Jian Zhang, Renjie Hou, Anshuang Su, Miao Wang, Heqiang Sun, Hai Xu, Wei Huang, Fei Peng, Shan Zhao
Perfluoroalkyl substances (PFAS), as persistent emerging contaminants, can migrate into rice systems through the soil-water interface (SWI) during irrigation, threatening food security and human health. However, the diffusion characteristics of PFAS at the SWI under carbon-based material regulation and their solute exchange kinetics remain unclear, particularly the quantitative differences between short-chain (PFBA) and long-chain (PFOA) PFAS behaviors. To address this, this study innovatively integrated molecularly imprinted polymer-diffusive gradients in thin films (MIP-DGT) and high-resolution pore water sampling (HR-Peeper) techniques to systematically investigate the regulatory mechanisms of control (WBC), rice husk biochar (RBC), and montmorillonite-modified biochar (MBC) on the migration and accumulation of PFBA and PFOA in the paddy sediment-water-plant system. The results showed that in WBC-treated soil, the surface C DGT -PFBA and C DGT -PFOA concentrations were 6.76 ± 1.44 ng L −1 and 7.21 ± 2.14 ng L −1 , respectively, while biochar treatments significantly inhibited PFAS migration to deeper layers. Compared to WBC, RBC reduced C DGT -PFBA and C DGT -PFOA in deeper soil layers by 32.80 % and 87.50 %, respectively, with modified biochar exhibiting even stronger retention effects. The constructed 2D-DIFS (DGT-induced fluxes in soils/sediments) model indicated that PFAS re-supply capacity (R-value) from soil to pore water declined with irrigation cycles. PFBA had shorter response times (T c ) and higher mobility, while PFOA was more immobilized due to higher adsorption rate (k −1 ) and partition coefficient (K d ). Notably, compared to WBC, RBC reduced PFBA and PFOA accumulation in rice organs by 24.21 ~ 26.26 %, confirming the dual role of carbon-based materials in altering PFAS interfacial behavior and thereby inhibiting plant uptake. This study clarifies PFAS migration and biotransport responses to carbon-based materials under irrigation, supporting strategies to mitigate PFAS contamination in farmland. • Enhanced MIP-DGT technology efficiently identifies and quantifies PFAS. • Biochar inhibits PFAS migration from overlying water to deeper soil layers. • Carbon-based materials can effectively alleviate PFAS pollution in plant organs. • PFOA tends to persist in soil, whereas PFBA is readily accumulated by plants. • PFAS re-supply capacity from soil solids to pore water diminishes over time.