Nonlinear ship waves and computational fluid dynamics.

Research works undertaken in the first author's laboratory at the University of Tokyo over the past 30 years are highlighted. Finding of the occurrence of nonlinear waves (named Free-Surface Shock Waves) in the vicinity of a ship advancing at constant speed provided the start-line for the progress of innovative technologies in the ship hull-form design. Based on these findings, a multitude of the Computational Fluid Dynamic (CFD) techniques have been developed over this period, and are highlighted in this paper. The TUMMAC code has been developed for wave problems, based on a rectangular grid system, while the WISDAM code treats both wave and viscous flow problems in the framework of a boundary-fitted grid system. These two techniques are able to cope with almost all fluid dynamical problems relating to ships, including the resistance, ship's motion and ride-comfort issues. Consequently, the two codes have contributed significantly to the progress in the technology of ship design, and now form an integral part of the ship-designing process.

Decomposition of polychlorinated biphenyls in soil with a dispersion mixture of metallic calcium and calcium oxide.

This study describes the decomposition of polychlorinated biphenyls (PCBs) in soil with dispersion mixtures of metallic calcium (Ca) and calcium oxide (CaO) at different temperatures. In these experiments, naturally moisturized and contaminated soil (1.0 g [31 ppm PCBs]), CaO (dried 2.0 wt%), and metallic Ca (0.01 g [0.25 mmol]) were introduced into a stainless steel pressure reactor under 0.1 MPa N(2) gas. The mixtures were stirred magnetically and heated at 260, 280, and 300 °C, respectively. Soil treatment with metallic Ca and CaO under various temperature conditions is extremely effective for degrading existing PCBs. Decomposition resulted from dechlorination (DC). Initial moisture in soil acted as a hydrogen source during stirring. Soil moisture can be beneficial for hydrodechlorination in the presence of metallic Ca and CaO. Furthermore, metallic Ca and CaO can greatly increase the number of collisions and mutual refinement. Treatment at 260, 280, and 300 °C combined with metallic Ca and CaO is effective for the decomposition (approximately 95 % DC) of PCBs in soil under natural moisture conditions.

Mechanochemical degradation of chlorinated contaminants in fly ash with a calcium-based degradation reagent.

This report presents our results in a low-temperature mechanochemical hydrodechlorination process applied to fly ash coming from a municipal waste incinerator in order to efficiently remove all traces of PCDDs, PCDFs and PCBs. We found that the most suitable degradation agent is a mixture of metallic calcium and calcium oxide. A sample of fly ash presenting a TEQ of 5200 pg g(-1) was completely detoxified (no traces of PCDDs, PCDFs and PCBs detected) after ball-milling at 400 rpm over night.

Polychlorinated dioxins, furans, and biphenyls in blood of children and adults living in a dioxin-contaminated area in Tokyo.

The soil of a residential area in Tokyo was found to contain dioxins, namely polychlorinated dioxins, furans, and dioxin-like biphenyls, the levels of which exceeded the environmental guideline [1,000 pg toxic equivalent (TEQ)/g] by up to 6.8 times. To assess the exposure levels of people living in this area and to study the possible relationship of blood dioxin concentrations of children with breast milk and/or formula feeding, a health survey was carried out in 2006, involving a total of 138 people, including 66 children aged 3-15 years, and blood dioxin concentrations and the characteristics and lifestyles of these people were analyzed. Mean ± standard error of the mean (SEM) of blood dioxin concentrations (pg/g-lipid) of group 1 (3-6 years old), group 2 (7-15 years old), and group 3 (≥16 years old) were 13 ± 1.9, 6.6 ± 0.65, and 10 ± 0.54, respectively. The congener/isomer profile of dioxins in blood samples differed markedly from that of the contaminated soil samples. According to the feeding mode of children, blood dioxin concentrations (pg/g-lipid) were 17 ± 2.9 for breast milk only, 7.4 ± 0.82 for both breast milk and formula, and 4.7 ± 1.1 for formula only, with a significant difference from one another. We conclude that people living in the dioxin-contaminated area are less likely to be exposed to excessive amounts of dioxins, and that blood dioxin concentrations of children aged 3-15 years seem to be strongly affected by breast feeding duration.

[Investigation of PCB pollution evaluation for Yusho victims using their preserved umblical cord].

