Recent advancements in peroxicoagulation process: An updated review.

The present article describes the recent advancements (since 2018) in peroxicoagulation (PC) process, which was introduced by Professor Enric Brillas and his group in 1997. Instead of checking the efficiency of PC process to degrade a targeted pollutant in synthetic wastewater, researchers started testing its efficacy for the treatment of complex real wastewater. Applications like disinfection and removal of heavy metals as well as oxidative removal of arsenite from water were tested recently. To improve the efficiency of PC process, modifications were made for electrode materials (both anode and cathode) and electrolytic cells. Performance of PC process in combination with other treatment technologies is also discussed.

Electrosorption of phenolic compounds from olive mill wastewater: Mass transport consideration under a transient regime through an alginate-activated carbon fixed-bed electrode.

Olive mill wastewater (OMWW) is an environmentally critical effluent, specifically due to its high content of phenolic compounds (PCs), which are hazardous due to their antimicrobial activities in water. However, their properties have good health effects at suitable doses. For the first time, the electrosorption of PCs from actual OMWW has been proposed for their possible recovery as value-added compounds, while decontaminating OMWW. A bio-sourced alginate-activated carbon (AC) fixed-bed electrode was prepared based on the reuse of olive pomace solid waste as powdered AC. At the optimal AC content (1% w/v), the internal ohmic drop voltage was lower (2.26 V) and the mass transport coefficient was higher (9.7 10-5 m s-1) along with the diffusivity (7.3 10-9 m2 s-1), which led to enhanced electrosorption rates. Afterward, an optimal electrode potential was obtained (-1.1 V vs. Ag/AgCl), while higher voltages led to faradaic reactions. Moreover, the adsorption capacity was lower (123 mg g-1) than that of electrosorption (170 mg g-1) and was even higher (307 mg g-1) with actual effluents. This was probably due to the influence of electromigration, which was confirmed by new models that could predict the electrosorption kinetics well considering mass transport and acid dissociation constants.

A critical review on the electrosorption of organic compounds in aqueous effluent - Influencing factors and engineering considerations.

Despite being an old process from the end of the 19th century, electrosorption has attracted renewed attention in recent years because of its unique properties and advantages compared to other separation technologies and due to the concomitant development of new porous electrode materials. Electrosorption offer the advantage to separate the pollutants from wastewater with the possibility of selectively adsorbing and desorbing the targeted compounds. A comprehensive review of electrosorption is provided with particular attention given to the electrosorption of organic compounds, unlike existing capacitive deionization review papers that only focus on inorganic salts. The background and principle of electrosorption are first presented, while the influence of the main parameters (e.g., electrode materials, electrode potential, physico-chemistry of the electrolyte solutions, type of compounds, co-sorption effect, reactor design, etc.) is then detailed and the modeling and engineering aspects are discussed. Finally, the main output and future prospects about recovery studies and combination between electro-sorption/desorption and degradation processes are given. This review particularly highlights that carbon-based materials have been mostly employed (85% of studies) as porous electrode in organics electrosorption, while existing studies lack of electrode stability and durability tests in real conditions. These electrodes have been implemented in a fixed-bed reactor design most of the time (43% of studies) due to enhanced mass transport. Moreover, the electrode potential is a major criterion: it should be applied in the non-faradaic domain otherwise unwanted reactions can easily occur, especially the corrosion of carbon from 0.21 V/standard hydrogen electrode or the water oxidation/reduction. Furthermore, there is lack of studies performed with actual effluents and without addition of supporting electrolyte, which is crucial for testing the real efficiency of the process. The associated predictive model will be required by considering the matrix effect along with transport phenomena and physico-chemical characteristics of targeted organic compounds.

Performance and dynamic modeling of a continuously operated pomace olive packed bed for olive mill wastewater treatment and phenol recovery.

