Mutagenicity of polyaromatic hydrocarbons by chemical models for cytochrome P450 in Ames assay

DNA damage is an important step in carcinogenesis. The Ames assay is a short-term screening of carcinogens that induce DNA damage. Most carcinogens require enzymatic activation through oxidation by cytochrome P450 (CYP450) in the presence of S9 mix. A combination of iron (Fe)(III) porphyrin and an oxidant is also able to oxidize compounds as an alternative metabolic pathway to CYP450. Previously it was reported that a chemical model containing a water-soluble 5,10,15,20-tetrakis(1-methylpyridinium4-yl)porphyrinatoiron(III) chloride (4-MPy) and tert-butyl hydroperoxide (t-BuOOH) activated aromatic amines and amides. In this study, a chemical model composed of an Fe porphyrin, water-insoluble 5,10,15,20-tetrakis(pentafluorophenyl)porphyrinatoiron(III) chloride (F₅P) or water-soluble 4-MPy was optimized with an oxidant – t-BuOOH, magnesium monoperoxyphthalate (MPPT), or iodosylbenzene (PhIO). Subsequently the mutagenicity of benzo[a]pyrene (B[a]P) and chrysene in Salmonella typhimurium TA strains was compared. B[a]P was activated by a combination of F₅P or 4-MPy plus MPPT or PhIO in S. typhimurium TA1538. The B[a]P-induced mutagenicity with F₅P plus oxidant was higher than 4-MPy plus oxidant. Mutagenicity of chrysene, a tetracyclic aromatic hydrocarbon, was not detected in the presence of F₅P/PhIO in S. typhimurium TA98, but was activated in the presence of F₅P/MPPT. The F₅P/MPPT activated other polyaromatic hydrocarbons (PAH) in the S. typhimurium TA98 assay including dibenz[a,c]anthracene, dibenz[a,h]anthracene, 3-methylcholanthrene, and benzo[a]anthracene. The results indicated that the F₅P/MPPT was the most efficient model for detecting PAH-induced mutagenicity in the Ames assay.     

Determination of bioavailable rhenium fraction in agricultural soils

Rhenium (Re) mobility in agricultural soils was studied in order to obtain information relevant to (99)Tc mobility in soil-to-plant systems. Since water soluble Tc and Re are highly bioavailable, extraction of Re with water was carried out in addition to a total Re determination in the soils. The geometric means of total Re for paddy field, upland field and other soils were 0.34, 0.23, and 0.28 ng g(-1), respectively, while those of water soluble Re (<0.45 microm membrane filterable) were 0.053, 0.015 and 0.008 ng g(-1), respectively. There were no differences for total Re among soil uses; however, the water soluble Re/total Re ratio was significantly higher in paddy field soils (16%) than in other soil uses (6% for upland fields and 3% for other uses). Rhenium mobility and plant availability were higher in paddy fields than in other agricultural fields, and similar phenomena would be expected for (99)Tc.     

Vertical fluxes and ecological significance of organic materials during the phytoplankton bloom during austral summer in Breid Bay,Antarctica

A mooring system consisting of an in situ fluorometer at a depth of 50 m and a time-series sediment trap at a depth of 110 m was deployed at the sediment trap site (70°11.536'S; 24°18.679'E; water depth: 300 m) in Breid Bay, Antarctica in austral summer from 28 December 1985 to 13 February 1986. Sinking particles, consisting of diatoms (mainly Thalassiosira antarctica), were analyzed for organic materials, stable carbon and nitrogen isotopes. Vertical fluxes of organic carbon and nitrogen were determined to be within the ranges of 12.3 to 116 mg C m^-2 d^-1 and 1.79 to 15.4 mg N m^-2 d^-1, respectively, with maxima in the middle of January 1986, after which time the organic carbon and nitrogen fluxes tended to decrease with a steep gradient. High values of ¹³C were found in the organic matter of the sinking particles collected before the middle of January, indicating that the organic matter was derived from the diatoms in the logarithmic phase of their growth. Increased abundance of glucose was found in the water-extractable carbohydrate, which was one of the sinking particles collected in the middle of January. This fact clearly indicated that the diatoms were no longer in the growth phase but rather in the stationary phase, because reserved glucan as well as various cellular organic materials were reportedly accumulated within the algal cells in the stationary phase. Fifteen species of protein amino acids with trace amounts of -alanine, -aminobutyric acid and ornithine were found in the sinking particles upon acid hydrolysis, but the amino acid composition of these samples had not been affected much by biological agents. The essential amino acid index was calculated for the sinking particles collected in the course of the sediment trap experiment. The indices obtained indicated that the sinking particles collected in Breid Bay were more ecologically significant than the sinking and suspended particles from deep waters.     

