Among pharmaceutical products (PPs) recalcitrant to water treatments, diclofenac shows a high toxicity and remains at high concentration in natural aquatic environments. The aim of this study concerns the understanding of the adsorption mechanism of this anionic PP onto two organoclays prepared with two long-alkyl chains cationic surfactants showing different chemical nature for various experimental pH and temperature conditions. The experimental data obtained by a set of complementary techniques (X-ray diffraction, elemental analyses, gas chromatography coupled with mass spectrometry, and Fourier transform infrared spectroscopy) and the use of Langmuir, Freundlich and Dubinin-Radushkevish equation models, reveal that organoclays show a good affinity to diclofenac which is enhanced as the temperature is under 35°C and for pH above 4.5 (i.e. >pKa of diclofenac) while the chemical nature of surfactant appears to play a minor role. The thermodynamic parameters derived from the fitting procedure point out the strong electrostatic interaction with organic cations adsorbed within the interlayer space in the organoclays for the adsorption of diclofenac. This study stress out the application of organoclays for the adsorption of a recalcitrant PPs in numerous aquatic compartments that can be used as a complement with activated carbon for waste water treatment.

Numerous adsorbent materials are developed and are able to face specific types of pollution, but none of them can manage the whole pollution. The purpose of this work is to develop a novel hybrid adsorbent, based on chitosan (CS) biopolymer, clay minerals and activated carbon (AC), having complementary adsorption properties and achieving a wide-spectrum water decontamination in a single treatment. Hybrid CS beads, containing dispersed clay and AC, were prepared from dispersions of solid adsorbents in a CS solution and its further coagulation in a basic medium. The porosity and the homogeneity of the hybrid beads were characterized by N₂ adsorption at 77 K and Cryo-Scanning Electron Microscopy respectively. The interaction between CS and clay was characterized using X-ray diffraction. Water content and the amount of each adsorbent in the hydrogel beads were determined by thermogravimetric analysis. Such a composite material was still porous and presented a wide adsorption spectrum. As shown by their adsorption kinetics, hydrophobic anionic clofibric acid (CBA) and cationic metoprolol (MTP) were well adsorbed on AC containing beads (21 and 26 mg/g), respectively. Clays containing beads showed interesting adsorption properties towards cationic Zn²⁺ and MTP. The obtained composite beads were able to adsorb all the pollutant types: Zinc cations, and hydrophobic-charged organic molecules, such as pharmaceutical derivatives (clofibric acid and MTP).

Chitosan (CS) hydrogel beads and hybrid beads made of a blending of CS hydrogels and Multilayer Graphene Oxide (MGO) were synthesized. The hybrid beads were prepared by gelation in NaOH solution of a 1 wt% CS acid solution with addition of MGO at either 1.5 wt% or 3 wt% loading rates. Prepared beads were characterized by infrared spectroscopy, thermogravimetric analysis (TGA), scanning electron cryo-microscopy and Brunauer–Emmett–Teller (BET) specific surface area measurements. Zn 2 + and Metoprolol (MTP) adsorption kinetics and isotherms were studied on the pristine and hybrid CS hydrogel beads. The adsorption kinetics of Zn 2 + and MTP in hybrid beads is limited by the diffusion to the MGO sites depending on their accessibility. While pure CS is not efficient for the MTP adsorption, the Langmuir-type isotherms of the 3 wt% MGO hydrogel beads (dose: 5 mg/100 mL) show 163 mg · g - 1 maximum adsorption uptake. The MTP adsorption kinetics and isotherm suggest a MTP trapping on the MGO anionic sites (carboxylate groups) by electrostatic interactions. The Zn 2 + adsorption capacities are the highest for the 3 wt% MGO hydrogel beads (236 mg · g - 1 ), and only of 40 mg · g - 1 for the pure CS beads. The presence of Zn 2 + adsorption sites in the hybrid bead, such as MGO carboxylate groups giving electrostatic interactions, and CS amine groups leading to complexation, provides synergic adsorption effects. The competitive adsorption of Zn 2 + with respect to MTP in equimolar mixture was observed on hybrid beads (dose: 200 mg/100 mL) at 2 mmol · L - 1 initial total concentration. At pollutant initial total concentration lower than 1.5 mmol · L - 1 , no competition occurs. The regeneration at pH 4 of the hybrid beads toward MTP or Zn 2 + adsorption was found to be 35–40% of the initial adsorption uptake for five adsorption/regeneration cycles.

Monodisperse amphiphilic diblock oligomers of C16 alkyl chains and vinyl alcohol units were prepared by aldol-group transfer polymerization and recycling size-exclusion chromatography separation to form a double-crystalline lamellar structure.

Activated carbon beads, some of which contain Fe₃O₄ nanoparticles or graphene oxide, were synthesized by thermal activation (700 °C) of chitosan hydrogel beads. Materials showed a multiporous scale (micro/meso/macro) and BET specific surface areas in the 260–572 m².g⁻¹ range. The adsorption kinetics of beads and powders resulting from their grinding were studied for a mixture of six micropollutants (bisphenol A, carbofuran, carbamazepine, diclofenac, dimethoate and imidacloprid) dissolved in spring water. While the adsorption kinetics on the beads (pH 7.3, 25 °C, 10–100 µg.L⁻¹) are slow (equilibrium time > 24 h), the powdered samples are more efficient: for an initial concentration of 50 μg.L⁻¹ of each pollutant (0.1 g.L⁻¹ of adsorbent), 50 to 99% of the micropollutants introduced into the solution were removed after 4 h of contact time. Depending on the pollutant nature, the adsorption isotherms (0.2–40 μg.L⁻¹) studied for an activated carbon powder containing Fe₃O₄ (1 mass %) are either of Langmuir or Freundlich type, or they follow Henry’s law and are related to the different properties of the molecules.