Temporal trends of persistent organochlorine residues in human adipose tissue from Japan, 1928-1985

The presence of pesticide residues in rain, throughfall, stemflow and in ambient air in two Italian forests affected by the forest damage phenomenon were investigated. Pesticides measured were: alachlor, atrazine, carbaryl, 2,4-D, diazinon, dichlobenil, fluazifop-butyl, MCPA, parathion, phorate and trifluralin. Rainwater samples were collected from May to October 1988 at Vallombrosa and Renon, air and atmospheric particulates were sampled during April-June 1989, only at Vallombrosa. A total of 146 samples of rainfall and 20 samples of ambient air were analysed and 49 out of 166 samples contained at least one active ingredient. Herbicides were more frequent than insecticides, and their concentrations were also higher (max 3.44 microg litre(-1)).     

Inhibitory effect of the iron chelator desferrioxamine (Desferal) on the generation of activated oxygen species by Chattonella marina

Recent studies demonstrated that the toxic red tide phytoplankton Chattonella spp. produce activated oxygen species such as superoxide anion (O ₂ ^- ), hydrogen peroxide (H₂O₂), and hydroxyl radicals (·OH), which may be responsible for the toxicity of this flagellate. However, the mechanism behind the production of these oxygen radicals and H₂O₂ by Chattonella spp. is largely unknown, and the physiological significance of activated oxygen species for Chattonella spp. is also unclear. In the present study, we investigated the involvement of iron in the generation of O ₂ ^- and H₂O₂ by C. marina. The generation of O ₂ ^- by C. marina was related to the growth phase; the highest rate of O ₂ ^- production was observed during the exponential growth phase. However, no such increase during the exponential growth phase was observed in C. marina growing in an iron-deficient medium, even though the growth of C. marina was not significantly affected by iron-deficiency during the first 4 d. In addition, the iron chelator desferrioxamine (Desferal) strongly inhibited the generation of both O ₂ ^- and H₂O₂ by C. marina in a concentration-dependent manner. The growth of C. marina was also inhibited by Desferal. Furthermore, in the presence of 500 M Desferal, C. marina-induced growth inhibition of the marine bacteria Vibrio alginolyticus was almost completely abolished. These results suggest that iron is required for the generation of activated oxygen species by C. marina, as well as for its own growth.     

Field Survey of Trans-boundary Air Pollution with High Time Resolution at Coastal Sites on the Sea of Japan during Winter in Japan}

An intensive field survey, with 6-h measurement intervals, of concentrations of chemical species in particulate matter and gaseous compounds was carried out at coastal sites on the Sea of Japan during winter. The concentration variation of SO₂(g) and HNO₃(g) were well correlated, whereas the NH₃(g) concentration variation had no correlation with those of SO₂(g) and HNO₃(g). The NH₄ ⁺ (p)/non-sea-salt- (nss-)SO₄ ^{2 −}(p) ratio in particulate matter was mainly affected by the location of the sampling site. One or more concentration peaks of nss-Ca^{2 +} for survey period were observed. Backward trajectories analyses for the highest nss-Ca^{2 +} concentration peaks showed some inconsistency in pathways. We consider that insufficient mixing of the atmosphere and/or insufficient time for the transported air pollutants to react with those discharged locally are the most likely explanations for the discrepancies between the measured products [HNO₃][NH₃] and the calculated values.     

Characterization of an adsorbed humin-like substance on an allophanic soil formed via catalytic polycondensation between catechol and glycine, and its adsorption capability to pentachlorophenol

An allophanic soil (AS) catalyzed the formation of dark-colored polymers via polycondensation reactions between catechol and glycine. The organic carbon content of the AS was increased from 0.16% to 1.3%, indicating that some of the dark-colored polymers had been adsorbed to the AS. The characteristics of the dark-colored polymers adsorbed on the AS were similar to those of a humin that is not extractable with an aqueous alkaline solution. Such a humin-like substance (HuLS) was separated from the AS by treatment with a mixture of HF and HCl. The HuLS and humic acid-like substance (HaLS), comprising the acid-insoluble fraction in the reaction mixture, were characterized by elemental analysis, size exclusion chromatography, pyrolysis-GC/MS and ¹³C NMR. However, the structural features of HaLS and HuLS had many points in common. These results suggest that HuLS-AS can be regarded as an organo-clay complex formed by the strong adsorption of HaLS to the AS. The adsorption of pentachlorophenol (PCP) to AS and HuLS-AS was examined at pH 5.5. At this pH, the zeta potential of the HuLS-AS showed a negative value. It would, therefore, be expected that pentachlorophenolate anions would adsorb with difficulty to HuLS-AS because of electrostatic repulsion. Nevertheless, the adsorption coefficient for PCP to HuLS-AS, as estimated by the Freundlich isotherm, was seven times larger than that for AS. These results show that HuLS, when adsorbed on the AS surface, has the capability to enhance the adsorption of PCP.     

