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1.
Planta ; 249(6): 1837-1849, 2019 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-30850862

RESUMO

MAIN CONCLUSION: Glufosinate is primarily toxic to plants due to a massive light-dependent generation of reactive oxygen species rather than ammonia accumulation or carbon assimilation inhibition. Glutamine synthetase (GS) plays a key role in plant nitrogen metabolism and photorespiration. Glufosinate (C5H12NO4P) targets GS and causes catastrophic consequences leading to rapid plant cell death, and the causes for phytoxicity have been attributed to ammonia accumulation and carbon assimilation restriction. This study aimed to examine the biochemical and physiological consequences of GS inhibition to identify the actual cause for rapid phytotoxicity. Monocotyledonous and dicotyledonous species with different forms of carbon assimilation (C3 versus C4) were selected as model plants. Glufosinate sensitivity was proportional to the uptake of herbicide between species. Herbicide uptake also correlated with the level of GS inhibition and ammonia accumulation in planta even with all species having the same levels of enzyme sensitivity in vitro. Depletion of both glutamine and glutamate occurred in glufosinate-treated leaves; however, amino acid starvation would be expected to cause a slow plant response. Ammonia accumulation in response to GS inhibition, often reported as the driver of glufosinate phytotoxicity, occurred in all species, but did not correlate with either reductions in carbon assimilation or cell death. This is supported by the fact that plants can accumulate high levels of ammonia but show low inhibition of carbon assimilation and absence of phytotoxicity. Glufosinate-treated plants showed a massive light-dependent generation of reactive oxygen species, followed by malondialdehyde accumulation. Consequently, we propose that glufosinate is toxic to plants not because of ammonia accumulation nor carbon assimilation inhibition, but the production of reactive oxygen species driving the catastrophic lipid peroxidation of the cell membranes and rapid cell death.


Assuntos
Amaranthus/efeitos dos fármacos , Aminobutiratos/toxicidade , Bassia scoparia/efeitos dos fármacos , Herbicidas/toxicidade , Poaceae/efeitos dos fármacos , Espécies Reativas de Oxigênio/metabolismo , Amaranthus/metabolismo , Amaranthus/efeitos da radiação , Aminobutiratos/efeitos da radiação , Amônia/metabolismo , Bassia scoparia/metabolismo , Bassia scoparia/efeitos da radiação , Carbono/metabolismo , Morte Celular/efeitos dos fármacos , Membrana Celular/efeitos dos fármacos , Glutamato-Amônia Ligase/antagonistas & inibidores , Herbicidas/efeitos da radiação , Luz , Peroxidação de Lipídeos/efeitos dos fármacos , Folhas de Planta/efeitos dos fármacos , Folhas de Planta/metabolismo , Folhas de Planta/efeitos da radiação , Proteínas de Plantas/antagonistas & inibidores , Poaceae/metabolismo , Poaceae/efeitos da radiação , Espécies Reativas de Oxigênio/efeitos da radiação
2.
Ecotoxicol Environ Saf ; 163: 620-628, 2018 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-30096663

RESUMO

Nanosized BaFe1-xCuxO3 powders were prepared using the Pechini method. To limit grain growth and agglomeration, the temperature of calcination was limited to 800 °C. For all samples, the cubic form of BaFeO2.75 was predominant with minor additional phases. Cu doping was found to have a remarkable effect on the structural cubic unit cell parameter as the Cu concentration increased. As shown by XRD,the samples were in the nanometer size range (17-63 nm). However, as the Cu concentration increases, the agglomeration increases with the highest surface area for the BaFe0.95Cu0.05O3 composition, which also displays the highest photocatalytic atrazine degradation. For this sample, more than 90% degradation of atrazine was obtained at the optimum conditions (120 min irradiation under visible light at pH 11 using 0.75 mg of the catalyst). The Atrazine degradation was found to follow the pseudo-order kinetics. GC/MS was used to detect the intermediates and the reaction pathways. All the prepared samples and produced waters at the end of the experiment were found to be nontoxic.


