Orientador: Ciro Cesar Zanini Branco / Banca: Rosana Marta Kolb / Banca: Régis de Campos Oliveira / Resumo: Vários estudos observacionais sobre macrófitas de ecossistemas lóticos têm contribuído com o aumento do conhecimento ecológico destes organismos nestes ambientes. Entretanto, ainda persistem lacunas importantes neste conhecimento, entre as quais estão as relações de causa e efeito que potencialmente existem entre perturbações provocadas pela atividade antrópica e aspectos da fisiologia e da ecologia destes organismos. Com o objetivo de superar, obviamente em parte, esta lacuna, o presente estudo propõe, através de experimentos laboratoriais, avaliar os efeitos de resíduos de herbicidas usados nas lavouras agrícolas, em especial aqueles a base de glifosato (Roundup®) e seu metabólito (AMPA), sobre parâmetros fotossintéticos de espécies de angiospermas aquáticas típicas de ecossistemas lóticos tropicais. As avaliações das taxas fotossintéticas e de respiração no escuro foram realizadas através da evolução do oxigênio dissolvido, aplicando-se a técnica das garrafas claras e escuras e da fluorescência de clorofila a, que foi avaliada com o fluorômetro subaquático Diving-PAM. Os valores dos parâmetros fotossintéticos medidos/calculados para cada tratamento avaliado foram submetidos à estatística descritiva e as eventuais diferenças entre eles foram avaliadas através da análise de variância utilizando o teste de Scott-Knott e o t-Student. Foram observados alguns poucos efeitos fitotóxicos associados às espécies de macrófitas estudadas, porém, quase nenhuma diferença... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Even with many observational studies regarding lotic ecosystems, macrophytes that have contributed with great knowledge about the ecology of these organisms in these environments. However, there are still important gaps in this knowledge, among which are the cause and effect relationships that potentially exist between disturbances caused by anthropic activity and aspects of the physiology and ecology of these organisms. With the objective of overcoming, in part, this gap, the present study proposes, through laboratory experiments, to evaluate the effects of herbicide residues used in agricultural crops, especially those based on glyphosate (Roundup®) and your metabolite (AMPA) on photosynthetic parameters of aquatic angiosperm species typical of tropical lotic ecosystems. The evaluation of photosynthetic rates and respiration in the dark were performed through the evolution of dissolved oxygen, applying the light and dark bottle technique and chlorophyll a fluorescence, which was evaluated with the Diving-PAM underwater fluorometer. The values of the photosynthetic parameters measured / calculated for each evaluated treatment were submitted to descriptive statistics and any differences between them were evaluated through analysis of variance using the Scott-Knott and t-Student test. In spite of this global pattern, species responded specificially to exposure to Roundup® and AMPA, and Egeria densa was the one that registered the greatest susceptibility to the loss of... (Complete abstract click electronic access below) / Mestre

