Orientador: Dagoberto Martins / Banca: Pedro Luis da Costa Aguiar Alves / Banca: Roberto Andreani Junior / Resumo: O objetivo do presente trabalho foi avaliar a influência de diferentes intervalos de chuva na eficiência de herbicidas aplicados em pós-emergência em quatro espécies de plantas daninhas: Ipomoea grandifolia, Senna obtusifolia, Brachiaria decumbens e Brachiaria plantaginea. O experimento foi conduzido em condições de casa-de-vegetação com uma planta por vaso, com capacidade de 2,5 L. O delineamento experimental utilizado foi o inteiramente casualizado, com quatro repetições, disposto em um esquema fatorial 7x8 (sete tratamentos químicos e oito intervalos de chuva) para as espécies dicotiledôneas e 6x8 (seis tratamentos herbicidas e oito intervalos de chuva) para as monocotiledôneas. Os tratamentos testados foram: glyphosate em cinco formulações comerciais (Roundup Original, Roundup WG, Roundup Transorb, Roundup Transorb R e Roundup Ultra) a 1.080 g e.a. ha-1, amonio-glufosinate a 400 g i.a. ha-1 e, apenas para as espécies dicotiledôneas utilizou-se o tratamento com 2,4-D a 1.000 g e.a. ha-1. A simulação de chuva de 20 mm foi realizada em oito intervalos de tempo após a aplicação dos herbicidas (15‟, 30‟, 1h, 2h, 4h, 6h, 8h e sem chuva). Foram realizadas avaliações visuais de controle das plantas aos 3, 7, 14, 21, 28 e 35 dias após a aplicação (DAA) para I. grandifolia,aos 3, 7, 14, 21 e 28 DAA para S. obtusifolia, aos 3, 7, 14 e 21 DAA para B. decumbens e aos 3, 7 e 14 DAA para B. plantaginea. Ao final do período de avaliação de cada espécie determinou-se a massa seca das plantas. Os resultados foram submetidos à análise de variância pelo Teste "F" e as médias dos tratamentos comparadas pelo teste de Tukey a 5% de probabilidade. Para plantas de I. grandifolia a ocorrência de chuvas após 15 minutos da aplicação do herbicida 2,4-D não afetou sua eficiência de controle, já os herbicidas amonio-glufosinate e glyphosate, em todas suas ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The aim of this study was to evaluate the influence of different intervals of rain in the efficiency of herbicides applied post-emergence in four weed species: Ipomoea grandifolia, Senna obtusifolia, Brachiaria decumbens and Brachiaria plantaginea. The experiment was conducted in conditions of green-house with one plant per pot, with a capacity of 2.5 L. The experiment was a completely randomized design with four replications, arranged in a 7x8 factorial arrangement (seven chemical treatments and eight intervals of rain) for dicotyledons and 6x8 (six and eight herbicide treatments rain intervals) for monocotyledons. The treatments were: glyphosate in five formulations (Roundup Original, Roundup WG, Transorb Roundup, Roundup and Roundup Ultra Transorb R) to 1080 g ae ha-1 ammonium-glufosinate at 400 g ai ha-1, and only for dicot species, we used treatment with 2,4-D and 1,000 g ha-1. The simulated rainfall of 20 mm was accomplished in eight intervals of time after herbicide application (15', 30', 1h, 2h, 4h, 6h, 8h and no rain). Visual evaluations of weed control at 3, 7, 14, 21, 28 and 35 days after application (DAA) for I. grandifolia, 3, 7, 14, 21 and 28 DAA for S. obtusifolia, 3, 7, 14 and 21 DAA for B. decumbens and at 3, 7 and 14 DAA for B. plantaginea. At the end of the trial period of each species determined the dry mass of plants. The results were subjected to analysis of variance test by "F" and the means were compared by Tukey test at 5% probability. For plants I. grandifolia to rainfall after 15 minutes of application of 2,4-D did not affect the efficiency of control because the herbicides glufosinate and glyphosate-ammonium, in all its formulations tested showed reduced efficiency of control when the occurrence of rainfall up to 8 hours after herbicide application and, with the exception of Roundup Original, all herbicides provided greater than 50% reductions in dry mass of ... (Complete abstract click electronic access below) / Mestre

The introduction of herbicide resistant crops offers producers many more options for weed control systems. These crops allow environmentally safe, non-selective herbicides to be used as selective herbicides, broadening the spectrum of weeds controlled, while not harming the crop. As these crops are very new on the market, investigation of their performance under various environmental conditions as well as in various weed control programs is needed. Liberty-link ® soybeans are resistant to the herbicide glufosinate, because of the incorporation of a gene encoding phosphinothricin acetyl-transferase (pat), which is able to detoxify glufosinate. Roundup-Ready ® soybeans are transformed with an altered, non-sensitive form of 5-enolpyruvylshikimate- 3-phosphate synthase (EPSPS), which confers glyphosate resistance. Field and greenhouse studies were conducted to determine the efficacy of glufosinate and glyphosate on annual and perennial weeds. Also to determine whether the use