Fused silica micro-structural changes associated with localized 10.6 {micro}m CO{sub 2} laser heating are reported. Spatially-resolved shifts in the high-frequency asymmetric stretch transverse-optic (TO) phonon mode of SiO{sub 2} were measured using confocal Raman microscopy, allowing construction of axial fictive temperature (T{sub f}) maps for various laser heating conditions. A Fourier conduction-based finite element model was employed to compute on-axis temperature-time histories, and, in conjunction with a Tool-Narayanaswamy form for structural relaxation, used to fit T{sub f}(z) profiles to extract relaxation parameters. Good agreement between the calculated and measured T{sub f} was found, yielding reasonable values for relaxation time and activation enthalpy in the laser-modified silica.

The average Industrial Hygienist (IH) loves a challenge, right? Okay, well here is one with more than a few twists. We start by going through the basics of a risk assessment. You have some chemical agents, a few workers, and the makings of your basic exposure characterization. However, you have no occupational exposure limit (OEL), essentially no toxicological basis, and no epidemiology. Now the real handicap is that you cannot use sampling pumps, cassettes, tubes, or any of the media in your toolbox, and the whole concept of mass-to-dose is out the window, even at high exposure levels. Of course, by the title, you knew we were talking about nanomaterials (NM). However, we wonder how many IHs know that this topic takes everything you know about your profession and turns it upside down. It takes the very foundations that you worked so hard in college and in the field to master and pulls it out from underneath you. It even takes the gold standard of our profession, the quantitative science of exposure assessment, and makes it look pretty darn rusty. Now with NM there is the potential to get some aspect of quantitative measurements, but the instruments are generally very …

This article discusses the development of Abraham model correlations for solvation characteristics of linear alcohols.

Goethite({alpha}-FeOOH), an abundant and highly reactive iron oxyhydroxide mineral, has been the subject of numerous stud-ies of environmental interface reactivity. However, such studies have been hampered by the lack of experimental constraints on aqueous interface structure, and especially of the surface water molecular arrangements. Structural information of this type is crucial because reactivity is dictated by the nature of the surface functional groups and the structure or distribution of water and electrolyte at the solid-solution interface. In this study we have investigated the goethite(100) surface using surface diffraction techniques, and have determined the relaxed surface structure, the surface functional groups, and the three dimensional nature of two distinct sorbed water layers. The crystal truncation rod (CTR) results show that the interface structure consists of a double hydroxyl, double water terminated interface with significant atom relaxations. Further, the double hydroxyl terminated surface dominates with an 89% contribution having a chiral subdomain structure on the(100) cleavage faces. The proposed interface stoichiometry is ((H{sub 2}O)-(H{sub 2}O)-OH{sub 2}-OH-Fe-O-O-Fe-R) with two types of terminal hydroxyls; a bidentate (B-type) hydroxo group and a monodentate (A-type) aquo group. Using the bond-valence approach the protonation states of the terminal hydroxyls are predicted to be OH type (bidentate hydroxyl …

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X-ray Emission Spectroscopy (XES) and Resonant Inverse Photoelectron Spectroscopy (RIPES) have been used to investigate the photon emission associated with the Ce3d5/2 and Ce3d3/2 thresholds. Strong resonant behavior has been observed in the RIPES of Ce Oxide near the 5/2 and 3/2 edges. Inverse Photoelectron Spectroscopy (IPES) and its high energy variant, Bremstrahlung Isochromat Spectroscopy (BIS), are powerful techniques that permit a direct interrogation of the low-lying unoccupied electronic structure of a variety of materials. Despite being handicapped by counting rates that are approximately four orders of magnitude less that the corresponding electron spectroscopies (Photoelectron Spectroscopy, PES, and X-ray Photoelectron Spectroscopy, XPS) both IPES and BIS have a long history of important contributions. Over time, an additional variant of this technique has appeared, where the kinetic energy (KE) of the incoming electron and photon energy (hv) of the emitted electron are roughly the same magnitude as the binding energy of a core level of the material in question. Under these circumstances and in analogy to Resonant Photoelectron Spectroscopy, a cross section resonance can occur, giving rise to Resonant Inverse Photoelectron Spectroscopy or RIPES. Here, we report the observation of RIPES in an f electron system, specifically the at the 3d{sub …

