MSPD procedure combined with GC-MS for the determination of procymidone, bifenthrin, malathion and pirimicarb in honey

A method based on matrix solid-phase dispersion and gas chromatography-mass spectrometry to determine procymidone, malathion, bifenthrin and pirimicarb in honey is described. The best results were obtained using 1.0 g of honey, 1.0 g of silica-gel as dispersant sorbent and acetonitrile as eluting solvent. The method was validated by fortified honey samples at three concentration levels (0.2, 0.5 to 1.0 mg kg-1). Average recoveries (n=7) ranged from 54 to 84%, with relative standard deviations between 3.7 and 8.5%. Detection and quantification limits attained by the developed method ranged from 0.02 to 0.08 mg kg-1 and 0.07 to 0.25 mg kg-1 for the honey, respectively.

In-house method validation and occurrence of alpha-, beta-endosulfan, endosulfan sulphate, lambda-cyhalothrin, procymidone and trifluralin residues in strawberry

A method for determination of organohalogen pesticides in strawberry by gas chromatography with electron capture detection was validated and applied in a monitoring program. Linearity, matrix effects, and day effect were evaluated for the analytes alpha-endosulfan, beta-endosulfan, endosulfan sulphate, lambda-cyhalothrin, procymidone, and trifluralin. The linear range varied according to the chromatographic response of the analyte. Significant matrix effects were observed. The mean recoveries ranged from 74.6 to 115.4%, with repeatability standard deviations between 1.6 and 21.0% and intermediate precision between 5.9 and 21.0%. Detection, quantification and decision limit, and detection capacity ranged from 0.003 to 0.007 mg/kg, 0.005 to 0.013 mg/kg; 0.003 to 3.128 mg/kg; and 0.005 to 3.266 mg/kg, respectively. The method was fit for the purpose of monitoring organohalogen residues in strawberries. Residues of these pesticides were detected in 124 of the 186 samples analyzed between 2009 and 2011 in the state of Minas Gerais. Nine of them did not comply with the current legislation requirements; among them, seven (3.8%) had residues of unauthorized pesticide for the culture of strawberry, one (0.5%) had residues above the maximum residue limit, and another one (0.5%) exhibited both non-conformities.

New voltammetry-based analytical method for indirect determination of procymidone in brazilian apples

Procymidone, a potentially carcinogenic and mutagenic pesticide, can contribute to environmental and human contamination when applied to apple crops. In this work, we propose a reliable and sensitive method to determine procymidone in Brazilian apples. The method involves differential pulse (DPV) and square-wave voltammetry (SWV) techniques on a glassy carbon electrode. In a supporting electrolyte solution of 0.5 mol L−1 NaOH, procymidone undergoes an irreversible one-electron oxidation at +1.42 V by cyclic voltammetric vs. Ag|AgCl, KCl 3 M reference electrode. The proposed DPV and SWV methods have a good linear response in the 8.00–20.0 mg L−1 range, with limits of detection (LOD) of 0.678 and 0.228 mg L−1, respectively, in the absence of the matrix. We obtained improved LOD (0.097 mg L−1) in the presence of apple matrix and the supporting electrolyte solution. We used three commercial apple samples to evaluate recovery, and we achieved recovery percentages ranging from 94.6 to 110 % for procymidone determinations. We also tested the proposed voltammetric method for reproducibility, repeatability, and potential interferents, and the results were satisfactory for electroanalytical purposes.

Analysis of six fungicides and one acaricide in still and fortified wines using solid-phase microextraction-gas chromatography/tandem mass spectrometry

A multiresidue gas chromatographic method for the determination of six fungicides (captan, chlorthalonil, folpet, iprodione, procymidone and vinclozolin) and one acaricide (dicofol) in still and fortified wines was developed. Solid-phase microextraction (SPME) was chosen for the extraction of the compounds from the studied matrices and tandem mass spectrometry (MS/MS) detection was used. The extraction consists in a solvent free and automated procedure and the detection is highly sensitive and selective. Good linearity was obtained with correlation coefficients of regression (R2) > 0.99 for all the compounds. Satisfactory results of repeatability and intermediate precision were obtained for most of the analytes (RSD < 20%). Recoveries from spiked wine ranged from 80.1% to 112.0%. Limits of quantification (LOQs) were considerably below the proposedmaximumresidue limits (MRLs) for these compounds in grapes and below the suggested limits for wine (MRLs/10), with the exception of captan.

