Removal of ciprofloxacin from aqueous solutions by ionic surfactant-modified carbon nanotubes

Ionic surfactants may impact removal efficiency of organic contaminants from aqueous solution, but research regarding the adsorption mechanisms on surfactant-modified carbon nanotubes (CNTs) was limited. In this study, three multi-walled and one single-walled CNTs were used as adsorbents to investigate the adsorption behavior and mechanisms of ciprofloxacin (CIP) on CNTs modified by ionic surfactants (cationic CTAB (Cetyltrimethylamnonium bromide) or anionic SDS (Sodium dodecyl sulfate)). More than 80% (82-88%) of the total removed CIP on CTAB-modified CNTs occurred within the first 6 h, much higher than that on SDS-modified CNTs (57-78%). Modeling adsorption kinetics demonstrated that CIP adsorption on surfactant-modified CNTs was controlled by multiple and faster processes, and both external mass transfer and intraparticle diffusion are limiting factors. Relative to SDS, CTAB was significantly (P < 0.001) concentration-dependent in suppressing CIP removal. Besides, the increase in 1/n values of Freundlich model with increasing CTAB concentration suggested that CTAB could be a stronger competitor for CIP adsorption. Hydrophobic interactions predominated zwitterionic CIP adsorption on all CNTs tested, while electrostatic interactions could help control ionizable CIP adsorption on surfactant-modified CNTs depending upon pH. CIP adsorption on modified SWCNTs significantly declined with increasing ionic strength from 1 mM to 100 mM relative to those multi-walled CNTs because the more favorable aggregation of SWCNTs reduced the CIP adsorption, irrespective of which surfactant was added. Significant desorption hysteresis of adsorbed CIP released by SDS and water was observed, but not by CTAB, by which 32.6-54.4% of adsorbed CIP were removed. For SDS-modified CNTs, the mean release ratio (RR) followed an order of MWCNTs (0.075) > MHCNTs (0.058) > SWCNTs (0.057) > MCCNTs (0.049), significantly (P < 0.001) lower than CTAB-CNTs (0.37-0.56). It can be predicted that the tested surfactants co-existing with CNTs depress removal efficiency of diverse contaminants similar to CIP in aqueous systems.