Abstract

Synthetic dyes in industrial effluents pose a significant risk to human health and the environment, so much effort has been expended to degrade them using various methods, including the use of clay minerals as catalysts. The purpose of this study was to advance understanding of the mechanisms for clay-catalyzed degradation of crystal violet (CV) and other triarylmethine dyes using three different vermiculite clays (Llano, Texas, VTx-1; Ojen, OV; and Russian, RV), a montmorillonite (SWy-1), and a Spanish sepiolite (SEP). While OV, RV, SWy-1, and SEP showed almost no activity with respect to dye degradation, VTx-1 caused complete removal of the dye from solution up to the equivalent of 200% of the cation exchange capacity of the clay. While large amounts of dye were removed from the solution, no change in basal spacing was observed by X-ray diffraction. The kinetics of removal of CV from solution began after a lag period of >10 days in a process that can be described by pseudo-second order kinetics. By comparison, adsorption of CV onto SWy-1 and SEP was immediate, without any lag period. Sonication treatment of the VTx-1 vermiculite suspension caused the CV removal process to begin immediately. Fourier-transform infrared measurements of adsorption of CV on clays revealed that for the OV and RV vermiculites, SEP sepiolite, and SWy-1 montmorillonite the spectra were similar to the original dye; the spectra of the VTx-1-dye differed considerably, however, exhibiting vibrations of methylene groups (–CH2–) which were not present in the CV molecule. The significant changes in the IR spectrum indicated that CV underwent degradation on the surface of the VTx-1 vermiculite. Carbon-content analysis led to the conclusion that degradation products remained bound to the clay. Similar effects were observed for two other triarylmethine dyes (malachite green and methyl green) added to VTx-1, indicated that it may, therefore, be considered suitable as a sorbent to remove and decompose such dyes from industrial effluents. Pretreatment by sonication would remove the need for long incubation times.

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