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This study investigated methylene blue (M degradation by the vacuum-ultraviolet/ultraviolet/persulfate (VUV/UV/PS) process using a mini-fluidic VUV/UV photoreaction system. Results show that MB degradation by the VUV/UV/PS process was significantly higher than that of the conventional UV/PS process, as the VUV photolysis of H2O and PS generated more reactive oxygen species (ROSs). HO• and SO4•-, identified as the main ROSs, were mostly consumed by dissolved organic carbon and Cl‒ in real waters, respectively. Additionally, the impacts o