DIRECT INFUSION ESI-MS APPLIED IN THE DETECTION OF BYPRODUCTS DUE TO REDUCTIVE DEGRADATION OF ACETAMIPRID BY ZERO-VALENT IRON

This study investigated the reductive degradation of acetamiprid (5 mg L-1) in aqueous medium (at pH 2.0) induced by zero-valent iron (50 mg). The process was monitored using high-performance liquid chromatography (HPLC) to determine the degradation rate as a function of reaction time, and direct infusion electrospray ionization mass spectrometry (DI-ESI-MS) to search for (and potentially characterize) any possible byproducts formed during degradation. The results obtained via HPLC showed that after 60 min, the degradation of the substrate reached nearly 100% in an acidic medium, whereas the mineralization rate (as determined by total organic carbon measurements) was as low as 3%. Data obtained by DI-ESI-MS showed that byproducts were formed mainly by insertions of hydrogen atoms into the nitrile, imine, and pyridine ring moieties, in addition to the observation of chlorine substitution by hydrogen replacement (hydrodechlorination) reactions.

Studies on Advanced Oxidation Processes for the Removal of Acetamiprid from Wastewater

Pollution of water with pesticides has become a threat to the man, material and environment. The pesticides released to the environment reach the water bodies through run off. Industrial wastewater from pesticide manufacturing industries contains pesticides at higher concentration and hence a major source of water pollution. Pesticides create a lot of health and environmental hazards which include diseases like cancer, liver and kidney disorders, reproductive disorders, fatal death, birth defects etc. Conventional wastewater treatment plants based on biological treatment are not efficient to remove these compounds to the desired level. Most of the pesticides are phyto-toxic i.e., they kill the microorganism responsible for the degradation and are recalcitrant in nature. Advanced oxidation process (AOP) is a class of oxidation techniques where hydroxyl radicals are employed for oxidation of pollutants. AOPs have the ability to totally mineralise the organic pollutants to CO2 and water. Different methods are employed for the generation of hydroxyl radicals in AOP systems. Acetamiprid is a neonicotinoid insecticide widely used to control sucking type insects on crops such as leafy vegetables, citrus fruits, pome fruits, grapes, cotton, ornamental flowers. It is now recommended as a substitute for organophosphorous pesticides. Since its use is increasing, its presence is increasingly found in the environment. It has high water solubility and is not easily biodegradable. It has the potential to pollute surface and ground waters. Here, the use of AOPs for the removal of acetamiprid from wastewater has been investigated. Five methods were selected for the study based on literature survey and preliminary experiments conducted. Fenton process, UV treatment, UV/ H2O2 process, photo-Fenton and photocatalysis using TiO2 were selected for study. Undoped TiO2 and TiO2 doped with Cu and Fe were prepared by sol-gel method. Characterisation of the prepared catalysts was done by X-ray diffraction, scanning electron microscope, differential thermal analysis and thermogravimetric analysis. Influence of major operating parameters on the removal of acetamiprid has been investigated. All the experiments were designed using central compoiste design (CCD) of response surface methodology (RSM). Model equations were developed for Fenton, UV/ H2O2, photo-Fenton and photocatalysis for predicting acetamiprid removal and total organic carbon (TOC) removal for different operating conditions. Quality of the models were analysed by statistical methods. Experimental validations were also done to confirm the quality of the models. Optimum conditions obtained by experiment were verified with that obtained using response optimiser. Fenton Process is the simplest and oldest AOP where hydrogen peroxide and iron are employed for the generation of hydroxyl radicals. Influence of H2O2 and Fe2+ on the acetamiprid removal and TOC removal by Fenton process were investigated and it was found that removal increases with increase in H2O2 and Fe2+ concentration. At an initial concentration of 50 mg/L acetamiprid, 200 mg/L H2O2 and 20 mg/L Fe2+ at pH 3 was found to be optimum for acetamiprid removal. For UV treatment effect of pH was studied and it was found that pH has not much effect on the removal rate. Addition of H2O2 to UV process increased the removal rate because of the hydroxyl radical formation due to photolyis of H2O2. An H2O2 concentration of 110 mg/L at pH 6 was found to be optimum for acetamiprid removal. With photo-Fenton drastic reduction in the treatment time was observed with 10 times reduction in the amount of reagents required. H2O2 concentration of 20 mg/L and Fe2+ concentration of 2 mg/L was found to be optimum at pH 3. With TiO2 photocatalysis improvement in the removal rate was noticed compared to UV treatment. Effect of Cu and Fe doping on the photocatalytic activity under UV light was studied and it was observed that Cu doping enhanced the removal rate slightly while Fe doping has decreased the removal rate. Maximum acetamiprid removal was observed for an optimum catalyst loading of 1000 mg/L and Cu concentration of 1 wt%. It was noticed that mineralisation efficiency of the processes is low compared to acetamiprid removal efficiency. This may be due to the presence of stable intermediate compounds formed during degradation Kinetic studies were conducted for all the treatment processes and it was found that all processes follow pseudo-first order kinetics. Kinetic constants were found out from the experimental data for all the processes and half lives were calculated. The rate of reaction was in the order, photo- Fenton>UV/ H2O2>Fenton> TiO2 photocatalysis>UV. Operating cost was calculated for the processes and it was found that photo-Fenton removes the acetamiprid at lowest operating cost in lesser time. A kinetic model was developed for photo-Fenton process using the elementary reaction data and mass balance equations for the species involved in the process. Variation of acetamiprid concentration with time for different H2O2 and Fe2+ concentration at pH 3 can be found out using this model. The model was validated by comparing the simulated concentration profiles with that obtained from experiments. This study established the viability of the selected AOPs for the removal of acetamiprid from wastewater. Of the studied AOPs photo- Fenton gives the highest removal efficiency with lowest operating cost within shortest time.

