Sample records for modeling mixing-controlled reactive

  1. Quadratic reactivity fuel cycle model

    Energy Technology Data Exchange (ETDEWEB)

    Lewins, J.D.


    For educational purposes it is highly desirable to provide simple yet realistic models for fuel cycle and fuel economy. In particular, a lumped model without recourse to detailed spatial calculations would be very helpful in providing the student with a proper understanding of the purposes of fuel cycle calculations. A teaching model for fuel cycle studies based on a lumped model assuming the summability of partial reactivities with a linear dependence of reactivity usefully illustrates fuel utilization concepts. The linear burnup model does not satisfactorily represent natural enrichment reactors. A better model, showing the trend of initial plutonium production before subsequent fuel burnup and fission product generation, is a quadratic fit. The study of M-batch cycles, reloading 1/Mth of the core at end of cycle, is now complicated by nonlinear equations. A complete account of the asymptotic cycle for any order of M-batch refueling can be given and compared with the linear model. A complete account of the transient cycle can be obtained readily in the two-batch model and this exact solution would be useful in verifying numerical marching models. It is convenient to treat the parabolic fit rho = 1 - tau/sup 2/ as a special case of the general quadratic fit rho = 1 - C/sub tau/ - (1 - C)tau/sup 2/ in suitably normalized reactivity and cycle time units. The parabolic results are given in this paper.

  2. A Mixed-control Mechanism Model of Proeutectoid Ferrite Growth under Non-equilibrium Interface Condition in Fe-C Alloys

    Institute of Scientific and Technical Information of China (English)

    Ruiheng WU; Xueyu RUAN; Hongbing ZHANG; T.Y.Hsu


    By combining the α/γ interface migration and the carbon diffusion at the interface in Fe-C alloys, a mathematical model is constructed to describe the mixed-control mechanism for proeutectoid ferrite formation from austenite. In this model, the α/γ interface is treated as non-equilibrium interface, i.e., the carbon concentration of austenite at γ/α interface is obtained through theoretical calculation, instead of that assumed as the local equilibrium concentration.For isothermal precipitation of ferrite in Fe-C alloys, the calculated results show that the rate of interface migration decreases monotonically during the whole process, while the rate of carbon diffusion from γ/α interface into austenite increases to a peak value and then decreases. The process of ferrite growth may be considered as composed of three stages: the period of rapid growth, slow growth and finishing stage. The results also show that the carbon concentration of austenite at γ/α interface could not reach the thermodynamic equilibrium value even at the last stage of ferrite growth.

  3. Langevin model for reactive transport in porous media (United States)

    Tartakovsky, Alexandre M.


    Existing continuum models for reactive transport in porous media tend to overestimate the extent of solute mixing and mixing-controlled reactions because the continuum models treat both the mechanical and diffusive mixings as an effective Fickian process. Recently, we have proposed a phenomenological Langevin model for flow and transport in porous media [A. M. Tartakovsky, D. M. Tartakovsky, and P. Meakin, Phys. Rev. Lett. 101, 044502 (2008)10.1103/PhysRevLett.101.044502]. In the Langevin model, the fluid flow in a porous continuum is governed by a combination of a Langevin equation and a continuity equation. Pore-scale velocity fluctuations, the source of mechanical dispersion, are represented by the white noise. The advective velocity (the solution of the Langevin flow equation) causes the mechanical dispersion of a solute. Molecular diffusion and sub-pore-scale Taylor-type dispersion are modeled by an effective stochastic advection-diffusion equation. Here, we propose a method for parameterization of the model for a synthetic porous medium, and we use the model to simulate multicomponent reactive transport in the porous medium. The detailed comparison of the results of the Langevin model with pore-scale and continuum (Darcy) simulations shows that: (1) for a wide range of Peclet numbers the Langevin model predicts the mass of reaction product more accurately than the Darcy model; (2) for small Peclet numbers predictions of both the Langevin and the Darcy models agree well with a prediction of the pore-scale model; and (3) the accuracy of the Langevin and Darcy model deteriorates with the increasing Peclet number but the accuracy of the Langevin model decreases more slowly than the accuracy of the Darcy model. These results show that the separate treatment of advective and diffusive mixing in the stochastic transport model is more accurate than the classical advection-dispersion theory, which uses a single effective diffusion coefficient (the dispersion

  4. Modelling Reactive and Proactive Behaviour in Simulation

    CERN Document Server

    Majid, Mazlina Abdul; Aickelin, Uwe


    This research investigated the simulation model behaviour of a traditional and combined discrete event as well as agent based simulation models when modelling human reactive and proactive behaviour in human centric complex systems. A departmental store was chosen as human centric complex case study where the operation system of a fitting room in WomensWear department was investigated. We have looked at ways to determine the efficiency of new management policies for the fitting room operation through simulating the reactive and proactive behaviour of staff towards customers. Once development of the simulation models and their verification had been done, we carried out a validation experiment in the form of a sensitivity analysis. Subsequently, we executed a statistical analysis where the mixed reactive and proactive behaviour experimental results were compared with some reactive experimental results from previously published works. Generally, this case study discovered that simple proactive individual behaviou...

  5. Modeling and simulation of reactive flows

    CERN Document Server

    Bortoli, De AL; Pereira, Felipe


    Modelling and Simulation of Reactive Flows presents information on modeling and how to numerically solve reactive flows. The book offers a distinctive approach that combines diffusion flames and geochemical flow problems, providing users with a comprehensive resource that bridges the gap for scientists, engineers, and the industry. Specifically, the book looks at the basic concepts related to reaction rates, chemical kinetics, and the development of reduced kinetic mechanisms. It considers the most common methods used in practical situations, along with equations for reactive flows, and va

  6. Hybrid multiscale simulation of a mixing-controlled reaction

    Energy Technology Data Exchange (ETDEWEB)

    Scheibe, Timothy D.; Schuchardt, Karen L.; Agarwal, Khushbu; Chase, Jared M.; Yang, Xiaofan; Palmer, Bruce J.; Tartakovsky, Alexandre M.; Elsethagen, Todd O.; Redden, George D.


    Continuum-scale models have been used to study subsurface flow, transport, and reactions for many years but lack the capability to resolve fine-grained processes. Recently, pore-scale models, which operate at scales of individual soil grains, have been developed to more accurately model and study pore-scale phenomena, such as mineral precipitation and dissolution reactions, microbially-mediated surface reactions, and other complex processes. However, these highly-resolved models are prohibitively expensive for modeling domains of sizes relevant to practical problems. To broaden the utility of pore-scale models for larger domains, we developed a hybrid multiscale model that initially simulates the full domain at the continuum scale and applies a pore-scale model only to areas of high reactivity. Since the location and number of pore-scale model regions in the model varies as the reactions proceed, an adaptive script defines the number and location of pore regions within each continuum iteration and initializes pore-scale simulations from macroscale information. Another script communicates information from the pore-scale simulation results back to the continuum scale. These components provide loose coupling between the pore- and continuum-scale codes into a single hybrid multiscale model implemented within the SWIFT workflow environment. In this paper, we consider an irreversible homogenous bimolecular reaction (two solutes reacting to form a third solute) in a 2D test problem. This paper is focused on the approach used for multiscale coupling between pore- and continuum-scale models, application to a realistic test problem, and implications of the results for predictive simulation of mixing-controlled reactions in porous media. Our results and analysis demonstrate that loose coupling provides a feasible, efficient and scalable approach for multiscale subsurface simulations.

  7. Modeling target erosion during reactive sputtering

    Energy Technology Data Exchange (ETDEWEB)

    Strijckmans, K., E-mail:; Depla, D.


    Highlights: • The erosion of a target is simulated with the RSD2013 software during reactive magnetron sputtering. • The influence of redeposition on the target state and on the hysteresis is explained. • The racetrack formation along the hysteresis and as function of the redeposition is quantified. • Comparison of the racetrack and the sputter profile shows clear differences. - Abstract: The influence of the reactive sputter conditions on the racetrack and the sputter profile for an Al/O{sub 2} DC reactive sputter system is studied by modeling. The role of redeposition, i.e. the deposition of sputtered material back on the target, is therefore taken into account. The used model RSD2013 is capable of simulating the effect of redeposition on the target condition in a spatial resolved way. Comparison between including and excluding redeposition in the RSD2013 model shows that the in-depth oxidation profile of the target differs. Modeling shows that it is important to distinguish between the formed racetrack, i.e. the erosion depth profile, and the sputter profile. The latter defines the distribution of the sputtered atoms in the vacuum chamber. As the target condition defines the sputter yield, it does determine the racetrack and the sputter profile of the planar circular target. Both the shape of the racetrack and the sputter profile change as function of the redeposition fraction as well as function of the oxygen flow change. Clear asymmetries and narrowing are observed for the racetrack shape. Similar effects are noticed for the sputter profile but to a different extent. Based on this study, the often heard misconception that the racetrack shape defines the distribution of the sputtered atoms during reactive sputtering is proven to be wrong.

  8. Impact of reactive settler models on simulated WWTP performance

    DEFF Research Database (Denmark)

    Gernaey, Krist; Jeppsson, Ulf; Batstone, Damien J.


    Including a reactive settler model in a wastewater treatment plant model allows representation of the biological reactions taking place in the sludge blanket in the settler, something that is neglected in many simulation studies. The idea of including a reactive settler model is investigated for ...

  9. Modeling and stability analysis of the nonlinear reactive sputtering process

    Directory of Open Access Journals (Sweden)

    György Katalin


    Full Text Available The model of the reactive sputtering process has been determined from the dynamic equilibrium of the reactive gas inside the chamber and the dynamic equilibrium of the sputtered metal atoms which form the compound with the reactive gas atoms on the surface of the substrate. The analytically obtained dynamical model is a system of nonlinear differential equations which can result in a histeresis-type input/output nonlinearity. The reactive sputtering process has been simulated by integrating these differential equations. Linearization has been applied for classical analysis of the sputtering process and control system design.

  10. Impact of reactive settler models on simulated WWTP performance. (United States)

    Gernaey, K V; Jeppsson, U; Batstone, D J; Ingildsen, P


    Including a reactive settler model in a wastewater treatment plant model allows representation of the biological reactions taking place in the sludge blanket in the settler, something that is neglected in many simulation studies. The idea of including a reactive settler model is investigated for an ASM1 case study. Simulations with a whole plant model including the non-reactive Takács settler model are used as a reference, and are compared to simulation results considering two reactive settler models. The first is a return sludge model block removing oxygen and a user-defined fraction of nitrate, combined with a non-reactive Takács settler. The second is a fully reactive ASM1 Takács settler model. Simulations with the ASM1 reactive settler model predicted a 15.3% and 7.4% improvement of the simulated N removal performance, for constant (steady-state) and dynamic influent conditions respectively. The oxygen/nitrate return sludge model block predicts a 10% improvement of N removal performance under dynamic conditions, and might be the better modelling option for ASM1 plants: it is computationally more efficient and it will not overrate the importance of decay processes in the settler.

  11. Reactive burn models and ignition & growth concept

    Energy Technology Data Exchange (ETDEWEB)

    Menikoff, Ralph S [Los Alamos National Laboratory; Shaw, Milton S [Los Alamos National Laboratory


    Plastic-bonded explosives are heterogeneous materials. Experimentally, shock initiation is sensitive to small amounts of porosity, due to the formation of hot spots (small localized regions of high temperature). This leads to the Ignition and Growth concept, introduced by Lee and Tarver in 1980, as the basis for reactive burn models. A homogeneized burn rate needs to account for three mesoscale physical effects (i) the density of burnt hot spots, which depends on the lead shock strength; (ii) the growth of the burn fronts triggered by hot spots, which depends on the local deflagration speed; (iii) a geometric factor that accounts for the overlap of deflagration wavelets from adjacent hot spots. These effects can be combined and the burn model defined by specifying the reaction progress variable {lambda}(t) as a function of a dimensionless reaction length {tau}{sub hs}(t)/{ell}{sub hs}, rather than by xpecifying an explicit burn rate. The length scale {ell}{sub hs} is the average distance between hot spots, which is proportional to [N{sub hs}(P{sub s})]{sup -1/3}, where N{sub hs} is the number density of hot spots activated by the lead shock. The reaction length {tau}{sub hs}(t) = {line_integral}{sub 0}{sup t} D(P(t'))dt' is the distance the burn front propagates from a single hot spot, where D is the deflagration speed and t is the time since the shock arrival. A key implementation issue is how to determine the lead shock strength in conjunction with a shock capturing scheme. They have developed a robust algorithm for this purpose based on the Hugoniot jump condition for the energy. The algorithm utilizes the time dependence of density, pressure and energy within each cell. The method is independent of the numerical dissipation used for shock capturing. It is local and can be used in one or more space dimensions. The burn model has a small number of parameters which can be calibrated to fit velocity gauge data from shock initiation experiments.

  12. Reactive burn models and ignition & growth concept

    Directory of Open Access Journals (Sweden)

    Shaw M.S.


    Full Text Available Plastic-bonded explosives are heterogeneous materials. Experimentally, shock initiation is sensitive to small amounts of porosity, due to the formation of hot spots (small localized regions of high temperature. This leads to the Ignition & Growth concept, introduced by LeeTarver in 1980, as the basis for reactive burn models. A homo- genized burn rate needs to account for three meso-scale physical effects: (i the density of active hot spots or burn centers; (ii the growth of the burn fronts triggered by the burn centers; (iii a geometric factor that accounts for the overlap of deflagration wavelets from adjacent burn centers. These effects can be combined and the burn model defined by specifying the reaction progress variable λ = g(s as a function of a dimensionless reaction length s(t = rbc/ℓbc, rather than by specifying an explicit burn rate. The length scale ℓbc(Ps = [Nbc(Ps]−1/3 is the average distance between burn centers, where Nbc is the number density of burn centers activated by the lead shock. The reaction length rbc(t = ∫t0 D(P(t′dt′ is the distance the burn front propagates from a single burn center, where D(P is the deflagration speed as a function of the local pressure and t is the time since the shock arrival. A key implementation issue is how to determine the lead shock strength in conjunction with a shock capturing scheme. We have developed a robust algorithm for this purpose based on the Hugoniot jump condition for the energy. The algorithm utilizes the time dependence of density, pressure and energy within each cell. The method is independent of the numerical dissipation used for shock capturing. It is local and can be used in one or more space dimensions. The burn model has a small number of parameters which can be calibrated to fit velocity gauge data from shock initiation experiments.

  13. Reactive puff model SCICHEM: Model enhancements and performance studies (United States)

    Chowdhury, B.; Karamchandani, P. K.; Sykes, R. I.; Henn, D. S.; Knipping, E.


    The SCICHEM model incorporates complete gas phase, aqueous and aerosol phase chemistry within a state-of-the-science Gaussian puff model SCIPUFF (Second-order Closure Integrated Puff). The model is a valuable tool that can be used to calculate the impacts of a single source or a small number of sources on downwind ozone and PM2.5. The model has flexible data requirements: it can be run with routine surface and upper air observations or with prognostic meteorological model outputs and source emissions are specified in a simple text format. This paper describes significant advances to the dispersion and chemistry components of the model in the latest release, SCICHEM 3.0. Some of the major advancements include modeling of skewed turbulence for convective boundary layer and updated chemistry schemes (CB05 gas phase chemical mechanism; AERO5 aerosol and aqueous modules). The results from SCICHEM 3.0 are compared with observations from a tracer study as well as aircraft measurements of reactive species in power plant plumes from two field studies. The results with the tracer experiment (Copenhagen study) show that the incorporation of skewed turbulence improves the calculation of tracer dispersion and transport. The comparisons with the Cumberland and Dolet Hills power plume measurements show good correlation between the observed and predicted concentrations of reactive gaseous species at most downwind distances from the source.

  14. Investigation of kinetics model of dc reactive sputtering

    Institute of Scientific and Technical Information of China (English)

    朱圣龙; 王福会; 吴维叓


    A novel physical sputtering kinetics model for reactive sputtering is presented.Reactive gas gettering effects and interactions among the characteristic parameters have been taken into account in the model.The data derived from the model accorded fairly well with experimental results.The relationship between the values of initial oxide coverage on the target and the ready states was depicted in the model.This relationship gives reasons for the difference of the threshold of reactive gas fluxes (Q) from the metal sputtering region to the oxide sputtering region and in reverse direction.The discontinuities in oxide coverage on the target surface (θ) versus reactive gas fluxes (Q) are referred to as the effects of reactive gas partial pressure (p) upon the forming rates of oxide on the surfaces of target (V0).The diversity of the oxygen flux threshold results from the variance of the initial values of oxide coverage on target.

  15. Modelling atmospheric OH-reactivity in a boreal forest ecosystem

    DEFF Research Database (Denmark)

    Mogensen, D.; Smolander, S.; Sogachev, Andrey;


    We have modelled the total atmospheric OH-reactivity in a boreal forest and investigated the individual contributions from gas phase inorganic species, isoprene, monoterpenes, and methane along with other important VOCs. Daily and seasonal variation in OH-reactivity for the year 2008 was examined...... as well as the vertical OH-reactivity profile. We have used SOSA; a one dimensional vertical chemistry-transport model (Boy et al., 2011a) together with measurements from Hyytiala, SMEAR II station, Southern Finland, conducted in August 2008. Model simulations only account for similar to 30......-50% of the total measured OH sink, and in our opinion, the reason for missing OH-reactivity is due to unmeasured unknown BVOCs, and limitations in our knowledge of atmospheric chemistry including uncertainties in rate constants. Furthermore, we found that the OH-reactivity correlates with both organic...

  16. Modelling atmospheric OH-reactivity in a boreal forest ecosystem

    DEFF Research Database (Denmark)

    Mogensen, D.; Smolander, S.; Sogachev, Andrey;


    We have modelled the total atmospheric OH-reactivity in a boreal forest and investigated the individual contributions from gas phase inorganic species, isoprene, monoterpenes, and methane along with other important VOCs. Daily and seasonal variation in OH-reactivity for the year 2008 was examined...

  17. Models of reactive oxygen species in cancer


    Lu, Weiqin; Ogasawara, Marcia A.; Huang, Peng


    Increased generation of reactive oxygen species (ROS) has been observed in cancer, degenerative diseases, and other pathological conditions. ROS can stimulate cell proliferation, promote genetic instability, and induce adaptive responses that enable cancer cells to maintain their malignant phenotypes. However, when cellular redox balance is severely disturbed, high levels of ROS may cause various damages leading to cell death. The studies of ROS effects on biological systems, their underlying...

  18. A synchronous paradigm for modeling stable reactive systems

    Energy Technology Data Exchange (ETDEWEB)

    Winter, V.L.


    This paper describes a modeling technique for single-agent reactive systems, that is influenced by the modeling paradigm of Parnas as well as by the synchronous paradigms of LUSTRE and ESTEREL. In this paradigm, single-agent reactive systems are modeled in a universe having a discrete clock. This discretization of time greatly reduces the temporal complexity of the model. He believes that the advantage of this reduction in temporal complexity is that the resulting model is in many ways better suited to automated software construction and analysis techniques (e.g., deductive synthesis, transformation, and verification) than models that are based on continuous representations of time.

  19. Modeling Biodegradation and Reactive Transport: Analytical and Numerical Models

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Y; Glascoe, L


    The computational modeling of the biodegradation of contaminated groundwater systems accounting for biochemical reactions coupled to contaminant transport is a valuable tool for both the field engineer/planner with limited computational resources and the expert computational researcher less constrained by time and computer power. There exists several analytical and numerical computer models that have been and are being developed to cover the practical needs put forth by users to fulfill this spectrum of computational demands. Generally, analytical models provide rapid and convenient screening tools running on very limited computational power, while numerical models can provide more detailed information with consequent requirements of greater computational time and effort. While these analytical and numerical computer models can provide accurate and adequate information to produce defensible remediation strategies, decisions based on inadequate modeling output or on over-analysis can have costly and risky consequences. In this chapter we consider both analytical and numerical modeling approaches to biodegradation and reactive transport. Both approaches are discussed and analyzed in terms of achieving bioremediation goals, recognizing that there is always a tradeoff between computational cost and the resolution of simulated systems.

  20. Multiple Estimation Architecture in Discrete-Time Adaptive Mixing Control

    Directory of Open Access Journals (Sweden)

    Simone Baldi


    Full Text Available Adaptive mixing control (AMC is a recently developed control scheme for uncertain plants, where the control action coming from a bank of precomputed controller is mixed based on the parameter estimates generated by an on-line parameter estimator. Even if the stability of the control scheme, also in the presence of modeling errors and disturbances, has been shown analytically, its transient performance might be sensitive to the initial conditions of the parameter estimator. In particular, for some initial conditions, transient oscillations may not be acceptable in practical applications. In order to account for such a possible phenomenon and to improve the learning capability of the adaptive scheme, in this paper a new mixing architecture is developed, involving the use of parallel parameter estimators, or multi-estimators, each one working on a small subset of the uncertainty set. A supervisory logic, using performance signals based on the past and present estimation error, selects the parameter estimate to determine the mixing of the controllers. The stability and robustness properties of the resulting approach, referred to as multi-estimator adaptive mixing control (Multi-AMC, are analytically established. Besides, extensive simulations demonstrate that the scheme improves the transient performance of the original AMC with a single estimator. The control scheme and the analysis are carried out in a discrete-time framework, for easier implementation of the method in digital control.

  1. Thermal-hydraulic modeling of reactivity accidents in MTR reactors

    Directory of Open Access Journals (Sweden)

    Khater Hany


    Full Text Available This paper describes the development of a dynamic model for the thermal-hydraulic analysis of MTR research reactors during a reactivity insertion accident. The model is formulated for coupling reactor kinetics with feedback reactivity and reactor core thermal-hydraulics. To represent the reactor core, two types of channels are considered, average and hot channels. The developed computer program is compiled and executed on a personal computer, using the FORTRAN language. The model is validated by safety-related benchmark calculations for MTR-TYPE reactors of IAEA 10 MW generic reactor for both slow and fast reactivity insertion transients. A good agreement is shown between the present model and the benchmark calculations. Then, the model is used for simulating the uncontrolled withdrawal of a control rod of an ETRR-2 reactor in transient with over power scram trip. The model results for ETRR-2 are analyzed and discussed.

  2. Chemical reactor modeling multiphase reactive flows

    CERN Document Server

    Jakobsen, Hugo A


    Chemical Reactor Modeling closes the gap between Chemical Reaction Engineering and Fluid Mechanics.  The second edition consists of two volumes: Volume 1: Fundamentals. Volume 2: Chemical Engineering Applications In volume 1 most of the fundamental theory is presented. A few numerical model simulation application examples are given to elucidate the link between theory and applications. In volume 2 the chemical reactor equipment to be modeled are described. Several engineering models are introduced and discussed. A survey of the frequently used numerical methods, algorithms and schemes is provided. A few practical engineering applications of the modeling tools are presented and discussed. The working principles of several experimental techniques employed in order to get data for model validation are outlined. The monograph is based on lectures regularly taught in the fourth and fifth years graduate courses in transport phenomena and chemical reactor modeling, and in a post graduate course in modern reactor m...

  3. Hard-sphere kinetic models for inert and reactive mixtures (United States)

    Polewczak, Jacek


    I consider stochastic variants of a simple reacting sphere (SRS) kinetic model (Xystris and Dahler 1978 J. Chem. Phys. 68 387-401, Qin and Dahler 1995 J. Chem. Phys. 103 725-50, Dahler and Qin 2003 J. Chem. Phys. 118 8396-404) for dense reacting mixtures. In contrast to the line-of-center models of chemical reactive models, in the SRS kinetic model, the microscopic reversibility (detailed balance) can be easily shown to be satisfied, and thus all mathematical aspects of the model can be fully justified. In the SRS model, the molecules behave as if they were single mass points with two internal states. Collisions may alter the internal states of the molecules, and this occurs when the kinetic energy associated with the reactive motion exceeds the activation energy. Reactive and non-reactive collision events are considered to be hard sphere-like. I consider a four component mixture A, B, A *, B *, in which the chemical reactions are of the type A+B\\rightleftharpoons {{A}\\ast}+{{B}\\ast} , with A * and B * being distinct species from A and B. This work extends the joined works with George Stell to the kinetic models of dense inert and reactive mixtures. The idea of introducing smearing-type effect in the collisional process results in a new class of stochastic kinetic models for both inert and reactive mixtures. In this paper the important new mathematical properties of such systems of kinetic equations are proven. The new results for stochastic revised Enskog system for inert mixtures are also provided.

  4. Modeling of titration experiments by a reactive transport model

    Institute of Scientific and Technical Information of China (English)

    Ma Hongyun; Samper Javier; Xin Xin


    Acid mine drainage (AMD) is commonly treated by neutralization with alkaline substances. This treatment is supported by titration experiments that illustrate the buffering mechanisms and estimate the base neutralization capacity (BNC) of the AMD. Detailed explanation of titration curves requires modeling with a hydro-chemical model. In this study the titration curves of water samples from the drainage of the As Pontes mine and the corresponding dumps have been investigated and six buffers are selected by analyzing those curves. Titration curves have been simulated by a reactive transport model to discover the detailed buffering mechanisms. These simulations show seven regions involving different buffering mechanism. The BNC is primarily from buffers of dissolved Fe, Al and hydrogen sulfate. The BNC can be approximated by: BNC = 3(CFe + CAl) + 0.05Csulfate, where the units are mol/L. The BNC of the sample from the mine is 9.25 × 10-3 mol/L and that of the dumps sample is 1.28 × 10-2 mol/L.

  5. Quantitative Models and Analysis for Reactive Systems

    DEFF Research Database (Denmark)

    Thrane, Claus

    phones and websites. Acknowledging that now more than ever, systems come in contact with the physical world, we need to revise the way we construct models and verification algorithms, to take into account the behavior of systems in the presence of approximate, or quantitative information, provided...... by the environment in which they are embedded. This thesis studies the semantics and properties of a model-based framework for re- active systems, in which models and specifications are assumed to contain quantifiable information, such as references to time or energy. Our goal is to develop a theory of approximation......, by studying how small changes to our models affect the verification results. A key source of motivation for this work can be found in The Embedded Systems Design Challenge [HS06] posed by Thomas A. Henzinger and Joseph Sifakis. It contains a call for advances in the state-of-the-art of systems verification...

  6. Mathematical Models of Tuberculosis Reactivation and Relapse

    Directory of Open Access Journals (Sweden)

    Robert Steven Wallis


    Full Text Available The natural history of human infection with Mycobacterium tuberculosis (Mtb is highly variable, as is the response to treatment of active tuberculosis. There is presently no direct means to identify individuals in whom Mtb infection has been eradicated, whether by a bactericidal immune response or sterilizing antimicrobial chemotherapy. Mathematical models can assist in such circumstances by measuring or predicting events that cannot be directly observed. The 3 models discussed in this review illustrate instances in which mathematical models were used to identify individuals with innate resistance to Mtb infection, determine the etiology of tuberculosis in patients treated with tumor necrosis factor antagonists, and predict the risk of relapse in persons undergoing tuberculosis treatment. These examples illustrate the power of various types of mathematic models to increase knowledge and thereby inform interventions in the present global tuberculosis epidemic.

  7. Assessment of parametric uncertainty for groundwater reactive transport modeling, (United States)

    Shi, Xiaoqing; Ye, Ming; Curtis, Gary P.; Miller, Geoffery L.; Meyer, Philip D.; Kohler, Matthias; Yabusaki, Steve; Wu, Jichun


    The validity of using Gaussian assumptions for model residuals in uncertainty quantification of a groundwater reactive transport model was evaluated in this study. Least squares regression methods explicitly assume Gaussian residuals, and the assumption leads to Gaussian likelihood functions, model parameters, and model predictions. While the Bayesian methods do not explicitly require the Gaussian assumption, Gaussian residuals are widely used. This paper shows that the residuals of the reactive transport model are non-Gaussian, heteroscedastic, and correlated in time; characterizing them requires using a generalized likelihood function such as the formal generalized likelihood function developed by Schoups and Vrugt (2010). For the surface complexation model considered in this study for simulating uranium reactive transport in groundwater, parametric uncertainty is quantified using the least squares regression methods and Bayesian methods with both Gaussian and formal generalized likelihood functions. While the least squares methods and Bayesian methods with Gaussian likelihood function produce similar Gaussian parameter distributions, the parameter distributions of Bayesian uncertainty quantification using the formal generalized likelihood function are non-Gaussian. In addition, predictive performance of formal generalized likelihood function is superior to that of least squares regression and Bayesian methods with Gaussian likelihood function. The Bayesian uncertainty quantification is conducted using the differential evolution adaptive metropolis (DREAM(zs)) algorithm; as a Markov chain Monte Carlo (MCMC) method, it is a robust tool for quantifying uncertainty in groundwater reactive transport models. For the surface complexation model, the regression-based local sensitivity analysis and Morris- and DREAM(ZS)-based global sensitivity analysis yield almost identical ranking of parameter importance. The uncertainty analysis may help select appropriate likelihood

  8. Quantitative Models and Analysis for Reactive Systems

    DEFF Research Database (Denmark)

    Thrane, Claus

    phones and websites. Acknowledging that now more than ever, systems come in contact with the physical world, we need to revise the way we construct models and verification algorithms, to take into account the behavior of systems in the presence of approximate, or quantitative information, provided......, allowing verification procedures to quantify judgements, on how suitable a model is for a given specification — hence mitigating the usual harsh distinction between satisfactory and non-satisfactory system designs. This information, among other things, allows us to evaluate the robustness of our framework......, by studying how small changes to our models affect the verification results. A key source of motivation for this work can be found in The Embedded Systems Design Challenge [HS06] posed by Thomas A. Henzinger and Joseph Sifakis. It contains a call for advances in the state-of-the-art of systems verification...


    Reactive transport modeling has been conducted to describe the performance of the permeable reactive barrier at the Coast Guard Support Center near Elizabeth City, NC. The reactive barrier was installed to treat groundwater contaminated by hexavalent chromium and chlorinated org...

  10. Measurements and models of reactive transport in geological media (United States)

    Berkowitz, Brian; Dror, Ishai; Hansen, Scott K.; Scher, Harvey


    Reactive chemical transport plays a key role in geological media across scales, from pore scale to aquifer scale. Systems can be altered by changes in solution chemistry and a wide variety of chemical transformations, including precipitation/dissolution reactions that cause feedbacks that directly affect the flow and transport regime. The combination of these processes with advective-dispersive-diffusive transport in heterogeneous media leads to a rich spectrum of complex dynamics. The principal challenge in modeling reactive transport is to account for the subtle effects of fluctuations in the flow field and species concentrations; spatial or temporal averaging generally suppresses these effects. Moreover, it is critical to ground model conceptualizations and test model outputs against laboratory experiments and field measurements. This review emphasizes the integration of these aspects, considering carefully designed and controlled experiments at both laboratory and field scales, in the context of development and solution of reactive transport models based on continuum-scale and particle tracking approaches. We first discuss laboratory experiments and field measurements that define the scope of the phenomena and provide data for model comparison. We continue by surveying models involving advection-dispersion-reaction equation and continuous time random walk formulations. The integration of measurements and models is then examined, considering a series of case studies in different frameworks. We delineate the underlying assumptions, and strengths and weaknesses, of these analyses, and the role of probabilistic effects. We also show the key importance of quantifying the spreading and mixing of reactive species, recognizing the role of small-scale physical and chemical fluctuations that control the initiation of reactions.

  11. Modeling Routing Overhead Generated by Wireless Reactive Routing Protocols

    CERN Document Server

    Javaid, Nadeem; Javaid, Akmal; Malik, Shahzad A


    In this paper, we have modeled the routing over- head generated by three reactive routing protocols; Ad-hoc On-demand Distance Vector (AODV), Dynamic Source Routing (DSR) and DYnamic MANET On-deman (DYMO). Routing performed by reactive protocols consists of two phases; route discovery and route maintenance. Total cost paid by a protocol for efficient routing is sum of the cost paid in the form of energy consumed and time spent. These protocols majorly focus on the optimization performed by expanding ring search algorithm to control the flooding generated by the mechanism of blind flooding. So, we have modeled the energy consumed and time spent per packet both for route discovery and route maintenance. The proposed framework is evaluated in NS-2 to compare performance of the chosen routing protocols.

  12. Representing Microbial Processes in Environmental Reactive Transport Models (United States)

    van Cappellen, P.


    Microorganisms play a key role in the biogeochemical functioning of the earth's surface and shallow subsurface. In the context of reactive transport modeling, a major challenge is to derive, parameterize, calibrate and verify mathematical expressions for microbially-mediated reactions in the environmental. This is best achieved by combining field observations, laboratory experiments, theoretical principles and modeling. Here, I will illustrate such an integrated approach for the case of microbial respiration processes in aquatic sediments. Important issues that will be covered include experimental design, model consistency and performance, as well as the bioenergetics and transient behavior of geomicrobial reaction systems.

  13. Modeling food matrix effects on chemical reactivity: Challenges and perspectives. (United States)

    Capuano, Edoardo; Oliviero, Teresa; van Boekel, Martinus A J S


    The same chemical reaction may be different in terms of its position of the equilibrium (i.e., thermodynamics) and its kinetics when studied in different foods. The diversity in the chemical composition of food and in its structural organization at macro-, meso-, and microscopic levels, that is, the food matrix, is responsible for this difference. In this viewpoint paper, the multiple, and interconnected ways the food matrix can affect chemical reactivity are summarized. Moreover, mechanistic and empirical approaches to explain and predict the effect of food matrix on chemical reactivity are described. Mechanistic models aim to quantify the effect of food matrix based on a detailed understanding of the chemical and physical phenomena occurring in food. Their applicability is limited at the moment to very simple food systems. Empirical modeling based on machine learning combined with data-mining techniques may represent an alternative, useful option to predict the effect of the food matrix on chemical reactivity and to identify chemical and physical properties to be further tested. In such a way the mechanistic understanding of the effect of the food matrix on chemical reactions can be improved.

  14. The CREST reactive-burn model for explosives

    Directory of Open Access Journals (Sweden)

    Maheswaran M-A.


    Full Text Available CREST is an innovative reactive-burn model that has been developed at AWE for simulating shock initiation and detonation propagation behaviour in explosives. The model has a different basis from other reactive-burn models in that its reaction rate is independent of local flow variables behind the shock wave e.g. pressure and temperature. The foundation for CREST, based on a detailed analysis of data from particle-velocity gauge experiments, is that the reaction rate depends only on the local shock strength and the time since the shock passed. Since a measure of shock strength is the entropy of the non-reacted explosive, which remains constant behind a shock, CREST uses an entropy-dependent reaction rate. This paper will provide an overview of the CREST model and its predictive capability. In particular, it will be shown that the model can predict a wide range of experimental phenomena for both shock initiation (e.g. the effects of porosity and initial temperature on sustained-shock and thin-flyer initiation and detonation propagation (e.g. the diameter effect curve and detonation failure cones using a single set of coefficients.

  15. Impact of mineralogical heterogeneity on reactive transport modelling (United States)

    Liu, Min; Shabaninejad, Mehdi; Mostaghimi, Peyman


    Impact of mineralogical heterogeneity of rocks in reactive modelling is investigated by applying a pore scale model based on the Lattice Boltzmann and Finite Volume Methods. Mass transport, chemical reaction and solid structure modification are included in the model. A two-dimensional mineral map of a sandstone rock is acquired using the imaging technique of QEMSCAN SEM with Energy-Dispersive X-ray Spectroscopy (EDS). The mineralogical heterogeneity is explored by conducting multi-mineral reaction simulations on images containing various minerals. The results are then compared with the prediction of single mineral dissolution modelling. Dissolution patterns and permeability variations of multi-mineral and single mineral reactions are presented. The errors of single mineral reaction modelling are also estimated. Numerical results show that mineralogical heterogeneity can cause significant errors in permeability prediction, if a uniform mineral distribution is assumed. The errors are smaller in high Péclet regimes than in low Péclet regimes in this sample.

  16. Unifying Model-Based and Reactive Programming within a Model-Based Executive (United States)

    Williams, Brian C.; Gupta, Vineet; Norvig, Peter (Technical Monitor)


    Real-time, model-based, deduction has recently emerged as a vital component in AI's tool box for developing highly autonomous reactive systems. Yet one of the current hurdles towards developing model-based reactive systems is the number of methods simultaneously employed, and their corresponding melange of programming and modeling languages. This paper offers an important step towards unification. We introduce RMPL, a rich modeling language that combines probabilistic, constraint-based modeling with reactive programming constructs, while offering a simple semantics in terms of hidden state Markov processes. We introduce probabilistic, hierarchical constraint automata (PHCA), which allow Markov processes to be expressed in a compact representation that preserves the modularity of RMPL programs. Finally, a model-based executive, called Reactive Burton is described that exploits this compact encoding to perform efficIent simulation, belief state update and control sequence generation.

  17. Formal Requirements Modeling for Reactive Systems with Coloured Petri Nets

    DEFF Research Database (Denmark)

    Tjell, Simon

    This dissertation presents the contributions of seven publications all concerned with the application of Coloured Petri Nets (CPN) to requirements modeling for reactive systems. The publications are introduced along with relevant background material and related work, and their contributions...... interface composed of recognizable artifacts and activities. The presentation of the three publications related to Use Cases is followed by a the presentation of a publication formalizing some of the guidelines applied for structuring the CPN requirements models|namely the guidelines that make it possible...... activity. The traces are automatically recorded during execution of the model. The second publication presents a formally specified framework for automating a large part of the tasks related to integrating Problem Frames with CPN. The framework is specified in VDM++, and allows the modeler to automatically...

  18. Physicochemical model for reactive sputtering of hot target (United States)

    Shapovalov, Viktor I.; Karzin, Vitaliy V.; Bondarenko, Anastasia S.


    A physicochemical model for reactive magnetron sputtering of a metal target is described in this paper. The target temperature in the model is defined as a function of the ion current density. Synthesis of the coating occurs due to the surface chemical reaction. The law of mass action, the Langmuir isotherm and the Arrhenius equation for non-isothermal conditions were used for mathematical description of the reaction. The model takes into consideration thermal electron emission and evaporation of the target surface. The system of eight algebraic equations, describing the model, was solved for the tantalum target sputtered in the oxygen environment. It was established that the hysteresis effect disappears with the increase of the ion current density.

  19. Control Rod Driveline Reactivity Feedback Model for Liquid Metal Reactors

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Young-Min; Jeong, Hae-Yong; Chang, Won-Pyo; Cho, Chung-Ho; Lee, Yong-Bum


    The thermal expansion of the control rod drivelines (CRDL) is one important passive mitigator under all unprotected accident conditions in the metal and oxide cores. When the CRDL are washed by hot sodium in the coolant outlet plenum, the CRDL thermally expands and causes the control rods to be inserted further down into the active core region, providing a negative reactivity feedback. Since the control rods are attached to the top of the vessel head and the core attaches to the bottom of the reactor vessel (RV), the expansion of the vessel wall as it heats will either lower the core or raise the control rods supports. This contrary thermal expansion of the reactor vessel wall pulls the control rods out of the core somewhat, providing a positive reactivity feedback. However this is not a safety factor early in a transient because its time constant is relatively large. The total elongated length is calculated by subtracting the vessel expansion from the CRDL expansion to determine the net control rod expansion into the core. The system-wide safety analysis code SSC-K includes the CRDL/RV reactivity feedback model in which control rod and vessel expansions are calculated using single-nod temperatures for the vessel and CRDL masses. The KALIMER design has the upper internal structures (UIS) in which the CRDLs are positioned outside the structure where they are exposed to the mixed sodium temperature exiting the core. A new method to determine the CRDL expansion is suggested. Two dimensional hot pool thermal hydraulic model (HP2D) originally developed for the analysis of the stratification phenomena in the hot pool is utilized for a detailed heat transfer between the CRDL mass and the hot pool coolant. However, the reactor vessel wall temperature is still calculated by a simple lumped model.

  20. New NIR Calibration Models Speed Biomass Composition and Reactivity Characterization

    Energy Technology Data Exchange (ETDEWEB)


    Obtaining accurate chemical composition and reactivity (measures of carbohydrate release and yield) information for biomass feedstocks in a timely manner is necessary for the commercialization of biofuels. This highlight describes NREL's work to use near-infrared (NIR) spectroscopy and partial least squares multivariate analysis to develop calibration models to predict the feedstock composition and the release and yield of soluble carbohydrates generated by a bench-scale dilute acid pretreatment and enzymatic hydrolysis assay. This highlight is being developed for the September 2015 Alliance S&T Board meeting.

  1. Modelling reactive transport in a phosphogypsum dump, Venezia, Italia (United States)

    Calcara, Massimo; Borgia, Andrea; Cattaneo, Laura; Bartolo, Sergio; Clemente, Gianni; Glauco Amoroso, Carlo; Lo Re, Fabio; Tozzato, Elena


    We develop a reactive-transport porous media flow model for a phosphogypsum dump located on the intertidal deposits of the Venetian Lagoon: 1. we construct a complex conceptual and geologic model from field data using the GMS™ graphical user interface; 2. the geological model is mapped onto a rectangular MODFLOW grid; 3. using the TMT2 FORTRAN90 code we translate this grid into the MESH, INCON and GENER input files for the TOUGH2 series of codes; 4. we run TOUGH-REACT to model flow and reactive transport in the dump and the sediments below it. The model includes 3 different dump materials (phosphogypsum, bituminous and hazardous wastes) with the pores saturated by specific fluids. The sediments below the dump are formed by an intertidal sequence of calcareous sands and silts, in addition to clays and organic deposits, all of which are initially saturated with lagoon salty waters. The recharge rain-water dilutes the dump fluids. In turn, the percolates from the dump react with the underlying sediments and the sea water that saturates them. Simulation results have been compared with chemical sampled analyses. In fact, in spite of the simplicity of our model we are able to show how the pH becomes neutral at a short distance below the dump, a fact observed during aquifer monitoring. The spatial and temporal evolution of dissolution and precipitation reactions occur in our model much alike reality. Mobility of some elements, such as divalent iron, are reduced by specific and concurrent conditions of pH from near-neutrality to moderately high values and positive redox potential; opposite conditions favour mobility of potentially toxic metals such as Cr, As Cd and Pb. Vertical movement are predominant. Trend should be therefore heavily influenced by pH and Eh values. If conditions are favourable to mobility, concentration of these substances in the bottom strata could be high. However, simulation suggest that the sediments tend to reduce the transport potential of

  2. Maximum likelihood Bayesian model averaging and its predictive analysis for groundwater reactive transport models (United States)

    Curtis, Gary P.; Lu, Dan; Ye, Ming


    While Bayesian model averaging (BMA) has been widely used in groundwater modeling, it is infrequently applied to groundwater reactive transport modeling because of multiple sources of uncertainty in the coupled hydrogeochemical processes and because of the long execution time of each model run. To resolve these problems, this study analyzed different levels of uncertainty in a hierarchical way, and used the maximum likelihood version of BMA, i.e., MLBMA, to improve the computational efficiency. This study demonstrates the applicability of MLBMA to groundwater reactive transport modeling in a synthetic case in which twenty-seven reactive transport models were designed to predict the reactive transport of hexavalent uranium (U(VI)) based on observations at a former uranium mill site near Naturita, CO. These reactive transport models contain three uncertain model components, i.e., parameterization of hydraulic conductivity, configuration of model boundary, and surface complexation reactions that simulate U(VI) adsorption. These uncertain model components were aggregated into the alternative models by integrating a hierarchical structure into MLBMA. The modeling results of the individual models and MLBMA were analyzed to investigate their predictive performance. The predictive logscore results show that MLBMA generally outperforms the best model, suggesting that using MLBMA is a sound strategy to achieve more robust model predictions relative to a single model. MLBMA works best when the alternative models are structurally distinct and have diverse model predictions. When correlation in model structure exists, two strategies were used to improve predictive performance by retaining structurally distinct models or assigning smaller prior model probabilities to correlated models. Since the synthetic models were designed using data from the Naturita site, the results of this study are expected to provide guidance for real-world modeling. Limitations of applying MLBMA to the

  3. Reactive Transport Modeling and Changes in Porosity at Reactive Interfaces in a HLW repository in Clay (United States)

    Samper, J.; Mon, A.; Montenegro, L.; Naves, A.; Fernández, J.


    High-level radioactive waste disposal in a deep geological repository is based on a multibarrier concept which combines natural barriers such as the geological formation and artificial barriers such as metallic containers, bentonite and concrete buffers and sealing materials. The stability and performance of the bentonite barrier could be affected by the corrosion products at the canister-bentonite interface and the hyperalkaline conditions caused by the degradation of concrete at the bentonite-concrete interface. Additionally, the host clay formation could also be affected by the hyperalkaline plume at the concrete-clay interface. Here we present a nonisothermal reactive transport model of the long-term interactions of the compacted bentonite with the corrosion products of a carbon-steel canister and the concrete liner of the engineered barrier of a high-level radioactive waste repository in clay. This problem involves large pH changes with a hyperalkaline high-pH plume, complex mineral dissolution/precipitation patterns, cation exchange reactions and proton surface complexation. These reactions lead to large changes in porosity which can even lead to pore clogging. Model results show that magnetite, the main corrosion product, precipitates and reduces significantly the porosity of the bentonite near the canister. The degradation of the concrete liner leads to the precipitation of secondary minerals and the reduction of the porosity of the bentonite and the clay formation at their interfaces with the concrete liner. The zones affected by pore clogging at the canister-bentonite, bentonite-concrete and concrete-clay interfaces at 1 Ma are equal to 10, 25 and 25 mm thick, respectively. The results of our simulations share many of the features of the models reported by others for engineered barrier systems at similar chemical conditions, including: 1) Narrow alteration zones; and 2) Pore clogging at the canister-bentonite, bentonite-concrete and concrete

  4. Adaptive Mesh Refinement in Reactive Transport Modeling of Subsurface Environments (United States)

    Molins, S.; Day, M.; Trebotich, D.; Graves, D. T.


    Adaptive mesh refinement (AMR) is a numerical technique for locally adjusting the resolution of computational grids. AMR makes it possible to superimpose levels of finer grids on the global computational grid in an adaptive manner allowing for more accurate calculations locally. AMR codes rely on the fundamental concept that the solution can be computed in different regions of the domain with different spatial resolutions. AMR codes have been applied to a wide range of problem including (but not limited to): fully compressible hydrodynamics, astrophysical flows, cosmological applications, combustion, blood flow, heat transfer in nuclear reactors, and land ice and atmospheric models for climate. In subsurface applications, in particular, reactive transport modeling, AMR may be particularly useful in accurately capturing concentration gradients (hence, reaction rates) that develop in localized areas of the simulation domain. Accurate evaluation of reaction rates is critical in many subsurface applications. In this contribution, we will discuss recent applications that bring to bear AMR capabilities on reactive transport problems from the pore scale to the flood plain scale.

  5. Modeling Reactive Transport in Coupled Groundwater-Conduit Systems (United States)

    Spiessl, S. M.; Sauter, M.; Zheng, C.; Viswanathan, H. S.


    Modeling reactive transport in coupled groundwater-conduit systems requires consideration of two transport time scales in the flow and transport models. Consider for example a subsurface mine consisting of a network of highly conductive shafts, drifts or ventilation raises (i.e., conduits) within the considerably less permeable ore material (i.e., matrix). In the conduits, potential contaminants can travel much more rapidly than in the background aquifer (matrix). Since conduits cannot necessarily be regarded as a continuum, double continuum models are only of limited use for simulation of contaminant transport in such coupled groundwater-conduit systems. This study utilizes a "hybrid" flow and transport model in which contaminants can in essence be transported at a slower time scale in the matrix and at a faster time scale in the conduits. The hybrid flow model uses an approach developed by Clemens et al. (1996), which is based on the modelling of flow in a discrete pipe network, coupled to a continuum representing the low-permeability inter-conduit matrix blocks. Laminar or turbulent flow can be simulated in the different pipes depending on the flow conditions in the model domain. The three-dimensional finite-difference groundwater flow model MODFLOW (Harbaugh and McDonald, 1996) is used to simulate flow in the continuum. Contaminant transport within the matrix is simulated with a continuum approach using the three-dimensional multi-species solute transport model MT3DMS (Zheng and Wang, 1999), while that in the conduit system is simulated with a one-dimensional advective transport model. As a first step for reactive transport modeling in such systems, only equilibrium reactions among multiple species are considered by coupling the hybrid transport model to a geochemical speciation package. An idealized mine network developed by Viswanathan and Sauter (2001) is used as a test problem in this study. The numerical experiment is based on reference date collected from

  6. Ignition and Growth Reactive Flow Model for IMX-101

    Energy Technology Data Exchange (ETDEWEB)

    Tarver, Craig M. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)


    A set of Ignition and Growth (I&G) reactive flow model parameters is developed for the explosive IMX-101 containing DNAN, NQ, and NTO using the available shock initiation and detonation wave propagation experimental data. The unreacted equation of state for IMX-101 is based on experimental data from gas gun experiments by Furnish et al. and is similar to that of TNT. The product equation of state for IMX-101 is based on CHEETAH chemical equilibrium calculations and cylinder test experimental data. The IMX-101 reaction rate parameters are developed using hydrodynamic reactive flow simulations of several shock initiation and detonation experiments. One set of I&G parameters does a good job of reproducing both shock initiation and detonation experimental data. This is due to the fact that IMX-101 reacts over a relatively small pressure range from about 7 GPa to 20 GPa (C-J pressure). Advanced experiments using embedded gauges and/or laser interferometry could lead to better parameters.

  7. To Model Chemical Reactivity in Heterogeneous Emulsions, Think Homogeneous Microemulsions. (United States)

    Bravo-Díaz, Carlos; Romsted, Laurence Stuart; Liu, Changyao; Losada-Barreiro, Sonia; Pastoriza-Gallego, Maria José; Gao, Xiang; Gu, Qing; Krishnan, Gunaseelan; Sánchez-Paz, Verónica; Zhang, Yongliang; Dar, Aijaz Ahmad


    Two important and unsolved problems in the food industry and also fundamental questions in colloid chemistry are how to measure molecular distributions, especially antioxidants (AOs), and how to model chemical reactivity, including AO efficiency in opaque emulsions. The key to understanding reactivity in organized surfactant media is that reaction mechanisms are consistent with a discrete structures-separate continuous regions duality. Aggregate structures in emulsions are determined by highly cooperative but weak organizing forces that allow reactants to diffuse at rates approaching their diffusion-controlled limit. Reactant distributions for slow thermal bimolecular reactions are in dynamic equilibrium, and their distributions are proportional to their relative solubilities in the oil, interfacial, and aqueous regions. Our chemical kinetic method is grounded in thermodynamics and combines a pseudophase model with methods for monitoring the reactions of AOs with a hydrophobic arenediazonium ion probe in opaque emulsions. We introduce (a) the logic and basic assumptions of the pseudophase model used to define the distributions of AOs among the oil, interfacial, and aqueous regions in microemulsions and emulsions and (b) the dye derivatization and linear sweep voltammetry methods for monitoring the rates of reaction in opaque emulsions. Our results show that this approach provides a unique, versatile, and robust method for obtaining quantitative estimates of AO partition coefficients or partition constants and distributions and interfacial rate constants in emulsions. The examples provided illustrate the effects of various emulsion properties on AO distributions such as oil hydrophobicity, emulsifier structure and HLB, temperature, droplet size, surfactant charge, and acidity on reactant distributions. Finally, we show that the chemical kinetic method provides a natural explanation for the cut-off effect, a maximum followed by a sharp reduction in AO efficiency with

  8. Physicochemical model for reactive sputtering of hot target

    Energy Technology Data Exchange (ETDEWEB)

    Shapovalov, Viktor I., E-mail:; Karzin, Vitaliy V.; Bondarenko, Anastasia S.


    A physicochemical model for reactive magnetron sputtering of a metal target is described in this paper. The target temperature in the model is defined as a function of the ion current density. Synthesis of the coating occurs due to the surface chemical reaction. The law of mass action, the Langmuir isotherm and the Arrhenius equation for non-isothermal conditions were used for mathematical description of the reaction. The model takes into consideration thermal electron emission and evaporation of the target surface. The system of eight algebraic equations, describing the model, was solved for the tantalum target sputtered in the oxygen environment. It was established that the hysteresis effect disappears with the increase of the ion current density. - Highlights: • When model is applied for a cold target, hysteresis width is proportional to the ion current density. • Two types of processes of hot target sputtering are possible, depending on the current density: with and without the hysteresis. • Sputtering process is dominant at current densities less than 50 A/m{sup 2} and evaporation can be neglected. • For current densities over 50 A/m{sup 2} the hysteresis width reaches its maximum and the role of evaporation increases.

  9. Modeling the reactivities of hydroxyl radical and ozone towards atmospheric organic chemicals using quantitative structure-reactivity relationship approaches. (United States)

    Gupta, Shikha; Basant, Nikita; Mohan, Dinesh; Singh, Kunwar P


    The persistence and the removal of organic chemicals from the atmosphere are largely determined by their reactions with the OH radical and O3. Experimental determinations of the kinetic rate constants of OH and O3 with a large number of chemicals are tedious and resource intensive and development of computational approaches has widely been advocated. Recently, ensemble machine learning (EML) methods have emerged as unbiased tools to establish relationship between independent and dependent variables having a nonlinear dependence. In this study, EML-based, temperature-dependent quantitative structure-reactivity relationship (QSRR) models have been developed for predicting the kinetic rate constants for OH (kOH) and O3 (kO3) reactions with diverse chemicals. Structural diversity of chemicals was evaluated using a Tanimoto similarity index. The generalization and prediction abilities of the constructed models were established through rigorous internal and external validation performed employing statistical checks. In test data, the EML QSRR models yielded correlation (R (2)) of ≥0.91 between the measured and the predicted reactivities. The applicability domains of the constructed models were determined using methods based on descriptors range, Euclidean distance, leverage, and standardization approaches. The prediction accuracies for the higher reactivity compounds were relatively better than those of the low reactivity compounds. Proposed EML QSRR models performed well and outperformed the previous reports. The proposed QSRR models can make predictions of rate constants at different temperatures. The proposed models can be useful tools in predicting the reactivities of chemicals towards OH radical and O3 in the atmosphere.

  10. Simulation of reactive processes related to biodegradation in aquifers. 1. Structure of the three-dimensional reactive transport model (United States)

    Schäfer, Dirk; Schäfer, Wolfgang; Kinzelbach, Wolfgang


    The reactive transport model TBC (transport, biochemistry, and chemistry) numerically solves the equations for reactive transport in three-dimensional saturated groundwater flow. A finite element approximation and a standard Galerkin method are used. Solute transport is coupled to microbially mediated organic carbon degradation. Microbial growth is assumed to follow Monod-type kinetics. Substrate consumption and release of metabolic products is coupled to microbial growth via yield coefficients and stoichiometric relations. Additionally, the effects of microbial activity on selected inorganic chemical species in the aquifer can be considered. TBC allows the user to specify a wide range of possible biochemical and chemical reactions in the input file. This makes TBC a powerful and flexible simulation tool. It was developed to simulate reactive processes related to in situ bioremediation, but further fields of application are laboratory column studies on redox processes coupled to organic carbon degradation, field cases of intrinsic biodegradation, and early diagenetic processes in sediments.

  11. Modeling reactive transport with particle tracking and kernel estimators (United States)

    Rahbaralam, Maryam; Fernandez-Garcia, Daniel; Sanchez-Vila, Xavier


    Groundwater reactive transport models are useful to assess and quantify the fate and transport of contaminants in subsurface media and are an essential tool for the analysis of coupled physical, chemical, and biological processes in Earth Systems. Particle Tracking Method (PTM) provides a computationally efficient and adaptable approach to solve the solute transport partial differential equation. On a molecular level, chemical reactions are the result of collisions, combinations, and/or decay of different species. For a well-mixed system, the chem- ical reactions are controlled by the classical thermodynamic rate coefficient. Each of these actions occurs with some probability that is a function of solute concentrations. PTM is based on considering that each particle actually represents a group of molecules. To properly simulate this system, an infinite number of particles is required, which is computationally unfeasible. On the other hand, a finite number of particles lead to a poor-mixed system which is limited by diffusion. Recent works have used this effect to actually model incomplete mix- ing in naturally occurring porous media. In this work, we demonstrate that this effect in most cases should be attributed to a defficient estimation of the concentrations and not to the occurrence of true incomplete mixing processes in porous media. To illustrate this, we show that a Kernel Density Estimation (KDE) of the concentrations can approach the well-mixed solution with a limited number of particles. KDEs provide weighting functions of each particle mass that expands its region of influence, hence providing a wider region for chemical reactions with time. Simulation results show that KDEs are powerful tools to improve state-of-the-art simulations of chemical reactions and indicates that incomplete mixing in diluted systems should be modeled based on alternative conceptual models and not on a limited number of particles.

  12. Microbially Mediated Kinetic Sulfur Isotope Fractionation: Reactive Transport Modeling Benchmark (United States)

    Wanner, C.; Druhan, J. L.; Cheng, Y.; Amos, R. T.; Steefel, C. I.; Ajo Franklin, J. B.


    Microbially mediated sulfate reduction is a ubiquitous process in many subsurface systems. Isotopic fractionation is characteristic of this anaerobic process, since sulfate reducing bacteria (SRB) favor the reduction of the lighter sulfate isotopologue (S32O42-) over the heavier isotopologue (S34O42-). Detection of isotopic shifts have been utilized as a proxy for the onset of sulfate reduction in subsurface systems such as oil reservoirs and aquifers undergoing uranium bioremediation. Reactive transport modeling (RTM) of kinetic sulfur isotope fractionation has been applied to field and laboratory studies. These RTM approaches employ different mathematical formulations in the representation of kinetic sulfur isotope fractionation. In order to test the various formulations, we propose a benchmark problem set for the simulation of kinetic sulfur isotope fractionation during microbially mediated sulfate reduction. The benchmark problem set is comprised of four problem levels and is based on a recent laboratory column experimental study of sulfur isotope fractionation. Pertinent processes impacting sulfur isotopic composition such as microbial sulfate reduction and dispersion are included in the problem set. To date, participating RTM codes are: CRUNCHTOPE, TOUGHREACT, MIN3P and THE GEOCHEMIST'S WORKBENCH. Preliminary results from various codes show reasonable agreement for the problem levels simulating sulfur isotope fractionation in 1D.

  13. Predictive modeling of reactive wetting and metal joining.

    Energy Technology Data Exchange (ETDEWEB)

    van Swol, Frank B.


    The performance, reproducibility and reliability of metal joints are complex functions of the detailed history of physical processes involved in their creation. Prediction and control of these processes constitutes an intrinsically challenging multi-physics problem involving heating and melting a metal alloy and reactive wetting. Understanding this process requires coupling strong molecularscale chemistry at the interface with microscopic (diffusion) and macroscopic mass transport (flow) inside the liquid followed by subsequent cooling and solidification of the new metal mixture. The final joint displays compositional heterogeneity and its resulting microstructure largely determines the success or failure of the entire component. At present there exists no computational tool at Sandia that can predict the formation and success of a braze joint, as current capabilities lack the ability to capture surface/interface reactions and their effect on interface properties. This situation precludes us from implementing a proactive strategy to deal with joining problems. Here, we describe what is needed to arrive at a predictive modeling and simulation capability for multicomponent metals with complicated phase diagrams for melting and solidification, incorporating dissolutive and composition-dependent wetting.

  14. Reactive surface area in geochemical models - Lessons learned from a natural analogue

    NARCIS (Netherlands)

    Koenen, M.; Wasch, L.J.


    Many uncertainties exist in geochemical modeling. Mineral reactive surface area is one of the uncertain parameters. QEMSCAN analyses are performed on sandstone samples from a Dutch CO2 natural analogue to determine reactive surface areas. Geochemical modeling is performed using QEMSCAN surface areas

  15. Modeling Stratospheric Constituents: Reactive Species That Regulate Ozone (United States)

    Salawitch, Ross J.


    Photochemical loss of stratospheric ozone occurs primarily by catalytic cycles whose rates are limited by the concentration of OH, HO2, NO2, ClO, and/or BrO as well as the concentration of either atomic oxygen or of ozone itself. Once the concentrations of these gases are established, the photochemical loss rate of O3 depends on the rate coefficient of only a handful of key reactions. We have developed a method for testing our understanding of stratospheric ozone photochemistry by comparing measured and modeled concentrations of reactive hydrogen, nitrogen, chlorine and bromine radicals using a photochemical steady state model constrained by observed concentrations of long-lived precursors (e.g., NO(y), Cl(y), Br(y), O3, H2O, CH4) and environmental parameters such as ozone column, reflectivity, and aerosol surface area. We will show based on analyses of observations obtained by aircraft, balloon, and satellite platforms during the POLARIS campaign that our overall understanding of the processes that regulate these radical species is very good. The most notable current discrepancies are the tendency to underestimate observed NO2 by 15 to 30% for air masses that experience near continuous solar illumination over a 24 hour period and the tendency to underestimate observed OH and H02 by about 10 to 20% during midday and by much larger amounts at high solar zenith angle (SZA > 85). Possible resolutions to these discrepancies will be discussed. This study was carried out in close collaboration with many members of the POLARIS science team.

  16. Modeling of the jack rabbit series of experiments with a temperature based reactive burn model (United States)

    Desbiens, Nicolas


    The Jack Rabbit experiments, performed by Lawrence Livermore National Laboratory, focus on detonation wave corner turning and shock desensitization. Indeed, while important for safety or charge design, the behaviour of explosives in these regimes is poorly understood. In this paper, our temperature based reactive burn model is calibrated for LX-17 and compared to the Jack Rabbit data. It is shown that our model can reproduce the corner turning and shock desensitization behaviour of four out of the five experiments.

  17. Review of reactive kinetic models describing reductive dechlorination of chlorinated ethenes in soil and groundwater

    DEFF Research Database (Denmark)

    Chambon, Julie Claire Claudia; Bjerg, Poul Løgstrup; Scheutz, Charlotte;


    Reductive dechlorination is a major degradation pathway of chlorinated ethenes in anaerobic subsurface environments, and reactive kinetic models describing the degradation process are needed in fate and transport models of these contaminants. However, reductive dechlorination is a complex biologi...

  18. Atmospheric OH reactivity in central London: observations, model predictions and estimates of in situ ozone production (United States)

    Whalley, Lisa K.; Stone, Daniel; Bandy, Brian; Dunmore, Rachel; Hamilton, Jacqueline F.; Hopkins, James; Lee, James D.; Lewis, Alastair C.; Heard, Dwayne E.


    Near-continuous measurements of hydroxyl radical (OH) reactivity in the urban background atmosphere of central London during the summer of 2012 are presented. OH reactivity behaviour is seen to be broadly dependent on air mass origin, with the highest reactivity and the most pronounced diurnal profile observed when air had passed over central London to the east, prior to measurement. Averaged over the entire observation period of 26 days, OH reactivity peaked at ˜ 27 s-1 in the morning, with a minimum of ˜ 15 s-1 during the afternoon. A maximum OH reactivity of 116 s-1 was recorded on one day during morning rush hour. A detailed box model using the Master Chemical Mechanism was used to calculate OH reactivity, and was constrained with an extended measurement data set of volatile organic compounds (VOCs) derived from a gas chromatography flame ionisation detector (GC-FID) and a two-dimensional GC instrument which included heavier molecular weight (up to C12) aliphatic VOCs, oxygenated VOCs and the biogenic VOCs α-pinene and limonene. Comparison was made between observed OH reactivity and modelled OH reactivity using (i) a standard suite of VOC measurements (C2-C8 hydrocarbons and a small selection of oxygenated VOCs) and (ii) a more comprehensive inventory including species up to C12. Modelled reactivities were lower than those measured (by 33 %) when only the reactivity of the standard VOC suite was considered. The difference between measured and modelled reactivity was improved, to within 15 %, if the reactivity of the higher VOCs (⩾ C9) was also considered, with the reactivity of the biogenic compounds of α-pinene and limonene and their oxidation products almost entirely responsible for this improvement. Further improvements in the model's ability to reproduce OH reactivity (to within 6 %) could be achieved if the reactivity and degradation mechanism of unassigned two-dimensional GC peaks were estimated. Neglecting the contribution of the higher VOCs (⩾ C

  19. Model-Based Testing of a Reactive System with Coloured Petri Nets

    DEFF Research Database (Denmark)

    Tjell, Simon


    In this paper, a reactive and nondeterministic system is tested. This is doneby applying a generic model that has been specified as a configurable Coloured PetriNet. In this way, model-based testing is possible for a wide class of reactive system atthe level of discrete events. Concurrently...... executed tasks are specified at a high levelof abstraction and test traces are collected through state space analysis of the model....

  20. Detailed characterization of a Comparative Reactivity Method (CRM) instrument for ambient OH reactivity measurements: experiments vs. modeling (United States)

    Michoud, Vincent; Locoge, Nadine; Dusanter, Sébastien


    The Hydroxyl radical (OH) is the main daytime oxidant in the troposphere, leading to the oxidation of Volatile Organic Compounds (VOCs) and the formation of harmful pollutants such as ozone (O3) and Secondary Organic Aerosols (SOA). While OH plays a key role in tropospheric chemistry, recent studies have highlighted that there are still uncertainties associated with the OH budget, i.e the identification of sources and sinks and the quantification of production and loss rates of this radical. It has been demonstrated that ambient measurements of the total OH loss rate (also called total OH reactivity) can be used to identify and reduce these uncertainties. In this context, the Comparative Reactivity Method (CRM), developed by Sinha et al. (ACP, 2008), is a promising technique to measure total OH reactivity in ambient air and has already been used during several field campaigns. This technique relies on monitoring competitive reactions of OH with ambient trace gases and a reference compound (pyrrole) in a sampling reactor to derive ambient OH reactivity. However, this technique requires a complex data processing chain that has yet to be carefully investigated in the laboratory. In this study, we present a detailed characterization of a CRM instrument developed at Mines Douai, France. Experiments have been performed to investigate the dependence of the CRM response on humidity, ambient NOx levels, and the pyrrole-to-OH ratio inside the sampling reactor. Box modelling of the chemistry occurring in the reactor has also been performed to assess our theoretical understanding of the CRM measurement. This work shows that the CRM response is sensitive to both humidity and NOx, which can be accounted for during data processing using parameterizations depending on the pyrrole-to-OH ratio. The agreement observed between laboratory studies and model results suggests a good understanding of the chemistry occurring in the sampling reactor and gives confidence in the CRM

  1. Reactive transport modeling for Cs retention: from batch to field experiments (United States)

    De Pourcq, K.; Ayora, C.; Carrera, J.; García-Gutiérrez, M.; Missana, T.; Mingarro, M.


    A Permeable Reactive Barrier has been designed to treat 137Cs polluted groundwater. In order to check both reactivity and permeability, laboratory batch and column tests combined with reactive transport modeling have been performed. The trapping mechanism is based on the sorption of cesium mainly on illite-containing clays. Batch experiments were conducted to obtain the partition coefficients (Kd) of different clay samples in solutions with different potassium concentration. A clear correlation of Kd values with potassium content was observed. The results were modeled with a cation-exchange model. The permeability of the reactive material is provided by the dispersion of the clay on a matrix of wooden shavings. Constant head tests allowed obtaining permeability values. Several column experiments with different flow rates were conducted to confirm the 137Cs retention under different conditions. A blind 1D reactive transport model based on the cation-exchange model was able to predict reasonably well the results of column experiments. The reactive transport model, validated with the column experiments, was used to investigate the performance and duration of 1m thick barrier under different scenarios (flow, clay proportion, 137Cs and K concentration). As expected, the sensitivity tests proved that the retention capacity of dissolved 137Cs in groundwater depends linearly on the amount of clay used in the filling material. As well, the operation time increases linearly when decreasing the flow rate. Finally, the concentration of potassium in inflow water has a remarkable and non-linear influence in the retention of 137Cs. Very high concentrations of potassium are the greatest threat and can lead to the unfeasibility of a permeable reactive barrier. Due to the Cs-K competition, the barrier is comparatively more efficient to treat high concentrations of 137Cs. Up to now, preliminary results from a field scale experiment have confirmed the reactivity and permeability

  2. Modeling of flow and reactive transport in IPARS

    KAUST Repository

    Wheeler, Mary Fanett


    In this work, we describe a number of efficient and locally conservative methods for subsurface flow and reactive transport that have been or are currently being implemented in the IPARS (Integrated Parallel and Accurate Reservoir Simulator). For flow problems, we consider discontinuous Galerkin (DG) methods and mortar mixed finite element methods. For transport problems, we employ discontinuous Galerkin methods and Godunov-mixed methods. For efficient treatment of reactive transport simulations, we present a number of state-of-the-art dynamic mesh adaptation strategies and implementations. Operator splitting approaches and iterative coupling techniques are also discussed. Finally, numerical examples are provided to illustrate the capability of IPARS to treat general biogeochemistry as well as the effectivity of mesh adaptations with DG for transport. © 2012 Bentham Science Publishers. All rights reserved.

  3. Modeling reactive flow and transport in natural systems

    Energy Technology Data Exchange (ETDEWEB)

    Lichtner, P.C. [Center for Nuclear Waste Regulatory Analyses, S.Antonio, TX (United States)


    A general formulation of reactive transport equations in a porous medium has been presented including homogeneous reactions of aqueous species, heterogenous reactions of minerals, and microbiological processes. The canonical form of chemical reactions was introduced and the transformation between primary or basis species derived. The use of parallel linearly-dependent reactions was discussed for incorporating different reaction rate mechanisms. It was demonstrated how the electron may be used in reactive transport equations with redox reactions formulated in terms of half-cell reactions. A single component system was investigated for both a one-dimensional porous medium and a two-dimensional geometry incorporating fracture-matrix interaction. Finally two multicomponent examples were considered using the computer code MULTIFLO of in situ leaching of copper ore and acid mine drainage.

  4. Modeling the dynamics of Plasmodium vivax infection and hypnozoite reactivation in vivo.

    Directory of Open Access Journals (Sweden)

    Adeshina I Adekunle


    Full Text Available The dynamics of Plasmodium vivax infection is characterized by reactivation of hypnozoites at varying time intervals. The relative contribution of new P. vivax infection and reactivation of dormant liver stage hypnozoites to initiation of blood stage infection is unclear. In this study, we investigate the contribution of new inoculations of P. vivax sporozoites to primary infection versus reactivation of hypnozoites by modeling the dynamics of P. vivax infection in Thailand in patients receiving treatment for either blood stage infection alone (chloroquine, or the blood and liver stages of infection (chloroquine + primaquine. In addition, we also analysed rates of infection in a study in Papua New Guinea (PNG where patients were treated with either artesunate, or artesunate + primaquine. Our results show that up to 96% of the P. vivax infection is due to hypnozoite reactivation in individuals living in endemic areas in Thailand. Similar analysis revealed the around 70% of infections in the PNG cohort were due to hypnozoite reactivation. We show how the age of the cohort, primaquine drug failure, and seasonality may affect estimates of the ratio of primary P. vivax infection to hypnozoite reactivation. Modeling of P. vivax primary infection and hypnozoite reactivation provides important insights into infection dynamics, and suggests that 90-96% of blood stage infections arise from hypnozoite reactivation. Major differences in infection kinetics between Thailand and PNG suggest the likelihood of drug failure in PNG.


