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Several conversion pathways of lignocellulosic biomass to advanced biofuels require or benefit from using concentrated sugar syrups of 600 g/L or greater. And while concentration may seem straightforward, thermal sugar degradation and energy efficiency remain major concerns. This study evaluated the trade-offs in product recovery, energy consumption, and economics between evaporative and membrane-based concentration methods. The degradation kinetics of xylose and glucose were characterized and applied to an evaporator process simulation. Though significant sugar loss was predicted for certain scenarios due to the Maillard reaction, industrially common falling-film plate evaporators offer short residence times (<5 min) and are expected to limit sugar losses. Membrane concentration experiments characterized flux and sugar rejection, but diminished flux occurred at >100 g/L. A second step using evaporation is necessary to achieve target concentrations. Techno-economic process model simulations evaluated the overall economics of concentrating a 35 g/L sugar stream to 600 g/L in a full-scale biorefinery. A two-step approach of preconcentrating using membranes and finishing with an evaporator consumed less energy than evaporation alone but was more expensive because of high capital expenses of the membrane units.

Nanomaterials are increasingly being used to improve the properties and functions of common building materials. A new type of self-cleaning cement incorporating TiO₂ nanomaterials (TiO₂-NMs) with photocatalytic properties is now marketed. This promising cement might provide air pollution-reducing properties but its environmental impact must be validated. During cement use and aging, an altered surface layer is formed that exhibits increased porosity. The surface layer thickness alteration and porosity increase with the cement degradation rate. The hardened cement paste leaching behavior has been fully documented, but the fate of incorporated TiO₂-NMs and their state during/after potential release is currently unknown. In this study, photocatalytic cement pastes with increasing initial porosity were leached at a lab-scale to produce a range of degradation rates concerning the altered layer porosity and thickness. No dissolved Ti was released during leaching, only particulate TiO₂-NM release was detected. The extent of release from this batch test simulating accelerated worst-case scenario was limited and ranged from 18.7 ± 2.1 to 33.5 ± 5.1 mg of Ti/m² of cement after 168 h of leaching. TiO₂-NMs released into neutral aquatic media (simulate pH of surface water) were not associated or coated by cement minerals. The TiO₂-NM release mechanism is suspected to start from freeing of TiO₂-NMs in the altered layer pore network due to partial cement paste dissolution followed by diffusion into the bulk pore solution to the surface. The extent of TiO₂-NM release was not solely related to the cement degradation rate.

There has been great progress in the development of technology for the conversion of lignocellulosic biomass to sugars and subsequent fermentation to fuels. However, plant lignin remains an untapped source of materials for production of fuels or high value chemicals. Biological cleavage of lignin has been well characterized in fungi, in which enzymes that create free radical intermediates are used to degrade this material. In contrast, a catabolic pathway for the stereospecific cleavage of β-aryl ether units that are found in lignin has been identified in Sphingobium sp. SYK-6 bacteria. β-Aryl ether units are typically abundant in lignin, corresponding to 50–70% of all of the intermonomer linkages. Consequently, a comprehensive understanding of enzymatic β-aryl ether (β-ether) cleavage is important for future efforts to biologically process lignin and its breakdown products. The crystal structures and biochemical characterization of the NAD-dependent dehydrogenases (LigD, LigO, and LigL) and the glutathione-dependent lyase LigG provide new insights into the early and late enzymes in the β-ether degradation pathway. We present detailed information on the cofactor and substrate binding sites and on the catalytic mechanisms of these enzymes, comparing them with other known members of their respective families. Information on the Lig enzymes provides new insight into their catalysis mechanisms and can inform future strategies for using aromatic oligomers derived from plant lignin as a source of valuable aromatic compounds for biofuels and other bioproducts.

In the post-Fukushima world, the stability of materials under extreme conditions is an important issue for the safety of nuclear reactors. Because the nuclear industry is going to continue using advanced zirconium cladding materials in the foreseeable future, it become critical to gain fundamental understanding of the several interconnected problems. First, what are the thermodynamic and kinetic factors affecting the oxidation and hydrogen pick-up by these materials at normal, off-normal conditions, and in long-term storage? Secondly, what protective coatings (if any) could be used in order to gain extremely valuable time at off-normal conditions, e.g., when temperature exceeds the critical value of 2200°F? Thirdly, the kinetics of oxidation of such protective coating or braiding needs to be quantified. Lastly, even if some degree of success is achieved along this path, it is absolutely critical to have automated inspection algorithms allowing identifying defects of cladding as soon as possible. This work strives to explore these interconnected factors from the most advanced computational perspective, utilizing such modern techniques as first-principles atomistic simulations, computational thermodynamics of materials, diffusion modeling, and the morphological algorithms of image processing for defect identification. Consequently, it consists of the four parts dealing with these four problem areas preceded by the introduction and formulation of the studied problems. In the 1st part an effort was made to employ computational thermodynamics and ab initio calculations to shed light upon the different stages of oxidation of ziraloys (2 and 4), the role of microstructure optimization in increasing their thermal stability, and the process of hydrogen pick-up, both in normal working conditions and in long-term storage. The 2nd part deals with the need to understand the influence and respective roles of the two different plasticity mechanisms in Zr nuclear alloys: twinning (at low T) and crystallographic slip (higher T’s). For that goal, a description of the advanced plasticity model is outlined featuring the non-associated flow rule in hcp materials including Zr. The 3rd part describes the kinetic theory of oxidation of the several materials considered to be perspective coating materials for Zr alloys: SiC and ZrSiO₄. In the 4th part novel and advanced projectional algorithms for defect identification in zircaloy coatings are described. In so doing, the author capitalized on some 12 years of his applied industrial research in this area. Our conclusions and recommendations are presented in the 5th part of this work, along with the list of used literature and the scripts for atomistic, thermodynamic, kinetic, and morphological computations.