Assuntos
Atrazina/efeitos da radiação , Herbicidas/efeitos da radiação , Luz , Óxidos/química , Atrazina/química , Catálise , Herbicidas/química , Cinética , Óxidos/efeitos da radiação , Fotólise , Temperatura
3.
Nat Commun ; 9(1): 2967, 2018 07 27.
Artigo em Inglês | MEDLINE | ID: mdl-30054483

RESUMO

Paraquat, as one of the most widely used herbicides globally, is highly toxic to humans, and chronic exposure and acute ingestion leads to high morbidity and mortality rates. Here, we report user-friendly, photo-responsive paraquat-loaded supramolecular vesicles, prepared via one-pot self-assembly of amphiphilic, ternary host-guest complexes between cucurbit[8]uril, paraquat, and an azobenzene derivative. In this vesicle formulation, paraquat is only released upon UV or sunlight irradiation that converts the azobenzene derivative from its trans- to its cis- form, which in turn dissociates the ternary host-guest complexations and the vesicles. The cytotoxicity evaluation of this vesicle formulation of paraquat on in vitro cell models, in vivo zebrafish models, and mouse models demonstrates an enhanced safety profile. Additionally, the PQ-loaded vesicles' herbicidal activity against a model of invasive weed is nearly identical to that of free paraquat under natural sunlight. This study provides a safe yet effective herbicide formulation.


Assuntos
Herbicidas/metabolismo , Herbicidas/efeitos da radiação , Herbicidas/toxicidade , Animais , Compostos Azo/química , Compostos Azo/metabolismo , Compostos Azo/efeitos da radiação , Compostos Azo/toxicidade , Células COS , Chlorocebus aethiops , Feminino , Herbicidas/química , Humanos , Rim/efeitos dos fármacos , Fígado/efeitos dos fármacos , Camundongos , Camundongos Endogâmicos C57BL , Modelos Animais , Paraquat/química , Paraquat/metabolismo , Paraquat/efeitos da radiação , Paraquat/toxicidade , Peixe-Zebra
4.
Environ Sci Process Impacts ; 20(8): 1123-1135, 2018 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-29974906

RESUMO

Pesticides are commonly applied on foliage, forming dry deposits on the leaf cuticular wax. However, their photochemical transformation in this lipophilic environment is much less understood compared with that in surface water. In this work, sunlight photolysis of six chlorinated phenoxyacetic acid herbicides (i.e., 2,4-D and structural analogues) was evaluated in four organic solvents, on quartz, and on paraffin wax. In solvents of low polarity (i.e., n-heptane and 2-propanol), direct photolysis of 2,4-D herbicides was enhanced due to the relatively high quantum yields in these solvents. Photolysis on paraffin wax was slower than photolysis on quartz by a factor of 3-9, but was comparable with that in solvents of low polarity. With environmentally relevant irradiation and surface loading, the half-lives of 2,4-D herbicides on paraffin wax were 27-159 h, which are within the same range reported for biodegradation, the dominant dissipation pathway in the current 2,4-D fate model. Product analyses showed that photoreductive dechlorination is the dominant pathway in organic solvents, accounting for 68-100% of parent compound decay. On quartz and paraffin wax surfaces, however, photoreductive dechlorination products accounted for <60% of parent compound decay. Combining kinetic modeling and product analyses, it was shown that neither could the two additional putative pathways (photosubstitution of chlorine by hydroxyl group and cleavage of the ether bond) fully account for the total phototransformation on surfaces. These results suggest that rapid photolysis on surfaces can be attributed to unique pathways that are absent in the organic solvent phase.


Assuntos
Ácido 2,4-Diclorofenoxiacético/efeitos da radiação , Herbicidas/efeitos da radiação , Folhas de Planta/química , Luz Solar , Meia-Vida , Cinética , Parafina , Fotólise , Quartzo , Solventes
5.
Environ Sci Pollut Res Int ; 25(30): 29848-29859, 2018 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-28718021

RESUMO

Bioherbicides appear as an ecofriendly alternative to synthetic herbicides, generally used for weed management, because they are supposed to have low side on human health and ecosystems. In this context, our work aims to study abiotic (i.e., photolysis) and biotic (i.e,. biodegradation) processes involved in the fate of leptospermone, a natural ß-triketone herbicide, by combining chemical and microbiological approaches. Under controlled conditions, the photolysis of leptospermone was sensitive to pH. Leptospermone has a half-life of 72 h under simulated solar light irradiations. Several transformation products, including hydroxy-leptospermone, were identified. For the first time, a bacterial strain able to degrade leptospermone was isolated from an arable soil. Based on its 16S ribosomal RNA (rRNA) gene sequence, it was affiliated to the Methylophilus group and was accordingly named as Methylophilus sp. LS1. Interestingly, we report that the abundance of OTUs, similar to the 16S rRNA gene sequence of Methylophilus sp. LS1, was strongly increased in soil treated with leptospermone. The leptospermone was completely dissipated by this bacteria, with a half-life time of 6 days, allowing concomitantly its growth. Hydroxy-leptospermone was identified in the bacterial culture as a major transformation product, allowing us to propose a pathway of transformation of leptospermone including both abiotic and biotic processes.


