Arsenate removal from aqueous solution by montmorillonite and organo-montmorillonite magnetic materials.

Magnetic-clay (MtMag) and magnetic-organoclay (O100MtMag) nanocomposites were synthesized, characterized and evaluated for arsenic adsorption. Batch arsenic adsorption experiments were performed varying pH conditions and initial As(V) concentration, while successive adsorption cycles were made in order to evaluate the materials reuse. The highest As(V) removal efficiency (9 ± 1 mg g-1 and 7.8 ± 0.8 mg g-1 for MtMag and O100MtMag, respectively) was found at pH 4.0, decreasing at neutral and alkaline conditions. From As(V) adsorption isotherm, two adsorption processes or two different surface sites were distinguished. Nanocomposites resulted composed by montmorillonite or organo-montmorillonite and magnetite as the principal iron oxide, with saturation magnetization of 8.5 ± 0.5 Am2 Kg-1 (MtMag) and 20.3 ± 0.5 Am2 Kg-1 (O100MtMag). Thus, both materials could be separated and recovered from aqueous solutions using external magnetic fields. Both materials allowed achieving arsenic concentrations lower than the World Health Organization (WHO) recommended concentration limit after two consecutive adsorption cycles (2.25 and 4.5 µg L-1 for MtMag and O100MtMag, respectively).

Norfloxacin adsorption on montmorillonite and carbon/montmorillonite hybrids: pH effects on the adsorption mechanism, and column assays.

The presence of norfloxacin antibiotic (NFX) in drinking water raises significant scientific concern due to the health and environmental problems that may cause. This study aimed to evaluate the NFX removal: 1) in batch adsorption at different pH values on montmorillonite (M) and montmorillonite-carbon hybrids (M-HC); 2) in continuous columns experiments, to assess the technological application of these hybrids as domestic filters, using one M-HC as adsorbent material ranging from 1% to 5%. Batch experiments showed that adsorption occurred in all the samples, being M the material with the highest adsorption capacity (95% of adsorption for cationic NFX). For the M-HC the adsorption seemed to be not strongly dependent of the pH (20%- 41% of adsorption). The characterization of adsorbents and NFX adsorption products (FTIR, XRD, and zeta potential analysis) disclosed that adsorption occurs at both the external surface and the interlayer space of M. For the M-HC synthesized without activation, the interlayer space seemed to be predominantly responsible; while for the activated M-HC the adsorption occurred at the external surface (its interlayer was destroyed). The column experiments revealed that the best adsorption capacity and highest flow were attained using 1% of adsorbent material in the column packing.

Adsorption of picloram on clays nontronite, illite and kaolinite: equilibrium and herbicide-clays surface complexes.

The picloram (PCM) adsorption on nontronite, illite and kaolinite was studied at pH 3, 5 and 7. The adsorption isotherms had well-fitted to Langmuir and Freundlich models equations. The interactions of PCM with the clay mineral surfaces exhibited an anionic profile adsorption, with a decrease in adsorption when the pH increases. The PCM adsorption capacity increases in the following order: kaolinite < illite < nontronite. The X-ray diffraction (XRD) analysis of PCM-clay samples revealed that the picloram molecule does not enter into the clays basal space. The interaction of PCM with clays surface sites through nitrogen of the pyridine ring was confirmed by X-ray photoelectron spectroscopy (XPS). Due to the anionic form of PCM, the adsorption onto the external and edges surface sites of the clay minerals was proposed.

Adsorption and characterization of MCPA on DDTMA- and raw-montmorillonite: Surface sites involved.

The 4-chloro-2-methylphenoxy acid (MCPA) is an herbicide widely used in agriculture, which generates a great concern about contamination of surface water and serious consequences for human health and the environment. In this work, the adsorption of MCPA on an Argentine montmorillonite (MMT) and its organo-montmorillonite product (OMMT) with different dodecyl trimethyl ammonium loading was investigated. MCPA adsorption on OMMT increases at least 3 times, with respect to the amount determined for MMT. X-ray diffraction and zeta potential analyses indicated the inner (interlayer) and outer surface participate as adsorption sites. Changes in surface electric charge and also interlayer expansion suggest that dimethyl amine (MCPA counterion) was also surface-adsorbed. The larger aggregates of OMMT, without and with MCPA, obtained compared to those of MMT samples, generate an improvement in the coagulation efficiency. This property, particularly after MCPA retention, allows an easier separation of the solids from the solution and enables a simple technological process application.

