Sorption of Th(IV) ions onto TiO2: Effects of contact time, ionic strength, thorium concentration and phosphate

Summary The sorption of Th(IV) onto TiO₂ was studied by the batch technique as a function of pH and ionic strength at moderate concentration (10^-4-10^-5 mol/l) and in the presence and absence of phosphate. It was found that the sorption rate of Th(IV) was relatively slow, the sorption percent was abruptly increased from pH 2 to 4, and the sorption was decreased with increasing ionic strength as a whole. In the concentration range of Th(IV) from trace concentration to 1.4 ^. 10^-4 mol/l and in the absence of phosphate, the sorption isotherms were roughly fitted the Freundlich equation at different ionic strengths and approximately constant pH. These sorption characteristics of Th(IV) onto TiO₂ were compared with those of uranyl on the same sorbent. In addition, the positive effect of phosphate on the sorption of Th(IV) onto TiO₂ was demonstrated obviously and can be attributed to strong surface binding of phosphate, and the subsequent formation of ternary surface complexes of Th(IV). The difference between the sorption characteristics of Th(IV) ions and uranyl ions onto TiO₂ is discussed.     

Comparative study on Th(IV) sorption on alumina and silica from aqueous solutions

The effects of pH, ionic strength and concentration on the sorption of Th(IV) on alumina and silica were investigated and the sorption isotherms of Th(IV) on alumina and silica at different pH values were determined. It was found for both sorbents that the absorbability of silica is less than that of alumina. The relative sorption rate of silica is similar to that of alumina. The sorption edges are similar to each other, that the insensitivity of sorption to ionic strength is about the same. These similarities between the sorbents suggest that the speciation of Th(IV) in aqueous solutions plays a significant, but subtle role, in controlling the sorption process, because the charges of both sorbents are distinctly different. The mechanism of Th(IV) sorption on alumina is distinctly different from that of the sorptions of Cs⁺, Eu³⁺ and Yb³⁺ on alumina, and similar to that of the sorption of Co(II) on alumina.     

Th(IV) adsorption on mesoporous molecular sieves: effects of contact time,solid content,pH, ionic strength,foreign ions and temperature

The mesoporous molecular sieves (Al-MCM-41) are synthesized with montmorillonite as silica–alumina source by hydrothermal method. The application of Al-MCM-41 for the adsorption of Th(IV) from aqueous solution is studied by batch technique. The effects of contact time, solid content, pH, ionic strength, foreign ions, and temperature are determined, and the results indicate that the adsorption of Th(IV) to Al-MCM-41 is strongly dependent on pH values but independent of ionic strength. The adsorption isotherms are simulated by D–R and Freundlich models well. The thermodynamic parameters (ΔH ⁰, ΔS ⁰, ΔG ⁰) are calculated from the temperature dependent adsorption isotherms at 293, 313 and 333 K, respectively, and the results suggest that the adsorption of Th(IV) on Al-MCM-41 is a spontaneous and endothermic process. Al-MCM-41 is a suitable material for the preconcentration of Th(IV) from large volumes of aqueous solutions.     

Synthesis, characterization, and application of titanate nanotubes for Th(IV) adsorption

Titanate nanotubes (TNTs) have been synthesized by a hydrothermal method using rutile TiO₂ powder as titanium source. The determination of the structure and morphology was characterized by XRD, FTIR, SEM and TEM. The results indicate that the TNTs successfully synthesized under hydrothermal conditions of 150 °C. The adsorption of Th(IV) on TNTs was studied as a function of contact time, pH values, ionic strength, initial Th(IV) concentration and temperature under ambient conditions by using batch technique. The results indicate that adsorption of Th(IV) on TNTs is strongly dependent on pH values, but weakly dependent on ionic strength; Adsorption kinetics was better described by the pseudo-second-order model. The adsorption isotherms are simulated by Langmuir and Freundlich models well. ΔG°, ΔH° and ΔS° free energy were calculated from experimental data, The results indicate that the adsorption of Th(IV) on TNTs is an endothermic and a spontaneous process, and increases with increasing temperature. The adsorption of Th(IV) on TNTs is mainly dominated by chemical sorption or surface complexation.     

