During electrochemical remediation of radionuclide, 235U, 238U, and 99Tc-contaminated aqueous solutions, pyroaurite-like phases, ideally [M(II)M(III)(OH)16CO3·4H2O] where M = Fe, were synthesized following coprecipitation with iron from metal iron electrodes. The effect of radionuclides on the transformation of amorphous precipitates to crystalline pyroaurite-like phases was investigated using X-ray diffraction (XRD), scanning electron microscopy with energy dispersive X-ray analysis, Fourier-transform infrared (FTIR) spectroscopy, and fluorescence spectroscopy. The synthetic iron carbonate hydroxide phases showed primary XRD peaks at 0.7 and 0.35 nm and FTIR spectra that indicated the presence of a brucite-like sheet structure with carbonate anions occupying the interlayer. Divalent and trivalent iron, eroded from the electrode, occupies the octahedral sites of the brucite-like sheets. The carbonate anions in the interlayer balance the excess positive charge from isomorphous substitution of the Fe2+ or Fe3+ by reduced uranium (U4+) and technetium (Tc4+). Because of the lower solubility associated with crystalline phases than amorphous phases, incorporation of radioactive contaminants into pyroaurite-like phases by electrochemical syntheses represents a more effective approach for removing U and Tc from contaminated aqueous solutions than traditional technologies.

The combination of zero-valent iron (ZVI) and a clay-type amendment is often observed to have a synergistic effect on the rate of reduction reactions. In the present study, electrochemical techniques were used to determine the mechanism of interaction between the iron (Fe) and smectite clay minerals. Iron electrodes coated with an evaporated smectite suspension (clay-modified iron electrodes, CMIEs) were prepared using five different smectites: SAz-1, SWa-1, STx-1, SWy-1, and SHCa-1. All the smectites were exchanged with Na+ and one sample of SWy-1 was also exchanged with Mg2+. Potentiodynamic polarization scans and cyclic voltammograms were taken using the CMIEs and uncoated but passivated Fe electrodes. These electrochemical experiments, along with measurements of the amount of Fe2+ and Fe3+ sorbed in the smectite coating, suggested that the smectite removed the passive layer of the underlying Fe electrode during the evaporation process. Cyclic voltammograms taken after the CMIEs were biased at the active-passive transition potential for varying amounts of time suggested that the smectite limited growth of a passive layer, preventing passivation. These results are attributed to the Brønsted acidity of the smectite as well as to its ability to sorb Fe cations. Oxides that did form on the surface of the Fe in the presence of the smectite when it was biased anodically were reduced at a different electrochemical potential from those that form on the surface of an uncoated Fe electrode under otherwise similar conditions; this difference suggested that the smectite reacted with the Fe2+ formed from the oxidation of the underlying Fe. No significant correlation could be found between the ability of the smectite to remove the Fe passive film and the smectite type. The results have implications for the mixing of sediments and Fe particles in permeable reactive barriers, underground storage of radioactive waste in steel canisters, and the use of smectite supports in preventing aggregation of nano-sized zero-valent iron.

Atrazine is the most widely used herbicide in the U.S. and has been detected in surface water and groundwater. Technologies are needed for onsite and in situ remediation of water and soil containing atrazine. We investigated the potential of using fine-grained, zero-valent iron (Fe0) to remove atrazine and promote its degradation in contaminated water and soil. Atrazine loss from aqueous solution increased with increasing Fe0 concentration (w/v). Agitating 20 μg 14C-ring-labeled atrazine L−1 with 10% Fe0 (w/v) removed 92% of the 14C from solution within 48 h. Only about 4% of the 14C lost from solution was extractable from the iron with 3 mM CaCl2 (readily available pool), 81% was extractable with CH3CN (potentially available pool), and 11% was unextractable residues. A companion experiment indicated that most of the 14C extracted from the iron with 3 mM CaCl2 after the 48-h Fe0 treatment was unaltered atrazine, while the CH3CN extract contained approximately 33% atrazine and 48% was unidentified atrazine transformation products. Treating a highly contaminated solution (20 mg atrazine L−1) with 20% Fe0 (w/v) removed 88% of the 14C (added as 14C-ring-labeled atrazine) from solution within 48 h. Deethylatrazine was the main atrazine transformation product detected in solution after treatment, but small amounts of deisopropylatrazine, didealkylatrazine, and hydroxyatrazine were also found. Treating Sharpsburg surface soil containing 1 mg atrazine kg−1 with Fe0 (2%, w/w) increased atrazine mineralization from 4.1 to 11.2% after 120 d. Pyrite (4% FeS2, w/w) also increased atrazine mineralization in surface soil, but was less effective in the presence of NO3 − or SO4 2− (100 mg kg−1 soil). Adding 2% Fe0 (w/w) and 100 mg NO3 − kg−1 to contaminated subsurface soil increased atrazine mineralization from 0.4 to 8.2% within 120 d, and unextractable residues increased from 4.6 to 9.8%. These results indicate iron can sorb atrazine and promote its transformation in water and soil.