WorldWideScience

Sample records for linear nonequilibrium sorption

  1. An Exact Solution for the Assessment of Nonequilibrium Sorption of Radionuclides in the Vadose Zone

    Drake, R. L.; Chen, J-S.

    2002-01-01

    In a report on model evaluation, the authors ran the HYDRUS Code, among other transport codes, to evaluate the impacts of nonequilibrium sorption sites on the time-evolution of 99Tc and 90Sr through the vadose zone. Since our evaluation was based on a rather low, annual recharge rate, many of the numerical results derived from HYDRUS indicated that the nonequilibrium sorption sites, in essence, acted as equilibrium sorption sites. To help explain these results, we considered a ''stripped-down'' version of the HYDRUS system. This ''stripped-down'' version possesses two dependent variables, one for the radionuclides in solution and the other for the radionuclides adsorbed to the nonequilibrium sites; and it possesses constant physical parameters. The resultant governing equation for the radionuclides in solution is a linear, advection-dispersion-reaction (i.e., radioactive decay) partial differential equation containing a history integral term accounting for the nonequilibrium sorption sites. It is this ''stripped-down'' version, which is the subject of this paper. We found an exact solution to this new version of the model. The exact solution is given in terms of a single definite integral of terms involving elementary functions of the independent variables and the system parameters. This integral possesses adequate convergence properties and is easy to evaluate, both in a quantitative matter and in a qualitative manner. The parameters that are considered in the system are as follows: the radionuclide's equilibrium partition coefficient between water and soil, the bulk density of the soil, the fractions of equilibrium/nonequilibrium sorption sites, the volumetric water content, the first order equilibrium adsorption rate constant, the first order radioactive decay rate constant, the liquid water soil tortuosity factor, the molecular diffusion coefficient in water, the longitudinal dispersivity factor, and the Darcian fluid flux density. In addition, the system

  2. Acceptability of inversely-modelled parameters for non-equilibrium sorption of pesticides in soil

    Horst, ter M.M.S.; Boesten, J.J.T.I.; Beinum, van W.; Beulke, S.

    2013-01-01

    Simulation of the increase of sorption in time is one of the options in higher tiers of pesticide regulatory leaching assessments to obtain more realistic leaching estimates. Therefore, accurate estimates of non-equilibrium sorption parameters are required as input for the pesticide leaching

  3. Linear response in the nonequilibrium zero range process

    Maes, Christian; Salazar, Alberto

    2014-01-01

    We explore a number of explicit response formulæ around the boundary driven zero range process to changes in the exit and entrance rates. In such a nonequilibrium regime kinetic (and not only thermodynamic) aspects make a difference in the response. Apart from a number of formal approaches, we illustrate a general decomposition of the linear response into entropic and frenetic contributions, the latter being realized from changes in the dynamical activity at the boundaries. In particular in this way one obtains nonlinear modifications to the Green–Kubo relation. We end by bringing some general remarks about the situation where that nonequilibrium response remains given by the (equilibrium) Kubo formula such as for the density profile in the boundary driven Lorentz gas

  4. Adiabatic Hamiltonian deformation, linear response theory, and nonequilibrium molecular dynamics

    Hoover, W.G.

    1980-01-01

    Although Hamiltonians of various kinds have previously been used to derive Green-Kubo relations for the transport coefficients, the particular choice described is uniquely related to thermodynamics. This nonequilibrium Hamiltonian formulation of fluid flow provides pedagogically simple routes to nonequilibrium fluxes and distribution functions, to theoretical understanding of long-time effects, and to new numerical methods for simulating systems far from equilibrium. The same methods are now being applied to solid-phase problems. At the relatively high frequencies used in the viscous fluid calculations described, solids typically behave elastically. Lower frequencies lead to the formation of dislocations and other defects, making it possible to study plastic flow. A property of the nonequilibrium equations of motion which might be profitably explored is their effective irreversibility. Because only a few particles are necessary to generate irreversible behavior, simulations using adiabatic deformations of the kind described here could perhaps elucidate the instability in the equations of motion responsible for irreversibility

  5. Stochastic linearization of turbulent dynamics of dispersive waves in equilibrium and non-equilibrium state

    Jiang, Shixiao W; Lu, Haihao; Zhou, Douglas; Cai, David

    2016-01-01

    Characterizing dispersive wave turbulence in the long time dynamics is central to understanding of many natural phenomena, e.g., in atmosphere ocean dynamics, nonlinear optics, and plasma physics. Using the β -Fermi–Pasta–Ulam nonlinear system as a prototypical example, we show that in thermal equilibrium and non-equilibrium steady state the turbulent state even in the strongly nonlinear regime possesses an effective linear stochastic structure in renormalized normal variables. In this framework, we can well characterize the spatiotemporal dynamics, which are dominated by long-wavelength renormalized waves. We further demonstrate that the energy flux is nearly saturated by the long-wavelength renormalized waves in non-equilibrium steady state. The scenario of such effective linear stochastic dynamics can be extended to study turbulent states in other nonlinear wave systems. (paper)

  6. Generalized multivariate Fokker-Planck equations derived from kinetic transport theory and linear nonequilibrium thermodynamics

    Frank, T.D.

    2002-01-01

    We study many particle systems in the context of mean field forces, concentration-dependent diffusion coefficients, generalized equilibrium distributions, and quantum statistics. Using kinetic transport theory and linear nonequilibrium thermodynamics we derive for these systems a generalized multivariate Fokker-Planck equation. It is shown that this Fokker-Planck equation describes relaxation processes, has stationary maximum entropy distributions, can have multiple stationary solutions and stationary solutions that differ from Boltzmann distributions

  7. Two-component fluid membranes near repulsive walls: Linearized hydrodynamics of equilibrium and nonequilibrium states.

    Sankararaman, Sumithra; Menon, Gautam I; Sunil Kumar, P B

    2002-09-01

    We study the linearized hydrodynamics of a two-component fluid membrane near a repulsive wall, using a model that incorporates curvature-concentration coupling as well as hydrodynamic interactions. This model is a simplified version of a recently proposed one [J.-B. Manneville et al., Phys. Rev. E 64, 021908 (2001)] for nonequilibrium force centers embedded in fluid membranes, such as light-activated bacteriorhodopsin pumps incorporated in phospholipid egg phosphatidyl choline (EPC) bilayers. The pump-membrane system is modeled as an impermeable, two-component bilayer fluid membrane in the presence of an ambient solvent, in which one component, representing active pumps, is described in terms of force dipoles displaced with respect to the bilayer midpoint. We first discuss the case in which such pumps are rendered inactive, computing the mode structure in the bulk as well as the modification of hydrodynamic properties by the presence of a nearby wall. These results should apply, more generally, to equilibrium fluid membranes comprised of two components, in which the effects of curvature-concentration coupling are significant, above the threshold for phase separation. We then discuss the fluctuations and mode structure in the steady state of active two-component membranes near a repulsive wall. We find that proximity to the wall smoothens membrane height fluctuations in the stable regime, resulting in a logarithmic scaling of the roughness even for initially tensionless membranes. This explicitly nonequilibrium result is a consequence of the incorporation of curvature-concentration coupling in our hydrodynamic treatment. This result also indicates that earlier scaling arguments which obtained an increase in the roughness of active membranes near repulsive walls upon neglecting the role played by such couplings may need to be reevaluated.

  8. Computer codes for three dimensional mass transport with non-linear sorption

    Noy, D.J.

    1985-03-01

    The report describes the mathematical background and data input to finite element programs for three dimensional mass transport in a porous medium. The transport equations are developed and sorption processes are included in a general way so that non-linear equilibrium relations can be introduced. The programs are described and a guide given to the construction of the required input data sets. Concluding remarks indicate that the calculations require substantial computer resources and suggest that comprehensive preliminary analysis with lower dimensional codes would be important in the assessment of field data. (author)

  9. Sorption of malachite green from aqueous solution by potato peel: Kinetics and equilibrium modeling using non-linear analysis method

    El-Khamsa Guechi

    2016-09-01

    Full Text Available Potato peel (PP was used as a biosorbent to remove malachite green (MG from aqueous solution under various operating conditions. The effect of the experimental parameters such as initial dye concentration, biosorbent dose, initial pH, stirring speed, temperature, ionic strength and biosorbent particle size was investigated through a number of batch sorption experiments. The sorption kinetic uptake for MG by PP at various initial dye concentrations was analyzed by non-linear method using pseudo-first, pseudo-second and pseudo-nth order models. It was found that the pseudo-nth order kinetic model was the best applicable model to describe the sorption kinetic data and the order n of sorption reaction was calculated in the range from 0.71 to 2.71. Three sorption isotherms namely the Langmuir, Freundlich and Redlich–Peterson isotherms in their non-linear forms were applied to the biosorption equilibrium data. Both the Langmuir and Redlich–Peterson models were found to fit the sorption isotherm data well, but the Redlich–Peterson model was better. Thermodynamic parameters show that the sorption process of MG is endothermic and more effective process at high temperatures. The results revealed that PP is very effective for the biosorption of MG from aqueous solutions.

  10. Second-order kinetic model for the sorption of cadmium onto tree fern: a comparison of linear and non-linear methods.

    Ho, Yuh-Shan

    2006-01-01

    A comparison was made of the linear least-squares method and a trial-and-error non-linear method of the widely used pseudo-second-order kinetic model for the sorption of cadmium onto ground-up tree fern. Four pseudo-second-order kinetic linear equations are discussed. Kinetic parameters obtained from the four kinetic linear equations using the linear method differed but they were the same when using the non-linear method. A type 1 pseudo-second-order linear kinetic model has the highest coefficient of determination. Results show that the non-linear method may be a better way to obtain the desired parameters.

  11. Nonequilibrium transition and pattern formation in a linear reaction-diffusion system with self-regulated kinetics

    Paul, Shibashis; Ghosh, Shyamolina; Ray, Deb Shankar

    2018-02-01

    We consider a reaction-diffusion system with linear, stochastic activator-inhibitor kinetics where the time evolution of concentration of a species at any spatial location depends on the relative average concentration of its neighbors. This self-regulating nature of kinetics brings in spatial correlation between the activator and the inhibitor. An interplay of this correlation in kinetics and disparity of diffusivities of the two species leads to symmetry breaking non-equilibrium transition resulting in stationary pattern formation. The role of initial noise strength and the linear reaction terms has been analyzed for pattern selection.

  12. Predicting sediment sorption coefficients for linear alkylbenzenesulfonate congeners from polyacrylate-water partition coefficients at different salinities.

    Rico Rico, A.; Droge, S.T.J.|info:eu-repo/dai/nl/304834017; Hermens, J.L.M.|info:eu-repo/dai/nl/069681384

    2010-01-01

    The effect of the molecular structure and the salinity on the sorption of the anionic surfactant linear alkylbenzenesulfonate (LAS) to marine sediment has been studied. The analysis of several individual LAS congeners in seawater and of one specific LAS congener at different dilutions of seawater

  13. Modeling chromatographic columns. Non-equilibrium packed-bed adsorption with non-linear adsorption isotherms

    Özdural, A.R.; Alkan, A.; Kerkhof, P.J.A.M.

    2004-01-01

    In this work a new mathematical model, based on non-equilibrium conditions, describing the dynamic adsorption of proteins in columns packed with spherical adsorbent particles is used to study the performance of chromatographic systems. Simulations of frontal chromatography, including axial

  14. The role of non-equilibrium fluxes in the relaxation processes of the linear chemical master equation.

    de Oliveira, Luciana Renata; Bazzani, Armando; Giampieri, Enrico; Castellani, Gastone C

    2014-08-14

    We propose a non-equilibrium thermodynamical description in terms of the Chemical Master Equation (CME) to characterize the dynamics of a chemical cycle chain reaction among m different species. These systems can be closed or open for energy and molecules exchange with the environment, which determines how they relax to the stationary state. Closed systems reach an equilibrium state (characterized by the detailed balance condition (D.B.)), while open systems will reach a non-equilibrium steady state (NESS). The principal difference between D.B. and NESS is due to the presence of chemical fluxes. In the D.B. condition the fluxes are absent while for the NESS case, the chemical fluxes are necessary for the state maintaining. All the biological systems are characterized by their "far from equilibrium behavior," hence the NESS is a good candidate for a realistic description of the dynamical and thermodynamical properties of living organisms. In this work we consider a CME written in terms of a discrete Kolmogorov forward equation, which lead us to write explicitly the non-equilibrium chemical fluxes. For systems in NESS, we show that there is a non-conservative "external vector field" whose is linearly proportional to the chemical fluxes. We also demonstrate that the modulation of these external fields does not change their stationary distributions, which ensure us to study the same system and outline the differences in the system's behavior when it switches from the D.B. regime to NESS. We were interested to see how the non-equilibrium fluxes influence the relaxation process during the reaching of the stationary distribution. By performing analytical and numerical analysis, our central result is that the presence of the non-equilibrium chemical fluxes reduces the characteristic relaxation time with respect to the D.B. condition. Within a biochemical and biological perspective, this result can be related to the "plasticity property" of biological systems and to their

  15. The role of non-equilibrium fluxes in the relaxation processes of the linear chemical master equation

    Oliveira, Luciana Renata de; Bazzani, Armando; Giampieri, Enrico; Castellani, Gastone C.

    2014-01-01

    We propose a non-equilibrium thermodynamical description in terms of the Chemical Master Equation (CME) to characterize the dynamics of a chemical cycle chain reaction among m different species. These systems can be closed or open for energy and molecules exchange with the environment, which determines how they relax to the stationary state. Closed systems reach an equilibrium state (characterized by the detailed balance condition (D.B.)), while open systems will reach a non-equilibrium steady state (NESS). The principal difference between D.B. and NESS is due to the presence of chemical fluxes. In the D.B. condition the fluxes are absent while for the NESS case, the chemical fluxes are necessary for the state maintaining. All the biological systems are characterized by their “far from equilibrium behavior,” hence the NESS is a good candidate for a realistic description of the dynamical and thermodynamical properties of living organisms. In this work we consider a CME written in terms of a discrete Kolmogorov forward equation, which lead us to write explicitly the non-equilibrium chemical fluxes. For systems in NESS, we show that there is a non-conservative “external vector field” whose is linearly proportional to the chemical fluxes. We also demonstrate that the modulation of these external fields does not change their stationary distributions, which ensure us to study the same system and outline the differences in the system's behavior when it switches from the D.B. regime to NESS. We were interested to see how the non-equilibrium fluxes influence the relaxation process during the reaching of the stationary distribution. By performing analytical and numerical analysis, our central result is that the presence of the non-equilibrium chemical fluxes reduces the characteristic relaxation time with respect to the D.B. condition. Within a biochemical and biological perspective, this result can be related to the “plasticity property” of biological

  16. Nonequilibrium molecular dynamics study of ring polymer melts under shear and elongation flows: A comparison with their linear analogs

    Yoon, Jeongha; Kim, Jinseong; Baig, Chunggi, E-mail: cbaig@unist.ac.kr [Department of Chemical Engineering, School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 689-798 (Korea, Republic of)

    2016-07-15

    We present detailed results for the structural and rheological properties of unknotted and unconcatenated ring polyethylene (PE) melts under shear and elongation flows via direct atomistic nonequilibrium molecular dynamics simulations. Short (C{sub 78}H{sub 156}) and long (C{sub 400}H{sub 800}) ring PE melts were subjected to planar Couette flow (PCF) and planar elongational flow (PEF) across a wide range of strain rates from linear to highly nonlinear flow regimes. The results are analyzed in detail through a direct comparison with those of the corresponding linear polymers. We found that, in comparison to their linear analogs, ring melts possess rather compact chain structures at or near the equilibrium state and exhibit a considerably lesser degree of structural deformation with respect to the applied flow strength under both PCF and PEF. The large structural resistance of ring polymers against an external flow field is attributed to the intrinsic closed-loop configuration of the ring and the topological constraint of nonconcatenation between ring chains in the melt. As a result, there appears to be a substantial discrepancy between ring and linear systems in terms of their structural and rheological properties such as chain orientation, the distribution of chain dimensions, viscosity, flow birefringence, hydrostatic pressure, the pair correlation function, and potential interaction energies. The findings and conclusions drawn in this work would be a useful guide in future exploration of the characteristic dynamical and relaxation mechanisms of ring polymers in bulk or confined systems under flowing conditions.

  17. The time-local view of nonequilibrium statistical mechanics. I. Linear theory of transport and relaxation

    der, R.

    1987-01-01

    The various approaches to nonequilibrium statistical mechanics may be subdivided into convolution and convolutionless (time-local) ones. While the former, put forward by Zwanzig, Mori, and others, are used most commonly, the latter are less well developed, but have proven very useful in recent applications. The aim of the present series of papers is to develop the time-local picture (TLP) of nonequilibrium statistical mechanics on a new footing and to consider its physical implications for topics such as the formulation of irreversible thermodynamics. The most natural approach to TLP is seen to derive from the Fourier-Laplace transformwidetilde{C}(z)) of pertinent time correlation functions, which on the physical sheet typically displays an essential singularity at z=∞ and a number of macroscopic and microscopic poles in the lower half-plane corresponding to long- and short-lived modes, respectively, the former giving rise to the autonomous macrodynamics, whereas the latter are interpreted as doorway modes mediating the transfer of information from relevant to irrelevant channels. Possible implications of this doorway mode concept for socalled extended irreversible thermodynamics are briefly discussed. The pole structure is used for deriving new kinds of generalized Green-Kubo relations expressing macroscopic quantities, transport coefficients, e.g., by contour integrals over current-current correlation functions obeying Hamiltonian dynamics, the contour integration replacing projection. The conventional Green-Kubo relations valid for conserved quantities only are rederived for illustration. Moreover,widetilde{C}(z) may be expressed by a Laurent series expansion in positive and negative powers of z, from which a rigorous, general, and straightforward method is developed for extracting all macroscopic quantities from so-called secularly divergent expansions ofwidetilde{C}(z) as obtained from the application of conventional many-body techniques to the calculation

  18. Noise-Induced Modulation of the Relaxation Kinetics around a Non-Equilibrium Steady State of Non-Linear Chemical Reaction Networks

    Ramaswamy, Rajesh; Sbalzarini, Ivo F; González-Segredo, Nélido

    2011-01-01

    Stochastic effects from correlated noise non-trivially modulate the kinetics of non-linear chemical reaction networks. This is especially important in systems where reactions are confined to small volumes and reactants are delivered in bursts. We characterise how the two noise sources confinement and burst modulate the relaxation kinetics of a non-linear reaction network around a non-equilibrium steady state. We find that the lifetimes of species change with burst input and confinement. Confi...

  19. Applicability of the Linear Sorption Isotherm Model to Represent Contaminant Transport Processes in Site Wide Performance Assessments

    FOGWELL, T.W.; LAST, G.V.

    2003-01-01

    The estimation of flux of contaminants through the vadose zone to the groundwater under varying geologic, hydrologic, and chemical conditions is key to making technically credible and sound decisions regarding soil site characterization and remediation, single-shell tank retrieval, and waste site closures (DOE 2000). One of the principal needs identified in the science and technology roadmap (DOE 2000) is the need to improve the conceptual and numerical models that describe the location of contaminants today, and to provide the basis for forecasting future movement of contaminants on both site-specific and site-wide scales. The State of Knowledge (DOE 1999) and Preliminary Concepts documents describe the importance of geochemical processes on the transport of contaminants through the Vadose Zone. These processes have been identified in the international list of Features, Events, and Processes (FEPs) (NEA 2000) and included in the list of FEPS currently being developed for Hanford Site assessments (Soler et al. 2001). The current vision for Hanford site-wide cumulative risk assessments as performed using the System Assessment Capability (SAC) is to represent contaminant adsorption using the linear isotherm (empirical distribution coefficient, K d ) sorption model. Integration Project Expert Panel (PEP) comments indicate that work is required to adequately justify the applicability of the linear sorption model, and to identify and defend the range of K d values that are adopted for assessments. The work plans developed for the Science and Technology (S and T) efforts, SAC, and the Core Projects must answer directly the question of ''Is there a scientific basis for the application of the linear sorption isotherm model to the complex wastes of the Hanford Site?'' This paper is intended to address these issues. The reason that well documented justification is required for using the linear sorption (K d ) model is that this approach is strictly empirical and is often

  20. Statistical mechanics of nonequilibrium liquids

    Evans, Denis J; Craig, D P; McWeeny, R

    1990-01-01

    Statistical Mechanics of Nonequilibrium Liquids deals with theoretical rheology. The book discusses nonlinear response of systems and outlines the statistical mechanical theory. In discussing the framework of nonequilibrium statistical mechanics, the book explains the derivation of a nonequilibrium analogue of the Gibbsian basis for equilibrium statistical mechanics. The book reviews the linear irreversible thermodynamics, the Liouville equation, and the Irving-Kirkwood procedure. The text then explains the Green-Kubo relations used in linear transport coefficients, the linear response theory,

  1. Isotherms and thermodynamics by linear and non-linear regression analysis for the sorption of methylene blue onto activated carbon: Comparison of various error functions

    Kumar, K. Vasanth; Porkodi, K.; Rocha, F.

    2008-01-01

    A comparison of linear and non-linear regression method in selecting the optimum isotherm was made to the experimental equilibrium data of methylene blue sorption by activated carbon. The r 2 was used to select the best fit linear theoretical isotherm. In the case of non-linear regression method, six error functions, namely coefficient of determination (r 2 ), hybrid fractional error function (HYBRID), Marquardt's percent standard deviation (MPSD), average relative error (ARE), sum of the errors squared (ERRSQ) and sum of the absolute errors (EABS) were used to predict the parameters involved in the two and three parameter isotherms and also to predict the optimum isotherm. For two parameter isotherm, MPSD was found to be the best error function in minimizing the error distribution between the experimental equilibrium data and predicted isotherms. In the case of three parameter isotherm, r 2 was found to be the best error function to minimize the error distribution structure between experimental equilibrium data and theoretical isotherms. The present study showed that the size of the error function alone is not a deciding factor to choose the optimum isotherm. In addition to the size of error function, the theory behind the predicted isotherm should be verified with the help of experimental data while selecting the optimum isotherm. A coefficient of non-determination, K 2 was explained and was found to be very useful in identifying the best error function while selecting the optimum isotherm

  2. Kinetics of non-equilibrium processes in non-linear crystals of lithium borates excited with synchrotron radiation

    Ogorodnikov, I N; Isaenko, L I; Zinin, E I; Kruzhalov, A V

    2000-01-01

    The paper presents the results of a study of the LiB sub 3 O sub 5 and Li sub 2 B sub 4 O sub 7 crystals by the use of the luminescent spectroscopy with the sub-nanosecond time resolution under excitation of the high-power synchrotron radiation. The commonness in the origin of the non-equilibrium processes in these crystals as well as the observed differences in the luminescence manifestations is discussed.

  3. Kinetics of non-equilibrium processes in non-linear crystals of lithium borates excited with synchrotron radiation

    Ogorodnikov, I.N. E-mail: ogo@dpt.ustu.ru; Pustovarov, V.A.; Isaenko, L.I.; Zinin, E.I.; Kruzhalov, A.V

    2000-06-21

    The paper presents the results of a study of the LiB{sub 3}O{sub 5} and Li{sub 2}B{sub 4}O{sub 7} crystals by the use of the luminescent spectroscopy with the sub-nanosecond time resolution under excitation of the high-power synchrotron radiation. The commonness in the origin of the non-equilibrium processes in these crystals as well as the observed differences in the luminescence manifestations is discussed.

  4. Experimental determination of sorption in fractured flow systems

    Zimmerman, Mitchell D.; Bennett, Philip C.; Sharp, John M.; Choi, Wan-Joo

    2002-09-01

    Fracture "skins" are alteration zones on fracture surfaces created by a variety of biological, chemical, and physical processes. Skins increase surface area, where sorption occurs, compared to the unaltered rock matrix. This study examines the sorption of organic solutes on altered fracture surfaces in an experimental fracture-flow apparatus. Fracture skins containing abundant metal oxides, clays, and organic material from the Breathitt Formation (Kentucky, USA) were collected in a manner such that skin surface integrity was maintained. The samples were reassembled in the lab in a flow-through apparatus that simulated ˜2.7 m of a linear fracture "conduit." A dual-tracer injection scheme was utilized with the sorbing or reactive tracer compared to a non-reactive tracer (chloride) injected simultaneously. Sorption was assessed from the ratio of the first temporal moments of the breakthrough curves and from the loss of reactive tracer mass and evaluated as a function of flow velocity and solute type. The breakthrough curves suggest dual-flow regimes in the fracture with both sorbing and non-sorbing flow fields. Significant sorption occurs for the reactive components, and sorption increased with decreasing flow rate and decreasing compound solubility. Based on moment analysis, however, there was little retardation of the center of solute mass. These data suggest that non-equilibrium sorption processes dominate and that slow desorption and boundary layer diffusion cause extensive tailing in the breakthrough curves.

  5. A Numerical Approach for Non-Linear Moisture Flow in Porous Materials with Account to Sorption Hysteresis

    Johannesson, Björn; Nyman, U.

    2010-01-01

    . History-dependent sorption behaviour is introduced by considering scanning curves between the bounding desorption and absorption curves. The method, therefore, makes it possible to calculate equilibrium water contents for arbitrary relative humidity variations at every material point considered...

  6. Noise-induced modulation of the relaxation kinetics around a non-equilibrium steady state of non-linear chemical reaction networks.

    Rajesh Ramaswamy

    2011-01-01

    Full Text Available Stochastic effects from correlated noise non-trivially modulate the kinetics of non-linear chemical reaction networks. This is especially important in systems where reactions are confined to small volumes and reactants are delivered in bursts. We characterise how the two noise sources confinement and burst modulate the relaxation kinetics of a non-linear reaction network around a non-equilibrium steady state. We find that the lifetimes of species change with burst input and confinement. Confinement increases the lifetimes of all species that are involved in any non-linear reaction as a reactant. Burst monotonically increases or decreases lifetimes. Competition between burst-induced and confinement-induced modulation may hence lead to a non-monotonic modulation. We quantify lifetime as the integral of the time autocorrelation function (ACF of concentration fluctuations around a non-equilibrium steady state of the reaction network. Furthermore, we look at the first and second derivatives of the ACF, each of which is affected in opposite ways by burst and confinement. This allows discriminating between these two noise sources. We analytically derive the ACF from the linear Fokker-Planck approximation of the chemical master equation in order to establish a baseline for the burst-induced modulation at low confinement. Effects of higher confinement are then studied using a partial-propensity stochastic simulation algorithm. The results presented here may help understand the mechanisms that deviate stochastic kinetics from its deterministic counterpart. In addition, they may be instrumental when using fluorescence-lifetime imaging microscopy (FLIM or fluorescence-correlation spectroscopy (FCS to measure confinement and burst in systems with known reaction rates, or, alternatively, to correct for the effects of confinement and burst when experimentally measuring reaction rates.

  7. Noise-induced modulation of the relaxation kinetics around a non-equilibrium steady state of non-linear chemical reaction networks.

    Ramaswamy, Rajesh; Sbalzarini, Ivo F; González-Segredo, Nélido

    2011-01-28

    Stochastic effects from correlated noise non-trivially modulate the kinetics of non-linear chemical reaction networks. This is especially important in systems where reactions are confined to small volumes and reactants are delivered in bursts. We characterise how the two noise sources confinement and burst modulate the relaxation kinetics of a non-linear reaction network around a non-equilibrium steady state. We find that the lifetimes of species change with burst input and confinement. Confinement increases the lifetimes of all species that are involved in any non-linear reaction as a reactant. Burst monotonically increases or decreases lifetimes. Competition between burst-induced and confinement-induced modulation may hence lead to a non-monotonic modulation. We quantify lifetime as the integral of the time autocorrelation function (ACF) of concentration fluctuations around a non-equilibrium steady state of the reaction network. Furthermore, we look at the first and second derivatives of the ACF, each of which is affected in opposite ways by burst and confinement. This allows discriminating between these two noise sources. We analytically derive the ACF from the linear Fokker-Planck approximation of the chemical master equation in order to establish a baseline for the burst-induced modulation at low confinement. Effects of higher confinement are then studied using a partial-propensity stochastic simulation algorithm. The results presented here may help understand the mechanisms that deviate stochastic kinetics from its deterministic counterpart. In addition, they may be instrumental when using fluorescence-lifetime imaging microscopy (FLIM) or fluorescence-correlation spectroscopy (FCS) to measure confinement and burst in systems with known reaction rates, or, alternatively, to correct for the effects of confinement and burst when experimentally measuring reaction rates.

  8. Nonequilibrium statistical physics

    Röpke, Gerd

    2013-01-01

    Authored by one of the top theoretical physicists in Germany, and a well-known authority in the field, this is the only coherent presentation of the subject suitable for masters and PhD students, as well as postdocs in physics and related disciplines.Starting from a general discussion of the nonequilibrium state, different standard approaches such as master equations, and kinetic and linear response theory, are derived after special assumptions. This allows for an insight into the problems of nonequilibrium physics, a discussion of the limits, and suggestions for improvements. Applications

  9. Nonequilibrium entropies

    Maes, Christian

    2012-01-01

    In contrast to the quite unique entropy concept useful for systems in (local) thermodynamic equilibrium, there is a variety of quite distinct nonequilibrium entropies, reflecting different physical points. We disentangle these entropies as they relate to heat, fluctuations, response, time asymmetry, variational principles, monotonicity, volume contraction or statistical forces. However, not all of those extensions yield state quantities as understood thermodynamically. At the end we sketch how aspects of dynamical activity can take over for obtaining an extended Clausius relation.

  10. Non-equilibrium thermodynamics

    De Groot, Sybren Ruurds

    1984-01-01

    The study of thermodynamics is especially timely today, as its concepts are being applied to problems in biology, biochemistry, electrochemistry, and engineering. This book treats irreversible processes and phenomena - non-equilibrium thermodynamics.S. R. de Groot and P. Mazur, Professors of Theoretical Physics, present a comprehensive and insightful survey of the foundations of the field, providing the only complete discussion of the fluctuating linear theory of irreversible thermodynamics. The application covers a wide range of topics: the theory of diffusion and heat conduction, fluid dyn

  11. Sorption mechanisms and sorption models

    Fedoroff, M.; Lefevre, G.; Duc, M.; Neskovic, C.; Milonjic, S.

    2004-01-01

    Sorption at the solid-liquid interfaces play a major role in many phenomena and technologies: chemical separations, catalysis, biological processes, transport of toxic and radioactive species in surface and underground waters. The long term safety of radioactive waste repositories is based on artificial and natural barriers, intended to sorb radionuclides after the moment when the storage matrixes and containers will be corroded. Predictions on the efficiency of sorption for more than 10 6 years have to be done in order to demonstrate the safety of such depositories, what is a goal never encountered in the history of sciences and technology. For all these purposes, and, especially for the long term prediction, acquiring of sorption data constitutes only a first step of studies. Modeling based on a very good knowledge of sorption mechanisms is needed. In this review, we shall examine the main approaches and models used to quantify sorption processes, including results taken from the literature and from our own studies. We shall compare sorption models and examine their adequacy with sorption mechanisms. The cited references are only a few examples of the numerous articles published in that field. (orig.)

  12. Non-equilibrium Economics

    Katalin Martinás

    2007-02-01

    Full Text Available A microeconomic, agent based framework to dynamic economics is formulated in a materialist approach. An axiomatic foundation of a non-equilibrium microeconomics is outlined. Economic activity is modelled as transformation and transport of commodities (materials owned by the agents. Rate of transformations (production intensity, and the rate of transport (trade are defined by the agents. Economic decision rules are derived from the observed economic behaviour. The non-linear equations are solved numerically for a model economy. Numerical solutions for simple model economies suggest that the some of the results of general equilibrium economics are consequences only of the equilibrium hypothesis. We show that perfect competition of selfish agents does not guarantee the stability of economic equilibrium, but cooperativity is needed, too.

  13. Sorption and Transport of Pharmaceutical chemicals in Organic- and Mineral-rich Soils

    Vulava, V. M.; Schwindaman, J.; Murphey, V.; Kuzma, S.; Cory, W.

    2011-12-01

    Pharmaceutical, active ingredients in personal care products (PhACs), and their derivative compounds are increasingly ubiquitous in surface waters across the world. Sorption and transport of four relatively common PhACs (naproxen, ibuprofen, cetirizine, and triclosan) in different natural soils was measured. All of these compounds are relatively hydrophobic (log KOW>2) and have acid/base functional groups, including one compound that is zwitterionic (cetirizine.) The main goal of this study was to correlate organic matter (OM) and clay content in natural soils and sediment with sorption and degradation of PhACs and ultimately their potential for transport within the subsurface environment. A- and B-horizon soils were collected from four sub-regions within a pristine managed forested watershed near Charleston, SC, with no apparent sources of anthropogenic contamination. These four soil series had varying OM content (fOC) between 0.4-9%, clay mineral content between 6-20%, and soil pH between 4.5-6. The A-horizon soils had higher fOC and lower clay content than the B-horizon soils. Sorption isotherms measured from batch sorption experimental data indicated a non-linear sorption relationship in all A- and B-horizon soils - stronger sorption was observed at lower PhAC concentrations and lower sorption at higher concentrations. Three PhACs (naproxen, ibuprofen, and triclosan) sorbed more strongly with higher fOC A-horizon soils compared with the B-horizon soils. These results show that soil OM had a significant role in strongly binding these three PhACs, which had the highest KOW values. In contrast, cetirizine, which is predominantly positively charged at pH below 8, strongly sorbed to soils with higher clay mineral content and least strongly to higher fOC soils. All sorption isotherms fitted well to the Freundlich model. For naproxen, ibuprofen, and triclosan, there was a strong and positive linear correlation between the Freundlich adsorption constant, Kf, and f

  14. Nonequilibrium molecular dynamics: The first 25 years

    Hoover, W.G.

    1992-08-01

    Equilibrium Molecular Dynamics has been generalized to simulate Nonequilibrium systems by adding sources of thermodynamic heat and work. This generalization incorporates microscopic mechanical definitions of macroscopic thermodynamic and hydrodynamic variables, such as temperature and stress, and augments atomistic forces with special boundary, constraint, and driving forces capable of doing work on, and exchanging heat with, an otherwise Newtonian system. The underlying Lyapunov instability of these nonequilibrium equations of motion links microscopic time-reversible deterministic trajectories to macroscopic time-irreversible hydrodynamic behavior as described by the Second Law of Thermodynamics. Green-Kubo linear-response theory has been checked. Nonlinear plastic deformation, intense heat conduction, shockwave propagation, and nonequilibrium phase transformation have all been simulated. The nonequilibrium techniques, coupled with qualitative improvements in parallel computer hardware, are enabling simulations to approximate real-world microscale and nanoscale experiments

  15. Nonequilibrium Phenomena in Plasmas

    Sharma, A Surjalal

    2005-01-01

    The complexity of plasmas arises mainly from their inherent nonlinearity and far from equilibrium nature. The nonequilibrium behavior of plasmas is evident in the natural settings, for example, in the Earth's magnetosphere. Similarly, laboratory plasmas such as fusion bottles also have their fair share of complex behavior. Nonequilibrium phenomena are intimately connected with statistical dynamics and form one of the growing research areas in modern nonlinear physics. These studies encompass the ideas of self-organization, phase transition, critical phenomena, self-organized criticality and turbulence. This book presents studies of complexity in the context of nonequilibrium phenomena using theory, modeling, simulations, and experiments, both in the laboratory and in nature.

  16. Sorption Behavior of Compressed CO2 and CH4 on Ultrathin Hybrid Poly(POSS-imide) Layers

    Raaijmakers, Michiel; Ogieglo, Wojciech; Wiese, M.; Wessling, Matthias; Nijmeijer, Arian; Benes, Nieck Edwin

    2015-01-01

    Sorption of compressed gases into thin polymeric films is essential for applications including gas sensors and membrane based gas separation. For glassy polymers, the sorption behavior is dependent on the nonequilibrium status of the polymer. The uptake of molecules by a polymer is generally

  17. Solute induced relaxation in glassy polymers: Experimental measurements and nonequilibrium thermodynamic model

    Minelli, Matteo; Doghieri, Ferruccio

    2014-01-01

    Data for kinetics of mass uptake from vapor sorption experiments in thin glassy polymer samples are here interpreted in terms of relaxation times for volume dilation. To this result, both models from non-equilibrium thermodynamics and from mechanics of volume relaxation contribute. Different kind of sorption experiments have been considered in order to facilitate the direct comparison between kinetics of solute induced volume dilation and corresponding data from process driven by pressure or temperature jumps

  18. Nonequilibrium quantum field theories

    Niemi, A.J.

    1988-01-01

    Combining the Feynman-Vernon influence functional formalism with the real-time formulation of finite-temperature quantum field theories we present a general approach to relativistic quantum field theories out of thermal equilibrium. We clarify the physical meaning of the additional fields encountered in the real-time formulation of quantum statistics and outline diagrammatic rules for perturbative nonequilibrium computations. We derive a generalization of Boltzmann's equation which gives a complete characterization of relativistic nonequilibrium phenomena. (orig.)

  19. Isotherm, kinetic, and thermodynamic study of ciprofloxacin sorption on sediments.

    Mutavdžić Pavlović, Dragana; Ćurković, Lidija; Grčić, Ivana; Šimić, Iva; Župan, Josip

    2017-04-01

    In this study, equilibrium isotherms, kinetics and thermodynamics of ciprofloxacin on seven sediments in a batch sorption process were examined. The effects of contact time, initial ciprofloxacin concentration, temperature and ionic strength on the sorption process were studied. The K d parameter from linear sorption model was determined by linear regression analysis, while the Freundlich and Dubinin-Radushkevich (D-R) sorption models were applied to describe the equilibrium isotherms by linear and nonlinear methods. The estimated K d values varied from 171 to 37,347 mL/g. The obtained values of E (free energy estimated from D-R isotherm model) were between 3.51 and 8.64 kJ/mol, which indicated a physical nature of ciprofloxacin sorption on studied sediments. According to obtained n values as measure of intensity of sorption estimate from Freundlich isotherm model (from 0.69 to 1.442), ciprofloxacin sorption on sediments can be categorized from poor to moderately difficult sorption characteristics. Kinetics data were best fitted by the pseudo-second-order model (R 2  > 0.999). Thermodynamic parameters including the Gibbs free energy (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) were calculated to estimate the nature of ciprofloxacin sorption. Results suggested that sorption on sediments was a spontaneous exothermic process.

  20. Prediction of metal sorption in soils

    Westrich, Henry R.; Anderson, Harold L. Jr.; Arthur, Sara E.; Brady, Patrick V.; Cygan, Randall T.; Liang, Jianjie; Zhang, Pengchu; Yee, N.

    2000-01-01

    Radionuclide transport in soils and groundwaters is routinely calculated in performance assessment (PA) codes using simplified conceptual models for radionuclide sorption, such as the K D approach for linear and reversible sorption. Model inaccuracies are typically addressed by adding layers of conservativeness (e.g., very low K D 's), and often result in failed transport predictions or substantial increases in site cleanup costs. Realistic assessments of radionuclide transport over a wide range of environmental conditions can proceed only from accurate, mechanistic models of the sorption process. They have focused on the sorption mechanisms and partition coefficients for Cs + , Sr 2+ and Ba 2+ (analogue for Ra 2+ ) onto iron oxides and clay minerals using an integrated approach that includes computer simulations, sorption/desorption measurements, and synchrotron analyses of metal sorbed substrates under geochemically realistic conditions. Sorption of Ba 2+ and Sr 2+ onto smectite is strong, pH-independent, and fully reversible, suggesting that cation exchange at the interlayer basal sites controls the sorption process. Sr 2+ sorbs weakly onto geothite and quartz, and is pH-dependent. Sr 2+ sorption onto a mixture of smectite and goethite, however, is pH- and concentration dependent. The adsorption capacity of montmorillonite is higher than that of goethite, which may be attributed to the high specific surface area and reaction site density of clays. The presence of goethite also appears to control the extent of metal desorption. In-situ, extended X-ray absorption fine structure (EXAFS) spectroscopic measurements for montmorillonite and goethite show that the first shell of adsorbed Ba 2+ is coordinated by 6 oxygens. The second adsorption shell, however, varies with the mineral surface coverage of adsorbed Ba 2+ and the mineral substrate. This suggests that Ba 2+ adsorption on mineral surfaces involves more than one mechanism and that the stability of sorbed

  1. Nonequilibrium thermodynamics of nucleation

    Schweizer, M.; Sagis, L.M.C.

    2014-01-01

    We present a novel approach to nucleation processes based on the GENERIC framework (general equation for the nonequilibrium reversible-irreversible coupling). Solely based on the GENERIC structure of time-evolution equations and thermodynamic consistency arguments of exchange processes between a

  2. Statistical thermodynamics of nonequilibrium processes

    Keizer, Joel

    1987-01-01

    The structure of the theory ofthermodynamics has changed enormously since its inception in the middle of the nineteenth century. Shortly after Thomson and Clausius enunciated their versions of the Second Law, Clausius, Maxwell, and Boltzmann began actively pursuing the molecular basis of thermo­ dynamics, work that culminated in the Boltzmann equation and the theory of transport processes in dilute gases. Much later, Onsager undertook the elucidation of the symmetry oftransport coefficients and, thereby, established himself as the father of the theory of nonequilibrium thermodynamics. Com­ bining the statistical ideas of Gibbs and Langevin with the phenomenological transport equations, Onsager and others went on to develop a consistent statistical theory of irreversible processes. The power of that theory is in its ability to relate measurable quantities, such as transport coefficients and thermodynamic derivatives, to the results of experimental measurements. As powerful as that theory is, it is linear and...

  3. Sorption of cesium and uranium to Feldspar

    Wijland, G.C.; Pennders, R.M.J.

    1990-07-01

    Within safety assessment studies, for nuclear waste disposal in deep geologic formations, calculation for the migration of radionuclides through the geosphere are often carried out with models taking sorption into account. In the past 8 years the insight grew that other physico-chemical processes, besides sorption, could affect migration behaviour. While the currently used transport models were being improved taking either linear or non-linear sorption into account, the coupling of geochemical and transport models came into scope. In spite of these developments models which are still based on the sorption theory are frequently applied in studying migration behaviour of radionuclides. This is caused by the necessity of making preliminary pronouncements, while coupled models are still in stage of development and thermodynamic data are very limited available. Therefore one has to obtain insight in the reliability of the models based on the sorption theory. within the sorption database there is a lack of knowledge about mineralogy, composition of the fluid and the experimental conditions underlying the data. Therefore the Expert Group on geochemical Modelling supported by the Finnish proposal in order to obtain insight in the possible deviation of the sorption coefficients that can be estimated from experiments performed with standard samples, fluid composition and experimental conditions. Nine laboratories from OECD membership countries took part in this intercalibration study. In the framework of the Dutch safety assessment studies the Dutch National Institute of Public health and Environmental protection (RIVM) has decided to participate in this exercise. In this report the results are presented of sorption experiments for cesium and natural Uranium to Feldspar. (H.W.). 4 refs.; 1 fig.; 7 tabs

  4. Column Chromatography To Obtain Organic Cation Sorption Isotherms.

    Jolin, William C; Sullivan, James; Vasudevan, Dharni; MacKay, Allison A

    2016-08-02

    Column chromatography was evaluated as a method to obtain organic cation sorption isotherms for environmental solids while using the peak skewness to identify the linear range of the sorption isotherm. Custom packed HPLC columns and standard batch sorption techniques were used to intercompare sorption isotherms and solid-water sorption coefficients (Kd) for four organic cations (benzylamine, 2,4-dichlorobenzylamine, phenyltrimethylammonium, oxytetracycline) with two aluminosilicate clay minerals and one soil. A comparison of Freundlich isotherm parameters revealed isotherm linearity or nonlinearity was not significantly different between column chromatography and traditional batch experiments. Importantly, skewness (a metric of eluting peak symmetry) analysis of eluting peaks can establish isotherm linearity, thereby enabling a less labor intensive means to generate the extensive data sets of linear Kd values required for the development of predictive sorption models. Our findings clearly show that column chromatography can reproduce sorption measures from conventional batch experiments with the benefit of lower labor-intensity, faster analysis times, and allow for consistent sorption measures across laboratories with distinct chromatography instrumentation.

  5. Effects of sorption behaviour on contaminant migration

    Melnyk, T.W.

    1985-11-01

    The effects of sorption behaviour on contaminant migration in groundwater systems are varied. Retardation of migration and dispersive effects can vary widely and contaminant concentration profiles can take a number of different shapes. This report examines the nature of some of these effects, especially those due to sorption behaviours that are dependent on the concentration of the contaminant in the groundwater. The effects are calculated using, in most cases, analytical solutions to the chemical equations imbedded in a simple reaction-cell or box-model transport algorithm. The hydrogeological parameters are held constant, and radioactive decay and hydrodynamic dispersion are excluded. A general discussion of the role of sorption equations in transport modelling is followed by presentation of migration results for a number of models of sorption behaviour varying from linear isotherms, Langmuir, Freundlich and ion-exchange isotherms, to precipitation reactions and multiple-site sorption reactions. The results are compared and general conclusions are drawn about the various migration behaviours calculated. The conclusions are that equilibrium sorption of trace contaminants can be modelled with linear isotherms (constant distribution coefficients or constant retardation factors) but the evaluation and extrapolation of the distribution coefficient are not easy. Nonlinear isotherms lead to unsymmetrical migration fronts. A comparison of Freundlich and linear isotherms is made. Sorption/desorption kinetic factors can be significant on the time scale of laboratory experiments and can cause large dispersive effects. Slow but important reactions can be missed altogether. Precipitation or mineralization behaviour cannot be modelled with constant distribution coefficients. Also, mineralization reactions can be kinetically slow even on the geological time scale. 89 refs

  6. Sorption by cation exchange

    Bradbury, M.H.; Baeyens, B.

    1994-04-01

    A procedure for introducing exchange into geochemical/surface complexation codes is described. Beginning with selectivity coefficients, K c , defined in terms of equivalent fractional ion occupancies, a general expression for the molar based exchange code input parameters, K ex , is derived. In natural systems the uptake of nuclides onto complex sorbents often occurs by more than one mechanism. The incorporation of cation exchange and surface complexation into a geochemical code therefore enables sorption by both mechanisms to be calculated simultaneously. The code and model concepts are tested against sets of experimental data from widely different sorption studies. A proposal is made to set up a data base of selectivity coefficients. Such a data base would form part of a more general one consisting of sorption mechanism specific parameters to be used in conjunction with geochemical/sorption codes to model and predict sorption. (author) 6 figs., 6 tabs., 26 refs

  7. Quantifying the effect of sorption and bioavailability of hydrophobic organic contaminants

    Zhang, W.; Bouwer, E.; Cunningham, A.

    1994-01-01

    In-situ bioremediation has been applied successfully at a few sites. Several restrictions presently exist which could greatly limit the effectiveness of this promising technology. Hydrophobic organic contaminants tend to sorb onto soil. However, microorganisms are most effective in utilizing substrates from the aqueous phase. Sorption tends to separate the direct contact between microorganisms and contaminants necessary for biodegradation to occur. A series of experiments, which represented scenarios with fast sorption/desorption, slow sorption/desorption, mass transfer across boundary layer and mass transfer within attached microorganisms (biofilm), was conducted to demonstrate the concentration effect and the mass transfer effect. A method has been developed to quantify bioavailability of organic contaminants in aquatic environments. Bioavailability Factor (B f ), a dimensionless parameter derived from mathematical models and verified by experimental results, has been formulated to describe the impact of equilibrium sorption, nonequilibrium sorption, and mass transfer processes on the rate and extent of biodegradation of petroleum hydrocarbons

  8. Non-equilibrium dynamics from RPMD and CMD.

    Welsch, Ralph; Song, Kai; Shi, Qiang; Althorpe, Stuart C; Miller, Thomas F

    2016-11-28

    We investigate the calculation of approximate non-equilibrium quantum time correlation functions (TCFs) using two popular path-integral-based molecular dynamics methods, ring-polymer molecular dynamics (RPMD) and centroid molecular dynamics (CMD). It is shown that for the cases of a sudden vertical excitation and an initial momentum impulse, both RPMD and CMD yield non-equilibrium TCFs for linear operators that are exact for high temperatures, in the t = 0 limit, and for harmonic potentials; the subset of these conditions that are preserved for non-equilibrium TCFs of non-linear operators is also discussed. Furthermore, it is shown that for these non-equilibrium initial conditions, both methods retain the connection to Matsubara dynamics that has previously been established for equilibrium initial conditions. Comparison of non-equilibrium TCFs from RPMD and CMD to Matsubara dynamics at short times reveals the orders in time to which the methods agree. Specifically, for the position-autocorrelation function associated with sudden vertical excitation, RPMD and CMD agree with Matsubara dynamics up to O(t 4 ) and O(t 1 ), respectively; for the position-autocorrelation function associated with an initial momentum impulse, RPMD and CMD agree with Matsubara dynamics up to O(t 5 ) and O(t 2 ), respectively. Numerical tests using model potentials for a wide range of non-equilibrium initial conditions show that RPMD and CMD yield non-equilibrium TCFs with an accuracy that is comparable to that for equilibrium TCFs. RPMD is also used to investigate excited-state proton transfer in a system-bath model, and it is compared to numerically exact calculations performed using a recently developed version of the Liouville space hierarchical equation of motion approach; again, similar accuracy is observed for non-equilibrium and equilibrium initial conditions.

  9. Sorption data bases and mechanistic sorption studies

    Bradbury, M.H.

    2000-01-01

    In common with many other countries with a nuclear programme, the Swiss concept for the disposal of radioactive waste is focused on deep burial in specially constructed repositories in geologically stable host rocks. Under such conditions, the most likely means whereby radionuclides might return to the biosphere involves their transport in slowly moving groundwater. The sorption of radionuclides by solid phases in the engineered barriers within the repository, and in the surrounding geological media, limits their release and retards their movement. Performance assessment studies for disposal concepts are carried out by Nagra, the National Cooperative for the Disposal of Radioactive Waste, in which various release scenarios are examined, and 'doses to man' calculated. The uptake of radionuclides by immobile phases is one of the pillars upon which the safety case rests. Hence, sorption databases are very important data sets for performance assessments. The methodology lying behind the construction of sorption databases, and some aspects of the supporting experimental work, are briefly described in this report. Flexible, long-term, focused research programmes are required to properly understand the radionuclide/rock/groundwater system, and this is an essential pre-requisite for producing robust state-of-the-art sorption databases. (author)

  10. Sorption data bases and mechanistic sorption studies

    Bradbury, M.H

    2000-07-01

    In common with many other countries with a nuclear programme, the Swiss concept for the disposal of radioactive waste is focused on deep burial in specially constructed repositories in geologically stable host rocks. Under such conditions, the most likely means whereby radionuclides might return to the biosphere involves their transport in slowly moving groundwater. The sorption of radionuclides by solid phases in the engineered barriers within the repository, and in the surrounding geological media, limits their release and retards their movement. Performance assessment studies for disposal concepts are carried out by Nagra, the National Cooperative for the Disposal of Radioactive Waste, in which various release scenarios are examined, and 'doses to man' calculated. The uptake of radionuclides by immobile phases is one of the pillars upon which the safety case rests. Hence, sorption databases are very important data sets for performance assessments. The methodology lying behind the construction of sorption databases, and some aspects of the supporting experimental work, are briefly described in this report. Flexible, long-term, focused research programmes are required to properly understand the radionuclide/rock/groundwater system, and this is an essential pre-requisite for producing robust state-of-the-art sorption databases. (author)

  11. Nonequilibrium effects in Isoscaling

    Dorso, C. O.; Lopez, J. A.

    2007-01-01

    In this work we study within a simple model different properties of the system that allow us to understand the properties of the isoscaling observable. We first show that isoscaling is a general property of fragmenting systems. We show this by using a simple generalized percolation model. We show that the usual isoscaling property can be obtained in the case of bond percolation in bichromatic lattices with any regular topology. In this case the probabilities of each color (isospin) are independent. We then explore the effect of introducing 'non-equilibrium' effects

  12. The nonequilibrium molecular dynamics

    Hoover, W.G.

    1992-03-01

    MOLECULAR DYNAMICS has been generalized in order to simulate a variety of NONEQUILIBRIUM systems. This generalization has been achieved by adopting microscopic mechanical definitions of macroscopic thermodynamic and hydrodynamic variables, such as temperature and stress. Some of the problems already treated include rapid plastic deformation, intense heat conduction, strong shockwaves simulation, and far-from-equilibrium phase transformations. Continuing advances in technique and in the modeling of interatomic forces, coupled with qualitative improvements in computer hardware, are enabling such simulations to approximate real-world microscale and nanoscale experiments

  13. Instabilities and nonequilibrium structures

    Tirapegui, E.; Villarroel, D.

    1987-01-01

    Physical systems can be studied both near to and far from equilibrium where instabilities appear. The behaviour in these two regions is reviewed in this book, from both the theoretical and application points of view. The influence of noise in these situations is an essential feature which cannot be ignored. It is therefore discussed using phenomenological and theoretical approaches for the numerous problems which still remain in the field. This volume should appeal to mathematicians and physicists interested in the areas of instability, bifurcation theory, dynamical systems, pattern formation, nonequilibrium structures and statistical mechanics. (Auth.)

  14. Sorption of curium by silica colloids: Effect of humic acid

    Kar, Aishwarya Soumitra; Kumar, Sumit; Tomar, B.S.; Manchanda, V.K.

    2011-01-01

    Sorption of curium by silica colloids has been studied as a function of pH and ionic strength using 244 Cm as a tracer. The sorption was found to increase with increasing pH and reach a saturation value of ∼95% at pH beyond 5.3. The effect of humic acid on the sorption of 244 Cm onto silica was studied by changing the order of addition of the metal ion and humic acid. In general, in the presence of humic acid (2 mg/L), the sorption increased at lower pH (<5) while it decreased in the pH range 6.5-8 and above pH 8, the sorption was found to increase again. As curium forms strong complex with humic acid, its presence results in the enhancement of curium sorption at lower pH. At higher pH the humic acid present in the solution competes with the surface sites for curium thus decreasing the sorption. The decrease in the Cm sorption in presence of humic acid was found to be less when humic acid was added after the addition of curium. Linear additive model qualitatively reproduced the profile of the Cm(III) sorption by silica in presence of humic acid at least in the lower pH region, however it failed to yield quantitative agreement with the experimental results. The results of the present study evidenced the incorporation of Cm into the silica matrix.

  15. A new algorithm for extended nonequilibrium molecular dynamics simulations of mixed flow

    Hunt, T.A.; Hunt, Thomas A.; Bernardi, Stefano; Todd, B.D.

    2010-01-01

    In this work, we develop a new algorithm for nonequilibrium molecular dynamics of fluids under planar mixed flow, a linear combination of planar elongational flow and planar Couette flow. To date, the only way of simulating mixed flow using nonequilibrium molecular dynamics techniques was to impose

  16. A nonequilibrium model for reactive contaminant transport through fractured porous media: Model development and semianalytical solution

    Joshi, Nitin; Ojha, C. S. P.; Sharma, P. K.

    2012-10-01

    In this study a conceptual model that accounts for the effects of nonequilibrium contaminant transport in a fractured porous media is developed. Present model accounts for both physical and sorption nonequilibrium. Analytical solution was developed using the Laplace transform technique, which was then numerically inverted to obtain solute concentration in the fracture matrix system. The semianalytical solution developed here can incorporate both semi-infinite and finite fracture matrix extent. In addition, the model can account for flexible boundary conditions and nonzero initial condition in the fracture matrix system. The present semianalytical solution was validated against the existing analytical solutions for the fracture matrix system. In order to differentiate between various sorption/transport mechanism different cases of sorption and mass transfer were analyzed by comparing the breakthrough curves and temporal moments. It was found that significant differences in the signature of sorption and mass transfer exists. Applicability of the developed model was evaluated by simulating the published experimental data of Calcium and Strontium transport in a single fracture. The present model simulated the experimental data reasonably well in comparison to the model based on equilibrium sorption assumption in fracture matrix system, and multi rate mass transfer model.

  17. Sorption properties of wool

    Radetić Maja M.

    2004-01-01

    Full Text Available Strict ecological legislation, especially in highly developed countries, imposed requirements for the purification of industrial effluents and the need for efficient oil clean up after sea and inland water spills. Although numerous processes have been developed, the application of sorbents is still one of the most efficient methods to remove heavy metal ions, dyes and crude oil from water. Recently, special attention was paid to sorbents based on natural fibres. A review of studies concerning the sorption properties of wool is presented in this paper. The presence of various functional groups on the wool fibre surface contributes to the efficient sorption of heavy metal ions and dyes. A hydrophobic, scaly surface and fibre crimp strongly influence the high sorption capacity of wool for oil. Wool has great sorption potential even as a recycled material. Accordingly, it can be used as a viable substitute to commercially available synthetic sorbents that show poor biodegradab ility.

  18. Moisture sorption of Thai red curry powder

    Sudathip Inchuen

    2009-12-01

    Full Text Available Moisture sorption study was conducted on Thai red curry powder prepared by two different drying methods, viz. microwave and hot-air drying. Moisture sorption isotherms of the red curry powder at 30 C and water activity in the range of 0.113-0.970 were determined by a static gravimetric method. The isotherms exhibited Type III behaviour. The moisture sorption data were fitted to several sorption models and a non-linear regression analysis method was used to evaluate the constants of the sorption equations. The fit was evaluated using the coefficient of determination (R2, the reduced chi-square (2 and the root mean square error (RMSE. The GAB model followed by the Lewiski-3 model gave the best fit to the experimental data. The monolayer moisture content, taken as the safe minimum moisture level in the red curry powder, was determined using the BET equation and was found to range between 0.080 - 0.085 gram water per gram dry matter.

  19. Sorption of polycyclic aromatic hydrocarbons on particulate organic matters

    Guo Xueyan; Luo Lei; Ma Yibing; Zhang Shuzhen

    2010-01-01

    Particulate organic matter (POM) is a key organic matter fraction which can influence soil fertility. Its interactions with hydrophobic organic pollutants (HOCs) have not been characterized and the mechanisms of retention of HOCs by POM remain unclear. In the present study, sorption behaviors of polycyclic aromatic hydrocarbons (PAHs) naphthalene (NAP), phenanthrene (PHE), and pyrene (PYR) by POMs separated from different soils were examined and the POMs were characterized by elemental analysis, solid state 13 C NMR, and Fourier transform infrared spectroscopy (FT-IR). The results indicated that POMs were mainly composed of aliphatic components with high polarity. The different original POMs showed similar chemical composition and configuration. Sorption behaviors of PAHs indicated that there was no significant difference in sorption capacity among the POMs. Sorption of NAP and PHE by POMs displayed a nonlinear isotherm, while sorption of PYR yielded a linear isotherm. No significant hysteresis and ionic strength effect were observed for PAH desorption from the POMs.

  20. Sorption behaviour of cobalt-60 on Suez Canal bottom sediments

    Abdel Gawad, S.A.; El-Shinawy, R.M.K.; Abdel Malik, W.E.Y.

    1981-01-01

    Mineralogical, elemental analysis and sorption behaviour of the Suez Canal bottom sediments in the Port Said area were investigated. It was found that the bottom sediment consist mainly of quartz, feldspars and traces of calcite mineral. The cation-exchange capacity was found to increase as the particle size of the sediment decreased. Sorption of 60 Co by the bottom sediment increased with contact time up to 6 h. Variation of the solution pH from 4 to 9 showed limited increase in the sorption of 60 Co. As carrier concentrations increase from 10 -7 N to 10 -3 N, sorption of Co was found to increase linearly following Freundlich isotherm. The presence of Mg 2+ and Fe 3+ in solution depressed the sorption of 60 Co by the sediments. The desorption of 60 Co from bottom sediment with distilled and Suez Canal water was found to increase with contact time. (author)

  1. A Lagrangian formalism for nonequilibrium ensembles

    Sobouti, Y.

    1989-08-01

    It is suggested to formulate a nonequilibrium ensemble theory by maximizing a time-integrated entropy constrained by Liouville's equation. This leads to distribution functions of the form f = Z -1 exp(-g/kT), where g(p,q,t) is a solution of Liouville's equation. A further requirement that the entropy should be an additivie functional of the integrals of Liouville's equation, limits the choice of g to linear superpositions of the nonlinearly independent integrals of motion. Time-dependent and time-independent integrals may participate in this superposition. (author). 14 refs

  2. Effect of humic acid on sorption of technetium by alumina

    Kumar, S.; Rawat, N.; Kar, A.S.; Tomar, B.S.; Manchanda, V.K.

    2011-01-01

    Highlights: → Tc sorption on alumina has been studied under aerobic as well anaerobic condition over pH 3-10. → Effect of humic acid on sorption of Tc by alumina has been investigated. → Linear additive modeling and surface complexation modeling were carried out to delineate the role of humic acid in Tc(IV) sorption in ternary system of Tc(IV)-humic acid-alumina. → Sorption of humic acid onto alumina and strong complexation of Tc(IV) with humic acid were found to govern the sorption of Tc(IV) in the ternary system. - Abstract: Sorption of technetium by alumina has been studied in absence as well as in presence of humic acid using 95 Tc m as a tracer. Measurements were carried out at fixed ionic strength (0.1 M NaClO 4 ) under varying pH (3-10) as well as redox (aerobic and reducing anaerobic) conditions. Under aerobic conditions, negligible sorption of technetium was observed onto alumina both in absence and in presence of humic acid. However, under reducing conditions (simulated with [Sn(II)] = 10 -6 M), presence of humic acid enhanced the sorption of technetium in the low pH region significantly and decreased at higher pH with respect to that in absence of humic acid. Linear additive as well as surface complexation modeling of Tc(IV) sorption in presence of humic acid indicated the predominant role of sorbed humic acid in deciding technetium sorption onto alumina.

  3. Definition of Nonequilibrium Entropy of General Systems

    Mei, Xiaochun

    1999-01-01

    The definition of nonequilibrium entropy is provided for the general nonequilibrium processes by connecting thermodynamics with statistical physics, and the principle of entropy increment in the nonequilibrium processes is also proved in the paper. The result shows that the definition of nonequilibrium entropy is not unique.

  4. Sorption of benzothiazoles onto sandy aquifer material under equilibrium and nonequlibrium conditions

    Kragulj Marijana M.

    2014-01-01

    Full Text Available In this study, the sorption behaviour of 1,3-benzothiazole (BT and 2-(methylthiobenzothiazole (MTBT was investigated on Danube geosorbent under equilibrium and nonequilibrium conditions. All sorption isotherms fitted well with the Freundlich model (R2=0.932-0.993. The results showed that organic matter of the Danube geosorbent has a higher sorption affinity for the more hydrophobic MTBT compared to BT. However, sorption-desorption experiments showed that MTBT was more easily desorbed than BT molecules, which indicates the importance of absorption relative to adsorption in the overall sorption mechanism of MTBT. In general, molecules of BT and MTBT were more easily desorbed in the lower concentration range, which resulted in an increase in the hysteresis indices with increasing concentrations. Column experiments revealed that retention of the investigated compounds on the aquifer material followed the compound’s hydrophobicity. BT showed a lower retention, in accordance with its lower sorption affinity obtained in the static experiments, while MTBT showed a greater sorption affinity, and thus had a longer retention time on the column. Thus during transport BT represent greater risk for groundwaters than MTBT. These results have increased our understanding of benzothiazoles sorption and desorption process which represent one of the most important factors which influence the behaviour of organic compounds in the environment.

