Adsorption of phthalic acid and salicylic acid and their effect on exchangeable Al capacity of variable-charge soils

Low-molecular-weight (LMW) organic acids may be adsorbed by soils and the adsorption could affect their biodegradation and efficiency in many soil processes. In the present study, the adsorption of phthalic acid and salicylic acid and their effect on the exchangeable Al capacity of variable-charge soils were investigated. The results indicated that phthalic acid and salicylic acid were adsorbed by four variable-charge soils to some extent, oxisols showed a greater adsorption capacity for organic acids than ultisols, and the ability of the four variable-charge soils to adsorb the organic acids at different pH generally followed the order Kunming oxisol > Xuwen oxisol > Jinxian ultisol > Lechang ultisol, which was closely related to their content of free iron oxides and amorphous iron and aluminum oxides. The adsorption of organic acids induced a decrease in the zeta potentials of soils and oxides. Goethite has greater adsorption capacity for organic acid than Xuwen oxisol and the adsorption of organic acids resulted in a bigger decrease in the zeta potential of goethite suspensions. After free iron oxides were removed, less organic acid was adsorbed by Xuwen oxisol and no change was observed in zeta potential for the soil suspension after organic acid was added. The presence of phthalic acid increased the capacity of exchangeable Al and the increment in the four variable-charge soils also followed the order Kunming oxisol > Xuwen oxisol > Lechang ultisol and Jinxian ultisol. The presence of salicylic acid increased the capacity of exchangeable Al in Kunming oxisol, Xuwen oxisol, and Jinxian ultisol, but decreased it in Lechang ultisol due to less adsorption of the acid and formation of soluble Al-salicylate complexes in solution. After free iron oxides were removed, less effect of organic acid on exchangeable Al was observed for Xuwen oxisol, which further confirmed that the iron oxides played a significant role in organic acid adsorption and had a consequent effect on the capacity of exchangeable Al in variable-charge soils. Therefore, the higher the content of iron oxides, the greater the adsorption of organic acids by soils and the greater the increase in soil exchangeable Al induced by the organic acids.     

Effect of low-molecular-weight organic anions on exchangeable aluminum capacity of variable charge soils

Low-molecular-weight (LMW) organic acids exist widely in soils and have been implicated in many soil processes, such as nutrient availability, translocation of metals, fate of heavy metals, and mineral weathering. In this paper, the effect of the LMW organic anions on the exchangeable aluminum of two variable-charge soils was examined. The results showed that the organic anions induced an increase or a decrease in the exchangeable Al, and the extent and direction of the effect depended on the nature of organic anions, surface chemical properties of soils, and pH. For example, at pH 4.5, the quantity of exchangeable Al of Oxisol in the control system was 2.65 mmol kg(-1), whereas the values in the citrate, oxalate, malonate, malate, tartarate, salicylate, and lactate systems increased by 3.25, 1.93, 1.95, 1.82, 1.28, 0.88, and 0.45 times, respectively. In contrast, the quantity of the exchangeable Al of Ultisol at pH 4.5 in the oxalate and the citrate systems decreased by 8.8 and 19.6%, respectively. The increase in the exchangeable Al was caused mainly by the increase in negative surface charge of the soils due to the specific adsorption of organic anions. The ability of organic anions at low concentrations to increase exchangeable Al for Oxisol followed the order citrate > oxalate and malonate > malate > tartarate > salicylate > maleate > lactate. This order is consistent with that of the effect of the adsorption of anions on the increase in the negative surface charge and/or the decrease in the positive surface charge of the soil. On the other hand, the organic anions could depress the exchangeable Al through the formation of soluble Al-organic anion complexes under certain conditions. The anions with small stability constants of Al-organic anion complexes, such as lactate, caused an increase in exchangeable Al with the change in surface charge of the soils, while those with large stability constants, such as citrate and oxalate, caused an increase in the exchangeable Al at low concentration and a decrease at high concentration.     