of ammonium sulfate (AMS) or pelargonic acid (PA), a 9-carbon fatty acid, as additives of glufosinate or glyphosate would increase their efficacy, while maintaining their safety on the transgenic soybeans. Three annual weeds: common lambsquarters, giant foxtail, sicklepod, as well as two perennial weeds: common milkweed and horsenettle were included in studies. Uptake, translocation, and metabolism of 14C-glufosinate + AMS or PA, were studied in the five weeds in order to determine the basis for their differential weed sensitivity to glufosinate, and the effect of the two additives. The effect of temperature on Liberty-Link ® and Roundup-Ready ® soybeans after application of glufosinate or glyphosate was investigated. Injury was quantified by measuring chlorophyll content of herbicide treated soybean trifoliolates. Uptake, translocation, and metabolism studies of 14C-glufosinate and 14C-glyphosate in transgenic soybeans were conducted to determine the potential cause for the observed temperature-dependent sensitivity. Since glufosinate is a synthetic analog of a naturally occurring bacterial toxin, it was tested for possible bactericidal activity on the soybean pathogen Pseudomonas syringae. Greenhouse and field-studies showed that the 5 weeds responded differently to glufosinate and glyphosate. Common milkweed was the most tolerant to glufosinate and common lambsquarters to glyphosate while giant foxtail was the most sensitive species to both herbicides. Some interactions between AMS or PA and glufosinate or glyphosate were also observed. Uptake and translocation studies showed that AMS increased the uptake of 14C-glufosinate in some weeds, whereas PA had only minimal effects on absorption and translocation of glufosinate. Metabolism of glufosinate was detected only in common lambsquarters. A rate dependent loss of chlorophyll in Liberty-Link ® soybeans treated with glufosinate was observed that was greater at 15° C than at 25° or 35° C. Metabolism studies showed a decrease in the rate of glufosinate metabolism 3 hours after treatment in Liberty-Link ® soybeans grown at 15° C versus 25° C. Conversely, chlorophyll loss in glyphosate-treated Roundup-Ready soybeans was greater at 35° C than at 15° or 25° C. Translocation studies showed a significantly greater percentage of absorbed 14C-glyphosate translocated to developing meristems at 35° C than at 15° C in Roundup-Ready® soybeans. Glufosinate concentrations of 1 mM and higher significantly inhibited the growth of Pseudomonas syringae (L-529) in liquid media cultures. Typical field use rates of glufosinate also reduced the number of live P. syringae on Liberty-Link® soybean leaves. Overall, the results of this research show that annual and perennial weeds differ in their sensitivity to glufosinate and glyphosate. Additives such as AMS and PA may enhance the efficacy of glufosinate on perennial weed species, and glyphosate in most weeds. Differences in weed sensitivity to herbicides and effects of additives can in most cases be explained by differences in absorption or metabolism. Variable temperatures may affect the engineered resistance of transgenic soybeans to the herbicides glufosinate and glyphosate. The herbicide glufosinate has some bacteriocidal activity on P. syringae. Nomenclature: Glufosinate, 2-amino-4-(hydroxymethylphosphinyl) butanoic acid; Glyphosate, N-(phosphonomethyl)glycine; PA, pelargonic acid (nanoic acid); AMS, ammonium sulfate; giant foxtail, Setaria faberi Herrm.; common lambsquarters, Chenopodium album L.; sicklepod, Cassia obtusifolia L.; horsenettle, Solanum carolinense L.; common milkweed, Ascleipias syriaca L. pat, phosphinothricin acetyl transferase; EPSPS, 5-enolpyruvylshikimate-3-phosphate synthase. / Master of Science

<p>In this thesis, I present a simple, sensitive and low cost electrochemical nanobiosensor for quantitative determination of the herbicides glufosinate, glyphosate and its metabolite aminomethylphosphonic acid (AMPA). Firstly, the nanostructured poly(2,5-dimethoxyaniline) (PDMA) materials were synthesized on gold electrode by the electrochemical &ldquo / soft template&rdquo / method using poly(4-styrenesulfonic acid) (PSS) as the dopant and structure-directing molecule. Fourier transform infrared (FTIR) spectroscopy, UV-Vis Spectroscopy, Transmission electron microscopy (TEM) and Scanning electron microscopy (SEM) studies inferred successful doping of the nanostructured PDMA film by PSS and that the template PSS directed the synthesis of both nanotubes and nanoparticles of PDMA with diameters less than 100 nm.</p>

