Qualitative and quantitative adsorption mechanisms of zinc ions from aqueous solutions onto dead carp derived biochar

Abstract

The objective of this study is to investigate the qualitative mechanisms of Zn²⁺ adsorption on carp biochars (CMBx) produced from dead carp at different temperatures (450–650 °C) and their quantitative contribution. The pseudo second order kinetic model and the Langmuir model could fit the kinetic and isothermal adsorption data well, respectively. The intra-particle diffusion was the main rate-limiting step but not the only rate-limiting step. The maximum adsorption capacity obtained from the Langmuir model for CMB650 was 87.7 mg g⁻¹ which was greater than those of other biochars. Precipitation with minerals, ion exchange, and complexation with functional groups (OFGs) were the main adsorption mechanisms. Quantum chemistry calculations confirmed that the functional groups (e.g., hydroxyl, carboxyl and CC) tended to bind with Zn²⁺ more strongly than with Ca²⁺ and Mg²⁺, because the structure of the complex formed by the former was more stable. The contribution of different adsorption mechanisms varied with the pyrolysis temperature to prepare biochar. With increasing pyrolysis temperature, the contribution of the interaction between Zn²⁺ and the minerals increased from 46.4% to 84.7%, while that of complexation with OFGs decreased from 41.7% to 4.7%. Overall, the mechanism of Zn²⁺ adsorption on CMB450 was dominated by complexation with OFGs and exchange with cations (accounting for 73.2%), while the mechanisms on CMB650 were dominated by the interaction with minerals. In view of the total adsorption capacity, 650 °C was the optimized pyrolysis temperature for CMBx preparation and adsorption treatment of Zn-contaminated water. These results are useful for screening effective biochars as engineered sorbents to treat Zn-containing wastewater.