  5. Modelling of a diffusion-sorption experiment on sandstone

    Smith, P.A.

    1989-11-01

    The results of a diffusion-sorption experiment on a sample of Darley Dale sandstone, using simulated groundwater spiked with a mixture of 125 I, 85 Sr and 137 Cs, are modelled by a one-dimensional porous medium approach in which sorption is described by Freundlich isotherms. The governing equations are solved analytically for the special case of a linear isotherm, and numerically using the computer code RANCHDIFF for non-linear isotherms. A set of time-dependent, ordinary differential equations is obtained using the Lagrange interpolation technique and integrated by Gear's variable order predictor-corrector method. It is shown that the sorption behaviour of 85 Sr can be modelled successfully by a linear isotherm, using a sorption parameter consistent with batch-sorption tests. The behaviour of 137 Cs may be modelled by a non-linear isotherm, but the amount of 137 Cs sorbed is less than that anticipated from batch-sorption tests. 125 I is assumed to be non-sorbing and is used to determine the porosity of the sandstone. (author) 10 figs., 4 tabs., 6 refs

  6. Metal sorption on kaolinite

    Westrich, H.R.; Brady, P.V.; Cygan, R.T.; Nagy, K.L.; Anderson, H.L.

    1997-01-01

    A key issue in performance assessment of low-level radioactive waste sites is predicting the transport and retardation of radionuclides through local soils under a variety of hydrologic and geochemical conditions. Improved transport codes should include a mechanistic model of radionuclide retardation. The authors have been investigating metal sorption (Cs + , Sr 2+ , and Ba 2+ ) on a simple clay mineral (kaolinite) to better understand the geochemical interactions of common soil minerals with contaminated groundwaters. These studies include detailed characterizations of kaolinite surfaces, experimental adsorption measurements, surface complexation modeling, and theoretical simulations of cation sorption. The aluminol edge (010) site has been identified as the most likely site for metal sorption on kaolinite in natural solutions. Relative metal binding strengths decrease from Ba 2+ to Sr 2+ to Cs + , with some portion sorbed on both kaolinite edges and basal surfaces. Some Cs + also appears to be irreversibly sorbed on both sites. Molecular dynamics simulations suggest that Cs + is sorbed at aluminol (010) edge sites as an inner-sphere complex and weakly sorbed as an outer-sphere complex on (001) basal surfaces. These results provide the basis to understand and predict metal sorption onto kaolinite, and a framework to characterize sorption processes on more complex clay minerals

  7. Interim report on modeling sorption with EQ3/6

    Viani, B.

    1988-01-01

    Reversible, equilibrium models of sorption to be incorporated into the EQ3/6 geochemical modeling package are summarized. Empirical sorption models as formulated in linear, Langmuir, and Freundlich isotherms will be developed as options to EQ3/6. This work will be done at LLNL. Options for modeling sorption using surface- complexation constructs (diffuse, constant capacitance, and triple-layer models) will also be developed. Development of the surface-complexation options will require part of the work be done under contract. 27 refs., 1 fig

  8. Optical orientation of the homogeneous nonequilibrium Bose-Einstein condensate of exciton polaritons

    Korenev, V. L.

    2012-07-01

    A simple model, describing the steady state of the nonequilibrium polarization of a homogeneous Bose-Einstein condensate of exciton polaritons, is considered. It explains the suppression of spin splitting of a nonequilibrium polariton condensate in an external magnetic field, the linear polarization, the linear-to-circular polarization conversion, and the unexpected sign of the circular polarization of the condensate all on equal footing. It is shown that inverse effects are possible, to wit, spontaneous circular polarization and the enhancement of spin splitting of a nonequilibrium condensate of polaritons.

  9. Anisotropic nonequilibrium hydrodynamic attractor

    Strickland, Michael; Noronha, Jorge; Denicol, Gabriel S.

    2018-02-01

    We determine the dynamical attractors associated with anisotropic hydrodynamics (aHydro) and the DNMR equations for a 0 +1 d conformal system using kinetic theory in the relaxation time approximation. We compare our results to the nonequilibrium attractor obtained from the exact solution of the 0 +1 d conformal Boltzmann equation, the Navier-Stokes theory, and the second-order Mueller-Israel-Stewart theory. We demonstrate that the aHydro attractor equation resums an infinite number of terms in the inverse Reynolds number. The resulting resummed aHydro attractor possesses a positive longitudinal-to-transverse pressure ratio and is virtually indistinguishable from the exact attractor. This suggests that an optimized hydrodynamic treatment of kinetic theory involves a resummation not only in gradients (Knudsen number) but also in the inverse Reynolds number. We also demonstrate that the DNMR result provides a better approximation of the exact kinetic theory attractor than the Mueller-Israel-Stewart theory. Finally, we introduce a new method for obtaining approximate aHydro equations which relies solely on an expansion in the inverse Reynolds number. We then carry this expansion out to the third order, and compare these third-order results to the exact kinetic theory solution.

  10. Sorption kinetics of diuron on volcanic ash derived soils.

    Cáceres-Jensen, Lizethly; Rodríguez-Becerra, Jorge; Parra-Rivero, Joselyn; Escudey, Mauricio; Barrientos, Lorena; Castro-Castillo, Vicente

    2013-10-15

    Diuron sorption kinetic was studied in Andisols, Inceptisol and Ultisols soils in view of their distinctive physical and chemical properties: acidic pH and variable surface charge. Two types of kinetic models were used to fit the experimental dates: those that allow to establish principal kinetic parameters and modeling of sorption process (pseudo-first-order, pseudo-second-order), and some ones frequently used to describe solute transport mechanisms of organic compounds on different sorbents intended for remediation purposes (Elovich equation, intraparticle diffusion, Boyd, and two-site nonequilibrium models). The best fit was obtained with the pseudo-second-order model. The rate constant and the initial rate constant values obtained through this model demonstrated the behavior of Diuron in each soil, in Andisols were observed the highest values for both parameters. The application of the models to describe solute transport mechanisms allowed establishing that in all soils the mass transfer controls the sorption kinetic across the boundary layer and intraparticle diffusion into macropores and micropores. The slowest sorption rate was observed on Ultisols, behavior which must be taken into account when the leaching potential of Diuron is considered. Copyright © 2013 Elsevier B.V. All rights reserved.

  11. Radionuclide sorption database for Swiss safety assessment

    McKinley, I.G.; Hadermann, J.

    1984-10-01

    Recommended sorption data for use in transport models for a Swiss High-Level Waste repository are presented. The models used in 'Project Gewaehr 1985' assume linear sorption isotherms and require elemental partition coefficient (Kd) data. On the basis of a literature search 'realistic' Kd data for 22 elements have been selected for weathered crystalline rock and sediments in contact with a reducing groundwater and also sediments with a less reducing groundwater. In an appendix sorption data for 28 elements on bentonite backfill are given. These data are supplemented with 'conservative' estimates taken to represent minimum reasonable values. Available data are discussed for each element clearly exhibiting (i) the large gaps in knowledge, (ii) their unbalanced distribution between different elements and, hence, (iii) the need for further experiments in the laboratory, the field and analogue studies. An overview of the theoretical concepts of sorption, experimental methodology and data interpretation is given in order to put the values into context. General problem areas are identified. (Auth.)

  12. Determination of Chlorinated Solvent Sorption by Porous Material-Application to Trichloroethene Vapor on Cement Mortar.

    Musielak, Marion; Brusseau, Mark L; Marcoux, Manuel; Morrison, Candice; Quintard, Michel

    2014-08-01

    Experiments have been performed to investigate the sorption of trichloroethene (TCE) vapor by concrete material or, more specifically, the cement mortar component. Gas-flow experiments were conducted using columns packed with small pieces of cement mortar obtained from the grinding of typical concrete material. Transport and retardation of TCE at high vapor concentrations (500 mg L -1 ) was compared to that of a non-reactive gas tracer (Sulfur Hexafluoride, SF6). The results show a large magnitude of retardation (retardation factor = 23) and sorption (sorption coefficient = 10.6 cm 3 g -1 ) for TCE, compared to negligible sorption for SF6. This magnitude of sorption obtained with pollutant vapor is much bigger than the one obtained for aqueous-flow experiments conducted for water-saturated systems. The considerable sorption exhibited for TCE under vapor-flow conditions is attributed to some combination of accumulation at the air-water interface and vapor-phase adsorption, both of which are anticipated to be significant for this system given the large surface area associated with the cement mortar. Transport of both SF6 and TCE was simulated successfully with a two-region physical non-equilibrium model, consistent with the dual-medium structure of the crushed cement mortar. This work emphasizes the importance of taking into account sorption phenomena when modeling transport of volatile organic compounds through concrete material, especially in regard to assessing vapor intrusion.

  13. Non-equilibrium phase transitions

    Henkel, Malte; Lübeck, Sven

    2009-01-01

    This book describes two main classes of non-equilibrium phase-transitions: (a) static and dynamics of transitions into an absorbing state, and (b) dynamical scaling in far-from-equilibrium relaxation behaviour and ageing. The first volume begins with an introductory chapter which recalls the main concepts of phase-transitions, set for the convenience of the reader in an equilibrium context. The extension to non-equilibrium systems is made by using directed percolation as the main paradigm of absorbing phase transitions and in view of the richness of the known results an entire chapter is devoted to it, including a discussion of recent experimental results. Scaling theories and a large set of both numerical and analytical methods for the study of non-equilibrium phase transitions are thoroughly discussed. The techniques used for directed percolation are then extended to other universality classes and many important results on model parameters are provided for easy reference.

  14. Sorption behaviour of perfluoroalkyl substances in soils.

    Milinovic, Jelena; Lacorte, Silvia; Vidal, Miquel; Rigol, Anna

    2015-04-01

    The sorption behaviour of three perfluoroalkyl substances (PFASs), perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutane sulfonic acid (PFBS), was studied in six soils with contrasting characteristics, especially in the organic carbon content. Sorption isotherms were obtained by equilibrating the soil samples with 0.01 mol L(-1) CaCl2 solutions spiked with increasing concentrations of the target PFAS. The sorption reversibility of PFASs was also tested for some of the samples. Liquid chromatography coupled to tandem mass spectrometry was used to quantify the target PFASs in the solutions. Both the Freundlich and linear models were appropriate to describe the sorption behaviour of PFASs in soils, and enabled us to derive solid-liquid distribution coefficients (Kd) for each compound in each soil. Kd values increased from 19 to 295 mL g(-1) for PFOS, from 2.2 to 38 mL g(-1) for PFOA and from 0.4 to 6.8 mL g(-1) for PFBS, and were positively correlated with the organic carbon content of the soil. KOC values obtained from the correlations were 710, 96 and 17 mL g(-1) for PFOS, PFOA and PFBS, respectively. Whereas Kd values decreased in the sequence PFOS>PFOA>PFBS, desorption yields were lower than 13% for PFOS, from 24 to 58% for PFOA, and from 32 to 60% for PFBS. This shows that the physicochemical characteristics of PFASs, basically their hydrophobicity, controlled their sorption behaviour in soils, with PFOS being the most irreversibly sorbed PFAS. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Technetium Sorption Media Review

    Duncan, J.B.; Kelly, S.E.; Robbins, R.A.; Adams, R.D.; Thorson, M.A.; Haass, C.C.

    2011-01-01

    This report presents information and references to aid in the selection of 99Tc sorption media for feasibility studies regarding the removal of 99Tc from Hanford's low activity waste. The report contains literature search material for sorption media (including ion exchange media) for the most tested media to date, including SuperLig 639, Reillex HPQ, TAM (Kruion), Purolite A520E and A530E, and Dowex 1X8. The U.S. Department of Energy (DOE), Office of River Protection (ORP) is responsible for management and completion of the River Protection Project (RPP) mission, which comprises both the Hanford Site tank farms and the Waste Treatment and Immobilization Plant (WTP). The RPP mission is to store, retrieve and treat Hanford's tank waste; store and dispose of treated wastes; and close the tank farm waste management areas and treatment facilities in a safe, environmentally compliant, cost-effective and energy-effective manner.

  16. TECHNETIUM SORPTION MEDIA REVIEW

    DUNCAN JB; KELLY SE; ROBBINS RA; ADAMS RD; THORSON MA; HAASS CC

    2011-08-25

    This report presents information and references to aid in the selection of 99Tc sorption media for feasibility studies regarding the removal of 99Tc from Hanford's low activity waste. The report contains literature search material for sorption media (including ion exchange media) for the most tested media to date, including SuperLig 639, Reillex HPQ, TAM (Kruion), Purolite A520E and A530E, and Dowex 1X8. The U.S. Department of Energy (DOE), Office of River Protection (ORP) is responsible for management and completion of the River Protection Project (RPP) mission, which comprises both the Hanford Site tank farms and the Waste Treatment and Immobilization Plant (WTP). The RPP mission is to store, retrieve and treat Hanford's tank waste; store and dispose of treated wastes; and close the tank farm waste management areas and treatment facilities in a safe, environmentally compliant, cost-effective and energy-effective manner.

  17. Open problems in non-equilibrium physics

    Kusnezov, D.

    1997-01-01

    The report contains viewgraphs on the following: approaches to non-equilibrium statistical mechanics; classical and quantum processes in chaotic environments; classical fields in non-equilibrium situations: real time dynamics at finite temperature; and phase transitions in non-equilibrium conditions

  18. Open problems in non-equilibrium physics

    Kusnezov, D.

    1997-09-22

    The report contains viewgraphs on the following: approaches to non-equilibrium statistical mechanics; classical and quantum processes in chaotic environments; classical fields in non-equilibrium situations: real time dynamics at finite temperature; and phase transitions in non-equilibrium conditions.

  19. Sorption of a nonionic surfactant Tween 80 by minerals and soils

    Kang, Soyoung, E-mail: soyoung@pusan.ac.kr; Jeong, Hoon Young, E-mail: hjeong@pusan.ac.kr

    2015-03-02

    Highlights: • Tween 80 sorption varies significantly among soil minerals. • Sorption mechanisms and atomic compositions explain to mineral-specific sorption. • Clay minerals and SOM in soils are the key contributors to Tween 80 sorption. • Hysteresis suggests the potential difficulty in removing residual surfactants. - Abstract: Batch experiments were conducted to evaluate Tween 80 sorption by oxides, aluminosilicates, and soils. For oxides, the sorption by silica and alumina follow linear isotherms, and that by hematite follows a Langmuir isotherm. Considering isotherm type and surface coverage, Tween 80 may partition into the silica/alumina–water interface, whereas it may bind to hematite surface sites. Among aluminosilicates, montmorillonite shows the greatest sorption due to the absorption of Tween 80 into interlayers. For other aluminosilicates, it sorbs to surfaces, with the sorption increasing as plagioclase < vermiculite < kaolinite. This results from the relative reactivity among surface sites: ≡NaOH, ≡CaOH << ≡SiOH < ≡AlOH. Experiments using dry- and wet-sieved soils reveal that fine-grained clay minerals, difficult to separate by dry-sieving, contribute significantly to Tween 80 sorption. The greater sorption by untreated soils than H{sub 2}O{sub 2}-treated soils indicates that soil organic matter is a vital sorbent. The sorption hysteresis, contributed to by clay minerals and soil organic matter, is characterized by the greater sorption during the desorption than the sorption stages. This suggests the potential difficulty in removing surfactants from soils. Also, sorption of surfactants can adversely affect surfactant-enhanced remediation by decreasing the aquifer permeability and the availability of surfactants for micellar solubilization.

  20. Sorption of actinides onto nanodiamonds

    Buchatskaya, Yulia; Romanchuk, Anna; Yakovlev, Ruslan; Kulakova, Inna [Lomonosov Moscow State Univ., Moscow (Russian Federation). Dept. of Chemistry; Shiryaev, Andrei [Russian Academy of Sciences, Moscow (Russian Federation). Frumkin Institute of Physical Chemistry and Electrochemistry; Russian Academy of Sciences, Moscow (Russian Federation). Inst. of Geology of Ore Deposits, Petrography, Mineralogy and Geochemistry; Kalmykov, Stepan [Lomonosov Moscow State Univ., Moscow (Russian Federation). Dept. of Chemistry; Russian Academy of Sciences, Moscow (Russian Federation). Frumkin Institute of Physical Chemistry and Electrochemistry; Russian Academy of Sciences, Moscow (Russian Federation). Vernadsky Institute of Geochemistry and Analytical Chemistry

    2015-06-01

    Detonation nanodiamonds (ND) present a significant part of nanocarbons group, which could be produced on commercial scale by detonation of explosives in a closed chamber. Their unique properties of high surface area, low weight and radiation resistance make ND a prospective candidate for applications in sorption processes in radiochemistry. To study the influence of surface chemistry on sorption properties, apristine sample of ND was treated with acids and hydrogen. The surface chemistry of the samples was characterised by infrared spectroscopy, X-ray photoelectron spectroscopy and Boehm titration. The sorption properties of ND were tested fordifferent radionuclides. The sorption capacity of ND was shown to be higher than those of commonly used radionuclide sorbents like activated carbon and compariable to other members of nanocarbon group like graphene oxide and carbon nanotubes. The sorption properties were shown to be influenced by the presence of oxygen-containing groups on the surface of ND. This represents an opportunity to increase the sorption capacity of ND.

  1. Sorption of actinides onto nanodiamonds

    Buchatskaya, Yulia; Romanchuk, Anna; Yakovlev, Ruslan; Kulakova, Inna; Shiryaev, Andrei; Russian Academy of Sciences, Moscow; Kalmykov, Stepan; Russian Academy of Sciences, Moscow; Russian Academy of Sciences, Moscow

    2015-01-01

    Detonation nanodiamonds (ND) present a significant part of nanocarbons group, which could be produced on commercial scale by detonation of explosives in a closed chamber. Their unique properties of high surface area, low weight and radiation resistance make ND a prospective candidate for applications in sorption processes in radiochemistry. To study the influence of surface chemistry on sorption properties, apristine sample of ND was treated with acids and hydrogen. The surface chemistry of the samples was characterised by infrared spectroscopy, X-ray photoelectron spectroscopy and Boehm titration. The sorption properties of ND were tested fordifferent radionuclides. The sorption capacity of ND was shown to be higher than those of commonly used radionuclide sorbents like activated carbon and compariable to other members of nanocarbon group like graphene oxide and carbon nanotubes. The sorption properties were shown to be influenced by the presence of oxygen-containing groups on the surface of ND. This represents an opportunity to increase the sorption capacity of ND.

  2. Review of sorption models, and their suitability for use in performance assessments

    Harvey, K.B.

    1997-02-01

    The sorption of radionuclides on mineral surfaces is an important mechanism for retarding the movement of radionuclides from a geological nuclear fuel disposal vault, through the geosphere, to the biosphere. Sorption processes are known to increase the travel times for some radionuclides by 103 to 106 times relative to the groundwater flow, and this delay can provide the opportunity for radioactive decay before the radionuclide enters the biosphere. Sorption models are, or can be, used as a means of including the effects of sorption in the transport equations which describe the movement of radionuclides through the geosphere. Sorption models are, or could be, based on sorption isotherms, such as the Langmuir and Freundlich isotherms, ion-exchange models, surface-complexation models, or parametric models that are, essentially, interpolated databases. All national nuclear fuel waste disposal programs currently assume the linear adsorption isotherm, which states that the degree of sorption on a surface is a linear function of the concentration of sorbing ion in solution. The sorption models that are, or could be, applied to the movement of radionuclides in the geosphere are reviewed. It is concluded that, at the present state of knowledge, no single model has been demonstrated to provide an adequate description of radionuclide sorption. Reasons for this inadequacy vary, ranging from lack of data, through restricted ability to describe sorption under a variety of conditions, to current levels of development of the models. It is concluded that a parametric model, associated with a linear sorption isotherm, is currently the most practical choice that can be made. Following the completion of an earlier draft of this report, a new approach to surface complexation modelling, the 'discrete-log-K-spectrum' model, was published. This model appears to have the potential to achieve a synthesis of many of the concepts used in sorption modelling. For this reason, a description of

  3. Non-equilibrium supramolecular polymerization.

    Sorrenti, Alessandro; Leira-Iglesias, Jorge; Markvoort, Albert J; de Greef, Tom F A; Hermans, Thomas M

    2017-09-18

    Supramolecular polymerization has been traditionally focused on the thermodynamic equilibrium state, where one-dimensional assemblies reside at the global minimum of the Gibbs free energy. The pathway and rate to reach the equilibrium state are irrelevant, and the resulting assemblies remain unchanged over time. In the past decade, the focus has shifted to kinetically trapped (non-dissipative non-equilibrium) structures that heavily depend on the method of preparation (i.e., pathway complexity), and where the assembly rates are of key importance. Kinetic models have greatly improved our understanding of competing pathways, and shown how to steer supramolecular polymerization in the desired direction (i.e., pathway selection). The most recent innovation in the field relies on energy or mass input that is dissipated to keep the system away from the thermodynamic equilibrium (or from other non-dissipative states). This tutorial review aims to provide the reader with a set of tools to identify different types of self-assembled states that have been explored so far. In particular, we aim to clarify the often unclear use of the term "non-equilibrium self-assembly" by subdividing systems into dissipative, and non-dissipative non-equilibrium states. Examples are given for each of the states, with a focus on non-dissipative non-equilibrium states found in one-dimensional supramolecular polymerization.

  4. Rheology via nonequilibrium molecular dynamics

    Hoover, W.G.

    1982-10-01

    The equilibrium molecular dynamics formulated by Newton, Lagrange, and Hamilton has been modified in order to simulate rheologial molecular flows with fast computers. This modified Nonequilibrium Molecular Dynamics (NEMD) has been applied to fluid and solid deformations, under both homogeneous and shock conditions, as well as to the transport of heat. The irreversible heating associated with dissipation could be controlled by carrying out isothermal NEMD calculations. The new isothermal NEMD equations of motion are consistent with Gauss' 1829 Least-Constraint principle as well as certain microscopic equilibrium and nonequilibrium statistical formulations due to Gibbs and Boltzmann. Application of isothermal NEMD revealed high-frequency and high-strain-rate behavior for simple fluids which resembled the behavior of polymer solutions and melts at lower frequencies and strain rates. For solids NEMD produces plastic flows consistent with experimental observations at much lower strain rates. The new nonequilibrium methods also suggest novel formulations of thermodynamics in nonequilibrium systems and shed light on the failure of the Principle of Material Frame Indifference

  5. Anomalous properties of hot dense nonequilibrium plasmas

    Ferrante, G; Zarcone, M; Uryupin, S A

    2005-01-01

    A concise overview of a number of anomalous properties of hot dense nonequilibrium plasmas is given. The possibility of quasistationary megagauss magnetic field generation due to Weibel instability is discussed for plasmas created in atom tunnel ionization. The collisionless absorption and reflection of a test electromagnetic wave normally impinging on the plasma with two-temperature bi-maxwellian electron velocity distribution function are studied. Due to the wave magnetic field influence on the electron kinetics in the skin layer the wave absorption and reflection significantly depend on the degree of the electron temperature anisotropy. The linearly polarized impinging wave during reflection transforms into an elliptically polarized one. The problem of transmission of an ultrashort laser pulse through a layer of dense plasma, formed as a result of ionization of a thin foil, is considered. It is shown that the strong photoelectron distribution anisotropy yields an anomalous penetration of the wave field through the foil

  6. Characterization of U(VI) Sorption-Desorption Processes and Model Upscaling

    Bai, Jing; Dong, Wenming; Ball, William P.

    2006-01-01

    U(VI) diffusion in silt/clay layers. Batch isotherm experiments were first used to confirm sorption isotherms under the intended test conditions and diffusion cell experiments were then conducted to explore the diffusion hypotheses. Important new information was obtained about the role of aqueous calcium and solid calcium carbonate in controlling sorption equilibrium with Hanford sediments. The retarded interparticle diffusion model with local sorption equilibrium was shown to very successfully simulate diffusion at high aqueous concentration of U(VI). By contrast, however, diffusion data obtained at low concentration suggested nonequilibrium of sorption even at diffusion time scales. Such nonequilibrium effects at low concentration are likely to be the result of sorption retarded intraparticle diffusion, and strong U(VI) sorption in the low concentration range

  7. Effects of sorption and temperature on solute transport in unsaturated steady flow

    Fuentes, H.R.; Polzer, W.L.; Essington, E.H.

    1986-01-01

    It is known that temperature affects physical and chemical processes and that these processes may alter the transport of solutes in the environment. Laboratory column studies were performed in unsaturated flow conditions with a composite pulse containing iodide, cobalt, cesium and strontium each at 10 -3 M. The experiments were performed with Bandelier Tuff and produced breakthrough curves that indicate significant changes in transport due to a temperature change from 25 0 C to 5 0 C for nonconservative solutes. Also, the interpretation of the temperature and sorption data suggest that the differences in transport between 5 0 C and 25 0 C for nonconservative solutes may be predicted in a qualitative manner from batch equilibrium and nonequilibrium sorption data and the theory of sorption used in deriving the modified Freundlich isotherm equation. These effects should be of concern in modeling and management of spills and waste disposal within this range of environmental temperatures

  8. Nonequilibrium mesoscopic transport: a genealogy

    Das, Mukunda P; Green, Frederick

    2012-01-01

    Models of nonequilibrium quantum transport underpin all modern electronic devices, from the largest scales to the smallest. Past simplifications such as coarse graining and bulk self-averaging served well to understand electronic materials. Such particular notions become inapplicable at mesoscopic dimensions, edging towards the truly quantum regime. Nevertheless a unifying thread continues to run through transport physics, animating the design of small-scale electronic technology: microscopic conservation and nonequilibrium dissipation. These fundamentals are inherent in quantum transport and gain even greater and more explicit experimental meaning in the passage to atomic-sized devices. We review their genesis, their theoretical context, and their governing role in the electronic response of meso- and nanoscopic systems. (topical review)

  9. Nonequilibrium statistical mechanics ensemble method

    Eu, Byung Chan

    1998-01-01

    In this monograph, nonequilibrium statistical mechanics is developed by means of ensemble methods on the basis of the Boltzmann equation, the generic Boltzmann equations for classical and quantum dilute gases, and a generalised Boltzmann equation for dense simple fluids The theories are developed in forms parallel with the equilibrium Gibbs ensemble theory in a way fully consistent with the laws of thermodynamics The generalised hydrodynamics equations are the integral part of the theory and describe the evolution of macroscopic processes in accordance with the laws of thermodynamics of systems far removed from equilibrium Audience This book will be of interest to researchers in the fields of statistical mechanics, condensed matter physics, gas dynamics, fluid dynamics, rheology, irreversible thermodynamics and nonequilibrium phenomena

  10. Nonequilibrium quantum fluctuations of work.

    Allahverdyan, A E

    2014-09-01

    The concept of work is basic for statistical thermodynamics. To gain a fuller understanding of work and its (quantum) features, it needs to be represented as an average of a fluctuating quantity. Here I focus on the work done between two moments of time for a thermally isolated quantum system driven by a time-dependent Hamiltonian. I formulate two natural conditions needed for the fluctuating work to be physically meaningful for a system that starts its evolution from a nonequilibrium state. The existing definitions do not satisfy these conditions due to issues that are traced back to noncommutativity. I propose a definition of fluctuating work that is free of previous drawbacks and that applies for a wide class of nonequilibrium initial states. It allows the deduction of a generalized work-fluctuation theorem that applies for an arbitrary (out-of-equilibrium) initial state.

  11. Computer simulation of nonequilibrium processes

    Wallace, D.C.

    1985-07-01

    The underlying concepts of nonequilibrium statistical mechanics, and of irreversible thermodynamics, will be described. The question at hand is then, how are these concepts to be realize in computer simulations of many-particle systems. The answer will be given for dissipative deformation processes in solids, on three hierarchical levels: heterogeneous plastic flow, dislocation dynamics, an molecular dynamics. Aplication to the shock process will be discussed

  12. Non-equilibrium transport in the quantum dot: quench dynamics and non-equilibrium steady state

    Culver, Adrian; Andrei, Natan

    We present an exact method of calculating the non-equilibrium current driven by a voltage drop across a quantum dot. The system is described by the two lead Anderson model at zero temperature with on-site Coulomb repulsion and non-interacting, linearized leads. We prepare the system in an initial state consisting of a free Fermi sea in each lead with the voltage drop given as the difference between the two Fermi levels. We quench the system by coupling the dot to the leads at t = 0 and following the time evolution of the wavefunction. In the long time limit a new type of Bethe Ansatz wavefunction emerges, which satisfies the Lippmann-Schwinger equation with the two Fermi seas serving as the boundary conditions. This exact, non-perturbative solution describes the non-equilibrium steady state of the system. We describe how to use this solution to compute the infinite time limit of the expectation value of the current operator at a given voltage, which would yield the I-V characteristic of the dot. Research supported by NSF Grant DMR 1410583.

  13. Non-equilibrium fluctuation-induced interactions

    Dean, David S

    2012-01-01

    We discuss non-equilibrium aspects of fluctuation-induced interactions. While the equilibrium behavior of such interactions has been extensively studied and is relatively well understood, the study of these interactions out of equilibrium is relatively new. We discuss recent results on the non-equilibrium behavior of systems whose dynamics is of the dissipative stochastic type and identify a number of outstanding problems concerning non-equilibrium fluctuation-induced interactions.

  14. Nonlinear chemical sorption isotherms in the assessment of nuclear fuel waste disposal

    Walker, J.R.; LeNeveu, D.M.

    1987-01-01

    Radionuclides emplaced in an underground disposal vault can possibly migrate from the vault, and through the geosphere, to enter Man's environment. Chemical sorption is a primary mechanism for retarding this migration. The effects of nonlinear chemical sorption isotherms on radionuclide transport are discussed. A method is given by which nonlinear isotherms can be approximated by the linear sorption isotherm used in the vault submodel. The relevance of nonlinear isotherms to transport in the geosphere is discussed, and it is shown that the linear isotherm model is conservative for deep geologic disposal. 22 refs

  15. The effect of particle size on sorption of estrogens, androgens and progestagens in aquatic sediment

    Sangster, Jodi L.; Oke, Hugues; Zhang, Yun; Bartelt-Hunt, Shannon L.

    2015-01-01

    Highlights: • Two sediments were used to evaluate the effects of particle size on steroid sorption. • Sorption capacity did not increase with decreasing particle size for all steroids. • Particle interactions affect the distribution of steroids within the whole sediments. • Preferential sorption to fine particles was observed. - Abstract: There is growing concern about the biologic effects of steroid hormones in impacted waterways. There is increasing evidence of enhanced transport and biological effects stemming from steroid hormones associated with soils or sediments; however, there are limited studies evaluating how steroid hormone distribution between various particle sizes within whole sediments affects steroid fate. In this study, sorption of 17β-estradiol, estrone, progesterone, and testosterone was evaluated to different size fractions of two natural sediments, a silty loam and a sandy sediment, to determine the steroid sorption capacity to each fraction and distribution within the whole sediment. Sorption isotherms for all steroid hormones fit linear sorption models. Sorption capacity was influenced more by organic carbon content than particle size. Interactions between size fractions were found to affect the distribution of steroids within the whole sediments. All four steroids preferentially sorbed to the clay and colloids in the silty loam sediment at the lowest aqueous concentration (1 ng/L) and as aqueous concentration increased, the distribution of sorbed steroid was similar to the distribution by weight of each size fraction within the whole sediment. In the sandy sediment, preferential sorption to fine particles was observed.

  16. Equilibrium sorption of cobalt, cesium, and strontium on Bandelier Tuff: analysis of alternative mathematical modeling

    Polzer, W.L.; Fuentes, H.R.; Essington, E.H.; Roensch, F.R.

    1985-01-01

    Sorption isotherms are derived from batch equilibrium data for cobalt, cesium and strontium on Bandelier Tuff. Experiments were conducted at an average temperature of 23 0 C and equilibrium was defined at 48 hours. The solute concentrations ranged from 0 to 500 mg/L. The radioactive isotopes 60 Co, 137 Cs, and 85 Sr were used to trace the sorption of the stable solutes. The Linear, Langmuir, Freundlich and a Modified Freundlich isotherm equations are evaluated. The Modified Freundlich isotherm equation is validated as a preferred general mathematical tool for representing the sorption of the three solutes. The empirical constants derived from the Modified Freundlich isotherm equation indicate that under dynamic flow conditions strontium will move most rapidly and cobalt least rapidly. On the other hand, chemical dispersion will be greatest for cesium and least for strontium. Hill Plots of the sorption data suggest that in the region of low saturation sorption of all three solutes is impeded by interactions among sorption sites; cobalt exhibits the greatest effect of interactions and strontium shows only a minimal effect. In the saturation region of 50% or more, sorption of cobalt is enhanced slightly by interactions among sorption sites whereas sorption of cesium and strontium appears to be independent of site interactions. 9 references, 4 figures, 2 tables

  17. The effect of particle size on sorption of estrogens, androgens and progestagens in aquatic sediment

    Sangster, Jodi L.; Oke, Hugues; Zhang, Yun; Bartelt-Hunt, Shannon L., E-mail: sbartelt2@unl.edu

    2015-12-15

    Highlights: • Two sediments were used to evaluate the effects of particle size on steroid sorption. • Sorption capacity did not increase with decreasing particle size for all steroids. • Particle interactions affect the distribution of steroids within the whole sediments. • Preferential sorption to fine particles was observed. - Abstract: There is growing concern about the biologic effects of steroid hormones in impacted waterways. There is increasing evidence of enhanced transport and biological effects stemming from steroid hormones associated with soils or sediments; however, there are limited studies evaluating how steroid hormone distribution between various particle sizes within whole sediments affects steroid fate. In this study, sorption of 17β-estradiol, estrone, progesterone, and testosterone was evaluated to different size fractions of two natural sediments, a silty loam and a sandy sediment, to determine the steroid sorption capacity to each fraction and distribution within the whole sediment. Sorption isotherms for all steroid hormones fit linear sorption models. Sorption capacity was influenced more by organic carbon content than particle size. Interactions between size fractions were found to affect the distribution of steroids within the whole sediments. All four steroids preferentially sorbed to the clay and colloids in the silty loam sediment at the lowest aqueous concentration (1 ng/L) and as aqueous concentration increased, the distribution of sorbed steroid was similar to the distribution by weight of each size fraction within the whole sediment. In the sandy sediment, preferential sorption to fine particles was observed.

  18. Sorption of neptunium(V) on opalinus clay under aerobic/anaerobic conditions

    Froehlich, D.R.; Amayri, S.; Drebert, J.; Reich, T.

    2011-01-01

    The interaction between neptunium(V) and a natural argillaceous rock (Opalinus Clay (OPA), Mont Terri, Switzerland) has been investigated in batch sorption experiments by varying pH (6-10), Np(V) concentration (10 -12 -10 -4 M), solid-to-liquid ratio (2-20 g/L), and partial pressure of CO 2 (10 -3.5 and 10 -2.3 atm) under aerobic/anaerobic conditions in saturated calcite solution. All batch experiments were carried out using well characterized aerobic and anaerobic dry powders of OPA. The results show a great influence of pH on Np(V) sorption. Under aerobic conditions sorption increases with increasing pH until maximum sorption is reached between pH 8-9. At pH > 9 sorption decreases due to the formation of negatively charged Np(V)-carbonate complexes. By increasing p CO 2 from 10 -3.5 to 10 -2.3 atm, the sorption edge is shifted ∼ 0.5 units to lower pH values. Under anaerobic conditions stronger sorption of 8 x 10 -6 M Np(V) was found, possibly due to partial reduction of Np(V) to Np(IV). The sorption of 8 x 10 -6 M Np(V) under aerobic conditions at pH 8.2 in saturated calcite solution increases continuously with increasing solid-to-liquid ratio of OPA in the range of 2-20 g/L with a constant K d value of 126 ± 13 L/kg. The sorption isotherm was measured over seven orders of magnitude in Np(V) concentration using 239 Np as tracer. The sorption isotherm could be divided in a part of linear sorption behaviour between 10 -13 -10 -9 M Np(V) and non-linear behaviour in the range of 10 -9 -10 -4 M Np(V). (orig.)

  19. Sorption data bases for generic Swiss argillaceous rock systems

    Bradbury, M. H.; Baeyens, B.; Thoenen, T.

    2010-09-01

    implies, these factors were used to convert the (predominantly) illite sorption values into sorption values valid for the defined generic conditions with regard to mineralogy and porewater composition. Conversion factors were used to adapt sorption values to mineralogy (CF min ), to pH value (CF pH ) and to radionuclide speciation (CF spec ). Finally, a Lab→Field conversion factor (CF Lab→Field ) was applied to adapt sorption data measured in dispersed systems (batch experiments) to intact rock under in-situ conditions. Calcareous rock is used in safety analyses as being representative of a clay rock which has lost most of its favorable sorption properties due to near-field effects such as alteration by an alkaline plume and subsequent processes. It is assumed that calcareous rocks do not contain any significant quantities of phyllosilicates and that only uptake data on calcite are relevant. Sorption data on calcite are extremely sparse and the uptake mechanisms are not fully understood. However, when the existing sorption data (log R d values) are plotted against the ionic radii of the respective metals, an acceptable linear correlation between these two quantities is found. This so-called linear free energy relationship is used to complement the sparse experimental data in the SDB for calcareous systems. (authors)

  20. Nonequilibrium theory of flame propagation

    Merzhanov, A.G.

    1995-01-01

    The nonequilibrium theory of flame propagation is considered as applied to the following three processes of wave propagation: the combustion waves of the second kind, the combustion waves with broad reaction zones, and the combustion waves with chemical stages. Kinetic and combustion wave parameters are presented for different in composition mixtures of boron and transition metals, such as Zr, Hf, Ti, Nb, Ta, Mo, as well as for the Ta-N, Zr-C-H, Nb-B-O systems to illustrate specific features of the above-mentioned processes [ru

  1. Sorption properties of carbon nanostructures

    Eletskii, Aleksandr V

    2004-01-01

    The current status of research in sorption properties of carbon nanotubes (CNTs) is reviewed. The structural peculiarities of CNTs, determining their sorption characteristics, are considered. The mechanisms of sorption of gaseous and condensed substances by such structures are analyzed. Special attention is paid to the problem of using CNTs for storing hydrogen and other gaseous substances. Methods for filling CNTs with liquid materials, based on capillary phenomena and wetting the graphite surface of the CNT with liquids of various nature, are considered. Properties of 'peapods' formed as a result of filling single-walled CNTs with fullerene molecules are reviewed. Also considered are perspectives on the applied usage of the sorption properties of CNTs in electrochemical and fuel cells, and material storage devices, as well as for producing superminiature metallic conductors. (reviews of topical problems)

  2. Sorption Behavior of Compressed CO2 and CH4 on Ultrathin Hybrid Poly(POSS-imide) Layers.

    Raaijmakers, Michiel J T; Ogieglo, Wojciech; Wiese, Martin; Wessling, Matthias; Nijmeijer, Arian; Benes, Nieck E

    2015-12-09

    Sorption of compressed gases into thin polymeric films is essential for applications including gas sensors and membrane based gas separation. For glassy polymers, the sorption behavior is dependent on the nonequilibrium status of the polymer. The uptake of molecules by a polymer is generally accompanied by dilation, or swelling, of the polymer material. In turn, this dilation can result in penetrant induced plasticization and physical aging that affect the nonequilibrium status of the polymer. Here, we investigate the dilation and sorption behavior of ultrathin membrane layers of a hybrid inorganic-organic network material that consists of alternating polyhedral oligomeric silsesquioxane and imide groups, upon exposure to compressed carbon dioxide and methane. The imide precursor contains fluoroalkene groups that provide affinity toward carbon dioxide, while the octa-functionalized silsesquioxane provides a high degree of cross-linking. This combination allows for extremely high sorption capacities, while structural rearrangements of the network are hindered. We study the simultaneous uptake of gases and dilation of the thin films at high pressures using spectroscopic ellipsometry measurements. Ellipsometry provides the changes in both the refractive index and the film thickness, and allows for accurate quantification of sorption and swelling. In contrast, gravimetric and volumetric measurements only provide a single parameter; this does not allow an accurate correction for, for instance, the changes in buoyancy because of the extensive geometrical changes of highly swelling films. The sorption behavior of the ultrathin hybrid layers depends on the fluoroalkene group content. At low pressure, the apparent molar volume of the gases is low compared to the liquid molar volume of carbon dioxide and methane, respectively. At high gas concentrations in the polymer film, the apparent molar volume of carbon dioxide and methane exceeds that of the liquid molar volume, and

  3. Non-equilibrium phase transition

    Mottola, E.; Cooper, F.M.; Bishop, A.R.; Habib, S.; Kluger, Y.; Jensen, N.G.

    1998-01-01

    This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). Non-equilibrium phase transitions play a central role in a very broad range of scientific areas, ranging from nuclear, particle, and astrophysics to condensed matter physics and the material and biological sciences. The aim of this project was to explore the path to a deeper and more fundamental understanding of the common physical principles underlying the complex real time dynamics of phase transitions. The main emphasis was on the development of general theoretical tools to deal with non-equilibrium processes, and of numerical methods robust enough to capture the time-evolving structures that occur in actual experimental situations. Specific applications to Laboratory multidivisional efforts in relativistic heavy-ion physics (transition to a new phase of nuclear matter consisting of a quark-gluon plasma) and layered high-temperature superconductors (critical currents and flux flow at the National High Magnetic Field Laboratory) were undertaken

  4. Non-dissipative effects in nonequilibrium systems

    Maes, Christian

    2018-01-01

    This book introduces and discusses both the fundamental aspects and the measurability of applications of time-symmetric kinetic quantities, outlining the features that constitute the non-dissipative branch of non-equilibrium physics. These specific features of non-equilibrium dynamics have largely been ignored in standard statistical mechanics texts. This introductory-level book offers novel material that does not take the traditional line of extending standard thermodynamics to the irreversible domain. It shows that although stationary dissipation is essentially equivalent with steady non-equilibrium and ubiquitous in complex phenomena, non-equilibrium is not determined solely by the time-antisymmetric sector of energy-entropy considerations. While this should not be very surprising, this book provides timely, simple reminders of the role of time-symmetric and kinetic aspects in the construction of non-equilibrium statistical mechanics.

  5. Aeroacoustic and aerodynamic applications of the theory of nonequilibrium thermodynamics

    Horne, W. Clifton; Smith, Charles A.; Karamcheti, Krishnamurty

    1991-01-01

    Recent developments in the field of nonequilibrium thermodynamics associated with viscous flows are examined and related to developments to the understanding of specific phenomena in aerodynamics and aeroacoustics. A key element of the nonequilibrium theory is the principle of minimum entropy production rate for steady dissipative processes near equilibrium, and variational calculus is used to apply this principle to several examples of viscous flow. A review of nonequilibrium thermodynamics and its role in fluid motion are presented. Several formulations are presented of the local entropy production rate and the local energy dissipation rate, two quantities that are of central importance to the theory. These expressions and the principle of minimum entropy production rate for steady viscous flows are used to identify parallel-wall channel flow and irrotational flow as having minimally dissipative velocity distributions. Features of irrotational, steady, viscous flow near an airfoil, such as the effect of trailing-edge radius on circulation, are also found to be compatible with the minimum principle. Finally, the minimum principle is used to interpret the stability of infinitesimal and finite amplitude disturbances in an initially laminar, parallel shear flow, with results that are consistent with experiment and linearized hydrodynamic stability theory. These results suggest that a thermodynamic approach may be useful in unifying the understanding of many diverse phenomena in aerodynamics and aeroacoustics.

  6. Effects of nonequilibrium adsorption on nuclide transport in a porous rock

    Shi-Ping Teng; Ching-Hor Lee

    1994-01-01

    An analytical solution covering the entire range of adsorption properties of rock has been derived for the migration of radionuclide in a porous rock matrix. The analysis takes into account the advective transport, hydrodynamic dispersion, adsorption between solid phase and liquid phase, and the radioactive decay. For adsorption of nuclide within the rock, the effects of no adsorption, linear nonequilibrium adsorption, and linear equilibrium adsorption are integrated into a generic transient analytical solution. The results indicate that the assumption of equilibrium adsorption can result in underestimation of the concentration profile in the early stages of migration. However, both the equilibrium and nonequilibrium profiles eventually approach the same value. It is also noted that for the case of nonequilibrium adsorption, plateaus appear in the concentration profile of the breakthrough curves. The effects of different adsorption rates are also analyzed

  7. The measurement and estimation method of the sorption of lead onto cementitious materials

    Nakanishi, Kiyoshi; Tsukamoto, Masaki; Fujita, Tomonari; Sugiyama, Daisuke

    2002-01-01

    Cementitious material is a potential waste packaging material for radioactive waste disposal, and is expected to provide chemical containment. In particular, the sorption of radionuclides onto cementitious material is a very important parameter when considering the release of radionuclides from radioactive waste. In this study, sorption of lead, onto hydrated Ordinary Portland Cement (OPC), OPC/Blast Furnace Slag blended cement (BFS), Highly containing Flyash and Silica Fume Cement (HFSC) and cement constituent minerals (portlandite, ettringite, hydrotalcite and C-S-H gels (Ca/Si = 0.9 and 1.65)) was measured using the batch sorption technique. Lead is one of the important nuclides for safety assessment. The obtained distribution ratios, Rd values, for sorption of lead onto hydrated (freshly cured) OPC and HFSC are very high:>1000 cm3g-1. The distribution ratio for sorption of lead onto OPC/BFS could not be determined quantitatively due to the precipitation of PbS. Comparing the Rd values onto cements and minerals, it was suggested the sorption onto C-S-H gel phases dominate the sorption for lead onto hydrated cements. Once a cementitious material is altered in the disposal environment, its sorption ability may be affected. The sorption of lead onto degraded OPC and degraded HFSC, which were altered in the presence of distilled water, was also measured. It was observed that the alteration did not cause changes that decreased the sorption of lead onto OPC and HFSC. An approach, in which it is assumed that each of the component phases contributes to the composite material, is proposed and discussed to describe the sorption of lead onto cement using a knowledge of the phase components in a linear additive manner. The results showed reasonably good agreement between the predicted and measured Rd values for lead onto freshly cured and altered cements. (author)

  8. Effect of sediment properties on the sorption of C12-2-LAS in marine and estuarine sediments

    Rico Rico, A.; Temara, A.; Behrends, T.; Hermens, J.L.M.

    2009-01-01

    Linear alkylbenzene sulfonates (LAS) are anionic high production volume surfactants used in the manufacture of cleaning products. Here, we have studied the effect of the characteristics of marine and estuarine sediments on the sorption of LAS. Sorption experiments were performed with single sediment

  9. INTRODUCTION: Nonequilibrium Processes in Plasmas

    Petrović, Zoran; Marić, Dragana; Malović, Gordana

    2009-07-01

    This book aims to give a cross section from a wide range of phenomena that, to different degrees, fall under the heading of non-equilibrium phenomenology. The selection is, of course, biased by the interests of the members of the scientific committee and of the FP6 Project 026328 IPB-CNP Reinforcing Experimental Centre for Non-equilibrium Studies with Application in Nano-technologies, Etching of Integrated Circuits and Environmental Research. Some of the papers included here are texts based on selected lectures presented at the Second International Workshop on Non-equilibrium Processes in Plasmas and Environmental Science. However, this volume is not just the proceedings of that conference as it contains a number of papers from authors that did not attend the conference. The goal was to put together a volume that would cover the interests of the project and support further work. It is published in the Institute of Physics journal Journal of Physics: Conference Series to ensure a wide accessibility of the articles. The texts presented here range from in-depth reviews of the current status and past achievements to progress reports of currently developed experimental devices and recently obtained still unpublished results. All papers have been refereed twice, first when speakers were selected based on their reputation and recently published results, and second after the paper was submitted both by the editorial board and individual assigned referees according to the standards of the conference and of the journal. Nevertheless, we still leave the responsibility (and honours) for the contents of the papers to the authors. The papers in this book are review articles that give a summary of the already published work or present the work in progress that will be published in full at a later date (or both). In the introduction to the first volume, in order to show how far reaching, ubiquitous and important non-equilibrium phenomena are, we claimed that ever since the early

  10. Nonequilibrium fluctuations in a resistor.

    Garnier, N; Ciliberto, S

    2005-06-01

    In small systems where relevant energies are comparable to thermal agitation, fluctuations are of the order of average values. In systems in thermodynamical equilibrium, the variance of these fluctuations can be related to the dissipation constant in the system, exploiting the fluctuation-dissipation theorem. In nonequilibrium steady systems, fluctuations theorems (FT) additionally describe symmetry properties of the probability density functions (PDFs) of the fluctuations of injected and dissipated energies. We experimentally probe a model system: an electrical dipole driven out of equilibrium by a small constant current I, and show that FT are experimentally accessible and valid. Furthermore, we stress that FT can be used to measure the dissipated power P = R I2 in the system by just studying the PDFs' symmetries.

  11. Gas Sorption, Diffusion, and Permeation in Nafion

    Mukaddam, Mohsin Ahmed

    2015-12-22

    The gas permeability of dry Nafion films was determined at 2 atm and 35 °C for He, H2, N2, O2, CO2, CH4, C2H6, and C3H8. In addition, gas sorption isotherms were determined by gravimetric and barometric techniques as a function of pressure up to 20 atm. Nafion exhibited linear sorption uptake for low-solubility gases, following Henry’s law, and convex behavior for highly sorbing condensable gases, indicating rubber-like behavior at 35 °C. XRD results demonstrated that Nafion contains bimodal amorphous chain domains with average d-spacing values of 2.3 and 5.3 Å. Only helium and hydrogen showed relatively high gas permeability of 37 and 7 barrers, respectively; all other gases exhibited low permeability that decreased significantly as penetrant size increased. Dry Nafion was characterized by extraordinarily high selectivities: He/H2 = 5.2, He/CH4 = 445, He/C2H6 = 1275, He/C3H8 = 7400, CO2/CH4 = 28, CO2/C2H6 = 79, CO2/C3H8 = 460, H2/CH4 = 84, H2/C2H6 = 241, and H2/C3H8 = 1400. These high selectivities could make Nafion a potential candidate membrane material for dry feeds for helium recovery and carbon dioxide separation from natural gas and removal of higher hydrocarbons from hydrogen-containing refinery gases.

  12. Thermodynamics of imidacloprid sorption in Croatian soils

    Milin, Čedomila; Broznic, Dalibor

    2015-04-01

    Neonicotinoids are increasingly replacing the organophosphate and methylcarbamate acetylcholinesterase inhibitors which are losing their effectiveness because of selection for resistant pest populations. Imidacloprid is the most important neonicotinoid with low soil persistence, high insecticidal potency and relatively low mammalian toxicity. In Croatia, imidacloprid is most commonly used in olive growing areas, including Istria and Kvarner islands, as an effective means of olive fruit fly infestation control. Sorption-desorption behavior of imidacloprid in six soils collected from five coastal regions in Croatia at 20, 30 and 40°C was investigated using batch equilibrium technique. Isothermal data were applied to Freundlich, Langmuir and Temkin equation, and the thermodynamic parameters ΔH°, ΔG°, ΔS° were calculated. The sorption isotherm curves were of non-linear and may be classified as L-type suggesting a relatively high sorption capacity for imidacloprid. Our results showed that the KFsor values decreased for all the tested soils as the temperature increases, indicating that the temperature strongly influence the sorption. Values of ΔG° were negative (-4.65 to -2.00 kJ/mol) indicating that at all experimental temperatures the interactions of imidacloprid with soils were spontaneous process. The negative and small ΔH° values (-19.79 to -8.89 kJ/mol) were in the range of weak forces, such as H-bonds, consistent with interactions and par¬titioning of the imidacloprid molecules into soil organic matter. The ΔS° values followed the range of -57.12 to -14.51 J/molK, suggesting that imidacloprid molecules lose entropy during transition from the solution phase to soil surface. It was found that imidacloprid desorption from soil was concentration and temperature dependent, i.e. at lower imidacloprid concentrations and temperature, lower desorption percentage occurred. Desorption studies revealed that hysteretic behavior under different temperature

  13. Evaluation of sorption distribution coefficient of Cs onto granite using sorption data collected in sorption database and sorption model

    Nagasaki, S.

    2013-01-01

    Based on the sorption distribution coefficients (K d ) of Cs onto granite collected from the JAERI Sorption Database (SDB), the parameters for a two-site model without the triple-layer structure were optimized. Comparing the experimentally measured K d values of Cs onto Mizunami granite carried out by JAEA with the K d values predicted by the model, the effect of the ionic strength on the K d values of Cs onto granite was evaluated. It was found that K d values could be determined using the content of biotite in granite at a sodium concentration ([Na]) of 1 x 10 -2 to 5 x 10 -1 mol/dm 3 . It was suggested that in high ionic strength solutions, the sorption of Cs onto other minerals such as microcline should also be taken into account. (author)

  14. Evaluation of sorption distribution coefficient of Cs onto granite using sorption data collected in sorption database and sorption model

    Nagasaki, S., E-mail: nagasas@mcmaster.ca [McMaster Univ., Hamilton, Ontario (Canada)

    2013-07-01

    Based on the sorption distribution coefficients (K{sub d}) of Cs onto granite collected from the JAERI Sorption Database (SDB), the parameters for a two-site model without the triple-layer structure were optimized. Comparing the experimentally measured K{sub d} values of Cs onto Mizunami granite carried out by JAEA with the K{sub d} values predicted by the model, the effect of the ionic strength on the K{sub d} values of Cs onto granite was evaluated. It was found that K{sub d} values could be determined using the content of biotite in granite at a sodium concentration ([Na]) of 1 x 10{sup -2} to 5 x 10{sup -1} mol/dm{sup 3} . It was suggested that in high ionic strength solutions, the sorption of Cs onto other minerals such as microcline should also be taken into account. (author)

  15. Sorption isotherms, GAB parameters and isosteric heat of sorption

    Quirijns, E.J.; Boxtel, van A.J.B.; Loon, van W.K.P.; Straten, van G.

    2005-01-01

    The diffusion-sorption drying model has been developed as a physics-based way to model the decreasing drying rate at low moisture contents. This new model is founded on the existence of different classes of water: free and bound water. The transition between these classes and the corresponding

  16. Link prediction based on nonequilibrium cooperation effect

    Li, Lanxi; Zhu, Xuzhen; Tian, Hui

    2018-04-01

    Link prediction in complex networks has become a common focus of many researchers. But most existing methods concentrate on neighbors, and rarely consider degree heterogeneity of two endpoints. Node degree represents the importance or status of endpoints. We describe the large-degree heterogeneity as the nonequilibrium between nodes. This nonequilibrium facilitates a stable cooperation between endpoints, so that two endpoints with large-degree heterogeneity tend to connect stably. We name such a phenomenon as the nonequilibrium cooperation effect. Therefore, this paper proposes a link prediction method based on the nonequilibrium cooperation effect to improve accuracy. Theoretical analysis will be processed in advance, and at the end, experiments will be performed in 12 real-world networks to compare the mainstream methods with our indices in the network through numerical analysis.

  17. Binary Component Sorption of Cadmium, and Copper Ions onto Yangtze River Sediments with Different Particle Sizes

    Jianxin Fan

    2017-11-01

    Full Text Available Sorption is a crucial process that influences immobilization and migration of heavy metals in an aqueous environment. Sediments represent one of the ultimate sinks for heavy metals discharged into water body. Moreover, the particle size of sediments plays an extremely important role in the immobilization of heavy metals. In this study, the sorption and desorption of cadmium (Cd and copper (Cu onto sediments with different particle sizes were investigated to predict the rate and capacity of sorption, to understand their environmental behaviors in an aqueous environment. Batch sorption and kinetic experiments were conducted to obtain the retained amount and rate of Cd and Cu in a binary system. Experimental data were simulated using sorption models to ascertain the sorption capacity and the kinetic rate. Results of European Communities Bureau of Reference (BCR sequential extraction showed the highest concentration of Cd (0.344 mg kg−1, and its distribution varied with sediment particle size and site. Furthermore, most of Cu (approximately 57% to 84% existed as a residual fraction. The sorption of Cu onto six sediments followed a pseudo-first order reaction, whereas that of Cd followed a pseudo-second order reaction. Additionally, the competitive Langmuir model fitted the batch sorption experimental data extremely well. The highest sorption capacities of Cd and Cu reach 0.641 mmol kg−1 and 62.3 mmol kg−1, respectively, on the smallest submerged sediment particles. The amounts of Cu and Cd desorbed (mmol kg−1 increased linearly with the initial concentration increasing. Thus, sediment texture is an important factor that influences the sorption of heavy metal onto sediments.

  18. Non-equilibrium dog-flea model

    Ackerson, Bruce J.

    2017-11-01

    We develop the open dog-flea model to serve as a check of proposed non-equilibrium theories of statistical mechanics. The model is developed in detail. Then it is applied to four recent models for non-equilibrium statistical mechanics. Comparison of the dog-flea solution with these different models allows checking claims and giving a concrete example of the theoretical models.

  19. Plasma wave instabilities in nonequilibrium graphene

    Aryal, Chinta M.; Hu, Ben Yu-Kuang; Jauho, Antti-Pekka

    2016-01-01

    We study two-stream instabilities in a nonequilibrium system in which a stream of electrons is injected into doped graphene. As with equivalent nonequilibrium parabolic band systems, we find that the graphene systems can support unstable charge-density waves whose amplitudes grow with time. We...... of the injected electrons that maximizes the growth rate increases with increasing | q |. We compare the range and strength of the instability in graphene to that of two- and three-dimensional parabolic band systems....

  20. Quantum thermodynamics: a nonequilibrium Green's function approach.

    Esposito, Massimiliano; Ochoa, Maicol A; Galperin, Michael

    2015-02-27

    We establish the foundations of a nonequilibrium theory of quantum thermodynamics for noninteracting open quantum systems strongly coupled to their reservoirs within the framework of the nonequilibrium Green's functions. The energy of the system and its coupling to the reservoirs are controlled by a slow external time-dependent force treated to first order beyond the quasistatic limit. We derive the four basic laws of thermodynamics and characterize reversible transformations. Stochastic thermodynamics is recovered in the weak coupling limit.

  1. Characterizing the sorption of polybrominated diphenyl ethers (PBDEs) to cotton and polyester fabrics under controlled conditions

    Saini, Amandeep [Department of Physical and Environmental Sciences, University of Toronto Scarborough, 1265 Military trail, Toronto, ON M1C 1A4 (Canada); Rauert, Cassandra [School of Geography, Earth and Environmental Sciences, University of Birmingham, Birmingham B15 2TT (United Kingdom); Simpson, Myrna J. [Department of Physical and Environmental Sciences, University of Toronto Scarborough, 1265 Military trail, Toronto, ON M1C 1A4 (Canada); Harrad, Stuart [School of Geography, Earth and Environmental Sciences, University of Birmingham, Birmingham B15 2TT (United Kingdom); Diamond, Miriam L., E-mail: miriam.diamond@utoronto.ca [Department of Earth Sciences, 22 Russell Street, University of Toronto, Toronto, ON M5S 3B1 (Canada); Department of Physical and Environmental Sciences, University of Toronto Scarborough, 1265 Military trail, Toronto, ON M1C 1A4 (Canada)

    2016-09-01

    Cotton and polyester, physically and chemically different fabrics, were characterized for sorption of gas-phase polybrominated diphenyl ethers (PBDEs). Scanning electron microscopic (SEM) images and BET specific surface area (BET-SSA) analysis showed cotton's high microsurface area; NMR analysis showed richness of hexose- and aromatic-carbon in cotton and polyester, respectively. Cotton and polyester sorbed similar concentrations of gas-phase PBDEs in chamber studies, when normalized to planar surface area. However, polyester concentrations were 20–50 times greater than cotton when normalized to BET-SSA, greater than the 10 times difference in BET-SSA. The difference in sorption between cotton and polyester is hypothesized to be due to ‘dilution’ due to cotton's large BET-SSA and/or greater affinity of PBDEs for aromatic-rich polyester. Similar fabric-air area normalized distribution coefficients (K'{sub D}, 10{sup 3} to 10{sup 4} m) for cotton and polyester support air-side controlled uptake under non-equilibrium conditions. K'{sub D} values imply that 1 m{sup 2} of cotton or polyester fabrics would sorb gas-phase PBDEs present in 10{sup 3} to 10{sup 4} m{sup 3} of equivalent air volume at room temperature over one week, assuming similar air flow conditions. Sorption of PBDEs to fabrics has implications for their fate indoors and human exposure. - Highlights: • Sorption of gas-phase PBDEs by cotton and polyester fabrics • Similar sorption to cotton and polyester per unit planar surface area • Greater sorption by polyester/BET-SSA; cotton's dilution or polyester’s affinity • 1 m{sup 2} fabric sorbs PBDEs in 10{sup 3} to 10{sup 4} m{sup 3} of equivalent air volume • Clothing likely a large indoor sink of PBDEs and influence human exposure.

  2. Aerospace Applications of Non-Equilibrium Plasma

    Blankson, Isaiah M.

    2016-01-01

    Nonequilibrium plasma/non-thermal plasma/cold plasmas are being used in a wide range of new applications in aeronautics, active flow control, heat transfer reduction, plasma-assisted ignition and combustion, noise suppression, and power generation. Industrial applications may be found in pollution control, materials surface treatment, and water purification. In order for these plasma processes to become practical, efficient means of ionization are necessary. A primary challenge for these applications is to create a desired non-equilibrium plasma in air by preventing the discharge from transitioning into an arc. Of particular interest is the impact on simulations and experimental data with and without detailed consideration of non-equilibrium effects, and the consequences of neglecting non-equilibrium. This presentation will provide an assessment of the presence and influence of non-equilibrium phenomena for various aerospace needs and applications. Specific examples to be considered will include the forward energy deposition of laser-induced non-equilibrium plasmoids for sonic boom mitigation, weakly ionized flows obtained from pulsed nanosecond discharges for an annular Hall type MHD generator duct for turbojet energy bypass, and fundamental mechanisms affecting the design and operation of novel plasma-assisted reactive systems in dielectric liquids (water purification, in-pipe modification of fuels, etc.).

  3. Sorption on inactive repository components

    Gardiner, M.P.; Smith, A.J.; Williams, S.J.

    1990-11-01

    The near-field of an intermediate level/low level radioactive waste repository will contain significant quantities of iron and steel, Magnox and Zircaloy. Their corrosion products may possess significant sorption capacity for radioelements. The sorption of americium and plutonium onto magnesium hydroxide, zirconium hydroxide, colloidal magnetite and colloidal haematite has been studied under conditions typical of the porewater of a cementitious near-field. R D values ≥ 10 5 m g -1 were measured for both actinides on the oxides and hydroxides. These values are at least as great as those measured on crushed 3:1 Blast Furnace Slag/Ordinary Portland cement. Competitive sorption experiments have shown that sorption onto the corrosion products does not take place in preference to that on the cement or the converse. Magnetite and haematite colloids are positively charged in cement-equilibrated water whilst zirconium hydroxide is negatively charged. Crushed cement was found to be positively charged. Simple experiments show that only a small proportion of haematite colloids is potentially mobile through a column of crushed cement. (author)

  4. Sorption on inactive repository components

    Gardiner, M.P.; Smith, A.J.; Williams, S.J.

