Activity and stability of bifunctional perovskite/carbon-based electrodes for the removal of antipyrine by electro-Fenton process.

Bifunctional perovskite/carbon-black(CB)/polytetrafluoroethylene(PTFE) electrodes for electro-generation and catalytic decomposition of hydrogen peroxide to oxidizing hydroxyl radicals have been fabricated. These electrodes were tested for electroFenton (EF) removal of antipyrine (ANT) as a model antipyretic and analgesic drug. The influence of the binder loading (20 and 40 wt % PTFE) and type of solvent (1,3-dipropanediol and water) was studied for the preparation of CB/PTFE electrodes. The electrode prepared with 20 wt % PTFE and water exhibited a low impedance and remarkable H2O2 electro-generation (about 1 g/L after 240 min, a production rate of ca. 6.5 mg/h·cm2). The incorporation of perovskite on CB/PTFE electrodes was also studied following two different methods: i) direct deposition on the CB/PTFE electrode surface and ii) addition in the own CB/PTFE/water paste used for the fabrication. Physicochemical and electrochemical characterization techniques were used for the electrode's characterization. The dispersion of perovskite particles in the own electrode matrix (method ii) exhibited a higher EF performance than the immobilisation onto the electrode surface (method i). EF experiments at 40 mA/cm2 and pH 7 (non-acidified conditions) showed ANT and TOC removals of 30% and 17%, respectively. The increase of current intensity up to 120 mA/cm2 achieved the complete removal of ANT and 92% of TOC mineralisation in 240 min. The bifunctional electrode also proved high stability and durability after 15 h of operation.

Ultrasonic processes for the advanced remediation of contaminated sediments.

Sediments play a fundamental role in the aquatic environment, so that the presence of contaminants poses severe concern for the possible negative effects on both environmental and human health. Sediment remediation is thus necessary to reduce pollutant concentrations and several techniques have been studied so far. A novel approach for sediment remediation is the use of Advanced Oxidation Processes, which include ultrasound (US). This paper focuses on the study of the ultrasonic effects for the simultaneous reduction of both organic and inorganic contaminants from sediments. To this end, the US technology was investigated as a stand-alone treatment as well as in combination with an electro-kinetic (EK) process, known to be effective in the removal of heavy metals from soil and sediments. The US remediation resulted in higher organic compound degradation, with an average 88% removal, but promising desorption yields (47-84%) were achieved for heavy metals as well. The combined EK/US process was found to be particularly effective for lead. Experimental outcomes highlighted the potential of the ultrasonic technology for the remediation of contaminated sediments and addressed some considerations for the possible scale-up.

Selecting the best piping arrangement for scaling-up an annular channel reactor: An experimental and computational fluid dynamics study.

This study is focused on the selection of the best piping arrangement for a pilot scale annular channel reactor intended for the remediation of waters and wastewaters. Two annular channel reactors composed of a single UV lamp and distinct piping arrangements were considered: (i) a novel reactor with tangential inlet/outlet pipes - the FluHelik reactor, and (ii) a conventional Jets reactor. These two reactors were manufactured at lab scale and characterized in terms of residence time distribution (RTD), radiant power and ability to degrade aqueous solutions spiked with a model compound - 3-amino-5-methylisoxazole (AMI) - by H2O2/UVC and UVC processes. Computational fluid dynamics (CFD) simulations were used to assess the hydrodynamics, RTD and UV radiation intensity distribution of both reactors at pilot scale. In general, experimental results at lab scale revealed quite similar RTDs, radiant powers and AMI degradation rates for both reactors. On the other hand, CFD simulations at pilot scale revealed the generation of a helical motion of fluid around the UVC lamp in the FluHelik reactor, inducing: (i) a longer contact time between fluid particles and UV light, (ii) more intense dynamics of macromixing as a result of larger velocity gradients, turbulent intensities and dispersion of RTD values around the peak, and (iii) a more homogeneous UV radiation distribution. In addition, the design of the FluHelik reactor can favor the implementation of various reactors in series, promoting its application at industrial scale. The FluHelik reactor was chosen for scaling-up. A pre-pilot scale treatment unit containing this reactor was constructed and its feasibility was proven.

Heterogeneous electro-Fenton as plausible technology for the degradation of imidazolinium-based ionic liquids.

