Fenton-like and potassium permanganate oxidations of PAH-contaminated soils: Impact of oxidant doses on PAH and polar PAC (polycyclic aromatic compound) behavior.

Potassium permanganate and Fenton-like oxidations were applied on two PAH-contaminated soils collected on former coking plant and gas plant sites. The impact of oxidant dose on the polycyclic aromatic compound (PAC) evolution, including 16 US-EPA PAHs, 11 oxygenated- and 4 nitrogen heterocyclic-PACs (O- and N-PACs) was studied for both treatments. The content of extractable organic matter and PACs was determined prior and after oxidation. Overall, permanganate treatment was more efficient than Fenton-like to decrease the PAH content, this latter being limited by the contamination availability. However, permanganate treatment resulted in incomplete PAH degradation, leading to the formation of O-PACs, that was limited with the application of higher dose. It underlines the importance of the dose and the oxidant type in the selection of oxidation parameters for remediation purpose, as improper use of oxidant can lead to the accumulation of oxidation by-products that could be as toxic as the parent compounds.

Behavior of PAH/mineral associations during thermodesorption: impact for the determination of mineral retention properties towards PAHs.

Polycyclic aromatic hydrocarbons (PAHs) associated with two minerals (silica sand and bentonite) presenting opposite retention properties were analyzed with a thermodesorption (Td)-GC-MS coupling in order to validate this technique as a new and rapid way to evaluate the solid sorption properties. Two analysis modes were used, evolved gas analysis (EGA) and Td with cryo-trap. EGA allowed a real-time monitoring of the compounds desorbed during a temperature program and gave a first screening of the samples while Td gave more precise indications on compound abundances for selected temperature ranges. When associated with silica sand, PAHs were released at relatively low temperatures (<300 °C) close to corresponding boiling point, whereas for the PAH/bentonite mixture, PAHs were desorbed at much higher temperatures; they were also present in much lower abundance and were associated with mono-aromatic compounds. With bentonite, the PAH abundances decreased and the mono-aromatics increased with the increasing PAH molecular weight. These results indicated a clear PAH retention by the bentonite due to polymerization, followed by a thermal cracking at higher temperatures. The Td-GC-MS was proven to efficiently underline differences in retention properties of two minerals, and this study highlights the great potential of this technique to evaluate compound/matrix bond strength and interaction.

Evaluation of matrices for the sorption and biodegradation of phenanthrene.

Permeable reactive barriers (PRBs), a new cost effective technology for the remediation of contaminated groundwater, have rarely been considered for PAH contamination. We evaluated three candidate matrices (activated carbon (AC), pouzzolana coated (PzF) or not (Pz) with heavy fuel oil) for phenanthrene (PHE) sorption capacity and the biodegradation of adsorbed PHE. Adsorption-desorption batch experiments showed higher sorption capacity of AC than PzF (60 fold) and Pz (1,500 fold). Sorption isotherms were not linear for all matrices as described by a Freundlich model. Phenanthrene desorption from AC and PzF within 48 h was limited (1-3%). Mineralization of (14)C-PHE by a PAH-degrading bacterial strain increased in the presence of AC and Pz (+16 and +12%). Among the three matrices, AC may be a good candidate for PRBs due to high adsorption, low desorption and increased PHE degradation.

A nonlinear parametric model for phenanthrene sorption.

Two models for phenanthrene sorption prediction are discussed and checked against experimental data. The first model, based on a two-site Langmuir expression, displays too large uncertainties. The second is based on a modified Langmuir relation and provides a better description of the whole dataset. It includes an experimentally derived relation between the site maximal concentration and chemical parameters of the substrate: TOC amount and polarity index (O+N)/C. The model is tested against sorption isotherms of phenanthrene acquired with six different substrates. Calculated values display satisfying accordance with experimental data. Validity of the model is tested with an isotherm that does not belong to the set of data used for the regression, with good results. Some discrepancies may arise from analytical uncertainty and structural aspects not included within the model.