Thermoelectric Properties of Lanthanum Sulfide

NASA Technical Reports Server (NTRS)

Wood, C.; Lockwood, R.; Parker, J. B.; Zoltan, A.; Zoltan, L. D.; Danielson, L.; Raag, V.

1987-01-01

Report describes measurement of Seebeck coefficient, electrical resistivity, thermal conductivity, and Hall effect in gamma-phase lanthanum sulfide with composition of La3-x S4. Results of study, part of search for high-temperature thermoelectric energy-conversion materials, indicate this sulfide behaves like extrinsic semiconductor over temperature range of 300 to 1,400 K, with degenerate carrier concentration controlled by stoichiometric ratio of La to S.

Sulfur diffusion in dacitic melt at various oxidation states: Implications for volcanic degassing

NASA Astrophysics Data System (ADS)

Lierenfeld, Matthias Bernhard; Zajacz, Zoltán; Bachmann, Olivier; Ulmer, Peter

2018-04-01

The diffusivity of S in a hydrous dacitic melt (4.5-6.0 wt.% H2O) has been investigated in the temperature (T) and pressure (P) range of 950 °C to 1100 °C and 200 to 250 MPa, respectively. Three series of experiments were conducted at relatively low oxygen fugacity (fO2) conditions [0.8 log units below fayalite-magnetite-quartz equilibrium (FMQ -0.8); referred to as "low fO2"] and high fO2 conditions (FMQ +2.5; referred to as "high fO2") to determine if the diffusivity of S is affected by its oxidation state and speciation. Sulfur concentration profiles were measured by electron microprobe and the diffusion coefficient (D) was calculated by fitting these profiles. Sulfur diffusion is approximately one order of magnitude faster when S is dominantly present as sulfide species (low fO2) in comparison to the sulfate dominated experiments (high fO2). The following Arrhenian equations were obtained for high and low fO2 conditions at 200 MPa: high fO2: D = 10-5.92±0.86 * exp ({-137.3±21.5 kJ/mol}/{RT}) low fO2: D = 10-5.18±1.39 * exp ({-125.7±34.4 kJ/mol}/{RT}) where D is the average diffusion coefficient in m2 s-1, R is the gas constant in 8.3144 J mol-1 K-1 and T is the temperature in K. Our results demonstrate for the first time in natural melts that S diffusion is strongly sensitive to fO2. Our S diffusivities under low fO2 conditions are only slightly slower of those found for H2O, suggesting that S can be rather efficiently purged from reduced dacitic melts during volcanic eruptions. However, for more oxidized systems (e.g. subduction zones), S diffusion will be much slower and will hinder equilibrium syn-eruptive degassing during rapid decompression. Therefore, we conclude that the "excess" measured during many explosive volcanic eruptions in arcs is dominantly derived from S-rich bubble accumulation in the eruptible portion of the magma reservoir.

Partitioning of V, Mn, Co, Ni, Cu, Zn, As, Mo, Ag, Sn, Sb, W, Au, Pb, and Bi between sulfide phases and hydrous basanite melt at upper mantle conditions

NASA Astrophysics Data System (ADS)

Li, Yuan; Audétat, Andreas

2012-11-01

The partitioning of 15 major to trace metals between monosulfide solid solution (MSS), sulfide liquid (SL) and mafic silicate melt (SM) was determined in piston-cylinder experiments performed at 1175-1300 °C, 1.5-3.0 GPa and oxygen fugacities ranging from 3.1 log units below to 1.0 log units above the quartz-fayalite-magnetite fO2 buffer, which conditions are representative of partial melting in the upper mantle in different tectonic settings. The silicate melt was produced by partial melting of a natural, amphibole-rich mantle source rock, resulting in hydrous (˜5 wt% H2O) basanitic melts similar to low-degree partial melts of metasomatized mantle, whereas the major element composition of the starting sulfide (˜52 wt% Fe; 39 wt% S; 7 wt% Ni; 2 wt% Cu) was similar to the average composition of sulfides in this environment. SL/SM partition coefficients are high (≥100) for Au, Ni, Cu, Ag, Bi, intermediate (1-100) for Co, Pb, Sn, Sb (±As, Mo), and low (≤1) for the remaining elements. MSS/SM partition coefficients are generally lower than SL/SM partition coefficients and are high (≥100) for Ni, Cu, Au, intermediate (1-100) for Co, Ag (±Bi, Mo), and low (≤1) for the remaining elements. Most sulfide-silicate melt partition coefficients vary as a function of fO2, with Mo, Bi, As (±W) varying by a factor >10 over the investigated fO2 range, Sb, Ag, Sn (±V) varying by a factor of 3-10, and Pb, Cu, Ni, Co, Au, Zn, Mn varying by a factor of 3-10. The partitioning data were used to model the behavior of Cu, Au, Ag, and Bi during partial melting of upper mantle and during fractional crystallization of primitive MORB and arc magmas. Sulfide phase relationships and comparison of the modeling results with reported Cu, Au, Ag, and Bi concentrations from MORB and arc magmas suggest that: (i) MSS is the dominant sulfide in the source region of arc magmas, and thus that Au/Cu ratios in the silicate melt and residual sulfides may decrease with increasing degree of partial melting, (ii) both MSS and sulfide liquid are precipitated during fractional crystallization of MORB, and (iii) fractional crystallization of arc magmas is strongly dominated by MSS.

Biogeochemical cycling in an organic-rich coastal marine basin. 8. A sulfur isotopic budget balanced by differential diffusion across the sediment-water interface

USGS Publications Warehouse

Chanton, J.P.; Martens, C.S.; Goldhaber, M.B.

1987-01-01

The sulfur isotopic composition of the sulfur fluxes occurring in the anoxic marine sediments of Cape Lookout Bight, N.C., U.S.A., was determined, and the result of isotopic mass balance was obtained via the differential diffusion model. Seasonal pore water sulfate ??34S measurements yielded a calculated sulfate input of 0.6%.. Sulfate transported into the sediments via diffusion appeared to be enriched in the lighter isotope because its concentration gradient was steeper, due to the increase in the measured isotopic composition of sulfate with depth. Similarly, the back diffusion of dissolved sulfide towards the sediment-water interface appeared enriched in the heavier isotope. The isotopic composition of this flux was calculated from measurements of the ??34S of dissolved sulfide and was determined to be 15.9%.. The isotopic composition of buried sulfide was determined to be -5.2%. and the detrital sulfur input was estimated to be -6.2%.. An isotope mass balance equation based upon the fluxes at the sediment-water interface successfully predicted the isotopic composition of the buried sulfur flux within 0.5%., thus confirming that isotopes diffuse in response to their individual concentration gradients. ?? 1987.

Gallium-bearing sphalerite in a metal-sulfide nodule of the Qingzhen (EH3) chondrite

NASA Technical Reports Server (NTRS)

Rambaldi, E. R.; Rajan, R. S.; Housley, R. M.; Wang, D.

1986-01-01

The composition and possible history of the Qingshen (EH3) chondrite is presented. The chondrite contains a population of spheroidal metal-sulfide nodules, which display textural evidence of reheating and melting. Evidence of metal sulfuration is also present, suggesting replacement of metal by sulfide during melting. This process has led to the nucleation of perryite along metal-sulfide interfaces. The Ga-bearing sphalerite that was found may have formed by injection of molten sulfide droplets into the metal followed by subsolidus diffusion of Ga from the metal into the sulfide. The latter may occur because of Ga supersaturation in the metal during progressive sulfuration and its decreased affinity for the metal phase during cooling below the taenite-kamacite transition point.

Photo-induced Mass Transport through Polymer Networks

NASA Astrophysics Data System (ADS)

Meng, Yuan; Anthamatten, Mitchell

2014-03-01

Among adaptable materials, photo-responsive polymers are especially attractive as they allow for spatiotemporal stimuli and response. We have recently developed a macromolecular network capable of photo-induced mass transport of covalently bound species. The system comprises of crosslinked chains that form an elastic network and photosensitive fluorescent arms that become mobile upon irradiation. We form loosely crosslinked polymer networks by Michael-Addition between multifunctional thiols and small molecule containing acrylate end-groups. The arms are connected to the network by allyl sulfide, that undergoes addition-fragmentation chain transfer (AFCT) in the presence of free radicals, releasing diffusible fluorophore. The networks are loaded with photoinitiator to allow for spatial modulation of the AFCT reactions. FRAP experiments within bulk elastomers are conducted to establish correlations between the fluorophore's diffusion coefficient and experimental variables such as network architecture, temperature and UV intensity. Photo-induced mass transport between two contacted films is demonstrated, and release of fluorophore into a solvent is investigated. Spatial and temporal control of mass transport could benefit drug release, printing, and sensing applications.

Synthesis and characterization of MoS2/Ti composite coatings on Ti6Al4V prepared by laser cladding

NASA Astrophysics Data System (ADS)

Yang, Rongjuan; Liu, Zongde; Wang, Yongtian; Yang, Guang; Li, Hongchuan

2013-02-01

The MoS2/Ti composite coating with sub-micron grade structure has been prepared on Ti6Al4V by laser method under argon protection. The morphology, microstructure, microhardness and friction coefficient of the coating were examined. The results indicated that the molybdenum disulfide was decomposed during melting and resolidification. The phase organization of composite coating mainly consisted of ternary element sulfides, molybdenum sulfides and titanium sulfides. The friction coefficient of and the surface roughness the MoS2/Ti coating were lower than those of Ti6Al4V. The composite coating exhibits excellent adhesion to the substrates, less surface roughness, good wear resistance and harder surface.

Layered Compounds and Intercalation Chemistry: An Example of Chemistry and Diffusion in Solids.

ERIC Educational Resources Information Center

Whittingham, M. Stanley; Chianelli, Russell R.

1980-01-01

Considers a few areas of oxide/sulfide and intercalation-type chemistry. Discusses synthesis of the disulfides of the metals of group IVB, VB, and VIB; the intercalation reaction between lithium and titanium disulfide; other intercalates; and sulfide catalysts. (CS)

Influence of acid volatile sulfides and metal concentrations on metal partitioning in contaminated sediments

USGS Publications Warehouse

Lee, J.-S.; Lee, B.-G.; Luoma, S.N.; Choi, H.J.; Koh, C.-H.; Brown, C.L.

2000-01-01

The influence of acid volatile sulfide (AVS) on the partitioning of Cd, Ni, and Zn in porewater (PW) and sediment as reactive metals (SEM, simultaneously extracted metals) was investigated in laboratory microcosms. Two spiking procedures were compared, and the effects of vertical geochemical gradients and infaunal activity were evaluated. Sediments were spiked with a Cd-Ni-Zn mixture (0.06, 3, 7.5 ??mol/g, respectively) containing four levels of AVS (0.5, 7.5, 15, 35 ??mol/g). The results were compared to sediments spiked with four levels of Cd-Ni-Zn mixtures at one AVS concentration (7.5 ??mol/g). A vertical redox gradient was generated in each treatment by an 18-d incubation with an oxidized water column. [AVS] in the surface sediments decreased by 65-95% due to oxidation during incubation; initial [AVS] was maintained at 0.5-7.5 cm depth. PW metal concentrations were correlated with [SEM - AVS] among all data. But PW metal concentrations were variable, causing the distribution coefficient, Kd(pw) (the ratio of [SEM] to PW metal concentrations) to vary by 2-3 orders of magnitude at a given [SEM - AVS]. One reason for the variability was that vertical profiles in PW metal concentrations appeared to be influenced by diffusion as well as [SEM - AVS]. The presence of animals appeared to enhance the diffusion of at least Zn. The generalization that PW metal concentrations are controlled by [SEM - AVS] is subject to some important qualifications if vertical gradients are complicated, metal concentrations vary, or equilibration times differ.The influence of acid volatile sulfide (AVS) on the partitioning of Cd, Ni, and Zn in porewater (PW) and sediment as reactive metals (SEM, simultaneously extracted metals) was investigated in laboratory microcosms. Two spiking procedures were compared, and the effects of vertical geochemical gradients and infaunal activity were evaluated. Sediments were spiked with a Cd-Ni-Zn mixture (0.06, 3, 7.5 ??mol/g, respectively) containing four levels of AVS (0.5, 7.5, 15, 35 ??mol/g). The results were compared to sediments spiked with four levels of Cd-Ni-Zn mixtures at one AVS concentration (7.5 ??mol/g). A vertical redox gradient was generated in each treatment by an 18-d incubation with an oxidized water column. [AVS] in the surface sediments decreased by 65-95% due to oxidation during incubation; initial [AVS] was maintained at 0.5-7.5 cm depth. PW metal concentrations were correlated with [SEM - AVS] among all data. But PW metal concentrations were variable, causing the distribution coefficient, Kdpw (the ratio of [SEM] to PW metal concentrations) to vary by 2-3 orders of magnitude at a given [SEM - AVS]. One reason for the variability was that vertical profiles in PW metal concentrations appeared to be influenced by diffusion as well as [SEM - AVS]. The presence of animals appeared to enhance the diffusion of at least Zn. The generalization that PW metal concentrations are controlled by [SEM - AVS] is subject to some important qualifications if vertical gradients are complicated, metal concentrations vary, or equilibration times differ.

Solubility of copper in silicate melts as function of oxygen and sulfur fugacities, temperature, and silicate composition

NASA Astrophysics Data System (ADS)

Holzheid, A.; Lodders, K.

2001-06-01

The solubility of Cu in silicate melts coexisting with liquid Cu(Fe) metal and liquid Cu(Fe) sulfide was determined experimentally at oxygen fugacities ranging from 10 -9.1 to 10 -13.6 bar and sulfur fugacities ranging from 10 -2.5 to 10 -6.3 bar at 1300°C. An iron oxide-free silicate of anorthite-diopside eutectic composition and a synthetic MgO-rich basaltic silicate (FeO-bearing) were used in the partitioning experiments. In S-containing systems, some of the metal reacted to metal sulfide. The silicates in the four systems investigated (Fe-free and S-free; Fe-containing and S-free; Fe-free and S-containing; Fe-containing and S-containing) had different colors depending on the dissolved Cu species and the presence of iron and/or sulfur. Irrespective of the presence of sulfur, the solubility of Cu in the silicate increases with increasing oxygen fugacity and metal/silicate partition coefficients for Cu decrease. Increasing the temperature from 1300°C to 1514°C increases the Cu solubility (decreases the metal/silicate partition coefficient) at an oxygen fugacity 0.5 log units below the iron-wüstite (IW) equilibrium in the Fe-free, S-free and Fe-containing, S-free systems. We infer the presence of monovalent Cu + ("CuO 0.5") in the silicate melt on the basis of the solubility of Cu as function of oxygen fugacity. Experiments containing iron yield a formal valence of ˜0.5 for Cu at very low oxygen fugacities, which is not observed in Fe-free systems. The low formal valence is explained by redox reactions between iron and copper in the silicate melts. There is no evidence for sulfidic dissolution of Cu in the silicates but sulfur has indirect effects on Cu partitioning. Iron metal/silicate partition coefficients depend on oxygen fugacity and on sulfur fugacity. Sulfidic dissolution of iron and oxide-sulfide exchange reactions with Cu cause a small increase in Cu metal/silicate partition coefficients. We derive an activity coefficient (γ CuO 0.5) of 10 ± 1 for liquid CuO 0.5 at 1300°C for the silicate melts used here. A comparison with literature data shows that log γ CuO 0.5 increases in proportion to the mass percentages [CaO +(Al 2O 3)/2] in silicate melts. We recommend the following equations for Cu metal/silicate and sulfide/silicate partitioning for geochemical and cosmochemical modeling if silicate composition and the activity of Cu in the metal or sulfide is known: log D met/sil = -0.48 - 0.25 · log fO 2 - log γ Cu metal + 0.02 · [CaO + (Al 2O 3)/2; wt%] silicate logD sul/sil=+0.76-0.25 · logfO 2+0.25logfS 2-logγ CS 0.5,sulfide +0.02 · [CaO+Al 2O 3/2;wt%] silicate. The derived Cu metal/silicate and metal/sulfide partition coefficients are applied to core formation in the Earth and Mars. The observed Cu abundances in the Earth cannot be easily explained by simple core-mantle equilibrium, but the observed Cu abundances for Mars are consistent with core-mantle equilibrium at low pressure and temperatures.

Sub-seafloor Processes and the Composition of Diffuse Hydrothermal Fluids

NASA Astrophysics Data System (ADS)

Butterfield, D. A.; Lilley, M. D.; Huber, J. A.; Baross, J. A.

2002-12-01

High-temperature water/rock reactions create the primary hydrothermal fluids that are diluted with cool, "crustal seawater" to produce low-temperature, diffuse hydrothermal vent fluids. By knowing the composition of each of the components that combine to produce diffuse fluids, one can compare the composition of calculated mixtures with the composition of sampled fluids, and thereby infer what chemical constituents have been affected by processes other than simple conservative mixing. Although there is always uncertainty in the composition of fluids from the sub-seafloor, some processes are significant enough to alter diffuse fluid compositions from the expected conservative mixtures of hot,primary fluid and "crustal seawater." When hydrothermal vents with a wide range of temperature are sampled, processes occurring in different thermal and chemical environments potentially can be discerned. At Axial Volcano (AV) on the Juan de Fuca ridge, methane clearly is produced in warm sub-seafloor environments at temperatures of ~ 100° or less. Based on culturing and phylogenetic analysis from the same water samples at AV, hyperthermophilic methanogens are present in water samples taken from vents ranging in temperature from 15 to 78° C. Ratios of hydrogen sulfide to pseudo-conservative tracers (dissolved silica or heat) at AV decrease when primary fluids are highly diluted with oxygenated seawater. Phylogenetic signatures of microbes closely related to sulfide-oxidizers are present in these same fluids. Hydrogen sulfide oxidation represents the dominant source of energy for chemosynthesis at AV, as in most hydrothermal systems, but a relatively small proportion of the total hydrogen sulfide available is actually oxidized, except at the very lowest temperatures.

Multifunctional reference electrode

DOEpatents

Redey, Laszlo; Vissers, Donald R.

1983-01-01

A multifunctional, low mass reference electrode of a nickel tube, thermocouple means inside the nickel tube electrically insulated therefrom for measuring the temperature thereof, a housing surrounding the nickel tube, an electrolyte having a fixed sulfide ion activity between the housing and the outer surface of the nickel tube forming the nickel/nickel sulfide/sulfide half-cell. An ion diffusion barrier is associated with the housing in contact with the electrolyte. Also disclosed is a cell using the reference electrode to measure characteristics of a working electrode.

Multifunctional reference electrode

DOEpatents

Redey, L.; Vissers, D.R.

1981-12-30

A multifunctional, low mass reference electrode of a nickel tube, thermocouple means inside the nickel tube electrically insulated therefrom for measuring the temperature thereof, a housing surrounding the nickel tube, an electrolyte having a fixed sulfide ion activity between the housing and the outer surface of the nickel tube forming the nickel/nickel sulfide/sulfide half-cell are described. An ion diffusion barrier is associated with the housing in contact with the electrolyte. Also disclosed is a cell using the reference electrode to measure characteristics of a working electrode.

Influence of sulfides on the tribological properties of composites produced by pulse electric current sintering

NASA Astrophysics Data System (ADS)

Kim, Seung Ho

2014-01-01

Self-lubricating Al2O3-15wt% ZrO2 composites with sulfides, such as molybdenum disulfide (MoS2) and tungsten disulfide (WS2) serving as solid lubricants, were fabricated by using the pulse electric current sintering (PECS) technique. The coefficient of friction (COF) of the Al2O3-15wt% ZrO2 composite without/with sulfides was in the range of 0.37-0.48 and 0.27-0.49, respectively. As the amount of sulfides increased, the COF and the wear rate decreased. The reduction in COF and wear rate of the sulfide-containing composite is caused by a reduction in shear stresses between the specimen and the tribological medium due to the formation of a lubricating film resulting from the lamellar structure of sulfides located on the worn surface.

Effect of concentration dependence of the diffusion coefficient on homogenization kinetics in multiphase binary alloy systems

NASA Technical Reports Server (NTRS)

Tenney, D. R.; Unnam, J.

1978-01-01

Diffusion calculations were performed to establish the conditions under which concentration dependence of the diffusion coefficient was important in single, two, and three phase binary alloy systems. Finite-difference solutions were obtained for each type of system using diffusion coefficient variations typical of those observed in real alloy systems. Solutions were also obtained using average diffusion coefficients determined by taking a logarithmic average of each diffusion coefficient variation considered. The constant diffusion coefficient solutions were used as reference in assessing diffusion coefficient variation effects. Calculations were performed for planar, cylindrical, and spherical geometries in order to compare the effect of diffusion coefficient variations with the effect of interface geometries. In most of the cases considered, the diffusion coefficient of the major-alloy phase was the key parameter that controlled the kinetics of interdiffusion.

Influence of Oxygen on Cu Distribution Behavior Between Molten Iron and FeS-Based Flux

NASA Astrophysics Data System (ADS)

Kang, Youngjo; Shin, Kil-Sun; Morita, Kazuki

2018-06-01

Cu distribution behavior between molten iron and a sulfide flux was investigated under different oxygen contents in the sulfide flux to clarify the effect of oxygen content in FeS-based flux on Cu removal. The activity coefficient of CuS0.5 could be experimentally estimated according to the oxygen content. Based on the present result, the possibility of Cu removal by sulfide flux containing a certain amount of oxide was discussed.

Influence of dissolved organic matter on the complexation of mercury under sulfidic conditions.

PubMed

Miller, Carrie L; Mason, Robert P; Gilmour, Cynthia C; Heyes, Andrew

2007-04-01

The complexation of Hg under sulfidic conditions influences its bioavailability for microbial methylation. Neutral dissolved Hg-sulfide complexes are readily available to Hg-methylating bacteria in culture, and thermodynamic models predict that inorganic Hg-sulfide complexes dominate dissolved Hg speciation under natural sulfidic conditions. However, these models have not been validated in the field. To examine the complexation of Hg in natural sulfidic waters, octanol/water partitioning methods were modified for use under environmentally relevant conditions, and a centrifuge ultrafiltration technique was developed. These techniques demonstrated much lower concentrations of dissolved Hg-sulfide complexes than predicted. Furthermore, the study revealed an interaction between Hg, dissolved organic matter (DOM), and sulfide that is not captured by current thermodynamic models. Whereas Hg forms strong complexes with DOM under oxic conditions, these complexes had not been expected to form in the presence of sulfide because of the stronger affinity of Hg for sulfide relative to its affinity for DOM. The observed interaction between Hg and DOM in the presence of sulfide likely involves the formation of a DOM-Hg-sulfide complex or results from the hydrophobic partitioning of neutral Hg-sulfide complexes into the higher-molecular-weight DOM. An understanding of the mechanism of this interaction and determination of complexation coefficients for the Hg-sulfide-DOM complex are needed to adequately assess how our new finding affects Hg bioavailability, sorption, and flux.

Diurnal shifts in co-distributions of sulfide and iron(II) and profiles of phosphate and ammonium in the rhizosphere of Zostera capricorni

NASA Astrophysics Data System (ADS)

Pagès, Anaïs; Welsh, David T.; Robertson, David; Panther, Jared G.; Schäfer, Jörg; Tomlinson, Rodger B.; Teasdale, Peter R.

2012-12-01

High resolution, two dimensional distributions of porewater iron(II) and sulfide were measured, using colourimetric DET (diffusive equilibration in a thin film) and DGT (diffusive gradients in a thin film) techniques, respectively, in Zostera capricorni colonised sediments under both light and dark conditions. Low resolution depth profiles of ammonium and phosphate were measured using conventional DET and DGT methods, respectively. Porewater iron(II) and sulfide distributions showed a high degree of spatial heterogeneity under both light and dark conditions, and distributions were characterised by a complex mosaic of sediment zones dominated by either iron(II) or sulfide. However, there was a clear shift in overall redox conditions between light and dark conditions. During light deployments, iron(II) and sulfide concentrations were generally low throughout the rhizosphere, apart from a few distinct "hotspots" of high concentration. Whereas during dark deployments, high concentrations of iron(II) were sometimes measured in the near surface sediments and sulfide depth distributions migrated towards the sediment surface. Profiles of porewater ammonium and phosphate demonstrated an increase in ammonium concentrations under dark compared to light conditions. Surprisingly, despite the large changes in iron(II) distributions between light and dark conditions, phosphate profiles remained similar, indicating that adsorption/release of phosphate by iron(III) hydr(oxide) mineral formation and reduction was not a major factor regulating porewater phosphate concentrations in these sediments or that phosphate uptake by the seagrass roots persisted during the dark period. Overall, the results demonstrate that the photosynthetic activity of the seagrass played a significant role in regulating sulfide, iron(II) and ammonium concentrations in the rhizosphere, due to rates of radial oxygen loss and ammonium uptake by the roots and rhizomes being lower under dark compared to light conditions. This cyclic production and reduction of iron(III) hydr(oxides) in the rhizosphere may act as a buffering system preventing sulfide accumulation.

Ground-water quality and geochemistry of aquifers associated with coal in the Allegheny and Monongahela formations, southeastern Ohio

USGS Publications Warehouse

Razem, A.C.; Sedam, A.C.

1985-01-01

Ground water from aquifers associated with coal beds in the Allegheny and Monongahela Formations in southeastern Ohio is predominantly a calcium magnesium bicarbonate type. Sodium bicarbonate type water is less common. Isolated areas of sodium chloride and calcium sulfate types also are present. The water is predominantly very hard, and has a median hardness concentration of 258 milligrams per liter as calcium carbonate and a median dissolved-solids concentration of 436 milligrams per liter. Few wells contain water with dissolved-solids concentrations in excess of 1,000 milligrams per liter. Bicarbonate concentration in ground water was found to be significantly different among coals, whereas concentrations of bicarbonate, hardness, calcium, magnesium, sodium, iron, manganese, and strontium were significantly different between ground water in the Allegheny and Monongahela Formations. Many constituents are significantly correlated, but few correlation coefficients are high. The presence of sulfate or iron is attributed to the kinetic mechanism operating during the oxidation of pyrite. The position along the sulfide or ferrous-iron oxidation pathways controls the reaction products of pyrite found in solution, and the formation of either the sulfate of iron constituents. The availability and rate of diffusion of oxygen in the formations exerts control on the water quality. Discriminant-function analysis correctly classifies 89 percent of the observations into the Allegheny or Monongahela Formations. As a verifications, 39 of 41 observations from another study were correctly classified by formation. The differences in water chemistry between the Allegheny and the Monongahela Formations are gradational and are attributed the oxidation of iron sulfide. The diffusion and availability of oxygen, which controls the chemical reaction, is regulated by the porosity and permeability of the rock with respect to oxygen and the presence or absence of carbonates, which controls the pH.

A hybrid artificial neural network and particle swarm optimization for prediction of removal of hazardous dye brilliant green from aqueous solution using zinc sulfide nanoparticle loaded on activated carbon.

PubMed

Ghaedi, M; Ansari, A; Bahari, F; Ghaedi, A M; Vafaei, A

2015-02-25

In the present study, zinc sulfide nanoparticle loaded on activated carbon (ZnS-NP-AC) simply was synthesized in the presence of ultrasound and characterized using different techniques such as SEM and BET analysis. Then, this material was used for brilliant green (BG) removal. To dependency of BG removal percentage toward various parameters including pH, adsorbent dosage, initial dye concentration and contact time were examined and optimized. The mechanism and rate of adsorption was ascertained by analyzing experimental data at various time to conventional kinetic models such as pseudo-first-order and second order, Elovich and intra-particle diffusion models. Comparison according to general criterion such as relative error in adsorption capacity and correlation coefficient confirm the usability of pseudo-second-order kinetic model for explanation of data. The Langmuir models is efficiently can explained the behavior of adsorption system to give full information about interaction of BG with ZnS-NP-AC. A multiple linear regression (MLR) and a hybrid of artificial neural network and partial swarm optimization (ANN-PSO) model were used for prediction of brilliant green adsorption onto ZnS-NP-AC. Comparison of the results obtained using offered models confirm higher ability of ANN model compare to the MLR model for prediction of BG adsorption onto ZnS-NP-AC. Using the optimal ANN-PSO model the coefficient of determination (R(2)) were 0.9610 and 0.9506; mean squared error (MSE) values were 0.0020 and 0.0022 for the training and testing data set, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

A hybrid artificial neural network and particle swarm optimization for prediction of removal of hazardous dye brilliant green from aqueous solution using zinc sulfide nanoparticle loaded on activated carbon

NASA Astrophysics Data System (ADS)

Ghaedi, M.; Ansari, A.; Bahari, F.; Ghaedi, A. M.; Vafaei, A.

2015-02-01

In the present study, zinc sulfide nanoparticle loaded on activated carbon (ZnS-NP-AC) simply was synthesized in the presence of ultrasound and characterized using different techniques such as SEM and BET analysis. Then, this material was used for brilliant green (BG) removal. To dependency of BG removal percentage toward various parameters including pH, adsorbent dosage, initial dye concentration and contact time were examined and optimized. The mechanism and rate of adsorption was ascertained by analyzing experimental data at various time to conventional kinetic models such as pseudo-first-order and second order, Elovich and intra-particle diffusion models. Comparison according to general criterion such as relative error in adsorption capacity and correlation coefficient confirm the usability of pseudo-second-order kinetic model for explanation of data. The Langmuir models is efficiently can explained the behavior of adsorption system to give full information about interaction of BG with ZnS-NP-AC. A multiple linear regression (MLR) and a hybrid of artificial neural network and partial swarm optimization (ANN-PSO) model were used for prediction of brilliant green adsorption onto ZnS-NP-AC. Comparison of the results obtained using offered models confirm higher ability of ANN model compare to the MLR model for prediction of BG adsorption onto ZnS-NP-AC. Using the optimal ANN-PSO model the coefficient of determination (R2) were 0.9610 and 0.9506; mean squared error (MSE) values were 0.0020 and 0.0022 for the training and testing data set, respectively.

Correlation of human papillomavirus status with apparent diffusion coefficient of diffusion-weighted MRI in head and neck squamous cell carcinomas.

PubMed

Driessen, Juliette P; van Bemmel, Alexander J M; van Kempen, Pauline M W; Janssen, Luuk M; Terhaard, Chris H J; Pameijer, Frank A; Willems, Stefan M; Stegeman, Inge; Grolman, Wilko; Philippens, Marielle E P

2016-04-01

Identification of prognostic patient characteristics in head and neck squamous cell carcinoma (HNSCC) is of great importance. Human papillomavirus (HPV)-positive HNSCCs have favorable response to (chemo)radiotherapy. Apparent diffusion coefficient, derived from diffusion-weighted MRI, has also shown to predict treatment response. The purpose of this study was to evaluate the correlation between HPV status and apparent diffusion coefficient. Seventy-three patients with histologically proven HNSCC were retrospectively analyzed. Mean pretreatment apparent diffusion coefficient was calculated by delineation of total tumor volume on diffusion-weighted MRI. HPV status was analyzed and correlated to apparent diffusion coefficient. Six HNSCCs were HPV-positive. HPV-positive HNSCC showed significantly lower apparent diffusion coefficient compared to HPV-negative. This correlation was independent of other patient characteristics. In HNSCC, positive HPV status correlates with low mean apparent diffusion coefficient. The favorable prognostic value of low pretreatment apparent diffusion coefficient might be partially attributed to patients with a positive HPV status. © 2015 Wiley Periodicals, Inc. Head Neck 38: E613-E618, 2016. © 2015 Wiley Periodicals, Inc.

Development of advanced thermoelectric materials, phase A

NASA Technical Reports Server (NTRS)

1980-01-01

Work performed on the chemical system characterized by chrome sulfide, chrome selenide, lanthanum selenide, and lanthanum sulfide is described. Most materials within the chemical systems possess the requisites for attractive thermoelectric materials. The preparation of the alloys is discussed. Graphs show the Seebeck coefficient, electrical resistivity, and thermal conductivity of various materials within the chemical systems. The results of selected doping are included.

Preliminary Investigation of the Role that DMS (Dimethyl Sulfide) and Cloud Cycles Play in the Formation of the Aerosol Size Distribution.

DTIC Science & Technology

1987-07-29

Osmotic and Activity Coefficients for Aqueous Methane Sulfonic Acid Solutions at 25 deg C," J. Chem. and Eng. Data 18... osmotic coefficient and MSA activity coefficient have been measured by Coving- ton et al. (1973). The water vapor pressure of the solution can be obtained...from f2L(M) M_ (7)6.5 x 10" where -f is the activity coefficient . Values of the osmotic coefficient and activity coefficient (from

Short-lived K2S Molecules in Superionic Potassium Sulfide

NASA Astrophysics Data System (ADS)

Okeya, Yusuke; Tsumuraya, Kazuo

2015-03-01

The first principles molecular dynamics method allows us to elucidate the formation of short-lived K2S molecular states in superionic potassium sulfide. The covalent and the Coulomb bonds exist between the ionized mobile potassiums and the ionized immobile sulfurs. Both the bonds induces indirect covalent and indirect Coulomb attractions between the di-interstitial potassiums on the mid-sulfurs, which forms the short-lived K2S molecular states. The covalent electron density also exists between short-lived potassium dimers. The three attractions reduce Haven's ratios of the potassiums in the conductor. The molecule formation indicates the electronic state of the conductor is intermediate between the ionic and covalent crystals. The absence of the long-lived potassium dimers implies a failure of the caterpillar diffusion model or the Frenkel-Kontorova chain model for the superionic diffusion of the potassiums in the sulfide. The incompletely ionized cations and anions reduce the Coulomb attractions between them which induces the sublattice melting of smaller size of the potassiums than the sulfurs.

Diffusion coefficients in organic-water solutions and comparison with Stokes-Einstein predictions

NASA Astrophysics Data System (ADS)

Evoy, E.; Kamal, S.; Bertram, A. K.

2017-12-01

Diffusion coefficients of organic species in particles containing secondary organic material (SOM) are necessary for predicting the growth and reactivity of these particles in the atmosphere. Previously, the Stokes-Einstein equation combined with viscosity measurements have been used to predict these diffusion coefficients. However, the accuracy of the Stokes-Einstein equation for predicting diffusion coefficients in SOM-water particles has not been quantified. To test the Stokes-Einstein equation, diffusion coefficients of fluorescent organic probe molecules were measured in citric acid-water and sorbitol-water solutions. These solutions were used as proxies for SOM-water particles found in the atmosphere. Measurements were performed as a function of water activity, ranging from 0.26-0.86, and as a function of viscosity ranging from 10-3 to 103 Pa s. Diffusion coefficients were measured using fluorescence recovery after photobleaching. The measured diffusion coefficients were compared with predictions made using the Stokes-Einstein equation combined with literature viscosity data. Within the uncertainties of the measurements, the measured diffusion coefficients agreed with the predicted diffusion coefficients, in all cases.

Irradiation of FeS: Implications for the Lifecycle of Sulfur in the Interstellar Medium and Presolar FeS Grains

NASA Technical Reports Server (NTRS)

Keller, Lindsay P.; Loeffler, M. J.; Christoffersen, R.; Dukes, C.; Rahman, Z.; Baragiola, R.

2010-01-01

Fe(Ni) sulfides are ubiquitous in chondritic meteorites and cometary samples where they are the dominant host of sulfur. Despite their abundance in these early solar system materials, their presence in interstellar and circumstellar environments is poorly understood. Fe-sulfides have been reported from astronomical observations of pre- and post-main sequence stars [1, 2] and occur as inclusions in bonafide circumstellar silicate grains [3, 4]. In cold, dense molecular cloud (MC) environments, sulfur is highly depleted from the gas phase [e.g. 5], yet observations of sulfur-bearing molecules in dense cores find a total abundance that is only a small fraction of the sulfur seen in diffuse regions [6], therefore the bulk of the depletion must reside in an abundant unobserved phase. In stark contrast, sulfur is essentially undepleted from the gas phase in the diffuse interstellar medium (ISM) [7-9], indicating that little sulfur is incorporated into solid grains in this environment. This is a rather puzzling observation unless Fe-sulfides are not produced in significant quantities in stellar outflows, or their lifetime in the ISM is very short due to rapid destruction. The main destruction mechanism is sputtering due to supernova shocks in the warm, diffuse ISM [10]. This process involves the reduction of Fe-sulfide with the production of Fe metal as a by-product and returning S to the gas phase. In order to test this hypothesis, we irradiated FeS and analyzed the resulting material using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM).

ANALYTIC FORMS OF THE PERPENDICULAR DIFFUSION COEFFICIENT IN NRMHD TURBULENCE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shalchi, A., E-mail: andreasm4@yahoo.com

2015-02-01

In the past different analytic limits for the perpendicular diffusion coefficient of energetic particles interacting with magnetic turbulence were discussed. These different limits or cases correspond to different transport modes describing how the particles are diffusing across the large-scale magnetic field. In the current paper we describe a new transport regime by considering the model of noisy reduced magnetohydrodynamic turbulence. We derive different analytic forms of the perpendicular diffusion coefficient, and while we do this, we focus on the aforementioned new transport mode. We show that for this turbulence model a small perpendicular diffusion coefficient can be obtained so thatmore » the latter diffusion coefficient is more than hundred times smaller than the parallel diffusion coefficient. This result is relevant to explain observations in the solar system where such small perpendicular diffusion coefficients have been reported.« less

A cryptic sulfur cycle driven by iron in the methane zone of marine sediment (Aarhus Bay, Denmark)

NASA Astrophysics Data System (ADS)

Holmkvist, Lars; Ferdelman, Timothy G.; Jørgensen, Bo Barker

2011-06-01

Sulfate reduction and sulfur-iron geochemistry were studied in 5-6 m deep gravity cores of Holocene mud from Aarhus Bay (Denmark). A goal was to understand whether sulfate is generated by re-oxidation of sulfide throughout the sulfate and methane zones, which might explain the abundance of active sulfate reducers deep below the main sulfate zone. Sulfate penetrated down to 130 cm where methane started to build up and where the concentration of free sulfide peaked at 5.5 mM. Below this sulfate-methane transition, sulfide diffused downwards to a sulfidization front at 520 cm depth, below which dissolved iron, Fe 2+, accumulated in the pore water. Sulfate reduction rates measured by 35S-tracer incubations in the sulfate zone were high due to high concentrations of reactive organic matter. Within the sulfate-methane transition, sulfate reduction was distinctly stimulated by the anaerobic oxidation of methane. In the methane zone below, sulfate remained at positive "background" concentrations of <0.5 mM down to the sulfidization front. Sulfate reduction decreased steeply to rates which at 300-500 cm depth were 0.2-1 pmol SO 42- cm -3 d -1, i.e., 4-5 orders of magnitude lower than rates measured near the sediment surface. The turn-over time of sulfate increased from 3 years at 12 cm depth to 100-1000 years down in the methane zone. Sulfate reduction in the methane zone accounted for only 0.1% of sulfate reduction in the entire sediment column and was apparently limited by the low pore water concentration of sulfate and the low availability of organic substrates. Amendment of the sediment with both sulfate and organic substrates immediately caused a 10- to 40-fold higher, "potential sulfate reduction" which showed that a physiologically intact community of sulfate reducing bacteria was present. The "background" sulfate concentration appears to be generated from the reaction of downwards diffusing sulfide with deeply buried Fe(III) species, such as poorly-reactive iron oxides or iron bound in reactive silicates. The oxidation of sulfide to sulfate in the sulfidic sediment may involve the formation of elemental sulfur and thiosulfate and their further disproportionation to sulfide and sulfate. The net reaction of sulfide and Fe(III) to form pyrite requires an additional oxidant, irrespective of the formation of sulfate. This could be CO 2 which is reduced with H 2 to methane. The methane subsequently diffuses upwards to become re-oxidized at the sulfate-methane transition and thereby removes excess reducing power and enables the formation of excess sulfate. We show here how the combination of these well-established sulfur-iron-carbon reactions may lead to the deep formation of sulfate and drive a cryptic sulfur cycle. The iron-rich post-glacial sediments underlying Holocene marine mud stimulate the strong sub-surface sulfide reoxidation observed in Aarhus Bay and are a result of the glacial to interglacial history of the Baltic Sea area. Yet, processes similar to the ones described here probably occur widespread in marine sediments, in particular along the ocean margins.

Organization of the Optical Society of America Photonic Science Topical Meeting Series. Volume 14. Photorefractive Materials Effects, and Devices Held in Beverly, Massachusetts on 29-31 July 1991

DTIC Science & Technology

1991-01-01

STUDENT CENTER the photorefractive effect in cadmium sulfide. The maximum gain coefficient measured is 0.3 cm-1 at 633 nm. The r:00 am-8:00 am BREAKFAST...OK, 74354, Tel: 918-542 1801 00 00- 00 Abstract NWe report the first observation of the photorefractive effect in Cadmium sulfide. The maximum gain...the exception of GaP [1] none of these materials can be used in the wavelength range of 600-700 nm. Cadmium Sulfide (CdS) has been extensively

Co-settling of Chromite and Sulfide Melt Droplets and Trace Element Partitioning between Sulfide and Silicate Melts

NASA Astrophysics Data System (ADS)

Manoochehri, S.; Schmidt, M. W.; Guenther, D.

2013-12-01

Gravitational settling of immiscible, dense sulfide melt droplets together with other cumulate phases such as chromite, combined with downward percolation of these droplets through a cumulate pile, is thought to be one of the possible processes leading to the formation of PGE rich sulfide deposits in layered mafic intrusions. Furthermore some chromitite seams in the Merensky Reef (Bushveld Complex) are considered to be acting as a filter or barrier for further downward percolation of sulfide melts into footwall layers. To investigate the feasibility of such mechanical processes and to study the partitioning behavior of 50 elements including transition metals and REEs (but not PGEs) between a silicate and a sulfide melt, two separate series of high temperature (1250-1380 °C) centrifuge-assisted experiments at 1000 g, 0.4-0.6 GPa were conducted. A synthetic silicate glass with a composition representative of the parental magma of the Bushveld Complex (~ 55 wt% SiO2) was mixed with pure FeS powder. For the first series of experiments, 15 or 25 wt% natural chromite with average grain sizes of ~ 5 or 31 μm were added to a mixture of silicate glass and FeS (10 wt%) adding 1 wt% water. For the second series, a mixture of the same glass and FeS was doped with 50 trace elements. These mixtures were first statically equilibrated and then centrifuged. In the first experimental series, sulfide melt droplets settled together with, but did not segregate from chromite grains even after centrifugation at 1000 g for 12 hours. A change in initial chromite grain size and proportions didn't have any effect on segregation. Without chromite, the starting mixture resulted in the formation of large sulfide melt pools together with finer droplets still disseminated through the silicate glass and both at the bottom of the capsule. The incomplete segregation of sulfide melt is interpreted as being due to high interfacial energies between sulfide and silicate melts/crystals which hinder both, the nucleation of newly formed sulfide droplets and the interconnectivity of separate droplets. The interfacial energies between sulfide melt and silicate or oxide crystals is even higher than for silicate melt, consequently in experiments with chromite, sulfide segregation is even more hindered. Partition coefficients of 50 elements between a sulfide and a silicate melt are determined as a function of differing temperature between 1250 - 1380 °C. As a proxy to investigate the bond strength of network modifier cations, the relation between the partition coefficients and ionic potentials of different groups of elements has been determined.

Electrostatic coupling between DNA and its counterions modulates the observed translational diffusion coefficients.

PubMed

Stellwagen, Earle; Stellwagen, Nancy C

2015-09-01

Free solution capillary electrophoresis (CE) is a useful technique for measuring the translational diffusion coefficients of charged analytes. The measurements are relatively fast if the polarity of the electric field is reversed to drive the analyte back and forth past the detection window during each run. We have tested the validity of the resulting diffusion coefficients using double-stranded DNA molecules ranging in size from 20 to 960 base pairs as the model system. The diffusion coefficients of small DNAs are equal to values in the literature measured by other techniques. However, the diffusion coefficients of DNA molecules larger than ∼30 base pairs are anomalously high and deviate increasingly from the literature values with increasing DNA molar mass. The anomalously high diffusion coefficients are due to electrostatic coupling between the DNA and its counterions. As a result, the measured diffusion coefficients vary with the diffusion coefficient of the counterion, as well as with cation concentration and electric field strength. These effects can be reduced or eliminated by measuring apparent diffusion coefficients of the DNA at several different electric field strengths and extrapolating the results to zero electric field.

The role of intra-NAPL diffusion on mass transfer from MGP residuals

NASA Astrophysics Data System (ADS)

Shafieiyoun, Saeid; Thomson, Neil R.

2018-06-01

An experimental and computational study was performed to investigate the role of multi-component intra-NAPL diffusion on NAPL-water mass transfer. Molecular weight and the NAPL component concentrations were determined to be the most important parameters affecting intra-NAPL diffusion coefficients. Four NAPLs with different viscosities but the same quantified mass were simulated. For a spherical NAPL body, a combination of NAPL properties and interphase mass transfer rate can result in internal diffusion limitations. When the main intra-NAPL diffusion coefficients are in the range of self-diffusion coefficients (10-5 to 10-6 cm2/s), dissolution is not limited by internal diffusion except for high mass transfer rate coefficients (>180 cm/day). For a complex and relatively high viscous NAPL (>50 g/(cm s)), smaller intra-NAPL diffusion coefficients (<10-8) are expected and even low mass transfer rate coefficients ( 6 cm/day) can result in diffusion-limited dissolution.

Moisture effect on mechanical properties of polymeric composite materials

NASA Astrophysics Data System (ADS)

Airale, A. G.; Carello, M.; Ferraris, A.; Sisca, L.

2016-05-01

The influence of moisture on the mechanical properties of fibre-reinforced polymer matrix composites (PMCs) was investigated. Four materials had been take into account considering: both 2×2-Twill woven carbon fibre or glass fibre, thermosetting matrix (Epoxy Resin) or thermoplastic matrix (Polyphenylene Sulfide). The specimens were submitted for 1800 hours to a hygrothermic test to evaluate moisture absorption on the basis of the Fick's law and finally tested to verify the mechanical properties (ultimate tensile strength). The results showed that the absorbed moisture decreases those properties of composites which were dominated by the matrix or the interface, while was not detectable the influence of water on the considered fibre. An important result is that the diffusion coefficient is highest for glass/PPS and lowest for carbon/epoxy composite material. The results give useful suggestions for the design of vehicle components that are exposed to environmental conditions (rain, snow and humidity).

Effective diffusion coefficient including the Marangoni effect

NASA Astrophysics Data System (ADS)

Kitahata, Hiroyuki; Yoshinaga, Natsuhiko

2018-04-01

Surface-active molecules supplied from a particle fixed at the water surface create a spatial gradient of the molecule concentration, resulting in Marangoni convection. Convective flow transports the molecules far from the particle, enhancing diffusion. We analytically derive the effective diffusion coefficient associated with the Marangoni convection rolls. The resulting estimated effective diffusion coefficient is consistent with our numerical results and the apparent diffusion coefficient measured in experiments.

Nanoengineering of 2D tin sulfide nanoflake arrays incorporated on polyaniline nanofibers with boosted capacitive behavior

NASA Astrophysics Data System (ADS)

Wang, Huanhuan; Chao, DongLiang; Liu, Jilei; Lin, Jianyi; Shen, Ze Xiang

2018-07-01

Nanoscale engineering plays an important role in designing novel electrode architecture and boosting energy storage in supercapacitors. Herein, we demonstrate the fabrication of freestanding tin sulfide based supercapacitor electrode using facile nucleation substrate control, i.e. polyaniline network. This is the first time that tin sulfide based material is fabricated as a binder-free electrode for supercapacitors. The first combination of tin sulfide and polyaniline also evokes synergistic effect to enhance the performance as the polyaniline nanofibers facilitate the growth of tin sulfide flakes in nanosize which is further proved helpful for improving the capacity and stability of the electrode. The as-obtained electrode of tin sulfide nanoflake arrays incorporated on polyaniline nanofibers (365 F g‑1 at 10 mV s‑1) exhibits superior electrochemical performance compared with micro-scaled tin sulfide (32 F g‑1 at 10 mV s‑1). The significantly improved pseudocapacitive and diffusive contributions of polyaniline nanofibers incorporated electrode are identified by quantitative kinetics analysis due to greatly decreased particle size and introduced mesopores, nanoclusters, and exposed edges. Profited from effective nanostructure engineering, a Na+ intercalation mechanism is also pointed out in boosting the electrochemical performance.

Element remobilization, "internal P-loading," and sediment-P reactivity researched by DGT (diffusive gradients in thin films) technique.

PubMed

Wu, Zhihao; Wang, Shengrui; He, Mengchang; Zhang, Li; Jiao, Lixin

2015-10-01

Labile P, Fe, and sulfide with the high spatial resolution in sediment porewater of five sites (A-E) of Dianchi Lake (China) were measured at same locations using AgI/Chelex-100, Chelex-100, and ferrihydrite DGT (diffusive gradients in thin films) probes. DGT derived P/Fe/S concentrations in sediment porewater on millimeter or sub-millimeter scale in order to reveal the element remobilization process and the mechanism of "internal P-loading" of sediments in Dianchi Lake. Decomposition of alga biomass in the uppermost sediment layer and the reductive dissolution of Fe-bound P in the anoxic sediment were the two main processes causing P release. A dynamic numerical model-DIFS (DGT-induced flux in sediments) was used to assess sediment-P reactivity (capacity of solid pool and rate of transfer) and P release risk by kinetic parameter-T C (1089∼20,450 s), distribution coefficient-K d (167.09∼502.0 cm(3) g(-1)), resupply parameter-R (from 0.242 to 0.518), and changes of dissolved/sorbed concentration, R and M at the microzone of DGT/porewater/sediment.

Modeling and experiments for the time-dependent diffusion coefficient during methane desorption from coal

NASA Astrophysics Data System (ADS)

Cheng-Wu, Li; Hong-Lai, Xue; Cheng, Guan; Wen-biao, Liu

2018-04-01

Statistical analysis shows that in the coal matrix, the diffusion coefficient for methane is time-varying, and its integral satisfies the formula μt κ /(1 + β κ ). Therefore, a so-called dynamic diffusion coefficient model (DDC model) is developed. To verify the suitability and accuracy of the DDC model, a series of gas diffusion experiments were conducted using coal particles of different sizes. The results show that the experimental data can be accurately described by the DDC and bidisperse models, but the fit to the DDC model is slightly better. For all coal samples, as time increases, the effective diffusion coefficient first shows a sudden drop, followed by a gradual decrease before stabilizing at longer times. The effective diffusion coefficient has a negative relationship with the size of the coal particle. Finally, the relationship between the constants of the DDC model and the effective diffusion coefficient is discussed. The constant α (μ/R 2 ) denotes the effective coefficient at the initial time, and the constants κ and β control the attenuation characteristic of the effective diffusion coefficient.

Continuous Diffusion Model for Concentration Dependence of Nitroxide EPR Parameters in Normal and Supercooled Water.

PubMed

Merunka, Dalibor; Peric, Miroslav

2017-05-25

Electron paramagnetic resonance (EPR) spectra of radicals in solution depend on their relative motion, which modulates the Heisenberg spin exchange and dipole-dipole interactions between them. To gain information on radical diffusion from EPR spectra demands both reliable spectral fitting to find the concentration coefficients of EPR parameters and valid expressions between the concentration and diffusion coefficients. Here, we measured EPR spectra of the 14 N- and 15 N-labeled perdeuterated TEMPONE radicals in normal and supercooled water at various concentrations. By fitting the EPR spectra to the functions based on the modified Bloch equations, we obtained the concentration coefficients for the spin dephasing, coherence transfer, and hyperfine splitting parameters. Assuming the continuous diffusion model for radical motion, the diffusion coefficients of radicals were calculated from the concentration coefficients using the standard relations and the relations derived from the kinetic equations for the spin evolution of a radical pair. The latter relations give better agreement between the diffusion coefficients calculated from different concentration coefficients. The diffusion coefficients are similar for both radicals, which supports the presented method. They decrease with lowering temperature slower than is predicted by the Stokes-Einstein relation and slower than the rotational diffusion coefficients, which is similar to the diffusion of water molecules in supercooled water.

Na, Rb and Cs partitioning between metal, silicate and sulfide: Implications for volatile depletion in terrestrial planets

NASA Astrophysics Data System (ADS)

Boujibar, A.; Fei, Y.; Du, Z.; Righter, K.; Bullock, E. S.

2017-12-01

Inner Solar System materials are known for their depletion in volatile elements, including the moderately volatile alkalis: Na, K, Rb, and Cs. The origin of this depletion is still uncertain, as several processes could have been involved, during the nebular condensation or planetary accretion. Volatile depletion is commonly estimated through comparison of alkali concentrations relatively to those of chondrites, assuming they remain in planetary mantles during core segregation. However, experimental studies show that substantial K can partition into metals that are enriched in sulfur and oxygen. Several models have also suggested that sulfides may have played an important role during episodes of sulfide segregation from a crystallizing magma ocean (sulfide matte) or accretion of S-rich planetary embryos. For Mercury, a sulfide layer could be present between core and mantle, due to immiscibility between Si-rich and S-rich metals. Therefore, here we investigate whether alkali elements (Na, Cs and Rb) could be partly sequestered in planetary cores during their differentiation. We conducted experiments at high pressure and temperature (1 to 5 GPa and up to 1900 °C) to determine partition coefficients of Na, Rb and Cs between metal and silicate. Our results show that pressure, temperature, sulfur and oxygen in metals enhance the partitioning of Na, Rb and Cs into metals, as previously found for K. For all three investigated alkalis (Na, Rb and Cs), we found a maximum partition coefficient of 1 between sulfides containing 13 wt% O and silicate melt. Therefore, S-rich cores or sulfide layers formed due to immiscibility in Fe-S-O systems could have acted as important geochemical reservoirs for alkali elements. Using our experimental data and different assumptions on initial bulk abundances, we evaluate volatile depletion in terrestrial planets, by comparing resulting mantle alkali concentrations after core segregation, with actual concentrations in the Earth's mantle.

Anisotropic diffusion of fluorescently labeled ATP in rat cardiomyocytes determined by raster image correlation spectroscopy

PubMed Central

Vendelin, Marko; Birkedal, Rikke

2008-01-01

A series of experimental data points to the existence of profound diffusion restrictions of ADP/ATP in rat cardiomyocytes. This assumption is required to explain the measurements of kinetics of respiration, sarcoplasmic reticulum loading with calcium, and kinetics of ATP-sensitive potassium channels. To be able to analyze and estimate the role of intracellular diffusion restrictions on bioenergetics, the intracellular diffusion coefficients of metabolites have to be determined. The aim of this work was to develop a practical method for determining diffusion coefficients in anisotropic medium and to estimate the overall diffusion coefficients of fluorescently labeled ATP in rat cardiomyocytes. For that, we have extended raster image correlation spectroscopy (RICS) protocols to be able to discriminate the anisotropy in the diffusion coefficient tensor. Using this extended protocol, we estimated diffusion coefficients of ATP labeled with the fluorescent conjugate Alexa Fluor 647 (Alexa-ATP). In the analysis, we assumed that the diffusion tensor can be described by two values: diffusion coefficient along the myofibril and that across it. The average diffusion coefficients found for Alexa-ATP were as follows: 83 ± 14 μm2/s in the longitudinal and 52 ± 16 μm2/s in the transverse directions (n = 8, mean ± SD). Those values are ∼2 (longitudinal) and ∼3.5 (transverse) times smaller than the diffusion coefficient value estimated for the surrounding solution. Such uneven reduction of average diffusion coefficient leads to anisotropic diffusion in rat cardiomyocytes. Although the source for such anisotropy is uncertain, we speculate that it may be induced by the ordered pattern of intracellular structures in rat cardiomyocytes. PMID:18815224

Fluid self-diffusion in Scots pine sapwood tracheid cells.

PubMed

Johannessen, Espen H; Hansen, Eddy W; Rosenholm, Jarl B

2006-02-09

The self-diffusion coefficients of water and toluene in Scots pine sapwood was measured using low field pulsed field gradient nuclear magnetic resonance (PFG-NMR). Wood chips of 8 mm diameter were saturated with the respective liquids, and liquid self-diffusion was then traced in one dimension orthogonal to the tracheid cell walls in the wood's radial direction. The experimental echo attenuation curves were exponential, and characteristic self-diffusion coefficients were produced for diffusion times spanning from very short times to times on the order of magnitude of seconds. Observed self-diffusion coefficients were decaying asymptotically as a function of diffusion time, an effect which was ascribed to the cell walls' restriction on confined liquid diffusion. The observed self-diffusion behavior in Scots pine sapwood was compared to self-diffusion coefficients obtained from simulations of diffusion in a square. Principles of molecular displacements in confined geometries were used for elucidating the wood's cellular structure from the observed diffusion coefficients. The results were compared with a mathematical model for diffusion between parallel planes.

Indium-bearing sulfides from the Hämmerlein skarn deposit, Erzgebirge, Germany: evidence for late-stage diffusion of indium into sphalerite

NASA Astrophysics Data System (ADS)

Bauer, Matthias E.; Seifert, Thomas; Burisch, Mathias; Krause, Joachim; Richter, Nancy; Gutzmer, Jens

2017-12-01

At the Hämmerlein skarn deposit, located in the western Erzgebirge (Germany), a major cassiterite-dominated Sn mineralization stage is spatially associated with a younger Zn-Cu-In sulfide mineralization stage. In this contribution, we provide the first detailed description of the Zn-Cu-In sulfide mineralization stage, based on field geological observations combined with detailed petrographic studies and electron probe microanalysis data. Indium-rich sulfide mineralization occurs as irregular, semi-massive lenses or as infill of short, discontinuous veinlets that crosscut the cassiterite-bearing skarn assemblage. Indium- and Cu-rich sphalerite and roquesite are found to be closely associated with In-bearing chalcopyrite. The highest In concentrations in sphalerite occur at the rims and along cracks of sphalerite grains. The distribution resembles diffusion profiles, suggesting that the In enrichment is due to an hydrothermal overprint that postdates the initial formation of both sphalerite and chalcopyrite. Textural relations illustrate that the diffusion fronts in sphalerite grains are thicker where they are in contact to anhedral masses of hematite and magnetite. Our observations suggest that In enrichment in sphalerite at the Hämmerlein skarn deposit is due to the decomposition of In-bearing chalcopyrite. The resultant release of Fe led to the formation of hematite and magnetite, whereas Cu and In were incorporated into sphalerite along grain boundaries and micro fractures. Incorporation into the sphalerite lattice took place by coupled substitution of Cu+ + In3+ ↔ 2Zn2+, suggesting that the concurrent availability of Cu and In may be an essential factor to enrich In in sphalerite in hydrothermal ore-forming environments.

On time-dependent diffusion coefficients arising from stochastic processes with memory

NASA Astrophysics Data System (ADS)

Carpio-Bernido, M. Victoria; Barredo, Wilson I.; Bernido, Christopher C.

2017-08-01

Time-dependent diffusion coefficients arise from anomalous diffusion encountered in many physical systems such as protein transport in cells. We compare these coefficients with those arising from analysis of stochastic processes with memory that go beyond fractional Brownian motion. Facilitated by the Hida white noise functional integral approach, diffusion propagators or probability density functions (pdf) are obtained and shown to be solutions of modified diffusion equations with time-dependent diffusion coefficients. This should be useful in the study of complex transport processes.

In Situ Effective Diffusion Coefficient Profiles in Live Biofilms Using Pulsed-Field Gradient Nuclear Magnetic Resonance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Renslow, Ryan S.; Majors, Paul D.; McLean, Jeffrey S.

2010-08-15

Diffusive mass transfer in biofilms is characterized by the effective diffusion coefficient. It is well-documented that the effective diffusion coefficient can vary by location in a biofilm. The current literature is dominated by effective diffusion coefficient measurements for distinct cell clusters and stratified biofilms showing this spatial variation. Regardless of whether distinct cell clusters or surface-averaging methods are used, position-dependent measurements of the effective diffusion coefficient are currently: 1) invasive to the biofilm, 2) performed under unnatural conditions, 3) lethal to cells, and/or 4) spatially restricted to only certain regions of the biofilm. Invasive measurements can lead to inaccurate resultsmore » and prohibit further (time dependent) measurements which are important for the mathematical modeling of biofilms. In this study our goals were to: 1) measure the effective diffusion coefficient for water in live biofilms, 2) monitor how the effective diffusion coefficient changes over time under growth conditions, and 3) correlate the effective diffusion coefficient with depth in the biofilm. We measured in situ two-dimensional effective diffusion coefficient maps within Shewanella oneidensis MR-1biofilms using pulsed-field gradient nuclear magnetic resonance methods, and used them to calculate surface-averaged relative effective diffusion coefficient (Drs) profiles. We found that 1) Drs decreased from the top of the biofilm to the bottom, 2) Drs profiles differed for biofilms of different ages, 3) Drs profiles changed over time and generally decreased with time, 4) all the biofilms showed very similar Drs profiles near the top of the biofilm, and 5) the Drs profile near the bottom of the biofilm was different for each biofilm. Practically, our results demonstrate that advanced biofilm models should use a variable effective diffusivity which changes with time and location in the biofilm.« less

Estimating the Diffusion Coefficients of Sugars Using Diffusion Experiments in Agar-Gel and Computer Simulations.

PubMed

Miyamoto, Shuichi; Atsuyama, Kenji; Ekino, Keisuke; Shin, Takashi

2018-01-01

The isolation of useful microbes is one of the traditional approaches for the lead generation in drug discovery. As an effective technique for microbe isolation, we recently developed a multidimensional diffusion-based gradient culture system of microbes. In order to enhance the utility of the system, it is favorable to have diffusion coefficients of nutrients such as sugars in the culture medium beforehand. We have, therefore, built a simple and convenient experimental system that uses agar-gel to observe diffusion. Next, we performed computer simulations-based on random-walk concepts-of the experimental diffusion system and derived correlation formulas that relate observable diffusion data to diffusion coefficients. Finally, we applied these correlation formulas to our experimentally-determined diffusion data to estimate the diffusion coefficients of sugars. Our values for these coefficients agree reasonably well with values published in the literature. The effectiveness of our simple technique, which has elucidated the diffusion coefficients of some molecules which are rarely reported (e.g., galactose, trehalose, and glycerol) is demonstrated by the strong correspondence between the literature values and those obtained in our experiments.

Study of diffusion coefficient of anhydrous trehalose glasses by using PFG-NMR spectroscopy

NASA Astrophysics Data System (ADS)

Kwon, Hyun-Joung; Takekawa, Reiji; Kawamura, Junichi; Tokuyama, Michio

2013-02-01

We investigated the temperature dependent long time self-diffusion coefficient of the anhydrous trehalose supercooled liquids by using pulsed field gradient nuclear magnetic resonance (PFG-NMR) spectroscopy. At the same temperature ranges, the diffusion coefficient convoluted from the α-relaxation time as Einstein-Smoluchowski relaxation, measured by using the dielectric loss spectroscopy are well overlapped with diffusion coefficients within experimental error. The temperature dependent diffusion coefficients obtained from different methods are normalized by fictive temperature and well satisfied the single master curve, proposed by Tokuyama.

Removal of sulfur compounds from petroleum refinery wastewater through adsorption on modified activated carbon.

PubMed

Ben Hariz, Ichrak; Al Ayni, Foued; Monser, Lotfi

2014-01-01

The adsorption of sulfur compounds from petroleum refinery wastewater on a chemically modified activated carbon (MAC) was investigated. The modification technique (nitric acid, hydrogen peroxide and thermal modification) enhanced the removal capacity of carbon and therefore decreases cost-effective removal of sulfide from refinery wastewater. Adsorption equilibrium and kinetics data were determined for sulfur removal from real refinery wastewater. The data were evaluated according to several adsorption isotherm and kinetics models. The Freundlich isotherm fitted well with the equilibrium data of sulfur on different adsorbents, whereas the kinetics data were best fitted by the pseudo-second-order model. Insights of sulfide removal mechanisms indicated that the sorption was controlled through the intraparticle diffusion mechanism with a significant contribution of film diffusion. The MAC adsorbent was found to have an effective removal capacity of approximately 2.5 times that of non-modified carbon. Using different MAC, sulfides were eliminated with a removal capacity of 52 mg g(-1). Therefore, MAC can be utilized as an effective and less expensive adsorbent for the reduction of sulfur in refinery wastewater.

Analytic expressions for ULF wave radiation belt radial diffusion coefficients

PubMed Central

Ozeke, Louis G; Mann, Ian R; Murphy, Kyle R; Jonathan Rae, I; Milling, David K

2014-01-01

We present analytic expressions for ULF wave-derived radiation belt radial diffusion coefficients, as a function of L and Kp, which can easily be incorporated into global radiation belt transport models. The diffusion coefficients are derived from statistical representations of ULF wave power, electric field power mapped from ground magnetometer data, and compressional magnetic field power from in situ measurements. We show that the overall electric and magnetic diffusion coefficients are to a good approximation both independent of energy. We present example 1-D radial diffusion results from simulations driven by CRRES-observed time-dependent energy spectra at the outer boundary, under the action of radial diffusion driven by the new ULF wave radial diffusion coefficients and with empirical chorus wave loss terms (as a function of energy, Kp and L). There is excellent agreement between the differential flux produced by the 1-D, Kp-driven, radial diffusion model and CRRES observations of differential electron flux at 0.976 MeV—even though the model does not include the effects of local internal acceleration sources. Our results highlight not only the importance of correct specification of radial diffusion coefficients for developing accurate models but also show significant promise for belt specification based on relatively simple models driven by solar wind parameters such as solar wind speed or geomagnetic indices such as Kp. Key Points Analytic expressions for the radial diffusion coefficients are presented The coefficients do not dependent on energy or wave m value The electric field diffusion coefficient dominates over the magnetic PMID:26167440

Diffusion coefficient of the protein in various crystallization solutions: The key to growing high-quality crystals in space

NASA Astrophysics Data System (ADS)

Tanaka, Hiroaki; Takahashi, Sachiko; Yamanaka, Mari; Yoshizaki, Izumi; Sato, Masaru; Sano, Satoshi; Motohara, Moritoshi; Kobayashi, Tomoyuki; Yoshitomi, Susumu; Tanaka, Tetsuo; Fukuyama, Seijiro

2006-09-01

The diffusion coefficients of lysozyme and alpha-amylase were measured in the various polyethylene glycol (PEG) solutions. Obtained diffusion coefficients were studied with the viscosity coefficient of the solution. It was found that the diffusion process of the protein was suppressed with a factor of vγ, where ν is a relative viscosity coefficient of the PEG solution. The value of γ is -0.64 at PEG1500 for both proteins. The value increased to -0.48 at PEG8000 for lysozyme, while decreased to -0.72 for alpha-amylase. The equation of an approximate diffusion coefficient at certain PEG molecular weight and concentration was roughly obtained.

Effect of thermal annealing on structural and optical properties of In{sub 2}S{sub 3} thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choudhary, Sonu, E-mail: sonuchoudhary1983@gmail.com

2015-08-28

There is a highly need of an alternate of toxic materials CdS for solar cell applications and indium sulfide is found the most suitable candidate to replace CdS due to its non-toxic and environmental friendly nature. In this paper, the effect of thermal annealing on the structural and optical properties of indium sulfide (In{sub 2}S{sub 3}) thin films is undertaken. The indium sulfide thin films of 121 nm were deposited on glass substrates employing thermal evaporation method. The films were subjected to the X-ray diffractometer and UV-Vis spectrophotometer respectively for structural and optical analysis. The XRD pattern show that themore » as-deposited thin film was amorphous in nature and crystallinity is found to be varied with annealing temperature. The optical analysis reveals that the optical band gap is varied with annealing. The optical parameters like absorption coefficient, extinction coefficient and refractive index were calculated. The results are in good agreement with available literature.« less

Extracting surface diffusion coefficients from batch adsorption measurement data: application of the classic Langmuir kinetics model.

PubMed

Chu, Khim Hoong

2017-11-09

Surface diffusion coefficients may be estimated by fitting solutions of a diffusion model to batch kinetic data. For non-linear systems, a numerical solution of the diffusion model's governing equations is generally required. We report here the application of the classic Langmuir kinetics model to extract surface diffusion coefficients from batch kinetic data. The use of the Langmuir kinetics model in lieu of the conventional surface diffusion model allows derivation of an analytical expression. The parameter estimation procedure requires determining the Langmuir rate coefficient from which the pertinent surface diffusion coefficient is calculated. Surface diffusion coefficients within the 10 -9 to 10 -6  cm 2 /s range obtained by fitting the Langmuir kinetics model to experimental kinetic data taken from the literature are found to be consistent with the corresponding values obtained from the traditional surface diffusion model. The virtue of this simplified parameter estimation method is that it reduces the computational complexity as the analytical expression involves only an algebraic equation in closed form which is easily evaluated by spreadsheet computation.

Temperature effects on diffusion coefficient for 6-gingerol and 6-shogaol in subcritical water extraction

NASA Astrophysics Data System (ADS)

Ilia Anisa, Nor; Azian, Noor; Sharizan, Mohd; Iwai, Yoshio

2014-04-01

6-gingerol and 6-shogaol are the main constituents as anti-inflammatory or bioactive compounds from zingiber officinale Roscoe. These bioactive compounds have been proven for inflammatory disease, antioxidatives and anticancer. The effect of temperature on diffusion coefficient for 6-gingerol and 6-shogaol were studied in subcritical water extraction. The diffusion coefficient was determined by Fick's second law. By neglecting external mass transfer and solid particle in spherical form, a linear portion of Ln (1-(Ct/Co)) versus time was plotted in determining the diffusion coefficient. 6-gingerol obtained the higher yield at 130°C with diffusion coefficient of 8.582x10-11 m2/s whilst for 6-shogaol, the higher yield and diffusion coefficient at 170°C and 19.417 × 10-11 m2/s.

Extreme enrichment of Se, Te, PGE and Au in Cu sulfide microdroplets: evidence from LA-ICP-MS analysis of sulfides in the Skaergaard Intrusion, east Greenland

NASA Astrophysics Data System (ADS)

Holwell, David A.; Keays, Reid R.; McDonald, Iain; Williams, Megan R.

2015-12-01

The Platinova Reef, in the Skaergaard Intrusion, east Greenland, is an example of a magmatic Cu-PGE-Au sulfide deposit formed in the latter stages of magmatic differentiation. As is characteristic with such deposits, it contains a low volume of sulfide, displays peak metal offsets and is Cu rich but Ni poor. However, even for such deposits, the Platinova Reef contains extremely low volumes of sulfide and the highest Pd and Au tenor sulfides of any magmatic ore deposit. Here, we present the first LA-ICP-MS analyses of sulfide microdroplets from the Platinova Reef, which show that they have the highest Se concentrations (up to 1200 ppm) and lowest S/Se ratios (190-700) of any known magmatic sulfide deposit and have significant Te enrichment. In addition, where sulfide volume increases, there is a change from high Pd-tenor microdroplets trapped in situ to larger, low tenor sulfides. The transition between these two sulfide regimes is marked by sharp peaks in Au, and then Te concentration, followed by a wider peak in Se, which gradually decreases with height. Mineralogical evidence implies that there is no significant post-magmatic hydrothermal S loss and that the metal profiles are essentially a function of magmatic processes. We propose that to generate these extreme precious and semimetal contents, the sulfides must have formed from an anomalously metal-rich package of magma, possibly formed via the dissolution of a previously PGE-enriched sulfide. Other processes such as kinetic diffusion may have also occurred alongside this to produce the ultra-high tenors. The characteristic metal offset pattern observed is largely controlled by partitioning effects, producing offset peaks in the order Pt+Pd>Au>Te>Se>Cu that are entirely consistent with published D values. This study confirms that extreme enrichment in sulfide droplets can occur in closed-system layered intrusions in situ, but this will characteristically form ore deposits that are so low in sulfide that they do not conform to conventional deposit models for Cu-Ni-PGE sulfides which require very high R factors, and settling of sulfide liquids.

Hydrogen sulfide production and volatilization in a polymictic eutrophic saline lake, Salton Sea, California.

PubMed

Reese, Brandi Kiel; Anderson, Michael A; Amrhein, Christopher

2008-11-15

The Salton Sea is a large shallow saline lake located in southern California that is noted for high sulfate concentrations, substantial algal productivity, and very warm water column temperatures. These conditions are well-suited for sulfide production, and sulfide has been implicated in summer fish kills, although no studies have been conducted to specifically understand hydrogen sulfide production and volatilization there. Despite polymictic mixing patterns and relatively short accumulation periods, the amount of sulfide produced is comparable to meromictic lakes. Sulfide levels in the Salton Sea reached concentrations of 1.2 mmol L(-1) of total free sulfide in the hypolimnion and 5.6 mmol L(-1) in the sediment pore water. Strong winds in late July mixed H2S into the surface water, where it depleted the entire water column of dissolved oxygen and reached a concentration of 0.1 mmol L(-1). Sulfide concentrations exceeded the toxicity threshold of tilapia (Oreochromis mossambicus) and combined with strong anoxia throughout the water column, resulted in a massive fish kill. The mixing of sulfide into the surface waters also increased atmospheric H2S concentrations, reaching 1.0 micromol m(-3). The flux of sulfide from the sediment into the water column was estimated to range from 2-3 mmol m(-2) day(-1) during the winter and up to 8 mmol m(-2) day(-1) during the summer. Application of the two-layer model for volatilization indicates that up to 19 mmol m(-2) day(-1) volatilized from the surface during the mixing event. We estimate that as much as 3400 Mg year(-1) or approximately 26% of sulfide that diffused into the water column from the deepest sediments may have been volatilized to the atmosphere.

Derivation of diffusion coefficient of a Brownian particle in tilted periodic potential from the coordinate moments

NASA Astrophysics Data System (ADS)

Zhang, Yunxin

2009-07-01

In this research, diffusion of an overdamped Brownian particle in the tilted periodic potential is investigated. Using the one-dimensional hopping model, the formulations of the mean velocity V and effective diffusion coefficient D of the Brownian particle have been obtained [B. Derrida, J. Stat. Phys. 31 (1983) 433]. Based on the relation between the effective diffusion coefficient and the moments of the mean first passage time, the formulation of effective diffusion coefficient D of the Brownian particle also has been obtained [P. Reimann, et al., Phys. Rev. E 65 (2002) 031104]. In this research, we'll give another analytical expression of the effective diffusion coefficient D from the moments of the particle's coordinate.

Corrosion resistant ceramic materials

DOEpatents

Kaun, Thomas D.

1995-01-01

Ceramic materials which exhibit stability in severely-corrosive environments having high alkali-metal activity, high sulfur/sulfide activity and/or molten halides at temperatures of 200.degree.-550.degree. C. or organic salt (including SO.sub.2 and SO.sub.2 Cl.sub.2) at temperatures of 25.degree.-200.degree. C. These sulfide ceramics form stoichiometric (single-phase) compounds with sulfides of Ca, Li, Na, K, Al, Mg, Si, Y, La, Ce, Ga, Ba, Zr and Sr and show melting-points that are sufficiently low and have excellent wettability with many metals (Fe, Ni, Mo) to easily form metal/ceramic seals. Ceramic compositions are also formulated to adequately match thermal expansion coefficient of adjacent metal components.

Corrosion resistant ceramic materials

DOEpatents

Kaun, Thomas D.

1996-01-01

Ceramic materials which exhibit stability in severely-corrosive environments having high alkali-metal activity, high sulfur/sulfide activity and/or molten halides at temperatures of 200.degree.-550.degree. C. or organic salt (including SO.sub.2 and SO.sub.2 Cl.sub.2) at temperatures of 25.degree.-200.degree. C. These sulfide ceramics form stoichiometric (single-phase) compounds with sulfides of Ca, Li, Na, K, Al, Mg, Si, Y, La, Ce, Ga, Ba, Zr and Sr and show melting-points that are sufficiently low and have excellent wettability with many metals (Fe, Ni, Mo) to easily form metal/ceramic seals. Ceramic compositions are also formulated to adequately match thermal expansion coefficient of adjacent metal components.

Corrosion resistant ceramic materials

DOEpatents

Kaun, T.D.

1996-07-23

Ceramic materials are disclosed which exhibit stability in severely-corrosive environments having high alkali-metal activity, high sulfur/sulfide activity and/or molten halides at temperatures of 200--550 C or organic salt (including SO{sub 2} and SO{sub 2}Cl{sub 2}) at temperatures of 25--200 C. These sulfide ceramics form stoichiometric (single-phase) compounds with sulfides of Ca, Li, Na, K, Al, Mg, Si, Y, La, Ce, Ga, Ba, Zr and Sr and show melting-points that are sufficiently low and have excellent wettability with many metals (Fe, Ni, Mo) to easily form metal/ceramic seals. Ceramic compositions are also formulated to adequately match thermal expansion coefficient of adjacent metal components. 1 fig.

Effective gaseous diffusion coefficients of select ultra-fine, super-fine and medium grain nuclear graphite

DOE PAGES

Kane, Joshua J.; Matthews, Austin C.; Orme, Christopher J.; ...

2018-05-05

Understanding “Where?” and “How much?” oxidation has occurred in a nuclear graphite component is critical to predicting any deleterious effects to physical, mechanical, and thermal properties. A key factor in answering these questions is characterizing the effective mass transport rates of gas species in nuclear graphites. Effective gas diffusion coefficients were determined for twenty-six graphite specimens spanning six modern grades of nuclear graphite. A correlation was established for the majority of grades examined allowing a reasonable estimate of the effective diffusion coefficient to be determined purely from an estimate of total porosity. The importance of Knudsen diffusion to the measuredmore » diffusion coefficients is also shown for modern grades. Furthermore, Knudsen diffusion has not historically been considered to contribute to measured diffusion coefficients of nuclear graphite.« less

Effective gaseous diffusion coefficients of select ultra-fine, super-fine and medium grain nuclear graphite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kane, Joshua J.; Matthews, Austin C.; Orme, Christopher J.

