Leon Margulies

MODEL FOR COMPETITIVE ADSORPTION OF ORGANIC CATIONS ON CLAYS

The adsorption on montmorillonite of two monovalent organic cations, methylene blue (MB) and thioflavin T (TFT), was studied in four different situations: (1) separate adsorption of MB or TFT; (2) competitive adsorption of TFT and Cs; (3) competitive adsorption of the two organic cations from their equimolar solutions; and (4) adsorption of TFT on a clay whose cation-exchange capacity (CEC) had been previously saturated with MB. MB and TFT adsorbed to as much as 120% and 140% of the CEC, respectively. Cs did not appear to compete with TFT for the adsorption sites of the clay. TFT molecules adsorbed more strongly than those of MB and displaced them from the clay surface. A model was developed to evaluate the strength of the clay-organic cation interactions. The specific binding of the cations to the negatively charged surface, determined by solving the electrostatic equations, appears to account for adsorption exceeding the CEC and formation of positively charged complexes, which are due to non-coulombic interactions between the organic ligands.The charge reversal predicted by the model beyond the CEC of the clay was confirmed by microelec-trophoretic experiments. Particles in a sample of montmorillonite loaded with 50 meq TFT/100 g clay moved to the positive electrode, whereas in samples containing the two dyes, MB and TFT, coadsorbed at a total concentration of 100–120 meq/100 g clay, the particles moved to the negative electrode. Binding coefficients describing the formation of neutral and charged complexes of TFT and the clay were larger than those for MB and the clay, thereby explaining the preferential adsorption of TFT observed experimentally. The binding coefficients for the formation of neutral complexes of either MB and TFT and the clay were more than six orders of magnitude larger than those previously reported for inorganic monovalent cations.

Use of methylene blue and crystal violet for determination of exchangeable cations in montmorillonite

A procedure for the determination of cation exchange capacity (CEC) and the amounts of exchangeable cations adsorbed to montmorillonite is proposed. The method consists of a single incubation of the clay in a suspension containing a low concentration of an organic dye of large binding affinity, followed by analysis of the displaced inorganic cations by inductively-coupled plasma emission spectrometry (ICPES). The CEC is obtained by taking the largest sum of displaced exchangeable cations. Montmorillonite suspensions were incubated with methylene blue (MB) or crystal violet (CV) at dye concentrations below 4 mM, for one, three or fourteen days. For total dye concentrations up to the CEC, all the dye was adsorbed and equivalent amounts of exchangeable cations were released. Both dyes could adsorb to the clay in excess of the CEC.After one day of incubation in the presence of dye concentrations of about 50% in excess of the CEC, the total amounts of cations released were reduced to below the CEC. This reduction was interpreted as due to massive aggregation of the clay particles induced by the dye. With CV the total amounts of cations released after three or fourteen days of incubation increased and became equal to the CEC.The same CEC was found for Na-, Ca- and SWy1 crude-montmorillonite, by employing either of the dyes.

Adsorption of monovalent organic cations on sepiolite; experimental results and model calculations

Adsorption of neutral organic molecules and the monovalent organic cations methylene blue (MB) and crystal violet (CV) to sepiolite was determined experimentally and investigated by an adsorption model. The largest amounts of MB and CV adsorbed were about 4-fold of the cation exchange capacity (CEC) of sepiolite. Consequently, it was proposed that most of the above described adsorption was to neutral sites of the clay. The adsorption model considered combines the Gouy-Chapman solution and specific binding in a closed system. The model was extended by allowing cation adsorption to neutral sites of the clay, in addition to adsorption to negatively charged sites and adsorption to neutral complexes formed from 1 cation adsorbed to a negative surface site. The amount of available neutral sites was determined from the adsorption of the neutral molecule Triton-X 100 (TX100). The model could adequately simulate the adsorption of the neutral molecules TX100 and crown ether 15-crown-5 (15C5) as well as the organic cations. Due to aggregation of MB molecules in solution, their adsorption was somewhat less than that of CV at the larger added concentrations. A consideration of the molecular dimensions of TX100, MB and CV suggested that their adsorption was mostly to external sites of the clay and that their entry to the sepiolite channels was largely excluded. This interpretation is supported by infrared spectroscopy (IR) measurements, which show large perturbations of the peak corresponding to vibrations of external Si-OH groups of the clay and confirm complete occupancy of external sites by MB and CV.

