Synthetic coprecipitates of exopolysaccharides and ferrihydrite. Part I: Characterization

Iron(III) (hydr)oxides formed at extracellular biosurfaces or in the presence of exopolymeric substances of microbes and plants may significantly differ in their structural and physical properties from their inorganic counterparts. We synthesized ferrihydrite (Fh) in solutions containing acid polysaccharides [polygalacturonic acid (PGA), alginate, xanthan] and compared its properties with that of an abiotic reference by means of X-ray diffraction, transmission electron microscopy, gas adsorption (N₂, CO₂), X-ray absorption spectroscopy, ⁵⁷Fe Mössbauer spectroscopy, and electrophoretic mobility measurements. The coprecipitates formed contained up to 37 wt% polymer. Two-line Fh was the dominant mineral phase in all precipitates. The efficacy of polymers to precipitate Fh at neutral pH was higher for polymers with more carboxyl C (PGA ∼ alginate > xanthan). Pure Fh had a specific surface area of 300 m²/g; coprecipitation of Fh with polymers reduced the detectable mineral surface area by up to 87%. Likewise, mineral micro- (<2 nm) and mesoporosity (2-10 nm) decreased by up to 85% with respect to pure Fh, indicative of a strong aggregation of Fh particles by polymers in freeze-dried state. C-1s STXM images showed the embedding of Fh particles in polymer matrices on the micrometer scale. Iron EXAFS spectroscopy revealed no significant changes in the local coordination of Fe(III) between pure Fh and Fh contained in PGA coprecipitates. ⁵⁷Fe Mössbauer spectra of coprecipitates confirmed Fh as dominant mineral phase with a slightly reduced particle size and crystallinity of coprecipitate-Fh compared to pure Fh and/or a limited magnetic super-exchange between Fh particles in the coprecipitates due to magnetic dilution by the polysaccharides. The pH_iep of pure Fh in 0.01 M NaClO₄ was 7.1. In contrast, coprecipitates of PGA and alginate had a pH_iep < 2. Considering the differences in specific surface area, porosity, and net charge between the coprecipitates and pure Fh, composites of exopolysaccharides and Fe(III) (hydr)oxides are expected to differ in their geochemical reactivity from pure Fe(III) (hydr)oxides, even if the minerals have a similar crystallinity.     

Meteoritic material at five large impact craters

Sixteen crater samples were analyzed by radiochemical neutron activation analysis for Ge, Ir, Ni, Os, Pd and Re. Two impact melt rock samples from Clearwater East (22 km) showed strong, uniform enrichments in all elements except Ge, corresponding to 7.4% C1 chondrite material. Interelement ratios suggest that the meteorite was a C1 (or C2) chondrite, not an iron, stony iron, or chondrite of another type. An Ivory Coast tektite (related to the 10 km Bosumtwi crater) was enriched in Ir + Os and Ni to about 0.04 and 1.6% of C1 chondrite levels, but in the absence of data on country rocks, the meteorite cannot yet be characterized.Impact melt rock samples from Clearwater West (32km), Manicouagan (70km), and Mistastin (28 km) showed no detectable meteoritic component. Upper limits, as Cl chondrite equivalent, were Os ≤ 2 × 10^?3% (~0.01 ppb), Ni ≤ 2 × 10^?1% (~20ppm). Possible causes are high impact velocity and/or a chemically inconspicuous meteorite (achondrite, Ir,Os-poor iron or stony iron). However, a more likely reason is that some fraction of the impact melt remains meteorite-free, especially at craters with central peaks.Clearwater East is the first terrestrial impact crater found to be associated with a stony meteorite. Apparently the consistent absence of stony projectiles at small craters (< 1 km diameter) reflects their destruction in the atmosphere, as proposed by Öpik.     

