Theoretical study of the dechlorination reaction pathways of octachlorodibenzo-p-dioxin

The dechlorination reaction pathways of 1,2,3,4,6,7,8,9-octachlorodibenzo-p-dioxin (OCDD) by the hydrogen atom are investigated by the density-functional theory B3PW91 method. The dechlorination reactions have large exothermicity and small activation energies. The activation energies (approximately 5 kcal/mol) of the sigma-complex formation due to the hydrogen addition are lower than those (approximately 9 kcal/mol) of the direct chlorine abstraction. It is suggested that the sigma-complex plays an important role in the reactions, although it has scarcely been shown in previous studies of the dechlorination of dioxins. The sigma-complex formation is favored at low temperatures and the chlorine abstraction is favored at high temperatures. Furthermore, it is found that the lateral positions have a marginal preference over the longitudinal positions. The dechlorination of OCDD by the hydrogen atom is thus not likely to result in a dominant formation of the laterally substituted toxic congeners.     

Ecological risk assessment of pollutant chemicals: extinction risk based on population-level effects

The extinction probability is one of the most useful endpoints that are utilized in conservation biology. A parallel approach is advocated for the ecological risk assessment of chemical pollutants. The presented framework estimates extinction probability induced by pollutant chemicals in order to evaluate ecological hazards of pollution, and is applicable to any biological community (aquatic or terrestrial). The analytical framework, which is based on stochastic population dynamics theory, is briefly explained. The extinction risk estimation is feasible if ecotoxicological data concerning pollutant effects on population growth rate of organisms (the intrinsic rate of natural increase), and if environmental exposure concentration is provided. Tentative risk estimation was made for some agrochemicals and surfactants on zooplankton populations (Daphnia) as target organisms.     

Specific accumulation of polychlorinated biphenyls and organochlorine pesticides in Japanese common squid as a bioindicator

Organochlorines (OCs) representing Persistent Organic Pollutants (POPs) such as PCBs (polychlorinated biphenyls), DDTs (DDT and its metabolites), CHLs (chlordane compounds), HCHs (hexachlorocyclohexane isomers) and HCB (hexachlorobenzene) were determined in the liver of Japanese common squid (Todarodes pacificus) collected from the waters around Japan (Japan Sea and western North Pacific Ocean). Among OCs concentrations, PCBs (upto 5600 ng/g lipid wt.) were the highest, and those of other OCs were in the order of DDT> CHLs > HCHs > HCB. Studies on growth trend and seasonal variation of OCs in this species suggest a rapid reflection of the pollution levels in seawater where and when they were collected, regardless of body-length and time of collection. These results indicate that Japanese common squid is a suitable bioindicator for monitoring OCs pollution in waters around Japan. With regard to the geographical distribution of OCs in this species collected from waters around Japan, OCs concentrations in specimens from Japan Sea were higher than those from the Pacific Ocean. This result might reflect some existing of local pollution sources of OCs around Japan Sea, and slower water exchange between Japan Sea and open ocean.     

Influence of chemical characteristics of humic substances on the partition coefficient of a chlorinated dioxin

The partition coefficients (Koc) of 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin (HpCDD) with respect to a variety of humic substances (HSs) were evaluated by a method involving solid-phase microextraction and gas chromatography-electron capture detection. The log Koc values for each of the HS samples were in the range of 6.4-7.7. The log Koc values for HAs from tropical peat, brown forest and ando soils were in the range of 7.3-7.6, similar to the calculated value for the octanol-water partition coefficient (log Koc=7.56). In contrast, the log Koc values for FAs and peat HAs were 0.5-1 unit lower than the calculated value. The parameters for the polarity of HSs, as calculated from (N+O)/C, O/C atomic ratios and the carboxyl group content, were numerically similar related to the log Koc for HpCDD. These results show that the Koc values for HpCDD are significantly influenced by the polarity of HSs.     

