Toxicological Stability of Ocimum basilicum Essential Oil and Its Major Components in the Control of Sitophilus zeamais.

Essential oils (EOs) are widely recognized as efficient and safe alternatives for controlling pest insects in foods. However, there is a lack of studies evaluating the toxicological stability of botanical insecticides in stored grains in order to establish criteria of use and ensure your efficiency. The objective of this work was to evaluate the toxicological stability of basil essential oil (O. basilicum) and its linalool and estragole components for Sitophilus zeamais (Motschulsky) adults in corn grains by fumigation. The identification of the chemical compounds of the essential oil was performed with a gas chromatograph coupled to a mass selective detector. Mortality of insects was assessed after 24 h exposure. After storage for six (EO) and two months (linalool and estragole) under different conditions of temperature (5, 20, and 35 °C) and light (with and without exposure to light), its toxicological stability was evaluated. Studies revealed that the essential oil of O. basilicum and its main components exhibited insecticidal potential against adults of S. zeamais. For greater toxicological stability, suitable storage conditions for them include absence of light and temperatures equal to or less than 20 °C.

Method Validation and Evaluation of Safrole Persistence in Cowpea Beans Using Headspace Solid-Phase Microextraction and Gas Chromatography.

Bioinsecticides are regarded as important alternatives for controlling agricultural pests. However, few studies have determined the persistence of these compounds in stored grains. This study aimed at optimizing and validating a fast and effective method for extraction and quantification of residues of safrole (the main component of Piper hispidinervum essential oil) in cowpea beans. It also sought to assess the persistence of this substance in the grains treated by contact and fumigation. The proposed method used headspace solid-phase microextraction (HS-SPME) and gas chromatography with a flame ionization detector (GC/FID). Factors such as temperature, extraction time and type of fiber were assessed to maximize the performance of the extraction technique. The performance of the method was appraised via the parameters selectivity, linearity, limit of detection (LOD), limit of quantification (LOQ), precision, and accuracy. The LOD and LOQ of safrole were 0.0057 and 0.019 µg kg-1, respectively and the determination coefficient (R2) was >0.99. The relative recovery ranged from 99.26 to 104.85, with a coefficient of variation <15%. The validated method was applied to assess the persistence of safrole residue in grains, where concentrations ranged from 1.095 to 0.052 µg kg-1 (contact) and from 2.16 to 0.12 µg kg -1 (fumigation). The levels measured up from the fifth day represented less than 1% of the initial concentration, proving that safrole have low persistence in cowpea beans, thus being safe for bioinsecticide use. Thus, this work is relevant not only for the extraction method developed, but also for the possible use of a natural insecticide in pest management in stored grains.

The efficacy of washing strategies in the elimination of fungicide residues and the alterations on the quality of bell peppers.

Food safety problems caused by pesticide residues in vegetables have become a top issue to raise public concern. In this study, bell peppers were grown in an experimental field and sprayed with two systemic (azoxystrobin and difenoconazole) and one contact (chlorothalonil) fungicides. Ozone (ozonated water and water continuously bubble with ozone) or conventional domestic (washing with distilled water, detergent, acetic acid, sodium bicarbonate, and sodium hypochlorite solutions) procedures were investigated to identify the most effective way to remove fungicide residues in bell peppers. The residues in the fruits and the washing solutions were determined by solid-liquid extraction with a low-temperature partition (SLE/LTP) and liquid-liquid extraction with a low-temperature partition (LLE/LTP), respectively, and analyzed by gas chromatography. Water continuously bubbled with ozone a concentration of 3 mg L-1 was the most efficient treatment with removal of fungicides residues ranging from 67% to 87%. However, similar treatment at a lower concentration (1 mg L-1) did not only efficiently removed fungicide residues (between 53% and 75%) but also preserving the quality of the fruit along a storage time of 13 days. Among the conventional solutions, sodium bicarbonate at 5% showed good efficiency removing between 60% and 81% of the fungicide residues from bell peppers, affecting the color quality of the fruit. Overall, the most affected physicochemical parameters in bell peppers after the treatments were weight loss, color, and vitamin C content.