A model for cation adsorption to clays and membranes

A cation adsorption model is presented and its recent applications are discussed. The model combines electrostatic equations with specific binding, and considers neutral and positively charged complexes between the negative surface sites and organic cations in a closed system. Extensions in the model account for dye aggregation in solution, and for the formation of solution complexes of inorganic cations, such as [M++ Cl−]+. The amounts of 45Ca2+ adsorbed to vesicles extracted from the plasma membranes of melon root cells could be adequately simulated and predicted. The binding coefficients determined for Ca2+, Na+, and Mg2+ are in the range of values previously deduced for binding to phospholipid components. Model calculations were applied to the test of hypotheses on the effect of salt stress on the growth of roots. The adsorption of monovalent organic cations to montmorillonite is characterized by binding coefficients that are at least six orders of magnitude larger than those of Na+, Mg2+, Ca2+, and Cd2+, or those of CdCl+ or CaCl+. Monovalent organic cations were found to adsorb 140–200% of the cation exchange capacity of the clay and to cause charge reversal. Deductions from adsorption results of acriflavin are consistent with those drawn from the application of other experimental methods. Preliminary results on the adsorption of divalent organic cations are presented. Agro-environmental applications of organo-clays are discussed.

Photoprotection of Bacillus thuringiensis kurstaki from ultraviolet irradiation

Irradiation of Bacillus thuringiensis var. kurstaki HD1 at 300-350 nm for up to 12 hr using a photochemical reactor results in a rapid loss of its toxicity to larvae of Heliothis armigera. Photoprotection of the toxic component was obtained by adsorption of cationic chromophores such as acriflavin (AF), methyl green, and rhodamine B to B. thuringiensis. AF gave the best photoprotection and a level of 0.42 mmol/g dye absorbed per gram of B. thuringiensis was highly toxic even after 12 hr of ultraviolet (uv) irradiation as compared to the control (77.5 and 5% of insect mortality, respectively). Ultraviolet and Fourier-transform infrared spectroscopic studies indicate molecular interactions between B. thuringiensis and AF. The nature of these interactions and energy or charge transfer as possible mechanisms of photoprotection are discussed. It is speculated that tryptophan residues are essential for the toxic effect of B. thuringiensis. It is suggested that photoprotection is attained as energy is transferred from the excited tryptophan moieties to the chromophore molecules.

Reduction of photodegradation and volatilization of herbicides in organo-clay formulations

The use of commercially available emulsifiable concentrate (EC) formulations of alachlor and metolachlor may be an environmental hazard because of their volatilization to the atmosphere and photodecomposition, which requires increased applied amounts. The objectives of this study were to develop organo-clay based formulations which would be less volatile and better protected from photodegradation. Bioassays have shown that the use of organo-clay formulations improves photoprotection, reduces volatilization and maintains herbicidal activity in the soil under laboratory and field conditions. Largest adsorption of herbicides by organo-clays correlates with an optimal reduction of photodecomposition and volatilization. It appears that the role of the organic cation, e.g., benzyltrimethylammonium (BTMA) is to enhance the adsorption of the non-polar herbicides to the organo-clay complex, whereas the actual photoprotection is mainly provided by the clay.

Adsorption of benzyltrimethylammonium and benzyltriethylammonium on montmorillonite; experimental studies and model calculations

The adsorption of the monovalent organic cations benzyltrimethylammonium (BTMA) and benzyltriethylammonium (BTEA) to montmorillonite was studied as a function of their concentrations and ionic strength. At low ionic strength the adsorbed amounts of BTMA and BTEA reached values of the cation exchange capacity (CEC) of the clay. An increase in the ionic strength resulted in reduction in the adsorbed amounts of the organic cations, unlike the pattern observed previously with organic monovalent cationic dyes. The reduction in adsorbed amounts of BTMA and BTEA depended on the inorganic cations according to the sequence Cs+ > Na+ > Li+, which follows the sequence of binding coefficients of these inorganic cations added. The type of the anion (that is, Cl−, ClO4−, SO42-) had no effect on the adsorbed amounts. An adsorption model which considers the electrostatic Gouy-Chapman equations, specific binding and closeness of the system could adequately simulate the adsorbed amounts of BTMA and BTEA and yield predictions for the effect of the ionic strength and concentration of electrolytes. The binding coefficient employed was K = 5000 M−1 for the formation of neutral complexes of BTMA and BTEA. This value is larger than those found for the inorganic cations but is several orders of magnitude below those found for the monovalent dyes. The binding coefficients for the formation of charged complexes of BTMA and BTEA were 20 and 5 M−1, respectively. The basal spacing of the clay did not change significantly with the adsorbed amounts of both BTMA and BTEA up to the CEC.

