Trimetallic Nanoalloy of NiFeCo Embedded in Phosphidated Nitrogen Doped Carbon Catalyst for Efficient Electro-Oxidation of Kraft Lignin.

Recently, electro-oxidation of kraft lignin has been reported as a prominent electrochemical reaction to generate hydrogen at lower overpotential in alkaline water electrolysis. However, this reaction is highly limited by the low performance of existing electrocatalysts. Herein, we report a novel yet effective catalyst that comprises nonprecious trimetallic (Ni, Fe, and Co) nanoalloy as a core in a phosphidated nitrogen-doped carbon shell (referred to as sample P-NiFeCo/NC) for efficient electro-oxidation of kraft lignin at different temperatures in alkaline medium. The as-synthesized catalyst electro-oxidizes lignin only at 0.2 V versus Hg/HgO, which is almost three times less positive potential than in the conventional oxygen evolution reaction (0.59 V versus Hg/HgO) at 6.4 mA/cm2 in 1 M KOH. The catalyst demonstrates a turnover frequency (TOF) three to five times greater in lignin containing 1 M KOH than that of pure 1 M KOH. More importantly, the catalyst P-NiFeCo/NC shows theoretical hydrogen production of about 0.37 µmoles/min in the presence of lignin, much higher than that in pure 1 M KOH (0.0078 µ moles/min). Thus, this work verifies the benefit of the NiFeCo nanoalloy incorporated in carbon matrix, providing the way to realize a highly active catalyst for the electro-oxidation of kraft lignin.

Degradation of commercial glyphosate-based herbicide via advanced oxidative processes in aqueous media and phytotoxicity evaluation using maize seeds.

Glyphosate is a herbicide that acts as a broad-spectrum, non-selective, post-emergence systemic pest controller. Its continuing, increasing, and excessive use in many countries in recent years poses a significant threat to the environment and human health due to the prevalence of this herbicide in water bodies and its impact on non-target organisms. In this context, it is essential to develop processes aimed at the non-selective degradation of glyphosate and its by-products. In this study, various advanced oxidative processes were applied: Fenton, electro-Fenton, photoelectro-oxidation, and photoelectro-Fenton, with the objective of oxidizing glyphosate in the commercial product Roundup®. The resultant oxidation products and the phytotoxicological effect on maize seed germination were also analyzed. Following each treatment, chemical oxygen demand (COD), total organic carbon (TOC), glyphosate degradation, and oxidation by-product formation were analyzed. The treated solutions were used to germinate maize seeds for 7 days in a germination chamber applying a photoperiod of 12 h at 24 °C. The % of germination, protein and hydrogen peroxide (H2O2) content, lipid peroxidation extent (MDA), and superoxide dismutase (SOD), peroxidase (POD), and catalase (CAT) activities were determined. The photoelectro-Fenton treatment was the most effective in degrading glyphosate, operating synergistically to break glyphosate bonds, thereby generating non-toxic short-chain molecules. Maize seed germination was satisfactory (> 50 %), but the persistent formation of reactive oxygen species (ROS) led to increased antioxidant activities of SOD, CAT, and POD enzymes acting in a compensatory manner against ROS, thus sustaining the photosynthetic apparatus. Hormesis, a stimulatory effect of glyphosate, was also observed in the presence of low concentrations of glyphosate.

Transition Metal Substituted Barium Hexaferrite-Modified Electrode: Application as Electrochemical Sensor of Acetaminophen.

This study used substituted barium hexaferrites, which were previously prepared and reported by the authors, to detect acetaminophen by the modification of a conventional glassy carbon electrode (GCE), which led to promising results. The synthesis of this electrode-modifying material was conducted using a citrate sol gel process. A test synthesis using glycerin and propylene glycol revealed that glycerin produced a better result, while less positive anodic potential values were associated with the electrooxidation of N-acetyl-p-aminophenol (NAP). Excellent electroactivity was exhibited by the cobalt-substituted barium-hexaferrite-nanomaterial-modified electrode. A good linear relationship between the concentration and the current response of acetaminophen (paracetamol) was obtained with a detection limit of (0.255 ± 0.005) µM for the Ba1.0Co1.22Fe11.41O18.11 GCE, (0.577 ± 0.007) µM for the Ba1.14Cu0.82Fe11.65O18.02 GCE, and (0.595 ± 0.008) µM for the bare GCE. The levels of NAP in a real sample of urine were quantitatively analyzed using the proposed method, with recovery ranges from 96.6% to 101.0% and 93.9% to 98.4% for the modified electrode with Cobalt-substituted barium hexaferrites (CoFM) and Copper-substituted barium hexaferrites (CuFM), respectively. These results confirm the high electrochemical activity of Ba1.0Co1.22Fe11.41O18.11 nanoparticles and thus their potential for use in the development of sensing devices for substances of pharmaceutical interest, such as acetaminophen (NAP).

