Radiolysis of aqueous phenol solutions with nanoparticles. 1. Phenol degradation and TOC removal in solutions containing TiO2 induced by UV,gamma-ray and electron beams

Aqueous phenol solutions containing TiO(2) nanoparticles were irradiated with ultraviolet (UV), gamma-ray and electron beams. Organic compounds were fully removed by each type of radiation in the presence of the particles. The absorbed energy of the ionizing radiation (gamma-ray and electron beams) needed for removal was much lower than that of UV photocatalysis. Phenol was decomposed by the ionizing radiation in the absence of the nanoparticles and the addition of TiO(2) had no significant effect on phenol decomposition rate. Instead, total organic carbon (TOC) removal using the ionizing radiation was accelerated drastically by TiO(2). It is suggested that TiO(2) particles affect the intermediate compounds produced through the decomposition of phenol. The amount of removed TOC per absorbed energy were compared in the absence and the presence of TiO(2) nanoparticles. Radiolysis with the nanoparticles showed consistently high rate and high efficiency of TOC removal.     

Nutrient dynamics and the eutrophication of shallow lakes Kasumigaura (Japan), Donghu (PR China), and Okeechobee (USA)

We compared the nutrient dynamics of three lakes that have been heavily influenced by point and non-point source pollution and other human activities. The lakes, located in Japan (Lake Kasumigaura), People's Republic of China (Lake Donghu), and the USA (Lake Okeechobee), all are relatively large (> 30 km2), very shallow (< 4 m mean depth), and eutrophic. In all three lakes we found strong interactions among the sediments, water column, and human activities. Important processes affecting nutrient dynamics included nitrogen fixation, light limitation due to resuspended sediments, and intense grazing on algae by cultured fish. As a result of these complex interactions, simple empirical models developed to predict in-lake responses of total phosphorus and algal biomass to external nutrient loads must be used with caution. While published models may provide 'good' results, in terms of model output matching actual data, this may not be due to accurate representation of lake processes in the models. The variable nutrient dynamics that we observed among the three study lakes appears to be typical for shallow lake systems. This indicates that a greater reliance on lake-specific research may be required for effective management, and a lesser role of inter-lake generalization than is possible for deeper, dimictic lake systems. Furthermore, accurate predictions of management impacts in shallow eutrophic lakes may require the use of relatively complex deterministic modeling tools.     

Studies on automated survey system of environmental chemicals by gas chromatography-mass spectrometry-computer I. Retrieval system of mass spectra

A retrieval system of mass spectra based upon the Probability Based Matching method was studied in order to apply it to survey the chemicals in environments by a gas chromatography-mass spectrometry-computer system. As retrieval indices, peak missing probability and relative confidence value were proposed.     

The effect of copper speciation on the formation of chlorinated aromatics on real municipal solid waste incinerator fly ash

A limited amount of information exists regarding the relationship between the chemical form of copper and the formation of chlorinated aromatics in fly ash. To understand the effects of the various forms of copper on the formation of chlorinated aromatics in real fly ash, we determined the chemical forms of copper present in various types of real fly ash using X-ray absorption near edge structure (XANES) and evaluated the relationship between the chemical forms of copper and the formation of chlorinated aromatics. Copper chloride hydroxide (CuCl2 x 3Cu(OH)2) and cuprous chloride (CuCl) were the predominant copper species found in real fly ash. Although pure cupric chloride (CuCl2) is known to be the most active catalyst for the formation of chlorinated aromatics under experimental conditions with synthetic fly ash, CuCl2 was not found in every real fly ash sample. The amount of copper chloride hydroxide was positively correlated with the formation of chlorinated aromatics in real fly ash and is, consequently, considered to be one of the key species involved in the formation of chlorinated aromatics.     

Morphologies of zinc oxide particles and their effects on photocatalysis

ZnO powders with different morphologies were synthesized by alkali precipitation, organo-zinc hydrolysis, and spray pyrolysis. Acetaldehyde decomposition was used as a probe reaction to evaluate the photocatalysis of these ZnO powders. We investigated the relationship between photocatalytic activity and crystallinity, surface area, or morphology. Results indicate that the photocatalytic activity of ZnO powder depends on crystallinity rather than surface area for the same original ZnO powders prepared by equal conditions other than the difference in calcination temperature. However, no direct relationship between photocatalytic activity and crystallinity or surface area was found for the differently original ZnO powders prepared by different methods, or the same method with different conditions. Instead, we find that the particle morphology significantly affects its photocatalysis.     

