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Title: Diversity in the species and fate of chlorine during TCE reduction by two nZVI with non-identical anaerobic corrosion mechanism.
Author: Yang X, Zhang C, Liu F, Tang J, Huang F, Zhang L.
Journal: Chemosphere; 2019 Sep; 230():230-238. PubMed ID: 31103869.
Abstract:
There have been many studies on TCE degradation by synthesized nanoscale zero-valent iron (nZVI^B) and commercial nanoscale zero-valent iron (nZVI^H), but the effect of anaerobic corrosion on the dechlorination pathways and speciation distribution of chlorine is still unclear. Compared with nZVI^H, nZVI^B has a faster degradation rate of TCE and formation rate of Cl^-(aq) (k_{SA, TCE} = 3.67 ± 0.85 × 10^-4 & 2.17 ± 0.13 × 10^-4 L·h^-1·m^-2 and k_{obs, Cl}^- = 0.344 ± 0.027 & 0.166 ± 0.010 μM·h^-1 for nZVI^B & nZVI^H, respectively). Based on the characterization of XRD, XPS and TEM during the anaerobic corrosion, the corrosion of nZVI^B was dramatic under the dissolution-reprecipitation mechanism; but that of nZVI^H was moderate and inward by maintaining the core-shell structure and shaping slightly rough and lumpy surface. Due to the different corrosion products (FeOOH for nZVI^B and Fe₃O₄/γ-Fe₂O₃ for nZVI^H) and the catalysis of boron on the nZVI^B surface, the preferential dechlorination pathway of TCE was not identical by hydrogenolysis (nZVI^B) vs. reductive β-elimination (nZVI^H). Meanwhile, the dechlorination pathway of nZVI^H was similar to that of ZVI and the reductive pathway to acetylene bypassed the formation of more toxic VC. This study shows that the high reactivity of nZVI^B results in rapid corrosion with the side effect of enhanced adsorption of VC while nZVI^H has a stable core-shell structure and less sorbed chlorine, which provides a new sight to access the ecological risk of nZVI due to the overlooked effect of non-identical corrosion.

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