title: Mechanisms of chromate adsorption on boehmite.
abstract: Adsorption reactions play an important role in the transport behavior of groundwater contaminants. Molecular-scale information is needed to elucidate the mechanisms by which ions coordinate to soil mineral surfaces. In this study, we characterized the mechanisms of chromate adsorption on boehmite (γ-AlOOH) using a combination of extended X-ray absorption fine structure (EXAFS) measurements, in situ attenuated total reflectance Fourier transform infrared spectroscopy, and quantum chemical calculations. The effects of pH, ionic strength, and aqueous chromate concentration were investigated. Our overall findings were that chromate primarily forms outer-sphere complexes on boehmite over a broad range of pH and aqueous concentrations. Additionally, a small fraction of monodentate and bidentate inner-sphere complexes are present under acidic conditions, as evidenced by two sets of chromate stretching vibrations at approximately 915, 870, and 780cm(-1), and 940, 890, 850, and 780cm(-1), respectively. The bidentate complex is supported by a best-fit CrAl distance in the EXAFS of 3.2Å. Results from DFT also support the formation of monodentate and bidentate complexes, which are predicted to results in Gibbs energy changes of -140.4 and -62.5kJmol(-1), respectively. These findings are consistent with the intermediate binding strength of chromate with respect to similar oxyanions such as sulfate and selenite. Overall, the surface species identified in this work can be used to develop a more accurate stoichiometric framework in mechanistic adsorption models.
authors.affiliation: University of Connecticut, Civil and Environmental Engineering, Storrs, CT 06269, USA. Electronic address: chad.johnston@engr.uconn.edu.
authors.forename: Chad P
authors.initials: CP
authors.lastname: Johnston
authors.affiliation: University of Connecticut, Civil and Environmental Engineering, Storrs, CT 06269, USA; National Technical University of Athens, School of Civil Engineering, Athens, Greece.
authors.forename: Maria
authors.initials: M
authors.lastname: Chrysochoou
mesh_terms: D000327:Adsorption; D000536:Aluminum Hydroxide / Q000737:chemistry*; D000537:Aluminum Oxide / Q000737:chemistry*; D002840:Chromates / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D008958:Models, Molecular; D009994:Osmolar Concentration; D017550:Spectroscopy, Fourier Transform Infrared; D014874:Water Pollutants, Chemical / Q000737:chemistry*; D056928:X-Ray Absorption Spectroscopy
chemical_list: D002840:Chromates; D014874:Water Pollutants, Chemical; D000536:Aluminum Hydroxide; C069471:aluminum oxide hydroxide; D000537:Aluminum Oxide
keywords: ATR-FTIR; Aluminum oxides; Density functional theory; EXAFS; Surface complexation