Depassivation of aged Fe 0 by divalent cations: correlation between contaminant degradation and surface complexation constants.

The dechlorination of trichloroethylene (TCE) by aged Fe(0) in the presence of a series of divalent cations was investigated with the result that while no significant degradation of TCE was observed in Milli-Q water or in solutions of Ba(2+), Sr(2+), or Ca(2+), very effective TCE removal was observed in solutions containing Mg(2+), Mn(2+), Co(2+), Fe(2+), Ni(2+), Zn(2+), Cu(2+), or Pb(2+). The rate constants of TCE removal in the presence of particular cations were positively correlated to the log K representing the affinity of the cations for hydrous ferric oxide (HFO) surface sites though the treatments with Co(2+) and Ni(2+) were found to provide particularly strong enhancement in TCE degradation rate. The extent of Fe(II) release to solution also increased with increase in log K, while the solution pH from both experimental measurement and thermodynamic calculation decreased with increasing log K. While the peak areas of Fe and O XPS spectra of the passivated ZVI in the presence of Ba(2+), Sr(2+), and Ca(2+) were very close to those in Milli-Q water, very significant increases in surface Fe and O (and OH) were observed in solutions of Mg(2+), Mn(2+), Co(2+), Fe(2+), Ni(2+), Zn(2+), Cu(2+) and Pb(2+), revealing that the surface oxide layer dissolution is consistent with the recovery of aged Fe(0) with respect to TCE degradation. The depassivation process is proposed to involve (i) surface complexation of cations on surface coatings of aged Fe(0), (ii) dissolution of the hydrated surface as a consequence of magnetite exposure, and (iii) transport of electrons from underlying Fe(0) via magnetite to TCE, resulting in TCE dechlorination and, for some cations (Co(2+), Ni(2+), Cu(2+), and Pb(2+)), reduction to their zero or +1 valence state (with potential for these reduced metals to enhance TCE degradation).