Effect of low-molecular-weight organic anions on surface charge of variable charge soils

Low-molecular-weight (LMW) organic acids exist widely in soils and have been implicated in many soil processes. In the present paper, the effect of the anions of four low-molecular-weight organic acids on the surface charge of three variable charge soils was investigated. The results showed that the presence of organic anions led to an increase in negative charge and a decrease in positive charge. Positive charges decreased to a larger extent than negative charges. The effect of different anions on surface charge followed the order citrate > malate > oxalate > acetate. For hyper-rhodic ferrasol and rhodic ferrasol, the change of positive charge decreased with the increase in pH, while that of negative charge increased with the increase in pH. Among different soils the extent of change in surface charge was related to their iron oxides content. When free iron oxides were removed from the soil, the effect of organic anions on surface charge decreased sharply. These findings may be of practical significance for variable charge soils low in nutrient-retaining capacity by increasing the retaining capacity for cations such as potassium and calcium considerably but decreasing that for anions such as nitrate remarkably.     

High ionic strength electrokinetics of melamine-formaldehyde latex

The electrokinetic potential of melamine-formaldehyde latex at high ionic strengths was measured by means of two different instruments. The present study confirms that the zeta potentials in 1 M 1-1 electrolyte solutions can be as high as +/-20 mV. The IEP of latex at low ionic strengths was at pH 11. The increase in the electrolyte concentration induced a shift in the IEP to low pH for all studied salts, and this indicates specific adsorption of the anions. The magnitude of the shift depends chiefly on the nature of the anion and increases in the series Cl < NO(3) = Br < I, and the nature of the cation (Li, Na, K, Cs) plays a rather insignificant role.     

Zeta Potential of Pyrophyllite in Aqueous Solutions of Alkaline and Alkaline Earth Metal Cations and Low‐Molecular‐Weight Organic Anions

Electrokinetic behavior of pyrophyllite in aqueous solutions of K⁺, Na⁺, Mg²⁺, and Ca²⁺ ions and effect of low‐molecular‐weight organic anions like acetate (C₂H₃O₂ ^?), oxalate (C₂O₄ ^2?), and citrate (C₆H₅O₇ ^3?) on the zeta potential was investigated. Pyrophyllite has higher negative zeta potential values in the presence of alkaline metal cations than in water, and it comes close to positive values in the presence of alkaline earth metal cations at low pH values. Results revealed that presence of low‐molecular‐weight organic anions led to a decrease in the zeta potential in the order of acetate>citrate>oxalate.     

Interaction between electrical double layers of soil colloids and Fe/Al oxides in suspensions

Phyllosilicates with net negative surface charge and Fe/Al oxides with net positive surface charge coexist in variable-charge soils, and the interaction between these oppositely charged particles affects the stability of mixed colloids, aggregation, and even the surface chemical properties of variable-charge soils. The interaction of the diffuse layers of electrical double layers between the negatively charged soil colloidal particles and the positively charged particles of goethite or gamma-Al(2)O(3) was investigated in this article through the comparison of zeta potentials between single-soil colloidal systems and binary systems containing soil colloids and Fe/Al oxides. The results showed that the presence of goethite and gamma-Al(2)O(3) increased the zeta potential of the binary system containing soil colloids and Fe/Al oxides, which clearly suggests the overlapping of the diffuse layers in soil colloids and Fe/Al oxides. The overlapping of the diffuse layers leads to a decrease in the effective negative charge density on soil colloid and thus causes a shift of pH-zeta potential curves toward the more positive-value side. The interaction of the electrical double layers is also related to the charge characteristics on the Fe/Al oxides: the higher the positive charge density on Fe/Al oxides, the stronger the interaction of the electrical double layers between the soil colloid particles and the Fe/Al oxides.     

