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1.
Mikrochim Acta ; 191(6): 319, 2024 05 10.
Artigo em Inglês | MEDLINE | ID: mdl-38727763

RESUMO

The high-residual and bioaccumulation property of organophosphorus pesticides (OPs) creates enormous risks towards the ecological environment and human health, promoting the research for smart adsorbents and detection methods. Herein, 2D hemin-bridged MOF nanozyme (2D-ZHM) was fabricated and applied to the efficient removal and ultrasensitive dual-mode aptasensing of OPs. On the one hand, the prepared 2D-ZHM contained Zr-OH groups with high affinity for phosphate groups, endowing it with selective recognition and high adsorption capacity for OPs (285.7 mg g-1 for glyphosate). On the other hand, the enhanced peroxidase-mimicking biocatalytic property of 2D-ZHM allowed rapid H2O2-directed transformation of 3,3',5,5'-tetramethylbenzidine to oxidic product, producing detectable colorimetric or photothermal signals. Using aptamers of specific recognition capacity, the rapid quantification of two typical OPs, glyphosate and omethoate, was realized with remarkable sensitivity and selectivity. The limit of detections (LODs) of glyphosate were 0.004 nM and 0.02 nM for colorimetric and photothermal methods, respectively, and the LODs of omethoate were 0.005 nM and 0.04 nM for colorimetric and photothermal methods, respectively. The constructed dual-mode aptasensing platform exhibited outstanding performance for monitoring OPs in water and fruit samples. This work provides a novel pathway to develop MOF-based artificial peroxidase and integrated platform for pollutant removal and multi-mode aptasensing.


Assuntos
Glicina , Glifosato , Hemina , Limite de Detecção , Estruturas Metalorgânicas , Praguicidas , Praguicidas/análise , Praguicidas/química , Estruturas Metalorgânicas/química , Hemina/química , Glicina/análogos & derivados , Glicina/química , Glicina/análise , Colorimetria/métodos , Benzidinas/química , Adsorção , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/química , Peróxido de Hidrogênio/química , Dimetoato/análise , Dimetoato/química , Aptâmeros de Nucleotídeos/química , Compostos Organofosforados/análise , Compostos Organofosforados/química
2.
J Sci Food Agric ; 102(14): 6612-6622, 2022 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-35596658

RESUMO

BACKGROUND: Ultrasound has the potential to increase microbial metabolic activity, so this study explored the stimulatory effect of ultrasound pre-treatment on the degradation of four common pesticides (fenitrothion, chlorpyrifos, profenofos, and dimethoate) during milk fermentation by Lactobacillus plantarum and its effect on yogurt quality. RESULTS: Appropriate ultrasound pretreatment significantly enhanced the growth of L. plantarum. The degradation percentages of pesticides increased by 19-38% under ultrasound treatment. Ultrasonic intensity, pulse duty cycle, and duration time were key factors affecting microbial growth and pesticide degradation. Under optimal ultrasonic pre-treatment conditions, the degradation rate constants of four pesticides were at least 3.4 times higher than those without sonication. In addition, such ultrasound pretreatment significantly shortened yogurt fermentation time, increased the water holding capacity, hardness and antioxidant activity of the yogurt, and improved the flavor quality of the yogurt. CONCLUSION: Ultrasonic pretreatment significantly accelerated the degradation of the four pesticides during yogurt fermentation. In addition, such ultrasound pretreatment increased the efficiency of yogurt making and improved the quality of yogurt in terms of water holding capacity, firmness, antioxidant activity, and flavor. These findings provide a basis for the application of ultrasound to the removal of pesticide residues and quality improvement of yogurt. © 2022 Society of Chemical Industry.


Assuntos
Clorpirifos , Resíduos de Praguicidas , Praguicidas , Terapia por Ultrassom , Animais , Antioxidantes/análise , Clorpirifos/análise , Dimetoato/análise , Fenitrotion/análise , Fenitrotion/metabolismo , Fermentação , Leite/química , Resíduos de Praguicidas/análise , Praguicidas/análise , Água/análise , Iogurte/análise
3.
Molecules ; 24(2)2019 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-30650543

RESUMO

Dimethoate (DMT) is an organophosphate insecticide commonly used to protect fruit trees and in particular olive trees. Since it is highly water-soluble, its use on olive trees is considered quite safe, because it flows away in the residual water during the oil extraction process. However, its use is strictly regulated, specially on organic cultures. The organic production chain certification is not trivial, since DMT rapidly degrades to omethoate (OMT) and both disappear in about two months. Therefore, simple, sensitive, cost-effective and accurate methods for the determination of dimethoate, possibly suitable for in-field application, can be of great interest. In this work, a quick screening method, possibly useful for organic cultures certification will be presented. DMT and OMT in water and on olive leaves have been detected by surface enhanced Raman spectroscopy (SERS) using portable instrumentations. On leaves, the SERS signals were measured with a reasonably good S/N ratio, allowing us to detect DMT at a concentration up to two orders of magnitude lower than the one usually recommended for in-field treatments. Moreover, detailed information on the DMT distribution on the leaves has been obtained by Raman line- (or area-) scanning experiments.


