Multivariate analysis of photo-Fenton degradation of the herbicides tebuthiuron, diuron and 2,4-D

The degradation of herbicides in aqueous solution by photo-Fenton process using ferrioxalate complex (FeOx) as source of Fe2+ was evaluated under blacklight irradiation. The commercial products of the herbicides tebuthiuron, diuron and 2,4-D were used. The multivariate analysis, more precisely, the response surface methodology was applied to evaluate the role of FeOx and hydrogen peroxide concentrations as variables in the degradation process, and in particular, to define the concentration ranges that result in the most efficient degradation of the herbicides. The degradation process was evaluated by the determination of the remaining total organic carbon content (TOC), by monitoring the decrease of the concentrations of the original compounds using HPLC and by the chloride ion release in the case of diuron and 2,4-D. Under optimized conditions, 20min were sufficient to mineralize 93% of TOC from 2,4-D and 90% of diuron, including oxalate. Complete dechlorination of these compounds was achieved after 10 min reaction. It was found that the most recalcitrant herbicide is tebuthiuron, while diuron shows the highest degradability. However, under optimized conditions the initial concentration of tebuthiuron was reduced to less than 15%, while diuron and 2,4-D were reduced to around 2% after only 1 min reaction. Furthermore, it was observed that the ferrioxalate complex plays a more important role than H2O2 in the photodegradation of these herbicides in the ranges of concentrations investigated. (C) 2004 Elsevier Ltd. All rights reserved.

Electroanalysis and determination of acetaldehyde in fuel ethanol using the reaction with 2,4-dinitrophenylhydrazine

The voltammetric reduction of acetaldehyde was studied in 0.1 M LiOH: LiCl (60: 40 v/v). Welldefined waves can be seen at -1.77 and -1.60 V with the use of hanging mercury and glassy carbon electrodes. Acetaldehyde was shown to react at room temperature with the 2,4-dinitrophenylhydrazine and the product exhibited a differential pulse voltammetric peak at -0.90V, which was well separated from the peaks of the derivative. This allowed the indirect determination of acetaldehyde in the presence of 0.1 M ethanol/tetrabutylammonium perchlorate after 10 min of reaction. Calibration graphs were obtained for 1.00 x 10(-6)-1.00 x 10(-4) M of acetaldehyde. The detection limit is 8.14 x 10(-7) M. The method has been applied satisfactorily to the determination of total aldehyde in fuel ethanol samples without any pretreatment.

Structure characterization of molecular complexes for non-linear optical materials. II. 1 : 1 complexes of 4-methyl-morpholine-N-oxide (1) and 3-picoline-N-oxide (2) with 2,4,6-trinitrophenol, studied by X-ray, AM1 and DFT calculations

(1) C6H2N3O7- center dot C5H12NO2+, Mr = 346.26, P2(1)/c, a = 7.2356(6), b = 10.5765(9), c = 19.593(2) angstrom, 3 beta=95.101(6)degrees, V = 1493.5(2) angstrom(3), Z = 4, R-1 = 0.0414; (2) C6H2N3O7- center dot C6H8NO+, Mr = 38.24, P2(1)/n, a = 7.8713(5), b = 6.1979(7), c = 28.697(3) angstrom, beta = 90.028(7)degrees, V = 1400.0(2) angstrom(3), Z = 4, R-1 = 0.0416. The packing units in both compounds consist of hydrogen bonded cation-anion pairs. The (hyper)polarizabilities have been calculated for the crystallographic and optimized molecules, by AM1 and at the DFT/B3LYP(6-31G**) level.

