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.     

Evaluation of mitogen-induced responses in marine mammal and human lymphocytes by in-vitro exposure of butyltins and non-ortho coplanar PCBs

The effects of exposure to butyltin compounds (BTs: tributyltin; TBT, dibutyltin; DBT and monobutyltin; MBT) and non-ortho coplanar PCBs (IUPAC 77, 126 and 169) on marine mammals and human lymphocyte were evaluated. Peripheral blood mononuclear cells (PBMCs) isolated from Dall's porpoises (Phocoenoides dalli), bottlenose dolphins (Tursiops truncatus), a California sealion (Zalophus californianus), a larga seal (Phocoa largha) and humans (Homo sapiens) were exposed at varying concentrations of BTs and coplanar PCBs. Concanavalin A (Con A)-stimulated mitogenesis found significantly suppressed (P<0.01) when the cells were exposed at 300 nM (89 ng/ml) of TBT and 330 nM of DBT (77 ng/ml), while MBT showed little cytotoxicity at treatment levels of up to 3,600 nM (620 ng/ml). BTs concentrations in the liver of Dall's porpoises from Japanese coastal waters ranged between 81-450 ng/g for TBT and 200-1,100 ng/g (wet wt.) for DBTs, which is greater than the cytotoxic levels registered in this study. In contrast, non-ortho coplanar PCBs did not suppress cell proliferation at concentrations of up to 30 nM (10 ng/ml). The residue levels of coplanar PCBs in the blubber of Dall's porpoises were 0.12-1.3 ng/g, which were one order of lower than those levels that do cell proliferation. When cells were exposed to a mixture of TBT/DBTand coplanar PCBs, the proliferation was significantly reduced to 33 nM DBT plus 34 nM CB-77 and 33 nM DBT plus 28 nM CB-169 mixtures, respectively. The investigations relating the contaminant-induced immunosuppression in marine mammals have been focused on persistent organochlorines such as PCBs. pesticides and dioxin compounds. However, this study suggested the possibility of BTs could also pose a serious threat to the immune functions in free-ranging marine mammals and humans.     

Participation of the C-type hemolymph lectin in mineralization of the acorn barnacle Megabalanus rosa

BRA-2, a major C-type lectin in the hemolymph of the acorn barnacle Megabalanus rosa was detected in shell-associated proteins. Immobilized BRA-2 promoted CaCO₃ crystallization as determined by an in vitro pH-drift mineralization assay. In nature, calcification occurs as wound repair in M. rosa after breakage of the shell plate. To observe this phenomenon, we inserted a rubber cube inside the mantle cavity of M. rosa through the basal plate, and kept the organisms in a tank for several weeks. The rubber cube was covered first with brownish-colored material, probably a melanin, and then with CaCO₃ 5 weeks after the insertion. In the CaCO₃-associated proteins, BRA-3, a minor component of M. rosa hemolymph lectins, was present in addition to BRA-2. The presence of both the lectins and their ligands on the hemocyte was also observed. These results suggest that the C-type lectins of the M. rosa hemolymph participate in mineralization as well as defense in these organisms.     

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.     

Hydrothermal treatment of MSWI bottom ash forming acid-resistant material

To recycle municipal solid waste incinerator (MSWI) bottom ash, synthesis of hydrothermal minerals from bottom ash was performed to stabilize heavy metals. MSWI bottom ash was mixed with SiO(2), Al(OH)(3), and Mg(OH)(2) so its chemical composition was similar to that of hydrothermal clay minerals. These solid specimens were mixed with water at a liquid/solid ratio of 5. The reaction temperature was 200 degrees C, and reactions were performed for 24-240h. Generation of kaolinite/smectite mixed-layer clay mineral was found in the samples after the reaction of the mixture of bottom ash, SiO(2), and Mg(OH)(2). Calcium silicate hydrate minerals such as tobermorite and xonotlite were also generated. X-ray powder diffraction suggested the presence of amorphous materials. Leaching tests at various pHs revealed that the concentration of heavy metals in the leachates from MSWI bottom ash hydrothermally treated with SiO(2) and Mg(OH)(2) was lower than that in leachates from non-treated bottom ash, especially under acid conditions. Hydrothermal treatment with modification of chemical composition may have potential for the recycling of MSWI bottom ash.     

Estimation of sources and inflow of dioxins and polycyclic aromatic hydrocarbons from the sediment core of Lake Suwa, Japan

To elucidate the historical changes in polychlorinated dibenzo-p-dioxin (PCDD), polychlorinated dibenzofuran (PCDF), coplanar polychlorinated biphenyl (co-PCB), and polycyclic aromatic hydrocarbon (PAH) inflows in Lake Suwa, their concentrations in the sediment core were analyzed in 5 cm interval. The maximum concentrations (depth cm) of PCDDs/DFs, co-PCBs, and PAHs were 25.2 ng/g dry (30-35 cm), 19.0 ng/g dry (30-35 cm), and 738, 795 ng/g dry (50-55 cm, 30-35 cm), respectively. Age and sedimentation rate of the sediment were estimated from the vertical changes in apparent density. Deposition rate of dioxins and PAHs were calculated from the concentration and sedimentation rate of the sediment. The results indicate that large amounts of dioxins and PAHs flowed into the lake in flood stage compared to normal stage.     