    Directory of Open Access Journals (Sweden)



    Full Text Available Fragmentation kinetics is employed to model a continuous reactive mixture. An explicit solution is found and experimental data on the catalytic cracking of a mixture of alkanes are used for deactivation and kinetic parameter estimation.

  6. Memories reactivated under ketamine are subsequently stronger: A potential pre-clinical behavioral model of psychosis. (United States)

    Honsberger, Michael J; Taylor, Jane R; Corlett, Philip R


    Sub-anesthetic doses of the NMDA antagonist ketamine have been shown to model the formation and stability of delusion in human subjects. The latter has been predicted to be due to aberrant prediction error resulting in enhanced destabilization of beliefs. To extend the scope of this model, we investigated the effect of administration of low dose systemic ketamine on memory in a rodent model of memory reconsolidation. Systemic ketamine was administered either prior to or immediately following auditory fear memory reactivation in rats. Memory strength was assessed by measuring freezing behavior 24h later. Follow up experiments were designed to investigate an effect of pre-reactivation ketamine on short-term memory (STM), closely related memories, and basolateral amygdala (BLA) specific destabilization mechanisms. Rats given pre-reactivation, but not post-reactivation, ketamine showed larger freezing responses 24h later compared to vehicle. This enhancement was not observed 3h after the memory reactivation, nor was it seen in a closely related contextual memory. Prior inhibition of a known destabilization mechanism in the BLA blocked the effect of pre-reactivation ketamine. Pre- but not post-reactivation ketamine enhances fear memory. These data together with recent data in human subjects supports a model of delusion fixity that proposes that aberrant prediction errors result in enhanced destabilization and strengthening of delusional belief. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. The Modeling and Simulation of Reactive Distillation for the Esterification Process

    Institute of Scientific and Technical Information of China (English)

    朱建华; 沈复


    In this paper,a generalized model of the reactive distillation processes was developed via rate-based approach. The homotopy-continuation method was employed to solve the complicated nonlinear model equations efficiently. The simulation on the reactive distillation processes was carried out with the profiles of stage temperature,composition and flow rate for both vapor and liquid phases obtained. Based on careful analysis of the simulation results, the pitfalls in experimental design were detected. Finally, a software package for the simulation of reactive distillation processes was developed.

  8. Deep removal of 4,6-dimethyldibenzothiophene from model transportation diesel fuels over reactive adsorbent

    Directory of Open Access Journals (Sweden)

    Shengqiang Wang


    Full Text Available This paper presents a new reactive adsorbent used to effectively remove 4,6-dimethyldibenzothiophene (4,6-DMDBT from model transportation diesel fuels. This reactive adsorbent was composed of formaldehyde, phosphotungstic acid and mesoporous silica gel. The experiment was based on an assumed condensation reaction of 4,6-DMDBT with formaldehyde using phosphotungstic acid as catalyst in pore spaces. The effect of temperature and the amount of formaldehyde and phosphotungstic acid loaded on the substrate were investigated in a batch system. In the breakthrough experiment, three different model diesel fuels containing 1000 mg/kg 4,6-DMDBT were pumped through a fixed-bed reactor packed with reactive adsorbent at constant temperature and atmospheric pressure, respectively. The experimental results showed that sulfur-free model fuel was obtained at 80ºC despite the presence of aromatics. The sulfur capacity of regenerated reactive adsorbent was almost totally recovered.

  9. Upscaling heterogeneity in aquifer reactivity via exposure-time concept: forward model. (United States)

    Seeboonruang, Uma; Ginn, Timothy R


    Reactive properties of aquifer solid phase materials play an important role in solute fate and transport in the natural subsurface on time scales ranging from years in contaminant remediation to millennia in dynamics of aqueous geochemistry. Quantitative tools for dealing with the impact of natural heterogeneity in solid phase reactivity on solute fate and transport are limited. Here we describe the use of a structural variable to keep track of solute flux exposure to reactive surfaces. With this approach, we develop a non-reactive tracer model that is useful for determining the signature of multi-scale reactive solid heterogeneity in terms of solute flux distributions at the field scale, given realizations of three-dimensional reactive site density fields. First, a governing Eulerian equation for the non-reactive tracer model is determined by an upscaling technique in which it is found that the exposure time of solution to reactive surface areas evolves via both a macroscopic velocity and a macroscopic dispersion in the artificial dimension of exposure time. Second, we focus on the Lagrangian approach in the context of a streamtube ensemble and demonstrate the use of the distribution of solute flux over the exposure time dimension in modeling two-dimensional transport of a solute undergoing simplified linear reversible reactions, in hypothetical conditions following prior laboratory experiments. The distribution of solute flux over exposure time in a given case is a signature of the impact of heterogeneous aquifer reactivity coupled with a particular physical heterogeneity, boundary conditions, and hydraulic gradient. Rigorous application of this approach in a simulation sense is limited here to linear kinetically controlled reactions.

  10. Benchmarking reactive transport models at a hillslope scale (United States)

    Kalbacher, T.; He, W.; Nixdorf, E.; Jang, E.; Fleckenstein, J. H.; Kolditz, O.


    The hillslope scale is an important transition between the field scale and the catchment scale. The water flow in the unsaturated zone of a hillslope can be highly dynamic, which can lead to dynamic changes of groundwater flow or stream outflow. Additionally, interactions among host rock formation, soil properties and recharge water from precipitation or anthropogenic activities (mining, agriculture etc.) can influence the water quality of groundwater and stream in the long term. To simulate reactive transport processes at such a scale is a challenging task. On the one hand, simulation of water flow in a coupled soil-aquifer system often involves solving of highly non-linear PDEs such as Richards equation; on the other hand, one has to consider complicated biogeochemical reactions (e.g. water-rock interactions, biological degradation, redox reactions). Both aspects are computationally expensive and have high requirements on the numerical precision and stabilities of the employed code. The primary goals of this study are as follows: i) Identify the bottlenecks and quantitatively analyse their influence on simulation of biogeochemical reactions at a hillslope scale; ii) find or suggest practical strategies to deal with these bottlenecks, thus to provide detailed hints for future improvements of reactive transport simulators. To achieve these goals, the parallelized reactive transport simulator OGS#IPhreeqc has been applied to simulate two benchmark examples. The first example is about uranium leaching based on Šimůnek et al. (2012), which considers the leaching of uranium from a mill tailing and accompanied mineral dissolution/precipitation. The geochemical system is then extended to include redox reactions in the second example. Based on these examples, the numerical stability and parallel performance of the tool is analysed. ReferenceŠimůnek, J., Jacques, D., Šejna, M., van Genuchten, M. T.: The HP2 program for HYDRUS (2D/3D), A coupled code for simulating two

  11. OH radical reactivity in an Indiana Forest: Measurements and model comparisons (United States)

    Sigler, P. S. R.; Bottorff, B.; Lew, M.; Stevens, P. S.; Leonardis, T.; Locoge, N.; Sklaveniti, S.; Dusanter, S.; Kundu, S.; Wood, E. C. D.; Gentner, D. R.


    The hydroxyl (OH) radicals plays an important role in the chemistry of the atmosphere. OH radical reactions initiate the oxidation of volatile organic compounds (VOCs) which can lead to the production of ozone and secondary organic aerosols in the atmosphere. In addition, reactions of OH radicals controls the lifetime of methane and other greenhouse gases that affect the radiative balance of the atmosphere. Previous measurements of total hydroxyl radical reactivity in forest environments have found discrepancies between measured values and those calculated from collocated measurements of biogenic VOC (BVOC) concentrations. Additional measurements of total OH reactivity together with measurements of BVOCs are needed to understand the source of this missing reactivity and to further constrain atmospheric chemistry models. Total hydroxyl radical (OH) reactivity was measured using a turbulent flow reactor were made during summer 2015 as part of the Indiana Radical, Reactivity and Ozone Production Intercomparison (IRRONIC). This campaign took place in a forested area at the Indiana Research and Teaching Preserve (IURTP) near the Bloomington campus characterized by high mixing ratios of isoprene and low mixing ratios of NOx. Measurements of a suite of VOCs and oxygenated VOCs was also conducted at the site, allowing a comparison of the observed reactivity with the expected OH reactivity from these measurements.

  12. Reactive attachment disorder--a theoretical model beyond attachment. (United States)

    Minnis, Helen; Marwick, Helen; Arthur, Julie; McLaughlin, Alexis


    Despite its importance in public health, reactive attachment disorder (RAD) is an under-researched and little used clinical category. Abnormalities of social relatedness have long been documented in children who have been abused, neglected or institutionalised, but there have been more recent efforts to define these behaviours within the psychiatric nosology. There has been an implicit assumption that the central deficit in RAD is in the attachment system, but this has caused controversy and may have blocked research. We propose that RAD is better construed within the framework of intersubjectivity, which has a central role in the development of core brain and social functions and may also have had an important role in the evolution of a key human characteristic-complex social functioning. This broader framework may potentially explain apparently diverse symptoms such as indiscriminate friendliness and negative or unpredictable reunion responses. Finally, we suggest that a change of name may be useful in progressing the field, but accept that this may be difficult until there is better agreement in the clinical and scientific communities about the core features and aetiology of this disorder.

  13. Numerical Simulation of High-Power Synthetic Jet Actuator Flowfield and its Influence on Mixing Control

    Institute of Scientific and Technical Information of China (English)


    Detailed two-dimensional unsteady numerical simulation is carried out to investigate a high-power synthetic jet actuator flow field and its design characteristic. Simultaneously, mixing control mechanism of coaxial jets with actuators is also studied. Firstly, excitation frequency (rotating speed), piston displacement and its exit slot width have effect on the controlling ability and controlling efficiency of actuator. With the invariable model and concerned parameters, the actuator becomes more desirable as the rotating speed increases. Average velocity and maximal velocity at the actuator exit section increase as the piston displacement enlarges or the exit slot width decreases. But the actuator does not always exhibit good performance with the narrower exit. Secondly, the synthetic jets also have the "push" effect on the coaxial jets, which results in the fluctuation of vorticity and temperature distribution of mixing fiowfield. Finally, the employment of synthetic jet actuator can achieve mixing enhancement significantly.

  14. The biopsychosocial model of stress in adolescence: self-awareness of performance versus stress reactivity. (United States)

    Rith-Najarian, Leslie R; McLaughlin, Katie A; Sheridan, Margaret A; Nock, Matthew K


    Extensive research among adults supports the biopsychosocial (BPS) model of challenge and threat, which describes relationships among stress appraisals, physiological stress reactivity, and performance; however, no previous studies have examined these relationships in adolescents. Perceptions of stressors as well as physiological reactivity to stress increase during adolescence, highlighting the importance of understanding the relationships among stress appraisals, physiological reactivity, and performance during this developmental period. In this study, 79 adolescent participants reported on stress appraisals before and after a Trier Social Stress Test in which they performed a speech task. Physiological stress reactivity was defined by changes in cardiac output and total peripheral resistance from a baseline rest period to the speech task, and performance on the speech was coded using an objective rating system. We observed in adolescents only two relationships found in past adult research on the BPS model variables: (1) pre-task stress appraisal predicted post-task stress appraisal and (2) performance predicted post-task stress appraisal. Physiological reactivity during the speech was unrelated to pre- and post-task stress appraisals and to performance. We conclude that the lack of association between post-task stress appraisal and physiological stress reactivity suggests that adolescents might have low self-awareness of physiological emotional arousal. Our findings further suggest that adolescent stress appraisals are based largely on their performance during stressful situations. Developmental implications of this potential lack of awareness of one's physiological and emotional state during adolescence are discussed.

  15. Solid phase studies and geochemical modelling of low-cost permeable reactive barriers

    Energy Technology Data Exchange (ETDEWEB)

    Bartzas, Georgios, E-mail: [Laboratory of Metallurgy, School of Mining and Metallurgical Engineering, National Technical University of Athens, Zografos Campus, 15780 Athens (Greece); Komnitsas, Kostas [Department of Mineral Resources Engineering, Technical University of Crete, 73100 Chania (Greece)


    A continuous column experiment was carried out under dynamic flow conditions in order to study the efficiency of low-cost permeable reactive barriers (PRBs) to remove several inorganic contaminants from acidic solutions. A 50:50 w/w waste iron/sand mixture was used as candidate reactive media in order to activate precipitation and promote sorption and reduction-oxidation mechanisms. Solid phase studies of the exhausted reactive products after column shutdown, using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD), confirmed that the principal Fe corrosion products identified in the reactive zone are amorphous iron (hydr)oxides (maghemite/magnetite and goethite), intermediate products (sulfate green rust), and amorphous metal sulfides such as amFeS and/or mackinawite. Geochemical modelling of the metal removal processes, including interactions between reactive media, heavy metal ions and sulfates, and interpretation of the ionic profiles was also carried out by using the speciation/mass transfer computer code PHREEQC-2 and the WATEQ4F database. Mineralogical characterization studies as well as geochemical modelling calculations also indicate that the effect of sulfate and silica sand on the efficiency of the reactive zone should be considered carefully during design and operation of low-cost field PRBs.

  16. Dynamic behaviour of reactive distillation tray columns described with a non-equilibrium cell model

    NARCIS (Netherlands)

    Baur, R.; Taylor, R.; Krishna, R.


    In this paper we develop a generic, dynamic, nonequilibrium (NEQ) cell model for reactive distillation (RD) tray columns. The features of our model are (1) the use of Maxwell–Stefan equations for describing mass transfer between fluid phases, (2) the reaction is assumed to take place in the liquid

  17. Lattice Boltzmann based multicomponent reactive transport model coupled with geochemical solver for scale simulations

    NARCIS (Netherlands)

    Patel, R.A.; Perko, J.; Jaques, D.; De Schutter, G.; Ye, G.; Van Breugel, K.


    A Lattice Boltzmann (LB) based reactive transport model intended to capture reactions and solid phase changes occurring at the pore scale is presented. The proposed approach uses LB method to compute multi component mass transport. The LB multi-component transport model is then coupled with the well

  18. New Fuel Pin Axial Expansion Reactivity Feedback Model in MARS-LMR

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Chiwoong; Ha, Kwiseok [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)


    In this study, the sensitivity tests are conducted. In the case of the UTOP event, a sensitivity test for the reactivity insertion amount and rate were conducted. This analysis can give a requirement for margin of control rod stop system (CRSS). For example, the CRSS in the PRISM designed based on the 0.4 $ reactivity insertion, which is analyzed with safety analysis of UTOP event. Moreover, the sensitivity tests for weighting factor in the core radial expansion reactivity feedback model were also carried out for all ATWS events. Currently, the reactivity feedback model for the PGSFR is not validated yet. However, the reactivity feedback models in the MARS-LMR are validating with various plant-based data including EBR-II SHRT. The ATWS events for the PGSFR classified in the design extended condition including UTOP, ULOF, and ULOHS are analyzed with MARS-LMR. In this study, the sensitivity tests for reactivity insertion amount and rate in the UTOP event are conducted. The reactivity insertion amount is obviously an influential parameter. The reactivity insertion amount can give a requirement for design of the CRSS, therefore, this sensitivity result is very important to the CRSS. In addition, sensitivity tests for the weighting factor in the radial expansion reactivity model are carried out. The weighting factor for a grid plate, W{sub GP}, which means contribution of feedback in the grid plate is changed for all unprotected events. The grid plate expansion is governed by a core inlet temperature. As the W{sub GP} is increased, the power in the UTOP and the ULOF is increased, however, the power in the ULOHS is decreased. The higher power during transient means lower reactivity feedback and smaller expansion. Thus, the core outlet temperature rise is dominant in the UTOP and ULOF events, however, the core inlet temperature rise is dominant in the ULOHS. Therefore, the grid plate expansion in the ULOHS is predominant. These analysis results will give better

  19. Pore scale modeling of reactive transport involved in geologic CO2 sequestration

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Qinjin [Los Alamos National Laboratory; Lichtner, Peter C [Los Alamos National Laboratory; Viswanathan, Hari S [Los Alamos National Laboratory; Abdel-fattah, Amr I [Los Alamos National Laboratory


    We apply a multi-component reactive transport lattice Boltzmann model developed in previolls studies to modeling the injection of a C02 saturated brine into various porous media structures at temperature T=25 and 80 C. The porous media are originally consisted of calcite. A chemical system consisting of Na+, Ca2+, Mg2+, H+, CO2(aq), and CI-is considered. The fluid flow, advection and diHusion of aqueous species, homogeneous reactions occurring in the bulk fluid, as weB as the dissolution of calcite and precipitation of dolomite are simulated at the pore scale. The effects of porous media structure on reactive transport are investigated. The results are compared with continuum scale modeling and the agreement and discrepancy are discussed. This work may shed some light on the fundamental physics occurring at the pore scale for reactive transport involved in geologic C02 sequestration.

  20. Non-Equilibrium Zeldovich-Von Neumann-Doring Theory and Reactive Flow Modeling of Detonation

    Energy Technology Data Exchange (ETDEWEB)

    Tarver, C M; Forbes, J W; Urtiew, P A


    This paper discusses the Non-Equilibrium Zeldovich - von Neumann - Doring (NEZND) theory of self-sustaining detonation waves and the Ignition and Growth reactive flow model of shock initiation and detonation wave propagation in solid explosives. The NEZND theory identified the non-equilibrium excitation processes that precede and follow the exothermic decomposition of a large high explosive molecule into several small reaction product molecules. The thermal energy deposited by the leading shock wave must be distributed to the vibrational modes of the explosive molecule before chemical reactions can occur. The induction time for the onset of the initial endothermic reactions can be calculated using high pressure, high temperature transition state theory. Since the chemical energy is released well behind the leading shock front of a detonation wave, a physical mechanism is required for this chemical energy to reinforce the leading shock front and maintain its overall constant velocity. This mechanism is the amplification of pressure wavelets in the reaction zone by the process of de-excitation of the initially highly vibrationally excited reaction product molecules. This process leads to the development of the three-dimensional structure of detonation waves observed for all explosives. For practical predictions of shock initiation and detonation in hydrodynamic codes, phenomenological reactive flow models have been developed. The Ignition and Growth reactive flow model of shock initiation and detonation in solid explosives has been very successful in describing the overall flow measured by embedded gauges and laser interferometry. This reactive flow model uses pressure and compression dependent reaction rates, because time resolved experimental temperature data is not yet available. Since all chemical reaction rates are ultimately controlled by temperature, the next generation of reactive flow models will use temperature dependent reaction rates. Progress on a

  1. Xanthan exopolysaccharide: Acid-base reactivity related to structure and conformation. A model for understanding the reactivity of degraded and colloidal soil organic matter


    Causse, Benjamin; HEYRAUD, Alain


    Bacterial cells and bacterial exopolysaccharides differ strongly in their respective colloidal and polymeric habits. This suggests different reactivities toward metals and protons, although recent studies point to the similarity of such substrates in terms of site density and metal complexation strength. The aim of this paper is to investigate the causes of this surprising uniqueness by studying the reactivity of a model exopolysaccharide, xanthan. NMR and molecular analysis were used to unam...

  2. PHT3D-UZF: A reactive transport model for variably-saturated porous media (United States)

    Wu, Ming Zhi; Post, Vincent E. A.; Salmon, S. Ursula; Morway, Eric; Prommer, H.


    A modified version of the MODFLOW/MT3DMS-based reactive transport model PHT3D was developed to extend current reactive transport capabilities to the variably-saturated component of the subsurface system and incorporate diffusive reactive transport of gaseous species. Referred to as PHT3D-UZF, this code incorporates flux terms calculated by MODFLOW's unsaturated-zone flow (UZF1) package. A volume-averaged approach similar to the method used in UZF-MT3DMS was adopted. The PHREEQC-based computation of chemical processes within PHT3D-UZF in combination with the analytical solution method of UZF1 allows for comprehensive reactive transport investigations (i.e., biogeochemical transformations) that jointly involve saturated and unsaturated zone processes. Intended for regional-scale applications, UZF1 simulates downward-only flux within the unsaturated zone. The model was tested by comparing simulation results with those of existing numerical models. The comparison was performed for several benchmark problems that cover a range of important hydrological and reactive transport processes. A 2D simulation scenario was defined to illustrate the geochemical evolution following dewatering in a sandy acid sulfate soil environment. Other potential applications include the simulation of biogeochemical processes in variably-saturated systems that track the transport and fate of agricultural pollutants, nutrients, natural and xenobiotic organic compounds and micropollutants such as pharmaceuticals, as well as the evolution of isotope patterns.

  3. Adsorbed polyelectrolyte coatings decrease Fe(0) nanoparticle reactivity with TCE in water: conceptual model and mechanisms. (United States)

    Phenrat, Tanapon; Liu, Yueqiang; Tilton, Robert D; Lowry, Gregory V


    The surfaces of reactive nanoscale zerovalent iron (NZVI) particles used for in situ groundwater remediation are modified with polymers or polyelectrolytes to enhance colloidal stability and mobility in the subsurface. However, surface modification decreases NZVI reactivity. Here, the TCE dechlorination rate and reaction products are measured as a function of adsorbed polyelectrolyte mass for three commercially available polyelectrolytes used for NZVI surface modification including poly(styrene sulfonate) (PSS), carboxymethyl cellulose (CMC), and polyaspartate (PAP). The adsorbed mass, extended layer thickness, and TCE-polyelectrolyte partition coefficient are measured and used to explain the effect of adsorbed polyelectrolyte on NZVI reactivity. For all modifiers, the dechlorination rate constant decreased nonlinearly with increasing surface excess, with a maximum of a 24-fold decrease in reactivity. The TCE dechlorination pathways were not affected. Consistent with Scheutjens-Fleer theory for homopolymer adsorption, the nonlinear relationship between the dechlorination rate and the surface excess of adsorbed polyelectrolyte suggests that adsorbed polyelectrolyte decreases reactivity primarily by blocking reactive surface sites at low surface excess where they adsorb relatively flat onto the NZVI surface, and by a combination of site blocking and decreasing the aqueous TCE concentration at the NZVI surface due to partitioning of TCE to adsorbed polyelectrolytes. This explanation is also consistent with the effect of adsorbed polyelectrolyte on acetylene formation. This conceptual model should apply to other medium and high molecular weight polymeric surface modifiers on nanoparticles, and potentially to adsorbed natural organic matter.

  4. Column Testing and 1D Reactive Transport Modeling to Evaluate Uranium Plume Persistence Processes

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Raymond H. [Navarro Research and Engineering, Inc.; Morrison, Stan [Navarro Research and Engineering, Inc.; Morris, Sarah [Navarro Research and Engineering, Inc.; Tigar, Aaron [Navarro Research and Engineering, Inc.; Dam, William [U.S. Department of Energy, Office of Legacy Management; Dayvault, Jalena [U.S. Department of Energy, Office of Legacy Management


    Motivation for Study: Natural flushing of contaminants at various U.S. Department of Energy Office of Legacy Management sites is not proceeding as quickly as predicted (plume persistence) Objectives: Help determine natural flushing rates using column tests. Use 1D reactive transport modeling to better understand the major processes that are creating plume persistence Approach: Core samples from under a former mill tailings area Tailings have been removed. Column leaching using lab-prepared water similar to nearby Gunnison River water. 1D reactive transport modeling to evaluate processes

  5. In silico pharmacophore modeling on known pyridinium oxime reactivators of cyclosarin (GF) inhibited AChE to Aid discovery of potential, more efficacious novel non-oxime reactivators. (United States)

    Bhattacharjee, Apurba K; Musilek, Kamil; Kuca, Kamil


    Cyclohexyl methylphosphonofluoridate (cyclosarin, cyclosin, GF) is a highly toxic organophosphorus (OP) nerve agent considered as potential warfare threats and known to be resistant to conventional oxime antidotal therapy. To aid discovery of novel antidotes for GF toxicity, a three-dimensional in silico pharmacophore model for reactivation efficacy against GF intoxication is presented. The model was generated from published experimental percentage reactivation data on oximes as changes of AChE/BuChE activities in the whole blood after cyclosarin intoxication and administration. The generated pharmacophore model was found to contain a hydrogen bond donor site and two ring aromatic sites as necessary optimal features for reactivation of GF intoxication. Stereo-electronic features of oximes reported by us earlier provided guidance to develop the model and were found to be consistent with the reported structure activity data. Furthermore, from virtual screening of two commercial databases, Maybridge and ChemNavigator using map-fitting of the model led us to identify two new non-oxime compounds showing reactivation efficacy within 10-fold range of 2-PAM for DFP-inhibited AChE. Since GF is a G simulator like DFP (diisopropylfluorophosphate), the model should have the potential for discovery of novel reactivators against GF intoxication.

  6. Coupled hydrogeological and reactive transport modelling of the Simpevarp area (Sweden)

    Energy Technology Data Exchange (ETDEWEB)

    Molinero, Jorge [Amphos XXI Consulting, S.L. Pg. de Rubi, 29-31, 08197 Valldoreix, Barcelona (Spain)], E-mail:; Raposo, Juan R.; Galindez, Juan M. [Escola Politecnica Superior, Universidade de Santiago de Compostela, Campus Universitario s/n, 27002 Lugo (Spain); Arcos, David; Guimera, Jordi [Amphos XXI Consulting, S.L. Pg. de Rubi, 29-31, 08197 Valldoreix, Barcelona (Spain)


    The Simpevarp area is one of the alternative sites being considered for the deep geological disposal of high level radioactive waste in Sweden. In this paper, a coupled regional groundwater flow and reactive solute transport model of the Simpevarp area is presented that integrates current hydrogeological and hydrochemical data of the area. The model simulates the current hydrochemical pattern of the groundwater system in the area. To that aim, a conceptual hydrochemical model was developed in order to represent the dominant chemical processes. Groundwater flow conditions were reproduced by taking into account fluid-density-dependent groundwater flow and regional hydrogeologic boundary conditions. Reactive solute transport calculations were performed on the basis of the velocity field so obtained. The model was calibrated and sensitivity analyses were carried out in order to investigate the effects of heterogeneities of hydraulic conductivity in the subsurface medium. Results provided by the reactive transport model are in good agreement with much of the measured hydrochemical data. This paper emphasizes the appropriateness of the use of reactive solute transport models when water-rock interaction reactions are involved, and demonstrates what powerful tools they are for the interpretation of hydrogeological and hydrochemical data from site geological repository characterization programs, by providing a qualitative framework for data analysis and testing of conceptual assumptions in a process-oriented approach.

  7. Modeling Of A Reactive Distillation Column: Methyl Tertiary Butyl Ether (Mtbe Simulation Studies

    Directory of Open Access Journals (Sweden)

    Ismail Mohd Saaid Abdul Rahman Mohamed and Subhash Bhatia


    Full Text Available A process simulation stage-wise reactive distillation column model formulated from equilibrium stage theory was developed. The algorithm for solving mathematical model represented by sets of differential-algebraic equations was based on relaxation method. Numerical integration scheme based on backward differentiation formula was selected for solving the stiffness of differential-algebraic equations. Simulations were performed on a personal computer (PC Pentium processor through a developed computer program using FORTRAN90 programming language. The proposed model was validated by comparing the simulated results with the published simulation results and with the pilot plant data from the literature. The model was capable of predicting high isobutene conversion for heterogeneous system, as desirable in industrial MTBE production process. The comparisons on temperature profiles, liquid composition profile and operating conditions of reactive distillation column also showed promising results. Therefore the proposed model can be used as a tool for the development and simulation of reactive distillation column.Keywords: Modeling, simulation, reactive distillation, relaxation method, equilibrium stage, heterogeneous, MTBE

  8. Nonspecific airway reactivity in a mouse model of asthma

    Energy Technology Data Exchange (ETDEWEB)

    Collie, D.D.; Wilder, J.A.; Bice, D.E.


    Animal models are indispensable for studies requiring an intact immune system, especially for studying the pathogenic mechanisms in atopic diseases, regulation of IgE production, and related biologic effects. Mice are particularly suitable and have been used extensively for such studies because their immune system is well characterized. Further, large numbers of mutants or inbred strains of mice are available that express deficiencies of individual immunologic processes, inflammatory cells, or mediator systems. By comparing reactions in such mice with appropriate control animals, the unique roles of individual cells or mediators may be characterized more precisely in the pathogenesis of atopic respiratory diseases including asthma. However, given that asthma in humans is characterized by the presence of airway hyperresponsiveness to specific and nonspecific stimuli, it is important that animal models of this disease exhibit similar physiologic abnormalities. In the past, the size of the mouse has limited its versatility in this regard. However, recent studies indicate the feasibility of measuring pulmonary responses in living mice, thus facilitating the physiologic evaluation of putative mouse models of human asthma that have been well charcterized at the immunologic and patholigic level. Future work will provide details of the morphometry of the methacholine-induced bronchoconstriction and will further seek to determine the relationship between cigarette smoke exposure and the development of NS-AHR in the transgenic mouse model.

  9. Modeling turbulence structure. Chemical kinetics interaction in turbulent reactive flows

    Energy Technology Data Exchange (ETDEWEB)

    Magnussen, B.F. [The Norwegian Univ. of Science and Technology, Trondheim (Norway)


    The challenge of the mathematical modelling is to transfer basic physical knowledge into a mathematical formulation such that this knowledge can be utilized in computational simulation of practical problems. The combustion phenomena can be subdivided into a large set of interconnected phenomena like flow, turbulence, thermodynamics, chemical kinetics, radiation, extinction, ignition etc. Combustion in one application differs from combustion in another area by the relative importance of the various phenomena. The difference in fuel, geometry and operational conditions often causes the differences. The computer offers the opportunity to treat the individual phenomena and their interactions by models with wide operational domains. The relative magnitude of the various phenomena therefore becomes the consequence of operational conditions and geometry and need not to be specified on the basis of experience for the given problem. In mathematical modelling of turbulent combustion, one of the big challenges is how to treat the interaction between the chemical reactions and the fluid flow i.e. the turbulence. Different scientists adhere to different concepts like the laminar flamelet approach, the pdf approach of the Eddy Dissipation Concept. Each of these approaches offers different opportunities and problems. All these models are based on a sound physical basis, however none of these have general validity in taking into consideration all detail of the physical chemical interaction. The merits of the models can only be judged by their ability to reproduce physical reality and consequences of operational and geometric conditions in a combustion system. The presentation demonstrates and discusses the development of a coherent combustion technology for energy conversion and safety based on the Eddy Dissipation Concept by Magnussen. (author) 30 refs.

  10. Surrogate model approach for improving the performance of reactive transport simulations (United States)

    Jatnieks, Janis; De Lucia, Marco; Sips, Mike; Dransch, Doris


    Reactive transport models can serve a large number of important geoscientific applications involving underground resources in industry and scientific research. It is common for simulation of reactive transport to consist of at least two coupled simulation models. First is a hydrodynamics simulator that is responsible for simulating the flow of groundwaters and transport of solutes. Hydrodynamics simulators are well established technology and can be very efficient. When hydrodynamics simulations are performed without coupled geochemistry, their spatial geometries can span millions of elements even when running on desktop workstations. Second is a geochemical simulation model that is coupled to the hydrodynamics simulator. Geochemical simulation models are much more computationally costly. This is a problem that makes reactive transport simulations spanning millions of spatial elements very difficult to achieve. To address this problem we propose to replace the coupled geochemical simulation model with a surrogate model. A surrogate is a statistical model created to include only the necessary subset of simulator complexity for a particular scenario. To demonstrate the viability of such an approach we tested it on a popular reactive transport benchmark problem that involves 1D Calcite transport. This is a published benchmark problem (Kolditz, 2012) for simulation models and for this reason we use it to test the surrogate model approach. To do this we tried a number of statistical models available through the caret and DiceEval packages for R, to be used as surrogate models. These were trained on randomly sampled subset of the input-output data from the geochemical simulation model used in the original reactive transport simulation. For validation we use the surrogate model to predict the simulator output using the part of sampled input data that was not used for training the statistical model. For this scenario we find that the multivariate adaptive regression splines

  11. Benchmarking a Visual-Basic based multi-component one-dimensional reactive transport modeling tool (United States)

    Torlapati, Jagadish; Prabhakar Clement, T.


    We present the details of a comprehensive numerical modeling tool, RT1D, which can be used for simulating biochemical and geochemical reactive transport problems. The code can be run within the standard Microsoft EXCEL Visual Basic platform, and it does not require any additional software tools. The code can be easily adapted by others for simulating different types of laboratory-scale reactive transport experiments. We illustrate the capabilities of the tool by solving five benchmark problems with varying levels of reaction complexity. These literature-derived benchmarks are used to highlight the versatility of the code for solving a variety of practical reactive transport problems. The benchmarks are described in detail to provide a comprehensive database, which can be used by model developers to test other numerical codes. The VBA code presented in the study is a practical tool that can be used by laboratory researchers for analyzing both batch and column datasets within an EXCEL platform.

  12. A Novel Lattice Boltzmann Model For Reactive Flows with Fast Chemistry

    Institute of Scientific and Technical Information of China (English)

    CHEN Sheng; LIU Zhao-Hui; HE Zhu; ZHANG Chao; TIAN Zhi-Wei; SHI Bao-Chang; ZHENG Chu-Guang


    @@ A novel lattice Boltzmann model, in which we take the ratio of temperature difference in the temperature field to the environment one to be more than one order of magnitude than before, is developed to simulate two dimensional reactive flows with fast chemistry. Different from the hybrid scheme for reactive flows [Comput.Phys. Commun. 129 (2000)267], this scheme is strictly in a pure lattice Boltzmann style (i.e., we solve the flow, temperature, and concentration fields using the lattice Boltzmann method only). Different from the recent non-coupled lattice Boltzmann scheme [Int. J. Mod. Phys. B 17(2003) 197], the fluid density in our model is coupled directly with the temperature. Excellent agreement between the present results and other numerical data shows that this scheme is an efficient numerical method for practical reactive flows with fast chemistry.

  13. SeSBench - An initiative to benchmark reactive transport models for environmental subsurface processes (United States)

    Jacques, Diederik


    As soil functions are governed by a multitude of interacting hydrological, geochemical and biological processes, simulation tools coupling mathematical models for interacting processes are needed. Coupled reactive transport models are a typical example of such coupled tools mainly focusing on hydrological and geochemical coupling (see e.g. Steefel et al., 2015). Mathematical and numerical complexity for both the tool itself or of the specific conceptual model can increase rapidly. Therefore, numerical verification of such type of models is a prerequisite for guaranteeing reliability and confidence and qualifying simulation tools and approaches for any further model application. In 2011, a first SeSBench -Subsurface Environmental Simulation Benchmarking- workshop was held in Berkeley (USA) followed by four other ones. The objective is to benchmark subsurface environmental simulation models and methods with a current focus on reactive transport processes. The final outcome was a special issue in Computational Geosciences (2015, issue 3 - Reactive transport benchmarks for subsurface environmental simulation) with a collection of 11 benchmarks. Benchmarks, proposed by the participants of the workshops, should be relevant for environmental or geo-engineering applications; the latter were mostly related to radioactive waste disposal issues - excluding benchmarks defined for pure mathematical reasons. Another important feature is the tiered approach within a benchmark with the definition of a single principle problem and different sub problems. The latter typically benchmarked individual or simplified processes (e.g. inert solute transport, simplified geochemical conceptual model) or geometries (e.g. batch or one-dimensional, homogeneous). Finally, three codes should be involved into a benchmark. The SeSBench initiative contributes to confidence building for applying reactive transport codes. Furthermore, it illustrates the use of those type of models for different

  14. On Numerical Considerations for Modeling Reactive Astrophysical Shocks

    CERN Document Server

    Papatheodore, Thomas L


    Simulating detonations in astrophysical environments is often complicated by numerical approximations to shock structure. A common prescription to ensure correct detonation speeds and associated quantities is to prohibit burning inside the numerically broadened shock (Fryxell et al. 1989). We have performed a series of simulations to verify the efficacy of this approximation and to understand how resolution and dimensionality might affect its use. Our results show that, in one dimension, prohibiting burning in the shock is important wherever the carbon burning length is not resolved, in keeping with the results of Fryxell et al. (1989). In two dimensions, we find that the prohibition of shock burning effectively inhibits the development of cellular structure for all but the most highly-resolved cases. We discuss the possible impacts this outcome may have on sub-grid models and detonation propagation in models of Type Ia supernovae, including potential impacts on observables.

  15. Reactive Aggregate Model Protecting Against Real-Time Threats (United States)


    SQL server and has four tables: Accumulator, BlockState, Epoc , Signature, and Weight. Accumulator columns were RemoteIP, Test1, Test2, Test3 and Time...block occurred. The Epoc table was a pivot necessary to convert the time stamps to Epoch time format. The Signature table held values indicative of...processing unit” of the RAMPART Figure 6. model. The RAMPART database exists on a Windows SQL server and has four tables: Accumulator, BlockState, Epoc

  16. Smoothed Particle Hydrodynamics Model for Reactive Transport and Mineral Precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Tartakovsky, Alexandre M.; Scheibe, Timothy D.; Redden, George; Meakin, Paul; Fang, Yilin


    A new Lagrangian particle model based on smoothed particle hydrodynamics was used to simulate pore scale precipitation reactions. The side-by-side injection of reacting solutions into two halves of a two-dimensional granular porous medium was simulated. Precipitation on grain surfaces occurred along a narrow zone in the middle of the domain, where the reacting solutes mixed to generate a supersaturated reaction product. The numerical simulations qualitatively reproduced the behavior observed in related laboratory experiments.

  17. Modeling the surface tension of complex, reactive organic-inorganic mixtures (United States)

    Schwier, A. N.; Viglione, G. A.; Li, Z.; McNeill, V. Faye


    Atmospheric aerosols can contain thousands of organic compounds which impact aerosol surface tension, affecting aerosol properties such as heterogeneous reactivity, ice nucleation, and cloud droplet formation. We present new experimental data for the surface tension of complex, reactive organic-inorganic aqueous mixtures mimicking tropospheric aerosols. Each solution contained 2-6 organic compounds, including methylglyoxal, glyoxal, formaldehyde, acetaldehyde, oxalic acid, succinic acid, leucine, alanine, glycine, and serine, with and without ammonium sulfate. We test two semi-empirical surface tension models and find that most reactive, complex, aqueous organic mixtures which do not contain salt are well described by a weighted Szyszkowski-Langmuir (S-L) model which was first presented by Henning et al. (2005). Two approaches for modeling the effects of salt were tested: (1) the Tuckermann approach (an extension of the Henning model with an additional explicit salt term), and (2) a new implicit method proposed here which employs experimental surface tension data obtained for each organic species in the presence of salt used with the Henning model. We recommend the use of method (2) for surface tension modeling of aerosol systems because the Henning model (using data obtained from organic-inorganic systems) and Tuckermann approach provide similar modeling results and goodness-of-fit (χ2) values, yet the Henning model is a simpler and more physical approach to modeling the effects of salt, requiring less empirically determined parameters.

  18. Multi-scale modeling of multi-component reactive transport in geothermal aquifers (United States)

    Nick, Hamidreza M.; Raoof, Amir; Wolf, Karl-Heinz; Bruhn, David


    In deep geothermal systems heat and chemical stresses can cause physical alterations, which may have a significant effect on flow and reaction rates. As a consequence it will lead to changes in permeability and porosity of the formations due to mineral precipitation and dissolution. Large-scale modeling of reactive transport in such systems is still challenging. A large area of uncertainty is the way in which the pore-scale information controlling the flow and reaction will behave at a larger scale. A possible choice is to use constitutive relationships relating, for example the permeability and porosity evolutions to the change in the pore geometry. While determining such relationships through laboratory experiments may be limited, pore-network modeling provides an alternative solution. In this work, we introduce a new workflow in which a hybrid Finite-Element Finite-Volume method [1,2] and a pore network modeling approach [3] are employed. Using the pore-scale model, relevant constitutive relations are developed. These relations are then embedded in the continuum-scale model. This approach enables us to study non-isothermal reactive transport in porous media while accounting for micro-scale features under realistic conditions. The performance and applicability of the proposed model is explored for different flow and reaction regimes. References: 1. Matthäi, S.K., et al.: Simulation of solute transport through fractured rock: a higher-order accurate finite-element finite-volume method permitting large time steps. Transport in porous media 83.2 (2010): 289-318. 2. Nick, H.M., et al.: Reactive dispersive contaminant transport in coastal aquifers: Numerical simulation of a reactive Henry problem. Journal of contaminant hydrology 145 (2012), 90-104. 3. Raoof A., et al.: PoreFlow: A Complex pore-network model for simulation of reactive transport in variably saturated porous media, Computers & Geosciences, 61, (2013), 160-174.

  19. Return of target material ions leads to a reduced hysteresis in reactive high power impulse magnetron sputtering: Model (United States)

    Kadlec, Stanislav; Čapek, Jiří


    A tendency to disappearing hysteresis in reactive High Power Impulse Magnetron Sputtering (HiPIMS) has been reported previously without full physical explanation. An analytical model of reactive pulsed sputtering including HiPIMS is presented. The model combines a Berg-type model of reactive sputtering with the global HiPIMS model of Christie-Vlček. Both time and area averaging is used to describe the macroscopic steady state, especially the reactive gas balance in the reactor. The most important effect in the presented model is covering of reacted parts of target by the returning ionized metal, effectively lowering the target coverage by reaction product at a given partial pressure. The return probability of ionized sputtered metal has been selected as a parameter to quantify the degree of HiPIMS effects. The model explains the reasons for reduced hysteresis in HiPIMS. The critical pumping speed was up to a factor of 7 lower in reactive HiPIMS compared to the mid-frequency magnetron sputtering. The model predicts reduced hysteresis in HiPIMS due to less negative slope of metal flux to substrates and of reactive gas sorption as functions of reactive gas partial pressure. Higher deposition rate of reactive HiPIMS compared to standard reactive sputtering is predicted for some parameter combinations. Comparison of the model with experiment exhibits good qualitative and quantitative agreement for three material combinations, namely, Ti-O2, Al-O2, and Ti-N2.

  20. Mathematical model of SPOC with a time dependent reactive field

    Energy Technology Data Exchange (ETDEWEB)

    Ohtaki, Masako [Department of Physics, School of Science and Engineering, Waseda University, Okubo, Shinjuku-ku, Tokyo 169-8555 (Japan)


    In general the muscle is in one of the two state possible states, relaxation or contraction. These contractions result from relative sliding of myosin and actin in the sarcomere, which is the contraction structure unit of skeletal muscle. The switching between two states is depending on the Ca2{sup +} concentrations. However another state has been detected between these two states. In the third state, that is SPontaneous Oscillatory Contraction (SPOC), sarcomere repeats contraction and extension spontaneously. Muscle fibers are composed of hundreds of sarcomeres in series and one sarcomea also is composed of hundreds of myosin. In microscopic, the force generated by actin and myosin interaction occurs stochastically. SPOC, however, is macroscopically observable and there are regular oscillations. To understand SPOC mechanism, we propose a model for SPOC based on chemical reaction including mechanical process.

  1. Mathematical model of SPOC with a time dependent reactive field (United States)

    Ohtaki, Masako


    In general the muscle is in one of the two state possible states, relaxation or contraction. These contractions result from relative sliding of myosin and actin in the sarcomere, which is the contraction structure unit of skeletal muscle. The switching between two states is depending on the Ca2+ concentrations. However another state has been detected between these two states. In the third state, that is SPontaneous Oscillatory Contraction (SPOC), sarcomere repeats contraction and extension spontaneously. Muscle fibers are composed of hundreds of sarcomeres in series and one sarcomea also is composed of hundreds of myosin. In microscopic, the force generated by actin and myosin interaction occurs stochastically. SPOC, however, is macroscopically observable and there are regular oscillations. To understand SPOC mechanism, we propose a model for SPOC based on chemical reaction including mechanical process.

  2. The effect of reactive power generation modeling on voltage stability analysis

    Energy Technology Data Exchange (ETDEWEB)

    Tovar, E.; Guizar, J.G.C. [Inst. de Investigaciones Electricas, Cuernavaca, Morelos (Mexico)


    One of the most significant concerns for power system planning and operation in many countries involves problems related to voltage instability in electrical power systems. Blackouts have been caused by voltage instability problems throughout the world during the last few decades. Several factors can contribute to long term voltage instability problems, including high active and reactive loading, operation of on load tap changer transformers, inadequate locally available reactive power resources, load characteristics at low voltage magnitudes and operation of relay protection. There is a significant need to evaluate an index which gives the operating point proximity to voltage instability. This paper examined the influence of generator voltage dependent reactive power production on system voltage stability using the minimum singular value from the Jacobian Matrix of the load flow formulation. The synchronous generator model considered voltage reactive power limits due to maximum armature current, maximum and minimum field current as well as under excitation limiters. The generation model used in this paper was included in an ordinary load flow program, and resulted from studies of a representative 62 bus Norwest control area Mexican system, which included 19 generators. Specifically, the paper discussed the generator model with particular reference to the maximum field current limit; armature current limit; minimum field current limit; and underexcitation limit. The singular value decomposition and computational results were also presented. It was concluded that as the loading of the system increases, the reactive power produced by the machines also increases, and that reactive power is delivered when the induced voltage is greater than the terminal voltage. 15 refs., 3 tabs., 2 figs.

  3. Model-data integration for predictive assessment of groundwater reactive transport systems

    NARCIS (Netherlands)

    Carniato, L.


    Predicting the evolution of groundwater contamination is a major concern for society, in particular when investments are made to remediate the contamination. Groundwater reactive transport models are valuable tools to integrate the available measurements in a consistent framework, improving our unde

  4. A Conceptual Framework for Predicting the Toxicity of Reactive Chemicals: Modeling Soft Electrophilicity (United States)

    Although the literature is replete with QSAR models developed for many toxic effects caused by reversible chemical interactions, the development of QSARs for the toxic effects of reactive chemicals lacks a consistent approach. While limitations exit, an appropriate starting-point...

  5. Coupled continuum modeling of fracture reactivation and induced seismicity during enhanced geothermal operations

    NARCIS (Netherlands)

    Wassing, B.B.T.; Wees, J.D. van; Fokker, P.A.


    We developed a coupled code to obtain a better understanding of the role of pore pressure changes in causing fracture reactivation and seismicity during EGS. We implemented constitutive models for fractures in a continuum approach, which is advantageous because of the ease of integration in existing

  6. A Conceptual Framework for Predicting the Toxicity of Reactive Chemicals: Modeling Soft Electrophilicity (United States)

    Although the literature is replete with QSAR models developed for many toxic effects caused by reversible chemical interactions, the development of QSARs for the toxic effects of reactive chemicals lacks a consistent approach. While limitations exit, an appropriate starting-point...

  7. Abiotic/biotic coupling in the rhizosphere: a reactive transport modeling analysis (United States)

    Lawrence, Corey R.; Steefel, Carl; Maher, Kate


    A new generation of models is needed to adequately simulate patterns of soil biogeochemical cycling in response changing global environmental drivers. For example, predicting the influence of climate change on soil organic matter storage and stability requires models capable of addressing complex biotic/abiotic interactions of rhizosphere and weathering processes. Reactive transport modeling provides a powerful framework simulating these interactions and the resulting influence on soil physical and chemical characteristics. Incorporation of organic reactions in an existing reactive transport model framework has yielded novel insights into soil weathering and development but much more work is required to adequately capture root and microbial dynamics in the rhizosphere. This endeavor provides many advantages over traditional soil biogeochemical models but also many challenges.

  8. Chemical modelling of Alkali Silica reaction: Influence of the reactive aggregate size distribution

    Energy Technology Data Exchange (ETDEWEB)

    Poyet, S. [CEA Saclay, DEN/DANS/DPC/SCCME/LECBA, F-91191 Gif Sur Yvette, (France); Sellier, A. [UPS, LMDC, INSA Toulouse, F-33077 Bordeaux 4, (France); Capra, B. [Oxand SA, F-77210 Avon (France); Foray, G. [Univ Lyon 1, L2MS, PETRA GC, F-69622 Villeurbanne (France); Torrenti, J.M. [IRSN, F-92262 Fontenay Aux Roses (France); Cognon, H. [EdF/DER Les Renardieres, F-77818 Moret Sur Loing (France); Bourdarot, E. [CIH Savoie Technolac, F-73373 Le Bourget du Lac (France)


    This article presents a new model which aims at predicting the expansion induced by Alkali Silica Reaction (ASR) and describing the chemical evolution of affected concretes. It is based on the description of the transport and reaction of alkalis and calcium ions within a Relative Elementary Volume (REV). It takes into account the influence of the reactive aggregate size grading on ASR, i.e. the effect of the simultaneous presence of different sized reactive aggregates within concrete. The constitutive equations are detailed and fitted using experimental results. Results from numerical simulations are presented and compared with experiments. (authors)

  9. Structural models of vanadate-dependent haloperoxidases and their reactivity

    Indian Academy of Sciences (India)

    Mannar R Maurya


    Vanadium(V) complexes with hydrazone-based ONO and ONN donor ligands that partly model active-site structures of vanadate-dependent haloperoxidases have been reported. On reaction with [VO(acac)2] (Hacac = acetylacetone) under nitrogen, these ligands generally provide oxovanadium(IV) complexes [VO(ONO)X] (X = solvent or nothing) and [VO(acac)(ONN)], respectively. Under aerobic conditions, these oxovanadium(IV) species undergo oxidation to give oxovanadium(V), dioxovanadium (V) or -oxobis{oxovanadium(V)} species depending upon the nature of the ligand. Anionic and neutral dioxovanadium(V) complexes slowly deoxygenate in methanol to give monooxo complexes [VO(OMe)(MeOH)(ONO)]. The anionic complexes [VO2(ONO)]- can also be converted in situ on acidification to oxohydroxo complexes [VO(OH)(HONO)]+ and to peroxo complexes [VO(O2)(ONO)]-, and thus to the species assumed to be intermediates in the haloperoxidases activity of the enzymes. In the presence of catechol (H2cat) and benzohydroxamic acid (H2bha), oxovanadium (IV) complexes, [VO (acac)(ONN)] gave mixed-chelate oxovanadium(V) complexes [VO(cat)(ONN)] and [VO(bha)(ONN)] respectively. These complexes are not very stable in solution and slowly convert to the corresponding dioxo species [VO2(ONN)] as observed by 51V NMR and electronic absorption spectroscopic studies.

  10. Application of a data assimilation method via an ensemble Kalman filter to reactive urea hydrolysis transport modeling

    Energy Technology Data Exchange (ETDEWEB)

    Juxiu Tong; Bill X. Hu; Hai Huang; Luanjin Guo; Jinzhong Yang


    With growing importance of water resources in the world, remediations of anthropogenic contaminations due to reactive solute transport become even more important. A good understanding of reactive rate parameters such as kinetic parameters is the key to accurately predicting reactive solute transport processes and designing corresponding remediation schemes. For modeling reactive solute transport, it is very difficult to estimate chemical reaction rate parameters due to complex processes of chemical reactions and limited available data. To find a method to get the reactive rate parameters for the reactive urea hydrolysis transport modeling and obtain more accurate prediction for the chemical concentrations, we developed a data assimilation method based on an ensemble Kalman filter (EnKF) method to calibrate reactive rate parameters for modeling urea hydrolysis transport in a synthetic one-dimensional column at laboratory scale and to update modeling prediction. We applied a constrained EnKF method to pose constraints to the updated reactive rate parameters and the predicted solute concentrations based on their physical meanings after the data assimilation calibration. From the study results we concluded that we could efficiently improve the chemical reactive rate parameters with the data assimilation method via the EnKF, and at the same time we could improve solute concentration prediction. The more data we assimilated, the more accurate the reactive rate parameters and concentration prediction. The filter divergence problem was also solved in this study.

  11. Immune response in lung cancer mouse model mimics human anti-Hu reactivity (United States)

    Kazarian, Meleeneh; Calbo, Joaquim; Proost, Natalie; Carpenter, Catherine L.; Berns, Anton; Laird-Offringa, Ite A.


    Most patients with paraneoplastic encephalomyelitis/sensory neuronopathy PEM/SN have small-cell lung cancer (SCLC) and develop antibodies against neuronal-specific Hu proteins, which are abnormally expressed in the tumor. Anti-Hu reactivity is present in ~16% of SCLC patients without PEM/SN. Here we test the hypothesis that engineered SCLC-prone mice may exhibit anti-Hu reactivity. We show that tumors from SCLC-prone mice misexpress Hu proteins, and 14% of mice harbor anti-Hu antibodies. Mice appear to show reactivity prior to clinical diagnosis of SCLC. This mouse model system will be useful to study SCLC-associated autoimmunity, its diagnostic value, and the potential protective role of oncoantigen-directed autoantibodies. PMID:19765830

  12. A process model of adolescents' triangulation into parents' marital conflict: the role of emotional reactivity. (United States)

    Buehler, Cheryl; Welsh, Deborah P


    This study examined adolescents' emotional reactivity to parents' marital conflict as a mediator of the association between triangulation and adolescents' internalizing problems in a sample of 2-parent families (N = 416)[corrected]. Four waves of annual, multiple-informant data were analyzed (youth ages 11-15 years). The authors used structural equation modeling and found that triangulation was associated with increases in adolescents' internalizing problems, controlling for marital hostility and adolescent externalizing problems. There also was an indirect pathway from triangulation to internalizing problems across time through youths' emotional reactivity. Moderating analyses indicated that the 2nd half of the pathway, the association between emotional reactivity and increased internalizing problems, characterized youth with lower levels of hopefulness and attachment to parents. The findings help detail why triangulation is a risk factor for adolescents' development and which youth will profit most from interventions focused on emotional regulation.

  13. Modeling variably saturated multispecies reactive groundwater solute transport with MODFLOW-UZF and RT3D (United States)

    Bailey, Ryan T.; Morway, Eric D.; Niswonger, Richard G.; Gates, Timothy K.


    A numerical model was developed that is capable of simulating multispecies reactive solute transport in variably saturated porous media. This model consists of a modified version of the reactive transport model RT3D (Reactive Transport in 3 Dimensions) that is linked to the Unsaturated-Zone Flow (UZF1) package and MODFLOW. Referred to as UZF-RT3D, the model is tested against published analytical benchmarks as well as other published contaminant transport models, including HYDRUS-1D, VS2DT, and SUTRA, and the coupled flow and transport modeling system of CATHY and TRAN3D. Comparisons in one-dimensional, two-dimensional, and three-dimensional variably saturated systems are explored. While several test cases are included to verify the correct implementation of variably saturated transport in UZF-RT3D, other cases are included to demonstrate the usefulness of the code in terms of model run-time and handling the reaction kinetics of multiple interacting species in variably saturated subsurface systems. As UZF1 relies on a kinematic-wave approximation for unsaturated flow that neglects the diffusive terms in Richards equation, UZF-RT3D can be used for large-scale aquifer systems for which the UZF1 formulation is reasonable, that is, capillary-pressure gradients can be neglected and soil parameters can be treated as homogeneous. Decreased model run-time and the ability to include site-specific chemical species and chemical reactions make UZF-RT3D an attractive model for efficient simulation of multispecies reactive transport in variably saturated large-scale subsurface systems.

  14. A COMSOL-GEMS interface for modeling coupled reactive-transport geochemical processes (United States)

    Azad, Vahid Jafari; Li, Chang; Verba, Circe; Ideker, Jason H.; Isgor, O. Burkan


    An interface was developed between COMSOL MultiphysicsTM finite element analysis software and (geo)chemical modeling platform, GEMS, for the reactive-transport modeling of (geo)chemical processes in variably saturated porous media. The two standalone software packages are managed from the interface that uses a non-iterative operator splitting technique to couple the transport (COMSOL) and reaction (GEMS) processes. The interface allows modeling media with complex chemistry (e.g. cement) using GEMS thermodynamic database formats. Benchmark comparisons show that the developed interface can be used to predict a variety of reactive-transport processes accurately. The full functionality of the interface was demonstrated to model transport processes, governed by extended Nernst-Plank equation, in Class H Portland cement samples in high pressure and temperature autoclaves simulating systems that are used to store captured carbon dioxide (CO2) in geological reservoirs.

  15. Distinguishing Environment and System in Coloured Petri Net Models of Reactive Systems

    DEFF Research Database (Denmark)

    Tjell, Simon


    This paper introduces and formally defines the environment-and-system-partitioned property for behavioral models of reactive systems expressed in the formal modeling language Coloured Petri Net. The purpose of the formalization is to make it possible to automatically validate any CPN model with r...... code-generation from models. A prototypical tool has been implemented for performing the structural analysis of Coloured Petri Net models and the principles of this tool is described. The aim of the paper is to make the guidelines and their formalized definitions along with a proof...

  16. In silico pharmacophore model for tabun-inhibited acetylcholinesterase reactivators: a study of their stereoelectronic properties. (United States)

    Bhattacharjee, Apurba K; Kuca, Kamil; Musilek, Kamil; Gordon, Richard K


    Organophosphorus (OP) nerve agents that inhibit acetylcholinesterase (AChE; EC function in the nervous system, causing acute intoxication. If untreated, death can result. Inhibited AChE can be reactivated by oximes, antidotes for OP exposure. However, OP intoxication caused by the nerve agent tabun (GA) is particularly resistant to oximes, which poorly reactivate GA-inhibited AChE. In an attempt to develop a rational strategy for the discovery and design of novel reactivators with lower toxicity and increased efficacy in reactivating GA-inhibited AChE, we developed the first in silico pharmacophore model for binding affinity of GA-inhibited AChE from a set of 11 oximes. Oximes were analyzed for stereoelectronic profiles and three-dimensional quantitative structure-activity relationship pharmacophores using ab initio quantum chemical and pharmacophore generation methods. Quantum chemical methods were sequentially used from semiempirical AM1 to hierarchical ab initio calculations to determine the stereoelectronic properties of nine oximes exhibiting affinity for binding to GA-inhibited AChE in vivo. The calculated stereoelectronic properties led us to develop the in silico pharmacophore model using CATALYST methodology. Specific stereoelectronic profiles including the distance between bisquarternary nitrogen atoms of the pyridinium ring in the oximes, hydrophilicity, surface area, nucleophilicity of the oxime oxygen, and location of the molecular orbitals on the isosurfaces have important roles for potencies for reactivating GA-inhibited AChE. The in silico pharmacophore model of oxime affinity for binding to GA-inhibited AChE was found to require a hydrogen bond acceptor, a hydrogen bond donor at the two terminal regions, and an aromatic ring in the central region of the oximes. The model was found to be well-correlated (R = 0.9) with experimental oxime affinity for binding to GA-inhibited AChE. Additional stereoelectronic features relating activity with

  17. A simple reactivity feedback model accounting for radial core expansion effects in the liquid metal fast reactor

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Young Min; Lee, Yong Bum; Chang, Won Pyo; Haha, Do Hee [KAERI, Taejon (Korea, Republic of)


    The radial core expansion due to the structure temperature rise is one of major negative reactivity insertion mechanisms in metallic fueled reactor. Thermal expansion is a result of both the laws of nature and the particular core design and it causes negative reactivity feedback by the combination of increased core volume captures and increased core surface leakage. The simple radial core expansion reactivity feedback model developed for the SSC-K code was evaluated by the code-to-code comparison analysis. From the comparison results, it can be stated that the radial core expansion reactivity feedback model employed into the SSC-K code may be reasonably accurate in the UTOP analysis.

  18. A Coupled Model of Multiphase Flow, Reactive Biogeochemical Transport, Thermal Transport and Geo-Mechanics. (United States)

    Tsai, C. H.; Yeh, G. T.


    In this investigation, a coupled model of multiphase flow, reactive biogeochemical transport, thermal transport and geo-mechanics in subsurface media is presented. It iteratively solves the mass conservation equation for fluid flow, thermal transport equation for temperature, reactive biogeochemical transport equations for concentration distributions, and solid momentum equation for displacement with successive linearization algorithm. With species-based equations of state, density of a phase in the system is obtained by summing up concentrations of all species. This circumvents the problem of having to use empirical functions. Moreover, reaction rates of all species are incorporated in mass conservation equation for fluid flow. Formation enthalpy of all species is included in the law of energy conservation as a source-sink term. Finite element methods are used to discretize the governing equations. Numerical experiments are presented to examine the accuracy and robustness of the proposed model. The results demonstrate the feasibility and capability of present model in subsurface media.

  19. GOBF-ARMA based model predictive control for an ideal reactive distillation column. (United States)

    Seban, Lalu; Kirubakaran, V; Roy, B K; Radhakrishnan, T K


    This paper discusses the control of an ideal reactive distillation column (RDC) using model predictive control (MPC) based on a combination of deterministic generalized orthonormal basis filter (GOBF) and stochastic autoregressive moving average (ARMA) models. Reactive distillation (RD) integrates reaction and distillation in a single process resulting in process and energy integration promoting green chemistry principles. Improved selectivity of products, increased conversion, better utilization and control of reaction heat, scope for difficult separations and the avoidance of azeotropes are some of the advantages that reactive distillation offers over conventional technique of distillation column after reactor. The introduction of an in situ separation in the reaction zone leads to complex interactions between vapor-liquid equilibrium, mass transfer rates, diffusion and chemical kinetics. RD with its high order and nonlinear dynamics, and multiple steady states is a good candidate for testing and verification of new control schemes. Here a combination of GOBF-ARMA models is used to catch and represent the dynamics of the RDC. This GOBF-ARMA model is then used to design an MPC scheme for the control of product purity of RDC under different operating constraints and conditions. The performance of proposed modeling and control using GOBF-ARMA based MPC is simulated and analyzed. The proposed controller is found to perform satisfactorily for reference tracking and disturbance rejection in RDC.

  20. Anthropogenic contamination of a phreatic drinking water winning: 3-dimensional reactive transport modelling (United States)

    Griffioen, J.; van der Grift, B.; Maas, D.; van den Brink, C.; Zaadnoordijk, J. W.


    Groundwater is contaminated at the regional scale by agricultural activities and atmospheric deposition. A 3-D transport model was set-up for a phreatic drinking water winning, where the groundwater composition was monitored accurately. The winning is situated at an area with unconsolidated Pleistocene deposits. The land use is nature and agriculture. Annual mass-balances were determined using a wide range of historic data. The modelling approach for the unsaturated zone was either simple box models (Cl, NO_3 and SO_4) or 1-D transport modelling using HYDRUS (Cd). The modelling approach for the saturated zone used a multiple solute version of MT3D, where denitrification associated with pyrite oxidation and sorption of Cd were included. The solute transport calculations were performed for the period 1950--2030. The results obtained for the year 2000 were used as input concentration for the period 2000--2030. A comparison between the calculated and the measured concentrations of groundwater abstracted for Cl, NO_3 and SO_4 yields the following. First, the input at the surface is rather well estimated. Second, the redox reactivity of the first two aquifers is negligible around the winning, which is confirmed by respiration experiments using anaerobically sampled aquifer sediments. The reactivity of the third aquifer, which is a marine deposit and lies at least 30 meters below surface, is considerable. The discrepancies between modelled and measured output are explained by lack of knowledge about the subsurface reactivity and/or wrong estimates of surface loading and leaching from the unsaturated zone. The patterns for other hydrogeochemical variables such as Ca, HCO_3 may further constrain this lack of knowledge. The results for Cd indicate that Cd becomes strongly retarded, despite the low reactivity of the sandy sediments. The winning is rather insensitive to Cd contamination (but the surface water drainage network is not). Two major uncertainties for input of Cd

  1. Modeling the surface tension of complex, reactive organic-inorganic mixtures

    Directory of Open Access Journals (Sweden)

    A. N. Schwier


    Full Text Available Atmospheric aerosols can contain thousands of organic compounds which impact aerosol surface tension, affecting aerosol properties such as cloud condensation nuclei (CCN ability. We present new experimental data for the surface tension of complex, reactive organic-inorganic aqueous mixtures mimicking tropospheric aerosols. Each solution contained 2–6 organic compounds, including methylglyoxal, glyoxal, formaldehyde, acetaldehyde, oxalic acid, succinic acid, leucine, alanine, glycine, and serine, with and without ammonium sulfate. We test two surface tension models and find that most reactive, complex, aqueous organic mixtures which do not contain salt are well-described by a weighted Szyszkowski–Langmuir (S–L model which was first presented by Henning et al. (2005. Two approaches for modeling the effects of salt were tested: (1 the Tuckermann approach (an extension of the Henning model with an additional explicit salt term, and (2 a new implicit method proposed here which employs experimental surface tension data obtained for each organic species in the presence of salt used with the Henning model. We recommend the use of method (2 for surface tension modeling because the Henning model (using data obtained from organic-inorganic systems and Tuckermann approach provide similar modeling fits and goodness of fit (χ2 values, yet the Henning model is a simpler and more physical approach to modeling the effects of salt, requiring less empirically determined parameters.

  2. The Reactive-Diffusive Length of OH and Ozone in Model Organic Aerosols. (United States)

    Lee, Lance; Wilson, Kevin


    A key step in the heterogeneous oxidation of atmospheric aerosols is the reaction of ozone (O3) and hydroxyl radicals (OH) at the gas-particle interface. The formation of reaction products and free radical intermediates and their spatial distribution inside the particle is a sensitive function of the length over which these oxidants diffuse prior to reaction. The reactive-diffusive length of OH and ozone at organic aerosol interfaces is determined by observing the change in the effective uptake coefficient for size-selected model aerosols comprising a reactive core and a thin nanometer-sized (0-12 nm) organic shell. The core and shell materials are selected so that they are immiscible and adopt an assumed core-shell configuration. The results indicate a reactive-diffusive length of 1.4 nm for hydroxyl (OH) radicals in squalane and 1.0 nm for ozone in squalene. Measurements for a purely diffusive system allow for an estimate for diffusion constant (1.6 × 10(-6) cm(2)/s) of ozone in squalane to be determined. The reactive-diffusive length offers a simple first order estimate of how shielding of aerosols by immiscible layers can alter estimates of oxidative lifetimes of aerosols in the atmosphere.

  3. Tuning surface reactivity by finite size effects: role of orbital symmetry in the d - band model (United States)

    Snijders, Paul; Yin, Xiangshi; Cooper, Valentino; Weitering, Hanno

    Catalytic activity depends sensitively on the strength of the interactions between reactant molecules and catalyst surface: too weak and the catalyst cannot capture enough molecules to react; too strong and the reaction products do not desorb, blocking further reactions. The ability to control the binding strength of molecules to metal surfaces is thus fundamental to the design of efficient and selective catalysts. Catalyst design often relies on increasing the interaction strength on relatively non-reactive materials by introducing active sites. Here, we present a complementary approach: we exploit finite size effects in the electronic structure of ultrathin Pd(111) films grown on Ru(0001) to tune their reactivity by changing the film thickness one atom layer at a time. While bulk Pd(111) is reactive toward oxygen, we find that Pd films thinner than 6 atom layers are surprisingly inert to oxidation. This observation can be explained with the d-band model only when it is applied to the orbitals directly involved in the bonding. The insight into orbital specific contributions to surface reactivity could be useful in the design of catalysts. This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.

  4. Tuberculosis genes expressed during persistence and reactivation in the resistant rabbit model


    Kesavan, Anup K.; Brooks, Megan; Tufariello, JoAnn; Chan, John; Manabe, Yukari C.


    As previously published, after aerosol infection with Mycobacterium tuberculosis H37Rv, New Zealand white rabbits established infection with active bacillary replication, but later contained disease to a paucibacillary state through an effective adaptive response consistent with latency. Despite the heterogeneity among outbred rabbits, the resistant response was uniform. Immunosuppression resulted in reactivation with increased lung bacillary burden. Using this rabbit model, we isolated bacil...

  5. Real catalysis on single crystalline model catalysts with in-situ reactivity measurement


    O. Shekhah; Ranke, W.; Schlögl, R.


    The pressure and materials gap between reactivity studies in UHV and real catalysis can only be overcome by application of in-situ methods for catalyst characterization and/or activity measurements under realistic pressure and temperature conditions. As a model reaction we study the economically important catalytic dehydrogenation of ethylbenzene (EB) to styrene (St) [1]. The technical catalyst consists of potassium-promoted iron oxides. We use single crystalline epitaxial layers of Fe2O3, Fe...

  6. Using Consensus Bayesian Network to Model the Reactive Oxygen Species Regulatory Pathway


    Liangdong Hu; Limin Wang


    Bayesian network is one of the most successful graph models for representing the reactive oxygen species regulatory pathway. With the increasing number of microarray measurements, it is possible to construct the bayesian network from microarray data directly. Although large numbers of bayesian network learning algorithms have been developed, when applying them to learn bayesian networks from microarray data, the accuracies are low due to that the databases they used to learn bayesian networks...

  7. A New Model for Reactive Wetting of Metal/Ceramic System

    Institute of Scientific and Technical Information of China (English)

    Fusheng Pan; Jian Chen; Tianmo Liu; Jing Zhang


    @@ A new model has been suggested for illustrating the effects of interfacial reactions on the wettability of metal / ceramic system. It is shown that both the free energy change released by the reaction (△Gr) and the change in the nature of interfaces (△δr) are the important factors affecting reactive wetting of metal / ceramic system, but sometimes either of them will become the decisive one.

  8. Safe motion planning for mobile agents: A model of reactive planning for multiple mobile agents

    Energy Technology Data Exchange (ETDEWEB)

    Fujimura, Kikuo.


    The problem of motion planning for multiple mobile agents is studied. Each planning agent independently plans its own action based on its map which contains a limited information about the environment. In an environment where more than one mobile agent interacts, the motions of the robots are uncertain and dynamic. A model for reactive agents is described and simulation results are presented to show their behavior patterns. 18 refs., 2 figs.

  9. Modelling and parameter estimation in reactive continuous mixtures: the catalytic cracking of alkanes - part II

    Directory of Open Access Journals (Sweden)



    Full Text Available Fragmentation kinetics is employed to model a continuous reactive mixture of alkanes under catalytic cracking conditions. Standard moment analysis techniques are employed, and a dynamic system for the time evolution of moments of the mixture's dimensionless concentration distribution function (DCDF is found. The time behavior of the DCDF is recovered with successive estimations of scaled gamma distributions using the moments time data.

  10. Reactive molecular dynamics models from ab initio molecular dynamics data using relative entropy minimization (United States)

    Arntsen, Christopher; Chen, Chen; Voth, Gregory A.


