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1.
J Environ Sci Health B ; 54(4): 226-236, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-30633640

RESUMO

Spent coffee grounds (SCG) have been used for the production of activated carbon (AC) by impregnation with different ratios of phosphoric acid at 600 °C, Xp (H3PO4/coffee): 3:130%, 4:130%, 3:150% and 4:150%. The obtained AC was characterized by BET, FTIR and SEM. BET surface area corresponds to 803.422 m2 g-1. The influences of the main parameters such as contact time, the pesticides initial concentration, adsorbent dose, pH and temperature on the efficiency of separation process were investigated during the batch operational mode. Results were modeled by adsorption isotherms: Langmuir, Freundlich and Temkin isotherms, which gave satisfactory correlation coefficients. The maximum adsorption capacities calculated from the Langmuir isotherms were 11.918 mg g-1 for carbendazim and 5.834 mg g-1 for linuron at room temperature. Adsorption kinetics of carbendazim and linuron have been studied by the pseudo-first-order, the pseudo-second-order and the intraparticle diffusion model. The results of adsorption kinetics have been fitted the best by pseudo-second-order model. The resulted data from FTIR characterization pointed to the presence of many functional groups on the AC surface. SCG adsorbent, as an eco-friendly and low-cost material, showed high potential for the removal of carbendazim and linuron from aqueous solutions.


Assuntos
Benzimidazóis/isolamento & purificação , Carbamatos/isolamento & purificação , Carvão Vegetal/química , Café/química , Linurona/isolamento & purificação , Purificação da Água/métodos , Adsorção , Benzimidazóis/química , Carbamatos/química , Cinética , Linurona/química , Ácidos Fosfóricos/química , Soluções/química , Espectroscopia de Infravermelho com Transformada de Fourier , Temperatura , Termodinâmica , Água/química , Poluentes Químicos da Água/química , Poluentes Químicos da Água/isolamento & purificação
2.
Ecotoxicol Environ Saf ; 168: 479-485, 2019 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-30423512

RESUMO

The dissipation of difenoconazole and linuron using an open-field experimental approach with carrots exposed to one-, two- and fivefold the recommended dose of the pesticides was evaluated to provide safe recommendation to ensure food safety of carrots. The pesticide residue analysis was performed with solid-liquid extraction with low temperature partitioning technique (SLE/LTP) followed by gas chromatography analysis. The recovery percentages of extracts obtained from samples of carrot passed through SLE/LTP extraction and fortified with difenoconazole and linuron pesticides varied from 93.4% to 106.3% and from 95.1% to 116.6%, respectively. The limit of detection for difenoconazole was 0.02 and 0.12 mg kg-1 for linuron. The limit of quantification for difenoconazole was 0.05 and 0.36 mg kg-1 for linuron. The degradation time for fifty percent of the applied pesticide at the different doses ranged from 2.4 to 3.6 days for difenoconazole and from 7.5 to 10.5 days for linuron. At the end of the pre-harvest interval, carrots treated with fivefold the recommended dose of both pesticides were considered unfit for consumption. Despite monitoring the degradation products of the applied pesticides by gas chromatography coupled to mass spectrometer, none degradation product was identified on the carrots.


Assuntos
Daucus carota/química , Dioxolanos/química , Linurona/química , Triazóis/química , Cromatografia Gasosa , Relação Dose-Resposta a Droga , Inocuidade dos Alimentos , Limite de Detecção , Resíduos de Praguicidas/análise , Praguicidas/química , Reprodutibilidade dos Testes
3.
Artigo em Inglês | MEDLINE | ID: mdl-28109972

