Coulometric determination of dissolved hydrogen with a multielectrolytic modified carbon felt electrode-based sensor

A multielectrolytic modified carbon electrode (MEMCE) was fabricated by the electrolytic-oxidation/reduction processes. First, the functional groups containing nitrogen atoms such as amino group were introduced by the electrode oxidation of carbon felt electrode in an ammonium carbamate aqueous solution, and next, this electrode was electroreduced in sulfuric acid. The redox waves between hydrogen ion and hydrogen molecule at highly positive potential range appeared in the cyclic voltammogram obtained by MEMCE. A coulometric cell using MEMCE with a catalytic activity of electrooxidation of hydrogen molecule was constructed and was used for the measurement of dissolved hydrogen. The typical current vs. time curve was obtained by the repetitive measurement of the dissolved hydrogen. These curves indicated that the measurement of dissolved hydrogen was finished completely in a very short time (ca. 10 sec). A linear relationship was obtained between the electrical charge needed for the electrooxidation process of hydrogen molecule and dissolved hydrogen concentration. This indicates that the developed coulometric method can be used for the determination of the dissolved hydrogen concentration.     

A comparitive study between the coal-biomass briquette and raw coal in SO2 pollution and adverse effects in rabbits

This study was conducted to evaluate the adverse health effects on rabbits exposed to SO₂ emitted indoors from burning coals, and compare differences between coal-biomass briquette (B.B.) and raw coal (R.C.). Thirty-six male rabbits were divided equally into three groups at random, and then exposed to burning R.C., B.B., and the third without burning coal (Control) for 90 days. Data showed that the average concentration of SO₂ in 24?h in R.C. was 13.04?mg?m^?3, which was 5-fold greater than B.B. (2.68?mg?m^?3) and 31-fold higher than control (0.41?mg?m^?3). After 45 days, the numbers of rabbits, with increased frequency of Comet cell was highest in R.C. After 90 days, the % positive Comet cell was significant at 10.36% in R.C., 5.42% in B.B., and 1.73% in Control. There was a nonlinear dose–effect relationship between % positive Comet cell and the concentration of SO₂. The incidence of interstitial pneumonia was 6/12 in R.C. and 4/12 in B.B. showing severe squamous metaplasia with atypical hyperplasia in bronchial epithelia in R.C. animals. The results of study indicate that use of B.B. reduced the emission of SO₂; but the smoke emitted from burning coal still produced DNA damage.     

Electrolytic aminated carbon materials for the electrocatalytic redox reactions of inorganic and organic compounds

Some kinds of amine groups can be introduced to the glassy carbon surface by the electrode oxidation of the carbon electrode surface in ammonium carbamate solution, and this amine groups modified electrode is named as an aminated glassy carbon electrode. The existences of not only primary amine but also secondary and tertially amines were confirmed by X ray photoelectron spectroscopy. The applications of the aminated carbon material for the electrocatalytic reductions of oxygen, hydrogen peroxide, and organic compounds such as quinones were carried out, and the effects of amination on the formation of electrocatalytic sites for many species were revealed. The electrocatalyzed cyclic voltammograms of metal ions and metal chelate compounds obtained by aminated glassy carbon electrodes are also discussed. Moreover, we intend to describe that the aminated carbon electrode can exhibit the large reduction waves of inorganic oxoacids such as N0₂? or bromide ion. The introduced functional groups containing nitrogen atom can change the distribution of the electron densities of the graphite carbon surface, and this specific electron distribution environment may generate the various electrocatalytic activities.     

Long-term stabilization of enzyme activity by immobilizing enzyme colony in polymaleimidostyrene-modified micelles

Amperometric biosensors fabricated by immobilizing enzyme colony in polymaleimidostyrene-modified micelles exhibited good sensitivity and great long-term stability. To our knowledge, there has not been a general design for various enzyme biosensors. Enzyme micelle membrane which is different from any of other conventional immobilization methods, is an innovative way and will be a well-developed biosensor technology to provide rapid and reliable measurements. The potential of using enzyme micelle membrane to fabricate biosensors will be of great hope.     

Removal of hydrogen chloride from gaseous streams using magnesium-aluminum oxide

Magnesium-aluminum oxide (Mg-Al oxide) obtained by thermal decomposition of Mg-Al layered double hydroxide (Mg-Al LDH) effectively removed HCl from gaseous streams. HCl removal was greater in the presence of added water vapor at all temperatures examined and increased with decreasing temperature in both the presence and absence of added water vapor. Wet and dry removal of gaseous HCl were attributed to the production of MgCl2 . 6H2O and MgCl2 . 4H2O, respectively. For the wet scrubbing process, the reconstruction reaction of Mg-Al LDH from Mg-Al oxide was the primary mechanism for increased HCl removal.     

