中日合作项目国内外危险化学品安全管理初步研究

按照中日合作项目《加强中国安全生产科学技术能力计划》,分析了日本、美国、加拿大、德国、欧盟和联合国等国际危险化学品安全管理现状,总结提出了实施风险评价、申报登记、风险控制、信息警示和员工培训等国际危险化学品安全管理方式及其特点。同时,结合中国危险化学品安全管理现状,提出了系统化建设危险化学品安全生产法规标准体系、制定作业场所危险化学品卫生要求、修订《危险化学品安全管理条例》等进一步建立健全中国危险化学品安全管理的对策和建议。这对完善中国危险化学品安全管理具有重要的参考意义。     

Congener-specific analysis of polychlorinated biphenyl in human blood from Japanese

Polychlorinated biphenyl (PCB) congeners were analyzed by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) of whole blood samples taken from 24 healthy adult Japanese volunteers (12 males and 12 females; age range 25–46 years). On average, 95 PCB congeners were detected in whole blood samples. The mean of total PCB concentration in whole blood was 771.9 pg g^–1 whole blood (139.6 ng per g-lipid). Congener-specific analysis identified the predominant PCB congeners as #153 (22.2), #180 (11.6), #138 (8.4), #182/187 (6.6), #118 (5.6), #163/164 (5.0), #99 (3.9), #74 (3.6), #146 (3.3), #170 (3.0) and #156 (2.2), representing 75.6 of all PCBs detected in the human blood samples. Among the predominant PCB congeners, #153, #180, #138, #187 #118, #99 and #74 had chlorine as the substituent at the 2-, 4- and 5- positions of the phenyl-ring. In human blood in Japanese individuals, it is assumed that these congeners would be characteristic of the entire population, based on the relation between PCB ingestion and metabolism. Measuring 209 PCB congeners has the advantage of providing detailed information regarding the congener distribution within the blood samples, which can be compared to congener patterns in other matrices. Congener-specific analysis of 209 PCB congeners is especially useful in evaluating human exposure to PCBs.     

Ground level ozone concentrations and its association with NOx and meteorological parameters in Kathmandu valley, Nepal

This paper summarizes the results of a yearlong continuous measurements of gaseous pollutants, NO, NO₂, NO_x and O₃ in the ambient air at Kathmandu valley. Measured concentration of the pollutants in study area is a function of time. NO, NO₂ and O₃ peak occurred in succession in presence of sunlight. At the time of maximum O₃ concentration most of the NO_x are utilized. The diurnal cycle of ground level ozone concentrations, revealed mid-day peak with lower nocturnal concentrations and inverse relationship exists between O₃ and NO_x, which are evidences of photochemical O₃ formation. The observed ground level ozone during monsoon is slight lower than the pre-monsoon value. Further, lack of rainfall and higher temperature, solar radiation in the pre-monsoon have given rise to the gradual build up of ozone and it is lowest during winter. Ground level ozone concentrations measured during bandha (general strike) and weekend are 19% and 13% higher than those measured during weekdays. The most effective ozone abatement strategy for Kathmandu Valley may be control of NO_x emissions.     

Effects of humic substances on the decomposition of 2,4-dichlorophenol by ozone after extraction from water into acetic acid through activated carbon

The objectives of this study are to clarify the behavior of humic substances throughout the processes of 2,4-dichlorophenol (2,4-DCP) adsorption on granular activated carbon (GAC) from water and extraction into acetic acid, and the influence of the extracted humic substances on the decomposition of 2,4-DCP by ozone in the acetic acid. The adsorption capacity of GAC for 2,4-DCP was not influenced by the humic substances preloaded to have equilibrium concentration of 24.9mg Cl(-1) (14.5mg Cg(-1)). The adsorption capacity of GAC for 2,4-DCP decreased to one tenth of new GAC after the first adsorption-extraction step because of only 16% desorption in the first step. However, 2,4-DCP adsorbed on GAC was completely extracted after the second step suggesting that GAC can be used as adsorbent to transfer 2,4-DCP from water to acetic acid. The concentration ratio of 2,4-DCP from water into acetic acid was around 2x10(5), whereas the concentration ratio of humic substances was about 3.5, indicating that 2,4-DCP was selectively adsorbed and extracted by this system. The first order degradation rate constant for 2,4-DCP by ozone in acetic acid increased with the addition of humic substances. The rate constant with 16mg Cl(-1) of humic substances was 2.6 times as high as that without humic substances. Humic substances behaved as a promoter for the degradation of 2,4-DCP by ozone.     