Chlorination of bisphenol A in aqueous media: formation of chlorinated bisphenol A congeners and degradation to chlorinated phenolic compounds

The chlorination of bisphenol A (BPA) in aqueous media was investigated in order to describe the degradation profile of this compound and the formation of chlorinated products. Aqueous solutions of BPA (approx. 1 mg/l) were chlorinated by sodium hypochlorite solution at room temperature and under weakly alkaline conditions. Chlorinated compounds were extracted with dichloromethane and determined by gas chromatography/mass spectrometry (GC/MS). BPA was consumed completely within 5 min of chlorination, when the initial chlorine concentration was 10.24 mg/l (molar ratio to BPA, 58.7). On the other hand, when the initial chlorine concentration was 1.03 mg/l (molar ratio, 6.56), 9.3% of BPA still remained after 60 min chlorination. Five chlorinated BPA congeners, 2-chlorobisphenol A (MCBPA), 2,6-dichlorobisphenol A (2,6-D2CBPA), 2,2'-dichlorobisphenol A (2,2'-D2CBPA), 2,2',6-trichlorobisphenol A (T3CBPA) and 2,2', 6,6'-tetrachlorobisphenol A (T4CBPA) were formed in the earlier stages of chlorination. Several chlorinated phenolic compounds, 2,4,6-trichlorophenol (T3CP), 2,6-dichloro-1,4-benzoquinone (D2CBQ), 2,6-dichloro-1,4-hydroquinone (D2CHQ), C9H10Cl2O2, C9H8Cl2O and C10H12Cl2O2, were also formed by further chlorination.     

Erythrocyte supply from the spleen and hemoconcentration in hypoxic yellowtail

Hematocrit and hemoglobin concentration of yellowtail blood elevated more than 30% during severe hypoxia for 35 or 40 min. About 40% of the hematocrit elevation is considered to have been caused by erythrocyte supply from the spleen, and about 60% by hemoconcentration due to water shift out of the circulating plasma. Osmotic swelling of erythrocytes is considered not to have occurred, judging from the constant level in the saturation index of the blood.     

Contamination of butyltin and phenyltin compounds in the marine environment of Otsuchi Bay, Japan

Butyltin (BT) and phenyltin (PT) compounds were measured in seawater, sediment, and biological samples collected from coastal areas of Otsuchi Bay, Japan. Tributyltin (TBT) compounds in seawater, sediment, plankton, mussels, scallops and fish were in the range of 0.008-0.074 microg liter(-1), 0.01-0.64 mg (kg dry wt)(-1), 0.24-9.8 mg (kg dry wt)(-1), 0.04-0.18 mg (kg wet wt)(-1), 0.10-0.13 mg (kg wet wt)(-1) and 0.01-0.02 mg (kg wet wt)(-1), respectively. Trace amount of PTs were found in seawater. The highest concentrations of TBT and triphenyltin (TPT) were found near a shipyard. Triorganotin compounds were more dominant than their metabolites. A positive correlation was observed between the concentrations of TBT and TPT in the mussels. Concentrations of TBT and TPT in mussels were high in the upper intertidal zone, and decreased toward the water.     

Dynamics of gonadosomatic index of fish with indeterminate fecundity between subsequent egg batches: application to Japanese anchovy Engraulis japonicus under captive conditions

The gonadosomatic index (GSI) is widely used as a simple measure of reproductive capacity, but its validity has often been questioned. This study showed the inter-spawning variation in the predicted GSI of Japanese anchovy using the gravimetric oocyte packing density method. Time course sampling showed that final oocyte maturation and subsequent ovulation occurred from afternoon to evening on the day of spawning. Oocyte in vitro assay, however, suggested that the timing of the spawning could be predetermined by midnight the day before spawning. Models predicted that the GSI of a female just after spawning gradually increases until the completion of germinal vesicle breakdown, after which it dramatically rises by 24–53 % per hour within a few hours of the onset of ovulation. This indicates that the predicted GSI of a female increases by 3.5 times within about 19 h before ovulation, even if the relative batch fecundity remains constant.     

Mercury volatilization by the most mercury-resistant bacteria from the seawater of Minamata Bay in various physiological conditions

The volatilization of mercuric chloride (HgCl₂) and methyl mercuric chloride (CH₃HgCl) by the 45 strains (35 Pseudoalteromonas sp., 2 Vibrio sp., 1 Aeromonas sp., and 7 unclassified) of the most mercury-resistant bacteria from Minamata Bay seawater was examined in various physiological conditions. The bacteria could grow and volatilize HgCl₂ in the liquid medium containing 1-10% NaCl. Two Pseudoalteromonas strains could grow and volatilize HgCl₂ at pH levels ranging from 5.0 to 10.0. The resting cells of 43 strains could volatilize HgCl₂ at concentrations ranging from 30 to 68% after 1-h incubation at 30vv°C. The resting cells of 41 strains could volatilize CH₃HgCl at concentrations ranging from 13 to 88% after 1-h incubation at 30vv°C. Ninety-two percent of mercury was removed from the phosphate buffer containing 0.1 7g/ml by a resting cell of Pseudoalteromonas strain H-4 after 30-min incubation at 30vv°C. We were able to screen the special bacteria, which could volatilize mercury compounds at a high rate in various physiological conditions, for the purpose of developing mercury removal methods using bacteria.