    We present two new multiscale molecular dynamics (MS-RMD) models for the hydrated excess proton in water developed directly from ab initio molecular dynamics (AIMD) simulation data of the same system. The potential of mean force along the proton transfer reaction coordinate and radial distribution functions for the MS-RMD models are shown to faithfully reproduce those of AIMD. The models are developed using an algorithm based on relative entropy minimization, thus demonstrating the ability of the method to rapidly generate accurate and highly efficient reactive MD force fields.

  11. Model-Based Requirements Analysis for Reactive Systems with UML Sequence Diagrams and Coloured Petri Nets

    DEFF Research Database (Denmark)

    Tjell, Simon; Lassen, Kristian Bisgaard


    In this paper, we describe a formal foundation for a specialized approach to automatically checking traces against real-time requirements. The traces are obtained from simulation of Coloured Petri Net (CPN) models of reactive systems. The real-time requirements are expressed in terms...... of a derivative of UML 2.0 high-level Sequence Diagrams. The automated requirement checking is part of a bigger tool framework in which VDM++ is applied to automatically generate initial CPN models based on Problem Diagrams. These models are manually enhanced to provide behavioral descriptions of the environment...

  12. Post Audit of a Field Scale Reactive Transport Model of Uranium at a Former Mill Site (United States)

    Curtis, G. P.


    Reactive transport of hexavalent uranium (U(VI)) in a shallow alluvial aquifer at a former uranium mill tailings site near Naturita CO has been monitored for nearly 30 years by the US Department of Energy and the US Geological Survey. Groundwater at the site has high concentrations of chloride, alkalinity and U(VI) as a owing to ore processing at the site from 1941 to 1974. We previously calibrated a multicomponent reactive transport model to data collected at the site from 1986 to 2001. A two dimensional nonreactive transport model used a uniform hydraulic conductivity which was estimated from observed chloride concentrations and tritium helium age dates. A reactive transport model for the 2km long site was developed by including an equilibrium U(VI) surface complexation model calibrated to laboratory data and calcite equilibrium. The calibrated model reproduced both nonreactive tracers as well as the observed U(VI), pH and alkalinity. Forward simulations for the period 2002-2015 conducted with the calibrated model predict significantly faster natural attenuation of U(VI) concentrations than has been observed by the persistent high U(VI) concentrations at the site. Alternative modeling approaches are being evaluating evaluated using recent data to determine if the persistence can be explained by multirate mass transfer models developed from experimental observations at the column scale(~0.2m), the laboratory tank scale (~2m), the field tracer test scale (~1-4m) or geophysical observation scale (~1-5m). Results of this comparison should provide insight into the persistence of U(VI) plumes and improved management options.

  13. From reactive to proactive and selective control: developing a richer model for stopping inappropriate responses. (United States)

    Aron, Adam R


    A better understanding of the neural systems underlying impulse control is important for psychiatry. Although most impulses are motivational or emotional rather than motoric per se, it is research into the neural architecture of motor response control that has made the greatest strides. This article reviews recent developments in the cognitive neuroscience of stopping responses. Most research of this kind has focused on reactive control-that is, how subjects stop a response outright when instructed by a signal. It is argued that reactive paradigms are limited as models of control relevant to psychiatry. Instead, a set of paradigms is advocated that begins to model proactive inhibitory control-that is, how a subject prepares to stop an upcoming response tendency. Proactive inhibitory control is generated according to the goals of the subject rather than by an external signal, and it can be selectively targeted at a particular response tendency. This may have wider validity than reactive control as an experimental model for stopping inappropriate responses.

  14. ParFlow.RT: Development and Verification of a New Reactive Transport Model (United States)

    Beisman, J. J., III


    In natural subsurface systems, total elemental fluxes are often heavily influenced by areas of disproportionately high reaction rates. These pockets of high reaction rates tend to occur at interfaces, such as the hyporheic zone, where a hydrologic flowpath converges with either a chemically distinct hydrologic flowpath or a reactive substrate. Understanding the affects that these highly reactive zones have on the behavior of shallow subsurface systems is integral to the accurate quantification of nutrient fluxes and biogeochemical cycling. Numerical simulations of these systems may be able to offer some insight. To that end, we have developed a new reactive transport model, ParFlow.RT, by coupling the parallel flow and transport code ParFlow with the geochemical engines of both PFLOTRAN and CrunchFlow. The coupling was accomplished via the Alquimia biogeochemistry API, which provides a unified interface to several geochemical codes and allows a relatively simple implementation of advanced geochemical functionality in flow and transport codes. This model uses an operator-splitting approach, where the transport and reaction steps are solved separately. Here, we present the details of this new model, and the results of verification simulations and biogeochemical cycling simulations of the DOE's East River field site outside of Gothic, CO.

  15. Effectiveness of reactive case detection for malaria elimination in three archetypical transmission settings: a modelling study. (United States)

    Gerardin, Jaline; Bever, Caitlin A; Bridenbecker, Daniel; Hamainza, Busiku; Silumbe, Kafula; Miller, John M; Eisele, Thomas P; Eckhoff, Philip A; Wenger, Edward A


    Reactive case detection could be a powerful tool in malaria elimination, as it selectively targets transmission pockets. However, field operations have yet to demonstrate under which conditions, if any, reactive case detection is best poised to push a region to elimination. This study uses mathematical modelling to assess how baseline transmission intensity and local interconnectedness affect the impact of reactive activities in the context of other possible intervention packages. Communities in Southern Province, Zambia, where elimination operations are currently underway, were used as representatives of three archetypes of malaria transmission: low-transmission, high household density; high-transmission, low household density; and high-transmission, high household density. Transmission at the spatially-connected household level was simulated with a dynamical model of malaria transmission, and local variation in vectorial capacity and intervention coverage were parameterized according to data collected from the area. Various potential intervention packages were imposed on each of the archetypical settings and the resulting likelihoods of elimination by the end of 2020 were compared. Simulations predict that success of elimination campaigns in both low- and high-transmission areas is strongly dependent on stemming the flow of imported infections, underscoring the need for regional-scale strategies capable of reducing transmission concurrently across many connected areas. In historically low-transmission areas, treatment of clinical malaria should form the cornerstone of elimination operations, as most malaria infections in these areas are symptomatic and onward transmission would be mitigated through health system strengthening; reactive case detection has minimal impact in these settings. In historically high-transmission areas, vector control and case management are crucial for limiting outbreak size, and the asymptomatic reservoir must be addressed through

  16. Direct coupling of a genome-scale microbial in silico model and a groundwater reactive transport model (United States)

    Fang, Yilin; Scheibe, Timothy D.; Mahadevan, Radhakrishnan; Garg, Srinath; Long, Philip E.; Lovley, Derek R.


    The activity of microorganisms often plays an important role in dynamic natural attenuation or engineered bioremediation of subsurface contaminants, such as chlorinated solvents, metals, and radionuclides. To evaluate and/or design bioremediated systems, quantitative reactive transport models are needed. State-of-the-art reactive transport models often ignore the microbial effects or simulate the microbial effects with static growth yield and constant reaction rate parameters over simulated conditions, while in reality microorganisms can dynamically modify their functionality (such as utilization of alternative respiratory pathways) in response to spatial and temporal variations in environmental conditions. Constraint-based genome-scale microbial in silico models, using genomic data and multiple-pathway reaction networks, have been shown to be able to simulate transient metabolism of some well studied microorganisms and identify growth rate, substrate uptake rates, and byproduct rates under different growth conditions. These rates can be identified and used to replace specific microbially-mediated reaction rates in a reactive transport model using local geochemical conditions as constraints. We previously demonstrated the potential utility of integrating a constraint-based microbial metabolism model with a reactive transport simulator as applied to bioremediation of uranium in groundwater. However, that work relied on an indirect coupling approach that was effective for initial demonstration but may not be extensible to more complex problems that are of significant interest (e.g., communities of microbial species and multiple constraining variables). Here, we extend that work by presenting and demonstrating a method of directly integrating a reactive transport model (FORTRAN code) with constraint-based in silico models solved with IBM ILOG CPLEX linear optimizer base system (C library). The models were integrated with BABEL, a language interoperability tool. The

  17. Altered explorative strategies and reactive coping style in the FSL rat model of depression

    Directory of Open Access Journals (Sweden)

    Salvatore eMagara


    Full Text Available Modeling depression in animals is based on the observation of behaviors interpreted as analogue to human symptoms. Typical tests used in experimental depression research are designed to evoke an either-or outcome. It is known that explorative and coping strategies are relevant for depression, however these aspects are generally not considered in animal behavioral testing. Here we investigate the Flinders Sensitive Line (FSL, a rat model of depression, compared to the Sprague-Dawley (SD rat in three independent tests where the animals are allowed to express a more extensive behavioral repertoire. The multivariate concentric square field™ (MCSF and the novel cage tests evoke exploratory behaviors in a novel environment and the home cage change test evokes social behaviors in the re-establishment of a social hierarchy. In the MCSF test, FSL rats exhibited less exploratory drive and more risk-assessment behavior compared to SD rats. When re-exposed to the arena, FSL, but not SD rats, increased their exploratory behavior compared to the first trial and displayed risk-assessment behavior to the same extent as SD rats. Thus, the behavior of FSL rats was more similar to that of SDs when the rats were familiar with the arena. In the novel cage test FSL rats exhibited a reactive coping style, consistent with the reduced exploration observed in the MCSF. Reactive coping is associated with less aggressive behavior. Accordingly, FSL rats displayed less aggressive behavior in the home cage change test. Taken together, our data show that FSL rats express altered explorative behavior and reactive coping style. Reduced interest is a core symptom of depression, and individuals with a reactive coping style are more vulnerable to the disease. Our results support the use of FSL rats as an animal model of depression and increase our understanding of the FSL rat beyond the behavioral dimensions targeted by the traditional depression-related tests.

  18. Modelling the biogeochemical cycle of silicon in soils using the reactive transport code MIN3P (United States)

    Gerard, F.; Mayer, K. U.; Hodson, M. J.; Meunier, J.


    We investigated the biogeochemical cycling of Si in an acidic brown soil covered by a coniferous forest (Douglas fir) based on a comprehensive data set and reactive transport modelling. Both published and original data enable us to make up a conceptual model on which the development of a numerical model is based. We modified the reactive transport code MIN3P, which solves thermodynamic and kinetic reactions coupled with vadose zone flow and solute transport. Simulations were performed for a one-dimensional heterogeneous soil profile and were constrained by observed data including daily soil temperature, plant transpiration, throughfall, and dissolved Si in solutions collected beneath the organic layer. Reactive transport modelling was first used to test the validity of the hypothesis that a dynamic balance between Si uptake by plants and release by weathering controls aqueous Si-concentrations. We were able to calibrate the model quite accurately by stepwise adjustment of the relevant parameters. The capability of the model to predict Si-concentrations was good. Mass balance calculations indicate that only 40% of the biogeochemical cycle of Si is controlled by weathering and that about 60% of Si-cycling is related to biological processes (i.e. Si uptake by plants and dissolution of biogenic Si). Such a large contribution of biological processes was not anticipated considering the temperate climate regime, but may be explained by the high biomass productivity of the planted coniferous species. The large contribution of passive Si-uptake by vegetation permits the conservation of seasonal concentration variations caused by temperature-induced weathering, although the modelling suggests that the latter process was of lesser importance relative to biological Si-cycling.

  19. A Plan for the Development of the Spatial Kinetics and the Detailed Reactivity Model for a Fast Reactor

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Y. M.; Jeong, H. Y.; Lee, Y. B.; Sim, Y. S


    The reactivity feedback effect of metallic fuel is determined by the fuel burnup characteristics, the configuration of core and fuel assembly, and the complicated interaction between the fuel assembly and core internal structures. Currently, a quite simple evaluation model is frequently applied for the calculation of reactivity feedback. The simple model usually induces some over-conservatism to compensate the simplification, which is an obstacle to take advantage of the positive characteristics of metallic fuel over the oxide fuel. Therefore, to develop a detailed reactivity feedback model and to remove the over-conservatism in the existing simple model would be the foundation to strengthen the economic and operational competitiveness of a liquid metal-cooled fast reactor. In the present study, the plan for the development of the detailed reactivity feedback model and the methodology to combine the spatial kinetics code with the thermal-hydraulic code have been set up, which are two prerequisites for the evaluation of the detailed reactivity feedback effect. The proposed detailed model is expected to be developed in short-term, thus, easily implemented in the SSC-K code. The development of the spatial kinetics code and the merging it to the detailed thermal-hydraulics code would be achieved in long-term, but finally minimize the uncertainty in the reactivity feedback evaluation by including the detailed thermal-hydraulic information in the reactivity calculation.

  20. Can Ising model and/or QKPZ equation properly describe reactive-wetting interface dynamics? (United States)

    Efraim, Yael; Taitelbaum, Haim


    The reactive-wetting process, e.g. spreading of a liquid droplet on a reactive substrate is known as a complex, non-linear process with high sensitivity to minor fluctuations. The dynamics and geometry of the interface (triple line) between the materials is supposed to shed light on the main mechanisms of the process. We recently studied a room temperature reactive-wetting system of a small (˜ 150 μm) Hg droplet that spreads on a thin (˜ 4000 Å) Ag substrate. We calculated the kinetic roughening exponents (growth and roughness), as well as the persistence exponent of points on the advancing interface. In this paper we address the question whether there exists a well-defined model to describe the interface dynamics of this system, by performing two sets of numerical simulations. The first one is a simulation of an interface propagating according to the QKPZ equation, and the second one is a landscape of an Ising chain with ferromagnetic interactions in zero temperature. We show that none of these models gives a full description of the dynamics of the experimental reactivewetting system, but each one of them has certain common growth properties with it. We conjecture that this results from a microscopic behavior different from the macroscopic one. The microscopic mechanism, reflected by the persistence exponent, resembles the Ising behavior, while in the macroscopic scale, exemplified by the growth exponent, the dynamics looks more like the QKPZ dynamics.

  1. In Situ Biostimulation at a Former Uranium Mill Tailings Site: Multicomponent Biogeochemical Reactive Transport Modeling (United States)

    Yabusaki, S.; Fang, Y.; Long, P.


    In situ biostimulation at a Former Uranium Mill Tailings Site: Multicomponent Biogeochemical Reactive Transport Modeling Field experiments conducted at a former uranium mill tailings site in western Colorado are being used to investigate microbially mediated immobilization of uranium as a potential future remediation option for such sites. While the general principle of biostimulating microbial communities to reduce aqueous hexavalent uranium to immobile uraninite has been demonstrated in the laboratory and field, the ability to predictably engineer long lasting immobilization will require a more complete understanding of field-scale processes and properties. For this study, numerical simulation of the flow field, geochemical conditions, and micriobial communities is used to interpret field-scale biogeochemical reactive transport observed during experiments performed in 2002 to 2004. One key issue is identifying bioavailable Fe(III) oxide, which is the principal electron acceptor utilized by the acetate- oxidizing Geobacter sp. These organisms are responsible for uranium bioreduction that results in the removal of sufficient U(VI) to lower uranium groundwater concentrations to at or near applicable standards. The depletion of bioavailable Fe(III) leads to succession by sulfate reducers that are considerably less effective at uranium bioreduction. An important modeling consideration are the abiotic reactions (e.g., mineral precipitation and dissolution, aqueous and surface complexation) involving the Fe(II) and sulfide produced during biostimulation. These components, strongly associated with the solid phases, may play an important role in the evolving reactivity of the mineral surfaces that are likely to impact long-term uranium immobilization.

  2. Reactive Transport Modeling of Microbe-mediated Fe (II) Oxidation for Enhanced Oil Recovery (United States)

    Surasani, V.; Li, L.


    Microbially Enhanced Oil Recovery (MEOR) aims to improve the recovery of entrapped heavy oil in depleted reservoirs using microbe-based technology. Reservoir ecosystems often contain diverse microbial communities those can interact with subsurface fluids and minerals through a network of nutrients and energy fluxes. Microbe-mediated reactions products include gases, biosurfactants, biopolymers those can alter the properties of oil and interfacial interactions between oil, brine, and rocks. In addition, the produced biomass and mineral precipitates can change the reservoir permeability profile and increase sweeping efficiency. Under subsurface conditions, the injection of nitrate and Fe (II) as the electron acceptor and donor allows bacteria to grow. The reaction products include minerals such as Fe(OH)3 and nitrogen containing gases. These reaction products can have large impact on oil and reservoir properties and can enhance the recovery of trapped oil. This work aims to understand the Fe(II) oxidation by nitrate under conditions relevant to MEOR. Reactive transport modeling is used to simulate the fluid flow, transport, and reactions involved in this process. Here we developed a complex reactive network for microbial mediated nitrate-dependent Fe (II) oxidation that involves both thermodynamic controlled aqueous reactions and kinetic controlled Fe (II) mineral reaction. Reactive transport modeling is used to understand and quantify the coupling between flow, transport, and reaction processes. Our results identify key parameter controls those are important for the alteration of permeability profile under field conditions.

  3. The sudden vector projection model for reactivity: mode specificity and bond selectivity made simple. (United States)

    Guo, Hua; Jiang, Bin


    CONSPECTUS: Mode specificity is defined by the differences in reactivity due to excitations in various reactant modes, while bond selectivity refers to selective bond breaking in a reaction. These phenomena not only shed light on reaction dynamics but also open the door for laser control of reactions. The existence of mode specificity and bond selectivity in a reaction indicates that not all forms of energy are equivalent in promoting the reactivity, thus defying a statistical treatment. They also allow the enhancement of reactivity and control product branching ratio. As a result, they are of central importance in chemistry. This Account discusses recent advances in our understanding of these nonstatistical phenomena. In particular, the newly proposed sudden vector projection (SVP) model and its applications are reviewed. The SVP model is based on the premise that the collision in many direct reactions is much faster than intramolecular vibrational energy redistribution in the reactants. In such a sudden limit, the coupling of a reactant mode with the reaction coordinate at the transition state, which dictates its ability to promote the reaction, is approximately quantified by the projection of the former onto the latter. The SVP model can be considered as a generalization of the venerable Polanyi's rules, which are based on the location of the barrier. The SVP model is instead based on properties of the saddle point and as a result capable of treating the translational, rotational, and multiple vibrational modes in reactions involving polyatomic reactants. In case of surface reactions, the involvement of surface atoms can also be examined. Taking advantage of microscopic reversibility, the SVP model has also been used to predict product energy disposal in reactions. This simple yet powerful rule of thumb has been successfully demonstrated in many reactions including uni- and bimolecular reactions in the gas phase and gas-surface reactions. The success of the SVP

  4. Tuberculosis genes expressed during persistence and reactivation in the resistant rabbit model. (United States)

    Kesavan, Anup K; Brooks, Megan; Tufariello, JoAnn; Chan, John; Manabe, Yukari C


    As previously published, after aerosol infection with Mycobacterium tuberculosis H37Rv, New Zealand white rabbits established infection with active bacillary replication, but later contained disease to a paucibacillary state through an effective adaptive response consistent with latency. Despite the heterogeneity among outbred rabbits, the resistant response was uniform. Immunosuppression resulted in reactivation with increased lung bacillary burden. Using this rabbit model, we isolated bacillary RNA from infected rabbit lungs and assessed transcriptional profiles of bacillary genes using RT-PCR to examine genes differentially regulated during active replication, persistence, steroid-induced reactivation, and post-steroid immune reconstitution. Genes involved in hypoxia response (fdxA), resuscitation promoting factors (rpfB), and DNA repair pathways (Rv2191) may be important in bacillary persistence. Further investigation into these gene pathways is warranted.

  5. Combined Active and Reactive Power Control of Wind Farms based on Model Predictive Control

    DEFF Research Database (Denmark)

    Zhao, Haoran; Wu, Qiuwei; Wang, Jianhui;


    This paper proposes a combined wind farm controller based on Model Predictive Control (MPC). Compared with the conventional decoupled active and reactive power control, the proposed control scheme considers the significant impact of active power on voltage variations due to the low X=R ratio...... of wind farm collector systems. The voltage control is improved. Besides, by coordination of active and reactive power, the Var capacity is optimized to prevent potential failures due to Var shortage, especially when the wind farm operates close to its full load. An analytical method is used to calculate...... the sensitivity coefficients to improve the computation efficiency and overcome the convergence problem. Two control modes are designed for both normal and emergency conditions. A wind farm with 20 wind turbines was used to verify the proposed combined control scheme....

  6. Using hybrid models to predict blood pressure reactivity to unsupported back based on anthropometric characteristics

    Institute of Scientific and Technical Information of China (English)

    Gurmanik KAUR‡; Ajat Shatru ARORA; Vijender Kumar JAIN


    Accurate blood pressure (BP) measurement is essential in epidemiological studies, screening programmes, and re-search studies as well as in clinical practice for the early detection and prevention of high BP-related risks such as coronary heart disease, stroke, and kidney failure. Posture of the participant plays a vital role in accurate measurement of BP. Guidelines on measurement of BP contain recommendations on the position of the back of the participants by advising that they should sit with supported back to avoid spuriously high readings. In this work, principal component analysis (PCA) is fused with forward stepwise regression (SWR), artificial neural network (ANN), adaptive neuro-fuzzy inference system (ANFIS), and the least squares support vector machine (LS-SVM) model for the prediction of BP reactivity to an unsupported back in normotensive and hypertensive participants. PCA is used to remove multi-collinearity among anthropometric predictor variables and to select a subset of com-ponents, termed‘principal components’ (PCs), from the original dataset. The selected PCs are fed into the proposed models for modeling and testing. The evaluation of the performance of the constructed models, using appropriate statistical indices, shows clearly that a PCA-based LS-SVM (PCA-LS-SVM) model is a promising approach for the prediction of BP reactivity in com-parison to others. This assessment demonstrates the importance and advantages posed by hybrid models for the prediction of variables in biomedical research studies.

  7. Reactive modelling of 1,2-DCA and DOC near the shoreline. (United States)

    Colombani, N; Pantano, A; Mastrocicco, M; Petitta, M


    1,2-Dichloroethane (1,2-DCA) was found to be the most abundant compound among chlorinated hydrocarbons detected in a petrochemical plant in southern Italy. This site is located near the coastline, and it is set above an unconfined coastal aquifer, where seawater intrusion is present. The presence of organic and inorganic contaminants at this site has required the implementation of remediation strategies, consisting of pumping wells (hydraulic barrier) and a horizontal flow barrier. The purpose of this work was to assess the influence of salt water intrusion on the degradation rate of 1,2-DCA. This was done on a three-dimensional domain relative to a limited portion of a well characterized field site, accounting for density-dependent flow and reactive transport modelling of 1,2-DCA and Dissolved Organic Carbon (DOC). The modelling procedure was performed employing SEAWAT-4.0 and PHT3D, to reproduce the complex three-dimensional flow and transport domain. In order to determine the fate of 1,2-DCA, detailed field investigations provided intensive depth profile information. Different, kinetically controlled degradation rates were simulated to explain the observed, selective degradation of pollutants in groundwater. Calibration of the model was accomplished by comparison with the two different sets of measurements obtained from the MLS devices and from pumping wells. With the calibrated model, it was possible to distinguish between dispersive non-reactive processes and bacterially mediated reactions. In the non-reactive model, 1,2-DCA sorption was simulated using linear sorption coefficient determined with field data and 1,2-DCA degradation was simulated using a first order decay coefficient using literature data as initial guess. Finally, on the reactive transport model, where a two-step approach with partial equilibrium approach was implemented, the effects of neglecting the cation exchange capacity, omitting density-dependent flow, and refining the vertical

  8. Constitutive Relations for Reactive Transport Modeling: Effects of Chemical Reactions on Multi-Phase Flow Properties (United States)

    Zhang, S.; Liu, H. H.; van Dijke, M. I.; Geiger, S.; Agar, S. M.


    The relationship between flow properties and chemical reactions is key to modeling subsurface reactive transport. This study develops closed-form equations to describe the effects of mineral precipitation and dissolution on multiphase flow properties (capillary pressure and relative permeabilities) of porous media. The model accounts for the fact that precipitation/dissolution only takes place in the water-filled part of pore space. The capillary tube concept was used to connect pore-scale changes to macroscopic hydraulic properties. Precipitation/dissolution induces changes in the pore radii of water-filled pores and consequently in the pore-size distribution. The updated pore-size distribution is converted back to a new capillary pressure-water saturation relation from which the new relative permeabilities are calculated. Pore network modeling is conducted on a Berea sandstone to validate the new continuum-scale relations. The pore network modeling results are satisfactorily predicted by the new closed-form equations. Currently the effects of chemical reactions on flow properties are represented as a relation between permeability and porosity in reactive transport modeling. Porosity is updated after chemical calculations from the change of mineral volumes, then permeability change is calculated from the porosity change using an empirical permeability-porosity relation, most commonly the Carman-Kozeny relation, or the Verma-Pruess relation. To the best of our knowledge, there are no closed-form relations available yet for the effects of chemical reactions on multi-phase flow properties, and thus currently these effects cannot be accounted for in reactive transport modeling. This work presents new constitutive relations to represent how chemical reactions affect multi-phase flow properties on the continuum scale based on the conceptual model of parallel capillary tubes. The parameters in our new relations are either pre-existing input in a multi-phase flow

  9. Astrocyte reactivity in related brain regions in a mouse model of MPTP-induced Parkinson's disease

    Institute of Scientific and Technical Information of China (English)

    Zhijun Zhang; Chunlin Xia; Yulin Dong; Guangming Lü; Juan Liu; Lin Ding; Hengjian Ni


    BACKGROUND: Severe injury to dopaminergic neuronal cell bodies and their axon terminals in the substantia nigra pars compacta (SNC) has been observed in both Parkinson's disease (PD) patients or in 1-methy-4-phenyl-1,2,3,6-tetrahydropyrindine(MPTP)-induced PD animal models, but only slight injury occurs in the adjacent ventral tegmental area (VTA). The mechanisms underlying this selective injury remain poorly understood.OBJECTIVE: To comparatively observe astrocyte reactivity in the SNC, caudate putamen (Cpu), VTA, and frontal association cortex (FrA).DESIGN, TIME AND SETTING: A cellular and molecular biology, randomized, controlled experiment was performed at the Institute of Neurobiology, Department of Human Anatomy, Medical School of Nantong University, between December 2006 and September 2008.MATERIALS: A total of 80 healthy adult male C57BL/6 mice were included in this study. MPTP was purchased from Sigma, USA.METHODS: Mice were randomly divided into a model group (n = 64) and a sham-operated group (n = 16). PD was induced in the mice from the model group by intraperitoneal injection of 20 mg/kg MPTP, once every three hours, for a total of 4 times.MAIN OUTCOME MEASURES: Tyrosine hydroxylase (TH)-immunoreactive neurons and glial fibrillary acidic protein (GFAP)-immunoreactive astrocytes were examined by dual immunofluorescence labeling. GFAP-immunoreactive astrocytes in the Cpu and FrA were determined by immunofluorescent staining. GFAP mRNA expression in the SNC, Cpu, VTA, and FrA was detected using real-time polymerase chain reaction. TH protein levels in the TH-immunoreactive axon terminals of the Cpu and FrA were detected by Western blotting.RESULTS: Numbers of TH-immunoreactive neurons in the SNC, and TH protein level in the Cpu, markedly decreased (by approximately 68%) 1 day after MPTP injection, and gradually increased at 3 days. Simultaneously, astrocyte reactivity was strengthened, in particular at 7 days. However, after MPTP injection, decreases in

  10. Moving from Batch to Field Using the RT3D Reactive Transport Modeling System (United States)

    Clement, T. P.; Gautam, T. R.


    The public domain reactive transport code RT3D (Clement, 1997) is a general-purpose numerical code for solving coupled, multi-species reactive transport in saturated groundwater systems. The code uses MODFLOW to simulate flow and several modules of MT3DMS to simulate the advection and dispersion processes. RT3D employs the operator-split strategy which allows the code solve the coupled reactive transport problem in a modular fashion. The coupling between reaction and transport is defined through a separate module where the reaction equations are specified. The code supports a versatile user-defined reaction option that allows users to define their own reaction system through a Fortran-90 subroutine, known as the RT3D-reaction package. Further a utility code, known as BATCHRXN, allows the users to independently test and debug their reaction package. To analyze a new reaction system at a batch scale, users should first run BATCHRXN to test the ability of their reaction package to model the batch data. After testing, the reaction package can simply be ported to the RT3D environment to study the model response under 1-, 2-, or 3-dimensional transport conditions. This paper presents example problems that demonstrate the methods for moving from batch to field-scale simulations using BATCHRXN and RT3D codes. The first example describes a simple first-order reaction system for simulating the sequential degradation of Tetrachloroethene (PCE) and its daughter products. The second example uses a relatively complex reaction system for describing the multiple degradation pathways of Tetrachloroethane (PCA) and its daughter products. References 1) Clement, T.P, RT3D - A modular computer code for simulating reactive multi-species transport in 3-Dimensional groundwater aquifers, Battelle Pacific Northwest National Laboratory Research Report, PNNL-SA-28967, September, 1997. Available at:

  11. Decreased reactivation of a herpes simplex virus type 1 (HSV-1) latency-associated transcript (LAT) mutant using the in vivo mouse UV-B model of induced reactivation. (United States)

    BenMohamed, Lbachir; Osorio, Nelson; Srivastava, Ruchi; Khan, Arif A; Simpson, Jennifer L; Wechsler, Steven L


    Blinding ocular herpetic disease in humans is due to herpes simplex virus type 1 (HSV-1) reactivations from latency, rather than to primary acute infection. The cellular and molecular immune mechanisms that control the HSV-1 latency-reactivation cycle remain to be fully elucidated. The aim of this study was to determine if reactivation of the HSV-1 latency-associated transcript (LAT) deletion mutant (dLAT2903) was impaired in this model, as it is in the rabbit model of induced and spontaneous reactivation and in the trigeminal ganglia (TG) explant-induced reactivation model in mice. The eyes of mice latently infected with wild-type HSV-1 strain McKrae (LAT((+)) virus) or dLAT2903 (LAT((-)) virus) were irradiated with UV-B, and reactivation was determined. We found that compared to LAT((-)) virus, LAT((+)) virus reactivated at a higher rate as determined by shedding of virus in tears on days 3 to 7 after UV-B treatment. Thus, the UV-B-induced reactivation mouse model of HSV-1 appears to be a useful small animal model for studying the mechanisms involved in how LAT enhances the HSV-1 reactivation phenotype. The utility of the model for investigating the immune evasion mechanisms regulating the HSV-1 latency/reactivation cycle and for testing the protective efficacy of candidate therapeutic vaccines and drugs is discussed.

  12. Models for evolution of reactive surface area during dissolution and precipitation (United States)

    Pedersen, Janne; Jettestuen, Espen; Hildebrand-Habel, Tania; Vinningland, Jan Ludvig; Vadla Madland, Merete; Korsnes, Reidar Inge; Hiorth, Aksel


    During water flooding of a reservoir, minerals can dissolve and/or precipitate if the injected water is out of equilibrium with the formation. A net mass transfer between solid and fluid will result in a dynamically changing pore space, which in turn may change the permeability and/or the porosity of the reservoir. When secondary minerals precipitate from solution they will form on top of the primary minerals on the pore walls, and hence the reactive surface area of the individual minerals constituting the porous medium will change. This will in turn affect the dissolution/precipitation rates. In this work we study three different models for the evolution of reactive surface areas during flooding of a core with a brine that is in disequilibrium with the rock. The three models differ in the way secondary minerals are distributed on the solid surface: In model I the whole surface area of both primary and secondary minerals is reactive; hence there will be no screening effect when secondary minerals form. In model II secondary minerals form as a monolayer on the primary minerals that will screen primary minerals from the flow. Model I and II represent two extremes regarding the screening effect; namely no screening (model I) and full screening (model II). Model III is motivated from observations of unflooded and flooded chalk using scanning electron microscopy (SEM). In this model secondary minerals are assumed to form preferentially near crystal defects, being e.g. dislocations in crystallographic pattern or grain contacts. Also the rate of precipitation for forming minerals varies for precipitation onto primary (dissimilar) minerals and precipitation onto secondary (similar) minerals. The three models are implemented into a lattice Boltzmann (LB) based geochemical simulator, and simulation results are compared to results from a 3 years long core flooding experiment with outcrop chalk flooded with 0.219M MgCl2 at 130°C, as well as SEM studies. Before flooding 98wt

  13. Comparison of numerical simulations of reactive transport and chemostat-like models

    Directory of Open Access Journals (Sweden)

    I. Haidar


    Full Text Available The objective of the paper is to evaluate the ability of reactive transport models and their numerical implementations (such as MIN3P to simulate simple microbial transformations in conditions of chemostat or gradostat models, that are popular in microbial ecology and waste treatment ecosystems. To make this comparison, we first consider an abstract ecosystem composed of a single limiting resource and a single microbial species that are carried by advection. In a second stage, we consider another microbial species in competition for the same limiting resource. Comparing the numerical solutions of the two models, we found that the numerical accuracy of simulations of advective transport models performed with MIN3P depends on the evolution of the concentrations of the microbial species: when the state of the system is close to a non-hyperbolic equilibrium, we observe a numerical inaccuracy that may be due to the discretization method used in numerical approximations of reactive transport equations. Therefore, one has to be cautious about the predictions given by the models.

  14. Small Signal Modeling Of Controller For Statcom Used In Distribution System For Reactive Power Management

    Directory of Open Access Journals (Sweden)

    Wahiddun Nisa


    Full Text Available In this paper non-linear model of the STATCOM is linearized and the following strategies have been adopted . Hence, a small signal model is adopted here. Here, the grid voltage lags the fundamental component of the STATCOM converter terminal voltage with a phase angle difference ' ' . Small signal modeling of the phase angle ' ' and modulation index ' m ' is also done. A single PI-controller for the reactive component current of the STATCOM has been designed. In this model, the DC-link capacitor voltage is held constant without using a separate controller. The STATCOM are designed using SVPWM technique. Through adjustment of the modulation index, fast modulation of the STATCOM reactive power output can be achieved due to high sensitivity of the same with respect to the output voltage of the STATCOM VSC. The model, with PI controllers has been simulated in MATLAB/SIMULINK environment with variation of the pre-charge voltage on the DClink capacitor with linear loads (inductive. Improvement of the power factor of the grid current is achieved for linear loads.

  15. On the multiplicity of solutions of the nonlinear reactive transport model

    Directory of Open Access Journals (Sweden)

    Elyas Shivanian


    Full Text Available The generalization of the nonlinear reaction–diffusion model in porous catalysts the so called one dimensional steady state reactive transport model is revisited. This model, which originates also in fluid and solute transport in soft tissues and microvessels, has been recently given analytical solution in terms of Taylor’s series for different families of reaction terms. This article considers the mentioned model without advective transport in the case of including Michaelis–Menten reaction term and shows that it is exactly solvable and furthermore, gives analytical exact solution in the implicit form for further physical interpretation. It is also revealed that the problem may admit unique or dual or even more triple solutions in some domains for the parameters of the model.

  16. Variable reactivity of particulate organic matter in a global ocean biogeochemical model (United States)

    Aumont, Olivier; van Hulten, Marco; Roy-Barman, Matthieu; Dutay, Jean-Claude; Éthé, Christian; Gehlen, Marion


    The marine biological carbon pump is dominated by the vertical transfer of particulate organic carbon (POC) from the surface ocean to its interior. The efficiency of this transfer plays an important role in controlling the amount of atmospheric carbon that is sequestered in the ocean. Furthermore, the abundance and composition of POC is critical for the removal of numerous trace elements by scavenging, a number of which, such as iron, are essential for the growth of marine organisms, including phytoplankton. Observations and laboratory experiments have shown that POC is composed of numerous organic compounds that can have very different reactivities. However, this variable reactivity of POC has never been extensively considered, especially in modelling studies. Here, we introduced in the global ocean biogeochemical model NEMO-PISCES a description of the variable composition of POC based on the theoretical reactivity continuum model proposed by Boudreau and Ruddick (1991). Our model experiments show that accounting for a variable lability of POC increases POC concentrations in the ocean's interior by 1 to 2 orders of magnitude. This increase is mainly the consequence of a better preservation of small particles that sink slowly from the surface. Comparison with observations is significantly improved both in abundance and in size distribution. Furthermore, the amount of carbon that reaches the sediments is increased by more than a factor of 2, which is in better agreement with global estimates of the sediment oxygen demand. The impact on the major macronutrients (nitrate and phosphate) remains modest. However, iron (Fe) distribution is strongly altered, especially in the upper mesopelagic zone as a result of more intense scavenging: vertical gradients in Fe are milder in the upper ocean, which appears to be closer to observations. Thus, our study shows that the variable lability of POC can play a critical role in the marine biogeochemical cycles which advocates for

  17. Imaging geochemical heterogeneities using inverse reactive transport modeling: An example relevant for characterizing arsenic mobilization and distribution

    DEFF Research Database (Denmark)

    Fakhreddine, Sarah; Lee, Jonghyun; Kitanidis, Peter K.


    -bearing reactive minerals as aquifer contaminants. We use synthetic applications to demonstrate the ability of inverse modeling techniques combined with mechanistic reactive transport models to image reactive mineral lenses in the subsurface and quantify estimation error using indirect, commonly measured...... such as managed aquifer recharge and recovery operations. The modeling investigation is carried out at various scales and considers different flow-through domains including (i) a ID lab-scale column (SO cm), (ii) a 2D lab-scale setup (60 cm x 30 cm) and (iii) a 2D field scale domain (20 nix 4 m). In these setups......, synthetic dissolved oxygen data and forward reactive transport simulations are used to image the spatial distribution of As-bearing pyrite using the Principal Component Geostatistical Approach (PCGA) for inverse modeling. (C) 2015 Elsevier Ltd. All rights reserved....

  18. Toward Optimized Bioclogging and Biocementation Through Combining Advanced Geophysical Monitoring and Reactive Transport Modeling Approaches (United States)

    Hubbard, C. G.; Hubbard, S. S.; Wu, Y.; Surasani, V.; Ajo Franklin, J. B.; Commer, M.; Dou, S.; Kwon, T.; Li, L.; Fouke, B. W.; Coates, J. D.


    Bioclogging and biocementation offer exciting opportunities for solutions to diverse problems ranging from soil stabilization to microbially enhanced hydrocarbon recovery. The effectiveness of bioclogging and biocementation strategies is governed by processes and properties ranging from microbial metabolism at the submicron scale, to changes in pore geometry at the pore scale, to geological heterogeneities at the field scale. Optimization of these strategies requires advances in mechanistic reactive transport modeling and geophysical monitoring methodologies. Our research focuses on (i) performing laboratory experiments to refine understanding of reaction networks and to quantify changes in hydrological properties (e.g. permeability), the evolution of biominerals and geophysical responses (focusing on seismic and electrical techniques); (ii) developing and using a reactive transport simulator capable of predicting the induced metabolic processes to numerically explore how to optimize the desired effect; and (iii) using loosely coupled reactive transport and geophysical simulators to explore detectability and resolvability of induced bioclogging and biocementation processes at the field scale using time-lapse geophysical methods. Here we present examples of our research focused on three different microbially-mediated methods to enhance hydrocarbon recovery through selective clogging of reservior thief zones, including: (a) biopolymer clogging through dextran production; (b) biomineral clogging through iron oxide precipitation; and (c) biomineral clogging through carbonate precipitation. We will compare the utility of these approaches for enhancing hydrocarbon recovery and will describe the utility of geophysical methods to remotely monitor associated field treatments.

  19. Verification of three-dimensional neutron kinetics model of TRAP-KS code regarding reactivity variations

    Energy Technology Data Exchange (ETDEWEB)

    Uvakin, Maxim A.; Alekhin, Grigory V.; Bykov, Mikhail A.; Zaitsev, Sergei I. [EDO ' GIDROPRESS' , Moscow Region, Podolsk (Russian Federation)


    This work deals with TRAP-KS code verification. TRAP-KS is used for coupled neutron and thermo-hydraulic process calculations of VVER reactors. The three-dimensional neutron kinetics model enables consideration of space effects, which are produced by energy field and feedback parameters variations. This feature has to be investigated especially for asymmetrical multiplying variations of core properties, power fluctuations and strong local perturbation insertion. The presented work consists of three test definitions. First, an asymmetrical control rod (CR) ejection during power operation is defined. This process leads to fast reactivity insertion with short-time power spike. As second task xenon oscillations are considered. Here, small negative reactivity insertion leads to power decreasing and induces space oscillations of xenon concentration. In the late phase, these oscillations are suppressed by external actions. As last test, an international code comparison for a hypothetical main steam line break (V1000CT-2, task 2) was performed. This scenario is interesting for asymmetrical positive reactivity insertion by decreasing coolant temperature in the affected loop.

  20. Elucidating reactivity regimes in cyclopentane oxidation: Jet stirred reactor experiments, computational chemistry, and kinetic modeling

    Energy Technology Data Exchange (ETDEWEB)

    Al Rashidi, Mariam J.; Thion, Sébastien; Togbé, Casimir; Dayma, Guillaume; Mehl, Marco; Dagaut, Philippe; Pitz, William J.; Zádor, Judit; Sarathy, S. Mani


    This study is concerned with the identification and quantification of species generated during the combustion of cyclopentane in a jet stirred reactor (JSR). Experiments were carried out for temperatures between 740 and 1250 K, equivalence ratios from 0.5 to 3.0, and at an operating pressure of 10 atm. The fuel concentration was kept at 0.1% and the residence time of the fuel/O2/N2 mixture was maintained at 0.7 s. The reactant, product, and intermediate species concentration profiles were measured using gas chromatography and Fourier transform infrared spectroscopy. The concentration profiles of cyclopentane indicate inhibition of reactivity between 850–1000 K for φ = 2.0 and φ = 3.0. This behavior is interesting, as it has not been observed previously for other fuel molecules, cyclic or non-cyclic. A kinetic model including both low- and high-temperature reaction pathways was developed and used to simulate the JSR experiments. The pressure-dependent rate coefficients of all relevant reactions lying on the PES of cyclopentyl + O2, as well as the C–C and C–H scission reactions of the cyclopentyl radical were calculated at the UCCSD(T)-F12b/cc-pVTZ-F12//M06-2X/6-311++G(d,p) level of theory. The simulations reproduced the unique reactivity trend of cyclopentane and the measured concentration profiles of intermediate and product species. Sensitivity and reaction path analyses indicate that this reactivity trend may be attributed to differences in the reactivity of allyl radical at different conditions, and it is highly sensitive to the C–C/C–H scission branching ratio of the cyclopentyl radical decomposition.

  1. Reactive transport modelling of biogeochemical processes and carbon isotope geochemistry inside a landfill leachate plume. (United States)

    van Breukelen, Boris M; Griffioen, Jasper; Röling, Wilfred F M; van Verseveld, Henk W


    The biogeochemical processes governing leachate attenuation inside a landfill leachate plume (Banisveld, the Netherlands) were revealed and quantified using the 1D reactive transport model PHREEQC-2. Biodegradation of dissolved organic carbon (DOC) was simulated assuming first-order oxidation of two DOC fractions with different reactivity, and was coupled to reductive dissolution of iron oxide. The following secondary geochemical processes were required in the model to match observations: kinetic precipitation of calcite and siderite, cation exchange, proton buffering and degassing. Rate constants for DOC oxidation and carbonate mineral precipitation were determined, and other model parameters were optimized using the nonlinear optimization program PEST by means of matching hydrochemical observations closely (pH, DIC, DOC, Na, K, Ca, Mg, NH4, Fe(II), SO4, Cl, CH4, saturation index of calcite and siderite). The modelling demonstrated the relevance and impact of various secondary geochemical processes on leachate plume evolution. Concomitant precipitation of siderite masked the act of iron reduction. Cation exchange resulted in release of Fe(II) from the pristine anaerobic aquifer to the leachate. Degassing, triggered by elevated CO2 pressures caused by carbonate precipitation and proton buffering at the front of the plume, explained the observed downstream decrease in methane concentration. Simulation of the carbon isotope geochemistry independently supported the proposed reaction network.

  2. Reactive Transport Models with Geomechanics to Mitigate Risks of CO2 Utilization and Storage

    Energy Technology Data Exchange (ETDEWEB)

    Deo, Milind [Univ. of Utah, Salt Lake City, UT (United States); Huang, Hai [Univ. of Utah, Salt Lake City, UT (United States); Kweon, Hyukmin [Univ. of Utah, Salt Lake City, UT (United States); Guo, Luanjing [Univ. of Utah, Salt Lake City, UT (United States)


    Reactivity of carbon dioxide (CO2), rocks and brine is important in a number of practical situations in carbon dioxide sequestration. Injectivity of CO2 will be affected by near wellbore dissolution or precipitation. Natural fractures or faults containing specific minerals may reactivate leading to induced seismicity. In this project, we first examined if the reactions between CO2, brine and rocks affect the nature of the porous medium and properties including petrophysical properties in the timeframe of the injection operations. This was done by carrying out experiments at sequestration conditions (2000 psi for corefloods and 2400 psi for batch experiments, and 600°C) with three different types of rocks – sandstone, limestone and dolomite. Experiments were performed in batch mode and corefloods were conducted over a two-week period. Batch experiments were performed with samples of differing surface area to understand the impact of surface area on overall reaction rates. Toughreact, a reactive transport model was used to interpret and understand the experimental results. The role of iron in dissolution and precipitation reactions was observed to be significant. Iron containing minerals – siderite and ankerite dissolved resulting in changes in porosity and permeability. Corefloods and batch experiments revealed similar patterns. With the right cationic balance, there is a possibility of precipitation of iron bearing carbonates. The results indicate that during injection operations mineralogical changes may lead to injectivity enhancements near the wellbore and petrophysical changes elsewhere in the system. Limestone and dolomite cores showed consistent dissolution at the entrance of the core. The dissolution led to formation of wormholes and interconnected dissolution zones. Results indicate that near wellbore dissolution in these rock-types may lead to rock failure. Micro-CT images of the cores before and after the experiments

  3. Identification and characterization of land use driven nitrogen fluxes using stable isotopes and reactive hydrologic modeling (United States)

    Macko, S. A.; O'Connell, M. T.


    The Najinhe watershed is a topographically diverse, mixed agricultural and urban region in northeastern China that provides opportunities for identification of the impact of land use on nitrogen cycling. In addition to agricultural soil amendments, seasonal variation in atmospheric flow introduces dry and wet deposition from urban and desert sources. Both agricultural amendments and atmospheric sources are significant non-point inputs of reactive N, at estimated annual rates of 450 kg/ha and 30 kg/ha respectively in the nearby North China Plain.Both historic and current land use has influenced the biological processing of nitrogen in a particular area. Soil conditions, including moisture, texture, and organic content, control the capacity of a parcel for processing reactive nitrogen. Compounds derived from natural and anthropogenic sources exhibit characteristic stable isotopes of nitrogen and oxygen that serve as tracers of origin as well as integrators of biological processes. Analysis of bulk soils (including both organic and inorganic N contents) in the system shows δ15N ranging from 1.3 - 8.6 ‰ suggesting varying influence of anthropogenic inputs, fertilizers, soil organic nitrogen, and atmospheric sources based on land use.A distributed hydrologic model coupled with one focusing on reactive transport is able to help determine locations with the highest impact on the dissolved N in this system. Spatial statistical methods are employed to determine the biogeochemical influence of model locations whereas δ18O on soil NO3- and δ15N measurements on NO3- and NH4+ in surface water and soil extracts are used to calibrate and validate model predictions based on measured precipitation and streamflow values. Sources are integrated using a Bayesian mixing model to determine likely fate and transport parameters for various N inputs to the watershed. The application of the coupled hydrologic and transport models to a landscape scale catchment suggests integration and

  4. Atmosphere Clouds Model Algorithm for Solving Optimal Reactive Power Dispatch Problem

    Directory of Open Access Journals (Sweden)

    Lenin Kanagasabai


    Full Text Available In this paper, a new method, called Atmosphere Clouds Model (ACM algorithm, used for solving optimal reactive power dispatch problem. ACM stochastic optimization algorithm stimulated from the behavior of cloud in the natural earth. ACM replicate the generation behavior, shift behavior and extend behavior of cloud. The projected (ACM algorithm has been tested on standard IEEE 30 bus test system and simulation results shows clearly about the superior performance of the proposed algorithm in plummeting the real power loss. Normal 0 false false false EN-IN X-NONE X-NONE

  5. The Reactive-Causal Architecture: Introducing an Emotion Model along with Theories of Needs (United States)

    Aydin, Ali Orhan; Orgun, Mehmet Ali

    In the entertainment application area, one of the major aims is to develop believable agents. To achieve this aim, agents should be highly autonomous, situated, flexible, and display affect. The Reactive-Causal Architecture (ReCau) is proposed to simulate these core attributes. In its current form, ReCau cannot explain the effects of emotions on intelligent behaviour. This study aims is to further improve the emotion model of ReCau to explain the effects of emotions on intelligent behaviour. This improvement allows ReCau to be emotional to support the development of believable agents.

  6. Integrated Modeling and Experimental Studies at the Meso Scale for Advanced Reactive Materials (United States)


    problem (VRP) and vacuum tracking method for non-ideal EOS The vacuum Riemann problem (VRP) is by definition a Riemann problem with vacuum initial condition...T E C H N IC A L R E P O R T DTRA-TR-16-76 Integrated Modeling and Experimental Studies at the Meso- Scale for Advanced Reactive in this grant was directed by Prof. D. Scott Stewart, (the Stewart-Group) and the experimental work and data collection was directed by Prof

  7. Reactive Flow Modeling of Liquid Explosives via ALE3D/Cheetah Simulations

    Energy Technology Data Exchange (ETDEWEB)

    Kuo, I W; Bastea, S; Fried, L E


    We carried out reactive flow simulations of liquid explosives such as nitromethane using the hydrodynamic code ALE3D coupled with equations of state and reaction kinetics modeled by the thermochemical code Cheetah. The simulation set-up was chosen to mimic cylinder experiments. For pure unconfined nitromethane we find that the failure diameter and detonation velocity dependence on charge diameter are in agreement with available experimental results. Such simulations are likely to be useful for determining detonability and failure behavior for a wide range of experimental conditions and explosive compounds.

  8. Reactive transport modeling at uranium in situ recovery sites: uncertainties in uranium sorption on iron hydroxides (United States)

    Johnson, Raymond H.; Tutu, Hlanganani; Brown, Adrian; Figueroa, Linda; Wolkersdorfer, Christian


    Geochemical changes that can occur down gradient from uranium in situ recovery (ISR) sites are important for various stakeholders to understand when evaluating potential effects on surrounding groundwater quality. If down gradient solid-phase material consists of sandstone with iron hydroxide coatings (no pyrite or organic carbon), sorption of uranium on iron hydroxides can control uranium mobility. Using one-dimensional reactive transport models with PHREEQC, two different geochemical databases, and various geochemical parameters, the uncertainties in uranium sorption on iron hydroxides are evaluated, because these oxidized zones create a greater risk for future uranium transport than fully reduced zones where uranium generally precipitates.

  9. Model for high rate gas flows in deformable and reactive porous beds

    Energy Technology Data Exchange (ETDEWEB)

    Weston, A M


    This report presents the development of a one dimensional planar Lagrange hydrodynamic computer model which describes the processes preceding detonation. The model treats gas flow, deflagration, and compaction in a porous bed of reactive material. The early part of deflagration to detonation experiment with porous HMX is simulated. Sensitivity of the simulation calculation to ignition and burn rate parameters is illustrated and discussed. The effects of changing the mean particle size of the porous material are investigated. There is widespread interest in runaway reaction hazards that may be associated with porosity in propellant and explosive materials. Experimentally, such reactions are initiated and observed in long, thick walled hollow tubes, filled with a granular porous bed of reactive material. We will present comparisons with an experiment on porous HMX to illustrate details of the model and to point out what we believe are important features of the observed phenomenon. A geometric finite element cell is devised that allows gas to flow through a compacting matrix. The experimental simulation considers the DDT process from initial squib burn through the onset of general matrix deflagration (convective burning), to the development of a fully dense compaction wave. While this simulation did not calculate turnover to detonation, it did illustrate that the transition occurred as soon as the compaction wave became fully dense. It is shown that deflagration and gas permeation lags compaction at the time of transition. This suggests that the actual transition involves an additional compaction dependent process. 18 references, 20 figures, 3 tables.

  10. Statistical model for combustion of high-metal magnesium-based hydro-reactive fuel

    Institute of Scientific and Technical Information of China (English)

    Hu Jian-Xin; Han Chao; Xia Zhi-Xun; Huang Li-Ya; Huang Xu


    We investigate experimentally and analytically the combustion behavior of a high-metal magnesium-based hydro-reactive fuel under high temperature gaseous atmosphere.The fuel studied in this paper contains 73% magnesium powders.An experimental system is designed and experimeuts are carried out in both argon and water vapor atmospheres.It is found that the burning surface temperature of the fuel is higher in water vapor than that in argon and both of them are higher than the melting point of magnesium,which indicates the molten state of magnesium particles in the burning surface of the fuel.Based on physical considerations and experimental results,a mathematical one-dimensional model is formulated to describe the combustion behavior of the high-metal magnesium-based hydro-reactive fuel.The model enables the evaluation of the burning surface temperature,the burning rate and the flame standoff distance each as a function of chamber pressure and water vapor concentration.The results predicted by the model show that the burning rate and the surface temperature increase when the chamber pressure and the water vapor concentration increase,which are in agreement with the observed experimental trends.

  11. Multiphase flow and multicomponent reactive transport model of the ventilation experiment in Opalinus clay

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, L.; Samper, J.; Montenegro, L.; Major, J.C.


    During the construction and operational phases of a high-level radioactive waste (HLW) repository constructed in a clay formation, ventilation of underground drifts will cause desaturation and oxidation of the rock. The Ventilation Experiment (VE) was performed in a 1.3 m diameter unlined horizontal microtunnel on Opalinus clay at Mont Terri underground research laboratory in Switzerland to evaluate the impact of desaturation on rock properties. A multiphase flow and reactive transport model of VE is presented here. The model accounts for liquid, vapor and air flow, evaporation/condensation and multicomponent reactive solute transport with kinetic dissolution of pyrite and siderite and local-equilibrium dissolution/precipitation of calcite, ferrihydrite, dolomite, gypsum and quartz. Model results reproduce measured vapor flow, liquid pressure and hydrochemical data and capture the trends of measured relative humidities, although such data are slightly overestimated near the rock interface due to uncertainties in the turbulence factor. Rock desaturation allows oxygen to diffuse into the rock and triggers pyrite oxidation, dissolution of calcite and siderite, precipitation of ferrihydrite, dolomite and gypsum and cation exchange. pH in the unsaturated rock varies from 7.8 to 8 and is buffered by calcite. Computed changes in the porosity and the permeability of Opalinus clay in the unsaturated zone caused by oxidation and mineral dissolution/precipitation are smaller than 5%. Therefore, rock properties are not expected to be affected significantly by ventilation of underground drifts during construction and operational phases of a HLW repository in clay.

  12. Reactive transport modeling of subsurface arsenic removal systems in rural Bangladesh. (United States)

    Rahman, M M; Bakker, M; Patty, C H L; Hassan, Z; Röling, W F M; Ahmed, K M; van Breukelen, B M


    Subsurface Arsenic Removal (SAR) is a technique for in-situ removal of arsenic from groundwater. Extracted groundwater is aerated and re-injected into an anoxic aquifer, where the oxygen in the injected water reacts with ferrous iron in the aquifer to form hydrous ferric oxide (HFO). Subsequent extraction of groundwater contains temporarily lower As concentrations, because As sorbs onto the HFO. Injection, storage, and extraction together is called a cycle. A reactive transport model (RTM) was developed in PHREEQC to determine the hydrogeochemical processes responsible for As (im)mobilization during experimental SAR operation performed in Bangladesh. Oxidation of Fe(II) and As(III) were modeled using kinetic-rate expressions. Cation exchange, precipitation of HFO, and surface complexation, were modeled as equilibrium processes. A best set of surface complexation reactions and corresponding equilibrium constants was adopted from previous studies to simulate all 20 cycles of a SAR experiment. The model gives a reasonable match with observed concentrations of different elements in the extracted water (e.g., the r(2) value of As was 0.59 or higher). As concentrations in the extracted water are governed by four major processes. First, As concentration decreases in response to the elevated pH of injection water and likewise increases when native neutral pH groundwater flows in. Second, the sorption capacity for As increases due to the gradual buildup of HFO. Third, As sorption is enhanced by preferential removal of As(V). Fourth, competitive sorption of Si limits the capacity of freshly precipitated HFO for As sorption. Transferability of the developed reactive transport model was demonstrated through successful application of the model, without further calibration, to two additional SAR sites in Bangladesh. This gives confidence that the model could be useful to assess potential SAR performance at locations in Bangladesh based on local hydrogeochemical conditions.

  13. Three-dimensional model for multi-component reactive transport with variable density groundwater flow (United States)

    Mao, X.; Prommer, H.; Barry, D.A.; Langevin, C.D.; Panteleit, B.; Li, L.


    PHWAT is a new model that couples a geochemical reaction model (PHREEQC-2) with a density-dependent groundwater flow and solute transport model (SEAWAT) using the split-operator approach. PHWAT was developed to simulate multi-component reactive transport in variable density groundwater flow. Fluid density in PHWAT depends not on only the concentration of a single species as in SEAWAT, but also the concentrations of other dissolved chemicals that can be subject to reactive processes. Simulation results of PHWAT and PHREEQC-2 were compared in their predictions of effluent concentration from a column experiment. Both models produced identical results, showing that PHWAT has correctly coupled the sub-packages. PHWAT was then applied to the simulation of a tank experiment in which seawater intrusion was accompanied by cation exchange. The density dependence of the intrusion and the snow-plough effect in the breakthrough curves were reflected in the model simulations, which were in good agreement with the measured breakthrough data. Comparison simulations that, in turn, excluded density effects and reactions allowed us to quantify the marked effect of ignoring these processes. Next, we explored numerical issues involved in the practical application of PHWAT using the example of a dense plume flowing into a tank containing fresh water. It was shown that PHWAT could model physically unstable flow and that numerical instabilities were suppressed. Physical instability developed in the model in accordance with the increase of the modified Rayleigh number for density-dependent flow, in agreement with previous research. ?? 2004 Elsevier Ltd. All rights reserved.

  14. Nucleic acid reactivity: challenges for next-generation semiempirical quantum models. (United States)

    Huang, Ming; Giese, Timothy J; York, Darrin M


    Semiempirical quantum models are routinely used to study mechanisms of RNA catalysis and phosphoryl transfer reactions using combined quantum mechanical (QM)/molecular mechanical methods. Herein, we provide a broad assessment of the performance of existing semiempirical quantum models to describe nucleic acid structure and reactivity to quantify their limitations and guide the development of next-generation quantum models with improved accuracy. Neglect of diatomic differential overlap and self-consistent density-functional tight-binding semiempirical models are evaluated against high-level QM benchmark calculations for seven biologically important datasets. The datasets include: proton affinities, polarizabilities, nucleobase dimer interactions, dimethyl phosphate anion, nucleoside sugar and glycosidic torsion conformations, and RNA phosphoryl transfer model reactions. As an additional baseline, comparisons are made with several commonly used density-functional models, including M062X and B3LYP (in some cases with dispersion corrections). The results show that, among the semiempirical models examined, the AM1/d-PhoT model is the most robust at predicting proton affinities. AM1/d-PhoT and DFTB3-3ob/OPhyd reproduce the MP2 potential energy surfaces of 6 associative RNA phosphoryl transfer model reactions reasonably well. Further, a recently developed linear-scaling "modified divide-and-conquer" model exhibits the most accurate results for binding energies of both hydrogen bonded and stacked nucleobase dimers. The semiempirical models considered here are shown to underestimate the isotropic polarizabilities of neutral molecules by approximately 30%. The semiempirical models also fail to adequately describe torsion profiles for the dimethyl phosphate anion, the nucleoside sugar ring puckers, and the rotations about the nucleoside glycosidic bond. The modeling of pentavalent phosphorus, particularly with thio substitutions often used experimentally as mechanistic

  15. Geophysical monitoring and reactive transport modeling of ureolytically-driven calcium carbonate precipitation

    Directory of Open Access Journals (Sweden)

    Taylor Joanna


    Full Text Available Abstract Ureolytically-driven calcium carbonate precipitation is the basis for a promising in-situ remediation method for sequestration of divalent radionuclide and trace metal ions. It has also been proposed for use in geotechnical engineering for soil strengthening applications. Monitoring the occurrence, spatial distribution, and temporal evolution of calcium carbonate precipitation in the subsurface is critical for evaluating the performance of this technology and for developing the predictive models needed for engineering application. In this study, we conducted laboratory column experiments using natural sediment and groundwater to evaluate the utility of geophysical (complex resistivity and seismic sensing methods, dynamic synchrotron x-ray computed tomography (micro-CT, and reactive transport modeling for tracking ureolytically-driven calcium carbonate precipitation processes under site relevant conditions. Reactive transport modeling with TOUGHREACT successfully simulated the changes of the major chemical components during urea hydrolysis. Even at the relatively low level of urea hydrolysis observed in the experiments, the simulations predicted an enhanced calcium carbonate precipitation rate that was 3-4 times greater than the baseline level. Reactive transport modeling results, geophysical monitoring data and micro-CT imaging correlated well with reaction processes validated by geochemical data. In particular, increases in ionic strength of the pore fluid during urea hydrolysis predicted by geochemical modeling were successfully captured by electrical conductivity measurements and confirmed by geochemical data. The low level of urea hydrolysis and calcium carbonate precipitation suggested by the model and geochemical data was corroborated by minor changes in seismic P-wave velocity measurements and micro-CT imaging; the latter provided direct evidence of sparsely distributed calcium carbonate precipitation. Ion exchange processes

  16. Geophysical monitoring and reactive transport modeling of ureolytically-driven calcium carbonate precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Y.; Ajo-Franklin, J.B.; Spycher, N.; Hubbard, S.S.; Zhang, G.; Williams, K.H.; Taylor, J.; Fujita, Y.; Smith, R.


    Ureolytically-driven calcium carbonate precipitation is the basis for a promising in-situ remediation method for sequestration of divalent radionuclide and trace metal ions. It has also been proposed for use in geotechnical engineering for soil strengthening applications. Monitoring the occurrence, spatial distribution, and temporal evolution of calcium carbonate precipitation in the subsurface is critical for evaluating the performance of this technology and for developing the predictive models needed for engineering application. In this study, we conducted laboratory column experiments using natural sediment and groundwater to evaluate the utility of geophysical (complex resistivity and seismic) sensing methods, dynamic synchrotron x-ray computed tomography (micro-CT), and reactive transport modeling for tracking ureolytically-driven calcium carbonate precipitation processes under site relevant conditions. Reactive transport modeling with TOUGHREACT successfully simulated the changes of the major chemical components during urea hydrolysis. Even at the relatively low level of urea hydrolysis observed in the experiments, the simulations predicted an enhanced calcium carbonate precipitation rate that was 3-4 times greater than the baseline level. Reactive transport modeling results, geophysical monitoring data and micro-CT imaging correlated well with reaction processes validated by geochemical data. In particular, increases in ionic strength of the pore fluid during urea hydrolysis predicted by geochemical modeling were successfully captured by electrical conductivity measurements and confirmed by geochemical data. The low level of urea hydrolysis and calcium carbonate precipitation suggested by the model and geochemical data was corroborated by minor changes in seismic P-wave velocity measurements and micro-CT imaging; the latter provided direct evidence of sparsely distributed calcium carbonate precipitation. Ion exchange processes promoted through NH{sub 4}{sup

  17. Geophysical monitoring and reactive transport modeling of ureolytically-driven calcium carbonate precipitation. (United States)

    Wu, Yuxin; Ajo-Franklin, Jonathan B; Spycher, Nicolas; Hubbard, Susan S; Zhang, Guoxiang; Williams, Kenneth H; Taylor, Joanna; Fujita, Yoshiko; Smith, Robert


    Ureolytically-driven calcium carbonate precipitation is the basis for a promising in-situ remediation method for sequestration of divalent radionuclide and trace metal ions. It has also been proposed for use in geotechnical engineering for soil strengthening applications. Monitoring the occurrence, spatial distribution, and temporal evolution of calcium carbonate precipitation in the subsurface is critical for evaluating the performance of this technology and for developing the predictive models needed for engineering application. In this study, we conducted laboratory column experiments using natural sediment and groundwater to evaluate the utility of geophysical (complex resistivity and seismic) sensing methods, dynamic synchrotron x-ray computed tomography (micro-CT), and reactive transport modeling for tracking ureolytically-driven calcium carbonate precipitation processes under site relevant conditions. Reactive transport modeling with TOUGHREACT successfully simulated the changes of the major chemical components during urea hydrolysis. Even at the relatively low level of urea hydrolysis observed in the experiments, the simulations predicted an enhanced calcium carbonate precipitation rate that was 3-4 times greater than the baseline level. Reactive transport modeling results, geophysical monitoring data and micro-CT imaging correlated well with reaction processes validated by geochemical data. In particular, increases in ionic strength of the pore fluid during urea hydrolysis predicted by geochemical modeling were successfully captured by electrical conductivity measurements and confirmed by geochemical data. The low level of urea hydrolysis and calcium carbonate precipitation suggested by the model and geochemical data was corroborated by minor changes in seismic P-wave velocity measurements and micro-CT imaging; the latter provided direct evidence of sparsely distributed calcium carbonate precipitation. Ion exchange processes promoted through NH4

  18. A Mouse Model of Latent Tuberculosis Infection to Study Intervention Strategies to Prevent Reactivation.

    Directory of Open Access Journals (Sweden)

    Andreas Kupz

    Full Text Available Infection with Mycobacterium tuberculosis (Mtb is the leading cause of death in human immunodeficiency virus (HIV+ individuals, particularly in Sub-Saharan Africa. Management of this deadly co-infection is a significant global health challenge that is exacerbated by the lack of efficient vaccines against both Mtb and HIV, as well as the lack of reliable and robust animal models for Mtb/HIV co-infection. Here we describe a tractable and reproducible mouse model to study the reactivation dynamics of latent Mtb infection following the loss of CD4+ T cells as it occurs in HIV-co-infected individuals. Whereas intradermally (i.d. infected C57BL/6 mice contained Mtb within the local draining lymph nodes, depletion of CD4+ cells led to progressive systemic spread of the bacteria and induction of lung pathology. To interrogate whether reactivation of Mtb after CD4+ T cell depletion can be reversed, we employed interleukin (IL-2/anti-IL-2 complex-mediated cell boost approaches. Although populations of non-CD4 lymphocytes, such as CD8+ memory T cells, natural killer (NK cells and double-negative (DN T cells significantly expanded after IL-2/anti-IL-2 complex treatment, progressive development of bacteremia and pathologic lung alterations could not be prevented. These data suggest that the failure to reverse Mtb reactivation is likely not due to anergy of the expanded cell subsets and rather indicates a limited potential for IL-2-complex-based therapies in the management of Mtb/HIV co-infection.

  19. Primary xenografts of human prostate tissue as a model to study angiogenesis induced by reactive stroma.

    Directory of Open Access Journals (Sweden)

    Viviana P Montecinos

    Full Text Available Characterization of the mechanism(s of androgen-driven human angiogenesis could have significant implications for modeling new forms of anti-angiogenic therapies for CaP and for developing targeted adjuvant therapies to improve efficacy of androgen-deprivation therapy. However, models of angiogenesis by human endothelial cells localized within an intact human prostate tissue architecture are until now extremely limited. This report characterizes the burst of angiogenesis by endogenous human blood vessels in primary xenografts of fresh surgical specimens of benign prostate or prostate cancer (CaP tissue that occurs between Days 6-14 after transplantation into SCID mice pre-implanted with testosterone pellets. The wave of human angiogenesis was preceded by androgen-mediated up-regulation of VEGF-A expression in the stromal compartment. The neo-vessel network anastomosed to the host mouse vascular system between Days 6-10 post-transplantation, the angiogenic response ceased by Day 15, and by Day 30 the vasculature had matured and stabilized, as indicated by a lack of leakage of serum components into the interstitial tissue space and by association of nascent endothelial cells with mural cells/pericytes. The angiogenic wave was concurrent with the appearance of a reactive stroma phenotype, as determined by staining for α-SMA, Vimentin, Tenascin, Calponin, Desmin and Masson's trichrome, but the reactive stroma phenotype appeared to be largely independent of androgen availability. Transplantation-induced angiogenesis by endogenous human endothelial cells present in primary xenografts of benign and malignant human prostate tissue was preceded by induction of androgen-driven expression of VEGF by the prostate stroma, and was concurrent with and the appearance of a reactive stroma phenotype. Androgen-modulated expression of VEGF-A appeared to be a causal regulator of angiogenesis, and possibly of stromal activation, in human prostate xenografts.

  20. Reactive transport of metal contaminants in alluvium - Model comparison and column simulation (United States)

    Brown, J.G.; Bassett, R.L.; Glynn, P.D.


    A comparative assessment of two reactive-transport models, PHREEQC and HYDROGEOCHEM (HGC), was done to determine the suitability of each for simulating the movement of acidic contamination in alluvium. For simulations that accounted for aqueous complexation, precipitation and dissolution, the breakthrough and rinseout curves generated by each model were similar. The differences in simulated equilibrium concentrations between models were minor and were related to (1) different units in model output, (2) different activity coefficients, and (3) ionic-strength calculations. When adsorption processes were added to the models, the rinseout pH simulated by PHREEQC using the diffuse double-layer adsorption model rose to a pH of 6 after pore volume 15, about 1 pore volume later than the pH simulated by HGC using the constant-capacitance model. In PHREEQC simulation of a laboratory column experiment, the inability of the model to match measured outflow concentrations of selected constituents was related to the evident lack of local geochemical equilibrium in the column. The difference in timing and size of measured and simulated breakthrough of selected constituents indicated that the redox and adsorption reactions in the column occurred slowly when compared with the modeled reactions. MINTEQA2 and PHREEQC simulations of the column experiment indicated that the number of surface sites that took part in adsorption reactions was less than that estimated from the measured concentration of Fe hydroxide in the alluvium.

  1. Reactive chemical transport in ground-water hydrology: Challenges to mathematical modeling

    Energy Technology Data Exchange (ETDEWEB)

    Narasimhan, T.N.; Apps, J.A.


