Non-degradable triazine substrates of atrazine and cyanuric acid hydrothermally and in supercritical water under the UV-illuminated photocatalytic cooperation

Strong oxidation by titanium dioxide photocatalysis can occur by photodegradation of organic contaminants in air and water. Some endocrine disruptors such as 2,4-dichlorophenoxy acetic acid (;;; ), 2,4-dichlorophenol (;;; ), nonylphenol (; ), bisphenol A (), diethyl phthalate (; ), etc. which can be neither biodegraded by bacteria nor degraded thermally can be degraded by TiO(2) photocatalytic treatment. However, incomplete photomineralization partly occurred, when TiO(2) photocatalytic degradation is employed for the treatment of certain endocrine disruptors. For example, no atrazine pesticide having triazine skeleton can be completely mineralized even by a photocatalytic procedure; the photodegradation of atrazine ultimately stops at the intermediate step of cyanuric acid, which cannot be photodegraded even after long illumination times ().In this study, the decomposition of atrazine and cyanuric acid was carried out with a device combining photocatalytic degradation in supercritical water (scH(2)O) or hydrothermal water (hyH(2)O). Atrazine and cyanuric acid can be degraded by the cooperation of either scH(2)O or hyH(2)O and UV illuminated TiO(2)-photocatalytic dispersed system under the fixed pressure of 23 MPa at 623 K or 683 K in a 120-ml Hastelloy batch reactor. The photocatalytic degradation method under high temperature and pressure has found appropriate for the photocatalytic oxidation of acetic acid and 2-chlorobiphenyl under continuous flow conditions at 160 degrees C and 20 atm (). In addition, the wet peroxide oxidation of PCBs by high temperature and pressure has been reported (). The main aims of this research are following. (i): the degradation of atrazine and cyanuric acid within the scH(2)O or hyH(2)O, (ii) the decomposition of atrazine and cyanuric acid catalyzed by TiO(2) particles under scH(2)O or hyH(2)O, and the synergistic effect for several reactions with TiO(2) and scH(2)O or hyH(2)O, and (iii) the mineralization yield of nitrogen and chlorine atoms concerning the chemical structures of atrazine or cyanuric acid (only nitrogen).     

Decomposition and removal of ionic liquid in aqueous solution by hydrothermal and photocatalytic treatment

We demonstrated a complete decomposition method for ionic liquids (ILs; organic cation part: butyl-methyl or ethyl-methyl imidazolium, and inorganic anion part: PF₆ ⁻, BF₄ ⁻ or Br⁻) in aqueous media by combining a hydrothermal mineralization method with a photocatalytic decomposition (PD) method. As a result, the hydrothermal treatment with Ca(OH)₂ mineralizer could effectively remove the inorganic anion part, such as PF₆ ⁻ or BF₄ ⁻ and the PD could decompose the organic cation part effectively. Therefore, the detoxification of ILs in aqueous media was accomplished by the present method.     

Iron-induced decomposition of perfluorohexanesulfonate in sub- and supercritical water

Decomposition of perfluorohexanesulfonate (PFHS), a bioaccumulative analogue of perfluorooctanesulfonate (PFOS), in sub- and supercritical water was investigated. Although PFHS was only slightly reactive in pure subcritical water at 350 degrees C, it decomposed to F(-) and SO(4)(2-) ions when the temperature was increased to 380 degrees C, at which temperature the water became supercritical state. Addition of zerovalent iron to the reaction system dramatically accelerated PFHS decomposition to F(-) ions in both sub- and supercritical water: for example, when the initial PFHS concentration was 741microM, the F(-) yields at 350 degrees C were 4.13-16.0 times as high as those in the absence of iron, depending on the amount and the particle size of the iron powder. After the reactions, small amounts of CO(2) and CF(3)H were also detected in the gas phase; these increased with temperature, and the amount of CF(3)H increased markedly when the reaction was carried out in supercritical water. Increasing the specific surface area of the iron powder markedly increased PFHS consumption and F(-) formation in the aqueous phase, which indicates that the reactions occurred on the iron surface and that the increased specific surface area was a key factor in accelerating the decomposition of PFHS to F(-) ions.     

N2O Emissions at Solid Waste Disposal Sites in Osaka City

Nitrous oxide (N₂O) is a trace gas contributing to stratospheric ozone depletion and global warming. Although a large quantity of information exists about N₂O emissions from various ecosystems, this study was initiated to demonstrate the features of N₂O emissions from sea-based waste disposal sites in Osaka City in relation to CH₄ emissions.