Understanding “Where?” and “How much?” oxidation has occurred in a nuclear graphite component is critical to predicting any deleterious effects to physical, mechanical, and thermal properties. A key factor in answering these questions is characterizing the effective mass transport rates of gas species in nuclear graphites. Effective gas diffusion coefficients were determined for twenty-six graphite specimens spanning six modern grades of nuclear graphite. A correlation was established for the majority of grades examined allowing a reasonable estimate of the effective diffusion coefficient to be determined purely from an estimate of total porosity. The importance of Knudsen diffusion to the measuredmore » diffusion coefficients is also shown for modern grades. Furthermore, Knudsen diffusion has not historically been considered to contribute to measured diffusion coefficients of nuclear graphite.« less

Copper Diffusion in Silicate Melts and Melt Inclusion Study on Volatiles in The Lunar Interior

NASA Astrophysics Data System (ADS)

Ni, Peng

This thesis focuses on the application of diffusion kinetics to both terrestrial and lunar geochemistry. In Chapters II and III, diffusivities of Cu in silicate melts were experimentally determined and used to discuss the role of Cu diffusion in formation of Cu ore deposits and also Cu isotope fractionation in tektites. In Chapters IV and V, lunar olivine-hosted melt inclusions are studied to understand their volatile loss during homogenization in lab, to estimate cooling rate for lunar Apollo sample 74220, and to estimate volatile abundance in the lunar mantle. Magmatic sulfide deposits and porphyry-type Cu deposits are two major types of Cu deposits that supply the world's Cu. In particular, porphyry-type Cu deposits provide ˜57% of the world's total discovered Cu. Recent studies suggest a potential role of diffusive transport of metals (e.g. Cu, Au, PGE, Mo) in the formation of magmatic sulfide deposits and porphyry-type deposits. Diffusivities of Cu in silicate melts, however, are poorly determined. In Chapters II and III of this thesis, Cu diffusion in basaltic melt and rhyolitic melts are studied by diffusion couple and chalcocite "dissolution" methods. Our results indicate high diffusivities of Cu and a general equation for Cu diffusion in silicate melts is obtained. The high diffusivity of Cu indicate that partition of Cu between the silicate phase and the sulfide or fluid phase can be assumed to be in equilibrium during the formation of magmatic sulfide deposits or porphyry-type deposits. In addition, our Cu diffusion data helps explain why Cu isotopes are more fractionated than Zn isotopes in tektites. Volatile abundances in the lunar mantle have profound implications for the origin of the Moon, which was thought to be bone-dry till about a decade ago, when trace amounts of H2O were detected in various types of lunar samples. In particular, high H2O concentrations comparable to mid-ocean ridge basalts were reported in lunar melt inclusions. There are still uncertainties, however, for lunar melt inclusion studies in at least two aspects. One is whether the low H2O/Ce ratios measured in homogenized crystalline inclusions are affected by the homogenization process. The other is that current estimation of volatile abundances in lunar mantle relies heavily on 74220, which is argued to be a local anomaly by some authors. In order to reach a conclusive answer on volatile abundances in lunar mantle, the above two questions have to be answered. To improve our understanding about these questions, in Chapter IV of this thesis, a series of experiments are carried out to understand possible volatile loss from lunar melt inclusions during homogenization. Our results indicate significant H2O loss from inclusions during homogenization in minutes, whereas loss of F, Cl or S is unlikely a concern under our experimental conditions. The most applicable way to preserve H2O during homogenization is to use large inclusions. In Chapter V of this thesis, volatile, trace and major element data for melt inclusions from 10020, 12040, 15016, 15647 and 74235 are reported. Our new data indicate large variation in H2O/Ce ratios from ˜77 to ˜1 across different lunar samples, which is at least partially due to H2O loss on lunar surface during cooling. In addition, evidences were found in F/Nd and S/Dy ratios that might suggest lunar mantle heterogeneity in terms of its volatile abundances.

Platinum and Palladium Exsolution Textures in Quenched Sulfide Melts

NASA Astrophysics Data System (ADS)

Reo, G.; Frank, M. R.; Loocke, M. P.; Macey, C. J.

2017-12-01

Magmatic sulfide ore deposits account for over 80% of the world's platinum group element (PGE) reserves. Layered mafic intrusions (LMIs), a type of magmatic sulfide ore deposit, contain alternating layers of silicate and sulfide mineralization that are thought to have coexisted as an immiscible silicate + sulfide melt pair. Platinum and palladium, the most common PGEs found in LMIs, heavily favor the sulfide melt. Nernst partition coefficients for Pt (D = wt% of Pt in sulfide/wt% of Pt in silicate) range from 102 to 109. This study examined the Pt- and Pd-bearing phases that formed from the quenched sulfide melts to better constrain the PGE-rich sulfide layers of LMIs system. Experiments were conducted with a basalt melt, sulfide melt, and Pt-Pd metal in a vertical tube furnace at 1100°C and 1 atm and with oxygen fugacity buffered to QFM (quartz-fayalite-magnetite). Following the experiments, run products containing both sulfide and silicate glasses (quenched melts) were analyzed by a Shimadzu EPMA-1720HT Electron Probe Microanalyzer. The focus here is on the quenched Fe-rich sulfides whereas data on the partitioning of Pt and Pd between the coexisting silicate and sulfide melts will be presented in the future. The sulfide samples were imaged in back-scattering mode and major and trace element concentrations of separate metal-rich phases in the sulfide matrix were ascertained through wavelength-dispersive x-ray spectroscopy. Three discernable PGE-rich phases were found to have exsolved from the sulfide matrix upon quenching of the sulfide melt. All of these phases had Fe and S of 21-24 and 16-22 wt.%, respectively. An irregularly shaped Pd- and Cu-rich sulfide phase ( 36 and 14 wt.%, respectively) makes up the majority of the exsolution product. A separate Pd- and Ni-rich phase ( 22 and 14 wt%, respectively) can be found as grains or rims adjacent to the exsolved Pd- and Cu-rich phase. A third Pd- and Pt-rich phase ( 26 and 18 wt.%, respectively) exhibits a dendritic quench texture and is usually surrounded by the sulfide matrix. These data indicate that multiple phases, each with a different Pt:Pd ratio can form upon quench of a homogenous sulfide melt. Thus, the analysis of PGE-rich sulfide domains within LMI may be best considered as a single phase when conducting exploration efforts.

Determination of diffusion coefficients of biocides on their passage through organic resin-based renders.

PubMed

Styszko, Katarzyna; Kupiec, Krzysztof

2016-10-01

In this study the diffusion coefficients of isoproturon, diuron and cybutryn in acrylate and silicone resin-based renders were determined. The diffusion coefficients were determined using measuring concentrations of biocides in the liquid phase after being in contact with renders for specific time intervals. The mathematical solution of the transient diffusion equation for an infinite plate contacted on one side with a limited volume of water was used to calculate the diffusion coefficient. The diffusion coefficients through the acrylate render were 8.10·10(-9) m(2) s(-1) for isoproturon, 1.96·10(-9) m(2) s(-1) for diuron and 1.53·10(-9) m(2) s(-1) for cybutryn. The results for the silicone render were lower by one order of magnitude. The compounds with a high diffusion coefficient for one polymer had likewise high values for the other polymer. Copyright © 2016 Elsevier Ltd. All rights reserved.

Simultaneous Rapid Determination of the Solubility and Diffusion Coefficients of a Poorly Water-Soluble Drug Based on a Novel UV Imaging System.

PubMed

Lu, Yan; Li, Mingzhong

2016-01-01

The solubility and diffusion coefficient are two of the most important physicochemical properties of a drug compound. In practice, both have been measured separately, which is time consuming. This work utilizes a novel technique of UV imaging to determine the solubility and diffusion coefficients of poorly water-soluble drugs simultaneously. A 2-step optimal method is proposed to determine the solubility and diffusion coefficients of a poorly water-soluble pharmaceutical substance based on the Fick's second law of diffusion and UV imaging measurements. Experimental results demonstrate that the proposed method can be used to determine the solubility and diffusion coefficients of a drug with reasonable accuracy, indicating that UV imaging may provide a new opportunity to accurately measure the solubility and diffusion coefficients of a poorly water-soluble drug simultaneously and rapidly. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Diffusion coefficients of organic molecules in sucrose-water solutions and comparison with Stokes-Einstein predictions

NASA Astrophysics Data System (ADS)

Chenyakin, Yuri; Ullmann, Dagny A.; Evoy, Erin; Renbaum-Wolff, Lindsay; Kamal, Saeid; Bertram, Allan K.

2017-02-01

The diffusion coefficients of organic species in secondary organic aerosol (SOA) particles are needed to predict the growth and reactivity of these particles in the atmosphere. Previously, viscosity measurements, along with the Stokes-Einstein relation, have been used to estimate the diffusion rates of organics within SOA particles or proxies of SOA particles. To test the Stokes-Einstein relation, we have measured the diffusion coefficients of three fluorescent organic dyes (fluorescein, rhodamine 6G and calcein) within sucrose-water solutions with varying water activity. Sucrose-water solutions were used as a proxy for SOA material found in the atmosphere. Diffusion coefficients were measured using fluorescence recovery after photobleaching. For the three dyes studied, the diffusion coefficients vary by 4-5 orders of magnitude as the water activity varied from 0.38 to 0.80, illustrating the sensitivity of the diffusion coefficients to the water content in the matrix. At the lowest water activity studied (0.38), the average diffusion coefficients were 1.9 × 10-13, 1.5 × 10-14 and 7.7 × 10-14 cm2 s-1 for fluorescein, rhodamine 6G and calcein, respectively. The measured diffusion coefficients were compared with predictions made using literature viscosities and the Stokes-Einstein relation. We found that at water activity ≥ 0.6 (which corresponds to a viscosity of ≤ 360 Pa s and Tg/T ≤ 0.81), predicted diffusion rates agreed with measured diffusion rates within the experimental uncertainty (Tg represents the glass transition temperature and T is the temperature of the measurements). When the water activity was 0.38 (which corresponds to a viscosity of 3.3 × 106 Pa s and a Tg/T of 0.94), the Stokes-Einstein relation underpredicted the diffusion coefficients of fluorescein, rhodamine 6G and calcein by a factor of 118 (minimum of 10 and maximum of 977), a factor of 17 (minimum of 3 and maximum of 104) and a factor of 70 (minimum of 8 and maximum of 494), respectively. This disagreement is significantly smaller than the disagreement observed when comparing measured and predicted diffusion coefficients of water in sucrose-water mixtures.

Mutual influence of molecular diffusion in gas and surface phases

NASA Astrophysics Data System (ADS)

Hori, Takuma; Kamino, Takafumi; Yoshimoto, Yuta; Takagi, Shu; Kinefuchi, Ikuya

2018-01-01

We develop molecular transport simulation methods that simultaneously deal with gas- and surface-phase diffusions to determine the effect of surface diffusion on the overall diffusion coefficients. The phenomenon of surface diffusion is incorporated into the test particle method and the mean square displacement method, which are typically employed only for gas-phase transport. It is found that for a simple cylindrical pore, the diffusion coefficients in the presence of surface diffusion calculated by these two methods show good agreement. We also confirm that both methods reproduce the analytical solution. Then, the diffusion coefficients for ink-bottle-shaped pores are calculated using the developed method. Our results show that surface diffusion assists molecular transport in the gas phase. Moreover, the surface tortuosity factor, which is known to be uniquely determined by physical structure, is influenced by the presence of gas-phase diffusion. This mutual influence of gas-phase diffusion and surface diffusion indicates that their simultaneous calculation is necessary for an accurate evaluation of the diffusion coefficients.

Molecular modeling of diffusion coefficient and ionic conductivity of CO2 in aqueous ionic solutions.

PubMed

Garcia-Ratés, Miquel; de Hemptinne, Jean-Charles; Bonet Avalos, Josep; Nieto-Draghi, Carlos

2012-03-08

Mass diffusion coefficients of CO(2)/brine mixtures under thermodynamic conditions of deep saline aquifers have been investigated by molecular simulation. The objective of this work is to provide estimates of the diffusion coefficient of CO(2) in salty water to compensate the lack of experimental data on this property. We analyzed the influence of temperature, CO(2) concentration,and salinity on the diffusion coefficient, the rotational diffusion, as well as the electrical conductivity. We observe an increase of the mass diffusion coefficient with the temperature, but no clear dependence is identified with the salinity or with the CO(2) mole fraction, if the system is overall dilute. In this case, we notice an important dispersion on the values of the diffusion coefficient which impairs any conclusive statement about the effect of the gas concentration on the mobility of CO(2) molecules. Rotational relaxation times for water and CO(2) increase by decreasing temperature or increasing the salt concentration. We propose a correlation for the self-diffusion coefficient of CO(2) in terms of the rotational relaxation time which can ultimately be used to estimate the mutual diffusion coefficient of CO(2) in brine. The electrical conductivity of the CO(2)-brine mixtures was also calculated under different thermodynamic conditions. Electrical conductivity tends to increase with the temperature and salt concentration. However, we do not observe any influence of this property with the CO(2) concentration at the studied regimes. Our results give a first evaluation of the variation of the CO(2)-brine mass diffusion coefficient, rotational relaxation times, and electrical conductivity under the thermodynamic conditions typically encountered in deep saline aquifers.

Spin Diffusion Coefficient of A1-PHASE of Superfluid 3He at Low Temperatures

NASA Astrophysics Data System (ADS)

Afzali, R.; Pashaee, F.

The spin diffusion coefficient tensor of the A1-phase of superfluid 3He at low temperatures and melting pressure is calculated using the Boltzmann equation approach and Pfitzner procedure. Then considering Bogoliubov-normal interaction, we show that the total spin diffusion is proportional to 1/T2, the spin diffusion coefficient of superfluid component D\\uparrowxzxz is proportional to T-2, and the spin diffusion coefficient of super-fluid component D\\uparrowxxxx (=D\\uarrowxyxy) is independent of temperature. Furthermore, it is seen that superfluid components play an important role in spin diffusion of the A1-phase.

Static and Dynamic Effects of Lateral Carrier Diffusion in Semiconductor Lasers

NASA Technical Reports Server (NTRS)

Li, Jian-Zhong; Cheung, Samson H.; Ning, C. Z.; Biegel, Bryan A. (Technical Monitor)

2002-01-01

Electron and hole diffusions in the plane of semiconductor quantum wells play an important part in the static and dynamic operations of semiconductor lasers. It is well known that the value of diffusion coefficients affects the threshold pumping current of a semiconductor laser. At the same time, the strength of carrier diffusion process is expected to affect the modulation bandwidth of an AC-modulated laser. It is important not only to investigate the combined DC and AC effects due to carrier diffusion, but also to separate the AC effects from that of the combined effects in order to provide design insights for high speed modulation. In this presentation, we apply a hydrodynamic model developed by the present authors recently from the semiconductor Bloch equations. The model allows microscopic calculation of the lateral carrier diffusion coefficient, which is a nonlinear function of the carrier density and plasma temperature. We first studied combined AC and DC effects of lateral carrier diffusion by studying the bandwidth dependence on diffusion coefficient at a given DC current under small signal modulation. The results show an increase of modulation bandwidth with decrease in the diffusion coefficient. We simultaneously studied the effects of nonlinearity in the diffusion coefficient. To clearly identify how much of the bandwidth increase is a result of decrease in the threshold pumping current for smaller diffusion coefficient, thus an effective increase of DC pumping, we study the bandwidth dependence on diffusion coefficient at a given relative pumping. A detailed comparison of the two cases will be presented.

Diffusion and mobility of atomic particles in a liquid

NASA Astrophysics Data System (ADS)

Smirnov, B. M.; Son, E. E.; Tereshonok, D. V.

2017-11-01

The diffusion coefficient of a test atom or molecule in a liquid is determined for the mechanism where the displacement of the test molecule results from the vibrations and motion of liquid molecules surrounding the test molecule and of the test particle itself. This leads to a random change in the coordinate of the test molecule, which eventually results in the diffusion motion of the test particle in space. Two models parameters of interaction of a particle and a liquid are used to find the activation energy of the diffusion process under consideration: the gas-kinetic cross section for scattering of test molecules in the parent gas and the Wigner-Seitz radius for test molecules. In the context of this approach, we have calculated the diffusion coefficient of atoms and molecules in water, where based on experimental data, we have constructed the dependence of the activation energy for the diffusion of test molecules in water on the interaction parameter and the temperature dependence for diffusion coefficient of atoms or molecules in water within the models considered. The statistically averaged difference of the activation energies for the diffusion coefficients of different test molecules in water that we have calculated based on each of the presented models does not exceed 10% of the diffusion coefficient itself. We have considered the diffusion of clusters in water and present the dependence of the diffusion coefficient on the cluster size. The accuracy of the presented formulas for the diffusion coefficient of atomic particles in water is estimated to be 50%.

Unsaturated soil moisture drying and wetting diffusion coefficient measurements in the laboratory.

DOT National Transportation Integrated Search

2009-09-01

ABSTRACTTransient moisture flow in an unsaturated soil in response to suction changes is controlled by the unsaturated moisture diffusion coefficient. The moisture diffusion coefficient can be determined by measuring suction profiles over time. The l...

Competition for sulfide among colorless and purple sulfur bacteria in cyanobacterial mats

NASA Technical Reports Server (NTRS)

Jorgensen, B. B.; Des Marais, D. J.

1986-01-01

The vertical zonation of light, O2, H2S, pH, and sulfur bacteria was studied in two benthic cyanobacterial mats from hypersaline ponds at Guerrero Negro, Baja California, Mexico. The physical-chemical gradients were analyzed in the upper few mm at < or = 100 micrometers spatial resolution by microelectrodes and by a fiber optic microprobe. In mats, where oxygen produced by photosynthesis diffused far below the depth of the photic zone, colorless sulfur bacteria (Beggiatoa sp.) were the dominant sulfide oxidizing organisms. In a mat, where the O2-H2S interface was close to the photic zone, but yet received no significant visible light, purple sulfur bacteria (Chromatium sp.) were the dominant sulfide oxidizers. Analysis of the spectral light distribution here showed that the penetration of only 1% of the incident near-IR light (800-900 nm) into the sulfide zone was sufficient for the mass development of Chromatium in a narrow band of 300 micromoles thickness. The balance between O2 and light penetration down into the sulfide zone thus determined in micro-scale which type of sulfur bacteria became dominant.

A novel approach to interpretation of the time-dependent self-diffusion coefficient as a probe of porous media geometry.

PubMed

Loskutov, V V; Sevriugin, V A

2013-05-01

This article presents a new approximation describing fluid diffusion in porous media. Time dependence of the self-diffusion coefficient D(t) in the permeable porous medium is studied based on the assumption that diffusant molecules move randomly. An analytical expression for time dependence of the self-diffusion coefficient was obtained in the following form: D(t)=(D0-D∞)exp(-D0t/λ)+D∞, where D0 is the self-diffusion coefficient of bulk fluid, D∞ is the asymptotic value of the self-diffusion coefficient in the limit of long time values (t→∞), λ is the characteristic parameter of this porous medium with dimensionality of length. Applicability of the solution obtained to the analysis of experimental data is shown. The possibility of passing to short-time and long-time regimes is discussed. Copyright © 2013 Elsevier Inc. All rights reserved.

Single-image diffusion coefficient measurements of proteins in free solution.

PubMed

Zareh, Shannon Kian; DeSantis, Michael C; Kessler, Jonathan M; Li, Je-Luen; Wang, Y M

2012-04-04

Diffusion coefficient measurements are important for many biological and material investigations, such as studies of particle dynamics and kinetics, and size determinations. Among current measurement methods, single particle tracking (SPT) offers the unique ability to simultaneously obtain location and diffusion information about a molecule while using only femtomoles of sample. However, the temporal resolution of SPT is limited to seconds for single-color-labeled samples. By directly imaging three-dimensional diffusing fluorescent proteins and studying the widths of their intensity profiles, we were able to determine the proteins' diffusion coefficients using single protein images of submillisecond exposure times. This simple method improves the temporal resolution of diffusion coefficient measurements to submilliseconds, and can be readily applied to a range of particle sizes in SPT investigations and applications in which diffusion coefficient measurements are needed, such as reaction kinetics and particle size determinations. Copyright © 2012 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Diffusion coefficients in systems with inclusion compounds. 1. alpha. -Cyclodextrin-L-phenylalanine-water at 25 degree C

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paduano, L.; Sartorio, R.; Vitagliano, V.

Diffusion coefficients in the ternary system {alpha}-cyclodextrin (at one concentration)-L-phenylalanine (at four concentrations)-water have been measured by using the Gouy interferometric technique. The effect of the inclusion equilibrium on the cross-term diffusion coefficients was observed. The measured diffusion coefficients in the ternary systems were used to calculate values of the binding constants. These values are in good agreement with the value obtained from calorimetric studies.

Banded Structures in Electron Pitch Angle Diffusion Coefficients from Resonant Wave Particle Interactions

NASA Technical Reports Server (NTRS)

Tripathi, A. K.; Singhal, R. P.; Khazanov, G. V.; Avanov, L. A.

2016-01-01

Electron pitch angle (D (alpha)) and momentum (D(pp)) diffusion coefficients have been calculated due to resonant interactions with electrostatic electron cyclotron harmonic (ECH) and whistler mode chorus waves. Calculations have been performed at two spatial locations L = 4.6 and 6.8 for electron energies 10 keV. Landau (n = 0) resonance and cyclotron harmonic resonances n = +/-1, +/-2,...+/-5 have been included in the calculations. It is found that diffusion coefficient versus pitch angle (alpha) profiles show large dips and oscillations or banded structures. The structures are more pronounced for ECH and lower band chorus (LBC) and particularly at location 4.6. Calculations of diffusion coefficients have also been performed for individual resonances. It is noticed that the main contribution of ECH waves in pitch angle diffusion coefficient is due to resonances n = +1 and n = +2. A major contribution to momentum diffusion coefficients appears from n = +2. However, the banded structures in D alpha and Dpp coefficients appear only in the profile of diffusion coefficients for n = +2. The contribution of other resonances to diffusion coefficients is found to be, in general, quite small or even negligible. For LBC and upper band chorus waves, the banded structures appear only in Landau resonance. The Dpp diffusion coefficient for ECH waves is one to two orders smaller than D alpha coefficients. For chorus waves, Dpp coefficients are about an order of magnitude smaller than D alpha coefficients for the case n does not = 0. In case of Landau resonance, the values of Dpp coefficient are generally larger than the values of D alpha coefficients particularly at lower energies. As an aid to the interpretation of results, we have also determined the resonant frequencies. For ECH waves, resonant frequencies have been estimated for wave normal angle 89 deg and harmonic resonances n = +1, +2, and +3, whereas for whistler mode waves, the frequencies have been calculated for angle 10 deg and Landau resonance. Further, in ECH waves, the banded structures appear for electron energies (is) greater than1 keV, and for whistler mode chorus waves, structures appear for energies greater than 2 keV at L = 4.6 and above 200 eV for L = 6.8. The results obtained in the present work will be helpful in the study of diffusion curves and will have important consequences for diffuse aurora and pancake distributions.

Banded Structures in Electron Pitch Angle Diffusion Coefficients from Resonant Wave-Particle Interactions

NASA Technical Reports Server (NTRS)

Tripathi, A. K.; Singhal, R. P.; Khazanov, G. V.; Avanov, L. A.

2016-01-01

Electron pitch angle (D(sub (alpha alpha))) and momentum (D(sub pp)) diffusion coefficients have been calculated due to resonant interactions with electrostatic electron cyclotron harmonic (ECH) and whistler mode chorus waves. Calculations have been performed at two spatial locations L=4.6 and 6.8 for electron energies less than or equal to 10 keV. Landau (n=0) resonance and cyclotron harmonic resonances n= +/- 1, +/-2, ... +/-5 have been included in the calculations. It is found that diffusion coefficient versus pitch angle (alpha) profiles show large dips and oscillations or banded structures. The structures are more pronounced for ECH and lower band chorus (LBC) and particularly at location 4.6. Calculations of diffusion coefficients have also been performed for individual resonances. It is noticed that the main contribution of ECH waves in pitch angle diffusion coefficient is due to resonances n=+1 and n=+2. A major contribution to momentum diffusion coefficients appears from n=+2. However, the banded structures in D(sub alpha alpha) and D(sub pp) coefficients appear only in the profile of diffusion coefficients for n=+2. The contribution of other resonances to diffusion coefficients is found to be, in general, quite small or even negligible. For LBC and upper band chorus waves, the banded structures appear only in Landau resonance. The D(sub pp) diffusion coefficient for ECH waves is one to two orders smaller than D(sub alpha alpha) coefficients. For chorus waves, D(sub pp) coefficients are about an order of magnitude smaller than D(sub alpha alpha) coefficients for the case n does not equal 0. In case of Landau resonance, the values of D(sub pp) coefficient are generally larger than the values of D(sub alpha alpha) coefficients particularly at lower energies. As an aid to the interpretation of results, we have also determined the resonant frequencies. For ECH waves, resonant frequencies have been estimated for wave normal angle 89 deg and harmonic resonances n= +1, +2, and +3, whereas for whistler mode waves, the frequencies have been calculated for angle 10 deg and Landau resonance. Further, in ECH waves, the banded structures appear for electron energies 1 greater than or equal to keV, and for whistler mode chorus waves, structures appear for energies greater than 2 keV at L=4.6 and above 200 eV for L=6.8. The results obtained in the present work will be helpful in the study of diffusion curves and will have important consequences for diffuse aurora and pancake distributions.

Bulk diffusion in a kinetically constrained lattice gas

NASA Astrophysics Data System (ADS)

Arita, Chikashi; Krapivsky, P. L.; Mallick, Kirone

2018-03-01

In the hydrodynamic regime, the evolution of a stochastic lattice gas with symmetric hopping rules is described by a diffusion equation with density-dependent diffusion coefficient encapsulating all microscopic details of the dynamics. This diffusion coefficient is, in principle, determined by a Green-Kubo formula. In practice, even when the equilibrium properties of a lattice gas are analytically known, the diffusion coefficient cannot be computed except when a lattice gas additionally satisfies the gradient condition. We develop a procedure to systematically obtain analytical approximations for the diffusion coefficient for non-gradient lattice gases with known equilibrium. The method relies on a variational formula found by Varadhan and Spohn which is a version of the Green-Kubo formula particularly suitable for diffusive lattice gases. Restricting the variational formula to finite-dimensional sub-spaces allows one to perform the minimization and gives upper bounds for the diffusion coefficient. We apply this approach to a kinetically constrained non-gradient lattice gas in two dimensions, viz. to the Kob-Andersen model on the square lattice.

Measurement of effective air diffusion coefficients for trichloroethene in undisturbed soil cores.

PubMed

Bartelt-Hunt, Shannon L; Smith, James A

2002-06-01

In this study, we measure effective diffusion coefficients for trichloroethene in undisturbed soil samples taken from Picatinny Arsenal, New Jersey. The measured effective diffusion coefficients ranged from 0.0053 to 0.0609 cm2/s over a range of air-filled porosity of 0.23-0.49. The experimental data were compared to several previously published relations that predict diffusion coefficients as a function of air-filled porosity and porosity. A multiple linear regression analysis was developed to determine if a modification of the exponents in Millington's [Science 130 (1959) 100] relation would better fit the experimental data. The literature relations appeared to generally underpredict the effective diffusion coefficient for the soil cores studied in this work. Inclusion of a particle-size distribution parameter, d10, did not significantly improve the fit of the linear regression equation. The effective diffusion coefficient and porosity data were used to recalculate estimates of diffusive flux through the subsurface made in a previous study performed at the field site. It was determined that the method of calculation used in the previous study resulted in an underprediction of diffusive flux from the subsurface. We conclude that although Millington's [Science 130 (1959) 100] relation works well to predict effective diffusion coefficients in homogeneous soils with relatively uniform particle-size distributions, it may be inaccurate for many natural soils with heterogeneous structure and/or non-uniform particle-size distributions.

Sulfidation of Co/Al[sub 2]O[sub 3] and CoMo/Al[sub 2]O[sub 3] catalysts studied by Moessbauer emission spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Craje, M.W.J.; Kraan, A.M. van der; Beer, V.H.J. de

1993-10-01

The structure of hydrodesulfurization catalysts is relevant to many industries. The sulfidation of uncalcined and calcined alumina-supported cobalt and cobalt-molybdenum catalysts was systematically studied by means of in situ Moessbauer emission spectroscopy (MES) at room temperature. The spectra obtained during the stepwise sulfidation of the uncalcined catalysts clearly resemble those observed for carbon-supported ones. Hence, the interpretation of the spectra of the alumina-supported catalysts is based on the conclusions drawn from the MES studies of the carbon-supported catalysts, which are less complex because Co ions do not diffuse into the support. It is demonstrated that not only in sulfided CoMo/Al[submore » 2]O[sub 3], but also in sulfided Co/Al[sub 2]O[sub 3], catalysts Co-sulfide species with a [open quotes]Co-Mo-S[close quotes]-type quadrupole splitting can be formed. It is concluded that the Co-sulfide species formed in sulfided Co/Al[sub 2]O[sub 3] and CoMo/Al[sub 2]O[sub 3] catalysts are essentially the same, only the particle size and ordering of the Co-sulfide species may differ, as in the case of Co/C and CoMo/C catalysts. The function of the Mo, which is present as MoS[sub 2], is merely to stabilize very small Co-sulfide particles, which in the limit contain only one single Co atom. Furthermore, it turns out that the value of the electric quadrupole splitting (Q.S. value) of the Co-sulfide phase in the sulfided catalysts depends on the sulfiding temperature and Co content. This observation leads to the conclusion that large Q.S. values point to the presence of very small Co-sulfide entities or particles (the lower limit being [open quotes]particles[close quotes] containing only one Co atom, such as proposed in the [open quotes]Co-Mo-S[close quotes] model), whereas small Q.S. values point to the presence of large Co-sulfide particles (the upper limit being crystalline Co[sub 9]S[sub 8]). 28 refs., 7 figs., 6 tabs.« less

Temperature-Dependent Rate Coefficients for the Reaction of CH2OO with Hydrogen Sulfide.

PubMed

Smith, Mica C; Chao, Wen; Kumar, Manoj; Francisco, Joseph S; Takahashi, Kaito; Lin, Jim Jr-Min

2017-02-09

The reaction of the simplest Criegee intermediate CH 2 OO with hydrogen sulfide was measured with transient UV absorption spectroscopy in a temperature-controlled flow reactor, and bimolecular rate coefficients were obtained from 278 to 318 K and from 100 to 500 Torr. The average rate coefficient at 298 K and 100 Torr was (1.7 ± 0.2) × 10 -13 cm 3 s -1 . The reaction was found to be independent of pressure and exhibited a weak negative temperature dependence. Ab initio quantum chemistry calculations of the temperature-dependent reaction rate coefficient at the QCISD(T)/CBS level are in reasonable agreement with the experiment. The reaction of CH 2 OO with H 2 S is 2-3 orders of magnitude faster than the reaction with H 2 O monomer. Though rates of CH 2 OO scavenging by water vapor under atmospheric conditions are primarily controlled by the reaction with water dimer, the H 2 S loss pathway will be dominated by the reaction with monomer. The agreement between experiment and theory for the CH 2 OO + H 2 S reaction lends credence to theoretical descriptions of other Criegee intermediate reactions that cannot easily be probed experimentally.

Speciation and Lability of Ag-, AgCl- and Ag2S-Nanoparticles in Soil Determined by X-ray Absorption Spectroscopy and Diffusive Gradients in Thin Films

EPA Science Inventory

Long-term speciation and lability of silver (Ag-), silver chloride (AgCl-) and silver sulfide nanoparticles (Ag₂S-NPs) in soil were studied by X-ray absorption spectroscopy (XAS), and newly developed "nano" Diffusive Gradients in Thin Films (DGT) devices. These nano-D...

Determination of the diffusion coefficient of hydrogen ion in hydrogels.

PubMed

Schuszter, Gábor; Gehér-Herczegh, Tünde; Szűcs, Árpád; Tóth, Ágota; Horváth, Dezső

2017-05-17

The role of diffusion in chemical pattern formation has been widely studied due to the great diversity of patterns emerging in reaction-diffusion systems, particularly in H + -autocatalytic reactions where hydrogels are applied to avoid convection. A custom-made conductometric cell is designed to measure the effective diffusion coefficient of a pair of strong electrolytes containing sodium ions or hydrogen ions with a common anion. This together with the individual diffusion coefficient for sodium ions, obtained from PFGSE-NMR spectroscopy, allows the determination of the diffusion coefficient of hydrogen ions in hydrogels. Numerical calculations are also performed to study the behavior of a diffusion-migration model describing ionic diffusion in our system. The method we present for one particular case may be extended for various hydrogels and diffusing ions (such as hydroxide) which are relevant e.g. for the development of pH-regulated self-healing mechanisms and hydrogels used for drug delivery.

Extensive database of liquid phase diffusion coefficients of some frequently used test molecules in reversed-phase liquid chromatography and hydrophilic interaction liquid chromatography.

PubMed

Song, Huiying; Vanderheyden, Yoachim; Adams, Erwin; Desmet, Gert; Cabooter, Deirdre

2016-07-15

Diffusion plays an important role in all aspects of band broadening in chromatography. An accurate knowledge of molecular diffusion coefficients in different mobile phases is therefore crucial in fundamental column performance studies. Correlations available in literature, such as the Wilke-Chang equation, can provide good approximations of molecular diffusion under reversed-phase conditions. However, these correlations have been demonstrated to be less accurate for mobile phases containing a large percentage of acetonitrile, as is the case in hydrophilic interaction liquid chromatography. A database of experimentally measured molecular diffusion coefficients of some 45 polar and apolar compounds that are frequently used as test molecules under hydrophilic interaction liquid chromatography and reversed-phase conditions is therefore presented. Special attention is given to diffusion coefficients of polar compounds obtained in large percentages of acetonitrile (>90%). The effect of the buffer concentration (5-10mM ammonium acetate) on the obtained diffusion coefficients is investigated and is demonstrated to mainly influence the molecular diffusion of charged molecules. Diffusion coefficients are measured using the Taylor-Aris method and hence deduced from the peak broadening of a solute when flowing through a long open tube. The validity of the set-up employed for the measurement of the diffusion coefficients is demonstrated by ruling out the occurrence of longitudinal diffusion, secondary flow interactions and extra-column effects, while it is also shown that radial equilibration in the 15m long capillary is effective. Copyright © 2016 Elsevier B.V. All rights reserved.

H2S Loss through Nalophan™ Bags: Contributions of Adsorption and Diffusion

PubMed Central

2017-01-01

Hydrogen-sulfide (H2S) is a molecule of small dimensions typically present in the odor emissions from different plants. The European Standard EN 13725:2003 set a maximum storage time allowed of 30 hours, during which the sampling bag has to maintain the mixture of odorants with minimal changes. This study investigates the H2S losses through Nalophan bags and it shows that nonnegligible losses of H2S can be observed. The percent H2S loss after 30 hrs with respect to the initial concentration is equal to 33%  ± 3% at a relative humidity of 20% and equal to 22%  ± 1% at a relative humidity of 60%. The average quantity of adsorbed H2S at 30 h is equal to 2.17 105 gH2S/gNalophan at a storage humidity of 20% and equal to 1.79 105 gH2S/gNalophan at a storage humidity of 60%. The diffusion coefficients of H2S through Nalophan, for these two humidity conditions tested, are comparable (i.e., 7.5 10−12 m2/sec at 20% humidity and 6.6 10−12 m2/sec at 60% humidity). PMID:28740857

Alternative waste residue materials for passive in situ prevention of sulfide-mine tailings oxidation: a field evaluation.

PubMed

Nason, Peter; Johnson, Raymond H; Neuschütz, Clara; Alakangas, Lena; Öhlander, Björn

2014-02-28

Novel solutions for sulfide-mine tailings remediation were evaluated in field-scale experiments on a former tailings repository in northern Sweden. Uncovered sulfide-tailings were compared to sewage-sludge biosolid amended tailings over 2 years. An application of a 0.2m single-layer sewage-sludge amendment was unsuccessful at preventing oxygen ingress to underlying tailings. It merely slowed the sulfide-oxidation rate by 20%. In addition, sludge-derived metals (Cu, Ni, Fe, and Zn) migrated and precipitated at the tailings-to-sludge interface. By using an additional 0.6m thick fly-ash sealing layer underlying the sewage sludge layer, a solution to mitigate oxygen transport to the underlying tailings and minimize sulfide-oxidation was found. The fly-ash acted as a hardened physical barrier that prevented oxygen diffusion and provided a trap for sludge-borne metals. Nevertheless, the biosolid application hampered the application, despite the advances in the effectiveness of the fly-ash layer, as sludge-borne nitrate leached through the cover system into the underlying tailings, oxidizing pyrite. This created a 0.3m deep oxidized zone in 6-years. This study highlights that using sewage sludge in unconventional cover systems is not always a practical solution for the remediation of sulfide-bearing mine tailings to mitigate against sulfide weathering and acid rock drainage formation. Copyright © 2014 Elsevier B.V. All rights reserved.

Sulfur transformations at the hydrogen sulfide/oxygen interface in stratified waters and in cyanobacterial mats

NASA Technical Reports Server (NTRS)

Cohen, Y.

1985-01-01

Stratified water bodies allow the development of several microbial plates along the water column. The microbial plates develop in relation to nutrient availability, light penetration, and the distribution of oxygen and sulfide. Sulfide is initially produced in the sediment by sulfate-reducing bacteria. It diffuses along the water column creating a zone of hydrogen sulfide/oxygen interface. In the chemocline of Solar Lake oxygen and sulfide coexist in a 0 to 10 cm layer that moves up and down during a diurnal cycle. The microbial plate at the chemocline is exposed to oxygen and hydrogen sulfide, alternating on a diurnal basis. The cyanobacteria occupying the interface switch from anoxygenic photosynthesis in the morning to oxygenic photosynthesis during the rest of the day which results in a temporal build up of elemental sulfur during the day and disappears at night due to both oxidation to thiosulfate and sulfate by thiobacilli, and reduction to hydrogen sulfide by Desulfuromonas sp. and anaerobically respiring cyanobacteria. Sulfate reduction was enhanced in the light at the surface of the cyanobacterial mats. Microsulfate reduction measurements showed enhanced activity of sulfate reduction even under high oxygen concentrations of 300 to 800 micrometer. Apparent aerobic SO sub 4 reduction activity is explained by the co-occurrence of H sub 2. The physiology of this apparent sulfate reduction activity is studied.

Alternative waste residue materials for passive in situ prevention of sulfide-mine tailings oxidation: A field evaluation

USGS Publications Warehouse

Nason, Peter; Johnson, Raymond H.; Neuschutz, Clara; Alakangas, Lena; Ohlander, Bjorn

2014-01-01

Novel solutions for sulfide-mine tailings remediation were evaluated in field-scale experiments on a former tailings repository in northern Sweden. Uncovered sulfide-tailings were compared to sewage-sludge biosolid amended tailings over 2 years. An application of a 0.2 m single-layer sewage-sludge amendment was unsuccessful at preventing oxygen ingress to underlying tailings. It merely slowed the sulfide-oxidation rate by 20%. In addition, sludge-derived metals (Cu, Ni, Fe, and Zn) migrated and precipitated at the tailings-to-sludge interface. By using an additional 0.6 m thick fly-ash sealing layer underlying the sewage sludge layer, a solution to mitigate oxygen transport to the underlying tailings and minimize sulfide-oxidation was found. The fly-ash acted as a hardened physical barrier that prevented oxygen diffusion and provided a trap for sludge-borne metals. Nevertheless, the biosolid application hampered the application, despite the advances in the effectiveness of the fly-ash layer, as sludge-borne nitrate leached through the cover system into the underlying tailings, oxidizing pyrite. This created a 0.3 m deep oxidized zone in 6-years. This study highlights that using sewage sludge in unconventional cover systems is not always a practical solution for the remediation of sulfide-bearing mine tailings to mitigate against sulfide weathering and acid rock drainage formation.

Multi-dimensional modeling of atmospheric copper-sulfidation corrosion on non-planar substrates.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Ken Shuang

2004-11-01

This report documents the author's efforts in the deterministic modeling of copper-sulfidation corrosion on non-planar substrates such as diodes and electrical connectors. A new framework based on Goma was developed for multi-dimensional modeling of atmospheric copper-sulfidation corrosion on non-planar substrates. In this framework, the moving sulfidation front is explicitly tracked by treating the finite-element mesh as a pseudo solid with an arbitrary Lagrangian-Eulerian formulation and repeatedly performing re-meshing using CUBIT and re-mapping using MAPVAR. Three one-dimensional studies were performed for verifying the framework in asymptotic regimes. Limited model validation was also carried out by comparing computed copper-sulfide thickness with experimentalmore » data. The framework was first demonstrated in modeling one-dimensional copper sulfidation with charge separation. It was found that both the thickness of the space-charge layers and the electrical potential at the sulfidation surface decrease rapidly as the Cu{sub 2}S layer thickens initially but eventually reach equilibrium values as Cu{sub 2}S layer becomes sufficiently thick; it was also found that electroneutrality is a reasonable approximation and that the electro-migration flux may be estimated by using the equilibrium potential difference between the sulfidation and annihilation surfaces when the Cu{sub 2}S layer is sufficiently thick. The framework was then employed to model copper sulfidation in the solid-state-diffusion controlled regime (i.e. stage II sulfidation) on a prototypical diode until a continuous Cu{sub 2}S film was formed on the diode surface. The framework was also applied to model copper sulfidation on an intermittent electrical contact between a gold-plated copper pin and gold-plated copper pad; the presence of Cu{sub 2}S was found to raise the effective electrical resistance drastically. Lastly, future research needs in modeling atmospheric copper sulfidation are discussed.« less

Method of producing microporous joints in metal bodies

DOEpatents

Danko, Joseph C.

1982-01-01

Tungsten is placed in contact with either molybdenum, tantalum, niobium, vanadium, rhenium, or other metal of atoms having a different diffusion coefficient than tungsten. The metals are heated so that the atoms having the higher diffusion coefficient migrate to the metal having the lower diffusion rate, leaving voids in the higher diffusion coefficient metal. Heating is continued until the voids are interconnected.

First-principles multiple-barrier diffusion theory. The case study of interstitial diffusion in CdTe

DOE PAGES

Yang, Ji -Hui; Park, Ji -Sang; Kang, Joongoo; ...

2015-02-17

The diffusion of particles in solid-state materials generally involves several sequential thermal-activation processes. However, presently, diffusion coefficient theory only deals with a single barrier, i.e., it lacks an accurate description to deal with multiple-barrier diffusion. Here, we develop a general diffusion coefficient theory for multiple-barrier diffusion. Using our diffusion theory and first-principles calculated hopping rates for each barrier, we calculate the diffusion coefficients of Cd, Cu, Te, and Cl interstitials in CdTe for their full multiple-barrier diffusion pathways. As a result, we found that the calculated diffusivity agrees well with the experimental measurement, thus justifying our theory, which is generalmore » for many other systems.« less

Gas-film coefficients for streams

USGS Publications Warehouse

Rathbun, R.E.; Tai, D.Y.

1983-01-01

Equations for predicting the gas-film coefficient for the volatilization of organic solutes from streams are developed. The film coefficient is a function of windspeed and water temperature. The dependence of the coefficient on windspeed is determined from published information on the evaporation of water from a canal. The dependence of the coefficient on temperature is determined from laboratory studies on the evaporation of water. Procedures for adjusting the coefficients for different organic solutes are based on the molecular diffusion coefficient and the molecular weight. The molecular weight procedure is easiest to use because of the availability of molecular weights. However, the theoretical basis of the procedure is questionable. The diffusion coefficient procedure is supported by considerable data. Questions, however, remain regarding the exact dependence of the film coefficint on the diffusion coefficient. It is suggested that the diffusion coefficient procedure with a 0.68-power dependence be used when precise estimate of the gas-film coefficient are needed and that the molecular weight procedure be used when only approximate estimates are needed.

An Ab Initio and Kinetic Monte Carlo Simulation Study of Lithium Ion Diffusion on Graphene

PubMed Central

Zhong, Kehua; Yang, Yanmin; Xu, Guigui; Zhang, Jian-Min; Huang, Zhigao

2017-01-01

The Li+ diffusion coefficients in Li+-adsorbed graphene systems were determined by combining first-principle calculations based on density functional theory with Kinetic Monte Carlo simulations. The calculated results indicate that the interactions between Li ions have a very important influence on lithium diffusion. Based on energy barriers directly obtained from first-principle calculations for single-Li+ and two-Li+ adsorbed systems, a new equation predicting energy barriers with more than two Li ions was deduced. Furthermore, it is found that the temperature dependence of Li+ diffusion coefficients fits well to the Arrhenius equation, rather than meeting the equation from electrochemical impedance spectroscopy applied to estimate experimental diffusion coefficients. Moreover, the calculated results also reveal that Li+ concentration dependence of diffusion coefficients roughly fits to the equation from electrochemical impedance spectroscopy in a low concentration region; however, it seriously deviates from the equation in a high concentration region. So, the equation from electrochemical impedance spectroscopy technique could not be simply used to estimate the Li+ diffusion coefficient for all Li+-adsorbed graphene systems with various Li+ concentrations. Our work suggests that interactions between Li ions, and among Li ion and host atoms will influence the Li+ diffusion, which determines that the Li+ intercalation dependence of Li+ diffusion coefficient should be changed and complex. PMID:28773122

On the Ageing of High Energy Lithium-Ion Batteries—Comprehensive Electrochemical Diffusivity Studies of Harvested Nickel Manganese Cobalt Electrodes

PubMed Central

Jaguemont, Joris; Van Den Bossche, Peter; Omar, Noshin; Van Mierlo, Joeri

2018-01-01

This paper examines the impact of the characterisation technique considered for the determination of the Li+ solid state diffusion coefficient in uncycled as in cycled Nickel Manganese Cobalt oxide (NMC) electrodes. As major characterisation techniques, Cyclic Voltammetry (CV), Galvanostatic Intermittent Titration Technique (GITT) and Electrochemical Impedance Spectroscopy (EIS) were systematically investigated. Li+ diffusion coefficients during the lithiation process of the uncycled and cycled electrodes determined by CV at 3.71 V are shown to be equal to 3.48×10−10 cm2·s−1 and 1.56×10−10 cm2·s−1 , respectively. The dependency of the Li+ diffusion with the lithium content in the electrodes is further studied in this paper with GITT and EIS. Diffusion coefficients calculated by GITT and EIS characterisations are shown to be in the range between 1.76×10−15 cm2·s−1 and 4.06×10−12 cm2·s−1, while demonstrating the same decreasing trend with the lithiation process of the electrodes. For both electrode types, diffusion coefficients calculated by CV show greater values compared to those determined by GITT and EIS. With ageing, CV and EIS techniques lead to diffusion coefficients in the electrodes at 3.71 V that are decreasing, in contrast to GITT for which results indicate increasing diffusion coefficient. After long-term cycling, ratios of the diffusion coefficients determined by GITT compared to CV become more significant with an increase about 1 order of magnitude, while no significant variation is seen between the diffusion coefficients calculated from EIS in comparison to CV. PMID:29360787

On the Ageing of High Energy Lithium-Ion Batteries-Comprehensive Electrochemical Diffusivity Studies of Harvested Nickel Manganese Cobalt Electrodes.

PubMed

Capron, Odile; Gopalakrishnan, Rahul; Jaguemont, Joris; Van Den Bossche, Peter; Omar, Noshin; Van Mierlo, Joeri

2018-01-23

This paper examines the impact of the characterisation technique considered for the determination of the L i + solid state diffusion coefficient in uncycled as in cycled Nickel Manganese Cobalt oxide (NMC) electrodes. As major characterisation techniques, Cyclic Voltammetry (CV), Galvanostatic Intermittent Titration Technique (GITT) and Electrochemical Impedance Spectroscopy (EIS) were systematically investigated. L i + diffusion coefficients during the lithiation process of the uncycled and cycled electrodes determined by CV at 3.71 V are shown to be equal to 3 . 48 × 10 - 10 cm 2 ·s - 1 and 1 . 56 × 10 - 10 cm 2 ·s - 1 , respectively. The dependency of the L i + diffusion with the lithium content in the electrodes is further studied in this paper with GITT and EIS. Diffusion coefficients calculated by GITT and EIS characterisations are shown to be in the range between 1 . 76 × 10 - 15 cm 2 ·s - 1 and 4 . 06 × 10 - 12 cm 2 ·s - 1 , while demonstrating the same decreasing trend with the lithiation process of the electrodes. For both electrode types, diffusion coefficients calculated by CV show greater values compared to those determined by GITT and EIS. With ageing, CV and EIS techniques lead to diffusion coefficients in the electrodes at 3.71 V that are decreasing, in contrast to GITT for which results indicate increasing diffusion coefficient. After long-term cycling, ratios of the diffusion coefficients determined by GITT compared to CV become more significant with an increase about 1 order of magnitude, while no significant variation is seen between the diffusion coefficients calculated from EIS in comparison to CV.

Leaching of Zinc Sulfide by Thiobacillus ferrooxidans: Bacterial Oxidation of the Sulfur Product Layer Increases the Rate of Zinc Sulfide Dissolution at High Concentrations of Ferrous Ions

PubMed Central

Fowler, T. A.; Crundwell, F. K.

1999-01-01

This paper reports the results of leaching experiments conducted with and without Thiobacillus ferrooxidans at the same conditions in solution. The extent of leaching of ZnS with bacteria is significantly higher than that without bacteria at high concentrations of ferrous ions. A porous layer of elemental sulfur is present on the surfaces of the chemically leached particles, while no sulfur is present on the surfaces of the bacterially leached particles. The analysis of the data using the shrinking-core model shows that the chemical leaching of ZnS is limited by the diffusion of ferrous ions through the sulfur product layer at high concentrations of ferrous ions. The analysis of the data shows that diffusion through the product layer does not limit the rate of dissolution when bacteria are present. This suggests that the action of T. ferrooxidans in oxidizing the sulfur formed on the particle surface is to remove the barrier to diffusion by ferrous ions. PMID:10583978

Diffusion and solubility coefficients determined by permeation and immersion experiments for organic solvents in HDPE geomembrane.

PubMed

Chao, Keh-Ping; Wang, Ping; Wang, Ya-Ting

2007-04-02

The chemical resistance of eight organic solvents in high density polyethylene (HDPE) geomembrane has been investigated using the ASTM F739 permeation method and the immersion test at different temperatures. The diffusion of the experimental organic solvents in HDPE geomembrane was non-Fickian kinetic, and the solubility coefficients can be consistent with the solubility parameter theory. The diffusion coefficients and solubility coefficients determined by the ASTM F739 method were significantly correlated to the immersion tests (p<0.001). The steady state permeation rates also showed a good agreement between ASTM F739 and immersion experiments (r(2)=0.973, p<0.001). Using a one-dimensional diffusion equation based on Fick's second law, the diffusion and solubility coefficients obtained by immersion test resulted in over estimates of the ASTM F739 permeation results. The modeling results indicated that the diffusion and solubility coefficients should be obtained using ASTM F739 method which closely simulates the practical application of HDPE as barriers in the field.

Radon diffusion coefficients in 360 waterproof materials of different chemical composition.

PubMed

Jiránek, M; Kotrbatá, M

2011-05-01

This paper summarises the results of radon diffusion coefficient measurements in 360 common waterproof materials available throughout Europe. The materials were grouped into 26 categories according to their chemical composition. It was found that the diffusion coefficients of materials used for protecting houses against radon vary within eight orders from 10(-15) to 10(-8) m(2) s(-1). The lowest values were obtained for bitumen membranes with an Al carrier film and for ethylene vinyl acetate membranes. The highest radon diffusion coefficient values were discovered for sodium bentonite membranes, rubber membranes made of ethylene propylene diene monomer and polymer cement coatings. The radon diffusion coefficients for waterproofings widely used for protecting houses, i.e. flexible polyvinyl chloride, high-, low-density polyethylene, polypropylene and bitumen membranes, vary in the range from 3 × 10(-12) to 3 × 10(-11) m(2) s(-1). Tests were performed which confirmed that the radon diffusion coefficient is also an effective tool for verifying the air-tightness of joints.

Electronic speckle pattern interferometry: a tool for determining diffusion and partition coefficients for proteins in gels.

PubMed

Karlsson, David; Zacchi, Guido; Axelsson, Anders

2002-01-01

The aim of this study was to demonstrate electronic speckle pattern interferometry (ESPI) as a powerful tool in determining diffusion coefficients and partition coefficients for proteins in gels. ESPI employs a CCD camera instead of a holographic plate as in conventional holographic interferometry. This gives the advantage of being able to choose the reference state freely. If a hologram at the reference state is taken and compared to a hologram during the diffusion process, an interferometric picture can be generated that describes the refraction index gradients and thus the concentration gradients in the gel as well as in the liquid. MATLAB is then used to fit Fick's law to the experimental data to obtain the diffusion coefficients in gel and liquid. The partition coefficient is obtained from the same experiment from the flux condition at the interface between gel and liquid. This makes the comparison between the different diffusants more reliable than when the measurements are performed in separate experiments. The diffusion and partitioning coefficients of lysozyme, BSA, and IgG in 4% agarose gel at pH 5.6 and in 0.1 M NaCl have been determined. In the gel the diffusion coefficients were 11.2 +/- 1.6, 4.8 +/- 0.6, and 3.0 +/- 0.3 m(2)/s for lysozyme, BSA, and IgG, respectively. The partition coefficients were determined to be 0.65 +/- 0.04, 0.44 +/- 0.06, and 0.51 +/- 0.04 for lysozyme, BSA, and IgG, respectively. The current study shows that ESPI is easy to use and gives diffusion coefficients and partition coefficients for proteins with sufficient accuracy from the same experiment.

Diffusion of rhodamine B and bovine serum albumin in fibrin gels seeded with primary endothelial cells.

PubMed

Shkilnyy, Andriy; Proulx, Pierre; Sharp, Jamie; Lepage, Martin; Vermette, Patrick

2012-05-01

Scaffolds with adequate mass transport properties are needed in many tissue engineering applications. Fibrin is considered a good biological material to fabricate such scaffolds. However, very little is known about mass transport in fibrin. Therefore, a method based on the analysis of fluorescence intensity for measuring the apparent diffusion coefficient of rhodamine B and fluorescein-labelled bovine serum albumin (FITC-BSA) is described. The experiments are performed in fibrin gels with and without human umbilical vein endothelial cells (HUVEC). The apparent diffusion coefficients of rhodamine B and FITC-BSA in fibrin (fibrinogen concentration of 4 mg/mL) with different cell densities are reported. A LIVE/DEAD(®) assay is performed to confirm the viability of HUVEC seeded at high densities. Diffusion coefficients for rhodamine B remain more or less constant up to 5×10(5) cells/mL and correlate well with literature values measured by other methods in water systems. This indicates that the presence of HUVEC in the fibrin gels (up to 5×10(5) cells/mL) has almost no effect on the diffusion coefficients. Higher cell densities (>5×10(5) cells/mL) result in a decrease of the diffusion coefficients. Diffusion coefficients of rhodamine B and FITC-BSA obtained by this method agree with diffusion coefficients in water predicted by the Stokes-Einstein equation. The experimental design used in this study can be applied to measure diffusion coefficients in different types of gels seeded or not with living cells. Copyright © 2012 Elsevier B.V. All rights reserved.

Ion radial diffusion in an electrostatic impulse model for stormtime ring current formation

NASA Technical Reports Server (NTRS)

Chen, Margaret W.; Schulz, Michael; Lyons, Larry R.; Gorney, David J.

1992-01-01

Two refinements to the quasi-linear theory of ion radial diffusion are proposed and examined analytically with simulations of particle trajectories. The resonance-broadening correction by Dungey (1965) is applied to the quasi-linear diffusion theory by Faelthammar (1965) for an individual model storm. Quasi-linear theory is then applied to the mean diffusion coefficients resulting from simulations of particle trajectories in 20 model storms. The correction for drift-resonance broadening results in quasi-linear diffusion coefficients with discrepancies from the corresponding simulated values that are reduced by a factor of about 3. Further reductions in the discrepancies are noted following the averaging of the quasi-linear diffusion coefficients, the simulated coefficients, and the resonance-broadened coefficients for the 20 storms. Quasi-linear theory provides good descriptions of particle transport for a single storm but performs even better in conjunction with the present ensemble-averaging.

Perpendicular Diffusion Coefficient of Comic Rays: The Presence of Weak Adiabatic Focusing

NASA Astrophysics Data System (ADS)

Wang, J. F.; Qin, G.; Ma, Q. M.; Song, T.; Yuan, S. B.

2017-08-01

The influence of adiabatic focusing on particle diffusion is an important topic in astrophysics and plasma physics. In the past, several authors have explored the influence of along-field adiabatic focusing on the parallel diffusion of charged energetic particles. In this paper, using the unified nonlinear transport theory developed by Shalchi and the method of He and Schlickeiser, we derive a new nonlinear perpendicular diffusion coefficient for a non-uniform background magnetic field. This formula demonstrates that the particle perpendicular diffusion coefficient is modified by along-field adiabatic focusing. For isotropic pitch-angle scattering and the weak adiabatic focusing limit, the derived perpendicular diffusion coefficient is independent of the sign of adiabatic focusing characteristic length. For the two-component model, we simplify the perpendicular diffusion coefficient up to the second order of the power series of the adiabatic focusing characteristic quantity. We find that the first-order modifying factor is equal to zero and that the sign of the second order is determined by the energy of the particles.

Thermodynamic properties and diffusion of water + methane binary mixtures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shvab, I.; Sadus, Richard J., E-mail: rsadus@swin.edu.au

2014-03-14

Thermodynamic and diffusion properties of water + methane mixtures in a single liquid phase are studied using NVT molecular dynamics. An extensive comparison is reported for the thermal pressure coefficient, compressibilities, expansion coefficients, heat capacities, Joule-Thomson coefficient, zero frequency speed of sound, and diffusion coefficient at methane concentrations up to 15% in the temperature range of 298–650 K. The simulations reveal a complex concentration dependence of the thermodynamic properties of water + methane mixtures. The compressibilities, heat capacities, and diffusion coefficients decrease with increasing methane concentration, whereas values of the thermal expansion coefficients and speed of sound increase. Increasing methanemore » concentration considerably retards the self-diffusion of both water and methane in the mixture. These effects are caused by changes in hydrogen bond network, solvation shell structure, and dynamics of water molecules induced by the solvation of methane at constant volume conditions.« less

Determination of Diffusion Coefficients in Cement-Based Materials: An Inverse Problem for the Nernst-Planck and Poisson Models

NASA Astrophysics Data System (ADS)

Szyszkiewicz-Warzecha, Krzysztof; Jasielec, Jerzy J.; Fausek, Janusz; Filipek, Robert

2016-08-01

Transport properties of ions have significant impact on the possibility of rebars corrosion thus the knowledge of a diffusion coefficient is important for reinforced concrete durability. Numerous tests for the determination of diffusion coefficients have been proposed but analysis of some of these tests show that they are too simplistic or even not valid. Hence, more rigorous models to calculate the coefficients should be employed. Here we propose the Nernst-Planck and Poisson equations, which take into account the concentration and electric potential field. Based on this model a special inverse method is presented for determination of a chloride diffusion coefficient. It requires the measurement of concentration profiles or flux on the boundary and solution of the NPP model to define the goal function. Finding the global minimum is equivalent to the determination of diffusion coefficients. Typical examples of the application of the presented method are given.

Kinetics of dodecanoic acid adsorption from caustic solution by activated carbon.

PubMed

Pendleton, Phillip; Wu, Sophie Hua

2003-10-15

This study examines the influences of adsorbent porosity and surface chemistry and of carbon dosage on dodecanoic acid adsorption kinetics from aqueous and 2 M NaOH solutions as batch adsorption processes. Both adsorbents are steam-activated carbons prepared from either coconut or coal precursors. Prior to use the adsorbents were washed in deionized water or 2 M NaOH. Mass transfer coefficients and effective overall diffusion coefficients indicate a minor contribution from adsorbent porosity. In contrast, high surface oxygen content impedes transport to and into the adsorbent structure. Carbon dosage shows a proportional increase in transport coefficients with increasing mass; these coefficients are constant when normalized per unit mass. Neither water nor NaOH treatment of the adsorbents has a significant influence on dodecanoic acid adsorption kinetics. Molecular and Knudsen diffusion coefficients are defined to demonstrate that the overall effective diffusion coefficient values and the diffusion process are controlled by surface diffusion.

A feasibility study for measuring stratospheric turbulence using metrac positioning system

NASA Technical Reports Server (NTRS)

Gage, K. S.; Jasperson, W. H.

1975-01-01

The feasibility of obtaining measurements of Lagrangian turbulence at stratospheric altitudes is demonstrated by using the METRAC System to track constant-level balloons. The basis for current estimates of diffusion coefficients are reviewed and it is pointed out that insufficient data is available upon which to base reliable estimates of vertical diffusion coefficients. It is concluded that diffusion coefficients could be directly obtained from Lagrangian turbulence measurements. The METRAC balloon tracking system is shown to possess the necessary precision in order to resolve the response of constant-level balloons to turbulence at stratospheric altitudes. A small sample of data recorded from a tropospheric tetroon flight tracked by the METRAC System is analyzed to obtain estimates of small-scale three-dimensional diffusion coefficients. It is recommended that this technique be employed to establish a climatology of diffusion coefficients and to ascertain the variation of these coefficients with altitude, season, and latitude.

Effective Stochastic Model for Reactive Transport

NASA Astrophysics Data System (ADS)

Tartakovsky, A. M.; Zheng, B.; Barajas-Solano, D. A.

2017-12-01

We propose an effective stochastic advection-diffusion-reaction (SADR) model. Unlike traditional advection-dispersion-reaction models, the SADR model describes mechanical and diffusive mixing as two separate processes. In the SADR model, the mechanical mixing is driven by random advective velocity with the variance given by the coefficient of mechanical dispersion. The diffusive mixing is modeled as a fickian diffusion with the effective diffusion coefficient. Both coefficients are given in terms of Peclet number (Pe) and the coefficient of molecular diffusion. We use the experimental results of to demonstrate that for transport and bimolecular reactions in porous media the SADR model is significantly more accurate than the traditional dispersion model, which overestimates the mass of the reaction product by as much as 25%.

Predicting Salt Permeability Coefficients in Highly Swollen, Highly Charged Ion Exchange Membranes.

PubMed

Kamcev, Jovan; Paul, Donald R; Manning, Gerald S; Freeman, Benny D

2017-02-01

This study presents a framework for predicting salt permeability coefficients in ion exchange membranes in contact with an aqueous salt solution. The model, based on the solution-diffusion mechanism, was tested using experimental salt permeability data for a series of commercial ion exchange membranes. Equilibrium salt partition coefficients were calculated using a thermodynamic framework (i.e., Donnan theory), incorporating Manning's counterion condensation theory to calculate ion activity coefficients in the membrane phase and the Pitzer model to calculate ion activity coefficients in the solution phase. The model predicted NaCl partition coefficients in a cation exchange membrane and two anion exchange membranes, as well as MgCl 2 partition coefficients in a cation exchange membrane, remarkably well at higher external salt concentrations (>0.1 M) and reasonably well at lower external salt concentrations (<0.1 M) with no adjustable parameters. Membrane ion diffusion coefficients were calculated using a combination of the Mackie and Meares model, which assumes ion diffusion in water-swollen polymers is affected by a tortuosity factor, and a model developed by Manning to account for electrostatic effects. Agreement between experimental and predicted salt diffusion coefficients was good with no adjustable parameters. Calculated salt partition and diffusion coefficients were combined within the framework of the solution-diffusion model to predict salt permeability coefficients. Agreement between model and experimental data was remarkably good. Additionally, a simplified version of the model was used to elucidate connections between membrane structure (e.g., fixed charge group concentration) and salt transport properties.

Protein diffusiophoresis and salt osmotic diffusion in aqueous solutions.

PubMed

Annunziata, Onofrio; Buzatu, Daniela; Albright, John G

2012-10-25

Diffusion of a solute can be induced by the concentration gradient of another solute in solution. This transport mechanism is known as cross-diffusion. We have investigated cross-diffusion in a ternary protein-salt-water system. Specifically, we measured the two cross-diffusion coefficients for the lysozyme-NaCl-water system at 25 °C and pH 4.5 as a function of protein and salt concentrations by Rayleigh interferometry. One cross-diffusion coefficient characterizes salt osmotic diffusion induced by a protein concentration gradient, and is related to protein-salt thermodynamic interactions as described by the theories of Donnan membrane equilibrium and protein preferential hydration. The other cross-diffusion coefficient characterizes protein diffusiophoresis induced by a salt concentration gradient, and is described as the difference between a preferential-interaction coefficient and a transport parameter. We first relate our experimental results to the protein net charge and the thermodynamic excess of water near the protein surface. We then extract the Stefan-Maxwell diffusion coefficient describing protein-salt interactions in water. We find that the value of this coefficient is negative, contrary to the friction interpretation of Stefan-Maxwell equations. This result is explained by considering protein hydration. Finally, protein diffusiophoresis is quantitatively examined by considering electrophoretic and hydration effects on protein migration and utilized to accurately estimate lysozyme electrophoretic mobility. To our knowledge, this is the first time that protein diffusiophoresis has been experimentally characterized and a protein-salt Stefan-Maxwell diffusion coefficient reported. This work represents a significant contribution for understanding and modeling the effect of concentration gradients in protein-salt aqueous systems relevant to diffusion-based mass-transfer technologies and transport in living systems.

Apparent diffusion coefficient evaluation for secondary changes in the cerebellum of rats after middle cerebral artery occlusion

PubMed Central

Yang, Yunjun; Gao, Lingyun; Fu, Jun; Zhang, Jun; Li, Yuxin; Yin, Bo; Chen, Weijian; Geng, Daoying

2013-01-01

Supratentorial cerebral infarction can cause functional inhibition of remote regions such as the cerebellum, which may be relevant to diaschisis. This phenomenon is often analyzed using positron emission tomography and single photon emission CT. However, these methods are expensive and radioactive. Thus, the present study quantified the changes of infarction core and remote regions after unilateral middle cerebral artery occlusion using apparent diffusion coefficient values. Diffusion-weighted imaging showed that the area of infarction core gradually increased to involve the cerebral cortex with increasing infarction time. Diffusion weighted imaging signals were initially increased and then stabilized by 24 hours. With increasing infarction time, the apparent diffusion coefficient value in the infarction core and remote bilateral cerebellum both gradually decreased, and then slightly increased 3–24 hours after infarction. Apparent diffusion coefficient values at remote regions (cerebellum) varied along with the change of supratentorial infarction core, suggesting that the phenomenon of diaschisis existed at the remote regions. Thus, apparent diffusion coefficient values and diffusion weighted imaging can be used to detect early diaschisis. PMID:25206615

A data-drive analysis for heavy quark diffusion coefficient

NASA Astrophysics Data System (ADS)

Xu, Yingru; Nahrgang, Marlene; Cao, Shanshan; Bernhard, Jonah E.; Bass, Steffen A.

2018-02-01

We apply a Bayesian model-to-data analysis on an improved Langevin framework to estimate the temperature and momentum dependence of the heavy quark diffusion coefficient in the quark-gluon plasma (QGP). The spatial diffusion coefficient is found to have a minimum around 1-3 near Tc in the zero momentum limit, and has a non-trivial momentum dependence. With the estimated diffusion coefficient, our improved Langevin model is able to simultaneously describe the D-meson RAA and v2 in three different systems at RHIC and the LHC.

Diffusion in the system K2O-SrO-SiO2. II - Cation self-diffusion coefficients.

NASA Technical Reports Server (NTRS)

Varshneya, A. K.; Cooper, A. R.

1972-01-01

The self-diffusion coefficients were measured by introducing a slab of glass previously irradiated in a reactor between two slabs of unirradiated glass. By heating the specimens, etching them sequentially and determining the radioactivity, self-diffusion coefficients for K and Sr were measured. It is pointed out that the results obtained in the investigations appear to support the proposal that the network of the base glass predominantly controls the activation energy for the diffusion of ions.

Estimation of Knudsen diffusion coefficients from tracer experiments conducted with a binary gas system and a porous medium.

PubMed

Hibi, Yoshihiko; Kashihara, Ayumi

2018-03-01

A previous study has reported that Knudsen diffusion coefficients obtained by tracer experiments conducted with a binary gas system and a porous medium are consistently smaller than those obtained by permeability experiments conducted with a single-gas system and a porous medium. To date, however, that study is the only one in which tracer experiments have been conducted with a binary gas system. Therefore, to confirm this difference in Knudsen diffusion coefficients, we used a method we had developed previously to conduct tracer experiments with a binary carbon dioxide-nitrogen gas system and five porous media with permeability coefficients ranging from 10 -13 to 10 -11  m 2 . The results showed that the Knudsen diffusion coefficient of N 2 (D N2 ) (cm 2 /s) was related to the effective permeability coefficient k e (m 2 ) as D N2  = 7.39 × 10 7 k e 0.767 . Thus, the Knudsen diffusion coefficients of N 2 obtained by our tracer experiments were consistently 1/27 of those obtained by permeability experiments conducted with many porous media and air by other researchers. By using an inversion simulation to fit the advection-diffusion equation to the distribution of concentrations at observation points calculated by mathematically solving the equation, we confirmed that the method used to obtain the Knudsen diffusion coefficient in this study yielded accurate values. Moreover, because the Knudsen diffusion coefficient did not differ when columns with two different lengths, 900 and 1500 mm, were used, this column property did not influence the flow of gas in the column. The equation of the dusty gas model already includes obstruction factors for Knudsen diffusion and molecular diffusion, which relate to medium heterogeneity and tortuosity and depend only on the structure of the porous medium. Furthermore, there is no need to take account of any additional correction factor for molecular diffusion except the obstruction factor because molecular diffusion is only treated in a multicomponent gas system. Thus, molecular diffusion considers only the obstruction factor related to tortuosity. Therefore, we introduced a correction factor for a multicomponent gas system into the DGM equation, multiplying the Knudsen diffusion coefficient, which includes the obstruction factor related to tortuosity, by this correction factor. From the present experimental results, the value of this correction factor was 1/27, and it depended only on the structure of the gas system in the porous medium. Copyright © 2018 Elsevier B.V. All rights reserved.

Estimation of Knudsen diffusion coefficients from tracer experiments conducted with a binary gas system and a porous medium

NASA Astrophysics Data System (ADS)

Hibi, Yoshihiko; Kashihara, Ayumi

2018-03-01

A previous study has reported that Knudsen diffusion coefficients obtained by tracer experiments conducted with a binary gas system and a porous medium are consistently smaller than those obtained by permeability experiments conducted with a single-gas system and a porous medium. To date, however, that study is the only one in which tracer experiments have been conducted with a binary gas system. Therefore, to confirm this difference in Knudsen diffusion coefficients, we used a method we had developed previously to conduct tracer experiments with a binary carbon dioxide-nitrogen gas system and five porous media with permeability coefficients ranging from 10-13 to 10-11 m2. The results showed that the Knudsen diffusion coefficient of N2 (DN2) (cm2/s) was related to the effective permeability coefficient ke (m2) as DN2 = 7.39 × 107ke0.767. Thus, the Knudsen diffusion coefficients of N2 obtained by our tracer experiments were consistently 1/27 of those obtained by permeability experiments conducted with many porous media and air by other researchers. By using an inversion simulation to fit the advection-diffusion equation to the distribution of concentrations at observation points calculated by mathematically solving the equation, we confirmed that the method used to obtain the Knudsen diffusion coefficient in this study yielded accurate values. Moreover, because the Knudsen diffusion coefficient did not differ when columns with two different lengths, 900 and 1500 mm, were used, this column property did not influence the flow of gas in the column. The equation of the dusty gas model already includes obstruction factors for Knudsen diffusion and molecular diffusion, which relate to medium heterogeneity and tortuosity and depend only on the structure of the porous medium. Furthermore, there is no need to take account of any additional correction factor for molecular diffusion except the obstruction factor because molecular diffusion is only treated in a multicomponent gas system. Thus, molecular diffusion considers only the obstruction factor related to tortuosity. Therefore, we introduced a correction factor for a multicomponent gas system into the DGM equation, multiplying the Knudsen diffusion coefficient, which includes the obstruction factor related to tortuosity, by this correction factor. From the present experimental results, the value of this correction factor was 1/27, and it depended only on the structure of the gas system in the porous medium.

Gene interference regulates aquaporin-4 expression in swollen tissue of rats with cerebral ischemic edema: Correlation with variation in apparent diffusion coefficient.

PubMed

Hu, Hui; Lu, Hong; He, Zhanping; Han, Xiangjun; Chen, Jing; Tu, Rong

2012-07-25

To investigate the effects of mRNA interference on aquaporin-4 expression in swollen tissue of rats with ischemic cerebral edema, and diagnose the significance of diffusion-weighted MRI, we injected 5 μL shRNA- aquaporin-4 (control group) or siRNA- aquaporin-4 solution (1:800) (RNA interference group) into the rat right basal ganglia immediately before occlusion of the middle cerebral artery. At 0.25 hours after occlusion of the middle cerebral artery, diffusion-weighted MRI displayed a high signal; within 2 hours, the relative apparent diffusion coefficient decreased markedly, aquaporin-4 expression increased rapidly, and intracellular edema was obviously aggravated; at 4 and 6 hours, the relative apparent diffusion coefficient slowly returned to control levels, aquaporin-4 expression slightly increased, and angioedema was observed. In the RNA interference group, during 0.25-6 hours after injection of siRNA- aquaporin-4 solution, the relative apparent diffusion coefficient slightly fluctuated and aquaporin-4 expression was upregulated; during 0.5-4 hours, the relative apparent diffusion coefficient was significantly higher, while aquaporin-4 expression was significantly lower when compared with the control group, and intracellular edema was markedly reduced; at 0.25 and 6 hours, the relative apparent diffusion coefficient and aquaporin-4 expression were similar when compared with the control group; obvious angioedema remained at 6 hours. Pearson's correlation test results showed that aquaporin-4 expression was negatively correlated with the apparent diffusion coefficient (r = -0.806, P < 0.01). These findings suggest that upregulated aquaporin-4 expression is likely to be the main molecular mechanism of intracellular edema and may be the molecular basis for decreased relative apparent diffusion coefficient. Aquaporin-4 gene interference can effectively inhibit the upregulation of aquaporin-4 expression during the stage of intracellular edema with time-effectiveness. Moreover, diffusion-weighted MRI can accurately detect intracellular edema.

The Search for Interstellar Sulfide Grains

NASA Technical Reports Server (NTRS)

Keller, Lindsay P.; Messenger, Scott

2010-01-01

The lifecycle of sulfur in the galaxy is poorly understood. Fe-sulfide grains are abundant in early solar system materials (e.g. meteorites and comets) and S is highly depleted from the gas phase in cold, dense molecular cloud environments. In stark contrast, sulfur is essentially undepleted from the gas phase in the diffuse interstellar medium, indicating that little sulfur is incorporated into solid grains in this environment. It is widely believed that sulfur is not a component of interstellar dust grains. This is a rather puzzling observation unless Fe-sulfides are not produced in significant quantities in stellar outflows, or their lifetime in the ISM is very short due to rapid destruction. Fe sulfide grains are ubiquitous in cometary samples where they are the dominant host of sulfur. The Fe-sulfides (primarily pyrrhotite; Fe(1-x)S) are common, both as discrete 0.5-10 micron-sized grains and as fine (5-10 nm) nanophase inclusions within amorphous silicate grains. Cometary dust particles contain high abundances of well-preserved presolar silicates and organic matter and we have suggested that they should contain presolar sulfides as well. This hypothesis is supported by the observation of abundant Fe-sulfides grains in dust around pre- and post-main sequence stars inferred from astronomical spectra showing a broad 23 micron IR feature due to FeS. Fe-sulfide grains also occur as inclusions in bona fide circumstellar amorphous silicate grains and as inclusions within deuterium-rich organic matter in cometary dust samples. Our irradiation experiments show that FeS is far more resistant to radiation damage than silicates. Consequently, we expect that Fe sulfide stardust should be as abundant as silicate stardust in solar system materials.

Combined inverse-forward artificial neural networks for fast and accurate estimation of the diffusion coefficients of cartilage based on multi-physics models.

PubMed

Arbabi, Vahid; Pouran, Behdad; Weinans, Harrie; Zadpoor, Amir A

2016-09-06

Analytical and numerical methods have been used to extract essential engineering parameters such as elastic modulus, Poisson׳s ratio, permeability and diffusion coefficient from experimental data in various types of biological tissues. The major limitation associated with analytical techniques is that they are often only applicable to problems with simplified assumptions. Numerical multi-physics methods, on the other hand, enable minimizing the simplified assumptions but require substantial computational expertise, which is not always available. In this paper, we propose a novel approach that combines inverse and forward artificial neural networks (ANNs) which enables fast and accurate estimation of the diffusion coefficient of cartilage without any need for computational modeling. In this approach, an inverse ANN is trained using our multi-zone biphasic-solute finite-bath computational model of diffusion in cartilage to estimate the diffusion coefficient of the various zones of cartilage given the concentration-time curves. Robust estimation of the diffusion coefficients, however, requires introducing certain levels of stochastic variations during the training process. Determining the required level of stochastic variation is performed by coupling the inverse ANN with a forward ANN that receives the diffusion coefficient as input and returns the concentration-time curve as output. Combined together, forward-inverse ANNs enable computationally inexperienced users to obtain accurate and fast estimation of the diffusion coefficients of cartilage zones. The diffusion coefficients estimated using the proposed approach are compared with those determined using direct scanning of the parameter space as the optimization approach. It has been shown that both approaches yield comparable results. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of diffuser vane shape on the performance of a centrifugal compressor stage

NASA Astrophysics Data System (ADS)

Reddy, T. Ch Siva; Ramana Murty, G. V.; Prasad, M. V. S. S. S. M.