Effect of Chlorella pyrenoidosa on fecal excretion and liver accumulation of polychlorinated dibenzo-p-dioxin in mice

The effect of Chlorella pyrenoidosa on fecal excretion and liver accumulation of polychlorinated dibenzo-p-dioxin in C57BL/6N mice administered dioxin was examined. Mice were administered 2.2 microg of 1,2,3,4,7,8-hexachlorodibenzo-p-dioxin (H6CDD) dissolved in corn oil once after a period of acclimatization, after which they were fed either a basal diet, a 10% C. pyrenoidosa diet, or a 10% Spinach diet, for five weeks. Among mice fed the 10% C. pyrenoidosa diet, cumulative fecal excretion of H6CDD over the first week following administration was significantly greater (9.2-fold) than that observed among mice fed the basal diet. Moreover, excretion during the fifth week following administration of H6CDD was still significantly greater (3.1-fold) among mice fed the 10% C. pyrenoidosa diet than among mice fed the basal diet. Five weeks after administration of H6CDD, liver accumulation of H6CDD in mice fed the 10% C. pyrenoidosa diet was significantly less than that observed among mice fed either the basal diet and the Spinach diet (by 27.9% and 34.8%, respectively). These findings suggest that C. pyrenoidosa may be useful in inhibiting the absorption of dioxins via food and the reabsorption of dioxins stored already in the body in the intestinal tract, thus preventing accumulation of dioxins within the body.     

Removal of lead from aqueous solutions by condensed tannin gel adsorbent

Lead has caused serious environmental pollution due to its toxicity, accumulation in food chains and persistence in nature.In this paper, lead removal from aqueous solutions was investigated using condensed tannin gel adsorbent synthesized from a natural tannin compound. It is found that the adsorption is strongly affected by pH values of aqueous solutions.Within pH range of 3.5-6,when initial lead concentration is 100 mg/L, removal efficiency is more than 90%.Adsorption equilibrium is reached within 150 minutes.The adsorption isotherm fits well with the Langmuir equation, by which the saturated adsorption uptake of 190 mg Pb^2 /g dry tannin gel adsorbent is obtained.By means of thermodynamics analysis,it is revealed that the process is exothermic and the adsorption heat is up to 38.4kJ/mol.With respect to high efficiency, moderate pH requirement and minimized second pollution, the tannin gel adsorbent exhibits a promising potential in the removal of lead from wastewater.     

A Mechanical Model for Sieving of Large Deposited Atmospheric Particulates in Surface Soil

A mechanical model for analyzing the sieving of large particulates in soil is proposed and a procedure for assessing soil contamination by airborne hazardous particulates is discussed. The model proposes that deposition of airborne particulates in soil is the results of transport processes of particulates in surface soil. The mechanical sieving of particulates is due to (a) trapping of particulates by the constricted necks of soil pores, (b) adhesion of particulates to pore walls, and (c) suspension in soil water. The probability of particulates being sieved is determined by the cumulative frequency of pore size distribution of the soil. The proposed model indicated that more than 95% of the falling particulates were sieved in the top 5 cm of the surface soil. Furthermore, the model estimated that the unrecorded initial fall of ¹³⁷Cs associated with contaminated particulates was in the range of 2229–2310 kBqm⁻² d⁻¹ and that the unrecorded initial depositions in the 1-cm surface layer were in the range from 129 to 135 kBqkg⁻¹ at a location of about 30 km from the Fukushima nuclear power plant.

