Studies on automated survey system of environmental chemicals by gas chromatography-mass spectrometry-computer II. Three dimensional mass chromatography

A three dimensional mass chromatography (TDMC), which is the extended method of mass chromatography, has been developed for the analysis of environmental chemicals. A considerable performance was suggested by the combination of TDMC to gas chromatography-mass spectrometry-computer system.     

Regional-specific emission inventory for NH3, N2O, and CH4 via animal farming in South, Southeast, and East Asia

Ammonia, nitrous oxide, and methane emission from animal farming of South, Southeast, and East Asia, in 2000, was estimated at about 4.7 Tg NH₃–N, 0.51 Tg N₂O–N, and 29.9 Tg CH₄, respectively, using the FAO database and countries’ statistic databases as activity data, and emission factors taking account of regional characteristics. Most of these atmospheric components, up to 60–80%, were produced in China and India. Pakistan, Bangladesh, and Indonesia, which were large source countries next to China and India, contributed more than a few percent of total emission of each atmospheric component. The largest emission livestock were cattle whose contribution was considerably high in South, Southeast, and East Asia; more than one-fourth of ammonia and nitrous oxide emissions: more than half of methane emission. The other major livestock for nitrous oxide and ammonia emissions were pigs. For methane emission, buffaloes were second source livestock. To provide spatial distributions of these gases, the emissions of county and district level were allocated into each 0.5° grid by means of the weighting by high-resolution land cover datasets. The regions with considerable high emissions of all components were able to be found at the Ganges delta and the Yellow River basin. The spatial distributions for ammonia and nitrous oxide emissions were similar but had a substantial difference from methane distribution.     

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.     

Residual organic fluorinated compounds from thermal treatment of PFOA,PFHxA and PFOS adsorbed onto granular activated carbon (GAC)

Perfluorooctanoic acid (PFOA), perfluorohexanoic acid (PFHxA) and perfluorooctane sulfonate (PFOS) adsorbed onto granular activated carbon (GAC) were thermally treated in N₂ gas stream. The purpose was to assess the fate of perfluoroalkyl and polyfluoroalkyl substances (PFASs) during thermal regeneration of GAC, which had been used for water treatment. Mineralized F, residual PFASs including short-chained species, and volatile organic fluorine (VOF) were determined. In a temperature condition of 700 °C, VOF were 13.2, 4.8, and 5.9 % as for PFOA, PFHxA, and PFOS. However, the VOF decreased to 0.1 %, if the GAC and off-gas were kept at 1000 °C. No PFASs remained in GAC at 700–1000 °C; at the same time, short-chained PFASs were slightly detected in the aqueous trapping of off-gas at 800 and 900 °C conditions. The destruction of PFASs on GAC could be perfect if the temperature is higher than 700 °C; however, the process is competitive against volatile escape from GAC. Destruction in gaseous phase needs a temperature as high as 1000 °C. Destruction of PFASs on the surface of GAC, volatile escape from the site, and thermolysis in gas phase should be considered, as to thermal regeneration of GAC.     

Effect of polyethylene addition to coal on hydrogasification enhancement

Hydrogasification of a coal/polyethylene mixture was carried out using a low concentration of polyethylene in the samples with the aim of industrial application. Coal/polyethylene mixtures in the ratio of 90:10 and 75:25 were used in this study. A hydrogasification experiment was conducted using a unique batch reactor at 1073 K under a 7.1 MPa hydrogen atmosphere. The reaction time varied from 1 to 80 s. The results revealed a methane yield from the mixtures that was noticeably greater than the values calculated from experimental results obtained from coal and polyethylene respectively, assuming no mutual influences. A significant synergistic effect was observed even when the polyethylene content was as low as 10 %. It is suggested that there might be an advantage in hydrogasification processes if waste plastics are mixed with coal, such content being practically assumed.     