RESUMO

Urea-based herbicides are applied in agriculture to control broadleaf and grassy weeds, acting to either inhibit photosynthesis at photosystem II (phenylureas) or to inhibit acetolactate synthase acetohydroxyacid synthase (sulfonylureas). While there are different chemical formulas for urea-based herbicides, the phenylureas are a widely used class in North America and have been detected in aquatic environments due to agricultural run-off. Here, we summarize the current state of the literature, synthesizing data on phenylureas and their biological effects in two non-target animals, fish and amphibians, with a primary focus on diuron and linuron. In fish, although the acutely lethal effects of diuron in early life stages appear to be >1mg/L, recent studies measuring sub-lethal behavioural and developmental endpoints suggest that diuron causes adverse effects at lower concentrations (i.e. <0.1mg/L). Considerably less toxicity data exist for amphibians, and this is a knowledge gap in the literature. In terms of sub-lethal effects and mode of action (MOA), linuron is well documented to have anti-androgenic effects in vertebrates, including fish. However, there are other MOAs that are not adequately assessed in toxicology studies. In order to identify additional potential MOAs, we conducted in silico analyses for linuron and diuron that were based upon transcriptome studies and chemical structure-function relationships (i.e. ToxCast™, Prediction of Activity Spectra of Substances). Based upon these analyses, we suggest that steroid biosynthesis, cholesterol metabolism and pregnane X receptor activation are common targets, and offer some new endpoints for future investigations of phenylurea herbicides in non-target animals.


Assuntos
Anfíbios/fisiologia , Disruptores Endócrinos/toxicidade , Peixes/fisiologia , Herbicidas/toxicidade , Resíduos de Praguicidas/toxicidade , Compostos de Fenilureia/toxicidade , Poluentes Químicos da Água/toxicidade , Anfíbios/embriologia , Anfíbios/crescimento & desenvolvimento , Animais , Hibridização Genômica Comparativa , Biologia Computacional , Diurona/química , Diurona/toxicidade , Disruptores Endócrinos/química , Peixes/embriologia , Peixes/crescimento & desenvolvimento , Herbicidas/química , Linurona/química , Linurona/toxicidade , Estrutura Molecular , Drogas Antiandrogênicas não Esteroides/química , Drogas Antiandrogênicas não Esteroides/toxicidade , Concentração Osmolar , Resíduos de Praguicidas/química , Compostos de Fenilureia/química , Relação Estrutura-Atividade , Transcriptoma/efeitos dos fármacos , Poluentes Químicos da Água/química
4.
Environ Technol ; 38(1): 78-84, 2017 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-27156531

RESUMO

A two-phase membrane extraction in a hollow fibre contactor with feed-stream recycle was applied to remove selected pesticides (tebufenozide, linuron, imidacloprid, acetamiprid and dimethoate) from their mixed aqueous solutions. The contactor consisted of 50 polypropylene hollow fibres impregnated with 5% tri-n-octylphosphine oxide in di-n-hexyl ether. For low-polar pesticides with log P ≥ 2 (tebufenozide and linuron), the maximum removal efficiency increased linearly from 85% to 96% with increasing the feed flow rate. The maximum removal efficiencies of more polar pesticides were significantly higher under feed recirculation (86%) than in a continuous single-pass operation (30%). It was found from the Wilson's plot that the mass transfer resistance of the liquid membrane can be neglected for low-polar pesticides. The pesticide removals from commercial formulations were similar to those from pure pesticide solutions, indicating that built-in adjuvants did not affect the extraction process.


Assuntos
Praguicidas/química , Eliminação de Resíduos Líquidos/métodos , Poluentes Químicos da Água/química , Dimetoato/química , Hidrazinas/química , Imidazóis/química , Resíduos Industriais , Linurona/química , Extração Líquido-Líquido , Membranas Artificiais , Neonicotinoides , Nitrocompostos/química , Compostos Organofosforados/química , Polipropilenos/química , Piridinas/química , Reciclagem , Eliminação de Resíduos Líquidos/instrumentação , Águas Residuárias/química
5.
Huan Jing Ke Xue ; 36(5): 1668-73, 2015 May.
Artigo em Chinês | MEDLINE | ID: mdl-26314114

RESUMO

Chlorination degradation of linuron was studied using the common disinfectant sodium hypochlorite, the effects of chlorine dosage, pH value, bromine ion concentrationand temperature were systematically investigated, and the formation characteristics of disinfection by-products (DBPs) during the chlorination reaction was analyzed. The results showed that the chlorination degradation kinetics of linuron by sodium hypochlorite could be well described by the second-order kinetic model. Moreover, pH values had a great impact on the degradation reaction, and the rate constant reached the maximum level at pH 7, and the base elementary reaction rate constants of HOCl and OCl- with linuron were 4.84 x 10(2) L · (mol · h)(-1) and 3.80 x 10(2) L · (mol · h)(-1), respectively. The reaction rate decreased with the addition of bromide ion and increased with increasing temperature. Furthermore, many kinds of disinfection by- products were produced during the chlorination degradation of linuron, including CF, DCAN, TCNM and halogen acetone. Under conditions of different solution pH and different bromide ion concentrations, there would be significant difference in the types and concentrations of disinfection by-products.


