Polycyclic aromatic hydrocarbons remobilization from contaminated porous media by (bio)surfactants washing.

Biosurfactants, surface-active agents produced by microorganisms, are increasingly studied for their potential use in soil remediation processes because they are more environmentally friendly than their chemically produced homologues. In this work, we report on the use of a crude biosurfactant produced by a bacterial consortium isolated from a PAHs-contaminated soil, compared with other (bio)surfactants (Tween80, Sodium dodecyl sulfate - SDS, rhamnolipids mix), to wash PAHs from a contaminated porous media. Assays were done using columns filled with sand or sand-clay mixtures (95:5) spiked with four model PAHs. The crude biosurfactant showed less adsorption to the [sand] and the [sand + clay] columns compared to Tween 80, SDS and the rhamnolipid mix. The biosurfactant showed the second best capacity to remove PAHs from the columns (as dissolved and particulate phases), both from [sand] and [sand + clay], after SDS when applied at lower concentrations than the other sufactants. The effluent concentrations of phenanthrene (PHE), pyrene (PYR) and benzo[a]pyrene (BAP) increased in the presence of the crude biosurfactant. Compared to the control experiment using only water, the global PAHs washed mass (amount of PAHs removed from the columns) increased between 9 and 1000 times for PHE and BAP in the [sand] column, and between 55 and 6000 times respectively for PHE and BAP in the [sand + clay] columns. Moreover, in the [sand + clay] columns, leaching of a part of the clays was observed in the SDS and the biosurfactant injections assays. This clay leaching resulted in higher PAHs removal, due not to desorption but rather to particulate transport. In the context of washing PAH-contaminated soils in biopiles or subsurface remediation, our results could help in sizing the remediation approach using an environmental friendly biosurfactant, before a pump-and-treat process.

Surface volatilization modeling of (semi-)volatile hydrophobic organic compounds: The role of reference compounds.

Volatilization of hazardous hydrophobic organic compounds is often observed in many water, wastewater and soil treatment (bio)processes. Several models have been developed to quantify and predict gas-liquid pollutant transfer, being the proportionality coefficient model (PCM) one of the most commonly used, particularly in wastewater treatment. The PCM is based on the use of oxygen as a reference compound, which has a low resistance to the transfer in the gas phase. However, this resistance might be important for (semi-)volatile organic compounds - or (semi-)VOCs, which may render the use of the PCM model inaccurate. This study proposes an experimental methodology and a modeling approach for the use of the two-reference compound model (2RCM) that considers both the liquid-side and the gas-side resistances, by using water and oxygen as references. Results showed that the 2RCM predicts more accurately the overall mass transfer coefficients than the PCM for a VOC and two semi-VOCs tested in this study. In addition, the 2RCM was found to be a more robust method to estimate mass transfer coefficient of any compound and its use can be extrapolated to all substances. Finally, the relevance and limitations of both models was established.

Evaluation of trace metal accumulation in six vegetable crops intercropped with phytostabilizing plant species, in a French urban wasteland.

The extensive development of agriculture in urban and peri-urban wastelands polluted with several trace elements (TE) poses risks to human health through contaminated food products. The objective was to explore the accumulation of TE in the various parts of vegetable crop plants (tomato, French bean, radish, potato, spinach, and leek) intercropped with phytostabilizing plant species (ryegrass and white clover, respectively). Field studies were conducted in a multicontaminated French urban wasteland with Cd, Cu, Pb and Zn, and an alkaline soil pH. Analyses of the respective non-edible parts of monocultured vegetable crops showed accumulation of all TE, mostly Zn, then Pb and Cu, and finally Cd. The corresponding TE accumulation factors (soil to plant) were all below 0.25. In the edible parts, average concentrations for TE were above the limit values, according to European and Chinese standards. TE contents in the phytostabilizing species chosen were in the same orders of magnitude and the same ranking as described for vegetable crops and most accumulation was in the roots. Unexpectedly, the presence of the phytostabilizing plants had a very strong positive impact on the soil to plant accumulation factor. Moreover, the edible plant parts were poorly impacted by the co-cropping with phytostabilizing plants.

Functional potential of sewage sludge digestate microbes to degrade aliphatic hydrocarbons during bioremediation of a petroleum hydrocarbons contaminated soil.

