Neoformation of Ni phyllosilicate upon Ni uptake on montmorillonite:: A kinetics study by powder and polarized extended X-ray absorption fine structure spectroscopy

Wet chemistry kinetics and powder and polarized extended X-ray absorption fine structure (EXAFS and P-EXAFS) spectroscopy were combined to investigate the mechanism of Ni uptake on montmorillonite, at pH 8, high ionic strength (0.2 M Ca(NO3)(2)), initial Ni concentration of 660 muM, and solid concentration of 5.3 g/L. Approximately 20% of Ni sorbed within the first 24 h; thereafter, the Ni uptake rate slowed, and 12% of the initial Ni concentration remained in solution after 206 d of reaction time. Powder EXAFS spectra collected on wet pastes at 1, 14, 90, and 206 d showed the presence of Ni-Ni pairs at similar to3.08 A in an amount that gradually increased with time. Results were interpreted by the nucleation of a Ni phase having either an alpha-Ni-hydroxide- or a Ni-phyllosilicate-like local structure. The latter possibility was confirmed by recording P-EXAFS spectra of a highly textured, self-supporting montmorillonite film prepared in the same conditions as the wet samples and equilibrated for 14 d. The orientation distribution of the c*-axes of individual clay particles off the film plane, as measured by quantitative texture analysis, was 32.8degrees full width at half maximum, and this value was used to correct from texture effect the effective numbers of Ni and Si nearest neighbors determined by P-EXAFS. Ni atoms were found to be surrounded by 2.6 +/- 0.5 Ni atoms at similar to3.08 Angstrom in the in-plane direction and by 4.2 +/- 0.5 Si atoms at 3.26 Angstrom in the out-of-plane direction. These structural parameters, but also the orientation and angular dependence of the Ni and Si shells, strongly support the formation of a Ni phyllosilicate having its layers parallel to the montmorillonite layers. The neoformation of a phyllosilicate on metal uptake on montmorillonite, documented herein for the first time, has important geochemical implications because this dioctahedral smectite is overwhelmingly present in the environment. The resulting sequestration of sorbed trace metals in sparingly soluble phyllosilicate structure may durably decrease their migration and bioavailability at the Earth's surface and near surface. Copyright (C) 2002 Elsevier Science Ltd.