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.     

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.

     

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.     

Maternal-fetal distribution and transfer of dioxins in pregnant women in Japan, and attempts to reduce maternal transfer with Chlorella (Chlorella pyrenoidosa) supplements

Dioxins can be transferred from mother to fetus via the placenta, or to nursing infants via breast milk, potentially causing developmental health problems in children. To assess pediatric health risks from dioxins, exposure of mothers and children to dioxins must be clarified. Methods of reducing maternal transfer of dioxins should also be investigated. Concentrations of 28 dioxin (polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and co-planar polychlorinated biphenyls) congeners in blood, adipose tissue, breast milk, cord blood and placenta collected from 44 pregnant Japanese women were measured. In addition, to investigate potential reductions in maternal transfer of dioxins, 23 pregnant women were instructed to take Chlorella pyrenoidosa supplements during pregnancy. Correlations were observed between dioxin total toxic equivalents (total TEQ) in blood and total TEQ in adipose tissue (r=0.913, P<0.0001), breast milk (r=0.695, P=0.0007), and cord blood (r=0.759, P<0.0001). Dioxin levels transferred to fetuses and nursing infants reflect cumulative maternal concentrations of dioxins. A linear regression equation was introduced to predict total TEQ in breast milk and cord blood from dioxin levels in maternal blood, which should prove useful in evaluating fetal and infant risk of dioxin exposure. Total TEQ in cord blood were approximately 26% lower than in maternal blood (P<0.0001). The results of this study suggest that transplacental transfer differs depending on the dioxin congener. Total TEQ in breast milk were approximately 30% lower in the Chlorella group than in controls (P=0.0113). This finding suggests that maternal transfer of dioxins can be reduced using dietary measures such as Chlorella supplements.     

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.     

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.     

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.     

Large-scale evaluation of the current level of polybrominated diphenyl ethers (PBDEs) in breast milk from 13 regions of Japan

Polybrominated diphenyl ethers (PBDEs) were measured in 2004 in 105 breast milk samples collected from 13 regions of Japan (Hokkaido, Akita, Miyagi, Tokyo, Gifu, Fukui, Kyoto, Hyogo, Wakayama, Shimane, Yamaguchi, Kochi and Okinawa). Six congeners (BDE-28, BDE-47, BDE-99, BDE-100, BDE-153 and BDE-154) were determined by gas chromatography /mass spectrometry (GC/MS). Total PBDE levels ranged from 0.01 to 23.0 ng/g lipid (geometric mean (GM), 1.34 ng/g lipid). BDE-47 (GM, 0.66 ng/g lipid, 59% of sigmaPBDE) was the most abundant congener present in breast milk and was detected in 99% of the samples. Total PBDE levels were higher in northern Japan than in other regions. We analyzed the effects of occupation, age, smoking status, alcohol consumption and number of deliveries on total PBDE levels. None of these factors were significantly associated with the level of PBDEs. The present study revealed that the current level of exposure to PBDEs in Japan is lower than that in the USA or Sweden. GMs (ng/g lipid) (GSD, geometric standard deviation) and medians (ng/g lipid) of PBDE levels in each district are as follows: Hokkaido 2.70 (1.70), 2.74; Akita 4.49 (2.19), 5.44; Miyagi 1.77 (4.37), 1.11; Tokyo 1.39 (2.09), 1.63, Gifu 2.83 (4.79), 2.23; Fukui 1.05 (2.34), 1.18; Kyoto 1.31 (2.95), 1.33; Hyogo 1.02 (2.69), 0.88; Wakayama 1.33 (3.80), 1.70; Shimane 0.83 (2.51), 0.66; Yamaguchi 1.74 (2.82), 1.76; Kochi 0.50 (2.69), 0.74 and Okinawa 1.91 (2.75), 1.22. This is the first large-scale study of current PBDE levels in breast milk in Japan.     

Effect of metal ions on decomposition of chlorinated organic substances by ozonation in acetic acid

The objective of this study is to find metal ions that enhance the ozone decomposition of chlorinated organic substances in acetic acid. Although the pseudo-first order degradation rate constant for 2,4-DCP by ozone in acetic acid in addition of Ca2+, Mg2+, Al3+ and Fe2+ were almost the same as that with no metal ion, the degradation rate in addition of Mn2+ and Fe3+ were 2.4 and 4.5 times as high as that with no metal ion, respectively. The presence of Fe3+ enhanced the degradation of 2,4-DCP by ozone in acetic acid because Fe3+-phenolate complex which have high reactivity with ozone was produced by the reaction between 2,4-DCP and Fe3+ in acetic acid.