Large-scale fires and time trends of PCDDS/DFs in sediments

Drastic increases in PCDDs/DFs concentrations were identified in the uppermost layers of a sediment core sample taken from the coastal area of Kobe City. As large-scale fires caused by the Great Hanshin-Awaji earthquake were deemed to be a possible cause, we performed additional sampling of sediment cores and surface sediment samples, estimating the total amount of PCDDs/DFs released from fires and presuming the load to sediments by individual transport routes, such as air and water, using an air diffusion model to investigate the influence of fires. The total amount of PCDDs/DFs released from fires was estimated at 2000 g-total PCDDs/DFs, 22 g-TEQ. Increases in PCDDs/DFs generated in fires were principally transported through water rather than air. If 20% of the total PCDDs/DFs formed in fires had entered water, it would correspond to the entire increase of PCDDs/DFs concentration in sediment cores.     

Determination of pesticides and chronic test with Daphnia magna for rainwater samples

Pesticides contained in rainwater were investigated in June and July 2001 in Yokohama. Although there were few farms and rice paddies near the sampling point, insecticides (fenitrothion and dichlorvos) and fungicides (chlorothalonil and futhalide) were detected by GC-MS and GC-FPD analysis. The maximum concentrations of dichlorvos and fenitrothion were 0.22 microg/L and 0.15 microg/L, respectively. Chronic tests with Daphnia magna were then conducted on two rainwater samples. Test solutions for these chronic tests were prepared by solid-phase extraction. In the case of the rainwater sampled on 25 July, the survival rate of D. magna was 100% after 21 days and no differences were found between the control and sample with regard to the average total number of live offspring produced per parent animal. However, a similar test with rainwater sampled on 14-15 June showed a marked toxic effect, since all the test animals were dead within 2 days. It is concluded that rainwater containing pesticides is an important ecological factor for freshwater plankton.     

Experimental induction of gonadal maturation and spawning in the giant jellyfish <Emphasis Type="Italic">Nemopilema nomurai</Emphasis> (Scyphozoa: Rhizostomeae)

We studied the processes of gonadal maturation, spawning, fertilization and embryonic development of the giant jellyfish Nemopilema nomurai, which has been blooming in recent years in the Sea of Japan. Healthy medusae actively swimming offshore had immature gonads, but damaged and ashore-drifted animals had relatively mature gonads. The animals maintained in a small net on the nearshore to mimic the drifted condition showed induced gonadal maturation by the increase in oocyte diameter and darkness in the matrix. A similar maturation process also occurred in isolated pieces of ovary incubated at the same temperature. Fully grown oocytes that probably stopped at the prophase of the first meiosis reinitiated maturation divisions in response to light exposure, and massive spawnings occurred 80–100 min after the exposure. The spawned oocytes were first released within the subgenital sinus, then transported peripherally and finally shed into the gastrovascular cavity. Maturation and spawning in male gonads were similar to those of females except that the male spawning occurred within 30 min after the light exposure and always preceded the female spawning. Hence, it was suggested that fertilization might take place in the female gastrovascular cavity by the sperm that came in from surrounding seawater by animals’ pumping activities after dawn. Having mechanical damages might promote fertilization success of this species in the Sea of Japan.     

Substance flow analysis of coplanar PCBs released from waste incineration processes

Previous reports have focused on the emission of coplanar polychlorinated biphenyls (Co-PCBs) which have a toxic mechanism similar to that of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/DFs) released from municipal solid waste (MSW) incineration. Such emissions accounted for a small percentage of all the dioxins (PCDDs/DFs and Co-PCBs) recorded at the toxicity equivalent (TEQ) level. There is, however, very little information about Co-PCBs, such as the quantities being released and their effect on overall environmental pollution. The aim of this research has been to clarify the substance flow of Co-PCBs from MSW incineration processes. The results reveal that whereas the input of Co-PCBs into the MSW incineration facilities in Kyoto City was 0.13–0.29 μg-TEQ per ton waste, the total output of Co-PCBs (the sum of Co-PCBs released from emission gas, fly ash, and bottom ash) was 4.9 μg-TEQ per ton waste. The total output was therefore found to be higher than the total input. Over 90% of the total PCBs were decomposed in the incineration process. In comparing the profiles of congeners and homologues, those in the MSW were found to be similar to those detected in the atmosphere and products containing PCBs, but different from those in the MSW incineration gas. Received: August 26, 1998 / Accepted: March 2, 1999     

Concentrations, enrichment and predominant sources of Sb and other trace elements in size classified airborne particulate matter collected in Tokyo from 1995 to 2004

