A comparative study on the autoxidation of dimethyl ether (DME) comparison with diethyl ether (DEE) and diisopropyl ether (DIPE)

The Japanese government is planning to introduce DME as a substituted energy for oil and LNG. Introduction of DME could contribute greatly to both the prevention of global warming and the formation of resource-recycling societies. In these circumstances, a safety assessment of DME is very important when DME is used on a large scale. There is a possibility that prolonged exposure in air induces autoxidation to produce explosive organic peroxides during transportation and storage of DME. Therefore, the reactivity of DME with oxygen and the mechanism of the autoxidation were investigated. Accelerating Rate Calorimetry (ARC) was used to evaluate the thermal stability of DME and DIPE, a known peroxide producers, under adiabatic and various atmospheric conditions. In ARC studies of DME under oxygen, exothermic decompositions were detected although its self-heating rate was low in comparison with DIPE. Oven storage tests were carried out and iodimetry was used to measure the concentration of peroxides produced from DME in comparison with DIPE and DEE. However, no products could be found for DME either by GC/MS or by iodimetry, while some evidence of autoxidation of both DEE and DIPE were obtained from these experiments.     

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.     

Correlation between stomach temperatures and ambient water temperatures in free-ranging loggerhead turtles,Caretta caretta

Instruments were attached to loggerhead turtles, Caretta caretta, at Kamoda Point, Japan in 1989 and on the Senri-coast, Japan in 1991. We simultaneously obtained stomach temperatures, ambient water temperatures and diving depths from four free-ranging loggerhead turtles during the internesting periods, using small recorders. These data were analyzed to understand how body temperature was maintained. Ambient water temperatures changed coincidentally when turtles moved up or down, but a stable stomach temperatures was maintained despite water temperature fluctuations of ca. 20 to 90 min in duration. Loggerhead turtles also experienced water temperature fluctuations longer than 24 h. Stomach temperatures responded to those water temperature changes with a time lag of several hours (160, 170, 230 and 240 min). Stomach temperatures were higher than ambient water temperatures throughout the experimental periods. The median values of the thermal difference between stomach and water temperatures were 1.1, 1.3, 1.5 and 1.7°C. The higher stomach temperatures are thought to be caused by metabolic heat production.     

Inactivation of SARS-CoV-2 by Ozonated Glycerol

We evaluated the SARS-CoV-2-inactivation activity of ozonated glycerol (OG). When a viral solution with 1% fetal bovine serum (FBS) was mixed with test solutions at a ratio of 1:19 and incubated for 20 s, OG with ozone concentrations of over 1000 ppm inactivated ≥ 94.38% of the virus. Extension of the reaction time to 1 h led to the inactivation of ≥ 99.82% of the virus (the viral titer was below the detection limit). Extension to 24 h resulted in concentrations over 200 ppm OG inactivating ≥ 99.87% of the virus (the viral titers were below the detection limit). Next, viral solutions with 1, 20, and 40% FBS were mixed with test solutions at a ratio of 1:19 and incubated for 5 min. Whereas the virucidal activity of 500 ppm OG was very limited in the presence of 1% FBS (79.47% inactivation), it increased in the presence of 20 and 40% FBS (95.13 and 97.95% inactivation, respectively; the viral titers were not below the detection limit). Meanwhile, over 1000 ppm OG inactivated ≥ 99.44% of the virus regardless of the FBS concentration (the viral titers were below the detection limit). Extension of the reaction time to 1 h led to 500 ppm OG inactivating ≥ 99.91 and ≥ 99.95% of the virus with 20 and 40% FBS, respectively (the viral titers were below the detection limit). These results suggested that OG might be useful as a virucidal agent against SARS-CoV-2.

