Vibrational spectroscopic characterization of some environmentally important organoarsenicals — A guide for understanding the nature of their surface complexes

Abstract

Organoarsenicals are found in the environment from the biomethylation of inorganic arsenic compounds and from anthropogenic sources. It is clear that organoarsenicals pose a health and an environmental risk due to their potential cycling to the most toxic forms of arsenic as a result of redox activity in soils and natural waters. The environmental fate of arsenic compounds depends to a large extent on the surface interactions with geosorbents, mainly minerals and organic matter. Hence, elucidating the nature of surface complexes is important in understanding binding mechanisms and thermodynamics. In this paper, we report the vibrational spectra of a number of organoarsenicals in the aqueous and solid phases using attenuated total internal reflectance Fourier transform infrared (ATR-FTIR), transmission FTIR, and Raman spectroscopies. Analysis of the aqueous phase spectra revealed that for completely deprotonated anions, increasing the organic substituents on the AsOx moiety results in increasing the frequency of v(AsOx), whereas the opposite trend is observed for completely protonated molecules. Analysis of solid phase spectra showed that incorporation of water molecules in the crystalline structure and extensive hydrogen bonding with neighboring molecules significantly affect As–O bond lengths and hence frequencies of v(AsOx). Results are discussed in the context of identifying geometry of organoarsenicals surface complexes in situ using the ATR-FTIR technique.Key words: ATR-FTIR, organoarsenicals; oxyanion adsorption, arsenate, in situ spectroscopy.