2014-04-01

The present paper reports the results of experimental investigations on the effect of diffuser vane shape on the performance of a centrifugal compressor stage. These studies were conducted on the chosen stage having a backward curved impeller of 500 mm tip diameter and 24.5 mm width and its design flow coefficient is ϕd=0.0535. Three different low solidity diffuser vane shapes namely uncambered aerofoil, constant thickness flat plate and circular arc cambered constant thickness plate were chosen as the variants for diffuser vane shape and all the three shapes have the same thickness to chord ratio (t/c=0.1). Flow coefficient, polytropic efficiency, total head coefficient, power coefficient and static pressure recovery coefficient were chosen as the parameters for evaluating the effect of diffuser vane shape on the stage performance. The results show that there is reasonable improvement in stage efficiency and total head coefficient with the use of the chosen diffuser vane shapes as compared to conventional vaneless diffuser. It is also noticed that the aero foil shaped LSD has shown better performance when compared to flat plate and circular arc profiles. The aerofoil vane shape of the diffuser blade is seen to be tolerant over a considerable range of incidence.

Application of the compensated Arrhenius formalism to self-diffusion: implications for ionic conductivity and dielectric relaxation.

PubMed

Petrowsky, Matt; Frech, Roger

2010-07-08

Self-diffusion coefficients are measured from -5 to 80 degrees C in a series of linear alcohols using pulsed field gradient NMR. The temperature dependence of these data is studied using a compensated Arrhenius formalism that assumes an Arrhenius-like expression for the diffusion coefficient; however, this expression includes a dielectric constant dependence in the exponential prefactor. Scaling temperature-dependent diffusion coefficients to isothermal diffusion coefficients so that the exponential prefactors cancel results in calculated energies of activation E(a). The exponential prefactor is determined by dividing the temperature-dependent diffusion coefficients by the Boltzmann term exp(-E(a)/RT). Plotting the prefactors versus the dielectric constant places the data on a single master curve. This procedure is identical to that previously used to study the temperature dependence of ionic conductivities and dielectric relaxation rate constants. The energies of activation determined from self-diffusion coefficients in the series of alcohols are strikingly similar to those calculated for the same series of alcohols from both dielectric relaxation rate constants and ionic conductivities of dilute electrolytes. The experimental results are described in terms of an activated transport mechanism that is mediated by relaxation of the solution molecules. This microscopic picture of transport is postulated to be common to diffusion, dielectric relaxation, and ionic transport.

Calculation method for steady-state pollutant concentration in mixing zones considering variable lateral diffusion coefficient.

PubMed

Wu, Wen; Wu, Zhouhu; Song, Zhiwen

2017-07-01

Prediction of the pollutant mixing zone (PMZ) near the discharge outfall in Huangshaxi shows large error when using the methods based on the constant lateral diffusion assumption. The discrepancy is due to the lack of consideration of the diffusion coefficient variation. The variable lateral diffusion coefficient is proposed to be a function of the longitudinal distance from the outfall. Analytical solution of the two-dimensional advection-diffusion equation of a pollutant is derived and discussed. Formulas to characterize the geometry of the PMZ are derived based on this solution, and a standard curve describing the boundary of the PMZ is obtained by proper choices of the normalization scales. The change of PMZ topology due to the variable diffusion coefficient is then discussed using these formulas. The criterion of assuming the lateral diffusion coefficient to be constant without large error in PMZ geometry is found. It is also demonstrated how to use these analytical formulas in the inverse problems including estimating the lateral diffusion coefficient in rivers by convenient measurements, and determining the maximum allowable discharge load based on the limitations of the geometrical scales of the PMZ. Finally, applications of the obtained formulas to onsite PMZ measurements in Huangshaxi present excellent agreement.

Boiling-induced formation of colloidal gold in black smoker hydrothermal fluids

USGS Publications Warehouse

Gartman, Amy; Hannington, Mark; Jamieson, John W.; Peterkin, Ben; Garbe-Schönberg, Dieter; Findlay, Alyssa J; Fuchs, Sebastian; Kwasnitschka, Tom

2017-01-01

Gold colloids occur in black smoker fluids from the Niua South hydrothermal vent field, Lau Basin (South Pacific Ocean), confirming the long-standing hypothesis that gold may undergo colloidal transport in hydrothermal fluids. Six black smoker vents, varying in temperature from 250 °C to 325 °C, were sampled; the 325 °C vent was boiling at the time of sampling and the 250 °C fluids were diffusely venting. Native gold particles ranging from <50 nm to 2 µm were identified in 4 of the fluid samples and were also observed to precipitate on the sampler during collection from the boiling vent. Total gold concentrations (dissolved and particulate) in the fluid samples range from 1.6 to 5.4 nM in the high-temperature, focused flow vents. Although the gold concentrations in the focused flow fluids are relatively high, they are lower than potential solubilities prior to boiling and indicate that precipitation was boiling induced, with sulfide lost upon boiling to exsolution and metal sulfide formation. Gold concentrations reach 26.7 nM in the 250 °C diffuse flow sample, and abundant native gold particles were also found in the fluids and associated sulfide chimney and are interpreted to be a product of colloid accumulation and growth following initial precipitation upon boiling. These results indicate that colloid-driven precipitation as a result of boiling, the persistence of colloids after boiling, and the accumulation of colloids in diffuse flow fluids are important mechanisms for the enrichment of gold in seafloor hydrothermal systems.

Diffusion in different models of active Brownian motion

NASA Astrophysics Data System (ADS)

Lindner, B.; Nicola, E. M.

2008-04-01

Active Brownian particles (ABP) have served as phenomenological models of self-propelled motion in biology. We study the effective diffusion coefficient of two one-dimensional ABP models (simplified depot model and Rayleigh-Helmholtz model) differing in their nonlinear friction functions. Depending on the choice of the friction function the diffusion coefficient does or does not attain a minimum as a function of noise intensity. We furthermore discuss the case of an additional bias breaking the left-right symmetry of the system. We show that this bias induces a drift and that it generally reduces the diffusion coefficient. For a finite range of values of the bias, both models can exhibit a maximum in the diffusion coefficient vs. noise intensity.

MEASUREMENT OF EFFECTIVE AIR DIFFUSION COEFFICIENTS FOR TRICHLOROETHENE IN UNDISTURBED SOIL CORES. (R826162)

EPA Science Inventory

Abstract

In this study, we measure effective diffusion coefficients for trichloroethene in undisturbed soil samples taken from Picatinny Arsenal, New Jersey. The measured effective diffusion coefficients ranged from 0.0053 to 0.0609 cm²/s over a range of air...

[Lethal myocardial injury associated with hydrogen sulfide poisoning: report of two cases].

PubMed

Inoue, Yukinori; Kumagai, Ken; Tanaka, Toshiharu; Yoshida, Satoru; Sekiguchi, Hiroshi; Kobayashi, Kaori; Hirose, Yasuo

2011-09-01

We investigated two cases of hydrogen sulfide poisoning in which the patients showed lethal myocardial injury. Both patients had planned to commit suicide by inhaling hydrogen sulfide. In case 1, a 17-year-old man was confused and was brought to our hospital by ambulance. An electrocardiogram (ECG) revealed diffuse elevation of the ST segment on the second hospital day. The patient recovered and was discharged from the hospital on the 15th day. However, he died suddenly on the 18th day. In case 2, a 21-year-old man was found lying on the floor and was admitted to our hospital. ECG showed tall T waves after 5 hr. Tachycardia and tachypnea occurred after 12 hr. After 16 hr, the ECG showed a marked elevation of the ST segment, and the patient developed cardiac arrest. Even though percutaneous cardiopulmonary support was used, he died on the 4th day. It is highly probable that myocardial injury asscociated with hydrogen sulfide poisoning was not caused by systemic hypoxia but by selective myocardial toxicity. These cases demonstrate that delayed presentation of a lethal myocardial injury should be considered while treating cases of hydrogen sulfide poisoning.

Thermodiffusion, molecular diffusion and Soret coefficient of binary and ternary mixtures of n-hexane, n-dodecane and toluene.

PubMed

Alonso de Mezquia, David; Wang, Zilin; Lapeira, Estela; Klein, Michael; Wiegand, Simone; Mounir Bou-Ali, M

2014-11-01

In this study, the thermodiffusion, molecular diffusion, and Soret coefficients of 12 binary mixtures composed of toluene, n-hexane and n-dodecane in the whole range of concentrations at atmospheric pressure and temperatures of 298.15 K and 308.15 K have been determined. The experimental measurements have been carried out using the Thermogravitational Column, the Sliding Symmetric Tubes and the Thermal Diffusion Forced Rayleigh Scattering techniques. The results obtained using the different techniques show a maximum deviation of 9% for the thermodiffusion coefficient, 8% for the molecular diffusion coefficient and 2% for the Soret coefficient. For the first time we report a decrease of the thermodiffusion coefficient with increasing ratio of the thermal expansion coefficient and viscosity for a binary mixture of an organic ring compound with a short n-alkane. This observation is discussed in terms of interactions between the different components. Additionally, the thermogravitational technique has been used to measure the thermodiffusion coefficients of four ternary mixtures consisting of toluene, n-hexane and n-dodecane at 298.15 K. In order to complete the study, the values obtained for the molecular diffusion coefficient in binary mixtures, and the thermodiffusion coefficient of binary and ternary mixtures have been compared with recently derived correlations.

Mass transport in polyelectrolyte solutions

NASA Astrophysics Data System (ADS)

Schipper, F. J. M.; Leyte, J. C.

1999-02-01

The self-diffusion coefficients of the three components of a salt-free heavy-water solution of polymethacrylic acid, completely neutralized with tetra-methylammonium hydroxide, were measured over a broad concentration range. Three concentration regions were observed for the self-diffusion of both the polyions and the counterions. At polyion concentrations below 0.01 mol monomer kg-1, the dilute concentration regime for the polymer, the polyion self-diffusion coefficient approaches the self-diffusion coefficient of a freely diffusing rod upon dilution. At polyelectrolyte concentrations above 0.1 mol monomer kg-1, the self-diffusion coefficients of the solvent, the counterions and the polymer decreased with concentration, suggesting that this decrease is due to a topological constraint on the motions of the components. In the intermediate-concentration region, the self-diffusion coefficients of the polyions and the counterions are independent of the concentration. The polyion dynamic behaviour is, in the intermediate- and high-concentration regions, reasonably well described by that of a hard sphere, with a radius of 3.7 nm. A correct prediction for the solvent dynamics is given by the obstruction effect of this hard sphere on the solvent. The relative counterion self-diffusion coefficient is predicted almost quantitatively over the entire concentration range with the Poisson-Boltzmann-Smoluchowski model for the spherical cell, provided that the sphere radius and the number of charges are chosen appropriately (approximately the number of charges in a persistence length). Using this model, the dependence of the counterion self-diffusion coefficient on the ionic strength, polyion concentration and counterion radius is calculated quantitatively over a large concentration range.

Platinum-group element geochemistry used to determine Cu and Au fertility in the Northparkes igneous suites, New South Wales, Australia

NASA Astrophysics Data System (ADS)

Hao, Hongda; Campbell, Ian H.; Park, Jung-Woo; Cooke, David R.

2017-11-01

Recent studies have shown that platinum-group elements (PGE) can be used to constrain the timing of sulfide saturation in evolving felsic systems. In this study, we report trace-element, PGE, Re and Au data for the barren and ore-associated suites of intermediate to felsic rocks from the Northparkes Cu-Au porphyry region, emphasizing the timing of sulfide saturation and its influence on the tenor of the associated hydrothermal mineralization. Two barren suites, the Goonumbla and Wombin Volcanics and associate intrusive rocks, are found in the region. Geochemical modelling shows that the barren suites are dominated by plagioclase-pyroxene fractionation, whereas the ore-associated Northparkes Cu-Au porphyry suite is characterized by plagioclase-amphibole fractionation, which requires the ore-bearing suite to have crystallized from a wetter magma than barren suites. The concentrations of PGE, Re and Au in the barren suites decrease continuously during fractional crystallization. This is attributed to early sulfide saturation with the fraction of immiscible sulfide precipitation required to produce the observed trend, being 0.13 and 0.16 wt.% for the Goonumbla and Wombin suites, respectively. The calculated partition coefficients for Au and Pd required to model the observed change in these elements with MgO are well below published values, indicating that R, the mass ratio of silicate to sulfide melt, played a significant role in controlling the rate of decline of these elements with fractionation. Palladium in the ore-associated suite, in contrast, first increases with fractionation then decreases abruptly at 1.2 wt.% MgO. The sharp decrease is attributed to the onset of sulfide precipitation. Platinum on the other hand shows a moderate decrease, starting from the highest MgO sample analysed, but then decreasing strongly from 1.2 wt.% MgO. The initial Pt decrease is attributed to precipitation of a platinum-group mineral (PGM), probably a Pt-Fe alloy, and the sharp decrease of both Pt and Pd at 1.2 wt.% MgO to sulfide saturation. We suggest that the Goonumbla and Wombin suites are barren because early sulfide saturation locked most of the Cu and Au in a sulfide phase in the cumulus pile of a deep parental magma chamber, well before volatile saturation, so that when the magma reached volatile saturation, it did not have access to the Cu and Au. This contrasts with the relatively late sulfide saturation in the ore-associated suite, which was followed shortly afterwards by volatile saturation. Rayleigh fractionation concentrated incompatible Cu and Au by at least a factor of five before volatile saturation. The short crystallization interval between immiscible sulfide and volatile saturation allowed some Au and Cu to be stripped from the evolving magma. Gold, with its higher partition coefficient into immiscible sulfide melts, was more affected than Cu. The result is a Cu-Au deposit. Our study also suggests that Rayleigh fractionation is as at least as important as the initial concentration of chalcophile elements in the parent magma in determining the fertility of felsic magma suites.

Influence of diffuse reflectance measurement accuracy on the scattering coefficient in determination of optical properties with integrating sphere optics (a secondary publication).

PubMed

Horibe, Takuro; Ishii, Katsunori; Fukutomi, Daichi; Awazu, Kunio

2015-12-30

An estimation error of the scattering coefficient of hemoglobin in the high absorption wavelength range has been observed in optical property calculations of blood-rich tissues. In this study, the relationship between the accuracy of diffuse reflectance measurement in the integrating sphere and calculated scattering coefficient was evaluated with a system to calculate optical properties combined with an integrating sphere setup and the inverse Monte Carlo simulation. Diffuse reflectance was measured with the integrating sphere using a small incident port diameter and optical properties were calculated. As a result, the estimation error of the scattering coefficient was improved by accurate measurement of diffuse reflectance. In the high absorption wavelength range, the accuracy of diffuse reflectance measurement has an effect on the calculated scattering coefficient.

Comparison of Experimental Methods for Estimating Matrix Diffusion Coefficients for Contaminant Transport Modeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Telfeyan, Katherine Christina; Ware, Stuart Douglas; Reimus, Paul William

Diffusion cell and diffusion wafer experiments were conducted to compare methods for estimating matrix diffusion coefficients in rock core samples from Pahute Mesa at the Nevada Nuclear Security Site (NNSS). A diffusion wafer method, in which a solute diffuses out of a rock matrix that is pre-saturated with water containing the solute, is presented as a simpler alternative to the traditional through-diffusion (diffusion cell) method. Both methods yielded estimates of matrix diffusion coefficients that were within the range of values previously reported for NNSS volcanic rocks. The difference between the estimates of the two methods ranged from 14 to 30%,more » and there was no systematic high or low bias of one method relative to the other. From a transport modeling perspective, these differences are relatively minor when one considers that other variables (e.g., fracture apertures, fracture spacings) influence matrix diffusion to a greater degree and tend to have greater uncertainty than diffusion coefficients. For the same relative random errors in concentration measurements, the diffusion cell method yields diffusion coefficient estimates that have less uncertainty than the wafer method. However, the wafer method is easier and less costly to implement and yields estimates more quickly, thus allowing a greater number of samples to be analyzed for the same cost and time. Given the relatively good agreement between the methods, and the lack of any apparent bias between the methods, the diffusion wafer method appears to offer advantages over the diffusion cell method if better statistical representation of a given set of rock samples is desired.« less

Comparison of experimental methods for estimating matrix diffusion coefficients for contaminant transport modeling

NASA Astrophysics Data System (ADS)

Telfeyan, Katherine; Ware, S. Doug; Reimus, Paul W.; Birdsell, Kay H.

2018-02-01

Diffusion cell and diffusion wafer experiments were conducted to compare methods for estimating effective matrix diffusion coefficients in rock core samples from Pahute Mesa at the Nevada Nuclear Security Site (NNSS). A diffusion wafer method, in which a solute diffuses out of a rock matrix that is pre-saturated with water containing the solute, is presented as a simpler alternative to the traditional through-diffusion (diffusion cell) method. Both methods yielded estimates of effective matrix diffusion coefficients that were within the range of values previously reported for NNSS volcanic rocks. The difference between the estimates of the two methods ranged from 14 to 30%, and there was no systematic high or low bias of one method relative to the other. From a transport modeling perspective, these differences are relatively minor when one considers that other variables (e.g., fracture apertures, fracture spacings) influence matrix diffusion to a greater degree and tend to have greater uncertainty than effective matrix diffusion coefficients. For the same relative random errors in concentration measurements, the diffusion cell method yields effective matrix diffusion coefficient estimates that have less uncertainty than the wafer method. However, the wafer method is easier and less costly to implement and yields estimates more quickly, thus allowing a greater number of samples to be analyzed for the same cost and time. Given the relatively good agreement between the methods, and the lack of any apparent bias between the methods, the diffusion wafer method appears to offer advantages over the diffusion cell method if better statistical representation of a given set of rock samples is desired.

Determination of pollutant diffusion coefficients in naturally formed biofilms using a single tube extractive membrane bioreactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, S.F.; Splendiani, A.; Freitas dos Santos, L.M.

A novel technique has been used to determine the effective diffusion coefficients for 1,1,2-trichloroethane (TCE), a nonreacting tracer, in biofilms growing on the external surface of a silicone rubber membrane tube during degradation of 1,2-dichloroethane (DCE) by Xanthobacter autotrophicus GJ10 and monochlorobenzene (MCB) by Pseudomonas JS150. Experiments were carried out in a single tube extractive membrane bioreactor (STEMB), whose configuration makes it possible to measure the transmembrane flux of substrates. A video imaging technique (VIT) was employed for in situ biofilm thickness measurement and recording. Diffusion coefficients of TCE in the biofilms and TCE mass transfer coefficients in the liquidmore » films adjacent to the biofilms were determined simultaneously using a resistances-in-series diffusion model. It was found that the flux and overall mass transfer coefficient of TCE decrease with increasing biofilm thickness, showing the importance of biofilm diffusion on the mass transfer process. Similar fluxes were observed for the nonreacting tracer (TCE) and the reactive substrates (MCB or DCE), suggesting that membrane-attached biofilm systems can be rate controlled primarily by substrate diffusion. The TCE diffusion coefficient in the JS150 biofilm appeared to be dependent on biofilm thickness, decreasing markedly for biofilm thicknesses of >1 mm. The values of the TCE diffusion coefficients in the JS150 biofilms <1-mm thick are approximately twice those in water and fall to around 30% of the water value for biofilms >1-mm thick.« less

Diffusion and plasticity at high temperature

NASA Astrophysics Data System (ADS)

Philibert, J.

1991-06-01

High temperature plastic deformation requires atomic migration whatever the mechanism of deformation. The constitutive equations contain a diffusion coefficient and the deformation rate follows an Arrhenius law. This paper will only discuss the case of viscous creep in order to elucidate the nature of the diffusion processes and the expression of the diffusion coefficient involved in alloys or compounds. La déformation plastique à haute température met en jeu des migrations atomiques, quel que soit le mécanisme de déformation. Les lois de comportement contiennent donc un coefficient de diffusion et la vitesse de déformation obéit à une loi d'Arrhenius. Dans cet article, qui ne conceme qu'un seul type de déformation, lefluage visqueux, on s'efforce de préciser la nature des processus de diffusion et du coefficient de diffusion mis en jeu dans le cas des alliages et des composés.

Theoretical and Experimental Investigation of the Translational Diffusion of Proteins in the Vicinity of Temperature-Induced Unfolding Transition.

PubMed

Molchanov, Stanislav; Faizullin, Dzhigangir A; Nesmelova, Irina V

2016-10-06

Translational diffusion is the most fundamental form of transport in chemical and biological systems. The diffusion coefficient is highly sensitive to changes in the size of the diffusing species; hence, it provides important information on the variety of macromolecular processes, such as self-assembly or folding-unfolding. Here, we investigate the behavior of the diffusion coefficient of a macromolecule in the vicinity of heat-induced transition from folded to unfolded state. We derive the equation that describes the diffusion coefficient of the macromolecule in the vicinity of the transition and use it to fit the experimental data from pulsed-field-gradient nuclear magnetic resonance (PFG NMR) experiments acquired for two globular proteins, lysozyme and RNase A, undergoing temperature-induced unfolding. A very good qualitative agreement between the theoretically derived diffusion coefficient and experimental data is observed.

Banded structures in electron pitch angle diffusion coefficients from resonant wave-particle interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tripathi, A. K., E-mail: aktrip2001@yahoo.co.in; Singhal, R. P., E-mail: rpsiitbhu@yahoo.com; Khazanov, G. V., E-mail: George.V.Khazanov@nasa.gov

2016-04-15

Electron pitch angle (D{sub αα}) and momentum (D{sub pp}) diffusion coefficients have been calculated due to resonant interactions with electrostatic electron cyclotron harmonic (ECH) and whistler mode chorus waves. Calculations have been performed at two spatial locations L = 4.6 and 6.8 for electron energies ≤10 keV. Landau (n = 0) resonance and cyclotron harmonic resonances n = ±1, ±2, … ±5 have been included in the calculations. It is found that diffusion coefficient versus pitch angle (α) profiles show large dips and oscillations or banded structures. The structures are more pronounced for ECH and lower band chorus (LBC) and particularly at location 4.6. Calculations of diffusionmore » coefficients have also been performed for individual resonances. It is noticed that the main contribution of ECH waves in pitch angle diffusion coefficient is due to resonances n = +1 and n = +2. A major contribution to momentum diffusion coefficients appears from n = +2. However, the banded structures in D{sub αα} and D{sub pp} coefficients appear only in the profile of diffusion coefficients for n = +2. The contribution of other resonances to diffusion coefficients is found to be, in general, quite small or even negligible. For LBC and upper band chorus waves, the banded structures appear only in Landau resonance. The D{sub pp} diffusion coefficient for ECH waves is one to two orders smaller than D{sub αα} coefficients. For chorus waves, D{sub pp} coefficients are about an order of magnitude smaller than D{sub αα} coefficients for the case n ≠ 0. In case of Landau resonance, the values of D{sub pp} coefficient are generally larger than the values of D{sub αα} coefficients particularly at lower energies. As an aid to the interpretation of results, we have also determined the resonant frequencies. For ECH waves, resonant frequencies have been estimated for wave normal angle 89° and harmonic resonances n = +1, +2, and +3, whereas for whistler mode waves, the frequencies have been calculated for angle 10° and Landau resonance. Further, in ECH waves, the banded structures appear for electron energies ≥1 keV, and for whistler mode chorus waves, structures appear for energies >2 keV at L = 4.6 and above 200 eV for L = 6.8. The results obtained in the present work will be helpful in the study of diffusion curves and will have important consequences for diffuse aurora and pancake distributions.« less

Three FORTRAN programs for finite-difference solutions to binary diffusion in one and two phases with composition-and time-dependent diffusion coefficients

USGS Publications Warehouse

Sanford, R.F.

1982-01-01

Geological examples of binary diffusion are numerous. They are potential indicators of the duration and rates of geological processes. Analytical solutions to the diffusion equations generally do not allow for variable diffusion coefficients, changing boundary conditions, and impingement of diffusion fields. The three programs presented here are based on Crank-Nicholson finite-difference approximations, which can take into account these complicating factors. Program 1 describes the diffusion of a component into an initially homogeneous phase that has a constant surface composition. Specifically it is written for Fe-Mg exchange in olivine at oxygen fugacities appropriate for the lunar crust, but other components, phases, or fugacities may be substituted by changing the values of the diffusion coefficient. Program 2 simulates the growth of exsolution lamellae. Program 3 describes the growth of reaction rims. These two programs are written for pseudobinary Ca-(Mg, Fe) exchange in pyroxenes. In all three programs, the diffusion coefficients and boundary conditions can be varied systematically with time. To enable users to employ widely different numerical values for diffusion coefficients and diffusion distance, the grid spacing in the space dimension and the increment by which the grid spacing in the time dimension is increased at each time step are input constants that can be varied each time the programs are run to yield a solution of the desired accuracy. ?? 1982.

Self diffusion of interacting membrane proteins.

PubMed Central

Abney, J R; Scalettar, B A; Owicki, J C

1989-01-01

A two-dimensional version of the generalized Smoluchowski equation is used to analyze the time (or distance) dependent self diffusion of interacting membrane proteins in concentrated membrane systems. This equation provides a well established starting point for descriptions of the diffusion of particles that interact through both direct and hydrodynamic forces; in this initial work only the effects of direct interactions are explicitly considered. Data describing diffusion in the presence of hard-core repulsions, soft repulsions, and soft repulsions with weak attractions are presented. The effect that interactions have on the self-diffusion coefficient of a real protein molecule from mouse liver gap junctions is also calculated. The results indicate that self diffusion is always inhibited by direct interactions; this observation is interpreted in terms of the caging that will exist at finite protein concentration. It is also noted that, over small distance scales, the diffusion coefficient is determined entirely by the very strong Brownian forces; therefore, as a function of displacement the self-diffusion coefficient decays (rapidly) from its value at infinite dilution to its steady-state interaction-averaged value. The steady-state self-diffusion coefficient describes motion over distance scales that range from approximately 10 nm to cellular dimensions and is the quantity measured in fluorescence recovery after photobleaching experiments. The short-ranged behavior of the diffusion coefficient is important on the interparticle-distance scale and may therefore influence the rate at which nearest-neighbor collisional processes take place. The hard-disk theoretical results presented here are in excellent agreement with lattice Monte-Carlo results obtained by other workers. The concentration dependence of experimentally measured diffusion coefficients of antibody-hapten complexes bound to the membrane surface is consistent with that predicted by the theory. The variation in experimental diffusion coefficients of integral membrane proteins is greater than that predicted by the theory, and may also reflect protein-induced perturbations in membrane viscosity. PMID:2720077

Determination of malignancy and characterization of hepatic tumor type with diffusion-weighted magnetic resonance imaging: comparison of apparent diffusion coefficient and intravoxel incoherent motion-derived measurements.

PubMed

Doblas, Sabrina; Wagner, Mathilde; Leitao, Helena S; Daire, Jean-Luc; Sinkus, Ralph; Vilgrain, Valérie; Van Beers, Bernard E

2013-10-01

The objective of this study was to compare the value of the apparent diffusion coefficient (ADC) determined with 3 b values and the intravoxel incoherent motion (IVIM)-derived parameters in the determination of malignancy and characterization of hepatic tumor type. Seventy-six patients with 86 solid hepatic lesions, including 8 hemangiomas, 20 lesions of focal nodular hyperplasia, 9 adenomas, 30 hepatocellular carcinomas, 13 metastases, and 6 cholangiocarcinomas, were assessed in this prospective study. Diffusion-weighted images were acquired with 11 b values to measure the ADCs (with b = 0, 150, and 500 s/mm) and the IVIM-derived parameters, namely, the pure diffusion coefficient and the perfusion-related diffusion fraction and coefficient. The diffusion parameters were compared between benign and malignant tumors and between tumor types, and their diagnostic value in identifying tumor malignancy was assessed. The apparent and pure diffusion coefficients were significantly higher in benign than in malignant tumors (benign: 2.32 [0.87] × 10 mm/s and 1.42 [0.37] × 10 mm/s vs malignant: 1.64 [0.51] × 10 mm/s and 1.14 [0.28] × 10 mm/s, respectively; P < 0.0001 and P = 0.0005), whereas the perfusion-related diffusion parameters did not differ significantly between the 2 groups. The apparent and pure diffusion coefficients provided similar accuracy in assessing tumor malignancy (areas under the receiver operating characteristic curve of 0.770 and 0.723, respectively). In the multigroup analysis, the ADC was found to be significantly higher in hemangiomas than in hepatocellular carcinomas, metastases, and cholangiocarcinomas. In the same manner, it was higher in lesions of focal nodular hyperplasia than in metastases and cholangiocarcinomas. However, the pure diffusion coefficient was significantly higher only in hemangiomas versus hepatocellular and cholangiocellular carcinomas. Compared with the ADC, the diffusion parameters derived from the IVIM model did not improve the determination of malignancy and characterization of hepatic tumor type.

Maxwell-Stefan diffusion coefficient estimation for ternary systems: an ideal ternary alcohol system.

PubMed

Allie-Ebrahim, Tariq; Zhu, Qingyu; Bräuer, Pierre; Moggridge, Geoff D; D'Agostino, Carmine

2017-06-21

The Maxwell-Stefan model is a popular diffusion model originally developed to model diffusion of gases, which can be considered thermodynamically ideal mixtures, although its application has been extended to model diffusion in non-ideal liquid mixtures as well. A drawback of the model is that it requires the Maxwell-Stefan diffusion coefficients, which are not based on measurable quantities but they have to be estimated. As a result, numerous estimation methods, such as the Darken model, have been proposed to estimate these diffusion coefficients. However, the Darken model was derived, and is only well defined, for binary systems. This model has been extended to ternary systems according to two proposed forms, one by R. Krishna and J. M. van Baten, Ind. Eng. Chem. Res., 2005, 44, 6939-6947 and the other by X. Liu, T. J. H. Vlugt and A. Bardow, Ind. Eng. Chem. Res., 2011, 50, 10350-10358. In this paper, the two forms have been analysed against the ideal ternary system of methanol/butan-1-ol/propan-1-ol and using experimental values of self-diffusion coefficients. In particular, using pulsed gradient stimulated echo nuclear magnetic resonance (PGSTE-NMR) we have measured the self-diffusion coefficients in various methanol/butan-1-ol/propan-1-ol mixtures. The experimental values of self-diffusion coefficients were then used as the input data required for the Darken model. The predictions of the two proposed multicomponent forms of this model were then compared to experimental values of mutual diffusion coefficients for the ideal alcohol ternary system. This experimental-based approach showed that the Liu's model gives better predictions compared to that of Krishna and van Baten, although it was only accurate to within 26%. Nonetheless, the multicomponent Darken model in conjunction with self-diffusion measurements from PGSTE-NMR represents an attractive method for a rapid estimation of mutual diffusion in multicomponent systems, especially when compared to exhaustive MD simulations.

Experimental study of mass diffusion coefficients of hydrogen in dimethyl phosphate and n-heptane

NASA Astrophysics Data System (ADS)

Guo, Y.; Zhu, L. K.; Zhang, Y. P.; Liu, J.; Guo, J. S.

2017-11-01

In this study, a laser holographic interferometer experimental system was developed for studying the gas-liquid mass diffusion coefficient. Then the experimental system’s uncertainty was analyzed to be at most ±0.2% therefore, this system was reliable. The mass diffusion coefficient of hydrogen in dimethyl phosphate and n-heptane was measured at atmospheric pressure in the temperature range of 273.15-338.15 K. Then, the experimental data were used to fit the correlations of the mass diffusion coefficient of hydrogen in dimethyl phosphate and n-heptane with temperature.

Chromatographic determination of the diffusion coefficients of light hydrocarbons in polymers

NASA Astrophysics Data System (ADS)

Yakubenko, E. E.; Korolev, A. A.; Chapala, P. P.; Bermeshev, M. V.; Kanat'eva, A. Yu.; Kurganov, A. A.

2017-01-01

Gas-chromatographic determination of the diffusion coefficients that allows for the compressibility of the mobile phase has been suggested. The diffusion coefficients were determined for light hydrocarbons C1-C4 in four polymers with a high free volume, which are candidates for use as gas-separating membranes. The diffusion coefficients calculated from chromatographic data were shown to be one or two orders of magnitude smaller than the values obtained by the membrane method. This may be due to the presence of an additional flow through the membrane caused by the pressure gradient across the membrane in membrane methods.

Field-scale effective matrix diffusion coefficient for fractured rock: results from literature survey.

PubMed

Zhou, Quanlin; Liu, Hui-Hai; Molz, Fred J; Zhang, Yingqi; Bodvarsson, Gudmundur S

2007-08-15

Matrix diffusion is an important mechanism for solute transport in fractured rock. We recently conducted a literature survey on the effective matrix diffusion coefficient, D(m)(e), a key parameter for describing matrix diffusion processes at the field scale. Forty field tracer tests at 15 fractured geologic sites were surveyed and selected for the study, based on data availability and quality. Field-scale D(m)(e) values were calculated, either directly using data reported in the literature, or by reanalyzing the corresponding field tracer tests. The reanalysis was conducted for the selected tracer tests using analytic or semi-analytic solutions for tracer transport in linear, radial, or interwell flow fields. Surveyed data show that the scale factor of the effective matrix diffusion coefficient (defined as the ratio of D(m)(e) to the lab-scale matrix diffusion coefficient, D(m), of the same tracer) is generally larger than one, indicating that the effective matrix diffusion coefficient in the field is comparatively larger than the matrix diffusion coefficient at the rock-core scale. This larger value can be attributed to the many mass-transfer processes at different scales in naturally heterogeneous, fractured rock systems. Furthermore, we observed a moderate, on average trend toward systematic increase in the scale factor with observation scale. This trend suggests that the effective matrix diffusion coefficient is likely to be statistically scale-dependent. The scale-factor value ranges from 0.5 to 884 for observation scales from 5 to 2000 m. At a given scale, the scale factor varies by two orders of magnitude, reflecting the influence of differing degrees of fractured rock heterogeneity at different geologic sites. In addition, the surveyed data indicate that field-scale longitudinal dispersivity generally increases with observation scale, which is consistent with previous studies. The scale-dependent field-scale matrix diffusion coefficient (and dispersivity) may have significant implications for assessing long-term, large-scale radionuclide and contaminant transport events in fractured rock, both for nuclear waste disposal and contaminant remediation.

Molecular dynamics simulation of real-fluid mutual diffusion coefficients with the Lennard-Jones potential model

NASA Astrophysics Data System (ADS)

Stoker, J. M.; Rowley, R. L.

1989-09-01

Mutual diffusion coefficients for selected alkanes in carbon tetrachloride were calculated using molecular dynamics and Lennard-Jones (LJ) potentials. Use of effective spherical LJ parameters is desirable when possible for two reasons: (i) computer time is saved due to the simplicity of the model and (ii) the number of parameters in the model is kept to a minimum. Results of this study indicate that mutual diffusivity is particularly sensitive to the molecular size cross parameter, σ12, and that the commonly used Lorentz-Berthelot rules are inadequate for mixtures in which the component structures differ significantly. Good agreement between simulated and experimental mutual diffusivities is obtained with a combining rule for σ12 which better represents these asymmetric mixtures using pure component LJ parameters obtained from self-diffusion coefficient data. The effect of alkane chain length on the mutual diffusion coefficient is correctly predicted. While the effects of alkane branching upon the diffusion coefficient are comparable in size to the uncertainty of these calculations, the qualitative trend due to branching is also correctly predicted by the MD results.

Time of Flight Electrochemistry: Diffusion Coefficient Measurements Using Interdigitated Array (IDA) Electrodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Fei; Kolesov, Grigory; Parkinson, Bruce A.

2014-09-26

A simple and straightforward method for measuring diffusion coefficients using interdigitated array (IDA) electrodes is reported. The method does not require that the exact electrode area be known but depends only the size of the gap between the IDA electrode pairs. Electroactive molecules produced at the generator electrode of the IDA by a voltage step or scan can diffuse to the collector electrode and the time delay before the current for the reverse electrochemical reaction is detected at the collector is used to calculate the diffusion coefficient. The measurement of the diffusion rate of Ru(NH3)6+2 in aqueous solution has beenmore » used as an example measuring diffusion coefficients using this method. Additionally, a digital simulation of the electrochemical response of the IDA electrodes was used to simulate the entire current/voltage/time behavior of the system and verify the experimentally measured diffusion coefficients. This work was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the Department of Energy, Office of Science, Office of Basic Energy Sciences.« less

Serial diffusion-weighted imaging in subacute sclerosing panencephalitis.

PubMed

Kanemura, Hideaki; Aihara, Masao

2008-06-01

Subacute sclerosing panencephalitis may be associated with clinical features of frontal lobe dysfunction. We previously reported that frontal lobe volume falls significantly as clinical stage progresses, using three-dimensional magnetic resonance imaging-based brain volumetry. The hypothesis that frontal volume increases correlate with clinical improvement, however, was not tested in our previous study. Therefore, we reevaluated our patient with subacute sclerosing panencephalitis, to determine whether apparent diffusion coefficient maps can characterize the clinical course of subacute sclerosing panencephalitis. We studied an 8-year-old boy with subacute sclerosing panencephalitis, using serial diffusion-weighted imaging magnetic resonance imaging, and measured the regional apparent diffusion coefficient. The regional apparent diffusion coefficient of the frontal lobe decreased significantly with clinical progression, whereas it increased to within normal range during clinical improvements. The apparent diffusion coefficient of the other regions did not change. These results suggest that the clinical signs of patients with subacute sclerosing panencephalitis are attributable to frontal lobe dysfunction, and that apparent diffusion coefficient measurements may be useful in predicting the clinical course of subacute sclerosing panencephalitis.

Quantitative differentiation of breast lesions at 3T diffusion-weighted imaging (DWI) using the ratio of distributed diffusion coefficient (DDC).

PubMed

Ertas, Gokhan; Onaygil, Can; Akin, Yasin; Kaya, Handan; Aribal, Erkin

2016-12-01

To investigate the accuracy of diffusion coefficients and diffusion coefficient ratios of breast lesions and of glandular breast tissue from mono- and stretched-exponential models for quantitative diagnosis in diffusion-weighted magnetic resonance imaging (MRI). We analyzed pathologically confirmed 170 lesions (85 benign and 85 malignant) imaged using a 3.0T MR scanner. Small regions of interest (ROIs) focusing on the highest signal intensity for lesions and also for glandular tissue of contralateral breast were obtained. Apparent diffusion coefficient (ADC) and distributed diffusion coefficient (DDC) were estimated by performing nonlinear fittings using mono- and stretched-exponential models, respectively. Coefficient ratios were calculated by dividing the lesion coefficient by the glandular tissue coefficient. A stretched exponential model provides significantly better fits then the monoexponential model (P < 0.001): 65% of the better fits for glandular tissue and 71% of the better fits for lesion. High correlation was found in diffusion coefficients (0.99-0.81 and coefficient ratios (0.94) between the models. The highest diagnostic accuracy was found by the DDC ratio (area under the curve [AUC] = 0.93) when compared with lesion DDC, ADC ratio, and lesion ADC (AUC = 0.91, 0.90, 0.90) but with no statistically significant difference (P > 0.05). At optimal thresholds, the DDC ratio achieves 93% sensitivity, 80% specificity, and 87% overall diagnostic accuracy, while ADC ratio leads to 89% sensitivity, 78% specificity, and 83% overall diagnostic accuracy. The stretched exponential model fits better with signal intensity measurements from both lesion and glandular tissue ROIs. Although the DDC ratio estimated by using the model shows a higher diagnostic accuracy than the ADC ratio, lesion DDC, and ADC, it is not statistically significant. J. Magn. Reson. Imaging 2016;44:1633-1641. © 2016 International Society for Magnetic Resonance in Medicine.

Diffusion coefficients of nitric oxide in water: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Pokharel, Sunil; Pantha, Nurapati; Adhikari, N. P.

2016-09-01

Self-diffusion coefficients along with the mutual diffusion coefficients of nitric oxide (NO) and SPC/E water (H2O) as solute and solvent of the mixture, have been studied within the framework of classical molecular dynamics level of calculations using GROMACS package. The radial distribution function (RDF) of the constituent compounds are calculated to study solute-solute, solute-solvent and solvent-solvent molecular interactions as a function of temperature. A dilute solution of five NO molecules (mole fraction 0.018) and 280 H2O molecules (mole fraction 0.982) has been taken as the sample. The self-diffusion coefficient of the solvent is calculated by using mean square displacement (MSD) where as that for solute (NO) is calculated by using MSD and velocity auto-correlation function (VACF). The results are then compared with the available experimental values. The results from the present work for water come in good agreement, very precise at low temperatures, with the experimental values. The diffusion coefficients of NO, on the other hands, agree well with the available theoretical studies, and also with experiment at low temperatures (up to 310 K). The results at the higher temperatures (up to 333 K), however, deviate significantly with the experimental observations. Also, the mutual diffusion coefficients of NO in water have been calculated by using Darken’s relation. The temperature dependence of the calculated diffusion coefficients follow the Arrhenius behavior.

The Gini coefficient: a methodological pilot study to assess fetal brain development employing postmortem diffusion MRI.

PubMed

Viehweger, Adrian; Riffert, Till; Dhital, Bibek; Knösche, Thomas R; Anwander, Alfred; Stepan, Holger; Sorge, Ina; Hirsch, Wolfgang

2014-10-01

Diffusion-weighted imaging (DWI) is important in the assessment of fetal brain development. However, it is clinically challenging and time-consuming to prepare neuromorphological examinations to assess real brain age and to detect abnormalities. To demonstrate that the Gini coefficient can be a simple, intuitive parameter for modelling fetal brain development. Postmortem fetal specimens(n = 28) were evaluated by diffusion-weighted imaging (DWI) on a 3-T MRI scanner using 60 directions, 0.7-mm isotropic voxels and b-values of 0, 150, 1,600 s/mm(2). Constrained spherical deconvolution (CSD) was used as the local diffusion model. Fractional anisotropy (FA), apparent diffusion coefficient (ADC) and complexity (CX) maps were generated. CX was defined as a novel diffusion metric. On the basis of those three parameters, the Gini coefficient was calculated. Study of fetal brain development in postmortem specimens was feasible using DWI. The Gini coefficient could be calculated for the combination of the three diffusion parameters. This multidimensional Gini coefficient correlated well with age (Adjusted R(2) = 0.59) between the ages of 17 and 26 gestational weeks. We propose a new method that uses an economics concept, the Gini coefficient, to describe the whole brain with one simple and intuitive measure, which can be used to assess the brain's developmental state.

Effective diffusion coefficients of DNAPL waste components in saturated low permeability soil materials

NASA Astrophysics Data System (ADS)

Ayral-Cinar, Derya; Demond, Avery H.

2017-12-01

Diffusion is regarded as the dominant transport mechanism into and out of low permeable subsurface lenses and layers in the subsurface. But, some reports of mass storage in such zones are higher than what might be attributable to diffusion, based on estimated diffusion coefficients. Despite the importance of diffusion to efforts to estimate the quantity of residual contamination in the subsurface, relatively few studies present measured diffusion coefficients of organic solutes in saturated low permeability soils. This study reports the diffusion coefficients of a trichloroethylene (TCE), and an anionic surfactant, Aerosol OT (AOT), in water-saturated silt and a silt-montmorillonite (25:75) mixture, obtained using steady-state experiments. The relative diffusivity ranged from 0.11 to 0.17 for all three compounds for the silt and the silt-clay mixture that was allowed to expand. In the case in which the swelling was constrained, the relative diffusivity was about 0.07. In addition, the relative diffusivity of 13C-labeled TCE through a water saturated silt-clay mixture that had contacted a field dense non-aqueous phase liquid (DNAPL) for 18 months was measured and equaled 0.001. These experimental results were compared with the estimates generated using common correlations, and it was found that, in all cases, the measured diffusion coefficients were significantly lower than the estimated. Thus, the discrepancy between mass accumulations observed in the field and the mass storage that can attributable to diffusion may be greater than previously believed.

The tracer diffusion coefficient of soft nanoparticles in a linear polymer matrix

DOE PAGES

Imel, Adam E.; Rostom, Sahar; Holley, Wade; ...

2017-03-09

The diffusion properties of nanoparticles in polymer nanocomposites are largely unknown and are often difficult to determine experimentally. To address this shortcoming, we have developed a novel method to determine the tracer diffusion coefficient of soft polystyrene nanoparticles in a linear polystyrene matrix. Monitoring the interdiffusion of soft nanoparticles into a linear polystyrene matrix provides the mutual diffusion coefficient of this system, from which the tracer diffusion coefficient of the soft nanoparticle can be determined using the slow mode theory. Utilizing this protocol, the role of nanoparticle molecular weight and rigidity on its tracer diffusion coefficient is provided. These resultsmore » demonstrate that the diffusive behavior of these soft nanoparticles differ from that of star polymers, which is surprising since our recent studies suggest that the nanoparticle interacts with a linear polymer similarly to that of a star polymer. It appears that these deformable nanoparticles mostly closely mimic the diffusive behavior of fractal macromolecular architectures or microgels, where the transport of the nanoparticle relies on the cooperative motion of neighboring linear chains. Finally, the less cross-linked, and thus more deformable, nanoparticles diffuse faster than the more highly crosslinked nanoparticles, presumably because the increased deformability allows the nanoparticle to distort and fit into available space.« less

Porewater dynamics of silver, lead and copper in coastal sediments and implications for benthic metal fluxes

USGS Publications Warehouse

Kalnejais, Linda H.; Martin, W. R.; Bothner, Michael H.

2015-01-01

To determine the conditions that lead to a diffusive release of dissolved metals from coastal sediments, porewater profiles of Ag, Cu, and Pb have been collected over seven years at two contrasting coastal sites in Massachusetts, USA. The Hingham Bay (HB) site is a contaminated location in Boston Harbor, while the Massachusetts Bay (MB) site is 11 km offshore and less impacted. At both sites, the biogeochemical cycles include scavenging by Fe-oxyhydroxides and release of dissolved metals when Fe-oxyhydroxides are reduced. Important differences in the metal cycles at the two sites, however, result from different redox conditions. Porewater sulfide and seasonal variation in redox zone depth is observed at HB, but not at MB. In summer, as the conditions become more reducing at HB, trace metals are precipitated as sulfides and are no longer associated with Fe-oxyhydroxides. Sulfide precipitation close to the sediment–water interface limits the trace metal flux in summer and autumn at HB, while in winter, oxidation of the sulfide phases drives high benthic fluxes of Cu and Ag, as oxic conditions return. The annual diffusive flux of Cu at HB is found to be significant and contributes to the higher than expected water column Cu concentrations observed in Boston Harbor. At MB, due to the lower sulfide concentrations, the association of trace metals with Fe-oxyhydroxides occurs throughout the year, leading to more stable fluxes. A surface enrichment of solid phase trace metals was found at MB and is attributed to the persistent scavenging by Fe-oxyhydroxides. This process is important, particularly at sites that are less reducing, because it maintains elevated metal concentrations at the surface despite the effects of bioturbation and sediment accumulation, and because it may increase the persistence of metal contamination in surface sediments.

Simultaneous characterization of lateral lipid and prothrombin diffusion coefficients by z-scan fluorescence correlation spectroscopy.

PubMed

Stefl, Martin; Kułakowska, Anna; Hof, Martin

2009-08-05

A new (to our knowledge) robust approach for the determination of lateral diffusion coefficients of weakly bound proteins is applied for the phosphatidylserine specific membrane interaction of bovine prothrombin. It is shown that z-scan fluorescence correlation spectroscopy in combination with pulsed interleaved dual excitation allows simultaneous monitoring of the lateral diffusion of labeled protein and phospholipids. Moreover, from the dependencies of the particle numbers on the axial sample positions at different protein concentrations phosphatidylserine-dependent equilibrium dissociation constants are derived confirming literature values. Increasing the amount of membrane-bound prothrombin retards the lateral protein and lipid diffusion, indicating coupling of both processes. The lateral diffusion coefficients of labeled lipids are considerably larger than the simultaneously determined lateral diffusion coefficients of prothrombin, which contradicts findings reported for the isolated N-terminus of prothrombin.

Transport of neutral solute across articular cartilage: the role of zonal diffusivities.

PubMed

Arbabi, V; Pouran, B; Weinans, H; Zadpoor, A A

2015-07-01

Transport of solutes through diffusion is an important metabolic mechanism for the avascular cartilage tissue. Three types of interconnected physical phenomena, namely mechanical, electrical, and chemical, are all involved in the physics of transport in cartilage. In this study, we use a carefully designed experimental-computational setup to separate the effects of mechanical and chemical factors from those of electrical charges. Axial diffusion of a neutral solute Iodixanol into cartilage was monitored using calibrated microcomputed tomography micro-CT images for up to 48 hr. A biphasic-solute computational model was fitted to the experimental data to determine the diffusion coefficients of cartilage. Cartilage was modeled either using one single diffusion coefficient (single-zone model) or using three diffusion coefficients corresponding to superficial, middle, and deep cartilage zones (multizone model). It was observed that the single-zone model cannot capture the entire concentration-time curve and under-predicts the near-equilibrium concentration values, whereas the multizone model could very well match the experimental data. The diffusion coefficient of the superficial zone was found to be at least one order of magnitude larger than that of the middle zone. Since neutral solutes were used, glycosaminoglycan (GAG) content cannot be the primary reason behind such large differences between the diffusion coefficients of the different cartilage zones. It is therefore concluded that other features of the different cartilage zones such as water content and the organization (orientation) of collagen fibers may be enough to cause large differences in diffusion coefficients through the cartilage thickness.

Modeling the formation of iron sulfide scales using thermodynamic simulation software

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anderko, A.; Shuler, P.J.

1998-12-31

A program has been developed for generating stability diagrams that concisely represent the thermodynamic state of multicomponent, multiphase aqueous systems in wide ranges of temperature and component concentrations. The diagrams are based on a thermodynamic model that combines the Helgeson-Kirkham-Flowers equation of state for standard-state properties with a solutions nonideality model based on the activity coefficient expressions developed by Bromley and Pitzer. The diagrams offer a flexible choice of independent variables, which include component concentrations in addition to the potential and pH. The stability diagrams are used to predict the conditions that favor the formation of stable and metastable ironmore » sulfide species, which are commonly deposited under oil field-related conditions. First, the diagrams have been applied to establish a sequence of transformations that iron sulfides undergo as they age. The predicted transformation sequences take into account environmental variables (e.g., hydrogen sulfide concentration, oxygen availability, etc.). The predictions are in agreement with experimental data on iron sulfide formation at the iron/solution interface and in bulk solution. The understanding of iron sulfide transformation sequences makes it possible to simulate experimental studies of H{sub 2}S/CO{sub 2} corrosion in the presence or absence of oxygen. A comparison with laboratory corrosion rate data under gas pipeline conditions indicates that the magnitude of corrosion rates can be correlated with the predicted stability of metastable iron sulfide phases.« less

Unifying diffusion and seepage for nonlinear gas transport in multiscale porous media

NASA Astrophysics Data System (ADS)

Song, Hongqing; Wang, Yuhe; Wang, Jiulong; Li, Zhengyi

2016-09-01

We unify the diffusion and seepage process for nonlinear gas transport in multiscale porous media via a proposed new general transport equation. A coherent theoretical derivation indicates the wall-molecule and molecule-molecule collisions drive the Knudsen and collective diffusive fluxes, and constitute the system pressure across the porous media. A new terminology, nominal diffusion coefficient can summarize Knudsen and collective diffusion coefficients. Physical and numerical experiments show the support of the new formulation and provide approaches to obtain the diffusion coefficient and permeability simultaneously. This work has important implication for natural gas extraction and greenhouse gases sequestration in geological formations.

Numerical study of centrifugal compressor stage vaneless diffusers

NASA Astrophysics Data System (ADS)

Galerkin, Y.; Soldatova, K.; Solovieva, O.

2015-08-01

The authors analyzed CFD calculations of flow in vaneless diffusers with relative width in range from 0.014 to 0.100 at inlet flow angles in range from 100 to 450 with different inlet velocity coefficients, Reynolds numbers and surface roughness. The aim is to simulate calculated performances by simple algebraic equations. The friction coefficient that represents head losses as friction losses is proposed for simulation. The friction coefficient and loss coefficient are directly connected by simple equation. The advantage is that friction coefficient changes comparatively little in range of studied parameters. Simple equations for this coefficient are proposed by the authors. The simulation accuracy is sufficient for practical calculations. To create the complete algebraic model of the vaneless diffuser the authors plan to widen this method of modeling to diffusers with different relative length and for wider range of Reynolds numbers.

Determination of partition and diffusion coefficients of formaldehyde in selected building materials and impact of relative humidity.

PubMed

Xu, Jing; Zhang, Jianshun S; Liu, Xiaoyu; Gao, Zhi

2012-06-01

The partition and effective diffusion coefficients of formaldehyde were measured for three materials (conventional gypsum wallboard, "green" gypsum wallboard, and "green" carpet) under three relative humidity (RH) conditions (20%, 50%, and 70% RH). The "green" materials contained recycled materials and were friendly to environment. A dynamic dual-chamber test method was used. Results showed that a higher relative humidity led to a larger effective diffusion coefficient for two kinds of wallboards and carpet. The carpet was also found to be very permeable resulting in an effective diffusion coefficient at the same order of magnitude with the formaldehyde diffusion coefficient in air. The partition coefficient (K(ma)) of formaldehyde in conventional wallboard was 1.52 times larger at 50% RH than at 20% RH, whereas it decreased slightly from 50% to 70% RH, presumably due to the combined effects of water solubility of formaldehyde and micro-pore blocking by condensed moisture at the high RH level. The partition coefficient of formaldehyde increased slightly with the increase of relative humidity in "green" wallboard and "green" carpet. At the same relative humidity level, the "green" wallboard had larger partition coefficient and effective diffusion coefficient than the conventional wallboard, presumably due to the micro-pore structure differences between the two materials. The data generated could be used to assess the sorption effects of formaldehyde on building materials and to evaluate its impact on the formaldehyde concentration in buildings.

Determination of diffusion coefficients of various livestock antibiotics in water at infinite dilution

NASA Astrophysics Data System (ADS)

Soriano, Allan N.; Adamos, Kristoni G.; Bonifacio, Pauline B.; Adornado, Adonis P.; Bungay, Vergel C.; Vairavan, Rajendaran

2017-11-01

The fate of antibiotics entering the environment raised concerns on the possible effect of antimicrobial resistance bacteria. Prediction of the fate and transport of these particles are needed to be determined, significantly the diffusion coefficient of antibiotic in water at infinite dilution. A systematic determination of diffusion coefficient of antibiotic in water at infinite dilution of five different kinds of livestock antibiotics namely: Amtyl, Ciprotyl, Doxylak Forte, Trisullak, and Vetracin Gold in the 293.15 to 313.15 K temperature range are reported through the use of the method involving the electrolytic conductivity measurements. A continuous stirred tank reactor is utilized to measure the electrolytic conductivities of the considered systems. These conductivities are correlated by using the Nernst-Haskell equation to determine the infinite dilution diffusion coefficient. Determined diffusion coefficients are based on the assumption that in dilute solution, these antibiotics behave as strong electrolyte from which H+ cation dissociate from the antibiotic's anion.

Determination of molecular diffusion coefficient in n-alkane binary mixtures: empirical correlations.

PubMed

De Mezquia, D Alonso; Bou-Ali, M Mounir; Larrañaga, M; Madariaga, J A; Santamaría, C

2012-03-08

In this work we have measured the molecular diffusion coefficient of the n-alkane binary series nC(i)-nC(6), nC(i)-nC(10), and nC(i)-nC(12) at 298 K and 1 atm and a mass fraction of 0.5 by using the so-called sliding symmetric tubes technique. The results show that the diffusion coefficient at this concentration is proportional to the inverse viscosity of the mixture. In addition, we have also measured the diffusion coefficient of the systems nC(12)-nC(6), nC(12)-nC(7), and nC(12)-nC(8) as a function of concentration. From the data obtained, it is shown that the diffusion coefficient of the n-alkane binary mixtures at any concentration can be calculated from the molecular weight of the components and the dynamic viscosity of the corresponding mixture at 50% mass fraction.

Measurement of the ferric diffusion coefficient in agarose and gelatine gels by utilization of the evolution of a radiation induced edge as reflected in relaxation rate images.

PubMed

Pedersen, T V; Olsen, D R; Skretting, A

1997-08-01

A method has been developed to determine the diffusion coefficients of ferric ions in ferrous sulphate doped gels. A radiation induced edge was created in the gel, and two spin-echo sequences were used to acquire a pair of images of the gel at different points of time. For each of these image pairs, a longitudinal relaxation rate image was derived. From profiles through these images, the standard deviations of the Gaussian functions that characterize diffusion were determined. These data provided the basis for the determination of the ferric diffusion coefficients by two different methods. Simulations indicate that the use of single spin-echo images in this procedure may in some cases lead to a significant underestimation of the diffusion coefficient. The technique was applied to different agarose and gelatine gels that were prepared, irradiated and imaged simultaneously. The results indicate that the diffusion coefficient is lower in a gelatine gel than in an agarose gel. Addition of xylenol orange to a gelatine gel lowers the diffusion coefficient from 1.45 to 0.81 mm2 h-1, at the cost of significantly lower Rl sensitivity. The addition of benzoic acid to the latter gel did not increase the Rl sensitivity.

Effects of different cooling treatments on water diffusion, microcirculation, and water content within exercised muscles: evaluation by magnetic resonance T2-weighted and diffusion-weighted imaging.

PubMed

Yanagisawa, Osamu; Takahashi, Hideyuki; Fukubayashi, Toru

2010-09-01

In this study, we determined the effects of different cooling treatments on exercised muscles. Seven adults underwent four post-exercise treatments (20-min ice-bag application, 60-min gel-pack application at 10 degrees C and 17 degrees C, and non-cooling treatment) with at least 1 week between treatments. Magnetic resonance diffusion- and T2-weighted images were obtained to calculate the apparent diffusion coefficients (apparent diffusion coefficient 1, which reflects intramuscular water diffusion and microcirculation, and apparent diffusion coefficient 2, which is approximately equal to the true diffusion coefficient that excludes as much of the effect of intramuscular microcirculation as possible) and the T2 values (intramuscular water content level) of the ankle dorsiflexors, respectively, before and after ankle dorsiflexion exercise and after post-exercise treatment. The T2 values increased significantly after exercise and returned to pre-exercise values after each treatment; no significant differences were observed among the four post-exercise treatments. Both apparent diffusion coefficients also increased significantly after exercise and decreased significantly after the three cooling treatments; no significant difference was detected among the three cooling treatments. Local cooling suppresses both water diffusion and microcirculation within exercised muscles. Moreover, although the treatment time was longer, adequate cooling effects could be achieved using the gel-pack applications at relatively mild cooling temperatures.

CO2 diffusion in champagne wines: a molecular dynamics study.

PubMed

Perret, Alexandre; Bonhommeau, David A; Liger-Belair, Gérard; Cours, Thibaud; Alijah, Alexander

2014-02-20

Although diffusion is considered as the main physical process responsible for the nucleation and growth of carbon dioxide bubbles in sparkling beverages, the role of each type of molecule in the diffusion process remains unclear. In the present study, we have used the TIP5P and SPC/E water models to perform force field molecular dynamics simulations of CO2 molecules in water and in a water/ethanol mixture respecting Champagne wine proportions. CO2 diffusion coefficients were computed by applying the generalized Fick's law for the determination of multicomponent diffusion coefficients, a law that simplifies to the standard Fick's law in the case of champagnes. The CO2 diffusion coefficients obtained in pure water and water/ethanol mixtures composed of TIP5P water molecules were always found to exceed the coefficients obtained in mixtures composed of SPC/E water molecules, a trend that was attributed to a larger propensity of SPC/E water molecules to form hydrogen bonds. Despite the fact that the SPC/E model is more accurate than the TIP5P model to compute water self-diffusion and CO2 diffusion in pure water, the diffusion coefficients of CO2 molecules in the water/ethanol mixture are in much better agreement with the experimental values of 1.4 - 1.5 × 10(-9) m(2)/s obtained for Champagne wines when the TIP5P model is employed. This difference was deemed to rely on the larger propensity of SPC/E water molecules to maintain the hydrogen-bonded network between water molecules and form new hydrogen bonds with ethanol, although statistical issues cannot be completely excluded. The remarkable agreement between the theoretical CO2 diffusion coefficients obtained within the TIP5P water/ethanol mixture and the experimental data specific to Champagne wines makes us infer that the diffusion coefficient in these emblematic hydroalcoholic sparkling beverages is expected to remain roughly constant whathever their proportions in sugars, glycerol, or peptides.

Comparison of experimental methods for estimating matrix diffusion coefficients for contaminant transport modeling

DOE PAGES

Telfeyan, Katherine Christina; Ware, Stuart Doug; Reimus, Paul William; ...

2018-01-31

Here, diffusion cell and diffusion wafer experiments were conducted to compare methods for estimating effective matrix diffusion coefficients in rock core samples from Pahute Mesa at the Nevada Nuclear Security Site (NNSS). A diffusion wafer method, in which a solute diffuses out of a rock matrix that is pre-saturated with water containing the solute, is presented as a simpler alternative to the traditional through-diffusion (diffusion cell) method. Both methods yielded estimates of effective matrix diffusion coefficients that were within the range of values previously reported for NNSS volcanic rocks. The difference between the estimates of the two methods ranged frommore » 14 to 30%, and there was no systematic high or low bias of one method relative to the other. From a transport modeling perspective, these differences are relatively minor when one considers that other variables (e.g., fracture apertures, fracture spacings) influence matrix diffusion to a greater degree and tend to have greater uncertainty than effective matrix diffusion coefficients. For the same relative random errors in concentration measurements, the diffusion cell method yields effective matrix diffusion coefficient estimates that have less uncertainty than the wafer method. However, the wafer method is easier and less costly to implement and yields estimates more quickly, thus allowing a greater number of samples to be analyzed for the same cost and time. Given the relatively good agreement between the methods, and the lack of any apparent bias between the methods, the diffusion wafer method appears to offer advantages over the diffusion cell method if better statistical representation of a given set of rock samples is desired.« less

Comparison of experimental methods for estimating matrix diffusion coefficients for contaminant transport modeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Telfeyan, Katherine Christina; Ware, Stuart Doug; Reimus, Paul William

Here, diffusion cell and diffusion wafer experiments were conducted to compare methods for estimating effective matrix diffusion coefficients in rock core samples from Pahute Mesa at the Nevada Nuclear Security Site (NNSS). A diffusion wafer method, in which a solute diffuses out of a rock matrix that is pre-saturated with water containing the solute, is presented as a simpler alternative to the traditional through-diffusion (diffusion cell) method. Both methods yielded estimates of effective matrix diffusion coefficients that were within the range of values previously reported for NNSS volcanic rocks. The difference between the estimates of the two methods ranged frommore » 14 to 30%, and there was no systematic high or low bias of one method relative to the other. From a transport modeling perspective, these differences are relatively minor when one considers that other variables (e.g., fracture apertures, fracture spacings) influence matrix diffusion to a greater degree and tend to have greater uncertainty than effective matrix diffusion coefficients. For the same relative random errors in concentration measurements, the diffusion cell method yields effective matrix diffusion coefficient estimates that have less uncertainty than the wafer method. However, the wafer method is easier and less costly to implement and yields estimates more quickly, thus allowing a greater number of samples to be analyzed for the same cost and time. Given the relatively good agreement between the methods, and the lack of any apparent bias between the methods, the diffusion wafer method appears to offer advantages over the diffusion cell method if better statistical representation of a given set of rock samples is desired.« less

Multispecies diffusion models: A study of uranyl species diffusion

NASA Astrophysics Data System (ADS)

Liu, Chongxuan; Shang, Jianying; Zachara, John M.

2011-12-01

Rigorous numerical description of multispecies diffusion requires coupling of species, charge, and aqueous and surface complexation reactions that collectively affect diffusive fluxes. The applicability of a fully coupled diffusion model is, however, often constrained by the availability of species self-diffusion coefficients, as well as by computational complication in imposing charge conservation. In this study, several diffusion models with variable complexity in charge and species coupling were formulated and compared to describe reactive multispecies diffusion in groundwater. Diffusion of uranyl [U(VI)] species was used as an example in demonstrating the effectiveness of the models in describing multispecies diffusion. Numerical simulations found that a diffusion model with a single, common diffusion coefficient for all species was sufficient to describe multispecies U(VI) diffusion under a steady state condition of major chemical composition, but not under transient chemical conditions. Simulations revealed that for multispecies U(VI) diffusion under transient chemical conditions, a fully coupled diffusion model could be well approximated by a component-based diffusion model when the diffusion coefficient for each chemical component was properly selected. The component-based diffusion model considers the difference in diffusion coefficients between chemical components, but not between the species within each chemical component. This treatment significantly enhanced computational efficiency at the expense of minor charge conservation. The charge balance in the component-based diffusion model can be enforced, if necessary, by adding a secondary migration term resulting from model simplification. The effect of ion activity coefficient gradients on multispecies diffusion is also discussed. The diffusion models were applied to describe U(VI) diffusive mass transfer in intragranular domains in two sediments collected from U.S. Department of Energy's Hanford 300A, where intragranular diffusion is a rate-limiting process controlling U(VI) adsorption and desorption. The grain-scale reactive diffusion model was able to describe U(VI) adsorption/desorption kinetics that had been previously described using a semiempirical, multirate model. Compared with the multirate model, the diffusion models have the advantage to provide spatiotemporal speciation evolution within the diffusion domains.

Inhibitory and bactericidal action of the biocorrosion agents «INCORGAS» and «AMDOR».

PubMed

Tsygankova, L E; Vigdorovich, V I; Esina, M N; Nazina, T N; Dubinskaya, E V

2014-06-01

Inhibiting action of A, B and M-X compositions against hydrosulfide corrosion of carbon steel, hydrogen diffusion through the steel membrane has been studied along with their bactericidal effect with respect to sulfate-reducing bacteria of Desulfomicrobium type. Bactericidal properties of the compositions have been studied in the Postgate medium. Corrosion tests have been made in the NACE medium saturated by hydrogen sulfide and carbon dioxide separately and together by methods of gravimetrical measurements and linear polarization resistance (LRP). Potentiodynamic polarization and electrochemical diffusion method have been used. Steel protection is determined in the inhibited solutions by combined action of corrosion products film and inhibitor. Presence of sulfate-reducing bacteria in medium increases hydrogen diffusion flux through the steel membrane by 2-3 times and essentially stimulates effect of the inhibitors. The inhibiting compositions decrease quantity of sulfate-reducing bacteria (SRB) by 95-98%. The obtained results testify about predominately bacteriostatic action of the inhibiting compositions, which has influence on the enzymatic systems of SRB cells responsible directly for the sulfate reduction because of substantially decreasing the biogenic hydrogen sulfide concentration in the system. © 2013 Elsevier B.V. All rights reserved.

Estimation of diffusion coefficients from voltammetric signals by support vector and gaussian process regression

PubMed Central

2014-01-01

Background Support vector regression (SVR) and Gaussian process regression (GPR) were used for the analysis of electroanalytical experimental data to estimate diffusion coefficients. Results For simulated cyclic voltammograms based on the EC, Eqr, and EqrC mechanisms these regression algorithms in combination with nonlinear kernel/covariance functions yielded diffusion coefficients with higher accuracy as compared to the standard approach of calculating diffusion coefficients relying on the Nicholson-Shain equation. The level of accuracy achieved by SVR and GPR is virtually independent of the rate constants governing the respective reaction steps. Further, the reduction of high-dimensional voltammetric signals by manual selection of typical voltammetric peak features decreased the performance of both regression algorithms compared to a reduction by downsampling or principal component analysis. After training on simulated data sets, diffusion coefficients were estimated by the regression algorithms for experimental data comprising voltammetric signals for three organometallic complexes. Conclusions Estimated diffusion coefficients closely matched the values determined by the parameter fitting method, but reduced the required computational time considerably for one of the reaction mechanisms. The automated processing of voltammograms according to the regression algorithms yields better results than the conventional analysis of peak-related data. PMID:24987463

The influence of screening of the polyion electrostatic potential on the counterion dynamics in polyelectrolyte solutions

NASA Astrophysics Data System (ADS)

Schipper, F. J. M.; Hollander, J. G.; Leyte, J. C.

1998-10-01

The self-diffusion coefficient of tetra-methylammonium counterion in solutions of polymethacrylic acid in 0953-8984/10/41/004/img1 has been measured over a broad polyion concentration range at a constant degree of neutralization and at different ratios of added monovalent or bivalent salt to polyions. A maximum counterion self-diffusion coefficient was observed as a function of polyion concentration. The value of the self-diffusion coefficient at the maximum did not depend on the valency of the added salt. The maximum was found at lower polymer concentrations and with a higher value, when the ratio of added salt to polyions was increased, as predicted by the Poisson-Boltzmann-Smoluchowski equation in the cylindrical cell model for polyelectrolytes. At higher polyion concentrations a maximum counterion self-diffusion coefficient against the ratio of added salt and polyions was observed, which has not been reported before. Upon increasing this ratio the electrostatic potential of the polyelectrolyte gets screened, leading to an increase of the counterion self-diffusion coefficient. Concentration effects of the added salt on the other hand ultimately lead to a decrease of the counterion self-diffusion coefficient, which explains the occurrence of a maximum.

Multilevel Preconditioners for Reaction-Diffusion Problems with Discontinuous Coefficients

DOE PAGES

Kolev, Tzanio V.; Xu, Jinchao; Zhu, Yunrong

2015-08-23

In this study, we extend some of the multilevel convergence results obtained by Xu and Zhu, to the case of second order linear reaction-diffusion equations. Specifically, we consider the multilevel preconditioners for solving the linear systems arising from the linear finite element approximation of the problem, where both diffusion and reaction coefficients are piecewise-constant functions. We discuss in detail the influence of both the discontinuous reaction and diffusion coefficients to the performance of the classical BPX and multigrid V-cycle preconditioner.

Note: On the relation between Lifson-Jackson and Derrida formulas for effective diffusion coefficient

NASA Astrophysics Data System (ADS)

Kalnin, Juris R.; Berezhkovskii, Alexander M.

2013-11-01

The Lifson-Jackson formula provides the effective free diffusion coefficient for a particle diffusing in an arbitrary one-dimensional periodic potential. Its counterpart, when the underlying dynamics is described in terms of an unbiased nearest-neighbor Markovian random walk on a one-dimensional periodic lattice is given by the formula obtained by Derrida. It is shown that the latter formula can be considered as a discretized version of the Lifson-Jackson formula with correctly chosen position-dependent diffusion coefficient.

Influence of Sulfide Nanoparticles on Dissolved Mercury and Zinc Quantification by Diffusive Gradient in Thin-Film Passive Samplers.

PubMed

Pham, Anh Le-Tuan; Johnson, Carol; Manley, Devon; Hsu-Kim, Heileen

2015-11-03

Diffusive gradient in thin-film (DGT) passive samplers are frequently used to monitor the concentrations of metals such as mercury and zinc in sediments and other aquatic environments. The application of these samplers generally presumes that they quantify only the dissolved fraction and not particle-bound metal species that are too large to migrate into the sampler. However, metals associated with very small nanoparticles (smaller than the pore size of DGT samplers) can be abundant in certain environments, yet the implications of these nanoparticles for DGT measurements are unclear. The objective of this study was to determine how the performance of the DGT sampler is affected by the presence of nanoparticulate species of Hg and Zn. DGT samplers were exposed to solutions containing known amounts of dissolved Hg(II) and nanoparticulate HgS (or dissolved Zn(II) and nanoparticulate ZnS). The amounts of Hg and Zn accumulated onto the DGT samplers were quantified over hours to days, and the rates of diffusion of the dissolved metal (i.e., the effective diffusion coefficient D) into the sampler's diffusion layer were calculated and compared for solutions containing varying concentrations of nanoparticles. The results suggested that the nanoparticles deposited on the surface of the samplers might have acted as sorbents, slowing the migration of the dissolved species into the samplers. The consequence was that the DGT sampler data underestimated the dissolved metal concentration in the solution. In addition, X-ray absorption spectroscopy was employed to determine the speciation of the Hg accumulated on the sampler binding layer, and the results indicated that HgS nanoparticles did not appear to directly contribute to the DGT measurement. Overall, our findings suggest that the deployment of DGT samplers in settings where nanoparticles are relevant (e.g., sediments) may result in DGT data that incorrectly estimated the dissolved metal concentrations. Models for metal uptake into the sampler may need to be reconsidered.

Consequences of using nonlinear particle trajectories to compute spatial diffusion coefficients. [for cosmic ray propagation in interstellar and interplanetary space

NASA Technical Reports Server (NTRS)

Goldstein, M. L.

1977-01-01

In a study of cosmic ray propagation in interstellar and interplanetary space, a perturbed orbit resonant scattering theory for pitch angle diffusion in a slab model of magnetostatic turbulence is slightly generalized and used to compute the diffusion coefficient for spatial propagation parallel to the mean magnetic field. This diffusion coefficient has been useful for describing the solar modulation of the galactic cosmic rays, and for explaining the diffusive phase in solar flares in which the initial anisotropy of the particle distribution decays to isotropy.

Translational diffusion coefficients of volatile compounds in various aqueous solutions at low and subzero temperatures.

PubMed

Covarrubias-Cervantes, Marco; Champion, Dominique; Debeaufort, Frédéric; Voilley, Andrée

2005-08-24

Translational diffusion coefficients (D(12)) of volatile compounds were measured in model media with the profile concentration method. The influence of sample temperature (from 25 to -10 degrees C) was studied on translational diffusion in sucrose or maltodextrin solutions at various concentrations. Results show that diffusivity of volatile compounds in sucrose solutions is controlled by temperature, molecule size, and the viscosity of the liquid phase as expected with the Stokes-Einstein equation; moreover, physicochemical interactions between volatile compounds and the medium are determinant for diffusion estimation. At negative temperature, the winding path induced by an ice crystal content of >70% lowered volatile compound diffusion. On the contrary, no influence on translational diffusion coefficients was observed for lower ice content.

Experimental Method Development for Estimating Solid-phase Diffusion Coefficients and Material/Air Partition Coefficients of SVOCs

EPA Science Inventory

The solid-phase diffusion coefficient (Dm) and material-air partition coefficient (Kma) are key parameters for characterizing the sources and transport of semivolatile organic compounds (SVOCs) in the indoor environment. In this work, a new experimental method was developed to es...

Diffusion of cations in chromia layers grown on iron-base alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lobnig, R.E.; Hennesen, K.; Grabke, H.J.

Diffusion of the cations Cr, Fe, Mn, and Ni in Cr{sub 2}O{sub 3} has been investigated at 1,173 K. The diffusion measurements were performed on chromia layers grown on the model alloys Fe-20Cr and Fe-20Cr-12Ni in order to consider effects of small amounts of dissolved alien cations in Cr{sub 2}O{sub 3}. The samples were diffusion annealed in H{sub 2}-H{sub 2}O at an oxygen partial pressure close to the Cr{sub 2}O{sub 3}/Cr equilibrium. For all tracers the lattice-diffusion coefficients are 3-5 orders of magnitude smaller than the grain-boundary diffusion coefficients. The lattice diffusivity of Mn is about two orders of magnitudemore » greater than the other lattice-diffusion coefficients, especially in Cr{sub 2}O{sub 3} grown on Fe-20Cr-12Ni. The values of the diffusion coefficients for Cr, Fe, and Ni are in the same range. Diffusion of the tracers in Cr{sub 2}O{sub 3} grown on different alloys did not show significant differences with the exception of Mn.« less

Many-body Effects in a Laterally Inhomogeneous Semiconductor Quantum Well

NASA Technical Reports Server (NTRS)

Ning, Cun-Zheng; Li, Jian-Zhong; Biegel, Bryan A. (Technical Monitor)

2002-01-01

Many body effects on conduction and diffusion of electrons and holes in a semiconductor quantum well are studied using a microscopic theory. The roles played by the screened Hartree-Fock (SHE) terms and the scattering terms are examined. It is found that the electron and hole conductivities depend only on the scattering terms, while the two-component electron-hole diffusion coefficients depend on both the SHE part and the scattering part. We show that, in the limit of the ambipolax diffusion approximation, however, the diffusion coefficients for carrier density and temperature are independent of electron-hole scattering. In particular, we found that the SHE terms lead to a reduction of density-diffusion coefficients and an increase in temperature-diffusion coefficients. Such a reduction or increase is explained in terms of a density-and temperature dependent energy landscape created by the bandgap renormalization.

Determination of the zincate diffusion coefficient and its application to alkaline battery problems

NASA Technical Reports Server (NTRS)

May, C. E.; Kautz, Harold E.

1978-01-01

The diffusion coefficient for the zincate ion at 24 C was found to be 9.9 X 10 to the minus 7th power squared cm per sec + or - 30 percent in 45 percent potassium hydroxide and 1.4 x 10 to the minus 7 squared cm per sec + or - 25 percent in 40 percent sodium hydroxide. Comparison of these values with literature values at different potassium hydroxide concentrations show that the Stokes-Einstein equation is obeyed. The diffusion coefficient is characteristic of the zincate ion (not the cation) and independent of its concentration. Calculations with the measured value of the diffusion coefficient show that the zinc concentration in an alkaline zincate half cell becomes uniform throughout in tens of hours by diffusion alone. Diffusion equations are derived which are applicable to finite size chambers. Details and discussion of the experimental method are also given.

Coiled to diffuse: Brownian motion of a helical bacterium.

PubMed

Butenko, Alexander V; Mogilko, Emma; Amitai, Lee; Pokroy, Boaz; Sloutskin, Eli

2012-09-11

We employ real-time three-dimensional confocal microscopy to follow the Brownian motion of a fixed helically shaped Leptospira interrogans (LI) bacterium. We extract from our measurements the translational and the rotational diffusion coefficients of this bacterium. A simple theoretical model is suggested, perfectly reproducing the experimental diffusion coefficients, with no tunable parameters. An older theoretical model, where edge effects are neglected, dramatically underestimates the observed rates of translation. Interestingly, the coiling of LI increases its rotational diffusion coefficient by a factor of 5, compared to a (hypothetical) rectified bacterium of the same contour length. Moreover, the translational diffusion coefficients would have decreased by a factor of ~1.5, if LI were rectified. This suggests that the spiral shape of the spirochaete bacteria, in addition to being employed for their active twisting motion, may also increase the ability of these bacteria to explore the surrounding fluid by passive Brownian diffusion.