Facile Synthesis of Unsupported Pd Aerogel for High Performance Formic Acid Microfluidic Fuel Cell.

In this work, unsupported Pd aerogel catalysts were synthesized for the very first time by using microwaves as a heating source followed by a lyophilization drying process and used towards formic acid electro-oxidation in a microfluidic fuel cell. Aerogels were also made by heating in a conventional oven to evaluate the microwave effect during the synthesis process of the unsupported Pd aerogels. The performance of the catalysts obtained by means of microwave heating favored the formic acid electro-oxidation with H2SO4 as the electrolyte. The aerogels' performance as anodic catalysts was carried out in a microfluidic fuel cell, giving power densities of up to 14 mW cm-2 when using mass loads of only 0.1 mg on a 0.019 cm2 electrode surface. The power densities of the aerogels obtained by microwave heating gave a performance superior to the resultant aerogel prepared using conventional heating and even better than a commercial Pd/C catalyst.

Decontamination of real urban sewage-comparison between Fenton and electrochemical oxidation.

Advanced oxidation processes have been used for wastewater treatment due to their capacity to reduce the organic loading and for their fast reactions. In this paper, we explore the viability of isolated and sequential use of electrochemical oxidation and Fenton processes into treatment of real raw urban sewage. The electrochemical process was carried out using DSA®-Cl2 electrodes and factorial planning in order to investigate the influence of pH, current density, and electrolyte. Fenton reaction was also used and H2O2 and Fe2+ concentration effects were investigated. The efficiency was estimated by chemical oxygen demand (COD) removal and in the optimized conditions the effluent was characterized by turbidity, suspended/dissolved/total solids, ammonia, chloride ions, free chlorine, nitrite, and potassium analysis and bioassays with Artemia ssp. and Lactuca sativa. The study demonstrated that the use of electrochemical technique followed by Fenton allowed an improvement in the degradation of organic matter and reduction of turbidity and solid content, reaching reductions of 86.8, 96.4, 99.4, 56.1, and 66.7% for COD, turbidity, SS, DS, and TS, respectively. The associated treatment also contributed to the reduction of energy consumption by 74.9%, from the 23.9 kWh m-3 observed during the electrochemical treatment isolated to the 6 kWh m-3 during the associated process. All the treatments presented toxicity reduction, with the electrochemical process achieving the best results.

Study of a coupled adsorption/electro-oxidation process as a tertiary treatment for tequila industry wastewater.

Vinasse wastewater from tequila industry that has been conventionally treated is usually characterized by a chemical oxygen demand (COD) above 150 mg L-1, which is the maximum content permitted for discharge by Mexican Regulation. In order to increase the wastewater quality, different processes were applied, and from the experimental results, the advantages and limitations were analyzed. In this way, although Fenton experiments showed acceptable COD removal efficiencies (79-90%), operation as well as cost limit its adoption as a viable technology. Therefore, additional experiments explored electro-Fenton (EF) as well as adsorption coupled to EF in a tubular reactor. The corresponding data revealed that there was no additional increase in COD removal performance probably due to the low oxygen solubility in the electrolytic solution and the high pH that prevents the existence of Fe2+ ions necessary for the Fenton mixture. In view of these results, when an activated carbon (AC) filter was coupled to polarization at current densities between 0.5 and 2 mA cm-2, removal efficiencies from 71 to 81%, corresponding to final COD of 78 to 33 mg L-1, were achieved. Also, the adsorbent surface was continuously regenerated, promoting a more efficient adsorption and a longer service life for the AC filter. In this case, by using a current density of 0.5 mA cm-2, COD was reduced to sufficiently small values for discharge into natural water bodies, maintaining low energy consumption and therefore acceptable operation costs.

The electro-oxidation of tetracycline hydrochloride in commercial DSA® modified by electrodeposited platinum.

