LAUSR

Abstract Systematic investigation on the adsorption performance of polystyrene-based nanospheres towards persistent organic pollutants (POPs) is of great importance to the design of high-capacity adsorbent and the toxicological risk assessment of nano plastic. In this study, a series of polystyrene-based nanospheres with controllable microstructures, have been constructed successfully as model adsorbents, by the strategies of emulsion polymerization, hyper-crosslinking and direct carbonization. In the form of Solid phase microextraction (SPME) coatings, the impacts of microstructures on the adsorption performance of constructed nanospheres have been highlighted, by employing benzene series, polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) as target adsorbates. Moreover, it is surprisingly found that the grafted F atoms make PS demonstrate better enrichment effects towards PCBs than the Cl atoms, mainly due to stronger sigma (σ)-hole interactions between F atoms and PCBs. In consideration of the most outstanding performance, the F-functionalized nanospheres (xFFNs)-coated SPME fiber is employed for the enrichment of PCBs from water samples, and the enrichment factors range from 1500 to 10030. After coupling the xFFNs-coated fiber with gas chromatography-mass spectrometry (GC-MS), highly sensitive analytical method is developed with detection limits of 0.08–0.89 ng L−1, realizing precise quantifications of trace PCBs in treated sewage samples.