Avaliação in vivo do potencial estrogênico de amostra de água para consumo humano produzida por estação de tratamento do estado de São Paulo

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Dinâmica populacional e manejo de leptocybe invasa (Hymenoptera: Eulophidae) em plantações de eucalipto

Pós-graduação em Ciência Florestal - FCA

Determinação do teor dos ingredientes ativos imidacloprida e clorpirifós em produtos técnicos formulados por CLUE-DAD

The use of pesticides to manage pest problems in agriculture has become a common practice around the world. Pesticides consist in chemical substances or biological agents that act preventing, destroying, repelling or mitigating the damage caused by pests in agriculture. In order to a successful treatment, the correct dosage of pesticide has to be applied for each kind of culture. In this context, this project aims to quantify the levels of the active ingredients Imidacloprid and Chlorpyrifos present in formulated technical products and compare with the reported in the ir commercial leaflets. The analyzes were performed by Ultra Performance Liquid Chromatography coupled to a photodiode array detector (CLUE-DAD). The identification of Imidacloprid and Chlorpyrifos in the samples was realized by comparison of the time of retention and UV spectre of those substances with the commercials patterns, resulting in a excellent method specificity of the method. In the scope of determination of active ingredients in formulated products, the method developed showed good sensitivity in the applied conditions, with suitables limits of detection (4,2.10-² mg L-¹ for Imidacloprid and 1,1.10-¹ mg L-¹ to Chlorpyrifos) and quantitation (1,4.10-¹ mg L-¹ and Imidacloprid 3,6.10-¹ mg L-¹ to Chlorpyrifos) for the concentrations found in matrices analyzed. Furthermore, good results were obtained to the method accuracy with coeficiente of variance values in the range of 0,6 to 0,7% for repeatability (intra-day) and 0,4 to 0,58% for intermediate precision (inter- day). The accuracy of the method was determined by recovery tests, the values were comprised in the range of 98 102%. According to the recommendations of the Associação Brasileira de Normas Técnicas, these values show good accuracy of the method. The concentrations obtained in the quantification of the active ingredients in formulated products showed values within permited by ABNT, 60.1% (w/v) ± 0.6%...

Potential endocrinedisruptor activity of drinking water samples

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Seletividade de inseticidas a alguns dos inimigos naturais na cultura do algodão

The aim of this work was study the selectivity of insecticides in favor of natural enemies in cotton (Gossypium hirsutum latifolium Hurtch Lr), DeltaOpal cultivar, in the city of Malhada (BA), and to know the associated beneficial fauna. The study was conducted at the agricultural year of 2010/2011. The design was conducted in randomized blocks with six treatments and four replications. The treatments were: (1) Fipronil 200 SC (0.38 L.ha-1); (2) Alphacypermethrin 100 SC (0.30 L.ha-1), (3) Lufenuron 50 EC (0.30 L.ha-1), (4) Imidacloprid 200 SC (0.30 L.ha-1), (5) Methyl parathion 600 EC (1.00 L.ha-1), and (6) control (water). The product was applied 80 days after emergence, and the evaluations were performed one day before application and 1, 7 and 14 days after application (DAA). The samples were taken using the sampling method beating cloth and Moericke traps. Natural enemies were brought to the laboratory for sorting, counting and identification by family. The toxicity of the products ranged according to the group of natural enemies. Imidacloprid is selective to the spiders and insecticides are moderately toxic (Methyl Parathion and Alphacypermethrin: 1 and 14th DAA; Lufenuron: 14th DAA) or toxic (Fipronil and Alphacypermethrin: 7th DAA). Fipronil (1 DAA), Alphacypermethrin (7th DAA) and Methyl  Parathion (14th DAA) are moderately toxic to adult ladybirds. The analyzed insecticides are toxic to the larvae of ladybirds, with more impact until seven days after the application, with the exception of Methyl Parathion classified, as innocuous until this period. The occurrence of 13 families of spiders and 18 families of parasitic Hymenoptera is registered in cotton agroecosystems in the region of Malhada, in the state of Bahia.

