Characterization of semi-volatile organic compounds emitted during heating of nitrogen-containing plastics at low temperature

Because of recent volume increases, appropriate management of plastic recycling, which generates various organic compounds, is required to ensure the chemical safety of the processes. The processing temperature and resin type are the important factors determining both the efficiency of the processes and the emission of chemicals. Therefore, we studied the thermal degradation of various plastics at various temperatures from 70 to 300 °C under oxygen-present conditions to identify the semi-volatile organic compounds (SVOCs) emitted and to understand their thermal behaviors. The plastics examined were nitrogen-containing resins, such as polyamide 6, polyurethane, melamine formaldehyde, urea formaldehyde and acrylonitrile-butadiene-styrene. Major commodity plastics were also investigated for comparison. In total, more than 500 SVOCs were detected as emissions from plastics. While various nitrogen-containing SVOCs were detected from nitrogen-containing resins, the major commodity plastics released only these, which possibly were included as additives. These results indicate that the nitrogen atoms in the SVOCs emitted originated from the resins and additives, and not from ambient air at low temperature. As a result of the detection of raw materials, degradation chemicals and by-products of the polymers in the emissions, we found that the variation in chemical species is dependent on the resins. Additives were also emitted from all the resins, meaning that these chemicals were also released to the environment at the temperature examined. In most cases, the numbers and concentrations of SVOCs increased with increasing heating temperature. The variation of thermal behaviors of SVOCs was related to the origins and chemical species of SVOCs.     

Studies on the fusion reaction in two species of Perophora (Ascidiacea)

Histological and electron microscopical studies were made on the fusion reaction between homogeneic stolons of the colonial ascidians Perophora japonica Oka and P. sagamiensis Tokioka. When two stolons make a tip-to-side contact, the epidermal cells of the lateral portion of one stolon become thick and form a protrusion. In the fusion reaction of P. japonica, epidermal cells of each stolon at the contact area extend cell processes immediately after contact. After an occurrence of degenerated epidermal cells, blood interchange between the two stolons is initiated by a partial elimination of the epidermal cells. Even after the establishment of blood interchange, the cuticlelike structure is often observed to remain at the contact area. In the fusion reaction of P. japonica, many amoebocytes are attached to the epidermal cells until the complete elimination of epidermal cells. In the fusion reaction of P. sagamiensis, many lymphocytes as well as amoebocytes are attached to the epidermal cells at the contact area.Contribution No. 461 of the Shimoda Marine Research Center     

Antimony in municipal waste.

Antimony content in municipal waste was studied. Sampled municipal waste was dried, crushed and analyzed. Antimony determinations were performed by Kjeldahl decomposition--batch hydride generation spectrometry and neutron activation analysis. Overall content of antimony in waste was 40-50 g/t raw waste. It was estimated than 20% of the annual production of antimony was discarded as municipal waste in Japan. Leaching of antimony from antimony-added materials may occur, because "small tips" involved considerable amounts of antimony.     

The contribution of azo dyes to the mutagenic activity of the Cristais River

To verify whether dyes emitted within the discharge of a dye processing plant were contributing to the mutagenicity repeatedly found in the Cristais River, Sao Paulo, Brazil, we chemically characterized the following mutagenic samples: the treated industrial effluent, raw and treated water, and the sludge produced by a Drinking Water Treatment Plant (DWTP) located approximately 6 km from the industrial discharge. Considering that 20% of the dyes used for coloring activities might be lost to wastewaters and knowing that several dyes have mutagenic activity, we decided to analyze the samples for the presence of dyes. Thin layer chromatographic analysis indicated the presence of three prevalent dyes in all samples, except for the drinking water. This combination of dyes corresponded to a commercial product used by the industry, and it tested positive in the Salmonella assay. The structures of the dye components were determined using proton magnetic resonance and mass spectrometric (MS) methods, and the dyes were tested for mutagenicity. The blue component was identified as the C.I. Disperse Blue 373, the violet as C.I. Disperse Violet 93, and the orange as C.I. Disperse Orange 37. The dyes showed mutagenic responses of 6300, 4600, and 280 revertants/microg for YG1041 with S9 respectively. A bioassay-directed fractionation/chemical analysis showed that the C.I. Disperse Blue 373 contributed 55% of the mutagenic activity of the DWTP sludge. We showed that these dyes contributed to the mutagenic activity found in the Cristais River environmental samples analyzed and are indirectly affecting the quality of the related drinking water. Therefore, we believe that this type of discharge should be more thoroughly characterized chemically and toxicologically. Additionally, human and ecological risks associated with the release of dye processing plant effluents should be more fully investigated, especially where the resultant water is taken for human consumption.     

