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This work developed calcium alginate (CA) embedded zero-valent iron (ZVI@CA) and CA embedded biochar (BC) immobilized microorganism (BC&Cell@CA) gel beads as alternative to conventional Fe⁰ permeable reactive barriers for treating groundwater contaminated with 2,4,6-trichlorophenol (2,4,6-TCP). Lab-scale and field-scale biochar-microorganism augmented PRBs (Bio-PRBs) were constructed and tested. The underlying mechanisms were revealed by a multi-source data calibrated multi-process reaction model, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and high-throughput sequencing. Moreover, calibrated advection-dispersion (a) coupled with the two-site sorption (K_d) and chemical-biological multi-process reaction (λ) model were used for revealing 2,4,6-TCP transport behavior and optimizing Bio-PRBs. Compared to that in the ZVI@CA (0.004 h^–1) system, the reaction rate (0 …