Determination of the zincate diffusion coefficient and its application to alkaline battery problems

NASA Technical Reports Server (NTRS)

May, C. E.; Kautz, H. E.

1978-01-01

The diffusion coefficient for the zincate ion at 24 C was found to be 9.9 x 10 to the -7th power sq cm/sec + or - 30% in 45% potassium hydroxide and 1.4 x 10 to the -7th power sq cm/sec + or - 25% in 40% sodium hydroxide. Comparison of these values with literature values at different potassium hydroxide concentrations show that the Stokes-Einstein equation is obeyed. The diffusion coefficient is characteristic of the zincate ion (not the cation) and independent of its concentration. Calculations with the measured value of the diffusion coefficient show that the zinc concentration in an alkaline zincate half-cell becomes uniform throughout in tens of hours by diffusion alone. Diffusion equations are derived which are applicable to finite-size chambers. Details and discussion of the experimental method are also given.

Hydrogen-permeable composite metal membrane and uses thereof

DOEpatents

Edlund, D.J.; Friesen, D.T.

1993-06-08

Various hydrogen production and hydrogen sulfide decomposition processes are disclosed that utilize composite metal membranes that contain an intermetallic diffusion barrier separating a hydrogen-permeable base metal and a hydrogen-permeable coating metal. The barrier is a thermally stable inorganic proton conductor.

The effect of recombination and attachment on meteor radar diffusion coefficient profiles

NASA Astrophysics Data System (ADS)

Lee, C. S.; Younger, J. P.; Reid, I. M.; Kim, Y. H.; Kim, J.-H.

2013-04-01

Estimates of the ambipolar diffusion coefficient producedusing meteor radar echo decay times display an increasing trend below 80-85 km, which is inconsistent with a diffusion-only theory of the evolution of meteor trails. Data from the 33 MHz meteor radar at King Sejong Station, Antarctica, have been compared with observations from the Aura Earth Observing System Microwave Limb Sounder satellite instrument. It has been found that the height at which the diffusion coefficient gradient reverses follows the height of a constant neutral atmospheric density surface. Numerical simulations of meteor trail diffusion including dissociative recombination with atmospheric ions and three-body attachment of free electrons to neutral molecules indicate that three-body attachment is responsible for the distortion of meteor radar diffusion coefficient profiles at heights below 90 km, including the gradient reversal below 80-85 km. Further investigation has revealed that meteor trails with low initial electron line density produce decay times more consistent with a diffusion-only model of meteor trail evolution.

Negative Correlation between the Diffusion Coefficient and Transcriptional Activity of the Glucocorticoid Receptor.

PubMed

Mikuni, Shintaro; Yamamoto, Johtaro; Horio, Takashi; Kinjo, Masataka

2017-08-25

The glucocorticoid receptor (GR) is a transcription factor, which interacts with DNA and other cofactors to regulate gene transcription. Binding to other partners in the cell nucleus alters the diffusion properties of GR. Raster image correlation spectroscopy (RICS) was applied to quantitatively characterize the diffusion properties of EGFP labeled human GR (EGFP-hGR) and its mutants in the cell nucleus. RICS is an image correlation technique that evaluates the spatial distribution of the diffusion coefficient as a diffusion map. Interestingly, we observed that the averaged diffusion coefficient of EGFP-hGR strongly and negatively correlated with its transcriptional activities in comparison to that of EGFP-hGR wild type and mutants with various transcriptional activities. This result suggests that the decreasing of the diffusion coefficient of hGR was reflected in the high-affinity binding to DNA. Moreover, the hyper-phosphorylation of hGR can enhance the transcriptional activity by reduction of the interaction between the hGR and the nuclear corepressors.

Rumor Diffusion in an Interests-Based Dynamic Social Network

PubMed Central

Mao, Xinjun; Guessoum, Zahia; Zhou, Huiping

2013-01-01

To research rumor diffusion in social friend network, based on interests, a dynamic friend network is proposed, which has the characteristics of clustering and community, and a diffusion model is also proposed. With this friend network and rumor diffusion model, based on the zombie-city model, some simulation experiments to analyze the characteristics of rumor diffusion in social friend networks have been conducted. The results show some interesting observations: (1) positive information may evolve to become a rumor through the diffusion process that people may modify the information by word of mouth; (2) with the same average degree, a random social network has a smaller clustering coefficient and is more beneficial for rumor diffusion than the dynamic friend network; (3) a rumor is spread more widely in a social network with a smaller global clustering coefficient than in a social network with a larger global clustering coefficient; and (4) a network with a smaller clustering coefficient has a larger efficiency. PMID:24453911

Rumor diffusion in an interests-based dynamic social network.

PubMed

Tang, Mingsheng; Mao, Xinjun; Guessoum, Zahia; Zhou, Huiping

2013-01-01

To research rumor diffusion in social friend network, based on interests, a dynamic friend network is proposed, which has the characteristics of clustering and community, and a diffusion model is also proposed. With this friend network and rumor diffusion model, based on the zombie-city model, some simulation experiments to analyze the characteristics of rumor diffusion in social friend networks have been conducted. The results show some interesting observations: (1) positive information may evolve to become a rumor through the diffusion process that people may modify the information by word of mouth; (2) with the same average degree, a random social network has a smaller clustering coefficient and is more beneficial for rumor diffusion than the dynamic friend network; (3) a rumor is spread more widely in a social network with a smaller global clustering coefficient than in a social network with a larger global clustering coefficient; and (4) a network with a smaller clustering coefficient has a larger efficiency.

Venus' superrotation, mixing length theory and eddy diffusion - A parametric study

NASA Technical Reports Server (NTRS)

Mayr, H. G.; Harris, I.; Schatten, K. H.; Stevens-Rayburn, D. R.; Chan, K. L.

1988-01-01

The concept of the Hadley mechanism is adopted to describe the axisymmetric circulation of the Venus atmosphere. It is shown that, for the atmosphere of a slowly rotating planet such as Venus, a form of the nonliner 'closure' (self-consistent solution) of the fluid dynamics system which constrains the magnitude of the eddy diffusion coefficients can be postulated. A nonlinear one-layer spectral model of the zonally symmetric circulation was then used to establish the relationship between the heat source, the meridional circulation, and the eddy diffusion coefficients, yielding large zonal velocities. Computer experiments indicated that proportional changes in the heat source and eddy diffusion coefficients do not significantly change the zonal velocities. It was also found that, for large eddy diffusion coefficients, the meridional velocity is virtually constant; below a threshold in the diffusion rate, the meridional velocity decreases; and, for large eddy diffusion and small heating rates, the zonal velocities decrease with decreasing planetary rotation rates.

Arbitrary-order corrections for finite-time drift and diffusion coefficients

NASA Astrophysics Data System (ADS)

Anteneodo, C.; Riera, R.

2009-09-01

We address a standard class of diffusion processes with linear drift and quadratic diffusion coefficients. These contributions to dynamic equations can be directly drawn from data time series. However, real data are constrained to finite sampling rates and therefore it is crucial to establish a suitable mathematical description of the required finite-time corrections. Based on Itô-Taylor expansions, we present the exact corrections to the finite-time drift and diffusion coefficients. These results allow to reconstruct the real hidden coefficients from the empirical estimates. We also derive higher-order finite-time expressions for the third and fourth conditional moments that furnish extra theoretical checks for this class of diffusion models. The analytical predictions are compared with the numerical outcomes of representative artificial time series.

Diffusion coefficient and shear viscosity of rigid water models.

PubMed

Tazi, Sami; Boţan, Alexandru; Salanne, Mathieu; Marry, Virginie; Turq, Pierre; Rotenberg, Benjamin

2012-07-18

We report the diffusion coefficient and viscosity of popular rigid water models: two non-polarizable ones (SPC/E with three sites, and TIP4P/2005 with four sites) and a polarizable one (Dang-Chang, four sites). We exploit the dependence of the diffusion coefficient on the system size (Yeh and Hummer 2004 J. Phys. Chem. B 108 15873) to obtain the size-independent value. This also provides an estimate of the viscosity of all water models, which we compare to the Green-Kubo result. In all cases, a good agreement is found. The TIP4P/2005 model is in better agreement with the experimental data for both diffusion and viscosity. The SPC/E and Dang-Chang models overestimate the diffusion coefficient and underestimate the viscosity.

Effective diffusion coefficients of DNAPL waste components in saturated low permeability soil materials.

PubMed

Ayral-Cinar, Derya; Demond, Avery H

2017-12-01

Diffusion is regarded as the dominant transport mechanism into and out of low permeable subsurface lenses and layers in the subsurface. But, some reports of mass storage in such zones are higher than what might be attributable to diffusion, based on estimated diffusion coefficients. Despite the importance of diffusion to efforts to estimate the quantity of residual contamination in the subsurface, relatively few studies present measured diffusion coefficients of organic solutes in saturated low permeability soils. This study reports the diffusion coefficients of a trichloroethylene (TCE), and an anionic surfactant, Aerosol OT (AOT), in water-saturated silt and a silt-montmorillonite (25:75) mixture, obtained using steady-state experiments. The relative diffusivity ranged from 0.11 to 0.17 for all three compounds for the silt and the silt-clay mixture that was allowed to expand. In the case in which the swelling was constrained, the relative diffusivity was about 0.07. In addition, the relative diffusivity of 13 C-labeled TCE through a water saturated silt-clay mixture that had contacted a field dense non-aqueous phase liquid (DNAPL) for 18months was measured and equaled 0.001. These experimental results were compared with the estimates generated using common correlations, and it was found that, in all cases, the measured diffusion coefficients were significantly lower than the estimated. Thus, the discrepancy between mass accumulations observed in the field and the mass storage that can attributable to diffusion may be greater than previously believed. Copyright © 2017. Published by Elsevier B.V.

Measurement of gas diffusion coefficient in liquid-saturated porous media using magnetic resonance imaging

NASA Astrophysics Data System (ADS)

Song, Yongchen; Hao, Min; Zhao, Yuechao; Zhang, Liang

2014-12-01

In this study, the dual-chamber pressure decay method and magnetic resonance imaging (MRI) were used to dynamically visualize the gas diffusion process in liquid-saturated porous media, and the relationship of concentration-distance for gas diffusing into liquid-saturated porous media at different times were obtained by MR images quantitative analysis. A non-iterative finite volume method was successfully applied to calculate the local gas diffusion coefficient in liquid-saturated porous media. The results agreed very well with the conventional pressure decay method, thus it demonstrates that the method was feasible of determining the local diffusion coefficient of gas in liquid-saturated porous media at different times during diffusion process.

Spectral Properties of Limit-Periodic Schrödinger Operators (PhD Thesis)

NASA Astrophysics Data System (ADS)

Gideonse, Hendrik David, XIX

The Acoustic Ramp is a wedge-shaped, number-theoretical quadratic-residue-type acoustic diffuser. Since the late 1970's, several methodologies for the testing and analysis of diffusers have been developed including, the ISO Scattering Coefficient and the AES Diffusion Coefficient. These coefficients are the source of some controversy today and this paper makes the attempt to investigate the benefits and weaknesses of these tools by using them to research and test the Acoustic Ramp. Several issues are exposed in using the coefficients, the most important of which being the validity of the comparison of the diffuser's behavior to that of a like sized flat panel. Further issues comprise of an intuitive disconnect between the perceived merits of polar plots and the numerical value of coefficients derived from the plots.

Distributional behavior of diffusion coefficients obtained by single trajectories in annealed transit time model

NASA Astrophysics Data System (ADS)

Akimoto, Takuma; Yamamoto, Eiji

2016-12-01

Local diffusion coefficients in disordered systems such as spin glass systems and living cells are highly heterogeneous and may change over time. Such a time-dependent and spatially heterogeneous environment results in irreproducibility of single-particle-tracking measurements. Irreproducibility of time-averaged observables has been theoretically studied in the context of weak ergodicity breaking in stochastic processes. Here, we provide rigorous descriptions of equilibrium and non-equilibrium diffusion processes for the annealed transit time model, which is a heterogeneous diffusion model in living cells. We give analytical solutions for the mean square displacement (MSD) and the relative standard deviation of the time-averaged MSD for equilibrium and non-equilibrium situations. We find that the time-averaged MSD grows linearly with time and that the time-averaged diffusion coefficients are intrinsically random (irreproducible) even in the long-time measurements in non-equilibrium situations. Furthermore, the distribution of the time-averaged diffusion coefficients converges to a universal distribution in the sense that it does not depend on initial conditions. Our findings pave the way for a theoretical understanding of distributional behavior of the time-averaged diffusion coefficients in disordered systems.

Measurement of diffusion coefficients important in modeling the absorption rate of carbon dioxide into aqueous N-methyldiethanolamine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rowley, R.L.; Adams, M.E.; Marshall, T.L.

1997-03-01

Natural gas processors use amine treating processes to remove the acid gases H{sub 2}S and CO{sub 2} from gas streams. Absorption rates of gaseous CO{sub 2} into aqueous N-methyldiethanolamine (MDEA) solutions were measured in a quiescent, inverted-tube diffusiometer by monitoring the rate of pressure drop. The absorption rate was found to be insensitive to the diffusion coefficient of CO{sub 2} in solution but very sensitive to the diffusion rate of bicarbonate and protonated MDEA ions. Evidence also suggested that chemical reaction equilibrium is rapid relative to diffusion. A numerical model was developed on the basis of these observations. The modelmore » was used to regress diffusion coefficients of bicarbonate and protonated amine, which must be equivalent by electroneutrality arguments, from measured absorption rates. Complete modeling of the absorption process also required data for the diffusion coefficient of MDEA in water. These were measured using a Taylor dispersion apparatus. CO{sub 2} absorption rates and diffusion coefficients of bicarbonate and protonated MDEA were obtained at 298.2 K and 318.2 K in solutions containing 20, 35, and 50 mass % MDEA in water.« less

Reference-material system for estimating health and environmental risks of selected material cycles and energy systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crowther, M.A.; Moskowitz, P.D.

1981-07-01

Sample analyses and detailed documentation are presented for a Reference Material System (RMS) to estimate health and environmental risks of different material cycles and energy systems. Data inputs described include: end-use material demands, efficiency coefficients, environmental emission coefficients, fuel demand coefficients, labor productivity estimates, and occupational health and safety coefficients. Application of this model permits analysts to estimate fuel use (e.g., Btu), occupational risk (e.g., fatalities), and environmental emissions (e.g., sulfur oxide) for specific material trajectories or complete energy systems. Model uncertainty is quantitatively defined by presenting a range of estimates for each data input. Systematic uncertainty not quantified relatesmore » to the boundaries chosen for analysis and reference system specification. Although the RMS can be used to analyze material system impacts for many different energy technologies, it was specifically used to examine the health and environmental risks of producing the following four types of photovoltaic devices: silicon n/p single-crystal cells produced by a Czochralski process; silicon metal/insulator/semiconductor (MIS) cells produced by a ribbon-growing process; cadmium sulfide/copper sulfide backwall cells produced by a spray deposition process; and gallium arsenide cells with 500X concentrator produced by a modified Czochralski process. Emission coefficients for particulates, sulfur dioxide and nitrogen dioxide; solid waste; total suspended solids in water; and, where applicable, air and solid waste residuals for arsenic, cadmium, gallium, and silicon are examined and presented. Where data are available the coefficients for particulates, sulfur oxides, and nitrogen oxides include both process and on-site fuel-burning emissions.« less

Interdiffusion, Intrinsic Diffusion, Atomic Mobility, and Vacancy Wind Effect in γ(bcc) Uranium-Molybdenum Alloy

NASA Astrophysics Data System (ADS)

Huang, Ke; Keiser, Dennis D.; Sohn, Yongho

2013-02-01

U-Mo alloys are being developed as low enrichment uranium fuels under the Reduced Enrichment for Research and Test Reactor (RERTR) Program. In order to understand the fundamental diffusion behavior of this system, solid-to-solid pure U vs Mo diffusion couples were assembled and annealed at 923 K, 973 K, 1073 K, 1173 K, and 1273 K (650 °C, 700 °C, 800 °C, 900 °C, and 1000 °C) for various times. The interdiffusion microstructures and concentration profiles were examined via scanning electron microscopy and electron probe microanalysis, respectively. As the Mo concentration increased from 2 to 26 at. pct, the interdiffusion coefficient decreased, while the activation energy increased. A Kirkendall marker plane was clearly identified in each diffusion couple and utilized to determine intrinsic diffusion coefficients. Uranium intrinsically diffused 5-10 times faster than Mo. Molar excess Gibbs free energy of U-Mo alloy was applied to calculate the thermodynamic factor using ideal, regular, and subregular solution models. Based on the intrinsic diffusion coefficients and thermodynamic factors, Manning's formalism was used to calculate the tracer diffusion coefficients, atomic mobilities, and vacancy wind parameters of U and Mo at the marker composition. The tracer diffusion coefficients and atomic mobilities of U were about five times larger than those of Mo, and the vacancy wind effect increased the intrinsic flux of U by approximately 30 pct.

Experimental investigation of turbulent diffusion of slightly buoyant droplets in locally isotropic turbulence

NASA Astrophysics Data System (ADS)

Gopalan, Balaji; Malkiel, Edwin; Katz, Joseph

2008-09-01

High-speed inline digital holographic cinematography is used for studying turbulent diffusion of slightly buoyant 0.5-1.2 mm diameter diesel droplets and 50 μm diameter neutral density particles. Experiments are performed in a 50×50×70 mm3 sample volume in a controlled, nearly isotropic turbulence facility, which is characterized by two dimensional particle image velocimetry. An automated tracking program has been used for measuring velocity time history of more than 17 000 droplets and 15 000 particles. For most of the present conditions, rms values of horizontal droplet velocity exceed those of the fluid. The rms values of droplet vertical velocity are higher than those of the fluid only for the highest turbulence level. The turbulent diffusion coefficient is calculated by integration of the ensemble-averaged Lagrangian velocity autocovariance. Trends of the asymptotic droplet diffusion coefficient are examined by noting that it can be viewed as a product of a mean square velocity and a diffusion time scale. To compare the effects of turbulence and buoyancy, the turbulence intensity (ui') is scaled by the droplet quiescent rise velocity (Uq). The droplet diffusion coefficients in horizontal and vertical directions are lower than those of the fluid at low normalized turbulence intensity, but exceed it with increasing normalized turbulence intensity. For most of the present conditions the droplet horizontal diffusion coefficient is higher than the vertical diffusion coefficient, consistent with trends of the droplet velocity fluctuations and in contrast to the trends of the diffusion timescales. The droplet diffusion coefficients scaled by the product of turbulence intensity and an integral length scale are a monotonically increasing function of ui'/Uq.

Gene interference regulates aquaporin-4 expression in swollen tissue of rats with cerebral ischemic edema

PubMed Central

Hu, Hui; Lu, Hong; He, Zhanping; Han, Xiangjun; Chen, Jing; Tu, Rong

2012-01-01

To investigate the effects of mRNA interference on aquaporin-4 expression in swollen tissue of rats with ischemic cerebral edema, and diagnose the significance of diffusion-weighted MRI, we injected 5 μL shRNA- aquaporin-4 (control group) or siRNA- aquaporin-4 solution (1:800) (RNA interference group) into the rat right basal ganglia immediately before occlusion of the middle cerebral artery. At 0.25 hours after occlusion of the middle cerebral artery, diffusion-weighted MRI displayed a high signal; within 2 hours, the relative apparent diffusion coefficient decreased markedly, aquaporin-4 expression increased rapidly, and intracellular edema was obviously aggravated; at 4 and 6 hours, the relative apparent diffusion coefficient slowly returned to control levels, aquaporin-4 expression slightly increased, and angioedema was observed. In the RNA interference group, during 0.25–6 hours after injection of siRNA- aquaporin-4 solution, the relative apparent diffusion coefficient slightly fluctuated and aquaporin-4 expression was upregulated; during 0.5–4 hours, the relative apparent diffusion coefficient was significantly higher, while aquaporin-4 expression was significantly lower when compared with the control group, and intracellular edema was markedly reduced; at 0.25 and 6 hours, the relative apparent diffusion coefficient and aquaporin-4 expression were similar when compared with the control group; obvious angioedema remained at 6 hours. Pearson's correlation test results showed that aquaporin-4 expression was negatively correlated with the apparent diffusion coefficient (r = −0.806, P < 0.01). These findings suggest that upregulated aquaporin-4 expression is likely to be the main molecular mechanism of intracellular edema and may be the molecular basis for decreased relative apparent diffusion coefficient. Aquaporin-4 gene interference can effectively inhibit the upregulation of aquaporin-4 expression during the stage of intracellular edema with time-effectiveness. Moreover, diffusion-weighted MRI can accurately detect intracellular edema. PMID:25657707

Perpendicular Diffusion Coefficient of Comic Rays: The Presence of Weak Adiabatic Focusing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, J. F.; Ma, Q. M.; Song, T.

The influence of adiabatic focusing on particle diffusion is an important topic in astrophysics and plasma physics. In the past, several authors have explored the influence of along-field adiabatic focusing on the parallel diffusion of charged energetic particles. In this paper, using the unified nonlinear transport theory developed by Shalchi and the method of He and Schlickeiser, we derive a new nonlinear perpendicular diffusion coefficient for a non-uniform background magnetic field. This formula demonstrates that the particle perpendicular diffusion coefficient is modified by along-field adiabatic focusing. For isotropic pitch-angle scattering and the weak adiabatic focusing limit, the derived perpendicular diffusionmore » coefficient is independent of the sign of adiabatic focusing characteristic length. For the two-component model, we simplify the perpendicular diffusion coefficient up to the second order of the power series of the adiabatic focusing characteristic quantity. We find that the first-order modifying factor is equal to zero and that the sign of the second order is determined by the energy of the particles.« less

Coupled Protein Diffusion and Folding in the Cell

PubMed Central

Guo, Minghao; Gelman, Hannah; Gruebele, Martin

2014-01-01

When a protein unfolds in the cell, its diffusion coefficient is affected by its increased hydrodynamic radius and by interactions of exposed hydrophobic residues with the cytoplasmic matrix, including chaperones. We characterize protein diffusion by photobleaching whole cells at a single point, and imaging the concentration change of fluorescent-labeled protein throughout the cell as a function of time. As a folded reference protein we use green fluorescent protein. The resulting region-dependent anomalous diffusion is well characterized by 2-D or 3-D diffusion equations coupled to a clustering algorithm that accounts for position-dependent diffusion. Then we study diffusion of a destabilized mutant of the enzyme phosphoglycerate kinase (PGK) and of its stable control inside the cell. Unlike the green fluorescent protein control's diffusion coefficient, PGK's diffusion coefficient is a non-monotonic function of temperature, signaling ‘sticking’ of the protein in the cytosol as it begins to unfold. The temperature-dependent increase and subsequent decrease of the PGK diffusion coefficient in the cytosol is greater than a simple size-scaling model suggests. Chaperone binding of the unfolding protein inside the cell is one plausible candidate for even slower diffusion of PGK, and we test the plausibility of this hypothesis experimentally, although we do not rule out other candidates. PMID:25436502

Coupled protein diffusion and folding in the cell.

PubMed

Guo, Minghao; Gelman, Hannah; Gruebele, Martin

2014-01-01

When a protein unfolds in the cell, its diffusion coefficient is affected by its increased hydrodynamic radius and by interactions of exposed hydrophobic residues with the cytoplasmic matrix, including chaperones. We characterize protein diffusion by photobleaching whole cells at a single point, and imaging the concentration change of fluorescent-labeled protein throughout the cell as a function of time. As a folded reference protein we use green fluorescent protein. The resulting region-dependent anomalous diffusion is well characterized by 2-D or 3-D diffusion equations coupled to a clustering algorithm that accounts for position-dependent diffusion. Then we study diffusion of a destabilized mutant of the enzyme phosphoglycerate kinase (PGK) and of its stable control inside the cell. Unlike the green fluorescent protein control's diffusion coefficient, PGK's diffusion coefficient is a non-monotonic function of temperature, signaling 'sticking' of the protein in the cytosol as it begins to unfold. The temperature-dependent increase and subsequent decrease of the PGK diffusion coefficient in the cytosol is greater than a simple size-scaling model suggests. Chaperone binding of the unfolding protein inside the cell is one plausible candidate for even slower diffusion of PGK, and we test the plausibility of this hypothesis experimentally, although we do not rule out other candidates.

Iron-Nickel Sulfide Compositional Ranges in CM Chondrites: No Simple Plan

NASA Technical Reports Server (NTRS)

Zolensky, Michael; Le, Loan

2003-01-01

Iron-nickel sulfides are found in most or all solar system environments, and are probably the only minerals found in all extraterrestrial materials on hand. Despite this ubiquity, they have only just begun the attention they deserve. The most common Fe-Ni sulfides in chondrites are troilite (FeS), pyrrhotite (Fe(1-x)S) and pentlandite (Fe,Ni)9S8. Troilite is believed to have resulted from sulfidation of metal (Fe-Ni) grains in an H2S-containing environment. Pyrrhotite is produced when friable troilite grains, which are exfoliated from the metal nucleus, are submitted to continued sulfidation. Some asteroids are known to have experienced aqueous alteration, forming products including new generations of sulfides (pyrrhotite and pentlandite). Pentlandite in particular is known to form during such alteration. However, experimental work by Lauretta has indicated that pentlandite may also have been formed during the initial sulfidation process, due to the faster diffusion rate of nickel into the forming sulfide, as compared to iron. Finally, there is considerable evidence for a family of phases intermediate between pyrrhotite and pentlandite, following the trend of the high temperature monosulfide solid solution, something not encountered in terrestrial rocks. Each sulfide has its own particular stability conditions, which have been determined for most phases. The long-term objective of our research is to characterize sulfides in chondritic materials in order to better establish the conditions under which they formed, and the subsequent processes they experienced. Ultimately, it will be possible to infer whether the sulfides in the chondrites were formed in the solar nebula or on asteroids, and if formed on the asteroids, deduce how much alteration has occurred there. Here we explore the relationships between the finest grain size portions of carbonaceous chondrites, these being matrix and chondrule rims; fine-grained materials are the most sensitive to their environment. This abstract is one of a series reporting results for chondrites, earlier work reported results for a much more limited set of CMs, as well as for CVs and CIs.

Determination of the diffusion coefficient and phase-transfer rate parameter in LaNi{sub 5} and MmNi{sub 3.6}Co{sub 0.8}Mn{sub 0.4}Al{sub 0.3} using microelectrodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lundqvist, A.; Lindbergh, G.

1998-11-01

A potential-step method for determining the diffusion coefficient and phase-transfer parameter in metal hydrides by using microelectrodes was investigated. It was shown that a large potential step is not enough to ensure a completely diffusion-limited mass transfer if a surface-phase transfer reaction takes place at a finite rate. It was shown, using a kinetic expression for the surface phase-transfer reaction, that the slope of the logarithm of the current vs. time curve will be constant both in the case of the mass-transfer limited by diffusion or by diffusion and a surface-phase transfer. The diffusion coefficient and phase-transfer rate parameter weremore » accurately determined for MmNi{sub 3.6}Co{sub 0.8}Mn{sub 0.4}Al{sub 0.3} using a fit to the whole transient. The diffusion coefficient was found to be (1.3 {+-} 0.3) {times} 10{sup {minus}13} m{sup 2}/s. The fit was good and showed that a pure diffusion model was not enough to explain the observed transient. The diffusion coefficient and phase-transfer rate parameter were also estimated for pure LaNi{sub 5}. A fit of the whole curve showed that neither a pure diffusion model nor a model including phase transfer could explain the whole transient.« less

Determination of diffusion coefficients of carbon dioxide in water between 268 and 473 K in a high-pressure capillary optical cell with in situ Raman spectroscopic measurements

USGS Publications Warehouse

Lu, Wanjun; Guo, Huirong; Chou, I.-Ming; Burruss, R.C.; Li, Lanlan

2013-01-01

Accurate values of diffusion coefficients for carbon dioxide in water and brine at reservoir conditions are essential to our understanding of transport behavior of carbon dioxide in subsurface pore space. However, the experimental data are limited to conditions at low temperatures and pressures. In this study, diffusive transfer of carbon dioxide in water at pressures up to 45 MPa and temperatures from 268 to 473 K was observed within an optical capillary cell via time-dependent Raman spectroscopy. Diffusion coefficients were estimated by the least-squares method for the measured variations in carbon dioxide concentration in the cell at various sample positions and time. At the constant pressure of 20 MPa, the measured diffusion coefficients of carbon dioxide in water increase with increasing temperature from 268 to 473 K. The relationship between diffusion coefficient of carbon dioxide in water [D(CO2) in m2/s] and temperature (T in K) was derived with Speedy–Angell power-law approach as: D(CO2)=D0[T/Ts-1]m where D0 = 13.942 × 10−9 m2/s, Ts = 227.0 K, and m = 1.7094. At constant temperature, diffusion coefficients of carbon dioxide in water decrease with pressure increase. However, this pressure effect is rather small (within a few percent).

Entropy-scaling laws for diffusion coefficients in liquid metals under high pressures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cao, Qi-Long, E-mail: qlcao@mail.ustc.edu.cn; Shao, Ju-Xiang; Wang, Fan-Hou, E-mail: eatonch@gmail.com

2015-04-07

Molecular dynamic simulations on the liquid copper and tungsten are used to investigate the empirical entropy-scaling laws D{sup *}=A exp(BS{sub ex}), proposed independently by Rosenfeld and Dzugutov for diffusion coefficient, under high pressure conditions. We show that the scaling laws hold rather well for them under high pressure conditions. Furthermore, both the original diffusion coefficients and the reduced diffusion coefficients exhibit an Arrhenius relationship D{sub M}=D{sub M}{sup 0} exp(−E{sub M}/K{sub B}T), (M=un,R,D) and the activation energy E{sub M} increases with increasing pressure, the diffusion pre-exponential factors (D{sub R}{sup 0} and D{sub D}{sup 0}) are nearly independent of the pressure and element. Themore » pair correlation entropy, S{sub 2}, depends linearly on the reciprocal temperature S{sub 2}=−E{sub S}/T, and the activation energy, E{sub S}, increases with increasing pressure. In particular, the ratios of the activation energies (E{sub un}, E{sub R}, and E{sub D}) obtained from diffusion coefficients to the activation energy, E{sub S}, obtained from the entropy keep constants in the whole pressure range. Therefore, the entropy-scaling laws for the diffusion coefficients and the Arrhenius law are linked via the temperature dependence of entropy.« less

Solute diffusion in liquid metals

NASA Technical Reports Server (NTRS)

Bhat, B. N.

1973-01-01

A gas model of diffusion in liquid metals is presented. In this model, ions of liquid metals are assumed to behave like the molecules in a dense gas. Diffusion coefficient of solute is discussed with reference to its mass, ionic size, and pair potential. The model is applied to the case of solute diffusion in liquid silver. An attempt was made to predict diffusion coefficients of solutes with reasonable accuracy.

Ferrimagnetic Iron Sulfide Formation and Methane Venting Across the Paleocene-Eocene Thermal Maximum in Shallow Marine Sediments, Ancient West Siberian Sea

NASA Astrophysics Data System (ADS)

Rudmin, Maxim; Roberts, Andrew P.; Horng, Chorng-Shern; Mazurov, Aleksey; Savinova, Olesya; Ruban, Aleksey; Kashapov, Roman; Veklich, Maxim

2018-01-01

Authigenesis of ferrimagnetic iron sulfide minerals (greigite and monoclinic pyrrhotite) occurred across the Paleocene-Eocene Thermal Maximum (PETM) within the Bakchar oolitic ironstone in southeastern Western Siberia. Co-occurrence of these minerals is associated with diagenetic environments that support anaerobic oxidation of methane, which has been validated by methane fluid inclusion analysis in the studied sediments. In modern settings, such ferrimagnetic iron sulfide formation is linked to upward methane diffusion in the presence of minor dissolved sulfide ions. The PETM was the most extreme Cenozoic global warming event and massive methane mobilization has been proposed as a major contributor to the globally observed warming and carbon isotope excursion associated with the PETM. The studied sediments provide rare direct evidence for methane mobilization during the PETM. Magnetic iron sulfide formation associated with methanogenesis in the studied sediments can be explained by enhanced local carbon burial across the PETM. While there is no strong evidence to link local methane venting with more widespread methane mobilization and global warming, the magnetic, petrographic, and geochemical approach used here is applicable to identifying authigenic minerals that provide telltale signatures of methane mobility that can be used to assess methane formation and mobilization through the PETM and other hyperthermal climatic events.

Matrix diffusion coefficients in volcanic rocks at the Nevada test site: influence of matrix porosity, matrix permeability, and fracture coating minerals.

PubMed

Reimus, Paul W; Callahan, Timothy J; Ware, S Doug; Haga, Marc J; Counce, Dale A

2007-08-15

Diffusion cell experiments were conducted to measure nonsorbing solute matrix diffusion coefficients in forty-seven different volcanic rock matrix samples from eight different locations (with multiple depth intervals represented at several locations) at the Nevada Test Site. The solutes used in the experiments included bromide, iodide, pentafluorobenzoate (PFBA), and tritiated water ((3)HHO). The porosity and saturated permeability of most of the diffusion cell samples were measured to evaluate the correlation of these two variables with tracer matrix diffusion coefficients divided by the free-water diffusion coefficient (D(m)/D*). To investigate the influence of fracture coating minerals on matrix diffusion, ten of the diffusion cells represented paired samples from the same depth interval in which one sample contained a fracture surface with mineral coatings and the other sample consisted of only pure matrix. The log of (D(m)/D*) was found to be positively correlated with both the matrix porosity and the log of matrix permeability. A multiple linear regression analysis indicated that both parameters contributed significantly to the regression at the 95% confidence level. However, the log of the matrix diffusion coefficient was more highly-correlated with the log of matrix permeability than with matrix porosity, which suggests that matrix diffusion coefficients, like matrix permeabilities, have a greater dependence on the interconnectedness of matrix porosity than on the matrix porosity itself. The regression equation for the volcanic rocks was found to provide satisfactory predictions of log(D(m)/D*) for other types of rocks with similar ranges of matrix porosity and permeability as the volcanic rocks, but it did a poorer job predicting log(D(m)/D*) for rocks with lower porosities and/or permeabilities. The presence of mineral coatings on fracture walls did not appear to have a significant effect on matrix diffusion in the ten paired diffusion cell experiments.

Matrix diffusion coefficients in volcanic rocks at the Nevada test site: Influence of matrix porosity, matrix permeability, and fracture coating minerals

NASA Astrophysics Data System (ADS)

Reimus, Paul W.; Callahan, Timothy J.; Ware, S. Doug; Haga, Marc J.; Counce, Dale A.

2007-08-01

Diffusion cell experiments were conducted to measure nonsorbing solute matrix diffusion coefficients in forty-seven different volcanic rock matrix samples from eight different locations (with multiple depth intervals represented at several locations) at the Nevada Test Site. The solutes used in the experiments included bromide, iodide, pentafluorobenzoate (PFBA), and tritiated water ( 3HHO). The porosity and saturated permeability of most of the diffusion cell samples were measured to evaluate the correlation of these two variables with tracer matrix diffusion coefficients divided by the free-water diffusion coefficient ( Dm/ D*). To investigate the influence of fracture coating minerals on matrix diffusion, ten of the diffusion cells represented paired samples from the same depth interval in which one sample contained a fracture surface with mineral coatings and the other sample consisted of only pure matrix. The log of ( Dm/ D*) was found to be positively correlated with both the matrix porosity and the log of matrix permeability. A multiple linear regression analysis indicated that both parameters contributed significantly to the regression at the 95% confidence level. However, the log of the matrix diffusion coefficient was more highly-correlated with the log of matrix permeability than with matrix porosity, which suggests that matrix diffusion coefficients, like matrix permeabilities, have a greater dependence on the interconnectedness of matrix porosity than on the matrix porosity itself. The regression equation for the volcanic rocks was found to provide satisfactory predictions of log( Dm/ D*) for other types of rocks with similar ranges of matrix porosity and permeability as the volcanic rocks, but it did a poorer job predicting log( Dm/ D*) for rocks with lower porosities and/or permeabilities. The presence of mineral coatings on fracture walls did not appear to have a significant effect on matrix diffusion in the ten paired diffusion cell experiments.

Photon diffusion coefficient in scattering and absorbing media.

PubMed

Pierrat, Romain; Greffet, Jean-Jacques; Carminati, Rémi

2006-05-01

We present a unified derivation of the photon diffusion coefficient for both steady-state and time-dependent transport in disordered absorbing media. The derivation is based on a modal analysis of the time-dependent radiative transfer equation. This approach confirms that the dynamic diffusion coefficient is given by the random-walk result D = cl(*)/3, where l(*) is the transport mean free path and c is the energy velocity, independent of the level of absorption. It also shows that the diffusion coefficient for steady-state transport, often used in biomedical optics, depends on absorption, in agreement with recent theoretical and experimental works. These two results resolve a recurrent controversy in light propagation and imaging in scattering media.

Molecular dynamics simulation of solute diffusion in Lennard-Jones fluids

NASA Astrophysics Data System (ADS)

Yamaguchi, T.; Kimura, Y.; Hirota, N.

We performed a molecular dynamics (MD) simulation for a system of 5 solute molecules in 495 solvent molecules interacting through the Lennard-Jones (LJ) 12-6 potential, in order to study solvent density effects on the diffusion coefficients in supercritical fluids. The effects of the size of the solute and the strength of the solute-solvent attractive interaction on the diffusion coefficient of the solute were examined. The diffusion coefficients of the solute molecules were calculated at T = 1.5 (in the LJ reduced unit), slightly above the critical temperature, from rho = 0.1 to rho = 0.95, where rho is the number density in the LJ reduced unit. The memory function in the generalized Langevin equation was calculated, in order to know the molecular origin of the friction on a solute. The memory function is separated into fast and slow components. The former arises from the solute-solvent repulsive interaction, and is interpreted as collisional Enskog-like friction. The interaction strength dependence of the collisional friction is larger in the low- and medium-density regions, which is consistent with the 'clustering' picture, i.e., the local density enhancement due to the solute-solvent attractive interaction. However, the slow component of the memory function suppresses the effect of the local density on the diffusion coefficients, and as a result the effect of the attractive interaction is smaller on the diffusion coefficients than on the local density. Nonetheless, the solvent density dependence of the effect of the attraction on the diffusion coefficient varies with the local density, and it is concluded that the local density is the principal factor that determines the interaction strength dependence of the diffusion coefficient in the low- and medium-density regions (p < 0.6).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sarman, Sten, E-mail: sarman@ownit.nu; Wang, Yong-Lei; Laaksonen, Aatto

The self-diffusion coefficients of nematic phases of various model systems consisting of regular convex calamitic and discotic ellipsoids and non-convex bodies such as bent-core molecules and soft ellipsoid strings have been obtained as functions of the shear rate in a shear flow. Then the self-diffusion coefficient is a second rank tensor with three different diagonal components and two off-diagonal components. These coefficients were found to be determined by a combination of two mechanisms, which previously have been found to govern the self-diffusion of shearing isotropic liquids, namely, (i) shear alignment enhancing the diffusion in the direction parallel to the streamlinesmore » and hindering the diffusion in the perpendicular directions and (ii) the distortion of the shell structure in the liquid whereby a molecule more readily can escape from a surrounding shell of nearest neighbors, so that the mobility increases in every direction. Thus, the diffusion parallel to the streamlines always increases with the shear rate since these mechanisms cooperate in this direction. In the perpendicular directions, these mechanisms counteract each other so that the behaviour becomes less regular. In the case of the nematic phases of the calamitic and discotic ellipsoids and of the bent core molecules, mechanism (ii) prevails so that the diffusion coefficients increase. However, the diffusion coefficients of the soft ellipsoid strings decrease in the direction of the velocity gradient because the broadsides of these molecules are oriented perpendicularly to this direction due the shear alignment (i). The cross coupling coefficient relating a gradient of tracer particles in the direction of the velocity gradient and their flow in the direction of the streamlines is negative and rather large, whereas the other coupling coefficient relating a gradient in the direction of the streamlines and a flow in the direction of the velocity gradient is very small.« less

[Lateral diffusion of saturated phosphatidylcholines in cholesterol-containing bilayers].

PubMed

Filippov, A V; Rudakova, M A; Oradd, G; Lindblom, J

2007-01-01

Lateral diffusion in oriented bilayers of saturated cholesterol-containing phosphatidylcholines, dipalmitoylphosphatidylcholine and dimyrilstoylphosphatidylcholine upon their limiting hydration has been studied by NMR with impulse gradient of magnetic field. For both systems, similar dependences of the coefficient of lateral diffusion on temperature and cholesterol concentration were observed, which agree with the phase diagram showing the presence of regions of ordered and unordered liquid-crystalline phases and a two-phase region. Under similar conditions, the coefficient of lateral diffusion for dipalmytoylphosphatidylcholine has lower values, which is in qualitative agreement with its greater molecular mass. A comparison of data for dipalmytoylphosphatidylcholine with the results obtained earlier for dipalmytoylsphyngomyelin/cholesterol under the same conditions shows, despite a similarity in phase diagrams, greater (two- to threefold) differences in the values of the coefficient of lateral diffusion and a different mode of dependence of the coefficient on cholesterol concentration. A comparison of data for dimyrilstoylphosphatidylcholine with the results obtained previously shows that the values of the coefficient of lateral diffusion and the mode of its dependence on cholesterol concentration coincide in the region of higher concentrations (more than 15 mole %) and differ in the region of lower concentrations (below 15 mole %). The discrepancies may be explained by different contents of water in the systems during the measurements. At a limiting hydration (more than 35%) of water, the coefficient of lateral diffusion decreases with increasing cholesterol concentration. If the content of water is about 25% (as a result of equilibrium hydration from vapors), the coefficient of lateral diffusion of phosphatidylcholine is probably independent of cholesterol concentration. This results from a denser packing of molecules in the bilayer at a lower water concentration, an effect that competes with the ordering effect of cholesterol.

Formation of iron sulphide in solar nebula

NASA Technical Reports Server (NTRS)

Kerridge, J. F.

1976-01-01

Noting that the iron sulfide in the Orgueil carbonaceous meteorite is an Fe-deficient monosulfide (pyrrhotite), it is suggested that such mineral chemistry is inconsistent with equilibrium condensation of the solar nebula and that the course of condensation may have been modified by kinetic effects. The effect of Ni on the reaction between Fe and S to produce FeS is examined, and possible reasons are considered for the fact that the cited meteorite differs in both crystal structure and Ni content from the predictions of equilibrium condensation. It is proposed that sulfide formation in the solar nebula may have been inhibited by sluggish diffusion, so that sulfur began to react with previously condensed troilite to form pyrrhotite. On this basis, observations of the Orgueil sulfides are shown to suggest that the course of solar-system condensation was modified by kinetic effects below about 700 K and that equilibrium may not have been achieved.

Understanding the initial irreversibility of metal sulfides for sodium-ion batteries via operando techniques

DOE PAGES

Wang, Liguang; Wang, Jiajun; Guo, Fangmin; ...

2018-11-13

Transition metal sulfides are promising high capacity anodes for sodium-ion batteries in terms of the conversion reaction with multiple alkali metal ions. Nonetheless, some inherent challenges such as sluggish sodium ion diffusion kinetics, large volume change, and poor cycle stability limit their implementation. Addressing these issues necessitates a comprehensive understanding the complex sodium ion storage mechanism particularly at the initial cycle. Here, taking nickel subsulfide as a model material, we reveal the complicated conversion reaction mechanism upon the first cycle by combining in operando 2D transmission X-ray microscopy with X-ray absorption spectroscopy, ex-situ 3D nano-tomography, high-energy X-ray diffraction and electrochemicalmore » impedance spectroscopy. This study demonstrates that the microstructure evolution, inherent slow sodium ions diffusion kinetics, and slow ion mobility at the two-phase interface contribute to the high irreversible capacity upon the first cycle. Finally, such understandings are critical for developing the conversion reaction materials with the desired electrochemical activity and stability.« less

Understanding the initial irreversibility of metal sulfides for sodium-ion batteries via operando techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Liguang; Wang, Jiajun; Guo, Fangmin

Transition metal sulfides are promising high capacity anodes for sodium-ion batteries in terms of the conversion reaction with multiple alkali metal ions. Nonetheless, some inherent challenges such as sluggish sodium ion diffusion kinetics, large volume change, and poor cycle stability limit their implementation. Addressing these issues necessitates a comprehensive understanding the complex sodium ion storage mechanism particularly at the initial cycle. Here, taking nickel subsulfide as a model material, we reveal the complicated conversion reaction mechanism upon the first cycle by combining in operando 2D transmission X-ray microscopy with X-ray absorption spectroscopy, ex-situ 3D nano-tomography, high-energy X-ray diffraction and electrochemicalmore » impedance spectroscopy. This study demonstrates that the microstructure evolution, inherent slow sodium ions diffusion kinetics, and slow ion mobility at the two-phase interface contribute to the high irreversible capacity upon the first cycle. Finally, such understandings are critical for developing the conversion reaction materials with the desired electrochemical activity and stability.« less

A novel multiple headspace extraction gas chromatographic method for measuring the diffusion coefficient of methanol in water and in olive oil.

PubMed

Zhang, Chun-Yun; Chai, Xin-Sheng

2015-03-13

A novel method for the determination of the diffusion coefficient (D) of methanol in water and olive oil has been developed. Based on multiple headspace extraction gas chromatography (MHE-GC), the methanol released from the liquid sample of interest in a closed sample vial was determined in a stepwise fashion. A theoretical model was derived to establish the relationship between the diffusion coefficient and the GC signals from MHE-GC measurements. The results showed that the present method has an excellent precision (RSD<1%) in the linear fitting procedure and good accuracy for the diffusion coefficients of methanol in both water and olive oil, when compared with data reported in the literature. The present method is simple and practical and can be a valuable tool for the determination of the diffusion coefficient of volatile analyte(s) into food simulants from food and beverage packaging material, both in research studies and in actual applications. Copyright © 2015 Elsevier B.V. All rights reserved.

Prediction of stream volatilization coefficients

USGS Publications Warehouse

Rathbun, Ronald E.

1990-01-01

Equations are developed for predicting the liquid-film and gas-film reference-substance parameters for quantifying volatilization of organic solutes from streams. Molecular weight and molecular-diffusion coefficients of the solute are used as correlating parameters. Equations for predicting molecular-diffusion coefficients of organic solutes in water and air are developed, with molecular weight and molal volume as parameters. Mean absolute errors of prediction for diffusion coefficients in water are 9.97% for the molecular-weight equation, 6.45% for the molal-volume equation. The mean absolute error for the diffusion coefficient in air is 5.79% for the molal-volume equation. Molecular weight is not a satisfactory correlating parameter for diffusion in air because two equations are necessary to describe the values in the data set. The best predictive equation for the liquid-film reference-substance parameter has a mean absolute error of 5.74%, with molal volume as the correlating parameter. The best equation for the gas-film parameter has a mean absolute error of 7.80%, with molecular weight as the correlating parameter.

Dissipative particle dynamics study of velocity autocorrelation function and self-diffusion coefficient in terms of interaction potential strength

NASA Astrophysics Data System (ADS)

Zohravi, Elnaz; Shirani, Ebrahim; Pishevar, Ahmadreza; Karimpour, Hossein

2018-07-01

This research focuses on numerically investigating the self-diffusion coefficient and velocity autocorrelation function (VACF) of a dissipative particle dynamics (DPD) fluid as a function of the conservative interaction strength. Analytic solutions to VACF and self-diffusion coefficients in DPD were obtained by many researchers in some restricted cases including ideal gases, without the account of conservative force. As departure from the ideal gas conditions are accentuated with increasing the relative proportion of conservative force, it is anticipated that the VACF should gradually deviate from its normally expected exponentially decay. This trend is confirmed through numerical simulations and an expression in terms of the conservative force parameter, density and temperature is proposed for the self-diffusion coefficient. As it concerned the VACF, the equivalent Langevin equation describing Brownian motion of particles with a harmonic potential is adapted to the problem and reveals an exponentially decaying oscillatory pattern influenced by the conservative force parameter, dissipative parameter and temperature. Although the proposed model for obtaining the self-diffusion coefficient with consideration of the conservative force could not be verified due to computational complexities, nonetheless the Arrhenius dependency of the self-diffusion coefficient to temperature and pressure permits to certify our model over a definite range of DPD parameters.

Interdiffusion and stress development in single-crystalline Pd/Ag bilayers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Noah, Martin A., E-mail: m.noah@is.mpg.de; Flötotto, David; Wang, Zumin

Interdiffusion and stress evolution in single-crystalline Pd/single-crystalline Ag thin films were investigated by Auger electron spectroscopy sputter-depth profiling and in-situ X-ray diffraction, respectively. The concentration-dependent chemical diffusion coefficient, as well as the impurity diffusion coefficient of Ag in Pd could be determined in the low temperature range of 356 °C–455 °C. As a consequence of the similarity of the strong concentration-dependences of the intrinsic diffusion coefficients, the chemical diffusion coefficient varies only over three orders of magnitude over the whole composition range, despite the large difference of six orders of magnitude of the self-diffusion coefficients of Ag in Ag and Pd inmore » Pd. It is shown that the Darken-Manning treatment should be adopted for interpretation of the experimental data; the Nernst-Planck treatment yielded physically unreasonable results. Apart from the development of compressive thermal stress, the development of stress in both sublayers separately could be ascribed to compositional stress (tensile in the Ag sublayer and compressive in the Pd sublayer) and dominant relaxation processes, especially in the Ag sublayer. The effect of these internal stresses on the values determined for the diffusion coefficients is shown to be negligible.« less

Controls on Highly Siderophile Element Concentrations in Martian Basalt: Sulfide Saturation and Under-Saturation

NASA Technical Reports Server (NTRS)

Righter, Kevin

2009-01-01

Highly siderophile elements (HSE; Re, Au and the platinum group elements) in shergottites exhibit a wide range from very high, similar to the terrestrial mantle, to very low, similar to sulfide saturated mid ocean ridge basalt (e.g., [1]). This large range has been difficult to explain without good constraints on sulfide saturation or under-saturation [2]. A new model for prediction of sulfide saturation places new constraints on this problem [3]. Shergottite data: For primitive shergottites, pressure and temperature estimates are between 1.2-1.5 GPa, and 1350-1470 C [4]. The range of oxygen fugacities is from FMQ-2 to IW, where the amount of Fe2O3 is low and thus does not have a significant effect on the S saturation values. Finally, the bulk compositions of shergottites have been reported in many recent studies (e.g., [5]). All of this information will be used to test whether shergottites are sulfide saturated [3]. Modeling values and results: The database for HSE partition coefficients has been growing with many new data for silicates and oxides [6-8] to complement a large sulfide database [9- 11]. Combining these data with simple batch melting models allows HSE contents of mantle melts to be estimated for sulfide-bearing vs. sulfide-free mantle. Combining such models with fractional crystallization modeling (e.g., [12]) allows HSE contents of more evolved liquids to be modeled. Most primitive shergottites have high HSE contents (and low S contents) that can be explained by sulfide under-saturated melting of the mantle. An exception is Dhofar 019 which has high S contents and very low HSE contents suggesting sulfide saturation. Most evolved basaltic shergottites have lower S contents than saturation, and intermediate HSE contents that can be explained by olivine, pyroxene, and chromite fractionation. An exception is EET A79001 lithology B, which has very low HSE contents and S contents higher than sulfide saturation values . evidence for sulfide saturation during late fractional crystallization. These results show that shergottite HSE contents are controlled by silicates, oxides, and sulfides. In addition, the mantle producing the most primitive shergottites did not contain near chondritic relative ratios of the HSEs like the terrestrial mantle, and did not experience a late chondritic veneer.

Diffusion heterogeneity tensor MRI (?-Dti): mathematics and initial applications in spinal cord regeneration after trauma - biomed 2009.

PubMed

Ellington, Benjamin M; Schmit, Brian D; Gourab, Krishnaj; Sieber-Blum, Maya; Hu, Yao F; Schmainda, Kathleen M

2009-01-01

Diffusion weighted magnetic resonance imaging (DWI) is a powerful tool for evaluation of microstructural anomalies in numerous central nervous system pathologies. Diffusion tensor imaging (DTI) allows for the magnitude and direction of water self diffusion to be estimated by sampling the apparent diffusion coefficient (ADC) in various directions. Clinical DWI and DTI performed at a single level of diffusion weighting, however, does not allow for multiple diffusion compartments to be elicited. Furthermore, assumptions made regarding the precise number of diffusion compartments intrinsic to the tissue of interest have resulted in a lack of consensus between investigations. To overcome these challenges, a stretched-exponential model of diffusion was applied to examine the diffusion coefficient and "heterogeneity index" within highly compartmentalized brain tumors. The purpose of the current study is to expand on the stretched-exponential model of diffusion to include directionality of both diffusion heterogeneity and apparent diffusion coefficient. This study develops the mathematics of this new technique along with an initial application in quantifying spinal cord regeneration following acute injection of epidermal neural crest stem cell (EPI-NCSC) grafts.

Adsorptive removal of catalyst poisons from coal gas for methanol synthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhatt, B.L.; Golden, T.C.; Hsiung, T.H.

1991-12-01

As an integral part of the liquid-phase methanol (LPMEOH) process development program, the present study evaluated adsorptive schemes to remove traces of catalyst poisons such as iron carbonyl, carbonyl sulfide, and hydrogen sulfide from coal gas on a pilot scale. Tests were conducted with coal gas from the Cool Water gasification plant at Daggett, California. Iron carbonyl, carbonyl sulfide, and hydrogen sulfide were effectively removed from the coal gas. The adsorption capacities of Linde H-Y zeolite and Calgon BPL carbon for Fe(CO){sub 5} compared well with previous bench-scale results at similar CO{sub 2} partial pressure. Adsorption of COS by Calgonmore » FCA carbon appeared to be chemical and nonregenerable by thermal treatment in nitrogen. A Cu/Zn catalyst removed H{sub 2}S very effectively. With the adsorption system on-line, a methanol catalyst showed stable activity during 120 h operation, demonstrating the feasibility of adsorptive removal of trace catalyst poisons from the synthesis gas. Mass transfer coefficients were estimated for Fe(CO){sub 5} and COS removal which can be directly used for design and scale up.« less

Effect of temperature on anoxic sulfide oxidation and denitrification in the bulk wastewater phase of sewer networks.

PubMed

Mathioudakis, V L; Aivasidis, A

2009-01-01

Artificial dosage of nitrate in sewer networks is considered as one of the most effective methods for odor and corrosion control. However, there is limited knowledge on the effect of temperature on the transformations that takes place during anoxic conditions. Thus, two groups of batch experiments were conducted to gain insight in the involved processes in bulk phase of a septic municipal wastewater. It can be concluded that sewer denitrification, in bulk phase, can be simplified in three stages. According to the experimental results, nitrate or nitrite is utilized for autotrophic denitrification with sulfide, while heterotrophic utilization is initiated after the completion of anoxic sulfide oxidation. Moreover, temperature is proved to have a significant impact on sewer denitrification kinetic profile, as it determines the extent of temporal nitrite accumulation. The temperature coefficient of each anoxic process, including sulfide oxidation, nitrate utilization and denitrification/nitrite utilization is experimentally calculated and temperature dependent equations are developed, providing the rate of all anoxic processes in bulk phase of sewer wastewater, in any given temperature.

Determination of diffusion coefficients and diffusion characteristics for chlorferon and diethylthiophosphate in Ca-alginate gel beads.

PubMed

Ha, Jiyeon; Engler, Cady R; Lee, Seung Jae

2008-07-01

Diffusion characteristics of chlorferon and diethylthiophosphate (DETP) in Ca-alginate gel beads were studied to assist in designing and operating bioreactor systems. Diffusion coefficients for chlorferon and DETP in Ca-alginate gel beads determined at conditions suitable for biodegradation studies were 2.70 x 10(-11) m(2)/s and 4.28 x 10(-11) m(2)/s, respectively. Diffusivities of chlorferon and DETP were influenced by several factors, including viscosity of the bulk solution, agitation speed, and the concentrations of diffusing substrate and immobilized cells. Diffusion coefficients increased with increasing agitation speed, probably due to poor mixing at low speed and some attrition of beads at high speeds. Diffusion coefficients also increased with decreasing substrate concentration. Increased cell concentration in the gel beads caused lower diffusivity. Theoretical models to predict diffusivities as a function of cell weight fraction overestimated the effective diffusivities for both chlorferon and DETP, but linear relations between effective diffusivity and cell weight fraction were derived from experimental data. Calcium-alginate gel beads with radii of 1.65-1.70 mm used in this study were not subject to diffusional limitations: external mass transfer resistances were negligible based on Biot number calculations and effectiveness factors indicated that internal mass transfer resistance was negligible. Therefore, the degradation rates of chlorferon and DETP inside Ca-alginate gel beads were reaction-limited. (c) 2007 Wiley Periodicals, Inc.

Diffusion coefficients of water in biobased hydrogel polymer matrices by nuclear magnetic resonance imaging

USDA-ARS?s Scientific Manuscript database

The diffusion coefficient of water in biobased hydrogels were measured utilizing a simple NMR method. This method tracks the migration of deuterium oxide through imaging data that is fit to a diffusion equation. The results show that a 5 wt% soybean oil based hydrogel gives aqueous diffusion of 1.37...

Portable vapor diffusion coefficient meter

DOEpatents

Ho, Clifford K [Albuquerque, NM

2007-06-12

An apparatus for measuring the effective vapor diffusion coefficient of a test vapor diffusing through a sample of porous media contained within a test chamber. A chemical sensor measures the time-varying concentration of vapor that has diffused a known distance through the porous media. A data processor contained within the apparatus compares the measured sensor data with analytical predictions of the response curve based on the transient diffusion equation using Fick's Law, iterating on the choice of an effective vapor diffusion coefficient until the difference between the predicted and measured curves is minimized. Optionally, a purge fluid can forced through the porous media, permitting the apparatus to also measure a gas-phase permeability. The apparatus can be made lightweight, self-powered, and portable for use in the field.

Communication: Coordinate-dependent diffusivity from single molecule trajectories

NASA Astrophysics Data System (ADS)

Berezhkovskii, Alexander M.; Makarov, Dmitrii E.

2017-11-01

Single-molecule observations of biomolecular folding are commonly interpreted using the model of one-dimensional diffusion along a reaction coordinate, with a coordinate-independent diffusion coefficient. Recent analysis, however, suggests that more general models are required to account for single-molecule measurements performed with high temporal resolution. Here, we consider one such generalization: a model where the diffusion coefficient can be an arbitrary function of the reaction coordinate. Assuming Brownian dynamics along this coordinate, we derive an exact expression for the coordinate-dependent diffusivity in terms of the splitting probability within an arbitrarily chosen interval and the mean transition path time between the interval boundaries. This formula can be used to estimate the effective diffusion coefficient along a reaction coordinate directly from single-molecule trajectories.

Diffusion of organic pollutants within a biofilm in porous media

NASA Astrophysics Data System (ADS)

Fan, Chihhao; Kao, Chen-Fei; Liu, You-Hsi

2017-04-01

The occurrence of aquatic pollution is an inevitable environmental impact resulting from human civilization and societal advancement. Either from the natural or anthropogenic sources, the aqueous contaminants enter the natural environment and aggravate its quality. To assure the aquatic environment quality, the attached-growth biological degradation is often applied to removing organic contaminants by introducing contaminated water into a porous media which is covered by microorganism. Additionally, many natural aquatic systems also form such similar mechanism to increase their self-purification capability. To better understand this transport phenomenon and degradation mechanism in the biofilm for future application, the mathematic characterization of organic contaminant diffusion within the biofilm requires further exploration. The present study aimed to formulate a mathematic representation to quantify the diffusion of the organic contaminant in the biofilm. The BOD was selected as the target contaminant. A series of experiments were conducted to quantify the BOD diffusion in the biofilm under the conditions of influent BOD variation from 50 to 300 mg/L, COD:N:P ratios of 100:5:1 and 100:15:3, with or without auxiliary aeration. For diffusion coefficient calculation, the boundary condition of zero diffusion at the interface between microbial phase and contact media was assumed. With the principle of conservation of mass, the removed contaminants equal those that diffuse into the biofilm, and eq 1 results, and the diffusion coefficient (i.e., eq 2) can be solved through calculus with equations from table of integral. ∂2Sf- Df ∂z2 = Rf (1) --(QSin--QSout)2Y--- Df = 2μmaxxf(Sb + Ks ln-Ks-) Sb+Ks (2) Using the obtained experimental data, the diffusion coefficient was calculated to be 2.02*10-6 m2/d with influent COD of 50 mg/L at COD:N:P ratio of 100:5:1 with aeration, and this coefficient increased to 6.02*10-6 m2/d as the influent concentration increased to 300 mg/L. Meanwhile, the diffusion coefficient decreased to 2.61*10-7 m2/d as the retention time increased to 3 hours. Generally, the variation in diffusion coefficients between different COD:N:P ratios exhibits similar pattern with a slight decrease for the ratio of 100:15:3. The difference in diffusion coefficients between 1 and 2 hours was apparently greater than that between 2 and 3 hours, implying the diffusion was a critical factor for contaminant removal for the treatment condition with retention time of 1 hour or less, because higher retention time leads to better microbial degradation due to sufficient contact time for biological reactions. For 1 hour retention time, the increase in diffusion coefficient becomes limited as the influent COD concentration was equal to or above 150 mg/L. These obtained diffusion coefficients were applied to estimating the treatment efficiency for real domestic sewage. The result was found that the estimated effluent BOD concentrations were quite comparable to that obtained through experimental measurements.

NMR investigation of water diffusion in different biofilm structures.

PubMed

Herrling, Maria P; Weisbrodt, Jessica; Kirkland, Catherine M; Williamson, Nathan H; Lackner, Susanne; Codd, Sarah L; Seymour, Joseph D; Guthausen, Gisela; Horn, Harald

2017-12-01

Mass transfer in biofilms is determined by diffusion. Different mostly invasive approaches have been used to measure diffusion coefficients in biofilms, however, data on heterogeneous biomass under realistic conditions is still missing. To non-invasively elucidate fluid-structure interactions in complex multispecies biofilms pulsed field gradient-nuclear magnetic resonance (PFG-NMR) was applied to measure the water diffusion in five different types of biomass aggregates: one type of sludge flocs, two types of biofilm, and two types of granules. Data analysis is an important issue when measuring heterogeneous systems and is shown to significantly influence the interpretation and understanding of water diffusion. With respect to numerical reproducibility and physico-chemical interpretation, different data processing methods were explored: (bi)-exponential data analysis and the Γ distribution model. Furthermore, the diffusion coefficient distribution in relation to relaxation was studied by D-T 2 maps obtained by 2D inverse Laplace transform (2D ILT). The results show that the effective diffusion coefficients for all biofilm samples ranged from 0.36 to 0.96 relative to that of water. NMR diffusion was linked to biofilm structure (e.g., biomass density, organic and inorganic matter) as observed by magnetic resonance imaging and to traditional biofilm parameters: diffusion was most restricted in granules with compact structures, and fast diffusion was found in heterotrophic biofilms with fluffy structures. The effective diffusion coefficients in the biomass were found to be broadly distributed because of internal biomass heterogeneities, such as gas bubbles, precipitates, and locally changing biofilm densities. Thus, estimations based on biofilm bulk properties in multispecies systems can be overestimated and mean diffusion coefficients might not be sufficiently informative to describe mass transport in biofilms and the near bulk. © 2017 Wiley Periodicals, Inc.

Diffusion of neutral and ionic species in charged membranes: boric acid, arsenite, and water.

PubMed

Goli, Esmaiel; Hiemstra, Tjisse; Van Riemsdijk, Willem H; Rahnemaie, Rasoul; Malakouti, Mohammad Jafar

2010-10-15

Dynamic ion speciation using DMT (Donnan membrane technique) requires insight into the physicochemical characteristics of diffusion in charged membranes (tortuosity, local diffusion coefficients) as well as ion accumulation. The latter can be precluded by studying the diffusion of neutral species, such as boric acid, B(OH)₃⁰(aq), arsenite, As(OH)₃⁰(aq), or water. In this study, the diffusion rate of B(OH)₃⁰ has been evaluated as a function of the concentration, pH, and ionic strength. The rate is linearly dependent on the concentration of solely the neutral species, without a significant contribution of negatively charged species such as B(OH)₄⁻, present at high pH. A striking finding is the very strong effect (factor of ~10) of the type of cation (K(+), Na(+), Ca(2+), Mg(2+), Al(3+), and H(+)) on the diffusion coefficient of B(OH)₃⁰ and also As(OH)₃⁰. The decrease of the diffusion coefficient can be rationalized as an enhancement of the mean viscosity of the confined solution in the membrane. The diffusion coefficients can be described by a semiempirical relationship, linking the mean viscosity of the confined solute of the membrane to the viscosity of the free solution. In proton-saturated membranes, as used in fuel cells, viscosity is relatively more enhanced; i.e., a stronger water network is formed. Extraordinarily, our B(OH)₃-calibrated model (in HNO₃) correctly predicts the reported diffusion coefficient of water (D(H₂O)), measured with ¹H NMR and quasi-elastic neutron scattering in H(+)-Nafion membranes. Upon drying these membranes, the local hydronium, H(H₂O)(n)(+), concentration and corresponding viscosity increase, resulting in a severe reduction of the diffusion coefficient (D(H₂O) ≈ 5-50 times), in agreement with the model. The present study has a second goal, i.e., development of the methodology for measuring the free concentration of neutral species in solution. Our data suggest that the free concentration can be measured with DMT in natural systems if one accounts for the variation in the cation composition of the membrane and corresponding viscosity/diffusion coefficient.

Kinetic modeling of ultrasound-assisted extraction of phenolic compounds from grape marc: influence of acoustic energy density and temperature.

PubMed

Tao, Yang; Zhang, Zhihang; Sun, Da-Wen

2014-07-01

The effects of acoustic energy density (6.8-47.4 W/L) and temperature (20-50 °C) on the extraction yields of total phenolics and tartaric esters during ultrasound-assisted extraction from grape marc were investigated in this study. The ultrasound treatment was performed in a 25-kHz ultrasound bath system and the 50% aqueous ethanol was used as the solvent. The initial extraction rate and final extraction yield increased with the increase of acoustic energy density and temperature. The two site kinetic model was used to simulate the kinetics of extraction process and the diffusion model based on the Fick's second law was employed to determine the effective diffusion coefficient of phenolics in grape marc. Both models gave satisfactory quality of data fit. The diffusion process was divided into one fast stage and one slow stage and the diffusion coefficients in both stages were calculated. Within the current experimental range, the diffusion coefficients of total phenolics and tartaric esters for both diffusion stages increased with acoustic energy density. Meanwhile, the rise of temperature also resulted in the increase of diffusion coefficients of phenolics except the diffusion coefficient of total phenolics in the fast stage, the value of which being the highest at 40 °C. Moreover, an empirical equation was suggested to correlate the effective diffusion coefficient of phenolics in grape marc with acoustic energy density and temperature. In addition, the performance comparison of ultrasound-assisted extraction and convention methods demonstrates that ultrasound is an effective and promising technology to extract bioactive substances from grape marc. Copyright © 2014 Elsevier B.V. All rights reserved.

Breast Cancer: Diffusion Kurtosis MR Imaging-Diagnostic Accuracy and Correlation with Clinical-Pathologic Factors.

PubMed

Sun, Kun; Chen, Xiaosong; Chai, Weimin; Fei, Xiaochun; Fu, Caixia; Yan, Xu; Zhan, Ying; Chen, Kemin; Shen, Kunwei; Yan, Fuhua

2015-10-01

To assess diagnostic accuracy with diffusion kurtosis imaging (DKI) in patients with breast lesions and to evaluate the potential association between DKI-derived parameters and breast cancer clinical-pathologic factors. Institutional review board approval and written informed consent were obtained. Data from 97 patients (mean age ± standard deviation, 45.7 years ± 13.1; range, 19-70 years) with 98 lesions (57 malignant and 41 benign) who were treated between January 2014 and April 2014 were retrospectively analyzed. DKI (with b values of 0-2800 sec/mm(2)) and conventional diffusion-weighted imaging data were acquired. Kurtosis and diffusion coefficients from DKI and apparent diffusion coefficients from diffusion-weighted imaging were measured by two radiologists. Student t test, Wilcoxon signed-rank test, Jonckheere-Terpstra test, receiver operating characteristic curves, and Spearman correlation were used for statistical analysis. Kurtosis coefficients were significantly higher in the malignant lesions than in the benign lesions (1.05 ± 0.22 vs 0.65 ± 0.11, respectively; P < .0001). Diffusivity and apparent diffusion coefficients in the malignant lesions were significantly lower than those in the benign lesions (1.13 ± 0.27 vs 1.97 ± 0.33 and 1.02 ± 0.18 vs 1.48 ± 0.33, respectively; P < .0001). Significantly higher specificity for differentiation of malignant from benign lesions was shown with the use of kurtosis and diffusivity coefficients than with the use of apparent diffusion coefficients (83% [34 of 41] and 83% [34 of 41] vs 76% [31 of 41], respectively; P < .0001) with equal sensitivity (95% [54 of 57]). In patients with invasive breast cancer, kurtosis was positively correlated with tumor histologic grade (r = 0.75) and expression of the Ki-67 protein (r = 0.55). Diffusivity was negatively correlated with tumor histologic grades (r = -0.44) and Ki-67 expression (r = -0.46). DKI showed higher specificity than did conventional diffusion-weighted imaging for assessment of benign and malignant breast lesions. Patients with grade 3 breast cancer or tumors with high expression of Ki-67 were associated with higher kurtosis and lower diffusivity coefficients; however, this association must be confirmed in prospective studies. (©) RSNA, 2015 Online supplemental material is available for this article.

Binding affinity and decontamination of dermal decontamination gel to model chemical warfare agent simulants.

PubMed

Cao, Yachao; Elmahdy, Akram; Zhu, Hanjiang; Hui, Xiaoying; Maibach, Howard

2018-05-01

Six chemical warfare agent simulants (trimethyl phosphate, dimethyl adipate, 2-chloroethyl methyl sulfide, diethyl adipate, chloroethyl phenyl sulfide and diethyl sebacate) were studied in in vitro human skin to explore relationship between dermal penetration/absorption and the mechanisms of simulant partitioning between stratum corneum (SC) and water as well as between dermal decontamination gel (DDGel) and water. Both binding affinity to and decontamination of simulants using DDGel were studied. Partition coefficients of six simulants between SC and water (Log P SC/w ) and between DDGel and water (Log P DDGel/w ) were determined. Results showed that DDGel has a similar or higher binding affinity to each simulant compared to SC. The relationship between Log P octanol/water and Log P SC/w as well as between Log P octanol/water and Log P DDGel/w demonstrated that partition coefficient of simulants correlated to their lipophilicity or hydrophilicity. Decontamination efficiency results with DDGel for these simulants were consistent with binding affinity results. Amounts of percentage dose of chemicals in DDGel of trimethyl phosphate, dimethyl adipate, 2-chloroethyl methyl sulfide, diethyl adipate, chloroethyl phenyl sulfide and diethyl sebacate were determined to be 61.15, 85.67, 75.91, 53.53, 89.89 and 76.58, with corresponding amounts absorbed in skin of 0.96, 0.65, 1.68, 0.72, 0.57 and 1.38, respectively. In vitro skin decontamination experiments coupled with a dermal absorption study demonstrated that DDGel can efficiently remove chemicals from skin surface, back-extract from the SC, and significantly reduced chemical penetration into skin or systemic absorption for all six simulants tested. Therefore, DDGel offers a great potential as a NextGen skin Decon platform technology for both military and civilian use. Copyright © 2018 John Wiley & Sons, Ltd.

Research and Development of Methods for Estimating Physicochemical Properties of Organic Compounds of Environmental Concern

DTIC Science & Technology

1979-02-01

coefficient (at equilibrium) when hysteresis is apparent. 6. Coefficient n in Freundlich equation for 1/n soil or sediment adsorption isotherms ýX - KC . 7...Biodegradation Chemical structures cal clasaes (e.g., Diffusion Correlations phenols). General Diffusion coefficients Equations terms for organic...OF THE FATE AND TRANSPORT OF ORGANIC CHEMICALS Adsorption coefficients: K, n* from Freundlich equation + Desorption coefficients: K’*, n’* from

Self-diffusion in the non-Newtonian regime of shearing liquid crystal model systems based on the Gay-Berne potential

NASA Astrophysics Data System (ADS)

Sarman, Sten; Wang, Yong-Lei; Laaksonen, Aatto

2016-02-01

The self-diffusion coefficients of nematic phases of various model systems consisting of regular convex calamitic and discotic ellipsoids and non-convex bodies such as bent-core molecules and soft ellipsoid strings have been obtained as functions of the shear rate in a shear flow. Then the self-diffusion coefficient is a second rank tensor with three different diagonal components and two off-diagonal components. These coefficients were found to be determined by a combination of two mechanisms, which previously have been found to govern the self-diffusion of shearing isotropic liquids, namely, (i) shear alignment enhancing the diffusion in the direction parallel to the streamlines and hindering the diffusion in the perpendicular directions and (ii) the distortion of the shell structure in the liquid whereby a molecule more readily can escape from a surrounding shell of nearest neighbors, so that the mobility increases in every direction. Thus, the diffusion parallel to the streamlines always increases with the shear rate since these mechanisms cooperate in this direction. In the perpendicular directions, these mechanisms counteract each other so that the behaviour becomes less regular. In the case of the nematic phases of the calamitic and discotic ellipsoids and of the bent core molecules, mechanism (ii) prevails so that the diffusion coefficients increase. However, the diffusion coefficients of the soft ellipsoid strings decrease in the direction of the velocity gradient because the broadsides of these molecules are oriented perpendicularly to this direction due the shear alignment (i). The cross coupling coefficient relating a gradient of tracer particles in the direction of the velocity gradient and their flow in the direction of the streamlines is negative and rather large, whereas the other coupling coefficient relating a gradient in the direction of the streamlines and a flow in the direction of the velocity gradient is very small.

Catalytic hydrotreating process

DOEpatents

Karr, Jr., Clarence; McCaskill, Kenneth B.

1978-01-01

Carbonaceous liquids boiling above about 300.degree. C such as tars, petroleum residuals, shale oils and coal-derived liquids are catalytically hydrotreated by introducing the carbonaceous liquid into a reaction zone at a temperature in the range of 300.degree. to 450.degree. C and a pressure in the range of 300 to 4000 psig for effecting contact between the carbonaceous liquid and a catalytic transition metal sulfide in the reaction zone as a layer on a hydrogen permeable transition metal substrate and then introducing hydrogen into the reaction zone by diffusing the hydrogen through the substrate to effect the hydrogenation of the carbonaceous liquid in the presence of the catalytic sulfide layer.

Experimental Determination of Impurity and Interdiffusion Coefficients in Seven Ti and Zr Binary Systems Using Diffusion Multiples

NASA Astrophysics Data System (ADS)

Chen, Zhangqi; Liu, Zi-Kui; Zhao, Ji-Cheng

2018-05-01

Diffusion coefficients of seven binary systems (Ti-Mo, Ti-Nb, Ti-Ta, Ti-Zr, Zr-Mo, Zr-Nb, and Zr-Ta) at 1200 °C, 1000 °C, and 800 °C were experimentally determined using three Ti-Mo-Nb-Ta-Zr diffusion multiples. Electron probe microanalysis (EPMA) was performed to collect concentration profiles at the binary diffusion regions. Forward simulation analysis (FSA) was then applied to extract both impurity and interdiffusion coefficients in Ti-rich and Zr-rich part of the bcc phase. Excellent agreements between our results and most of the literature data validate the high-throughput approach combining FSA with diffusion multiples to obtain a large amount of systematic diffusion data, which will help establish the diffusion (mobility) databases for the design and development of biomedical and structural Ti alloys.

Diffusion modulation of DNA by toehold exchange

NASA Astrophysics Data System (ADS)

Rodjanapanyakul, Thanapop; Takabatake, Fumi; Abe, Keita; Kawamata, Ibuki; Nomura, Shinichiro M.; Murata, Satoshi

2018-05-01

We propose a method to control the diffusion speed of DNA molecules with a target sequence in a polymer solution. The interaction between solute DNA and diffusion-suppressing DNA that has been anchored to a polymer matrix is modulated by the concentration of the third DNA molecule called the competitor by a mechanism called toehold exchange. Experimental results show that the sequence-specific modulation of the diffusion coefficient is successfully achieved. The diffusion coefficient can be modulated up to sixfold by changing the concentration of the competitor. The specificity of the modulation is also verified under the coexistence of a set of DNA with noninteracting base sequences. With this mechanism, we are able to control the diffusion coefficient of individual DNA species by the concentration of another DNA species. This methodology introduces a programmability to a DNA-based reaction-diffusion system.

Experimental Determination of Impurity and Interdiffusion Coefficients in Seven Ti and Zr Binary Systems Using Diffusion Multiples

NASA Astrophysics Data System (ADS)

Chen, Zhangqi; Liu, Zi-Kui; Zhao, Ji-Cheng

2018-07-01

Diffusion coefficients of seven binary systems (Ti-Mo, Ti-Nb, Ti-Ta, Ti-Zr, Zr-Mo, Zr-Nb, and Zr-Ta) at 1200 °C, 1000 °C, and 800 °C were experimentally determined using three Ti-Mo-Nb-Ta-Zr diffusion multiples. Electron probe microanalysis (EPMA) was performed to collect concentration profiles at the binary diffusion regions. Forward simulation analysis (FSA) was then applied to extract both impurity and interdiffusion coefficients in Ti-rich and Zr-rich part of the bcc phase. Excellent agreements between our results and most of the literature data validate the high-throughput approach combining FSA with diffusion multiples to obtain a large amount of systematic diffusion data, which will help establish the diffusion (mobility) databases for the design and development of biomedical and structural Ti alloys.