    1990-07-01

    The near-field of an intermediate level/low level radioactive waste repository will contain significant quantities of iron and steel, Magnox and Zircaloy. Their corrosion products may possess significant sorption capacity for radioelements. The sorption of americium and plutonium onto magnesium hydroxide, zirconium hydroxide, colloidal magnetite and colloidal haematite has been studied under conditions typical of the porewater of a cementitious near-field. R D values ≥ 10 5 ml g -1 were measured for both actinides on the oxides and hydroxides. These values are at least as great at those measured on crushed 3:1 Blast Furnace Slag/Ordinary Portland Cement. Competitive sorption experiments have shown that sorption onto the corrosion products does not take place in preference to that on the cement or the converse. Magnetite and haematite colloids are positively charged in cement-equilibrated water whilst zirconium hydroxide is negatively charged. Crushed cement was found to be positively charged. Simple experiments show that only a small proportion of haematite colloids is potentially mobile through a column of crushed cement. (author)

  5. Non-equilibrium versus equilibrium emission of complex fragments from hot nuclei

    Viola, V.E.; Kwiatkowski, K.; Yennello, S.; Fields, D.E.

    1989-01-01

    The relative contributions of equilibrium and non-equilibrium mechanisms for intermediate-mass fragment emission have been deduced for Z=3-14 fragments formed in 3 He- and 14 N-induced reactions on Ag and Au targets. Complete inclusive excitation function measurements have been performed for 3 He projectiles from E/A=67 to 1,200 MeV and for 14 N from E/A=20 to 50 MeV. The data are consistent with a picture in which equilibrated emission is important at the lowest energies, but with increasing bombarding energy the cross sections are increasingly dominated by non-equilibrium processes. Non-equilibrium emission is also shown to be favored for light fragments relative to heavy fragments. These results are supported by coincidence studies of intermediate-mass fragments tagged by linear momentum transfer measurements

  6. An expression of excess work during the transition between nonequilibrium steady states

    Yuge, Tatsuro

    2014-01-01

    Excess work is a nondiverging part of the work during the transition between nonequilibrium steady states (NESSs). It is a central quantity in steady-state thermodynamics (SST), which is a candidate for nonequilibrium thermodynamics theory. We derive an expression of excess work during quasistatic transitions between NESSs by using the macroscopic linear response relation of the NESS. This expression is a line integral of a vector potential in the space of control parameters. We show a relationship between the vector potential and the response function of the NESS, and thus obtain a relationship between the SST and a macroscopic quantity. We also connect the macroscopic formulation to microscopic physics through a microscopic expression of the nonequilibrium response function, which gives a result that is consistent with previous studies. (paper)

  7. Emergence of a fluctuation relation for heat in nonequilibrium Landauer processes

    Taranto, Philip; Modi, Kavan; Pollock, Felix A.

    2018-05-01

    In a generalized framework for the Landauer erasure protocol, we study bounds on the heat dissipated in typical nonequilibrium quantum processes. In contrast to thermodynamic processes, quantum fluctuations are not suppressed in the nonequilibrium regime and cannot be ignored, making such processes difficult to understand and treat. Here we derive an emergent fluctuation relation that virtually guarantees the average heat produced to be dissipated into the reservoir either when the system or reservoir is large (or both) or when the temperature is high. The implication of our result is that for nonequilibrium processes, heat fluctuations away from its average value are suppressed independently of the underlying dynamics exponentially quickly in the dimension of the larger subsystem and linearly in the inverse temperature. We achieve these results by generalizing a concentration of measure relation for subsystem states to the case where the global state is mixed.

  8. Nonequilibrium excitations and transport of Dirac electrons in electric-field-driven graphene

    Li, Jiajun; Han, Jong E.

    2018-05-01

    We investigate nonequilibrium excitations and charge transport in charge-neutral graphene driven with dc electric field by using the nonequilibrium Green's-function technique. Due to the vanishing Fermi surface, electrons are subject to nontrivial nonequilibrium excitations such as highly anisotropic momentum distribution of electron-hole pairs, an analog of the Schwinger effect. We show that the electron-hole excitations, initiated by the Landau-Zener tunneling with a superlinear I V relation I ∝E3 /2 , reaches a steady state dominated by the dissipation due to optical phonons, resulting in a marginally sublinear I V with I ∝E , in agreement with recent experiments. The linear I V starts to show the sign of current saturation as the graphene is doped away from the Dirac point, and recovers the semiclassical relation for the saturated velocity. We give a detailed discussion on the nonequilibrium charge creation and the relation between the electron-phonon scattering rate and the electric field in the steady-state limit. We explain how the apparent Ohmic I V is recovered near the Dirac point. We propose a mechanism where the peculiar nonequilibrium electron-hole creation can be utilized in a infrared device.

  9. Preliminary report on the statistical evaluation of sorption data: Sorption as a function of mineralogy, temperature, time, and particle size

    Beckman, R.; Thomas, K.; Crowe, B.

    1988-05-01

    This report studies the transport of radionuclides from a repository to the environment by dissolution of the stored solid-waste form and subsequent transport in water. The sorption process may retard this movement of radionuclides from the repository to the accessible environment. A measure of this retardation process is the sorption ratio, R/sub D/, where R/sub D/ = (activity in solid phase per unit mass of solid)(activity in solution per unit volume of solution). In this study, predictions of the R/sub D/ values for the elements barium, cerium, cesium, europium, and strontium are developed from linear regression techniques. An R/sub D/ value was obtained for numerous drill core samples. Additional data include the particle size of the rock, temperature condition during the experiment, concentration of the sorbing element, and length of the sorption experiment. Preliminary regression results based on these data show that the temperature and length of the experiment are the most significant factors influencing the R/sub D/ values. Particle size has a slight effect, and based on a small amount of data, it appears that concentration had no effect. The x-ray diffraction data are used to classify the samples by mineralogy, and regression techniques are used to develop estimates of the R/sub D/ values. Zeolite abundance of 10% or more with some addition of clay increases the sorption values significantly. 12 refs., 3 figs., 6 tabs

  10. A study of sorption mechanism onto cement hydrates by isotherm measurements

    Sugiyama, Daisuke; Fujita, Tomonari

    2003-01-01

    In the concept for TRU waste disposal in Japan, cement is a potential waste packaging and backfilling material and is expected to provide chemical containment. In particular, the sorption of radionuclides onto cement material, which controls the aqueous concentrations of elements in the porewater, is a very important parameter when considering the release of radionuclides from the near field of a repository. Many safety assessment calculations currently assume radionuclide retardation as linear sorption equilibrium and describe it with a distribution ratio (R d value). In this study, the sorption mechanism is discussed by measuring the sorption isotherm of caesium, strontium and thorium onto Ordinary Portland Cement (OPC) and Calcium Silicate Hydrate (C-S-H gel), to justify and support this assumption. In addition, the effect of competitive sorption between thorium and uranium and other groundwater ions is studied by examining sorption using a range of sodium chloride concentrations to simulate different groundwater ionic strengths. Based on the experimental results, we have showed that: Caesium and strontium sorb by substitution for Ca in C-S-H phases and the presence of some calcium sites with different ion-exchange log K values is suggested; Thorium would be fixed in a surface co-precipitation to form a solubility-limiting phase. The results of sorption experiments are reasonably well modelled by the ion-exchange model for caesium and strontium and the surface co-precipitation model for thorium, respectively. (author)

  11. Experimental study and modelling of selenite sorption onto illite and smectite clays.

    Missana, T; Alonso, U; García-Gutiérrez, M

    2009-06-15

    This study provides a large set of experimental selenite sorption data for pure smectite and illite. Similar sorption behavior existed in both clays: linear within a large range of the Se concentrations investigated (from 1x10(-10) to 1x10(-3) M); and independent of ionic strength. Selenite sorption was also analysed in the illite/smectite system with the clays mixed in two different proportions, as follows: (a) 30% illite-70% smectite and (b) 43% illite-57% smectite. The objective of the study was to provide the simplest model possible to fit the experimental data, a model also capable of describing selenite sorption in binary illite/smectite clay systems. Selenite sorption data, separately obtained in the single mineral systems, were modeled using both a one- and a two-site non-electrostatic model that took into account the formation of two complexes at the edge sites of the clay. Although the use of a two-site model slightly improved the fit of data at a pH below 4, the simpler one-site model reproduced satisfactorily all the sorption data from pH 3 to 8. The complexation constants obtained by fitting sorption data of the individual minerals were incorporated into a model to predict the adsorption of selenium in the illite/smectite mixtures; the model's predictions were consistent with the experimental adsorption data.

  12. Linear optical absorption spectra of mesoscopic structures in intense THz fields: Free-particle properties

    Johnsen, Kristinn; Jauho, Antti-Pekka

    1998-01-01

    We theoretically study the effect of THz radiation on the linear optical absorption spectra of semiconductor structures. A general theoretical framework, based on nonequilibrium Green functions, is formulated and applied to the calculation of linear optical absorption spectrum for several...

  13. Evaluating equilibrium and non-equilibrium transport of bromide and isoproturon in disturbed and undisturbed soil columns

    Dousset, S.; Thevenot, M.; Pot, V.; Šimunek, J.; Andreux, F.

    2007-12-01

    In this study, displacement experiments of isoproturon were conducted in disturbed and undisturbed columns of a silty clay loam soil under similar rainfall intensities. Solute transport occurred under saturated conditions in the undisturbed soil and under unsaturated conditions in the sieved soil because of a greater bulk density of the compacted undisturbed soil compared to the sieved soil. The objective of this work was to determine transport characteristics of isoproturon relative to bromide tracer. Triplicate column experiments were performed with sieved (structure partially destroyed to simulate conventional tillage) and undisturbed (structure preserved) soils. Bromide experimental breakthrough curves were analyzed using convective-dispersive and dual-permeability (DP) models (HYDRUS-1D). Isoproturon breakthrough curves (BTCs) were analyzed using the DP model that considered either chemical equilibrium or non-equilibrium transport. The DP model described the bromide elution curves of the sieved soil columns well, whereas it overestimated the tailing of the bromide BTCs of the undisturbed soil columns. A higher degree of physical non-equilibrium was found in the undisturbed soil, where 56% of total water was contained in the slow-flow matrix, compared to 26% in the sieved soil. Isoproturon BTCs were best described in both sieved and undisturbed soil columns using the DP model combined with the chemical non-equilibrium. Higher degradation rates were obtained in the transport experiments than in batch studies, for both soils. This was likely caused by hysteresis in sorption of isoproturon. However, it cannot be ruled out that higher degradation rates were due, at least in part, to the adopted first-order model. Results showed that for similar rainfall intensity, physical and chemical non-equilibrium were greater in the saturated undisturbed soil than in the unsaturated sieved soil. Results also suggested faster transport of isoproturon in the undisturbed soil due

  14. Sorption studies of radioiodine on soils with special references to soil microbial biomass

    Bors, J. (Niedersaechsisches Inst. fuer Radiooekologie, Hannover (Germany, F.R.)); Erten, H. (Bilkent Univ., Ankara (Turkey). Dept. of Chemistry); Martens, R. (Bundesforschungsanstalt fuer Landwirtschaft, Braunschweig (Germany, F.R.). Inst. fuer Bodenbiologie)

    1991-01-01

    In batch experiments with two types of soils, chernozem and podzol, radioiodine ({sup 125}I) showed an initial rapid sorption, followed by a long and slow further increase. Very little sorption (R{sub d} < 1) was detected in clay minerals. Generally, higher R{sub d}-values were observed for the chernozem soil, characterized by a higher amount of organic substance and of soil biomass. The sorption process was predominantly irreversible, the isotherms were linear at low ion concentrations and deviated from linearity starting at 10{sup -5} mmol.ml{sup -1}. Sorption ratio was found to increase with increasing volume to mass ratio. The composition of liquid phases (bidistilled water, synthetic soil water, rain water) highly affected iodine sorption. In experiments with KBr solution, the sorption of I{sup -} was found to be strongly preferred to Br{sup -}. Incubation of soil samples under varied conditions (decreased or increased soil biomass, O{sub 2}-concentration, incubation temperature, soil water content and storage conditions) delivered indications for the participation of soil microflora in iodine immobilization. Test with isolated soil bacteria and fungi showed that radioiodine can be incorporated by soil microorganisms under certain conditions only: Considerable uptake of radioiodine was found in washed (NaCl, CaCl{sub 2}) cells with both bacteria and fungi, but no incorporation was detected into cells incubated with radioiodine in the culture medium. (orig.).

  15. Sorption studies of radioiodine on soils with special references to soil microbial biomass

    Bors, J.; Erten, H.; Martens, R.

    1991-01-01

    In batch experiments with two types of soils, chernozem and podzol, radioiodine ( 125 I) showed an initial rapid sorption, followed by a long and slow further increase. Very little sorption (R d d -values were observed for the chernozem soil, characterized by a higher amount of organic substance and of soil biomass. The sorption process was predominantly irreversible, the isotherms were linear at low ion concentrations and deviated from linearity starting at 10 -5 mmol.ml -1 . Sorption ratio was found to increase with increasing volume to mass ratio. The composition of liquid phases (bidistilled water, synthetic soil water, rain water) highly affected iodine sorption. In experiments with KBr solution, the sorption of I - was found to be strongly preferred to Br - . Incubation of soil samples under varied conditions (decreased or increased soil biomass, O 2 -concentration, incubation temperature, soil water content and storage conditions) delivered indications for the participation of soil microflora in iodine immobilization. Test with isolated soil bacteria and fungi showed that radioiodine can be incorporated by soil microorganisms under certain conditions only: Considerable uptake of radioiodine was found in washed (NaCl, CaCl 2 ) cells with both bacteria and fungi, but no incorporation was detected into cells incubated with radioiodine in the culture medium. (orig.)

  16. Equilibrium sampling by reweighting nonequilibrium simulation trajectories.

    Yang, Cheng; Wan, Biao; Xu, Shun; Wang, Yanting; Zhou, Xin

    2016-03-01

    Based on equilibrium molecular simulations, it is usually difficult to efficiently visit the whole conformational space of complex systems, which are separated into some metastable regions by high free energy barriers. Nonequilibrium simulations could enhance transitions among these metastable regions and then be applied to sample equilibrium distributions in complex systems, since the associated nonequilibrium effects can be removed by employing the Jarzynski equality (JE). Here we present such a systematical method, named reweighted nonequilibrium ensemble dynamics (RNED), to efficiently sample equilibrium conformations. The RNED is a combination of the JE and our previous reweighted ensemble dynamics (RED) method. The original JE reproduces equilibrium from lots of nonequilibrium trajectories but requires that the initial distribution of these trajectories is equilibrium. The RED reweights many equilibrium trajectories from an arbitrary initial distribution to get the equilibrium distribution, whereas the RNED has both advantages of the two methods, reproducing equilibrium from lots of nonequilibrium simulation trajectories with an arbitrary initial conformational distribution. We illustrated the application of the RNED in a toy model and in a Lennard-Jones fluid to detect its liquid-solid phase coexistence. The results indicate that the RNED sufficiently extends the application of both the original JE and the RED in equilibrium sampling of complex systems.

  17. Surface complexation modeling of zinc sorption onto ferrihydrite.

    Dyer, James A; Trivedi, Paras; Scrivner, Noel C; Sparks, Donald L

    2004-02-01

    A previous study involving lead(II) [Pb(II)] sorption onto ferrihydrite over a wide range of conditions highlighted the advantages of combining molecular- and macroscopic-scale investigations with surface complexation modeling to predict Pb(II) speciation and partitioning in aqueous systems. In this work, an extensive collection of new macroscopic and spectroscopic data was used to assess the ability of the modified triple-layer model (TLM) to predict single-solute zinc(II) [Zn(II)] sorption onto 2-line ferrihydrite in NaNO(3) solutions as a function of pH, ionic strength, and concentration. Regression of constant-pH isotherm data, together with potentiometric titration and pH edge data, was a much more rigorous test of the modified TLM than fitting pH edge data alone. When coupled with valuable input from spectroscopic analyses, good fits of the isotherm data were obtained with a one-species, one-Zn-sorption-site model using the bidentate-mononuclear surface complex, (triple bond FeO)(2)Zn; however, surprisingly, both the density of Zn(II) sorption sites and the value of the best-fit equilibrium "constant" for the bidentate-mononuclear complex had to be adjusted with pH to adequately fit the isotherm data. Although spectroscopy provided some evidence for multinuclear surface complex formation at surface loadings approaching site saturation at pH >/=6.5, the assumption of a bidentate-mononuclear surface complex provided acceptable fits of the sorption data over the entire range of conditions studied. Regressing edge data in the absence of isotherm and spectroscopic data resulted in a fair number of surface-species/site-type combinations that provided acceptable fits of the edge data, but unacceptable fits of the isotherm data. A linear relationship between logK((triple bond FeO)2Zn) and pH was found, given by logK((triple bond FeO)2Znat1g/l)=2.058 (pH)-6.131. In addition, a surface activity coefficient term was introduced to the model to reduce the ionic strength

  18. Non-Equilibrium Thermodynamics in Multiphase Flows

    Mauri, Roberto

    2013-01-01

    Non-equilibrium thermodynamics is a general framework that allows the macroscopic description of irreversible processes. This book introduces non-equilibrium thermodynamics and its applications to the rheology of multiphase flows. The subject is relevant to graduate students in chemical and mechanical engineering, physics and material science. This book is divided into two parts. The first part presents the theory of non-equilibrium thermodynamics, reviewing its essential features and showing, when possible, some applications. The second part of this book deals with how the general theory can be applied to model multiphase flows and, in particular, how to determine their constitutive relations. Each chapter contains problems at the end, the solutions of which are given at the end of the book. No prior knowledge of statistical mechanics is required; the necessary prerequisites are elements of transport phenomena and on thermodynamics. “The style of the book is mathematical, but nonetheless it remains very re...

  19. Nonequilibrium statistical physics a modern perspective

    Livi, Roberto

    2017-01-01

    Statistical mechanics has been proven to be successful at describing physical systems at thermodynamic equilibrium. Since most natural phenomena occur in nonequilibrium conditions, the present challenge is to find suitable physical approaches for such conditions: this book provides a pedagogical pathway that explores various perspectives. The use of clear language, and explanatory figures and diagrams to describe models, simulations and experimental findings makes the book a valuable resource for undergraduate and graduate students, and also for lecturers organizing teaching at varying levels of experience in the field. Written in three parts, it covers basic and traditional concepts of nonequilibrium physics, modern aspects concerning nonequilibrium phase transitions, and application-orientated topics from a modern perspective. A broad range of topics is covered, including Langevin equations, Levy processes, directed percolation, kinetic roughening and pattern formation.

  20. Nonequilibrium molecular dynamics theory, algorithms and applications

    Todd, Billy D

    2017-01-01

    Written by two specialists with over twenty-five years of experience in the field, this valuable text presents a wide range of topics within the growing field of nonequilibrium molecular dynamics (NEMD). It introduces theories which are fundamental to the field - namely, nonequilibrium statistical mechanics and nonequilibrium thermodynamics - and provides state-of-the-art algorithms and advice for designing reliable NEMD code, as well as examining applications for both atomic and molecular fluids. It discusses homogenous and inhomogenous flows and pays considerable attention to highly confined fluids, such as nanofluidics. In addition to statistical mechanics and thermodynamics, the book covers the themes of temperature and thermodynamic fluxes and their computation, the theory and algorithms for homogenous shear and elongational flows, response theory and its applications, heat and mass transport algorithms, applications in molecular rheology, highly confined fluids (nanofluidics), the phenomenon of slip and...

  1. Nonequilibrium thermodynamics of restricted Boltzmann machines

    Salazar, Domingos S. P.

    2017-08-01

    In this work, we analyze the nonequilibrium thermodynamics of a class of neural networks known as restricted Boltzmann machines (RBMs) in the context of unsupervised learning. We show how the network is described as a discrete Markov process and how the detailed balance condition and the Maxwell-Boltzmann equilibrium distribution are sufficient conditions for a complete thermodynamics description, including nonequilibrium fluctuation theorems. Numerical simulations in a fully trained RBM are performed and the heat exchange fluctuation theorem is verified with excellent agreement to the theory. We observe how the contrastive divergence functional, mostly used in unsupervised learning of RBMs, is closely related to nonequilibrium thermodynamic quantities. We also use the framework to interpret the estimation of the partition function of RBMs with the annealed importance sampling method from a thermodynamics standpoint. Finally, we argue that unsupervised learning of RBMs is equivalent to a work protocol in a system driven by the laws of thermodynamics in the absence of labeled data.

  2. Nonequilibrium thermodynamics of restricted Boltzmann machines.

    Salazar, Domingos S P

    2017-08-01

    In this work, we analyze the nonequilibrium thermodynamics of a class of neural networks known as restricted Boltzmann machines (RBMs) in the context of unsupervised learning. We show how the network is described as a discrete Markov process and how the detailed balance condition and the Maxwell-Boltzmann equilibrium distribution are sufficient conditions for a complete thermodynamics description, including nonequilibrium fluctuation theorems. Numerical simulations in a fully trained RBM are performed and the heat exchange fluctuation theorem is verified with excellent agreement to the theory. We observe how the contrastive divergence functional, mostly used in unsupervised learning of RBMs, is closely related to nonequilibrium thermodynamic quantities. We also use the framework to interpret the estimation of the partition function of RBMs with the annealed importance sampling method from a thermodynamics standpoint. Finally, we argue that unsupervised learning of RBMs is equivalent to a work protocol in a system driven by the laws of thermodynamics in the absence of labeled data.

  3. Sorption Energy Maps of Clay Mineral Surfaces

    Cygan, Randall T.; Kirkpatrick, R. James

    1999-01-01

    A molecular-level understanding of mineral-water interactions is critical for the evaluation and prediction of the sorption properties of clay minerals that may be used in various chemical and radioactive waste disposal methods. Molecular models of metal sorption incorporate empirical energy force fields, based on molecular orbital calculations and spectroscopic data, that account for Coulombic, van der Waals attractive, and short-range repulsive energies. The summation of the non-bonded energy terms at equally-spaced grid points surrounding a mineral substrate provides a three dimensional potential energy grid. The energy map can be used to determine the optimal sorption sites of metal ions on the exposed surfaces of the mineral. By using this approach, we have evaluated the crystallographic and compositional control of metal sorption on the surfaces of kaolinite and illite. Estimates of the relative sorption energy and most stable sorption sites are derived based on a rigid ion approximation

  4. Linking Equilibrium and Nonequilibrium Dynamics in Glass-Forming Systems

    Mauro, John C.; Guo, Xiaoju; Smedskjær, Morten Mattrup

    , we show that the nonequilibrium glassy dynamics are intimately connected with the equilibrium liquid dynamics. This is accomplished by deriving a new functional form for the thermal history dependence of nonequilibrium viscosity, which is validated against experimental measurements of industrial...

  5. Canonical operator formulation of nonequilibrium thermodynamics

    Mehrafarin, M.

    1992-09-01

    A novel formulation of nonequilibrium thermodynamics is proposed which emphasises the fundamental role played by the Boltzmann constant k in fluctuations. The equivalence of this and the stochastic formulation is demonstrated. The k → 0 limit of this theory yields the classical deterministic description of nonequilibrium thermodynamics. The new formulation possesses unique features which bear two important results namely the thermodynamic uncertainty principle and the quantisation of entropy production rate. Such a theory becomes indispensable whenever fluctuations play a significant role. (author). 7 refs

  6. Nonideal plasmas as non-equilibrium media

    Morozov, I V; Norman, G E; Valuev, A A; Valuev, I A

    2003-01-01

    Various aspects of the collective behaviour of non-equilibrium nonideal plasmas are studied. The relaxation of kinetic energy to the equilibrium state is simulated by the molecular dynamics (MD) method for two-component non-degenerate strongly non-equilibrium plasmas. The initial non-exponential stage, its duration and the subsequent exponential stage of the relaxation process are studied for a wide range of ion charge, nonideality parameter and ion mass. A simulation model of the nonideal plasma excited by an electron beam is proposed. An approach is developed to calculate the dynamic structure factor in non-stationary conditions. Instability increment is obtained from MD simulations

  7. On the excess energy of nonequilibrium plasma

    Timofeev, A. V.

    2012-01-01

    The energy that can be released in plasma due to the onset of instability (the excess plasma energy) is estimated. Three potentially unstable plasma states are considered, namely, plasma with an anisotropic Maxwellian velocity distribution of plasma particles, plasma with a two-beam velocity distribution, and an inhomogeneous plasma in a magnetic field with a local Maxwellian velocity distribution. The excess energy can serve as a measure of the degree to which plasma is nonequilibrium. In particular, this quantity can be used to compare plasmas in different nonequilibrium states.

  8. Shape characteristics of equilibrium and non-equilibrium fractal clusters.

    Mansfield, Marc L; Douglas, Jack F

    2013-07-28

    It is often difficult in practice to discriminate between equilibrium and non-equilibrium nanoparticle or colloidal-particle clusters that form through aggregation in gas or solution phases. Scattering studies often permit the determination of an apparent fractal dimension, but both equilibrium and non-equilibrium clusters in three dimensions frequently have fractal dimensions near 2, so that it is often not possible to discriminate on the basis of this geometrical property. A survey of the anisotropy of a wide variety of polymeric structures (linear and ring random and self-avoiding random walks, percolation clusters, lattice animals, diffusion-limited aggregates, and Eden clusters) based on the principal components of both the radius of gyration and electric polarizability tensor indicates, perhaps counter-intuitively, that self-similar equilibrium clusters tend to be intrinsically anisotropic at all sizes, while non-equilibrium processes such as diffusion-limited aggregation or Eden growth tend to be isotropic in the large-mass limit, providing a potential means of discriminating these clusters experimentally if anisotropy could be determined along with the fractal dimension. Equilibrium polymer structures, such as flexible polymer chains, are normally self-similar due to the existence of only a single relevant length scale, and are thus anisotropic at all length scales, while non-equilibrium polymer structures that grow irreversibly in time eventually become isotropic if there is no difference in the average growth rates in different directions. There is apparently no proof of these general trends and little theoretical insight into what controls the universal anisotropy in equilibrium polymer structures of various kinds. This is an obvious topic of theoretical investigation, as well as a matter of practical interest. To address this general problem, we consider two experimentally accessible ratios, one between the hydrodynamic and gyration radii, the other

  9. Applicability of microautoradiography to sorption studies

    Thompson, J.L.; Wolfsberg, K.

    1979-01-01

    The technique of microautoradiography was applied to the study of the sorption of uranium and americium on five rock types which exist at the Nevada Test Site. It was found that autoradiograms could be prepared in a few days which would allow the specific minerals responsible for sorption to be identified. Furthermore, the state of aggregation of the sorbed species was clearly indicated. It was concluded that microautoradiography was a useful adjunct to currently used methods for studying sorption of certain radionuclides

  10. Characterization of nonequilibrium states of trapped Bose–Einstein condensates

    Yukalov, V. I.; Novikov, A. N.; Bagnato, V. S.

    2018-06-01

    The generation of different nonequilibrium states in trapped Bose–Einstein condensates is studied by numerically solving the nonlinear Schrödinger equation. Inducing nonequilibrium states by shaking a trap creates the following states: weak nonequilibrium, the state of vortex germs, the state of vortex rings, the state of straight vortex lines, the state of deformed vortices, vortex turbulence, grain turbulence, and wave turbulence. A characterization of nonequilibrium states is advanced by introducing effective temperature, Fresnel number, and Mach number.

  11. Strontium sorption on Savannah River Plant soils

    Hoeffner, S.L.

    1984-12-01

    A laboratory study of strontium-85 sorption was conducted using Savannah River Plant soil and groundwater from the low-level waste burial ground. Systematic variation of soil and water composition indicates that strontium sorption is most strongly a function of pH. Changes in clay content and in K + , Ca 2+ , or Mg 2+ concentrations influence strontium sorption indirectly through the slight pH changes which result. The ions Na + , Cl - , and NO 3 - have no effect. Ferrous ion, added to groundwater to simulate the conditions of water at the bottom of waste trenches, did not account for low strontium sorption observed with some trench waters

  12. Quantum distribution function of nonequilibrium system

    Sogo, Kiyoshi; Fujimoto, Yasushi.

    1990-03-01

    A path integral representation is derived for the Wigner distribution function of a nonequilibrium system coupled with heat bath. Under appropriate conditions, the Wigner distribution function approaches an equilibrium distribution, which manifests shifting and broadening of spectral lines due to the interaction with heat bath. It is shown that the equilibrium distribution becomes the quantum canonical distribution in the vanishing coupling constant limit. (author)

  13. Nonequilibrium Molecular Energy Coupling and Conversion Mechanisms

    2016-08-28

    resolved temperature measurements, by pure rotational picosecond broadband Coherent Anti-Stokes Raman Spectroscopy ( CARS ), and kinetic modeling...rotational ps CARS for thermometry measurements in highly transient nonequilibrium plasmas. Rotational-translational temperatures are measured for time...primarily on localized flow heating on sub-acoustic time scale, and for assessing feasibility of high-speed aerodynamic flow control by vibrational

  14. Non-equilibrium thermodynamics and physical kinetics

    Bikkin, Halid

    2014-01-01

    This graduate textbook covers contemporary directions of non-equilibrium statistical mechanics as well as classical methods of kinetics. With one of the main propositions being to avoid terms such as "obviously" and "it is easy to show", this treatise is an easy-to-read introduction into this traditional, yet vibrant field.

  15. Introduction to the nonequilibrium functional renormalization group

    Berges, J.; Mesterházy, D.

    2012-01-01

    In these lectures we introduce the functional renormalization group out of equilibrium. While in thermal equilibrium typically a Euclidean formulation is adequate, nonequilibrium properties require real-time descriptions. For quantum systems specified by a given density matrix at initial time, a generating functional for real-time correlation functions can be written down using the Schwinger-Keldysh closed time path. This can be used to construct a nonequilibrium functional renormalization group along similar lines as for Euclidean field theories in thermal equilibrium. Important differences include the absence of a fluctuation-dissipation relation for general out-of-equilibrium situations. The nonequilibrium renormalization group takes on a particularly simple form at a fixed point, where the corresponding scale-invariant system becomes independent of the details of the initial density matrix. We discuss some basic examples, for which we derive a hierarchy of fixed point solutions with increasing complexity from vacuum and thermal equilibrium to nonequilibrium. The latter solutions are then associated to the phenomenon of turbulence in quantum field theory.

  16. Generators of nonequilibrium low-temperature plasma

    Dautov, G.Yu.

    1988-01-01

    Results are described of a study and of the characteristics of sources of a non-equilibrium gas-discharge plasma. The plasma generators considered include glow, high frequency, and arc discharge generators. Thermodynamic, ionic, and electronic processes occurring in the plasmas are evaluated

  17. Non-equilibrium modelling of distillation

    Wesselingh, JA; Darton, R

    1997-01-01

    There are nasty conceptual problems in the classical way of describing distillation columns via equilibrium stages, and efficiencies or HETP's. We can nowadays avoid these problems by simulating the behaviour of a complete column in one go using a non-equilibrium model. Such a model has phase

  18. Evolution and non-equilibrium physics

    Becker, Nikolaj; Sibani, Paolo

    2014-01-01

    We argue that the stochastic dynamics of interacting agents which replicate, mutate and die constitutes a non-equilibrium physical process akin to aging in complex materials. Specifically, our study uses extensive computer simulations of the Tangled Nature Model (TNM) of biological evolution...

  19. Experimental Study and modelling of the Sorption of Selenite and Europium Onto Smectite and Illite Clays

    Missana, T.; Alonso, U.; Garcia-Gutierrez, M.

    2009-01-01

    This study provides a large set of experimental selenite sorption data for pure smectite and illite. Similar sorption behavior existed in both clays: linear within a large range of the Se concentrations investigated and independent of ionic strength. Selenite sorption was also analysed in the illite/smectite system with the clays mixed in two different proportions. The objective of the study was to provide the simplest model possible to fit the experimental data, a model also capable of describing selenite sorption in binary illite/smectite clay systems. Selenite sorption data were modeled using both a one-and a two-site non-electrostatic model that took into account the formation of two complexes at the edge sites of the clay. The complexation constants obtained by fitting sorption data of the individual minerals were incorporated into a model to predict the adsorption of selenium in the illite/ smectite mixtures; the models predictions were consistent with the experimental adsorption data. (Author) 42 refs

  20. Experimental Study and modelling of the Sorption of Selenite and Europium Onto Smectite and Illite Clays

    Missana, T.; Alonso, U.; Garcia-Gutierrez, M.

    2009-10-12

    This study provides a large set of experimental selenite sorption data for pure smectite and illite. Similar sorption behavior existed in both clays: linear within a large range of the Se concentrations investigated and independent of ionic strength. Selenite sorption was also analysed in the illite/smectite system with the clays mixed in two different proportions. The objective of the study was to provide the simplest model possible to fit the experimental data, a model also capable of describing selenite sorption in binary illite/smectite clay systems. Selenite sorption data were modeled using both a one-and a two-site non-electrostatic model that took into account the formation of two complexes at the edge sites of the clay. The complexation constants obtained by fitting sorption data of the individual minerals were incorporated into a model to predict the adsorption of selenium in the illite/ smectite mixtures; the models predictions were consistent with the experimental adsorption data. (Author) 42 refs.

  1. Nonequilibrium chiral fluid dynamics including dissipation and noise

    Nahrgang, Marlene; Herold, Christoph; Bleicher, Marcus; Leupold, Stefan

    2011-01-01

    We present a consistent theoretical approach for the study of nonequilibrium effects in chiral fluid dynamics within the framework of the linear σ model with constituent quarks. Treating the quarks as an equilibrated heat bath, we use the influence functional formalism to obtain a Langevin equation for the σ field. This allows us to calculate the explicit form of the damping coefficient and the noise correlators. For a self-consistent derivation of both the dynamics of the σ field and the quark fluid, we have to employ the 2PI (two-particle irreducible) effective action formalism. The energy dissipation from the field to the fluid is treated in the exact formalism of the 2PI effective action where a conserved energy-momentum tensor can be constructed. We derive its form and comment on approximations generating additional terms in the energy-momentum balance of the entire system.

  2. Nonequilibrium quark production in the expanding QCD plasma

    Tanji, Naoto; Berges, Jürgen

    2018-02-01

    We perform real-time lattice simulations of nonequilibrium quark production in the longitudinally expanding QCD plasma. Starting from a highly occupied gluonic state with vacuum quark sector, we extract the time evolution of quark and gluon number densities per unit transverse area and rapidity. The total quark number shows after an initial rapid increase an almost linear growth with time. Remarkably, this growth rate appears to be consistent with a simple kinetic theory estimate involving only two-to-two scattering processes in small-angle approximation. This extends previous findings about the role of two-to-two scatterings for purely gluonic dynamics in accordance with the early stages of the bottom-up thermalization scenario.

  3. Newton-Krylov methods applied to nonequilibrium radiation diffusion

    Knoll, D.A.; Rider, W.J.; Olsen, G.L.

    1998-01-01

    The authors present results of applying a matrix-free Newton-Krylov method to a nonequilibrium radiation diffusion problem. Here, there is no use of operator splitting, and Newton's method is used to convert the nonlinearities within a time step. Since the nonlinear residual is formed, it is used to monitor convergence. It is demonstrated that a simple Picard-based linearization produces a sufficient preconditioning matrix for the Krylov method, thus elevating the need to form or store a Jacobian matrix for Newton's method. They discuss the possibility that the Newton-Krylov approach may allow larger time steps, without loss of accuracy, as compared to an operator split approach where nonlinearities are not converged within a time step

  4. Kinetic theory of nonequilibrium ensembles, irreversible thermodynamics, and generalized hydrodynamics

    Eu, Byung Chan

    2016-01-01

    This book presents the fundamentals of irreversible thermodynamics for nonlinear transport processes in gases and liquids, as well as for generalized hydrodynamics extending the classical hydrodynamics of Navier, Stokes, Fourier, and Fick. Together with its companion volume on relativistic theories, it provides a comprehensive picture of the kinetic theory formulated from the viewpoint of nonequilibrium ensembles in both nonrelativistic and, in Vol. 2, relativistic contexts. Theories of macroscopic irreversible processes must strictly conform to the thermodynamic laws at every step and in all approximations that enter their derivation from the mechanical principles. Upholding this as the inviolable tenet, the author develops theories of irreversible transport processes in fluids (gases or liquids) on the basis of irreversible kinetic equations satisfying the H theorem. They apply regardless of whether the processes are near to or far removed from equilibrium, or whether they are linear or nonlinear with respe...

  5. Nonequilibrium statistical operator in hot-electron transport theory

    Xing, D.Y.; Liu, M.

    1991-09-01

    The Nonequilibrium Statistical Operator method developed by Zubarev is generalized and applied to the study of hot-electron transport in semiconductors. The steady-state balance equations for momentum and energy are derived to the lowest order in the electron-lattice coupling. We show that the derived balance equations are exactly the same as those obtained by Lei and Ting. This equivalence stems from the fact that to the linear order in the electron-lattice coupling, two statistical density matrices have identical effect when they are used to calculate the average value of a dynamical operator. The application to the steady-state and transient hot-electron transport in multivalley semiconductors is also discussed. (author). 28 refs, 1 fig

  6. Specific heat, polarization and heat conduction in microwave heating systems: A nonequilibrium thermodynamic point of view

    Bergese, Paolo

    2006-01-01

    A microwave (MW) field can induce in a dielectric material an oscillatory polarization. By this mechanism part of the energy carried by the waves is converted into chaotic agitation, and the material heats up. MW heating is a nonequilibrium phenomenon, while conventional heating can generally be considered as quasi-static. Excess (or nonthermal) effects of MWs with respect to conventional heating lie in this difference. Macroscopically, MW heating can be described in the framework of linear nonequilibrium thermodynamics (NET). This approach indicates that in a dielectric material under MW heating the specific heat has a dynamic component linked to the variation of polarization with temperature, and that polarization and heat conduction are intertwined. In particular, linear NET provides a new phenomenological equation for heat conduction that is composed of the classic Fourier's law and an additional term due to polarization relaxation. This term quantitatively describes the excess effect of MWs on thermal conduction

  7. Linear response theory for quantum open systems

    Wei, J. H.; Yan, YiJing

    2011-01-01

    Basing on the theory of Feynman's influence functional and its hierarchical equations of motion, we develop a linear response theory for quantum open systems. Our theory provides an effective way to calculate dynamical observables of a quantum open system at its steady-state, which can be applied to various fields of non-equilibrium condensed matter physics.

  8. Sorption of radionuclides on inorganic sorbents

    Rajec, P.; Matel, L.

    1995-01-01

    The sorption of cesium, strontium, plutonium and americium from water solution on natural zeolite, clay minerals, synthetic zeolites and ferrocyanides in silica gel matrix was studied. The same experiments but with synthetic zeolites irradiated by the dose 100 kGy proved no change in sorption properties. 1 tab., 4 refs

  9. Nitrate Sorption in an Agricultural Soil Profile

    Wissem Hamdi

    2013-01-01

    Full Text Available Increasing concentrations of in surface water and groundwater can cause ecological and public health effects and has come under increased scrutiny by both environmental scientists and regulatory agencies. For many regions though, including the Sahel of Tunisia, little is known about the sorption capacity of soils. In this project we measured sorption by a profile of an iso-humic soil from Chott Meriem, Tunisia. Soil samples were collected from four soil depths (0–25, 25–60, 60–90, and 90–120 cm on 1 June 2011, and their sorption capacity was determined using batch experiments under laboratory conditions. The effects of contact time, the initial concentration, and the soil-solution ratio on sorption were investigated. In general, the results suggested that was weakly retained by the Chott Meriem soil profile. The quantity of sorption increased with depth, contact time, initial concentration, and soil-solution ratios. To evaluate the sorption capacities of the soil samples at concentrations ranging between 25 and 150 mg L−1 experimental data were fitted to both Freundlich and Langmuir isotherm sorption models. The results indicated that Freundlich model was better for describing sorption in this soil profile.

  10. A FIXED BED SORPTION SYSTEM FOR DEFLUORIDATION OF GROUND WATER

    Ayoob Sulaiman

    2009-06-01

    Full Text Available The presence of excess fluoride in ground water has become a global threat with as many as 200 million people affected in more than 35 countries in all the continents. Of late, there have been significant advances in the knowledge base regarding the effects of excess fluoride on human health. As a result, defluoridation of ground water is regarded as one of the key areas of attention among the universal water community triggering global research. This study describes the sorptive responses of a newly developed adsorbent, alumina cement granules (ALC, in its real-life application in fixed beds, for removing fluoride from the ground waters of a rural Indian village. ALC exhibited almost consistent scavenging capacity at various bed depths in column studies with an enhanced adsorption potential of 0.818 mg/g at a flow rate of 4 ml/min. The Thomas model was examined to describe the sorption process. The process design parameters of the column were obtained by linear regression of the model. In all the conditions examined, the Thomas model could consistently predict its characteristic parameters and describe the breakthrough sorption profiles in the whole range of sorption process.

  11. Extra entropy production due to non-equilibrium phase transitions in relativistic heavy ion reactions

    Csernai, L.P.; Lukacs, B.

    1984-04-01

    In a fluid-dynamical model the extra entropy production is calculated which arises from a non-equilibrium phase transition from nuclear to quark matter. The dynamics of processes producing extra entropy are treated in linear approximation. It is shown that there is a considerable extra entropy production provided the transition is not too fast. In measuring the entropy at the break-up, an excess entropy might signalize the phase transition to a transient quark-gluon plasma. (D.Gy.)

  12. Sorption of mercury on chemically synthesized polyaniline

    Remya Devi, P.S.; Verma, R.; Sudersanan, M.

    2006-01-01

    Sorption of inorganic mercury (Hg 2+ ) and methyl mercury, on chemically synthesized polyaniline, in 0.1-10N HCl solutions has been studied. Hg 2+ is strongly sorbed at low acidities and the extent of sorption decreases with increase in acidity. The sorption of methyl mercury is very low in the HCl concentration range studied. Sorption of Hg 2+ on polyaniline in 0.1-10N LiCl and H 2 SO 4 solutions has also been studied. The analysis of the data indicates that the sorption of Hg 2+ depends on the degree of protonation of polyaniline and the nature of mercury(II) chloride complexes in solution. X-ray photoelectron spectroscopy analysis (XPS) of polyaniline sorbed with mercury show that mercury is bound as Hg 2+ . Sorbed mercury is quantitatively eluted from polyaniline with 0.5N HNO 3 . Polyaniline can be used for separation and pre-concentration of inorganic mercury from aqueous samples. (author)

  13. Phenanthrene sorption on biochar-amended soils

    Kahawaththa Gamage, Inoka Damayanthi Kumari; Moldrup, Per; Paradelo Pérez, Marcos

    2014-01-01

    on their influences on the sorption of environmental contaminants. In a field-based study at two experimental sites in Denmark, we investigated the effect of birch wood-derived biochar (Skogans kol) on the sorption of phenanthrene in soils with different properties. The soil sorption coefficient, Kd (L kg-1......), of phenanthrene was measured on sandy loam and loamy sand soils which have received from zero up to 100 t ha-1 of biochar. Results show that birch wood biochar had a higher Kd compared to soils. Furthermore, the application of birch wood biochar enhanced the sorption of phenanthrene in agricultural soils...... carbon, while it negatively correlated with clay content. The results also revealed that biochar-mineral interactions play an important role in the sorption of phenanthrene in biochar-amended soil....

  14. Cobalt sorption onto Savannah River Plant soils

    Hoeffner, S.L.

    1985-06-01

    A laboratory study of cobalt-60 sorption was conducted using Savannah River Plant soil and groundwater from the low-level waste burial ground. Systematic variation of soil and water composition indicates that cobalt sorption is most strongly a function of pH. Over a pH range of 2 to 9, the distribution coefficient ranged from 2 to more than 10,000 mL/g. Changes in clay content and in K + , Ca 2+ , or Mg 2+ concentrations influence cobalt sorption indirectly through the slight pH changes which result. The ions Na + , Cl - , and NO 3 - have no effect on cobalt sorption. Ferrous ion, added to groundwater to simulate the condition of water at the bottom of the waste trenches, accounts for part of the decrease in cobalt sorption observed with trench waters. 17 refs., 3 figs., 4 tabs

  15. Sorption of biodegradation end products of nonylphenol polyethoxylates onto activated sludge.

    Hung, Nguyen Viet; Tateda, Masafumi; Ike, Michihiko; Fujita, Masanori; Tsunoi, Shinji; Tanaka, Minoru

    2004-01-01

    Nonylphenol(NP), nonylphenoxy acetic acid (NP1EC), nonylphenol monoethoxy acetic acid (NP2EC), nonylphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate (NP2EO) are biodegradation end products (BEPs) of nonionic surfactant nonylphenolpolyethoxylates (NPnEO). In this research, sorption of these compounds onto model activated sludge was characterized. Sorption equilibrium experiments showed that NP, NP1EO and NP2EO reached equilibrium in about 12 h, while equilibrium of NP1EC and NP2EC were reached earlier, in about 4 h. In sorption isotherm experiments, obtained equilibrium data at 28 degrees C fitted well to Freundlich sorption model for all investigated compounds. For NP1EC, in addition to Freundlich, equilibrium data also fitted well to Langmuir model. Linear sorption model was also tried, and equilibrium data of all NP, NP1EO, NP2EO and NP2EC except NP1EC fitted well to this model. Calculated Freundlich coefficient (K(F)) and linear sorption coefficient (K(D)) showed that sorption capacity of the investigated compounds were in order NP > NP2EO > NP1EO > NP1EC approximately NP2EC. For NP, NP1EO and NP2EO, high values of calculated K(F) and K(D) indicated an easy uptake of these compounds from aqueous phase onto activated sludge. Whereas, NP1EC and NP2EC with low values of K(F) and K(D) absorbed weakly to activated sludge and tended to preferably remain in aqueous phase.

  16. Generalized nonequilibrium capillary relations for two-phase flow through heterogeneous media.

    Amaziane, Brahim; Milišić, Josipa Pina; Panfilov, Mikhail; Pankratov, Leonid

    2012-01-01

    For two-phase flow in porous media, the natural medium heterogeneity necessarily gives rise to capillary nonequilibrium effects. The relaxation to the equilibrium is a slow process which should be introduced in macroscopic flow models. Many nonequilibrium models are based on a phenomenological approach. At the same time there exists a rigorous mathematical way to develop the nonequilibrium equations. Its formalism, developed by Bourgeat and Panfilov [Computational Geosciences 2, 191 (1998)], is based on the homogenization of the microscale flow equations over medium heterogeneities. In contrast with the mentioned paper, in which the case of a sufficiently fast relaxation was analyzed, we consider the case of long relaxation, which leads to the appearance of long-term memory on the macroscale. Due to coupling between the nonlinearity and nonlocality in time, the macroscopic model remains, however, incompletely homogenized, in the general case. At the same time, frequently only the relationship for the nonequilibrium capillary pressure is of interest for applications. In the present paper, we obtain such an exact relationship in two different independent forms for the case of long-term memory. This relationship is more general than that obtained by Bourgeat and Panfilov. In addition, we prove the comparison theorem which determines the upper and lower bounds for the macroscopic model. These bounds represent linear flow models, which are completely homogenized. The results obtained are illustrated by numerical simulations.

  17. Effect of competing cations on strontium sorption to surficial sediments

    Bunde, R.L.; Rosentreter, J.J.

    1995-01-01

    The following study was conducted to determine strontium distribution coefficients (K d 'S) of a surficial sediment at the Idaho National Engineering Laboratory (INEL), Idaho. Batch experimental techniques were used to determine K d 's which describe the partitioning of a solute between the solution and solid phase. A surficial sediment was mixed with synthesized aqueous solutions designed to chemically simulate wastewater disposed to infiltrations ponds near the Idaho Chemical Processing Plant at the INEL with respect to major ionic character and pH. The effects of variable concentrations of competing cations (sodium, potassium, calcium and magnesium) on strontium sorption were investigated at a fixed pH of 8.00. The pH of the natural system shows no appreciable variation, whereas a marked variability in cation concentration has been noted. Strontium sorption was impacted to a greater degree by the concentration of calcium and magnesium in solution than by the presence of sodium or potassium. However, extreme sodium solution concentrations of 1.0 to 5.0 g/L dramatically reduced strontium sorption. In all cases, strontium K d 's decreased as the concentration of calcium and magnesium in solution increased. Linear isotherm model K d 's ranged from 12.0 to 84.7 mL/g. Analysis of data from these experiments indicated that moderate concentrations of calcium and magnesium (less than 40 mg/L) and high concentrations of sodium (1.0 to 5.0 g/L) in wastewater increase strontium mobility by decreasing the sorption of strontium on surficial sediments beneath infiltration ponds at the INEL

  18. Sorption and Transport of Ranitidine in Natural Soils

    Gaynor, A. J.; Vulava, V. M.

    2013-12-01

    -horizon than to A-horizon soils, implying a strong preference for soils higher in clay content. Freundlich model (q = Kf Cn, where Kf and n are fitting parameters) fit the sorption isotherms. Glass chromatography columns packed with soil were used for column experiments. Ranitidine tracer was injected into saturated soil columns and the breakthrough tracer concentrations were plotted as a function of time. The shape of these breakthrough curves indicated that there were two distinct sorption sites on soils - organic matter and clay minerals - which influenced tracer transport. A two-region, nonequilibrium transport code was used to model the breakthrough curves. These experiments indicate that ranitidine sorbs more strongly to clay-rich soils than to organic-rich soils. The presence of amine functional groups in ranitidine's chemical structure results in its acidic behavior in the soil solution. In acidic solutions, the cationic form of ranitidine likely forms ionic bonds with negatively charged clay surfaces. Other components of ranitidine are likely to form covalent bonds with organic matter. The data shows the complex nature of ranitidine in interactions with environmental surfaces.

  19. Effect of humic substances on P sorption capacity of three different soils

    Delgado, Antonio

    2010-05-01

    Organic matter decreases P sorption by soils. It has been demonstrated the effect of low molecular weight compounds decreasing P adsorption on active surfaces and the effect of humic and fulvic acids inhibiting the precipitation of hydroxyapatite and favouring the formation of more soluble phosphates. This contributes to increase the recovery of applied P fertilizer. The objective of this work was to study the effect of 4 different humic substances (commercially available and provided by Tradecorp Internacional S.A.) on the sorption capacity of three soils differing widely in chemical properties (two calcareous from south Spain, pH 8 and 8.5, and other acidic from Brazil, pH 5.9 and 50 % of exchangeable basic cations). To this end, sorption isotherms were performed at a soil:0.01 M CaCl2 ratio of 1:10 at 6, 30 and 90 days. 2.5 mg of humic substances per g of soil were added to the solution. Data were fitted to the best model and linearized sorption curves for each humic substance were compared with the linearized sorption curve for the control without humic substances application (intersection point and slopes). Soil from Brazil showed a much higher sorption capacity (400 mg P kg-1 soil sorbed at 1 mg L-1 of P in the solution at 1 day) than the other two soils (50 and 100 mg P kg-1). Slow reactions significantly contributed to P sorption in the three soils, amounts sorbed at 90 days being twice than those sorbed at 1 day. Two of the products increased P sorption in the soil from Brazil at 1 day. At 90 days all the products increased P sorption significantly. This increased P sorption can be only explained by metal complexation by the substances applied, which may result in organo-metallic compounds with a high P sorption capacity. This effect was independent of the proportion of humic and fulvic acids in the applied products because the amounts of metal complexed by these compouds depend on the amount of functional groups to coordinate with metals. In the Spanish

  20. Sorption-desorption of imidacloprid onto a lacustrine Egyptian soil and its clay and humic acid fractions.

    Kandil, Mahrous M; El-Aswad, Ahmed F; Koskinen, William C

    2015-01-01

    Sorption-desorption of the insecticide imidacloprid 1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine onto a lacustrine sandy clay loam Egyptian soil and its clay and humic acid (HA) fractions was investigated in 24-h batch equilibrium experiments. Imidacloprid (IMDA) sorption-desorption isotherms onto the three sorbents were found to belong to a non-linear L-type and were best described by the Freundlich model. The value of the IMDA adsorption distribution coefficient, Kd(ads), varied according to its initial concentration and was ranged 40-84 for HA, 14-58 for clay and 1.85-4.15 for bulk soil. Freundlich sorption coefficient, Kf(ads), values were 63.0, 39.7 and 4.0 for HA, clay and bulk soil, respectively. The normalized soil Koc value for imidacloprid sorption was ∼800 indicating its slight mobility in soils. Nonlinear sorption isotherms were indicated by 1/n(ads) values imidacloprid sorption process with all tested sorbents. Gibbs free energy (ΔG) values indicated a spontaneous and physicosorption process for IMDA and a more favorable sorption to HA than clay and soil. In conclusion, although the humic acid fraction showed the highest capacity and affinity for imidacloprid sorption, the clay fraction contributed to approximately 95% of soil-sorbed insecticide. Clay and humic acid fractions were found to be the major two factors controlling IMDA sorption in soils. The slight mobility of IMDA in soils and the hysteresis phenomenon associated with the irreversibility of its sorption onto, mainly, clay and organic matter of soils make its leachability unlikely to occur.

  1. Nonequilibrium recombination after a curved shock wave

    Wen, Chihyung; Hornung, Hans

    2010-02-01

    The effect of nonequilibrium recombination after a curved two-dimensional shock wave in a hypervelocity dissociating flow of an inviscid Lighthill-Freeman gas is considered. An analytical solution is obtained with the effective shock values derived by Hornung (1976) [5] and the assumption that the flow is ‘quasi-frozen’ after a thin dissociating layer near the shock. The solution gives the expression of dissociation fraction as a function of temperature on a streamline. A rule of thumb can then be provided to check the validity of binary scaling for experimental conditions and a tool to determine the limiting streamline that delineates the validity zone of binary scaling. The effects on the nonequilibrium chemical reaction of the large difference in free stream temperature between free-piston shock tunnel and equivalent flight conditions are discussed. Numerical examples are presented and the results are compared with solutions obtained with two-dimensional Euler equations using the code of Candler (1988) [10].

  2. Sorption behavior of cesium onto bentonite colloid

    Iijima, Kazuki; Masuda, Tsuguya; Tomura, Tsutomu

    2004-01-01

    It is considered that bentonite colloid might be generated from bentonite which will be used as buffer material in geological disposal system, and can facilitate the migration of radionuclides by means of sorption. In order to examine this characteristic, sorption and desorption experiments of Cs onto bentonite colloid were carried out to obtain its distribution coefficient (Kd) and information on the reversibility of its sorption. In addition, particle size distribution and shape of colloid were investigated and their effect on the sorption behavior was discussed. Kds for Cs were around 20 m 3 /kg for sorption and 30 m 3 /kg for desorption, in which sorbed Cs was desorbed by 8.4x10 -4 mol/l of NaCl solution. These values did not show any dependencies on Cs concentration and duration of sorption and desorption. The first 20% of sorbed Cs was desorbed reversibly at least. Most of colloidal particles were larger than 200 nm and TEM micrographs showed they had only several sheets of the clay crystal. Obtained Kds for colloidal bentonite were larger than those for powdered bentonite. This can be caused by difference of competing ions in the solution, characteristics of contained smectite, or sorption site density. (author)

  3. Sorption of uranyl ions on hydrous oxides

    Gupta, A.R.; Venkataramani, B.

    1988-01-01

    Sorption of uranyl ions on hydrous titanium oxide (HTiO), magnetite (MAG), and hydrous thorium oxide (HThO) has been studied as a function of pH. Hydrous oxides have been characterized by their pH-titration curves, intrinsic dissociation constants (pK ai * ) and point of zero charge (pH pzc ). The fraction of protonated surface hydroxyl groups as well as the surface pH (pH surf ) as a function of solution pH have been computed. The distribution of various hydrolyzed species of uranyl ions with solution pH have been compared with uranyl sorption isotherm on these oxides. Sorption edge in all the cases occurs when free hydroxyl groups are available on the surface and pH surf is sufficiently high to favor the formation of dimer-like species on the surface. A new model for the sorption process, called surface hydrolysis model, which explains these and other features of uranyl sorption on hydrous oxides has been proposed. The model visualizes the sorption process as linking of uranyl ions with two adjacent free surface hydroxyl groups without deprotonation (provided the surface pH is high for the hydrolysis of uranyl ions) and formation of dimer-like structures on the surface. The new model has been successfully applied to the present and other available data on uranyl ion sorption on hydrous oxides. (author)

  4. Sorption equilibria of ethanol on cork.

    Lequin, Sonia; Chassagne, David; Karbowiak, Thomas; Bellat, Jean-Pierre

    2013-06-05

    We report here for the first time a thermodynamic study of gaseous ethanol sorption on raw cork powder and plate. Our study aims at a better understanding of the reactivity of this material when used as a stopper under enological conditions, thus in close contact with a hydroethanolic solution, wine. Sorption−desorption isotherms were accurately measured by thermogravimetry at 298 K in a large range of relative pressures. Sorption enthalpies were determined by calorimetry as a function of loading. Sorption−desorption isotherms exhibit a hysteresis loop probably due to the swelling of the material and the absorption of ethanol. Surprisingly, the sorption enthalpy of ethanol becomes lower than the liquefaction enthalpy as the filling increases. This result could be attributed to the swelling of the material, which would generate endothermic effects. Sorption of SO₂ on cork containing ethanol was also studied. When the ethanol content in cork is 2 wt %, the amount of SO₂ sorbed is divided by 2. Thus, ethanol does not enhance the sorption rate for SO₂ but, on the contrary, decreases the SO₂ sorption activity onto cork, probably because of competitive sorption mechanisms.

  5. Sorption of streptococcus faecium to glass

    Oerstavik, D.

    1977-01-01

    A method has been developed by which to study the sorption of Streptococcus faecium to soda-lime cover glasses. Conditions were chosen to minimize the influence on sorption of bacterial polymer production, passive sorption being studied rather than attachment mediated by metabolic activities. Sorption of S. faecium increased with increasing temperature (to 50degC), time, and cell concentration, but equilibrium apparently was not reached even after incubation for 8 hours or at a cell concentration of 3 x 10 10 per ml. Sorption increased with solute molarity up to 0.1 M concentration of NaCl and KCl, indicating an effect of the electrical double layers on the apposition of cells to the glass surface. Desorption of bacteria could be obtained after multiple washings of the glasses in buffer or by the action of Tween 80, but not if sorbed bacteria were left in distilled water, various salt solutions, urea, or in suspensions of unlabelled bacteria. It was concluded that sorption occurred as a result of chemical interactions between the glass and the cell surface. Tween 80 at a concentration of 1 per cent inhibited sorption to 26 per cent of buffer controls, 2 M urea was less effective, and 1 M NaCl was without effect. It is suggested that hydrophobic interactions may be of importance in the binding of S. faecium to glass. (author)

  6. Lattice Boltzmann approach for complex nonequilibrium flows.

    Montessori, A; Prestininzi, P; La Rocca, M; Succi, S

    2015-10-01

    We present a lattice Boltzmann realization of Grad's extended hydrodynamic approach to nonequilibrium flows. This is achieved by using higher-order isotropic lattices coupled with a higher-order regularization procedure. The method is assessed for flow across parallel plates and three-dimensional flows in porous media, showing excellent agreement of the mass flow with analytical and numerical solutions of the Boltzmann equation across the full range of Knudsen numbers, from the hydrodynamic regime to ballistic motion.

  7. Efficiency bounds for nonequilibrium heat engines

    Mehta, Pankaj; Polkovnikov, Anatoli

    2013-01-01

    We analyze the efficiency of thermal engines (either quantum or classical) working with a single heat reservoir like an atmosphere. The engine first gets an energy intake, which can be done in an arbitrary nonequilibrium way e.g. combustion of fuel. Then the engine performs the work and returns to the initial state. We distinguish two general classes of engines where the working body first equilibrates within itself and then performs the work (ergodic engine) or when it performs the work before equilibrating (non-ergodic engine). We show that in both cases the second law of thermodynamics limits their efficiency. For ergodic engines we find a rigorous upper bound for the efficiency, which is strictly smaller than the equivalent Carnot efficiency. I.e. the Carnot efficiency can be never achieved in single reservoir heat engines. For non-ergodic engines the efficiency can be higher and can exceed the equilibrium Carnot bound. By extending the fundamental thermodynamic relation to nonequilibrium processes, we find a rigorous thermodynamic bound for the efficiency of both ergodic and non-ergodic engines and show that it is given by the relative entropy of the nonequilibrium and initial equilibrium distributions. These results suggest a new general strategy for designing more efficient engines. We illustrate our ideas by using simple examples. -- Highlights: ► Derived efficiency bounds for heat engines working with a single reservoir. ► Analyzed both ergodic and non-ergodic engines. ► Showed that non-ergodic engines can be more efficient. ► Extended fundamental thermodynamic relation to arbitrary nonequilibrium processes

  8. Nonequilibrium Phase Transitions Associated with DNA Replication

    2011-02-11

    polymerases) catalyzing the growth of a DNA primer strand (the nascent chain of nucleotides complementary to the template strand) based on the Watson ...the fraction (error rate) of monomers for which y, where y is the correct Watson - Crick complementary base of , can be obtained by ¼ X...Nonequilibrium Phase Transitions Associated with DNA Replication Hyung-June Woo* and Anders Wallqvist Biotechnology High Performance Computing

  9. Nonequilibrium statistical averages and thermo field dynamics

    Marinaro, A.; Scarpetta, Q.

    1984-01-01

    An extension of thermo field dynamics is proposed, which permits the computation of nonequilibrium statistical averages. The Brownian motion of a quantum oscillator is treated as an example. In conclusion it is pointed out that the procedure proposed to computation of time-dependent statistical average gives the correct two-point Green function for the damped oscillator. A simple extension can be used to compute two-point Green functions of free particles

  10. Heavy metal sorption by microalgae

    Sandau, E.; Sandau, P.; Pulz, O.

    1996-01-01

    Viable microalgae are known to be able to accumulate heavy metals (bioaccumulation). Against a background of the increasing environmental risks caused by heavy metals, the microalgae Chlorella vulgaris and Spirulina platensis and their potential for the biological removal of heavy metals from aqueous solutions were taken as an example for investigation. Small-scale cultivation tests (50 l) with Cd-resistant cells of Chlorella vulgaris have shown that approx. 40% of the added 10 mg Cd/l was removed from the solution within seven days. At this heavy metal concentration sensitive cells died. Non-viable microalgae are able to eliminate heavy metal ions in a short time by biosorption in uncomplicated systems, without any toxicity problems. Compared with original biomasses, the sorption capacity of microalgal by-products changes only insignificantly. Their low price makes them economical. (orig.)

  11. Metal Sorption to Dolomite Surfaces

    Brady, P.V.; Papenguth, H.W.; Kelly, J.W.