Assuntos
Praguicidas/análise , Análise Espectral Raman , Dimetoato/análise , Estrutura Molecular , Olea/química , Resíduos de Praguicidas/análise , Folhas de Planta/química , Análise Espectral Raman/métodos , Poluição Química da Água
4.
Environ Sci Pollut Res Int ; 25(35): 35130-35142, 2018 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-30328041

RESUMO

In this study, a new magnetic adsorbent based on magnetite-sporopollenin/graphene oxide (Fe3O4-SP/GO) was successfully developed. The adsorbent was applied for magnetic solid phase extraction (MSPE) of three selected polar organophosphorus pesticides (OPPs), namely, dimethoate, phenthoate, and phosphamidon, prior to gas chromatography analysis with electron capture detection (GC-µECD). The Fe3O4-SP/GO adsorbent combines the advantages of superior adsorption capability of the modified sporopollenin (SP) with graphene oxide (GO) and magnetite (Fe3O4) for easy isolation from sample solution. Several MSPE parameters were optimized. Under optimized conditions, excellent linearity (R2 ≥ 0.9994) was achieved using matrix match calibration in the range of 0.1 to 500 ng mL-1. The limit of detection (LOD) method (S/N = 3) was from 0.02 to 0.05 ng mL-1. The developed Fe3O4-SP/GO MSPE method was successfully applied for the determination of these three polar OPPs in cucumber, long beans, bell pepper, and tomato samples. Good recoveries (81.0-120.0%) and good relative standard deviation (RSD) (1.4-7.8%, n = 3) were obtained for the spiked OPPs (1 ng mL-1) from real samples. This study is beneficial for adsorptive removal of toxic pesticide compounds from vegetable samples.


Assuntos
Óxido Ferroso-Férrico/química , Grafite/química , Praguicidas/química , Verduras/química , Adsorção , Biopolímeros/química , Carotenoides/química , Cromatografia Gasosa , Dimetoato/análise , Limite de Detecção , Solanum lycopersicum , Magnetismo , Nanopartículas de Magnetita/química , Compostos Orgânicos/análise , Óxidos/química , Praguicidas/análise , Extração em Fase Sólida/métodos
5.
Anal Chim Acta ; 1035: 60-69, 2018 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-30224145

RESUMO

This work describes the development of a new selective photocontrollable molecularly imprinted-based sorbent for the selective enrichment/pre-concentration of dimethoate from spiked olive oil samples. To achieve this goal an improved molecularly imprinted strategy relying on the embedding of a functional monomer containing an azobenzene chromophore as light-responsive element, on the crosslinked tridimensional molecular imprinted network, has been assessed. To address the mechanisms underlying template recognition and uptake/release of the analyte from the functional imprinted material, computational studies using a quantum chemical approach, have been explored. This new functional sorbent provides a straightforward controllable uptake/release of the target template using light as the stimuli tool, which is highly advantageous due to light manipulation characteristics, such as superior clean, precision and remote controllable properties. In general, this work will contribute to the implementation of a photoswitchable analytical methodology that proves to be suitable for the selective isolation and further quantification of dimethoate from olive oil matrices at levels similar to the maximum residues limits imposed by the legislation. The limits of detection, calculated based on 3σ, was 1.6 mgL-1 and the limit of quantification, based on 10σ, was 5.2 mgL-1. The implemented sample preparation shows high reproducibility and recoveries (93.3 ±â€¯0.4%).