The solid waste of olive oil extraction processes (olive pomace, OP) was converted into activated carbon (AC) by treating it with NaOH and then encapsulating it within sodium alginate (SA) in beads by crosslinking (SA-AC beads). The prepared SA-AC beads were utilized as an adsorbent for the elimination and recovery of phenolic compounds (PCs) from olive mill wastewater (OMWW) following a zero liquid and waste discharge approach to implement and promote the circular economy concept. The novel AC and SA-AC beads were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR) and Brunauer, Emmett and Teller (BET) analysis. The adsorption performance of these beads was evaluated in batch and fixed-bed reactors operated in a concurrent flow system. The results revealed that an adsorption capacity of 68 mg g-1 was attained for 4000 mg L-1 phenolic compounds. The kinetics of the adsorption process of the PCs fit a pseudo second-order model, and the most likely mechanism took place in two stages. The adsorption isotherm conformed to the Langmuir model, representing the monolayer adsorption of the phenolic compounds. The dynamic models were used, and they accurately represented the breakthrough curves. Considering PC recovery and process reusability, a regeneration experiment of SA-AC beads was carried out in fixed-bed reactors. SA-AC beads showed a high percentage desorption >40% using ethanol and were efficient after several cycles of OMWW treatment and phenol recovery.

Cost comparison of advanced oxidation processes for wastewater treatment using accumulated oxygen-equivalent criteria.

Advanced oxidation processes (AOPs) have received a lot of attention over the years as advanced physico-chemical polishing wastewater treatments to remove biorefractory pollutants. Additionally, many studies report their excellent degradation and mineralization performance as stand-alone technologies too, demonstrating the versatility of these processes; however, there is a lack of suitable methods to compare the performance (in terms of removal efficiency and operating costs) of different AOPs in the same conditions. In this context, the goal of this paper is to propose a systematic investigation by introducing a novel criterion, namely the accumulated oxygen-equivalent chemical-oxidation dose (AOCD), to systematically compare the diverse AOPs available: ozonation, H2O2 photolysis, Fenton, photo-Fenton, electro-Fenton and photoelectro-Fenton (paired with anodic oxidation, for the latter two). For each of these, the cost efficiency was determined by optimizing the operating conditions for the removal of phenol, selected as a model pollutant (1.4 mM, equivalent to 100 mg-C L-1). The operating costs considered sludge management, chemical use and electricity consumption. Among all AOPs, electro-Fenton was the most cost-effective (108 - 125 € m-3), notwithstanding the mineralization target (50%, 75% and 99%), owing to its electrocatalytic behavior. Chemical Fenton proved competitive too up to 50% of mineralization, meaning that it could also be considered as a cost-effective pre-treatment solution. AOCD was the lowest for electro-Fenton, which could be attributed to its excellent faradaic yield, while UV-based processes generally required the highest dose. The AOCD criterion could serve as a baseline for AOP comparison and prove useful for the legislator to determine the "best available techniques" as defined by the Industrial Emissions European Union Directive 2010/75/EU.

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.

Influence of number of azo bonds and mass transport limitations towards the elimination capacity of continuous electrochemical process for the removal of textile industrial dyes.

This study focusses on the electrochemical decomposition of synthetic azo dyes (RO16, RR120 and DR80) using stainless steel electrodes, which is efficient, cost effective and industrially driven process. The experiments were carried out in a continuous electrochemical reactor and the effects of influencing parameters (initial concentration of dye, electrolyte concentration, pH) governing the process efficiency was studied. The interaction between the influencing parameters was investigated using Response Surface Methodology (RSM) and the regression value obtained for the generated model was above 0.9 for all the three dyes. The elimination capacity of electrochemical reactor was studied for the continuous removal of azo dyes with different ranges of concentration (100-400 mg L-1) and flow rate (0.1-0.5 L h-1). The maximum elimination capacity was obtained at a flow rate of 0.5 L h-1 for 300 mg L-1 of initial concentration of dye for RO16 and RR120 whereas it was 0.5 L h-1 for 400 mg L-1 of DR80. Further, a general dimensionless current density relation has been established for stirred tank reactor and allowed characterizing the relationship between kinetics and mass transport contributing to the overall reaction rate. The results quantitatively confirmed that the rate of electrochemical decolorization increased with the increasing initial dye concentration and flow rate due to the mass transport limitation. As newly established, the decolorization is also directly linked to the number of azo bonds.

Advanced electrocatalytic pre-treatment to improve the biodegradability of real wastewater from the electronics industry - A detailed investigation study.

