Changes in Zn speciation during soil formation from Zn-rich limestones

In order to better understand the long-term speciation and fractionation of Zn in soils, we investigated three soils naturally enriched in Zn (237–864 mg/kg Zn) from the weathering of Zn-rich limestones (40–207 mg/kg Zn) using extended X-ray absorption fine structure (EXAFS) spectroscopy and sequential extractions. The analysis of bulk EXAFS spectra by linear combination fitting (LCF) indicated that Zn in the oolitic limestones was mainly present as Zn-containing calcite (at site Dornach), Zn-containing goethite (Gurnigel) and Zn-containing goethite and sphalerite (Liestal). Correspondingly, extraction of the powdered rocks with 1 M NH₄-acetate at pH 6.0 mobilized only minor fractions of Zn from the Gurnigel and Liestal limestones (<30%), but most Zn from the Dornach rock (81%). In the Dornach soil, part of the Zn released from the dissolving limestone was subsequently incorporated into pedogenic hydroxy-interlayered vermiculite (Zn-HIV, 30%) and Zn-containing kaolinite (30%) and adsorbed or complexed by soil organic and inorganic components (40%). The Gurnigel and Liestal soils contained substantial amounts of Zn-containing goethite (50%) stemming from the parent rock, smaller amounts (20%) of Zn-containing kaolinite (and possibly Zn-HIV), as well as adsorbed or complexed Zn-species (30%). In the soil from Liestal, sphalerite was only found in trace amounts, indicating its dissolution during soil formation. In sequential extractions, large percentages of Zn (55–85%) were extracted in recalcitrant extraction steps, confirming that Zn-HIV, Zn-containing kaolinite and Zn-containing goethite are highly resistant to weathering. These Zn-bearing phases thus represent long-term hosts for Zn in soils over thousands of years. The capability of these phases to immobilize Zn in heavily contaminated soils may however be limited by their uptake capacity (especially HIV and kaolinite) or their abundance in soil.     

Multi-metal contaminant dynamics in temporarily flooded soil under sulfate limitation

In many river basins, floodplain soils have accumulated a variety of metal contaminants, which might be released during periods of flooding. We investigated the dynamics of copper, cadmium, lead, zinc, and nickel in a contaminated freshwater floodplain soil under a realistic sulfate-limited flooding regime in microcosm experiments. We found that most contaminants were initially mobilized by processes driven by the reductive dissolution of Fe(III) and Mn(IV, III) (hydr)oxides. Subsequently, bacterial sulfate respiration resulted in the transformation of the entire available sulfate (2.3 mmol/kg) into chromous reducible sulfur (CRS). Cu K-edge X-ray absorption fine structure (XAFS) spectroscopy revealed that the soil Cu speciation changed from predominantly Cu(II) bound to soil organic matter (SOM) intermittently to 14% metallic Cu(0) and subsequently to 66% copper sulfide (Cu_xS). These Cu_xS precipitates accounted for most of the formed CRS, suggesting that Cu_xS was the dominant sulfide phase formed in the flooded soil. Sequential metal extractions, in agreement with CRS results, suggested that easily mobilizable Cd was completely and Pb partially sequestered in sulfide precipitates, controlling their dissolved concentrations to below detection limits. In contrast, Zn and Ni (as well as Fe) were hardly sequestered into sulfide phases, so that micromolar levels of dissolved Zn and Ni (and millimolar dissolved Fe(II)) persisted in the reduced soil. The finding that Cu, Cd, and Pb were sequestered (but hardly any Zn, Ni, and Fe) is consistent with the thermodynamically predicted sulfide ladder following the increasing solubility products of the respective metal sulfides. The observation that Cd and Pb were sequestered in sulfides despite the presence of remaining SOM-bound Cu(II) suggested that the kinetics of Cu(II) desorption, diffusion, and/or Cu_xS precipitation interfered with the sulfide ladder. We conclude that the dynamics of multiple metal contaminants are intimately coupled under sulfate limitation by the relative thermodynamic stabilities and formation kinetics of the respective metal sulfides.     

