Purpose The aim of this study was to evaluate the roles of aluminum-based minerals, especially their surface Lewis acid sites (LASs), on the transformation and fate of chloroacetanilide herbicide contaminants when nucleophilic reagents are present. Materials and methods Batch experiments were used to study propachlor transformation processes under different reaction conditions. The surface bonding of aluminas before and after interacting with propachlor and dithionite were characterized by Fourier transform infrared (FTIR) spectra. The LASs on different aluminas, acting as the key role for accelerating the propachlor transformation, were analyzed by pyridine adsorption/FTIR spectroscopic technique. Results and discussion Rates of dithionite-initiated propachlor dechlorination were increased in the presence of aluminas. Transformation efficiencies of propachlor on different aluminas were found to be as γ-Al 2 O 3  > γ-AlOOH > α-Al 2 O 3 . A higher reaction temperature, higher pH, and higher alumina dosage can further increase the propachlor dechlorination rate. The addition of citric acid may block the active sites on alumina and reduce propachlor transformation by dithionite. FTIR and pyridine adsorption/diffuse reflectance Fourier transform infrared spectroscopy indicated that Al–S and Al–O bonds on the LASs of alumna play a key role in accelerating propachlor transformation. Conclusions LASs on alumina surfaces can effectively accelerate the propachlor transformation by dithionite. The strong electron accepting ability of LASs gives dithionite a favorable affinity to form surface sulfur compounds, which are stronger reductants and nucleophilic reagents for propachlor dechlorination. The intensities of LASs on alumina surfaces can be used to control the rate of propachlor transformation by dithionite.