Association of dissolved aluminum with silica: Connecting molecular structure to surface reactivity using NMR     

J.R. Houston  J.L. Herberg  S.A. Carroll 《Geochimica et cosmochimica acta》2008,72(14):3326-3337

We studied uptake mechanisms for dissolved Al on amorphous silica by combining bulk-solution chemistry experiments with solid-state Nuclear Magnetic Resonance techniques (²⁷Al magic-angle spinning (MAS) NMR, ²⁷Al{¹H} cross-polarization (CP) MAS NMR and ²⁹Si{¹H} CP-MAS NMR). We find that reaction of Al (1 mM) with amorphous silica consists of at least three reaction pathways; (1) adsorption of Al to surface silanol sites, (2) surface-enhanced precipitation of an aluminum hydroxide, and (3) bulk precipitation of an aluminosilicate phase. From the NMR speciation and water chemistry data, we calculate that 0.20 (±0.04) tetrahedral Al atoms nm⁻² sorb to the silica surface. Once the surface has sorbed roughly half of the total dissolved Al (∼8% site coverage), aluminum hydroxides and aluminosilicates precipitate from solution. These precipitation reactions are dependent upon solution pH and total dissolved silica concentration. We find that the Si:Al stoichiometry of the aluminosilicate precipitate is roughly 1:1 and suggest a chemical formula of NaAlSiO₄ in which Na⁺ acts as the charge compensating cation. For the adsorption of Al, we propose a surface-controlled reaction mechanism where Al sorbs as an inner-sphere coordination complex at the silica surface. Analogous to the hydrolysis of , we suggest that rapid deprotonation by surface hydroxyls followed by dehydration of ligated waters results in four-coordinate (>SiOH)₂Al(OH)₂ sites at the surface of amorphous silica.  相似文献   

Borehole diffusive flux apparatus for characterizing diffusive mass-transfer in subsurface systems     

Mark L. Brusseau  Kenneth C. Carroll  Zhilin Guo  Jon Mainhagu 《Environmental Earth Sciences》2018,77(18):648

The concept of the Borehole Diffusive Flux Apparatus (BDFA) is presented herein. The BDFA is an innovative apparatus designed to provide continuous direct access to an undisturbed column of sediment that can be monitored at multiple discrete vertical intervals to provide high-resolution characterization of local-scale mass transfer and attenuation. The conceptual basis and technical design of the device are presented, along with an example of borehole design and installation at a field site. Mathematical simulations are used to illustrate its application for two scenarios. The results of these simulations indicate that test periods of several weeks to a few months should be sufficient to obtain robust results. The device has the potential to improve our ability to characterize critical mass-transfer and attenuation processes and to quantify the associated rates. This information is key to the evaluation of remediation alternatives, for enhancing the accuracy of mathematical models, and to support more effective long-term management of large groundwater contaminant plumes present at many sites.  相似文献   

Sedimentary studies in the Shenandoah Valley of Virginia     

Dorothy Carroll 《International Journal of Earth Sciences》1955,43(2):383-384

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Chemical spots on the surface of the strongly magnetic Herbig Ae star HD 101412     

S. P. Jrvinen  S. Hubrig  M. Schller  I. Ilyin  T. A. Carroll  H. Korhonen 《Astronomische Nachrichten》2016,337(3):329-338

Due to the knowledge of the rotation period and the presence of a rather strong surface magnetic field, the sharp‐lined young Herbig Ae star HD 101412 with a rotation period of 42 d has become one of the most well‐studied targets among the Herbig Ae stars. High‐resolution HARPS polarimetric spectra of HD 101412 were recently obtained on seven different epochs. Our study of the spectral variability over the part of the rotation cycle covered by HARPS observations reveals that the line profiles of the elements Mg, Si, Ca, Ti, Cr, Mn, Fe, and Sr are clearly variable while He exhibits variability that is opposite to the behaviour of the other elements studied. Since classical Ap stars usually show a relationship between the magnetic field geometry and the distribution of element spots, we used in our magnetic field measurements different line samples belonging to the three elements with the most numerous spectral lines, Ti, Cr, and Fe. Over the time interval covered by the available spectra, the longitudinal magnetic field changes sign from negative to positive polarity. The distribution of field values obtained using Ti, Cr, and Fe lines is, however, completely different compared to the magnetic field values determined in previous low‐resolution FORS 2 measurements, where hydrogen Balmer lines are the main contributors to the magnetic field measurements, indicating the presence of concentration of the studied iron‐peak elements in the region of the magnetic equator. Further, we discuss the potential role of contamination by the surrounding warm circumstellar matter in the appearance of Zeeman features obtained using Ti lines. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)  相似文献   