Stefan-Maxwell Relations and Heat Flux with Anisotropic Transport Coefficients for Ionized Gases in a Magnetic Field with Application to the Problem of Ambipolar Diffusion

NASA Astrophysics Data System (ADS)

Kolesnichenko, A. V.; Marov, M. Ya.

2018-01-01

The defining relations for the thermodynamic diffusion and heat fluxes in a multicomponent, partially ionized gas mixture in an external electromagnetic field have been obtained by the methods of the kinetic theory. Generalized Stefan-Maxwell relations and algebraic equations for anisotropic transport coefficients (the multicomponent diffusion, thermal diffusion, electric and thermoelectric conductivity coefficients as well as the thermal diffusion ratios) associated with diffusion-thermal processes have been derived. The defining second-order equations are derived by the Chapman-Enskog procedure using Sonine polynomial expansions. The modified Stefan-Maxwell relations are used for the description of ambipolar diffusion in the Earth's ionospheric plasma (in the F region) composed of electrons, ions of many species, and neutral particles in a strong electromagnetic field.

Determination of diffusion coefficients of hydrogen and deuterium in Zr-2.5%Nb pressure tube material using hot vacuum extraction-quadrupole mass spectrometry

NASA Astrophysics Data System (ADS)

Shrivastava, Komal Chandra; Kulkarni, A. S.; Ramanjaneyulu, P. S.; Sunil, Saurav; Saxena, M. K.; Singh, R. N.; Tomar, B. S.; Ramakumar, K. L.

2015-06-01

The diffusion coefficients of hydrogen and deuterium in Zr-2.5%Nb alloy were measured in the temperature range 523 to 673 K, employing hot vacuum extraction-quadrupole mass spectrometry (HVE-QMS). One end of the Zr-2.5%Nb alloy specimens was charged electrolytically with the desired hydrogen isotope. After annealing at different temperatures for a predetermined time, the specimens were cut into thin slices, which were analyzed for their H2/D2 content using the HVE-QMS technique. The depth profile data were fitted into the equation representing the solution of Fick's second law of diffusion. The activation energy of hydrogen/deuterium diffusion was obtained from the Arrhenius relation between the diffusion coefficient and temperature. The temperature dependent diffusion coefficient can be represented as DH = 1.41 × 10-7 exp(-36,000/RT) and DD = 6.16 × 10-8 exp(-35,262/RT) for hydrogen and deuterium, respectively.

Dynamics of the DNA repair proteins WRN and BLM in the nucleoplasm and nucleoli.

PubMed

Bendtsen, Kristian Moss; Jensen, Martin Borch; May, Alfred; Rasmussen, Lene Juel; Trusina, Ala; Bohr, Vilhelm A; Jensen, Mogens H

2014-11-01

We have investigated the mobility of two EGFP-tagged DNA repair proteins, WRN and BLM. In particular, we focused on the dynamics in two locations, the nucleoli and the nucleoplasm. We found that both WRN and BLM use a "DNA-scanning" mechanism, with rapid binding-unbinding to DNA resulting in effective diffusion. In the nucleoplasm WRN and BLM have effective diffusion coefficients of 1.62 and 1.34 μm(2)/s, respectively. Likewise, the dynamics in the nucleoli are also best described by effective diffusion, but with diffusion coefficients a factor of ten lower than in the nucleoplasm. From this large reduction in diffusion coefficient we were able to classify WRN and BLM as DNA damage scanners. In addition to WRN and BLM we also classified other DNA damage proteins and found they all fall into one of two categories. Either they are scanners, similar to WRN and BLM, with very low diffusion coefficients, suggesting a scanning mechanism, or they are almost freely diffusing, suggesting that they interact with DNA only after initiation of a DNA damage response.

Connecting the molecular scale to the continuum scale for diffusion processes in smectite-rich porous media.

PubMed

Bourg, Ian C; Sposito, Garrison

2010-03-15

In this paper, we address the manner in which the continuum-scale diffusive properties of smectite-rich porous media arise from their molecular- and pore-scale features. Our starting point is a successful model of the continuum-scale apparent diffusion coefficient for water tracers and cations, which decomposes it as a sum of pore-scale terms describing diffusion in macropore and interlayer "compartments." We then apply molecular dynamics (MD) simulations to determine molecular-scale diffusion coefficients D(interlayer) of water tracers and representative cations (Na(+), Cs(+), Sr(2+)) in Na-smectite interlayers. We find that a remarkably simple expression relates D(interlayer) to the pore-scale parameter δ(nanopore) ≤ 1, a constrictivity factor that accounts for the lower mobility in interlayers as compared to macropores: δ(nanopore) = D(interlayer)/D(0), where D(0) is the diffusion coefficient in bulk liquid water. Using this scaling expression, we can accurately predict the apparent diffusion coefficients of tracers H(2)0, Na(+), Sr(2+), and Cs(+) in compacted Na-smectite-rich materials.

New method and installation for rapid determination of radon diffusion coefficient in various materials.

PubMed

Tsapalov, Andrey; Gulabyants, Loren; Livshits, Mihail; Kovler, Konstantin

2014-04-01

The mathematical apparatus and the experimental installation for the rapid determination of radon diffusion coefficient in various materials are developed. The single test lasts not longer than 18 h and allows testing numerous materials, such as gaseous and liquid media, as well as soil, concrete and radon-proof membranes, in which diffusion coefficient of radon may vary in an extremely wide range, from 1·10(-12) to 5·10(-5) m(2)/s. The uncertainty of radon diffusion coefficient estimation depends on the permeability of the sample and varies from about 5% (for the most permeable materials) to 40% (for less permeable materials, such as radon-proof membranes). Copyright © 2014. Published by Elsevier Ltd.

Prediction and validation of diffusion coefficients in a model drug delivery system using microsecond atomistic molecular dynamics simulation and vapour sorption analysis.

PubMed

Forrey, Christopher; Saylor, David M; Silverstein, Joshua S; Douglas, Jack F; Davis, Eric M; Elabd, Yossef A

2014-10-14

Diffusion of small to medium sized molecules in polymeric medical device materials underlies a broad range of public health concerns related to unintended leaching from or uptake into implantable medical devices. However, obtaining accurate diffusion coefficients for such systems at physiological temperature represents a formidable challenge, both experimentally and computationally. While molecular dynamics simulation has been used to accurately predict the diffusion coefficients, D, of a handful of gases in various polymers, this success has not been extended to molecules larger than gases, e.g., condensable vapours, liquids, and drugs. We present atomistic molecular dynamics simulation predictions of diffusion in a model drug eluting system that represent a dramatic improvement in accuracy compared to previous simulation predictions for comparable systems. We find that, for simulations of insufficient duration, sub-diffusive dynamics can lead to dramatic over-prediction of D. We present useful metrics for monitoring the extent of sub-diffusive dynamics and explore how these metrics correlate to error in D. We also identify a relationship between diffusion and fast dynamics in our system, which may serve as a means to more rapidly predict diffusion in slowly diffusing systems. Our work provides important precedent and essential insights for utilizing atomistic molecular dynamics simulations to predict diffusion coefficients of small to medium sized molecules in condensed soft matter systems.

Measurement of the Diffusion Coefficient of Water in RP-3 and RP-5 Jet Fuels Using Digital Holography Interferometry

NASA Astrophysics Data System (ADS)

Li, Chaoyue; Feng, Shiyu; Shao, Lei; Pan, Jun; Liu, Weihua

2018-04-01

The diffusion coefficient of water in jet fuel was measured employing double-exposure digital holographic interferometry to clarify the diffusion process and make the aircraft fuel system safe. The experimental method and apparatus are introduced in detail, and the digital image processing program is coded in MATLAB according to the theory of the Fourier transform. At temperatures ranging from 278.15 K to 333.15 K in intervals of 5 K, the diffusion coefficient of water in RP-3 and RP-5 jet fuels ranges from 2.6967 × 10 -10 m2·s-1 to 8.7332 × 10 -10 m2·s-1 and from 2.3517 × 10 -10 m2·s-1 to 8.0099 × 10-10 m2·s-1, respectively. The relationship between the measured diffusion coefficient and temperature can be well fitted by the Arrhenius law. The diffusion coefficient of water in RP-3 jet fuel is higher than that of water in RP-5 jet fuel at the same temperature. Furthermore, the viscosities of the two jet fuels were measured and found to be expressible in the form of the Arrhenius equation. The relationship among the diffusion coefficient, viscosity and temperature is analyzed according to the classic prediction model, namely the Stokes-Einstein correlation, and this correlation is further revised via experimental data to obtain a more accurate predication result.

Effect of the computational domain size and shape on the self-diffusion coefficient in a Lennard-Jones liquid.

PubMed

Kikugawa, Gota; Ando, Shotaro; Suzuki, Jo; Naruke, Yoichi; Nakano, Takeo; Ohara, Taku

2015-01-14

In the present study, molecular dynamics (MD) simulations on the monatomic Lennard-Jones liquid in a periodic boundary system were performed in order to elucidate the effect of the computational domain size and shape on the self-diffusion coefficient measured by the system. So far, the system size dependence in cubic computational domains has been intensively investigated and these studies showed that the diffusion coefficient depends linearly on the inverse of the system size, which is theoretically predicted based on the hydrodynamic interaction. We examined the system size effect not only in the cubic cell systems but also in rectangular cell systems which were created by changing one side length of the cubic cell with the system density kept constant. As a result, the diffusion coefficient in the direction perpendicular to the long side of the rectangular cell significantly increases more or less linearly with the side length. On the other hand, the diffusion coefficient in the direction along the long side is almost constant or slightly decreases. Consequently, anisotropy of the diffusion coefficient emerges in a rectangular cell with periodic boundary conditions even in a bulk liquid simulation. This unexpected result is of critical importance because rectangular fluid systems confined in nanospace, which are present in realistic nanoscale technologies, have been widely studied in recent MD simulations. In order to elucidate the underlying mechanism for this serious system shape effect on the diffusion property, the correlation structures of particle velocities were examined.

Molecular-dynamics simulation of mutual diffusion in nonideal liquid mixtures

NASA Astrophysics Data System (ADS)

Rowley, R. L.; Stoker, J. M.; Giles, N. F.

1991-05-01

The mutual-diffusion coefficients, D 12, of n-hexane, n-heptane, and n-octane in chloroform were modeled using equilibrium molecular-dynamics (MD) simulations of simple Lennard-Jones (LJ) fluids. Pure-component LJ parameters were obtained by comparison of simulations to experimental self-diffusion coefficients. While values of “effective” LJ parameters are not expected to simulate accurately diverse thermophysical properties over a wide range of conditions, it was recently shown that effective parameters obtained from pure self-diffusion coefficients can accurately model mutual diffusion in ideal, liquid mixtures. In this work, similar simulations are used to model diffusion in nonideal mixtures. The same combining rules used in the previous study for the cross-interaction parameters were found to be adequate to represent the composition dependence of D 12. The effect of alkane chain length on D 12 is also correctly predicted by the simulations. A commonly used assumption in empirical correlations of D 12, that its kinetic portion is a simple, compositional average of the intradiffusion coefficients, is inconsistent with the simulation results. In fact, the value of the kinetic portion of D 12 was often outside the range of values bracketed by the two intradiffusion coefficients for the nonideal system modeled here.

Communication: A method to compute the transport coefficient of pure fluids diffusing through planar interfaces from equilibrium molecular dynamics simulations.

PubMed

Vermorel, Romain; Oulebsir, Fouad; Galliero, Guillaume

2017-09-14

The computation of diffusion coefficients in molecular systems ranks among the most useful applications of equilibrium molecular dynamics simulations. However, when dealing with the problem of fluid diffusion through vanishingly thin interfaces, classical techniques are not applicable. This is because the volume of space in which molecules diffuse is ill-defined. In such conditions, non-equilibrium techniques allow for the computation of transport coefficients per unit interface width, but their weak point lies in their inability to isolate the contribution of the different physical mechanisms prone to impact the flux of permeating molecules. In this work, we propose a simple and accurate method to compute the diffusional transport coefficient of a pure fluid through a planar interface from equilibrium molecular dynamics simulations, in the form of a diffusion coefficient per unit interface width. In order to demonstrate its validity and accuracy, we apply our method to the case study of a dilute gas diffusing through a smoothly repulsive single-layer porous solid. We believe this complementary technique can benefit to the interpretation of the results obtained on single-layer membranes by means of complex non-equilibrium methods.

Fluorescence correlation spectroscopy experiments to quantify free diffusion coefficients in reaction-diffusion systems: The case of Ca2 + and its dyes

NASA Astrophysics Data System (ADS)

Sigaut, Lorena; Villarruel, Cecilia; Ponce, María Laura; Ponce Dawson, Silvina

2017-06-01

Many cell signaling pathways involve the diffusion of messengers that bind and unbind to and from intracellular components. Quantifying their net transport rate under different conditions then requires having separate estimates of their free diffusion coefficient and binding or unbinding rates. In this paper, we show how performing sets of fluorescence correlation spectroscopy (FCS) experiments under different conditions, it is possible to quantify free diffusion coefficients and on and off rates of reaction-diffusion systems. We develop the theory and present a practical implementation for the case of the universal second messenger, calcium (Ca2 +) and single-wavelength dyes that increase their fluorescence upon Ca2 + binding. We validate the approach with experiments performed in aqueous solutions containing Ca2 + and Fluo4 dextran (both in its high and low affinity versions). Performing FCS experiments with tetramethylrhodamine-dextran in Xenopus laevis oocytes, we infer the corresponding free diffusion coefficients in the cytosol of these cells. Our approach can be extended to other physiologically relevant reaction-diffusion systems to quantify biophysical parameters that determine the dynamics of various variables of interest.

Transport diffusion in deformed carbon nanotubes

NASA Astrophysics Data System (ADS)

Feng, Jiamei; Chen, Peirong; Zheng, Dongqin; Zhong, Weirong

2018-03-01

Using non-equilibrium molecular dynamics and Monte Carlo methods, we have studied the transport diffusion of gas in deformed carbon nanotubes. Perfect carbon nanotube and various deformed carbon nanotubes are modeled as transport channels. It is found that the transport diffusion coefficient of gas does not change in twisted carbon nanotubes, but changes in XY-distortion, Z-distortion and local defect carbon nanotubes comparing with that of the perfect carbon nanotube. Furthermore, the change of transport diffusion coefficient is found to be associated with the deformation factor. The relationship between transport diffusion coefficient and temperature is also discussed in this paper. Our results may contribute to understanding the mechanism of molecular transport in nano-channel.

The surface diffusion coefficient for an arbitrarily curved fluid-fluid interface. (I). General expression

NASA Astrophysics Data System (ADS)

M. C. Sagis, Leonard

2001-03-01

In this paper, we develop a theory for the calculation of the surface diffusion coefficient for an arbitrarily curved fluid-fluid interface. The theory is valid for systems in hydrodynamic equilibrium, with zero mass-averaged velocities in the bulk and interfacial regions. We restrict our attention to systems with isotropic bulk phases, and an interfacial region that is isotropic in the plane parallel to the dividing surface. The dividing surface is assumed to be a simple interface, without memory effects or yield stresses. We derive an expression for the surface diffusion coefficient in terms of two parameters of the interfacial region: the coefficient for plane-parallel diffusion D (AB)aa(ξ) , and the driving force d(B)I||(ξ) . This driving force is the parallel component of the driving force for diffusion in the interfacial region. We derive an expression for this driving force using the entropy balance.

Correlation Between the Field Line and Particle Diffusion Coefficients in the Stochastic Fields of a Tokamak

NASA Astrophysics Data System (ADS)

Calvin, Mark; Punjabi, Alkesh

1996-11-01

We use the method of quasi-magnetic surfaces to calculate the correlation between the field line and particle diffusion coefficients. The magnetic topology of a tokamak is perturbed by a spectrum of neighboring resonant resistive modes. The Hamiltonian equations of motion for the field line are integrated numerically. Poincare plots of the quasi-magnetic surfaces are generated initially and after the field line has traversed a considerable distance. From the areas of the quasi-magnetic surfaces and the field line distance, we estimate the field line diffusion coefficient. We start plasma particles on the initial quasi-surface, and calculate the particle diffusion coefficient from our Monte Carlo method (Punjabi A., Boozer A., Lam M., Kim H. and Burke K., J. Plasma Phys.), 44, 405 (1990). We then estimate the correlation between the particle and field diffusion as the strength of the resistive modes is varied.

Computation of thermodynamic and transport properties to predict thermophoretic effects in an argon-krypton mixture

NASA Astrophysics Data System (ADS)

Miller, Nicholas A. T.; Daivis, Peter J.; Snook, Ian K.; Todd, B. D.

2013-10-01

Thermophoresis is the movement of molecules caused by a temperature gradient. Here we report the results of a study of thermophoresis using non-equilibrium molecular dynamics simulations of a confined argon-krypton fluid subject to two different temperatures at thermostated walls. The resulting temperature profile between the walls is used along with the Soret coefficient to predict the concentration profile that develops across the channel. We obtain the Soret coefficient by calculating the mutual diffusion and thermal diffusion coefficients. We report an appropriate method for calculating the transport coefficients for binary systems, using the Green-Kubo integrals and radial distribution functions obtained from equilibrium molecular dynamics simulations of the bulk fluid. Our method has the unique advantage of separating the mutual diffusion and thermal diffusion coefficients, and calculating the sign and magnitude of their individual contributions to thermophoresis in binary mixtures.

Development of a technique for the in vivo assessment of flatulence in dogs.

PubMed

Collins, S B; Perez-Camargo, G; Gettinby, G; Butterwick, R F; Batt, R M; Giffard, C J

2001-07-01

To develop a noninvasive method for the in vivo assessment of flatulence in dogs. 8 adult dogs. Rectal gases were collected via a perforated tube held close to each dog's anus and attached to a monitoring pump fitted with a sensor that recorded hydrogen sulfide concentrations every 20 seconds. Patterns of flatulence were monitored for 14 hours after feeding on 4 days, and within- and between-dog variation was assessed over 4 hours on 4 consecutive days. Rate of hydrogen sulfide production (flatulence index) and frequency and number of emissions were evaluated as potential indicators of flatus characteristics. An odor judge assigned an odor rating to each flatulence episode, and the relationship between that rating and hydrogen sulfide concentration was determined. Flatulence patterns varied within and between dogs. Variation was most pronounced for flatulence index; mean coefficients of variance within dogs over time and between dogs on each day were 75 and 103%, respectively. Flatus with hydrogen sulfide concentrations > 1 parts per million could be detected by the odor judge, and severity of malodor was highly correlated with hydrogen sulfide concentration. Odor ratings were accurately predicted by use of the equation 1.51 X hydrogen sulfide concentration(0.28). The technique described in this report appears to provide sensitive, reliable, and relevant data and will enable further studies of the factors that influence flatulence in dogs. Use of this technique also has the potential to aid in investigations of colonic physiology and pathology.

Partitioning of palladium, iridium, platinum, and gold between sulfide liquid and basalt melt at 1,200 degree C

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stone, W.E.; Crocket, J.H.; Fleet, M.E.

1990-08-01

Iron-nickel monosulfide and basalt glass containing trace amounts of PGE equilibrated at 1,200{degree}C, and f{sub o{sub 2}} = 10{sup {minus}9.2} (close to the wustite-magnetite buffer) and f{sub s{sub 2}} = 10{sup {minus}0.9}, have been analyzed for noble metals by radiochemical and instrumental neutron activation analysis. The average contents of PGE in coexisting Fe-Ni sulfide and basalt glass, respectively, are Pd, 50 ppm and 0.5 ppb; Ir, 50 ppm and 0.5 ppb; Pt, 100 ppm and 10 ppb; and Au, 0.7 ppm and 0.8 ppb. The sulfide liquid-silicate melt partition coefficients (D values) for the noble metals are (9 {plus minus}more » 7) {times} 10{sup 4} for Pd, (1 {plus minus} 0.7) {times} 10{sup 5} for Ir, (9 {plus minus} 6) {times} 10{sup 3} Pt, and (1 {plus minus} 0.9) {times} 10{sup 3} for Au. The noble metals are strongly partitioned into sulfide liquid, but the affinity of Pd and Ir for sulfide liquid is about 50 times greater than that of Pt and about 500 times greater than that of Au. The D values indicate that equilibrium partitioning between immiscible sulfide liquid and basalt magma would result in fractionation of the noble metals, which differs significantly from that generally observed in nature.« less

Molecular Diffusion Coefficients: Experimental Determination and Demonstration.

ERIC Educational Resources Information Center

Fate, Gwendolyn; Lynn, David G.

1990-01-01

Presented are laboratory methods which allow the demonstration and determination of the diffusion coefficients of compounds ranging in size from water to small proteins. Included are the procedures involving the use of a spectrometer, UV cell, triterated agar, and oxygen diffusion. Results including quantification are described. (CW)

Recurrence of Seagrass Mortality in Florida Bay: The Role of Climate Change and Implications for Carbon Sequestration

NASA Astrophysics Data System (ADS)

Yarbro, L.; Carlson, P. R., Jr.

2016-02-01

Catastrophic mortality of seagrass in Florida Bay (USA) from 1987 to 1991 resulted in the complete loss of thousands of hectares of dense Thalassia testudinum beds. At that time, acutely toxic levels of dissolved sulfide in sediments were determined to be the proximal cause of seagrass mortality, but the mechanisms responsible for sulfide accumulation in sediments were not demonstrated. With the recurrence of seagrass mortality in Florida Bay in summer 2015, we show that several processes create the conditions that lead to sulfide toxicity and catastrophic mortality of Thalassia. Regional drought and elevated water temperature lead to hypersalinity, particularly in the northern Bay. In addition, evaporation of seawater on mudbanks and microtidal flow patterns create stratified brine layers in basins adjacent to mudbanks. Because of very high seagrass shoot densities and limited tidal exchange, brine layers limit oxygen diffusion and prevent oxidation of sulfide in sediments and bottom water, exposing roots, rhizomes and lateral meristems of Thalassia to acutely toxic levels of sulfide, causing extensive mortality. Dead belowground tissues provide labile carbon sources to sulfate-reducing bacteria enhancing sulfide production and creating a positive feedback loop of increasing sulfide toxicity leading to further seagrass death. The carbon sequestration capacity of these dense seagrass communities is diminished three ways: 1) export of dead seagrass shoots and leaves as floating wrack, 2) in situ decomposition of roots, rhizomes, and some leaf material, and 3) reduced areal productivity of surviving seagrasses. Climate analyses show that, in the short term ( 50 years), higher water temperatures and evaporation rates might result in recurring seagrass mortality events. However, in the long term, sea level rise will increase tidal exchange and flushing in Florida Bay reducing the likelihood of seagrass mortality.

Including scattering within the room acoustics diffusion model: An analytical approach.

PubMed

Foy, Cédric; Picaut, Judicaël; Valeau, Vincent

2016-10-01

Over the last 20 years, a statistical acoustic model has been developed to predict the reverberant sound field in buildings. This model is based on the assumption that the propagation of the reverberant sound field follows a transport process and, as an approximation, a diffusion process that can be easily solved numerically. This model, initially designed and validated for rooms with purely diffuse reflections, is extended in the present study to mixed reflections, with a proportion of specular and diffuse reflections defined by a scattering coefficient. The proposed mathematical developments lead to an analytical expression of the diffusion constant that is a function of the scattering coefficient, but also on the absorption coefficient of the walls. The results obtained with this extended diffusion model are then compared with the classical diffusion model, as well as with a sound particles tracing approach considering mixed wall reflections. The comparison shows a good agreement for long rooms with uniform low absorption (α = 0.01) and uniform scattering. For a larger absorption (α = 0.1), the agreement is moderate, due to the fact that the proposed expression of the diffusion coefficient does not vary spatially. In addition, the proposed model is for now limited to uniform diffusion and should be extended in the future to more general cases.

A quantitative property-property relationship for the internal diffusion coefficients of organic compounds in solid materials.

PubMed

Huang, L; Fantke, P; Ernstoff, A; Jolliet, O

2017-11-01

Indoor releases of organic chemicals encapsulated in solid materials are major contributors to human exposures and are directly related to the internal diffusion coefficient in solid materials. Existing correlations to estimate the diffusion coefficient are only valid for a limited number of chemical-material combinations. This paper develops and evaluates a quantitative property-property relationship (QPPR) to predict diffusion coefficients for a wide range of organic chemicals and materials. We first compiled a training dataset of 1103 measured diffusion coefficients for 158 chemicals in 32 consolidated material types. Following a detailed analysis of the temperature influence, we developed a multiple linear regression model to predict diffusion coefficients as a function of chemical molecular weight (MW), temperature, and material type (adjusted R 2 of .93). The internal validations showed the model to be robust, stable and not a result of chance correlation. The external validation against two separate prediction datasets demonstrated the model has good predicting ability within its applicability domain (Rext2>.8), namely MW between 30 and 1178 g/mol and temperature between 4 and 180°C. By covering a much wider range of organic chemicals and materials, this QPPR facilitates high-throughput estimates of human exposures for chemicals encapsulated in solid materials. © 2017 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Interpretation of diffusion coefficients in nanostructured materials from random walk numerical simulation.

PubMed

Anta, Juan A; Mora-Seró, Iván; Dittrich, Thomas; Bisquert, Juan

2008-08-14

We make use of the numerical simulation random walk (RWNS) method to compute the "jump" diffusion coefficient of electrons in nanostructured materials via mean-square displacement. First, a summary of analytical results is given that relates the diffusion coefficient obtained from RWNS to those in the multiple-trapping (MT) and hopping models. Simulations are performed in a three-dimensional lattice of trap sites with energies distributed according to an exponential distribution and with a step-function distribution centered at the Fermi level. It is observed that once the stationary state is reached, the ensemble of particles follow Fermi-Dirac statistics with a well-defined Fermi level. In this stationary situation the diffusion coefficient obeys the theoretical predictions so that RWNS effectively reproduces the MT model. Mobilities can be also computed when an electrical bias is applied and they are observed to comply with the Einstein relation when compared with steady-state diffusion coefficients. The evolution of the system towards the stationary situation is also studied. When the diffusion coefficients are monitored along simulation time a transition from anomalous to trap-limited transport is observed. The nature of this transition is discussed in terms of the evolution of electron distribution and the Fermi level. All these results will facilitate the use of RW simulation and related methods to interpret steady-state as well as transient experimental techniques.

Computer Aided Design of Integrated Circuit Fabrication Processes for VLSI Devices

DTIC Science & Technology

1980-01-01

diffusion coefficient and surface conc,,tration of the chlorine as well as any field present; X is related to the ratio ol the diffusion coefficient to...with polysilicon gat(. .ed contacts, the interaction of oxidation, segregation and diffusion in all regions of the simulation space is a critical

Chemical and Isotopic Characterization of Waters in Rio Tinto, Spain, Shows Possible Origin of the Blueberry Haematite Nodules in Meridiani Planum, Mars

NASA Astrophysics Data System (ADS)

Coleman, M. L.; Hubbard, C. G.; Mielke, R. E.; Black, S.

2005-12-01

Meridiani Planum sediments formed in an acid environment and include jarosite and other evaporitic sulfate minerals. Nodular spheroidal concretions appear to have grown in situ and are predominantly hematite. The source of the Rio Tinto, S. Spain, drains an area of extensive sulfide mineralization and is dominated by acid mine drainage processes. The system is not a Mars analog but potentially similar processes of sulfide oxidation produce sulfate rich waters which feed into the river and precipitate a large range of evaporitic sulfates including jarosite. Iron oxide minerals associated with the evaporites are either dispersed or bedded but not nodular. The water compositions appear to be mixtures of a few discreet end-members: the two most significant occur in undiluted form as inputs to the river and are relevant to many such systems. They both have all sulfur totally oxidized as sulfate. The first is a bright red water, pH ~1.5, Fe/S 0.5 and 23 g/L iron which is greater than 95% Fe3+. Its sulfate oxygen isotope composition is +2‰SMOW and about +7‰, relative to the water O isotope composition. These data indicate pyrite oxidation by Fe3+ with O in sulfate coming mainly from water. The second end-member is a pale green water, pH ~0.7, Fe/S 0.7, 50 g/L iron present mainly as Fe2+ and O isotope composition of sulfate about +6‰SMOW , about +12.5‰ relative to the water O value. Oxygen in sulfate comes mainly from atmospheric oxygen resulting from pyrite oxidation by molecular oxygen dissolved in water. Although the Rio Tinto system reactions probably are microbiologically mediated (relevant genera have been identified there) similar processes could occur abiotically but more slowly. Meridiani Planum sediments and nodules can be described by a plausible set of similar end-member processes. The primary source of sulfate is oxidation of sulfides present in basalt (pyrite, FeS2 or pyrrhotite, FeS) and weathering would have produced oxidized sulfate rich solutions at low pH. Ground water migration could produce evaporitic ponds where various bedded sulfate mineral sediments could form. The intergranular pore-spaces would be water filled. Most terrestrial spheroidal nodular concretions form by radial diffusion in pore-water of a chemical component of a very different oxidation state from that of the surrounding water. A nodular concretion is most usually formed by the reaction of the diffusive component with others in the pore-water. There are two main possible reaction sets for formation of the Blueberries that are consistent with all current data. 1. Local concentrations of organic matter (pre-biotic or biotic) formed reduction spots in which a small amount of Fe3+ either in solution or from evaporite mineral salts, was reduced to Fe2+ and then diffused radially to form an iron oxide nodule by reaction with inwardly diffusing dissolved oxygen. 2. Similar local concentrations of organic matter could also have engendered sulfate reduction and consequent outward diffusion of dissolved sulfide reacted with iron in solution to produce an iron sulfide nodule, subsequently oxidized in situ to hematite (maybe via goethite). Our current work is successfully identifying chemical and stable isotopic characteristics for both microbial and abiotic modes of all relevant reactions.

Microscopic Interpretation and Generalization of the Bloch-Torrey Equation for Diffusion Magnetic Resonance

PubMed Central

Seroussi, Inbar; Grebenkov, Denis S.; Pasternak, Ofer; Sochen, Nir

2017-01-01

In order to bridge microscopic molecular motion with macroscopic diffusion MR signal in complex structures, we propose a general stochastic model for molecular motion in a magnetic field. The Fokker-Planck equation of this model governs the probability density function describing the diffusion-magnetization propagator. From the propagator we derive a generalized version of the Bloch-Torrey equation and the relation to the random phase approach. This derivation does not require assumptions such as a spatially constant diffusion coefficient, or ad-hoc selection of a propagator. In particular, the boundary conditions that implicitly incorporate the microstructure into the diffusion MR signal can now be included explicitly through a spatially varying diffusion coefficient. While our generalization is reduced to the conventional Bloch-Torrey equation for piecewise constant diffusion coefficients, it also predicts scenarios in which an additional term to the equation is required to fully describe the MR signal. PMID:28242566

Secondary Ion Mass Spectrometry for Mg Tracer Diffusion: Issues and Solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tuggle, Jay; Giordani, Andrew; Kulkarni, Nagraj S

2014-01-01

A Secondary Ion Mass Spectrometry (SIMS) method has been developed to measure stable Mg isotope tracer diffusion. This SIMS method was then used to calculate Mg self- diffusivities and the data was verified against historical data measured using radio tracers. The SIMS method has been validated as a reliable alternative to the radio-tracer technique for the measurement of Mg self-diffusion coefficients and can be used as a routine method for determining diffusion coefficients.

An experimental study of Fe-Ni exchange between sulfide melt and olivine at upper mantle conditions: implications for mantle sulfide compositions and phase equilibria

NASA Astrophysics Data System (ADS)

Zhang, Zhou; von der Handt, Anette; Hirschmann, Marc M.

2018-03-01

The behavior of nickel in the Earth's mantle is controlled by sulfide melt-olivine reaction. Prior to this study, experiments were carried out at low pressures with narrow range of Ni/Fe in sulfide melt. As the mantle becomes more reduced with depth, experiments at comparable conditions provide an assessment of the effect of pressure at low-oxygen fugacity conditions. In this study, we constrain the Fe-Ni composition of molten sulfide in the Earth's upper mantle via sulfide melt-olivine reaction experiments at 2 GPa, 1200 and 1400 °C, with sulfide melt X_{{{Ni}}}^{{{Sulfide}}}={{Ni}}/{{Ni+{Fe}}} (atomic ratio) ranging from 0 to 0.94. To verify the approach to equilibrium and to explore the effect of {f_{{{O}2}}} on Fe-Ni exchange between phases, four different suites of experiments were conducted, varying in their experimental geometry and initial composition. Effects of Ni secondary fluorescence on olivine analyses were corrected using the PENELOPE algorithm (Baró et al., Nucl Instrum Methods Phys Res B 100:31-46, 1995), "zero time" experiments, and measurements before and after dissolution of surrounding sulfides. Oxygen fugacities in the experiments, estimated from the measured O contents of sulfide melts and from the compositions of coexisting olivines, were 3.0 ± 1.0 log units more reduced than the fayalite-magnetite-quartz (FMQ) buffer (suite 1, 2 and 3), and FMQ - 1 or more oxidized (suite 4). For the reduced (suites 1-3) experiments, Fe-Ni distribution coefficients K_{{D}}{}={(X_{{{Ni}}}^{{{sulfide}}}/X_{{{Fe}}}^{{{sulfide}}})}/{(X_{{{Ni}}^{{{olivine}}}/X_{{{Fe}}}^{{{olivine}}})}} are small, averaging 10.0 ± 5.7, with little variation as a function of total Ni content. More oxidized experiments (suite 4) give larger values of K D (21.1-25.2). Compared to previous determinations at 100 kPa, values of K D from this study are chiefly lower, in large part owing to the more reduced conditions of the experiments. The observed difference does not seem attributable to differences in temperature and pressure between experimental studies. It may be related in part to the effects of metal/sulfur ratio in sulfide melt. Application of these results to the composition of molten sulfide in peridotite indicates that compositions are intermediate in composition (X_{{{Ni}}}^{{{sulfide}}} 0.4-0.6) in the shallow mantle at 50 km, becomes more Ni rich with depth as the O content of the melt diminishes, reaching a maximum (0.6-0.7) at depths near 80-120 km, and then becomes more Fe rich in the deeper mantle where conditions are more reduced, approaching (X_{{{Ni}}}^{{{sulfide}}} 0.28) > 140 km depth. Because Ni-rich sulfide in the shallow upper mantle melts at lower temperature than more Fe-rich compositions, mantle sulfide is likely molten in much of the deep continental lithosphere, including regions of diamond formation.

Diffuse reflectance relations based on diffusion dipole theory for large absorption and reduced scattering

NASA Astrophysics Data System (ADS)

Bremmer, Rolf H.; van Gemert, Martin J. C.; Faber, Dirk J.; van Leeuwen, Ton G.; Aalders, Maurice C. G.

2013-08-01

Diffuse reflectance spectra are used to determine the optical properties of biological samples. In medicine and forensic science, the turbid objects under study often possess large absorption and/or scattering properties. However, data analysis is frequently based on the diffusion approximation to the radiative transfer equation, implying that it is limited to tissues where the reduced scattering coefficient dominates over the absorption coefficient. Nevertheless, up to absorption coefficients of 20 m at reduced scattering coefficients of 1 and 11.5 mm-1, we observed excellent agreement (r2=0.994) between reflectance measurements of phantoms and the diffuse reflectance equation proposed by Zonios et al. [Appl. Opt. 38, 6628-6637 (1999)], derived as an approximation to one of the diffusion dipole equations of Farrell et al. [Med. Phys. 19, 879-888 (1992)]. However, two parameters were fitted to all phantom experiments, including strongly absorbing samples, implying that the reflectance equation differs from diffusion theory. Yet, the exact diffusion dipole approximation at high reduced scattering and absorption also showed agreement with the phantom measurements. The mathematical structure of the diffuse reflectance relation used, derived by Zonios et al. [Appl. Opt. 38, 6628-6637 (1999)], explains this observation. In conclusion, diffuse reflectance relations derived as an approximation to the diffusion dipole theory of Farrell et al. can analyze reflectance ratios accurately, even for much larger absorption than reduced scattering coefficients. This allows calibration of fiber-probe set-ups so that the object's diffuse reflectance can be related to its absorption even when large. These findings will greatly expand the application of diffuse reflection spectroscopy. In medicine, it may allow the use of blue/green wavelengths and measurements on whole blood, and in forensic science, it may allow inclusion of objects such as blood stains and cloth at crime scenes.

Investigating Whistler Mode Wave Diffusion Coefficients at Mars

NASA Astrophysics Data System (ADS)

Shane, A. D.; Liemohn, M. W.; Xu, S.; Florie, C.

2017-12-01

Observations of electron pitch angle distributions have suggested collisions are not the only pitch angle scattering process occurring in the Martian ionosphere. This unknown scattering process is causing high energy electrons (>100 eV) to become isotropized. Whistler mode waves are one pitch angle scattering mechanism known to preferentially scatter high energy electrons in certain plasma regimes. The distribution of whistler mode wave diffusion coefficients are dependent on the background magnetic field strength and thermal electron density, as well as the frequency and wave normal angle of the wave. We have solved for the whistler mode wave diffusion coefficients using the quasi-linear diffusion equations and have integrated them into a superthermal electron transport (STET) model. Preliminary runs have produced results that qualitatively match the observed electron pitch angle distributions at Mars. We performed parametric sweeps over magnetic field, thermal electron density, wave frequency, and wave normal angle to understand the relationship between the plasma parameters and the diffusion coefficient distributions, but also to investigate what regimes whistler mode waves scatter only high energy electrons. Increasing the magnetic field strength and lowering the thermal electron density shifts the distribution of diffusion coefficients toward higher energies and lower pitch angles. We have created an algorithm to identify Mars Atmosphere Volatile and EvolutioN (MAVEN) observations of high energy isotropic pitch angle distributions in the Martian ionosphere. We are able to map these distributions at Mars, and compare the conditions under which these are observed at Mars with the results of our parametric sweeps. Lastly, we will also look at each term in the kinetic diffusion equation to determine if the energy and mixed diffusion coefficients are important enough to incorporate into STET as well.

Toward Precision and Reproducibility of Diffusion Tensor Imaging: A Multicenter Diffusion Phantom and Traveling Volunteer Study.

PubMed

Palacios, E M; Martin, A J; Boss, M A; Ezekiel, F; Chang, Y S; Yuh, E L; Vassar, M J; Schnyer, D M; MacDonald, C L; Crawford, K L; Irimia, A; Toga, A W; Mukherjee, P

2017-03-01

Precision medicine is an approach to disease diagnosis, treatment, and prevention that relies on quantitative biomarkers that minimize the variability of individual patient measurements. The aim of this study was to assess the intersite variability after harmonization of a high-angular-resolution 3T diffusion tensor imaging protocol across 13 scanners at the 11 academic medical centers participating in the Transforming Research and Clinical Knowledge in Traumatic Brain Injury multisite study. Diffusion MR imaging was acquired from a novel isotropic diffusion phantom developed at the National Institute of Standards and Technology and from the brain of a traveling volunteer on thirteen 3T MR imaging scanners representing 3 major vendors (GE Healthcare, Philips Healthcare, and Siemens). Means of the DTI parameters and their coefficients of variation across scanners were calculated for each DTI metric and white matter tract. For the National Institute of Standards and Technology diffusion phantom, the coefficients of variation of the apparent diffusion coefficient across the 13 scanners was <3.8% for a range of diffusivities from 0.4 to 1.1 × 10 -6 mm 2 /s. For the volunteer, the coefficients of variations across scanners of the 4 primary DTI metrics, each averaged over the entire white matter skeleton, were all <5%. In individual white matter tracts, large central pathways showed good reproducibility with the coefficients of variation consistently below 5%. However, smaller tracts showed more variability, with the coefficients of variation of some DTI metrics reaching 10%. The results suggest the feasibility of standardizing DTI across 3T scanners from different MR imaging vendors in a large-scale neuroimaging research study. © 2017 by American Journal of Neuroradiology.

Modified free volume theory of self-diffusion and molecular theory of shear viscosity of liquid carbon dioxide.

PubMed

Nasrabad, Afshin Eskandari; Laghaei, Rozita; Eu, Byung Chan

2005-04-28

In previous work on the density fluctuation theory of transport coefficients of liquids, it was necessary to use empirical self-diffusion coefficients to calculate the transport coefficients (e.g., shear viscosity of carbon dioxide). In this work, the necessity of empirical input of the self-diffusion coefficients in the calculation of shear viscosity is removed, and the theory is thus made a self-contained molecular theory of transport coefficients of liquids, albeit it contains an empirical parameter in the subcritical regime. The required self-diffusion coefficients of liquid carbon dioxide are calculated by using the modified free volume theory for which the generic van der Waals equation of state and Monte Carlo simulations are combined to accurately compute the mean free volume by means of statistical mechanics. They have been computed as a function of density along four different isotherms and isobars. A Lennard-Jones site-site interaction potential was used to model the molecular carbon dioxide interaction. The density and temperature dependence of the theoretical self-diffusion coefficients are shown to be in excellent agreement with experimental data when the minimum critical free volume is identified with the molecular volume. The self-diffusion coefficients thus computed are then used to compute the density and temperature dependence of the shear viscosity of liquid carbon dioxide by employing the density fluctuation theory formula for shear viscosity as reported in an earlier paper (J. Chem. Phys. 2000, 112, 7118). The theoretical shear viscosity is shown to be robust and yields excellent density and temperature dependence for carbon dioxide. The pair correlation function appearing in the theory has been computed by Monte Carlo simulations.

Anomalous diffusion and dynamics of fluorescence recovery after photobleaching in the random-comb model

NASA Astrophysics Data System (ADS)

Yuste, S. B.; Abad, E.; Baumgaertner, A.

2016-07-01

We address the problem of diffusion on a comb whose teeth display varying lengths. Specifically, the length ℓ of each tooth is drawn from a probability distribution displaying power law behavior at large ℓ ,P (ℓ ) ˜ℓ-(1 +α ) (α >0 ). To start with, we focus on the computation of the anomalous diffusion coefficient for the subdiffusive motion along the backbone. This quantity is subsequently used as an input to compute concentration recovery curves mimicking fluorescence recovery after photobleaching experiments in comblike geometries such as spiny dendrites. Our method is based on the mean-field description provided by the well-tested continuous time random-walk approach for the random-comb model, and the obtained analytical result for the diffusion coefficient is confirmed by numerical simulations of a random walk with finite steps in time and space along the backbone and the teeth. We subsequently incorporate retardation effects arising from binding-unbinding kinetics into our model and obtain a scaling law characterizing the corresponding change in the diffusion coefficient. Finally, we show that recovery curves obtained with the help of the analytical expression for the anomalous diffusion coefficient cannot be fitted perfectly by a model based on scaled Brownian motion, i.e., a standard diffusion equation with a time-dependent diffusion coefficient. However, differences between the exact curves and such fits are small, thereby providing justification for the practical use of models relying on scaled Brownian motion as a fitting procedure for recovery curves arising from particle diffusion in comblike systems.

Molecular dynamics simulation of three plastic additives' diffusion in polyethylene terephthalate.

PubMed

Li, Bo; Wang, Zhi-Wei; Lin, Qin-Bao; Hu, Chang-Ying

2017-06-01

Accurate diffusion coefficient data of additives in a polymer are of paramount importance for estimating the migration of the additives over time. This paper shows how this diffusion coefficient can be estimated for three plastic additives [2-(2'-hydroxy-5'-methylphenyl) (UV-P), 2,6-di-tert-butyl-4-methylphenol (BHT) and di-(2-ethylhexyl) phthalate (DEHP)] in polyethylene terephthalate (PET) using the molecular dynamics (MD) simulation method. MD simulations were performed at temperatures of 293-433 K. The diffusion coefficient was calculated through the Einstein relationship connecting the data of mean-square displacement at different times. Comparison of the diffusion coefficients simulated by the MD simulation technique, predicted by the Piringer model and experiments, showed that, except for a few samples, the MD-simulated values were in agreement with the experimental values within one order of magnitude. Furthermore, the diffusion process for additives is discussed in detail, and four factors - the interaction energy between additive molecules and PET, fractional free volume, molecular shape and size, and self-diffusion of the polymer - are proposed to illustrate the microscopic diffusion mechanism. The movement trajectories of additives in PET cell models suggested that the additive molecules oscillate slowly rather than hopping for a long time. Occasionally, when a sufficiently large hole was created adjacently, the molecule could undergo spatial motion by jumping into the free-volume hole and consequently start a continuous oscillation and hop. The results indicate that MD simulation is a useful approach for predicting the microstructure and diffusion coefficient of plastic additives, and help to estimate the migration level of additives from PET packaging.

Fractal Theory and Field Cover Experiments: Implications for the Fractal Characteristics and Radon Diffusion Behavior of Soils and Rocks.

PubMed

Tan, Wanyu; Li, Yongmei; Tan, Kaixuan; Duan, Xianzhe; Liu, Dong; Liu, Zehua

2016-12-01

Radon diffusion and transport through different media is a complex process affected by many factors. In this study, the fractal theories and field covering experiments were used to study the fractal characteristics of particle size distribution (PSD) of six kinds of geotechnical materials (e.g., waste rock, sand, laterite, kaolin, mixture of sand and laterite, and mixture of waste rock and laterite) and their effects on radon diffusion. In addition, the radon diffusion coefficient and diffusion length were calculated. Moreover, new formulas for estimating diffusion coefficient and diffusion length functional of fractal dimension d of PSD were proposed. These results demonstrate the following points: (1) the fractal dimension d of the PSD can be used to characterize the property of soils and rocks in the studies of radon diffusion behavior; (2) the diffusion coefficient and diffusion length decrease with increasing fractal dimension of PSD; and (3) the effectiveness of final covers in reducing radon exhalation of uranium tailings impoundments can be evaluated on the basis of the fractal dimension of PSD of materials.

Sulfidation of 310 stainless steel at sulfur potentials encountered in coal conversion systems

NASA Technical Reports Server (NTRS)

Rao, D. B.; Nelson, H. G.

1976-01-01

The sulfidation of SAE 310 stainless steel was carried out in gas mixtures of hydrogen and hydrogen sulfide over a range of sulfur potentials anticipated in advanced coal gasification processes. The kinetics, composition, and morphology of sulfide scale formation were studied at a fixed temperature of 1,065 K over a range of sulfur potentials from .00015 Nm to the -2nd power to 900 Nm to the -2nd power. At all sulfur potentials investigated, the sulfide scales were found to be multilayered. The relative thickness of the individual layers as well as the composition was found to depend on the sulfur potential. The reaction was found to obey the parabolic rate law after an initial transient period. Considerably longer transient periods were found to be due to unsteady state conditions resulting from compositional variations in the spinel layer. The sulfur pressure dependence on the parabolic rate constant was found to best fit the equation K sub p equals const. (P sub S2) to the 1/nth power, where n equals 3.7. The growth of the outer layers was found to be primarily due to the diffusion of metal ions, iron being the predominant species. The inner layer growth was due to the dissociation of the primary product at the alloy scale interface and depended on the activity of chromium.

Measurement of diffusion coefficients of VOCs for building materials: review and development of a calculation procedure.

PubMed

Haghighat, F; Lee, C S; Ghaly, W S

2002-06-01

The measurement and prediction of building material emission rates have been the subject of intensive research over the past decade, resulting in the development of advanced sensory and chemical analysis measurement techniques as well as the development of analytical and numerical models. One of the important input parameters for these models is the diffusion coefficient. Several experimental techniques have been applied to estimate the diffusion coefficient. An extensive literature review of the techniques used to measure this coefficient was carried out, for building materials exposed to volatile organic compounds (VOC). This paper reviews these techniques; it also analyses the results and discusses the possible causes of difference in the reported data. It was noted that the discrepancy between the different results was mainly because of the assumptions made in and the techniques used to analyze the data. For a given technique, the results show that there can be a difference of up to 700% in the reported data. Moreover, the paper proposes what is referred to as the mass exchanger method, to calculate diffusion coefficients considering both diffusion and convection. The results obtained by this mass exchanger method were compared with those obtained by the existing method considering only diffusion. It was demonstrated that, for porous materials, the convection resistance could not be ignored when compared with the diffusion resistance.

Apparent Diffusion Coefficient and Dynamic Contrast-Enhanced Magnetic Resonance Imaging in Pancreatic Cancer: Characteristics and Correlation With Histopathologic Parameters.

PubMed

Ma, Wanling; Li, Na; Zhao, Weiwei; Ren, Jing; Wei, Mengqi; Yang, Yong; Wang, Yingmei; Fu, Xin; Zhang, Zhuoli; Larson, Andrew C; Huan, Yi

2016-01-01

To clarify diffusion and perfusion abnormalities and evaluate correlation between apparent diffusion coefficient (ADC), MR perfusion and histopathologic parameters of pancreatic cancer (PC). Eighteen patients with PC underwent diffusion-weighted imaging and dynamic contrast-enhanced magnetic resonance imaging (DCE-MRI). Parameters of DCE-MRI and ADC of cancer and non-cancerous tissue were compared. Correlation between the rate constant that represents transfer of contrast agent from the arterial blood into the extravascular extracellular space (K, volume of the extravascular extracellular space per unit volume of tissue (Ve), and ADC of PC and histopathologic parameters were analyzed. The rate constant that represents transfer of contrast agent from the extravascular extracellular space into blood plasma, K, tissue volume fraction occupied by vascular space, and ADC of PC were significantly lower than nontumoral pancreases. Ve of PC was significantly higher than that of nontumoral pancreas. Apparent diffusion coefficient and K values of PC were negatively correlated to fibrosis content and fibroblast activation protein staining score. Fibrosis content was positively correlated to Ve. Apparent diffusion coefficient values and parameters of DCE-MRI can differentiate PC from nontumoral pancreases. There are correlations between ADC, K, Ve, and fibrosis content of PC. Fibroblast activation protein staining score of PC is negatively correlated to ADC and K. Apparent diffusion coefficient, K, and Ve may be feasible to predict prognosis of PC.

An improved strip FRAP method for estimating diffusion coefficients: correcting for the degree of photobleaching.

PubMed

Yang, J; Köhler, K; Davis, D M; Burroughs, N J

2010-06-01

Fluorescence recovery after photobleaching is a widely established method for the estimation of diffusion coefficients, strip bleaching with an associated recovery curve analysis being one of the simplest techniques. However, its implementation requires near 100% bleaching in the region of interest with negligible fluorescence loss outside, both constraints being hard to achieve concomitantly for fast diffusing molecules. We demonstrate that when these requirements are not met there is an error in the estimation of the diffusion coefficient D, either an under- or overestimation depending on which assumption is violated the most. We propose a simple modification to the recovery curve analysis incorporating the concept of the relative bleached mass m giving a revised recovery time parametrization tau=m(2)w(2)/4piD for a strip of width w. This modified model removes the requirement of 100% bleaching in the region of interest and allows for limited diffusion of the fluorophore during bleaching. We validate our method by estimating the (volume) diffusion coefficient of FITC-labelled IgG in 60% glycerol solution, D= 4.09 +/- 0.21 microm(2) s(-1), and the (surface) diffusion coefficient of a green-fluorescent protein-tagged class I MHC protein expressed at the surface of a human B cell line, D= 0.32 +/- 0.03 microm(2) s(-1) for a population of cells.

Approximation of effective moisture-diffusion coefficient to characterize performance of a barrier coating

NASA Astrophysics Data System (ADS)

Nagai, Shingo

2013-11-01

We report estimation of the effective diffusion coefficient of moisture through a barrier coating to develop an encapsulation technology for the thin-film electronics industry. This investigation targeted a silicon oxide (SiOx) film that was deposited on a plastic substrate by a large-process-area web coater. Using the finite difference method based on diffusion theory, our estimation of the effective diffusion coefficient of a SiOx film corresponded to that of bulk glass that was previously reported. This result suggested that the low diffusivities of barrier films can be obtained on a mass-production level in the factory. In this investigation, experimental observations and mathematical confirmation revealed the limit of the water vapor transmission rate on the single barrier coating.

Calculation of the fractional interstitial component of boron diffusion and segregation coefficient of boron in Si0.8Ge0.2

NASA Astrophysics Data System (ADS)

Fang, Tilden T.; Fang, Wingra T. C.; Griffin, Peter B.; Plummer, James D.

1996-02-01

Investigation of boron diffusion in strained silicon germanium buried layers reveals a fractional interstitial component of boron diffusion (fBI) in Se0.8Ge0.2 approximately equal to the fBI value in silicon. In conjunction with computer-simulated boron profiles, the results yield an absolute lower-bound of fBI in Si0.8Ge0.2 of ˜0.8. In addition, the experimental methodology provides a unique vehicle for measuring the segregation coefficient; oxidation-enhanced diffusion is used instead of an extended, inert anneal to rapidly diffuse the dopant to equilibrium levels across the interface, allowing the segregation coefficient to be measured more quickly.

Sulfide Generated by Sulfate Reduction is a Primary Controller of the Occurrence of Wild Rice (Zizania palustris) in Shallow Aquatic Ecosystems

NASA Astrophysics Data System (ADS)

Myrbo, A.; Swain, E. B.; Engstrom, D. R.; Coleman Wasik, J.; Brenner, J.; Dykhuizen Shore, M.; Peters, E. B.; Blaha, G.

2017-11-01

Field observations suggest that surface water sulfate concentrations control the distribution of wild rice, an aquatic grass (Zizania palustris). However, hydroponic studies show that sulfate is not toxic to wild rice at even unrealistically high concentrations. To determine how sulfate might directly or indirectly affect wild rice, potential wild rice habitat was characterized for 64 chemical and physical variables in over 100 sites spanning a relatively steep climatic and geological gradient in Minnesota. Habitat suitability was assessed by comparing the occurrence of wild rice with the field variables, through binary logistic regression. This analysis demonstrated that sulfide in sediment pore water, generated by the microbial reduction of sulfate that diffuses or advects into the sediment, is the primary control of wild rice occurrence. Water temperature and water transparency independently control the suitability of habitat for wild rice. In addition to generating phytotoxic sulfide, sulfate reduction also supports anaerobic decomposition of organic matter, releasing nutrients that can compound the harm of direct sulfide toxicity. These results are important because they show that increases in sulfate loading to surface water can have multiple negative consequences for ecosystems, even though sulfate itself is relatively benign.

Note on coefficient matrices from stochastic Galerkin methods for random diffusion equations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou Tao, E-mail: tzhou@lsec.cc.ac.c; Tang Tao, E-mail: ttang@hkbu.edu.h

2010-11-01

In a recent work by Xiu and Shen [D. Xiu, J. Shen, Efficient stochastic Galerkin methods for random diffusion equations, J. Comput. Phys. 228 (2009) 266-281], the Galerkin methods are used to solve stochastic diffusion equations in random media, where some properties for the coefficient matrix of the resulting system are provided. They also posed an open question on the properties of the coefficient matrix. In this work, we will provide some results related to the open question.

Separation of Electric Fields Into Potential and Inductive Parts, and Implications for Radial Diffusion

NASA Astrophysics Data System (ADS)

Chan, A. A.; Ilie, R.; Elkington, S. R.; Albert, J.; Huie, W.

2017-12-01

It has been traditional to separate radiation belt radial-diffusion coefficients into two contributions: an "electrostatic" diffusion coefficient, which is assumed to be due to a potential (non-inductive) electric field, and an "electromagnetic" diffusion coefficient , which is assumed to be due to the combined effect of an inductive electric field and the corresponding time-dependent magnetic field. One difficulty in implementing this separation when using magnetospheric fields obtained from measurements, or from MHD simulations, is that only the total electric field is given; the separation of the electric field into potential and inductive parts is not readily available. In this work we separate the electric field using a numerical method based on the Helmholtz decomposition of the total motional electric field calculated by the BATS-R-US MHD code. The inner boundary for the electric potential is based on the Ridley Ionospheric Model solution and we assume floating boundary conditions in the solar wind. Using different idealized solar wind drivers, including a solar wind density that is oscillating at a single frequency or with a broad spectrum of frequencies, we calculate potential and inductive electric fields, electric and magnetic power spectral densities, and corresponding radial diffusion coefficients. Simulations driven by idealized solar wind conditions show a clear separation of the potential and inductive contributions to the power spectral densities and diffusion coefficients. Simulations with more realistic solar wind drivers are underway to better assess the use of electrostatic and electromagnetic diffusion coefficients in understanding ULF wave-particle interactions in Earth's radiation belts.

The Effect of a Fluorophore Photo-Physics on the Lipid Vesicle Diffusion Coefficient Studied by Fluorescence Correlation Spectroscopy.

PubMed

Drabik, Dominik; Przybyło, Magda; Sikorski, Aleksander; Langner, Marek

2016-03-01

Fluorescence Correlation Spectroscopy (FCS) is a technique, which allows determination of the diffusion coefficient and concentration of fluorescent objects suspended in the solution. The measured parameter is the fluctuation of the fluorescence signal emitted by diffusing molecules. When 100 nm DOPC vesicles labeled with various fluorescent dyes (Fluorescein-PE, NBD-PE, Atto488 DOPE or βBodipy FL) were measured, different values of diffusion coefficients have been obtained. These diffusion coefficients were different from the expected values measured using the dynamic light scattering method (DLS). The FCS was initially developed for solutions containing small fluorescent molecules therefore the observed inconsistency may result from the nature of vesicle suspension itself. The duration of the fluorescence signal may depend on the following factors: the exposure time of the labeled object to the excitation beam, the photo-physical properties (e.g., stability) of a fluorophore, the theoretical model used for the calculations of the diffusion coefficient and optical properties of the vesicle suspension. The diffusion coefficients determined for differently labeled liposomes show that its dependence on vesicle size and quantity of fluorescent probed used for labeling was significant demonstrating that the fluorescence properties of the fluorophore itself (bleaching and/or blinking) were critical factors for a correct outcome of FCS experiment. The new, based on combined FCS and DLS measurements, method for the determination of the focal volume prove itself to be useful for the evaluation of a fluorescence dye with respect to its applicability for FCS experiment.

Effects of molecular size and structure on self-diffusion coefficient and viscosity for saturated hydrocarbons having six carbon atoms.

PubMed

Iwahashi, Makio; Kasahara, Yasutoshi

2007-01-01

Self-diffusion coefficients and viscosities for the saturated hydrocarbons having six carbon atoms such as hexane, 2-methylpentane (2MP), 3-methylpentane (3MP), 2,2-dimethylbutane (22DMB), 2,3-dimethylbutane (23DMB), methylcyclopentane (McP) and cyclohexane (cH) were measured at various constant temperatures; obtained results were discussed in connection with their molar volumes, molecular structures and thermodynamic properties. The values of self-diffusion coefficients as the microscopic property were inversely proportional to those of viscosities as the macroscopic property. The order of their viscosities was almost same to those of their melting temperatures and enthalpies of fusion, which reflect the attractive interactions among their molecules. On the other hand, the order of the self-diffusion coefficients inversely related to the order of the melting temperatures and the enthalpies of the fusion. Namely, the compound having the larger attractive interaction mostly shows the less mobility in its liquid state, e.g., cyclohexane (cH), having the largest attractive interaction and the smallest molar volume exhibits an extremely large viscosity and small self-diffusion coefficient comparing with other hydrocarbons. However, a significant exception was 22DMB, being most close to a sphere: In spite of the smallest attractive interaction and the largest molar volume of 22DMB in the all samples, it has the thirdly larger viscosity and the thirdly smaller self-diffusion coefficient. Consequently, the dynamical properties such as self-diffusion and viscosity for the saturated hydrocarbons are determined not only by their attractive interactions but also by their molecular structures.

Relativistic collective diffusion in one-dimensional systems

NASA Astrophysics Data System (ADS)

Lin, Gui-Wu; Lam, Yu-Yiu; Zheng, Dong-Qin; Zhong, Wei-Rong

2018-05-01

The relativistic collective diffusion in one-dimensional molecular system is investigated through nonequilibrium molecular dynamics with Monte Carlo methods. We have proposed the relationship among the speed, the temperature, the density distribution and the collective diffusion coefficient of particles in a relativistic moving system. It is found that the relativistic speed of the system has no effect on the temperature, but the collective diffusion coefficient decreases to zero as the velocity of the system approaches to the speed of light. The collective diffusion coefficient is modified as D‧ = D(1 ‑w2 c2 )3 2 for satisfying the relativistic circumstances. The present results may contribute to the understanding of the behavior of the particles transport diffusion in a high speed system, as well as enlighten the study of biological metabolism at relativistic high speed situation.

Macromolecule diffusion and confinement in prokaryotic cells.

PubMed

Mika, Jacek T; Poolman, Bert

2011-02-01

We review recent observations on the mobility of macromolecules and their spatial organization in live bacterial cells. We outline the major fluorescence microscopy-based methods to determine the mobility and thus the diffusion coefficients (D) of molecules, which is not trivial in small cells. The extremely high macromolecule crowding of prokaryotes is used to rationalize the reported lower diffusion coefficients as compared to eukaryotes, and we speculate on the nature of the barriers for diffusion observed for proteins (and mRNAs) in vivo. Building on in vitro experiments and modeling studies, we evaluate the size dependence of diffusion coefficients for macromolecules in vivo, in case of both water-soluble and integral membrane proteins. We comment on the possibilities of anomalous diffusion and provide examples where the macromolecule mobility may be limiting biological processes. Copyright © 2010 Elsevier Ltd. All rights reserved.

Coupled low-energy - ring current plasma diffusion in the Jovian magnetosphere

NASA Technical Reports Server (NTRS)

Summers, D.; Siscoe, G. L.

1985-01-01

The outwardly diffusing Iogenic plasma and the simultaneously inwardly diffusing ring current plasma in the Jovian magnetosphere are described using a coupled diffusion model which incorporates the effects of the pressure gradient of the ring current into the cross-L diffusion coefficient. The coupled diffusion coefficient is derived by calculating the total energy available to drive the diffusion process. The condition is imposed that the diffusion coefficient takes on a local minimum value at some point in the region L = 7-8, at which point the gradient of the Io plasma density is specified as ramp value given by Siscoe et al. (1981). The hypothesis that the pressure gradient of the ring current causes the diminution of radial plasma transport is tested, and solution profiles for the Iogenic and ring current plasma densities are obtained which imply that the Io plasma ramp is caused by a high-density, low-energy component of the ring current hitherto unobserved directly.

Self diffusion of alkaline-Earth in Ca-Mg-aluminosilicate melts: Experimental improvements on the determination of the self-diffusion coefficients

NASA Technical Reports Server (NTRS)

Paillat, O.; Wasserburg, G. J.

1993-01-01

Experimental studies of self-diffusion isotopes in silicate melts often have quite large uncertainties when comparing one study to another. We designed an experiment in order to improve the precision of the results by simultaneously studying several elements (Mg, Ca, Sr, Ba) during the same experiment thereby greatly reducing the relative experimental uncertainties. Results show that the uncertainties on the diffusion coefficients can be reduced to 10 percent, allowing a more reliable comparison of differences of self-diffusion coefficients of the elements. This type of experiment permits us to study precisely and simultaneously several elements with no restriction on any element. We also designed an experiment to investigate the possible effects of multicomponent diffusion during Mg self-diffusion experiments by comparing cases where the concentrations of the elements and the isotopic compositions are different. The results suggest that there are differences between the effective means of transport. This approach should allow us to investigate the importance of multicomponent diffusion in silicate melts.

Diffusion Coefficients from Molecular Dynamics Simulations in Binary and Ternary Mixtures

NASA Astrophysics Data System (ADS)

Liu, Xin; Schnell, Sondre K.; Simon, Jean-Marc; Krüger, Peter; Bedeaux, Dick; Kjelstrup, Signe; Bardow, André; Vlugt, Thijs J. H.

2013-07-01

Multicomponent diffusion in liquids is ubiquitous in (bio)chemical processes. It has gained considerable and increasing interest as it is often the rate limiting step in a process. In this paper, we review methods for calculating diffusion coefficients from molecular simulation and predictive engineering models. The main achievements of our research during the past years can be summarized as follows: (1) we introduced a consistent method for computing Fick diffusion coefficients using equilibrium molecular dynamics simulations; (2) we developed a multicomponent Darken equation for the description of the concentration dependence of Maxwell-Stefan diffusivities. In the case of infinite dilution, the multicomponent Darken equation provides an expression for [InlineEquation not available: see fulltext.] which can be used to parametrize the generalized Vignes equation; and (3) a predictive model for self-diffusivities was proposed for the parametrization of the multicomponent Darken equation. This equation accurately describes the concentration dependence of self-diffusivities in weakly associating systems. With these methods, a sound framework for the prediction of mutual diffusion in liquids is achieved.

Partitioning and diffusion of PBDEs through an HDPE geomembrane.

PubMed

Rowe, R Kerry; Saheli, Pooneh T; Rutter, Allison

2016-09-01

Polybrominated diphenyl ether (PBDE) has been measured in MSW landfill leachate and its migration through a modern landfill liner has not been investigated previously. To assure environmental protection, it is important to evaluate the efficacy of landfill liners for controlling the release of PBDE to the environment to a negligible level. The partitioning and diffusion of a commercial mixture of PBDEs (DE-71: predominantly containing six congeners) with respect to a high-density polyethylene (HDPE) geomembrane is examined. The results show that the partitioning coefficients of the six congeners in this mixture range from 700,000 to 7,500,000 and the diffusion coefficients range from 1.3 to 6.0×10(-15)m(2)/s depending on the congener. This combination of very high partitioning coefficients and very low diffusion coefficients suggest that a well constructed HDPE geomembrane liner will be an extremely effective barrier for PBDEs with respect to diffusion from a municipal solid waste landfill, as illustrated by an example. The results for pure diffusion scenario showed that the congeners investigated meet the guidelines by at least a factor of three for an effective geomembrane liner where diffusion is the controlling transport mechanism. Copyright © 2016 Elsevier Ltd. All rights reserved.

DIFF--A 7090 Fortran Program to Determine Neutron Diffusion Constants Relating to a Six-Group Calculation; DIFF--UN PROGRAMME FOR TRAN 7090 POUR DETERMINER LES CONSTANTES DE DIFFUSION NEUTRONIQUE RELATIVES A UN CALCUL A SIX GROUPES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Plelnevaux, C.

The computer program DIFF, in Fortran for the IBM 7090, for calculating the neutron diffusion coefficients and attenuation areas (L/sup 2/) necessary for multigroup diffusion calculations for reactor shielding is described. Diffusion coefficients and values of the inverse attenuation length are given for a six group calculation for several interesting shielding materials. (D.C.W.)

Thermal diffusion behavior of nonionic surfactants in water.

PubMed

Ning, Hui; Kita, Rio; Kriegs, Hartmut; Luettmer-Strathmann, Jutta; Wiegand, Simone

2006-06-08

We studied the thermal diffusion behavior of hexaethylene glycol monododecyl ether (C12E6) in water by means of thermal diffusion forced Rayleigh scattering (TDFRS) and determined Soret coefficients, thermal diffusion coefficients, and diffusion constants at different temperatures and concentrations. At low surfactant concentrations, the measured Soret coefficient is positive, which implies that surfactant micelles move toward the cold region in a temperature gradient. For C12E6/water at a high surfactant concentration of w1 = 90 wt % and a temperature of T = 25 degrees C, however, a negative Soret coefficient S(T) was observed. Because the concentration part of the TDFRS diffraction signal for binary systems is expected to consist of a single mode, we were surprised to find a second, slow mode for C12E6/water system in a certain temperature and concentration range. To clarify the origin of this second mode, we investigated also, tetraethylene glycol monohexyl ether (C6E4), tetraethylene glycol monooctyl ether (C8E4), pentaethylene glycol monododecyl ether (C12E5), and octaethylene glycol monohexadecyl ether (C16E8) and compared the results with the previous results for octaethylene glycol monodecyl ether (C10E8). Except for C6E4 and C10E8, a second slow mode was observed in all systems usually for state points close to the phase boundary. The diffusion coefficient and Soret coefficient derived from the fast mode can be identified as the typical mutual diffusion and Soret coefficients of the micellar solutions and compare well with the independently determined diffusion coefficients in a dynamic light scattering experiment. Experiments with added salt show that the slow mode is suppressed by the addition of w(NaCl) = 0.02 mol/L sodium chloride. This suggests that the slow mode is related to the small amount of absorbing ionic dye, less than 10(-5) by weight, which is added in TDFRS experiments to create a temperature grating. The origin of the slow mode of the TDFRS signal will be tentatively interpreted in terms of a ternary mixture of neutral micelles, dye-charged micelles, and water.

Short-time self-diffusion coefficient of a particle in a colloidal suspension bounded by a microchannel: Virial expansions and simulation

NASA Astrophysics Data System (ADS)

Kȩdzierski, Marcin; Wajnryb, Eligiusz

2011-10-01

Self-diffusion of colloidal particles confined to a cylindrical microchannel is considered theoretically and numerically. Virial expansion of the self-diffusion coefficient is performed. Two-body and three-body hydrodynamic interactions are evaluated with high precision using the multipole method. The multipole expansion algorithm is also used to perform numerical simulations of the self-diffusion coefficient, valid for all possible particle packing fractions. Comparison with earlier results shows that the widely used method of reflections is insufficient for calculations of hydrodynamic interactions even for small packing fractions and small particles radii, contrary to the prevalent opinion.

Oxygen chemical diffusion in hypo-stoichiometric MOX

NASA Astrophysics Data System (ADS)

Kato, Masato; Morimoto, Kyoichi; Tamura, Tetsuya; Sunaoshi, Takeo; Konashi, Kenji; Aono, Shigenori; Kashimura, Motoaki

2009-06-01

Kinetics of the oxygen-to-metal ratio change in (U 0.8Pu 0.2)O 2-x and (U 0.7Pu 0.3)O 2-x was evaluated in the temperature range of 1523-1623 K using a thermo-gravimetric technique. The oxygen chemical diffusion coefficients were decided as a function of temperature from the kinetics of the reduction process under a hypo-stoichiometric composition. The diffusion coefficient of (U 0.7Pu 0.3)O 2-x was smaller than that of (U 0.8Pu 0.2)O 2-x. No strong dependence was observed for the diffusion coefficient on the O/M variation of samples.

Diffusion relaxation times of nonequilibrium isolated small bodies and their solid phase ensembles to equilibrium states

NASA Astrophysics Data System (ADS)

Tovbin, Yu. K.

2017-08-01

The possibility of obtaining analytical estimates in a diffusion approximation of the times needed by nonequilibrium small bodies to relax to their equilibrium states based on knowledge of the mass transfer coefficient is considered. This coefficient is expressed as the product of the self-diffusion coefficient and the thermodynamic factor. A set of equations for the diffusion transport of mixture components is formulated, characteristic scales of the size of microheterogeneous phases are identified, and effective mass transfer coefficients are constructed for them. Allowing for the developed interface of coexisting and immiscible phases along with the porosity of solid phases is discussed. This approach can be applied to the diffusion equalization of concentrations of solid mixture components in many physicochemical systems: the mutual diffusion of components in multicomponent systems (alloys, semiconductors, solid mixtures of inert gases) and the mass transfer of an absorbed mobile component in the voids of a matrix consisting of slow components or a mixed composition of mobile and slow components (e.g., hydrogen in metals, oxygen in oxides, and the transfer of molecules through membranes of different natures, including polymeric).

Study of Water Absorption in Raffia vinifera Fibres from Bandjoun, Cameroon

PubMed Central

Sikame Tagne, N. R.; Njeugna, E.; Fogue, M.; Drean, J.-Y.; Nzeukou, A.; Fokwa, D.

2014-01-01

The study is focused on the water diffusion phenomenon through the Raffia vinifera fibre from the stem. The knowledge on the behavior of those fibres in presence of liquid during the realization of biocomposite, is necessary. The parameters like percentage of water gain at the point of saturation, modelling of the kinetic of water absorption, and the effective diffusion coefficient were the main objectives. Along a stem of raffia, twelve zones of sampling were defined. From Fick's 2nd law of diffusion, a new model was proposed and evaluated compared to four other models at a constant temperature of 23°C. From the proposed model, the effective diffusion coefficient was deduced. The percentage of water gain was in the range of 303–662%. The proposed model fitted better to the experimental data. The estimated diffusion coefficient was evaluated during the initial phase and at the final phase. In any cross section located along the stem of Raffia vinifera, it was found that the effective diffusion coefficient increases from the periphery to the centre during the initial and final phases. PMID:24592199

Measurement of CO2 diffusivity for carbon sequestration: a microfluidic approach for reservoir-specific analysis.

PubMed

Sell, Andrew; Fadaei, Hossein; Kim, Myeongsub; Sinton, David

2013-01-02

Predicting carbon dioxide (CO(2)) security and capacity in sequestration requires knowledge of CO(2) diffusion into reservoir fluids. In this paper we demonstrate a microfluidic based approach to measuring the mutual diffusion coefficient of carbon dioxide in water and brine. The approach enables formation of fresh CO(2)-liquid interfaces; the resulting diffusion is quantified by imaging fluorescence quenching of a pH-dependent dye, and subsequent analyses. This method was applied to study the effects of site-specific variables--CO(2) pressure and salinity levels--on the diffusion coefficient. In contrast to established, macro-scale pressure-volume-temperature cell methods that require large sample volumes and testing periods of hours/days, this approach requires only microliters of sample, provides results within minutes, and isolates diffusive mass transport from convective effects. The measured diffusion coefficient of CO(2) in water was constant (1.86 [± 0.26] × 10(-9) m(2)/s) over the range of pressures (5-50 bar) tested at 26 °C, in agreement with existing models. The effects of salinity were measured with solutions of 0-5 M NaCl, where the diffusion coefficient varied up to 3 times. These experimental data support existing theory and demonstrate the applicability of this method for reservoir-specific testing.

Statistical theory of diffusion in concentrated bcc and fcc alloys and concentration dependencies of diffusion coefficients in bcc alloys FeCu, FeMn, FeNi, and FeCr

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vaks, V. G.; Khromov, K. Yu., E-mail: khromov-ky@nrcki.ru; Pankratov, I. R.

2016-07-15

The statistical theory of diffusion in concentrated bcc and fcc alloys with arbitrary pairwise interatomic interactions based on the master equation approach is developed. Vacancy–atom correlations are described using both the second-shell-jump and the nearest-neighbor-jump approximations which are shown to be usually sufficiently accurate. General expressions for Onsager coefficients in terms of microscopic interatomic interactions and some statistical averages are given. Both the analytical kinetic mean-field and the Monte Carlo methods for finding these averages are described. The theory developed is used to describe sharp concentration dependencies of diffusion coefficients in several iron-based alloy systems. For the bcc alloys FeCu,more » FeMn, and FeNi, we predict the notable increase of the iron self-diffusion coefficient with solute concentration c, up to several times, even though values of c possible for these alloys do not exceed some percent. For the bcc alloys FeCr at high temperatures T ≳ 1400 K, we show that the very strong and peculiar concentration dependencies of both tracer and chemical diffusion coefficients observed in these alloys can be naturally explained by the theory, without invoking exotic models discussed earlier.« less

Ion conduction mechanisms and thermal properties of hydrated and anhydrous phosphoric acids studied with 1H, 2H, and 31P NMR.

PubMed

Aihara, Yuichi; Sonai, Atsuo; Hattori, Mineyuki; Hayamizu, Kikuko

2006-12-14

To understand the behaviors of phosphoric acids in fuel cells, the ion conduction mechanisms of phosphoric acids in condensed states without free water and in a monomer state with water were studied by measuring the ionic conductivity (sigma) using AC impedance, thermal properties, and self-diffusion coefficients (D) and spin-lattice relaxation times (T1) with multinuclear NMR. The self-diffusion coefficient of the protons (H+ or H3O+), H2O, and H located around the phosphate were always larger than the diffusion coefficients of the phosphates and the disparity increased with increasing phosphate concentration. The diffusion coefficients of the samples containing D2O paralleled those in the protonated samples. Since the 1H NMR T1 values exhibited a minimum with temperature, it was possible to determine the correlation times and they were found to be of nanosecond order for a distance of nanometer order for a flip. The agreement of the ionic conductivities measured directly and those calculated from the diffusion coefficients indicates that the ion conduction obeys the Nernst-Einstein equation in the condensed phosphoric acids. The proton diffusion plays a dominant role in the ion conduction, especially in the condensed phosphoric acids.

Interdiffusion and Intrinsic Diffusion in the Mg-Al System

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brennan, Sarah; Bermudez, Katrina; Sohn, Yong Ho

2012-01-01

Solid-to-solid diffusion couples were assembled and annealed to examine the diffusion between pure Mg (99.96%) and Al (99.999%). Diffusion anneals were carried out at 300 , 350 , and 400 C for 720, 360, and 240 hours, respectively. Optical and scanning electron microscopes were utilized to identify the formation of the intermetallic phases, -Al12Mg17 and -Al3Mg2 and absence of the -phase in the diffusion couples. Thicknesses of the -Al12Mg17 and -Al3Mg2 phases were measured and the parabolic growth constants were calculated to determine the activation energies for the growth, 165 and 86 KJ/mole, respectively. Concentration profiles were determined with electronmore » microprobe analysis using pure elemental standards. Composition-dependent interdiffusion coefficients in Mg-solid solution, -Al12Mg17 and - Al3Mg2 and Al-solid solutions were calculated based on the Boltzmann-Matano analysis. Average effective interdiffusion coefficients for each phase were also calculated, and the magnitude was the highest for the -Al3Mg2 phase, followed by -Al12Mg17, Al-solid solution and Mg-solid solution. Intrinsic diffusion coefficients based on Huemann s analysis (e.g., marker plane) were determined for the ~38 at.% Mg in the -Al3Mg2 phase. Activation energies and the pre-exponential factors for the inter- and intrinsic diffusion coefficients were calculated for the temperature range examined. The -Al3Mg2 phase was found to have the lowest activation energies for growth and interdiffusion among all four phases studied. At the marker location in the -Al3Mg2 phase, the intrinsic diffusion of Al was found to be faster than that of Mg. Extrapolations of the impurity diffusion coefficients in the terminal solid solutions were made and compared to the available self- and impurity diffusion data from literature. Thermodynamic factor, tracer diffusion coefficients and atomic mobilities at the marker plane composition were approximated using available literature values of Mg activity in the -Al3Mg2 phase.« less

Two-photon absorption in arsenic sulfide glasses

NASA Astrophysics Data System (ADS)

Chunaev, D. S.; Snopatin, G. E.; Plotnichenko, V. G.; Karasik, A. Ya.

