scholarly journals A Statistical Approach for Analysis of Dissolution Rates Including Surface Morphology

Minerals ◽  
2019 ◽  
Vol 9 (8) ◽  
pp. 458 ◽  
Author(s):  
Elisabete Trindade Pedrosa ◽  
Inna Kurganskaya ◽  
Cornelius Fischer ◽  
Andreas Luttge
Keyword(s):  
Mineral Dissolution ◽  
Etch Pits ◽  
Dissolution Rates ◽  
Calcite Dissolution ◽  
Crystal Dissolution ◽  
Vertical Scanning Interferometry ◽  
Surface Morphologies ◽  
Micrometer Scale ◽  
Flow Experiments

Understanding mineral dissolution is relevant for natural and industrial processes that involve the interaction of crystalline solids and fluids. The dissolution of slow dissolving minerals is typically surface controlled as opposed to diffusion/transport controlled. At these conditions, the dissolution rate is no longer constant in time or space, an outcome observed in rate maps and correspondent rate spectra. The contribution and statistical prevalence of different dissolution mechanisms is not known. Aiming to contribute to close this gap, we present a statistical analysis of the variability of calcite dissolution rates at the nano- to micrometer scale. A calcite-cemented sandstone was used to perform flow experiments. Dissolution of the calcite-filled rock pores was measured using vertical scanning interferometry. The resultant types of surface morphologies influenced the outcome of dissolution. We provide a statistical description of these morphologies and show their temporal evolution as an alternative to the lack of rate spatial variability in rate constants. Crystal size impacts dissolution rates most probably due to the contribution of the crystal edges. We propose a new methodology to analyze the highest rates (tales of rate spectra) that represent the formation of deeper etch pits. These results have application to the parametrization and upscaling of geochemical kinetic models, the characterization of industrial solid materials and the fundamental understanding of crystal dissolution.

Etch pit distribution on calcite cleavage surfaces – experiments and simulation

2020 ◽  
Author(s):  
Ricarda D. Rohlfs ◽  
Elisabete Trindade Pedrosa ◽  
Inna Kurganskaya ◽  
Cornelius Fischer ◽  
Andreas Luttge
Keyword(s):  
Spatial Distribution ◽  
Kinetic Monte Carlo ◽  
Pure Water ◽  
Heterogeneous Material ◽  
Driving Mechanism ◽  
Etch Pits ◽  
Surface Evolution ◽  
Crystal Dissolution ◽  
Etch Pit ◽  
Vertical Scanning Interferometry

<p>During the dissolution at a calcite cleavage face, etch pits open around defects. Atomic steps moving outwards from these pit centres are currently considered the general driving mechanism of this dissolution process that results in heterogeneous material flux from the surface. This means that the defects that generate the etch pits are crucial for the surface evolution. Recent kinetic Monte Carlo (kMC) simulation results indicate that not only the density but also the spatial distribution of defects is critical for the influence on dissolution.</p><p>In kMC simulations used for crystal dissolution, defect positions are input and can be defined in various ways, e.g., at pre-defined coordinates or randomly drawn from a distribution. The user is free in defining the defects, although it can generally be considered reasonable to choose defect densities and distributions as close as possible to what is expected to occur in nature and technical systems.</p><p>The actual spatial distribution of screw dislocations in calcite and their influence on rate variability are still not entirely known. To make the calcite kMC simulations comparable with experimental results, we experimentally determined the etch pit distributions, analyzed them and subsequently used them as input for further kMC studies.</p><p>While the direct measurement of defects in the crystal structure is extremely difficult, the indirect approach of measuring etch pits that have formed around defect outcrops during the beginning of dissolution is more feasible. For this, cleaved calcite single crystals were etched using ultra-pure water for 3 to 4 hours to obtain a significant amount of etch pits on the surface. The topography of the crystal surfaces was analysed using Vertical Scanning Interferometry (VSI). The resulting topography maps were stitched to gain a larger area for better statistics, and the centres of visible etch pits marked. This generates two-dimensional point patterns that describe the actual defect distribution more accurately than purely randomly generated coordinates without further constraints.</p><p>Based on data analysis of the experiments, we will show the resulting point distributions and synthetic patterns with similar underlying statistics. Using these as input for modelling, we then calculate kMC simulations and geometrical models of a system close to the calcite single crystal from our experiment, and compare them also to simulations using different defect positions as input.</p>

scholarly journals Direct Observation of Microbial Inhibition of Calcite Dissolution

2004 ◽  
Vol 70 (3) ◽  
pp. 1627-1632 ◽  
Author(s):  
Andreas L�ttge ◽  
Pamela G. Conrad
Keyword(s):  
Crystal Surface ◽  
Shewanella Oneidensis ◽  
High Energy ◽  
Significant Inhibition ◽  
Mineral Dissolution ◽  
Experimental Methodology ◽  
Dissolution Behavior ◽  
Bacterial Cells ◽  
Etch Pits ◽  
Calcite Dissolution

