Phthalic acid complexation and the dissolution of forsteritic glass studied via in situ FTIR and X-ray scattering     

Peter M. Morris 《Geochimica et cosmochimica acta》2008,72(8):1970-1985

Multiple Internal Reflection Fourier Transform Infra-Red (MIR-FTIR) spectroscopy was developed and used for in situ flow-through experiments designed to study the process of organic acid promoted silicate dissolution. In tandem with the FTIR analysis, ex situ X-ray scattering was used to perform detailed analyses of the changes in the surface structure and chemistry resulting from the dissolution process. Phthalic acid and forsteritic glass that had been Chemically Vapour Deposited (CVD) onto an internal reflection element were used as reactants, and the MIR-FTIR results showed that phthalic acid may promote dissolution by directly binding to exposed Mg metal ion centers on the solid surface. Integrated infrared absorption intensity as a function of time shows that phthalic acid attachment apparently follows a t^1/2 dependence, indicating that attachment is a diffusive process. The diffusion coefficient of phthalic acid was estimated to be approximately 7 × 10⁻⁶ cm² s⁻¹ in the solution near the interface with the glass. Shifts in the infrared absorption structure of the phthalate complexed with the surface compared to the solute species indicate that phthalate forms a seven-membered ring chelate complex. This bidentate complex efficiently depletes Mg from the glass surface, such that after reaction as much as 95% of the Mg may be removed. Surface depletion in Mg causes adsorbate density to fall after an initial attachment stage for the organic ligand. In addition, the infrared analysis shows that silica in the near surface polymerizes after Mg removal, presumably to maintain charge balance. X-ray reflectivity shows that the dissolution rate of forsteritic glass at pH 4 based on Mg removal in such flow-through experiments was equal to 4 × 10⁻¹² mol cm⁻² s⁻¹ (geometric surface area normalized). Reflectivity also shows how the surface mass density decreases during reaction from 2.64 g cm⁻³ to 2.2 g cm⁻³, consistent with preferential loss of Mg from the surface. Auxiliary batch experiments with forsteritic glass films deposited onto soda glass were also completed to add further constraints to the mechanism of reaction. By combining reflectivity with diffuse scatter measurements it is shown that the primary interface changes little in terms of atomic-scale roughness even after removal of several hundred angstroms of material. These measurements unequivocally show how a dicarboxylic acid bonds to and may chelate the dissolution of a magnesium-bearing silicate. At the molecular level the solid surface retreat may best be described by a depinning model where Mg is preferentially removed and residual silica tetrahedra polymerize and act to episodically “pin” the surface.  相似文献   

Thermal evolution and physics of melt extraction on the ureilite parent body     

Lionel Wilson  Cyrena Anne Goodrich 《Geochimica et cosmochimica acta》2008,72(24):6154-6176

We develop a physical model of the thermal history of the ureilite parent body (UPB) that numerically tracks the history of its heating, hydration, dehydration, partial melting and smelting as a function of its formation time and the initial values of its composition, formation temperature and water ice content. Petrologic and chemical data from the main group (non-polymict) ureilite meteorites, which sample the interior of the UPB between depths corresponding to pressures in the range 3-10 MPa, are used to constrain the model. We find that to achieve the ∼30% melting inferred for ureilites from all sampled depths, the UPB must have had a radius between ∼80 and ∼130 km and must have accreted about 0.55 Ma after CAI formation. Melting began in the body at ∼1 Ma after CAI, and the time at which 30% melting was reached varied with depth in the asteroid but was always between ∼4.5 and ∼5.8 Ma after CAI. The total rate at which melt was produced in the UPB varied from more than 100 m³ s⁻¹ in the very early stages of melting at ∼1 Ma after CAI to ∼5 m³ s⁻¹ between 2 and 3 Ma after CAI, decreasing to extremely small values as the end of melting was approached beyond ∼5 Ma. Although the initial period of high melt production occupied only a short time around 1 Ma after CAI, it corresponded to ∼half (16%) of total silicate melting, and all strictly basaltic (i.e. plagioclase-saturated) melts must have been produced during this period.A very efficient melt transport network, consisting of a hierarchy of veins and larger pathways (dikes), developed quickly at the start of melting, ensuring rapid (timescales of months) transport of any single parcel of melt to shallow levels, thus ensuring that chemical interaction between melts and the rocks through which they subsequently passed was negligible. Volatile (mainly carbon monoxide) production due to smelting began at the start of silicate melting in the shallowest parts of the UPB and at later times at greater depths. Except at the very start and very end of melting, the volatile content of the melts produced was always high - generally between 15 and 35 mass % - and most of the melt produced was erupted at the surface of the UPB with speeds well in excess of the escape velocity and was lost into space. However, we show that 30% melting at the 3 MPa pressure level was only possible if ∼15% of the total melt produced in the asteroid was retained as a small number (∼5) of very extensive, sill-like intrusions centered at a depth of ∼7 km below the surface, near the base of the ∼8 km thick outer crust of the asteroid that was maintained at temperatures below the basalt solidus by conductive heat loss to the surface. The horizontal extents of these sills occupied about 75% of the surface area of the UPB, and the sills acted as buffers between the steady supply of melt from depth and the intermittent explosive eruption of the melt into space. We infer that samples from these intrusions are preserved as the rare feldspathic (loosely basaltic) clasts in polymict ureilites, and show that the cooling histories of the sills are consistent with these clasts reaching isotopic closure at ∼5 Ma after CAI, as given by ²⁶Al-²⁶Mg, ⁵³Mn-⁵³Cr and Pb-Pb age dates.  相似文献   