Seletividade de produtos fitossanitários utilizados na cultura da soja para pupas de Trichogramma pretiosum Riley, 1879 (Hymenoptera: Trichogrammatidae)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Effect of contact and systemic insecticides on the sharpshooter Bucephalogonia xanthophis (Hemiptera: cicadellidae), a vector of Xylella fastidiosa in citrus

The knockdown and toxic effects of insecticides of different chemical groups and modes of action registered for citrus in Brazil were investigated for effective control of Bucephalogonia xanthophis, a sharpshooter vector of Xylella fastidiosa in citrus. The active ingredients dimethoate (1.2 mL/1.2L), imidacloprid (0.24 mL/1.2L) and lambda-cyhalothrin (0.24 mL/1.2L), as well as a control (water), were sprayed onto branches of potted-citrus nursery trees to evaluate the effect of residual contact. The insects were confined on sprayed branches by using sleeve cages, in groups of 10 per branch (5 branches/treatment). Lambdacyhalothrin showed a knockdown effect on B. xanthophis (>70% mortality within 2 h of exposure), and the residues were effective for approximately one wk. Imidacloprid, lambdacyhalothrin and dimethoate suppressed the vector populations for up to 3 wk after application, when the insects were exposed to sprayed plants for at least 24 h. In another experiment, 2 neonicotinoid insecticides (thiamethoxam and imidacloprid) were applied by soil drench to potted nursery trees, in order to study their systemic effect, i.e., mortality by ingestion on sharpshooter adults. Thiamethoxam and imidacloprid effectively controlled the vectors at all concentrations tested, when the insects were exposed to treated plants for 24 h (>80% mortality) or 48 h (near 100% mortality). The knockdown effect of thiamethoxam and lambda-cyhalothrin might be particularly important to prevent vector transmission of X. fastidiosa in citrus groves.

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.

Sublethal effects of a common neonicotinoid pesticide, thiamethoxam, on honey bees: impact on locomotion and thermoregulation

Neonicotinoids have been pointed to as a factor responsible for the increased honey bee colony losses in the last decades. Many studies have investigated the effects of the first marketed neonicotinoid, imidacloprid, while fewer have focused on thiamethoxam. One recent study showed that sublethal doses of thiamethoxam lead to colony failure by decreasing forager homing flight success. We thus decided to investigate the mechanism which caused this phenomenon. Our hypothesis was that this effect was caused by impairment of forager locomotion abilities. Therefore we tested the effects of sublethal acute and chronic exposures to thiamethoxam on forager walking (Chapter 2) and flight (Chapter 3) performances. The acute treatment (1.34 ng/bee) affected walking locomotion firstly triggering hyperactivity (30 min post-treatment) and then impairing motor functioning (60 min post-treatment). 2-day continuous exposures to thiamethoxam (32.5, 45 ppb) elicited fewer effects on walking locomotion, however both exposure modes elicited an increased positive phototaxis. Similarly, in flight experiments, the single dose (1.34 ng/bee) elicited hyperactivity shortly after intoxication (increased flight duration and distance), while longer and continuous exposures (32.5, 45 ppb) impaired forager motor functions (decreased flight duration, distance, velocity). It is known that flight muscles temperature needs to be precisely regulated by bees during flight. Therefore, we further hypothesized that the impaired flight performances of neonicotinoid intoxicated bees were caused also by thermoregulation anomalies. We tested the effects that acute thiamethoxam exposures (0.2, 1, 2 ng/bee) elicit on forager thorax temperature (Chapter 4). Foragers treated with high doses exhibited hyperthermia or hypothermia when respectively exposed to high or low environmental temperatures. In summary, we show that sublethal doses of thiamethoxam affected forager walking and flight locomotion, phototaxis and thermoregulation. We also display the intricate mode of action of thiamethoxam which triggered, at different extents, inverse sublethal effects in relation to time and dose.

Clinical, laboratory and pathological findings in dogs experimentally infected with Angiostrongylus vasorum

The aim of this comparative study was to investigate the development of clinical signs and accompanying haematological, coproscopic and pathological findings as a basis for the monitoring of health condition of Angiostrongylus vasorum infected dogs. Six beagles were orally inoculated with 50 (n=3) or 500 (n=3) A. vasorum third stage larvae (L3) obtained from experimentally infected Biomphalaria glabrata snails. Two dogs were treated with moxidectin/imidacloprid spot-on solution and two further dogs with an oral experimental compound 92 days post infection (dpi), and were necropsied 166 dpi. Two untreated control dogs were necropsied 97 dpi. Prepatency was 47-49 days. Dogs inoculated with 500 L3 exhibited earlier (from 42 dpi) and more severe respiratory signs. Clinical signs resolved 12 days after treatment and larval excretion stopped within 20 days in all four treated dogs. Upon necropsy, 10 and 170 adult worms were recovered from the untreated dogs inoculated with 50 and 500 L3, respectively. Adult worms were also found in two treated dogs, in the absence of L1 or eggs. Despite heavy A. vasorum infection load and severe pulmonary changes including vascular thrombosis, only mild haematological changes were observed. Eosinophilia was absent but the presence of plasma cells was observed. Neutrophilic leucocytes showed a transient increase but only after treatment. Signs for coagulopathies were slight; nevertheless coagulation parameters were inoculation dose dependent. Ten weeks after treatment pulmonary fibrosis was still present. Infections starting from 50 L3 of A. vasorum had a massive impact on lung tissues and therefore on the health of affected dogs, particularly after prepatency, although only mild haematological abnormalities were evident.

