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.     

Experimental study of cell pattern formation induced by internal heat sources in a horizontal fluid layer

This study determines the flow structure in a convection cell with an internally heated layer by PIV to elucidate the convection cell transition mechanisms. The vertical velocity component is determined and the cell behaviour with respect to Rayleigh number is investigated quantitatively. Cell expansion process is described as a consequence of development of the descending flow at the centre of cells. The results suggest that a spoke-like structure is stable in this system in ideal conditions and a double-cell structure is formed when there are restrictions on the system, i.e. finite lateral boundaries.     

Microstructural Analysis of Liquid-Phase-Sintered β-Silicon Carbide

The microstructures of fine-grained β-SiC materials with α-SiC seeds annealed either with or without uniaxial pressure at 1900°C for 4 h in an argon atmosphere were investigated using analytical electron microscopy and high-resolution electron microscopy (HREM). An applied annealing pressure can greatly retard phase transformation and grain growth. The material annealed with pressure consisted of fine grains with β-SiC as a major phase. In contrast, the microstructure in the material annealed without pressure consisted of elongated grains with half α-SiC. Energy-dispersive X-ray analysis showed no differences in the amount of segregation of aluminum and oxygen atoms at grain boundaries, but did show a significant difference in the segregation of yttrium atoms at grain boundaries along SiC grains for the two materials. The increased segregation of yttrium ions at grain boundaries caused by the applied pressure might be the reason for the retarded phase transformation and grain growth. HREM showed a thin secondary phase of 1 nm at the grain boundary interface for both materials. The development of a composite grain consisting of a mixture of β/α polytypes during annealing was a feature common to both materials. The possible mechanisms for grain growth and phase transformation are discussed.     

Defect structures and dopant solution states of Hf-doped Si3N4 ceramics

Transition-metal-doped silicon nitride ceramics have attracted much attention as gate materials for semiconductors because of their electrical properties as well as chemical and thermal stability. The present study aims to clarify the defect structures of Hf-doped β-Si₃N₄ by theoretical calculations and scanning transmission electron microscopy (STEM). First-principles calculations based on a hybrid functional method were performed. It was found that Hf dopants are mainly substituted for the Si sites and can be occasionally located at interstitial sites in the lattice of β-Si₃N₄. The substitution sites of Hf dopants predicted by the first-principles calculations were also confirmed by the high-resolution STEM images.     

A survey of perfluorooctane sulfonate and related perfluorinated organic compounds in water,fish, birds,and humans from Japan

Occurrence of perfluorooctane sulfonate (PFOS) in the tissues of humans and wildlife is well documented. In this study, concentrations and distribution of PFOS, perfluorohexane sulfonate (PFHS), and perfluorobutane sulfonate (PFBS) were determined in samples of surface water, fish and bird blood and livers, and human blood collected in Japan. Notable concentrations of PFOS were found in surface water and fish from Tokyo Bay. PFOS was found in all of the 78 samples of fish blood and liver analyzed. Based on the concentrations of PFOS in water and in fish livers, bioconcentration factors were calculated to range from 274 to 41 600. Concentrations of PFOS in the blood of Japanese human volunteers ranged from 2.4 to 14 ng/mL. PFHS was detected in 33% of the fishes analyzed, at concentrations severalfold less than those of PFOS.     

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.     

Weighting matrix of quadratic performance index and design method of optimal deadbeat control system

A method of determination of the weighting matrix of the quadratic performance index and a method of design of an optimal deadbeat control system are discussed. First, the relationship between the weighting matrix of the quadratic performance index and the extra poles of the overparametrized pulse transfer function model is indicated. Next, a method of design of an optimal deadbeat control system is explained. Lastly, to demonstrate the effectiveness of the proposed method, some numerical examples are presented. © 2000 Scripta Technica, Electr Eng Jpn, 133(1): 53–63, 2000