2016-10-01

The two-photon absorption coefficient of 1047-{\\text{nm}} light in {\\text{As}}35{\\text{S}}65 chalcogenide glass has been measured. CW probe radiation has been used to observe the linear absorption in glass induced by two-photon excitation. The induced absorption lifetime was found to be ∼ 2 {\\text{ms}}.

Influence of relative air/water flow velocity on oxygen mass transfer in gravity sewers.

PubMed

Carrera, Lucie; Springer, Fanny; Lipeme-Kouyi, Gislain; Buffiere, Pierre

2017-04-01

Problems related to hydrogen sulfide may be serious for both network stakeholders and the public in terms of health, sustainability of the sewer structure and urban comfort. H 2 S emission models are generally theoretical and simplified in terms of environmental conditions. Although air transport characteristics in sewers must play a role in the fate of hydrogen sulfide, only a limited number of studies have investigated this issue. The aim of this study was to better understand H 2 S liquid to gas transfer by highlighting the link between the mass transfer coefficient and the turbulence in the air flow and the water flow. For experimental safety reasons, O 2 was taken as a model compound. The oxygen mass transfer coefficients were obtained using a mass balance in plug flow. The mass transfer coefficient was not impacted by the range of the interface air-flow velocity values tested (0.55-2.28 m·s -1 ) or the water velocity values (0.06-0.55 m·s -1 ). Using the ratio between k L,O 2 to k L,H 2 S , the H 2 S mass transfer behavior in a gravity pipe in the same hydraulic conditions can be predicted.

A novel microbial habitat in the mid-ocean ridge subseafloor

PubMed Central

Summit, Melanie; Baross, John A.

2001-01-01

The subseafloor at the mid-ocean ridge is predicted to be an excellent microbial habitat, because there is abundant space, fluid flow, and geochemical energy in the porous, hydrothermally influenced oceanic crust. These characteristics also make it a good analog for potential subsurface extraterrestrial habitats. Subseafloor environments created by the mixing of hot hydrothermal fluids and seawater are predicted to be particularly energy-rich, and hyperthermophilic microorganisms that broadly reflect such predictions are ejected from these systems in low-temperature (≈15°C), basalt-hosted diffuse effluents. Seven hyperthermophilic heterotrophs isolated from low-temperature diffuse fluids exiting the basaltic crust in and near two hydrothermal vent fields on the Endeavour Segment, Juan de Fuca Ridge, were compared phylogenetically and physiologically to six similarly enriched hyperthermophiles from samples associated with seafloor metal sulfide structures. The 13 organisms fell into four distinct groups: one group of two organisms corresponding to the genus Pyrococcus and three groups corresponding to the genus Thermococcus. Of these three groups, one was composed solely of sulfide-derived organisms, and the other two related groups were composed of subseafloor organisms. There was no evidence of restricted exchange of organisms between sulfide and subseafloor habitats, and therefore this phylogenetic distinction indicates a selective force operating between the two habitats. Hypotheses regarding the habitat differences were generated through comparison of the physiology of the two groups of hyperthermophiles; some potential differences between these habitats include fluid flow stability, metal ion concentrations, and sources of complex organic matter. PMID:11226209

Comparative exploration of hydrogen sulfide and water transmembrane free energy surfaces via orthogonal space tempering free energy sampling

DOE PAGES

Lv, Chao; Aitchison, Erick W.; Wu, Dongsheng; ...

2015-06-29

Hydrogen sulfide (H 2S), a commonly known toxic gas compound, possesses unique chemical features that allow this small solute molecule to quickly diffuse through cell membranes. Taking advantage of the recent orthogonal space tempering (OST) method, we comparatively mapped the transmembrane free energy landscapes of H 2S and its structural analogue, water (H 2O), seeking to decipher the molecular determinants that govern their drastically different permeabilities. Here, as revealed by our OST sampling results, in contrast to the highly polar water solute, hydrogen sulfide is evidently amphipathic, and thus inside membrane is favorably localized at the interfacial region, that is,more » the interface between the polar head-group and nonpolar acyl chain regions. Because the membrane binding affinity of H 2S is mainly governed by its small hydrophobic moiety and the barrier height inbetween the interfacial region and the membrane center is largely determined by its moderate polarity, the transmembrane free energy barriers to encounter by this toxic molecule are very small. Moreover when H2S diffuses from the bulk solution to the membrane center, the above two effects nearly cancel each other, so as to lead to a negligible free energy difference. Lastly, this study not only explains why H 2S can quickly pass through cell membranes but also provides a practical illustration on how to use the OST free energy sampling method to conveniently analyze complex molecular processes.« less

Comparative exploration of hydrogen sulfide and water transmembrane free energy surfaces via orthogonal space tempering free energy sampling.

PubMed

Lv, Chao; Aitchison, Erick W; Wu, Dongsheng; Zheng, Lianqing; Cheng, Xiaolin; Yang, Wei

2016-03-05

Hydrogen sulfide (H2 S), a commonly known toxic gas compound, possesses unique chemical features that allow this small solute molecule to quickly diffuse through cell membranes. Taking advantage of the recent orthogonal space tempering (OST) method, we comparatively mapped the transmembrane free energy landscapes of H2 S and its structural analogue, water (H2 O), seeking to decipher the molecular determinants that govern their drastically different permeabilities. As revealed by our OST sampling results, in contrast to the highly polar water solute, hydrogen sulfide is evidently amphipathic, and thus inside membrane is favorably localized at the interfacial region, that is, the interface between the polar head-group and nonpolar acyl chain regions. Because the membrane binding affinity of H2 S is mainly governed by its small hydrophobic moiety and the barrier height inbetween the interfacial region and the membrane center is largely determined by its moderate polarity, the transmembrane free energy barriers to encounter by this toxic molecule are very small. Moreover when H2 S diffuses from the bulk solution to the membrane center, the above two effects nearly cancel each other, so as to lead to a negligible free energy difference. This study not only explains why H2 S can quickly pass through cell membranes but also provides a practical illustration on how to use the OST free energy sampling method to conveniently analyze complex molecular processes. © 2015 Wiley Periodicals, Inc. © 2015 Wiley Periodicals, Inc.

Discrimination between diffuse and point sources of arsenic at Zimapán, Hidalgo state, Mexico.

PubMed

Sracek, Ondra; Armienta, María Aurora; Rodríguez, Ramiro; Villaseñor, Guadalupe

2010-01-01

There are two principal sources of arsenic in Zimapán. Point sources are linked to mining and smelting activities and especially to mine tailings. Diffuse sources are not well defined and are linked to regional flow systems in carbonate rocks. Both sources are caused by the oxidation of arsenic-rich sulfidic mineralization. Point sources are characterized by Ca-SO(4)-HCO(3) ground water type and relatively enriched values of deltaD, delta(18)O, and delta(34)S(SO(4)). Diffuse sources are characterized by Ca-Na-HCO(3) type of ground water and more depleted values of deltaD, delta(18)O, and delta(34)S(SO(4)). Values of deltaD and delta(18)O indicate similar altitude of recharge for both arsenic sources and stronger impact of evaporation for point sources in mine tailings. There are also different values of delta(34)S(SO(4)) for both sources, presumably due to different types of mineralization or isotopic zonality in deposits. In Principal Component Analysis (PCA), the principal component 1 (PC1), which describes the impact of sulfide oxidation and neutralization by the dissolution of carbonates, has higher values in samples from point sources. In spite of similar concentrations of As in ground water affected by diffuse sources and point sources (mean values 0.21 mg L(-1) and 0.31 mg L(-1), respectively, in the years from 2003 to 2008), the diffuse sources have more impact on the health of population in Zimapán. This is caused by the extraction of ground water from wells tapping regional flow system. In contrast, wells located in the proximity of mine tailings are not generally used for water supply.

Sucrose diffusion in aqueous solution

PubMed Central

Murray, Benjamin J.

2016-01-01

The diffusion of sugar in aqueous solution is important both in nature and in technological applications, yet measurements of diffusion coefficients at low water content are scarce. We report directly measured sucrose diffusion coefficients in aqueous solution. Our technique utilises a Raman isotope tracer method to monitor the diffusion of non-deuterated and deuterated sucrose across a boundary between the two aqueous solutions. At a water activity of 0.4 (equivalent to 90 wt% sucrose) at room temperature, the diffusion coefficient of sucrose was determined to be approximately four orders of magnitude smaller than that of water in the same material. Using literature viscosity data, we show that, although inappropriate for the prediction of water diffusion, the Stokes–Einstein equation works well for predicting sucrose diffusion under the conditions studied. As well as providing information of importance to the fundamental understanding of diffusion in binary solutions, these data have technological, pharmaceutical and medical implications, for example in cryopreservation. Moreover, in the atmosphere, slow organic diffusion may have important implications for aerosol growth, chemistry and evaporation, where processes may be limited by the inability of a molecule to diffuse between the bulk and the surface of a particle. PMID:27364512

High-grade glioma diffusive modeling using statistical tissue information and diffusion tensors extracted from atlases.

PubMed

Roniotis, Alexandros; Manikis, Georgios C; Sakkalis, Vangelis; Zervakis, Michalis E; Karatzanis, Ioannis; Marias, Kostas

2012-03-01

Glioma, especially glioblastoma, is a leading cause of brain cancer fatality involving highly invasive and neoplastic growth. Diffusive models of glioma growth use variations of the diffusion-reaction equation in order to simulate the invasive patterns of glioma cells by approximating the spatiotemporal change of glioma cell concentration. The most advanced diffusive models take into consideration the heterogeneous velocity of glioma in gray and white matter, by using two different discrete diffusion coefficients in these areas. Moreover, by using diffusion tensor imaging (DTI), they simulate the anisotropic migration of glioma cells, which is facilitated along white fibers, assuming diffusion tensors with different diffusion coefficients along each candidate direction of growth. Our study extends this concept by fully exploiting the proportions of white and gray matter extracted by normal brain atlases, rather than discretizing diffusion coefficients. Moreover, the proportions of white and gray matter, as well as the diffusion tensors, are extracted by the respective atlases; thus, no DTI processing is needed. Finally, we applied this novel glioma growth model on real data and the results indicate that prognostication rates can be improved. © 2012 IEEE

Mercury's Magma Ocean

NASA Astrophysics Data System (ADS)

Parman, S. W.; Parmentier, E. M.; Wang, S.

2016-12-01

The crystallization of Mercury's magma ocean (MMO) would follow a significantly different path than the terrestrial or lunar magma ocean. Evidence from the MESSENGER mission [1] indicates that Mercury's interior has an oxygen fugacity (fO2) orders of magnitude lower any other terrestrial planet (3-8 log units below the iron-wustite buffer = IW-3 to IW-8; [2]). At these conditions, silicate melts and minerals have negligible Fe contents. All Fe is present in sulfides or metal. Thus, the build up of Fe in the last dregs of the lunar magma ocean, that is so important to its evolution, would not happen in the MMO. There would be no overturn or plagioclase flotation crust. Sulfur solubility in silicate melts increases dramatically at low fO2, from 1 wt% at IW-3 to 8wt% at IW-8 [3]. Thus it is possible, perhaps probable, that km-thick layers of sulfide formed during MMO crystallization. Some of the sulfides (e.g. CaS) have high partition coefficients for trace elements and so could control the spatial distribution of radioactive heat producing elements such as U, Th and K. This in turn would have first order effects on the thermal and chemical evolution of the planet. The distribution of the sulfide layers depend upon the density of the sulfides that form in the MMO. At such low fO2, S forms compounds with a range of elements not typical for other planets: Ca, Mg, Na, K. The densities of these sulfides vary widely, with Mg and Ca-rich sulfides being more dense than estimated MMO densities, and Na and K-rich sulfides being less dense than the MMO. Thus sulfide sinking and floating may produce substantial chemical layering on Mercury, potentially including an Mg-Ca rich deep layer and a Na-K rich shallow layer or possibly floatation crust. The total amount of S in the MMO depends on the fO2 and the bulk S content of Mercury, both of which are poorly constrained. In the most extreme case, if the MMO had an fO2of IW-8 and was sulfide saturated from the start, a total equivalent layer of sulfide up to 50 km could form (Figure 1). [1] Nittler et al (2011) Science 333: 847-1850., [2] Zolotov et al (2013), JGR 118: 138-146. [3] Berthet et al (2009) GCA 73: 6402-6420.

Analysis on the Oversize Blast Furnace Desulfurization and a Sulfide Capacity Prediction Model Based on Congregated Electron Phase

NASA Astrophysics Data System (ADS)

Zhenyang, Wang; Jianliang, Zhang; Gang, An; Zhengjian, Liu; Zhengming, Cheng; Junjie, Huang; Jingwei, Zhang

2016-02-01

Through analyzed and regressed the actual productive desulfurization data from the oversize blast furnace (5500 m3) in north China, the relationship between the sulfur distribution parameters and the slag composition in actual production situation was investigated. As the slag and hot metal phases have their own balance sulfur content or sulfur partial pressure in gas phase, respectively, the non-equilibrium of sulfur among gas, slag, and metal phases leads to the transmission and distribution of sulfur. Combined with sulfur transmission reactions between gas, slag and metal phases, C/CO pairs equilibrium, and Wagner model, the measured sulfide capacity can be acquired using sulfur distribution ratio, sulfur activity coefficient, and oxygen activity in hot metal. Based on the theory of congregated electron phase, a new sulfide capacity prediction model (CEPM) has been developed, which has a good liner relationship with the measured sulfide capacity. Thus, using the burden structure for BF, the ironmaking slag composition can be obtained simply and can be used to reliably predict the ironmaking slag desulfurization ability a few hours later after charging under a certain temperature by CEPM.

Diffusion coefficients of rare earth elements in fcc Fe: A first-principles study

NASA Astrophysics Data System (ADS)

Wang, Haiyan; Gao, Xueyun; Ren, Huiping; Chen, Shuming; Yao, Zhaofeng

2018-01-01

The diffusion data and corresponding detailed insights are particularly important for the understanding of the related kinetic processes in Fe based alloys, e.g. solute strengthening, phase transition, solution treatment etc. We present a density function theory study of the diffusivity of self and solutes (La, Ce, Y and Nb) in fcc Fe. The five-frequency model was employed to calculate the microscopic parameters in the correlation factors of the solute diffusion. The interactions of the solutes with the first nearest-neighbor vacancy (1nn) are all attractive, and can be well understood on the basis of the combination of the strain-relief effects and the electronic effects. It is found that among the investigated species, Ce is the fastest diffusing solute in fcc Fe matrix followed by Nb, and the diffusion coefficients of these two solutes are about an order of magnitude higher than that of Fe self-diffusion. And the results show that the diffusion coefficient of La is slightly higher than that of Y, and both species are comparable to that of Fe self-diffusion.

Analysis of diffusion and binding in cells using the RICS approach.

PubMed

Digman, Michelle A; Gratton, Enrico

2009-04-01

The movement of macromolecules in cells is assumed to occur either through active transport or by diffusion. However, the determination of the diffusion coefficients in cells using fluctuation methods or FRAP frequently give diffusion coefficient that are orders of magnitude smaller than the diffusion coefficients measured for the same macromolecule in solution. It is assumed that the cell internal viscosity is partially responsible for this decrease in the apparent diffusion. When the apparent diffusion is too slow to be due to cytoplasm viscosity, it is assumed that weak binding of the macromolecules to immobile or quasi immobile structures is taking place. In this article, we derive equations for fitting of the RICS (Raster-scan Image Correlations Spectroscopy) data in cells to a model that includes transient binding to immobile structures, and we show that under some conditions, the spatio-temporal correlation provided by the RICS approach can distinguish the process of diffusion and weak binding. We apply the method to determine the diffusion in the cytoplasm and binding of Focal Adhesion Kinase-EGFP to adhesions in MEF cells.

Backstepping-based boundary control design for a fractional reaction diffusion system with a space-dependent diffusion coefficient.

PubMed

Chen, Juan; Cui, Baotong; Chen, YangQuan

2018-06-11

This paper presents a boundary feedback control design for a fractional reaction diffusion (FRD) system with a space-dependent (non-constant) diffusion coefficient via the backstepping method. The contribution of this paper is to generalize the results of backstepping-based boundary feedback control for a FRD system with a space-independent (constant) diffusion coefficient to the case of space-dependent diffusivity. For the boundary stabilization problem of this case, a designed integral transformation treats it as a problem of solving a hyperbolic partial differential equation (PDE) of transformation's kernel, then the well posedness of the kernel PDE is solved for the plant with non-constant diffusivity. Furthermore, by the fractional Lyapunov stability (Mittag-Leffler stability) theory and the backstepping-based boundary feedback controller, the Mittag-Leffler stability of the closed-loop FRD system with non-constant diffusivity is proved. Finally, an extensive numerical example for this closed-loop FRD system with non-constant diffusivity is presented to verify the effectiveness of our proposed controller. Copyright © 2018 ISA. Published by Elsevier Ltd. All rights reserved.

Neutral solute transport across osteochondral interface: A finite element approach.

PubMed

Arbabi, Vahid; Pouran, Behdad; Weinans, Harrie; Zadpoor, Amir A

2016-12-08

Investigation of the solute transfer across articular cartilage and subchondral bone plate could nurture the understanding of the mechanisms of osteoarthritis (OA) progression. In the current study, we approached the transport of neutral solutes in human (slight OA) and equine (healthy) samples using both computed tomography and biphasic-solute finite element modeling. We developed a multi-zone biphasic-solute finite element model (FEM) accounting for the inhomogeneity of articular cartilage (superficial, middle and deep zones) and subchondral bone plate. Fitting the FEM model to the concentration-time curves of the cartilage and the equilibrium concentration of the subchondral plate/calcified cartilage enabled determination of the diffusion coefficients in the superficial, middle and deep zones of cartilage and subchondral plate. We found slightly higher diffusion coefficients for all zones in the human samples as compared to the equine samples. Generally the diffusion coefficient in the superficial zone of human samples was about 3-fold higher than the middle zone, the diffusion coefficient of the middle zone was 1.5-fold higher than that of the deep zone, and the diffusion coefficient of the deep zone was 1.5-fold higher than that of the subchondral plate/calcified cartilage. Those ratios for equine samples were 9, 2 and 1.5, respectively. Regardless of the species considered, there is a gradual decrease of the diffusion coefficient as one approaches the subchondral plate, whereas the rate of decrease is dependent on the type of species. Copyright © 2016 Elsevier Ltd. All rights reserved.

Mutual diffusion coefficients of heptane isomers in nitrogen: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Chae, Kyungchan; Violi, Angela

2011-01-01

The accurate knowledge of transport properties of pure and mixture fluids is essential for the design of various chemical and mechanical systems that include fluxes of mass, momentum, and energy. In this study we determine the mutual diffusion coefficients of mixtures composed of heptane isomers and nitrogen using molecular dynamics (MD) simulations with fully atomistic intermolecular potential parameters, in conjunction with the Green-Kubo formula. The computed results were compared with the values obtained using the Chapman-Enskog (C-E) equation with Lennard-Jones (LJ) potential parameters derived from the correlations of state values: MD simulations predict a maximum difference of 6% among isomers while the C-E equation presents that of 3% in the mutual diffusion coefficients in the temperature range 500-1000 K. The comparison of two approaches implies that the corresponding state principle can be applied to the models, which are only weakly affected by the anisotropy of the interaction potentials and the large uncertainty will be included in its application for complex polyatomic molecules. The MD simulations successfully address the pure effects of molecular structure among isomers on mutual diffusion coefficients by revealing that the differences of the total mutual diffusion coefficients for the six mixtures are caused mainly by heptane isomers. The cross interaction potential parameters, collision diameter σ _{12}, and potential energy well depth \\varepsilon _{12} of heptane isomers and nitrogen mixtures were also computed from the mutual diffusion coefficients.

Microscale diffusion measurements and simulation of a scaffold with a permeable strut.

PubMed

Lee, Seung Youl; Lee, Byung Ryong; Lee, Jongwan; Kim, Seongjun; Kim, Jung Kyung; Jeong, Young Hun; Jin, Songwan

2013-10-10

Electrospun nanofibrous structures provide good performance to scaffolds in tissue engineering. We measured the local diffusion coefficients of 3-kDa FITC-dextran in line patterns of electrospun nanofibrous structures fabricated by the direct-write electrospinning (DWES) technique using the fluorescence recovery after photobleaching (FRAP) method. No significant differences were detected between DWES line patterns fabricated with polymer supplied at flow rates of 0.1 and 0.5 mL/h. The oxygen diffusion coefficients of samples were estimated to be ~92%-94% of the oxygen diffusion coefficient in water based on the measured diffusion coefficient of 3-kDa FITC-dextran. We also simulated cell growth and distribution within spatially patterned scaffolds with struts consisting of either oxygen-permeable or non-permeable material. The permeable strut scaffolds exhibited enhanced cell growth. Saturated depths at which cells could grow to confluence were 15% deeper for the permeable strut scaffolds than for the non-permeable strut scaffold.

Determination of diffusion coefficient in disordered organic semiconductors

NASA Astrophysics Data System (ADS)

Rani, Varsha; Sharma, Akanksha; Ghosh, Subhasis

2016-05-01

Charge carrier transport in organic semiconductors is dominated by positional and energetic disorder in Gaussian density of states (GDOS) and is characterized by hopping through localized states. Due to the immobilization of charge carriers in these localized states, significant non-uniform carrier distribution exists, resulting diffusive transport. A simple, nevertheless powerful technique to determine diffusion coefficient D in disordered organic semiconductors has been presented. Diffusion coefficients of charge carriers in two technologically important organic molecular semiconductors, Pentacene and copper phthalocyanine (CuPc) have been measured from current-voltage (J-V) characteristics of Al/Pentacene/Au and Al/CuPc/Au based Schottky diodes. Ideality factor g and carrier mobility μ have been calculated from the exponential and space charge limited region respectively of J-V characteristics. Classical Einstein relation is not valid in organic semiconductors due to energetic disorders in DOS. Using generalized Einstein relation, diffusion coefficients have been obtained to be 1.31×10-6 and 1.73×10-7 cm2/s for Pentacene and CuPc respectively.

Transport coefficients in high-temperature ionized air flows with electronic excitation

NASA Astrophysics Data System (ADS)

Istomin, V. A.; Oblapenko, G. P.

2018-01-01

Transport coefficients are studied in high-temperature ionized air mixtures using the modified Chapman-Enskog method. The 11-component mixture N2/N2+/N /N+/O2/O2+/O /O+/N O /N O+/e- , taking into account the rotational and vibrational degrees of freedom of molecules and electronic degrees of freedom of both atomic and molecular species, is considered. Using the PAINeT software package, developed by the authors of the paper, in wide temperature range calculations of the thermal conductivity, thermal diffusion, diffusion, and shear viscosity coefficients for an equilibrium ionized air mixture and non-equilibrium flow conditions for mixture compositions, characteristic of those in shock tube experiments and re-entry conditions, are performed. For the equilibrium air case, the computed transport coefficients are compared to those obtained using simplified kinetic theory algorithms. It is shown that neglecting electronic excitation leads to a significant underestimation of the thermal conductivity coefficient at temperatures higher than 25 000 K. For non-equilibrium test cases, it is shown that the thermal diffusion coefficients of neutral species and the self-diffusion coefficients of all species are strongly affected by the mixture composition, while the thermal conductivity coefficient is most strongly influenced by the degree of ionization of the flow. Neglecting electronic excitation causes noticeable underestimation of the thermal conductivity coefficient at temperatures higher than 20 000 K.

METAL DIFFUSION IN SMOOTHED PARTICLE HYDRODYNAMICS SIMULATIONS OF DWARF GALAXIES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Williamson, David; Martel, Hugo; Kawata, Daisuke, E-mail: david-john.williamson.1@ulaval.ca

2016-05-10

We perform a series of smoothed particle hydrodynamics simulations of isolated dwarf galaxies to compare different metal mixing models. In particular, we examine the role of diffusion in the production of enriched outflows and in determining the metallicity distributions of gas and stars. We investigate different diffusion strengths by changing the pre-factor of the diffusion coefficient, by varying how the diffusion coefficient is calculated from the local velocity distribution, and by varying whether the speed of sound is included as a velocity term. Stronger diffusion produces a tighter [O/Fe]–[Fe/H] distribution in the gas and cuts off the gas metallicity distributionmore » function at lower metallicities. Diffusion suppresses the formation of low-metallicity stars, even with weak diffusion, and also strips metals from enriched outflows. This produces a remarkably tight correlation between “metal mass-loading” (mean metal outflow rate divided by mean metal production rate) and the strength of diffusion, even when the diffusion coefficient is calculated in different ways. The effectiveness of outflows at removing metals from dwarf galaxies and the metal distribution of the gas is thus dependent on the strength of diffusion. By contrast, we show that the metallicities of stars are not strongly dependent on the strength of diffusion, provided that some diffusion is present.« less

Comparisons among MRI signs, apparent diffusion coefficient, and fractional anisotropy in dogs with a solitary intracranial meningioma or histiocytic sarcoma.

PubMed

Wada, Masae; Hasegawa, Daisuke; Hamamoto, Yuji; Yu, Yoshihiko; Fujiwara-Igarashi, Aki; Fujita, Michio

2017-07-01

Although MRI has become widely used in small animal practice, little is known about the validity of advanced MRI techniques such as diffusion-weighted imaging and diffusion tensor imaging. The aim of this retrospective analytical observational study was to investigate the characteristics of diffusion parameters, that is the apparent diffusion coefficient and fractional anisotropy, in dogs with a solitary intracranial meningioma or histiocytic sarcoma. Dogs were included based on the performance of diffusion MRI and histological confirmation. Statistical analyses were performed to compare apparent diffusion coefficient and fractional anisotropy for the two types of tumor in the intra- and peritumoral regions. Eleven cases with meningioma and six with histiocytic sarcoma satisfied the inclusion criteria. Significant differences in apparent diffusion coefficient value (× 10 -3 mm 2 /s) between meningioma vs. histiocytic sarcoma were recognized in intratumoral small (1.07 vs. 0.76) and large (1.04 vs. 0.77) regions of interest, in the peritumoral margin (0.93 vs. 1.08), and in the T2 high region (1.21 vs. 1.41). Significant differences in fractional anisotropy values were found in the peritumoral margin (0.29 vs. 0.24) and the T2 high region (0.24 vs. 0.17). The current study identified differences in measurements of apparent diffusion coefficient and fractional anisotropy for meningioma and histiocytic sarcoma in a small sample of dogs. In addition, we observed that all cases of intracranial histiocytic sarcoma showed leptomeningeal enhancement and/or mass formation invading into the sulci in the contrast study. Future studies are needed to determine the sensitivity of these imaging characteristics for differentiating between these tumor types. © 2017 American College of Veterinary Radiology.

An improved procedure for determining grain boundary diffusion coefficients from averaged concentration profiles

NASA Astrophysics Data System (ADS)

Gryaznov, D.; Fleig, J.; Maier, J.

2008-03-01

Whipple's solution of the problem of grain boundary diffusion and Le Claire's relation, which is often used to determine grain boundary diffusion coefficients, are examined for a broad range of ratios of grain boundary to bulk diffusivities Δ and diffusion times t. Different reasons leading to errors in determining the grain boundary diffusivity (DGB) when using Le Claire's relation are discussed. It is shown that nonlinearities of the diffusion profiles in lnCav-y6/5 plots and deviations from "Le Claire's constant" (-0.78) are the major error sources (Cav=averaged concentration, y =coordinate in diffusion direction). An improved relation (replacing Le Claire's constant) is suggested for analyzing diffusion profiles particularly suited for small diffusion lengths (short times) as often required in diffusion experiments on nanocrystalline materials.

Diffusion kinetics of the glucose/glucose oxidase system in swift heavy ion track-based biosensors

NASA Astrophysics Data System (ADS)

Fink, Dietmar; Vacik, Jiri; Hnatowicz, V.; Muñoz Hernandez, G.; Garcia Arrelano, H.; Alfonta, Lital; Kiv, Arik

2017-05-01

For understanding of the diffusion kinetics and their optimization in swift heavy ion track-based biosensors, recently a diffusion simulation was performed. This simulation aimed at yielding the degree of enrichment of the enzymatic reaction products in the highly confined space of the etched ion tracks. A bunch of curves was obtained for the description of such sensors that depend only on the ratio of the diffusion coefficient of the products to that of the analyte within the tracks. As hitherto none of these two diffusion coefficients is accurately known, the present work was undertaken. The results of this paper allow one to quantify the previous simulation and hence yield realistic predictions of glucose-based biosensors. At this occasion, also the influence of the etched track radius on the diffusion coefficients was measured and compared with earlier prediction.

Measurement of shear-induced diffusion of red blood cells using dynamic light scattering-optical coherence tomography

NASA Astrophysics Data System (ADS)

Tang, Jianbo; Erdener, Sefik Evren; Li, Baoqiang; Fu, Buyin; Sakadzic, Sava; Carp, Stefan A.; Lee, Jonghwan; Boas, David A.

2018-02-01

Dynamic Light Scattering-Optical Coherence Tomography (DLS-OCT) takes the advantages of using DLS to measure particle flow and diffusion within an OCT resolution-constrained 3D volume, enabling the simultaneous measurements of absolute RBC velocity and diffusion coefficient with high spatial resolution. In this work, we applied DLS-OCT to measure both RBC velocity and the shear-induced diffusion coefficient within penetrating venules of the somatosensory cortex of anesthetized mice. Blood flow laminar profile measurements indicate a blunted laminar flow profile, and the degree of blunting decreases with increasing vessel diameter. The measured shear-induced diffusion coefficient was proportional to the flow shear rate with a magnitude of 0.1 to 0.5 × 10-6 mm2 . These results provide important experimental support for the recent theoretical explanation for why DCS is dominantly sensitive to RBC diffusive motion.

Comparison of nanoparticle diffusion using fluorescence correlation spectroscopy and differential dynamic microscopy within concentrated polymer solutions

NASA Astrophysics Data System (ADS)

Shokeen, Namita; Issa, Christopher; Mukhopadhyay, Ashis

2017-12-01

We studied the diffusion of nanoparticles (NPs) within aqueous entangled solutions of polyethylene oxide (PEO) by using two different optical techniques. Fluorescence correlation spectroscopy, a method widely used to investigate nanoparticle dynamics in polymer solution, was used to measure the long-time diffusion coefficient (D) of 25 nm radius particles within high molecular weight, Mw = 600 kg/mol PEO in water solutions. Differential dynamic microscopy (DDM) was used to determine the wave-vector dependent dynamics of NPs within the same polymer solutions. Our results showed good agreement between the two methods, including demonstration of normal diffusion and almost identical diffusion coefficients obtained by both techniques. The research extends the scope of DDM to study the dynamics and rheological properties of soft matter at a nanoscale. The measured diffusion coefficients followed a scaling theory, which can be explained by the coupling between polymer dynamics and NP motion.

The Steady-State Transport of Oxygen through Hemoglobin Solutions

PubMed Central

Keller, K. H.; Friedlander, S. K.

1966-01-01

The steady-state transport of oxygen through hemoglobin solutions was studied to identify the mechanism of the diffusion augmentation observed at low oxygen tensions. A novel technique employing a platinum-silver oxygen electrode was developed to measure the effective diffusion coefficient of oxygen in steady-state transport. The measurements were made over a wider range of hemoglobin and oxygen concentrations than previously reported. Values of the Brownian motion diffusion coefficient of oxygen in hemoglobin solution were obtained as well as measurements of facilitated transport at low oxygen tensions. Transport rates up to ten times greater than ordinary diffusion rates were found. Predictions of oxygen flux were made assuming that the oxyhemoglobin transport coefficient was equal to the Brownian motion diffusivity which was measured in a separate set of experiments. The close correlation between prediction and experiment indicates that the diffusion of oxyhemoglobin is the mechanism by which steady-state oxygen transport is facilitated. PMID:5943608

Exciton diffusion coefficient measurement in ZnO nanowires under electron beam irradiation.

PubMed

Donatini, Fabrice; Pernot, Julien

2018-03-09

In semiconductor nanowires (NWs) the exciton diffusion coefficient can be determined using a scanning electron microscope fitted with a cathodoluminescence system. High spatial and temporal resolution cathodoluminescence experiments are needed to measure independently the exciton diffusion length and lifetime in single NWs. However, both diffusion length and lifetime can be affected by the electron beam bombardment during observation and measurement. Thus, in this work the exciton lifetime in a ZnO NW is measured versus the electron beam dose (EBD) via a time-resolved cathodoluminescence experiment with a temporal resolution of 50 ps. The behavior of the measured exciton lifetime is consistent with our recent work on the EBD dependence of the exciton diffusion length in similar NWs investigated under comparable SEM conditions. Combining the two results, the exciton diffusion coefficient in ZnO is determined at room temperature and is found constant over the full span of EBD.

Lateral diffusion of proteins in the periplasm of Escherichia coli.

PubMed Central

Brass, J M; Higgins, C F; Foley, M; Rugman, P A; Birmingham, J; Garland, P B

1986-01-01

We have introduced biologically active, fluorescently labeled maltose-binding protein into the periplasmic space of Escherichia coli and measured its lateral diffusion coefficient by the fluorescence photobleaching recovery method. Diffusion of this protein in the periplasm was found to be surprisingly low (lateral diffusion coefficient, 0.9 X 10(-10) cm2 s-1), about 1,000-fold lower than would be expected for diffusion in aqueous medium and almost 100-fold lower than for an equivalent-size protein in the cytoplasm. Galactose-binding protein, myoglobin, and cytochrome c were also introduced into the periplasm and had diffusion coefficients identical to that determined for the maltose-binding protein. For all proteins nearly 100% recovery of fluorescence was obtained after photobleaching, indicating that the periplasm is a single contiguous compartment surrounding the cell. These data have considerable implications for periplasmic structure and for the role of periplasmic proteins in transport and chemotaxis. Images PMID:3005237

Complex Analysis of Diffusion Transport and Microstructure of an Intervertebral Disk.

PubMed

Byvaltsev, V A; Kolesnikov, S I; Belykh, E G; Stepanov, I A; Kalinin, A A; Bardonova, L A; Sudakov, N P; Klimenkov, I V; Nikiforov, S B; Semenov, A V; Perfil'ev, D V; Bespyatykh, I V; Antipina, S L; Giers, M; Prul, M

2017-12-01

We studied the relationship between diffusion transport and morphological and microstructural organization of extracellular matrix of human intervertebral disk. Specimens of the lumbar intervertebral disks without abnormalities were studied ex vivo by diffusion-weighed magnetic resonance imaging, histological and immunohistochemical methods, and electron microscopy. Distribution of the diffusion coefficient in various compartments of the intervertebral disk was studied. Significant correlations between diffusion coefficient and cell density in the nucleus pulposus, posterior aspects of annulus fibrosus, and endplate at the level of the posterior annulus fibrosus were detected for each disk. In disks with nucleus pulposus diffusion coefficient below 15×10 -4 mm 2 /sec, collagens X and XI were detected apart from aggrecan and collagens I and II. The results supplement the concept on the relationship between the microstructure and cell composition of various compartments of the intervertebral disk and parameters of nutrient transport.

Nature of self-diffusion in two-dimensional fluids

NASA Astrophysics Data System (ADS)

Choi, Bongsik; Han, Kyeong Hwan; Kim, Changho; Talkner, Peter; Kidera, Akinori; Lee, Eok Kyun

2017-12-01

Self-diffusion in a two-dimensional simple fluid is investigated by both analytical and numerical means. We investigate the anomalous aspects of self-diffusion in two-dimensional fluids with regards to the mean square displacement, the time-dependent diffusion coefficient, and the velocity autocorrelation function (VACF) using a consistency equation relating these quantities. We numerically confirm the consistency equation by extensive molecular dynamics simulations for finite systems, corroborate earlier results indicating that the kinematic viscosity approaches a finite, non-vanishing value in the thermodynamic limit, and establish the finite size behavior of the diffusion coefficient. We obtain the exact solution of the consistency equation in the thermodynamic limit and use this solution to determine the large time asymptotics of the mean square displacement, the diffusion coefficient, and the VACF. An asymptotic decay law of the VACF resembles the previously known self-consistent form, 1/(t\\sqrt{{ln}t}), however with a rescaled time.

Influence of Hydrogen Sulfide Exposure on the Transport and Structural Properties of the Metal–Organic Framework ZIF-8

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dutta, Akshita; Tymi?ska, Nina; Zhu, Guanghui

In this paper, the interaction between hydrogen sulfide and ZIF-8 was studied via structural characterizations and guest molecule diffusion measurements. It was found that hydrogen sulfide reacts with the ZIF-8 external particle surface to form a surface barrier that excludes the uptake of larger molecules (ethanol) and slows down the uptake of smaller molecules (carbon dioxide). Nonetheless, bulk transport properties were unaltered, as supported by pulsed field gradient nuclear magnetic resonance studies. Dispersion-corrected density functional theory calculations revealed that H 2S is consumed by reactions occurring at the ZIF external surface. These reactions result in water and defect formation, bothmore » of which were found to be exothermic and independent of both crystallographic facets ({001} and {110}) and surface termination. Finally, we concluded that these surface reactions lead to structural and chemical changes to the ZIF-8 external surface that generate surface barriers to molecular transport.« less

Dynamic characteristics of sulfur, iron and phosphorus in coastal polluted sediments, north China.

PubMed

Sun, Qiyao; Sheng, Yanqing; Yang, Jian; Di Bonito, Marcello; Mortimer, Robert J G

2016-12-01

The cycling of sulfur (S), iron (Fe) and phosphorus (P) in sediments and pore water can impact the water quality of overlying water. In a heavily polluted river estuary (Yantai, China), vertical profiles of fluxes of dissolved sulfide, Fe 2+ and dissolved reactive phosphorus (DRP) in sediment pore water were investigated by the Diffusive Gradients in Thin films technique (DGT). Vertical fluxes of S, Fe, P in intertidal sediment showed the availability of DRP increased while the sulfide decreased with depth in surface sediment, indicating that sulfide accumulation could enhance P release in anoxic sediment. In sites with contrasting salinity, the relative dominance of iron and sulfate reduction was different, with iron reduction dominant over sulfate reduction in the upper sediment at an intertidal site but the reverse true in a freshwater site, with the other process dominating at depth in each case. Phosphate release was largely controlled by iron reduction. Copyright © 2016 Elsevier Ltd. All rights reserved.

Influence of Hydrogen Sulfide Exposure on the Transport and Structural Properties of the Metal–Organic Framework ZIF-8

DOE PAGES

Dutta, Akshita; Tymi?ska, Nina; Zhu, Guanghui; ...

2018-03-09

In this paper, the interaction between hydrogen sulfide and ZIF-8 was studied via structural characterizations and guest molecule diffusion measurements. It was found that hydrogen sulfide reacts with the ZIF-8 external particle surface to form a surface barrier that excludes the uptake of larger molecules (ethanol) and slows down the uptake of smaller molecules (carbon dioxide). Nonetheless, bulk transport properties were unaltered, as supported by pulsed field gradient nuclear magnetic resonance studies. Dispersion-corrected density functional theory calculations revealed that H 2S is consumed by reactions occurring at the ZIF external surface. These reactions result in water and defect formation, bothmore » of which were found to be exothermic and independent of both crystallographic facets ({001} and {110}) and surface termination. Finally, we concluded that these surface reactions lead to structural and chemical changes to the ZIF-8 external surface that generate surface barriers to molecular transport.« less

Interfacial Mechanism in Lithium-Sulfur Batteries: How Salts Mediate the Structure Evolution and Dynamics.

PubMed

Lang, Shuang-Yan; Xiao, Rui-Juan; Gu, Lin; Guo, Yu-Guo; Wen, Rui; Wan, Li-Jun

2018-06-08

Lithium-sulfur batteries possess favorable potential for energy-storage applications due to their high specific capacity and the low cost of sulfur. Intensive understanding of the interfacial mechanism, especially the polysulfide formation and transformation under complex electrochemical environment, is crucial for the build-up of advanced batteries. Here we report the direct visualization of interfacial evolution and dynamic transformation of the sulfides mediated by the lithium salts via real-time atomic force microscopy monitoring inside a working battery. The observations indicate that the lithium salts influence the structures and processes of sulfide deposition/decomposition during discharge/charge. Moreover, the distinct ion interaction and diffusion in electrolytes manipulate the interfacial reactions determining the kinetics of the sulfide transformation. Our findings provide deep insights into surface dynamics of lithium-sulfur reactions revealing the salt-mediated mechanisms at nanoscale, which contribute to the profound understanding of the interfacial processes for the optimized design of lithium-sulfur batteries.

Hydrogen sulfide capture by limestone and dolomite at elevated pressure. 2: Sorbent particle conversion modeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zevenhoven, C.A.P.; Yrjas, K.P.; Hupa, M.M.

1996-03-01

The physical structure of a limestone or dolomite to be used in in-bed sulfur capture in fluidized bed gasifiers has a great impact on the efficiency of sulfur capture and sorbent use. In this study an unreacted shrinking core model with variable effective diffusivity is applied to sulfidation test data from a pressurized thermogravimetric apparatus (P-TGA) for a set of physically and chemically different limestone and dolomite samples. The particle size was 250--300 {micro}m for all sorbents, which were characterized by chemical composition analysis, particle density measurement, mercury porosimetry, and BET internal surface measurement. Tests were done under typical conditionsmore » for a pressurized fluidized-bed gasifier, i.e., 20% CO{sub 2}, 950 C, 20 bar. At these conditions the limestone remains uncalcined, while the dolomite is half-calcined. Additional tests were done at low CO{sub 2} partial pressures, yielding calcined limestone and fully calcined dolomite. The generalized model allows for determination of values for the initial reaction rate and product layer diffusivity.« less

An inverse moisture diffusion algorithm for the determination of diffusion coefficient

Treesearch

Jen Y. Liu; William T. Simpson; Steve P. Verrill

2000-01-01

The finite difference approximation is applied to estimate the moisture-dependent diffusion coefficient by utilizing test data of isothermal moisture desorption in northern red oak (Quercus rubra). The test data contain moisture distributions at discrete locations across the thickness of specimens, which coincides with the radial direction of northern red oak, and at...

An inverse moisture diffusion algorithm for the determination of diffusion coefficient

Treesearch

Jen Y. Liu; William T. Simpson; Steve P. Verrill

2001-01-01

The finite difference approximation is applied to estimate the moisture-dependent diffusion coefficient by utilizing test data of isothermal moisture desorption in northern red oak (Quercus rubra). The test data contain moisture distributions at discrete locations across the thickness of specimens, which coincides with the radial direction of northern red oak, and at...

Correlation Between Minimum Apparent Diffusion Coefficient (ADCmin) and Tumor Cellularity: A Meta-analysis.

PubMed

Surov, Alexey; Meyer, Hans Jonas; Wienke, Andreas

2017-07-01

Diffusion-weighted imaging (DWI) is a magnetic resonance imaging (MRI) technique based on measure of water diffusion that can provide information about tissue microstructure, especially about cell count. Increase of cell density induces restriction of water diffusion and decreases apparent diffusion coefficient (ADC). ADC can be divided into three sub-parameters: ADC minimum or ADC min , mean ADC or ADC mean and ADC maximum or ADC max Some studies have suggested that ADC min shows stronger correlations with cell count in comparison to other ADC fractions and may be used as a parameter for estimation of tumor cellularity. The aim of the present meta-analysis was to summarize correlation coefficients between ADC min and cellularity in different tumors based on large patient data. For this analysis, MEDLINE database was screened for associations between ADC and cell count in different tumors up to September 2016. For this work, only data regarding ADC min were included. Overall, 12 publications with 317 patients were identified. Spearman's correlation coefficient was used to analyze associations between ADC min and cellularity. The reported Pearson correlation coefficients in some publications were converted into Spearman correlation coefficients. The pooled correlation coefficient for all included studies was ρ=-0.59 (95% confidence interval (CI)=-0.72 to -0.45), heterogeneity Tau 2 =0.04 (p<0.0001), I 2 =73%, test for overall effect Z=8.67 (p<0.00001). ADC min correlated moderately with tumor cellularity. The calculated correlation coefficient is not stronger in comparison to the reported coefficient for ADC mean and, therefore, ADC min does not represent a better means to reflect cellularity. Copyright© 2017, International Institute of Anticancer Research (Dr. George J. Delinasios), All rights reserved.

Molecular dynamics simulation of imidazolium-based ionic liquids. I. Dynamics and diffusion coefficient.

PubMed

Kowsari, M H; Alavi, Saman; Ashrafizaadeh, Mahmud; Najafi, Bijan

2008-12-14

Molecular dynamics simulations are used to study the dynamics and transport properties of 12 room-temperature ionic liquids of the 1-alkyl-3-methylimidazolium [amim](+) (alkyl = methyl, ethyl, propyl, and butyl) family with PF(6)(-), NO(3)(-), and Cl(-) counterions. The explicit atom transferable force field of Canongia Lopes et al. [J. Phys. Chem. B 108, 2038 (2004)] is used in the simulations. In this first part, the dynamics of the ionic liquids are characterized by studying the mean-square displacement (MSD) and the velocity autocorrelation function (VACF) for the centers of mass of the ions at 400 K. Trajectory averaging was employed to evaluate the diffusion coefficients at two temperatures from the linear slope of MSD(t) functions in the range of 150-300 ps and from the integration of the VACF(t) functions at 400 K. Detailed comparisons are made between the diffusion results from the MSD and VACF methods. The diffusion coefficients from the integration of the VACFs are closer to experimental values than the diffusion coefficients calculated from the slope of MSDs. Both methods can show good agreement with experiment in predicting relative trends in the diffusion coefficients and determining the role of the cation and anion structures on the dynamical behavior of this family of ionic liquids. The MSD and self-diffusion of relatively heavier imidazolium cations are larger than those of the lighter anions from the Einstein results, except for the case of [bmim][Cl]. The cationic transference number generally decreases with temperature, in good agreement with experiments. For the same anion, the cationic transference numbers decrease with increasing length of the alkyl chain, and for the same cation, the trends in the cationic transference numbers are [NO(3)](-) < [Cl](-) < [PF(6)](-). The trends in the diffusion coefficient in the series of cations with identical anions are [emim](+) > [pmim](+) > [bmim](+) and those for anions with identical cations are [NO(3)](-) > [PF(6)](-) > [Cl](-). The [dmim](+) has a relatively low diffusion coefficient due to its symmetric structure and good packing in the liquid phase. The major factor for determining the magnitude of the self-diffusion is the geometric shape of the anion of the ionic liquid. Other important factors are the ion size and the charge delocalization in the anion.

Mass diffusion coefficient measurement for vitreous humor using FEM and MRI

NASA Astrophysics Data System (ADS)

Rattanakijsuntorn, Komsan; Penkova, Anita; Sadha, Satwindar S.

2018-01-01

In early studies, the ‘contour method’ for determining the diffusion coefficient of the vitreous humor was developed. This technique relied on careful injection of an MRI contrast agent (surrogate drug) into the vitreous humor of fresh bovine eyes, and tracking the contours of the contrast agent in time. In addition, an analytical solution was developed for the theoretical contours built on point source model for the injected surrogate drug. The match between theoretical and experimental contours as a least square fit, while floating the diffusion coefficient, led to the value of the diffusion coefficient. This method had its limitation that the initial injection of the surrogate had to be spherical or ellipsoidal because of the analytical result based on the point-source model. With a new finite element model for the analysis in this study, the technique is much less restrictive and handles irregular shapes of the initial bolus. The fresh bovine eyes were used for drug diffusion study in the vitreous and three contrast agents of different molecular masses: gadolinium-diethylenetriaminepentaacetic acid (Gd-DTPA, 938 Da), non-ionic gadoteridol (Prohance, 559 Da), and bovine albumin conjugated with gadolinium (Galbumin, 74 kDa) were used as drug surrogates to visualize the diffusion process by MRI. The 3D finite element model was developed to determine the diffusion coefficients of these surrogates with the images from MRI. This method can be used for other types of bioporous media provided the concentration profile can be visualized (by methods such as MRI or fluorescence).

New sensitive micro-measurements of dynamic surface tension and diffusion coefficients: Validated and tested for the adsorption of 1-Octanol at a microscopic air-water interface and its dissolution into water.

PubMed

Kinoshita, Koji; Parra, Elisa; Needham, David

2017-02-15

Currently available dynamic surface tension (DST) measurement methods, such as Wilhelmy plate, droplet- or bubble-based methods, still have various experimental limitations such as the large size of the interface, convection in the solution, or a certain "dead time" at initial measurement. These limitations create inconsistencies for the kinetic analysis of surfactant adsorption/desorption, especially significant for ionic surfactants. Here, the "micropipette interfacial area-expansion method" was introduced and validated as a new DST measurement having a high enough sensitivity to detect diffusion controlled molecular adsorption at the air-water interfaces. To validate the new technique, the diffusion coefficient of 1-Octanol in water was investigated with existing models: the Ward Tordai model for the long time adsorption regime (1-100s), and the Langmuir and Frumkin adsorption isotherm models for surface excess concentration. We found that the measured diffusion coefficient of 1-Octanol, 7.2±0.8×10 -6 cm 2 /s, showed excellent agreement with the result from an alternative method, "single microdroplet catching method", to measure the diffusion coefficient from diffusion-controlled microdroplet dissolution, 7.3±0.1×10 -6 cm 2 /s. These new techniques for determining adsorption and diffusion coefficients can apply for a range of surface active molecules, especially the less-characterized ionic surfactants, and biological compounds such as lipids, peptides, and proteins. Copyright © 2016 Elsevier Inc. All rights reserved.

Anomalous diffusion and scaling in coupled stochastic processes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bel, Golan; Nemenman, Ilya

2009-01-01

Inspired by problems in biochemical kinetics, we study statistical properties of an overdamped Langevin processes with the friction coefficient depending on the state of a similar, unobserved, process. Integrating out the latter, we derive the Pocker-Planck the friction coefficient of the first depends on the state of the second. Integrating out the latter, we derive the Focker-Planck equation for the probability distribution of the former. This has the fonn of diffusion equation with time-dependent diffusion coefficient, resulting in an anomalous diffusion. The diffusion exponent can not be predicted using a simple scaling argument, and anomalous scaling appears as well. Themore » diffusion exponent of the Weiss-Havlin comb model is derived as a special case, and the same exponent holds even for weakly coupled processes. We compare our theoretical predictions with numerical simulations and find an excellent agreement. The findings caution against treating biochemical systems with unobserved dynamical degrees of freedom by means of standandard, diffusive Langevin descritpion.« less

Influence of structure properties on protein-protein interactions-QSAR modeling of changes in diffusion coefficients.

PubMed

Bauer, Katharina Christin; Hämmerling, Frank; Kittelmann, Jörg; Dürr, Cathrin; Görlich, Fabian; Hubbuch, Jürgen

2017-04-01

Information about protein-protein interactions provides valuable knowledge about the phase behavior of protein solutions during the biopharmaceutical production process. Up to date it is possible to capture their overall impact by an experimentally determined potential of mean force. For the description of this potential, the second virial coefficient B22, the diffusion interaction parameter kD, the storage modulus G', or the diffusion coefficient D is applied. In silico methods do not only have the potential to predict these parameters, but also to provide deeper understanding of the molecular origin of the protein-protein interactions by correlating the data to the protein's three-dimensional structure. This methodology furthermore allows a lower sample consumption and less experimental effort. Of all in silico methods, QSAR modeling, which correlates the properties of the molecule's structure with the experimental behavior, seems to be particularly suitable for this purpose. To verify this, the study reported here dealt with the determination of a QSAR model for the diffusion coefficient of proteins. This model consisted of diffusion coefficients for six different model proteins at various pH values and NaCl concentrations. The generated QSAR model showed a good correlation between experimental and predicted data with a coefficient of determination R2 = 0.9 and a good predictability for an external test set with R2 = 0.91. The information about the properties affecting protein-protein interactions present in solution was in agreement with experiment and theory. Furthermore, the model was able to give a more detailed picture of the protein properties influencing the diffusion coefficient and the acting protein-protein interactions. Biotechnol. Bioeng. 2017;114: 821-831. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Multiple-scattering coefficients and absorption controlled diffusive processes

NASA Astrophysics Data System (ADS)

Godoy, Salvador; García-Colín, L. S.; Micenmacher, Victor

1999-11-01

Multiple-scattering transmission and reflection coefficients (T,R) are introduced in addition to the diffusion coefficient D for the description of ballistic diffusion in the presence of absorption. For 1D (one-dimensional) systems, the measurement of only one between T and D imposes restrictions on the possible values of the other. If D is measured, then T is bounded between the Landauer and Lambert-Beer equations. Measurements of both (T,D) imply the theoretical knowledge of the microscopic absorption Σa and scattering rΣs cross sections.

Calibration-free concentration analysis for an analyte prone to self-association.

PubMed

Imamura, Hiroshi; Honda, Shinya

2017-01-01

Calibration-free concentration analysis (CFCA) based on surface plasmon resonance uses the diffusion coefficient of an analyte to determine the concentration of that analyte in a bulk solution. In general, CFCA is avoided when investigating analytes prone to self-association, as the heterogeneous diffusion coefficient results in a loss of precision. The derivation for self-association of the analyte was presented here. By using the diffusion coefficient for the monomeric state, CFCA provides the lowest possible concentration even though the analyte is self-associated. Copyright © 2016 Elsevier Inc. All rights reserved.

A novel method for effective diffusion coefficient measurement in gas diffusion media of polymer electrolyte fuel cells

NASA Astrophysics Data System (ADS)

Yang, Linlin; Sun, Hai; Fu, Xudong; Wang, Suli; Jiang, Luhua; Sun, Gongquan

2014-07-01

A novel method for measuring effective diffusion coefficient of porous materials is developed. The oxygen concentration gradient is established by an air-breathing proton exchange membrane fuel cell (PEMFC). The porous sample is set in a sample holder located in the cathode plate of the PEMFC. At a given oxygen flux, the effective diffusion coefficients are related to the difference of oxygen concentration across the samples, which can be correlated with the differences of the output voltage of the PEMFC with and without inserting the sample in the cathode plate. Compared to the conventional electrical conductivity method, this method is more reliable for measuring non-wetting samples.

Critical role for mesoscale eddy diffusion in supplying oxygen to hypoxic ocean waters

NASA Astrophysics Data System (ADS)

Gnanadesikan, Anand; Bianchi, Daniele; Pradal, Marie-Aude

2013-10-01

of the oceanic lateral eddy diffusion coefficient Aredi vary by more than an order of magnitude, ranging from less than a few hundred m2/s to thousands of m2/s. This uncertainty has first-order implications for the intensity of oceanic hypoxia, which is poorly simulated by the current generation of Earth System Models. Using satellite-based estimate of oxygen consumption in hypoxic waters to estimate the required diffusion coefficient for these waters gives a value of order 1000 m2/s. Varying Aredi across a suite of Earth System Models yields a broadly consistent result given a thermocline diapycnal diffusion coefficient of 1 × 10-5 m2/s.

Lateral mobility of plasma membrane proteins in dividing eggs of the loach (Misgurnus fossilis): Regional differences and changes during the cell cycle.

PubMed

Bozhkova, V P; Budayova, M; Kvasnicka, P; Cigankova, N; Chorvat, D

1994-12-01

Regional differences in lateral diffusion rates of fluorescence-labeled proteins have been studied in the plasma membrane of dividing eggs of the loach (Misgurnus fossilis) by fluorescence recovery after photobleaching (FRAP). Apparent animal-vegetal differences in fluorescence intensity, lateral diffusion coefficients, and fractions of mobile proteins have been found, with all these quantities being higher in the animal pole region than in the yolk region. Cyclic changes in protein diffusion coefficients and mobile fractions during the first few cell cycles have also been recorded. Soon after the end of a cleavage, the diffusion coefficient reaches its minimal value and increases rapidly before the next cleavage.

Hybrid diffusion-P3 equation in N-layered turbid media: steady-state domain.

PubMed

Shi, Zhenzhi; Zhao, Huijuan; Xu, Kexin

2011-10-01

This paper discusses light propagation in N-layered turbid media. The hybrid diffusion-P3 equation is solved for an N-layered finite or infinite turbid medium in the steady-state domain for one point source using the extrapolated boundary condition. The Fourier transform formalism is applied to derive the analytical solutions of the fluence rate in Fourier space. Two inverse Fourier transform methods are developed to calculate the fluence rate in real space. In addition, the solutions of the hybrid diffusion-P3 equation are compared to the solutions of the diffusion equation and the Monte Carlo simulation. For the case of small absorption coefficients, the solutions of the N-layered diffusion equation and hybrid diffusion-P3 equation are almost equivalent and are in agreement with the Monte Carlo simulation. For the case of large absorption coefficients, the model of the hybrid diffusion-P3 equation is more precise than that of the diffusion equation. In conclusion, the model of the hybrid diffusion-P3 equation can replace the diffusion equation for modeling light propagation in the N-layered turbid media for a wide range of absorption coefficients.

Wanted: Scalable Tracers for Diffusion Measurements

PubMed Central

2015-01-01

Scalable tracers are potentially a useful tool to examine diffusion mechanisms and to predict diffusion coefficients, particularly for hindered diffusion in complex, heterogeneous, or crowded systems. Scalable tracers are defined as a series of tracers varying in size but with the same shape, structure, surface chemistry, deformability, and diffusion mechanism. Both chemical homology and constant dynamics are required. In particular, branching must not vary with size, and there must be no transition between ordinary diffusion and reptation. Measurements using scalable tracers yield the mean diffusion coefficient as a function of size alone; measurements using nonscalable tracers yield the variation due to differences in the other properties. Candidate scalable tracers are discussed for two-dimensional (2D) diffusion in membranes and three-dimensional diffusion in aqueous solutions. Correlations to predict the mean diffusion coefficient of globular biomolecules from molecular mass are reviewed briefly. Specific suggestions for the 3D case include the use of synthetic dendrimers or random hyperbranched polymers instead of dextran and the use of core–shell quantum dots. Another useful tool would be a series of scalable tracers varying in deformability alone, prepared by varying the density of crosslinking in a polymer to make say “reinforced Ficoll” or “reinforced hyperbranched polyglycerol.” PMID:25319586

Diffusion measurement from observed transverse beam echoes

DOE PAGES

Sen, Tanaji; Fischer, Wolfram

2017-01-09

For this research, we study the measurement of transverse diffusion through beam echoes. We revisit earlier observations of echoes in RHIC and apply an updated theoretical model to these measurements. We consider three possible models for the diffusion coefficient and show that only one is consistent with measured echo amplitudes and pulse widths. This model allows us to parameterize the diffusion coefficients as functions of bunch charge. We demonstrate that echoes can be used to measure diffusion much quicker than present methods and could be useful to a variety of hadron synchrotrons.

Random diffusion and leverage effect in financial markets.

PubMed

Perelló, Josep; Masoliver, Jaume

2003-03-01

We prove that Brownian market models with random diffusion coefficients provide an exact measure of the leverage effect [J-P. Bouchaud et al., Phys. Rev. Lett. 87, 228701 (2001)]. This empirical fact asserts that past returns are anticorrelated with future diffusion coefficient. Several models with random diffusion have been suggested but without a quantitative study of the leverage effect. Our analysis lets us to fully estimate all parameters involved and allows a deeper study of correlated random diffusion models that may have practical implications for many aspects of financial markets.

Nonlinear optical properties of hybridized CdS/ZnS-PVP sols

NASA Astrophysics Data System (ADS)

Kulagina, A. S.; Evstropiev, S. K.; Khrebtov, A. I.

2017-11-01

Hybrid composites of CdS-core ZnS-shell nanoparticles embedded in polyvinylpyrrolidone (PVP) matrixes have been prepared and characterized. Cadmium sulfide (CdS) nanocrystals were grown in water-propanol-2 solutions containing high-molecular (Ms=1300000) polyvinylpyrrolidone (PVP) at room temperature using cadmium nitrate and sodium sulfide as the cadmium and sulfur sources, respectively. The CdS/ZnS-PVP suspensions have promising optical properties for nanocomposite films based on. Nonlinear optical properties of diluted CdS/ZnS sols were studied at 532 nm and 5 ns laser pulses by using the Z-scan technique. Dependence of the nonlinear-optical coefficients on the CdS weight has been obtained.

Comparison of the Radiative Two-Flux and Diffusion Approximations

NASA Technical Reports Server (NTRS)

Spuckler, Charles M.

2006-01-01

Approximate solutions are sometimes used to determine the heat transfer and temperatures in a semitransparent material in which conduction and thermal radiation are acting. A comparison of the Milne-Eddington two-flux approximation and the diffusion approximation for combined conduction and radiation heat transfer in a ceramic material was preformed to determine the accuracy of the diffusion solution. A plane gray semitransparent layer without a substrate and a non-gray semitransparent plane layer on an opaque substrate were considered. For the plane gray layer the material is semitransparent for all wavelengths and the scattering and absorption coefficients do not vary with wavelength. For the non-gray plane layer the material is semitransparent with constant absorption and scattering coefficients up to a specified wavelength. At higher wavelengths the non-gray plane layer is assumed to be opaque. The layers are heated on one side and cooled on the other by diffuse radiation and convection. The scattering and absorption coefficients were varied. The error in the diffusion approximation compared to the Milne-Eddington two flux approximation was obtained as a function of scattering coefficient and absorption coefficient. The percent difference in interface temperatures and heat flux through the layer obtained using the Milne-Eddington two-flux and diffusion approximations are presented as a function of scattering coefficient and absorption coefficient. The largest errors occur for high scattering and low absorption except for the back surface temperature of the plane gray layer where the error is also larger at low scattering and low absorption. It is shown that the accuracy of the diffusion approximation can be improved for some scattering and absorption conditions if a reflectance obtained from a Kubelka-Munk type two flux theory is used instead of a reflection obtained from the Fresnel equation. The Kubelka-Munk reflectance accounts for surface reflection and radiation scattered back by internal scattering sites while the Fresnel reflection only accounts for surface reflections.

Non-destructive testing method for determining the solvent diffusion coefficient in the porous materials products

NASA Astrophysics Data System (ADS)

Belyaev, V. P.; Mishchenko, S. V.; Belyaev, P. S.

2018-01-01

Ensuring non-destructive testing of products in industry is an urgent task. Most of the modern methods for determining the diffusion coefficient in porous materials have been developed for bodies of a given configuration and size. This leads to the need for finished products destruction to make experimental samples from them. The purpose of this study is the development of a dynamic method that allows operatively determine the diffusion coefficient in finished products from porous materials without destroying them. The method is designed to investigate the solvents diffusion coefficient in building constructions from materials having a porous structure: brick, concrete and aerated concrete, gypsum, cement, gypsum or silicate solutions, gas silicate blocks, heat insulators, etc. A mathematical model of the method is constructed. The influence of the design and measuring device operating parameters on the method accuracy is studied. The application results of the developed method for structural porous products are presented.

Identification of diffusive transport properties of poly(vinyl alcohol) hydrogels from reservoir test.

PubMed

Kazimierska-Drobny, Katarzyna; Kaczmarek, Mariusz

2013-12-01

In this paper the identification of diffusion coefficient, retardation factor and surface distribution coefficient for selected salts in poly(vinyl alcohol) hydrogels is performed. The identification of the transport parameters is based on the previously developed inverse problem technique using experimental data from the reservoir test and the solution of the diffusive transport equation with linear equilibrium sorption. The estimated values of diffusion coefficient are: for physiological fluid (6.30±0.10)×10(-10) m(2)/s, for 1 M NaCl (6.42±0.39)×10(-10) m(2)/s, and for 1 M KCl (7.94±0.38)×10(-10) m(2)/s. The retardation factor for all tested materials and salts is equal or close to one. The average value of the effective surface distribution coefficient is equal to 0.5. © 2013 Elsevier B.V. All rights reserved.

Diffusion and Electric Mobility of KCI within Isolated Cuticles of Citrus aurantium 1

PubMed Central

Tyree, Melvin T.; Wescott, Charles R.; Tabor, Christopher A.; Morse, Anne D.

1992-01-01

Fick's second law has been used to predict the time course of electrical conductance change in isolated cuticles following the rapid change in bathing solution (KCI) from concentration C to 0.1 C. The theoretical time course is dependent on the coefficient of diffusion of KCI in the cuticle and the cuticle thickness. Experimental results, obtained from cuticles isolated from sour orange (Citrus aurantium), fit with a diffusion model of an isolated cuticle in which about 90% of the conductance change following a solution change is due to salts diffusing from polar pores in the wax, and 10% of the change is due to salt diffusion from the wax. Short and long time constants for the washout of KCI were found to be 0.11 and 3.8 hours, respectively. These time constants correspond to KCI diffusion coefficients of 1 × 10−15 and 3 × 10−17 square meters per second, respectively. The larger coefficient is close to the diffusion coefficient for water in polar pores of Citrus reported elsewhere (M Becker, G Kerstiens, J Schönherr [1986] Trees 1: 54-60). This supports our interpretation of the washout kinetics of KCI following a change in concentration of bathing solution. PMID:16668971

A diffusivity model for predicting VOC diffusion in porous building materials based on fractal theory.

PubMed

Liu, Yanfeng; Zhou, Xiaojun; Wang, Dengjia; Song, Cong; Liu, Jiaping

2015-12-15

Most building materials are porous media, and the internal diffusion coefficients of such materials have an important influences on the emission characteristics of volatile organic compounds (VOCs). The pore structure of porous building materials has a significant impact on the diffusion coefficient. However, the complex structural characteristics bring great difficulties to the model development. The existing prediction models of the diffusion coefficient are flawed and need to be improved. Using scanning electron microscope (SEM) observations and mercury intrusion porosimetry (MIP) tests of typical porous building materials, this study developed a new diffusivity model: the multistage series-connection fractal capillary-bundle (MSFC) model. The model considers the variable-diameter capillaries formed by macropores connected in series as the main mass transfer paths, and the diameter distribution of the capillary bundles obeys a fractal power law in the cross section. In addition, the tortuosity of the macrocapillary segments with different diameters is obtained by the fractal theory. Mesopores serve as the connections between the macrocapillary segments rather than as the main mass transfer paths. The theoretical results obtained using the MSFC model yielded a highly accurate prediction of the diffusion coefficients and were in a good agreement with the VOC concentration measurements in the environmental test chamber. Copyright © 2015 Elsevier B.V. All rights reserved.

Boron diffusion in bcc-Fe studied by first-principles calculations

NASA Astrophysics Data System (ADS)

Xianglong, Li; Ping, Wu; Ruijie, Yang; Dan, Yan; Sen, Chen; Shiping, Zhang; Ning, Chen

2016-03-01

The diffusion mechanism of boron in bcc-Fe has been studied by first-principles calculations. The diffusion coefficients of the interstitial mechanism, the B-monovacancy complex mechanism, and the B-divacancy complex mechanism have been calculated. The calculated diffusion coefficient of the interstitial mechanism is D0 = 1.05 × 10-7 exp (-0.75 eV/kT) m2 · s-1, while the diffusion coefficients of the B-monovacancy and the B-divacancy complex mechanisms are D1 = 1.22 × 10-6 f1 exp (-2.27 eV/kT) m2 · s-1 and D2 ≈ 8.36 × 10-6 exp (-4.81 eV/kT) m2 · s-1, respectively. The results indicate that the dominant diffusion mechanism in bcc-Fe is the interstitial mechanism through an octahedral interstitial site instead of the complex mechanism. The calculated diffusion coefficient is in accordance with the reported experiment results measured in Fe-3%Si-B alloy (bcc structure). Since the non-equilibrium segregation of boron is based on the diffusion of the complexes as suggested by the theory, our calculation reasonably explains why the non-equilibrium segregation of boron is not observed in bcc-Fe in experiments. Project supported by the National Natural Science Foundation of China (Grant No. 51276016) and the National Basic Research Program of China (Grant No. 2012CB720406).

Transfer coefficients in ultracold strongly coupled plasma

NASA Astrophysics Data System (ADS)

Bobrov, A. A.; Vorob'ev, V. S.; Zelener, B. V.

2018-03-01

We use both analytical and molecular dynamic methods for electron transfer coefficients in an ultracold plasma when its temperature is small and the coupling parameter characterizing the interaction of electrons and ions exceeds unity. For these conditions, we use the approach of nearest neighbor to determine the average electron (ion) diffusion coefficient and to calculate other electron transfer coefficients (viscosity and electrical and thermal conductivities). Molecular dynamics simulations produce electronic and ionic diffusion coefficients, confirming the reliability of these results. The results compare favorably with experimental and numerical data from earlier studies.

Response of radiation belt simulations to different radial diffusion coefficients for relativistic and ultra-relativistic electrons

NASA Astrophysics Data System (ADS)

Drozdov, Alexander; Mann, Ian; Baker, Daniel N.; Subbotin, Dmitriy; Ozeke, Louis; Shprits, Yuri; Kellerman, Adam

Two parameterizations of the resonant wave-particle interactions of electrons with ULF waves in the magnetosphere by Brautigam and Albert [2000] and Ozeke et al. [2012] are evaluated using the Versatile Electron Radiation Belt (VERB) diffusion code to estimate the effect of changing a diffusion coefficient on the radiation belt simulation. The period of investigation includes geomagnetically quiet and active time. The simulations take into account wave-particle interactions represented by radial diffusion transport, local acceleration, losses due to pitch-angle diffusion, and mixed diffusion. 1. Brautigam, D. H., and J. M. Albert (2000), Radial diffusion analysis of outer radiation belt electrons during the October 9, 1990, magnetic storm, J. Geophys. Res., 105(A1), 291-309, doi:10.1029/1999JA900344 2. Ozeke, L. G., I. R. Mann, K. R. Murphy, I. J. Rae, D. K. Milling, S. R. Elkington, A. A. Chan, and H. J. Singer (2012), ULF wave derived radiation belt radial diffusion coefficients, J. Geophys. Res., 117, A04222, doi:10.1029/2011JA017463.

Augmentation of oxygen transport by various hemoglobins as determined by pulsed field gradient NMR.

PubMed

Budhiraja, Vikas; Hellums, J David; Post, Jan F M

2002-11-01

Diffusion of oxyhemoglobin has been shown to augment the oxygen transport inside the red blood cells. Measurement of hemoglobin diffusion coefficients by pulsed-field gradient (PFG) nuclear magnetic resonance (NMR) technique can be used for estimating this augmentation effect. Self-diffusion coefficients of polymerized and unpolymerized bovine hemoglobin (Hb) and several other proteins were measured using this technique. The Hb diffusion coefficient was used to determine the effective permeability of oxygen and augmentation of oxygen transport through samples of Hb solutions due to diffusion of oxyhemoglobin. The values compared well with our previous diffusion cell measurements of effective diffusivity and augmentation. Our NMR studies show that even at low concentrations the augmentation of oxygen transport due to diffusion can be significant. The PFG NMR technique can thus provide an accurate and easy method for measuring augmentation of oxygen transport, especially in dilute samples of Hb. The results on polyhemoglobin and high-molecular-weight hemoglobin are of both basic interest and practical value in assessing the promise and performance of hemoglobin-based blood substitutes.

Investigation of weldable iron-aluminum alloys for corrosion protection in high temperature oxidizing-sulfidizing environments

NASA Astrophysics Data System (ADS)

Banovic, Stephen William

The objective of the present study was to investigate the corrosion behavior of weldable Fe-Al alloys in environments representative of low NOx gas compositions, i.e., high partial pressures of sulfur [p(S2)] and low partial pressures of oxygen [p(O2)]. Through an integrated experimental approach involving thermogravimetric techniques, post-exposure metallographic examination of the corroded samples, and detailed chemical microanalyses of the reaction scales, the effects of aluminum content, temperature, and gas composition on the corrosion behavior were observed. The corrosion behavior of Fe-Al alloys was found to be directly related to the type and morphology of corrosion product that formed during high temperature exposure in the oxidizing/sulfidizing environment. The inhibition stage was characterized by growth of a thin, gamma alumina scale that suppressed excessive degradation of the substrate at all temperatures. Localized mechanical failure of the initial passive scale, in combination with the inability to re-establish itself, was found to result in nodular growth of non-protective sulfide phases across the sample face due to short circuit diffusion through the gamma alumina layer. With the remnants of the initial gamma scale found between the outer and inner scale, it was concluded that these layers grew by iron diffusion outward and sulfur diffusion inward, respectively. The corrosion rate observed during development of these morphologies was directly related to the density of the nodules on the surface and the exposure temperature. The final period observed was the steady-state stage. This behavior was encountered from the onset of exposure for all Fe-5 wt% Al alloys tested, or upon coalescence of the nodular growths. After initially high corrosion rates, the weight gains were found to increase at a steady rate as subsequent growth occurred via diffusion through the continuous scale. Determination of the corrosion product growth mechanism could not be directly obtained from the thermogravimetric data. For samples with relatively high weight gains, enhanced scale growth at the comers and edges of the sample, as well as the morphology of the multi-layered, multi-phase corrosion products, violated the assumptions necessary for data manipulation by this means. The results from this study indicate that weldable compositions of Fe-Al alloys (10 wt% Al) show excellent corrosion resistance to aggressive low NO x gas compositions in the service temperature range (below 600°C). With the potential promise for applications requiring a combination of weldability and corrosion resistance in moderately reducing environments, these alloys are viable candidates for further evaluation for use as sulfidation resistant weld overlay coatings. (Abstract shortened by UMI.)

Relative Roles of Gap Junction Channels and Cytoplasm in Cell-to-Cell Diffusion of Fluorescent Tracers

NASA Astrophysics Data System (ADS)

Safranyos, Richard G. A.; Caveney, Stanley; Miller, James G.; Petersen, Nils O.

1987-04-01

Intercellular (tissue) diffusion of molecules requires cytoplasmic diffusion and diffusion through gap junctional (or cell-to-cell) channels. The rates of tissue and cytoplasmic diffusion of fluorescent tracers, expressed as an effective diffusion coefficient, De, and a cytoplasmic diffusion coefficient, Dcyt, have been measured among the developing epidermal cells of a larval beetle, Tenebrio molitor L., to determine the contribution of the junctional channels to intercellular diffusion. Tracer diffusion was measured by injecting fluorescent tracers into cells and quantitating the rate of subsequent spread into adjacent cells. Cytoplasmic diffusion was determined by fluorescence photobleaching. These experiments show that gap junctional channels constitute approximately 70-80% of the total cell-to-cell resistance to the diffusion of organic tracers at high concentrations in this tissue. At low concentrations, however, the binding of tracer to cytoplasm slows down the cytoplasmic diffusion, which may limit intercellular diffusion.

Diffusion of protein through the human cornea.

PubMed

Charalel, Resmi A; Engberg, Kristin; Noolandi, Jaan; Cochran, Jennifer R; Frank, Curtis; Ta, Christopher N

2012-01-01

To determine the rate of diffusion of myoglobin and bovine serum albumin (BSA) through the human cornea. These small proteins have hydrodynamic diameters of approximately 4.4 and 7.2 nm, and molecular weights of 16.7 and 66 kDa, for myoglobin and BSA, respectively. Diffusion coefficients were measured using a diffusion chamber where the protein of interest and balanced salt solution were in different chambers separated by an ex vivo human cornea. Protein concentrations in the balanced salt solution chamber were measured over time. Diffusion coefficients were calculated using equations derived from Fick's law and conservation of mass in a closed system. Our experiments demonstrate that the diffusion coefficient of myoglobin is 5.5 ± 0.9 × 10(-8) cm(2)/s (n = 8; SD = 1.3 × 10(-8) cm(2)/s; 95% CI: 4.6 × 10(-8) to 6.4 × 10(-8) cm(2)/s) and the diffusion coefficient of BSA is 3.1 ± 1.0 × 10(-8) cm(2)/s (n = 8; SD = 1.4 × 10(-8) cm(2)/s; 95% CI: 2.1 × 10(-8) to 4.1 × 10(-8) cm(2)/s). Our study suggests that molecules as large as 7.2 nm may be able to passively diffuse through the human cornea. With applications in pharmacotherapy and the development of an artificial cornea, further experiments are warranted to fully understand the limits of human corneal diffusion and its clinical relevance. Copyright © 2012 S. Karger AG, Basel.

The electron diffusion coefficient in Jupiter's magnetosphere

NASA Technical Reports Server (NTRS)

Birmingham, T.; Northrop, T.; Baxter, R.; Hess, W.; Lojko, M.

1974-01-01

A steady-state model of Jupiter's electron radiation belt is developed. The model includes injection from the solar wind, radial diffusion, energy degradation by synchrotron radiation, and absorption at Jupiter's surface. A diffusion coefficient of the form D sub RR/R sub J squared = k times R to the m-th power is assumed, and then observed data on synchrotron radiation are used to fit the model. The free parameters determined from this fit are m = 1.95 plus or minus 0.5, k = 1.7 plus or minus 0.5 x 10 to the 9th power per sec, and the magnetic moment of injected particles equals 770 plus or minus 300 MeV/G. The value of m shows quite clearly that the diffusion is not caused by magnetic pumping by a variable solar wind or by a fluctuating convection electric field. The process might be field line exchange driven by atmospheric-ionospheric winds; our diffusion coefficient has roughly the same radial dependence but is considerably smaller in magnitude than the upper bound diffusion coefficients recently suggested for this process by Brice and McDonough (1973) and Jacques and Davis (1972).

In situ estimation of the effective chemical diffusion coefficient of a rock matrix in a fractured aquifer

USGS Publications Warehouse

Gebrekristos, R.A.; Shapiro, A.M.; Usher, B.H.

