X-ray absorption and photoelectron spectroscopy investigation of selenite reduction by FeII-bearing minerals

The long-lived radionuclide 79Se is one of the elements of concern for the safe storage of high-level nuclear waste, since clay minerals in engineered barriers and natural aquifer sediments strongly adsorb cationic species, but to lesser extent anions like selenate (SeVIO4(2-)) and selenite (SeIVO3(2-)). Previous investigations have demonstrated, however, that SeIV and SeVI are reduced by surface-associated FeII, thereby forming insoluble Se0 and Fe selenides. Here we show that the mixed FeII/III (hydr)oxides green rust and magnetite, and the FeII sulfide mackinawite reduce selenite rapidly (< 1 day) to FeSe, while the slightly slower reduction by the FeII carbonate siderite produces elemental Se. In the case of mackinawite, both S(-II) and FeII surface atoms are oxidized at a ratio of one to four by producing a defective mackinawite surface. Comparison of these spectroscopic results with thermodynamic equilibrium modeling provides evidence that the nature of reduction end product in these FeII systems is controlled by the concentration of HSe(-); Se0 forms only at lower HSe(-) concentrations related to slower HSeO3(-) reduction kinetics. Even under thermodynamically unstable conditions, the initially formed Se solid phases may remain stable for longer periods since their low solubility prevents the dissolution required for a phase transformation into more stable solids. The reduction by Fe2+-montmorillonite is generally much slower and restricted to a pH range, where selenite is adsorbed (pH < 7), stressing the importance of a heterogeneous, surface-enhanced electron transfer reaction. Although the solids precipitated by the redox reaction are nanocrystalline, their solubility remains below 6.3 x 10(-8) M. No evidence for aqueous metal selenide colloids nor for Se sorption to colloidal phases was found. Since FeII phases like the ones investigated here should be ubiquitous in the near field of nuclear waste disposals as well as in the surrounding aquifers, mobility of the fission product 79Se may be much lower than previously assumed.     

Temperature-associated dynamics of songbird winter distributions and abundances

Using Christmas Bird Count data, we analyze the annual spatio-temporal abundances of six passerine species in the upper Great Plains, US (1960-1990). This study provides new insight into how global warming could cause separation of species within present-day communities. We find that winter relative abundances of similarly-sized songbirds are differentially affected by ambient winter temperature. As such, average annual winter temperature fluctuations (i.e., severity of winter) are significantly (P < 0.05) correlated with the relative abundances of three species while the other three are not. Our conditional probability-of-occurrence analysis indicates that the abundances of the three temperature-associated species declined markedly below -4 degrees C while the abundances of the other three species fluctuated little from 8 degrees C to -16 degrees C. We conclude that even in colder climates i) the winter distributions of some, but not all, songbirds are directly or indirectly limited by temperature; and ii) these birds have dynamic abundances that can quickly respond to temperature changes.     

Fate of RDX and TNT in agronomic plants

Phytoremediation is of great interest to remediate soil contaminated with hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4,6-trinitrotoluene (TNT). The ability of 4 agronomic plants (maize, soybean, wheat and rice) to take up these explosives and their fate in plants were investigated. Plants were grown for 42 days on soil contaminated with [(14)C]RDX or [(14)C]TNT. Then, each part was analyzed for its radioactivity content and the percentage of bound and soluble residues was determined following extractions. Extracts were analyzed by radio-HPLC. More than 80% of uptaken RDX was translocated to aerial tissues, up to 64.5 mgg(-1) of RDX. By contrast, TNT was little translocated to leaves since less than 25% of uptaken TNT was accumulated in aerial parts. Concentrations of TNT residues were 20 times lower than for RDX uptake. TNT was highly metabolized to bound residues (more than 50% of radioactivity) whereas RDX was mainly found in its parent form in aerial parts.     

Incest avoidance,fluctuating asymmetry,and the consequences of inbreeding in Iridomyrmex humilis,an ant with multiple queen colonies

Summary Inbreeding may have important consequences for the genetic structure of social insects and thus for sex ratios and the evolution of sociality and multiple queen (polygynous) colonies. The influence of kinship on mating preferences was investigated in a polygynous ant species, Iridomyrmex humilis, which has within-nest mating. When females were presented simultaneously with a brother that had been reared in the same colony until the pupal stage and an unrelated male produced in another colony, females mated preferentially with the unrelated male. The role of environmental colony-derived cues was tested in a second experiment where females were presented with two unrelated males, one of which had been reared in the same colony until the pupal stage (i.e., as in the previous experiment), while the other had been produced in another colony. In this experiment there was no preferential mating with familiar or unfamiliar males, suggesting that colony-derived cues might not be important in mating preferences. Inbreeding was shown to have no strong effect on the reproductive output of queens as measured by the number of worker and sexual pupae produced. The level of fluctuating asymmetry of workers produced by inbreeding queens was not significantly higher than that of non-inbreeding queens. Finally, colonies headed by inbreeding queens did not produce adult diploid males. Based on the current hypotheses of sex-determination the most plausible explanations for the absence of diploid-male-producing colonies are that (i) workers recognized and eliminated these males early in their development, and/or (ii) there are multiple sex-determining loci in this species. It is suggested that even if inbreeding effects on colony productivity are absent or low, incest avoidance mechanisms may have evolved and been maintained if inbreeding queens produce a higher proportion of unviable offspring. Correspondence to: L. Keller at the present address     