Sorption of Th(IV) on goethite: effects of pH,ionic strength,FA and phosphate

Sorption of thorium (IV) on goethite was investigated as a function of contact time, pH, ionic strength, anions, solid-to-liquid ratio (m/V) and Th(IV) concentration using batch technique. The results showed that the sorption of Th(IV) was strong pH-dependence, and increased from ~10 to ~100% over the pH range of 2.0–4.0, and then kept a constant level in the higher pH range. The sorption of Th(IV) increased with increasing m/V and independent of ionic strength. It was clear that phosphate and FA significantly enhanced Th(IV) sorption on goethite. The sorption and desorption isotherms were investigated at pH 2.90 ± 0.05 and analyzed with Freundlich and Langmuir models, respectively. Compared to Langmuir model, Freundlich model could fit the experimental data better, according to the high relative coefficients.     

Effects of nitrate,fulvate, phosphate,phthalate, salicylate and catechol on the sorption of uranyl onto SiO<Subscript>2</Subscript>: a comparative study

We have performed a large number of batch sorption experiments of uranyl onto SiO₂ and examined the effects of nitrate or ionic strength, phosphate, fulvic acid(FA), phthalic acid (PH), salicylic acid (SA), and catechol (CA) on the uranyl sorption onto SiO₂. Three sorption edges and three sorption isotherms at ionic strengths 0.05, 0.1, and 0.5 mol/L KNO₃ were used to investigate the effect of ionic strength or nitrate on the sorption and the Langmuir, Freundlich, and Dubinin-Radushkevich models are used to simulate the sorption isotherms, respectively. Five sorption edges in the presence of phosphate, FA, PH, SA, and CA were compared with that in the absence of complexing ligand. The results suggest that the effect of complexation of uranyl with nitrate on the uranyl sorption can be negligible and the sorption can be described Freundlich and D-R model very well. The positive effect of phosphate on the uranyl sorption was found, though the extent of effect was decreased with increasing pH. The positive effect and the negative effect of FA on the uranyl sorption were found at low pH and high pH ranges, respectively. The sorption edge of uranyl sorption remained unaffected in the presence of PH in the pH 2–10. In the presence of SA, the no effect and the negative effect on the uranyl sorption were, respectively, found at low pH and high pH ranges. The negative effect of CA on the uranyl sorption was found in the pH 2–10.     

Oxide-dependent adsorption of a model membrane phospholipid, dipalmitoylphosphatidylcholine: bulk adsorption isotherms

The importance of substrate chemistry and structure on supported phospholipid bilayer design and functionality is only recently being recognized. Our goal is to investigate systematically the substrate-dependence of phospholipid adsorption with an emphasis on oxide surface chemistry and to determine the dominant controlling forces. We obtained bulk adsorption isotherms at 55 degrees C for dipalmitoylphosphatidylcholine (DPPC) at pH values of 5.0, 7.2, and 9.0 and at two ionic strengths with and without Ca(2+), on quartz (alpha-SiO(2)), rutile (alpha-TiO(2)), and corundum (alpha-Al(2)O(3)), which represent a wide a range of points of zero charge (PZC). Adsorption was strongly oxide- and pH-dependent. At pH 5.0, adsorption increased as quartz < rutile approximately corundum, while at pH 7.2 and 9.0, the trend was quartz approximately rutile < corundum. Adsorption decreased with increasing pH (increasing negative surface charge), although adsorption occurred even at pH > or = PZC of the oxides. These trends indicate that adsorption is controlled by attractive van der Waals forces and further modified by electrostatic interactions of oxide surface sites with the negatively charged phosphate ester (-R(PO(4)-)R'-) portion of the DPPC headgroup. Also, the maximum observed adsorption on negatively charged oxide surfaces corresponded to roughly two bilayers, whereas significantly higher adsorption of up to four bilayers occurred on positively charged surfaces. Calcium ions promote adsorption beyond a second bilayer, regardless of the sign of oxide surface charge. We develop a conceptual model for the structure of the electric double layer to explain these observations.     

