Clinoptilolite-Based Adsorbents for Paracetamol Removal

This study investigates the adsorption of paracetamol from aqueous solutions using natural clinoptilolite and its modified forms. The raw zeolite (p-CLI) was converted into its protonic (H-CLI) and organo-modified (o-CLI) counterparts through ammonium exchange and calcination, and treatment with hexadecyltrimethylammonium bromide (HDTMA-Br), respectively. The materials were characterized by XRD, FT-IR, and SEM analyses. XRD confirmed that the clinoptilolite crystalline framework was preserved after both modifications, while FT-IR and SEM revealed partial removal of exchangeable cations in H-CLI and the formation of an HDTMA-derived organic layer on the external surface of o-CLI. Adsorption experiments were carried out under batch conditions at initial paracetamol concentrations of 0.5-10 mg/L, and equilibrium paracetamol concentrations were determined using differential pulse voltammetry (DPV). The raw clinoptilolite exhibited negligible adsorption capacity (<0.10 mg/g) due to its hydrophilic surface and microporous framework, which limit interaction with neutral organic molecules. Conversion to the protonic form slightly enhanced the adsorption performance (~0.15 mg/g), while HDTMA modification resulted in a modest additional increase (~0.25 mg/g), attributed to the formation of hydrophobic and organophilic surface sites. Overall, the results indicate that surface functionalization can improve the affinity of clinoptilolite toward weakly polar pharmaceuticals; however, the adsorption capacities remain limited. The novelty of this work lies in combining voltametric quantification with a direct comparison of proton-exchanged and surfactant-modified clinoptilolite to elucidate how specific structural and surface changes influence paracetamol uptake.