David Huguenot

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.

Electrochemical advanced oxidation and biological processes for wastewater treatment: a review of the combined approaches

As pollution becomes one of the biggest environmental challenges of the twenty-first century, pollution of water threatens the very existence of humanity, making immediate action a priority. The most persistent and hazardous pollutants come from industrial and agricultural activities; therefore, effective treatment of this wastewater prior to discharge into the natural environment is the solution. Advanced oxidation processes (AOPs) have caused increased interest due to their ability to degrade hazardous substances in contrast to other methods, which mainly only transfer pollution from wastewater to sludge, a membrane filter, or an adsorbent. Among a great variety of different AOPs, a group of electrochemical advanced oxidation processes (EAOPs), including electro-Fenton, is emerging as an environmental-friendly and effective treatment process for the destruction of persistent hazardous contaminants. The only concern that slows down a large-scale implementation is energy consumption and related investment and operational costs. A combination of EAOPs with biological treatment is an interesting solution. In such a synergetic way, removal efficiency is maximized, while minimizing operational costs. The goal of this review is to present cutting-edge research for treatment of three common and problematic pollutants and effluents: dyes and textile wastewater, olive processing wastewater, and pharmaceuticals and hospital wastewater. Each of these types is regarded in terms of recent scientific research on individual electrochemical, individual biological and a combined synergetic treatment.

Comparative bioremediation of heavy metals and petroleum hydrocarbons co-contaminated soil by natural attenuation, phytoremediation, bioaugmentation and bioaugmentation-assisted phytoremediation

Biological remediation technologies are an environmentally friendly approach for the treatment of polluted soils. This study evaluated through a pot experiment four bioremediation strategies: a) natural attenuation, b) phytoremediation with alfalfa (Medicago sativa L.), c) bioaugmentation with Pseudomonas aeruginosa and d) bioaugmentation-assisted phytoremediation, for the treatment of a co-contaminated soil presenting moderate levels of heavy metals (Cu, Pb and Zn at 87, 100 and 110mgkg(-1) DW, respectively) and petroleum hydrocarbons (3800mgkg(-1) DW). As demonstrated by plant biomass and selected physiological parameters alfalfa plants were able to tolerate and grow in the co-contaminated soil, especially when soil was inoculated with P. aeruginosa, which promoted plant growth (56% and 105% increase for shoots and roots, respectively) and appeared to alleviate plant stress. The content of heavy metals in alfalfa plants was limited and followed the order: Zn>Cu>Pb. Heavy metals were mainly concentrated in plant roots and were poorly translocated, favouring their stabilization in the root zone. Bioaugmentation of planted soil with P. aeruginosa generally led to a decrease of plant metal concentration and translocation. The highest degree of total petroleum hydrocarbon removal was obtained for bioaugmentation-assisted phytoremediation treatment (68%), followed by bioaugmentation (59%), phytoremediation (47%) and natural attenuation (37%). The results of this study demonstrated that the combined use of plant and bacteria was the most advantageous option for the treatment of the present co-contaminated soil, as compared to natural attenuation, bioaugmentation or phytoremediation applied alone.

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.

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.

Enhanced Phytoremediation: A Review of Low Molecular Weight Organic Acids and Surfactants Used as Amendments

The contamination of soils with inorganic and organic pollutants is a diffuse environmental issue of significant relevance. Phytoremediation has been proposed as an economically feasible and sustainable remediation technology even if low bioavailability of contaminants constitutes one of the main limitations restricting the success of phytotechnologies. To overcome this constraint the addition of biodegradable amendments has been recently proposed in alternative to synthetic ones. This article presents an overview of two types of biodegradable soil amendments: low molecular weight organic acids and surfactants, evaluating the feasibility of their application in the frame of soil remediation throughout enhanced phytoremediation.

Selection of low cost materials for the sorption of copper and herbicides as single or mixed compounds in increasing complexity matrices.

