Slow-release formulations of sulfometuron incorporated in micelles adsorbed on montmorillonite

The design and tests of slow-release formulations of sulfometuron (SFM), an anionic sulfonylurea herbicide, are described. The formulations are based on incorporation of the herbicide in octadecyltrimethylammonium (ODTMA) micelles, which adsorb on a clay mineral, montmorillonite. An optimization of herbicide/micelle clay ratios yielded high adsorption of SFM (95%), and at a 1% (w/w) water suspension only 0.5% of the adsorbed SFM was released at times varying from hours to 9 days. An analytical test in Seville soil showed that under excessive irrigation (400 mm) 100% of the commercial formulation leached, whereas the micelle-clay formulations showed only 50-65% elution. A plant bioassay in Rehovot soil showed that the commercial dispersible granule formulation (Oust, 75% ai sulfometuron methyl) yielded only 23% root elongation inhibition at the top 5 cm of the soil, whereas complete inhibition was achieved with the micelle-clay formulation. The detected concentration of SFM for the micelle-clay formulation at a depth of 15-20 cm was half of that detected for the commercial one, indicating a reduction in leaching when applying the micelle-clay formulation. A 10-fold reduction in the applied dose of SFM in the micelle-clay formulations resulted in good herbicidal activity of 60-87% inhibition. These characteristics make the new formulation promising from the environmental and economic points of view.     

Montmorillonite-phenyltrimethylammonium yields environmentally improved formulations of hydrophobic herbicides

This study aimed to design formulations of hydrophobic herbicides, alachlor and metolachlor, by adsorbing them on the clay mineral montmorillonite preadsorbed by the small organic cation phenyltrimethylammonium (PTMA). An adsorption model that considers electrostatics and specific binding and the possibility of cation adsorption above the cation exchange capacity (CEC) could explain and yield predictions for PTMA adsorption in the presence of NaCl concentrations from 0 to 500 mM. Adsorption of alachlor and metolachlor from aqueous solution on a clay mineral preadsorbed by PTMA was determined by GC and modeled by Langmuir equation. Herbicide interactions with the organoclay were studied by Fourier transform infrared spectroscopy. Leaching of herbicides was determined by a bioassay using a column technique and Setaria viridis as a test plant. The adsorbed amounts of alachlor and metolachlor on montmorillonite preadsorbed by PTMA at a loading of 0. 5 mol/kg (Mont-PTMA0.5) were higher than at a loading up to the CEC, that is, 0.8 mol/kg, and were higher than those obtained by using several other organic cations. Herbicide formulations based on Mont-PTMA0.5 yielded the largest shifts of the infrared peaks of the herbicides. These formulations based on Mont-PTMA0.5 gave slower release and showed improved weed control in comparison with formulations based on other organoclays. These formulations maintained herbicidal activity in the topsoil and yielded the most significant reduction in herbicide leaching.     

Organo-clay formulation of acetochlor for reduced movement in soil.

This study aimed to design ecologically acceptable formulations of acetochlor by adsorbing it on montmorillonite exchanged by a small organic cation, phenyltrimethylammonium (PTMA). Adsorption of acetochlor on the clay mineral exchanged with different organic cations and its release from these complexes were determined by GC and modeled by Langmuir equation. Interactions between acetochlor molecules and the exchanged organic cation on the clay surface were studied by Fourier transform infrared spectroscopy. Leaching of acetochlor in soil was determined by a bioassay using a column technique and Setaria viridis as a test plant. The adsorbed amounts of acetochlor on montmorillonite exchanged by PTMA at a loading of 0.5 mmol/g of clay were higher than at a loading up to the cation-exchange capacity, i.e., 0.8 mmol/g, and were higher than obtained by using a clay mineral exchanged by other organic cations. Preloading montmorillonite by PTMA at 0.5 mmol/g yielded maximal shifts of the infrared peaks of the herbicide. The above formulation of acetochlor yielded slow release in water and showed improved weed control in field and greenhouse experiments in comparison with the commercial formulation. The PTMA-clay formulation of acetochlor maintained herbicidal activity in the topsoil and yielded the most significant reduction in herbicide leaching and persistence under field conditions. The application of this formulation can minimize the risk to groundwater and can reduce the applied rates.     