Assuntos
Compostos Azo/química , Benzoatos/química , Dimetoato/análise , Contaminação de Alimentos/análise , Impressão Molecular/métodos , Azeite de Oliva/química , Compostos Azo/síntese química , Benzoatos/síntese química , Dimetoato/isolamento & purificação , Inseticidas/análise , Isomerismo , Limite de Detecção , Fotoquímica/métodos , Reprodutibilidade dos Testes , Espectroscopia de Infravermelho com Transformada de Fourier
6.
Talanta ; 174: 599-604, 2017 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-28738628

RESUMO

The aim of this work was to demonstrate the potentialities of the use of a molecularly imprinted (MIP) sensor coupled to a microextraction by packed sorbent (MEPS) strategy for the selective and sensitive detection of dimethoate in real samples. A dimethoate-polypyrrole MIP film was realised by cyclic voltammetry (CV) on the surface of a glassy carbon electrode (GCE). Being dimethoate electro-inactive, K3[Fe(CN)6] was used as probe for the indirect quantification of the analyte via the decrease of redox peaks observed upon binding of the target analyte. Detection of dimethoate at low nanomolar range was achieved with linearity in the 0.1-1nM range. Relative standard deviation calculated for different electrodes at 0.5nM of dimethoate was < 3% and selectivity was very satisfactory being the response for omethoate only 23% of dimethoate. A MEPS strategy for the extraction of dimethoate from a challenging matrix as wheat flour was then used in conjunction with the MIP electrochemical sensor. The procedure applied to flour samples spiked with dimethoate at 0.5 MRL, MRL, and 1.5 MRL gave very favourable comparison with a validated UHPLC-MS/MS method with deviations in the -21% /+17% range, demonstrating the feasibility of the approach as screening assay. This work clearly shows that the sequential use of a microextraction based procedure and electrochemical sensing system is low cost, easy to realise and use and can open new perspectives for the development of selective sensing system to be used in field or decentralised lab testing for the selective screening of target analytes.


Assuntos
Dimetoato/análise , Dimetoato/isolamento & purificação , Farinha/análise , Impressão Molecular , Polímeros/síntese química , Microextração em Fase Sólida/métodos , Triticum/química , Carbono/química , Eletroquímica , Eletrodos
7.
Chemosphere ; 166: 292-299, 2017 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-27700995

RESUMO

This article discusses the adsorption of four organophosphorus pesticides-diazinon, dimethoate, methyl parathion, and sulfotep-in soil samples from four sites-Komchén, Xcanatún, Chablekal and Mocochá- in the northwest of Yucatan, Mexico. These pesticides have been detected in groundwater at concentrations greater than 5 (µg/L) during recent monitoring campaigns in the study area. In this region, groundwater contamination is exacerbated by its karst aquifer, which is susceptible to contamination and is considered very vulnerable. The experimental work was carried out using the batch equilibrium technique. Pesticide analyses by solid-phase extraction and gas chromatography were performed. The equilibrium adsorption data were analyzed by Henry, Langmuir and Freundlich models. The results indicate that the Freundlich model provides the best correlation of the experimental data. Freundlich adsorption coefficients Kf were in the range of 1.62-2.35 for sulfotep, 2.43 to 3.25 for dimethoate, from 5.54 to 9.27 for methyl parathion, and 3.22 to 5.17 for diazinon. Freundlich adsorption coefficients were normalized to the content of organic carbon in the soil to estimate the sorption coefficient of organic carbon (KOC). KOC values were in the range of 9.45-71.80, indicated that four pesticides have low adsorption on the four studied soils, which represents a high risk of contamination to the aquifer.


Assuntos
Diazinon/análise , Dimetoato/análise , Metil Paration/análise , Compostos Organotiofosforados/análise , Praguicidas/análise , Fosfatos/química , Poluentes do Solo/análise , Adsorção , Carbono/química , Poluentes Ambientais , Recuperação e Remediação Ambiental , Água Subterrânea/química , México , Solo/química
8.
Chemosphere ; 166: 21-30, 2017 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-27681257

