The transformation of trichloroethylene (TCE) in natural mineral iron disulfide (pyrite) aqueous suspension under different oxygen conditions was investigated in laboratory batch experiments. TCE transformation was pursued by monitoring its disappearance and products released with time. The effect of oxygen was studied by varying the initial dissolved oxygen concentration (DO(i)) inside each reactor. Transformation rates depended strongly on DO(i) in the system. In anaerobic pyrite suspension, TCE did not transform as it did under aerobic conditions. The transformation rate increased with an increase in DO(i). The TCE transformation kinetics was fitted to a pseudo-first-order reaction with a rate constant k (h(-1)) varying from 0.004 to 0.013 for closed systems with DO(i) varying from 0.017 to 0.268 mmol/L under the experimental conditions. In the aerobic systems, TCE transformed to several organic acids including dichloroacetic acid, glyoxylic acid, oxalic acid, formic acid, and finally to CO2 and chloride ion. Dichloroacetic acid was the only chlorinated intermediate found. Both TCE and the pyrite surface were oxidized in the presence of O2. Oxygen consumption profiles showed O2 was the common oxidant in both TCE and pyrite oxidation reactions. Ferric ion cannot be used as an alternative oxidant to oxygen for TCE transformation.
We have demonstrated previously that there is an abnormal expression of sphingomyelin (SM) deacylase in the epidermis of patients with atopic dermatitis (ADe). In the present study, we have prepared N-[palmitic acid-1-(14)C]SM and N-[palmitic acid-1-(14)C]glucosylceramide (GCer) to use as substrates and have quantified SM deacylase activity by detecting the release of [(14)C]palmitic acid in extracts of the stratum corneum or the epidermis of ADe patients. In studies using [palmitic acid-1-(14)C]SM as a substrate, a pH dependency of catalytic activity with a peak at pH 5.0 was found. Preparative SDS/PAGE using an extract of ADe epidermis revealed that the molecular mass of SM deacylase is 40000 Da, which is consistent with its apparent molecular mass of 42000 Da estimated by gel-filtration analysis of stratum corneum extracts. Analytical isoelectric focusing (IEF) chromatography demonstrated that the pI values of SM deacylase, beta-glucocerebrosidase (GlcCDase), sphingomyelinase (SMase) and acid ceramidase were 4.2, 7.4, 7.0 and 5.7, respectively. In enzymic analysis using pI-4.2 SM deacylase partially purified by IEF, which had no detectable contamination with acid ceramidase, GlcCDase or SMase, radio-TLC analysis revealed that radiolabelled sphingosylphosphocholine or [1-(14)C]palmitic acid was enzymically liberated from [choline-methyl-(14)C]SM or N-[palmitoyl-1-(14)C]GCer, respectively, used as substrates. Further the pI-4.2 protein purified from extracts of the stratum corneum of ADe patients was able to hydrolyse N-[palmitoyl-1-(14)C]SM and GCer, but not N-[palmitoyl-1-(14)C]ceramide. These results indicate that a hitherto undiscovered epidermal enzyme, termed here glucosylceramide sphingomyelin deacylase, is expressed in the skin of ADe patients, which plays an important role in ceramide deficiency (including acylceramides) in the stratum corneum.
Little is known about offshore tsunami deposits, although they have the potential to improve palaeotsunami reconstructions, especially in areas with limited preservation of onshore tsunami deposits. We analysed 44 sediment cores collected in 2012 at water depths of 14–30 m in Sendai Bay, north‐eastern Japan, to identify the deposits of the 2011 Tohoku‐oki tsunami with the aid of 134Cs released from the Fukushima‐Daiichi Nuclear Plant. The preserved tsunami deposits in the inner shelf are interbedded with very fine sand and mud, showing similar features to storm deposits. In the shoreface, a distinct layer of coarse sand overlies fine sand, appearing to have originated as beach sand transported offshore by the tsunami backwash. The coarse sand fades offshore around the boundary between the shoreface and inner shelf. Many of the core sites show evidence that surface sediment was reworked, probably by post‐tsunami storm waves, suggesting that further reworking would make the ultimate preservation of the tsunami deposits unlikely.
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