Antimicrobial activities of bacterial cellulose - Silver montmorillonite nanocomposites for wound healing.

A nanocomposite based on bacterial cellulose (BC) containing montmorillonite (MMT) modified with silver (BC-MMT-Ag) was developed to be used as potential scaffold for wound healing. Montmorillonite was suspended in silver nitrate solution to incorporate silver in the matrix by ion exchange. The derivative silver clay suspension was used to modify bacterial cellulose membranes by ex situ technique. The BC nanocomposite was analyzed by thermal analysis, scanning electron microscopy, Fourier transform infrared and electron dispersion spectroscopies, X-ray diffraction, and rehydration capacity. The antimicrobial activity of the silver montmorillonite-bacterial cellulose nanocomposite was challenged in cultures of Gram(+) Staphylococcus aureus and Gram(-) Pseudomonas aeruginosa, and showed inhibition of growth in agar plates and biofilm formation as revealed by live-dead assay. Cytotoxicity of BC nanocomposites containing 1% to 25% of MMT-Ag showed good in vitro biocompatibility with L929 fibroblast cells.

Kinetic and equilibrium adsorption of two post-harvest fungicides onto copper-exchanged montmorillonite: synergic and antagonistic effects of both fungicides' presence.

The simultaneous adsorption of both imazalil (IMZ) and thiabendazole (TBZ) fungicides in a Cu2+-exchanged Mt was studied in this work. Kinetic studies were used to determine the rate law which describes the adsorption of individual fungicides onto the adsorbent. Adsorption isotherm of individual and combined fungicides was done to evaluate synergic or antagonistic effects. The Mt-Cu material considerably improved TBZ and/or IMZ adsorption from aqueous suspensions with respect to raw Mt, leading to removal efficiencies higher than 99% after 10 min of contact time for TBZ and IMZ Ci = 15 and 40 mg/L, respectively, when a solid dosage = 1 g/L was used. The adsorption sites involved were determined by a combination of X-ray diffraction (XRD) determinations and electron paramagnetic resonance (EPR), indicating that fungicides were bonded to Cu2+ cations, while the rate limiting step was the formation of coordination bonds. The adsorption mechanism proposed is that of ligand exchange between water and fungicide molecules in the metal coordination sphere. The single-crystal structure for the IMZ-Cu2+ complex indicated that four molecules were bounded to the copper centers, while two molecules of TBZ are bounded to copper explaining the higher IMZ uptake capacity for the Mt-Cu material. Graphical abstract.

Glyphosate behavior at soil and mineral-water interfaces.

Adsorption isotherms and surface coverage of glyphosate, N-phosphonomethylglycine (PMG), in aqueous suspensions of three Argentine soils with different mineralogical composition were measured as a function of PMG concentration and pH. Zeta potential curves for PMG/soils system were also determined. Montmorillonite and soil sample surface charges were negative and increased as the amount of adsorbed PMG increased, showing that the surface complexes are more negative than those formed during the surface protonation. PMG adsorption on soils were described using Langmuir isotherms and the affinity constants, and the maximum surface coverage was estimated at pH 4 and 7 using a two-term Langmuir isotherm, the mineralogical composition percentages, and maximum surface coverage and Langmuir constants for pure minerals. The influence of organic matter (OM) and iron content of soils on the PMG adsorption was evaluated. The surface coverage of PMG decreased when the OM and iron content decreased for minerals and soils.

Some aspects of the adsorption of glyphosate and its degradation products on montmorillonite.

The most worldwide used herbicide is glyphosate, phosphonomethylglycine (PMG). Consequently, a significant amount of PMG, its metabolites (sarcosine, SAR, and aminomethylphosphonic acid, AMPA) and the degradation product, methylphosphonic acid (MPA), reaches the soil, which acts as final sink. Because clays are one of the most reactive components of soils, expansive clays such as montmorillonite (Mt) are used to retain agriculture contaminants with some success. In this work, as a preliminary step for the evaluation of the risk that PMG, SAR, AMPA, and MPA occurrence could have on the environment, their adsorption on Mt surface was performed. The adsorption process was analyzed at constant adsorbate concentrations and two pH values to take into account the different protonation states of the amino group. DTA, XRD, zeta potential measurements, and XPS were used to identify the interactions or association mechanisms with the clay surface, the entry of adsorbates into the Mt interlayer, and electric charge changes on the Mt surface, and evaluate the acid-base surface complex constants, respectively. The interlayer thickness in acid media indicated that adsorbates are able to enter the interlayer in planar form. Besides, for the Mt-PMG sample, some PMG molecules could be also inserted as a bilayer or with a tilt angle of 52.4° in the interlayer. However, in alkaline media, the interlayer thickness indicated that the adsorbate arrangement differed from that of acidic media where PMG and MPA could have more than one orientation. The surface complex deprotonation constants were determined for the =NH+2 â‡† =NH+H+ process, being 3.0, 5.0, and 7.3 for PMG, AMPA, and SAR, respectively.