The Isoelectric Point of an Exotic Oxide: Tellurium (IV) Oxide

The pH-dependent surface charging of tellurium (IV) oxide has been studied. The isoelectric point (IEP) of tellurium (IV) oxide was determined by microelectrophoresis in various 1-1 electrolytes over a concentration range of 0.001–0.1 M. In all electrolytes studied and irrespective of their concentration the zeta potential of TeO₂ was negative over the pH range 3–12. In other words the IEP of TeO₂ is at pH below 3 (if any). TeO₂ specifically adsorbs ionic surfactants, and their presence strongly affects the zeta potential. In contrast the effect of multivalent inorganic ions on the zeta potential of TeO₂ is rather insignificant (no shift in the IEP). In this respect TeO₂ is very different from metal oxides.     

Effect of the adsorption of lithium and borate species on the zeta potential of particles of cobalt ferrite, nickel ferrite, and magnetite

Zetametric measurements on suspensions of oxide particles (cobalt ferrite, nickel ferrite, and magnetite) representative of corrosion products from primary circuits of pressurized water reactors were performed at 25 and 70 degrees C in the presence of lithium and borate species. No effect of lithium ions was observed. Borate species cause a decrease of the isoelectric point (IEP), attributed to the sorption of borate as a negative complex MOB(OH)3(-). A predictive model based on thermodynamic calculations (2-pK and diffuse layer models) of the surface acidity constants from the data of acid-base titrations combined with an empirical relationship between the surface potential Psi 0 and the zeta potential determined by zetametry was developed. A whole set of parameters valid at 25 degrees C, in a range of ionic strength between 10(-4) and 10(-2) molL(-1) and in a range of pH between 4 and 8, was determined for this model. Increase of temperature to 70 degrees C in the presence of borate results in a decrease of IEP for cobalt ferrite and an increase of the IEP for nickel ferrite.     

Effect of ionic environments on the adsorption and diffusion characteristics of serine alkaline protease enzyme in polyethersulfone ultrafiltration membranes

Static adsorption of serine alkaline protease (SAP) enzyme on hydrophobic polyether sulfone (PES) ultrafiltration membranes in different ionic environments was investigated. The amount of SAP adsorbed on membranes was the lowest at its isoelectric point (IEP) where the maximum adsorption was obtained below the IEP of the enzyme. The extent of SAP adsorption in the phosphate buffer solutions including different salts followed the order: (NH4)2HPO4 > KH2PO4 > Na2HPO4-NaH2PO4 (buffer) > CaCl2 > ((NH4)2HPO4 + H2PO4 + CaCl2), which was consistent with the Hofmeister series. The zeta potentials of membranes contacted with the ionic species were calculated by streaming potential measurements and found that the increase in ionic strength decreased the electrical double layer thickness leading to a decrease in adsorption. A model based on mass balance was developed to calculate the diffusion coefficient of SAP in PES membranes. Employing experimental data evaluated in a diffusion cell along with the data of adsorption isotherms, diffusion coefficients of SAP in PES membranes in the presence of different ionic species were calculated. To detect the structural changes occurred, membrane surfaces were analysed by Fourier transform infrared-attenuated total reflectance (FTIR-ATR) measurements.     

The zeta potential of kaolin suspensions measured by electrophoresis and electroacoustics

The zeta potentials of kaolin dilute and concentrated suspensions were monitored using the techniques of electrophoresis and electroacoustics, respectively. The effect of addition of salt (KCl), a polymer material (Triton X-100), and an anionic surfactant (sodium dodecyl sulphate, SDS) on the suspension properties was investigated by electrophoresis. Electroacoustics was employed for the measurement of zeta potentials for the highest possible kaolin content in suspension and the effect of dilution. The effect of aging of a freshly prepared sample and kaolin isoelectric point was also studied. Using both techniques it was noted that there was no isoelectric point, just a maximum value in the magnitude of the kaolin suspension zeta potential. These maxima were observed also in the presence of Triton X-100 and SDS. An increase of the concentration of KCl and SDS in suspension shifted the maxima towards more acidic values, while in the presence of Triton X-100 the position of the zeta potential maxima remained constant. Electroacoustic techniques revealed that a freshly prepared concentrated suspension requires about six hours to equilibrate to achieve a steady zeta potential. Diluting the concentrated suspensions led to decrease of the zeta potential as ions bound to the surface desorbed and screened the surface charge. The zeta potential maxima remained unchanged even after heating the powder in an oven at 200°C (to remove any organic material) thereby suggesting that the most likely explanation for the maxima is isomorphic substitution.     

