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

Tatsuya Hattori  Takumi Saito  Andreas C. Scheinost  Shinya Nagasaki 《Geochimica et cosmochimica acta》2009,73(20):5975-1439

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.  相似文献   

Rapid and cyclic aeolian deposition during the Last Glacial in European loess: a high-resolution record from Nussloch, Germany   总被引：1，自引：0，他引：1  

Pierre Antoine  Denis-Didier Rousseau  Olivier Moine  Stphane Kunesch  Christine Hatt  Andreas Lang  Hlne Tissoux  Ludwig Zller 《Quaternary Science Reviews》2009,28(25-26):2955-2973

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).  相似文献   

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

Vishnu Reddy  Juan A. Sanchez  Andreas Nathues  Nicholas A. Moskovitz  Jian-Yang Li  Edward A. Cloutis  Ken Archer  Roy A. Tucker  Michael J. Gaffey  J. Paul Mann  Holger Sierks  Ulrich Schade 《Icarus》2012,217(1):153-168

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).  相似文献   

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

Jürgen Oberst  Valéry Lainey  Christophe Le Poncin-Lafitte  Veronique Dehant  Pascal Rosenblatt  Stephan Ulamec  Jens Biele  J?rn Spurmann  Ralph Kahle  Volker Klein  Ulrich Schreiber  Anja Schlicht  Nicolas Rambaux  Philippe Laurent  Beno?t Noyelles  Bernard Foulon  Alexander Zakharov  Leonid Gurvits  Denis Uchaev  Scott Murchie  Cheryl Reed  Slava G. Turyshev  Jesus Gil  Mariella Graziano  Konrad Willner  Kai Wickhusen  Andreas Pasewaldt  Marita W?hlisch  Harald Hoffmann 《Experimental Astronomy》2012,34(2):243-271

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.  相似文献   

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

Heiko Paeth  Anja Scholten  Petra Friederichs  Andreas Hense 《Global and Planetary Change》2008,60(3-4):265-288

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.  相似文献   

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

Holtstam  Dan  Cámara  Fernando  Skogby  Henrik  Karlsson  Andreas  Langhof  Jörgen 《Mineralogy and Petrology》2019,113(1):7-16

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...  相似文献   

Geochemical evidence of aeolian deposits in European soils     

Andreas J. Scheib  Manfred Birke  Enrico Dinelli  GEMAS Project Team 《Boreas: An International Journal of Quaternary Research》2014,43(1):175-192

Hafnium (Hf) and zirconium (Zr) concentrations measured in over 4100 agricultural soil samples from Europe were assessed with the focus on their relationship to the distribution of aeolian deposits, such as loess and coversands. Comparison of extractable (aqua regia; ICP‐MS) and total (XRFS) concentrations shows that only 1.0 to 1.7% of the total Hf and Zr is chemically extractable because of the resistant nature of their host minerals. Resistate minerals, such as zircon, are commonly found in the predominantly silty fraction of loess deposits. In this study a statistical analysis of total Hf and Zr soil data from areas with and without loess was carried out to derive threshold values of 10 mg kg^?1 (Hf) and 318 mg kg^?1 (Zr). These values were subsequently applied across the project area in an attempt to indicate the presence of aeolian deposits. The spatial distribution of above‐threshold concentrations suggests a more extensive and coherent loess belt across central and eastern Europe, providing additional evidence of loess across Brittany, Aquitaine and near the Vosges mountains in France as well as in the basins of central and northern Spain. Above‐threshold concentrations were also detected in loess regardless of its thickness, emphasising the importance of the abundance of zircon in the upper part of the soil profile rather than the actual thickness of the deposit. Soil data however, failed to indicate various loess facies within most of the Pannonian Basin, suggesting that this approach only works where deposits contain a sufficient amount of zircon. This may also explain why the extensive coversands across northern Germany and Poland were largely undetected. This study demonstrates that continental‐scale soil geochemical data can help identify and map the distribution of zircon‐rich loess and coversand, and subsequently enhance and improve current knowledge of the extent of these deposits.  相似文献   

Climatology of Ozone, PAN, CO, and NMHC in the Free Troposphere Over the Southern North Atlantic   总被引：1，自引：0，他引：1  