Assuntos
Desinfecção , Água Potável/química , Halogenação , Linurona/química , Purificação da Água , Bromo , Cloro , Desinfetantes , Halogênios , Cinética , Hipoclorito de Sódio
6.
J Environ Sci Health B ; 50(8): 544-51, 2015.
Artigo em Inglês | MEDLINE | ID: mdl-26065514

RESUMO

Biochar is increasingly been used as a soil amendment to improve water-holding capacity, reduce nutrient leaching, increase soil pH, and also as a means to reduce contamination through sorption of heavy metals or organic pollutants. The sorption behavior of three phenylurea herbicides (monuron, diuron and linuron) on five biochars (Enhanced Biochar, Hog Waste, Turkey Litter, Walnut Shell and Wood Feedstock) and an agricultural soil (Yolo silt loam) was investigated using a batch equilibration method. Sorption isotherms of herbicides to biochars were well described by the Freundlich model (R(2) = 0.93-0.97). The adsorption KF values ranged from 6.94 to 1306.95 mg kg(-1) and indicated the sorption of herbicides in the biochars and Yolo soil was in the sequence of linuron > diuron > monuron and walnut shell biochar > wood feedstock biochar > turkey litter biochar > enhanced biochar > hog waste biochar > Yolo soil. These data show that sorption of herbicides to biochar can have both positive (reduced off-site transport) and negative (reduced herbicide efficacy) implications and specific biochar properties, such as H/C ratio and surface area, should be considered together with soil type, agriculture chemical and climate condition in biochar application to agricultural soil to optimize the system for both agricultural and environmental benefits.


Assuntos
Carvão Vegetal/química , Herbicidas/química , Compostos de Fenilureia/química , Poluentes do Solo/química , Solo/química , Adsorção , Agricultura , Diurona/química , Linurona/química , Esterco , Compostos de Metilureia/química , Madeira
7.
Sci Total Environ ; 476-477: 611-21, 2014 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-24496034

RESUMO

Dissipation kinetics of pesticides belonging to three chemical groups (linuron, diazinon and myclobutanil) was studied in an unamended agricultural soil and in this soil amended with three organic residues: sewage sludge (SS), grape marc (GM) and spent mushroom substrate (SMS). The soils were incubated with the residues outdoors for one and 12 months. Mineralized, extracted and non-extractable fractions were also studied for (14)C-linuron and (14)C-diazinon. The dissipation kinetics was fitted to single first-order or first-order multicompartment models. The dissipation rate (k) decreased in the order diazinon>linuron>myclobutanil, and DT50 values decreased for linuron (1.6-4.8 times) or increased for myclobutanil (1.7-2.6 times) and diazinon (1.8-2.3 times) in the amended soils relative to the unamended soil. The lowest DT50 values for the three pesticides were recorded in GM-amended soil, and the highest values in SMS-amended soil. After 12 months of soil incubation, DT50 values decreased in both the unamended and amended soils for linuron, but increased for the unamended and SMS-amended soil for diazinon and myclobutanil. A certain relationship was observed between the sorption of pesticides by the soils and DT50 values, although it was significant only for myclobutanil (p<0.05). Dissipation mechanism recorded the lowest mineralization of (14)C-pesticides in the GM-soil despite the highest dissipation rate in this soil. The extracted (14)C-residues decreased with incubation time, with increased formation of non-extractable residues, higher in amended soils relative to the unamended soil. Soil dehydrogenase activity was, in general, stimulated by the addition of the organic amendments and pesticides to the soil after one month and 12 months of incubation. The results obtained revealed that the simultaneous use of amendments and pesticides in soils requires a previous study in order to check the environmental specific persistence of these compounds and their effectiveness in amended soils.