Conventional water treatments are generally inadequate for degradation of emerging pollutants such as ionic liquids (ILs). The use of heterogeneous electro-Fenton (HEF) has attracted great interest, due to its ability to efficiently oxidize a wide range of organic pollutants operating in cycles or in continuous mode. In this study, the removal of a complex IL from the imidazolinium family (1,3-Bis(2,4,6-trimethylphenyl)imidazolinium chloride), by means of HEF using iron alginate spheres as catalyst has been investigated, resulting in significant TOC decay after 6 h. The optimization of the key process parameters (current, IL concentration and catalyst dosage) has been performed using a Box-Behnken experimental design and achieving 76.98% of TOC abatement in 2 h of treatment. Current proved to be a crucial parameter and high catalyst dosage is required to achieve the maximum removal. In addition, an insight about the availability of iron into the reactor and the evolution of several intermediates has been carried out by employing differential pulse voltammetry on screen-printed carbon electrodes. The evolution of the different voltammetric peaks confirmed the influence of iron release, and the generation of several iron complexes has permitted the comprehension of the degradation pathway, which has been validated by chromatographic techniques.

p-Nitrophenol degradation by electro-Fenton process: Pathway, kinetic model and optimization using central composite design.

The chemical process scale-up, from lab studies to industrial production, is challenging and requires deep knowledge of the kinetic model and the reactions that take place in the system. This knowledge is also useful in order to be employed for the reactor design and the determination of the optimal operational conditions. In this study, a model substituted phenol such as p-nitrophenol was degraded by electro-Fenton process and the reaction products yielded along the treatment were recorded. The kinetic model was developed using Matlab software and was based on main reactions that occurred until total mineralization which allowed predicting the degradation pathway under this advanced oxidation process. The predicted concentration profiles of p-nitrophenol, their intermediates and by-products in electro-Fenton process were validated with experimental assays and the results were consistent. Finally, based on the developed kinetic model the degradation process was optimized using central composite design taking as key parameters the ferrous ion concentration and current density.

Sequential two-column electro-Fenton-photolytic reactor for the treatment of winery wastewater.

The high amount of winery wastewaters produced each year makes their treatment a priority issue due to their problematic characteristics such as acid pH, high concentration of organic load and colourful compounds. Furthermore, some of these effluents can have dissolved pesticides, due to the previous grape treatments, which are recalcitrant to conventional treatments. Recently, photo-electro-Fenton process has been reported as an effective procedure to mineralize different organic contaminants and a promising technology for the treatment of these complex matrixes. However, the reactors available for applying this process are scarce and they show several limitations. In this study, a sequential two-column reactor for the photo-electro-Fenton treatment was designed and evaluated for the treatment of different pesticides, pirimicarb and pyrimethanil, used in wine production. Both studied pesticides were efficiently removed, and the transformation products were determined. Finally, the treatment of a complex aqueous matrix composed by winery wastewater and the previously studied pesticides was carried out in the designed sequential reactor. The high removals of TOC and COD reached and the low energy consumption demonstrated the efficiency of this new configuration.

Degradation of thiamethoxam by the synergetic effect between anodic oxidation and Fenton reactions.

In this work, a comparative study using anodic oxidation, Fenton and electro-Fenton treatments was performed in order to determine the synergic effect for the removal of thiamethoxan. The results determined that electro-Fenton process showed high efficiency in comparison with Fenton or anodic oxidation. After that, this hybrid process was optimized and the influence of iron catalyst concentration and applied current intensity on the degradation and mineralization were evaluated. Degradation profiles were monitored by high performance liquid chromatography (HPLC) being satisfactorily described by pseudo-first order kinetic model. At the optimal experimental conditions (300mA and 0.2mM Fe(+2)), the complete degradation of thiamethoxam was achieved after 10min. On the other hand, mineralization of thiamethoxam was monitored by total organic carbon (TOC) decay reaching more than 92% of TOC removal after 8h. Furthermore, a plausible mineralization pathway for the thiamethoxam degradation was proposed based on the identification of by-products such as aromatic intermediates, carboxylic acids and inorganic ions released throughout electro-Fenton process.

Removal of metal and organic pollutants from wastewater by a sequential selective technique.

In this study the application of a sequential selective system that combined biosorption with biodegradation was evaluated as a feasible process for the removal of Cr(VI) and m-cresol from effluents. Cr(VI) biosorption on pretreated chestnut shells showed 100% metal removal and modelling efforts demonstrated that the pseudo-second order kinetic model and Langmuir isotherm fit well the process behaviour. Thus, the treated stream was an appropriate environment for the biodegradation of m-cresol using a laccase-producer fungus, Phlebia radiata. Two bioreactor configurations, rotating drum and modified-airlift, were studied using the fungus grown on chestnut shells, which act as support-substrate as well as oxidative enzyme inductor increasing the laccase activity up to 1000UL(-1). The best bioreactor, rotating drum, reached 100% removal in 7days. Finally, the best configuration for the sequential selective system was modelled operating in continuous mode by the breakthrough curves generated using FASTv2.0 and the design bioreactor flow model.

