Mechanisms of Arsenic Adsorption on Amorphous Oxides Evaluated Using Macroscopic Measurements, Vibrational Spectroscopy, and Surface Complexation Modeling.

Arsenic adsorption on amorphous aluminum and iron oxides was investigated as a function of solution pH, solution ionic strength, and redox state. In this study in situ Raman and Fourier transform infrared (FTIR) spectroscopic methods were combined with sorption techniques, electrophoretic mobility measurements, and surface complexation modeling to study the interaction of As(III) and As(V) with amorphous oxide surfaces. The speciation of As(III) and As(V) in aqueous solution was examined using Raman and attenuated total reflectance (ATR)-FTIR methods as a function of solution pH. The position of the As-O stretching bands, for both As(III) and As(V), are strongly pH dependent. Assignment of the observed As-O bands and their shift in position with pH was confirmed using semiempirical molecular orbital calculations. Similar pH-dependent frequency shifts are observed in the vibrational bands of As species sorbed on amorphous Al and Fe oxides. The mechanisms of As sorption to these surfaces based on the spectroscopic, sorption, and electrophoretic mobility measurements are as follows: arsenate forms inner-sphere surface complexes on both amorphous Al and Fe oxide while arsenite forms both inner- and outer-sphere surface complexes on amorphous Fe oxide and outer-sphere surface complexes on amorphous Al oxide. These surface configurations were used to constrain the input parameters of the surface complexation models. Inclusion of microscopic and macroscopic experimental results is a powerful technique that maximizes chemical significance of the modeling approach. Copyright 2001 Academic Press.