Photodechlorination of octachlorodibenzothiophene and octachlorodibenzofuran: comparison of experimental degradation pathways with degradation pathways predicted by DFT

Polychlorodibenzothiophenes (PCDTs) are sulfur analogues of polychlorodibenzofurans (PCDFs) and have been detected in environmental samples. We used density functional theory calculations (Gaussian 98W) to predict the photodechlorination pathways of octachlorodibenzothiophene (OCDT) and octachlorodibenzofuran (OCDF) in hexane, and we compared the predicted pathways with those observed during UV irradiation experiments. OCDT and OCDF were observed to degrade through first-order dechlorination processes, and the rate constant for OCDT was less than one-third that for OCDF. The main experimental photodechlorination pathways of OCDT and OCDF led to hexachlorinated and tetrachlorinated congeners, respectively; that is, the photodechlorination pathway of OCDT differed from that of OCDF. On the assumption that the dechlorination mechanisms involved radical reactions, we used DFT calculations to estimate bond-dissociation energies and single-point energies of OCDT and OCDF and their dechlorinated congeners, and we used the resulting information, along with hypotheses regarding the rate-controlling step of the degradations, to predict theoretical degradation pathways. We propose that reaction of dechlorinated radicals with a hydrogen donor was the rate-controlling step for OCDT and that C-Cl bond dissociation by UV light was the rate-controlling step for OCDF.     

Characterization of Pu concentration and its isotopic composition in soils of Gansu in northwestern China

The total ^239+240Pu activities and ²⁴⁰Pu/²³⁹Pu atom ratios in surface soil samples (0–5 cm) in the Kumtag Desert in western Gansu Province, and in a soil core sample in Lanzhou were investigated using a sector-field ICP-MS. In the surface soil samples, ^239+240Pu activities in fine particles (<150 μm) were 1.3–2.1 times of those in coarse particles (150 μm–1 mm) which ranged from 0.005 to 0.157 mBq/g. Atom ratios of ²⁴⁰Pu/²³⁹Pu in the surface soils ranged from 0.168 to 0.192 with a mean of 0.182 ± 0.008. The mean ratio was similar to the typical global fallout value although the Kumtag Desert was believed to have received close-in fallout derived from Chinese nuclear weapons tests mainly conducted in the 1970s. Furthermore, the mean ²⁴⁰Pu/²³⁹Pu atom ratio observed in the soil core sample in Lanzhou was similar to the typical global fallout value. In the soil core sample, ^239+240Pu activities in the various layers ranged from 0.012 to 0.23 mBq/g, and the inventory of ^239+240Pu (32.4 Bq/m², 0–23 cm) was slightly lower than that expected from global fallout (42 Bq/m²) at the same latitude. Rapid downward migration of Pu isotopes was observed in Lanzhou soil core sample layers. The contribution of the 10-cm deep top layers of surface soils to total inventory was only 17%, while the contribution of deeper layers (10–23 cm) was as high as 83%. The ^239+240Pu activity levels and ²⁴⁰Pu/²³⁹Pu atom ratios in soils in Gansu Province, China are similar to those in atmospheric deposition samples collected in the spring in recent years in Japan.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in invertebrate animals from a rural beach in Japan

PCDDs and PCDFs were analyzed by high resolution GC MS in several invertebrate animals collected from a rural beach in Japan. PCDDs and PCDFs were detected in all samples. Total concentration of PCDDs and PCDFs ranged 8.8–120 pg g⁻¹ wet and 3.5–38 pg g⁻¹ wet, respectively. TEQs of invertebrate animals examined ranged from 0.048 pg g⁻¹ wet in sea slug to 0.91 pg g⁻¹ wet in mussel. Isomer profiles in all samples were similar to each other despite of variety of species. Their major sources are estimated to be herbicides such as CNP and PCP, and combustion by using a statistical analysis of isomer profiles.     

