Aging (or longevity) is one of the most important and potentially limiting factors in the use of nano-Fe 0 to reduce groundwater contaminants. We investigated the aging of Fe H2 (Toda RNIP-10DS) in water with a focus on changes in (i) the composition and structure of the particles (by XRD, TEM, XPS, and bulk Fe 0 content) and (ii) the reactivity of the particles (by carbon tetrachloride reaction kinetics, electrochemical corrosion potentials, and H 2 production rates). Our results show that Fe H2 becomes more reactive between 0 and ∼2 days exposure to water and then gradually loses reactivity over the next few hundred days. These changes in reactivity correlate with evidence for rapid destruction of the original Fe(III) oxide film on Fe H2 during immersion and the subsequent formation of a new passivating mixed-valence Fe(II)-Fe(III) oxide shell. The effect of aging on the rate of carbon tetrachloride reduction was best described by the corrosion potential of Fe H2 , whereas the yield of chloroform from this reaction correlated best with the rate of H 2 production. The behavior of unaged nano-Fe 0 in the laboratory may be similar to that in field-scale applications for source-zone treatment due to the short reaction times involved. Long-term aged Fe H2 acquires properties that are relatively stable over weeks or even months.

Reactions mediated by iron mineral surfaces play an important role in the fate of organic contaminants in both natural and engineered systems. As such reactions proceed, the size, morphology, and even the phase of iron oxide minerals can change, leading to altered reactivity. The reductive degradation of 4-chloronitrobenzene and trichloronitromethane by Fe(II) associated with goethite (alpha-FeOOH) was examined by performing sequential-spike batch experiments. The particle size and size distribution of the pre- and postreaction particles were quantified using transmission electron microscopy (TEM). Results demonstrate that the degradation reactions result in goethite growth in the c-direction. Furthermore, pseudo-first-order reaction rate constants for the degradation of 4-chloronitrobenzene and trichloronitromethane and for the loss of aqueous Fe(II) decrease dramatically with each subsequent injection of organic compound and Fe(II). This result indicates that the newly formed material, which TEM and X-ray diffraction results confirm is goethite, is progressively less reactive than the original goethite. These results represent an important step toward elucidating the link between mineral surface changes and the evolving kinetics of contaminant degradation at the mineral-water interface.