Assuntos
Modelos Químicos , Praguicidas/química , Poluentes do Solo/química , Solo/química , Agaricales , Agricultura , Diazinon/química , Linurona/química , Nitrilas/química , Esgotos , Triazóis/química
8.
Environ Sci Pollut Res Int ; 21(4): 2654-62, 2014 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-24122163

RESUMO

Sorption and biodegradation are the main mechanisms for the removal of endocrine disruptor compounds (EDs) from both solid and liquid matrices. There are recent evidences about the capacity of white-rot fungi to decontaminate water systems from phenolic EDs by means of their ligninolytic enzymes. Most of the available studies report the removal of EDs by biodegradation or adsorption separately. This study assessed the simultaneous removal of five EDs­the xenoestrogens bisphenol A (BPA), ethynilestradiol (EE2), and 4-n-nonylphenol (NP), and the herbicide linuron and the insecticide dimethoate­from a municipal landfill leachate (MLL) using a combined sorption/bioremoval approach. The adsorption matrices used were potato dextrose agar alone or added with each of the following adsorbent materials: ground almond shells, a coffee compost, a coconut fiber, and a river sediment. These matrices were either not inoculated or inoculated with the fungus Pleurotus ostreatus and superimposed on the MLL. The residual amount of each ED in the MLL was quantified after 4, 7, 12, and 20 days by HPLC analysis and UV detection. Preliminary experiments showed that (1) all EDs did not degrade significantly in the untreatedMLL for at least 28 days, (2) the mycelial growth of P. ostreatus was largely stimulated by components of the MLL, and (3) the enrichment of potato dextrose agar with any adsorbent material favored the fungal growth for 8 days after inoculation. A prompt relevant disappearance of EDs in the MLL occurred both without and, especially, with fungal activity, with the only exception of the very water soluble dimethoate that was poorly adsorbed and possibly degraded only during the first few days of experiments. An almost complete removal of phenolic EDs, especially EE2 and NP, occurred after 20 days or much earlier and was generally enhanced by the adsorbent materials used. Data obtained indicated that both adsorption and biodegradation mechanisms contribute significantly to MLL decontamination from the EDs studied and that the efficacy of the methodology adopted is directly related to the hydrophobicity of the contaminant.


Assuntos
Disruptores Endócrinos/química , Disruptores Endócrinos/metabolismo , Pleurotus/metabolismo , Poluentes Químicos da Água/química , Poluentes Químicos da Água/metabolismo , Adsorção , Compostos Benzidrílicos/química , Compostos Benzidrílicos/metabolismo , Biodegradação Ambiental , Cocos , Descontaminação , Dimetoato/química , Dimetoato/metabolismo , Etinilestradiol/química , Etinilestradiol/metabolismo , Sedimentos Geológicos/química , Linurona/química , Linurona/metabolismo , Fenóis/química , Fenóis/metabolismo , Prunus , Instalações de Eliminação de Resíduos
9.
Environ Monit Assess ; 185(10): 8109-14, 2013 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-23525775

RESUMO

It is widely recognised that complex interactions occur between chemicals in mixtures. In many agricultural situations, the use of tank mixes and complex spray programs is a common practice. Insecticides, fungicides and a herbicide being applied in potato protection were used in this research. Interactions between linuron and insecticides, such as thiamethoxam or clothianidin, and fungicides, such as mancozeb or chlorothalonil, were examined in soil. The degradation rate of linuron in soil during laboratory incubation in six treatments was studied. Mixtures of linuron with mancozeb in sandy loam and clay loam soils had a significant effect on the persistence of this herbicide. For example, for the same herbicide, t 1/2 values for linuron were from 37 days in sandy loam to 44 days in clay loam. These values changed (64-67 days) when thiamethoxam and mancozeb were in soil. When mancozeb was added only, the half-life values were from 59 to 62 days, respectively. Other mixtures with chlorothalonil, thiamethoxam and clothianidin did not have any effect. In order to compare linuron degradation rates in soils, a single first-order model and expanded statistical analysis were used.


Assuntos
Modelos Químicos , Praguicidas/análise , Poluentes do Solo/análise , Solo/química , Meia-Vida , Linurona/química , Praguicidas/química , Poluentes do Solo/química
10.
Environ Sci Pollut Res Int ; 20(2): 855-61, 2013 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-23128990