Morphological evolution of dissolving feldspar particles with anisotropic surface kinetics and implications for dissolution rate normalization and grain size dependence: A kinetic modeling study

With previous two-dimensional (2D) simulations based on surface-specific feldspar dissolution succeeding in relating the macroscopic feldspar kinetics to the molecular-scale surface reactions of Si and Al atoms ( [Zhang and Lüttge, 2008] and [Zhang and Lüttge, 2009]), we extended our modeling effort to three-dimensional (3D) feldspar particle dissolution simulations. Bearing on the same theoretical basis, the 3D feldspar particle dissolution simulations have verified the anisotropic surface kinetics observed in the 2D surface-specific simulations. The combined effect of saturation state, pH, and temperature on the surface kinetics anisotropy has been subsequently evaluated, found offering diverse options for morphological evolution of dissolving feldspar nanoparticles with varying grain sizes and starting shapes. Among the three primary faces on the simulated feldspar surface, the (1 0 0) face has the biggest dissolution rate across an extensively wide saturation state range and thus acquires a higher percentage of the surface area upon dissolution. The slowest dissolution occurs to either (0 0 1) or (0 1 0) faces depending on the bond energies of Si-(O)-Si (Φ_Si-O-Si/kT) and Al-(O)-Si (Φ_Al-O-Si/kT). When the ratio of Φ_Si-O-Si/kT to Φ_Al-O-Si/kT changes from 6:3 to 7:5, the dissolution rates of three primary faces change from the trend of (1 0 0) > (0 1 0) > (0 0 1) to the trend of (1 0 0) > (0 0 1) > (0 1 0). The rate difference between faces becomes more distinct and accordingly edge rounding becomes more significant. Feldspar nanoparticles also experience an increasing degree of edge rounding from far-from-equilibrium to close-to-equilibrium. Furthermore, we assessed the connection between the continuous morphological modification and the variation in the bulk dissolution rate during the dissolution of a single feldspar particle. Different normalization treatments equivalent to the commonly used mass, cube assumption, sphere assumption, geometric surface area, and reactive surface area normalizations have been used to normalize the bulk dissolution rate. For each of the treatments, time consistence and grain size dependence of the normalized dissolution rate have been evaluated and the results revealed significant dependences on the magnitude of surface kinetic anisotropy under differing environmental conditions. In general, the normalized dissolution rates are strongly dependent on grain size. Time-consistent normalization treatment varies with the investigated condition. The modeling results suggest that the sphere-, cube-, and BET-normalized dissolution rates are appropriate under the far-from-equilibrium conditions at low pH where these normalizations are time-consistent and are slightly dependent on grain size.     

The structure of monomeric and dimeric uranyl adsorption complexes on gibbsite: A combined DFT and EXAFS study