    1999-01-01

    Potential human intrusion into the Waste Isolation Pilot Plant (WIPP) might release actinides into the Culebra Dolomite where sorption reactions will affect of radiotoxicity from the repository. Using a limited residence time reactor the authors have measured Ca, Mg, Nd adsorption/exchange as a function of ionic strength, P CO2 , and pH at 25 C. By the same approach, but using as input radioactive tracers, adsorption/exchange of Am, Pu, U, and Np on dolomite were measured as a function of ionic strength, P CO2 , and pH at 25 C. Metal adsorption is typically favored at high pH. Calcium and Mg adsorb in near-stoichiometric proportions except at high pH. Adsorption of Ca and Mg is diminished at high ionic strengths (e.g., 0.5M NaCl) pointing to association of Na + with the dolomite surface, and the possibility that Ca and Mg sorb as hydrated, outer-sphere complexes. Sulfate amplifies sorption of Ca and Mg, and possibly Nd as well. Exchange of Nd for surface Ca is favored at high pH, and when Ca levels are low. Exchange for Ca appears to control attachment of actinides to dolomite as well, and high levels of Ca 2+ in solution will decrease Kds. At the same time, to the extent that high P CO2 increase Ca 2+ levels, JK d s will decrease with CO 2 levels as well, but only if sorbing actinide-carbonate complexes are not observed to form (Am-carbonate complexes appear to sorb; Pu-complexes might sorb as well; U-carbonate complexation leads to desorption). This indirect CO 2 effect is observed primarily at, and above, neutral pH. High NaCl levels do not appear to affect to actinide K d s

  12. Sorption of methylxanthines by different sorbents

    Dmitrienko, S. G.; Andreeva, E. Yu.; Tolmacheva, V. V.; Terent'eva, E. A.

    2013-05-01

    Sorption of caffeine, theophylline, theobromine, diprophylline, and pentoxyphylline on different sorbents (supercross-linked polystyrene, surface-modified copolymer of styrene and divinylbenzene Strata-X, and carbon nanomaterials Taunit and Diasorb-100-C16T) was studied in a static mode in an effort to find new sorbents suitable for sorption isolation and concentration of methylxanthines. The peculiarities of sorption of methylxanthines were explained in relation to the solution acidity, the nature of the sorbates and their concentration, the nature of the solvent, and the structural characteristics of the sorbents.

  13. Sorption isolation of strontium from seawater

    Avramenko, V.A.; Zheleznov, V.V.; Kaplun, E.V.; Sokol'nitskaya, T.A.; Yukhkam, A.A.

    2001-01-01

    Sorption isolation of strontium from seawater is considered and prospects of use of selective adsorbents for purification of seawater or liquid radioactive wastes mixed with seawater from 90 Sr are discussed. Comparative analysis of sorptive properties of adsorbents of different nature is done. It is shown that sorption-reagent materials developed by authors can to afford effective separation of 90 Sr from seawater. Possible mechanism of strontium sorption by these adsorbents is considered. The prospect of their use for purification of liquid radioactive wastes from strontium is shown [ru

  14. Effects of oil dispersant on solubilization, sorption and desorption of polycyclic aromatic hydrocarbons in sediment–seawater systems

    Zhao, Xiao; Gong, Yanyan; O’Reilly, S.E.; Zhao, Dongye

    2015-01-01

    Highlights: • Oil dispersant enhances solubilization of PAHs more effectively than surfactants. • Dispersant and dispersed oil enhance sediment sorption of PAHs and induce hysteresis. • Partitioning to sediment-sorbed dispersant is the mechanism for enhanced PAH uptake. • Dual-mode models well simulate dispersant-facilitated sorption of PAHs on sediment. • Deepwater conditions reduce solubilization of PAHs and lessen dispersant effects. - Abstract: This work investigated effects of a prototype oil dispersant on solubilization, sorption and desorption of three model PAHs in sediment–seawater systems. Increasing dispersant dosage linearly enhanced solubility for all PAHs. Conversely, the dispersant enhanced the sediment uptake of the PAHs, and induced significant desorption hysteresis. Such contrasting effects (adsolubilization vs. solubilization) of dispersant were found dependent of the dispersant concentration and PAH hydrophobicity. The dual-mode models adequately simulated the sorption kinetics and isotherms, and quantified dispersant-enhanced PAH uptake. Sorption of naphthalene and 1-methylnaphthalene by sediment positively correlated with uptake of the dispersant, while sorption of pyrene dropped sharply when the dispersant exceeded its critical micelle concentration (CMC). The deepwater conditions diminished the dispersant effects on solubilization, but enhanced uptake of the PAHs, albeit sorption of the dispersant was lowered. The information may aid in understanding roles of dispersants on distribution, fate and transport of petroleum PAHs in marine systems

  15. Differences in sorption behavior of the herbicide 4-chloro-2-methylphenoxyacetic acid on artificial soils as a function of soil pre-aging.

    Waldner, Georg; Friesl-Hanl, Wolfgang; Haberhauer, Georg; Gerzabek, Martin H

    The sorption behavior of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) to three different artificial soil mixtures was investigated. Artificial soils serve as model systems for improving understanding of sorption phenomena. The soils consisted of quartz, ferrihydrite, illite, montmorillonite, and charcoal. In a previous study, several selected mixtures had been inoculated with organic matter, and microbial aging (incubation) had been performed for different periods of time (3, 12, and 18 months) before conducting the sorption experiments. The effect of this pre-incubation time on the sorption behavior was determined. Interaction of MCPA with soil surfaces was monitored by aqueous phase sorption experiments, using high-performance liquid chromatography/ultraviolet and in selected cases Fourier-transformed infrared spectroscopy. The sorption behavior showed large differences between differently aged soils; Freundlich and linear sorption model fits (with sorption constants K f , 1/ n exponents, and K d values, respectively) were given for pH = 3 and the unbuffered pH of ∼7. The largest extent of sorption from diluted solutions was found on the surfaces with a pre-incubation time of 3 months. Sorption increased at acidic pH values. Regarding the influence of aging of artificial soils, the following conclusions were drawn: young artificial soils exhibit stronger sorption at lower concentrations, with a larger K f value than aged soils. A correlation with organic carbon content was not confirmed. Thus, the sorption characteristics of the soils are more influenced by the aging of the organic carbon than by the organic carbon content itself.

  16. Nonequilibrium Statistical Operator Method and Generalized Kinetic Equations

    Kuzemsky, A. L.

    2018-01-01

    We consider some principal problems of nonequilibrium statistical thermodynamics in the framework of the Zubarev nonequilibrium statistical operator approach. We present a brief comparative analysis of some approaches to describing irreversible processes based on the concept of nonequilibrium Gibbs ensembles and their applicability to describing nonequilibrium processes. We discuss the derivation of generalized kinetic equations for a system in a heat bath. We obtain and analyze a damped Schrödinger-type equation for a dynamical system in a heat bath. We study the dynamical behavior of a particle in a medium taking the dissipation effects into account. We consider the scattering problem for neutrons in a nonequilibrium medium and derive a generalized Van Hove formula. We show that the nonequilibrium statistical operator method is an effective, convenient tool for describing irreversible processes in condensed matter.

  17. PCB congener sorption to carbonaceous sediment components: Macroscopic comparison and characterization of sorption kinetics and mechanism

    Choi, Hyeok; Al-Abed, Souhail R.

    2009-01-01

    Sorption of polychlorinated biphenyls (PCBs) to sediment is a key process in determining their mobility, bioavailability, and chemical decomposition in aquatic environments. In order to examine the validity of currently used interpretation approaches for PCBs sorption, comparative results on 2-chlorobiphenyl sorption to carbonaceous components in sediments (activated carbon, carbon black, coal, soot, graphite, flyash, wood) were macroscopically correlated with the structural, morphological, crystallographic, and compositional properties of the carbonaceous components. Since the Freundlich sorption constant, K F (L kg -1 ) spanned several orders of magnitude, ranging from log K F of 6.13-5.27 for activated carbon, 5.04 for carbon black, 3.83 for coal to 3.08 for wood, organic carbon partitioning approach should be more specifically categorized, considering the various forms, nature and origins of organic carbon in sediment. Sorption rate constants and fraction parameters, which were numerically defined from empirical kinetic model with fast and slow sorption fractions, were closely related to the physicochemical properties of the carbonaceous components. Sorption interpretation approaches with a specific property and viewpoint, such as organic carbon partitioning, soot carbon distribution, or surface area correlation, did not properly explain the overall results on sorption capacity, fast and slow sorption kinetics, and partitioning coefficient. It is also important to emphasize the heterogeneous nature of sediment and the difficulties of encompassing the partitioning among its carbonaceous components.

  18. PCB congener sorption to carbonaceous sediment components: Macroscopic comparison and characterization of sorption kinetics and mechanism

    Choi, Hyeok [National Risk Management Research Laboratory, U.S. Environmental Protection Agency, 26 West Martin Luther King Drive, Cincinnati, OH 45268 (United States); Al-Abed, Souhail R., E-mail: al-abed.souhail@epa.gov [National Risk Management Research Laboratory, U.S. Environmental Protection Agency, 26 West Martin Luther King Drive, Cincinnati, OH 45268 (United States)

    2009-06-15

    Sorption of polychlorinated biphenyls (PCBs) to sediment is a key process in determining their mobility, bioavailability, and chemical decomposition in aquatic environments. In order to examine the validity of currently used interpretation approaches for PCBs sorption, comparative results on 2-chlorobiphenyl sorption to carbonaceous components in sediments (activated carbon, carbon black, coal, soot, graphite, flyash, wood) were macroscopically correlated with the structural, morphological, crystallographic, and compositional properties of the carbonaceous components. Since the Freundlich sorption constant, K{sub F} (L kg{sup -1}) spanned several orders of magnitude, ranging from log K{sub F} of 6.13-5.27 for activated carbon, 5.04 for carbon black, 3.83 for coal to 3.08 for wood, organic carbon partitioning approach should be more specifically categorized, considering the various forms, nature and origins of organic carbon in sediment. Sorption rate constants and fraction parameters, which were numerically defined from empirical kinetic model with fast and slow sorption fractions, were closely related to the physicochemical properties of the carbonaceous components. Sorption interpretation approaches with a specific property and viewpoint, such as organic carbon partitioning, soot carbon distribution, or surface area correlation, did not properly explain the overall results on sorption capacity, fast and slow sorption kinetics, and partitioning coefficient. It is also important to emphasize the heterogeneous nature of sediment and the difficulties of encompassing the partitioning among its carbonaceous components.

  19. On nonequilibrium many-body systems. 1: The nonequilibrium statistical operator method

    Algarte, A.C.S.; Vasconcellos, A.R.; Luzzi, R.; Sampaio, A.J.C.

    1985-01-01

    The theoretical aspects involved in the treatment of many-body systems strongly departed from equilibrium are discussed. The nonequilibrium statistical operator (NSO) method is considered in detail. Using Jaynes' maximum entropy formalism complemented with an ad hoc hypothesis a nonequilibrium statistical operator is obtained. This approach introduces irreversibility from the outset and we recover statistical operators like those of Green-Mori and Zubarev as particular cases. The connection with Generalized Thermodynamics and the construction of nonlinear transport equations are briefly described. (Author) [pt

  20. Improved understanding of tributyltin sorption on natural and biochar-amended sediments.

    Xiao, Xiaoyu; Sheng, G Daniel; Qiu, Yuping

    2011-12-01

    A poor understanding of tributyltin (TBT) sorption on sediments has hindered an accurate evaluation of its environmental fate. The present study determined TBT sorption by a freshwater sediment (BH) and a coastal marine sediment (TZ) as influenced by pH, salinity, and biochar (BC) amendment into TZ. The isotherms were essentially linear, with K(OC) values in the range of 10(4) to 10(5) L/kg. Tributyltin sorption at pH 3.56 and 8.00 occurred mainly via partitioning. It reached maxima at pH equal to its pK(a) (=6.25) because of added ion exchange. A salinity increase from 5 to 35 practical salinity units enhanced TBT sorption at pH 3.56 and 8.00 on TZ by approximately 30% and on BH by approximately 80%, ascribed to the salting-out effect that reduced the solubilities of tributyltin hydroxide (TBTOH) and tributyltin chloride (TBTCl). At pH 6.25, the same salinity increase reduced TBT sorption on TZ by approximately 20% but enhanced TBT sorption on BH by approximately 35%. This was attributed to the enhancing role of salting out and the reducing role of metal competition for ion exchange. Tributyltin was two orders of magnitude more effectively sorbed by BC than by total organic carbon of TZ, mainly because of the high level of surface area of the BC. Although BC affinity for TBT may be significantly diminished when present in TZ, it was considered to be the primary contributor to TBT sorption from water. Biochar may thus be used to immobilize TBT in sediment for potential remediation. Copyright © 2011 SETAC.

  1. Behavior of Cs in Grimsel granodiorite. Sorption on main minerals and crushed rock

    Muuri, Eveliina; Ikonen, Jussi; Matara-aho, Minja; Voutilainen, Mikko; Siitari-Kauppi, Marja [Helsinki Univ. (Finland). Dept. of Chemistry; Lindberg, Antero [Geological Survey of Finland, Espoo (Finland); Holgersson, Stellan [Chalmers University of Technology, Goeteborg (Sweden). Dept. of Chemical and Biological Engineering, Nuclear Chemistry; Martin, Andrew [Nagra (National Cooperative for the Disposal of Radioactive Waste), Wettingen (Switzerland)

    2016-11-01

    In this study the sorption of cesium was investigated on four different minerals; quartz, plagioclase, potassium feldspar and biotite as well as granodiorite obtained from the Grimsel test site in Switzerland. The experiments were conducted in the presence of the weakly saline Grimsel groundwater simulant by determining the distribution coefficients using batch sorption experiments and PHREEQC-modelling across a large concentration range. In addition, the purity of the minerals was measured by XRD and the specific surface areas by BET method using krypton. The distribution coefficients of cesium were largest on biotite (0.304±0.005 m{sup 3}/kg in 10{sup -8} M). Furthermore, the sorption of cesium on quartz was found to be negligibly small in all investigated concentrations and the sorption of cesium on potassium feldspar and plagioclase showed similar behavior against a concentration isotherm with distribution coefficients of 0.0368±0.0004 m{sup 3}/kg and 0.18±0.04 m{sup 3}/kg in 10{sup -8} M. Finally, cesium sorption behavior on crushed granodiorite followed the trend of one of its most abundant mineral, plagioclase with distribution coefficient values of 0.107±0.003 m{sup 3}/kg in 10{sup -8} M. At low concentrations (<1.0.10{sup -6} M) cesium was sorbed on the frayed edge sites of biotite and once these sites are fully occupied cesium sorbs additionally to the Type II and Planar sites. As a consequence, the sorption of cesium on biotite is decreased at concentrations >1.0.10{sup -6} M. Secondly cesium sorption on potassium feldspar and plagioclase showed similar non-linear behavior with varying concentration. The results were used to assist the interpretation of cesium diffusion process in the 2.5 year in-situ experiment carried out in the underground laboratory at Grimsel test site in Switzerland (2007-2009).

  2. Sorption behavior of nonylphenol (NP) on sewage-irrigated soil: Kinetic and thermodynamic studies

    Liao, Xiaoping; Zhang, Caixiang; Yao, Linlin; Li, Jiale; Liu, Min; Xu, Liang; Evalde, Mulindankaka

    2014-01-01

    The reuse of wastewater for irrigation of agricultural land is a well established resources management practice but has the disadvantage of inputting various forms of contaminants into the terrestrial environment including nonylphenol (NP), a well known endocrine disrupting substance. To elucidate the environmental fate and transport of NP, the sorption behavior on sewage-irrigated soil was studied by batch experiment. It was found that sorption processes of NP on different sorbents (soil, humic acid (HA) and silica) could be expressed well using two compartment pseudo first-order model, where both surface and intra-particle diffusion were probable rate-controlling processes. Linear model could better express the sorption of NP on soil, black carbon (BC) and mineral (e.g., SiO 2 ) except HA than Freundlich model. The large value of distribution coefficients of normalized organic carbon (K oc ) on soils indicated that NP was limited to migrate to deep soil. The higher desorption partition coefficient of NP on soil showed enhanced hysteresis. According to the experimental data, the calculated thermodynamic parameters implied that the sorption reaction on sewage-irrigation was spontaneous, exothermic and entropy decreasing process. The amount of soil organic matter (SOM) dominated the sorption capacity, whereas the sorption behavior of NP on soil showed no significant correlation with ionic strength. - Highlights: • Both surface and intra-particle diffusion were rate-controlling processes. • Soil composition influences the partition activity of NP. • Soil organic matter has dominated the sorption capacity of NP on soil. • NP molecule was limited to migrate to deep soil in sewage-irrigated area

  3. Carbon dioxide sorption on EDTA modified halloysite

    Waszczuk Patrycja

    2016-01-01

    Full Text Available In this paper the sorption study of CO2 on EDTA surface modified halloysite was conducted. In the paper chemical modification of halloysite from the Dunino deposit (Poland and its influence on sorption of CO2 are presented. A halloysite samples were washed with water-EDTA 1% solution, centrifuged to separate liquid and impurities and dried. The samples were tested for the sorption capacity using a manometric method with pressure up to 3 MPa. A Langmuir adsorption model was fitted to the data. The results showed that EDTA had a limited effect on the increase of sorption potential at low pressure and the samples exhibited similar results to that ones treated solely with the water solution.

  4. Sorption of metaldehyde using granular activated carbon

    S. Salvestrini

    2017-09-01

    Full Text Available In this work, the ability of granular activated carbon (GAC to sorb metaldehyde was evaluated. The kinetic data could be described by an intra-particle diffusion model, which indicated that the porosity of the sorbent strongly influenced the rate of sorption. The analysis of the equilibrium sorption data revealed that ionic strength and temperature did not play any significant role in the metaldehyde uptake. The sorption isotherms were successfully predicted by the Freundlich model. The GAC used in this paper exhibited a higher affinity and sorption capacity for metaldehyde with respect to other GACs studied in previous works, probably as a result of its higher specific surface area and high point of zero charge.

  5. Study of sorption of technetium on pyrrhotine

    Shen Dong; Fan Xianhua; Su Xiguang; Zeng Jishu

    2001-01-01

    The sorption behaviors of technetium on pyrrhotine are studied with batch experiment and dilute sulfuric acid is used to dissolve the technetium adsorbed on pyrrhotine. Sorption and desorption experiment are performed under aerobic and anaerobic conditions (inert gas box). The results show that a significant sorption of technetium on pyrrhotine is found under aerobic and anaerobic conditions, and the sorption on the mineral is supposed to be due to the reduction of TcO 4 - to insoluble TcO 2 ·nH 2 O. Desorption process of the sorbed technetium into dilute sulfuric acid is found to be different under aerobic and anaerobic conditions. On addition of H 2 O 2 to the leach solution a sudden increase of the technetium concentration is observed

  6. Radionuclide sorption on granitic drill core material

    Eriksen, T.E.; Locklund, B.

    1987-11-01

    Distribution ratios were determined for Sr-85, Cs-134 and Eu-152 on crushed granite and fissure coating/filling material from Stripa mines. Measurements were also carried out on intact fissure surfaces. The experimental data for Sr-85, Cs-134 on crushed material can be accomodated by a sorption model based on the assumption that the crushed material consists of porous spheres with outer and inner surfaces available for sorption. In the case of Eu-152 only sorption on the outer surfaces of the crushed material was observed. The absence of sorption on inner surfaces is most probably due to high depletion of the more strongly sorbed Eu-152 in the water phase and very low diffusivity of Eu-152 in the sorbed state. (orig./HP)

  7. Electrical Conductivity of Charged Particle Systems and Zubarev's Nonequilibrium Statistical Operator Method

    Röpke, G.

    2018-01-01

    One of the fundamental problems in physics that are not yet rigorously solved is the statistical mechanics of nonequilibrium processes. An important contribution to describing irreversible behavior starting from reversible Hamiltonian dynamics was given by D. N. Zubarev, who invented the method of the nonequilibrium statistical operator. We discuss this approach, in particular, the extended von Neumann equation, and as an example consider the electrical conductivity of a system of charged particles. We consider the selection of the set of relevant observables. We show the relation between kinetic theory and linear response theory. Using thermodynamic Green's functions, we present a systematic treatment of correlation functions, but the convergence needs investigation. We compare different expressions for the conductivity and list open questions.

  8. Dynamics of unstable sound waves in a non-equilibrium medium at the nonlinear stage

    Khrapov, Sergey; Khoperskov, Alexander

    2018-03-01

    A new dispersion equation is obtained for a non-equilibrium medium with an exponential relaxation model of a vibrationally excited gas. We have researched the dependencies of the pump source and the heat removal on the medium thermodynamic parameters. The boundaries of sound waves stability regions in a non-equilibrium gas have been determined. The nonlinear stage of sound waves instability development in a vibrationally excited gas has been investigated within CSPH-TVD and MUSCL numerical schemes using parallel technologies OpenMP-CUDA. We have obtained a good agreement of numerical simulation results with the linear perturbations dynamics at the initial stage of the sound waves growth caused by instability. At the nonlinear stage, the sound waves amplitude reaches the maximum value that leads to the formation of shock waves system.

  9. Sorption of heteropoly acids by polyurethane foam

    Dmitreinko, S.G.; Goncharova, L.V.; Runov, V.K.; Zakharov, V.N.; Aslanova, L.A.

    1997-01-01

    Sorption of oxidized and reduced forms of molybdosilicic, molybdophosphoric and molybdovanadophosphoric acids by polyurethane foam based on ethers and esters is studied. On the basis of sorption dependence on solution pH, polyurethane foam type and spectral characteristics of sorbates the suggestion has been made that in the polyurethane foam phase there are two main types of sorbent-sorbate interaction: electrostatic (ion-ion) and with hydrogen bond formation: and it is impossible to determine the contribution of every interaction

  10. Sorption of organophosphate esters by carbon nanotubes

    Yan, Wei; Yan, Li [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); Duan, Jinming [School of Environmental and Municipal Engineering, Xi’an University of Architecture and Technology, Xi’an 710055 (China); Jing, Chuanyong, E-mail: cyjing@rcees.ac.cn [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China)

    2014-05-01

    Graphical abstract: The interfacial interactions between the OPE molecules and CNTs. - Highlights: • Oxygen-containing groups on CNTs change the sorption property for OPEs. • Molecular configuration of OPEs has insignificant impact on their sorption. • Hydrophobic, π–π EDA and Brønsted acid–base interaction occurred between the CNTs and OPEs. - Abstract: Insights from the molecular-level mechanism of sorption of organophosphate esters (OPEs) on carbon nanotubes (CNTs) can further our understanding of the fate and transport of OPEs in the environment. The motivation for our study was to explore the sorption process of OPEs on multi-walled CNTs (MWCNTs), single-walled CNTs (SWCNTs) and their oxidized counterparts (O-MWCNTs and O-SWCNTs), and its molecular mechanism over a wide concentration range. The sorption isotherm results revealed that the hydrophobicity of OPEs dominated their affinities on a given CNT and the π–π electron donor–acceptor (EDA) interaction also played an important role in the sorption of aromatic OPEs. This π–π EDA interaction, verified with Raman and FT-IR spectroscopy, could restrict the radial vibration of SWCNTs and affect the deformation vibration γ(CH) bands of OPE molecules. The OPE surface coverage on CNTs, estimated using the nonlinear Dubinin–Ashtakhov model, indicated that the oxygen-containing functional groups on CNTs could interact with water molecules by H-bonding, resulting in a decrease in effective sorption sites. In addition, FTIR analysis also confirmed the occurrence of Brønsted acid–base interactions between OPEs and surface OH groups of SWCNTs. Our results should provide mechanistic insights into the sorption mechanism of OPE contaminants on CNTs.

  11. Sorption of fomesafen in Brazilian soils

    Silva,G.R.; D'Antonino,L.; Faustino,L.A.; Silva,A.A.; Ferreira,F.A.; Texeira,C.C.

    2013-01-01

    The study of the dynamics of a herbicide in the soil focus on the interactions with environmental components to obtain agronomic efficiency, ensuring selectivity to the culture and risk reduction of environmental impact. This study evaluated the sorption process of fomesafen in the Brazilian soils Ultisol, Cambisol, and Organosol. Besides soil, washed sand was used as an inert material for determination of the sorption ratio of fomesafen in the soil. The bioassay method was applied, using Sor...

  12. Kinetics of strontium sorption in calcium phosphate

    Bacic, S.; Komarov, V.F.; Vukovic, Z.

    1989-01-01

    Kinetics of strontium sorption by highly dispersed solids: tricalcium phosphate (Ca 3 (PO 4 ) 2 , TCP) and hydroxyapatite (Ca 5 (PO 4 ) 3 )H, HAP) were investigated. Analysis of sorption data was made taking into consideration composition and morphology of ultra micro particles. Conclusion is that the isomorphous strontium impurity is structurally sensitive element for calcium phosphate. It was determined that the beginning of strontium desorption corresponds to the beginning of transformation of the TCP - HAP (author)

  13. Effects of Citrate and Arginine on Sorption of Nickel to Yazd Sepiolite and Calcite

    Ahmadreza Sheikhhosseini

    2017-03-01

    , and W was the mass (g of the sorbent. The Langmuir, Freundlich and linear isotherm models were fitted to sorption data using Graphpad prism 5.0. For kinetic study,30 mL of 0.01 M CaCl2 solution, with or without 0.1 mM citrate or arginine, containing Ni at a concentration corresponding to the maximum sorption capacity of each mineral (estimated from sorption isotherms were transferred into 50-ml polyethylene centrifuge tubes containing 0.3 g of sepiolite or calcite. The suspensions were shaken (180±2 rpm, 25 °C continuously and after 0.5, 1.5, 3, 6, 12, 18 and 24 hours, corresponding tubes were centrifuged (4000×g for 10 min and supernatants were analyzed for Ni concentration by atomic absorption spectrophotometer. Using Graphpad prism 5.0, kinetic data were fitted to Pseudo-first order, pseudo-second order and power function kinetic models. Results: With or without ligands, the Langmuir model was the best description of Ni sorption to sepiolite while the linear model was the best fit of calcite data showing the physical nature of Ni sorption by this mineral. Kinetics of Ni sorption to sepiolite and calcite were best described by power function model. In the presence of citrate, both capacity and rate of sorption of Ni to sepiolite decreased. There was no considerable change in sorption of Ni to calcite. In the presence of arginine, however, sorption capacity of minerals for Ni increased. Arginine enhanced the rate of Ni sorption on all three minerals. Citrate showed opposing effects on Ni sorption kinetics depending on the studied minerals. Totally, citrate and arginine had opposite effects on sorption of Ni to sepiolite and calcite. Conclusion: Organic ligands can change sorption characteristics of the minerals. It seems that citrate decreases sorption of Ni to sepiolite but its effect on Ni sorption to calcite is negligible, while arginine increases Ni sorption to both minerals. Our results suggested that presence of citrate and arginine in soil influence Ni

  14. Enforcing conservation laws in nonequilibrium cluster perturbation theory

    Gramsch, Christian; Potthoff, Michael

    2017-05-01

    Using the recently introduced time-local formulation of the nonequilibrium cluster perturbation theory (CPT), we construct a generalization of the approach such that macroscopic conservation laws are respected. This is achieved by exploiting the freedom for the choice of the starting point of the all-order perturbation theory in the intercluster hopping. The proposed conserving CPT is a self-consistent propagation scheme which respects the conservation of energy, particle number, and spin, which treats short-range correlations exactly up to the linear scale of the cluster, and which represents a mean-field-like approach on length scales beyond the cluster size. Using Green's functions, conservation laws are formulated as local constraints on the local spin-dependent particle and the doublon density. We consider them as conditional equations to self-consistently fix the time-dependent intracluster one-particle parameters. Thanks to the intrinsic causality of the CPT, this can be set up as a step-by-step time propagation scheme with a computational effort scaling linearly with the maximum propagation time and exponentially in the cluster size. As a proof of concept, we consider the dynamics of the two-dimensional, particle-hole-symmetric Hubbard model following a weak interaction quench by simply employing two-site clusters only. Conservation laws are satisfied by construction. We demonstrate that enforcing them has strong impact on the dynamics. While the doublon density is strongly oscillating within plain CPT, a monotonic relaxation is observed within the conserving CPT.

  15. Iodine sorption by microwave irradiated hydrotalcites

    Paredes, S.P. [Universidad Autonoma de Puebla, Facultad de Ciencias Quimicas, C.P. 72570, Puebla, Pue (Mexico); Instituto Politecnico Nacional, ESIQIE, C.P. 07738, Mexico, D.F. (Mexico); Fetter, G. [Universidad Autonoma de Puebla, Facultad de Ciencias Quimicas, C.P. 72570, Puebla, Pue (Mexico)]. E-mail: geolarfetter@yahoo.com.mx; Bosch, P. [Universidad Nacional Autonoma de Mexico, Instituto de Investigaciones en Materiales, C.P. 04510, Mexico, D.F. (Mexico); Bulbulian, S. [Instituto Nacional de Investigaciones Nucleares, A.P. 18-1027, C.P. 11801, Mexico, D.F. (Mexico)

    2006-12-15

    Mg-Al hydrotalcite-like compounds (HT) were prepared by the microwave method on the one hand with ethoxide-acetylacetonate and on the other with acetylacetonate as precursors. They presented a maximum sorption capacity of 2.179 and 1.517 meq of {sup 131}I{sup -}/g of hydrotalcite respectively. When the hydrotalcites were calcined and rehydrated in a {sup 131}I{sup -} solution, iodine sorption decreased in both samples to 1.515 and 1.446, respectively. The corresponding value for nitrated hydrotalcite which was prepared by the conventional method for comparison purposes, was 0.570. The radionuclide content in hydrotalcites was determined by {gamma}-spectrometry. {sup 131}I{sup -} sorption is dependent on two main parameters: one is the type of the interlayer organic material and the second the surface area. It was found that hydrotalcites prepared with ethoxide-acetylacetonate were better sorbents for {sup 131}I{sup -} than those with acetylacetonate. Still, if the specific surface area increased, {sup 131}I{sup -}sorption increased as well; nitrated HT resulted in low specific surface area and a low sorption capacity. It is, therefore, concluded that organic residues present in the samples prepared by the microwave method favor the sorption of radioactive anions, in particular {sup 131}I{sup -} if compared with nitrated and/or carbonate interlayered hydrotalcites.

  16. Migration and sorption phenomena in packaged foods.

    Gnanasekharan, V; Floros, J D

    1997-10-01

    Rapidly developing analytical capabilities and continuously evolving stringent regulations have made food/package interactions a subject of intense research. This article focuses on: (1) the migration of package components such as oligomers and monomers, processing aids, additives, and residual reactants in to packaged foods, and (2) sorption of food components such as flavors, lipids, and moisture into packages. Principles of diffusion and thermodynamics are utilized to describe the mathematics of migration and sorption. Mathematical models are developed from first principles, and their applicability is illustrated using numerical simulations and published data. Simulations indicate that available models are system (polymer-penetrant) specific. Furthermore, some models best describe the early stages of migration/sorption, whereas others should be used for the late stages of these phenomena. Migration- and/or sorption-related problems with respect to glass, metal, paper-based and polymeric packaging materials are discussed, and their importance is illustrated using published examples. The effects of migrating and absorbed components on food safety, quality, and the environment are presented for various foods and packaging materials. The impact of currently popular packaging techniques such as microwavable, ovenable, and retortable packaging on migration and sorption are discussed with examples. Analytical techniques for investigating migration and sorption phenomena in food packaging are critically reviewed, with special emphasis on the use and characteristics of food-simulating liquids (FSLs). Finally, domestic and international regulations concerning migration in packaged foods, and their impact on food packaging is briefly presented.

  17. VALIDITY OF EXCESS ENTROPY PRODUCTION CRITERION OF THERMODYNAMIC STABILITY FOR NONEQUILIBRIUM STEADY STATES

    吴金平

    1991-01-01

    The relation between the excess entropy production criterion of thermodynamic stabilityfor nonequilibrium states and kinetic linear stability principle is discussed. It is shown thatthe condition required by the excess entropy production criterion generally is sufficient, butnot necessary to judge the system stability. The condition required by the excess entropyproduction criterion is stronger than that of the linear stability principle. Only when theproduct matrix between the linearized matrix of kinetic equations and matrix of quadraticform of second-order excess entropy is symmetric, is the condition required by the excessentropy production criterion that the steady steate is asymptotically stable (δ_xP>0) necessaryand sufficient. The counterexample given by Fox to prove that the excess entropy, (δ~2S)ss,is not a Liapunov function is incorrect. Contradictory to his conclusion, the counterexampleis just a positive one that proves that the excess entropy is a Liapunov function. Moreover,the excess entropy production criterion is not limited by symmetric conditions of the linear-ized matrix of kinetic equations. The excess entropy around nonequilibrium steady states,(δ~2S)ss, is a Liapunov function of thermodynamic system.

  18. Detailed sorption characteristics of the anti-diabetic drug metformin and its transformation product guanylurea in agricultural soils.

    Briones, Rowena M; Sarmah, Ajit K

    2018-07-15

    Detection of metformin, an antidiabetic drug and its transformation product guanylurea in various environmental matrices such as surface water and groundwater, coupled with their effects on aquatic organisms warrant an understanding of the compounds fate and behaviour in the environment. Batch studies were conducted with the aim of evaluating the sorption of these two emerging contaminants in six New Zealand agricultural soils of contrasting physico-chemical properties. Kinetic studies revealed that metformin and guanylurea sorption in Te Kowhai soil was very rapid initially achieving 90% sorption within the first 4 and 13h, respectively. Fit of several isotherm models to the measured batch sorption data showed that the hybrid models Langmuir-Freundlich and Redlich-Peterson best described the isotherms. Freundlich isotherm showed higher linearity for guanylurea (n F =0.58-0.93) in all soils compared to metformin (n F =0.25-0.71). A linear isotherm was fitted at environmentally relevant low concentrations (< 3mg/L) of target compounds and calculated values of sorption distribution coefficient (K d ) were in the range of 8.97 to 53.49L/kg for metformin and between 10.6 and 37.51L/kg for guanylurea. Sorption of both metformin and guanylurea was dependent on the soil characteristics, however, no generalisation could be made as to which had higher affinity to soils studied. Pearson's correlation and multiple regression analyses indicate that Si/Al (p=0.042) and clay (p=0.015) significantly influenced metformin K d values, whereas the soil's cation exchange capacity (p=0.024) is the single most significant factor determining guanylurea sorption in soils. It is likely that the type of minerals present in soils and its ion-exchange capacity could play an important role in metformin and guanylurea sorption, respectively. Copyright © 2018. Published by Elsevier B.V.

  19. Influence of sorption competition on sorption data for MX-80 bentonite used in performance assessment

    Bradbury, M.H.; Baeyens, B.; Marques Fernandes, M.

    2012-01-01

    Document available in extended abstract form only. In order to obtain a (quasi) mechanistic understanding of radionuclide uptake on clay minerals and argillaceous rocks, the majority of sorption experiments have been carried out on purified clay minerals such as montmorillonite and illite at trace concentrations (sorption edges), or as a function of concentration (sorption isotherms), with a single radionuclide under well-defined conditions in simple background electrolytes. As a result of such studies the 2 site proto-lysis non electrostatic surface complexation cation exchange (2SPNE SC/CE) sorption model, was developed and has been successfully applied to quantitatively describe the uptake of numerous radionuclides of differing valences as a function of pH and concentration on montmorillonite. In a deep geological repository for high level waste, stable impurities arise from many sources: they are present in the pore waters, in the tunnel back fill materials and host rock formations, they arise from the corrosion of the carbon steel canister and finally they are dissolved from the spent fuel and vitrified high level waste simultaneously with the radionuclides. These impurities, which are an integral part of a realistic repository system, can potentially compete with radionuclides for the sorption sites on the backfill materials and host rock and thus reduce their uptake on them. The influence of competitive sorption is not intrinsically included (or only partly so) in the sorption model. It is clearly an inherently important issue to quantify the influence of sorption competition on the transport of released radionuclides through the multi-barrier system in a deep repository. In this study an extreme case of a competitive sorption scenario in the near field of a HLW repository is presented. Two factors are considered: one associated with the high concentrations and the other with competitive sorption effects. The tendency in both cases is to cause a reduction in

  20. Radionuclides sorption in clay soils

    Siraky, G.; Lewis, C.; Hamlat, S.; Nollmann, C.E.

    1987-01-01

    The sorption behaviour of clay soils is examined through a parametric study of the distribution coefficient (Kd) for the radionuclides of interest, Cs and Sr. This work is a preliminary stage of the migration studies of these nuclides in a porous medium (ground of Ezeiza, Argentina) and the evaluation of radiologic impact of the removal of low and intermediate activity wastes in shallow trenches. The determination of Kd is performed by a static technique or batch. The phases are separated by centrifugation at 20000 g during 1 hour. The activity of supernatant solution of Cs-137 and Sr-85 is measured in a detecting system of I Na(Tl) well-type. Two types of parameters were changed: a) those related to the determination method: phase separation (centrifugation vs. centrifugation plus filtration); equilibrium period, ratio solid/liquid; b) those related to the geochemical system: pH of contact solution, carrier concentration, competitive ions, ionic strength, desorption. It was observed that the modification of parameters in the Kd-measurement does not change the order of magnitude of results. (Author)

  1. Simple models of equilibrium and nonequilibrium phenomena

    Lebowitz, J.L.

    1987-01-01

    This volume consists of two chapters of particular interest to researchers in the field of statistical mechanics. The first chapter is based on the premise that the best way to understand the qualitative properties that characterize many-body (i.e. macroscopic) systems is to study 'a number of the more significant model systems which, at least in principle are susceptible of complete analysis'. The second chapter deals exclusively with nonequilibrium phenomena. It reviews the theory of fluctuations in open systems to which they have made important contributions. Simple but interesting model examples are emphasised

  2. Nonequilibrium fermion production in quantum field theory

    Pruschke, Jens

    2010-01-01

    The creation of matter in the early universe or in relativistic heavy-ion collisions is inevitable connected to nonequilibrium physics. One of the key challenges is the explanation of the corresponding thermalization process following nonequilibrium instabilities. The role of fermionic quantum fields in such scenarios is discussed in the literature by using approximations of field theories which neglect important quantum corrections. This thesis goes beyond such approximations. A quantum field theory where scalar bosons interact with Dirac fermions via a Yukawa coupling is analyzed in the 2PI effective action formalism. The chosen approximation allows for a correct description of the dynamics including nonequilibrium instabilities. In particular, fermion-boson loop corrections allow to study the interaction of fermions with large boson fluctuations. The applied initial conditions generate nonequilibrium instabilities like parametric resonance or spinodal instabilities. The equations of motion for correlation functions are solved numerically and major characteristics of the fermion dynamics are described by analytical solutions. New mechanisms for the production of fermions are found. Simulations in the case of spinodal instability show that unstable boson fluctuations induce exponentially growing fermion modes with approximately the same growth rate. If the unstable regime lasts long enough a thermalization of the infrared part of the fermion occupation number occurs on time scales much shorter than the time scale on which bosonic quantum fields thermalize. Fermions acquire an excess of occupation in the ultraviolet regime compared to a Fermi-Dirac statistic characterized by a power-law with exponent two. The fermion production mechanism via parametric resonance is found to be most efficient after the instability ends. Quantum corrections then provide a very efficient particle creation mechanism which is interpreted as an amplification of decay processes. The ratio

  3. Universality in Nonequilibrium Lattice Systems Theoretical Foundations

    Ódor, Géza

    2008-01-01

    Universal scaling behavior is an attractive feature in statistical physics because a wide range of models can be classified purely in terms of their collective behavior due to a diverging correlation length. This book provides a comprehensive overview of dynamical universality classes occurring in nonequilibrium systems defined on regular lattices. The factors determining these diverse universality classes have yet to be fully understood, but the book attempts to summarize our present knowledge, taking them into account systematically.The book helps the reader to navigate in the zoo of basic m

  4. Nonequilibrium fermion production in quantum field theory

    Pruschke, Jens

    2010-06-16

    The creation of matter in the early universe or in relativistic heavy-ion collisions is inevitable connected to nonequilibrium physics. One of the key challenges is the explanation of the corresponding thermalization process following nonequilibrium instabilities. The role of fermionic quantum fields in such scenarios is discussed in the literature by using approximations of field theories which neglect important quantum corrections. This thesis goes beyond such approximations. A quantum field theory where scalar bosons interact with Dirac fermions via a Yukawa coupling is analyzed in the 2PI effective action formalism. The chosen approximation allows for a correct description of the dynamics including nonequilibrium instabilities. In particular, fermion-boson loop corrections allow to study the interaction of fermions with large boson fluctuations. The applied initial conditions generate nonequilibrium instabilities like parametric resonance or spinodal instabilities. The equations of motion for correlation functions are solved numerically and major characteristics of the fermion dynamics are described by analytical solutions. New mechanisms for the production of fermions are found. Simulations in the case of spinodal instability show that unstable boson fluctuations induce exponentially growing fermion modes with approximately the same growth rate. If the unstable regime lasts long enough a thermalization of the infrared part of the fermion occupation number occurs on time scales much shorter than the time scale on which bosonic quantum fields thermalize. Fermions acquire an excess of occupation in the ultraviolet regime compared to a Fermi-Dirac statistic characterized by a power-law with exponent two. The fermion production mechanism via parametric resonance is found to be most efficient after the instability ends. Quantum corrections then provide a very efficient particle creation mechanism which is interpreted as an amplification of decay processes. The ratio

  5. Origins of scaling relations in nonequilibrium growth

    Escudero, Carlos; Korutcheva, Elka

    2012-01-01

    Scaling and hyperscaling laws provide exact relations among critical exponents describing the behavior of a system at criticality. For nonequilibrium growth models with a conserved drift, there exist few of them. One such relation is α + z = 4, found to be inexact in a renormalization group calculation for several classical models in this field. Herein, we focus on the two-dimensional case and show that it is possible to construct conserved surface growth equations for which the relation α + z = 4 is exact in the renormalization group sense. We explain the presence of this scaling law in terms of the existence of geometric principles dominating the dynamics. (paper)

  6. Neptunium(V) sorption on kaolinite

    Amayri, S.; Jermolajev, A.; Reich, T. [Mainz Univ. (Germany). Inst. of Nuclear Chemistry

    2011-07-01

    The sorption behavior of neptunium(V) onto the clay mineral kaolinite was studied in batch experiments under different experimental conditions: [Np(V)] = 7 x 10{sup -12}-8 x 10{sup -6} M, solid-to-liquid ratio 2-20 g L{sup -1}, I = 0.1 and 0.01 M NaClO{sub 4}, pH = 6-10, ambient air and Ar atmosphere. The short-lived isotope {sup 239}Np (T{sub 1/2} = 2.36 d) was used instead of {sup 237}Np (T{sub 1/2} = 2.14 x 10{sup 6} a) to study the sorption behavior of Np(V) at environmentally-relevant concentrations, i.e., 7 x 10{sup -12} M Np. In addition, {sup 239}Np(V) served as tracer to measure sorption isotherms over six orders of magnitude in Np concentration (4.8 x 10{sup -12}-1.0 x 10{sup -4} M). The results show that Np(V) sorption on kaolinite is strongly influenced by pH, CO{sub 2}, and ionic strength. The sorption of 8 x 10{sup -6} M Np(V) at pH 9.0, and ionic strength of 0.1 M NaClO{sub 4} was proportional to the solid-to-liquid ratio of kaolinite in the range of 2-10 g L{sup -1}. In the absence of CO{sub 2}, the Np(V) uptake increased continuously with increasing pH value up to 97% at pH 10. Under ambient CO{sub 2}, the sorption of Np decreased above pH 8 up to zero at pH 10. An increase of Np(V) concentration from 7 x 10{sup -12} to 8 x 10{sup -6} M resulted in a shift of the sorption pH edge by up to one pH unit to higher pH values. The ionic strength influenced the Np(V) sorption onto kaolinite only in the presence of ambient CO{sub 2}. Under Ar atmosphere the sorption of Np(V) was independent from ionic strength, indicating the formation of inner-sphere complexes of Np(V) with kaolinite. Time-dependent batch experiments at pH 9.0 under ambient CO{sub 2} showed that the sorption of Np(V) on kaolinite is fast and fully reversible over six orders in Np(V) concentration. (orig.)

  7. Sorption behavior of neptunium on bentonite -- Effect of calcium ion on the sorption

    Kozai, Naofumi; Ohnuki, Toshihiko; Muraoka, Susumu

    1995-01-01

    The sorption behavior of neptunium on bentonite was studied with batch type sorption and desorption experiments over a pH range of 2 to 8. A series of parallel studies using Na-smectite, Ca-smectite and admixtures of Na-smectite and calcite quantified the capacity of Ca 2+ (which occurs in bentonite as an exchangeable cation of smectite and as a component of calcite) to inhibit the sorption of neptunium. The distribution coefficient (K d ) of neptunium for bentonite was constant from pH 2 to 7, while for pure Na-smectite K d increased below pH 5 due to specific sorption of neptunium on Na-smectite. Specific sorption was defined as occurring when neptunium could be desorbed by a strong acid (1 M HCl) but was stable in the presence of 1 M KCl. It was found that the quantity of neptunium sorbed on Na-smectite was inversely proportional to the concentration of Ca 2+ in solution, an effect most pronounced at pH 2+ limits the specific sorption capacity of Na-smectite for neptunium. Similarly, in the mixture of Na-smectite and calcite, sufficient Ca 2+ was solubilized to depress neptunium sorption. This investigation demonstrates that Ca 2+ contained in bentonite as exchangeable cation and released from calcite reduces the specific sorption of neptunium

  8. Gallium sorption on montmorillonite and illite colloids: Experimental study and modelling by ionic exchange and surface complexation

    Benedicto, Ana; Degueldre, Claude; Missana, Tiziana

    2014-01-01

    Highlights: • Ga sorption onto illite and montmorillonite was studied and modelled for the first time. • The developed sorption model was able to well explain Ga sorption in both clays. • Number of free parameters was reduced applying the linear free energy relationship. • Cationic exchange dominate sorption at pH < 4.5; surface complexation at higher pH. - Abstract: The migration of metals as gallium (Ga) in the environment is highly influenced by their sorption on clay minerals, as montmorillonite and illite. Given the increased usage of gallium in the industry and the medicine, the Ga-associated waste may result in environmental problems. Ga sorption experiments were carried out on montmorillonite and illite colloids in a wide range of pH, ionic strength and Ga concentration. A Ga sorption model was developed combining ionic exchange and surface complexation on the edge sites (silanol and aluminol-like) of the clay sheets. The complexation constants were estimated as far as possible from the Ga hydrolysis constants applying the linear free energy relationship (LFER), which allowed to reduce the number of free parameters in the model. The Ga sorption behaviour was very similar on illite and montmorillonite: decreasing tendency with pH and dependency on ionic strength at very acidic conditions. The experimental data modelling suggests that the Ga sorption reactions avoid the Ga precipitation, which is predicted in absence of clay colloids between pH 3.5 and 5.5. Assuming this hypothesis, clay colloids would affect Ga aqueous speciation, preventing precipitation in favour of sorption. Ga sorption on montmorillonite and illite can be explained on the basis of three main reactions: Ga 3+ exchange at very acidic conditions (pH < ∼3.8); Ga(OH) 4 - complexation on protonated weak sites in acidic-neutral conditions (between pH ∼5.2 and pH ∼7.9); and Ga(OH) 3 complexation on strong sites at basic conditions (pH > ∼7.9)

  9. Technetium sorption by stibnite from natural water

    Peretroukhine, V.; Sergeant, C.; Deves, G.; Poulain, S.; Vesvres, M.H.; Thomas, B.; Simonoff, M.

    2006-01-01

    The sorption of technetium by powdered and polished mineral stibnite Sb 2 S 3 has been investigated in simulated and natural underground waters from the Meuse/Haute-Marne region (France). The sorption by powdered stibnite has been found to be complete under both aerobic and anaerobic conditions in batch experiments. The sorption rate is higher in the absence of oxygen than under aerobic condition. Increasing the temperature from 30 C to 60 C results in a rise of the sorption rate by 9.1 and 27 times under anaerobic and aerobic conditions, respectively. The observed differences in sorption kinetics in the presence and in absence of oxygen are explained by the interaction of oxygen with sulfide ion in aerobic conditions and by the reduction of technetium(VII) by iron(II) and by other impurities present in natural water and in the mineral, and by the subsequent sorption of Tc(IV) on stibnite under anaerobic conditions. The sorption on a polished mineral surface resulted in the formation of a technetium film, probably Tc 2 S 7 , with a thickness of 1-3 μg Tc/cm 2 pH 3-6 and 4-12 μg Tc/cm 2 at 9-12. The simultaneous formation of stibnite colloids with adsorbed technetium occurs at pH 9-12. The study of the technetium film on the mineral by proton induced X-ray emission analysis showed it to be at least one order of magnitude thinner on the SiO 2 impurities than on the main Sb 2 S 3 component and the iron impurities. (orig.)

  10. Computer simulation of molecular sorption in zeolites

    Calmiano, Mark Daniel

    2001-01-01

    The work presented in this thesis encompasses the computer simulation of molecular sorption. In Chapter 1 we outline the aims and objectives of this work. Chapter 2 follows in which an introduction to sorption in zeolites is presented, with discussion of structure and properties of the main zeolites studied. Chapter 2 concludes with a description of the principles and theories of adsorption. In Chapter 3 we describe the methodology behind the work carried out in this thesis. In Chapter 4 we present our first computational study, that of the sorption of krypton in silicalite. We describe work carried out to investigate low energy sorption sites of krypton in silicalite where we observe krypton to preferentially sorb into straight and sinusoidal channels over channel intersections. We simulate single step type I adsorption isotherms and use molecular dynamics to study the diffusion of krypton and obtain division coefficients and the activation energy. We compare our results to previous experimental and computational studies where we show our work to be in good agreement. In Chapter 5 we present a systematic study of the sorption of oxygen and nitrogen in five lithium substituted zeolites using a transferable interatomic potential that we have developed from ab initio calculations. We show increased loading of nitrogen compared to oxygen in all five zeolites studied as expected and simulate adsorption isotherms, which we compare to experimental and simulated data in the literature. In Chapter 6 we present work on the sorption of ferrocene in the zeolite NaY. We show that a simulated, low energy sorption site for ferrocene is correctly located by comparing to X-ray powder diffraction results for this same system. The thesis concludes with some overall conclusions and discussion of opportunities for future work. (author)

  11. Sorption of caesium and strontium onto calcium silicate hydrate in saline groundwater

    Sugiyama, D.; Fujita, T.

    2005-01-01

    Full text of publication follows: In the concept for radioactive waste disposal in Japan, cement is a potential waste packaging and backfilling material and is expected to provide chemical containment. The sorption of radionuclides onto cement materials, which controls the aqueous concentrations of elements in the pore-water, is a very important parameter when considering the release of radionuclides from the near field of a cementitious radioactive waste repository. Many safety assessment calculations currently assume radionuclide retardation as linear sorption equilibrium and describe it with a distribution ratio (R d value). In this study, the sorption mechanism is discussed by measuring the sorption isotherm of caesium, strontium (10 -5 ∼ 10 -2 mol dm -3 ) and sodium (10 -4 ∼ 10 -1 mol dm -3 ) onto Calcium Silicate Hydrate (C-S-H gel, Ca/Si 0.65 ∼ 1.2) at a liquid:solid ratio of 100:1, to support the assumption. In addition, the competitive sorption between caesium or strontium, and sodium is studied by sorption measurements using a range of sodium chloride concentration to simulate different ionic strengths in saline groundwater. The initial and equilibrated aqueous compositions were measured in the sorption experiments and it was found that caesium, strontium and sodium were sorbed by substitution for Ca in C-S-H phases by examining the mass balance. Based on the experimental results, we propose a modelling approach in which the ion-exchange model is employed and the presence of some calcium sites with different ion-exchange log K values in C-S-H is assumed by considering the composition and the structure of C-S-H. The modelling calculation results predict the measured Rd values well and also describe the competition of sorption of caesium or strontium, and sodium in the experiments. The log K values for sorption of each cation element decreased as Ca/Si ratio of C-S-H gel increased. This agrees with the trend that C-S-H gel is negatively charged at low

  12. Nonequilibrium dynamics in an interacting Fe-C nanoparticle system

    Jönsson, P.; Hansen, Mikkel Fougt; Nordblad, P.

    2000-01-01

    Nonequilibrium dynamics in an interacting Fe-C nanoparticle sample, exhibiting a low-temperature spin-glass-like phase, has been studied by low-frequency ac susceptibility and magnetic relaxation experiments. The nonequilibrium behavior shows characteristic spin-glass features, but some qualitative...

  13. Non-equilibrium spectroscopy of high-Tc superconductors

    Krasnov, V M

    2009-01-01

    In superconductors, recombination of two non-equilibrium quasiparticles into a Cooper pair results in emission of excitation that mediates superconductivity. This is the basis of the proposed new type of 'non-equilibrium' spectroscopy of high T c superconductors, which may open a possibility for direct and unambiguous determination of the coupling mechanism of high T c superconductivity. In case of low T c superconductors, the feasibility of such the non-equilibrium spectroscopy was demonstrated in classical phonon generation-detection experiments almost four decades ago. Recently it was demonstrated that a similar technique can be used for high T c superconductors, using natural intrinsic Josephson junctions both for injection of non-equilibrium quasiparticles and for detection of the non-equilibrium radiation. Here I analyze theoretically non-equilibrium phenomena in intrinsic Josephson junctions. It is shown that extreme non-equilibrium state can be achieved at bias equal to integer number of the gap voltage, which can lead to laser-like emission from the stack. I argue that identification of the boson type, constituting this non-equilibrium radiation would unambiguously reveal the coupling mechanism of high Tc superconductors.

  14. Exploring Chemical and Thermal Non-equilibrium in Nitrogen Arcs

    Ghorui, S; Das, A K

    2012-01-01

    Plasma torches operating with nitrogen are of special importance as they can operate with usual tungsten based refractory electrodes and offer radical rich non-oxidizing high temperature environment for plasma chemistry. Strong gradients in temperature as well as species densities and huge convective fluxes lead to varying degrees of chemical non-equilibrium in associated regions. An axi-symmetric two-temperature chemical non-equilibrium model of a nitrogen plasma torch has been developed to understand the effects of thermal and chemical non-equilibrium in arcs. A 2-D finite volume CFD code in association with a non-equilibrium property routine enabled extraction of steady state self-consistent distributions of various plasma quantities inside the torch under various thermal and chemical non-equilibrium conditions. Chemical non-equilibrium has been incorporated through computation of diffusive and convective fluxes in each finite volume cell in every iteration and associating corresponding thermodynamic and transport properties through the scheme of 'chemical non-equilibrium parameter' introduced by Ghorui et. al. Recombination coefficient data from Nahar et. al. and radiation data from Krey and Morris have been used in the simulation. Results are presented for distributions of temperature, pressure, velocity, current density, electric potential, species densities and chemical non-equilibrium effects. Obtained results are compared with similar results under LTE.

  15. Pedotransfer functions for isoproturon sorption on soils and vadose zone materials.

    Moeys, Julien; Bergheaud, Valérie; Coquet, Yves

    2011-10-01

    Sorption coefficients (the linear K(D) or the non-linear K(F) and N(F)) are critical parameters in models of pesticide transport to groundwater or surface water. In this work, a dataset of isoproturon sorption coefficients and corresponding soil properties (264 K(D) and 55 K(F)) was compiled, and pedotransfer functions were built for predicting isoproturon sorption in soils and vadose zone materials. These were benchmarked against various other prediction methods. The results show that the organic carbon content (OC) and pH are the two main soil properties influencing isoproturon K(D) . The pedotransfer function is K(D) = 1.7822 + 0.0162 OC(1.5) - 0.1958 pH (K(D) in L kg(-1) and OC in g kg(-1)). For low-OC soils (OC isoproturon sorption in soils in unsampled locations should rely, whenever possible, and by order of preference, on (a) site- or soil-specific pedotransfer functions, (b) pedotransfer functions calibrated on a large dataset, (c) K(OC) values calculated on a large dataset or (d) K(OC) values taken from existing pesticide properties databases. Copyright © 2011 Society of Chemical Industry.

  16. Non-equilibrium many body dynamics

    Creutz, M.; Gyulassy, M.

    1997-01-01

    This Riken BNL Research Center Symposium on Non-Equilibrium Many Body Physics was held on September 23-25, 1997 as part of the official opening ceremony of the Center at Brookhaven National Lab. A major objective of theoretical work at the center is to elaborate on the full spectrum of strong interaction physics based on QCD, including the physics of confinement and chiral symmetry breaking, the parton structure of hadrons and nuclei, and the phenomenology of ultra-relativistic nuclear collisions related to the up-coming experiments at RHIC. The opportunities and challenges of nuclear and particle physics in this area naturally involve aspects of the many body problem common to many other fields. The aim of this symposium was to find common theoretical threads in the area of non-equilibrium physics and modern transport theories. The program consisted of invited talks on a variety topics from the fields of atomic, condensed matter, plasma, astrophysics, cosmology, and chemistry, in addition to nuclear and particle physics. Separate abstracts have been indexed into the database for contributions to this workshop

  17. Nonequilibrium dynamical mean-field theory

    Eckstein, Martin

    2009-12-21

    The aim of this thesis is the investigation of strongly interacting quantum many-particle systems in nonequilibrium by means of the dynamical mean-field theory (DMFT). An efficient numerical implementation of the nonequilibrium DMFT equations within the Keldysh formalism is provided, as well a discussion of several approaches to solve effective single-site problem to which lattice models such as the Hubbard-model are mapped within DMFT. DMFT is then used to study the relaxation of the thermodynamic state after a sudden increase of the interaction parameter in two different models: the Hubbard model and the Falicov-Kimball model. In the latter case an exact solution can be given, which shows that the state does not even thermalize after infinite waiting times. For a slow change of the interaction, a transition to adiabatic behavior is found. The Hubbard model, on the other hand, shows a very sensitive dependence of the relaxation on the interaction, which may be called a dynamical phase transition. Rapid thermalization only occurs at the interaction parameter which corresponds to this transition. (orig.)

  18. Nonequilibrium dynamical mean-field theory

    Eckstein, Martin

    2009-01-01

    The aim of this thesis is the investigation of strongly interacting quantum many-particle systems in nonequilibrium by means of the dynamical mean-field theory (DMFT). An efficient numerical implementation of the nonequilibrium DMFT equations within the Keldysh formalism is provided, as well a discussion of several approaches to solve effective single-site problem to which lattice models such as the Hubbard-model are mapped within DMFT. DMFT is then used to study the relaxation of the thermodynamic state after a sudden increase of the interaction parameter in two different models: the Hubbard model and the Falicov-Kimball model. In the latter case an exact solution can be given, which shows that the state does not even thermalize after infinite waiting times. For a slow change of the interaction, a transition to adiabatic behavior is found. The Hubbard model, on the other hand, shows a very sensitive dependence of the relaxation on the interaction, which may be called a dynamical phase transition. Rapid thermalization only occurs at the interaction parameter which corresponds to this transition. (orig.)

  19. Nonequilibrium free diffusion in seed leachate

    Ortiz G., Luis; Riquelme P., Pablo; Guzmán, R.

    2013-11-01

    In this work, we use a Schlieren-like Near Field Scattering (SNFS) setup to study nonequilibrium free diffusion behavior of a colloidal solution obtained from seeds leachate. The main objective is to compare the temporal behavior of the diffusion coefficient of seed leachate with an electric conductivity based vigor test. SNFS sizing measurements, based on Mie theory, were carried out to ensure its reliability and sensitivity. Then, we performed a typical nonequilibrium free diffusion experiment of a glycerol-water mixture. In this way, we confirmed that SNFS setup is sensitive to giant concentration fluctuations of nanocolloidal solutions. The results obtained in this stage reproduce properly the data reported elsewhere in literature. Moreover, seed leachate diffuse, in water, in a similar way that glycerol does. In both cases we used the same method (dynamic structure factor) to determine thermo-physical properties. We show that time evolution of diffusion coefficient of Lupinus Albus leachate exhibits three defined regimes as electric conductivity measurements. The results also exhibit a correspondence between the behavior of the diffusion coefficient and electric conductivity values of the two regions in the temporal range studied. Finally, we discuss biological processes involved in germination that could modulate this dependence, and the role played by the electrolytic nature of solutes.

  20. Phase transitions in nonequilibrium traffic theory

    Zhang, H.M.

    2000-02-01

    This paper uses the center difference scheme of Lax-Friedrichs to numerically solve a newly developed continuum traffic flow theory and the kinematic theory of Lighthill and Whitham, and Richards, and it studies the flow-concentration phase transitions in flow containing both shock and rarefaction waves. A homogeneous road with finite length was modeled by both theories. Numerical simulations show that both theories yield nearly identical results for two representative Riemann problems--one has a shock solution and the other a rarefaction wave solution. Their phase transition curves, however, are different: those derived from the new theory have two branches--one for acceleration flow and one for deceleration flow, whereas those derived from the LWR theory comprise a single curve--the equilibrium curve. The phase transition curves in the shock case agree well with certain experimental observations but disagree with others. This disagreement may be resolved by studying transitions among nonequilibrium states, which awaits further development of a more accurate finite difference approximation of the nonequilibrium theory.

  1. Non-equilibrium many body dynamics

    Creutz, M.; Gyulassy, M.

    1997-09-22

    This Riken BNL Research Center Symposium on Non-Equilibrium Many Body Physics was held on September 23-25, 1997 as part of the official opening ceremony of the Center at Brookhaven National Lab. A major objective of theoretical work at the center is to elaborate on the full spectrum of strong interaction physics based on QCD, including the physics of confinement and chiral symmetry breaking, the parton structure of hadrons and nuclei, and the phenomenology of ultra-relativistic nuclear collisions related to the up-coming experiments at RHIC. The opportunities and challenges of nuclear and particle physics in this area naturally involve aspects of the many body problem common to many other fields. The aim of this symposium was to find common theoretical threads in the area of non-equilibrium physics and modern transport theories. The program consisted of invited talks on a variety topics from the fields of atomic, condensed matter, plasma, astrophysics, cosmology, and chemistry, in addition to nuclear and particle physics. Separate abstracts have been indexed into the database for contributions to this workshop.

  2. Small angle neutron scattering (SANS) under non-equilibrium conditions

    Oberthur, R.C.

    1984-01-01

    The use of small angle neutron scattering (SANS) for the study of systems under non-equilibrium conditions is illustrated by three types of experiments in the field of polymer research: - the relaxation of a system from an initial non-equilibrium state towards equilibrium, - the cyclic or repetitive installation of a series of non-equilibrium states in a system, - the steady non-equilibrium state maintained by a constant dissipation of energy within the system. Characteristic times obtained in these experiments with SANS are compared with the times obtained from quasi-elastic neutron and light scattering, which yield information about the equilibrium dynamics of the system. The limits of SANS applied to non-equilibrium systems for the measurement of relaxation times at different length scales are shown and compared to the limits of quasielastic neutron and light scattering

  3. Sorption of cesium in intact rock

    Puukko, E.

