Sustainable lindane waste remediation: Surfactant-driven residual DNAPL extraction and oxidation in a real landfill (LIFE SURFING).

The LIFE SURFING Project was carried out at the Bailin Landfill in Sabiñánigo, Spain (2020-2022), applying Surfactant Enhanced Aquifer Remediation (SEAR) and In Situ Chemical Oxidation (S-ISCO) in a 60-meter test cell beneath the old landfill, to remediate a contaminated aquifer with dense non-aqueous phase liquid (DNAPL) from nearby lindane production. The project overcame traditional extraction limitations, successfully preventing groundwater pollution from reaching the river. In spring 2022, two SEAR interventions involved the injection of 9.3 m3 (SEAR-1) and 6 m3 (SEAR-2) of aqueous solutions containing 20 g/L of the non-ionic surfactant E-Mulse 3®, with bromide (around 150 mg/L) serving as a conservative tracer. 7.1 and 6.0 m3 were extracted in SEAR-1 and SEAR-2, respectively, recovered 60-70 % of the injected bromide and 30-40 % of the surfactant, confirming surfactant adsorption by the soil. Approximately 130 kg of DNAPL were removed, with over 90 % mobilized and 10 % solubilized. A surfactant-to-DNAPL recovery mass ratio of 2.6 was obtained, a successful value for a fractured aquifer. In September 2022, the S-ISCO phase entailed injecting 22 m3 of a solution containing persulfate (40 g/L), E-Mulse 3® (4 g/L), and NaOH (8.75 g/L) in pulses over 48 h, oxidizing around 20 kg of DNAPL and ensuring low toxicity levels after that. Preceding the SEAR and S-ISCO trials, 2020 and 2021 were dedicated to detailed groundwater flow characterizations, including hydrological and tracer studies. These preliminary investigations allowed the design of a barrier zone between 317 and 557 m from the test cell and the river, situated 900 m away. This zone, integrating alkali dosing, aeration, vapor extraction, and oxidant injection, effectively prevented the escape of fluids to the river. Neither surfactants nor contaminants were detected in river waters post-treatment. The absence of residual phase in test cell wells and reduction of chlorinated compound levels in groundwater were noticed till one year after S-ISCO.

Remediation of groundwater polluted with lindane production wastes by conductive-diamond electrochemical oxidation.

This work studies the remediation of groundwater saturated with dense non-aqueous phase liquid (DNAPL) from lindane production wastes by electrochemical oxidation. DNAPL-saturated groundwater contains up to 26 chlorinated organic compounds (COCs), including different isomers of hexachlorocyclohexane (HCH). To do this, polluted groundwater was electrolysed using boron-doped diamond (BDD) and stainless steel (SS) as anode and cathode, respectively, and the influence of the current density on COCs removal was evaluated in the range from 5 to 50 mA cm-2. Results show that current densities higher than 25 mA cm-2 lead to the complete removal and mineralisation of all COCs identified in groundwater. The higher the current density, the higher the COCs removal rate. At lower current densities (5 mA cm-2), chlorobenzenes were completely removed, and degradations above 90 % were reached for COCs with more than five chlorine atoms in their molecules. The use of BDD anodes promotes the electrochemical generation of powerful reactive species, such as persulfate, hypochlorite or hydroxyl radicals, that contribute to the degradation and mineralisation of COCs. The applied current density also influences the generation of these species. Finally, no acute toxicity towards Vibrio fischeri was observed for the treated groundwater after the electrochemical oxidation performed at 5 and 10 mA cm-2. These findings demonstrate that electrochemical oxidation with BDD anodes at moderate current densities is a promising alternative for the remediation of actual groundwater contaminated with DNAPLs.

Solar-assisted oxidation of organochlorine pesticides in groundwater using persulfate and ferrioxalate.

