Hydrous ferric oxide precipitation in the presence of nonmetabolizing bacteria: Constraints on the mechanism of a biotic effect

We have used room temperature and cryogenic ⁵⁷Fe Mössbauer spectroscopy, powder X-ray diffraction (pXRD), mineral magnetometry, and transmission electron microscopy (TEM), to study the synthetic precipitation of hydrous ferric oxides (HFOs) prepared either in the absence (abiotic, a-HFO) or presence (biotic, b-HFO) of nonmetabolizing bacterial cells (Bacillus subtilis or Bacillus licheniformis, ∼10⁸ cells/mL) and under otherwise identical chemical conditions, starting from Fe(II) (10⁻², 10⁻³, or 10⁻⁴ mol/L) under open oxic conditions and at different pH (6-9). We have also performed the first Mössbauer spectroscopy measurements of bacterial cell wall (Bacillus subtilis) surface complexed Fe, where Fe(III) (10^−3.5-10^−4.5 mol/L) was added to a fixed concentration of cells (∼10⁸ cells/mL) under open oxic conditions and at various pH (2.5-4.3). We find that non-metabolic bacterial cell wall surface complexation of Fe is not passive in that it affects Fe speciation in at least two ways: (1) it can reduce Fe(III) to sorbed-Fe²⁺ by a proposed steric and charge transfer effect and (2) it stabilizes Fe(II) as sorbed-Fe²⁺ against ambient oxidation. The cell wall sorption of Fe occurs in a manner that is not compatible with incorporation into the HFO structure (different coordination environment and stabilization of the ferrous state) and the cell wall-sorbed Fe is not chemically bonded to the HFO particle when they coexist (the sorbed Fe is not magnetically polarized by the HFO particle in its magnetically ordered state). This invalidates the concept that sorption is the first step in a heterogeneous nucleation of HFO onto bacterial cell walls. Both the a-HFOs and the b-HFOs are predominantly varieties of ferrihydrite (Fh), often containing admixtures of nanophase lepidocrocite (nLp), yet they show significant abiotic/biotic differences: Biotic Fh has less intraparticle (including surface region) atomic order (Mössbauer quadrupole splitting), smaller primary particle size (magnetometry blocking temperature), weaker Fe to particle bond strength (Mössbauer center shift), and no six-line Fh (6L-Fh) admixture (pXRD, magnetometry). Contrary to current belief, we find that 6L-Fh appears to be precipitated directly, under a-HFO conditions, from either Fe(II) or Fe(III), and depending on Fe concentration and pH, whereas the presence of bacteria disables all such 6L-Fh precipitation and produces two-line Fh (2L-Fh)-like biotic coprecipitates. Given the nature of the differences between a-HFO and b-HFO and their synthesis condition dependences, several biotic precipitation mechanisms (template effect, near-cell environment effect, catalyzed nucleation and/or growth effect, and substrate-based coprecipitation) are ruled out. The prevailing present view of a template or heterogeneous nucleation barrier reduction effect, in particular, is shown not to be the cause of the large observed biotic effects on the resulting HFOs. The only proposed mechanism (relevant to Fh) that is consistent with all our observations is coprecipitation with and possible surface poisoning by ancillary bacteriagenic compounds. That bacterial cell wall functional groups are redox active and the characteristics of biotic (i.e., natural) HFOs compared to those of abiotic (i.e., synthetic) HFOs have several possible biogeochemical implications regarding Fe cycling, in the photic zones of water columns in particular.     