Headspace Solid-Phase Microextraction: Validation of the Method and Determination of Allyl Isothiocyanate Persistence in Cowpea Beans.

Essential oils are widely recognized as an efficient and safe alternative for controlling pests in foods. However, a few studies have determined the persistence of these compounds in stored grains. The present study optimized and validated a fast and effective method for extraction and quantification of allyl isothiocyanate (AITC-the main component of mustard essential oil) residue in cowpea beans. It also investigated the persistence of this substance in the grains. The proposed method employs headspace solid-phase microextraction (HS-SPME) and gas chromatography with a flame ionization detector (GC/FID). For optimizing it, a central composite design (CCD) was used, where the best conditions for the extraction of the AITC were achieved using 15 min fiber exposure at 30 °C. The performance of the method was assessed by studying selectivity, linearity, limits of detection (LOD) and quantification (LOQ), precision, and accuracy. The LOD and LOQ for AITC were 0.11 and 0.33 µg kg-1, respectively. The determination coefficient (R 2) was above 0.99. The relative recovery rate ranged from 108.2 to 114.8%, with an interday coefficient of variation below 9%. After 36 h, no residue was detected in the samples, demonstrating that the AITC has low persistence and can be safely used as a bioinsecticide for grains.

Optimal Extraction of Ocimum basilicum Essential Oil by Association of Ultrasound and Hydrodistillation and Its Potential as a Biopesticide against a Major Stored Grains Pest.

The essential oil of basil (Ocimum basilicum) has significant biological activity against insect pests and can be extracted through various techniques. This work aimed to optimize and validate the extraction process of the essential oil of O. basilicum submitted to different drying temperatures of the leaves and extracted by the combination of a Clevenger method and ultrasound. The biological activity of the extracted oil under different conditions was evaluated for potential control of Sitophilus zeamais. The extraction method was optimized according to the sonication time by ultrasound (0, 8, 19, 31 and 38 min) and hydrodistillation (20, 30, 45, 60 and 70 min) and drying temperature (20, 30, 45, 60 and 70 °C). The bioactivity of the essential oil was assessed against adults of S. zeamais and the effects of each variable and its interactions on the mortality of the insects were evaluated. The best yield of essential oil was obtained with the longest sonication and hydrodistillation times and the lowest drying temperature of leaves. Higher toxicity of the essential oil against S. zeamais was obtained by the use of ultrasound for its extraction. The identification and the relative percentage of the compounds of the essential oil were performed with a gas chromatograph coupled to a mass selective detector. The performance of the method was assessed by studying selectivity, linearity, limits of detection (LOD) and quantification (LOQ), precision and accuracy. The LOD and LOQ values for linalool were 2.19 and 6.62 µg mL-1 and for estragole 2.001 and 6.063 µg mL-1, respectively. The coefficients of determination (R2) were >0.99. The average recoveries ranged between 71 and 106%, with coefficient of variation ≤6.4%.

Use of ozone and detergent for removal of pesticides and improving storage quality of tomato.

The efficiencies of two conventional domestic procedures (immersion in pure water and detergent solution at 0.25 and 1%) and two treatments using ozone (immersion in water with bubbling O3 and immersion in ozonated water, both at 1 and 3 mg L-1) were evaluated for the removal of residues of the fungicides azoxystrobin, chlorothalonil and difenoconazole in tomatoes. The fungicides were sprayed on the fruits at the recommended concentration for the crop. The residues in the tomatoes and in the washing solutions were determined by extraction with low-temperature partition techniques and analysis by gas chromatography. More concentrated solutions were more effective in removing pesticide residues. The water bubbled with ozone at 3 mg L-1 was the most efficient treatment for the removal of fungicides, reaching a reduction of 70-90% of the residues. However, the treatments with the lowest concentration of ozone had lower loss of fruit mass during storage.

Eugenol diffusion coefficient and its potential to control Sitophilus zeamais in rice.