Eficiência de Inseticidas no Controle de Pragas em Sementes e Mudas de Pau-rosa (Aniba rosaeodora Ducke), em Viveiros, Manaus, Amazonas

O pau-rosa (Aniba rosaeodora) é conhecido pela presença do álcool linalol, que fornece um odor forte e perfumado em todas as partes da planta. A sua exploração na Amazônia ao longo dos últimos anos, para utilização do linalol como fixador de perfumes, coloca o pau-rosa em risco de extinção, a sua frutificação irregular aumenta a dificuldade em se obter sementes para a produção de mudas e, além disso, parte de sua produção é perdida face ao ataque de pragas nas sementes. Em razão desses fatores o presente estudo teve como objetivo realizar a aplicação de inseticidas nas sementes e mudas em viveiro a fim de evitar ou minimizar o ataque de pragas, aumentando, assim, a produção de mudas. Utilizou-se um total de 300 sementes, distribuídas em 2 tratamentos e 1 testemunha. Cada tratamento (n = 100) foi constituído por 4 repetições (bandejas) com 25 sementes. O inseticida utilizado nos tratamentos foi acetamiprid e fipronil nas concentrações de 0,09 mg/planta e 0,18 mg/planta, respectivamente, para o tratamento 1 (T1) e o tratamento 2 (T2), distribuídos na forma de sachês. O T1 recebeu a aplicação de 1 sachê e o T2 a aplicação de dois sachês, enterrados com areia lavada nas sementeiras. Para avaliar os resultados foi feita uma análise de Variância (ANOVA), usando o programa Systat 9 e as médias comparadas pelo teste de Tukey em nível de 5%. As taxas de germinação foram: testemunha com 62%; T1 com 73% e T2 com 79%. Houve ataque de insetos em sementes apenas na testemunha com 23% do total (n = 100) e os resultados foram estatisticamente significativos (F = 31,263; p < 0,001). Houve diferenças significativas apenas entre a altura das plântulas nos tratamentos T1 e T2 e a testemunha (F = 15,090; p < 0,001). A principal praga identificada atacando as sementes foi Heilipus odoratus (Coleoptera: Curculionidae). Recomenda-se, portanto, a concentração de 0,09 mg de acetamiprid e fipronil distribuídos em sachês nas sementeiras e no transplantio para diminuir o ataque de pragas em sementes e mudas de pau-rosa em viveiros.