The recent fault scarps of the Western Alps (France): Tectonic surface ruptures or gravitational sackung scarps? A combined mapping, geomorphic, levelling, and Be dating approach

In the Western Alps, some recent scarps were previously interpreted as surface ruptures of tectonic reverse and normal faults that agree with microseismicity and GPS measurements. Our analysis shows that in fact there are hundreds of recent scarps, up to 30 m high and 2.1 km long, with only pure normal motions. They share the same characteristics as typical sackung scarps. The scarps are mainly uphill facing, parallel to the ridge crests and the contour lines. They are relatively short (less than 2.1 km) with respect to tectonic fault ruptures, and organized in swarms. They cut screes and relict rock glaciers with a slow (commonly 1 mm/year) average slip rate. In the Aiguilles Grives massif these sackung scarps clearly express the gravitational toppling of sub-vertical bedding planes in hard rocks. In contrast, the Belledonne Outer Crystalline Massif exhibits scarps that stem from the gravitational reactivation of conjugate tectonic faults. The recent faults extend to about 1600 m beneath the Rognier ridge crest, but are always above the valley floor. The main scarp swarm is 9.2 km long and constitutes the largest sackung ever described in the Western Alps. ¹⁰Be dating of a scarp and offset surfaces shows that > 4 m slip may have occurred rapidly (in less than 3800 years) sometimes between the end of the glaciation and 8800 ± 1900 years ago. This dating, together with the location of some faults far from the deep glacial valleys, suggests that sagging might have been triggered by strong earthquakes during a post-glacial period of probably enhanced seismicity. The Belledonne and Synclinal Median faults (just beneath the Rognier sackung) could have been the sources of this seismicity.     

Speciation and role of iron in cloud droplets at the puy de Dôme station

Iron is the most abundant transition metal in the atmosphere and can play a significant role in cloudwater chemistry where its reactivity is closely related to the partitioning between Fe(II) and Fe(III). The objective of this work is to determine the total iron content and the iron speciation in a free tropospheric site, and to understand which factors influence these parameters. We collected 147 samples of cloudwater during 34 cloud events over a period of four years at the puy de Dôme summit. Besides iron we measured other chemical compounds, solar radiation, physico-chemical and meteorological parameters potentially connected with iron reactivity. The total iron concentrations ranged from 0.1 to 9.1 μM with the major frequency occurring at low levels. The pH and presence of organic complexants seem to be the most significant factors connected with total dissolved iron; while the iron oxidation state seems to be an independent factor. Light intensity, presence of complexants or oxidants (H₂O₂) do not influence the Fe(II)/Fe(Total) ratio, that was quite constant at about 0.75. This could be due to the potential redox that forces the Fe(II)-Fe(III) couple to the reduced form or, more probably to the complexation by Natural Organic Matter, that can stabilize iron in its reduced form and prevent further oxidation. Our field measurements did not show the diurnal cycle observed in surface water and predicted by models of atmospheric chemistry. This result prompts a more careful review of the role of iron and, by analogy, all the transition metals in atmospheric liquid phase, often over-estimated in the literature.     

Ptolemaic Transformation in Keplerian Problem

We propose the Ptolemaic transformation: a canonical change of variables reducing the Keplerian motion to the form of a perturbed Hamiltonian problem. As a solution of the unperturbed case, the Ptolemaic variables define an intermediary orbit, accurate up to the first power of eccentricity, like in the kinematic model of Claudius Ptolemy. In order to normalize the perturbed Hamiltonian we modify the recurrent Lie series algorithm of HoriuuMersman. The modified algorithm accounts for the loss of a term's order during the evaluation of a Poisson bracket, and thus can be also applied in resonance problems. The normalized Hamiltonian consists of a single Keplerian term; the mean Ptolemaic variables occur to be trivial, linear functions of the Delaunay actions and angles. The generator of the transformation may serve to expand various functions in Poisson series of eccentricity and mean anomaly.     

