Regional and seasonal characteristics of emission sources of fine airborne particulate matter collected in the center and suburbs of Tokyo, Japan as determined by multielement analysis and source receptor models

Airborne particulate matter, suspected to induce adverse effects on human health, have been one of the most important concerns regarding recent air pollution issues in Japan. To characterize regional and seasonal variations in emission sources of fine airborne particulate matter (d < 2 microm), monthly samples (n = 36 for each site) were collected at urban (Tokyo), suburban (Maebashi), and mountainous (Akagi) sites in Japan from April 2003 to March 2006. Multielement analysis of chemical species (Na, Al, K, Ca, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Sb, and Pb) was performed by inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry. The combined source receptor model, which consists of positive matrix factorization and chemical mass balance, determined the contributions of nine emission sources (local and continental soils, road dust, coal and oil combustion, waste incineration, steel industry, brake wear, and diesel exhaust) to the observed elemental concentrations. Large regional differences were identified in the source contributions among the observational sites. Diesel exhaust was identified as the most significant source (70% of identified contributions) at the urban site. Local and continental soils, coal combustion, and diesel exhaust were intricately assigned (20-30% each) to the suburban site. Continental soil was the predominant source (65%) at the mountainous site. Respective significant source contributions dominated the seasonal variations of total elemental concentrations at each site. These results suggest that a better understanding of the regional and seasonal characteristics of impacting emission sources will be important for improving regional environments.     

Effective collection of hydrophobic organic pollutants in water with aluminum hydroxide and hydrophobically modified polyacrylic acid

Polyacrylic acid was hydrophobically modified with dodecylamine and used as a coagulant for coprecipitation of hydrophobic organic pollutants from water. The polymer coagulant induced effective aggregation of aluminum hydroxide having hydrophobic regions which are essential for the incorporation of hydrophobic organic pollutants. Recoveries of the organic pollutants increased with increasing the dodecylamine content, which indicated that the dodecylamine moiety played an important role in the formation of hydrophobic area on the precipitate. Different hydrophobic organic pollutants that had hardly been removed by the conventional coprecipitation were successfully collected by the proposed method.     

Comparison of Surface Organic Compound Mass Spectrum Patterns by LD-TOFMS for Megalopolis Atmospheric Particles and Diesel Exhaust Particles (DEP)

PM_2.5 and PM₁₀ samples for megalopolis atmospheric particles were collected at Shinjuku, Tokyo in December 1998–January 1999 and August 1999, for two weeks both in winter and summer, with a 24 hr sampling interval. Sampling of PM_2.5 and PM₁₀ in diesel exhaust particles (DEP) was carried out using an automobile exhaust testing system, with a diesel truck placed on a chassis dynamometer. Sampling conditions included idling, constant speed of 40 km hr^-1, M-15 test pattern and 60%-revolution/40%-load of maximum power. Mass spectrums of organic compounds adhering to the surface of the PM_2.5 and PM₁₀ samples were analyzed by laser desorption time-of-flight mass spectrometry (LD-TOFMS, analytical mass range: m/z 1–m/z 380 000). LD-TOFMS analysis of those samples revealed consistently the detection of low-mass organic compounds up to m/z 800. For the megalopolis atmospheric particles, the mass spectrum pattern of wintertime samples was almost the same as that of the summertime samples for both PM_2.5 and PM₁₀. The major peak was m/z 177, and the minor peaks were m/z 84, 94, 101, 163, 189 and 235. The mass spectrum pattern of DEP was the same for all samples under all test conditions. The major peak was m/z 101, and other detected peaks were small.     