Variation in estrogenic activity among fractions of a commercial nonylphenol by high performance liquid chromatography

Estrogenic activity by recombinant yeast screen assay of the commercial NP was considerably higher when compared with that of n-nonylphenol (n-NP). Fractionation of the commercial NP by high performance liquid chromatography (HPLC) afforded seven isomers: 4-(1,3-dimethyl-1-propyl-butyl)-phenol, 4-(1,1,3-trimethyl-hexyl)-phenol, 4-(1,1-dimethyl-3-ethyl-pentyl)-phenol, 4-(1,1,4-trimethyl-hexyl)-phenol, 4-(1-methyl-1-propyl-pentyl)-phenol, 4-(1,1,2-trimethyl-hexyl)-phenol and 4-(1-ethyl-1-methyl-hexyl)-phenol. The structures of these isomers were determined by GC-MS and nuclear magnetic resonance spectroscopy (NMR). All of these isomers possessed tertiary alpha-carbon in their chemical structures. Another tertiary NP, 4-(1,1-dimethyl-heptyl)-phenol was synthesized in the present study and this synthetic NP also exhibited the estrogenic activity. One fractionated compound was identified as one of decylphenol, 4-(1-ethyl-1,4,4-trimethyl-pentyl)-phenol. The isomer, 4-(1,1,4-trimethyl-hexyl)-phenol exhibited the highest estrogenic activity corresponding to 1/10000 that of 17beta-estradiol (E2). The activity of n-NP was the least. This suggests that it may be possible to develop a technical NP mixture with relatively low estrogenic activity.     

Organohalogen compounds and their metabolites in the blood of Japanese amberjack (Seriola quinqueradiata) and scalloped hammerhead shark (Sphyrna lewini) from Japanese coastal waters

Information on accumulation of polychlorinated biphenyl metabolites (OH-PCBs) and hydroxylated polybrominated diphenyl ethers (OH-PBDEs) in the blood of marine fish is limited. The present study, we determined the residue levels and patterns of PCBs, OH-PCBs, PBDEs, OH-PBDEs and methoxylated PBDEs (MeO-PBDEs) in the blood collected from scalloped hammerhead shark (Sphyrna lewini) and Japanese amberjack (Seriola quinqueradiata), species of predatory fish at Japanese coastal waters. The predominant homologues found in Japanese amberjacks were mono- and di-chlorinated OH-PCBs, and scalloped hammerhead sharks were octa-chlorinated OH-PCBs. The predominant OH-PCB isomers were lower-chlorinated OH-PCBs such as 6OH-CB2 and 2'OH-CB9 in Japanese amberjacks. This result suggests that exposure of Japanese amberjacks to lower-chlorinated OH-PCBs might be from the ambient aquatic environment. In scalloped hammerhead sharks, 4,4'diOH-CB202, 4OH-CB201 and 4OH-CB146 were the predominant isomers accounting for approximately 60% of the total OH-PCBs. The predominant MeO-PBDE isomers were 6MeO-BDE47 followed by 2'MeO-BDE68 in both species. As for OH-PBDE isomers, 6OH-BDE47 was predominant followed by 2'OH-BDE68 in Japanese amberjacks and scalloped hammerhead sharks. Residue levels of ΣMeO-PBDEs and ΣOH-PBDEs showed a significant positive correlation (p=0.029). This result suggests that MeO-PBDEs and OH-PBDEs share a common source or a metabolic pathway in fishes. Characteristic differences found in the profiles of OH-PCBs and OH-PBDEs in Japanese amberjack and scalloped hammerhead shark show the need for further studies on the differences in exposure profiles, metabolic capacities and toxic effects in fish.     

Effects of dioxins and polychlorinated biphenyls (PCBs) on thyroid function in infants born in Japan – the second report from research on environmental health

Dioxins (PCDD + PCDF) and polychlorinated biphenyl (PCB) are potentially hazardous compounds and have structural similarity to thyroid hormones. Our research group on “Dioxins and PCB in Human Milk” was organized in 1997 and has been active for the past three years. We collected breast milk from 80 mothers living in Tokyo, Saitama, Ishikawa and Osaka Prefecture in Japan at 5, 30, 150, 300 postpartum days and measured PCDDs, PCDFs and PCBs during 1998–1999. We added another 20 prefectures and cities during 1999–2000. Breast milk was obtained from 415 mothers at 30 postpartum days (breast-feeding group). Blood was taken from infants who were breast-fed at the age of 1 year for evaluation of thyroid and immune functions. Blood was also taken from 53 infants who were bottle-fed (bottle-feeding group) as a control. Serum T4, T3, FT4 and TSH levels in the breast-feeding (n=337) and bottle-feeding (n=53) groups were within normal ranges and were not significantly different between the two groups. Although there were a large geographic differences of dioxins and co-PCB content in breast milk, there were no differences in serum T4, T3, FT4, TSH levels and no significant correlation between the mean serum levels of TSH and TEQ in breast milk. There was a significant correlation between serum TSH at 1 year of age and that from blood on dried filter paper TSH at 5 days of age. We concluded that dioxin intake from breast milk in Japanese infants did not impair thyroid function. However, long-term effects remain to be evaluated.     

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.