Polychlorinated dibenzo-p-dioxins and dibenzofurans in sediment, soil, fish, shellfish and crab samples from Tokyo Bay area, Japan

Concentrations of tetra- to octa-chlorinated dibenzo-p-dioxins and dibenzofurans in samples collected in or near Tokyo Bay, Japan, with a densely inhabited catchment area, were congener-specifically determined and discussed. Analyzed in this study were samples of surface sediment covering the whole bay area, reference soil representing atmospheric impact, and fish, shellfish and crab commonly consumed as food. The range of concentrations were comparable to or higher than those in other parts of Japan. The origins of these compounds in the catchment area of the bay were investigated in terms of homolog and isomeric compositions in the sediment samples. Biota-sediment accumulation factors for benthic species declined as the degree of chlorination increased.     

Examination of dioxin fluxes recorded in dated aquatic-sediment cores in the Kanto region of Japan using multivariate data analysis

Past dioxin (coplanar polychlorinated biphenyl (Co-PCB), 2,3,7,8-substituted polychlorinated dibenzo-p-dioxin (PCDD) and 2,3,7,8-substituted polychlorinated dibenzofuran (PCDF)) fluxes recorded in dated aquatic-sediment cores were analyzed using principal component analysis (PCA). The data set consisted of samples from four cores collected from the Kanto region of Japan. Time trends and spatial differences in the dioxin flux were examined, and the potential relationship to emission sources was investigated. Twenty-five compounds and 58 core slices, corresponding to the later half of the 20th century, were subjected to the analysis. The PCA of both log-transformed and maximum-value-standardized data successfully divided the dioxin compounds into a small number of groups, and three similar clusters of Co-PCBs, PCDDs and penta- to hepta-CDFs were identified. PCB formulations used in the past are judged to have been responsible for the major part of the Co-PCB flux recorded in the sediment cores. However, the relationship to emission sources needs further investigation. It is suggested that most 2,3,7,8-substituted PCDDs and PCDFs are different from Co-PCBs in their emission sources or movements in the environment. The subcore clusters obtained from the PCA of log-transformed data show that the cores from different sampling areas exhibited distinct dioxin fluxes and compositions. Common time trends among the cores were more effectively summarized by the PCA of maximum-value-standardized data focusing on relative time trends. PC scores show that recently the flux of each dioxin compound in the four cores has been generally declining after having reached a peak.     

Alteration of manganese distribution in organs of rats treated with streptozotocin

This work was carried out under the Visiting Researcher's Programme of the Research Reactor Institute, Kyoto University.     

Formation of PCDF, PCDD, PCB, and PCN in de novo synthesis from PAH: mechanistic aspects and correlation to fluidized bed incinerators

The difference of polychlorinated dibenzofurans (PCDF) isomer patterns between stoker type incinerators and some fluidized bed incinerators (FBI) is a key to understand the formation mechanisms in both types of incinerators. The total yield and the isomer patterns of PCDF, polychlorinated biphenyls (PCB), polychlorinated naphthalenes (PCN), and polychlorinated benzenes (PCBz) formed via de novo synthesis from polycyclic aromatic hydrocarbons (PAH) indicate that chlorinated aromatics in the FBI are formed as a result of PAH breakdown. The detailed analysis of the isomer patterns of PCDF, PCB and PCN gives a first insight into the transformation mechanism of the PAHs and the sequence of degradation, chlorination and oxygen insertion. The major chlorination takes part at the position of the C-C cleavage during degradation of the PAHs. Further chlorination of the hydrogen position of the former PAH takes part preferably in ortho-position to this chlorination or is directed by incorporated oxygen. A perylene structure in soot is proposed as basis for the observed PCDF pattern in the FBI. Polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated phenols (PxCP) were formed in lower concentrations from the de novo experiments indicating an additional formation pathway for these compounds in the FBI.     

Respiratory uptake kinetics of neutral hydrophobic organic chemicals in a marine benthic fish, Pseudopleuronectes yokohamae

We investigated the respiratory uptake kinetics of polychlorinated biphenyls (PCBs), organohalogen pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs), and 2,2′,4,4′-tetrabrominated diphenyl ether (BDE #47) in a marine benthic fish, Pseudopleuronectes yokohamae. The respiratory uptake efficiencies (E_W) of the chemicals, of which there have been no reports for the majority of persistent organic pollutants (POPs), were obtained by measuring the respiratory uptake rate constants (k₁) and the oxygen consumption rates of fish. Fish were exposed to water in which these chemicals were dissolved at environmentally relevant concentrations for 28 d, followed by 168 d of depuration in clean seawater. The k₁ and E_W values for 99 compounds were obtained, and they ranged from 2000 to 42 000 L kg-lipid⁻¹ d⁻¹ and from 0.060 to 1.3, respectively. The E_W values of the chemicals, except for PAHs, tended to increase with increasing values of the log octanol–water partition coefficients (K_OW) of the chemicals up to a log K_OW of 5. For log K_OW in the range 3–5, the E_W values in this study were much lower than those in a published study (about one-third). As a result of analysis by a two-phase resistance model, the resistance of transport rates to the lipid phase in this study was lower than was the case in the published study. These findings indicate that the E_W predicted by the published study for log K_OW in the range 3–5 may differ among fish species and water temperature, and further study is needed.     

The effects of soil and Trifolium repens (white clover) on the fate of estrogen

In this study, we investigated the behavior of estrogens in the rhizosphere of white clover (Trifolium repens, clover hereafter) with two different pot tests, using soil and agar as growth media. In a pot test using agar spiked with estrogen, the estrogen concentration in the agar with clover decreased to non-detectable levels within one month, while in the agar without clover, 60% of initially added estrogen remained after one month. The half-lives of estrone (E1) and 17β -estradiol (E2) in the agar with clover were 2.4–3.8 and 13.2 d, respectively. The dissipation of E1 followed first-order rate law, while that of E2 fitted a zero-order reaction, indicating that they had different mechanisms of dissipation from agar. In the soil pot test, the behavior of E1 and E2 was not influenced by clover. An initial rapid decrease in the amount of estrogen extracted by methanol/acetic acid was followed by persistence for 1–3 months, regardless of presence of clover. Moreover, in three weeks E1 and E2 were only partly degraded by microbes extracted from the soil used in the pot test. In this study, abiotic degradation of estrogens and sorption of estrogen to soil, rather than the effects of soil microbes and clover, contributed to the initial rapid dissipation of estrogens in the soil. However, the results of the agar pot test suggested that vegetation such as clover may significantly contribute to removal of estrogens when estrogens in aqueous phase are discharged with surface runoff and preferential flow after heavy rain in agricultural fields, or when present in soils with low estrogen sorptivity.     

Remediation of cadmium contamination in paddy soils by washing with chemicals: selection of washing chemicals

The efficiencies of neutral salts, strong acids, and chelates were tested for extracting cadmium (Cd) from three paddy soils. The higher the selectivity of the cations of the added neutral salts toward soil adsorption sites, the lower the pH in the extracts and the more soil Cd could be extracted. In addition, soil carbon and nitrogen contents and mineral composition were closely associated with the amount of Cd extracted. Calcium chloride and iron(III) chloride were selected as wash chemicals to restore Cd-contaminated paddy soils in situ. Washing with calcium chloride led to the formation of Cd chloride complexes, enhancing Cd extraction from the soils. The washing also substantially decreased soil levels of exchangeable and acid-soluble Cd, which are the major forms of bioavailable Cd for rice (Oryza sativa L.). The optimum conditions for in situ soil washing were also determined for calcium chloride.