The Competitive Adsorption of Chromate and Sulfate on Ni-Substituted Magnetite Surfaces: An ATR-FTIR Study

With similar chemical properties and geometrical configurations, sulfate and chromate display interesting competitive adsorption on mineral surfaces. Although such issues have been investigated on several Fe (hydr)oxide surfaces, e.g., ferrihydrite, goethite and hematite, the competitive adsorption on magnetite surfaces and the constraint mechanism have seldom been studied. This impedes the understanding of the transfer and fate of chromate and sulfate on magnetite surfaces, as magnetite is not only a useful adsorbent but also an efficient reductant to decrease the mobility and toxicity of chromium. In the present study, the geometries of the competitive adsorption of chromate and sulfate on Ni-substituted magnetite surfaces over a pH range of 4–9 were investigated using in situ attenuated total reflectance Fourier transform infrared spectroscopy and two-dimensional correlation analysis. In individual adsorption, nonprotonated monodentate mononuclear (NMM) complexes dominated chromate adsorption, accompanied by a few bidentate binuclear (BB) complexes. For sulfate, NMM complexes and outer-sphere (OS) species predominated under acidic and neutral–alkaline conditions, respectively. The above variation in adsorption configuration resulted in the different adsorption competitiveness between chromate and sulfate at different pH values. Specifically, the NMM complexes of chromate were substituted by NMM sulfate complexes under acidic conditions and vice versa. However, under neutral and alkaline conditions, the OS species of sulfate scarcely affected the adsorption of chromate. The adsorption affinity of chromate and sulfate on Ni-substituted magnetite increased in the following order: OS complex (sulfate) < NMM complexes (chromate) < NMM complexes (sulfate).