Role of Nb2O5 Crystal Phases on the Photocatalytic Conversion of Lignin Model Molecules and Selectivity for Value-Added Products.

The photocatalytic conversion in aqueous media of phenol and guaiacol as a lignin model compound using Nb2O5 with different crystal phases was studied. Nb2O5 particles were synthesized using hydrothermal methods, where it was observed that changes in the solvent control their morphology and crystal phase. Different photocatalytic behavior of Nb2O5 was observed with the selected model compounds, indicating that its selection directly impacts the resulting conversion and selectivity rates as well as the reaction pathway, highlighting the relevance of model molecule selection. Photocatalytic conversion of phenol showed conversion rate (C%) up to 25 % after 2 h irradiation and high selectivity (S%) to pyrogallol (up to 50 %). Orthorhombic Nb2O5 spheres favored conversion through free hydroxyl radicals while monoclinic rods did not convert phenol. Guaiacol photocatalytic oxidation showed high conversion rate but lower selectivity. Orthorhombic and monoclinic Nb2O5 favored the formation of resorcinol with S % ~0.43 % (C % ~33 %) and ~13 % (C % ~27 %) respectively. The mixture of both phases enhanced the guaiacol conversion rate to ~55 % with ~17 % of selectivity to salicylaldehyde. The use of radical scavengers provided information to elucidate the reaction pathway for these model compounds, showing that different reaction pathways may be obtained for the same photocatalyst if the model compound is changed.

Enhanced catalytic reduction of emerging contaminant by using magnetic CuFe2O4@MIL-100(Fe) in Fenton-based electrochemical processes.

Fenton-based electrochemical processes (FEPs) using newly engineered 3D photocatalyst nanocomposites have garnered significant attention owing to their ability to remove emerging contaminants. Despite the development of numerous materials, there is still a need to enhance their efficiency, stability, and recyclability to address the limitations of FEPs. This study seeks to address this issue by investigating sustainable methods to engineer novel 3D core-shell photocatalyst composites for application in FEPs. These materials can update the photo-assisted FEPs activity, and magnetism can be helpful for the easy recyclability of the catalyst. Herein, we successfully synthesized a magnetic and photoactive CuFe2O4@MIL-100(Fe) (CM) composite through sustainable methods and assessed its morphological structure and physicochemical and photocatalytic properties. The catalytic performance of CM was investigated in an undivided RuO2/air-diffusion cell to treat Cefadroxil. The results show that heterogeneous photoelectro-Fenton (HPEF) (100% in 120 min) has higher degradation efficiency than electro-Fenton (100% in 210 min) and electrooxidation (73.3% in 300 min) processes. The superior degradation efficiency of HPEF is attributed to the formation of a large amount of hydroxyl radicals indicating the excellent photocatalytic activity of the material due to the direct excitation of the Fe-O cluster, which boosts the redox reaction of Fe2+/Fe3+. Key operational parameters such as pH, catalyst concentration, current density, and CuFe2O4 proportion on MIL-100(Fe) in the composite were optimized in the HPEF process. The optimized composite exhibited good stability and easy recyclability, allowing high removal efficiency, which can be kept up after five cycles of 90 min. High degradation performance was observed using natural sunlight radiations. Additionally, possible catalytic degradation mechanisms in HPEFs were proposed based on radical quenching experiments. This study has significant potential to contribute to the development of more sustainable and effective water treatment strategies.

Degradation of contaminants of emerging concern in a secondary effluent using synthesized MOF-derived photoanodes: A comparative study between photo-, electro- and photoelectrocatalysis.

Three metal-organic framework (MOF)-based photoanodes were prepared by deposition on TiO2 nanotubes using Ti as substrate (Ti/TiO2NT): i) Ti/TiO2NT-Au@ZIF-8, ii) Ti/TiO2NT-Ru3(BTC)2, iii) Ti/TiO2NT-UiO-66(Zr)NH2. These photoanodes were characterized by FEG-SEM, EDX and DRX. The analyses showed a successful modification and a high homogeneity of the different MOFs on the Ti/TiO2NT surface. The photoanodes were studied in the degradation of Contaminants of Emerging Concern (CECs) in a spiked secondary effluent from a Municipal Wastewater Treatment Plant (MWWTP). Sodium diclofenac (DCF), sulfamethazine (SMT) and carbamazepine (CBZ) were used as CECs at low concentration (200 µg/L each CEC). The samples were preconcentrated using Solid Phase Extraction (SPE) and analyzed by a HPLC-DAD system. The MOF-based photoanodes exhibited a high photoelectrochemical (PEC) activity towards the oxidation of CECs, achieving up to 50%, 70% and 80% of removal using Ti/TiO2NT-Au@ZIF-8, Ti/TiO2NT-UiO-66(Zr)NH2, Ti/TiO2NT-Ru3(BTC), respectively. The influence of the generation of hydroxyl radical was then studied. The results indicate that PEC degradation using Ti/TiO2NT-Ru3(BTC)2 and Ti/TiO2NT-UiO-66(Zr)NH2 is more affected by the concentration of the radical.