Redução de aplicações de inseticidas através da adoção de táticas de manejo integrado do Triozoida limbata (Enderlein, 1918) (Hemiptera: triozidae) em goiabeira

A praga de goiabeira que tem requerido maior frequência de controle, na região de Jaboticabal-SP, nos últimos anos, é o psilídeo Triozoida limbata. Assim, esta pesquisa objetivou: a) Comparar táticas de controle de T. limbata baseadas no monitoramento e na seletividade de inseticidas, visando a diminuir as aplicações; b) Registrar e correlacionar os inimigos naturais habitantes no agroecossistema goiabeira com a praga-chave e com fatores meteorológicos; c) Constatar se o controle de T. limbata afeta a população de moscas-das-frutas, e d) Verificar a eficiência de inseticidas adequados ao MIP, no controle de T. limbata. O experimento foi conduzido com a cultivar Paluma, em 2004, no município de Vista Alegre do Alto-SP. As estratégias utilizadas foram (doses em g.i.a./100L de água): testemunha; imidacloprid (4,0); imidacloprid + beta-cyfluthrin (2,5 + 0,3); acetamiprid (4,0); fenpropathrin (15,0), e tratamento convencional regional. Através dos resultados, conclui-se que é possível diminuir o número de aplicações e utilizar inseticidas menos agressivos ao meio ambiente e ao homem, com a adoção do monitoramento de T. limbata e aplicação no nível de ação. As densidades populacionais dos inimigos naturais (Scymnus spp., Cycloneda sanguinea, Azia luteipes, Crysoperla spp., Polybia spp., Brachygastra spp.) apresentam correlações positivas com as densidades populacionais de T. limbata. As flutuações populacionais de T. limbata e dos inimigos naturais não são alteradas pelos fatores meteorológicos (precipitação e temperatura), em pomar irrigado. A população de Anastrepha spp. é minimizada quando as aplicações são para controlar T. limbata. Os inseticidas imidacloprid, imidacloprid + beta-cyfluthrin, acetamiprid e fenpropathrin são eficientes no controle de T. limbata.

Redução de aplicações de inseticidas através da adoção de táticas de manejo integrado do Triozoida limbata (Enderlein, 1918) (Hemiptera: triozidae) em goiabeira

The guava tree pest that has been requesting larger control frequency, in the area of Jaboticabal - São Paulo in the last years, is the psilideo Triozoida limbata. Thus, the objectives of this research were: a) Compare control tactics T. limbata based on monitoring and selectivity of insecticide to decrease the applications; b) To register and to correlate the natural enemies in habitants in guava tree ecosystem with the key pest and with meteorological factors; c) See if the control of T. limbata affects the population of fruit flies and d) To verify the efficiency of appropriate insecticides to IMP, in control of T. limbata. The experiment was conducted in 2004, in an orchard of Paluma cultivar in Vista Alegre do Alto, SP. The used strategies were (doses in g.a.i./100L water): control; imidacloprid + beta-cyfluthrin (2.5 + 0.3); acetamiprid (4.0); fenpropathrin (15.0) and regional conventional treatment. It was concluding that is possible to reduce the number of applications of less aggressive insecticides to the environment and the man, with the adoption of monitoring of T. limbata and implementing the action level. The natural enemies' populations densities (Scymnus spp., Cycloneda sanguinea, Azia luteipes, Crysoperla spp., Polybia spp., Brachygastra ssp.) present positive correlations with the populations of T. limbata. Population fluctuations of T. limbata and natural enemies are not altered by meteorological factors (precipitation and temperature) in irrigated orchard. The population of Anastrepha spp. is minimized when of the applications is for control T. limbata. The insecticides imidacloprid, imidacloprid + beta-cyfluthrin, acetamiprid and fenpropathrin are efficient in the control of T. limbata.

