Retention of Metamitron by Model and Natural Particulate Matter

Abstract

Adsorption isotherms of metamitron on model soil colloidal components: kaolinite, illite, montmorillonite, iron oxide and humic acid, and their binary associations were obtained using a batch equilibration procedure. Sorption parameters, K_f and n_f, were calculated by fitting the sorption data to the Freundlich equation and results obtained for binary associations were compared with those obtained for the individual model components. The sorption efficiency of the humic acids and their binary associations was measured as Koc. The adsorption behaviour of the < 2 μm fraction of two soils from Southern Spain was also studied as natural particulate matter. Montmorillonite and humic acids were found to be the most important components responsible for metamitron retention by the model adsorbents studied. On the contrary, metamitron showed little interaction with kaolinite, illite or iron oxide. These individual adsorption behaviours were reproduced in the montmorillonite-iron oxide-humic acid binary systems, but with differences suggesting changes on the surface properties upon association. Differences in Koc values of isolated humic acids and their associations indicate that the interaction transforms the humic acid surfaces and suggest different types of bonding between colloids and metamitron. The results obtained with model adsorbents and their associations were in agreement with the highest adsorption of metamitron found for the natural clay fraction of two soils which displayed the largest adsorption in that with the highest content in montmorillonite and organic carbon. The importance of organic matter and montmorillonite in metamitron adsorption by colloidal components was also shown by the decrease in K_f and the increase in Koc observed after removal of organic matter from the soil clay fraction with the highest organic carbon content.     

Sorption interactions of volatile organic compounds with organoclays under different humidities by using linear solvation energy relationships

Organoclays are usually used as sorbents to reduce the spread of organic compounds and to remove them at contaminated sites. The sorption equilibrium and the mechanisms of volatile organic compounds (VOCs) on organoclays under different humidities are helpful for developing efficient organoclays and for predicting the fate of VOCs in the environment. In this study, the organoclay was synthesized through exchanging inorganic cations by hexadecyltrimethyl ammonium (HDTMA) into montmorillonite, resulting in 12?% of organic content. The surface area of organoclay was smaller than the unmodified clay due to the incorporation of organic cations into the interlayer. Both adsorption on organoclay surface and partition into the incorporated HDTMA in organoclay played roles on the sorption process. Compared the sorption coefficients in montmorillonite and different modified clays, the incorporated organic cations overcame the inhibition effect of hydrophilic surface of clay on the sorption process of hydrophobic organic compounds from water. The sorption coefficients of VOC vapors on organoclay were further characterized using a linear solvation energy relationship (LSER). The fitted LSER equations were obtained by a multiple regression of the sorption coefficients of 22 probe chemicals against their solvation parameters. The coefficients of the five-parameter LSER equations showed that high HDTMA-content montmorillonite interacts with VOC molecules mainly through dispersion, partly through dipolarity/polarizability and hydrogen-bonds as well as with negative π-/n-electron pair interaction. The interaction analysis by LSERs suggests that the potential predominant factors governing the sorption of VOCs are dispersion interactions under all tested humidity conditions, similar with the lower level modified clay. The derived LSER equations successfully fit the sorption coefficients of VOCs on organoclay under different humidity conditions. It is helpful to design better toxic vapor removal strategy and evaluate the fate of organic contaminants in the environment.     

Effect of the intercalation conditions of a montmorillonite with octadecylamine

Intercalation of montmorillonite with octadecylamine under several conditions is reported. Octadecylamine was protonated in situ with HCl to obtain octadecylammonium cations. Water and water/ethanol mixtures were used as reaction medium, and the ratios amine/clay and HCl/amine were also varied. Intercalation was successful when the amine/clay ratio was in the range 1-3 mmol/g; optimal results were obtained for an amine/clay ratio of 2.0 mmol/g. For a given amine/clay ratio, the HCl/amine ratio also influences the intercalation. Basal spacings of the intercalated solids were between 13.4-36.7 angstroms. The amount of organic matter incorporated into the solids also varied widely; up to 40 wt% is fixed. Specific surface area is very low in all the intercalated solids because of the blockage of the clay porosity by the organic molecules. Co-intercalation of octadecylammonium and of the inorganic polycation [Al13O4(OH)24(H2O)12]7+ was also considered, giving rise to intercalated solids with basal spacings between 17 and 22 A, also with a high fixation of organic matter.     