Adsorption of human serum albumin (HSA) onto colloidal TiO2 particles, Part I

The adsorption of human serum albumin (HSA) onto colloidal TiO2 (P25 Degussa) particles was studied in NaCl electrolyte at different solution pH and ionic strength. The HSA-TiO2 interactions were studied using adsorption isotherms and the electrokinetic properties of HSA-covered TiO2 particles were monitored by electrophoretic mobility measurements. The adsorption behavior shows a remarkable dependence of the maximum coverage degree on pH and was almost independent of the ionic strength. Other characteristic features such as maximum adsorption values at the protein isoelectric point (IEP approximately 4.7) and low-affinity isotherms that showed surface saturation even under unfavorable electrostatic conditions (at pH values far away from the HSA IEP and TiO2 PZC) were observed. Structural and electrostatic effects can explain the diminution of HSA adsorption under these conditions, assuming that protein molecules behave as soft particles. Adsorption reactions are discussed, taking into account acid-base functional groups of the protein and the surface oxide in different pH ranges, considering various types of interactions.     

Effects of pH and ionic strength on the adsorption of phosphate and arsenate at the goethite-water interface

The surface properties of a well-crystallized synthetic goethite have been studied by acid-base potentiometric titrations, electrophoresis, and phosphate and arsenate adsorption isotherms at different pH and electrolyte concentrations. The PZC and IEP of the studied goethite were 9.3+/-0.1 and 9.3+/-0.2, respectively. Phosphate and arsenate adsorption decrease as the pH increases in either 0.1 or 0.01 M KNO(3) solutions. Phosphate adsorption is more sensitive to changes in pH and ionic strength than that of arsenate. The combined effects of pH and ionic strength result in higher phosphate adsorption in acidic media at most ionic strengths, but result in lower phosphate adsorption in basic media and low ionic strengths. The CD-MUSIC model yields rather good fit of the experimental data. For phosphate it was necessary to postulate the presence of three inner-sphere surface complexes (monodentate nonprotonated, bidentate nonprotonated, and bidentate protonated). In contrast, arsenate could be well described by postulating only the presence of the two bidenate species. A small improvement of the arsenate adsorption data could be achieved by assuming the presence of a monodentate protonated species. Model predictions are in agreement with spectroscopic evidence, which suggest, especially for the case of arsenate, that mainly bidentate inner-sphere complexes are formed at the goethite-water interface.     

Alumina interaction with AMPS-MPEG random copolymers III. Effect of PEG segment length on adsorption, electrokinetic and rheological behavior

The effect of different 2-acrylamido-2-methylpropanesulfonic acid sodium salt (AMPS)-methoxypolyethyleneglycol methacrylate (MPEG) comb-like copolymers on the adsorption behavior, electrokinetic and rheological properties of alumina suspensions has been investigated. The change in adsorption isotherms with the content of the two monomers, the medium pH and the ionic strength indicated that the interaction of these copolymers was found to be controlled by both the fraction of ionic groups on the polymer and by the length of the polyethyleneglycol (PEG) segments. Adsorption of the copolymers on alumina particles is accompanied by a shift in the IEP toward acid pH values and may lead to a charge reversal above a certain level. The presence of the PEG segment equally affects the magnitude of the zeta potential by moving the shear plane forward. Addition of the copolymers greatly affects the rheological behavior of the suspension; the viscosity at a defined shear rate decreases and reaches an optimum, which is all the lower as the fraction of the ionic groups is higher. The dispersing effect of the copolymer was controlled by both the ionization level of the copolymer and by the length of the PEG segments.     

