Insights into the surface complexation of dimethylarsinic acid on iron (oxyhydr)oxides from ATR-FTIR studies and quantum chemical calculations.
The surface chemistry of methylated arsenicals with ubiquitous geosorbents and industrial catalysts is poorly understood. These arsenic compounds pose both a health and an environmental risk in addition to being a challenge to the energy industry. We report herein a detailed spectroscopic analysis of the surface structure of dimethylarsinic acid (DMA) adsorbed on hematite and goethite using attenuated total internal reflectance Fourier transform infrared spectroscopy (ATR-FTIR). Spectra of adsorbed DMA, DMA(ads), were collected in situ as a function of pH and ionic strength, using both H(2)O and D(2)O at 298 K in flow mode. Experimental data were complemented with DFT calculations of geometries and frequencies of hydrated DMA-iron oxide clusters. Results indicate the simultaneous formation of inner- and outer-sphere complexes with distinct spectral components. Desorption behavior of DMA due to chloride and phosphate was studied as a function of time from the decrease in the absorbance of apparent spectral features. The impact of our studies on the environmental fate of DMA in geochemical environments and the design of technologies to reduce arsenic content in fuels are discussed.
Adamescu
Adrian
A
Chemistry Department, Wilfrid Laurier University, Waterloo, Ontario N2L 3C5, Canada.
Mitchell
William
W
Hamilton
I P
IP
Al-Abadleh
Hind A
HA
D002101:Cacodylic Acid / Q000737:chemistry*; D005290:Ferric Compounds / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D009994:Osmolar Concentration; D011789:Quantum Theory; D017550:Spectroscopy, Fourier Transform Infrared / Q000379:methods*; D013499:Surface Properties
D005290:Ferric Compounds; C000499:ferric oxide; D002101:Cacodylic Acid