APM was collected and trace elements existing in the particles were monitored since May 1995 in this study. APM sample was collected separately by size (d < 2 microm, 2-11 microm and >11 microm) on the roof of the university building (45 m above ground) in the campus of Faculty of Science and Engineering, Chuo University, Tokyo, Japan, using an Anderson low volume air sampler. The collected sample was digested by HNO3, H2O2 and HF using a microwave oven, and major elements (Na, Mg, Al, K, Ca and Fe) were measured by ICP-AES, and trace elements (Li, Be, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, As, Se, Mo, Cd, Sb, Ba and Pb) were measured by ICP-MS. It was observed that the APM concentration was higher between the winter and the spring, compared to during the summer. The enrichment factor was calculated for each element in each set of APM (d < 2 microm, 2-11 microm and >11 microm). Seasonal trends of enrichment factors were examined, and the elements were classified into 3 groups according to the common seasonal behavior. It is likely that the elements in the same group have common origins. Toxic pollutant elements (Sb, Se, Cd, Pb and As) were found in small particles with d of <2 microm in concentrated levels. Antimony (Sb) had the highest enrichment factor, and the results suggested that Sb level in APM was extremely high. The origins of Sb were sought, and wastes from plastic incineration and brake pad wears of automobiles were suspected. Each set of APM (d < 2 microm, 2-11 microm and >11 microm) was classified by the shape, and the shape-dependent constituents of a single APM particle were quantitatively measured by SEM-EDX. High concentration of Sb was found in APM <2 microm and square particles. Particles less than 2 microm and square shaped particles were major particles produced by actual car braking experiments. From these experimental results it was concluded that the source of Sb in squared APM <2 microm is considered to be from brake pad wear.     

A simulation model for Japanese sardine (Sardinops melanostictus) migrations in the western North Pacific

A two-dimensional individual-based model coupled with fish bioenergetics was developed to simulate migration and growth of Japanese sardine (Sardinops melanostictus) in the western North Pacific. In the model, fish movement is controlled by feeding and spawning migrations with passive transport by simulated ocean current. Feeding migration was assumed to be governed by search for local optimal habitats, which is estimated by the spatial distribution of net growth rate of a sardine bioenergetics model. The forage density is one of the most important factors which determines the geographical distributions of Japanese sardine during their feeding migrations. Spawning migration was modeled by an artificial neural network (ANN) with an input layer composed of five neurons that receive environmental information (surface temperature, temperature change experienced, current speed, day length and distance from land). Once the weight of the ANN was determined, the fish movement was solved by combining with the feeding migration model. To obtain the weights of the ANN, three experiments were conducted in which (1) the ANN was trained with back propagation (BP) method with optimum training data, (2) genetic algorithm (GA) was used to adjust the weights and (3) the weights of the ANN were decided by the GA with BP, respectively. BP is a supervised learning technique for training ANNs. GA is a search technique used in computing to find approximate solutions, such as optimization of parameters. Condition factor of sardine in the model is used as a factor of optimization in the GA works. The methods using only BP or GA did not work to search the appropriate weights in the ANN for spawning migration. In the third method, which is a combined approach of GA with BP, the model reproduced the most realistic spawning migration of Japanese sardine. The changes in temperature and day length are important factors for the orientation cues of Japanese sardine according to the sensitivity analysis of the weights of the ANN.     

Effect of alumina and zirconia as binders on the activity of Fe-BEA for NH<Subscript>3</Subscript>-SCR of NO

Fe-BEA catalysts are active for the NH3-SCR of NO. For industrial application, a binder should be added to the Fe-BEA catalysts to make them tightly adhere to the monoliths. The addition of alumina and zirconia as binders to the Fe-BEA led to a different effect on NO conversion. The catalytic activity of the mixed samples was evaluated by the temperature programmed procedure in a flow-reactor system, and the mechanism was analyzed via SEM, BET, XRD and XPS. It was found that larger iron particles were formed by the migration of parent iron particles in the Fe-BEA catalyst with alumina. This led to the increase of Fe³⁺ magnitude and iron cluster, enhancing the abilities of NO oxidation and storage. Accordingly, the SCR activity increased slightly in low temperature but decreased sharply in high temperature. For the Fe-BEA with zirconia sample, NO oxidation and storage abilities decreased due to the less iron clusters. The increase of Fe³⁺ magnitude resulted in higher catalytic oxidation ability, which gave rise to little change in the SCR activity compared with the Fe-BEA.