RESUMO

A new graphene-based tetraethoxysilane-methyltrimethoxysilane sol-gel hybrid magnetic nanocomposite (Fe3O4@G-TEOS-MTMOS) was synthesised, characterized and successfully applied in magnetic solid-phase extraction (MSPE) for simultaneous analysis of polar and non-polar organophosphorus pesticides from several water samples. The Fe3O4@G-TEOS-MTMOS nanocomposite was characterized using Fourier transform-infrared spectroscopy, energy-dispersive X-ray spectroscopy, field emission scanning electron microscopy and X-ray diffraction. Separation, determination and quantification were achieved using gas chromatography coupled with micro electron capture detector. Adsorption capacity of the sorbent was calculated using Langmuir equation. MSPE was linear in the range 100-1000 pg mL-1 for phosphamidon and dimethoate, and 10-100 pg mL-1 for chlorpyrifos and diazinon, with limit of detection (S/N = 3) of 19.8, 23.7, 1.4 and 2.9 pg mL-1 for phosphamidon, dimethoate, diazinon and chlorpyrifos, respectively. The LODs obtained is well below the maximum residual level (100 pg mL-1) as set by European Union for pesticides in drinking water. Acceptable precision (%RSD) was achieved for intra-day (1.3-8.7%, n = 3) and inter-day (7.6-17.8%, n = 15) analyses. Fe3O4@G-TEOS-MTMOS showed high adsorption capacity (54.4-76.3 mg g-1) for the selected OPPs. No pesticide residues were detected in the water samples analysed. Excellent extraction recoveries (83-105%) were obtained for the spiked OPPs from tap, river, lake and sea water samples. The newly synthesised Fe3O4@G-TEOS-MTMOS showed high potential as adsorbent for OPPs analysis.


Assuntos
Grafite/química , Magnetismo , Nanocompostos/química , Resíduos de Praguicidas/análise , Praguicidas/análise , Extração em Fase Sólida/métodos , Adsorção , Calibragem , Clorpirifos/análise , Cromatografia Gasosa , Diazinon/análise , Dimetoato/análise , Compostos Férricos/química , Lagos/análise , Limite de Detecção , Compostos Orgânicos/química , Óxidos/química , Transição de Fase , Fosfamidona/análise , Fósforo/química , Rios , Silanos , Solventes/química , Espectroscopia de Infravermelho com Transformada de Fourier , Difração de Raios X
9.
Environ Sci Pollut Res Int ; 22(19): 15104-12, 2015 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-26003089

RESUMO

Three types of chitosan with high (3.40 × 10(6)), medium (2.11 × 10(5)), and low (5.89 × 10(4)) molecular weights were chosen as ligands to synthesize chitosan magnesium, calcium, iron(III), and zinc coordination complexes. Degradation of four organophosphorous pesticides (dichlorvos, omethoate, dimethoate, and chlorpyrifos) by the above complexes in a heterogeneous system was studied using solid-phase extraction (SPE) and gas chromatography (GC). The degradation effect is related to the different types of chitosan, metal, and organophosphorus pesticides (OPs). Complexes of transition metals and the low molecular weight chitosan showed high hydrolytic activity. The chitosan-iron(III) complex was further used to study its catalytic kinetics on the hydrolysis of OPs. At pH 7.0 and 20 °C, the half-life of dichlorvos hydrolyzed by chitosan iron(III) was 52 h, whereas that of spontaneous dichlorvos hydrolysis was 105 h. The degradation ratio of omethoate and dimethoate increased to 38 and 52 %, respectively, which were 34 and 48 % higher than the control after 6 days at pH 7.0 and 20 °C. For all tested conditions, an increase of pH and temperature resulted in a higher degradation rate.


Assuntos
Quitosana/química , Complexos de Coordenação/química , Compostos Férricos/química , Compostos Organofosforados/análise , Praguicidas/análise , Catálise , Clorpirifos/análise , Cromatografia Gasosa , Diclorvós/análise , Dimetoato/análogos & derivados , Dimetoato/análise , Recuperação e Remediação Ambiental , Meia-Vida , Hidrólise , Cinética , Extração em Fase Sólida , Temperatura
10.
Food Chem ; 187: 331-7, 2015 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-25977034

RESUMO

A novel restricted access materials (RAM) combined to molecularly imprinted polymers (MIPs), using malathion as template molecule and glycidilmethacrylate (GMA) as pro-hydrophilic co-monomer, were prepared for the first time. RAM-MIPs with hydrophilic external layer were characterized by scanning electron microscopy and recognition and selectivity properties were compared with the restricted access materials-non-molecularly imprinted polymers (RAM-NIPs) and unmodified MIPs. RAM-MIPs were used as the adsorbent enclosed in solid phase extraction column and several important extraction parameters were comprehensively optimized to evaluate the extraction performance. Under the optimum extraction conditions, RAM-MIPs exhibited comparable or even higher selectivity with greater extraction capacity toward six kinds of organophosphorus pesticides (including malathion, ethoprophos, phorate, terbufos, dimethoate, and fenamiphos) compared with the MIPs and commercial solid phase extraction columns. The RAM-MIPs solid phase extraction coupled with gas chromatography was successfully applied to simultaneously determine six kinds of organophosphorus pesticides from honey sample. The new established method showed good linearity in the range of 0.01-1.0 µg mL(-1), low limits of detection (0.0005-0.0019 µg mL(-1)), acceptable reproducibility (RSD, 2.26-4.81%, n = 6), and satisfactory relative recoveries (90.9-97.6%). It was demonstrated that RAM-MIPs solid phase extraction with excellent selectivity and restricted access function was a simple, rapid, selective, and effective sample pretreatment method.


