Mechanisms of Individual and Simultaneous Adsorption of Antibiotics and Dyes onto Halloysite Nanoclay and Regeneration of Saturated Adsorbent via Cold Plasma Bubbling

Abstract

Halloysite nanoclay (HNC) was examined as an adsorbent for the individual and simultaneous removal of antibiotic enrofloxacin (ENRO) and methylene blue (MB) from aqueous solutions, alongside its regeneration via cold atmospheric plasma (CAP) bubbling. Initially, batch kinetics and isotherm studies were carried out, while the effect of several parameters was evaluated. Both ENRO and MB adsorption onto HNC was better described by Langmuir model, with its maximum adsorption capacity being 34.80 and 27.66 mg/g, respectively. A Pseudo-second order model fitted the experimental data satisfactorily, suggesting chemisorption (through electrostatic interactions) as the prevailing adsorption mechanism, whereas adsorption was also controlled by film diffusion. In the binary system, the presence of MB seemed to act antagonistically to the adsorption of ENRO. The saturated adsorbent was regenerated inside a CAP microbubble reactor and its adsorption capacity was re-tested by applying new adsorption cycles. CAP bubbling was able to efficiently regenerate saturated HNC with low energy requirements (16.67 Wh/g-adsorbent) in contrast to Fenton oxidation. Most importantly, the enhanced adsorption capacity of the CAP-regenerated HNC (compared to raw HNC), when applied in new adsorption cycles, indicated its activation during the regeneration process. The present study provides a green, sustainable and highly effective alternative for water remediation where pharmaceutical and dyes co-exist.