Diethylene glycol is an extremely toxic substance to humans. Recently, cases of beer contamination in Brazil have raised awareness of the need for developing simple screening methods to evaluate this type of compound. This research developed a liquid-liquid extraction with low-temperature partitioning technique to determine diethylene glycol in beer via gas chromatography. Employing a flame-ionization detector simplifies the method, lowers its cost and therefore, it can be used as screening step to assess the possibility of contamination. A gas chromatograph coupled to a mass spectrometer would be used only for a confirmatory analysis. The optimized method was validated for the main figures of merit, and it proved to be adequate, with good values of recovery rate (94-106%), limit of detection (3.0 mg L-1), and quantification (10.0 mg L-1). Accuracy, in terms of repeatability and intermediate accuracy, showed variation coefficients lower than or equal to 20%. This method was applied to 28 samples of beers marketed in Brazil, and diethylene glycol was found above the limit of detection in three of them (10.7%). These results were confirmed by a gas chromatograph coupled to a mass spectrometer, which showed the reliability of the screening method for determining diethylene glycol in beer samples.

Ozone and hypochlorite are used for the disinfection of water and is essential to monitor these. In this paper, methods based on digital images were developed to determine these analytes in waters using the malachite green dye. The oxidation of the reagent with ozone was very fast and with hypochlorite occurred in 10 min in pseudo-first-order kinetics. New software called ICCA was developed for the capture and processing of red, green and blue (RGB) data, which is planned for digital image analysis. In addition, the recently proposed parameters analytical resolution and N9 were used to define some study conditions. An evaluation of different response functions and white correction of the webcam were done, having thrown some light on the subject to this theme. Their optimization showed a linear range from 0.6 mg L-1 to 5.0/6.0 mg L-1 (O3/Cl, respectively). The figures of merit were similar for both. The methods were validated and the recoveries achieved were between 85.0 and 96.0% (ozone) and 101.0 and 119.0% (hypochlorite).

The liquid-liquid extraction with low-temperature partitioning technique (LLE/LTP) was miniaturized to determine the pesticides chlorpyrifos, bifenthrin, λ-cyhalothrin, and deltamethrin in a biological matrix, by gas chromatography. The method was proposed for fetal-bovine serum samples (500 μL), by using a full factorial design (23) with one center point. The evaluated factors included the volume of water added to the sample (1000 μL), volume of extraction solvent (500 μL) and stirring time (60 s) – a cleanup step was not necessary. The method was validated for the main figures of merit. The results indicated that the LLE/LTP/GC/ECD miniaturized method was efficient in extracting pesticides from blood-serum samples (75 to 115%). It showed both selectivity and sensitiveness, with limits of quantification (LOQ) ranging from 8 at 17 μg L-1;. Once validated, the method was applied to blood-serum samples of rural workers from a city in the Brazilian state of Minas Gerais. In that case, the presence of chlorpyrifos was detected in two of the samples.

Pesticides are used globally to protect food against pest attack. This study evaluates the dissipation of bifenthrin and deltamethrin residues in unhulled rice and the translocation of these insecticide residues in husked rice stored at 25 °C in a biochemical oxygen demand (BOD) incubator for 35 days. For pesticide determination, the simple and efficient solid-liquid extraction methods with low temperature partition (SLE/LTP) followed by gas chromatography with electron capture detection (GC-ECD), for unhulled and husked rice were optimized and validated. These methods produced results of validated parameters consistent with Brazilian legislation, showing good efficiency (recovery rate above 95%) and limit of quantification (LOQ) < 0.090 mg kg−1 for bifenthrin and LOQ < 0.070 mg kg−1 for deltamethrin. There was a 40% dissipation of deltamethrin residues after 15 days of storage of the unhulled rice. For the insecticide bifenthrin, dissipation during the 35 days of storage was not verified. The remaining residues of dissipation in the rice grains were below the maximum residue level (MRL) prescribed by the law. The insecticide residues did not translocate in the husked rice grains destined for final consumption.

According to results of the Program of Analysis of Pesticide Residues in Foods of the National Agency of Sanitary in Brazil (2013 to 2015) the zucchini, Cucurbita pepo L is one of the non-hardy vegetables, that presented higher contamination index by pesticides residues. One of these agrochemicals is carbofuran, which although not authorized for this crop, is commonly and illegally used for whitefly control. The objective of this study was to optimize the solid-liquid extraction method with low temperature partitioning (SLE/LTP) for the determination of carbofuran residues in zucchini by high performance liquid chromatography with ultraviolet detector (HPLC-UV). The optimization was performed with a complete factorial design, 2³ to evaluate the simultaneous performance of three factors in two levels, in triplicate. The optimized SLE/LTP-HPLC/UV method showed to be selective, simple and efficient, consuming a small amount of sample and solvent extractor. The average recovery percentage was 75.88%. Samples of zucchini purchased in the Itumbiara-GO trade, Brazil, and submitted to the optimized method did not present carbofuran residues.