2008-01-01

An in situ method of estimating the effective diffusion coefficient for a chemical constituent that diffuses into the primary porosity of a rock is developed by abruptly changing the concentration of the dissolved constituent in a borehole in contact with the rock matrix and monitoring the time-varying concentration. The experiment was conducted in a borehole completed in mudstone on the campus of the University of the Free State in Bloemfontein, South Africa. Numerous tracer tests were conducted at this site, which left a residual concentration of sodium chloride in boreholes that diffused into the rock matrix over a period of years. Fresh water was introduced into a borehole in contact with the mudstone, and the time-varying increase of chloride was observed by monitoring the electrical conductivity (EC) at various depths in the borehole. Estimates of the effective diffusion coefficient were obtained by interpreting measurements of EC over 34 d. The effective diffusion coefficient at a depth of 36 m was approximately 7.8??10-6 m2/d, but was sensitive to the assumed matrix porosity. The formation factor and mass flux for the mudstone were also estimated from the experiment. ?? Springer-Verlag 2007.

Understanding of Relationship between Phospholipid Membrane Permeability and Self-Diffusion Coefficients of Some Drugs and Biologically Active Compounds in Model Solvents.

PubMed

Blokhina, Svetlana V; Volkova, Tatyana V; Golubev, Vasiliy A; Perlovich, German L

2017-10-02

In this work we measured self-diffusion coefficients of 5 drugs (aspirin, caffeine, ethionamide, salicylic acid, and paracetamol) and 11 biologically active compounds of similar structure in deuterated water and 1-octanol by NMR. It has been found that an increase in the van der Waals volume of the molecules of the studied substances result in reduction of their diffusion mobility in both solvents. The analysis of the experimental data showed the influence of chemical nature and structural isomerization of the molecules on the diffusion mobility. Apparent permeability coefficients of the studied compounds were determined using an artificial phospholipid membrane made of egg lecithin as a model of in vivo absorption. Distribution coefficients in 1-octanol/buffer pH 7.4 system were measured. For the first time the model of the passive diffusion through the phospholipid membrane was validated based on the experimental data. To this end, the passive diffusion was considered as an additive process of molecule passage through the aqueous boundary layer before the membrane and 1-octanol barrier simulating the lipid layer of the membrane.

Effect of Hydrodynamic Interactions on Self-Diffusion of Quasi-Two-Dimensional Colloidal Hard Spheres.

PubMed

Thorneywork, Alice L; Rozas, Roberto E; Dullens, Roel P A; Horbach, Jürgen

2015-12-31

We compare experimental results from a quasi-two-dimensional colloidal hard sphere fluid to a Monte Carlo simulation of hard disks with small particle displacements. The experimental short-time self-diffusion coefficient D(S) scaled by the diffusion coefficient at infinite dilution, D(0), strongly depends on the area fraction, pointing to significant hydrodynamic interactions at short times in the experiment, which are absent in the simulation. In contrast, the area fraction dependence of the experimental long-time self-diffusion coefficient D(L)/D(0) is in quantitative agreement with D(L)/D(0) obtained from the simulation. This indicates that the reduction in the particle mobility at short times due to hydrodynamic interactions does not lead to a proportional reduction in the long-time self-diffusion coefficient. Furthermore, the quantitative agreement between experiment and simulation at long times indicates that hydrodynamic interactions effectively do not affect the dependence of D(L)/D(0) on the area fraction. In light of this, we discuss the link between structure and long-time self-diffusion in terms of a configurational excess entropy and do not find a simple exponential relation between these quantities for all fluid area fractions.

Diffusion models for corona formation in metagabbros from the Western Grenville Province, Canada

NASA Astrophysics Data System (ADS)

Grant, Shona M.

1988-01-01

Metagabbro bodies in SW Grenville Province display a variety of disequilibrium corona textures between spinel-clouded plagioclase and primary olivine or opaque oxide. Textural evidence favours a single-stage, subsolidus origin for the olivine coronas and diffusive mass transfer is believed to have been the rate-controlling process. Irreversible thermodynamics have been used to model two different garnet symplectite-bearing corona sequences in terms of steady state diffusion. In the models the flux of each component is related to the chemical potential gradients of all diffusing species by the Onsager or L-coefficients for diffusion. These coefficients are analogous to experimentally determined diffusion coefficients ( d), but relate the flux of components to chemical potential rather than concentration gradients. The major constraint on the relative values of Onsager coefficients comes from the observed mole fraction, X, of garnet in the symplectites; in (amph-gt) symplectites X {Gt/Sym}˜0.80, compared with ˜0.75 in (cpx-gt) symplectites. Several models using simple oxide components, and two different modifications of the reactant plagioclase composition, give the following qualitative results: the very low mobility of aluminium appears to control the rate of corona formation. Mg and Fe have similar mobility, and Mg can be up to 6 8 times more mobile than sodium. Determination of calcium mobility is problematical because of a proposed interaction with cross-coefficient terms reflecting “uphill” Ca-diffusion, i.e., calcium diffusing up its own chemical potential gradient. If these terms are not introduced, it is difficult to generate the required proportions of garnet in the symplectite. However, at moderate values of the cross-coefficient ratios, Mg can be up to 4 6 times more mobile than calcium ( L MgMg/LCaCa<4 6) and calcium must be 3 4 times more mobile than aluminium ( L CaCa/LAlAl>3).

Interpreting high time resolution galactic cosmic ray observations in a diffusive context

NASA Astrophysics Data System (ADS)

Jordan, A.; Spence, H. E.; Blake, J. B.; Shaul, D. A.

2009-12-01

We interpret galactic cosmic ray (GCR) variations near Earth within a diffusive context. The variations occur on time-/size-scales ranging from Forbush decreases (Fds), to substructure embedded within Fds, to smaller amplitude and shorter duration variations during relatively benign interplanetary conditions. We use high time resolution GCR observations from the High Sensitivity Telescope (HIST) on Polar and from the Spectrometer for INTEGRAL (SPI) and also use solar wind plasma and magnetic field observations from ACE and/or Wind. To calculate the coefficient of diffusion, we combine these datasets with a simple convection-diffusion model for relativistic charged particles in a magnetic field. We find reasonable agreement between our and previous estimates of the coefficient. We also show whether changes in the coefficient of diffusion are sufficient to explain the above GCR variations.

Space, energy and anisotropy effects on effective cross sections and diffusion coefficients in the resonance region

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meftah, B.

1982-01-01

Present methods used in reactor analysis do not include adequately the effect of anisotropic scattering in the calculation of resonance effective cross sections. Also the assumption that the streaming term ..cap omega...del Phi is conserved when the total, absorption and transfer cross sections are conserved, is bad because the leakage from a heterogeneous cell will not be conserved and is strongly anisotropic. A third major consideration is the coupling between different regions in a multiregion reactor; currently this effect is being completely ignored. To assess the magnitude of these effects, a code based on integral transport formalism with linear anisotropicmore » scattering was developed. Also, a more adequate formulation of the diffusion coefficient in a heterogeneous cell was derived. Two reactors, one fast, ZPR-6/5, and one thermal, TRX-3, were selected for the study. The study showed that, in general, the inclusion of linear scattering anisotropy increases the cell effective capture cross section of U-238. The increase was up to 2% in TRX-3 and 0.5% in ZPR-6/5. The effect on the multiplication factor was -0.003% ..delta..k/k for ZPR-6/5 and -0.05% ..delta..k/k for TRX-3. For the case of the diffusion coefficient, the combined effect of heterogeneity and linear anisotropy gave an increase of up to 29% in the parallel diffusion coefficient of TRX-3 and 5% in the parallel diffusion coefficient of ZPR-6/5. In contrast, the change in the perpendicular diffusion coefficient did not exceed 2% in both systems.« less

Effects of vitamin D receptor knockout on cornea epithelium gap junctions.

PubMed

Lu, Xiaowen; Watsky, Mitchell A

2014-05-06

Gap junctions are present in all corneal cell types and have been shown to have a critical role in cell phenotype determination. Vitamin D has been shown to influence cell differentiation, and recent work demonstrates the presence of vitamin D in the ocular anterior segment. This study measured and compared gap junction diffusion coefficients among different cornea epithelium phenotypes and in keratocytes using a noninvasive technique, fluorescence recovery after photobleaching (FRAP), and examined the influence of vitamin D receptor (VDR) knockout on epithelial gap junction communication in intact corneas. Previous gap junction studies in cornea epithelium and keratocytes were performed using cultured cells or ex vivo invasive techniques. These invasive techniques were unable to measure diffusion coefficients and likely were disruptive to normal cell physiology. Corneas from VDR knockout and control mice were stained with 5(6)-carboxyfluorescein diacetate (CFDA). Gap junction diffusion coefficients of the corneal epithelium phenotypes and of keratocytes, residing in intact corneas, were detected using FRAP. Diffusion coefficients equaled 18.7, 9.8, 5.6, and 4.2 μm(2)/s for superficial squamous cells, middle wing cells, basal cells, and keratocytes, respectively. Corneal thickness, superficial cell size, and the superficial squamous cell diffusion coefficient of 10-week-old VDR knockout mice were significantly lower than those of control mice (P < 0.01). The superficial cell diffusion coefficient of heterozygous mice was significantly lower than control mice (P < 0.05). Our results demonstrate differences in gap junction dye spread among the epithelial cell phenotypes, mirroring the epithelial developmental axis. The VDR knockout influences previously unreported cell-to-cell communication in superficial epithelium.

Solubility and diffusion of oxygen in phospholipid membranes.

PubMed

Möller, Matías N; Li, Qian; Chinnaraj, Mathivanan; Cheung, Herbert C; Lancaster, Jack R; Denicola, Ana

2016-11-01

The transport of oxygen and other nonelectrolytes across lipid membranes is known to depend on both diffusion and solubility in the bilayer, and to be affected by changes in the physical state and by the lipid composition, especially the content of cholesterol and unsaturated fatty acids. However, it is not known how these factors affect diffusion and solubility separately. Herein we measured the partition coefficient of oxygen in liposome membranes of dilauroyl-, dimiristoyl- and dipalmitoylphosphatidylcholine in buffer at different temperatures using the equilibrium-shift method with electrochemical detection. The apparent diffusion coefficient was measured following the fluorescence quenching of 1-pyrenedodecanoate inserted in the liposome bilayers under the same conditions. The partition coefficient varied with the temperature and the physical state of the membrane, from below 1 in the gel state to above 2.8 in the liquid-crystalline state in DMPC and DPPC membranes. The partition coefficient was directly proportional to the partial molar volume and was then associated to the increase in free-volume in the membrane as a function of temperature. The apparent diffusion coefficients were corrected by the partition coefficients and found to be nearly the same, with a null dependence on viscosity and physical state of the membrane, probably because the pyrene is disturbing the surrounding lipids and thus becoming insensitive to changes in membrane viscosity. Combining our results with those of others, it is apparent that both solubility and diffusion increase when increasing the temperature or when comparing a membrane in the gel to one in the fluid state. Copyright © 2016 Elsevier B.V. All rights reserved.

Biogeochemical cycles of carbon, sulfur, and free oxygen in a microbial mat

NASA Technical Reports Server (NTRS)

Canfield, Donald E.; Des Marais, David J.

1993-01-01

Complete budgets for carbon and oxygen have been constructed for cyanobacterial mats dominated by Microcoleus chthonoplastes from the evaporating ponds of a salt works. We infer from the data the various sinks for O2 as well as the sources of carbon for primary production. Although seasonal variability exists, a major percentage of the O2 produced during the day did not diffuse out of the mat but was used within the mat to oxidize both organic carbon and the sulfide produced by sulfate reduction. At night, most of the O2 that diffused into the mat was used to oxidize sulfide, with O2 respiration of minor importance. During the day, the internal mat processes of sulfate reduction and O2 respiration generated as much or more inorganic carbon (DIC) for primary production as diffusion into the mat. Oxygenic photosynthesis was the most important process of carbon fixation. At night, the DIC lost from the mat was mostly from sulfate reduction. Elemental fluxes across the mat/brine interface indicated that carbon with an oxidation state of greater than zero was taken up by the mat during the day and liberated from the mat at night. Overall, carbon with an average oxidation state of near zero accumulated in the mat. Both carbon fixation and carbon oxidation rates varied with temperature by a similar amount.

Molecular dynamics simulation of diffusion and electrical conductivity in montmorillonite interlayers

DOE PAGES

Greathouse, Jeffery A.; Cygan, Randall T.; Fredrich, Joanne T.; ...

2016-01-20

In this study, the diffusion of water and ions in the interlayer region of smectite clay minerals represents a direct probe of the type and strength of clay–fluid interactions. Interlayer diffusion also represents an important link between molecular simulation and macroscopic experiments. Here we use molecular dynamics simulation to investigate trends in cation and water diffusion in montmorillonite interlayers, looking specifically at the effects of layer charge, interlayer cation and cation charge (sodium or calcium), water content, and temperature. For Na-montmorillonite, the largest increase in ion and water diffusion coefficients occurs between the one-layer and two-layer hydrates, corresponding to themore » transition from inner-sphere to outer-sphere surface complexes. Calculated activation energies for ion and water diffusion in Na-montmorillonite are similar to each other and to the water hydrogen bond energy, suggesting the breaking of water–water and water–clay hydrogen bonds as a likely mechanism for interlayer diffusion. A comparison of interlayer diffusion with that of bulk electrolyte solutions reveals a clear trend of decreasing diffusion coefficient with increasing electrolyte concentration, and in most cases the interlayer diffusion results are nearly coincident with the corresponding bulk solutions. Trends in electrical conductivities computed from the ion diffusion coefficients are also compared.« less

Multiphasic modeling of charged solute transport across articular cartilage: Application of multi-zone finite-bath model.

PubMed

Arbabi, Vahid; Pouran, Behdad; Weinans, Harrie; Zadpoor, Amir A

2016-06-14

Charged and uncharged solutes penetrate through cartilage to maintain the metabolic function of chondrocytes and to possibly restore or further breakdown the cartilage tissue in different stages of osteoarthritis. In this study the transport of charged solutes across the various zones of cartilage was quantified, taken into account the physicochemical interactions between the solute and the cartilage constituents. A multiphasic finite-bath finite element (FE) model was developed to simulate equine cartilage diffusion experiments that used a negatively charged contrast agent (ioxaglate) in combination with serial micro-computed tomography (micro-CT) to measure the diffusion. By comparing the FE model with the experimental data both the diffusion coefficient of ioxaglate and the fixed charge density (FCD) were obtained. In the multiphasic model, cartilage was divided into multiple (three) zones to help understand how diffusion coefficient and FCD vary across cartilage thickness. The direct effects of charged solute-FCD interaction on diffusion were investigated by comparing the diffusion coefficients derived from the multiphasic and biphasic-solute models. We found a relationship between the FCD obtained by the multiphasic model and ioxaglate partitioning obtained from micro-CT experiments. Using our multi-zone multiphasic model, diffusion coefficient of the superficial zone was up to ten-fold higher than that of the middle zone, while the FCD of the middle zone was up to almost two-fold higher than that of the superficial zone. In conclusion, the developed finite-bath multiphasic model provides us with a non-destructive method by which we could obtain both diffusion coefficient and FCD of different cartilage zones. The outcomes of the current work will also help understand how charge of the bath affects the diffusion of a charged molecule and also predict the diffusion behavior of a charged solute across articular cartilage. Copyright © 2016 Elsevier Ltd. All rights reserved.

Seasonal Variability in Global Eddy Diffusion and the Effect on Thermospheric Neutral Density

NASA Astrophysics Data System (ADS)

Pilinski, M.; Crowley, G.

2014-12-01

We describe a method for making single-satellite estimates of the seasonal variability in global-average eddy diffusion coefficients. Eddy diffusion values as a function of time between January 2004 and January 2008 were estimated from residuals of neutral density measurements made by the CHallenging Minisatellite Payload (CHAMP) and simulations made using the Thermosphere Ionosphere Mesosphere Electrodynamics - Global Circulation Model (TIME-GCM). The eddy diffusion coefficient results are quantitatively consistent with previous estimates based on satellite drag observations and are qualitatively consistent with other measurement methods such as sodium lidar observations and eddy-diffusivity models. The eddy diffusion coefficient values estimated between January 2004 and January 2008 were then used to generate new TIME-GCM results. Based on these results, the RMS difference between the TIME-GCM model and density data from a variety of satellites is reduced by an average of 5%. This result, indicates that global thermospheric density modeling can be improved by using data from a single satellite like CHAMP. This approach also demonstrates how eddy diffusion could be estimated in near real-time from satellite observations and used to drive a global circulation model like TIME-GCM. Although the use of global values improves modeled neutral densities, there are some limitations of this method, which are discussed, including that the latitude-dependence of the seasonal neutral-density signal is not completely captured by a global variation of eddy diffusion coefficients. This demonstrates the need for a latitude-dependent specification of eddy diffusion consistent with diffusion observations made by other techniques.

Seasonal variability in global eddy diffusion and the effect on neutral density

NASA Astrophysics Data System (ADS)

Pilinski, M. D.; Crowley, G.

2015-04-01

We describe a method for making single-satellite estimates of the seasonal variability in global-average eddy diffusion coefficients. Eddy diffusion values as a function of time were estimated from residuals of neutral density measurements made by the Challenging Minisatellite Payload (CHAMP) and simulations made using the thermosphere-ionosphere-mesosphere electrodynamics global circulation model (TIME-GCM). The eddy diffusion coefficient results are quantitatively consistent with previous estimates based on satellite drag observations and are qualitatively consistent with other measurement methods such as sodium lidar observations and eddy diffusivity models. Eddy diffusion coefficient values estimated between January 2004 and January 2008 were then used to generate new TIME-GCM results. Based on these results, the root-mean-square sum for the TIME-GCM model is reduced by an average of 5% when compared to density data from a variety of satellites, indicating that the fidelity of global density modeling can be improved by using data from a single satellite like CHAMP. This approach also demonstrates that eddy diffusion could be estimated in near real-time from satellite observations and used to drive a global circulation model like TIME-GCM. Although the use of global values improves modeled neutral densities, there are limitations to this method, which are discussed, including that the latitude dependence of the seasonal neutral-density signal is not completely captured by a global variation of eddy diffusion coefficients. This demonstrates the need for a latitude-dependent specification of eddy diffusion which is also consistent with diffusion observations made by other techniques.

A MS, SEM-EDX and XRD study of Ti or Cu-doped zinc ferrites as regenerable sorbents for hot coal gas desulfurization

NASA Astrophysics Data System (ADS)

Ahmed, M. A.; García, E.; Alonso, L.; Palacios, J. M.

2000-02-01

Kinetic studies in thermobalance carried out by several authors previously have shown that small concentrations of TiO 2 or CuO can increase substantially the overall sulfidation rate of zinc ferrites, as regenerable sorbents for hot coal gas desulfurization. These oxides modify the textural properties of both the fresh or regenerated and the sulfided sorbent, modifying consequently the sulfidation rate because it is a partially diffusion-controlled process. However, by using grain models it is shown that most of the observed changes are due to changes in the intrinsic reactivity of the sorbent. Detailed studies of characterization in previous papers using different techniques have failed in revealing differential chemical changes that could be associated with a different behavior. In fact, the only significant changes observed in these studies were an apparent disappearance in fresh sorbents calcined at very high temperatures of the Raman effect, and a slight shift of the XPS binding energy of Fe levels, indicating a probable site migration and/or a change of the oxidation state. These characterization results, however, were not completely conclusive and additional efforts should be undertaken. In this paper more sensitive techniques such as Mössbauer spectroscopy (MS), powder X-ray diffraction (XRD) and scanning electron microscopy (SEM-EDX), have been used for the characterization of fresh, regenerated and sulfided sorbents. The study shows that the addition of TiO 2 or CuO induce substantial structural changes in zinc ferrites that can explain their apparent enhancing effect on the overall sulfidation reactivity. Additionally, this effect is decreased as the number of sulfidation-regeneration cycles increases, probably explaining the performance decay exhibited by these sorbents in multicycle tests in a fixed bed reactor.

Membrane-based microchannel device for continuous quantitative extraction of dissolved free sulfide from water and from oil.

PubMed

Toda, Kei; Ebisu, Yuki; Hirota, Kazutoshi; Ohira, Shin-Ichi

2012-09-05

Underground fluids are important natural sources of drinking water, geothermal energy, and oil-based fuels. To facilitate the surveying of such underground fluids, a novel microchannel extraction device was investigated for in-line continuous analysis and flow injection analysis of sulfide levels in water and in oil. Of the four designs investigated, the honeycomb-patterned microchannel extraction (HMCE) device was found to offer the most effective liquid-liquid extraction. In the HMCE device, a thin silicone membrane was sandwiched between two polydimethylsiloxane plates in which honeycomb-patterned microchannels had been fabricated. The identical patterns on the two plates were accurately aligned. The extracted sulfide was detected by quenching monitoring of fluorescein mercuric acetate (FMA). The sulfide extraction efficiencies from water and oil samples of the HMCE device and of three other designs (two annular and one rectangular channel) were examined theoretically and experimentally. The best performance was obtained with the HMCE device because of its thin sample layer (small diffusion distance) and large interface area. Quantitative extraction from both water and oil could be obtained using the HMCE device. The estimated limit of detection for continuous monitoring was 0.05 μM, and sulfide concentrations in the range of 0.15-10 μM could be determined when the acceptor was 5 μM FMA alkaline solution. The method was applied to natural water analysis using flow injection mode, and the data agreed with those obtained using headspace gas chromatography-flame photometric detection. The analysis of hydrogen sulfide levels in prepared oil samples was also performed. The proposed device is expected to be used for real time survey of oil wells and groundwater wells. Copyright © 2012 Elsevier B.V. All rights reserved.

Geodiversity of hydrothermal processes along the Mid-Atlantic Ridge and ultramafic-hosted mineralization: A new type of oceanic Cu-Zn-Co-Au volcanogenic massive sulfide deposit

NASA Astrophysics Data System (ADS)

Fouquet, Yves; Cambon, Pierre; Etoubleau, Joël; Charlou, Jean Luc; Ondréas, Hélène; Barriga, Fernando J. A. S.; Cherkashov, Georgy; Semkova, Tatiana; Poroshina, Irina; Bohn, M.; Donval, Jean Pierre; Henry, Katell; Murphy, Pamela; Rouxel, Olivier

Several hydrothermal deposits associated with ultramafic rocks have recently been found along slow spreading ridges with a low magmatic budget. Three preferential settings are identified: (1) rift valley walls near the amagmatic ends of ridge segments; (2) nontransform offsets; and (3) ultramafic domes at inside corners of ridge transform-fault intersections. The exposed mantle at these sites is often interpreted to be a detachment fault. Hydrothermal cells in ultramafic rocks may be driven by regional heat flow, cooling gabbroic intrusions, and exothermic heat produced during serpentinization. Along the Mid-Atlantic Ridge (MAR), hydrothermal deposits in ultramafic rocks include the following: (1) sulfide mounds related to high-temperature low-pH fluids (Logatchev, Rainbow, and Ashadze); (2) carbonate chimneys related to low-temperature, high-pH fluids (Lost City); (3) low-temperature diffuse venting and high-methane discharge associated with silica, minor sulfides, manganese oxides, and pervasive alteration (Saldanha); and (4) stockwork quartz veins with sulfides at the base of detachment faults (15°05'N). These settings are closely linked to preferential circulation of fluid along permeable detachment faults. Compared to mineralization in basaltic environments, sulfide deposits associated with ultramafic rocks are enriched in Cu, Zn, Co, Au, and Ni. Gold has a bimodal distribution in low-temperature Zn-rich and in high-temperature Cu-rich mineral assemblages. The Cu-Zn-Co-Au deposits along the MAR seem to be more abundant than in ophiolites on land. This may be because ultramafic-hosted volcanogenic massive sulfide deposits on slow spreading ridges are usually not accreted to continental margins during obduction and may constitute a specific marine type of mineralization.

Treatment of high-strength sulfate wastewater using an autotrophic biocathode in view of elemental sulfur recovery.

PubMed

Blázquez, Enric; Gabriel, David; Baeza, Juan Antonio; Guisasola, Albert

2016-11-15

Treatment of high-strength sulfate wastewaters is becoming a research issue not only for its optimal management but also for the possibility of recovering elemental sulfur. Moreover, sulfate-rich wastewater production is expected to grow due to the increased SO 2 emission contained in flue gases which are treated by chemical absorption in water. Bioelectrochemical systems (BESs) are a promising alternative for sulfate reduction with a lack of electron donor, since hydrogen can be generated in situ from electricity. However, complete sulfate reduction leads to hydrogen sulfide as final sulfur compound. This work is the first to demonstrate that, in addition to an efficient sulfate-rich wastewater treatment, elemental sulfur could be recovered in a biocathode of a BES under oxygen limiting conditions. The key of the process is the biological oxidation of sulfide to elemental sulfur simultaneously to the sulfate reduction in the cathode using the oxygen produced in the anode that diffuses through the membrane. High sulfate reduction rates (up to 388 mg S-SO 4 2-  L -1  d -1 ) were observed linked to a low production of sulfide. Accumulation of elemental sulfur over graphite fibers of the biocathode was demonstrated by energy dispersive spectrometry, discarding the presence of metal sulfides. Microbial community analysis of the cathode biofilm demonstrated the presence of sulfate-reducing bacteria (mainly Desulfovibrio sp.) and sulfide-oxidizing bacteria (mainly Sulfuricurvum sp.). Hence, this biocathode allows simultaneous biological sulfate reduction and biological sulfide oxidation to elemental sulfur, opening up a novel process for recovering sulfur from sulfate-rich wastewaters. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ti diffusion in ion prebombarded MgO(100). I. A model for quantitative analysis

NASA Astrophysics Data System (ADS)

Lu, M.; Lupu, C.; Styve, V. J.; Lee, S. M.; Rabalais, J. W.

2002-01-01

Enhancement of Ti diffusion in MgO(100) prebombarded with 7 keV Ar+ has been observed. Diffusion was induced by annealing to 1000 °C following the prebombardment and Ti evaporation. Such a sample geometry and experimental procedure alleviates the continuous provision of freely mobile defects introduced by ion irradiation during annealing for diffusion, making diffusion proceed in a non-steady-state condition. Diffusion penetration profiles were obtained by using secondary ion mass spectrometry depth profiling techniques. A model that includes a depth-dependent diffusion coefficient was proposed, which successfully explains the observed non-steady-state radiation enhanced diffusion. The diffusion coefficients are of the order of 10-20 m2/s and are enhanced due to the defect structure inflected by the Ar+ prebombardment.

Imaging and quantification of trans-membrane protein diffusion in living bacteria.

PubMed

Oswald, Felix; L M Bank, Ernst; Bollen, Yves J M; Peterman, Erwin J G

2014-07-07

The cytoplasmic membrane forms the barrier between any cell's interior and the outside world. It contains many proteins that enable essential processes such as the transmission of signals, the uptake of nutrients, and cell division. In the case of prokaryotes, which do not contain intracellular membranes, the cytoplasmic membrane also contains proteins for respiration and protein folding. Mutual interactions and specific localization of these proteins depend on two-dimensional diffusion driven by thermal fluctuations. The experimental investigation of membrane-protein diffusion in bacteria is challenging due to their small size, only a few times larger than the resolution of an optical microscope. Here, we review fluorescence microscopy-based methods to study diffusion of membrane proteins in living bacteria. The main focus is on data-analysis tools to extract diffusion coefficients from single-particle tracking data obtained by single-molecule fluorescence microscopy. We introduce a novel approach, IPODD (inverse projection of displacement distributions), to obtain diffusion coefficients from the usually obtained 2-D projected diffusion trajectories of the highly 3-D curved bacterial membrane. This method provides, in contrast to traditional mean-squared-displacement methods, correct diffusion coefficients and allows unravelling of heterogeneously diffusing populations.

Apparent diffusion coefficient of the normal human brain for various experimental conditions

NASA Astrophysics Data System (ADS)

Moraru, Luminita; Dimitrievici, Lucian

2017-01-01

Diffusion-Weighted Magnetic Resonance Imaging (DW-MRI) is being increasingly used to assess both brain tissues and cerebrospinal fluid integrity. In this paper we study inter-site reproducibility of the apparent diffusion coefficient values for the main cerebral tissues such as gray matter, white matter and into cerebrospinal fluid and for three different stacks of slices that were spaced at L = 79.8, 84.9 and 90 mm. We assessed the impact of the attenuation factor and diffusion gradient on the results reproducibility.

Diffusion tensor magnetic resonance imaging of the pancreas.

PubMed

Nissan, Noam; Golan, Talia; Furman-Haran, Edna; Apter, Sara; Inbar, Yael; Ariche, Arie; Bar-Zakay, Barak; Goldes, Yuri; Schvimer, Michael; Grobgeld, Dov; Degani, Hadassa

2014-01-01

To develop a diffusion-tensor-imaging (DTI) protocol that is sensitive to the complex diffusion and perfusion properties of the healthy and malignant pancreas tissues. Twenty-eight healthy volunteers and nine patients with pancreatic-ductal-adenocacinoma (PDAC), were scanned at 3T with T2-weighted and DTI sequences. Healthy volunteers were also scanned with multi-b diffusion-weighted-imaging (DWI), whereas a standard clinical protocol complemented the PDAC patients' scans. Image processing at pixel resolution yielded parametric maps of three directional diffusion coefficients λ1, λ2, λ3, apparent diffusion coefficient (ADC), and fractional anisotropy (FA), as well as a λ1-vector map, and a main diffusion-direction map. DTI measurements of healthy pancreatic tissue at b-values 0,500 s/mm² yielded: λ1 = (2.65±0.35)×10⁻³, λ2 = (1.87±0.22)×10⁻³, λ3 = (1.20±0.18)×10⁻³, ADC = (1.91±0.22)×10⁻³ (all in mm²/s units) and FA = 0.38±0.06. Using b-values of 100,500 s/mm² led to a significant reduction in λ1, λ2, λ3 and ADC (p<.0001) and a significant increase (p<0.0001) in FA. The reduction in the diffusion coefficients suggested a contribution of a fast intra-voxel-incoherent-motion (IVIM) component at b≤100 s/mm², which was confirmed by the multi-b DWI results. In PDACs, λ1, λ2, λ3 and ADC in both 0,500 s/mm² and 100,500 s/mm² b-values sets, as well as the reduction in these diffusion coefficients between the two sets, were significantly lower in comparison to the distal normal pancreatic tissue, suggesting higher cellularity and diminution of the fast-IVIM component in the cancer tissue. DTI using two reference b-values 0 and 100 s/mm² enabled characterization of the water diffusion and anisotropy of the healthy pancreas, taking into account a contribution of IVIM. The reduction in the diffusion coefficients of PDAC, as compared to normal pancreatic tissue, and the smaller change in these coefficients in PDAC when the reference b-value was modified from 0 to 100 s/mm², helped identifying the presence of malignancy.

Anisotropic Brownian motion in ordered phases of DNA fragments.

PubMed

Dobrindt, J; Rodrigo Teixeira da Silva, E; Alves, C; Oliveira, C L P; Nallet, F; Andreoli de Oliveira, E; Navailles, L

2012-01-01

Using Fluorescence Recovery After Photobleaching, we investigate the Brownian motion of DNA rod-like fragments in two distinct anisotropic phases with a local nematic symmetry. The height of the measurement volume ensures the averaging of the anisotropy of the in-plane diffusive motion parallel or perpendicular to the local nematic director in aligned domains. Still, as shown in using a model specifically designed to handle such a situation and predicting a non-Gaussian shape for the bleached spot as fluorescence recovery proceeds, the two distinct diffusion coefficients of the DNA particles can be retrieved from data analysis. In the first system investigated (a ternary DNA-lipid lamellar complex), the magnitude and anisotropy of the diffusion coefficient of the DNA fragments confined by the lipid bilayers are obtained for the first time. In the second, binary DNA-solvent system, the magnitude of the diffusion coefficient is found to decrease markedly as DNA concentration is increased from isotropic to cholesteric phase. In addition, the diffusion coefficient anisotropy measured within cholesteric domains in the phase coexistence region increases with concentration, and eventually reaches a high value in the cholesteric phase.

System-size corrections for self-diffusion coefficients calculated from molecular dynamics simulations: The case of CO2, n-alkanes, and poly(ethylene glycol) dimethyl ethers

NASA Astrophysics Data System (ADS)

Moultos, Othonas A.; Zhang, Yong; Tsimpanogiannis, Ioannis N.; Economou, Ioannis G.; Maginn, Edward J.

2016-08-01

Molecular dynamics simulations were carried out to study the self-diffusion coefficients of CO2, methane, propane, n-hexane, n-hexadecane, and various poly(ethylene glycol) dimethyl ethers (glymes in short, CH3O-(CH2CH2O)n-CH3 with n = 1, 2, 3, and 4, labeled as G1, G2, G3, and G4, respectively) at different conditions. Various system sizes were examined. The widely used Yeh and Hummer [J. Phys. Chem. B 108, 15873 (2004)] correction for the prediction of diffusion coefficient at the thermodynamic limit was applied and shown to be accurate in all cases compared to extrapolated values at infinite system size. The magnitude of correction, in all cases examined, is significant, with the smallest systems examined giving for some cases a self-diffusion coefficient approximately 15% lower than the infinite system-size extrapolated value. The results suggest that finite size corrections to computed self-diffusivities must be used in order to obtain accurate results.

Liquid Aluminum: Atomic diffusion and viscosity from ab initio molecular dynamics

PubMed Central

Jakse, Noel; Pasturel, Alain

2013-01-01

We present a study of dynamic properties of liquid aluminum using density-functional theory within the local-density (LDA) and generalized gradient (GGA) approximations. We determine the temperature dependence of the self-diffusion coefficient as well the viscosity using direct methods. Comparisons with experimental data favor the LDA approximation to compute dynamic properties of liquid aluminum. We show that the GGA approximation induce more important backscattering effects due to an enhancement of the icosahedral short range order (ISRO) that impact directly dynamic properties like the self-diffusion coefficient. All these results are then used to test the Stokes-Einstein relation and the universal scaling law relating the diffusion coefficient and the excess entropy of a liquid. PMID:24190311

Data-driven analysis for the temperature and momentum dependence of the heavy-quark diffusion coefficient in relativistic heavy-ion collisions

NASA Astrophysics Data System (ADS)

Xu, Yingru; Bernhard, Jonah E.; Bass, Steffen A.; Nahrgang, Marlene; Cao, Shanshan

2018-01-01

By applying a Bayesian model-to-data analysis, we estimate the temperature and momentum dependence of the heavy quark diffusion coefficient in an improved Langevin framework. The posterior range of the diffusion coefficient is obtained by performing a Markov chain Monte Carlo random walk and calibrating on the experimental data of D -meson RAA and v2 in three different collision systems at the Relativistic Heavy-Ion Collidaer (RHIC) and the Large Hadron Collider (LHC): Au-Au collisions at 200 GeV and Pb-Pb collisions at 2.76 and 5.02 TeV. The spatial diffusion coefficient is found to be consistent with lattice QCD calculations and comparable with other models' estimation. We demonstrate the capability of our improved Langevin model to simultaneously describe the RAA and v2 at both RHIC and the LHC energies, as well as the higher order flow coefficient such as D meson v3. We show that by applying a Bayesian analysis, we are able to quantitatively and systematically study the heavy flavor dynamics in heavy-ion collisions.

Modeling cesium ion exchange on fixed-bed columns of crystalline silicotitanate granules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Latheef, I.M.; Huckman, M.E.; Anthony, R.G.

2000-05-01

A mathematical model is presented to simulate Cs exchange in fixed-bed columns of a novel crystalline silicotitanate (CST) material, UOP IONSIV IE-911. A local equilibrium is assumed between the macropores and the solid crystals for the particle material balance. Axial dispersed flow and film mass-transfer resistance are incorporated into the column model. Cs equilibrium isotherms and diffusion coefficients were measured experimentally, and dispersion and film mass-transfer coefficients were estimated from correlations. Cs exchange column experiments were conducted in 5--5.7 M Na solutions and simulated using the proposed model. Best-fit diffusion coefficients from column simulations were compared with previously reported batchmore » values of Gu et al. and Huckman. Cs diffusion coefficients for the column were between 2.5 and 5.0 x 10{sup {minus}11} m{sup 2}/s for 5--5.7 M Na solutions. The effect of the isotherm shape on the Cs diffusion coefficient was investigated. The proposed model provides good fits to experimental data and may be utilized in designing commercial-scale units.« less

Swelling mechanism of urea cross-linked starch-lignin films in water.

PubMed

Sarwono, Ariyanti; Man, Zakaria; Bustam, M Azmi; Subbarao, Duvvuri; Idris, Alamin; Muhammad, Nawshad; Khan, Amir Sada; Ullah, Zahoor

2018-06-01

Coating fertilizer particles with thin films is a possibility to control fertilizer release rates. It is observed that novel urea cross-linked starch-lignin composite thin films, prepared by solution casting, swell on coming into contact with water due to the increase in volume by water uptake by diffusion. The effect of lignin content, varied from 0% to 20% in steps of 5% at three different temperatures (25°C, 35°C and 45°C), on swelling of the film was investigated. By gravimetric analysis, the equilibrium water uptake and diffusion coefficient decrease with lignin content, indicating that the addition of lignin increases the hydrophobicity of the films. When temperature increases, the diffusion coefficient and the amount of water absorbed tend to increase. Assuming that swelling of the thin film is by water uptake by diffusion, the diffusion coefficient is estimated. The estimated diffusion coefficient decreases from 4.3 to 2.1 × 10 -7  cm 2 /s at 25°C, from 5.3 to 2.9 × 10 -7  cm 2 /s at 35°C and from 6.2 to 3.8 × 10 -7  cm 2 /s at 45°C depending on the lignin content. Activation energy for the increase in diffusion coefficient with temperature is observed to be 16.55 kJ/mol. An empirical model of water uptake as a function of percentage of lignin and temperature was also developed based on Fick's law.

Generalized Einstein relation for the mutual diffusion coefficient of a binary fluid mixture.

PubMed

Felderhof, B U

2017-08-21

The method employed by Einstein to derive his famous relation between the diffusion coefficient and the friction coefficient of a Brownian particle is used to derive a generalized Einstein relation for the mutual diffusion coefficient of a binary fluid mixture. The expression is compared with the one derived by de Groot and Mazur from irreversible thermodynamics and later by Batchelor for a Brownian suspension. A different result was derived by several other workers in irreversible thermodynamics. For a nearly incompressible solution, the generalized Einstein relation agrees with the expression derived by de Groot and Mazur. The two expressions also agree to first order in solute density. For a Brownian suspension, the result derived from the generalized Smoluchowski equation agrees with both expressions.

Damage and recovery characteristics of lithium-containing solar cells.

NASA Technical Reports Server (NTRS)

Faith, T. J.

1971-01-01

Damage and recovery characteristics were measured on lithium-containing solar cells irradiated by 1-MeV electrons. Empirical expressions for cell recovery time, diffusion-length damage coefficient immediately after irradiation, and diffusion-length damage coefficient after recovery were derived using results of short-circuit current, diffusion-length, and reverse-bias capacitance measurements. The damage coefficients were expressed in terms of a single lithium density parameter, the lithium gradient. A fluence dependence was also established, this dependence being the same for both the immediate-post-irradiation and post-recovery cases. Cell recovery rates were found to increase linearly with lithium gradient.

Relation between the structural parameters of metallic glasses at the onset crystallization temperatures and threshold values of the effective diffusion coefficients

NASA Astrophysics Data System (ADS)

Tkatch, V. I.; Svyrydova, K. A.; Vasiliev, S. V.; Kovalenko, O. V.

2017-08-01

Using the results of differential scanning calorimetry and X-ray diffractometry, an analysis has been carried out of the initial stages of the eutectic and primary mechanisms of crystallization of a series of metallic glasses based on Fe and Al with the established temperature dependences of the effective diffusion coefficients. Analytical relationships, which relate the volume density of crystallites formed in the glasses at the temperatures of the onset of crystallization with the values of the effective diffusion coefficients at these temperatures have been proposed. It has been established that, in the glasses, the crystallization of which begins at the lower boundary of the threshold values of the effective diffusion coefficients ( 10-20 m2/s), structures are formed with the volume density of crystallites on the order of 1023-1024 m-3 and, at the upper boundary (10-18 m2/s), of the order of 1018 and 1020 m-3 in the glasses that are crystallized via the eutectic and primary mechanisms, respectively. Good agreement between the calculated and experimental estimates indicates that the threshold values of the effective diffusion coefficients are the main factors that determine the structure of glasses at the initial stages of crystallization.

Spectrophotometric Method for Differentiation of Human Skin Melanoma. II. Diagnostic Characteristics

NASA Astrophysics Data System (ADS)

Petruk, V. G.; Ivanov, A. P.; Kvaternyuk, S. M.; Barunb, V. V.

2016-05-01

Experimental data on the spectral dependences of the optical diffuse reflection coefficient for skin from different people with melanoma or nevus are presented in the form of the probability density of the diffuse reflection coefficient for the corresponding pigmented lesions. We propose a noninvasive technique for differentiating between malignant and benign tumors, based on measuring the diffuse reflection coefficient for a specific patient and comparing the value obtained with a pre-set threshold. If the experimental result is below the threshold, then it is concluded that the person has melanoma; otherwise, no melanoma is present. As an example, we consider the wavelength 870 nm. We determine the risk of malignant transformation of a nevus (its transition to melanoma) for different measured diffuse reflection coefficients. We have studied the errors in the method, its operating characteristics and probability characteristics as the threshold diffuse reflection coefficient is varied. We find that the diagnostic confidence, sensitivity, specificity, and effectiveness (accuracy) parameters are maximum (>0.82) for a threshold of 0.45-0.47. The operating characteristics for the proposed technique exceed the corresponding parameters for other familiar optical approaches to melanoma diagnosis. Its distinguishing feature is operation at only one wavelength, and consequently implementation of the experimental technique is simplified and made less expensive.

Correlation time and diffusion coefficient imaging: application to a granular flow system.

PubMed

Caprihan, A; Seymour, J D

2000-05-01

A parametric method for spatially resolved measurements for velocity autocorrelation functions, R(u)(tau) = , expressed as a sum of exponentials, is presented. The method is applied to a granular flow system of 2-mm oil-filled spheres rotated in a half-filled horizontal cylinder, which is an Ornstein-Uhlenbeck process with velocity autocorrelation function R(u)(tau) = e(- ||tau ||/tau(c)), where tau(c) is the correlation time and D = tau(c) is the diffusion coefficient. The pulsed-field-gradient NMR method consists of applying three different gradient pulse sequences of varying motion sensitivity to distinguish the range of correlation times present for particle motion. Time-dependent apparent diffusion coefficients are measured for these three sequences and tau(c) and D are then calculated from the apparent diffusion coefficient images. For the cylinder rotation rate of 2.3 rad/s, the axial diffusion coefficient at the top center of the free surface was 5.5 x 10(-6) m(2)/s, the correlation time was 3 ms, and the velocity fluctuation or granular temperature was 1.8 x 10(-3) m(2)/s(2). This method is also applicable to study transport in systems involving turbulence and porous media flows. Copyright 2000 Academic Press.

Sensitivity study on durability variables of marine concrete structures

NASA Astrophysics Data System (ADS)

Zhou, Xin'gang; Li, Kefei

2013-06-01

In order to study the influence of parameters on durability of marine concrete structures, the parameter's sensitivity analysis was studied in this paper. With the Fick's 2nd law of diffusion and the deterministic sensitivity analysis method (DSA), the sensitivity factors of apparent surface chloride content, apparent chloride diffusion coefficient and its time dependent attenuation factor were analyzed. The results of the analysis show that the impact of design variables on concrete durability was different. The values of sensitivity factor of chloride diffusion coefficient and its time dependent attenuation factor were higher than others. Relative less error in chloride diffusion coefficient and its time dependent attenuation coefficient induces a bigger error in concrete durability design and life prediction. According to probability sensitivity analysis (PSA), the influence of mean value and variance of concrete durability design variables on the durability failure probability was studied. The results of the study provide quantitative measures of the importance of concrete durability design and life prediction variables. It was concluded that the chloride diffusion coefficient and its time dependent attenuation factor have more influence on the reliability of marine concrete structural durability. In durability design and life prediction of marine concrete structures, it was very important to reduce the measure and statistic error of durability design variables.

Quasilinear diffusion coefficients in a finite Larmor radius expansion for ion cyclotron heated plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Jungpyo; Wright, John; Bertelli, Nicola

In this study, a reduced model of quasilinear velocity diffusion by a small Larmor radius approximation is derived to couple the Maxwell’s equations and the Fokker Planck equation self-consistently for the ion cyclotron range of frequency waves in a tokamak. The reduced model ensures the important properties of the full model by Kennel-Engelmann diffusion, such as diffusion directions, wave polarizations, and H-theorem. The kinetic energy change (Wdot ) is used to derive the reduced model diffusion coefficients for the fundamental damping (n = 1) and the second harmonic damping (n = 2) to the lowest order of the finite Larmormore » radius expansion. The quasilinear diffusion coefficients are implemented in a coupled code (TORIC-CQL3D) with the equivalent reduced model of the dielectric tensor. We also present the simulations of the ITER minority heating scenario, in which the reduced model is verified within the allowable errors from the full model results.« less

Nature of self-diffusion in two-dimensional fluids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choi, Bongsik; Han, Kyeong Hwan; Kim, Changho

Self-diffusion in a two-dimensional simple fluid is investigated by both analytical and numerical means. We investigate the anomalous aspects of self-diffusion in two-dimensional fluids with regards to the mean square displacement, the time-dependent diffusion coefficient, and the velocity autocorrelation function (VACF) using a consistency equation relating these quantities. Here, we numerically confirm the consistency equation by extensive molecular dynamics simulations for finite systems, corroborate earlier results indicating that the kinematic viscosity approaches a finite, non-vanishing value in the thermodynamic limit, and establish the finite size behavior of the diffusion coefficient. We obtain the exact solution of the consistency equation in the thermodynamic limit and use this solution to determine the large time asymptotics of the mean square displacement, the diffusion coefficient, and the VACF. An asymptotic decay law of the VACF resembles the previously known self-consistent form, 1/(more » $$t\\sqrt{In t)}$$ however with a rescaled time.« less

Nature of self-diffusion in two-dimensional fluids

DOE PAGES

Choi, Bongsik; Han, Kyeong Hwan; Kim, Changho; ...

2017-12-18

Self-diffusion in a two-dimensional simple fluid is investigated by both analytical and numerical means. We investigate the anomalous aspects of self-diffusion in two-dimensional fluids with regards to the mean square displacement, the time-dependent diffusion coefficient, and the velocity autocorrelation function (VACF) using a consistency equation relating these quantities. Here, we numerically confirm the consistency equation by extensive molecular dynamics simulations for finite systems, corroborate earlier results indicating that the kinematic viscosity approaches a finite, non-vanishing value in the thermodynamic limit, and establish the finite size behavior of the diffusion coefficient. We obtain the exact solution of the consistency equation in the thermodynamic limit and use this solution to determine the large time asymptotics of the mean square displacement, the diffusion coefficient, and the VACF. An asymptotic decay law of the VACF resembles the previously known self-consistent form, 1/(more » $$t\\sqrt{In t)}$$ however with a rescaled time.« less

Quasilinear diffusion coefficients in a finite Larmor radius expansion for ion cyclotron heated plasmas

DOE PAGES

Lee, Jungpyo; Wright, John; Bertelli, Nicola; ...

2017-04-24

In this study, a reduced model of quasilinear velocity diffusion by a small Larmor radius approximation is derived to couple the Maxwell’s equations and the Fokker Planck equation self-consistently for the ion cyclotron range of frequency waves in a tokamak. The reduced model ensures the important properties of the full model by Kennel-Engelmann diffusion, such as diffusion directions, wave polarizations, and H-theorem. The kinetic energy change (Wdot ) is used to derive the reduced model diffusion coefficients for the fundamental damping (n = 1) and the second harmonic damping (n = 2) to the lowest order of the finite Larmormore » radius expansion. The quasilinear diffusion coefficients are implemented in a coupled code (TORIC-CQL3D) with the equivalent reduced model of the dielectric tensor. We also present the simulations of the ITER minority heating scenario, in which the reduced model is verified within the allowable errors from the full model results.« less

Simple Analytical Forms of the Perpendicular Diffusion Coefficient for Two-component Turbulence. III. Damping Model of Dynamical Turbulence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gammon, M.; Shalchi, A., E-mail: andreasm4@yahoo.com

2017-10-01

In several astrophysical applications one needs analytical forms of cosmic-ray diffusion parameters. Some examples are studies of diffusive shock acceleration and solar modulation. In the current article we explore perpendicular diffusion based on the unified nonlinear transport theory. While we focused on magnetostatic turbulence in Paper I, we included the effect of dynamical turbulence in Paper II of the series. In the latter paper we assumed that the temporal correlation time does not depend on the wavenumber. More realistic models have been proposed in the past, such as the so-called damping model of dynamical turbulence. In the present paper wemore » derive analytical forms for the perpendicular diffusion coefficient of energetic particles in two-component turbulence for this type of time-dependent turbulence. We present new formulas for the perpendicular diffusion coefficient and we derive a condition for which the magnetostatic result is recovered.« less

A new coarse-grained model for E. coli cytoplasm: accurate calculation of the diffusion coefficient of proteins and observation of anomalous diffusion.

PubMed

Hasnain, Sabeeha; McClendon, Christopher L; Hsu, Monica T; Jacobson, Matthew P; Bandyopadhyay, Pradipta

2014-01-01

A new coarse-grained model of the E. coli cytoplasm is developed by describing the proteins of the cytoplasm as flexible units consisting of one or more spheres that follow Brownian dynamics (BD), with hydrodynamic interactions (HI) accounted for by a mean-field approach. Extensive BD simulations were performed to calculate the diffusion coefficients of three different proteins in the cellular environment. The results are in close agreement with experimental or previously simulated values, where available. Control simulations without HI showed that use of HI is essential to obtain accurate diffusion coefficients. Anomalous diffusion inside the crowded cellular medium was investigated with Fractional Brownian motion analysis, and found to be present in this model. By running a series of control simulations in which various forces were removed systematically, it was found that repulsive interactions (volume exclusion) are the main cause for anomalous diffusion, with a secondary contribution from HI.

Symplastic Transport of Carboxyfluorescein in Staminal Hairs of Setcreasea purpurea Is Diffusive and Includes Loss to the Vacuole.

PubMed

Tucker, J E; Mauzerall, D; Tucker, E B

1989-07-01

The kinetics of symplastic transport in staminal hairs of Setcreasea purpurea was studied. The tip cell of a staminal hair was microinjected with carboxyfluorescein (CF) and the symplastic transport of this CF was videotaped and the digital data analyzed to produce kinetic curves. Using a finite difference equation for diffusion between cells and for loss of dye into the vacuole, kinetic curves were calculated and fitted to the observed data. These curves were matched with data from actual microinjection experiments by adjusting K (the coefficient of intercellular junction diffusion) and L (the coefficient of intracellular loss) until a minimum in the least squares difference between the curves was obtained. (a) Symplastic transport of CF was governed by diffusion through intercellular pores (plasmodesmata) and intracellular loss. Diffusion within the cell cytoplasm was never limiting. (b) Each cell and its plasmodesmata must be considered as its own diffusion system. Therefore, a diffusion coefficient cannot be calculated for an entire chain of cells. (c) The movement through plasmodesmata in either direction was the same since the data are fit by a diffusion equation. (d) Diffusion through the intercellular pores was estimated to be slower than diffusion through similar pores filled with water.

Symplastic Transport of Carboxyfluorescein in Staminal Hairs of Setcreasea purpurea Is Diffusive and Includes Loss to the Vacuole 1

PubMed Central

Tucker, Joseph E.; Mauzerall, David; Tucker, Edward B.

1989-01-01

The kinetics of symplastic transport in staminal hairs of Setcreasea purpurea was studied. The tip cell of a staminal hair was microinjected with carboxyfluorescein (CF) and the symplastic transport of this CF was videotaped and the digital data analyzed to produce kinetic curves. Using a finite difference equation for diffusion between cells and for loss of dye into the vacuole, kinetic curves were calculated and fitted to the observed data. These curves were matched with data from actual microinjection experiments by adjusting K (the coefficient of intercellular junction diffusion) and L (the coefficient of intracellular loss) until a minimum in the least squares difference between the curves was obtained. (a) Symplastic transport of CF was governed by diffusion through intercellular pores (plasmodesmata) and intracellular loss. Diffusion within the cell cytoplasm was never limiting. (b) Each cell and its plasmodesmata must be considered as its own diffusion system. Therefore, a diffusion coefficient cannot be calculated for an entire chain of cells. (c) The movement through plasmodesmata in either direction was the same since the data are fit by a diffusion equation. (d) Diffusion through the intercellular pores was estimated to be slower than diffusion through similar pores filled with water. PMID:16666864

Facile and low temperature route to synthesis of CuS nanostructure in mesoporous material by solvothermal method.

PubMed

Sohrabnezhad, Sh; Zanjanchi, M A; Hosseingholizadeh, S; Rahnama, R

2014-04-05

The synthesis of CuS nanomaterial in MCM-41 matrix has been realized by chemical synthesis between MCM-41, copper sulfate pentahydrate and thiourea via a solvothermal method in ethylene glycol and water, separately. X-ray diffraction analysis (XRD), diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and fourier transform infrared (FT-IR) were used to characterize the products. At synthesized CuS/MCM-41 sample in ethylene glycol, X-ray diffraction and diffuse reflectance spectroscopy showed pure covellite phase of copper sulfide with high crystality. But prepared CuS/MCM-41 sample in water shows the covellite, chalcocite and the djurleite phase of copper sulfide nanostructures. The formation of CuS nanostructures was confirmed by FT-IR. Photocatalytic activity of CuS/MCM-41 nanocomposites was studied for degradation of Methylene Blue (MB) under visible light. The CuS/MCM-41 nanocomposite is more effective nanocatalyst than synthesized CuS/MCM-41 sample in water for degradation of methylene blue. Several parameters were examined, catalyst amount (0.1-1gL(-1)), pH (1-13) and initial concentration of MB (0.96-10ppm). The extent of degradation was estimated from the residual concentration by spectrophotometrically. The support size was obtained in the range 60-145nm by TEM. In the same way, the average size of copper sulfide in CuSMCM-41E and CuS/MCM-41W nanostructures were obtained about 10nm and 16nm, respectively. Copyright © 2013 Elsevier B.V. All rights reserved.

Precise measurement of the self-diffusion coefficient for poly(ethylene glycol) in aqueous solution using uniform oligomers

NASA Astrophysics Data System (ADS)

Shimada, Kayori; Kato, Haruhisa; Saito, Takeshi; Matsuyama, Shigetomo; Kinugasa, Shinichi

2005-06-01

Uniform poly(ethylene glycol) (PEG) oligomers, with a degree of polymerization n =1-40, were separated by preparative supercritical fluid chromatography from commercial monodispersed samples. Diffusion coefficients, D, for separated uniform PEG oligomers were measured in dilute solutions of deuterium oxide (D2O) at 30 ° C, using pulsed-field gradient nuclear magnetic resonance. The measured D for each molecular weight was extrapolated to infinite dilution. Diffusion coefficients obtained at infinite dilution follow the scaling behavior of Zimm-type diffusion, even in the lower molecular weight range. Molecular-dynamics simulations for PEG in H2O also showed this scaling behavior, and reproduced close hydrodynamic interactions between PEG and water. These findings suggest that diffusion of PEG in water is dominated by hydrodynamic interaction over a wide molecular weight range, including at low molecular weights around 1000.

THE IMPLICIT CONTRIBUTION OF SLAB MODES TO THE PERPENDICULAR DIFFUSION COEFFICIENT OF PARTICLES INTERACTING WITH TWO-COMPONENT TURBULENCE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shalchi, A., E-mail: andreasm4@yahoo.com

2016-10-20

We explore the transport of energetic particles in two-component turbulence in which the stochastic magnetic field is assumed to be a superposition of slab and two-dimensional modes. It is known that in magnetostatic slab turbulence, the motion of particles across the mean magnetic field is subdiffusive. If a two-dimensional component is added, diffusion is recovered. It was also shown before that in two-component turbulence, the slab modes do not explicitly contribute to the perpendicular diffusion coefficient. In the current paper, the implicit contribution of slab modes is explored and it is shown that this contribution leads to a reduction ofmore » the perpendicular diffusion coefficient. This effect improves the agreement between simulations and analytical theory. Furthermore, the obtained results are relevant for investigations of diffusive shock acceleration.« less

Diffusion of CO2 in Large Crystals of Cu-BTC MOF.

PubMed

Tovar, Trenton M; Zhao, Junjie; Nunn, William T; Barton, Heather F; Peterson, Gregory W; Parsons, Gregory N; LeVan, M Douglas

2016-09-14

Carbon dioxide adsorption in metal-organic frameworks has been widely studied for applications in carbon capture and sequestration. A critical component that has been largely overlooked is the measurement of diffusion rates. This paper describes a new reproducible procedure to synthesize millimeter-scale Cu-BTC single crystals using concentrated reactants and an acetic acid modulator. Microscopic images, X-ray diffraction patterns, Brunauer-Emmett-Teller surface areas, and thermogravimetric analysis results all confirm the high quality of these Cu-BTC single crystals. The large crystal size aids in the accurate measurement of micropore diffusion coefficients. Concentration-swing frequency response performed at varying gas-phase concentrations gives diffusion coefficients that show very little dependence on the loading up to pressures of 0.1 bar. The measured micropore diffusion coefficient for CO2 in Cu-BTC is 1.7 × 10(-9) m(2)/s.

Analysis of Particle Transport in DIII-D H-mode Plasma with a Generalized Pinch-Diffusion Model

NASA Astrophysics Data System (ADS)

Owen, L. W.; Stacey, W. M.; Groebner, R. J.; Callen, J. D.; Bonnin, X.

2009-11-01

Interpretative analyses of particle transport in the pedestal region of H-mode plasmas typically yield diffusion coefficients that are very small (<0.1 m^2/s) in the steep gradient region when a purely diffusive particle flux is fitted to the experimental density gradients. Previous evaluation of the particle and momentum balance equations using the experimental data indicated that the pedestal profiles are consistent with transport described by a pinch-diffusion particle flux relation [1]. This type of model is used to calculate the diffusion coefficient and pinch velocity in the core for an inter-ELM H-mode plasma in the DIII-D discharge 98889. Full-plasma SOPLS simulations using neutral beam particle and energy sources from ONETWO calculations and the model transport coefficients show good agreement with the measured density pedestal profile. 6pt [1] W.M. Stacey and R.J. Groebner, Phys. Plasmas 12, 042504 (2005).

Thermodynamic assessment of oxygen diffusion in non-stoichiometric UO2±x from experimental data and Frenkel pair modeling

NASA Astrophysics Data System (ADS)

Berthinier, C.; Rado, C.; Chatillon, C.; Hodaj, F.

2013-02-01

The self and chemical diffusion of oxygen in the non-stoichiometric domain of the UO2 compound is analyzed from the point of view of experimental determinations and modeling from Frenkel pair defects. The correlation between the self-diffusion and the chemical diffusion coefficients is analyzed using the Darken coefficient calculated from a thermodynamic description of the UO2±x phase. This description was obtained from an optimization of thermodynamic and phase diagram data and modeling with different point defects, including the Frenkel pair point defects. The proposed diffusion coefficients correspond to the 300-2300 K temperature range and to the full composition range of the non stoichiometric UO2 compound. These values will be used for the simulation of the oxidation and ignition of the uranium carbide in different oxygen atmospheres that starts at temperatures as low as 400 K.

Proton transfer and the diffusion of H+ and OH- ions along water wires.

PubMed

Lee, Song Hi; Rasaiah, Jayendran C

2013-09-28

Hydrogen and hydroxide ion transport in narrow carbon nanotubes (CNTs) of diameter 8.1 Å and lengths up to 582 Å are investigated by molecular dynamics simulations using a dissociating water model. The diffusion coefficients of the free ions in an open chain are significantly larger than in periodically replicated wires that necessarily contain D or L end defects, and both are higher than they are in bulk water. The free hydroxide ion diffuses faster than the free hydronium ion in short CNTs, unlike diffusion in liquid water, and both coefficients increase and converge to nearly the same value with increasing tube length. The diffusion coefficients of the two ions increase further when the tubes are immersed in a water reservoir and they move easily out of the tube, suggesting an additional pathway for proton transport via OH(-) ions in biological channels.

Combined measurement of surface, grain boundary and lattice diffusion coefficients on olivine bi-crystals

NASA Astrophysics Data System (ADS)

Marquardt, Katharina; Dohmen, Ralf; Wagner, Johannes

2014-05-01

Diffusion along interface and grain boundaries provides an efficient pathway and may control chemical transport in rocks as well as their mechanical strength. Besides the significant relevance of these diffusion processes for various geologic processes, experimental data are still very limited (e.g., Dohmen & Milke, 2010). Most of these data were measured using polycrystalline materials and the formalism of LeClaire (1951) to fit integrated concentration depth profiles. To correctly apply this formalism, certain boundary conditions of the diffusion problem need to be fulfilled, e.g., surface diffusion is ignored, and furthermore the lattice diffusion coefficient has to be known from other studies or is an additional fitting parameter, which produces some ambiguity in the derived grain boundary diffusion coefficients. We developed an experimental setup where we can measure the lattice and grain boundary diffusion coefficients simultaneously but independent and demonstrate the relevance of surface diffusion for typical grain boundary diffusion experiments. We performed Mg2SiO4 bicrystal diffusion experiments, where a single grain boundary is covered by a thin-film of pure Ni2SiO4 acting as diffusant source, produced by pulsed laser deposition. The investigated grain boundary is a 60° (011)/[100]. This specific grain boundary configuration was modeled using molecular dynamics for comparison with the experimental observations in the transmission electron microscope (TEM). Both, experiment and model are in good agreement regarding the misorientation, whereas there are still some disagreements regarding the strain fields along the grain boundary that are of outmost importance for the strengths of the material. The subsequent diffusion experiments were carried out in the temperature range between 800° and 1450° C. The inter diffusion profiles were measured using the TEMs energy dispersive x-ray spectrometer standardized using the Cliff-Lorimer equation and EMPA measurements. To evaluate the obtained diffusion profiles we adapted the isolated grain boundary model, first proposed by Fisher (1951) to match several observations: (i) Anisotropic diffusion in forsterite, (ii) fast diffusion along the grain boundary, (iii) fast diffusion on the surface of the sample. The latter process is needed to explain an additional flux of material from the surface into the grain boundary. Surface and grain boundary diffusion coefficients are on the order of 10000 times faster than diffusion in the lattice. Another observation was that in some regions the diffusion profiles in the lattice were greatly extended. TEM observations suggest here that surface defects (nano-cracks, ect.) have been present, which apparently enhanced the diffusion through the bulk lattice. Dohmen, R., & Milke, R. (2010). Diffusion in Polycrystalline Materials: Grain Boundaries, Mathematical Models, and Experimental Data. Reviews in Mineralogy and Geochemistry, 72(1), 921-970. Fisher, J. C. (1951). Calculations of Diffusion Penetration Curves for Surface and Grain Boundary Diffusion. Journal of Applied Physics, 22(1), 74-77. Le Claire, A. D. (1951). Grain boundary diffusion in metals. Philosophical Magazine A, 42(328), 468-474.

Optimal estimation of diffusion coefficients from single-particle trajectories

NASA Astrophysics Data System (ADS)

Vestergaard, Christian L.; Blainey, Paul C.; Flyvbjerg, Henrik

2014-02-01

How does one optimally determine the diffusion coefficient of a diffusing particle from a single-time-lapse recorded trajectory of the particle? We answer this question with an explicit, unbiased, and practically optimal covariance-based estimator (CVE). This estimator is regression-free and is far superior to commonly used methods based on measured mean squared displacements. In experimentally relevant parameter ranges, it also outperforms the analytically intractable and computationally more demanding maximum likelihood estimator (MLE). For the case of diffusion on a flexible and fluctuating substrate, the CVE is biased by substrate motion. However, given some long time series and a substrate under some tension, an extended MLE can separate particle diffusion on the substrate from substrate motion in the laboratory frame. This provides benchmarks that allow removal of bias caused by substrate fluctuations in CVE. The resulting unbiased CVE is optimal also for short time series on a fluctuating substrate. We have applied our estimators to human 8-oxoguanine DNA glycolase proteins diffusing on flow-stretched DNA, a fluctuating substrate, and found that diffusion coefficients are severely overestimated if substrate fluctuations are not accounted for.

Measurements of exciton diffusion by degenerate four-wave mixing in CdS1-xSex

NASA Astrophysics Data System (ADS)

Schwab, H.; Pantke, K.-H.; Hvam, J. M.; Klingshirn, C.

1992-09-01

We performed transient-grating experiments to study the diffusion of excitons in CdS1-xSex mixed crystals. The decay of the initially created exciton density grating is well described for t<=1 ns by a stretched-exponential function. For later times this decay changes over to a behavior that is well fitted by a simple exponential function. During resonant excitation of the localized states, we find the diffusion coefficient (D) to be considerably smaller than in the binary compounds CdSe and CdS. At 4.2 K, D is below our experimental resolution which is about 0.025 cm2/s. With increasing lattice temperature (Tlattice) the diffusion coefficient increases. It was therefore possible to prove, in a diffusion experiment, that at Tlattice<=5 K the excitons are localized, while the exciton-phonon interaction leads to a delocalization and thus to the onset of diffusion. It was possible to deduce the diffusion coefficient of the extended excitons as well as the energetic position of the mobility edge.

A scaled-ionic-charge simulation model that reproduces enhanced and suppressed water diffusion in aqueous salt solutions.

PubMed

Kann, Z R; Skinner, J L

2014-09-14

Non-polarizable models for ions and water quantitatively and qualitatively misrepresent the salt concentration dependence of water diffusion in electrolyte solutions. In particular, experiment shows that the water diffusion coefficient increases in the presence of salts of low charge density (e.g., CsI), whereas the results of simulations with non-polarizable models show a decrease of the water diffusion coefficient in all alkali halide solutions. We present a simple charge-scaling method based on the ratio of the solvent dielectric constants from simulation and experiment. Using an ion model that was developed independently of a solvent, i.e., in the crystalline solid, this method improves the water diffusion trends across a range of water models. When used with a good-quality water model, e.g., TIP4P/2005 or E3B, this method recovers the qualitative behaviour of the water diffusion trends. The model and method used were also shown to give good results for other structural and dynamic properties including solution density, radial distribution functions, and ion diffusion coefficients.

Superdiffusion revisited in view of collisionless reconnection

NASA Astrophysics Data System (ADS)

Treumann, R. A.; Baumjohann, W.

2014-06-01

The concept of diffusion in collisionless space plasmas like those near the magnetopause and in the geomagnetic tail during reconnection is reexamined making use of the division of particle orbits into waiting orbits and break-outs into ballistic motion lying at the bottom, for instance, of Lévy flights. The rms average displacement in this case increases with time, describing superdiffusion, though faster than classical, is still a weak process, being however strong enough to support fast reconnection. Referring to two kinds of numerical particle-in-cell simulations we determine the anomalous diffusion coefficient, the anomalous collision frequency on which the diffusion process is based, and construct a relation between the diffusion coefficients and the resistive scale. The anomalous collision frequency from electron pseudo-viscosity in reconnection turns out to be of the order of the lower-hybrid frequency with the latter providing a lower limit, thus making similar assumptions physically meaningful. Tentative though not completely justified use of the κ distribution yields κ ≈ 6 in the reconnection diffusion region and, for the anomalous diffusion coefficient, the order of several times Bohm diffusivity.

Analysis of ligand-protein exchange by Clustering of Ligand Diffusion Coefficient Pairs (CoLD-CoP)

NASA Astrophysics Data System (ADS)

Snyder, David A.; Chantova, Mihaela; Chaudhry, Saadia

2015-06-01

NMR spectroscopy is a powerful tool in describing protein structures and protein activity for pharmaceutical and biochemical development. This study describes a method to determine weak binding ligands in biological systems by using hierarchic diffusion coefficient clustering of multidimensional data obtained with a 400 MHz Bruker NMR. Comparison of DOSY spectrums of ligands of the chemical library in the presence and absence of target proteins show translational diffusion rates for small molecules upon interaction with macromolecules. For weak binders such as compounds found in fragment libraries, changes in diffusion rates upon macromolecular binding are on the order of the precision of DOSY diffusion measurements, and identifying such subtle shifts in diffusion requires careful statistical analysis. The "CoLD-CoP" (Clustering of Ligand Diffusion Coefficient Pairs) method presented here uses SAHN clustering to identify protein-binders in a chemical library or even a not fully characterized metabolite mixture. We will show how DOSY NMR and the "CoLD-CoP" method complement each other in identifying the most suitable candidates for lysozyme and wheat germ acid phosphatase.

Electrochemical measurements of diffusion coefficients and activity coefficients for MnCl2 in molten eutectic LiCl-KCl

NASA Astrophysics Data System (ADS)

Horvath, D.; Rappleye, D.; Bagri, P.; Simpson, M. F.

2017-09-01

An electrochemical study of manganese chloride in molten salt mixtures of eutectic LiCl-KCl was carried out using a variety of electrochemical methods in a high temperature cell including cyclic voltammetry (CV), chronopotentiometry (CP), chronoamperometry (CA), and open circuit potentiometry. Single step reduction from Mn2+ to Mn(0) was observed on both W and Mo working electrodes. Using a combination of these methods, measurements were made of activity coefficient and diffusion coefficient for MnCl2 in LiCl-KCl as a function of concentration (3.54 × 10-4 to 3.60 × 10-3 mol fraction of MnCl2) at 773K. From OCP measurements, values for activity coefficient varied from 0.014 to 0.0071. Diffusion coefficients varied with concentration and differed based on measurement method (CV, CA, or CP). Based on cyclic Mn(II) ranged from 1.1 to 2.8 × 10-5 cm2/s depending on concentration.

Platinum-group element, Gold, Silver and Base Metal distribution in compositionally zoned sulfide droplets from the Medvezky Creek Mine, Noril'sk, Russia

USGS Publications Warehouse

Barnes, S.-J.; Cox, R.A.; Zientek, M.L.

2006-01-01

Concentrations of Ag, Au, Cd, Co, Re, Zn and Platinum-group elements (PGE) have been determined in sulfide minerals from zoned sulfide droplets of the Noril'sk 1 Medvezky Creek Mine. The aims of the study were; to establish whether these elements are located in the major sulfide minerals (pentlandite, pyrrhotite, chalcopyrite and cubanite), to establish whether the elements show a preference for a particular sulfide mineral and to investigate the model, which suggests that the zonation in the droplets is caused by the crystal fractionation of monosulfide solid solution (mss). Nickel, Cu, Ag, Re, Os, Ir, Ru, Rh and Pd, were found to be largely located in the major sulfide minerals. In contrast, less than 25% of the Au, Cd, Pt and Zn in the rock was found to be present in these sulfides. Osmium, Ir, Ru, Rh and Re were found to be concentrated in pyrrhotite and pentlandite. Palladium and Co was found to be concentrated in pentlandite. Silver, Cd and Zn concentrations are highest in chalcopyrite and cubanite. Gold and platinum showed no preference for any of the major sulfide minerals. The enrichment of Os, Ir, Ru, Rh and Re in pyrrhotite and pentlandite (exsolution products of mss) and the low levels of these elements in the cubanite and chalcopyrite (exsolution products of intermediate solid solution, iss) support the mss crystal fractionation model, because Os, Ir, Ru, Rh and Re are compatible with mss. The enrichment of Ag, Cd and Zn in chalcopyrite and cubanite also supports the mss fractionation model these minerals are derived from the fractionated liquid and these elements are incompatible with mss and thus should be enriched in the fractionated liquid. Gold and Pt do not partition into either iss or mss and become sufficiently enriched in the final fractionated liquid to crystallize among the iss and mss grains as tellurides, bismithides and alloys. During pentlandite exsolution Pd appears to have diffused from the Cu-rich portion of the droplet into pentlandite. ?? Springer-Verlag 2006.

Atomic layer deposition of metal sulfide materials

DOE PAGES

Dasgupta, Neil P.; Meng, Xiangbo; Elam, Jeffrey W.; ...

2015-01-12

The field of nanoscience is delivering increasingly intricate yet elegant geometric structures incorporating an ever-expanding palette of materials. Atomic layer deposition (ALD) is a powerful driver of this field, providing exceptionally conformal coatings spanning the periodic table and atomic-scale precision independent of substrate geometry. This versatility is intrinsic to ALD and results from sequential and self-limiting surface reactions. This characteristic facilitates digital synthesis, in which the film grows linearly with the number of reaction cycles. While the majority of ALD processes identified to date produce metal oxides, novel applications in areas such as energy storage, catalysis, and nanophotonics are motivatingmore » interest in sulfide materials. Recent progress in ALD of sulfides has expanded the diversity of accessible materials as well as a more complete understanding of the unique chalcogenide surface chemistry. ALD of sulfide materials typically uses metalorganic precursors and hydrogen sulfide (H 2S). As in oxide ALD, the precursor chemistry is critical to controlling both the film growth and properties including roughness, crystallinity, and impurity levels. By modification of the precursor sequence, multicomponent sulfides have been deposited, although challenges remain because of the higher propensity for cation exchange reactions, greater diffusion rates, and unintentional annealing of this more labile class of materials. A deeper understanding of these surface chemical reactions has been achieved through a combination of in situ studies and quantum-chemical calculations. As this understanding matures, so does our ability to deterministically tailor film properties to new applications and more sophisticated devices. This Account highlights the attributes of ALD chemistry that are unique to metal sulfides and surveys recent applications of these materials in photovoltaics, energy storage, and photonics. Within each application space, the benefits and challenges of novel ALD processes are emphasized and common trends are summarized. We conclude with a perspective on potential future directions for metal chalcogenide ALD as well as untapped opportunities. As a result, we consider challenges that must be addressed prior to implementing ALD metal sulfides into future device architectures.« less

The effect of laterite density on radon diffusion behavior.

PubMed

Li, Yongmei; Tan, Wanyu; Tan, Kaixuan; Liu, Zehua; Fang, Qi; Lv, Junwen; Duan, Xianzhe; Liu, Zhenzhong; Guo, Yueyue

2018-02-01

Radon generated in porous media such as soils and rocks migrates into indoor and outdoor air mainly by diffusion, possessing significant hazards to human health. In order to reduce these hazards of radon, it is of great importance to study the diffusion behavior of radon. In this study, we systematically measured the radon diffusion coefficient of laterite with the density ranging from 0.917gcm -3 to 2.238gcm -3 , and studied the effect of laterite density on the radon diffusion. The results show that the radon diffusion coefficient of the laterite generally decreases with the increasing laterite density. In addition, three possible relationships between the radon diffusion coefficient and the laterite density are found out as follows: (1) the linear correlation with a slope of -4.48 × 10 -6 for laterite with density ranging from 0.917 to 1.095gcm -3 , (2) the exponential correlation for laterite with density from 1.095 to 1.63gcm -3 , (3) linear correlation with a slope of -3.1 × 10 -7 for laterite with density from 1.63 to 2.238gcm -3 . The complex relationship between the radon diffusion coefficient and density is caused by the change of porosity and tortuosity of the laterite. Therefore, we suggest that a suitable density should be adopted while using the laterite to effectively cover uranium tailings or economically produce building materials that can curb the radon exhalation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Numerical convergence of the self-diffusion coefficient and viscosity obtained with Thomas-Fermi-Dirac molecular dynamics.

PubMed

Danel, J-F; Kazandjian, L; Zérah, G

2012-06-01

Computations of the self-diffusion coefficient and viscosity in warm dense matter are presented with an emphasis on obtaining numerical convergence and a careful evaluation of the standard deviation. The transport coefficients are computed with the Green-Kubo relation and orbital-free molecular dynamics at the Thomas-Fermi-Dirac level. The numerical parameters are varied until the Green-Kubo integral is equal to a constant in the t→+∞ limit; the transport coefficients are deduced from this constant and not by extrapolation of the Green-Kubo integral. The latter method, which gives rise to an unknown error, is tested for the computation of viscosity; it appears that it should be used with caution. In the large domain of coupling constant considered, both the self-diffusion coefficient and viscosity turn out to be well approximated by simple analytical laws using a single effective atomic number calculated in the average-atom model.

Numerical convergence of the self-diffusion coefficient and viscosity obtained with Thomas-Fermi-Dirac molecular dynamics

NASA Astrophysics Data System (ADS)

Danel, J.-F.; Kazandjian, L.; Zérah, G.

2012-06-01

Computations of the self-diffusion coefficient and viscosity in warm dense matter are presented with an emphasis on obtaining numerical convergence and a careful evaluation of the standard deviation. The transport coefficients are computed with the Green-Kubo relation and orbital-free molecular dynamics at the Thomas-Fermi-Dirac level. The numerical parameters are varied until the Green-Kubo integral is equal to a constant in the t→+∞ limit; the transport coefficients are deduced from this constant and not by extrapolation of the Green-Kubo integral. The latter method, which gives rise to an unknown error, is tested for the computation of viscosity; it appears that it should be used with caution. In the large domain of coupling constant considered, both the self-diffusion coefficient and viscosity turn out to be well approximated by simple analytical laws using a single effective atomic number calculated in the average-atom model.

Revealing mesoscopic structural universality with diffusion.

PubMed

Novikov, Dmitry S; Jensen, Jens H; Helpern, Joseph A; Fieremans, Els

2014-04-08

Measuring molecular diffusion is widely used for characterizing materials and living organisms noninvasively. This characterization relies on relations between macroscopic diffusion metrics and structure at the mesoscopic scale commensurate with the diffusion length. Establishing such relations remains a fundamental challenge, hindering progress in materials science, porous media, and biomedical imaging. Here we show that the dynamical exponent in the time dependence of the diffusion coefficient distinguishes between the universality classes of the mesoscopic structural complexity. Our approach enables the interpretation of diffusion measurements by objectively selecting and modeling the most relevant structural features. As an example, the specific values of the dynamical exponent allow us to identify the relevant mesoscopic structure affecting MRI-measured water diffusion in muscles and in brain, and to elucidate the structural changes behind the decrease of diffusion coefficient in ischemic stroke.

