Photocatalytic decomposition of crotamiton over aqueous TiO(2) suspensions: determination of intermediates and the reaction pathway

The photocatalytic degradation of crotamiton in aqueous solution using TiO₂ was investigated. To investigate the effect of initial pH, the photodegradation behaviors of three types of pharmaceuticals were compared (crotamiton, clofibric acid, sulfamethoxazole). The degradation rates of crotamiton in the pH range 3-9 were nearly equal, but those of clofibric acid and sulfamethoxazole were affected by pH. At pH > 6.5, TiO₂ particles, clofibric acid and sulfamethoxazole had negative charge, therefore, the repulsive force between TiO₂ particles and anionic pharmaceuticals occurred and a low reaction rate at high pH was observed. The effect of UV intensity and TiO₂ concentration on photodegradation efficiency was also investigated. Linear and logarithmical relationships between UV intensity, TiO₂ concentration and the reaction rate constant were confirmed. Furthermore, the structures of photodegradation intermediates formed concomitantly with the disappearance of crotamiton were estimated. Seven intermediates were characterized by LC/MS/MS analyses, and it was assumed that the photocatalytic degradation of crotamiton was initiated by the attack of electrophilic hydroxyl radicals on aromatic rings and alkyl chains.     

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.     

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.     

Lysis of cyanobacteria with volatile organic compounds

One of bacteria collected from Lake Sagami, Japan, Brevibacillus sp., was found to have a lytic activity of cyanobacteria, but did not produce active compounds. Instead, the co-culturing of Microcystis with the Brevibacillus sp. enhanced the production of two volatile compounds, beta-cyclocitral and 3-methyl-1-butanol, and the former had a characteristic lytic activity. It was confirmed that these volatile compounds were derived from the cyanobacteria themselves. beta-Ionone, geosmin and 2-methylisoborneol derived from cyanobacteria and similar volatile compounds, terpenoids, produced by plants also had a lytic activity. The minimum inhibitory concentration values of the cyanobacterial metabolites were estimated to be higher than those of compounds from plants except for a few compounds. Among them, beta-cyclocitral only produced a characteristic color change of culture broth from green to blue. This color change is similar to the phenomenon observed when a sudden decline in growth of cyanobacteria begins in a natural environment.     

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

The Science of Nature -     

90Sr, 137Cs and (239,240)Pu concentration surface water time series in the Pacific and Indian Oceans--WOMARS results

Under an IAEA's Co-ordinated Research Project "Worldwide Marine Radioactivity Studies (WOMARS)" 90Sr, 137Cs and (239,240)Pu concentration surface water time series in the Pacific and Indian Oceans have been investigated. The Pacific and Indian Oceans were divided into 17 latitudinal boxes according to ocean circulation, global fallout patterns and the location of nuclear weapons test sites. The present levels and time trends in radionuclide concentrations in surface water for each box were studied and the corresponding effective half-lives were estimated. For the year 2000, the estimated average 90Sr, 137Cs and (239,240)Pu concentrations in surface waters of the Pacific and Indian Oceans varied from 0.1 to 1.5 mBq/L, 0.1 to 2.8 mBq/L, and 0.1 to 5.2 microBq/L, respectively. The mean effective half-lives for 90Sr and 137Cs in surface water were 12+/-1 years for the North, 20+/-1 years for the South and 21+/-2 years for the Equatorial Pacific. For (239,240)Pu the corresponding mean effective half-lives were 7+/-1 years for the North, 12+/-4 years for the South and 10+/-2 years for the Equatorial Pacific. For the Indian Ocean the mean effective half-lives of 137Cs and (239,240)Pu were 21+/-2 years and 9+/-1 years, respectively. There is evidence that fallout removal rates before 1970 were faster than those observed during recent decades. The estimated surface water concentrations of 90Sr, 137Cs and (239,240)Pu in latitudinal belts of the Pacific and Indian Oceans for the year 2000 may be used as the average levels so that any new contribution from nuclear facilities, nuclear weapons test sites, radioactive waste dumping sites and from possible nuclear accidents can be identified.     

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.