CMS films the temperature dependence of the tunneling magnetoresistance is not related to changes in the interface moments. However, the existence of residual Mn oxide at the CMS/barrier interface could be a contributing factor.

The formation of regularly-spaced metal nanostructures in selectively-placed insulating nanowires is an important step toward realization of a wide range of nano-scale electronic and opto-electronic devices. Here we report templated synthesis of Au nanospheres embedded in silica nanowires, with nanospheres consistently spaced with a period equal to three times their diameter. Under appropriate conditions, nanowires form exclusively on Si nanostructures because of enhanced local oxidation and reduced melting temperatures relative to templates with larger dimensions. We explain the spacing of the nanospheres with a general model based on a vapor-liquid-solid mechanism, in which an Au/Si alloy dendrite remains liquid in the nanotube until a critical Si concentration is achieved locally by silicon oxide-generated nanowire growth. Additional Si oxidation then locally reduces the surface energy of the Au-rich alloy by creating a new surface with minimum area inside of the nanotube. The isolated liquid domain subsequently evolves to become an Au nanosphere, and the process is repeated.

The accidental overfilling of waste liquid from tank BX-102 at the Hanford Site in 1951 put about 10 metric tons of U(VI) into the vadose zone. In order to understand the dominant geochemical reactions and transport processes occurred during the initial infiltration and help understand current spatial distribution, we simulated the waste liquid spilling event in laboratory sediment columns using synthesized metal waste solution. We found that, as the plume propagating through sediments, pH decreased greatly (as much as 4 units) at the moving plume front. Infiltration flow rates strongly affect U behavior. Slower flow rates resulted in higher sediment-associated U concentrations, and higher flow rates ({ge} 5 cm/day) permitted practically unretarded U transport. Therefore, given the very high K{sub sat} of most of Hanford formation, the low permeability zones within the sediment could have been most important in retaining high concentrations of U during initial release into the vadose zone. Massive amount of colloids, including U-colloids, formed at the plume fronts. Total U concentrations (aqueous and colloid) within plume fronts exceeded the source concentration by up to 5-fold. Uranium colloid formation and accumulation at the neutralized plume front could be one mechanism responsible for highly heterogeneous U distribution observed …

A dynamic pore-scale network model is presented for investigating the effects of interfacial tension and oil-water viscosity on relative permeability during chemical flooding. This model takes into account both viscous and capillary forces in analyzing the impact of chemical properties on flow behavior or displacement configuration, as opposed to the conventional or invasion percolation algorithm which incorporates capillary pressure only. The study results indicate that both water and oil relative-permeability curves are dependent strongly on interfacial tension as well as an oil-water viscosity ratio. In particular, water and oil relative-permeability curves are both found to shift upward as interfacial tension is reduced, and they both tend to become linear versus saturation once interfacial tension is at low values. In addition, the oil-water viscosity ratio appears to have only a small effect under conditions of high interfacial tension. When the interfacial tension is low, however, water relative permeability decreases more rapidly (with the increase in the aqueous-phase viscosity) than oil relative permeability. The breakthrough saturation of the aqueous phase during chemical flooding tends to decrease with the reduction of interfacial tension and may also be affected by the oil-water viscosity ratio.

A strong effect of a moderately elevated surface temperature on net carbon deposition and deuterium co-deposition in the DIII-D divertor was observed under detached conditions. A DiMES sample with a gap 2 mm wide and 18 mm deep was exposed to lower-single-null (LSN) L-mode plasmas first at room temperature, and then at 200 C. At the elevated temperature, deuterium co-deposition in the gap was reduced by an order of magnitude. At the plasma-facing surface of the heated sample net carbon erosion was measured at a rate of 3 nm/s, whereas without heating net deposition is normally observed under detachment. In a related experiment three sets of molybdenum mirrors recessed 2 cm below the divertor floor were exposed to identical LSN ELMy H-mode discharges. The first set of mirrors exposed at ambient temperature exhibited net carbon deposition at a rate of up to 3.7 nm/s and suffered a significant drop in reflectivity. In contrast, two other mirror sets exposed at elevated temperatures between 90 C and 175 C exhibited practically no carbon deposition.

This project supplemented our regular DOE grant from the Basic Energy Sciences organization with the goal of fostering industrial partnerships and student internships. During the project period, we have interacted with between 15 and 20 companies in the optical fiber telecommunications equipment industry, and our students have participated in a number of highly visible projects with companies such as Ciena, Science Applications International Corporation, KDD, ATT, Virtual Photonics, Inc., Phaethon Telecommunications, PhotonEx, and others. The project led to many successful interactions and numerous job offers for our students.

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It is well known that at present, exact averaging of the equations for flow and transport in random porous media have been proposed for limited special fields. Moreover, approximate averaging methods--for example, the convergence behavior and the accuracy of truncated perturbation series--are not well studied, and in addition, calculation of high-order perturbations is very complicated. These problems have for a long time stimulated attempts to find the answer to the question: Are there in existence some, exact, and sufficiently general forms of averaged equations? Here, we present an approach for finding the general exactly averaged system of basic equations for steady flow with sources in unbounded stochastically homogeneous fields. We do this by using (1) the existence and some general properties of Green's functions for the appropriate stochastic problem, and (2) some information about the random field of conductivity. This approach enables us to find the form of the averaged equations without directly solving the stochastic equations or using the usual assumption regarding any small parameters. In the common case of a stochastically homogeneous conductivity field we present the exactly averaged new basic nonlocal equation with a unique kernel-vector. We show that in the case of some type of global …

