Permanganate oxidation of polycyclic aromatic compounds (PAHs and polar PACs): column experiments with DNAPL at residual saturation.

Permanganate is an oxidant usually applied for in situ soil remediation due to its persistence underground. It has already shown great efficiency for dense nonaqueous phase liquid (DNAPL) degradation under batch experiment conditions. In the present study, experimental permanganate oxidation of a DNAPL - coal tar - sampled in the groundwater of a former coking plant was carried out in a glass bead column. Several glass bead columns were spiked with coal tar using the drainage-imbibition method to mimic on-site pollution spread at residual saturation as best as possible. The leaching of organic pollutants was monitored as the columns were flushed by successive sequences: successive injections of hot water, permanganate solution for oxidation, and ambient temperature water, completed by two injections of a tracer before and after oxidation. Sixteen conventional US-EPA PAHs and selected polar PACs were analyzed in the DNAPL remaining in the columns at the end of the experiment and in the particles collected at several steps of the flushing sequences. Permanganate oxidation of the pollutants was rapidly limited by interfacial aging of the DNAPL drops. Moreover, at the applied flow rate chosen to be representative of in situ injections and groundwater velocities, the reaction time was not sufficient to reach high degradation yields but induced the formation and the leaching of oxygenated PACs.

FerrateVI oxidation of polycyclic aromatic compounds (PAHs and polar PACs) on DNAPL-spiked sand: degradation efficiency and oxygenated by-product formation compared to conventional oxidants.

In situ chemical oxidations are known to remediate PAH contaminations in groundwater and soils. In this study, batch-scale oxidations aim to compare the PAC (polycyclic aromatic compound) degradation of three oxidation processes traditionally applied for soil treatment: permanganate, heat-activated persulfate (60 °C) and Fenton-like activated by magnetite, to results obtained with ferrates (FeVI). Widely studied for water treatments, ferrates are efficient on a wide range of pollutants with the advantage of producing nontoxic ferric sludge after reaction. However, fewer works focus on their action on soil, especially on semi-industrial grade ferrates (compatible with field application). Oxidations were carried out on sand spiked with dense non-aqueous phase liquid (DNAPL) sampled in the groundwater of a former coking plant. Conventional 16 US-EPA PAHs and polar PACs were monitored, especially potential oxygenated by-products that can be more harmful than parent-PAHs. After seven reaction days, only the Fenton-like showed limited degradation. Highest efficiencies were obtained for heat-activated persulfate with no O-PAC ketones formed. Permanganate gave important degradation, but ketones were generated in large amount. The tested ferrates not only gave slightly lower yields due to their auto-decomposition but also induced O-PAC ketone production, suggesting a reactional pathway dominated by oxidoreductive electron transfer, rather than a radical one.