Persistent organochlorine residues in human breast milk from Hanoi and Hochiminh City, Vietnam: contamination, accumulation kinetics and risk assessment for infants

Despite the ban on persistent organochlorines (OCs) in most of the developed nations, their usage continued until recently in many Asian developing countries including Vietnam, for agricultural purposes and vector-borne disease eradication programs. In this study, we collected human breast milk samples from the two big cities in Vietnam: Hanoi (n=42) and Hochiminh (n=44) and determined the concentrations of persistent OCs such as PCBs, DDT and its metabolites (DDTs), hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB), chlordane compounds (CHLs) and tris-4-chlorophenyl-methane (TCPMe). The contamination pattern of OCs was in the order of DDTs > PCBs > HCHs > CHLs approximately HCB approximately TCPMe. Compilation of available data indicated that DDT residue levels in human breast milk from Vietnam were among the highest values reported for Asian developing countries as well as developed nations. This result suggests recent usage of DDTs in both north and south Vietnam. Interestingly, in both cities, the p,p'-DDT portion was higher in multiparas than those in primiparas. Considering the fact that the interval between the first and the second child of a mother in Vietnam is usually short, this result probably indicates continuous intake of DDTs in the population. Analysis of infant exposure to DDTs via breast milk suggested that the daily intake rates for number of individuals are close to or above the threshold for adverse effects which may raise concern on children health.     

Distribution of antigenic sites common to vertebrate tropomyosin in tunicate muscle

The similarity of immunological characteristics of vertebrate and tunicate tropomyosins was studied with special regard to the phylogeny of tunicates. The antigenic sites common to vertebrate skeletal muscle tropomyosin was detected by immunohistochemical methods in the tail muscle of ascidians and muscle bands of thaliaceans, but not in the tail muscle of appendicularians. From this result, the phylogeny of the tunicate is speculated and compared with that postulated in studles of comparative morphology and taxonomy.Contribution No. 327 from the Shimoda Marine Research Center, The University of Tsukuba, Japan.     

Comparison of trace element accumulation in Baikal seals (Pusa sibirica), Caspian seals (Pusa caspica) and northern fur seals (Callorhinus ursinus)

Concentrations of 18 trace elements (V, Cr, Mn, Co, Cu, Zn, Se, Rb, Sr, Zr, Mo, Ag, Cd, Sb, Cs, Hg, Tl and Pb) were determined in liver, kidney, muscle and hair of Baikal seals, Caspian seals and northern fur seals. All the three species showed the highest concentrations of Hg, V, Mn, Se and Ag in liver, Cd, Co and Tl in kidney, and Cs in muscle among the soft tissues examined. The highest burdens of Zn, Rb and Cs were observed in muscle, Mo and Ag in liver, and Sb and Pb in hair in all the three species. Concentrations of non-essential elements, Rb, Cd, Cs and Hg, showed significant positive correlations among liver, kidney and muscle, whereas correlation coefficients for essential elements, Mn, Co, Cu, Zn and Se, between the three tissues were generally low for all the species, suggesting that homeostasis controls the concentrations of essential elements but not the non-essential elements in the tissues of these animals. Significant age-dependent increase was found in the concentrations of V, Se and Ag in liver and Hg in liver and kidney of all the three species. Hair concentrations showed significant positive correlations with Zn levels in liver and kidney and Hg in muscle for Caspian seals, Hg in liver and kidney for Baikal seals, and Pb in liver for northern fur seals. Furthermore, regression analysis using the data in the present study and in the literature showed significant positive correlations between Hg levels in hair, and liver, kidney and muscle for various species of pinnipeds. These results indicate the possibility of using hair samples for monitoring these trace elements in pinnipeds.     