PCB and dioxin-like PCB (DL-PCB) in 28 umbilical cords preserved from the time when 3 Yusho victims and 11 healthy subjects gave birth were examined in order to investigate the pollution evaluation with both the compounds in Yusho victims on the basis of the analytical value. As a result, in a period of 1968 to the 70s immediately after Yusho incident, the total concentration of the 12 DL-PCB isomers in both the Yusho victims s and healthy subjects was very high. After that, the total DL-PCB concentration decreased temporally. However, there was not observed a significant difference in the concentration and composition of both contaminants between the two groups.

Global contamination of coplanar polybrominated/chlorinated biphenyls (Co-PXBs) in the market fishes from Japan.

Polybrominated chlorinated biphenyls (PXBs, X=Br, Cl) are a group of environmental contaminants that have not been studied previously. The introduction of the second halogen to the biphenyl backbone increases the number of possible congeners to more than 9000. Only a limited number of PXBs are commercially available. In order to determine the occurrence of these compounds in environmental matrices, an isotope dilution HRGC/HRMS method for determination of five co-planar polybrominated/chlorinated biphenyls (Co-PXBs) in biota was developed. The method detection limit for these compounds ranged between 0.05 and 0.5 pg/g for 4'-monobromo-3,3',4,5-tetrachlorobiphenyl and 3',4',5'-tribromo-3,4-dichlorobiphenyl, respectively. Concentrations of five co-planar polybrominated and chlorinated biphenyls in eighteen different fish fillets from Japanese markets ranged between 4 and 46 pg/g wet weight for mink whale and young yellow-tail fish. These values are substantially lower than those reported for Co-PCBs; however, it should be noted that due to the unavailability of standards, identification and quantification of all the isomers was not possible.

Analytical method for determination of dinitropyrenes using gas chromatography-high-resolution mass spectrometry.

A gas chromatography-high-resolution mass spectrometry method has been developed for the determination of dinitropyrenes (DNPs). DNPs were reduced to the corresponding diaminopyrenes with sodium hydrosulfide, and the reduced DNPs were derivatized with N-methyl-bis(trifluoroacetamide). The sensitivity of this method was up to 10 times that of high-performance liquid chromatography with fluorescence detection. The detection limits for 1,3-, 1,6-, and 1,8-DNPs were in the 0.90-1.1 pg range. The concentrations were corrected with a correction factor determined from the recovery of an internal standard. The recovery of deuterium-labeled 6-nitrochrysene was at least 87%. This new method was utilized for quantitative determination of DNPs in Standard Reference Material (SRM) 1975 available from the US National Institute of Standards and Technology. Three DNP isomers were measured in SRM 1975 at 0.571-1.59 microg/g.

Formation of toxic chemicals including dioxin-related compounds by combustion from a small home waste incinerator.

We investigated combustion in a small home waste incinerator and analyzed both flue gas and residual ash for formation of the dioxin-related compounds polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and coplanar polychlorinated biphenyls and their precursors polychlorinated benzenes, polychlorinated phenols, polychlorinated diphenyl ethers, and polychlorinated biphenyls. Particularly, we investigated the effect of the incinerated material's composition on both the congener ratios of released compounds and the total concentration of all congeners of each compound. Eight different samples were prepared for incineration with four samples consist entirely paper, dead leaves, natural wood, or building materials. The remaining four samples contained mostly paper, but also other components such as fiber, non-chlorine-containing plastics, chlorine-containing plastics, and copper electric wire. The presence of non-chlorine-containing plastic in combustion samples did not increase overall dioxin or dioxin-precursor emissions. In contrast, chlorine-containing plastic resulted in a several-fold increase in total polychlorinated dioxins released, in both flue gas and residual ash. Copper wire resulted in a further several-fold increase in total polychlorinated dioxins and dioxin precursors released, with one exception: the addition of chlorine-containing plastic resulted in a many-fold increase in polychlorinated biphenyls, but only a modest further increase ( approximately 52%) with the further addition of copper. Homologue ratios tended toward higher-chlorine compounds as chlorine-containing plastic and Cu were added, but the results were far from uniform. Our results show that toxic dioxin release from small home waste incinerators must be considered significant, especially if even small amounts of chlorine-containing plastics or copper are burned.

Optimization of the purification method for dioxin analysis in human serum and temporal changes in background dioxin levels in the general population.