JHK observations of faint standard stars in the Mauna Kea Observatories near-infrared photometric system     

S. K. Leggett  M. J. Currie  W. P. Varricatt  T. G. Hawarden  A. J. Adamson  J. Buckle  T. Carroll  J. K. Davies  C. J. Davis  T. H. Kerr  O. P. Kuhn  M. S. Seigar  T. Wold 《Monthly notices of the Royal Astronomical Society》2006,373(2):781-792

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Towards a theory of targeting     

John P. Blair  Michael C. Carroll 《Applied geography (Sevenoaks, England)》2012,32(1):61-65

A representative economic model is used to analyze local policies to reestablish full employment. It addresses three types of barriers: 1. Rigid wages, 2. Occupational (or industrial) immobility, and 3. Geographic immobility. These factors are considered in the framework of three types of policies: 1. Laissez-faire, 2. Narrowly targeted employment incentives, and 3. Broadly targeted incentives. The paper concludes that the usefulness of the abstract model will depends upon the ability of local development officials to combine the implications of the model with information about the local economic development narrative. In turn, the narrative depends upon an in-depth local knowledge of history, institutions, practices and personalities.  相似文献   

Adsorption kinetics of CO2, CH4, and their equimolar mixture on coal from the Black Warrior Basin,West-Central Alabama     

M.S. Gruszkiewicz  M.T. Naney  J.G. Blencoe  D.R. Cole  J.C. Pashin  R.E. Carroll 《International Journal of Coal Geology》2009,77(1-2):23-33

Laboratory experiments were conducted to investigate the adsorption kinetic behavior of pure and mixed gases (CO_2, CH₄, approximately equimolar CO₂ + CH₄ mixtures, and He) on a coal sample obtained from the Black Warrior Basin at the Littleton Mine (Twin Pine Coal Company), Jefferson County, west-central Alabama. The sample was from the Mary Lee coal zone of the Pottsville Formation (Lower Pennsylvanian). Experiments with three size fractions (45–150 µm, 1–2 mm, and 5–10 mm) of crushed coal were performed at 40 °C and 35 °C over a pressure range of 1.4–6.9 MPa to simulate coalbed methane reservoir conditions in the Black Warrior Basin and provide data relevant for enhanced coalbed methane recovery operations. The following key observations were made: (1) CO₂ adsorption on both dry and water-saturated coal is much more rapid than CH₄ adsorption; (2) water saturation decreases the rates of CO₂ and CH₄ adsorption on coal surfaces, but it appears to have minimal effects on the final magnitude of CO₂ or CH₄ adsorption if the coal is not previously exposed to CO₂; (3) retention of adsorbed CO₂ on coal surfaces is significant even with extreme pressure cycling; and (4) adsorption is significantly faster for the 45–150 μm size fraction compared to the two coarser fractions.  相似文献   

