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Aluminum substitution is common in iron (hydr)oxides in subsurface environments, and can significantly modify mineral interactions with contaminants. However, few studies investigate Cr(VI) adsorption and its subsequent mobility on Al-substituted iron (hydr)oxide surfaces. Here shows that Al substitution gradually modifies hematite crystals from 101, 112, 110 and 104 faceted rhombohedra to 001 faceted plates, resulting in a general decrease in Cr(VI) adsorption density and favoring of monodentate mononuclear over bidentate binuclear Cr(VI