Transport of reactive colloids and contaminants in groundwater: effect of nonlinear kinetic interactions

Transport of reactive colloids in groundwater may enhance the transport of contaminants in groundwater. Often, the interpretation of results of transport experiments is not a simple task as both reactions of colloids with the solid matrix and reactions of contaminants with the solid matrix and mobile and immobile colloids may be time dependent and nonlinear. Further colloid transport properties may differ from solute transport properties. In this paper, a one-dimensional model for coupled and contaminant in a porous medium (COLTRAP) is presented together with simulation results. Calculated breakthrough curves (BTC's) during contamination and decontamination show systematically the effect of nonlinear and kinetic interactions on contaminant transport in the presence of reactive colloids, and the effect of colloid transport properties that differ from solute transport properties. It is shown that in case of linear kinetic reactions, the rate of exchange of mobile and immobile colloids have a large impact on the shape of BTC's even if the solid matrix is saturated with respect to colloids. BTC's during the contamination and decontamination phase have identical shapes in this case. Moreover, the slow reactions of contaminants and colloids may lead to unretarded breakthrough of contaminants. Independent of reaction rates, nonlinear reactions lead to BTC's that are steeper during contamination than in the linear case. A characteristic aspect of nonlinear sorption is that shapes of BTC's differ during the contamination and decontamination phase. It has been observed that shapes of some of the simulated adsorption and desorption curves are similar as shapes found in experiments reported in literature. This stresses the importance of incorporating both kinetics and nonlinearity in models for coupled colloid and contaminant transport and the capability of COLTRAP to interpret experimental results. Finally, to figure out whether nonlinear processes play a role, it is very important to consider both contamination and decontamination in transport experiments.     

Modelling of diffusion-limited retardation of contaminants in hydraulically and lithologically nonuniform media

A new reactive transport modelling approach and examples of its application are presented, dealing with the impact of sorption/desorption kinetics on the spreading of solutes, e.g. organic contaminants, in groundwater. Slow sorption/desorption is known from the literature to be strongly responsible for the retardation of organic contaminants. The modelling concept applied in this paper quantifies sorption/desorption kinetics by an intra-particle diffusion approach. According to this idea, solute uptake by or release from the aquifer material is modelled at small scale by a "slow" diffusion process where the diffusion coefficient is reduced as compared to the aqueous diffusion coefficient due to (i) the size and shape of intra-particle pores and (ii) retarded transport of solutes within intra-particle pores governed by a nonlinear sorption isotherm. This process-based concept has the advantage of requiring only measurable model parameters, thus avoiding fitting parameters like first-order rate coefficients.In addition, the approach presented here allows for modelling of slow sorption/desorption in lithologically nonuniform media. Therefore, it accounts for well-known experimental findings indicating that sorptive properties depend on (i) the grain size distribution of the aquifer material and (ii) the lithological composition (e.g. percentage of quartz, sandstone, limestone, etc.) of each grain size fraction. The small-scale physico-chemical model describing sorption/desorption is coupled to a large-scale model of groundwater flow and solute transport. Consequently, hydraulic heterogeneities may also be considered by the overall model. This coupling is regarded as an essential prerequisite for simulating field-scale scenarios which will be addressed by a forthcoming publication.This paper focuses on mathematical model formulation, implementation of the numerical code and lab-scale model applications highlighting the sorption and desorption behavior of an organic contaminant (Phenanthrene) with regard to three lithocomponents exhibiting different sorptive properties. In particular, it is shown that breakthrough curves (BTCs) for lithologically nonuniform media cannot be obtained via simple arithmetic averaging of breakthrough curves for lithologically uniform media. In addition, as no analytical solutions are available for model validation purposes, simulation results are compared to measurements from lab-scale column experiments. The model results indicate that the new code can be regarded as a valuable tool for predicting long-term contaminant uptake or release, which may last for several hundreds of years for some lithocomponents. In particular, breakthrough curves simulated by pure forward modelling reproduce experimental data much better than a calibrated standard first-order kinetics reactive transport model, thus indicating that the new approach is of high quality and may be advantageously used for supporting the design of remediation strategies at contaminated sites where some lithocomponents and/or grain size classes may provide a long-term pollutant source.     