We investigated the structure of uranyl sorption complexes on gibbsite (pH 5.6-9.7) by two independent methods, density functional theory (DFT) calculations and extended X-ray absorption fine structure (EXAFS) spectroscopy at the U-L_III edge. To model the gibbsite surface with DFT, we tested two Al (hydr)oxide clusters, a dimer and a hexamer. Based on polarization, structure, and relaxation energies during geometry optimization, the hexamer cluster was found to be the more appropriate model. An additional advantage of the hexamer model is that it represents both edges and basal faces of gibbsite. The DFT calculations of (monomeric) uranyl sorption complexes show an energetic preference for the corner-sharing versus the edge-sharing configuration on gibbsite edges. The energy difference is so small, however, that possibly both surface species may coexist. In contrast to the edge sites, sorption to basal sites was energetically not favorable. EXAFS spectroscopy revealed in all investigated samples the same interatomic distances of the uranyl coordination environment (R_U-Oax ≈ 1.80 Å, R_U-Oeq ≈ 2.40 Å), and towards the gibbsite surface (R_U-O ≈ 2.87 Å, R_U-Al ≈ 3.38 Å). In addition, two U-U distances were observed, 3.92 Å at pH 9.7 and 4.30 Å at pH 5.6, both with coordination numbers of ∼1. The short U-U distance is close to that of the aqueous uranyl hydroxo dimer, UO₂(OH)₂, reported as 3.875 Å in the literature, but significantly longer than that of aqueous trimers (3.81-3.82 Å), suggesting sorption of uranyl dimers at alkaline pH. The longer U-U distance (4.30 Å) at acidic pH, however, is not in line with known aqueous uranyl polymer complexes. Based on the EXAFS findings we further refined dimeric surface complexes with DFT. We propose two structural models: in the acidic region, the observed long U-U distance can be explained with a distortion of the uranyl dimer to form both a corner-sharing and an edge-sharing linkage to neighboring Al octahedra, leading to R_U-U = 4.150 Å. In the alkaline region, a corner-sharing uranyl dimer complex is the most favorable. The U-O path at ∼2.87 Å in the EXAFS spectra arises from the oxygen atom linking two Al cations in corner-sharing arrangement. The adsorption structures obtained by DFT calculations are in good agreement with the structural parameters from EXAFS analysis: U-Al (3.394 Å), U-U (3.949 Å), and U-O (2.823 Å) for the alkaline pH model, and U-Al (3.279 Å), U-U (4.150 Å), and U-O (2.743 Å) for the acidic pH model. This work shows that by combining EXAFS and DFT, consistent structural models for uranyl sorption complexes can be obtained, which are relevant to predict the migration behavior of uranium at nuclear facilities.     

Rapid and cyclic aeolian deposition during the Last Glacial in European loess: a high-resolution record from Nussloch, Germany

This paper reports the results of an investigation of the Weichselian Upper Pleniglacial loess sequences of Nussloch (Rhine Valley, Germany) based on stratigraphy, palaeopedology, sedimentology, palynology, malacology and geochemistry (δ¹³C), supported by radiocarbon, TL and OSL dating. Grain-size and magnetic susceptibility records are taken at 5 cm intervals from the Upper Pleniglacial (UPG) loess. The data indicate cyclic variations in loess deposition between ca 34 and 17 ka, when the sedimentation rate is especially high (1.0–1.2 m per ka for more than 10 m). The grain-size index (GSI: ratio of coarse silt versus fine silt and clay) shows variations, which are assumed to be an indirect measurement of wind intensity. The sedimentation rate, interpreted from the profiles, indicates high values in loess (Loess events LE-1 to LE-7) and low or negligible values in tundra gley horizons G1 to G8. OSL ages from the loess and ¹⁴C dates from organic matter in the loess show that loess deposition was rapid but was interrupted by shorter periods of reduced aeolian sedimentation. Comparison between the data from Nussloch and other European sequences demonstrates a progressive coarsening of the loess deposits between ca 30 and 22 ka. This coarsening trend ends with a short but major grain-size decrease and is followed by an increase to a new maximum at 20 ± 2 ka (“W” shape). Correlation between the loess GSI and the Greenland ice-core dust records, suggests a global connection between North Atlantic and Western European global atmospheric circulation and wind regimes. In addition, the typical Upper Pleniglacial loess deposition begins at ca 30–31 ka, close to Heinrich event (HE) 3, and the main period of loess sedimentation at about 25 ± 2 ka is coeval to HE 2. Correlation of magnetic susceptibility and grain-size records shows that the periods, characterised by high GSI, coincide with an increase in the amount of ferromagnetic minerals reworked from the Rhine alluvial plain. They suggest enhancement in the frequency of the storms from N–NW. These results are integrated within a palaeogeographical model of dust transport and deposition in Western Europe for the Weichselian Upper Pleniglacial (or Late Pleniglacial).     