<p>In this thesis, I present a simple, sensitive and low cost electrochemical nanobiosensor for quantitative determination of the herbicides glufosinate, glyphosate and its metabolite aminomethylphosphonic acid (AMPA). Firstly, the nanostructured poly(2,5-dimethoxyaniline) (PDMA) materials were synthesized on gold electrode by the electrochemical &ldquo / soft template&rdquo / method using poly(4-styrenesulfonic acid) (PSS) as the dopant and structure-directing molecule. Fourier transform infrared (FTIR) spectroscopy, UV-Vis Spectroscopy, Transmission electron microscopy (TEM) and Scanning electron microscopy (SEM) studies inferred successful doping of the nanostructured PDMA film by PSS and that the template PSS directed the synthesis of both nanotubes and nanoparticles of PDMA with diameters less than 100 nm.</p>

Philosophiae Doctor - PhD / In this thesis, I present a simple, sensitive and low cost electrochemical nanobiosensor for quantitative determination of the herbicides glufosinate, glyphosate and its metabolite aminomethylphosphonic acid (AMPA). Firstly, the nanostructured poly(2,5-dimethoxyaniline) (PDMA) materials were synthesized on gold electrode by the electrochemical "template"method using poly(4-styrenesulfonic acid) (PSS) as the dopant and structure-directing molecule. Fourier transform infrared (FTIR) spectroscopy, UV-Vis Spectroscopy, Transmission electron microscopy (TEM) and Scanning electron microscopy (SEM) studies inferred successful doping of the nanostructured PDMA film by PSS and that the template PSS directed the synthesis of both nanotubes and nanoparticles of PDMA with diameters less than 100 nm. / South Africa

Une étude ayant pour objectif d'évaluer différentes séquences d'herbicides en condition de doses réduites, a été mise en place à la station agronomique de l'Université Laval pendant trois ans. Huit séquences culturales de maïs (Zea mays) et de soya (Glycine max) tolérant au glyphosate et au glufosinate ont été testées avec quatre doses d'herbicides. Les résultats montrent que l'emploi du glufosinate trois ou deux années de suite en remplacement d'une utilisation continue du glyphosate paraît difficilement envisageable. Des problèmes de répression et des baisses de rendement sont visibles en présence d'une flore mixte (présence de graminées annuelles en particulier). L'utilisation de doses réduites de glufosinate n'est pas conseillée pour les mêmes raisons. Concernant le glyphosate, une réduction d'un quart de la dose homologuée semble réalisable du point de vue des rendements des cultures, mais présente toutefois un risque d'augmentation de la banque de graines au bout de deux années d'utilisation répétée.

Zoysiagrass (Zoysia spp.) is utilized as a warm-season turfgrass because of its density, visual quality, stress tolerance, and reduced input requirements. Turf managers often exploit winter dormancy in warm-season turfgrass to apply nonselective herbicides such as glyphosate and glufosinate to control winter annual weeds. Although this weed control strategy is common in bermudagrass (Cynodon spp.), it has been less adopted in zoysiagrass due to unexplainable turf injury. Many university extension publications recommend against applying nonselective herbicides to dormant zoysiagrass despite promotional language found in a few peer-reviewed publications and product labels. Previous researchers have used vague terminology such as "applied to dormant zoysiagrass" or "applied prior to zoysiagrass green-up" to describe herbicide application timings. These ambiguous terms have led to confusion since zoysiagrass typically has subcanopy green leaves and stems throughout the winter dormancy period. No research has sought to explain why some turfgrass managers are observing zoysiagrass injury when the literature only offers evidence that these herbicides do not injure dormant zoysiagrass. We sought to explore various herbicides, prevailing temperatures surrounding application, heat unit based application timings, and spray penetration into zoysiagrass canopies as possible contributors to zoysiagrass injury. The results indicated that a wide range of herbicides may be safely used in dormant zoysiagrass. However, as zoysiagrass begins to produce more green leaves, herbicides such as metsulfuron, glyphosate, glufosinate, flumioxazin, and diquat become too injurious. Glufosinate was consistently more injurious regardless of application timing than glyphosate and other herbicides. When temperatures were 10 °C for 7 d following treatment, a delayed effect of glyphosate and glufosinate effect on digitally-assessed green cover loss was noted on zoysiagrass sprigs. In subsequent studies on turf plugs, a 14-d incubation period at 10 °C reduced glyphosate but not glufosinate effects on turf green color reduction. Glyphosate applied at 125, and 200 GDD5C can safely be applied to zoysiagrass while glufosinate applied at the same timings caused inconsistent and often unacceptable zoysiagrass injury in field studies conducted at Blacksburg, VA, Starkville, MS, and Virginia Beach, VA. Zoysiagrass green leaf density was described as a function of accumulated heat units consistently across years and locations but variably by turf mowing height. Turf normalized difference vegetative index was primarily governed by green turf cover but reduced by herbicide treatments, especially when