Rainer Schmitt  Andreas Volz-Thomas 《Journal of Atmospheric Chemistry》1997,28(1-3):245-262

Free tropospheric measurements of ozone, peroxyacetylnitrate andprecursors (CO, NMHC) that were made within the framework of the EUROTRACsub-project TOR (Tropospheric Ozone Research) between 1990 and 1995 at theGAW station Izana, Tenerife (28°18N, 16°30W) arediscussed. The average annual cycles reveal the importance of transport fromnorthern mid-latitudes and the role of photo-chemistry. According toair-mass trajectories, which were supplied to us from AEROCE(Atmosphere/Ocean Chemistry Experiment), transport from northernmid-latitudes is associated with high precursor concentrations in winter,whereas ozone concentrations in winter are not much influenced by transportpatterns, suggesting a rather uniform distribution over the northern part ofthe Northern Hemisphere around mean value of 43 ± 5 ppb. In summer,high ozone concentrations of up to 90 ppb are often encountered duringtransport from north, while the levels of precursors are much lower than inwinter, because of photochemical destruction. Trajectories from southerlylatitudes and the Sahara usually have the lowest ozone concentrationsassociated with them.  相似文献   

Tektonische Beulen im Watteneis vor Büsum     

Andreas Pilger 《International Journal of Earth Sciences》1950,38(2):139-144

Zusammenfassung In der vorliegenden Arbeit werden Aufwölbungen im Eis der Wattenküste vor Büsum mit den von H. Cloos beschriebenen Beulen in der Erdoberfläche verglichen. Beide entstehen durch vertikalen Druck von unten ohne Sehnenverkürzung, in deren Folge sich Spalten im Scheitel der Gewölbe bilden. Die völlige übereinstimmung in Form und Entstehung beider Erscheinungen lä\t die Watteisbeulen als geeignetes Beispiel erscheinen, um den Werdegang der Gro\formen zu verfolgen. Die kurze Notiz von H. Cloos über einen Scheitelgraben im Eise (1948) erschien erst nach Abschlu\ dieses Aufsatzes.  相似文献   

Effect of asymmetrical street canyons on pedestrian thermal comfort in warm-humid climate of Cuba     

José?Rodríguez-AlgecirasEmail authorView author&#;s OrcID profile  Abel?Tablada  Andreas?Matzarakis 《Theoretical and Applied Climatology》2018,133(3-4):663-679

Walkability and livability in cities can be enhanced by creating comfortable environments in the streets. The profile of an urban street canyon has a substantial impact on outdoor thermal conditions at pedestrian level. This paper deals with the effect of asymmetrical street canyon profiles, common in the historical centre of Camagüey, Cuba, on outdoor thermal comfort. Temporal-spatial analyses are conducted using the Heliodon2 and the RayMan model, which enable the generation of accurate predictions about solar radiation and thermal conditions of urban spaces, respectively. On these models, urban settings are represented by asymmetrical street canyons with five different height-to-width ratios and four street axis orientations (N-S, NE-SW, E-W, SE-NW). Results are evaluated for daytime hours across the street canyon, by means of the physiologically equivalent temperature (PET index) which allows the evaluation of the bioclimatic conditions of outdoor environments. Our findings revealed that high profiles (façades) located on the east-facing side of N-S streets, on the southeast-facing side of NE-SW streets, on the south-facing side of E-W street, and on the southwest-facing side of SE-NW streets, are recommended to reduce the total number of hours under thermal stress. E-W street canyons are the most thermally stressed ones, with extreme PET values around 36 °C. Deviating from this orientation ameliorates the heat stress with reductions of up to 4 h in summer. For all analysed E-W orientations, only about one fifth of the street can be comfortable, especially for high aspect ratios (H/W > 3). Optimal subzones in the street are next to the north side of the E-W street, northwest side of the NE-SW street, and southwest side of the SE-NW street. Besides, when the highest profile is located on the east side of N-S streets, then the subzone next to the east-facing façade is recommendable for pedestrians. The proposed urban guidelines enable urban planners to create and renovate urban spaces which are more efficient in diminishing pedestrian thermal stress.  相似文献