Concentrations, enrichment and predominant sources of Sb and other trace elements in size classified airborne particulate matter collected in Tokyo from 1995 to 2004

APM was collected and trace elements existing in the particles were monitored since May 1995 in this study. APM sample was collected separately by size (d < 2 microm, 2-11 microm and >11 microm) on the roof of the university building (45 m above ground) in the campus of Faculty of Science and Engineering, Chuo University, Tokyo, Japan, using an Anderson low volume air sampler. The collected sample was digested by HNO3, H2O2 and HF using a microwave oven, and major elements (Na, Mg, Al, K, Ca and Fe) were measured by ICP-AES, and trace elements (Li, Be, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, As, Se, Mo, Cd, Sb, Ba and Pb) were measured by ICP-MS. It was observed that the APM concentration was higher between the winter and the spring, compared to during the summer. The enrichment factor was calculated for each element in each set of APM (d < 2 microm, 2-11 microm and >11 microm). Seasonal trends of enrichment factors were examined, and the elements were classified into 3 groups according to the common seasonal behavior. It is likely that the elements in the same group have common origins. Toxic pollutant elements (Sb, Se, Cd, Pb and As) were found in small particles with d of <2 microm in concentrated levels. Antimony (Sb) had the highest enrichment factor, and the results suggested that Sb level in APM was extremely high. The origins of Sb were sought, and wastes from plastic incineration and brake pad wears of automobiles were suspected. Each set of APM (d < 2 microm, 2-11 microm and >11 microm) was classified by the shape, and the shape-dependent constituents of a single APM particle were quantitatively measured by SEM-EDX. High concentration of Sb was found in APM <2 microm and square particles. Particles less than 2 microm and square shaped particles were major particles produced by actual car braking experiments. From these experimental results it was concluded that the source of Sb in squared APM <2 microm is considered to be from brake pad wear.     

Oxygen Permeability and Biodegradability of Polyuronic Acids Prepared from Polysaccharides by TEMPO-Mediated Oxidation

Polyuronic acids, i.e., amylouronic acid, cellouronic acid and chitouronic acid, were prepared from starch, cellulose and chitin, respectively, by the 2,2,6,6-tetramethylpiperidine-1-oxy radical (TEMPO)-mediated oxidation, and their gas-barrier properties and biodegradability were studied in consideration to use the polyuronic acids as flexible packaging films or coating materials. Cellouronic acid and amylouronic acid had excellent oxygen-barrier properties similar to that of poly(vinyl alcohol) (PVA), while chitouronic acid did not. The regular chemical structures of the former two polyuronic acids with no bulky substituents or adducts may have brought about such high oxygen-barrier levels. An oxidized product prepared form fine microcrystalline cellulose by the TEMPO-mediated oxidation was not completely dissolved in water, but became a paste. However, this paste also formed sufficiently smooth films by coating, and had good gas-barrier property. All polyuronic acids prepared were biodegradable; cellouronic acid and chitouronic acid had high degrees of biodegradability, while amylouronic acid had quite low value. These various characteristics are significant for end use of these new polyuronic acids as gas-barrier materials for biodegradable packaging.     

Numerical analysis of gas explosion inside two rooms connected by ducts

Simulations of gas explosion of hydrogen/air mixture inside two rooms connected by ducts are carried out. Scalar transport chemical reaction model and LES turbulence model are utilized to reduce the calculation load and to conduct real-scale analysis. The effects of ignition source locations and volume of ignited room are analyzed, and the time history of pressure and rate of pressure rise in each room are focused in this study. When the volume of the ignited room is larger than the other room, the high pressure from the other room causes a force to act on the partition to the ignited room. This study indicates that the current technique can predict specific features of gas explosions inside two rooms connected by the ducts.     

Degradation of dibromophenols by UV irradiation

We examined the degradation of dibromophenols （DBPs）, i.e. 2,4-DBP, 2,6-DBP and 3,5-DBP by ultraviolet （UV） irradiation and estimated the relationship between degradability and molecular orbital properties of each dibromopbenol. The removal of DBPs under a UV lamp system was successfully performed in an aqueous solution. After 5 min of irradiation, the initial DBPs concentration of 20 mg/L was decreased to below 1 mg/L, and about 60% of bromide ion was released. A decrease in the concentration of dissolved organic carbon （DOC） suggested the mineralization of DBPs, The mineralization may occur after release of bromide ions because the decrease of DOC was slower than the release of bromide ions. The degradability of 3,5-DBP was slightly lower than 2,6-DBP and 2,4-DBE Molecular orbital calculation suggested that the electrophilic frontier density and the highest occupied molecular orbital （HOMO） energy may be related to the degradability of DBPs.