Assuntos
Mel/análise , Impressão Molecular/métodos , Compostos Organofosforados/análise , Praguicidas/análise , Polímeros/química , Extração em Fase Sólida/métodos , Dimetoato/análise , Malation/análise , Microscopia Eletrônica de Varredura , Organotiofosfatos , Compostos Organotiofosforados/análise , Forato/análise , Reprodutibilidade dos Testes
11.
Huan Jing Ke Xue ; 36(9): 3486-92, 2015 Sep.
Artigo em Chinês | MEDLINE | ID: mdl-26717714

RESUMO

This study aims to investigate the concentrations of organophosphorus pesticides (OPs) in fresh vegetables. A total of Z14 samples from seven types of vegetables were collected from the suburb in Changchun City. The OPs were analyzed by gas chromatography coupled with flame photometric detector (GC-FPD). Target hazard quotients (THQ) were applied to estimate the potential health risk to inhabitants. Results showed that OPs concentrations exceeded the Maximum Residue Limit (MRL) in more than 23. 4% samples, and were not detected in only 7. 9% samples. Detection rates of OPs was as follow in the decreased order: diazinon (82. 2%) > phorate (45. 8%) > dimethoate (29. 4%) > parathion-methyl (27. 6%) > omethoate (23. 8%) > dichlorvos (22. 9%) > fenitrothion (21%) > fenthion (18. 7%) > parathion (18. 2%) > methamidophos (17. 3%) > malathion (12. 1%). The percentages above MRL for leaves were higher than for non-leafy vegetables. The order of percentages of OPs above MRL was as follows: green onion (82. 5%) > radish (37. 5%) > red pepper (17. 2%) > Chinese vegetable (14. 3%) > cucumber (3. 2%) > eggplant (2. 9%) > tomato (0%). 49. 5% vegetables samples showed more than one OP. The average target hazard quotients (ave THQ) were all less than one and the average Hazard Index (ave HI) was 0. 462, so that inhabitants who expose average OP levels may not experience adverse health effects.


Assuntos
Contaminação de Alimentos/análise , Compostos Organofosforados/análise , Resíduos de Praguicidas/análise , Verduras/química , China , Cromatografia Gasosa , Dimetoato/análogos & derivados , Dimetoato/análise , Compostos Organotiofosforados/análise , Medição de Risco
12.
Chemosphere ; 111: 458-63, 2014 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-24997952

RESUMO

Compound-specific isotope analysis (CSIA) has been established as a tool to study the environmental fate of a wide range of contaminants. In this study, CSIA was developed to analyse the stable carbon isotope signatures of the widely used organophosphorus pesticides: dichlorvos, omethoate and dimethoate. The linearity of the GC-C-IRMS system was tested for target pesticides and led to an acceptable isotope composition within the uncertainty of the instrument. In order to assess the accuracy of the developed method, the effect of the evaporation procedure on measured carbon isotope composition (δ(13)C) values was studied and showed that concentration by evaporation of solvents had no significant isotope effect. The CSIA was then applied to investigate isotope fractionation of the hydrolysis and photolysis of selected pesticides. The carbon isotope fractionation of tested pesticides was quantified by the Rayleigh model, which revealed a bulk enrichment factor (ε) of -0.2±0.1‰ for hydrolysis of dichlorvos, -1.0±0.1‰ and -3.7±1.1‰ for hydrolysis and photolysis of dimethoate respectively. This study is a first step towards the application of CSIA to trace the transport and degradation of organophosphorus pesticides in the environment.