Photometric,spectral phase and temperature effects on 4 Vesta and HED meteorites: Implications for the Dawn mission

Phase angle and temperature are two important parameters that affect the photometric and spectral behavior of planetary surfaces in telescopic and spacecraft data. We have derived photometric and spectral phase functions for the Asteroid 4 Vesta, the first target of the Dawn mission, using ground-based telescopes operating at visible and near-infrared wavelengths (0.4–2.5 μm). Photometric lightcurve observations of Vesta were conducted on 15 nights at a phase angle range of 3.8–25.7° using duplicates of the seven narrowband Dawn Framing Camera filters (0.4–1.0 μm). Rotationally resolved visible (0.4–0.7 μm) and near-IR spectral observations (0.7–2.5 μm) were obtained on four nights over a similar phase angle range. Our Vesta photometric observations suggest the phase slope is between 0.019 and 0.029 mag/deg. The G parameter ranges from 0.22 to 0.37 consistent with previous results (e.g., Lagerkvist, C.-I., Magnusson, P., Williams, I.P., Buontempo, M.E., Argyle, R.W., Morrison, L.V. [1992]. Astron. Astrophys. Suppl. Ser. 94, 43–71; Piironen, J., Magnusson, P., Lagerkvist, C.-I., Williams, I.P., Buontempo, M.E., Morrison, L.V. [1997]. Astron. Astrophys. Suppl. Ser. 121, 489–497; Hasegawa, S. et al. [2009]. Lunar Planet. Sci. 40. ID 1503) within the uncertainty. We found that in the phase angle range of 0° < α ? 25° for every 10° increase in phase angle Vesta’s visible slope (0.5–0.7 μm) increases 20%, Band I and Band II depths increase 2.35% and 1.5% respectively, and the BAR value increase 0.30. Phase angle spectral measurements of the eucrite Moama in the lab show a decrease in Band I and Band II depths and BAR from the lowest phase angle 13° to 30°, followed by possible small increases up to 90°, and then a dramatic drop between 90° and 120° phase angle. Temperature-induced spectral effects shift the Band I and II centers of the pyroxene bands to longer wavelengths with increasing temperature. We have derived new correction equations using a temperature series (80–400 K) of HED meteorite spectra that will enable interpretation of telescopic and spacecraft spectral data using laboratory calibrations at room temperature (300 K).     

GETEMME—a mission to explore the Martian satellites and the fundamentals of solar system physics

GETEMME (Gravity, Einstein??s Theory, and Exploration of the Martian Moons?? Environment), a mission which is being proposed in ESA??s Cosmic Vision program, shall be launched for Mars on a Soyuz Fregat in 2020. The spacecraft will initially rendezvous with Phobos and Deimos in order to carry out a comprehensive mapping and characterization of the two satellites and to deploy passive Laser retro-reflectors on their surfaces. In the second stage of the mission, the spacecraft will be transferred into a lower 1500-km Mars orbit, to carry out routine Laser range measurements to the reflectors on Phobos and Deimos. Also, asynchronous two-way Laser ranging measurements between the spacecraft and stations of the ILRS (International Laser Ranging Service) on Earth are foreseen. An onboard accelerometer will ensure a high accuracy for the spacecraft orbit determination. The inversion of all range and accelerometer data will allow us to determine or improve dramatically on a host of dynamic parameters of the Martian satellite system. From the complex motion and rotation of Phobos and Deimos we will obtain clues on internal structures and the origins of the satellites. Also, crucial data on the time-varying gravity field of Mars related to climate variation and internal structure will be obtained. Ranging measurements will also be essential to improve on several parameters in fundamental physics, such as the Post-Newtonian parameter ?? as well as time-rate changes of the gravitational constant and the Lense-Thirring effect. Measurements by GETEMME will firmly embed Mars and its satellites into the Solar System reference frame.     

Uncertainties in climate change prediction: El Niño-Southern Oscillation and monsoons

