Nonequilibrium sorption of phenols onto geosorbents: the impact of pH on intraparticle mass transfer

While the pH effect on sorption equilibrium of weak acids on natural sorbents was investigated in a number of studies, less is known about the pH dependence of sorption kinetics. This paper investigates the impact of pH on sorption kinetics during the transport of some selected phenols through a sandy aquifer material. Breakthrough curves measured in column experiments were analyzed using a mass transfer based nonequilibrium model designated as dispersed flow, film and particle diffusion model (DF-FPDM). In this model, the rate limiting intraparticle diffusion is characterized by the mass transfer coefficient, kSaV, which can be determined from breakthrough curves by curve fitting. The experimental results indicate that the kSaV is pH-dependent and inversely correlated with the pH-dependent distribution coefficient, K(d,app). Regression equations are presented that may be used to estimate approximate values of intraparticle mass transfer coefficients on the basis of experimentally determined or LFER predicted distribution coefficients.     

Characterization of metal adsorption kinetic properties in batch and fixed-bed reactors

Copper adsorption kinetic properties in batch and fixed-bed reactors were studied in this paper. The isothermal adsorption experiments showed that the copper adsorption capacity of a granular activated carbon (Filtrasorb 200) increased when ionic strength was higher. The presence of EDTA diminished the adsorption. An intraparticle diffusion model and a fixed-bed model were successfully used to describe the batch kinetic and fixed-bed operation behaviors. The kinetics became faster when the solution pH was not controlled, implying that the surface precipitation caused some metal uptake. The external mass transfer coefficient, the diffusivity and the dispersion coefficient were obtained from the modeling. It was found that both external mass transfer and dispersion coefficients increased when the flow rate was higher. Finally effects of kinetic parameters on simulation of fixed-bed operation were conducted.     

Transport of particulate material and dissolved tracer in a highly permeable porous medium: comparison of the transfer parameters

We are experimentally studying, by means of short-pulse injection, the transport and deposition kinetics of suspended particles (silts of the order of 10 microm) in a highly permeable medium consisting of a column of gravel. In our experiments, the breakthrough curves (BTCs) are well described by analytical solutions of a convection/dispersion model with first-order deposition kinetics. All the transport parameters calculated by the model for both particles and dissolved tracer depend on the flow rate. We demonstrate the existence of a critical flow rate, determined experimentally, beyond which the transfer time for the particles is longer than that for the tracer. This phenomenon is unusual in comparison with the results available in the literature. The increase in transfer time of particles in comparison to tracer leads us to assume a purely mechanical phenomenon, that is, collision between particles and grains of the medium with instantaneous reset in motion when the flow rate is sufficient to avoid settling. Thanks to the polydispersivity of the injected suspension and the control of grain size at the outlet, it can also be determined that the coarser particles are recovered before the finer particles, as expected when one considers the size-exclusion effect.     

Contaminant transport in dual-porosity media with dissolved organic matter and bacteria present as mobile colloids

In riverbank filtration, contaminant transport is affected by colloidal particles such as dissolved organic matter (DOM) and bacterial particles. In addition, the subsurface heterogeneity influences the behavior of contaminant transport in riverbank filtration. A mathematical model is developed to describe the contaminant transport in dual-porosity media in the presence of DOM and bacteria as mobile colloids. In the model development, a porous medium is divided into the mobile and immobile regions to consider the presence of ineffective micropores in physically heterogeneous riverbanks. We assume that the contaminant transport in the mobile region is controlled by the advection and dispersion while the contaminant transport in the immobile region occurs due to the molecular diffusion. The contaminant transfer between the mobile and immobile regions takes place by diffusive mass transfer. The mobile region is conceptualized as a four-phase system: two mobile colloidal phases, an aqueous phase, and a solid matrix. The complete set of governing equations is solved numerically with a fully implicit finite difference method. The model results show that in riverbank filtration, the contaminant can migrate further than expected due to the presence of DOM and bacteria. In addition, the contaminant mobility increases further in the presence of the immobile region in aquifers. A sensitivity analysis shows that in dual-porosity media, earlier breakthrough of the contaminant takes place as the volumetric fraction of the mobile region decreases. It is also demonstrated that as the contaminant mass transfer rate coefficient between the mobile and immobile regions increases, the contaminant concentration gradient between the two regions reverses at earlier pore volumes. The contaminant mass transfer coefficient between the mobile and immobile regions mainly controls the tailing effect of the contaminant breakthrough. The contaminant breakthrough curves are sensitive to changes in contaminant adsorption and desorption rate coefficients on DOM and bacteria. In situations where the contaminant is released in the presence of DOM and bacteria in dual-porosity media, the early breakthrough and tailing occur due to the colloidal facilitation and presence of immobile regions.     