Low cost materials (sugar beet pulp, corncob, corncob char, perlite, vermiculite, sand, sediment) have been tested for their ability to quickly sorb copper, glyphosate, diuron and 3,4-dichloroaniline (3,4-DCA) as single or mixed compounds. Tests have been performed in increasingly complex liquid matrices: ultra pure water (UPW), runoff water (RW) and sediment extract medium (SEM). Highest sorption levels in UPW are achieved with corncob char for Cu (93%), glyphosate (74%), diuron (98%) and 3,4-DCA (99%). Other ready-to-use adequate sorbents are sugar beet pulp for Cu and sand for glyphosate, diuron and 3,4-DCA. Sorption levels obtained in UPW are significantly altered in SEM as a result of its higher dissolved organic carbon concentration, tenuous changes being obtained with RW. Interactions between herbicides and Cu are pointed out: higher sorption level is observed for glyphosate in mixture with Cu, as it is observed with diuron and 3,4-DCA when mixed with all other pollutants. Langmuir model has been found to better fit the data for copper, whereas Freundlich one has been found more relevant for diuron and 3,4-DCA. Our results stress the need for studying adsorption in different matrices when searching for sorbents to be used in field conditions.

Leaching and selective zinc recovery from acidic leachates of zinc metallurgical leach residues

Zinc (Zn) leaching yields and kinetics from three different zinc plant leach residues (ZLR) generated in different periods (ZLR1>30 years, ZLR2 5-30 years and ZLR3<2 years) were investigated. The factors affecting the Zn leaching rate such as solid to liquid ratio, temperature, acid concentration and agitation were optimized. Under optimum conditions, 46.2 (±4.3), 23.3 (±2.7) and 17.6 (±1.2) mg of Zn can be extracted per gram of ZLR1, ZLR2 and ZLR3, respectively. The Zn leaching kinetics of ZLRs follow the shrinking core diffusion model. The activation energy required to leach Zn from ZLR1, ZLR2 and ZLR3 were estimated to be 2.24kcal/mol, 6.63kcal/mol and 11.7kcal/mol, respectively, by the Arrhenius equation. The order of the reaction with respect to the sulfuric acid concentration was also determined as 0.20, 0.56, and 0.87 for ZLR1, ZLR2 and ZLR3, respectively. Zn was selectively recovered from the leachates by adjusting the initial pH and by the addition of sodium hydroxide and sodium sulfide. More than 90% of Zn was selectively recovered as sphalerite from the ZLR polymetallic leachates by chemical sulfide precipitation.

Bioremediation of copper-contaminated soils by bacteria

Although copper (Cu) is an essential micronutrient for all living organisms, it can be toxic at low concentrations. Its beneficial effects are therefore only observed for a narrow range of concentrations. Anthropogenic activities such as fungicide spraying and mining have resulted in the Cu contamination of environmental compartments (soil, water and sediment) at levels sometimes exceeding the toxicity threshold. This review focuses on the bioremediation of copper-contaminated soils. The mechanisms by which microorganisms, and in particular bacteria, can mobilize or immobilize Cu in soils are described and the corresponding bioremediation strategies—of varying levels of maturity—are addressed: (i) bioleaching as a process for the ex situ recovery of Cu from Cu-bearing solids, (ii) bioimmobilization to limit the in situ leaching of Cu into groundwater and (iii) bioaugmentation-assisted phytoextraction as an innovative process for in situ enhancement of Cu removal from soil. For each application, the specific conditions required to achieve the desired effect and the practical methods for control of the microbial processes were specified.

Characteristics of PAH tar oil contaminated soils—Black particles, resins and implications for treatment strategies

Tar oil contamination is a major environmental concern due to health impacts of polycyclic aromatic hydrocarbons (PAH) and the difficulty of reaching acceptable remediation end-points. Six tar oil-contaminated soils with different industrial histories were compared to investigate contamination characteristics by black particles. Here we provide a simple method tested on 6 soils to visualize and identify large amounts of black particles (BP) as either solid aggregates of resinified and weathered tar oil or various wood/coke/coal-like materials derived from the contamination history. These materials contain 2-10 times higher PAH concentrations than the average soil and were dominantly found in the sand fraction containing 42-86% of the total PAH. The PAH contamination in the different granulometric fractions was directly proportional to the respective total organic carbon content, since the PAH were associated to the carbonaceous particulate materials. Significantly lower (bio)availability of PAH associated to these carbonaceous phases is widely recognized, thus limiting the efficiency of remediation techniques. We provide a conceptual model of the limited mass transfer of PAH from resinated tar oil phases to the water phase and emphasize the options to physically separate BP based on their lower bulk density and slower settling velocity.