Effect of silica sand on activation energy for diffusion of sodium ions in montmorillonite and silica sand mixture

The effect of silica sand on the diffusion of sodium ions in mixtures of montmorillonite and silica sand was studied by measuring the apparent diffusion coefficients, activation energies for diffusion, and the basal spacing of the mixed samples. These diffusion experiments suggest that the apparent diffusion coefficients of sodium ions in the mixed samples were almost the same as those of pure montmorillonite samples having the same partial dry densities of montmorillonite. The activation energy dependence for diffusion of sodium ions on the partial dry density was different between the mixed samples and the pure montmorillonite samples. The activation energy increased by adding silica sand at the partial dry density of 1.0 Mg m(-3), and decreased by adding silica sand at the partial dry densities higher than 1.2 Mg m(-3). A change in the XRD profile was observed after adding silica sand at the partial dry density of 1.6 Mg m(-3). Here, a three-water-layer hydrate state of montmorillonite was found in the mixed sample whereas only a two-water-layer hydrate state was observed in the pure montmorillonite sample. These experimental results suggest that silica sand changed the montmorillonite microstructure in the mixed samples, which then altered the sodium-ion diffusion process.     

Isomer distribution of nitrotriphenylenes in airborne particles, diesel exhaust particles, and the products of gas-phase radical-initiated nitration of triphenylene

The formation of mutagenic nitro-polycyclic aromatic hydrocarbons (NPAHs) 1- and 2-nitrotriphenylene (1- and 2-NTP) via gas-phase OH or NO₃ radical-initiated reactions of triphenylene was demonstrated for the first time using a flow reaction system. In contrast with the results of conventional electrophilic nitration, 2-NTP was formed in larger yield than 1-NTP, but this is consistent with the mechanism proposed for gas-phase radical-initiated nitration of PAH. In diesel exhaust particle (DEP) samples, both 1- and 2-NTP were identified and their concentrations determined, as well as 1-nitropyrene (1-NP), which is a representative combustion-derived NPAH: the mean concentrations of 1-NTP, 2-NTP, and 1-NP were 4.7, 1.9, and 32 pmol mg_DEP^–1, respectively. The mean 2-NTP/1-NTP, 1-NTP/1-NP, and 2-NTP/1-NP ratios in samples of airborne particles collected in a residential area in Osaka, Japan, were>1.55,<0.25, and 0.37, respectively; these values are much higher than those of the DEP samples. This finding indicates that there is another source for airborne NTPs, especially 2-NTP, apart from diesel exhaust. These results strongly suggest that airborne NTPs originate from atmospheric processes such as radical-initiated reactions of triphenylene, and this has a significant influence on the atmospheric occurrence of NTPs.     

Polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs) and monobromo-polychlorinated dibenzo-p-dioxins/dibenzofurans (MoBPXDD/Fs) in the atmosphere and bulk deposition in Kyoto, Japan

Polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs) and monobromo-polychlorinated dibenzo-p-dioxins/dibenzofurans (MoBPXDD/Fs) in atmosphere, bulk atmospheric deposition and soil in Kyoto, which is an urban city in Japan, were measured. Decabromodiphenyl ether (D(10)BDE, BDE-209) was detected in relatively high concentrations compared to other PBDE congeners in most samples. Similar results, in which D(10)BDE was predominantly detected, were reported in other studies in Japan. However, these homologue profiles differ from those of studies conducted in North America. The partitioning of semivolatile organic compounds between atmospheric gas phase and particulate-associated phase is an important factor in their environmental behavior. In this study, atmospheric particulate phase fraction (f(P)) of the brominated compounds increased with increasing bromine number, and f(P) was higher in samples collected in winter than in those collected in summer. Moreover, f(P) of PBDFs and MoBPXDFs was higher than that of PCDFs with the same halogen number. These results agree well with expectations from the vapor pressure of the brominated compounds and PCDD/Fs. Among the brominated compounds in the atmosphere, the level of MoBPXDD/Fs correlates positively with that of PCDD/Fs. This relationship has been previously observed in waste incineration samples. These results suggest that one of the sources of MoBPXDD/Fs in the atmosphere is incineration byproduct. The level of PBDD/Fs seems to correlate positively with that of PBDEs. This relationship suggest that the PBDD/Fs in the atmosphere relate to PBDEs, which is an impurity of PBDE products, or formed by the manufacture or combustion of plastics containing PBDEs.     

