Organobentonites have been applied for the removal of two common non-steroidal anti-inflammatory drugs, ibuprofen (IBU) and diclofenac sodium (DS), from aqueous solutions. Two surfactants, one with and the other without benzyl group (octadecyldimethylbenzylammonium chloride, ODMBA, and hexadecyltrimethylammonium bromide, HDTMA), in amounts equivalent to 50, 75, and 100% of the cation exchange capacity of bentonite were used for the preparation of organobentonites. Successful modification of bentonite was confirmed by several methods: X-ray powder diffraction (XRPD), point of the zero charge (pH_PZC), determination of exchanged inorganic cations in bentonite, determination of textural properties, and scanning electron microscopy (SEM). Kinetic and thermodynamic data on the adsorption of IBU and DS showed that drug adsorption was controlled by the type and the amount of surfactant incorporated into the bentonite and by their arrangement in the interlayer space and at the surface of organobentonites. The adsorption of both drugs increased with an increase in the amount of both surfactants in organobentonites. The presence of the benzyl group in organobentonites enhanced the adsorption of IBU and DS and was more pronounced for IBU. Drug adsorption fits the pseudo-second-order kinetic model the best. The thermodynamic data revealed that the adsorption process was endothermic in nature and with increase of the amount of both surfactants drug adsorption processes were more spontaneous. The results obtained from this study revealed that adsorbents based on surfactants modified bentonite are promising candidates for IBU and DS removal from contaminated water.

This work aimed to test composites (surfactant modified zeolites prepared by treatment of natural zeolites—clinoptilolite (IZ CLI) and/or phillipsite (PHIL75)-rich tuffs with two different amounts of cationic surfactants: cetylpyridinium chloride (CPyCl) and Arquad^® 2HT-75 (ARQ)) for the adsorption of salicylic acid (SA)—a common contaminant of emerging concern. Adsorption of SA was studied at different initial drug concentrations (in the range of 2–100 mg/L) in water solution. The Langmuir isotherm model showed the highest adsorption was achieved by bilayer composite of IZ CLI and CPyCl—around 11 mg/g. Kinetic runs were performed by using the initial drug concentration of 20 mg/L in the time interval from 0 to 75 min and pseudo-second order had good correlation with experimental data. The influence of the four different temperatures on the SA adsorption was also investigated and thermodynamic parameters suggested that the adsorption drug onto composites is an exothermic and nonspontaneous process, followed by the decrease of randomness at the solid/liquid interface during the adsorption. Zeta potential and Fourier-transform infrared spectroscopy with attenuated total reflectance (FTIR-ATR) had been performed for the characterization of composites after adsorption of SA confirming the presence of the drug at composite surfaces.

Modified phillipsite samples were prepared with two different amounts (monolayer and bilayer coverage) of surfactants octadecyldimethylbenzylammonium chloride (O) and dodecylamine (D). Composites were characterized by Fourier transform infrared spectroscopy with attenuated total reflectance (FTIR–ATR), thermal analysis and determination of zeta potential, and subsequently tested for removal of diclofenac sodium (DCF). Drug adsorption experiments were performed under different initial DCF concentrations and different contact times. In order to investigate the influence of the chemical structure of surfactants used for modification of phillipsite on the preparation and properties of composites and DCF adsorption, experimental data were compared with previously published results on DCF adsorption by composites containing phillipsite and the same amounts of surfactants cetylpyridinium chloride (C) and Arquad^®2HT-75 (A). DCF adsorption isotherms for O and D composites showed a better fit with the Langmuir model with maximum adsorption capacities between 12.3 and 38.4 mg/g and are similar to those for C and A composites, while kinetics run followed a pseudo-second-order model. Composites containing either benzyl or pyridine functional groups showed higher adsorption of DCF, implying that surfactant structure has a significant impact on drug adsorption. Drug adsorption onto O, D, C and A composites was also confirmed by FTIR–ATR spectroscopy and zeta potential measurements.