The in-situ reduction of zero-valent iron (ZVI) is an effective method for removing chlorinated aliphatic hydrocarbons (CAHs) from groundwater. The heterogeneity of environmental conditions is also crucial in affecting dechlorination efficiency. Until now, the effect of Sulfate (SO42-) on ZVI activity has been debated, and the related mechanism research on SO42- behaviour during the abiotic reduction process of chlorinated alkanes is still lacking. In this study, the impacts of SO42- concentrations (0, 2, 4, 8, 80 mM) on the degradation of 1,1,2-trichloroethane (1,1,2-TCA) by micron-size ZVI (mZVI) and nano-size ZVI (nZVI) were systematically investigated. For mZVI, Kobs increased by 0.6 (2 mM), 0.5 (4 mM), 1.1 (8 mM), and 1.6 times (80 mM). For nZVI, Kobs decreased by 32% (2 mM), 39% (4 mM), 45% (8 mM), and 9% (80 mM). The results showed that SO42- increased the rate of 1,1,2-TCA degradation by mZVI but weakened the reduction performance of nZVI; however, this inhibition was reduced when the concentration reached 80 mM. SO42- controlled the degradation of 1,1,2-TCA mainly through the formation of different iron-sulfate complexes on the ZVI surface: water-soluble bidentate iron-sulfate complexes formed on the mZVI surface promoted the corrosion of the oxide layer and accelerated the reduction of 1,1,2-TCA, monodentate complexes mainly formed on the nZVI surface inhibited the reduction of 1,1,2-TCA by blocking surface sites. These results demonstrate the proof of concept to assist land managers in the field application of ZVI technology for the remediation of CAHs contaminated sites with different background concentrations of SO42-.
Keywords: 1,1,2-trichloroethane; Zero-valent iron; reductive dechlorination; sulfate; surface complexes.