    2014-04-01

    The mass distribution coefficient K d is used in performance assessment (PA) to describe sorption of a radionuclide on rock. The R d is determined using crushed rock which causes uncertainty in converting the R d values to K d values for intact rock. This work describes a method to determine the equilibrium of sorption on intact rock. The rock types of the planned Olkiluoto waste disposal site were T-series mica gneiss (T-MGN), T-series tonalite granodiorite granite gneiss (T-TGG), P-series tonalite granodiorite granite gneiss (P-TGG) and pegmatitic granite (PGR). These rocks contain different amount of biotite which is the main sorbing mineral. The sorption of cesium on intact rock slices was studied by applying an electrical field to speed up migration of cesium into the rock. Cesium is in the solution as a noncomplex cation Cs + and it is sorbed by ion exchange. The tracer used in the experiments was 134 Cs. The experimental sorption on the intact rock is compared with values calculated using the in house cation exchange sorption model (HYRL model) in PHREEQC program. The observed sorption on T-MGN and T-TGG rocks was close to the calculated values. Two PGR samples were from a depth of 70 m and three samples were from a depth of 150 m. Cesium sorbed more than predicted on the two 70 m PGR samples. The sorption of Cs on the three 150 m PGR samples was small which was consistent with the calculations. The pegmatitic granite PGR has the smallest content of biotite of the four rock types. In the case of P-TGG rock the observed values of sorption were only half of the calculated values. Two kind of slices were cut from P-TGG drill core. The slices were against and to the direction of the foliation of the biotite rims. The sorption of cesium on P-TGG rock was same in both cases. The results indicated that there was no effect of the directions of the electric field and the foliation of biotite in the P-TGG rock. (orig.)

  4. Recent progress in sorption mechanisms and models

    Fedoroff, M.; Lefevre, G.

    2005-01-01

    Full text of publication follows: Sorption-desorption phenomena play an important role in the migration of radioactive species in surface and underground waters. In order to predict the transport of these species, we need a good knowledge of sorption processes and data, together with reliable models able to be included in transport calculation. Traditional approaches based on experimentally determined distribution coefficients (Kd) and sorption isotherms have a limited predictive capability, since they are very sensitive to the numerous parameters characterizing the solution and the solid. Models based on thermodynamic equilibria were developed to account for the influence these parameters: the ion exchange model and the surface complexation models (2-pK mono-site, 1-pK multi-site, with several different electrostatic models: CCM, DLM, BSM, TLM,...). Although these models are very useful, studies performed in recent years showed that they have important theoretical and experimental limitations, which result in the fact that we must be very careful when we use them for extrapolating sorption data to long term and to large natural systems. Among all problems which can be found are: the possibility to fit a set of experimental data with different models, sometimes bad adequacy with the real sorption processes, some theoretical limitations such as a rigorous definition of reference and standard states in surface equilibria, slow kinetics which prevent from equilibrium achievement, irreversibility, solubility and evolution of solid phases... Through the increase of the number of sensitive spectroscopic methods, we are now able to know more about sorption processes at the atomic scale. Models such as the 1-pK CD-MUSIC model can account for the influence of orientation of the faces of the solid. More and more examples of the influence of this orientation on the sorption properties are known. Calculations performed by 'ab initio' modeling is also useful to predict the

  5. The NEA sorption data base (SDB)

    Ruegger, B.; Ticknor, K.

    1992-01-01

    The current NEA Sorption Data Base is developed to replace the former International Sorption Information Retrieval System (ISIRS) initiated at Pacific Northwest Laboratory and contains about 11,000 distribution coefficients with corresponding experimental condition parameters describing sorption of key nuclides for a large variety of solid and liquid phases. The SDB is designed to run on a micro-computer using the commercially available database software dBASE III Plus. For each recorded sorption experiment, the SDB provides a bibliographical reference, the most complete characterization of the solid and liquid phases available, a description of the experimental conditions and the distribution coefficient or retardation factor for each element studied. When available, parameters such as temperature, initial radionuclide concentration, pH, Eh, contact time, solid to solution ratio, sample origin, oxidation state and type of solution are included. The SDB provides information for a wide variety of rocks or geological materials, buffer backfill candidates, concretes/cements, elements (Am, Cs, Co, I, Np, Pu, Ra, Sr, Se, Tc, U and, to a lesser extent, Ag, Ba, C, Ce, Eu, Fe, Mn, Mo, Na, Nb, Ni, Pd, Pm, Ru, Sb, Sn, Y, Zn, and Zr), or radioisotopes. A compilation of sorption data like SDB provide a readily available source of data for radioactive waste repository performance assessments when site specific data are not available or essential, for example, during a site selection phase. 2 appendices

  6. Radionuclide sorption from the safety evaluation perspective

    1992-01-01

    Research and development directed towards the assessment of the long-term performance of radioactive waste disposal systems has been recognised as a priority area with a strong need for international co-operation and co-ordination. The ultimate aims is to promote the quality and credibility of safety assessment techniques for radioactive waste disposal. Sorption in the geosphere is one of the key processes for retarding the transport of radionuclide from the underground disposal facility to the biosphere. In many cases, sorption in the near field and in the biosphere is also important. A workshop, organised to favor discussion around a small number of invited papers, was held in October 1991: - to evaluate critically the way sorption processes are incorporated in performance assessment models; - to identify open issues of high priority, and; - to propose future activities to resolve these issues. These proceedings reproduce the invited papers and the conclusions and recommendations adopted by the workshop. Eight papers are in the INIS SCOPE. The main subjects studied are: sorption database comparison, sorption database development and three case studies, experimental techniques, adsorption models

  7. Sorption of radionuclides by tertiary clays

    Wagner, J.F.; Czurda, K.A.

    1990-01-01

    The sorption capacity of different clay types for some metals (Co, Cs, Sr and Zn), occurring as common radionuclides in radioactive waste deposits, had been analysed by a static (batch technique) and a dynamic method (percolation tests, in which the driving force is a hydraulic gradient). Sorption capacity generally increased with an increasing pH of solution. A decrease of sorption capacity had been observed in the order Zn > Cs ≥ Co > Sr for the batch and Cs > Zn > Sr > Co for the percolation tests. Clay marls showed a distinctly higher sorption respectively retention capacity as pure clays. Sorption capacity depends on solution parameters like type and concentration of radionuclide, pH, salt concentration, etc., and on rock parameters like mineral content (e.g. swelling clay minerals and carbonates), organic material, rock pH, micro fabric, etc. A third parameter of great influence is the contact time between clay and solution. The adsorption isotherms reflect two different adsorption mechanisms: a very rapid adsorption (a few minutes) on the external surfaces of clay minerals and a slow adsorption process (weeks and longer), due to the diffusion of metal ions into the interlayer space of clay minerals. 12 refs., 9 figs., 1 tab

  8. Temperature in non-equilibrium states: a review of open problems and current proposals

    Casas-Vazquez, J; Jou, D

    2003-01-01

    The conceptual problems arising in the definition and measurement of temperature in non-equilibrium states are discussed in this paper in situations where the local-equilibrium hypothesis is no longer satisfactory. This is a necessary and urgent discussion because of the increasing interest in thermodynamic theories beyond local equilibrium, in computer simulations, in non-linear statistical mechanics, in new experiments, and in technological applications of nanoscale systems and material sciences. First, we briefly review the concept of temperature from the perspectives of equilibrium thermodynamics and statistical mechanics. Afterwards, we explore which of the equilibrium concepts may be extrapolated beyond local equilibrium and which of them should be modified, then we review several attempts to define temperature in non-equilibrium situations from macroscopic and microscopic bases. A wide review of proposals is offered on effective non-equilibrium temperatures and their application to ideal and real gases, electromagnetic radiation, nuclear collisions, granular systems, glasses, sheared fluids, amorphous semiconductors and turbulent fluids. The consistency between the different relativistic transformation laws for temperature is discussed in the new light gained from this perspective. A wide bibliography is provided in order to foster further research in this field

  9. Sorption of heavy metals by the soil fungi 'Aspergillus niger' and Mucor rouxii

    Mullen, M.D.; Wolf, D.C.; Beveridge, T.J.; Bailey, G.W.

    1992-01-01

    Sorption of the nitrate salts of cadmium(II), copper(II), lanthanum(III) and silver(I) by two fungi, Aspergillus niger and Mucor rouxii, was evaluated using Freundlich adsorption isotherms and energy dispersive X-ray electron microscopy. The linearized Freundlich isotherm described the metal sorption data well for metal concentrations of 5 microM-1 mM metal. Differences in metal binding were observed among metals, as well as between fungal species. Calculated Freundlich K values indicated that metal binding decreased in the order La(3+) > or = Ag(+) > Cu(2+) > Cd(2+). However, sorption of Ag(+) was greater than that of La(3+) from solutions of 0.1 and 1 mM metal and likely due to precipitation at the cell wall surface. At the 1 mM initial concentration, there were no significant differences between the two fungi in metal sorption, except for Ag(+) binding. At the 5 microM concentration, there was no difference between the fungi in their sorption capacities for the four metals. Electron microscopy-energy dispersive X-ray analysis indicated that silver precipitated onto cells as colloidal silver. The results indicate that Freundlich isotherms may be useful for describing short-term metal sorption by fungal biomass and for comparison with other soil constituents in standardized systems. (Copyright (c) 1992 Pergamon Press plc.)

  10. How the sorption of benzene in soils contaminated with aromatic hydrocarbons is affected by the presence of biofuels

    Maria Manuela Carvalho

    2015-04-01

    Full Text Available The increasing use of biofuels as additives to gasoline may have potential indirect effects on the efficiency of soil remediation technologies used to remediate fuel spills. This problem has not yet been studied. Sorption is one of the controlling processes in soil remediation. The effect of biofuels on sorption and phase distribution of contaminants by different natural soils has not been reported on the literature. The present work examines how two different biofuels, n-butanol and soybean biodiesel, affect benzene sorption in two naturally occurring subsoils (granite and limestone. Sorption isotherms were made with soils deliberately contaminated with benzene, benzene and n-butanol and benzene plus biodiesel, using lab-scale reactors operated at constant temperature, each one loaded with 700 grams of wet sterilized soil. For each type of soil, five isotherms were determined corresponding to different contamination profiles. It was concluded that sorption was strongly affected by the nature of the soil. The partition of benzene into the different phases of the soil was significantly affected by the presence of biofuels. The experimental data was fitted to conventional sorption models, Freundlich, Langmuir and a second order polynomial. Model parameters were determined using a non-linear least squares (NLLS optimization algorithm and showed a good agreement between experimental and fitted data.

  11. Influence of soil properties on vapor-phase sorption of trichloroethylene

    Bekele, Dawit N.; Naidu, Ravi; Chadalavada, Sreenivasulu

    2016-01-01

    Highlights: • Vapor intrusion is a major exposure pathway for volatile hydrocarbons. • Certainty in transport processes enhances vapor intrusion model precision. • Detailed understanding of vadose zone vapor transport processes save resources. • Vapor sorption near-steady-state conditions at sites may take months or years. • Type of clay fractions equitably affects sorption of trichloroethylene vapor. - Abstract: Current practices in health risk assessment from vapor intrusion (VI) using mathematical models are based on assumptions that the subsurface sorption equilibrium is attained. The time required for sorption to reach near-steady-state conditions at sites may take months or years to achieve. This study investigated the vapor phase attenuation of trichloroethylene (TCE) in five soils varying widely in clay and organic matter content using repacked columns. The primary indicators of TCE sorption were vapor retardation rate (R_t), the time required for the TCE vapor to pass through the soil column, and specific volume of retention (V_R), and total volume of TCE retained in soil. Results show TCE vapor retardation is mainly due to the rapid partitioning of the compound to SOM. However, the specific volume of retention of clayey soils with secondary mineral particles was higher. Linear regression analyses of the SOM and clay fraction with V_R show that a unit increase in clay fraction results in higher sorption of TCE (V_R) than the SOM. However, partitioning of TCE vapor was not consistent with the samples' surface areas but was mainly a function of the type of secondary minerals present in soils.

  12. Influence of soil properties on vapor-phase sorption of trichloroethylene

    Bekele, Dawit N. [Global Center for Environmental Remediation, University of Newcastle, Callaghan, NSW 2308 (Australia); CRC for Contamination Assessment & Remediation of the Environment, Building X (Environmental Sciences Building), University of South Australia, Mawson Lakes, SA 5095 (Australia); Naidu, Ravi, E-mail: Ravi.Naidu@newcastle.edu.au [Global Center for Environmental Remediation, University of Newcastle, Callaghan, NSW 2308 (Australia); CRC for Contamination Assessment & Remediation of the Environment, Building X (Environmental Sciences Building), University of South Australia, Mawson Lakes, SA 5095 (Australia); Chadalavada, Sreenivasulu [Global Center for Environmental Remediation, University of Newcastle, Callaghan, NSW 2308 (Australia); CRC for Contamination Assessment & Remediation of the Environment, Building X (Environmental Sciences Building), University of South Australia, Mawson Lakes, SA 5095 (Australia)

    2016-04-05

    Highlights: • Vapor intrusion is a major exposure pathway for volatile hydrocarbons. • Certainty in transport processes enhances vapor intrusion model precision. • Detailed understanding of vadose zone vapor transport processes save resources. • Vapor sorption near-steady-state conditions at sites may take months or years. • Type of clay fractions equitably affects sorption of trichloroethylene vapor. - Abstract: Current practices in health risk assessment from vapor intrusion (VI) using mathematical models are based on assumptions that the subsurface sorption equilibrium is attained. The time required for sorption to reach near-steady-state conditions at sites may take months or years to achieve. This study investigated the vapor phase attenuation of trichloroethylene (TCE) in five soils varying widely in clay and organic matter content using repacked columns. The primary indicators of TCE sorption were vapor retardation rate (R{sub t}), the time required for the TCE vapor to pass through the soil column, and specific volume of retention (V{sub R}), and total volume of TCE retained in soil. Results show TCE vapor retardation is mainly due to the rapid partitioning of the compound to SOM. However, the specific volume of retention of clayey soils with secondary mineral particles was higher. Linear regression analyses of the SOM and clay fraction with V{sub R} show that a unit increase in clay fraction results in higher sorption of TCE (V{sub R}) than the SOM. However, partitioning of TCE vapor was not consistent with the samples' surface areas but was mainly a function of the type of secondary minerals present in soils.

  13. Characterization of aqueous interactions of copper-doped phosphate-based glasses by vapour sorption.

    Stähli, Christoph; Shah Mohammadi, Maziar; Waters, Kristian E; Nazhat, Showan N

    2014-07-01

    Owing to their adjustable dissolution properties, phosphate-based glasses (PGs) are promising materials for the controlled release of bioinorganics, such as copper ions. This study describes a vapour sorption method that allowed for the investigation of the kinetics and mechanisms of aqueous interactions of PGs of the formulation 50P2O5-30CaO-(20-x)Na2O-xCuO (x=0, 1, 5 and 10mol.%). Initial characterization was performed using (31)P magic angle spinning nuclear magnetic resonance and attenuated total reflectance-Fourier transform infrared spectroscopy. Increasing CuO content resulted in chemical shifts of the predominant Q(2) NMR peak and of the (POP)as and (PO(-)) Fourier transform infrared absorptions, owing to the higher strength of the POCu bond compared to PONa. Vapour sorption and desorption were gravimetrically measured in PG powders exposed to variable relative humidity (RH). Sorption was negligible below 70% RH and increased exponentially with RH from 70 to 90%, where it exhibited a negative correlation with CuO content. Vapour sorption in 0% and 1% CuO glasses resulted in phosphate chain hydration and hydrolysis, as evidenced by protonated Q(0)(1H) and Q(1)(1H) species. Dissolution rates in deionized water showed a linear correlation (R(2)>0.99) with vapour sorption. Furthermore, cation release rates could be predicted based on dissolution rates and PG composition. The release of orthophosphate and short polyphosphate species corroborates the action of hydrolysis and was correlated with pH changes. In conclusion, the agreement between vapour sorption and routine characterization techniques in water demonstrates the potential of this method for the study of PG aqueous reactions. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  14. Sorption of cesium and strontium from concentrated brines by backfill barrier materials

    Winslow, C.D.

    1981-03-01

    The sorption of radionuclides from potentially intruding groundwater at a nuclear waste repository is a major chemical function of backfill barriers. In this study, various materials (including clays, zeolites and an inorganic ion exchanger) were screened for the sorption of the fission products cesium and strontium in concentrated brines. Representative brines A and B for the Waste Isolation Pilot Plant (WIPP), a proposed radioactive waste repository and test facility in bedded salt were used. Sorption properties were quantified using empirical distribution coefficients, k/sub d/. Of the materials examined, sodium titanate had the highest k/sub d/ for the sorption of Sr(II) in both brine A (k/sub d/ = 125 ml/g) and brine B(k/sub d/ = 500 to 600 ml/g). A mordenite-type zeolite was the most effective getter for Cs(I) in brine A (k/sub d = 27 ml/g), while illite yielded the highest k/sub d/ for Cs(I) in brine B (k/sub d/ = 115 ml/g). The relative merit of these k/sub d/ values is evaluated in terms of calculated estimates of breakthrough times for a backfill barrier containing the getter. Results show that a backfill mixture containing these getters is potentially an effective barrier to the migration of Sr(II) and Cs(I), although further study (especially for the sorption of cesium from brine A) is recommended. Initial mechanistic studies revealed competing ion effects which would support an ion exchange mechanism. K/sub d/'s were constant over a Sr(II) concentration range of 10 -11 to 10 -5 M and a Cs(I) concentration range of 10 -8 to 10 -5 M, supporting the choice of a linear sorption isotherm as a model for the results. Constant batch composition was shown to be attained within one week

  15. Sorption of Atrazine in Tropical Soil by Biochar Prepared from Cassava Waste

    Hui Deng

    2014-09-01

    Full Text Available Biochar (BC is a carbonaceous and porous product generated from the incomplete combustion of biomass and has been recognized as an efficient adsorbent. This study evaluated the ability of BC to sorb atrazine pesticide in tropical soil, and explored potential environmental values of BC on mitigating organic micro-pollutants. BC was produced from cassava waste via pyrolyzation under oxygen-limiting conditions at 350, 550, and 750 °C (MS350, MS550, and MS750, respectively. Three biochars were characterized and investigated as sorbents for the removal atrazine from tropical soil. BC pyrolyzed at higher temperatures more quickly reached equilibrium. The pseudo-second-order model perfectly simulated the sorption kinetics for atrazine with the coefficients R2 above 0.996, and the sorption amount at equilibrium (qe was 0.016 mg/g for MS350, 0.025 mg/g for MS550 and 0.050 mg/g for MS750. The isotherms of MS350 displayed relatively linear behavior, whereas the sorption of atrazine on MS550 and MS750 followed a nonlinear isotherm. The sorption data were well described by the Freundlich model with logKF of 0.476 for MS350, 0.771 for MS550, 1.865 for MS750. A thermodynamic study indicated that the sorption of atrazine in BC-added soil was a spontaneous and endothermic process and was primarily controlled by physisorption. In addition, lower pH was conducive to the sorption of atrazine in BC-added soil.

  16. Sorption kinetics of Cs and Sr in sediments of a Savannah River Site reservoir

    Stephens, J.A.

    1997-07-01

    Laboratory measurements of the sorption and desorption of 134 Cs and 85 Sr to sediments were conducted. These sediments were sampled from the profundal zone of Par Pond at the Savannah River Site, Aiken, South Carolina. The isotopes 134 Cs and 85 Sr were used to trace the sorption properties of the main contaminants found in the reservoir which are 137 Cs and 90 Sr respectively. The sorption behavior of these two elements was studied using spiked sediment/water slurries of a known mass to volume ratio. The results reveal that Sr undergoes significant reversible sorption while a fraction of Cs irreversibly sorbs to the sediment. The calculated distribution coefficient Kd at equilibrium was (3 ± 0.6) x 10 3 for 134 Cs after 60 d and (1 ± 0.2) x 10 3 for 85 Sr after 7 d at pH ∼ 6 and slurry ratio of 1:1000 g/ml. The K d for 134 Cs ranged from 2 x 10 2 to 3 x 10 4 depending on pH and conductivity. The 85 Sr reached equilibrium in a few days, while 134 Cs reached an apparent equilibrium in 1--2 months. The K d for 134 Cs was a function of the slurry ratio, pH, conductivity, and contact time. These factors were interrelated since the sediments released ions to the slurry mixture which decreased the pH and increased the conductivity. A sorption isotherm measured for 134 Cs was linear at water concentrations from 60 mBq/ml to 20 Bq/ml. A kinetic model was proposed to describe the basic sorption of 134 Cs to Par Pond sediments under homogeneous laboratory conditions

  17. Imidacloprid sorption and transport in cropland, grass buffer and riparian buffer soils

    Satkowski, Laura E.; Goyne, Keith W.; Anderson, Stephen H.; Lerch, Robert N.; Allen, Craig R.; Snow, Daniel D.

    2018-01-01

    An understanding of neonicotinoid sorption and transport in soil is critical for determining and mitigating environmental risk associated with the most widely used class of insecticides. The objective of this study was to evaluate mobility and transport of the neonicotinoid imidacloprid (ICD) in soils collected from cropland, grass vegetative buffer strip (VBS), and riparian VBS soils. Soils were collected at six randomly chosen sites within grids that encompassed all three land uses. Single-point equilibrium batch sorption experiments were conducted using radio-labeled (14C) ICD to determine solid–solution partition coefficients (Kd). Column experiments were conducted using soils collected from the three vegetation treatments at one site by packing soil into glass columns. Water flow was characterized by applying Br− as a nonreactive tracer. A single pulse of 14C-ICD was then applied, and ICD leaching was monitored for up to 45 d. Bromide and ICD breakthrough curves for each column were simulated using CXTFIT and HYDRUS-1D models. Sorption results indicated that ICD sorbs more strongly to riparian VBS (Kd = 22.6 L kg−1) than crop (Kd = 11.3 L kg−1) soils. Soil organic C was the strongest predictor of ICD sorption (p < 0.0001). The column transport study found mean peak concentrations of ICD at 5.83, 10.84, and 23.8 pore volumes for crop, grass VBS, and riparian VBS soils, respectively. HYDRUS-1D results indicated that the two-site, one-rate linear reversible model best described results of the breakthrough curves, indicating the complexity of ICD sorption and demonstrating its mobility in soil. Greater sorption and longer retention by the grass and riparian VBS soils than the cropland soil suggests that VBS may be a viable means to mitigate ICD loss from agroecosystems, thereby preventing ICD transport into surface water, groundwater, or drinking water resources.

  18. Sorption behaviour of radioactive technetium in soils

    Xia Deying

    1996-01-01

    The sorption behaviour of technetium in different soils has been studied by batch experiments under aerobic conditions. The soil samples have been taken to study the characteristics and to derive the pH-Eh values. In addition, the activated carbon and reduced iron powder have been selected as additives to the JAERI sand according to the former research work, so that the technetium sorption behaviour in the artificial soils can be studied under similar conditions. The experimental results show that all these soil samples except for the gluey soil have a very small distribution coefficient for Tc, while the artificial soils have a very large distribution coefficient for Tc. Besides, for artificial soils, the distribution coefficient (R d ) values will become larger and larger when more additive is added and more contact time is allowed. The physico-chemical fixation processes and possible sorption modes have been discussed as well

  19. Sorption of Europium in zirconium silicate

    Garcia R, G.

    2004-01-01

    Some minerals have the property of sipping radioactive metals in solution, that it takes advantage to manufacture contention barriers that are placed in the repositories of nuclear wastes. The more recent investigations are focused in the development of new technologies guided to the sorption of alpha emissors on minerals which avoid their dispersion in the environment. In an effort to contribute to the understanding of this type of properties, some studies of sorption of Europium III are presented like homologous of the americium, on the surface of zirconium silicate (ZrSiO 4 ). In this work the results of sorption experiences are presented as well as the interpretation of the phenomena of the formation of species in the surface of the zirconium silicate. (Author)

  20. Sorption of radioactive technetium on pyrrhotine

    Shen, D.; Fan, X.H.; Su, X.G.; Zeng, J.S.; Dong, Y.

    2002-01-01

    The sorption behavior of technetium on pyrrhotine was studied with batch experiments and diluted sulfuric acid (less than 2.88 mol/l) was used to dissolve the technetium adsorbed on pyrrhotine. A significant sorption of technetium on pyrrhotine was observed under aerobic and anaerobic conditions, and the sorption on the mineral was supposed to be due to the reduction of TcO 4 - to insoluble TcO 2 x nH 2 O. Sorbed technetium on the mineral could be desorbed by diluted sulfuric acid. The maximum desorption ratio under aerobic conditions was much higher than that of under anaerobic conditions, meanwhile, the desorption rates under anaerobic conditions were higher than that of under aerobic conditions in the initial stage of the experiments. (author)

  1. Water sorption and transport in dry crispy bread crust

    Meinders, M.B.J.; Nieuwenhuijzen, van N.H.; Tromp, R.H.; Hamer, R.J.; Vliet, van T.

    2010-01-01

    Water sorption and dynamical properties of bread crust have been studied using gravimetric sorption experiments. Water uptake and loss were followed while relative humidity (RH) was stepwise in- or decreased (isotherm experiment) or varied between two adjusted values (oscillatory experiment).

  2. The sorption of acids in cellular side of apple pressing

    Asoev, M.G.; Mukhiddinov, Z.K.

    1994-01-01

    Equilibrium swell of sample refuse after separation of water is use for study of sorption of hydrochloric acid. Quantity adsorb acids set a price to difference her concentration before and after equilibrium sorption

  3. Molecular simulation of polycyclic aromatic hydrocarbon sorption to black carbon

    Haftka, J.J.H.; Parsons, J.R.; Govers, H.A.J.

    2009-01-01

    Strong sorption of hydrophobic organic contaminants to soot or black carbon (BC) is an important environmental process limiting the bioremediation potential of contaminated soils and sediments. Reliable methods to predict BC sorption coefficients for organic contaminants are therefore required. A

  4. Role of Sink Density in Nonequilibrium Chemical Redistribution in Alloys

    Martínez, Enrique; Senninger, Oriane; Caro, Alfredo; Soisson, Frédéric; Nastar, Maylise; Uberuaga, Blas P.

    2018-03-01

    Nonequilibrium chemical redistribution in open systems submitted to external forces, such as particle irradiation, leads to changes in the structural properties of the material, potentially driving the system to failure. Such redistribution is controlled by the complex interplay between the production of point defects, atomic transport rates, and the sink character of the microstructure. In this work, we analyze this interplay by means of a kinetic Monte Carlo (KMC) framework with an underlying atomistic model for the Fe-Cr model alloy to study the effect of ideal defect sinks on Cr concentration profiles, with a particular focus on the role of interface density. We observe that the amount of segregation decreases linearly with decreasing interface spacing. Within the framework of the thermodynamics of irreversible processes, a general analytical model is derived and assessed against the KMC simulations to elucidate the structure-property relationship of this system. Interestingly, in the kinetic regime where elimination of point defects at sinks is dominant over bulk recombination, the solute segregation does not directly depend on the dose rate but only on the density of sinks. This model provides new insight into the design of microstructures that mitigate chemical redistribution and improve radiation tolerance.

  5. Tritium sorption on protective coatings for concrete

    Miller, J.M.; Senohrabek, J.A.; Allsop, P.A.

    1992-11-01

    Because of the high sorption level of tritium on unprotected concrete, a program to examine the effectiveness of various concrete coatings and sealants in reducing tritium sorption was undertaken, and various exposure conditions were examined. Coatings of epoxy, polyurethane, bituminous sealant, bituminous sealant covered with polyvinylidene chloride wrap, alkyd paint, and sodium silicate were investigated with tritium (HTO) vapor concentration, humidity and contact time being varied. An exposure to HT was also carried out, and the effect of humidity on the tritium desorption rate was investigated. The relative effectiveness of the coatings was in the order of bituminous sealant + wrap > bituminous sealant > solvent-based epoxy > 100%-solids epoxy > alkyd paint > sodium silicate. The commercially available coatings for concrete resulted in tritium sorption being reduced to less than 7% of unprotected concrete. This was improved to ∼0.1% with the use of the Saran wrap (polyvinylidene chloride). The amount of tritium sorbed was proportional to tritium concentration. The total tritium sorbed decreased with an increase in humidity. A saturation effect was observed with increasing exposure time for both the coated and unprotected samples. Under the test conditions, complete saturation was not achieved within the maximum 8-hour contact time, except for the solvent-based epoxy. The desorption rate increased with a higher-humidity air purge stream. HT desorbed more rapidly than HTO, but the amount sorbed was smaller. The experimental program showed that HTO sorption by concrete can be significantly reduced with the proper choice of coating. However, tritium sorption on concrete and proposed coatings will continue to be a concern until the effects of the various conditions that affect the adsorption and desorption of tritium are firmly established for both chronic and acute tritium release conditions. Material sorption characteristics must also be considered in

  6. On the derivation of a sorption database

    Ewart, F.T.; Haworth, A.; Wisbey, S.J.

    1992-01-01

    The safety arguments in support of many radioactive waste repository concepts are heavily dependent on the existence of a sorption reaction. Such a reaction will, in the near field, reduce the magnitude of the release of a number of hazardous radionuclides so that their release to the geosphere is dispersed in time. In the geosphere, the sorption reactions provide a mechanism whereby the migration of the elements released from the repository is retarded and the radioisotopes then subsequently decay. The processes involved in sorption cannot in many cases be satisfactorily represented in thermodynamic terms such as are employed in the description of dissolution and precipitation. Experiments that investigate these reactions are not easy to perform. The sorption parameters that are obtained experimentally for the near field relate, in the UK case, to sorption on to a cementitious surface. These surfaces, since they consist substantially of calcium hydroxide or calcium silicate hydrates, control the aqueous chemistry, do not permit pH changes to be made and limit the range of concentrations of sorbate that may be used. In the far field, on the other hand, the surfaces are not in general so active with respect to the solution chemistry and data can be obtained across a wide spectrum of aqueous chemistries. These data, although they may be useful in testing and parameterizing models, may not have validity under field conditions since the minerals will, inevitably, react to the changes in water chemistry, over geological timescales. The uncertainties in the experimental data are, for many elements and solids, balanced by a reasonable agreement between workers in the values of the parameters used to describe sorption. 22 refs., 1 fig., 1 tab

  7. Sorption Properties of Some Romanian Gingerbread

    Tulbure Anca

    2014-06-01

    Full Text Available Water activity of gingerbread is very important for keeping the product freshness and shelf life. Water activity is influenced by composition, water content and temperature. The water content of gingerbread could vary according with storage condition. i.e. rH. 11 gingerbread samples were analysed. The water content and water activity lies between 7.0 and 12.6% and respectively 0.590 and 0.715. The sorption isotherms were determined at 30°C by gravimetric method. The moisture sorption is influenced by composition, especially sweeteners and humectants. Honey and invert sugar have the same impact on gingerbread higroscopicity.

  8. Sorption of radionuclides on hard rocks

    Berry, J.A.; Bourke, P.J.; Green, A.; Littleboy, A.K.

    1987-09-01

    Methods for measuring sorption on hard rocks, particularly of strontium, caesium, neptunium and americium on Darley Dale sandstone and Welsh slate have been investigated. The methods tried included batch tests with crushed rock and tests of simultaneous diffusion and convection with sorption on intact rock. High pressures (800m H 2 O) were used in the convective tests to pump water quickly through the rock samples and to measure high sorptivities in times shorter than those needed in the diffusive methods with intact samples. (author)

  9. A Sorption Hysteresis Model For Cellulosic Materials

    Frandsen, Henrik Lund; Damkilde, Lars

    2006-01-01

    The equilibrium concentration of adsorbed water in cellulosic materials is dependent on the history of the variations of vapor pressure in the ambient air, i.e. sorption hysteresis. Existing models to describe this phenomenon such as the independent domain theory have numerical drawbacks and....../or imply accounting for the entire history variations of every material point. This paper presents a sorption hysteresis model based on a state formulation and expressed in closed-form solutions, which makes it suitable for implementation into a numerical method....

  10. Sorption of natural uranium by algerian bentonite

    Megouda, N.; Kadi, H.; Hamla, M.S.; Brahimi, H.

    2004-01-01

    Full text.Batch sorption experiments have been used to assess the sorption behaviour of uranium onto natural and drilling bentonites. The operating parameters (pH, aolis-liquid ratio, particle size, time and initial uranium concentration) influenced the rate of adsorption. The distribution coefficient (Kd) range values at equilibrium time are 45.95-1079.26 ml/g and 32.81-463053 ml/g for the drilling and natural bentonites respectively. The equilibrium isotherms show that the data correlate with both Freundlich and Langmuir models

  11. Non-equilibrium effects in the plasmas

    Einfeld, D.

    1975-01-01

    Radial dependences of non-equilibrium effects of a He plasma were studied in a wall-stabilized short-time discharge. The electron density (nsub(e) = 2.5 x 10 22 m -3 ), the electron temperature and the equilibrium shift were determined by calculations of the continuum beam density and the beam densities of one He-I and one He-II line, respectively. In the discharge axis, the overpopulation factors of the ground state of He-I and He-II are about 75. As the distance to the axis increases, they increase for He-I and decrease for He-II. Except for the usual errors of measurement, the overpopulation factors found here correspond to those calculated from the balance equations (Drawin). (orig./AK) [de

  12. Non-equilibrium in flowing atmospheric plasmas

    Haas, J.C.M. de.

    1986-01-01

    This thesis deals with the fundamental aspects of two different plasmas applied in technological processes. The first one is the cesium seeded argon plasma in a closed cycle Magnetohydrodynamic (MHD) generator, the second is the thermal argon plasma in a cascade arc with an imposed flow. In Chapter 2 the influence of non-equilibrium on the mass and energy balances of a plasma is worked out. The general theory presented there can be applied to both the plasma in an MHD generator and to the cascade arc with imposed flow. Introductions to these plasmas are given in the Chapters 3 and 6 respectively. These chapters are both followed by two chapters which treat the theoretical and the experimental investigations. The results are summarized in Chapter 9. (Auth.)

  13. Landau superfluids as nonequilibrium stationary states

    Wreszinski, Walter F.

    2015-01-01

    We define a superfluid state to be a nonequilibrium stationary state (NESS), which, at zero temperature, satisfies certain metastability conditions, which physically express that there should be a sufficiently small energy-momentum transfer between the particles of the fluid and the surroundings (e.g., pipe). It is shown that two models, the Girardeau model and the Huang-Yang-Luttinger (HYL) model, describe superfluids in this sense and, moreover, that, in the case of the HYL model, the metastability condition is directly related to Nozières’ conjecture that, due to the repulsive interaction, the condensate does not suffer fragmentation into two (or more) parts, thereby assuring its quantum coherence. The models are rigorous examples of NESS in which the system is not finite, but rather a many-body system

  14. Non-equilibrium quantum heat machines

    Alicki, Robert; Gelbwaser-Klimovsky, David

    2015-11-01

    Standard heat machines (engine, heat pump, refrigerator) are composed of a system (working fluid) coupled to at least two equilibrium baths at different temperatures and periodically driven by an external device (piston or rotor) sometimes called the work reservoir. The aim of this paper is to go beyond this scheme by considering environments which are stationary but cannot be decomposed into a few baths at thermal equilibrium. Such situations are important, for example in solar cells, chemical machines in biology, various realizations of laser cooling or nanoscopic machines driven by laser radiation. We classify non-equilibrium baths depending on their thermodynamic behavior and show that the efficiency of heat machines powered by them is limited by the generalized Carnot bound.

  15. Nonequilibrium work relation in a macroscopic system

    Sughiyama, Yuki; Ohzeki, Masayuki

    2013-01-01

    We reconsider a well-known relationship between the fluctuation theorem and the second law of thermodynamics by evaluating stochastic evolution of the density field (probability measure valued process). In order to establish a bridge between microscopic and macroscopic behaviors, we must take the thermodynamic limit of a stochastic dynamical system following the standard procedure in statistical mechanics. The thermodynamic path characterizing a dynamical behavior in the macroscopic scale can be formulated as an infimum of the action functional for the stochastic evolution of the density field. In our formulation, the second law of thermodynamics can be derived only by symmetry of the action functional without recourse to the Jarzynski equality. Our formulation leads to a nontrivial nonequilibrium work relation for metastable (quasi-stationary) states, which are peculiar in the macroscopic system. We propose a prescription for computing the free energy for metastable states based on the resultant work relation. (paper)

  16. Nonequilibrium Thermodynamics of Driven Disordered Materials

    Bouchbinder, Eran

    2011-03-01

    We present a nonequilibrium thermodynamic framework for describing the dynamics of driven disordered solids (noncrystalline solids near and below their glass temperature, soft glassy materials such as colloidal suspensions and heavily dislocated polycrystalline solids). A central idea in our approach is that the set of mechanically stable configurations, i.e. the part of the system that is described by inherent structures, evolves slowly as compared to thermal vibrations and is characterized by an effective disorder temperature. Our thermodynamics-motivated equations of motion for the flow of energy and entropy are supplemented by coarse-grained internal variables that carry information about the relevant microscopic physics. Applications of this framework to amorphous visco-plasticity (Shear-Transformation-Zone theory), glassy memory effects (the Kovacs effect) and dislocation-mediated polycrystalline plasticity will be briefly discussed.

  17. Nonequilibrium Chromosome Looping via Molecular Slip Links

    Brackley, C. A.; Johnson, J.; Michieletto, D.; Morozov, A. N.; Nicodemi, M.; Cook, P. R.; Marenduzzo, D.

    2017-09-01

    We propose a model for the formation of chromatin loops based on the diffusive sliding of molecular slip links. These mimic the behavior of molecules like cohesin, which, along with the CTCF protein, stabilize loops which contribute to organizing the genome. By combining 3D Brownian dynamics simulations and 1D exactly solvable nonequilibrium models, we show that diffusive sliding is sufficient to account for the strong bias in favor of convergent CTCF-mediated chromosome loops observed experimentally. We also find that the diffusive motion of multiple slip links along chromatin is rectified by an intriguing ratchet effect that arises if slip links bind to the chromatin at a preferred "loading site." This emergent collective behavior favors the extrusion of loops which are much larger than the ones formed by single slip links.

  18. Magnetic polarons in a nonequilibrium polariton condensate

    Mietki, Paweł; Matuszewski, Michał

    2017-09-01

    We consider a condensate of exciton polaritons in a diluted magnetic semiconductor microcavity. Such a system may exhibit magnetic self-trapping in the case of sufficiently strong coupling between polaritons and magnetic ions embedded in the semiconductor. We investigate the effect of the nonequilibrium nature of exciton polaritons on the physics of the resulting self-trapped magnetic polarons. We find that multiple polarons can exist at the same time, and we derive a critical condition for self-trapping that is different from the one predicted previously in the equilibrium case. Using the Bogoliubov-de Gennes approximation, we calculate the excitation spectrum and provide a physical explanation in terms of the effective magnetic attraction between polaritons, mediated by the ion subsystem.

  19. Non-equilibrium quantum heat machines

    Alicki, Robert; Gelbwaser-Klimovsky, David

    2015-01-01

    Standard heat machines (engine, heat pump, refrigerator) are composed of a system (working fluid) coupled to at least two equilibrium baths at different temperatures and periodically driven by an external device (piston or rotor) sometimes called the work reservoir. The aim of this paper is to go beyond this scheme by considering environments which are stationary but cannot be decomposed into a few baths at thermal equilibrium. Such situations are important, for example in solar cells, chemical machines in biology, various realizations of laser cooling or nanoscopic machines driven by laser radiation. We classify non-equilibrium baths depending on their thermodynamic behavior and show that the efficiency of heat machines powered by them is limited by the generalized Carnot bound. (paper)

  20. MMS two-phase nonequilibrium pressurizer

    Oh, S.J.; Sursock, J.P.

    1987-01-01

    The pressurizer of a nuclear steam supply system establishes and maintains the nuclear plant primary loop pressure within the prescribed limit. It is a vertical cylindrical vessel which provides a water reserve and a steam surge chamber to accommodate coolant density changes during operation. To adjust the pressure to a desired value, electric heaters are provided in its lower section and the spray nozzles are provided in its upper section. Also, to protect against the buildup of the excess pressure, the pressurizer has two different types of relief valves, i.e., power operated relief valve and the safety relief valve. The pressurizer model implemented to the MMS is described in detail. In particular, the handling of the nonequilibrium condition, surgeline CCFL (Counter-current Flooding Limitation), and the level tracking model are described in detail. Next, the simulation of the Shippingport pressurizer load drop test is reported

  1. Stochastic approach to equilibrium and nonequilibrium thermodynamics.

    Tomé, Tânia; de Oliveira, Mário J

    2015-04-01

    We develop the stochastic approach to thermodynamics based on stochastic dynamics, which can be discrete (master equation) and continuous (Fokker-Planck equation), and on two assumptions concerning entropy. The first is the definition of entropy itself and the second the definition of entropy production rate, which is non-negative and vanishes in thermodynamic equilibrium. Based on these assumptions, we study interacting systems with many degrees of freedom in equilibrium or out of thermodynamic equilibrium and how the macroscopic laws are derived from the stochastic dynamics. These studies include the quasiequilibrium processes; the convexity of the equilibrium surface; the monotonic time behavior of thermodynamic potentials, including entropy; the bilinear form of the entropy production rate; the Onsager coefficients and reciprocal relations; and the nonequilibrium steady states of chemical reactions.

  2. Non-equilibrium synergistic effects in atmospheric pressure plasmas.

    Guo, Heng; Zhang, Xiao-Ning; Chen, Jian; Li, He-Ping; Ostrikov, Kostya Ken

    2018-03-19

    Non-equilibrium is one of the important features of an atmospheric gas discharge plasma. It involves complicated physical-chemical processes and plays a key role in various actual plasma processing. In this report, a novel complete non-equilibrium model is developed to reveal the non-equilibrium synergistic effects for the atmospheric-pressure low-temperature plasmas (AP-LTPs). It combines a thermal-chemical non-equilibrium fluid model for the quasi-neutral plasma region and a simplified sheath model for the electrode sheath region. The free-burning argon arc is selected as a model system because both the electrical-thermal-chemical equilibrium and non-equilibrium regions are involved simultaneously in this arc plasma system. The modeling results indicate for the first time that it is the strong and synergistic interactions among the mass, momentum and energy transfer processes that determine the self-consistent non-equilibrium characteristics of the AP-LTPs. An energy transfer process related to the non-uniform spatial distributions of the electron-to-heavy-particle temperature ratio has also been discovered for the first time. It has a significant influence for self-consistently predicting the transition region between the "hot" and "cold" equilibrium regions of an AP-LTP system. The modeling results would provide an instructive guidance for predicting and possibly controlling the non-equilibrium particle-energy transportation process in various AP-LTPs in future.

  3. Nanoscale hotspots due to nonequilibrium thermal transport

    Sinha, Sanjiv; Goodson, Kenneth E.

    2004-01-01

    Recent experimental and modeling efforts have been directed towards the issue of temperature localization and hotspot formation in the vicinity of nanoscale heat generating devices. The nonequilibrium transport conditions which develop around these nanoscale devices results in elevated temperatures near the heat source which can not be predicted by continuum diffusion theory. Efforts to determine the severity of this temperature localization phenomena in silicon devices near and above room temperature are of technological importance to the development of microelectronics and other nanotechnologies. In this work, we have developed a new modeling tool in order to explore the magnitude of the additional thermal resistance which forms around nanoscale hotspots from temperatures of 100-1000K. The models are based on a two fluid approximation in which thermal energy is transferred between ''stationary'' optical phonons and fast propagating acoustic phonon modes. The results of the model have shown excellent agreement with experimental results of localized hotspots in silicon at lower temperatures. The model predicts that the effect of added thermal resistance due to the nonequilibrium phonon distribution is greatest at lower temperatures, but is maintained out to temperatures of 1000K. The resistance predicted by the numerical code can be easily integrated with continuum models in order to predict the temperature distribution around nanoscale heat sources with improved accuracy. Additional research efforts also focused on the measurements of the thermal resistance of silicon thin films at higher temperatures, with a focus on polycrystalline silicon. This work was intended to provide much needed experimental data on the thermal transport properties for micro and nanoscale devices built with this material. Initial experiments have shown that the exposure of polycrystalline silicon to high temperatures may induce recrystallization and radically increase the thermal

  4. Phase transitions, scaling and renormalisation in nonequilibrium systems

    Hanney, T.E.

    2002-01-01

    Nonequilibrium phase transitions and critical phenomena in simple lattice-based interacting particle models are considered. Specific models of interest are exclusion models in low dimensions, with particular reference to the asymmetric simple exclusion process (ASEP) which provides a testbed for many of the calculations. The aim of the thesis is to devise approximate scaling techniques for such models which account for fluctuations and which are more widely applicable than methods pursuing an exact solution. Scaling techniques which have been applied to models described by a linear equation of motion are extended to the case where the equation of motion is nonlinear. These methods capture the dynamic transition in the ASEP but fail to properly account for the nonlinearity in their predictions for the dynamic exponent, z. A new and widely applicable real space renormalisation group procedure is developed. It provides a direct and transparent scaling method to extract universal and non-universal properties of the steady state and dynamic critical behaviour in the boundary-driven ASEP in one dimension. In particular, we obtain a flow diagram for the problem from which we can interpret all the qualitative features of the (exactly known) steady state phase diagram and which predicts the exact value for the critical point. Further, the dynamic scaling is consistent with a crossover between diflusive behaviour near the zero current fixed point and z = 3/2 dynamics at the critical fixed point. Extensions to include disorder, to higher dimensions, and to other models are all possible using the method. Using the mapping between the Master equation and the Schroedinger equation in imaginary time, this scaling procedure is rephrased as a new blocking for quantum-spin systems. Existing methods of real space renormalisation for quantum-spin systems are applied to a variety of previously unconsidered exclusion models. In particular, it is shown how such techniques can be applied

  5. Linear algebra

    Shilov, Georgi E

    1977-01-01

    Covers determinants, linear spaces, systems of linear equations, linear functions of a vector argument, coordinate transformations, the canonical form of the matrix of a linear operator, bilinear and quadratic forms, Euclidean spaces, unitary spaces, quadratic forms in Euclidean and unitary spaces, finite-dimensional space. Problems with hints and answers.

  6. The sorption behaviour of 99Tc on activated carbon

    Xia Deying; Zeng Jishu

    2004-01-01

    The sorption behaviour of 99 Tc on apricot-pit activated carbon with batch experiment is studied. The influence of such factors as sorbent particle size, temperature, pH value on sorption ratio, and the Freundlich sorption isotherms are reported in this paper. (author)

  7. Suitability of Moshi Pumice for Phosphorus Sorption in Constructed ...

    The study of Moshi Pumice's phosphorus sorption behaviours and properties was carried out in laboratory scale where by 1-2 mm, 2-4 mm and 4-8 mm grains were tested using batch experiments. The results show that Moshi Pumice has high phosphorus sorption capacity. The sorption capacity for the Moshi Pumice was ...

  8. Phosphorus sorption in relation to soil grain size and geochemical ...

    By using stepwise regression, the combination of Al, Fe, clay and Ca predicted more than 94% of the variation in the P sorption capacity of soils samples from Simiyu and Kagera basins. These four soil properties, which are strongly related to P sorption, could therefore be used as quick tests for predicting the P sorption ...

  9. Sorption of Heterocyclic Organic Compounds to Multiwalled Carbon Nanotubes.

    Metzelder, Florian; Funck, Matin; Schmidt, Torsten C

    2018-01-16

    Sorption is an important natural and technical process. Sorption coefficients are typically determined in batch experiments, but this may be challenging for weakly sorbing compounds. An alternative method enabling analysis of those compounds is column chromatography. A column packed with the sorbent is used and sorption data are determined by relating sorbate retention to that of a nonretarded tracer. In this study, column chromatography was applied for the first time to study sorption of previously hardly investigated heterocyclic organic compounds to multiwalled carbon nanotubes (MWCNTs). Sorption data for these compounds are very limited in literature, and weak sorption is expected from predictions. Deuterium oxide was used as nonretarded tracer. Sorption isotherms were well described by the Freundlich model and data showed reasonable agreement with predicted values. Sorption was exothermic and physisorption was observed. H-bonding may contribute to overall sorption, which is supported by reduced sorption with increasing ionic strength due to blocking of functional groups. Lowering pH reduced sorption of ionizable compounds, due to electrostatic repulsion at pH 3 where sorbent as well as sorbates were positively charged. Overall, column chromatography was successfully used to study sorption of heterocyclic compounds to MWCNTs and could be applied for other carbon-based sorbents.

  10. Attenuation of polychlorinated biphenyl sorption to charcoal by humic acids

    Koelmans, A.A.; Meulman, B.; Meijer, T.; Jonker, M.T.O.

    2009-01-01

    Strong sorption to black carbon may limit the environmental risks of organic pollutants, but interactions with cosorbing humic acid (HA) may interfere. We studied the attenuative effect of HA additions on the sorption of polychlorinated biphenyls (PCBs) to a charcoal. "Intrinsic" sorption to

  11. Sorption mechanisms of perfluorinated compounds on carbon nanotubes

    Deng Shubo; Zhang Qiaoying; Nie Yao; Wei Haoran; Wang Bin; Huang Jun; Yu Gang; Xing Baoshan

    2012-01-01

    Sorption of perfluorinated compounds (PFCs) on carbon nanotubes (CNTs) is critical for understanding their subsequent transport and fate in aqueous environments, but the sorption mechanisms remain largely unknown. In this study, the sorption of six PFCs on CNTs increased with increasing C-F chain length when they had a same functional group, and the CNTs with hydroxyl and carboxyl groups had much lower adsorbed amount than the pristine CNTs, indicating that hydrophobic interaction dominated the sorption of PFCs on the CNTs. Electrostatic repulsion suppressed the sorption of PFCs on the CNTs, resulting in the lower sorption with increasing pH. Hydrogen bonding interaction was negligible. The hydrophobic C-F chains can be closely adsorbed on the CNTs surface in parallel to the axis or along the curvature, making it impossible to form micelles on the CNT surface, leading to the lower sorption than other adsorbents. Highlights: ► Sorption capacities of PFOA on different CNTs are less than that on activated carbon and resins. ► Hydrophobic interaction is principally involved in the sorption of PFCs on CNTs. ► Electrostatic repulsion suppresses the sorption of PFCs on CNTs. - Hydrophobic interaction dominated the sorption of perfluorinated compounds on carbon nanotubes, while electrostatic repulsion suppressed their sorption.

  12. Kinetic and equilibrium study for the sorption of cadmium(II) ions from aqueous phase by eucalyptus bark

    Ghodbane, Ilhem; Nouri, Loubna; Hamdaoui, Oualid; Chiha, Mahdi

    2008-01-01

    The efficiency of eucalyptus bark as a low cost sorbent for removing cadmium ions from aqueous solution has been investigated in batch mode. The equilibrium data could be well described by the Langmuir isotherm but a worse fit was obtained by the Freundlich model. The five linearized forms of the Langmuir equation as well as the non-linear curve fitting analysis method were discussed. Results show that the non-linear method may be a better way to obtain the Langmuir parameters. Maximum cadmium uptake obtained at a temperature of 20 deg. C was 14.53 mg g -1 . The influence of temperature on the sorption isotherms of cadmium has been also studied. The monolayer sorption capacity increased from 14.53 to 16.47 when the temperature was raised from 20 to 50 deg. C. The ΔG o values were negative, which indicates that the sorption was spontaneous in nature. The effect of experimental parameters such as contact time, cadmium initial concentration, sorbent dose, temperature, solution initial pH, agitation speed, and ionic strength on the sorption kinetics of cadmium was investigated. Pseudo-second-order model was evaluated using the six linear forms as well as the non-linear curve fitting analysis method. Modeling of kinetic results shows that sorption process is best described by the pseudo-second-order model using the non-linear method. The pseudo-second-order model parameters were function of the initial concentration, the sorbent dose, the solution pH, the agitation speed, the temperature, and the ionic strength

  13. Hydration and sorption characteristics of a polyfunctional weak-base anion exchanger after the sorption of vanillin and ethylvanillin

    Rodionova, D. O.; Voronyuk, I. V.; Eliseeva, T. V.

    2016-07-01

    Features of the sorption of substituted aromatic aldehydes by a weak-base anion exchanger under equilibrium conditions are investigated using vanillin and ethylvanillin as examples. Analysis of the sorption isotherms of carbonyl compounds at different temperatures allows us to calculate the equilibrium characteristics of their sorption and assess the entropy and enthalpy contributions to the energy of the process. Hydration characteristics of the macroporous weak-base anion exchanger before and after the sorption of aromatic aldehydes are compared.

  14. Model Based Control of Moisture Sorption in a Historical Interior

    P. Zítek

    2005-01-01

    Full Text Available This paper deals with a novel scheme for microclimate control in historical exhibition rooms, inhibiting moisture sorption phenomena that are inadmissible from the preventive conservation point of view. The impact of air humidity is the most significant harmful exposure for a great deal of the cultural heritage deposited in remote historical buildings. Leaving the interior temperature to run almost its spontaneous yearly cycle, the proposed non-linear model-based control protects exhibits from harmful variations in moisture content by compensating the temperature drifts with an adequate adjustment of the air humidity. Already implemented in a medieval interior since 1999, the proposed microclimate control has proved capable of permanently maintaining constant a desirable moisture content in organic or porous materials in the interior of a building. 

  15. A suggested approach toward measuring sorption and applying sorption data to repository performance assessment

    Rundberg, R.S.

    1991-01-01

    The sorption of radioisotopes in relation to geologic disposal of radioactive wastes is discussed. Properties of the radioactive materials, rocks, and minerals, and the chemistry involved are described. 51 refs., 12 figs. CBS

  16. Sorption of fission nuclides on model milk components. II. Sorption of radiostrontium on hydroxyapatite in milk and whey

    Rosskopfova, O.; Kopunec, R.; Matel, L.; Macasek, F.

    1999-01-01

    In this work the whey was chosen as a model solution of liquid phase for sorption study of strontium on hydroxyapatite. The whey was obtained using two methods - ultracentrifugation and precipitation of casein. The sorption was studied at a different pH and at a different concentration of calcium. The sorption of strontium on hydroxyapatite from milk was studied, too. (authors)

  17. Development of mechanistic sorption model and treatment of uncertainties for Ni sorption on montmorillonite/bentonite

    Ochs, Michael; Ganter, Charlotte; Tachi, Yukio; Suyama, Tadahiro; Yui, Mikazu

    2011-02-01

    Sorption and diffusion of radionuclides in buffer materials (bentonite) are the key processes in the safe geological disposal of radioactive waste, because migration of radionuclides in this barrier is expected to be diffusion-controlled and retarded by sorption processes. It is therefore necessary to understand the detailed/coupled processes of sorption and diffusion in compacted bentonite and develop mechanistic /predictive models, so that reliable parameters can be set under a variety of geochemical conditions relevant to performance assessment (PA). For this purpose, JAEA has developed the integrated sorption and diffusion (ISD) model/database in montmorillonite/bentonite systems. The main goal of the mechanistic model/database development is to provide a tool for a consistent explanation, prediction, and uncertainty assessment of K d as well as diffusion parameters needed for the quantification of radionuclide transport. The present report focuses on developing the thermodynamic sorption model (TSM) and on the quantification and handling of model uncertainties in applications, based on illustrating by example of Ni sorption on montmorillonite/bentonite. This includes 1) a summary of the present state of the art of thermodynamic sorption modeling, 2) a discussion of the selection of surface species and model design appropriate for the present purpose, 3) possible sources and representations of TSM uncertainties, and 4) details of modeling, testing and uncertainty evaluation for Ni sorption. Two fundamentally different approaches are presented and compared for representing TSM uncertainties: 1) TSM parameter uncertainties calculated by FITEQL optimization routines and some statistical procedure, 2) overall error estimated by direct comparison of modeled and experimental K d values. The overall error in K d is viewed as the best representation of model uncertainty in ISD model/database development. (author)

  18. Gas Sorption, Diffusion, and Permeation in Nafion

    Mukaddam, Mohsin Ahmed; Litwiller, Eric; Pinnau, Ingo

    2015-01-01

    The gas permeability of dry Nafion films was determined at 2 atm and 35 °C for He, H2, N2, O2, CO2, CH4, C2H6, and C3H8. In addition, gas sorption isotherms were determined by gravimetric and barometric techniques as a function of pressure up to 20

  19. Development of a microminiature sorption cooler

    Burger, Johannes; Holland, Harry; ter Brake, Marcel; Rogalla, Horst; Wade, Larry

    1997-01-01

    The development of a microcooler for operations below 80 K, for low temperature electronic devices requiring small cooling powers of the order of 10 mW is described. A sorption compressor combined with Joule-Thomson (JT) expansion was selected for miniaturization. The advantage of the system is

  20. Sorption of radiocalcium on human hair

    Rakovic, M.; Pilecka, N.

    1987-01-01

    The sorption of 45 Ca on hair from a 45 CaCl 2 solution (2.5x10 -3 mol l -1 ) was studied. The calcium amounts sorbed in 1 min to 5 h range between 0.8 and 7.2% with respect to the originally present calcium in hair. (author) 3 refs

  1. Sorption of methanol in alkali exchange zeolites

    Rep, M.; Rep, M.; Corma, Avelino; Palomares, A.E.; Palomares gimeno, A.E.; van Ommen, J.G.; Lefferts, Leonardus; Lercher, J.A.

    2000-01-01

    Metal cation methanol sorption complexes in MFI (ZSM5), MOR and X have been studied by in situ i.r. spectroscopy in order to understand the nature of interactions of methanol in the molecular sieve pores. The results show that (a) a freely vibrating hydroxy and methyl group of methanol exist on

  2. Modelling Ni diffusion in bentonite using different sorption models

    Pfingsten, W.; Baeyens, B.; Bradbury, M.

    2010-01-01

    different modelling approaches a) an analytical solution with constant Kd using a constant Ni(II) concentration level at x = 0 (e.g. at the canister surface) and zero Ni(II) initial background concentration in the bentonite, b) a numerical 'constant K d approach' taking into account the initial Ni(II) background concentration in the bentonite pore water, and c) a reactive transport approach using the code MCOTAC in one-dimensional spatial geometry with an incorporated mechanistic sorption model which includes surface proto-lysis, surface complexation and cation exchange reactions. Charge balance is explicitly formulated for the surface complexation reactions. Selectivity coefficients and surface complexation data for Ni(II) were taken from Bradbury and Baeyens (2005); the related Fe(II) data were obtained from the Linear Free Energy Relationship (LFER) contained in the same publication. The Ni(II) breakthrough in the bentonite was calculated for different Ni(II) concentration levels with and without considering competition with Fe(II) on exchange and surface complexation sites for different Fe(II) concentrations in the bentonite pore water. The comparison allows the following observations to be made: for trace Ni(II) concentrations, the numerical 'constant K d approach' yield similar results to the reactive transport approach. For higher Ni(II) concentrations, the calculated Ni(II) breakthroughs differ from each other: the reactive transport approach yields an earlier breakthrough than the numerical 'constant K d approach' for a Ni concentration level of 10 -5 M. However, for a Ni(II) concentration level of 10 -4 M, the reactive transport approach yield a later but steeper breakthrough, reaching the maximum Ni(II) concentration level earlier than the numerical 'constant K d approach'. Fe(II) competition reactions could only be taken into account using the reactive transport approach. The results yield a general dependency of the Ni

  3. Thermodynamic Properties, Sorption Isotherms and Glass Transition Temperature of Cape Gooseberry (Physalis peruviana L.

    Jessica López

    2014-01-01

    Full Text Available Adsorption and desorption isotherms of fresh and dried Cape gooseberry (Physalis peruviana L. were determined at three temperatures (20, 40 and 60 °C using a gravimetric technique. The data obtained were fitted to several models including Guggenheim-Anderson- De Boer (GAB, Brunauer-Emmett-Teller (BET, Henderson, Caurie, Smith, Oswin, Halsey and Iglesias-Chirife. A non-linear least square regression analysis was used to evaluate the models. The Iglesias-Chirife model fitted best the experimental data. Isosteric heat of sorption was also determined from the equilibrium sorption data using the Clausius-Clapeyron equation and was found to decrease exponentially with increasing moisture content. The enthalpy-entropy compensation theory was applied to the sorption isotherms and indicated an enthalpy-controlled sorption process. Glass transition temperature (Tg of Cape gooseberry was also determined by differential scanning calorimetry and modelled as a function of moisture content with the Gordon-Taylor, the Roos and the Khalloufi models, which proved to be excellent tools for predicting glass transition of Cape gooseberry.

  4. Radionuclide sorption kinetics and column sorption studies with Columbia River basalts

    Barney, G.S.

    1983-09-01

    The kinetics of radionuclide sorption and desorption reactions in basalt-groundwater systems were evaluated at 60 degrees C using a batch equilibration method. It was found that many sorption reactions on surfaces of fresh (unaltered) basalt from the Umtanum and Cohassett flows are slow. Some reactions require more than 50 days to reach a steady state. Sorption of neptunium and uranium in oxidizing (air saturated) groundwater appears to be controlled by slow reduction of these elements by the basalt surfaces. The resulting lower oxidation states are more strongly sorbed. Technetium and selenium, which are anionic under oxidizing conditions, are not measurably sorbed on fresh basalt surfaces, but are slightly sorbed on the altered surfaces of flow top basalt. Under reducing conditions, where the groundwater contains dilute hydrazine, sorption is faster for neptunium, uranium, technetium, selenium, and lead. Plutonium sorption rates were not affected by the groundwater Eh. It was shown that radium was precipitated rather than sorbed under the conditions of these experiments. Umtanum flow top material sorbed radionuclides much faster than fresh basalt surfaces due to its greater surface area and cation exchange capacity. Desorption rates for plutonium, uranium, neptunium, technetium, and selenium were generally much less than sorption rates (especially for reducing conditions). These radionuclides are irreversibly sorbed on the basalts. 25 refs., 20 figs., 19 tabs

  5. Radionuclide sorption on crushed and intact granitic rock

    Eriksen, Tryggve E.; Locklund, Birgitta

    1989-05-01

    The specific surface areas and distribution ratios for sorption of 85 Sr, 137 Cs and 152 Eu were measured for crushed and intact granite rock. The experimental data can be accommodated by a sorption model encompassing sorption on outer and inner surface. It is clearly demonstrated that the time required to obtain reliable Kd-values for the sorption of strongly sorbing radionuclides like 152 Eu is very long due to solution depletion and slow diffusion into the rock. A combination of surface area measurements and batch sorption with small particles may therefore be preferable when studying strongly sorbing nuclides. (authors) (17 figs., 6 tabs.)

