Adsorption of l-aspartate to rutile (α-TiO₂): Experimental and theoretical surface complexation studies     

Caroline M. Jonsson  Christopher L. Jonsson  Charlene Estrada  Dimitri A. Sverjensky  H. James Cleaves II 《Geochimica et cosmochimica acta》2010,74(8):2356-22386

Interactions between aqueous amino acids and mineral surfaces influence many geochemical processes from biomineralization to the origin of life. However, the specific reactions involved and the attachment mechanisms are mostly unknown. We have studied the adsorption of l-aspartate on the surface of rutile (α-TiO₂, pH_PPZC = 5.4) in NaCl(aq) over a wide range of pH, ligand-to-solid ratio and ionic strength, using potentiometric titrations and batch adsorption experiments. The adsorption is favored below pH 6 with a maximum of 1.2 μmol of adsorbed aspartate per m² of rutile at pH 4 in our experiments. The adsorption decreases at higher pH because the negatively charged aspartate molecule is repelled by the negatively charged rutile surface above pH_PPZC. At pH values of 3-5, aspartate adsorption increases with decreasing ionic strength. The adsorption of aspartate on rutile is very similar to that previously published for glutamate (Jonsson et al., 2009). An extended triple-layer model was used to provide a quantitative thermodynamic characterization of the aspartate adsorption data. Two reaction stoichiometries identical in reaction stoichiometry to those for glutamate were needed. At low surface coverages, aspartate, like glutamate, may form a bridging-bidentate surface species binding through both carboxyl groups, i.e. “lying down” on the rutile surface. At high surface coverages, the reaction stoichiometry for aspartate was interpreted differently compared to glutamate: it likely involves an outer-sphere or hydrogen bonded aspartate surface species, as opposed to a partly inner-sphere complex for glutamate. Both the proposed aspartate species are qualitatively consistent with previously published ATR-FTIR spectroscopic results for aspartate on amorphous titanium dioxide. The surface complexation model for aspartate was tested against experimental data for the potentiometric titration of aspartate in the presence of rutile. In addition, the model correctly predicted a decrease of the isoelectric point with increased aspartate concentration consistent with previously published studies of the aspartate-anatase system. Prediction of the surface speciation of aspartate on rutile indicates that the relative proportions of the two complexes are a strong function of environmental conditions, which should be taken into account in considerations of geochemical systems involving the interactions of biomolecules and minerals in electrolyte solutions.  相似文献   

The Meteoritical Bulletin,No. 94, September 2008     

Michael K. WEISBERG  Caroline SMITH  Gretchen BENEDIX  Luigi FOLCO  Kevin RIGHTER  Jutta ZIPFEL  Akira YAMAGUCHI  Hasnaa CHENNAOUI AOUDJEHANE 《Meteoritics & planetary science》2008,43(9):1551-1584

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Deglacial radiocarbon history of tropical Atlantic thermocline waters: absence of CO2 reservoir purging signal     

Caroline Cléroux  Peter deMenocal  Thomas Guilderson 《Quaternary Science Reviews》2011,30(15-16):1875-1882

A current scenario to explain much of the atmospheric CO₂ increase during the Glacial to Holocene climate transition requires the outgassing of a deep, old oceanic CO₂ reservoir thought to be located in the Southern Ocean. In this scenario, CO₂-rich and ¹⁴C-depleted subsurface Antarctic-sourced water, ventilates the thermocline where it is purged to the atmosphere in the equatorial regions, a view that has been met with conflicting results. Using a novel approach (paired surface and deep-dwelling planktonic foraminifer radiocarbon analyses), we document that the equatorial Atlantic thermocline did not see old, ¹⁴C-depleted water, which would be characteristic of the proposed isolated deep ocean CO₂ reservoir. Data from several studies concur that, during the deglaciation, Antarctic intermediate waters were contributing to Atlantic thermocline waters even more than today, therefore, our observations challenge the current purging hypothesis. Together with other studies, these results suggest that the mechanism responsible for the deglacial CO₂ rise cannot invoke contemporary circulation modes and/or thermocline ventilation pathways.  相似文献   

Identification of the natural product 2,3,4,5-tetrabromo-1-methylpyrrole in Pacific biota, passive samplers and seagrass from Queensland, Australia     

Gaul S  Bendig P  Olbrich D  Rosenfelder N  Ruff P  Gaus C  Mueller JF  Vetter W 《Marine pollution bulletin》2011,62(11):2463-2468

Halogenated natural products (HNPs) are frequently detected in marine organisms. High HNP concentrations have previously been found in marine mammals from the Great Barrier Reef, Australia, including in the blubber of herbivorous dugongs (Dugong dugon). To identify the source of HNPs we initially focused on the analysis of Australian seagrass (Halophila ovalis) which serves as the principal food source for dugongs. GC/MS analysis of the seagrass indicated the presence of several organobromine compounds. One compound was identified as 2,3,4,5-tetrabromo-1-methylpyrrole (TBMP) by synthesis. Subsequent analysis of semipermeable membrane devices demonstrated that the photo-sensitive TBMP is widespread in the Great Barrier Reef (Queensland, Australia). The detection of larger TBMP concentrations in fish fillets from Chile and traces in mussels from New Zealand indicated that this potential HNP may be distributed throughout the Southern Pacific Ocean.  相似文献   