Alumina interaction with AMPS-MPEG random copolymers I. Adsorption and electrokinetic behavior

Adsorption of brush copolymers, bearing sulfonate groups and polyethylene glycol segments, on to alumina particles in suspension in water has been investigated. Study of the adsorption isotherms revealed that the copolymers displayed a strong affinity for the surface of the alumina regardless of the fraction of ionic groups on the polymer. For poly(ethylene glycol) content greater than 50%, the adsorption isotherms revealed an initial adsorption plateau followed by a second one. The shape of the adsorption isotherms was interpreted in terms of the polymer configuration at the solid-to-liquid interface. The effects of the pH and the ionic force on adsorption were studied and connected to the effects of interaction between chain segments at the surface of the alumina particles. Changes in the electrokinetic properties of the alumina particles after addition of the copolymers were investigated by following the zeta potential of particles as a function of pH. In the presence of the copolymer continuous shift of the isoelectric point IEP to a more acidic values was observed. Beyond a certain concentration the zeta potential remained negative regardless of the pH.     

Am(III) adsorption on oxides of aluminium and silicon: effects of humic substances,pH, and ionic strength

The adsorption of Am(III) (total concentration 10(-9) mol/l) on alumina, silica, and hematite was studied by a batch technique. The effects of pH, ionic strength, and humic substances on the adsorption of Am(III) on alumina and silica were investigated, and the adsorption isotherms of Am(III) on alumina and silica at different pH values were determined. It was found that compared with the adsorption of Am(III) on alumina, the adsorbability of silica on the basis of mass is less, the relative adsorption rate on silica is slower, the sensitivity of adsorption on silica to ionic strength is less, the dependence of adsorption on silica on pH is gentler, and consequently that the adsorption characteristics of Am(III) on alumina and silica are distinctly different. The negative effect of fulvic acid on the adsorption on silica and the positive effect of humic acid on the adsorption on alumina were found. In contrast to the Am(III) adsorption on alumina and silica, a tremendously high adsorbability of Am(III) on hematite was found. The sequence of adsorbabilities of Am(III) on the basis of mass is Fe2O3 > Al2O3 > SiO2.     

The ionic strength effect on microcystin and natural organic matter surrogate adsorption onto PAC

This work aims to contribute to a better understanding of the ionic strength effect on microcystin and natural organic matter (NOM) surrogate adsorption by analyzing the importance of adsorbate molecular size, and surface concentration. Adsorption kinetics and/or isotherms were performed on PAC Norit SA-UF for four microcystin variants (MC-LR, MC-LY, MC-LW, MC-LF), and three NOM surrogates (salicylic acid (SA), tannic acid (TA), Aldrich humic acid (AHA)) at different solution ionic strengths. Results showed that the ionic strength effect depends upon the adsorbate surface concentration, cation charge (mono or divalent), and adsorbate molecular size. Potassium seemed not to affect the MC-LR adsorption, while calcium enhanced MC-LR kinetics and adsorption capacity. K+ and, particularly, Ca2+ improved the adsorption kinetics of the other microcystin variants. For identical surface concentration and ionic strength, the impact of K+ and Ca2+ on NOM surrogates depended on the adsorbate molecular size: K+ effect was only observed for AHA, whereas Ca2+ caused no effect on SA adsorption, slightly enhanced TA adsorption, and greatly enhanced AHA adsorption. MC-LR isotherms with two salt concentrations (KCl or CaCl2) indicated that, for the studied range of equilibrium surface concentration (5.3-18.7 mg/g), an enhanced adsorption regime prevails, and no transition regime was observed.     

