挥发性氯代烃在湿润土壤中的平衡吸附研究

吸附是挥发性氯代烃(volatile chlorinated hydrocarbons,VCHs)赋存于土壤的主要机制之一.开展动态吸附实验,研究了4种常见VCHs污染物在我国8种典型土壤中的吸附平衡关系.结果表明,土壤在干燥条件下对VCHs气体的吸附能力要远大于湿润条件,且随含水率的升高吸附能力急剧下降,在含水率达到10%以后土壤吸附量趋于稳定.湿润土壤对三氯乙烯(TCE)、四氯乙烯(PCE)、1,1,1-三氯乙烷(MC)气体的吸附等温线符合Henry型吸附等温式,而1,1,2-三氯乙烷(1,1,2-TCA)符合Freundlich模型.VCHs在湿润土壤中的吸附量总体上与土壤有机碳(soil organic carbon,SOC)含量呈正相关,且受SOC类型和化合物极性影响较大.弱极性的TCE、PCE在土壤中的吸附能力与SOC含量呈严格正相关,而极性的MC、1,1,2-TCA在黑土等高碳土壤中不仅与SOC含量有关,还受到SOC物质组成的影响.建立了TCE和PCE在湿润土壤中的平衡吸附量预测模型,预测值与实测值相关性良好(n=80,R2=0.98).     

Effects of copper chloride on formation of polychlorinated dibenzo-p-dioxins in model waste incineration

Combustion experiments in a laboratory-scale fluidized-bed reactor were conducted to elucidate the effects of copper chloride as a catalyst on polychlorinated dibenzo-p-dioxins (PCDDs) formation in municipal waste incineration. We used model wastes with and without copper chloride (CuCl₂ · 2H₂O), both of which contained polyvinyl chloride as a chlorine source. Combustion temperature was set to 900 °C, and the amount of air supplied was twice the stoichiometric ratio. The experimental setup was carefully planned to suppress the influences of experimental conditions except the waste composition. Results of these experiments showed that copper chloride in the waste increased the amount of PCDDs formed and made the homologue profile to shift towards the highly chlorinated species. Copper chloride contributes to the PCDDs formation by promoting chlorination, whereby the reaction is important in that organic matter is chlorinated directly by copper compounds. Copper chloride did not exert a great influence on the isomer distribution patterns of PCDDs, while there appeared a significant difference in the case of PCDFs. This points out the difference of the major formation mechanisms between PCDDs and PCDFs. PCDDs are less formed by the catalytic reactions from carbon/polycyclic aromatic hydrocarbons than PCDFs in our experimental conditions.     

Estimating the mitigation effect of Tokai earthquake measures on housing damage: a counterfactual approach

This paper evaluates the mitigation effect of Tokai earthquake measures on housing damage using a counterfactual approach. It focuses on those measures that stimulate ex‐ante investment in disaster prevention in the supposedly affected area, including earthquake‐proof retrofitting and improved housing construction; the effect of the measures on housing losses is estimated monetarily. The study compares factual disaster damage computed using a real distribution of houses with counterfactual damage to a hypothetical housing distribution that would occur if the measures were not implemented. The key findings are: (i) the disaster mitigation effects of Tokai earthquake measures on housing amount to approximately JPY 18 billion (USD 0.18 billion) for Yamanashi Prefecture and JPY 0.26 trillion (USD 2.6 billion) for Shizuoka Prefecture, which would be at the centre of the event; (ii) a before–after comparison biases estimates of the mitigation effect; and (iii) statistically, the measures do not mitigate the housing damage predicted for an earthquake in Tokai.     

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.     

Chlorinated polycyclic aromatic hydrocarbons in surface sediment from Maowei Sea,Guangxi, China: occurrence,distribution, and source apportionment

Environmental Science and Pollution Research - Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) with three to five aromatic rings have been documented to ubiquitously occur in environmental...     

