Enhanced heavy metal adsorption on microplastics by incorporating flame retardant hexabromocyclododecanes: Mechanisms...

Microplastics (MPs) are known to act as carriers of heavy metals; however, little is known about the intrinsic chemical additives of MPs, such as hexabromocyclododecane (HBCD), in terms of the adsorption behaviors and migration risks of heavy metals on MPs. Here, we reported the potential mechanisms and risks of HBCD inherent in polystyrene (PS) MPs with Cu(II), Ni(II), and Zn(II) adsorption/desorption. A comparison of the adsorption capacity of the metals onto HBCD/PS composites (HBCD/PS) MPs (10.31-20.76 μmol/g), pure MPs (0-3.60 μmol/g), and natural minerals (0.11-13.88 μmol/g) showed that the addition of HBCD significantly promoted the metals adsorption onto the HBCD/PS MPs, and even exceeded that of natural particles. Isotherms and thermodynamic data suggested that the adsorption process of the metals onto the HBCD/PS MPs was spontaneous and endothermic, and that the adsorption was a mainly multi-ion process with an inclined direction. Furthermore, the results of SEM-EDS, FTIR, and XPS analyses, as well as density functional theory well explained that the metals were mainly adsorbed on the -O and -Br groups of the HBCD/PS MPs via electrostatic interactions and surface complexation. More importantly, by comparing the desorption activity with natural river water and seawater, HBCD inherent in MPs can enhance the long-range transfer of metals carried by the HBCD/PS MPs from contamination sources to potential sink like oceans. Thus, the HBCD/PS MPs with high loading of Cu(II), Ni(II), and Zn(II) could be potential secondary sources of these metals in seawater. Overall, these findings revealed the potential risks of flame retardant in MPs associated with metal migration, and advocated that flame retardant-related waste MPs should be included in coastal sustainable development.