The Adsorption of Herbicides and Pesticides on Clay Minerals and Soils. Part 2. Atrazine

The adsorption of atrazine and two model compounds,2-chloropyrimidine and 3-chloropyridine on clay minerals(bentonite, montmorillonite and kaolinite), organic matter (humic acid) and soil (with and without organic matter) has beenstudied using FT-infrared spectroscopy (IR), thermogravimetric analysis (TGA), high pressureliquid chromatography (HPLC) and X-ray diffraction (XRD).3-Chloropyridine, 2-chloropyrimidine and atrazine were adsorbedthrough hydrogen bonding on bentonite, montmorillonite, humic acid and soil. In addition tohydrogen bonding, protonation of 3-chloropyridine and atrazine was also observed.In the adsorption of 2-chloropyrimidine on bentonite and montmorillonitean ion exchange mechanism also occurred. No adsorption of 3-chloropyridine or 2-chloropyrimidine wasobserved on the kaolinite clay mineral.Both the clay minerals and organic matter of soil contribute tothe adsorption of organic compounds on soil but the clay minerals bentonite and montmorilloniteplay a major role in their adsorption on soil.     

Real time HR-MAS NMR: application in reaction optimization, mechanism elucidation and kinetic analysis for heterogeneous reagent catalyzed small molecule chemistry

A novel application of in situ (1)H high-resolution magic angle spinning (HR-MAS) NMR technique for real-time monitoring of H(2)SO(4)-silica promoted formation of 2, 2-disubstituted quinozolin-4(3H)-ones is reported. The detailed NMR spectroscopic data led to elucidation of the mechanism, reaction optimization, kinetics and quantitative analysis of the product accurately and efficiently. The translation of the optimized parameters obtained by (1)H HR-MAS NMR in the wet laboratory provided similar results. It is proposed that (1)H HR-MAS has a potential utility for optimization of various organic transformations in solid supported catalyzed reactions.     

The Adsorption of Herbicides and Pesticides on Clay Minerals and Soils. Part 1. Isoproturon

The adsorption of isoproturon and two model compounds, N,N-dimethylurea and4-isopropylaniline, on clay minerals (bentonite,montmorillonite and kaolinite), organic matter (humic acid) and soil (with and without organic matter) has been studied using FT-infrared spectroscopy (IR), thermogravimetric analysis (TGA), high pressure liquid chromatography (HPLC) and X-ray diffraction (XRD).N,N-dimethylurea interacted with bentonite and montmorillonite by the coordination of the carbonyl group, directly or indirectly through water molecules, with exchangeable cations. Adsorption on humic acid was due to hydrogen bonding with the active sites of the adsorbent. The amino group ofN,N-dimethylurea appears tobe relatively inactive during adsorption. The mechanisms involved in the adsorption of 4-isopropylaniline were hydrogen bonding and protonation. No adsorption of 4-isopropylaniline was observed on kaolinite. The investigation of isoproturon suggested that both the carbonyl and amino groups of isoproturon were involved in interactions with the active sites of the adsorbents. Both the clay minerals and organic matter of soil contribute to the adsorption of organic compounds on soil but the clay minerals bentonite and montmorillonite play a major role in their adsorption on soil.     

Adsorption of phenanthrene on organoclays from distilled and saline water

Isotherms of phenanthrene adsorption on different organoclay complexes were obtained using the HPLC technique to understand the adsorption behavior and to characterize the effect of sodium chloride (NaCl) on the adsorption. The adsorbed amounts of phenanthrene on montmorillonite exchanged by organic cations such as tetraheptylammonium, benzyltrimethylammonium, hexadecyltrimethylammonium, or tetraphenylphosphonium were several times higher than those obtained using montmorillonite clay without surface modification. At the same equilibrium concentration, the adsorbed amount of phenanthrene is higher on clay modified with benzyltrimethylammonium than on clay modified with hexadecyltrimethylammonium or other cations. Adsorption of phenanthrene on clay modified with benzyltrimethylammonium increased dramatically as the concentration of NaCl increased up to 150 g/l in the aqueous solution. The shape of the curves obtained can be classified as S-type. The adsorption data obtained from salinity experiments support a mathematical model that links the Langmuir constant with the salinity constant. This model may be useful to predict the equilibrium concentration of a contaminant in saline solution. FTIR studies showed strong interactions between the aromatic rings of phenanthrene and the preadsorbed benzyltrimethylammonium on clay surfaces.     

