Influences of pH and metal ions on the interactions of oxytetracycline onto nano-hydroxyapatite and their co-adsorption behavior in aqueous solution

Abstract

In this study, interaction of oxytetracycline (OTC) onto nano-hydroxyapatite (nHAP) was evaluated as affected by pH and metal ions. Results showed that the adsorption process of OTC was highly pH- and metallic species-dependent. The amount of sorbed OTC at four pH were in the order of pH 8.0 > pH 10.0 > pH 5.5 > pH 3.0 and reached equilibrium around 120 min, indicating adsorption affinity of four species to nHAP followed the order of OTC− > OTC2− > OTC± > OTC+. Adding metal ions greatly increased the distribution coefficient (Kd) of OTC between adsorbents and aqueous phases, following the order of Fe3+ > Cu2+ > Pb2+ > Cd2+ = Ca2+ in the pH range of 3.0–10.0. Moreover, the co-adsorption behavior of OTC and heavy metals onto nHAP was also explored at pH 5.5 for the first time. OTC adsorption was significantly enhanced with the co-existence of 0.25 mmol/L Cu2+ or Pb2+. Inversely, the presence of 0.25 mmol/L OTC slightly led to the improvement of Cu2+ adsorption and depression of Pb2+ adsorption, yet Pb2+ adsorption was obviously promoted with the co-existence of 0.1 mmol/L OTC. Meanwhile, adsorption of OTC and Cd2+ showed unapparent variation in single or binary systems. The bridging effect involving metal ions, O- and N- containing groups in OTC molecules, and CaOH or POH sites of nHAP resulted in the formation of ternary complexes which were responsible for the promotion of their adsorption, while dissolution-precipitation was another key mechanism with the co-existence of Pb2+.