Treatment of single and mixed pesticide formulations by solar photoelectro-Fenton using a flow plant

Solutions of single real formulations of herbicides tebuthiuron and ametryn have been degraded by anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF) and solar photoelectro-Fenton (SPEF). The assays were made in a flow plant of 2.5 L equipped with a boron-doped diamond (BDD)/air-diffusion cell and a solar planar photoreactor. Main oxidants were hydroxyl radicals formed from water discharge at the BDD anode and in the bulk from Fenton's reaction between added Fe2+ and cathodically generated H2O2. Partial mineralization was achieved for all the treatments, with the relative oxidation ability growing in the sequence: AO-H2O2 < EF < SPEF. The superiority of SPEF over EF was related to the contribution of photo-oxidation of intermediates and/or their Fe(III) complexes upon sunlight irradiation. No short-linear carboxylic acids were identified, whereas heteroatoms were mainly released as NO3- and SO42- ions. For herbicide contents < 0.18 mM in EF and SPEF, a very rapid pseudo-first-order decay kinetics was related to the oxidation of the Fe(II) complexes of each herbicide at short time, whereupon a much slower pseudo-first-order kinetics associated with the decay of their Fe(III) complexes was observed. Ametryn disappeared more quickly than tebuthiuron, but its solutions were more poorly mineralized. The effect of j and substrate concentration on the performance of SPEF was examined. Mixtures of both formulations were efficiently treated by SPEF, showing similar but slower decays than single solutions. Four primary heteroaromatic products were detected by GC-MS upon prolonged electrolysis of an equimolar mixture. Our results indicate that SPEF is viable for the treatment of water contaminated with tebuthiuron and ametryn herbicides, either single or mixed

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

Antituberculosis drug isoniazid degraded by electro-Fenton and photoelectro-Fenton processes using a boron-doped diamond anode and a carbon-PTFE air-diffusion cathode

Solutions with 0.65 mM of the antituberculosis drug isoniazid (INH) in 0.050 M Na2SO4 at pH 3.0 were treated by electro-Fenton (EF) and UVA photoelectro-Fenton (PEF) processes using a cell with a BDD anode and a carbon-PTFE air-diffusion cathode. The influence of current density on degradation, mineralization rate, and current efficiency has been thoroughly evaluated in EF. The effect of the metallic catalyst (Fe2+ or Fe3+) and the formation of products like short-chain linear aliphatic carboxylic acids were assessed in PEF. Two consecutive pseudo-first-order kinetic regions were found using Fe2+ as catalyst. In the first region, at short time, the drug was rapidly oxidized by ●OH, whereas in the second region, at longer time, a resulting Fe(III)-INH complex was much more slowly removed by oxidants. INH disappeared completely at 300 min by EF, attaining 88 and 94% mineralization at 66.6 and 100 mA cm-2, respectively. Isonicotinamide and its hydroxylated derivative were identified as aromatic products of INH by GC-MS and oxalic, oxamic, and formic acids were quantified by ion-exclusion HPLC. The PEF treatment of a real wastewater polluted with the drug led to slower INH and TOC abatements because of the parallel destruction of its natural organic matter content

Ensuring the overall combustion of herbicide metribuzin by electrochemical advanced oxidation processes. Study of operation variables, kinetics and degradation routes

