RESUMO

Copper oxide nanoparticles (CuONPs) have been produced on a large scale because they can be applied across various fields, especially in nano-enabled healthcare and agricultural products. However, the increasing use of CuONPs leads to their release and accumulation into the environment. The CuONPs uptaken by seeds and their implications on germination behavior have been reported, but little is known or understood about their impact on photosynthesis in seed tissues. To fill knowledge gaps, this study evaluated the effects of CuONP concentrations (0-300 mg L-1) on the photosynthetic activity of Inga laurina seeds. The microscopy data showed that CuONPs had an average size distribution of 57.5 ± 0.7 nm. Copper ion release and production of reactive oxygen species (ROS) by CuONPs were also evaluated by dialysis and spectroscopy experiments, respectively. CuONPs were not able to intrinsically generate ROS and released a low content of Cu2⁺ ions (4.5%, w/w). Time evolution of chlorophyll fluorescence imaging and laser-induced fluorescence spectroscopy were used to monitor the seeds subjected to nanoparticles during 168 h. The data demonstrate that CuONPs affected the steady-state maximum chlorophyll fluorescence ( F m ' ), the photochemical efficiency of photosystem II ( F v / F m ), and non-photochemical quenching ( NPQ ) of Inga laurina seeds over time. Besides, the NPQ significantly increased at the seed development stage, near the root protrusion stage, probably due to energy dissipation at this germination step. Additionally, the results indicated that CuONPs can change the oscillatory rhythms of energy dissipation of the seeds, disturbing the circadian clock. In conclusion, the results indicate that CuONPs can affect the photosynthetic behavior of I. laurina seeds. These findings open opportunities for using chlorophyll fluorescence as a non-destructive tool to evaluate nanoparticle impact on photosynthetic activity in seed tissues.

Assuntos

RESUMO

This study reports curcumin as an efficient photolarvicide against Aedes aegypti larvae under natural light illumination. Larval mortality and pupal formation were monitored daily for 21 days under simulated field conditions. In a sucrose-containing formulation, a lethal time 50 (LT50) of 3 days was found using curcumin at 4.6 mg L-1. This formulation promoted no larval toxicity in the absence of illumination, and sucrose alone did not induce larval phototoxicity. The photodegradation byproducts (intermediates) of curcumin were determined and the photodegradation mechanisms proposed. Intermediates with m/z 194, 278, and 370 were found and characterized using LC-MS. The ecotoxicity of the byproducts on non-target organisms (Daphnia, fish, and green algae) indicates that the intermediates do not exhibit any destructive potential for aquatic organisms. The results of photodegradation and ecotoxicity suggest that curcumin is environmentally safe for non-target organisms and, therefore, can be considered for population control of Ae. aegypti.

Assuntos

RESUMO

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.

Assuntos

RESUMO

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.

Assuntos

RESUMO

Nimesulide (Nim) degradation in ultrapure water (UW) and municipal sewage (MS) via UV-ABC/H2O2 was investigated. The variables included in the experimental design were time, initial Nim, and initial H2O2 concentrations. Resulting decreases in Nim concentration (monitored by high performance liquid chromatography (HPLC) using a photodiode array detector operating at a maximum UV absorbance of 300 nm), mineralization (from total organic carbon (TOC) measurements), and ecotoxicity (assays employing the bioindicators Daphnia similis, Artemia salina, and Allium cepa) were also studied. Degradation rates of 90% or higher were found for 15-20 min reaction times, employing combinations of [H2O2] = 50-150 mg L-1 and [Nim] = 8.5-15 mg L-1 prepared with MS. Mineralization rates of 70% and higher were attained within 60 min of reaction for [Nim] = 15 mg L-1 prepared in MS with [H2O2] = 100 mg L-1. Nim by-products were detected and possible degradation pathways proposed. Ecotoxicity evaluation using A. salina, D. similis, and A. cepa revealed that the treated samples had significantly lower toxicity. Exposure to treated samples resulted in survival rates of 79% for A. salina and over 90% for D. similis. No root growth inhibition was observed in A. cepa exposed to treated samples, whereas exposure to untreated samples inhibited root growth by 60%. Statistical analysis revealed elimination of cytotoxicity and reduction of genotoxicity against A. cepa. The results showed that the UV-ABC/H2O2 process can be employed as a pre- or post-treatment method to remove Nim from contaminated wastewater.

Assuntos

RESUMO

Electro-oxidation with electrogenerated H2O2 (EO-H2O2) was applied to treat acidic aqueous solutions of 4-aminoantipyrine (4-AA), a persistent drug metabolite of dipyrone, in sulfate medium. Trials were made using a boron-doped diamond anode in the presence of H2O2 electrogenerated on site. A 24 central composite design (CCD) was employed to evaluate the effect of four independent variables, namely current density (j), pH, 4-AA concentration and electrolysis time, on the percentages of degradation and mineralization, as well as on mineralization current efficiency (MCE). Predicted responses agreed with observed values, showing linear trendlines with good R2 and R2adj values. The degradation was optimum at j=77.5mAcm-2, pH3.5 and 62.5mgL-1 4-AA, leading to 63% and 99% removal after 3 and 7min, respectively. For those solutions, the largest mineralization was found at j=77.5mAcm-2, attaining 45% abatement at 175min. Low MCE values were obtained in all electrolyses. An initial route for 4-AA degradation is proposed based on one dimer and eleven aromatic and aliphatic intermediates detected in the treated solutions at pH3.5 by LC-MS. The initial 62.5mgL-1 solution at pH3.5 presented acute toxicity on Artemia salina larvae, with LC50=13.6mgL-1, being substantially reduced after 3 and 7min of EO-H2O2 at j=77.5mAcm-2 due to the formation of less toxic derivatives.