Assuntos
Herbicidas/metabolismo , Herbicidas/efeitos da radiação , Methylophilus/metabolismo , Floroglucinol/análogos & derivados , Biodegradação Ambiental , Methylophilus/genética , Floroglucinol/metabolismo , Floroglucinol/efeitos da radiação , Fotólise , RNA Ribossômico 16S/genética , Microbiologia do Solo , Luz Solar
6.
Environ Sci Process Impacts ; 18(10): 1305-1315, 2016 Oct 12.
Artigo em Inglês | MEDLINE | ID: mdl-27711795

RESUMO

The photodegradation rate of the herbicide imazethapyr on epicuticular waxes of soybean and corn plants was investigated. Plant age, relative humidity, temperature, and number of light banks were varied during plant growth, analyzed statistically, and examined to determine if these factors had an effect on the photodegradation of imazethapyr. Through ultraviolet/visible (UV-Vis) and fluorescence spectroscopy, epicuticular wax characteristics of soybean and corn plants were explored, were used to confirm observations determined statistically, and explain correlations between the rate constants and the composition of the epicuticular waxes. Plant age, the interaction between plant age and light, and the quadratic dependence on temperature were all determined to have a significant impact on the photodegradation rate of imazethapyr on the epicuticular waxes of soybean plants. As for the photodegradation rate on the epicuticular waxes of corn plants, the number of light banks used during growing and temperature were significant factors.


Assuntos
Glycine max , Herbicidas/efeitos da radiação , Ácidos Nicotínicos/efeitos da radiação , Ceras , Zea mays , Luz , Fotólise , Folhas de Planta
7.
Sci Total Environ ; 569-570: 518-526, 2016 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-27366982

RESUMO

Gamma radiation has been used to induce the degradation of compounds used as plasticizers and herbicides such as phthalic acid (PA), bisphenol A (BPA), diphenolic acid (DPA), 2,4-dichlorophenoxy-acetic acid (2,4-D), and 4-chloro-2-methylphenoxyacetic acid (MCPA) in aqueous solution, determining the dose constants, removal percentages, and radiation-chemical yields. The reaction rate constants of hydroxyl radical (HO), hydrated electron (eaq(-)) and hydrogen atom (H) with these pollutants were also obtained by means of competition kinetics, using 3-aminopyridine and atrazine as reference compounds. The results indicated that the elimination of these pollutants with gamma radiation mainly follows the oxidative pathway through reaction with HO radicals. The degradation by-products from the five pollutants were determined, detecting that the hydroxylation of the corresponding parent compounds was the main chemical process in the degradation of the pollutants. Moreover, a high decrease in the chemical oxygen demand has been observed for all pollutants. As expected, the degradation by-products generated by the irradiation of PA, BPA and DPA showed a lower toxicity than the parent compounds, however, in the case of 2,4-D and MCPA irradiation, interestingly, their by-products were more toxic than the corresponding original compounds.


Assuntos
Raios gama , Herbicidas/efeitos da radiação , Plastificantes/efeitos da radiação , Eliminação de Resíduos Líquidos/métodos , Poluentes Químicos da Água/química , Poluentes Químicos da Água/efeitos da radiação
8.
Chemosphere ; 146: 51-9, 2016 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-26706931

RESUMO

The calcined layered double hydroxides (cLDHs) Ti-doped and undoped MgFe for this study were prepared by co-precipitation method followed by calcination at 500 °C. The as-prepared samples were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Brunauer Emmett Teller (BET) and UV-Vis diffuse reflectance spectrum (DRS) techniques and tested for adsorption and photodegradation (including photocatalytic and photo-Fenton-like) of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) in aqueous solutions under visible light irradiation. In the range of studied operating conditions, the as-prepared samples exhibited excellent photo-Fenton-like activity, leading to more than 80-95% degradation of 2,4,5-T at initial concentration of 100 mg L(-1) with 4 g calcined LDHs per liter, was accomplished in 360 min, while 2,4,5-T half-life time was as short as 99-182 min. The kinetics of adsorption and photodegradation of 2,4,5-T were also discussed. These results offered a green, low cost and high efficiency photocatalyst for environmental remediation.