A major concern in the development of enhanced geothermal systems (EGS) is achieving and maintaining adequate injectivity, while avoiding the development of preferential short-circuiting flow paths such as those caused by thermally-induced stress cracking. Past researches have tended to focus primarily on thermal and hydraulic stimulation. Recent studies suggest that chemical stimulation may improve the performance of EGS reservoirs. Geothermal injection wells are often drilled into formations containing reactive minerals such as calcite. Injecting aqueous chemical agents such as mineral acids, could be effective for mineral dissolution and porosity enhancement at distances of several meters around a well. An alternative to treatment with strong acids is the use of supercritical (SC) CO{sub 2} as stimulation agent for an aqueous-based EGS. Reactive transport modeling is used to investigate the effectiveness of this method. We used the thermal condition and mineralogical composition from a well of Desert Peak EGS site, to examine ways in which mixtures of water and CO{sub 2} can be injected to enhance porosity.

Development of cellulosic biofuels from non-food crops is currently an area of intense research interest. Tailoring depolymerizing enzymes to particular feedstocks and pretreatment conditions is one promising avenue of research in this area. Here we added a green-waste compost inoculum to switchgrass (Panicum virgatum) and simulated thermophilic composting in a bioreactor to select for a switchgrass-adapted community and to facilitate targeted discovery of glycoside hydrolases. Small-subunit (SSU) rRNA-based community profiles revealed that the microbial community changed dramatically between the initial and switchgrass-adapted compost (SAC) with some bacterial populations being enriched over 20-fold. We obtained 225 Mbp of 454-titanium pyrosequence data from the SAC community and conservatively identified 800 genes encoding glycoside hydrolase domains that were biased toward depolymerizing grass cell wall components. Of these, {approx}10% were putative cellulases mostly belonging to families GH5 and GH9. We synthesized two SAC GH9 genes with codon optimization for heterologous expression in Escherichia coli and observed activity for one on carboxymethyl cellulose. The active GH9 enzyme has a temperature optimum of 50 C and pH range of 5.5 to 8 consistent with the composting conditions applied. We demonstrate that microbial communities adapt to switchgrass decomposition using simulated composting condition and that full-length genes can …

Increases in the dimensions of strike-slip faults including fault length, thickness of fault rock and the surrounding damage zone collectively provide quantitative definition of fault growth and are commonly measured in terms of the maximum fault slip. The field observations indicate that a common mechanism for fault growth in the brittle upper crust is fault lengthening by linkage and coalescence of neighboring fault segments or strands, and fault rock-zone widening into highly fractured inner damage zone via cataclastic deformation. The most important underlying mechanical reason in both cases is prior weakening of the rocks surrounding a fault's core and between neighboring fault segments by faulting-related fractures. In this paper, using field observations together with effective medium models, we analyze the reduction in the effective elastic properties of rock in terms of density of the fault-related brittle fractures and fracture intersection angles controlled primarily by the splay angles. Fracture densities or equivalent fracture spacing values corresponding to the vanishing Young's, shear, and quasi-pure shear moduli were obtained by extrapolation from the calculated range of these parameters. The fracture densities or the equivalent spacing values obtained using this method compare well with the field data measured along scan lines across the faults …

Analysis of compression wave propagation in a poroelastic medium predicts a peak of reflection from a high-permeability layer in the low-frequency end of the spectrum. An explicit formula expresses the resonant frequency through the elastic moduli of the solid skeleton, the permeability of the reservoir rock, the fluid viscosity and compressibility, and the reservoir thickness. This result is obtained through a low-frequency asymptotic analysis of Biot's model of poroelasticity. A review of the derivation of the main equations from the Hooke's law, momentum and mass balance equations, and Darcy's law suggests an alternative new physical interpretation of some coefficients of the classical poroelasticity. The velocity of wave propagation, the attenuation factor, and the wave number, are expressed in the form of power series with respect to a small dimensionless parameter. The absolute value of this parameter is equal to the product of the kinematic reservoir fluid mobility and the wave frequency. Retaining only the leading terms of the series leads to explicit and relatively simple expressions for the reflection and transmission coefficients for a planar wave crossing an interface between two permeable media, as well as wave reflection from a thin highly-permeable layer (a lens). Practical applications of the obtained …

Article on calculations predicting a large inverse H/D kinetic isotope effect on the rate of tunneling in the ring opening of cyclopropylcarbinyl radical.

