Raman spectroscopic study of the hydrogen and arsenate bonding environment in isostructural synthetic arsenates of the variscite group—M³⁺ AsO₄·2H₂O (M³⁺ = Fe, Al, In and Ga): implications for arsenic release in water

Abstract

Abstract The Raman spectra of synthetic compounds equivalent to the variscite group: FeAsO 4 ·2H 2 O AlAsO 4 ·2H 2 O, GaAsO 4 ·2H 2 O, and InAsO 4 ·2H 2 O are reported. In particular, upon comparison of FeAsO 4 ·2H 2 O to AlAsO 4 ·2H 2 O, it is observed that the Type II (weak) H‐bond lengths in the latter are slightly longer, which is postulated to affect the stability (As release) in water at pH 5 and 7. Arsenate stretching and bending vibrations were found to be distinct in terms of spectral structure and therefore well suited for fingerprinting. The calculated AsO bond strengths from existing crystallographic data showed no significant variations. The strongest ν 1 (AsO 4 3− ) stretch was used to monitor the AsO bonding interactions in the four AsOM units, where a shift of 114 cm −1 was observed in the order FeAsO 4 ·2H 2 O (lowest) < InAsO 4 ·2H 2 O < GaAsO 4 ·2H 2 O < AlAsO 4 ·2H 2 O (highest); this order also followed exactly the measured arsenic release of these phases. This shift in ν 1 (AsO 4 3− ) position was rationalized to stem from the differences in the electronegativities of the M 3+ cations. The trends mentioned above were verified and found to also hold for the isostructural phosphate analogues strengite (FePO 4 ·2H 2 O) and variscite (AlPO 4 ·2H 2 O) using published data. Therefore, it is postulated that, as observed with the stability of solution complexes, there may be a correlation between the electronegativity of the M 3+ cation in these isostructural phases and their stability (As or P release) in water. Copyright © 2010 John Wiley & Sons, Ltd.