Tetracycline hydrochloride (TCH) electro-oxidation by commercial DSA® and commercial DSA® modified by platinum electrodeposition was evaluated. The electrodeposition was carried out at constant potential (E = - 0.73 V vs RHE) in different times (1200, 2400, and 4800 s). Scanning electron microscopy (SEM) images show that Pt electrodeposits have elongated shape particle forming a uniform surface, and energy dispersive spectroscopy (EDS) data confirms the presence of Pt on the surface. The electrochemical characterization by cyclic voltammetry showed an increase of the electrochemically active area (EAA) in function of the Pt electrodeposition time. The electro-oxidation of the TCH 0.45 mmol L-1 in H2SO4 0.1 mol L-1 solution was evaluated according to the applied current densities (j = 25, 50, 100 mA cm-2). Both the amount of platinum deposited and j showed a slight improvement in the efficiency of TCH removal, reaching 97.2% of TCH removal to DSA®/Pt4800 and 100 mA cm-2. The TCH mineralization (TOC removal), the percentage of mineralization current efficiency (MCE%), and energy consumption were 15.8%, 0.2649%, and 7.4138 kWh (g TOC)-1, respectively. The DSA®/Pt electrodes showed higher stability to TCH electro-oxidation, indicating to be a promising material for the electro-oxidation of organic pollutants.

Layered platforms of Ti4O7 as flow-through anodes for intensifying the electro-oxidation of bentazon.

In this study, we prepared Ti4O7 porous electrodes with continuous layered structures characterized by different layer-to-layer distance (from 2 to 10 µm) but the same total void fraction (88-90%), to modulate the electrodes' permeability and the volumetric electrochemical surface area (from 90 to 840 cm2 cm-3). These platforms were evaluated as anodes in the electro-oxidation (EO) of bentazon in a three-electrode cell under galvanostatic conditions, operated both in traditional batch (TB) or batch recycle flow-through (BRFT) modes. The performance was significantly enhanced when the liquid was recirculated through the lamellar structure of the electrodes. In BRFT mode, the electrode interlayer gap was found to be a key factor to control the bentazon and total organic carbon (TOC) conversions. For the best conditions evaluated (BRFT, 10 µm-interlayered Ti4O7 electrodes with a volumetric surface area of 90 cm2 cm-3), the effect of the applied current (1 or 3 mA) and liquid flow rate (10, 12 or 14 mL. min-1) was investigated. Specific energy consumption (SEC) values were estimated to reveal the performance of each of the EO treatments from an energetic point of view. The use of 10 µm-interlayered Ti4O7 electrodes at 1 mA in BRFT mode at a flow rate of 14 mL min-1 showed the best results, yielding 85% bentazon removal, 57% mineralization and SEC values of 0.006 kWh.gTOC-1 after 6 h of treatment. This contribution highlights the use of layered Ti4O7 electrodes as a promising strategy for intensifying EO processes, pointing to a trade-off between the accessibility to the internal electrode structure and the volumetric electrode surface area to enhance the contact between the target molecules and the hydroxyl radicals physisorbed on the electrode surface, while minimizing simultaneously the energy requirements.

Electro-Oxidation-Plasma Treatment for Azo Dye Carmoisine (Acid Red 14) in an Aqueous Solution.

Currently, azo dye Carmoisine is an additive that is widely used in the food processing industry sector. However, limited biodegradability in the environment has become a major concern regarding the removal of azo dye. In this study, the degradation of azo dye Carmoisine (acid red 14) in an aqueous solution was studied by using a sequenced process of electro-oxidation-plasma at atmospheric pressure (EO-PAP). Both the efficiency and effectiveness of the process were compared individually. To ascertain the behavior of azo dye Carmoisine over the degradation process, the variations in its physical characteristics were analyzed with a voltage-current relationship, optical emission spectra (OES) and temperature. On the other hand, chemical variables were analyzed by finding out pH, electrical conductivity, absorbance (UV/VIS Spectrophotometry), chemical oxygen demand (COD), cyclic voltammetry (CV), energy consumption and cost. The sequenced process (EO-PAP) increased degradation efficiency, reaching 100% for azo dye Carmoisine (acid red 14) in 60 min. It was observed that the introduction of small quantities of iron metal ions (Fe2+/Fe3+) as catalysts into the plasma process and the hydrogen peroxide formed in plasma electrical discharge led to the formation of larger amounts of hydroxyl radicals, thus promoting a better performance in the degradation of azo dye. This sequenced process increased the decolorization process.

Effect of the Random Defects Generated on the Surface of Pt(111) on the Electro-oxidation of Ethanol: An Electrochemical Study.