Modification of a Brazilian natural clay and catalytic activity in heterogeneous photo-Fenton process.

The catalytic activity of a Brazilian natural clay modified with the immobilization of iron oxide was applied in the heterogeneous Fenton process for the degradation of the antibiotic sulfathiazole (STZ). The clay without any treatment indicated a lamellar type material with mesoporous distribution that presents a heterogeneous mixture of phases (type 1:1 and 2:1 structures), with a predominance of quartz, montmorillonite, gibbsite and kaolinite, and with SiO2, Al2O3, Fe2O3, K2O, TiO2, MgO as major oxides. Its high absorption in the UV-Vis ranges with a bandgap energy of 1.9 eV was attributed to the presence of hematite. It was observed that the effects of the addition of starch before heat treatment, and impregnation with iron, modified the clay surface. F rom the X-ray photoelectron spectroscopy analysis it was concluded that a structural reorganization is related to the conversion of the various iron oxide phases into hematite, as well as promoting an increase in Fe2+/ Fe3+ redox reactions allowing rapid degradation of STZ. The catalyst impregnated with iron and treated at 600 °C showed to be an economical and versatile catalyst with high catalytic efficiency (>97% STZ degradation after 60 min), with small differences according to the type of LED device used. Furthermore, it presented high stability and reusability reaching 93% degradation of STZ after four cycles of reuse with low consumption of H2O2.

Gallic acid influence on azo dyes oxidation by Fenton processes.

The present work consisted in evaluating the effect of a natural plant reducer, gallic acid (GA), on the discolouration/oxidation of two azo dyes by Fenton processes (Fe3+/H2O2 and Fe2+/H2O2). A kinetic study was performed to better interpret the discolouration data at different temperatures. The 1st-order kinetic model presented the best fit for the experimental data of methyl orange discolouration, while the 2nd-order was better for chromotrope 2R. Due to the addition of GA and the temperature rise, there were increases in discolouration and in the reaction rate constant values. As a highlight, it was possible to verify the reduction of the apparent activation energy (Ea) due to the presence of GA. For example, Ea for discolouring methyl orange corresponded to 81.5 and 53.6 kJ.mol-1 by Fe2+/H2O2 and Fe2+/H2O2/GA, respectively. Thus, it can be inferred that the GA reduces the energy barrier to increase the oxidation of dyes by Fenton processes.

Effect of cysteine using Fenton processes on decolorizing different dyes: a kinetic study.

Amino acid cysteine has been used as reducing mediator with the aim of improving dye degradation by homogeneous Fenton processes (Fe2+/H2O2 and Fe3+/H2O2). Through its known Fe3+-reducing activity, this amino acid can enhance the production of reactive oxygen species as HO• (hydroxyl radical) and its pro-oxidant properties have been verified while decolorizing diverse dyes in the present work. Its presence enhanced decolorization of Methyl Orange, Phenol Red, Safranin T, Rhodamine B, Reactive Black 5 and Reactive Yellow 2, mainly in reactions initially containing Fe3+ as a catalyst (Fe3+-reactions). E.g. Fe3+/H2O2 and Fe3+/H2O2/cysteine systems decolorized 27% and 44% of Phenol Red after 60 min, respectively. A kinetic modeling analysis has revealed that 1st-order and mainly 2nd-order kinetic models were well fitted to both Fe2+- and Fe3+-reactions data. Improvements in reaction rate constants have been observed by adding cysteine. In experiments performed at varied temperatures, it was found a decrease in activation energy (Ea) due to cysteine addition while decolorizing Safranin T: Ea decreased from 104.6 to 88.9 kJ mol-1 for Fe3+-reactions and from 81.0 to 52.2 kJ mol-1 for Fe2+-reactions. Therefore, it was found that cysteine decreases the energy barrier so as to improve Fenton-based decolorization reactions.