Photocatalytic removal of fenitrothion in pure and natural waters by photo-Fenton reaction

The photocatalytic removal kinetics of fenitrothion at a concentration of 0.5mgl(-1) in pure and natural waters were investigated in Fe(III)/H2O2/UV-Vis, Fe(III)/UV-Vis and H2O2/UV-Vis oxidation systems, with respect to decreases in fenitrothion concentrations with irradiation time using a solar simulator. Fenitrothion concentrations were determined by HPLC analysis. Furthermore, total mineralization of fenitrothion in these systems was evaluated by monitoring the decreases in DOC concentrations with solar simulator irradiation time by TOC analysis. It was shown that the degradation rate of fenitrothion was much faster in the Fe(III)/H2O2/UV-Vis system than the Fe(III)/UV-Vis and H2O2/UV-Vis systems in both pure and river waters. Consequently, the mineralization rate of fenitrothion was much faster in the Fe(III)/H2O2/UV-Vis system than in the other two systems. The high *OH generation rate measured in the Fe(III)/H2O2/UV-Vis system was the key to faster degradation of fenitrothion. Increases in the concentrations of H2O2 and Fe led to better final degradation of fenitrothion. These results suggest that the photo-Fenton reaction (Fe(III)/H2O2/UV-Vis) system is likely to be an effective method for removing fenitrothion from contaminated natural waters.     

Association of the mutagenicity of airborne particles with the direct emission from combustion processes investigated in Osaka, Japan

The association of the direct-acting mutagenicity of soluble organic fraction of airborne particles toward Salmonella typhimurium YG1024 strain with the direct emission was investigated at a roadside and at a residential area in Osaka, Japan. The direct-acting mutagenicity was evaluated as mutagenic activity per unit volume of ambient air (rev m⁻³) and/or that per airborne particulate weight collected on a filter (rev mg⁻¹). The annual or diurnal changes of the mutagenicity of airborne particles at the residential site showed similar patterns to those of some gaseous pollutants such as NO₂ and SO₂, which were emitted from combustion processes. This result indicates that the mutagenicity is mainly attributable to the primary emissions. From the analysis of the relationship between the wind sector and the mutagenic intensity, rev m⁻³ and rev mg⁻¹ values were strongly affected by the emissions from the fixed sources and from the mobile sources, respectively. The rev m⁻³ value and concentration of 1-nitropyrene (1-NP) in unit per m³ at the roadside were a factor of 2.6 and 2.8 higher than those at the residential site, respectively, but the rev mg⁻¹ value and concentration of 1-NP in unit per mg at the roadside were substantially comparable to those at the residential area. These observations suggest that the characteristics of the airborne particles can be attributed to the automotive emissions even at the suburban area.     

Bioconcentration factor of relatively low concentrations of chlorophenols in Japanese medaka

Bioconcentration factors (BCF) for pentachlorophenol (PCP) and 2,4-dichlorophenol (2,4-DCP) in Japanese medaka (Oryzias latipes) were determined at five different concentrations of the chemicals, between 0.1 and 10 microg/l (PCP), 0.3 and 30 microg/l (2,4-DCP), in the ambient water. Medaka were exposed to each chemicals in a continuous-flow system during the embryonic development period and 60 days after hatching from eggs collected in the laboratory. Both the exposure time and the aqueous concentrations are much more realistic and closer to natural aquatic environments than those used in conventional BCF studies. The BCF values of PCP were from (4.9+/-2.8)x10(3) at the aqueous concentration of 0.074+/-0.028 microg/l to (2.1+/-1.4)x10(3) at 9.70+/-0.56 microg/l. The BCF value of 2,4-DCP were from (3.4+/-3.0)x10(2) at 0.235+/-0.060 microg/l to 92+/-27 at 27.3+/-1.6 microg/l. Generally, BCF values increased as the aqueous concentrations of PCP or 2,4-DCP decreased. This finding suggests that a relatively low and realistic aqueous concentration of these compounds is necessary to more accurately determine their BCF values in natural aquatic environments. Conventional BCF experiments at higher aqueous concentrations may underestimate the BCF values.     