applied at greater than 200 GDD5C. Substantial spray deposition occurred to subcanopy tissue regardless of nozzle type, pressure and height above the zoysiagrass canopy based on spectrophotometric assessment of a colorant admixture. However, increasing nozzle height above the turf canopy and avoiding air induction type nozzles significantly reduced the percentage of green tissue exposed at lower canopy levels. Absorption of radio-labeled glyphosate and glufosinate was up to four times greater when exposed to zoysiagrass stems compared to leaves. Glyphosate translocated more than glufosinate and both herbicides moved more readily from stem to leaf than from leaf to stem / Doctor of Philosophy / Zoysiagrass (Zoysia spp.) is utilized as a warm-season turfgrass because of its density, visual quality, stress tolerance, and reduced input requirements. Being that zoysiagrass is a warm-season turfgrass, it enters a dormancy period during the winter months. During this period, zoysiagrasses' active growth is halted, and leaves lose their green color and turn a golden-brown color. The winter dormancy period presents turfgrass managers with a unique opportunity to apply nonselective herbicides such as glyphosate and glufosinate to control a broad spectrum of winter annual weeds. Although this weed control strategy is common in bermudagrass (Cynodon spp.), it has been less adopted in zoysiagrass due to turfgrass managers observing unexplainable turfgrass injury. Many university extension publications recommend against applying nonselective herbicides to dormant zoysiagrass despite language found in peer-reviewed publications and product labels suggesting they could be safely applied. Previous researchers have used vague terminology such as "applied to dormant zoysiagrass" or "applied prior to zoysiagrass green-up" to describe herbicide application timings. These terms have led to confusion about when to make these applications since zoysiagrass typically has subcanopy green leaves and stems throughout the winter dormancy period. No research has sought to explain why some turfgrass managers observe zoysiagrass injury when the literature only offers evidence that these herbicides do not injure dormant zoysiagrass. Research projects were designed to explore various herbicides, temperatures surrounding herbicide applications, application timings, and spray penetration into zoysiagrass canopies as possible contributors to zoysiagrass injury. The results indicated that a wide range of herbicides may be safely used in dormant and semidormant zoysiagrass. However, as zoysiagrass begins to produce more green leaves and stems, herbicides such as metsulfuron, glyphosate, glufosinate, flumioxazin, and diquat become too injurious and should be avoided. Across multiple research studies, glufosinate was consistently more injurious regardless of application timing than glyphosate and other herbicides. When temperatures were 10 °C for 7-d following treatment, it delayed zoysaigrass response to glyphosate and glufosinate. In a subsequent study, when temperatures were at 10 °C for a 14-d period, glyphosate and the nontreated reached 50% green cover at the same time, which suggests cold temperatures could mitigate glyphosate injury on zoysiagrass over a 14-d period. The 10 ° temperature only delayed glufosinate injury on zoysiagrass, and no safening was observed. The results also indicated that as temperatures increased, glyphosate and glufosinate rate in which injury was observed increased on the zoysiagrass. Glyphosate applied at 125, and 200 GDD5C can safely be applied to zoysiagrass while glufosinate applied at the same timings caused inconsistent and often unacceptable zoysiagrass injury in field studies conducted at Blacksburg, VA, Starkville, MS, and Virginia Beach, VA. Zoysiagrass injury increased when glyphosate and glufosinate were applied later into the spring when more green leaves were present regardless of location. Accumulated heat units and zoysiagrass green leaf density were closely related, indicating that accumulated heat units could be a useful tool for turfgrass managers to track zoysiagrass spring green-up. Substantial spray deposition was found on subcanopy zoysiagrass leaves and stems regardless of nozzle type, pressure, and height above the zoysiagrass canopy based on recovered colorant at the upper, middle and lower levels of the zoysiagrass canopy. However, avoiding air induction-type nozzles and raising spray height may slightly decrease penetration of spray droplets into a zoysiagrass subcanopy, but a large percentage of droplets still reached the middle and lower canopy layers in this research. Absorption of radio-labeled glyphosate and glufosinate was up to four times greater when applied directly to zoysiagrass stolen compared to leaves. Glyphosate translocated more than glufosinate, and both herbicides moved more readily from stem to leaf than from leaf to stem. These data suggest limiting the number of green zoysiagrass leaves at application would be an effective method to avoid injury zoysiagrass when applying nonselective herbicides