For the first time, real effluents from the micro-electronics industry were treated by paired advanced electrocatalysis, combining electro-Fenton (EF) with anodic oxidation (AO). A detailed characterization of the effluents was performed, showing that isopropanol (IPA) and acetone were the main constituents of the wastewater. Both compounds were completely degraded during the first 120 min of treatment. By monitoring the degradation intermediates, an oxidation pathway was proposed, which includes short-chain carboxylic acids as the main end-organic compounds. While carbon brush served as the cathode, two anode materials were utilized: boron-doped diamond (BDD) and carbon-PTFE cloth (CC). Despite the lower mineralization efficiency showed by CC as compared to BDD (76.5% of TOC removal with CC vs 94.0% of TOC removal with BDD after 4 h), CC showed potential to increase the BOD5/COD ratio of the effluent that reached 0.7 after only 45 min (0.6 in 30 min with BDD). These results suggest that the electrolysis time could be kept short, improving the cost-effectiveness of the process, especially if CC is used. Overall, the results point out the suitability of advanced electrocatalysis to treat real electronics wastewater with low energy requirements, short treatment times and cost-effective electrode materials.

Fate of inorganic nitrogen species under homogeneous Fenton combined with electro-oxidation/reduction treatments in synthetic solutions and reclaimed municipal wastewater.

The fate of inorganic nitrogen species has been studied for the first time in electro-Fenton (EF) conditions in acid media. A redox cycle is first obtained and validated with a kinetic model in synthetic solution and highlights the removal of nitrite that is quickly oxidized into nitrate while the reduction conditions are sufficient to reduce nitrate into ammonium cation. However, NH4+ and gaseous nitrogen accumulate in such solution. The study in reclaimed municipal wastewater emphasize the removal of NH4+ with formation of chloramines in the presence of initial chloride ions, a species widely present in wastewater effluent. Contrastingly, NO3- remain constant all along the electrolysis even after 2.1 Ah L-1. The oxidation conditions were not sufficient to produce perchlorate while chlorate accumulated in solution. Therefore, it limits the use of EF for direct use for drinking water purpose but could be considered as complementary treatment for wastewater reuse applications.

Iron-impregnated zeolite catalyst for efficient removal of micropollutants at very low concentration from Meurthe river.

In this paper, for the first time, faujasite Y zeolite impregnated with iron (III) was employed as a catalyst to remove a real cocktail of micropollutants inside real water samples from the Meurthe river by the means of the heterogeneous photo-Fenton process. The catalyst was prepared by the wet impregnation method using iron (III) nitrate nonahydrate as iron precursor. First, an optimization of the process parameters was conducted using phenol as model macro-pollutant. The hydrogen peroxide concentration, the light wavelength (UV and visible) and intensity, the iron loading immobilized, as well as the pH of the solution were investigated. Complete photo-Fenton degradation of the contaminant was achieved using faujasite containing 20 wt.% of iron, under UV light, and in the presence of 0.007 mol/L of H2O2 at pH 5.5. In a second step, the optimized process was used with real water samples from the Meurthe river. Twenty-one micropollutants (endocrine disruptors, pharmaceuticals, personal care products, and perfluorinated compounds) including 17 pharmaceutical compounds were specifically targeted, detected, and quantified. All the initial concentrations remained in the range of nanogram per liter (0.8-88 ng/L). The majority of the micropollutants had a large affinity for the surface of the iron-impregnated faujasite. Our results emphasized the very good efficiency of the photo-Fenton process with a cocktail of a minimum of 21 micropollutants. Except for sulfamethoxazole and PFOA, the concentrations of all the other microcontaminants (bisphenol A, carbamazepine, carbamazepine-10,11-epoxide, clarithromycin, diclofenac, estrone, ibuprofen, ketoprofen, lidocaine, naproxen, PFOS, triclosan, etc.) became lower than the limit of quantification of the LC-MS/MS after 30 min or 6 h of photo-Fenton treatment depending on their initial concentrations. The photo-Fenton degradation of PFOA can be neglected. The photo-Fenton degradation of sulfamethoxazole obeys first-order kinetics in the presence of the cocktail of the other micropollutants.

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.

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.

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.