RESUMO

This study describes the performance of electro-Fenton (EF) and photoelectro-Fenton (PEF) processes to degrade the herbicide tebuthiuron (TBH) in 0.050 M Na2SO4 at pH = 3.0. Experiments were performed in an undivided cell equipped with a boron-doped diamond (BDD) or Pt anode and an air-diffusion cathode that produces H2O2. Physisorbed hydroxyl radicals (M(OH)) generated from water oxidation at the anode and/or free OH formed from Fenton's reaction acted as main oxidants. All processes became much more effective using a BDD anode because of the higher oxidation power of BDD(OH). Sulfate and nitrate were the predominant ions released during TBH destruction. In both, EF and PEF treatments, two distinct kinetic regimes were observed, the first one corresponding to the oxidation of free TBH by OH and the second one to that of the Fe(III)-TBH complex by M(OH). The effect of Fe2+ and TBH concentrations on the kinetics of both regions has been examined. Moreover, a poor mineralization was reached with Pt anode, whereas almost total mineralization was attained by EF and PEF with BDD. Both processes showed analogous mineralization rates because the intermediates produced could not be photodegraded by UVA light. Gas chromatography-mass spectrometry analysis of electrolyzed solutions revealed the generation of eight heteroaromatics along with 1,3-dimethylurea, which have been included in a reaction pathway proposed for the initial degradation of TBH.

Assuntos

RESUMO

The abatement of valproic acid sodium salt (VA) via photo-Fenton process was investigated to evaluate the effect of irradiation type. Three different light sources have been used: UVA (black light blue lamps, BLB reactor), UVC (UVC reactor) and simulated sunlight in a Solarbox (SB). Using the highest concentrations of Fe2+ (10mgL-1) and H2O2 (150mgL-1), 100% of VA degradation was observed in BLB and UVC devices, and 89.7% in Solarbox. Regarding mineralization, 67.4% and 76.4% of TOC conversion were achieved in BLB and UVC, respectively. In Solarbox, mineralization was negligible. Treated solutions under UVA or UVC radiation became biodegradable (BOD5/COD≥0.25), which was not observed in Solarbox where BOD5/COD achieved was only 0.20. Regarding to toxicity (Vibrio Fischeri method), all processes have promoted the overall toxicity reduction of VA solution. Transformation products were identified by a LC-ESI-TOF mass spectrometer, and degradation pathways were proposed. Operating costs and the energy needed by mg of VA removed were estimated and compared, for the different installations, showing that UVA can remove around 3 times more VA than SB and 2 times more VA than UVC, under the same conditions.

Assuntos

RESUMO

A solution with 0.38 mM of the pesticide propoxur (PX) at pH 3.0 has been comparatively treated by electrochemical oxidation with electrogenerated H2O2 (EO-H2O2), electro-Fenton (EF), and photoelectro-Fenton (PEF). The trials were carried out with a 100-mL boron-doped diamond (BDD)/air-diffusion cell. The EO-H2O2 process had the lowest oxidation ability due to the slow reaction of intermediates with •OH produced from water discharge at the BDD anode. The EF treatment yielded quicker mineralization due to the additional •OH formed between added Fe2+ and electrogenerated H2O2. The PEF process was the most powerful since it led to total mineralization by the combined oxidative action of hydroxyl radicals and UVA irradiation. The PX decay agreed with a pseudo-first-order kinetics in EO-H2O2, whereas in EF and PEF, it obeyed a much faster pseudo-first-order kinetics followed by a much slower one, which are related to the oxidation of its Fe(II) and Fe(III) complexes, respectively. EO-H2O2 showed similar oxidation ability within the pH range 3.0-9.0. The effect of current density and Fe2+ and substrate contents on the performance of the EF process was examined. Two primary aromatic products were identified by LC-MS during PX degradation.

Assuntos

RESUMO

This study employed direct UV-ABC photolysis and the UV-ABC/H2O2 process to investigate the degradation of tolfenamic acid (TA), a common anti-inflammatory drug used in both human and veterinary medicine. A 23 factorial design with added center point was used to evaluate the effect of three independent variables-namely, H2O2 concentration ([H2O2]), TA concentration ([TA]), and experiment time (time)-on TA degradation and H2O2 photolysis during UV-ABC/H2O2 treatment using a high-pressure mercury vapor lamp (photon flux of 2.6307 × 104 J s-1) as the UV irradiation source. The responses yielded similar values, revealing a linear behavior, with correlation coefficients R = 0.9968 and Radj = 0.9921 for TA degradation and R = 0.9828 and Radj = 0.9570 for H2O2 photolysis. The most efficient combination of variables was [H2O2] = 255 mg L-1 and [TA] = 25 mg L-1, resulting in 100% TA degradation and 98.87% H2O2 photolysis by 90 min of treatment. Additionally, the second-order kinetic constant of the reaction between TA and HO● was determined using a competitive kinetic model, employing 2,4-dichlorophenoxyacetic acid (2,4D) as the reference compound. The kinetic constant was 1.9 × 1010 M-1 s-1 in alkaline medium. TA degradation by direct photolysis generated quinone imines as by-products, responsible for the formation of a dark red "internal filter" that increased the value of acute toxicity to Artemia salina. The UV-ABC/H2O2 process did not promote formation of quinone imines by 90 min of treatment and therefore did not increase acute toxicity values. Several by-products generated during TA degradation were identified and possible degradation pathways for the UV-ABC and UV-ABC/H2O2 processes were proposed.

Assuntos