Assuntos
Diclorvós/análise , Dimetoato/análogos & derivados , Dimetoato/análise , Poluentes Ambientais/análise , Praguicidas/análise , Isótopos de Carbono/análise , Hidrólise , Fotólise
13.
J Agric Food Chem ; 61(22): 5397-403, 2013 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-23687955

RESUMO

This article presents a novel application of dispersive microextraction based on "magnetic water" (m-water) for the purification of organophosphorus pesticides (methamidophos, omethoate, monocrotophos) from cold-pressed vegetable oils. In the present study, a trace amount of water (extractant) was adsorbed on bare Fe3O4 by hydrophilic interaction to form m-water. Rapid extraction can be achieved while the m-water is dispersed in the sample solution with the aid of a vigorous vortex. After extraction, the analyte-adsorbed m-water can be readily isolated from the sample solution by a magnet, which could greatly simplify the operation and reduce the whole pretreatment time. Several parameters affecting the extraction efficiency were investigated, and under the optimized conditions, a simple and effective method for pesticide analysis was established by coupling with gas chromatography/mass spectrometry (GC/MS). The linearity range of the proposed method was 2-100 ng/g with satisfactory correlation coefficients (R) of 0.9997-0.9998, and the limits of quantification (LOQ) for the target compounds were in the range of 0.70-1.27 ng/g. In addition, the reproducibility was obtained by evaluating the intra- and interday precisions with relative standard deviations (RSDs) less than 7.2% and 6.5%, respectively. Finally, the established "magnetic water" microextraction method was successfully applied for the determination of pesticide residues in several kinds of cold-pressed vegetable oils.


Assuntos
Contaminação de Alimentos , Inspeção de Alimentos/métodos , Compostos Organofosforados/análise , Resíduos de Praguicidas/análise , Praguicidas/análise , Óleos de Plantas/química , Água/química , Métodos Analíticos de Preparação de Amostras , China , Dimetoato/análogos & derivados , Dimetoato/análise , Dimetoato/química , Cromatografia Gasosa-Espectrometria de Massas , Microextração em Fase Líquida , Fenômenos Magnéticos , Monocrotofós/análise , Monocrotofós/química , Compostos Organofosforados/química , Compostos Organotiofosforados/análise , Compostos Organotiofosforados/química , Resíduos de Praguicidas/química , Praguicidas/química
14.
Sensors (Basel) ; 12(6): 7893-904, 2012.
Artigo em Inglês | MEDLINE | ID: mdl-22969377

RESUMO

This work presents the development of bioassays and biosensors for the detection of insecticides widely used in the treatment of olive trees. The systems are based on the covalent immobilisation of acetylcholinesterase on magnetic microbeads using either colorimetry or amperometry as detection technique. The magnetic beads were immobilised on screen-printed electrodes or microtitration plates and tested using standard solutions and real samples. The developed devices showed good analytical performances with limits of detection much lower than the maximum residue limit tolerated by international regulations, as well as a good reproducibility and stability.


Assuntos
Acetilcolinesterase/metabolismo , Enzimas Imobilizadas/metabolismo , Magnetismo , Microesferas , Praguicidas/análise , Óleos de Plantas/química , Animais , Técnicas Biossensoriais , Colorimetria , Dimetoato/análogos & derivados , Dimetoato/análise , Técnicas Eletroquímicas , Concentração Inibidora 50 , Inseticidas/análise , Inseticidas/química , Cinética , Malation/análogos & derivados , Malation/análise , Azeite de Oliva , Organofosfatos/análise , Organofosfatos/química , Compostos Organotiofosforados/análise , Praguicidas/química , Fatores de Tempo
15.
Bull Environ Contam Toxicol ; 87(3): 312-8, 2011 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-21681400

RESUMO

Infiltration galleries are among the oldest known means used for small public water fountains. Owing to its ancestral origin they are usually associated with high quality water. Thirty-one compounds, including pesticides and estrogens from different chemical families, were analysed in waters from infiltration galleries collected in Alto Douro Demarcated Wine region (North of Portugal). A total of twelve compounds were detected in the water samples. Nine of these compounds are described as presenting evidence or potential evidence of interfering with the hormone system of humans and wildlife. Although concentrations of the target analytes were relatively low, many of them below their limit of quantification, four compounds were above quantification limit and two of them even above the legal limit of 0.1 µg/L: dimethoate (30.38 ng/L), folpet (64.35 ng/L), terbuthylazine-desethyl (22.28 to 292.36 ng/L) and terbuthylazine (22.49 to 369.33 ng/L).