The oxidation of hexachlorocyclohexane isomers in the aqueous phase (Milli-Q and groundwater) was studied using persulfate activated by ferrioxalate and solar light at circumneutral pH. The experiments were conducted in a solar simulator reactor with local radiation fluxes qw= 1.12·10-7 E cm-2s-1 and in compound parabolic collectors with solar light (qw≈10-7 E cm-2s-1) for 390 min. The effect of activator dosage (18-125 µM ferrioxalate) and persulfate concentration (520-2600 µM) on hexachlorocyclohexane conversion and oxalate and oxidant consumption was analyzed. Conversion of about 95% of ß isomer was achieved at 390 min using 1300 µM of initial persulfate and 63 µM of Fe3+ concentration despite this ß isomer being the most recalcitrant to oxidation (XHexachlorocyclohexanes=0.98). Dechlorination above 80% was achieved under these conditions, analyzing the chlorides released into the water. The influence of chloride and bicarbonate on hexachlorocyclohexanes degradation was analyzed in milli-Q water and in groundwater. Hexachlorocyclohexane conversion at 390 min decreases from 98% to 83, 75 and 65% in the presence of chloride, bicarbonate or groundwater, respectively. Results obtained with compound parabolic collectors and solar light using 2600 µM Na2S2O8 and 63 µM Fe for removing hexachlorocyclohexanes agreed with those from the solar simulator reactor, supporting using solar light to activate persulfate for sustainable abatement of persistent organic pollutants in aqueous matrixes.

Disinfection of polymicrobial urines by electrochemical oxidation: Removal of antibiotic-resistant bacteria and genes.

In this work, data obtained from the University Hospital Complex of Albacete (Spain) were selected as a case study to carry out the disinfection experiments. To do this, different configurations of electrochemical reactors were tested for the disinfection of complex urines. Results showed that 4-6 logs bacterial removal were achieved for every bacterium tested when working with a microfluidic flow-through reactor after 180 min (0.423 Ah dm-3). The MIKROZON® cell reached a total disinfection after 60 min (1.212 Ah dm-3), causing severe damages induced in the cell walls observed in SEM images. The concentration profiles of the electrogenerated disinfectants in solution could explain the differences observed. Additionally, a mean decrease in the ARGs concentration ranked as follows: blaKPC (4.18-logs) > blaTEM (3.96-logs) > ermB (3.23-logs) using the MIKROZON® cell. This electro-ozonizer could be considered as a suitable alternative to reduce the risk of antibiotic resistance spread. Hence, this study provides an insight into different electrochemical reactors for the disinfection of complex hospital urine matrices and contributes to reduce the spread of antibiotic resistance through the elimination of ARGs. A topic of great importance nowadays that needs to be further studied.

Electrochemical Technologies to Decrease the Chemical Risk of Hospital Wastewater and Urine.

The inefficiency of conventional biological processes to remove pharmaceutical compounds (PhCs) in wastewater is leading to their accumulation in aquatic environments. These compounds are characterized by high toxicity, high antibiotic activity and low biodegradability, and their presence is causing serious environmental risks. Because much of the PhCs consumed by humans are excreted in the urine, hospital effluents have been considered one of the main routes of entry of PhCs into the environment. In this work, a critical review of the technologies employed for the removal of PhCs in hospital wastewater was carried out. This review provides an overview of the current state of the developed technologies for decreasing the chemical risks associated with the presence of PhCs in hospital wastewater or urine in the last years, including conventional treatments (filtration, adsorption, or biological processes), advanced oxidation processes (AOPs) and electrochemical advanced oxidation processes (EAOPs).

A review on disinfection technologies for controlling the antibiotic resistance spread.

The occurrence of antibiotic-resistant bacteria (ARB) in water bodies poses a sanitary and environmental risk. These ARB and other mobile genetic elements can be easily spread from hospital facilities, the point in which, for sure, they are more concentrated. For this reason, novel clean and efficient technologies are being developed for allowing to remove these ARB and other mobile genetic elements before their uncontrolled spread. In this paper, a review on the recent knowledge about the state of the art of the main disinfection technologies to control the antibiotic resistance spread from natural water, wastewater, and hospital wastewater (including urine matrices) is reported. These technologies involve not only conventional processes, but also the recent advances on advanced oxidation processes (AOPs), including electrochemical advanced oxidation processes (EAOPs). This review summarizes the state of the art on the applicability of these technologies and also focuses on the description of the disinfection mechanisms by each technology, highlighting the promising impact of EAOPs on the remediation of this important environmental and health problem.

A tube-in-tube membrane microreactor for tertiary treatment of urban wastewaters by photo-Fenton at neutral pH: A proof of concept.