RESUMO

Pesticides that contain a halogen functional group have been destructed by means of detonative combustion. The following compounds were examined: (1) atrazine-2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine-herbicide; (2) bromophos-O,4-bromo-2,5-dichlorophenyl O,O-dimethyl phosphorothioate-insecticide; (3) chloridazon-5-amino-4-chloro-2-phenylopyridazin-3(2H)-one-herbicide; (4) linuron-3-(3,4-dichlorophenyl)-1-metoxy-1-methylurea-herbicide; (5) metoxychlor-1,1,1-trichloro-2,2-bis(4-metoxyphenyl)ethane-insecticide and acaricide; and (6) trichlorfon-dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate-insecticide. Explosive material has been produced on the basis of ammonium nitrate, which served as an oxidizer while the pesticides were used as fuels. Composition of the explosive was adjusted in such a way as to respect thermodynamic parameters. Detonative decomposition of the mixtures has been carried out in shot-holes pre-drilled in soil. Efficiency of the pesticide decomposition has been examined with gas chromatography in order to determine pesticides residues in the environment. It was found that for some, the amount of pesticides in some compounds in the analyzed samples after decomposition was below the determination threshold of the applied method.


Assuntos
Substâncias Explosivas/química , Praguicidas/química , Atrazina/química , Cromatografia Gasosa , Linurona/química , Metoxicloro/química , Nitratos/química , Organotiofosfatos/química , Resíduos de Praguicidas/química , Piridazinas/química , Poluentes do Solo/análise , Poluentes do Solo/química , Triclorfon/química
11.
Sensors (Basel) ; 12(1): 148-61, 2012.
Artigo em Inglês | MEDLINE | ID: mdl-22368461

RESUMO

This paper summarises the results of voltammetric studies on the herbicide 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (Linuron), using a carbon paste electrode containing tricresyl phosphate (TCP-CPE) as liquid binder. The principal experimental conditions, such as the pH effect, investigated in Britton-Robinson buffer solutions (pH 2.0-7.0), the peak characteristics for the analyte of interest, or instrumental parameters for the differential pulse voltammetric mode were optimized for the method. As found out, the best electroanalytical performance of the TCP-CPE was achieved at pH 2.0, whereby the oxidation peak of Linuron appeared at ca. +1.3 V vs. SCE. The analytical procedure developed offers good linearity in the concentration range of 1.25-44.20 µg mL(-1) (1.77 × 10(-4)-5.05 × 10(-6) mol L(-1)), showing-for the first time-the applicability of the TCP-CPE for anodic oxidations in direct voltammetry (without accumulation). The method was then verified by determining Linuron in a spiked river water sample and a commercial formulation and the results obtained agreed well with those obtained by the reference HPLC/UV determination.


Assuntos
Carbono/química , Técnicas Eletroquímicas/métodos , Herbicidas/análise , Linurona/análise , Tritolil Fosfatos/química , Eletrodos , Herbicidas/química , Concentração de Íons de Hidrogênio , Linurona/química , Reprodutibilidade dos Testes , Rios/química
12.
Ultrason Sonochem ; 18(5): 1107-12, 2011 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-21482475

RESUMO

The degradation of the phenylurea monolinuron (MLN) by ultrasound irradiation alone and in the presence of TiO(2) was investigated in aqueous solution. The experiments were carried out at low and high frequency (20 and 800 kHz) in complete darkness. The degradation of MLN by ultrasounds occurred mainly by a radical pathway, as shown the inhibitory effect of adding tert-butanol and bicarbonate ions to scavenge hydroxyl radicals. However, CO(3)(-) radicals were formed with bicarbonate and reacted in turn with MLN. In this study, the degradation rate of MLN and the rate constant of H(2)O(2) formation were used to evaluate the oxidative sonochemical efficiency. It was shown that ultrasound efficiency was improved in the presence of nanoparticles of TiO(2) and SiO(2) only at 20 kHz. These particles provide nucleation sites for cavitation bubbles at their surface, leading to an increase in the number of bubbles when the liquid is irradiated by ultrasound, thereby enhancing sonochemical reaction yield. In the case of TiO(2), sonochemical efficiency was found to be greater than with SiO(2) for the same mass introduced. In addition to the increase in the number of cavitation bubbles, activated species may be formed at the TiO(2) surface that promote the formation of H(2)O(2) and the decomposition of MLN.