    For a long time, earth scientists have qualitatively recognized that mineral assemblages in soils and rocks conform to established principles of chemistry. In the early 1960's geochemists began systematizing this knowledge by developing quantitative thermodynamic models based on equilibrium considerations. These models have since been coupled with advective-dispersive-diffusive transport models, already developed by ground-water hydrologists. Spurred by a need for handling difficult environmental issues related to ground-water contamination, these models are being improved, refined and applied to realistic problems of interest. There is little doubt that these models will play an important role in solving important problems of engineering as well as science over the coming years. Even as these models are being used practically, there is scope for their improvement and many challenges lie ahead. In addition to improving the conceptual basis of the governing equations, much remains to be done to incorporate kinetic processes and biological mediation into extant chemical equilibrium models. Much also remains to be learned about the limits to which model predictability can be reasonably taken. The purpose of this paper is to broadly assess the current status of knowledge in modeling reactive chemical transport and to identify the challenges that lie ahead.

  2. Oxidation of a model alkane aerosol by OH radical: the emergent nature of reactive uptake. (United States)

    Houle, F A; Hinsberg, W D; Wilson, K R


    An accurate description of the evolution of organic aerosol in the Earth's atmosphere is essential for climate models. However, the complexity of multiphase chemical and physical transformations has been challenging to describe at the level required to predict aerosol lifetimes and changes in chemical composition. In this work a model is presented that reproduces experimental data for the early stages of oxidative aging of squalane aerosol by hydroxyl radical (OH), a process governed by reactive uptake of gas phase species onto the particle surface. Simulations coupling free radical reactions and Fickian diffusion are used to elucidate how the measured uptake coefficient reflects the elementary steps of sticking of OH to the aerosol as a result of a gas-surface collision, followed by very rapid abstraction of hydrogen and subsequent free radical reactions. It is found that the uptake coefficient is not equivalent to a sticking coefficient or an accommodation coefficient: it is an intrinsically emergent process that depends upon particle size, viscosity, and OH concentration. An expression is derived to examine how these factors control reactive uptake over a broad range of atmospheric and laboratory conditions, and is shown to be consistent with simulation results. Well-mixed, liquid behavior is found to depend on the reaction conditions in addition to the nature of the organic species in the aerosol particle.

  3. Modeling and Evaluating Enhancements in Expanding Ring Search Algorithm for Wireless Reactive Protocols

    CERN Document Server

    Javaid, N; Dridi, K; Khan, Z A; Bouk, S H


    In case of high dynamic topology, reactive routing protocols provide quick convergence by faster route discoveries and route maintenance. Frequent roadcasts reduce routing efficiency in terms of broadcast cost; Bk, and expected time cost; E[t]. These costs are optimized using different mechanisms. So, we select three reactive routing protocols; Ad-hoc On-demand Distance Vector (AODV), Dynamic Source Routing (DSR), and DYnamic Manet On-demad (DYMO). We model expanding Ring Search (ERS); an optimization mechanism in the selected protocols to reduce Bk and E[t]. A novel contribution of this work is enhancement of default ERS in the protocols to optimize Bk and E[t]. Using NS-2, we evaluate and compare default-ERS used by these protocols; AODV-ERS1, DSR-ERS1 and DYMO-ERS1 with enhanced-ERS; AODVERS2, DSR-ERS2 and DYMO-ERS2. From modeling and analytical comparison, we deduce that by adjusting Time-To-Live (T TL) value of a network, efficient optimizations of Bk and E[t] can be achieved.

  4. An experimentally validated contactless acoustic energy transfer model with resistive-reactive electrical loading (United States)

    Shahab, S.; Gray, M.; Erturk, A.


    This paper investigates analytical modeling and experimental validation of Ultrasonic Acoustic Energy Transfer (UAET) for low-power electricity transfer to exploit in wireless applications ranging from medical implants to underwater sensor systems. A piezoelectric receiver bar is excited by incident acoustic waves originating from a source of known strength located at a specific distance from the receiver. The receiver is a free-free piezoelectric cylinder operating in the 33- mode of piezoelectricity with a fundamental resonance frequency above the audible frequency range. In order to extract the electrical power output, the piezoelectric receiver bar is shunted to a generalized resistive-reactive circuit. The goal is to quantify the electrical power delivered to the load (connected to the receiver) in terms of the source strength. Experimental validations are presented along with parameter optimization studies. Sensitivity of the electrical power output to the excitation frequency in the neighborhood of the receiver's underwater resonance frequency, source-to-receiver distance, and source-strength level are reported. Resistive and resistive-reactive electrical loading cases are discussed for performance enhancement and frequency-wise robustness. Simulations and experiments reveal that the presented multiphysics analytical model for UAET can be used to predict the coupled system dynamics with very good accuracy.

  5. A two-fluid model for reactive dilute solid-liquid mixtures with phase changes (United States)

    Reis, Martina Costa; Wang, Yongqi


    Based on the Eulerian spatial averaging theory and the Müller-Liu entropy principle, a two-fluid model for reactive dilute solid-liquid mixtures is presented. Initially, some averaging theorems and properties of average quantities are discussed and, then, averaged balance equations including interfacial source terms are postulated. Moreover, constitutive equations are proposed for a reactive dilute solid-liquid mixture, where the formation of the solid phase is due to a precipitation chemical reaction that involves ions dissolved in the liquid phase. To this end, principles of constitutive theory are used to propose linearized constitutive equations that account for diffusion, heat conduction, viscous and drag effects, and interfacial deformations. A particularity of the model is that the mass interfacial source term is regarded as an independent constitutive variable. The obtained results show that the inclusion of the mass interfacial source term into the set of independent constitutive variables permits to easily describe the phase changes associated with precipitation chemical reactions.

  6. Modeling and analysis of time-dependent processes in a chemically reactive mixture (United States)

    Ramos, M. P.; Ribeiro, C.; Soares, A. J.


    In this paper, we study the propagation of sound waves and the dynamics of local wave disturbances induced by spontaneous internal fluctuations in a reactive mixture. We consider a non-diffusive, non-heat conducting and non-viscous mixture described by an Eulerian set of evolution equations. The model is derived from the kinetic theory in a hydrodynamic regime of a fast chemical reaction. The reactive source terms are explicitly computed from the kinetic theory and are built in the model in a proper way. For both time-dependent problems, we first derive the appropriate dispersion relation, which retains the main effects of the chemical process, and then investigate the influence of the chemical reaction on the properties of interest in the problems studied here. We complete our study by developing a rather detailed analysis using the Hydrogen-Chlorine system as reference. Several numerical computations are included illustrating the behavior of the phase velocity and attenuation coefficient in a low-frequency regime and describing the spectrum of the eigenmodes in the small wavenumber limit.

  7. A two-fluid model for reactive dilute solid-liquid mixtures with phase changes (United States)

    Reis, Martina Costa; Wang, Yongqi


    Based on the Eulerian spatial averaging theory and the Müller-Liu entropy principle, a two-fluid model for reactive dilute solid-liquid mixtures is presented. Initially, some averaging theorems and properties of average quantities are discussed and, then, averaged balance equations including interfacial source terms are postulated. Moreover, constitutive equations are proposed for a reactive dilute solid-liquid mixture, where the formation of the solid phase is due to a precipitation chemical reaction that involves ions dissolved in the liquid phase. To this end, principles of constitutive theory are used to propose linearized constitutive equations that account for diffusion, heat conduction, viscous and drag effects, and interfacial deformations. A particularity of the model is that the mass interfacial source term is regarded as an independent constitutive variable. The obtained results show that the inclusion of the mass interfacial source term into the set of independent constitutive variables permits to easily describe the phase changes associated with precipitation chemical reactions.

  8. Variably saturated flow and multicomponent biogeochemical reactive transport modeling of a uranium bioremediation field experiment. (United States)

    Yabusaki, Steven B; Fang, Yilin; Williams, Kenneth H; Murray, Christopher J; Ward, Andy L; Dayvault, Richard D; Waichler, Scott R; Newcomer, Darrell R; Spane, Frank A; Long, Philip E


    Three-dimensional, coupled variably saturated flow and biogeochemical reactive transport modeling of a 2008 in situ uranium bioremediation field experiment is used to better understand the interplay of transport and biogeochemical reactions controlling uranium behavior under pulsed acetate amendment, seasonal water table variation, spatially variable physical (hydraulic conductivity, porosity) and geochemical (reactive surface area) material properties. While the simulation of the 2008 Big Rusty acetate biostimulation field experiment in Rifle, Colorado was generally consistent with behaviors identified in previous field experiments at the Rifle IFRC site, the additional process and property detail provided several new insights. A principal conclusion from this work is that uranium bioreduction is most effective when acetate, in excess of the sulfate-reducing bacteria demand, is available to the metal-reducing bacteria. The inclusion of an initially small population of slow growing sulfate-reducing bacteria identified in proteomic analyses led to an additional source of Fe(II) from the dissolution of Fe(III) minerals promoted by biogenic sulfide. The falling water table during the experiment significantly reduced the saturated thickness of the aquifer and resulted in reactants and products, as well as unmitigated uranium, in the newly unsaturated vadose zone. High permeability sandy gravel structures resulted in locally high flow rates in the vicinity of injection wells that increased acetate dilution. In downgradient locations, these structures created preferential flow paths for acetate delivery that enhanced local zones of TEAP reactivity and subsidiary reactions. Conversely, smaller transport rates associated with the lower permeability lithofacies (e.g., fine) and vadose zone were shown to limit acetate access and reaction. Once accessed by acetate, however, these same zones limited subsequent acetate dilution and provided longer residence times that resulted

  9. Modeling reactive geochemical transport of concentrated aqueous solutions in variably saturated media

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Guoxiang; Zheng, Zuoping; Wan, Jiamin


    Concentrated aqueous solutions (CAS) have unique thermodynamic and physical properties. Chemical components in CAS are incompletely dissociated, especially those containing divalent or polyvalent ions. The problem is further complicated by the interaction between CAS flow processes and the naturally heterogeneous sediments. As the CAS migrates through the porous media, the composition may be altered subject to fluid-rock interactions. To effectively model reactive transport of CAS, we must take into account ion-interaction. A combination of the Pitzer ion-interaction and the ion-association model would be an appropriate way to deal with multiple-component systems if the Pitzer' parameters and thermodynamic data of dissolved components and the related minerals are available. To quantify the complicated coupling of CAS flow and transport, as well as the involved chemical reactions in natural and engineered systems, we have substantially extended an existing reactive biogeochemical transport code, BIO-CORE{sup 2D}{copyright}, by incorporating a comprehensive Pitzer ion-interaction model. In the present paper, the model, and two test cases against measured data were briefly introduced. Finally we present an application to simulate a laboratory column experiment studying the leakage of the high alkaline waste fluid stored in Hanford (a site of the U.S. Department of Energy, located in Washington State, USA). With the Pitzer ion-interaction ionic activity model, our simulation captures measured pH evolution. The simulation indicates that all the reactions controlling the pH evolution, including cation exchanges, mineral precipitation and dissolution, are coupled.

  10. Final Report Coupling in silico microbial models with reactive transport models to predict the fate of contaminants in the subsurface.

    Energy Technology Data Exchange (ETDEWEB)

    Lovley, Derek R.


    This project successfully accomplished its goal of coupling genome-scale metabolic models with hydrological and geochemical models to predict the activity of subsurface microorganisms during uranium bioremediation. Furthermore, it was demonstrated how this modeling approach can be used to develop new strategies to optimize bioremediation. The approach of coupling genome-scale metabolic models with reactive transport modeling is now well enough established that it has been adopted by other DOE investigators studying uranium bioremediation. Furthermore, the basic principles developed during our studies will be applicable to much broader investigations of microbial activities, not only for other types of bioremediation, but microbial metabolism in diversity of environments. This approach has the potential to make an important contribution to predicting the impact of environmental perturbations on the cycling of carbon and other biogeochemical cycles.

  11. Thermochemical process for seasonal storage of solar energy: characterization and modeling of a high-density reactive bed


    Michel, Benoit; Mazet, Nathalie; Mauran, Sylvain; Stitou, Driss; Jing XU


    International audience; This paper focuses on the characterization and modeling of a solid/gas thermochemical reaction between a porous reactive bed and moist air flowing through it. The aim is the optimization of both energy density and permeability of the reactive bed, in order to realize a high density thermochemical system for seasonal thermal storage for house heating application. Several samples with different implementation parameters (density, binder, diffuser, porous bed texture) hav...

  12. Using consensus bayesian network to model the reactive oxygen species regulatory pathway. (United States)

    Hu, Liangdong; Wang, Limin


    Bayesian network is one of the most successful graph models for representing the reactive oxygen species regulatory pathway. With the increasing number of microarray measurements, it is possible to construct the bayesian network from microarray data directly. Although large numbers of bayesian network learning algorithms have been developed, when applying them to learn bayesian networks from microarray data, the accuracies are low due to that the databases they used to learn bayesian networks contain too few microarray data. In this paper, we propose a consensus bayesian network which is constructed by combining bayesian networks from relevant literatures and bayesian networks learned from microarray data. It would have a higher accuracy than the bayesian networks learned from one database. In the experiment, we validated the bayesian network combination algorithm on several classic machine learning databases and used the consensus bayesian network to model the Escherichia coli's ROS pathway.

  13. Reactive flow modeling of initial density effect on divergence JB-9014 detonation driving (United States)

    Yu, Xin; Huang, Kuibang; Zheng, Miao


    A serious of experiments were designed and the results were represented in this paper, in which 2mm thickness cooper shells were impacted by explosives named JB-9014 with different densities, and the surface velocities of the OFHC shells were measured. The comparison of experimental data shows the free surface velocity of the OFHC shell increase with the IHE density. Numerical modeling, which occupied phenomenological reactive flow rate model using the two-dimensional Lagrange hydrodynamic code, were carried out to simulate the above experiments, and empirical adjustments on detonation velocity and pressure and Pier Tang's adjustments on EOS of detonation products were both introduced in our numerical simulation work. The computational results agree well with that of experiments, and the numerical results with original parameters of products and the adjusted ones of JB-9014 could describe the density effect distinctly.

  14. A model for reactive nonadiabatic transitions: Comparison between exact numerical and approximate analytical results (United States)

    Child, M. S.; Baer, M.


    Exact diabatic/adiabatic branching ratios and final state distributions are presented for a reactive model for nonadiabatic transitions, applicable to situations where the coupling term is approximately constant over the region where the interpotential seam crosses the two valleys. Comparison is made with the Bauer-Fischer-Gilmore (BFG) and Franck-Condon (FC) models for a variety of situations. A new index γ=(vRΔGR/vrΔGR), where subscripts R and r denote translational and vibrational variables, respectively, is introduced as a measure of the validity of the two approximations. The FC approximation is shown to become exact for γ≳≳1, while the BFG approximation is preferred for γ<<1.

  15. On the in vivo photochemical rate parameters for PDT reactive oxygen species modeling (United States)

    Kim, Michele M.; Ghogare, Ashwini A.; Greer, Alexander; Zhu, Timothy C.


    Photosensitizer photochemical parameters are crucial data in accurate dosimetry for photodynamic therapy (PDT) based on photochemical modeling. Progress has been made in the last few decades in determining the photochemical properties of commonly used photosensitizers (PS), but mostly in solution or in vitro. Recent developments allow for the estimation of some of these photochemical parameters in vivo. This review will cover the currently available in vivo photochemical properties of photosensitizers as well as the techniques for measuring those parameters. Furthermore, photochemical parameters that are independent of environmental factors or are universal for different photosensitizers will be examined. Most photosensitizers discussed in this review are of the type II (singlet oxygen) photooxidation category, although type I photosensitizers that involve other reactive oxygen species (ROS) will be discussed as well. The compilation of these parameters will be essential for ROS modeling of PDT.

  16. Determination of reactivity parameters of model carbons, cokes and flame-chars

    DEFF Research Database (Denmark)

    Sørensen, Lasse Holst; Gjernes, Erik; Jessen, Thomas


    Reactivity profiles are defined and measured with thermogravimetry for a dense metallurgical Longyear coke, a polymer-derived porous active carbon, Carboxen 1000, and three flame-chars, Illinois #6, Pittsburgh #8 and New Mexico Blue #1. For each sample it is found that the reactivity profile can ...... reactivity measure is used to rank fuels with very different structural profiles, at varying levels of burnout, temperature and oxygen partial pressure. Keyword: TGA,Reactivity,Coal...

  17. Reactive Transport Modeling and Geophysical Monitoring of Bioclogging at Reservoir Scale (United States)

    Surasani, V.; Commer, M.; Ajo Franklin, J. B.; Li, L.; Hubbard, S. S.


    In Microbial-Enhanced-Hydrocarbon-Recovery (MEHR), preferential bioclogging targets the growth of the biofilms (def. immobilized biopolymers with active cells embodied in it) in highly permeable thief zones to enhance sweep efficiency in oil reservoirs. During MEHR, understanding and controlling bioclogging is hindered by the lack of advanced modeling and monitoring tools; these deficiencies contribute to suboptimal performance. Our focus in this study was on developing a systematic approach to understand and monitor bioclogging at the reservoir scale using a combination of reactive transport modeling and geophysical imaging tools (EM & seismic). In this study, we created a realistic reservoir model from a heterogeneous gas reservoir in the Southern Sacramento basin, California; the model well (Citizen Green #1) was characterized using sonic, electrical, nuclear, and NMR logs for hydrologic and geophysical properties. From the simplified 2D log data model, a strip of size 150m x75m with several high permeability streaks is identified for bioclogging simulation experiments. From the NMR log data it is observed that a good linear correlation exist between logarithmic permeability (0.55- 3.34 log (mD)) versus porosity (0.041-0.28). L. mesenteroides was chosen as the model bacteria. In the presence of sucrose, it enzymatically catalyzes the production of dextran, a useful bioclogging agent. Using microbial kinetics from our laboratory experiment and reservoir heterogeneity, a reactive transport model (RTM) is established for two kinds of bioclogging treatments based on whether microbes are present in situ or are supplied externally. In both cases, sucrose media (1.5 M) is injected at the rate of 1 liter/s for 20 days into the center of high permeable strip to stimulate microbes. Simulations show that the high dextran production was deep into the formation from the injection well. This phenomenon can be explained precisely with bacterial kinetics and injection rate. In

  18. Are reactive transport models reliable tools for reconstructing historical contamination scenarios? (United States)

    Clement, P.


    models to reconstruct the historical concentration levels. In this presentation, I will first briefly review the details of the contamination problem and the modeling results. Later I will use the field study to answer the following questions: 1) Are reactive transport modeling tools sufficiently reliable for reconstructing historical VOC contamination at field sites? 2) What are the benefits of using reactive transport models for resolving policy problems related to a groundwater risk/exposure assessment problem? Finally, we will use this example to answer a rhetorical question—-how much complexity is too much complexity?

  19. Development and application of a reactive plume-in-grid model: evaluation over Greater Paris

    Directory of Open Access Journals (Sweden)

    I. Korsakissok


    Full Text Available Emissions from major point sources are badly represented by classical Eulerian models. An overestimation of the horizontal plume dilution, a bad representation of the vertical diffusion as well as an incorrect estimate of the chemical reaction rates are the main limitations of such models in the vicinity of major point sources. The plume-in-grid method is a multiscale modeling technique that couples a local-scale Gaussian puff model with an Eulerian model in order to better represent these emissions. We present the plume-in-grid model developed in the air quality modeling system Polyphemus, with full gaseous chemistry. The model is evaluated on the metropolitan Île-de-France region, during six months (summer 2001. The subgrid-scale treatment is used for 89 major point sources, a selection based on the emission rates of NOx and SO2. Results with and without the subgrid treatment of point emissions are compared, and their performance by comparison to the observations at measurement stations is assessed. A sensitivity study is also carried out, on several local-scale parameters as well as on the vertical diffusion within the urban area.

    Primary pollutants are shown to be the most impacted by the plume-in-grid treatment, with a decrease in RMSE by up to about -17% for SO2 and -7% for NO at measurement stations. SO2 is the most impacted pollutant, since the point sources account for an important part of the total SO2 emissions, whereas NOx emissions are mostly due to traffic. The spatial impact of the subgrid treatment is localized in the vicinity of the sources, especially for reactive species (NOx and O3. Reactive species are mostly sensitive to the local-scale parameters, such as the time step between two puff emissions which influences the in-plume chemical reactions, whereas the almost-passive species SO2 is more sensitive to the

  20. Reactive Kripke semantics

    CERN Document Server

    Gabbay, Dov M


    This text offers an extension to the traditional Kripke semantics for non-classical logics by adding the notion of reactivity. Reactive Kripke models change their accessibility relation as we progress in the evaluation process of formulas in the model. This feature makes the reactive Kripke semantics strictly stronger and more applicable than the traditional one. Here we investigate the properties and axiomatisations of this new and most effective semantics, and we offer a wide landscape of applications of the idea of reactivity. Applied topics include reactive automata, reactive grammars, rea

  1. Modeling non-isothermal multiphase multi-species reactive chemical transport in geologic media

    Energy Technology Data Exchange (ETDEWEB)

    Tianfu Xu; Gerard, F.; Pruess, K.; Brimhall, G.


    The assessment of mineral deposits, the analysis of hydrothermal convection systems, the performance of radioactive, urban and industrial waste disposal, the study of groundwater pollution, and the understanding of natural groundwater quality patterns all require modeling tools that can consider both the transport of dissolved species as well as their interactions with solid (or other) phases in geologic media and engineered barriers. Here, a general multi-species reactive transport formulation has been developed, which is applicable to homogeneous and/or heterogeneous reactions that can proceed either subject to local equilibrium conditions or kinetic rates under non-isothermal multiphase flow conditions. Two numerical solution methods, the direct substitution approach (DSA) and sequential iteration approach (SIA) for solving the coupled complex subsurface thermo-physical-chemical processes, are described. An efficient sequential iteration approach, which solves transport of solutes and chemical reactions sequentially and iteratively, is proposed for the current reactive chemical transport computer code development. The coupled flow (water, vapor, air and heat) and solute transport equations are also solved sequentially. The existing multiphase flow code TOUGH2 and geochemical code EQ3/6 are used to implement this SIA. The flow chart of the coupled code TOUGH2-EQ3/6, required modifications of the existing codes and additional subroutines needed are presented.

  2. Parametric Study of ReaxFF Simulation Parameters for Molecular Dynamics Modeling of Reactive Carbon Gases. (United States)

    Jensen, Benjamin D; Bandyopadhyay, Ananyo; Wise, Kristopher E; Odegard, Gregory M


    The development of innovative carbon-based materials can be greatly facilitated by molecular modeling techniques. Although the Reax Force Field (ReaxFF) can be used to simulate the chemical behavior of carbon-based systems, the simulation settings required for accurate predictions have not been fully explored. Using the ReaxFF, molecular dynamics (MD) simulations are used to simulate the chemical behavior of pure carbon and hydrocarbon reactive gases that are involved in the formation of carbon structures such as graphite, buckyballs, amorphous carbon, and carbon nanotubes. It is determined that the maximum simulation time step that can be used in MD simulations with the ReaxFF is dependent on the simulated temperature and selected parameter set, as are the predicted reaction rates. It is also determined that different carbon-based reactive gases react at different rates, and that the predicted equilibrium structures are generally the same for the different ReaxFF parameter sets, except in the case of the predicted formation of large graphitic structures with the Chenoweth parameter set under specific conditions.

  3. Sonic hedgehog stimulates neurite outgrowth in a mechanical stretch model of reactive-astrogliosis. (United States)

    Berretta, Antonio; Gowing, Emma K; Jasoni, Christine L; Clarkson, Andrew N


    Although recovery following a stroke is limited, undamaged neurons under the right conditions can establish new connections and take on-board lost functions. Sonic hedgehog (Shh) signaling is integral for developmental axon growth, but its role after injury has not been fully examined. To investigate the effects of Shh on neuronal sprouting after injury, we used an in vitro model of glial scar, whereby cortical astrocytes were mechanically traumatized to mimic reactive astrogliosis observed after stroke. This mechanical trauma impaired neurite outgrowth from post-natal cortical neurons plated on top of reactive astrocytes. Addition of Shh to the media, however, resulted in a concentration-dependent increase in neurite outgrowth. This response was inhibited by cyclopamine and activated by oxysterol 20(S)-hydroxycholesterol, both of which modulate the activity of the Shh co-receptor Smoothened (Smo), demonstrating that Shh-mediated neurite outgrowth is Smo-dependent. In addition, neurite outgrowth was not associated with an increase in Gli-1 transcription, but could be inhibited by PP2, a selective inhibitor of Src family kinases. These results demonstrate that neurons exposed to the neurite growth inhibitory environment associated with a glial scar can be stimulated by Shh, with signaling occurring through a non-canonical pathway, to overcome this suppression and stimulate neurite outgrowth.

  4. Modelling of reactive transport in a sedimentary basin affected by a glaciation/deglaciation event

    Energy Technology Data Exchange (ETDEWEB)

    Bea, S.A.; Mayer, U. [Univ. of British Columbia, Dept. of Earth and Ocean Sciences, Vancouver, BC (Canada); MacQuarrie, K.T.B. [Univ. of New Brunswick, Dept. of Civil Engineering, Fredericton, NB (Canada)


    Canada's plan for the long-term care of used nuclear fuel is containment and isolation in a Deep Geologic Repository (DGR) constructed in a suitable sedimentary or crystalline rock formation. In sedimentary basins fluid migration and geochemical conditions may be impacted by multiple interacting processes including density-dependent groundwater flow, solute transport, heat transfer, mechanical loading, and rock-water interactions. Understanding the interactions among these processes is important when assessing the long-term hydrodynamic and geochemical stability of sedimentary basins during glaciation/deglaciation events. To improve the capability to investigate these processes, an enhanced version of the reactive transport code MIN3P (i.e. MIN3P-NWMO) was developed and tested. The processes incorporated in the new model were evaluated by simulating reactive transport in a hypothetical sedimentary basin affected by a simplified glaciation scenario consisting of a single cycle of ice sheet advance and retreat. The simulations are used to provide an illustrative assessment of the hydrogeological and geochemical stability of this sedimentary basin over a time period of 32,500 years. The results suggest a high degree of geochemical stability. (author)

  5. Experimental Study and Reactive Transport Modeling of Boric Acid Leaching of Concrete

    Directory of Open Access Journals (Sweden)

    Chiang K.-T. K.


    Full Text Available Borated water leakage through spent fuel pools (SFPs at pressurized water reactors is a concern because it could cause corrosion of reinforcement steel in the concrete structure, compromise the integrity of the structure, or cause unmonitored releases of contaminated water to the environment. Experimental data indicate that pH is a critical parameter that determines the corrosion susceptibility of rebar in borated water and the degree of concrete degradation by boric acid leaching. In this study, reactive transport modeling of concrete leaching by borated water was performed to provide information on the solution pH in the concrete crack or matrix and the degree of concrete degradation at different locations of an SFP concrete structure exposed to borated water. Simulations up to 100 years were performed using different boric acid concentrations, crack apertures, and solution flow rates. Concrete cylinders were immersed in boric acid solutions for several months and the mineralogical changes and boric acid penetration in the concrete cylinder were evaluated as a function of time. The depths of concrete leaching by boric acid solution derived from the reactive transport simulations were compared with the measured boric acid penetration depth.

  6. Study on Reactive Adsorption Desulfurization of Model Gasoline on Ni/ZnO-HY Adsorbent

    Institute of Scientific and Technical Information of China (English)

    Huang Huan; Salissou M. Nour; Yi Dezhi; Meng Xuan; Shi Li


    The reactive adsorption desulfurization of model gasoline was carried out on Ni/ZnO-HY adsorbent. The Ni/ZnO-HY adsorbent was characterized by N2 adsorption-desorption test (BET), X-ray diffractometry (XRD), and tempera-ture-programmed reduction (TPR) analysis. The test results have demonstrated that HY-zeolite is a feasible support for Ni/ZnO components used in reactive adsorption desulfurization. The results of XRD and TPR analyses showed that most of nickel element was present as Ni2+species with only a small part existing as Ni3+species, and the Ni2+species had interac-tions with HY-zeolite. Under the conditions of this study, which speciifed a 50%ratio of HY-zeolite in the adsorbent, a Zn/Ni molar ratio of 10, and a reduction temperature of 400℃, the Ni/ZnO-HY adsorbent showed the best desulfurization per-formance. The sulfur capacity of Ni/ZnO-HY adsorbent could be recovered to 92.19%of the fresh one after being subjected to regeneration at 500℃, and could be maintained at 82.17%of the fresh one after 5 regeneration cycles.

  7. Evaluating remedial alternatives for an acid mine drainage stream: Application of a reactive transport model (United States)

    Runkel, R.L.; Kimball, B.A.


    A reactive transport model based on one-dimensional transport and equilibrium chemistry is applied to synoptic data from an acid mine drainage stream. Model inputs include streamflow estimates based on tracer dilution, inflow chemistry based on synoptic sampling, and equilibrium constants describing acid/base, complexation, precipitation/dissolution, and sorption reactions. The dominant features of observed spatial profiles in pH and metal concentration are reproduced along the 3.5-km study reach by simulating the precipitation of Fe(III) and Al solid phases and the sorption of Cu, As, and Pb onto freshly precipitated iron-(III) oxides. Given this quantitative description of existing conditions, additional simulations are conducted to estimate the streamwater quality that could result from two hypothetical remediation plans. Both remediation plans involve the addition of CaCO3 to raise the pH of a small, acidic inflow from ???2.4 to ???7.0. This pH increase results in a reduced metal load that is routed downstream by the reactive transport model, thereby providing an estimate of post-remediation water quality. The first remediation plan assumes a closed system wherein inflow Fe(II) is not oxidized by the treatment system; under the second remediation plan, an open system is assumed, and Fe(II) is oxidized within the treatment system. Both plans increase instream pH and substantially reduce total and dissolved concentrations of Al, As, Cu, and Fe(II+III) at the terminus of the study reach. Dissolved Pb concentrations are reduced by ???18% under the first remediation plan due to sorption onto iron-(III) oxides within the treatment system and stream channel. In contrast, iron(III) oxides are limiting under the second remediation plan, and removal of dissolved Pb occurs primarily within the treatment system. This limitation results in an increase in dissolved Pb concentrations over existing conditions as additional downstream sources of Pb are not attenuated by

  8. Development of a numerical reactive transport modelling framework - Concept & Case Studies (United States)

    Kalbacher, T.; Jang, E.; He, W.; Shao, H.; Zolfaghari, R.; Kolditz, O.


    Civilization and in particular agriculture worldwide depends on the availability of clean freshwater resources stored in the underlying soil and aquifer systems. Unfortunately, water quality is often deteriorating, which is e.g. due to the extensive use of fertilizers or pesticides in agriculture or infiltrating waste water from cities and industries. All groundwater bodies commonly discharge into the nearby surface-water bodies like streams, lakes, or springs, and soil water is a direct water source for the biosphere. Therefore, bio-hydro-geochemical reaction systems along flow paths of the unsaturated as well as the saturated zone can have a strong impact on aquatic and terrestrial ecosystems. The simulation of such reactive transport problems in different hydrological compartments can help to understanding the comprehensive processes chain. One way to evaluate the water quality in space and time is to model the mass transport in soil and/or groundwater together with the contemporaneous chemical reactions numerically. Such physical and bio- hydro- geochemical driven forward simulations are usually solved by standard finite differences, finite element or finite volume methods, but simulating these scenarios at catchment scales is a challenging task due to the extreme computational load, numerical stability issues and different scale-dependencies. The main focus of the present study is the numerical simulation of reactive transport processes in heterogeneous porous media at large scales, i.e. from field scale, over hill slopes towards catchment scale. The objective of the study is, to develop a robust modelling framework which allows to identify appropriate levels of heterogeneity as well as the possibly dominating structural features (e.g. S-shaped clay lenses) with respect to specific reaction systems. The presented modelling framework will describe the functional interaction of different numerical methods and high performing computing (HPC) techniques by the use

  9. CFD modeling of reactive pollutant dispersion in simplified urban configurations with different chemical mechanisms (United States)

    Sanchez, Beatriz; Santiago, Jose-Luis; Martilli, Alberto; Palacios, Magdalena; Kirchner, Frank


    An accurate understanding of urban air quality requires considering a coupled behavior between the dispersion of reactive pollutants and atmospheric dynamics. Currently, urban air pollution is mostly dominated by traffic emission, where nitrogen oxides (NOx) and volatile organic compounds (VOCs) are the primary emitted pollutants. However, modeling reactive pollutants with a large set of chemical reactions, using a computational fluid dynamic (CFD) model, requires a large amount of computational (CPU) time. In this sense, the selection of the chemical reactions needed in different atmospheric conditions becomes essential in finding the best compromise between CPU time and accuracy. The purpose of this work is to assess the differences in NO and NO2 concentrations by considering three chemical approaches: (a) passive tracers (non-reactive), (b) the NOx-O3 photostationary state and (c) a reduced complex chemical mechanism based on 23 species and 25 reactions. The appraisal of the effects of chemical reactions focuses on studying the NO and NO2 dispersion in comparison with the tracer behavior within the street. In turn, the effect of including VOC reactions is also analyzed taking into account several VOC / NOx ratios of traffic emission. Given that the NO and NO2 dispersion can also be affected by atmospheric conditions, such as wind flow or the background concentration from season-dependent pollutants, in this work the influence of wind speeds and background O3 concentrations are studied. The results show that the presence of ozone in the street plays an important role in NO and NO2 concentrations. Therefore, greater differences linked to the chemical approach used are found with higher O3 concentrations and faster wind speeds. This bears relation to the vertical flux as a function of ambient wind speed since it increases the pollutant exchange between the street and the overlying air. This detailed study allows one to ascertain under which atmospheric conditions

  10. The reasoned/reactive model: A new approach to examining eating decisions among female college dieters and nondieters. (United States)

    Ruhl, Holly; Holub, Shayla C; Dolan, Elaine A


    Female college students are prone to unhealthy eating patterns that can impact long-term health. This study examined female students' healthy and unhealthy eating behaviors with three decision-making models. Specifically, the theory of reasoned action, prototype/willingness model, and new reasoned/reactive model were compared to determine how reasoned (logical) and reactive (impulsive) factors relate to dietary decisions. Females (N=583, Mage=20.89years) completed measures on reasoned cognitions about foods (attitudes, subjective norms, nutrition knowledge, intentions to eat foods), reactive cognitions about foods (prototypes, affect, willingness to eat foods), dieting, and food consumption. Structural equation modeling (SEM) revealed the new reasoned/reactive model to be the preeminent model for examining eating behaviors. This model showed that attitudes were related to intentions and willingness to eat healthy and unhealthy foods. Affect was related to willingness to eat healthy and unhealthy foods, whereas nutrition knowledge was related to intentions and willingness to eat healthy foods only. Intentions and willingness were related to healthy and unhealthy food consumption. Dieting status played a moderating role in the model and revealed mean-level differences between dieters and nondieters. This study highlights the importance of specific factors in relation to female students' eating decisions and unveils a comprehensive model for examining health behaviors. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Detailed characterizations of the new Mines Douai comparative reactivity method instrument via laboratory experiments and modeling (United States)

    Michoud, V.; Hansen, R. F.; Locoge, N.; Stevens, P. S.; Dusanter, S.


    The hydroxyl (OH) radical is an important oxidant in the troposphere, which controls the lifetime of most air quality- and climate-related trace gases. However, there are still uncertainties concerning its atmospheric budget, and integrated measurements of OH sinks have been valuable to improve this aspect. Among the analytical tools used for measuring total OH reactivity in ambient air, the comparative reactivity method (CRM) is spreading rapidly in the atmospheric community. However, measurement artifacts have been highlighted for this technique, and additional work is needed to fully characterize them. In this study, we present the new Mines Douai CRM instrument, with an emphasis on the corrections that need to be applied to ambient measurements of total OH reactivity. Measurement artifacts identified in the literature have been investigated, including (1) a correction for a change in relative humidity between the measurement steps leading to different OH levels, (2) the formation of spurious OH in the sampling reactor when hydroperoxy radicals (HO2) react with nitrogen monoxide (NO), (3) not operating the CRM under pseudo-first-order kinetics, and (4) the dilution of ambient air inside the reactor. The dependences of these artifacts on various measurable parameters, such as the pyrrole-to-OH ratio and the bimolecular reaction rate constants of ambient trace gases with OH, have also been studied. Based on these observations, parameterizations are proposed to correct ambient OH reactivity measurements. On average, corrections of 5.2 ± 3.2, 9.2 ± 15.7, and 8.5 ± 5.8 s-1 were respectively observed for (1), (2) and (3) during a field campaign performed in Dunkirk, France (summer 2014). Numerical simulations have been performed using a box model to check whether experimental observations mentioned above are consistent with our understanding of the chemistry occurring in the CRM reactor. Two different chemical mechanisms have been shown to reproduce the magnitude

  12. A new mobile-immobile model for reactive solute transport with scale-dependent dispersion (United States)

    Gao, Guangyao; Zhan, Hongbin; Feng, Shaoyuan; Fu, Bojie; Ma, Ying; Huang, Guanhua


    This study proposed a new mobile-immobile model (MIM) to describe reactive solute transport with scale-dependent dispersion in heterogeneous porous media. The model was derived from the conventional MIM but assumed the dispersivity to be a linear or exponential function of travel distance. The linear adsorption and the first-order degradation of solute were also considered in the model. The Laplace transform technique and the de Hoog numerical Laplace inversion method were applied to solve the developed model. Solute breakthrough curves (BTCs) obtained from MIM with scale-dependent and constant dispersions were compared, and a constant effective dispersivity was provided to reflect the lumped scale-dependent dispersion effect. The effective dispersivity was calculated by arithmetically averaging the distance-dependent dispersivity. With this effective dispersivity, MIM could produce similar BTC as that from MIM with scale-dependent dispersion in porous media with moderate heterogeneity. The applicability of the proposed new model was tested with concentration data from a 1,250-cm long and highly heterogeneous soil column. The simulation results indicated that MIM with constant and linear distance-dependent dispersivities were unable to adequately describe the measured BTCs in the column, while MIM with exponential distance-dependent dispersivity satisfactorily captured the evolution of BTCs.

  13. Crystal Growth Models of Dexamethasone Sodium Phosphate in a MSMPR Reactive Crystallizer

    Institute of Scientific and Technical Information of China (English)

    郝红勋; 王静康; 王永莉; 侯宝红


    The reactive crystallization process of dexamethasone sodium phosphate was investigated in a continuous mixed-suspension, mixed-product-removal(MSMPR) crystallizer. Analyzing experimental data, it was found that the growth of product crystal was size-dependent. The Bransom, CR, ASL, M J2 and M J3 size-dependent growth models were discussed in details. Using experimental steady state population density data of dexamethasone sodium phosphate, parameters of five size-dependent growth models were determined by the method of non-linear least-squares. By comparison of experimental population density and linear growth rate data with those obtained from the five size-dependent growth models, it was found that the MJ3 model predicts the growth more accurately than do the other four models. Based on the theory of population balance, the crystal nucleation and growth rate equations of dexamethasone sodium phosphate were determined by non-linear regression method. The effects of different operation parameters such as supersaturation, magma density and temperature on the quality of product crystal were also discussed, and the optimal operation conditions were derived.

  14. Image-based modeling of flow and reactive transport in porous media (United States)

    Qin, Chao-Zhong; Hoang, Tuong; Verhoosel, Clemens V.; Harald van Brummelen, E.; Wijshoff, Herman M. A.


    Due to the availability of powerful computational resources and high-resolution acquisition of material structures, image-based modeling has become an important tool in studying pore-scale flow and transport processes in porous media [Scheibe et al., 2015]. It is also playing an important role in the upscaling study for developing macroscale porous media models. Usually, the pore structure of a porous medium is directly discretized by the voxels obtained from visualization techniques (e.g. micro CT scanning), which can avoid the complex generation of computational mesh. However, this discretization may considerably overestimate the interfacial areas between solid walls and pore spaces. As a result, it could impact the numerical predictions of reactive transport and immiscible two-phase flow. In this work, two types of image-based models are used to study single-phase flow and reactive transport in a porous medium of sintered glass beads. One model is from a well-established voxel-based simulation tool. The other is based on the mixed isogeometric finite cell method [Hoang et al., 2016], which has been implemented in the open source Nutils ( The finite cell method can be used in combination with isogeometric analysis to enable the higher-order discretization of problems on complex volumetric domains. A particularly interesting application of this immersed simulation technique is image-based analysis, where the geometry is smoothly approximated by segmentation of a B-spline level set approximation of scan data [Verhoosel et al., 2015]. Through a number of case studies by the two models, we will show the advantages and disadvantages of each model in modeling single-phase flow and reactive transport in porous media. Particularly, we will highlight the importance of preserving high-resolution interfaces between solid walls and pore spaces in image-based modeling of porous media. References Hoang, T., C. V. Verhoosel, F. Auricchio, E. H. van

  15. Data preprocessing for parameter estimation. An application to a reactive bimolecular transport model

    CERN Document Server

    Cuch, Daniel A; Hasi, Claudio D El


    In this work we are concerned with the inverse problem of the estimation of modeling parameters for a reactive bimolecular transport based on experimental data that is non-uniformly distributed along the interval where the process takes place. We proposed a methodology that can help to determine the intervals where most of the data should be taken in order to obtain a good estimation of the parameters. For the purpose of reducing the cost of laboratory experiments, we propose to simulate data where is needed and it is not available, a PreProcesing Data Fitting (PPDF).We applied this strategy on the estimation of parameters for an advection-diffusion-reaction problem in a porous media. Each step is explained in detail and simulation results are shown and compared with previous ones.

  16. Methods for modeling impact-induced reactivity changes in small reactors.

    Energy Technology Data Exchange (ETDEWEB)

    Tallman, Tyler N.; Radel, Tracy E.; Smith, Jeffrey A.; Villa, Daniel L.; Smith, Brandon M. (U. of Wisconsin, Madison, WI); Radel, Ross F.; Lipinski, Ronald J.; Wilson, Paul Philip Hood (U. of Wisconsin, Madison, WI)


    This paper describes techniques for determining impact deformation and the subsequent reactivity change for a space reactor impacting the ground following a potential launch accident or for large fuel bundles in a shipping container following an accident. This technique could be used to determine the margin of subcriticality for such potential accidents. Specifically, the approach couples a finite element continuum mechanics model (Pronto3D or Presto) with a neutronics code (MCNP). DAGMC, developed at the University of Wisconsin-Madison, is used to enable MCNP geometric queries to be performed using Pronto3D output. This paper summarizes what has been done historically for reactor launch analysis, describes the impact criticality analysis methodology, and presents preliminary results using representative reactor designs.

  17. Validating Mechanistic Sorption Model Parameters and Processes for Reactive Transport in Alluvium

    Energy Technology Data Exchange (ETDEWEB)

    Zavarin, M; Roberts, S K; Rose, T P; Phinney, D L


    The laboratory batch and flow-through experiments presented in this report provide a basis for validating the mechanistic surface complexation and ion exchange model we use in our hydrologic source term (HST) simulations. Batch sorption experiments were used to examine the effect of solution composition on sorption. Flow-through experiments provided for an analysis of the transport behavior of sorbing elements and tracers which includes dispersion and fluid accessibility effects. Analysis of downstream flow-through column fluids allowed for evaluation of weakly-sorbing element transport. Secondary Ion Mass Spectrometry (SIMS) analysis of the core after completion of the flow-through experiments permitted the evaluation of transport of strongly sorbing elements. A comparison between these data and model predictions provides additional constraints to our model and improves our confidence in near-field HST model parameters. In general, cesium, strontium, samarium, europium, neptunium, and uranium behavior could be accurately predicted using our mechanistic approach but only after some adjustment was made to the model parameters. The required adjustments included a reduction in strontium affinity for smectite, an increase in cesium affinity for smectite and illite, a reduction in iron oxide and calcite reactive surface area, and a change in clinoptilolite reaction constants to reflect a more recently published set of data. In general, these adjustments are justifiable because they fall within a range consistent with our understanding of the parameter uncertainties. These modeling results suggest that the uncertainty in the sorption model parameters must be accounted for to validate the mechanistic approach. The uncertainties in predicting the sorptive behavior of U-1a and UE-5n alluvium also suggest that these uncertainties must be propagated to nearfield HST and large-scale corrective action unit (CAU) models.

  18. Modelling the reactive nitrogen budget across Germany using LOTOS-EUROS between 2000 and 2013 (United States)

    Schaap, Martijn; Banzhaf, Sabine; Hendriks, Carlijn; Kranenburg, Richard


    Nitrogen deposition causes soil acidification and enhances eutrophication causing biodiversity loss. Currently, a major contribution to N-deposition derives from ammonia. Furthermore, ammonia contributes to the formation of secondary inorganic aerosol, a major contributor to atmospheric particulate matter levels. The aerosol formation provides a means of long range transport of reactive nitrogen as the life time of the aerosols is larger than that of ammonia itself. Despite its central role in these environmental threats, little is known about the ammonia budget. In this study we report on recent modelling study to assess the ammonia and reactive nitrogen budget over Germany for a period of 14 years (2000-2013). Prior to the long term simulation the process descriptions in the LOTOS-EUROS CTM were updated and a sensitivity simulation was performed showing that the impact of the compensation point for ammonia and the changes in aerosol deposition had the largest impact against earlier studies. Next, sensitivity simulations were performed to assess the impact of newly reported emissions totals (with 30 higher emissions caused by adjusted emission factors for fertilizer spreading), different spatial and temporal emission variability. Long term evaluation showed that the model is well able to reproduce the variability in wet deposition fluxes induced by varying precipitation amounts, but that systematic changes remain. These sensitivity simulations showed that detailing the seasonal emission variability is more important to remove systematic differences than lowering the uncertainty in dry deposition parametrization. Evaluation with the ammonia retrievals of the IASI satellite confirm that the newly reported emission data for fertilizer application have positive impacts on the modelled ammonia distribution. The new emission information confirms an emission area observed by the satellite in the northeast of Germany, which was previously absent from the national scale

  19. Measurement and modelling of reactive transport in geological barriers for nuclear waste containment. (United States)

    Xiong, Qingrong; Joseph, Claudia; Schmeide, Katja; Jivkov, Andrey P


    Compacted clays are considered as excellent candidates for barriers to radionuclide transport in future repositories for nuclear waste due to their very low hydraulic permeability. Diffusion is the dominant transport mechanism, controlled by a nano-scale pore system. Assessment of the clays' long-term containment function requires adequate modelling of such pore systems and their evolution. Existing characterisation techniques do not provide complete pore space information for effective modelling, such as pore and throat size distributions and connectivity. Special network models for reactive transport are proposed here using the complimentary character of the pore space and the solid phase. This balances the insufficient characterisation information and provides the means for future mechanical-physical-chemical coupling. The anisotropy and heterogeneity of clays is represented using different length parameters and percentage of pores in different directions. Resulting networks are described as mathematical graphs with efficient discrete calculus formulation of transport. Opalinus Clay (OPA) is chosen as an example. Experimental data for the tritiated water (HTO) and U(vi) diffusion through OPA are presented. Calculated diffusion coefficients of HTO and uranium species are within the ranges of the experimentally determined data in different clay directions. This verifies the proposed pore network model and validates that uranium complexes are diffusing as neutral species in OPA. In the case of U(vi) diffusion the method is extended to account for sorption and convection. Rather than changing pore radii by coarse grained mathematical formula, physical sorption is simulated in each pore, which is more accurate and realistic.

  20. Analysis of reactive routing protocols for mobile ad hoc networks in Markov models

    Institute of Scientific and Technical Information of China (English)

    WANG Han-xing; HU Xi; FANG Jian-chao; JIA Wei-jia


    Mobile ad hoc networks (MANETs) have become a hot issue in the area of wireless networks for their non-infrastructure and mobile features. In this paper, a MANET is modeled so that the length of each link in the network is considered as a birthdeath process and the space is reused for n times in the flooding process, which is named as an n-spatial reuse birth-death model (n-SRBDM). We analyze the performance of the network under the dynamic source routing protocol (DSR) which is a famous reactive routing protocol. Some performance parameters of the route discovery are studied such as the probability distribution and the expectation of the flooding distance, the probability that a route is discovered by a query packet with a hop limit, the probability that a request packet finds a τ-time-valid route or a symmetric-valid route, and the average time needed to discover a valid route. For the route maintenance, some parameters are introduced and studied such as the average frequency of route recovery and the average time of a route to be valid. We compare the two models with spatial reuse and without spatial reuse by evaluating these parameters. It is shown that the spatial reuse model is much more effective in routing.

  1. Reactive transport modelling of a high-pH infiltration test in concrete (United States)

    Chaparro, M. Carme; Soler, Josep M.; Saaltink, Maarten W.; Mäder, Urs K.


    A laboratory-scale tracer test was carried out to characterize the transport properties of concrete from the Radioactive Waste Disposal Facility at El Cabril (Spain). A hyperalkaline solution (K-Ca-OH, pH = 13.2) was injected into a concrete sample under a high entry pressure in order to perform the experiment within a reasonable time span, obtaining a decrease of permeability by a factor of 1000. The concentrations of the tracers, major elements (Ca2+, SO4 2 - , K+ and Na+) and pH were measured at the outlet of the concrete sample. A reactive transport model was built based on a double porosity conceptual model, which considers diffusion between a mobile zone, where water can flow, and an immobile zone without any advective transport. The numerical model assumed that all reactions took place in the immobile zone. The cement paste consists of C-S-H gel, portlandite, ettringite, calcite and gypsum, together with residual alite and belite. Two different models were compared, one with portlandite in equilibrium (high initial surface area) and another one with portlandite reaction controlled by kinetics (low initial surface area). Overall the results show dissolution of alite, belite, gypsum, quartz, C-S-H gel and ettringite and precipitation of portlandite and calcite. Permeability could have decreased due to mineral precipitation.

  2. Using Reactive Transport Modeling to Evaluate the Source Term at Yucca Mountain

    Energy Technology Data Exchange (ETDEWEB)

    Y. Chen


    The conventional approach of source-term evaluation for performance assessment of nuclear waste repositories uses speciation-solubility modeling tools and assumes pure phases of radioelements control their solubility. This assumption may not reflect reality, as most radioelements (except for U) may not form their own pure phases. As a result, solubility limits predicted using the conventional approach are several orders of magnitude higher then the concentrations of radioelements measured in spent fuel dissolution experiments. This paper presents the author's attempt of using a non-conventional approach to evaluate source term of radionuclide release for Yucca Mountain. Based on the general reactive-transport code AREST-CT, a model for spent fuel dissolution and secondary phase precipitation has been constructed. The model accounts for both equilibrium and kinetic reactions. Its predictions have been compared against laboratory experiments and natural analogues. It is found that without calibrations, the simulated results match laboratory and field observations very well in many aspects. More important is the fact that no contradictions between them have been found. This provides confidence in the predictive power of the model. Based on the concept of Np incorporated into uranyl minerals, the model not only predicts a lower Np source-term than that given by conventional Np solubility models, but also produces results which are consistent with laboratory measurements and observations. Moreover, two hypotheses, whether Np enters tertiary uranyl minerals or not, have been tested by comparing model predictions against laboratory observations, the results favor the former. It is concluded that this non-conventional approach of source term evaluation not only eliminates over-conservatism in conventional solubility approach to some extent, but also gives a realistic representation of the system of interest, which is a prerequisite for truly understanding the long

  3. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Fan [ORNL; Yeh, Gour-Tsyh [University of Central Florida, Orlando; Parker, Jack C [ORNL; Brooks, Scott C [ORNL; Pace, Molly [ORNL; Kim, Young Jin [ORNL; Jardine, Philip M [ORNL; Watson, David B [ORNL


    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing NE equilibrium reactions and a set of reactive transport equations of M-NE kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.

  4. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions (United States)

    Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C.; Brooks, Scott C.; Pace, Molly N.; Kim, Young-Jin; Jardine, Philip M.; Watson, David B.


    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing NE equilibrium reactions and a set of reactive transport equations of M- NE kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.

  5. Reactive transport modeling of coupled inorganic and organic processes in groundwater

    Energy Technology Data Exchange (ETDEWEB)

    Brun, Adam


    The main goals of this project are to develop and apply a reactive transport code for simulation of coupled organic and inorganic processes in the pollution plume in the ground water down-gradient from the Vejen landfill, Denmark. The detailed field investigations in this aquifer have previously revealed a complex pattern of strongly interdependent organic and inorganic processes. These processes occur simultaneously in a flow and transport system where the mixing of reactive species is influenced by the rather complex geology in the vicinity of the landfill. The removal of organic matter is influenced by the presence of various electron acceptors that also are involved in various inorganic geochemical reactions. It was concluded from the investigations that degradation of organic matter, complexation, mineral precipitation and dissolution, ion-exchange and inorganic redox reactions, as a minimum, should be included in the formulation of the model. The coupling of the organic and inorganic processes is developed based on a literature study. All inorganic processes are as an approximation described as equilibriumm processes. The organic processes are described by a maximum degradation rate that is decreased according to the availability of the participants in the processes, the actual pH, and the presence of inhibiting species. The reactive transport code consists of three separate codes, a flow and transport code, a geochemical code, and a biodegradation code. An iterative solution scheme couples the three codes. The coupled code was successfully verified for simple problems for which analytical solutions exist. For more complex problems the code was tested on synthetic cases and expected plume behavior was successfully simulated. Application of the code to the Vejen landfill aquifer was successful to the degree that the redox zonation down-gradient from the landfill was simulated correctly and that several of the simulated plumes showed a reasonable agreement with

  6. Detailed characterizations of a Comparative Reactivity Method (CRM) instrument: experiments vs. modelling (United States)

    Michoud, V.; Hansen, R. F.; Locoge, N.; Stevens, P. S.; Dusanter, S.


    The Hydroxyl radical (OH) is an important oxidant in the daytime troposphere that controls the lifetime of most trace gases, whose oxidation leads to the formation of harmful secondary pollutants such as ozone (O3) and Secondary Organic Aerosols (SOA). In spite of the importance of OH, uncertainties remain concerning its atmospheric budget and integrated measurements of the total sink of OH can help reducing these uncertainties. In this context, several methods have been developed to measure the first-order loss rate of ambient OH, called total OH reactivity. Among these techniques, the Comparative Reactivity Method (CRM) is promising and has already been widely used in the field and in atmospheric simulation chambers. This technique relies on monitoring competitive OH reactions between a reference molecule (pyrrole) and compounds present in ambient air inside a sampling reactor. However, artefacts and interferences exist for this method and a thorough characterization of the CRM technique is needed. In this study, we present a detailed characterization of a CRM instrument, assessing the corrections that need to be applied on ambient measurements. The main corrections are, in the order of their integration in the data processing: (1) a correction for a change in relative humidity between zero air and ambient air, (2) a correction for the formation of spurious OH when artificially produced HO2 react with NO in the sampling reactor, and (3) a correction for a deviation from pseudo first-order kinetics. The dependences of these artefacts to various measurable parameters, such as the pyrrole-to-OH ratio or the bimolecular reaction rate constants of ambient trace gases with OH are also studied. From these dependences, parameterizations are proposed to correct the OH reactivity measurements from the abovementioned artefacts. A comparison of experimental and simulation results is then discussed. The simulations were performed using a 0-D box model including either (1) a

  7. Modelling On Photogeneration Of Hydroxyl Radical In Surface Waters And Its Reactivity Towards Pharmaceutical Wastes (United States)

    Das, Radha; Vione, Davide; Rubertelli, Francesca; Maurino, Valter; Minero, Claudio; Barbati, Stéphane; Chiron, Serge


    This paper reports a simple model to describe the formation and reactivity of hydroxyl radicals in the whole column of freshwater lakes. It is based on empirical irradiation data and is a function of the water chemical composition (the photochemically significant parameters NPOC, nitrate, nitrite, carbonate and bicarbonate), the lake conformation best expressed as the average depth, and the water absorption spectrum in a simplified Lambert-Beer approach. The purpose is to derive the lifetime of dissolved molecules, due to reaction with •OH, on the basis of their second-order rate constants with the hydroxyl radical. The model was applied to two compounds of pharmaceutical wastes ibuprofen and carbamazepine, for which the second-order rate constants for reaction with the hydroxyl radical were measured by means of the competition kinetics with 2-propanol. The measured values of the rate constants are 1.0×1010 and 1.6×1010M-1 s-1 for ibuprofen and carbamazepine, respectively. The model suggests that the lifetime of a given compound can be very variable in different lakes, even more than the lifetime of different compounds in the same lake. It can be concluded that as far as the reaction with •OH, is concerned the concepts of photolability and photostability, traditionally attached to definite compounds, are ecosystem-dependent at least as much as they depend on the molecule under consideration.

  8. Expanding the role of reactive transport models in critical zone processes (United States)

    Li, Li; Maher, Kate; Navarre-Sitchler, Alexis; Druhan, Jennifer; Meile, Christof; Lawrence, Corey; Moore, Joel; Perdrial, Julia; Sullivan, Pamela; Thompson, Aaron; Jin, Lixin; Bolton, Edward W.; Brantley, Susan L.; Dietrich, William E.; Mayer, K. Ulrich; Steefel, Carl; Valocchi, Albert J.; Zachara, John M.; Kocar, Benjamin D.; McIntosh, Jennifer; Tutolo, Benjamin M.; Kumar, Mukesh; Sonnenthal, Eric; Bao, Chen; Beisman, Joe


    Models test our understanding of processes and can reach beyond the spatial and temporal scales of measurements. Multi-component Reactive Transport Models (RTMs), initially developed more than three decades ago, have been used extensively to explore the interactions of geothermal, hydrologic, geochemical, and geobiological processes in subsurface systems. Driven by extensive data sets now available from intensive measurement efforts, there is a pressing need to couple RTMs with other community models to explore non-linear interactions among the atmosphere, hydrosphere, biosphere, and geosphere. Here we briefly review the history of RTM development, summarize the current state of RTM approaches, and identify new research directions, opportunities, and infrastructure needs to broaden the use of RTMs. In particular, we envision the expanded use of RTMs in advancing process understanding in the Critical Zone, the veneer of the Earth that extends from the top of vegetation to the bottom of groundwater. We argue that, although parsimonious models are essential at larger scales, process-based models offer tools to explore the highly nonlinear coupling that characterizes natural systems. We present seven testable hypotheses that emphasize the unique capabilities of process-based RTMs for (1) elucidating chemical weathering and its physical and biogeochemical drivers; (2) understanding the interactions among roots, micro-organisms, carbon, water, and minerals in the rhizosphere; (3) assessing the effects of heterogeneity across spatial and temporal scales; and (4) integrating the vast quantity of novel data, including “omics” data (genomics, transcriptomics, proteomics, metabolomics), elemental concentration and speciation data, and isotope data into our understanding of complex earth surface systems. With strong support from data-driven sciences, we are now in an exciting era where integration of RTM framework into other community models will facilitate process

  9. Sleep disturbances in highly stress reactive mice: Modeling endophenotypes of major depression

    Directory of Open Access Journals (Sweden)

    Landgraf Rainer


    Full Text Available Abstract Background Neuronal mechanisms underlying affective disorders such as major depression (MD are still poorly understood. By selectively breeding mice for high (HR, intermediate (IR, or low (LR reactivity of the hypothalamic-pituitary-adrenocortical (HPA axis, we recently established a new genetic animal model of extremes in stress reactivity (SR. Studies characterizing this SR mouse model on the behavioral, endocrine, and neurobiological levels revealed several similarities with key endophenotypes observed in MD patients. HR mice were shown to have changes in rhythmicity and sleep measures such as rapid eye movement sleep (REMS and non-REM sleep (NREMS as well as in slow wave activity, indicative of reduced sleep efficacy and increased REMS. In the present study we were interested in how far a detailed spectral analysis of several electroencephalogram (EEG parameters, including relevant frequency bands, could reveal further alterations of sleep architecture in this animal model. Eight adult males of each of the three breeding lines were equipped with epidural EEG and intramuscular electromyogram (EMG electrodes. After recovery, EEG and EMG recordings were performed for two days. Results Differences in the amount of REMS and wakefulness and in the number of transitions between vigilance states were found in HR mice, when compared with IR and LR animals. Increased frequencies of transitions from NREMS to REMS and from REMS to wakefulness in HR animals were robust across the light-dark cycle. Detailed statistical analyses of spectral EEG parameters showed that especially during NREMS the power of the theta (6-9 Hz, alpha (10-15 Hz and eta (16-22.75 Hz bands was significantly different between the three breeding lines. Well defined distributions of significant power differences could be assigned to different times during the light and the dark phase. Especially during NREMS, group differences were robust and could be continuously monitored

  10. The treatment of uncertainties in reactive pollution dispersion models at urban scales. (United States)

    Tomlin, A S; Ziehn, T; Goodman, P; Tate, J E; Dixon, N S


    The ability to predict NO2 concentrations ([NO2]) within urban street networks is important for the evaluation of strategies to reduce exposure to NO2. However, models aiming to make such predictions involve the coupling of several complex processes: traffic emissions under different levels of congestion; dispersion via turbulent mixing; chemical processes of relevance at the street-scale. Parameterisations of these processes are challenging to quantify with precision. Predictions are therefore subject to uncertainties which should be taken into account when using models within decision making. This paper presents an analysis of mean [NO2] predictions from such a complex modelling system applied to a street canyon within the city of York, UK including the treatment of model uncertainties and their causes. The model system consists of a micro-scale traffic simulation and emissions model, and a Reynolds averaged turbulent flow model coupled to a reactive Lagrangian particle dispersion model. The analysis focuses on the sensitivity of predicted in-street increments of [NO2] at different locations in the street to uncertainties in the model inputs. These include physical characteristics such as background wind direction, temperature and background ozone concentrations; traffic parameters such as overall demand and primary NO2 fraction; as well as model parameterisations such as roughness lengths, turbulent time- and length-scales and chemical reaction rate coefficients. Predicted [NO2] is shown to be relatively robust with respect to model parameterisations, although there are significant sensitivities to the activation energy for the reaction NO + O3 as well as the canyon wall roughness length. Under off-peak traffic conditions, demand is the key traffic parameter. Under peak conditions where the network saturates, road-side [NO2] is relatively insensitive to changes in demand and more sensitive to the primary NO2 fraction. The most important physical parameter was

  11. Modelling cross-reactivity and memory in the cellular adaptive immune response to influenza infection in the host. (United States)

    Yan, Ada W C; Cao, Pengxing; Heffernan, Jane M; McVernon, Jodie; Quinn, Kylie M; La Gruta, Nicole L; Laurie, Karen L; McCaw, James M


    The cellular adaptive immune response plays a key role in resolving influenza infection. Experiments where individuals are successively infected with different strains within a short timeframe provide insight into the underlying viral dynamics and the role of a cross-reactive immune response in resolving an acute infection. We construct a mathematical model of within-host influenza viral dynamics including three possible factors which determine the strength of the cross-reactive cellular adaptive immune response: the initial naive T cell number, the avidity of the interaction between T cells and the epitopes presented by infected cells, and the epitope abundance per infected cell. Our model explains the experimentally observed shortening of a second infection when cross-reactivity is present, and shows that memory in the cellular adaptive immune response is necessary to protect against a second infection. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. A nonequilibrium model for reactive contaminant transport through fractured porous media: Model development and semianalytical solution (United States)

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


    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.

  13. Reactive molecular dynamics simulation and chemical kinetic modeling of pyrolysis and combustion of n-dodecane

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Quan-De [College of Chemistry, Sichuan University, Chengdu (China); Wang, Jing-Bo; Li, Juan-Qin; Tan, Ning-Xin; Li, Xiang-Yuan [College of Chemical Engineering, Sichuan University, Chengdu (China)


    The initiation mechanisms and kinetics of pyrolysis and combustion of n-dodecane are investigated by using the reactive molecular dynamics (ReaxFF MD) simulation and chemical kinetic modeling. From ReaxFF MD simulations, we find the initiation mechanisms of pyrolysis of n-dodecane are mainly through two pathways, (1) the cleavage of C-C bond to form smaller hydrocarbon radicals, and (2) the dehydrogenation reaction to form an H radical and the corresponding n-C{sub 12}H{sub 25} radical. Another pathway is the H-abstraction reactions by small radicals including H, CH{sub 3}, and C{sub 2}H{sub 5}, which are the products after the initiation reaction of n-dodecane pyrolysis. ReaxFF MD simulations lead to reasonable Arrhenius parameters compared with experimental results based on first-order kinetic analysis of n-dodecane pyrolysis. The density/pressure effects on the pyrolysis of n-dodecane are also analyzed. By appropriate mapping of the length and time from macroscopic kinetic modeling to ReaxFF MD, a simple comparison of the conversion of n-dodecane from ReaxFF MD simulations and that from kinetic modeling is performed. In addition, the oxidation of n-dodecane is studied by ReaxFF MD simulations. We find that formaldehyde molecule is an important intermediate in the oxidation of n-dodecane, which has been confirmed by kinetic modeling, and ReaxFF leads to reasonable reaction pathways for the oxidation of n-dodecane. These results indicate that ReaxFF MD simulations can give an atomistic description of the initiation mechanism and product distributions of pyrolysis and combustion for hydrocarbon fuels, and can be further used to provide molecular based robust kinetic reaction mechanism for chemical kinetic modeling of hydrocarbon fuels. (author)

  14. Measurement and modeling of engineered nanoparticle transport and aging dynamics in a reactive porous medium (United States)

    Naftaly, Aviv; Dror, Ishai; Berkowitz, Brian


    A continuous time random walk particle tracking (CTRW-PT) method was employed to model flow cell experiments that measured transport of engineered nanoparticles (ENPs) in a reactive porous medium. The experiments involved a water-saturated medium containing negatively charged, polyacrylamide beads, resembling many natural soils and aquifer materials, and having the same refraction index as water. Negatively and positively charged ENPs were injected into a uniform flow field in a 3-D horizontal flow cell, and the spatial and temporal concentrations of the evolving ENP plumes were obtained via image analysis. As a benchmark, and to calibrate the model, Congo red tracer was employed in 1-D column and 3-D flow cell experiments, containing the same beads. Negatively charged Au and Ag ENPs demonstrated migration patterns resembling those of the tracer but were slightly more dispersive; the transport was well represented by the CTRW-PT model. In contrast, positively charged AgNPs displayed an unusual behavior: establishment of an initial plume of essentially immobilized ENPs, followed by development of a secondary, freely migrating plume. The mobile plume was found to contain ENPs that, with aging, exhibited aggregation and charge inversion, becoming negatively charged and mobile. In this case, the CTRW-PT model was modified to include a probabilistic law for particle immobilization, to account for the decreasing tendency (over distance and time) of the positively charged AgNPs to attach to the porous medium. The agreement between experimental results and modeling suggests that the CTRW-PT framework can account for the non-Fickian and surface-charge-dependent transport and aging exhibited by ENPs in porous media.

  15. Subsurface Multiphase Flow and Multicomponent Reactive Transport Modeling using High-Performance Computing

    Energy Technology Data Exchange (ETDEWEB)

    Hammond, Glenn E.; Lichtner, Peter C.; Lu, Chuan


    Numerical modeling has become a critical tool to the Department of Energy for evaluating the environmental impact of alternative energy sources and remediation strategies for legacy waste sites. Unfortunately, the physical and chemical complexity of many sites overwhelms the capabilities of even most “state of the art” groundwater models. Of particular concern are the representation of highly-heterogeneous stratified rock/soil layers in the subsurface and the biological and geochemical interactions of chemical species within multiple fluid phases. Clearly, there is a need for higher-resolution modeling (i.e. more spatial, temporal, and chemical degrees of freedom) and increasingly mechanistic descriptions of subsurface physicochemical processes. We present research being performed in the development of PFLOTRAN, a parallel multiphase flow and multicomponent reactive transport model. Written in Fortran90, PFLOTRAN is founded upon PETSc data structures and solvers and has exhibited impressive strong scalability on up to 4000 processors on the ORNL Cray XT3. We are employing PFLOTRAN in the simulation of uranium transport at the Hanford 300 Area, a contaminated site of major concern to the Department of Energy, the State of Washington, and other government agencies where overly-simplistic historical modeling erroneously predicted decade removal times for uranium by ambient groundwater flow. By leveraging the billions of degrees of freedom available through high-performance computation using tens of thousands of processors, we can better characterize the release of uranium into groundwater and its subsequent transport to the Columbia River, and thereby better understand and evaluate the effectiveness of various proposed remediation strategies.

  16. Carotene reactivity in pink grapefruit juice elucidated from model systems and multiresponse modeling. (United States)

    Achir, Nawel; Hadjal, Thiziri; Madani, Khodir; Dornier, Manuel; Dhuique-Mayer, Claudie


    This study was carried out to assess the impact of pink grapefruit juice composition and structure on the degradation kinetics of lycopene and β-carotene using model systems and multiresponse modeling. Carotenes were heated at four temperatures in their native matrix (juice) or were extracted and incorporated in water/ethanol emulsion systems formulated with or without ascorbic acid or naringin. Kinetic analysis showed that the rate constants and activation energy were lower for lycopene than for β-carotene in the juice, while this trend was inversed in the model system. Multiresponse modeling was used to analyze the role of ascorbic acid and naringin in carotene degradation. Ascorbic acid had a very low impact, while naringin significantly increased the carotene degradation and isomerization rates. We concluded that lycopene was more sensitive to thermal degradation and phytochemical interactions than β-carotene, but this behavior was masked in the fruit juice matrix by better structural protection.

  17. Multiagent-Based Reactive Power Sharing and Control Model for Islanded Microgrids

    DEFF Research Database (Denmark)

    Chen, Feixiong; Chen, Minyou; Li, Qiang


    In islanded microgrids (MGs), the reactive power cannot be shared proportionally among distributed generators (DGs) with conventional droop control, due to the mismatch in feeder impedances. For the purpose of proportional reactive power sharing, a multiagent system (MAS) based distributed control...

  18. Reactivity modeling of the visbreaking of Athabasca bitumen using molecular representations

    Energy Technology Data Exchange (ETDEWEB)

    McCaffrey, W.C.; Gray, M.R. [Alberta Univ., Edmonton, AB (Canada). Dept. of Chemical and Materials Engineering; Dettman, H.D. [Natural Resources Canada, Devon, AB (Canada). CANMET Energy Technology Centre


    The visbreaking of an Athabasca bitumen feedstock was modeled using a Monte Carlo approach. A rule based construction algorithm was then used to create a molecular representation for the Athabasca bitumen. The molecular representation was consistent with many types of data, including 13C-NMR spectroscopy, 1H-NMR spectroscopy, elemental analysis, vapor pressure osmometry, and simulated distillation. Molecular representations that contained a minimum number of molecules were produced using sequential optimization. Each feed molecule was represented using connection and structural matrices. Model compound reactivity studies published in the literature were used to determine the probability of cracking of various C-C and CS bonds. These probabilities were used in a continuous reaction algorithm that used matrix transformations to react feed molecules into product molecules. The reaction simulations were broken down into reaction steps. At each reaction step, molecules were first stochastically chosen to react, and then specific bonds were stochastically chosen to crack. The boiling point of each molecule in the feed and product fractions was calculated using the group contribution theory. The aromaticity, molecular weight, and sulfur content of the cracked liquid product were found to be consistent with the experimental properties.