This work presents a disruptive approach to promote highly-efficient photo-Fenton process at neutral pH under continuous mode operation. The system consists of a tube-in-tube membrane reactor designed for continuous-flow titration of low iron doses to the annular reaction zone (ARZ). A concentrated acidic ferrous ion (Fe2+) solution is fed by the lumen-side of the membrane, permeating through the membrane pores (inside-out mode), being dosed and uniformly delivered to the membrane shell-side. Polluted water, containing amoxicillin (AMX) and oxidant (H2O2), flows continuously in the reactor annulus (space between the membrane shell-side and an outer quartz tube). The catalyst radial dispersion is enhanced by the helicoidal movement of water around the membrane shell-side, efficiently promoting its contact with H2O2 and UV light. The efficiency of photochemical and photocatalytic oxidation was evaluated as a function of catalyst dose, catalyst injection mode (radial permeation vs injection upstream from the reactor inlet), light source (UVA vs UVC) and aqueous solution matrix (synthetic vs real wastewater). At steady-state, photo-Fenton reaction with Fe2+ radial addition, driven by UVC light, showed the highest AMX removal for synthetic (∼65%, removal rate of 44 µMAMX/min, using [Fe2+]ARZ = 2 mg/L and [H2O2]inlet = 10 mg/L) and real municipal wastewaters (∼45%, removal rate of 31 µMAMX/min, with [Fe2+]ARZ = 5 mg/L and [H2O2]inlet = 40 mg/L), with a residence time of only 4.6 s.

Enhancement of UV disinfection of urine matrixes by electrochemical oxidation.

This work focuses on the removal of antibiotic-resistant bacteria (ARB) contained in hospital urines by UV disinfection enhanced by electrochemical oxidation to overcome the limitations of both single processes in the disinfection of this type of effluents. UV disinfection, electrolysis, and photoelectrolysis of synthetic hospital urine intensified with K. pneumoniae were studied. The influence of the current density and the anode material was assessed on the disinfection performance of combined processes and the resulting synergies and/or antagonisms of coupling both technologies were also evaluated. Results show that the population of bacteria contained in hospital urine is only reduced by 3 orders of magnitude during UV disinfection. Electrolysis leads to complete disinfection of hospital urine when working at 50 A m-2 using Boron Doped Diamond (BDD) and Mixed Metal Oxides (MMO) as anodes. The coupling of electrolysis to the UV disinfection process leads to the highest disinfection rates, attaining a complete removal of ARB for all the current densities and anode materials tested. The use of MMO anodes leads to higher synergies than BDD electrodes. Results confirm that UV disinfection can be enhanced by electrolysis for the removal of ARB in urine, considering both technical and economic aspects.

Improving the biodegradability of hospital urines polluted with chloramphenicol by the application of electrochemical oxidation.

This work focuses on improving the biodegradability of hospital urines polluted with antibiotics by electrochemical advanced oxidation processes (EAOPs). To do this, chloramphenicol (CAP) has been used as a model compound and the influence of anodic material (Boron Doped Diamond (BDD) and Mixed Metal Oxide (MMO)) and current density (1.25-5 mA cm-2) on the toxicity and the biodegradability was evaluated. Results show that a complete CAP removal was attained using BDD anodes, being the process more efficient at the lowest current density tested (1.25 mA cm-2). Conversely, after passing 4 Ah dm-3, only 35% of CAP removal is reached using MMO anodes, regardless of the current density applied. Furthermore, a kinetic study demonstrated that there is a clear competitive oxidation between the target antibiotic and the organic compounds naturally contained in urine, regardless the current density and the anode material used. During the first stages of the electrolysis, acute toxicity is around 1% EC50 but it increases once CAP and its organic intermediates have been degraded. The formation and accumulation of inorganic oxidants may justify the remaining acute toxicity. This also helps to explain the trend observed in the rapid biodegradability assays. Finally, a 60% of standard biodegradability (Zahn-Wellens test) was achieved which suggests that electrochemical oxidation with BDD anodes could be the most appropriate technology to reduce the hazard of hospital urines at the operating conditions tested.

Sono- and photoelectrocatalytic processes for the removal of ionic liquids based on the 1-butyl-3-methylimidazolium cation.

