Surface modification of alumina nanofibres for the selective adsorption of alachlor and imazaquin herbicides

The effective removal of pollutants using a thermally and chemically stable substrate that has controllable absorption properties is a goal of water treatment. In this study, the surfaces of thin alumina (γ-Al2O3) nanofibres were modified by the grafting either of two organosilane agents, 3-chloro-propyl-triethoxysilane (CPTES) and octyl-triethoxysilane (OTES). These modified materials were then trialed as absorbents for the removal of two herbicides, alachlor and imazaquin from water. The formation of organic groups during the functionalisation process established super hydrophobic sites on the surfaces of the nanofibres. This super hydrophobic group is a kind of protruding adsorption site which facilitates the intimate contact with the pollutants. OTES grafted substrate were shown to be more selective for alachlor while imazaquin selectivity is shown by the CPTES grafted substrate. Kinetics studies revealed that imazaquin was rapidly adsorbed on CPTES-modified surfaces. However, the adsorption of alachlor by OTES grafted surface was achieved more slowly.

Modelagem molecular voltada para a construção de um nanobiossensor para detecção do herbicida Imazaquin

In this study, our goal was develop and describe a molecular model of the enzyme-inhibiting interaction which can be used for an optimized projection of a Microscope Force Atomic nanobiosensor to detect pesticides molecules, used in agriculture, to evaluate its accordance with limit levels stipulated in valid legislation for its use. The studied herbicide (imazaquin) is a typical member of imidazolinone family and is an inhibitor of the enzymatic activity of Acetohydroxiacid Synthase (AHAS) enzyme that is responsible for the first step of pathway for the synthesis of side-chains in amino acids. The analysis of this enzyme property in the presence of its cofactors was made to obtain structural information and charge distribution of the molecular surface to evaluate its capacity of became immobilized on the Microscopy Atomic Force tip. The computational simulation of the system, using Molecular Dynamics, was possible with the force-field parameters for the cofactor and the herbicides obtained by the online tool SwissParam and it was implemented in force-field CHARMM27, used by software GROMACS; then appropriated simulations were made to validate the new parameters. The molecular orientation of the AHAS was defined based on electrostatic map and the availability of the herbicide in the active site. Steered Molecular Dynamics (SMD) Simulations, followed by quantum mechanics calculations for more representative frames, according to the sequential QM/MM methodology, in a specific direction of extraction of the herbicide from the active site. Therefore, external harmonic forces were applied with similar force constants of AFM cantilever for to simulate herbicide detection experiments by the proposed nanobiosensor. Force value of 1391 pN and binding energy of -14048.52 kJ mol-1 were calculated.