Comparación de los resultados obtenidos en el estudio de la toxicidad de diferentes plaguicidas sobre dos especies de miridos, aplicando la metodología de la OILB

Nesidiocoris tenuis (Router) (Hemiptera: Miridae) y Macrolophus basicornis (Stål) (Hemiptera: Miridae), son dos depredadores utilizados en el control de plagas del tomate, principalmente Tuta absoluta (Meyrick) (Lepidoptera: Gelechiidae), en España y Brasil respectivamente. Se ha estudiado la toxicidad residual de ocho modernos plaguicidas en adultos de estas dos especies de miridos, siguiendo la metodología recomendada por la Organización Internacional de Lucha Biológica e Integrada (OILB). Los ensayos se realizaron en dos laboratorios diferentes: Unidad de Protección Vegetal (ETSIA, UPM) y Laboratorio de Estudios de Selectividad (UFLA, Lavras-Brasil). Los insecticidas empleados en ambos laboratorios contenían el mismo ingrediente activo cuando fue posible (en el caso de Deltametrina y Flubendiamida) o pertenecían al mismo grupo de modo de acción principal según la clasificación del IRAC (Comité de Acción para la Resistencia a los Insecticidas): Spirotetramat, Metaflumizona y Sulfoxaflor en España y Spiromesifen, Indoxacarb e Imidacloprid en Brasil, respectivamente. Se evaluó la mortalidad durante los 3 días de exposición a los residuos y cuando fue posible, la descendencia de los supervivientes. Se comparan los resultados y las categorías de toxicología OILB obtenidas para los insecticidas estudiados.

Public Perceptions and Pesticides - A Case Study of the Willapa Bay Oyster Bed Spraying Permit of 2015

Thesis (Master's)--University of Washington, 2016-06

Evaluación de insecticidas químicos alternados con botánicos como opciones de manejo de mosca blanca (Bemisia tabaci, Gennadius) y otros insectos plagas en tomate (Solanum lycopersicum L.), en Tisma, Masaya 2016

La mosca blanca (Bemisia tabaci, Genn.) y los Geminivirus son los principales agentes de daño causantes de problemas fitosanitarios severos para los productores de tomate (Solanum lycopersicum, L.), este insecto provoca importantes pérdidas económicas, disminuyendo los rendimientos al afectar la calidad de frutos. En base a esta esta situación se realizó un estudio en el municipio de Tisma, Masaya en el período comprendido entre Julio y Septiembre del 2015 para evaluar la efectividad que tiene para controlar plagas los insecticidas químicos alternados con botánicos, los tratamientos evaluados fueron: Engeo alternado con Chile+Ajo+Jabón, Imidacloprid alternado con Madero Negro, Abamectina alternado con Neem, Monarca alternado con Chile+ajo y testigo (agua). Las variables evaluadas fueron, número de mosca blanca por planta, incidencia y severidad del daño de virosis por planta, número de Halticus sp por planta, número de Aphis sp por planta, número de Liriomyza sp por planta, numero de Arañas por planta, rendimiento en kg/ha. De los tratamientos evaluados, el menor número de moscas blancas, Halticus sp y menor porcentaje de incidencia y severidad lo presentó el tratamiento Abamectina alternado con Neem. El análisis económico determinó que el tratamiento que obtuvo el mayor rendimiento comercial fue Abamectina alternado con Neem. Se concluye que Abamectina alternado con Neem es el tratamiento que resultó más efectivo para el manejo de mosca blanca y otros insectos plagas.

Development of gene expression-based biomarkers of exposure to metals and pesticides in the freshwater amphipod Hyalella azteca