Effect of solution saturation state and temperature on diopside dissolution     

Suvasis Dixit  Susan A Carroll 《Geochemical transactions》2007,8(1):1-14

Steady-state dissolution rates of diopside are measured as a function of solution saturation state using a titanium flow-through reactor at pH 7.5 and temperature ranging from 125 to 175°C. Diopside dissolved stoichiometrically under all experimental conditions and rates were not dependent on sample history. At each temperature, rates continuously decreased by two orders of magnitude as equilibrium was approached and did not exhibit a dissolution plateau of constant rates at high degrees of undersaturation. The variation of diopside dissolution rates with solution saturation can be described equally well with a ion exchange model based on transition state theory or pit nucleation model based on crystal growth/dissolution theory from 125 to 175°C. At 175°C, both models over predict dissolution rates by two orders of magnitude indicating that a secondary phase precipitated in the experiments. The ion exchange model assumes the formation of a Si-rich, Mg-deficient precursor complex. Lack of dependence of rates on steady-state aqueous calcium concentration supports the formation of such a complex, which is formed by exchange of protons for magnesium ions at the surface. Fit to the experimental data yields where the Mg-H exchange coefficient, n = 1.39, the apparent activation energy, E _a = 332 kJ mol^-1, and the apparent rate constant, k = 10^41.2 mol diopside cm^-2 s^-1. Fits to the data with the pit nucleation model suggest that diopside dissolution proceeds through retreat of steps developed by nucleation of pits created homogeneously at the mineral surface or at defect sites, where homogeneous nucleation occurs at lower degrees of saturation than defect-assisted nucleation. Rate expressions for each mechanism (i) were fit to where the step edge energy (α) for homogeneously nucleated pits were higher (275 to 65 mJ m^-2) than the pits nucleated at defects (39 to 65 mJ m^-2) and the activation energy associated with the temperature dependence of site density and the kinetic coefficient for homogeneously nucleated pits (E_{b-homogeneous} = 2.59 × 10^-16 mJ K^-1) were lower than the pits nucleated at defects (E_{b-defect assisted} = 8.44 × 10^-16 mJ K^-1).  相似文献   

An Analysis Platform for Multiscale Hydrogeologic Modeling with Emphasis on Hybrid Multiscale Methods          下载免费PDF全文

Timothy D. Scheibe  Ellyn M. Murphy  Xingyuan Chen  Amy K. Rice  Kenneth C. Carroll  Bruce J. Palmer  Alexandre M. Tartakovsky  Ilenia Battiato  Brian D. Wood 《Ground water》2015,53(1):38-56

One of the most significant challenges faced by hydrogeologic modelers is the disparity between the spatial and temporal scales at which fundamental flow, transport, and reaction processes can best be understood and quantified (e.g., microscopic to pore scales and seconds to days) and at which practical model predictions are needed (e.g., plume to aquifer scales and years to centuries). While the multiscale nature of hydrogeologic problems is widely recognized, technological limitations in computation and characterization restrict most practical modeling efforts to fairly coarse representations of heterogeneous properties and processes. For some modern problems, the necessary level of simplification is such that model parameters may lose physical meaning and model predictive ability is questionable for any conditions other than those to which the model was calibrated. Recently, there has been broad interest across a wide range of scientific and engineering disciplines in simulation approaches that more rigorously account for the multiscale nature of systems of interest. In this article, we review a number of such approaches and propose a classification scheme for defining different types of multiscale simulation methods and those classes of problems to which they are most applicable. Our classification scheme is presented in terms of a flowchart (Multiscale Analysis Platform), and defines several different motifs of multiscale simulation. Within each motif, the member methods are reviewed and example applications are discussed. We focus attention on hybrid multiscale methods, in which two or more models with different physics described at fundamentally different scales are directly coupled within a single simulation. Very recently these methods have begun to be applied to groundwater flow and transport simulations, and we discuss these applications in the context of our classification scheme. As computational and characterization capabilities continue to improve, we envision that hybrid multiscale modeling will become more common and also a viable alternative to conventional single‐scale models in the near future.  相似文献   

A Paddock to reef monitoring and modelling framework for the Great Barrier Reef: Paddock and catchment component     

Carroll C  Waters D  Vardy S  Silburn DM  Attard S  Thorburn PJ  Davis AM  Halpin N  Schmidt M  Wilson B  Clark A 《Marine pollution bulletin》2012,65(4-9):136-149

Targets for improvements in water quality entering the Great Barrier Reef (GBR) have been set through the Reef Water Quality Protection Plan (Reef Plan). To measure and report on progress towards the targets set a program has been established that combines monitoring and modelling at paddock through to catchment and reef scales; the Paddock to Reef Integrated Monitoring, Modelling and Reporting Program (Paddock to Reef Program). This program aims to provide evidence of links between land management activities, water quality and reef health. Five lines of evidence are used: the effectiveness of management practices to improve water quality; the prevalence of management practice adoption and change in catchment indicators; long-term monitoring of catchment water quality; paddock & catchment modelling to provide a relative assessment of progress towards meeting targets; and finally marine monitoring of GBR water quality and reef ecosystem health. This paper outlines the first four lines of evidence.  相似文献