Measurements and theoretical interpretation of points of zero charge/potential of BSA protein

The points of zero charge/potential of proteins depend not only on pH but also on how they are measured. They depend also on background salt solution type and concentration. The protein isoelectric point (IEP) is determined by electrokinetical measurements, whereas the isoionic point (IIP) is determined by potentiometric titrations. Here we use potentiometric titration and zeta potential (ζ) measurements at different NaCl concentrations to study systematically the effect of ionic strength on the IEP and IIP of bovine serum albumin (BSA) aqueous solutions. It is found that high ionic strengths produce a shift of both points toward lower (IEP) and higher (IIP) pH values. This result was already reported more than 60 years ago. At that time, the only available theory was the purely electrostatic Debye-Hu?ckel theory. It was not able to predict the opposite trends of IIP and IEP with ionic strength increase. Here, we extend that theory to admit both electrostatic and nonelectrostatic (NES) dispersion interactions. The use of a modified Poisson-Boltzmann equation for a simple model system (a charge regulated spherical colloidal particle in NaCl salt solutions), that includes these ion specific interactions, allows us to explain the opposite trends observed for isoelectric point (zero zeta potential) and isoionic point (zero protein charge) of BSA. At higher concentrations, an excess of the anion (with stronger NES interactions than the cation) is adsorbed at the surface due to an attractive ionic NES potential. This makes the potential relatively more negative. Consequently, the IEP is pushed toward lower pH. But the charge regulation condition means that the surface charge becomes relatively more positive as the surface potential becomes more negative. Consequently, the IIP (measuring charge) shifts toward higher pH as concentration increases, in the opposite direction from the IEP (measuring potential).     

Zeta potential of shape-controlled TiO2 nanoparticles with surfactants

Zeta potential of shape- and size-controlled TiO₂ nanoparticles obtained with the introduction of surfactants during synthesis was measured at different pH values. A unique finding is that TiO₂ nanoparticles shaped by sodium dodecyl sulfate (SDS) have double isoelectric points (IEPs), while other shape-controlled TiO₂ nanoparticles have only one IEP. The double IEPs might be due to the complex chemistry of TiO₂ nanoparticles with the presence of impurities (Na, S, C, etc.). At neutral pH, shape- and size-controlled TiO₂ nanoparticles have more negative zeta potential values and lower IEPs than TiO₂ nanoparticles obtained without the addition of surfactants during synthesis and the commercial anatase TiO₂ nanoparticles Degussa P-25. The lower IEPs could be attributed to the presence of carbonates on particle surfaces. The IEP value of TiO₂ nanoparticles increases with an increase in calcination temperature. The results suggest that the zeta potential of TiO₂ nanoparticles can be manipulated with the addition of surfactants during the synthesis process.     

Dipolar anions are not preferentially attracted to the oil/water interface

Homogenization of hexadecane in water at pH 9 gives the same surface charge density in the presence of 0.2 mM thiocyanate or acetate anions as in the presence of chloride, indicating that these dipolar anions are not preferentially adsorbed at the oil/water interface. The decrease in the zeta potential of the emulsion droplets as the sodium salts of iodate, thiocyanate, or acetate are added from 0.1 to 10 mM is the same as that when sodium chloride is added, leading to the same conclusion. Increasing the sodium hydroxide concentration from pH 9 to 11.5 has a different effect on the zeta potential, consistent with the specific adsorption of hydroxide ion at the oil/water interface.     

