Temperature dependence of goethite dissolution promoted by trihydroxamate siderophores

This article reports an investigation of the temperature dependence of goethite dissolution kinetics in the presence of desferrioxamine B (DFO-B), a trihydroxamate siderophore, and its acetyl derivative, desferrioxamine D1 (DFO-D1). At 25 and 40°C, DFO-D1 dissolved goethite at twice the rate of DFO-B, whereas at 55°C, the behavior of the two ligands was almost the same. Increasing the temperature from 25 to 55°C caused little or no significant change in DFO-B or DFO-D1 adsorption by goethite. A pseudo-first-order rate coefficient for dissolution, calculated as the ratio of the mass-normalized dissolution rate coefficient to the surface excess of siderophore, was approximately the same at 25 and 40°C for both siderophores. At 55°C, however, this rate coefficient for DFO-D1 was about half that for DFO-B. Analysis of the temperature dependence of the mass-normalized dissolution rate coefficient via the Arrhenius equation led to an apparent activation energy that was larger for DFO-B than for DFO-D1, but much smaller than that reported for the proton-promoted dissolution of goethite. A compensation law was found to relate the pre-exponential factor to the apparent activation energy in the Arrhenius equation, in agreement with what has been noted for the proton-promoted dissolution of oxide minerals and for the complexation of Fe³⁺ by DFO-B and simple hydroxamate ligands in aqueous solution. Analysis of these results suggested that the siderophores adsorb on goethite with a only single hydroxamate group in bidentate ligation with an Fe(III) center.     

Numerical calculation of Thomson scattering from inhomogeneous models of the corona,and application to streamers of the 1970 and 1972 eclipses

A general computer program has been developed to numerically integrate the Thomson scattered light from arbitrary inhomogeneous models of the solar corona. Conversion from the observer's to solar coordinates is totally general to eliminate restrictions on the lines-of-sight that may be investigated. The tangential and radial components (K _t and K _r ),or any combination thereof, are calculated. Four separate output modes are available, corresponding to the common formats used for coronal brightness and polarization data.This program was used to investigate the major NW streamer of the 1972 eclipse. The bifurcated profile of this feature is reproduced by the projection effect of a radially expanding blade, or fan, whose longitudinal axis is twisted to follow an underlying magnetic neutral line on the solar surface. Thus a purely geometrical effect accounts for the observed intensity profile. Published brightness data for the NE streamer of the 1970 eclipse are also reinterpreted using the radially-expanding fan model. The axial density gradients of 1970 and 1972 features are found to be virtually identical from 3 to 8 R .     

Biogeochemistry of iron oxidation in a circumneutral freshwater habitat

Iron(II) oxidation in natural waters at circumneutral pH, often regarded as an abiotic process, is frequently biologically mediated at iron-rich redox gradients. West Berry Creek, a small circumneutral tributary that flows through a mixed coniferous forest in Big Basin State Park, California, contains localized iron (hydr)oxide precipitates at points along its course where anoxic groundwater meets oxygenated creek water. These mixing zones establish redox gradients that may be exploited by microbes forming microbial mats that are intimately associated with iron (hydr)oxide precipitates. Water sampling revealed strong correlations between the concentrations of aqueous inorganic species, suggesting a rock-weathering source for most of these solutes. Liquid chromatography–electrospray ionization–mass spectrometry techniques detected significant concentrations of organic exudates, including low molecular mass organic acids and siderophores, indicating that active biogeochemical cycling of iron is occurring in the creek. X-ray diffraction and elemental analysis showed the precipitates to be amorphous, or possibly poorly crystalline, iron-rich minerals. Clone libraries developed from 16S rDNA sequences extracted from microbial mat communities associated with the precipitates revealed the presence of microorganisms related to the neutrophilic iron oxidizing bacteria Gallionella and Sideroxydans. Sequences from these libraries also indicated the presence of significant populations of organisms related to bacteria in the genera Aquaspirillum, Pseudomonas, Sphingomonas, and Nitrospira. These geosymbiotic systems appear to be significant not only for the biogeochemical cycling of iron in the creek, but also for the cycling of organic species, inorganic nutrients, and trace metals.     