Assuntos
Ácido 2,4,5-Triclorofenoxiacético/química , Herbicidas/química , Hidróxidos/química , Poluentes Químicos da Água/química , Ácido 2,4,5-Triclorofenoxiacético/efeitos da radiação , Adsorção , Herbicidas/efeitos da radiação , Ferro/química , Magnésio/química , Fotólise , Titânio/química , Poluentes Químicos da Água/efeitos da radiação
9.
Environ Technol ; 37(2): 172-82, 2016.
Artigo em Inglês | MEDLINE | ID: mdl-26102217

RESUMO

The photodegradation of the herbicide fenuron (1,1-dimethyl-3-phenylurea) by using a natural iron oxide (NIO), α-Fe2O3, in aqueous solution at acidic pH has been undertaken. The NIO was characterized by the Raman spectroscopy method. The degradation pathways and the formation of degradation products were studied. A high-pressure mercury lamp and sunlight were employed as light source. Fenuron photodegradation using NIO with oxalic acid followed the pseudo-first-order kinetics, the optimal experimental conditions were [oxalic acid]0 = 10(-3) M and [NIO] = 0.1 g L(-1) at pH 3. A UVA/NIO/oxalic acid system led to a low fenuron half-life (60 min). The results were even better when solar light is used (30 min). The variables studied were the doses of iron oxide, of carboxylic acids, the solution pH and the effect of sunlight irradiation. The effects of four carboxylic acids, oxalic, citric, tartaric and malic acids, on the fenuron photodegradation with NIO have been investigated, oxalic acid was the most effective carboxylic acid used at pH 3. A similar trend was observed for the removal of total organic carbon (TOC), 75% of TOC was removed. The analytical study showed many aromatic intermediates, short-chain carboxylic acids and inorganic ion.


Assuntos
Ácidos Carboxílicos/química , Compostos Férricos/química , Herbicidas/efeitos da radiação , Compostos de Fenilureia/efeitos da radiação , Fotólise , Eliminação de Resíduos Líquidos/métodos , Meia-Vida , Herbicidas/química , Oxirredução , Compostos de Fenilureia/química , Luz Solar
10.
J Agric Food Chem ; 63(50): 10768-77, 2015 Dec 23.
Artigo em Inglês | MEDLINE | ID: mdl-26616105

RESUMO

The photodegradation of the imidazolinone herbicides imazamox, imazapic, imazaquin, and imazamethabenz-methyl has been investigated in phosphate-buffered solutions and buffered solutions containing natural organic matter (NOM). The hydrolysis of imazamethabenz-methyl, the only imidazolinone herbicide susceptible to hydrolysis, was also examined. The rate of hydrolysis of imazamethabenz-methyl increased with increasing pH, with the para isomer degrading more rapidly than the meta isomer. All photodegradation rate constants increased with pH and plateaued after pH 5.2. All imidzaolinones degraded more quickly under 253.7 nm lamps as compared to degradation under 310 nm lamps. Imazamox and imazapic degraded more rapidly than imazaquin at all pH values and had higher quantum yields. In addition, imazamox and imazapic quantum yields increased as a function of pH, whereas imazaquin quantum yields showed no trend as a function of pH. Photodegradation reaction rate constants decreased as the concentration of NOM was increased in the solutions due to the effect of light screening. Formulas for the proposed photoproducts for imazamox, imazapic, and imazaquin in pH 7 phosphate buffers were identified, and structures for the photoproducts are proposed.


Assuntos
Benzoatos/química , Herbicidas/química , Imidazóis/química , Fotólise , Quinolinas/química , Soluções , Biodegradação Ambiental , Herbicidas/efeitos da radiação , Concentração de Íons de Hidrogênio , Hidrólise , Estrutura Molecular , Ácidos Nicotínicos/química , Água
11.
J Hazard Mater ; 288: 147-57, 2015 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-25725267

