Dissolution/precipitation kinetics of boehmite and gibbsite: Application of a pH-relaxation technique to study near-equilibrium rates     

Pascale Bnzeth  Donald A. Palmer  David J. Wesolowski 《Geochimica et cosmochimica acta》2008,72(10):2429-2453

The dissolution and precipitation rates of boehmite, AlOOH, at 100.3 °C and limited precipitation kinetics of gibbsite, Al(OH)₃, at 50.0 °C were measured in neutral to basic solutions at 0.1 molal ionic strength (NaCl + NaOH + NaAl(OH)₄) near-equilibrium using a pH-jump technique with a hydrogen-electrode concentration cell. This approach allowed relatively rapid reactions to be studied from under- and over-saturation by continuous in situ pH monitoring after addition of basic or acidic titrant, respectively, to a pre-equilibrated, well-stirred suspension of the solid powder. The magnitude of each perturbation was kept small to maintain near-equilibrium conditions. For the case of boehmite, multiple pH-jumps at different starting pHs from over- and under-saturated solutions gave the same observed, first order rate constant consistent with the simple or elementary reaction: .

This relaxation technique allowed us to apply a steady-state approximation to the change in aluminum concentration within the overall principle of detailed balancing and gave a resulting mean rate constant, (2.2 ± 0.3) × 10⁻⁵ kg m⁻² s⁻¹, corresponding to a 1σ uncertainty of 15%, in good agreement with those obtained from the traditional approach of considering the rate of reaction as a function of saturation index. Using the more traditional treatment, all dissolution and precipitation data for boehmite at 100.3 °C were found to follow closely the simple rate expression:

R_net,boehmite=10^-5.485{m_OH^-}{1-exp(ΔG_r/RT)}, with R_net in units of mol m⁻² s⁻¹. This is consistent with Transition State Theory for a reversible elementary reaction that is first order in OH⁻ concentration involving a single critical activated complex. The relationship applies over the experimental ΔG_r range of 0.4–5.5 kJ mol⁻¹ for precipitation and −0.1 to −1.9 kJ mol⁻¹ for dissolution, and the pH_m ≡ −log(mH⁺) range of 6–9.6. The gibbsite precipitation data at 50 °C could also be treated adequately with the same model:R_net,gibbsite=10^-5.86{m_OH^-}{1-exp(ΔG_r/RT)}, over a more limited experimental range of ΔG_r (0.7–3.7 kJ mol⁻¹) and pH_m (8.2–9.7).  相似文献   

Geochemistry of suspended matter from the Baltic Sea 2. Results of bulk trace metal analysis by AAS     

Lutz Brügmann  Paul C. Bernard  Rene van Grieken 《Marine Chemistry》1992,38(3-4)

In 1984, on a transect covering the whole Baltic Sea and parts of the adjacent North Sea, 160 water samples were taken and analysed for their concentrations of particulate and dissolved metals. In addition, the suspended materials were investigated for their elemental bulk composition.The particulate fractions represented from about 5% (Cd, Cu and Ni) to 50% (Fe and Pb) of the total (particulate plus dissolved) concentrations. For some elements (Ba, Cd, Cu, Pb and Zn), the particulate matter from the surface microlayer was enriched with respect to those suspended materials taken from 0.2 m depth. This could reflect the atmospheric input of metal-rich aerosols. In anoxic deep waters, maximum contents of Zn (6400 μg g⁻¹), Cu (1330 μg g⁻¹) and Cd (12 μg g⁻¹) were observed in the particulate matter, indicating sulphidic forms. On the other hand, under oxic conditions the distribution coefficients (K_d) decreased with the water depth (Cd, Fe and Pb).Relative to global background levels, the particulate matter contained metal “excesses” amounting to more than 90% of the total contents (Cd, Mn, Pb and Zn). Automated electron probe X-ray microanalysis (EPXMA) revealed that the elemental composition of sediments is mainly governed by post-depositional processes of early diagenesis and is only weakly related to the composition of suspended matter in the overlying water body. For instance, in relation to surface mud sediments of the central Baltic net-sedimentation basins, Zn, Cd, Cu and Mn had 30–100% higher levels in the suspended materials. The general pattern of metal contents of particulate matter taken from 10 m depth on a transect between the Bothnian Bay and the North Sea were—possibly as a result of anthropogenic inputs—rather similar for Pb, Zn and Cu. For Fe and Mn, the distribution patterns along the transect were probably governed by the natural loading characteristics and by the biogeochemistry of those elements.  相似文献   