Accumulation of Hg and other heavy metals in the Javan mongoose (Herpestes javanicus) captured on Amamioshima Island, Japan

Concentrations of 22 elements (Mg, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Mo, Ag, Cd, Sb, Cs, Ba, Tl, total Hg (T-Hg), Pb) and organic Hg (O-Hg) were examined in the liver, kidney and brain of the Javan mongoose (Herpestes javanicus) and in liver of the Amami rabbit (Pentalagus furnessi) from Amamioshima Island in Japan. Relatively high levels of T-Hg levels (from 1.75 to 55.5 microg g-1 wet wt.) were found in the Javan mongoose. As for a comparison of hepatic T-Hg concentrations between the two areas, there was no significant difference between the Javan mongoose in Amamioshima and those in the Okinawa islands. In addition, T-Hg levels in the livers of the Amami rabbit were the same as in the livers of other herbivorous mammals. Taken together, it suggested that T-Hg accumulation in the livers of the Javan mongoose was not affected by the environment but by a specific physiological mechanism. The comparison of Hg and other heavy metal accumulations between terrestrial mammals (13 species, 61 individuals) including the Javan mongoose and marine mammals (18 species, 508 individuals) were also discussed.     

Geographical distribution of polybrominated diphenyl ethers (PBDEs) and organochlorines in small cetaceans from Asian waters

Polybrominated diphenyl ethers (PBDEs) are one of the flame retardants widely used in plastics, textiles, electronic appliances, and electrical household appliances. In this study, PBDEs and organochlorine compounds (OCs) were determined in the archived samples from the Environmental Specimen Bank for Global Monitoring (es-BANK) at Ehime University. The blubber of cetaceans found stranded along the coasts of Japan, Hong Kong, the Philippines and India during the period from 1990 to 2001 were employed for chemical analysis to understand the present status of contamination and the specific accumulation of PBDEs. PBDEs were detected in all the cetacean samples analyzed, and concentrations were one or two orders of magnitude lower than for PCBs and DDTs. Concentrations of PBDEs ranged from a low value of 6.0 ng/g lipid wt. in spinner dolphin (Stenella longirostris) from India to a high value of 6000 ng/g lipid wt. in Indo-Pacific humpback dolphin (Sousa chinensis) from Hong Kong. No difference in PBDE levels between coastal and offshore species from Japan was observed, implying the existence of pollution sources in this region other than Japan. Highest concentrations of PBDEs were found in animals from Hong Kong, followed by Japan, and much lower levels from the Philippines and India, suggesting that developing nations may also have pollution sources of PBDEs. Geographical distribution of PBDEs in Asian waters was different from PCBs but similar to DDTs.     

New energy policy and low-carbon society in Japan after the Great East Japan Earthquake

The Great East Japan Earthquake in March 2011 devastated the eastern region of Japan.Due to the resulting nuclear accident,Japanese Cabinet decided to revise its energy policies.The Energy and Environment Council in National Policy Unit published options on the nation’s scenarios for energy and economy in 2030.We estimated the economic impacts of the options to national economy and households in 2030.Finally,we clarified significant factors to establish a secure,affluent and low-carbon society based on the energy scenarios.     

Indirect identification of an unstable intermediate in γ-HCH degradation by Pseudomonas paucimobilis UT26

While a postulated intermediate, 1,3,4,5-tetrachlorocyclohexa-1,4-diene(1,4-TCDN), is one of the key-compounds in γ-hexachlorocyclohexane(γ-HCH) degradation by Pseudomonas paucimobilis UT26(UT26), it has neither been isolated nor identified yet. Thus, an indirect identification was attempted to demonstrate its existence by a chemical oxidation of the microbial degradation products in situ.

1,2,4,5-Tetrachlorobenzene(1,2,4,5-TeCB) was newly produced by the chemical oxidation with hydrogen peroxide under iron(II) of W medium containing degradation products in situ of γ-1,3,4,5,6-pentachlorocyclohexene(γ-PCCH) by Escherichia coli MV1184(E. coli) which possesses the dehydrochlorinating activity of UT26. The chemical oxidation required the preceding enzymatic reactions to γ-PCCH by E. coli for the production of 1,2,4,5-TeCB. In facts, 1,2,4,5-TeCB was not produced from γ-PCCH by either of the chemical or enzymatic reaction alone.

Considering these results and the fact that hydrogen peroxide is known to dehydrogenate chemical compounds, it was concluded that 1,2,4,5-TeCB was produced directly from the unstable intermediate, 1,4-TCDN, on yielded from γ-PCCH by an enzymatic dehydrochlorination.     

The influence of lower extremity postures on kinematics and injuries of cyclists in vehicle side collisions

Objective: A cyclist assumes various cyclic postures of the lower extremities while pushing the pedals in a rotary motion while pedaling. In order to protect cyclists in collisions, it is necessary to understand what influence these postures have on the global kinematics and injuries of the cyclist.