Quantifying the Effects of Well Development in Unconsolidated Material

A fully instrumented physical model was designed and built to reproduce development by surging and monitor its effects during surging and after development. The model simulates a horizontal layer in a confined aquifer with control of vertical overburden pressure. An automatic apparatus produced development by surging in successive phases up to 24 hours. Aquifer tests in steady-state conditions were performed between successive phases. The paper reports the main results of three experiments performed with Johnson screens 200 mm in diameter; they had slot sizes between the D₅₄ and D₇₀ of the aquifer soil. This soil was placed under controlled conditions, and initial homogeneity was obtained as confirmed by initial control tests. Pore pressures (and thus hydraulic heads) were continuously monitored during development phases and aquifer tests by 22 electronic piezometers at distances between 0 and 1 m from the screen. These piezometers measured water pressures every 0.1 s when required. Solid particles passing through the screen were recovered to study the solid yield and the gradation of particles. Positive and negative values of local gradients reached values up to 400 close to the screen at the beginning of development and decreased with time of development. These high values produced high seepage forces displacing particles in the aquifer. The well yield was increased by a factor of 6 after development. These model test results confirmed empirical criteria on entrance velocity, internal stability criteria, and field values of "sand" production by development. In addition, they enabled a quantification of skin effects to be considered in interpreting an aquifer test.     

Fundamental processes controlling the first stage of alteration of a basalt glass by seawater: an experimental study between 200° and 320°C

The first stage of alteration of a basalt glass by seawater has been studied experimentally between 200° and 320°C under vapor pressure, following both the chemical evolution of the reacting solutions during the experiments and the chemical and mineralogical transformations of the altered glass surface via microprobe, scanning transmission electron microscope and resonant nuclear reactions.The alteration is controlled by diffusion of dissolved species through an altered layer and not by surface chemical reaction. Selective removal of cations with respect to SiO₂ leads to the formation of a thick, porous protonated surface layer enriched in SiO₂. Aqueous diffusion of dissolved species from the reacting glass and from solution through the pores of this layer results in the formation of an amorphous silicate gel which is the precursor of normal crystalline clays (saponites) appearing in a later stage.Computer simulations of the alteration generated with the EQ3/6 computer software package account for the chemical composition of the rim and the sequence of secondary minerals found in the experiments.     

Keplerian expansions in terms of Henrard's practical variables

Formulae for the Keplerian expansions in terms of Henrard's practical variables are given. Two different methods were applied: one using the Bessel functions and one based on the Lie transforms. The former involves less series products, but the latter is more flexible and universal.     

Hydrological conditions over the western Mediterranean basin during the deposition of the cold Sapropel 6 (ca. 175 kyr BP)

A new oxygen isotope record is reported from a stalagmite collected in the Argentarola Cave located on the Tyrrhenian coast of Italy. As shown from observations and numerical modeling of δ¹⁸O in modern precipitation, the recorded δ¹⁸O variability for this zone is dominated by the amount of precipitation (so-called ‘amount effect’). The δ¹⁸O profile measured in the stalagmite is characterized by a prominent negative excursion (ca. 2-3‰) between 180 and 170 kyr BP. This paleoclimatic feature is interpreted as being due to a relatively wet period which occurred during the penultimate glacial period, more precisely, during Marine Isotope Stage 6.5. This pluvial phase is shown to correspond chronologically to the deposition of the sapropel event 6 (S6). Although this particular sapropel event occurred during a cold phase, the δ¹⁸O excursion is similar to those corresponding to other sapropels (S4, S3 and S2). The evidence for humid conditions during S6 in the western Mediterranean basin agrees with previous studies based on deep-sea sediment cores. Taken collectively, the data suggest that during sapropel events dilution of ocean surface waters was not restricted to the output of the river Nile but was rather widespread over the entire Mediterranean Sea due to increased rainfall.     

Datation Ar/Ar des leucogranites sous couverture du complexe plutonique de Charroux–Civray (Vienne)Ar/Ar dating of leucogranites in the sediment-covered Charroux–Civray complex (Vienne)

⁴⁰Ar/³⁹Ar dating on muscovites, performed on leucogranitic intrusions of Charroux–Civray plutonic complex, points out the existence of two peraluminous magmatic activities, whose equivalents are known in the Limousin: (1) garnet-bearing leucogranitic veins at ca. 340 Ma; (2) a specialised leucogranite associated with W ± Sn deposits at ca 310 Ma. However, available ⁴⁰Ar/³⁹Ar data do not allow us to provide further data concerning the age and the geometry at depth of a large leucogranitic body identified by geophysics. To cite this article: P. Alexandre et al., C. R. Geoscience 334 (2002) 1141–1148.