Zircon M257 ‐ a Homogeneous Natural Reference Material for the Ion Microprobe U‐Pb Analysis of Zircon     

Lutz Nasdala  Wolfgang Hofmeister  Nicholas Norberg  James M. Martinson  Fernando Corfu  Wolfgang Dörr  Sandra L. Kamo  Allen K. Kennedy  Andreas Kronz  Peter W. Reiners  Dirk Frei  Jan Kosler  Yusheng Wan  Jens Götze  Tobias Häger  Alfred Kröner  John W. Valley 《Geostandards and Geoanalytical Research》2008,32(3):247-265

We introduce and propose zircon M257 as a future reference material for the determination of zircon U‐Pb ages by means of secondary ion mass spectrometry. This light brownish, flawless, cut gemstone specimen from Sri Lanka weighed 5.14 g (25.7 carats). Zircon M257 has TIMS‐determined, mean isotopic ratios (2s uncertainties) of 0.09100 ± 0.00003 for ²⁰⁶pb/²³⁸U and 0.7392 ± 0.0003 for ²⁰⁷pb/²³⁵U. Its ²⁰⁶pb/²³⁸U age is 561.3 ± 0.3 Ma (unweighted mean, uncertainty quoted at the 95% confidence level); the U‐Pb system is concordant within uncertainty of decay constants. Zircon M257 contains ～ 840 μg g^?1 U (Th/U ～ 0.27). The material exhibits remarkably low heterogeneity, with a virtual absence of any internal textures even in cathodoluminescence images. The uniform, moderate degree of radiation damage (estimated from the expansion of unit‐cell parameters, broadening of Raman spectral parameters and density) corresponds well, within the “Sri Lankan trends”, with actinide concentrations, U‐Pb age, and the calculated alpha fluence of 1.66 × 10¹⁸ g^?1. This, and a (U+Th)/He age of 419 ± 9 Ma (2s), enables us to exclude any unusual thermal history or heat treatment, which could potentially have affected the retention of radiogenic Pb. The oxygen isotope ratio of this zircon is 13.9%o VSMOW suggesting a metamorphic genesis in a marble or calc‐silicate skarn.  相似文献   

The influence of the coast on the dynamics of upwelling fronts: Part II. Numerical simulations     

Pascale Bouruet-Aubertot  Vincent Echevin 《Dynamics of Atmospheres and Oceans》2002,36(1-3)

We investigated the dynamics of upwelling fronts near a coast. This work was first motivated by laboratory experiments [Bouruet-Aubertot, Linden, Dyn. Atmos. Oceans, 2002] in which the front is produced by the adjustment of a buoyant fluid initially confined within a bottomless cylinder. It was shown that cyclonic eddies consisting of coastal waters are enhanced when the front is unstable near the coast (the outer vertical boundary). The purpose of this paper is to provide further insights into this process. We reproduced the experimental configuration using a three-dimensional model of the primitive equations. We first show that for coastal fronts more potential energy, in terms of the maximum available potential energy, is released than for open-ocean fronts. Therefore, waves of larger amplitude are generated during the adjustment and the mean flow that establishes has a higher kinetic energy in the former case. Then as baroclinic instability starts and wave crests reach the boundary, cyclonic eddies are enhanced as in the laboratory experiments and in a similar way. However, in contrast to the laboratory experiments, offshore advection of cyclonic eddies can occur in two stages, depending on the spatial organization of the baroclinic wave. When the baroclinic wave consists of the sum of different modes and is thus highly asymmetric, the offshore advection of cyclonic eddies occurs just after their enhancement at the boundary, as in the laboratory experiments. By contrast, when a single-mode baroclinic wave develops, neighboring cyclonic eddies first merge before being advected offshore. Very different behavior is observed for open-ocean fronts. First a mixed baroclinic–barotropic instability grows. Then the eddies transfer their energy to the mean flow and the barotropic and baroclinic instabilities start again. An excellent agreement is obtained with the main result obtained in the laboratory experiments: the ratio between growth rates of surface cyclonic and anticyclonic vorticity increases as the instability develops nearer to the coast.  相似文献   

