Seletividade de glyphosate isolado ou em misturas para soja RR em aplicações sequenciais

O uso de misturas de herbicidas latifolicidas com o glyphosate tem sido uma alternativa para o controle de plantas daninhas resistentes ao glyphosate ou de difícil controle nos cultivos de soja RR. Este trabalho teve o objetivo de avaliar a seletividade de aplicações sequenciais de glyphosate, isolado ou em mistura com latifolicidas, para a soja RR. As aplicações dos tratamentos foram feitas em plantas de soja cultivar CD214 RR nos estádios de desenvolvimento V1 a V2 e V3 a V4. Os herbicidas e as respectivas doses (g i.a. ha-1) utilizadas foram: glyphosate (g e.a. ha-1) isolado (720/480, 720/720, 960/960 e 1.200/1.200) e as misturas de glyphosate + cloransulam-methyl (720 + 15,12/480 + 15,12), glyphosate + fomesafen (720 + 62,5/480 + 62,5), glyphosate + lactofen (720 + 36/480 + 36), glyphosate + chlorimuron-ethyl (720 + 6,25/480 + 6,25), glyphosate + flumiclorac-pentyl (720 + 15/480 + 15), glyphosate + bentazon (720 + 240/480 + 240) e glyphosate + imazethapyr (720 + 40/480 + 40). O delineamento adotado foi o de blocos casualizados, em esquema de parcelas subdivididas, com quatro repetições. As variáveis avaliadas foram: fitointoxicação, altura de plantas, estande, fechamento do dossel, número de vagens por planta, massa de cem grãos e produtividade. Todos os tratamentos promoveram efeitos visuais de fitointoxicação na cultura da soja; todavia, em nenhuma das situações estudadas houve prejuízo no rendimento de grãos.

Novel technology for preparation of optically active chemicals

Asymmetric synthesis using modified heterogeneous catalysts has gained lots of interest in the production of optically pure chemicals, such as pharmaceuticals, nutraceuticals, fragrances and agrochemicals. Heterogeneous modified catalysts capable of inducing high enantioselectivities are preferred in industrial scale due to their superior separation and handling properties. The topic has been intensively investigated both in industry and academia. The enantioselective hydrogenation of ethyl benzoylformate (EBF) to (R)-ethyl mandelate over (-)-cinchonidine (CD)-modified Pt/Al2O3 catalyst in a laboratory-scale semi-batch reactor was studied as a function of modifier concentration, reaction temperature, stirring rate and catalyst particle size. The main product was always (R)-ethyl mandelate while small amounts of (S)-ethyl mandelate were obtained as by product. The kinetic results showed higher enantioselectivity and lower initial rates approaching asymptotically to a constant value as the amount of modifier was increased. Additionally, catalyst deactivation due to presence of impurities in the feed was prominent in some cases; therefore activated carbon was used as a cleaning agent of the raw material to remove impurities prior to catalyst addition. Detailed characterizations methods (SEM, EDX, TPR, BET, chemisorption, particle size distribution) of the catalysts were carried out. Solvent effects were also studied in the semi-batch reactor. Solvents with dielectric constant (e) between 2 and 25 were applied. The enantiomeric excess (ee) increased with an increase of the dielectric coefficient up to a maximum followed by a nonlinear decrease. A kinetic model was proposed for the enantioselectivity dependence on the dielectric constant based on the Kirkwood treatment. The non-linear dependence of ee on (e) successfully described the variation of ee in different solvents. Systematic kinetic experiments were carried out in the semi-batch reactor. Toluene was used as a solvent. Based on these results, a kinetic model based on the assumption of different number of sites was developed. Density functional theory calculations were applied to study the energetics of the EBF adsorption on pure Pt(1 1 1). The hydrogenation rate constants were determined along with the adsorption parameters by non-linear regression analysis. A comparison between the model and the experimental data revealed a very good correspondence. Transient experiments in a fixed-bed reactor were also carried out in this work. The results demonstrated that continuous enantioselective hydrogenation of EBF in hexane/2-propanol 90/10 (v/v) is possible and that continuous feeding of (-)-cinchonidine is needed to maintain a high steady-state enantioselectivity. The catalyst showed a good stability and high enantioselectivity was achieved in the fixed-bed reactor. Chromatographic separation of (R)- and (S)-ethyl mandelate originating from the continuous reactor was investigated. A commercial column filled with a chiral resin was chosen as a perspective preparative-scale adsorbent. Since the adsorption equilibrium isotherms were linear within the entire investigated range of concentrations, they were determined by pulse experiments for the isomers present in a post-reaction mixture. Breakthrough curves were measured and described successfully by the dispersive plug flow model with a linear driving force approximation. The focus of this research project was the development of a new integrated production concept of optically active chemicals by combining heterogeneous catalysis and chromatographic separation technology. The proposed work is fundamental research in advanced process technology aiming to improve efficiency and enable clean and environmentally benign production of enantiomeric pure chemicals.