Adsorption behavior of light green anionic dye using cationic surfactant-modified wheat straw in batch and column mode

An agricultural by-product, natural wheat straw (NWS), was soaked in 1 % cationic surfactant (hexadecylpyridinium bromide, CPB) solution for 24 h (at 293 K), and modified wheat straw (MWS) was obtained. Analysis of FTIR, XFR, and nitrogen element showed that CPB was adsorbed onto surface of NWS. Then, MWS was used as adsorbent for the removal of light green dye (LG, anionic dye) from aqueous solution. The experiment was performed in batch and column mode at room temperature (293 K). Sodium chloride (up to 0.1 mol/L) existed in solution was not favor of LG dye adsorption. The equilibrium data were better described by Langmuir isotherm, and adsorption capacity of q _m from Langmuir model was 70.01?±?3.39 mg/g. In fixed-bed column adsorption mode, the effects of initial LG concentration (30, 50, 70 mg/L) and flow rate (6.5, 9.0, 14.5 mL/min) on adsorption were presented. Thomas and modified dose–response models were used to predict the breakthrough curves using nonlinear analysis method, and both models can fit the breakthrough curves. Theoretical and experimental breakthrough curves were drawn and compared. The results implied that MWS can be used as adsorbent material to remove LG from aqueous solution.     

Dynamic behaviour of Cd2+ adsorption in equilibrium batch studies by CaCO3 −-rich Corbicula fluminea shell

This work presents the structural and adsorption properties of the CaCO₃ ^?-rich Corbicula fluminea shell as a natural and economic adsorbent to remove Cd ions from aqueous solutions under batch studies. Experiments were conducted with different contact times, various initial concentrations, initial solution pH and serial biosorbent dosage to examine the dynamic characterization of the adsorption and its influence on Cd uptake capacity. The characterization of the C. fluminea shell using SEM/EDX revealed that the adsorbent surface is mostly impregnated by small particles of potentially calcium salts. The dominant Cd adsorption mechanism is strongly pH and concentration dependent. A maximum Cd removal efficiency of 96.20 % was obtained at pH 7 while the optimum adsorbent dosage was observed as 5 g/L. The Langmuir isotherm was discovered to be more suitable to represent the experimental equilibrium isotherm results with higher correlation coefficients (R ²?>?0.98) than Freundlich (R ²?<?0.97).The correlation coefficient values (p?<?0.01) indicated the superiority of the Langmuir isotherm over the Freundlich isotherm.     

Analysis of the migration of instantaneously injected cesium in artificial fractures of Lac du Bonnet granite, Manitoba, Canada

Breakthrough curves of ¹³⁷Cs and tritiated water injected instantaneously into artificial fractures in Lac du Bonnet granite were analyzed using the analytical solution for a single rock-fracture system and assuming the linear sorption isotherm of the solute. Parameters of nuclide diffusion and sorption in rock matrices, obtained by fitting, varied depending on the flow velocity in the fractures. According to theoretical calculations, different fracture flow velocities lead to different diffusion distances of nuclides in matrices at the same injection volume. As microscopic inhomogeneity is considered to exist in the rock matrix, the average diffusion-sorption characteristics of the matrix within the diffusion distance may have varied with the fracture flow velocity. Surface sorption was marked in fractures that had relatively high matrix sorption-diffusion capacities. The phenomenon was interpreted using the theoretical relationships developed between the surface sorption, matrix sorption and pore diffusion coefficient, and the porosity of matrices.The effect of the nonlinear sorption of solute was examined by numerically solving model equations that incorporate the nonlinear isotherm. This incorporation may contribute to the reduction of deviations between theoretical and experimental BTC's.     