Degradation phenomena and inference of their underlying mechanisms during 2 C cycle aging in a cell design comprising {l_brace}LiMn1/3Ni1/3Co1/3O2 + LiMn2O4{r_brace} composite positive electrode are studied and reported in this work. We describe how aging phenomena in the cells were studied and incremental capacity analysis applied to infer cell degradation mechanisms in the cycle aging process. Two stages of degradation were observed in the life cycle under this aging regime. In the first stage, we conclude that loss of lithium inventory was the cause of capacity fade. As a result of such parasitic loss, the cell further suffered from loss of active materials in the second stage, in which the positive electrode kinetics was hampered and the capacity loss accelerated.

The object of this work was to identify correlations between performance losses of Pt electrocatalysts on carbon support materials and the chemical and morphological parameters that describe them. Accelerated stress testing, with an upper potential of 1.2 V, was used to monitor changes to cathode properties, including kinetic performance and effective platinum surface area losses. The structure and chemical compositions were studied using X-ray Photoelectron Spectroscopy and Scanning Electron Microscopy coupled with Digital Image Processing. As this is an ongoing study, it is difficult to draw firm conclusions, though a trend between support surface area overall performance loss was found to exist.

This report documents the progress made through FY 2010 on a project initiated in FY 2006 to help address uncertainties related to the rates of hydrolysis in groundwater at the Hanford Site for carbon tetrachloride (CT) and chloroform (CF). The study also explores the possible effects of contact with minerals and sediment (i.e., heterogeneous hydrolysis) on these rates. The research was initiated to decrease the uncertainties in abiotic degradation rates of CT and chloroform CF associated with temperature and possible heterogeneous effects. After 2 years of data collection, the first evidence for heterogeneous effects was identified for hydrolysis of CT, and preliminary evidence for the effects of different mineral types on CF hydrolysis rates also was reported. The CT data showed no difference among mineral types, whereas significant differences were seen in the CF results, perhaps due to the fact that CF hydrolyzes by both neutral and base-catalyzed mechanisms whereas CT follows only the neutral hydrolysis path. In this report, we review the project objectives, organization, and technical approaches taken, update the status and results of the hydrolysis-rate experiments after 4 years of experimentation (i.e., through FY 2010), and provide a brief discussion of how these results add to scientific understanding of the behavior of the CT/CF plume at the Hanford Site.

O-ethyl S-(2-diisopropylaminoethyl)phosphonothiolate (VX) is the most toxic of the conventional chemical warfare agents. It is a persistent compound, an attribute derived from its relative involatility and slow rates of hydrolysis. These properties suggest that VX can linger in an exposed environment for extended periods of time long after the air has cleared. Concern over prolonged risk from VX exposure is exacerbated by the fact that it poses a dermal contact hazard. Hence a detailed understanding of volatilization rates, and degradation pathways and rates occurring in various environments is needed. Historically, volatilization has not been considered to be an important mechanism for VX depletion, but recent studies have shown that a significant fraction of VX may volatilize, depending on the matrix. A significant body of research has been conducted over the years to unravel VX degradation reaction pathways and to quantify the rates at which they proceed. Rigorous measurement of degradation rates is frequently difficult, and thus in many cases the degradation of VX has been described in terms of half lives, while in fewer instances rate constants have been measured. This variable approach to describing degradation kinetics reflects uncertainty regarding the exact nature of the degradation mechanisms. In this review, rates of VX degradation are compared on the basis of pseudo-first order rate constants, in order to provide a basis for assessing likelihood of VX persistence in a given environment. An issue of specific concern is that one VX degradation pathway produces S-2-(diisopropylaminoethyl) methylphosphonothioic acid (known as EA2192), which is a degradation product that retains much of the original toxicity of VX. Consequently degradation pathways and rates for EA2192 are also discussed.

This report documents the progress made through FY 2009 on a project initiated in FY 2006 to help address uncertainties related to the rates of hydrolysis in groundwater for carbon tetrachloride (CT) and chloroform (CF). The study seeks also to explore the possible effects of contact with minerals and sediment (i.e., heterogeneous hydrolysis) on these rates. In previous years the work was funded as two separate projects by various sponsors, all of whom received their funding from the U.S. Department of Energy (DOE). In FY2009, the projects were combined and funded by CH2MHill Plateau Remediation Corporation (CHPRC). Work in FY2009 was performed by staff at the Pacific Northwest National Laboratory (PNNL). Staff from the State University of New York at Cortland (SUNY–Cortland) contributed in previous years.

A hydrogen peroxide-based decontaminant, Decon Green, is efficacious for the decontamination of chemical agents VX (S-2-(diisopropylamino)ethyl O-ethyl methylphosphonothioate), GD (Soman, pinacolyl methylphosphonofluoridate), and HD (mustard, bis(2-chloroethyl) sulfide); the biological agent anthrax (Bacillus anthracis); and radiological isotopes Cs-137 and Co-60; thus demonstrating the ability of this decontamination approach to ameliorate the aftermath of all three types of weapons of mass destruction (WMD). Reaction mechanisms afforded for the chemical agents are discussed as are rationales for the enhanced removal efficacy of recalcitrant 60Co on certain surfaces. Decontaminants of this nature can be deployed, and are effective, at very low temperatures (-32 °C), as shown for studies done with VX and HD simulants, without the need for external heat sources. Finally, the efficacy of a lower-logistics, dry decontaminant powder concentrate (utilizing the solid active-oxygen compounds peracetyl borate and Peroxydone) which can be reconstituted with water in the field prior to use, is presented.