Bio-ethanol valorization towards C4s including 1-butanol over metal modified alumina and zeolite catalysts

Bio-ethanol has been used as a fuel additive in modern society aimed at reducing CO2-emissions and dependence on oil. However, ethanol is unsuitable as fuel supplement in higher proportions due to its physico-chemical properties. One option to counteract the negative effects is to upgrade ethanol in a continuous fixed bed reactor to more valuable C4 products such as 1-butanol providing chemical similarity with traditional gasoline components. Bio-ethanol based valorization products also have other end-uses than just fuel additives. E.g. 1-butanol and ethyl acetate are well characterised industrial solvents and platform chemicals providing greener alternatives. The modern approach is to apply heterogeneous catalysts in the investigated reactions. The research was concentrated on aluminium oxide (Al2O3) and zeolites that were used as catalysts and catalyst supports. The metals supported (Cu, Ni, Co) gave very different product profiles and, thus, a profound view of different catalyst preparation methods and characterisation techniques was necessary. Additionally, acidity and basicity of the catalyst surface have an important role in determining the product profile. It was observed that ordinary determination of acid strength was not enough to explain all the phenomena e.g. the reaction mechanism. One of the main findings of the thesis is based on the catalytically active site which originates from crystallite structure. As a consequence, the overall evaluation of different by-products and intermediates was carried out by combining the information. Further kinetic analysis was carried out on metal (Cu, Ni, Co) supported self-prepared alumina catalysts. The thesis gives information for further catalyst developments aimed to scale-up towards industrially feasible operations.

Doses e épocas de aplicação de regulador de crescimento em híbridos de milho

A fim de avaliar o efeito do regulador de crescimento trinexapac-ethyl em diferentes doses e épocas de aplicação em dois híbridos de milho, instalaram-se dois experimentos em Ponta Grossa, PR, Brasil, no ano agrícola de 2010/11. O delineamento experimental foi o de blocos ao acaso, em esquema fatorial 4 x 4 (doses x épocas de aplicação), com quatro repetições. Os tratamentos constaram da aplicação do trinexapac-ethyl (Moddus®) nas doses de 0,0, 187,5, 375,0 e 562,5 g ha-1 nos estádios V2, V4, V6 e V8 do milho, nos híbridos Status TL e Maximus TLTG. Avaliaram-se características agronômicas, componentes de produção e produtividade. A época de aplicação do trinexapac-ethyl não afetou características agronômicas e a produtividade dos dois híbridos de milho. Em relação à dose do regulador, somente o Maximus TLTG mostrou aumento da largura e diminuição do comprimento das folhas com o incremento da dose do produto, sem efeitos substanciais nos componentes da produção e na produtividade. Os resultados mostraram pouca resposta dos híbridos avaliados à dose e época de aplicação do trinexapac-ethyl; ao contrário do trigo, o uso na cultura deve ser mais bem avaliado, especialmente em relação à dose do produto e à reação de híbridos.

Impacto de herbicidas em isolados de Trichoderma spp.