Assuntos
Drenagem Sanitária , Disruptores Endócrinos/análise , Monitoramento Ambiental , Praguicidas/análise , Poluentes Químicos da Água/análise , Abastecimento de Água/análise , Animais , Animais Selvagens , Dimetoato/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Humanos , Ftalimidas/análise , Portugal , Medição de Risco , Triazinas/análise , Abastecimento de Água/normas
16.
Anal Chim Acta ; 678(1): 63-72, 2010 Sep 23.
Artigo em Inglês | MEDLINE | ID: mdl-20869506

RESUMO

The sensitive multiresidual analytical method for simultaneous analysis of 14 most commonly used agricultural pesticides in Serbia was developed and optimized. The selected insecticides, fungicides and herbicides belong to seven chemical classes (organophosphates, neonicotinoids, carbamates, diacylhydrazines, benzimidazoles, triazines and phenylureas). The method was based on solid-phase extraction followed by liquid chromatography-tandem mass spectrometry. The following parameters that may affect the SPE procedure efficiency were optimized: the sorbent type in combination with different elution solvents, the sample pH and the sample volume. For each pesticide, MS(n) analysis was performed and distinctive ions and transitions were selected for identification and quantification, as well as for confirmation purposes. External matrix-matched calibration method was used to eliminate variable matrix effect and ensure precise quantification. Good recoveries (72-129%), and low limits of detection (0.4-5.5 ng L(-1)) and quantification (1.1-18.2 ng L(-1)) were achieved for all selected pesticides. The developed and optimized method was successfully applied in the analysis of several river waters, as well as ground waters in Serbia, influenced by agriculture. The most frequently detected pesticide was carbendazim. Dimethoate, carbofuran and propazine were also found in the investigated samples.


Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Água Doce/análise , Praguicidas/análise , Espectrometria de Massas por Ionização por Electrospray/métodos , Poluentes Químicos da Água/análise , Benzimidazóis/análise , Benzimidazóis/isolamento & purificação , Carbamatos/análise , Carbamatos/isolamento & purificação , Carbofurano/análise , Carbofurano/isolamento & purificação , Dimetoato/análise , Dimetoato/isolamento & purificação , Praguicidas/isolamento & purificação , Extração em Fase Sólida , Triazinas/análise , Triazinas/isolamento & purificação , Poluentes Químicos da Água/isolamento & purificação
17.
Shokuhin Eiseigaku Zasshi ; 51(3): 122-7, 2010.
Artigo em Japonês | MEDLINE | ID: mdl-20595793

RESUMO

We studied the simultaneous determination of acephate, methamidophos, and omethoate in animal and fishery products, their processed foods, and honey by means of liquid chromatography coupled with mass spectrometry (LC-MS). The sample was extracted with ethyl acetate in the presence of anhydrous Na(2)SO(4) (and diatomaceous earth for honey). An aliquot of the crude sample extract was loaded into the GPC system, and the pesticide fraction was selectively collected. The extract was cleaned up on a PSA mini-column, and determined by a column-switching ESI-SIM mode LC-MS. Mean recoveries (2 replicates x 5 days) of compounds from eleven kinds of samples, except honey, fortified at the analyte concentration of 0.05 microg/g were from 71.4% to 98.4%. The repeatability relative standard deviation values were < or =12.5%, and the intermediate reproducibility relative standard deviation values were < or =14.1%. In honey, the recoveries were improved to 97.6-98.6% by using highly purified surrogates.


Assuntos
Dimetoato/análogos & derivados , Produtos Pesqueiros/análise , Mel/análise , Inseticidas/análise , Carne/análise , Compostos Organotiofosforados/análise , Animais , Cromatografia Líquida , Dimetoato/análise , Ovos/análise , Manipulação de Alimentos , Espectrometria de Massas , Fosforamidas
18.
Talanta ; 81(4-5): 1380-6, 2010 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-20441911

RESUMO

An analytical method using solid phase extraction (SPE) and analysis by gas chromatography/mass spectrometry (GC-MS) was developed to determine trace levels of a variety of 41 agricultural pesticides and selected transformation products in high-elevation surface waters. Large-volume water sampling (up to 100L) was employed because it was anticipated that pesticide contamination, if present, would be at very low levels. The target compounds comprise pesticides (and selected oxygen transformation products) known to have been extensively used in agriculture in the San Joaquin Valley, CA, USA. Solid phase extraction using the polymeric resin Abselut Nexus was optimized to extract the pesticide analytes from water samples. A single determinative method using GC-MS with electron ionization was used for all the analytes. Recoveries from 100L of reagent water at 100pg/L and 1ng/L concentrations were generally greater than 75%, although dimethoate, disulfoton, and phorate were not recovered. Analysis of the extracts without cleanup yielded detection limits for the remaining 38 analytes between 0.1 and 30ng/L. A silica cleanup with separate analysis of 3 eluant fractions improved detection limits for 37 of the compounds to between 6 and 600pg/L in high-elevation surface waters.