  6. Sorption and migration of neptunium in porous sedimentary materials

    Tanaka, Tadao; Mukai, Masayuki; Nakayama, Shinichi

    2005-01-01

    Column migration experiments of neptunium were conducted for porous sedimentary materials: coastal sand, tuffaceous sand, ando soil, reddish soil, yellowish soil and loess, and migration behavior, sorption mechanisms and chemical formation of Np were investigated. The migration behavior of Np in each material was much different each other, due to chemical formation in solution and/or sorption mechanism of Np. Mathematical models of different concepts were applied to the experimental results to interpret the sorption mechanism and the migration behavior. It can be concluded that both of instantaneous equilibrium sorption and sorption-desorption kinetics have to be considered to model the Np migration in sedimentary materials. (author)

  7. Sorption of niobium on boreal forest soil

    Soederlund, Mervi; Hakanen, Martti; Lehto, Jukka [Helsinki Univ. (Finland). Lab. of Radiochemistry

    2015-07-01

    The sorption of niobium (Nb) was investigated on humus and mineral soil samples taken from various depths of a four-metre deep forest soil pit on Olkiluoto Island, southwestern Finland. Mass distribution coefficients, K{sub d}, were determined in batch sorption tests. The steady state of Nb sorption was observed in the mineral soil samples already after one week of equilibration, and sorption decreased with depth from a very high value of 185000 mL/g at 0.7 m to 54000 mL/g at 3.4 m. The reason behind this decrease is probably the tenfold reduction in the specific surface area of the soil at the same depth range. Distribution coefficients were clearly lower in the humus layer (1000 mL/g). The K{sub d} values determined in pure water at a pH range of 4.7-6.5 were at a high level (above 55000 mL/g), but decreased dramatically above pH 6.5, corresponding to the change in the major Nb species from the neutral Nb(OH){sub 5} to the low-sorbing anionic Nb(OH){sub 6}{sup -} and Nb(OH){sub 7}{sup 2-}. However, the K{sub d} values in the model soil solution were in the slightly alkaline range an order of magnitude higher than in pure water, which is probably caused by the formation of calcium niobate surface precipitate or electrostatic interaction between surface-sorbed calcium and solute Nb. Among nine soil constituent minerals kaolinite performed best in retaining Nb in both pure water and model soil solution at pH 8, whereas potassium feldspar showed the poorest sorption. The K{sub d} value for kaolinite was above 500000 mL/g in both solutions, while the respective potassium feldspar values were in the range of 120-220 mL/g.

  8. Modeling Fission Product Sorption in Graphite Structures

    Szlufarska, Izabela; Morgan, Dane; Allen, Todd

    2013-01-01

    The goal of this project is to determine changes in adsorption and desorption of fission products to/from nuclear-grade graphite in response to a changing chemical environment. First, the project team will employ principle calculations and thermodynamic analysis to predict stability of fission products on graphite in the presence of structural defects commonly observed in very high-temperature reactor (VHTR) graphites. Desorption rates will be determined as a function of partial pressure of oxygen and iodine, relative humidity, and temperature. They will then carry out experimental characterization to determine the statistical distribution of structural features. This structural information will yield distributions of binding sites to be used as an input for a sorption model. Sorption isotherms calculated under this project will contribute to understanding of the physical bases of the source terms that are used in higher-level codes that model fission product transport and retention in graphite. The project will include the following tasks: Perform structural characterization of the VHTR graphite to determine crystallographic phases, defect structures and their distribution, volume fraction of coke, and amount of sp2 versus sp3 bonding. This information will be used as guidance for ab initio modeling and as input for sorptivity models; Perform ab initio calculations of binding energies to determine stability of fission products on the different sorption sites present in nuclear graphite microstructures. The project will use density functional theory (DFT) methods to calculate binding energies in vacuum and in oxidizing environments. The team will also calculate stability of iodine complexes with fission products on graphite sorption sites; Model graphite sorption isotherms to quantify concentration of fission products in graphite. The binding energies will be combined with a Langmuir isotherm statistical model to predict the sorbed concentration of fission products

  9. Rate of tunneling nonequilibrium quasiparticles in superconducting qubits

    Ansari, Mohammad H

    2015-01-01

    In superconducting qubits the lifetime of quantum states cannot be prolonged arbitrarily by decreasing temperature. At low temperature quasiparticles tunneling between the electromagnetic environment and superconducting islands takes the condensate state out of equilibrium due to charge imbalance. We obtain the tunneling rate from a phenomenological model of non-equilibrium, where nonequilibrium quasiparticle tunnelling stimulates a temperature-dependent chemical potential shift in the superconductor. As a result we obtain a non-monotonic behavior for relaxation rate as a function of temperature. Depending on the fabrication parameters for some qubits, the lowest tunneling rate of nonequilibrium quasiparticles can take place only near the onset temperature below which nonequilibrium quasiparticles dominate over equilibrium one. Our theory also indicates that such tunnelings can influence the probability of transitions in qubits through a coupling to the zero-point energy of phase fluctuations. (paper)

  10. Nonequilibrium electron transport through quantum dots in the Kondo regime

    Wölfle, Peter; Paaske, Jens; Rosch, Achim

    2005-01-01

    Electron transport at large bias voltage through quantum dots in the Kondo regime is described within the perturbative renormalization group extended to nonequilibrium. The conductance, local magnetization, dynamical spin susceptibility and local spectral function are calculated. We show how...

  11. Nonequilibrium constitutive models for RELAP5/MOD2

    Lin, J.C.; Trapp, J.A.; Riemke, R.A.; Ransom, V.H.

    1983-01-01

    RELAP5/MOD2 is a new version of RELAP5 containing improved modeling features that provide a generic pressurized-water transient simulation capability. In particular, the nonequilibrium modeling capability has been generalized to include conditions that occur in operational transients including repressurization and emergency-feed-water injection with loss-of-coolant accidents. The improvements include addition of a second energy equation to the hydrodynamic model, addition of nonequilibrium heat-transfer models, and the associated nonequilibrium vapor-generation models. The objective of this paper is to describe these models and to report the developmental assessment results obtained from similar of several separate effects experiments. The assessment shows that RELAP5 calculated results are in good agreement with data and the nonequilibrium phenomena are properly modeled

  12. Non-Equilibrium Thermodynamics of Self-Replicating Protocells

    Fellermann, Harold; Corominas-Murtra, Bernat; Hansen, Per Lyngs

    2018-01-01

    We provide a non-equilibrium thermodynamic description of the life-cycle of a droplet based, chemically feasible, system of protocells. By coupling the protocells metabolic kinetics with its thermodynamics, we demonstrate how the system can be driven out of equilibrium to ensure protocell growth...... and replication. This coupling allows us to derive the equations of evolution and to rigorously demonstrate how growth and replication life-cycle can be understood as a non-equilibrium thermodynamic cycle. The process does not appeal to genetic information or inheritance, and is based only on non......-equilibrium physics considerations. Our non-equilibrium thermodynamic description of simple, yet realistic, processes of protocell growth and replication, represents an advance in our physical understanding of a central biological phenomenon both in connection to the origin of life and for modern biology....

  13. Equilibrium and non-equilibrium phenomena in arcs and torches

    Mullen, van der J.J.A.M.

    2000-01-01

    A general treatment of non-equilibrium plasma aspects is obtained by relating transport fluxes to equilibrium restoring processes in so-called disturbed Bilateral Relations. The (non) equilibrium stage of a small microwave induced plasma serves as case study.

  14. Electrolytes: transport properties and non-equilibrium thermodynamics

    Miller, D.G.

    1980-12-01

    This paper presents a review on the application of non-equilibrium thermodynamics to transport in electrolyte solutions, and some recent experimental work and results for mutual diffusion in electrolyte solutions

  15. Foundations of atmospheric pressure non-equilibrium plasmas

    Bruggeman, Peter J.; Iza, Felipe; Brandenburg, Ronny

    2017-12-01

    Non-equilibrium plasmas have been intensively studied over the past century in the context of material processing, environmental remediation, ozone generation, excimer lamps and plasma display panels. Research on atmospheric pressure non-equilibrium plasmas intensified over the last two decades leading to a large variety of plasma sources that have been developed for an extended application range including chemical conversion, medicine, chemical analysis and disinfection. The fundamental understanding of these discharges is emerging but there remain a lot of unexplained phenomena in these intrinsically complex plasmas. The properties of non-equilibrium plasmas at atmospheric pressure span over a huge range of electron densities as well as heavy particle and electron temperatures. This paper provides an overview of the key underlying processes that are important for the generation and stabilization of atmospheric pressure non-equilibrium plasmas. The unique physical and chemical properties of theses discharges are also summarized.

  16. Some recent developments in non-equilibrium statistical physics

    : ... This canonical prescription is the starting point for studying a system in ... abilistic approach to non-equilibrium dynamics by treating the case of Markovian ..... equation in this network between the incoming flux and the outgoing flux at each.

  17. SORPTION OF Au(III BY Saccharomyces cerevisiae BIOMASS

    Amaria Amaria

    2010-07-01

    Full Text Available Au(III sorption by S. cerevisiae biomass extracted from beer waste industry was investigated. Experimentally, the sorption was conducted in batch method. This research involved five steps: 1 identification the functional groups present in the S. cerevisiae biomass by infrared spectroscopic technique, 2 determination of optimum pH, 3 determination of the sorption capacity and energy, 4 determination of the sorption type by conducting desorption of sorbed Au(III using specific eluents having different desorption capacity such as H2O (van der Waals, KNO3 (ion exchange, HNO3 (hydrogen bond, and tiourea (coordination bond, 5 determination of effective eluents in Au(III desorption by partial desorption of sorbed Au(III using thiourea, NaCN and KI. The remaining Au(III concentrations in filtrate were analyzed using Atomic Absorption Spectrophotometer. The results showed that: 1 Functional groups of S. cerevisiae biomass that involved in the sorption processes were hydroxyl (-OH, carboxylate (-COO- and amine (-NH2, 2 maximum sorption was occurred at pH 4, equal to 98.19% of total sorption, 3 The sorption capacity of biomass was 133.33 mg/g (6.7682E-04 mol/g and was involved sorption energy 23.03 kJ mol-1, 4 Sorption type was dominated by coordination bond, 5 NaCN was effective eluent to strip Au(III close to 100%.   Keywords: sorption, desorption, S. cerevisiae biomass, Au(III

  18. Density-functional method for nonequilibrium electron transport

    Brandbyge, Mads; Mozos, J.L.; Ordejon, P.

    2002-01-01

    the contact and the electrodes on the same footing. The effect of the finite bias (including self-consistency and the solution of the electrostatic problem) is taken into account using nonequilibrium Green's functions. We relate the nonequilibrium Green's function expressions to the more transparent scheme...... wires connected to aluminum electrodes with extended or finite cross section, (ii) single atom gold wires, and finally (iii) large carbon nanotube systems with point defects....

  19. Complex Dynamics in Nonequilibrium Economics and Chemistry

    Wen, Kehong

    Complex dynamics provides a new approach in dealing with economic complexity. We study interactively the empirical and theoretical aspects of business cycles. The way of exploring complexity is similar to that in the study of an oscillatory chemical system (BZ system)--a model for modeling complex behavior. We contribute in simulating qualitatively the complex periodic patterns observed from the controlled BZ experiments to narrow the gap between modeling and experiment. The gap between theory and reality is much wider in economics, which involves studies of human expectations and decisions, the essential difference from natural sciences. Our empirical and theoretical studies make substantial progress in closing this gap. With the help from the new development in nonequilibrium physics, i.e., the complex spectral theory, we advance our technique in detecting characteristic time scales from empirical economic data. We obtain correlation resonances, which give oscillating modes with decays for correlation decomposition, from different time series including S&P 500, M2, crude oil spot prices, and GNP. The time scales found are strikingly compatible with business experiences and other studies in business cycles. They reveal the non-Markovian nature of coherent markets. The resonances enhance the evidence of economic chaos obtained by using other tests. The evolving multi-humped distributions produced by the moving-time -window technique reveal the nonequilibrium nature of economic behavior. They reproduce the American economic history of booms and busts. The studies seem to provide a way out of the debate on chaos versus noise and unify the cyclical and stochastic approaches in explaining business fluctuations. Based on these findings and new expectation formulation, we construct a business cycle model which gives qualitatively compatible patterns to those found empirically. The soft-bouncing oscillator model provides a better alternative than the harmonic oscillator

  20. Nonequilibrium emergent phenomena in organic molecular solids

    Mitrano, Matteo

    2015-07-15

    The manipulation of matter with ultrashort laser pulses is a relevant research field from both a fundamental and an applied perspective, owing to the efficient coupling to the electronic degrees of freedom on femtosecond timescales and the ability to induce transient phases that cannot be realized in equilibrium scenarios. Strongly correlated materials are a natural environment for the observation of such novel and emergent out-of-equilibrium physics because small modifications to the electron-electron interactions can induce transitions between remarkably different macroscopic phases. One of the most effective means of modifying the effective electron-electron interactions is to perturb the crystal structure through pressure, strain or even light. However, it remains largely unexplored how perturbing the structural degrees of freedom affects the electron dynamics of the transiently driven states and how the interplay of correlations and electron-lattice interactions determine the intrinsic timescales of these nonequilibrium states. This thesis investigates how to control the light-induced nonequilibrium electronic properties in strongly correlated organics, that are highly tunable with moderate variations of external parameters, by perturbing their structural degrees of freedom, either via static pressures or vibrational excitation. We study the role of correlations in determining the relaxation rate of holes (holons) and double occupancies (doublons) in a solid state Mott insulator, the ET-F{sub 2}TCNQ, driven across a transient insulator-to-metal transition. By mapping holon-doublon lifetimes onto the ground-state electronic interactions, we found that the decay rate of the photoinjected quasiparticles depends on the degree of correlation between carriers and is affected by the presence of a competition between local recombination and delocalization of holon-doublon pairs. By optically controlling the effective correlations in organic molecular crystals through

  1. An online re-linearization scheme suited for Model Predictive and Linear Quadratic Control

    Henriksen, Lars Christian; Poulsen, Niels Kjølstad

    This technical note documents the equations for primal-dual interior-point quadratic programming problem solver used for MPC. The algorithm exploits the special structure of the MPC problem and is able to reduce the computational burden such that the computational burden scales with prediction...... horizon length in a linear way rather than cubic, which would be the case if the structure was not exploited. It is also shown how models used for design of model-based controllers, e.g. linear quadratic and model predictive, can be linearized both at equilibrium and non-equilibrium points, making...

  2. Sepiolite functionalized with N-[3-(trimethoxysilylpropyl]-ethylenediamine triacetic acid trisodium salt. Part II: Sorption of Ni2+ from aqueous solutions

    Lazarević Slavica S.

    2016-01-01

    Full Text Available sorption of Ni2+ on the sepiolite functionalized by covalent grafting of N-[3-(trimethoxysilylpropyl]ethylenediamine triacetic acid trisodium salt, MSEAS, was studied in batch experiments as a function of the initial metal concentration, the equilibration time, pH value, and temperature. The modification of sepiolite resulted in an enhanced Ni2+ retention with a capacity of 0.261 mmol/g at 298 K. The retention of Ni2+ ions occurred dominantly by specific sorption and exchange of Mg2+ ions from the sepiolite structure. The sorption process followed pseudo-second-order kinetics. The sorption equilibrium results were best described by the non-linear form of the Langmuir Sorption Equation. The values of the thermodynamic parameters (enthalpy, free energy and entropy were calculated from temperature dependent sorption isotherms and these values showed that the sorption of Ni2+ onto modified sepiolite was endothermic. [Projekat Ministarstva nauke Republike Srbije, br. III 45019 i FP7 NANOTECH FTM No. 245916

  3. Thermodynamic sorption modelling in support of radioactive waste disposal safety cases - NEA sorption project phase III

    2012-01-01

    A central safety function of radioactive waste disposal repositories is the prevention or sufficient retardation of radionuclide migration to the biosphere. Performance assessment exercises in various countries, and for a range of disposal scenarios, have demonstrated that one of the most important processes providing this safety function is the sorption of radionuclides along potential migration paths beyond the engineered barriers. Thermodynamic sorption models (TSMs) are key for improving confidence in assumptions made about such radionuclide sorption when preparing a repository's safety case. This report presents guidelines for TSM development as well as their application in repository performance assessments. They will be of particular interest to the sorption modelling community and radionuclide migration modellers in developing safety cases for radioactive waste disposal Contents: 1 - Thermodynamic sorption models and radionuclide migration: Sorption and radionuclide migration; Applications of TSMs in radioactive waste disposal studies; Requirements for a scientifically defensible, calibrated TSM applicable to radioactive waste disposal; Current status of TSMs in radioactive waste management; 2 - Theoretical basis of TSMs and options in model development: Conceptual building blocks of TSMs and integration with aqueous chemistry; The TSM representation of sorption and relationship with Kd values; Theoretical basis of TSMs; Example of TSM for uranyl sorption; Options in TSM development; Illustration of TSM development and effects of modelling choices; Summary: TSMs for constraining Kd values - impact of modelling choices; 3 - Determination of parameters for TSMs: Overview of experimental determination of TSM parameters; Theoretical estimation methods of selected model parameters; Case study: sorption modelling of trivalent lanthanides/actinides on illite; Indicative values for certain TSM parameters; Parameter uncertainty; Illustration of parameter sensitivity

  4. Achieving Radiation Tolerance through Non-Equilibrium Grain Boundary Structures.

    Vetterick, Gregory A; Gruber, Jacob; Suri, Pranav K; Baldwin, Jon K; Kirk, Marquis A; Baldo, Pete; Wang, Yong Q; Misra, Amit; Tucker, Garritt J; Taheri, Mitra L

    2017-09-25

    Many methods used to produce nanocrystalline (NC) materials leave behind non-equilibrium grain boundaries (GBs) containing excess free volume and higher energy than their equilibrium counterparts with identical 5 degrees of freedom. Since non-equilibrium GBs have increased amounts of both strain and free volume, these boundaries may act as more efficient sinks for the excess interstitials and vacancies produced in a material under irradiation as compared to equilibrium GBs. The relative sink strengths of equilibrium and non-equilibrium GBs were explored by comparing the behavior of annealed (equilibrium) and as-deposited (non-equilibrium) NC iron films on irradiation. These results were coupled with atomistic simulations to better reveal the underlying processes occurring on timescales too short to capture using in situ TEM. After irradiation, NC iron with non-equilibrium GBs contains both a smaller number density of defect clusters and a smaller average defect cluster size. Simulations showed that excess free volume contribute to a decreased survival rate of point defects in cascades occurring adjacent to the GB and that these boundaries undergo less dramatic changes in structure upon irradiation. These results suggest that non-equilibrium GBs act as more efficient sinks for defects and could be utilized to create more radiation tolerant materials in future.

  5. The influence of Fe(II) competition on the sorption and migration of Ni(II) in MX-80 bentonite

    Pfingsten, Wilfried; Bradbury, Mike; Baeyens, Bart

    2011-01-01

    Highlights: → We model the diffusion of Ni(II) through bentonite using different sorption models. → We examine sorption competition of Fe(II) and Ni(II) at different concentrations. → Ni(II) breakthrough is 15 times earlier with Fe(II) sorption competition. → Ni(II) sorption is non-linear and depends on the Fe(II) concentration levels. → Sorption competition is important and has to be modelled by reactive transport codes. - Abstract: The results from batch sorption experiments on montmorillonite systems have demonstrated that bivalent transition metals compete with one another for sorption sites. For safety analysis studies of high level radioactive waste repositories with compacted bentonite near fields, the importance of competitive sorption on the migration of radionuclides needs to be evaluated. Under reducing conditions, the bentonite porewater chosen has a Fe(II) concentration of ∼5.3 x 10 -5 M through saturation with siderite. The purpose of this paper is to assess the influence of such high Fe(II) concentrations on the transport of Ni(II) through compacted bentonite, Ni(II) was chosen as an example of a bivalent transition metal. The one-dimensional calculations were carried out at different Ni(II) equilibrium concentrations at the boundary (Ni(II) EQBM ) with the reactive transport code MCOTAC incorporating the two site protolysis non electrostatic surface complexation/cation exchange sorption model, MCOTAC-sorb. At a Ni(II) EQBM level of 10 -7 M without Fe(II) competition, the reactive transport calculations using a constant K d approach and the MCOTAC-sorb calculation yielded the same breakthrough curves. At higher Ni(II) EQBM (10 -5 M), the model calculations with MCOTAC-sorb indicated a breakthrough which was shifted to later times by a factor of ∼5 compared with the use of the constant K d approach. When sorption competition was included in the calculations, the magnitude of the influence depended on the sorption characteristics of the

  6. Benzene and MTBE Sorption in Fine Grain Sediments

    Leal-Bautista, R. M.; Lenczewski, M. E.

    2003-12-01

    The practice of adding methyl tert-butyl ether (MTBE) to gasoline started in the late 1970s and increased dramatically in the 1990s. MTBE first was added as a substitute for tetra-ethyl lead then later as a fuel oxygenate. Although the use of MTBE has resulted in significant reduction in air pollution, it has become a significant groundwater contaminant due to its high solubility in water, high environmental mobility, and low potential for biodegradation. A recent report (1999-2001) by the Metropolitan Water District of Southern California in collaboration with United State Geological Survey and the Oregon Health and Science University found that MTBE was the second most frequent detected volatile organic compound in groundwater. In Illinois, MTBE has been found in 26 of the 1,800 public water supplies. MTBE has also been blended in Mexico into two types of gasoline sold in the country by the state oil company (PEMEX) but is not monitored in groundwater at this time. Early research on MTBE considered it unable to adsorb to soils and sediments, however, by increasing the organic matter and decreasing the size of the grains (silts or clays) this may increase sorption. The objective of this study is to determine if fine grained materials have the potential for sorption of MTBE due to its high specific surface area (10-700 m 2/g) and potentially high organic matter (0.5-3.8%). The experiment consisted of sorption isotherms to glacial tills from DeKalb, Illinois and lacustrine clays from Chalco, Mexico. Experiments were performed with various concentrations of MTBE and benzene (10, 50, 100, 500 and 1000 ug/L) at 10° C and 25° C. Results showed a range of values for the distribution coefficient (Kd, linear model). At 10° C the Kd value for MTBE was 0.187 mL/g for lacustrine clay while the glacial loess had a value of 0.009 mL/g. The highest Kd values with MTBE were 0.2859 mL/g for organic rich lacustrine clays and 0.014 mL/g for glacial loess at 25° C. The highest

  7. Physico-chemical characterisation and sorption measurements of Cs, Sr, Ni, Eu, Th, Sn and Se on Opalinus clay from Mont Terri

    Lauber, Matthias; Baeyens, Bart; Bradbury, Michael H.

    2000-12-01

    Opalinus Clay is currently under investigation as a potential host rock for the disposal of high level and long-lived intermediate radioactive waste. A throughout physico-chemical characterisation was carried out on a bore core sample from the underground rock laboratory Mont Terri (Canton Jura). The results of these investigations indicate that the major characteristics (mineralogy, cation exchange capacity, cation occupancies, selectivity coefficients, chloride and sulphate inventories) were very similar to a different core sample, previously used for pore water modelling studies. It was concluded that the pore water compositions derived in the earlier studies were reliable and could be used in this work. The organic matter which dissolved from the Opalinus Clay rock was not humic or fulvic acids and the concentration remaining in the liquid phase in the sorption experiments was < 0.5 ppm C. The organic matter is therefore considered to have little or no influence on the sorption behaviour of the studied radionuclides. Redox potential measurements of the Opalinus Clay/synthetic pore water system inside the glove boxes indicated anoxic conditions. The main focus of the experimental work presented here is on the sorption behaviour of Cs (I), Sr (II), Ni (II), Eu (III), Th (IV), Sn (IV) and Se (IV) on Opalinus Clay equilibrated with synthetic pore waters at pH 6.3 and 8. Sorption isotherms were measured for Cs, Ni, Eu, Th and Se. Single point data were measured for Sr and Sn. For all radionuclides studied the sorption kinetics were measured first. The times required to complete the sorption on the Opalinus Clay varied between one day for Th and one month for Ni and Se. Within the concentration ranges under study the uptake of Cs, Ni, Eu and Se on Opalinus Clay was non-linear, whereas for Th a linear sorption behaviour was observed. For Ni, Eu and Th the sorption increased with increasing pH. For Cs a pH independent sorption behaviour was observed. The concentration

  8. Nonequilibrium landscape theory of neural networks.

    Yan, Han; Zhao, Lei; Hu, Liang; Wang, Xidi; Wang, Erkang; Wang, Jin

    2013-11-05

    The brain map project aims to map out the neuron connections of the human brain. Even with all of the wirings mapped out, the global and physical understandings of the function and behavior are still challenging. Hopfield quantified the learning and memory process of symmetrically connected neural networks globally through equilibrium energy. The energy basins of attractions represent memories, and the memory retrieval dynamics is determined by the energy gradient. However, the realistic neural networks are asymmetrically connected, and oscillations cannot emerge from symmetric neural networks. Here, we developed a nonequilibrium landscape-flux theory for realistic asymmetrically connected neural networks. We uncovered the underlying potential landscape and the associated Lyapunov function for quantifying the global stability and function. We found the dynamics and oscillations in human brains responsible for cognitive processes and physiological rhythm regulations are determined not only by the landscape gradient but also by the flux. We found that the flux is closely related to the degrees of the asymmetric connections in neural networks and is the origin of the neural oscillations. The neural oscillation landscape shows a closed-ring attractor topology. The landscape gradient attracts the network down to the ring. The flux is responsible for coherent oscillations on the ring. We suggest the flux may provide the driving force for associations among memories. We applied our theory to rapid-eye movement sleep cycle. We identified the key regulation factors for function through global sensitivity analysis of landscape topography against wirings, which are in good agreements with experiments.

  9. Nonequilibrium landscape theory of neural networks

    Yan, Han; Zhao, Lei; Hu, Liang; Wang, Xidi; Wang, Erkang; Wang, Jin

    2013-01-01

    The brain map project aims to map out the neuron connections of the human brain. Even with all of the wirings mapped out, the global and physical understandings of the function and behavior are still challenging. Hopfield quantified the learning and memory process of symmetrically connected neural networks globally through equilibrium energy. The energy basins of attractions represent memories, and the memory retrieval dynamics is determined by the energy gradient. However, the realistic neural networks are asymmetrically connected, and oscillations cannot emerge from symmetric neural networks. Here, we developed a nonequilibrium landscape–flux theory for realistic asymmetrically connected neural networks. We uncovered the underlying potential landscape and the associated Lyapunov function for quantifying the global stability and function. We found the dynamics and oscillations in human brains responsible for cognitive processes and physiological rhythm regulations are determined not only by the landscape gradient but also by the flux. We found that the flux is closely related to the degrees of the asymmetric connections in neural networks and is the origin of the neural oscillations. The neural oscillation landscape shows a closed-ring attractor topology. The landscape gradient attracts the network down to the ring. The flux is responsible for coherent oscillations on the ring. We suggest the flux may provide the driving force for associations among memories. We applied our theory to rapid-eye movement sleep cycle. We identified the key regulation factors for function through global sensitivity analysis of landscape topography against wirings, which are in good agreements with experiments. PMID:24145451

  10. Fluctuations When Driving Between Nonequilibrium Steady States

    Riechers, Paul M.; Crutchfield, James P.

    2017-08-01

    Maintained by environmental fluxes, biological systems are thermodynamic processes that operate far from equilibrium without detailed-balanced dynamics. Yet, they often exhibit well defined nonequilibrium steady states (NESSs). More importantly, critical thermodynamic functionality arises directly from transitions among their NESSs, driven by environmental switching. Here, we identify the constraints on excess heat and dissipated work necessary to control a system that is kept far from equilibrium by background, uncontrolled "housekeeping" forces. We do this by extending the Crooks fluctuation theorem to transitions among NESSs, without invoking an unphysical dual dynamics. This and corresponding integral fluctuation theorems determine how much work must be expended when controlling systems maintained far from equilibrium. This generalizes thermodynamic feedback control theory, showing that Maxwellian Demons can leverage mesoscopic-state information to take advantage of the excess energetics in NESS transitions. We also generalize an approach recently used to determine the work dissipated when driving between functionally relevant configurations of an active energy-consuming complex system. Altogether, these results highlight universal thermodynamic laws that apply to the accessible degrees of freedom within the effective dynamic at any emergent level of hierarchical organization. By way of illustration, we analyze a voltage-gated sodium ion channel whose molecular conformational dynamics play a critical functional role in propagating action potentials in mammalian neuronal membranes.

  11. Defluoridation by Bacteriogenic Iron Oxides: Sorption Studies

    Evans, K.; Ferris, F.

    2009-05-01

    At concentrations above 1 mg/L, fluoride in drinking water can lead to dental and skeletal fluorosis, a disease that causes mottling of the teeth, calcification of ligaments, crippling bone deformities and many other physiological disorders that can, ultimately, lead to death. Conservative estimates are that fluorosis afflicts tens of millions of people worldwide. As there is no treatment for fluorosis, prevention is the only means of controlling the disease. While numerous defluoridation techniques have been explored, no single method has been found to be both effective and inexpensive enough to implement widely. Our research began in India, with a large-scale geochemical study of the groundwater in a fluoride-contaminated region of Orissa. Having developed a better understanding of the geochemical relationships that exist between fluoride and other parameters present in an affected area, as well as the complex relationships that arise among those parameters that can impact the presence of fluoride, we began investigating certain remediation scenarios involving iron oxides. A common approach to remediation involves the partitioning of fluoride from groundwater by sorption onto a variety of materials, one of the most effective of which is iron oxide whose surface area acts as a scavenger for fluoride. In the presence of iron oxidizing bacteria, the oxidation rate of iron has been shown to be ˜6 times greater than in their absence; fluoride should, therefore, be removed from an aqueous environment by bacteriogenic iron oxides (BIOS) much more quickly than by abiotic iron oxides. Most recently, sorption studies have been conducted using both BIOS and synthetic hydrous ferric oxides in order to compare the behavior between biotic and abiotic sorbents. These studies have provided sorption isotherms that allow comparison of fluoride removed by sorption to BIOS versus synthetic iron oxides. Sorption affinity constants have also been determined, which allow for the

  12. Physical phenomena in a low-temperature non-equilibrium plasma and in MHD generators with non-equilibrium conductivity

    Velikhov, E.P.; Golubev, V.S.; Dykhne, A.M.

    1976-01-01

    The paper assesses the position in 1975 of theoretical and experimental work on the physics of a magnetohydrodynamic generator with non-equilibrium plasma conductivity. This research started at the beginning of the 1960s; as work on the properties of thermally non-equilibrium plasma in magnetic fields and also in MHD generator ducts progressed, a number of phenomena were discovered and investigated that had either been unknown in plasma physics or had remained uninvestigated until that time: ionization instability and ionization turbulence of plasma in a magnetic field, acoustic instability of a plasma with anisotropic conductivity, the non-equilibrium ionization wave and the energy balance of a non-equilibrium plasma. At the same time, it was discovered what physical requirements an MHD generator with non-equilibrium conductivity must satisfy to achieve high efficiency in converting the thermal or kinetic energy of the gas flow into electric energy. The experiments on MHD power generation with thermally non-equilibrium plasma carried out up to 1975 indicated that it should be possible to achieve conversion efficiencies of up to 20-30%. (author)

  13. Evidence of micropore filling for sorption of nonpolar organic contaminants by condensed organic matter.

    Ran, Yong; Yang, Yu; Xing, Baoshan; Pignatello, Joseph J; Kwon, Seokjoo; Su, Wei; Zhou, Li

    2013-01-01

    Although microporosity and surface area of natural organic matter (NOM) are crucial for mechanistic evaluation of the sorption process for nonpolar organic contaminants (NOCs), they have been underestimated by the N adsorption technique. We investigated the CO-derived internal hydrophobic microporosity () and specific surface area (SSA) obtained on dry samples and related them to sorption behaviors of NOCs in water for a wide range of condensed NOM samples. The is obtained from the total CO-derived microporosity by subtracting out the contribution of the outer surfaces of minerals and NOM using N adsorption-derived parameters. The correlation between or CO-SSA and fractional organic carbon content () is very significant, demonstrating that much of the microporosity is associated with internal NOM matrices. The average and CO-SSA are, respectively, 75.1 μL g organic carbon (OC) and 185 m g OC from the correlation analysis. The rigid aliphatic carbon significantly contributes to the microporosity of the Pahokee peat. A strong linear correlation is demonstrated between / and the OC-normalized sorption capacity at the liquid or subcooled liquid-state water solubility calculated via the Freundlich equation for each of four NOCs (phenanthrene, naphthalene, 1,3,5-trichlorobenzene, and 1,2-dichlorobenzene). We concluded that micropore filling ("adsorption") contributes to NOC sorption by condensed NOM, but the exact contribution requires knowing the relationship between the dry-state, CO-determined microporosity and the wet-state, NOC-available microporosity of the organic matter. The findings offer new clues for explaining the nonideal sorption behaviors of NOCs. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

  14. Sorption of strontium and fractal scaling of the heterogeneous media in a candidate VLLW disposal site

    Jinsheng Wang; Rui Zuo; Yanguo Teng; Zongjian Sun; Qinhong Hu

    2010-01-01

    Because of the deposit and accumulation from the debris flow, the heterogeneous geological characteristics is obvious for a candidate very low level waste (VLLW) disposal site, with the grain size ranging from tens of microns to 75 cm. Therefore, it is challenging to directly measure the sorption capacity of the media and the distribution coefficient of some radionuclides, such as strontium. We have studies the correlation of the particle mass content with different grade size and the sorption capacity, which is important in the modeling of radionuclide migration in the heterogeneous disposal site. A total of three deep pits and five shallow trenches were excavated, and 21 solid samples were collected for laboratory experiments. The grade and percentage of the different-sized particles were obtained, and the fractal dimension (D) of the media was calculated from the results of sieved experiments. Steady state sorption time and sorption isotherm of strontium was determined in the heterogeneous media, and sorption and distribution of strontium in the heterogeneous media were evaluated by the relationship between the mass percentage and distribution coefficient (K d ) of the fine-particle media, which was comprised of selected particles with a diameter less than 1 mm, and the correlation on the K d and D was regressed fit. The results indicated that fractal dimension bounded from 2.39 to 2.62 in the media, and K d values of strontium ranged between 119 and 126 in the fine-particle media, and corresponding value was 11 and 43 in the original media. The correlation between K d and D was approximately linear. (author)

  15. Testosterone sorption and desorption: Effects of soil particle size

    Qi, Yong, E-mail: yqi01@unomaha.edu [Civil Engineering Dept., University of Nebraska-Lincoln at Omaha Campus, Omaha, NE 68182 (United States); Zhang, Tian C. [Civil Engineering Dept., University of Nebraska-Lincoln at Omaha Campus, Omaha, NE 68182 (United States); Ren, Yongzheng [School of Environmental Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China)

    2014-08-30

    Graphical abstract: - Highlights: • Smaller soil particles have higher sorption and lower desorption rates. • The sorption capacity ranks as clay > silt > sand. • Small particles like clays have less potential for desorption. • Colloids (clays) have high potential to facilitate the transport of hormones in soil–water environments. - Abstract: Soils contain a wide range of particles of different diameters with different mobility during rainfall events. Effects of soil particles on sorption and desorption behaviors of steroid hormones have not been investigated. In this study, wet sieve washing and repeated sedimentation methods were used to fractionate the soils into five ranges. The sorption and desorption properties and related mechanisms of testosterone in batch reactors filled with fractionated soil particles were evaluated. Results of sorption and desorption kinetics indicate that small soil particles have higher sorption and lower desorption rates than that of big ones. Thermodynamic results show the sorption processes are spontaneous and exothermal. The sorption capacity ranks as clay > silt > sand, depending mainly on specific surface area and surface functional groups. The urea control test shows that hydrogen bonding contributes to testosterone sorption onto clay and silt but not on sand. Desorption tests indicate sorption is 36–65% irreversible from clay to sand. Clays have highest desorption hysteresis among these five soil fractions, indicating small particles like clays have less potential for desorption. The results provide indirect evidence on the colloid (clay)-facilitated transport of hormones (micro-pollutants) in soil environments.

  16. Effect of natural organic materials on cadmium and neptunium sorption

    Kung, K.S.; Triay, I.R.

    1994-01-01

    In a batch sorption study of the effect of naturally occurring organic materials on the sorption of cadmium and neptunium on oxides and tuff surfaces, the model sorbents were synthetic goethite, boehmite, amorphous silicon oxides, and a crushed tuff material from Yucca Mountain, Nevada. An amino acid, 3-(3,4-dihydroxypheny)-DL-alanine (DOPA), and an aquatic-originated fulvic material, Nordic aquatic fulvic acid (NAFA), were used as model organic chemicals. Sorption isotherm results showed that DOPA sorption followed the order aluminum oxide > iron oxide > silicon oxide and that the amount of DOAP sorption for a given sorbent increased as the solution pH was raised. The sorption of cadmium and neptunium on the iron oxide was about ten times higher than that on the aluminum oxide. The sorption of cadmium and neptunium on natural tuff material was much lower than that on aluminum and iron oxides. The sorption of cadmium on iron and aluminum oxides was found to be influenced by the presence of DOPA, and increasing the amount of DOPA coating resulted in higher cadmium sorption on aluminum oxide. However, for iron oxide, cadmium sorption decreased with increasing DOPA concentration. The presence of the model organic materials DOPA and NAFA did not affect the sorption of neptunium on tuff material or on the iron and aluminum oxides. Spectroscopic results indicate that cadmium complexes strongly with DOPA. Therefore, the effect of the organic material, DOPA, on the cadmium sorption is readily observed. However, neptunium is possibly complexed weakly with organic material. Thus, DOPA and NAFA have little effect on neptunium sorption on all sorbents selected for study

  17. Highly sensitive sorption-luminescence determination of trace europium with preconcentration on silica chemically modified with iminodiacetic acid

    Voronina, R.D.; Zorov, N.B.

    2007-01-01

    Features of a sorption-luminescence method for the determination of trace europium were studied. The method includes the preliminary sorption of europium at pH 7.1 from solutions with silica chemically modified with iminodiacetic acid, the subsequent treatment of the sorbent with 2-thenoyltrifluoroacetone at pH 8.0, and the measurement of the intensity of luminescence of the surface three-component europium complex at 613 nm. The effect of moisture as the quencher of luminescence of the surface europium complex was studied, and techniques for its removal were proposed. Sorption in the static mode provides the detection limit of europium of 7 x 10 -5 g/ml. The calibration plot is linear in the range of two orders of magnitude of europium concentration in solutions. The relative standard deviation in the determination of 1.5 x 10 -2 μg/ml europium is 5%. In the dynamic mode of sorption from 1000 ml of an analyzed solution with the use of sorption-desorption, the detection limit of europium of 8 x 10 -7 μg/ml was attained [ru

  18. Sorption of actinides in granitic rock

    Allard, B

    1982-11-01

    The sorption of americium (III), neptunium(V) and plutonium on geologic media under oxic conditions has been measured by a batch technique. The aqueous phase was a synthetic groundwater or 4M NaCl solution. The solid phase was a pure mineral, representative of igneous rocks, or granite. Altogether 40 different minerals and rocks were used. The effects of pH and the ionic strength of the aqueous phase as well as of the cation exchange capacity and the surface/mass ratio of the solid sorbent are discussed. Empirical equations giving the distribution coefficient as a function of pH in the environmental pH-range 7-9 are suggested. Some observations and conclusions concerning sorption mechanisms are given. (author)

  19. Sorption analyses in materials science: selected oxides

    Fuller, E.L. Jr.; Condon, J.B.; Eager, M.H.; Jones, L.L.

    1981-01-01

    Physical adsorption studies have been shown to be extremely valuable in studying the chemistry and structure of dispersed materials. Many processes rely on the access to the large amount of surface made available by the high degree of dispersion. Conversely, there are many applications where consolidation of the dispersed solids is required. Several systems (silica gel, alumina catalysts, mineralogic alumino-silicates, and yttrium oxide plasters) have been studied to show the type and amount of chemical and structural information that can be obtained. Some review of current theories is given and additional concepts are developed based on statistical and thermodynamic arguments. The results are applied to sorption data to show that detailed sorption analyses are extremely useful and can provide valuable information that is difficult to obtain by any other means. Considerable emphasis has been placed on data analyses and interpretation of a nonclassical nature to show the potential of such studies that is often not recognized nor utilized

  20. Sorption of zinc on human teeth

    Helal, A.; Amin, H.; Alian, G.

    1997-01-01

    Zinc containing dental amalgams are sometimes used as fillings by dentists. The freshly mixed mass of the amalgam alloy and liquid mercury packed or condensed into a prepared tooth cavity. Zinc has been included in amalgams alloys up to 2% as an aid in manufacturing by helping to produce clean sound castings of the ingots. Although such restorations have a relatively long service life, they are subject to corrosion and galvanic action, thus releasing metallic products into the oral environment. The aim of this paper is to investigate the uptake (sorption) of Zinc ionic species on human teeth using the radioactive tracer technique. For this purpose the isotope Zn-65 produced from pile-irradiation of zinc metal was used. The various liquids studied were drinking water (tap water), tea, coffee, red tea and chicken soup. Sorption was studied through immersion of a single human tooth (extracted) in each of these liquids

  1. Sorption of 60 Co on inorganic solids

    Granados C, F.; Bulbulian G, S.; Mardel V, B.

    2003-01-01

    The behavior of sorption of the 60 Co in aqueous solution under static conditions to different values of pH of the aqueous solution (1, 3, 5, 7, and 10) on MgO, MnO 2 , SnO, TiO 2 , activated carbon and calcinate hydrotalcite was investigated. It was found that the best sorbents of the 60 Co was the MnO 2 , activated carbon and TiO 2 whose sorption was incremented when increasing the pH value of the aqueous solutions, in the one case of the hydrated oxides, the 60 Co interacted with the electrically charged surface of the sorbents that depends on the pH of the solution and of the point of zero charge (zpc) of the sorbent. (Author)

  2. Noble metal extraction and sorption concentrating

    Petrukhin, O.M.; Malofeeva, G.I.

    1985-01-01

    Works performed in the USSR Academy of Sciences GEOCHI laboratory of extraction methods and devoted to selectivity problems of extraction and sorption methods of platinum metal, cadmium and indium concentrating in analytical chemistry are discussed. On choosing complexino. reagent main attention is paid to the selectivity variation based on different stability of metal complexes. Platinum metals are extracted in the form of ion associates when usinq hard, mainly oxyqen-containing, extractants. Coordination-solvated metal complexes are extracted white usinq extractants containing sulfur, trivalent phosphorus and aromatic nitroqen as donor anions. Selectivity is maximum for sulfur- and nitroren-containinq extractants and sorbents. In case of the group extraction of platinum metals sorption is preferable and in case of selective extraction of individual metals, especially, in case of need of relative concentratinq extraction is preferable

  3. Uranium sorption on tezontle volcanic rock

    Lopez M, B. E.; Duran B, J. M.; Iturbe G, J. L.; Olguin G, M. T.

    2009-01-01

    It is described a study that demonstrates that hexavalent uranium ions were sorbed by the naturally occurring mineral using a batch technique. This mineral is found in abundant quantities in Mexico. Our study focused on the separation of U Vi from synthetic aqueous systems of both H 2 O-UO 2 (NO 3 ) 2 .6H 2 O (acid) and H 2 O-Na 4 [UO 2 (CO 3 ) 3 ] (basic). The chemical speciation was performed by using high voltage electrophoresis, and the uranium content was determined by UV-Vis spectroscopy. The quantified U(Vi) sorption by tezontle from acidic and basic systems was 2.72 and 1.68 μmol/g, respectively, and the sorption behavior is discussed considering the surface charge of the tezontle at different ph values based on the point of zero charge characteristic of this material. (Author)

  4. Sorption of phenanthrene on agricultural soils

    Soares, Antonio; Møldrup, Per; Minh, Luong Nhat

    2013-01-01

    Polyaromatic hydrocarbon (PAH) sorption to soil is a key process deciding the transport and fate of PAH, and potential toxic impacts in the soil and groundwater ecosystems, for example in connection with atmospheric PAH deposition on soils. There are numerous studies on PAH sorption in relatively......, 0.25–1-m depth) by the single-point adsorption method. The organic carbon partition coefficient, KOC (liter per kilogram) for topsoils was found generally to fall between the KOC values estimated by the two most frequently used models for PAH partitioning, the Abdul et al. (Hazardous Waste...... & Hazardous Materials 4(3):211–222, 1987) model and Karickhoff et al. (Water Research 13:241–248, 1979) model. A less-recognized model by Karickhoff (Chemosphere 10:833–846, 1981), yielding a KOC of 14,918 L kg−1, closely corresponded to the average measured KOC value for the topsoils, and this model...

  5. Sorption of radionuclides on London clay

    Berry, J.A.; Bourke, P.J.; Green, A.; Littleboy, A.K.

    1989-02-01

    Techniques for studying the sorption of radionuclides on London clay have been investigated. This work involved the use of through-diffusion, in-diffusion, high-pressure convection and batch methods to study the sorption of iodide, strontium, caesium and americium. Through-diffusion and high-pressure convection methods were found to be most useful for investigating weakly and moderately sorbing nuclides and give realistic values for sorptivity. The batch technique remains the most practical method of obtaining large quantities of data within a relatively short timescale but gives very high sorptivity values. It is however very useful for intercomparisons of nuclides or geological media. The in-diffusion method requires further refinement for use with strongly sorbing nuclides. Good agreement between through-diffusion and high-pressure convection methods was obtained for the sorptivity of strontium, whilst trends observed for caesium by through-diffusion were confirmed by batch measurements. (author)

  6. Positron Spectroscopy of Nanodiamonds after Hydrogen Sorption

    Lyudmila Nikitina

    2018-01-01

    Full Text Available The structure and defects of nanodiamonds influence the hydrogen sorption capacity. Positronium can be used as a sensor for detecting places with the most efficient capture of hydrogen atoms. Hydrogenation of carbon materials was performed from gas atmosphere. The concentration of hydrogen absorbed by the sample depends on the temperature and pressure. The concentration 1.2 wt % is achieved at the temperature of 243 K and the pressure of 0.6 MPa. The hydrogen saturation of nanodiamonds changes the positron lifetime. Increase of sorption cycle numbers effects the positron lifetime, as well as the parameters of the Doppler broadening of annihilation line. The electron-positron annihilation being a sensitive method, it allows detecting the electron density fluctuation of the carbon material after hydrogen saturation.

  7. Sorption studies of radioelements on geological materials

    Berry, John A.; Yui, Mikazu; Kitamura, Akira

    2007-11-01

    Batch sorption experiments have been carried out to study the sorption of uranium, technetium, curium, neptunium, actinium, protactinium, polonium, americium and plutonium onto bentonite, granodiorite and tuff. Mathematical modelling using the HARPHRQ program and the HATCHES database was carried out to predict the speciation of uranium and technetium in the equilibrated seawater, and neptunium, americium and plutonium in the rock equilibrated water. Review of the literature for thermodynamic data for curium, actinium, protactinium and polonium was carried out. Where sufficient data were available, predictions of the speciation and solubility were made. This report is a summary report of the experimental work conducted by AEA Technology during April 1991-March 1998, and the main results have been presented at Material Research Society Symposium Proceedings and published as proceedings of them. (author)

  8. Sorption behaviour of herbicides in soils

    Luchini, L.C.; Wiendl, F.M.; Ruegg, E.F.; Instituto Biologico, Sao Paulo

    1988-01-01

    Environmental contamination by herbicides is related with the sorption phenomenon of these compounds in the soils. The behaviour of paraquat, 2,4-D and diuron was studied in soils with different physico-chemical properties, through the Freundlich adsorption and desorption isotherms, using 14 C-radiolabeled herbicides. Results of the range of the adsorption-desorption of each herbicide was related mainly with the chemical characteristics of these compounds. (author) [pt

  9. Phosphate sorption characteristics of European alpine soils

    Kaňa, Jiří; Kopáček, Jiří; Camarero, L.; Garcia-Pausas, J.

    2011-01-01

    Roč. 75, č. 3 (2011), s. 862-870 ISSN 0361-5995 R&D Projects: GA ČR(CZ) GA526/09/0567; GA AV ČR(CZ) KJB600960907 Grant - others:EU EMERGE(CZ) EVK1-CT-1999-00032 Institutional research plan: CEZ:AV0Z60170517 Keywords : phosphate sorption * alpine soil s * acidification Subject RIV: DJ - Water Pollution ; Quality Impact factor: 1.979, year: 2011

  10. Moisture sorption isotherms of dehydrated whey proteins

    Suzana Rimac Brnčić

    2010-03-01

    Full Text Available Moisture sorption isotherms describe the relation between the moisture content of the dry material (food and relative humidity of the surrounding environment. The data obtained are important in modelling of drying process conditions, packaging and shelf-life stability of food that will provide maximum retaining of aroma, colour and texture as well as nutritive and biological value. The objective of this research was to establish the equilibrium moisture content and water activity, as well as monolayer value of two commercial powdered whey protein isolates before and after tribomechanical micronisation and enzymatic hydrolysis, respectively. At the same time it was necessary to evaluate the best moisture sorption isotherm equation to fit the experimental data. The equilibrium moisture contents in investigated samples were determined using standard gravimetric method at 20 °C. The range of water activities was 0.11 to 0.75. The monolayer moisture content was estimated from sorption data using Brunauer-Emmett-Teller (BET and Guggenheim-Anderson-de Boer (GAB models. The results have shown that tribomechanically treated whey protein isolates as well as protein hydrolizates had lower monolayer moisture content values as well as higher corresponding water activity. Therefore, in spite of the fact that they have lower moisture content, they can be storage at higher relative humidity compared to untreated samples. BET model gave better fit to experimental sorption data for a water activity range from 0.11-0.54, while GAB model gave the closest fit for a water activity to 0.75.

  11. Moisture sorption isotherms of dehydrated whey proteins

    Suzana Rimac Brnčić; Vesna Lelas; Zoran Herceg; Marija Badanjak

    2010-01-01

    Moisture sorption isotherms describe the relation between the moisture content of the dry material (food) and relative humidity of the surrounding environment. The data obtained are important in modelling of drying process conditions, packaging and shelf-life stability of food that will provide maximum retaining of aroma, colour and texture as well as nutritive and biological value. The objective of this research was to establish the equilibrium moisture content and water activity, as well as...

  12. Sorption studies of caesium by complex hexacyanoferrates

    Jacobi, D.

    1992-01-01

    A comprehensive literature review was carried out on the preparation of complex hexacyanoferrates in a granular form suitable for use in a packed column. The preparation of sodium nickel hexacyanoferrate using a freeze-thaw method was studied in detail and a method developed to produce a consistent and reproducible granular product. The equilibrium and sorption kinetics were studied using batch and column tests, and the process modelled to predict performance under various conditions. (author)

  13. Conceptual developments of non-equilibrium statistical mechanics in the early days of Japan

    Ichiyanagi, Masakazu

    1995-11-01

    This paper reviews the research in nonequilibrium statistical mechanics made in Japan in the period between 1930 and 1960. Nearly thirty years have passed since the discovery of the exact formula for the electrical conductivity. With the rise of the linear response theory, the methods and results of which are quickly grasped by anyone, its rationale was pushed aside and even at the stage where the formulation was still incomplete some authors hurried to make physical applications. Such an attitude robbed it of most of its interest for the average physicist, who would approach an understanding of some basic concept, not through abstract and logical analysis but by simply increasing his technical experiences with the concept. The purpose of this review is to rescue the linear response theory from being labeled a mathematical tool and to show that it has considerable physical content. Many key papers, originally written in Japanese, are reproduced.

  14. Linear gate

    Suwono.

    1978-01-01

    A linear gate providing a variable gate duration from 0,40μsec to 4μsec was developed. The electronic circuity consists of a linear circuit and an enable circuit. The input signal can be either unipolar or bipolar. If the input signal is bipolar, the negative portion will be filtered. The operation of the linear gate is controlled by the application of a positive enable pulse. (author)

  15. Sorption of antimony on human teeth

    Nofal, M.; Amin, H.; Alian, G.

    1997-01-01

    The study of the uptake of toxic elements on human teeth represents an interesting research area, as the fate of these elements when present in the human food is of health significance. Since antimony is one of the common toxic elements and since, the chemical behaviour of antimony is similar to that of arsenic, one of the most important toxic elements commonly encountered in cases of food poisoning, it has been decided to investigate its uptake on human teeth and on other restoration materials. The radioactive tracer technique was used to evaluate the concentration of antimony sorbed on teeth. This tracer was obtained by irradiation of antimony metal in the reactor, subsequent dissolution in concentrated sulphuric acid, evaporation to dryness and making the solution 6 M in Hydrochloric acid (1). Antimony prepared in this way is in the trivalent state (Sb III). Sorption was studied in water, tea, coffee, red tea and chicken soup. The highest sorption was achieved from water and chicken soup and least sorption was noticed in case of coffee. The results are presented in the form of the depletion of the radioactivity (A) of antimony with time in presence of a tooth in water and other drinks

  16. Sorption of radon-222 to natural sediments

    Wong, C.S.; Chin, Y.P.; Gschwend, P.M.

    1992-01-01

    The sorption of radon to sediments was investigated, since this may affect the use of porewater radon profiles for estimating bed irrigation rates. Batch experiments showed that radon has an organic-carbon-normalized sediment-water partition coefficient (K oc , L kg oc -1 ) of 21.1 ± 2.9 for a Boston Harbor sediment, 25.3 ± 2.1 for a Charles River sediment, and 22.4 ± 2.6 for a Buzzards Bay sediment. These values are in close agreement with predictions using radon's octanol-water partition coefficient (K ow ), which was measured to be 32.4 ± 1.5. Temperature and ionic strength effects on K oc were estimated to be small. Given rapid sorption kinetics, the authors suggest that slurry stripping techniques used by many investigators to measure 222 Rn in sediment samples collect both sorbed and dissolved radon. Sorption effects were included in a transport model to obtain revised estimates of irrigation rates from existing literature profiles. Irrigation rates had to be increased over previously reported values in proportion to the sediment organic matter content

  17. Radionuclide sorption studies on abyssal red clays

    Erickson, K.L.

    1979-01-01

    The radionuclide sorption properties of a widely distributed abyssal red clay are being experimentally investigated using batch equilibration techniques. This paper summarizes sorption equilibrium data obtained when 0.68 N NaCl solutions containing either Tc, U, Pu, Am or Cm were contacted with samples of the red clay and also summarizes some initial results from experiments designed to determine the relative selectivity of the clay for various nuclides. Under mildly oxidizing conditions, the sorption equilibrium distribution coefficients for technetium were essentially zero. At solution-phase nuclide concentrations on the order of 10 -6 M and less and at solution pH values of about 6.9, the distribution coefficients for plutonium were about 3 x 10 3 m1/gm and for uranium, americium, and curium were about 10 5 ml/gm or greater. However, at solution pH values of about 2.7, the distribution coefficients for each of the nuclides were greatly diminished. Initial experiments conducted in order to determine the relative selectivity of the clay for cesium, barium, and cerium, indicated that the silicate phases in the clay were selective for cesium over barium and cerium. These experiments also indicated that the hydrous oxide phases were selective for cerium over barium and for barium over cesium

  18. Lead sorption-desorption from organic residues.

    Duarte Zaragoza, Victor M; Carrillo, Rogelio; Gutierrez Castorena, Carmen M

    2011-01-01

    Sorption and desorption are mechanisms involved in the reduction of metal mobility and bioavailability in organic materials. Metal release from substrates is controlled by desorption. The capacity of coffee husk and pulp residues, vermicompost and cow manure to adsorb Pb2+ was evaluated. The mechanisms involved in the sorption process were also studied. Organic materials retained high concentrations of lead (up to 36,000 mg L(-1)); however, the mechanisms of sorption varied according to the characteristics of each material: degree of decomposition, pH, cation exchange capacity and percentage of organic matter. Vermicompost and manure removed 98% of the Pb from solution. Lead precipitated in manure and vermicompost, forming lead oxide (PbO) and lead ferrite (PbFe4O7). Adsorption isotherms did not fit to the typical Freundlich and Langmuir equations. Not only specific and non-specific adsorption was observed, but also precipitation and coprecipitation. Lead desorption from vermicompost and cow manure was less than 2%. For remediation of Pb-polluted sites, the application of vermicompost and manure is recommended in places with alkaline soils because Pb precipitation can be induced, whereas coffee pulp residue is recommended for acidic soils where Pb is adsorbed.

  19. Linear Accelerators

    Vretenar, M

    2014-01-01

    The main features of radio-frequency linear accelerators are introduced, reviewing the different types of accelerating structures and presenting the main characteristics aspects of linac beam dynamics

  20. Modeling volatile organic compounds sorption on dry building materials using double-exponential model

    Deng, Baoqing; Ge, Di; Li, Jiajia; Guo, Yuan; Kim, Chang Nyung

    2013-01-01

    A double-exponential surface sink model for VOCs sorption on building materials is presented. Here, the diffusion of VOCs in the material is neglected and the material is viewed as a surface sink. The VOCs concentration in the air adjacent to the material surface is introduced and assumed to always maintain equilibrium with the material-phase concentration. It is assumed that the sorption can be described by mass transfer between the room air and the air adjacent to the material surface. The mass transfer coefficient is evaluated from the empirical correlation, and the equilibrium constant can be obtained by linear fitting to the experimental data. The present model is validated through experiments in small and large test chambers. The predicted results accord well with the experimental data in both the adsorption stage and desorption stage. The model avoids the ambiguity of model constants found in other surface sink models and is easy to scale up

  1. Mathematical Modeling of Moisture Sorption Isotherms and Determination of Isosteric Heats of Sorption of Ziziphus Leaves

    Amel Saad

    2014-01-01

    Full Text Available Desorption and adsorption equilibrium moisture isotherms of Ziziphus spina-christi leaves were determined using the gravimetric-static method at 30, 40, and 50°C for water activity (aw ranging from 0.057 to 0.898. At a given aw, the results show that the moisture content decreases with increasing temperature. A hysteresis effect was observed. The experimental data of sorption were fitted by eight models (GAB, BET, Henderson-Thompson, modified-Chung Pfost, Halsey, Oswin, Peleg, and Adam and Shove. After evaluating the models according to several criteria, the Peleg and Oswin models were found to be the most suitable for describing the sorption curves. The net isosteric heats of desorption and adsorption of Ziziphus spina-christi leaves were calculated by applying the Clausius-Clapeyron equation to the sorption isotherms and an expression for predicting these thermodynamic properties was given.

  2. Linearization Method and Linear Complexity

    Tanaka, Hidema

    We focus on the relationship between the linearization method and linear complexity and show that the linearization method is another effective technique for calculating linear complexity. We analyze its effectiveness by comparing with the logic circuit method. We compare the relevant conditions and necessary computational cost with those of the Berlekamp-Massey algorithm and the Games-Chan algorithm. The significant property of a linearization method is that it needs no output sequence from a pseudo-random number generator (PRNG) because it calculates linear complexity using the algebraic expression of its algorithm. When a PRNG has n [bit] stages (registers or internal states), the necessary computational cost is smaller than O(2n). On the other hand, the Berlekamp-Massey algorithm needs O(N2) where N(≅2n) denotes period. Since existing methods calculate using the output sequence, an initial value of PRNG influences a resultant value of linear complexity. Therefore, a linear complexity is generally given as an estimate value. On the other hand, a linearization method calculates from an algorithm of PRNG, it can determine the lower bound of linear complexity.

  3. Geochemical modelling of the sorption of tetravalent radioelements

    Bond, K.A.; Tweed, C.J.

    1991-05-01

    The results of an experimental study of the sorption of a range of tetravalent radioelements, plutonium (IV), tin (IV), thorium(IV) and uranium(IV), onto clay at pH8 and pH11 have been successfully simulated using a triple layer sorption model. The model has been incorporated into HARPHRQ, a geochemical program based on PHREEQE. The model has been parameterised using data for sorption onto ferric oxyhydroxide and goethite. The effects of hydroxycarboxylic acids on the sorption process have also been investigated experimentally. It was generally observed that in the presence of 2x10 -3 M gluconate, sorption was reduced by up two orders of magnitude. The model has satisfactorily simulated these lower sorptivities, through assuming competing sorption and complexation reactions. This work, therefore, further confirms the need to take account of such organic materials in safety assessment modelling. (author)

  4. Investigation of metal ions sorption of brown peat moss powder

    Kelus, Nadezhda; Blokhina, Elena; Novikov, Dmitry; Novikova, Yaroslavna; Chuchalin, Vladimir

    2017-11-01

    For regularities research of sorptive extraction of heavy metal ions by cellulose and its derivates from aquatic solution of electrolytes it is necessary to find possible mechanism of sorption process and to choice a model describing this process. The present article investigates the regularities of aliovalent metals sorption on brown peat moss powder. The results show that sorption isotherm of Al3+ ions is described by Freundlich isotherm and sorption isotherms of Na+ i Ni2+ are described by Langmuir isotherm. To identify the mechanisms of brown peat moss powder sorption the IR-spectra of the initial brown peat moss powder samples and brown peat moss powder samples after Ni (II) sorption were studied. Metal ion binding mechanisms by brown peat moss powder points to ion exchange, physical adsorption, and complex formation with hydroxyl and carboxyl groups.

  5. Nonlinear and Nonequilibrium Dynamics in Geomaterials

    TenCate, James A.; Pasqualini, Donatella; Habib, Salman; Heitmann, Katrin; Higdon, David; Johnson, Paul A.

    2004-01-01

    The transition from linear to nonlinear dynamical elasticity in rocks is of considerable interest in seismic wave propagation as well as in understanding the basic dynamical processes in consolidated granular materials. We have carried out a careful experimental investigation of this transition for Berea and Fontainebleau sandstones. Below a well-characterized strain, the materials behave linearly, transitioning beyond that point to a nonlinear behavior which can be accurately captured by a s...

  6. Sorption of citalopram, irbesartan and fexofenadine in soils: Estimation of sorption coefficients from soil properties.

    Klement, Aleš; Kodešová, Radka; Bauerová, Martina; Golovko, Oksana; Kočárek, Martin; Fér, Miroslav; Koba, Olga; Nikodem, Antonín; Grabic, Roman

    2018-03-01

    The sorption of 3 pharmaceuticals, which may exist in 4 different forms depending on the solution pH (irbesartan in cationic, neutral and anionic, fexofenadine in cationic, zwitter-ionic and anionic, and citalopram cationic and neutral), in seven different soils was studied. The measured sorption isotherms were described by Freundlich equations, and the sorption coefficients, K F (for the fixed n exponent for each compound), were related to the soil properties to derive relationships for estimating the sorption coefficients from the soil properties (i.e., pedotransfer rules). The largest sorption was obtained for citalopram (average K F value for n = 1 was 1838 cm 3  g -1 ) followed by fexofenadine (K F  = 35.1 cm 3/n μg 1-1/n g -1 , n = 1.19) and irbesartan (K F  = 3.96 cm 3/n μg 1-1/n g -1 , n = 1.10). The behavior of citalopram (CIT) in soils was different than the behaviors of irbesartan (IRB) and fexofenadine (FEX). Different trends were documented according to the correlation coefficients between the K F values for different compounds (R IRB,FEX  = 0.895, p-valuesoil properties in the pedotransfer functions. While the K F value for citalopram was positively related to base cation saturation (BCS) or sorption complex saturation (SCS) and negatively correlated to the organic carbon content (Cox), the K F values of irbesartan and fexofenadine were negatively related to BCS, SCS or the clay content and positively related to Cox. The best estimates were obtained by combining BCS and Cox for citalopram (R 2  = 93.4), SCS and Cox for irbesartan (R 2  = 96.3), and clay content and Cox for fexofenadine (R 2  = 82.9). Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Asymptotic analysis of discrete schemes for non-equilibrium radiation diffusion

    Cui, Xia; Yuan, Guang-wei; Shen, Zhi-jun

    2016-01-01

    Motivated by providing well-behaved fully discrete schemes in practice, this paper extends the asymptotic analysis on time integration methods for non-equilibrium radiation diffusion in [2] to space discretizations. Therein studies were carried out on a two-temperature model with Larsen's flux-limited diffusion operator, both the implicitly balanced (IB) and linearly implicit (LI) methods were shown asymptotic-preserving. In this paper, we focus on asymptotic analysis for space discrete schemes in dimensions one and two. First, in construction of the schemes, in contrast to traditional first-order approximations, asymmetric second-order accurate spatial approximations are devised for flux-limiters on boundary, and discrete schemes with second-order accuracy on global spatial domain are acquired consequently. Then by employing formal asymptotic analysis, the first-order asymptotic-preserving property for these schemes and furthermore for the fully discrete schemes is shown. Finally, with the help of manufactured solutions, numerical tests are performed, which demonstrate quantitatively the fully discrete schemes with IB time evolution indeed have the accuracy and asymptotic convergence as theory predicts, hence are well qualified for both non-equilibrium and equilibrium radiation diffusion. - Highlights: • Provide AP fully discrete schemes for non-equilibrium radiation diffusion. • Propose second order accurate schemes by asymmetric approach for boundary flux-limiter. • Show first order AP property of spatially and fully discrete schemes with IB evolution. • Devise subtle artificial solutions; verify accuracy and AP property quantitatively. • Ideas can be generalized to 3-dimensional problems and higher order implicit schemes.

