Groundwater transport modeling with nonlinear sorption and intraparticle diffusion

Despite recent advances in the mechanistic understanding of sorption in groundwater systems, most contaminant transport models provide limited support for nonideal sorption processes such as nonlinear isotherms and/or diffusion-limited sorption. However, recent developments in the conceptualization of “dual mode” sorption for hydrophobic organic contaminants have provided more realistic and mechanistically sound alternatives to the commonly used Langmuir and Freundlich models. To support the inclusion of both nonlinear and diffusion-limited sorption processes in groundwater transport models, this paper presents two numerical algorithms based on the split operator approach. For the nonlinear equilibrium scenario, the commonly used two-step split operator algorithm has been modified to provide a more robust treatment of complex multi-parameter isotherms such as the Polanyi-partitioning model. For diffusion-limited sorption, a flexible three step split-operator procedure is presented to simulate intraparticle diffusion in multiple spherical particles with different sizes and nonlinear isotherms. Numerical experiments confirmed the accuracy of both algorithms for several candidate isotherms. However, the primary advantages of the algorithms are: (1) flexibility to accommodate any isotherm equation including “dual mode” and similar expressions, and (2) ease of adapting existing grid-based transport models of any dimensionality to include nonlinear sorption and/or intraparticle diffusion. Comparisons are developed for one-dimensional transport scenarios with different isotherms and particle configurations. Illustrative results highlight (1) the potential influence of isotherm model selection on solute transport predictions, and (2) the combined effects of intraparticle diffusion and nonlinear sorption on the plume transport and flushing for both single-particle and multi-particle scenarios.     

Competitive sorption of persistent organic pollutants onto microplastics in the marine environment

Plastics are known to sorb persistent organic pollutants from seawater. However, studies to quantify sorption rates have only considered the affinity of chemicals in isolation, unlike the conditions in the environment where contaminants are present as complex mixtures. Here we examine whether phenanthrene and 4,4′-DDT, in a mixture, compete for sorption sites onto PVC with no added additives (unplasticised PVC or uPVC) and Ultra-High Molecular Weight polyethylene. Interactions were investigated by exposing particles of uPVC and UHMW PE to mixtures of 3H and 14C radiolabelled Phe and DDT. Changes in sorption capacity were modelled by applying a Freundlich binding sorption isotherms. An Extended Langmuir Model and an Interaction Factor Model were also applied to predict equilibrium concentrations of pollutants onto plastic. This study showed that in a bi-solute system, DDT exhibited no significantly different sorption behaviour than in single solute systems. However, DDT did appear to interfere with the sorption of Phe onto plastic, indicating an antagonistic effect.     

Modeling the effects of nonlinear equilibrium sorption on the transport of solute plumes in saturated heterogeneous porous media

Transport of sorbing solutes in 2D steady and heterogeneous flow fields is modeled using a particle tracking random walk technique. The solute is injected as an instantaneous pulse over a finite area. Cases of linear and Freundlich sorption isotherms are considered. Local pore velocity and mechanical dispersion are used to describe the solute transport mechanisms at the local scale. This paper addresses the impact of the degree of heterogeneity and correlation lengths of the log-hydraulic conductivity field as well as negative correlation between the log-hydraulic conductivity field and the log-sorption affinity field on the behavior of the plume of a sorbing chemical. Behavior of the plume is quantified in terms of longitudinal spatial moments: center-of-mass displacement, variance, 95% range, and skewness. The range appears to be a better measure of the spread in the plumes with Freundlich sorption because of plume asymmetry. It has been found that the range varied linearly with the travelled distance, regardless of the sorption isotherm. This linear relationship is important for extrapolation of results to predict behavior beyond simulated times and distances. It was observed that the flow domain heterogeneity slightly enhanced the spreading of nonlinearly sorbing solutes in comparison to that which occurred for the homogeneous flow domain, whereas the spreading enhancement in the case of linear sorption was much more pronounced. In the case of Freundlich sorption, this enhancement led to further deceleration of the solute plume movement as a result of increased retardation coefficients produced by smaller concentrations. It was also observed that, except for plumes with linear sorption, correlation between the hydraulic conductivity and the sorption affinity fields had minimal effect on the spatial moments of solute plumes with nonlinear sorption.     