O uso de microrganismos é uma alternativa para o controle de doenças em plantas. Todavia, é prudente verificar a interação desse com os demais métodos de controle empregados em determinada cultura. Dessa forma, objetivou-se avaliar a fungitoxicidade dos herbicidas sobre o crescimento e desenvolvimento dos isolados de Trichoderma spp. Utilizou-se o delineamento inteiramente casualizado, em esquema fatorial 6 x 6 x 4, com quatro repetições. O fator A correspondeu aos herbicidas pendimethalin, clomazone, carfentrazone-ethyl, oxadiazon, thiobencarb + propanil e byspiribac-sodium; o fator B, às doses dos herbicidas - 0, 25, 50, 75, 100 e 200% da dose recomendada; e o fator C, aos isolados de Trichoderma spp. AJAM 18, CE 66, TRI 01 e TRI 02. O ensaio foi realizado em condições in vitro; avaliaram-se o crescimento micelial radial (CMR) e a esporulação dos isolados após aplicação dos herbicidas. Observaram-se diferenças de sensibilidade dos isolados para o mesmo produto testado. O oxadiazon reduziu o CMR dos isolados AJAM 18 e TRI 01 em 66 e 35%, respectivamente. No entanto, reduziu apenas 16% do CMR do isolado TRI 02 e não alterou o CMR do isolado CE 66 mesmo em 200% da dose recomendada. Verificaram-se diferentes efeitos dos produtos em cada isolado. A mistura comercial de thiobencarb+propanil foi altamente tóxica aos isolados de Trichoderma spp., com reduções em torno de 85% no CMR e no número de esporos. Por outro lado, o byspiribac-sodium pouco afetou os isolados, apresentando reduções inferiores a 10% no CMR e na esporulação. O carfentrazone-ethyl e byspiribac-sodium demonstraram ser compatíveis com os isolados de Trichoderma spp. estudados.

Manejo de Conyza bonariensis resistente ao glyphosate: coberturas de inverno e herbicidas em pré-semeadura da soja

Conyza bonariensis tornou-se a principal planta daninha da cultura da soja no Sul do Brasil, em decorrência da evolução para resistência ao herbicida glyphosate. O objetivo deste trabalho foi avaliar o efeito de diferentes coberturas de inverno e da associação de manejo de dessecação pré-semeadura da soja, visando ao controle de C. bonariensis resistente ao glyphosate. Um experimento foi conduzido em campo, na safra 2010/2011. Os tratamentos foram conduzidos em esquema de parcelas subdivididas, em que as coberturas de inverno foram alocadas nas parcelas principais: aveia-preta, nabo, ervilhaca, azevém, trigo e pousio. Nas subparcelas, foram alocados os tratamentos de manejo de dessecação pré-semeadura da soja: glyphosate (720 g e.a ha-1), glyphosate (720 g e.a ha-1) + 2,4-D (1.050 g e.a ha-1), glyphosate (720 g e.a ha-1) + 2,4-D (1.050 g e.a ha-1)/paraquat (200 g i.a ha-1) + diuron (100 g i.a ha-1), glyphosate (720 g e.a ha-1) + chlorimuron-ethyl (80 g i.a ha-1), glyphosate (720 g e.a ha-1) + chlorimuron-ethyl (80 g i.a ha-1)/paraquat (200 g i.a ha-1) + diuron (100 g i.a ha‑1) e roçada. O nabo foi a espécie de cobertura que produziu o maior volume de massa seca durante o inverno, enquanto a ervilhaca foi a que apresentou maior efeito supressor sobre a germinação e o desenvolvimento inicial de C. bonariensis. Associações de glyphosate com 2,4-D ou chlorimuron-ethyl, seguidas da aplicação sequencial de paraquat + diuron, causaram maior redução na infestação de C. bonariensis.

On-line determination of residual collector concentration in flotation process

Valuable minerals can be recovered by using froth flotation. This is a widely used separation technique in mineral processing. In a flotation cell hydrophobic particles attach on air bubbles dispersed in the slurry and rise on the top of the cell. Valuable particles are made hydrophobic by adding collector chemicals in the slurry. With the help of a frother reagent a stable froth forms on the top of the cell and the froth with valuable minerals, i.e. the concentrate, can be removed for further processing. Normally the collector is dosed on the basis of the feed rate of the flotation circuit and the head grade of the valuable metal. However, also the mineral composition of the ore affects the consumption of the collector, i.e. how much is adsorbed on the mineral surfaces. Therefore it is worth monitoring the residual collector concentration in the flotation tailings. Excess usage of collector causes unnecessary costs and may even disturb the process. In the literature part of the Master’s thesis the basics of flotation process and collector chemicals are introduced. Capillary electrophoresis (CE), an analytical technique suitable for detecting collector chemicals, is also reviewed. In the experimental part of the thesis the development of an on-line CE method for monitoring the concentration of collector chemicals in a flotation process and the results of a measurement campaign are presented. It was possible to determine the quality and quantity of collector chemicals in nickel flotation tailings at a concentrator plant with the developed on-line CE method. Sodium ethyl xanthate and sodium isopropyl xanthate residuals were found in the tailings and slight correlation between the measured concentrations and the dosage amounts could be seen.