Ionic liquids for the concomitant use in extremophiles lysis and extremozymes extraction.

Ionic liquids have been successfully proposed to modify membrane permeability in cultures of a model extremophilic bacterium Thermus thermophilus HB27, which makes up the first time that aqueous solutions of these molten salts are applied in downstream stages of this kind of microorganisms. The presence of 1g/L of C10MIMCl entails a great solubilisation of cell biomass, thus allowing the release of intracellular and membrane-bound enzyme. The influence on the enzyme activity of two inorganic salts such as Na2CO3 and (NH4)2SO4, selected on the basis of their high salting out potential and biocompatibility with enzymes, respectively, was investigated. In parallel, their ability to trigger phase segregation was confirmed in the presence of the enzyme crude, leading to very high levels of enzyme extraction (96%). The validity of the strategy was confirmed by operating at bioreactor scale, and the main bioprocess parameters were obtained by modelling the experimental data.

Hybrid sequential treatment of aromatic hydrocarbon-polluted effluents using non-ionic surfactants as solubilizers and extractants.

A treatment train combining a biological and a physical approach was investigated for the first time in order to remediate polycyclic aromatic hydrocarbons (PAHs)-polluted effluents. Given the hydrophobic nature of these contaminants, the presence of non-ionic surfactants is compulsory to allow their bioavailability. The presence of these surfactants also entails an advantage in order to ease contaminant removal by the formation of aqueous two-phase systems (ATPS). The segregation ability of environmentally benign salts such as potassium tartrate, citrate, and oxalate was discussed for extracting phenanthrene (PHE), pyrene (PYR), and benzo[a]anthracene (BaA). The biological remediation efficiency reached circa 60% for PHE and PYR, and more than 80% for BaA. The coupling of ATPS subsequent stage by using potassium citrate allowed increasing the total PAH remediation yields higher than 97% of PAH removal. The viability of the proposed solution was investigated at industrial scale by using the software tool SuperPro Designer.

Box-Behnken methodology for Cr (VI) and leather dyes removal by an eco-friendly biosorbent: F. vesiculosus.

This study focused on leather industrial effluents treatment by biosorption using Fucus vesiculosus as low-cost adsorbent. These effluents are yellowish-brown color and high concentration of Cr (VI). Therefore, biosorption process was optimized using response surface methodology based on Box-Behnken design operating with a simulated leather effluent obtained by mixture of Cr (VI) solution and four leather dyes. The key variables selected were initial solution pH, biomass dosage and CaCl2 concentration in the pretreatment stage. The statistical analysis shows that pH has a negligible effect, being the biomass dosage and CaCl2 concentration the most significant variables. At optimal conditions, 98% of Cr (VI) and 88% of dyes removal can be achieved. Freundlich fitted better to the obtained equilibrium data for all studied systems than Temkin, Langmuir or D-R models. In addition, the use of the final biosorbent as support-substrate to grown of enzyme producer fungi, Pleurotus ostreatus, was also demonstrated.

Novel physico-biological treatment for the remediation of textile dyes-containing industrial effluents.

In this work, a novel remediation strategy consisting of a sequential biological and physical process is proposed to remove dyes from a textile polluted effluent. The decolorization ability of Anoxybacillus flavithermus in an aqueous effluent containing two representative textile finishing dyes (Reactive Black 5 and Acid Black 48, as di-azo and antraquinone class, respectively) was proved. The decolorization efficiency for a mixture of both dyes reached almost 60% in less than 12h, which points out the suitability of the selected microorganism. In a sequential stage, an aqueous biphasic system consisting of non-ionic surfactants and a potassium-based organic salt, acting as the salting out agent, was investigated. The phase segregation potential of the selected salts was evaluated in the light of different thermodynamic models, and remediation levels higher than 99% were reached.

Assessment of Arthrobacter viscosus as reactive medium for forming permeable reactive biobarrier applied to PAHs remediation.

