Methane Oxidation on Perovskite-Type Ca(Mn1−xTix)O3−δ

X-ray photoelectron spectroscopy was performed to elucidate the catalytic activity of CH₄ oxidation on perovskite-type Ca(Mn_{1− x} Ti _x )O_3−δ synthesized at 1173 K in a flow of oxygen from a gel with citric acid and ethylene glycol. The Mn ion content decreases and the ratio of the Mn³⁺ ion in the Mn ion increases with increases in x . Ca(Mn_{1− x} Ti _x )O_3−δ has a high catalytic activity of CH₄ oxidation at x =0.4. These results indicate that the catalytic activity strongly depends on the Mn³⁺ ion content of the surface.     

Selective formation of CH3OH in the photocatalytic reduction of CO2 with H2O on titanium oxides highly dispersed within zeolites and mesoporous molecular sieves

Highly dispersed titanium oxide catalysts have been prepared within zeolite cavities as well as in the zeolite framework and utilized as photocatalysts for the reduction of CO₂ with H₂O to produce CH₄ and CH₃OH at 328 K. In situ photoluminescence, ESR, diffuse reflectance absorption and XAFS investigations indicate that the titanium oxide species are highly dispersed within the zeolite cavities and framework and exist in tetrahedral coordination. The charge transfer excited state of the highly dispersed titanium oxide species play a significant role in the reduction of CO₂ with H₂O with a high selectivity for the formation of CH₃OH, while the catalysts involving the aggregated octahedrally coordinated titanium oxide species show a high selectivity to produce CH₄, being similar to reactions on the powdered TiO₂ catalysts. Ti-mesoporous molecular sieves exhibit high photocatalytic reactivity for the formation of CH₃OH, its reactivity being much higher than the powdered TiO₂ catalysts. The addition of Pt onto the highly dispersed titanium oxide catalysts promotes the charge separation which leads to an increase in the formation of CH₄ in place of CH₃OH formation.     

Control of nano-sized interlayer space of lamellar vanadyl benzylphosphate

Nano-sized interlayer space of lamellar vanadyl benzylphosphate was controlled by water content in starting solution. Depending on the water content, three types of lamellar vanadyl benzylphosphate having basal spacings of 1.4 nm, 1.9 nm and 2.3 nm were obtained. It was suggested that the difference in the concentrations of benzyl and hydroxyl groups in the interlayer leads to the variation of the interlayer space.     

A Coupled MPM-FDM Analysis Method for Multi-Phase Elasto-Plastic Soils

The Material Point Method (MPM), as proposed by Sulsky et al. (1994), has been developed to simulate large deformations and failure evolution involving different material phases in a single computational domain. A continuum body is divided into a finite number of subregions represented by Lagrangian material points, while the governing equations are formulated and solved with the Eulerian grid. Since this grid can be chosen arbitrarily, mesh tangling does not appear in the MPM. To design a simple but robust spatial discretization procedure, the MPM is coupled with the finite difference method (FDM) in the present study for simulating fully and partially saturated elasto-plastic soil responses based on the simplified three-phase method. Governing equations for the soil skeleton and the pore fluid are discretized by the MPM and FDM, respectively. Soil-water coupled analyses for fully saturated soils and seepage-deformation coupled analyses for unsaturated soils are performed, and the potential of the proposed method is demonstrated via numerical examples.     

Exposure and risk assessment of zinc in Japanese surface waters

In recent years, due to concerns on the potential effects of zinc on aquatic biota, zinc is receiving particular attention from regulatory agencies. A comprehensive exposure and risk assessment of zinc in Japanese surface waters was conducted to provide a scientific basis for developing realistic risk reduction measures for zinc. Emissions from corrosion contribute approximately 37% of the total zinc emissions to surface water in Japan. The zinc concentration distributions estimated using 12 years of monitoring data from 2075 sites by a maximum likelihood method indicated that the mean concentrations have gradually declined. The threshold concentrations (HC5 and PHC5) derived from organism- and population-level species sensitivity distributions were estimated to be 27 and 107 μg/L for total zinc, respectively. The risk characterization identified that during 1991-2002, 14.5-26.8% of the monitoring sites likely exceeded the HC5, whereas only 0.7-3.5% likely exceeded the PHC5. Evaluation of the effect of stormwater runoff to zinc concentrations in a river showed that zinc concentrations in river water increased significantly from roadway drainage flowing into the river. The cost-effectiveness analyses demonstrated that enforcement of the zinc national effluent standard may be effective at a certain level for public water areas in Japan; however, the degree of the effectiveness is highly dependent on the characteristics (e.g., sources and background) of the watersheds. An emissions and exposure assessment along with cost-effectiveness analysis is crucial for developing realistic and appropriate ecological risk management of zinc. The zinc RAD in Japan illustrated that in any “state-of-the science” method used, some degree of ecological risk from zinc can be observed in some Japanese water environments. On the other hand, zinc is a beneficial material for human industrial activities. Because zinc is an element, its role in industrial activities would be difficult to be substituted by other metals with less toxicity. In addition to improving science-based risk assessment methodologies which often focus on the toxicological perspectives, it is important to develop a more robust framework considering a trade-off between a damage in ecosystem and a benefit in human activities. Zinc can be a role model for it.     

