An integrated sorption-diffusion model for the calculation of consistent distribution and diffusion coefficients in compacted bentonite

A thermodynamic sorption model and a diffusion model based on electric double layer (EDL) theory are integrated to yield a surface chemical model that treats porewater chemistry, surface reactions, and the influence of charged pore walls on diffusing ions in a consistent fashion. The relative contribution of Stern and diffuse layer to the compensation of the permanent surface charge represents a key parameter; it is optimized for the diffusion of Cs in Kunipia-F bentonite, at a dry density of 400 kg/m3. The model is then directly used to predict apparent diffusivities (Da) of Cs, Sr, Cl-, I- and TcO4- and corresponding distribution coefficients (Kd) of Cs and Sr in different bentonites as a function of dry density, without any further adjustment of surface chemical and EDL parameters. Effective diffusivities (De) for Cs, HTO, and TcO4- are also calculated. All calculated values (Da, De, Kd) are fully consistent with each other. A comparison with published, measured data shows that the present model allows a good prediction and consistent explanation of (i) apparent and effective diffusivities for cations, anions, and neutral species in compacted bentonite, and of (ii) Kd values in batch and compacted systems.     

Sensitivity analysis of radionuclide migration in compacted bentonite: a mechanistic model approach

Mechanistic model calculations for the migration of Cs, Ra, Am and Pb in compacted bentonite have been carried out to evaluate sensitivities with respect to different parameter variations. A surface chemical speciation/electric double layer model is used to calculate: (i) porewater composition and radionuclide speciation in solution and at the bentonite surface, yielding the distribution of mobile and sorbed species and (ii) interaction of diffusing species with negatively charged pore walls to obtain diffusion parameters. The basic scenario considers the interaction of compacted bentonite with a fresh-type groundwater; variations include the presence of bentonite impurities and saline groundwater. It is shown that these scenarios result in significant variations of porewater composition that affect migration via three mechanisms that can partly compensate each other: (1) effects on sorption through radionuclide complexation in solution, and competition of major cations for surface sites; (2) changes in radionuclide solution speciation leading to different diffusing species under different conditions; (3) effects on diffusion through changes in the electric double layer properties of the clay pores as a function of ionic strength.     

Inverse modeling of multicomponent reactive transport through single and dual porosity media

Compacted bentonite is foreseen as buffer material for high-level radioactive waste in deep geological repositories because it provides hydraulic isolation, chemical stability, and radionuclide sorption. A wide range of laboratory tests were performed within the framework of FEBEX (Full-scale Engineered Barrier EXperiment) project to characterize buffer properties and develop numerical models for FEBEX bentonite. Here we present inverse single and dual-continuum multicomponent reactive transport models of a long-term permeation test performed on a 2.5 cm long sample of FEBEX bentonite. Initial saline bentonite porewater was flushed with 5.5 pore volumes of fresh granitic water. Water flux and chemical composition of effluent waters were monitored during almost 4 years. The model accounts for solute advection and diffusion and geochemical reactions such as aqueous complexation, acid-base, cation exchange, protonation/deprotonation by surface complexation and dissolution/precipitation of calcite, chalcedony and gypsum. All of these processes are assumed at local equilibrium. Similar to previous studies of bentonite porewater chemistry on batch systems which attest the relevance of protonation/deprotonation on buffering pH, our results confirm that protonation/deprotonation is a key process in maintaining a stable pH under dynamic transport conditions. Breakthrough curves of reactive species are more sensitive to initial porewater concentration than to effective diffusion coefficient. Optimum estimates of initial porewater chemistry of saturated compacted FEBEX bentonite are obtained by solving the inverse problem of multicomponent reactive transport. While the single-continuum model reproduces the trends of measured data for most chemical species, it fails to match properly the long tails of most breakthrough curves. Such limitation is overcome by resorting to a dual-continuum reactive transport model.     