This article reports the electrochemical degradation of the herbicide metribuzin (MTZ) in sulfate medium by advanced oxidation processes like anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF) and UVA photoelectro-Fenton (PEF). A boron-doped diamond (BDD) anode was combined with an air-diffusion cathode with ability to produce H2O2. Unprecedented overall combustion was feasible by all methods at a constant current density (j) ≥100.0 mA cm−2. The total organic carbon (TOC) removal achieved by AO-H2O2 was independent from pH within the range 3.0-9.0, whereas the oscillatory dependence of the pseudo-first-order MTZ decay rate constant with this variable was ascribed to adsorption on the BDD surface. In EF and PEF at pH 3.0, 0.50 mM Fe2+ was determined as optimum catalyst content and the MTZ removal showed two consecutive pseudo-first-order kinetic stages. These were related to the fast reaction of the target molecule with OH formed from Fenton's reaction, followed by a slower attack of physisorbed BDD(OH) onto Fe(III)-MTZ complexes. The effect of j and MTZ content on decay kinetics and TOC removal was examined. PEF was the best treatment due to the decomposition of photoactive intermediates by UVA radiation, yielding total mineralization of a 0.523 mM herbicide solution after 420 min of electrolysis at 100.0 mA cm−2. A thorough reaction pathway for MTZ degradation is proposed from the sixteen heteroaromatic by-products and three aliphatic molecules identified by GC-MS and LC-MS/MS. Oxalic and oxamic acids were detected as final carboxylic acids by ion-exclusion HPLC

Effective degradation of phenacetin in wastewater by (photo)electro-Fenton processes: Investigation of variables, acute toxicity, and intermediates

Electro-Fenton (EF) and solar photoelectro-Fenton (SPEF) processes were employed at different scales to degrade phenacetin (PNT), the first synthetic analgesic. EF experiments were conducted at lab scale, whereas SPEF experiments were performed in an 8 L pre-pilot plant using an electrochemical filter-press cell. Under optimal conditions (25 mg L−1 PNT, 25.3 mg L−1 Fe2+, and current density of 59.5 mA cm−2), EF resulted in degradation and mineralization degrees of 83.9% and 45.2% at 14 and 230 min, respectively. Similarly, PNT was spiked into real wastewater from a municipal secondary treatment plant, resulting in degradation of 68.0% and mineralization of 39.4%, with an energy consumption of 7.0 kWh g−1. The optimal conditions of SPEF (16.8 mg L−1 Fe2+ and current density of 45.9 mA cm−2) led to degradation and mineralization degrees of 55.9% and 37.1% at 36 and 181 min, respectively, with a low energy consumption of 0.142 kWh g−1. Both processes effectively detoxified the solutions, as demonstrated by tests with Artemia salina and Lactuca sativa. Three distinct degradation pathways were proposed based on the identification of eleven reaction intermediates formed upon •OH attack. In conclusion, the low energy cost of the SPEF process underscores its potential for pharmaceutical degradation in wastewater

Exploring innovative Leishmaniasis treatment: drug targets from pre-clinical to clinical findings

Leishmaniasis is a group of tropical diseases caused by parasitic protozoa belonging to the genus Leishmania. The disease is categorized in cutaneous leishmaniasis (CL), mucocutaneous leishmaniasis (MCL), and visceral leishmaniasis (VL). The conventional treatment is complex and can present high toxicity and therapeutic failures. Thus, there is a continuing need to develop new treatments. In this review, we focus on the novel molecules described in the literature with potential leishmanicidal activity, categorizing them in pre-clinical (invitro, invivo), drug repurposing and clinical research.This research was funded by Conselho Nacional de Desenvolvimento Científico e Tecnológico for the Scientific grants (CNPq 301964/2019-0 Chamada No. 06/2019, Chamada CNPq No. 01/2019) and Portuguese Science and Technology Foundation, Ministry of Science and Education (FCT/MEC) through the sponsorship of the project M-ERA-NET-0004/2015-PAIRED (strategic fund), co-financed by FEDER, under the Partnership Agreement PT2020. We would like to thank Tiago Branquinho Oliveira for the help provided in drawing Figure 3.info:eu-repo/semantics/publishedVersio

Quasi-stationary simulations of the directed percolation universality class in d = 3 dimensions

We present quasi-stationary simulations of three-dimensional models with a single absorbing configuration, namely the contact process (CP), the susceptible-infected-susceptible (SIS) model and the contact replication process (CRP). The moment ratios of the order parameters for the DP class in three dimensions were set up using the well established SIS and CP models. We also show that the mean-field exponent for d = 3 reported previously for the CRP (Ferreira 2005 Phys. Rev. E 71 017104) is a transient observed in the spreading analysis