Aplicação de carepa de aço para degradação de 2,4-dinitrofenol por meio de sistema de oxidação avançada do tipo Fenton / Application of steel waste for 2.4-dinitrophenol degradation through Fenton type advanced oxidation system

RESUMO Considerado um poluente prioritário de reconhecida toxicidade e recalcitrância, o 2,4-dinitrofenol (2,4-DNF) presente em águas residuárias dificulta tratamentos convencionais, especialmente os de princípio biológico, como lagoas aeradas e sistema de lodos ativados. Em função de sua potencialidade de transformar a estrutura de poluentes em elementos de capacidade poluidora reduzida, os processos oxidativos avançados (POAs) representam atualmente uma alternativa para o tratamento de efluentes contaminados com compostos dessa natureza. A presente pesquisa teve como objetivo realizar estudos de degradação de 2,4-DNF em solução aquosa por meio de processos de oxidação avançada do tipo Fenton utilizando uma fonte não convencional de ferro na forma de um resíduo siderúrgico (carepa de aço). A condução de um delineamento experimental fundamentado em planejamento fatorial de experimentos revelou que as variáveis quantidade de peróxido de hidrogênio e de carepa influenciaram significativamente a degradação de 2,4-DNF, proporcionando, em condições otimizadas (20 g de carepa, 0,5 mL de H2O2 em pH 3), elevada eficiência na degradação tanto do composto modelo quanto de seus intermediários reacionais, tendo reduzido também a toxicidade aguda medida na forma de inibição de crescimento de E. coli. Ensaios adicionais sugeriram que os mecanismos reacionais pelos quais ocorre a degradação do 2,4-DNF são mediados tanto pela superfície das partículas de carepa quanto pelo ferro lixiviado, caracterizando o processo como uma combinação de oxidação homogênea e heterogênea. Finalmente, ensaios de reusabilidade e operação em reator de fluxo contínuo sugeriram significativa potencialidade do sistema carepa/H2O2.

ABSTRACT Considered a priority pollutant of recognized toxicity and recalcitrance, 2.4-dinitrophenol (2.4-DNP) present in wastewater hinders conventional treatments such as filtration, chemical coagulation, activated sludge system and activated carbon adsorption. Due to the potential of advanced oxidation processes (AOP) to transform the structure of pollutants into elements of reduced pollutant capacity, they presently represent an alternative for the treatment of effluents contaminated with these compounds. The present research aimed to study the degradation of 2.4-DNP in aqueous solution through advanced Fenton-type oxidation processes, using an unconventional source of iron in the form of a steel residue (steel waste). The conduction of an experimental design based on the factorial planning of experiments revealed that the variables hydrogen peroxide quantity and scale significantly influenced 2.4-DNF degradation, providing, under optimized conditions (20 g of steel waste, 0.5 mL of H2O2 at pH 3) high degradation efficiency of both the model compound and its reaction intermediates, as well as reducing acute toxicity, measured as E. coli growth inhibition. Further trials have suggested that the reaction mechanisms by which 2.4-DNF degradation occurs are mediated by both the surface of steel waste particles and the leached iron, characterizing the process as a combination of homogeneous and heterogeneous oxidation. Finally, reusability and continuous flow reactor operation tests suggested the significant potential of the steel waste/ H2O2 system.

On the performance of distinct electrochemical and solar-based advanced oxidation processes to mineralize the insecticide imidacloprid.

