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.

The contamination of water bodies by pesticide residues through direct flow, leaching and other methods has motivated the development of analytical methods for the determination of these compounds in water. A vortex-assisted liquid-liquid microextraction method followed by gas chromatography coupled to mass spectrometry for the determination of anilazine, linuron, prothiofos, and tebuconazole residues in water samples from the culture and processing of potatoes (Solanum tuberosum L.) was optimized. The complete factorial design and the central rotational compound design combined with the desirability function were used to evaluate and optimize the parameters of the method. The optimized conditions for extracting the pesticides were as follows: 316 µL of toluene, no sodium chloride addition, and a stirring time of 187 s. The method presented an enrichment factor of 142.4 times and good linearity, precision and accuracy, with limits of detection (LOD) of 0.005 - 0.007 mg L-1 and limits of quantification (LOQ) of 0.016 - 0.022 mg L-1. The co-extractives of the wastewater samples caused the suppression of the chromatographic response of linuron and prothiofos by 7.82 and 27.63%, respectively. The analyte concentrations in the wastewater samples from the industrial shing process, manual potato washing, and dam water were either lower than the LODs of the method or were absent.

A new method has been developed to determine trace levels of organophosphorus pesticide parathion-methyl in water samples by using dispersive liquid-liquid microextraction (DLLME), followed by gas chromatograph coupled with electron capture detector (GC/ECD) analysis. The optimized and validated method showed high extraction recovery (101.1%), high enrichment factor (57.3), low limits of detection and quantification, 0.083 and 0.250 µg L-1, respectively. The established DLLME-GC/ECD method has been successfully applied for the evaluation of the photodegradation of the parathion-methyl by UV254nm radiation in different conditions of pH and temperature. The parathion-methyl photodegradation at pH 3 and 35 °C achieved > 99.5% after 120 min of exposition. For this condition, it was observed the kinetic rate of 0.0515 min-1, the quantum yield of 1.22 × 10-5 mol Einstein-1 and a half-life time of 13.46 min. All experimental conditions tested proved to be strongly influenced by pH and temperature. The application of the optimized process in distilled and drinking water spiked with parathion-methyl provided residues of this pesticide at levels below the maximum permitted by Brazilian legislation, which is 9.0 µg L-1.

ABSTRACT The implementation of the ozonation process in the milling industry to control insect pests and improve wheat flour qualities requires understanding the behavior of ozone during ozonation. Therefore, this study aimed to investigate the reaction kinetics of ozone gas in wheat flour. Wheat flour ozonation at concentrations of 0.54, 1.07, 1.61 and 2.14 mg L−1 was used in a prototype consisting of a cylinder and a mixing system with a helical thread. The iodometric titration method was used to quantify the ozone concentration in the air stream. The reaction kinetics were characterized by determining the saturation time and the decomposition kinetics (decay rate and half-life time). With increasing ozone concentration, less time was required to saturate the wheat flour. The saturation times were 812, 434, 370 and 342 min for ozone concentrations of 0.54, 1.07, 1.61 and 2.14 mg L−1, respectively. Increasing the ozone concentration did not influence the constant decay rate and half-life time. The ozone decomposition kinetics could be represented by a first-order model, with a decay rate constant of 0.23±0.008 min−1 and a half-life time of 3.02±0.081 min.

Due to uncontrolled use of pesticides and disregard for harvest intervals, some pesticide residue is present in various foods. Treatments using ozone as an alternative for food decontamination have been studied in recent years due to ozone’s high oxidation potential even at low concentrations. The present work aimed to evaluate chlorothalonil removal from table grapes by the immersion of fruit in distilled water continuously bubbled with ozone gas. This strategy allowed the removal of 60% of chlorothalonil from table grapes (pulp and skin), regardless of ozone concentration. Ozone treatment of table grapes at a gas concentration of 3 mg L−1 changed most of the quality parameters evaluated. Treatment at 2 mg L−1 maintained the fruit quality for a longer storage period compared to the untreated control table grapes.

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.

Three analytical methods for the determination of BTEX in water were optimized and validated. With the best method the analytes were extracted of 10 mL of sample with 2.50 g of NaCl in headspace vial of 20 mL by HS and SPME to 40 ºC for 30 min for adsorption and to 250 ºC for 4 min for desorption and were analyzed by GC-MS. The recovery was between 97.9% and 104.3%, and the limit of detection was 2.4 ng L-1 for o-xylene. This method was using to analyze BTEX in water supply and surface water in Ouro Preto city. No sample had concentrations of BTEX above the legislation.