Surface complexation of U(VI) on goethite (α-FeOOH)     

David M. Sherman  Caroline L. Peacock  Christopher G. Hubbard 《Geochimica et cosmochimica acta》2008,72(2):298-310

Sorption of U(VI) to goethite is a fundamental control on the mobility of uranium in soil and groundwater. Here, we investigated the sorption of U on goethite using EXAFS spectroscopy, batch sorption experiments and DFT calculations of the energetics and structures of possible surface complexes. Based on EXAFS spectra, it has previously been proposed that U(VI), as the uranyl cation , sorbs to Fe oxide hydroxide phases by forming a bidentate edge-sharing (E2) surface complex, >Fe(OH)₂UO₂(H₂O)_n. Here, we argue that this complex alone cannot account for the sorption capacity of goethite (α-FeOOH). Moreover, we show that all of the EXAFS signal attributed to the E2 complex can be accounted for by multiple scattering. We propose that the dominant surface complex in CO₂-free systems is a bidentate corner-sharing (C2) complex, (>FeOH)₂UO₂(H₂O)₃ which can form on the dominant {101} surface. However, in the presence of CO₂, we find an enhancement of UO₂ sorption at low pH and attribute this to a (>FeO)CO₂UO₂ ternary complex. With increasing pH, U(VI) desorbs by the formation of aqueous carbonate and hydroxyl complexes. However, this desorption is preceded by the formation of a second ternary surface complex (>FeOH)₂UO₂CO₃. The three proposed surface complexes, (>FeOH)₂UO₂(H₂O)₃, >FeOCO₂UO₂, and (>FeOH)₂UO₂CO₃ are consistent with EXAFS spectra. Using these complexes, we developed a surface complexation model for U on goethite with a 1-pK model for surface protonation, an extended Stern model for surface electrostatics and inclusion of all known UO₂-OH-CO₃ aqueous complexes in the current thermodynamic database. The model gives an excellent fit to our sorption experiments done in both ambient and reduced CO₂ environments at surface loadings of 0.02-2.0 wt% U.  相似文献   

Kinetic studies of the rate of dissolution of silica and diatom tests in sea water     

Lucinda M. L. Hubbard  John P. Riley 《Journal of Oceanography》1984,40(2):148-154

Kinetic studies have been carried out on the dissolution of 10μm beads of silica and of the siliceous tests of two species of diatoms (Thalassiosira fluviatus andSkeletonema costatum) in sea water at 10–50°C and over the pH range 6–9. At all temperatures dissolution of the biogenous silica occurred most rapidly at pH 8 and most slowly at pH 6. First order kinetics were closely followed when the silica was present in a considerable excess over that required for saturation, the rate being proportional to the area of the silica. Apparent deviation from this type of kinetics occurred when there was insufficient silica to bring about saturation. This was undoubtedly due to the progressive decrease in the surface area which takes place as the particle dissolves. Application of the rather simplistic model developed by Kamataniet al. (1980), which makes allowance for this decrease, gave a close correspondence with the data until ∼ 90% of the silica had dissolved.  相似文献   

The Jovian surface condition and cooling rate     

W.B. Hubbard 《Icarus》1977,30(2):305-310

A theory which is almost fully analytic is used to investigate Jupiter's cooling rate. We find that a simple model of contraction with adiabatic interior structure gives a total cooling time to the present which is in good agreement with the age of the solar system. The interplay between the surface condition and the cooling rate is exhibited and discussed. The current rate of change of the effective temperature is calculated to be ?1°K/0.145×10⁹ yr. Discrepancies with fully numerical investigations of the Jovian age and cooling rate are noted.  相似文献   

The evolving role of voluntarism in ageing rural communities   总被引：1，自引：0，他引：1  

Mark W. Skinner  Alun E. Joseph 《New Zealand geographer》2007,63(2):119-129

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Wet tropospheric effects on precise relative GPS height determination   总被引：6，自引：0，他引：6  