Water contamination by contaminants of emerging concern is one of the main challenges to be solved by our desired sustainable society. In the same time, different technologies for water treatment are becoming enough mature to be implemented. In this work, two different advanced oxidation processes (AOP) were investigated: i) electrochemical processes (electrochemical, photoassisted electrochemical, electro Fered-Fenton, and photo-electro Fered-Fenton - PEF-Fered) using a BDD and DSA® electrodes under UVA and UVC irradiation (9 W) and ii) solar-based AOP using four distinct oxidants (HOCl, H2O2, S2O82-, HSO5-) in the presence or absence of Fe2+ ions to oxidize and mineralize imidacloprid (IMD: 50 mg L-1) containing solutions. The PEF-Fered (1.0 mM Fe2+ and 50 mg L-1 h-1 H2O2) under UVA or UVC irradiation and HOCl/UVC (NaCl 17 mM) processes using a BDD and DSA® electrodes (10 mA cm -2), respectively, performed equally well to completely oxidize and mineralize (∼90%) IMD at the expense of only ∼0.3 kWh g-1. Low amounts and highly oxidized byproducts identified through liquid chromatography tandem mass spectrometry were observed for the HOCl/UVC process using a DSA® electrode. Concerning the solar-based AOP, all assessed oxidants (4 mM h-1) successfully oxidized IMD within 3 h of treatment, whereas only H2O2 and HOCl led to significant (∼60%) TOC abatement after 6 h treatment. The use of Fe2+ (0.5 or 1.0 mM) had no significant improvement in the oxidation and mineralization of IMD.

Simultaneous degradation of 30 pharmaceuticals by anodic oxidation: Main intermediaries and by-products.

The anodic oxidation (AO) of 30 pharmaceuticals including antibiotics, hormones, antihistaminics, anti-inflammatories, antidepressants, antihypertensives, and antiulcer agents, in solutions containing different supporting electrolytes media (0.05 M Na2SO4, 0.05 M NaCl, and 0.05 M Na2SO4 + 0.05 M NaCl) at natural pH was studied. A boron-doped diamond (BDD) electrode and a stainless-steel electrode were used as anode and cathode, respectively, and three current densities of 6, 20, and 40 mA cm-2 were applied. The results showed high mineralization rates, above 85%, in all the tested electrolytic media. 25 intermediaries produced during the electrooxidation were identified, depending on the supporting electrolyte together with the formation of carboxylic acids, NO3-, SO42- and NH4+ ions. The formation of intermediates in chloride medium produced an increase in absorbance. Finally, a real secondary effluent spiked with the 30 pharmaceuticals was treated by AO applying 6 mA cm-2 at natural pH and without addition of supporting electrolyte, reaching c.a. 90% mineralization after 300 min, with an energy consumption of 18.95 kW h m-3 equivalent to 2.90 USD m-3. A degradation scheme for the mixture of emerging contaminants in both electrolytic media is proposed. Thus, the application of anodic oxidation generates a high concentration of hydroxyl radicals that favors the mineralization of the pharmaceuticals present in the spiked secondary effluent sample.

Elimination of pharmaceutical pollutants by solar photoelectro-Fenton process in a pilot plant.

In this study, the simultaneous degradation of antibiotics (ampicillin, sulfamethazine, and tetracycline; and non-steroidal anti-inflammatories (diclofenac and salicylic acid)) including the total organic carbon abatement by solar photoelectro-Fenton process was assessed. Eight liters of solution containing the mixture of the five pharmaceuticals in 1 mmol L-1 Fe2+, 0.05 mol L-1 Na2SO4 at pH 3 and 35 °C were electrolyzed applying different current densities (j = 10, 25, and 50 mA cm-2) in a solar-electrochemical pilot plant. The pilot plant was equipped with an electrochemical filter press cell with a dimensionally stable anode (DSA type) and an air-diffusion cathode coupled to a solar photoreactor exposed directly to sunlight radiation. All pharmaceuticals were degraded during the first 10 min. A TOC removal efficiency of 99.2% after 100 min of treatment with an energy consumption of 534.23 kW h (kgTOC)-1 and 7.15 kW h m-3 was achieved. The pharmaceutical concentration decay followed a pseudo-first-order kinetics. The specific energy per unit of mass of ampicillin, diclofenac, salicylic acid, sulfamethazine, and tetracycline was obtained at 11.73, 19.56, 35.2, 11.73, and 39.32 kW h (kgPD)-1 for ampicillin, diclofenac, salicylic acid, sulfamethazine, and tetracycline, respectively. With our results, we demonstrated that SPEF is an emerging technology for the treatment of this type of pollutants in short time.

Influence of ruthenium doping on UV- and visible-light photoelectrocatalytic color removal from dye solutions using a TiO2 nanotube array photoanode.

