The mobility of thorium in natural waters at low temperatures

Thermodynamic properties of 32 dissolved thorium species and 9 thorium-bearing solid phases have been collected from the literature, critically evaluated and estimated where necessary for 25°C and 1 atm pressure. Although the data are incomplete, especially for thorium minerals and organic complexes, some tentative conclusions can be drawn. Dissolved thorium is almost invariably complexed in natural waters. For example, based on ligand concentrations typical of ground water (ΣCl = 10 ppm, ΣF = 0.3 ppm, ΣSO₄ = 100 ppm, andΣPO₄ = 0.1 ppm), the predominant thorium species are Th(SO₄)⁰₂, ThF²⁺₂, and Th(HPO₄)₂⁰below pH ≈ 4.5; Th(HPO₄)^2?₃ from about pH 4.5 to 7.5; and Th(OH)⁰₄ above pH 7.5. Based on stability constants for thorium citrate, oxalate and EDTA complexes, it seems likely that organic complexes predominate over inorganic complexes of thorium in organic-rich stream waters, swamp waters, soil horizons, and waterlogged recent sediments. The thorium dissolved in seawater is probably present in organic complexes and as Th(OH)⁰₄. The tendency for thorium to form strong complexes enhances its potential for transport in natural waters by many orders of magnitude below pH 7 in the case of inorganic complexing, and below about pH 8 when organic complexing is important. The existence of complexes in addition to those formed with hydroxyl, is apparent from the fact that measured dissolved thorium in fresh surface waters (pH values generally 5–8) usually ranges from about 0.01 to 1 ppb and in surface seawater (pH = 8.1) is about 0.00064 ppb. This may be contrasted with the computed solubility of thorianite in pure water which is only 0.00001 ppb Th as Th(OH)⁰₄ above pH 5. Although complexing increases the solubility of thorium-bearing heavy minerals below pH 8, maximum thorium concentrations in natural waters are probably limited in general by the paucity and slow solution rate of these minerals and by sorption processes, rather than by mineral-solution equilibria.     

The mineralogic transformation of ferrihydrite induced by heterogeneous reaction with bioreduced anthraquinone disulfonate (AQDS) and the role of phosphate

Bioreduced anthraquinone-2,6-disulfonate (AH₂DS; dihydro-anthraquinone) was reacted with a 2-line, Si-substituted ferrihydrite under anoxic conditions at neutral pH in PIPES buffer. Phosphate (P) and bicarbonate (C); common adsorptive oxyanions and media/buffer components known to effect ferrihydrite mineralization; and Fe(II)_aq (as a catalytic mineralization agent) were used in comparative experiments. Heterogeneous AH₂DS oxidation coupled with Fe(III) reduction occurred within 0.13-1 day, with mineralogic transformation occurring thereafter. The product suite included lepidocrocite, goethite, and/or magnetite, with proportions varing with reductant:oxidant ratio (r:o) and the presence of P or C. Lepidocrocite was the primary product at low r:o in the absence of P or C, with evidence for multiple formation pathways. Phosphate inhibited reductive recrystallization, while C promoted goethite formation. Stoichiometric magnetite was the sole product at higher r:o in the absence and presence of P. Lepidocrocite was the primary mineralization product in the Fe(II)_aq system, with magnetite observed at near equal amounts when Fe(II) was high [Fe(II)/Fe(III)] = 0.5 and P was absent. P had a greater effect on reductive mineralization in the Fe(II)_aq system, while AQDS was more effective than Fe(II)_aq in promoting magnetite formation. The mineral products of the direct AH₂DS-driven reductive reaction are different from those observed in AH₂DS-ferrihydite systems with metal reducing bacteria, particularly in presence of P.     

Midsummer metabolism of an eelgrass community

Eelgrass (Zostera marina) is the dominant member of an important intertidal ecosystem found in many parts of the world. In this preliminary study the metabolism of the entire eelgrass community, including epiphytic plants and other organisms, has been measured in Great South Bay on Long Island, New York. In July it is in equilibrium and consumes as much oxygen as it produces, but in August both photosynthesis and respriation are reduced, with a net increase in oxygen production. This is due largely to the rapid growth of epiphytes during that month.     

A radiation-driven disc wind model for massive young stellar objects

The generation of magnetic fields by a battery, operating in an ion–electron plasma around a Kerr black hole, is studied in the 3+1 split of the Kerr metric. It is found that the gravitomagnetic contributions to the electron partial pressure are able to drive currents. The strength of the equilibrium magnetic field should be higher than for the classical Biermann battery, which is found to operate in this relativistic context as well, since the gravitomagnetic driving terms can less easily be quenched than the classical ones. In axisymmetry the battery can induce only toroidal magnetic fields. Once a toroidal magnetic field is present, however, the coupling of gravitomagnetic and electromagnetic fields generates a poloidal magnetic field even in axisymmetry. A rotating black hole, embedded in plasma, will therefore always generate toroidal and poloidal magnetic fields.     

Biogeochemistry of iron in an acidic lake

In this paper, the fate of iron in Lake Cristallina, an acidic lake in the Alps of Switzerland, is discussed. A simple conceptual model is developed in order to explain the observed diel variation in dissolved iron(II) concentration. Biotite weathering provides reduced iron that is oxidized and subsequently precipitated in the lake. The amorphous Fe(III)hydroxide (FeOOH xH₂O), found in the sediments of Lake Cristallina, is an Fe(II) oxidation product. This oxygenation reaction is most probably catalyzed by bacteria surfaces, as indicated by the relatively high estimated oxidation rate compared to the oxidation rate of the homogeneous oxidation of inorganic Fe(II) species at the ambient pH of Lake Cristallina (pH 5.4 at 4 °C) and by the scanning electron micrograph pictures. Under the influence of light, these amorphous iron(III)hydroxide phases are reductively dissolved. The net concentration of Fe(II) reflects the balance of the reductive dissolution and the oxidation/precipitation reactions and tends to parallel the light intensity, leading to a diurnal variation in the Fe(II) concentration. The rate of the photochemical reductive dissolution of Lake Cristallina iron(III)hydroxides is greatly enhanced in situ and in the laboratory by addition of oxalate to the lake water.     

Scalar fluxes from urban street canyons. Part I: Laboratory simulation

Flow over urban surfaces depends on surface morphology and interaction with the boundary layer above. However, the effect of the flow on scalar fluxes is hard to quantify. The naphthalene sublimation technique was used to quantify scalar vertical fluxes out of a street canyon under neutral conditions. For an array of eight canyons with aspect ratio H/W=0.75 (here, H is building height and W is the street width), increased flux was observed in the first two or three canyons for moderate and low roughness upstream. This is consistent with predictions of the length scale for initial adjustment of flow to an urban canopy. The flux was constant after the initial adjustment region and thus dependent only on local geometry. For a street canyon in the equilibrium part of the array, each facet of the street canyon was coated with naphthalene to simulate scalar release from street, walls and roof, to evaluate the effect of street canyon geometry on fluxes for H/W=0.25, 0.6, 1 and 2. Fluxes from the roof and downstream wall were considerably larger than fluxes from the street and upstream wall, and only the flux from the downstream wall exhibited a simple decrease with H/W. For each H/W there was a monotonic decrease between downstream wall, street and upstream wall transfer. This suggests that flow decelerates around the recirculation region in the lee of the upstream building, i.e. a recirculating jet rather than a symmetrical vortex. The addition of a second source within the street canyon resulted in reduced fluxes from each facet for H/W>0.25, due to increased concentration of naphthalene in the canyon air.