改性沸石对低浓度氨氮废水的动态吸附

采用氯化钠溶液对甘肃白银天然沸石改性,以低浓度氨氮(NH4+-N)废水为处理对象,对比了天然沸石和改性沸石的动态吸附特性并绘制穿透曲线,利用Origin软件对实验数据分析处理,得出穿透曲线的通式。结果表明:在相同条件下,改性沸石的穿透时间和吸附饱和时间都比天然沸石的长约1.5倍;沸石经氯化钠改性后,对NH4+-N的吸附速率和饱和吸附量都明显提高,吸附性能显著改善。Origin软件对水溶液中NH4+-N的吸附穿透曲线的Logistic模型回归式具有较高的精度,该模型可以很好地反映沸石吸附剂的动态吸附过程。     

Transport modeling of copper and cadmium with linear and nonlinear retardation factors

The predictive accuracy of using the one-dimensional advection–dispersion equation to evaluate the fate and transport of solute in a soil column is usually dependent on the proper determination of chemical retardation factors. Typically, the distribution coefficient (K_d) obtained by fitting the linear sorption isotherm has been extensively used to consider general geochemical reactions on solute transport in a low-concentration range. However, the linear distribution coefficient cannot be adequately utilized to describe the solute fate at a higher concentration level. This study employed the nonlinear equilibrium-controlled sorption parameters to determine the retardation factor used in column leaching experiments. Copper and cadmium transportation in a lateritic silty-clay soil column was examined. Through the explicit finite-difference calculations with a third-order total-variation-diminishing (TVD) numerical solution scheme, all results of the theoretical copper and cadmium breakthrough curves (BTCs) simulated by using the Freundlich nonlinear retardation factors revealed good agreement with the experimental observations.     

Application of HYDRUS 1D model for assessment of phenol–soil adsorption dynamics

Laboratory-scale batch, vertical, and horizontal column experiments were conducted to investigate the attenuative capacity of a fine-grained clayey soil of local origin in the surrounding of a steel plant wastewater discharge site in West Bengal, India, for removal of phenol. Linear, Langmuir, and Freundlich isotherm plots from batch experimental data revealed that Freundlich isotherm model was reasonably fitted (R ²?=?0.94). The breakthrough column experiments were also carried out with different soil bed heights (5, 10, and 15 cm) under uniform flow to study the hydraulic movements of phenol by evaluating time concentration flow behavior using bromide as a tracer. The horizontal migration test was also conducted in the laboratory using adsorptive phenol and nonreactive bromide tracer to explore the movement of solute in a horizontal distance. The hydrodynamic dispersion coefficients (D) in the vertical and horizontal directions in the soil were estimated using nonlinear least-square parameter optimization method in CXTFIT model. In addition, the equilibrium convection dispersion model in HYDRUS 1D was also examined to simulate the fate and transport of phenol in vertical and horizontal directions using Freundlich isotherm constants and estimated hydrodynamic parameters as input in the model. The model efficacy and validation were examined through statistical parameters such as the coefficient of determination (R ²), root mean square error and design of index (d).     

Modelling the solute transport under nonequilibrium conditions on the basis of mass transfer equations

A solute transport model that describes nonequilibrium adsorption in soil/groundwater systems by mass transfer equations for film and intraparticle diffusion is presented. The model is useful in cases where breakthrough curve spreading cannot be explained by dispersion only. To evaluate its validity, the model was applied to several data sets from column experiments. The validity was also proved by a comparison with an analytical solution for the limiting case of predominating dispersion. Furthermore, a sensitivity analysis was performed to illustrate the influence of different process and sorption parameters (pore water velocity, intraparticle mass transfer coefficient, isotherm nonlinearity) on the shape of the calculated breakthrough curves. The application of the proposed model is discussed in comparison to the widely used dispersed flow/local equilibrium model, and a relationship between both models, which is based on a lumped parameter approach, is shown.     

Development of a fuzzy-stochastic nonlinear model to incorporate aleatoric and epistemic uncertainty

Site uncertainties significantly influence groundwater flow and contaminant transport predictions. Aleatoric and epistemic uncertainty are both identified in site characterization and represented using proper uncertainty theories. When one theory best represents one parameter whereas a different theory may be more suitable for another parameter, the hybrid propagation of aleatoric (random) and epistemic (nonrandom) uncertainties will occur. The computational challenges of joint propagation of aleatoric and epistemic uncertainty through groundwater flow and contaminant transport models are significant. A fuzzy-stochastic nonlinear model was developed in this paper to incorporate these two types of uncertain site information and reduce the computational cost. The results show that (1) the computational cost using the nonlinear model is reduced compared with that of using the sparse grid algorithm and Monte Carlo methods; (2) the uncertainty of hydraulic conductivity (K) significantly influences the water head and solute distribution at the observation wells compared to other uncertain parameters, such as the storage coefficient and the distribution coefficient (K_d); and (3) the combination of multiple uncertain parameters substantially affects the simulation results. Neglecting site uncertainties may lead to unrealistic predictions.     