Nickel Sorption Mechanisms in a Pyrophyllite-Montmorillonite Mixture

Nickel sorption on pyrophyllite, montmorillonite and a 1:1 pyrophyllite-montmorillonite mixture was studied at pH 7.5 and a reaction time of 40 min. The main modes of Ni uptake under these reaction conditions are adsorption on montmorillonite and surface precipitation on pyrophyllite. For the clay mixture, where adsorption on the montmorillonite component and surface precipitation on the pyrophyllite component compete for Ni uptake, X-ray absorption fine structure spectroscopy (XAFS) was used to estimate the distribution of Ni over the mixture components. This was done by comparison to pyrophyllite-montmorillonite mixtures with known Ni distributions over the mixture components. Nickel uptake on singly reacted pyrophyllite was slightly higher than on singly reacted montmorillonite. This was consistent with the XAFS results for the clay mixture, which suggested that the pyrophyllite component sorbed slightly more Ni than the montmorillonite component. Our findings suggested that both adsorption and surface precipitation were important mechanisms in the overall Ni uptake in the clay mixture, and that neither sorption mechanism truly out-competed the other in the reaction time of 40 min employed. Therefore, both mechanisms should be considered when modeling Ni sorption in similar systems. Copyright 1999 Academic Press.     

Character of transitions causing the physicochemical aging of a sapric histosol

Physicochemical aging of soil organic matter is assured by the dynamic character of weak interactions stabilizing its supramolecular structure. However, aging is difficult to monitor, due to low organic matter content in most soils and relatively large time constants. In order to overcome those problems, a model soil, sapric histosol, was exposed to the accelerated aging after a short heating event to 110 °C, and its thermal characteristics were monitored over several months. Classical and temperature modulated differential scanning calorimetry, microcalorimetry and solid-state NMR were used to elucidate the character of involved transitions. The heating event caused separation of an initially broad transition into two processes; a melting, which showed almost no response on the previous heating and a step transition, which is associated with the disruption of water molecule bridges (WaMB) between molecular segments of organic matter. Both processes are preceded by a preparatory phase, starting at subambient temperatures, in which aliphatic domains probably recrystallize and water molecules condensate forming WaMB stabilizing the physical structure of sapric histosol. The aliphatic moieties showed a particular behavior reflected in higher imperfection in crystallite structure upon slow cooling, which was attributed to their interaction with surrounding porous and heterogeneous structures. The results show that soil organic matter aging, considered as a natural process driven by thermodynamic principles, is caused by successive development of WaMB. This is potentially accompanied by recrystallization of aliphatic structures and both processes lead to higher physicochemical stability of soil organic matter.     

Effect of Organic Modification on the Compatibilization Efficiency of Clay in an Immiscible Polymer Blend

Summary: This communication describes the effect of organic modifier miscibility with the matrices, and the effect of the initial interlayer spacing of the organoclay, on the overall morphology and properties of an immiscible polycarbonate/poly(methyl methacrylate) blend. By varying the organic‐modifier‐specific interactions with the blend matrices at the same time as changing the initial interlayer spacing of the organoclay, different levels of compatibilization were revealed. The evidence for the interfacial compatibilization of the organoclay was assessed by scanning electron microscopy observations and was supported by differential scanning calorimetry analyses. The effect on the level of clay exfoliation was also examined.

Differential scanning calorimetry scans of virgin, montmorillonite, and various organically modified montmorillonite‐compatibilized 40PC/60PMMA blends     

Study of the behaviour of azinphos-methyl in a clay mineral by batch and column leaching

Research efforts dealing with the processes affecting the transport of pesticides in soils are needed in order to prevent further damage of surface and groundwater reserves. Although organic matter has been recognised as the most important contributor to the adsorption of non-ionic organic pesticides in soils, in some cases clay minerals may have an important role in the retention of these compounds. The present study was designed to improve the knowledge of the behaviour of azinphos-methyl in soils. Coefficients from adsorption isotherms and HPLC analysis of soil column leachates were used in this work for predicting pesticide mobility in soils. The studied clay mineral was a Spanish bentonite with a predominant montmorillonite fraction. The results showed that azinphos-methyl was adsorbed on the clay mineral and demonstrated the catalytic effect of bentonite on the hydrolysis of the pesticide.     

