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The use of plants and microorganisms to mitigate sediment contaminated by copper was studied in microcosms that mimic the functioning of a stormwater basin (SWB) connected to vineyard watershed. The impact of phytoremediation and bioaugmentation with siderophore-producing bacteria on the fate of Cu was studied in two contrasted (batch vs. semi-continuous) hydraulic regimes. The fate of copper was characterised following its discharge at the outlet of the microcosms, its pore water concentration in the sediment, the assessment of its bioaccessible fraction in the rhizosphere and the measurement of its content in plant tissues. Physico-chemical (pH, redox potential) and biological parameters (total heterotrophic bacteria) were also monitored. As expected, the results showed a clear impact of the hydraulic regime on the redox potential and thus on the pore water concentration of Cu. Copper in pore water was also dependent on the frequency of Cu-polluted water discharges. Repeated bioaugmentation increased the total heterotrophic microflora as well as the Cu bioaccessibility in the rhizosphere and increased the amount of Cu extracted by Phragmites australis by a factor of ~2. Sugar beet pulp, used as a filter to avoid copper flushing, retained 20 % of outcoming Cu and led to an overall retention of Cu higher than 94 % when arranged at the outlet of microcosms. Bioaugmentation clearly improved the phytoextraction rate of Cu in a small-scaled SWB designed to mimic the functioning of a full-size SWB connected to vineyard watershed. Highlights: - Cu phytoextraction in constructed wetlands much depends on the hydraulic regime and on the frequency of Cu-polluted water discharges - Cu phytoextraction increases with time and plant density - Cu bioaccessibility can be increased by bioaugmentation with siderophore-producing bacteria [ABSTRACT FROM AUTHOR]

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., Competing Interests: Declaration of Competing Interest The authors declare that they have no competing interests., (Copyright © 2022 Elsevier B.V. All rights reserved.)

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., (Copyright © 2021 Elsevier B.V. All rights reserved.)

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., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

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., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2020 Elsevier B.V. All rights reserved.)

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 ([Fe 2+ ] and current) of the electro-Fenton process were optimized. An optimal concentration of 0.2 mM of Fe 2+ 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 NO 3 - and NH 4 + during electro-Fenton pre-treatment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

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 NH 4 NO 3 , and 14.2 g/L of Na 2 HPO 4 , 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)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2018 Elsevier B.V. All rights reserved.)

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., (Copyright © 2019. Published by Elsevier B.V.)

The main objectives of this work are to investigate the consequences of different chemical treatments (i.e. potassium hydroxide (KOH) and hydrogen peroxide (H 2 O 2 )) 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% H 2 O 2 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 H 2 O 2 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 H 2 O 2 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., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

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 BOD 5 /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.

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 Pb 2+ and Cd 2+ spontaneous removal by impregnation of the polymer in the solution, and the electro-elimination method, consisting of removal of Pb 2+ and Cd 2+ ions from the solution by applying a small electrical current (5 mA) to the polymer film, were developed: the evolution of Pb 2+ and Cd 2+ 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 Pb 2+ and Cd 2+ 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 Pb 2+ and Cd 2+ 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 Pb 2+ and Cd 2+ . The removal efficiency values were, respectively, for Pb 2+ and Cd 2+ , 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 Pb 2+ and Cd 2+ , led to removal efficiency values of, respectively for Pb 2+ and Cd 2+ , 76-77 and 58-59% by the immersion method, and of 82-90 and 80-83%, by the electro-elimination method.

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.

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., (Copyright © 2017. Published by Elsevier B.V.)

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., (Copyright © 2017 Elsevier B.V. All rights reserved.)

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., (Copyright © 2016 Elsevier B.V. All rights reserved.)

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.