Unveiling the crucial role of iron oxide transformation in simultaneous immobilization of nanoplastics and organic matter

Nanoplastics (NPs) have been found in natural environments. However, the sequestration of NPs and natural organic matter (NOM) coupled with the Fe(III) hydrolysis and subsequent iron oxides transformation remains unclear. Here, we investigated the behaviors of NPs during the dynamic transformation process of iron oxides in the presence of humic acids (HA). The quantification results of europium chelate-labeled polystyrene (PS) NPs and HA indicate that 87.60 % of NPs and 49.45 % of HA were sequestered in the precipitate by the end of the transformation (240 h). High-angle annular dark-field-scanning transmission electron microscopy-energy dispersive X-ray spectroscopy (HAADF-STEM-EDS) images show that NPs were doped into iron oxides during the recrystallization of ferrihydrite aggregates, while HA were adsorbed or penetrated into the nanoscale pores on the mineral surfaces, suggesting the formation of a stable iron oxides-NPs-NOM ternary nanocomplex with a core-shell structure. Fourier transform infrared spectrometer (FTIR) and two-dimensional correlation spectroscopy (2D-COS) analysis indicate that functional groups of iron oxides and HA, including hydroxyl, carboxyl, and FeO bonds, played a role in the binding process. In the presence of HA, the stability of the coprecipitation system was enhanced due to the increased electrostatic repulsion, which facilitated the full incorporation of NPs with iron oxides. These findings provide a new insight into the simultaneous immobilization of NPs and NOM.