Given the insecticidal potential of eugenol as a fumigant, this work aimed to determine the diffusion coefficient of eugenol emanating from a pure standard solution (99%), as well as from clove essential oil (Eugenia caryophillata Thunb. (Myrtaceae)) through rice grain; to chemically analyse the volatile composition of commercially available eugenol and clove essential oil; and to evaluate the mortality of Sitophilus zeamais Motschulsky (Coleoptera: curculionidae) after exposure to eugenol inside a test chamber filled with rice. The solid phase microextraction method of extracting and quantifying eugenol by gas chromatography presented a good analytical response for the quantification of the analyte. There was no significant difference between the diffusion coefficient of eugenol diffusing from pure eugenol or from clove essential oil. The diffusion coefficient of eugenol through rice with the conditions herein adopted is 1.09 × 10-3 cm2 s-1. The characterization of clove essential oil confirmed the presence of eugenol as its major component (74.25%). A difference was observed in the composition of the distinct phases evaluated. The exposure of adult S. zeamais to diffused eugenol from pure eugenol over seven days resulted in significantly higher mortality rates (~37%) than eugenol diffused from clove essential oil (~11%). No differences in mortality rates were observed in individuals placed at different positions inside the test chamber during eugenol fumigation.

Insecticidal activity of Vanillosmopsis arborea essential oil and of its major constituent α-bisabolol against Callosobruchus maculatus (Coleoptera: Chrysomelidae).

Vigna unguiculata, one of the most important legumes, mainly in underdeveloped countries, is susceptible to post-harvest losses in storage by Callosobruchus maculatus (Fabricius, 1775) (Coleoptera: Chrysomelidae). The work evaluated the toxicity, inhibition of oviposition, instantaneous rate of population growth (ri) and the development of fumigated C. maculatus with the essential oil of Vanillosmopsis arborea and its major constituent, α-bisabolol. The experimental units consisted of 0.8 L flasks treated with concentrations of 1.2-11.2 µL L-1of air of the essential oil of V. arborea or its major constituent applied to disks of filter paper. α-Bisabolol was quantified as 409.33 mL L-1 of the essential oil. The development rate of C. maculatus was evaluated by daily adult counts. Oviposition was evaluated at lethal concentrations (LC50, LC25, LC10 and LC1). The LC50 and LC95 of the essential oil of V. arborea and α-bisabolol were 5.23 and 12.97 µL L-1 of air and 2.47 and 8.82 µL L-1 of air, respectively. At some concentrations, the α-bisabolol was more toxic to males than to females of the insect. Increased concentrations of the essential oil reduced the ri, rate of development, oviposition, and number of eggs of C. maculatus and therefore have potential for pest control.

Difenoconazole and linuron dissipation kinetics in carrots under open-field conditions.

The dissipation of difenoconazole and linuron using an open-field experimental approach with carrots exposed to one-, two- and fivefold the recommended dose of the pesticides was evaluated to provide safe recommendation to ensure food safety of carrots. The pesticide residue analysis was performed with solid-liquid extraction with low temperature partitioning technique (SLE/LTP) followed by gas chromatography analysis. The recovery percentages of extracts obtained from samples of carrot passed through SLE/LTP extraction and fortified with difenoconazole and linuron pesticides varied from 93.4% to 106.3% and from 95.1% to 116.6%, respectively. The limit of detection for difenoconazole was 0.02 and 0.12 mg kg-1 for linuron. The limit of quantification for difenoconazole was 0.05 and 0.36 mg kg-1 for linuron. The degradation time for fifty percent of the applied pesticide at the different doses ranged from 2.4 to 3.6 days for difenoconazole and from 7.5 to 10.5 days for linuron. At the end of the pre-harvest interval, carrots treated with fivefold the recommended dose of both pesticides were considered unfit for consumption. Despite monitoring the degradation products of the applied pesticides by gas chromatography coupled to mass spectrometer, none degradation product was identified on the carrots.