Selective modification of clay minerals for the adsorption of herbicides widely used in olive groves

Ground and surface water contamination by herbicides applied to olive groves in Spain and other Mediterranean countries is demanding strategies to prevent and remediate the environmental problems repeatedly caused by such herbicides. In this study, six different organic cations (L-carnitine, spermine, hexadimethrine, tyramine, phenyltrimethylammonium, and hexadecyltrimethylammonium) were incorporated into Na-rich Wyoming montmorillonite (SWy-2) and Ca-rich Arizona montmorillonite (SAz-1) at two different loadings (50% and 100% of the cation exchange capacity of the clays) as a strategy to enhance the affinity of the clay minerals for three herbicides widely used in olive groves: terbuthylazine, diuron, and MCPA. The modified montmorillonites were characterized and tested as adsorbents of the herbicides through batch adsorption tests. At the experimental conditions used, some of the modified montmorillonites removed more than 95% of the herbicide initially present in aqueous solution, whereas the unmodified clays removed less than 15%. All three herbicides displayed very strong affinities for SAz-1 exchanged with hexadecyltrimethylammonium cations, particularly when these were incorporated at 100% of the cation exchange capacity of the clay mineral. Terbuthylazine and diuron also displayed very strong affinities for SWy-2 exchanged with L-carnitine and spermine, respectively. The chemical characteristics of the organic cation greatly influenced the adsorptive properties of the resultant organoclay. The herbicides were in general reversibly adsorbed by the modified clays. The results indicate that some of the tested modified clays could be suitable for the removal of the assayed herbicides from contaminated water and also as possible supports for the design of slow release formulations of such herbicides to attenuate their environmental impact when used in high-risk scenarios such as olive groves.     

Herbicide solubilization in micelle-clay composites as a basis for controlled release sulfentrazone and metolachlor formulations

Sulfentrazone and metolachlor have been detected in groundwater due to extensive leaching. To reduce herbicide leaching and increase weed control, we have developed, designed, and tested controlled release formulations (CRFs) for both herbicides based on their solubilizion in cationic micelles and adsorption of the mixed micelles (surfactant and herbicide) on a clay mineral, montmorillonite. A better understanding of solubilizing anionic (sulfentrazone) and nonionic (metolachlor) organic molecules in cationic micelles was reached. The percent of active ingredient in the formulations was much higher than previously designed CRFs due to the enhanced solubilization of the herbicides in the micelles and due to their adsorption on the clay. Both CRFs demonstrated controlled release (compared to the commercial formulations) when applied to a thin soil layer. A bioassay in soil columns determined that the new sulfentrazone and metolachlor CRFs significantly improve weed control and reduce leaching (for the latter) in comparison with the commercial formulations.     

Adsorption and binding of peptides on homoionic montmorillonite and kaolinite

The adsorption and binding (amount retained after extensive washing) of peptides (two, three or four amino acids with isoelectric points ranging from pH 3.31 to 6.81) on montmorillonite (M) and kaolinite (K) made homoionic to H, Na, Ca, Zn, Al or La were studied. The amount of peplide adsorbed or bound varied with the type of clay, the type of cation saturating the clay, and the constitutive amino acids of the peptides. Di-, tri- and tetraglycine were adsorbed to a greater extent on M than on K. A larger amount of the basic peptide, l-alanyl-l-lysine, than of the acidic peptide, l-aspartylglycine, was adsorbed. The heterocyclic peptides, l-histidylglycine and l-prolyl-l-phenylalanylglycyl-l-lysine, were preferentially adsorbed on M homoionic to di- and trivalent cations. Only l-aspartylglycine, l-histidylglycine. l-alanyl-l-lysine and l-prolyl-l-phenylalanylglycyl-l-lysine were bound on M, and only diglycine, tetraglycine and l-prolyl-l-phenylalanylglycyl-l-lysine were bound on K.     