Broadening of polymer chromatographic signals: Analysis, quantification and correction through effective diffusion coefficients.

PubMed

Suárez, Inmaculada; Coto, Baudilio

2015-08-14

Average molecular weights and polydispersity indexes are some of the most important parameters considered in the polymer characterization. Usually, gel permeation chromatography (GPC) and multi angle light scattering (MALS) are used for this determination, but GPC values are overestimated due to the dispersion introduced by the column separation. Several procedures were proposed to correct such effect usually involving more complex calibration processes. In this work, a new method of calculation has been considered including diffusion effects. An equation for the concentration profile due to diffusion effects along the GPC column was considered to be a Fickian function and polystyrene narrow standards were used to determine effective diffusion coefficients. The molecular weight distribution function of mono and poly disperse polymers was interpreted as a sum of several Fickian functions representing a sample formed by only few kind of polymer chains with specific molecular weight and diffusion coefficient. Proposed model accurately fit the concentration profile along the whole elution time range as checked by the computed standard deviation. Molecular weights obtained by this new method are similar to those obtained by MALS or traditional GPC while polydispersity index values are intermediate between those obtained by the traditional GPC combined to Universal Calibration method and the MALS method. Values for Pearson and Lin coefficients shows improvement in the correlation of polydispersity index values determined by GPC and MALS methods when diffusion coefficients and new methods are used. Copyright © 2015 Elsevier B.V. All rights reserved.

Mutual diffusion of binary liquid mixtures containing methanol, ethanol, acetone, benzene, cyclohexane, toluene, and carbon tetrachloride

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guevara-Carrion, Gabriela; Janzen, Tatjana; Muñoz-Muñoz, Y. Mauricio

Mutual diffusion coefficients of all 20 binary liquid mixtures that can be formed out of methanol, ethanol, acetone, benzene, cyclohexane, toluene, and carbon tetrachloride without a miscibility gap are studied at ambient conditions of temperature and pressure in the entire composition range. The considered mixtures show a varying mixing behavior from almost ideal to strongly non-ideal. Predictive molecular dynamics simulations employing the Green-Kubo formalism are carried out. Radial distribution functions are analyzed to gain an understanding of the liquid structure influencing the diffusion processes. It is shown that cluster formation in mixtures containing one alcoholic component has a significant impactmore » on the diffusion process. The estimation of the thermodynamic factor from experimental vapor-liquid equilibrium data is investigated, considering three excess Gibbs energy models, i.e., Wilson, NRTL, and UNIQUAC. It is found that the Wilson model yields the thermodynamic factor that best suits the simulation results for the prediction of the Fick diffusion coefficient. Four semi-empirical methods for the prediction of the self-diffusion coefficients and nine predictive equations for the Fick diffusion coefficient are assessed and it is found that methods based on local composition models are more reliable. Finally, the shear viscosity and thermal conductivity are predicted and in most cases favorably compared with experimental literature values.« less

Adenosine triphosphate diffusion through poly(ethylene glycol) diacrylate hydrogels can be tuned by cross-link density as measured by PFG-NMR

NASA Astrophysics Data System (ADS)

Majer, Günter; Southan, Alexander

2017-06-01

The diffusion of small molecules through hydrogels is of great importance for many applications. Especially in biological contexts, the diffusion of nutrients through hydrogel networks defines whether cells can survive inside the hydrogel or not. In this contribution, hydrogels based on poly(ethylene glycol) diacrylate with mesh sizes ranging from ξ = 1.1 to 12.9 nm are prepared using polymers with number-average molecular weights between Mn = 700 and 8000 g/mol. Precise measurements of diffusion coefficients D of adenosine triphosphate (ATP), an important energy carrier in biological systems, in these hydrogels are performed by pulsed field gradient nuclear magnetic resonance. Depending on the mesh size, ξ, and on the polymer volume fraction of the hydrogel after swelling, ϕ, it is possible to tune the relative ATP diffusion coefficient D/D0 in the hydrogels to values between 0.14 and 0.77 compared to the ATP diffusion coefficient D0 in water. The diffusion coefficients of ATP in these hydrogels are compared with predictions of various mathematical expressions developed under different model assumptions. The experimental data are found to be in good agreement with the predictions of a modified obstruction model or the free volume theory in combination with the sieving behavior of the polymer chains. No reasonable agreement was found with the pure hydrodynamic model.

Self-diffusion of electrolyte species in model battery electrodes using Magic Angle Spinning and Pulsed Field Gradient Nuclear Magnetic Resonance

NASA Astrophysics Data System (ADS)

Tambio, Sacris Jeru; Deschamps, Michaël; Sarou-Kanian, Vincent; Etiemble, Aurélien; Douillard, Thierry; Maire, Eric; Lestriez, Bernard

2017-09-01

Lithium-ion batteries are electrochemical storage devices using the electrochemical activity of the lithium ion in relation to intercalation compounds owing to mass transport phenomena through diffusion. Diffusion of the lithium ion in the electrode pores has been poorly understood due to the lack of experimental techniques for measuring its self-diffusion coefficient in porous media. Magic-Angle Spinning, Pulsed Field Gradient, Stimulated-Echo Nuclear Magnetic Resonance (MAS-PFG-STE NMR) was used here for the first time to measure the self-diffusion coefficients of the electrolyte species in the LP30 battery electrolyte (i.e. a 1 M solution of LiPF6 dissolved in 1:1 Ethylene Carbonate - Dimethyl Carbonate) in model composites. These composite electrodes were made of alumina, carbon black and PVdF-HFP. Alumina's magnetic susceptibility is close to the measured magnetic susceptibility of the LP30 electrolyte thereby limiting undesirable internal field gradients. Interestingly, the self-diffusion coefficient of lithium ions decreases with increasing carbon content. FIB-SEM was used to describe the 3D geometry of the samples. The comparison between the reduction of self-diffusion coefficients as measured by PFG-NMR and as geometrically derived from FIB/SEM tortuosity values highlights the contribution of specific interactions at the material/electrolyte interface on the lithium transport properties.

New insight into the ZnO sulfidation reaction: mechanism and kinetics modeling of the ZnS outward growth.

PubMed

Neveux, Laure; Chiche, David; Pérez-Pellitero, Javier; Favergeon, Loïc; Gay, Anne-Sophie; Pijolat, Michèle

2013-02-07

Zinc oxide based materials are commonly used for the final desulfurization of synthesis gas in Fischer-Tropsch based XTL processes. Although the ZnO sulfidation reaction has been widely studied, little is known about the transformation at the crystal scale, its detailed mechanism and kinetics. A model ZnO material with well-determined characteristics (particle size and shape) has been synthesized to perform this study. Characterizations of sulfided samples (using XRD, TEM and electron diffraction) have shown the formation of oriented polycrystalline ZnS nanoparticles with a predominant hexagonal form (wurtzite phase). TEM observations also have evidenced an outward development of the ZnS phase, showing zinc and oxygen diffusion from the ZnO-ZnS internal interface to the surface of the ZnS particle. The kinetics of ZnO sulfidation by H(2)S has been investigated using isothermal and isobaric thermogravimetry. Kinetic tests have been performed that show that nucleation of ZnS is instantaneous compared to the growth process. A reaction mechanism composed of eight elementary steps has been proposed to account for these results, and various possible rate laws have been determined upon approximation of the rate-determining step. Thermogravimetry experiments performed in a wide range of H(2)S and H(2)O partial pressures have shown that the ZnO sulfidation reaction rate has a nonlinear variation with H(2)S partial pressure at the same time no significant influence of water vapor on reaction kinetics has been observed. From these observations, a mixed kinetics of external interface reaction with water desorption and oxygen diffusion has been determined to control the reaction kinetics and the proposed mechanism has been validated. However, the formation of voids at the ZnO-ZnS internal interface, characterized by TEM and electron tomography, strongly slows down the reaction rate. Therefore, the impact of the decreasing ZnO-ZnS internal interface on reaction kinetics has been taken into account in the reaction rate expression. In this way the void formation at the interface has been modeled considering a random nucleation followed by an isotropic growth of cavities. Very good agreement has been observed between both experimental and calculated rates after taking into account the decrease in the ZnO-ZnS internal interface.

Transscleral diffusion of ethacrynic acid and sodium fluorescein

PubMed Central

Lin, Cheng-Wen; Wang, Yong; Challa, Pratap; Epstein, David L.

2007-01-01

Purpose One of the current limitations in developing novel glaucoma drugs that target the trabecular meshwork (TM) is the induced corneal toxicity from eyedrop formulations. To avoid the corneal toxicity, an alternative approach would be to deliver TM drugs through the sclera. To this end, we quantified ex vivo diffusion coefficient of a potential TM drug, ethacrynic acid (ECA), and investigated mechanisms of ECA transport in the sclera. Methods An Ussing-type diffusion apparatus was built to measure the apparent diffusion coefficient of ECA in fresh porcine sclera at 4 °C. To understand mechanisms of ECA transport, we quantified the transscleral transport of a fluorescent tracer, sodium fluorescein (NaF), that has a similar molecular weight but is more hydrophilic compared to ECA. Furthermore, we developed a mathematical model to simulate the transport processes and used it to analyze the experimental data. The model was also used to investigate the dependence of diffusion coefficients on volume fraction of viable cells and the binding of NaF and ECA to scleral tissues. Results The diffusion coefficients of ECA and NaF in the sclera were 48.5±15.1x10-7 cm2/s (n=9) and 5.23±1.93x10-7 cm2/s (n=8), respectively. Both diffusion coefficients were insensitive to cell shrinkage caused by ECA during the diffusion experiments and cell damage caused by the storage of tissues ex vivo before the experiments. Binding of ECA to scleral tissues could not be detected. The apparent maximum binding capacity and the apparent equilibrium dissociation constant for NaF were 80±5 mM and 2.5±0.5 mM (n=3), respectively. Conclusions These data demonstrated that ECA diffusion was minimally hindered by structures in the sclera, presumably due to the lack of cells and binding sites for ECA in the sclera. PMID:17356511

Effect of hydrodynamic interactions on the diffusion of integral membrane proteins: diffusion in plasma membranes.

PubMed Central

Bussell, S J; Koch, D L; Hammer, D A

1995-01-01

Tracer diffusion coefficients of integral membrane proteins (IMPs) in intact plasma membranes are often much lower than those found in blebbed, organelle, and reconstituted membranes. We calculate the contribution of hydrodynamic interactions to the tracer, gradient, and rotational diffusion of IMPs in plasma membranes. Because of the presence of immobile IMPs, Brinkman's equation governs the hydrodynamics in plasma membranes. Solutions of Brinkman's equation enable the calculation of short-time diffusion coefficients of IMPs. There is a large reduction in particle mobilities when a fraction of them is immobile, and as the fraction increases, the mobilities of the mobile particles continue to decrease. Combination of the hydrodynamic mobilities with Monte Carlo simulation results, which incorporate excluded area effects, enable the calculation of long-time diffusion coefficients. We use our calculations to analyze results for tracer diffusivities in several different systems. In erythrocytes, we find that the hydrodynamic theory, when combined with excluded area effects, closes the gap between existing theory and experiment for the mobility of band 3, with the remaining discrepancy likely due to direct obstruction of band 3 lateral mobility by the spectrin network. In lymphocytes, the combined hydrodynamic-excluded area theory provides a plausible explanation for the reduced mobility of sIg molecules induced by binding concanavalin A-coated platelets. However, the theory does not explain all reported cases of "anchorage modulation" in all cell types in which receptor mobilities are reduced after binding by concanavalin A-coated platelets. The hydrodynamic theory provides an explanation of why protein lateral mobilities are restricted in plasma membranes and why, in many systems, deletion of the cytoplasmic tail of a receptor has little effect on diffusion rates. However, much more data are needed to test the theory definitively. We also predict that gradient and tracer diffusivities are the same to leading order. Finally, we have calculated rotational diffusion coefficients in plasma membranes. They decrease less rapidly than translational diffusion coefficients with increasing protein immobilization, and the results agree qualitatively with the limited experimental data available. PMID:7612825

Hepatocellular carcinoma: short-term reproducibility of apparent diffusion coefficient and intravoxel incoherent motion parameters at 3.0T.

PubMed

Kakite, Suguru; Dyvorne, Hadrien; Besa, Cecilia; Cooper, Nancy; Facciuto, Marcelo; Donnerhack, Claudia; Taouli, Bachir

2015-01-01

To evaluate short-term test-retest and interobserver reproducibility of IVIM (intravoxel incoherent motion) diffusion parameters and ADC (apparent diffusion coefficient) of hepatocellular carcinoma (HCC) and liver parenchyma at 3.0T. In this prospective Institutional Review Board (IRB)-approved study, 11 patients were scanned twice using a free-breathing single-shot echo-planar-imaging, diffusion-weighted imaging (DWI) sequence using 4 b values (b = 0, 50, 500, 1000 s/mm(2)) and IVIM DWI using 16 b values (0-800 s/mm(2)) at 3.0T. IVIM parameters (D: true diffusion coefficient, D*: pseudodiffusion coefficient, PF: perfusion fraction) and ADC (using 4 b and 16 b) were calculated. Short-term test-retest and interobserver reproducibility of IVIM parameters and ADC were assessed by measuring correlation coefficient, coefficient of variation (CV), and Bland-Altman limits of agreements (BA-LA). Fifteen HCCs were assessed in 10 patients. Reproducibility of IVIM metrics in HCC was poor for D* and PF (mean CV 60.6% and 37.3%, BA-LA: -161.6% to 135.3% and -66.2% to 101.0%, for D* and PF, respectively), good for D and ADC (CV 19.7% and <16%, BA-LA -57.4% to 36.3% and -38.2 to 34.1%, for D and ADC, respectively). Interobserver reproducibility was on the same order of test-retest reproducibility except for PF in HCC. Reproducibility of diffusion parameters was better in liver parenchyma compared to HCC. Poor reproducibility of D*/PF and good reproducibility for D/ADC were observed in HCC and liver parenchyma. These findings may have implications for trials using DWI in HCC. © 2014 Wiley Periodicals, Inc.

Effect of sharp maximum in ion diffusivity for liquid xenon

NASA Astrophysics Data System (ADS)

Lankin, A. V.; Orekhov, M. A.

2016-11-01

Ion diffusion in a liquid usually could be treated as a movement of an ion cluster in a viscous media. For small ions this leads to a special feature: diffusion coefficient is either independent of the ion size or increases with it. We find a different behavior for small ions in liquid xenon. Calculation of the dependence of an ion diffusion coefficient in liquid xenon on the ion size is carried out. Classical molecular dynamics method is applied. Calculated dependence of the ion diffusion coefficient on its radius has sharp maximums at the ion radiuses 1.75 and 2 Å. Every maximum is placed between two regions with different stable ion cluster configurations. This leads to the instability of these configurations in a small region between them. Consequently ion with radius near 1.75 or 2 Å could jump from one configuration to another. This increases the speed of the diffusion. A simple qualitative model for this effect is suggested. The decomposition of the ion movement into continuous and jump diffusion shows that continuous part of the diffusion is the same as for the ion cluster in the stable region.

Precise Inference and Characterization of Structural Organization (PICASO) of tissue from molecular diffusion

PubMed Central

Ning, Lipeng; Özarslan, Evren; Westin, Carl-Fredrik; Rathi, Yogesh

2017-01-01

Inferring the microstructure of complex media from the diffusive motion of molecules is a challenging problem in diffusion physics. In this paper, we introduce a novel representation of diffusion MRI (dMRI) signal from tissue with spatially-varying diffusivity using a diffusion disturbance function. This disturbance function contains information about the (intra-voxel) spatial fluctuations in diffusivity due to restrictions, hindrances and tissue heterogeneity of the underlying tissue substrate. We derive the short- and long-range disturbance coefficients from this disturbance function to characterize the tissue structure and organization. Moreover, we provide an exact relation between the disturbance coefficients and the time-varying moments of the diffusion propagator, as well as their relation to specific tissue microstructural information such as the intra-axonal volume fraction and the apparent axon radius. The proposed approach is quite general and can model dMRI signal for any type of gradient sequence (rectangular, oscillating, etc.) without using the Gaussian phase approximation. The relevance of the proposed PICASO model is explored using Monte-Carlo simulations and in-vivo dMRI data. The results show that the estimated disturbance coefficients can distinguish different types of microstructural organization of axons. PMID:27751940

Mesoscopic structure of neuronal tracts from time-dependent diffusion

PubMed Central

Burcaw, Lauren M.; Fieremans, Els; Novikov, Dmitry S.

2015-01-01

Interpreting brain diffusion MRI measurements in terms of neuronal structure at a micrometer level is an exciting unresolved problem. Here we consider diffusion transverse to a bundle of fibers, and show theoretically, as well as using Monte Carlo simulations and measurements in a phantom made of parallel fibers mimicking axons, that the time dependent diffusion coefficient approaches its macroscopic limit slowly, in a (lnt)/t fashion. The logarithmic singularity arises due to short range disorder in the fiber packing. We identify short range disorder in axonal fibers based on histological data from the splenium, and argue that the time dependent contribution to the overall diffusion coefficient from the extra-axonal water dominates that of the intra-axonal water. This dominance may explain the bias in measuring axon diameters in clinical settings. The short range disorder is also reflected in the linear frequency dependence of the diffusion coefficient measured with oscillating gradients, in agreement with recent experiments. Our results relate the measured diffusion to the mesoscopic structure of neuronal tissue, uncovering the sensitivity of diffusion metrics to axonal arrangement within a fiber tract, and providing an alternative interpretation of axonal diameter mapping techniques. PMID:25837598

Precise Inference and Characterization of Structural Organization (PICASO) of tissue from molecular diffusion.

PubMed

Ning, Lipeng; Özarslan, Evren; Westin, Carl-Fredrik; Rathi, Yogesh

2017-02-01

Inferring the microstructure of complex media from the diffusive motion of molecules is a challenging problem in diffusion physics. In this paper, we introduce a novel representation of diffusion MRI (dMRI) signal from tissue with spatially-varying diffusivity using a diffusion disturbance function. This disturbance function contains information about the (intra-voxel) spatial fluctuations in diffusivity due to restrictions, hindrances and tissue heterogeneity of the underlying tissue substrate. We derive the short- and long-range disturbance coefficients from this disturbance function to characterize the tissue structure and organization. Moreover, we provide an exact relation between the disturbance coefficients and the time-varying moments of the diffusion propagator, as well as their relation to specific tissue microstructural information such as the intra-axonal volume fraction and the apparent axon radius. The proposed approach is quite general and can model dMRI signal for any type of gradient sequence (rectangular, oscillating, etc.) without using the Gaussian phase approximation. The relevance of the proposed PICASO model is explored using Monte-Carlo simulations and in-vivo dMRI data. The results show that the estimated disturbance coefficients can distinguish different types of microstructural organization of axons. Copyright © 2016 Elsevier Inc. All rights reserved.

Mesoscopic structure of neuronal tracts from time-dependent diffusion.

PubMed

Burcaw, Lauren M; Fieremans, Els; Novikov, Dmitry S

2015-07-01

Interpreting brain diffusion MRI measurements in terms of neuronal structure at a micrometer level is an exciting unresolved problem. Here we consider diffusion transverse to a bundle of fibers, and show theoretically, as well as using Monte Carlo simulations and measurements in a phantom made of parallel fibers mimicking axons, that the time dependent diffusion coefficient approaches its macroscopic limit slowly, in a (ln t)/t fashion. The logarithmic singularity arises due to short range disorder in the fiber packing. We identify short range disorder in axonal fibers based on histological data from the splenium, and argue that the time dependent contribution to the overall diffusion coefficient from the extra-axonal water dominates that of the intra-axonal water. This dominance may explain the bias in measuring axon diameters in clinical settings. The short range disorder is also reflected in the asymptotically linear frequency dependence of the diffusion coefficient measured with oscillating gradients, in agreement with recent experiments. Our results relate the measured diffusion to the mesoscopic structure of neuronal tissue, uncovering the sensitivity of diffusion metrics to axonal arrangement within a fiber tract, and providing an alternative interpretation of axonal diameter mapping techniques. Copyright © 2015 Elsevier Inc. All rights reserved.

Preparation of Cu2ZnSnS4 nano-crystalline powder by mechano-chemical method

NASA Astrophysics Data System (ADS)

Alirezazadeh, Farzaneh; Sheibani, Saeed; Rashchi, Fereshteh

2018-01-01

Copper zinc tin sulfide (Cu2ZnSnS4, CZTS) is one of the most promising ceramic materials as an absorber layer in solar cells due to its suitable band gap, high absorption coefficient and non-toxic and environmental friendly constituent elements. In this work, nano-crystalline CZTS powder was synthesized by mechanical milling. Elemental powders of Cu, Zn, Sn and were mixed in atomic ratio of 2:1:1:4 according to the stoichiometry of Cu2ZnSnS4 and then milled in a planetary high energy ball mill under argon atmosphere. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and diffusion reflectance spectroscopy (DRS). XRD results confirm the formation of single-phase CZTS with kesterite structure after 20 h of milling. Also, the mean crystallite size was about 35 nm. SEM results show that after 20 h of milling, the product has a relatively uniform particle size distribution. Optical properties of the product indicate that the band gap of prepared CZTS is 1.6 eV which is near to the optimum value for photovoltaic solar cells showing as a light absorber material in solar energy applications.

Self-diffusion of Si and O in diopside-anorthite melt at high pressures

NASA Astrophysics Data System (ADS)

Tinker, David; Lesher, Charles E.; Hutcheon, Ian D.

2003-01-01

Self-diffusion coefficients for Si and O in Di 58An 42 liquid were measured from 1 to 4 GPa and temperatures from 1510 to 1764°C. Glass starting powders enriched in 18O and 28Si were mated to isotopically normal glass powders to form simple diffusion couples, and self-diffusion experiments were conducted in the piston cylinder device (1 and 2 GPa) and in the multianvil apparatus (3.5 and 4 GPa). Profiles of 18O/ 16O and 29,30Si/ 28Si were measured using secondary ion mass spectrometry. Self-diffusion coefficients for O (D(O)) are slightly greater than self-diffusion coefficients for Si (D(Si)) and are often the same within error. For example, D(O) = 4.20 ± 0.42 × 10 -11 m 2/s and D(Si) = 3.65 ± 0.37 × 10 -11 m 2/s at 1 GPa and 1662°C. Activation energies for self-diffusion are 215 ± 13 kJ/mol for O and 227 ± 13 kJ/mol for Si. Activation volumes for self-diffusion are -2.1 ± 0.4 cm 3/mol and -2.3 ± 0.4 cm 3/mol for O and Si, respectively. The similar self-diffusion coefficients for Si and O, similar activation energies, and small, negative activation volumes are consistent with Si and O transport by a cooperative diffusion mechanism, most likely involving the formation and disassociation of a high-coordinated intermediate species. The small absolute magnitudes of the activation volumes imply that Di 58An 42 liquid is close to a transition from negative to positive activation volume, and Adam-Gibbs theory suggests that this transition is linked to the existence of a critical fraction (˜0.6) of bridging oxygen.

Establishment of a Physical Model for Solute Diffusion in Hydrogel: Understanding the Diffusion of Proteins in Poly(sulfobetaine methacrylate) Hydrogel.

PubMed

Zhou, Yuhang; Li, Junjie; Zhang, Ying; Dong, Dianyu; Zhang, Ershuai; Ji, Feng; Qin, Zhihui; Yang, Jun; Yao, Fanglian

2017-02-02

Prediction of the diffusion coefficient of solute, especially bioactive molecules, in hydrogel is significant in the biomedical field. Considering the randomness of solute movement in a hydrogel network, a physical diffusion RMP-1 model based on obstruction theory was established in this study. The physical properties of the solute and the polymer chain and their interactions were introduced into this model. Furthermore, models RMP-2 and RMP-3 were established to understand and predict the diffusion behaviors of proteins in hydrogel. In addition, zwitterionic poly(sulfobetaine methacrylate) (PSBMA) hydrogels with wide range and fine adjustable mesh sizes were prepared and used as efficient experimental platforms for model validation. The Flory characteristic ratios, Flory-Huggins parameter, mesh size, and polymer chain radii of PSBMA hydrogels were determined. The diffusion coefficients of the proteins (bovine serum albumin, immunoglobulin G, and lysozyme) in PSBMA hydrogels were studied by the fluorescence recovery after photobleaching technique. The measured diffusion coefficients were compared with the predictions of obstruction models, and it was found that our model presented an excellent predictive ability. Furthermore, the assessment of our model revealed that protein diffusion in PSBMA hydrogel would be affected by the physical properties of the protein and the PSBMA network. It was also confirmed that the diffusion behaviors of protein in zwitterionic hydrogels can be adjusted by changing the cross-linking density of the hydrogel and the ionic strength of the swelling medium. Our model is expected to possess accurate predictive ability for the diffusion coefficient of solute in hydrogel, which will be widely used in the biomedical field.

Diffusion across the modified polyethylene separator GX in the heat-sterilizable AgO-Zn battery

NASA Technical Reports Server (NTRS)

Lutwack, R.

1973-01-01

Models of diffusion across an inert membrane have been studied using the computer program CINDA. The models were constructed to simulate various conditions obtained in the consideration of the diffusion of Ag (OH)2 ions in the AgO-Zn battery. The effects on concentrations across the membrane at the steady state and on the fluxout as a function of time were used to examine the consequences of stepwise reducing the number of sources of ions, of stepwise blocking the source and sink surfaces, of varying the magnitude of the diffusion coefficient for a uniform membrane, of varying the diffusion coefficient across the membrane, and of excluding volumes to diffusion.

Diffusion of multi-isotopic chemical species in molten silicates

NASA Astrophysics Data System (ADS)

Watkins, James M.; Liang, Yan; Richter, Frank; Ryerson, Frederick J.; DePaolo, Donald J.

2014-08-01

Diffusion experiments in a simplified Na2O-CaO-SiO2 liquid system are used to develop a general formulation for the fractionation of Ca isotopes during liquid-phase diffusion. Although chemical diffusion is a well-studied process, the mathematical description of the effects of diffusion on the separate isotopes of a chemical element is surprisingly underdeveloped and uncertain. Kinetic theory predicts a mass dependence on isotopic mobility, but it is unknown how this translates into a mass dependence on effective binary diffusion coefficients, or more generally, the chemical diffusion coefficients that are housed in a multicomponent diffusion matrix. Our experiments are designed to measure Ca mobility, effective binary diffusion coefficients, the multicomponent diffusion matrix, and the effects of chemical diffusion on Ca isotopes in a liquid of single composition. We carried out two chemical diffusion experiments and one self-diffusion experiment, all at 1250 °C and 0.7 GPa and using a bulk composition for which other information is available from the literature. The self-diffusion experiment is used to determine the mobility of Ca in the absence of diffusive fluxes of other liquid components. The chemical diffusion experiments are designed to determine the effect on Ca isotope fractionation of changing the counter-diffusing component from fast-diffusing Na2O to slow-diffusing SiO2. When Na2O is the main counter-diffusing species, CaO diffusion is fast and larger Ca isotopic effects are generated. When SiO2 is the main counter-diffusing species, CaO diffusion is slow and smaller Ca isotopic effects are observed. In both experiments, the liquid is initially isotopically homogeneous, and during the experiment Ca isotopes become fractionated by diffusion. The results are used as a test of a new general expression for the diffusion of isotopes in a multicomponent liquid system that accounts for both self diffusion and the effects of counter-diffusing species. Our results show that (1) diffusive isotopic fractionations depend on the direction of diffusion in composition space, (2) diffusive isotopic fractionations scale with effective binary diffusion coefficient, as previously noted by Watkins et al. (2011), (3) self-diffusion is not decoupled from chemical diffusion, (4) self diffusion can be faster than or slower than chemical diffusion and (5) off-diagonal terms in the chemical diffusion matrix have isotopic mass-dependence. The results imply that relatively large isotopic fractionations can be generated by multicomponent diffusion even in the absence of large concentration gradients of the diffusing element. The new formulations for isotope diffusion can be tested with further experimentation and provide an improved framework for interpreting mass-dependent isotopic variations in natural liquids.

Accurate determination of the diffusion coefficient of proteins by Fourier analysis with whole column imaging detection.

PubMed

Zarabadi, Atefeh S; Pawliszyn, Janusz

2015-02-17

Analysis in the frequency domain is considered a powerful tool to elicit precise information from spectroscopic signals. In this study, the Fourier transformation technique is employed to determine the diffusion coefficient (D) of a number of proteins in the frequency domain. Analytical approaches are investigated for determination of D from both experimental and data treatment viewpoints. The diffusion process is modeled to calculate diffusion coefficients based on the Fourier transformation solution to Fick's law equation, and its results are compared to time domain results. The simulations characterize optimum spatial and temporal conditions and demonstrate the noise tolerance of the method. The proposed model is validated by its application for the electropherograms from the diffusion path of a set of proteins. Real-time dynamic scanning is conducted to monitor dispersion by employing whole column imaging detection technology in combination with capillary isoelectric focusing (CIEF) and the imaging plug flow (iPF) experiment. These experimental techniques provide different peak shapes, which are utilized to demonstrate the Fourier transformation ability in extracting diffusion coefficients out of irregular shape signals. Experimental results confirmed that the Fourier transformation procedure substantially enhanced the accuracy of the determined values compared to those obtained in the time domain.

Characterization of Ultrasound Energy Diffusion Due to Small-Size Damage on an Aluminum Plate Using Piezoceramic Transducers

PubMed Central

Lu, Guangtao; Feng, Qian; Li, Yourong; Wang, Hao; Song, Gangbing

2017-01-01

During the propagation of ultrasonic waves in structures, there is usually energy loss due to ultrasound energy diffusion and dissipation. The aim of this research is to characterize the ultrasound energy diffusion that occurs due to small-size damage on an aluminum plate using piezoceramic transducers, for the future purpose of developing a damage detection algorithm. The ultrasonic energy diffusion coefficient is related to the damage distributed in the medium. Meanwhile, the ultrasonic energy dissipation coefficient is related to the inhomogeneity of the medium. Both are usually employed to describe the characteristics of ultrasound energy diffusion. The existence of multimodes of Lamb waves in metallic plate structures results in the asynchronous energy transport of different modes. The mode of Lamb waves has a great influence on ultrasound energy diffusion as a result, and thus has to be chosen appropriately. In order to study the characteristics of ultrasound energy diffusion in metallic plate structures, an experimental setup of an aluminum plate with a through-hole, whose diameter varies from 0.6 mm to 1.2 mm, is used as the test specimen with the help of piezoceramic transducers. The experimental results of two categories of damages at different locations reveal that the existence of damage changes the energy transport between the actuator and the sensor. Also, when there is only one dominate mode of Lamb wave excited in the structure, the ultrasound energy diffusion coefficient decreases approximately linearly with the diameter of the simulated damage. Meanwhile, the ultrasonic energy dissipation coefficient increases approximately linearly with the diameter of the simulated damage. However, when two or more modes of Lamb waves are excited, due to the existence of different group velocities between the different modes, the energy transport of the different modes is asynchronous, and the ultrasonic energy diffusion is not strictly linear with the size of the damage. Therefore, it is recommended that only one dominant mode of Lamb wave should be excited during the characterization process, in order to ensure that the linear relationship between the damage size and the characteristic parameters is maintained. In addition, the findings from this paper demonstrate the potential of developing future damage detection algorithms using the linear relationships between damage size and the ultrasound energy diffusion coefficient or ultrasonic energy dissipation coefficient when a single dominant mode is excited. PMID:29207530

Dependence of Exciton Diffusion Length and Diffusion Coefficient on Photophysical Parameters in Bulk Heterojunction Organic Solar Cells

NASA Astrophysics Data System (ADS)

Yeboah, Douglas; Singh, Jai

2017-11-01

Recently, the dependence of exciton diffusion length (LD ) on some photophysical parameters of organic solids has been experimentally demonstrated, however no systematic theoretical analysis of this phenomenon has been carried out. We have conducted a theoretical study by using the Förster resonance energy transfer and Dexter carrier transfer mechanisms together with the Einstein-Smoluchowski diffusion equation to derive analytical models for the diffusion lengths (LD ) and diffusion coefficients (D) of singlet (S) and triplet (T) excitons in organic solids as functions of spectral overlap integral (J) , photoluminescence (PL) quantum yield (φD ) , dipole moment (μT ) and refractive index (n) of the photoactive material. The exciton diffusion lengths and diffusion coefficients in some selected organic solids were calculated, and we found that the singlet exciton diffusion length (LDS ) increases with φD and J, and decreases with n. Also, the triplet exciton diffusion length (LDT ) increases with φD and decreases with μT . These may be achieved through doping the organic solids into broad optical energy gap host materials as observed in previous experiments. The calculated exciton diffusion lengths are compared with experimental values and a reasonably good agreement is found between them. The results presented are expected to provide insight relevant to the synthesis of new organic solids for fabrication of bulk heterojunction organic solar cells characterized by better power conversion efficiency.

Effects of molecular weight on the diffusion coefficient of aquatic dissolved organic matter and humic substances.

PubMed

Balch, J; Guéguen, C

2015-01-01

In situ measurements of labile metal species using diffusive gradients in thin films (DGT) passive samplers are based on the diffusion rates of individual species. Although most studies have dealt with chemically isolated humic substances, the diffusion of dissolved organic matter (DOM) across the hydrogel is not well understood. In this study, the diffusion coefficient (D) and molecular weight (MW) of 11 aquatic DOM and 4 humic substances (HS) were determined. Natural, unaltered aquatic DOM was capable of diffusing across the diffusive gel membrane with D values ranging from 2.48×10(-6) to 5.31×10(-6) cm(2) s(-1). Humic substances had diffusion coefficient values ranging from 3.48×10(-6) to 6.05×10(-6) cm(2) s(-1), congruent with previous studies. Molecular weight of aquatic DOM and HS samples (∼500-1750 Da) measured using asymmetrical flow field-flow fractionation (AF4) strongly influenced D, with larger molecular weight DOM having lower D values. No noticeable changes in DOM size properties were observed during the diffusion process, suggesting that DOM remains intact following diffusion across the diffusive gel. The influence of molecular weight on DOM mobility will assist in further understanding and development of the DGT technique and the uptake and mobility of contaminants associated with DOM in aquatic environments. Copyright © 2014 Elsevier Ltd. All rights reserved.

Method of preparing corrosion resistant composite materials

DOEpatents

Kaun, Thomas D.

1993-01-01

Method of manufacture of ceramic materials which require stability in severely-corrosive environment having high alkali-metal activity, high sulfur/sulfide activity and/or molten halides at temperatures of 200.degree.-550.degree. C. or organic salt (including SO.sub.2 and SO.sub.2 Cl.sub.2) at temperatures of 25.degree.-200.degree. C. These surfide ceramics form stoichiometric (single-phase) compounds with sulfides of Ca, Li, Na, K, Al, Mg, Si, Y, La, Ce, Ga, Ba, Zr and Sr and show melting-points that are sufficiently low and have excellent wettability with many metals (Fe, Ni, Mo) to easily form metal/ceramic seals. Ceramic compositions are also formulated to adequately match thermal expansion coefficient of adjacent metal components.

Observatory enabled discovery of diffuse discharge temperature structure

NASA Astrophysics Data System (ADS)

Bemis, K. G.; Lee, R.; Ivakin, A. N.

2016-12-01

Underwater cabled observatories provide long term but short time and spatial scale measurements of hydrothermal discharge properties. For the first time, an intricate picture of diffuse discharge has been captured at both Axial Volcano (Axial) and the Main Endeavour Field (MEF) on the Juan de Fuca Ridge. This study combines thermistor (3D array, 2D array and spot) and acoustic data to compare the statistical and distribution characteristics of diffuse discharge for narrow crack flow (at ASHES field on Axial) and distributive flow out of a sulfide structure (at Grotto vent in MEF). Two surprising observations seem to apply to both styles of diffuse discharge: (1) thermal variance scales with the mean temperature suggesting coherent flow structures exist in the form of plumes, wakes or boundary layers, and (2) thermal hot spots are persistently localized in space, despite tidal current disruption. Thermal variance was measured at ASHES using a 3D thermistor array (TMPSF) with 10 s sampling over two years and at Grotto using 2D thermistor arrays with 1 hr sampling over several years and a ROV-held CTD (Seabird 39plus) with 0.5 second sampling over several minutes. For locations with temperatures greater than ambient, the variance in temperature scales with the mean temperature. This unusual statistical property is characteristic of self-similar flows like plumes, wakes, and boundary layers and arises from the bounded mixing of a cooling high temperature fluid with a cold ambient fluid. Thus this observation implies an underlying coherence to the diffuse discharge that has not yet been adequately captured or described. A coherent flow like a plume should have a discoverable spatial pattern, albeit one that may vary with the influence of tides. Acoustic observations ( 1m diameter footprint) of the Grotto sulfide edifice found stable local hot spots of diffuse discharge that sway with tides. In contrast, the 3D thermistor array at ASHES sees very localized (single thermistor) hot spots that persist for months. Is this a fundamental difference between two styles of diffuse discharge? Alternate conceptual models of diffuse discharge are used to place localized observations in a spatial context and develop a rigorous understanding of the spatial and temporal pattern of diffuse discharge for both crack and distributive styles.

Investigation of heat and mass transfer under the influence of variable diffusion coefficient and thermal conductivity

NASA Astrophysics Data System (ADS)

Mohyud Din, S. T.; Zubair, T.; Usman, M.; Hamid, M.; Rafiq, M.; Mohsin, S.

2018-04-01

This study is devoted to analyze the influence of variable diffusion coefficient and variable thermal conductivity on heat and mass transfer in Casson fluid flow. The behavior of concentration and temperature profiles in the presence of Joule heating and viscous dissipation is also studied. The dimensionless conversation laws with suitable BCs are solved via Modified Gegenbauer Wavelets Method (MGWM). It has been observed that increase in Casson fluid parameter (β ) and parameter ɛ enhances the Nusselt number. Moreover, Nusselt number of Newtonian fluid is less than that of the Casson fluid. The phenomenon of mass transport can be increased by solute of variable diffusion coefficient rather than solute of constant diffusion coefficient. A detailed analysis of results is appropriately highlighted. The obtained results, error estimates, and convergence analysis reconfirm the credibility of proposed algorithm. It is concluded that MGWM is an appropriate tool to tackle nonlinear physical models and hence may be extended to some other nonlinear problems of diversified physical nature also.

Multi-charge-state molecular dynamics and self-diffusion coefficient in the warm dense matter regime

NASA Astrophysics Data System (ADS)

Fu, Yongsheng; Hou, Yong; Kang, Dongdong; Gao, Cheng; Jin, Fengtao; Yuan, Jianmin

2018-01-01

We present a multi-ion molecular dynamics (MIMD) simulation and apply it to calculating the self-diffusion coefficients of ions with different charge-states in the warm dense matter (WDM) regime. First, the method is used for the self-consistent calculation of electron structures of different charge-state ions in the ion sphere, with the ion-sphere radii being determined by the plasma density and the ion charges. The ionic fraction is then obtained by solving the Saha equation, taking account of interactions among different charge-state ions in the system, and ion-ion pair potentials are computed using the modified Gordon-Kim method in the framework of temperature-dependent density functional theory on the basis of the electron structures. Finally, MIMD is used to calculate ionic self-diffusion coefficients from the velocity correlation function according to the Green-Kubo relation. A comparison with the results of the average-atom model shows that different statistical processes will influence the ionic diffusion coefficient in the WDM regime.

Method for Calculating the Optical Diffuse Reflection Coefficient for the Ocular Fundus

NASA Astrophysics Data System (ADS)

Lisenko, S. A.; Kugeiko, M. M.

2016-07-01

We have developed a method for calculating the optical diffuse reflection coefficient for the ocular fundus, taking into account multiple scattering of light in its layers (retina, epithelium, choroid) and multiple refl ection of light between layers. The method is based on the formulas for optical "combination" of the layers of the medium, in which the optical parameters of the layers (absorption and scattering coefficients) are replaced by some effective values, different for cases of directional and diffuse illumination of the layer. Coefficients relating the effective optical parameters of the layers and the actual values were established based on the results of a Monte Carlo numerical simulation of radiation transport in the medium. We estimate the uncertainties in retrieval of the structural and morphological parameters for the fundus from its diffuse reflectance spectrum using our method. We show that the simulated spectra correspond to the experimental data and that the estimates of the fundus parameters obtained as a result of solving the inverse problem are reasonable.

Random walk numerical simulation for hopping transport at finite carrier concentrations: diffusion coefficient and transport energy concept.

PubMed

Gonzalez-Vazquez, J P; Anta, Juan A; Bisquert, Juan

2009-11-28

The random walk numerical simulation (RWNS) method is used to compute diffusion coefficients for hopping transport in a fully disordered medium at finite carrier concentrations. We use Miller-Abrahams jumping rates and an exponential distribution of energies to compute the hopping times in the random walk simulation. The computed diffusion coefficient shows an exponential dependence with respect to Fermi-level and Arrhenius behavior with respect to temperature. This result indicates that there is a well-defined transport level implicit to the system dynamics. To establish the origin of this transport level we construct histograms to monitor the energies of the most visited sites. In addition, we construct "corrected" histograms where backward moves are removed. Since these moves do not contribute to transport, these histograms provide a better estimation of the effective transport level energy. The analysis of this concept in connection with the Fermi-level dependence of the diffusion coefficient and the regime of interest for the functioning of dye-sensitised solar cells is thoroughly discussed.

Self-diffusion Coefficient and Structure of Binary n-Alkane Mixtures at the Liquid-Vapor Interfaces.

PubMed

Chilukoti, Hari Krishna; Kikugawa, Gota; Ohara, Taku

2015-10-15

The self-diffusion coefficient and molecular-scale structure of several binary n-alkane liquid mixtures in the liquid-vapor interface regions have been examined using molecular dynamics simulations. It was observed that in hexane-tetracosane mixture hexane molecules are accumulated in the liquid-vapor interface region and the accumulation intensity decreases with increase in a molar fraction of hexane in the examined range. Molecular alignment and configuration in the interface region of the liquid mixture change with a molar fraction of hexane. The self-diffusion coefficient in the direction parallel to the interface of both tetracosane and hexane in their binary mixture increases in the interface region. It was found that the self-diffusion coefficient of both tetracosane and hexane in their binary mixture is considerably higher in the vapor side of the interface region as the molar fraction of hexane goes lower, which is mostly due to the increase in local free volume caused by the local structure of the liquid in the interface region.

Measuring a diffusion coefficient by single-particle tracking: statistical analysis of experimental mean squared displacement curves.

PubMed

Ernst, Dominique; Köhler, Jürgen

2013-01-21

We provide experimental results on the accuracy of diffusion coefficients obtained by a mean squared displacement (MSD) analysis of single-particle trajectories. We have recorded very long trajectories comprising more than 1.5 × 10(5) data points and decomposed these long trajectories into shorter segments providing us with ensembles of trajectories of variable lengths. This enabled a statistical analysis of the resulting MSD curves as a function of the lengths of the segments. We find that the relative error of the diffusion coefficient can be minimized by taking an optimum number of points into account for fitting the MSD curves, and that this optimum does not depend on the segment length. Yet, the magnitude of the relative error for the diffusion coefficient does, and achieving an accuracy in the order of 10% requires the recording of trajectories with about 1000 data points. Finally, we compare our results with theoretical predictions and find very good qualitative and quantitative agreement between experiment and theory.

Pc 5 Spectral Density at ULTIMA stataions and its Radial Diffusion Coefficients for REE

NASA Astrophysics Data System (ADS)

Fujimoto, A.; Tokunaga, T.; Abe, S.; Uozumi, T.; Yoshikawa, A.; Mann, I. R.; Chi, P. J.; Engebretson, M. J.; Yumoto, K.

2009-12-01

Pc 5 magnetic pulsations with frequencies between 1.67 and 6.67 mHz, are believed to contribute to the Relativistic Electron Enhancement (REE) in the outer radiation belt during magnetic storms. Ground-based observations suggested that high-speed solar wind and large-amplitude Pc 5 waves with a long duration during the storm recovery phase are closely associated with the production of relativistic electrons [Baker et al., 1998; Rostoker et al., 1998; Mathie and Mann, 2000; O’Brien et al., 2001, 2003]. On the other hand, many relativistic electron acceleration mechanisms have been proposed theoretically. They are separated roughly into two themes: in situ acceleration at L lower than 6.6 by wave particle interactions (as internal source acceleration mechanisms) [Liu et al., 1999; Summers et al., 1999; Summers and Ma, 2000] and acceleration by radial diffusion to transport and accelerate a source population of electrons from the outer to the inner magnetosphere (as external source acceleration mechanisms) [Elkington et al., 1999, 2003; Hudson et al., 2000; Kim et al., 2001]. One possible external source acceleration mechanism is the resonant interaction with ULF toroidal and poloidal waves. In order to verify which of the two mechanisms is more effective for the REE, we have to examine the time variation of electron phase space density. Electron phase space density is not directly measured, but we can estimate radial diffusion coefficients using observational electric and magnetic data. The goal of this paper is to get more reliable radial diffusion coefficient from ground-based observational magnetic field and to show reasonability of it for radial diffusion model. We use the global magnetometer data obtained from ULTIMA (Ultra Large Terrestrial International Magnetic Array, see http://www.serc.kyushu-u.ac.jp/ultima/ultima.html) stations, to precisely define the radial diffusion timescales. The ULTIMA includes McMAC, CARISAM, 210MM and MAGDAS/CPMN magnetometer arrays. The radial diffusion coefficient can be given from the magnetic field power spectral density as a function of L, frequency (f) and m-number (m) in the Pc 5 frequency range during the REE related magnetic storms [see Brautigam et al., 2005]. We can fit Pc 5 power spectral density (L, f, m) using the ULTIMA data. The m-number of global Pc 5 pulsation on the ground is found to be almost less than 5. This is consistent with m-number required in the radial diffusion theory by Elkington et al. [1999, 2003]. We will compare the observationally estimated diffusion coefficient with theoretical diffusion coefficient [e.g. Elkington et al., 2006], and discuss adequacy of our diffusion coefficient.

Siderophile and chalcophile metals as tracers of the evolution of the Siberian Trap in the Noril'sk region, Russia

NASA Astrophysics Data System (ADS)

Brügmann, G. E.; Naldrett, A. J.; Asif, M.; Lightfoot, P. C.; Gorbachev, N. S.; Fedorenko, V. A.

1993-05-01

In this study Cu, Ni, and platinum-group elements (PGE) were determined in a sequence of basaltic and picritic lavas from the Siberian Trap in the Noril'sk area of Russia to constrain genetic relationships between the basalts and the petrogenesis of Ni-Cu-PGE sulfide deposits associated with the Talnakh and Noril'sk intrusions. In the most primitive basalts (8-19 wt% MgO) of the Tuklonsky (Tk) suite, Pt and Pd concentrations range from 4-13 ppb, increasing with decreasing MgO content; whereas Ir contents decrease with MgO from 0.8-0.05 ppb. The contrasting behavior of these elements, which all have very high sulfide-silicate partition coefficients, as well as the primitive mantle-like ratios of Cu/Y and Pd/Y, suggests that these magmas were not sulfide-saturated. The high PGE abundances imply that their parental magmas were also not sulfide saturated during partial melting in the mantle. Due to sulfide segregation, the overlying basalts of the Nadezhdinsky (Nd) series are low in Cu and Ni (52 and 38 ppm, respectively); highly depleted in all PGE; and have very low Cu/Y, Pd/Y, and Pd/Cu ratios. However, in stratigraphically higher levels, Cu, Ni, and PGE concentrations increase systematically through the Morongovsky (Mr) suite to reach a concentration plateau in the uppermost Mokulaevsky (Mk) suite (Pt 8 ppb; Pd: 9 ppb; Ir: 0.12 ppb; Rh: 0.4 ppb). At the same time, ratios such as Cu/Y increase and approach primitive mantle values. However, ratios involving PGE, such as Pd/Y, remain low, suggesting the removal of small amounts of sulfide (0.01-0.03%). The compositional variations in the basalts and the sulfide liquids can be quantitatively described by fractional segregation of a sulfide liquid in an open- or closed-system magma chamber. The latter model suggests that the basalts represent the eruption products of a zoned magma chamber in which light magma, with crustal components contaminated, overlies less contaminated, denser magma. Crustal contamination caused sulfide saturation, and the resulting sulfide liquids settled through a magma column and accumulated at the bottom of the chamber. In this model, the sulfide liquid is not in equilibrium with the whole magma mass, and sulfide segregation is compared with the zone-refining process of metallurgy. The sulfides become more enriched as they move through the magma; and although the magma left behind is depleted in PGE, Cu, and Ni, their concentrations also increase with depth. Eventually, the magma chamber is emptied from the top to the bottom, producing the flood basalt sequence and the associated intrusions and ore deposits. In the open-system model, sulfide saturation was initially caused by assimilation of crustal material by the Tuklonsky magma. Continuous and simultaneous replenishment, assimilation, and crystallization processes formed the lower Nd lavas. The concurrent removal of 0.5-1% sulfide strongly depleted these magmas in chalcophile and siderophile metals. Due to the continuous replenishment of the magma chamber with uncontaminated PGE-rich magma, succeeding lavas (Mr, Mk) show diminishing signs of crustal contamination and become less sulfide-saturated, as indicated by the increasing Ni, Cu, and PGE abundances. During the evolution of the chamber, the magma remained sulfur-saturated, and sulfides accumulated at the base. The composition of the sulfide ores could be regarded as a mixture consisting of low Ni-, Cu-, and PGE-sulfides derived with a low silicate/sulfide ratio (100) from the Tk-Nd magma and high Ni-, Cu-, and PGE-sulfides formed with a high ratio (10,000) from the Mr-Mk magma.

Molecular dynamics simulations of propane in slit shaped silica nano-pores: direct comparison with quasielastic neutron scattering experiments.

PubMed

Gautam, Siddharth; Le, Thu; Striolo, Alberto; Cole, David

2017-12-13

Molecular motion under confinement has important implications for a variety of applications including gas recovery and catalysis. Propane confined in mesoporous silica aerogel as studied using quasielastic neutron scattering (QENS) showed anomalous pressure dependence in its diffusion coefficient (J. Phys. Chem. C, 2015, 119, 18188). Molecular dynamics (MD) simulations are often employed to complement the information obtained from QENS experiments. Here, we report an MD simulation study to probe the anomalous pressure dependence of propane diffusion in silica aerogel. Comparison is attempted based on the self-diffusion coefficients and on the time scales of the decay of the simulated intermediate scattering functions. While the self-diffusion coefficients obtained from the simulated mean squared displacement profiles do not exhibit the anomalous pressure dependence observed in the experiments, the time scales of the decay of the intermediate scattering functions calculated from the simulation data match the corresponding quantities obtained in the QENS experiment and thus confirm the anomalous pressure dependence of the diffusion coefficient. The origin of the anomaly in pressure dependence lies in the presence of an adsorbed layer of propane molecules that seems to dominate the confined propane dynamics at low pressure, thereby lowering the diffusion coefficient. Further, time scales for rotational motion obtained from the simulations explain the absence of rotational contribution to the QENS spectra in the experiments. In particular, the rotational motion of the simulated propane molecules is found to exhibit large angular jumps at lower pressure. The present MD simulation work thus reveals important new insights into the origin of anomalous pressure dependence of propane diffusivity in silica mesopores and supplements the information obtained experimentally by QENS data.

LETTER TO THE EDITOR: Fractal diffusion coefficient from dynamical zeta functions

NASA Astrophysics Data System (ADS)

Cristadoro, Giampaolo

2006-03-01

Dynamical zeta functions provide a powerful method to analyse low-dimensional dynamical systems when the underlying symbolic dynamics is under control. On the other hand, even simple one-dimensional maps can show an intricate structure of the grammar rules that may lead to a non-smooth dependence of global observables on parameters changes. A paradigmatic example is the fractal diffusion coefficient arising in a simple piecewise linear one-dimensional map of the real line. Using the Baladi-Ruelle generalization of the Milnor-Thurnston kneading determinant, we provide the exact dynamical zeta function for such a map and compute the diffusion coefficient from its smallest zero.

Particle image diffusometry: Resolving diffusion coefficient field from microscopy movie data without particle tracking

NASA Astrophysics Data System (ADS)

Hanasaki, Itsuo; Ooi, Yuto

2018-06-01

We propose a technique to evaluate the field of diffusion coefficient for particle dispersion where the Brownian motion is heterogeneous in space and single particle tracking (SPT) analysis is hindered by high concentration of the particles and/or their small size. We realize this "particle image diffusometry" by the principle of the differential dynamic microscopy (DDM). We extend the DDM by introducing the automated objective decision of the scaling regime itself. Label-free evaluation of spatially non-uniform diffusion coefficients without SPT is useful in the diverse applications including crystal nucleation and glass transition where non-invasive observation is desired.

ICP-MS measurement of diffusion coefficients of Cs in NBG-18 graphite

NASA Astrophysics Data System (ADS)

Carter, L. M.; Brockman, J. D.; Robertson, J. D.; Loyalka, S. K.

2015-11-01

Graphite is used in the HGTR/VHTR as moderator and it also functions as a barrier to fission product release. Therefore, an elucidation of transport of fission products in reactor-grade graphite is required. We have measured diffusion coefficients of Cs in graphite NBG-18 using the release method, wherein we infused spheres of NBG-18 with Cs and measured the release rates in the temperature range of 1090-1395 K. We have obtained: These seem to be the first reported values of Cs diffusion coefficients in NBG-18. The values are lower than those reported for other graphites in the literature.

Determination of diffusion coefficients in polypyrrole thin films using a current pulse relaxation method

NASA Technical Reports Server (NTRS)

Penner, Reginald M.; Vandyke, Leon S.; Martin, Charles R.

1987-01-01

The current pulse E sub oc relaxation method and its application to the determination of diffusion coefficients in electrochemically synthesized polypyrrole thin films is described. Diffusion coefficients for such films in Et4NBF4 and MeCN are determined for a series of submicron film thicknesses. Measurement of the double-layer capacitance, C sub dl, and the resistance, R sub u, of polypyrrole thin films as a function of potential obtained with the galvanostatic pulse method is reported. Measurements of the electrolyte concentration in reduced polypyrrole films are also presented to aid in the interpretation of the data.

Sound propagation in urban areas: a periodic disposition of buildings.

PubMed

Picaut, J; Hardy, J; Simon, L

1999-10-01

A numerical simulation of background noise propagation is performed for a network of hexagonal buildings. The obtained results suggest that the prediction of background noise in urban spaces is possible by means of a modified diffusion equation using two parameters: the diffusion coefficient that expresses the spreading out of noise resulting from diffuse scattering and multiple reflections by buildings, and an attenuation term accounting for the wall absorption, atmospheric attenuation, and absorption by the open top. The dependence of the diffusion coefficient with geometrical shapes and the diffusive nature of the buildings are investigated in the case of a periodic disposition of hexagonal buildings.

Anomalous diffusion of poly(ethylene oxide) in agarose gels.

PubMed

Brenner, Tom; Matsukawa, Shingo

2016-11-01

We report on the effect of probe size and diffusion time of poly(ethylene) oxide in agarose gels. Time-dependence of the diffusion coefficient, reflecting anomalous diffusion, was observed for poly(ethylene) oxide chains with hydrodynamic radii exceeding about 20nm at an agarose concentration of 2%. The main conclusion is that the pore distribution includes pores that are only several nm across, in agreement with scattering reports in the literature. Interpretation of the diffusion coefficient dependence on the probe size based on a model of entangled rigid rods yielded a rod length of 72nm. Copyright © 2016. Published by Elsevier B.V.

Clinical applications and characteristics of apparent diffusion coefficient maps for the brain of two dogs.

PubMed

Kim, Boeun; Yi, Kangjae; Jung, Sunyoung; Ji, Seoyeon; Choi, Mincheol; Yoon, Junghee

2014-01-01

Diffusion-weighted imaging (DWI) and apparent diffusion coefficient (ADC) mapping are functional magnetic resonance imaging techniques for detecting water diffusion. DWI and the ADC map were performed for intracranial lesions in two dogs. In necrotizing leukoencephalitis, cavitated lesions contained a hypointense center with a hyperintense periphery on DWI, and hyperintense signals on the ADC maps. In metastatic sarcoma, masses including a necrotic region were hypointense with DWI, and hyperintense on the ADC map with hyperintense perilesional edema on DWI and ADC map. Since DWI and ADC data reflect the altered water diffusion, they can provide additional information at the molecular level.

Self-diffusion and conductivity in an ultracold strongly coupled plasma: Calculation by the method of molecular dynamics

NASA Astrophysics Data System (ADS)

Zelener, B. B.; Zelener, B. V.; Manykin, E. A.; Bronin, S. Ya; Bobrov, A. A.; Khikhlukha, D. R.

2018-01-01

We present results of calculations by the method of molecular dynamics of self-diffusion and conductivity of electron and ion components of ultracold plasma in a comparison with available theoretical and experimental data. For the ion self-diffusion coefficient, good agreement was obtained with experiments on ultracold plasma. The results of the calculation of self-diffusion also agree well with other calculations performed for the same values of the coupling parameter, but at high temperatures. The difference in the results of the conductivity calculations on the basis of the current autocorrelation function and on the basis of the diffusion coefficient is discussed.

Experimental Partitioning of Chalcophile Elements between Mantle Silicate Minerals and Basaltic Melt at High Pressures and Temperatures - Implications for Sulfur Geochemistry of Mantle and Crust

NASA Astrophysics Data System (ADS)

Dasgupta, R.; Jego, S.; Ding, S.; Li, Y.; Lee, C. T.

2015-12-01

The behavior of chalcophile elements during mantle melting, melt extraction, and basalt differentiation is critical for formation of ore deposits and geochemical model and evolution of crust-mantle system. While chalcophile elements are strongly partitioned into sulfides, their behavior with different extent of melting, in particular, in the absence of sulfides, can only be modeled with complete knowledge of the partitioning behavior of these elements between dominant mantle minerals and basaltic melt with or without dissolved sulfide (S2-). However, experimental data on mineral-melt partitioning are lacking for many chalcophile elements. Crystallization experiments were conducted at 3 GPa and 1450-1600 °C using a piston cylinder and synthetic silicate melt compositions similar to low-degree partial melt of peridotite. Starting silicate mixes doped with 100-300 ppm of each of various chalcophile elements were loaded into Pt/graphite double capsules. To test the effect of dissolved sulfur in silicate melt on mineral-melt partitioning of chalcophile elements, experiments were conducted on both sulfur-free and sulfur-bearing (1100-1400 ppm S in melt) systems. Experimental phases were analyzed by EPMA (for major elements and S) and LA-ICP-MS (for trace elements). All experiments produced an assemblage of cpx + melt ± garnet ± olivine ± spinel and yielded new partition coefficients (D) for Sn, Zn, Mo, Sb, Bi, Pb, and Se for cpx/melt, olivine/melt, and garnet/melt pairs. Derived Ds (mineral/basalt) reveal little effect of S2- in the melt on mineral-melt partition coefficients of the measured chalcophile elements, with Ds for Zn, Mo, Bi, Pb decreasing by less than a factor of 2 from S-free to S-bearing melt systems or remaining similar, within error, between S-free and S-bearing melt systems. By combining our data with existing partitioning data between sulfide phases and silicate melt we model the fractionation of these elements during mantle melting and basalt crystallization. The model results are compared with the chalcophile element abundance in oceanic basalts. We will discuss the implications of our new partitioning data and model results on sulfur and chalcophile element geochemistry of mantle source regions of ocean floor basalts and the fate of sulfides during mantle melting.

Characterizing the reflectivity of handheld display devices.

PubMed

Liu, Peter; Badano, Aldo

2014-08-01

With increased use of handheld and tablet display devices for viewing medical images, methods for consistently measuring reflectivity of the devices are needed. In this note, the authors report on the characterization of diffuse reflections for handheld display devices including mobile phones and tablets using methods recommended by the American Association of Physicists in Medicine Task Group 18 (TG18). The authors modified the diffuse reflectance coefficient measurement method outlined in the TG18 report. The authors measured seven handheld display devices (two phones and five tablets) and three workstation displays. The device was attached to a black panel with Velcro. To study the effect of the back surface on the diffuse reflectance coefficient, the authors created Styrofoam masks with different size square openings and placed it in front of the device. Overall, for each display device, measurements of illuminance and reflected luminance on the display screen were taken. The authors measured with no mask, with masks of varying size, and with display-size masks, and calculated the corresponding diffuse reflectance coefficient. For all handhelds, the diffuse reflectance coefficient measured with no back panel were lower than measurements performed with a mask. The authors found an overall increase in reflectivity as the size of the mask decreases. For workstations displays, diffuse reflectance coefficients were higher when no back panel was used, and higher than with masks. In all cases, as luminance increased, illuminance increased, but not at the same rate. Since the size of handheld displays is smaller than that of workstation devices, the TG18 method suffers from a dependency on illumination condition. The authors show that the diffuse reflection coefficients can vary depending on the nature of the back surface of the illuminating box. The variability in the diffuse coefficient can be as large as 20% depending on the size of the mask. For all measurements, both luminance and illuminance increased as the size of the display window decreased. The TG18 method does not account for this variability. The authors conclude that the method requires a definitive description of the back panel used in the light source setup. The methods described in the TG18 document may need to be improved to provide consistent comparisons of desktop monitors, phones, and tablets.

Arrays of hierarchical nickel sulfides/MoS2 nanosheets supported on carbon nanotubes backbone as advanced anode materials for asymmetric supercapacitor

NASA Astrophysics Data System (ADS)

Yang, Xijia; Zhao, Lijun; Lian, Jianshe

2017-03-01

One-dimensional (1D) hierarchical structures composed of nickel sulfides/MoS2 (NMS) supported on carbon nanotube (CNT) are fabricated through a one-step facile glucose-assisted hydrothermal method (NMS/CNT). The curled and tangled 1D structure is intertwined with each other and constructs three-dimensional (3D) porous networks, providing easy access of electrolyte. Meanwhile, the formation of metallic 1T-2H hybridized MoS2 and the synergistic effect between the MoS2 layers and nickel sulfides (NS) nanoparticles promotes the ions diffusion on the surface of the electrode, and the void space formed between NMS sheets can endure volume change in redox process for more stable structures. Therefore, the assembled NMS/CNT//activated carbon (AC) asymmetric supercapacitor manifests favorable specific capacitance of 108 F g-1 at 0.5 A g-1, along with a high energy density of 40 Wh kg-1 and good cycling stability of almost 100% capacity maintained after 10,000 cycles, implying it's the promising candidate for energy storage.

Extending the Diffuse Layer Model of Surface Acidity Behavior: III. Estimating Bound Site Activity Coefficients

EPA Science Inventory

Although detailed thermodynamic analyses of the 2-pK diffuse layer surface complexation model generally specify bound site activity coefficients for the purpose of accounting for those non-ideal excess free energies contributing to bound site electrochemical potentials, in applic...

Revealing mesoscopic structural universality with diffusion

PubMed Central

Novikov, Dmitry S.; Jensen, Jens H.; Helpern, Joseph A.; Fieremans, Els

2014-01-01

Measuring molecular diffusion is widely used for characterizing materials and living organisms noninvasively. This characterization relies on relations between macroscopic diffusion metrics and structure at the mesoscopic scale commensurate with the diffusion length. Establishing such relations remains a fundamental challenge, hindering progress in materials science, porous media, and biomedical imaging. Here we show that the dynamical exponent in the time dependence of the diffusion coefficient distinguishes between the universality classes of the mesoscopic structural complexity. Our approach enables the interpretation of diffusion measurements by objectively selecting and modeling the most relevant structural features. As an example, the specific values of the dynamical exponent allow us to identify the relevant mesoscopic structure affecting MRI-measured water diffusion in muscles and in brain, and to elucidate the structural changes behind the decrease of diffusion coefficient in ischemic stroke. PMID:24706873

Synchronization criteria for generalized reaction-diffusion neural networks via periodically intermittent control.

PubMed

Gan, Qintao; Lv, Tianshi; Fu, Zhenhua

2016-04-01

In this paper, the synchronization problem for a class of generalized neural networks with time-varying delays and reaction-diffusion terms is investigated concerning Neumann boundary conditions in terms of p-norm. The proposed generalized neural networks model includes reaction-diffusion local field neural networks and reaction-diffusion static neural networks as its special cases. By establishing a new inequality, some simple and useful conditions are obtained analytically to guarantee the global exponential synchronization of the addressed neural networks under the periodically intermittent control. According to the theoretical results, the influences of diffusion coefficients, diffusion space, and control rate on synchronization are analyzed. Finally, the feasibility and effectiveness of the proposed methods are shown by simulation examples, and by choosing different diffusion coefficients, diffusion spaces, and control rates, different controlled synchronization states can be obtained.

Diffusion of biomass pyrolysis products in H-ZSM-5 by molecular dynamics simulations

DOE PAGES

Bu, Lintao; Nimlos, Mark R.; Robichaud, David J.; ...

2016-12-13

Diffusion of biomass pyrolysis vapors and their upgraded products is an essential catalytic property of zeolites during catalytic fast pyrolysis and likely plays a critical role in the selectivity of these catalysts. Characterizing the diffusivities of representative biofuel molecules is critical to understand shape selectivity and interpret product distribution. Yet, experimental measurements on the diffusivities of oxygenated biofuel molecules at pyrolysis temperatures are very limited in the literature. As an alternative approach, we conducted MD simulations to measure the diffusion coefficients of several selected molecules that are representative of biomass pyrolysis vapors, namely water, methanol, glycolaldehyde, and toluene in H-ZSM-5more » zeolite. The results show the diffusion coefficients calculated via MD simulations are consistent with available NMR measurements at room temperature. The effect of molecular weight and molecular critical diameter on the diffusivity among the chosen model compounds is also examined. Furthermore, we have characterized the diffusivities of representative biofuel molecules, namely xylene isomers, in H-ZSM-5. Our calculations determined that the ratio of the diffusion coefficients for xylene isomers is p-xylene: o-xylene: m-xylene ≈ 83:3:1 at 700 K. Furthermore, our results also demonstrate the different diffusivity between p-xylene and toluene is due to the molecular orientations when the molecules diffuse along the channels in H-ZSM-5 and provide deep insight into the effect of molecular orientation on its diffusivity.« less

Molecular dynamics simulation of the diffusion of uranium species in clay pores.

PubMed

Liu, Xiao-yu; Wang, Lu-hua; Zheng, Zhong; Kang, Ming-liang; Li, Chun; Liu, Chun-li

2013-01-15

Molecular dynamics simulations were carried out to investigate the diffusive behavior of aqueous uranium species in montmorillonite pores. Three uranium species (UO(2)(2+), UO(2)CO(3), UO(2)(CO(3))(2)(2-)) were confirmed in both the adsorbed and diffuse layers. UO(2)(CO(3))(3)(4-) was neglected in the subsequent analysis due to its scare occurrence. The species-based diffusion coefficients in montmorillonite pores were then calculated, and compared with the water mobility and their diffusivity in aqueous solution/feldspar nanosized fractures. Three factors were considered that affected the diffusive behavior of the uranium species: the mobility of water, the self-diffusion coefficient of the aqueous species, and the electrostatic forces between the negatively charged surface and charged molecules. The mobility of U species in the adsorbed layer decreased in the following sequence: UO(2)(2+)>UO(2)CO(3)>UO(2)(CO(3))(2)(2-). In the diffuse layer, we obtained the highest diffusion coefficient for UO(2)(CO(3))(2)(2-) with the value of 5.48×10(-10) m(2) s(-1), which was faster than UO(2)(2+). For these two charged species, the influence of electrostatic forces on the diffusion of solutes in the diffuse layer is overwhelming, whereas the influence of self-diffusion and water mobility is minor. Our study demonstrated that the negatively charged uranyl carbonate complex must be addressed in the safety assessment of potential radioactive waste disposal systems. Copyright © 2012 Elsevier B.V. All rights reserved.

Energetic and dynamic analysis of transport of Na + and K + through a cyclic peptide nanotube in water and in lipid bilayers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Yeonho; Lee, Ji Hye; Hwang, Hoon

Potential of mean force (PMF) profiles and position-dependent diffusion coefficients of Na + and K + are calculated to elucidate the translocation of ions through a cyclic peptide nanotube, composed of 8 × cyclo[-(D-Leu-Trp) 4-] rings, in water and in hydrated DMPC bilayers. The PMF profiles and PMF decomposition analysis for the monovalent cations show that favorable interactions of the cations with the CPN as well as the lipid bilayer and dehydration free energy penalties are two major competing factors which determine the free energy surface for ion transport through CPNs both in water and lipid bilayers, and that themore » selectivity of CPNs to cations mainly arises from favorable interaction energies of cations with CPNs and lipid bilayers that are more dominant than the dehydration penalties. Calculations of the position-dependent diffusion coefficients and dynamic friction kernels of the cations indicate that the dehydration process along with the molecular rearrangements occurring outside the channel and the coupling of the ion motions with the chain-structured water movements inside the channel lead to decrease of the diffusion coefficients far away from the channel entrance and also reduced coefficients inside the channel. Here the PMF and diffusivity profiles for Na + and K + reveal that the energetics of ion transport through the CPN are governed by global interactions of ions with all the components in the system while the diffusivity of ions through the channel is mostly determined by local interactions of ions with the confined water molecules inside the channel. Comparison of Na + and K + ion distributions based on overdamped Brownian dynamics simulations based on the PMF and diffusivity profiles with the corresponding results from molecular dynamics shows good agreement, indicating accuracy of the Bayesian inference method for determining diffusion coefficients in this application. In addition this work shows that position-dependent diffusion coefficients of ions are required to explain the dynamics and conductance of ions through the CPN properly.« less

Energetic and dynamic analysis of transport of Na + and K + through a cyclic peptide nanotube in water and in lipid bilayers

DOE PAGES

Song, Yeonho; Lee, Ji Hye; Hwang, Hoon; ...

2016-11-04

Potential of mean force (PMF) profiles and position-dependent diffusion coefficients of Na + and K + are calculated to elucidate the translocation of ions through a cyclic peptide nanotube, composed of 8 × cyclo[-(D-Leu-Trp) 4-] rings, in water and in hydrated DMPC bilayers. The PMF profiles and PMF decomposition analysis for the monovalent cations show that favorable interactions of the cations with the CPN as well as the lipid bilayer and dehydration free energy penalties are two major competing factors which determine the free energy surface for ion transport through CPNs both in water and lipid bilayers, and that themore » selectivity of CPNs to cations mainly arises from favorable interaction energies of cations with CPNs and lipid bilayers that are more dominant than the dehydration penalties. Calculations of the position-dependent diffusion coefficients and dynamic friction kernels of the cations indicate that the dehydration process along with the molecular rearrangements occurring outside the channel and the coupling of the ion motions with the chain-structured water movements inside the channel lead to decrease of the diffusion coefficients far away from the channel entrance and also reduced coefficients inside the channel. Here the PMF and diffusivity profiles for Na + and K + reveal that the energetics of ion transport through the CPN are governed by global interactions of ions with all the components in the system while the diffusivity of ions through the channel is mostly determined by local interactions of ions with the confined water molecules inside the channel. Comparison of Na + and K + ion distributions based on overdamped Brownian dynamics simulations based on the PMF and diffusivity profiles with the corresponding results from molecular dynamics shows good agreement, indicating accuracy of the Bayesian inference method for determining diffusion coefficients in this application. In addition this work shows that position-dependent diffusion coefficients of ions are required to explain the dynamics and conductance of ions through the CPN properly.« less

DCE-MRI-Derived Volume Transfer Constant (Ktrans) and DWI Apparent Diffusion Coefficient as Predictive Markers of Short- and Long-Term Efficacy of Chemoradiotherapy in Patients With Esophageal Cancer.

PubMed

Ye, Zhi-Min; Dai, Shu-Jun; Yan, Feng-Qin; Wang, Lei; Fang, Jun; Fu, Zhen-Fu; Wang, Yue-Zhen

2018-01-01

This study aimed to evaluate both the short- and long-term efficacies of chemoradiotherapy in relation to the treatment of esophageal cancer . This was achieved through the use of dynamic contrast-enhanced magnetic resonance imaging-derived volume transfer constant and diffusion weighted imaging-derived apparent diffusion coefficient . Patients with esophageal cancer were assigned into the sensitive and resistant groups based on respective efficacies in chemoradiotherapy. Dynamic contrast-enhanced magnetic resonance imaging and diffusion weighted imaging were used to measure volume transfer constant and apparent diffusion coefficient, while computed tomography was used to calculate tumor size reduction rate. Pearson correlation analyses were conducted to analyze correlation between volume transfer constant, apparent diffusion coefficient, and the tumor size reduction rate. Receiver operating characteristic curve was constructed to analyze the short-term efficacy of volume transfer constant and apparent diffusion coefficient, while Kaplan-Meier curve was employed for survival rate analysis. Cox proportional hazard model was used for the risk factors for prognosis of patients with esophageal cancer. Our results indicated reduced levels of volume transfer constant, while increased levels were observed in ADC min , ADC mean , and ADC max following chemoradiotherapy. A negative correlation was determined between ADC min , ADC mean , and ADC max , as well as in the tumor size reduction rate prior to chemoradiotherapy, whereas a positive correlation was uncovered postchemoradiotherapy. Volume transfer constant was positively correlated with tumor size reduction rate both before and after chemoradiotherapy. The 5-year survival rate of patients with esophageal cancer having high ADC min , ADC mean , and ADC max and volume transfer constant before chemoradiotherapy was greater than those with respectively lower values. According to the Cox proportional hazard model, ADC mean , clinical stage, degree of differentiation, and tumor stage were all confirmed as being independent risk factors in regard to the prognosis of patients with EC. The findings of this study provide evidence suggesting that volume transfer constant and apparent diffusion coefficient as being tools allowing for the evaluation of both the short- and long-term efficacies of chemoradiotherapy esophageal cancer treatment.

Spectrophotometric Method for Differentiation of Human Skin Melanoma. I. Optical Diffuse Reflection Coefficient

NASA Astrophysics Data System (ADS)

Petruk, V. G.; Ivanov, A. P.; Kvaternyuk, S. M.; Barun, V. V.

2016-03-01

We have designed an experimental setup, based on two integrating spheres, that lets us measure the optical diffuse reflectance spectra (diffuse reflection coefficient vs. wavelength) of human skin quickly under clinical conditions in vivo. For the wavelength interval 520-1100 nm, we give the values of the diffuse reflection coefficient for healthy tissue, skin with a benign nevus, and skin with a malignant melanoma for a large group of test subjects. We experimentally established a number of wavelengths in the red-near IR region of the spectrum which can be used for early differential diagnosis of nevi and melanoma in patient cancer screening. According to the Kramer-Welch test, the probability of the diffuse reflection coefficient for skin with melanoma and a nevus having different distributions is >0.94, and at many wavelengths it is >0.999. By solving the inverse problem, we estimated the changes in a number of structural and biophysical parameters of the tissue on going from healthy skin to nevus and melanoma. The results obtained can provide a basis for developing a clinical approach to identifying the risk of malignant transformation of the skin before surgery and histological analysis of the tissue.

Two-cation competition in ionic-liquid-modified electrolytes for lithium ion batteries.

PubMed

Lee, Sang-Young; Yong, Hyun Hang; Lee, Young Joo; Kim, Seok Koo; Ahn, Soonho

2005-07-21

It is a common observation that when ionic liquids are added to electrolytes the performances of lithium ion cells become poor, while the thermal safeties of the electrolytes might be improved. In this study, this behavior is investigated based on the kinetics of ionic diffusion. As a model ionic liquid, we chose butyldimethylimidazolium hexafluorophosphate (BDMIPF(6)). The common solvent was propylene carbonate (PC), and lithium hexafluorophosphate (LiPF(6)) was selected as the lithium conducting salt. Ionic diffusion coefficients are estimated by using a pulsed field gradient NMR technique. From a basic study on the model electrolytes (BDMIPF(6) in PC, LiPF(6) in PC, and BDMIPF(6) + LiPF(6) in PC), it was found that the BDMI(+) from BDMIPF(6) shows larger diffusion coefficients than the Li(+) from LiPF(6). However, the anionic (PF(6)(-)) diffusion coefficients present little difference between the model electrolytes. The higher diffusion coefficient of BDMI(+) than that of Li(+) suggests that the poor C-rate performance of lithium ion cells containing ionic liquids as an electrolyte component can be attributed to the two-cation competition between Li(+) and BDMI(+).

Application of New Chorus Wave Model from Van Allen Probe Observations in Earth's Radiation Belt Modeling

NASA Astrophysics Data System (ADS)

Wang, D.; Shprits, Y.; Spasojevic, M.; Zhu, H.; Aseev, N.; Drozdov, A.; Kellerman, A. C.

2017-12-01

In situ satellite observations, theoretical studies and model simulations suggested that chorus waves play a significant role in the dynamic evolution of relativistic electrons in the Earth's radiation belts. In this study, we developed new wave frequency and amplitude models that depend on Magnetic Local Time (MLT)-, L-shell, latitude- and geomagnetic conditions indexed by Kp for upper-band and lower-band chorus waves using measurements from the Electric and Magnetic Field Instrument Suite and Integrated Science (EMFISIS) instrument onboard the Van Allen Probes. Utilizing the quasi-linear full diffusion code, we calculated corresponding diffusion coefficients in each MLT sector (1 hour resolution) for upper-band and lower-band chorus waves according to the new developed wave models. Compared with former parameterizations of chorus waves, the new parameterizations result in differences in diffusion coefficients that depend on energy and pitch angle. Utilizing obtained diffusion coefficients, lifetime of energetic electrons is parameterized accordingly. In addition, to investigate effects of obtained diffusion coefficients in different MLT sectors and under different geomagnetic conditions, we performed simulations using four-dimensional Versatile Electron Radiation Belt simulations and validated results against observations.