228Ra, 226Ra, 224Ra and 223Ra in potential sources and sinks of land-derived material in the German Bight of the North Sea: implications for the use of radium as a tracer     

Caroline Schmidt  Claudia Hanfland  Pierre Regnier  Philippe Van Cappellen  Michael Schl��ter  Ulrich Knauthe  Ingrid Stimac  Walter Geibert 《Geo-Marine Letters》2011,31(4):259-269

Activities of the naturally occurring radium nuclides ²²⁸Ra, ²²⁶Ra, ²²⁴Ra and ²²³Ra were determined in waters of the open German Bight and adjacent nearshore areas in the North Sea, in order to explore the potential use of radium isotopes as natural tracers of land–ocean interaction in an environment characterised by extensive tidal flats, as well as riverine and groundwater influx. Data collected at various tidal phases from the Weser Estuary (²²⁸Ra: 46.3 ± 4.6; ²²⁶Ra: 17.1 ± 1.1; ²²⁴Ra: 26.1 ± 8.2 to 36.5 ± 6.1; ²²³Ra: 1.8 ± 0.1 to 4.0 ± 0.4), tidal flats near Sahlenburg (²²⁸Ra: 39.3 ± 3.8 to 46.0 ± 4.5; ²²⁶Ra: 15.5 ± 1.5 to 16.5 ± 1.7; ²²⁴Ra: 34.3 ± 2.2 to 85.3 ± 6.3; ²²³Ra: 3.6 ± 0.5 to 8.0 ± 1.2), freshwater seeps on tidal flats near Sahlenburg (²²⁸Ra: 42.1 ± 4.1; ²²⁶Ra: 21.3 ± 2.2; ²²⁴Ra: 5.1 ± 0.9; ²²³Ra: 2.6 ± 1.3) and also in permanently inundated parts of the North Sea (²²⁸Ra: 23.0 ± 2.3 to 28.2 ± 2.8; ²²⁶Ra: 8.2 ± 0.8 to 11.8 ± 1.2; ²²⁴Ra: 3.1 ± 1.0 to 10.1 ± 0.9; ²²³Ra: 0.1 ± 0.02 to 0.9 ± 0.05; units: disintegrations per minute per 100 kg water sample) reveal that, except for the fresh groundwater, the potential end-members of nearshore water mass mixing have quite similar radium signatures, excluding a simple discrimination between the sources. However, the decreasing activities of the short-lived ²²⁴Ra and ²²³Ra isotopes recorded towards the island of Helgoland in the central German Bight show a potential to constrain fluxes of land-derived material to the open North Sea. The largest source for all radium isotopes is generally found on the vast tidal flats and in the Weser Estuary. Future work could meaningfully combine this so-called radium quartet approach with investigations of radon activity. Indeed, preliminary data from a tidal flat site with fresh groundwater seepage reveal a ²²²Rn signal that is clearly lower in seawater.  相似文献   

Prehistoric life: Evolution and the fossil record,by Bruce S. Lieberman & Roger L. Kaesler. John Wiley & Sons,Chichester, 2010. No. of pages: viii+385 pp. Price: UK£39.95. ISBN 978‐0‐632‐04472‐6 (paperback).     

Caroline J. Buttler 《Geological Journal》2014,49(1):109-109

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Dynamical relaxation and the orbits of low-mass extrasolar planets   总被引：1，自引：0，他引：1  

Caroline Terquem  John C. B. Papaloizou 《Monthly notices of the Royal Astronomical Society》2002,332(2):L39-L43

We consider the evolution of a system containing a population of massive planets formed rapidly through a fragmentation process occurring on a scale on the order of 100 au and a lower mass planet that assembles in a disc on a much longer time-scale. During the formation phase, the inner planet is kept on a circular orbit owing to tidal interaction with the disc, while the outer planets undergo dynamical relaxation. Interaction with the massive planets left in the system after the inner planet forms may increase the eccentricity of the inner orbit to high values, producing systems similar to those observed.  相似文献   

Functional Performance of Three Invasive <Emphasis Type="Italic">Marenzelleria</Emphasis> Species Under Contrasting Ecological Conditions Within the Baltic Sea     

Cintia O. Quintana  Caroline Raymond  Francisco J. A. Nascimento  Stefano Bonaglia  Stefan Forster  Jonas S. Gunnarsson  Erik Kristensen 《Estuaries and Coasts》2018,41(6):1766-1781