Hydrodynamic and towing characteristics of a modified model of the Clarke Jet Net

In a series of studies to develop an effective high speed plankton sampler, hydrodynamic research was carried out on a modified model of the Clarke Jet Net. A theoretical analysis of the motion of the sampler was made using an IBM 7040 computer, and test tows were made in an experimental ship tank and at sea. To maintain the roll angle of the sampler at approximately zero, a v-shape bridle was applied. A pair of towing holes should be selected for the particular range of towing velocity. The calculated longitudinal stability seemed good in all the cases examined. Towing tests in the ship tank at 2 to 3 m/sec revealed sufficient stability. The motion of the sampler at speeds higher than 3 m/sec can be assumed from hydrodynamic coefficients derived from the ship tank experiment. Towing-cable characteristics, assumed by computation, indicated that about 500 m at 6 kt and 1,000 m at 12 kt should be paid out to lower the sampler down to 100 m. The effect of the sampler on the cable is found only adjacent to it and is almost negligible beyond 50 m from it in depth. Results of sea tests at 6 and 9 kt confirmed the stability of the sampler. Examination of the catch suggested that the present model can be used, with some modifications, for the quantitative and qualitative sampling of large zooplankton.Contribution No. 231 from the Seikai Regional Fisheries Research Laboratory, Nagasaki.     

Metal distribution in incineration residues of municipal solid waste (MSW) in Japan

This study aimed to identify distribution of metals and the influential factors on metal concentrations in incineration residues. Bottom ash and fly ash were sampled from 19 stoker and seven fluidized bed incinerators, which were selected to have a variety of furnace capacity, furnace temperature, and input waste. In the results, shredded bulky waste in input waste increased the concentration of some metals, such as Cd and Pb, and the effect was confirmed by analysis of shredded bulky waste. During MSW incineration, lithophilic metals such as Fe, Cu, Cr, and Al remained mainly in the bottom ash while Cd volatilized from the furnace and condensed to the fly ash. About two thirds of Pb and Zn was found in the bottom ash despite their high volatility. Finally, based on the results obtained in this study, the amount of metal in incineration residues of MSW was calculated and the loss of metal was estimated in terms of mass and money. A considerable amount of metal was found to be lost as waste material by landfilling of incineration residues.     

Finite element analysis of knee injury risks in car-to-pedestrian impacts

In vehicle-pedestrian collisions, lower extremities of pedestrians are frequently injured by vehicle front structures. In this study, a finite element (FE) model of THUMS (total human model for safety) was modified in order to assess injuries to a pedestrian lower extremity. Dynamic impact responses of the knee joint of the FE model were validated on the basis of data from the literature. Since in real-world accidents, the vehicle bumper can impact the lower extremities in various situations, the relations between lower extremity injury risk and impact conditions, such as between impact location, angle, and impactor stiffness, were analyzed. The FE simulation demonstrated that the motion of the lower extremity may be classified into a contact effect of the impactor and an inertia effect from a thigh or leg. In the contact phase, the stress of the bone is high in the area contacted by the impactor, which can cause fracture. Thus, in this phase the impactor stiffness affects the fracture risk of bone. In the inertia phase, the behavior of the lower extremity depends on the impact locations and angles, and the knee ligament forces become high according to the lower extremity behavior. The force of the collateral ligament is high compared with other knee ligaments, due to knee valgus motions in vehicle-pedestrian collisions.     