Editorial     

Peter Riches 《Proceedings of the Geologists' Association. Geologists' Association》2008,119(3-4):207

  相似文献   

Airports, mobility and the calculative architecture of affective control   总被引：2，自引：0，他引：2  

Peter Adey 《Geoforum》2008,39(1):438-451

Drawing on work surrounding the theorisation of concepts such as mobility, affect and emotion, the paper argues that their control is now being intertwined in places like airports which are employing a number of techniques that engineer affects. Airport affect is enacted, in one way, by planning and designing the situational affective context one inhabits - throwing up structures of ethological possibility that shape capacities for the corporeal body to move and be moved. It is shown that the engineering of airport affect is premised upon a wider discursive framework of calculation and indeterminacy, and that selective techniques summon a number of different modalities of control. The paper concludes with a series of implications for the understanding of power, and the study of mobility, emotion and affect.  相似文献   

Atmospheric mercury near Salmon Falls Creek Reservoir in southern Idaho     

Michael L. Abbott  Che-Jen Lin  Peter Martian  Jeffrey J. Einerson 《Applied Geochemistry》2008

Gaseous elemental mercury (GEM) and reactive gaseous mercury (RGM) were measured over 2-week seasonal field campaigns near Salmon Falls Creek Reservoir in south-central Idaho from the summer of 2005 through the fall of 2006 and over the entire summer of 2006 using automated Tekran Hg analyzers. GEM, RGM, and particulate Hg (HgP) were also measured at a secondary site 90 km to the west in southwestern Idaho during the summer of 2006. The study was performed to characterize Hg air concentrations in the southern Idaho area for the first time, estimate Hg dry deposition rates, and investigate the source of observed elevated concentrations. High seasonal variability was observed with the highest GEM (1.91 ± 0.9 ng m⁻³) and RGM (8.1 ± 5.6 pg m⁻³) concentrations occurring in the summer and lower values in the winter (1.32 ± 0.3 ng m⁻³, 3.2 ± 2.9 pg m⁻³ for GEM, RGM, respectively). The summer-average HgP concentrations were generally below detection limit (0.6 ± 1 pg m⁻³). Seasonally averaged deposition velocities calculated using a resistance model were 0.034 ± 0.032, 0.043 ± 0.040, 0.00084 ± 0.0017 and 0.00036 ± 0.0011 cm s⁻¹ for GEM (spring, summer, fall and winter, respectively) and 0.50 ± 0.39, 0.40 ± 0.31, 0.51 ± 0.43 and 0.76 ± 0.57 cm s⁻¹ for RGM. The total annual RGM + GEM dry deposition estimate was calculated to be 11.9 ± 3.3 μg m⁻², or about 2/3 of the total (wet + dry) deposition estimate for the area. Periodic elevated short-term GEM (2.2–12 ng m⁻³) and RGM (50–150 pg m⁻³) events were observed primarily during the warm seasons. Back-trajectory modeling and PSCF analysis indicate predominant source directions to the SE (western Utah, northeastern Nevada) and SW (north-central Nevada) with fewer inputs from the NW (southeastern Oregon and southwestern Idaho).  相似文献   

The passivation of calcite by acid mine water. Column experiments with ferric sulfate and ferric chloride solutions at pH 2   总被引：2，自引：1，他引：1  

Josep M. Soler  Marco Boi  Jos Luis Mogolln  Jordi Cama  Carlos Ayora  Peter S. Nico  Nobumichi Tamura  Martin Kunz 《Applied Geochemistry》2008,23(12):3579-3588

