Hydrogeochemical analysis of processes affecting HCH removal using ZVI-based treatment technology

In the 1960s, ca. 3000–5000 tons of HCH residue were disposed of in an overburden dump at the Hájek kaolin/uranium mine site (Czech Republic). The dump leachate, which has a 136 μg/l average total content of hexachlorocyclohexane (HCH) isomers, discharges into a local creek and contaminates the ecosystem. A full-scale prototype for the treatment of dump leachate comprised three sequential stages: 1) permeable reactive modules filled with macro-zerovalent iron (mZVI), 2) a biosorption module and 3) an aerobic wetland module. After commissioning, HCH removal efficiency reached 95%, but decreased to 70% over the following 230 days, primarily due to the efficiency of the mZVI modules dropping from 76% to 39%. Hydrogeochemical analysis and geochemical modelling revealed that the reduction in efficiency was mainly caused by passivation of mZVI surfaces and clogging of mZVI pore spaces through precipitation of goethite, calcite and rhodochrosite, or siderite and magnetite instead of goethite where boundary conditions for O₂ differed. XRD analysis of the solid phase from the mZVI modules confirmed the geochemical modelling results. The major part of the precipitated products (46–66 wt%) comprised a ferric hydroxide amorphous phase, especially in the initial mZVI module inlet, with goethite the second most abundant precipitate (10–40 wt%). Siderite and calcite also mainly precipitated in the initial module inlet. In conclusion, mZVI appears to be a suitable reductant for HCH; however, the longevity of the ZVI-based treatment system was negatively affected by precipitates in the presence of high concentrations of iron, manganese and carbonate species.