  8. Influence of selected factors on strontium sorption on bentonites

    Galambos, M.; Kufcakova, J.; Rajec, P.

    2007-01-01

    Sorption on bentonite will play an important role in retarding the migration of radionuclides from a waste repository. Bentonite is a natural clay and one of the most promising candidates for use as a buffer material in the geological disposal systems for high-level nuclear waste. It is intended to isolate metal canisters with highly radioactive waste products from the surrounding rocks because of its ability to retard the movement of radionuclides by sorption. Bentonite is characterized by low permeability, water swelling capability and excellent sorption potential for cationic radionuclides. To correctly assess the sorption potential of radionuclides on bentonite is essential for the development of predictive migration models. The sorption of strontium on bentonite from different Slovak deposits - Jelsovy potok, Kopernica and Lieskovec has been investigated under various experimental conditions, such as contact time, sorbate concentrations, presence of complementary cation. Sorption was studied using the batch technique. The uptake of Sr was rapid and equilibrium was reached almost instantaneously. The instantaneous uptake may be due to adsorption and/or exchange of the metal with some ions on the surface of the adsorbent. The best sorption characteristics distinguish bentonite Kopernica, sorption capacity for Sr of the fraction under 45 mm is 0,48 mmol·g -1 for Sr. The highest values of distribution coefficient were reached for the bentonite Jelsovy potok. Radiation stability has been investigated, the higher sorption parameters were observed for the irradiated bentonites, which can be explained by the increase of specific surface of the bentonite samples. The presence of complementary cations depresses the sorption of Sr on bentonite. Cations Ca 2+ exhibit higher effect on cesium sorption than the Na 2+ ions. Results indicate that the sorption of Sr 2+ on bentonite will be affected by the presence of high concentrations of various salts in the waste water

  9. suitability of murram for phosphorus sorption in constructed wetlands

    Mimi

    sorption isotherms, determination of Phosphorus sorption capacity of the substrates, determination of. Phosphorus sorption as the function of time and determination of effect of temperature on the ... (Na2O + K2O) % SiO2. %. P2O5. %. TiO2. %. LOI. %. 19.2. 1.3. 0.69. 5.13. 0.05. 6.7. 61.9. 0.04. 0.51. 4.4. As presented in ...

  10. Mechanism of cesium sorption on potassium titanium hexacyanoferrate

    Sun Yongxia; Xu Shiping; Song Chongli

    1998-01-01

    The mechanism of cesium sorption on potassium titanium hexacyanoferrate is described. The dependence of the sorption speed on temperature, particle granule size, and the stirring speed is studied. The results show that the sorption process is controlled by liquid film diffusion and particle diffusion. An exchange reaction occurs mainly between K + in the exchanger and Cs + in the solution, i.e. potassium titanium hexacyanoferrate, and Cs + of simulated high-level liquid waste

  11. Linear algebra

    Said-Houari, Belkacem

    2017-01-01

    This self-contained, clearly written textbook on linear algebra is easily accessible for students. It begins with the simple linear equation and generalizes several notions from this equation for the system of linear equations and introduces the main ideas using matrices. It then offers a detailed chapter on determinants and introduces the main ideas with detailed proofs. The third chapter introduces the Euclidean spaces using very simple geometric ideas and discusses various major inequalities and identities. These ideas offer a solid basis for understanding general Hilbert spaces in functional analysis. The following two chapters address general vector spaces, including some rigorous proofs to all the main results, and linear transformation: areas that are ignored or are poorly explained in many textbooks. Chapter 6 introduces the idea of matrices using linear transformation, which is easier to understand than the usual theory of matrices approach. The final two chapters are more advanced, introducing t...

  12. Anaerobic degradation of linear alkylbenzene sulfonate

    Mogensen, Anders Skibsted; Haagensen, Frank; Ahring, Birgitte Kiær

    2003-01-01

    Linear alkylbenzene sulfonate (LAS) found in wastewater is removed in the wastewater treatment facilities by sorption and aerobic biodegradation. The anaerobic digestion of sewage sludge has not been shown to contribute to the removal. The concentration of LAS based on dry matter typically...... increases during anaerobic stabilization due to transformation of easily degradable organic matter. Hence, LAS is regarded as resistant to biodegradation under anaerobic conditions. We present data from a lab-scale semi-continuously stirred tank reactor (CSTR) spiked with linear dodecylbenzene sulfonate (C...

  13. Development of Web-based Software for Sorption Database

    Han, Byoung Sub; Lee, Jae Min; Seo, Min Seok; Kim, Dong Keon

    2009-08-01

    Sorption studies of radionuclides are important parts of research on radioactive waste disposal which is commonly faced in most countries where nuclear programs (power production, a variety of peaceful applications, and research) are implemented. The Sorption Database (DB) plays a very important role in the safety assessment of the radioactive waste disposal. The Sorption DB which is opened externally can be used as reference material of establishing a national policy by improving and changing the pre-developed Sorption program to be web-based. From the industrial point of view, if the Sorption DB is opened to the outside, the safety-related confidence can be achieved for nuclear industry. As the information of Sorption DB is opened, not only credibility can be provided to the administration, local governments and nearby residents, but also input of the collected information can be achieved by online. In addition, the reference material and external awareness/reliability about the domestic level of the Sorption DB management system and the current state can be achieved internationally. In order to provide the information of Sorption DB to users in more efficient way, the analysis and complement of management and search capability for the existing Sorption DB program have been performed and web-based management system has been built to provide services to users. In addition, by applying statistical techniques, it has been designed and implemented to display the accuracy and error of the information

  14. Determining Sorption Rate by a Continuous Gravimetric Method

    Hall, Monicia R; Procell, Lawrence R; Bartram, Philip W; Shuely, Wendel J

    2003-01-01

    ... were automatically recorded in an Excel file while CARC coupons were submerged in solvent. Initial sorption rates were determined for butyl acetate, butyl ether, cyclohexane and propylene carbonate...

  15. The sorption of polonium, actinium and protactinium onto geological materials

    Baston, G.M.N.; Berry, J.A.; Brownsword, M.; Heath, T.G.; Ilett, D.J.; McCrohon, R.; Tweed, C.J.; Yui, M.

    1999-01-01

    This paper describes a combined experimental and modeling program of generic sorption studies to increase confidence in the performance assessment for a potential high-level radioactive waste repository in Japan. The sorption of polonium, actinium and protactinium onto geological materials has been investigated. Sorption of these radioelements onto bentonite, tuff and granodiorite from equilibrated de-ionized water was studied under reducing conditions at room temperature. In addition, the sorption of actinium and protactinium was investigated at 60 C. Thermodynamic chemical modeling was carried out to aid interpretation of the results

  16. The sorption of polonium, actinium and protactinium onto geological materials

    Baston, G.M.N.; Berry, J.A.; Brownsword, M.; Heath, T.G.; Ilett, D.J.; McCrohon, R.; Tweed, C.J.; Yui, M.

    1999-07-01

    This paper describes a combined experimental and modeling program of generic sorption studies to increase confidence in the performance assessment for a potential high-level radioactive waste repository in Japan. The sorption of polonium, actinium and protactinium onto geological materials has been investigated. Sorption of these radioelements onto bentonite, tuff and granodiorite from equilibrated de-ionized water was studied under reducing conditions at room temperature. In addition, the sorption of actinium and protactinium was investigated at 60 C. Thermodynamic chemical modeling was carried out to aid interpretation of the results.

  17. Comparison of neptunium sorption results using batch and column techniques

    Triay, I.R.; Furlano, A.C.; Weaver, S.C.; Chipera, S.J.; Bish, D.L.

    1996-08-01

    We used crushed-rock columns to study the sorption retardation of neptunium by zeolitic, devitrified, and vitric tuffs typical of those at the site of the potential high-level nuclear waste repository at Yucca Mountain, Nevada. We used two sodium bicarbonate waters (groundwater from Well J-13 at the site and water prepared to simulate groundwater from Well UE-25p No. 1) under oxidizing conditions. It was found that values of the sorption distribution coefficient, Kd, obtained from these column experiments under flowing conditions, regardless of the water or the water velocity used, agreed well with those obtained earlier from batch sorption experiments under static conditions. The batch sorption distribution coefficient can be used to predict the arrival time for neptunium eluted through the columns. On the other hand, the elution curves showed dispersivity, which implies that neptunium sorption in these tuffs may be nonlinear, irreversible, or noninstantaneous. As a result, use of a batch sorption distribution coefficient to calculate neptunium transport through Yucca Mountain tuffs would yield conservative values for neptunium release from the site. We also noted that neptunium (present as the anionic neptunyl carbonate complex) never eluted prior to tritiated water, which implies that charge exclusion does not appear to exclude neptunium from the tuff pores. The column experiments corroborated the trends observed in batch sorption experiments: neptunium sorption onto devitrified and vitric tuffs is minimal and sorption onto zeolitic tuffs decreases as the amount of sodium and bicarbonate/carbonate in the water increases

  18. Experimental study of strontium sorption on fissure filling material

    Eriksen, T E; Cui, Daqing [Royal Institute of Technology, Stockholm (Sweden). Dept. of Chemistry

    1994-12-01

    We have carried out a comparative study of sorption and desorption of strontium in groundwater on separated magnetic and size fractions of fissure filling material taken from natural fissures in granitic rock. Complete reversibility of the sorption process was demonstrated by identical Freundlich isotherms, isotopic exchangeability and pH dependence of the distribution coefficients Rd. The sorption was found to be strongly pH dependent in the range 3-11. The pH effect can be accommodated in the sorption model by considering the surface areas and surface charges of the minerals in the fissure filling material. 20 refs, 9 figs, 3 tabs.

  19. Experimental study of strontium sorption on fissure filling material

    Eriksen, T.E.; Cui, Daqing

    1994-12-01

    We have carried out a comparative study of sorption and desorption of strontium in groundwater on separated magnetic and size fractions of fissure filling material taken from natural fissures in granitic rock. Complete reversibility of the sorption process was demonstrated by identical Freundlich isotherms, isotopic exchangeability and pH dependence of the distribution coefficients Rd. The sorption was found to be strongly pH dependent in the range 3-11. The pH effect can be accommodated in the sorption model by considering the surface areas and surface charges of the minerals in the fissure filling material. 20 refs, 9 figs, 3 tabs

  20. Acquisition of sorption isotherms for modified woods by the use of dynamic vapour sorption instrumentation. Principles and Practice

    Engelund, Emil Tang; Klamer, Morten; Venås, Thomas Mark

    2010-01-01

    The complex wood-water relationship has been the topic of numerous studies. Sorption isotherms – in particular – have been derived for hundreds of wood species, their sap- and heartwood sections as well as for decayed, engineered and modified wood materials. However, the traditional methods...... for obtaining sorption isotherms are very time consuming. With new dynamic vapour sorption (DVS) instrumentation, the acquisition of data for constructing sorption isotherms is suddenly dramatically lowered. Where the traditional methods often required months, data can now be obtained in a matter of days...... depending on the number of data points required. The fast data acquisition makes DVS a useful tool in studying the sorption properties of wood, and especially in studying the effect of different modification treatments on these properties. This study includes an investigation of the sorption properties...

  1. Modeling, Measurements, and Fundamental Database Development for Nonequilibrium Hypersonic Aerothermodynamics

    Bose, Deepak

    2012-01-01

    The design of entry vehicles requires predictions of aerothermal environment during the hypersonic phase of their flight trajectories. These predictions are made using computational fluid dynamics (CFD) codes that often rely on physics and chemistry models of nonequilibrium processes. The primary processes of interest are gas phase chemistry, internal energy relaxation, electronic excitation, nonequilibrium emission and absorption of radiation, and gas-surface interaction leading to surface recession and catalytic recombination. NASAs Hypersonics Project is advancing the state-of-the-art in modeling of nonequilibrium phenomena by making detailed spectroscopic measurements in shock tube and arcjets, using ab-initio quantum mechanical techniques develop fundamental chemistry and spectroscopic databases, making fundamental measurements of finite-rate gas surface interactions, implementing of detailed mechanisms in the state-of-the-art CFD codes, The development of new models is based on validation with relevant experiments. We will present the latest developments and a roadmap for the technical areas mentioned above

  2. Nonequilibrium thermodynamics and fluctuation relations for small systems

    Cao Liang; Ke Pu; Qiao Li-Yan; Zheng Zhi-Gang

    2014-01-01

    In this review, we give a retrospect of the recent progress in nonequilibrium statistical mechanics and thermodynamics in small dynamical systems. For systems with only a few number of particles, fluctuations and nonlinearity become significant and contribute to the nonequilibrium behaviors of the systems, hence the statistical properties and thermodynamics should be carefully studied. We review recent developments of this topic by starting from the Gallavotti—Cohen fluctuation theorem, and then to the Evans—Searles transient fluctuation theorem, Jarzynski free-energy equality, and the Crooks fluctuation relation. We also investigate the nonequilibrium free energy theorem for trajectories involving changes of the heat bath temperature and propose a generalized free-energy relation. It should be noticed that the non-Markovian property of the heat bath may lead to the violation of the free-energy relation. (topical review - statistical physics and complex systems)

  3. Non-equilibrium phase transitions in complex plasma

    Suetterlin, K R; Raeth, C; Ivlev, A V; Thomas, H M; Khrapak, S; Zhdanov, S; Rubin-Zuzic, M; Morfill, G E; Wysocki, A; Loewen, H; Goedheer, W J; Fortov, V E; Lipaev, A M; Molotkov, V I; Petrov, O F

    2010-01-01

    Complex plasma being the 'plasma state of soft matter' is especially suitable for investigations of non-equilibrium phase transitions. Non-equilibrium phase transitions can manifest in dissipative structures or self-organization. Two specific examples are lane formation and phase separation. Using the permanent microgravity laboratory PK-3 Plus, operating onboard the International Space Station, we performed unique experiments with binary mixtures of complex plasmas that showed both lane formation and phase separation. These observations have been augmented by comprehensive numerical and theoretical studies. In this paper we present an overview of our most important results. In addition we put our results in context with research of complex plasmas, binary systems and non-equilibrium phase transitions. Necessary and promising future complex plasma experiments on phase separation and lane formation are briefly discussed.

  4. Linear algebra

    Stoll, R R

    1968-01-01

    Linear Algebra is intended to be used as a text for a one-semester course in linear algebra at the undergraduate level. The treatment of the subject will be both useful to students of mathematics and those interested primarily in applications of the theory. The major prerequisite for mastering the material is the readiness of the student to reason abstractly. Specifically, this calls for an understanding of the fact that axioms are assumptions and that theorems are logical consequences of one or more axioms. Familiarity with calculus and linear differential equations is required for understand

  5. Inviscid flux-splitting algorithms for real gases with non-equilibrium chemistry

    Shuen, Jian-Shun; Liou, Meng-Sing; Van Leer, Bram

    1990-01-01

    Formulations of inviscid flux splitting algorithms for chemical nonequilibrium gases are presented. A chemical system for air dissociation and recombination is described. Numerical results for one-dimensional shock tube and nozzle flows of air in chemical nonequilibrium are examined.

  6. Time Dependent Hartree Fock Equation: Gateway to Nonequilibrium Plasmas

    Dufty, James W.

    2007-01-01

    This is the Final Technical Report for DE-FG02-2ER54677 award 'Time Dependent Hartree Fock Equation - Gateway to Nonequilibrium Plasmas'. Research has focused on the nonequilibrium dynamics of electrons in the presence of ions, both via basic quantum theory and via semi-classical molecular dynamics (MD) simulation. In addition, fundamental notions of dissipative dynamics have been explored for models of grains and dust, and for scalar fields (temperature) in turbulent edge plasmas. The specific topics addressed were Quantum Kinetic Theory for Metallic Clusters, Semi-classical MD Simulation of Plasmas , and Effects of Dissipative Dynamics.

  7. Introduction to nonequilibrium statistical mechanics with quantum field theory

    Kita, Takafumi

    2010-01-01

    In this article, we present a concise and self-contained introduction to nonequilibrium statistical mechanics with quantum field theory by considering an ensemble of interacting identical bosons or fermions as an example. Readers are assumed to be familiar with the Matsubara formalism of equilibrium statistical mechanics such as Feynman diagrams, the proper self-energy, and Dyson's equation. The aims are threefold: (1) to explain the fundamentals of nonequilibrium quantum field theory as simple as possible on the basis of the knowledge of the equilibrium counterpart; (2) to elucidate the hierarchy in describing nonequilibrium systems from Dyson's equation on the Keldysh contour to the Navier-Stokes equation in fluid mechanics via quantum transport equations and the Boltzmann equation; (3) to derive an expression of nonequilibrium entropy that evolves with time. In stage (1), we introduce nonequilibrium Green's function and the self-energy uniquely on the round-trip Keldysh contour, thereby avoiding possible confusions that may arise from defining multiple Green's functions at the very beginning. We try to present the Feynman rules for the perturbation expansion as simple as possible. In particular, we focus on the self-consistent perturbation expansion with the Luttinger-Ward thermodynamic functional, i.e., Baym's Φ-derivable approximation, which has a crucial property for nonequilibrium systems of obeying various conservation laws automatically. We also show how the two-particle correlations can be calculated within the Φ-derivable approximation, i.e., an issue of how to handle the 'Bogoliubov-Born-Green-Kirkwood-Yvons (BBGKY) hierarchy'. Aim (2) is performed through successive reductions of relevant variables with the Wigner transformation, the gradient expansion based on the Groenewold-Moyal product, and Enskog's expansion from local equilibrium. This part may be helpful for convincing readers that nonequilibrium systems can be handled microscopically with

  8. Limiting processes in non-equilibrium classical statistical mechanics

    Jancel, R.

    1983-01-01

    After a recall of the basic principles of the statistical mechanics, the results of ergodic theory, the transient at the thermodynamic limit and his link with the transport theory near the equilibrium are analyzed. The fundamental problems put by the description of non-equilibrium macroscopic systems are investigated and the kinetic methods are stated. The problems of the non-equilibrium statistical mechanics are analyzed: irreversibility and coarse-graining, macroscopic variables and kinetic description, autonomous reduced descriptions, limit processes, BBGKY hierarchy, limit theorems [fr

  9. Convection with local thermal non-equilibrium and microfluidic effects

    Straughan, Brian

    2015-01-01

    This book is one of the first devoted to an account of theories of thermal convection which involve local thermal non-equilibrium effects, including a concentration on microfluidic effects. The text introduces convection with local thermal non-equilibrium effects in extraordinary detail, making it easy for readers newer to the subject area to understand. This book is unique in the fact that it addresses a large number of convection theories and provides many new results which are not available elsewhere. This book will be useful to researchers from engineering, fluid mechanics, and applied mathematics, particularly those interested in microfluidics and porous media.

  10. Forces and energy dissipation in inhomogeneous non-equilibrium superconductors

    Poluehktov, Yu.M.; Slezov, V.V.

    1987-01-01

    The phenomenological theory of volume forces and dissipation processes in inhomogeneous non-equilibrium superconductors near temperature transition from the normal to superconducting state is constructed. The approach is based on application of dynamic equations of superconductivity formulated on the basis of the Lagrangian formalism. These equations are generalized the Ginzburg-Landau theory in the nonstationary non-equilibrium case for ''foul'' superconductors. The value estimations of volume forces arising in inhomogeneities during relaxation of an order parameter and when the electrical field is penetrated into the superconductor, are given

  11. Experimental approaches for studying non-equilibrium atmospheric plasma jets

    Shashurin, A., E-mail: ashashur@purdue.edu [School of Aeronautics & Astronautics, Purdue University, West Lafayette, Indiana 47907 (United States); Keidar, M. [Department of Mechanical and Aerospace Engineering, The George Washington University, Washington, District of Columbia 20052 (United States)

    2015-12-15

    This work reviews recent research efforts undertaken in the area non-equilibrium atmospheric plasma jets with special focus on experimental approaches. Physics of small non-equilibrium atmospheric plasma jets operating in kHz frequency range at powers around few Watts will be analyzed, including mechanism of breakdown, process of ionization front propagation, electrical coupling of the ionization front with the discharge electrodes, distributions of excited and ionized species, discharge current spreading, transient dynamics of various plasma parameters, etc. Experimental diagnostic approaches utilized in the field will be considered, including Rayleigh microwave scattering, Thomson laser scattering, electrostatic streamer scatterers, optical emission spectroscopy, fast photographing, etc.

  12. Linear programming

    Solow, Daniel

    2014-01-01

    This text covers the basic theory and computation for a first course in linear programming, including substantial material on mathematical proof techniques and sophisticated computation methods. Includes Appendix on using Excel. 1984 edition.

  13. Linear algebra

    Liesen, Jörg

    2015-01-01

    This self-contained textbook takes a matrix-oriented approach to linear algebra and presents a complete theory, including all details and proofs, culminating in the Jordan canonical form and its proof. Throughout the development, the applicability of the results is highlighted. Additionally, the book presents special topics from applied linear algebra including matrix functions, the singular value decomposition, the Kronecker product and linear matrix equations. The matrix-oriented approach to linear algebra leads to a better intuition and a deeper understanding of the abstract concepts, and therefore simplifies their use in real world applications. Some of these applications are presented in detailed examples. In several ‘MATLAB-Minutes’ students can comprehend the concepts and results using computational experiments. Necessary basics for the use of MATLAB are presented in a short introduction. Students can also actively work with the material and practice their mathematical skills in more than 300 exerc...

  14. Linear algebra

    Berberian, Sterling K

    2014-01-01

    Introductory treatment covers basic theory of vector spaces and linear maps - dimension, determinants, eigenvalues, and eigenvectors - plus more advanced topics such as the study of canonical forms for matrices. 1992 edition.

  15. Linear Models

    Searle, Shayle R

    2012-01-01

    This 1971 classic on linear models is once again available--as a Wiley Classics Library Edition. It features material that can be understood by any statistician who understands matrix algebra and basic statistical methods.

  16. Lower bounds for ballistic current and noise in non-equilibrium quantum steady states

    Benjamin Doyon

    2015-03-01

    Full Text Available Let an infinite, homogeneous, many-body quantum system be unitarily evolved for a long time from a state where two halves are independently thermalized. One says that a non-equilibrium steady state emerges if there are nonzero steady currents in the central region. In particular, their presence is a signature of ballistic transport. We analyze the consequences of the current observable being a conserved density; near equilibrium this is known to give rise to linear wave propagation and a nonzero Drude peak. Using the Lieb–Robinson bound, we derive, under a certain regularity condition, a lower bound for the non-equilibrium steady-state current determined by equilibrium averages. This shows and quantifies the presence of ballistic transport far from equilibrium. The inequality suggests the definition of “nonlinear sound velocities”, which specialize to the sound velocity near equilibrium in non-integrable models, and “generalized sound velocities”, which encode generalized Gibbs thermalization in integrable models. These are bounded by the Lieb–Robinson velocity. The inequality also gives rise to a bound on the energy current noise in the case of pure energy transport. We show that the inequality is satisfied in many models where exact results are available, and that it is saturated at one-dimensional criticality.

  17. Systematic approach to leptogenesis in nonequilibrium QFT: Vertex contribution to the CP-violating parameter

    Garny, M.; Hohenegger, A.; Kartavtsev, A.; Lindner, M.

    2009-01-01

    The generation of a baryon asymmetry via leptogenesis is usually studied by means of classical kinetic equations whose applicability to processes in the hot and expanding early universe is questionable. The approximations implied by the state-of-the-art description can be tested in a first-principle approach based on nonequilibrium field theory techniques. Here, we apply the Schwinger-Keldysh/Kadanoff-Baym formalism to a simple toy model of leptogenesis. We find that, within the toy model, medium effects increase the vertex contribution to the CP-violating parameter. At high temperatures it is a few times larger than in vacuum and asymptotically reaches the vacuum value as the temperature decreases. Contrary to the results obtained earlier in the framework of thermal field theory, the corrections are only linear in the particle number densities. An important feature of the Kadanoff-Baym formalism is that it is free of the double-counting problem, i.e. no need for real intermediate state subtraction arises. In particular, this means that the structure of the equations automatically ensures that the asymmetry vanishes in equilibrium. These results give a first glimpse into a number of new and interesting effects that can be studied in the framework of nonequilibrium field theory.

  18. Nonequilibrium Langevin dynamics: A demonstration study of shear flow fluctuations in a simple fluid

    Belousov, Roman; Cohen, E. G. D.; Rondoni, Lamberto

    2017-08-01

    The present paper is based on a recent success of the second-order stochastic fluctuation theory in describing time autocorrelations of equilibrium and nonequilibrium physical systems. In particular, it was shown to yield values of the related deterministic parameters of the Langevin equation for a Couette flow in a microscopic molecular dynamics model of a simple fluid. In this paper we find all the remaining constants of the stochastic dynamics, which then is simulated numerically and compared directly with the original physical system. By using these data, we study in detail the accuracy and precision of a second-order Langevin model for nonequilibrium physical systems theoretically and computationally. We find an intriguing relation between an applied external force and cumulants of the resulting flow fluctuations. This is characterized by a linear dependence of an athermal cumulant ratio, an apposite quantity introduced here. In addition, we discuss how the order of a given Langevin dynamics can be raised systematically by introducing colored noise.

  19. 3.3. Sorption activity of cross-linked polymers of ethynyl-piperidol

    Khalikov, D.Kh.

    2012-01-01

    The sorption activity of cross-linked polymers of ethynyl-piperidol was studied. The bilirubin sorption was studied as well. The kinetic of bilirubin sorption and human serum albumin at their joint presence in hydrogel solutions was defined. Bilirubin sorption and change of albumin composition was considered. The sorption of middle molecular peptides was considered as well. The sorption of endogenous toxin by means of ethynyl-piperidol polymers was done.

  20. General multi-group macroscopic modeling for thermo-chemical non-equilibrium gas mixtures

    Liu, Yen, E-mail: yen.liu@nasa.gov; Vinokur, Marcel [NASA Ames Research Center, Moffett Field, California 94035 (United States); Panesi, Marco; Sahai, Amal [University of Illinois, Urbana-Champaign, Illinois 61801 (United States)

    2015-04-07

    This paper opens a new door to macroscopic modeling for thermal and chemical non-equilibrium. In a game-changing approach, we discard conventional theories and practices stemming from the separation of internal energy modes and the Landau-Teller relaxation equation. Instead, we solve the fundamental microscopic equations in their moment forms but seek only optimum representations for the microscopic state distribution function that provides converged and time accurate solutions for certain macroscopic quantities at all times. The modeling makes no ad hoc assumptions or simplifications at the microscopic level and includes all possible collisional and radiative processes; it therefore retains all non-equilibrium fluid physics. We formulate the thermal and chemical non-equilibrium macroscopic equations and rate coefficients in a coupled and unified fashion for gases undergoing completely general transitions. All collisional partners can have internal structures and can change their internal energy states after transitions. The model is based on the reconstruction of the state distribution function. The internal energy space is subdivided into multiple groups in order to better describe non-equilibrium state distributions. The logarithm of the distribution function in each group is expressed as a power series in internal energy based on the maximum entropy principle. The method of weighted residuals is applied to the microscopic equations to obtain macroscopic moment equations and rate coefficients succinctly to any order. The model’s accuracy depends only on the assumed expression of the state distribution function and the number of groups used and can be self-checked for accuracy and convergence. We show that the macroscopic internal energy transfer, similar to mass and momentum transfers, occurs through nonlinear collisional processes and is not a simple relaxation process described by, e.g., the Landau-Teller equation. Unlike the classical vibrational energy

  1. General multi-group macroscopic modeling for thermo-chemical non-equilibrium gas mixtures

    Liu, Yen; Panesi, Marco; Sahai, Amal; Vinokur, Marcel

    2015-04-01

    This paper opens a new door to macroscopic modeling for thermal and chemical non-equilibrium. In a game-changing approach, we discard conventional theories and practices stemming from the separation of internal energy modes and the Landau-Teller relaxation equation. Instead, we solve the fundamental microscopic equations in their moment forms but seek only optimum representations for the microscopic state distribution function that provides converged and time accurate solutions for certain macroscopic quantities at all times. The modeling makes no ad hoc assumptions or simplifications at the microscopic level and includes all possible collisional and radiative processes; it therefore retains all non-equilibrium fluid physics. We formulate the thermal and chemical non-equilibrium macroscopic equations and rate coefficients in a coupled and unified fashion for gases undergoing completely general transitions. All collisional partners can have internal structures and can change their internal energy states after transitions. The model is based on the reconstruction of the state distribution function. The internal energy space is subdivided into multiple groups in order to better describe non-equilibrium state distributions. The logarithm of the distribution function in each group is expressed as a power series in internal energy based on the maximum entropy principle. The method of weighted residuals is applied to the microscopic equations to obtain macroscopic moment equations and rate coefficients succinctly to any order. The model's accuracy depends only on the assumed expression of the state distribution function and the number of groups used and can be self-checked for accuracy and convergence. We show that the macroscopic internal energy transfer, similar to mass and momentum transfers, occurs through nonlinear collisional processes and is not a simple relaxation process described by, e.g., the Landau-Teller equation. Unlike the classical vibrational energy

  2. General multi-group macroscopic modeling for thermo-chemical non-equilibrium gas mixtures.

    Liu, Yen; Panesi, Marco; Sahai, Amal; Vinokur, Marcel

    2015-04-07

    This paper opens a new door to macroscopic modeling for thermal and chemical non-equilibrium. In a game-changing approach, we discard conventional theories and practices stemming from the separation of internal energy modes and the Landau-Teller relaxation equation. Instead, we solve the fundamental microscopic equations in their moment forms but seek only optimum representations for the microscopic state distribution function that provides converged and time accurate solutions for certain macroscopic quantities at all times. The modeling makes no ad hoc assumptions or simplifications at the microscopic level and includes all possible collisional and radiative processes; it therefore retains all non-equilibrium fluid physics. We formulate the thermal and chemical non-equilibrium macroscopic equations and rate coefficients in a coupled and unified fashion for gases undergoing completely general transitions. All collisional partners can have internal structures and can change their internal energy states after transitions. The model is based on the reconstruction of the state distribution function. The internal energy space is subdivided into multiple groups in order to better describe non-equilibrium state distributions. The logarithm of the distribution function in each group is expressed as a power series in internal energy based on the maximum entropy principle. The method of weighted residuals is applied to the microscopic equations to obtain macroscopic moment equations and rate coefficients succinctly to any order. The model's accuracy depends only on the assumed expression of the state distribution function and the number of groups used and can be self-checked for accuracy and convergence. We show that the macroscopic internal energy transfer, similar to mass and momentum transfers, occurs through nonlinear collisional processes and is not a simple relaxation process described by, e.g., the Landau-Teller equation. Unlike the classical vibrational energy

  3. General multi-group macroscopic modeling for thermo-chemical non-equilibrium gas mixtures

    Liu, Yen; Vinokur, Marcel; Panesi, Marco; Sahai, Amal

    2015-01-01

    This paper opens a new door to macroscopic modeling for thermal and chemical non-equilibrium. In a game-changing approach, we discard conventional theories and practices stemming from the separation of internal energy modes and the Landau-Teller relaxation equation. Instead, we solve the fundamental microscopic equations in their moment forms but seek only optimum representations for the microscopic state distribution function that provides converged and time accurate solutions for certain macroscopic quantities at all times. The modeling makes no ad hoc assumptions or simplifications at the microscopic level and includes all possible collisional and radiative processes; it therefore retains all non-equilibrium fluid physics. We formulate the thermal and chemical non-equilibrium macroscopic equations and rate coefficients in a coupled and unified fashion for gases undergoing completely general transitions. All collisional partners can have internal structures and can change their internal energy states after transitions. The model is based on the reconstruction of the state distribution function. The internal energy space is subdivided into multiple groups in order to better describe non-equilibrium state distributions. The logarithm of the distribution function in each group is expressed as a power series in internal energy based on the maximum entropy principle. The method of weighted residuals is applied to the microscopic equations to obtain macroscopic moment equations and rate coefficients succinctly to any order. The model’s accuracy depends only on the assumed expression of the state distribution function and the number of groups used and can be self-checked for accuracy and convergence. We show that the macroscopic internal energy transfer, similar to mass and momentum transfers, occurs through nonlinear collisional processes and is not a simple relaxation process described by, e.g., the Landau-Teller equation. Unlike the classical vibrational energy

  4. Sorption of nitrate onto amine-crosslinked wheat straw: characteristics, column sorption and desorption properties.

    Xing, Xu; Gao, Bao-Yu; Zhong, Qian-Qian; Yue, Qin-Yan; Li, Qian

    2011-02-15

    The nitrate removal process was evaluated using a fixed-bed column packed with amine-crosslinked wheat straw (AC-WS). Column sorption and desorption characteristics of nitrate were studied extensively. Solid-state (13)C NMR and zeta potential analysis validated the existence of crosslinked amine groups in AC-WS. Raman shift of the nitrate peaks suggested the electrostatic attraction between the adsorbed ions and positively charged amine sites. The column sorption capacity (q(ed)) of the AC-WS for nitrate was 87.27 mg g(-1) in comparison with the raw WS of 0.57 mg g(-1). Nitrate sorption in column was affected by bed height, influent nitrate concentration, flow rate and pH, and of all these, influent pH demonstrated an essential effect on the performance of the column. In addition, desorption and dynamic elution tests were repeated for several cycles, with high desorption rate and slight losses in its initial column sorption capacity. Copyright © 2010 Elsevier B.V. All rights reserved.

  5. LINEAR ACCELERATOR

    Christofilos, N.C.; Polk, I.J.

    1959-02-17

    Improvements in linear particle accelerators are described. A drift tube system for a linear ion accelerator reduces gap capacity between adjacent drift tube ends. This is accomplished by reducing the ratio of the diameter of the drift tube to the diameter of the resonant cavity. Concentration of magnetic field intensity at the longitudinal midpoint of the external sunface of each drift tube is reduced by increasing the external drift tube diameter at the longitudinal center region.

  6. Humidity sorption on natural building stone

    Franzen, C.; Mirwald, P.

    2003-04-01

    processes, physical, chemical or biological, depend on the presence of water. Like most porous materials building stone respond on humidity by water uptake. The sorption isotherm represents the equilibrium moisture, specific for each material. The determination of the isotherm for stone of low and small porosity like marble is difficult. With the help of a newly developed water sorption analysis chamber [2], which allows the simultaneous measurement of 11 samples, good results on stone/rock samples have been obtained. Even at marble species with pore volumes lower than 0.4 % isotherms are measured. This analytical method offers new insights in the pore behaviour of low porosity materials. The advantages of this technique which supplements other techniques (e.g. BET, Hg-porosimetry) are: i) the testing agent is identical to the weathering agent, water; ii) the atmospheric parameters at the measurement reflect the natural conditions - thus no changes to the material properties have to be considered; iii) due to the small diameter of the water molecule (~0.28 nm), smaller pores are reached than e.g. with N2 (~0.31 nm). Sorption isotherms of sandstone (Baumberg, Obernkirchen, Groeden), granite (Brixen), and marble (Sterzing, Laas) are presented. Particular as to marbles the resolution is considerably higher. A previously observed negative hysteresis [3] seems an effect due to limited data resolution. [1] Snethlage, R. (1984) Steinkonservierung, Bayer. LA Denkmalpflege, Ah. 22, 203 S. [2] Griesser, U.J., Dillenz, J. (2002) Neuartiges, vollautomatisches Feuchtesorptionsprüfgerät mit hohem Probendurchsatz, Feuchtetag 2002, Weimar, 85-93. [3] Fimmel, R. (1996) Verwitterungsverhalten der alpinen Marmore von Laas und Sterzing, Diss. Univ. Ibk, 116 S.

  7. EXAFS study of plutonium sorption onto kaolinite

    Reich, T.Y.; Banik, L.; Buda, R.A.; Amayri, S.; Drebert, J.; Kratz, J.V.; Trautmann, N.; Reich, T.; Ageev, A.L.; Korshunov, M.E.

    2007-01-01

    The uptake mechanism of plutonium by kaolinite was investigated by applying X-ray absorption spectroscopy to batch sorption samples (total Pu concentrations 1 and 10 μM; 4 g kaolinite/L in 0.1 M NaClO 4 ; 1 ≤ pH ≤ 9; presence and absence of ambient CO 2 ). For XAFS measurements, one sample was prepared from a Pu(III) solution at pH 6 under argon atmosphere. Three samples were obtained by sorption of Pu(IV) at pH I, 4, and 9 in an air-equilibrated system. The Pu L III -edge XANES spectra indicated that in all samples, including the Pu(III) sample, plutonium is sorbed at the kaolinite surface as Pu(IV). The Pu L III -edge k 3 -weighted EXAFS spectra showed eight oxygen atoms at an average Pu-O distance of 2.3 angstrom. Two Pu atoms were detected at ∼ 3.7 angstrom in all spectra, indicating the formation of polynuclear Pu(IV) species at the kaolinite surface. For the sample prepared from Pu(III) solution, an additional Pu-O shell at 3.2 angstrom was observed. The spectra of samples prepared from Pu(IV) included a Pu-Al/Si co-ordination shell at approximately 3.6 angstrom, indicating formation of inner-sphere sorption complexes. The structural models used in the least-squares fits were confirmed by an alternative EXAFS data analysis approach based on a modified Tikhonov regularization method. (authors)

  8. Sorption of pesticides to aquifer minerals

    Clausen, Liselotte; Fabricius, Ida Lykke

    2000-01-01

    This paper summarizes results from a work were the sorption of five pesticides on seven minerals were studied in order to quantify the adsorption to different mineral surfaces. Investigated mineral phases are: quartz, calcite, kaolinite, a-alumina, and three iron oxides (2-line ferrihydrite......, goethite, lepidocrocite). Selected pesticides are: atrazine, isoproturon, mecoprop, 2,4-D, and bentazone. The results demonstrate that pesticides adsorb to pure mineral surfaces. However, the size of the adsorption depends on the type of pesticide and the type of mineral....

  9. Tritium sorption by cement and subsequent release

    Ono, F.; Tanaka, S.; Yamawaki, M.

    1994-01-01

    In a fusion reactor or tritium handling facilities, contamination of concrete by tritium and subsequent release from it to the reactor or experimental rooms is a matter of problem for safety control of tritium and management of operational environment. In order to evaluate these tritium behavior, interaction of tritiated water with concrete or cement should be clarified. In the present study, HTO sorption and subsequent release from cement were studied by combining various experimental methods. From the basic studies on tritium-cement interactions, it has become possible to evaluate tritium uptake by cement or concrete and subsequent tritium release behavior as well as tritium removing methods from them

  10. Sorption of radiostrontium from liquid metallic rubidium

    Zhujkov, B.L.; Kokhnyuk, V.M.; Vincent, J.S.

    2008-01-01

    One studied the radiostrontium (in particular, 82 Sr) sorption from the liquid metallic Rb in various inorganic sorbents (both metals and oxides). One studied the temperature dependence and the dynamics of the adsorption and put forward an interpretation of the observed mechanisms. The elaborated approach enables to extract 82 Sr efficiently from the Rb targets upon their irradiation by the accelerated protons. One studies various procedures and the applicability of the process to ensure elaboration of a new highly efficient process to produce 82 Sr, in particular, with the targets of the circulating Rb [ru

  11. Pu sorption to activated conglomerate anaerobic bacteria

    Sasaki, Takayuki; Kudo, Akira

    2001-01-01

    The sorption of Pu to the anaerobic bacteria activated under specific conditions of temperature, pH and depleted nutrients after long dormant period was investigated. After 4 h at neutral pH, the distribution coefficient (K d ) between bacteria and aqueous phase at 308 and 278 K had around 10 3 to 10 4 . After over 5 days, however, the K d at only 308 K had increased to over 10 5 . Sterilized (dead) and dormant anaerobic bacteria adsorbed Pu to the same extent. (author)

  12. Radionuclide sorption in Yucca Mountain tuffs with J-13 well water: Neptunium, uranium, and plutonium. Yucca Mountain site characterization program milestone 3338

    Triay, I.R.; Cotter, C.R.; Kraus, S.M.; Huddleston, M.H.

    1996-08-01

    We studied the retardation of actinides (neptunium, uranium, and plutonium) by sorption as a function of radionuclide concentration in water from Well J-13 and of tuffs from Yucca Mountain. Three major tuff types were examined: devitrified, vitric, and zeolitic. To identify the sorbing minerals in the tuffs, we conducted batch sorption experiments with pure mineral separates. These experiments were performed with water from Well J-13 (a sodium bicarbonate groundwater) under oxidizing conditions in the pH range from 7 to 8.5. The results indicate that all actinides studied sorb strongly to synthetic hematite and also that Np(V) and U(VI) do not sorb appreciably to devitrified or vitric tuffs, albite, or quartz. The sorption of neptunium onto clinoptilolite-rich tuffs and pure clinoptilolite can be fitted with a sorption distribution coefficient in the concentration range from 1 X 10 -7 to 3 X 10 -5 M. The sorption of uranium onto clinoptilolite-rich tuffs and pure clinoptilolite is not linear in the concentration range from 8 X 10 -8 to 1 X 10 -4 M, and it can be fitted with nonlinear isotherm models (such as the Langmuir or the Freundlich Isotherms). The sorption of neptunium and uranium onto clinoptilolite in J-13 well water increases with decreasing pH in the range from 7 to 8.5. The sorption of plutonium (initially in the Pu(V) oxidation state) onto tuffs and pure mineral separates in J-13 well water at pH 7 is significant. Plutonium sorption decreases as a function of tuff type in the order: zeolitic > vitric > devitrified; and as a function of mineralogy in the order: hematite > clinoptilolite > albite > quartz

  13. Sorption of Triangular Silver Nanoplates on Polyurethane Foam

    Furletov, A. A.; Apyari, V. V.; Garshev, A. V.; Volkov, P. A.; Tolmacheva, V. V.; Dmitrienko, S. G.

    2018-02-01

    The sorption of triangular silver nanoplates on polyurethane foam is investigated as a procedure for creating a nanocomposite sensing material for subsequent use in optical means of chemical analysis. Triangular silver nanoplates are synthesized and characterized, and a simple sorption technique for the formation of a composite material based on these nanoplates is proposed.

  14. Sorption and desorption of diuron in Oxisol under biochar application

    Fabiano André Petter

    Full Text Available ABSTRACT The objective of this study was to verify the kinetics of sorption and desorption of diuron in an Oxisol under application of biochar. The samples were collected in a field experiment conducted in randomized design blocks consisted of 2 base fertilization levels (0 and 400 kg∙ha−1 NPK 00-20-20 fertilizer formula and 3 doses of biochar (0, 8 and 16 Mg∙ha−1. In the evaluation of sorption and desorption, Batch Equilibrium method was used. The kinetics of sorption and desorption of diuron, total organic carbon, fulvic acid, humic acid and humin, pH and partition coefficient to organic carbon were evaluated. The Freundlich isotherm was adjusted appropriately to describe diuron sorption kinetics in all the studied treatments. The application of biochar provided increment in the sorption (Kf and reduction in the desorption of diuron in 64 and 44%, respectively. This effect is attributed to the biochar contribution to the total organic carbon and C-humin and of these to diuron through hydrophobic interactions and hydrogen bonds. The positive correlation between the partition coefficient to organic carbon and Kf confirms the importance of soil organic compartment in the sorption of diuron. There was no competition of NPK fertilizer for the same sorption site of diuron. The increase and reduction in sorption and desorption, respectively, show that the application of biochar is an important alternative for the remediation of soil leaching of diuron, especially in sandy soils.

  15. Kinetics and reversibility of micropollutant sorption in sludge.

    Barret, Maialen; Carrère, Hélène; Patau, Mathieu; Patureau, Dominique

    2011-10-01

    The fate of micropollutants throughout wastewater treatment systems is highly dependent on their sorption interactions with sludge matter. In this study, both the sorption and desorption kinetics of polycyclic aromatic hydrocarbons (PAHs) in activated sludge were shown to be very rapid in comparison to biodegradation kinetics. It was concluded that PAH transfer does not limit their biodegradation and that their fate is governed by the sorption/desorption equilibrium state. The effect of contact time between sludge and PAHs was also investigated. It was shown that aging did not influence the sorption/desorption equilibrium although PAH losses during aging suggest that sequestration phenomena had occurred. This implies that for PAH sorption assessment within treatment processes there is no need to include a contact time dimension. As a consequence, thanks to an innovative approach taking into account sorption equilibria and sequestration, this work has demonstrated that studies in the literature which, in main, deal with micropollutant sorption in sewage sludge with only a short contact time can be extrapolated to real systems in which sorption, desorption and aging occur.

  16. CO2 sorption of a ceramic separation membrane

    Wormeester, Herbert; Benes, Nieck Edwin; Spijksma, G.I.; Verweij, H.; Poelsema, Bene

    2004-01-01

    The ellipsometric characterization of the CO2 sorption of a silica membrane provides a fast and accurate technique for the characterization of maximum sorption and the heat of adsorption. Both parameters are evaluated for the 73 nm thick silica layer as well as the 1650 nm thick supporting γ-layer.

  17. Status report on SIRS: sorption information retrieval system

    Hostetler, D.D.; Serne, R.J.; Baldwin, A.J.; Petrie, G.M.

    1980-11-01

    Two major uses were identified for the Sorption Information Retrieval System: (1) to aid geochemists in the elucidation of sorption mechanisms; and (2) to aid safety assessment modelers in selection of Kds for any given scenerio. Other benefits such as providing an auditable vehicle for the Kd selection were also discussed

  18. Effect of humic acid (HA) on sulfonamide sorption by biochars

    Lian, Fei; Sun, Binbin; Chen, Xi; Zhu, Lingyan; Liu, Zhongqi; Xing, Baoshan

    2015-01-01

    Effect of quantity and fractionation of loaded humic acid (HA) on biochar sorption for sulfonamides was investigated. The HA was applied in two different modes, i.e. pre-coating and co-introduction with sorbate. In pre-coating mode, the polar fractions of HA tended to interact with low-temperature biochars via H-bonding, while the hydrophobic fractions were likely to be adsorbed by high-temperature biochars through hydrophobic and π-π interactions, leading to different composition and structure of the HA adlayers. The influences of HA fractionation on biochar sorption for sulfonamides varied significantly, depending on the nature of interaction between HA fraction and sorbate. Meanwhile, co-introduction of HA with sulfonamides revealed that the effect of HA on sulfonamide sorption was also dependent on HA concentration. These findings suggest that the amount and fractionation of adsorbed HA are tailored by the surface properties of underlying biochars, which differently affect the sorption for organic contaminants. - Highlights: • Effect of quantity and fractionation of coated HA on sorption of sulfonamides by BC was studied. • Fractionation of coated HA is tailored by surface properties of BC. • Roles of HA in BC sorption depend on interaction between HA adlayer and sorbate. • Roles of HA in sulfonamide sorption by BC also depend on HA aqueous concentration. - The quantity and fractionation of adsorbed HA play a major role in sulfonamide sorption by biochars

  19. Sorption of malachite green (MG) by cassava stem biochar (CSB ...

    Cassava stem biochar (CSB) was produced by pyrolyzing CS at 500°C for 2 hours at nitrogen environment. Proximate and ultimate analyses were conducted on CS and CSB. Batch sorption experiment on synthetic MG wastewater was optimized for the sorbent dosage, MG solution pH and contact time. Sorption data was ...

  20. Competitive sorption of heavy metals by water hyacinth roots.

    Zheng, Jia-Chuan; Liu, Hou-Qi; Feng, Hui-Min; Li, Wen-Wei; Lam, Michael Hon-Wah; Lam, Paul Kwan-Sing; Yu, Han-Qing

    2016-12-01

    Heavy metal pollution is a global issue severely constraining aquaculture practices, not only deteriorating the aquatic environment but also threatening the aquaculture production. One promising solution is adopting aquaponics systems where a synergy can be established between aquaculture and aquatic plants for metal sorption, but the interactions of multiple metals in such aquatic plants are poorly understood. In this study, we investigated the absorption behaviors of Cu(II) and Cd(II) in water by water hyacinth roots in both single- and binary-metal systems. Cu(II) and Cd(II) were individually removed by water hyacinth roots at high efficiency, accompanied with release of protons and cations such as Ca 2+ and Mg 2+ . However, in a binary-metal arrangement, the Cd(II) sorption was significantly inhibited by Cu(II), and the higher sorption affinity of Cu(II) accounted for its competitive sorption advantage. Ionic exchange was identified as a predominant mechanism of the metal sorption by water hyacinth roots, and the amine and oxygen-containing groups are the main binding sites accounting for metal sorption via chelation or coordination. This study highlights the interactive impacts of different metals during their sorption by water hyacinth roots and elucidates the underlying mechanism of metal competitive sorption, which may provide useful implications for optimization of phytoremediation system and development of more sustainable aquaculture industry. Copyright © 2016 Elsevier Ltd. All rights reserved.

  1. Analysis of ideal sorption compressor cycles operating with gas mixtures

    Tzabar, N.; ter Brake, H.J.M.

    2018-01-01

    Sorption-based compressors are thermally driven and because of the absence of moving parts they are vibration free, and have the potential for long life. Sorption-based compressors have been reported to operate Joule–Thomson (JT) cryogenic coolers with pure working fluids. However, using mixed

  2. Picloram and Aminopyralid Sorption to Soil and Clay Minerals

    Aminopyralid sorption data are lacking, and these data are needed to predict off-target transport and plant available herbicide in soil solution. The objective of this research was to determine the sorption of picloram and aminopyralid to five soils and three clay minerals and determine if the pote...

  3. Hysteresis and Temperature Dependency of Moisture Sorption – New Measurements

    Rode, Carsten; Hansen, Kurt Kielsgaard

    2011-01-01

    measurements of hysteresis and temperature dependency of the moisture sorption characteristics of three different porous building materials: aerated concrete, cement paste and spruce. Scanning curves are measured for all three materials where periods with adsorption and desorption interrupt each other...... intermittently. For one of the materials, aerated concrete, the sorption curves are determined at three different temperatures....

  4. Sorption of fluoroquinolones and sulfonamides in 13 Brazilian soils.

    Leal, Rafael Marques Pereira; Alleoni, Luis Reynaldo Ferracciú; Tornisielo, Valdemar Luiz; Regitano, Jussara Borges

    2013-08-01

    Animal production is a leading economic activity in Brazil and antibiotics are widely used. However, the occurrence, behavior, and impacts of antibiotics in Brazilian soils are still poorly known. We evaluated the sorption behavior of four fluoroquinolones (norfloxacin, ciprofloxacin, danofloxacin, and enrofloxacin) and five sulfonamides (sulfadiazine, sulfachloropyridazine, sulfamethoxazole, sulfadimidine, and sulfathiazole) in 13 Brazilian soils with contrasting physical, chemical, and mineralogical properties. Fluoroquinolone sorption was very high (Kd≥544 L kg(-1)) whereas sulfonamide sorption ranged from low to high (Kd=0.7-70.1 L kg(-1)), consistent with previous reports in the literature. Soil texture and cation exchange capacity were the soil attributes that most affected sorption. Cation exchange was the most important sorption mechanism for the fluoroquinolones in highly weathered tropical soils, although cation bridging and ion pairing could not be ruled out. Hydrophobic partition played an important role in the sorption of the sulfonamides, but sorption was also affected by non-hydrophobic interactions with organic and/or mineral surfaces. Sorption for both compound classes tended to be higher in soils with high Al and Fe oxihydroxide contents, but they were not correlated with Kd values. No direct effect of soil pH was seen. The fluoroquinolones are not expected to leach even in worst-case scenarios (soils rich in sand and poor in organic carbon), whereas soil attributes dictate leaching potential for the sulfonamides. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. Associating Physical and Chemical Properties to Evaluate Buffer Materials by Th and U Sorption

    Jan, Yi-Lin; Chen, Tzu-Yun; Cheng, Hwai-Ping; Hsu, Chun-Nan; Tseng, Chia-Liang; Wei,Yuan-Yaw; Yang, Jen-Yan; Ke, Cheng-Hsiung; Chuang, Jui-Tang; Teng, Shi-Ping

    2003-02-27

    The physical and chemical properties of buffer materials to be used for a radwaste disposal repository should be evaluated prior to use. In a conventional approach, independent studies of physical and/or chemical characteristics are conducted. This study investigated the relationship between the plastic index (PI) and distribution ratio (Rd) of buffer materials composed of varying ratios of quartz sand and bentonite. Thorium (Th) and Uranium (U) were the nuclides of interest, and both synthetic groundwater and seawater were used as the liquid phases to simulate conditions representative of deep geological disposal within an island. Atterberg tests were used to determine PI values, and batch sorption experiments were employed to measure Rd values. The results show that Th reached maximum sorption behavior when the bentonite content exceeded 30 % of the mixture. Contrariwise, the sorption of U increased linearly with bentonite content, up to bentonite contents of 100%, and this correlation was present regardless of the liquid phase used. A further result is that U has a better additivity with respect to Rd than Th in both synthetic groundwater and synthetic seawater. These results will allow a determination of more effective buffer material composition, and improved estimates of the overall Rd of the buffer material mixture from the Rd of each mineral component.

  6. Effects of chemical oxidation on sorption and desorption of PAHs in typical Chinese soils

    Chen Wei; Hou Lei; Luo Xiaoli; Zhu Lingyan

    2009-01-01

    In situ chemical oxidation is a commonly applied soil and groundwater remediation technology, but can have significant effects on soil properties, which in turn might affect fate and transport of organic contaminants. In this study, it was found that oxidation treatment resulted mainly in breakdown of soil organic matter (SOM) components. Sorption of naphthalene and phenanthrene to the original soils and the KMnO 4 -treated soils was linear, indicating that hydrophobic partitioning to SOM was the predominant mechanism for sorption. Desorption from the original and treated soils was highly resistant, and was well modeled with a biphasic desorption model. Desorption of residual naphthalene after treating naphthalene-contaminated soils with different doses of KMnO 4 also followed the biphasic desorption model very well. It appears that neither changes of soil properties caused by chemical oxidation nor direct chemical oxidation of contaminated soils had a noticeable effect on the nature of PAH-SOM interactions. - Chemical oxidation of soils had little effect on the mechanisms controlling sorption and desorption of PAHs.

  7. Sorption and mobility of 14C-fenamiphos in Brazilian soils.

    Cáceres, Tanya; Venkateswarlu, Kadiyala

    2018-02-02

    Although fenamiphos is widely used as an insecticide and nematicide in bowling greens and agriculture, information on its sorption in tropical soils is limited. In this study, mobility, sorption, and desorption dynamics of 14 C-fenamiphos in three contrasting Brazilian soils were examined both in batch and column experiments. Fenamiphos sorption coefficients (K d ) were 2.33, 3.86, and 3.9 L kg -1 for the three soils tested. The insecticide exhibited linear adsorption isotherms in all the three soils, and desorption was in a range of 30-40% during a 72-h period. With its low mobility, fenamiphos did not percolate through the soil profile even after 48 h. However, there is a risk of leaching to water bodies due to runoff because of its high solubility in water. In view of the fact that fenamiphos and its oxidation products are highly toxic to aquatic invertebrates and could affect the soil microbial activities even at low concentrations, the present information is of great importance in risk assessment of fenamiphos in the environment.

  8. Diffusion and sorption on hardened cement pastes - experiments and modelling results

    Jakob, A.; Sarott, F.-A.; Spieler, P.

    1999-08-01

    Large parts of repositories for low and intermediate level radioactive waste consist of cementitious materials. Radionuclides are transported by diffusion in the cement matrix or, in case of fractured or highly permeable cement, by advection and dispersion. In this work we aim at a mechanistic understanding of diffusion processes of some reactive tracers. On the laboratory scale, ten through-diffusion experiments were performed to study these processes for Cl{sup -}, I{sup -}, Cs{sup +} and Ni{sup 2+} ions in a Sulphate Resisting Portland Cement (SRPC) equilibrated with an artificial pore water. Some of the experiments continued up to nearly three years with daily measurements. In all the experiments, a cement disk initially saturated with an artificial pore water was exposed on one side to a highly diluted solution containing the species of interest. On the second side, a near-zero concentration boundary was maintained to drive through-diffusion of the tracer. The changes of concentrations on both sides of the samples were monitored, allowing careful mass balances. From these data, values of the diffusive flux and the mass of tracer taken up by the cementitious material were determined as a function of time. In the subsequent modelling, the time histories of these tracer breakthroughs were fitted using five different models. The simplest model neglects all retarding mechanisms except pure diffusion. More complex models either account for instantaneous equilibrium sorption in form of linear or non-linear (Freundlich) sorption or for first-order sorption kinetics where the forward reaction may be linear or non-linear according to the Freundlich isotherm, while the back-reaction is linear. Hence, the analysis allows the extraction of the diffusion coefficient and parameter values for the sorption isotherm or rate-constants for sorption and desorption. The fits to the experimental data were carried out by an automated Marquardt-Levenberg procedure yielding error

  9. Sorption of Np (Ⅴ) on Beishan granite fracture filling materials

    Jiang Tao; Wang Bo; Bao Liangjin; Zhou Duo; Long Haoqi; Song Zhixin; Chen Xi

    2012-01-01

    The sorption behaviors of Np (Ⅴ) on the granite fracture filling materials were studied by batch experiments under anaerobic in Beishan groundwater. The impact of pH of groundwater, CO 3 2- , humic acid and different components of granite fracture filling materials on sorption of Np (Ⅴ) was investigated. The results show that the granite fracture filling materials have strong capacity of Np (Ⅴ) adsorption. The value of K d , for Np (Ⅴ) sorption on the granite fracture filling materials is 843 mL/g. With the increase of pH, the value of K d increases at first and then decreases. K d of Np sorption on granite fracture filling materials in the presence of CO 3 2- and humic acid decreases. The chlorite and feldspar are major contributors to the sorption of Np (Ⅴ) on Beishan granite fracture filling materials. (authors)

  10. Sorption of perfluoroalkyl substances to two types of minerals.

    Hellsing, Maja S; Josefsson, Sarah; Hughes, Arwel V; Ahrens, Lutz

    2016-09-01

    The sorption of perfluoroalkyl substances (PFASs) was investigated for two model soil mineral surfaces, alumina (Al2O3) and silica (SiO2), on molecular level using neutron scattering. The PFASs were selected (i.e. perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorooctane sulfonic acid (PFOS)) to examine the role of hydrophobic chain length and hydrophilic functional group on their sorption behaviour. All four PFASs were found to sorb to alumina surface (positively charged) forming a hydrated layer consisting of 50% PFASs. The PFAS solubility limit, which decrease with chain length, was found to strongly influence the sorption behaviour. The sorbed PFAS layer could easily be removed by gentle rinsing with water, indicating release upon rainfall in the environment. No sorption was observed for PFOA and PFOS at silica surface (negatively charged), showing electrostatic interaction being the driving force in the sorption process. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Sorption mechanisms of metals to graphene oxide

    Showalter, Allison R; Bunker, Bruce A; Duster, Thomas A; Szymanowski, Jennifer E S; Na, Chongzheng; Fein, Jeremy B

    2016-01-01

    Environmental toxic metal contamination remediation and prevention is an ongoing issue. Graphene oxide is highly sorptive for many heavy metals over a wide pH range under different ionic strength conditions. We present x-ray absorption fine structure (XAFS) spectroscopy results investigating the binding environment of Pb(II), Cd(II) and U(VI) ions onto multi-layered graphene oxide (MLGO). Analysis indicates that the dominant sorption mechanism of Pb to MLGO changes as a function of pH, with increasing inner sphere contribution as pH increases. In contrast, the sorption mechanism of Cd to MLGO remains constant under the studied pH range. This adsorption mechanism is an electrostatic attraction between the hydrated Cd +2 ion and the MLGO surface. The U(VI), present as the uranyl ion, changes only subtly as a function of pH and is bound to the surface via an inner sphere bond. Knowledge of the binding mechanism for each metal is necessary to help in optimizing environmental remediation or prevention in filtration systems. (paper)

  12. Mercury Sorption onto Malt Spent Rootlets

    Manariotis, I. D.; Anagnostopoulos, V.; Karapanagioti, H. K.; Chrysikopoulos, C.

    2011-12-01

    Mercury is a metal of particular concern due to its toxicity even at relatively low concentrations. The maximum permissible level for mercury in drinking water set by the European Union is 0.001 mg/L. Mercury is released into the environment via four principal pathways: (1) natural processes; i.e. a volcanic eruption, (2) incidental to some other activity; i.e. coal burning power plants, (3) accidentally during the manufacture, breakage or disposal of products that have mercury put into them deliberately, and (4) direct use in industrial settings. The present study focuses on the removal of mercury (II) from aqueous solutions via sorption onto Malt Spent Rootlets (MSR). Batch experiments were conducted employing MSR with size ranging from 0.18 to 1 mm. The effects of pH, mercury concentration, contact time, and solid to liquid ratio on mercury sorption onto MSR were investigated. The highest mercury removal from the aqueous phase, of 41%, was observed at pH of 5.

  13. Tritium sorption by cement and subsequent release

    Ono, F.; Yamawaki, M.

    1995-01-01

    In a fusion reactor or tritium-handling facilities, contamination of concrete by tritium and subsequent release from it to the reator or experimental room is a matter of problem for safe control of tritium and management of operational environment. In order to evaluate this tritium behavior, interaction of tritiated water with concrete or cement should be clarified. In the present study, HTO sorption and subsequent release from cement were experimentally studied.(1)Sorption experiments were conducted using columns packed with cement particles of different sizes. From the analysis of the breakthrough curve, tritium diffusivity in macropores and microparticles were evaluated.(2)From the short-term tritium release experiments, effective desorption rate constants were evaluated and the effects of temperature and moisture were studied.(3)In the long-term tritium release experiments to 6000h, the tritium release mechanism was found to be composed of three kinds of water: initially from capillary water, and in the second stage from gel water and from the water in the cement crystal.(4)Tritium release behavior by heat treatment to 800 C was studied. A high temperature above 600 C was required for the tritium trapped in the crystal water to be released. (orig.)