Rapid diagnosis of resistance to imidazolinone herbicides in barnyardgrass (Echinochloa crus-galli) and control of resistant biotypes with alternative herbicides

The resistance of barnyardgrass (Echinochloa crus-galli) to imidazolinone herbicides is a worldwide problem in paddy fields. A rapid diagnosis is required for the selection of adequate prevention and control practices. The objectives of this study were to develop expedite bioassays to identify the resistance to imidazolinone herbicides in barnyardgrass and to evaluate the efficacy of alternative herbicides for the post-emergence control of resistant biotypes. Three experiments were conducted to develop methods for diagnosis of resistance to imazethapyr and imazapyr + imazapic in barnyardgrass at the seed, seedling and tiller stages, and to carry out a pot experiment to determine the efficacy of six herbicides applied at post-emergence in 13 biotypes of barnyardgrass resistant to imidazolinones. The seed soaking bioassay was not able to differentiate the resistant and susceptible biotypes. The resistance of barnyardgrass to imidazolinones was effectively discriminated in the seedlings and tiller bioassays seven days after incubation at the concentrations of 0.001 and 0.0001 mM, respectively, for both imazethapyr and imazapyr + imazapic. The biotypes identified as resistant to imidazolinones showed different patterns of susceptibility to penoxsulam, bispyribac-sodium and pyrazosulfuron-ethyl, and were all controlled with profoxydim and cyhalofop-butyl. The seedling and tiller bioassays are effective in the diagnosis of barnyardgrass resistance to imidazolinone herbicides, providing an on-season opportunity to identify the need to use alternative herbicides to be applied at post-emergence for the control of the resistant biotypes.

Effect of plant regulators on growth and flowering of 'Meyer' zoysiagrass

This trial aimed to evaluate the effect of sequential applications of different plant regulators over growth and flower rachis emission of 'Meyer' zoysiagrass (Zoysia japonica). The study was conducted on 15-month old green turfgrass under a randomized complete block design with four replications. The following plant regulator and doses were tested: trinexapac-ethyl (113+113, 226+113, 226+226, 452+113, 452+226, 452+452, 678+339 e 904+452 g a.i./ha-1), prohexadione-calcium (100+100 e 200+200 g a.i. ha-1) and bispyribac-sodium (40+40 e 60+60 g a.i. ha-1), as well as an untreated control. The turfgrass was mowed again at 3.0 cm aboveground and the second plant regulator was applied when 'Meyer' zoysiagrass was between 5.0 and 6.0 cm high. The effect of the treatments was visually rated for visual injury, plant height, height and number of flower rachis, and total dry mass production of clippings. Only bispyribac-sodium had visual symptoms of injury on 'Meyer' zoysiagrass, and no intoxication was observed at 28 days after the second application (DAAB). The sequential applications of trinexapac-ethyl, prohexadione-calcium and bispyribac-sodium reduced by more than 80% the total clipping dry mass produced by 'Meyer' zoysiagrass. All the plant regulators tested also showed promising results in reducing the height and emission of rachis, especially when trinexapac-ethyl was applied at the doses 452+452, 678+339 and 904+452 g a.i. ha-1. 'Meyer' zoysiagrass turfgrass can be handled with the sequential application of a plant regulator, which reduces the need for mowing over a period up to 110 days after the application of the second plant regulator, and it also avoids deleterious visual effects over turfgrass.