Highly toxic coplanar PCBs: occurrence, source, persistency and toxic implications to wildlife and humans

Isomer-specific determinations of PCB congeners in a wide variety of animal species such as fish, marine mammals (whale, dolphin and porpoise) and terrestrial mammals (dog, cat and human) revealed the environmental occurrence of highly toxic coplanar 3,3',4,4'-tetrachlorobiphenyl (T(4)CB), 3,3',4,4',5-pentachlorobiphenyl (P(5)CB) and 3,3',4,4',5,5'-hexachlorobiphenyl (H(6)CB) within a range of few pg g(-1) to several ten ng g(-1) in fat tissues (except fish) on a wet weight basis. Detection of these toxic residues in wild specimens collected from remote areas such as the North Pacific suggests the already widespread distribution of coplanar PCBs as in the case of general PCB pollution. The clear positive correlations between concentrations of total PCBs and each of the three coplanar PCBs obtained in all mammals analysed suggest that the sources of coplanar PCB contamination to the environment are mainly commercial PCB preparations. Comparison of the composition of three toxic coplanar PCBs in commercial PCB mixtures and in the various animals indicates the relative metabolisability of these congeners as follows: 3,3',4,4'-T4CB>3,3',4,4',5-P5CB>3,3',4,4',5,5'-H6CB. Moreover, marine mammals seem to have lower potency to metabolise the coplanar PCBs in comparison with terrestrial mammals. In human adipose tissues, the concentrations of coplanar PCBs were found to be much higher than 2,3,7,8-tetrachlorodibenzo-p-dioxin (T(4)CDD), 2,3,4,7,8-pentachlorodibenzofuran (P(5)CDF) and other toxic congeners. 'T(4)CDD-equivalent' analysis based on the enzyme induction potencies and the residues of these toxic chemicals indicates that 3,3',4,4',5-P(5)CB may impose a greater toxic threat than dioxins and furans to the humans and probably to wildlife also.     

Correlation coefficients between the dioxin levels in mother's milk and the distances to the nearest waste incinerator which was the largest source of dioxins from each mother's place of residence in Tokyo, Japan

BACKGROUND: To observe the relationship between the PCDD/F and Co-PCB levels in samples of human breast milk and nearby waste incinerators in Tokyo, Japan. METHODS: Breast milk was taken from 240 mothers residing in Tokyo, Japan to measure and analyze the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs; 14 congeners), polychlorinated dibenzofurans (PCDFs; 15 congeners), and coplanar polychlorinated biphenyls (Co-PCBs; 12 congeners) contained in the fat. Individual milk samples (about 50 ml) were obtained from the mothers 30 days after delivery, between the months of June and September in 1999 and 2000. A map of Tokyo was used to measure the distances between each mother's place of residence and the closest public and industrial waste incinerators. RESULTS: The distances to the nearest waste incinerators bore no apparent correlations with the congeners of PCDD/Fs and Co-PCBs. The distances were also uncorrelated with the mean toxic equivalent quantities (TEQs) of PCDD/Fs (the sum of PCDDs and PCDFs), Co-PCBs, and the total PCDD/Fs and Co-PCBs. CONCLUSIONS: Although waste incinerators were the largest source of dioxins in Japan at the time of the study, the dioxins levels of mother's milk bore no apparent relationships with the distances between the mothers' domiciles and the nearest waste incinerators. In this study, several meaningful factors were not taken into account, namely, the wind direction, the level of dioxin emitted from each incinerator, the level of environmental pollution of dioxins, and the average time the mothers stayed at home each day. A full understanding of these points awaits future studies.