Investigation of the different binding edge sites for Zn on montmorillonite using P-EXAFS - The strong/weak site concept in the 2SPNE SC/CE sorption model

The 2 site protolysis non electrostatic surface complexation and cation exchange (2SPNE SC/CE) sorption model has been used over the past decade or so to quantitatively describe the uptake of metals with oxidation states from II to VI on 2:1 clay minerals; montmorillonite and illite. One of the main features in this model is that there are two broad categories of amphoteric edge sorption sites; the so called strong ((SOH)-O-S) and weak ((SOH)-O-W1) sites. Because of their different sorption characteristics, it was expected that the coordination environments of the surface complexes on the two site types would be different. Zn isotherm data on two montmorillonites, Milos and STx-1, were measured and modelled using the 2SPNE SC/CE sorption model. The results were used to define the most favourable experimental conditions under which Zn sorption was either dominated by the strong ((SOH)-O-S, similar to 2 mmol kg(-1)) or by the weak sites ((SOH)-O-W1, similar to 40 mmol kg(-1)). Highly oriented self-supporting films were prepared for polarised extended X-ray absorption fine structure (P-EXAFS) investigations. Montmorillonites often contain Zn incorporated in the clay matrix. The Zn bound in this form was quantified and the results from the analysis of the P-EXAFS spectra were taken into account in the interpretation of the spectra measured at low Zn loadings (similar to 2 mmol kg(-1)) and medium Zn loadings (similar to 30 mmol kg(-1)). The Zn spectra on the strong sites exhibited a pronounced angular dependency and formed surface complexes in the continuity of the Al-octahedral sheets at the montmorillonite edges. In contrast, the Zn weak site spectra showed only a weak angular dependency. The spectroscopic evidence indicates the existence of two distinct groups of edge surface binding sites which is consistent with a multi-site sorption model and in particular with the strong/weak site concept intrinsic to the 2SPNE S/CE sorption model. (C) 2011 Elsevier Ltd. All rights reserved.