The influences of pH and ionic strength on the sorption of tylosin on goethite

As one of the widely used antibiotics in the world, the environmental risks of tylosin (TYL) received more and more attention. In order to assess its environmental fate and ecological effects accurately, it is necessary to understand the sorption properties of TYL on the soils/sediments. The sorption of TYL on goethite at different pH and ionic strength conditions were measured through a series of batch experiments and the sorption data of TYL were fitted by Freundlich and dual-mode sorption models. It was obvious that sorption was strongly dependent on pH and ionic strength. Sorption capacity of TYL increased as the pH increased and ionic strength decreased. The pH and ionic strength-dependent trends might be related with complexation between cationic/neutral TYL species and goethite. The sorption affinity of TYL on goethite decreased as ionic strength increased, which only occurred at higher TYL concentrations, suggested that inner complex might have dominated process at low concentrations and outer complex might occur at higher concentrations of TYL. Spectroscopic evidence indicated that tricarbonylamide and hydroxyl functional groups of TYL might be accounted for the sorption on mineral surfaces. The experimental data of TYL sorption could be fitted by surface complexation model (FITEQL), indicating that ≡FeOH with TYL interaction could be reasonably represented as a complex formation of a monoacid with discrete sites on goethite. The sorption mechanism of TYL might be related with surface complexation, electrostatic repulsion, and H-bounding on goethite. It should be noticed that the heterogeneous of sorption affinity of TYL on goethite at various environment to assess its environment risk.     

Long-term geochemical evolution of the near field repository: insights from reactive transport modelling and experimental evidences

The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept.In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution–precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca.     

Sorption of naphthoic acids and quinoline compounds to estuarine sediment

The sorption of 16 ionizable organic compounds (IOCs) to an estuarine sediment was measured in synthetic estuarine water as a function of IOC concentration (1-100 microM) at fixed ionic strength (0.4 M), pH (7.6), and sediment concentration (0.018 g sediment kg(-1) suspension). Of the 16 IOCs, 11 were naphthoic acids and five were quinoline compounds. The linear sorption distribution coefficient (Kd) was used to correlate sorption to IOC physicochemical and molecular characteristics. With respect to naphthoic acid, sorption increased with the addition of ortho-substituent groups and with increasing chain length of the 1-acid group, and the greatest increase occurred with ortho-hydroxyl, carbonyl, and carboxyl groups. With respect to quinoline, sorption decreased with substituent group addition (except for nitro group) and with additional heterocyclic N atoms. For the naphthoic acids, log Kd exhibited a positive correlation with water solubility (log Sw) indicative of sorption primarily to mineral surfaces under the solution chemistry. For the quinoline compounds, log Kd exhibited a negative correlation with log Sw and a positive correlation with n-octanol/water partition coefficient (log K(OW)) indicative of sorption primarily to organic matter. For both compounds, poor or no correlations were established between log Kd and acid dissociation constant (pKa1), and between log Kd and a variety of molecular connectivity indexes. The results from this study demonstrate that the sorption of IOCs differ depending on their backbone structure and may differ between parent compound and ionizable degradation product.     

Investigation of solution chemistry effects on sorption behavior of Cu(II) on ZSM-5 zeolite

The sorption of Cu(II) from an aqueous solution using ZSM-5 zeolite was investigated by batch technique under ambient conditions. Sorption was investigated as a function of pH, ionic strength, foreign ions, humic substances, and temperature. The results indicate that the sorption of Cu(II) on ZSM-5 zeolite is strongly dependent on pH. Sorption is dependent on ionic strength at low pH, but independent of ionic strength at high pH values. The presence of humic/fluvic acid (HA/FA) enhances the sorption of Cu(II) on ZSM-5 zeolite at low pH values, and reduces Cu(II) sorption at high pH values. Sorption isotherms were well simulated by the Langmuir model. Thermodynamic parameters (i.e., deltaH0, deltaS0 and deltaG0) for the sorption of Cu(II) were determined from temperature-dependent sorption isotherms at 293.15, 313.15, and 333.15 K, respectively. Results indicate that the sorption process of Cu(II) on ZSM-5 zeolite is spontaneous and endothermic.     

Sorption of ametryn and imazethapyr in twenty-five soils from Pakistan and Australia.