RESUMO

The degradation of atrazine was investigated in aqueous solution by gamma-ray irradiation. 8.11 µM initial atrazine concentration could be completely removed in N2 saturated solution by applying 3500 Gy radiation dose at a dose rate of 296 Gy h(-1). Significant removal of atrazine (i.e., 39.4%) was observed at an absorbed dose of 1184 Gy in air saturated solution and the removal efficiency was promoted to 50.5 and 65.4% in the presence of N2O and N2 gases, respectively. The relative contributions of hydrated electron, hydroxyl radical and hydrogen radical toward atrazine degradation were determined as ratio of observed dose constant (kobs) and found to be 5: 3: 1 for keaq(-): k·OH: kH·, respectively. The degradation efficiency of atrazine was 69.5, 55.6 and 37.3% at pH 12.1, 1.7 and 5.7, respectively. A degradation mechanism was proposed based on the identified degradation by-products by gas chromatography-mass spectrometry. Taking the relative contributions of oxidative and reductive species to atrazine degradation into account, reductive pathway proved to be a better approach for the radiolytic treatment of atrazine contaminated water.


Assuntos
Atrazina/química , Atrazina/efeitos da radiação , Herbicidas/química , Herbicidas/efeitos da radiação , Radical Hidroxila/química , Prótons , Cromatografia Gasosa-Espectrometria de Massas , Concentração de Íons de Hidrogênio , Cinética , Eliminação de Resíduos Líquidos , Poluentes Químicos da Água , Purificação da Água , Raios X
12.
Chemosphere ; 119: 601-607, 2015 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-25128892

RESUMO

This work models the phototransformation kinetics in surface waters of five phenylurea herbicides (diuron, fenuron, isoproturon, metoxuron and chlortoluron), for which important photochemical parameters are available in the literature (direct photolysis quantum yields and reaction rate constants with ·OH, CO3(-·) and the triplet states of chromophoric dissolved organic matter, (3)CDOM*). Model calculations suggest that isoproturon and metoxuron would be the least photochemically persistent and diuron the most persistent compound. Reactions with ·OH and (3)CDOM* would be the main phototransformation pathways for all compounds in the majority of environmental conditions. Reaction with CO3(-) could be important in waters with low dissolved organic carbon (DOC), while direct photolysis would be negligible for fenuron, quite important for chlortoluron, and somewhat significant for the other compounds. The direct photolysis of metoxuron and diuron is known to increase toxicity, and such a photoreaction pathway would be enhanced at intermediate DOC values (1-4 mg C L(1)). The reaction between phenylureas and ·OH is known to produce toxic intermediates, differently from (3)CDOM*. Therefore, the shift of reactivity from ·OH to (3)CDOM* with increasing DOC could reduce the environmental impact of photochemical transformation.


Assuntos
Água Doce/química , Substâncias Perigosas/análise , Herbicidas/análise , Compostos de Fenilureia/análise , Fotólise , Poluentes Químicos da Água/análise , Substâncias Perigosas/química , Substâncias Perigosas/efeitos da radiação , Herbicidas/química , Herbicidas/efeitos da radiação , Cinética , Modelos Químicos , Compostos de Fenilureia/química , Compostos de Fenilureia/efeitos da radiação , Poluentes Químicos da Água/química , Poluentes Químicos da Água/efeitos da radiação
13.
J Environ Sci (China) ; 26(6): 1332-9, 2014 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-25079845

RESUMO

We used a ultrasound/Fe(2+)/H2O2 process in continuous dosing mode to degrade the alachlor. Experimental results indicated that lower pH levels enhanced the degradation and mineralization of alachlor. The maximum alachlor degradation (initial alachlor concentration of 50 mg/L) was as high as 100% at pH 3 with ultrasound of 100 Watts, 20 mg/L of Fe(2+), 2 mg/min of H2O2 and 20°C within 60 min reaction combined with 46.8% total organic carbon removal. Higher reaction temperatures inhibited the degradation of alachlor. Adequate dosages of Fe(2+) and H2O2 in ultrasound/Fe(2+)/H2O2 process not only enhance the degradation efficiency of alachlor but also save the operational cost than the sole ultrasound or Fenton process. A continuous dosing mode ultrasound/Fe(2+)/H2O2 process was proven as an effective method to degrade the alachlor.