Sewage sludge digestate is a valuable organic waste which can be used as fertilizer in soil bioremediation. Sewage sludge digestate is not only a good source of nutrients but is also rich in bacteria carrying alkB genes, which are involved in aliphatic hydrocarbons metabolism. Increase of alkB genes ratio in polluted soils has been observed to improve bioremediation efficiency. In this study, for the first time, the genetic potential of indigenous microorganisms of digestate to degrade petroleum products was assessed. The objectives were to study petroleum hydrocarbons (PHCs) removal together with shifts in soil taxa and changes in the concentration of alkB genes after digestate application. Initial alkB genes concentration in contaminated soils and digestate was 1.5% and 4.5%, respectively. During soil incubation with digestate, alkB genes percentage increased up to 11.5% and after the addition of bacteria immobilized onto biochar this value increased up to 60%. Application of digestate positively affected soil respiration and bacterial density, which was concomitant with enhanced PHCs degradation. Incubation of soil amended with digestate resulted in 74% PHCs decrease in 2 months, while extra addition of bacteria immobilized onto biochar increased this value up to 95%. The use of digestate affected the microbial community profiles by increasing initial bacterial density and diversity, including taxa containing recognized PHCs degraders. This study reveals the great potential of digestate as a soil amendment which additionally improves the abundance of alkB genes in petroleum contaminated soils.

Remediation of soils contaminated by hydrophobic organic compounds: How to recover extracting agents from soil washing solutions?

A lot of soil (particularly, former industrial and military sites) has been contaminated by various highly toxic contaminants such as petroleum hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), polychlorobiphenyls (PCBs) or chlorinated solvents. Soil remediation is now required for their promotion into new industrial or real estate activities. Therefore, the soil washing (SW) process enhanced by the use of extracting agents (EAs) such as surfactants or cyclodextrins (CDs) has been developed for the removal of hydrophobic organic compounds (HOCs) from contaminated soils. The use of extracting agents allows improving the transfer of HOCs from the soil-sorbed fraction to the washing solution. However, using large amount of extracting agents is also a critical drawback for cost-effectiveness of the SW process. The aim of this review is to examine how extracting agents might be recovered from SW solutions for reuse. Various separation processes are able to recover large amounts of extracting agents according to the physicochemical characteristics of target pollutants and extracting agents. However, an additional treatment step is required for the degradation of recovered pollutants. SW solutions may also undergo degradation processes such as advanced oxidation processes (AOPs) with in situ production of oxidants. Partial recovery of extracting agents can be achieved according to operating conditions and reaction kinetics between organic compounds and oxidant species. The suitability of each process is discussed according to the various physicochemical characteristics of SW solutions. A particular attention is paid to the anodic oxidation process, which allows either a selective degradation of the target pollutants or a complete removal of the organic load depending on the operating conditions.

Electro-Fenton treatment of a complex pharmaceutical mixture: Mineralization efficiency and biodegradability enhancement.

Combination of the electro-Fenton process with a post-biological treatment could represent a cost-effective solution for application of electrochemical advanced oxidation processes. The objective of this study was to assess this treatment strategy in the case of a complex pharmaceutical mixture. First, main operating parameters ([Fe2+] and current) of the electro-Fenton process were optimized. An optimal concentration of 0.2 mM of Fe2+ was obtained for mineralization of the pharmaceutical mixture. An optimal current of 400 mA was also obtained for degradation of caffeine and 5-fluorouracil in the mixture. However, mineralization of the effluent was continuously improved when increasing the current owing to the promotion of mineralization of organic compounds at the BDD anode. Besides, energy efficiency was decreased at prolonged treatment time because of mass transport limitation. Interestingly, it was observed a strong biodegradability enhancement of the solution after short treatment times (<3 h) at 500 and 1000 mA, which can be related to the degradation of parent compounds into more biodegradable by-products. The need for an acclimation time of the biomass to the pre-treated effluent was also emphasized, most probably because of the formation of some toxic by-products as observed during acute toxicity tests. Therefore, a biological post-treatment could represent a cost-effective solution for the removal of biodegradable residual organic compounds as well as for the removal of nitrogen released from mineralization of organic compounds under the form of NO3- and NH4+ during electro-Fenton pre-treatment.

Production of biosurfactant using the endemic bacterial community of a PAHs contaminated soil, and its potential use for PAHs remobilization.