     

Dynamics of PCDDs/DFs and coplanar-PCBs in an aquatic food chain of Tokyo Bay

Concentrations and accumulation profiles of PCDDs/DFs and coplanar-PCBs (co-PCBs) in aquatic biota (e.g., plankton, shellfish, benthic invertebrate, and fish) and sediment from Tokyo Bay were examined to elucidate the relationship between bioaccumulation and trophic level in the food web as determined by the stable nitrogen isotope analysis. Bioaccumulation patterns of PCDDs/DFs and co-PCBs varied greatly among congeners. Accumulation patterns of PCDDs/DFs and co-PCBs are not solely explained by their physicochemical properties. Biota-sediment accumulation factors (BSAFs) for co-PCBs in biota from Tokyo Bay were significantly greater than those of PCDDs/DFs. Furthermore, the slopes of the plots of delta15N and BSAF values and water solubility of 2,3,7,8-substituted PCDDs/DFs and co-PCBs were highly correlated. The results of our study would provide the valuable information to understand the accumulation properties of PCDDs/DFs and co-PCBs that can be used as a scientific basis to determine the sediment quality criteria of PCDDs/DFs and co-PCBs.     

Evaluation of an ecosystem model in ecological risk assessment of chemicals

We used a Lake Suwa version of Comprehensive Aquatic Systems Model (CASM_SUWA) to demonstrate the risk estimation of 10 different chemicals and examined the applicability and reliability of the model in ecological risk assessment by qualitatively and quantitatively comparing with the results of studies on multiple species using mesocosm tests. The qualitative comparison of the model results with those of the reported mesocosm tests indicated that some evidence observed in mesocosm studies supported the indirect effects predicted from simulation using the model. The comparison of the concentration levels at which 20% biomass reduction (BR20) in the most sensitive population estimated from the model with the no-observed effect concentration values derived from multiple species mesocosm tests (MS-NOEC) suggested that both data were related to each other and the model can be used to help in the determination of an ecological acceptable level of chemicals in aquatic environments. The analysis of the potential of indirect effects of a chemical for fish population indicated that the magnitude of the potential of indirect effects was quantified based on the ratio of BR50 to LC50 for fish population.     

Trends in the enantiomeric composition of polychlorinated biphenyl atropisomers in human breast milk

For the precise estimation of the risk to human health caused by persistent organic pollutants (POPs), it is important to discuss enantiomer fraction value (EF value) because it is reported that behaviors such as stability and toxicity of enantiomers are quite different in human body. Among POPs, polychlorinated biphenyl (PCB) is known as one of the most persistent compounds in human breast milk samples. The main exposure source of PCB for human body is mostly from food especially in seafood. The contamination of fish and shellfish has been a serious problem for the Japanese, who consume a large amount of fish in their diet. PCBs have 19 congeners which are chlorine-substituted in 3- or 4- ortho positions are known to have enantiomers. In this study, we analyzed PCB 183 (2,2′,3,4,4′,5′,6-hepta CB) in human breast milk and fish samples enantioselectively and revealed the time trends of the EF value. Though EF value of PCB 183 in fish samples sustained close to racemate (EF?=?0.5) from 1982 to 2012, that in breast milk increased over time. This fact indicates that (+)-PCB-183 has greater bioaccumulation potential than (-)-PCB-183 in human body; therefore, the toxicity of (+)-PCB-183 should be emphasized.     

A GIS-based evaluation of the effect of decontamination on effective doses due to long-term external exposures in Fukushima

Despite the enormous cost of radiation decontamination, there has been almost no quantitative discussion on how much it would reduce the long-term external radiation exposure in the Evacuation Zone and Planned Evacuation Zone (restricted zone) in Fukushima. The aim of this study is to assess the effectiveness of decontamination and return options and to identify important parameters for estimating the long-term cumulated effective dose (CED) during 15, 30 and 70 year period using data on land-use, population and decontamination in the restricted zone (about 1100 km²) in Fukushima.     

Photodegradation fates of cis-chlordane, trans-chlordane, and heptachlor in ethanol

cis-Chlordane, trans-chlordane, and heptachlor were photodegraded in ethanol, and their degradation fates and degradation products were determined by a computational chemical method. The most degradable material was heptachlor (first-order reaction constant k=0.13 min(-1)). Chlorine balances changed during UV irradiation, and the chlorine atoms in chlordane and heptachlor were eventually mineralized. cis-Chlordane, trans-chlordane and heptachlor each generated two di-dechlorinated products. Reactivities at various positions in these compounds were predicted on the basis of bond dissociation energies calculated by nonempirical molecular orbital calculation (Gaussian 98W).