Adsorption of zearalenone by organomodified natural zeolitic tuff

Adsorption of zearalenone (ZEN) by natural zeolitic tuff, modified with different numbers of octadecyldimethylbenzylammonium (ODMBA) ions, was investigated. The results of solid-state 1H NMR analysis of the starting material suggested that zeolitic tuff is rich in mineral clinoptilolite, confirming the results of previous thermal stability study. Three organozeolites (OZ-2, OZ-5, and OZ-10) were prepared with ODMBA surface coverages of 20, 50, and 100 mmol/100 g. The mechanism of ZEN sorption by the three organozeolites was investigated through the determination of the adsorption isotherms at pH 3, 7, and 9. Adsorption of ZEN by organozeolites was best represented by a linear type of isotherm at pH 3, while at pH 7 and 9, adsorption of ZEN by organozeolites followed a nonlinear (Langmuir) type of isotherm. The different shape of the ZEN adsorption isotherms for the three organozeolites with different levels of ODMBA at the zeolitic surface at different pH values suggests that the adsorption mechanism may be dependent on the form of ZEN in solution. Since, at pH 3, ZEN exists in solution as the neutral form, the linear isotherms at pH 3 suggested that hydrophobic interactions are probably responsible for adsorption of neutral, hydrophobic ZEN onto the hydrophobic surface of the organozeolites. At pH 7, the phenolate anion is present in water solution, while at pH 9, ZEN is almost entirely in the anionic form. The nonlinear isotherms obtained for ZEN adsorption by the three organozeolites suggest that sorption appears to be the result of the adsorption process as well as partitioning.     

Study of chromium(VI) adsorption onto modified activated carbons with respect to analytical application

Two different types of modification of activated carbon, by treatment with concentrated solution of HNO₃ and outgassing treatment at high temperature, were studied in order to obtain the most effective adsorption of chromium(VI) ions from water solution. The basic parameters affecting the adsorption capacity of Cr(VI) ions on modified activated carbons were studied in details and the effect of modifications of activated carbons has been determined by studying the initial runs of adsorption isotherms. The obtained Cr(VI) adsorption isotherms were well fitted in the Freundlich equation. The reduction of Cr(VI) to Cr(III) and further ion exchange mechanism of adsorption onto oxidizing activated carbon and surface precipitation to Cr(OH)₃ in case of outgassing activated carbon were found as the main adsorption mechanisms of Cr(VI) ions onto modified activated carbons. Presence of chlorides and nitrates in studied adsorption system strongly decreased the adsorption ability of Cr(VI) onto outgassing activated carbon and mechanism of this behavior is proposed.     

烷基硫酸钠在二氧化钛上的吸附研究

表面活性剂在氧化物表面上的吸附,因其在浮选中的重要作用而被广泛研究。但迄今为上的工作多是关于表面活性离子在电性相反的氧化物表面上,例如阳离子表面活性剂在带负电的氧化物表面上的吸附,而对电性相同的表面活性离子的吸附则很少涉及,虽然许多实际问题中遇到的是后一种情形。本工作研究了烷基硫酸钠在带负电的TiO₂表面上的吸附,根据吸附与电泳的实验结果计算了吸附自由能,并提出了可能的吸附机理。     

Conducting polymer/alumina composites as viable adsorbents for the removal of fluoride ions from aqueous solution

The polyaniline/alumina (PANi-AlO) and polypyrrole/alumina (PPy-AlO) composites were prepared and characterized by FT-IR, SEM and X-ray diffraction studies and were employed as adsorbents for the removal of fluoride ions from aqueous solution by the batch sorption method. The amount of fluoride ions adsorbed per unit mass of the adsorbents was observed to be higher than that by the individual constituents. The maximal amount of adsorption is 6.6 mg/g for PANi-AlO and for PPy-AlO it is 8 mg/g. The Langmuir and Freundlich isotherms were used to describe adsorption equilibrium. The kinetics of the adsorption process was investigated using Natarajan-Khalaf equation and intraparticle diffusion model. FT-IR and XRD pattern of the adsorbent, before and after the adsorption is recorded to get better insight into the mechanism of the adsorption process. The results of equilibrium and spectral investigations revealed that the mechanism of fluoride ion removal by these composites involve both the formation of aluminium-fluoro complexes on the alumina surface and doping/dopant-exchange of fluoride ions in the polymer.     