ABSTRACT Vertical scanning interferometry (VSI) provides a method for quantification of surface topography at the angstrom to nanometer level. Time-dependent VSI measurements can be used to study the surface-normal retreat across crystal and other solid surfaces during dissolution or corrosion processes. Therefore, VSI can be used to directly and nondestructively measure mineral dissolution rates with high precision. We have used this method to compare the abiotic dissolution behavior of a representative calcite (CaCO3) cleavage face with that observed upon addition of an environmental microbe, Shewanella oneidensis MR-1, to the crystal surface. From our direct observations, we have concluded that the presence of the microbes results in a significant inhibition of the rate of calcite dissolution. This inhibition appears to be a 2nd-order effect that is related to the formation of etch pits. The opening of etch pits was greatly inhibited in the presence of added bacteria, suggesting that the bacterial cells exert their effect by inhibiting the formation of etch pits at high-energy sites at the crystal surface caused by lattice defects, e.g., screw or point dislocations. The experimental methodology thus provides a nondestructive, directly quantifiable, and easily visualized view of the interactions of microbes and minerals during weathering (or corrosion) processes or during mineral precipitation.

Assessing the Effect of Dissolved Organic Ligands on Mineral Dissolution Rates: an Example from Calcite Dissolution

1996 ◽  
Vol 465 ◽  
Author(s):  
Teri DeMaio ◽  
D. E. Grandstaff
Keyword(s):  
Dissolution Rate ◽  
Organic Ligand ◽  
Mineral Dissolution ◽  
Organic Ligands ◽  
Dissolution Rates ◽  
Surface Complexes ◽  
Calcite Dissolution ◽  
Low Concentrations ◽  
Rate Versus ◽  
Metal Ligand

ABSTRACTExperiments suggest that dissolved organic ligands may primarily modify mineral dissolution rates by three mechanisms: (1) metal-ligand (M-L) complex formation in solution, which increases the degree of undersaturation, (2) formation of surface M-L complexes that attack the surface, and (3) formation of surface complexes which passivate or “protect” the surface. Mechanisms (1) and (2) increase the dissolution rate and the third decreases it compared with organic-free solutions. The types and importance of these mechanisms may be assessed from plots of dissolution rate versus degree of undersaturation.To illustrate this technique, calcite, a common repository cementing and vein-filling mineral, was dissolved at pH 7.8 and 22°C in Na-Ca-HCO3-Cl solutions with low concentrations of three organic ligands. Low citrate concentrations (50 μm) increased the dissolution rate consistent with mechanism (1). Oxalate decreased the rate, consistent with mechanism (3). Low phthalate concentration (< 50 μM) decreased calcite dissolution rates; however, higher concentrations increased the dissolution rates, which became faster than in inorganic solutions. Thus, phthalate exhibits both mechanisms (2) and (3) at different concentrations. In such cases linear extrapolations of dissolution rates from high organic ligand concentrations may not be valid.

scholarly journals Demonstration of an integrated nanophotonic chip-scale alkali vapor magnetometer using inverse design

2021 ◽  
Vol 10 (1) ◽  
Author(s):  
Yoel Sebbag ◽  
Eliran Talker ◽  
Alex Naiman ◽  
Yefim Barash ◽  
Uriel Levy
Keyword(s):  
Spatial Resolution ◽  
Near Field ◽  
Computer Assisted ◽  
Experimental Characterization ◽  
Optical Isolation ◽  
New Concepts ◽  
On Chip ◽  
The Cost ◽  
Micrometer Scale

AbstractRecently, there has been growing interest in the miniaturization and integration of atomic-based quantum technologies. In addition to the obvious advantages brought by such integration in facilitating mass production, reducing the footprint, and reducing the cost, the flexibility offered by on-chip integration enables the development of new concepts and capabilities. In particular, recent advanced techniques based on computer-assisted optimization algorithms enable the development of newly engineered photonic structures with unconventional functionalities. Taking this concept further, we hereby demonstrate the design, fabrication, and experimental characterization of an integrated nanophotonic-atomic chip magnetometer based on alkali vapor with a micrometer-scale spatial resolution and a magnetic sensitivity of 700 pT/√Hz. The presented platform paves the way for future applications using integrated photonic–atomic chips, including high-spatial-resolution magnetometry, near-field vectorial imaging, magnetically induced switching, and optical isolation.