Assuntos
Linurona/análogos & derivados , Sonicação/métodos , Poluentes Químicos da Água/química , Poluentes Químicos da Água/efeitos da radiação , Purificação da Água/métodos , Água/química , Linurona/química , Linurona/isolamento & purificação , Linurona/efeitos da radiação , Doses de Radiação , Poluentes Químicos da Água/isolamento & purificação
13.
Environ Sci Pollut Res Int ; 18(6): 949-57, 2011 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-21287284

RESUMO

INTRODUCTION: Photodegradation and hydrolysis of two substituted urea herbicides, monolinuron [3-(4-chlorophenyl)-1-methoxy-1-methylurea] and linuron [3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea], and one organophosphorous insecticide, phoxim [2-(diethoxyphosphinothioyloxyimino)-2-phenylacetonitrile], were studied using buffered sterilized distilled water (pH 4, 7 and 9). METHODS: Experiments were performed in the absence and presence of light (320-740 nm), while the effect of nitrates and humic acids on photodegradation was investigated for all pH values. An analytical method was developed and validated for the determination of target compounds in water samples using liquid chromatography positive ion electrospray-mass spectrometry. RESULTS: According to the results, substituted ureas neither hydrolyzed, at all tested pH values, nor photodegraded at pH 7 and 9. Slow photodegradation of the compounds was observed at pH 4. During 70 days of light exposure, initial concentrations of linuron and monolinuron were decreased by 54% and 31%, respectively, while the presence of nitrates slightly enhanced photodegradation of these compounds. On the other hand, phoxim was found to be very unstable for all the tested conditions and an increase of pH resulted to higher degradation. During hydrolysis experiments, the degradation of the compound ranged from 41% (pH 4) to 85% (pH 9) and the half-lives varied from 10 h (pH 9) to 204 h (pH 4). The presence of light enhanced phoxim degradation and as a result half-lives of 37, 22 and 9h were calculated for pH 4, 7 and 9, respectively. The addition of nitrates and humic acids did not significantly affect the photodegradation of phoxim. CONCLUSIONS: The results indicated that among the three tested pesticides, phoxim found to be the most sensitive in both photodegradation and hydrolysis.


Assuntos
Herbicidas/análise , Inseticidas/análise , Linurona/análogos & derivados , Compostos Organotiofosforados/análise , Fotólise , Ureia/análise , Cromatografia Líquida , Herbicidas/química , Concentração de Íons de Hidrogênio , Hidrólise , Inseticidas/química , Linurona/análise , Linurona/química , Compostos Organotiofosforados/química , Espectrometria de Massas por Ionização por Electrospray , Ureia/química , Água/química
14.
Talanta ; 83(5): 1763-8, 2011 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-21238781

RESUMO

A carbon paste electrode was used for the electrochemical determination of linuron concentrations in water and vegetable extracts. Optimal conditions were established with respect to electrode activation (electrochemical pretreatment), time accumulation, potential accumulation, scan rate, and pH. The limit of detection achieved with a pre-concentration step was 23.0 µg L(-1). Recovery measurements in vegetable extract and natural water samples were in the range of 98-103%, indicating that the proposed electrochemical method can be employed to analyze linuron in these matrices. The determination results were in good agreement with HPLC results.


Assuntos
Carbono/química , Linurona/química , Verduras/química , Água/química , Cromatografia Líquida de Alta Pressão , Eletroquímica/métodos , Eletrodos , Herbicidas/química , Linurona/análise , Estrutura Molecular , Potenciometria
15.
Chemosphere ; 82(10): 1415-21, 2011 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-21183199

RESUMO

A study has been made of the effect a reactive barrier made of pine (softwood) or oak (hardwood) wood intercalated in a sandy soil column has on the retention of linuron, alachlor and metalaxyl (pesticides with contrasting physicochemical characteristics). The leaching of pesticides has been carried out under a saturated flow regime and breakthrough curves (BTCs) have been obtained at flow rates of 1 m Lmin(-1) (all pesticides) and 3 m Lmin(-1) (linuron). The cumulative curves in the unmodified soil indicate a leaching of pesticides >80% of the total amount of compound added. After barrier intercalation, linuron leaching decreases significantly and a modification of the leaching kinetics of alachlor and metalaxyl has been observed. The theoretical R factors increased ∼2.6-3.3, 1.2-1.6-fold, and 1.4-1.7-fold and the concentration of the maximum peak decreased ∼6-12-fold, 2-4-fold and 1.2-2-fold for linuron, alachlor and metalaxyl, respectively. When considering the three pesticides, significant correlations have been found between the theoretical retardation factor (R) and the pore volume corresponding to the maximum peaks of the BTCs (r=0.77; p<0.05) or the total volume leached (r=-0.78; p<0.05). The results reveal the efficacy of reactive wood barriers to decrease the leaching of pesticides from point sources of pollution depends on the type of wood, the hydrophobicity of the pesticide and the adopted water flow rate. Pine was more effective than oak in decreasing the leaching of hydrophobic pesticide linuron or in decreasing the maximum peak concentration of the less hydrophobic pesticides in soils. Efficacy of these wood barriers was limited for the least hydrophobic pesticide metalaxyl.