THEORETICAL MODELING OF IONIC SURFACTANT ADSORPTION ON MINERAL OXIDE SURFACES

A model for the adsorption of ionic surfactants on oppositely charged solid surfaces of uniform charge density is developed. The model is based on the assumption that, on the solid surface, adsorbed surfactant monomers, monolayered and bilayered surfactant aggregates of different sizes and specifically adsorbing ions of added electrolyte constitute a mixture of hard discs. It means that only excluded area interactions between the surface discs are taken into account. To avoid a rapid two-dimensional condensation of the adsorbed surfactant the potential energy per molecule in the surface aggregates, which is a sum of chemical and electrostatic interactions, is assumed to decrease linearly with the increasing aggregate size. The electrostatic interactions of ionic species with the charged solid surface are described in terms of the Guy-Chapman theory of the double layer formation. The appropriate equations for adsorption isotherms of surfactant and electrolyte ions are derived and used to predict the experimental adsorption isotherms of DTAB on the precipitated silica at two different salt concentrations in the aqueous solution, On the basis of the obtained results the evolution of the adsorbed phase structure and the charge of silica particles with an increasing surface coverage is discussed.     

Oleic acid adsorption-desorption isotherms on the surface of high-dispersity ferrites from a solution in carbon tetrachloride

The equilibrium adsorption method was used to comparatively study the adsorption-desorption isotherms of oleic acid on the surfaces of manganese and copper ferrites from a solution in carbon tetrachloride. The adsorption isotherms of the fatty acid were described in terms of the theory of volume filling of micropores. The theory was used to calculate the limiting adsorption values, characteristic energy, and porous space volumes. The isotherm of oleic acid adsorption on the surface of manganese ferrite from a solution in carbon tetrachloride was similar to the isotherms of fatty acid adsorption from solutions in heptane, whereas the isotherm of adsorption on the surface of copper ferrite was similar to the isotherms of fatty acid adsorption from hexane. The limiting adsorption from carbon tetrachloride was higher on the surface of manganese ferrite than on the surface of copper ferrite. The adsorption-desorption isotherms contained hysteresis loops.     

Nanoparticles of octakis[3-(3-amino-1,2,4-triazole)propyl]octasilsesquioxane as ligands for Cu(II), Ni(II), Cd(II), Zn(II), and Fe(III) in aqueous solution

Nanoparticles of octakis[3-(3-amino-1,2,4-triazole)propyl]octasilsesquioxane (ATZ-SSQ) were tested as ligands for transition-metal ions in aqueous solution with a special attention to sorption isotherms, ligand-metal interaction, and determination of metal ions in natural waters. The adsorption potential of the material ATZ-SSQ was compared with related [3(3-amino-1,2,4-triazole)propyl]silica gel (ATZ-SG). The adsorption was performed using a batchwise process and both organofunctionalized surfaces showed the ability to adsorb the metal ions from aqueous solution. The Langmuir model was used to simulate the sorption isotherms. The results suggest that the sorption of these metals on ATZ-SSQ and ATZ-SG occurs mainly by surface complexation. The equilibrium condition is reached at time lower than 3 min for ATZ-SSQ, while for ATZ-SG is only reached at time of 25 min. The maximum metal ion uptake values for ATZ-SSQ were higher than the corresponding values achieved with the ATZ-SG. In order to obtain more information on the ligand-metal interaction of the complexes on the surface of the ATZ-SSQ nanomaterial, ESR study with various degrees of copper loadings was carried out. The ATZ-SSQ was tested for the determination (in flow using a column technique) of the metal ions present in natural waters.     

The adsorption of alkylpyridinium chlorides and their effect on the interfacial behavior of quartz

This research was directed at understanding cationic surfactant adsorption phenomena on wet-ground natural quartz, mainly with dodecylpyridinium chloride as the model surfactant. How these surfactant ions adsorb at the interface was delineated through measurements of adsorption isotherms, zeta potentials, suspension stability, contact angles, induction times, and flotation response. Hydrocarbon chain association of adsorbed surfactant ions (or self-association) leads to four distinct adsorption regions as the concentration of surfactant is increased in solution. The same four regions manifest themselves in the behavior of all of the interfacial processes studied. At low concentrations, adsorption is controlled primarily by electrostatic interactions, but when the adsorbed surfactant ions begin to associate into hemimicelles at the surface, hydrophobic chain interactions control the adsorption process. The results of experiments with alkylpyridinium chlorides of 12, 14 and 16 carbon atoms can be normalized in terms of their CMCs, which clearly show that surface aggregation phenomena are driven by the same hydrophobic interactions that lead to micelle formation in bulk solution.     

