X-ray absorption spectroscopic investigation of arsenite and arsenate adsorption at the aluminum oxide-water interface

We investigated the As(III) and As(V) adsorption complexes forming at the g amma -Al2O3/water interface as a function of pH and ionic strength (I), usi ng a combination of adsorption envelopes, electrophoretic mobility (EM) mea surements, and X-ray absorption spectroscopy (XAS). The As adsorption envel opes show that (1) As(III) adsorption increases with increasing pH and is i nsensitive to I changes (0.01 and 0.8 M NaNO3) at pH 3-4.5, while adsorptio n decreases with increasing I between pH 4.5 and 9.0, and (2) As(V) adsorpt ion decreases with increasing pH and is insensitive to I changes at pH 3.5- 10. The EM measurements show that As(III) adsorption does not significantly change the EM values of gamma -Al2O3 suspension in 0.1 M NaNO3 at pH 4-8, whereas As(V) adsorption lowered the EM values at pH 4-10. The EXAFS data i ndicate that both As(III) and As(V) form inner-sphere complexes with a bide ntate binuclear configuration, as evidenced by a As(III)-Al bond distance o f congruent to3.22 Angstrom and a As(V)-Al bond distance of congruent to3.1 1 Angstrom. The As(III) XANES spectra, however, show that outer-sphere comp lexes are formed in addition to inner-sphere complexes and that the importa nce of outer-sphere As(III) complexes increases with increasing pH (5.5 to 8) and with decreasing I. In short, the data indicate for As(III) that inne r- and outer-sphere adsorption coexist whereas for As(V) inner-sphere compl exes are predominant under our experimental conditions, (C) 2001 Academic P ress.