Lithofacies succession of maar crater deposits in the Eifel area (Germany)   总被引：2，自引：0，他引：2  

M. Pirrung  C. Fischer  G. Büchel  R. Gaupp  H. Lutz  F. -O. Neuffer 《地学学报》2003,15(2):125-132

ABSTRACT Maar craters often contain exceptionally preserved fossils and maar sediments may reflect detailed environmental changes. Volcanosedimentary processes in a Middle Eocene maar crater lake are illustrated by the deposits of Eckfeld Maar in the Tertiary Hocheifel Volcanic Field (Rhenish Massif, Germany). The maar origin of the basin is evident from a circular negative gravity anomaly which indicates a low-density funnel-shaped basin filling. From the facies analysis of an Eocene (Eckfeld) and a Pleistocene (Döttingen) maar we develop a lithozone classification for the interpretation of maar sediments: syn-/post-eruptive breccias are followed by a fining-upwards sequence of lacustrine mud with coarse layers and final swamp deposits. From the facies analysis and regional geological data we reconstruct the pre- to post-eruptive history of a maar crater prior to post-Eocene uplift. These observations can be used for the interpretation of Tertiary and Quaternary maar craters that are ideal fossil and sediment traps.  相似文献   

Paleontological records indicate the occurrence of open woodlands in a dry inland climate at the present-day Arctic coast in western Beringia during the Last Interglacial     

Frank Kienast  Sebastian Wetterich  Svetlana Kuzmina  Lutz Schirrmeister  Andrei A. Andreev  Pavel Tarasov  Larisa Nazarova  Annette Kossler  Larisa Frolova  Viktor V. Kunitsky 《Quaternary Science Reviews》2011,30(17-18):2134-2159

Permafrost records, accessible at outcrops along the coast of Oyogos Yar at the Dmitry Laptev Strait, NE-Siberia, provide unique insights into the environmental history of Western Beringia during the Last Interglacial. The remains of terrestrial and freshwater organisms, including plants, coleopterans, chironomids, cladocerans, ostracods and molluscs, have been preserved in the frozen deposits of a shallow paleo-lake and indicate a boreal climate at the present-day arctic mainland coast during the Last Interglacial. Terrestrial beetle and plant remains suggest the former existence of open forest-tundra with larch (Larix dahurica), tree alder (Alnus incana), birch and alder shrubs (Duschekia fruticosa, Betula fruticosa, Betula divaricata, Betula nana), interspersed with patches of steppe and meadows. Consequently, the tree line was shifted to at least 270 km north of its current position. Aquatic organisms, such as chironomids, cladocerans, ostracods, molluscs and hydrophytes, indicate the formation of a shallow lake as the result of thermokarst processes. Steppe plants and beetles suggest low net precipitation. Littoral pioneer plants and chironomids indicate intense lake level fluctuations due to high evaporation. Many of the organisms are thermophilous, indicating a mean air temperature of the warmest month that was greater than 13 °C, which is above the minimum requirements for tree growth. These temperatures are in contrast to the modern values of less than 4 °C in the study area. The terrestrial and freshwater organism remains were found at a coastal exposure that was only 3.5 m above sea level and in a position where they should have been under sea during the Last Interglacial when the global sea level was 6–10 m higher than the current levels. The results suggest that during the last warm stage, the site was inland, and its modern coastal situation is the result of tectonic subsidence.  相似文献   

Experimental impact cratering: A summary of the major results of the MEMIN research unit          下载免费PDF全文

