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.     

Whole-stream response to nitrate loading in three streams draining agricultural landscapes

Physical, chemical, hydrologic, and biologic factors affecting nitrate (NO3(-)) removal were evaluated in three agricultural streams draining orchard/dairy and row crop settings. Using 3-d "snapshots" during biotically active periods, we estimated reach-level NO3(-) sources, NO3(-) mass balance, in-stream processing (nitrification, denitrification, and NO3(-) uptake), and NO3(-) retention potential associated with surface water transport and ground water discharge. Ground water contributed 5 to 11% to stream discharge along the study reaches and 8 to 42% of gross NO3(-) input. Streambed processes potentially reduced 45 to 75% of ground water NO3(-) before discharge to surface water. In all streams, transient storage was of little importance for surface water NO3(-) retention. Estimated nitrification (1.6-4.4 mg N m(-2) h(-1)) and unamended denitrification rates (2.0-16.3 mg N m(-2) h(-1)) in sediment slurries were high relative to pristine streams. Denitrification of NO3(-) was largely independent of nitrification because both stream and ground water were sources of NO3(-). Unamended denitrification rates extrapolated to the reach-scale accounted for <5% of NO3(-) exported from the reaches minimally reducing downstream loads. Nitrate retention as a percentage of gross NO3(-) inputs was >30% in an organic-poor, autotrophic stream with the lowest denitrification potentials and highest benthic chlorophyll a, photosynthesis/respiration ratio, pH, dissolved oxygen, and diurnal NO3(-) variation. Biotic processing potentially removed 75% of ground water NO3(-) at this site, suggesting an important role for photosynthetic assimilation of ground water NO3(-) relative to subsurface denitrification as water passed directly through benthic diatom beds.     

Metals and selenium in wild animals from Norwegian areas close to Russian nickel smelters

This paper reports the concentrations of metals (Al, As, Cd, Cr, Cu, Hg, Ni, Pb, and/or Zn) and selenium (Se) in kidney and/or liver samples from capercaillie (Tetrao urogallus), willow ptarmigan (Lagopus lagopus), hares (Lepus timidus), common shrews (Sorex araneus) and grey-sided voles (Clethrionomus rufocanus) from the Norwegian areas most heavily contaminated by pollutants from the Russian smelters on the Kola peninsula. In addition to comparing areas that differed in expected pollution rate within Sør-Varanger, comparisons are drawn with reference data from other parts of Norway. The relatively highest levels of metals were found for Cu and Ni in the sub-area most heavily exposed to pollution from the smelters. Also the highest Cr concentrations were found in the areas closest to the smelters. In this study, there is evidence for a direct link between increased metal concentrations in wild animals and pollution from the Russian smelters for Cu and Ni and to some extent for Cr. relatively high concentration of Hg and slight increases in Pb are also documented, but regional differences within Sør-Varanger indicate no direct relationship to the Russian smelters. No samples showed concentrations of any of the analysed metals in excess of the limits where negative effects on animals can be measured.     

New Evidence for the presence of arsenocholine in shrimps (Pandalus borealis) by use of pyrolysis gas chromatography — atomic absorption spectrometry/mass spectrometry

An analytical method for the structure elucidation of quarternary organoarsenic compounds in trace amounts in fish and crustaceans has been developed in this laboratory. The two major organoarsenicals found in shrimps have been separated by ion-exchange chromatography and their stucture has been studied by the use of pyrolysis gas chromatography. Their degradation in the pyrolyzer unit has been studied by the use of atomic absorption spectrophotometer or mass spectrometer as detectors. A comparison of the analytical data of these substances and data from synthetic reference substances show complete agreement. The structures of reference compounds have been confirmed by use of nuclear magnetic resonance spectrometry and fast atom bombardment (FAB) mass spectrometry. It is demonstrated that both of the organoarsenic compounds in shrimps have a trimethylarsonio moiety e.g. the compounds have a quarternary structure. Furthermore, the more basic organoarsenic compound has a mass spectrometric fragmentation pattern similar to synthetic arsenocholine and acetylarsenocholine. Treatment of arsenobetaine with hot base produces trimethylarsineoxide in a high yield (96%). Arsenocholine, however, remains unchanged during this treatment. Treatment with sodium benzenethiolate does not result in chemical demethylation, which shows that this method together with gas chromatography-mass spectrometry is not feasible for confirmation of its structure.     

Obtaining access to coastal areas for large-scale mussel farming: obstacles and possibilities

Eutrophication in the coastal waters of the northern part of the Swedish west coast is causing structural and functional changes to the coastal ecosystems. Large-scale mussel farming is proposed in the Program of Measures, required by the EU Water Framework Directive to reduce the nutrients in the coastal water and improve water quality over a transition period of 10-20 years. Ownership, land parcelling, conflicts of interest, and the protection of coastal water are obstructing accessibility to suitable water areas for the establishment of mussel farming plants. This paper studies the obstacles and possibilities in the relevant laws and legal regulations governing the accessibility to coastal waters for large-scale mussel farming. Alternative ways to solve the problem are shown and discussed, within the framework of the Planning and Building Act, the Environmental Code and the laws concerning land-parceling and property. It is shown that the Planning and Building Act, when used in a proper manner, can provide useful instruments for society to gain access to coastal water for mussel farming plants with the purpose of improving the ecological status of the water.     

Modelling future soil chemistry at a highly polluted forest site at Istebna in Southern Poland using the "SAFE" model

The multi-layer dynamic model SAFE was applied to the forested catchment Istebna (Southern Poland), to study recovery from acidification. Environmental pollution in the area has been historically high. The model uses data from an intensive monitoring plot established in 1999 in a spruce stand, which was planted in 1880. Observations showed that the soil was depleted of base cations. The measured base saturation in 1999 was between 5 and 8% in the different soil layers. Model predictions assuming full implementation of the UNECE 1999 Gothenburg Protocol and present day base cation deposition show that the base saturation will slowly increase to 20% by 2100. Despite large emission reductions, Istebna still suffers from the very high loads of acidifying input during the past decades. Soil recovery depends on future emissions especially on base cation deposition. The recovery will be even slower if the base cation deposition decreases further.