Sorption of ametryn and imazethapyr in 25 soils from Pakistan and Australia was investigated using the batch method. The soils varied widely in their intrinsic capacities to sorb these herbicides as shown by the sorption coefficients, Kd, which ranged from 0.59 to 47.6 for ametryn and 0.02 to 6.94 for imazethapyr. Generally the alkaline soils of Pakistan had much lower Kd values of both herbicides than the soils of Australia. Both soil pH and soil organic carbon (SOC) were correlated significantly with the sorption of ametryn, whereas only soil pH was strongly correlated with imazethapyr sorption. No correlation was found between Kd values of the herbicides and the clay contents of the soils. Multiple regression analysis showed that Kd values were better correlated (r2=0.94 and 0.89 for ametryn and imazethapyr, respectively) if SOC and pH were simultaneously taken into account. The study indicated that sorption of these herbicides in the alkaline soils of Pakistan was low and consequently there is considerable risk of groundwater contamination.     

Retention of Cd, Zn and Co on hydroxyapatite filters

This study qualifies and quantifies the immobilization of Cd, Zn and Co, (used as models of bivalent metal ions due to their relevant toxicity) in filters of synthetic hydroxyapatite (HAP) [Ca5(PO4)3OH]. They were flushed with solutions containing Cd (1 x 10(-5)M), Zn and Co (1 x 10(-4)M) at constant pH (8.6) and ionic strength (0.01 M). The concentration of these metal ions in the outlet was measured by ICP-OEM spectroscopy. The software PHREEQC (version 2.4.2) was used to model sorption process and the potential effect of salinity (KCl), pH, alkalinity (NaHCO3) and hardness (CaCl2) over the efficiency of the treatment. Results showed an excellent retention capacity of HAP for Cd, Zn and Co. Sorption data were successfully described considering a mix model of surface complexation onto phosphate surface groups, ionic exchange in surface calcium sites and the precipitation of ZnO. Co exchange and surface complexation constants (Kex and Kc) were taken from previous experiments, while KexCd=0.32 and KcCd=0.63 were estimated from our modeling results. Predictive values of metal ion sorption show that: (a) an increase in hardness does not play a significant role in the retention capacity of these metals on HAP; (b) an increase in alkalinity promotes the precipitation of MeCO3 which could alter the hydrodynamic of the column; (c) a decrease in pH and an increase in salinity inhibit ZnO precipitation enhancing Zn and Cd adsorption and decreasing Co retention on HAP.     

Retardation capacity of organophilic bentonite for anionic fission products

Sorption and diffusivity of iodide and pertechnetate (I- and TcO4-) on MX-80 bentonite with different hexadecylpyridinium (HDPy+) loadings were studied using equilibrium solutions of different ionic strengths. In HDPy(+)-modified bentonite, iodide and pertechnetate ions exhibited increasing sorption (characterized by the distribution ratio, Rd), while Cs+ and Sr2+ showed decreasing sorption with increasing organophilicity. In case of medium-loading levels, the simultaneous sorption of anions (I- and TcO4-) and cations (Cs+ and Sr2+) was observed. Sorption of ions was influenced by the composition of the electrolytes employed. It decreased gradually with increasing ionic strength of the electrolyte solutions. The experiments revealed the general tendency that the diffusivity (Da [cm2.s-1]) for iodide and pertechnetate decreases with increasing organophilicity and increases with increasing ionic strength of the equilibrium solutions, confirming the results of the sorption experiments. Additionally, some mineralogical and chemical investigations, like IR spectral analysis of the organo-bentonite samples and exchange behavior of HDPy+, were performed. On the basis of these analyses, it was concluded that the alkylammonium ions are sorbed as (1) HDPy+ cations, (2) HDPyCl molecules and (3) micelles with decreasing binding intensities in this order.     