Sorption behavior of nonylphenol on marine sediments: effect of temperature, medium, sediment organic carbon and surfactant

The sorption behavior of nonylphenol (NP, a toxic endocrine disruptor) on marine sediments was studied in detail through a series of kinetic and thermodynamic sorption experiments. The results showed that the sorption reaction of NP on marine sediments reached equilibrium in 1.5 h and that it accorded well with the non-linear Ho-McKay pseudo-second-order model. The sorption isotherms of NP on H₂O-treated sediments could be well described by the Linear isotherm model, while the sorption isotherm on H₂O₂-treated sediments could be well fitted with the Freundlich isotherm model. A positive correlation was found between the distribution coefficient (K_d) and the sediment organic carbon contents. The medium salinity showed a positive relation with the K_d and a negative relation with the dissolved organic carbon (DOC). Hexadecyl trimethyl ammonium bromide (CTAB) enhanced the sorption amount of NP the most, while sodium dodecylbenzenesulfonate (SDBS) enhanced it the least. The sorption reaction of NP on marine sediments was a spontaneous, physical, exothermic and entropy-decreasing process.     

太湖地区丘陵旱地土壤磷的吸持解吸特征

旱地土壤中流失的磷是地表水体中磷的重要来源,本文通过模拟实验对比太湖地区丘陵旱地土壤和水稻土对磷的吸持解吸特征,结果表明虽然旱地土壤对磷的固定能力略高于水稻土,但由于旱地土壤的有效磷水平普遍高于水稻土,因而前者磷的吸持饱和度（DPS）要大大高于后者,这就决定了旱地土壤中的磷被淋溶或以溶解态随径流流失的风险和数量也同于水稻土,磷吸持饱和度是土壤磷素水平和土壤固磷能力的综合指标,更能反映土壤固相中的磷进入液相的难易程序,可以作为评价水－土界面磷迁移能力 重要指标。     

Computerprogramm „ADSORB”︁ — ein optimiertes mathematisches Verfahren zur Charakterisierung organischer Vielstoffgemische in Wässern mittels Adsorptionsanalyse

The computing program ?ADSORB”? allows a very fast mathematical evaluation of adsorption isotherms for the preparation of adsorption analyses. With the program ?ADSORB”? it is possible to calculate any number of pseudocomponents of organic multicomponent mixtures of different adsorbability. Only few minutes are required for the mathematical evaluation of an sorption analysis by means of ?ADSORB”?. adsorption analysis, adsorption isotherm, mathematical modelling     

Ionic Liquid Modified Resin for the Adsorptive Removal of Dibutyl Phthalate: Equilibrium,Kinetic, and Thermodynamic Studies

This study evaluated the adsorptive properties of dibutyl phthalate (DBP) on room temperature ionic liquid (RTIL) modified XAD‐4 resin. The modified RTIL‐XAD 4 sorbent was characterized by FTIR. Effect of varying experimental conditions such as pH, contact time, temperature, shaking speed, concentrations, and interfering species were investigated by batch adsorption experiments. Adsorption was found to be most favorable at pH 6 within 30 min. Experimental data were evaluated in terms of kinetic, equilibrium, and thermodynamic modeling. Kinetics of the sorption was found to follow pseudo second order rate equation whereas Freundlich and D–R isotherms were the most suitable models to explain sorption phenomenon. Thermodynamically sorption was endothermic, irreversible, and spontaneous in nature.     

Sorption site capacities for Cs on the sedimentary rock in Horonobe area

The sorption behavior of radionuclides depends on the content of minerals in geological media. The sorption of radionuclides on minerals has been interpreted as the uptake on the sorption sites on mineral surfaces. However, conventional investigations such as X-ray diffraction analysis cannot avoid large errors in quantification of minerals. Furthermore, the discrepancies of sorption behavior have been often found even on the same kind of minerals. Therefore, the sorption site capacity cannot be effectively estimated by the quantification of minerals. In this study, the sorption site on sedimentary rock sampled in Horonobe area, where the Horonobe Underground Research Center, JAEA, is located, was estimated from the Cs sorption isotherms obtained by sorption experiments. To deduce the fitting parameters, illite content estimated from the amount of extracted K by alkylammonium treatment and smectite content estimated from the cation exchange capacity measurement were introduced to the fitting procedure. The result shows that the sorption site capacities of smectite and illite in the sedimentary rock in Horonobe area are 1.3–1.7 × 10⁻⁴ and 1.4–4.0 × 10⁻⁵ eq/g, respectively.     