EFFECTS OF 2,4-DICHLOROPHENOXYACETIC ACID (2,4-D) ON OPEN-FIELD BEHAVIOR AND NEUROCHEMICAL PARAMETERS OF RATS

The effects of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) on the central nervous system (CNS) were studied in rats. Behavioural and neurochemical studies were performed. Results show that acute and oral administration of dimethylamine 2,4-D was able to decrease locomotion and rearing frequencies and to increase immobility duration of rats observed in an open-field test. Treatment of rats with p-chlorophenylalanine (PCPA) was unable to change rat's open-field behaviour; 5-hydroxytryptophan (5-HTP) administration not only increased locomotion and rearing frequences but also decreased immobility duration. Pretreatment of the rats with PCPA and 5-HTP decreased and increased dimethylamine 2,4-D effects, respectively. The herbicide was not able to change the striatal levels of dopamine and homovanilic acid but decreased the striatal levels of serotonin (5-HT), as observed for the doses of 100 and 200 mg/kg and increased those of 5-hydroxyindoleacetic acid (5-HIAA) as measured after the 200 mg/kg dose treatment. When the levels of serotonin and 5-HIAA were measured at the brain stem level, only those of 5-HIAA were modified, being increased by diethylamine 2,4-D (60; 100 and 200 mg/kg); this increment on 5-HIAA levels was observed even 1 hr after pesticide administration. Further analysis showed that 2,4-D concentrations chromatographycally detected both in serum and brain of the intoxicated animals were dose-dependent, being found as early as 1 hr after the smaller dose of the herbicide used (10 mg/kg). The results suggest that diethylamine 2,4-D modify 5-HT functional activity within the CNS. Thus, the effects of the herbicide on open-field behaviour of rats could be attributed to a direct or indirect pesticide action on serotoninergic systems.

Acute, subchronic and chronic 2,4-dichlorophenoxyacetic acid (2,4-D) intoxication in rats

The acute, subchronic and chronic toxicities of 2,4- dichlorophenoxyacetic acid (2,4-D) were studied in rats. Animals were exposed acutely (600 mg/kg), subchronically (200 ppm for 30 d) and chronically (200 ppm for 180 d) to 2,4-D by the oral route. Clinical, laboratory and histopathological methods were used as indicators of toxicity. After acute exposure, the herbicide decreased locomotor activity and induced ataxia, sedation, muscular weakness (mainly of the hind quarters) and gasping for breath; increased aspartate aminotransferase (AST), alanine aminotransferase (ALT), lactate dehydrogenase (LDH), alkaline phosphatase (AP), amylase activities and creatinine levels; decreased total protein (TP) and glucose levels; and increased hematocrit values. Subchronic and chronic 2,4-D exposures did not induce overt clinical signs or symptoms of intoxication. However, subchronic herbicide exposure increased AST activity and albumin and hematocrit values, and chronic exposure increased AST, AP and LDH activities, decreased amylase and glucose levels, but did not change hematocrit values. Chromatographic analysis of the serum of chronically exposed rats showed the presence of the herbicide; the amount found (3.76 ± 1.16 mg/ml) suggested the absence of 2,4-D accumulation within the body. Although macroscopic or histopathological lesions were not observed in acutely, subchronically or chronically 2,4-D exposed rats, the laboratory data obtained suggest tissue injuries after dosing, since the results are considered early indicators of primarily hepatic and muscle tissue damage.

Determination of 2,4-D and dicamba in food crops by MEKC

The determination of 2,4-D (2,4-dichlorophenoxyacetic acid) and Dicamba (2-methoxy-3,6-dichlorobenzoic acid) residues in sugar cane, rice and corn was performed by a supercritical fluid extraction (SFE) method using CO2/acetone as extraction mix and an SFE apparatus developed in our laboratory. The extracts were cleaned up after extraction by both liquid- liquid partition and a Florisil column. Micellar electrokinetic capillary chromatography (MEKC) coupled with ultraviolet on-column detection was used for the analysis of these pesticides. The detection limits were improved by the preparation of a special detection cell with an increased pathlength that gave detection limits of ca. 0.6 pg for 2,4-D and Dicamba. Our results demonstrated that capillary electrophoresis can be a powerful new analytical tool for pesticide residue analysis.