CGAr92194 {α-[1,3-dioxolan-2-yl-methoxy)imino]benzeneacetonitrile} is a herbicide safener that is used as a seed dressing agent (1.25 g ai/kg seeds) to protect grain sorghum [<i>Sorghum bicolor</i> (L.) Moench] against metolachlor [2-chloroi-<u>N</u>-(2-ethyl-6-methylphenyl-<u>N</u>-(2-methoxy1-methylethyl)acetamide] injury. The potential adverse phytotoxic effects and the mechanisms of the protective action of this safener were studied in laboratory experiments. Adverse phytotoxicity was assessed by comparing CGA-92194 and the herbicide safeners cyometrinil {(Z)-α[(cyanomethoxy)imino]benzeneacetonitrile} and flurazole [phenylmethyl 2-chloro-4-(trifluromethyl)-5-thiazolecarboxylate] for their effects on CO₂ fixation, protein, DNA, RNA and lipid syntheses of enzymatically isolated leaf cells of soybean [<u>Clycine max</u> (L.) Merr]. At physiological concentrations of less than 10 μM, CGA-92194, cyometrinil and flurazole were stimulatory of all metabolic processes. At 100 μM, the safeners were inhibitory of the five processes with flurazole being the most potent. The mechanisms of the safening action of CGA-92194 were studied by examining the potential interactions of this safener with metolachlor at the levels of uptake and macromolecular syntheses in enzymatically isolated leaf mesophyll protoplasts of grain sorghum. The influence of CGA-92194 on the <i>in vitro</i> reactivity of metolachlor with glutathione (GSH) and it metabolism by sorghum seedlings were also examined. When CGA-92194 and metolachlor were given simultaneously, CGA-92194 enhanced the uptake of ¹⁴C-metolachlor into the sorghum protoplasts in a concentration-dependent pattern. Thus, interference with herbicide uptake is not involved in the protective action of this safener Treatments with metolachlor and CGA-92194 in combination inhibited the incorporation of ¹⁴C-uracil, ³H-thymidine and ¹⁴C-acetate into sorghum protoplast macromolecules less than metolachlor given alone, suggesting the potential involvement of a competitive antagonism in the mechanism of action of CGA-92194. The metabolic activity and growth of sorghum seedlings grown from CGA-92194-pretreated seeds was significantly lower than that of seedlings grown from untreated seeds at 10 or 20 days after planting, The relationship of these effects of CGA-92194 to its safening action is unclear at the present time. CGA-92194 increased the <i>in vitro</i> chemica1 reactivity of metolachlor for GSH in a concentration-dependent pattern, Sorghum seedlings grown from safener-pretreated seeds enhanced ¹⁴C-metolachlor absorption and stimulated its metabolism <u>via</u> conjugation to GSH. This stimulation was reduced by tridiphane [2-(3,5-dichlorophenyl)-2-(2,2,2-trichloroethy1)- oxirane] a potent inhibitor of plant GSH-<u>S</u>-transference enzymes, These results indicate that a safener-induced stimulation of the spontaneous or enzymatic conjugation of metolachlor with GSH is most likely involved in the protective action of CGA-92194. It is suggested that the safening mechanism of action of CGA—92194 involves a sequence of multilevel interactions which together contribute to the overall protection of grain sorghum from metolachlor injury. / Ph. D. / incomplete_metadata

Rimsulfuron {N-[[ 4,6-dimethoxy-2-pyrimidinal)amino ]carbonyl]-3-( ethylsulfonyl)-2-pyridinesulfonamide} is a new sulfonylurea herbicide under development by E.I. Dupont de· Nemours & Company Inc. for preemergence and postemergence grass and broadleaf weed control in Solanaceous vegetable crops. The efficacy and selectivity of rimsulfuron were determined in potatoes, transplanted tomatoes, and transplanted peppers in field studies in 1991, 1992, and 1993. Treatments included rimsulfuron and metribuzin alone and in combination in potatoes and tomatoes, rimsulfuron alone in peppers, and sequential applications of rimsulfuron in tomatoes and peppers. Application timings included preemergence and postemergence in potatoes, while only post-transplant applications were evaluated in tomatoes and peppers. Preemergence applications of rimsulfuron controlled weeds if rainfall was received within a few days following application. Control was often greater in potatoes and tomatoes than in peppers. These differences likely relate to more frequent rainfall events in potatoes and tomatoes than in the later-planted peppers. / Master of Science