Biosurfactants are surface-active agents produced by microorganisms whose use in soil remediation processes is increasingly discussed as a more environmentally friendly alternative than chemically produced surfactants. In this work, we report the production of a biosurfactant by a bacterial community extracted from a polluted soil, mainly impacted by PAHs, in order to use it in a soil-washing process coupled with bioremediation. Nutrient balance was a critical parameter to optimize the production. Best conditions for biosurfactant production were found to be 20 g/L of glucose, 2 g/L of NH4NO3, and 14.2 g/L of Na2HPO4, corresponding to a C/N/P molar ratio equal to 13/1/2. Purification of the produced biosurfactant by acidification and double extraction with dichloromethane as a solvent allowed measuring the Critical Micellar Concentration (CMC) as equal to 42 mg/L. The capacity of the purified biosurfactant to increase the apparent solubility of four reference PAHs (naphthalene, phenanthrene, pyrene and benzo[a]pyrene) was completed. The solubilisation ratios, in mg of PAH/g of biosurfactant for phenanthrene, pyrene and benzo[a]pyrene are 0.214, 0.1204 and 0.0068, respectively. Identification of the bacteria found in the colony producing the biosurfactant showed the presence of bacteria able to produce biosurfactant (Enterobacteriaceae, Pseudomonas), as well as, others able to degrade PAHs (Microbacterium, Pseudomonas, Rhodanobacteraceae).

Effect of digestate application on microbial respiration and bacterial communities' diversity during bioremediation of weathered petroleum hydrocarbons contaminated soils.

Digestate is an organic by-product of biogas production via anaerobic digestion processes and has a great potential as soil fertilizer due to concentrated nutrients. In this study, we examined digestate as a potential nutrient and microbial seeding for bioremediation of weathered (aged) petroleum hydrocarbon contaminated soils. We analysed 6 different treatments in microcosm using two industrial soils having different textures: a clay rich soil and a sandy soil. After 30 days of incubation, the highest total petroleum hydrocarbons (TPH) removal was observed in microcosms containing digestate together with bulking agent (17.8% and 12.7% higher than control in clay rich soil and sandy soil, respectively) or digestate together with immobilized bacteria (13.4% and 9% higher than control in clay rich soil and sandy soil, respectively). After digestate application microbial respiration was enhanced in sandy soil and inhibited in clay rich soil due to aggregates formation. After bulking agent addition to clay rich soil aggregates size was reduced and oxygen uptake was improved. Application of digestate to soil resulted in the development of distinct microbial groups in amended and non-amended soils. Genera containing species able to degrade TPH like Acinetobacter and Mycobacterium were abundant in digestate and in soil amended with digestate. Quantification of alkB genes, encoding alkane monoxygenase, revealed high concentration of these genes in digestate bacterial community. After application of digestate, the level of alkB genes significantly increased in soils and remained high until the end of the treatment. The study revealed great potential of digestate as a nutrient and bacteria source for soil bioremediation.

Lead sorption by biochar produced from digestates: Consequences of chemical modification and washing.

The main objectives of this work are to investigate the consequences of different chemical treatments (i.e. potassium hydroxide (KOH) and hydrogen peroxide (H2O2)) and the effect of biochar washing on the Pb sorption capacity. Biochars derived from sewage sludge digestate and the organic fraction of municipal solid waste digestate were separately modified with 2 M KOH or 10% H2O2 followed by semi-continuous or continuous washing with ultrapure water using batch or a column reactor, respectively. The results showed that the Pb adsorption capacity could be enhanced by chemical treatment of sludge-based biochar. Indeed, for municipal solid waste biochar, the Pb maximum sorption capacity was improved from 73 mg g-1 for unmodified biochar to 90 mg g-1 and 106 mg g-1 after H2O2 and KOH treatment, respectively. In the case of sewage sludge biochar, it increased from 6.5 mg g-1 (unmodified biochar) to 25 mg g-1 for H2O2 treatment. The sorption capacity was not determined after KOH treatment, since the Langmuir model did not fit the experimental data. The study also highlights that insufficient washing after KOH treatment can strongly hinder Pb sorption due to the release of organic matter from the modified biochar. This organic matter may interact in solution with Pb, resulting in an inhibition of its sorption onto the biochar surface. Continuous column-washing of modified biochars was able to correct this issue, highlighting the importance of implementing a proper treated biochar washing procedure.

Removal of lead and cadmium from aqueous solutions by using 4-amino-3-hydroxynaphthalene sulfonic acid-doped polypyrrole films.

