Extended X-ray absorption fine structure (EXAFS) spectroscopy combined with statistical F-tests is used to investigate the local atomic structures of Ni(II) adsorbed on Na-rectorite. The EXAFS analysis results of Ni(II) sorption samples indicate that the first coordination shell consists of similar to 6 O at the Ni-O interatomic distance (R) of similar to 2.04 angstrom. The presence of Ni backscattering at RNi-Ni = similar to 3.06 angstrom in the second coordination shell suggests the formation of Ni(II) precipitate. The results of F-tests show that the Ni(II) precipitate is Ni-Al layered double hydroxide (LDH). Our results demonstrate that Ni(II) ions are retained via different mechanisms depending on solution conditions. At low pH, Ni retention is controlled mainly by the outer-sphere surface complexation. With increasing pH, outer-sphere and inner-sphere surface complexation dominate Ni uptake. Furthermore, Ni surface loading increases with temperature increasing at pH 6.5 due to the formation of inner-sphere surface complexes and Ni-Al LDH. The formation of Ni-Al LDH becomes the dominate mechanism at the elevated pH and temperature. In the presence of humic substances, the sorption of Ni(II) on Na-rectorite is dominated by the formation of ternary surface complexes. These results are important to understand the physicochemical behavior of Ni(II) in the natural environment. (c) 2013 Elsevier B.V. All rights reserved.