The mineral alteration in the concrete barrier and in the clay formation around long-lived intermediate-level radioactive waste in the French deep geological disposal concept is evaluated using numerical modeling. There are concerns that the mineralogical composition of the surrounded clay will not be stable under the high alkaline pore fluid conditions caused by concrete (pH {approx} 12). Conversely, the infiltration of CO{sub 2}-rich groundwater from the clay formation into initially unsaturated concrete, at the high temperature (T {approx} 70 C) produced from the decay of radionuclides, could cause carbonation, thereby potentially affecting critical performance functions of this barrier. This could also lead to significant changes in porosity, which would affect aqueous diffusive transport of long-lived radionuclides. All these processes are therefore intimately coupled and advanced reactive transport models are required for long-term performance assessment. The uncertainty in predictions of these models is one major question that must be answered. A mass-transfer model response to an alkaline perturbation in clay with standard model values is first simulated using the two-phase non-isothermal reactive transport code TOUGHREACT. The selection of input parameters is thereafter designed to sample uncertainties in a wide range of physico-chemical processes without making a priori assumptions about the relative …

Bioremediation of metals and radionuclides has had manyfield tests, demonstrations, and full-scale implementations in recentyears. Field research in this area has occurred for many different metalsand radionuclides using a wide array of strategies. These strategies canbe generally characterized in six major categories: biotransformation,bioaccumulation/bisorption, biodegradation of chelators, volatilization,treatment trains, and natural attenuation. For all field applicationsthere are a number of critical biogeochemical issues that most beaddressed for the successful field application. Monitoring andcharacterization parameters that are enabling to bioremediation of metalsand radionuclides are presented here. For each of the strategies a casestudy is presented to demonstrate a field application that uses thisstrategy.

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Arc and glow discharges are defined based on their cathode processes. Arcs are characterized by collective electron emission, which can be stationary with hot cathodes (thermionic arcs), or non-stationary with cold cathodes (cathodic arcs). A brief review on cathodic arc properties serves as the starting point to better understand arcing phenomena in sputtering. Although arcing occurs in both metal and reactive sputtering, it is more of an issue in the reactive case. Arcing occurs if sufficiently high field strength leads to thermal runaway of an electron emission site. The role of insulating layers and surface potential adjustment through current leakage is highlighted. In the situation of magnetron sputtering with ''racetrack'', the need for a model with two spatial dimensions is shown. In many cases, arcing is initiated by breakdown of dielectric layers and inclusions. It is most efficiently prevented if formation and excessive charge-up of dielectric layers and inclusions can be avoided.

The VARIANT module of the DIF3D code has been upgraded to utilize surface-dependent discontinuity factors. The performance of the new capability is verified using two-dimensional core cases with control rods in reflector and fuel blocks. Cross sections for VHTR components were generated using the DRAGON and HELIOS codes. For rodded block cross sections, the DRAGON calculations used a single-block model or the multi-block models combined with MCNP4C flux solutions, whereas the HELIOS calculations utilized multi-block models. Results from core calculations indicate that multiplication factor, block power, and control rod worth are significantly improved by using surface-dependent discontinuity factors.

Data from a recently installed insertable magnetic probe array in the Sustained Spheromak Physics Experiment (SSPX) [E. B. Hooper et al., Nucl. Fusion 39, 863 (1999)] is compared against NIMROD [C. R. Sovinec et al., J. Comp. Phys. 195, 355 (2004)], a full 3D resistive magnetohydrodynamic code that is used to simulate SSPX plasmas. The experiment probe consists of a linear array of chip inductors arranged in clusters that are spaced every 2 cm, and spans the entire machine radius at the flux conserver midplane. Both the experiment and the numerical simulations show the appearance, shortly after breakdown, of a column with a hollow current profile that precedes magnetic reconnection, a process essential to the formation of closed magnetic flux surfaces. However, there are differences between the experiment and the simulation in how the column evolves after it is formed. These differences are studied to help identify the mechanisms that eventually lead to closed-flux surfaces (azimuthally averaged) and flux amplification, which occur in both the experiment and the simulation.

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 …

This work compares two novel techniques for the fabrication of ceramic scaffolds for bone tissue engineering with complex porosity: robocasting and freeze casting. Both techniques are based on the preparation of concentrated ceramic suspensions with suitable properties for the process. In robocasting, the computer-guided deposition of the suspensions is used to build porous materials with designed three dimensional (3-D) geometries and microstructures. Freeze casting uses ice crystals as a template to form porous lamellar ceramic materials. Preliminary results on the compressive strengths of the materials are also reported.

Plasma polarization spectroscopy work done by our group since the 3rd US-Japan PPS Workshop is overviewed. Theoretically, the polarization dependence on various electron distribution functions for He-like, Ne-like, and Ni-like x-ray transitions for a wide range of Z has been investigated. In particular, this study was focused on the polarization dependence for monoenergetic and steep electron distribution functions. The diagnostically important spectral lines and features of K-, L-, and M-shell ions were identified which can be used in x-ray spectropolarimetry of plasma. Importance of polarization-sensitive LLNL Electron Beam Ion Trap data is emphasized. The results of the UNR polarization-sensitive Ti and Mo x-pinch experiments are discussed.

We examine strong field atomic physics in a wavelength region (3-4 microns) where very little work has previously been done. The soft photon energy allows the exploration of one-electron atoms with low binding energies (alkali metals). We find that photoionization spectra differ from rare gas studies at shorter wavelengths due to more complex ion core potentials. Harmonic generation is studied, and we find that harmonic bandwidths are consistent with theory and the possibility of compression to pulse widths much shorter than that of the driving pulse. Harmonic yields in the visible and W are sufficient for a complete study of their amplitude and phase characteristics.