Environmental Fate of Neonicotinoids and Classification of Their Potential Risks to Hypogean, Epygean, and Surface Water Ecosystems in Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Microarray analysis of cytochrome P450 mediated insecticide resistance in Drosophila

Insecticide resistance in laboratory selected Drosophila strains has been associated with upregulation of a range of different cytochrome P450s, however in recent field isolates of D. melanogaster resistance to DDT and other compounds is conferred by one P450 gene, Cyp6g1. Using microarray analysis of all Drosophila P450 genes, here we show that different P450 genes such as Cyp12d1 and Cyp6a8 can also be selected using DDT in the laboratory. We also show, however, that a homolog of Cyp6g1 is over-expressed in a field resistant strain of D. simulans. In order to determine why Cyp6g1 is so widely selected in the field we examine the pattern of cross-resistance of both resistant strains and transgenic flies over-expressing Cyp6g1 alone. We show that all three DDT selected P450s can confer resistance to the neonicotinoid imidacloprid but that Cyp6a8 confers no cross-resistance to malathion. Transgenic flies over-expressing Cyp6g1 also show cross-resistance to other neonicotinoids such as acetamiprid and nitenpyram. We suggest that the broad level of cross-resistance shown by Cyp6g1 may have facilitated its selection as a resistance gene in natural Drosophila populations. (C) 2003 Elsevier B.V. Ltd. All rights reserved.

Determination of pesticides multiresidues in shallow groundwater in a cotton-growing region of Mato Grosso, Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Efeito do tratamento químico na qualidade sanitária e fisiológica de sementes de soja infectadas por Sclerotinia sclerotiorum

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

Avaliação da contaminação de águas por resíduos de pesticidas em área de cultura de algodão: região de Primavera do Leste - MT

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Efeitos de inseticidas na sobrevivência e no comportamento de abelhas

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Análise do efeito de inseticidas neonicotinóides sobre a orientação e coleta de alimento de operárias de Apis mellifera L., 1758 (Hymenoptera: Apidae)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Ricerca di contaminanti in tessuti animali e in alimenti destinati all'uomo.

La contaminazione chimica rappresenta uno dei rischi principali per la sicurezza alimentare e può arrecare anche gravi danni alla salute umana. Rientrano in questa tesi di dottorato tre famiglie di contaminanti: Micotossine, Metalli e Insetticidi. La ricerca di aflatossina B1 è stata effettuata su 90 confezioni di farina, sia biologici sia convenzionali. La presenza della micotossina è stata rilevata solo nelle farine di mais. Solo un campione di produzione convenzionale ha superato il limite di 2 ppb definito per legge. Il dato di maggior rilievo è stato che il quantitativo di 5 grammi di campionamento si è dimostrato non rappresentativo sul totale della confezione commerciale di farina. Più attendibile si è invece dimostrato un campionamento di 20 grammi. L’aflatossina M1 è stata ricercata in 58 campioni di latte di cui 35 sono risultati positivi. Tuttavia, i livelli riscontrati erano costantemente inferiori al limite previsto per legge. Sono stati sottoposti a estrazione e purificazione, e analizzati con metodica HPLC-FL per la ricerca di Ocratossina A, 114 campioni di bile, 35 campioni di plasma, 40 campioni di rene prelevati da polli in Giordania. Le analisi hanno fornito risultati costantemente negativi. Sono stati analizzati 72 campioni (30 di muscolo, 29 di fegato e 13 di rene) prelevati da 30 bovini nel macello di Irbid (Giordania), di età compresa tra 8 e 30 mesi e provenienti da allevamenti diversi, per la ricerca di 13 elementi essenziali e non essenziali. In questo studio nessun campione supera i livelli massimi stabiliti dalla normativa europea per quanto riguarda gli elementi considerati. Infine, sono stati analizzati 37 campioni di latte ovino e 31 campioni di latte bovino, prelevati in Giordania in diversi allevamenti, per la ricerca di 4 neonicotinoidi (imidacloprid, acetamiprid, thiamethoxam e thiacloprid). I campioni, analizzati con sistema HPLC/MS/MS, sono risultati costantemente negativi ai quattro neonicotinoidi ricercati.