Degradation kinetics of organic matter in dairy industry wastewater by flotation/ozonation processes / Cinética de degradação da matéria orgânica nas águas residuárias da indústria de laticínios pelos processos de flotação/ozonização

This study evaluated the adjustment of four kinetic models and their respective parameters on data of dairy wastewater treatment by the physico-chemical process of flotation and ozonation. The experiment was implemented during the year 2014, with all the tests in triplicate. The treatments were carried out at different pH levels (3.6, 7.0 and 10.4), and flotation/ozonation was catalyzed by manganese (Mn2+) in neutral level (pH 7.0). Best removal efficiencies for chemical oxygen demand (COD) were obtained in acidic medium, with removals greater than 75% after 20 min of treatment. There was no significant difference with regards to addition of Mn2+ on COD removal by the physicochemical process. The kinetic models that best fit to the experimental data, for all treatments, were the asymptotic (residual) model and that of Chan and Chu. Treatment in acidic medium showed the highest values of the kinetic parameters for the adjusted model, obtaining a k coefficient equal to 0.2394 min-1 for the asymptotic model and kinetic coefficient 1/ of 0.4816 min-1 for the Chan and Chu model, both presenting a determination coefficient greater than 99%.

Neste estudo, avaliou-se o ajuste de quatro modelos cinéticos (modelo de escoamento pistonado, mistura completa, assintótico ou residual e de Chan e Chu e seus respectivos parâmetros, na degradação da matéria orgânica presente no efluente de laticínios pelo processo físico-químico de flotação e ozonização. O experimento foi implementado durante o ano de 2014, com todos os testes em triplicata, os s tratamentos foram realizados sob diferentes pHs (3,6; 7,0 e 10,4), além da flotação/ozonização catalisada pelo manganês (Mn2+) em meio neutro. Observando que em meio ácido ocorreram as melhores eficiências de remoção da demanda química de oxigênio (DQO), tendo sido obtida uma remoção superior a 75% em 20 min de tratamento. Não houve diferença significativa em relação à adição de Mn2+ ao processo físico-químico. Os modelos que mais se ajustaram aos dados experimentais, para todos os tratamentos realizados, foram o modelo assintótico e o de Chan e Chu. O tratamento em meio ácido foi o que apresentou os maiores valores dos parâmetros cinéticos para os modelos ajustados, obtendo-se para o modelo assintótico, coeficiente k igual a 0,2394 min-1, e para o modelo de Chan e Chu, coeficiente cinético 1/ de 0,4816 min-1, apresentando para ambos os modelos um coeficiente de determinação superior a 99%.

Ozone treatment for pesticide removal from carrots: Optimization by response surface methodology.

The present study aimed to optimize ozone (O3) treatments, as gas and dissolved in water, to remove difenoconazole and linuron in carrots. We employed a central composite design to study three variables governing the efficacy of treatments: O3 concentration, temperature and treatment time. The temperature did not influence the efficacy of treatments. The removal percentage of pesticides increases with increases in ozone concentration and the time of treatment. O3 application promoted the removal of more than 80% of pesticides when the roots were exposed for approximately 120min at 5 and 10mgL-1, respectively, in treatments with O3 as gas and dissolved in water. After storage, pesticide removal was higher than 98% for difenoconazole and 95% for linuron. The degradation products from the pesticides resulting from treatment were monitored, but none were found. This is the first report demonstrating the removal of difenoconazole and linuron from carrots by ozone.

Lasioderma serricorne (Coleoptera: Anobiidae): First Report on Black Sesame (Sesamum indicum).

Insect pests may make food products and by-products unfit for human consumption. This study reports the occurrence of Lasioderma serricorne (Coleoptera: Anobiidae) in packaged seeds of black Sesamum indicum. An intact plastic pot of S. indicum seeds was purchased by a consumer in a supermarket in Divinópolis, Minas Gerais state, Brazil, in April 2014 and was kept at his home for 3 months. Two hundred adults of this insect (196 dead and 4 alive) were counted in the pot with the seeds, besides three live larvae. This insect fed on S. indicum seeds, making them unfit for consumption. L. serricorne feed on and reproduce in S. indicum seeds stored in plastic packaging.