Laboratory studies were conducted to investigate the mode of action of a new herbicide, isouron (N-(5-(1,1-dimethylethyl)-3-isoxazolyl)-N,N-dimethylurea). These studies included two plant metabolites of isouron, a monomethylurea (N-(5-(1,1-dimethylethyl)-3-isoxazolyl)-N-methylurea) and a urea derivative (N-(5-(1,1-dimethylethyl)-3-isoxazolyl)-urea). The compounds were examined for their effects on four metabolic processes of enzymatically isolated soybean (Glycine max L.) leaf cells. The processes examined were photosynthesis, protein, ribonucleic acid (RNA) and lipid synthesis. Relative incorporation of radiolabeled precursors was the parameter measured to assess herbicidal effects. Results indicate that isouron and its monomethylurea derivative possess similar herbicidal properties. The urea derivative revealed substantially reduced herbicidal effectiveness. The primary mode of action of these compounds appears to be inhibition of photosynthesis. Experiments to determine an I₅₀ value for isouron and experiments to evaluate the influence of an antioxidant EDU (N-(2-(2-oxo-1-imidazolidinyl)ethyl)-N’-phenylurea) and a singlet oxygen quencher DABCO (1,4-diazobicyclo-(2,2,2)-octane) on the photosynthetic inhibition and chlorophyll breakdown induced by isouron were also conducted. An I₅₀ value of 0.51 uM was calculated for isouron. There was no significant influence of EDU or DABCO on isouron toxicity. Greenhouse experiments were conducted to assess the interactions of isouron and four herbicide antidotes on two varieties of corn (Zea mays L.), Dekalb 'XL72AA' and 'XL67', and wheat (Triticum aestivum L.), 'Tyler' and 'McNair 1003'. Antidotes used were naphthalic anhydride (1,8 naphthalic anhydride), R-25788 (N,N-diallyl-2,2-dichloroacetamide), CGA-43089 (α-((cyanomethoxy)imino)benzene acetonitrile) and CGA-92194 (α-((1,3-dioxolan-2-yl-methoxy)imino)benzene acetonitrile. Statistically significant antagonistic interactions between herbicide and antidote were observed in both wheat and corn. Synergistic interactions were also recorded. The order of antidotal effectiveness on corn was determined to be: NA > CGA-43089 > CGA-92194 > R-25788 and in wheat: NA > CGA-43089 > R-25788 (CGA-92194 severely limited germination). Visual observation of both corn and wheat plants indicated that nonantidoted isouron was very toxic to these crops. / Master of Science

The biological actions of the herbicides SC-0224 (trimethylsulfonium carboxymethylaminomethylphosphonate) and glyphosate [N-(phosphonomethyl)glycine] (PMG) were compared. In each study trimethylsulfonium iodide (TMS-I) was included as a treatment because the trimethylsulfonium ion is a constituent of the SC-0224 molecular structure. In inflated duckweed (Lemna gibba L.), both formulated and technical grade forms of SC-0224 were found to be much more phytotoxic to duckweed than either formulated or technical grade forms of glyphosate. The growth inhibition caused by glyphosate was partially prevented by different combinations of the aromatic amino acids phenylalanine, tyrosine, and tryptophan; whereas, the duckweed growth inhibition caused by SC-0224 could not be reduced by the same amino acid combinations. TMS-I and SC-0224 were found to be equally phytotoxic to duckweed. SC-0224 caused larger increases than glyphosate in the pool levels of amino acids; the increases caused by SC-0224 were similar, however, to those caused by trimethylsulfonium iodide. Expressed on a per gram fresh weight basis none of the chemical treatments caused significant changes in soluble protein or the incorporation of ¹⁴C-leucine into soluble protein. On a per flask basis (allowing for decreased growth in treated flasks), both herbicides and TMS-I caused significant decreases in soluble protein and ¹⁴C-leucine incorporation. SC-0224 and TMS-I caused larger decreases than glyphosate in both cases but the SC-0224 and TMS-I treatments were not significantly different. These data indicate that differences in the phytotoxicity of SC-0224 .and glyphosate may be due to the action of the trimethylsulfonium ion of the SC-0224 structure. The effects of these herbicides on the conversion of shikimate to anthranilate in a cell-free extract of Klebsiella pneumoniae ATCC 25306 were also compared. SC-0224 and glyphosate equally inhibited the production of anthranilate indicating that SC-0224 has action similar to glyphosate on the shikimate pathway. The effects of these herbicides on photosynthetic electron transport (the Hill reaction) was determined using isolated thylakoids from Alaska pea (Pisum sativum L.). The action of SC-0224 was compared with the action of glyphosate, TMS-I and diuron [3-(3,4-dichorophenyl)-1,1-dimethylurea]. SC-0224, glyphosate and TMS-I did not inhibit the Hill reaction at concentrations up to 10 mM; whereas, diuron caused an almost total inhibition at 0.10 mM. The results of this study indicate that SC-0224 is not an inhibitor of photosynthetic electron transport. These studies indicate that both constituents of the SC-0224 structure, TMS and PMG, are phytotoxic and may act independently. / Ph. D.