In the present work, the Pt(111) surface was disordered by controlling the density of {110}- and {100}-type defects. The cyclic voltammogram (CV) of a disordered surface in acid media consists of three contributions within the hydrogen adsorption/desorption region: one from the well-ordered Pt(111) symmetry and the other two transformed from the {111}-symmetry with contributions of {110}- and {100}-type surface defects. The ethanol oxidation reaction (EOR) was studied on these disordered surfaces. Electrochemical studies were performed in 0.1 M HClO4 +0.1 M ethanol using cyclic voltammetry and chronoamperometry. Changes in current densities associated to the specific potentials at which each oxidation peak appears suggest that different surface domains of disordered platinum oxidize ethanol independently. Additionally, as the surface-defect density increases, the EOR is catalysed better. This tendency is directly observed from the CV parameters because the onset and peak potentials are shifted to less positive values and accompanied by increases in the oxidation-peak current on disordered surfaces. Similarly, the CO oxidation striping confirmed this same tendency. Chronoamperometric experiments showed two opposite behaviors at short oxidation times (0.1 s). The EOR was quickly catalyzed on the most disordered surface, Pt(111)-16, and was then rapidly deactivated. These results provide fundamental information on the EOR, which contributes to the atomic-level understanding of real catalysts.

The long and successful journey of electrochemically active amino acids. From fundamental adsorption studies to potential surface engineering tools

ABSTRACT Proteins have been the subject of electrochemical studies. It is possible to apply electrochemical techniques to obtain information about their structure due to the presence of five electroactive amino acids that can be oriented to the outside of the peptidic chain. These amino acids are L-Tryptophan (L-Trp), L-Tyrosine (L-Tyr), L-Histidine (L-His), L-Methionine (L-Met) and L-Cysteine (L-Cys); their electrochemical behavior being subject of extensive research, but it is still controversial. No spectroscopic investigations have been reported on L-Trp, and due to the short life time of the intermediates, ex situ techniques cannot be employed, leading to a never-ending discussion about possible intermediates. In the L-Tyr and L-His cases, spectroelectrochemical studies were performed and different intermediates were observed, suggesting that some intermediates may be observed under specific conditions, as proposed for L-Cys. This amino acid is the most interesting among the electroactive ones because of the presence of a thiol moiety at its side chain, leading to a wide range of oxidation states. It can adsorb onto surfaces of different crystallographic orientation in stereoselective conformation, modifying the surface for different applications.as a surface engineering tool since it plays the role of as an anchor for the growing of nanocrystals inside proteic templates.

Online monitoring of electrocatalytic reactions of alcohols at platinum and gold electrodes in acidic, neutral and alkaline media by capillary electrophoresis with contactless conductivity detection (EC-CE-C4 D).

An EC-CE-C4 D flow system was applied to the investigation of electrocatalytic processes by monitoring carboxylic acids formed during the electro-oxidation at various potentials of primary alcohols (mixture of 1 mmol/L of ethanol, n-propanol, n-butanol and n-pentanol) in acidic, neutral and alkaline media. The electro-oxidation was carried out on gold and platinum disk electrodes (3 mm of diameter) in a thin-layer electrochemical flow cell. Products were sampled 50 µm apart from the electrode directly into the capillary. All the generated carboxylates were determined in near real time (less than 2 min) by CE-C4 D in counter-flow mode, with Tris/HCl buffer solution (pH 8.6) as BGE. Long sequences of 5-min experiments were run automatically, exploring the applied potential, electrolysis time and solution composition. Electro-oxidation at 1.5 V (versus Ag/AgCl quasi-reference) during 50 s in acidic medium was found appropriate for both Pt and Au electrodes when the determination of alcohols after derivatization is intended. A noteworthy selectivity effect was observed on the Au electrode. The signal corresponding to pentanoate is similar on both electrodes while the signal of ethanoate (acetate) is four times larger on gold than on platinum. The carboxylate signals were lower in alkaline medium (below the determination limit on Pt) than in acidic and neutral media. On gold, the formation of carboxylates was anticipated (0.85 V in alkaline medium versus 1.40 V in neutral medium). The automatic online monitoring of electrochemical processes by EC-CE-C4 D holds great potential to investigate ionic/ionizable intermediates/products of new electrocatalysts and/or alternative fuels.

Evaluation of single and stack membraneless enzymatic fuel cells based on ethanol in simulated body fluids.