Parâmetros de maturação de frutos de tomate como pH, ºBrix, acidez e teores de licopeno e β-caroteno foram avaliados. Cinco agrotóxicos foram quantificados em extratos orgânicos de tomate em diferentes fases de maturação. A técnica de extração sólido-líquido com partição em baixa temperatura (ESL-PBT) foi utilizada para a obtenção desses extratos orgânicos. O efeito da matriz tomate foi calculado a partir dos resultados da análise por cromatografia gasosa com detector de captura de elétrons (CG-DCE). Correlações entre os parâmetros de maturação e efeito matriz foram estudadas. A correlação entre o teor de carotenoides e o efeito matriz foi elevada para todos os pesticidas estudados. Os resultados indicam que o efeito produzido pela matriz tomate está correlacionada com a presença de licopeno e β-caroteno em extratos orgânicos. A análise de componentes principais (PCA) mostrou que o licopeno, caroteno e a mistura de ambos têm efeitos significativos sobre a resposta cromatográfica de pesticidas.

Some parameters of tomato fruits ripening such as color, pH, ºBrix, acidity and lycopene and β-carotene content were evaluated during the ripening of fruits. Five pesticides were quantified in organic extracts derived from tomatoes at different stages of maturation. The solid-liquid extraction technique with partition at low temperature (SLE-PLT) was used to obtain these organic extracts. The matrix effect of tomato was calculated from the results of analysis by gas chromatography with electron capture detector (GC-ECD). Correlations between maturation parameters and matrix effect were performed. The correlation between the content of carotenoids and matrix effect was high for all pesticides studied. The results indicate that the effect produced by the tomato matrix is correlated with the presence of lycopene and β-carotene in organic extracts. The principal component analysis (PCA) showed that lycopene, carotene and the mixture of both have significant effects on the chromatographic response of pesticides, separating them into distinct groups.

O uso indiscriminado de agrotóxicos em morangos pode torná-los impróprios para consumo. Neste estudo, o método extração sólido-líquido com partição em baixa temperatura (SLE/LTP) acoplado a cromatografia gasosa com detector por captura de elétrons (GC/ECD) foi otimizado. O método proposto foi validado pela análise de amostras fortificadas do branco da matriz. Os limites de detecção (LOD) variaram entre 4 e 16 µg kg-1, enquanto que os limites de quantificação (LOQ) variaram entre 13 e 47 µg kg-1. Boas recuperações (79-111%) e precisão (< 15%) foram obtidos para todos os compostos na matriz. Este método foi aplicado com sucesso na análise de resíduos de agrotóxicos encontrados em morangos coletados de sete fazendas do Vale do Jequitinhonha (MG, Brasil). Os resultados revelaram a presença de azoxistrobina, clorotalonil, difenoconazol e iprodiona nas amostras de morango.

The indiscriminate use of pesticides in strawberries can often make this crop unfit for consumption. In this study, the method of solid-liquid extraction with low-temperature partitioning (SLE/LTP) coupled with gas chromatography with electron capture detection (GC/ECD) was optimized. The proposed analytical method was validated by the analysis of spiked blank matrix samples. Limits of detection (LOD) varied between 4 and 16 µg kg-1, whereas limits of quantification (LOQ) ranged from 13 to 47 µg kg-1. Good recoveries (79-111%) and precision values (< 15%) were obtained for all compounds in the target matrix. This method has been successfully applied to the analysis of residues of pesticides found in strawberries collected from seven farms in the High Jequitinhonha Valley (MG, Brazil). The results revealed the presence of azoxystrobin, chlorothalonil, difenoconazole and iprodione in the strawberry samples.

The sugarcane industry has huge potential for biorefinery concept application, given its development in recent years. In this context, cane sugar straw has become an attractive raw material for biofuel production. This study aims to investigate the chemical composition of cane sugar straw from different regions of Brazil, and to optimize a hydrothermal pretreatment stage for cellulosic ethanol production. Results of chemical characterization of the cane sugar straw for the regions assessed indicated little influence of place on straw chemical composition. Hydrothermal pretreatment showed high efficiency in hemicellulose removal. Hydrothermal pretreatments operating with temperatures of 190 and 210 ºC presented satisfactory results, reaching values close to 100% hydrolysis.

