Aplicação da cromatografia gasosa bidimensional abrangente com microdetector de captura de elétrons para determinação de agrotóxicos em sedimentos

Analysis of seven pesticides in sediments was successfully achieved using comprehensive two-dimensional gas chromatography with micro-electron capture detection, as it provided higher sensitivity and less matrix interference. Repeatability and intermediate precision of peak areas and heights were less than 4% and the recovery percentage for the analytes ranged from 52 to 115%. Instrumental LOD and LOQ were in the range of 0.60 to 2.31 μg L-1 and 1.83 to 5.62 μg L-1, respectively. Concentrations of 3.34 μg kg-1 (dry basis) for trifloxystrobin and azoxystrobin (below the LOQ) were found in a sediment sample.

Principais técnicas de preparo de amostra para a determinação de resíduos de agrotóxicos em água por cromatografia líquida com detecção por arranjo de diodos e por espectrometria de massas

The determination of pesticide residues in water samples by Liquid Chromatography require sample preparation for extraction and enrichment of the analytes with the minimization of interferences to achieve adequate detection limits. The Solid Phase Extraction (SPE), Solid Phase Microextraction (SPME), Stir Bar Sorptive Extraction (SBSE) and Dispersive Liquid-Liquid Microextraction (DLLME) techniques have been widely used for extraction of pesticides in water. In this review, the principles of these sample preparation techniques associated with the analysis by Liquid Chromatography with Diode Array Detection (LC-DAD) or Mass Spectrometry (LC-MS) are described and an overview of several applications were presented and discussed.

Craqueamento termo-catalítico da mistura óleo de fritura usado-lodo de estamparia têxtil para a produção de óleo com baixo índice de acidez

In this work, cracking experiments were performed to carry out the thermal conversion of the mixture of used frying oil and textile stamping sludge in continuous reactor. The textile stamping sludge was used to catalyze the reaction of thermal cracking. The physical and chemical properties of the oil produced were analyzed. Among the results of this analysis the level of acidity in the range of 12 mg KOH/g stands out. Low levels of acidity as this particular mean better quality oil. In this regard it is important that further researches on processes of conversion of residual oil occur.

Análise de agrotóxicos em água usando extração líquido-líquido com partição em baixa temperatura por cromatografia líquida de alta eficiência

This study optimized and validated the liquid-liquid extraction technique with partition at low temperature (LLE-PLT) for identification and quantification of four pesticides (chlorpyrifos, λ-cyhalothrin, permethrin, bifenthrin) in water samples. Analyses were performed by HPLC-UV. The technique was efficient for pesticide recovery with extraction exceeding 86%. Chromatographic response was linear for the four compounds in the 10-45 µg L-1 range, with correlation coefficients greater than 0.99. Limits of detection and quantitation were less than 3.5 µg L-1 and equal to 10 µg L-1, respectively. The proposed method was applied to 29 water samples from the Jaíba Project in northern Minas Gerais.

Comparação dos métodos de determinação da estabilidade oxidativa de biodiesel B100, em mistura com antioxidantes sintéticos: aplicação do delineamento simplex-centroide com variável de processo

The Rancimat and accelerated stove tests were used to determine the oxidative stability of B100 biodiesel mixed with synthetic antioxidants. The predictive equations, with process variable, were obtained by applying a simplex-centroid design. Regardless of the antioxidant used, all assays carried out with the accelerated stove test presented storage time longer than 177.88 d, the greatest value obtained by applying the Rancimat test. The t test, applied to the parameters containing the process variable, showed a statistically significant difference (at the level of 5%) between the methods used.

Revisão dos tratamentos químicos da fibra natural para mistura com poliolefinas

The use of natural fibers as reinforcement in polymer composites has been a focus of interest. However, these composites exhibit lower mechanical properties than those of pure polymers because of the low interfacial interactions between the hydrophobic polymer matrix and the hydrophilic fiber. To overcome this problem, different chemical treatments applied to the fibers have been reported. One of the most used treatments is mercerization, which can improve adhesion between the fiber and polymeric matrix. Another chemical treatment involves the use of acids (stearic and oleic acids). The chemically treated fibers used in composite materials showed improved mechanical properties.