Globe fringerush (Fimbristylis miliacea) cross resistance to als-inhibitor herbicides under field conditions in irrigated rice in the south of Brazil

ALS-inhibiting herbicides usually provide adequate weed control in irrigated rice fields. After consecutive years of use, the Cyperaceae species, globe fringerush (Fimbristylis miliacea) began to show resistance to ALS (acetolactate synthase) inhibitors. Globe fringerush is one of the most problematic herbicide-resistant weeds in irrigated rice in the state of Santa Catarina in the South of Brazil. The objective of this research was to examine cross resistance of globe fringerush to ALS inhibitors, under field conditions. Two experiments were conducted in a rice field naturally infested with ALS-resistant globe fringerush in Santa Catarina, in the 2008/09 and 2009/10 cropping seasons. The experimental units were arranged in randomized complete block design, with five replicates, consisting of two factors (herbicide and dose) in a 4 x 5 factorial arrangement. ALS herbicides included bispyribac-sodium, ethoxysulfuron, pyrazosulfuron-ethyl and penoxsulam. Six-leaf globe fringerush was sprayed with herbicide doses of 0, 0.5, 1, 2 and 4X the recommended doses in a spray volume of 200 L ha-1. The number of rice culm, filled and sterile grains, plant height, dry shoot biomass and grain yield were recorded. Globe fringerush control was evaluated 28 and 70 days after herbicide application (DAA); shoots were harvested at 13 weeks after herbicide application and dry weight recorded. Competition with globe fringerush reduced the number of culm and rice grain yield. The globe fringerush biotype in this field was resistant to all ALS herbicides tested. Penoxsulam had the highest level of activity among treatments at 28 and 70 DAA, but the control level was only 50% and 42%, respectively, in the second year of assessment. This was not enough to prevent rice yield loss. Alternative herbicides and weed control strategies are necessary to avoid yield losses in rice fields infested with ALS-resistant biotypes of globe fringerush.

Herbicide selectivity in alfalfa crops

This study aimed to determine the selectivity of herbicides applied in pre- and post-emergence for alfalfa crops. Three separate experiments were carried out under greenhouse conditions. The first experiment was arranged in a completely randomized design with three replications in a 4 x 11 + 1 factorial scheme , with eleven herbicides (bentazon, chlorimuron-ethyl, fomesafen, fluazifop-p-butyl, saflufenacil, imazethapyr, clethodim, nicosulfuron, imazaquin, haloxyfop-methyl and MSMA), four doses of each herbicide (0.5 D, 0.75 D, 1.0 D and 1.25 D, where D = recommended dose), plus an untreated control. The products were applied to alfalfa plants at the stage of 4 to 5 leaf pairs. In the second experiment, the effect of pre-emergent herbicides on early alfalfa development was observed through a completely randomized design with five replications in a 3 x 4 x 2 factorial scheme, with three herbicides (hexazinone, atrazine + simazine, S-metolachlor), four doses (0.5 D, 0.75 D, 1.0 D and 1.25 D), and two types of soil texture (loamy and clay soil), plus an untreated control. The third experiment evaluated the action of atrazine, 2,550 g ha-1; clomazone - 600 g ha-1; diclosulam - 25 g ha-1; diuron+hexazinone - 936 + 264 g ha-1 and diuron+hexazinone +sulfometuron - 1,386 + 391 + 33.35 g ha-1 on alfalfa sown at different times after herbicide application. The effects of the treatments on alfalfa were evaluated according to visual phytotoxicity symptoms, plant height, and biomass of roots and shoots. Among the herbicides applied at post-emergence, imazethapyr, clethodim, haloxyfop-p-methyl and MSMA were selective for alfalfa, while among those applied at pre-emergence, none were selective, regardless of soil texture. The results of the third experiment showed that the herbicides diclosulam, hexazinone + diuron and atrazine caused less toxicity in alfalfa plants.

Effect of selectivity of herbicides and plant growth regulators used in sugarcane crops on immature stages of Trichogramma galloi (Hymenoptera: Trichogrammatidae)

Herbicides and plant growth regulators are often used in sugarcane management. However, the use of non-selective pesticides can cause adverse effects on the efficiency of beneficial insects in integrated pest management. Within this context, this study aimed to evaluate the effect of such products on the immature stages of the parasitoid Trichogramma galloi. Eggs of Diatraea saccharalis containing the parasitoid at the egg-larva stage and at the prepupal and pupal stages were immersed in test solutions of the following pesticides (maximum recommended doses for sugarcane): herbicides clomazone and diuron + hexazinone, and plant growth regulators trinexapac-ethyl and sulfometuron-methyl. The biological properties evaluated were emergence (F1 and F2) and number of eggs parasitized by T. galloi (F1). The products were classified according to percentage of reduction in emergence and parasitism: harmless (<30%), slightly harmful (30-79%), moderately harmful (80-99%) and harmful (>99%). The pesticides evaluated were considered to be harmless or slightly harmful to immature T. galloi and, thus, their use should be preferred for preserving this parasitoid species in sugarcane management programs.