A comparison of water solubilities by the flask and micro-column methods

A comparative examination of the two procedures of the OECD Test Guideline: Water Solubility was undertaken using carbazole, fluoranthene, anthracene, hexachlorobenzene, p-nitroaniline and diphenylamine. The flask method was modified to provide for dissolution of the solute from the surface of glass beads. By the proposed flask method, one can accurately measure the water solubility down to the order of 10 μg/L as well as those of the order of %. The micro-column method, which requires a number of concentration determinations to ensure that a saturated solution has been obtained, is recommended for the solubility range of 10 mg/L through 10 μg/L. The flask method using the procedures described in this study, covers the range of solubility above 10 μg/L with only two determinations one being a simple preliminary test and the other a precise measurement.     

Studies on automated survey system of environmental chemicals by gas chromatography-mass spectrometry-computer II. Three dimensional mass chromatography

A three dimensional mass chromatography (TDMC), which is the extended method of mass chromatography, has been developed for the analysis of environmental chemicals. A considerable performance was suggested by the combination of TDMC to gas chromatography-mass spectrometry-computer system.     

Evidence for seasonal mate limitation in populations of an intertidal amphipod, Corophium volutator (Pallas)

Potential rates of reproduction (PRR) differ between the sexes of many animal species. Adult sex ratios together with PRR are expected to determine the operational sex ratio (OSR) defined as the ratio of fertilizable females to sexually active males at any given time. OSR is expected to determine the degree to which one sex competes for another—the limiting sex. We explored the potential for mate limitation in an intertidal amphipod, Corophium volutator (Pallas). Males have higher PRR than females, but males may be limiting because of extreme female-biased sex ratios observed in this species. Consistent with this idea, late season females were less likely to be ovigerous and had smaller size-specific clutches, both of which were associated with seasonal declines in availability of males of reproductive size. Seasonal changes in ovigery could not be explained by seasonal changes across sites in other factors (e.g., female body size or phenology of breeding). Smaller females were less likely to become ovigerous later in the season at three of four sites. Seasonal reductions in clutch size also occurred among small females expected to be reproducing for their first time. In complimentary laboratory experiments, reduced likelihood of ovigery and reduced fecundity occurred when the number of receptive females was increased relative to availability of a reproductively active male. Our results suggest male mate limitation can occur seasonally in this species and that male limitation is regionally widespread and may affect recruitment.     

Fluorescence and metal-ion recognition properties of acetylacetone-based ligands

A new acetylacetone-based ligand (Ligand 1) bearing pyrene unit was synthesized and the fluorescence and metal-ion recognition properties were investigated in the presence of a different metal ion in acetonitrile solution. The fluorescence emission of Ligand 1 was strongly quenched by complexation with Cu²⁺ while no significant change was observed in the presence of other metal ions. The metal-ion selectivity changed from Cu²⁺ to Ni²⁺ when glycine moiety (–NH–CH₂–CO–) was introduced into Ligand 1 as spacer. This result implies that hydrogen-bonding induced by the glycine moiety affects the binding ability of ligands to metal ions, resulting in change of the metal-ion selectivity.     

Antimony mobility in Japanese agricultural soils and the factors affecting antimony sorption behavior

The mobility of antimony (Sb) in Japanese agricultural soils was studied by radiotracer experiments using 124Sb tracer. The soil-solution distribution coefficients (Kd) of Sb were measured for 110 soil samples. These Kds ranged from 1 to 2065 L kg(-1); the geometric mean was 62 L kg(-1) excluding one extremely high value, 2065 L kg(-1). Experimental measurement of Kd showed a decrease with both increasing pH and increasing phosphate concentration. The latter suggested that one aspect of the Sb sorption phenomena in Japanese soil was influenced by specific adsorption of anions such as phosphate. However, other aspects could not be explained by this specific adsorption mechanism, because only 20-40% of soil-sorbed Sb could be extracted by phosphate solution.