PHOTOSTABILIZATION OF A NITROMETHYLENE HETEROCYCLE INSECTICIDE ON THE SURFACE OF MONTMORILLONITE

The photochemical stability of the insecticidal compound tetrahydro-2-(nitromethylene)-2H-1,3-thiazine (NMH) adsorbed on montmorillonite (Mont), in the presence or in the absence of a second organic chromophore was studied. Two different organic dyes were investigated as possible stabilizers of NMH: the divalent cation methyl green (MG) and the monovalent cation thioflavin T (TFT). Samples of free NMH and of the adsorption complexes Mont-NMH, Mont-MG-NMH, and Mont-TFT-NMH were exposed to direct sunlight, and the residual insecticidal activity was estimated. Some photostabilization of the pesticide adsorbed to the clay was observed. The highest degree of photoprotection was achieved in samples containing 0.5 mmole of TFT and 0.2 mmole of NMH/g clay. Increasing the load of TFT to 0.8 mmole/g clay resulted in a complete loss of photostabilization. The interactions of the organic molecules at the clay surface were studied by UV-VIS absorption and Fourier-transform infrared spectroscopy. For the Mont-NMH and Mont-MG-NMH complexes, the observed photostabilization is probably due to clay-NMH interactions. In the Mont-TFT-NMH complex specific interactions between the cationic dye and the pesticide molecules probably occurred as well.

Movement of metolachlor in soil: effect of new organo-clay formulations

The use of commercially available formulations of metolachlor has resulted in its leaching and migration to water sources. Formulations of metolachlor designed to reduce its leaching in soil have been prepared by adding the herbicide dissolved in an organic solvent or in water to organo-clay complexes. Best formulations were made when the organo-clay complex was formed by adsorbing the monovalent organic cations benzyltrimethylammonium (BTMA) or benzyltriethylammonium (BTEA) onto sodium montmorillonite (Mont) at 0.5 or 0.8 mole kg−1 clay. Adsorption of metolachlor to organo-clays followed the sequence Mont-BTMA 0.5 > Mont-BTMA 0.8 > Mont-BTEA 0.8 > Mont-BTEA 0.5 > Mont. Fourier transform infrared (FTIR) analysis demonstrated the occurrence of shifts of several peaks of adsorbed metolachlor relative to the free herbicide, indicating the existence of strong interactions between metolachlor molecules and the organo-clay surface. Leaching studies employing organo-clay and commercial formulations were carried out under greenhouse and field conditions. Metolachlor applied as organo-clay formulations leached less than the commercial formulation. Organo-clay formulations prepared by adding the herbicide as a water solution showed less leaching in the soil profile than those made by using organic solvent. Under greenhouse conditions, the herbicidal activity of organo-clay formulations was similar to that of the commercial one. Under field conditions, leaching from Mont-BTMA 0.5-metolachlor was less than that from the commercial formulation, demonstrating the environmental and agricultural advantages of the organo-clay formulations of metolachlor. © 1999 Society of Chemical Industry

Adsorption of methyl green on montmorillonite

Adsorption of the dye methyl green (MG) on Na -montmorillonite (Clay) takes place through a cation exchange mechanism. At low and high MG loads, each MG molecule replaces approximately two and one Na+ ions, respectively. Interactions between MG and Clay were studied using visible absorption and FTIR spectroscopies, and the orientation of the adsorbed molecules were determined by infrared linear dichroism and X-ray powder diffraction. The dye molecules are preferentially oriented with their plane parallel to the clay surface. The influence of MG load on the adsorption of two additional organic molecules, benzyl benzoate and benzophenone, was also studied.