Assuntos
Acetamidas/análise , Alanina/análogos & derivados , Linurona/análise , Poluentes do Solo/análise , Acetamidas/química , Alanina/análise , Alanina/química , Fungicidas Industriais/análise , Fungicidas Industriais/química , Herbicidas/análise , Herbicidas/química , Cinética , Linurona/química , Dióxido de Silício/química , Poluentes do Solo/química , Poluição Química da Água/prevenção & controle , Madeira/química
16.
J Agric Food Chem ; 58(20): 10935-44, 2010 Oct 27.
Artigo em Inglês | MEDLINE | ID: mdl-20886880

RESUMO

Metabolism of xenobiotics in plants usually occurs in three phases, phase I (primary metabolism), phase II (conjugation processes), and phase III (storage). The uptake and metabolism of [(14)C]diuron and [(14)C]linuron were investigated in wheat and radish. Seeds were sown in quartz sand and irrigated with a nutrient solution of either radioactive herbicide. Plants were harvested after two weeks, and metabolites were extracted and then analyzed by radio-reverse-high-performance liquid chromatography (HPLC). Uptake of the two molecules was higher in radish compared to wheat. Translocation of parent compounds and related metabolites from roots to aerial plant parts was important, especially for radish. A large proportion of extractable residues were found in radish whereas nonextractable residues amounted to 30% in wheat, mainly associated with roots. Chemical structure of metabolites was thereafter identified by acid, alkaline, and enzymatic hydrolyses followed by electrospray ionization mass spectrometry (ESI-MS) and proton nuclear magnetic resonance spectroscopy ((1)H NMR). This study highlighted the presence of diuron and linuron metabolites conjugated to sugars in addition to N-demethylation and N-demethoxylation products.


Assuntos
Diurona/metabolismo , Herbicidas/metabolismo , Linurona/metabolismo , Raphanus/metabolismo , Triticum/metabolismo , Radioisótopos de Carbono/análise , Radioisótopos de Carbono/metabolismo , Diurona/química , Herbicidas/química , Linurona/química , Raphanus/química , Triticum/química
17.
J Hazard Mater ; 180(1-3): 514-23, 2010 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-20471749

RESUMO

A comprehensive study of the degradation of linuron, one of the phenylurea herbicides, was conducted by using different treatment processes including UV, ozonation and UV/O(3). The effect of various anions on the performance of ozonation has been examined. N-terminus demethoxylation, photohydrolysis with or without dechlorination, and N-terminus demethylation have been found to be the major mechanisms in the linuron decay under the irradiation of UV at 254 nm while N-terminus demethoxylation, dechlorination and hydroxylation on benzene ring was observed to be involved in the ozonation process. Eight new intermediates were identified in UV process in this study compared with previous studies. Different decay pathways were proposed based on the identified intermediates in the three studied processes. UV/O(3) has demonstrated the best performance among these three processes in terms of LNR decay, mineralization, dechlorination and de-nitrogenation.


Assuntos
Herbicidas/química , Linurona/química , Ozônio/química , Raios Ultravioleta , Ânions
18.
Waste Manag ; 30(1): 41-9, 2010 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-19783419

RESUMO

The fate and effect of the herbicides linuron and metribuzin on the co-composting of sewage sludge and green waste were addressed in this work. The experiments were conducted in metal cubic containers of 1.0m(3) volume simulating a windrow composting system. A mixture of sludge and green waste was prepared at a ratio of 1:5 v/v. The mixture was split in four equal parts and the two herbicides were added, using a pressure sprayer, as sole or mixed pollutant in each of the three mixtures. The forth mixture was composted without any addition of herbicide, to serve as control. Temperature, physicochemical characteristics, herbicide concentration, carbon dioxide emission, methane emission and microbiological parameters were measured either daily or every time the mixtures were turned, for a period of 80 days. Both herbicides' concentration decreased significantly resulting in removal efficiencies of 99.1-99.7% and 95.8-96.0% for linuron and metribuzin, respectively. Incubation of microbiologically inactive mixtures at a temperature schedule following the spontaneous temperature evolution in the composters resulted in very little (1-11%) decomposition for both herbicides. Comparison of the variation of physicochemical parameters and microbial populations during composting indicated that both herbicides did not affect the composting process.