Water pollution by heavy metals is a great health concern worldwide. Lead and cadmium are among the most toxic heavy metals because they are dangerous for the human and aquatic lives. In this work, the removal of lead and cadmium from aqueous solutions has been studied using electrosynthesized 4-amino-3-hydroxynaphthalene-1-sulfonic acid-doped polypyrrole (AHNSA-PPy) films as a new adsorbent. Two distinct methods, including the immersion method, based on the Pb2+ and Cd2+ spontaneous removal by impregnation of the polymer in the solution, and the electro-elimination method, consisting of removal of Pb2+ and Cd2+ ions from the solution by applying a small electrical current (5 mA) to the polymer film, were developed: the evolution of Pb2+ and Cd2+ concentrations with time was monitored by inductively coupled plasma optical emission spectrometry (ICP-OES). The effect of pH on the adsorption and electro-elimination of Pb2+ and Cd2+ using the AHNSA-PPy film was investigated and optimized, showing that the ionic adsorption and electro-elimination processes were highly pH-dependent. The kinetics of Pb2+ and Cd2+ adsorption and electro-elimination were found to follow second-order curves. The maximum adsorption capacity values of the AHNSA-PPy film were 64.0 and 50.4 mg/g, respectively, for Pb2+ and Cd2+. The removal efficiency values were, respectively, for Pb2+ and Cd2+, 80 and 63% by the immersion method, and 93 and 85% by the electro-elimination method. Application of both methods to Senegal natural waters, fortified with Pb2+ and Cd2+, led to removal efficiency values of, respectively for Pb2+ and Cd2+, 76-77 and 58-59% by the immersion method, and of 82-90 and 80-83%, by the electro-elimination method.

Bioelectro-Fenton: evaluation of a combined biological-advanced oxidation treatment for pharmaceutical wastewater.

Electro-Fenton (EF), an advanced oxidation process, can be combined with a biological process for efficient treatment of wastewater containing refractory pollutants such as pharmaceuticals. In this study, a biological process was implemented in a sequencing batch reactor (SBR), which was either preceded or followed by EF treatment. The main goal was to evaluate the potential of two sequences of a combined electrochemical-biological process: EF/SBR and SBR/EF for the treatment of real wastewater spiked with 0.1 mM of caffeine and 5-fluorouracil. The biological removal of COD and pharmaceuticals was improved by extending the acclimation time and increasing concentration of biomass in the SBR. Hardly biodegradable caffeine and COD were completely removed during the EF post-treatment (SBR/EF). During the EF/SBR sequence, complete removal of pharmaceuticals was achieved by EF within 30 min at applied current 800 mA. With a current of 500 and 800 mA, the initially very low BOD5/COD ratio increased up to 0.38 and 0.58, respectively, after 30 min. The efficiency of the biological post-treatment was influenced by the biodegradability enhancement after EF pre-treatment. The choice of an adequate sequence of such a combined process is significantly related to the wastewater characteristics as well as the treatment objectives.

Removal mechanisms in aerobic slurry bioreactors for remediation of soils and sediments polluted with hydrophobic organic compounds: An overview.

Hydrophobic organic compound (HOC)-contaminated soils are a great environmental and public health concern nowadays. Further research is necessary to develop environmental friendly biotechnologies that allows public and private sectors to implement efficient and adaptable treatment approaches. Aerobic soil-slurry bioreactor technology has emerged as an effective and feasible technique with a high remediation potential, especially for silt and clay soil fractions, which often contain the highest pollutant concentration levels and are usually difficult to remove by implementing conventional methods. However, the mechanisms involved in the HOC removal in bioslurry reactor are still not completely understood. Gas-liquid and solid-liquid mass transfer, mass transport and biodegradation phenomena are the main known processes taking place in slurry bioreactors. This review compiles the most up-to-date information available about these phenomena and tries to link them, enlightening the possible interactions between parameters. It gathers the basic information needed to understand the complex bioremediation technology and raises awareness of some considerations that should be made.

Influence of activated sewage sludge amendment on PAH removal efficiency from a naturally contaminated soil: application of the landfarming treatment.

The removal of polycyclic aromatic hydrocarbons (PAHs) from a naturally co-contaminated soil by PAHs and heavy metals with an initial concentration of 620 mg of total PAHs kg-1 dry soil was investigated. The efficiency of landfarming in removing phenanthrene, pyrene, benzo(a)pyrene and the group of total 16 US EPA PAHs was evaluated. The process was biostimulated by adding centrifuged activated sewage sludge (SS) as an organic amendment. The tested ratios of contaminated soil to SS were 1:2, 1:1, 1:0.5 and 1:0 as wet weight basis. The process performance was monitored through chemical, microbiological and ecotoxicological analyses during 105 days of incubation. The results of analyses demonstrated that the treatment without centrifuged SS achieved a significantly higher total 16 US EPA PAH removal efficiency (i.e. 32%) compared to treatments with amendment. In the same treatment, the removal efficiency of the PAH bioavailable fraction was 100% for phenanthrene, benzo(a)pyrene and the group of total 16 US EPA PAHs, whereas 76% for pyrene. Ecotoxicity test performed with bioluminescent bacteria Vibrio fischeri confirmed the effectiveness of landfarming. Finally, the results showed that indigenous microorganisms under certain and controlled operating conditions have greater potential for PAH biodegradation compared to allochthonous microorganisms.

