Emmanuel Mousset

Removal of hydrophobic organic pollutants from soil washing/flushing solutions: A critical review

The release of hydrophobic organoxenobiotics such as polycyclic aromatic hydrocarbons, petroleum hydrocarbons or polychlorobiphenyls results in long-term contamination of soils and groundwaters. This constitutes a common concern as these compounds have high potential toxicological impact. Therefore, the development of cost-effective processes with high pollutant removal efficiency is a major challenge for researchers and soil remediation companies. Soil washing (SW) and soil flushing (SF) processes enhanced by the use of extracting agents (surfactants, biosurfactants, cyclodextrins etc.) are conceivable and efficient approaches. However, this generates high strength effluents containing large amount of extracting agent. For the treatment of these SW/SF solutions, the goal is to remove target pollutants and to recover extracting agents for further SW/SF steps. Heterogeneous photocatalysis, technologies based on Fenton reaction chemistry (including homogeneous photocatalysis such as photo-Fenton), ozonation, electrochemical processes and biological treatments have been investigated. Main advantages and drawbacks as well as target pollutant removal mechanisms are reviewed and compared. Promising integrated treatments, particularly the use of a selective adsorption step of target pollutants and the combination of advanced oxidation processes with biological treatments, are also discussed.

Influence of solubilizing agents (cyclodextrin or surfactant) on phenanthrene degradation by electro-Fenton process - Study of soil washing recycling possibilities and environmental impact

One of the aims in soil washing treatment is to reuse the extracting agent and to remove the pollutant in the meantime. Thus, electro-Fenton (EF) degradation of synthetic soil washing solutions heavily loaded with phenanthrene was suggested for the first time. Two solubilising agents hydroxypropyl-beta-cyclodextrin (HPCD) and Tween 80(®) (TW 80) were chosen as cyclodextrin (CD) and surfactant representatives, respectively. In order to reuse HPCD and to degrade the pollutant simultaneously, the following optimal parameters were determined: [Fe(2+)] = 0.05 mM (catalyst), I = 2000 mA, and natural solution pH (around 6), without any adjustment. Only 50% of TW 80 (still higher than the critical micelle concentration (CMC)) can be reused against 90% in the case of HPCD while phenanthrene is completely degraded in the meantime, after only 180 min of treatment. This can be explained by the ternary complex formation (Fe(2+)-HPCD-organic pollutant) (equilibrium constant K = 56 mM(-1)) that allows OH to directly degrade the contaminant. This confirms that Fe(2+) plays an important role as a catalyst since it can promote formation of hydroxyl radicals near the pollutant and minimize HPCD degradation. After 2 h of treatment, HPCD/phenanthrene solution got better biodegradability (BOD5/COD = 0.1) and lower toxicity (80% inhibition of luminescence of Vibrio fischeri bacteria) than TW 80/phenanthrene (BOD5/COD = 0.08; 99% inhibition of V. fischeri bacteria). According to these data, HPCD employed in this integrated (soil washing + EF degradation) approach gave promising results in order to be reused whereas the pollutant is degraded in the meanwhile.

Combination of surfactant enhanced soil washing and electro-Fenton process for the treatment of soils contaminated by petroleum hydrocarbons

In order to improve the efficiency of soil washing treatment of hydrocarbon contaminated soils, an innovative combination of this soil treatment technique with an electrochemical advanced oxidation process (i.e. electro-Fenton (EF)) has been proposed. An ex situ soil column washing experiment was performed on a genuinely diesel-contaminated soil. The washing solution was enriched with surfactant Tween 80 at different concentrations, higher than the critical micellar concentration (CMC). The impact of soil washing was evaluated on the hydrocarbons concentration in the leachates collected at the bottom of the soil columns. These eluates were then studied for their degradation potential by EF treatment. Results showed that a concentration of 5% of Tween 80 was required to enhance hydrocarbons extraction from the soil. Even with this Tween 80 concentration, the efficiency of the treatment remained very low (only 1% after 24 h of washing). Electrochemical treatments performed thereafter with EF on the collected eluates revealed that the quasi-complete mineralization (>99.5%) of the hydrocarbons was achieved within 32 h according to a linear kinetic trend. Toxicity was higher than in the initial solution and reached 95% of inhibition of Vibrio fischeri bacteria measured by Microtox method, demonstrating the presence of remaining toxic compounds even after the complete degradation. Finally, the biodegradability (BOD₅/COD ratio) reached a maximum of 20% after 20 h of EF treatment, which is not enough to implement a combined treatment with a biological treatment process.

Soil Washing/Flushing Treatments of Organic Pollutants Enhanced by Cyclodextrins and Integrated Treatments: State of the Art

Soils contaminated by hydrophobic organic pollutants are a common concern because they are extremely difficult to remove and their potential toxicological impacts are significant. As an alternative to traditional pump-and-treat technologies, soil washing and soil flushing are conceivable and efficient approaches. Extracting agents such as cyclodextrins are compared to traditional surfactants, cosolvents, and less conventional agents. Ability of cyclodextrin derivatives to form a ternary pollutant-cyclodextrin-iron complex allows discussing about promising integrated treatments requiring modified Fenton treatments such as electro-Fenton process with or without combination to a biological step and a recirculation loop.

Impact of electrochemical treatment of soil washing solution on PAH degradation efficiency and soil respirometry.

The remediation of a genuinely PAH-contaminated soil was performed, for the first time, through a new and complete investigation, including PAH extraction followed by advanced oxidation treatment of the washing solution and its recirculation, and an analysis of the impact of the PAH extraction on soil respirometry. The study has been performed on the remediation of genuine PAH-contaminated soil, in the following three steps: (i) PAH extraction with soil washing (SW) techniques, (ii) PAH degradation with an electro-Fenton (EF) process, and (iii) recirculation of the partially oxidized effluent for another SW cycle. The following criteria were monitored during the successive washing cycles: PAH extraction efficiency, PAH oxidation rates and yields, extracting agent recovery, soil microbial activity, and pH of soil. Two representative extracting agents were compared: hydroxypropyl-beta-cyclodextrin (HPCD) and a non-ionic surfactant, Tween(®) 80. Six PAH with different numbers of rings were monitored: acenaphthene (ACE), phenanthrene (PHE), fluoranthene (FLA), pyrene (PYR), benzo(a)pyrene (BaP), and benzo(g,h,i)perylene (BghiP). Tween(®) 80 showed much better PAH extraction efficiency (after several SW cycles) than HPCD, regardless of the number of washing cycles. Based on successive SW experiments, a new mathematical relation taking into account the soil/water partition coefficient (Kd*) was established, and could predict the amount of each PAH extracted by the surfactant with a good correlation with experimental results (R(2) > 0.975). More HPCD was recovered (89%) than Tween(®) 80 (79%), while the monitored pollutants were completely degraded (>99%) after 4 h and 8 h, respectively. Even after being washed with partially oxidized solutions, the Tween(®) 80 solutions extracted significantly more PAH than HPCD and promoted better soil microbial activity, with higher oxygen consumption rates. Moreover, neither the oxidation by-products nor the acidic media (pH approximately 3) of the partially oxidized solution inhibited the general soil microbial activity during the washing cycle.