Organo-clay formulations of the hydrophobic herbicide norflurazon yield reduced leaching

The study aimed to reduce leaching of the hydrophobic herbicide norflurazon (4-chloro-5-methylamino-2-(alpha,alpha, alpha)-trifluoro-m-tolylpyridazin-3-(2H)-one) by adsorbing it on clays or organo-clays. The surface of the clay mineral montmorillonite was modified from hydrophilic to hydrophobic by preadsorbing it with organic cations, of which thioflavin-T (TFT) at a loading corresponding to (5)/(8) of the cation-exchange capacity of the clay mineral yielded the highest affinity of adsorption of norflurazon. Pillared clay (PC) used without organic cations exhibited enhanced affinity for norflurazon adsorption, much higher than that of montmorillonite or sepiolite. Fourier transform infrared (FTIR) results showed interactions between aromatic moieties of preadsorbed TFT and the herbicide. Stronger interaction of the herbicide with a clay mineral or organo-clay corresponded to its slower release. Formulations prepared on the basis of montmorillonite-TFT and PC were more effective in reducing herbicide leaching in soil columns in comparison to the commercial formulation, whereas the herbicidal efficiencies were comparable.     

胡敏酸对铵钾在粘土矿物上交互作用的影响

Interaction of ammonium (NH+4) and potassium (K+) is typical in field soils. However, the effects of organic matter on interaction of NH+4 and K+have not been thoroughly investigated. In this study, we examined the changes in major physicochemical properties of three clay minerals (kaolinite, illite, and montmorillonite) after humic acid (HA) coating and evaluated the influences of these changes on the interaction of NH+4 and K+on clay minerals using batch experiments. After HA coating, the cation exchange capacity (CEC) and specific surface area (SSA) of montmorillonite decreased significantly, while little decrease in CEC and SSA occurred in illite and only a slight increase in CEC was found in kaolinite. Humic acid coating significantly increased cation adsorption and preference for NH+4, and this effect was more obvious on clay minerals with a lower CEC. Results of Fourier transform infrared spectrometry analysis showed that HA coating promoted the formation of H-bonds between the adsorbed NH+4 and the organo-mineral complexes. HA coating increased cation fixation capacity on montmorillonite and kaolinite, but the opposite occurred on illite. In addition, HA coating increased the competitiveness of NH+4 on fixation sites. These results showed that HA coating affected both the nature of clay mineral surfaces and the reactions of NH+4 and K+with clay minerals, which might influence the availability of nutrient cations to plants in field soils amended with organic matter.     

Adsorption mechanisms of thiazafluron in mineral soil clay components

The adsorption of the herbicide thiazafluron, 1,3-dimethyl-1-(5-trifluoromethyl-1,3,4-thiadiazol-2-yl)urea, by three smectites, illite, kaolinite, ferrihydrite and the clay fraction of an illitic soil (54.9% illite, 17.0% montmorillonite and 24.9% kaolinite) and a montmorillonitic soil (33.9% illite, 55.0% montmorillonite and 11.1% kaolinite) has been determined. Thiazafluron adsorbed on neither kaolinite nor iron oxide. The adsorption isotherms on smectites and illite conformed to the Freundlich equation. Values of K_f-obtained for smectites were larger than for the illite and increased as the layer charge of the smectite decreased. Desorption of thiazafluron on smectites was shown to be highly irreversible. Adsorption isotherms of thiazafluron on different homoionic montmorillonite samples suggest an important role of the exchangeable cations in the adsorption. Infrared spectra and X-ray diffraction analysis of the complexes of thiazafluron with homoionic montmorillonites indicated that thiazafluron adsorbs in the interlamellar space of the smectites, mainly by substitution of water molecules associated with the exchangeable cations through the carbonyl-amide group and formation of H-bonds or waterbridge between the NH group of the amide and the basal oxygens of the montmorillonite. The illitic soil clay adsorbed more of the herbicide than the montmorillonitic one did, suggesting that illite and montmorillonite may be present in soils in altered forms giving rise to different adsorption capacities from those of the pure minerals.     