Response of barley (<i>Hordeum vulgare</i> L.) and wheat (<i>Triticum aestivum</i> L.) to root-applied chlorsulfuron (2-chloro N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] carbonyl] benzenesulfonamide), a herbicide for use in small grains, was investigated. The results showed that, although wheat roots take up more chlorsulfuron than barley roots, barley was less tolerant to chlorsulfuron and chlorsulfuron was more mobile in barley. This study indicated that difference in uptake or translocation cannot explain the differential response of the two species to root-applied chlorsulfuron. In an interaction study, significant chlorsulfuron antagonism on ryegrass (<i>Lolium multiflorum</i> Lam.) control by diclofop {(±)[-2-[4-(2,4-dichlorophenoxy) phenoxy) propanoic acid} was observed. Greenhouse experiments showed that the tolerance of corn (<i>Zea mays</i> L.) to chlorsulfuron and metsulfuron (2-[[[[(4-methoxy-6-methyl-l,3,5-triazin- -2-yl) amino] carbonyl] amino] sulfonyl] benzoic acid) was greatly increased by seed dressing with the herbicide safener NA (1,8-naphthalic anhydride). The soil behavior of chlorsulfuron was studied in the field, greenhouse and laboratory. In the field, corn adequately tolerated soil residues present 10 months following postemergence application of chlorsulfuron at 10 to 120 g/ha. However, at the same site and rates, residues from chlorsulfuron injured corn when sampled 2 months after application. In laboratory studies chlorsulfuron was moderately adsorbed by organic matter but showed low affinity to clay. R_f values calculated from soil thin-layer chromatography closely correlated with the mobility of chlorsulfuron leached with 16.8 cm of water over a 14-day period in hand-packed soil columns. In the soil thin-layer chromatography, chlorsulfuron mobility was positively and negatively correlated with pH and organic matter, respectively. The results indicated that chlorsulfuron could be mobile in low organic matter and non-acidic soils. The relationship of chlorsulfuron phytotoxicity to soil physical and chemical properties was also evaluated. Organic matter was inversely related to chlorsulfuron phytotoxicity while no such relationship to clay content was observed. The adsorption of chlorsulfuron decreased with increasing soil pH whereas desorption was greater at alkaline pH. / Ph. D.

Herbicide safeners (protectants, antidotes) are used to protect crop plants from herbicide injury. Currently our understanding of the mechanisms involved in the protection of plants by safeners is not well defined; therefore, investigations were conducted to elucidate the mechanism(s) of action of the oxime ether safeners. Molecular comparisons of selected herbicide-safener combinations using computer-aided molecular modeling revealed that the chemical structures of safeners and herbicides are very similar at the molecular level; and, indicate that these compounds could bind at the same active site of the target protein or they may serve as inducers of metabolic enzymes which detoxify herbicides. Metolachlor at 10 μM and seed-applied CGA-133205 had no effect on germination while treatment with seed-applied oxabetrinil significantly reduced germination of grain sorghum. Results from experiments on ¹⁴C-acetate incorporation into lipids indicate that metolachlor and the oxime ether safeners influence lipid metabolism causing a redistribution of carbon in the lipid fractions of germinating sorghum roots. Results from studies with acetyl-CoA carboxylase indicate that this enzyme is not a target site for either metolachlor or the oxime ether safeners. Metolachlor and the oxime ether safeners enhanced glutathione levels in grain sorghum seedlings at 12 to 48 hr after imbibition was initiated with oxabetrinil being more stimulatory than metolachlor or CGA-133205. Glutathione reductase activity was also stimulated in safener-treated grain sorghum seedlings. Both safeners slightly enhanced nonenzymatic and enzymatic conjugation of metolachlor with reduced glutathione. Oxabetrinil conjugated enzymatically or nonenzymatically with reduced glutathione at a slow rate, but CGA-133205 did not. These data suggest that during the early stages of seed germination and seedling development of grain sorghum, safeners can enhance the detoxication of metolachlor by enhancing glutathione levels and enzymatic and nonenzymatic conjugation of metolachlor with glutathione. It appears that oxabetrinil and CGA-133205 are conferring protection to grain sorghum by increasing the rate of metolachlor metabolism. / Ph. D.