Accumulation features of persistent organochlorines in resident and migratory birds from Asia

Concentrations of organochlorine contaminants including polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), chlordane compounds (CHLs), hexachlorobenzene (HCB) were determined in the resident and migratory birds, which were collected from India, Japan, Philippines, Russia (Lake Baikal) and Vietnam. Accumulation patterns of organochlorine concentrations in resident birds suggested that the predominant contaminants of each country were as follows: Japan--PCBs Philippines--PCBs and CHLs, India--HCHs and DDTs, Vietnam--DDTs, and Lake Baikal--PCBs and DDTs. The migratory birds from Philippines and Vietnam retained mostly the highest concentrations of DDTs among the organochlorines analyzed, indicating the presence of stopover and breeding grounds of those birds in China and Russia. On the other hand, migratory birds from India and Lake Baikal showed different patterns of organochlorine residues, reflecting that each species has inherent migratory routes and thus has exposure to different contaminants. Species which have breeding grounds around the Red Sea and Persian Gulf showed high levels of PCBs, indicating the presence of areas heavily polluted by PCBs in the Middle East.     

Juvenile hormone agonists affect the occurrence of male Daphnia

The water flea Daphnia magna reproduces primarily by cyclic parthenogenesis. Environmental stimuli that signal a change to adverse conditions induce the organisms to switch from parthenogenesis to gamogenetic reproduction. During the gamogenetic period, they produce male daphnids and dormant resting eggs, which can survive prolonged periods of environmental adversity. However, little is known about the mechanisms associated with the switch from parthenogenesis to gamogenetic reproduction. We investigated the effects of several juvenoids on sex determination in Daphnia. Females less than 24 h old were exposed to various concentrations of the test substance and were observed for 21 days. It was found that they can trigger the appearance of male daphnids: the percentage of males in the population increases to a level greater than what occurs under ordinary environmental conditions. We found that methylfarnesoate, juvenile hormone III, methoprene, and the phenoxyphenoxy derivatives pyriproxyfen and fenoxycarb (both insecticides) reduced the production of offspring and produced sex ratios dominated by male daphnids. Pyriproxyfen and fenoxycarb showed striking effects at low concentrations. Exposure to either of these chemicals at a concentration of 330 ngl(-1) caused adult females to produce almost all male neonates. Methylfarnesoate, juvenile hormone III, and methoprene showed an effect in inducing male production at higher concentrations (3.7 x 10(3), 3.3 x 10(5), and 1.3 x 10(5) ngl(-1), respectively). Our findings suggest that juvenile hormone agonists, including some insecticides, affect the chemical signaling responsible for inducing the production of male offspring.     

Concentrations and composition of PCB congeners in the air around stored used capacitors containing PCB insulator oil in a suburb of Bangkok, Thailand

Accumulation of Zn, Cu, Pb and Cd was studied in snails fed for 120 days on diets contaminated with each metal separately and with all metals mixed together. The concentrations of Zn in food were in the range 39 to 12 200 mg kg(-1), Cu 9-1640 mg kg(-1), Pb 0.4-12 700 mg kg(-1), and Cd 0.16-146 mg kg(-1) on a dry weight basis. At the highest concentrations of all metals the consumption rates decreased significantly. For the remaining concentrations, Zn and Cu were accumulated in soft tissue in proportion to their concentrations in food. The lowest treatments of Pb and Cd did not cause any increase in soft tissue concentrations of these metals but at average treatments, a clear increase was observed. Copper was accumulated especially efficiently, exceeding concentrations in food throughout the whole range of treatments. Except for the lower end of experimental treatments, Zn was accumulated approximately in direct proportion to its concentration in the diet. Lead was the most efficiently regulated metal, with soft tissue concentrations always substantially lower than in food. Approximately 60% of Zn, 90% of Cu, 43% of Pb and 68% of Cd on average was assimilated from food. The assimilation efficiency of food alone was ca 74%. The concentrations of metals in shells increased significantly with exposure, but (with one exception) the concentrations in shells did not exceed 5% of those found in soft tissue. We argue that snails are more important as agents of food-chain transport of Cu and Cd, than of Zn or Pb. Our results indicate also that snails are not able to deposit significant quantities of metals in their shells, at least during the time scale of our laboratory experiment.     

Trace elements accumulation and their variations with growth, sex and habitat: effects on Formosan squirrel (Callosciurus erythraeus)

Formosan squirrels are considered a useful bio-indicator because their habitat exists within that of humans. Therefore, concentrations of 19 trace elements were determined in tissues of this species for assessment of environmental pollution in urban Kamakura and rural Izuohshima. Results of analyses revealed high Cu concentrations in the livers of Formosan squirrels. Moreover, concentrations of some trace elements from automobile exhausts-V, Zn, Cu and As-in the specimens from Kamakura were higher than those from Izuohshima. These results reflect the presence of pollution caused by human activities in Kamakura.