Migration of Cs through quartz sand: experimental results and modeling approaches

We present results from experiments on the migration of ¹³⁷Cs through columns containing quartz sand. Times for ¹³⁷Cs movement through these columns and the quantity of ¹³⁷Cs adsorbed by the sand decreased as the ionic strength of the pore water increased from 0.002 to 0.1 m. The breakthrough curves were characterized by a slow approach towards steady-state concentrations as well as by long tails, indicating that ¹³⁷Cs adsorption to the sand grains was, at least in part, controlled by rate-limited reactions. Various formulations for solute mass transfer were tested for their ability to fit the experimental breakthrough curves. Based on a statistical analysis, a nonlinear, two-site model was identified as the most appropriate for describing the suite of experimental data. Variation in the model parameter that describes the rate of ¹³⁷Cs adsorption to the sand showed no consistent pattern with changes in ionic strength. In contrast, model parameters describing the sorption capacity of the sand grains and the fraction of kinetic sorption sites on the sand decreased with increasing ionic strength. The parameter describing the rate of ¹³⁷Cs desorption varied directly with changes in ionic strength.     

2,4-二氯苯酚在土壤中的吸附及其批实验与柱实验的分配系数比较

为了研究2,4-二氯苯酚在土壤中的吸附及比较其批实验与柱实验的分配系数Kd,开展了2,4-二氯苯酚的批实验（不同液固比条件下）和柱实验。通过分析结果可知,在批实验中,不同液固比条件下2,4-二氯苯酚达到平衡的时间类似,都在60～70 h,吸附动力学曲线符合伪二级动力学方程,吸附规律是：液固比越大,平衡吸附量增大,反应速率常数K2减小,初始吸附速率常数减小;Kd随液固比增大而降低,范围在2.91～2.12 L/kg。柱实验结果表明,2,4-二氯苯酚的贯穿曲线可以很好地用化学非平衡模型来拟合,通过模型拟合得到的Kd值要低于批实验的结果。该研究对表征2,4-二氯苯酚在环境中的行为、预测其对土壤和地下水的污染及其治理提供了依据。     

Modification of Langmuir isotherm in solution systems--definition and utilization of concentration dependent factor

The Langmuir isotherm, originally derived for the adsorption of gas molecules on solid surfaces, was modified to fit the adsorption isotherm of solutes onto solid surfaces in solution systems. The aim of this modification is based on the fact that direct application of the Langmuir isotherm to solution systems often leads to poor data fitting. In the present communication, it is shown that the level of data fitting to the Langmuir isotherm of literature data can be improved by a simple modification introducing a concentration dependent factor, X. The key concept of the modification lies in that the concentration of solute affects both adsorption and desorption stages. As a first approximation, we adopted a single-term polynomial for both processes of adsorption and desorption. Based on reanalysis of literature data of adsorption in solution, we confirmed that indeed the modified Langmuir isotherm more accurately describes the experimental observations. Furthermore, we proposed that the concentration dependent factor could be associated with the surface heterogeneity index that was introduced in a few other modified Langmuir isotherms. Some advantages and limitations of proposed modified Langmuir isotherm are also discussed.     