In this work, sono- and photoelectrolysis of synthetic wastewaters polluted with the ionic liquids 1-Butyl-3-methylimidazolium acetate (BmimAc) and chloride (BmimCl) were investigated with diamond anodes. The results were compared to those attained by enhancing bare electrolysis with irradiation by UV light or with the application of high-frequency ultrasound (US). Despite its complex heterocyclic structure, the Bmim+ cation was successfully depleted with the three technologies that were tested and was mainly transformed into four different organic intermediates, an inorganic nitrogen species and carbon dioxide. Regardless of the technology that was evaluated, removal of the heterocyclic ring is much less efficient (and much slower) than oxidation of the counter ion. In turn, the counter ion influences the rate of removal of the ionic liquid cation. Thus, the electrolysis and photoelectrolysis of BmimAc are much less efficient than sonoelectrolysis, but their differences become much less important in the case of BmimCl. In this later case, the most efficient technology is photoelectrolysis. This result is directly related to the generation of free radicals in the solution by irradiation of the electrochemical system with UV light, which contributes significantly to the removal of Bmim+.

Degradation of dye Procion Red MX-5B by electrolytic and electro-irradiated technologies using diamond electrodes.

This work focuses on the treatment of synthetic wastewater polluted with dye Procion Red MX-5B by different Electrochemical Advanced Oxidation Processes (EAOP) based on diamond anodes. The influence of the current density and the supporting electrolyte has been studied on dye removal and total mineralization of the organic matter. Results show that electrolysis with diamond electrodes is a suitable technology for an efficient degradation of dye. Nonetheless, the process efficiency increases when using chloride as supporting electrolyte because of the electrochemical generation of hypochlorite in wastewater which significantly contribute to dye removal. On the contrary, the total mineralization of the organic matter is more efficient in sulfate media. In this case, large amounts of peroxodisulfate are electrogenerated, favoring the complete removal of total organic carbon (TOC). On the other hand, lower current densities (10 mA cm-2) lead to a more efficient removal of both dye and TOC due to the mass transfer limitations of the technology. Finally, the coupling of UV light irradiation or ultrasound to electrolysis significantly improves the process performance, being photoelectrolysis the most efficient technology for the treatment of wastewater polluted with Procion Red MX-5B. This fact is due to the potential production of free chlorine or sulfate radicals that takes place by the activation of the electrogenerated oxidants. These species are more reactive than oxidants and, therefore, they quickly attack the organic matter present in wastewater.

Electrolysis with diamond anodes: Eventually, there are refractory species!

In this work, synthetic wastewater polluted with ionic liquid 1-butyl-3-methylimidazolium (Bmim) bis(trifluoromethanesulfonyl)imide (NTf2) undergoes four electrolytic treatments with diamond anodes (bare electrolysis, electrolysis enhanced with peroxosulfate promoters, irradiated with UV light and with US) and results obtained were compared with those obtained with the application of Catalytic Wet Peroxide Oxidation (CWPO). Despite its complex heterocyclic structure, Bmim+ cation is successfully depleted with the five technologies tested, being transformed into intermediates that eventually can be mineralized. Photoelectrolysis attained the lowest concentration of intermediates, while CWPO is the technology less efficient in their degradation. However, the most surprising result is that concentration of NTf2- anion does not change during the five advanced oxidation processes tested, pointing out its strong refractory character, being the first species that exhibits this character in wastewater undergoing electrolysis with diamond. This means that the hydroxyl and sulfate radicals mediated oxidation and the direct electrolysis are inefficient for breaking the C-S, C-F and S-N bounds of the NTf2- anion, which is a very interesting mechanistic information to understand the complex processes undergone in electrolysis with diamond.

Electrolytic and electro-irradiated technologies for the removal of chloramphenicol in synthetic urine with diamond anodes.