Improving diquat efficacy on grasses by adding adjuvants to the spray solution before use

The effect of five adjuvants (non-ionic surfactant, paraffinic oil, vegetable oil, mixture of fatty acids methyl esters plus surfactant blend, and organosilicone) on diquat efficacy was assessed on poverty brome, sterile oat, and Italian ryegrass in field and pot experiments. All tank mixtures with diquat increased diquat efficacy from 50-54% to 77-98% as for fresh weight reduction, indicating significant enhancement of diquat efficacy on grasses. The increased efficacy was most likely attributed to better droplet retention and diffusion on the leaf surfaces. When combined with non-ionic surfactant, diquat showed slightly more rapid control of grass weeds (i.e. symptoms were visible within a few hours after application).

Multiple resistance of Conyza sumatrensis to Chlorimuron­ethyl and to Glyphosate

Weed resistance to herbicides has been a major issue in Brazil, mainly due to the inefficiency of the herbicides used in no-till areas and to the high cost of these herbicide treatments. Failures in controlling the weed Conyza have been reported in Western and Northern grain crop areas in Paraná (Brazil). This work aimed to evaluate the potential occurrence of C. sumatrensis biotypes resistant to the herbicides chlorimuron-ethyl and glyphosate. Experiments were carried out under greenhouse conditions with four biotypes (Cascavel-2, Toledo-4, Tupãssi-6, and Assis Chateaubriand-7) possibly resistant to, as well as a population considered susceptible to chlorimuron-ethyl and glyphosate. To obtain dose-response curves, eight herbicide doses of chlorimuron-ethyl (0, 2.5, 5, 10, 20, 40, 80 and 160 g ha-1) and glyphosate (0, 90, 180, 360, 720, 1,440, 2,880 and 5,760 g e.a. ha-1) were applied and weed control and shoot biomass evaluations were made. Results provided evidence that two biotypes (Cascavel-2 and Tupãssi-6) were resistant to glyphosate and four biotypes (Cascavel-2, Toledo-4, Tupãssi-6 and Assis Chateaubriand-7) were resistant to chlorimuron­ethyl. Multiple resistance to glyphosate and chlorimuron was confirmed for biotypes Cascavel­2 and Tupãssi 6. This is the first report on multiple resistance in Conyza sumatrensis, worldwide.

PHYSIOLOGICAL QUALITY OF SOYBEAN SEEDS DEPENDING ON THE PREHARVEST DESICCATION

ABSTRACTDepending on the cultivar, the use of desiccants in the preharvest can favor maintenance of physiological quality. The objective of the study was to assess the physiological quality of soybean seeds as due to the use of apreharvest desiccant and desiccation time in two harvests (2011/12 and 2012/13). The treatments were five soybean cultivars, two growth stages of application, a control (without desiccant application), and three desiccants (glufosinate-ammonium, carfentrazone-ethyl and paraquat) (2011/12 harvest). In the 2012/13 harvest the carfentrazone-ethyl desiccant was replaced by diquat. The physiological quality of seeds was assessed by the percentage of viability and vigor (cold test, tetrazolium test and accelerated aging test). In 2011/12 harvest, there was an early harvest in six days with the use of glufosinate-ammonium and paraquat desiccants, when desiccation was done in stage R7.1, with maintenance of seed quality; however it was dependent on the cultivar. In the 2012/13 harvest there was no early harvesting due to the presence of rain in the preharvest and the use of desiccation did not affect the physiological quality of the seeds either. Cultivar NA5909 RG was more tolerant to remaining in the cultivation environment and maintained higher viability than 90% and greater vigor of 71% by the cold test compared to cultivar BMX Turbo (2011/12 harvest). It is concluded that desiccation can be a viable alternative to the soybean early harvesting, but it depends on the cultivar, the time of desiccation, the active principle of the desiccant and the absence of rain in preharvest.