Desenvolvimento de metodologias analíticas para a determinação de resíduos de pesticidas em Vinhos do Douro e Vinhos do Porto

A produção de vinho é uma actividade de elevada importância ao nível económico, ambiental e social. Como tal, a protecção da vinha e/ou da uva através da utilização de pesticidas assume um papel fundamental nesta actividade, permitindo um aumento no rendimento da produção. No entanto, a transferência destes compostos da uva para o vinho é inevitável, ocorrendo, na maioria dos casos, em quantidades reduzidas. Apesar de, geralmente, a quantidade de pesticidas que pode ser transferida para o vinho não apresentar problemas relevantes para a saúde pública, o desenvolvimento de metodologias que permitam garantir um controlo rigoroso da qualidade do vinho é de elevada importância. O controlo deste produto, assim como de qualquer produto alimentar, não deve ser de certa forma virtual, levando a uma desconfiança crescente do consumidor. Ao longo deste trabalho foram desenvolvidos dois métodos para a determinação de pesticidas em diferentes tipos de vinhos, por SPME-GC-MS/MS. O primeiro método desenvolvido visa a determinação de 8 pesticidas organofosforados e o segundo método permite a determinação de 7 pesticidas, 4 organoclorados e 3 dicarboximidas. Foram estudadas quatro matrizes diferentes: vinho branco do Douro, vinho tinto do Douro, vinho branco do Porto e vinho tinto do Porto. As metodologias adoptadas permitiram a obtenção de bons resultados, apesar das condições adoptadas não serem as mais vantajosas para alguns dos compostos estudados. Dada a complexidade das matrizes, a detecção por espectrometria de massa mostrou ser fundamental para a identificação inequívoca de cada um dos pesticidas. Verificaram-se, de um modo geral, bons resultados ao nível da linearidade, para as gamas de concentrações escolhidas, para os dois métodos. Obtiveram-se também bons resultados para os limites de detecção e quantificação, cujos valores se situam abaixo dos limites máximos de resíduos para as uvas, impostos pela regulamentação europeia, para a maioria dos compostos. No caso dos organofosforados, os limites de detecção variam entre 0,05 μg/L e 13,00 μg/L para os pesticidas clorpirifos-metilo e metidatião, respectivamente. Os limites de quantificação variam entre 0,18 μg/L e 43,32 μg/L, também para os pesticidas clorpirifos-metilo e metidatião. No que se refere ao método para os pesticidas organoclorados e dicarboximidas, foram calculados vários limites de detecção para cada composto, em cada matriz estudada, a partir das rectas de calibração diárias, resultando num conjunto de valores com variações significativas entre cada um, para o mesmo pesticida e na mesma matriz. No entanto, apenas os limites de quantificação foram validados, recorrendo-se aos estudos de repetibilidade e precisão intermédia. Obtiveram-se os seguintes limites de quantificação: captana 52,10 μg/L; clortalonil 20,95 μg/L; dicofol 4,37 μg/L; folpete 93,60 μg/L; iprodiona 274,70 μg/L; procimidona 76,04 μg/L e vinclozolina 10,03 μg/L. Os pesticidas metidatião e captana apresentam-se como os compostos mais problemáticos, uma vez que os limites de quantificação obtidos não permitem a garantia do cumprimento dos limites máximos de resíduos regulamentados. Demonstra-se também que, apesar do efeito de matriz ser significativo na determinação de todos os compostos analisados, o mesmo pode ser atenuado, procedendo-se às calibrações nas respectivas matrizes. Observaram-se variações significativas ao nível da resposta do equipamento ao longo do tempo, quer pela alteração das condições operatórias, quer pela decomposição de alguns compostos ao longo do tempo. Este efeito, evidenciado nos estudos das precisões intermédias e repetibilidades, levou à adopção de um método de validação diferente para a determinação de pesticidas organoclorados e dicarboximidas, recorrendo-se então a calibrações diárias e sequências de trabalho mais pequenas.