Investigating the structure–property relationship of aromatic–aliphatic polyamide/layered silicate hybrid films

Surface treated montmorillonite was used to prepare nanocomposites with aromatic–aliphatic polyamide by solution intercalation technique. The polyamide chains were produced through polycondensation of 4-aminophenyl sulfone with sebacoyl chloride in dimethyl acetamide. Compatibility between the polymer and organoclay was achieved through carbonyl chloride end-capped amide chains prepared by adding extra sebacoyl chloride near the end of polymerization reaction. The nanocomposites morphology and clay dispersion were investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Delaminated and intercalated morphologies were observed for different loading of organoclay. Tensile strength and modulus improved for nanocomposites with optimum organoclay content (10-wt.%). Thermal stability and glass transition temperature of nanocomposites increased relative to pristine polyamide with augmenting organoclay content. Water uptake of these materials decreased as compared to the neat polyamide indicating reduced permeability.     

Adsorbed para-nitrophenol on HDTMAB organoclay--a TEM and infrared spectroscopic study

para-Nitrophenol adsorbed on hexadecyltrimethylammonium bromide modified montmorillonite has been studied using a combination of X-ray diffraction TEM and infrared spectroscopy. Upon formation of the organoclay, the properties change from hydrophilic to hydrophobic. It is proposed that para-nitrophenol is adsorbed onto the water in the cation hydration sphere of the organoclay. As the cation is replaced by the surfactant molecules the para-nitrophenol replaces the surfactant molecules in the clay interlayer. Significant changes in the water vibrations occur in this process. Bands attributed to CH stretching and bending vibrations in general decrease as the concentration of the surfactant (CEC) increases up to 1.0 CEC. After this concentration the bands increase approaching a value the same as that of the surfactant. Strong changes occur in the HCH deformation modes of the methyl groups of the surfactant. These changes are attributed to the methyl groups locking into the siloxane surface of the montmorillonite. Such a concept is supported by changes in the SiO stretching bands of the montmorillonite siloxane surface. This study demonstrates that para-nitrophenol will penetrate into the untreated clay interlayer and replace the intercalated surfactant in surfactant modified clay, resulting in the change of the arrangement of the intercalated surfactant.     

Grafting of swelling clay materials with 3-aminopropyltriethoxysilane

The grafting reaction between a trifunctional silylating agent and two kinds of 2:1 type layered silicates was studied using FTIR, XRD, TGA, and 29Si CP/MAS NMR. XRD patterns clearly indicate the introduction of 3-aminopropyltriethoxysilane (gamma-APS) into the clay interlayer. In the natural montmorillonite, gamma-APS adopts a parallel-bilayer arrangement, while it adopts a parallel-monolayer arrangement in the synthetic fluorohectorite. These different silane arrangements have a prominent effect on the mechanism of the condensation reaction within the clay gallery. In natural montmorillonite, the parallel-bilayer arrangement of gamma-APS results in bidentate (T2) and tridendate (T3) molecular environments, while the parallel-monolayer arrangement leads to monodentate (T1), as indicated by 29Si CP/MAS NMR spectra. This study demonstrates that the silylation reaction and the interlayer microstructure of the grafting products strongly depend on the original clay materials.     

Effects of montmorillonite modification on optical properties of heterogeneous nematic liquid crystal – clay mineral nanocomposites

Investigations of montmorillonite (MMT) clay mineral modification effects on electro‐optical properties of nanocomposites, based on the nematic liquid crystal 4‐pentyl‐4′‐cyanobiphenyl (5CB) and MMT have been carried out. Only the composite with MMT modified by an organic surface‐active substance, dioctadecyldimethylammonium chloride, has been shown to manifest electro‐optical memory effect and contrast. A polar dopant (acetone), added to the mixture, significantly increases composite homogeneity. Results of IR spectroscopy measurements lead to the conclusion, that there is a mutual influence of components on each other in organoclay systems, which appears as an alignment of near‐surface layers of both the organic and inorganic components of the composite. Due to such interactions these systems show electro‐optical contrast and memory effect. A composite with organophobic Na‐MMT does not show these electro‐optical properties, due to the absence of component interactions, as shown by IR spectroscopic data.     