Technological applications of organo-montmorillonites in the removal of pyrimethanil from water: adsorption/desorption and flocculation studies.

Pyrimethanil (2-aniline-4, 6-dimethylpyrimidine, PRM) is used in fruit packing plants to control fungal infections and diseases. The effluents greatly polluted with this fungicide, as a point source contamination, need to be technologically treated for their regeneration before they reach water bodies. This work evaluates the use of organo-montmorillonites, synthetized in our laboratory, for their application in adsorption and coagulation/flocculation processes for the removal of PRM from water. The adsorption-desorption performance of PRM in a raw montmorillonite (Mt) and several organo-montmorillonites (organo-Mt) obtained by different amounts and types of exchanged surfactants (octadecyltrimethylammonium (ODTMA) and didodecyldimethylammonium (DDAB) bromides and benzyltrimethylammonium chloride (BTMA)) was studied. The PRM adsorption on raw Mt was assigned mainly to an interlayer occupancy, while hydrophobic interactions between PRM and the surfactants in the exchanged samples increased PRM adsorption, which was correlated with the surfactant loading. PRM desorption showed irreversible behavior in raw Mt, which changed to reversible for organo-Mt samples, and was also correlated with the increase of surfactant loading.Two of the organo-Mt with high surfactant loading (twice the CEC) were assayed for the removal of commercial PRM in coagulation/flocculation tests, and their performance was compared to that of the native clay (Mt). The use of the organo-Mt produced flocculation at a very low ratio (0.5 g L-1), whereas no flocculation was observed with Mt. These results proved the feasibility of the use of organo-Mt for the treatment of wastewater contaminated with PRM using a low organo-Mt/liquid ratio.

Slow-release formulations of the herbicide picloram by using Fe-Al pillared montmorillonite.

Slow-release formulations of the herbicide picloram (PCM, 4-amino-3,5,6-trichloropyridine-2-carboxylic acid) were designed based on its adsorption on pillared clays (pillared clays (PILCs)) for reducing the water-polluting risk derived from its use in conventional formulations. Fe-Al PILCs were synthesized by the reaction of Na+-montmorillonite (SWy-2) with base-hydrolyzed solutions of Fe and Al. The Fe/(Fe + Al) ratios used were 0.15 and 0.50. The PCM adsorption isotherms on Fe-Al PILCs were well fitted to Langmuir and Freundlich models. The PCM adsorption capacity depended on the Fe content in the PILCs. Slow-release formulations were prepared by enhanced adsorption of the herbicide from PCM-cyclodextrin (CD) complexes in solution. CDs were able to enhance up to 2.5-fold the solubility of PCM by the formation of inclusion complexes where the ring moiety of the herbicide was partially trapped within the CD cavity. Competitive adsorption of anions such as sulfate, phosphate, and chloride as well as the FTIR analysis of PCM-PILC complexes provided evidence of formation of inner sphere complexes of PCM-CD on Fe-Al PILCs. Release of the herbicide in a sandy soil was lower from Fe-Al PILC formulations relative to a PCM commercial formulation.

Chromium removal by zeolite-rich materials obtained from an exhausted FCC catalyst: Influence of chromium incorporation on the sorbent structure.

A spent FCC catalyst was converted into a zeolitic mixture, and the product obtained was afterward used as trapping material for Cr(III) species frequently found in aqueous solutions. Eventual changes in the sorbent structure produced by Cr incorporation were studied by different characterization techniques such as point of zero charge determinations (PZC), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), and infrared absorption (FTIR). The XRD and FTIR analyses indicated that chromium incorporation produces an amorphization of the material, and PZC measurements show no surface adsorption of charged chromium species. SEM and EDX analyses clearly show that after chromium sorption, the initial microspheroidal catalyst morphology was maintained, and the presence of chromium species was mainly detected in the outer microsphere surface, where the zeolite crystals were hydrothermally grown.