Le glufosinate d’ammonium (GLA) est un herbicide organophosphoré couramment utilisé en agriculture. De nombreux cas d’ingestions intentionnelles ont mis en évidence sa neurotoxicité. Cependant, ses effets sur le neurodéveloppement ne sont peu étudiés. En effet, le cerveau est une cible importante du GLA en raison de son homologie de structure avec le glutamate, principal neurotransmetteur excitateur du système nerveux central. Des résultats précédents du laboratoire ont permis de montrer qu’une exposition périnatale à de faibles doses de GLA induisait des perturbations de la neurogenèse et de la migration des neuroblastes au niveau de la zone sous ventriculaire vers les bulbes olfactifs. Ces modifications sont associées à l’apparition de troubles du spectre autistique dans la descendance. Ma thèse s’inscrit dans la continuité de ses travaux en abordant les aspects cellulaires et moléculaires mis en jeux lors d’une exposition précoce au GLA. Etant donné que dans la vie de tous les jours, nous sommes continuellement exposés aux pesticides mais également à leurs métabolites, j’ai étudié en parallèle les effets du principal métabolite du GLA, l’acide 4-méthylphosphinyl-2-oxo-butanoïque (PPO).Le premier travail de ma thèse a été de développer un protocole in vitro de culture primaire de cellules souches neurales issues de la zone sous-ventriculaire de souris pour l’analyse des effets neurotoxiques du GLA et du PPO. Les résultats de la première étude de ma thèse montrent une induction d’un stress oxydatif lié impliquant le système glutamatergique et associé à une perturbation de l’homéostasie calcique. Etant donné que les cellules souches neurales sont sensibles aux effets d’un stress oxydatif, dans une seconde étude, j’ai étudié l’impact de ces effets sur les mécanismes de différenciation cellulaire des cellules souches neurales. Mes résultats indiquent un effet significatif d’une exposition au GLA et au PPO sur la formation et le maintien de la niche neurogénique sous-ventriculaire in vitro. Le GLA et le PPO interfèrent avec la formation de l’épithélium épendymaire et induisent une perturbation dans la différenciation neurogliale des cellules souches neurales, sans influencer leur capacité de croissance ou de prolifération.L’ensemble des données de cette thèse mettent l’accent sur l’intérêt d’étudier les mécanismes cellulaires et moléculaires liés à la neurotoxicité des substances actives des pesticides, des métabolites de ces mêmes pesticides, mais également des mélanges substances actives-métabolites auxquels nous sommes continuellement exposés dans notre environnement. / The glufosinate-ammonium (GLA) is an organophosphorus herbicide commonly used in agriculture. Many cases of intentional ingestions have highlighted its neurotoxicity. However, its effects on neurodevelopment are not well studied. Indeed, the brain is an important target of GLA due to its structural homology with glutamate, the main excitatory neurotransmitter of the central nervous system. Our previous data are shown that a perinatal exposure to low doses of GLA induces disturbances in neurogenesis and in neuroblasts migration from the subventricular zone to the olfactory bulbs. These changes are associated with the development of autism spectrum disorders in the offspring. My thesis is in the continuity of his work and addresses the cellular and molecular aspects involved in early exposure to GLA. Since we are continuously exposed to pesticides, but also to their metabolites, I studied in parallel the effects of the main metabolite of GLA, the 4 methylphosphinyl-2-oxo-butanoic acid (PPO).The first work of my thesis was to develop an in vitro protocol for the primary culture of neural stem cells from the subventricular zone of mice, for the analysis of the neurotoxic effects of GLA and PPO. The results of the first study of my thesis showed an induction of related oxidative stress involving the glutamatergic system, and associated with a disruption of calcium homeostasis. Since neural stem cells are sensitive to the effects of oxidative stress, in a second study, I studied the impact of these effects on the cellular differentiation mechanisms of neural stem cells. My results indicated a significant effect of exposure to GLA and PPO on the formation and maintenance of the subventricular neurogenic niche in vitro. GLA and PPO interfere with the formation of ependyma and induce a disruption in the neuroglial differentiation of neural stem cells, without influencing their growth or proliferation capacity.All these data highlight on the interest of studying the cellular and molecular mechanisms linked to the neurotoxicity of the active substances of pesticides, the metabolites of these same pesticides, but also the mixtures of active substances and metabolites to which we are continuously exposed in our environment.