Towards sustainable microplastic cleanup: Al/Fe ionotropic chitosan hydrogels for efficient PET removal

Chitosan (CHI) was modified with iron and aluminum salts to create ionotropic beads, Fe-CHI and Al-CHI, for the removal of polyethylene terephthalate microplastics (PET-MP) from water. Infrared spectroscopy revealed reduced hydrogen bonding associated with N-H vibration of CHI (3500-3100 cm^-1) due to the interaction with the metal ions, and absorption peaks between 500 and 916 cm⁻¹ predominantly due to metal-oxygen stretching vibrations. The swelling behavior of the beads increased with temperature but decreased as pH and metal doping concentration increased. Conductivity and PET-MP removal efficiency improved with higher metal ion concentrations, with Al-CHI exhibiting greater swelling and conductivity compared to Fe-CHI. The highest efficiency for MP remediation was recorded at low pH levels. MP adsorption decreased with rising temperatures and varied with pH changes due to protonation and deprotonation reactions of CHI, along with the various cationic and anionic species formed by the metals. At pH 7, MP removal by Fe-CHI beads declined as the doping concentration increased, attributed to specific Fe species that emerged at this pH. The zeta potential measurements showed that both the beads and the MP were in an unstable range at low pH but shifted towards stability at higher pH levels. Re-adsorption efficiencies exceeded 70% for both low and high-doped Fe-CHI and Al-CHI beads when tested with ~ 40 MP/mL of MP suspension over three different cycles. Overall, the use of ionotropic CHI beads offers a promising, eco-friendly method for effectively reducing PET-MPs in water.