Research to develop a predicting system of mammalian subacute toxicity (3) construction of a predictive toxicokinetics model

A new predictive toxicokinetics model was developed to estimate subacute toxicity (target organs, severity, etc.) of non-congeneric industrial chemicals, where the chemical structures and physico-chemical properties are only available. Thus, a physiological pharmacokinetics model, which consists of blood, liver, kidney (these were experimentally found as major toxicological targets), muscle and fat compartments , was established to simulate the chemical concentrations in organs/tissues with pharmacokinetic parameters by means of Runge-Kutta-Gill algorithm. The pliarmacokinetic parameters, i.e. absorption rate, absorption ratio, hepatic extraction ratio of metabolism and renal clearance were calculated by using separately established Quantitative Structure-Pharmacokinetics Relationship equations. The developed predictive model was then applied to simulations of 43 non-congeneric industrial chemicals. The chemical concentrations in organs/tissues after single oral administration were simulated, and their maximum concentrations (Cmax's) and area tinder the concentration-time curves (AUC's) were calculated.Fast Inverse Laplace Transform was newly applied for the purpose of simulation of 28-day repeated dose toxicity.Simulated concentrations of 28 days repeated dose were, however, found to be the same as those of simple repetitions of a single administration per day because of the short half-lives of non-congeneric industrial chemicals.A comparison of subacute toxicity data with Cmax's and AUC's in a single dose scenario suggested that the organs/tissues with relatively high concentrations of tested chemical substances were the most sensitive targets within a chemical.Chemical concentrations in liver, for instance, were correlated with the severity of hepatotoxicity among the chemicals. It was also suggested that to improve and widen the present approach, data of metabolite and reactivity of non-congeneric industrial chemicals to organs/tissues, receptors, etc. should be incorporated into the model.     

The induction of larval settlement and metamorphosis of two sea urchins,Pseudocentrotus depressus and Anthocidaris crassispina,by free fatty acids extracted from the coralline red alga Corallina pilulifera

Lipophilic inducers of larval settlement and metamorphosis of Pseudocentrotus depressus and Anthocidaris crassispina, two commercially important sea urchin species in Japan, were isolated from the foliose coralline red alga Corallina pilulifera (collected in 1990 near Saga, Japan) and identified. Larval assays of the fractions obtained by silica gel column chromatography of the total lipids showed that non-polar groups of lipids were effective at inducing larval settlement and metamorphosis. The effective fractions were further subjected to gel filtration (Sephadex LH-20) and also to silica gel column chromatography, and the effective components isolated as single spots by thin-layer chromatography. The components at a concentration of ca. 0.4 mg paper^-1 (sample was adsorbed on a paper with 20 cm²) induced high rates of larval settlement of both P. depressus and A. crassispina. Chemical analyses of the components revealed a mixture of free fatty acids (FFAs), dominated by eicosapentaenoic acid (20:5, 41 to 50%), palmitic acid (16:0, 11 to 17%), arachidonic acid (20:4, 9 to 15%), and palmitoleic acid (16:1, 4 to 5%). In assays with the four standard FFAs, only 20:4 and 20:5 induced larval settlement and metamorphosis of the two species, while 16:0 and 16:1 were ineffective. The larvae underwent significant rates of settlement and metamorphosis in response to the two former FFAs at levels as low as 0.18 mg paper^-1. Amongst the free fatty acid components of the alga, 20:5 was isolated as the chemical inducer of larval settlement and metamorphosis of the sea urchins in the laboratory.     

Improved method for the formation of recycled resins from depolymerized products of waste fiber-reinforced plastics: simple and effective purification of recovered monomers by washing with water

The synthesis of recycled plastics from recovered monomeric materials obtained from the depolymerization reaction of fiber-reinforced plastics (FRP) was examined. The depolymerization reaction of FRP in the presence of N,N-dimethylaminopyridine (DMAP) smoothly yielded the corresponding monomers, which mainly consisted of dimethyl phthalates. The polymerization reaction with this monomer failed to form the corresponding unsaturated polyesters due to contamination by N-methyl-4-pyridone, a decomposition product of DMAP. An efficient purification of the recovered monomer was achieved by washing with water, and the purified monomer successfully yielded the corresponding polymers. A hardness test revealed that the polymers were as hard as the polyester made from virgin materials. The present modification provides a practical method for the preparation of recycled plastics from depolymerized plastics.     

Thermal analysis of polyethylene glycol: evolved gas analysis with ion attachment mass spectrometry

The thermal decomposition of polyethylene glycol was investigated by using a technique combining evolved gas analysis (time-resolved pyrolysis) with ion-attachment mass spectrometry. This technique allows the detection of intact pyrolysis products and, therefore, offers the opportunity for direct real-time monitoring of thermal by-products. Unstable products can thus be detected; for instance, many highly reactive organic peroxides, such as CH₃OOH and HOCH₂OOH, were found in this study. Classification analysis revealed 10 major compositional formulas among the product species: C_nH_2n+2O, C_nH_2n+2O₂, C_nH_2n+2O₃, C_nH_2n+2O₄, C_nH_2n+2O₅, C_nH_2n+2O₆, C_nH_2n+2O₇, C_nH_2nO, C_nH_2nO₂, and HO(CH₂CH₂O)_nH ethylene glycol oligomers. The Li⁺ ion adduct mass spectra showed a characteristic profile in terms of both the appearance of unique components and the distribution of pyrolysis products. Among the products of the thermal decomposition of PEG, formaldehyde (HCHO) and organic peroxides were particularly interesting. Formaldehyde, one of the 10 most abundant products, is a known human carcinogen. The detection of peroxides suggests that they may form during the incineration of PEG, which may have important environmental implications. The existence of peroxide products may have implications for chemical evolution in incinerator systems.     