A copula-based inference to piecewise exponential models under dependent censoring,with application to time to metamorphosis of salamander larvae

In ecology and evolutionary biology, controlled animal experiments are often conducted to measure time to metamorphosis which is possibly censored by the competing risk of death and the follow-up end. This paper considers the problem of estimating the survival function of time-to-event when it is subject to dependent censoring. When the censorship is due to competing risks, the traditional assumption of independent censorship may not be satisfied, and hence, the usual application of the Kaplan–Meier estimator yields a biased estimation for the survival function of the event time. This paper follows an assumed copula approach (Zheng and Klein in Biometrika 82(1):127–138, 1995) to adjust for dependence between the event time of interest and the competing event time. While the literature on an assumed copula approach has mostly focused on semiparametric settings, we alternatively consider a parametric approach with piecewise exponential models for fitting the survival function. We develop maximum likelihood estimation under the piecewise exponential models with an assumed copula. A goodness-of-fit procedure is also developed, which touches upon the identifiability issue of the copula. We conduct simulations to examine the performance of the proposed method and compare it with an existing semiparametric method. The method is applied to real data analysis on time to metamorphosis for salamander larvae living in Hokkaido, Japan (Michimae et al. in Evol Ecol Res 16:617–629, 2014).     

Studies on automated survey system of environmental chemicals by gas chromatography-mass spectrometry-computer I. Retrieval system of mass spectra

A retrieval system of mass spectra based upon the Probability Based Matching method was studied in order to apply it to survey the chemicals in environments by a gas chromatography-mass spectrometry-computer system. As retrieval indices, peak missing probability and relative confidence value were proposed.     

Short-time exposure to mono-n-butyl phthalate (MBP)-induced oxidative stress associated with DNA damage and the atrophy of the testis in pubertal rats

Phthalates are widely used as plasticizer in various consumer domestic products and are known to disturb the male reproductive function in rodents. This study investigated the involvement of oxidative stress and the atrophy of the testes in pubertal rats exposed to mono-n-butyl phthalate (MBP). Four-week-old pubertal male rats were separated into three groups. In group I, 21 rats were fed rat chow containing 2 % MBP for 3 days. In group II, 21 rats were fed rat chow containing 2 % MBP for 3 days and antioxidant vitamins C (250 mg/kg/day) and E (50 mg/kg/day) were injected daily. In group III, 21 rats were fed standard rat chow and used as controls. After 3 days, each testis was weighed and the germ cell development was evaluated using the Johnsen score. The urinary 8-hydroxy-2′-deoxyguanosine (8-OHdG) levels were measured as a biological marker of oxidative DNA damage. The mean testis weight was significantly lower for group I than groups II or III (p?<?0.05). The mean Johnsen score was significantly lower for group I than for groups II or III (p?<?0.05). Urinary 8-OHdG concentrations were higher in group I than in groups II or III. Short-time exposure to MBP may therefore induce oxidative DNA damage in rat testes, while antioxidant vitamins administered during exposure may protect against this stress.     

Comparative study on indoor air quality in Japan and China: Characteristics of residential indoor and outdoor VOCs

We conducted a comparative study on the indoor air quality for Japan and China to investigate aromatic volatile organic compounds (VOCs) in indoor microenvironments (living room, bedroom, and kitchen) and outdoors in summer and winter during 2006–2007. Samples were taken from Shizuoka in Japan and Hangzhou in China, which are urban cities with similar latitudes. Throughout the samplings, the indoor and outdoor concentrations of many of the targeted VOCs (benzene, toluene, ethylbenzene, xylenes, and trimethylbenzenes) in China were significantly higher than those in Japan. The indoor concentrations of VOCs in Japan were somewhat consistent with those outdoors, whereas those in China tended to be higher than those outdoors. Here, we investigated the differences in VOC concentrations between Japan and China. Compositional analysis of indoor and outdoor VOCs showed bilateral differences; the contribution of benzene in China was remarkably higher than that in Japan. Significant correlations (p < 0.05) for benzene were observed among the concentrations in indoor microenvironments and between the outdoors and living rooms or kitchens in Japan. In China, however, significant correlations were observed only between living rooms and bedrooms. These findings suggest differences in strengths of indoor VOC emissions between Japan and China. The source characterizations were also investigated using principal component analysis/absolute principal component scores. It was found that outdoor sources including vehicle emission and industrial sources, and human activity could be significant sources of indoor VOC pollution in Japan and China respectively. In addition, the lifetime cancer risks estimated from unit risks and geometric mean indoor concentrations of carcinogenic VOCs were 2.3 × 10^?5 in Japan and 21 × 10^?5 in China, indicating that the exposure risks in China were approximately 10 times higher than those in Japan.