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Substance flow analysis of brominated flame retardants and related compounds in waste TV sets in Japan

We conducted time-series substance flow analysis of two types of brominated flame retardants (BFRs)--polybrominated diphenyl ethers (PBDEs) and tetrabromobisphenol A (TBBPA)--and two types of related compounds--Sb (used with BFRs for flame inhibition) and polybrominated dibenzo dioxins and furans (PBDDs/DFs: unintended byproducts)--in five size categories of waste TV sets in Japan. Two scenarios were created with BFR substitutions and compared to a "business as usual" scenario in order to obtain basic information for strategic product management. The results showed that the use of DecaBDE in rear and front covers of TV sets began in fiscal 1987-1990 and 1993-1996, respectively, and that TBBPA was used to some extent as a substitute for DecaBDE in the 90s. The amount of waste Br in the plastic covers is predicted to increase until at least fiscal 2020 due to the increasing size of TV sets. Although substitution of BFRs with non-BFRs in Japan by 2006 will reduce waste Br, the amount in waste TV sets will not peak until fiscal 2009. The results will help inform decisions in Japan regarding the recovery and disposal of waste TV sets. The methods used would benefit waste managers faced with similar issues in other countries.     

Combustible and incombustible speciation of Cl and S in various components of municipal solid waste

Chlorine (Cl) and sulfur (S) in municipal solid waste (MSW) are important reactive elements during combustion. They generate the acidic pollutants HCl and SOx, and, furthermore, produce and suppress organic chlorinated compounds. Nevertheless, few practical reports about Cl and S content in MSW have been published. In combustion and recycling processes, both combustible Cl and S, and incombustible Cl and S species are equally important. This paper presents the results of a comprehensive study about combustible and incombustible Cl and S in MSW components, including kitchen garbage, paper, textiles, wood and leaves, plastics and small chips. By integrating this collected data with data about MSW composition, not only the overall content of Cl and S in MSW, but also the origins of both combustible and incombustible Cl and S were estimated. The average Cl content in bulk MSW was 3.7 g/kg of raw MSW, of which 2.7 and 1.0 g/kg were combustible and incombustible, respectively. The Cl contribution from plastics was 76% and 27% with respect to combustible and incombustible states. The average S content in bulk MSW was 0.81 g/kg of raw MSW, of which 0.46 g/kg was combustible and 0.35 g/kg was incombustible. Combustible S was mainly due to synthetic textiles, while incombustible S was primarily from paper.     

Waste wood recycling as animal bedding and development of bio-monitoring tool using the CALUX assay

Animal bedding made of waste wood samples from seven different plants in Japan were chemically analyzed in terms of persistent organic pollutants (POPs) including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/DFs), coplanar polychlorinated biphenyls (Co-PCBs), drin compounds, chlordane compounds and various inorganic toxic compounds (Cr, Cu, As, B, Cd and Pb) to investigate the chemical characteristics and levels of contamination. Further investigation was conducted to determine the success of applying the Chemically Activated Luciferase Expression (CALUX) bioassay to the waste wood samples in combination with a cleanup procedure for the detection of dioxin-like compounds in order to develop the CALUX bioassay as a rapid and cost-effective screening/monitoring method and a contributive tool to risk management in the waste wood recycling process. For the cleanup procedure, crude extracts from wood samples were prepared by dimethylsulfoxide (DMSO)/n-hexane extraction, and then the extracts were processed by silica gel-44% sulfuric acid reflux treatment at 70 degrees C for 60 min to yield the bioassay fractions. The presence of POPs and inorganic toxic compounds were confirmed in most of the litter samples. In particular, Co-PCBs in one sample (litter dust) showed a high concentration level (1200000 pg/g, 240 pg TEQ/g), suggesting the potential for contamination from demolition waste. The CALUX assay-determined TEQs (CALUX-TEQs) were significantly high in the sample after DMSO/n-hexane extraction, probably due to labile aryl hydrocarbon receptor (AhR) ligands such as PAHs; however, they were remarkably reduced through a single silica gel-44% sulfuric acid reflux treatment. The ratio between CALUX-TEQ values and WHO toxicity equivalent values (WHO-TEQ) obtained by congener-specific chemical analysis ranged from 0.058 to 22 and show comparatively good agreement. Underestimation in some samples, however, was observed where WHO-TEQ values of Co-PCBs contributed greatly to total WHO-TEQ values. Reasons for this gap could be lower CALUX assay-determined relative potencies (REPs) than the WHO-TEFs for these congeners or AhR-antagonistic effects of non dioxin-like PCBs which coexist at higher concentration than Co-PCBs. The CALUX assay is proposed as a promising application in the recycling process of wooden materials.