Sulfosulfuron incorporated in micelles adsorbed on montmorillonite for slow release formulations

Slow release formulations of the anionic herbicide sulfosulfuron (SFS) were prepared by incorporating it in micelles of an organic cation octadecyltrimethylammonium, which adsorb on the clay-mineral montmorillonite. The fraction of SFS adsorbed on the micelle-clay complex reached 98%, whereas for monomer-clay complexes, its adsorption was insignificant. Fluorescence studies showed surface contact between the micelles and the clay surface. The rate of SFS release from the micelle-clay formulations in aqueous suspensions was slow (<1%, 72 h). Spraying SFS formulations on a thin soil layer in a funnel, followed by irrigations (50 mm), resulted in complete elution of SFS from the commercial formulation (dispersible granular) versus 4% from the micelle-clay formulation. A plant bioassay in Rehovot soil showed that these respective formulations yielded 23 and 65% of shoot growth inhibition of foxtail. Consequently, the slow release micelle-clay formulations of SFS yield significantly reduced leaching and enhanced biological activity, thus providing environmental and agricultural advantages.     

Adsorption,desorption and extractability of Zn in some Algerian soils under orange cultivation

The Zn adsorption/desorption in some Algerian soils, which are under orange cultivation, was studied and the results obtained were analyzed using Langmuir equation. The maximum amount of Zn adsorbed, in majority of cases, varies between 60 and 80 % of the cation exchange capacity. As regards sequential desorption, the EDTA desorbed about 80 %of the Zn adsorbed, whereas, the desorption through 1 N KCI averaged about 15 % only. The adsorption maximum (Sm) and desorption maximum (Rm) correlate significantly with various soils properties, like clay content, cation exchange capacity and pH. The calculation of distribution coefficient (Kd) and adsorption density of Zn (r) indicates that the metal above 2.5 · 10 ions/m2 is adsorbed through ion exchange, whereas below this value, the ion is most possibly adsorbed due to specific adsorption mechanisms.     

Reactions of nucleic acid bases with inorganic soil constituents

The adsorption at pH's 4, 6 and 8 of adenine, guanine, cytosine, thymine and uracil on clays (montmorillonite, illite and kaolinite), Fe- and Al-oxides (goethite, hematite and gibbsite), a soil, and on a laboratory-prepared fulvic acid-montmorillonite complex was investigated. Portions of the clays and soil were saturated with H⁺, Fe³⁺ and Ca²⁺.Quantitatively, the extent of adsorption of nucleic acid bases by the clays was proportional to their exchange capacities, but the nature of the dominant cation had only minor effects. By contrast, the adsorption was strongly affected by pH, tending to decrease with increase in pH. Adsorption on goethite and gibbsite was lower than that on clays, while adsorption of nucleic acid bases on soils was slightly lower than that on oxides. The fulvic acid-montmorillonite complex adsorbed substantial, although smaller amounts of purines and pyrimidines, than did montmorillonite alone. The main adsorption mechanism at pH 4 appeared to be cation exchange whereas at pH 8 complex formation between the nucleic acid bases and cations on inorganic surfaces seemed to occur.The results of this and earlier work show that both inorganic and organic soil constituents adsorb nucleic acid bases. Which adsorption reaction predominates will depend on the clay and organic matter content and on the pH.     

POSITIVE ADSORPTION FROM MIXTURES OF THREE ELECTROLYTE SOLUTIONS

The double layer theory was used for estimating the relative amounts of positively adsorbed cations when a mixture of three salts with mono-, di-, and trivalent cations is present in clay electrolyte systems. It is shown that the adsorbed cations are dominated by the trivalent cation when the salts are present at equal concentrations.     