  19. Performance Evaluation of Two Reactive Routing Protocols of MANET using Group Mobility Model

    Directory of Open Access Journals (Sweden)

    Harminder S. Bindra


    Full Text Available Mobile ad-hoc network is a collection of wireless mobile hosts forming a temporary network without the aid of any stand-alone infrastructure or centralized administration. Mobile ad-hoc network have the attributes such as wireless connection, continuously changing topology, distributed operation and ease of deployment. In this paper we have compared the performance of two reactive MANET routing protocol AODV and DSR by using Group mobility model. Both share similar On-Demand behavior, but the protocol's internal mechanism leads to significant performance difference. We have analyzed the performance of protocols by varying network load, mobility and type of traffic (CBR and TCP. Group Mobility model has been generated by IMPORTANT (Impact of Mobility Patterns on Routing in Ad-hoc NeTwork tool. A detailed simulation has been carried out in NS2. The metrics used for performance analysis are Packet Delivery Fraction, Average end-to-end Delay, Routing Overhead and Normalized Routing Load. It has been observed that AODV gives better performance in CBR traffic and real time delivery of packet. Where as DSR gives better results in TCP traffic and under restricted bandwidth condition.

  20. Ignition and growth reactive flow modeling of recent HMX/TATB detonation experiments (United States)

    Tarver, Craig M.


    Two experimental studies in which faster HMX detonation waves produced oblique detonation waves in adjoining slower detonating TATB charges were modeled using the Ignition and Growth (I&G) reactive flow detonation model parameters for PBX 9501 (95% HMX / 2.5% Estane / 2.5% BDNPA/F) and PBX 9502 (95% TATB / 5% Kel-F binder). Matignon et al. used X1 explosive (96% HMX / 4% binder) to drive an oblique detonation wave into an attached charge of T2 explosive (97% TATB / 3% binder). The flow angles were measured in the T2 shock initiation region and in steady T2 detonation. Anderson et al. used detonating PBX 9501 slabs of various thicknesses ranging from 0.56 mm to 2.5 mm to create oblique detonation waves in 8 mm thick slabs of PBX 9502. Several diagnostics were employed to: photograph the waves; measure detonation velocities and flow angles; and determine the output of the PBX 9501 slabs, the PBX 9502 slabs, and the "initiation regions" using LiF windows and PDV probes.

  1. Reasoned versus reactive prediction of behaviour: a meta-analysis of the prototype willingness model. (United States)

    Todd, Jemma; Kothe, Emily; Mullan, Barbara; Monds, Lauren


    The prototype willingness model (PWM) was designed to extend expectancy-value models of health behaviour by also including a heuristic, or social reactive pathway, to better explain health-risk behaviours in adolescents and young adults. The pathway includes prototype, i.e., images of a typical person who engages in a behaviour, and willingness to engage in behaviour. The current study describes a meta-analysis of predictive research using the PWM and explores the role of the heuristic pathway and intentions in predicting behaviour. Eighty-one studies met inclusion criteria. Overall, the PWM was supported and explained 20.5% of the variance in behaviour. Willingness explained 4.9% of the variance in behaviour over and above intention, although intention tended to be more strongly related to behaviour than was willingness. The strength of the PWM relationships tended to vary according to the behaviour being tested, with alcohol consumption being the behaviour best explained. Age was also an important moderator, and, as expected, PWM behaviour was best accounted for within adolescent samples. Results were heterogeneous even after moderators were taken into consideration. This meta-analysis provides support for the PWM and may be used to inform future interventions that can be tailored for at-risk populations.

  2. Pareto optimal calibration of highly nonlinear reactive transport groundwater models using particle swarm optimization (United States)

    Siade, A. J.; Prommer, H.; Welter, D.


    Groundwater management and remediation requires the implementation of numerical models in order to evaluate the potential anthropogenic impacts on aquifer systems. In many situations, the numerical model must, not only be able to simulate groundwater flow and transport, but also geochemical and biological processes. Each process being simulated carries with it a set of parameters that must be identified, along with differing potential sources of model-structure error. Various data types are often collected in the field and then used to calibrate the numerical model; however, these data types can represent very different processes and can subsequently be sensitive to the model parameters in extremely complex ways. Therefore, developing an appropriate weighting strategy to address the contributions of each data type to the overall least-squares objective function is not straightforward. This is further compounded by the presence of potential sources of model-structure errors that manifest themselves differently for each observation data type. Finally, reactive transport models are highly nonlinear, which can lead to convergence failure for algorithms operating on the assumption of local linearity. In this study, we propose a variation of the popular, particle swarm optimization algorithm to address trade-offs associated with the calibration of one data type over another. This method removes the need to specify weights between observation groups and instead, produces a multi-dimensional Pareto front that illustrates the trade-offs between data types. We use the PEST++ run manager, along with the standard PEST input/output structure, to implement parallel programming across multiple desktop computers using TCP/IP communications. This allows for very large swarms of particles without the need of a supercomputing facility. The method was applied to a case study in which modeling was used to gain insight into the mobilization of arsenic at a deepwell injection site

  3. Development and application of a reactive plume-in-grid model: evaluation over Greater Paris

    Directory of Open Access Journals (Sweden)

    I. Korsakissok


    Full Text Available Emissions from major point sources are badly represented by classical Eulerian models. An overestimation of the horizontal plume dilution, a bad representation of the vertical diffusion as well as an incorrect estimate of the chemical reaction rates are the main limitations of such models in the vicinity of major point sources. The plume-in-grid method is a multiscale modeling technique that couples a local-scale Gaussian puff model with an Eulerian model in order to better represent these emissions. We present the plume-in-grid model developed in the air quality modeling system Polyphemus, with full gaseous chemistry. The model is evaluated on the metropolitan Île-de-France region, during six months (summer 2001. The subgrid-scale treatment is used for 89 major point sources, a selection based on the emission rates of NOx and SO2. Results with and without the subgrid treatment of point emissions are compared, and their performance by comparison to the observations on measurement stations is assessed. A sensitivity study is also carried out, on several local-scale parameters as well as on the vertical diffusion within the urban area.

    Primary pollutants are shown to be the most impacted by the plume-in-grid treatment. SO2 is the most impacted pollutant, since the point sources account for an important part of the total SO2 emissions, whereas NOx emissions are mostly due to traffic. The spatial impact of the subgrid treatment is localized in the vicinity of the sources, especially for reactive species (NOx and O3. Ozone is mostly sensitive to the time step between two puff emissions which influences the in-plume chemical reactions, whereas the almost-passive species SO2 is more sensitive to the injection time, which determines the duration of the subgrid-scale treatment.

    Future developments include an extension to handle aerosol chemistry

  4. Pore network and pore scale modeling of reactive transport in porous media (United States)

    Adler, P. M.; Vu, T. M.; Varloteaux, C.; Bekri, S.


    The study of the evolution of a porous medium where a reactive fluid flows is conditioned by the accurate determination of three macroscopic parameters governing the solute displacement, namely the solute velocity, dispersion and mean reaction rate. Of course, a possible application of such studies is CO2 sequestration. This presentation proposes to approach the determination of these parameters by two different ways and to compare them; both are on the pore scale. In the first one called PNM (for pore-network model), a pore-network is extracted from micro tomography images of a real porous medium. This network is composed of spherical pores joined by circular tubes; it is used to calculate transport macroscopic parameters and porosity-permeability evolution during the reactive transport flow as functions of dimensionless numbers representing the reaction and flow rate regimes. The flow is calculated by using Kirchhoff laws. Transport is determined in the asymptotic regime where the solute concentration undergoes an exponential evolution with time. In the second approach called PSM (for pore scale model), the pore-network model is used as a three dimensional medium which is discretized by the Level Set Method. The Stokes equations are solved in order to determine the local flow field and the corresponding permeability. The solute concentration is obtained by solving the local convection-diffusion equation in the 3D pore-network; numerical dispersion is reduced by a Flux Limiting Scheme. Two different geometries of porous media are addressed by both numerical codes. The first pore-network geometry is used to validate the PNM assumptions, whereas the second pore-network is defined for a better understanding of the dominant solute distribution. One of the main results obtained with the first pore-network is the dependence of the concentration profile on the Péclet number Pe in the pore-bodies. When this number increases, one has to switch from an assumption of

  5. Coupled Reactive Transport Modeling of CO2 Injection in Mt. Simon Sandstone Formation, Midwest USA (United States)

    Liu, F.; Lu, P.; Zhu, C.; Xiao, Y.


    CO2 sequestration in deep geological formations is one of the promising options for CO2 emission reduction. While several large scale CO2 injections in saline aquifers have shown to be successful for the short-term, there is still a lack of fundamental understanding on key issues such as CO2 storage capacity, injectivity, and security over multiple spatial and temporal scales that need to be addressed. To advance these understandings, we applied multi-phase coupled reactive mass transport modeling to investigate the fate of injected CO2 and reservoir responses to the injection into Mt. Simon Formation. We developed both 1-D and 2-D reactive transport models in a radial region of 10,000 m surrounding a CO2 injection well to represent the Mt. Simon sandstone formation, which is a major regional deep saline reservoir in the Midwest, USA. Supercritical CO2 is injected into the formation for 100 years, and the modeling continues till 10,000 years to monitor both short-term and long-term behavior of injected CO2 and the associated rock-fluid interactions. CO2 co-injection with H2S and SO2 is also simulated to represent the flue gases from coal gasification and combustion in the Illinois Basin. The injection of CO2 results in acidified zones (pH ~3 and 5) adjacent to the wellbore, causing progressive water-rock interactions in the surrounding region. In accordance with the extensive dissolution of authigenic K-feldspar, sequential precipitations of secondary carbonates and clay minerals are predicted in this zone. The vertical profiles of CO2 show fingering pattern from the top of the reservoir to the bottom due to the density variation of CO2-impregnated brine, which facilitate convection induced mixing and solubility trapping. Most of the injected CO2 remains within a radial distance of 2500 m at the end of 10,000 years and is sequestered and immobilized by solubility and residual trapping. Mineral trapping via secondary carbonates, including calcite, magnesite

  6. Numerical Modelling of Multi-Phase Multi-Component Reactive Transport in the Earth's interior (United States)

    Oliveira, Beñat; Afonso, Juan Carlos; Zlotnik, Sergio; Tilhac, Romain


    We present a conceptual and numerical approach to model processes in the Earth's interior that involve multiple phases that simultaneously interact thermally, mechanically and chemically. The approach is truly multiphase in the sense that each dynamic phase is explicitly modelled with an individual set of mass, momentum, energy and chemical mass balance equations coupled via interfacial interaction terms. It is also truly multi-component in the sense that the compositions of the system and its constituent thermodynamic phases are expressed by a full set of fundamental chemical components (e.g. SiO_2, Al_2O_3, MgO, etc) rather than proxies. In contrast to previous approaches these chemical components evolve, react with, and partition into, different phases with different physical properties according to an internally-consistent thermodynamic model. This enables a thermodynamically-consistent coupling of the governing set of balance equations. Interfacial processes such as surface tensions and/or surface energy contributions to the dynamics and energetics of the system are also taken into account. The model presented here describes the evolution of systems governed by Multi-Phase Multi-Component Reactive Transport (MPMCRT) based on Ensemble Averaging and Classical Irreversible Thermodynamics principles. This novel approach provides a flexible platform to study the dynamics and non-linear feedbacks occurring within various natural systems at different scales. This notably includes major- and trace-element transport, diffusion-controlled trace-element re-equilibration or rheological changes associated with melt generation and migration in the Earth's mantle.

  7. A consistent geochemical modelling approach for the leaching and reactive transport of major and trace elements in MSWI bottom ash

    NARCIS (Netherlands)

    Dijkstra, J.J.; Meeussen, J.C.L.; Sloot, van der H.A.; Comans, R.N.J.


    To improve the long-term environmental risk assessment of waste applications, a predictive "multi-surface" modelling approach has been developed to simultaneously predict the leaching and reactive transport of a broad range of major and trace elements (i.e., pH, Na, Al, Fe, Ca, SO4, Mg, Si, PO4, CO3

  8. Patterns of Children's Adrenocortical Reactivity to Interparental Conflict and Associations with Child Adjustment: A Growth Mixture Modeling Approach (United States)

    Koss, Kalsea J.; George, Melissa R. W.; Davies, Patrick T.; Cicchetti, Dante; Cummings, E. Mark; Sturge-Apple, Melissa L.


    Examining children's physiological functioning is an important direction for understanding the links between interparental conflict and child adjustment. Utilizing growth mixture modeling, the present study examined children's cortisol reactivity patterns in response to a marital dispute. Analyses revealed three different patterns of cortisol…

  9. Patterns of Children's Adrenocortical Reactivity to Interparental Conflict and Associations with Child Adjustment: A Growth Mixture Modeling Approach (United States)

    Koss, Kalsea J.; George, Melissa R. W.; Davies, Patrick T.; Cicchetti, Dante; Cummings, E. Mark; Sturge-Apple, Melissa L.


    Examining children's physiological functioning is an important direction for understanding the links between interparental conflict and child adjustment. Utilizing growth mixture modeling, the present study examined children's cortisol reactivity patterns in response to a marital dispute. Analyses revealed three different patterns of cortisol…

  10. A consistent geochemical modelling approach for the leaching and reactive transport of major and trace elements in MSWI bottom ash

    NARCIS (Netherlands)

    Dijkstra, J.J.; Meeussen, J.C.L.; Sloot, van der H.A.; Comans, R.N.J.


    To improve the long-term environmental risk assessment of waste applications, a predictive "multi-surface" modelling approach has been developed to simultaneously predict the leaching and reactive transport of a broad range of major and trace elements (i.e., pH, Na, Al, Fe, Ca, SO4, Mg, Si, PO4, CO3

  11. Reactive transport modeling in variably saturated porous media with OGS-IPhreeqc (United States)

    He, W.; Beyer, C.; Fleckenstein, J. H.; Jang, E.; Kalbacher, T.; Shao, H.; Wang, W.; Kolditz, O.


    Worldwide, sustainable water resource management becomes an increasingly challenging task due to the growth of population and extensive applications of fertilizer in agriculture. Moreover, climate change causes further stresses to both water quantity and quality. Reactive transport modeling in the coupled soil-aquifer system is a viable approach to assess the impacts of different land use and groundwater exploitation scenarios on the water resources. However, the application of this approach is usually limited in spatial scale and to simplified geochemical systems due to the huge computational expense involved. Such computational expense is not only caused by solving the high non-linearity of the initial boundary value problems of water flow in the unsaturated zone numerically with rather fine spatial and temporal discretization for the correct mass balance and numerical stability, but also by the intensive computational task of quantifying geochemical reactions. In the present study, a flexible and efficient tool for large scale reactive transport modeling in variably saturated porous media and its applications are presented. The open source scientific software OpenGeoSys (OGS) is coupled with the IPhreeqc module of the geochemical solver PHREEQC. The new coupling approach makes full use of advantages from both codes: OGS provides a flexible choice of different numerical approaches for simulation of water flow in the vadose zone such as the pressure-based or mixed forms of Richards equation; whereas the IPhreeqc module leads to a simplification of data storage and its communication with OGS, which greatly facilitates the coupling and code updating. Moreover, a parallelization scheme with MPI (Message Passing Interface) is applied, in which the computational task of water flow and mass transport is partitioned through domain decomposition, whereas the efficient parallelization of geochemical reactions is achieved by smart allocation of computational workload over

  12. Reactive transport modeling in the subsurface environment with OGS-IPhreeqc (United States)

    He, Wenkui; Beyer, Christof; Fleckenstein, Jan; Jang, Eunseon; Kalbacher, Thomas; Naumov, Dimitri; Shao, Haibing; Wang, Wenqing; Kolditz, Olaf


    Worldwide, sustainable water resource management becomes an increasingly challenging task due to the growth of population and extensive applications of fertilizer in agriculture. Moreover, climate change causes further stresses to both water quantity and quality. Reactive transport modeling in the coupled soil-aquifer system is a viable approach to assess the impacts of different land use and groundwater exploitation scenarios on the water resources. However, the application of this approach is usually limited in spatial scale and to simplified geochemical systems due to the huge computational expense involved. Such computational expense is not only caused by solving the high non-linearity of the initial boundary value problems of water flow in the unsaturated zone numerically with rather fine spatial and temporal discretization for the correct mass balance and numerical stability, but also by the intensive computational task of quantifying geochemical reactions. In the present study, a flexible and efficient tool for large scale reactive transport modeling in variably saturated porous media and its applications are presented. The open source scientific software OpenGeoSys (OGS) is coupled with the IPhreeqc module of the geochemical solver PHREEQC. The new coupling approach makes full use of advantages from both codes: OGS provides a flexible choice of different numerical approaches for simulation of water flow in the vadose zone such as the pressure-based or mixed forms of Richards equation; whereas the IPhreeqc module leads to a simplification of data storage and its communication with OGS, which greatly facilitates the coupling and code updating. Moreover, a parallelization scheme with MPI (Message Passing Interface) is applied, in which the computational task of water flow and mass transport is partitioned through domain decomposition, whereas the efficient parallelization of geochemical reactions is achieved by smart allocation of computational workload over

  13. Reactive transport modeling of CO2 injection in the Farnsworth, Texas hydrocarbon field (United States)

    Ahmmed, B.; Appold, M. S.; McPherson, B. J. O. L.; Grigg, R.; White, M. D.


    The Farnsworth hydrocarbon field in northern Texas has been an experimental site for CO2 sequestration and enhanced oil recovery for the U.S. Department of Energy-sponsored Southwest Partnership (SWP) since April, 2013. CO2 is to be injected into the Pennsylvanian Morrow Sandstone at a rate of 200,000 tonnes per year for at least five years. The Morrow is a quartz-rich sandstone that lies at a depth of about 2400 m. Pore water in the Morrow has a total dissolved solids content of about 3600 mg/L dominated by Na, Cl, bicarbonate, and Ca. A reactive solute transport model was constructed for a 1700 × 1700 × 95 m volume using the TOUGHREACT software and the ECO2N equation of state for aqueous brine and CO2. Simulations were carried out to 100 years. The results showed immiscible CO2 gas to be concentrated in a lateral plume extending radially from the well screen, its ascent impeded by vigorous lateral groundwater flow in the more permeable upper Morrow. CO2 was much more widespread in aqueous solution, lowering pH throughout much of the model volume after 100 years, to a minimum of about 4.7. The low reactivity of the Morrow Sandstone due to its quartz-rich matrix and dilute pore fluid resulted in little mineral precipitation or dissolution, with net volume changes for any mineral no higher than order 10-4. The simulations predicted net dissolution of albite, calcite, and chlorite, and net precipitation of dawsonite, illite, and magnesite. The Morrow matrix was predicted to undergo slight net dissolution overall, resulting in porosity increases of up to 0.01%, suggesting that the Morrow would be resistant to significant changes in hydraulic properties as a result of the proposed amount of CO2 injection. For the 100 year simulation times calculated thus far, only a small fraction of the injected CO2 would be sequestered as carbonate minerals, with most of the injected CO2 dissolved in the aqueous phase.

  14. Large-scale modeling of reactive solute transport in fracture zones of granitic bedrocks (United States)

    Molinero, Jorge; Samper, Javier


    Final disposal of high-level radioactive waste in deep repositories located in fractured granite formations is being considered by several countries. The assessment of the safety of such repositories requires using numerical models of groundwater flow, solute transport and chemical processes. These models are being developed from data and knowledge gained from in situ experiments such as the Redox Zone Experiment carried out at the underground laboratory of Äspö in Sweden. This experiment aimed at evaluating the effects of the construction of the access tunnel on the hydrogeological and hydrochemical conditions of a fracture zone intersected by the tunnel. Most chemical species showed dilution trends except for bicarbonate and sulphate which unexpectedly increased with time. Molinero and Samper [Molinero, J. and Samper, J. Groundwater flow and solute transport in fracture zones: an improved model for a large-scale field experiment at Äspö (Sweden). J. Hydraul. Res., 42, Extra Issue, 157-172] presented a two-dimensional water flow and solute transport finite element model which reproduced measured drawdowns and dilution curves of conservative species. Here we extend their model by using a reactive transport which accounts for aqueous complexation, acid-base, redox processes, dissolution-precipitation of calcite, quartz, hematite and pyrite, and cation exchange between Na + and Ca 2+. The model provides field-scale estimates of cation exchange capacity of the fracture zone and redox potential of groundwater recharge. It serves also to identify the mineral phases controlling the solubility of iron. In addition, the model is useful to test the relevance of several geochemical processes. Model results rule out calcite dissolution as the process causing the increase in bicarbonate concentration and reject the following possible sources of sulphate: (1) pyrite dissolution, (2) leaching of alkaline sulphate-rich waters from a nearby rock landfill and (3) dissolution of

  15. Reactive transport in porous media for CO2 sequestration: Pore scale modeling using the lattice Boltzmann method (United States)

    Gao, Jinfang; Xing, Huilin; Tian, Zhiwei; Pearce, Julie K.; Sedek, Mohamed; Golding, Suzanne D.; Rudolph, Victor


    Injection of CO2 subsurface may lead to chemical reactivity of rock where CO2 is dissolved in groundwater. This process can modify pore networks to increase or decrease porosity through mineral dissolution and precipitation. A lattice Boltzmann (LB) based computational model study on the pore scale reactive transport in three dimensional heterogeneous porous media (sandstone consisting of both reactive and non-reactive minerals) is described. This study examines how fluid transport in porous materials subject to reactive conditions is affected by unsteady state local reactions and unstable dissolution fronts. The reaction of a calcite cemented core sub-plug from the Hutton Sandstone of the Surat Basin, Australia, is used as a study case. In particular, the work studies the interaction of acidic fluid (an aqueous solution with an elevated concentration of carbonic acid) with reactive (e.g. calcite) and assumed non-reactive (e.g. quartz) mineral surfaces, mineral dissolution and mass transfer, and resultant porosity change. The proposed model is implemented in our custom LBM code and suitable for studies of multiple mineral reactions with disparate reaction rates. A model for carbonic acid reaction with calcite cemented sandstone in the CO2-water-rock system is verified through laboratory experimental data including micro-CT characterization before and after core reaction at reservoir conditions. The experimentally validated model shows: (1) the dissolution of calcite cement forms conductive channels at the pore scale, and enables the generation of pore throats and connectivity; (2) the model is able to simulate the reaction process until the reaction equilibrium status is achieved (around 1440 days); (3) calcite constituting a volume of around 9.6% of the whole core volume is dissolved and porosity is consequently increased from 1.1% to 10.7% on reaching equilibrium; (4) more than a third of the calcite (constituting 7.4% of the total core volume) is unaffected

  16. Exposure-time based modeling of nonlinear reactive transport in porous media subject to physical and geochemical heterogeneity (United States)

    Sanz-Prat, Alicia; Lu, Chuanhe; Amos, Richard T.; Finkel, Michael; Blowes, David W.; Cirpka, Olaf A.


    the two types of biomass at late times. Results obtained by mapping the exposure-time based results to the two-dimensional domain are compared with simulations based on the two-dimensional, spatially explicit advection-dispersion-reaction equation. Once quasi-steady state has been reached, we find a good agreement in terms of the chemical-compound concentrations between the two approaches inside the reactive zones, whereas the exposure-time based model is not able to capture reactions occurring in the zones with zero electron-donor release. We conclude that exposure-time models provide good approximations of nonlinear bio-reactive transport when transverse mixing is not the overall controlling process and all reactions are essentially restricted to distinct reactive zones.

  17. Exposure-time based modeling of nonlinear reactive transport in porous media subject to physical and geochemical heterogeneity. (United States)

    Sanz-Prat, Alicia; Lu, Chuanhe; Amos, Richard T; Finkel, Michael; Blowes, David W; Cirpka, Olaf A


    the two types of biomass at late times. Results obtained by mapping the exposure-time based results to the two-dimensional domain are compared with simulations based on the two-dimensional, spatially explicit advection-dispersion-reaction equation. Once quasi-steady state has been reached, we find a good agreement in terms of the chemical-compound concentrations between the two approaches inside the reactive zones, whereas the exposure-time based model is not able to capture reactions occurring in the zones with zero electron-donor release. We conclude that exposure-time models provide good approximations of nonlinear bio-reactive transport when transverse mixing is not the overall controlling process and all reactions are essentially restricted to distinct reactive zones.

  18. Numerical modelling of fault reactivation in carbonate rocks under fluid depletion conditions - 2D generic models with a small isolated fault (United States)

    Zhang, Yanhua; Clennell, Michael B.; Delle Piane, Claudio; Ahmed, Shakil; Sarout, Joel


    This generic 2D elastic-plastic modelling investigated the reactivation of a small isolated and critically-stressed fault in carbonate rocks at a reservoir depth level for fluid depletion and normal-faulting stress conditions. The model properties and boundary conditions are based on field and laboratory experimental data from a carbonate reservoir. The results show that a pore pressure perturbation of -25 MPa by depletion can lead to the reactivation of the fault and parts of the surrounding damage zones, producing normal-faulting downthrows and strain localization. The mechanism triggering fault reactivation in a carbonate field is the increase of shear stresses with pore-pressure reduction, due to the decrease of the absolute horizontal stress, which leads to an expanded Mohr's circle and mechanical failure, consistent with the predictions of previous poroelastic models. Two scenarios for fault and damage-zone permeability development are explored: (1) large permeability enhancement of a sealing fault upon reactivation, and (2) fault and damage zone permeability development governed by effective mean stress. In the first scenario, the fault becomes highly permeable to across- and along-fault fluid transport, removing local pore pressure highs/lows arising from the presence of the initially sealing fault. In the second scenario, reactivation induces small permeability enhancement in the fault and parts of damage zones, followed by small post-reactivation permeability reduction. Such permeability changes do not appear to change the original flow capacity of the fault or modify the fluid flow velocity fields dramatically.

  19. Incorporating Geochemical And Microbial Kinetics In Reactive Transport Models For Generation Of Acid Rock Drainage (United States)

    Andre, B. J.; Rajaram, H.; Silverstein, J.


    diffusion model at the scale of a single rock is developed incorporating the proposed kinetic rate expressions. Simulations of initiation, washout and AMD flows are discussed to gain a better understanding of the role of porosity, effective diffusivity and reactive surface area in generating AMD. Simulations indicate that flow boundary conditions control generation of acid rock drainage as porosity increases.

  20. Model neural prostheses with integrated microfluidics: a potential intervention strategy for controlling reactive cell and tissue responses. (United States)

    Retterer, Scott T; Smith, Karen L; Bjornsson, Christopher S; Neeves, Keith B; Spence, Andrew J H; Turner, James N; Shain, William; Isaacson, Michael S


    Model silicon intracortical probes with microfluidic channels were fabricated and tested to examine the feasibility of using diffusion-mediated delivery to deliver therapeutic agents into the volume of tissue exhibiting reactive responses to implanted devices. Three-dimensional probe structures with microfluidic channels were fabricated using surface micromachining and deep reactive ion etching (DRIE) techniques. In vitro functional tests of devices were performed using fluorescence microscopy to record the transient release of Texas Red labeled transferrin (TR-transferrin) and dextran (TR-dextran) from the microchannels into 1% w/v agarose gel. In vivo performance was characterized by inserting devices loaded with TR-transferrin into the premotor cortex of adult male rats. Brain sections were imaged using confocal microscopy. Diffusion of TR-transferrin into the extracellular space and uptake by cells up to 400 microm from the implantation site was observed in brain slices taken 1 h postinsertion. The reactive tissue volume, as indicated by the presence of phosphorylated mitogen-activated protein kinases (MAPKs), was characterized using immunohistochemistry and confocal microscopy. The reactive tissue volume extended 600, 800, and 400 microm radially from the implantation site at 1 h, 24 h, and 6 weeks following insertion, respectively. These results indicate that diffusion-mediated delivery can be part of an effective intervention strategy for the treatment of reactive tissue responses around chronically implanted intracortical probes.

  1. Reactive transport of gentisic acid in a hematite-coated sand column: Experimental study and modeling (United States)

    Hanna, K.; Rusch, B.; Lassabatere, L.; Hofmann, A.; Humbert, B.


    The adsorption of gentisic acid (GA) by hematite nano-particles was examined under static and dynamic conditions by conducting batch and column tests. To simulate natural sediments, the iron oxide was deposited on 10 μm quartz particles. The GA adsorption was described by a surface complexation model fitted to pH-adsorption curves with GA concentrations of 0.1-1 mM in a pH range of 3-10. The surface was described with one type of site ( tbnd FeOH°), while gentisic acid at the surface was described by two surface complexes ( tbnd FeLH 2°, log Kint = 8.9 and tbnd FeLH -, log Kint = -8.2). Modeling was conducted with PHREEQC-2 using the MINTEQ database. From a kinetic point of view, the intrinsic chemical reactions were likely to be the rate-limiting step of sorption (˜10 -3 s -1) while external and internal mass transfer rates (˜10 2 s -1) were much faster. Under flow through conditions (column), adsorption of GA to hematite-coated sand was about 7-times lower than under turbulent mixing (batch). This difference could not be explained by chemical adsorption kinetics as shown by test calculations run with HYDRUS-1D software. Surface complexation model simulations however successfully described the data when the surface area was adjusted, suggesting that under flow conditions the accessibility to the reactive surface sites was reduced. The exact mechanism responsible for the increased mobility of GA could not be determined but some parameters suggested that decreased external mass transfer between solution and surface may play a significant role under flow through conditions.

  2. Uranium transport in a crushed granodiorite: experiments and reactive transport modeling. (United States)

    Dittrich, T M; Reimus, P W


    The primary objective of this study was to develop and demonstrate an experimental method to refine and better parameterize process models for reactive contaminant transport in aqueous subsurface environments and to reduce conservatism in such models without attempting to fully describe the geochemical system. Uranium was used as an example of a moderately adsorbing contaminant because of its relevance in geologic disposal of spent nuclear fuel. A fractured granodiorite from the Grimsel Test Site (GTS) in Switzerland was selected because this system has been studied extensively and field experiments have been conducted with radionuclides including uranium. We evaluated the role of pH, porous media size fraction, and flow interruptions on uranium transport. Rock cores drilled from the GTS were shipped to Los Alamos National Laboratory, characterized by x-ray diffraction and optical microscopy, and used in uranium batch sorption and column breakthrough experiments. A synthetic water was prepared that represented the porewater that would be present after groundwater interacts with bentonite backfill material near a nuclear waste package. Uranium was conservatively transported at pH8.8. Significant adsorption and subsequent desorption was observed at pH ~7, with long desorption tails resulting after switching the column injection solution to uranium-free groundwater. Our experiments were designed to better interrogate this slow desorption behavior. A three-site model predicted sorption rate constants for a pH7.2 solution with a 75-150 μm granodiorite fraction to be 3.5, 0.012, and 0.012 mL/g-h for the forward reactions and 0.49, 0.0025, and 0.001 h(-1) for the reverse reactions. Surface site densities were 1.3, 0.042, and 0.042 μmol/g for the first, second, and third sites, respectively. 10-year simulations show that including a slow binding site increases the arrival time of a uranium pulse by ~70%.

  3. Experiment and Reactive-Burn Modeling in the RDX Based Explosive XTX 8004 (United States)

    Johnson, Carl; Murphy, Mike; Gustavsen, Rick; Jackson, Scott; Vincent, Samuel


    XTX 8004 consists of 80 wt. % cyclotrimethylenetrinitramine (RDX), and 20 wt. % Sylgard 182, a silicone rubber used as a binder. Nominal density is 1.5 g/cm3. Uncured XTX 8004 is putty like and can be molded or extruded. The XTX 8004 detonation product Hugoniot calibration was obtained from cylinder tests using a genetic algorithm approach to parameterize a Jones-Wilkins-Lee (JWL) equation of state. Additionally, we conducted four gas-gun experiments that were instrumented with embedded electromagnetic particle velocity gauges. These provided wave profiles to which we calibrated an Ignition and Growth reactive burn (IGRB) model in ALE3D for 1-D shock to detonation transitions. Further, acceptor and donor XTX 8004 were extruded into opposite sides of a monolithic polymethylmethacrylate (PMMA) block with a known thickness of PMMA forming the attenuator plate, the so-called monolithic gap test (MGT). Detonation and initiation in the XTX 8004 was recorded using multiple ultra-high-speed images of the position of the shock front in the PMMA. Input to the acceptor charge was estimated from stress wave profiles photographed inside the attenuator as well as with photonic Doppler velocimetry (PDV) measurements of the free surface velocity beneath the attenuator plate. Results were simulated using IGRB in ALE3D. Parameterization of IGRB to 1-D vs. 2-D experiments will be discussed.

  4. Aerosol and cloud chemistry of amines from CCS - reactivity experiments and numerical modeling (United States)

    Weller, Christian; Tilgner, Andreas; Herrmann, Hartmut


    Capturing CO2 from the exhaust of power plants using amine scrubbing is a common technology. Therefore, amines can be released during the carbon capture process. To investigate the tropospheric chemical fate of amines from CO2 capturing processes and their oxidation products, the impact of aqueous aerosol particles and cloud droplets on the amine chemistry has been considered. Aqueous phase reactivity experiments of NO3 radicals and ozone with relevant amines and their corresponding nitrosamines were performed. Furthermore, nitrosamine formation and nitrosamine photolysis was investigated during laboratory experiments. These experiments implicated that aqueous phase photolysis can be an effective sink for nitrosamines and that ozone is unreactive towards amines and nitrosamines. Multiphase phase oxidation schemes of amines, nitrosamines and amides were developed, coupled to the existing multiphase chemistry mechanism CAPRAM and built into the Lagrangian parcel model SPACCIM using published and newly measured data. As a result, both deliquescent particles and cloud droplets are important compartments for the multiphase processing of amines and their products. Amines can be readily oxidised by OH radicals in the gas and cloud phase during daytime summer conditions. However, amine oxidation is restricted during winter conditions with low photochemical activity leading to long lifetimes of amines. The importance of the gas and aqueous phase depends strongly on the partitioning of the different amines. Furthermore, the simulations revealed that the aqueous formation of nitrosamines in aerosol particles and could droplets is not a relevant process under tropospheric conditions.

  5. Biological stress reactivity as an index of the two polarities of the experience model. (United States)

    Silva, Jaime R; Vivanco-Carlevari, Anastassia; Barrientos, Mauricio; Martínez, Claudio; Salazar, Luis A; Krause, Mariane


    The two-polarities model of personality argues that experience is organized around two axes: interpersonal relatedness and self-definition. Differential emphasis on one of these poles defines adaptive and pathological experiences, generating anaclitic or introjective tendencies. The anaclitic pattern, on one hand, has been conceptually related with an exaggerated emphasis on interpersonal relatedness. On the other hand, the introjective pattern has been connected to high levels of self-criticism. The aim of this study was to investigate the psychophysiological basis for this relationship. Specifically, we hypothesized that the anaclitic individual should have a higher biological reactivity to stress (BRS), measured by the cortisol concentration in saliva, in an interpersonal stress induction protocol (Trier Social Stress Test). Contrary to what was expected, the results indicated that introjective participants presented a higher BSR than the anaclitic group. Interestingly, in contrast to their higher BSR, the introjective group reported a diminished subjective stress in relation to the average. In the anaclitic group, a tendency that goes in the opposite direction was found. Theoretical implications of these findings were discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Synthesis, structure and reactivity of Ni site models of [NiFeSe] hydrogenases. (United States)

    Wombwell, Claire; Reisner, Erwin


    A series of structural models of the Ni centre in [NiFeSe] hydrogenases has been developed which exhibits key structural features of the Ni site in the H2 cycling enzyme. Specifically, two complexes with a hydrogenase-analogous four-coordinate 'NiS3Se' primary coordination sphere and complexes with a 'NiS2Se2' and a 'NiS4' core are reported. The reactivity of the complexes towards oxygen and protons shows some relevance to the chemistry of [NiFeSe] hydrogenases. Exposure of a 'NiS3Se' complex to atmospheric oxygen results in the oxidation of the selenolate group in the complex to a diselenide, which is released from the nickel site. Oxidation of the selenolate ligand on Ni occurs approximately four times faster than oxidation with the analogous sulfur complex. Reaction of the complexes with one equivalent of HBF4 results in protonation of the monodentate chalcogenolate and the release of this ligand from the metal centre as a thiol or selenol. Unrelated to their biomimetic nature, the complexes serve also as molecular precursors to modify electrodes with Ni-S-Se containing particles by electrochemical deposition. The activated electrodes evolve H2 in pH neutral water with an electrocatalytic onset potential of -0.6 V and a current density of 15 μA cm(-2) at -0.75 V vs. NHE.

  7. AIREBO-M: A reactive model for hydrocarbons at extreme pressures

    Energy Technology Data Exchange (ETDEWEB)

    O’Connor, Thomas C., E-mail:; Robbins, Mark O., E-mail: [Department of Physics and Astronomy, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Andzelm, Jan, E-mail: [Macromolecular Science and Technology Branch, U.S. Army Research Laboratory, Aberdeen, Maryland 21005 (United States)


    The Adaptive Intermolecular Reactive Empirical Bond Order potential (AIREBO) for hydrocarbons has been widely used to study dynamic bonding processes under ambient conditions. However, its intermolecular interactions are modeled by a Lennard-Jones (LJ) potential whose unphysically divergent power-law repulsion causes AIREBO to fail when applied to systems at high pressure. We present a modified potential, AIREBO-M, where we have replaced the singular Lennard-Jones potential with a Morse potential. We optimize the new functional form to improve intermolecular steric repulsions, while preserving the ambient thermodynamics of the original potentials as much as possible. The potential is fit to experimental measurements of the layer spacing of graphite up to 14 GPa and first principles calculations of steric interactions between small alkanes. To validate AIREBO-M’s accuracy and transferability, we apply it to a graphite bilayer and orthorhombic polyethylene. AIREBO-M gives bilayer compression consistent with quantum calculations, and it accurately reproduces the quasistatic and shock compression of orthorhombic polyethlyene up to at least 40 GPa.

  8. Reactivation in working memory: an attractor network model of free recall. (United States)

    Lansner, Anders; Marklund, Petter; Sikström, Sverker; Nilsson, Lars-Göran


    The dynamic nature of human working memory, the general-purpose system for processing continuous input, while keeping no longer externally available information active in the background, is well captured in immediate free recall of supraspan word-lists. Free recall tasks produce several benchmark memory phenomena, like the U-shaped serial position curve, reflecting enhanced memory for early and late list items. To account for empirical data, including primacy and recency as well as contiguity effects, we propose here a neurobiologically based neural network model that unifies short- and long-term forms of memory and challenges both the standard view of working memory as persistent activity and dual-store accounts of free recall. Rapidly expressed and volatile synaptic plasticity, modulated intrinsic excitability, and spike-frequency adaptation are suggested as key cellular mechanisms underlying working memory encoding, reactivation and recall. Recent findings on the synaptic and molecular mechanisms behind early LTP and on spiking activity during delayed-match-to-sample tasks support this view.

  9. Reactive flow modeling of small scale detonation failure experiments for a baseline non-ideal explosive (United States)

    Kittell, David E.; Cummock, Nick R.; Son, Steven F.


    Small scale characterization experiments using only 1-5 g of a baseline ammonium nitrate plus fuel oil (ANFO) explosive are discussed and simulated using an ignition and growth reactive flow model. There exists a strong need for the small scale characterization of non-ideal explosives in order to adequately survey the wide parameter space in sample composition, density, and microstructure of these materials. However, it is largely unknown in the scientific community whether any useful or meaningful result may be obtained from detonation failure, and whether a minimum sample size or level of confinement exists for the experiments. In this work, it is shown that the parameters of an ignition and growth rate law may be calibrated using the small scale data, which is obtained from a 35 GHz microwave interferometer. Calibration is feasible when the samples are heavily confined and overdriven; this conclusion is supported with detailed simulation output, including pressure and reaction contours inside the ANFO samples. The resulting shock wave velocity is most likely a combined chemical-mechanical response, and simulations of these experiments require an accurate unreacted equation of state (EOS) in addition to the calibrated reaction rate. Other experiments are proposed to gain further insight into the detonation failure data, as well as to help discriminate between the role of the EOS and reaction rate in predicting the measured outcome.

  10. Reactivation in working memory: an attractor network model of free recall.

    Directory of Open Access Journals (Sweden)

    Anders Lansner

    Full Text Available The dynamic nature of human working memory, the general-purpose system for processing continuous input, while keeping no longer externally available information active in the background, is well captured in immediate free recall of supraspan word-lists. Free recall tasks produce several benchmark memory phenomena, like the U-shaped serial position curve, reflecting enhanced memory for early and late list items. To account for empirical data, including primacy and recency as well as contiguity effects, we propose here a neurobiologically based neural network model that unifies short- and long-term forms of memory and challenges both the standard view of working memory as persistent activity and dual-store accounts of free recall. Rapidly expressed and volatile synaptic plasticity, modulated intrinsic excitability, and spike-frequency adaptation are suggested as key cellular mechanisms underlying working memory encoding, reactivation and recall. Recent findings on the synaptic and molecular mechanisms behind early LTP and on spiking activity during delayed-match-to-sample tasks support this view.

  11. Reactive flow models of the Anarraaq Zn-Pb-Ag deposit, Red Dog district, Alaska (United States)

    Schardt, C.; Garven, G.; Kelley, K.D.; Leach, D.L.


    The Red Dog ore deposit district in the Brooks Range of northern Alaska is host to several high-grade, shale-hosted Zn + Pb deposits. Due to the complex history and deformation of these ore deposits, the geological and hydrological conditions at the time of formation are poorly understood. Using geological observations and fluid inclusion data as constraints, numerical heat and fluid flow simulations of the Anarraaq ore deposit environment and coupled reactive flow simulations of a section of the ore body were conducted to gain more insight into the conditions of ore body formation. Results suggest that the ore body and associated base metal zonation may have formed by the mixing of oxidized, saline, metal-bearing hydrothermal fluids (source. Forward modeling results also predict the distribution of pyrite and quartz in agreement with field observations and indicate a reaction front moving from the initial mixing interface into the radiolarite rocks. Heuristic mass calculations suggest that ore grades and base metal accumulation comparable to those found in the field (18% Zn, 5% Pb) are predicted to be reached after about 0.3 My for initial conditions (30 ppm Zn, 3 ppm Pb; 20% deposition efficiency). ?? Springer-Verlag 2008.

  12. Reactive flow models of the Anarraaq Zn-Pb-Ag deposit, Red Dog district, Alaska (United States)

    Schardt, Christian; Garven, Grant; Kelley, Karen D.; Leach, David L.


    The Red Dog ore deposit district in the Brooks Range of northern Alaska is host to several high-grade, shale-hosted Zn + Pb deposits. Due to the complex history and deformation of these ore deposits, the geological and hydrological conditions at the time of formation are poorly understood. Using geological observations and fluid inclusion data as constraints, numerical heat and fluid flow simulations of the Anarraaq ore deposit environment and coupled reactive flow simulations of a section of the ore body were conducted to gain more insight into the conditions of ore body formation. Results suggest that the ore body and associated base metal zonation may have formed by the mixing of oxidized, saline, metal-bearing hydrothermal fluids (<200°C) with reducing, HS-rich pore fluids within radiolarite-rich host rocks. Sphalerite and galena concentrations and base metal sulfide distribution are primarily controlled by the nature of the pore fluids, i.e., the extent and duration of the HS- source. Forward modeling results also predict the distribution of pyrite and quartz in agreement with field observations and indicate a reaction front moving from the initial mixing interface into the radiolarite rocks. Heuristic mass calculations suggest that ore grades and base metal accumulation comparable to those found in the field (18% Zn, 5% Pb) are predicted to be reached after about 0.3 My for initial conditions (30 ppm Zn, 3 ppm Pb; 20% deposition efficiency).

  13. Modeling experiments on the deceleration and reactivation of Kangerlussuup Sermusa, West Greenland (United States)

    Rezvanbehbahani, S.; Stearns, L. A.; van der Veen, C. J.; Catania, G. A.


    Seasonal variations in outlet glacier velocity due to basal sliding are well-documented and typically involve acceleration early in the melt season due to enhanced sliding as a result of inefficient drainage of surface water reaching the bed. However, velocity observations from Kangerlussuup Sermusa (KS) in West Greenland contradict this pattern. Instead, ice velocity at KS shows no significant change in early spring compared with the previous winter. This sluggish response of the glacier to spring melt is often followed by an extreme, and short-lived, deceleration. For example, in August 2010, the lower 20 km of the trunk decelerated from about 1600 m a-1 to less than 250 m a-1; this event was followed by a rapid reactivation back to the previous velocity in less than 60 days. Available records since 2006 show that the sequence of steady spring velocity, followed by summer deceleration, and rapid fall reactivation occurs annually; however, the magnitudes of deceleration vary. In this regard, the response of KS to regional environmental forcings is unique compared to its neighboring glaciers. In this study, we investigate whether the unique behavior of KS can be explained by the interaction between changes in basal conditions and the local geometry of the glacier. We model the glacier flow by solving full-Stokes equations using the finite element method in the open-source FEniCS framework. Assuming isothermal ice within the lower trunk, we run experiments on the mechanical properties and boundary conditions of the glacier. These experiments include spatio-temporal changes in basal slipperiness, periodic melt-water influx to the bed, and ice viscosity variations due to changes in melt-water supply to the bed. We also conduct sensitivity analyses on the glacier flow with different ice geometries (e.g. thickness and surface slope) to investigate conditions under which we can produce the unique seasonal behavior of KS. Finally, we assess the impact of the combination

  14. Reactive Power Compensation Method Considering Minimum Effective Reactive Power Reserve (United States)

    Gong, Yiyu; Zhang, Kai; Pu, Zhang; Li, Xuenan; Zuo, Xianghong; Zhen, Jiao; Sudan, Teng


    According to the calculation model of minimum generator reactive power reserve of power system voltage stability under the premise of the guarantee, the reactive power management system with reactive power compensation combined generator, the formation of a multi-objective optimization problem, propose a reactive power reserve is considered the minimum generator reactive power compensation optimization method. This method through the improvement of the objective function and constraint conditions, when the system load growth, relying solely on reactive power generation system can not meet the requirement of safe operation, increase the reactive power reserve to solve the problem of minimum generator reactive power compensation in the case of load node.

  15. Regional CO2 flux estimates from estuarine environments: a reactive-transport modeling approach (United States)

    Goossens, Nicolas; Laruelle, Goulven G.; Arndt, Sandra; Regnier, Pierre


    Estuaries are key components of the land-ocean continuum and play an important role in the global carbon cycle. Large amounts of terrestrial carbon are channelled through estuaries before reaching the ocean. During estuarine transit, numerous biogeochemical processes transform the carbon flux, resulting in a significant CO2 evasion flux to the atmosphere. The global estuarine CO2 outgassing is evaluated at 0.25±0.25 PgC yr-1. Yet, these estimates rely on the extrapolation of local measurements and the scarcity of such measurements conducts to large uncertainties. Furthermore, the global quantification is biased towards anthropogenically impacted estuarine systems located in industrialized countries. Here we provide a first assessment of the estuarine carbon budget and, in particular, CO2 evasion fluxes using a generic and effective reactive-transport model (RTM) approach that is applicable at the regional scale. The new approach is based on the mutual dependency between estuarine geometry and hydrodynamics and uses idealized estuarine geometries. Global river databases (GLORICH) and watershed model outputs (GlobalNEWS) are used to quantify input fluxes for the generic estuarine model. The new modeling approach provides not only a quantification of the estuarine carbon budget, but also allows disentangling the relative contributions of biogeochemical and physical processes to estuarine CO2 emissions. Preliminary results are presented for the North Eastern coast of the US. Model results are consistent with observations and indicate that the net heterotrophy of these systems is the major contributor to estuarine CO2 fluxes (>50%), followed by outgassing of supersaturated riverine waters and nitrification. Results also highlight the strong seasonality in the biogeochemical dynamics. In addition, significant heterogeneity is observed across different estuaries due to spatial heterogeneities in climate forcing, estuarine geometry or riverine input fluxes. The proposed

  16. Modelling of Magnetron Sputtering of Tungsten Oxide with Reactive Gas Pulsing



    Reactive sputtering is one of the most commonly employed processes for the deposition of thin films. However, the range of applications is limited by inherent instabilities, which necessitates the use of a complex feedback control of reactive gas (RG) partial pressure. Recently pulsing of the RG has been suggested as a possible alternative. In this report, the concept of periodically switching the RG flow between two different values is applied to the deposition of tungsten oxide. The trends ...

  17. The Development and Application of Reactive Transport Modeling Techniques to Study Radionuclide Migration at Yucca Mountain, NV

    Energy Technology Data Exchange (ETDEWEB)

    Viswanathan, Hari Selvi


    Yucca Mountain, Nevada has been chosen as a possible site for the first high level radioactive waste repository in the United States. As part of the site investigation studies, we need to make scientifically rigorous estimations of radionuclide migration in the event of a repository breach. Performance assessment models used to make these estimations are computationally intensive. We have developed two reactive transport modeling techniques to simulate radionuclide transport at Yucca Mountain: (1) the selective coupling approach applied to the convection-dispersion-reaction (CDR) model and (2) a reactive stream tube approach (RST). These models were designed to capture the important processes that influence radionuclide migration while being computationally efficient. The conventional method of modeling reactive transport models is to solve a coupled set of multi-dimensional partial differential equations for the relevant chemical components in the system. We have developed an iterative solution technique, denoted the selective coupling method, that represents a versatile alternative to traditional uncoupled iterative techniques and the filly coupled global implicit method. We show that selective coupling results in computational and memory savings relative to these approaches. We develop RST as an alternative to the CDR method for solving large two- or three-dimensional reactive transport simulations for cases in which one is interested in predicting the flux across a specific control plane. In the RST method, the multidimensional problem is reduced to a series of one-dimensional transport simulations along streamlines. The key assumption with RST is that mixing at the control plane approximates the transverse dispersion between streamlines. We compare the CDR and RST approaches for several scenarios that are relevant to the Yucca Mountain Project. For example, we apply the CDR and RST approaches to model an ongoing field experiment called the Unsaturated Zone

  18. Assessing the performance of a permeable reactive barrier-aquifer system using a dual-domain solute transport model (United States)

    Chen, Jui-Sheng; Hsu, Shao-Yiu; Li, Ming-Hsu; Liu, Chen-Wuing


    Transport behavior through a permeable reactive barrier (PRB)-aquifer system is complicated because of the different physical and chemical properties of the PRB and the aquifer. Dual-domain solute transport models are efficient tools for better understanding the various processes and mechanisms of reactive solute transport through a PRB-aquifer system. This study develops a dual-domain analytical model to assess the physical and chemical processes of two-dimensional reactive solute transport through a PRB-aquifer system. The dispersion processes of a dual-domain system on the solute transport are investigated. The results show that the dispersion parameters in a dual-domain system synchronously govern the dynamic shape of the contaminant plume. The low longitudinal and transverse dispersion coefficients of a dual-domain system may restrict the spreading of the plume and elevate the plume's concentration level. The derived analytical solution is applied to explore how the different reactive transport processes affect the performance of a PRB-aquifer system. The results show that the first-order decay rate constant of the PRB has a critical effect on the performance of the PRB-aquifer system, whereas the effects of the physical dispersion properties on PRB performance are less significant.

  19. Evaluation of Proactive, Reactive and Hybrid Ad hoc Routing Protocol for various Battery models in VANET using Qualnet

    CERN Document Server

    Sharma, Manish


    In VANET high speed is the real characteristics which leads frequent breakdown, interference etc. In this paper we studied various Ad hoc routing protocols, Reactive, Proactive & Hybrid, taking into consideration various VANET parameters like speed, altitude etc in real traffic scenario and evaluated them for various battery models for energy conservation.. The AODV and DYMO (Reactive), OLSR (Proactive) and ZRP (hybrid) protocols are compared for battery models Duracell AA(MX- 1500),Duracell AAA(MN-2400),Duracell AAA(MX-2400), Duracell C-MN(MN-1400),Panasonic AA standard using Qualnet as a Simulation tool. Since Energy conservation is main focus area nowadays. Hence performance of the protocols with various battery models counts and helps to make a right selection. Varying parameters of VANET shows that in the real traffic scenarios proactive protocol performs more efficiently for energy conservation.

  20. Modeling dry deposition of reactive nitrogen in China with RAMS-CMAQ (United States)

    Han, Xiao; Zhang, Meigen; Skorokhod, Andrei; Kou, Xingxia


    China has the world highest production of reactive nitrogen (Nr), and the Nr consumption increased sharply during the last decade. However, the potential environmental influence of dry nitrogen (N) deposition in China remains uncertain due to that the long-term measurement or remote sensing of various N species are difficult. This requires a better understanding of dry N deposition over China in its various forms and including magnitude and distribution features. Thus, the air quality modeling system RAMS-CMAQ was applied to simulate dry deposition of Nr over China from 2010 to 2014. The model results were then analyzed to investigate the long-term spatial and temporal distributions of major inorganic nitrogen (N) components (10 species) and selected organic N components (5 species). Comparisons between modeled and observed deposition rates and surface mass concentrations showed generally good agreement. Model results indicated a total dry N deposition budget of 9.31 Tg N yr-1 in China, including 4.29 Tg N yr-1 as NOy and 4.43 Tg N yr-1 as NH3. NOy was the main component of dry N deposition in the Beijing-Tianjin-Hebei area (0.31 Tg N yr-1), the Yangtze River Delta (0.29 Tg N yr-1), and the Pearl River Delta (0.09 Tg N yr-1), where the major megacity clusters of China are located. NH3 was the main component of dry N deposition in Shandong province (0.24 Tg N yr-1), Northeast China (0.46 Tg N yr-1), the Sichuan Basin (0.48 Tg N yr-1), and central China (0.95 Tg N yr-1), where the major agricultural regions are located. The highest values of the deposition flux for NH3 occurred in Shandong province (19.40 kg N ha-1 yr-1) and Beijing-Tianjin-Hebei (17.20 kg N ha-1 yr-1). The seasonal variation of total dry N deposition was obvious in the east part of China, and was higher in July and lower in January. The spatio-temporal variations and major sources of dry N deposition were strongly heterogeneous, implying that the comprehensive pollution control strategies should be

  1. Long-term reactive transport modelling of stabilized/solidified waste: from dynamic leaching tests to disposal scenarios

    Energy Technology Data Exchange (ETDEWEB)

    Windt, Laurent de [Ecole des Mines de Paris, CG-Hydrodynamics and Reaction Group, 35 R. St-Honore, 77300 Fontainebleau (France)]. E-mail:; Badreddine, Rabia [INERIS, Direction des Risques Chroniques, Unite Dechets et Sites Pollues, Parc Technologique Alata BP 2, 60550 Verneuil-en-Halatte (France); Lagneau, Vincent [Ecole des Mines de Paris, CG-Hydrodynamics and Reaction Group, 35 R. St-Honore, 77300 Fontainebleau (France)


    Environmental impact assessment of hazardous waste disposal relies, among others, on standardized leaching tests characterized by a strong coupling between diffusion and chemical processes. In that respect, this study shows that reactive transport modelling is a useful tool to extrapolate laboratory results to site conditions characterized by lower solution/solid (L/S) ratios, site specific geometry, infiltration, etc. A cement solidified/stabilized (S/S) waste containing lead is investigated as a typical example. The reactive transport model developed in a previous study to simulate the initial state of the waste as well as laboratory batch and dynamic tests is first summarized. Using the same numerical code (HYTEC), this model is then integrated to a simplified waste disposal scenario assuming a defective cover and rain water infiltration. The coupled evolution of the S/S waste chemistry and the pollutant plume migration are modelled assessing the importance of the cracking state of the monolithic waste. The studied configurations correspond to an undamaged and fully sealed system, a few main fractures between undamaged monoliths and, finally, a dense crack-network in the monoliths. The model considers the potential effects of cracking, first the increase of rain water and carbon dioxide infiltration and, secondly, the increase of L/S ratio and reactive surfaces, using either explicit fracture representation or dual porosity approaches.

  2. Goethite surface reactivity: III. Unifying arsenate adsorption behavior through a variable crystal face - Site density model (United States)

    Salazar-Camacho, Carlos; Villalobos, Mario


    goethite, may be performed for each preparation either by experimental determination of site saturation by an index ion (e.g., chromate), or by achieving congruency of proton adsorption data with those of ideal goethites when plotted as percentage of proton-reactive ( lbond2 FeOH + lbond2 Fe 3OH) sites occupied. The surface arsenate complexes proposed additionally explained: (1) the higher affinity of goethite for As(V) than for Cr(VI) at high pH, and thus the gentle slope of the arsenate pH adsorption edges; and (2) the lower adsorption capacity for As(V) than for Cr(VI) at low pH on low-surface area goethites, through incomplete lbond2 FeOH site occupancy of As(V). The model is very promising as a practical means of predicting the adsorption behavior of arsenate on any goethite preparation, and may extend to predictive capabilities for adsorption behavior of many other relevant oxyanions, as well as for explaining differences in ligand-promoted surface transformation processes on goethite as a function of particle size.

  3. Assessment of RELAP5 point kinetic model against reactivity insertion transient in the IAEA 10 MW MTR research reactor

    Energy Technology Data Exchange (ETDEWEB)

    Hamidouche, T., E-mail: t.hamidouche@crna.d [Division de l' Environnement, de la Surete et des Dechets Radioactifs, Centre de Recherche Nucleaire d' Alger, 02 Boulevard Frantz Fanon, BP 399 Alger RP (Algeria); Bousbia-Salah, A. [DIMNP - University of Pisa, Via Diotisalvi 02, 56126 Pisa (Italy)


    The current study emphasizes an aspect related to the assessment of a model embedded in a computer code. The study concerns more particularly the point neutron kinetics model of the RELAP5/Mod3 code which is worldwide used. The model is assessed against positive reactivity insertion transient taking into account calculations involving thermal-hydraulic feedback as well as transients with no feedback effects. It was concluded that the RELAP5 point kinetics model provides unphysical power evolution trends due most probably to a bug during the programming process.

  4. Reactive transport modeling of secondary water quality impacts due to anaerobic bioremediation (United States)

    Ng, G. H. C.; Bekins, B. A.; Kent, D. B.; Borden, R. C.; Tillotson, J.


    Bioremediation using electron donor addition produces reducing conditions in an aquifer that promote the anaerobic biodegradation of contaminants such as chlorinated solvents. There is growing concern about secondary water quality impacts (SWQIs) triggered by the injection of electron donors, due to redox reactions with electron acceptors other than the target contaminant. Secondary plumes, including those with elevated concentrations of Mn(II), Fe(II), and CH4, may create long-lasting impairment of water quality. Understanding conditions that control the production and attenuation of SWQIs is needed for guiding responsible bioremediation strategies that limit unintended consequences. Using a reactive transport model developed with data from long-term anaerobic biodegradation monitoring sites, we simulate diverse geochemical scenarios to examine the sensitivity of secondary plume extent and persistence to a range of aquifer properties and treatment implementations. Data compiled from anaerobic bioremediation sites, which include variable physical and geochemical relationships, provide the basis for the conditions evaluated. Our simulations show that reduced metal and CH4 plumes may be significantly attenuated due to immobilization (through sorption and/or precipitation) and outgassing, respectively, and that recovery time to background conditions depends strongly on the chemical forms of reduced metals on sediments. Unsurprisingly, scenarios that do not easily allow outgassing (e.g. deeper injections) led to higher CH4 concentrations, and scenarios with higher hydraulic conductivity produced more dilute concentrations of secondary species. Results are sensitive to the assumed capacity for Fe(II) sorption and reductive dissolution rates of Fe(III) oxides, which control Fe(II) concentrations. Simulations also demonstrated the potential importance of chemical reactions between different secondary components. For example, limited CH4 loss from outgassing and Fe

  5. Coupled flow and geomechanics modeling of fracture reactivation and induced seismicity in the Basel geothermal field (United States)

    Tyukhova, A.; Castineira, D.; Juanes, R.


    Triggered and induced seismicity is at the cornerstone of discussions surrounding a wide range of subsurface technologies, e.g. unconventional hydrocarbon recovery, geologic carbon sequestration, underground gas storage, and geothermal energy extraction. We revisit the geothermal experiment in Basel, Switzerland, in which over 11 thousand cubic meters of water were injected into deep fractured crystalline rock. The injection took place in December 2006 and was performed at a single injection well, in three stages with increasing injection rate. Seismicity in the region increased during the experiment—with most of the seismic events occurring in the month following injection—and declined slowly after, but with seismic events still being recorded years after injection. The increase in seismicity is caused by reactivation of the pre-existing fractures: an increase in pore pressure decreases the normal effective stress across the fracture, which according to the Mohr-Coulomb failure criterion are therefore more prone to slip. The underlying processes, however, may be more complex. It is unclear the role that enhanced hydraulic connectivity in the fracture network plays on triggered seismicity, and on the emergence of seismicity clusters in space. It is also unclear what determines the delay between injection and recorded seismicity, and whether it can be explained by means of pressure propagation and/or dynamic weakening of fractures due to a drop in the friction coefficient as a result of decreased roughness from fracture slip. Here, we employ a computational model of coupled flow and geomechanics to quantitatively assess the impact of fluid injection on the recorded seismicity. We develop a simulation model that incorporates more than ten fractures, whose location, rake and dip are consistent with clusters of seismicity from a relocation of hypocenters and focal mechanisms. We adopt a multiscale description of flow (representing these fractures planes explicitly

  6. a Method to Correct Yield Surface Drift in Soil Plasticity Under Mixed Control and Explicit Integration (United States)

    Mattsson, Hans; Axelsson, Kennet; Klisinski, Marek


    When applying an explicit integration algorithm in e.g. soil plasticity, the predicted stress point at the end of an elastoplastic increment of loading might not be situated on the updated current yield surface. This so-called yield surface drift could generally be held under control by using small integration steps. Another possibility, when circumstances might demand larger steps, is to adopt a drift correction method. In this paper, a drift correction method for mixed control in soil plasticity, under drained as well as undrained conditions, is proposed. By simulating triaxial tests in a Constitutive Driver, the capability and efficiency of this correction method, under different choices of implementation, have been analysed. It was concluded that the proposed drift correction method, for quite marginal additional computational cost, was able to correct successfully for yield surface drift giving results in close agreement to those obtained with a very large number of integration steps.

  7. OS3D/GIMRT software for modeling multicomponent-multidimensional reactive transport

    Energy Technology Data Exchange (ETDEWEB)

    CI Steefel; SB Yabusaki


    OS3D/GIMRT is a numerical software package for simulating multicomponent reactive transport in porous media. The package consists of two principal components: (1) the code OS3D (Operator Splitting 3-Dimensional Reactive Transport) which simulates reactive transport by either splitting the reaction and transport steps in time, i.e., the classic time or operator splitting approach, or by iterating sequentially between reactions and transport, and (2) the code GIMRT (Global Implicit Multicomponent Reactive Transport) which treats up to two dimensional reactive transport with a one step or global implicit approach. Although the two codes do not yet have totally identical capabilities, they can be run from the same input file, allowing comparisons to be made between the two approaches in many cases. The advantages and disadvantages of the two approaches are discussed more fully below, but in general OS3D is designed for simulation of transient concentration fronts, particularly under high Peclet number transport conditions, because of its use of a total variation diminishing or TVD transport algorithm. GIMRT is suited for simulating water-rock alteration over long periods of time where the aqueous concentration field is at or close to a quasi-stationary state and the numerical transport errors are less important. Where water-rock interaction occurs over geological periods of time, GIMRT may be preferable to OS3D because of its ability to take larger time steps.

  8. Modelling of the reactive sputtering process with non-uniform discharge current density and different temperature conditions (United States)

    Vašina, P; Hytková, T; Eliáš, M


    The majority of current models of the reactive magnetron sputtering assume a uniform shape of the discharge current density and the same temperature near the target and the substrate. However, in the real experimental set-up, the presence of the magnetic field causes high density plasma to form in front of the cathode in the shape of a toroid. Consequently, the discharge current density is laterally non-uniform. In addition to this, the heating of the background gas by sputtered particles, which is usually referred to as the gas rarefaction, plays an important role. This paper presents an extended model of the reactive magnetron sputtering that assumes the non-uniform discharge current density and which accommodates the gas rarefaction effect. It is devoted mainly to the study of the behaviour of the reactive sputtering rather that to the prediction of the coating properties. Outputs of this model are compared with those that assume uniform discharge current density and uniform temperature profile in the deposition chamber. Particular attention is paid to the modelling of the radial variation of the target composition near transitions from the metallic to the compound mode and vice versa. A study of the target utilization in the metallic and compound mode is performed for two different discharge current density profiles corresponding to typical two pole and multipole magnetics available on the market now. Different shapes of the discharge current density were tested. Finally, hysteresis curves are plotted for various temperature conditions in the reactor.

  9. Quadratic models of AC-DC power flow and optimal reactive power flow with HVDC and UPFC controls

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Juan; Yan, Wei; Wen, Lili [The Key Laboratory of High Voltage Engineering and Electrical New Technology, Ministry of Education, Electrical Engineering College of Chongqing University, Chongqing 400030 (China); Li, Wenyuan [British Columbia Transmission Corporation (BCTC), Suite 1100, Four Bentall Center, 1055 Dunsmuir Street, P.O. Box 49260, Vancouver, BC (Canada)


    Quadratic models of power flow (PF) and optimal reactive power flow (ORPF) for AC-DC power systems are proposed in the paper. Voltage magnitudes at the two sides of ideal converter transformers are used as additional state variables to build the quadratic models. Effects of converter controls on equality constraints are considered. The quadratic expression of unified power flow controller (UPFC) is also developed and incorporated into the proposed models. The proposed PF model retaining nonlinearity has a better convergence feature and requires less CPU time compared to traditional PF models. The Hessian matrices in the quadratic AC-DC ORPF model are constant and need to be calculated only once in the entire optimization process, which speeds up the calculation greatly. Results obtained from the four IEEE test systems and an actual utility system indicate that the proposed quadratic models achieve a superior performance than conventional models. (author)

  10. Chemical weathering rates in deep-sea sediments: Comparison of multicomponent reactive transport models and estimates based on 234U (United States)

    Maher, K.; Steefel, C. I.; Depaolo, D. J.


    Chemical weathering rates in natural systems are typically much slower than expected based on experiments and theory. There are several possible explanations. However, because it has been difficult to determine what effects in particular reduce the rates in specific settings, natural rates remain difficult to predict. Silicate-rich deep-sea sediments provide an ideal in-situ laboratory for investigating weathering rates because certain potentially important factors, such as advective transport through heterogeneous media, limitations on the availability of reactive surface area due to low porosity and/or cementation, unsaturated flow conditions, and seasonal variations in fluid flux and temperature, do not occur in this setting. Geochemical profiles from Site 984 in the North Atlantic are modeled using a multi-component reactive transport model (CRUNCH) to determine in-situ rates of plagioclase dissolution and other diagenetic processes, including sulfate reduction and anaerobic methane oxidation. Various possible processes which might contribute to slower rates in the field are considered, including the effect of mineral saturation state, secondary precipitation of clays, inhibition by dissolved aluminum, and the availability of reactive surface area. The reactive transport model includes an isotopic solid-solution formulation that tracks the isotopic composition of precipitating (calcite) and dissolving (plagioclase and calcite) phases, thus allowing the determination of plagioclase dissolution rates. The rate constants for plagioclase determined by geochemical transport modeling of major element profiles are within the same range determined from U-series calculations and suggest that natural weathering rates for this system are on the order of 10-17.5 to 10-17.7 mol/m2/sec assuming estimates of reactive surface area are correct, several orders of magnitude slower than laboratory-derived rates. The slow plagioclase rates are most likely due to the fact that

  11. Implementing fluid dynamics obtained from GeoPET in reactive transport models (United States)

    Lippmann-Pipke, Johanna; Eichelbaum, Sebastian; Kulenkampff, Johannes


    Flow and transport simulations in geomaterials are commonly conducted on high-resolution tomograms (μCT) of the pore structure or stochastic models that are calibrated with measured integral quantities, like break through curves (BTC). Yet, there existed virtually no method for experimental verification of the simulated velocity distribution results. Positron emission tomography (PET) has unrivaled sensitivity and robustness for non-destructive, quantitative, spatio-temporal measurement of tracer concentrations in body tissue. In the past decade, we empowered PET for its applicability in opaque/geological media - GeoPET (Kulenkampff et al.; Kulenkampff et al., 2008; Zakhnini et al., 2013) and have developed detailed correction schemes to bring the images into sharp focus. Thereby it is the appropriate method for experimental verification and calibration of computer simulations of pore-scale transport by means of the observed propagation of a tracer pulse, c_PET(x,y,z,t). In parallel, we aimed at deriving velocity and porosity distributions directly from our concentration time series of fluid flow processes in geomaterials. This would allow us to directly benefit from lab scale observations and to parameterize respective numerical transport models. For this we have developed a robust spatiotemporal (3D+t) parameter extraction algorithm. Here, we will present its functionality, and demonstrate the use of obtained velocity distributions in finite element simulations of reactive transport processes on drill core scale. Kulenkampff, J., Gruendig, M., Zakhnini, A., Gerasch, R., and Lippmann-Pipke, J.: Process tomography of diffusion with PET for evaluating anisotropy and heterogeneity, Clay Minerals, in press. Kulenkampff, J., Gründig, M., Richter, M., and Enzmann, F.: Evaluation of positron emission tomography for visualisation of migration processes in geomaterials, Physics and Chemistry of the Earth, 33, 937-942, 2008. Zakhnini, A., Kulenkampff, J., Sauerzapf, S

  12. Modeling of fault reactivation and induced seismicity during hydraulic fracturing of shale-gas reservoirs

    Energy Technology Data Exchange (ETDEWEB)

    Rutqvist, Jonny; Rinaldi, Antonio P.; Cappa, Frédéric; Moridis, George J.