Inventário de agrotóxicos e risco de contaminação química dos recursos hídricos no semiárido cearense

The first diagnosis of risk of environmental contamination was conducted for an area of intense agricultural activity in the semiarid cearense (Baixo Jaguaribe and Litoral de Aracati area). We verified the use of 201 rural products (pesticides) in the region, comprising 151 active ingredients. Regarding the active ingredients evaluated, 15.9% were associated with sediment and 29.8% were dissolved in surface water. The study showed that 13.2% to 36.4% of the active ingredients evaluated were classified as potential contaminants of groundwater resources. The study also revealed the most abundant pesticides and which environmental compartment must be evaluated.

Determinação de resíduos de agrotóxicos em leite bovino empregando método QuEChERS modificado e GC-MS/MS

Considering the possibility that pesticides used in cattle raising produce residues in milk and cause harm to public health, this study developed a multiresidue method for determination of pesticide residues in bovine milk, using a modified QuEChERS method for sample preparation, and quantification by GC-MS/MS. The method proved to be efficient, resulting in satisfactory recoveries in the range 71.1 to 117.4%, for 45 of the 48 compounds analyzed with RSD values < 17.3%. The method LOD and LOQ were3.0 and 10.0 µg L-1, respectively, except for cyfluthrin which showed 7.5 and 25.0 µg L-1.

Avaliação de risco ambiental de ambientes aquáticos afetados pelo uso de agrotóxicos

Ecological risk assessment is a process evaluating the likelihood that adverse ecological effects may occur or are occurring as a result of exposure to one or more substances. Relevant information needed to predict risks from pesticides includes their physical chemical properties, mobility in soil, persistence in the environment, and bioaccumulation and toxicity in relevant organisms. Although currently a requirement for pesticide registration in Brazil, this process is not yet fully implemented in the country. This review aims to outline the principles of environmental risk assessment for pesticides, focusing on aquatic organisms, and to discuss the studies and efforts conducted in Brazil in this area.

MONITORAMENTO DE RESÍDUOS DE AGROTÓXICOS DA CLASSE DOS ORGANOFOSFORADOS POR CGDFC EM AMOSTRAS DE LEITE FLUÍDO E EM PÓ

Samples of whole fluid pasteurized, UHT and powdered milk were analyzed for the presence of organophosphorus pesticide residues (OPR) using the QuEChERS method with detection by GC-FPD and confirmation by UPLC-MS/MS. A total of 23% of fluid milk samples and 27% of powdered milk samples contained at least one organophosphorus residue. The OPR found in the samples showed these can reach the milk and remain even after pasteurization, sterilization and drying processes. Some domestic sanitary residues were also present in the powdered milk samples. These residues have no LMR in Brazilian food legislation and are therefore not taken into account in food intake evaluations. There was an unidentified chromatographic peak in 30% of all the liquid and powdered milk samples, indicating the presence of some other contaminant.

COMPARAÇÃO DE MÉTODOS POR CROMATOGRAFIA LÍQUIDA NA DETERMINAÇÃO DE MULTIRRESÍDUOS DE AGROTÓXICOS EM MORANGOS

Liquid chromatography is often used for the determination of pesticide multiresidues in foods. In Brazil, the strawberry crop is an example of a food with high levels of irregularities because of the application of pesticides. This is a major concern from the perspective of food safety, environmental protection, and certification for food export. The purpose of this study is to evaluate and compare chromatographic separation and detection methods in relation to a newly developed and validated method using ultra high performance liquid chromatography (LC) coupled with tandem mass spectrometry (MS/MS) for the analytical determination of pesticides in strawberries. The comparisons were based on evaluations of the analysis time, consumption of the solvent in the mobile phase, injection volume, detectability, matrix effect, and recovery. The results showed that the LC–MS/MS and UHPLC–MS/MS techniques were both extremely efficient at analyzing pesticide residues with different physico-chemical parameters that were present at low concentrations in a complex matrix. The UHPLC separation method provided better chromatographic performance and productivity, which contributed favorably to routine analytical determinations. Detection by MS/MS had better detectability and selectivity compared with the diode array detector.