The photocatalytic activity of TiO2 anodes was enhanced by synthesizing Ru-doped Ti|TiO2 nanotube arrays. Such photoanodes were fabricated via Ti anodization followed by Ru impregnation and annealing. The X-ray diffractograms revealed that anatase was the main TiO2 phase, while rutile was slightly present in all samples. Scanning electron microscopy evidenced a uniform morphology in all samples, with nanotube diameter ranging from 60 to 120 nm. The bias potential for the photoelectrochemical (PEC) treatment was selected from the electrochemical characterization of each electrode, made via linear sweep voltammetry. All the Ru-doped TiO2 nanotube array photoanodes showed a peak photocurrent (PP) and a saturation photocurrent (SP) upon their illumination with UV or visible light. In contrast, the undoped TiO2 nanotubes only showed the SP, which was higher than that reached with the Ru-doped photoanodes using UV light. An exception was the Ru(0.15 wt%)-doped TiO2, whose SP was comparable under visible light. Using that anode, the activity enhancement during the PEC treatment of a Terasil Blue dye solution at Ebias(PP) was much higher than that attained at Ebias(SP). The percentage of color removal at 120 min with the Ru(0.15 wt%)-doped TiO2 was 98% and 55% in PEC with UV and visible light, respectively, being much greater than 82% and 28% achieved in photocatalysis. The moderate visible-light photoactivity of the Ru-doped TiO2 nanotube arrays suggests their convenience to work under solar PEC conditions, aiming at using a large portion of the solar spectrum.

Nafcillin degradation by heterogeneous electro-Fenton process using Fe, Cu and Fe/Cu nanoparticles.

Heterogeneous electro-Fenton (HEF) is as an alternative to the conventional electro-Fenton (EF) process. HEF uses a solid phase catalyst, whereas EF employs a solubilized one. This implies that in HEF, material can be recovered through a simple separation process such as filtration or magnetic separation in HEF. HEF also has the advantage of not requires a previous pH adjustment, which facilitates working in a higher pH range. In this work, Fe, Cu and Fe/Cu bimetallic nanoparticles (Fe/Cu NPs) were synthesized, characterized and used for the degradation of Nafcillin (NAF). The effect of the adsorption and the anodic oxidation (AO-H2O2) process was tested to assess their influence on HEF. NAF adsorption did not exceed 24% of antibiotic removal and the AO-H2O2 process eliminated the total NAF after 240 min of electrolysis. Through the HEF process, the antibiotic was completely removed using Fe/Cu NPs after 7.0 min of electrolysis, while these NPs, mineralization reached 41% after 240 min. In this case, NAF degradation occurs mainly due to the generation of hydroxyl radicals in the BDD electrode, and the Fenton reaction with Fe and Cu NPs. The main organic intermediates produced during the degradation of NAF by HEF were identified allowing the proposal of degradation pathway. Finally, the antibiotic was also completely eliminated from a wastewater from slaughterhouse after 15 min of treatment by HEF and using Fe/Cu bimetallic NPs.

Physical-Chemical Study of Anthracene Selective Oxidation by a Fe(III)-Phenylporhyrin Derivative.

In this work, we studied the anthracene oxidation by hydroxyl radicals. Hydroxyl radical was generated by reaction of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin Fe (III) (TPPFe) with hydrogen peroxide under visible radiation at a nitrogen atmosphere. The TPPFe was synthesized by Adler Method followed by metal complexation with Fe (III) chloride hexahydrate. Hydroxyl radical was detected by fluorescence emission spectroscopy and we studied kinetic of anthracene selective oxidation by hydroxyl radicals through the differential method. The TPPFe was characterized by UV-Vis spectrophotometry, Dynamic Light Scattering (DLS) and Scanning Electron Microscopy (SEM) measurements. The results indicated that TPPFE was compound by micro-particles with a size distribution of around 2500 nm. Kinetic results showed that the apparent rate constant for the oxidation of anthracene increased exponentially on as temperature increases, furthermore, the activation energy for the Anthracene oxidation by hydroxyl radicals under visible irradiation was 51.3 kJ/mol. Finally, anthraquinone was the main byproduct generated after oxidation of anthracene by TPP-Fe under visible irradiation.

The use of nanovermiculite catalyst in the study of removal of the organic load and degradation of atrazine via ozone process in RPB reactor.

The main objective of this study is the degradation of a synthetic solution of atrazine by a modified vermiculite catalyzed ozonation, in a rotating packed bed (RPB) reactor. A 0.5 L RPB reactor was used to perform the experiments, using a Central Composite Design (CCD) response surface to construct the quadratic model based on the factors: pH, catalyst concentration and reactor rotation frequency. The response variable was the removal of the organic load measured in terms of Chemical Oxygen Demand (COD). After the complete quadratic model was constructed through the response surface, the COD degradation process had an optimal removal of 41% under the following conditions: pH 8.0, rotation of 1150 rpm and catalyst concentration 0.66 g L-1.

