The mechanisms involved in the activation of persulfate by nanosized zero-valent iron (NZVI) were elucidated and the NZVI transformation products identified. Two distinct reaction stages, in terms of the kinetics and radical formation mechanism, were found when phenol was oxidized by the persulfate/NZVI system. In the initial stage, lasting 10 min, Fe was consumed rapidly and sulfate radicals were produced through activation by aqueous Fe. The second stage was governed by Fe catalyzed activation in the presence of aqueous Fe and iron (oxyhydr)oxides in the NZVI shells. The second stage was 3 orders of magnitude slower than the initial stage. An electron balance showed that the sulfate radical yield per mole of persulfate was more than two times higher in the persulfate/NZVI system than in the persulfate/Fe system. Radicals were believed to be produced more efficiently in the persulfate/NZVI system because aqueous Fe was supplied slowly, preventing sulfate radicals being scavenged by excess aqueous Fe. In the second stage, the multilayered shell conducted electrons, and magnetite in the shell provided electrons for the activation of persulfate. Iron speciation analysis (including X-ray absorption spectroscopy) results indicated that a shrinking core/growing shell model explained NZVI transformation during the persulfate/NZVI process.

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Atmospherically stable NZVI (nanoscale zero-valent iron) particles were produced by modifying shell layers of Fe(H2) NZVI particles (RNIP-10DS) by using a controlled air contact method. Shell-modified NZVI particles were resistant to rapid aerial oxidation and were shown to have TCE degradation rate constants that were equivalent to 78% of those of pristine NZVI particles. Fe(H2) NZVI particles that were vigorously contacted with air (rapidly oxidized) showed a substantially compromised reactivity. Aging of shell-modified particles in water for one day resulted in a rate increase of 54%, implying that depassivation of the shell would play an important role in enhancing reactivity. Aging of shell-modified particles in air led to rate decreases by 14% and 46% in cases of one week and two months of aging, respectively. A series of instrumental analyses using transmission electron microscopy, X-ray diffractography, X-ray photoelectron spectroscopy, and X-ray absorption near-edge structure showed that the shells of modified NZVI particles primarily consisted of magnetite (Fe(3)O(4)). Analyses also implied that the new magnetite layer produced during shell modification was protective against shell passivation. Aging of shell-modified particles in water yielded another major mineral phase, goethite (alpha-FeOOH), whereas aging in air produced additional shell phases such as wustite (FeO), hematite (alpha-Fe(2)O(3)), and maghemite (gamma-Fe(2)O(3)).

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