Heavy metals removal in fixed-bed column by the macro fungus Pycnoporus sanguineus

The ability of Pycnoporus sanguineus to adsorb heavy metals from aqueous solution was investigated in fixed-bed column studies. The experiments were conducted to study the effect of important design parameters such as column bed height, flow rate and initial concentration of solution. The breakthrough profiles were obtained in these studies. A mathematical model based on external mass transfer and pore diffusion was used for the prediction of mass transfer coefficient and effective diffusivity of metals in macro-fungi bed. Experimental breakthrough profiles were compared with the simulated breakthrough profiles obtained from the mathematical model. Bed Depth Service Time (BDST) model was used to analyse the experimental data and evaluated the performance of biosorption column. The BDST model parameters needed for the design of biosorption columns were evaluated for lead, copper and cadmium removal in the column. The columns were regenerated by eluting the metal ions using 0.1 M hydrochloric acid solution after the adsorption studies. The columns were subjected to repeated cycles of adsorption of same metal ions and desorption to evaluate the removal efficiency after adsorption-desorption.     

A stochastic-advective transport model for NAPL dissolution and degradation in non-uniform flows in porous media

Remediation schemes for contaminated sites are often evaluated to assess their potential for source zone reduction of mass, or treatment of the contaminant between the source and a control plane (CP) to achieve regulatory limits. In this study, we utilize a stochastic stream tube model to explain the behavior of breakthrough curves (BTCs) across a CP. At the local scale, mass dissolution at the source is combined with an advection model with first-order decay for the dissolved plume. Field-scale averaging is then employed to account for spatial variation in mass within the source zone, and variation in the velocity field. Under the assumption of instantaneous mass transfer from the source to the moving liquid, semi-analytical expressions for the BTC and temporal moments are developed, followed by derivation of expressions for effective velocity, dispersion, and degradation coefficients using the method of moments. It is found that degradation strongly influences the behavior of moments and the effective parameters. While increased heterogeneity in the velocity field results in increased dispersion, degradation causes the center of mass of the plume to shift to earlier times, and reduces the dispersion of the BTC by lowering the concentrations in the tail. Modified definitions of effective parameters are presented for degrading solutes to account for the normalization constant (zeroth moment) that keeps changing with time or distance to the CP. It is shown that anomalous dispersion can result for high degradation rates combined with wide variation in velocity fluctuations. Implications of model results on estimating cleanup times and fulfillment of regulatory limits are discussed. Relating mass removal at the source to flux reductions past a control plane is confounded by many factors. Increased heterogeneity in velocity fields causes mass fluxes past a control plane to persist, however, aggressive remediation between the source and CP can reduce these fluxes.     

The influence of mass transfer on solute transport in column experiments with an aggregated soil

The spreading of concentration fronts in dynamic column experiments conducted with a porous, aggregated soil is analyzed by means of a previously documented transport model (DFPSDM) that accounts for longitudinal dispersion, external mass transfer in the boundary layer surrounding the aggregate particles, and diffusion in the intra-aggregate pores. The data are drawn from a previous report on the transport of tritiated water, chloride, and calcium ion in a column filled with Ione soil having an average aggregate particle diameter of 0.34 cm, at pore water velocities from 3 to 143 cm/h. The parameters for dispersion, external mass transfer, and internal diffusion were predicted for the experimental conditions by means of generalized correlations, independent of the column data. The predicted degree of solute front-spreading agreed well with the experimental observations. Consistent with the aggregate porosity of 45%, the tortuosity factor for internal pore diffusion was approximately equal to 2. Quantitative criteria for the spreading influence of the three mechanisms are evaluated with respect to the column data. Hydrodynamic dispersion is thought to have governed the front shape in the experiments at low velocity, and internal pore diffusion is believed to have dominated at high velocity; the external mass transfer resistance played a minor role under all conditions. A transport model such as DFPSDM is useful for interpreting column data with regard to the mechanisms controlling concentration front dynamics, but care must be exercised to avoid confounding the effects of the relevant processes.     