Single, binary, and multicomponent sorption of iron and manganese on lignite

Acid mine drainage (AMD) has long been a significant environmental problem resulting from the microbial oxidation of iron pyrite in the presence of water and air, affording an acidic solution that contains toxic metal ions. The main objective of this study was to remove metal ions [Fe(II), Fe(III), Mn(II), Zn(II)] from AMD using lignite, a low-cost adsorbent. The lignite sorbent was utilized for the sorption of ferrous, ferric, manganese, zinc, and calcium ions in aqueous solutions. Studies were performed at different pH to find optimum pH. Equilibrium isotherms were determined to assess the maximum adsorption capacity of lignite for different metal ions. Sorption capacities were compared in single, binary, ternary, and multicomponent systems. The sorption data are correlated with Freundlich and Langmuir isotherms in each system. Both Freundlich and Langmuir isotherms fit the data reasonably well in terms of regression coefficients. Sorption studies were also performed at different temperatures to obtain the thermodynamic parameters of the process. The maximum lignite adsorption capacities at 25 degrees C were 34.22, 25.84, and 11.90 mg/g for Fe(II), Mn(II), and Fe(III), respectively. Adsorption of Fe(2+) (24.70 mg/g at 10 degrees C and 46.46 mg/g at 40 degrees C) increased with increased temperature, while Mn(2+) adsorption (28.11 mg/g at 10 degrees C and 7.70 mg/g at 40 degrees C) decreased with increased temperature.     

Removal of copper from aqueous solutions by adsorption on activated carbons

The adsorption isotherms of Cu(II) ions from aqueous solutions in the concentration range 40–1000 mg l⁻¹ on two samples of granulated and two samples of activated carbon fibres containing varying amounts of associated oxygen have been reported. The adsorption isotherms are type I of BET classification showing initially a rapid adsorption tending to be asymptotic at higher concentrations. The amounts of oxygen associated with the carbon surface has been enhanced by oxidation with nitric acid and ammonium persulphate in the solution phase and with oxygen gas at 350°C and decreased by degassing of the oxidized carbon samples at 400, 650 and 950°C. The adsorption of Cu(II) ions increases on oxidation and decreases on degassing. The increase in adsorption on oxidation depends on the nature of the oxidative treatment while the decrease in adsorption on degassing depends on the temperature of degassing. This has been attributed to the increase in the carbon–oxygen acidic surface groups on oxidation and their decrease on degassing. Suitable mechanisms consistent with the results have been proposed.     

Surface tension and adsorption of electrolytes at the aqueous solution-gas interface

The surface tension of aqueous solutions of hydrogen, sodium, and potassium chlorides was measured. The excess adsorption isotherms for electrolyte adsorption at the liquid-gas interface were obtained. The dependence of the surface tension on the solute concentration exhibits an extremal character, with the onset surface-inactivity of electrolytes being observed at concentrations above 0.3 M. The composition of the surface layer was demonstrated to be governed by the energy of solvation, while the extrema in the surface tension and excess adsorption isotherms are associated with the behavior of individual ions in the adsorption layer of the interphase interface.     

Influence of pH,ionic strength,foreign ions and FA on adsorption of radiocobalt on goethite

This work contributed to the adsorption of radiocobalt on goethite as a function of contact time, pH, ionic strength and foreign ions in the absence and presence of fulvic acid (FA) under ambient conditions. The results indicated that adsorption of Co(II) was dependent on ionic strength and foreign ions at low pH values (pH < 7.8), and independent of ionic strength and foreign ions at high pH values (pH > 7.8). Outer-sphere surface complexation and/or ion exchange were the main mechanisms of Co(II) adsorption on goethite at low pH values, whereas inner-sphere surface complexation was the main adsorption mechanism at high pH values. The presence of FA enhanced Co(II) adsorption at low pH values, but reduced Co(II) adsorption at high pH values. The thermodynamic data (ΔH ⁰, ΔS ⁰, ΔG ⁰) were calculated from the temperature dependent adsorption isotherms, and the results suggested that adsorption process of Co(II) on goethite was spontaneous and endothermic. The results are crucial to understand the physicochemical behavior of Co(II) in the nature environment.     