Biomimetic particles: optimization of phospholipid bilayer coverage on silica and colloid stabilization

The effect of ionic strength and pH on phosphatidylcholine (PC) adsorption from vesicles on silica nanoparticles was investigated over a range of NaCl concentrations (0.1-150 mM) at pH 6.3 and 7.4 from determination of adsorption isotherms, colloid stability, particle sizing, and zeta-potentials. At and above 10 mM ionic strength, pH 6.3, high-affinity adsorption isotherms with limiting adsorption indicative of one-bilayer deposition on each silica particle were obtained. At 10 mM ionic strength, adsorption isotherms indicated lower affinity between PC and silica at pH 7.4 than at pH 6.3, suggesting a role of hydrogen bonding between silanol on silica and phosphate on PC in promoting bilayer deposition at low pH. Under conditions where high affinity and bilayer deposition were achieved, silica sedimentation documented from photographs was absent, suggesting particle stabilization induced by bilayer coverage. However, at physiological (150 mM NaCl) or close to physiological ionic strength (140 mM NaCl), the large colloid stability similarly achieved at pH 6.3 or 7.4 suggested the major role of van der Waals attraction between the PC bilayer vesicle and silica particle in determining bilayer deposition. The effect of increasing ionic strength was increasing van der Waals attraction, which caused PC vesicle disruption with bilayer deposition and bilayer-induced silica stabilization.     

The impact of ionic strength and background electrolyte on pH measurements in metal ion adsorption experiments

Our understanding of metal ion adsorption to clay minerals has progressed significantly over the past several decades, and theories have been promulgated to describe and predict the impacts of pH, ionic strength, and background solution composition on the extent of adsorption. Studies evaluating the effects of ionic strength on adsorption typically employ a broad range of background electrolyte concentrations. Measurement of pH in these systems can be inaccurate when pH values are measured with liquid junction pH probes calibrated with standard buffers due to changes in the liquid junction potential between standard, low ionic strength (0.05 M) buffers and high ionic strength solutions (>0.1 M). The objective of this research is to determine the extent of the error in pH values measured at high ionic strength, and to develop an approach for accurately measuring pH over a range of ionic strengths using a combined pH electrode. To achieve this objective, the adsorption of cobalt (10(-5) M) onto gibbsite (10 g/L) from various electrolyte solutions (0.01-1 M) was studied. The pH measurements were determined from calibrations with standard buffers and ionic strength corrected buffer calibrations. The results show a significant effect of the aqueous solution background electrolyte anion and ionic strength on pH measurement. The 0.5 and 1 M ionic strength metal ion adsorption edges shifted to lower pH with increasing ionic strength when pH was calibrated with standard buffers whereas no shift in the adsorption edges was observed when calibrated with ionic strength corrected buffers. Therefore, to obtain an accurate pH measurement, pH calibration should contain the same electrolyte and ionic strength as the samples.     

A titration study on alumina-coated rutile pigments

A series of potentiometric titrations was carried out on alumina coated rutile pigments. The point of intersection of the adsorption isotherms obtained at three ionic strengths was independent of the titration speed, hence these experiments are considered to give a reliable estimate of the i. e. p. of the sample. The adsorption isotherms are, however, irreversible and the uptake of protons and hydroxyl ions is dependent upon titration speed. The irreversibility of the isotherms appears to be related to the slow drift in the pH of the pigment suspension that takes place during the titration. This pH drift is due to 1) a partial dissolution of the alumina coating and 2) a slow movement of protons into and out of the coating on the pigment.     

Adsorption characteristics of As(V), Se(IV), and V(V) onto activated alumina: effects of pH, surface loading, and ionic strength

Arsenic, selenium, and vanadium are major anionic elements of concern in drinking water. This research investigated the adsorption characteristics of As(V), Se(IV), and V(V) onto a commercial activated alumina (AA) under different pH, surface loading, and ionic strength conditions using batch systems. The results indicated that the adsorption of these elements was significantly affected by pH and the surface loading. However, ionic strength generally did not impact their adsorption, indicating that the electrostatic effect on the adsorption of these elements was relatively not important compared to surface chemical reactions. A speciation-based adsorption model was used to simulate the adsorption of As(V), Se(IV), and V(V) by activated alumina and to determine the adsorption constants of different element species. This model can satisfactorily predict the adsorption of these elements in a broad pH range from 1.5 to 12 and a wide surface loading range from 1.0 to 50 mg/g activated alumina for different sorbent concentrations, using the same set of adsorption constants.     

