David Contreras

Experimental design of Fenton and photo-Fenton reactions for the treatment of ampicillin solutions

This paper discusses the degradation of the antibiotic ampicillin (AMP) by Fenton and photo-Fenton reactions. The influence of the three main variables that govern the degradation kinetic (pH, H(2)O(2) and Fe(II) concentrations) was evaluated with a circumscribed central composite (CCC) model and a response surface methodology (RSM). The optimal conditions for Fenton and photo-Fenton reactions are very similar: pH 3.5, around 400 micromol L(-1) H(2)O(2) and 87 micromol L(-1) Fe(II). Under such optimized conditions, the complete AMP removal was reached after 10 min and 3 min for Fenton and photo-Fenton reactions, respectively. A very similar removal profile in the first 2 min of reaction was observed for both systems with a high degree of degradation (close to 90%). After a 2-min treatment, the Fenton reaction became slower, and the IR product analysis suggests the formation of different oxidation intermediates. This observation was confirmed by the COD and TOC evolution during the reactions. The oxidation degree, measured as Average Oxidation State (AOS), indicates that the photo-Fenton reaction produces faster most of the oxidation intermediates. The antibacterial activity (AA) of the oxidized samples was determined using the inhibition halo methodology on agar plates cultured with Staphylococcus aureus bacteria. The course of AA is concomitant with the AMP removal, which indicates that the long-term intermediates do not present antibiotic properties.

In field arsenic removal from natural water by zero-valent iron assisted by solar radiation

An in situ arsenic removal method applicable to highly contaminated water is presented. The method is based in the use of steel wool, lemon juice and solar radiation. The method was evaluated using water from the Camarones River, Atacama Desert in northern Chile, in which the arsenic concentration ranges between 1000 and 1300 microg L(-1). Response surface method analysis was used to optimize the amount of zero-valent iron (steel wool) and the citrate concentration (lemon juice) to be used. The optimal conditions when using solar radiation to remove arsenic from natural water from the Camarones river are: 1.3 g L(-1) of steel wool and one drop (ca. 0.04 mL) of lemon juice. Under these conditions, removal percentages are higher than 99.5% and the final arsenic concentration is below 10 microg L(-1). This highly effective arsenic removal method is easy to use and inexpensive to implement.

Enhanced hydroxyl radical production by dihydroxybenzene-driven Fenton reactions: implications for wood biodegradation.

Brown rot fungi degrade wood, in initial stages, mainly through hydroxyl radicals (•OH) produced by Fenton reactions. These Fenton reactions can be promoted by dihydroxybenzenes (DHBs), which can chelate and reduce Fe(III), increasing the reactivity for different substrates. This mechanism allows the extensive degradation of carbohydrates and the oxidation of lignin during wood biodegradation by brown rot fungi. To understand the enhanced reactivity in these systems, kinetics experiments were carried out, measuring •OH formation by the spin-trapping technique of electron paramagnetic resonance spectroscopy. As models of the fungal DHBs, 1,2-dihydroxybenzene (catechol), 2,3-dihydroxybenzoic acid and 3,4-dihydroxybenzoic acid were utilized as well as 1,2-dihydroxy-3,5-benzenedisulfonate as a non-Fe(III)-reducing substance for comparison. Higher amounts and maintained concentrations of •OH were observed in the driven Fenton reactions versus the unmodified Fenton process. A linear correlation between the logarithms of complex stability constants and the •OH production was observed, suggesting participation of such complexes in the radical production.

Mecanismo e aplicações da reação de fenton assistida por compostos fenólicos redutores de ferro

The mechanism and applications of the Fenton reaction assisted by iron-reducing phenolic compounds (IRPC) is reviewed. The presence of IRPC leads to the formation of a larger number of free radicals. The relationship between the redox potential and the IRPC structure is discussed. The effect of humic substances in the degradation of xenobiotics is also included, since these substances are able to reduce metallic ions. The natural occurrence of Fe3+/H2O2/IRPC in wood biodegradation processes, as well as their application is also discussed. The review concludes with the advantages of the Fe3+/H2O2/IRPC systems and some considerations for further process optimization and their applications at industrial levels.