O principal objetivo deste trabalho foi avaliar a presença de resíduos de clorpirifós e tiametoxam em amostras de batata e solo em diferentes circunstâncias, após a otimização e validação da técnica de extração sólido-líquido e partição em baixa temperatura. Porcentagens de recuperação entre 93% e 105% foram obtidas para os pesticidas nas amostras. O método otimizado e validado foi aplicado às amostras de batata obtidas em supermercado e foi obtido resíduo de clorpirifós na concentração de 0,67 mg kg-1. Batatas cultivadas no campo foram tratadas com os pesticidas em diferentes dias e resíduo de clorpirifós foi detectado. As batatas cultivadas em vasos foram tratadas com clorpirifós e tiametoxam somente no plantio. Após 91 dias, foi observada uma concentração de tiametoxam acima do LMR permitido. O método proposto foi eficiente na determinação de clorpirifós e tiametoxam e foi concluído que o monitoramento de agrotóxicos deve ser realizado periodicamente para garantir a qualidade dos produtos e a saúde do consumidor.

The main objective of this work was to evaluate the presence of residues of chlorpyrifos and thiamethoxam in potato and soil samples under different circumstances after optimization and validation of solid-liquid extraction and partitioning at low temperature technique. Recovery percentages between 93% and 105% were obtained for pesticides in the samples. The optimized and validated method was applied to potatoes from supermarkets and it was obtained chlorpyrifos residue at concentrations of 0.67 mg kg-1. Potatoes grown in the field were treated with pesticide on different days and chlorpyrifos was the only residue detected. The potatoes grown in pots were treated with chlorpyrifos and thiamethoxam only at planting. After 91 days, it was observed the concentration of thiamethoxam in the potatoes higher than the tolerable MRL. The proposed method was efficient in the determination of chlorpyrifos and thiamethoxam and it was concluded that the monitoring of pesticides in food must be performed periodically to ensure the product quality and the safety of consumer's health.

Um método para determinação simultânea de 14 agrotóxicos (organoclorados e piretroides) em água foi desenvolvido utilizando microextração em gota única (SDME) e cromatografia gasosa com detector de captura por elétrons. Variáveis experimentais incluindo solvente orgânico, volume da microgota, tempo de extração, volume e velocidade de agitação da amostra e adição de sal foram avaliadas a fim de maximizar o desempenho da técnica SDME. Coeficientes de variação (CV), abaixo de 20% e recuperações relativas entre 71 e 107% indicaram boa precisão e exatidão do método. O protocolo desenvolvido também mostrou seletividade e boa linearidade com coeficientes de correlação (r) superiores a 0,99. Os limites de detecção dos analitos de interesse apresentaram-se entre 0,003 e 0,6 µg L-1, todos abaixo dos respectivos níveis máximos de contaminantes para água potável. Amostras de água potável foram analisadas utilizando o método proposto e nenhum dos pesticidas foi detectado.

A method for simultaneous determination of 14 pesticides (organochlorine and pyrethroid) in water was developed using the single drop microextraction (SDME) and gas chromatography with an electron capture detector. Experimental variables including organic solvent, volume of the microdrop, extraction time, volume and stirring speed of the sample and the addition of salt were evaluated to maximize the performance of the SDME technique. Coefficients of variation (CV) lower than 20% and relative recoveries between 71 and 107% indicated good precision and accuracy of the method. The developed protocol also showed selectivity and good linearity with correlation coefficients (r) greater than 0.99. Limits of detection of the analytes of interest were between 0.003 and 0.6 µg L-1, all below the respective maximum contaminant levels (MCL) for drinking water. Drinking water samples were analyzed using the proposed method and none of the pesticides were detected.

Carbamatos são os pesticidas mais frequentemente encontrados em alimentos e bebidas de coloração escura em casos de intoxicação acidental ou intencional. Neste trabalho, extração líquido-líquido com partição em baixa temperatura (LLE-LTP) foi otimizada e validada para determinação dos carbamatos aldicarb, carbofuran e carbaril em bebidas de sucos de uva e leite achocolatado. Este método envolve a extração com acetonitrila, partição líquido-líquido em baixa temperatura e análise por cromatografia líquida de alta eficiência com detecção ultravioleta (HPLC-UV). O método é rápido, eficiente e de baixo custo, emprega pequenos volumes de solvente por amostra e não necessita de limpeza dos extratos. O método de extração foi seletivo e apresentou porcentagens de extração acima de 90%. As premissas relacionadas com os testes estatísticos de linearidade foram verificadas e confirmadas. O método de extração e análise foi validado com resultados satisfatórios e pode ser aplicado em análises de rotina e forenses.