Thomas Kenkmann  Alex Deutsch  Klaus Thoma  Matthias Ebert  Michael H. Poelchau  Elmar Buhl  Eva-Regine Carl  Andreas N. Danilewsky  Georg Dresen  Anja Dufresne  Nathanaël Durr  Lars Ehm  Christian Grosse  Max Gulde  Nicole Güldemeister  Christopher Hamann  Lutz Hecht  Stefan Hiermaier  Tobias Hoerth  Astrid Kowitz  Falko Langenhorst  Bernd Lexow  Hanns-Peter Liermann  Robert Luther  Ulrich Mansfeld  Dorothee Moser  Manuel Raith  Wolf Uwe Reimold  Martin Sauer  Frank Schäfer  Ralf Thomas Schmitt  Frank Sommer  Jakob Wilk  Rebecca Winkler  Kai Wünnemann 《Meteoritics & planetary science》2018,53(8):1543-1568

This paper reviews major findings of the Multidisciplinary Experimental and Modeling Impact Crater Research Network (MEMIN). MEMIN is a consortium, funded from 2009 till 2017 by the German Research Foundation, and is aimed at investigating impact cratering processes by experimental and modeling approaches. The vision of this network has been to comprehensively quantify impact processes by conducting a strictly controlled experimental campaign at the laboratory scale, together with a multidisciplinary analytical approach. Central to MEMIN has been the use of powerful two-stage light-gas accelerators capable of producing impact craters in the decimeter size range in solid rocks that allowed detailed spatial analyses of petrophysical, structural, and geochemical changes in target rocks and ejecta. In addition, explosive setups, membrane-driven diamond anvil cells, as well as laser irradiation and split Hopkinson pressure bar technologies have been used to study the response of minerals and rocks to shock and dynamic loading as well as high-temperature conditions. We used Seeberger sandstone, Taunus quartzite, Carrara marble, and Weibern tuff as major target rock types. In concert with the experiments we conducted mesoscale numerical simulations of shock wave propagation in heterogeneous rocks resolving the complex response of grains and pores to compressive, shear, and tensile loading and macroscale modeling of crater formation and fracturing. Major results comprise (1) projectile–target interaction, (2) various aspects of shock metamorphism with special focus on low shock pressures and effects of target porosity and water saturation, (3) crater morphologies and cratering efficiencies in various nonporous and porous lithologies, (4) in situ target damage, (5) ejecta dynamics, and (6) geophysical survey of experimental craters.  相似文献   

Mauer – the type site of Homo heidelbergensis: palaeoenvironment and age     

Günther A. Wagner  Lutz Christian Maul  Manfred Löscher  H. Dieter Schreiber 《Quaternary Science Reviews》2011,30(11-12):1464-1473

The mandible of Homo heidelbergensis was found 1907 in the sand pit Grafenrain at Mauer in coarse fluvial sands 24 m below the surface, deposited in a former course of the Neckar River. These ‘Mauer sands’ are overlain by a series of glacial-climate loess deposits with intercalated interglacial palaeosols, which can be correlated with Quaternary climate history, thus indicating an early Middle Pleistocene age for H. heidelbergensis. The ‘Mauer sands’ are famous for their rather rich mammal fauna, which clearly indicates interglacial climate conditions. The faunal evidence – in particular the micromammals – place the ‘Mauer sands’ into MIS 15 or MIS 13 although most stratigraphic arguments favour correlation to MIS 15 and therefore to an age of ca 600 ka.  相似文献   

Projected changes of rainfall seasonality and dry spells in a high greenhouse gas emissions scenario     

Salvatore Pascale  Valerio Lucarini  Xue Feng  Amilcare Porporato  Shabeh ul Hasson 《Climate Dynamics》2016,46(3-4):1331-1350

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An approach for estimating time-variable rates from geodetic time series   总被引：1，自引：0，他引：1  

Olga Didova  Brian Gunter  Riccardo Riva  Roland Klees  Lutz Roese-Koerner 《Journal of Geodesy》2016,90(11):1207-1221

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