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.

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.

Leaching and selective copper recovery from acidic leachates of Três Marias zinc plant (MG, Brazil) metallurgical purification residues.

Zinc plant purification residue (ZPR), a typical Zn-hydrometallurgical waste, was collected from the Três Marias Zn plant (MG, Brazil). ZPR was characterized for its metal content and fractionation, mineralogy, toxicity and leachability. Toxicity characteristics leaching procedure (TCLP) and European Community Bureau of Reference (BCR) sequential extraction results revealed that this ZPR displays high percentages of metals (Cd, Cu, Zn and Pb) in the highly mobilizable fractions, increasing its hazardous potential. Bulk chemical analysis, pH dependent leaching and acid (H2SO4) leaching studies confirm that the ZPR is polymetallic, rich in Cd, Cu and Zn. The sulfuric acid concentration (1 M), agitation speed (450 rpm), temperature (40 °C) and pulp density (20 g L(-1)) were optimized to leach the maximum amount of heavy metals (Cd, Cu and Zn). Under optimum conditions, more than 50%, 70% and 60% of the total Cd, Cu and Zn present in the ZPR can be leached, respectively. The metals in the acid leachates were investigated for metal sulfide precipitation with an emphasis on selective Cu recovery. Metal sulfide precipitation process parameters such as initial pH and Cu to sulfide ratio were optimized as pH 1.5 and 1:0.5 (Cu:sulfide) mass ratio, respectively. Under optimum conditions, more than 95% of Cu can be selectively recovered from the polymetallic ZPR leachates. The Cu precipitates characterization studies reveal that they are approximately 0.1 µm in diameter and mainly consist of Cu and S. XRD analysis showed covellite (CuS), chalcanthite (CuSO4·5H2O) and natrochalcite (NaCu2(SO4)2(OH)·H2O) as the mineral phases. ZPRs can thus be considered as an alternative resource for copper production.

Fractionation and leachability of heavy metals from aged and recent Zn metallurgical leach residues from the Três Marias zinc plant (Minas Gerais, Brazil).

Various mineral processing operations to produce pure metals from mineral ores generate sludges, residues, and other unwanted by-products/wastes. As a general practice, these wastes are either stored in a reservoir or disposed in the surrounding of mining/smelting areas, which might cause adverse environmental impacts. Therefore, it is important to understand the various characteristics like heavy metal leaching features and potential toxicity of these metallurgical wastes. In this study, zinc plant leach residues (ZLRs) were collected from a currently operating Zn metallurgical industry located in Minas Gerais (Brazil) and investigated for their potential toxicity, fractionation, and leachability. Three different ZLR samples (ZLR1, ZLR2, and ZLR3) were collected, based on their age of production and deposition. They mainly consisted of Fe (6-11.5 %), Zn (2.5 to 5.0 %), and Pb (1.5 to 2.5 %) and minor concentrations of Al, Cd, Cu, and Mn, depending on the sample age. Toxicity Characteristic Leaching Procedure (TCLP) results revealed that these wastes are hazardous for the environment. Accelerated Community Bureau of Reference (BCR) sequential extraction clearly showed that potentially toxic heavy metals such as Cd, Cu, Pb, and Zn can be released into the environment in high quantities under mild acidic conditions. The results of the liquid-solid partitioning as a function of pH showed that pH plays an important role in the leachability of metals from these residues. At low pH (pH 2.5), high concentrations of metals can be leached: 67, 25, and 7 % of Zn can be leached from leach residues ZLR1, ZLR2, and ZLR3, respectively. The release of metals decreased with increasing pH. Geochemical modeling of the pH-dependent leaching was also performed to determine which geochemical process controls the leachability/solubility of the heavy metals. This study showed that the studied ZLRs contain significant concentrations of non-residual extractable fractions of Zn and can be seen as a potential secondary resource for Zn.

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.

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.