    We have conducted numerical simulation studies to assess the potential for injection-induced fault reactivation and notable seismic events associated with shale-gas hydraulic fracturing operations. The modeling is generally tuned towards conditions usually encountered in the Marcellus shale play in the Northeastern US at an approximate depth of 1500 m (~;;4,500 feet). Our modeling simulations indicate that when faults are present, micro-seismic events are possible, the magnitude of which is somewhat larger than the one associated with micro-seismic events originating from regular hydraulic fracturing because of the larger surface area that is available for rupture. The results of our simulations indicated fault rupture lengths of about 10 to 20 m, which, in rare cases can extend to over 100 m, depending on the fault permeability, the in situ stress field, and the fault strength properties. In addition to a single event rupture length of 10 to 20 m, repeated events and aseismic slip amounted to a total rupture length of 50 m, along with a shear offset displacement of less than 0.01 m. This indicates that the possibility of hydraulically induced fractures at great depth (thousands of meters) causing activation of faults and creation of a new flow path that can reach shallow groundwater resources (or even the surface) is remote. The expected low permeability of faults in producible shale is clearly a limiting factor for the possible rupture length and seismic magnitude. In fact, for a fault that is initially nearly-impermeable, the only possibility of larger fault slip event would be opening by hydraulic fracturing; this would allow pressure to penetrate the matrix along the fault and to reduce the frictional strength over a sufficiently large fault surface patch. However, our simulation results show that if the fault is initially impermeable, hydraulic fracturing along the fault results in numerous small micro-seismic events along with the propagation, effectively

  13. An efficient computational model to predict protonation at the amide nitrogen and reactivity along the C-N rotational pathway. (United States)

    Szostak, Roman; Aubé, Jeffrey; Szostak, Michal


    N-Protonation of amides is critical in numerous biological processes, including amide bonds proteolysis and protein folding as well as in organic synthesis as a method to activate amide bonds towards unconventional reactivity. A computational model enabling prediction of protonation at the amide bond nitrogen atom along the C-N rotational pathway is reported. Notably, this study provides a blueprint for the rational design and application of amides with a controlled degree of rotation in synthetic chemistry and biology.

  14. Electrical Resistivity Modeling of a Permeable Reactive Barrier for Vista Engineering Technologies: Summary

    Energy Technology Data Exchange (ETDEWEB)

    Ramirez, A L; Daily, W D


    We have performed a numerical modeling study that evaluated the capacity of electrical resistance tomography (ERT) to detect flaws in a passive reactive barrier (PRB). The model barrier is based on a real barrier described in the literature Slater and Binley (2003). It consists of highly conducting, granular iron emplaced within a trench. We assumed that the barrier was filled with a mixture of iron and sand, and that vertical electrode arrays were embedded within the barrier. We have considered (a) characterization and (b) monitoring scenarios. For (a), the objective is to use tomographs of absolute resistivity to detect construction flaws and inhomogeneities in iron distribution shortly after installation. For (b), the objective is to use resistivity change tomographs to detect iron oxidation and barrier plugging as a function of time. The study considered varying PRB hole sizes and locations. For any given model, a hole was located right next to and near the center of an electrode array (maximum sensitivity and resolution expected), at the center between two electrode arrays (moderate sensitivity and resolution), or near the bottom centered between the two arrays (minimum sensitivity and resolution). We also considered various hole sizes. The smallest hole considered had a height and a width of 0.33 m (0.11 m{sup 2}), or 1/2 of the electrode spacing within an array; the depth of the hole was always equal to the thickness of the barrier (0.66m). The largest hole had a height and a width of 1.22 m (1.74 m{sup 2}). We also modeled a medium sized hole with a height and a width of 0.66 m (0.44 m{sup 2}). The PRB material had an electrical resistivity of 0.3 ohm-m (sand/iron mix) while the hole's resistivity was 3.0 ohm-m. The study also considered various array aspect ratios because it is well known that aspect ratio controls sensitivity and resolution when line arrays of electrodes are used (Ramirez et al., 1993). Aspect ratio is defined as the distance between

  15. Experimental study of the effect of void reactivity feedback on the behavior of the scaled model boiling water reactor (United States)

    Meftah, Khaled

    A Scaled Model Boiling Water Reactor (SMBWR) model uses low pressure (i.e., 0.095 MPa) water in a heated channel 0.5 meters in length with four electrically heated fuel simulator rods. The axial void profile in the channel is measured using conductivity probes and the power to the heaters is modulated according to the void fraction to simulate void reactivity feedback. The steam from the heated channel is passed through a valve that reduces the pressure to 0.012 MPa where the steam is condensed in conditions similar to those found in a conventional BWR condenser. The feedwater flow rate, heater power, and instrumentation in the facility are controlled and monitored through a Quadra 950 computer running LabVIEW software. The void fraction signals are analyzed to identify the different flow regimes and determine the vapor velocity in the SMBWR channel using features of the probability density function and power spectral density. The void coefficient of reactivity is modified in the BWR scale model through the LabVIEW interface and the effect on the behavior of the channel is directly observed. The system response is reported for abrupt stepwise pressure changes and abrupt stepwise power changes. The response is typical of that expected for a BWR. The void reactivity feedback effect is also examined by analyzing the frequency response of the channel void fraction at steady state.

  16. Global Modelling of the total OH reactivity: validation against measurements and atmospheric implications of the 'missing' sink (United States)

    Ferracci, Valerio; Archibald, Alexander T.; Pyle, John A.


    The removal of most trace gases emitted into the atmosphere is primarily initiated by reaction with the hydroxyl radical, OH. A number of field campaigns over the last two decades have observed the presence of a "missing" sink of the OH radical in a variety of regions across the planet, from urban areas to remote forests: comparison of the direct measurements of the OH loss rate, also known as total OH reactivity, with the sum of individual known OH sinks (obtained via the simultaneous detection of species such as volatile organic compounds and nitrogen oxides) indicated that, in some cases, up to 80% of the total OH loss rate was unaccounted for. The implications of this finding are significant, as a potentially major OH sink operating in the atmosphere is not currently accounted for in atmospheric models: the presence of an additional OH sink might, for instance, lead to an increase in the atmospheric lifetime of a number of trace species, including high-impact greenhouse gases such as methane. The only modelling of the total OH reactivity is currently performed on a regional scale; a thorough assessment of the impact of the missing sink on the chemistry and climate of the planet by global modelling is therefore highly desirable. In this work a chemistry-climate model (the Met Office's Unified Model with the United Kingdom Chemistry and Aerosols scheme, UM-UKCA) was used to calculate the total OH reactivity at the planetary boundary layer. The model output was validated against available field measurements to verify that the known OH sinks observed in the field were reproduced correctly by the model: a good agreement was found between the data from more than 30 field campaigns and the model output. Following this, the effects of introducing novel OH sinks in the chemistry scheme were investigated. The first step was the introduction in the model of the newly characterised reactions of peroxy radicals (RO2) with OH, the kinetics and products of which have only

  17. Bivariate genetic modeling of cardiovascular stress reactivity : Does stress uncover genetic variance?

    NARCIS (Netherlands)

    De Geus, Eco J. C.; Kupper, Nina; Boomsma, Dorret I.; Snieder, Harold


    Objective: To test the existence of gene-by-stress interaction by assessing cardiovascular stress reactivity in monozygotic and dizygotic twins. Methods: We studied 160 adolescent (mean age 16.7 +/- 2.0 years; range 13-22 years) and 212 middle-aged twin pairs (mean age 44.2 +/- 6.7 years; range 34-6

  18. Modeling reactive scattering of F(2P) at a liquid squalane interface: a hybrid QM/MM molecular dynamics study. (United States)

    Radak, Brian K; Yockel, Scott; Kim, Dongwook; Schatz, George C


    To better understand the reactivity of gases with liquid surfaces, experimentalists have recently probed the reactive scattering of atomic fluorine at the surface of liquid squalane (C(30)H(62)). In this paper we further this research by simulating this scattering process at collision energies of 0.5 and 1.0 eV using a hybrid QM/MM molecular dynamics scheme. To model the structure of the liquid surface, classical molecular dynamics calculations were performed utilizing the OPLS-AA force field. During the F + squalane molecular dynamics simulation, QM/MM calculations are performed at every trajectory step by combining the MSINDO semiempirical Hamiltonian with OPLS-AA and using a dynamic partitioning of the atoms in the QM or MM regions via a "seed atom" method. This computational model provides a type of "on-the-fly" direct dynamics applicable to larger scale chemical processes that include the making/breaking of chemical bonds not available in standard force field models. Our results show that H abstraction is the only reactive scattering pathway and that most trajectories result in reactive scattering. Reaction statistics at the squalane surface are discussed, including variation of the results with incident angle and collision energy, and the probability of reaction as a function of carbon atom type, collision depth, and residence time. Product states, including angular distributions and final translational and rovibrational energies, are also considered and found to be significantly affected by the exothermic reaction energy for H abstraction. The vibrational distributions are in good agreement with recent experiments, but the rotational distributions are dominated by a nonthermal component while the experiments, which involve thermal incident energies, show comparable thermal and nonthermal contributions. Results for O + squalane at 1.0 eV, which we also present, show analogous comparisons with experiment, with OH vibrational distributions which are cold and

  19. A Reactive-Transport Model Describing Methanogen Growth and Methane Production in Diffuse Flow Vents at Axial Seamount (United States)

    Algar, C. K.


    Hydrogenotrophic methanogenesis is an important mode of metabolism in deep-sea hydrothermal vents. Diffuse vent fluids often show a depletion in hydrogen with a corresponding increase in methane relative to pure-mixing of end member fluid and seawater, and genomic surveys show an enrichment in genetic sequences associated with known methanogens. However, because we cannot directly sample the subseafloor habitat where these organisms are living, constraining the size and activity of these populations remains a challenge and limits our ability to quantify the role they play in vent biogeochemistry. Reactive-transport modeling may provide a useful tool for approaching this problem. Here we present a reactive-transport model describing methane production along the flow-path of hydrothermal fluid from its high temperature end-member to diffuse venting at the seafloor. The model is set up to reflect conditions at several diffuse vents in the Axial Seamount. The model describes the growth of the two dominant thermophilic methanogens, Methanothermococcus and Methanocaldococcus, observed at Axial seamount. Monod and Arrhenius constants for Methanothermococcus thermolithotrophicus and Methanocaldococcus jannaschii were obtained for the model using chemostat and bottle experiments at varying temperatures. The model is used to investigate the influence of different mixing regimes on the subseafloor populations of these methanogens. By varying the model flow path length and subseafloor cell concentrations, and fitting to observed hydrogen and methane concentrations in the venting fluid, the subseafloor biomass, fluid residence time, and methane production rate can be constrained.

  20. Reactive Programming in Java

    CERN Document Server

    CERN. Geneva


    Reactive Programming in gaining a lot of excitement. Many libraries, tools, and frameworks are beginning to make use of reactive libraries. Besides, applications dealing with big data or high frequency data can benefit from this programming paradigm. Come to this presentation to learn about what reactive programming is, what kind of problems it solves, how it solves them. We will take an example oriented approach to learning the programming model and the abstraction.

  1. Scale up tools in reactive extrusion and compounding processes. Could 1D-computer modeling be helpful? (United States)

    Pradel, J.-L.; David, C.; Quinebèche, S.; Blondel, P.


    Industrial scale-up (or scale down) in Compounding and Reactive Extrusion processes is one of the most critical R&D challenges. Indeed, most of High Performances Polymers are obtained within a reactive compounding involving chemistry: free radical grafting, in situ compatibilization, rheology control... but also side reactions: oxidation, branching, chain scission... As described by basic Arrhenius and kinetics laws, the competition between all chemical reactions depends on residence time distribution and temperature. Then, to ensure the best possible scale up methodology, we need tools to match thermal history of the formulation along the screws from a lab scale twin screw extruder to an industrial one. This paper proposes a comparison between standard scale-up laws and the use of Computer modeling Software such as Ludovic® applied and compared to experimental data. Scaling data from a compounding line to another one, applying general rules (for example at constant specific mechanical energy), shows differences between experimental and computed data, and error depends on the screw speed range. For more accurate prediction, 1D-Computer Modeling could be used to optimize the process conditions to ensure the best scale-up product, especially in temperature sensitive reactive extrusion processes. When the product temperature along the screws is the key, Ludovic® software could help to compute the temperature profile along the screws and extrapolate conditions, even screw profile, on industrial extruders.

  2. S100B Inhibitor Pentamidine Attenuates Reactive Gliosis and Reduces Neuronal Loss in a Mouse Model of Alzheimer's Disease. (United States)

    Cirillo, Carla; Capoccia, Elena; Iuvone, Teresa; Cuomo, Rosario; Sarnelli, Giovanni; Steardo, Luca; Esposito, Giuseppe


    Among the different signaling molecules released during reactive gliosis occurring in Alzheimer's disease (AD), the astrocyte-derived S100B protein plays a key role in neuroinflammation, one of the hallmarks of the disease. The use of pharmacological tools targeting S100B may be crucial to embank its effects and some of the pathological features of AD. The antiprotozoal drug pentamidine is a good candidate since it directly blocks S100B activity by inhibiting its interaction with the tumor suppressor p53. We used a mouse model of amyloid beta- (Aβ-) induced AD, which is characterized by reactive gliosis and neuroinflammation in the brain, and we evaluated the effect of pentamidine on the main S100B-mediated events. Pentamidine caused the reduction of glial fibrillary acidic protein, S100B, and RAGE protein expression, which are signs of reactive gliosis, and induced p53 expression in astrocytes. Pentamidine also reduced the expression of proinflammatory mediators and markers, thus reducing neuroinflammation in AD brain. In parallel, we observed a significant neuroprotection exerted by pentamidine on CA1 pyramidal neurons. We demonstrated that pentamidine inhibits Aβ-induced gliosis and neuroinflammation in an animal model of AD, thus playing a role in slowing down the course of the disease.

  3. Effect of chemical degradation on fluxes of reactive compounds – a study with a stochastic Lagrangian transport model

    Directory of Open Access Journals (Sweden)

    J. Rinne


    Full Text Available In the analyses of VOC fluxes measured above plant canopies, one usually assumes the flux above canopy to equal the exchange at the surface. Thus one assumes the chemical degradation to be much slower than the turbulent transport. We used a stochastic Lagrangian transport model in which the chemical degradation was described as first order decay in order to study the effect of the chemical degradation on above canopy fluxes of chemically reactive species. With the model we explored the sensitivity of the ratio of the above canopy flux to the surface emission on several parameters such as chemical lifetime of the compound, friction velocity, stability, and canopy density. Our results show that friction velocity and chemical lifetime affected the loss during transport the most. The canopy density had a significant effect if the chemically reactive compound was emitted from the forest floor. We used the results of the simulations together with oxidant data measured during HUMPPA-COPEC-2010 campaign at a Scots pine site to estimate the effect of the chemistry on fluxes of three typical biogenic VOCs, isoprene, α-pinene, and β-caryophyllene. Of these, the chemical degradation had a major effect on the fluxes of the most reactive species β-caryophyllene, while the fluxes of α-pinene were affected during nighttime. For these two compounds representing the mono- and sesquiterpenes groups, the effect of chemical degradation had also a significant diurnal cycle with the highest chemical loss at night. The different day and night time loss terms need to be accounted for, when measured fluxes of reactive compounds are used to reveal relations between primary emission and environmental parameters.

  4. Modeling psychotic and cognitive symptoms of affective disorders: Disrupted latent inhibition and reversal learning deficits in highly stress reactive mice. (United States)

    Knapman, A; Heinzmann, J-M; Holsboer, F; Landgraf, R; Touma, C


    Increased stress reactivity has repeatedly been reported in patients suffering from psychiatric diseases including schizophrenia and major depression. These disorders also have other symptoms in common, such as cognitive deficits and psychotic-like behavior. We have therefore investigated if increased stress reactivity is associated with these phenotypic endpoints in an animal model of affective disorders. The stress reactivity mouse model used in this study consists of three CD-1-derived mouse lines, that have been selectively bred for high (HR), intermediate (IR) or low (LR) stress reactivity. Male mice from these three breeding lines were subjected to a reversal learning task and latent inhibition (Li) was assessed using a conditioned taste aversion paradigm. Furthermore, as the dopaminergic system is involved in both Li and reversal learning, the dopamine 1 receptor (D1R), dopamine 2 receptor (D2R) and dopamine transporter (DAT) mRNA expression levels were assessed in relevant brain areas of these animals. The results demonstrate that HR mice show perseveration in the reversal learning task and have disrupted Li. Furthermore, compared to LR mice, HR mice have decreased D2R mRNA levels in the ventral tegmental area, as well as decreased D1R mRNA levels in the cingulate cortex, and an increased expression of D2R mRNA in the nucleus accumbens. Taken together, these results demonstrate that the HR mice display cognitive deficits associated with psychotic-like behavior, similar to those observed in patients suffering from schizophrenia and major depression and could be utilized in the search for better treatment strategies for these symptoms of psychiatric disorders.

  5. Integration of Genome-Scale Metabolic Nodels of Iron-Reducing Bacteria With Subsurface Flow and Geochemical Reactive Transport Models (United States)

    Scheibe, T. D.; Mahadevan, R.; Fang, Y.; Garg, S.; Long, P. E.; Lovley, D. M.


    Several field and laboratory experiments have demonstrated that the growth and activity of iron-reducing bacteria can be stimulated in many subsurface environments by amendment of groundwater with a soluble electron donor. Under strong iron-reducing conditions, these organisms mediate reactions that can impact a wide range of subsurface contaminants including chlorinated hydrocarbons, metals, and radionuclides. Therefore there is strong interest in in-situ bioremediation as a potential technology for cleanup of contaminated aquifers. To evaluate and design bioremediation systems, as well as to evaluate the viability of monitored natural attenuation as an alternative, quantitative models of biogeochemically reactive transport are needed. To date, most such models represent microbial activity in terms of kinetic rate (e.g., Monod- type) formulations. Such models do not account for fundamental changes in microbial functionality (such as utilization of alternative respiratory pathways) that occur as the result of spatial and temporal variations in the geochemical environment experienced by microorganisms. Constraint-based genome-scale in silico models of microbial metabolism present an alternative to simplified rate formulations that provide flexibility to account for changes in microbial function in response to local geochemical conditions. We have developed and applied a methodology for coupling a constraint-based in silico model of Geobacter sulfurreducens with a conventional model of groundwater flow, transport, and geochemical reaction. Two uses of the in silico model are tested: 1) incorporation of modified microbial growth yield coefficients based on the in silico model, and 2) variation of reaction rates in a reactive transport model based on in silico modeling of a range of local geochemical conditions. Preliminary results from this integrated model will be presented.

  6. Investigating Uranium Mobility Using Stable Isotope Partitioning of 238U/235U and a Reactive Transport Model (United States)

    Bizjack, M.; Johnson, T. M.; Druhan, J. L.; Shiel, A. E.


    We report a numerical reactive transport model which explicitly incorporates the effectively stable isotopes of uranium (U) and the factors that influence their partitioning in bioactive systems. The model reproduces trends observed in U isotope ratios and concentration measurements from a field experiment, thereby improving interpretations of U isotope ratios as a tracer for U reactive transport. A major factor contributing to U storage and transport is its redox state, which is commonly influenced by the availability of organic carbon to support metal-reducing microbial communities. Both laboratory and field experiments have demonstrated that biogenic reduction of U(VI) fractionates the stable isotope ratio 238U/235U, producing an isotopically heavy solid U(IV) product. It has also been shown that other common reactive transport processes involving U do not fractionate isotopes to a consistently measurable level, which suggests the capacity to quantify the extent of bioreduction occurring in groundwater containing U using 238U/235U ratios. A recent study of a U bioremediation experiment at the Rifle IFRC site (Colorado, USA) applied Rayleigh distillation models to quantify U stable isotope fractionation observed during acetate amendment. The application of these simplified models were fit to the observations only by invoking a "memory-effect," or a constant source of low-concentration, unfractionated U(VI). In order to more accurately interpret the measured U isotope ratios, we present a multi-component reactive transport model using the CrunchTope software. This approach is capable of quantifying the cycling and partitioning of individual U isotopes through a realistic network of transport and reaction pathways including reduction, oxidation, and microbial growth. The model incorporates physical heterogeneity of the aquifer sediments through zones of decreased permeability, which replicate the observed bromide tracer, major ion chemistry, U concentration, and U

  7. Effect of nonlinear void reactivity on bifurcation characteristics of a lumped-parameter model of a BWR: A study relevant to RBMK

    Energy Technology Data Exchange (ETDEWEB)

    Verma, Dinkar, E-mail: [Nuclear Engineering and Technology Program, Indian Institute of Technology Kanpur, Kanpur 208 016 (India); Kalra, Manjeet Singh, E-mail: [DIT University, Dehradun 248 009 (India); Wahi, Pankaj, E-mail: [Department of Mechanical Engineering, Indian Institute of Technology Kanpur, Kanpur 208 016 (India)


    Highlights: • A simplified model with nonlinear void reactivity feedback is studied. • Method of multiple scales for nonlinear analysis and oscillation characteristics. • Second order void reactivity dominates in determining system dynamics. • Opposing signs of linear and quadratic void reactivity enhances global safety. - Abstract: In the present work, the effect of nonlinear void reactivity on the dynamics of a simplified lumped-parameter model for a boiling water reactor (BWR) is investigated. A mathematical model of five differential equations comprising of neutronics and thermal-hydraulics encompassing the nonlinearities associated with both the reactivity feedbacks and the heat transfer process has been used. To this end, we have considered parameters relevant to RBMK for which the void reactivity is known to be nonlinear. A nonlinear analysis of the model exploiting the method of multiple time scales (MMTS) predicts the occurrence of the two types of Hopf bifurcation, namely subcritical and supercritical, leading to the evolution of limit cycles for a range of parameters. Numerical simulations have been performed to verify the analytical results obtained by MMTS. The study shows that the nonlinear reactivity has a significant influence on the system dynamics. A parametric study with varying nominal reactor power and operating conditions in coolant channel has also been performed which shows the effect of change in concerned parameter on the boundary between regions of sub- and super-critical Hopf bifurcations in the space constituted by the two coefficients of reactivities viz. the void and the Doppler coefficient of reactivities. In particular, we find that introduction of a negative quadratic term in the void reactivity feedback significantly increases the supercritical region and dominates in determining the system dynamics.

  8. Development of Modeling Methods and Tools for Predicting Coupled Reactive Transport Processes in Porous Media at Multiple Scales

    Energy Technology Data Exchange (ETDEWEB)

    Clement, T Prabhakar; Barnett, Mark O; Zheng, Chunmiao; Jones, Norman L


    DE-FG02-06ER64213: Development of Modeling Methods and Tools for Predicting Coupled Reactive Transport Processes in Porous Media at Multiple Scales Investigators: T. Prabhakar Clement (PD/PI) and Mark O. Barnett (Auburn), Chunmiao Zheng (Univ. of Alabama), and Norman L. Jones (BYU). The objective of this project was to develop scalable modeling approaches for predicting the reactive transport of metal contaminants. We studied two contaminants, a radioactive cation [U(VI)] and a metal(loid) oxyanion system [As(III/V)], and investigated their interactions with two types of subsurface materials, iron and manganese oxyhydroxides. We also developed modeling methods for describing the experimental results. Overall, the project supported 25 researchers at three universities. Produced 15 journal articles, 3 book chapters, 6 PhD dissertations and 6 MS theses. Three key journal articles are: 1) Jeppu et al., A scalable surface complexation modeling framework for predicting arsenate adsorption on goethite-coated sands, Environ. Eng. Sci., 27(2): 147-158, 2010. 2) Loganathan et al., Scaling of adsorption reactions: U(VI) experiments and modeling, Applied Geochemistry, 24 (11), 2051-2060, 2009. 3) Phillippi, et al., Theoretical solid/solution ratio effects on adsorption and transport: uranium (VI) and carbonate, Soil Sci. Soci. of America, 71:329-335, 2007

  9. Modelling and Optimization for Deposition of SiOxNy Films by Radio-Frequency Reactive Sputtering

    Institute of Scientific and Technical Information of China (English)

    XU Wen-Bin; DONG Shu-Rong; WANG De-Miao


    SiOxNy films are deposited by reactive sputtering from a Si target in Ar/O2/N2 atmospheres. In order to achieve the control of film composition and to keep a high deposition rate at the same time, a new sputtering model based on Berg's work is provided for the condition of double reactive gases. Analysis based on this model shows that the deposition process can easily enter the target-poisoning mode when the preset gas flow (N2 in this work)is too high, and the film composition will change from nitrogen-rich to SiO2-like with the increase of oxygen supply while keeping the N2 supply constant. The modelling results are confirmed in the deposition process of SiOxNy. Target self-bias voltages during sputtering are measured to characterize the different sputtering modes.FTIR-spectra and dielectric measurements are used to testify the model prediction of composition. Finally, an optimized sputtering condition is selected with the O2/N2 flow ratio varying from 0 to 1 and N2 supply fixed at 1 sccm. Average deposition rate of 17nm/min is obtained under this selected condition, which has suggested the model validity and potential for industry applications.

  10. Engineering-geological model of the landslide of Güevejar (S Spain) reactivated by historical earthquakes (United States)

    Delgado, José; García-Tortosa, Francisco J.; Garrido, Jesús; Giner, José; Lenti, Luca; López-Casado, Carlos; Martino, Salvatore; Peláez, José A.; Sanz de Galdeano, Carlos; Soler, Juan L.


    Landslides are a common ground effect induced by earthquakes of moderate to large magnitude. Most of them correspond to first-time instabilities induced by the seismic event, being the reactivation of pre-existing landslides less frequent in practice. The landslide of Güevejar (Granada province, S Spain) represents a case study of landslide that was reactivated, at least, two times by far field earthquakes: the Mw 8.7, 1755, Lisbon earthquake (with estimated epicentral distance of 680 km), and the Mw 6.5, 1884, Andalucia event (estimated epicentral distance of 45 km), but not by near field events of moderate magnitude (Mw 50 m) sliding surface. The engineering-geological model constitutes the first step in an ongoing research devoted to understand how it could be reactivated during far field events. The authors would like to thank the ERDF of European Union for financial support via project "Monitorización sísmica de deslizamientos. Criterios de reactivación y alerta temprana" of the "Programa Operativo FEDER de Andalucía 2007-2015". We also thank all Public Works Agency and Ministry of Public Works and Housing of the Regional Government of Andalusia.

  11. Attenuation of pyrite oxidation with a fly ash pre-barrier: Reactive transport modelling of column experiments

    Energy Technology Data Exchange (ETDEWEB)

    Perez-Lopez, R.; Cama, J.; Nieto, J.M.; Ayora, C.; Saaltink, M.W. [University of Huelva, Huelva (Spain). Dept. of Geology


    Conventional permeable reactive barriers (PRBs) for passive treatment of groundwater contaminated by acid mine drainage (AMD) use limestone as reactive material that neutralizes water acidity. However, the limestone-alkalinity potential ceases as inevitable precipitation of secondary metal-phases on grain surfaces occurs, limiting its efficiency. In the present study, fly ash derived from coal combustion is investigated as an alternative alkalinity generating material for the passive treatment of AMD using solution-saturated column experiments. Unlike conventional systems, the utilization of fly ash in a pre-barrier to intercept the non-polluted recharge water before this water reacts with pyrite-rich wastes is proposed. Chemical variation in the columns was interpreted with the reactive transport code RETRASO. In parallel, kinetics of fly ash dissolution at alkaline pH were studied using flow-through experiments and incorporated into the model. In a saturated column filled solely with pyritic sludge-quartz sand (1: 10), oxidation took place at acidic conditions (pH 3.7). According to SO{sub 4}{sup 2-} release and pH, pyrite dissolution occurred favourably in the solution-saturated porous medium until dissolved O{sub 2} was totally consumed. In a second saturated column, pyrite oxidation took place at alkaline conditions (pH 10.45) as acidity was neutralized by fly ash dissolution in a previous level. At this pH Fe release from pyrite dissolution was immediately depleted as Fe-oxy(hydroxide) phases that precipitated on the pyrite grains, forming Fe-coatings (microencapsulation). With time, pyrite microencapsulation inhibited oxidation in practically 97% of the pyritic sludge. Rapid pyrite-surface passivation decreased its reactivity, preventing AMD production in the relatively short term.


    Directory of Open Access Journals (Sweden)

    Joshua Onome Imoniana


    Full Text Available The main objective of this study was to compare and contrast the three philosophies of management control models in the process of decision-making, namely reactive, proactive and the coactive. Research methodology was based on literature review and descriptive/exploratory approach. Additionally, a survey of 20 service organizations was carried out in order to make the analysis wider-reaching. In order to do that, the following steps were followed: firstly, fundamentals of reactive, proactive and coactive models were highlighted; secondly, management behaviors in the three approaches were compared, with concepts and their practical application being highlighted, thus retrieving managerial relationships in the organization. In so doing, we draw the hypothesis that middle and top managers who adopt control models that are distant from a more coactive one, usually spend a greater number of working hours in problem-solving, leaving little or no time for planning purposes. Finally, for study consolidation purpose, we have adopted qualitative data collection, whereby a content analysis was carried out with the assistance of six categories. Results have shown the need for a change in management paradigms so that firms are not only compared through financial perspectives, without considering the analysis of management control models which, according to this study, directly influence the operational results of the organizations.

  13. A reactive burn model for shock initiation in a PBX: scaling and separability based on the hot spot concept

    Energy Technology Data Exchange (ETDEWEB)

    Show, Milton S [Los Alamos National Laboratory; Menikoff, Ralph [Los Alamos National Laboratory


    In the formulation of a reactive burn model for shock initiation, we endeavor to incorporate a number of effects based on the underlying physical concept of hot spot ignition followed by the growth of reaction due to diverging deflagration fronts. The passage of a shock front sets the initial condition for reaction, leading to a fraction of the hot spots that completely burn while others will quench. The form of the rate model is chosen to incorporate approximations based on the physical picture. In particular, the approximations imply scaling relations that are then used to mathematically separate various contributions. That is, the model is modular and refinements can be applied separately without changing the other contributions. For example, the effect of initial temperature, porosity, etc. predominantly enter the characterization of the non-quenching hot spot distribution. A large collection of velocity gauge data is shown to be well represented by the model with a very small number of parameters.

  14. The mineral dissolution rate conundrum: Insights from reactive transport modeling of U isotopes and pore fluid chemistry in marine sediments (United States)

    Maher, Kate; Steefel, Carl I.; DePaolo, Donald J.; Viani, Brian E.


    Pore water chemistry and 234U/ 238U activity ratios from fine-grained sediment cored by the Ocean Drilling Project at Site 984 in the North Atlantic were used as constraints in modeling in situ rates of plagioclase dissolution with the multicomponent reactive transport code Crunch. The reactive transport model includes a solid-solution formulation to enable the use of the 234U/ 238U activity ratios in the solid and fluid as a tracer of mineral dissolution. The isotopic profiles are combined with profiles of the major element chemistry (especially alkalinity and calcium) to determine whether the apparent discrepancy between laboratory and field dissolution rates still exists when a mechanistic reactive transport model is used to interpret rates in a natural system. A suite of reactions, including sulfate reduction and methane production, anaerobic methane oxidation, CaCO 3 precipitation, dissolution of plagioclase, and precipitation of secondary clay minerals, along with diffusive transport and fluid and solid burial, control the pore fluid chemistry in Site 984 sediments. The surface area of plagioclase in intimate contact with the pore fluid is estimated to be 6.9 m 2/g based on both grain geometry and on the depletion of 234U/ 238U in the sediment via α-recoil loss. Various rate laws for plagioclase dissolution are considered in the modeling, including those based on (1) a linear transition state theory (TST) model, (2) a nonlinear dependence on the undersaturation of the pore water with respect to plagioclase, and (3) the effect of inhibition by dissolved aluminum. The major element and isotopic methods predict similar dissolution rate constants if additional lowering of the pore water 234U/ 238U activity ratio is attributed to isotopic exchange via recrystallization of marine calcite, which makes up about 10-20% of the Site 984 sediment. The calculated dissolution rate for plagioclase corresponds to a rate constant that is about 10 2 to 10 5 times smaller than

  15. A systems approach to model natural variation in reactive properties of bacterial ribosomes

    Directory of Open Access Journals (Sweden)

    Schmidt Thomas M


    Full Text Available Abstract Background Natural variation in protein output from translation in bacteria and archaea may be an organism-specific property of the ribosome. This paper adopts a systems approach to model the protein output as a measure of specific ribosome reactive properties in a ribosome-mediated translation apparatus. We use the steady-state assumption to define a transition state complex for the ribosome, coupled with mRNA, tRNA, amino acids and reaction factors, as a subsystem that allows a focus on the completed translational output as a measure of specific properties of the ribosome. Results In analogy to the steady-state reaction of an enzyme complex, we propose a steady-state translation complex for mRNA from any gene, and derive a maximum specific translation activity, Ta(max, as a property of the ribosomal reaction complex. Ta(max has units of a-protein output per time per a-specific mRNA. A related property of the ribosome, T˜a(max⁡ MathType@MTEF@5@5@+=feaagaart1ev2aaatCvAUfKttLearuWrP9MDH5MBPbIqV92AaeXatLxBI9gBaebbnrfifHhDYfgasaacPC6xNi=xH8viVGI8Gi=hEeeu0xXdbba9frFj0xb9qqpG0dXdb9aspeI8k8fiI+fsY=rqGqVepae9pg0db9vqaiVgFr0xfr=xfr=xc9adbaqaaeGaciGaaiaabeqaaeqabiWaaaGcbaGafmivaqLbaGaadaWgaaWcbaGaemyyaeMaeiikaGIagiyBa0MaeiyyaeMaeiiEaGNaeiykaKcabeaaaaa@3464@, has units of a-protein per time per total RNA with the relationship T˜a(max⁡ MathType@MTEF@5@5@+=feaagaart1ev2aaatCvAUfKttLearuWrP9MDH5MBPbIqV92AaeXatLxBI9gBaebbnrfifHhDYfgasaacPC6xNi=xH8viVGI8Gi=hEeeu0xXdbba9frFj0xb9qqpG0dXdb9aspeI8k8fiI+fsY=rqGqVepae9pg0db9vqaiVgFr0xfr=xfr=xc9adbaqaaeGaciGaaiaabeqaaeqabiWaaaGcbaGafmivaqLbaGaadaWgaaWcbaGaemyyaeMaeiikaGIagiyBa0MaeiyyaeMaeiiEaGNaeiykaKcabeaaaaa@3464@ = ρa Ta(max, where ρa represents the fraction of total RNA committed to translation output of Pa from gene a message. Ta(max as a ribosome property is analogous to kcat for a purified enzyme, and T˜a(max⁡ MathType@MTEF@5@5@+=feaagaart1ev2aaatCvAUfKttLearuWrP9MDH5MBPbIqV92AaeXatLxBI9g

  16. Simulation of experimental breakthrough curves using multiprocess non-equilibrium model for reactive solute transport in stratified porous media

    Indian Academy of Sciences (India)

    Deepak Swami; P K Sharma; C S P Ojha


    In this paper, we have studied the behaviour of reactive solute transport through stratified porous medium under the influence of multi-process nonequilibrium transport model. Various experiments were carried out in the laboratory and the experimental breakthrough curves were observed at spatially placed sampling points for stratified porous medium. Batch sorption studies were also performed to estimate the sorption parameters of the material used in stratified aquifer system. The effects of distance dependent dispersion and tailing are visible in the experimental breakthrough curves. The presence of physical and chemical non-equilibrium are observed from the pattern of breakthrough curves. Multi-process non-equilibrium model represents the combined effect of physical and chemical non-ideality in the stratified aquifer system. The results show that the incorporation of distance dependent dispersivity in multi-process non-equilibrium model provides best fit of observed data through stratified porous media. Also, the exponential distance dependent dispersivity is more suitable for large distances and at small distances, linear or constant dispersivity function can be considered for simulating reactive solute in stratified porous medium.

  17. QSAR models for the reactivation of sarin inhibited acetylcholinesterase by quaternary pyridinium oximes based on Monte Carlo method. (United States)

    Veselinović, Aleksandar M; Veselinović, Jovana B; Toropov, Andrey A; Toropova, Alla P; Nikolić, Goran M


    Monte Carlo method has been used as a computational tool for building QSAR models for the reactivation of sarin inhibited acetylcholinesterase (AChE) by quaternary pyridinium oximes. Simplified molecular input line entry system (SMILES) together with hydrogen-suppressed graph (HSG) was used to represent molecular structure. Total number of considered oximes was 46 and activity was defined as logarithm of the AChE reactivation percentage by oximes with concentration of 0.001 M. One-variable models have been calculated with CORAL software for one data split into training, calibration and test set. Computational experiments indicated that this approach can satisfactorily predict the desired endpoint. Best QSAR model had the following statistical parameters: for training set r2=0.7096, s=0.177, MAE=0.148; calibration set: r2=0.6759, s=0.330, MAE=0.271 and test set: r2=0.8620, s=0.182, MAE=0.150. Structural indicators (SMILES based molecular fragments) for the increase and the decrease of the stated activity are defined. Using defined structural alerts computer aided design of new oxime derivatives with desired activity is presented.

  18. Morphometric analysis of NADPH diaphorase reactive neurons in a rat model of focal excitotoxic striatal injury. (United States)

    Freire, Marco Aurelio M; Guimaraes, Joanilson S; Santos, Jose Ronaldo; Simplício, Hougelle; Gomes-Leal, Walace


    Excitotoxicity is the major component in neuropathological conditions, related to harmful action of imbalanced concentrations of glutamate and its agonists in the nervous tissue, ultimately resulting in cell death. In the present study, we evaluated the effects of an acute striatal lesion induced by a focal N-methyl-D-aspartate (NMDA) microinjection on the morphometry of NADPH diaphorase-reactive neurons (NADPH-d(+) ), a subset of cells which release nitric oxide (NO) in the brain and are known by its resistance in pathological conditions. Two hundred and forty NADPH-d neurons from NMDA-lesioned striatum and contralateral counterpart were tridimensionally reconstructed at 1, 3 and 7 post-lesion days (PLDs). Cell body and dendritic field areas, length of dendrites by order and fractal dimension were analyzed. There were no significant morphometric differences when NADPH-d(+) neurons from lesioned and control striatal regions were compared among PLDs evaluated. Conversely, a conspicuous pallor in striatal neuropil reactivity was evidenced, especially in latter survival time. In addition, we observed a noticeable inflammatory response induced by NMDA. Our results suggest that NADPH-d(+) neurons were spared from deleterious effects of acute NMDA excitotoxic damage in the striatum, reinforcing the notion that this cell group is selectively resistant to injury in the nervous system.

  19. Statistical key variable analysis and model-based control for improvement performance in a deep reactive ion etching process

    Institute of Scientific and Technical Information of China (English)

    Chen Shan; Pan Tianhong; Li Zhengming; Jang Shi-Shang


    This paper proposes to develop a data-driven via's depth estimator of the deep reactive ion etching process based on statistical identification of key variables.Several feature extraction algorithms are presented to reduce the high-dimensional data and effectively undertake the subsequent virtual metrology (VM) model building process.With the available on-line VM model,the model-based controller is hence readily applicable to improve the quality ofa via's depth.Real operational data taken from a industrial manufacturing process are used to verify the effectiveness of the proposed method.The results demonstrate that the proposed method can decrease the MSE from 2.2 × 10-2 to 9 × 10-4 and has great potential in improving the existing DRIE process.

  20. A box model study on photochemical interactions between VOCs and reactive halogen species in the marine boundary layer

    Directory of Open Access Journals (Sweden)

    K. Toyota


    Full Text Available A new chemical scheme is developed for the multiphase photochemical box model SEAMAC (size-SEgregated Aerosol model for Marine Air Chemistry to investigate photochemical interactions between volatile organic compounds (VOCs and reactive halogen species in the marine boundary layer (MBL. Based primarily on critically evaluated kinetic and photochemical rate parameters as well as a protocol for chemical mechanism development, the new scheme has achieved a near-explicit description of oxidative degradation of up to C3-hydrocarbons (CH4, C2H6, C3H8, C2H4, C3H6, and C2H2 initiated by reactions with OH radicals, Cl- and Br-atoms, and O3. Rate constants and product yields for reactions involving halogen species are taken from the literature where available, but the majority of them need to be estimated. In particular, addition reactions of halogen atoms with alkenes will result in forming halogenated organic intermediates, whose photochemical loss rates are carefully evaluated in the present work. Model calculations with the new chemical scheme reveal that the oceanic emissions of acetaldehyde (CH3CHO and alkenes (especially C3H6 are important factors for regulating reactive halogen chemistry in the MBL by promoting the conversion of Br atoms into HBr or more stable brominated intermediates in the organic form. The latter include brominated hydroperoxides, bromoacetaldehyde, and bromoacetone, which sequester bromine from a reactive inorganic pool. The total mixing ratio of brominated organic species thus produced is likely to reach 10-20% or more of that of inorganic gaseous bromine species over wide regions over the ocean. The reaction between Br atoms and C2H2 is shown to be unimportant for determining the degree of bromine activation in the remote MBL. These results imply that reactive halogen chemistry can mediate a link between the oceanic emissions of VOCs and the behaviors of compounds that are sensitive to halogen chemistry such as dimethyl

  1. Reactive transport modelling to infer changes in soil hydraulic properties induced by non-conventional water irrigation (United States)

    Valdes-Abellan, Javier; Jiménez-Martínez, Joaquín; Candela, Lucila; Jacques, Diederik; Kohfahl, Claus; Tamoh, Karim


    The use of non-conventional water (e.g., treated wastewater, desalinated water) for different purposes is increasing in many water scarce regions of the world. Its use for irrigation may have potential drawbacks, because of mineral dissolution/precipitation processes, such as changes in soil physical and hydraulic properties (e.g., porosity, permeability), modifying infiltration and aquifer recharge processes or blocking root growth. Prediction of soil and groundwater impacts is essential for achieving sustainable agricultural practices. A numerical model to solve unsaturated water flow and non-isothermal multicomponent reactive transport has been modified implementing the spatio-temporal evolution of soil physical and hydraulic properties. A long-term process simulation (30 years) of agricultural irrigation with desalinated water, based on a calibrated/validated 1D numerical model in a semi-arid region, is presented. Different scenarios conditioning reactive transport (i.e., rainwater irrigation, lack of gypsum in the soil profile, and lower partial pressure of CO2 (pCO2)) have also been considered. Results show that although boundary conditions and mineral soil composition highly influence the reactive processes, dissolution/precipitation of carbonate species is triggered mainly by pCO2, closely related to plant roots. Calcite dissolution occurs in the root zone, precipitation takes place under it and at the soil surface, which will lead a root growth blockage and a direct soil evaporation decrease, respectively. For the studied soil, a gypsum dissolution up to 40 cm depth is expected at long-term, with a general increase of porosity and hydraulic conductivity.

  2. Comparative assessment of continuum-scale models of bimolecular reactive transport in porous media under pre-asymptotic conditions (United States)

    Porta, G. M.; Ceriotti, G.; Thovert, J.-F.


    We compare the ability of various continuum-scale models to reproduce the key features of a transport setting associated with a bimolecular reaction taking place in the fluid phase and numerically simulated at the pore-scale level in a disordered porous medium. We start by considering a continuum-scale formulation which results from formal upscaling of this reactive transport process by means of volume averaging. The resulting (upscaled) continuum-scale system of equations includes nonlocal integro-differential terms and the effective parameters embedded in the model are quantified directly through computed pore-scale fluid velocity and pore space geometry attributes. The results obtained through this predictive model formulation are then compared against those provided by available effective continuum models which require calibration through parameter estimation. Our analysis considers two models recently proposed in the literature which are designed to embed incomplete mixing arising from the presence of fast reactions under advection-dominated transport conditions. We show that best estimates of the parameters of these two models heavily depend on the type of data employed for model calibration. Our upscaled nonlocal formulation enables us to reproduce most of the critical features observed through pore-scale simulation without any model calibration. As such, our results clearly show that embedding into a continuum-scale model the information content associated with pore-scale geometrical features and fluid velocity yields improved interpretation of typically available continuum-scale transport observations.

  3. A travel time-based approach to model kinetic sorption in highly heterogeneous porous media via reactive hydrofacies (United States)

    Finkel, Michael; Grathwohl, Peter; Cirpka, Olaf A.


    We present a semianalytical model for the transport of solutes being subject to sorption in porous aquifers. We couple a travel time-based model of advective transport with a spherical diffusion model of kinetic sorption in nonuniform material mixtures. The model is formulated in the Laplace domain and transformed to the time domain by numerical inversion. By this, three-dimensional transport of solutes undergoing mass transfer between aqueous and solid phases can be simulated very efficiently. The model addresses both hydraulic and reactive heterogeneity of porous aquifers by means of hydrofacies, which function as homogeneous but nonuniform subunits. The total exposure time to each of these subunits controls the magnitude of sorption effects, whereas the particular sequence of facies through which the solute passes is irrelevant. We apply the model to simulate the transport of phenanthrene in a fluvio-glacial aquifer, for which the hydrofacies distribution is known at high resolution, the lithological composition of each facies has been analyzed, and sorption properties of the lithological components are available. Taking the fully resolved hydrofacies model as reference, we evaluate different approximations referring to lower information levels, reflecting shortcomings in typical modeling projects. The most important feature for a good description of both the main breakthrough and tailing of phenanthrene is the nonuniformity of the porous medium. While spatial heterogeneity of chemical properties might be neglected without introducing a large error, an approximation of the facies' composition in terms of a uniform substitute material considerably compromises the quality of the modeling result.

  4. Reactive transport model of the formation of oxide-type Ni-laterite profiles (Punta Gorda, Moa Bay, Cuba) (United States)

    Domènech, Cristina; Galí, Salvador; Villanova-de-Benavent, Cristina; Soler, Josep M.; Proenza, Joaquín A.


    Oxide-type Ni-laterite deposits are characterized by a dominant limonite zone with goethite as the economically most important Ni ore mineral and a thin zone of hydrous Mg silicate-rich saprolite beneath the magnesium discontinuity. Fe, less soluble, is mainly retained forming goethite, while Ni is redeposited at greater depth in a Fe(III) and Ni-rich serpentine (serpentine II) or in goethite, where it adsorbs or substitutes for Fe in the mineral structure. Here, a 1D reactive transport model, using CrunchFlow, of Punta Gorda oxide-type Ni-laterite deposit (Moa Bay, Cuba) formation is presented. The model reproduces the formation of the different laterite horizons in the profile from an initial, partially serpentinized peridotite, in 106 years, validating the conceptual model of the formation of this kind of deposits in which a narrow saprolite horizon rich in Ni-bearing serpentine is formed above peridotite parent rock and a thick limonite horizon is formed over saprolite. Results also confirm that sorption of Ni onto goethite can explain the weight percent of Ni found in the Moa goethite. Sensitivity analyses accounting for the effect of key parameters (composition, dissolution rate, carbonate concentration, quartz precipitation) on the model results are also presented. It is found that aqueous carbonate concentration and quartz precipitation significantly affects the laterization process rate, while the effect of the composition of secondary serpentine or of mineral dissolution rates is minor. The results of this reactive transport modeling have proven useful to validate the conceptual models derived from field observations.

  5. Modeling the reactive halogen plume from Ambrym volcano and its impact on the troposphere with the CCATT-BRAMS mesoscale model


    Jourdain, L.; T. J. Roberts; M. Pirre; Josse, B.


    Ambrym volcano (Vanuatu, Southwest Pacific) is one of the largest sources of continuous volcanic emissions worldwide. As well as releasing SO2 that is oxidized to sulfate, volcanic plumes in the troposphere are shown to undergo reactive halogen chemistry whose atmospheric impacts have been little explored to date. Here, two-way nested simulations were performed with the regional scale model CCATT-BRAMS to test our understanding of the volcano plume chemical...

  6. A global plasma model for reactive deposition of compound films by modulated pulsed power magnetron sputtering discharges (United States)

    Zheng, B. C.; Wu, Z. L.; Wu, B.; Li, Y. G.; Lei, M. K.


    A spatially averaged, time-dependent global plasma model has been developed to describe the reactive deposition of a TiAlSiN thin film by modulated pulsed power magnetron sputtering (MPPMS) discharges in Ar/N2 mixture gas, based on the particle balance and the energy balance in the ionization region, and considering the formation and erosion of the compound at the target surface. The modeling results show that, with increasing the N2 partial pressure from 0% to 40% at a constant working pressure of 0.3 Pa, the electron temperature during the strongly ionized period increases from 4 to 7 eV and the effective power transfer coefficient, which represents the power fraction that effectively heats the electrons and maintains the discharge, increases from about 4% to 7%; with increasing the working pressure from 0.1 to 0.7 Pa at a constant N2 partial pressure of 25%, the electron temperature decreases from 10 to 4 eV and the effective power transfer coefficient decreases from 8% to 5%. Using the modeled plasma parameters to evaluate the kinetic energy of arriving ions, the ion-to-neutral flux ratio of deposited species, and the substrate heating, the variations of process parameters that increase these values lead to an enhanced adatom mobility at the target surface and an increased input energy to the substrate, corresponding to the experimental observation of surface roughness reduction, the microstructure transition from the columnar structure to the dense featureless structure, and the enhancement of phase separation. At higher N2 partial pressure or lower working pressure, the modeling results demonstrate an increase in electron temperature, which shifts the discharge balance of Ti species from Ti+ to Ti2+ and results in a higher return fraction of Ti species, corresponding to the higher Al/Ti ratio of deposited films at these conditions. The modeling results are well correlated with the experimental observation of the composition variation and the microstructure

  7. Disulfiram Reactivates Latent HIV-1 in a Bcl-2-Transduced Primary CD4+ T Cell Model without Inducing Global T Cell Activation▿† (United States)

    Xing, Sifei; Bullen, Cynthia K.; Shroff, Neeta S.; Shan, Liang; Yang, Hung-Chih; Manucci, Jordyn L.; Bhat, Shridhar; Zhang, Hao; Margolick, Joseph B.; Quinn, Thomas C.; Margolis, David M.; Siliciano, Janet D.; Siliciano, Robert F.


    Highly active antiretroviral therapy (HAART) can reduce plasma HIV-1 levels to below the detection limit. However, due to the latent reservoir in resting CD4+ cells, HAART is not curative. Elimination of this reservoir is critical to curing HIV-1 infection. Agents that reactivate latent HIV-1 through nonspecific T cell activation are toxic. Here we demonstrate in a primary CD4+ T cell model that the FDA-approved drug disulfiram reactivates latent HIV-1 without global T cell activation. The extent to which disulfiram reactivates latent HIV-1 in patient cells is unclear, but the drug alone or in combination may be useful in future eradication strategies. PMID:21471244

  8. Modelling poly(p-phenylene teraphthalamide) at Extreme Tensile Loading using Reactive Potentials (United States)

    Yilmaz, Dundar


    Aromatic polyamides classified as rigid-rod polymers due to orientation of their monomers. Because of their excellent mechanical and thermal properties, aramids are widely used in the industry. For example DuPont's brand Kevlar, for its commercial aromatic polyamide polymer, due to wide usage of this polymer in ballistic applications, habitually used as a nickname for bulletproof vests. In order to engineer these ballistic fabrics, material properties of aramid fibers should be studied. In this work we focused on the poly(p-phenylene teraphthalamide) PPTA fiber, known as brand name Kevlar. We employed Reactive potentials to simulate PPTA polymer under tensile loading. We first simulated both amorphous and crystalline phases of PPTA. We also introduced defects with varying densities. We further analysed the recorded atomic positions data to understand how tensile load distributed and failure mechanisms at extreme tensile loads. This work supported by TUBITAK under Grant No: 113F358.

  9. Low temperature syntheses and reactivity of Cu2O2 active-site models. (United States)

    Citek, Cooper; Herres-Pawlis, Sonja; Stack, T Daniel P


    Nature's facility with dioxygen outmatches modern chemistry in the oxidation and oxygenation of materials and substrates for biosynthesis and cellular metabolism. The Earth's most abundant naturally occurring oxidant is-frankly-poorly understood and controlled, and thus underused. Copper-based enzyme metallocofactors are ubiquitous to the efficient consumption of dioxygen by all domains of life. Over the last several decades, we have joined many research groups in the study of copper- and dioxygen-dependent enzymes through close investigation of synthetically derived, small-molecule active-site analogs. Simple copper-dioxygen clusters bearing structural and spectroscopic similarity to dioxygen-activating enzymes can be probed for their fundamental geometrical, electronic, and reactive properties using the tools available to inorganic and synthetic chemistry. Our exploration of the copper-dioxygen arena has sustained product evaluation of the key dynamics and reactivity of binuclear Cu2O2 compounds. Almost exclusively operating at low temperatures, from -78 °C to solution characterization even at -125 °C, we have identified numerous compounds supported by simple and easily accessed, low molecular weight ligands-chiefly families of bidentate diamine chelates. We have found that by stripping away complexity in comparison to extended protein tertiary structures or sophisticated, multinucleating architectures, we can experimentally manipulate activated compounds and open pathways of reactivity toward exogenous substrates that both inform on and extend fundamental mechanisms of oxygenase enzymes. Our recent successes have advanced understanding of the tyrosinase enzyme, and related hemocyanin and NspF, and the copper membrane monooxygenases, specifically particulate methane monooxygenase (pMMO) and ammonia monooxygenase (AMO). Tyrosinase, ubiquitously distributed throughout life, is fundamental to the copper-based oxidation of phenols and the production of chromophores

  10. A Model-Based Methodology for Integrated Design and Operation of Reactive Distillation Processes

    DEFF Research Database (Denmark)

    Mansouri, Seyed Soheil; Sales-Cruz, Mauricio; Huusom, Jakob Kjøbsted


    and resolved. A new approach isto tackle process intensification and controllability issues in an integrated manner, in the early stages of process design. This integrated and simultaneous synthesis approach provides optimal operation and moreefficient control of complex intensified systems that suffice...... bubble point algorithm is used to compute the reactive vapor-liquid equilibrium data set.The operation of the RDC at the highest driving force and other candidate points is compared through openloop and closed-loop analysis. By application of this methodology it is shown that designing the process atthe......Process intensification is a new approach that has the potential to improve existing processes as well as new designs of processes to achieve more profitable and sustainable production. However, many issues with respect to their implementation and operation is not clear; for example, the question...

  11. Application of reactive transport modelling to growth and transport of microorganisms in the capillary fringe

    CERN Document Server

    Hron, Pavel; Bastian, Peter; Gallert, Claudia; Winter, Josef; Ippisch, Olaf


    A multicomponent multiphase reactive transport simulator has been developed to facilitate the investigation of a large variety of phenomena in porous media including component transport, diffusion, microbiological growth and decay, cell attachment and detachment and phase exchange. The coupled problem is solved using operator splitting. This approach allows a flexible adaptation of the solution strategy to the concrete problem. Moreover, the individual submodels were optimised to be able to describe behaviour of Escherichia coli (HB101 K12 pGLO) in the capillary fringe in the presence or absence of dissolved organic carbon and oxygen under steady-state and flow conditions. Steady-state and flow through experiments in a Hele-Shaw cell, filled with quartz sand, were conducted to study eutrophic bacterial growth and transport in both saturated and unsaturated porous media. As E. coli cells can form the green fluorescent protein (GFP), the cell densities, calculated by evaluation of measured fluorescence intensit...

  12. Towards an efficient multiscale modeling of low-dimensional reactive systems: study of numerical closure procedures

    CERN Document Server

    Mazzi, Giacomo; Samaey, Giovanni


    In this paper, we present a study on how to develop an efficient multiscale simulation strategy for the dynamics of chemically active systems on low-dimensional supports. Such reactions are encountered in a wide variety of situations, ranging from heterogeneous catalysis to electrochemical or (membrane) biological processes, to cite a few. We analyzed in this context different techniques within the framework of an important multiscale approach known as the equation free method (EFM), which "bridges the multiscale gap" by building microscopic configurations using macroscopic-level information only. We hereby considered two simple reactive processes on a one-dimensional lattice, the simplicity of which allowed for an in-depth understanding of the parameters controlling the efficiency of this approach. We demonstrate in particular that it is not enough to base the EFM on the time evolution of the average concentrations of particles on the lattice, but that the time evolution of clusters of particles has to be in...

  13. Shock simulations of a single-site coarse-grain RDX model using the dissipative particle dynamics method with reactivity (United States)

    Sellers, Michael S.; Lísal, Martin; Schweigert, Igor; Larentzos, James P.; Brennan, John K.


    In discrete particle simulations, when an atomistic model is coarse-grained, a tradeoff is made: a boost in computational speed for a reduction in accuracy. The Dissipative Particle Dynamics (DPD) methods help to recover lost accuracy of the viscous and thermal properties, while giving back a relatively small amount of computational speed. Since its initial development for polymers, one of the most notable extensions of DPD has been the introduction of chemical reactivity, called DPD-RX. In 2007, Maillet, Soulard, and Stoltz introduced implicit chemical reactivity in DPD through the concept of particle reactors and simulated the decomposition of liquid nitromethane. We present an extended and generalized version of the DPD-RX method, and have applied it to solid hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Demonstration simulations of reacting RDX are performed under shock conditions using a recently developed single-site coarse-grain model and a reduced RDX decomposition mechanism. A description of the methods used to simulate RDX and its transition to hot product gases within DPD-RX is presented. Additionally, we discuss several examples of the effect of shock speed and microstructure on the corresponding material chemistry.

  14. QSAR Models for the Reactivation of Sarin Inhibited AChE by Quaternary Pyridinium Oximes Based on Monte Carlo Method. (United States)

    Veselinović, Aleksandar M; Veselinović, Jovana B; Toropov, Andrey A; Toropova, Alla P; Nikolić, Goran M


    For three random splits, one-variable models of oximes reactivation of sarin inhibited acetylcholinesterase (logarithm of the AChE reactivation percentage by oximes with concentration of 0.001 M) have been calculated with CORAL software. The total number of considered oximes was 42. Simplified molecular input line entry system (SMILES) and hydrogen-suppressed graph (HSG) are used to represent the molecular structure. Using CORAL software by means of the calculation with Monte Carlo optimization of the so called correlation weights for the molecular fragments, optimal SMILES-based descriptors were defined, which are correlated with an endpoint for the training set. The predictability of these descriptors for an external test are estimated. In this study hybrid representation HSG together with SMILES was used. The "classic" scheme (i.e. split data into the training set and test set) of building up quantitative structure-activity relationships was employed. Computational experiments indicated that this approach can satisfactorily predict the desired endpoint. Best model had following statistical characteristics n=32, r2= 0.6012, s= 0.279, F= 45 for training and n=10, r2= 0.9301, s= 0.076, Rm2=0.9206 for test set.

  15. A time-asymptotic one equation non-equilibrium model for reactive transport in a two phase porous medium (United States)

    Yohan, D.; Gerald, D.; Magali, G.; Michel, Q.


    The general problem of transport and reaction in multiphase porous media has been a subject of extensive studies during the last decades. For example, biologically mediated porous media have seen a long history of research from the environmental engineering point of view. Biofilms (aggregate of microorganisms coated in a polymer matrix generated by bacteria) have been particularly examined within the context of bioremediation in the subsurface zone. Five types of models may be used to describe these kinds of physical system: 1) one-equation local mass equilibrium models when the assumption of local mass equilibrium is valid 2) two equations models when the assumption of local mass equilibrium is not valid 3) one equation non-equilibrium models 4) mixed models coupling equations solved at two different scales 5) one equation time-asymptotic models. In this presentation, we use the method of volume averaging with closure to extend the time- asymptotic model at the Darcy scale to the reactive case. Closure problems are solved for simple unit cells, and the macro-scale model is validated against pore-scale simulations.

  16. Reactive transport modeling of plug-flow reactor experiments: quartz and tuff dissolution at 240°C (United States)

    Johnson, James W.; Knauss, Kevin G.; Glassley, William E.; DeLoach, Laura D.; Tompson, Andrew F. B.


    Extension of reactive transport modeling to predict the coupled thermal, hydrological, and chemical evolution of complex geological systems is predicated on successful application of the approach to simulate well-constrained physical experiments. In this study, steady-state effluent concentrations and dissolution/precipitation features associated with crushed quartz and tuff dissolution at 240°C have been determined experimentally using a plug-flow reactor (PFR) and scanning electron microscopy (SEM) techniques, then modeled with the reactive transport simulator GIMRT ( Steefel and Yabusaki, 1996) using a linear rate law from transition state theory (TST) . For quartz dissolution, interdependence of the specific surface area ( Am) and reaction rate constant ( km) predicted from the modeling agrees closely with that obtained from an analytical solution to the reaction-transport equation without diffusion/dispersion, verifying the advection-dominant nature of the PFR experiments. Independently-determined Aqtz and kqtz from the literature are shown to be internally consistent with respect to the model and analytical interdependence, implying appropriateness of the linear TST rate law and adequacy of BET-determined Am for use in modeling PFR experiments. Applications of this integrated approach for monomineralic dissolution include assessment of internal consistency among independent Am and km data, estimation of km from BET-determined Am, and rapid evaluation of alternative rate laws. For tuff dissolution, accurate simulation of the experimental steady-state effluent concentrations (to within 3% for Na, Al and K; to within 15% for Si and Ca) and dearth of alteration phases (complex systems for which development of experimental analogs is impractical or impossible.

  17. The average local ionization energy as a tool for identifying reactive sites on defect-containing model graphene systems. (United States)

    Murray, Jane S; Shields, Zenaida Peralta-Inga; Lane, Pat; Macaveiu, Laura; Bulat, Felipe A


    In a continuing effort to further explore the use of the average local ionization energy [Formula: see text] as a computational tool, we have investigated how well [Formula: see text] computed on molecular surfaces serves as a predictive tool for identifying the sites of the more reactive electrons in several nonplanar defect-containing model graphene systems, each containing one or more pentagons. They include corannulene (C20H10), two inverse Stone-Thrower-Wales defect-containing structures C26H12 and C42H16, and a nanotube cap model C22H6, whose end is formed by three fused pentagons. Coronene (C24H12) has been included as a reference planar defect-free graphene model. We have optimized the structures of these systems as well as several monohydrogenated derivatives at the B3PW91/6-31G* level, and have computed their I(r) on molecular surfaces corresponding to the 0.001 au, 0.003 au and 0.005 au contours of the electronic density. We find that (1) the convex sides of the interior carbons of the nonplanar models are more reactive than the concave sides, and (2) the magnitudes of the lowest I(r) surface minima (the I S, min) correlate well with the interaction energies for hydrogenation at these sites. These I S, min values decrease in magnitude as the nonplanarity of the site increases, consistent with earlier studies. A practical benefit of the use of I(r) is that a single calculation suffices to characterize the numerous sites on a large molecular system, such as graphene and defect-containing graphene models.

  18. Mixing-controlled uncertainty in long-term predictions of acid rock drainage from heterogeneous waste-rock piles (United States)

    Pedretti, D.; Beckie, R. D.; Mayer, K. U.


    The chemistry of drainage from waste-rock piles at mine sites is difficult to predict because of a number of uncertainties including heterogeneous reactive mineral content, distribution of minerals, weathering rates and physical flow properties. In this presentation, we examine the effects of mixing on drainage chemistry over timescales of 100s of years. We use a 1-D streamtube conceptualization of flow in waste rocks and multicomponent reactive transport modeling. We simplify the reactive system to consist of acid-producing sulfide minerals and acid-neutralizing carbonate minerals and secondary sulfate and iron oxide minerals. We create multiple realizations of waste-rock piles with distinct distributions of reactive minerals along each flow path and examine the uncertainty of drainage geochemistry through time. The limited mixing of streamtubes that is characteristic of the vertical unsaturated flow in many waste-rock piles, allows individual flowpaths to sustain acid or neutral conditions to the base of the pile, where the streamtubes mix. Consequently, mixing and the acidity/alkalinity balance of the streamtube waters, and not the overall acid- and base-producing mineral contents, control the instantaneous discharge chemistry. Our results show that the limited mixing implied by preferential flow and the heterogeneous distribution of mineral contents lead to large uncertainty in drainage chemistry over short and medium time scales. However, over longer timescales when one of either the acid-producing or neutralizing primary phases is depleted, the drainage chemistry becomes less controlled by mixing and in turn less uncertain. A correct understanding of the temporal variability of uncertainty is key to make informed long-term decisions in mining settings regarding the management of waste material.

  19. An ionization region model of the reactive Ar/O2 high power impulse magnetron sputtering discharge (United States)

    Gudmundsson, J. T.; Lundin, D.; Brenning, N.; Raadu, M. A.; Huo, Chunqing; Minea, T. M.


    A new reactive ionization region model (R-IRM) is developed to describe the reactive Ar/O2 high power impulse magnetron sputtering (HiPIMS) discharge with a titanium target. It is then applied to study the temporal behavior of the discharge plasma parameters such as electron density, the neutral and ion composition, the ionization fraction of the sputtered vapor, the oxygen dissociation fraction, and the composition of the discharge current. We study and compare the discharge properties when the discharge is operated in the two well established operating modes, the metal mode and the poisoned mode. Experimentally, it is found that in the metal mode the discharge current waveform displays a typical non-reactive evolution, while in the poisoned mode the discharge current waveform becomes distinctly triangular and the current increases significantly. Using the R-IRM we explore the current increase and find that when the discharge is operated in the metal mode Ar+ and Ti+ -ions contribute most significantly (roughly equal amounts) to the discharge current while in the poisoned mode the Ar+ -ions contribute most significantly to the discharge current and the contribution of O+ -ions, Ti+ -ions, and secondary electron emission is much smaller. Furthermore, we find that recycling of atoms coming from the target, that are subsequently ionized, is required for the current generation in both modes of operation. From the R-IRM results it is found that in the metal mode self-sputter recycling dominates and in the poisoned mode working gas recycling dominates. We also show that working gas recycling can lead to very high discharge currents but never to a runaway. It is concluded that the dominating type of recycling determines the discharge current waveform.

  20. Numerical algorithms based on Galerkin methods for the modeling of reactive interfaces in photoelectrochemical (PEC) solar cells (United States)

    Harmon, Michael; Gamba, Irene M.; Ren, Kui


    This work concerns the numerical solution of a coupled system of self-consistent reaction-drift-diffusion-Poisson equations that describes the macroscopic dynamics of charge transport in photoelectrochemical (PEC) solar cells with reactive semiconductor and electrolyte interfaces. We present three numerical algorithms, mainly based on a mixed finite element and a local discontinuous Galerkin method for spatial discretization, with carefully chosen numerical fluxes, and implicit-explicit time stepping techniques, for solving the time-dependent nonlinear systems of partial differential equations. We perform computational simulations under various model parameters to demonstrate the performance of the proposed numerical algorithms as well as the impact of these parameters on the solution to the model.

  1. Modeling the reactive halogen plume from Ambrym volcano and its impact on the troposphere with the CCATT-BRAMS mesoscale model

    Directory of Open Access Journals (Sweden)

    L. Jourdain


    Full Text Available Ambrym volcano (Vanuatu, Southwest Pacific is one of the largest sources of continuous volcanic emissions worldwide. As well as releasing SO2 that is oxidized to sulfate, volcanic plumes in the troposphere are shown to undergo reactive halogen chemistry whose atmospheric impacts have been little explored to date. Here, two-way nested simulations were performed with the regional scale model CCATT-BRAMS to test our understanding of the volcano plume chemical processing and to assess the impact of Ambrym on atmospheric chemistry at local and regional scales. We focus on an episode of extreme passive degassing that occurred in early 2005 and for which airborne DOAS measurements of SO2 and BrO columns, in the near downwind plume, have been reported. The model was developed to include reactive halogen chemistry and a volcanic emission source specific to this extreme degassing event. SO2 simulated columns show very good quantitative agreement with the DOAS observations as well as with OMI data, suggesting that the plume direction as well as its dilution are well represented. Simulations are presented with and without a high-temperature initialization that includes radicals formed by high temperature partial oxidation of magmatic gases by ambient air. When included high-temperature chemistry initialization, the model is able to capture the observed BrO/SO2 trend with distance from the vent in the near downwind plume. However, the maximum of BrO columns enhancement is still underestimated by a factor 3. The model identifies total in-plume depletion of ozone (15 ppbv as a limiting factor to the partitioning of reactive bromine into BrO, of particular importance in this very strong plume at low background ozone conditions. Impacts of Ambrym in the Southwest Pacific region were also evaluated. As the plume disperses regionally, reactive halogen chemistry continues on sulfate aerosols produced by SO2 oxidation and promotes BrCl formation. Ozone depletion is

  2. Modeling of coulpled deformation and permeability evolution during fault reactivation induced by deep underground injection of CO2

    Energy Technology Data Exchange (ETDEWEB)

    Cappa, F.; Rutqvist, J.


    The interaction between mechanical deformation and fluid flow in fault zones gives rise to a host of coupled hydromechanical processes fundamental to fault instability, induced seismicity, and associated fluid migration. In this paper, we discuss these coupled processes in general and describe three modeling approaches that have been considered to analyze fluid flow and stress coupling in fault-instability processes. First, fault hydromechanical models were tested to investigate fault behavior using different mechanical modeling approaches, including slip interface and finite-thickness elements with isotropic or anisotropic elasto-plastic constitutive models. The results of this investigation showed that fault hydromechanical behavior can be appropriately represented with the least complex alternative, using a finite-thickness element and isotropic plasticity. We utilized this pragmatic approach coupled with a strain-permeability model to study hydromechanical effects on fault instability during deep underground injection of CO{sub 2}. We demonstrated how such a modeling approach can be applied to determine the likelihood of fault reactivation and to estimate the associated loss of CO{sub 2} from the injection zone. It is shown that shear-enhanced permeability initiated where the fault intersects the injection zone plays an important role in propagating fault instability and permeability enhancement through the overlying caprock.

  3. Assessing Cognitive and Affective Empathy Through the Interpersonal Reactivity Index: An Argument Against a Two-Factor Model. (United States)

    Chrysikou, Evangelia G; Thompson, W Jake


    One aspect of higher order social cognition is empathy, a psychological construct comprising a cognitive (recognizing emotions) and an affective (responding to emotions) component. The complex nature of empathy complicates the accurate measurement of these components. The most widely used measure of empathy is the Interpersonal Reactivity Index (IRI). However, the factor structure of the IRI as it is predominantly used in the psychological literature differs from Davis's original four-factor model in that it arbitrarily combines the subscales to form two factors: cognitive and affective empathy. This two-factor model of the IRI, although popular, has yet to be examined for psychometric support. In the current study, we examine, for the first time, the validity of this alternative model. A confirmatory factor analysis showed poor model fit for this two-factor structure. Additional analyses offered support for the original four-factor model, as well as a hierarchical model for the scale. In line with previous findings, females scored higher on the IRI than males. Our findings indicate that the IRI, as it is currently used in the literature, does not accurately measure cognitive and affective empathy and highlight the advantages of using the original four-factor structure of the scale for empathy assessments. © The Author(s) 2015.

  4. The Weird World, and Equally Weird Measurement Models: Reactive Indicators and the Validity Revolution (United States)

    Hayduk, Leslie A.; Robinson, Hannah Pazderka; Cummings, Greta G.; Boadu, Kwame; Verbeek, Eric L.; Perks, Thomas A.