Animated molecular dynamics simulations of hydrated caesium-smectite interlayers

Computer animation of center of mass coordinates obtained from 800 ps molecular dynamics simulations of Cs-smectite hydrates (1/3 and 2/3 water monolayers) provided information concerning the structure and dynamics of the interlayer region that could not be obtained through traditional simulation analysis methods. Cs⁺ formed inner sphere complexes with the mineral surface, and could be seen to jump from one attracting location near a layer charge site to the next, while water molecules were observed to migrate from the hydration shell of one ion to that of another. Neighboring ions maintained a partial hydration shell by sharing water molecules, such that a single water molecule hydrated two ions simultaneously for hundreds of picoseconds. Cs-montmorillonite hydrates featured the largest extent of this sharing interaction, because interlayer ions were able to inhabit positions near surface cavities as well as at their edges, close to oxygen triads. The greater positional freedom of Cs⁺ within the montmorillonite interlayer, a result of structural hydroxyl orientation and low tetrahedral charge, promoted the optimization of distances between cations and water molecules required for water sharing. Preference of Cs⁺ for locations near oxygen triads was observed within interlayer beidellite and hectorite. Water molecules also could be seen to interact directly with the mineral surface, entering its surface cavities to approach attracting charge sites and structural hydroxyls. With increasing water content, water molecules exhibited increased frequency and duration of both cavity habitation and water sharing interactions. Competition between Cs⁺ and water molecules for surface sites was evident. These important cooperative and competitive features of interlayer molecular behavior were uniquely revealed by animation of an otherwise highly complex simulation output.     

Manganese(III) binding to a pyoverdine siderophore produced by a manganese(II)-oxidizing bacterium

The possible roles of siderophores (high affinity chelators of iron(III)) in the biogeochemistry of manganese remain unknown. Here we investigate the interaction of Mn(III) with a pyoverdine-type siderophore (PVD_MnB1) produced by the model Mn(II)-oxidizing bacterium Pseudomonas putida strain MnB1. PVD_MnB1 confirmed typical pyoverdine behavior with respect to: (a) its absorption spectrum at 350-600 nm, both in the absence and presence of Fe(III), (b) the quenching of its fluorescence by Fe(III), (c) the formation of a 1:1 complex with Fe(III), and (d) the thermodynamic stability constant of its Fe(III) complex. The Mn(III) complex of PVD_MnB1 had a 1:1 Mn:pvd molar ratio, showed fluorescence quenching, and exhibited a light absorption spectrum (A_max = 408-410 nm) different from that of either PVD_MnB1-Fe(III) or uncomplexed PVD_MnB1. Mn(III) competed strongly with Fe(III) for binding by PVD_MnB1 in culture filtrates (pH 8, 4°C). Equilibration with citrate, a metal-binding ligand, did not detectably release Mn from its PVD_MnB1 complex at a citrate/PVD_MnB1 molar ratio of 830 (pH 8, 4°C), whereas pyrophosphate under the same conditions removed 55% of the Mn from its PVD_MnB1 complex. Most of the PVD_MnB1-complexed Mn was released by reaction with ascorbate, a reducing agent, or with EDTA, a ligand that is also oxidized by Mn(III). Data on the competition for binding to PVD_MnB1 by Fe(III) vs. Mn(III) were used to determine a thermodynamic stability constant (nominally at 4°C) for the neutral species MnHPVD_MnB1 (log K = 47.5 ± 0.5, infinite dilution reference state). This value was larger than that determined for FeHPVD_MnB1 (log K = 44.6 ± 0.5). This result has important implications for the metabolism, solubility, speciation, and redox cycling of manganese, as well as for the biologic uptake of iron.     

Motional modes of dilatational waves in elastic porous media containing two immiscible fluids

Numerical simulations of dilatational waves in an elastic porous medium containing two immiscible viscous compressible fluids indicate that three types of wave occur, but the modes of dilatory motion corresponding to the three waves remain uncharacterized as functions of relative saturation. In the present paper, we address this problem by deriving normal coordinates for the three dilatational waves based on the general poroelasticity equations of Lo et al. 2005 [13]. The normal coordinates provide a theoretical foundation with which to characterize the motional modes in terms of six connecting coefficients that depend in a well defined way on inertial drag, viscous drag, and elasticity properties. Using numerical calculations of the connecting coefficients in the seismic frequency range for an unconsolidated sand containing water and air as a representative example relevant to hydrologic applications, we confirm that the dilatational wave whose speed is greatest corresponds to the motional mode in which the solid framework and the two pore fluids always move in phase, regardless of water saturation, in agreement with the classic Biot theory of the fast compressional wave in a water-saturated porous medium. For the wave which propagates second fastest, we show, apparently for the first time, that the solid framework moves in phase with water, but out of phase with air [Mode (III)], if the water saturation is below about 0.8, whereas the solid framework moves out of phase with both pore fluids [Mode (IV)] above this water saturation. The transition from Mode (III) to Mode (IV) corresponds to that between the capillarity-dominated region of the water retention curve and the region reflecting air-entry conditions near full water saturation. The second of the two modes corresponds exactly to the slow compressional wave in classic Biot theory, whereas the first mode is possible only in a two-fluid system undergoing capillary pressure fluctuations. For the wave which has the smallest speed, the dilatational mode is dominated by the motions of the two pore fluids, which are always out of phase, a result that is consistent with the proposition that this wave is caused by capillary pressure fluctuations.     