Sorption of polycyclic aromatic hydrocarbons (PAHs) on glass surfaces

Sorption of polycyclic aromatic hydrocarbons (PAHs) to glass commonly used in laboratories was studied. Sorption coefficients (K_d) of five selected PAHs to borosilicate glass surfaces were measured using column chromatography. A linear relationship between log K_d and the corresponding water solubility of the subcooled liquid (log S_w) of the investigated PAHs was observed. Based on the determined sorption coefficients our data revealed that mass loss caused by sorption on glass walls strongly depends on the ratio of solution volume to contacted surface area (V/S). The influence of solution chemistry such as ionic strength, solution pH, presence of cosolvent, and the influence of temperature on the sorption process were investigated. In the presence of ionic strength, sorption coefficients concurrently increased but less than a factor of 2 up to 0.005 M calcium chloride concentration. However, further increasing ionic strength had no influence on K_d. The cosolvent reduced sorption at a concentration of methanol in water above 0.5% (v/v); however, for benzo[a]pyrene even with 10% (v/v) methanol the mass loss would be still higher than 10% (with a V/S ratio less than 0.25). Significant effects of the solution pH and temperature were not observed. These results suggest that van der Waal’s forces dominate the sorption process. In the analysis of highly hydrophobic PAHs in aqueous samples, mass loss due to sorption on glass walls should be accounted for in the final result if untreated glass is used. The presented relationship between log K_d and log S_w may help to decide if such a correction is necessary. Furthermore, the frequently used silanization of glass surfaces may not be sufficient to suppress sorption for large PAHs.     

Solute transport properties of compacted Ca-bentonite used in FEBEX project

The present Spanish concept of a deep geological high level waste repository includes an engineered clay barrier around the canister. The clay presents a very high sorption capability for radionuclides and a very small hydraulic conductivity, so that the migration process of solutes is limited by sorption and diffusion processes. Therefore, diffusion and distribution coefficients in compacted bentonite (i.e. in "realistic" liquid to solid ratio conditions) are the main parameters that have to be obtained in order to characterise solute transport that could be produced after the canister breakdown. Through-Diffusion (TD) and In-Diffusion (ID) experiments with HTO, Sr, Cs and Se were carried out using compacted FEBEX bentonite, which is the reference material for the Spanish concept of radioactive waste disposal. Experiments were interpreted by means of available analytical solutions that allow the estimation of diffusion coefficients and, in some cases, distribution coefficients. Analytical solutions are simple to use, but rely on hypotheses that do not hold in all the experiments. These experiments were interpreted also using an automatic parameter estimation code that overcomes the limitations of analytical solutions. Numerical interpretation allows the simultaneous estimation of porosity, diffusion and distribution coefficients, accounts for the role of porous sinters and time-varying boundary concentrations, and can use different types of raw concentration data.     

Influence of the presence of heavy metals and surface-active compounds on the sorption of bisphenol A to sediment

The effects of different heavy metals (Cd, Pb), cationic surfactants cetyltrimethylammonium bromide (CTAB), anionic surfactant sodium dodecylbenzenesulfonate (SDBS) and the chemistry of the solution (pH and ionic strength) on the sorption of bisphenol A (BPA) to sediment were studied. Results showed that the presence of Cd and Pb caused a significant increase on the sorption of BPA to sediment and the sorption isotherms were in good agreement with Freundlich equation. The effect of surfactants on the adsorption of BPA onto sediment was found to strongly depend on the type of the surfactants. The presence of CTAB promoted BPA sorption and the amount of BPA adsorbed onto sediment increased linearly with concentration of CTAB. In contrast, the presence of anionic surfactant (SDBS) caused a slight reduction on the sorption of BPA. It was also found that the sorption behavior of BPA was affected by solution pH and ionic strength. The larger amount of BPA was absorbed with higher ionic strength and lower pH. This study may provide important insights into the understanding of the transport and fate of BPA in the environment.     

