title: Atom exchange between aqueous Fe(II) and goethite: an Fe isotope tracer study.
abstract: The reaction of aqueous Fe(II) with Fe(III) oxides is a complex process, comprising sorption, electron transfer, and in some cases, reductive dissolution and transformation to secondary minerals. To better understand the dynamics of these reactions, we measured the extent and rate of Fe isotope exchange between aqueous Fe(II) and goethite using a 57Fe isotope tracer approach. We observed near-complete exchange of Fe atoms between the aqueous phase and goethite nanorods over a 30-day time period. Despite direct isotopic evidence for extensive mixing between the aqueous and goethite Fe, no phase transformation was observed, nor did the size or shape of the goethite rods change appreciably. High-resolution transmission electron microscopy images, however, appear to indicate that some recrystallization of the goethite particles may have occurred. Near-complete exchange of Fe between aqueous Fe(II) and goethite, coupled with negligible change in the goethite mineralogy and morphology, suggests a mechanism of coupled growth (via sorption and electron transfer) and dissolution at separate crystallographic goethite sites. We propose that sorption and dissolution sites are linked via conduction through the bulk crystal, as was recently demonstrated for hematite. Extensive mixing between aqueous Fe(II) and goethite, a relatively stable iron oxide, has significant implications for heavy metal sequestration and release (e.g., arsenic and uranium), as well as reduction of soil and groundwater contaminants.
authors.affiliation: Department of Civil and Environmental Engineering, University of Iowa, 4105 Seamans Center, Iowa City, Iowa 52242, USA.
authors.forename: Robert M
authors.initials: RM
authors.lastname: Handler
authors.forename: Brian L
authors.initials: BL
authors.lastname: Beard
authors.forename: Clark M
authors.initials: CM
authors.lastname: Johnson
authors.forename: Michelle M
authors.initials: MM
authors.lastname: Scherer