Heterogeneous loss of HO2 by KCl,synthetic sea salt,and natural seawater aerosol particles

The HO₂ uptake to aerosol particles is potentially significant sink for the HO₂ radical in the marine atmosphere. To assess the heterogeneous loss of HO₂ on marine aerosol particles, we have investigated the uptake coefficients (γ) of HO₂ for submicron aerosol particles of KCl, synthetic sea salt, and natural seawater under ambient conditions (760 Torr and 296 ± 2 K) using an aerosol flow tube (AFT) coupled with a chemical conversion/laser-induced fluorescence (CC/LIF) technique. γ values determined for dry and wet aerosols of KCl were 0.02 ± 0.01 and 0.07 ± 0.03 at 66% and 75% RH, respectively, while γ values for those doped with CuSO₄ was 0.55 ± 0.19 at 75% RH. γ values determined for synthetic sea-salt particles were 0.07 ± 0.03, 0.12 ± 0.04 and 0.13 ± 0.04 at 35%, 50%, 75% RH, respectively, while γ values for natural seawater particles were 0.10 ± 0.03, 0.11 ± 0.02 and 0.10 ± 0.03 at 35%, 50%, 75% RH, respectively. We recommend a HO₂ uptake coefficient in marine areas of 0.1 for modeling and estimated the contribution of heterogeneous loss of HO₂ by sea-salt aerosol particles in marine areas using a box model. Our box-model simulations suggested that daytime maximum HO₂ concentrations decreased to 87–94% of the values without heterogeneous loss.     

Age-Dependent Factors Affecting Thoracic Response: A Finite Element Study Focused on Japanese Elderly Occupants

Objectives: The ultimate goal of this research is to reduce thoracic injuries due to traffic crashes, especially in the elderly. The specific objective is to develop and validate a full-body finite element model under 2 distinct settings that account for factors relevant for thoracic fragility of elderly: one setting representative of an average size male and one representative of an average size Japanese elderly male.

Methods: A new thorax finite element model was developed from medical images of a 71-year-old average Japanese male elderly size (161cm, 60 kg) postmortem human subject (PMHS). The model was validated at component and assembled levels against original series of published test data obtained from the same elderly specimen. The model was completed with extremities and head of a model previously developed. The rib cage and the thoracic flesh materials were assigned age-dependent properties and the model geometry was scaled up to simulate a 50th percentile male. Thereafter, the model was validated against existing biomechanical data for younger and elderly subjects, including hub-to-thorax impacts and frontal impact sled PMHS test data. Finally, a parametric study was conducted with the new models to understand the effect of size and aging factors on thoracic response and risk of rib fractures.

Results: The model behaved in agreement with tabletop test experiments in intact, denuded, and eviscerated tissue conditions. In frontal impact sled conditions, the model showed good 3-dimensional head and spine kinematics, as well as rib cage multipoint deflections. When properties representative of an aging person were simulated, both the rib cage deformation and the predicted number of rib fractures increased. The effects of age factors such as rib cortical thickness, mechanical properties, and failure thresholds on the model responses were consistent with the literature. Aged and thereby softened flesh reduced load transfer between ribs; the coupling of the rib cage was reduced. Aged costal cartilage increased the severity of the diagonal belt loading sustained by the lower loaded rib cage.

Conclusions: When age-specific parameters were implemented in a finite element (FE) model of the thorax, the rib cage kinematics and thorax injury risk increased. When the effect of size was isolated, 2 factors, in addition to rib material properties, were found to be important: flesh and costal cartilage properties. These 2 were identified to affect rib cage deformation mechanisms and may potentially increase the risk of rib fractures.     

Behavior of PCNs, PCDDs, PCDFs, and dioxin-like PCBs in the thermal destruction of wastes containing PCNs

In the first known study to characterize the emissions of polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (dl-PCBs) from the thermal treatment of wastes containing PCNs, the formation and decomposition behavior of these pollutants was investigated both at laboratory scale and at plant scale. Exhaust gas measurements from laboratory-scale combustion of rubber belts containing PCNs (FB belts) were used as the basis for calculations predicting that the incremental dioxin toxic equivalency (TEQ) emissions from municipal solid waste (MSW) incinerators would be less than 0.1 ng/m3 N. In order to directly examine co-incineration of FB belts with MSW and to address potential differences between the laboratory experiment and full-scale MSW incinerators, experiments were conducted using a larger scale thermal treatment test facility with sampling and analysis at several points in the thermal treatment process. Congener specific analysis of PCNs clearly showed that both destruction and synthesis simultaneously occurred during combustion in the kiln. Most of the PCNs were destroyed by secondary combustion, and almost all PCNs were removed after flue gas treatment. Almost all PCDDs/DFs were synthesized as by-products of kiln combustion, most of them were destroyed by the secondary combustion, and almost all dioxins (PCDDs/DFs and dl-PCBs) were removed after flue gas treatment. The TEQ emission levels were less than 0.1 ng/m3 N for all plant-scale tests, and differences in TEQ emission levels were very small. Adding wastes containing PCNs to MSW will not influence thermal treatment emissions to the environment from modern solid waste incinerators.