Photodegradation of dichloroacetic acid and 2,4-dichlorophenol by ferrioxalate/H2O2 system

The photo-Fenton process using potassium ferrioxalate as a mediator in the photodegradation reaction of organochloride compounds in an aqueous medium was investigated. The influence of parameters such as hydrogen peroxide and ferrioxalate concentrations and initial pH, was evaluated using dichloroacetic acid (DCA) as a model compound under black-light lamp irradiation. An upflow annular photoreactor, operating in a single pass or recirculating mode was used during photodegradation experiments with artificial light. The extent of the release of chloride ions was used to evaluate the photodegradation reaction. The optimum pH range observed was 2.5-2.8. The efficiency of DCA dechlorination increased with increasing concentrations of H2O2 and potassium ferrioxalate, reaching a plateau after the addition of 6 and 1.5 mmol/L of those reagents, respectively. The total organic carbon (TOC) content in DCA and 2,4-dichlorophenol (DCP) solutions was compared with the chloride released after photodegradation. The influence of natural solar light intensity, measured at 365 nm, was evaluated for the dechlorination of DCA on typical summer's days showing a linear dependency. The photodegradation of DCA using black-light lamp and solar irradiation was compared.

Solar photodegradation of dichloroacetic acid and 2,4-dichlorophenol using an enhanced photo-Fenton process

The photo-Fenton process using potassium ferrioxalate as a mediator was investigated for the photodegradation of dichloracetic acid (DCA) and 2,4-dichlorophenol (DCP) in aqueous medium using solar light as source of irradiation. The influence of the solution depth, the light intensity and the effect of stirring the solution during irradiation process were evaluated using DCA as a model compound. A negligible influence of stirring the solution was observed when the concentration of ferrioxalate (FeOx) was 0.8 mM and solution depth was 4.5 or 14 cm. The optimum FeOx concentration determined for solution depths between 4.5 and 14 cm was 0.8 mM considering total organic carbon (TOC) removal during DCA irradiation. The high efficiency of the photo-Fenton process was demonstrated on summer days, when only 10 min of exposition (around noon) were sufficient to completely destroy the organic carbon of a 1.0 mM DCA solution in the presence of 0.8 mM FeOx and 6.0 mM H2O2 using a solution depth of 4.5 cm. It was observed that the photodegradation efficiency increases linearly with the solar light intensity up to values around 15 Wm-2 but this linear relationship does not hold above this value showing a square root dependence. The photodegradation of a solution of DCP/FeOx showed a lower TOC removal rate than that observed for DCA/FeOx, achieving ∼90% after 35 min irradiation under 19 Wm-2, while under this light intensity, the same TOC removal of DCA/FeOx was achieved in only 10 min irradiation. © 2002 Elsevier Science Ltd. All rights reserved.

Breve revisão de métodos de determinação de resíduos do herbicida á cido 2,4-diclorofenoxiacético (2,4-D)

This paper supplies a revision about the main techniques of extraction, clean-up and pre-concentration of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) in water and soil samples, as well as chromatographic methods and immune assays for its identification and quantification.

Absorption and translocation of 2,4-D in plants of Memora peregrina

The objective of this work was to evaluate absorption and translocation of the herbicide 2,4-D in plants of Memora peregrina. The herbicide 2,4-D was used alone with the formulation DMA 806 BR and associated with the herbicide picloram in the commercial product Padron. Levels of radioactivity on the treated leaves were determined in sample obtained after washing them with methanol and chloroform at different times after the application of the radiolabelled formulation (1, 2, 4, 8, 24, and 48 h). Translocation was evaluated by cutting plants between stem and root. The parts obtained were: root, stem, leaf treated, leaves above the leaf treated, leaves below the leaf treated, and leaf opposite of the leaf treated. These parts were weighted, dried, ground, burnt, and radioactivity in the samples was determined. The results suggest that the translocation of the radioactive herbicide 2,4-D was insignificant in plants of M. peregrina in the two treatments evaluated. Absorption of 14C 2,4-D in the treatment with DMA 806 BR and the mixture of DMA 806 BR plus Padron had the same behavior. These observations explain the inefficient control obtained with this herbicide in plant species under study.