Effects of low-molecular-weight organic ligands and phosphate on DNA adsorption by soil colloids and minerals

Adsorption of DNA on montmorillonite, kaolinite, goethite and soil clays from an Alfisol in the presence of citrate, tartrate and phosphate was studied. A marked decrease in DNA adsorption was observed on montmorillonite and kaolinite with increasing anion concentrations from 0 to 5 mM. However, the amount of DNA adsorbed by montmorillonite and kaolinite was enhanced when ligand concentration was higher than 5 mM. In the system of soil colloids and goethite, with the increase of anion concentrations, a steady decrease was found and the ability of ligands in depressing DNA adsorption followed the sequence: phosphate > citrate > tartrate. Compared to H2O2-treated clays (inorganic clays), a sharp decrease in DNA adsorption was observed on goethite and organo-mineral complexes (organic clays) with increasing ligand concentrations. The results suggest that the influence of anions on DNA adsorption varies with the type and concentration of anion as well as the surface properties of soil components. Introduction of DNA into the system before the addition of ligands had the greatest amount of DNA adsorption on soil colloids and goethite. Organic and inorganic ligands promoted DNA adsorption on montmorillonite and kaolinite when ligands were introduced into the system before the addition of DNA. The results obtained in this study have important implications for the understanding of the persistence and fate of DNA in soil environments especially rhizosphere soil where various organic and inorganic ligands are active.     

Simultaneous control of electrostatic micellar partition and electroosmotic flow-rate by anion-dominated partition into zwitterionic micelles

The zeta potentials of zwitterionic micelles and capillary walls have been evaluated with capillary electrophoresis. The zeta potential of the micelles is predominantly determined by the nature of anions, while cations of identical valence have marginal effects; the linear relation has been found between the induced zeta potential and the hydration energy of an anion. The zeta potential of the capillary wall is also varied with anionic natures, and there is a good correlation between micellar and capillary wall zeta potential. This strongly suggests that the zeta potential of capillary walls is determined by the partition of anions into the surfactant layer formed on the capillary wall. Thus, we can simultaneously control both the electroosmotic flow-rate and micellar surface potential (in turn electrostatic interaction between micelles and ionic solutes) by varying the type and concentration of electrolytes. This idea has been applied to the separation of aromatic cationic solutes.     

Surface behavior of nickel powders in aqueous suspensions

The colloidal behavior of nickel aqueous suspensions is studied and compared to that of NiO suspensions. Under acidic conditions, nickel readily dissolves, but no dissolution takes place at basic pH. Zeta potential is studied as a function of pH, showing that the isoelectric point (IEP) occurs at pH 3.5-4. Above the IEP there is a zeta potential plateau, which is associated to the predominance of NiO(OH) species. At pH 9 a new decrease in zeta potential is associated to NiO predominance. XPS studies support that suspensions prepared at pH >9 lead to NiO-enriched species, while suspensions prepared at lower pH form NiO(OH) species.     

Effect of pH on monolayer properties of colloidal silica particles at the air/water interface

Monodisperse colloidal silica particles were prepared by the St?ber method and hydrophobized by grafting a silane coupling agent, octadecyltrimethoxysilane. Two different types of silica particles, i.e., hydrophilic and hydrophobic silica particles were spread at the air/water interface to form the Langmuir monolayers. Monolayer properties of those particles were investigated by measuring surface pressure–area (π–A) isotherms at different subphase pH. At pH above the isoelectric point (IEP) of silica, as pH increased the π–A isotherms for the hydrophobic particles slightly shifted to larger surface area whereas those for the hydrophilic particles showed a reverse trend. At pH below the IEP, the π–A isotherms for both types of particles shifted to much larger surface area with different shapes. In order to analyze the π–A isotherm results further, the time dependence of π was examined. When pH is above the IEP, the π for the hydrophilic particles significantly decreased with increasing time and it did more at higher pH. On the other hand, the decrease in π for the hydrophobic particles was insignificant regardless of pH. For both types of silica particles, the decrease in π was minimal at pH below the IEP. These results were discussed in terms of particle desorption into the water subphase and interparticle electrostatic repulsion which is directly influenced by zeta potential.     