    Researchers using structural equation modeling (SEM) aspire to learn about the world by seeking models with causal specifications that match the causal forces extant in the world. This quest for a model matching existing worldly causal forces constitutes an ontology that orients, or perhaps reorients, thinking about measurement validity. This…

  5. The reactive element effect of ceria particle dispersion on alumina growth: A model based on microstructural observations (United States)

    Wang, X.; Peng, X.; Tan, X.; Wang, F.


    The oxidation kinetics of alumina-forming metals can be affected by adding a small amount of a reactive (normally rare earth) element oxide (RExOy) and the segregation of the reactive element (RE) ions to the growing alumina grain boundaries (GBs) has been considered as a responsible reason. However, this interpretation remains a controversial issue as to how RE ions are produced by RExOy which is thermodynamically and chemically stable in metals. The question is answered by a model that is based on transmission electron microscopy (TEM) investigation of a CeO2-dispersed nickel aluminide oxidized in air at 1100 °C. The CeO2 dispersion is incorporated into the alumina scale by the inward growth of inner α-Al2O3, where it partially dissolves producing tetravalent Ce cations which then transform to trivalent cations by trapping electrons. The trivalent cations segregate to the α-Al2O3 GBs and diffuse outward along first the GBs and later the twin boundaries (TBs) in the outer γ-Al2O3 layer, being precipitated as Ce2O3 particles near surface.

  6. Riluzole neuroprotection in a parkinson's disease model involves suppression of reactive astrocytosis but not GLT-1 regulation

    Directory of Open Access Journals (Sweden)

    Carbone Marica


    Full Text Available Abstract Background Riluzole is a neuroprotective drug used in the treatment of motor neurone disease. Recent evidence suggests that riluzole can up-regulate the expression and activity of the astrocyte glutamate transporter, GLT-1. Given that regulation of glutamate transport is predicted to be neuroprotective in Parkinson's disease, we tested the effect of riluzole in parkinsonian rats which had received a unilateral 6-hydroxydopamine injection into the median forebrain bundle. Results Rats were treated with intraperitoneal riluzole (4 mg/kg or 8 mg/kg, 1 hour before the lesion then once daily for seven days. Riluzole produced a modest but significant attenuation of dopamine neurone degeneration, assessed by suppression of amphetamine-induced rotations, preservation of tyrosine hydroxylase positive neuronal cell bodies in the substantia nigra pars compacta and attenuation of striatal tyrosine hydroxylase protein loss. Seven days after 6-hydroxydopamine lesion, reactive astrocytosis was observed in the striatum, as determined by increases in expression of glial fibrillary acidic protein, however the glutamate transporter, GLT-1, which is also expressed in astrocytes was not regulated by the lesion. Conclusions The results confirm that riluzole is a neuroprotective agent in a rodent model of parkinson's disease. Riluzole administration did not regulate GLT-1 levels but significantly reduced GFAP levels, in the lesioned striatum. Riluzole suppression of reactive astrocytosis is an intriguing finding which might contribute to the neuroprotective effects of this drug.

  7. Inhibiting C-Reactive Protein for the Treatment of Cardiovascular Disease: Promising Evidence from Rodent Models

    Directory of Open Access Journals (Sweden)

    Alexander J. Szalai


    Full Text Available Raised blood C-reactive protein (CRP level is a predictor of cardiovascular events, but whether blood CRP is causal in the disease process is unknown. The latter would best be defined by pharmacological inhibition of the protein in the context of a randomized case-control study. However, no CRP specific drug is currently available so such a prospective study cannot be performed. Blood CRP is synthesized primarily in the liver and the liver is an organ where antisense oligonucleotide (ASO drugs accumulate. Taking advantage of this we evaluated the efficacy of CRP specific ASOs in rodents with experimentally induced cardiovascular damage. Treating rats for 4 weeks with a rat CRP-specific ASO achieved >60% reduction of blood CRP. Notably, this effect was associated with improved heart function and pathology following myocardial infarction (induced by ligation of the left anterior descending artery. Likewise in human CRP transgenic mice treated for 2 weeks with a human CRP-specific ASO, blood human CRP was reduced by >70% and carotid artery patency was improved (2 weeks after surgical ligation. CRP specific ASOs might pave the way towards a placebo-controlled trial that could clarify the role of CRP in cardiovascular disease.

  8. Reactive transport and mineral dissolution in fractured and porous rock: experiments, models and field observations (United States)

    Dutka, Filip; Osselin, Florian; Kondratiuk, Paweł; Szymczak, Piotr


    We analyze the evolution of the shape of a dissolving porous body immersed in a reactive fluid. First, we consider the case of a semi-infinite body and transport-limited dissolution and show that in this case the resulting shape is parabolic. We derive the dissolution rate of such shapes depending on the contrast of permeabilities between the body and the surrounding matrix both in two and three spatial dimensions. Next, we consider a problem of the dissolution of a finite-sized porous object in a Hele-Shaw cell. We study this system both experimentally and numerically. In the experiment, we use a microfluidic chip with a gypsum block inserted in between two parallel polycarbonate plates. By changing the flow rate and the distance between the plates we can scan a relatively wide range of Péclet and Damköhler numbers, which characterize the relative magnitude of advection, diffusion and reaction in the system. The evolving geometries are captured by a camera and then analyzed by image-processing techniques. The experiments show a number of unexpected regularities. In particular, the upstream (trailing) edge of the dissolving object is shown to advance with a constant velocity whereas its curvature is changing in time. If the object had initially a sharp tip pointing upstream, its radius of curvature first increases and then decreases in time. Finally, we compare the obtained dissolution shapes with the natural forms such as pinnacles in a surface karst.

  9. Sirtuin modulators control reactive gliosis in an in vitro model of Alzheimer’s disease

    Directory of Open Access Journals (Sweden)

    Caterina eScuderi


    Full Text Available Among neurodegenerative disorders, Alzheimer’s disease (AD represents the most common cause of dementia in the elderly. Several genetic and environmental factors have been identified, however aging represents the most important risk factor in the development of AD. To date, no effective treatments to prevent or slow this dementia are available. Sirtuins (SIRTs are a family of NAD+-dependent enzymes, implicated in the control of a variety of biological processes that have the potential to modulate neurodegeneration. Here we tested the hypothesis that activation of SIRT1 or inhibition of SIRT2 would prevent reactive gliosis which is considered one of the most important hallmark of AD. Primary rat astrocytes were activated with beta amyloid 1-42 (Aβ 1-42 and treated with resveratrol (RSV or AGK-2, a SIRT1 activator and a SIRT2-selective inhibitor, respectively. Results showed that both RSV and AGK-2 were able to reduce astrocyte activation as well as the production of pro-inflammatory mediators. These data disclose novel findings about the therapeutic potential of SIRT modulators, and suggest novel strategies for AD treatment.

  10. A theoretical framework for modeling dilution enhancement of non-reactive solutes in heterogeneous porous media. (United States)

    de Barros, F P J; Fiori, A; Boso, F; Bellin, A


    Spatial heterogeneity of the hydraulic properties of geological porous formations leads to erratically shaped solute clouds, thus increasing the edge area of the solute body and augmenting the dilution rate. In this study, we provide a theoretical framework to quantify dilution of a non-reactive solute within a steady state flow as affected by the spatial variability of the hydraulic conductivity. Embracing the Lagrangian concentration framework, we obtain explicit semi-analytical expressions for the dilution index as a function of the structural parameters of the random hydraulic conductivity field, under the assumptions of uniform-in-the-average flow, small injection source and weak-to-mild heterogeneity. Results show how the dilution enhancement of the solute cloud is strongly dependent on both the statistical anisotropy ratio and the heterogeneity level of the porous medium. The explicit semi-analytical solution also captures the temporal evolution of the dilution rate; for the early- and late-time limits, the proposed solution recovers previous results from the literature, while at intermediate times it reflects the increasing interplay between large-scale advection and local-scale dispersion. The performance of the theoretical framework is verified with high resolution numerical results and successfully tested against the Cape Cod field data.

  11. Comparative modeling of fault reactivation and seismicity in geologic carbon storage and shale-gas reservoir stimulation (United States)

    Rutqvist, Jonny; Rinaldi, Antonio; Cappa, Frederic


    The potential for fault reactivation and induced seismicity are issues of concern related to both geologic CO2 sequestration and stimulation of shale-gas reservoirs. It is well known that underground injection may cause induced seismicity depending on site-specific conditions, such a stress and rock properties and injection parameters. To date no sizeable seismic event that could be felt by the local population has been documented associated with CO2 sequestration activities. In the case of shale-gas fracturing, only a few cases of felt seismicity have been documented out of hundreds of thousands of hydraulic fracturing stimulation stages. In this paper we summarize and review numerical simulations of injection-induced fault reactivation and induced seismicity associated with both underground CO2 injection and hydraulic fracturing of shale-gas reservoirs. The simulations were conducted with TOUGH-FLAC, a simulator for coupled multiphase flow and geomechanical modeling. In this case we employed both 2D and 3D models with an explicit representation of a fault. A strain softening Mohr-Coulomb model was used to model a slip-weakening fault slip behavior, enabling modeling of sudden slip that was interpreted as a seismic event, with a moment magnitude evaluated using formulas from seismology. In the case of CO2 sequestration, injection rates corresponding to expected industrial scale CO2 storage operations were used, raising the reservoir pressure until the fault was reactivated. For the assumed model settings, it took a few months of continuous injection to increase the reservoir pressure sufficiently to cause the fault to reactivate. In the case of shale-gas fracturing we considered that the injection fluid during one typical 3-hour fracturing stage was channelized into a fault along with the hydraulic fracturing process. Overall, the analysis shows that while the CO2 geologic sequestration in deep sedimentary formations are capable of producing notable events (e

  12. Engineering model of the electric drives of separation device for simulation of automatic control systems of reactive power compensation by means of serially connected capacitors (United States)

    Juromskiy, V. M.


    It is developed a mathematical model for an electric drive of high-speed separation device in terms of the modeling dynamic systems Simulink, MATLAB. The model is focused on the study of the automatic control systems of the power factor (Cosφ) of an actuator by compensating the reactive component of the total power by switching a capacitor bank in series with the actuator. The model is based on the methodology of the structural modeling of dynamic processes.

  13. Final Report for LDRD Project 05-ERD-050: "Developing a Reactive Chemistry Capability for the NARAC Operational Model (LODI)"

    Energy Technology Data Exchange (ETDEWEB)

    Cameron-Smith, P; Grant, K; Connell, P


    In support of the National Security efforts of LLNL, this project addressed the existing imbalance between dispersion and chemical capabilities of LODI (Lagrangian Operational Dispersion Integrator--the NARAC operational dispersion model). We have demonstrated potentially large effects of atmospheric chemistry on the impact of chemical releases (e.g., industrial chemicals and nerve agents). Prior to our work, LODI could only handle chains of first-order losses (exponential decays) that were independent of time and space, limiting NARAC's capability to respond when reactive chemistry is important. We significantly upgraded the chemistry and aerosol capability of LODI to handle (1) arbitrary networks of chemical reactions, (2) mixing and reactions with ambient species, (3) evaporation and condensation of aerosols, and (4) heat liberated from chemical reactions and aerosol condensation (which can cause a cold and dense plume hugging the ground to rise into the atmosphere, then descend to the ground again as droplets). When this is made operational, it will significantly improve NARAC's ability to respond to terrorist attacks and industrial accidents that involve reactive chemistry, including many chemical agents and toxic industrial chemicals (TICS). As a dual-use, the resulting model also has the potential to be a state-of-the-art air-quality model. Chemical releases are the most common type of airborne hazardous release and many operational applications involve such scenarios. The new capability we developed is therefore relevant to the needs of the Department of Energy (DOE), Department of Homeland Security (DHS) and Department of Defense (DoD).

  14. Regulatory effect of Dimethyl Sulfoxide (DMSO) on astrocytic reactivity in a murine model of cerebral infarction by arterial embolization. (United States)

    Lapuente Chala, Catalina; Rengifo Valbuena, Carlos Augusto; Avila Rodríguez, Marco Fidel; Céspedes Rubio, Angel


    The pathophysiology of cerebral ischemia is essential for early diagnosis, neurologic recovery, the early onset of drug treatment and the prognosis of ischemic events. Experimental models of cerebral ischemia can be used to evaluate the cellular response phenomena and possible neurological protection by drugs. To characterize the cellular changes in the neuronal population and astrocytic response by the effect of Dimethyl Sulfoxide (DMSO) on a model of ischemia caused by cerebral embolism. Twenty Wistar rats were divided into four groups (n= 5). The infarct was induced with α-bovine thrombin (40 NIH/Unit.). The treated group received 90 mg (100 μL) of DMSO in saline (1:1 v/v) intraperitoneally for 5 days; ischemic controls received only NaCl (placebo) and two non-ischemic groups (simulated) received NaCl and DMSO respectively. We evaluated the neuronal (anti-NeuN) and astrocytic immune-reactivity (anti-GFAP). The results were analyzed by densitometry (NIH Image J-Fiji 1.45 software) and analysis of variance (ANOVA) with the Graph pad software (Prism 5). Cerebral embolism induced reproducible and reliable lesions in the cortex and hippocampus (CA1)., similar to those of focal models. DMSO did not reverse the loss of post-ischemia neuronal immune-reactivity, but prevented the morphological damage of neurons, and significantly reduced astrocytic hyperactivity in the somato-sensory cortex and CA1 (p DMSO on astrocyte hyperreactivity and neuronal-astroglial cytoarchitecture , gives it potential neuroprotective properties for the treatment of thromboembolic cerebral ischemia in the acute phase.

  15. Vertical distribution of denitrification in an estuarine sediment: integrating sediment flowthrough reactor experiments and microprofiling via reactive transport modeling. (United States)

    Laverman, Anniet M; Meile, Christof; Van Cappellen, Philippe; Wieringa, Elze B A


    Denitrifying activity in a sediment from the freshwater part of a polluted estuary in northwest Europe was quantified using two independent approaches. High-resolution N(2)O microprofiles were recorded in sediment cores to which acetylene was added to the overlying water and injected laterally into the sediment. The vertical distribution of the rate of denitrification supported by nitrate uptake from the overlying water was then derived from the time series N(2)O concentration profiles. The rates obtained for the core incubations were compared to the rates predicted by a forward reactive transport model, which included rate expression for denitrification calibrated with potential rate measurements obtained in flowthrough reactors containing undisturbed, 1-cm-thick sediment slices. The two approaches yielded comparable rate profiles, with a near-surface, 2- to 3-mm narrow zone of denitrification and maximum in situ rates on the order of 200 to 300 nmol cm(-3) h(-1). The maximum in situ rates were about twofold lower than the maximum potential rate for the 0- to 1-cm depth interval of the sediment, indicating that in situ denitrification was nitrate limited. The experimentally and model-derived rates of denitrification implied that there was nitrate uptake by the sediment at a rate that was on the order of 50 (+/- 10) nmol cm(-2) h(-1), which agreed well with direct nitrate flux measurements for core incubations. Reactive transport model calculations showed that benthic uptake of nitrate at the site is particularly sensitive to the nitrate concentration in the overlying water and the maximum potential rate of denitrification in the sediment.

  16. An in-depth comparison of latent HIV-1 reactivation in multiple cell model systems and resting CD4+ T cells from aviremic patients.

    Directory of Open Access Journals (Sweden)

    Celsa A Spina

    Full Text Available The possibility of HIV-1 eradication has been limited by the existence of latently infected cellular reservoirs. Studies to examine control of HIV latency and potential reactivation have been hindered by the small numbers of latently infected cells found in vivo. Major conceptual leaps have been facilitated by the use of latently infected T cell lines and primary cells. However, notable differences exist among cell model systems. Furthermore, screening efforts in specific cell models have identified drug candidates for "anti-latency" therapy, which often fail to reactivate HIV uniformly across different models. Therefore, the activity of a given drug candidate, demonstrated in a particular cellular model, cannot reliably predict its activity in other cell model systems or in infected patient cells, tested ex vivo. This situation represents a critical knowledge gap that adversely affects our ability to identify promising treatment compounds and hinders the advancement of drug testing into relevant animal models and clinical trials. To begin to understand the biological characteristics that are inherent to each HIV-1 latency model, we compared the response properties of five primary T cell models, four J-Lat cell models and those obtained with a viral outgrowth assay using patient-derived infected cells. A panel of thirteen stimuli that are known to reactivate HIV by defined mechanisms of action was selected and tested in parallel in all models. Our results indicate that no single in vitro cell model alone is able to capture accurately the ex vivo response characteristics of latently infected T cells from patients. Most cell models demonstrated that sensitivity to HIV reactivation was skewed toward or against specific drug classes. Protein kinase C agonists and PHA reactivated latent HIV uniformly across models, although drugs in most other classes did not.

  17. An In-Depth Comparison of Latent HIV-1 Reactivation in Multiple Cell Model Systems and Resting CD4+ T Cells from Aviremic Patients (United States)

    Spina, Celsa A.; Anderson, Jenny; Archin, Nancie M.; Bosque, Alberto; Chan, Jonathan; Famiglietti, Marylinda; Greene, Warner C.; Kashuba, Angela; Lewin, Sharon R.; Margolis, David M.; Mau, Matthew; Ruelas, Debbie; Saleh, Suha; Shirakawa, Kotaro; Siliciano, Robert F.; Singhania, Akul; Soto, Paula C.; Terry, Valeri H.; Verdin, Eric; Woelk, Christopher; Wooden, Stacey; Xing, Sifei; Planelles, Vicente


    The possibility of HIV-1 eradication has been limited by the existence of latently infected cellular reservoirs. Studies to examine control of HIV latency and potential reactivation have been hindered by the small numbers of latently infected cells found in vivo. Major conceptual leaps have been facilitated by the use of latently infected T cell lines and primary cells. However, notable differences exist among cell model systems. Furthermore, screening efforts in specific cell models have identified drug candidates for “anti-latency” therapy, which often fail to reactivate HIV uniformly across different models. Therefore, the activity of a given drug candidate, demonstrated in a particular cellular model, cannot reliably predict its activity in other cell model systems or in infected patient cells, tested ex vivo. This situation represents a critical knowledge gap that adversely affects our ability to identify promising treatment compounds and hinders the advancement of drug testing into relevant animal models and clinical trials. To begin to understand the biological characteristics that are inherent to each HIV-1 latency model, we compared the response properties of five primary T cell models, four J-Lat cell models and those obtained with a viral outgrowth assay using patient-derived infected cells. A panel of thirteen stimuli that are known to reactivate HIV by defined mechanisms of action was selected and tested in parallel in all models. Our results indicate that no single in vitro cell model alone is able to capture accurately the ex vivo response characteristics of latently infected T cells from patients. Most cell models demonstrated that sensitivity to HIV reactivation was skewed toward or against specific drug classes. Protein kinase C agonists and PHA reactivated latent HIV uniformly across models, although drugs in most other classes did not. PMID:24385908

  18. Study of Uranium Transport Utilizing Reactive Numerical Modeling and Experimental Data from Heterogeneous Intermediate-Scale Tanks (United States)

    Rodriguez, D.; Miller, A.; Honeyman, B.


    The study of the transport of contaminants in groundwater is critical in order to mitigate risks to downstream receptors from sites where past releases of these contaminants has resulted in the degradation of the water quality of the underlying aquifer. In most cases, the fate and transport of these contaminants occurs in a chemically and physically heterogeneous environment; thereby making the prediction of the ultimate fate of these contaminants difficult. In order to better understand the fundamental processes that have the greatest effect on the transport of these contaminants, careful laboratory study must be completed in a controlled environment. Once the experimental data has been generated, the validation of numerical models may then be achieved. Questions on the management of contaminated sites may center on the long-term release (e.g., desorption, dissolution) behavior of contaminated geomedia. Data on the release of contaminants is often derived from bench-scale experiments or, in rare cases, through field-scale experiments. A central question, however, is how molecular-scale processes (e.g., bond breaking) are expressed at the macroscale. This presentation describes part of a collaborative study between the Colorado School of Mines, the USGS and Lawrence Berkeley National Lab on upscaling pore-scale processes to understanding field-scale observations. In the work described here, two experiments were conducted in two intermediate-scale tanks (2.44 m x 1.22 m x 7.6 cm and 2.44 m x 0.61 m x 7.6 cm) to generate data to quantify the processes of uranium dissolution and transport in fully saturated conditions, and to evaluate the ability of two reactive transport models to capture the relevant processes and predict U behavior at the intermediate scale. Each tank was designed so that spatial samples could be collected from the side of the tank, as well as samples from the effluent end of the tank. The larger tank was packed with a less than 2mm fraction of a

  19. Reactive standard deontic logic


    Gabbay, Dov M.; Straßer, Christian


    We introduce a reactive variant of SDL (standard deontic logic): SDLR1 (reactive standard deontic logic). Given a Kripkean view on the semantics of SDL in terms of directed graphs where arrows -> represent the accessibility relation between worlds, reactive models add two elements: arrows -> are labelled as 'active' or 'inactive', and double arrows a dagger connect arrows, e.g. (x(1) -> x(2)) a dagger (x(3) -> x(4)). The idea is that passing through x(1) -> x(2) activates a switch represented...

  20. Description of the Mountain Cloud Chemistry Program version of the PLUVIUS MOD 5. 0 reactive storm simulation model

    Energy Technology Data Exchange (ETDEWEB)

    Luecken, D.J.; Whiteman, C.D.; Chapman, E.G.; Andrews, G.L.; Bader, D.C.


    Damage to forest ecosystems on mountains in the eastern United States has prompted a study conducted for the US Environmental Protection Agency's Mountain Cloud Chemistry Program (MCCP). This study has led to the development of a numerical model called MCCP PLUVIUS, which has been used to investigate the chemical transformations and cloud droplet deposition in shallow, nonprecipitating orographic clouds. The MCCP PLUVIUS model was developed as a specialized version of the existing PLUVIUS MOD 5.0 reactive storm model. It is capable of simulating aerosol scavenging, nonreactive gas scavenging, aqueous phase SO/sub 2/ reactions, and cloud water deposition. A description of the new model is provided along with information on model inputs and outputs, as well as suggestions for its further development. The MCCP PLUVIUS incorporates a new method to determine the depth of the layer of air which flows over a mountaintop to produce an orographic cloud event. It provides a new method for calculating hydrogen ion concentrations, and provides updated expressions and values for solubility, dissociation and reaction rate constants.

  1. One-Dimensional Transport with Equilibrium Chemistry (OTEQ) - A Reactive Transport Model for Streams and Rivers (United States)

    Runkel, Robert L.


    OTEQ is a mathematical simulation model used to characterize the fate and transport of waterborne solutes in streams and rivers. The model is formed by coupling a solute transport model with a chemical equilibrium submodel. The solute transport model is based on OTIS, a model that considers the physical processes of advection, dispersion, lateral inflow, and transient storage. The equilibrium submodel is based on MINTEQ, a model that considers the speciation and complexation of aqueous species, acid-base reactions, precipitation/dissolution, and sorption. Within OTEQ, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (waterborne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach. The model's ability to simulate pH, precipitation/dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between instream chemistry and hydrologic transport at the field scale. This report details the development and application of OTEQ. Sections of the report describe model theory, input/output specifications, model applications, and installation instructions. OTEQ may be obtained over the Internet at

  2. Development of a Coolant Analysis Model for the Sodium Reactivity Calculation in the KALIMER Core

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Won Pyo; Lee, Yong Bum


    The present research concerns about developing a computational algorithm for the analysis of post boiling fuel temperature, based on the sodium boiling model proposed by USNRC. The model selection comes from the fact that the analysis of LMR sodium boiling had already been done using this model being coupled with SSC-L, and therefore its theory is believed to be a quite adequate option for compatibility to SSC-K. Physical phenomena characterizing UTO, ULOF, and ULOHS for KALIMER are analyzed for evaluation of the developed algorithm. The results obtained from the calculation are also compared with those of a previous model to confirm physical consistencies.

  3. Prediction of dissolved reactive phosphorus losses from small agricultural catchments: calibration and validation of a parsimonious model

    Directory of Open Access Journals (Sweden)

    C. Hahn


    Full Text Available Eutrophication of surface waters due to diffuse phosphorus (P losses continues to be a severe water quality problem worldwide, causing the loss of ecosystem functions of the respective water bodies. Phosphorus in runoff often originates from a small fraction of a catchment only. Targeting mitigation measures to these critical source areas (CSAs is expected to be most efficient and cost-effective, but requires suitable tools. Here we investigated the capability of the parsimonious Rainfall-Runoff-Phosphorus (RRP model to identify CSAs in grassland-dominated catchments based on readily available soil and topographic data. After simultaneous calibration on runoff data from four small hilly catchments on the Swiss Plateau, the model was validated on a different catchment in the same region without further calibration. The RRP model adequately simulated the discharge and dissolved reactive P (DRP export from the validation catchment. Sensitivity analysis showed that the model predictions were robust with respect to the classification of soils into "poorly drained" and "well drained", based on the available soil map. Comparing spatial hydrological model predictions with field data from the validation catchment provided further evidence that the assumptions underlying the model are valid and that the model adequately accounts for the dominant P export processes in the target region. Thus, the parsimonious RRP model is a valuable tool that can be used to determine CSAs. Despite the considerable predictive uncertainty regarding the spatial extent of CSAs, the RRP can provide guidance for the implementation of mitigation measures. The model helps to identify those parts of a catchment where high DRP losses are expected or can be excluded with high confidence. Legacy P was predicted to be the dominant source for DRP losses and thus, in combination with hydrologic active areas, a high risk for water quality.

  4. Reactive Hypoglycemia (United States)

    ... from low blood sugar (hypoglycemia) that occurs while fasting. Signs and symptoms of reactive hypoglycemia may include ... and very important. It's also important to include physical activity in your daily routine. Your doctor can help ...

  5. Reactive Arthritis

    Directory of Open Access Journals (Sweden)

    Eren Erken


    Full Text Available Reactive arthritis is an acute, sterile, non-suppurative and inflammatory arthropaty which has occured as a result of an infectious processes, mostly after gastrointestinal and genitourinary tract infections. Reiter syndrome is a frequent type of reactive arthritis. Both reactive arthritis and Reiter syndrome belong to the group of seronegative spondyloarthropathies, associated with HLA-B27 positivity and characterized by ongoing inflammation after an infectious episode. The classical triad of Reiter syndrome is defined as arthritis, conjuctivitis and urethritis and is seen only in one third of patients with Reiter syndrome. Recently, seronegative asymmetric arthritis and typical extraarticular involvement are thought to be adequate for the diagnosis. However, there is no established criteria for the diagnosis of reactive arthritis and the number of randomized and controlled studies about the therapy is not enough. [Archives Medical Review Journal 2013; 22(3.000: 283-299

  6. Use of a multi-species reactive transport model to simulate chloride ingress in mortar exposed to NaCl solution or sea-water

    DEFF Research Database (Denmark)

    Jensen, Mads Mønster; De Weerdt, K.; Johannesson, Björn;


    Simulations of ion ingress in Portland cement mortar using a multi-species reactive mass transport model are compared with experimental test results. The model is an extended version of the Poisson–Nernst–Planck equations, accounting for chemical equilibrium. Saturated mortar samples were exposed...

  7. Contaminant transport at a waste residue deposit: 1. Inverse flow and non-reactive transport modelling

    DEFF Research Database (Denmark)

    Sonnenborg, Torben Obel; Engesgaard, Peter Knudegaard; Rosbjerg, Dan


    and transport simulation model is combined with nonlinear least squares multiple regression. The U.S. Geological Survey method of characteristics model is used to simulate flow and transport, and the optimization part is solved using a Levenberg-Marquardt algorithm. The sensitivity of the optimization approach...

  8. Neutral-point voltage dynamic model of three-level NPC inverter for reactive load

    DEFF Research Database (Denmark)

    Maheshwari, Ram Krishan; Munk-Nielsen, Stig; Busquets-Monge, Sergio


    A three-level neutral-point-clamped inverter needs a controller for the neutral-point voltage. Typically, the controller design is based on a dynamic model. The dynamic model of the neutral-point voltage depends on the pulse width modulation technique used for the inverter. A pulse width modulati...

  9. Modelling the dispersion and transport of reactive pollutants in a deep urban street canyon: using large-eddy simulation. (United States)

    Zhong, Jian; Cai, Xiao-Ming; Bloss, William James


    This study investigates the dispersion and transport of reactive pollutants in a deep urban street canyon with an aspect ratio of 2 under neutral meteorological conditions using large-eddy simulation. The spatial variation of pollutants is significant due to the existence of two unsteady vortices. The deviation of species abundance from chemical equilibrium for the upper vortex is greater than that for the lower vortex. The interplay of dynamics and chemistry is investigated using two metrics: the photostationary state defect, and the inferred ozone production rate. The latter is found to be negative at all locations within the canyon, pointing to a systematic negative offset to ozone production rates inferred by analogous approaches in environments with incomplete mixing of emissions. This study demonstrates an approach to quantify parameters for a simplified two-box model, which could support traffic management and urban planning strategies and personal exposure assessment.

  10. Investigating the influence of subsurface heterogeneity on chemical weathering in the critical zone using high resolution reactive transport models (United States)

    Pandey, S.; Rajaram, H.


    The critical zone (CZ) represents a major life-sustaining realm of the terrestrial surface. The processes controlling the development and transformation of the CZ are important to continued health of the planet as human influence continues to grow. The CZ encompasses the shallow subsurface, a region of reaction, unsaturated flow, and transport. Chemical weathering in the subsurface is one of the important processes involved in the formation and functioning of the CZ. We present two case studies of reactive transport modeling to investigate the influence of subsurface heterogeneity and unsaturated flow on chemical weathering processes in the CZ. The model is implemented using the reactive transport code PFLOTRAN. Heterogeneity in subsurface flow is represented using multiple realizations of conductive fracture networks in a hillslope cross-section. The first case study is motivated by observations at the Boulder Creek Critical Zone Observatory (BCCZO) including extensive hydrologic and geochemical datasets. The simulations show that fractures greatly enhance weathering as compared to a homogeneous porous medium. Simulations of north-facing slope hydrology with prolonged snowmelt pulses also increases weathering rates, showing the importance of slope aspect on weathering intensity. Recent work elucidates deteriorating water quality caused by climate change in the CZ of watersheds where acid rock drainage (ARD) occurs. The more complex reactions of ARD require a customized kinetic reaction module with PFLOTRAN. The second case study explores the mechanisms by which changes in hydrologic forcing, air and ground temperatures, and water table elevations influence ARD. For instance, unreacted pyrite exposed by a water table drop was shown to produce a 125% increase in annual pyrite oxidization rate, which provides one explanation for increased ARD.

  11. Modelling and Validation of Synthesis of Poly Lactic Acid Using an Alternative Energy Source through a Continuous Reactive Extrusion Process

    Directory of Open Access Journals (Sweden)

    Satya P. Dubey


    Full Text Available PLA is one of the most promising bio-compostable and bio-degradable thermoplastic polymers made from renewable sources. PLA is generally produced by ring opening polymerization (ROP of lactide using the metallic/bimetallic catalyst (Sn, Zn, and Al or other organic catalysts in a suitable solvent. In this work, reactive extrusion experiments using stannous octoate Sn(Oct2 and tri-phenyl phosphine (PPh3 were considered to perform ROP of lactide. Ultrasound energy source was used for activating and/or boosting the polymerization as an alternative energy (AE source. Ludovic® software, designed for simulation of the extrusion process, had to be modified in order to simulate the reactive extrusion of lactide and for the application of an AE source in an extruder. A mathematical model for the ROP of lactide reaction was developed to estimate the kinetics of the polymerization process. The isothermal curves generated through this model were then used by Ludovic software to simulate the “reactive” extrusion process of ROP of lactide. Results from the experiments and simulations were compared to validate the simulation methodology. It was observed that the application of an AE source boosts the polymerization of lactide monomers. However, it was also observed that the predicted residence time was shorter than the experimental one. There is potentially a case for reducing the residence time distribution (RTD in Ludovic® due to the ‘liquid’ monomer flow in the extruder. Although this change in parameters resulted in validation of the simulation, it was concluded that further research is needed to validate this assumption.

  12. Thermal-mechanical-chemical responses of polymer-bonded explosives using a mesoscopic reactive model under impact loading. (United States)

    Wang, XinJie; Wu, YanQing; Huang, FengLei


    A mesoscopic framework is developed to quantify the thermal-mechanical-chemical responses of polymer-bonded explosive (PBX) samples under impact loading. A mesoscopic reactive model is developed for the cyclotetramethylenetetranitramine (HMX) crystal, which incorporates nonlinear elasticity, crystal plasticity, and temperature-dependent chemical reaction. The proposed model was implemented in the finite element code ABAQUS by the user subroutine VUMAT. A series of three-dimensional mesoscale models were constructed and calculated under low-strength impact loading scenarios from 100m/s to 600m/s where only the first wave transit is studied. Crystal anisotropy and microstructural heterogeneity are responsible for the nonuniform stress field and fluctuations of the stress wave front. At a critical impact velocity (≥300m/s), a chemical reaction is triggered because the temperature contributed by the volumetric and plastic works is sufficiently high. Physical quantities, including stress, temperature, and extent of reaction, are homogenized from those across the microstructure at the mesoscale to compare with macroscale measurements, which will advance the continuum-level models. The framework presented in this study has important implications in understanding hot spot ignition processes and improving predictive capabilities in energetic materials.

  13. Review of pore network modelling of porous media: Experimental characterisations, network constructions and applications to reactive transport (United States)

    Xiong, Qingrong; Baychev, Todor G.; Jivkov, Andrey P.


    Pore network models have been applied widely for simulating a variety of different physical and chemical processes, including phase exchange, non-Newtonian displacement, non-Darcy flow, reactive transport and thermodynamically consistent oil layers. The realism of such modelling, i.e. the credibility of their predictions, depends to a large extent on the quality of the correspondence between the pore space of a given medium and the pore network constructed as its representation. The main experimental techniques for pore space characterisation, including direct imaging, mercury intrusion porosimetry and gas adsorption, are firstly summarised. A review of the main pore network construction techniques is then presented. Particular focus is given on how such constructions are adapted to the data from experimentally characterised pore systems. Current applications of pore network models are considered, with special emphasis on the effects of adsorption, dissolution and precipitation, as well as biomass growth, on transport coefficients. Pore network models are found to be a valuable tool for understanding and predicting meso-scale phenomena, linking single pore processes, where other techniques are more accurate, and the homogenised continuum porous media, used by engineering community.

  14. An adaptive hybrid EnKF-OI scheme for efficient state-parameter estimation of reactive contaminant transport models

    KAUST Repository

    El Gharamti, Mohamad


    Reactive contaminant transport models are used by hydrologists to simulate and study the migration and fate of industrial waste in subsurface aquifers. Accurate transport modeling of such waste requires clear understanding of the system\\'s parameters, such as sorption and biodegradation. In this study, we present an efficient sequential data assimilation scheme that computes accurate estimates of aquifer contamination and spatially variable sorption coefficients. This assimilation scheme is based on a hybrid formulation of the ensemble Kalman filter (EnKF) and optimal interpolation (OI) in which solute concentration measurements are assimilated via a recursive dual estimation of sorption coefficients and contaminant state variables. This hybrid EnKF-OI scheme is used to mitigate background covariance limitations due to ensemble under-sampling and neglected model errors. Numerical experiments are conducted with a two-dimensional synthetic aquifer in which cobalt-60, a radioactive contaminant, is leached in a saturated heterogeneous clayey sandstone zone. Assimilation experiments are investigated under different settings and sources of model and observational errors. Simulation results demonstrate that the proposed hybrid EnKF-OI scheme successfully recovers both the contaminant and the sorption rate and reduces their uncertainties. Sensitivity analyses also suggest that the adaptive hybrid scheme remains effective with small ensembles, allowing to reduce the ensemble size by up to 80% with respect to the standard EnKF scheme. © 2014 Elsevier Ltd.

  15. Hybrid approach combining dissipative particle dynamics and finite-difference diffusion model: simulation of reactive polymer coupling and interfacial polymerization. (United States)

    Berezkin, Anatoly V; Kudryavtsev, Yaroslav V


    A novel hybrid approach combining dissipative particle dynamics (DPD) and finite difference (FD) solution of partial differential equations is proposed to simulate complex reaction-diffusion phenomena in heterogeneous systems. DPD is used for the detailed molecular modeling of mass transfer, chemical reactions, and phase separation near the liquid∕liquid interface, while FD approach is applied to describe the large-scale diffusion of reactants outside the reaction zone. A smooth, self-consistent procedure of matching the solute concentration is performed in the buffer region between the DPD and FD domains. The new model is tested on a simple model system admitting an analytical solution for the diffusion controlled regime and then applied to simulate practically important heterogeneous processes of (i) reactive coupling between immiscible end-functionalized polymers and (ii) interfacial polymerization of two monomers dissolved in immiscible solvents. The results obtained due to extending the space and time scales accessible to modeling provide new insights into the kinetics and mechanism of those processes and demonstrate high robustness and accuracy of the novel technique.

  16. An adaptive sparse-grid high-order stochastic collocation method for Bayesian inference in groundwater reactive transport modeling

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Guannan [ORNL; Webster, Clayton G [ORNL; Gunzburger, Max D [ORNL


    Although Bayesian analysis has become vital to the quantification of prediction uncertainty in groundwater modeling, its application has been hindered due to the computational cost associated with numerous model executions needed for exploring the posterior probability density function (PPDF) of model parameters. This is particularly the case when the PPDF is estimated using Markov Chain Monte Carlo (MCMC) sampling. In this study, we develop a new approach that improves computational efficiency of Bayesian inference by constructing a surrogate system based on an adaptive sparse-grid high-order stochastic collocation (aSG-hSC) method. Unlike previous works using first-order hierarchical basis, we utilize a compactly supported higher-order hierar- chical basis to construct the surrogate system, resulting in a significant reduction in the number of computational simulations required. In addition, we use hierarchical surplus as an error indi- cator to determine adaptive sparse grids. This allows local refinement in the uncertain domain and/or anisotropic detection with respect to the random model parameters, which further improves computational efficiency. Finally, we incorporate a global optimization technique and propose an iterative algorithm for building the surrogate system for the PPDF with multiple significant modes. Once the surrogate system is determined, the PPDF can be evaluated by sampling the surrogate system directly with very little computational cost. The developed method is evaluated first using a simple analytical density function with multiple modes and then using two synthetic groundwater reactive transport models. The groundwater models represent different levels of complexity; the first example involves coupled linear reactions and the second example simulates nonlinear ura- nium surface complexation. The results show that the aSG-hSC is an effective and efficient tool for Bayesian inference in groundwater modeling in comparison with conventional

  17. Reactive transport modeling of geochemical controls on secondary water quality impacts at a crude oil spill site near Bemidji, MN (United States)

    Ng, Gene-Hua Crystal.; Bekins, Barbara A.; Cozzarelli, Isabelle M.; Baedecker, Mary Jo; Bennett, Philip C.; Amos, Richard T.; Herkelrath, William N.


    Anaerobic biodegradation of organic amendments and contaminants in aquifers can trigger secondary water quality impacts that impair groundwater resources. Reactive transport models help elucidate how diverse geochemical reactions control the spatiotemporal evolution of these impacts. Using extensive monitoring data from a crude oil spill site near Bemidji, Minnesota (USA), we implemented a comprehensive model that simulates secondary plumes of depleted dissolved O2 and elevated concentrations of Mn2+, Fe2+, CH4, and Ca2+ over a two-dimensional cross section for 30 years following the spill. The model produces observed changes by representing multiple oil constituents and coupled carbonate and hydroxide chemistry. The model includes reactions with carbonates and Fe and Mn mineral phases, outgassing of CH4 and CO2 gas phases, and sorption of Fe, Mn, and H+. Model results demonstrate that most of the carbon loss from the oil (70%) occurs through direct outgassing from the oil source zone, greatly limiting the amount of CH4 cycled down-gradient. The vast majority of reduced Fe is strongly attenuated on sediments, with most (91%) in the sorbed form in the model. Ferrous carbonates constitute a small fraction of the reduced Fe in simulations, but may be important for furthering the reduction of ferric oxides. The combined effect of concomitant redox reactions, sorption, and dissolved CO2 inputs from source-zone degradation successfully reproduced observed pH. The model demonstrates that secondary water quality impacts may depend strongly on organic carbon properties, and impacts may decrease due to sorption and direct outgassing from the source zone.

  18. Reactive Solute Transport in Streams: 1. Development of an Equilibrium-Based Model (United States)

    Runkel, Robert L.; Bencala, Kenneth E.; Broshears, Robert E.; Chapra, Steven C.


    An equilibrium-based solute transport model is developed for the simulation of trace metal fate and transport in streams. The model is formed by coupling a solute transport model with a chemical equilibrium submodel based on MINTEQ. The solute transport model considers the physical processes of advection, dispersion, lateral inflow, and transient storage, while the equilibrium submodel considers the speciation and complexation of aqueous species, precipitation/dissolution and sorption. Within the model, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (water-borne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach.

  19. Reactive solute transport in streams. 1. Development of an equilibrium- based model (United States)

    Runkel, R.L.; Bencala, K.E.; Broshears, R.E.; Chapra, S.C.


    An equilibrium-based solute transport model is developed for the simulation of trace metal fate and transport in streams. The model is formed by coupling a solute transport model with a chemical equilibrium submodel based on MINTEQ. The solute transport model considers the physical processes of advection, dispersion, lateral inflow, and transient storage, while the equilibrium submodel considers the speciation and complexation of aqueous species, precipitation/dissolution and sorption. Within the model, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (water-borne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach.

  20. Reactive transport modelling of As- and P-species in the rhizosphere (United States)

    Szegedi, K.; Vetterlein, D.; Jahn, R.


    The toxic arsenate competes with the nutrient phosphate for binding sites in soil, i.e. at goethite or ferrihydrite surfaces and for binding sites at root membranes. P in soil can be mobilised by plants through exudation of organic anions like citrate or by release of protons. These mechanisms may alter the competition between As(V) and P for binding sites and thus enhance arsenate transfer into the food chain. In a compartment system experiment with corn plants the temporal and spatial dynamics of different parameters (soil solution P, As(V), citrate and proton concentration) were measured with different initial application rates of goethite (Vetterlein et al, 2007). For the integration of the different parameters the experiment was modelled using the RhizoMath code (Szegedi et al, 2008), that is based on coupling the mathematical package MATLAB with the geochemical code PHREEQC. The initialization module of RhizoMath was used to determine the number of surface binding sites of goethite and values of the equilibrium constants of corresponding stoichiometric equations describing the surface complexation of As(V) on goethite as given in Szegedi et al. (2008). The transport module of RhizoMath was used to model transport and speciation in the compartment system. Although the model was able to qualitatively represent experimental observations, a quantitative agreement between modelled and measured data could not be achieved. Thus, in a second step, the transport module was extended with a root compartment factor that expresses the relative coverage of the root compartment by the roots and the active root surface behind the unit area of the compartment cross section. This allowed modelling a growing plant in the compartment system. As temporal changes in water flux and nutrient demand are not necessarily identical, temporal changes in water flux and nutrient demand were scaled independently from each other, using constant, linear or measured water consumption and leaf

  1. Reactive Transport Modeling of Induced Calcite Precipitation Reaction Fronts in Porous Media Using A Parallel, Fully Coupled, Fully Implicit Approach (United States)

    Guo, L.; Huang, H.; Gaston, D.; Redden, G. D.; Fox, D. T.; Fujita, Y.


    Inducing mineral precipitation in the subsurface is one potential strategy for immobilizing trace metal and radionuclide contaminants. Generating mineral precipitates in situ can be achieved by manipulating chemical conditions, typically through injection or in situ generation of reactants. How these reactants transport, mix and react within the medium controls the spatial distribution and composition of the resulting mineral phases. Multiple processes, including fluid flow, dispersive/diffusive transport of reactants, biogeochemical reactions and changes in porosity-permeability, are tightly coupled over a number of scales. Numerical modeling can be used to investigate the nonlinear coupling effects of these processes which are quite challenging to explore experimentally. Many subsurface reactive transport simulators employ a de-coupled or operator-splitting approach where transport equations and batch chemistry reactions are solved sequentially. However, such an approach has limited applicability for biogeochemical systems with fast kinetics and strong coupling between chemical reactions and medium properties. A massively parallel, fully coupled, fully implicit Reactive Transport simulator (referred to as “RAT”) based on a parallel multi-physics object-oriented simulation framework (MOOSE) has been developed at the Idaho National Laboratory. Within this simulator, systems of transport and reaction equations can be solved simultaneously in a fully coupled, fully implicit manner using the Jacobian Free Newton-Krylov (JFNK) method with additional advanced computing capabilities such as (1) physics-based preconditioning for solution convergence acceleration, (2) massively parallel computing and scalability, and (3) adaptive mesh refinements for 2D and 3D structured and unstructured mesh. The simulator was first tested against analytical solutions, then applied to simulating induced calcium carbonate mineral precipitation in 1D columns and 2D flow cells as analogs

  2. Numerical Modeling of Reactive Multiphase Flow for FCC and Hot Gas Desulfurization Circulating Fluidized Beds

    Energy Technology Data Exchange (ETDEWEB)

    Miller, Aubrey L. [WSU Research Corporation, Morgantown, WV (USA)


    This work was carried out to understand the behavior of the solid and gas phases in a CFB riser. Only the riser is modeled as a straight pipe. A model with linear algebraic approximation to solids viscosity of the form, {musubs} = 5.34{epsisubs}, ({espisubs} is the solids volume fraction) with an appropriate boundary condition at the wall obtained by approximate momentum balance solution at the wall to acount for the solids recirculation is tested against experimental results. The work done was to predict the flow patterns in the CFB risers from available experimental data, including data from a 7.5-cm-ID CFB riser at the Illinois Institute of Technology and data from a 20.0-cm-ID CFB riser at the Particulate Solid Research, Inc., facility. This research aims at modeling the removal of hydrogen sulfide from hot coal gas using zinc oxide as the sorbent in a circulating fluidized bed and in the process indentifying the parameters that affect the performance of the sulfidation reactor. Two different gas-solid reaction models, the unreacted shrinking core (USC) and the grain model were applied to take into account chemical reaction resistances. Also two different approaches were used to affect the hydrodynamics of the process streams. The first model takes into account the effect of micro-scale particle clustering by adjusting the gas-particle drag law and the second one assumes a turbulent core with pseudo-steady state boundary condition at the wall. A comparison is made with experimental results.

  3. Modeling Solute Reactivity in a Phreatic Solution Conduit Penetrating a Karst Aquifer (United States)

    Field, M.


    A two-dimensional model for solute migration, transformation, and sorption in a phreatic solution conduit penetrating a karst aquifer is presented in which the solute is anthropogenic to the natural system. Transformation of a reacting solute in a solution conduit has generally been accepted as likely occurring but actual physical measurements and mathematical analyses of the suspected process are lacking, primarily because of the logistics of sample collection and the complexities associated with solute transport through solution conduits. The model demonstrates how a reacting solute might be converted to a product solute some of which then diffuses to the solution conduit wall where it may become adsorbed. Model effects vary for laminar flow and turbulent flow in the axial direction. Laminar and turbulent diffusion in the radial direction also exhibits marked differences. In addition to single reaction zones simulations considered multiple adjacent and nonadjacent reaction zones, both with varying reaction rates. Reaction zones were found to enhance subsequent reactions due to some overlap resulting from the hydrodynamic dispersion caused by the axial flow. The simulations showed that varying the reaction rate coefficient strongly affects solute reactions, but that varying deposition coefficients had only minimal impacts. Application of the model to a tracer test that used the tracer dye, Rhodamine WT which readily converts to deaminoalkylated Rhodamine WT after release, illustrates how the model may be used to suggest a possible cause for less than 100% tracer mass recovery. In terms of pollutants in a karst aquifer the model suggests a possible explanation for pollutant transformation in a solution conduit.

  4. Reactive nitrogen in Mexico City and its relation to ozone-precursor sensitivity: results from photochemical models

    Directory of Open Access Journals (Sweden)

    S. Sillman


    Full Text Available We use results of a 3-D photochemistry/transport model for ozone formation in Mexico City during events in 1997 to investigate ambient concentrations of reactive nitrogen in relation to ozone-precursor sensitivity. Previous results from other locations suggest that ratios such as O3/NOy and H2O2/HNO3 might provide measurement-based indicators for NOx-sensitive or VOC-sensitive conditions. Mexico City presents a different environment due to its high concentrations of VOC and high level of pollutants in general. The model predicts a correlation between PAN and O3 with relatively high PAN/O3 (0.07, which is still lower than measured values. The model PAN is comparable with results from a model for Paris but much higher than were found in Nashville in both models and measurements. The difference can be explained by the lower temperature in Mexico City relative to Nashville. Model HNO3 in Mexico City is unusually low for an urban area and PAN/HNO3 is very high, probably due to the high ratio of reactivity-weighted VOC to NOx. The model predicts that VOC-sensitive chemistry in Mexico is associated with high NOx, NOy and NOx/NOy and with low O3/NOy and H2O2/HNO3, suggesting that these indicators work well for Mexico City. The relation between ozone-precursor sensitivity and either O3/NOz or O3/HNO3 is more ambiguous. VOC-sensitive conditions are associated with higher O3/HNO3 than would be found in NOx-sensitive conditions, but model O3/HNO3 associated with both NOx-sensitive and VOC-sensitive chemistry is higher in Mexico than in other cities. The model predicts mixed sensitivity to NOx and VOC in Mexico City, with a

  5. Reactive nitrogen in Mexico City and its relation to ozone-precursor sensitivity: results from photochemical models

    Directory of Open Access Journals (Sweden)

    S. Sillman


    Full Text Available We use results of a 3-D photochemistry/transport model for ozone formation in Mexico City during events in 1997 to investigate ambient concentrations of reactive nitrogen in relation to ozone-precursor sensitivity. Previous results from other locations suggest that ratios such as O3/NOy and H2O2/HNO3 might provide measurement-based indicators for NOx-sensitive or VOC-sensitive conditions. Mexico City presents a different environment due to its high concentrations of VOC and high level of pollutants in general. The model predicts a correlation between PAN and O3 with relatively high PAN/O3 (0.07, which is still lower than measured values. The model PAN is comparable with results from a model for Paris but much higher than were found in Nashville in both models and measurements. The difference is due in part to the lower temperature in Mexico City relative to Nashville. Model HNO3 in Mexico City is unusually low for an urban area and PAN/HNO3 is very high, probably due to the high ratio of reactivity-weighted VOC to NOx. The model predicts that VOC-sensitive chemistry in Mexico is associated with high NOx, NOy and NOx/NOy and with low O3/NOy and H2O2/HNO3, suggesting that these indicators work well for Mexico City. The relation between ozone-precursor sensitivity and either O3/NOz or O3/HNO3 is more ambiguous. VOC-sensitive conditions are associated with higher O3/HNO3 than would be found in NOx-sensitive conditions, but model O3/HNO3 associated with both NOx-sensitive and VOC-sensitive chemistry is higher in Mexico than in other cities. The model predicts a mixed pattern of ozone-precursor sensitivity in Mexico City, with

  6. A model for reactive porous transport during re-wetting of hardened concrete

    CERN Document Server

    Chapwanya, Michael; Stockie, John M


    We develop a mathematical model that captures the transport of liquid water in hardened concrete, as well as the chemical reactions that occur between the infiltrating water and the residual calcium silicate compounds that reside in the porous concrete matrix. We investigate the hypothesis that the reaction product -- calcium silicate hydrate gel -- clogs the pores within the concrete thereby hindering water transport. Using numerical simulations, we determine the sensitivity of the model solution to changes in various physical parameters, and compare to experimental results available in the literature.

  7. A reactive transport modelling approach to assess the leaching potential of hydraulic fracturing fluids associated with coal seam gas extraction (United States)

    Mallants, Dirk; Simunek, Jirka; Gerke, Kirill


    Coal Seam Gas production generates large volumes of "produced" water that may contain compounds originating from the use of hydraulic fracturing fluids. Such produced water also contains elevated concentrations of naturally occurring inorganic and organic compounds, and usually has a high salinity. Leaching of produced water from storage ponds may occur as a result of flooding or containment failure. Some produced water is used for irrigation of specific crops tolerant to elevated salt levels. These chemicals may potentially contaminate soil, shallow groundwater, and groundwater, as well as receiving surface waters. This paper presents an application of scenario modelling using the reactive transport model for variably-saturated media HP1 (coupled HYDRUS-1D and PHREEQC). We evaluate the fate of hydraulic fracturing chemicals and naturally occurring chemicals in soil as a result of unintentional release from storage ponds or when produced water from Coal Seam Gas operations is used in irrigation practices. We present a review of exposure pathways and relevant hydro-bio-geo-chemical processes, a collation of physico-chemical properties of organic/inorganic contaminants as input to a set of generic simulations of transport and attenuation in variably saturated soil profiles. We demonstrate the ability to model the coupled processes of flow and transport in soil of contaminants associated with hydraulic fracturing fluids and naturally occurring contaminants.

  8. A multiscale three-zone reactive mixing model for engineering a scale separation in enzymatic hydrolysis of cellulose. (United States)

    Chakraborty, Saikat; Raju, Satyanarayana; Pal, Ramendra Kishor


    This multiscale three-zone reactive mixing model provides a theoretical framework for engineering a scale separation in batch enzymatic hydrolysis of cellulose to strategize significant leaps in glucose yields. Formulated using the Liapunov-Schmidt method of the classical bifurcation theory, our model explores the multiscale spatiotemporal dynamics between the fundamental processes of macromixing (convection) and micromixing (diffusion) of the enzymes (Endoglucanase, Exoglucanase, β-glucasidase) and reducing sugars, adsorption and desorption of enzymes on the solid cellulosic substrates, and the product-inhibited liquid and solid phase enzymatic reactions that depolymerize microcrystalline cellulose (Avicel). The model is validated for a range of substrate loadings (2-5%) using our experimental results for the two asymptotic cases of no mixing and continuous mixing, as well as for the macro/micro scale-separated optimal mixing strategy that increases the glucose yield by up to 26% by macromixing completely for an initial period followed by micromixing for the remaining duration of the hydrolysis. Copyright © 2014 Elsevier Ltd. All rights reserved.

  9. Reactive transport modeling of long-term secondary water quality impacts of a crude oil spill at Bemidji, Minnesota (United States)

    Ng, G. C.; Bekins, B. A.; Cozzarelli, I.; Baedecker, M. J.; Amos, R. T.


    The groundwater impacts from a crude oil pipeline rupture in 1979 near Bemidji, Minnesota, have been continuously and intensively investigated for almost 30 years. Previous studies on the resulting plume have significantly contributed to the understanding of natural attenuation processes. The Bemidji site also offers valuable insights on the potential long-term impacts caused by anaerobic bioremediation approaches such as electron donor addition. There has been increased concern about the "secondary impacts" of electron donor addition - including groundwater plumes with reduced dissolved oxygen and elevated levels of methane and other dissolved inorganic components - yet long term information is not yet available at remediation sites. Bemidji provides an example of long term water quality changes resulting from anaerobic biodegradation. While previous Bemidji modeling efforts have largely focused on the fate of the crude oil, we provide a modeling study that aims to also properly represent further evolution of the plume. This requires more comprehensive modeling than has been previously carried out at the site. We have implemented the reactive transport model PHT3D for 2-dimensional simulations that include not only kinetic degradation of organic carbon via redox reactions, but also represent mineral phases, sorption processes, out-gassing of methane and CO2, full carbonate chemistry, and re-oxidation reactions. The model is constrained using a full suite of observations on various oil constituents and dissolved and solid components that span the 30 years since the spill - a uniquely extensive data set on long term conditions. The secondary impacts at Bemidji consist of a plume containing significant methane, depleted dissolved oxygen, and dissolved iron. Our work demonstrates that the secondary plume evolution is very sensitive to the proper characterization of the electron donor (organic carbon) source, naturally-occurring mineral electron acceptors, and

  10. Reactive-transport modeling of fly ash-wate-brines interactions from laboratory-scale column studies (United States)

    Mbugua, John M.; Catherine Ngila, J.; Kindness, Andrew; Demlie, Molla

    Dynamic leaching tests are important studies that provide more insights into time-dependent leaching mechanisms of any given solid waste. Hydrogeochemical modeling using PHREEQC was applied for column modeling of two ash recipes and brines generated from South African coal utility plants, Sasol and Eskom. The modeling results were part of a larger ash-brine study aimed at acquiring knowledge on (i) quantification and characterization of the products formed when ash is in contact with wate-brines in different scenarios, (ii) the mineralogical changes associated with wate-brine-ash interactions over time, (iii) species concentration, and (iv) leaching and transport controlling factors. The column modeling was successfully identified and quantified as important reactive mineralogical phases controlling major, minor and trace elements' release. The pH of the solution was found to be a very important controlling factor in leaching chemistry. The highest mineralogical transformation took place in the first 10 days of ash contact with either water or brines, and within 0.1 m from the column inflow. Many of the major and trace elements Ca, Mg, Na, K, Sr, S(VI), Fe, are leached easily into water systems and their concentration fronts were high at the beginning (within 0.1 m from the column inflow and within the first 10 days) upon contact with the liquid phase. However, their concentration decreased with time until a steady state was reached. Modeling results also revealed that geochemical reactions taking place during ash-wate-brine interactions does affect the porosity of the ash, whereas the leaching processes lead to increased porosity. Besides supporting experimental data, modeling results gave predictive insights on leaching of elements which may directly impact on the environment, particularly ground water. These predictions will help develop scenarios and offer potential guide for future sustainable waste management practices as a way of addressing the co

  11. Reactive transport in surface sediments. I. Model complexity and software quality

    NARCIS (Netherlands)

    Meysman, F.J.R.; Middelburg, J.J.; Herman, P.M.J.; Heip, C.H.R.


    Analysis of three recent diagenetic model codes (OMEXDIA, CANDI and STEADYSED) revealed that codes have a rigid, static and problem-specific character, leaving little autonomy for the application user. The resulting lack of flexibility and extensibility, and the associated need for ground-level repr

  12. Comprehensive atmospheric modeling of reactive cyclic siloxanes and their oxidation products (United States)

    Janechek, Nathan J.; Hansen, Kaj M.; Stanier, Charles O.


    Cyclic volatile methyl siloxanes (cVMSs) are important components in personal care products that transport and react in the atmosphere. Octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and their gas-phase oxidation products have been incorporated into the Community Multiscale Air Quality (CMAQ) model. Gas-phase oxidation products, as the precursor to secondary organic aerosol from this compound class, were included to quantify the maximum potential for aerosol formation from gas-phase reactions with OH. Four 1-month periods were modeled to quantify typical concentrations, seasonal variability, spatial patterns, and vertical profiles. Typical model concentrations showed parent compounds were highly dependent on population density as cities had monthly averaged peak D5 concentrations up to 432 ng m-3. Peak oxidized D5 concentrations were significantly less, up to 9 ng m-3, and were located downwind of major urban areas. Model results were compared to available measurements and previous simulation results. Seasonal variation was analyzed and differences in seasonal influences were observed between urban and rural locations. Parent compound concentrations in urban and peri-urban locations were sensitive to transport factors, while parent compounds in rural areas and oxidized product concentrations were influenced by large-scale seasonal variability in OH.

  13. Reactivity of fly ash: extension and application of a shrinking core model

    NARCIS (Netherlands)

    Brouwers, Jos; van Eijk, R.J.


    In the present paper a theoretical study is presented on the dissolution (reaction) of pulverised powder coal fly ash. A shrinking core model is derived for hollow spheres that contain two regions (outer hull and inner region). The resulting analytical equations are applied to the dissolution

  14. Three-dimensional model of stellacyanin and its implications for electron transfer reactivity

    DEFF Research Database (Denmark)

    Wherland, S; Farver, O; Pecht, I


    . The structure also indicates that a carbonyl oxygen atom is near the copper, thus the site may have analogy to the Alcaligenes denitrificans azurin (Az) site, although the amino acid sequence is more homologous to that of Pc. The model indicates that aspartate 49, reductively labeled by Cr(III), is near...

  15. A Simple Model for the Vertical Transport of Reactive Species in the Convective Atmospheric Boundary Layer

    DEFF Research Database (Denmark)

    Kristensen, Leif; Lenschow, Donald H.; Gurarie, David


    with standard parameterizations. This leads to formulations for profiles of the turbulent diffusivity and the ratio of temperature-scalar covariance to the flux of the passive scalar. The model is then extended to solving, in terms of profiles of mean concentrations and fluxes, the NO x –O3 triad problem...

  16. A constructed wetland model for synthetic reactive dye wastewater treatment by narrow-leaved cattails (Typha angustifolia Linn.). (United States)

    Nilratnisakorn, S; Thiravetyan, P; Nakbanpote, W


    Textile wastewater is contaminated by reactive dye causing unattractive levels of wastewater color, high pH and high salt content when discharged into public water systems. Decolorization of textile wastewater by plant, phytoremediation, is an alternative, sustainable method which is suitable for long term operation. Narrow-leaved cattails are one species of wetland plant with efficiency for decolorizing and remediating textile wastewater. In addition, chemical oxygen demand (COD) can be lowered and dye residue can be removed. The plant also showed a good salt tolerance even after being exposed to a salt solution for 15 days. The narrow-leaved cattails were set up in a constructed wetland model with a vertical flow system operating from bottom to top for synthetic reactive dye wastewater (SRDW) removal. Narrow-leaved cattails could achieve the removal of SRDW at approximately 0.8 g(SRDW) m(-2) day(-1). Decolorization of SRDW by this plant was approximately 60%. The advantage of this method is that it is suitable for textile wastewater management and improvement of wetland. These plants could lower COD, remove dye, sodium and total dissolved solids (TDS) whereas other biological and chemical methods could not remove TDS and dye in the same time. These results suggested that the spongy cell structure of this plant has the ability to absorb large amounts of water and nutrients. Physico-chemical analysis revealed increasing amounts of sulfur, silicon, iron and calcium in the plant leafs and roots after exposure to wastewater. Proteins or amide groups in the plant might help in textile dye removal. Regarding decolorization, this plant accumulates dye in the intercellular space and still grows in this SRDW condition. Hence, it can be noted here that narrow-leaved cattails are efficient for textile dye wastewater treatment.

  17. Purinergic 2Y1 receptor stimulation decreases cerebral edema and reactive gliosis in a traumatic brain injury model. (United States)

    Talley Watts, Lora; Sprague, Shane; Zheng, Wei; Garling, R Justin; Jimenez, David; Digicaylioglu, Murat; Lechleiter, James


    Traumatic brain injury (TBI) is the leading cause of death and disability in children and young adults. Neuroprotective agents that may promote repair or counteract damage after injury do not currently exist. We recently reported that stimulation of the purinergic receptor subtype P2Y(1)R using 2-methylthioladenosine 5' diphosphate (2MeSADP) significantly reduced cytotoxic edema induced by photothrombosis. Here, we tested whether P2Y(1)R stimulation was neuroprotective after TBI. A controlled closed head injury model was established for mice using a pneumatic impact device. Brains were harvested at 1, 3, or 7 days post-injury and assayed for morphological changes by immunocytochemistry, Western blot analysis, and wet/dry weight. Cerebral edema and expression of both aquaporin type 4 and glial fibrillary acidic protein were increased at all time points examined. Immunocytochemical measurements in both cortical and hippocampal slices also revealed significant neuronal swelling and reactive gliosis. Treatment of mice with 2MeSADP (100 μM) or MRS2365 (100 μM) 30 min after trauma significantly reduced all post-injury symptoms of TBI including edema, neuronal swelling, reactive gliosis, and AQ4 expression. The neuroprotective effect was lost in IP(3)R2-/- mice treated with 2MeSADP. Immunocytochemical labeling of brain slices confirmed that P2Y(1)R expression was defined to cortical and hippocampal astrocytes, but not neurons. Taken together, the data show that stimulation of astrocytic P2Y(1)Rs significantly reduces brain injury after acute trauma and is mediated by the IP(3)-signaling pathway. We suggest that enhancing astrocyte mitochondrial metabolism offers a promising neuroprotective strategy for a broad range of brain injuries.

  18. Acrolein stimulates the synthesis of IL-6 and C-reactive protein (CRP) in thrombosis model mice and cultured cells. (United States)

    Saiki, Ryotaro; Hayashi, Daisuke; Ikuo, Yukiko; Nishimura, Kazuhiro; Ishii, Itsuko; Kobayashi, Kaoru; Chiba, Kan; Toida, Toshihiko; Kashiwagi, Keiko; Igarashi, Kazuei


    Measurements of protein-conjugated acrolein (PC-Acro), IL-6, and C-reactive protein (CRP) in plasma were useful for identifying silent brain infarction with high sensitivity and specificity. The aim of this study was to determine whether acrolein causes increased production of IL-6 and CRP in thrombosis model mice and cultured cells. In mice with photochemically induced thrombosis, acrolein produced at the locus of infarction increased the level of IL-6 and then CRP in plasma. This was confirmed in cell culture systems - acrolein stimulated the production of IL-6 in mouse neuroblastoma Neuro-2a cells, mouse macrophage-like J774.1 cells, and human umbilical vein endothelial cells (HUVEC), and IL-6 in turn stimulated the production of CRP in human hepatocarcinoma cells. The level of IL-6 mRNA was increased by acrolein through an increase in phosphorylation of the transcription factors, c-Jun, and NF-κB p65. Furthermore, CRP stimulated IL-6 production in mouse macrophage-like J774.1 cells and HUVEC. IL-6 functioned as a protective factor against acrolein toxicity in Neuro-2a cells and HUVEC. These results show that acrolein stimulates the synthesis of IL-6 and CRP, which function as protecting factors against acrolein toxicity, and that the combined measurement of PC-Acro, IL-6, and CRP is effective for identification of silent brain infarction. The combined measurements of protein-conjugated acrolein (PC-Acro), IL-6, and C-reactive protein (CRP) in plasma were useful for identifying silent brain infarction. The aim of this study was to determine whether acrolein causes increased production of IL-6 and CRP, and indeed acrolein increased IL-6 synthesis and IL-6 in turn increased CRP synthesis. Furthermore, IL-6 decreased acrolein toxicity in several cell lines.

  19. Biogenic silica dissolution in diatom aggregates: insights from reactive transport modelling

    KAUST Repository

    Moriceau, B


    © Inter-Research 2014. Diatom aggregates contribute significantly to the vertical sinking flux of particulate matter in the ocean. These fragile structures form a specific microhabitat for the aggregated cells, but their internal chemical and physical characteristics remain largely unknown. Studies on the impact of aggregation on the Si cycle led to apparent inconsistency. Despite a lower biogenic silica (bSiO2) dissolution rate and diffusion of the silicic acid (dSi) being similar in aggregates and in sea-water, dSi surprisingly accumulates in aggregates. A reaction-diffusion model helps to clarify this incoherence by reconstructing dSi accumulation measured during batch experiments with aggregated and non-aggregated Skeletonema marinoi and Chaetoceros decipiens. The model calculates the effective bSiO2 dissolution rate as opposed to the experimental apparent bSiO2 dissolution rate, which is the results of the effective dissolution of bSiO2 and transport of dSi out of the aggregate. In the model, dSi transport out of the aggregate is modulated by alternatively considering retention (decrease of the dSi diffusion constant) and adsorption (reversible chemical bonds between dSi and the aggregate matrix) processes. Modelled bSiO2 dissolution is modulated by the impact of dSi concentration inside aggregates and diatom viability, as enhanced persistence of metabolically active diatoms has been observed in aggregates. Adsorption better explains dSi accumulation within and outside aggregates, raising the possible importance of dSi travelling within aggregates to the deep sea (potentially representing 20% of the total silica flux). The model indicates that bSiO2 dissolution is effectively decreased in aggregates mainly due to higher diatom viability but also to other parameters discussed herein.

  20. Coupled modeling of non-isothermal multiphase flow, solutetransport and reactive chemistry in porous and fractured media: 1. ModelDevelopment and Validation

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Tianfu; Pruess, Karsten


    Coupled modeling of subsurface multiphase fluid and heat flow, solute transport and chemical reactions can be used for the assessment of acid mine drainage remediation, mineral deposition, waste disposal sites, hydrothermal convection, contaminant transport, and groundwater quality. Here they present a numerical simulation model, TOUGHREACT, which considers non-isothermal multi-component chemical transport in both liquid and gas phases. A wide range of subsurface thermo-physical-chemical processes is considered. The model can be applied to one-, two- or three-dimensional porous and fractured media with physical and chemical heterogeneity. The model can accommodate any number of chemical species present in liquid, gas and solid phases. A variety of equilibrium chemical reactions is considered, such as aqueous complexation, gas dissolution/exsolution, cation exchange, and surface complexation. Mineral dissolution/precipitation can proceed either subject to local equilibrium or kinetic conditions. The coupled model employs a sequential iteration approach with reasonable computing efficiency. The development of the governing equations and numerical approach is presented along with the discussion of the model implementation and capabilities. The model is verified for a wide range of subsurface physical and chemical processes. The model is well suited for flow and reactive transport in variably saturated porous and fractured media. In the second of this two-part paper, three applications covering a variety of problems are presented to illustrate the capabilities of the model.

  1. Modeling reactive transport in deformable porous media using the theory of interacting continua.

    Energy Technology Data Exchange (ETDEWEB)

    Turner, Daniel Zack


    This report gives an overview of the work done as part of an Early Career LDRD aimed at modeling flow induced damage of materials involving chemical reactions, deformation of the porous matrix, and complex flow phenomena. The numerical formulation is motivated by a mixture theory or theory of interacting continua type approach to coupling the behavior of the fluid and the porous matrix. Results for the proposed method are presented for several engineering problems of interest including carbon dioxide sequestration, hydraulic fracturing, and energetic materials applications. This work is intended to create a general framework for flow induced damage that can be further developed in each of the particular areas addressed below. The results show both convincing proof of the methodologies potential and the need for further validation of the models developed.

  2. Endogenous Reactivity in a Dynamic Model of Consumer’s Choice

    Directory of Open Access Journals (Sweden)

    Ahmad K. Naimzada


    Full Text Available We move from a boundedly rational consumer model (Naimzada and Tramontana, 2008, 2010 characterized by a gradient-like decisional process in which, under particular parameters conditions, the asymptotical convergence to the optimal choice does not happen but it does under a least squared learning mechanism. In the present paper, we prove that even a less sophisticated learning mechanism leads to convergence to the rational choice and also prove that convergence is ensured when both learning mechanisms are available. The stability results that we obtain give more strength to the rational behavior assumption of the original model; in fact, the less demanding is the learning mechanism ensuring convergence to the rational behavior, the higher is the probability that even quite naive consumers will learn the composition of their optimum consumption bundles.

