Arsenite sequestration at the surface of nano-Fe(OH)2, ferrous-carbonate hydroxide, and green-rust after bioreduction of arsenic-sorbed lepidocrocite by Shewanella putrefaciens

X-ray Absorption Fine Structure (XAFS) spectroscopy was used in combination with high resolution transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS), X-ray energy dispersive spectroscopy (XEDS), X-ray powder diffraction, and Mössbauer spectroscopy to obtain detailed information on arsenic and iron speciation in the products of anaerobic reduction of pure and As(V)- or As(III)-adsorbed lepidocrocite (γ-FeOOH) by Shewanella putrefaciens ATCC 12099. We found that this strain of S. putrefaciens is capable of using Fe(III) in lepidocrocite and As(V) in solution or adsorbed on lepidocrocite surfaces as electron acceptors. Bioreduction of lepidocrocite in the absence of arsenic resulted in the formation of hydroxycarbonate green rust 1 [Fe^II₄Fe^III₂(OH)₁₂CO₃: GR1(CO₃)], which completely converted into ferrous-carbonate hydroxide (Fe^II₂(OH)₂CO₃: FCH) over nine months. This study thus provides the first evidence of bacterial reduction of stoichiometric GR1(CO₃) into FCH. Bioreduction of As(III)-adsorbed lepidocrocite also led to the formation of GR1(CO₃) prior to formation of FCH, but the presence of As(III) slows down this transformation, leading to the co-occurrence of both phases after 22-month of aging. At the end of this experiment, As(III) was found to be adsorbed on the surfaces of GR1(CO₃) and FCH. After five months, bioreduction of As(V)-bearing lepidocrocite led directly to the formation of FCH in association with nanometer-sized particles of a minor As-rich Fe(OH)₂ phase, with no evidence for green rust formation. In this five-month experiment, As(V) was fully converted to As(III), which was dominantly sorbed at the surface of the Fe(OH)₂ nanoparticles as oligomers binding to the edges of Fe(OH)₆ octahedra at the edges of the octahedral layers of Fe(OH)₂. These multinuclear As(III) surface complexes are characterized by As-As pairs at a distance of 3.32 ± 0.02 Å and by As-Fe pairs at a distance of 3.50 ± 0.02 Å and represent a new type of As(III) surface complex. Chemical analyses show that the majority of As(III) produced in the experiments with As present is associated with iron-bearing hydroxycarbonate or hydroxide solids, reinforcing the idea that, at least under some circumstances, bacterial reduction can promote As(III) sequestration instead of mobilizing it into solution.     

Presumed magnetic biosignatures observed in magnetite derived from abiotic reductive alteration of nanogoethite

The oriented chains of nanoscale Fe-oxide particles produced by magnetotactic bacteria are a striking example of biomineralization. Several distinguishing features of magnetite particles that comprise bacterial magnetosomes have been proposed to collectively constitute a biosignature of magnetotactic bacteria (Thomas-Keprta et al., 2001). These features include high crystallinity, chemical purity, a single-domain magnetic structure, well-defined crystal morphology, and arrangement of particles in chain structures. Here, we show that magnetite derived from the inorganic breakdown of nanocrystalline goethite exhibits magnetic properties and morphologies remarkably similar to those of biogenic magnetite from magnetosomes. During heating in reducing conditions, oriented nanogoethite aggregates undergo dehydroxylation and transform into stoichiometric magnetite. We demonstrate that highly crystalline single-domain magnetite with euhedral grain morphologies produced abiogenically from goethite meets several of the biogenicity criteria commonly used for the identi?cation of magnetofossils. Furthermore, the suboxic conditions necessary for magnetofossil preservation in sediments are conducive to the reductive alteration of nanogoethite, as well as the preservation of detrital magnetite originally formed from goethite. The findings of this study have potential implications for the identification of biogenic magnetite, particularly in older sediments where diagenesis commonly disrupts the chain structure of magnetosomes. Our results indicate that isolated magnetofossils cannot be positively distinguished from inorganic magnetite on the basis of their magnetic properties and morphology, and that intact chain structures remain the only reliable distinguishing feature of fossil magnetosomes.     