Modeling field-scale cosolvent flooding for DNAPL source zone remediation

A three-dimensional, compositional, multiphase flow simulator was used to model a field-scale test of DNAPL removal by cosolvent flooding. The DNAPL at this site was tetrachloroethylene (PCE), and the flooding solution was an ethanol/water mixture, with up to 95% ethanol. The numerical model, UTCHEM accounts for the equilibrium phase behavior and multiphase flow of a ternary ethanol-PCE-water system. Simulations of enhanced cosolvent flooding using a kinetic interphase mass transfer approach show that when a very high concentration of alcohol is injected, the DNAPL/water/alcohol mixture forms a single phase and local mass transfer limitations become irrelevant. The field simulations were carried out in three steps. At the first level, a simple uncalibrated layered model is developed. This model is capable of roughly reproducing the production well concentrations of alcohol, but not of PCE. A more refined (but uncalibrated) permeability model is able to accurately simulate the breakthrough concentrations of injected alcohol from the production wells, but is unable to accurately predict the PCE removal. The final model uses a calibration of the initial PCE distribution to get good matches with the PCE effluent curves from the extraction wells. It is evident that the effectiveness of DNAPL source zone remediation is mainly affected by characteristics of the spatial heterogeneity of porous media and the variable (and unknown) DNAPL distribution. The inherent uncertainty in the DNAPL distribution at real field sites means that some form of calibration of the initial contaminant distribution will almost always be required to match contaminant effluent breakthrough curves.     

Development of a continuously stirred flow cell for investigating sorption mass transfer

This paper introduces a new reversible-flow design for a continuously stirred reactor used to study sorption mass transfer in soil and solvent systems. The stirred reactor has potential advantages over conventional packed column or batch reactors because it isolates intraparticle sorption rate limitations from advective-dispersive transport, yet allows changes to flux through the reactor for analysis of sorption kinetics under dynamic conditions. Previously, stirred reactors have often failed due to clogging of sediment on the effluent frit. The reverse-flow backwashing design allows longer life and higher confidence in maintaining mixed conditions than previous designs. Mass transfer 'rate coefficients estimated from stirred and column experiments are compared; both techniques produced results consistent with a published correlation. The data also show that fitted sorption mass transfer coefficients can be strongly dependent on the choice of equilibrium partition coefficient (i.e. batch or first-moment derived values), and that the conventional two-site sorption kinetics model fails to accurately predict sorption mass transfer in the presence of changing solvent velocity through the reactor.     

Estimating first-order reaction rate coefficient for transport with nonequilibrium linear mass transfer in heterogeneous media

A travel-time based approach is developed for estimating first-order reaction rate coefficients for transport with nonequilibrium linear mass transfer in heterogeneous media. Tracer transport in the mobile domain is characterized by a travel-time distribution, and mass transfer rates are described by a convolution product of concentrations in the mobile domain and a memory function rather than predefining the mass transfer model. A constant first-order reaction is assumed to occur only in the mobile domain. Analytical solutions in Laplace domain can be derived for both conservative and reactive breakthrough curves (BTCs). Temporal-moment analyses are presented by using the first and second moments of conservative and reactive BTCs and the mass consumption of the reactant for an inverse Gaussian travel-time distribution. In terms of moment matching, there is no need for one to specify the mass transfer model. With the same capacity ratio and the mean retention time, all mass transfer models will lead to the same moment-derived reaction rate coefficients. In addition, the consideration of mass transfer generally yields larger estimations of the reaction rate coefficient than models ignoring mass transfer. Furthermore, the capacity ratio and the mean retention time have opposite influences on the estimation of the reaction rate coefficient: the first-order reaction rate coefficient is positively linearly proportional to the capacity ratio, but negatively linearly proportional to the mean retention time.     