Hospital effluents are a major source for the occurrence of pharmaceuticals in the environment. In this work, the treatment of synthetic urine polluted with chloramphenicol is studied by using three different conductive-diamond electrochemical oxidation technologies: electrolysis (single electrolysis), photoelectrolysis and high-frequency ultrasound sonoelectrolysis. These technologies were evaluated at 10 and 100 mA cm-2. Results shows that not only chloramphenicol but also other organics contained in urine are completely mineralized by electrolysis. Ammonium is the main inorganic nitrogen species formed and it can react with the electrogenerated hypochlorite, favouring the formation of chloramines. These species prevent the potential formation of perchlorate from chlorides contained in urine at low current densities (10 mA cm-2) and delay its occurrence at high current densities (100 mA cm-2). On the other hand, irradiation of ultraviolet (UV) light or high-frequency ultrasound (US) produce changes in the performance of the electrolytic treatment, but these changes are not as important as in other cases of study shown in the literature. Nonetheless, the effect of electroirradiated technologies seems to be higher and depends on the type of pollutant when working at low current densities (10 mA cm-2). It is positive in the case of the degradation of the antibiotic and the uric acid and negative in the case of urea where there is a clear antagonistic effect. Production of oxidants increases with the current density although in lower ratio than expected. These results are of great importance because clearly point out that electrolytic technologies can be applied to minimize the diffuse pollution associated to pharmaceuticals before discharge into municipal sewers.

Synergistic integration of sonochemical and electrochemical disinfection with DSA anodes.

This work focuses on the disinfection actual urban wastewater by the combination of ultrasound (US) irradiation and electrodisinfection with Dimensionally Stable Anodes (DSA). First, the inactivation of Escherichia coli (E. coli) during the sonochemical disinfection was studied at increasing ultrasound power. Results showed that it was not possible to achieve a complete disinfection, even at the highest US power (200 W) dosed by the experimental device used. Next, the electrodisinfection with DSA anodes at different current densities was studied, finding that it was necessary a minimum current density of 11.46 A m(-2) to reach the complete disinfection. Finally, an integrated sonoelectrodisinfection process was studied. Results showed a synergistic effect when coupling US irradiation with DSA electrodisinfection, with a synergy coefficient higher than 200% of the disinfection rate attained for the highest US power applied. In this process, hypochlorite and chloramines were identified as the main reagents for the disinfection process (neither chlorate nor perchlorate were detected), and the presence of trihalomethanes was far below acceptable values. Confirming this synergistic effect with DSA anodes opens the door to novel efficient disinfection processes, limiting the occurrence of hazardous disinfection by-products.

Scale-up of electrolytic and photoelectrolytic processes for water reclaiming: a preliminary study.

This work focuses on the scale-up of electrochemical and photoelectrochemical oxidation processes with diamond anodes for the removal of organic pollutants and disinfection of treated urban wastewater, two of the most important parameters for the reclaiming of wastewater. The removal of organics was studied with actual biologically treated urban wastewater intensified with 100 mg dm(-3) of caffeine, added as a trace organic pollutant. The disinfection was also studied with biologically treated urban wastewater, and Escherichia coli was used to monitor the efficiency of the process. Results obtained with a single DiaCell® 101 were compared with those obtained with a single-stack DiaCell® 1001 and with a pilot plant made up of five of these stacks. Results obtained demonstrate that scale-up is not a simple but a very complex process, in which not only the electrode and the irradiation dose are important but also mass transfer conditions. Enhanced mass transport conditions have a determining and very positive effect on the removal of organics and a negative effect on the disinfection. Likewise, ultraviolet (UV) irradiation affects in a different way in the different setups used, having a great influence on the removal of complex organics and on the speciation of oxidants produced during disinfection. This works helps to understand the key differences observed in the scale-up, and it is a first approach for future works focused on the real application of conductive diamond electrochemical oxidation.

Electrolytic and electro-irradiated processes with diamond anodes for the oxidation of persistent pollutants and disinfection of urban treated wastewater.

This paper analyzes the advantages and drawbacks of the combination of UV irradiation with electrolysis with the aim to give insight about the feasibility of the application of this technology for the reclaiming of conventionally-treated wastewater. The oxidation of synthetic solutions containing five selected model complex pollutants has been compared, showing that UV irradiation improves the results of electrolysis for progesterone, metoprolol and caffeine and deteriorates the performance for the degradation of sulfamethoxazole and dimethyl-phthalate. Differences observed becomes lower when mineralization is compared showing that the effects of UV irradiation are diluted when a mixture of species is oxidized. Results suggest that high ThOD/TOC (Theoretical Oxygen Demand/Total Organic Carbon) ratios improve the synergistic coupling of technologies while low values lead to a clear antagonistic effect. Because during oxidation progress this ratio is decreased, the observed effect on mineralization is much lower than in the oxidation of the raw molecule. Opposite to this low effect on the oxidation of organics, the improvement in the performance of the disinfection by coupling UV to electrolysis is much clearer. In addition, UV irradiation modifies significantly the chlorine speciation and helps to prevent the formation of hazardous species such as chlorate and perchlorate during the electrochemical processes.