Photocatalyzed degradation of flumequine by doped TiO2 and simulated solar light

Titanium dioxide was obtained in its pure form (TiO2) and in the presence of urea (u-TiO2) and thiourea (t-TiO2) using the sol-gel technique. The obtained powders were characterized by BET surface area analysis, Infrared Spectroscopy, Diffuse Reflectance Spectroscopy and the Rietveld refinement of XRD measurements. All the prepared catalysts show high anatase content (>99%). The a and b-cell parameters of anatase increase in the order TiO2<u-TiO2<t-TiO2, while the c-parameter presents the opposite trend. Because of the interplay in cell dimensions, the cell grows thicker and shorter when prepared in the presence of urea and thiourea, respectively. The cell volume decreases in the order t-TiO2>u-TiO2>TiO2. The photocatalytic activities of the samples were determined on flumequine under solar-simulated irradiation. The most active catalysts were u-TiO2 and t-TiO2, reaching values over 90% of flumequine degradation after 15 min irradiation, compared with values of 55% for the pure TiO2 catalyst. Changing simultaneously the catalyst amount (t-TiO2) and pH, multivariate analysis using the response surface methodology was used to determine the roughly optimal conditions for flumequine degradation. The optimized conditions found were pH below 7 and a catalyst amount of 1.6 g L(-1).

FENTON REACTION DRIVEN BY IRON LIGANDS

ABSTRACT One of the most important sources of reactive oxygen species (ROS) in biological systems is the Fenton reaction. In this, the Fe 2+ or Fe 3+ reacts with H 2 O 2 to produce ROS as the hydroxyl radical (∙OH), superoxide radical (O 2∙- ) and singlet oxygen ( 1 O 2 ).The main ROS, responsible for the high oxidizing power of the Fenton reaction, is not clear. Some authors claim that the principal reactive species is ∙OH, while others propose a ferryl specie (Fe 4+ or [FeO] 2+ ) ( 1, 2 ) . Recently, have been proposed that the kind of reaction species produced depends mainly of pH and the iron composition of the coordination sphere. This is highlighted for Fe 3+ , because in mono and (some) bis-complexes Fe is reduced to Fe 2+ and there are some positions occupied by water or hydroxide ligands, readily to be exchanged by H 2 O 2 . On the other hand, in tris-complexes there are not any positions occupied by water or hydroxide, avoiding the formation of peroxo-complexes, necessary for Fenton or Fenton like reaction.The 1,2-dihydroxybenzenes (DHBs) have been described as modulators of Fenton reaction. The DHBs driven Fenton reaction have been used for environmental applications as an advanced oxidation process. Furthermore, these systems participate in different biological process, as the wood biodegradation by fungi and oxidative stress in neurodegenerative diseases.In this review, the effect of 1,2-dihydroxybenzenes on the activated species production by the Fenton and Fenton like reaction will be discussed and its participation in different systems.

The Reactivity and Reaction Pathway of Fenton Reactions Driven by Substituted 1,2-Dihydroxybenzenes

Fenton systems are interesting alternatives to advanced oxidation processes (AOPs) applied in soil or water remediation. 1,2-Dihydroxybenzenes (1,2-DHBs) are able to amplify the reactivity of Fenton systems and have been extensively studied in biological systems and for AOP applications. To develop efficient AOPs based on Fenton systems driven by 1,2-DHBs, the change in reactivity mediated by different 1,2-DHBs must be understood. For this, a systematic study of the reactivity of Fenton-like systems driven by 1,2-DHBs with different substituents at position 4 was performed. The substituent effect was analyzed using the Hammett constant (σ), which has positive values for electron-withdrawing groups (EWGs) and negative values for electron-donating groups (EDGs). The reactivity of each system was determined from the degradation of a recalcitrant azo dye and hydroxyl radical (HO·) production. The relationship between these reactivities and the ability of each 1,2-DHB to reduce Fe(III) was determined. From these results, we propose two pathways for HO· production. The pathway for Fenton-like systems driven by 1,2-DHBs with EDGs depends only on the Fe(III) reduction mediated by 1,2-DHB. In Fenton-like reactions driven by 1,2-DHBs with EWGs, the Fe(III) reduction is not primarily responsible for increasing the HO· production by this system in the early stages.