Assuntos
Acetamidas/química , Herbicidas/química , Peróxido de Hidrogênio/química , Ferro/química , Poluentes Químicos da Água/química , Acetamidas/efeitos da radiação , Estudos de Viabilidade , Herbicidas/efeitos da radiação , Som , Temperatura , Águas Residuárias/química , Poluentes Químicos da Água/efeitos da radiação
14.
Talanta ; 127: 169-74, 2014 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-24913872

RESUMO

Nonelectroactive acetochlor can be indirectly determined through the photocatalytical degradation of acetochlor. A derivative visible light photoelectrochemical sensor for indirect detection of the herbicide acetochlor using TiO2-poly(3-hexylthiophene)-ionic liquid nanocomposite is constructed. Poly(3-hexylthiophene) (P3HT) was synthesized via chemical oxidative polymerization with anhydrous FeCl3 as oxidant, 3-hexylthiophene as monomer, chloroform as solvent, and the functional TiO2 nanoparticles were facilely prepared by blending TiO2 nanoparticles and P3HT at room temperature ionic liquid, 1-Butyl-3-methylimidazolium hexafluorophosphate solution. Operational parameters, including the photolysis time, ratios of TiO2 to P3HT, bias voltage and pH of buffer solution have been optimized. Under optimal conditions, the proposed photoelectrochemical method could detect acetochlor ranging from 0.5 to 20 µmol L(-1) with a detection limit of 0.2 nmol L(-1) at a signal-to-noise ratio of 3. The assay results of acetochlor in water samples with the proposed method were in acceptable agreement with those of the gas chromatograph-mass spectrometer (GC-MS) method. The promising sensor opens a new opportunity for fast, portable, and sensitive analysis of acetochlor in environmental samples.


Assuntos
Herbicidas/análise , Nanocompostos/química , Tiofenos/química , Titânio/química , Toluidinas/análise , Carbono/química , Técnicas Eletroquímicas , Eletrodos , Herbicidas/química , Herbicidas/efeitos da radiação , Imidazóis/química , Líquidos Iônicos/química , Luz , Processos Fotoquímicos , Toluidinas/química , Toluidinas/efeitos da radiação
15.
Environ Sci Process Impacts ; 16(9): 2098-107, 2014 Sep 20.
Artigo em Inglês | MEDLINE | ID: mdl-24828085

RESUMO

Photolytic transformation of organic contaminants in wetlands can be mediated by chromophoric dissolved organic matter (CDOM), which in turn can lose its reactivity from photobleaching. We collected water from a small agricultural wetland (Ohio), Kawai Nui Marsh (Hawaii), the Everglades (Florida), and Okefenokee Swamp (Georgia) to assess the effect of photobleaching on the photofate of two herbicides, acetochlor and isoproturon. Analyte-spiked water samples were irradiated using a solar simulator and monitored for changes in CDOM light absorbance and dissolved oxygen. Photobleaching did not significantly impact the indirect photolysis rates of either herbicide over 24 hours of irradiation. Surprisingly, the opposite effect was observed with isoproturon, which accelerated DOM photobleaching. This phenomenon was more pronounced in higher-CDOM waters, and we believe that the redox pathway between triplet-state CDOM and isoproturon may be responsible for our observations. By contrast, acetochlor indirect photolysis was dependent on reaction with the hydroxyl radical and did not accelerate photobleaching of wetland water as much as isoproturon. Finally, herbicide indirect photolysis rate constants did not correlate strongly to any one chemical or optical property of the sampled waters.


Assuntos
Herbicidas/efeitos da radiação , Compostos de Fenilureia/efeitos da radiação , Toluidinas/efeitos da radiação , Poluentes Químicos da Água/efeitos da radiação , Áreas Alagadas , Oxigênio/análise , Fotodegradação , Fotólise , Luz Solar , Estados Unidos
16.
J Hazard Mater ; 275: 166-74, 2014 Jun 30.
Artigo em Inglês | MEDLINE | ID: mdl-24862347

RESUMO

The effectiveness of sonolysis (US), photolysis (UV), and sonophotolysis (USUV) for the degradation of atrazine (ATZ) was investigated. An untypical kinetics analysis was found useful to describe the combined process, which is compatible to pseudo first-order kinetics. The heterogeneous environments of two different ultrasounds (20 and 400 kHz) were evaluated. The heterogeneous distribution of ATZ in the ultrasonic solution was found critical in determining the reaction rates at different frequencies. The presence of NaCl would promote/inhibit the rates by the growth and decline of "salting out" effect and surface tension. The benefits of combining these two processes were for the first time investigated from the aspect of promoting the intermediates degradation which were resistant in individual processes. UV caused a rapid transformation of ATZ to 2-hydroxyatrazine (OIET), which was insensitive to UV irradiation; however, US and USUV were able to degrade OIET and other intermediates through •OH attack. On the other hand, UV irradiation also could promote radical generation via H2O2 decomposition, thereby resulting in less accumulation of more hydrophilic intermediates, which are difficult to degradation in the US process. Reaction pathways for ATZ degradation by all three processes are proposed. USUV achieved the greatest degree of ATZ mineralization with more than 60% TOC removed, contributed solely by the oxidation of side chains. Ammeline was found to be the only end-product in both US and USUV processes.