Average N₂O emissions at an active landfill (S-Site) were several times higher than those at a closed landfill (N Site). Average CH₄ emissions were also much greater at the S-Site. Regarding the nature of N₂O emissions, remarkable emissions often were observed with aerobic waste layers at the N-Site, suggesting almost inversely related N₂O emissions with CH₄ production at the N-Site. However, at the S-Site a few exceptionally high N₂O emissions were noted in cases of high CH₄ emissions.     

Light-induced degradation of perfluorocarboxylic acids in the presence of titanium dioxide

The UV-photon-induced degradation of heptafluorobutanoic acid was investigated in acidic aqueous solutions in the presence of titanium dioxide. Heptafluorobutanoic acid could be degraded with this photocatalyst in a light-induced reaction generating carbon dioxide and fluoride anions. Carbon dioxide evolution in a significant amount occurred only in the presence of molecular oxygen and the photocatalyst. The light-induced degradation of trifluoroacetic acid, pentafluoropropanoic acid, nonafluorobutanoic acid, pentadecafluorooctanoic acid, nonafluorobutanesulfonic acid, and heptadecafluorooctanesulfonic acid in the presence of titanium dioxide was also studied. The perfluorocarboxylic acids under investigation are degraded to generate CO(2) and fluoride anions while both perfluorinated sulfonic acids are persistent under the experimental conditions employed in this study. For all compounds photonic efficiencies of the mineralization reaction were estimated to be smaller than 1x10(-5). To increase the photocatalytic activity mixed systems containing homogeneous phosphotungstic acid and heterogeneous titanium dioxide catalysts were also investigated. In the mixtures of these two photocatalysts, the formation rate of CO(2) increased with illumination time.     

Direkte Konfigurationskorrelation zwischen (—)-α-Oxy-β-phenylpropionsäure und (—)-Weinsäure

The Science of Nature -     

Occupational accidents while walking on stairways

Nagata, H., 1991. Occupational accidents while walking on stairways. Safety Science, 14: 199–211.An analysis of occupational injury data related to falls while walking on stairways, and the causes associated with these stair accidents is described. The study was based on labour casualty reports. A total of 1486 stair accidents including 10 deaths, were collected from occupational accidents occurring within greater Tokyo. From these reports 425 cases were selected to undertake actual surveys including personal interviews, direct observations and field measurements. For the purpose of comparison with stairs where no accidents had been reported, a total of 1043 stairs were selected at random from drawings of various buildings.Nine fatal victims had received head injuries. Nearly half of the non-fatal victims received bruises mostly to the legs and feet. Most accidents occurred while descending stairways in haste. Young female employees wearing high or semi-high heeled footwear were relatively prone to fall on stairs. In winter, more stair accidents tended to occur to some extent. The proportion of female accidents was relatively higher than for males when compared to their population ratios. Employees were especially prone to receive injuries by misstep on straight flights of stairs.     

Chlorine promotes antimony volatilization in municipal waste incineration

Antimony volatilization in municipal waste incineration was studied. Two municipal waste samples and antimony(III) oxide (Sb₄O₆) were heated to 500°C and 700°C in an air stream in a quartz furnace. The volatilization of Sb₄O₆ occurred more at 700°C that at 500°C. Conversely, antimony volatilization form municipal waste was stronger at 500°C than at 700°C. This implies that antimony from municipal waste is volatilized as chloride instead of oxide. The chlorine sources for antimony chlorination, a gas-phase reaction involving hydrochloric acid and a solid-phase reaction of inorganic chlorine, e.g., CaCl₂, were compared. Only the solid-phase reaction could offer enough active chlorine to induce chlorination of antimony oxide. Received: July 2, 1998 / Accepted: January 28, 1999     

Photodegradation mechanism for bisphenol A at the TiO2/H2O interfaces

Bisphenol A (BPA) can be decomposed photocatalytically under UV-illumination in aqueous TiO2 dispersion. The two methyl groups in BPA were initially attacked with .OH and/or .OOH radicals having strong oxidizing power, followed by the cleavage of the two phenyl moieties. Finally, the photomineralization to CO2 gas occurred via oxidative processes involving carboxylic acids and aldehydes. The decomposition of structurally similar substances of 4,4'-ethylidenebisphenol (EBP) and 4,4'-methylenebisphenol (MBP) was compared. The decomposition of BPA gave more kinds of intermediates such as 4-isopropylphenol, 4-ethylphenol, etc. On the other hand, that of EBP gave mainly 4-isopropylphenol and that of MBP gave a predominant product of 4-hydroxybenzaldehyde. These photooxidative pathways were proposed on the base of the evidence of oxidative intermediate formation.