Setting the most robust effluent level under severe uncertainty: Application of information-gap decision theory to chemical management

Decisions in ecological risk management for chemical substances must be made based on incomplete information due to uncertainties. To protect the ecosystems from the adverse effect of chemicals, a precautionary approach is often taken. The precautionary approach, which is based on conservative assumptions about the risks of chemical substances, can be applied selecting management models and data. This approach can lead to an adequate margin of safety for ecosystems by reducing exposure to harmful substances, either by reducing the use of target chemicals or putting in place strict water quality criteria. However, the reduction of chemical use or effluent concentrations typically entails a financial burden. The cost effectiveness of the precautionary approach may be small. Hence, we need to develop a formulaic methodology in chemical risk management that can sufficiently protect ecosystems in a cost-effective way, even when we do not have sufficient information for chemical management. Information-gap decision theory can provide the formulaic methodology. Information-gap decision theory determines which action is the most robust to uncertainty by guaranteeing an acceptable outcome under the largest degree of uncertainty without requiring information about the extent of parameter uncertainty at the outset. In this paper, we illustrate the application of information-gap decision theory to derive a framework for setting effluent limits of pollutants for point sources under uncertainty. Our application incorporates a cost for reduction in pollutant emission and a cost to wildlife species affected by the pollutant. Our framework enables us to settle upon actions to deal with severe uncertainty in ecological risk management of chemicals.     

Behaviour of selected endocrine-disrupting chemicals in three sewage treatment plants of Beijing, China

Occurrence and fate of eight kinds of selected endocrine-disrupting compounds (EDCs) in three sewage treatment plants (STPs) of Beijing, China was investigated. These EDCs, composed of 4-octylphenol (4-OP), 4-n-nonylphenol (4-n-NP), bisphenol A (BPA), estrone (E1), 17α-estradiol (17α-E2), 17β-estradiol (E2), estriol (E3) and 17α-ethinylestradiol (EE2), in every step of STPs, were simultaneously analysed by gas chromatography/mass spectrometry after derivatisation. All the EDCs were detected in the influents of three STPs, and BPA was the most abundant compound. The concentrations of EDCs ranged from 36.6 ng/l of 17α-E2 (STP C) to 1342.3 ng/l of BPA (STP B) in the influent sewages and from below limits of detection of E2 and E3 (STP C) to 142.5 ng/l of E1 (STP B) in the effluent sewages. The STPs could not remove alkylphenols effectively from the aqueous phase with less than 40% reduction. BPA decreased over 90%, and steroid estrogens achieved considerable reductions from 64.8% of E2 to 94.9% of E3. Generally, biological treatment was more effective in removing alkylphenols, BPA and natural estrogens from the aqueous phase than primary treatment. However, the synthetic estrogen, EE2, was mostly removed by the primary treatment with about 63.5% reduction. It is the first time that the concentration of 17α-E2 in the sewage of China was reported in this paper. The compound might have a bearing with the waste effluents of dairy farms around urban area of Beijing.     

Influence of paint chips on lead concentration in the soil of public playgrounds in Tokyo

Lead concentration in the surface soils from 31 playgrounds in a ward in Tokyo was measured to examine if paint chips, peeled off from playing equipment installed in the playgrounds, contribute to elevated Pb concentration in the soil of public playgrounds. Lead concentration in the paint chips sampled from playgrounds ranged from 0.003 to 8.9%. Lead concentration in the surface soil ranged from 15.2 to 237 mg kg(-1) (average, 55.5 mg kg(-1)) and higher Pb concentration was found in the soil near painted playing equipment indicating that paint chips from playing equipment contributed to increase soil Pb level of playgrounds in Tokyo. The degree of peeling-off of paint on the surface of playing equipment in the public playground (peeling-off index: POI) positively correlated with Pb concentration in the soil (Spearman rank-correlation coefficient, r = 0.366, p = 0.043). The stronger correlation between Pb concentration and isotope ratios (207Pb/206Pb and Pb conc., r = 0.536, p = 0.002, 208Pb/206Pb and Pb conc. r = 0.600, p < 0.001) than that between Pb and POI indicated that gasoline Pb contributed more to the playground-to-playground variation in soil Pb concentration. It was concluded that both gasoline Pb of the past and paint chips contributed to increased Pb concentration in the surface soil of playgrounds in Tokyo, though the contribution of paint chips is smaller than gasoline Pb.