Spectroscopic studies of arsenic retention onto biotite

Biotite is a constituent Fe-bearing mineral of Delta subsoils in India and Bangladesh and has been hypothesized as a primary source of arsenic (As). The adsorption behavior of As onto structural Fe(II, III)-bearing biotite fractions ( <50 mu m) was investigated in the pH range of 4-8 under a CO(2)-free, anoxic condition (O(2)<1 ppmv) using X-ray Photoelectron Spectroscopy (XPS) and X-ray Absorption Spectroscopy (XAS). The batch experiments indicate that As adsorption is strongly pH dependent and that As(V) adsorbs more efficiently than As(III). X-ray Absorption Near-Edge Structure (XANES) spectra show no oxidation or reduction of As by biotite after reaction with As(III) or As(V) solutions for 3 days. Extended X-ray Absorption Fine Structure (EXAFS) spectroscopic results suggest that As(III) forms bidentate mononuclear edge-sharing ((2)E) and bidentate binuclear corner-sharing ((2)C) surface complexes at pH 7.7 as indicated by average As-Fe bond distances at 3.00 +/- 0.02 angstrom and 3.37 +/- 0.03 angstrom respectively. The surface speciation retrieved by XPS does not provide any evidence of reduction of As(V) on biotite after 30 days further confirming the thermodynamic prediction and the XANES results. This study has therefore significant environmental implications for As contaminated areas, where biotite retards the release of As into reducing groundwater. The changes in soil redox conditions and weathering of biotite may likely contribute to the occurrence of high As in groundwater. (C) 2010 Elsevier B.V. All rights reserved.