A high-resolution non-invasive approach to quantify oxygen transport across the capillary fringe and within the underlying groundwater

Oxygen transport across the capillary fringe is relevant for many biogeochemical processes. We present a non-invasive technique, based on optode technology, to measure high-resolution concentration profiles of oxygen across the unsaturated/saturated interface. By conducting a series of quasi two-dimensional flow-through laboratory experiments, we show that vertical hydrodynamic dispersion in the water-saturated part of the capillary fringe is the process limiting the mass transfer of oxygen. A number of experimental conditions were tested in order to investigate the influence of grain size and horizontal flow velocity on transverse vertical dispersion in the capillary fringe. In the same setup, analogous experiments were simultaneously carried out in the fully water-saturated zone, therefore allowing a direct comparison with oxygen transfer across the capillary fringe. The outcomes of the experiments under various conditions show that oxygen transport in the two zones of interest (i.e., the unsaturated/saturated interface and the saturated zone) is characterized by very similar transverse dispersion coefficients. An influence of the capillary fringe morphology on oxygen transport has not been observed. These results may be explained by the narrow grain size distribution used in the experiments, leading to a steep decline in water saturation at the unsaturated/saturated interface and to the absence of trapped gas in this transition zone. We also modeled flow (applying the van Genuchten and the Brooks-Corey relationships) and two-dimensional transport across the capillary fringe, obtaining simulated profiles of equivalent aqueous oxygen concentration that were in good agreement with the observations.     

Removal of metal ions from the complexed solutions in fixed bed using a strong-acid ion exchange resin

Fixed bed removal of equimolar metal ions (Co²⁺, Ni²⁺, Mn²⁺, Sr²⁺) from aqueous solutions using a strong-acid resin was examined. The solution contained a water-soluble complexing agent including ethylenediaminetetraacetic acid, nitrilotriacetic acid, and citric acid. Experiments were performed under different solution pH and molar concentration ratios of complexing agent to the total metals. It was shown from batch studies that the equilibrium exchange of metals and the resin mainly depended on solution pH, and partly on the type of complexing agent used. A mass transfer model was proposed to describe the breakthrough curves of the resin bed, which contained two parameters (τ and k) estimated from the observed breakthrough data. The calculated breakthrough curves agreed well with the measured ones (standard deviation <6%). In fixed bed tests at low pH (=2), the type of complexing agent had little effect on the breakthrough data. For a given complexing agent, the metal with a larger overall formation constant (K_f) showed a smaller exchange capacity. For a given metal ion, the complexing agent with a larger K_f also revealed a smaller exchange capacity.     

A two-region nonequilibrium model for solute transport in solution conduits in karstic aquifers

A two-region nonequilibrium model was used to calibrate initial solute-transport parameter estimates generated from tracer-breakthrough curves (TBCs) developed from tracer tests conducted in uni-axial solution conduits in karstic aquifers. Two-region nonequilibrium models account for partitioning of solute into mobile- and immobile-fluid regions to produce a more representative model fit to the strong tails associated with TBCs than do equilibrium models. The nonequilibrium model resulted in an increase in average flow velocities and a decrease in longitudinal dispersion coefficients over comparable estimates using an equilibrium model. Increases in velocity and decreases in dispersion were obtained at the expense of including parameters that describe solute partitioning and mass transfer rate for the mobile- and immobile-fluid regions. In addition, nonidentifiable sorption and mass transfer parameters for the immobile-fluid regions could only be described in terms of upper and lower bounds using readily determined identifiable ratios representing solute partitioning and system constraints based on known physical properties. The identifiable ratios and system constraints serve to minimize model nonuniqueness and renders the nonidentification problem trivial.     

Using chemical models for evaluating the geochemical confinement capacity of a geological barrier application to the Centre de Stockage de l'Aube (France)

The feasibility of using a chemical reaction-based approach for evaluating and modelling the role of adsorption reactions in determining the geochernical confinement capacity of natural geological barriers is being studied as part of an on-going R & D programme. The confined superficial aquifer underlying the Centre de Stockage de l'Aube facility, a geological barrier for this site, has been used as a case study with the following aims. First, development of a site characterisation protocol and demonstration of its use to determine the principal geochemical characteristics of aquifer materials using batch experiments and to represent the information obtained in terms of a chemical model. The experimental results obtained for Ni²⁺ partitioning as a function of total Ni, pH, total Ca and total solid can be satisfactorily represented in terms of reactions with an ion exchange site and a single amphoteric surface hydroxyl site with ferrihydrite reaction constants. A second objective is the incorporation of the reactions in a coupled geochemistry/transport code, and to verify the applicability of the coupled code predictions for Ni²⁺ mass transfer by comparison with the results obtained during column tracer experiments. The breakthrough curve and equilibrium solid phase Ni loading, predicted by a one-dimensional coupled model for a column tracer experiment, agree closely with observed data.Additional studies are underway to reduce model conditionality, to extend the adsorption model to other analogue cations and anions, to incorporate the effect of natural organic matter and to take into consideration precipitation/dissolution of amorphous Fe surface phases.     