Preparation of mesoporous silica replica using ordered mesoporous carbon by vapor phase transport of silica source

A new vapor phase transport (VPT) technique to prepare an inverse silica replica of an ordered mesoporous carbon was developed. Tetraethyl orthosilicate (TEOS) was infiltrated in mesoporous carbon CMK-3 as the hard template at 180 °C for 48 h under an autogenous pressure in an autoclave in the presence of water. The samples obtained by removal of CMK-3 retained structural regularity of CMK-3 with little shrinkage of framework, which were characterized by SAXRD, N₂ adsorption, TG-DTA, and SEM. Influence of preparation temperature on the loading amount of silica was investigated. The multi-step replication process was monitored by characterizing the replicated materials as well as intermediate composites.     

One-Step Oxidation of Benzene to Phenol over Cu/Ti/HZSM-5 Catalysts

The gas-phase catalytic oxidation of benzene over copper supported on HZSM-5 added with titanium (Cu/Ti/HZSM-5) was carried out by using molecular oxygen as an oxidant. Phenol was effectively produced by the titanium addition to Cu/HZSM-5. The titanium addition to Cu/HZSM-5 induces the easy reduction of Cu²⁺ species to Cu⁺ species in the catalysts, and the produced Cu⁺ species seems to produce the phenol effectively.     

Congener-specific carbon isotopic analysis of technical PCB and PCN mixtures using two-dimensional gas chromatography-isotope ratio mass spectrometry

Analysis of stable carbon isotope fractionation is a useful method to study the sources and fate of anthropogenic organic contaminants such as polychlorinated biphenyls (PCBs) in the environment. To evaluate the utility of carbon isotopes, determination of isotopic ratios of 13C/12C in source materials, for example, technical PCB preparations, is needed. In this study, we determined delta13C values of 31 chlorobiphenyl (CB) congeners in 18 technical PCB preparations and 15 chloronaphthalene (CN) congeners in 6 polychlorinated naphthalene preparations using two-dimensional gas chromatography-combustion furnace-isotope ratio mass spectrometry (2DGC-C-IRMS). Development of 2DGC-IRMS enabled improved resolution and sensitivity of compound-specific carbon isotope analysis (CSIA) of CB or CN congeners. Delta13C values of PCB congeners ranged from -34.4 (Delors) to -22.0/1000 (Sovol). Analogous PCB preparations with similar chlorine content, but different geographical origin, had different delta13C values. PCB preparations from Eastern European countries--Delors, Sovol, Trichlorodiphenyl, and Chlorofen--had distinct delta13C values. PCB mixtures showed increased 13C depletion with increasing chlorine content. Delta13C values for individual CB congeners varied depending on the degree of chlorination in technical mixtures. Delta13C values of CN congeners in Halowaxes ranged from -26.3 to -21.7/1000 and these values are within the ranges observed for PCBs. This study establishes the range of delta13C values in technical PCB and PCN preparations, which may prove to be useful in the determination of sources of these compounds in the environment. This is the first study to employ 2DGC-IRMS analysis of delta13C values in technical PCB and PCN preparations.     

Improved polyhydroxybutyrate (PHB) production in transgenic tobacco by enhancing translation efficiency of bacterial PHB biosynthetic genes

Polyhydroxybutyrate [P(3HB)] was produced in the transgenic tobacco harboring the genes encoding acetoacetyl-CoA reductase (PhaB) and polyhydroxyalkanoate synthase (PhaC) from Ralstonia eutropha (Cupriavidus necator) with optimized codon usage for expression in tobacco. P(3HB) contents in the transformants (0.2mg/g dry cell weight in average) harboring the codon-optimized phaB gene was twofold higher than the control transformants harboring the wild-type phaB gene. The immunodetection revealed an increased production of PhaB in leaves, indicating that the enhanced expression of PhaB was effective to increase P(3HB) production in tobacco. In contrast, codon-optimization of the phaC gene exhibited no apparent effect on P(3HB) production. This result suggests that the efficiency of PhaB-catalyzed reaction contributed to the flux toward P(3HB) biosynthesis in tobacco leaves.