Assuntos
Técnicas de Química Analítica , Resíduos de Praguicidas/análise , Praguicidas/análise , Extração em Fase Sólida/métodos , Purificação da Água/métodos , Água/química , Absorção , Agricultura/métodos , Dimetoato/análise , Dissulfóton/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Resíduos de Praguicidas/isolamento & purificação , Praguicidas/isolamento & purificação , Forato/análise , Dióxido de Silício/química , Temperatura , Poluentes da Água/análise
19.
J Chromatogr B Analyt Technol Biomed Life Sci ; 878(17-18): 1234-45, 2010 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-20106727

RESUMO

Dimethoate is an organophosphorus toxicant used in agri- and horticulture as a systemic broad-spectrum insecticide. It also exhibits toxic activity towards mammalian organism provoked by catalytic desulfuration in the liver producing its oxon-derivative omethoate thus inhibiting acetylcholinesterase, initiating cholinergic crisis and ultimately leading to death by respiratory paralysis and cardiovascular collapse. Pharmaco- and toxicokinetic studies in animal models help to broaden basic understanding of medical intervention by antidotes and supportive care. Therefore, we developed and validated a LC-ESI-MS/MS method suitable for the simultaneous, selective, precise (RSD(intra-day) 1-8%; RSD(inter-day) 5-14%), accurate (intra-day: 95-107%; inter-day: 90-115%), and robust quantification of both pesticides from porcine urine and plasma after deproteinization by precipitation and extensive dilution (1:11,250 for plasma and 1:40,000 for urine). Accordingly, lower limits of quantification (0.24-0.49 microg/ml plasma and 0.78-1.56 microg/ml urine) and lower limits of detection (0.12-0.24 microg/ml plasma and 0.39-0.78 microg/ml urine) were equivalent to quite low absolute on-column amounts (1.1-2.1 pg for plasma and 2.0-3.9 pg for urine). The calibration range (0.24-250 microg/ml plasma and 0.78-200 microg/ml urine) was subdivided into two linear ranges (r(2)>or=0.998) each covering nearly two orders of magnitude. The lack of any interfering peak in 6 individual blank specimens from plasma and urine demonstrated the high selectivity of the method. Furthermore, extensive sample dilution causing lowest concentration of potentially interfering matrix ingredients prompted us to develop and validate an additional flow-injection method (FI-ESI-MS/MS). Validation characteristics were as good as for the chromatographic method but sample throughput was enhanced by a factor of 6. Effects on ionization provoked by plasma and urine matrix from 6 individuals as well as in the presence of therapeutics (antidotes) administered in an animal study were investigated systematically underlying in the reliability of the presented methods. Both methods were applied to porcine samples derived from an in vivo animal study.


Assuntos
Cromatografia Líquida/métodos , Dimetoato/análogos & derivados , Dimetoato/análise , Análise de Injeção de Fluxo/métodos , Inseticidas/análise , Espectrometria de Massas por Ionização por Electrospray/métodos , Espectrometria de Massas em Tandem/métodos , Animais , Dimetoato/sangue , Dimetoato/química , Dimetoato/urina , Estabilidade de Medicamentos , Inseticidas/sangue , Inseticidas/química , Inseticidas/urina , Modelos Lineares , Reprodutibilidade dos Testes , Sensibilidade e Especificidade , Suínos
20.
Environ Monit Assess ; 169(1-4): 37-43, 2010 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-19757120

RESUMO

A total of 75 animals between 1.5 and 8 years old were randomly selected for the study. Of these, 57.8% were cross-bred animals and the rest were non-descript. Moreover, 61.8% of the animals under study were brought for slaughter from local sources and the rest from farm houses. Samples collected from five districts revealed contamination with traces of organochlorine pesticides (0.01-0.22 microg g(-1)) and organophosphorus pesticides (0.111-0.098 microg g(-1)). In general, all the raw meat samples possessed dichlorodiphenyltrichloroethane at the highest level. Contamination was highest in cow meat samples and lowest in chicken samples. No particular district-wise trend was obtained for the pesticides selected for analysis. Subsequent decontamination study revealed that cooking is the best option in reducing pesticide load in raw meat samples. Cooked chicken is the safest foodstuff for consumption.


Assuntos
Contaminação de Alimentos/prevenção & controle , Inocuidade dos Alimentos/métodos , Carne/análise , Praguicidas/análise , DDT/análise , Dimetoato/análise , Endossulfano/análise , Contaminação de Alimentos/análise , Hexaclorocicloexano/análise , Hidrocarbonetos Clorados/análise , Malation/análise , Medição de Risco
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