Abiotic reduction of nitroaromatic contaminants by iron(II) complexes with organothiol ligands

Environmental Toxicology and Chemistry
Daisuke NakaTimothy J Strathmann

Abstract

Complexation of Fe(II) by dissolved and surface-bound ligands can significantly modify the metal's redox reactivity, and recent work reveals that Fe(II) complexes with selected classes of organic ligands are potent reductants that may contribute to the natural attenuation of subsurface contaminants. In the present study, we investigated the reactivity of Fe(II)-organothiol ligand complexes with nitroaromatic contaminants (NACs; ArNO(2)). Experimental results show that NACs are unreactive in Fe(2+)-only and ligand-only solutions but are reduced to the corresponding aniline compounds (ArNH(2)) in solutions containing both Fe(II) and a number of organothiol ligands. Observed reaction rates are highly dependent on the structure of the Fe(II)-complexing ligand, solution composition, Fe(II) speciation, and NAC structure. For two model ligands, cysteine and thioglycolic acid, observed pseudo-first order rate constants for 4-chloronitrobenzene reduction (k(obs); 1/s) are linearly correlated with the concentration of the respective 1:2 Fe(II)- organothiol complexes (FeL(2)(2-)), and k(obs) measurements are accurately predicted by k(obs) = k(FeL(2-)(2))[FeL(2-)(2)], where k(FeL(2-)(2)) = 1.70 (+/-0.59) 1/M/s and 26.0 (+/-4.8) 1/M/s for c...Continue Reading

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