Assuntos
Linurona/química , Esgotos/química , Triazinas/química , Biodegradação Ambiental , Dióxido de Carbono/química , Físico-Química/métodos , Herbicidas/química , Cinética , Metano/química , Eliminação de Resíduos/métodos , Solo , Temperatura , Fatores de Tempo , Gerenciamento de Resíduos
19.
Talanta ; 80(2): 493-8, 2009 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-19836510

RESUMO

Partitioned dispersive liquid-liquid microextraction (PDLLME), using THF as the dispersive solvent and dichloromethane as the extraction solvent, was utilized to isolate and concentrate phenylurea herbicides (PUHs) from aqueous samples. In PDLLME, a dispersive solvent should be able to partition in the organic extractant droplets to effectively extract the polar organic compounds from aqueous samples. The mixture of the water-immiscible extractant and the partitioned dispersive solvent was obtained by centrifugation, dried under low pressure, reconstituted in methanol-water mixture (1:1), and injected into a HPLC system for the determination of PUHs. The enrichment factors of the PUHs ranged from 68 to 126 under the optimal conditions. The linear range was 0.5-100 ng ml(-1) for each analyte, the relative standard deviations of PUHs were in the range of 1.5-5.9% (n=5), and the detection limits (signal-to-noise ratio of 3) ranged from 0.10 to 0.28 ng ml(-1) for the herbicides. The range of intraday precision (n=5) for PUHs at the levels of 0.5, 5, and 50 ng ml(-1) were 3.0-5.9%, 1.8-3.3%, and 2.2-3.6%, respectively. The range of interday precision (n=5) at 0.5, 5, and 50 ng ml(-1) were 0.4-1.8%, 1.2-2.4%, and 0.9-2.3%, respectively. The recoveries of PUHs from three spiked river water samples, at a level of 10 ng ml(-1), were 91.2-104.1%. Due to its rapidity, ease of operation, and high recovery, PDLLME can be utilized to isolate and concentrate organic environmental contaminants such as PUHs from aqueous samples.


Assuntos
Métodos Analíticos de Preparação de Amostras/métodos , Fracionamento Químico/métodos , Herbicidas/análise , Compostos de Fenilureia/análise , Cromatografia Líquida de Alta Pressão , Água Doce/análise , Água Doce/química , Herbicidas/química , Herbicidas/isolamento & purificação , Linurona/análogos & derivados , Linurona/análise , Linurona/química , Estrutura Molecular , Compostos de Fenilureia/química , Compostos de Fenilureia/isolamento & purificação , Espectrofotometria Ultravioleta , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/química
20.
Environ Sci Technol ; 43(16): 6183-9, 2009 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-19746711

RESUMO

The application of TiO2/H2O/Vis (visible light) process for the aqueous degradation of linuron (LNR) has been investigated. The performance of TiO/H2O2/Vis process has been compared with other processes such as TiO2/H2O2 in the dark, TiO2/Vis, and H2O2 is in terms of LNR decay. The result showed that more than 70% LNR could be decomposed in the TiO2/H2O2/Vis. The degradation mechanism of LNR by TiO2/H2O2/Vis process has been verified through investigation of the effects of various radical scavengers on the performance of this system, monitoring the generation of photocurrent, and comparing the intermediates and decay pathways of LNR by UV-TiO2 and TiO2/ H2O2/Vis processes with 16 and 17 intermediates identified, respectively. It has been revealed that demethoxylation and demethylation through alkylic-oxidation is the major mechanism of LNR degradation while dechlorination (hydroxylation at the chlorine site) and direct hydroxylation on the benzene ring is minor in both processes. Mineralization and release of chlorine and nitrogen have been also studied.


Assuntos
Peróxido de Hidrogênio/química , Luz , Linurona/química , Titânio/química , Catálise/efeitos da radiação , Eletricidade , Sequestradores de Radicais Livres/química , Suspensões , Raios Ultravioleta
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