Sorption and desorption of imidazolium based ionic liquids in different soil types

This study investigates the influence of the two different clay minerals kaolinite and smectite as well as of organic matter on the cation sorption and desorption behaviour of three imidazolium based ionic liquids -1-butyl-3-methyl-imidazolium tetrafluoroborate (IM14 BF(4)), 1-methyl-3-octyl-imidazolium tetrafluoroborate (IM18 BF(4)) and 1-butyl-3-methyl-imidazolium bis[(trifluoromethyl)sulfonyl]imide (IM14 (CF(3)SO(2))(2)N) - in soil. The German standard soil Lufa 2.2 - a natural soil classified as a loamy sand - was the basis substrate for the different soil compositions and also served as a reference soil. The addition of organic matter and clays increases the sorption of the substances and in particular smectite had striking effects on the sorption capacity for all three ionic liquids indicating that ionic interactions play an important role for sorption and desorption processes of ionic liquids in soil. One exception was for kaolinite-containing soils and the IM14 cation: with (CF(3)SO(2))(2)N(-) as an anion the sorption was identical at either 10 wt% or 15 wt% clay content, and with BF(4)(-) sorption was even lower at 15 wt% kaolinite than at 10 wt%. Desorption was weak for IM18 BF(4), presumably owing to the longer alkyl side chain. With regard to the influence of kaolinite on desorption, the same pattern was observed as it was found for the sorption of IM14 BF(4) and IM14 (CF(3)SO(2))(2)N.     

天然及CaCl2改性沸石对四环素的吸附

通过静态吸附实验研究了水中四环素在天然和CaCl2改性沸石上的吸附行为及机制。实验表明,天然沸石对四环素具有吸附能力,CaCl2改性可以提高沸石对四环素的吸附能力。天然和改性沸石对四环素的吸附符合拟二级动力学模型,颗粒内扩散不是吸附过程的主要控制步骤。Freundlich和Dubinin-Radushkevich(D-R)等温吸附模型可以较好地描述实验所用2种沸石对四环素的吸附行为,D-R等温方程拟合结果显示吸附过程包含离子交换作用。通过对天然和改性沸石吸附四环素前后溶液中主要阳离子浓度变化分析证实了该吸附过程包含离子交换作用。实验研究了pH值变化对沸石吸附四环素的影响,当pH=3～5时,天然和改性沸石对四环素的吸附量均随pH值的增加而急剧下降,而pH=5～10时,天然和改性沸石对四环素的吸附量变化均不明显,推测可能是离子交换作用和化学沉淀吸附作用所致。另外,实验还初步探索了溶液离子强度对沸石吸附四环素的影响情况,随着溶液中Na+和Ca2+离子强度的增加,吸附量先急剧降低随后趋向平稳,进一步说明了沸石对四环素的吸附过程不是由单一机制控制的。     

Cesium migration in saturated silica sand and Hanford sediments as impacted by ionic strength

Large amounts of 137Cs have been accidentally released to the subsurface from the Hanford nuclear site in the state of Washington, USA. The cesium-containing liquids varied in ionic strengths, and often had high electrolyte contents, mainly in the form of NaNO3 and NaOH, reaching concentrations up to several moles per liter. In this study, we investigated the effect of ionic strengths on Cs migration through two types of porous media: silica sand and Hanford sediments. Cesium sorption and transport was studied in 1, 10, 100, and 1000 mM NaCl electrolyte solutions at pH 10. Sorption isotherms were constructed from batch equilibrium experiments and the batch-derived sorption parameters were compared with column breakthrough curves. Column transport experiments were analyzed with a two-site equilibrium-nonequilibrium model. Cesium sorption to the silica sand in batch experiments showed a linear sorption isotherm for all ionic strengths, which matched well with the results from the column experiments at 100 and 1000 mM ionic strength; however, the column experiments at 1 and 10 mM ionic strength indicated a nonlinear sorption behavior of Cs to the silica sand. Transport through silica sand occurred under one-site sorption and equilibrium conditions. Cesium sorption to Hanford sediments in both batch and column experiments was best described with a nonlinear Freundlich isotherm. The column experiments indicated that Cs transport in Hanford sediments occurred under two-site equilibrium and nonequilibrium sorption. The effect of ionic strength on Cs transport was much more pronounced in Hanford sediments than in silica sands. Effective retardation factors of Cs during transport through Hanford sediments were reduced by a factor of 10 when the ionic strength increased from 100 to 1000 mM; for silica sand, the effective retardation was reduced by a factor of 10 when ionic strength increased from 1 to 1000 mM. A two order of magnitude change in ionic strength was needed in the silica sand to observe the same change in Cs retardation as in Hanford sediments.     