Kinetics and isotherm modeling of azoxystrobin and imidacloprid retention in biomixtures

The paper reports the kinetics and adsorption isotherm modeling for imidacloprid (IMIDA) and azoxystrobin (AZOXY) in rice straw (RS)/corn cob (CC) and peat (P)/compost (C) based biomixtures. The pseudo-first-order (PFO), pseudo-second-order (PSO), Elovich and intraparticle diffusion models were used to describe the kinetics. The adsorption data were subjected to the Langmuir and the Freundlich isotherms. Results (r²_Adj values) suggested that the modified Elovich model was the best suited to explain the kinetics of IMIDA sorption while different models explained AZOXY sorption kinetics in different biomixtures (PFO in RS?+?C and RS?+?P; PSO in CC?+?P and Elovich in CC?+?C). Biomixtures varied in their capacity to adsorb both pesticides and the adsorption coefficient (K_d) values were 116.8–369.24 (AZOXY) and 24.2–293.4 (IMIDA). The Freundlich isotherm better explained the sorption of both pesticides. Comparison analysis of linear and nonlinear method for estimating the Freundlich adsorption constants was made. In general, r²_Adj values were higher for the nonlinear fit (AZOXY?=?0.938–0.982; IMIDA?=?0.91–0.970) than the linear fit (AZOXY?=?0.886–0.993; IMIDA?=?0.870–0.974) suggesting that the nonlinear Freundlich equation better explained the sorption. The rice straw-based biomixtures performed better in adsorbing both the pesticides and can be used in bio-purification systems.     

聚丙烯酸水凝胶对氯化-1-丁基-3-甲基咪唑离子液体的吸附热力学和动力学研究

通过水溶液聚合法制备了聚丙烯酸水凝胶（polyacrylic acid,PAA）,研究了溶液酸碱度和温度对聚丙烯酸水凝胶吸附氯化1-丁基3-甲基咪唑离子液体的影响。结果表明,水凝胶对氯化1-丁基3-甲基咪唑离子液体的吸附量随溶液pH值增大而逐渐增大,pH=2～4时增幅明显,而pH大于4时变化趋于缓慢;随温度的升高而逐渐降低。该等温吸附行为基本符合Langmuir吸附等温式,由二级吸附动力学模型获得的吸附过程活化能（Ea=52.470 kJ/mol）可以看出,PAA对氯化1-丁基3-甲基咪唑的吸附属于化学吸附范畴。     

Kinetic, equilibrium isotherm and thermodynamic studies of Cr(VI) adsorption onto low-cost adsorbent developed from peanut shell activated with phosphoric acid

A particular agricultural waste, peanut shell, has been used as precursor for activated carbon production by chemical activation with H₃PO₄. Unoxidized activated carbon was prepared in nitrogen atmosphere which was then heated in air at a desired temperature to get oxidized activated carbon. The prepared carbons were characterized for surface area, surface morphology, and pore volume and utilized for the removal of Cr(VI) from aqueous solution. Batch mode experiments were conducted to study the effects of pH, contact time, particle size, adsorbent dose, initial concentration of adsorbate, and temperature on the adsorption of Cr(VI). Cr(VI) adsorption was significantly dependent on solution pH, and the optimum adsorption was observed at pH 2. Pseudo-first-order, pseudo-second-order, and intraparticle diffusion models were used to analyze the kinetic data obtained at different initial Cr(VI) concentrations. The adsorption kinetic data were described very well by the pseudo-second-order model. Equilibrium isotherm data were analyzed by the Langmuir, Freundlich, and Temkin models. The results showed that the Langmuir adsorption isotherm model fitted the data better in the temperature range studied. The adsorption capacity which was found to increase with temperature showed the endothermic nature of Cr(VI) adsorption. The thermodynamic parameters, such as Gibb’s Free energy change (ΔG°), standard enthalpy change (ΔH°), and standard entropy change (ΔS°) were evaluated.     

Determination of the Adsorption Isotherm of Vapor-Phase Mercury Chloride on Powdered Activated Carbon Using Thermogravimetric Analysis