Bacterial communities in different locations, seasons and segments of a dairy wastewater treatment system consisting of six segments

A dairy wastewater treatment system composed of the 1st segment (no aeration) equipped with a facility for the destruction of milk fat particles, four successive aerobic treatment segments with activated sludge and a final sludge settlement segment was developed. The activated sludge is circulated through the six segments by settling sediments (activated sludge) in the 6th segment and sending the sediments beck to the 1st and 2nd segments. Microbiota was examined using samples from the non-aerated 1st and aerated 2nd segments obtained from two farms using the same system in summer or winter. Principal component analysis showed that the change in microbiota from the 1st to 2nd segments concomitant with effective wastewater treatment is affected by the concentrations of activated sludge and organic matter (biological oxygen demand [BOD]), and dissolved oxygen (DO) content. Microbiota from five segments (1st and four successive aerobic segments) in one location was also examined. Although the activated sludge is circulating throughout all the segments, microbiota fluctuation was observed. The observed successive changes in microbiota reflected the changes in the concentrations of organic matter and other physicochemical conditions (such as DO), suggesting that the microbiota is flexibly changeable depending on the environmental condition in the segments. The genera Dechloromonas, Zoogloea and Leptothrix are frequently observed in this wastewater treatment system throughout the analyses of microbiota in this study.     

Pharmacophagous acquisition of clerodendrins by the turnip sawfly (Athalia rosae ruficornis) and their role in the mating behavior

Summary. Adults of the turnip sawfly, Athalia rosae ruficornis (Tenthredinidae: Hymenoptera), frequently visit a plant, Clerodendron trichotomum (Verbenaceae), and feed pharmacophagously on the glandular trichomes on the leaf surface. A series of neo-clerodane diterpenoids (e.g. clerodendrins B and D) contained in glandular organs on the leaf surface stimulate feeding of the sawflies (both males and females). The adults fed selectively on the trichomes were found to sequester a series of the bitter-tasting diterpenes (clerodendrin D, ajugachin A, athaliadiol) in the body tissues, which suggested their primary role as defense substances against predators. Females fed on Clerodendron leaves or on clerodendrin B or D were more successful in mating than unfed females. Thus, females seem to obtain an advantage in mating success through the acquisition of the defensive principles from the Clerodendron plant. Received 20 April 1999; accepted 29 June 1999     

Removal of organic matter and disinfection by-products precursors in a hybrid process combining ozonation with ceramic membrane ultrafiltration

The performance of an integrated process including coagulation, ozonation, ceramic ultrafiltration (UF) and biologic activated carbon (BAC) filtration was investigated for the removal of organic matter and disinfection by-products (DBPs) precursors from micro-polluted surface water. A pilot scale plant with the capacity of 120 m³ per day was set up and operated for the treatment of drinking water. Ceramic membranes were used with the filtration area of 50 m² and a pore size of 60 nm. Dissolved organic matter was divided into five fractions including hydrophobic acid (HoA), base (HoB) and neutral (HoN), weakly hydrophobic acid (WHoA) and hydrophilic matter (HiM) by DAX-8 and XAD-4 resins. The experiment results showed that the removal of organic matter was significantly improved with ozonation in advance. In sum, the integrated process removed 73% of dissolved organic carbon (DOC), 87% of UV₂₅₄, 77% of trihalomethane (THMs) precursors, 76% of haloacetic acid (HAAs) precursors, 83%of trichloracetic aldehyde (CH) precursor, 77% of dichloroacetonitrile (DCAN) precursor, 51% of trichloroacetonitrile (TCAN) precursor, 96% of 1,1,1-trichloroacetone (TCP) precursor and 63% of trichloronitromethane (TCNM) precursor. Hydrophobic organic matter was converted into hydrophilic organic matter during ozonation/UF, while the organic matter with molecular weight of 1000–3000 Da was remarkably decreased and converted into lower molecular weight organic matter ranged from 200–500 Da. DOC had a close linear relationship with the formation potential of DBPs.