Characterization of fibroblast morphology on bioactive surfaces using vertical scanning interferometry

2006 ◽  
Vol 25 (8) ◽  
pp. 523-533 ◽  
Author(s):  
Christopher M. Revell ◽  
Jeffrey A. Dietrich ◽  
C. Corey Scott ◽  
Andreas Luttge ◽  
L. Scott Baggett ◽  
...  
Keyword(s):  
Bioactive Surfaces ◽  
Vertical Scanning Interferometry

Precision Coating of ta-C Films on Quartz Surfaces

2020 ◽  
Author(s):  
Kotaro Kawai ◽  
Yuki Hirata ◽  
Hiroki Akasaka ◽  
Naoto Ohtake
Keyword(s):  
Cutting Tools ◽  
Three Dimensional ◽  
High Hardness ◽  
Carbon Films ◽  
Vacuum Arc ◽  
High Wear Resistance ◽  
Chemical Inertness ◽  
Filtered Cathodic Vacuum Arc ◽  
Surface Morphologies

Abstract Diamond-like carbon (DLC) films have excellent properties such as high hardness, low friction coefficient, high wear resistance, chemical inertness and so on. Because DLC film is considered as an effective coating material to improve their surface properties, this films are used in various applications such as parts for automobiles engines, hard disk surfaces, cutting tools and dies, and so on. DLC films consist of a mixture of sp2 bonded carbon atoms and sp3 bonded carbon atoms. Among them, ta-C film is known as the hardest and strongest film since it mainly consists of sp3 bonded carbon atoms. One of deposition methods to form ta-C is Filtered Cathodic Vacuum Arc (FCVA). The characteristic of this method is that it is possible to remove the droplets and form a high-quality film.. However, even though lots of mechanical components which require ta-C coating have three-dimensionally shapes, it is difficult to coat ta-C film three dimensionally by using FCVA process. At present, researches on 3D deposition of amorphous carbon films on three dimensional components is still insufficient, and investigation reports on the deposition mechanism and characterization of the deposited films are even more limited. In this study, we tried to deposit films on 3D components by the FCVA method and evaluated the microstructure and surface morphologies of films. Although films were coated successfully in the entire surfaces, different properties were showed depending on the location of components. These properties were investigated by Raman spectroscopy and laser microscope.

Micro-Scale Flow Simulations and Permeability Estimation of Cleat Networks in Coal

2016 ◽  
Vol 846 ◽  
pp. 42-47
Author(s):  
J. Busse ◽  
S. Galindo Torres ◽  
Alexander Scheuermann ◽  
L. Li ◽  
D. Bringemeier
Keyword(s):  
Gas Flow ◽  
Structural Information ◽  
Porous Matrix ◽  
Groundwater Levels ◽  
Micro Scale ◽  
Wide Range ◽  
Boltzmann Method ◽  
The Impact ◽  
Flow Experiments

Coal mining raises a number of environmental and operational challenges, including the impact of changing groundwater levels and flow patterns on adjacent aquifer and surface water systems. Therefore it is of paramount importance to fully understand the flow of water and gases in the geological system on all scales. Flow in coal seams takes place on a wide range of scales from large faults and fractures to the micro-structure of a porous matrix intersected by a characteristic cleat network. On the micro-scale these cleats provide the principal source of permeability for fluid and gas flow. Description of the behaviour of the flow within the network is challenging due to the variations in number, sizing, orientation, aperture and connectivity at a given site. This paper presents a methodology to simulate flow and investigate the permeability of fractured media. A profound characterization of the geometry of the cleat network in micrometer resolution can be derived by CT-scans. The structural information is fed into a Lattice Boltzmann Method (LBM) based model that allows the implementation of virtual flow experiments. With the application of suitable hydraulic boundary conditions the full permeability tensor can be calculated in 3D.

Latent disciplinal clashes concerning the batch dissolution of minerals, and their wider implications

2018 ◽  
Vol 15 (2) ◽  
pp. 113 ◽  
Author(s):  
Victor W. Truesdale ◽  
Jim Greenwood
Keyword(s):  
Large Scale ◽  
Dissolution Kinetics ◽  
Mineral Dissolution ◽  
Atomic Scale ◽  
Rate Equations ◽  
Silicate Mineral ◽  
Waste Products ◽  
Calcite Dissolution ◽  
Macro Scale ◽  
Made In

Environmental contextMineral dissolution kinetics are important to understand natural processes including those increasingly used to store waste carbon dioxide and highly radio-active nuclides, and those involved in the amelioration of climate change and sea-level rise. We highlight a mistake made in the fundamental science that has retarded progress in the field for over 40 years. Its removal suggests improved ways to approach dissolution studies. AbstractMineral dissolution kinetics are fundamental to biogeochemistry, and to the application of science to reduce the deleterious effects of humanity’s waste products, e.g. CO2 and radio-nuclides. However, a mistake made in the selection of the rate equation appropriate for use at the macro-scale of the aquatic environment has stymied growth in major aspects of the subject for some 40 years. This paper identifies the mistake, shows how it represents a latent disciplinal clash between two rate equations, and explores the misunderstandings that resulted from it. The paper also briefly explores other disciplinal clashes. Using the example of calcite dissolution, the paper also shows how the phenomenon of ‘non-ideal’ dissolution, which is prevalent in alumino-silicate mineral dissolution, as well as with calcite, has obscured the clash. The paper provides new information on plausible mechanisms, the absence of which has contributed to the problem. Finally, it argues that disciplinal clashes need to be minimised so that a rigorous description of dissolution at the large scale can be matched to findings at the atomic, or near-atomic, scale.

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