The purpose of this work is to evaluate single and double-cell membraneless microfluidic fuel cells (MMFCs) that operate in the presence of simulated body fluids SBF, human serum and blood enriched with ethanol as fuels. The study was performed using the alcohol dehydrogenase enzyme immobilised by covalent binding through an array composed of carbon Toray paper as support and a layer of poly(methylene blue)/tetrabutylammonium bromide/Nafion and glutaraldehyde (3D bioanode electrode). The single MMFC was tested in a hybrid microfluidic fuel cell using Pt/C as the cathode. A cell voltage of 1.035V and power density of 3.154mWcm-2 were observed, which is the highest performance reported to date. The stability and durability were tested through chronoamperometry and polarisation/performance curves obtained at different days, which demonstrated a slow decrease in the power density on day 10 (14%) and day 20 (26%). Additionally, the cell was tested for ethanol oxidation in simulated body fluid (SBF) with ionic composition similar to human blood plasma. Those tests resulted in 0.93V of cell voltage and a power density close to 1.237mWcm-2. The double cell MMFC (Stack) was tested using serum and human blood enriched with ethanol. The stack operated with blood in a serial connection showed an excellent cell performance (0.716mWcm-2), demonstrating the feasibility of employing human blood as energy source.

Mechanistic proposal for the electrochemical and sonoelectrochemical oxidation of thiram on a boron-doped diamond anode.

A comparative study was carried out of sonochemical (SCh), electrochemical (ECh) and sonoelectrochemical (SECh) strategies for the degradation of the fungicide thiram in dilute aqueous solution. The SCh and SECh studies were performed using a sonicator equipped with an 11 mm titanium-alloy probe and operated at 20 kHz with a power intensity of 523 W cm(-2). In the ECh and SECh investigations, galvanostatic electrolyses were implemented using a single compartment electrochemical cell with a boron-doped diamond electrode as anode and applied current densities in the range 10-50 mA cm(-2). For these processes, the decrease in concentration of thiram was monitored by high performance liquid chromatographic (HPLC) analysis and values of current efficiency and energy consumption were determined. The results showed that the rate of degradation of thiram and the amount of energy consumed were directly proportional to the applied current density, while current efficiency was inversely related to current density. The kinetics of thiram degradation followed a pseudo first order model with apparent rate constants in the region of 10(-3)min(-1). Thiram in aqueous solution was subjected to "exhaustive" degradation by ECh and SECh processes for 5h at applied current densities of 35 mA cm(-2) and the intermediates/byproducts so-formed were identified by HPLC-mass spectrometry. Mechanisms of the degradation reactions have been proposed on the basis of the results obtained.

Degradation and inactivation of adenovirus in water by photo-electro-oxidation / Degradação e inativação de adenovírus na água por fotoeletrooxidação

The present study analyzed the efficiency of the photo-electro-oxidation process as a method for degradation and inactivation of adenovirus in water. The experimental design employed a solution prepared from sterile water containing 5.107 genomic copies/L (gc/L) of a standard strain of human adenovirus type 5 (HAdV-5) divided into two equal parts, one to serve as control and one treated by photo-electro-oxidation (PEO) for 3 hours and with a 5A current. Samples collected throughout the exposure process were analyzed by real-time polymerase chain reaction (qPCR) for viral genome identification and quantitation. Prior to gene extraction, a parallel DNAse treatment step was carried out to assess the integrity of viral particles. Integrated cell culture (ICC) analyses assessed the viability of infection in a cell culture. The tested process proved effective for viral degradation, with a 7 log10 reduction in viral load after 60 minutes of treatment. The DNAse-treated samples exhibited complete reduction of viral load after a 75 minute exposure to the process, and ICC analyses showed completely non-viable viral particles at 30 minutes of treatment.