Collocation resolution of the oceanic geoid based on satellite altimetry

The approach presented is directed toward a specific adaptation of the least‐squares collocation with noise, yielding smooth predictions of geophysical quantities. The smoothing corresponds here to a truncated gravity field equivalent to an (n’, n') spherical‐harmonic expansion. This is reflected in the truncation, at the degree n‘, of the pertinent covariance and cross‐covariance functions in most (but not all) instances. The smooth predictions of geophysical quantities, made in an equilateral grid corresponding to the truncation degree n‘, serve in constructing contour maps after having been densified for the needs of a contour routine. Such a densification is carried out efficiently via errorless collocation with the degree truncation n‘ throughout. Consistent with this procedure, “residuals” at observation points (i.e., discrepancies between the contour map and the data) are computed using the same algorithm. The complete collocation approach is utilized for a 2° resolution of the earth's gravity field with emphasis on the oceanic geoid, based on the residuals from a global spherical‐harmonic adjustment of SEASAT altimetry. The presented results include contour maps of geoid undulations and gravity anomalies. They are compared to the results of a point‐mass adjustment, another technique based on the spherical‐harmonic adjustment. The agreement between these two techniques is found to be excellent.     

Abrupt onset of carbonate deposition in Lake Kivu during the 1960s: response to recent environmental changes

This study interprets the recent history of Lake Kivu, a tropical lake in the East African Rift Valley. The current gross sedimentation was characterized from a moored sediment trap array deployed over 2 years. The past net sedimentation was investigated with three short cores from two different basins. Diatom assemblages from cores were interpreted as reflecting changes in mixing depth, surface salinity and nutrient availability. The contemporary sediment trap data indicate seasonal variability, governed by diatom blooms during the annual mixing in the dry season, similar to Lakes Malawi and Tanganyika. The ratio of settling fluxes to net sediment accumulation rates implies mineralization rates of 80–90% at the sediment-water interface. The sediment cores revealed an abrupt change ~40 years ago, when carbonate precipitation started. Since the 1960s, deep-water methane concentrations, nutrient fluxes and soil mineral inputs have increased considerably and diatom assemblages have altered. These modifications probably resulted from a combination of three factors, commonly altering lake systems: the introduction of a non-native fish species, eutrophication, and hydrological changes inducing greater upwelling. Both the fish introduction and increased rainfall occurred at the time when the onset of carbonate precipitation was observed, whereas catchment population growth accompanied by intensified land use increased the flux of soil minerals already since the early twentieth century due to more intense erosion.     

Mapping of erosion rates in marly badlands based on a coupling of anatomical changes in exposed roots with slope maps derived from LiDAR data

Black marls form very extensive outcrops in the Alps and constitute some of the most eroded terrains, thus causing major problems of sedimentation in artificial storage systems (e.g. reservoirs) and river systems. In the experimental catchments near Draix (France), soil erosion rates have been measured in the past at the plot scale through a detailed monitoring of surface elevation changes and at the catchment scale through continuous monitoring of sediment yield in traps at basin outlets. More recently, erosion rates have been determined by means of dendrogeomorphic techniques in three monitored catchments of the Draix basin. A total of 48 exposed roots of Scots pine have been sampled and anatomical variations in annual growth rings resulting from denudation analysed. At the plot scale, average medium‐term soil erosion rates derived from exposed roots vary between 1·8 and 13·8 mm yr^?1 (average: 5·9 mm yr^?1) and values are significantly correlated with slope angle. The dendrogeomorphic record of point‐scale soil erosion rates matches very well with soil erosion rates measured in the Draix basins. Based on the point‐scale measurements and dendrogeomorphic results obtained at the point scale, a linear regression model involving slope angle was derived and coupled to high‐resolution slope maps obtained from a LiDAR‐generated digital elevation model so as to generate high‐resolution soil erosion maps. The resulting regression model is statistically significant and average soil erosion rates obtained from the areal erosion map (5·8, 5·2 and 6·2 mm yr^?1 for the Roubine, Moulin and Laval catchments, respectively) prove to be well in concert with average annual erosion rates measured in traps at the outlet of these catchments since 1985 (6·3, 4·1 and 6·4 mm yr^?1). This contribution demonstrates that dendrogeomorphic analyses of roots clearly have significant potential and that they are a powerful tool for the quantification and mapping of soil erosion rates in areas where measurements of past erosion is lacking. Copyright © 2011 John Wiley & Sons, Ltd.     

