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The era of advanced computer simulations in materials science enables a great potential to design in silico computational experiments for (nano-)material performance. The adsorption efficiency of nanoparticles in various environments can be unveiled by atomistic models and computer simulations. Arsenic (As) is one of the important globally distributed contaminants with a hazardous impact on human health and environment, and it can strongly bind with iron nanocrystals (e.g., hematite (Fe 2 O 3)) depending on their shape and size. Here, we developed a novel Kinetic Monte Carlo (KMC) model capable of exploring and delineating shape-efficiency dependence for Fe 2 O 3 nanocrystals in contact with arsenate-contaminated water. This newly designed model demonstrated the performance of nanocrystals for removal of toxic (As) ions on their surface. The current model opens new avenues for designing further advanced KMC models for nanoparticles-toxic ions interactions, under varying environmentally relevant situations, e.g., groundwater, wetlands, and water treatment systems. In addition to bidentate adsorption complexes, implemented in the model presented, monodentate and outer-sphere adsorption complexes should be incorporated into the KMC model. Detailed environmental controls can be addressed by implementation of pH and background ions. [Display omitted] • Statistical mechanics is applied to reveal adsorption mechanisms of toxic ions. • Arsenate (As(V)) adsorption was modeled on iron oxide (hematite) nanocrystals. • As(V) concentration in water-nanoparticle system is efficiently predicted. • As(V) adsorption depends on shape of iron oxide nanocrystals. [ABSTRACT FROM AUTHOR]

• Pure hematite crystal mainly exposes {101}, {12}, {110} and {104} facets. • Al substitution for Fe decreases Cr(VI) adsorption density on hematite. • Cr(VI) forms more monodentate mononuclear complexes on Al-doped hematite surfaces. • Involvement of Fe2+ promotes Cr(VI) reduction and fixation on hematite. 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) adsorption complexes. Consequently, the mobility of Cr(VI) might be increased in environments with an abundance of Al-containing iron (hydr)oxides. However, pre-adsorption of Fe2+ on hematite promotes Cr(VI) adsorption, reduction and fixation, and Al-substituted hematite removes more Cr(VI) than pure hematite. Similarly, although addition of Fe2+ to Cr(VI)-adsorbed hematite remobilizes a small proportion of Cr, it greatly increases the proportion of Cr fixed. As the coexistence of Fe2+ and iron (hydr)oxides is common in subsurface environments, Al-containing iron (hydr)oxides will promote Cr(VI) uptake and retention, with a significant proportion fixed as Cr(III), limiting Cr mobility and toxicity. These results offer new insights into how iron (hydr)oxides might control the behaviors of other high-valence redox-sensitive contaminants, and provide a platform for modeling such processes in complex soil and sediment systems. [ABSTRACT FROM AUTHOR]