Single and competitive sorption properties and mechanism of functionalized biochar for removing sulfonamide antibiotics from water

Single and competitive sorption of ionisable sulphonamides sulfamethazine, sulfamethoxazole and sulfathiazole on functionalized biochar was highly pH dependent. The equilibrium data were well represented by both Langmuir and Freundlich models for single solutes, and by the Langmuir model for competitive solutes. Sorption capacity and distribution coefficient values decreased as sulfathiazole > sulfamethoxazole > sulfamethazine. The sorption capacity of each antibiotic in competitive mode is about three times lower than in single solute sorption. The kinetics data were best described by the pseudo second-order (PSO) model for single solutes, and by PSO and intra-particle diffusion models for competitive solutes. Adsorption mechanism was governed by pore filling through diffusion process. The findings from pH shift, FTIR spectra and Raman band shift showed that sorption of neutral sulfonamide species occurred mainly due to strong H-bonds followed by π⁺-π electron-donor-acceptor (EDA), and by Lewis acid-base interaction. Moreover, EDA was the main mechanism for the sorption of positive sulfonamides species. The sorption of negative species was mainly regulated by proton exchange with water forming negative charge assisted H-bond (CAHB), followed by the neutralization of –OH groups by H⁺released from functionalized biochar surface; in addition π-π electron-acceptor-acceptor (EAA) interaction played an important role.