A. H. Dodson  P. J. Shardlow  L. C. M. Hubbard  G. Elgered  P. O. J. Jarlemark 《Journal of Geodesy》1996,70(4):188-202

Summary Considerable interest has been generated recently in the use of the Global Positioning System (GPS) for precise height determination. A major error source in these measurements is the propagation delay due to atmospheric water vapour. In order to achieve the high precisions required for such applications as absolute sea-level monitoring improvement of wet delay modelling is necessary. Results from a GPS campaign show a significant correlation (0.91) between the variability of the wet delay measured using a water vapour radiometer (WVR) at the Onsala site and the absolute value of the residual error in the height determination of a 134 km baseline from Onsala to Jönköping. This correlation indicates that the atmosphericvariability as inferred from the WVR data includes information on the quality of the GPS height estimate. During periods of high atmospheric activity, e.g., during the passage of a weather front, the use of a six-parameter gradient model reduces the spread for the vertical coordinate from 40 mm to 20 mm (with standard deviations of 17 mm and 9 mm respectively) over the 134 km baseline (less than 1 × 10^–7) using 8 hour data spans on 11 different days over a six month period.  相似文献   

Sediment rejection by recent scleractinian corals: a key to palaeo-environmental reconstruction     

Julia A. E. B. Hubbard  Yvonne P. Pocock 《International Journal of Earth Sciences》1972,61(2):598-626

26 of the 59 living species of scleractinian corals found in Western Atlantic and Caribbean waters, less than 68 metres deep, and two fungiid genera from the Pacific are analysed in terms of their behaviour, sediment rejecting properties, functional morphology and distribution patterns.The contrasting behaviour and skeletal structure of the two solitary fungiids provides evidence for the construction of a theoretical mechanical model which is applied to the subsequent interpretation of the more complex colonial reef corals from the Atlantic province.Regional distribution patterns, growth forms and calical orientations of the Atlantic species and their associated sediment types were noted in dives across transects in extreme environments in the Caribbean. Representative samples were then selected from the five functional ecological niches in the Florida keys, and subjected to inundations of sized and painted carbonate sand particles in the laboratory. The coral was filmed before the sedimentary influx, on impact and during rejection. The skeletons were then extracted and dissected to construct a mechanical model compatible with their behavioural functions.There are four means of sediment rejection: distension by the stomodeal up-take of water, tentacular action, ciliary beat, and mucus entanglement. Differences in sediment rejection are ascribed to two factors (1) variations in the polyps' distensional capacity, and (2) the geometry of the calice.A theoretical model of characteristic scleractinian distribution patterns on an Atlantic patch reef mirrors regional distribution patterns. The sediment rejecting experiments are used as additional evidence for interpreting other behavioural activities of greater consequence e.g. food gathering and the removal of excrement.Theoretical models are described for the relationship of calical form to polypal function and calcical orientation to distribution patterns on the corallum; and also variations in growth form. Ecological distributions, in local patch reef and regional occurrences, are outlined in terms of the recent scleractinian corals of the Atlantic province. These models are tested against some rugose and tabulate coral distributions in the Irish Carboniferous.

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Zusammenfassung 26 der 59 Korallenarten (Scleractinia), die im westlichen Atlantik und der Karibischen See in weniger als 68 m Wassertiefe leben, und 2 Fungia-Gattungen des Pazifiks werden auf Verhalten, Fähigkeit Sediment abzuschütteln und funktioneller Morphologie untersucht. Aufgrund der Gegensätze in Verhalten und Skelettstruktur der beiden Fungia-Einzelkorallen wird ein theoretisches Modell erarbeitet, das dann auf die komplizierteren koloniebildenden Korallen angewandt wird.Regionale Verteilung, Wuchsformen und Kelchorientierung der atlantischen Korallen und die dazugehörigen Sedimente wurden in Tauchgängen in extremen Bereichen der Karibischen See erfaßt. Repräsentative Korallen-Exemplare wurden dann von fünf ökologisch definierten Bereichen der Florida Keys gesammelt und im Labor mit sortierten und gefärbten Karbonatsandkörnern überschüttet. Die Korallen wurden vor dem Experiment, während des Schüttens und des Abschüttelns gefilmt. Danach wurden die Skelette herauspräpariert und ein mechanisches Modell entwickelt, das die verhaltensbedingten Funktionen berücksichtigt.Das Sediment wird mit Hilfe von vier Mechanismen abgeschütteln: Ausdehnung der Weichteile durch Aufnahme von Wasser, Tentakelbewegungen, Ziliarbewegungen und Schleimumwicklung. Unterschiede in der Fähigkeit, Sediment abzuschütteln, wurden auf 1. Unterschiede in der Fähigkeit des Polypen, sich auszudehnen, und 2. Unterschiede in der Kelchform zurückgeführt.Ein theoretisches Modell der Korallenverteilung auf einem isolierten Riff spiegelt die Grundzüge regionaler Verteilung wider. Die Sedimentabschüttel-Experimente ergeben zusätzliche Anhaltspunkte für die Interpretation anderer Verrichtungen von größerer Bedeutung, z. B. Nahrungsaufnahme und Entfernung von Exkrementen. Theoretische Modelle für das Verhältnis von Kelchform zu Polypenfunktion und von Kelchorientierung zur Position auf dem Korallenstock und zu Wuchformunterschieden werden beschrieben.Ökologische Verteilungen, lokal und regional, werden anhand der rezenten Korallen des Atlantiks aufgezeigt. Diese Modelle werden dann am Beispiel der Verteilung rugosen und tabulaten Korallen im Karbon Irlands getestet.