Characterization of phosphorus interaction with sediments affected by acid mine drainage-relation with the sediment composition

Phosphorus sorption capacity was investigated in surface sediments derived from an abandoned zinclead mine area located in northeastern Algeria. The forms and the distribution of phosphorus in the raw sediment were identified using the sequential chemical extractions method. Batch experiments were done to study the adsorption kinetics and isotherms. The pH effect was evaluated by macroscopic and infrared analyses. In raw sediment, speciation results show that phosphorus is dominantly bound to oxyhydroxides. Sorption experiments demonstrate that phosphorus uptake is principally related to sediment composition. The nature of the dominant iron oxyhydroxide has a substantial role in the adsorption capacity and the mechanism interaction. The adsorption kinetics can be described by the second order and Elovich models. The isotherms data are successfully modeled by the Temkin equation.The maximum phosphorus removal is reached under acidic pH. Spectroscopic analyses reveal that the predominance of jarosite implies electrostatic interaction with sediment particles. However, in the case of schwertmannite predominance, phosphate ions are adsorbed by the ligand exchange mechanism.     

Characterization of phosphorus sorption on the sediments of Yangtze River Estuary and its adjacent areas

This paper studied the kinetics, isotherm and thermodynamics of phosphorus sorption onto the sediments of the Yangtze River estuary and its adjacent waters, as well as the sediments' compositions and physicochemical properties. The process could be described well by a two-compartment first order equation. The sorbed phosphorus mainly consisted of Ex-P and Fe-P, with Ex-P being the dominant. The equilibrium isotherms could be fitted well with a modified Langmuir equation. The calculations of the thermodynamic parameters indicated that the process was spontaneous and exothermic. The CEC and the fractions of clay, calcite and organic matter were correlated with the sorption parameters, while the surface proton charge of the sediments was significantly negatively correlated with them. Considering the kinetics and phosphorus forms changes during the process, the sorption in our study could be considered that the physical process plays an important role.     

Batch and Column Experiments to Support Heavy Metals (Cu,Zn, and Mn) Transport Modeling in Alluvial Sediments Between the Mogan Lake and the Eymir Lake,Gölbaşı, Ankara

This article describes laboratory batch sorption and column transport experiments that were conducted using heterogeneous alluvial sediments with a wide physical characteristic from wells, located between Lake Mogan and Lake Eymir, Gölbaşı, Ankara. The batch sorption experiment was conducted in two separate systems, that is, single and multicomponents. Single batch experiment was performed to determine equilibrium condition between the heavy metal ions and the soil adsorption sites. The sorption isotherms data from multibatch experiments were used to calculate the sorption parameters. Single batch experiment indicated that equilibrium was attained within 9 days from the start of the sorption test. As a result of multicomponents batch experiments, for Zn and Mn, the sorption process was well described by the Freundlich or Langmuir isotherm model, whereas sorption of Cu was better described by the linear isotherm model. The K_d of Cu were found to be highest in soil 1 (32550.350 L kg⁻¹) and lowest in soil 5 (18170.76 L kg⁻¹). The maximum and minimum sorption capacity values for Zn were found to be in soil 1 (10985.148 mg kg⁻¹) and in soil 2 (8597.14 mg kg⁻¹) units, respectively. [Correction added after online publication 15 July, 2010: In the preceding sentence, the words “minimum” and “maximum” were initially switched.] Similarly, soil 1 (7587.391 mg kg⁻¹) and soil 5 (4908.695 mg kg⁻¹) units provided the maximum and minimum values for Mn. In the column experiments, flow and tracer transport was studied under saturated conditions using conservative tracer to determine the transport parameters. Transport parameter values were obtained by curve-fitting using the nonlinear least-squares optimization code CXTFIT. Results of the column experiments indicated that the dispersivity values obtained for soil samples were in the range of 0.024 to 1.13 cm.     

Modeling plume behavior for nonlinearly sorbing solutes in saturated homogeneous porous media

Transport of a sorbing solute in a two-dimensional steady and uniform flow field is modeled using a particle tracking random walk method. The solute is initially introduced from an instantaneous point source. Cases of linear and nonlinear sorption isotherms are considered. Local pore velocity and mechanical dispersion are used to describe the solute transport mechanisms at the local scale. The numerical simulation of solute particle transport yields the large scale behavior of the solute plume. Behavior of the plume is quantified in terms of the center-of-mass displacement distance, relative velocity of the center-of-mass, mass breakthrough curves, spread variance, and longitudinal skewness. The nonlinear sorption isotherm affects the plume behavior in the following way relative to the linear isotherm: (1) the plume velocity decreases exponentially with time; (2) the longitudinal variance increases nonlinearly with time; (3) the solute front is steepened and tailing is enhanced     