CaAl ratio and composition of the Earth's upper mantle

Undifferentiated meteorites (chondrites) have the same relative abundances of refractory lithophile elements (Ca, Al, Ti, Sc, REE, etc.), despite variable absolute concentrations. The reasonable assumption of chondritic ratios among refractory elements in the bulk Earth is used to constrain the chemical composition of the upper mantle in the following way: Correlations of the compatible refractory elements Ca, Al, Ti, Sc and Yb with MgO are worldwide very similar in suites of spinel-lherzolite xenoliths from basaltic rocks. Such suites represent upper mantle material depleted to differing degrees by extraction of partial melts. From these refractory elements vs. MgO correlations, ratios of pairs of refractory elements were calculated at various MgO contents. Chondritic $\text{Al}\text{Ti}$ and $\text{Sc}\text{Ti}$ ratios were only obtained for MgO contents below 36%. A chrondritic $\text{Sc}\text{Yb}$ ratio requires an MgO content above 35%. We therefore accept 35.5% as the most reasonable MgO content of undepleted upper mantle. This MgO content is slightly below the spinel-lherzolite with the lowest measured MgO content (36.22%). The corresponding Al₂O₃ content of 4.75% is higher than in previous estimates of upper mantle composition. The concentrations of other elements were obtained from similar correlations at a MgO content of 35.5%. The resulting present upper mantle composition is enriched in refractory elements by a factor of 1.49 relative to Si and Cl and by a factor of 1.12 for Mg relative to Si and Cl. These enrichments are in the same range as those for the Vigarano type carbonaceous chondrites. The Mg/Mg + Fe ratio of 89 is slightly lower than previous estimates.The $\text{Ca}\text{Al}$ ratio in spinel lherzolite suites is, however, uniformly higher worldwide than the chondritic ratio by about 15%. Orogenic peridotites as well as komatiites appear to have similar non-chondritic $\text{Ca}\text{Al}$ ratios. It is therefore suggested that this non-chondritic $\text{Ca}\text{Al}$ ratio is a characteristic of the upper mantle, possibly since the Archean. A minor fractionation of about 4% of garnet in an early, global melting event (deep magma ocean?) is presented as the most likely cause for the high $\text{Ca}\text{Al}\text{-}\text{ratio}$. In this case the addition of 4% of such a garnet component to the undepleted present upper mantle would be required to obtain the composition of the primordial upper mantle. The $\text{Ca}\text{Al}\text{-}\text{ratio}$ of this primordial mantle would be 15% higher than that of the undepleted present upper mantle, resulting in an enrichment of refractory elements of 1.70 ($\text{Al}\text{Si}$ relative to Cl) for the primordial upper mantle.     

Heterogeneous accretion,composition and core–mantle differentiation of the Earth

A model of core formation is presented that involves the Earth accreting heterogeneously through a series of impacts with smaller differentiated bodies. Each collision results in the impactor's metallic core reacting with a magma ocean before merging with the Earth's proto-core. The bulk compositions of accreting planetesimals are represented by average solar system abundances of non-volatile elements (i.e. CI-chondritic), with 22% enhancement of refractory elements and oxygen contents that are defined mainly by the Fe metal/FeO silicate ratio. Based on an anhydrous bulk chemistry, the compositions of coexisting core-forming metallic liquid and peridotitic silicate liquid are calculated by mass balance using experimentally-determined metal/silicate partition coefficients for the elements Fe, Si, O, Ni, Co, W, Nb, V, Ta and Cr. Oxygen fugacity is fixed by the partitioning of Fe between metal and silicate and depends on temperature, pressure and the oxygen content of the starting composition. Model parameters are determined by fitting the calculated mantle composition to the primitive mantle composition using least squares minimization. Models that involve homogeneous accretion or single-stage core formation do not provide acceptable fits. In the most successful models, involving 24 impacting bodies, the initial 60–70% (by mass) of the Earth accretes from highly-reduced material with the final 30–40% of accreted mass being more oxidised, which is consistent with results of dynamical accretion simulations. In order to obtain satisfactory fits for Ni, Co and W, it is required that the larger (and later) impactor cores fail to equilibrate completely before merging with the Earth's proto-core, as proposed previously on the basis of Hf-W isotopic studies. Estimated equilibration conditions may be consistent with magma oceans extending to the core–mantle boundary, thus making core formation extremely efficient. The model enables the compositional evolution of the Earth's mantle and core to be predicted throughout the course of accretion. The results are consistent with the late accretion of the Earth's water inventory, possibly with a late veneer after core formation was complete. Finally, the core is predicted to contain ~ 5 wt.% Ni, ~ 8 wt.% Si, ~ 2 wt.% S and ~ 0.5 wt.% O.     

