Solventless Delignification of Wood Flour with TiO2/poly(ethylene oxide) Photocatalyst System

A novel solventless delignification of a defatted Picea glehnii wood flour sample was performed using a TiO₂/polyethylene oxide (PEO) photocatalyst system. A cell wall structure of the wood flour was directly observed, showing that its lignin fraction was removed by the photodegradation. The total lignin amount was slightly decreased as compared with that of the pristine sample, and the vanillin formation was confirmed by the ¹H-NMR measurement. The TiO₂ worked as a radical initiator, and simultaneously acid and aldehyde compounds produced by the PEO photolysis did as an accelerator for the solventless delignification. Although the photocatalyst system showed high delignification activity even for a low molecular lignin model, the delignification of the wood flour sample was confined to the surface. It was found that the suppressed delignification behavior was due to crosslinked structure of lignin.     

Optimization of enhanced biological phosphorus removal after periods of low loading.

Enhanced biological phosphorus removal is a well-established technology for the treatment of municipal wastewater. However, increased effluent phosphorus concentrations have been reported after periods (days) of low organic loading. The purpose of this study was to evaluate different operating strategies to prevent discharge of effluent after such low-loading periods. Mechanisms leading to these operational problems have been related to the reduction of polyphosphate-accumulating organisms (PAOs) and their storage compounds (polyhydroxy alkanoates [PHA]). Increased effluent phosphorus concentrations can be the result of an imbalance between influent loading and PAOs in the system and an imbalance between phosphorus release and uptake rates. The following operating conditions were tested in their ability to prevent a reduction of PHA and of overall biomass during low organic loading conditions: (a) unchanged operation, (b) reduced aeration time, (c) reduced sludge wastage, and (d) combination of reduced aeration time and reduced sludge wastage. Experiments were performed in a laboratory-scale anaerobic-aerobic sequencing batch reactor, using acetate as the carbon source. Without operational adjustments, phosphorus-release rates decreased during low-loading periods but recovered rapidly. Phosphorus-uptake rates also decreased, and the recovery typically required several days to increase to normal levels. The combination of reduced aeration time and reduced sludge wastage allowed the maintenance of constant levels of both PHA and overall biomass. A mathematical model was used to explain the influence of the tested operating conditions on PAO and PHA concentrations. While experimental results were in general agreement with model predictions, the kinetic expression for phosphorus uptake deviated significantly for the first 24 hours after low-loading conditions. Mechanisms leading to these deviations need to be further investigated.     

Distribution of Poly(β-propiolactone) Aerobic Degrading Microorganisms in Different Environments

The distribution of degading microorganisms of high molecular weight poly(-propiolactone) (PPL), whose individual structural units are similar to those of poly(-hydroxybutyrate) (PHB) and poly(€-caprolactone) (PCL), was examined. Despite the fact that PPL is a chemosynthetic polymer, many kinds of PPL-degrading microorganisms were found to be distributed as resident populations widely in natural environments. A total of 77 strains of PPL-degrading microorganisms was isolated. From standard physiological and biochemical tests, at least 41 strains were referred to as Bacillus species. Microbial degradation of fibrous PPL proceeded rapidly in some enrichment cultures but was not as complete as that of PHB. Most of the isolated PPL-degrading microorganisms were determined to be PCL degraders and/or PHB degraders. Therefore, it can be assumed that mostly PPL is recognized by the microorganisms as PHB or another natural substrate of the same type as which PCL is regarded. Microbial degradation of PPL was confirmed by some Bacillus strains from type culture collections. The similarity of microbial degradation between PPL and PCL was found to be very close.     

Evaluation of fecal pollution of river sediment by detection of urobilin

In this study, we attempted to establish a new indicator for fecal pollution of river sediment using a sensitive detection method for urobilin. Urobilin contained in sediment was extracted with an alkaline buffer solution. The suitable buffer solution for extraction of urobilin consisted of 0.1 M Tris-HCl buffer (pH 10.0) containing 0.1 m sodium chloride. The ratio of sediment to buffer was 1:10. The distribution of urobilin in river sediment was studied by this method. The amount of urobilin in the river sediment of Tokyo (urban) and the Miura peninsula (rural) area was surveyed. Large quantities of urobilin were detected in the sediments of the urban rivers, but it was scarce in the rural rivers. Urobilin showed a higher content in sediment than in water. Urobilin in river sediment is distributed in large amounts in the lower reaches, where the water is polluted with domestic sewage and industrial waste, but is scarce in the upper streams. The amount of urobilin decreases to the lower layers.     

Study on anisotropy of effective diffusion coefficient and activation energy for deuterated water in compacted sodium bentonite

To quantify the effects of temperature on the diffusivity of deuterated water (HDO) in compacted sodium bentonite, through-diffusion experiments were conducted at elevated temperatures ranging from 298 to 333 K. Kunipia F (Na-montmorillonite content>98 wt.%; Kunimine Industries) was compacted to a dry density of 0.9 or 1.35 Mg/m(3). As montmorillonite particles were oriented perpendicular to the direction of compaction, the anisotropy of diffusivity was investigated both parallel and normal to the preferred orientation of the montmorillonite. The effective diffusion coefficient D(e) of HDO was larger when the diffusional direction was parallel as opposed to normal to the preferred orientation for both dry densities. The magnitude of D(e) and the anisotropy for HDO were in good accordance with previously reported results for tritiated water at room temperature. Activation energies of D(e) were isotropic and increased with increasing dry density over the range of 19-25 kJ/mol. This relationship was considered to be due to both pore structure development and the high activation energy of water near the montmorillonite surface.     