Sorption behavior of phenanthrene in Yangtze estuarine sediments: sequential separation

In the present study, phenanthrene was chosen as the probe compound for determining the sorption of PAHs in sediments from Yangtze estuary and nearby coastal area, China. Sorption isotherms were fitted well by the Freundlich and dual models, respectively. Selected sediments were further sequentially separated to remove the carbonate and organic carbon (OC). Calculated OC sorption capacity values based on both H₂O₂ oxidization and 375 °C combustion methods were similar and comparable to the K_oc values estimated by the empirical linear sorption equations. Both sorption models and sorption data using sequentially separated samples achieve the similar conclusions: (1) the partition behavior dominated by OC in sediments with f_oc > 0.01; (2) for sediments with 0.001 < f_oc < 0.01, OC dominated sorption at relatively high aqueous concentration; whereas mineral phase adsorption dominated sorption at lower concentration especially when C_w/S_w was in the range of 0.0001-0.001 in natural aqueous system.     

Incorporating nonlinear isotherms into robust multilayer sorptive barrier design

Sorptive barrier technologies have emerged as useful tools for addressing a wide range of remediation problems. When simulating barrier performance, numerous isotherm expressions are available for relating aqueous and sorbed concentrations. However, isotherm selection is non-trivial because alternative expressions may yield comparable fits to experimental data. Additionally, concentration data collected for parameter fitting is often outside the range of concentrations relevant to simulating barrier performance. This incompatibility necessitates extrapolation of isotherm behavior during simulation–optimization. Consequently, equally plausible isotherms may predict significantly different barrier performance.Numerical experiments involving organic contaminants were performed to examine the influence of isotherm selection and extrapolation on optimal barrier design. Ten isotherms were calibrated to existing experimental data and evaluated using information-theoretic selection criteria. When incorporated into simulation–optimization, extrapolation effects were clearly evident and optimal designs varied according to the chosen isotherm. To ensure robust barrier design in the presence of such variability, a simple methodology is proposed that utilizes a piecewise-minimum isotherm concept. By favoring plausible isotherms that predict the least amount of sorption, the methodology encourages conservative barrier design while respecting available data.     

Contaminant transport in fractured chalk: laboratory and field experiments

Laboratory experiments were performed on chalk samples from Denmark and Israel to determine diffusion and distribution coefficients. Batch tests were used to define sorption isotherms for naphthalene and o-xylene. Linear sorption isotherms were observed and described with Henry-isotherms. Because of the high purity and low contents of clay minerals and organic carbon, Danish and white Israeli chalk generally have low retardation capacities. Contrarily, gray Israeli chalk, with organic carbon fractions as high as 1.092%, remarkably retards organic contaminants. The K(OC) concept is not applicable to predicting distribution coefficients based on the organic carbon content in the chalk samples. Effective diffusivities of o-xylene, naphthalene, and several artificial tracers were determined using through-diffusion experiments. Based on measured diffusion coefficients and available literature values, a chalk specific exponent of 2.36 for Archie's law was derived, allowing a satisfactory estimate of relative diffusivities in chalk. A field-scale tracer test with uranine and lithium was performed in the Negev desert (Israel) to examine the transferability of diffusivities determined on small rock samples in the laboratory. Due to low recovery rates of the tracer, a modified single fissure dispersion model was used for inverse modeling of the breakthrough curves. Resulting diffusivities deviate insignificantly from the laboratory values, which are considered to be representative for the investigated part of the aquifer and applicable in transport models.     

Sorption of ortho‐Phenylphenol to Soils

Conflicting sorption coefficients for ortho‐phenylphenol (OPP) have been reported in the literatures, which resulted in the conflicting assessments on OPP mobility in soil. To ascertain the sorption coefficient of OPP, batch experiments were performed based on OECD guideline 106, using three types of soils. Headspace solid‐phase microextraction (HS‐SPME) and GC‐MS were applied to the determination of OPP concentration in the liquid phase. The sorption isotherms obtained for all three soils under equilibrium conditions were described well, assuming linear sorption. The organic carbon normalized distribution coefficients (K_oc) ranged from 894 to 1703 L kg^?1, which suggested that OPP is moderately mobile in soil. The results also showed that the K_oc value of OPP can be predicted precisely from K_ow, whereas it was underestimated by one order of magnitude when water solubility is used.     