Experimental determination of Ni diffusion coefficients in olivine and their dependence on temperature, composition, oxygen fugacity, and crystallographic orientation

Diffusion couple experiments were carried out with San Carlos olivine (Fo₉₀) and NiFe alloys (Ni₁₀₀, Ni₉₇Fe₃, Ni₉₀Fe₁₀) or other olivine compositions (Fo₁₀₀, Fo₂₅) in order to determine the dependence on temperature, oxygen fugacity, composition and crystallographic orientation of Ni diffusion coefficient (D_Ni) in olivine. Experiments at 1 atmosphere total pressure cover a temperature range of 900-1445°C with run durations from 48 to 2155 h at different oxygen fugacities. In an Arrhenius plot the best fit for all data for Fo₉₀ yields an activation energy (E_D) of 220 ± 14 kJ/mol and an fO₂ dependence of (1/4.25)·Δ log fO₂ = Δ log D_Ni. The relationship between diffusion coefficients along different crystallographic axes at 1200°C is given by D_[001] ≈ 6·D_[100] ≈ 6·D_[010]. D_Ni depends strongly on the major element (i.e. Fe/Mg) composition of olivine and decreases by about 1 order of magnitude as the olivine composition changes from Fo₃₅ to Fo₉₀. Thus, experimental investigations in Fe-free systems cannot be applied to natural samples. For calculation of residence times or cooling rates the present Ni data yield shorter timescales compared to those obtained using diffusion data published until now.In addition to Ni diffusion coefficients, Fe-Mg, Mn and Ca diffusion data were obtained from some of the same diffusion couples (Fo₉₀-Fo₁₀₀). It is found that the activation energies, E_D[Ni] ≅ E_D[Fe-Mg] ≅ E_D[Mn] ≤ E_D[Ca]. All diffusion coefficients are strongly dependent on the major element composition of olivine.     

Camel Donga: A Eucrite with High Metal Content

Abstract— The Camel Donga eucrite is unique since it contains about 2% metallic iron. Chemical composition, mineralogy, and noble gas contents of Camel Donga are, however, indistinguishable from other eucrites. The bulk iron content and the composition of the metal show that the Camel Donga metal was formed by reduction of FeO and FeS, probably through loss of S₂ and SO₂. Since coarse- and fine-grained lithologies are affected it is likely that the reduction occurred after brecciation. The inhomogeneous distribution of metal suggests that reduction is limited to areas where sulfides were present. The fact that major parts of the meteorite still contain sulfides, in many cases associated with metal, indicates that the reduction process did not go to completion. A comparatively short heating period is suggested, perhaps in an ejecta blanket.     