好氧反硝化去除低浓度NO_x的动力学模型研究

在好氧条件下,对利用生物滴滤塔（bio-trickling filter,BTF）反硝化净化废气中NOx的过程进行了理论模型探讨,并用实验结果进行了验证。在分析NOx在BTF内传质以及生物降解过程的基础上,建立了NOx在气相和生物膜相的质量守恒方程,结合Fick定律和好氧条件下的Monod微生物反应动力学方程,最终得到了NOx在BTF中＂吸附-微生物降解＂过程的动力学方程。模型计算值与实验结果表明,BTF中好氧反硝化过程为一级反应过程,利用该模型可以较好地模拟进口浓度、停留时间等因素对出口浓度的影响,对实际应用具有指导意义。     

A large-scale experiment on mass transfer of trichloroethylene from the unsaturated zone of a sandy aquifer to its interfaces

A large-scale experiment was conducted to investigate the transport of trichloroethylene (TCE) vapors in the unsaturated zone and to determine the mass transfer to the groundwater and the atmosphere. The experiment involved injection of 5 1 of TCE in the unsaturated zone under controlled conditions, with multidepth sampling of gas and water through the unsaturated zone and across the capillary zone into underlying groundwater. The mass transfer of TCE vapors from the vadose zone to the atmosphere was quantified using a vertical flux chamber. A special soil water sampler was used to monitor transport across the capillary fringe. Experimental data indicated that TCE in the unsaturated zone was mainly transported to the atmosphere and this exchange reduced significantly the potential for groundwater pollution. The maximum measured TCE flux to the atmosphere was about 3 g/m(2)/day. Observed and calculated fluxes based on vertical TCE vapor concentration gradients and Fick's law were in good agreement. This confirms that TCE vapor transport under the experimental conditions was governed essentially by molecular diffusion. TCE vapors also caused a lower, but significant contamination of the underlying groundwater by dispersion across the capillary fringe with a corresponding maximum flux of about 0.1 g/m(2)/day. This mass transfer to groundwater is partly uncertain due to an inadvertent entry of some nonaqueous phase liquid (NAPL) from the source area into the saturated zone. Application of an analytical solution to estimate the TCE flux from the unsaturated zone to the groundwater indicated that this phenomenon is not only influenced by molecular diffusion but also by vertical dispersion. The mass balance indicates that, under the given experimental conditions (e.g. proximity of the source emplacement relative to the soil surface, relatively high permeable porous medium), nearly 95% of the initial TCE mass was transferred to the atmosphere.     

Modelling tritium and phosphorus transport by preferential flow in structured soil

Subsurface solute transport through structured soil is studied by model interpretation of experimental breakthrough curves from tritium and phosphorus tracer tests in three intact soil monoliths. Similar geochemical conditions, with nearly neutral pH, were maintained in all the experiments. Observed transport differences for the same tracer are thus mainly due to differences in the physical transport process between the different monoliths. The modelling is based on a probabilistic Lagrangian approach that decouples physical and chemical mass transfer and transformation processes from pure and stochastic advection. Thereby, it enables explicit quantification of the physical transport process through preferential flow paths, honouring all independently available experimental information. Modelling of the tritium breakthrough curves yields a probability density function of non-reactive solute travel time that is coupled with a reaction model for linear, non-equilibrium sorption–desorption to describe the phosphorus transport. The tritium model results indicate that significant preferential flow occurs in all the experimental soil monoliths, ranging from 60–100% of the total water flow moving through only 25–40% of the total water content. In agreement with the fact that geochemical conditions were similar in all experiments, phosphorus model results yield consistent first-order kinetic parameter values for the sorption–desorption process in two of the three soil monoliths; phosphorus transport through the third monolith cannot be modelled because the apparent mean transport rate of phosphorus is anomalously rapid relative to the non-adsorptive tritium transport. The occurrence of preferential flow alters the whole shape of the phosphorus breakthrough curve, not least the peak mass flux and concentration values, and increases the transported phosphorus mass by 2–3 times relative to the estimated mass transport without preferential flow in the two modelled monoliths.     