Development of a SPME-GC-ECD methodology for selected pesticides in must and wine samples

A method for the determination of some pesticide residues in must and wine samples was developed using solid-phase microextraction (SPME) and gas chromatography – electron capture detection (GC/ECD). The procedure only needs dilution as sample pre-treatment and is therefore simple, fast and solvent-free. Eight fungicides (vinclozolin, procymidone, iprodione, penconazole, fenarimol, folpet, nuarimol and hexaconazole), one insecticide (chlorpyriphos) and two acaricides (bromopropylate and tetradifon) can be quantified. Good linearity was observed for all the compounds in the range 5–100 µg/L. The reproducibility of the measurements was found acceptable (with RSD’s below 20%). Detection limits of 11 µg/L, on average, are sufficiently below the proposed maximum residue limits (MRL’s) for these compounds in wine. The analytical method was applied to the determination of these compounds in Portuguese must and wine samples from the Demarcated Region of Alentejo, where any residues could be detected.

White mold intensity on common bean in response to plant density, irrigation frequency, grass mulching, Trichoderma spp., and fungicide

The purpose of this study was to evaluate the efficiency of integrated managements on white mold control on common bean. Initially, in vitro testing was made to assess the antagonism of 11 Trichoderma isolates against Sclerotinia sclerotiorum and to investigate fungicides (fluazinam and procymidone) inhibitory effects on those fungi. In two field experiments the following combinations were tested: irrigation frequencies (seven or 14 days), plant densities (six or 12 plants per meter), and three disease controls (untreated control, fungicide or Trichoderma spp.). In a third experiment plant densities were replaced by grass mulching treatments (with or without mulching). Fluazinam was applied at 45 and 55 days after emergence (DAE). The antagonists T. harzianum (experiments 1 and 3) and T. stromatica (experiment 2) were applied through sprinkler irrigation at 10 and 25 DAE, respectively. Most of the Trichoderma spp. were effective against the pathogen in vitro. Fluazinam was more toxic than procymidone to both the pathogen and the antagonist. Fungicide applications increased yield between 32 % and 41 %. In field one application of Trichoderma spp. did not reduce disease intensity and did not increase yield. The reduction from 12 to six plants per meter did not decrease yield, and disease severity diminished in one of the two experiments. It is concluded that of the strategies for white mold control just reduction of plant density and applications of fungicide were efficient.

Design of a simple detection cell with extended optical path length for capillary electrophoresis: Application to multiresidue pesticide analysis

Absorbance detection in capillary electrophoresis (CE), offers an excellent mass sensitivity, but poor concentration detection limits owing to very small injection volumes (normally I to 10 nL). This aspect can be a limiting factor in the applicability of CE/UV to detect species at trace levels, particularly pesticide residues. In the present work, the optical path length of an on-column detection cell was increased through a proper connection of the column (75 mu m i.d.) to a capillary detection cell of 180 mu m optical path length in order to improve detectability. It is shown that the cell with an extended optical path length results in a significant gain in terms of signal to noise ratio. The effect of the increase in the optical path length has been evaluated for six pesticides, namely, carbendazim, thiabendazole, imazalil, procymidone triadimefon, and prochloraz. The resulting optical enhancement of the detection cell provided detection limits of ca. 0.3 mu g/mL for the studied compounds, thus enabling the residue analysis by CE/UV.

Pesticides in the distilled spirits of wine and its byproducts

The fate of eight fungicides (benalaxyl, fenarimol, iprodione, metalaxyl, myclobutanil, procymidone, triadimefon, and vinclozolin) and five insecticides (dimethoate, fenthion, methidathion, parathion methyl, and quinalphos) in wine and its byproducts (cake and lees) during the production of distilled spirits was studied. Among the pesticides studied, only fenthion, quinalphos, and vinclozolin residues were present in the distilled spirits. During wine distillation, respectively 13% and 5% of the initial residues of fenthion and vinclozolin were transferred to the distilled spirit. Low percentages (2% for fenthion and 0.1% for vinclozolin) of these active ingredients (AI) also passed from the lees to the final-distilled spirit, when samples were fortified at 10.1 and 26.1 ppm for fenthion and vinclozolin, respectively. Quinalphos passed only from the lees to the final-distilled spirit in percentages lower than 1% when samples were fortified at the highest concentration (4.6 ppm).

Ação de fungicidas e acibenzolar-se-methyl no controle da pinta preta do tomateiro

Pós-graduação em Agronomia (Proteção de Plantas) - FCA

Métodos de aplicação e de avaliação do residual de fungicidas no controle de mofo-branco em soja e feijão

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)