This article offers a comparison of strategies and policies for building distributed digital preservation infrastructure.

A continuing goal in catalysis is the transformation of processes from homogeneous to heterogeneous. To this end, nanoparticles represent a new frontier in heterogeneous catalysis, where this conversion is supplemented by the ability to obtain new or divergent reactivity and selectivity. We report a novel method for applying heterogeneous catalysts to known homogeneous catalytic reactions through the design and synthesis of electrophilic platinum nanoparticles. These nanoparticles are selectively oxidized by the hypervalent iodine species PhICl{sub 2}, and catalyze a range of {pi}-bond activation reactions previously only homogeneously catalyzed. Multiple experimental methods are utilized to unambiguously verify the heterogeneity of the catalytic process. The discovery of treatments for nanoparticles that induce the desired homogeneous catalytic activity should lead to the further development of reactions previously inaccessible in heterogeneous catalysis. Furthermore, our size and capping agent study revealed that Pt PAMAM dendrimer-capped nanoparticles demonstrate superior activity and recyclability compared to larger, polymer-capped analogues.

We have conducted experiments on both the Vulcan and Titan laser facilities to study hot electron generation and transport in the context of fast ignition. Cu wires attached to Al cones were used to investigate the effect on coupling efficiency of plasma surround and the pre-formed plasma inside the cone. We found that with thin cones 15% of laser energy is coupled to the 40{micro}m diameter wire emulating a 40{micro}m fast ignition spot. Thick cone walls, simulating plasma in fast ignition, reduce coupling by x4. An increase of prepulse level inside the cone by a factor of 50 reduces coupling by a factor of 3.

Many perceive the implementation of environmental regulatory policy, especially concerning non-point source pollution from irrigated agriculture, as being less efficient in the United States than in many other countries. This is partly a result of the stakeholder involvement process but is also a reflection of the inability to make effective use of Environmental Decision Support Systems (EDSS) to facilitate technical information exchange with stakeholders and to provide a forum for innovative ideas for controlling non-point source pollutant loading. This paper describes one of the success stories where a standardized Environmental Protection Agency (EPA) methodology was modified to better suit regulation of a trace element in agricultural subsurface drainage and information technology was developed to help guide stakeholders, provide assurances to the public and encourage innovation while improving compliance with State water quality objectives. The geographic focus of the paper is the western San Joaquin Valley where, in 1985, evapoconcentration of selenium in agricultural subsurface drainage water, diverted into large ponds within a federal wildlife refuge, caused teratogenecity in waterfowl embryos and in other sensitive wildlife species. The fallout from this environmental disaster was a concerted attempt by State and Federal water agencies to regulate non-point source loads of the trace …

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A numerical experiment was carried out to test whether the patchy CO{sub 2} emission patterns observed at the ZERT release facility are caused by the presence of packers that divide the horizontal injection well into six CO2-injection zones. A three-dimensional model of the horizontal well and cobble-soil system was developed and simulations using TOUGH2/EOS7CA were carried out. Simulation results show patchy emissions for the seven-packer (six-injection-zone) configuration of the field test. Numerical experiments were then conducted for the cases of 24 packers (23 injection zones) and an effectively infinite number of packers. The time to surface breakthrough and the number of patches increased as the number of packers increased suggesting that packers and associated along pipe flow are the origin of the patchy emissions. In addition, it was observed that early breakthrough occurs at locations where the horizontal well pipe is shallow and installed mostly in soil rather than the deeper cobble. In the cases where the pipe is installed at shallow depths and directly in the soil, higher pipe gas saturations occur than where the pipe is installed slightly deeper in the cobble. It is believed this is an effect mostly relevant to the model rather than the field …

During an incident of national significance involving radioactive materials protective action guides (PAGs) are established to protect workers and the public from harmful exposure levels of radioactive materials. The PAGs are stated in terms of dose and must be converted to measurable quantities in various media (DRLs). This workshop will present the current PAGs, methods for converting the PAGs to DRLs, and using the Data Quality Objectives process in the Multi-agency Radiological Laboratory Analytical Protocols Manual (MARLAP), derive measurement quality objectives (MQOs) for the laboratories. Examples from the Empire 09 exercise will be used in this presentation.