Conductive diamond sono-electrochemical disinfection (CDSED) for municipal wastewater reclamation.

In the present work, the disinfection of actual effluents from a municipal wastewater treatment plant (WWTP) by a conductive diamond sono-electrochemical process was assessed. First, efficiency of single electrodisinfection process with diamond anodes (without the contribution of ultrasounds) was studied, finding that the total disinfection can be attained at current charges applied below 0.02kAhm(-3). It was also found that the main disinfection mechanism is the attack of Escherichia coli (E. coli) by the disinfectants produced in the electrochemical cell and that the production of chlorates is avoided when working at current densities not higher than 1.27Am(-2). Next, a marked synergistic effect was found when coupling ultrasound (US) irradiation to the electrochemical system (sono-electrochemical disinfection). This increase in the disinfection rate was found to be related to the suppression of the agglomeration of E. coli cells and the enhancement in the production of disinfectant species.

Effect of bipolar electrode material on the reclamation of urban wastewater by an integrated electrodisinfection/electrocoagulation process.

This work presents an integrated electrodisinfection/electrocoagulation (ED-EC) process for urban wastewater reuse that employs iron bipolar electrodes. Boron doped diamond (BDD) was used as the anode and stainless steel (SS) as the cathode. A perforated iron plate was introduced between the anode and cathode to function as a bipolar electrode. This ED-EC combined cell makes it possible to conduct the simultaneous removal of microbiological content and elimination of turbidity from urban wastewater. The results show that current densities greater than or equal to 6.70 A m(-2) enable complete disinfection of the effluent and the removal of more than 90% of its initial turbidity. Hypochlorite and chloramines formed during the ED-EC process were found to be the main compounds responsible for the disinfection process. Furthermore, a cell configuration of cathode (inlet)-anode (outlet) improves the process performance by enhancing turbidity removal. Finally, the influence of the bipolar electrode material (iron or aluminium) was assessed. The results indicate that the efficiency of the electrodisinfection process depends mainly on the anodic material and is not influenced by the material of the bipolar electrode. In contrast, the removal of turbidity is more efficient when using iron as a bipolar electrode, especially at low current densities, due to the formation of a passive layer on the aluminium that hinders the dissolution of the bipolar electrode.

Optimization of an integrated electrodisinfection/electrocoagulation process with Al bipolar electrodes for urban wastewater reclamation.

In this work, a novel integrated electrochemical process for urban wastewater regeneration is described. The electrochemical cell consists in a Boron Doped Diamond (BDD) or a Dimensionally Stable Anode (DSA) as anode, a Stainless Steel (SS) as cathode and a perforated aluminum plate, which behaves as bipolar electrode, between anode and cathode. Thus, in this cell, it is possible to carry out, at the same time, two different electrochemical processes: electrodisinfection (ED) and electrocoagulation (EC). The treatment of urban wastewater with different anodes and different operating conditions is studied. First of all, in order to check the process performance, experiments with synthetic wastewaters were carried out, showing that it is possible to achieve a 100% of turbidity removal by the electrodissolution of the bipolar electrode. Next, the effect of the current density and the anode material are studied during the ED-EC process of actual effluents. Results show that it is possible to remove Escherichia coli and turbidity simultaneously of an actual effluent from a WasteWater Treatment Facility (WWTF). The use of BDD anodes allows to remove the E. coli completely at an applied electric charge of 0.0077 A h dm(-3) when working with a current density of 6.65 A m(-2). On the other hand, with DSA anodes, the current density necessary to achieve the total removal of E. coli is higher (11.12 A m(-2)) than that required with BDD anodes. Finally, the influence of cell flow path and flow rate have been studied. Results show that the performance of the process strongly depends on the characteristics of the initial effluent (E. coli concentration and Cl(-)/NH(4)(+) initial ratio) and that a cell configuration cathode (inlet)-anode (outlet) and a higher flow rate enhance the removal of the turbidity from the treated effluent.