  3. Integrating Stable Isotope - Reactive Transport Model Approach for Assessment of Chlorinated Solvent Degradation (United States)


    NAME(S) AND ADDRESS(ES) University of Oklahoma, 100 E. Boyd St., SEC 810 Norman , OK 73019-2115 8. PERFORMING ORGANIZATION REPORT NUMBER Delft...cost added by basic 0-D modeling of CSIA data is relatively low in comparison to the complete cost of sample collection and CSIA analytical work; and...Section 5.6. Given relatively low concentrations of the contaminants in a number of monitoring wells at the Demonstration Site, further optimization

  4. A reactive transport model for mercury fate in soil--application to different anthropogenic pollution sources. (United States)

    Leterme, Bertrand; Blanc, Philippe; Jacques, Diederik


    Soil systems are a common receptor of anthropogenic mercury (Hg) contamination. Soils play an important role in the containment or dispersion of pollution to surface water, groundwater or the atmosphere. A one-dimensional model for simulating Hg fate and transport for variably saturated and transient flow conditions is presented. The model is developed using the HP1 code, which couples HYDRUS-1D for the water flow and solute transport to PHREEQC for geochemical reactions. The main processes included are Hg aqueous speciation and complexation, sorption to soil organic matter, dissolution of cinnabar and liquid Hg, and Hg reduction and volatilization. Processes such as atmospheric wet and dry deposition, vegetation litter fall and uptake are neglected because they are less relevant in the case of high Hg concentrations resulting from anthropogenic activities. A test case is presented, assuming a hypothetical sandy soil profile and a simulation time frame of 50 years of daily atmospheric inputs. Mercury fate and transport are simulated for three different sources of Hg (cinnabar, residual liquid mercury or aqueous mercuric chloride), as well as for combinations of these sources. Results are presented and discussed with focus on Hg volatilization to the atmosphere, Hg leaching at the bottom of the soil profile and the remaining Hg in or below the initially contaminated soil layer. In the test case, Hg volatilization was negligible because the reduction of Hg(2+) to Hg(0) was inhibited by the low concentration of dissolved Hg. Hg leaching was mainly caused by complexation of Hg(2+) with thiol groups of dissolved organic matter, because in the geochemical model used, this reaction only had a higher equilibrium constant than the sorption reactions. Immobilization of Hg in the initially polluted horizon was enhanced by Hg(2+) sorption onto humic and fulvic acids (which are more abundant than thiols). Potential benefits of the model for risk management and remediation of

  5. Modeling the Influence of Transport on Chemical Reactivity in Microbial Membranes: Mineral Precipitation/Dissolution Reactions. (United States)

    Felmy, A. R.; Liu, C.; Clark, S.; Straatsma, T.; Rustad, J.


    It has long been known that microorganisms can alter the chemical composition of their immediate surroundings and influence such processes as ion uptake or adsorption and mineral precipitation dissolution. However, only recently have molecular imaging and molecular modeling capabilities been developed that begin to shed light on the nature of these processes at the nm to um scale at the surface of bacterial membranes. In this presentation we will show the results of recent molecular simulations of microbial surface reactions and describe our efforts to develop accurate non-equilibrium thermodynamic models for the microbial surface that can describe ion uptake and surface induced mineral precipitation. The thermodynamic models include the influence of the bacterial electrical double layer on the uptake of ions from solution and the removal, or exclusion, of ions from the surface of the cell, non-equilibrium diffusion and chemical reaction within the membrane, as well as a new thermodynamic approach to representing ion activities within the microbial membrane. In the latter case, the variability in the water content within the microbial membrane has a significant influence on the calculated mineral saturation indices. In such cases, we will propose the use of recently developed mixed solvent-electrolyte formalisms. Recent experimental data for mixed-solvent electrolyte systems will also be presented to demonstrate the potential impact of the variable water content on calculated ion activities within the membrane.

  6. Structure-reactivity modeling using mixture-based representation of chemical reactions (United States)

    Polishchuk, Pavel; Madzhidov, Timur; Gimadiev, Timur; Bodrov, Andrey; Nugmanov, Ramil; Varnek, Alexandre


    We describe a novel approach of reaction representation as a combination of two mixtures: a mixture of reactants and a mixture of products. In turn, each mixture can be encoded using an earlier reported approach involving simplex descriptors (SiRMS). The feature vector representing these two mixtures results from either concatenated product and reactant descriptors or the difference between descriptors of products and reactants. This reaction representation doesn't need an explicit labeling of a reaction center. The rigorous "product-out" cross-validation (CV) strategy has been suggested. Unlike the naïve "reaction-out" CV approach based on a random selection of items, the proposed one provides with more realistic estimation of prediction accuracy for reactions resulting in novel products. The new methodology has been applied to model rate constants of E2 reactions. It has been demonstrated that the use of the fragment control domain applicability approach significantly increases prediction accuracy of the models. The models obtained with new "mixture" approach performed better than those required either explicit (Condensed Graph of Reaction) or implicit (reaction fingerprints) reaction center labeling.

  7. In situ measurements and modeling of reactive trace gases in a small biomass burning plume (United States)

    Müller, Markus; Anderson, Bruce E.; Beyersdorf, Andreas J.; Crawford, James H.; Diskin, Glenn S.; Eichler, Philipp; Fried, Alan; Keutsch, Frank N.; Mikoviny, Tomas; Thornhill, Kenneth L.; Walega, James G.; Weinheimer, Andrew J.; Yang, Melissa; Yokelson, Robert J.; Wisthaler, Armin


    An instrumented NASA P-3B aircraft was used for airborne sampling of trace gases in a plume that had emanated from a small forest understory fire in Georgia, USA. The plume was sampled at its origin to derive emission factors and followed ˜ 13.6 km downwind to observe chemical changes during the first hour of atmospheric aging. The P-3B payload included a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS), which measured non-methane organic gases (NMOGs) at unprecedented spatiotemporal resolution (10 m spatial/0.1 s temporal). Quantitative emission data are reported for CO2, CO, NO, NO2, HONO, NH3, and 16 NMOGs (formaldehyde, methanol, acetonitrile, propene, acetaldehyde, formic acid, acetone plus its isomer propanal, acetic acid plus its isomer glycolaldehyde, furan, isoprene plus isomeric pentadienes and cyclopentene, methyl vinyl ketone plus its isomers crotonaldehyde and methacrolein, methylglyoxal, hydroxy acetone plus its isomers methyl acetate and propionic acid, benzene, 2,3-butanedione, and 2-furfural) with molar emission ratios relative to CO larger than 1 ppbV ppmV-1. Formaldehyde, acetaldehyde, 2-furfural, and methanol dominated NMOG emissions. No NMOGs with more than 10 carbon atoms were observed at mixing ratios larger than 50 pptV ppmV-1 CO. Downwind plume chemistry was investigated using the observations and a 0-D photochemical box model simulation. The model was run on a nearly explicit chemical mechanism (MCM v3.3) and initialized with measured emission data. Ozone formation during the first hour of atmospheric aging was well captured by the model, with carbonyls (formaldehyde, acetaldehyde, 2,3-butanedione, methylglyoxal, 2-furfural) in addition to CO and CH4 being the main drivers of peroxy radical chemistry. The model also accurately reproduced the sequestration of NOx into peroxyacetyl nitrate (PAN) and the OH-initiated degradation of furan and 2-furfural at an average OH concentration of 7.45 ± 1.07 × 106 cm-3 in the


    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Chen


    An important question for the Carbon Capture, Storage, and Utility program is “can we adequately predict the CO2 plume migration?” For tracking CO2 plume development, the Sleipner project in the Norwegian North Sea provides more time-lapse seismic monitoring data than any other sites, but significant uncertainties still exist for some of the reservoir parameters. In Part I, we assessed model uncertainties by applying two multi-phase compositional simulators to the Sleipner Benchmark model for the uppermost layer (Layer 9) of the Utsira Sand and calibrated our model against the time-lapsed seismic monitoring data for the site from 1999 to 2010. Approximate match with the observed plume was achieved by introducing lateral permeability anisotropy, adding CH4 into the CO2 stream, and adjusting the reservoir temperatures. Model-predicted gas saturation, CO2 accumulation thickness, and CO2 solubility in brine—none were used as calibration metrics—were all comparable with the interpretations of the seismic data in the literature. In Part II & III, we evaluated the uncertainties of predicted long-term CO2 fate up to 10,000 years, due to uncertain reaction kinetics. Under four scenarios of the kinetic rate laws, the temporal and spatial evolution of CO2 partitioning into the four trapping mechanisms (hydrodynamic/structural, solubility, residual/capillary, and mineral) was simulated with ToughReact, taking into account the CO2-brine-rock reactions and the multi-phase reactive flow and mass transport. Modeling results show that different rate laws for mineral dissolution and precipitation reactions resulted in different predicted amounts of trapped CO2 by carbonate minerals, with scenarios of the conventional linear rate law for feldspar dissolution having twice as much mineral trapping (21% of the injected CO2) as scenarios with a Burch-type or Alekseyev et al.–type rate law for feldspar dissolution (11%). So far, most reactive transport modeling (RTM) studies for

  9. Modelling of the reactive transport of organic pollutants in ground water; Modellierung des reaktiven Transports organischer Schadstoffe im Grundwasser

    Energy Technology Data Exchange (ETDEWEB)

    Schaefer, W. [Heidelberg Univ. (Germany). Inst. fuer Umweltphysik


    The book describes reactive transport of organic pollutants in ground water and its quantitative monitoring by means of numerical reaction transport models. A brief introduction dealing with the importance of and hazards to ground water and opportunities for making use of ground water models is followed by a more detailed chapter on organic pollutants in ground water. Here the focus is on organochlorine compounds and mineral oil products. Described are propagation mechanisms for these substances in the ground and, especially, their degradability in ground water. A separate chapter is dedicated to possibilities for cleaning up polluted ground water aquifers. The most important decontamination techniques are presented, with special emphasis on in-situ processes with hydraulic components. Moreover, this chapter discusses the self-cleaning capability of aquifers and the benefits of the application of models to ground water cleanup. In the fourth chapter the individual components of reaction transport models are indicated. Here it is, inter alia, differences in the formulation of reaction models as to their complexity, and coupling between suspended matter transport and reaction processes that are dealt with. This chapter ends with a comprehensive survey of literature regarding the application of suspended matter transport models to real ground water accidents. Chapter 5 consists of a description of the capability and principle of function of the reaction transport model TBC (transport biochemism/chemism). This model is used in the two described applications to the reactive transport of organic pollutants in ground water. (orig.) [German] Inhalt des vorliegenden Buches ist die Darstellung des reaktiven Transports organischer Schadstoffe im Grundwasser und dessen quantitative Erfassung mithilfe numerischer Reaktions-Transportmodelle. Auf eine kurze Einleitung zur Bedeutung und Gefaehrdung von Grundwasser und zu den Einsatzmoeglichkeiten von Grundwassermodellen folgt ein

  10. Modeling Biogeochemical Reactive Transport in Fractured Granites: Implications for the Performance of a Deep Geological Repository (United States)

    Molinero, J.; Samper, J.; Pedersen, K.; Puigdomenech, I.


    Several countries around the world are considering deep repositories in fractured granitic formations for the final disposal of high-level radioactive waste. Evaluating the long term safety of such repositories requires sound conceptual and numerical models which are being developed from data and knowledge gained from in situ experiments carried out at deep underground laboratories such as that of Žsp” in Sweden. One of the key aspects for performance assessment concerns to groundwater redox conditions because: (a) the presence of oxygen will affect to the corrosion of canisters, (b) possible production of hydrogen sulphide from sulphate reduction will also have a negative effect on these metallic containers, and (c) several long-lived radionuclides are much more soluble and mobile under oxidizing conditions. Several projects have been performed at Žsp” to investigate different aspects of the groundwater redox evolution. The vast amount of in situ-generated information has been used in this work to set up coupled hydrobiogeochemical models. Numerical models account for saturated groundwater flow, solute transport by advection, dispersion and molecular diffusion, geochemical reactions involving both the liquid and solid phases, and microbially-catallyzed processes. For the Žsp” site, modelling results provide quantitative support for the following conclusions. (A) At the operational phase of the repository, shallow fresh groundwater could reach the depth of the underground facility. Shallow groundwaters loose dissolved oxygen during the infiltration through soil layers and then, respiration of dissolved organic matter is induced along the flow paths through the reduction of Fe(III)-bearing minerals of the fracture zones. Microbial anaerobic respiration of DOC provides additional reducing capacity at the depth of the tunnel. (B) After repository closure, atmospheric oxygen will remain trapped within the tunnel. Abiotic consumption of this oxygen has been

  11. Process-based reactive transport model to quantify arsenic mobility during aquifer storage and recovery of potable water. (United States)

    Wallis, Ilka; Prommer, Henning; Pichler, Thomas; Post, Vincent; Norton, Stuart B; Annable, Michael D; Simmons, Craig T


    Aquifer storage and recovery (ASR) is an aquifer recharge technique in which water is injected in an aquifer during periods of surplus and withdrawn from the same well during periods of deficit. It is a critical component of the long-term water supply plan in various regions, including Florida, USA. Here, the viability of ASR as a safe and cost-effective water resource is currently being tested at a number of sites due to elevated arsenic concentrations detected during groundwater recovery. In this study, we developed a process-based reactive transport model of the coupled physical and geochemical mechanisms controlling the fate of arsenic during ASR. We analyzed multicycle hydrochemical data from a well-documented affected southwest Floridan site and evaluated a conceptual/numerical model in which (i) arsenic is initially released during pyrite oxidation triggered by the injection of oxygenated water (ii) then largely complexes to neo-formed hydrous ferric oxides before (iii) being remobilized during recovery as a result of both dissolution of hydrous ferric oxides and displacement from sorption sites by competing anions.

  12. Numerical modelling of methane oxidation efficiency and coupled water-gas-heat reactive transfer in a sloping landfill cover. (United States)

    Feng, S; Ng, C W W; Leung, A K; Liu, H W


    Microbial aerobic methane oxidation in unsaturated landfill cover involves coupled water, gas and heat reactive transfer. The coupled process is complex and its influence on methane oxidation efficiency is not clear, especially in steep covers where spatial variations of water, gas and heat are significant. In this study, two-dimensional finite element numerical simulations were carried out to evaluate the performance of unsaturated sloping cover. The numerical model was calibrated using a set of flume model test data, and was then subsequently used for parametric study. A new method that considers transient changes of methane concentration during the estimation of the methane oxidation efficiency was proposed and compared against existing methods. It was found that a steeper cover had a lower oxidation efficiency due to enhanced downslope water flow, during which desaturation of soil promoted gas transport and hence landfill gas emission. This effect was magnified as the cover angle and landfill gas generation rate at the bottom of the cover increased. Assuming the steady-state methane concentration in a cover would result in a non-conservative overestimation of oxidation efficiency, especially when a steep cover was subjected to rainfall infiltration. By considering the transient methane concentration, the newly-modified method can give a more accurate oxidation efficiency. Copyright © 2017. Published by Elsevier Ltd.

  13. Unbound position II in MXCXXC metallochaperone model peptides impacts metal binding mode and reactivity: Distinct similarities to whole proteins. (United States)

    Shoshan, Michal S; Dekel, Noa; Goch, Wojciech; Shalev, Deborah E; Danieli, Tsafi; Lebendiker, Mario; Bal, Wojciech; Tshuva, Edit Y


    The effect of position II in the binding sequence of copper metallochaperones, which varies between Thr and His, was investigated through structural analysis and affinity and oxidation kinetic studies of model peptides. A first Cys-Cu(I)-Cys model obtained for the His peptide at acidic and neutral pH, correlated with higher affinity and more rapid oxidation of its complex; in contrast, the Thr peptide with the Cys-Cu(I)-Met coordination under neutral conditions demonstrated weaker and pH dependent binding. Studies with human antioxidant protein 1 (Atox1) and three of its mutants where S residues were replaced with Ala suggested that (a) the binding affinity is influenced more by the binding sequence than by the protein fold (b) pH may play a role in binding reactivity, and (c) mutating the Met impacted the affinity and oxidation rate more drastically than did mutating one of the Cys, supporting its important role in protein function. Position II thus plays a dominant role in metal binding and transport.

  14. Multi-component reactive transport modeling of natural attenuation of an acid groundwater plume at a uranium mill tailings site (United States)

    Zhu, Chen; Hu, Fang Q.; Burden, David S.


    Natural attenuation of an acidic plume in the aquifer underneath a uranium mill tailings pond in Wyoming, USA was simulated using the multi-component reactive transport code PHREEQC. A one-dimensional model was constructed for the site and the model included advective-dispersive transport, aqueous speciation of 11 components, and precipitation-dissolution of six minerals. Transport simulation was performed for a reclamation scenario in which the source of acidic seepage will be terminated after 5 years and the plume will then be flushed by uncontaminated upgradient groundwater. Simulations show that successive pH buffer reactions with calcite, Al(OH) 3(a), and Fe(OH) 3(a) create distinct geochemical zones and most reactions occur at the boundaries of geochemical zones. The complex interplay of physical transport processes and chemical reactions produce multiple concentration waves. For SO 42- transport, the concentration waves are related to advection-dispersion, and gypsum precipitation and dissolution. Wave speeds from numerical simulations compare well to an analytical solution for wave propagation.

  15. Accelerating Neuronal Aging in In Vitro Model Brain Disorders: a Focus on Reactive Oxygen Species

    Directory of Open Access Journals (Sweden)

    Priscila Britto Campos


    Full Text Available In this review, we discuss insights gained through the use of stem cell preparations regarding the modeling of neurological diseases, the need for aging neurons derived from pluripotent stem cells to further advance the study of late-onset adult neurological diseases, and the extent to which mechanisms linked to the mismanagement of ROS. The context of these issues can be revealed using the three disease states of Parkinson’s (PD, Alzheimer’s (AD, and schizophrenia, as considerable insights have been gained into these conditions through the use of stem cells in terms of disease etiologies and the role of oxidative stress. The latter subject is a primary area of interest of our group. After discussing the molecular models of accelerated aging, we highlight the role of ROS for the three diseases explored here. Importantly, we do not seek to provide an extensive account of all genetic mutations for each of the three disorders discussed in this review, but we aim instead to provide a conceptual framework that could maximize the gains from merging the approaches of stem cell microsystems and the study of oxidative stress in disease in order to optimize therapeutics and determine new molecular targets against oxidative stress that spare stem cell proliferation and development.

  16. The analysis of reactively loaded microstrip antennas by finite difference time domain modelling (United States)

    Hilton, G. S.; Beach, M. A.; Railton, C. J.


    In recent years, much interest has been shown in the use of printed circuit antennas in mobile satellite and communications terminals at microwave frequencies. Although such antennas have many advantages in weight and profile size over more conventional reflector/horn configurations, they do, however, suffer from an inherently narrow bandwidth. A way of optimizing the bandwidth of such antennas by an electronic tuning technique using a loaded probe mounted within the antenna structure is examined, and the resulting far-field radiation patterns are shown. Simulation results from a 2D finite difference time domain (FDTD) model for a rectangular microstrip antenna loaded with shorting pins are given and compared to results obtained with an actual antenna. It is hoped that this work will result in a design package for the analysis of microstrip patch antenna elements.

  17. Structural models of vanadate-dependent haloperoxidases, their reactivity, immobilization on polymer support and catalytic activities

    Indian Academy of Sciences (India)

    Mannar R Maurya


    The design of structural and functional models of enzymes vanadate-dependent haloperoxidases (VHPO) and the isolation and/or generation of species having {VO(H2O)}, {VO2}, {VO(OH)} and {VO(O2)} cores, proposed as intermediate(s) during catalytic action, in solution have been studied. Catalytic potential of these complexes have been tested for oxo-transfer as well as oxidative bromination and sulfide oxidation reactions. Some of the oxidovanadium(IV) and dioxidovanadium(V) complexes have been immobilized on polymer support in order to improve their recycle ability during catalytic activities and turn over number. The formulations of the polymer-anchored complexes are based on the respective neat complexes and conclusions drawn from the various characterization studies. These catalysts have successfully been used for all catalytic reactions mentioned above. These catalysts are stable and recyclable.

  18. A reactive transport model for the quantification of risks induced by groundwater heat pump systems in urban aquifers (United States)

    García-Gil, Alejandro; Epting, Jannis; Ayora, Carlos; Garrido, Eduardo; Vázquez-Suñé, Enric; Huggenberger, Peter; Gimenez, Ana Cristina


    Shallow geothermal resource exploitation through the use of groundwater heat pump systems not only has hydraulic and thermal effects on the environment but also induces physicochemical changes that can compromise the operability of installations. This study focuses on chemical clogging and dissolution subsidence processes observed during the geothermal re-injection of pumped groundwater into an urban aquifer. To explain these phenomena, two transient reactive transport models of a groundwater heat pump installation in an alluvial aquifer were used to reproduce groundwater-solid matrix interactions occurring in a surrounding aquifer environment during system operation. The models couple groundwater flow, heat and solute transport together with chemical reactions. In these models, the permeability distribution in space changes with precipitation-dissolution reactions over time. The simulations allowed us to estimate the calcite precipitation rates and porosity variations over space and time as a function of existent hydraulic gradients in an aquifer as well as the intensity of CO2 exchanges with the atmosphere. The results obtained from the numerical model show how CO2 exolution processes that occur during groundwater reinjection into an aquifer and calcite precipitation are related to hydraulic efficiency losses in exploitation systems. Finally, the performance of reinjection wells was evaluated over time according to different scenarios until the systems were fully obstructed. Our simulations also show a reduction in hydraulic conductivity that forces re-injected water to flow downwards, thereby enhancing the dissolution of evaporitic bedrock and producing subsidence that can ultimately result in a dramatic collapse of the injection well infrastructure.

  19. Modeling of coupled heat transfer and reactive transport processesin porous media: Application to seepage studies at Yucca Mountain, Nevada

    Energy Technology Data Exchange (ETDEWEB)

    Mukhopadhyay, Sumit; Sonnenthal, Eric L.; Spycher, Nicolas


    When hot radioactive waste is placed in subsurface tunnels, a series of complex changes occurs in the surrounding medium. The water in the pore space of the medium undergoes vaporization and boiling. Subsequently, vapor migrates out of the matrix pore space, moving away from the tunnel through the permeable fracture network. This migration is propelled by buoyancy, by the increased vapor pressure caused by heating and boiling, and through local convection. In cooler regions, the vapor condenses on fracture walls, where it drains through the fracture network. Slow imbibition of water thereafter leads to gradual rewetting of the rock matrix. These thermal and hydrological processes also bring about chemical changes in the medium. Amorphous silica precipitates from boiling and evaporation, and calcite from heating and CO2 volatilization. The precipitation of amorphous silica, and to a much lesser extent calcite, results in long-term permeability reduction. Evaporative concentration also results in the precipitation of gypsum (or anhydrite), halite, fluorite and other salts. These evaporative minerals eventually redissolve after the boiling period is over, however, their precipitation results in a significant temporary decrease in permeability. Reduction of permeability is also associated with changes in fracture capillary characteristics. In short, the coupled thermal-hydrological-chemical (THC) processes dynamically alter the hydrological properties of the rock. A model based on the TOUGHREACT reactive transport software is presented here to investigate the impact of THC processes on flow near an emplacement tunnel at Yucca Mountain, Nevada. We show how transient changes in hydrological properties caused by THC processes often lead to local flow channeling and saturation increases above the tunnel. For models that include only permeability changes to fractures, such local flow channeling may lead to seepage relative to models where THC effects are ignored. However

  20. Modeling of coupled heat transfer and reactive transport processesin porous media: Application to seepage studies at Yucca Mountain, Nevada

    Energy Technology Data Exchange (ETDEWEB)

    Mukhopadhyay, S.; Sonnenthal, E.L.; Spycher, N.


    When hot radioactive waste is placed in subsurface tunnels, a series of complex changes occurs in the surrounding medium. The water in the pore space of the medium undergoes vaporization and boiling. Subsequently, vapor migrates out of the matrix pore space, moving away from the tunnel through the permeable fracture network. This migration is propelled by buoyancy, by the increased vapor pressure caused by heating and boiling, and through local convection. In cooler regions, the vapor condenses on fracture walls, where it drains through the fracture network. Slow imbibition of water thereafter leads to gradual rewetting of the rock matrix. These thermal and hydrological processes also bring about chemical changes in the medium. Amorphous silica precipitates from boiling and evaporation, and calcite from heating and CO{sub 2} volatilization. The precipitation of amorphous silica, and to a much lesser extent calcite, results in long-term permeability reduction. Evaporative concentration also results in the precipitation of gypsum (or anhydrite), halite, fluorite and other salts. These evaporative minerals eventually redissolve after the boiling period is over, however, their precipitation results in a significant temporary decrease in permeability. Reduction of permeability is also associated with changes in fracture capillary characteristics. In short, the coupled thermal-hydrological-chemical (THC) processes dynamically alter the hydrological properties of the rock. A model based on the TOUGHREACT reactive transport software is presented here to investigate the impact of THC processes on flow near an emplacement tunnel at Yucca Mountain, Nevada. We show how transient changes in hydrological properties caused by THC processes often lead to local flow channeling and saturation increases above the tunnel. For models that include only permeability changes to fractures, such local flow channeling may lead to seepage relative to models where THC effects are ignored

  1. Phosphorus dynamics in lake sediments: Insights from field study and reactive-transport modeling (United States)

    Dittrich, Maria; Markovic, Stefan; Cadena, Sandra; Doan, Phuong T. K.; Watson, Sue; Mugalingam, Shan


    Phosphorus is an indispensable nutrient for organisms in aquatic systems and its availability often controls primary productivity. At the sediment-water interface, intensive microbiological, geochemical and physical processes determine the fraction of organic matter, nutrients and pollutants released into the overlying water. Therefore, detailed understanding of the processes occurring in the top centimeters of the sediment is essential for the assessment of water quality and the management of surface waters. In cases where measurements are impossible or expensive, diagenetic modelling is required to investigate the interplay among the processes, verify concepts and predict potential system behavior. The main aims of this study are to identify and predict the dynamics of phosphorus (P) in sediments and gain insight into the mechanism of P release from sediments under varying environmental conditions. We measured redox, O2 and pH profiles with micro-sensors at the sediment-water interface; analyzed phosphate and metals (Fe, Mn, Al, Ca) content in pore waters collected using in situ samplers, so called "peepers"; determined P binding forms using sequential extraction and analyzed metals associated with each fraction. Following the sediment analysis, P binding forms were divided in five groups: inert, carbonate-bound, organic, redox-sensitive, and labile P. Using the flux of organic and inorganic matter as dynamic boundary conditions, the diagenetic model simulates P internal loading and predicts P retention. This presentation will discuss the results of two years studies on P dynamics at the sediment-water interface in three different lakes ranging from heavy-polluted Hamilton Harbor and Bay of Quinte to pristine Georgian Bay in Ontario, Canada.

  2. Neural progenitor cells attenuate inflammatory reactivity and neuronal loss in an animal model of inflamed AD brain

    Directory of Open Access Journals (Sweden)

    Wang Yu


    Full Text Available Abstract Background Transplantation of neural progenitor cells (NPC constitutes a putative therapeutic maneuver for use in treatment of neurodegenerative diseases. At present, effects of NPC transplantation in Alzheimer's disease (AD brain are largely unknown and a primary objective of this work was to demonstrate possible efficacy of NPC administration in an animal model of AD. The benefits of transplantation could involve a spectrum of effects including replacement of endogenous neurons or by conferring neuroprotection with enhancement of neurotrophic factors or diminishing levels of neurotoxic agents. Since chronic inflammation is a characteristic property of AD brain, we considered that transplantation of NPC could have particular utility in inhibiting ongoing inflammatory reactivity. We have tested intrahippocampal transplantation of NPC for efficacy in attenuating inflammatory responses and for neuroprotection in beta-amyloid (Aβ1-42 peptide-injected rat hippocampus. Methods Spheres of neural progenitor cells were grown from dissociated telencephalon tissue of rat embryos. NPC were infected with lentiviral vector green fluorescent protein (GFP with subsequent cell transplantation into rat hippocampus previously injected (3 d prior with Aβ1-42 peptide or PBS control. Immunohistochemical analysis was carried out (7 d post-NPC transplantation, 10 d post-peptide/PBS injection for GFP, microgliosis (Iba-1 marker, astrogliosis (GFAP marker, neuron viability (MAP-2 marker and levels of the proinflammatory cytokine, TNF-α. Results Successful infection of cultured NPC with lentiviral vector green fluorescent protein (GFP was demonstrated prior to cell transplantation into rat hippocampus. In vivo, immunohistochemical staining showed migration of GFP-positive cells, in a region of dentate gyrus between Aβ1-42/PBS injection site and NPC transplantation site, was increased ×2.8-fold with Aβ1-42 compared to PBS injection. Double immunostaining in

  3. Modeling neuroendocrine stress reactivity in salivary cortisol: adjusting for peak latency variability. (United States)

    Lopez-Duran, Nestor L; Mayer, Stefanie E; Abelson, James L


    In this report, we present growth curve modeling (GCM) with landmark registration as an alternative statistical approach for the analysis of time series cortisol data. This approach addresses an often-ignored but critical source of variability in salivary cortisol analyses: individual and group differences in the time latency of post-stress peak concentrations. It allows for the simultaneous examination of cortisol changes before and after the peak while controlling for timing differences, and thus provides additional information that can help elucidate group differences in the underlying biological processes (e.g., intensity of response, regulatory capacity). We tested whether GCM with landmark registration is more sensitive than traditional statistical approaches (e.g., repeated measures ANOVA--rANOVA) in identifying sex differences in salivary cortisol responses to a psychosocial stressor (Trier Social Stress Test--TSST) in healthy adults (mean age 23). We used plasma ACTH measures as our "standard" and show that the new approach confirms in salivary cortisol the ACTH finding that males had longer peak latencies, higher post-stress peaks but a more intense post-peak decline. This finding would have been missed if only saliva cortisol was available and only more traditional analytic methods were used. This new approach may provide neuroendocrine researchers with a highly sensitive complementary tool to examine the dynamics of the cortisol response in a way that reduces risk of false negative findings when blood samples are not feasible.

  4. Upscaling of the specific surface area for reactive transport modelling in fractured rock (United States)

    Cvetkovic, Vladimir


    The impact of flow heterogeneity on chemical transport from single to multiple fractures, is investigated. The emphasis is on the dynamic nature of the specific surface area (SSA) due to heterogeneity of the flow, relative to a purely geometrical definition. It is shown how to account for SSA as a random variable in modelling multi-component reactions. The flow-dependent SSA is interpreted probabilistically, following inert tracer particles along individual fractures. Upscaling to a fracture network is proposed as a time-domain random walk based on the statistics of SSA for single fractures. Statistics of SSA are investigated for three correlation structures of transmissivity, one classical multi-gaussian, and two non-Gaussian. The coefficient of variation of single fracture SSA decreases monotonously with the distance over the fracture length; the CV of the upscaled SSA reduces further such that after ca 20 fractures it is under 0.1 for a disconnected field, and around 0.2 for connected and multi-gaussian fields. This implies that after 10-20 fractures, uncertainty in SSA is significantly reduced, justifying the use of an effective value. A conservative, lower bound for the dimensionless upscaled effective SSA was found to be 1, suitable for all heterogeneity structures, assuming the cubic hydraulic law applicable.

  5. Empirical valence bond models for reactive potential energy surfaces: a parallel multilevel genetic program approach. (United States)

    Bellucci, Michael A; Coker, David F


    We describe a new method for constructing empirical valence bond potential energy surfaces using a parallel multilevel genetic program (PMLGP). Genetic programs can be used to perform an efficient search through function space and parameter space to find the best functions and sets of parameters that fit energies obtained by ab initio electronic structure calculations. Building on the traditional genetic program approach, the PMLGP utilizes a hierarchy of genetic programming on two different levels. The lower level genetic programs are used to optimize coevolving populations in parallel while the higher level genetic program (HLGP) is used to optimize the genetic operator probabilities of the lower level genetic programs. The HLGP allows the algorithm to dynamically learn the mutation or combination of mutations that most effectively increase the fitness of the populations, causing a significant increase in the algorithm's accuracy and efficiency. The algorithm's accuracy and efficiency is tested against a standard parallel genetic program with a variety of one-dimensional test cases. Subsequently, the PMLGP is utilized to obtain an accurate empirical valence bond model for proton transfer in 3-hydroxy-gamma-pyrone in gas phase and protic solvent.

  6. Reactive transport model of growth and methane production by high-temperature methanogens in hydrothermal regions of the subseafloor (United States)

    Stewart, L. C.; Algar, C. K.; Topçuoğlu, B. D.; Fortunato, C. S.; Larson, B. I.; Proskurowski, G. K.; Butterfield, D. A.; Vallino, J. J.; Huber, J. A.; Holden, J. F.


    Hydrogenotrophic methanogens are keystone high-temperature autotrophs in deep-sea hydrothermal vents and tracers of habitability and biogeochemical activity in the hydrothermally active subseafloor. At Axial Seamount, nearly all thermophilic methanogens are Methanothermococcus and Methanocaldococcus species, making this site amenable to modeling through pure culture laboratory experiments coupled with field studies. Based on field microcosm incubations with 1.2 mM, 20 μM, or no hydrogen, the growth of methanogens at 55°C and 80°C is limited primarily by temperature and hydrogen availability, with ammonium amendment showing no consistent effect on total methane output. The Arrhenius constants for methane production by Methanocaldococcus jannaschii (optimum 82°C) and Methanothermococcus thermolithotrophicus (optimum 65°C) were determined in pure culture bottle experiments. The Monod constants for hydrogen concentration were measured by growing both organisms in a 2-liter chemostat at two dilution rates; 55°C, 65°C and 82°C; and variable hydrogen concentrations. M. jannaschii showed higher ks and Vmax constants than M. thermolithotrophicus. In the field, hydrogen and methane concentrations in hydrothermal end-member and low-temperature diffuse fluids were measured, and the concentrations of methanogens that grow at 55°C and 80°C in diffuse fluids were determined using most-probable-number estimates. Methane concentration anomalies in diffuse fluids relative to end-member hydrothermal concentrations and methanogen cell concentrations are being used to constrain a 1-D reactive transport model using the laboratory-determined Arrhenius and Monod constants for methane production by these organisms. By varying flow path length and subseafloor cell concentrations in the model, our goal is to determine solutions for the potential depth of the subseafloor biosphere coupled with the amount of methanogenic biomass it contains.

  7. Techno-economical optimization of Reactive Blue 19 removal by combined electrocoagulation/coagulation process through MOPSO using RSM and ANFIS models. (United States)

    Taheri, M; Alavi Moghaddam, M R; Arami, M


    In this research, Response Surface Methodology (RSM) and Adaptive Neuro Fuzzy Inference System (ANFIS) models were applied for optimization of Reactive Blue 19 removal using combined electrocoagulation/coagulation process through Multi-Objective Particle Swarm Optimization (MOPSO). By applying RSM, the effects of five independent parameters including applied current, reaction time, initial dye concentration, initial pH and dosage of Poly Aluminum Chloride were studied. According to the RSM results, all the independent parameters are equally important in dye removal efficiency. In addition, ANFIS was applied for dye removal efficiency and operating costs modeling. High R(2) values (≥85%) indicate that the predictions of RSM and ANFIS models are acceptable for both responses. ANFIS was also used in MOPSO for finding the best techno-economical Reactive Blue 19 elimination conditions according to RSM design. Through MOPSO and the selected ANFIS model, Minimum and maximum values of 58.27% and 99.67% dye removal efficiencies were obtained, respectively.

  8. Different reactive oxygen species lead to distinct changes of cellular metal ions in the eukaryotic model organism Saccharomyces cerevisiae. (United States)

    Wu, Ming J; O'Doherty, Patrick J; Murphy, Patricia A; Lyons, Victoria; Christophersen, Melinda; Rogers, Peter J; Bailey, Trevor D; Higgins, Vincent J


    Elemental uptake and export of the cell are tightly regulated thereby maintaining the ionomic homeostasis. This equilibrium can be disrupted upon exposure to exogenous reactive oxygen species (ROS), leading to reduction or elevation of the intracellular metal ions. In this study, the ionomic composition in the eukaryotic model organism Saccharomyces cerevisiae was profiled using the inductively-coupled plasma optical emission spectrometer (ICP-OES) following the treatment with individual ROS, including hydrogen peroxide, cumen hydroperoxide, linoleic acid hydroperoxide (LAH), the superoxide-generating agent menadione, the thiol-oxidising agent diamide [diazine-dicarboxylic acid-bis(dimethylamide)], dimedone and peroxynitrite. The findings demonstrated that different ROS resulted in distinct changes in cellular metal ions. Aluminium (Al(3+)) level rose up to 50-fold after the diamide treatment. Cellular potassium (K(+)) in LAH-treated cells was 26-fold less compared to the non-treated controls. The diamide-induced Al(3+) accumulation was further validated by the enhanced Al(3+) uptake along the time course and diamide doses. Pre-incubation of yeast with individual elements including iron, copper, manganese and magnesium failed to block diamide-induced Al(3+) uptake, suggesting Al(3+)-specific transporters could be involved in Al(3+) uptake. Furthermore, LAH-induced potassium depletion was validated by a rescue experiment in which addition of potassium increased yeast growth in LAH-containing media by 26% compared to LAH alone. Taken together, the data, for the first time, demonstrated the linkage between ionomic profiles and individual oxidative conditions.

  9. Procalcitonin and C-reactive protein-based decision tree model for distinguishing PFAPA flares from acute infections. (United States)

    Kraszewska-Głomba, Barbara; Szymańska-Toczek, Zofia; Szenborn, Leszek


    As no specific laboratory test has been identified, PFAPA (periodic fever, aphthous stomatitis, pharyngitis and cervical adenitis) remains a diagnosis of exclusion. We searched for a practical use of procalcitonin (PCT) and C-reactive protein (CRP) in distinguishing PFAPA attacks from acute bacterial and viral infections. Levels of PCT and CRP were measured in 38 patients with PFAPA and 81 children diagnosed with an acute bacterial (n=42) or viral (n=39) infection. Statistical analysis with the use of the C4.5 algorithm resulted in the following decision tree: viral infection if CRP≤19.1 mg/L; otherwise for cases with CRP>19.1 mg/L: bacterial infection if PCT>0.65ng/mL, PFAPA if PCT≤0.65 ng/mL. The model was tested using a 10-fold cross validation and in an independent test cohort (n=30), the rule's overall accuracy was 76.4% and 90% respectively. Although limited by a small sample size, the obtained decision tree might present a potential diagnostic tool for distinguishing PFAPA flares from acute infections when interpreted cautiously and with reference to the clinical context.

  10. Procalcitonin and C-reactive protein-based decision tree model for distinguishing PFAPA flares from acute infections

    Directory of Open Access Journals (Sweden)

    Barbara Kraszewska-Głomba


    Full Text Available As no specific laboratory test has been identified, PFAPA (periodic fever, aphthous stomatitis, pharyngitis and cervical adenitis remains a diagnosis of exclusion. We searched for a practical use of procalcitonin (PCT and C-reactive protein (CRP in distinguishing PFAPA attacks from acute bacterial and viral infections. Levels of PCT and CRP were measured in 38 patients with PFAPA and 81 children diagnosed with an acute bacterial (n=42 or viral (n=39 infection. Statistical analysis with the use of the C4.5 algorithm resulted in the following decision tree: viral infection if CRP≤19.1 mg/L; otherwise for cases with CRP>19.1 mg/L: bacterial infection if PCT>0.65ng/mL, PFAPA if PCT≤0.65 ng/mL. The model was tested using a 10-fold cross validation and in an independent test cohort (n=30, the rule’s overall accuracy was 76.4% and 90% respectively. Although limited by a small sample size, the obtained decision tree might present a potential diagnostic tool for distinguishing PFAPA flares from acute infections when interpreted cautiously and with reference to the clinical context.

  11. Passiflora manicata (Juss.) aqueous leaf extract protects against reactive oxygen species and protein glycation in vitro and ex vivo models. (United States)

    da Silva Morrone, Maurilio; de Assis, Adriano Martimbianco; da Rocha, Ricardo Fagundes; Gasparotto, Juciano; Gazola, Andressa Córneo; Costa, Geison Modesti; Zucolotto, Silvana Maria; Castellanos, Leonardo H; Ramos, Freddy A; Schenkel, Eloir Paulo; Reginatto, Flávio Henrique; Gelain, Daniel Pens; Moreira, José C F


    The leaf extracts of many species of genus Passiflora have been extensively investigated for their biological activities on several rat tissues, but mainly in the central nervous system and liver. They posses anxiolytic-like, sedative effects and antioxidant properties. Evidences suggest a key role of C-glycosylflavonoids in the biological activities of Passiflora extracts. Some species (such as P. manicata) of the genus are still poorly investigated for their chemical and biological activity. In this work, we aim to investigate both antioxidant and antiglycation properties of aqueous extract of P. manicata leaves (PMLE) in vitro and ex vivo models. Crude extract showed the C-glycosylflavonoid isovitexin as the major compound. Isoorientin and vitexin were also identified. In TRAP/TAR assay, PMLE showed a significant antioxidant activity. PMLE at concentrations of 10 and 100 μg mL⁻¹ significantly decreasing LDH leakage in rat liver slices. Antioxidant effect also was observed by decreased in oxidative damage markers in slices hence hydrogen peroxide was added as oxidative stress inductor. PMLE inhibited protein glycation at all concentrations tested. In summary, P. manicata aqueous leaf extract possess protective properties against reactive oxygen species and also protein glycation, and could be considered a new source of natural antioxidants.

  12. Reactive oxygen species, DNA damage, and error-prone repair: a model for genomic instability with progression in myeloid leukemia? (United States)

    Rassool, Feyruz V; Gaymes, Terry J; Omidvar, Nader; Brady, Nicola; Beurlet, Stephanie; Pla, Marika; Reboul, Murielle; Lea, Nicholas; Chomienne, Christine; Thomas, Nicholas S B; Mufti, Ghulam J; Padua, Rose Ann


    Myelodysplastic syndromes (MDS) comprise a heterogeneous group of disorders characterized by ineffective hematopoiesis, with an increased propensity to develop acute myelogenous leukemia (AML). The molecular basis for MDS progression is unknown, but a key element in MDS disease progression is loss of chromosomal material (genomic instability). Using our two-step mouse model for myeloid leukemic disease progression involving overexpression of human mutant NRAS and BCL2 genes, we show that there is a stepwise increase in the frequency of DNA damage leading to an increased frequency of error-prone repair of double-strand breaks (DSB) by nonhomologous end-joining. There is a concomitant increase in reactive oxygen species (ROS) in these transgenic mice with disease progression. Importantly, RAC1, an essential component of the ROS-producing NADPH oxidase, is downstream of RAS, and we show that ROS production in NRAS/BCL2 mice is in part dependent on RAC1 activity. DNA damage and error-prone repair can be decreased or reversed in vivo by N-acetyl cysteine antioxidant treatment. Our data link gene abnormalities to constitutive DNA damage and increased DSB repair errors in vivo and provide a mechanism for an increase in the error rate of DNA repair with MDS disease progression. These data suggest treatment strategies that target RAS/RAC pathways and ROS production in human MDS/AML.

  13. Multiphase Reactive Transport modeling of Stable Isotope Fractionation of Infiltrating Unsaturated Zone Pore Water and Vapor Using TOUGHREACT

    Energy Technology Data Exchange (ETDEWEB)

    Singleton, Michael J.; Sonnenthal, Eric L.; Conrad, Mark E.; DePaolo, Donald J.


    Numerical simulations of transport and isotope fractionation provide a method to quantitatively interpret vadose zone pore water stable isotope depth profiles based on soil properties, climatic conditions, and infiltration. We incorporate the temperature-dependent equilibration of stable isotopic species between water and water vapor, and their differing diffusive transport properties into the thermodynamic database of the reactive transport code TOUGHREACT. These simulations are used to illustrate the evolution of stable isotope profiles in semiarid regions where recharge during wet seasons disturbs the drying profile traditionally associated with vadose zone pore waters. Alternating wet and dry seasons lead to annual fluctuations in moisture content, capillary pressure, and stable isotope compositions in the vadose zone. Periodic infiltration models capture the effects of seasonal increases in precipitation and predict stable isotope profiles that are distinct from those observed under drying (zero infiltration) conditions. After infiltration, evaporation causes a shift to higher 18O and D values, which are preserved in the deeper pore waters. The magnitude of the isotopic composition shift preserved in deep vadose zone pore waters varies inversely with the rate of infiltration.

  14. Determination of the intrinsic reactivities for carbon dioxide gasification of rice husk chars through using random pore model. (United States)

    Gao, Xiaoyan; Zhang, Yaning; Li, Bingxi; Zhao, Yijun; Jiang, Baocheng


    Rice husk is abundantly available and environmentally friendly, and char-CO2 gasification is of great importance for the biomass gasification process. The intrinsic reaction rates of carbon dioxide gasification with rice husk chars derived from different pyrolysis temperatures were investigated in this study by conducting thermogravimetric analysis (TGA) measurements. The effects of gasification temperature and reactant partial pressure on the char-CO2 gasification were investigated and the random pore model (RPM) was used to determine the intrinsic kinetic parameters based on the experimental data. The results obtained from this study show that the activation energy, reaction order and pre-exponential factor varied in the ranges of 226.65-232.28kJ/mol, 0.288-0.346 and 2.38×10(5)-2.82×10(5)1/sPa(n) for the rice husk chars pyrolyzed at 700-900°C, respectively. All the determination coefficients between the RPM predictions and experimental results were higher than 0.906, indicating the RPM is reliable for determining and evaluating the intrinsic reactivities of rice husk chars.

  15. Using the pseudophase kinetic model to interpret chemical reactivity in ionic emulsions: determining antioxidant partition constants and interfacial rate constants. (United States)

    Gu, Qing; Bravo-Díaz, Carlos; Romsted, Laurence S


    Kinetic results obtained in cationic and anionic emulsions show for the first time that pseudophase kinetic models give reasonable estimates of the partition constants of reactants, here t-butylhydroquinone (TBHQ) between the oil and interfacial region, P(O)(I), and the water and interfacial region, P(W)(I), and of the interfacial rate constant, k(I), for the reaction with an arenediazonium ion in emulsions containing a 1:1 volume ratio of a medium chain length triglyceride, MCT, and aqueous acid or buffer. The results provide: (a) an explanation for the large difference in pH, >4 pH units, required to run the reaction in CTAB (pH 1.54, added HBr) and SDS (pH 5.71, acetate buffer) emulsions; (b) reasonable estimates of PO(I) and k(I) in the CTAB emulsions; (c) a sensible interpretation of added counterion effects based on ion exchange in SDS emulsions (Na(+)/H3O(+) ion exchange in the interfacial region) and Donnan equilibrium in CTAB emulsions (Br(-) increasing the interfacial H3O(+)); and (d) the significance of the effect of the much greater solubility of TBHQ in MCT versus octane, 1000/1, as the oil. These results should aid in interpreting the effects of ionic surfactants on chemical reactivity in emulsions in general and in selecting the most efficient antioxidant for particular food applications.

  16. Penetration Deep into Tissues of Reactive Oxygen Species Generated in Floating-Electrode Dielectric Barrier Discharge (FE-DBD): in Vitro Agarose Gel Model Mimicking an Open Wound

    CERN Document Server

    Dobrynin, Danil; Friedman, Gary; Fridman, Alexander


    In this manuscript we present an in vitro model based on agarose gel that can be used to simulate a dirty, oily, bloody, and morphologically complex surface of, for example, an open wound. We show this models effectiveness in simulating depth of penetration of reactive species generated in plasma deep into tissue of a rat and confirm the penetration depths with agarose gel model. We envision that in the future such a model could be used to study plasma discharges (and other modalities) and minimize the use of live animals: plasma can be optimized on the agarose gel wound model and then finally verified using an actual wound.

  17. [Low reactive laser therapy]. (United States)

    Saeki, Shigeru


    The type, characteristics and effect of low reactive laser equipment used for pain treatment in Japan are described in this section. Currently, low reactive laser therapy equipments marketed and used in Japan include diode laser therapeutic device with semiconductor as a medium consisting of aluminum, gallium and arsenic. Low reactive laser equipment comes in three models, the first type has a capacity of generating 1,000 mW output, and the second type has a capacity of generating 10 W output. The third type has four channels of output, 60, 100, 140 and 180 mW and we can select one channel out of the four channels. This model is also used as a portable device because of its light weight, and we can carry it to wards and to the outside of the hospital. Semiconductor laser has the capacity of deepest penetration and the effect tends to increase proportionally to the increasing output. Low reactive laser therapy is less invasive and lower incidence of complications. Although low reactive laser therapy might be effective for various pain disorders, the effect is different depending on the type of pain. We should keep in mind that this therapy will not give good pain relief equally in all patients with pain.

  18. Reactive Systems

    DEFF Research Database (Denmark)

    Aceto, Luca; Ingolfsdottir, Anna; Larsen, Kim Guldstrand

    A reactive system comprises networks of computing components, achieving their goals through interaction among themselves and their environment. Thus even relatively small systems may exhibit unexpectedly complex behaviours. As moreover reactive systems are often used in safety critical systems......, the need for mathematically based formal methodology is increasingly important. There are many books that look at particular methodologies for such systems. This book offers a more balanced introduction for graduate students and describes the various approaches, their strengths and weaknesses, and when...... they are best used. Milner's CCS and its operational semantics are introduced, together with the notions of behavioural equivalences based on bisimulation techniques and with recursive extensions of Hennessy-Milner logic. In the second part of the book, the presented theories are extended to take timing issues...

  19. Environmental turbulent mixing controls on air-water gas exchange in marine and aquatic systems (United States)

    Zappa, Christopher J.; McGillis, Wade R.; Raymond, Peter A.; Edson, James B.; Hintsa, Eric J.; Zemmelink, Hendrik J.; Dacey, John W. H.; Ho, David T.


    Air-water gas transfer influences CO2 and other climatically important trace gas fluxes on regional and global scales, yet the magnitude of the transfer is not well known. Widely used models of gas exchange rates are based on empirical relationships linked to wind speed, even though physical processes other than wind are known to play important roles. Here the first field investigations are described supporting a new mechanistic model based on surface water turbulence that predicts gas exchange for a range of aquatic and marine processes. Findings indicate that the gas transfer rate varies linearly with the turbulent dissipation rate to the ${^1}\\!/{_4 power in a range of systems with different types of forcing - in the coastal ocean, in a macro-tidal river estuary, in a large tidal freshwater river, and in a model (i.e., artificial) ocean. These results have important implications for understanding carbon cycling.

  20. Kekulé-based Valence Bond Model.Ⅱ. Diels-Alder Reactivity of Polycyclic Aromatic Hydrocarbons

    Institute of Scientific and Technical Information of China (English)

    MA,Jing(马晶); LI,Shu-Hua(黎书华); JIANG,Yuan-Sheng(江元生)


    The Kekule-based valence bond ( VB ) method was employed to study the ground state properties of 52 polycyclic aromatic hydrocarbons. The reactivity indices defined upon our VB calculations were demonstrated to be capable of quantitatively interpreting the secnd order rate constants of the Diels-Alder reactions. The qualitative trends of the reactivities of many homologous series can be also explained based on the local aromaticity index defined in this work.

  1. A Universal Reactive Machine

    DEFF Research Database (Denmark)

    Andersen, Henrik Reif; Mørk, Simon; Sørensen, Morten U.


    Turing showed the existence of a model universal for the set of Turing machines in the sense that given an encoding of any Turing machine asinput the universal Turing machine simulates it. We introduce the concept of universality for reactive systems and construct a CCS processuniversal...

  2. The proinflammatory RAGE/NF-κB pathway is involved in neuronal damage and reactive gliosis in a model of sleep apnea by intermittent hypoxia. (United States)

    Angelo, Maria Florencia; Aguirre, Alejandra; Avilés Reyes, Rolando X; Villarreal, Alejandro; Lukin, Jerónimo; Melendez, Matías; Vanasco, Virginia; Barker, Phil; Alvarez, Silvia; Epstein, Alberto; Jerusalinsky, Diana; Ramos, Alberto Javier


    Sleep apnea (SA) causes long-lasting changes in neuronal circuitry, which persist even in patients successfully treated for the acute effects of the disease. Evidence obtained from the intermittent hypoxia (IH) experimental model of SA has shown neuronal death, impairment in learning and memory and reactive gliosis that may account for cognitive and structural alterations observed in human patients. However, little is known about the mechanism controlling these deleterious effects that may be useful as therapeutic targets in SA. The Receptor for Advanced Glycation End products (RAGE) and its downstream effector Nuclear Factor Kappa B (NF-κB) have been related to neuronal death and astroglial conversion to the pro-inflammatory neurodegenerative phenotype. RAGE expression and its ligand S100B were shown to be increased in experimental models of SA. We here used dissociated mixed hippocampal cell cultures and male Wistar rats exposed to IH cycles and observed that NF-κB is activated in glial cells and neurons after IH. To disclose the relative contribution of the S100B/RAGE/NF-κB pathway to neuronal damage and reactive gliosis after IH we performed sequential loss of function studies using RAGE or S100B neutralizing antibodies, a herpes simplex virus (HSV)-derived amplicon vector that induces the expression of RAGEΔcyto (dominant negative RAGE) and a chemical blocker of NF-κB. Our results show that NF-κB activation peaks 3 days after IH exposure, and that RAGE or NF-κB blockage during this critical period significantly improves neuronal survival and reduces reactive gliosis. Both in vitro and in vivo, S100B blockage altered reactive gliosis but did not have significant effects on neuronal survival. We conclude that both RAGE and downstream NF-κB signaling are centrally involved in the neuronal alterations found in SA models, and that blockage of these pathways is a tempting strategy for preventing neuronal degeneration and reactive gliosis in SA.

  3. Towards a Model of Reactive-Cracking: the Role of Reactions, Elasticity and Surface Energy Driven Flow in Poro-elastic Media (United States)

    Evans, O.; Spiegelman, M. W.; Wilson, C. R.; Kelemen, P. B.


    Many critical processes can be described by reactive fluid flow in brittle media, including hydration/alteration of oceanic plates near spreading ridges, chemical weathering, and dehydration/decarbonation of subducting plates. Such hydration reactions can produce volume changes that may induce stresses large enough to drive fracture in the rock, in turn exposing new reactive surface and modifying the permeability. A better understanding of this potentially rich feedback could also be critical in the design of engineered systems for geologic carbon sequestration. To aid understanding of these processes we have developed a macroscopic continuum description of reactive fluid flow in an elastically deformable porous media. We explore the behaviour of this model by considering a simplified hydration reaction (e.g. olivine + H20 -> serpentine + brucite). In a closed system, these hydration reactions will continue to consume available fluids until the permeability reaches zero, leaving behind it a highly stressed residuum. Our model demonstrates this limiting behaviour, and that the elastic stresses generated are large enough to cause failure/fracture of the host rock. Whilst it is understood that `reactive fracture' is an important mechanism for the continued evolution of this process, it is also proposed that imbibition/surface energy driven flow may play a role. Through a simplified set of computational experiments, we investigate the relative roles of elasticity and surface energy in both a non-reactive purely poro-elastic framework, and then in the presence of reaction. We demonstrate that surface energy can drive rapid diffusion of porosity, thus allowing the reaction to propagate over larger areas. As we expect both surface energy and fracture/failure to be of importance in these processes, we plan to integrate the current model into one that allows for fracture once critical stresses are exceeded.

  4. Using reactive transport codes to provide mechanistic biogeochemistry representations in global land surface models: CLM-PFLOTRAN 1.0

    Directory of Open Access Journals (Sweden)

    G. Tang


    Full Text Available We explore coupling to a configurable subsurface reactive transport code as a flexible and extensible approach to biogeochemistry in land surface models; our goal is to facilitate testing of alternative models and incorporation of new understanding. A reaction network with the CLM-CN decomposition, nitrification, denitrification, and plant uptake is used as an example. We implement the reactions in the open-source PFLOTRAN code, coupled with the Community Land Model (CLM, and test at Arctic, temperate, and tropical sites. To make the reaction network designed for use in explicit time stepping in CLM compatible with the implicit time stepping used in PFLOTRAN, the Monod substrate rate-limiting function with a residual concentration is used to represent the limitation of nitrogen availability on plant uptake and immobilization. To achieve accurate, efficient, and robust numerical solutions, care needs to be taken to use scaling, clipping, or log transformation to avoid negative concentrations during the Newton iterations. With a tight relative update tolerance to avoid false convergence, an accurate solution can be achieved with about 50 % more computing time than CLM in point mode site simulations using either the scaling or clipping methods. The log transformation method takes 60–100 % more computing time than CLM. The computing time increases slightly for clipping and scaling; it increases substantially for log transformation for half saturation decrease from 10−3 to 10−9 mol m−3, which normally results in decreasing nitrogen concentrations. The frequent occurrence of very low concentrations (e.g. below nanomolar can increase the computing time for clipping or scaling by about 20 %; computing time can be doubled for log transformation. Caution needs to be taken in choosing the appropriate scaling factor because a small value caused by a negative update to a small concentration may diminish the update and result in false convergence even

  5. Reactive transport modeling of the long-term effects of CO2 storage in the P18 depleted gas field (United States)

    Tambach, T. J.; Koenen, M.; Wasch, L. J.; Loeve, D.; Maas, J. G.


    Depleted gas fields are an import CO2 storage sink for The Netherlands, with a total storage capacity of more than 3 Gtonne. The CO2 sources are located at relatively short distances from potential storage reservoirs and an infrastructure for (cross-border) gas transport over large distances already exists. Several depleted gas fields in the subsurface of the Netherlands have yet been evaluated as potential locations for CO2 storage (for example the K12-B field). The P18 gas field is located in the offshore of The Netherlands and is currently evaluated as potential CO2 storage reservoir. The aim of this study is to predict the long-term effects of CO2 injection into the P18 field using reactive transport modeling (TOUGHREACT). The storage reservoir is described using the mineralogy and petrophysical characteristics of three geological layers in a radial (R,Z) reservoir model with top depth of 3456 m, a thickness of 98 m, and 3300 grid cells. The initial reservoir temperature was defined as 90 degrees C with an initial (depletion) pressure of 20.0 bars. Capillary pressure curves are based on empirical relations. The CO2 is injected uniformly distributed over the model height, at a constant rate of 35 kg/s (1.1 Mton/year), and a temperature of 40 degrees C for 30 years. The well is then shut-in with a reservoir pressure of approximately 375 bar. The simulations are continued up to 10,000 years for computing the long-term effects in the reservoir. The results show that the near-well area is dried out during injection, leading to salt precipitation and reduced permeability during injection. Condensation of the evaporated water occurs outside the near-well area. Water imbibition is modelled after shut in of the well, leading to rewetting of the near-well area and redissolution of the salt. Most geochemical reactions need water to occur, including well-cement minerals, and therefore predictions of water flow after well shut-ins are important to take into account

  6. A SCOPING STUDY: Development of Probabilistic Risk Assessment Models for Reactivity Insertion Accidents During Shutdown In U.S. Commercial Light Water Reactors

    Energy Technology Data Exchange (ETDEWEB)

    S. Khericha


    This report documents the scoping study of developing generic simplified fuel damage risk models for quantitative analysis from inadvertent reactivity insertion events during shutdown (SD) in light water pressurized and boiling water reactors. In the past, nuclear fuel reactivity accidents have been analyzed both mainly deterministically and probabilistically for at-power and SD operations of nuclear power plants (NPPs). Since then, many NPPs had power up-rates and longer refueling intervals, which resulted in fuel configurations that may potentially respond differently (in an undesirable way) to reactivity accidents. Also, as shown in a recent event, several inadvertent operator actions caused potential nuclear fuel reactivity insertion accident during SD operations. The set inadvertent operator actions are likely to be plant- and operation-state specific and could lead to accident sequences. This study is an outcome of the concern which arose after the inadvertent withdrawal of control rods at Dresden Unit 3 in 2008 due to operator actions in the plant inadvertently three control rods were withdrawn from the reactor without knowledge of the main control room operator. The purpose of this Standardized Plant Analysis Risk (SPAR) Model development project is to develop simplified SPAR Models that can be used by staff analysts to perform risk analyses of operating events and/or conditions occurring during SD operation. These types of accident scenarios are dominated by the operator actions, (e.g., misalignment of valves, failure to follow procedures and errors of commissions). Human error probabilities specific to this model were assessed using the methodology developed for SPAR model human error evaluations. The event trees, fault trees, basic event data and data sources for the model are provided in the report. The end state is defined as the reactor becomes critical. The scoping study includes a brief literature search/review of historical events, developments of

  7. Modelling of the reactive transport for rock salt-brine in geological repository systems based on improved thermodynamic database (Invited) (United States)

    Müller, W.; Alkan, H.; Xie, M.; Moog, H.; Sonnenthal, E. L.


    The release and migration of toxic contaminants from the disposed wastes is one of the main issues in long-term safety assessment of geological repositories. In the engineered and geological barriers around the nuclear waste emplacements chemical interactions between the components of the system may affect the isolation properties considerably. As the chemical issues change the transport properties in the near and far field of a nuclear repository, modelling of the transport should also take the chemistry into account. The reactive transport modelling consists of two main components: a code that combines the possible chemical reactions with thermo-hydrogeological processes interactively and a thermodynamic databank supporting the required parameters for the calculation of the chemical reactions. In the last decade many thermo-hydrogeological codes were upgraded to include the modelling of the chemical processes. TOUGHREACT is one of these codes. This is an extension of the well known simulator TOUGH2 for modelling geoprocesses. The code is developed by LBNL (Lawrence Berkeley National Laboratory, Univ. of California) for the simulation of the multi-phase transport of gas and liquid in porous media including heat transfer. After the release of its first version in 1998, this code has been applied and improved many times in conjunction with considerations for nuclear waste emplacement. A recent version has been extended to calculate ion activities in concentrated salt solutions applying the Pitzer model. In TOUGHREACT, the incorporated equation of state module ECO2N is applied as the EOS module for non-isothermal multiphase flow in a fluid system of H2O-NaCl-CO2. The partitioning of H2O and CO2 between liquid and gas phases is modelled as a function of temperature, pressure, and salinity. This module is applicable for waste repositories being expected to generate or having originally CO2 in the fluid system. The enhanced TOUGHREACT uses an EQ3/6-formatted database

  8. Different Reactive Oxygen Species Lead to Distinct Changes of Cellular Metal Ions in the Eukaryotic Model Organism Saccharomyces cerevisiae

    Directory of Open Access Journals (Sweden)

    Peter J. Rogers


    Full Text Available Elemental uptake and export of the cell are tightly regulated thereby maintaining the ionomic homeostasis. This equilibrium can be disrupted upon exposure to exogenous reactive oxygen species (ROS, leading to reduction or elevation of the intracellular metal ions. In this study, the ionomic composition in the eukaryotic model organism Saccharomyces cerevisiae was profiled using the inductively-coupled plasma optical emission spectrometer (ICP-OES following the treatment with individual ROS, including hydrogen peroxide, cumen hydroperoxide, linoleic acid hydroperoxide (LAH, the superoxide-generating agent menadione, the thiol-oxidising agent diamide [diazine-dicarboxylic acid-bis(dimethylamide], dimedone and peroxynitrite. The findings demonstrated that different ROS resulted in distinct changes in cellular metal ions. Aluminium (Al3+ level rose up to 50-fold after the diamide treatment. Cellular potassium (K+ in LAH-treated cells was 26-fold less compared to the non-treated controls. The diamide-induced Al3+ accumulation was further validated by the enhanced Al3+ uptake along the time course and diamide doses. Pre-incubation of yeast with individual elements including iron, copper, manganese and magnesium failed to block diamide-induced Al3+ uptake, suggesting Al3+-specific transporters could be involved in Al3+ uptake. Furthermore, LAH-induced potassium depletion was validated by a rescue experiment in which addition of potassium increased yeast growth in LAH-containing media by 26% compared to LAH alone. Taken together, the data, for the first time, demonstrated the linkage between ionomic profiles and individual oxidative conditions.


    Directory of Open Access Journals (Sweden)

    Ji-Hun Park


    Full Text Available The D-galactose (D-gal-induced animal model, generated by repeated subcutaneous D-gal injections over approximately 6 weeks, has been frequently used for diabetes and aging research. However, little research has investigated the direct correlation between D-gal and autoantibody formation despite several reports on diabetes-and aging-related autoantibodies. The purpose of this study was to determine whether repetitive injection of D-gal can induce autoantibody production in mice. First, we used Bovine Serum Albumin (BSA and Advanced Glycation End products (AGE-BSA as the test antigens. The immunoreactivity of serum samples from mice treated with D-gal for 6 weeks was evaluated using Enzyme-Linked Immunosorbent Assay (ELISA. We found that serum samples of D-gal-treated mice had significantly high antibody titers against both BSA and AGE-BSA. Furthermore, the result showed that aminoguanidine treatment, an AGE inhibitor tended to decrease this immunoreactivity. The results of competitive inhibition ELISA using BSA and AGE-BSA as the competitors suggested that the serum samples from D-gal-treated mice contained antibodies not only against BSA but also specific to AGE-BSA. To assess whether the immunoreactivity against BSA is comparable to that against Mouse Serum Albumin (MSA, we examined the reactivity of D-gal-induced antibodies against MSA. Unexpectedly, D-gal-induced antibodies did not react with MSA. This suggests that the production of antibodies by D-gal is in response to an unknown antigen(s, aside from MSA, in mice and that this unknown antigen(s may share similar sequences or three-dimensional structures with BSA.

  10. Use of a Three-Dimensional Reactive Solute Transport Model for Evaluation of Bioreactor Placement in Stream Restoration. (United States)

    Cui, Zhengtao; Welty, Claire; Gold, Arthur J; Groffman, Peter M; Kaushal, Sujay S; Miller, Andrew J


    A three-dimensional groundwater flow and multispecies reactive transport model was used to strategically design placement of bioreactors in the subsurface to achieve maximum removal of nitrate along restored stream reaches. Two hypothetical stream restoration scenarios were evaluated over stream reaches of 40 and 94 m: a step-pool scenario and a channel re-meandering scenario. For the step-pool scenario, bioreactors were placed at locations where mass fluxes of groundwater and nitrate were highest. Bioreactors installed over 50% of the total channel length of a step-pool scenario (located to intercept maximum groundwater and nitrate mass flux) removed nitrate-N entering the channel at a rate of 36.5 kg N yr (100 g N d), achieving about 65% of the removal of a whole-length bioreactor. Bioreactor placement for the re-meandering scenario was designed using a criterion of either highest nitrate mass flux or highest groundwater flux, but not both, because they did not occur together. Bioreactors installed at maximum nitrate flux locations (53% of the total channel length) on the western bank removed nitrate-N entering the channel at 62.0 kg N yr (170 g N d), achieving 85% of nitrate-N removal of whole-length bioreactors for the re-meandering scenario. Bioreactors installed at maximum groundwater flux locations on the western bank along approximately 40% of the re-meandering channel achieved about 65% of nitrate removal of whole-length bioreactors. Placing bioreactors at maximum nitrate flux locations improved denitrification efficiency. Due to low groundwater velocities, bioreactor nitrate-N removal was found to be nitrate limited for all scenarios.

  11. What Is Reactive Arthritis? (United States)

    ... Arthritis PDF Version Size: 69 KB November 2014 What is Reactive Arthritis? Fast Facts: An Easy-to- ... Information About Reactive Arthritis and Other Related Conditions What Causes Reactive Arthritis? Sometimes, reactive arthritis is set ...

  12. Modeling of Calcite Precipitation Driven by Bacteria-facilitated Urea Hydrolysis in A Flow Column Using A Fully Coupled, Fully Implicit Parallel Reactive Transport Simulator (United States)

    Guo, L.; Huang, H.; Gaston, D.; Redden, G. D.


    One approach for immobilizing subsurface metal contaminants involves stimulating the in situ production of mineral phases that sequester or isolate contaminants. One example is using calcium carbonate to immobilize strontium. The success of such approaches depends on understanding how various processes of flow, transport, reaction and resulting porosity-permeability change couple in subsurface systems. Reactive transport models are often used for such purpose. Current subsurface reactive transport simulators typically involve a de-coupled solution approach, such as operator-splitting, that solves the transport equations for components and batch chemistry sequentially, which has limited applicability for many biogeochemical processes with fast kinetics and strong medium property-reaction interactions. A massively parallel, fully coupled, fully implicit reactive transport simulator has been developed based on a parallel multi-physics object oriented software environment computing framework (MOOSE) developed at the Idaho National Laboratory. Within this simulator, the system of transport and reaction equations is solved simultaneously in a fully coupled manner using the Jacobian Free Newton-Krylov (JFNK) method with preconditioning. The simulator was applied to model reactive transport in a one-dimensional column where conditions that favor calcium carbonate precipitation are generated by urea hydrolysis that is catalyzed by urease enzyme. Simulation results are compared to both laboratory column experiments and those obtained using the reactive transport simulator STOMP in terms of: the spatial and temporal distributions of precipitates and reaction rates and other major species in the reaction system; the changes in porosity and permeability; and the computing efficiency based on wall clock simulation time.

  13. Computational methods for reactive transport modeling: An extended law of mass-action, xLMA, method for multiphase equilibrium calculations (United States)

    Leal, Allan M. M.; Kulik, Dmitrii A.; Kosakowski, Georg; Saar, Martin O.


    We present an extended law of mass-action (xLMA) method for multiphase equilibrium calculations and apply it in the context of reactive transport modeling. This extended LMA formulation differs from its conventional counterpart in that (i) it is directly derived from the Gibbs energy minimization (GEM) problem (i.e., the fundamental problem that describes the state of equilibrium of a chemical system under constant temperature and pressure); and (ii) it extends the conventional mass-action equations with Lagrange multipliers from the Gibbs energy minimization problem, which can be interpreted as stability indices of the chemical species. Accounting for these multipliers enables the method to determine all stable phases without presuming their types (e.g., aqueous, gaseous) or their presence in the equilibrium state. Therefore, the here proposed xLMA method inherits traits of Gibbs energy minimization algorithms that allow it to naturally detect the phases present in equilibrium, which can be single-component phases (e.g., pure solids or liquids) or non-ideal multi-component phases (e.g., aqueous, melts, gaseous, solid solutions, adsorption, or ion exchange). Moreover, our xLMA method requires no technique that tentatively adds or removes reactions based on phase stability indices (e.g., saturation indices for minerals), since the extended mass-action