Elastic behavior of geomechanical systems with interacting (but not intersecting) fractures is treated using generalizations of the Backus and the Schoenberg-Muir methods for analyzing layered systems whose layers are intrinsically anisotropic due to locally aligned fractures. By permitting the axis of symmetry of the locally anisotropic compliance matrix for individual layers to differ from that of the layering direction, we derive analytical formulas for interacting fractured regions with arbitrary orientations to each other. This procedure provides a systematic tool for studying how contiguous, but not yet intersecting, fractured domains interact, and provides a direct (though approximate) means of predicting when and how such interactions lead to more dramatic weakening effects and ultimately to failure of these complicated systems. The method permits decomposition of the system elastic behavior into specific eigenmodes that can all be analyzed, and provides a better understanding about which of these specific modes are expected to be most important to the evolving failure process.

Interferometric Synthetic Aperture Radar (InSAR), gathered over the In Salah CO{sub 2} storage project in Algeria, provides an early indication that satellite-based geodetic methods can be effective in monitoring the geological storage of carbon dioxide. An injected volume of 3 million tons of carbon dioxide, from one of the first large-scale carbon sequestration efforts, produces a measurable surface displacement of approximately 5 mm/year. Using geophysical inverse techniques we are able to infer flow within the reservoir layer and within a seismically detected fracture/ fault zone intersecting the reservoir. We find that, if we use the best available elastic Earth model, the fluid flow need only occur in the vicinity of the reservoir layer. However, flow associated with the injection of the carbon dioxide does appear to extend several kilometers laterally within the reservoir, following the fracture/fault zone.

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We report that iron-reducing bacteria are primary mediators of anaerobic carbon oxidation in upland tropical soils spanning a rainfall gradient (3500 - 5000 mm yr-1) in northeast Puerto Rico. The abundant rainfall and high net primary productivity of these tropical forests provide optimal soil habitat for iron-reducing and iron-oxidizing bacteria. Spatially and temporally dynamic redox conditions make iron-transforming microbial communities central to the belowground carbon cycle in these wet tropical forests. The exceedingly high abundance of iron-reducing bacteria (up to 1.2 x 10{sup 9} cells per gram soil) indicated that they possess extensive metabolic capacity to catalyze the reduction of iron minerals. In soils from the higher rainfall sites, measured rates of ferric iron reduction could account for up to 44 % of organic carbon oxidation. Iron reducers appeared to compete with methanogens when labile carbon availability was limited. We found large numbers of bacteria that oxidize reduced iron at sites with high rates of iron reduction and large numbers of iron-reducers. the coexistence of large populations of ironreducing and iron-oxidizing bacteria is evidence for rapid iron cycling between its reduced and oxidized states, and suggests that mutualistic interactions among these bacteria ultimately fuel organic carbon oxidation and inhibit CH4 …

The deposition of films under normal and off-normal angle of incidence has been investigated to show the relevance of non-sticking of and self-sputtering by energetic ions, leading to the formation of neutral atoms. The flow of energetic ions was obtained using a filtered cathodic arc system in high vacuum and therefore the ion flux had a broad energy distribution of typically 50-100 eV per ion. The range of materials included Cu, Ag, Au, Ti, and Ni. Consistent with molecular dynamics simulations published in the literature, the experiments show, for all materials, that the combined effects of non-sticking and self-sputtering are very significant, especially for large off-normal angles. Modest heating and intentional introduction of oxygen background affect the results.

The National Compact Stellarator Experiment's (NCSX) modular coils presented a number of engineering and manufacturing challenges due to their complex shapes, requirements for high dimensional accuracy and high current density requirements due to space constraints. Being the first of their kind, these coils required the implementation of many new manufacturing and measuring techniques and procedures. This was the first time that these manufacturing techniques and methods were applied in the production of coils at the laboratory. This resulted in a steep learning curve for the first several coils. Through the effective use of procedures, tooling modifications, involvement and ownership by the manufacturing workforce, and an emphasis on safety, the assembly team was able to reduce the manufacturing times and improve upon the manufacturing methods. This paper will discuss the learning curve and steps that were taken to improve the manufacturing efficiency and reduce the manufacturing times for the modular coils without forfeiting quality.