Reductive dechlorination of organochlorine pesticides in soils from an abandoned manufacturing facility by zero-valent iron

Several experiments and a model were constructed using conventional granular zero-valent iron (ZVI) particles as the reducing agent to study the reductive dechlorination characteristics of hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethane (DDTs) in soils from a former pesticide-manufacturing site. The results showed that ZVI had good ability for the reductive dechlorination for both HCHs and DDTs. The reductive dechlorination of HCHs and DDTs proceeded at different rates. The pseudo first-order constants of HCHs were greater than those of DDTs. The reductive dechlorination rates in a descending order were γ-HCH > δ-HCH > β-HCH > α-HCH > o,p'-DDT > p,p'-DDT > p,p'-DDE. To discuss the major influential factors over the reductive dechlorination rates of HCHs and DDTs by ZVI, 22 quantum chemical descriptors were computed with the density functional theory at B3LYP/6-31G* level, which characterizes different molecular structures and physicochemical properties of HCHs and DDTs. A polyparameter linear free energy relationship (LFER) model was established, which correlates the reductive dechlorination properties of pollutants with their structural descriptors. Using the partial least squares (PLS) analysis, an optimal two-parameter LFER model was established. q+ and qCl- were more important factors in determining the dechlorination rate of OCPs in the chemical reductive reaction. This optimal model was stable and had good predictability. The model study also showed that the coefficient value of q+ was 0.511, which positively correlated with the reductive dechlorination rate constant, whereas qCl- was negatively correlated with it. The reductive dechlorination rate of pollutants appears to be limited mainly by the rate of dissolution in the aqueous phase. This model can be used to explain the degradation potential of organochlorine pesticides (OCPs) and the trend of residues changing during the soil remediation. Therefore, the study is of practical importance for understanding the process of dechlorination in the presence of multiple OCPs and the development of remediation techniques for the soils contaminated by OCPs.