Trace metals (e.g. Ni, Zn) leached from industrial and agricultural processes are often simultaneously present in contaminated soils and sediments. Their mobility, bioavailability, and ecotoxicity are affected by sorption and cosorption at mineral/solution interfaces. Cosorption of trace metals has been investigated at the macroscopic level, but there is not a clear understanding of the molecular-scale cosorption processes due to lack of spectroscopic information. In this study, Ni and Zn cosorption to aluminum oxides (γ-Al₂O₃) in binary-sorbate systems were compared to their sorption in single-sorbate systems as a function of pH using both macroscopic batch experiments and synchrotron-based X-ray absorption fine structure spectroscopy. At pH 6.0, Ni and Zn were sorbed as inner-sphere surface complexes and competed for the limited number of reactive sites on γ-Al₂O₃. In binary-sorbate systems, Ni had no effect on Zn sorption, owning to its lower affinity for the metal oxide surface. In contrast, Zn had a higher affinity for the metal oxide surface and reduced Ni sorption. At pH 7.5, Ni and Zn were sorbed as mixed-metal surface precipitates, including Ni–Al layered double hydroxides (LDHs), Zn–Al LDHs, and likely Ni–Zn–Al layered triple/ternary hydroxides. Additionally, at pH 7.5, Ni and Zn do not exhibit competitive sorption effects in the binary system. Taken together, these results indicated that pH critically influenced the reaction products, and provides a crucial scientific basis to understand the potential mobility, bioavailability, and ecotoxicity of Ni and Zn in natural and contaminated geochemical environments.

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