Sequestered carbon on clay mineral probed by electron paramagnetic resonance and X-ray photoelectron spectroscopy

This paper describes the interaction among soil organic matter components with kaolinite, an important clay mineral present in tropical soils, especially in Brazil. XPS data show that the soil organic matter adsorbed on kaolinite has aromatic and aliphatic structures, with phenolic and/or alcoholic functions and carbonyl carbons (CO) of amide and/or carboxylic groups. The N1s spectrum of the kaolinite shows an asymmetric peak that is assigned to amide and protonated ammines probably from humin. The interaction between them is strong enough to resist chemical oxidative or reductive attack besides loose amide functionalities. EPR data show that reductive treatment reduces some Fe3+ of the kaolinite structure, loosing organic components. A schematic representation of the reduction of structural Fe3+ in the concentrated domains and consequently increased concentration of Fe3+ ions in diluted domains of the spectrum is presented. This reinforces the hypothesis that humin is a stable carbon sink in soils when adsorbed to clays.     

Flexible polyurethane nanocomposite foam: Synthesis and properties

Flexible polyurethane (PU) nanocomposite foams were synthesized using organically modified montmorillonite clay (Cloisite 30B). The dispersion of organoclay was considered both in the isocyanate and polyol matrixes. Silicate layers of organoclay can be exfoliated in PU matrix by use of two steps mixing process. The presence of clay increased the cell density and reduced the cell size compared to the conventional PU foam. Clay dispersion was investigated by X-ray diffraction (XRD). The morphology and properties of PU nanocomposite foams were also studied. Generally, mechanical properties by addition of clay were improved. Foams in which clay was firstly dispersed in the isocyanate, showed better dispersion due to affinity of OH group on the clay surface to react with NCO groups. Better properties have been achieved with these nanofoams.     

Polymer-clay nanocomposites: chemical grafting of polystyrene onto Cloisite 20A

An account of the experiments on preparing polystyrene(PS) nanocomposites through grafting the polymer onto organophilic montmorillonite is reported.Cloisite 20A was reacted with vinyltrichlorosilane to replace the edge hydroxyl groups of the clay with a vinyl moiety.Because the reaction may liberate HC1,it was performed in the presence of sodium hydrogencarbonate to prevent the exchange of quaternary alkylammonium cations with H~+ ions.Only the silanol groups on the edge of the clay react with vinyltrichlorosilane.The radical polymerization of the product with styrene as a vinyl monomer leads to chemical grafting of PS onto the montmorillonite surface.The homopolymer formed during polymerization was separated from the grafted organoclay by Soxhlet extraction.Chemical grafting of the polymer onto Cloisite 20A was confirmed by infrared spectroscopy.The prepared nanocomposite materials and the grafted nano-particles were studied by XRD.Exfoliated nanocomposites may be obtained for 0.5 wt%-l wt%clay content.The nanocomposites were studied by thermogravimertic analysis(TGA) dynamic thermal analysis(DTA) and dynamic mechanical analysis (DMTA).     

Interactions of Methyl Orange with Cyclodextrin/Sodium-Montmorillonite Systems Probed by UV-Visible Spectroscopy

Clay mineral colloids play important roles in the adsorption of polar organic contaminants in the environment. Similarly, cyclodextrins (CD) can entrap poorly water-soluble organic compounds. A combination of CDs and clay minerals affords great opportunities to investigate simultaneously complexation and adsorption processes involving organic contaminants. In this work, we investigated in situ the extent of adsorption and/or complexation of a molecular probe, methyl orange (MO), in CD/sodium montmorillonite systems using UV-visible spectroscopy. The anion form of MO interacts with the clay surface via cationic bridges, whereas the cation form is weakly adsorbed by a cation-exchange mechanism. Further, in acidic media, there is a local competition between MO and the montmorillonite surface for H(+) ions. This inhibits protonation of MO in the immediate vicinity of the clay. The presence of CDs, however, perturbs the favored process of proton scavenging by the clay. In particular, in betaCD-clay systems, betaCD-complexed MO can compete successfully with the clay for H(+) ions. The shielding effect of betaCD appears to play a key role in preventing the deprotonation of complexed MO. Copyright 2001 Academic Press.