Persulfate activation with rice husk-based magnetic biochar for degrading PAEs in marine sediments

Phthalate esters (PAEs) can interfere with the endocrine systems of humans and wildlife. The main objective of this study was to evaluate the suitability of a composite for remediating marine sediments contaminated with PAEs. The composite was synthesized with magnetite nanoparticles (Fe3O4) and rice husk biochar (RHB) by using chemical co-precipitation. Fe3O4, RHB, and Fe3O4–RHB substantially activated sodium persulfate (Na2S2O8, PS) oxidation to form SO4−• and thus degrade PAEs in marine sediments in a slurry system. The morphology and structural composition of the magnetic composites were examined using XRD, FTIR, environmental scanning electron microscopy–energy-dispersive X-ray spectrometry, and superconducting quantum interference device. The Fe3O4–RHB composites were confirmed to be prepared successfully. The influences of various parameters, including the PS concentration, composite loading, and initial pH, were investigated. The concentration of high-molecular-weight PAEs (HPAEs) in sediment was much higher than that of low-molecular-weight PAEs (LPAEs); di-(2-ethylhexyl) phthalate (DEHP) was an especially salient marker of PAE contamination in sediments. Furthermore, increasing the PS and Fe3O4–RHB doses accelerated PAE oxidation at pH 3.0; 83% degradation of PAEs was achieved when the PS and Fe3O4–RHB concentrations were increased to 2.3 × 10−2 mM and 1.67 g/L, respectively. LPAEs such as dibutyl phthalate (DnBP) are easier to degrade than HPAEs such as DEHP, diisononyl phthalate (DINP), and diisodecyl phthalate (DIDP). In addition, possible activation mechanisms of the interactions between S2O82− and Fe2+/Fe3+ on the Fe3O4 surface, which involve an efficient electron transfer mediator of the RHB oxygen functional groups promoting the generation of SO4−• in the Fe3O4–RHB/PS system, were clarified. Thus, the Fe3O4–RHB/PS oxidation process is expected to be a viable method for remediating PAE-contaminated marine sediment.