First Report on Evaluation of Basic Nutritional and Antioxidant Properties of Moringa Oleifera Lam. from Caribbean Island of Saint Lucia.

Moringa oleifera Lam. has been considered as a multipurpose tree. The studies on it focus on its variable nutritional benefits. It is growing in many regions, but information about nutritional properties of those growing in the Caribbean is missing. The present study focused on biochemical analysis of main nutritional and antioxidant properties in plant material-dried leaves and seeds-of Moringa oleifera. The composition of lipids, proteins, and vitamin E was evaluated in powdered dried leaves and seeds. Fatty acids were evaluated in oil extracted from the moringa seeds. Potential antioxidant properties of the moringa were evaluated in extract from crushed and powdered leaves, as well as from the powdered seeds. The total amounts of lipids, proteins, and vitamin E were higher in powdered seeds (31.85%, 35.13%, and 220.61 mg/kg) than in powdered leaves (12.48%, 20.54%, and 178.10 mg/kg). The main compound of fatty acids presented oleic acid (76.78%) in seeds' oil and oleic (25.01%), palmitic (24.84%), and linolenic (24.71%) acids in leaves. Neohesperidin (126.8 mg/kg), followed by chlorogenic acid (99.96 mg/kg) and quercetin (43.44 and 21.44 mg/kg) were main phenolic compounds identified. Total phenols in powdered leaves' extract (635.6 mg GAE/L) was higher than in powdered seeds' extract (229.5 mg GAE/L). The activity against superoxide radical and hydroxyl radical was 92.4% and 73.1% by leaves' powder extract and 83.6% and 60.7% by crushed-leaf extract; seed-powder extract exhibited a pro-oxidation activity (-68.4%) against superoxide radical and the lowest antioxidant effect against the hydroxyl radical (55.0%).

Apple Phenolic Extracts Strongly Inhibit α-Glucosidase Activity.

The beneficial health effects of apple consumption are well known, however, little is known about the potential of its phenolic fractions to inhibit α-glucosidases and thereafter to treat diseases related to the carbohydrate metabolism, such as postprandial hyperglycemia and diabetes. In the present study, the α-glucosidase inhibition and antioxidant activity of different phenolic fractions of apple were evaluated using the 2,2-diphenyl-1-picrylhydrazyl and hydroxyl radical scavenging activity. Moreover, the phenolic fractions were chemically characterized by LC-MS in order to identify the compounds responsible for the biological properties. The purified extract (not fractionated) had the highest α-glucosidase and hydroxyl radical inhibitions. The purified extract and fractions III and IV were more active against the enzyme activity than the positive control acarbose, the drug used by diabetic patients to treat postprandial hyperglycaemia. Our results show that apple phenolic extracts strongly inhibit α-glucosidase acitivity, validating their potential to be used in the management of type 2 diabetes.

Enzymatic preparation of fructooligosaccharides-rich burdock syrup with enhanced antioxidative properties

Background: Burdock (Arctium lappa L.) is a fructan-rich plant with prebiotic potential. The aim of this study was to develop an efficient enzymatic route to prepare fructooligosaccharides (FOS)-rich and highly antioxidative syrup using burdock root as a raw material. Results: Endo-inulinase significantly improved the yield of FOS 2.4-fold while tannase pretreatment further increased the yield of FOS 2.8-fold. Other enzymes, including endo-polygalacturonase, endo-glucanase and endo-xylanase, were able to increase the yield of total soluble sugar by 11.1% (w/w). By this process, a new enzymatic process for burdock syrup was developed and the yield of burdock syrup increased by 25% (w/w), whereas with FOS, total soluble sugars, total soluble protein and total soluble polyphenols were enhanced to 28.8%, 53.3%, 8.9% and 3.3% (w/w), respectively. Additionally, the scavenging abilities of DPPH and hydroxyl radicals, and total antioxidant capacity of the syrup were increased by 23.7%, 51.8% and 35.4%, respectively. Conclusions: Our results could be applied to the development of efficient extraction of valuable products from agricultural materials using enzyme-mediated methods.

