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.

Aging as the main factor controlling PAH and polar-PAC (polycyclic aromatic compound) release mechanisms in historically coal-tar-contaminated soils.

In industrial sites, historically contaminated by coal tar (abandoned coking and manufactured gas plants), other families of organic pollutants than the 16 PAHs (polycyclic aromatic hydrocarbons) classified by the US-EPA can occur and induce potential risk for groundwater resources. Polar PACs (polycyclic aromatic compounds), especially oxygenated and nitrogenated PACs (O-PACs and N-PACs), are present in the initial pollution and can also be generated over time (i.e., O-PACs). Their aqueous solubilities are much greater than those of the PAHs. For these reasons, we need to increase our knowledge on polar PACs in order to better predict their behavior and the potential on-site risk. Batch leaching tests were carried out under various conditions of temperature, ionic strength, and availability of pollutants to determine the mechanisms and key parameters controlling their release. The results show a release of low-molecular-weight PAHs and polar PACs mainly by dissolution, while higher molecular weight PAHs are mainly released in association with colloids. Aging mainly controls the former mechanism, and ionic strength mainly controls the latter. Temperature increased both dissolution and colloidal mobilization. The Raoult law predicts the PAC equilibrium concentration for soils presenting high pollutant availability, but this law overestimates PAC concentration in aged soils (low pollutant availability). This is mainly due to limitation of PAC diffusion within coal-tar particles with aging. The most soluble PACs (especially polar PACs) are the most sensitive to aging. For better prediction of the PAC behavior in soils and water resources management, aging needs to be taken into account.

Evolution of dissolved organic matter during abiotic oxidation of coal tar--comparison with contaminated soils under natural attenuation.

In former coal transformation plants (coking and gas ones), the major organic contamination of soils is coal tar, mainly composed of polycyclic aromatic compounds (PACs). Air oxidation of a fresh coal tar was chosen to simulate the abiotic natural attenuation impact on PAC-contaminated soils. Water-leaching experiments were subsequently performed on fresh and oxidized coal tars to study the influence of oxidation on dissolved organic matter (DOM) quality and quantity. The characterization of the DOM was performed using a combination of molecular and spectroscopic techniques (high-performance liquid chromatography-size-exclusion chromatography (HPLC-SEC), 3D fluorescence, and gas chromatography coupled with mass spectrometry (GC-MS)) and compared with the DOM from contaminated soils sampled on the field exposed to natural attenuation for several decades. An increase in the oxygenated polycyclic aromatic compound concentrations was observed with abiotic oxidation both in the coal tar and the associated DOM. Polycyclic aromatic hydrocarbon concentrations in the leachates exceeded pure water solubility limits, suggesting that co-solvation with other soluble organic compounds occurred. Furthermore, emission excitation matrix analysis combined with synchronous fluorescence spectra interpretation and size-exclusion chromatography suggests that oxidation induced condensation reactions which were responsible for the formation of higher-molecular weight compounds and potentially mobilized by water. Thus, the current composition of the DOM in aged soils may at least partly result from (1) a depletion in lower-molecular weight compounds of the initial contamination stock and (2) an oxidative condensation leading to the formation of a higher-molecular weight fraction. Abiotic oxidation and water leaching may therefore be a significant combination contributing to the evolution of coal tar-contaminated soils under natural attenuation.