Megacrysts and xenoliths in kimberlite,Elliott County,Kentucky: A mantle sample from beneath the Permian Appalachian Plateau

Two kimberlite pipes in Elliott County contain rare ultramafic xenoliths and abundant megacrysts of olivine (Fo_85–93), garnet (0.21–9.07% Cr₂O₃), picroilmenite, phlogopite, Cr-poor clinopyroxene (0.56–0.88% Cr₂O₃), and Cr-poor orthopyroxene (<0.03–0.34% Cr₂O₃) in a matrix of olivine (Fo_88–92), picroilmenite, Cr-spinel, magnetite, perovskite, pyrrhotite, calcite, and hydrous silicates. Rare clinopyroxene-ilmenite intergrowths also occur. Garnets show correlation of mg (0.79–0.86) and CaO (4.54–7.10%) with Cr₂O₃ content; the more Mg-rich garnets have more uvarovite in solution. Clinopyroxene megacrysts show a general decrease in Cr₂O₃ and increase in TiO₂ (0.38–0.56%) with decreasing mg (0.87–0.91). Clinopyroxene megacrysts are more Cr-rich than clinopyroxene in clinopyroxene-ilmenite intergrowths (0.06–0.38% Cr₂O₃) and less Cr-rich than peridotite clinopyroxenes (1.39–1.46% Cr₂O₃). Orthopyroxene megacrysts and orthopyroxene inclusions in olivine megacrysts form two populations: high-Ca, high-Al (1.09–1.16% CaO and 1.16–1.18% Al₂O₃) and low-Ca, low-Al (0.35–0.46% CaO and 0.67–0.74% Al₂O₃). Three orthopyroxenes belonging to a low-Ca subgroup of the high-Ca, high-Al group were also identified (0.86–0.98% CaO and 0.95–1.01% Al₂O₃). The high-Ca, high-Al group (Group I) has lower mg (0.88–0.90) than low-Ca, low-Al group (Group II) with mg=0.92–0.93; low mg orthopyroxenes (Group Ia) have lower Cr₂O₃ and higher TiO₂ than high mg orthopyroxenes (Group II). The orthopyroxene megacrysts have lower Cr₂O₃ than peridotite orthopyroxenes (0.46–0.57% Cr₂O₃). Diopside solvus temperatures indicate equilibration of clinopyroxene megacrysts at 1,165°–1,390° C and 1,295°–1,335° C for clinopyroxene in clinopyroxene-ilmenite intergrowths. P-T estimates for orthopyroxene megacrysts are bimodal: high-Ca, high-Al (Group I) orthopyroxenes equilibrated at 1,165°–1,255° C and 51–53 kb (± 5kb) and the low-Ca, low-Al (Group II) orthopyroxenes equilibrated at 970°–1,020°C and 46–56 kb (± 5kb). Garnet peridotites equilibrated at 1,240°–1,360° C and 47–49 kb. Spinel peridotites have discordant temperatures of 720°–835° C (using spinel-olivine Fe/Mg) and 865°–1,125° C (Al in orthopyroxene).Megacrysts probably precipitated from a fractionating liquid at >150 km depth. They are not disaggregated peridotite because: (1) of large crystal size (up to 1.5 cm), (2) compositions are distinctly different from peridotite phases, and (3) they display fractionation trends. The high mg, low T orthopyroxenes and the clustering of olivine rims near Fo_89–90 reflect liquid changes to higher MgO contents due to (1) assimilation of wall-rock and/or (2) an increase in Fe³⁺/Fe²⁺ and subsequently MgO/FeO as a result of an increase in f _o.