Adsorption of fluoride ions onto carbonaceous materials

The characteristics of fluoride ion adsorption onto carbonaceous materials were derived as adsorption isotherms at different temperatures and in different pH solutions. The fluoride ion was adsorbed into pores in carbonaceous materials produced from wood; the larger the specific surface area, the more fluoride ions adsorbed. Bone char was the most effective adsorbent. The composition of bone char includes calcium phosphate, calcium carbonate, and so on. This suggests that the phosphate ion in bone char was exchanged with a fluoride ion. Moreover, the mechanism of fluoride ion adsorption onto bone char is clearly chemical in nature because the amount of fluoride ion adsorbed onto bone char increased with increasing temperature and decreasing pH. The amount of fluoride ion adsorbed onto bone char was also shown to depend on the concentration of sodium chloride in solution because of the "salting-out" effect. The adsorption of fluoride ion onto bone char is endothermic. Bone char can be utilized to remove fluoride ions from drinking water.     

Adsorption Isotherms of Cetylpyridinium Chloride with Iron III Salts at Air/Water and Silica/Water Interfaces

The interaction of iron III salts and cetylpyridinium chloride (CPC) has been studied at the air/water and silica/water interfaces. The surface tension of cetylpyridinium chloride has been determined in aqueous solutions in the presence of iron III chloride and iron III nitrate at two constant pH values, namely, 3.5 and 1.2. It is shown that the surface tension of the cationic surfactant depends upon the ionic strength of the solution through the pH adjustment in the presence of the former salt but not in the presence of the latter. The effect of iron III nitrate on the surface tension of CPC is similar to that of potassium nitrate, indicating that the iron III various-hydrolyzed species do not interfere with the composition of the air/water interface. The competitive adsorption of iron III nitrate salt and the cationic surfactant at a silica/water interface was next investigated. The adsorption isotherms were determined at pH 3.5. It is shown that although the iron III ions, which were added to the silica dispersion in the presence of the cetylpyridinium ions, were strongly bound to the anionic surface sites, the surfactant ions are not salted out in the solution but remain in close vicinity of the silica surface. Conversely as the cationic surfactant is added first to the silica dispersion in the presence of the adsorbed iron III ions, the metal ions and the surfactant ions are both coadsorbed onto the silica surface. It is suggested that iron III hydrolyzed or free cations and the cationic surfactant molecules may not compete for the same adsorption sites onto the silica surface.     

Comparative study of Cr(III) adsorption by carbon nanotubes and active carbons

The adsorption of trivalent chromium ions from aqueous solutions on the surface of carbon materials, namely, multiwall carbon nanotubes (NTs) and two samples of active carbon, is studied depending on pH and adsorbate concentration in the system. Isotherms of Cr(III) adsorption by the aforementioned materials are obtained. It is shown that chromium ions are predominantly bound by surface carboxyl groups. The adsorption of chromium ions reduces the electrokinetic potential of NTs and, at chromium concentrations C _Cr(III) > 10^–5 M, leads to the reversal of the surface charge. The adsorption value decreases in the series NT > Merck carbon > Norit carbon, in contrast to an increase in the adsorbate affinity to the adsorbent in this series, as determined from the slope of the initial section of the Langmuir isotherms. Small amounts of chromium ions sorbed at low concentrations in solution (C _Cr(III) ≤ 10^–5 M) are comparable with the concentration of hydrogen ions displaced from the surface, thus making it possible to suppose the existence of an ionexchange adsorption mechanism. As the concentration of Cr(III) increases, the equivalent displacement of H⁺ is violated, thereby indicating the development of other adsorption mechanisms (complexation).     

Kinetics and equilibrium adsorption of Cu(II), Cd(II), and Ni(II) ions by chitosan functionalized with 2[-bis-(pyridylmethyl)aminomethyl]-4-methyl-6-formylphenol

Chitosan biopolymer chemically modified with the complexation agent 2[-bis-(pyridylmethyl)aminomethyl]-4-methyl-6-formylphenol (BPMAMF) was employed to study the kinetics and the equilibrium adsorption of Cu(II), Cd(II), and Ni(II) metal ions as functions of the pH solution. The maximum adsorption of Cu(II) was found at pH 6.0, while the Cd(II) and Ni(II) maximum adsorption occurred in acidic media, at pH 2.0 and 3.0, respectively. The kinetics was evaluated utilizing the pseudo-first-order and pseudo-second-order equation models and the equilibrium data were analyzed by Langmuir and Freundlich isotherms models. The adsorption kinetics follows the mechanism of the pseudo-second-order equation for all studied systems and this mechanism suggests that the adsorption rate of metal ions by CHS-BPMAMF depends on the number of ions on the adsorbent surface, as well as on their number at equilibrium. The best interpretation for the equilibrium data was given by the Langmuir isotherm and the maximum adsorption capacities were 109 mg g-1 for Cu(II), 38.5 mg g-1 for Cd(II), and 9.6 mg g-1 for Ni(II). The obtained results show that chitosan modified with BPMAMF ligand presented higher adsorption capacity for Cu(II) in all studied pH ranges.     