A 4-week laboratory experiment investigated the behaviour (survival and bioirrigation) and impact of the invasive polychaetes Marenzelleria viridis, M. neglecta and M. arctia on sediment-water solutes exchange, porewater chemistry, and Fe and P interactions in high-salinity sandy sediment (HSS) and low-salinity muddy sediment (LSM) from the Baltic Sea. M. viridis showed deep burrowing with efficient bioirrigation (11 L m^?2 day^?1) and high survival (71%) in HSS, while M. arctia exhibited shallow burrowing with high bioirrigation (12 L m^?2 day^?1) and survival (88%) in LSM. M. neglecta behaved poorly in both ecological settings (bioirrigation, 5–6 L m^?2 day^?1; survival, 21–44%). The deep M. viridis bioirrigation enhanced total microbial CO₂ (TCO₂) production in HSS by 175% with a net efflux of NH₄⁺ and PO₄^3?, at rates 3- to 27-fold higher than for the other species. Although the shallow and intense bioirrigation of M. arctia in LSM stimulated microbial TCO₂ production to some extent (61% enhancement), the nutrient fluxes close to zero indicate that it effectively prevented the P release. Porewater Fe:PO₄^3? ratios revealed that the oxidizing effect of M. arctia bioirrigation increased the PO₄^3? adsorption capacity of LSM twofold relative to defaunated controls while no buffering of PO₄^3? was detected in M. viridis HSS treatment. Therefore, the different behaviour of the three species in various environments and the sharp contrast between M. viridis and M. arctia effects on C, N and P cycling must be considered carefully when the ecological role of Marenzelleria species in the Baltic Sea is evaluated.  相似文献   

Laboratory simulation of terrestrial meteorite weathering using the Bensour (LL6) ordinary chondrite     

Martin R. Lee  Caroline L. Smith  Sarah H. Gordon  Mark E. Hodson 《Meteoritics & planetary science》2006,41(8):1123-1138

Abstract— Laboratory dissolution experiments using the LL6 ordinary chondrite Bensour demonstrate that meteoritic minerals readily react with distilled water at low temperatures, liberating ions into solution and forming reaction products. Three experiments were performed, all for 68 days and at atmospheric fO₂ but using a range of water/rock ratios and different temperatures. Experiments 1 and 2 were batch experiments and undertaken at room temperature, whereas in experiment 3, condensed boiling water was dripped onto meteorite subsamples within a Soxhlet extractor. Solutions from experiment 1 were chemically analyzed at the end of the experiment, whereas aliquots were extracted from experiments 2 and 3 for analysis at regular intervals. In all three experiments, a very significant proportion of the Na, Cl, and K within the Bensour subsamples entered solution, demonstrating that chlorapatite and feldspar were especially susceptible to dissolution. Concentrations of Mg, Al, Si, Ca, and Fe in solution were strongly affected by the precipitation of reaction products and Mg and Ca may also have been removed by sorption. Calculations predict saturation of experimental solutions with respect to Al hydroxides, Fe oxides, and Fe (oxy)hydroxides, which would have frequently been accompanied by hydrous aluminosilicates. Some reaction products were identified and include silica, a Mg‐rich silicate, Fe oxides, and Fe (oxy)hydroxides. The implications of these results are that even very short periods of subaerial exposure of ordinary chondrites will lead to dissolution of primary minerals and crystallization of weathering products that are likely to include aluminosilicates and silicates, Mg‐Ca carbonates, and sulfates in addition to the ubiquitous Fe oxides and (oxy)hydroxides.  相似文献   

Scour effects on the response of laterally loaded piles considering stress history of sand     

Cheng Lin  Caroline Bennett  Jie Han  Robert L. Parsons 《Computers and Geotechnics》2010,37(7-8):1008-1014

Scour is the removal of soils around pile foundations of bridges or offshore platforms, resulting in reduced capacity of the foundations in either lateral or vertical direction. A common way to analyze the scour-affected pile foundations is to remove the scoured soil layers while keeping the properties of the remaining soil unchanged. However, this approach ignores the fact that the remaining soil experiences different stress histories before and after scour, which can be expected to change the properties of the remaining soil. As a result, the resistance of the remaining soil provided to the pile foundation may be different. The present study focused on the response of laterally loaded pile foundations in sand under scour considering the stress history of the remaining sand. Relative density and coefficient of lateral earth pressure of the sand were evaluated when it changed from a normally consolidated (NC) soil to an over-consolidated (OC) soil due to scour. The relative density was then used to estimate other properties of sand, e.g., unit weight, friction angle, and modulus of subgrade reaction of the sand based on their correlation. The lateral load–deflection (p–y) curve for a pile in sand was modified and input into the computer software, LPILE Plus V 5.0, to account for the effect of the stress history induced by scour. A field test was referenced as an example to compare the calculated results from the modified p–y curves with those from the initially developed p–y curves for the tested sand. The results showed that the change in the over-consolidation ratio (OCR) resulted in the most significant effect on the lateral soil resistance among all the effects due to the changes in the properties of the remaining sand. The sand changing from an NC to OC state increased the lateral soil resistance to the pile foundation. Ignoring the stress history would result in a conservative design of laterally loaded piles under scour.  相似文献