Coupled discrete element and finite volume solution of two classical soil mechanics problems

One dimensional solutions for the classic critical upward seepage gradient/quick condition and the time rate of consolidation problems are obtained using coupled routines for the finite volume method (FVM) and discrete element method (DEM), and the results compared with the analytical solutions. The two phase flow in a system composed of fluid and solid is simulated with the fluid phase modeled by solving the averaged Navier–Stokes equation using the FVM and the solid phase is modeled using the DEM. A framework is described for the coupling of two open source computer codes: YADE-OpenDEM for the discrete element method and OpenFOAM for the computational fluid dynamics. The particle–fluid interaction is quantified using a semi-empirical relationship proposed by Ergun [12]. The two classical verification problems are used to explore issues encountered when using coupled flow DEM codes, namely, the appropriate time step size for both the fluid and mechanical solution processes, the choice of the viscous damping coefficient, and the number of solid particles per finite fluid volume.     

A new scenario for the last magmatic eruption of La Soufrière of Guadeloupe (Lesser Antilles) in 1530 A.D. Evidence from stratigraphy radiocarbon dating and magmatic evolution of erupted products

La Soufrière of Guadeloupe is a dangerous volcano characterized over the last decade by moderate seismic and fumarolic unrest. In the last 15,000 years it has experienced phreatic and magmatic eruptions and unusually numerous flank collapse events sometimes associated with a magmatic eruption. We propose a new age of 1530 A.D. and a new eruptive scenario for the last magmatic eruption on the basis of a novel statistical analysis of radiocarbon age dates, and new field and geochemical data. This eruption is the only magmatic eruption likely to have occurred in Guadeloupe during the last 1400 years. The eruption mainly involved an andesitic magma which, in the first phase of the eruption, partially mixed with a slightly more differentiated magma stored in a small and shallow magma chamber. Ascent of magma to the surface generated a partial collapse of the hydrothermally altered edifice that increased the magma discharge and led to a sub-plinian phase with scoria fallout and column-collapse pyroclastic flows followed by near-vent pyroclastic scoria fountains. The eruption ended with growth of a lava dome. Our revised interpretation of the last magmatic eruption of La Soufrière constitutes the most likely key to a future magmatic eruption scenario for this volcano which displays strong evidence of unrest since 1992.     

Simulation of the interaction of galactic cosmic‐ray protons with meteoroids: On the production of radionuclides in thick gabbro and iron targets irradiated isotropically with 1.6 GeV protons