Polycyclic aromatic hydrocarbons (PAHs) are significant environmental contaminants as they are present naturally as well as anthropogenically in soil, air and water. In spite of their low solubility, PAHs are spread to the environment, and they are present in surface water, industrial effluent or groundwater. Amongst all remediation technologies for treating groundwater contaminated with PAHs, the use of a permeable reactive biobarrier (PRBB) appears to be the most cost-effective, energy efficient, and environmentally sound approach. In this technology, the microorganisms are used as reactive medium to degrade or stabilize the contaminants. The main limits of this approach are that the microorganisms or consortium used for forming the PRBB should show adequate characteristics. They must be retained in the barrier-forming biofilm, and they should also have degradative ability for the target pollutants. The aim of the present work is to evaluate the viability of Arthrobacter viscosus as bioreactive medium for forming PRBB. Initially, the ability of A. viscosus to remove PAHs, benzo[a]anthracene 100 µM and phenanthrene 100 µM was evaluated operating in a batch bench-scale bioreactor. In both cases, total benzo[a]anthracene and phenanthrene removals were obtained after 7 and 3 days, respectively. Furthermore, the viability of the microorganisms was evaluated in the presence of chromium in a continuous mode. As a final point, the adhesion of A. viscosus to sepiolite forming a bioreactive material to build PRBB was demonstrated. In view of the attained results, it can be concluded that A. viscosus could be a suitable microorganism to form a bioreactive medium for PAHs remediation.

Using iron-loaded sepiolite obtained by adsorption as a catalyst in the electro-Fenton oxidation of Reactive Black 5.

This study explores the possibility of using iron-loaded sepiolite, obtained by recovering iron from polluted water, as a catalyst in the electro-Fenton oxidation of organic pollutants in textile effluents. The removal of iron ions from aqueous solution by adsorption on sepiolite was studied in batch tests at iron concentrations between 100 and 1,000 ppm. Electro-Fenton experiments were carried out in an electrochemical cell with a working volume of 0.15 L, an air flow of 1 L/min, and 3 g of iron-loaded sepiolite. An electric field was applied using a boron-doped diamond anode and a graphite sheet cathode connected to a direct current power supply with a constant potential drop. Reactive Black 5 (100 mg/L) was selected as the model dye. The adsorption isotherms proved the ability of the used adsorbent. The removal of the iron ion by adsorption on sepiolite was in the range of 80-100 % for the studied concentration range. The Langmuir and Freundlich isotherms were found to be applicable in terms of the relatively high regression values. Iron-loaded sepiolite could be used as an effective heterogeneous catalyst for the degradation of organic dyes in the electro-Fenton process. Successive batch processes were performed at optimal working conditions (5 V and pH 2). The results indicate the suitability of the proposed combined process, adsorption to iron remediation followed by the application of the obtained iron-loaded sepiolite to the electro-Fenton technique, to oxidize polluted effluents.

Development of permeable reactive biobarrier for the removal of PAHs by Trichoderma longibrachiatum.

In this work, the formation of permeable reactive biobarriers (PRBBs) using Trichoderma longibrachiatum over nylon sponge as bioreactive medium for removal of polycyclic aromatic hydrocarbons (PAHs) was studied. Colony formation was pretested without PAH presence by inoculation of fungus into nylon sponge. The fungus formed a large quantity of strongly adhesive biofilm among nylon sponge. Afterwards, the ability of the developed bioreactive medium was tested to remediate phenanthrene in aqueous medium and in soil. In aqueous medium, a 90% of phenanthrene concentration reduction was observed after 14 d. However, the pollutant removal in soil requires previous fungus colonization and the attained level was around 70% after 28 d. Subsequently, the formed bioreactive material was used in a glass column reactor to evaluate its application as PRBBs. Mixtures of phenanthrene, benzo[a]anthracene and pyrene at several concentrations, from 100 to 400 µM, were treated. In all cases, the performance of the PRBB was satisfactory and total PAH removals were achieved. These results suggest that PRBBs of T. longibrachiatum supported on nylon sponge can be an effective method for the treatment of PAHs.

Polymerisation of Kraft lignin from black liquors by laccase from Myceliophthora thermophila: effect of operational conditions and black liquor origin.

The capacity of laccase from Myceliophthora thermophila to promote the oxidative polymerisation of Kraft lignin (KL) was evaluated in several conditions of pH, temperature, enzyme dosage and treatment time. Moreover, different black liquors from the Kraft cooking of Eucalyptus globulus and mixture of Pinus pinaster/E. globulus were evaluated in order to determine the effect of the KL source on the polymerisation reaction. Furthermore, one of these black liquors was fractionated by sequential organic solvent fractionation and the polymerisation of the corresponding fractions was tested. Polymerisation products were analysed by size exclusion chromatography and Fourier transform infrared spectroscopy. The results provide evidence of notable lignin modifications after incubation with laccase. Structural oxidation and a notably molecular weight increase were attained, reaching a polymer of 69-fold its initial molecular weight depending on the raw lignin. Moreover, optimum values of reaction conditions were obtained: pH 7.3, 70°C, 2UmL(-1) and 2h.

