Spectroscopic Investigation of Cr(III)- and Cr(VI)-treated Nanoscale Zerovalent Iron

The reaction of hexavalent chromium (Cr(VI)) with zerovalent iron (Fe0) during soil and groundwater remediation is an important environmental process. This study used several techniques including X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy to investigate nanometer scale Fe0 particles (nano Fe0) treated with Cr(III) and Cr(VI). X-ray diffraction and XPS analyses of oxidized nano Fe0 showed the crystalline Fe(III) phase is composed of lepidocrocite (gamma-FeOOH). Results of XPS Cr 2p data and Cr K-edge X-ray absorption near edge spectroscopy (XANES) provided evidence that Cr(VI) was entirely reduced to Cr(III) by nano Fe0 with no residual Cr(VI) after reaction. In addition, XPS and XANES results of Cr(III) precipitated as Cr(OH)3 in the presence of corroding nano Fe0 were nearly identical to the Cr(VI)-nano Fe0 reaction product. Detailed analysis of XPS O 1s line spectra revealed that both Cr(III)- and Cr(VI)-treated nano Fe0 yielded a predominantly hydroxylated Cr(OH)3 and/ or a mixed phase CrxFe(1 - x)(OH)3 product. The structure of the Cr(III)- and Cr(VI)-treated nano Fe0 determined using extended X-ray absorption fine structure spectroscopy (EXAFS) revealed octahedral Cr(III) with Cr-O interatomic distances between 1.97 and 1.98 A for both Cr(III) and Cr(VI) treatments and a pronounced Cr-Cr second interatomic shell at 3.01 A. Our results suggest that the reaction product of Cr(VI)-treated nano Fe0 is either a poorly ordered Cr(OH)3 precipitate or possibly a mixed phase CrxFe(1 - x)(OH)3 product, both of which are highly insoluble under environmental conditions.