Assuntos
Atrazina/efeitos da radiação , Herbicidas/efeitos da radiação , Sonicação , Raios Ultravioleta , Purificação da Água/métodos , Atrazina/química , Herbicidas/química , Microbolhas , Oxirredução , Fotólise , Cloreto de Sódio/química , Triazinas/química
17.
Environ Technol ; 35(1-4): 407-15, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-24600881

RESUMO

Semiconductor-mediated hydrogen peroxide-assisted photocatalytic degradation of a selected herbicide, Bentazone (1) has been investigated in aqueous suspensions of TiO2 under a variety of conditions. The degradation was studied by monitoring the depletion in total organic carbon content as a function of irradiation time. The degradation kinetics was investigated under different conditions such as type of TiO2 (Anatase/Anatase-Rutile mixture), reaction pH, catalyst dosage and hydrogen peroxide (H202) concentration. The degradation rates were found to be strongly influenced by all the above parameters. Titanium dioxide Degussa P25 was found to be more efficient as compared with other two commercially available TiO2 powders like Hombikat UV100 and PC500 from Millennium Inorganic Chemicals. Gas Chromatography-Mass Spectrometry (GC-MS) analysis of the irradiated mixture of Bentazone (1) indicates the formation of several intermediate products which have been characterized on the basis of molecular ion/mass fragmentation pattern and also on comparison with the National Institute of Standards and Technology (NIST) library. Plausible mechanism for the formation of different products during photocatalytic treatment of Bentazone in the presence of TiO2 has been proposed. The use of H202 substantially increased the efficiency of TiO2 photocatalytic degradation.


Assuntos
Benzotiadiazinas/química , Herbicidas/química , Minerais/química , Titânio/química , Poluentes Químicos da Água/química , Purificação da Água/métodos , Água/química , Benzotiadiazinas/isolamento & purificação , Benzotiadiazinas/efeitos da radiação , Herbicidas/isolamento & purificação , Herbicidas/efeitos da radiação , Luz , Fotoquímica/instrumentação , Fotoquímica/métodos , Semicondutores , Suspensões , Titânio/efeitos da radiação , Poluentes Químicos da Água/isolamento & purificação , Poluentes Químicos da Água/efeitos da radiação , Purificação da Água/instrumentação
18.
J Environ Sci Health B ; 48(11): 919-26, 2013.
Artigo em Inglês | MEDLINE | ID: mdl-23998303

RESUMO

Photolysis of oxyfluorfen, an herbicide of the nitrodiphenyl ether class, was studied in aqueous methanol under UV and sunlight. UV irradiation was carried out in a borosilicate glass photoreactor (containing 250 ppm oxyfluorfen in 50% aqueous methanol) equipped with a quartz filter and 125 watt mercury lamp (maximum output 254 nm) at 25 ± 1°C. Sunlight irradiation was conducted at 28 ± 1°C in borosilicate Erlenmeyer flasks containing 250 ppm oxyfluorfen in 50% aqueous methanol. The samples from both the irradiated conditions were withdrawn at a definite time interval and extracted to measure oxyfluorfen content by gas chromatography-flame ionization detector for rate study. The half-life values were 20 hours and 2.7 days under UV and sunlight exposure, respectively. Photolysis of oxyfluorfen yielded 13 photoproducts of which three were characterized by infrared spectrophotometer and (1)H NMR and (13)C NMR spectroscopy. The rest of the photoproducts were identified by gas chromatography-mass spectrometry (GC-MS) and thin layer chromatography (TLC). An ionization potential 70 eV was used for electron impact-mass spectrometry (EI-MS) and methane was used as reagent gas for chemical ionization-mass spectrometry (CI-MS). Two of the photoproducts were also synthesized for comparison. The main phototransformation pathways of oxyfluorfen involved nitro reduction, dechlorination, and hydrolysis as well as nucleophiles displacement reaction.