Comparison of polybrominated diphenyl ethers in fish, vegetables, and meats and levels in human milk of nursing women in Japan

At present, little is known about the occurrence of polybrominated diphenyl ethers (PBDEs) in fish and food products sold in Japan. To investigate whether human exposure to PBDEs through the diet is significant, the concentrations of PBDEs were determined in fish and in meat and vegetables sold in two food markets in the city of Hirakata, Osaka prefecture. The concentrations of PBDEs in the breast milk of 12 primiparae nursing women at one month after delivery also were determined to ascertain the relationship between the levels found in the diet and levels in humans. sigma PBDE concentrations ranged between 21 and 1650 pg/g fresh weight in the edible tissues of five species of fish and one shellfish species. The highest concentrations were measured in yellow-fin tuna, followed by short-necked clam, salmon, yellowtail, mackerel and young yellowtail. Interestingly, sigma PBDE concentrations were not statistically significantly different in two cultured mackerel samples from Japan and mackerel collected from northern European waters. sigma PBDE concentrations in beef, pork and chicken meat (ranging between 6.25 and 63.6 pg/g fresh weight) and in three different vegetables (ranging between 38.4 and 134 pg/g fresh weight) were significantly lower than the concentrations in fish. In human milk, sigma PBDE concentrations ranged between 668 and 2840 pg/g lipid basis, which is comparable to the levels in populations of nursing women reported in Sweden and elsewhere. There was a strong positive relationship between PBDE concentrations in human milk and dietary intake of fish and shellfish, which was established in the women from responses to a questionaire on food consumption habits. The results of this study of food products commonly consumed in Japan and the levels found in nursing women raise a concern about low level PBDE contamination of fish and other foods intended for human consumption.     

Surrogate study for dioxins from municipal waste incinerator in startup condition: applicability as a dioxin control indicator and an organohalogen emission warning

Dioxins and their surrogates were continuously monitored during the startup of two municipal waste in cinerators (MWIs). The surrogates studied included low-volatility organohalogen compounds (LVOH) sampled by online systems, as well as chlorobenzenes (CBs) and chlorophenols (CPs). The changes in levels of LVOH, CBs, and CPs corresponded well with the trend of the toxicity equivalent quantity (TEQ). The correlation of LVOH with TEQ was fairly good, whereas that of CBs and CPs with TEQ was not consistent. The correlation of LVOH with TEQ involved a memory effect related to the delayed emission of less volatile compounds. The isomer analysis of the dioxins present under startup conditions showed evidence of the memory effect, i.e., highly chlorinated isomers were emitted slowly, whereas low-chlorinated isomers and LVOH decreased rapidly as the temperature rose. LVOH cannot act as a perfect dioxin surrogate, but it can give a versatile, quick, and comprehensive warning of the presence of organohalogen compounds because it is free from the memory effect and covers many kinds of organohalogen compounds, including dioxins.     

Formation of toxic chemicals including dioxin-related compounds by combustion from a small home waste incinerator

We investigated combustion in a small home waste incinerator and analyzed both flue gas and residual ash for formation of the dioxin-related compounds polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and coplanar polychlorinated biphenyls and their precursors polychlorinated benzenes, polychlorinated phenols, polychlorinated diphenyl ethers, and polychlorinated biphenyls. Particularly, we investigated the effect of the incinerated material's composition on both the congener ratios of released compounds and the total concentration of all congeners of each compound. Eight different samples were prepared for incineration with four samples consist entirely paper, dead leaves, natural wood, or building materials. The remaining four samples contained mostly paper, but also other components such as fiber, non-chlorine-containing plastics, chlorine-containing plastics, and copper electric wire. The presence of non-chlorine-containing plastic in combustion samples did not increase overall dioxin or dioxin-precursor emissions. In contrast, chlorine-containing plastic resulted in a several-fold increase in total polychlorinated dioxins released, in both flue gas and residual ash. Copper wire resulted in a further several-fold increase in total polychlorinated dioxins and dioxin precursors released, with one exception: the addition of chlorine-containing plastic resulted in a many-fold increase in polychlorinated biphenyls, but only a modest further increase ( approximately 52%) with the further addition of copper. Homologue ratios tended toward higher-chlorine compounds as chlorine-containing plastic and Cu were added, but the results were far from uniform. Our results show that toxic dioxin release from small home waste incinerators must be considered significant, especially if even small amounts of chlorine-containing plastics or copper are burned.     

Optimization of the purification method for dioxin analysis in human serum and temporal changes in background dioxin levels in the general population

To perform high quality and high throughput measurements, complicated purification procedure by two rounds of open column chromatography was simplified by appraising the components and adding a sufficient amount of adsorbents to the column. The procedure consists of two open column techniques using a multi-layer silica gel column and an active carbon dispersed silica gel column. This purification procedure is used in "Standard manual for dioxin analysis in human blood" published in 2000 (Ministry of Health and Welfare, Japan, 2000). Consequently, a purification procedure using only 1 g of 10% AgNO(3)/silica gel can remove the matrix of blood serum as effectively as a multi-layer silica gel column. In addition, 0.1 g of carbon silica gel, equivalent to 1/10 the weight used currently in analyses, separates and recovers the dioxins in purified extract of blood serum. Furthermore, changes in the background level in the general population were clarified by monitoring the dioxin concentrations in human blood. The dioxin concentrations and ratios in blood in the general population remained at a tolerable level for three months. Therefore, the blood serum was available for the detection of a remarkable elevation in dioxins level considered to be indicative of contamination due to high-density exposure.