Determinação de carbaril utilizando testes ELISA (Enzyme-linked immunosorbent assay) e CLAE com detecção por arranjo de diodos

ELISAs have been applied to pesticide residue analysis due to their high sensitivity and selectivity. However, some ELISAs performance may be affected by matrix components. In this work, ELISA for carbaryl in water samples was checked for interference by naturally occurring fulvic acids. The results suggested that the high fulvic acid concentration (ž³30 mg L-1) and acidic pH conditions (pH 4.0) interfere with the signal detection decreasing the method sensitivity. A dilution of the samples and adjust to pH 8.0 are appropriate to minimize the matrix interferences in the ELISA method. Good correlation between ELISA and HPLC-DAD results was observed.

Contaminação do ambiente aquático por pesticidas. Estudo de caso: águas usadas para consumo humano em Primavera do Leste, Mato Grosso - análise preliminar

A preliminary analyses of the possible contamination of superficial and underground water by the active ingredients of the pesticide products used in the surroundings of the urban area of Primavera do Leste, Mato Grosso, Brazil, was carried out. A description of the study region and of its environmental characteristics, which can favor the contamination of the local aquatic environment, was presented. The EPA screening criteria, the groundwater ubiquity score (GUS) and the criteria proposed by Goss were used to evaluate which pesticides might contaminate the local waters. Among the active ingredients studied, several present risks to the local aquatic environment.

Extração em fase sólida (SPE) e micro extração em fase sólida (SPME) de piretróides em água

The pyrethroids bifenthrin, permethrin, cypermethrin and deltamethrin were extracted by solid phase extraction (SPE) and solid phase microextraction (SPME). The analysis were performed on a gas chromatograph with electron capture detection (GC-ECD). Octadecil Silano-C18, Florisil and Silica stationary phases were studied for SPE. Better results were obtained for Florisil which gave recoveries from 80% to 108%. Pyrethroids extraction by SPME showed a linear response and a detection limit of 10 pg ml-1. Although the data showed that the two extraction methods were able to isolate the pesticide residues from water samples, the best results were obtained by using SPME which is more sensitive, faster, cheeper, being a more useful technique for the analysis of pyrethroids in drinking water.

Análise de resíduos de pesticidas em tomates por cromatografia em camada delgada

Pesticide residues are determined by thin layer chromatography (TLC) using the Hill reaction as a detection method. Tomatoes samples without pesticide were fortified with atrazine, diuron, chloroxuron and metribuzin, and were applyed in silica gel plates with the help of a microsyringe. The pesticides were elued with ethyl acetate. There was no need of cleaning up because no interference was noticed. After the revelation of the plates, the diameters of the spots were measure by using a rule. The range of the determined concentration for all the pesticides was from 0.1 to1.0 ng/muL. The results obtained through TLC can be used for semi-quantitative analysis.The results obtained were compared to gas and liquid chromatography, showing good agreement between both techniques.

Extração por fluido supercrítico de alguns inseticidas carbamatos em amostras de batata, com determinação por HPLC/fluorescência e confirmação por HPLC/espectrometria de massas

Six supercritical fluid extraction (SFE) methods were tested, by varying the following operational parameters: CO2 pressure, time and temperature of extraction, type and proportion of static modifier, and Hydromatrix®/sample rate into cell. Firstly, insecticide carbamates were extracted from spiked potatoes samples (fortification level of 0,5 mg.Kg-1) by using SPE procedures, and then final extracts were analyzed HPLC/fluorescence. Good performance was observed with SFE methods that operated with values of temperature and CO2 pressure of 50 ºC and 350 bar, respectively. Best efficiency was obtained when it was used acetonitrile as a modifier (3% on the cell volume), and Hydromatrix®/sample rate of 2:1. Static time was of 1 min; total extraction time was of 35 min; dynamic extraction was performed with 15 mL of CO2, and it was used methanol (2 mL) for the dissolution of the final residue. In such conditions, pesticide recoveries varied from 72 to 94%, depending on the analyzed compound. In higher extraction temperatures, a rapid degradation was observed for some compounds, such as aldicarb and carbaryl; presence of their metabolites was further confirmed by HPLC-APCI/MS in positive mode. Detection limits for chromatographic analysis varied from 0,2 to 1,3 ng.

Otimização dos parâmetros de extração para determinação multiresíduo de pesticidas em amostras de água empregando microextração em fase sólida

In this study the factors that affect the extraction of pesticide residues from water samples for their determination by solid-phase micro-extraction (SPME) and GC/MS were optimized. The fiber polymer, the extraction mode, the ionic strength, the stirring rate, the pH and the extraction time were the most significant parameters evaluated. The recovery obtained with the proposed method ranged from 94 to 110% and the sensitivity of the method, determined by calculating the detection limit (DL), ranged from 0.004 to 0.1 mug l-1. The results obtained with spiked real samples, at the 0.1 mug l-1 level, showed acceptable conformity with the expected values.

Quantificação do pesticida diclorvos por voltametria de onda quadrada em águas puras e naturais

This work reports the use of square wave voltammetry (SWV) to analyse the electrochemical reduction of dichlorvos (2, 2-dichlorovinyl-dimethylphosphate) in spiked pure and natural waters. SWV measurements were carried out in 0.5 mol L-1 Na2SO4 aqueous solutions at pH 5, prepared with water originated from three different sources, namely, one sample of purified water and others from two urban creeks in São Carlos County. In all cases, two reduction peaks were observed, at potentials of -0.15 and -1.05 V vs Ag/AgCl, with both current and potential being dependent on pesticide concentration. This allowed the calculation of the following detection limits: 1.0, 2.5 and 3.0x10-8 mol L-1 for purified, Gregorio creek and Monjolinho creek waters, respectively, in a working range between 2.0x10-7 and 1.4x10-6 mol L-1. Recovery measurements found values higher than 80% in all cases, for an added concentration of 4.0 x 10-7 mol L-1 of dichlorvos in each solution. All analytical experiments were performed in triplicate and showed a standard deviation always less than 3%.