Abstract

This study investigated the use of thermogravimetric analysis (TGA) to determine the adsorptive capacity and adsorption isotherm of vapor-phase mercury chloride on powdered activated carbon (PAC). The technique is commonly applied to remove mercury-containing air pollutants from gas streams emitted from municipal solid waste incinerators. An alternative form of powdered activated carbon derived from a pyrolyzed tire char was prepared for use herein. The capacity of waste tire-derived PAC to adsorb vapor-phase HgCl₂ was successfully measured using a self-designed TGA adsorption system. Experimental results showed that the maximum adsorptive capacities of HgCl₂ were 1.75, 0.688, and 0.230 mg of HgCl₂ per gram of powdered activated carbon derived from carbon black at 30, 70, and 150 °C for 500 µg/m³ of HgCl₂, respectively. Four adsorption isotherms obtained using the Langmuir, Freundlich, Redlich-Peterson, and Brunauer–Emmett–Teller (BET) models were used to simulate the adsorption of HgCl₂. The comparison of experimental data associated with the four adsorption isotherms indicated that BET fit the experimental results better than did the other isotherms at 30 °C, whereas the Freundlich isotherm fit the experimental results better at 70 and 150 °C. Furthermore, the calculations of the parameters associated with Langmuir and Freundlich isotherms revealed that the adsorption of HgCl₂ by PAC-derived carbon black favored adsorption at various HgCl₂ concentrations and temperatures.     

Sorption of hydrophobic organic pollutants in saturated soil systems

Sorption equilibria and rates were characterized for a matrix of four aquifer sands and two slightly to moderately hydrophobic organic solutes (nitrobenzene and lindane), and the effects of sorption on the behavior of these solutes in saturated systems of the soils were determined. Experimental data were used to test and evaluate a variety of mathematical models for predicting contaminant fate and transport in groundwater systems.Observed equilibrium relationships between soil and solution phase solute concentrations were found to be described best by the nonlinear Freundlich isotherm model. It was further determined that the sorption process in the systems tested is rate controlled, requiring several days to approach equilibrium in completely mixed batch reactors. Subsequent modeling of solute transport in continuous flow soil column reactors was found to be most successful when rate-controlled models were used, the best results were obtained with a dual-resistance model incorporating the coupled mass transport steps of boundary-layer and intraparticle diffusion.     

废弃物基活性炭吸附挥发性有机污染物特性的研究

研究了废弃物基活性炭对挥发性有机污染物中的典型组分--甲苯的吸附特性.结果表明,废弃物基活性炭吸附甲苯等温线的类型系优惠型吸附等温线,表明具有良好的吸附能力;同时其吸附甲苯时穿透时间的对数与甲苯入口浓度的对数之间具有良好的线性相关性,即可由吸附高浓度甲苯时的穿透时间估算低浓度时的穿透时间;动态吸附时废弃物基活性炭的中孔对甲苯亦具有一定的吸附性能.     

Effects of reduced contaminant loading on downgradient water quality in an idealized two-layer granular porous media

The following explores the issue of how reductions in contaminant loading to plumes will effect downgradient water quality. An idealized scenario of two adjacent layers of uniform geologic media, one transmissive and the other low permeability, is considered. A high concentration source, similar to a thin DNAPL pool, is introduced in the transmissive layer immediately above the low permeability layer. While the source is active, dissolved constituents are driven along the contact by advection and into the low permeability layer by transverse diffusion. Removing the source reverses the concentration gradient between the layers, driving back diffusion of contaminants from the low permeability layer. Laboratory studies involving four contaminants demonstrate that 15 to 44% of the introduced contaminant moves into the low permeability zone (along a distance of 87 cm in a sand tank) over a period of 25 days. The greatest movement of contaminants into the low permeability zone is seen with the contaminants with the greatest sorption coefficients. A unique two-dimensional analytical solution is developed for the two-layer scenario. Processes addressed include advection; transverse dispersion; adsorption and degradation in the transmissive zones; and diffusion, adsorption, and degradation in the low permeability layer. Laboratory data agree favorably with the analytical solutions. Collectively, the laboratory results and analytical solutions provide a basis for testing other modeling approaches that can be applied to more complex problems. A set of field-scale scenarios are considered using the analytical solutions. Results indicate that improvement in water quality associated with source removal diminish with distance downgradient of the source. Furthermore, contaminant degradation and contaminant adsorption in the stagnant zone are shown to be critical factors governing the timing and magnitude of downgradient improvements in water quality. For five of six scenarios considered, observed improvements in water quality 100 m downgradient of the source fall in the range of 1 to 2 orders of magnitude 15 years after complete source removal. The sixth scenario, involving a contaminant half-life of three years and no adsorption, shows greater than three order of magnitude improvements in downgradient water quality within one year of source removal.