Toxicities and effects of insecticidal toxic baits to control Drosophila suzukii and Zaprionus indianus (Diptera: Drosophilidae).

BACKGROUND: Drosophila suzukii is a primary insect pest that causes direct damage to fruits with a thin epidermis such as strawberries, cherries and blueberries. In strawberry fields, the co-occurrence of D. suzukii and Zaprionus indianus has increased production losses. This study evaluated the toxicities and effects of insecticidal baits to control adults and larvae of both D. suzukii and Z. indianus . RESULTS: Organophosphate (dimethoate and malathion), spinosyn (spinosad and spinetoram), pyrethroid (lambda-cyhalothrin) and diamide (cyantraniliprole) insecticides exhibited high toxicity to both adults and larvae of D. suzukii and Z. indianus (mortality > 80%) in topical and dip bioassays. However, when the insecticides were mixed with a feeding attractant, a positive effect was observed only for adults of D. suzukii . Insecticides containing neonicotinoids (acetamiprid and thiamethoxam) and pyrolle (chlorfenapyr) caused intermediate mortality to adults of D. suzukii (40?60%) and low mortality for Z. indianus (mortality < 23%); however, these compounds reduced the larval infestation of the two species by 55?86%. Botanical (azadirachtin) and sulphur insecticides exhibited low toxicity (mortality < 40%) on adults and larvae of both species. CONCLUSION: Dimethoate, malathion, spinosad, spinetoram, lambda-cyhalothrin and cyantraniliprole are highly toxic to both larvaeandadultsof D. suzukii and Z.indianus .Theuseoftoxicbaitsforadultsof D. suzukii couldbeanalternativeinmanagement of this species. © 2016 Society of Chemical Industry Keywords: spotted-wing drosophila; fig fly; chemical control; strawberry; toxic bait; pest control.

Toxicities and effects of insecticidal toxic baits to control Drosophila suzukii and Zaprionus indianus (Diptera: Drosophilidae).

BACKGROUND: Drosophila suzukii is a primary insect pest that causes direct damage to fruits with a thin epidermis such as strawberries, cherries and blueberries. In strawberry fields, the co-occurrence of D. suzukii and Zaprionus indianus has increased production losses. This study evaluated the toxicities and effects of insecticidal baits to control adults and larvae of both D. suzukii and Z. indianus . RESULTS: Organophosphate (dimethoate and malathion), spinosyn (spinosad and spinetoram), pyrethroid (lambda-cyhalothrin) and diamide (cyantraniliprole) insecticides exhibited high toxicity to both adults and larvae of D. suzukii and Z. indianus (mortality > 80%) in topical and dip bioassays. However, when the insecticides were mixed with a feeding attractant, a positive effect was observed only for adults of D. suzukii . Insecticides containing neonicotinoids (acetamiprid and thiamethoxam) and pyrolle (chlorfenapyr) caused intermediate mortality to adults of D. suzukii (40?60%) and low mortality for Z. indianus (mortality < 23%); however, these compounds reduced the larval infestation of the two species by 55?86%. Botanical (azadirachtin) and sulphur insecticides exhibited low toxicity (mortality < 40%) on adults and larvae of both species. CONCLUSION: Dimethoate, malathion, spinosad, spinetoram, lambda-cyhalothrin and cyantraniliprole are highly toxic to both larvaeandadultsof D. suzukii and Z.indianus .Theuseoftoxicbaitsforadultsof D. suzukii couldbeanalternativeinmanagement of this species. © 2016 Society of Chemical Industry Keywords: spotted-wing drosophila; fig fly; chemical control; strawberry; toxic bait; pest control.