The simultaneous adsorption of both imazalil (IMZ) and thiabendazole (TBZ) fungicides in a Cu 2+-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 C i = 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 Cu 2+ 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-Cu 2+ 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.
To improve hexavalent chromium (Cr(VI)) retention of montmorillonite (Mt) at pH 3, Mt sample was subjected to different treatments: thermal ones at 600 °C or 950 °C, 2 h, or mechanical grinding for 300 s. Then, the obtained products were loaded with different octadecyl trimethyl ammonium loading and 50% and 100% of Mt cation exchange capacity (CEC). The samples were characterized by several techniques at each stage. Differential thermogravimetric analysis (DTGA) performed on the products allowed determining the actual surfactant amount related to the internal or external surface by cation exchange and Van der Waals (VdW) mechanisms, respectively, taking into account the CEC of the thermal or mechanical pretreated Mt base sample used. X-ray diffraction (XRD) analyses revealed that the surfactant loading allowed the reversal of the collapsed interlayer after both treatments. The samples subjected to the thermal treatment at 600 °C and the raw Mt samples exhibit higher positive zeta potential values than the mechanical pretreated Mt ones with 100% of the CEC surfactant loaded at pH 3. This was directly related to the external surface covered by the surfactant. The agreement between the results of the surfactant coverage on the external surface and Cr(VI) removal at pH 3 indicates that the electrostatic mechanism is the main driving force for the sorption of Cr(VI). These synthesized sorbents achieve similar Cr(VI) retention using less than half the surfactant amount of already published studies.
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