Assuntos
Éteres Difenil Halogenados/efeitos da radiação , Herbicidas/efeitos da radiação , Fotólise , Luz Solar , Raios Ultravioleta , Cromatografia em Camada Fina , Cromatografia Gasosa-Espectrometria de Massas , Meia-Vida , Éteres Difenil Halogenados/química , Herbicidas/química , Espectroscopia de Ressonância Magnética , Metanol/química , Espectrofotometria Infravermelho
19.
J Environ Sci Health B ; 48(11): 927-34, 2013.
Artigo em Inglês | MEDLINE | ID: mdl-23998304

RESUMO

The degradation of atrazine in aqueous solution by UV or UV/H2O2 processes, and the toxic effects of the degradation products were explored. The mineralization of atrazine was not observed in the UV irradiation process, resulting in the production of hydroxyatrazine (OIET) as the final product. In the UV/H2O2 process, the final product was ammeline (OAAT), which was obtained by two different pathways of reaction: dechlorination followed by hydroxylation, and the de-alkylation of atrazine. The by-products of the reaction of dechlorination followed by hydroxylation were OIET and hydroxydeethyl atrazine (OIAT), and those of de-alkylation were deisopropyl atrazine (CEAT), deethyl atrazine (CIAT), and deethyldeisopropyl atrazine (CAAT). OIAT and OAAT appeared to be quite stable in the degradation of atrazine by the UV/H2O2 process. In a toxicity test using Daphnia magna, the acute toxic unit (TUa) was less than 1 of TUa (100/EC50, %) in the UV/H2O2 process after 30 min of reaction time, while 1.2 to 1.3 of TUa was observed in the UV process. The TUa values of atrazine and the degradation products have the following decreasing order: OIET> Atrazine> CEAT≈CIAT> CAAT. OIAT and OAAT did not show any toxic effects.


Assuntos
Atrazina/química , Atrazina/efeitos da radiação , Herbicidas/química , Herbicidas/efeitos da radiação , Peróxido de Hidrogênio/química , Raios Ultravioleta , Animais , Cromatografia Líquida , Daphnia/efeitos dos fármacos , Espectrometria de Massas , Testes de Toxicidade
20.
Environ Technol ; 34(5-8): 1043-51, 2013.
Artigo em Inglês | MEDLINE | ID: mdl-23837356

RESUMO

The breakdown of pesticides has been promoted by many methods for clean up of contaminated soil and wastewaters. The main goal is to decrease the toxicity of the parent compound to achieve non-toxic compounds or even, when complete mineralization occurs, carbon dioxide and water. Therefore, electrochemical degradation (potentiostatic and galvanostatic) of both the pesticide atrazine and cyanuric acid (CA) at boron-doped diamond (BDD) and Ti/Ru0.3Ti0.7O2 dimensionally stable anode (DSA) electrodes, in different supporting electrolytes (NaCl and Na2SO4), is presented with the aim of establishing the influence of the operational parameters on the process efficiency. The results demonstrate that both the electrode material and the supporting electrolyte have a strong influence on the rate of atrazine removal. In the chloride medium, the rate of atrazine removal is always greater than in sulfate under all conditions employed. Furthermore, in the sulfate medium, atrazine degradation was significant only at the BDD electrode. The total organic carbon (TOC) load decreased by 79% and 56% at the BDD and DSA electrodes, respectively, in the chloride medium. This trend was maintained in the sulfate medium but the TOC removal was lower (i.e. 33% and 13% at BDD and DSA electrodes, respectively). CA, a stable atrazine degradation intermediate, was also studied and it is efficiently removed using the BDD electrode in both media, mainly when high current densities are employed. The use of the BDD electrode in the chloride medium not only degrades atrazine but also mineralized cyanuric acid leading to the higher TOC removal.


Assuntos
Atrazina/química , Boro/química , Diamante/química , Eletroquímica/instrumentação , Triazinas/química , Poluentes Químicos da Água/química , Purificação da Água/instrumentação , Atrazina/isolamento & purificação , Atrazina/efeitos da radiação , Eletrodos , Desenho de Equipamento , Análise de Falha de Equipamento , Herbicidas/química , Herbicidas/isolamento & purificação , Herbicidas/efeitos da radiação , Óxidos/química , Triazinas/isolamento & purificação , Triazinas/efeitos da radiação , Poluentes Químicos da Água/isolamento & purificação , Poluentes Químicos da Água/efeitos da radiação
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