Constant denudation rates in a high alpine catchment for the last 6 kyrs

Terrestrial cosmogenic nuclides (TCN) have widely been used as proxies in determining denudation rates in catchments. Most studies were limited to samples from modern active streams, thus little is known about the magnitude and causes of TCN variability on millennial time scales. In this work we present a 6 kyrs long, high resolution record of ¹⁰Be concentrations (n = 18), which were measured in sediment cores from an alluvial fan delta at the outlet of the Fedoz Valley in the Swiss Alps. This record is paired with a 3‐year time series (n = 4) of ¹⁰Be measured in sediment from the active stream currently feeding this fan delta. The temporal trend in the ¹⁰Be concentrations after correction for postdepositional production of ¹⁰Be was found to be overall constant and in good agreement with the modern river ¹⁰Be concentration. The calculated mean catchment‐wide denudation rate amounts to 0.73 ± 0.18 mm yr^?1. This fairly constant level of ¹⁰Be concentrations can be caused by a constant denudation rate over time within the catchment or alternatively by a buffered signal. In this contribution we suggest that the large alluvial floodplain in the Fedoz Valley may act as an efficient buffer on Holocene time scales in which sediments with different ¹⁰Be signatures are mixed. Therefore, presumable variations in the ¹⁰Be signals derived from changes in denudation under a fluctuating Holocene climate are only poorly transferred to the catchment outlet and not recorded in the ¹⁰Be record. However, despite the absence of high frequency signals, we propose that the buffered and averaged ¹⁰Be signal could be meaningfully and faithfully interpreted in terms of long‐term catchment‐averaged denudation rate. Our study suggests that alluvial buffers play an important role in regulating the ¹⁰Be signal exported by some alpine settings that needs to be taken into account and further investigated. Copyright © 2016 John Wiley & Sons, Ltd.     

THE CHEMISTRY OF HAVERÖ UREILITE

The concentrations of 41 major, minor and trace elements were determined in Haverö ureilite. In addition to the analysis on bulk samples a number of separates were measured, too, including hand-picked samples of the dark carbonaceous, diamond-rich inclusions and two metal fractions. It was found that one metal fraction had an extraordinarily high Ir/Au-ratio of 19. According to the concentrations of the noble metals and of nickel, gallium, tungsten and rhenium this metal represents, most probably, the siderophile portion of a high temperature condensate, i.e., the pattern of these elements is very similar to that found in Allende inclusions (Wänke et al., 1972)     

Soil formation and weathering in a permafrost environment of the Swiss Alps: a multi‐parameter and non‐steady‐state approach

Spatially discontinuous permafrost conditions frequently occur in the European Alps. How soils under such conditions have evolved and how they may react to climate warming is largely unknown. This study focuses on the comparison of nearby soils that are characterised by the presence or absence of permafrost (active‐layer thickness: 2–3 m) in the alpine (tundra) and subalpine (forest) range of the Eastern Swiss Alps using a multi‐method (geochemical and mineralogical) approach. Moreover, a new non‐steady‐state concept was applied to determine rates of chemical weathering, soil erosion, soil formation, soil denudation, and soil production. Long‐term chemical weathering rates, soil formation and erosion rates were assessed by using immobile elements, fine‐earth stocks and meteoric ¹⁰Be. In addition, the weathering index (K + Ca)/Ti, the amount of Fe‐ and Al‐oxyhydroxides and clay minerals characteristics were considered. All methods indicated that the differences between permafrost‐affected and non‐permafrost‐affected soils were small. Furthermore, the soils did not uniformly differ in their weathering behaviour. A tendency towards less intense weathering in soils that were affected by permafrost was noted: at most sites, weathering rates, the proportion of oxyhydroxides and the weathering stage of clay minerals were lower in permafrost soils. In part, erosion rates were higher at the permafrost sites and accounted for 79–97% of the denudation rates. In general, soil formation rates (8.8–86.7 t/km²/yr) were in the expected range for Alpine soils. Independent of permafrost conditions, it seems that the local microenvironment (particularly vegetation and subsequently soil organic matter) has strongly influenced denudation rates. As the climate has varied since the beginning of soil evolution, the conditions for soil formation and weathering were not stable over time. Soil evolution in high Alpine settings is complex owing to, among others, spatio‐temporal variations of permafrost conditions and thus climate. This makes predictions of future behaviour very difficult. Copyright © 2016 John Wiley & Sons, Ltd.