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Résumé 26 espèces vivantes de coraux scléractiniens sur 59, furent découvertes dans l'Atlantique-Ouest et les eaux des Caraïbes, à moins de 68 m de fond; 2 genera fungiid du Pacifique sont analysés en fonction de leur comportement, des propriétés de rejet des sédiments dont ils font preuve, de leur morphologie fonctionelle et de leurs reséaux de distribution.Le contraste dans le compartement et dans la structure squelettique des deux fungiids solitaires, justifie la construction d'un modèle théorique mécanique qui est appliqué à l'interprétation suivante des coraux de récif coloniaux et plus complexes que l'on trouve dans la région atlantique.Les réseaux de distribution régionale, les formes de croissances d'orientations calicales de l'espèce atlantique et les types de sédiments qui leur sont associés, ont été remarqués lors de plongées aux environs extrêmes de la mer Caraïbe. Des échantillons représentatifs ont ensuite été sélectionnés dans les cinq niches écologiques fonctionelles des cayes de Floride. Puis ont été soumis, en laboratoire à des inondations de particules de sable carbonaté taillées et teintes. Le corail a été filmé avant l'entrée des sédiments, pendant l'opération et pendant le rejet. Les squelettes, ont ensuite été extraits et disséqués pour construire un modèle mécanique compatible avec leurs fonctions de compartement.Il existe quatre modes de rejet des sédiments: dilatation par absorbsion stomodéal d'eau, action tentaculaire, action ciliaire et enveloppement de mucus.Les différences dans le rejet de sédiments sont imputables a deux facteurs (1) les variations de la capacité dimensionelle du polype et (2) la géométrie du calice. Un modèle théorique des réseaux le distribution scléractiniènne, charactéristique sur un petit récif atlantique, réflecte des sébeaux de distribution régionale. Les expériences sur le rejet de sédiments, sont utilisées comme preuve supplémentaire à l'interprétation d'autres activités de comportement, comme par exemple, la recherche de nourriture ou l'émission d'éxcréments.Les modèles théoriques sont décrits pour permettre le rapport entre la forme calicale et la fonction polypale, plus entre l'orientation calicale et les résaux de distribution sur le corallum, ainsi que pour étudier les variations dans les formes de croissance. L'étude des coraux scléractiniens récents de la province atlantique, permet d'établir une ébauche de leur répartition écologique, aussi bien sur les petits récifs locaux qu'au niveau des incidences régionales. Les modèles sont également testés grace à des répartitions de coraux rugueux et tabulates dans le Carbonifière Irlandais.

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Planetary elements for 10 000 000 years     

C. J. Cohen  E. C. Hubbard  Claus Oesterwinter 《Celestial Mechanics and Dynamical Astronomy》1973,7(4):438-448

In 1950 Brouwer and van Woerkom published a secular theory of the variations of the planetary elements in analytical form. In the present paper we provide a graphical representation of this theory in the form of element plots for a time span of ten million years.  相似文献   

On the Radii of Close-in Giant Planets     

Burrows A  Guillot T  Hubbard WB  Marley MS  Saumon D  Lunine JI  Sudarsky D 《The Astrophysical journal》2000,534(1):L97-L100