Adsorbed solution model for prediction of normal-phase chromatography process with varying composition of the mobile phase

The adsorbed solution model has been used to predict competitive adsorption equilibria of the solute and the active component of mobile phase in a normal-phase liquid chromatography system. The inputs to the calculations were the single adsorption isotherms accounting for energetic heterogeneity of the adsorbent surface and non-ideality of the mobile phase solution. The competitive adsorption model has been coupled with a model of the column dynamics and used for simulating of chromatography process at different mobile phase composition. The predictions have been verified by comparing the simulated and experimental chromatograms. The model allowed quantitative prediction of chromatography process on the basis of the pure-species adsorption isotherms.     

Sulfate adsorption and surface precipitation on a volcanic ash soil (allophanic andisol)

Sulfate strongly adsorbs on metal oxides and soils with variable charges. However, its surface precipitation has not been clearly evaluated and its adsorption mechanism has been in dispute. In the present study, an allophanic andisol, a typical volcanic ash soil having both negative and positive variable charges, was used to identify the adsorption mechanism of sulfate. Sulfate adsorption isotherms were obtained by a batch method at pH values of 4, 5, 6, and 7 in a wide range of concentrations in an Na-H-SO(4)-OH system. Theoretical isotherms were applied to the measured values for the evaluation. The surface precipitation was detected by the measured adsorption isotherms, and the BET isotherm confirmed the presence of multilayer adsorption. Stronger and weaker adsorption sites were suggested by using the Langmuir isotherm for the monolayer adsorption. The adsorption energies obtained from the Langmuir equation and recent spectroscopic analysis suggested that the stronger adsorption corresponded to an inner-sphere surface complex and that the weaker adsorption corresponded to outer-sphere surface complexation. The BET and Langmuir equations showed three types of adsorption mechanisms for the sulfate adsorption on the soil.     

表面活性剂和聚乙烯吡咯烷酮在ZrO2上的吸附对其悬浮体稳定性的影响

研究了水溶液中十二烷基苯磺酸钠（ＳＤＢＳ）、溴代十四烷基吡啶（ＴＰＢ）和聚乙烯吡咯烷酮（ＰＶＰ）在ＺｒＯ２上的吸附及对ＺｒＯ２水悬浮体稳定性的影响。结果表明：ｐＨ＝２．４时ＳＤＢＳ在ＺｒＯ２上的吸附等湿线为ＬＳ型，ｐＨ＝７．０时ＴＰＢ的吸附等温线为Ｓ型，吸附等温线与ＺｒＯ２粒子ζ电势变化同线有大体一致的关系。在最大吸附量时ＺｒＯ２粒子ζ电势较大，且吸附的表面活性剂离子形成大部分亲水基朝向水相的表面     

Adsorption of cesium (I) from aqueous solution using oxidized multiwall carbon nanotubes

Multiwall carbon nanotubes (MWCNTs) were modified by nitric acid solution and then used to study the adsorption of cesium from aqueous solution using a batch technique under ambient conditions. As produced and oxidized MWCNTs were characterized by nitrogen adsorption/desorption, Boehm’s titration method and Fourier transform infrared spectroscopy. The physical properties of MWCNTs such as functional groups, total number of acid sites and specific surface area were greatly improved after oxidation, and these were responsible for more sorption of cesium from aqueous solution and made them more dispersible in water. The adsorption of cesium ions as a function of contact time, initial concentration of cesium, pH, ionic strength and oxidized MWCNT concentrations was also investigated. The results showed that cesium adsorption percentage strongly depended on the pH value, oxidized MWCNT content and on the solution ionic strength. Kinetic data indicated that the adsorption process achieved equilibrium within 80 min. Equilibrium data for as produced and oxidized MWCNTs was well described by both Freundlich and Langmuir isotherms. The dominant mechanism of cesium adsorption on oxidized MWCNTs may be mainly attributed to ion exchange. This study suggests that oxidized MWCNTs can be a promising candidate for the removal of cesium from nuclear waste solution.