Development of Polymeric and Polymer‐Based Hybrid Adsorbents for Chromium Removal from Aqueous Solution

Ferric oxide‐loaded hybrid sorbents are environmentally benign and exhibit sorption behaviors for chromium removal from waters. In the current study, glycidyl methacrylate‐based polymer (GMD) and nanosized ferric oxide loaded glycidyl methacrylate‐based polymer (GMDFe) were prepared and assayed to examine the effect of ferric oxide loading on chromium sorption from aqueous solution for the first time from the equilibrium and kinetic points of view. The experimental equilibrium data, suitably fitted by the Langmuir and Freundlich isotherms, have shown that ferric oxide loaded hybrid sorbent exhibits higher adsorption capacity than glycidyl methacrylate‐based polymer (GMD). The Langmuir isotherm model was found to be the most suitable one for the Cr(VI) adsorption. The maximum adsorption capacities of GMD and GMDFe sorbents were determined at pH 4 as 109.54 and 157.52 mg/g, respectively. A series of column experiments was carried out to determine the breakthrough curves. The column was regenerated by eluting Cr(VI) using NaOH (10% w/v) solution after adsorption studies.     

Specific surface area as a maturity index of lunar fines

Mature surface fines have an equilibrium specific surface area of about 0.6 m²/g, the equivalent mean particle size being about 3 μm. The adsorption behavior of inert gases (reversible isotherms) indicates that the particles are also non-porous in the size range of pores 10–300Å. Apparently in mature soils there is a balance in the forces which cause fining, attrition, pore filling and growth of lunar dust grains. Immature, lightly irradiated soils usually have coarser grains which reduce in size as aging proceeds. The specific surface area, determined by nitrogen or krypton sorption at 77°K, is a valuable index of soil maturity.     

Effects of geosorbent and solution properties on sorption and desorption of PAHs

Characteristics of phenanthrene and pyrene's sorption and desorption on two local soils in solutions of simulated groundwater,simulated lung fluid,and simulated saliva were studied with batch equilibrium experiments to understand the fate of PAHs in the karst region of southwestern China and to assess the environmental exposure and the health risk of PAHs.The results showed that the sorption and desorption isotherms of phenanthrene and pyrene on two target soils in the three solution systems could be adequately described by the Freundlich model,while the fitted isotherm parameters for the simulated groundwater solution distinguished notably from those for the simulated body fluid solutions.For the sorption experiments,in the simulated groundwater,the n values were 0.722 and 0.672 for phenanthrene and were 0.724 and0.663 for pyrene,respectively,on the yellow soil and the limestone soil;The log KF values were 3.118 and 3.323 for phenanthrene and were 3.648 and 3.846 for pyrene,respectively,on the yellow soil and the limestone soil.In the simulated body fluids,the n values for phenanthrene and pyrene ranged from 0.622 to 0.836 and from 0.590 to0.865,respectively,and the log KF values of phenanthrene and pyrene ranged from 2.845 to 3.327 and from 3.344 to3.779,respectively.For the desorption experiments,in the simulated groundwater,the n values were 0.662 and 0.744 for phenanthrene and were 0.702 and 0.647 for pyrene,respectively,on the yellow soil and the limestone soil.The log K_F values were 3.666 and 3.686 for phenanthrene and were 4.128 and 4.225 for pyrene,respectively,on the yellow soil and the limestone soil.In the simulated body fluids,the n values for phenanthrene and pyrene ranged from 0.612 to 0.668 and from 0.631 to 0.819,respectively,and the log KF values of phenanthrene and pyrene ranged from 3.134 to 3.407 and from 3.533 to 3.839,respectively.The limestone soil had relatively higher log KF values but lower K_(OC) values compared to those of the yellow soil,indicated that the nature of sorbent soils played the dominant role in sorption and desorption behaviors of PAHs.The experimental results showed a remarkable differences in sorption and desorption behaviors of PAHs in simulated body fluids and groundwater.The nonlinearities of measured isotherms and the measured sorption capacities of soils in simulated body fluids were significantly lower than corresponding those in the simulated groundwater,and HI values for simulated body fluids systems were significantly smaller than corresponding those for the simulated groundwater systems.The results underscore cautions in assessing environmental exposure and health risks of PAHs based on their sorption-desorption data in simulated groundwater as this is traditionally done.