Biomimetic sensor based on 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H- porphyrin iron (III) chloride and MWCNT for selective detection of 2,4-D

Exploitation of the electronic properties of carbon nanotubes for the development of voltammetric and amperometric sensors to monitor analytes of environmental relevance has increased in recent years. This work reports the development of a biomimetic sensor based on a carbon paste modified with 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphyrin iron (III) chloride (a biomimetic catalyst of the P450 enzyme) and multi-wall carbon nanotubes (MWCNT), for the sensitive and selective detection of the herbicide 2,4- dichlorophenoxyacetic acid (2,4-D). The sensor was evaluated using cyclic voltammetry and amperometry, for electrochemical characterization and quantification purposes, respectively. Amperometric analyses were carried out at -100 mV vs. Ag/AgCl(KClsat), using a 0.1 mol L-1 phosphate buffer solution at pH 6.0 as the support electrolyte. Under these optimized analytical conditions, the sensor showed a linear response between 9.9 × 10-6 and 1.4 × 10-4 mol L-1, a sensitivity of 1.8 × 104 (±429) μA L mol -1, and limits of detection and quantification of 2.1 × 10 -6 and 6.8 × 10-6 mol L-1, respectively. The incorporation of functionalized MWCNT in the carbon paste resulted in a 10-fold increase in the response, compared to that of the biomimetic sensor without MWCNT. In addition, the low applied potential (-100 mV) used to obtain high sensitivity also contributed to the excellent selectivity of the proposed sensor. The viability of the application of this sensor for analysis of soil samples was confirmed by satisfactory recovery values, with a mean of 96% and RSD of 2.1% (n = 3). © 2013 Elsevier B.V.

A new hybrid polyhedral cubic silsesquioxane chemically modified with 4-amino-5-(4-pyridyl)-4H-1,2,4-triazole-3-thiol (APTT) and copper hexacyanoferrate(III) for voltammetric determination of nitrite

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Alterations in the duodenum myenteric neurons of Wistar rats after ingesting of 2,4 dichlorophenoxyacetic acid

The 2,4 dichlorophenoxyacetic acid (2,4-D) is a systemic herbicide whose effects in animal organic systems have been examined in previous studies, being the neurotoxicity considered the predominant effect. However, the studies that detect the 2,4-D neurotoxicity have merely focused in the central nervous system, and therefore, little is known about the effect of this herbicide in the enteric nervous system. This study aimed to verifying the 2,4-D effects on the myenteric neurons in duodenum of Wistar rats. Ten 60-day-old male Wistar rats (Rattus norvegicus) were divided in two groups: control group (C) that did not receive 2,4-D and experimental group (E) that received 5.0 mg of 2,4-D/kg for 15 days. At the end of experimental period, the animal were euthanized, the duodenum was collected and processed for NADPH-diaphorase histochemical analysis in order to expose the nitrergic myenteric neurons (NADPH-dp). In the light microscopy analysis, the whole-mount preparation obtained from duodenum of each animal were image-captured in 120 and 40 fields, for quantitative and morphometric analyses of myenteric neurons, respectively. The neuronal density was not affected when comparing the two groups, but an increase (p > 0.05) of 8.5% was observed in the cell body area of neurons in the E group. In conclusion, the ingestion of 2,4-D at a dosage of 5.0 mg/kg body weight for 15 days does not change the neuronal density, but promotes the hypertrophy of NADPH-dp myenteric neurons in duodenum of the rats of this study.

2,4-Dichlorophenoxyacetic acid (2,4-D) degradation promoted by nanoparticulate zerovalent iron (nZVI) in aerobic suspensions

Reactive species generated by Fe0 oxidation promoted by O2 (catalyzed or not by ligands) are able to degrade contaminant compounds like the herbicide 2,4-dichlorophenoxyacetic acid. The degradation of 2,4-D was influenced by the concentrations of zero valent iron (ZVI) and different ligands, as well as by pH. In the absence of ligands, the highest 2,4-D degradation rate was obtained at pH 3, while the highest percentage degradation (50%) was achieved at pH 5 after 120 min of reaction. Among the ligands studied (DTPA, EDTA, glycine, oxalate, and citrate), only ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) significantly enhanced oxidation of 2,4-D. This increase in oxidation was observed at all pH values tested (including neutral to alkaline conditions), indicating the feasibility of the technique for treatment of contaminated water. In the presence of EDTA, the oxidation rate was greater at pH 3 than at pH 5 or 7. Increasing the EDTA concentration increased the rate and percentage of 2,4-D degradation, however increasing the Fe0 concentration resulted in the opposite behavior. It was found that degradation of EDTA and 2,4-D occurred simultaneously, and that the new methodology avoided any 2,4-D removal by adsorption/coprecipitation. © 2013 Elsevier Ltd.