X-ray absorption and photoelectron spectroscopy investigation of selenite reduction by Fe-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 (Se^VIO₄²⁻) and selenite (Se^IVO₃²⁻). Previous investigations have demonstrated, however, that Se^IV and Se^VI are reduced by surface-associated Fe^II, thereby forming insoluble Se⁰ and Fe selenides. Here we show that the mixed Fe^II/^III (hydr)oxides green rust and magnetite, and the Fe^II sulfide mackinawite reduce selenite rapidly (< 1 day) to FeSe, while the slightly slower reduction by the Fe^II carbonate siderite produces elemental Se. In the case of mackinawite, both S^−II and Fe^II 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 Fe^II 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 × 10^− 8 M. No evidence for aqueous metal selenide colloids nor for Se sorption to colloidal phases was found. Since Fe^II 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.     

Uncertainty in Agricultural CH<Subscript>4</Subscript> AND N<Subscript>2</Subscript>O Emissions from Finland – Possibilities to Increase Accuracy in Emission Estimates

According to the United Nations Framework Convention on Climate Change (UNFCCC) and Kyoto Protocol under it, industrial countries have to estimate their greenhouse gas emissions annually, and assess the uncertainties in these estimates. In Finland, agricultural methane (CH₄) and nitrous oxide (N_2O) emissions represent 7% of anthropogenic greenhouse gas emissions, and globally the share is much higher. Agriculture is one of the most uncertain emission categories (representing over 20% of greenhouse gas inventory uncertainty in Finland), due to both high natural variability of the emission sources and poor knowledge of the emission-generating processes. In this paper, we present an uncertainty estimate of agricultural CH₄ and N₂O emissions from Finland in 2002. Uncertainties were estimated based on measurement data, literature and expert judgement, and total uncertainty in agriculture was calculated using Monte Carlo simulation. According to the calculations, agricultural CH₄ and N₂O emissions from Finland were 3.7 to 7.8 Tg carbon dioxide (CO₂) equivalents, 5.4 Tg being the mean value.Estimates of CH₄ emissions are more reliable than those of N₂O. N₂O from agricultural soils was the most uncertain emission category, and the uncertainty was not reduced by using available national measurement data of N₂O fluxes. Sensitivity study revealed that the uncertainty in total agricultural inventory could be 7% points lower, if more accurate emission estimation methods were used, including 1) improved data collection in area estimates of organic soils, 2) climate-specific methods for N₂O from agricultural soils as already presented in literature, and 3) more detailed CH₄ estimation methods for enteric fermentation which can be achieved by investigating national circumstances and digestible systems of animals in more detail.     

The Role of Fungal Symbioses in the Adaptation of Plants to High Stress Environments

All plants studied in natural ecosystemsare symbiotic with fungi that either resideentirely (endophytes) or partially(mycorrhizae) within plants. Thesesymbioses appear to adapt to biotic andabiotic stresses and may be responsible forthe survival of both plant hosts and fungalsymbionts in high stress habitats. Here wedescribe the role of symbiotic fungi inplant stress tolerance and present astrategy based on adaptive symbiosis topotentially mitigate the impacts of globalchange on plant communities.     

Measurements of phytol in estuarine suspended organic matter

The unsaturated isoprenoid alcohol phytol is a constituent of the major chlorophyll species a and b and, as such, should be useful as an estimator for chlorophyll values. A method for the extraction of phytol from estuarine suspended organic matter and analysis by gas-liquid chromatography (GLC) is described. Comparisons of the GLC method for phytol-chlorophyll analyses and a spectrophotometric chlorophyll method indicate that the GLC method gives values in good agreement with the spectrophotometric procedure. Similar trends in suspended chlorophyll values were observed in Narragansett Bay (Rhode Island, USA) water samples using the GLC method and a fluorometric procedure. The results of these studies indicate that the GLC method provides reliable analyses of chlorophyll and, although more time-consuming, has the advantage that other organic species can be analyzed in the same sample, thus providing additional information on its chemical composition.     

An Optimised Direct Lysis Method for Viral RNA Extraction and Detection of Foodborne Viruses on Fruits and Vegetables

Detection of norovirus (NoV) and hepatitis A virus (HAV) on fruits and vegetables using current standard methodologies can be inefficient. Method optimisat     

The effects of benomyl and its breakdown products carbendazim and butyl isocyanate on the structure and function of tracheal ciliated cells

Abstract

The effects of the fungicide benomyl and its breakdown products, carbendazim and butyl isocyanate, were examined on canine tracheal epithelial tissue in primary culture. Changes in ciliary frequencies were monitored with an optical spectrum analysis system. Serial dilutions of the test compounds were prepared in 100% corn oil and applied to the cell cultures for intervals up to 6 hours and frequencies measured at intervals of 15 minutes to 1 hour. Benomyl and butyl isocyanate caused concentration‐dependent decreases in ciliary beat frequency. Benomyl at 300 μg/ml (3 mM) caused ciliostasis within 75 minutes of exposure. Butyl isocyanate at a molar concentration three times lower than benomyl (1 mM) caused a similar response, although within 30 minutes. The IBC₅₀ for benomyl was 0.75 mM, while for butyl isocyanate it was 0.52 mM. Carbendazim caused a moderate decrease in frequency over a 6 hour exposure period. Benomyl caused moderate to severe swelling of the mitochondria of ciliated epithelial cells with other cell organelles appearing normal. Butyl isocyanate did not cause any noticeable effect on cell ultrastructure and the apparently low rate of penetration of carbendazim into cells made it impossible to obtain an effect which justified ultrastructural analysis. It appears, at least for benomyl and butyl isocyanate, that while the physiological effect of these two compounds (inhibition of ciliary beat) is the same, the sites of action in the cell may be different.