Call number: LD2668 .T4 1985 G672 / Master of Science

Orientador: Ulisses Rocha Antuniassi / Banca: Otavio Jorge Grigoli Abi-Saab / Banca: Caio Antonio Carbonari / Banca: Paulo Roberto Arbex Silva / Banca: Rone Batista de Oliveira / Resumo: A correta aplicação de produtos fitossanitários resulta em minimização de perdas, e mitigação de danos ambientais. A busca por uma operação de aplicação otimizada tornou a mistura em tanque de produtos fitossanitários uma prática comumente utilizada em todo o mundo. Entretanto, a mistura em tanque pode resultar em alterações físicas na calda, interferindo no espectro de gotas e no risco de deriva. Técnicas para redução de deriva devem ser utilizadas neste processo, especialmente na aplicação de herbicidas. Nesse contexto, este trabalho teve como objetivo avaliar o espectro de gotas e o potencial de deriva gerado por caldas contendo os herbicida 2,4-D e glyphosate em diferentes condições de misturas, aplicadas com duas pontas diferentes. Em uma formulação composta de herbicida 2,4-D sal colina incluindo uma tecnologia para redução da deriva. Esta formulação foi comparada a uma formulação convencional de 2,4-D sal dimetilamina (DMA) de maneira isolada e em pré mistura com glyphosate (sal potássico e sal dimetilamina) e uma mistura pronta (2,4-D sal colina + glyphosate sal dimetilamina). Para isto foram comparados vinte tratamentos, sendo cada tratamento representado por uma calda, constituídas das misturas ou não entre os herbicidas. As avaliações dos tratamentos foram realizadas em dois experimentos. O primeiro pulverizado com uma ponta de jato plano de uso estendido (Teejet XR 11002) e outro com uma ponta jato plano de indução de ar (Teejet AIXR 11002). A pressão de trabalho ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The correct application of pesticides results in loss minimization, and mitigation of environmental damage. The search for an optimal implementation of operation has the mixture in a practical defensive tank commonly used throughout the world. However, the tank-mix can result in physical changes in the spray solution, interferes with droplet spectrum and the risk of drift. Drift reduction techniques to be used in this process, including the application of herbicides. In this context, this study aims to evaluate the spectrum of drops and the potential drift generated by spraying solutions containing the herbicide 2,4-D and glyphosate in different conditions of mixtures applied with two different nozzles. A formulation containing 2,4-D salt choline including a technology for reduction of drift was used. This formulation was compared to a conventional formulation of 2,4-D dimethylamine salt (DMA) in isolation and premix with glyphosate (potassium salt and dimethylamine salt) and a ready mixed (2,4-D + glyphosate salt choline salt dimethylamine). Twenty treatments were compared, each treatment being represented by a spray solution consisting of mixtures of herbicides or not. The treatments were evaluated in two experiments. A sprayed with a jet nozzle extended use plan (Teejet XR 11002) and one with a nozzle jet air induction plan (Teejet AIXR 11002) both at 280 kPa. The Volumetric Median Diameter (VMD) and the percentage of droplets smaller than 105 µm (V105) were obtained from ... (Complete abstract click electronic access below) / Doutor

The objective of this Ph.D. research was to identify new and novel mechanisms of wild radish (Raphanus raphanistrum L.) resistance to photosystem II (PSII) inhibitors, auxinics, and acetohydroxyacid synthase (AHAS) inhibitors. PSIIinhibitor resistance was demonstrated to be target-site based, and conferred by a Ser264 to Gly substitution of the D1 protein. Auxinic resistance was associated with reduced herbicide translocation to the meristematic regions of resistant wild radish plants. Two new resistance mutations of wild radish AHAS were discovered, including one encoding the globally rare Asp376 to Glu substitution, and another encoding an Ala122 to Tyr substitution, which has never been identified or assessed for resistance in plants previously. Characterization of the frequency and distribution of AHAS resistance mutations in wild radish from the WA wheatbelt revealed that Glu376 was widespread, and that some mutations of AHAS are more common than others. Computer simulation was used to examine the molecular basis of resistance-endowing AHAS target-site mutations. Furthermore, through the computer-aided analysis, residues were identified with the potential to confer resistance upon substitution, but which have not previously been assessed for this possibility. Results from this Ph.D. research demonstrate that diverse, unrelated mechanisms of resistance to PSII inhibitors, auxinics, and AHAS inhibitors have evolved in wild radish of the WA wheatbelt, and that these mechanisms have accumulated in some populations.