Phosphate adsorption by Na−, Mg− and Ca−saturated soil clays

Phosphate adsorption by the homoionic clay (Na, Ca, Mg) of three soils with widely varying mineralogy obeyed the Langmuir isotherm. The Langmuir constants b and k were a function both of the nature of the dominant clay mineral present and of the saturating cations following the order: Ca⁺⁺ ? Mg⁺⁺ ? Na⁺. This order was in agreement with those predicted by the diffuse double layer theory. The sample having montmorillonite when saturated with sodium, exhibited a negative adsorption of phosphorus which changed to a large positive adsorption in the presence of 0.1 N NaCl; It was concluded that the exchangeable cations influenced the extent of P adsorption by controlling the accessibility of the edge clay surfaces to phosphate ions.     

Interactions between montmorillonite and fulvic acid

The isotherms at 20°C for the adsorption of ¹⁴C-labelled fulvic acid from aqueous solutions by montmorillonite containing different exchangeable cations, have been determined. Below a concentration of 0.45 mg/ml and at near neutral pH, all samples give linear isotherms, the slope of which increases in the order Ba²⁺ < Ca²⁺ < Zn²⁺ < La³⁺ < Al³⁺ <Cu²⁺ < Fe³⁺. In the absence of interlayer expansion, the shape of the isotherms is interpreted in terms of solute entry into intercrystalline pores within a clay domain. The affinity of fulvic acid for the clay surface is related to the ionic potential or polarising power of the exchangeable cation. It is inferred that fulvic acid adsorbs by hydrogen bonding between an anionic group of the acid and a water molecule in the primary hydration shell of the saturating cation. Comparison of the data with those for the humic acid extracted from the same organic matter source, indicates that secondary interactions between adsorbed molecules or directly with the montmorillonite surface, contribute to the overall affinity. With samples saturated with Al³⁺, Fe³⁺, and Cu²⁺ ions, part of the adsorbed fulvic acid may also be attached to the clay by a complexation reaction involving the metals as such, or when they exist as polyhydroxy compounds at the mineral surface.     

电解质种类和浓度影响磷酸根解吸的机理研究

本文研究了吸附性阳离子、电解质浓度和组成影响几种矿物和土壤吸附态磷的解吸的机理。结果表明,吸附性阳离子影响磷酸根解吸与离子桥有关。桥接静电场愈强,被束缚磷的释放就愈困难。电解质阳离子对磷酸根解吸的影响则取决于其对表面负电荷的屏蔽效应。阳离子电价高,屏蔽作用大,磷解吸就少。电解质浓度影响吸附态磷的解吸主要与表面电位的变化有关。当pH>PZC值时,提高电解质浓度降低表面负电位,从而减少磷的吸附;当pH<PZC时,提高电解质浓度则降低表面正电位,促进磷的解吸。磷酸根解吸盐效应零点(P_PZSE)值一般都介于土壤或矿物样品吸附磷酸根前后测得的两个PZC值之间。不同浓度电解质溶液中磷解吸量之差与吸附层电位变化量(△ψ_x)呈正相关。     

THE INTERACTION OF PARAQUAT (1: 1'-DIMETHYL 4:4'-DIPYRIDYLIUM DICHLORIDE) WITH MINERAL SOILS

Investigation of the adsorption of 1:1′-dimethyl 4:4′-dipyridylium (paraquat) dichloride by a range of soils, using a solution-equilibration technique, has shown that the adsorption is characterized by three factors: 1. Up to a limiting value, defined as the Strong Adsorption Capacity (SAC), the solution concentration of paraquat is reduced below the level of chemical detection by suspended soil: this strongly adsorbed paraquat is preferentially held against 0.1 to 2.0N solutions of ammonium ion. A range of strengths of adsorption probably exists within the strong adsorption range, but the greater part of the strongly adsorbed material is de-activated herbicidally; this accounts for the herbicidal de-activation of paraquat in soils. 2. Removal of soil organic matter by treatment with hydrogen peroxide usually does not greatly change the SAC. Strong adsorption of paraquat is primarily a property of clay minerals, and the presence of expanding lattice minerals is of particular importance. 3. For fortifications above the strong adsorption region, there is a region of weaker adsorption but the total adsorption capacities of soils at saturation are less than their cation exchange capacities for inorganic cations. Taken with the difficulty of displacement, this indicates that the adsorption of paraquat is strongly influenced by factors other than simple electrostatic interaction.     