The sensitivity of climate phenomena in the low latitudes to enhanced greenhouse conditions is a scientific issue of high relevance to billions of people in the poorest countries of the globe. So far, most studies dealt with individual model results. In the present analysis, we refer to 79 coupled ocean–atmosphere simulations from 12 different climate models under 6 different IPCC scenarios. The basic question is as to what extent various state-of-the-art climate models agree in predicting changes in the main features of El Niño-Southern Oscillation (ENSO) and the monsoon climates in South Asia and West Africa. The individual model runs are compared with observational data in order to judge whether the spatio-temporal characteristics of ENSO are well reproduced. The model experiments can be grouped into multi-model ensembles. Thus, climate change signals in the classical index time series, in the principal components and in the time series of interannual variability can be evaluated against the background of internal variability and model uncertainty.There are large differences between the individual model predictions until the end of the 21st century, especially in terms of monsoon rainfall and the Southern Oscillation index (SOI). The majority of the models tends to project La Niña-like anomalies in the SOI and an intensification of the summer monsoon precipitation in India and West Africa. However, the response barely exceeds the level of natural variability and the systematic intermodel variations are larger than the impact of different IPCC scenarios. Nonetheless, there is one prominent climate change signal, which stands out from model variations and internal noise: All forced model experiments agree in predicting a substantial warming in the eastern tropical Pacific. This oceanic heating does not necessarily lead to a modification of ENSO towards more frequent El Niño and/or La Niña events. It simply represents a change in the background state of ENSO. Indeed, we did not find convincing multi-model evidence for a modification of the wavelet spectra in terms of ENSO or the monsoons. Some models suggest an intensification of the annual cycle but this signal is fairly model-dependent. Thus, large model uncertainty still exists with respect to the future behaviour of climate in the low latitudes. This has to be taken into account when addressing climate change signals in individual model experiments and ensembles.     

Description and recognition of potassic-richterite,an amphibole supergroup mineral from the Pajsberg ore field,Värmland,Sweden

Mineralogy and Petrology - Potassic-richterite, ideally AKB(NaCa)CMg5TSi8O22W(OH)2, is recognized as a valid member of the amphibole supergroup (IMA-CNMNC 2017–102). Type material is from the...     

Thermal evolution of an ancient subduction interface revealed by Lue Hf garnet geochronology,Halilba■? Complex(Anatolia)

The thermal structure of subduction zones exerts a major influence on deep-seated mechanical and chemical processes controlling arc magmatism, seismicity, and global element cycles. Accretionary complexes exposed inland may comprise tectonic blocks with contrasting pressureetemperature(Pe T)histories, making it possible to investigate the dynamics and thermal evolution of former subduction interfaces. With this aim, we present new Lue Hf geochronological results for mafic rocks of the Halilbag?Complex(Anatolia) that evolved along different thermal gradients. Samples include a lawsoniteeepidote blueschist, a lawsoniteeepidote eclogite, and an epidote eclogite(all with counter-clockwise Pe T paths),a prograde lawsonite blueschist with a "hairpin"-type Pe T path, and a garnet amphibolite from the overlying sub-ophiolitic metamorphic sole. Equilibrium phase diagrams suggest that the garnet amphibolite formed at w0.6 -0.7 GPa and 800 -850℃, whereas the prograde lawsonite blueschist records burial from 2.1 GPa and 420℃ to 2.6 GPa and 520℃. Well-defined Lue Hf isochrons were obtained for the epidote eclogite(92.38 ± 0.22 Ma) and the lawsoniteeepidote blueschist(90.19 ± 0.54 Ma),suggesting rapid garnet growth. The lawsoniteeepidote eclogite(87.30 ± 0.39 Ma) and the prograde lawsonite blueschist(ca. 86 Ma) are younger, whereas the garnet amphibolite(104.5 ± 3.5 Ma) is older.Our data reveal a consistent trend of progressively decreasing geothermal gradient from granulite-facies conditions at ~104 Ma to the epidote-eclogite facies around 92 Ma, and the lawsonite blueschist-facies between 90 Ma and 86 Ma. Three Lue Hf garnet dates(between 92 Ma and 87 Ma) weighted toward the growth of post-peak rims(as indicated by Lu distribution in garnet) suggest that the HP/LT rocks were exhumed continuously and not episodically. We infer that HP/LT metamorphic rocks within the Halilbag?Complex were subjected to continuous return flow, with "warm" rocks being exhumed during the tectonic burial of "cold" ones. Our results, combined with regional geological constraints, allow us to speculate that subduction started at a transform fault near a mid-oceanic spreading centre. Following its formation, this ancient subduction interface evolved thermally over more than 15 Myr, most likely as a result of heat dissipation rather than crustal underplating.