Column experiments, simulating the behavior of passive treatment systems for acid mine drainage, have been performed. Acid solutions (HCl or H₂SO₄, pH 2), with initial concentrations of Fe(III) ranging from 250 to 1500 mg L⁻¹, were injected into column reactors packed with calcite grains at a constant flow rate. The composition of the solutions was monitored during the experiments. At the end of the experiments (passivation of the columns), the composition and structure of the solids were measured. The dissolution of calcite in the columns caused an increase in pH and the release of Ca into the solution, leading to the precipitation of gypsum and Fe–oxyhydroxysulfates (Fe(III)–SO₄–H⁺ solutions) or Fe–oxyhydroxychlorides (Fe(III)–Cl–H⁺ solutions). The columns worked as an efficient barrier for some time, increasing the pH of the circulating solutions from 2 to 6–7 and removing its metal content. However, after some time (several weeks, depending on the conditions), the columns became chemically inert. The results showed that passivation time increased with decreasing anion and metal content of the solutions. Gypsum was the phase responsible for the passivation of calcite in the experiments with Fe(III)–SO₄–H⁺ solutions. Schwertmannite and goethite appeared as the Fe(III) secondary phases in those experiments. Akaganeite was the phase responsible for the passivation of the system in the experiments with Fe(III)–Cl–H⁺ solutions.  相似文献   

Defect properties of albite     

Stephan Lowitzer  Dan J. Wilson  Björn Winkler  Victor Milman  Julian D. Gale 《Physics and Chemistry of Minerals》2008,35(3):129-135

Knowledge of the defect properties of Lunar and Mercurian minerals has recently become important, with the advent of models which attempt to explain the formation of the thin exosphere of these celestial bodies. Here, we have calculated the formation energies of sodium and oxygen vacancies in the mineral albite (NaAlSi₃O₈), as well as the Schottky defect energy for the removal of a Na₂O unit. We have employed both the supercell and Mott–Littleton approaches, using Kohn–Sham density functional theory and classical interatomic potential methods. As well as reporting the defect energies and structures, we comment upon the relative merits of the methods used.  相似文献   

Millennium-long recession of limestone facades in London     

Peter Brimblecombe  Carlota M. Grossi 《Environmental Geology》2008,56(3-4):463-471

Historical data on the temperature and precipitation data for London has been combined with output from the Hadley Model to estimate the climate of London for the period 1100–2100 CE. This has been converted to other parameters such as freeze–thaw frequency and snowfall relevant to the weathering of stone facades. The pollutant concentrations have been estimated for the same period, with the historical values taken from single box modelling and future values from changes likely given current policy within the metropolis. These values are used in the Lipfert model to show that the recession from karst weathering dominates across the period, while the contributions of sulphur deposition seem notable only across a shorter period 1700–2000 CE. Observations of the late seventeenth century suggest London architects witnessed a notable increase in the recession rate and attributed “fretting quality” to “smoaks of the sea-coal”. The recession rates measured in the late twentieth century lend some support to the estimates from the Lipfert model. The recession looks to increase only slightly, and frost shattering will decrease while salt weathering is likely to increase.  相似文献   

Flexural isostatic response of the Alps to increased Quaternary erosion recorded by foreland basin remnants,SE France     

Jean‐Daniel Champagnac  Peter Van Der Beek  Gaël Diraison  Samuel Dauphin 《地学学报》2008,20(3):213-220

We test the hypothesis that flexural isostatic compensation of the mass removed by enhanced Quaternary erosion is responsible for uplift of the Western European Alps and their forelands. We use two well‐preserved and well‐dated (1.8 Ma) abandonment surfaces of foreland basin remnants in SE France (the Chambaran and Valensole plateaux) as passive benchmarks for tilting of the foreland. Estimating their initial slope from morphometric scaling relationships, we determine bulk post‐depositional tilting of 0.5–0.8% for these surfaces. The calculated isostatic response of the Alpine lithosphere to erosional unloading, using the method recently proposed by Champagnac et al. [Geology 35 (2007) 195–198] , yields a predicted tilting of 0.3–0.4% in the considered areas, explaining approximately half of the determined post‐depositional tilting. Such long‐term deformation being insensitive to cyclic loading/unloading because of glaciations, we suspect the other half to be related to as yet undetermined long‐wavelength and long‐lived tectonic process(es).  相似文献   

The delay between solar activity and density changes in the upper atmosphere     

Peter W. Blum 《Planetary and Space Science》1968,16(12):1427-1440

Since 1958 it is known that there exists a response time of the upper atmosphere to changes in solar activity. This response time is best described as the lag between the 27-day variation of solar decimeter flux and the observed density changes of the upper atmosphere. Roemer obtained as a mean observational value for this lag 1.0 ± 0.12 days. Volland's simplified version of the Harris-Priester model of the upper atmosphere is used to calculate the delay which can be expected from theory. Only the effect of solar EUV radiation is taken into account. A possible influence of the corpuscular component of the solar radiation is not included in our estimate.

The calculations are carried out for the Harris-Priester model with solar activity index and a variation of . The resulting delay is 0.6 days. The calculated amplitude of the variations of the diurnal average temperatures during the solar 27-days cycle is in very good agreement with Jacchia's empirical formula.  相似文献