  14. Sorption of uranium by cellulose derivatives

    Muroi, M.; Imai, S.; Hamaguchi, A.

    1985-01-01

    The sorption behaviour of uranium was investigated by batch and column methods using four cellulose derivatives, two having an amino group and two having an amino group plus a dithiocarboxylate group. All four derivatives showed maximum uranium sorption from pure water in the neutral region or from artificial sea water in the acidic region. In the batch method, quantitative removal of 100 μg of uranium from 50 ml of water at pH 5.0 was achieved by equilibration with 50 mg of any of the four sorbents. The percentage removal under these conditions decreased gradually with increasing concentration of uranium above 100 μg per 50 ml. A similar high percentage removal of uranium was achieved using artificial sea water. In the column method, quantitative removal of 5 μg of uranium from 1l of water at pH 6.7 was achieved with 200 mg of either of the two sorbents. Similar quantitative removal of uranium was achieved from 1l of artificial sea water at pH 5.4 with 500 mg of either of the two sorbents. (author)

  15. Uranium sorption on tezontle volcanic rock

    Lopez M, B. E.; Duran B, J. M.; Iturbe G, J. L.; Olguin G, M. T., E-mail: beatriz.lopez@inin.gob.m [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)

    2009-07-01

    It is described a study that demonstrates that hexavalent uranium ions were sorbed by the naturally occurring mineral using a batch technique. This mineral is found in abundant quantities in Mexico. Our study focused on the separation of U Vi from synthetic aqueous systems of both H{sub 2}O-UO{sub 2}(NO{sub 3}){sub 2}.6H{sub 2}O (acid) and H{sub 2}O-Na{sub 4}[UO{sub 2}(CO{sub 3}){sub 3}] (basic). The chemical speciation was performed by using high voltage electrophoresis, and the uranium content was determined by UV-Vis spectroscopy. The quantified U(Vi) sorption by tezontle from acidic and basic systems was 2.72 and 1.68 mumol/g, respectively, and the sorption behavior is discussed considering the surface charge of the tezontle at different ph values based on the point of zero charge characteristic of this material. (Author)

  16. Status of sorption information retrieval system

    Hostetler, D.D.; Serne, R.J.; Brandstetter, A.

    1979-09-01

    A Sorption Information Retrieval System (SIRS) is being designed to provide an efficient, computerized, data base for information on radionuclide sorption in geologic media. The data bank will include Kd values for a large number of radionuclides occurring in radioactive wastes originating from the commercial nuclear power industry. Kd values determined to date span several groundwater compositions and a wide variety of rock types and minerals. The data system will not only include Kd values, but also background information on the experiments themselves. This will allow the potential user to retrieve not only the Kd values of interest but also sufficient information to evaluate the accuracy and usefulness of the data. During FY-1979, the logic structure of the system was designed, the software programmed, the data categories selected, and the data format specified. About 40% of the approximately 5000 Kd experiments performed by the Waste Isolation Safety Assessment Program (WISAP) and its subcontractors during FY-1977 and FY-1978 have been evaluated, coded and keypunched. Additional software improvements and system testing are needed before the system will be fully operational. A workshop requested by the NEA was held to discuss potential internatioal participation in the data system

  17. Linear regression

    Olive, David J

    2017-01-01

    This text covers both multiple linear regression and some experimental design models. The text uses the response plot to visualize the model and to detect outliers, does not assume that the error distribution has a known parametric distribution, develops prediction intervals that work when the error distribution is unknown, suggests bootstrap hypothesis tests that may be useful for inference after variable selection, and develops prediction regions and large sample theory for the multivariate linear regression model that has m response variables. A relationship between multivariate prediction regions and confidence regions provides a simple way to bootstrap confidence regions. These confidence regions often provide a practical method for testing hypotheses. There is also a chapter on generalized linear models and generalized additive models. There are many R functions to produce response and residual plots, to simulate prediction intervals and hypothesis tests, to detect outliers, and to choose response trans...

  18. Linear Colliders

    Alcaraz, J.

    2001-01-01

    After several years of study e''+ e''- linear colliders in the TeV range have emerged as the major and optimal high-energy physics projects for the post-LHC era. These notes summarize the present status form the main accelerator and detector features to their physics potential. The LHC era. These notes summarize the present status, from the main accelerator and detector features to their physics potential. The LHC is expected to provide first discoveries in the new energy domain, whereas an e''+ e''- linear collider in the 500 GeV-1 TeV will be able to complement it to an unprecedented level of precision in any possible areas: Higgs, signals beyond the SM and electroweak measurements. It is evident that the Linear Collider program will constitute a major step in the understanding of the nature of the new physics beyond the Standard Model. (Author) 22 refs

  19. Linear algebra

    Edwards, Harold M

    1995-01-01

    In his new undergraduate textbook, Harold M Edwards proposes a radically new and thoroughly algorithmic approach to linear algebra Originally inspired by the constructive philosophy of mathematics championed in the 19th century by Leopold Kronecker, the approach is well suited to students in the computer-dominated late 20th century Each proof is an algorithm described in English that can be translated into the computer language the class is using and put to work solving problems and generating new examples, making the study of linear algebra a truly interactive experience Designed for a one-semester course, this text adopts an algorithmic approach to linear algebra giving the student many examples to work through and copious exercises to test their skills and extend their knowledge of the subject Students at all levels will find much interactive instruction in this text while teachers will find stimulating examples and methods of approach to the subject

  20. Violations of local equilibrium and linear response in classical lattice systems

    Aoki, Kenichiro; Kusnezov, Dimitri

    2003-01-01

    We quantitatively and systematically analyze how local equilibrium, and linear response in transport are violated as systems move far from equilibrium. This is done by studying heat flow in classical lattice models with and without bulk transport behavior, in 1-3 dimensions, at various temperatures. Equations of motion for the system are integrated numerically to construct the non-equilibrium steady states. Linear response and local equilibrium assumptions are seen to break down in a similar manner. We quantify the breakdown through the analysis of both microscopic and macroscopic observables and examine its transformation properties under general redefinitions of the non-equilibrium temperature

  1. Nonequilibrium thermodynamic fluctuations and phase transition in black holes

    Su, R.; Cai, R.; Yu, P.K.N.

    1994-01-01

    Landau nonequilibrium fluctuation and phase transition theory is applied to the discussion of the phase transition of black holes. Some second moments of relevant thermodynamical quantities for Kerr-Newman black holes are estimated. A theorem governing the divergence of some second moments and the occurrence of the phase transition in black holes is given

  2. D.C.-arc plasma generator for nonequilibrium plasmachemical processes

    Kvaltin, J.

    1990-06-01

    The analysis is made of the conditions for generation of nonequilibrium plasma in a plasmachemical reactor, and the design is described of a d.c. arc plasma generator based on the integral criterion. Results of measuring potentials on the plasma column of this generator are presented. (author)

  3. SRB states and nonequilibrium statistical mechanics close to equilibrium

    Gallavotti, Giovannni; Ruelle, David

    1996-01-01

    Nonequilibrium statistical mechanics close to equilibrium is studied using SRB states and a formula for their derivatives with respect to parameters. We write general expressions for the thermodynamic fluxes (or currents) and the transport coefficients, generalizing previous results. In this framework we give a general proof of the Onsager reciprocity relations.

  4. Non-equilibrium microwave plasma for efficient high temperature chemistry

    van den Bekerom, D.C.M.; den Harder, N.; Minea, T.; Palomares Linares, J.M.; Bongers, W.; van de Sanden, M.C.M.; van Rooij, G.J.

    2017-01-01

    This article describes a flowing microwave reactor that is used to drive efficient non-equilibrium chemistry for the application of conversion/activation of stable molecules such as CO2, N2 and CH4. The goal of the procedure described here is to measure the in situ gas temperature and gas

  5. Complex temporal and spatial patterns in nonequilibrium processes

    Swinney, H.L.

    1992-01-01

    We have used dynamical systems methods to study and characterize bifurcations and pattern formation in a variety of nonequilibrium systems. In this paper we describe our work on dynamical systems, chemical oscillations and chaos, chemical spatial patterns, instabilities in fluid dynamics, electrodeposition clusters, the ballast resistor, and crack propagation

  6. Nonlinear and Nonequilibrium Spin Injection in Magnetic Tunneling Junctions

    Guo, Hong

    2007-03-01

    Quantitative analysis of charge and spin quantum transport in spintronic devices requires an atomistic first principles approach that can handle nonlinear and nonequilibrium transport conditions. We have developed an approach for this purpose based on real space density functional theory (DFT) carried out within the Keldysh nonequilibrium Green's function formalism (NEGF). We report theoretical analysis of nonlinear and nonequilibrium spin injection and quantum transport in Fe/MgO/Fe trilayer structures as a function of external bias voltage. Devices with well relaxed atomic structures and with FeO oxidization layers are investigated as a function of external bias voltage. We also report calculations of nonequilibrium spin injection into molecular layers and graphene. Comparisons to experimental data will be presented. Work in collaborations with: Derek Waldron, Vladimir Timochevski (McGill University); Ke Xia (Institute of Physics, Chinese Academy of Science, Beijing, China); Eric Zhu, Jian Wang (University of Hong Kong); Paul Haney, and Allan MacDonald (University of Texas at Austin).

  7. Effects of vacancies on overshooting in nonequilibrium ordering processes

    Gilhøj, Henriette; Jeppesen, Claus; Mouritsen, Ole G.

    1996-01-01

    The effects of annealed site dilution on the nonequilibrium ordering process in the two-dimensional Ising model with a nonconserved order parameter have been studied using Monte Carlo simulation. It is found that the transient development of a local order that is larger than the equilibrium order...

  8. Principle of Entropy Maximization for Nonequilibrium Steady States

    Shapiro, Alexander; Stenby, Erling Halfdan

    2002-01-01

    The goal of this contribution is to find out to what extent the principle of entropy maximization, which serves as a basis for the equilibrium thermodynamics, may be generalized onto non-equilibrium steady states. We prove a theorem that, in the system of thermodynamic coordinates, where entropy...

  9. Supersymmetric Field Theory of Non-Equilibrium Thermodynamic System

    Olemskoi, Alexander I.; Brazhnyi, Valerii A.

    1998-01-01

    On the basis of Langevin equation the optimal SUSY field scheme is formulated to discribe a non-equilibrium thermodynamic system with quenched disorder and non-ergodicity effects. Thermodynamic and isothermal susceptibilities, memory parameter and irreversible response are determined at different temperatures and quenched disorder intensities.

  10. Fluctuation and dissipation in nonequilibrium quantum field theory

    Ramos, Rudnei O.

    1994-01-01

    The nonequilibrium dynamics of a scalar field is studied using perturbation theory and a real time finite temperature formulation. The evolution equation for the scalar field is explicitly obtained, and terms responsible for noise (fluctuations) and dissipation are identified and studied in the high temperature limit. (author)

  11. Nonequilibrium Enhances Adaptation Efficiency of Stochastic Biochemical Systems.

    Chen Jia

    Full Text Available Adaptation is a crucial biological function possessed by many sensory systems. Early work has shown that some influential equilibrium models can achieve accurate adaptation. However, recent studies indicate that there are close relationships between adaptation and nonequilibrium. In this paper, we provide an explanation of these two seemingly contradictory results based on Markov models with relatively simple networks. We show that as the nonequilibrium driving becomes stronger, the system under consideration will undergo a phase transition along a fixed direction: from non-adaptation to simple adaptation then to oscillatory adaptation, while the transition in the opposite direction is forbidden. This indicates that although adaptation may be observed in equilibrium systems, it tends to occur in systems far away from equilibrium. In addition, we find that nonequilibrium will improve the performance of adaptation by enhancing the adaptation efficiency. All these results provide a deeper insight into the connection between adaptation and nonequilibrium. Finally, we use a more complicated network model of bacterial chemotaxis to validate the main results of this paper.

  12. Applications of non-equilibrium plasma in chemical processes

    Patino, P.; Castro, A.

    2003-01-01

    By means of optical emission spectroscopy the population of O( 3 P) in a non-equilibrium, high voltage, oxygen plasma, and O( 3 P), H and OH in another of steam in radio frequency, have been followed. Reactions of both plasmas with liquid hydrocarbons have produced oxidation and/or hydrogenation, depending on the conditions of each one. (Author)

  13. Non-equilibrium and band tailing in organic conductors

    . Non-equilibrium ... Introduction. Study of organic conductors and semiconductors continues to generate interest with the ... Band tailing reduces band gap or the acti- ..... (9), we can identify Eg(0) with the focal point and is proportional to P2. 1 .

  14. Measures of trajectory ensemble disparity in nonequilibrium statistical dynamics

    Crooks, Gavin E; Sivak, David A

    2011-01-01

    Many interesting divergence measures between conjugate ensembles of nonequilibrium trajectories can be experimentally determined from the work distribution of the process. Herein, we review the statistical and physical significance of several of these measures, in particular the relative entropy (dissipation), Jeffreys divergence (hysteresis), Jensen–Shannon divergence (time-asymmetry), Chernoff divergence (work cumulant generating function), and Rényi divergence

  15. Coherence enhanced quantum metrology in a nonequilibrium optical molecule

    Wang, Zhihai; Wu, Wei; Cui, Guodong; Wang, Jin

    2018-03-01

    We explore the quantum metrology in an optical molecular system coupled to two environments with different temperatures, using a quantum master equation beyond secular approximation. We discover that the steady-state coherence originating from and sustained by the nonequilibrium condition can enhance quantum metrology. We also study the quantitative measures of the nonequilibrium condition in terms of the curl flux, heat current and entropy production at the steady state. They are found to grow with temperature difference. However, an apparent paradox arises considering the contrary behaviors of the steady-state coherence and the nonequilibrium measures in relation to the inter-cavity coupling strength. This paradox is resolved by decomposing the heat current into a population part and a coherence part. Only the latter, the coherence part of the heat current, is tightly connected to the steady-state coherence and behaves similarly with respect to the inter-cavity coupling strength. Interestingly, the coherence part of the heat current flows from the low-temperature reservoir to the high-temperature reservoir, opposite to the direction of the population heat current. Our work offers a viable way to enhance quantum metrology for open quantum systems through steady-state coherence sustained by the nonequilibrium condition, which can be controlled and manipulated to maximize its utility. The potential applications go beyond quantum metrology and extend to areas such as device designing, quantum computation and quantum technology in general.

  16. Nonequilibrium two-dimensional Ising model with stationary uphill diffusion

    Colangeli, Matteo; Giardinà, Cristian; Giberti, Claudio; Vernia, Cecilia

    2018-03-01

    Usually, in a nonequilibrium setting, a current brings mass from the highest density regions to the lowest density ones. Although rare, the opposite phenomenon (known as "uphill diffusion") has also been observed in multicomponent systems, where it appears as an artificial effect of the interaction among components. We show here that uphill diffusion can be a substantial effect, i.e., it may occur even in single component systems as a consequence of some external work. To this aim we consider the two-dimensional ferromagnetic Ising model in contact with two reservoirs that fix, at the left and the right boundaries, magnetizations of the same magnitude but of opposite signs.We provide numerical evidence that a class of nonequilibrium steady states exists in which, by tuning the reservoir magnetizations, the current in the system changes from "downhill" to "uphill". Moreover, we also show that, in such nonequilibrium setup, the current vanishes when the reservoir magnetization attains a value approaching, in the large volume limit, the magnetization of the equilibrium dynamics, thus establishing a relation between equilibrium and nonequilibrium properties.

  17. Electron systems out of equilibrium: nonequilibrium Green's function approach

    Špička, Václav; Velický, Bedřich; Kalvová, Anděla

    2014-01-01

    Roč. 28, č. 23 (2014), "1430013-1"-"1430013-103" ISSN 0217-9792 R&D Projects: GA ČR GAP204/12/0897 Institutional support: RVO:68378271 Keywords : nonequilibrium statistical physics * transients * quantum transport the ory Subject RIV: BE - The oretical Physics Impact factor: 0.937, year: 2014

  18. Fluctuation theorems and orbital magnetism in nonequilibrium state

    We study Langevin dynamics of a driven charged particle in the presence as well as in the absence of magnetic field. We discuss the validity of various work fluctuation theorems using different model potentials and external drives. We also show that one can generate an orbital magnetic moment in a nonequilibrium state ...

  19. On the forces and fluxes in non-equilibrium thermodynamics

    Kitahara, Kazuo

    1986-01-01

    A formulation of non-equilibrium thermodynamics of continuum systems based on local equilibrium assumption is reported. Thermodynamic forces are defined from a generalized local entropy and irreversible fluxes are defined as non-advective parts of fluxes of conservative quantities. The validity of the general evolution criterion and its generalization is discussed. (author)

  20. p-Nitrophenol, phenol and aniline sorption by organo-clays

    Ko, C.H.; Fan Chihhao; Chiang, P.N.; Wang, M.K.; Lin, K.C.

    2007-01-01

    The aims of this study were to make use of organo-clays (i.e., Cloisite-10A, Cloisite-15A, Cloisite-30B and Cloisite-93A), to remove p-nitrophenol, phenol and aniline of organic pollutants. The organo-clays were characterized by X-ray diffraction (XRD). Sorption isotherm, kinetic and pH effect of p-nitrophenol, phenol and aniline sorbed by four organo-clays were evaluated. The d-spacings (0 0 1) of the XRD peak of Cloisite-10A, Cloisite-15A, Cloisite-30B and Cloisite-93A are 1.98, 2.76, 1.93 and 2.64 nm, respectively. The d(0 0 1)-spacings of XRD indicated that these p-nitropheno, phenol and aniline could penetrate into the interlayer of clays and expand the d(0 0 1)-spacings. The linear sorption isotherm of constant partition was employed to describe the sorption isotherms of phenols sorbed by organo-clays through hydrophobic-hydrophobic chemical reactions. The parabolic diffusion and power-function of kinetic models were employed to describe properly the kinetic experiments. The rate limiting step of the p-nitrophenol sorption reactions on organo-clays were diffusion-controlled processes (i.e., 15A, 30B, 93A) and chemical-controlled process for 10A organo-clays. The pre-exponential factor of the p-nitrophenol sorbed by four organo-clays showed the trend as follows: 10A > 30B > 93A > 15A. The efficiency of these organo-clays in removing phenol compounds in water treatments merit further study

  1. Practical issues relating to soil column chromatography for sorption parameter determination.

    Bi, Erping; Schmidt, Torsten C; Haderlein, Stefan B

    2010-08-01

    Determination of sorption distribution coefficients (K(d)) of organic compounds by a dynamic soil column chromatography (SCC) method was developed and validated. Eurosoil 4, quartz, and alumina were chosen as exemplary packing materials. Heterocyclic aromatic compounds were selected in the validation of SCC. The prerequisites of SCC with regard to column dimension, packing procedure, and sample injection volume are discussed. Reproducible soil column packing was achieved by addition of a pre-column and an HPLC pump for subsequent compression of the packed material. Various methods to determine retention times from breakthrough curves are discussed and the use of the half mass method is recommended. To dilute soil with inert material can prevent column-clogging and help to complete experiments in a reasonable period of time. For the chosen probe compounds, quartz rather than alumina proved a suitable dilution material. Non-equilibrium issue can be overcome by conducting the experiments under different flowrates and/or performing numerical simulation. Copyright 2010 Elsevier Ltd. All rights reserved.

  2. Sorption and diffusion of Cs and I in concrete

    Andersson, K.; Torstenfelt, B.; Allard, B.

    1983-01-01

    Concrete has been suggested as a possible encapsulation material for long-term storage of low and medium level radioactive waste. At an underground storage of concrete encapsulated waste, a slow release of radioactive elements into the groundwater by diffusion through the concrete must be considered in the safety analysis. The diffusion may be delayed by sorption reactions on the solid. A wide range of long-lived radionuclides may be present in the low and medium level radioactive waste. Here, the sorption and diffusion of iodide and cesium on slag cement paste and concrete has been studied. The influence of four different water phases (pore water, groundwater, Baltic Sea water and sea water) as well as the influence of some added species (carbonate, sulphate and magnesium) has been investigated. A significant sorption of iodide on cement paste in contact with pore water was observed, indicating that the diffusion may be expected to be retarded in this medium. For cesium the highest sorption was found for concrete and groundwater. This means that the sorption increases as the concrete is weathered. Low or insignificant sorption was found for the cement paste, indicating that the ballast is responsible for the Cs-sorption. Carbonatization enhances the Cs-sorption by about a factor of 3. The diffusivity of Cs in concrete and cement paste was determined to between 2x10 - 14 and 8x10 - 14 m 2 /s in pore water (where an insignificant sorption was observed). The choice of ballast as well as addition of suitable getters with high sorption of the long-lived radionuclides might decrease the mass transfer rate through the cement. (Authors)

  3. Nonequilibrium current-carrying steady states in the anisotropic X Y spin chain

    Lancaster, Jarrett L.

    2016-05-01

    Out-of-equilibrium behavior is explored in the one-dimensional anisotropic X Y model. Initially preparing the system in the isotropic X X model with a linearly varying magnetic field to create a domain-wall magnetization profile, dynamics is generated by rapidly changing the exchange interaction anisotropy and external magnetic field. Relaxation to a nonequilibrium steady state is studied analytically at the critical transverse Ising point, where correlation functions may be computed in closed form. For arbitrary values of anisotropy and external field, an effective generalized Gibbs' ensemble is shown to accurately describe observables in the long-time limit. Additionally, we find spatial oscillations in the exponentially decaying, transverse spin-spin correlation functions with wavelength set by the magnetization jump across the initial domain wall. This wavelength depends only weakly on anisotropy and magnetic field in contrast to the current, which is highly dependent on these parameters.

  4. Influence of turbulent fluctuations on non-equilibrium chemical reactions in the flow

    Molchanov, A. M.; Yanyshev, D. S.; Bykov, L. V.

    2017-11-01

    In chemically nonequilibrium flows the problem of calculation of sources (formation rates) in equations for chemical species is of utter importance. Formation rate of each component is a non-linear function of mixture density, temperature and concentration of species. Thus the suggestion that the mean rate may be determined via mean values of the flow parameters could lead to significant errors. One of the most accurate approaches here is utilization of probability density function (PDF). In this paper the method for constructing such PDFs is developed. The developed model was verified by comparison with the experimental data. On the example of supersonic combustion it was shown that while the overall effect on the averaged flow field is often negligible, the point of ignition can be considerably shifted up the flow.

  5. On microscopic stress nonequilibrium: Application to the magnetopause

    Wu, Z.J.

    1986-01-01

    The main purpose of this paper is to propose the concept of microscopic stress nonequilibrium (or simply micro-nonequilibrium) in plasma physics. This concept arises as a consequence of the insolubility of the steady-state Vlasov-Maxwell equations (or the kinetic-field equations in general) under certain conditions. In what follows: (1) A general stress equilibrium condition for tangential plasma discontinuities is derived from the Maxwell tensor and the plasma stress tensor. (2) An equivalent equilibrium condition, which takes the form of equations of motion of a ''fictitious particle'', is also derived from the above condition. (3) A general solution of the distribution functions is derived according to Jeans's theorem or Liouville's theorem for the solar wind particles in a tangential magnetopause. (4) This solution is applied to the equilibrium condition to investigate the equilibrium state of the tangential magnetopause. Both Parker's tail-region and Wu's dawn-side ''nonequilibria''are confirmed to be micro-nonequilibria because of the violation of the above equilibrium condition. (5) The effects of various factors in micro-nonequilibria are discussed. It is found that randomly trapped particles and inwards electric field in the magnetopause layer generally cannot relieve the dawn-side or tail-region micro-nonequilibria; and that a northward magnetic field in the solar wind generally can suppress the dawn-side nonequilibrium, while a southward field can jeopardize a dusk-side Vlasov equilibrium. (6) Discussion: The concept of ''micro-nonequilibrium'' may become of importance in basic plasma dynamics. It is also possible that the micro-nonequilibrium may play a fundamental role in solar wind particles entering the magnetopause and in magnetospheric substorms

  6. Sorption of lipophilic organic compunds to wood and implications for their environmental fate

    Trapp, Stefan; Miglioranza, S.B.; Mosbæk, Hans

    2001-01-01

    The sorption from water to wood (KWood) of 10 organic chemicals (logKOW, 1.48-6.20) was experimentally determined for oak (Quercus robur) and basket willow (Salix viminalis). Linear regression yielded log KWood ) -0.27 (( 0.25) + 0.632 (( 0.063)log KOW for oak (r ) 0.90, n ) 27) and log KWood ) -...... time. If metabolism inside the stem occurs, wood can serve as a “safe sink” for environmental chemicals. This might be of use in phytoremediation....

  7. Approximate method of calculation of non-equilibrium flow parameters of chemically reacting nitrogen tetroxide in the variable cross-section channels with energy exchange

    Bazhin, M.A.; Fedosenko, G.Eh.; Shiryaeva, N.M.; Mal'ko, M.V.

    1986-01-01

    It is shown that adiabatic non-equilibrium chemically reacting gas flow with energy exchange in a variable cross-section channel may be subdivided into five possible types: 1) quasi-equilibrium flow; 2) flow in the linear region of deviation from equilibrium state; 3) quasi-frozen flow; 4) flow in the linear region of deviation from frozen state; 5) non-equilibrium flow. Criteria of quasi-equilibrium and quazi-frozen flows, including factors of external action of chemically reacting gas on flow, allow to obtain simple but sufficiently reliable approximate method of calculation of flow parameters. The considered method for solving the problem of chemically reacting nitrogen tetroxide in the variable cross-section channel with energy exchange can be used for evaluation of chemical reaction kinetics on the flow parameter in the stages of axial-flow and radial-flow turbines and in another practical problems

  8. Design and Synthesis of Nonequilibrium Systems.

    Cheng, Chuyang; McGonigal, Paul R; Stoddart, J Fraser; Astumian, R Dean

    2015-09-22

    The active transport of ions and molecules across cell membranes is essential to creating the concentration gradients that sustain life in all living organisms, be they bacteria, fungi, plants, animals or Homo sapiens. Nature uses active transport everywhere for everything. Molecular biologists have long been attracted to the study of active transport and continue to this day to investigate and elucidate the tertiary structures of the complex motor proteins that sustain it, while physicists, interested in nonequilibrium statistical mechanics, have developed theoretical models to describe the driven ratcheting motions that are crucial to its function. The increasingly detailed understanding that contemporary science has acquired relating to active transport, however, has yet to lead to the design and construction of artificial molecular motors capable of employing ratchet-driven motions that can also perform work against concentration gradients. Mechanically interlocked molecules (MIMs) in the form of pseudo- and semirotaxanes are showing some encouraging signs in meeting these goals. This review summarizes recent progress in making artificial molecular motors that can perform work by "pumping" tetracationic rings into high-energy states. The launching pad is a bistable [2]rotaxane whose dumbbell component contains two electron-donating recognition sites, one, a tetrathiafulvalene (TTF) unit, which interacts more strongly with the ring component, cyclobis(paraquat-p-phenylene) (CBPQT(4+)), containing two electron-accepting bipyridinium units, than does the other 1,5-dioxynaphthalene (DNP) unit. Switching can be induced electrochemically by oxidizing the TTF unit to a TTF(•+) radical cation, whereupon Coulombic repulsion takes care of moving the ring to the DNP unit. Reduction of the radical cation resets the switch. Molecular switches operate at, or close to, equilibrium. Any work done during one switching event is undone during the reset. Molecular motors, on the

  9. Sorption of cesium in young till soils

    Lusa, Merja; Lempinen, Janne; Ahola, Hanna; Soederlund, Mervi; Lehto, Jukka [Helsinki Univ. (Finland). Laboratory of Radiochemistry; Lahdenperae, Anne-Maj [Saanio and Riekkola Oy, Consulting Engineers, Helsinki (Finland); Ikonen, Ari T.K. [Posiva Oy, Eurajoki (Finland)

    2014-10-01

    Soil samples from three forest soil pits were examined down to a depth of approximately three metres using 1 M ammonium acetate extraction and microwave-assisted extraction with concentrated nitric acid (HNO{sub 3}), to study the binding of cesium (Cs) at Olkiluoto Island, southern Finland. Ammonium acetate was used to extract the readily exchangeable Cs fractions roughly representing the Cs fraction in soil which is available for plants. Microwave-assisted HNO{sub 3} extraction dissolves various minerals, e.g. carbonates, most sulphides, arsenides, selenides, phosphates, molybdates, sulphates, iron (Fe) and manganese (Mn) oxides and some silicates (olivine, biotite, zeolite), and reflects the total Cs concentrations. Cs was mostly found in the strongly bound fraction obtained through HNO{sub 3} extraction. The average Cs concentrations found in this fraction were 3.53 ± 0.30 mg/kg (d.w.), 3.06 ± 1.86 mg/kg (d.w.) and 1.83 ± 0.42 mg/kg (d.w.) in the three soil pits, respectively. The average exchangeable Cs found in the ammonium acetate extraction in all three sampling pits was 0.015 ± 0.008 mg/kg (d.w.). In addition, Cs concentrations in the soil solution were determined and in situ distribution coefficients (K{sub d}) for Cs were calculated. Furthermore, the in situ K{sub d} data was compared with the Cs K{sub d} data obtained using the model batch experiments. The in situ K{sub d} values were observed to fairly well follow the trend of batch sorption data with respect to soil depth, but on average the batch distribution coefficients were almost an order of magnitude higher than the in situ K{sub d} data. In situ Cs sorption data could be satisfactory fitted with the Langmuir sorption isotherm, but the Freundlich isotherm failed to fit the data. Finally, distribution coefficients were calculated by an ion exchange approach using soil solution data, the cation exchange capacity (CEC) as well as Cs to sodium (Na) and Cs to potassium (K) ion exchange selectivity

  10. A suggested approach toward measuring sorption and applying sorption data to repository performance assessment

    Rundberg, R.S.

    1992-01-01

    The prediction of radionuclide migration for the purpose of assessing the safety of a nuclear waste repository will be based on a collective knowledge of hydrologic and geochemical properties of the surrounding rock and groundwater. This knowledge along with assumption about the interactions of radionuclides with groundwater and minerals form the scientific basis for a model capable of accurately predicting the repository's performance. Because the interaction of radionuclides in geochemical systems is known to be complicated, several fundamental and empirical approaches to measuring the interaction between radionuclides and the geologic barrier have been developed. The approaches applied to the measurement of sorption involve the use of pure minerals, intact, or crushed rock in dynamic and static experiments. Each approach has its advantages and disadvantages. There is no single best method for providing sorption data for performance assessment models which can be applied without invoking information derived from multiple experiments. 53 refs., 12 figs

  11. Study of sorption processes of copper on synthetic hydroxyapatite

    Rosskopfova, O.; Galambos, M.; Ometakova, J.; Rajec, P.; Caplovicova, M.

    2012-01-01

    The sorption of copper on synthetic hydroxyapatite was investigated using a batch method and radiotracer technique. The hydroxyapatite sample prepared by a wet precipitation process was of high crystallinity with Ca/P ratio of 1.688. The sorption of copper on hydroxyapatite was pH independent ranging from 4 to 6 as a result of buffering properties of hydroxyapatite. The adsorption of copper was rapid and the percentage of Cu sorption was >98% during the first 15-30 min of the contact time. The experimental data for sorption of copper have been interpreted in the term of Langmuir isotherm. The sorption of Cu 2+ ions was performed by ion-exchange with Ca 2+ cations on the crystal surface of hydroxyapatite under experimental conditions. The competition effect of Zn 2+ , Fe 2+ and Pb 2+ towards Cu 2+ sorption was stronger than that of Co 2+ , Ni 2+ and Ca 2+ ions. The ability of the bivalent cations to depress the sorption of copper on hydroxyapatite was in the following order Pb 2+ > Fe 2+ > Zn 2+ > Co 2+ ∼ Ni 2+ . (author)

  12. Sorption of U(VI) species on hydroxyapatite

    Thakur, P.; Moore, R.C.; Choppin, G.R.

    2005-01-01

    The sorption of uranyl (UO 2 2+ ) cations to hydroxyapatite was studied as a function of the amount of sorbent, ionic strength, U(VI) concentration, pH and temperature. The rate of uranyl sorption on hydroxyapatite decreased with increased uranyl concentrations. The amount sorbed decreased with increased ionic strength and increased with pH to a maximum at 7-8. The sorption data for UO 2 2+ were fitted well by the Freundlich and Dubinin-Radushkevich (D-R) isotherms. The anions Cl - , NO 3 - , SO 4 2- and CH 3 COO - decreased the sorption of uranium on hydroxyapatite while S 2 O 3 2- slightly increased it. The sorbed uranium was desorbed by 0.10 M and 1.00 M solutions of HCl and HNO 3 . The thermodynamic parameters for the sorption of UO 2 2+ were measured at temperatures of 298, 313, 323 and 333 K. The temperature dependence confirmed an endothermic heat of sorption. The activation energy for the sorption process was calculated to be +2.75±0.02 kJ/mol. (orig.)

  13. Artificial Weathering of Biotite and Uranium Sorption Characteristics

    Lee, Seung Yeop; Baik, Min Hoon; Lee, Jae Kwang

    2009-01-01

    An experiment for uranium sorption onto fresh and weathered biotites was performed. After centrifugation, concentrations of uranium in the supernatants were analyzed using ICP-MS, and biotite samples were investigated using XRD and SEM. With powdered biotites (<3 mm in size), we have conducted uranium sorption experiments about fresh and weathered biotites to obtain uranium sorption amounts in various pH conditions. The uranium sorption was not high at a low pH (e.g., pH 3), but increased with increasing pH. There were lower uranium sorption by the weathered biotites than by the fresh ones, and the difference was much larger at higher pH (e.g., pH 11). The lower sorption values of uranium by the weathered biotites may be caused by a change of mineral surfaces and a chemical behavior of surrounding dissolved elements. It seems that the uranium-mineral interaction has been diminished, especially, in the weathered biotite by a destruction and dissolution of preferential sorption sites on the mineral surfaces and by the colloidal formation from dissolved elements.

  14. Mechanisms of metal sorption by biochars: Biochar characteristics and modifications.

    Li, Hongbo; Dong, Xiaoling; da Silva, Evandro B; de Oliveira, Letuzia M; Chen, Yanshan; Ma, Lena Q

    2017-07-01

    Biochar produced by thermal decomposition of biomass under oxygen-limited conditions has received increasing attention as a cost-effective sorbent to treat metal-contaminated waters. However, there is a lack of information on the roles of different sorption mechanisms for different metals and recent development of biochar modification to enhance metal sorption capacity, which is critical for biochar field application. This review summarizes the characteristics of biochar (e.g., surface area, porosity, pH, surface charge, functional groups, and mineral components) and main mechanisms governing sorption of As, Cr, Cd, Pb, and Hg by biochar. Biochar properties vary considerably with feedstock material and pyrolysis temperature, with high temperature producing biochars with higher surface area, porosity, pH, and mineral contents, but less functional groups. Different mechanisms dominate sorption of As (complexation and electrostatic interactions), Cr (electrostatic interactions, reduction, and complexation), Cd and Pb (complexation, cation exchange, and precipitation), and Hg (complexation and reduction). Besides sorption mechanisms, recent advance in modifying biochar by loading with minerals, reductants, organic functional groups, and nanoparticles, and activation with alkali solution to enhance metal sorption capacity is discussed. Future research needs for field application of biochar include competitive sorption mechanisms of co-existing metals, biochar reuse, and cost reduction of biochar production. Published by Elsevier Ltd.

  15. Role of interlayer hydration in lincomycin sorption by smectite clays.

    Wang, Cuiping; Ding, Yunjie; Teppen, Brian J; Boyd, Stephen A; Song, Cunyi; Li, Hui

    2009-08-15

    Lincomycin, an antibiotic widely administered as a veterinary medicine, is frequently detected in water. Little is known about the soil-water distribution of lincomycin despite the fact that this is a major determinant of its environmental fate and potential for exposure. Cation exchange was found to be the primary mechanism responsible for lincomycin sorption by soil clay minerals. This was evidenced by pH-dependent sorption, and competition with inorganic cations for sorptive sites. As solution pH increased, lincomycin sorption decreased. The extent of reduction was consistent with the decrease in cationic lincomycin species in solution. The presence of Ca2+ in solution diminished lincomycin sorption. Clay interlayer hydration status strongly influenced lincomycin adsorption. Smectites with the charge deficit from isomorphic substitution in tetrahedral layers (i.e., saponite) manifest a less hydrated interlayer environment resulting in greater sorption than that by octahedrally substituted clays (i.e., montmorillonite). Strongly hydrated exchangeable cations resulted in a more hydrated clay interlayer environment reducing sorption in the order of Ca- smectite. X-ray diffraction revealed that lincomycin was intercalated in smectite clay interlayers. Sorption capacity was limited by clay surface area rather than by cation exchange capacity. Smectite interlayer hydration was shown to be a major, yet previously unrecognized, factor influencing the cation exchange process of lincomycin on aluminosilicate mineral surfaces.

  16. Web-based sorption database (KAERI-SDB)

    Lee, Jae Kwang; Baik, Min Hoon

    2010-10-01

    Radionuclide sorption data is necessary for the safety assessment of radioactive waste disposal. However the accessibility to the nuclide sorption database is limited. The web-based sorption database (KAERI-SDB) was developed to provide sorption data in a convenient way. The development of the KAERI-SDB was achieved by improving the performance of pre-existing sorption DB programme (SDB-21C) and incorporating the user requirement. The KAERI-SDB was designed that users can access it by using a web browser. Main functions of the KAERI-SDB include (1) log-in/join, (2) search and store of sorption data and (3) scatter plot chart and index chart. It is expected that the KAERI-SDB is widely applied to the safety assessment of radioactive waste disposal by enhancing the accessibility to experts and practitioner related the nuclear industry and governmental administration. It is also expected that reliabilities for the radioactive waste disposal increased by opening the web-based sorption DB to public

  17. A mechanistic approach to the generation of sorption databases

    Bradbury, M.H.; Baeyens, B.

    1992-01-01

    Sorption of radionuclides in the near and far fields of an underground nuclear waste repository is one of the most important processes retarding their release to the environment. In the vast majority of cases sorption data have been presented in terms of empirical parameters such as distribution coefficients and isotherm equations. A consequence of this empirical methodology is that the sorption data are only strictly valid under the experimental conditions at which they were measured. Implicit in this approach is the need to generate large amounts of data and fitting parameters necessary for an empirical description of sorption under all realistically conceivable conditions which may arise in space and time along the migration pathway to Man. An alternative approach to the problem is to try to understand, and develop model descriptions of, underlying retention mechanisms and to identify those systems parameters which essentially determine the extent of sorption. The aim of this work is to see to what extent currently existing mechanistic models, together with their associated data, can be applied to predict sorption data from laboratory experiments on natural systems. This paper describes the current status of this work which is very much in an early stage of development. An example is given whereby model predictions are compared with laboratory results for the sorption of Np at trace concentrations under oxidizing conditions on a series of minerals relevant to granite formations. 31 refs., 11 figs., 5 tabs

  18. Water vapor sorption thermodynamics of the Nafion ionomer membrane.

    Wadsö, Lars; Jannasch, Patric

    2013-07-18

    The water interactions of polymer electrolyte membranes are of significant interest when these materials are used in, for example, fuel cells. We have therefore studied the sorption thermodynamics of Nafion with a sorption calorimeter that simultaneously measures the sorption isotherm and the mixing (sorption) enthalpy. This unique method is suitable for investigating the sorption thermodynamics of ionic polymers. The measurements were made at 25 °C on a series of samples dried at different temperatures from 25 to 120 °C. The sorption isotherms indicate that the samples dried at 120 °C lost about 0.8 more water molecules per sulfonic group during the drying than did the samples dried at 25 °C, and this result was verified gravimetrically. The mixing enthalpies showed several peaks or plateaus for the samples dried at 60-120 °C. This behavior was seen up to about 2 water molecules per sulfonic group. As these peaks were not directly related to any feature in the sorption isotherm, they probably have their origin in a secondary process, such as a reorganization of the polymer.

  19. Sorption of strontium by magnetically modified yeast cells

    Hu Yantao; Ji Yanqin; Tian Qing; Shao Xianzhang; Shi Jianhe; Ivo Safarik; Zhang Shengdong; Li Jinying

    2008-01-01

    Magnetically modified fodder's yeast (Kluyveromyces fragilis) cells using water based magnetic fluid, were characterized by scanning electron microscopy (SEM) and Vibrating Sample Magnetometer (VSM). The sorption-desorption properties of Sr 2+ by these yeast cells from nitrate salt of Sr 2+ were studied. The results demonstrated that the Sr 2+ sorption volume by these cells enhanced with increasing pH and reached a plateau between pH 4.0 and 7.0. A minor effect by temperature was observed. The sorption volumes are 19.5 mg/g and 53.5 mg/g from 10 ppm and 40 ppm Sr 2+ solution respectively within 20 min. The sorption of Sr 2+ in these cells can be desorbed under 0.1 mol/L HNO 3 solution. The maximum Sr 2+ sorption volume is 96.7 mg/g at 20℃. The sorption characteristic fits Langmuir model well with 140.8 mg/g calculated maximum sorption volume by these yeast cells. (authors)

  20. Linear programming

    Karloff, Howard

    1991-01-01

    To this reviewer’s knowledge, this is the first book accessible to the upper division undergraduate or beginning graduate student that surveys linear programming from the Simplex Method…via the Ellipsoid algorithm to Karmarkar’s algorithm. Moreover, its point of view is algorithmic and thus it provides both a history and a case history of work in complexity theory. The presentation is admirable; Karloff's style is informal (even humorous at times) without sacrificing anything necessary for understanding. Diagrams (including horizontal brackets that group terms) aid in providing clarity. The end-of-chapter notes are helpful...Recommended highly for acquisition, since it is not only a textbook, but can also be used for independent reading and study. —Choice Reviews The reader will be well served by reading the monograph from cover to cover. The author succeeds in providing a concise, readable, understandable introduction to modern linear programming. —Mathematics of Computing This is a textbook intend...

  1. Plutonium sorption to nanocast mesoporous carbon

    Parsons-Moss, Tashi; Wang, Deborah; Jones, Stephen; Olive, Daniel; Nitsche, Heino [California Univ., Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Laboratory, Berkeley, CA (United States). Nuclear Science Div.; Tueysuez, Harun [Lawrence Berkeley National Laboratory, Berkeley, CA (United States). Nuclear Science Div.; Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany)

    2014-09-01

    Nanocast ordered mesoporous carbons are attractive as sorbents because of their extremely high surface areas and large pore volumes. This paper compares Pu uptake, added as Pu(VI), to both untreated and chemically oxidized CMK-(carbon molecular sieves from KAIST) type mesoporous carbon with that to a commercial amorphous activated carbon. The CMK was synthesized via nanocasting by using cubic ordered mesoporous silica KIT-6 as a hard template, and characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and nitrogen adsorption. A portion of the CMK was oxidized by treatment with nitric acid, and will be called OX CMK. The three carbon powders have similar particle morphology, and high BET surface areas. The activated carbon is disordered, while the CMK materials show large domains of ordered cubic mesostructure. The CMK material seems to have more oxygen-containing functional groups than the activated carbon, and the oxidation of the CMK increased the density of these groups, especially - COOH, thus lowering the point of zero charge (PZC) of the material. Batch studies of all 3 materials with plutonium solutions, in a 0.1 M NaClO{sub 4} matrix were performed to investigate pH dependence, sorption kinetics, Pu uptake capacities, competition with ethylenediaminetetraacetic acid (EDTA) in solution, and Pu desorption. Both CMK materials demonstrated high Pu sorption from solutions of pH 3 or greater, and the oxidized CMK also showed high sorption from pH 2 solutions. The activated carbon bound less Pu, and at a much slower rate than CMK. All other batch experiments were carried out in pH 4 solutions. The Pu uptake from low-concentration solutions was faster for the oxidized CMK than for untreated CMK, but in more concentrated samples (∝ 250 μM Pu), the Pu uptake kinetics and apparent capacity were the same for oxidized and untreated CMK. The 23-h Pu uptake capacity of the CMK

  2. Sorption compressor/mechanical expander hybrid refrigeration

    Jones, J. A.; Britcliffe, M.

    1987-01-01

    Experience with Deep Space Network (DSN) ground-based cryogenic refrigerators has proved the reliability of the basic two-stage Gifford-McMahon helium refrigerator. A very long life cryogenic refrigeration system appears possible by combining this expansion system or a turbo expansion system with a hydride sorption compressor in place of the usual motor driven piston compressor. To test the feasibility of this system, a commercial Gifford-McMahon refrigerator was tested using hydrogen gas as the working fluid. Although no attempt was made to optimize the system for hydrogen operation, the refrigerator developed 1.3 W at 30 K and 6.6 W at 60 K. The results of the test and of theoretical performances of the hybrid compressor coupled to these expansion systems are presented.

  3. Retention/sorption and geochemical modelling

    Arcos, D.; Grandia, F.; Domenech, C. [Enviros Spain, S.L., Barcelona (Spain); SCK-CEN, Mol (Belgium); Sellin, P. [SKB - Swedish Nuclear Fuel and Waste Management, SE, Stockholm (Sweden); Hunter, F.M.I.; Bate, F.; Heath, T.G.; Hoch, A. [Serco Assurance, Oxfordshire (United Kingdom); Werme, L.O. [SKB - Svensk Karnbranslehantering AB, Stockholm (Sweden); Bruggeman, C.; Maes, I.A.; Breynaert, E.; Vancluysen, J. [Leuven Katholieke Univ., Lab. for Colloid Chemistry (Belgium); Montavon, G.; Guo, Z. [Ecole des Mines, 44 - Nantes (France); Riebe, B.; Bunnenberg, C.; Meleshyn, A. [Leibniz Univ. Hannover, Zentrum fur Strahlenschutz und Radiookologie, Hannover (Germany); Dultz, S. [Leibniz Univ. Hannover, Institut fur Bodenkunde, Hannover (Germany)

    2007-07-01

    This session gathers 4 articles dealing with: the long-term geochemical evolution of the near field of a KBS-3 HLNW repository: insights from reactive transport modelling (D. Arcos, F. Grandia, C. Domenech, P. Sellin); the investigation of iron transport into bentonite from anaerobically corroding steel: a geochemical modelling study (F.M.I. Hunter, F. Bate, T.G. Heath, A. Hoch, L.O. Werme); SeO{sub 3}{sup 2-} adsorption on conditioned Na-illite: XAS spectroscopy, kinetics, surface complexation model and influence of compaction (C. Bruggeman, A. Maes, G. Montavon, E. Breynaert, Z. Guo, J. Vancluysen); the influence of temperature and gamma-irradiation on the anion sorption capacity of modified bentonites (B. Riebe, C. Bunnenberg, A. Meleshyn, S. Dultz)

  4. Sorption of radionuclides on a soil

    Fukui, Masami

    1979-01-01

    Disposal of radioactive wastes into the ground has been discussed, and this paper emphasized significance of the investigation for underground water flow and for the prediction of radionuclides through a stratified aquifer using column experiments to evaluate the internal radiation dose. Distributions and redistributions of radionuclides in a sandy layer were observed to identify the sorption model which predicts the behavior, and the underground water flow in the Plio-Pleistocene Osaka Group was investigated as an example, by mean of the measurement of 222 Rn concentration, the pumping technique and the tracer technique using the activation analysis. Then, the estimation of radioactive concentration in the underground water was worked out for the boundary condition of steady state inflow of liquid wastes and of which the 90 Sr are leached from the solidified body, moreover, the equation which easily evaluates the suitability of the disposal site was proposed. These approach may be useful for the actual site selection of radioactive wastes disposal. (author)

  5. Study of the radium sorption/desorption on goethite

    Bassot, S.; Stammose, D.; Mallet, C.; Lefebvre, C.; Ferreux, J.-M.

    2000-01-01

    The oxi-hydroxides, present at trace level in uranium mill tailings, are responsible of about 70% of the 226 radium sorption, half being fixed on crystallized forms. This radionuclide (half time=1622y), present at high level (50 to 100kBq.kg -1 ), can be released in groundwater, involving a possible contamination of the food chain (actual concentration limit=0.37Bq.1 -1 ). So, it is very important to point out the mechanisms of the radium sorption/desorption on crystallized oxi-hydroxides as a function of chemical conditions of the system. The radium sorption on synthetic goethite α-FeOOH has been studied as a function of contact time, initial radium activity, pH, sodium and calcium concentrations. The results show that, after one hour of contact time (necessary to reach equilibrium), the radium sorption increases widely in a pH range 6-7. The increase of Na + concentration is without influence on the radium sorption, indicating the low interactions between sodium and surface sites. At the opposite, the presence of calcium in solution decreases widely the radium sorption, that indicates a competition between calcium and radium for the same kind of sorption sites of the oxi-hydroxide surface. The percentage of radium desorbed increases widely with time, from 1 to 120h and becomes constant at a time higher than 120h. This long equilibrium time for desorption in comparison with sorption one can be explain by a local evolution of the sorption sites of the solid, which become less accessible for the solution in contact. (author)

  6. Sorption of Metal Ions on Clay Minerals.

    Schlegel; Manceau; Chateigner; Charlet

    1999-07-01

    The local structural environment of Co sorbed on hectorite (a magnesian smectite) has been investigated by polarized EXAFS (P-EXAFS) spectroscopy on a self-supporting film of Co-sorbed hectorite. This sorption sample was prepared by contacting Co and hectorite at pH 6.5 and at high ionic strength (0.3 M NaNO3) to favor pH-dependent sorption reaction over cation exchange. A self-supporting film was elaborated after 120 h of reacting time, when apparent quasi-equilibrium conditions were attained. The half-width at half maximum of the orientation distribution of c* axis of individual clay platelets off the film normal was determined by quantitative texture analysis, and found to be equal to 18.9 degrees. Co K-edge P-EXAFS spectra were recorded at angles between the incident beam and the film normal equal to 0 degrees, 35 degrees, 50 degrees, and 60 degrees; the 90 degrees spectrum was obtained by extrapolation. Spectral analysis led to the identification of the two nearest cationic subshells containing 1.6 +/- 0.4 Mg at 3.03 Å and 2.2 +/- 0.5 Si at 3.27 Å. These distances are respectively characteristic of edge-sharing linkages between Mg and Co octahedra and of corner-sharing linkages between Co octahedra and Si tetrahedra, as in clay structures. The angular dependence of the Co-Mg and Co-Si contributions indicates that Co-Mg pairs are oriented parallel to the film plane, whereas Co-Si pairs are not. These results are interpreted by the formation of Co inner-sphere mononuclear surface complexes located at the edges of hectorite platelets, in the continuity of the (Mg, Li) octahedral sheet. Copyright 1999 Academic Press.

  7. SORPTION OF Cu2+ IONS ONTO DIATOMITE CONSTITUENTS

    Vasile Rusu

    2009-06-01

    Full Text Available Studies of the sorption capacity towards Cu2+ ions of diatomite from the Ghidirim location of RM, as well as of the extracted clay phase are presented. Separated clay fraction from diatomic material is clean enough, and especially is rich in montmorillonite. Maximum sorption capacity for studied clay fraction is achieved by rising the temperature of calcination treatment up to 200oC. At higher temperatures the lattice of montmorillonite is contracted and its sorption capacity towards Cu2+ ions decreases strongly.

  8. Modeling and Prediction of Soil Water Vapor Sorption Isotherms

    Arthur, Emmanuel; Tuller, Markus; Moldrup, Per

    2015-01-01

    Soil water vapor sorption isotherms describe the relationship between water activity (aw) and moisture content along adsorption and desorption paths. The isotherms are important for modeling numerous soil processes and are also used to estimate several soil (specific surface area, clay content.......93) for a wide range of soils; and (ii) develop and test regression models for estimating the isotherms from clay content. Preliminary results show reasonable fits of the majority of the investigated empirical and theoretical models to the measured data although some models were not capable to fit both sorption...... directions accurately. Evaluation of the developed prediction equations showed good estimation of the sorption/desorption isotherms for tested soils....

  9. Sorption and desorption of diuron in Oxisol under biochar application

    Petter, Fabiano André; Ferreira, Tamara Santos; Sinhorin, Adilson Paulo; Lima, Larissa Borges de; Morais, Leidimar Alves de; Pacheco, Leandro Pereira

    2016-01-01

    ABSTRACT The objective of this study was to verify the kinetics of sorption and desorption of diuron in an Oxisol under application of biochar. The samples were collected in a field experiment conducted in randomized design blocks consisted of 2 base fertilization levels (0 and 400 kg∙ha−1 NPK 00-20-20 fertilizer formula) and 3 doses of biochar (0, 8 and 16 Mg∙ha−1). In the evaluation of sorption and desorption, Batch Equilibrium method was used. The kinetics of sorption and desorption of diu...

  10. Implementation of sorption hysteresis in multi-Fickian moisture transport

    Frandsen, Henrik Lund; Svensson, Staffan

    2007-01-01

    In the cellular structure of wood, bound-water diffusion and water-vapor diffusion interact via sorption in a complex moisture-transportation system. At low relative humidities, moisture transport may be modeled by a Fickian diffusion equation with a good approximation. At higher relative......-35% in moisture content. Hence, for a precise moisture content computation, sorption hysteresis must be taken into account. The present paper explains the relation between sorption hysteresis and multi-Fickian moisture transport, and clarifies how models for the two phenomena are coupled. To illustrate...

  11. Sorption of molybdenum by cellulose polyphosphate from acid solutions

    Luneva, N.K.; Oputina, A.G.; Ermolenko, I.N.

    1985-01-01

    The sorption of molybdenum on cellulose polyphosphate from acid solutions of ammonium molybdate depending on the phosphorus content in samples, concentration and pH of the solution, sorption time is studied. It is shown that a maximum molybdenum content on the cellulose samples with different phosphorus content is pointed out at an ammonium molybdate concentration 0.02 M. Saturation of the sorption curve is attained at molar ratio of adsrbed molybdenum to phosphorus 1:4. In case of small fillings the compound with molybdenum to phosphorus ratio 1:10 is formed

  12. Sorption of Co2+ on modified inorganic materials

    Hanzel, R.; Rajec, P.

    1999-01-01

    The aim of this study was preparation and characterization of sorbents on the base a silica-gel matrix with immobilized functional group (imidazole or crown-ether). Sorption of cobalt from aqueous solutions on prepared sorbents in static conditions (by 'batch' method) in the dependence of concentration, pH value,, as well as kinetics of sorption were studied. The influence of heavy or toxic metals [Hg(II), Cd(II), Mn(II), Zn(II), Cu(II), Fe(III), Cr(III), Al(III), Na and K] on sorption of cobalt was studied, too

  13. Arsenic Sorption on Mechanically Activated Magnetite and Olivine

    Zdenka Bujňáková

    2012-12-01

    Full Text Available Arsenic sorption on mechanically activated minerals such as magnetite Fe3O4 (Kiruna, Sweden and olivine (Mg,Fe2SiO4 (Ǻheim,Norway has been studied and compared in this work. Experiments were carried out with non-activated and mechanically activatedsamples. The activation of both minerals was performed in a planetary mill at different milling conditions. The specific surface areaand consequent sorption activity were enhanced by mechanical activation. The using of olivine seems to be better than magnetite fromthe point of view of milling time, which is necessary for achievement of the same sorption effect.

  14. Sorption of trace cesium on 21 Hanford Site sediment types

    Routson, R.C.; Barney, G.S.; Smith, R.M.; Delegard, C.A.

    1980-03-01

    Sorption of trace cesium (Cs) was measured on 21 Hanford Site sediment types. A Box-Behnken statistical design was used to develop empirical-statistical equations predicting 137 Cs sorption as a function of the equilibrium concentrations of macroions Na + , K + , and Ca +2 in solution over the concentration ranges of 3.0 to 0.001M, 0.2 to 0.002M, and 0.2 to 0.002M, respectively. These equations are required to estimate trace Cs transport from Hanford ground disposal sites. Average Cs sorption equations for the 21 sediments will be presented and discussed

  15. Integrated sorption and diffusion model for bentonite. Part 1. Clay-water interaction and sorption modeling in dispersed systems

    Tachi, Yukio; Suyama, Tadahiro; Ochs, Michael

    2014-01-01

    To predict the long-term migration of radionuclides (RNs) under variable conditions within the framework of safety analyses for geological disposal, thermodynamic sorption models are very powerful tools. The integrated sorption and diffusion (ISD) model for compacted bentonite was developed to achieve a consistent combination of clay–water interaction, sorption, and diffusion models. The basic premise considered in the ISD model was to consistently use the same simple surface model design and parameters for describing RNs sorption/diffusion as well as clay surface and porewater chemistry. A simple 1-site non-electrostatic surface complexation model in combination with a 1-site ion exchange model was selected to keep sorption model characteristics relatively robust for compacted systems. Fundamental parameters for the proposed model were evaluated from surface titration data for purified montmorillonite. The resulting basic model was then parameterized on the basis of selected published sorption data-sets for Np(V), Am(III), and U(VI) in dispersed systems, which cover a range of key geochemical conditions such as pH, ionic strength, and carbonate concentration. The sorption trends for these RNs can be quantitatively described by the model considering a full suite of surface species including hydrolytic and carbonate species. The application of these models to the description of diffusive-sorptive transport in compacted bentonites is presented in Part 2. (author)

  16. Development of a Self-Consistent Model of Plutonium Sorption: Quantification of Sorption Enthalpy and Ligand-Promoted Dissolution

    Powell, Brian [Clemson Univ., SC (United States); Kaplan, Daniel I [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Arai, Yuji [Univ. of Illinois, Urbana-Champaign, IL (United States); Becker, Udo [Univ. of Michigan, Ann Arbor, MI (United States); Ewing, Rod [Stanford Univ., CA (United States)

    2016-12-29

    This university lead SBR project is a collaboration lead by Dr. Brian Powell (Clemson University) with co-principal investigators Dan Kaplan (Savannah River National Laboratory), Yuji Arai (presently at the University of Illinois), Udo Becker (U of Michigan) and Rod Ewing (presently at Stanford University). Hypothesis: The underlying hypothesis of this work is that strong interactions of plutonium with mineral surfaces are due to formation of inner sphere complexes with a limited number of high-energy surface sites, which results in sorption hysteresis where Pu(IV) is the predominant sorbed oxidation state. The energetic favorability of the Pu(IV) surface complex is strongly influenced by positive sorption entropies, which are mechanistically driven by displacement of solvating water molecules from the actinide and mineral surface during sorption. Objectives: The overarching objective of this work is to examine Pu(IV) and Pu(V) sorption to pure metal (oxyhydr)oxide minerals and sediments using variable temperature batch sorption, X-ray absorption spectroscopy, electron microscopy, and quantum-mechanical and empirical-potential calculations. The data will be compiled into a self-consistent surface complexation model. The novelty of this effort lies largely in the manner the information from these measurements and calculations will be combined into a model that will be used to evaluate the thermodynamics of plutonium sorption reactions as well as predict sorption of plutonium to sediments from DOE sites using a component additivity approach.

  17. Environmental Conditions Influencing Sorption of Inorganic Anions to Multiwalled Carbon Nanotubes Studied by Column Chromatography.

    Metzelder, Florian; Schmidt, Torsten C

    2017-05-02

    Sorption to carbon-based nanomaterials is typically studied in batch experiments. An alternative method offering advantages to study sorption is column chromatography. Sorbent packed columns are used and sorption data are determined by relating sorbate retention to that of a nonretarded tracer. We have now for the first time applied this technique to study the influence of environmental conditions on sorption of inorganic anions (bromide, nitrite, nitrate, and iodide) to multiwalled carbon nanotubes. Deuterium oxide was used as nonretarded tracer. Sorption isotherms were best described by the Freundlich model. Sorption increased in the order bromide 4.5 the surface charge was negative, but sorption was still detectable at pH 6 and 9. Consequently, other forces than electrostatic attraction contributed to sorption. These forces may include H-bonding as indicated by sorption enthalpy determined by variation of column temperature. Overall, column chromatography represents a promising alternative in sorption studies to reveal sorbent properties.

  18. A facilitated diffusion model constrained by the probability isotherm: a pedagogical exercise in intuitive non-equilibrium thermodynamics.

    Chapman, Brian

    2017-06-01

    This paper seeks to develop a more thermodynamically sound pedagogy for students of biological transport than is currently available from either of the competing schools of linear non-equilibrium thermodynamics (LNET) or Michaelis-Menten kinetics (MMK). To this end, a minimal model of facilitated diffusion was constructed comprising four reversible steps: cis- substrate binding, cis → trans bound enzyme shuttling, trans -substrate dissociation and trans → cis free enzyme shuttling. All model parameters were subject to the second law constraint of the probability isotherm, which determined the unidirectional and net rates for each step and for the overall reaction through the law of mass action. Rapid equilibration scenarios require sensitive 'tuning' of the thermodynamic binding parameters to the equilibrium substrate concentration. All non-equilibrium scenarios show sigmoidal force-flux relations, with only a minority of cases having their quasi -linear portions close to equilibrium. Few cases fulfil the expectations of MMK relating reaction rates to enzyme saturation. This new approach illuminates and extends the concept of rate-limiting steps by focusing on the free energy dissipation associated with each reaction step and thereby deducing its respective relative chemical impedance. The crucial importance of an enzyme's being thermodynamically 'tuned' to its particular task, dependent on the cis- and trans- substrate concentrations with which it deals, is consistent with the occurrence of numerous isoforms for enzymes that transport a given substrate in physiologically different circumstances. This approach to kinetic modelling, being aligned with neither MMK nor LNET, is best described as intuitive non-equilibrium thermodynamics, and is recommended as a useful adjunct to the design and interpretation of experiments in biotransport.

  19. Force-dominated non-equilibrium oxidation kinetics of tantalum

    Kar, Prasenjit; Wang, Ke; Liang, Hong

    2008-01-01

    Using a combined electrochemical and mechanical manipulation technique, we compared the equilibrium and non-equilibrium oxidation processes and states of tantalum. Experimentally, a setup was developed with an electrochemical system attached to a sliding mechanical configuration capable of friction force measurement. The surface chemistry of a sliding surface, i.e., tantalum, was modified through the electrolyte. The mechanically applied force was fixed and the dynamics of the surface was monitored in situ through a force sensor. The formation of non-equilibrium oxidation states of tantalum was found in oxidation limiting environment of acetic acid. An oxidative environment of deionized water saturated with KCl was used as comparison. We proposed a modified Arrhenius-Eyring equation in which the mechanical factor was considered. We found that the mechanical energy induced the non-stable-state reactions leading to metastable oxidation states of tantalum. This equation can be used to predict mechanochemical reactions that are important in many industrial applications

  20. On Equivalence of Nonequilibrium Thermodynamic and Statistical Entropies

    Purushottam D. Gujrati

    2015-02-01

    Full Text Available We review the concept of nonequilibrium thermodynamic entropy and observables and internal variables as state variables, introduced recently by us, and provide a simple first principle derivation of additive statistical entropy, applicable to all nonequilibrium states by treating thermodynamics as an experimental science. We establish their numerical equivalence in several cases, which includes the most important case when the thermodynamic entropy is a state function. We discuss various interesting aspects of the two entropies and show that the number of microstates in the Boltzmann entropy includes all possible microstates of non-zero probabilities even if the system is trapped in a disjoint component of the microstate space. We show that negative thermodynamic entropy can appear from nonnegative statistical entropy.