Transport of molybdenum in a biosolid-amended alkaline soil

The transport of molybdenum (Mo) in a biosolid-amended, alkaline, agricultural soil was examined in the research reported herein. Batch-equilibrium and miscible-displacement experiments were conducted to examine the transport of Mo in soil with and without 10% by weight biosolid amendment. The results of geochemical modeling, conducted using PHREEQC, indicated that no mineral dissolution or precipitation reactions were expected for the system under the prevailing conditions. Sorption equilibrium coefficients (Kd) obtained from moment analysis of the Mo breakthrough curves were similar to those calculated from the results of the batch-equilibrium experiments. Mo sorption was greater for the biosolid-amended soil (Kd of 1.3 versus 0.35). Sorption of Mo was shown to be linear, rate limited, and reversible for both unamended and amended soil. The results suggest that Mo associated with biosolid-amended soils is relatively bioavailable and mobile.     

天然及CaCl_2改性沸石对四环素的吸附

通过静态吸附实验研究了水中四环素在天然和CaCl2改性沸石上的吸附行为及机制。实验表明,天然沸石对四环素具有吸附能力,CaCl2改性可以提高沸石对四环素的吸附能力。天然和改性沸石对四环素的吸附符合拟二级动力学模型,颗粒内扩散不是吸附过程的主要控制步骤。Freundlich和Dubinin-Radushkevich（D-R）等温吸附模型可以较好地描述实验所用2种沸石对四环素的吸附行为,D-R等温方程拟合结果显示吸附过程包含离子交换作用。通过对天然和改性沸石吸附四环素前后溶液中主要阳离子浓度变化分析证实了该吸附过程包含离子交换作用。实验研究了pH值变化对沸石吸附四环素的影响,当pH=3～5时,天然和改性沸石对四环素的吸附量均随pH值的增加而急剧下降,而pH=5～10时,天然和改性沸石对四环素的吸附量变化均不明显,推测可能是离子交换作用和化学沉淀吸附作用所致。另外,实验还初步探索了溶液离子强度对沸石吸附四环素的影响情况,随着溶液中Na＋和Ca2＋离子强度的增加,吸附量先急剧降低随后趋向平稳,进一步说明了沸石对四环素的吸附过程不是由单一机制控制的。     

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.     

Sorption of chlorimuron-ethyl on montmorillonite clays: effects of exchangeable cations,pH, and ionic strength

Sorption interaction of chlorimuron-ethyl with montmorillonite clays was investigated under varied types of exchangeable cation, pH, and ionic strength conditions. Chlorimuron-ethyl sorption on bentonites exhibited pronounced cation dependency, and the sorption ability increased as the sequence Ca²⁺- < Na⁺- < Al³⁺- < Fe³⁺-bentonite, due to different sorption mechanisms, whereas the cation dependency was influenced by the clay type and much weaker for montmorillonites. The decrease of pH at the range of 4.0–6.0 prominently increased sorption of chlorimuron-ethyl on all cation-exchanged montmorillonite clays, and nearly a neglected sorption (about 2 %) can be observed at pH over 7.0. In the presence of CaCl₂, sorption of chlorimuron-ethyl on Fe³⁺-bentonite was promoted because of complexion of Ca²⁺ and the surface of Fe³⁺-bentonite. However, as the concentration of CaCl₂ increased, chlorimuron-ethyl sorption on Ca²⁺- and Fe³⁺-exchanged bentonite decreased, suggesting that Ca bridging was not the prevailing mechanism for sorption of chlorimuron-ethyl on these clays. Furthermore, chlorimuron-ethyl sorption was relatively sensitive to pH, and the change of pH may obscure effect of other factors on the sorption, so it was quite necessary to control pH at a constant value when the effect of other factor was being studied.