Adsorptive removal of U(VI) and Th(IV) from aqueous solutions using polymer-based electrospun PEO/PLLA fibrous membranes

Fibrous membranes based on poly(ethylene oxide) and poly(l-lactide) fabricated by electrospinning were evaluated for the first time as substrates for the adsorption of tetravalent thorium (Th(IV)) and hexavalent uranium (U(VI)) from aqueous media. The membranes consisted of microfibers with diameters of approximately 2 μm as revealed by scanning electron microscopy. The adsorption of Th(IV) and U(VI) on the membrane was investigated as a function of pH, ionic strength and initial metal concentration under normal atmospheric conditions. The experimental data indicated increased affinity of the membrane for Th(IV) and U(VI), which was pH depended and reaches maximum values (>90 %) for Th(IV) and U(VI) at pH 3 and pH 6.5, respectively. The maximum adsorption capacity (q _max) at optimum conditions was evaluated from the Langmuir isotherm and was found to amount 50.08 and 9.3 mmol kg^?1 for Th(IV) and U(VI), respectively. In addition, studies on the effect of ionic strength on the adsorption efficiency did not show any significant effect indicating that the adsorption of Th(IV) and U(VI) on the membrane was most probably based on specific interactions and the formation of inner-sphere surface complexes. The significantly higher adsorption efficiency of the membrane for Th(IV) in acidic media (pH ≤ 3) could be utilized for a pH-triggered, selective separation of Th(IV) from U(VI) from aqueous media.     

Intersection of isotherms for phosphate adsorption on hematite

Adsorption isotherms for phosphate on hematite were prepared at pH 3.39, 4.16, 5.10, 5.63, and 6.71 in this study. It was found that the adsorption isotherms at pH 5.63 and 6.71 intersected those at pH 4.16 and 5.10. Using surface complexation theory, this study demonstrates that the intersection of adsorption isotherms results from (1) phosphate being adsorbed mainly as protonated complexes at pH 4.16 and 5.10 but as nonprotonated complexes at pH 5.63 and 6.71; (2) the electric potential (psi) at the surface of hematite changing with pH at a rate less than 29.5 mV per pH unit (-d psi /dpH approximately equal 8.9 mV/pH). Fundamentally, however, it seems that the dominance of an imperfect (001) crystal face in the hematite sample is responsible for a low value of -d psi/dpH and the intersection of adsorption isotherms. The adsorption behavior may be regarded as characteristic behavior of protonation of adsorbed phosphate on an oxide with a small value of -d psi / dpH.     

The adsorption-desorption process of bovine serum albumin on carbon nanotubes

The aim of this work is to study the adsorption-desorption process of bovine serum albumin (BSA) on carbon nanotubes (CNT) by reflectometry. The effect of the surface properties was analyzed by comparing the behavior of BSA on silica. The experiments were performed by reflectometry at different BSA concentrations, at pH 3.0, 4.8, and 7.0 and at two ionic strengths. Protein desorption was induced by either dilution with buffer or the addition of SDS. The initial adsorption rate is controlled by the attachment of BSA molecules to the surface, and strongly diminishes at pH 7. Adsorption isotherms reflect the high affinity of BSA for both sorbent surfaces and reach well-defined plateau values that depend on the pH, being the highest at pH 4.8 on CNT. Experiments performed at different ionic strengths (NaCl added) showed a less pronounced effect. Dilution does not induce desorption on either surface however, the addition of SDS removes protein only from the silica surface.