Abstract— Thick spherical targets made of gabbro (R = 25 cm) and of steel (R = 10 cm) were irradiated isotropically with 1.6 GeV protons at the Saturne synchrotron at Laboratoire National Saturne (LNS)/CEN Saclay in order to simulate the interaction in space of galactic cosmic‐ray (GCR) protons with stony and iron meteoroids. Proton fluences of 1.32 × 10¹⁴ cm^?2 and 2.45 × 10¹⁴ cm^?2 were received by the gabbro and iron sphere, respectively, which corresponds to cosmic‐ray exposure ages of about 1.6 and 3.0 Ma. Both artificial meteoroids contained large numbers of high‐purity target foils of up to 28 elements at different depths. In these individual target foils, elementary production rates of radionuclides and rare gas isotopes were measured by x‐ and γ‐spectrometry, by low‐level counting, accelerator mass spectrometry (AMS), and by conventional rare gas mass spectrometry. Also samples of the gabbro itself were analyzed. Up to now, for each of the experiments, ～500 target‐product combinations were investigated of which the results for radionuclides are presented here. The experimental production rates show a wide range of depth profiles reflecting the differences between low‐, medium‐, and high‐energy products. The influence of the stony and iron matrices on the production of secondary particles and on particle transport, in general, and consequently on the production rates is clearly exhibited by the phenomenology of the production rates as well as by a detailed theoretical analysis. Theoretical production rates were calculated in an a priori way by folding depth‐dependent spectra of primary and secondary protons and secondary neutrons calculated by Monte Carlo techniques with the excitation functions of the underlying nuclear reactions. Discrepancies of up to a factor of 2 between the experimental and a priori calculated depth profiles are attributed to the poor quality of the mostly theoretical neutron excitation functions. Improved neutron excitation functions were obtained by least‐squares deconvolution techniques from experimental thick‐target production rates of up to five thick‐target experiments in which isotropic irradiations were performed. A posteriori calculations using the adjusted neutron cross sections describe the measured depth profiles of all these simulation experiments within 9%. The thus validated model calculations provide a basis for reliable physical model calculations of the production rates of cosmogenic nuclides in stony and iron meteorites as well as in lunar samples and terrestrial materials.     

Preliminary report on radiocarbon dating of cryptoendolithic microorganisms

The existence of microbial communities living inside desert rocks has been reported by FRIEDMANN et al. (1967, 1976), first in rocks collected from the hot and dry Negev desert and later in rocks in the frigid Ross Desert of Southern Victoria Land, Antarctica. The extremely inhospitable climatic conditions in both places has led to the suggestion that these organisms have very low rates of metabolism and may, in addition, be very old (FRIEDMANN 1982). Our preliminary measurements showed a 14C deficiency indicating a carbon age in the order of magnitude of 10(3) years.     

Arsenite sorption at the magnetite-water interface during aqueous precipitation of magnetite: EXAFS evidence for a new arsenite surface complex

The interaction of aqueous As(III) with magnetite during its precipitation from aqueous solution at neutral pH has been studied as a function of initial As/Fe ratio. Arsenite is sequestered via surface adsorption and surface precipitation reactions, which in turn influence the crystal growth of magnetite. Sorption samples were characterized using EXAFS spectroscopy at the As K-edge in combination with HRTEM observations, energy dispersive X-ray analysis at the nanoscale, electron energy loss spectroscopy at the Fe L₃-edge, and XRD-Rietveld analyses of reaction products. Our results show that As(III) forms predominantly tridentate hexanuclear As(III)O₃ complexes (³C), where the As(III)O₃ pyramids occupy vacant tetrahedral sites on {1 1 1} surfaces of magnetite particles. This is the first time such a tridentate surface complex has been observed for arsenic. This complex, with a dominant As-Fe distance of 3.53 ± 0.02 Å, occurs in all samples examined except the one with the highest As/Fe ratio (0.33). In addition, at the two highest As/Fe ratios (0.133 and 0.333) arsenite tends to form mononuclear edge-sharing As(III)O₃ species (²E) within a highly soluble amorphous As(III)-Fe(III,II)-containing precipitate. At the two lowest As/Fe ratios (0.007 and 0.033), our results indicate the presence of additional As(III) species with a dominant As-Fe distance of 3.30 ± 0.02 Å, for which a possible structural model is proposed. The tridentate ³C As(III)O₃ complexes on the {1 1 1} magnetite surface, together with this additional As(III) species, dramatically lower the solubility of arsenite in the anoxic model systems studied. They may thus play an important role in lowering arsenite solubility in putative magnetite-based water treatment processes, as well as in natural iron-rich anoxic media, especially during the reductive dissolution-precipitation of iron minerals in anoxic environments.