Diversity in the species and fate of chlorine during TCE reduction by two nZVI with non-identical anaerobic corrosion mechanism

There have been many studies on TCE degradation by synthesized nanoscale zero-valent iron (nZVIB) and commercial nanoscale zero-valent iron (nZVIH), but the effect of anaerobic corrosion on the dechlorination pathways and speciation distribution of chlorine is still unclear. Compared with nZVIH, nZVIB has a faster degradation rate of TCE and formation rate of Cl−(aq) (kSA, TCE = 3.67 ± 0.85 × 10−4 & 2.17 ± 0.13 × 10−4 L·h−1·m−2 and kobs, Cl− = 0.344 ± 0.027 & 0.166 ± 0.010 μM·h−1 for nZVIB & nZVIH, respectively). Based on the characterization of XRD, XPS and TEM during the anaerobic corrosion, the corrosion of nZVIB was dramatic under the dissolution-reprecipitation mechanism; but that of nZVIH 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 nZVIB and Fe3O4/γ-Fe2O3 for nZVIH) and the catalysis of boron on the nZVIB surface, the preferential dechlorination pathway of TCE was not identical by hydrogenolysis (nZVIB) vs. reductive β-elimination (nZVIH). Meanwhile, the dechlorination pathway of nZVIH 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 nZVIB results in rapid corrosion with the side effect of enhanced adsorption of VC while nZVIH 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.