Análise de praguicidas organofosforados em água por extração em fase sólida (SPE) utilizando discos C18 e cromatografia em fase gasosa: avaliação da contaminação do reservatório de Furnas (MG-Brasil)

Solid phase extraction (SPE) in C18 disks has been optimized and validated for extraction of 5 organophosphorus (OP) pesticides in water. Extraction has been followed by separation and detection by gas chromatography/flame photometry. Excellent linearity was obtained for all compounds (r greater than 0.99), with CVs between 1.0-6.9%, recoveries between 73-95% and quantification limits between 2.5-5.0 µg L-1. Samples from Furnas dam were analyzed monthly during one year and 10% showed OP pesticide residues.

Método multirresíduo para monitoramento de contaminação ambiental de pesticidas na região de Bauru (SP) usando mel como bio-indicador

The presence of residues of the major groups of pesticides (organohalogen, organophosphorous, pyrethroids and organonitrogen) in representative samples of honey produced in Bauru (state of São Paulo, Brazil) was investigated from 1999 through2004. A multiresidue method was applied to honey samples to determine 48 pesticides with recoveries ranging from 76 to 95%. The limits of detection found were lower than 10 µg/kg for GC-MS-SIM. The results indicated that most pesticides found in the samples belonged to the organohalogen and organonitrogen groups. Residues of malathion were detected in almost all of the samples in high concentration.

Ensaio de proficiência para análise de ditiocarbamatos em polpa de banana

A proficiency assay of the determination of dithiocarbamate pesticide residues in banana was carried out. Fourteen laboratories participated in this study. Homogeneity and stability testing were performed by INCQS on the samples sent to the laboratories. Analytical results supplied by the pesticide residues laboratory of the VWA/KvW, Amsterdam, Holland, were used to define the designated value for the thiram concentration in the study samples. RESULTS: Fifty percent of the participating laboratories had satisfactory results. Efforts are needed to improve the precision of the analytical results and to decrease the number of false negative results observed.

Avaliação da reação foto-fenton na decomposição de resíduos de carrapaticida

Experimental procedures based on factorial design and surface response methodology were applied to establishe experimental conditions for the decomposition of a 1:400 (v/v) Supocade® (chlorfenvinphos 13.8% and cypermethrin 2.6%) solution, used to control cattle ticks. Experiments exploring photo-oxidative reactions were performed with and without UV radiation, fixing exposition time and pesticide volume, and varying the oxidant mixture. The use of 3.6 mmol L-1 Fe2+ plus 1.9 mol L-1 H2O2 plus UV radiation provided destruction of 94% of the original carbon content and reduction of aromatic, aliphatic and carbinolic compounds, evaluated by determination of residual carbon content by ICP OES and NMR analysis.

Contaminação de águas subterrâneas por pesticidas: avaliação preliminar

A discussion about groundwater contamination is presented in this work. Contamination by agricultural activity, more specifically by pesticides is emphasized. Indirect and direct estimates could be used to predict pesticide behavior in soil, and consequently, to evaluate the potential of groundwater contamination. These results could be applied to advise about the possibility of groundwater contamination by pesticides, and to provide subsidies for making decisions more quickly and efficiently.

Diagnóstico espaço-temporal da ocorrência de herbicidas nas águas superficiais e sedimentos do Rio Corumbataí e principais afluentes

Residues of herbicides from sugarcane were monitored in waters and sediments of Corumbataí River and tributaries. Ametryne, atrazine, simazine, hexazinone, glyphosate, and clomazone were detected in water samples, with negligible levels of ametryne and glyphosate in sediment samples. The area of recharge of the Guarani aquifer presented the highest triazine and clomazone levels. The triazines were detected at higher levels, with atrazine above Brazil's potability and quality standards. Total herbicide levels at some sampling points were 13 times higher than the European Community potability limit. There is no Brazilian standard for ametryne, although the risk is larger due to ametryne's higher toxicity for the aquatic biota.

Avaliação do impacto da agricultura em áreas de proteção ambiental, pertencentes à bacia hidrográfica do rio ribeira de iguape, São Paulo

In order to ascertain the impact of agricultural activities on water quality of the Ribeira de Iguape River Basin in the state of São Paulo, surface water areas for catchment and drinking water have been characterized. The sampling period covered March/2002 - February/2003 and January/2004 at 10 different catchment points. SPE-LC-UV/Vis was used to monitor various pesticide classes such as carbamates, triazines and nitroanilines. The results revealed that water quality is associated with seasonal variation. Of 152 samples analyzed, only 24% showed the presence of pesticides, particulary during the wet season. High variability in pH, turbidity and color were observed.

Desenvolvimento e validação de método de análise de glifosato em grãos de soja

The main objective of this work is to develop an efficient procedure to determine glyphosate in soybean grains. The cleanup of the aqueous extracts was done in two steps, beginning with liquid-liquid partitioning and then solid-phase extraction with anion exchange resin. After derivatization with a mixture of trifluoroacetic anhydride (TFAA) and trifluoroethanol (TFE), quantification was done by gas chromatography coupled to mass spectrometry. The mean recovery and RSD of the spiked samples were, respectively, 80.5% and 3.1% at level 0.200 mg kg-1, 93.3% and 18.7% at level 0.500 mg kg-1 and 92% and 3.5% at level 1.000 mg kg-1. The method was linear in the working range (correlation coefficient = 0.9965).