Surface charging of layered double hydroxides during dynamic interactions of anions at the interfaces

In this research, we investigated the effect of dynamic anion adsorption/exchange on the surface charging property of Mg(2)AlClLDH and Mg(2)AlCO(3)LDH particles that show the average zeta potential of 41 and 34 mV in the as-prepared suspension, respectively. The addition of NaCl up to 3x10(-3) M in the suspension does not obviously affect the zeta potential of both LDHs, which can be attributed to the less affinity of Cl(-) to LDH. The introduction of Na(2)CO(3) severely reduces the zeta potential at the CO(3)(2-) concentration higher than 1x10(-4) M, and to the negative value in both LDH systems at ca. 2x10(-3) M, which is presumably resulted from the exchange and the re-orientation of CO(3)(2-) in a tilt/vertical style on the surface. All four organic anions (dodecyl sulfate, folate, citrate and polyacrylate) also significantly affect the zeta potential of the LDH particles. At the lower concentrations of organic anionic groups (<1x10(-4) M), the zeta potential was slightly affected, i.e. limited exchange/adsorption. However, the concentration increasing to some point suddenly decreases and reverses the zeta potential of the LDH particles, which is presumably caused by the hydrophobic interactions that bind the hydrophobic hydrocarbon chains (especially in dodecyl sulfate) into the micelle-like bilayer bunches on the LDH surface. In addition, the effect of pH in 5.5-11.0 on the LDH particle surface charging is mainly reflected through the conversion of CO(3)(2-) to HCO(3)(-)/H(2)CO(3) when pH decreases from ca. 11 to 6, with limited contribution from protonation/deprotonation and exchange/adsorption.     

The Hofmeister Anion Effect on Ionophore‐based Ion‐selective Nanospheres Containing Solvatochromic Dyes

Recently reported ionophore‐based ion‐selective nanospheres contained pH‐independent and positively charged solvatochromic dyes. Here, we evaluate systematically the effect of anions to the fluorescence response of the nanospheres. The anion interference was found significant for anion concentrations above 10 mM. The sensor responses in the presence of various anion background was studied. While target ion (K⁺) causes the fluorescence of the nanospheres to decrease, increasing anion background also leads to lower fluorescence intensity. Lipophilic anions such as ClO₄^?, SCN^?, and I^? exhibited much more interference than hydrophilic anions (e. g., NO₃^?, Cl^?, F^?, SO₄^2?). The trend of the anion interference followed the Hofmeister series. A theoretical model was also demonstrated based on anion adsorption on the surface of the nanospheres.     

Effect of the Supporting Electrolyte on the Adsorption of Octanoic Acid at the Mercury/Electrolyte Interface

The adsorption and the changes in the interfacial composition of octanoic acid at the mercury/electrolyte interface was studied by measuring the differential capacitance at different concentrations of the supporting electrolyte, at various supporting electrolyte systems and at various temperatures. The adsorption was followed by means of capacity-potential curves in the short-term region and capacity-time transients in the long-term region at selected potentials, in all the potential ranges. A decrease of the capacitance with time was observed in most cases, followed either by a constant capacitance value or by its increase. In the short-term region, anion-surfactant complexes are formed, where the anions act as bridges between the perpendicularly oriented surfactant molecules. The larger is the negative charge of the anion, the more negative will be the charge of the anion-surfactant complex leading to a shift of the potential of maximal adsorption to more positive values. The formation of metastable condensed films is best when the hydration of the anion and its size are not too large. In the long-term region the observed increase of the capacity with time can be explained as an exchange of the metastable condensed film by a hemimicellar surface state. Here, the anions act as cores of the hemimicelles, and the hydrophilic acid groups of the amphiphiles contact the solution. Two contrary effects determine the formation of the hemimicelles. The greater is the specific adsorption of the anions, the larger is the formation of hemimicelles and the increase of the capacity. With an increase in the ability of the anions to break the water structure (lyotropic or Hofmeister series), the formation of hemimicelles will be decreased. Copyright 2000 Academic Press.