Estimation of the amount of dry deposition in an urban area (Kobe city, Japan) by the inferential method

The amount of dry deposition of SO₂(g) and HNO₃(g) in an urban area in Japan has been estimated by the inferential method. The mean annual dry deposition of SO₂(g) (2.91 kgS/ha/year) was close to or less than that in the Clean Air Status and Trends Network (CASTNet) of the U.S. (3.59 kgS/ha/year). The mean annual dry deposition of HNO₃(g) (10.8 kgN/ha/year) was approximately six times larger than that in CASTNet (1.85 kgN/ha/year). The proportions of dry/(dry+wet) deposition for sulfur and nitrogen were 0.301 and 0.785, respectively.     

Temporal Trends of Non-sea Salt Sulfate and Nitrate in Wet Deposition in Japan

Temporal trends of non-sea salt (nss-) sulfate and nitrate were analyzed from nationwide precipitation chemistry measurements provided by the Ministry of the Environment (MOE) for the 1988–2002 fiscal years (April–March). The concentrations and deposition of nss-sulfate were found to be decreasing, and those of nitrate were stable or slightly increasing at most sites. These deposition trends were discussed from the viewpoint of emissions of SO₂ and NO_X during the period of interest. Because monitoring techniques have changed in the number of active sites, samplers, and analytical methods during the operation period, the median of all annual depositions measured in Japan in a specific year was selected as the annual representative. The contribution of specific emission sources was also calculated for 1990 on the basis of the nss-sulfate and nitrate deposition in Japan obtained with a model simulation in which the model did not include volcanic emissions from Mt. Oyama, Miyakejima Island, which began to erupt suddenly and violently in 2000. For nss-sulfate, the calculated deposition agrees well with the intensity and trends of the median up to 1999. After 2000, a higher deposition than calculated in the preceding years was evident, which is attributable to the volcanic SO₂ from Mt. Oyama. For nitrate, both the calculated and observed depositions were slightly increasing; however, the calculation was found to exceed the observation.     

PCBs and organochlorine pesticides (OCPs) in edible fish and shellfish from China

A wide variety of fish and shellfish were collected from local supermarkets of Dalian, Tianjin and Shanghai in China and analyzed for the concentrations of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) such as hexachlorobenzene (HCB), hexachlorocyclohexane isomers (HCHs), chlordane compounds (CHLs, including trans-chlordane, cis-chlordane, trans-nonachlor and cis-nonachlor) and dichlorodiphenyltrichloroethane (DDT) and its metabolites (DDTs, including o,p'-DDE, p,p'-DDE, o,p'-DDD, p,p'-DDD, o,p'-DDT and p,p'-DDT). Concentrations of PCBs in samples collected from Dalian, Tianjin and Shanghai ranged from 1.11 to 8.04 ng/g, 1.26 to 5.60 ng/g and 0.83 to 11.4 ng/g on wet weight basis, respectively. The concentrations were lower compared to those in developed countries such as Japan and Italy. Average concentrations of HCB, HCHs, CHLs and DDTs were 0.38, 0.92, 0.47 and 28.9 ng/g on wet weight basis, respectively. The daily intake of PCBs and organochlorine pesticides ingested by people living in these cities in China through fish and shellfish was estimated and compared with those observed in other areas.     

Dioxin-like potencies and extractable organohalogens (EOX) in medical, municipal and domestic waste incinerator ashes in Japan

Ash samples collected from medical, municipal and small-scale domestic incinerators in Japan were tested for dioxin-like activity using bioassay technique (ethoxyresorufin-O-deethylase: EROD assay) and for extractable organohalogens (EOX) using instrumental neutron activation analysis in order to estimate potential toxicity and responsible chemicals in those samples. Crude extracts and fractions cleaned-up for dioxin analysis from the samples were used for the analysis. The ranges of dioxins in the ashes were between 2.23 and 12.29 ng TEQ/g (dry weight). Relative potency ranges estimated by EROD assay in the medical incinerator ashes were 3.8-17.6 times higher than the results of conventional chemical analysis. EOX analysis suggested that ash samples contained plenty of organochlorine compounds apart from chlorinated dioxins. In addition, medical waste incinerator ashes were considered to have relatively higher amount of organoiodine compounds. In the cleaned-up fractions, bioassay potency ranges were lower than those in the crude extracts. However, some samples still exhibited higher potency than expected from chemical analysis. Though some polycyclic aromatic hydrocarbons were found in the fractions, the amounts were relatively low (0.39-10.56 ng/g). The results imply that some bioactive organohalogens that cannot be detected in the conventional chemical analysis might have potential for dioxin-like toxicity, and contribute to higher bioassay activities. The combination of the chemical analysis with the bioassay and EOX provides rough figure of dioxin-like toxicity and suggests types of organohalogen compounds that should be identified as a part of dioxin analysis for control emission from an incineration plant.     

Important sequence for overexpression of NADH oxidase gene from Thermus thermophilus HB8 in Escherichia coli

Enzymes fixed on the electrode of biosensor are gradually inactivated and the electrode is discarded after using several times. In order to prepare the stable biosensor, we try to use a stable enzyme from extreme thermophilic bacteria, Thermus thermophilus HB8. It is very important that a stable enzyme from T. thermophilus HB8 is overproduced in Escherichia coli, for the purpose of enough supply of enzyme. Thereby, we determined the important sequence for overexpression of NADH oxidase (nox) gene from T. thermophilus HB8 in E. coli. As a result, it is revealed that ten nucleotides sequence, GAAATTAACT, in the upstream of start codon of nox gene was important for its overexpression in E. coli.