Urban climate in the Tokyo metropolitan area in Japan

Long-term climate changes related with urbanization in Tokyo, Japan, and recent temperature and heavy rainfall distribution in the Tokyo metropolitan area are reviewed. A relatively high temperature increase in annual mean temperature at the rate of 3.0°C/century was detected in Tokyo for the period 1901–2015. Some observational evidence showed the existence of both thermal and mechanical effects of urbanization on recent heavy rainfall occurrences, and modeling studies also support precipitation enhancement. Urban influences were recognized in other climatological elements, such as number of fog days, relative humidity, and wind circulation.     

Research on leachate recirculation from different types of landfills

Landfills can produce a great amount of leachate containing highly concentrated organic matter. This is especially true for the initial leachate from landfilled municipal solid wastes (MSW) that generally has concentrations of COD(Cr) and BOD(5) up to 80,000 and 50,000mg/L, respectively. The leachate could be disposed by means of recirculating technique, which decomposes the organics through the action of proliferating microorganisms and thereby purifies the leachate, and simultaneously accelerates organic decomposition through water saturation control. Data from experimental results indicated that leachate recirculating could reduce the organic concentration considerably, with a maximum reduction rate of COD(Cr) over 95%; and, using a semi-aerobic process, NH(3)-N concentration of treated leachate could be under 10mg/L. In addition, the organic concentration in MSW decreased greatly.     

Evaluation of data quality in Japanese National Forest Inventory

We evaluated the quality of data being collected for the Japanese National Forest Inventory (NFI). The inventory program commenced in 1999 but has not incorporated a quality assurance (QA) program; we sought to determine what effect this was having on the quality of data being collected. Forty-eight plots in four prefectures were measured by operational field teams and then remeasured by a control team that made careful and unhurried measurements. The paired data were evaluated, including diameter, total height, tree count, species richness, and topographic condition. Compared to the control team, all field teams of each prefecture tended to significantly underestimate all of the continuous variables. Most variables had larger variability in the inventory data than has been reported in the published literature. The findings of consistent bias and large variation in the field team measurements call for urgent implementation of a quality assurance program (extensive field training and regular remeasurement) in the Japanese NFI to improve data quality, and this conclusion could be applied to the inventory system of any country that does not include a QA program.     

Formation of recycled plastics from depolymerized monomers derived from waste fiber-reinforced plastics

To develop a new method for the chemical recycling of plastics, we examined the formation of recycled polymers from the recovered monomeric materials of solubilized waste fiber-reinforced plastics (FRP) under supercritical alcoholic conditions. Treatment of waste FRP with supercritical MeOH resulted in the formation of monomeric organic compounds that mainly contained dimethyl phthalate (DMP) and propylene glycol. The presence of these materials was confirmed by gas chromatography and nuclear magnetic resonance analyses and they were mixed with new DMP and glycols in various ratios to form unsaturated polyesters. The polymerization progressed successfully for all mixing ratios of the recovered and new DMP. Hardness tests on these recycled polymers indicated that the polymer made from a 1:1 mixture of recovered and new dimethyl phthalate had almost the same level of hardness as the polymers made from new materials. We also examined the formation of recycled FRP by using glass fibers and monomeric materials recovered through the present depolymerization method. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6     

Efficient chemical recycling of waste fiber-reinforced plastics: use of reduced amounts of dimethylaminopyridine and activated charcoal for the purification of recovered monomer

We have achieved major improvements in the efficient chemical recycling of waste fiber-reinforced plastics (FRPs). The effects of reduction in the amounts of dimethylaminopyridine (DMAP) used for depolymerization were examined. The treatment of waste FRP in the presence of 1 or 2 wt% DMAP resulted in the successful recovery of monomeric materials that could be employed in the polymerization process to produce recycled plastic. The separation of linker units from glass fiber, however, was unsuccessful. The purity of the recovered monomeric material, when treated with activated charcoal, was improved to about 70%. This resulted in effective decoloration of the recovered monomer. Finally, the purified material, after undergoing repolymerization, provided high-quality recycled plastic comparable to new plastics produced from new monomers.     

Improved preparation of recycled polymers in chemical recycling of fiber-reinforced plastics and molding of test product using recycled polymers

We examined an improved preparation method of recycled unsaturated polyester resin from recovered monomeric materials obtained from the depolymerization of fiber-reinforced plastics (FRPs). The formation of unsaturated polyester progressed smoothly in the presence of catalytic amounts of Ca(OAc)₂ and Ti(OBu)₄. The quality of the resin was estimated by the durometer hardness test. The strength test of FRP board prepared from recycled resin showed sufficient hardness for practical use (about 94% of the tensile strength of new resin). We examined the recycled resin by using it to mold successfully an actual test product.