Synthesis and applications of bismuth-impregnated biochars originated from spent coffee grounds for efficient adsorption of radioactive iodine: A mechanism study

The adsorption of radioactive iodine, which is capable of presenting high mobility in aquatic ecosystems and generating undesirable health effects in humans (e.g., thyroid gland dysfunction), was comprehensively examined using pristine spent coffee ground biochar (SCGB) and bismuth-impregnated spent coffee ground biochar (Bi@SCGB) to provide valuable insights into the variations in the adsorption capacity and mechanisms after pretreatment with Bi(NO₃)₃. The greater adsorption of radioactive iodine toward Bi@SCGB (adsorption capacity (Qₑ) = 253.71 μg/g) compared to that for SCGB (Qₑ = 23.32 μg/g) and its reduced adsorption capability at higher pH values provide evidence that the adsorption of radioactive iodine with SCGB and Bi@SCGB is strongly influenced by the presence of bismuth materials and the electrostatic repulsion between their negatively charged surfaces and negatively charged radioactive iodine (IO₃⁻). The calculated R² values for the adsorption kinetics and isotherms support that chemisorption plays a crucial role in the adsorption of radioactive iodine by SCGB and Bi@SCGB in aqueous phases. The adsorption of radioactive iodine onto SCGB was linearly correlated with the contact time (h¹/²), and the diffusion of intra-particle predominantly determined the adsorption rate of radioactive iodine onto Bi@SCGB (Cₛₜₐgₑ II (129.20) > Cₛₜₐgₑ I (42.33)). Thermodynamic studies revealed that the adsorption of radioactive iodine toward SCGB (ΔG° = −8.47 to −7.83 kJ/mol; ΔH° = −13.93 kJ/mol) occurred exothermically and that for Bi@SCGB (ΔG° = −15.90 to −13.89 kJ/mol; ΔH° = 5.88 kJ/mol) proceeded endothermically and spontaneously. The X-ray photoelectron spectroscopy (XPS) analysis of SCGB and Bi@SCGB before and after the adsorption of radioactive iodine suggest the conclusion that the change in the primary adsorption mechanism from electrostatic attraction to surface precipitation upon the impregnation of bismuth materials on the surfaces of spent coffee ground biochars is beneficial for the adsorption of radioactive iodine in aqueous phases.