Physicochemical changes of myofibrillar proteins of squid (Argentinus ilex) induced by hydroxyl radical generating system.

The effect of a hydroxyl radical generating system (HRGS), which contained FeCl3, sodium ascorbate, and different concentrations of H2O2, on the physiochemical properties of myofibrillar protein (MP) from squid mantles, has been investigated. The effect of different exposure times to HRGS was also considered. Compared to non-oxidized MP, a significant (p < 0.05) increase in carbonyl content (more than 50% of its original content) and protein solubility, as well as in surface hydrophobicity, was observed in the oxidative MP. With different treatment times, a sharp decrease (p < 0.05) in sulfhydryl content was detected. In addition, hydroxyl radical treatment significantly reduced the MP gel's texture properties, whiteness and water holding capacity, especially at higher concentrations of H2O2. This observation could be attributed to extensive disorderly and less compact structure of MP gels. The results demonstrate the negative effect of HRGS on the structural and functional properties of MP from squid mantles.

Towards understanding of heterogeneous Fenton reaction using carbon-Fe catalysts coupled to in-situ H2O2 electro-generation as clean technology for wastewater treatment.

Iron-supported catalyst on granular activated carbon was prepared for its use in heterogeneous Fenton reaction coupled to an in situ H2O2 electro-generation. For this process, an electrolysis cell was employed, using carbon felt as cathode and graphite as anode. A solution of H2O2 (electrogenerated at a rate of 30 mg L-1 h-1) was obtained using a current intensity of 12 mA. In order to promote the decomposition of H2O2 to OH, a Carbon-Fe catalyst was used. This catalyst was prepared by incipient wet impregnation using FeSO4 as precursor salt to obtain samples with 9% wt of iron. Samples were characterized by EDX, FTIR and XPS spectroscopy before and after wastewater treatment using phenol as model molecule. Two iron oxidation states on the samples were found, Fe2+ and Fe3+. The ratio between Fe2+/Fe3+ was 1.29 which was later reduced to 0.92 after Fenton process; this might be associated with the metal oxidation (Fe2+ to Fe+3) occurring during Fenton-reaction, thus indicating that H2O2 decomposition was carried out by Fe2+ on carbon surface. Detection and quantification of hydroxyl radical were carried out by fluorescence spectroscopy, obtaining a radical concentration of 3.5 µM in solution. Iron in solution were determined, showing a concentration of 0.1 mg L-1, making evident that the supported metal is stable and the reaction is carried out in a heterogeneous phase. Results showed an environmentally friendly process that can generate reagents in situ, with high efficiencies in the degradation of pollutants and minimizing the formation of toxic byproducts, which are common in conventional treatments.

Influence of electrolysis conditions on the treatment of herbicide bentazon using artificial UVA radiation and sunlight. Identification of oxidation products.

The main objective of this work is to demonstrate the viability of solar photoelectro-Fenton (SPEF) process to degrade pesticides in urban wastewater matrix, selecting the herbicide bentazon as a model molecule. In order to provide a correct assessment of the role of the different oxidants and catalysts involved, bentazon was comparatively treated by anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF) and UVA-assisted EF (i.e., PEF) processes as well, either in sulfate or chloride media. Trials were made in a stirred tank reactor with an air-diffusion cathode and a boron-doped diamond (BDD), RuO2-based or Pt anode. In chlorinated matrices, the herbicide disappeared more rapidly using a RuO2-based anode because of the generated active chlorine. The best mineralization performance was always obtained using BDD due to its higher oxidation power, which allowed the complete destruction of refractory chloroderivatives. A concentration of 0.50 mM Fe2+ was found optimal to catalyze Fenton's reaction, largely enhancing the mineralization process under the action of OH. Among photo-assisted treatments, sunlight was proven superior to a UVA lamp to promote the photolysis of intermediates, owing to its greater UV irradiance and contribution of visible photons, although PEF also allowed achieving a large mineralization. In all cases, bentazon decay obeyed a pseudo-first-order kinetics. SPEF treatment in urban wastewater using BDD at only 16.6 mA cm-2 yielded 63.2% mineralization. A thorough, original reaction pathway for bentazon degradation is proposed, including seven non-chlorinated aromatics, sixteen chloroaromatics and two chloroaliphatics identified by GC-MS, most of them not previously reported in literature. Ion-exclusion HPLC allowed the detection of seven short-chain linear carboxylic acids.