Formation of 2,4–D complexes on montmorillonites – an ab initio molecular dynamics study

Sorption of the anionic form of the pesticide 2,4–D (2,4–dichlorophenoxyacetic acid) on the surface of the clay mineral montmorillonite was investigated using a short-time ab initio molecular dynamics (MD) simulation at room temperature. Three different situations were modelled: sorption on a dry surface, on a hydrated surface and an intercalation between montmorillonite layers. In all three cases, the calcium cation compensates the excess negative charge of the montmorillonite layer and the negative charge of the 2,4–D anion. It was found that in all models with direct contact of the Ca²⁺ cation with the montmorillonite layer, the most stable position of Ca²⁺ is above the ditrigonal hole of the mineral layer. While in the case of a dry surface very stable bidentate binding is created between the 2,4–D anion and the Ca²⁺ cation, the formation of the monodentate complexes is preferred in all models that include water molecules. Hydrogen bonds formed between water molecules and the 2,4–D anion make a considerable contribution to the formation of the monodentate complexes. Tetrahedral substitutions in the montmorillonite layer have a significant effect on the formation of the complexes of any type. However, the MD simulations did not support the role of Ca²⁺ as a cation bridge in the adsorption mechanism. Calculations showed that hydrated 2,4–D···Ca²⁺ complexes are thermodynamically more stable than complexes in which the Ca²⁺ cation acts as a bridge to the surface. On the other hand, it is possible that phyllosilicates with a greater concentration of isomorphic substitutions (e.g. mica) will be able to form stable surface complexes with a cation bridge mechanism.     

THE MICROPORE SIZE DISTRIBUTIONS OF CLAY MINERAL SYSTEMS

The micropore (<100 Å) size distributions of compacted clay mineral systems have been examined by means of low-temperature N₂ sorption isotherms to saturation. The calculation of pore sizes was based on the application of the Kelvin equation, corrected for the adsorbed film thickness, to the parallel plate model. Clay-mineral systems have been shown to exist with a high degree of parallel alignment of the plate-shaped crystals. This results in a high proportion of microporosity and in relatively discrete pore sizes. In montmorillonite clays much intercrystalline overlap area in the dry matrix is inaccessible to N₂ sorption. The structure of these systems may be governed partly by the effect, in suspension, of electrostatic interaction between the charged particles on crystal size, but largely by mechanical interaction on sedimentation and the size of the exchangeable cations present.     

Lead ion adsorption on montmorillonite–Al hydroxide polymer systems

Clay–Al hydroxide polymer systems (CAlHO) can bind heavy metals effectively. Their adsorption behaviour depends on the type of metal. We studied the dependence of Al‐loading and pH on the adsorption of Pb to Na‐saturated montmorillonite–Al hydroxide polymer systems. The available binding sites on the Al hydroxide polymers (AlHO) had a strong affinity for Pb ions, whereas a minor amount of Pb was bound to the clay surface. The pH had a pronounced effect on the Pb binding to the AlHO. At pH 6.0, AlHO effectively adsorbed Pb. The amount of Pb adsorbed to the AlHO, expressed per mole Al, increased with increasing amount of AlHO fixed. Lead bound to the AlHO could easily be removed by exchange and is therefore reversibly bound to the AlHO. Probably, Pb is outer‐sphere bound to the AlHO and an electrostatic bonding mechanism is involved. At pH 5.0 there was almost no adsorption of Pb to the AlHO, and the adsorption of Pb to the clay surface was limited because Al³⁺ ions competed with Pb²⁺ for exchangeable sites. At pH 6.6 and relatively large Pb concentrations, separate precipitates of Pb(OH)₂ and Al(OH)₃ were formed. Results from experiments in pure clay systems suggest that the Pb(OH)₂ precipitate was present as positively charged Pb polymers.