Method: Finite element (FE) analyses using models of a cyclist, bicycle, and car were conducted. In the simulations, the Total Human Model of Safety (THUMS) occupant model was employed as a cyclist, and the simulation was set up such that the cyclist was hit from its side by a car. Three representative postures of the lower extremities of the cyclist were examined, and the kinematics and injury risk of the cyclist were compared to those obtained by a pedestrian FE model. The risk of a lower extremity injury was assessed based on the knee shear displacement and the tibia bending moment.

Results: When the knee position of the cyclist was higher than the hood leading edge, the hood leading edge contacted the leg of the cyclist, and the pelvis slid over the hood top and the wrap-around distance (WAD) of the cyclist's head was large. The knee was shear loaded by the hood leading edge, and the anterior cruciate ligament (ACL) ruptured. The tibia bending moment was less than the injury threshold. When the cyclist's knee position was lower than the hood leading edge, the hood leading edge contacted the thigh of the cyclist, and the cyclist rotated with the femur as the pivot point about the hood leading edge. In this case, the head impact location of the cyclist against the car was comparable to that of the pedestrian collision. The knee shear displacement and the tibia bending moment were less than the injury thresholds.

Conclusion: The knee height of the cyclist relative to the hood leading edge affected the global kinematics and the head impact location against the car. The loading mode of the lower extremities was also dependent on the initial positions of the lower extremities relative to the car structures. In the foot up and front posture, the knee was loaded in a lateral shear direction by the hood leading edge and as a result the ACL ruptured. The bicycle frame and the struck-side lower extremity interacted and could influence the loadings on lower extremities.     

Growth and reproductive biology of the small penaeid shrimp Trachysalambria curvirostris in Tokyo Bay

We investigated the growth and reproductive biology of the penaeid shrimp Trachysalambria curvirostris in Tokyo Bay, Japan, by monthly bottom-trawl surveys from May 2002 to December 2004. We also examined oogenesis in T. curvirostris by histological observation of the ovary. Females grew faster and attained a larger body size for age than males. The growth rate was high in summer and low in winter and was likely to be associated with seasonal changes in water temperature. The carapace length (CL) at which 50% of females contained vitellogenic oocytes was estimated to be 17.0 mm. The reproductive season extended from May to October. Young-of-the-year appeared in October and could be traced across the months on CL histograms to the following September or October, indicating a 1-year life cycle. This extended reproductive season, together with our observation of asynchronous development of oocytes in the ovary, suggests that multiple spawning by individual females may occur during the reproductive season. Postovulated oocytes were not found among the samples we collected during the daytime, suggesting that final oocyte maturation and spawning occur at night. Cortical crypts in the cytoplasm of the oocyte, considered to be a general feature of oogenesis in penaeid shrimps, were not found in T. curvirostris, even in oocytes undergoing germinal vesicle breakdown. This result implies that the cortical reaction after spawning of T. curvirostris may be different from that of other penaeid shrimps.     

The pollution and ecological risk of endosulfan in soil of Huai’an city, China

Endosulfan, a persistent organic pollutant newly listed under the Stockholm Convention, is currently widely produced and used as a pesticide in China. Concentrations of endosulfans (including α-, β-isomers, and their metabolite endosulfan sulfate) were determined in surface soil collected from Huai’an city, where the largest endosulfan producer is located. The concentrations of Σendosulfan (sum of α-endosulfan, β-endosulfan, and endosulfan sulfate) at all sites ranged from 0.28 to 44.81?ng/g dry weight (dw), following a lognormal distribution. The geometric mean was 1.09?ng/g dw, and the geometric standard deviation was 3.02. The β-endosulfan levels were consistently greater than those of α-isomer. The concentration ratios of α-endosulfan to β-endosulfan ranged from 0.03 to 0.70, which were much lower than the commercial endosulfan mixture. This is because that α-endosulfan is more volatile and degrades faster than β-endosulfan in soil. The contour map of Σendosulfan levels in soil indicates that the factory was the point pollution source with the highest endosulfan level in its surrounding area, especially the southern area. However, the non-point agricultural sources are more important. Based on Monte Carlo simulation, the Σendosulfan inventory in soil in Huai’an is estimated to be 0.8–3.0 tons. In order to understand the potential ecological risk of endosulfan, the Monte Carlo-based hazard quotient distribution was estimated and showed that Σendosulfan posed a potentially high risk to soil organisms. To our knowledge, this study is the first that reports soil pollution and risk of endosulfan around the manufacturer in China. This study will help China’s implementation of Stockholm Convention for the reduction and elimination of endosulfan in future.