Metabolic fate of [14C]-2,4-dichlorophenol in macrophytes

The metabolic fate of 2,4-dichlorophenol (DCP) was investigated in six macrophytes representing different life forms. Salvinia natans and Lemna minor were chosen as surface-floating plants, Glyceria maxima and Mentha aquatica as emergent species and Myriophyllum spicatum and Hippuris vulgaris as submerged aquatic plants. After uptake of a [U-phenyl-14C]-DCP solution followed by a 48 h water chase, whole plants (L. minor, S. natans) or excised shoots were harvested and aqueous extracts were analysed by high performance liquid chromatography (HPLC). Metabolites were then isolated, submitted to enzymatic or chemical hydrolyses and characterised by electrospray ionisation-mass spectrometric analyses. Whereas DCP monoglucosides or more complex monoglucoside esters, either malonyl or acetyl, were found in most species, an unusual glucosyl-pentose conjugate was identified as the DCP major metabolite in L. minor and G. maxima. Our results showed for the first time the ability of five macrophytes to uptake and metabolise DCP and the characterisation of their metabolic pathways of DCP biotransformation.     

Portal absorption of 14C after ingestion of spiked milk with 14C-phenanthrene, 14C-benzo[a]pyrene or 14C-TCDD in growing pigs

Polycyclic aromatic hydrocarbons (PAHs) and dioxins are lipophilic organic pollutants occurring widely in the terrestrial environment. In order to study the PAHs and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) transfer in the food chain, pigs have been fed with milk mixed either with 14C-phenanthrene, with 14C-benzo[a]pyrene or with 14C-TCDD. The analysis of portal and arterial blood radioactivity showed that both PAHs and TCDD were absorbed with a maximum concentration at 4-6 h after milk ingestion. Then, the blood radioactivity decreased to reach background levels 24 h after milk ingestion. Furthermore, the portal and arterial blood radioactivities were higher for phenanthrene (even if the injected load was the lowest) than these of benzo[a]pyrene or these of TCDD, in agreement with their lipophilicity and water solubility difference. Main 14C absorption occurred during the 1-3 h time period after ingestion for 14C-phenanthrene and during the 3-6 h time period for 14C-benzo[a]pyrene and for 14C-TCDD. 14C portal absorption rate was high for 14C-phenanthrene (95%), it was close to 33% for 14C-benzo[a]pyrene and very low for 14C-TCDD (9%). These results indicate that the three studied molecules have a quite different behaviour during digestion and absorption. Phenanthrene is greatly absorbed and its absorption occurs via the blood system, whereas benzo[a]pyrene and TCDD are partly and weakly absorbed respectively. However these two molecules are mainly absorbed via the portal vein.     

Extractable soil lipids and microbial activity as affected by Bt and non Bt maize grown on a silty clay loam soil

Pyrolysis-gas (Py-GC) chromatography was used to characterize extractable lipids from Bt and non-Bt maize shoots and soils collected at time of harvesting. Py-GC-MS (mass spectrometry) showed that the concentrations of total alkenes identified in non-Bt shoots and soils were 47.9 and 21.3% higher than in Bt maize shoots and soils, respectively. N-alkanes identified were of similar orders of magnitude in Bt and non-Bt maize shoots, but were 28.6% higher in Bt than in non-Bt soils. Bt maize shoots contained 29.7% more n-fatty acids than non-Bt maize shoots, whereas the concentrations of n-fatty acids in Bt soils were twice as high as those in non-Bt soils. Concentrations of unsaturated fatty acids in Bt maize shoots were 22.1% higher than those in non-Bt maize shoots, while concentrations of unsaturated fatty acids were 22.5% higher in non-Bt than in Bt soils. The cumulative CO2-C evolved from soils under Bt and non-Bt crops was 30.5% lower under Bt as compared to non-Bt crops, whereas when maize shoots were added to Bt and non-Bt soils, the decrease in CO2-C evolved were 16.5 and 23.6%, respectively. Our data showed that the cultivation of Bt maize significantly increased the saturated to unsaturated lipid ratios in soils which appeared to negatively affect microbial activity.     

Disposition and metabolic profiling of [14C]-decabromodiphenyl ether in pregnant Wistar rats

Fully brominated diphenyl ether, decabromodiphenyl ether (DBDE), is one of the most widely used brominated flame retardants worldwide. Little data is available about the metabolic fate of DBDE in animal models and nothing at all about the extent of foetal exposure. In this work, pregnant Wistar rats were force-fed with 99.8% pure [14C]-DBDE over 96 h at a late stage of gestation (days 16 to 19). More than 19% of the administered dose was recovered in tissues and carcasses, demonstrating efficient absorption of DBDE despite its high molecular weight and low solubility. The highest concentrations of DBDE residues were found in endocrine glands (adrenals, ovaries) and in the liver, with lower values recorded for fat. In all tissue extracts, most of the radioactivity was associated with unchanged DBDE. The use of high-grade purity [14C]-DBDE allowed quantification of several metabolites present both in maternal tissues and in foetuses. These biotransformation products accounted for 9-27% of the extractable radioactivity in tissues and 14% of that in foetuses. Three nona-BDEs and one octa-BDE were identified by LC-APPI/MS. The unequivocal characterisation of a hydroxylated octa-BDE isolated from liver was confirmed by NMR. In rat, the main metabolic pathways of DBDE are debromination and oxidation. DBDE, and very likely most of its metabolites, are able to cross the placental barrier in rat. Metabolic profiles, obtained in vivo for the first time, demonstrated the presence of DBDE and major biotransformation products in endocrine glands as well as in foetuses. The biological activity of these metabolites still needs to be assessed in order to better understand the potential toxicity of DBDE.