Reactivity of catecholamine-driven Fenton reaction and its relationships with iron(III) speciation

Abstract Introduction: Fenton reaction is the main source of free radicals in biological systems. The reactivity of this reaction can be modified by several factors, among these iron ligands are important. Catecholamine (dopamine, epinephrine, and norepinephrine) are able to form Fe(III) complexes whose extension in the coordination number depends upon the pH. Fe(III)-catecholamine complexes have been related with the development of several pathologies. Methods: In this work, the ability of catecholamines to enhance the oxidative degradation of an organic substrate (veratryl alcohol, VA) through Fenton and Fenton-like reactions was studied. The initial VA degradation rate at different pH values and its relationship to the different iron species present in solution were determined. Furthermore, the oxidative degradation of VA after 24 hours of reaction and its main oxidation products were also determined. Results: The catecholamine-driven Fenton and Fenton-like systems showed higher VA degradation compared to unmodified Fenton or Fenton-like systems, which also showed an increase in the oxidation state of the VA degradation product. All of this oxidative degradation takes place at pH values lower than 5.50, where the primarily responsible species would be the Fe(III) mono-complex. Conclusion: The presence of Fe(III) mono-complex is essential in the ability of catecholamines to increase the oxidative capacity of Fenton systems.

Oxidative degradation of sulfathiazole by Fenton and photo-Fenton reactions

This article presents experimental results on 47 μmol L−1 sulfathiazole (STZ) degradation by Fenton and photo-Fenton reactions using multivariate analysis. The optimal experimental conditions for reactions were obtained by Response Surface Methodology (RSM). In the case of the Fenton reactions there were 192 μmol L−1 ferrous ions (Fe(II)) and 1856 μmol L−1 hydrogen peroxide (H2O2), as compared with 157 μmol L−1 (Fe(II)) and 1219 μmol L−1 (H2O2) for photo-Fenton reactions. Under these conditions, around 90% of STZ degradation were achieved after 8 minutes treatment by Fenton and photo-Fenton reactions, respectively. Moreover, a marked difference was observed in the total organic carbon (TOC) removal after 60-min treatment, achieving 30% and 75% for the Fenton and photo-Fenton reactions, respectively. Acetic, maleic, succinic and oxamic acids could be identified as main Fenton oxidation intermediates. A similar pattern was found in the case of photo-Fenton reaction, including the presence of oxalic acid and ammonia at short periods of irradiation with UV-A. The calculated values of Average Oxidation State (AOS) corroborate the formation of oxidized products from the initial steps of the reaction.

SUPERVISED PATTERN RECOGNITION TECHNIQUES FOR CLASSIFICATION OF EUCALYPTUS SPECIES FROM LEAVES NIR SPECTRA

Three supervised pattern recognition methods (SPRM) were evaluated to discriminate between Eucalyptus globulus and Eucalyptus nitens species applying near infrared (NIR) spectroscopy on leaves. The methods used were k-nearest neighbor (KNN), soft modeling class analogy (SIMCA) and discriminant partial least squares (PLS-DA). First and second derivatives were used as transform techniques and mean-center (MC) and autoscaling (AS) as preprocessing techniques. The training set was constitued by 288 samples and 20 samples were used as validation set. A significant difference between the assayed methods was not observed, however best results for separation of classes and prediction rate were obtained when first derivative and MC were used for all the recognition pattern methods. Use of leaves and NIR spectroscopy avoids the destructive usual wood analysis in forest industries and facilities the fast classification of these species for forest applications.