The Development of a Sampling System for the Determination of Odor Emission Rates from Areal Surfaces: Part II. Mathematical Model

Abstract

An improved design for an odor emission hood was examined in the laboratory using ammonia emission from a water surface. The experimental ammonia convective mass transfer coefficients from a diluted ammonia solution were determined at velocities of 0.3 m/s to 0.8 m/s using the odor emission hood. The theoretical ammonia convective mass transfer coefficients were also predicted by boundary layer theory under laminar flow conditions. It was found that experimental data were only 10% below theoretical predictions at an air velocity of 0.3 m/s to 0.6 m/s. The maximum velocity was limited to 0.6 m/s by the geometric size, shape and aerodynamic stability of the hood. At 0.33 m/s, the smallest variation of mass transfer coefficients was measured. The odor emission rate was found to be a function of air velocity to the power 0.5 in accordance with boundary layer theory. An odor sampling system based upon the odor emission hood provides a way to quantify the potential odor emission strength in sewage treatment plants, for odor dispersion modeling and odor control.     

Modeling of non-reactive solute transport in fractured clayey till during variable flow rate and time

Fractures and biopores can act as preferential flow paths in clay aquitards and may rapidly transmit contaminants into underlying aquifers. Reliable numerical models for assessment of groundwater contamination from such aquitards are needed for planning, regulatory and remediation purposes. In this investigation, high resolution preferential water-saturated flow and bromide transport data were used to evaluate the suitability of equivalent porous medium (EPM), dual porosity (DP) and discrete fracture/matrix diffusion (DFMD) numerical modeling approaches for assessment of flow and non-reactive solute transport in clayey till. The experimental data were obtained from four large undisturbed soil columns (taken from 1.5 to 3.5 m depth) in which biopores and channels along fractures controlled 96-99% of water-saturated flow. Simulating the transport data with the EPM effective porosity model (FRACTRAN in EPM mode) was not successful because calibrated effective porosity for the same column had to be varied up to 1 order of magnitude in order to simulate solute breakthrough for the applied flow rates between 11 and 49 mm/day. Attempts to simulate the same data with the DP models CXTFIT and MODFLOW/MT3D were also unsuccessful because fitted values for dispersion, mobile zone porosity, and mass transfer coefficient between mobile and immobile zones varied several orders of magnitude for the different flow rates, and because dispersion values were furthermore not physically realistic. Only the DFMD modeling approach (FRACTRAN in DFMD mode) was capable to simulate the observed changes in solute transport behavior during alternating flow rate without changing values of calibrated fracture spacing and fracture aperture to represent the macropores.     

Experimental Zn(II) retention in a sandy loam soil by very small columns

The use of column experiments, usually performed to better approximate field conditions, may provide information that is not available from batch experiments. In such experiments heavy metals are often adsorbed until saturation followed by desorption experiments. When the affinity of the metal to soil is high, the retention factor (R) could be greater than thousands and the duration of experiments can become impractically long. In order to use reasonable laboratory time, the flow rate should be increased or the column size decreased. The increase in flow rate produces undesirable kinetic and dispersion effects, so we used very small soil columns (pore volume = 0.31–0.70 ml) and relatively high flow rates (0.03–0.12 ml min⁻¹) in studies of Zn(II) adsorption and retention in soils. Conservative tracer flow column experiments under saturation conditions were carried out to determine flow parameters for different flow rates. Column pore volume (V_p), Peclet numbers (Pe) and longitudinal dispersion coefficients (D_L) were determined from breakthrough curves. The effect of type of electrolyte and ionic strength on the Zn(II) retention onto soil was determined. The influence of flow rate and bed height on the retention coefficient and on the mass transfer zone was also studied. The effect of different influent Zn(II) concentrations on the R values obtained was analyzed. Freundlich parameters from column experiments were compared with batch ones. The leaching efficiency of different electrolytes, salts of weak organic acids and EDTA was also studied.