To perform high quality and high throughput measurements, complicated purification procedure by two rounds of open column chromatography was simplified by appraising the components and adding a sufficient amount of adsorbents to the column. The procedure consists of two open column techniques using a multi-layer silica gel column and an active carbon dispersed silica gel column. This purification procedure is used in "Standard manual for dioxin analysis in human blood" published in 2000 (Ministry of Health and Welfare, Japan, 2000). Consequently, a purification procedure using only 1 g of 10% AgNO(3)/silica gel can remove the matrix of blood serum as effectively as a multi-layer silica gel column. In addition, 0.1 g of carbon silica gel, equivalent to 1/10 the weight used currently in analyses, separates and recovers the dioxins in purified extract of blood serum. Furthermore, changes in the background level in the general population were clarified by monitoring the dioxin concentrations in human blood. The dioxin concentrations and ratios in blood in the general population remained at a tolerable level for three months. Therefore, the blood serum was available for the detection of a remarkable elevation in dioxins level considered to be indicative of contamination due to high-density exposure.

Assessment of human exposure to PCDDs, PCDFs and Co-PCBs using hair as a human pollution indicator sample I: Development of analytical method for human hair and evaluation for exposure assessment.

Dioxins including polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and co-planar polychlorinated biphenyls (Co-PCBs) are highly toxic. Even at environmental pollution levels, they cause hormonal damage in women, and they have been shown to induce immunosuppression and genital function damage in humans. In this study, a new method using isotope dilution was established to detect PCDDs, PCDFs and Co-PCBs in human hair. This method, comprised of washing and cutting of hair, alkaline decomposition, hexane extraction, multilayer silica gel column chromatography, high performance liquid chromatography with a porous graphite carbon column and analysis by high resolution gas chromatography/high resolution mass spectrometry, enabled us to analyze PCDDs, PCDFs and Co-PCBs at trace levels of less than pg/g with good reproducibility. In addition, there was a correlation between some isomers in human hair and blood collected from identical donors. Human hair analysis is useful to evaluate human risk assessment including that due to environmental pollution.

Comparison of polybrominated diphenyl ethers in fish, vegetables, and meats and levels in human milk of nursing women in Japan.

At present, little is known about the occurrence of polybrominated diphenyl ethers (PBDEs) in fish and food products sold in Japan. To investigate whether human exposure to PBDEs through the diet is significant, the concentrations of PBDEs were determined in fish and in meat and vegetables sold in two food markets in the city of Hirakata, Osaka prefecture. The concentrations of PBDEs in the breast milk of 12 primiparae nursing women at one month after delivery also were determined to ascertain the relationship between the levels found in the diet and levels in humans. sigma PBDE concentrations ranged between 21 and 1650 pg/g fresh weight in the edible tissues of five species of fish and one shellfish species. The highest concentrations were measured in yellow-fin tuna, followed by short-necked clam, salmon, yellowtail, mackerel and young yellowtail. Interestingly, sigma PBDE concentrations were not statistically significantly different in two cultured mackerel samples from Japan and mackerel collected from northern European waters. sigma PBDE concentrations in beef, pork and chicken meat (ranging between 6.25 and 63.6 pg/g fresh weight) and in three different vegetables (ranging between 38.4 and 134 pg/g fresh weight) were significantly lower than the concentrations in fish. In human milk, sigma PBDE concentrations ranged between 668 and 2840 pg/g lipid basis, which is comparable to the levels in populations of nursing women reported in Sweden and elsewhere. There was a strong positive relationship between PBDE concentrations in human milk and dietary intake of fish and shellfish, which was established in the women from responses to a questionaire on food consumption habits. The results of this study of food products commonly consumed in Japan and the levels found in nursing women raise a concern about low level PBDE contamination of fish and other foods intended for human consumption.

Formation of dioxin analogs by open-air incineration of waste wood and by fire of buildings and houses concerning Hanshin Great Earthquake in Japan.

Ash samples were collected from site of open-air incineration and fire concerning Hanshin Great Earthquake which occurred in western Japan in the early morning of 17 January 1995. The average concentrations of total sum of PCDDs, PCDFs and Co-PCBs in ash collected from wood scrap of broken building fire site, house fire site, shoe-making factory fire site and electric appliances store fire site were 541, 442, 859 and 22,800 pgTEQ/g, respectively. Particularly, PCDFs among dioxin analogs generated remarkably at sites with a high TEQ. In addition, 79,000 t of ash was totally produced at five open-air incineration sites, and consequently the formation amount of PCDDs, PCDFs and Co-PCBs was estimated to be 70.7 gTEQ on the basis of these analytical data.