Fungicidas e mistura de fungicidas no controle do oídio da soja

Dois experimentos foram conduzidos em Londrina/PR para avaliar a eficácia de fungicidas e suas misturas no controle do oídio (Microsphaera diffusa) da soja (Glycine max). Uma aplicação dos produtos foi feita no estádio R4 da soja cv. EMBRAPA 48. Os melhores resultados foram obtidos com os seguintes fungicidas: tebuconazol-1 e tebuconazol-2, carbendazim-1 e carbendazim-2 (produtos comerciais diferentes). Teste 1 - tebuconazol-2 (150 g i. a./ha), prochloraz + propiconazol (225 + 62,5), propiconazole + carbendazim-1 (50 + 175) e tebuconazol-1 + propiconazol (75 + 62,5); Teste 2 - carbendazim-1 (250), carbendazim-2 (250) e tebuconazol-2 (100).

Efeito do silicato de potássio isoladamente ou em mistura com fungicida no controle da requeima da batateira

Este trabalho teve como objetivo avaliar o efeito da aplicação foliar de silicato de potássio, isoladamente ou em mistura com diferentes doses do fungicida, no controle da requeima, causada por Phytophthora infestans, da batateira. O experimento foi conduzido em condições de campo utilizando-se o delineamento em blocos casualizados com 8 tratamentos e 4 repetições. A cultivar de batata usada foi a Asterix. Foi utilizado o fungicida Cimoxanil + Mancozeb (60 + 700 g/Kg i.a.) e silicato de potássio na dose de 60 g/L (pH = 5,5). Os tratamentos (T) utilizados foram: T1 - Testemunha; T2 - Cimoxanil + Mancozeb (2,0 Kg/ha); T3 - Cimoxanil + Mancozeb (2,5 Kg/ha); T4 - Cimoxanil + Mancozeb (2,0 Kg/ha) + silicato de potássio; T5 - Cimoxanil + Mancozeb (2,5 Kg/ha) + silicato de potássio; T6 - Cimoxanil + Mancozeb (3,0 Kg/ha) + silicato de potássio; T7 - silicato de potássio e T8 - Cimoxanil + Mancozeb (3,0 Kg/ha). As pulverizações foram realizadas semanalmente. A severidade da requeima foi avaliada utilizando-se uma escala descritiva com notas de 0 a 100%. Os resultados da severidade foram utilizados para calcular a área abaixo da curva do progresso da requeima (AACPR). A AACPR foi de 72,5; 23,8; 18,3; 29,5; 19,7; 17,9; 68,3 e 16,3, respectivamente, nos tratamentos T1, T2, T3, T4, T5, T6, T7 e T8. Os tratamentos 3, 5, 6 e 8 foram os mais eficientes (menores AACPRs e maiores rendimentos) no controle da requeima. O silicato de potássio não foi eficiente e não apresentou nenhum efeito aditivo quando misturado ao fungicida no controle da requeima.

Estabilização química do subleito de estradas: influência do tempo decorrido entre a mistura e a compactação na resistência mecânica de misturas solo-RBI Grade 81

Este artigo aborda o estudo da influência do tempo decorrido entre mistura e compactação na resistência mecânica de três solos da Zona da Mata Norte de Minas Gerais, Brasil, quando estabilizados com 4% de RBI Grade 81, em relação ao peso de solo seco. Um solo residual maduro (solo 1) e dois solos residuais jovens (solos 2 e 3) de gnáisse foram utilizados no presente estudo. O programa de ensaios de laboratório englobou: (i) tempos decorridos entre mistura e compactação: 0, 4, 8 e 24 horas; (ii) energia de compactação: Proctor Modificado; (iii) período de cura das misturas: 7 dias; e (iv) determinação da resistência mecânica: média de três determinações da resistência à compressão não-confinada. Os resultados desta pesquisa indicam que: (i) o tempo decorrido entre mistura e compactação dos corpos-de-prova influenciou significativamente o parâmetro resistência à compressão não confinada das misturas; (ii) 4 horas foi o tempo ótimo entre mistura e compactação para as misturas dos solos 1 e 2 com RBI Grade 81; e (iii) no solo 3, foi observado um melhor resultado para a compactação imediatamente após a mistura.