Carbamates are the pesticides most commonly found in dark colored foods and beverages in cases of accidental or intentional poisoning. In this work, the liquid-liquid extraction with low temperature partitioning (LLE-LTP) was optimized and validated for determination of the carbamates aldicarb, carbofuran and carbaryl in grape juice and chocolate milk beverages. This method involved extraction with acetonitrile, liquid-liquid partition at low temperature and the analysis by high performance liquid chromatography with ultraviolet detection (HPLC-UV). The method is rapid, efficient and of low-cost, employing small volumes of solvent per sample and requiring no cleanup of the extracts. The extraction methodology was selective and presented recovery percentages above 90%. The premises related to the statistical linearity tests were checked and confirmed. The method of extraction and analysis was validated with satisfactory results, and may be applied in forensic and routine analysis.

O efeito de matriz em análises por cromatografia gasosa é atribuído à presença de coextrativos na fase orgânica obtidos em processo de extração. Este trabalho relata o estudo da quantificação do aumento da resposta cromatográfica para quatro pesticidas em extratos orgânicos de tomate obtidos por extração sólido-líquido com purificação em baixa temperatura (ESL-PBT). Os pesticidas clorpirifós, l-cialotrina, cipermetrina e deltametrina apresentaram aumento da resposta cromatográfica depois da saturação do sistema cromatográfico com múltiplas injeções de extrato orgânico de tomate. Verificou-se também que quanto maior o tempo de retenção, maior o efeito de matriz, e o padrão interno reduz o efeito deste, mas não o elimina. O efeito de matriz medido pelas curvas analíticas (em acetonitrila e extrato da matriz) foi 27% para o clorpirifós, 46% para l-cialotrina, 96% para cipermetrina e 180% para deltametrina.

The matrix effect in gas chromatographic analysis is attributed to the presence of coextractives in organic phase obtained in the extraction process. This work reports the quantification study of increased chromatographic response of four pesticides in organic extracts of tomato extracted by solid-liquid extraction with low temperature purification (SLE-LTP). The pesticides chlorpyrifos, λ-cyhalothrin, cypermethrin and deltamethrin showed an increased chromatographic response after the saturation of the chromatographic system with multiple injections of organic extracts of tomato. It was also found that the greater the retention time, the greater the matrix effect, and that the internal standard reduces the matrix effect but does not eliminate it. The matrix effect measured by the analytical curves (in acetonitrile and matrix extract) was 27% for chlorpyrifos, 46% for λ-cyhalothrin, 96% for cypermethrin and 180% for deltamethrin.

A method for simultaneous analysis of trihalomethanes and organochloride and pyrethroid pesticides in water utilizing SPME-HS and GC-ECD was developed. In the optimized method 25 mL of water containing 2% (w/v) Na2HPO4 were heated to 60 °C for 50 min. The fiber (PDMS - 100 μm) was exposed to a headspace for the same period. For all analytes it was found that LOQ < MCL (Maximum Contaminant Level), CV < 20% and r > 0.9. The method was applied to potable and surface water samples. Some trihalomethanes were encountered in potable waters, at levels below the MCL.

Multiresidue methods for pesticides monitoring by GC are commonly employed, however, it is well known that the presence of compounds of the matrix introduces errors during the quantiûcation. The main consequence of matrix effect is an increasing or decreasing analyte signal after the GC saturation with extracts of matrix. In this paper, the influence of constituents of nine matrices on the quantification of the four pesticides by GC-ECD was studied. Variation of signal was evaluated by PCA and HCA, and results showed that the constituents of tomato increased the signal (until 300%), while extracts of apple decreased (until -20%). Variation the analyte signal in the presence of the matrix in respect to the same analyte in solvent (standard solution) also was observed, mainly for liver extract (until 270%).

The lack of accuracy of a chromatographic method can be associated with the matrix effect. This effect is observed in pesticide quantification by gas chromatography when the chromatographic signals of standards prepared in solvents are compared with those of the analyte in extracts of complex matrices. In the competition between the matrix components and the pesticides for the active sites of the liner, a larger amount of pesticides is transferred to the column, giving apparent extractions above 100%. In this work, we discuss factors that contribute to the matrix effect and present some attempts to overcome the problem.