Resumo O presente estudo analisou a eficiência do processo de fotoeletrooxidação como metodologia para a degradação e inativação de adenovírus em água. A concepção experimental emprega uma solução preparada a partir de água estéril contendo 5,107 cópias genômicas/L (gc/L) de uma amostra padrão de adenovírus humano tipo 5 (HAdV-5), dividida em duas partes iguais, uma para servir como controle e outra tratada por fotoeletrooxidação (PEO) durante 3 horas e com uma corrente de 5A. As amostras recolhidas durante o processo de exposição foram analisadas por PCR quantitativo em tempo real (qPCR) para identificação e quantificação do genoma viral. Antes da extração de ácidos nucleicos, um passo de tratamento com DNAse paralelo foi realizado para avaliar a integridade das partículas virais. Um ensaio de qPCR integrado à cultura de células (ICC-qPCR) permitiu analisar a viabilidade de infecção em uma cultura de células. O processo mostrou-se eficaz testada para a degradação viral, com uma redução de 7 log10 da carga viral após 60 minutos de tratamento. As amostras tratadas com DNAse exibiram redução completa da carga viral após uma exposição de 75 minutos ao processo, e a análise de ICC-qPCR mostrou partículas virais completamente não-viáveis ​​em 30 minutos de tratamento.

Degradation and inactivation of adenovirus in water by photo-electro-oxidation

The present study analyzed the efficiency of the photo-electro-oxidation process as a method for degradation and inactivation of adenovirus in water. The experimental design employed a solution prepared from sterile water containing 5.107 genomic copies/L (gc/L) of a standard strain of human adenovirus type 5 (HAdV-5) divided into two equal parts, one to serve as control and one treated by photo-electro-oxidation (PEO) for 3 hours and with a 5A current. Samples collected throughout the exposure process were analyzed by real-time polymerase chain reaction (qPCR) for viral genome identification and quantitation. Prior to gene extraction, a parallel DNAse treatment step was carried out to assess the integrity of viral particles. Integrated cell culture (ICC) analyses assessed the viability of infection in a cell culture. The tested process proved effective for viral degradation, with a 7 log10 reduction in viral load after 60 minutes of treatment. The DNAse-treated samples exhibited complete reduction of viral load after a 75 minute exposure to the process, and ICC analyses showed completely non-viable viral particles at 30 minutes of treatment.

Resumo O presente estudo analisou a eficiência do processo de fotoeletrooxidação como metodologia para a degradação e inativação de adenovírus em água. A concepção experimental emprega uma solução preparada a partir de água estéril contendo 5,107 cópias genômicas/L (gc/L) de uma amostra padrão de adenovírus humano tipo 5 (HAdV-5), dividida em duas partes iguais, uma para servir como controle e outra tratada por fotoeletrooxidação (PEO) durante 3 horas e com uma corrente de 5A. As amostras recolhidas durante o processo de exposição foram analisadas por PCR quantitativo em tempo real (qPCR) para identificação e quantificação do genoma viral. Antes da extração de ácidos nucleicos, um passo de tratamento com DNAse paralelo foi realizado para avaliar a integridade das partículas virais. Um ensaio de qPCR integrado à cultura de células (ICC-qPCR) permitiu analisar a viabilidade de infecção em uma cultura de células. O processo mostrou-se eficaz testada para a degradação viral, com uma redução de 7 log10 da carga viral após 60 minutos de tratamento. As amostras tratadas com DNAse exibiram redução completa da carga viral após uma exposição de 75 minutos ao processo, e a análise de ICC-qPCR mostrou partículas virais completamente não-viáveis em 30 minutos de tratamento.

Degradation of 1-hydroxy-2,4-dinitrobenzene from aqueous solutions by electrochemical oxidation: role of anodic material.

Electrochemical oxidation (ECOx) of 1-hydroxy-2,4-dinitrobenzene (or 2,4-dinitrophenol: 2,4-DNP) in aqueous solutions by electrolysis under galvanostatic control was studied at Pb/PbO2, Ti/SnO2, Ti/IrxRuySnO2 and Si/BDD anodes as a function of current density applied. Oxidative degradation of 2,4-DNP has clearly shown that electrode material and the current density applied were important parameters to optimize the oxidation process. It was observed that 2,4-DNP was oxidized at few substrates to CO2 with different results, obtaining good removal efficiencies at Pb/PbO2, Ti/SnO2 and Si/BDD anodes. Trends in degradation way depend on the production of hydroxyl radicals (OH) on these anodic materials, as confirmed in this study. Furthermore, HPLC results suggested that two kinds of intermediates were generated, polyhydroxylated intermediates and carboxylic acids. The formation of these polyhydroxylated intermediates seems to be associated with the denitration step and substitution by OH radicals on aromatic rings, this being the first proposed step in the reaction mechanism. These compounds were successively oxidized, followed by the opening of aromatic rings and the formation of a series of carboxylic acids which were at the end oxidized into CO2 and H2O. On the basis of these information, a reaction scheme was proposed for each type of anode used for 2,4-D oxidation.