Ecological risk assessment (ERA) is a framework for monitoring risks of exposure and adverse effects of environmental stressors to populations or communities of interest. One tool of ERA is the biomarker, which is a characteristic of an organism that reliably indicates exposure to or effects of a stressor like chemical pollution. Traditional biomarkers which rely on characteristics at the tissue level and higher often detect only acute exposures to stressors. Sensitive molecular biomarkers may detect lower stressor levels than traditional biomarkers, which helps inform risk mitigation and restoration efforts before populations and communities are irreversibly affected. In this study I developed gene expression-based molecular biomarkers of exposure to metals and insecticides in the model toxicological freshwater amphipod Hyalella azteca. My goals were to not only create sensitive molecular biomarkers for these chemicals, but also to show the utility and versatility of H. azteca in molecular studies for toxicology and risk assessment. I sequenced and assembled the H. azteca transcriptome to identify reference and stress-response gene transcripts suitable for expression monitoring. I exposed H. azteca to sub-lethal concentrations of metals (cadmium and copper) and insecticides (DDT, permethrin, and imidacloprid). Reference genes used to create normalization factors were determined for each exposure using the programs BestKeeper, GeNorm, and NormFinder. Both metals increased expression of a nuclear transcription factor (Cnc), an ABC transporter (Mrp4), and a heat shock protein (Hsp90), giving evidence of general metal exposure signature. Cadmium uniquely increased expression of a DNA repair protein (Rad51) and increased Mrp4 expression more than copper (7-fold increase compared to 2-fold increase). Together these may be unique biomarkers distinguishing cadmium and copper exposures. DDT increased expression of Hsp90, Mrp4, and the immune response gene Lgbp. Permethrin increased expression of a cytochrome P450 (Cyp2j2) and decreased expression of the immune response gene Lectin-1. Imidacloprid did not affect gene expression. Unique biomarkers were seen for DDT and permethrin, but the genes studied were not sensitive enough to detect imidacloprid at the levels used here. I demonstrated that gene expression in H. azteca detects specific chemical exposures at sub-lethal concentrations, making expression monitoring using this amphipod a useful and sensitive biomarker for risk assessment of chemical exposure.

Otimização e validação de métodos empregando DLLME e DLLME-SFO para a extração simultânea de agrotóxicos multiclasse em água mineral

O Rio Grande Sul destaca-se no cenário nacional como grande produtor de diversas culturas, as quais demandam grande quantidade de agrotóxicos das mais diversas classes químicas e toxicidades. No entanto a intensa utilização destes compostos torna-se uma preocupação devido a possíveis contaminações das águas superficiais e subterrâneas. Em virtude da degradação dos mananciais a água mineral passou a ser uma das fontes mais utilizadas para o consumo humano, pois tem-se a percepção de que a mesma possui melhor qualidade que a água tratada, além disso acredita-se que a mesma esta isenta de substâncias orgânicas prejudiciais à saúde humana. Neste trabalho, foi realizada a determinação dos agrotóxicos atrazina, simazina, imazapique, imazetapir, imidacloprido, ciproconazol, tebuconazol e epoxiconazol em água mineral empregando a Microextração Líquido-Líquido Dispersiva (DLLME), Microextração Líquido-Líquido Dispersiva com Solidificação da Gota Orgânica Flutuante (DLLME-SFO) e Cromatografia Líquida acoplada à Espectrometria de Massas em série com fonte de ionização por Eletronebulização (LC-ESI-MS/MS). Para o método empregando DLLME e LC-ESI-MS/MS foram otimizados alguns fatores como o tipo e volume de solvente extrator e dispersor e pH. Após a otimização dos parâmetros de extração, fragmentação dos compostos e separação cromatográfica, o método foi validado avaliando-se curva analítica, linearidade, limites de detecção e quantificação, precisão (repetitividade e precisão intermediária) e exatidão (recuperação). Todas as curvas analíticas apresentaram valores de r maiores que 0,999. Os Limites de Quantificação (LOQs) para o método estiveram na faixa de 5 a 500 ng L-1. Foram obtidas recuperações entre 102 - 120% para a repetibilidade e entre 92 e 110% para a precisão intermediária, com RSD de 2 a 10% para todos os compostos. Para o método empregando DLLME-SFO e LC-ESI-MS/MS foram avaliados alguns parâmetros que afetam a eficiência da extração como, tipo e volume de solvente extrator e dispersor, força iônica e pH. Nas condições ótimas de extração todas as curvas analíticas apresentaram valores de r maiores que 0,997. Os LOQs para o método variaram entre 12,5 - 125 ng L-1. As recuperações foram entre 70 e 118% para a repetitividade e entre 76 e 95% para a precisão intermediária, com RSD de 2 a 18% para todos os compostos. Com relação ao Efeito Matriz (EM) avaliado para todos os compostos pelos dois métodos, foi observado baixo EM. Isso indicou que não é necessário utilizar a curva analítica preparada no extrato branco da matriz para a quantificação destes analitos. Ambos os métodos foram aplicados para a determinação de resíduos de agrotóxicos em amostras de água mineral provenientes de diferentes regiões do estado do Rio Grande do Sul e não foram encontrados resíduos de agrotóxicos nas amostras analisadas. Os métodos validados apresentaram como principais vantagens baixo consumo de solventes orgânicos e amostra, rapidez, altos fatores de concentração e recuperações dentro da faixa aceitável. Os limites de quantificação dos métodos ficaram abaixo dos limites máximos de resíduos permitidos pela legislação brasileira para agrotóxicos em água mineral.