Approaching chlorpyrifos bioelimination at bench scale bioreactor.

Chlorpyrifos (CP) is one of the most commonly applied insecticides for control of pests and insects. The inappropriate use of this kind of chemicals has caused heavy contamination of many terrestrial and aquatic ecosystems thus representing a great environmental and health risk. The main purpose of this work is to investigate novel microbial agents (Pseudomonas stutzeri and the previously obtained consortium LB2) with the ability to degrade CP from polluted effluents. This goal was achieved by operating at different lab scales (flask and bioreactor) and operation modes (batch and fed-batch). Very low degradation and biomass levels were detected in cultures performed with the consortium LB2. In contrast, near complete CP degradation was reached by P. stutzeri at the optimal conditions in less than 1 month, showing a depletion rate of 0.054 h(-1). The scale-up at bench scale stirred tank bioreactor allowed improving the specific degradation rate in ten folds and total CP degradation was obtained after 2 days. Moreover, biomass and biodegradation profiles were modelled to reach a better characterization of the bioremediation process.

Viability of phenanthrene biodegradation by an isolated bacterial consortium: optimization and scale-up.

In the present work, biodegradation of phenanthrene by a bacterial consortium (LB2), isolated from lab-polluted soils has been investigated. The 16S rRNA gene-based molecular analysis revealed that the bacterial consortium LB2 consisted of two strains showing a very high homology with Staphylococcus warneri and Bacillus pumilus. The optimization of phenanthrene degradation by the consortium LB2, using a central composite face-centered design was carried out taking into account three important parameters such as temperature, pH, and phenanthrene concentration. Near complete phenanthrene degradation was reached by consortium LB2 at the optimal conditions (pH of 7.5 and 37.5 °C) in less than 48 h. Moreover, the efficiency of phenanthrene biodegradation was assessed by using logistic and Luedeking and Piret-type models. Finally, the process was implemented at bench-scale bioreactor and the main degradation routes were identified based on GC-MS data.

Optimisation of decolourisation and degradation of Reactive Black 5 dye under electro-Fenton process using Fe alginate gel beads.

The aim of this work was to improve the ability of the electro-Fenton process using Fe alginate gel beads for the remediation of wastewater contaminated with synthetic dyes and using a model diazo dye such as Reactive Black 5 (RB5). Batch experiments were conducted to study the effects of main parameters, such as voltage, pH and iron concentration. Dye decolourisation, reduction of chemical oxygen demand (COD) and energy consumption were studied. Central composite face-centred experimental design matrix and response surface methodology were applied to design the experiments and to evaluate the interactive effects of the three studied parameters. A total of 20 experimental runs were set, and the kinetic data were analysed using first-order and second-order models. In all cases, the experimental data were fitted to the empirical second-order model with a suitable degree for the maximum decolourisation of RB5, COD reduction and energy consumption by electro-Fenton-Fe alginate gel beads treatment. Working with the obtained empirical model, the optimisation of the process was carried out. The second-order polynomial regression model suggests that the optimum conditions for attaining maximum decolourisation, COD reduction and energy consumption are voltage, 5.69 V; pH 2.24 and iron concentration, 2.68 mM. Moreover, the fixation of iron on alginate beads suggests that the degradation process can be developed under this electro-Fenton process in repeated batches and in a continuous mode.

Electro-Fenton decolourisation of dyes in an airlift continuous reactor using iron alginate beads.

In this study, electro-Fenton dye degradation was performed in an airlift continuous reactor configuration by harnessing the catalytic activity of Fe alginate gel beads. Electro-Fenton experiments were carried out in an airlift reactor with a working volume of 1.5 L, air flow of 1.5 L/min and 115 g of Fe alginate gel beads. An electric field was applied by two graphite bars connected to a direct current power supply with a constant potential drop. In this study, Lissamine Green B and Reactive Black 5 were selected as model dyes. Fe alginate gel beads can be used as an effective heterogeneous catalyst for the degradation of organic dyes in the electro-Fenton process, as they are more efficient than the conventional electrochemical techniques. At optimal working conditions (3 V and pH 2), the continuous process was performed. For both dyes, the degree of decolourisation increases when the residence time augments. Taking into account hydrodynamic and kinetic behaviour, a model to describe the reactor profile was obtained, and the standard deviation between experimental and theoretical data was lower than 6%. The results indicate the suitability of the electro-Fenton technique to oxidise polluted effluents in the presence of Fe alginate gel beads. Moreover, the operation is possible in a continuous airlift reactor, due to the entrapment of iron in the alginate matrix.