     

Monitoring OH-PCBs in PCB transport worker’s urine as a non-invasive exposure assessment tool

In this study, we analyzed hydroxylated polychlorinated biphenyls (OH-PCBs) in urine of both PCB transport workers and PCB researchers. A method to monitor OH-PCB in urine was developed. Urine was solid-phase extracted with 0.1% ammonia/ methanol (v/v) and glucuronic acid/sulfate conjugates and then decomposed using β-glucuronidase/arylsulfatase. After alkaline digestion/derivatization, the concentration of OH-PCBs was determined by HRGC/HRMS-SIM. In the first sampling campaign, the worker’s OH-PCB levels increased several fold after the PCB waste transportation work, indicating exposure to PCBs. The concentration of OH-PCBs in PCB transport workers’ urine (0.55~11 μg/g creatinine (Cre)) was higher than in PCB researchers’ urine (< 0.20 μg/g Cre). However, also a slight increase of OH-PCBs was observed in the researchers doing the air sampling at PCB storage area. In the second sampling, after recommended PCB exposure reduction measures had been enacted, the worker’s PCB levels did not increase during handling of PCB equipment. This suggests that applied safety measures improved the situation. Hydroxylated trichlorobiphenyls (OH-TrCBs) were identified as a major homolog of OH-PCBs in urine. Also, hydroxylated tetrachlorobiphenyls (OH-TeCBs) to hydroxylated hexachlorobiphenyls (OH-HxCBs) were detected. For the sum of ten selected major indicators, a strong correlation to total OH-PCBs were found and these can possibly be used as non-invasive biomarkers of PCB exposure in workers managing PCB capacitors and transformer oils. We suggest that monitoring of OH-PCBs in PCB management projects could be considered a non-invasive way to detect exposure. It could also be used as a tool to assess and improve PCB management. This is highly relevant considering the fact that in the next 10 years, approx. 14 million tons of PCB waste need to be managed. Also, the selected populations could be screened to assess whether exposure at work, school, or home has taken place.     

Ultra-High Efficiency Photovoltaic Cells for Large Scale Solar Power Generation

The primary targets of our project are to drastically improve the photovoltaic conversion efficiency and to develop new energy storage and delivery technologies. Our approach to obtain an efficiency over 40% starts from the improvement of III–V multi-junction solar cells by introducing a novel material for each cell realizing an ideal combination of bandgaps and lattice-matching. Further improvement incorporates quantum structures such as stacked quantum wells and quantum dots, which allow higher degree of freedom in the design of the bandgap and the lattice strain. Highly controlled arrangement of either quantum dots or quantum wells permits the coupling of the wavefunctions, and thus forms intermediate bands in the bandgap of a host material, which allows multiple photon absorption theoretically leading to a conversion efficiency exceeding 50%. In addition to such improvements, microfabrication technology for the integrated high-efficiency cells and the development of novel material systems that realizes high efficiency and low cost at the same time are investigated.     

Contribution of transboundary air pollution to ionic concentrations in fog in the Kinki Region of Japan

To estimate the contribution of transboundary transported air pollutants from other Asian countries to Japan in ionic concentrations in fog water in March 2005, the Community Multiscale Air Quality (CMAQ) modeling system was utilized with meteorological fields produced by the 5th generation Mesoscale Model (MM5). For meteorological predictions, the model well reproduced the surface meteorological variables, particularly temperature and humidity, and generally captured fog occurrence. For chemical predictions, most of the model-predicted monthly mean concentrations were approximately within a factor of 2 of the observations, indicating that the model well simulated the long-range atmospheric transport from the Asian Continent to Japan. For SO₄^2?, NO₃^? and NH₄⁺, the contribution rates of the transboundary air pollution in the Kinki Region of Japan ranged from 69 to 82% for aerosols, from 47 to 87% for ionic concentrations in rain, and from 55 to 79% for ionic concentrations in fog. The study found that the transboundary air pollution also affected ionic concentrations in fog as well as aerosol concentrations and ionic concentrations in rain.