The recent discovery that the close-in extrasolar giant planet HD 209458b transits its star has provided a first-of-its-kind measurement of the planet's radius and mass. In addition, there is a provocative detection of the light reflected off of the giant planet tau Bootis b. Including the effects of stellar irradiation, we estimate the general behavior of radius/age trajectories for such planets and interpret the large measured radii of HD 209458b and tau Boo b in that context. We find that HD 209458b must be a hydrogen-rich gas giant. Furthermore, the large radius of a close-in gas giant is not due to the thermal expansion of its atmosphere but to the high residual entropy that remains throughout its bulk by dint of its early proximity to a luminous primary. The large stellar flux does not inflate the planet but retards its otherwise inexorable contraction from a more extended configuration at birth. This implies either that such a planet was formed near its current orbital distance or that it migrated in from larger distances (>/=0.5 AU), no later than a few times 107 yr of birth.  相似文献   

Trace elements in ocean ridge basalts     

R.W. Kay  N.J. Hubbard 《Earth and Planetary Science Letters》1978,38(1):95-116

A correlary of sea floor spreading is that the production rate of ocean ridge basalts exceeds that of all other volcanic rocks on the earth combined. Basalts of the ocean ridges bring with them a continuous record in space and time of the chemical characteristics of the underlying mantle. The chemical record is once removed, due to chemical fractionation during partial melting. Chemical fractionations can be evaluated by assuming that peridotite melting has proceeded to an olivine-orthopyroxene stage, in which case the ratios of a number of magmaphile elements in the extracted melt closely match the ratios in the mantle. Comparison of ocean ridge basalts and chondritic meteorites reveals systematic patterns of element fractionation, and what is probably a double depletion in some elements. The first depletion is in volatile elements and is due to high accretion temperatures of a large percentage of the earth from the solar nebula. The second depletion is in the largest, most highly charged lithophile elements (“incompatible elements”), probably because the mantle source of the basalts was melted previously, and the melt, enriched in these elements, was removed. Migration of melt relative to solid under ocean ridges and oceanic plates, element fractionation at subduction zones, and fractional melting of amphibolite in the Precambrian are possible mechanisms for depleting the mantle in incompatible elements. Ratios of transition metals in the mantle source of ocean ridge basalts are close to chondritic, and contrast to the extreme depletion of refractory siderophile elements, the reason for which remains uncertain. Variation of ocean ridge basalt chemistry along the length of the ridge has been correlated with ridge elevation. Thus chemically anomalous ridge segments up to 1000 km long appear to broadly coincide with regions of high magma production (plumes, hot spots). Basalt heterogeneity at a single location indicates mantle heterogeneity on a smaller scale. Variation of ocean ridge basalt chemistry with time has not been established, in fact, criteria for recognizing old oceanic crust in ophiolite terrains are currently under debate. The similarity of rare earth element patterns in basalt from ocean ridges, back-arc basins, some young island arcs, and some continental flood basalts illustrates the dangers of tectonic labeling by rare earth element pattern.  相似文献   

Effects of mass loss for highly-irradiated giant planets     

W.B. Hubbard  M.F. Hattori  I. Hubeny 《Icarus》2007,187(2):358-364

We present calculations for the evolution and surviving mass of highly-irradiated extrasolar giant planets (EGPs) at orbital semimajor axes ranging from 0.023 to 0.057 AU using a generalized scaled theory for mass loss, together with new surface-condition grids for hot EGPs and a consistent treatment of tidal truncation. Theoretical estimates for the rate of energy-limited hydrogen escape from giant-planet atmospheres differ by two orders of magnitude, when one holds planetary mass, composition, and irradiation constant. Baraffe et al. [Baraffe, I., Selsis, F., Chabrier, G., Barman, T.S., Allard, F., Hauschildt, P.H., Lammer, H., 2004. Astron. Astrophys. 419, L13-L16] predict the highest rate, based on the theory of Lammer et al. [Lammer, H., Selsis, F., Ribas, I., Guinan, E.F., Bauer, S.J., Weiss, W.W., 2003. Astrophys. J. 598, L121-L124]. Scaling the theory of Watson et al. [Watson, A.J., Donahue, T.M., Walker, J.C.G., 1981. Icarus 48, 150-166] to parameters for a highly-irradiated exoplanet, we find an escape rate ∼¹⁰² lower than Baraffe's. With the scaled Watson theory we find modest mass loss, occurring early in the history of a hot EGP. In this theory, mass loss including the effect of Roche-lobe overflow becomes significant primarily for masses below a Saturn mass, for semimajor axes ?0.023 AU. This contrasts with the Baraffe model, where hot EGPs are claimed to be remnants of much more massive bodies, originally several times Jupiter and still losing substantial mass fractions at present.  相似文献