Nanostructured metal oxides as adsorbents and photocatalysts

This research underlines the extensive application of nanostructured metal oxides in environmental systems such as hazardous waste remediation and water purification. This study tries to forge a new understanding of the complexity of adsorption and photocatalysis in the process of water treatment. Sodium niobate doped with a different amount of tantalum, was prepared via a hydrothermal reaction and was observed to be able to adsorb highly hazardous bivalent radioactive isotopes such as Sr2+ and Ra2+ions. This study facilitates the preparation of Nb-based adsorbents for efficiently removing toxic radioactive ions from contaminated water and also identifies the importance of understanding the influence of heterovalent substitution in microporous frameworks. Clay adsorbents were prepared via a two-step method to remove anionic and non-ionic herbicides from water. Firstly, layered beidellite clay was treated with acid in a hydrothermal process; secondly, common silane coupling agents, 3-chloro-propyl trimethoxysilane or triethoxy silane, were grafted onto the acid treated samples to prepare the adsorption materials. In order to isolate the effect of the clay surface, we compared the adsorption property of clay adsorbents with ƒ×-Al2O3 nanofibres grafted with the same functional groups. Thin alumina (£^-Al2O3) nanofibres were modified by the grafting of two organosilane agents 3-chloropropyltriethoxysilane and octyl triethoxysilane onto the surface, for the adsorptive removal of alachlor and imazaquin herbicides from water. The formation of organic groups during the functionalisation process established super hydrophobic sites along the surfaces and those non-polar regions of the surfaces were able to make close contact with the organic pollutants. A new structure of anatase crystals linked to clay fragments was synthesised by the reaction of TiOSO4 with laponite clay for the degradation of pesticides. Based on the Ti/clay ratio, these new catalysts showed a high degradation rate when compared with P25. Moreover, immobilized TiO2 on laponite clay fragments could be readily separated out from a slurry system after the photocatalytic reaction. Using a series of partial phase transition methods, an effective catalyst with fibril morphology was prepared for the degradation of different types of phenols and trace amount of herbicides from water. Both H-titanate and TiO2-(B) fibres coated with anatase nanocrystal were studied. When compared with a laponite clay photocatalyst, it was found that anatase dotted TiO2-(B) fibres prepared by a 45 h hydrothermal treatment followed by calcination were not only superior in performance in photocatalysis but could also be readily separated from a slurry system after photocatalytic reactions. This study has laid the foundation for the development of the ability to fabricate highly efficient nanostructured solids for the removal of radioactive ions and organic pollutants from contaminated water. These results now seem set to contribute to the development of advanced water purification devices in the future. These modified nanostructured materials with unusual properties have broadened their application range beyond their traditional use as adsorbents, to also encompass the storage of nuclear waste after concentrating from contaminated water.

Removal of herbicides from aqueous solutions by modified forms of montmorillonite

This investigation for the removal of agricultural pollutants, imazaquin and atrazine was conducted using montmorillonite (MMT) exchanged with organic cations through ion exchange. The study found that the adsorption of the herbicides was affected by the degree of organic cation saturations, the size of organic cations and the different natures of the herbicides. The modified clays intercalated with the larger surfactant molecules at the higher concentrations tended to enhance the adsorption of imazaquin and atrazine. In particular, the organoclays were highly efficient for the removal of imazaquin while the adsorption of atrazine was minimal due to the different hydrophobicities. Both imazaquin and atrazine were influenced by the changes of pH. The amphoteric imazaquin exists as an anion at the pH 5–7 and the anionic imazaquin was protonated to a neutral and further a cationic form when the pH is lower. The weak base, atrazine was also protonated at lower pH values. The anionic imazaquin had a strong affinity to the organoclays on the external surface as well as in the interlayer space of the MMT through electrostatic and hydrophobic interactions. In this study, the electrostatic interaction can be the primary mechanism involved during the adsorption process. This study also investigated a comparative adsorption for the imazaquin and atrazine and the lower adsorption of atrazine was enhanced and this phenomenon was due to the synergetic effect. This work highlights a potential mechanism for the removal of specific persistence herbicides from the environment.

Selective herbicide strategies for use in Australian desmanthus seed crops

Grass and broad-leaved weeds can reduce both yields and product marketability of desmanthus (Desmanthus virgatus) seed crops, even when cultural control strategies are used. Selective herbicides might economically control these weeds, but, prior to this study, the few herbicides tolerated by desmanthus did not control key weed contaminants of desmanthus seed crops. In this study, the tolerance of desmanthus cv. Marc to 55 herbicides used for selective weed control in other leguminous crops was assessed in 1 pot trial and 3 Queensland field trials. One field trial assessed the tolerance of desmanthus seedlings to combinations of the most promising pre-emergent and post emergent herbicides. The pre-emergent herbicides, imazaquin, imazethapyr, pendimethalin, oryzalin and trifluralin, gave useful weed control with very little crop damage. The post-emergent herbicides, haloxyfop, clethodim, propyzamide, carbetamide and dalapon, were safe for controlling grass weeds in desmanthus. Selective post-emergence control of broad-leaved weeds was achieved using bentazone, bromoxynil and imazethapyr. One trial investigated salvaging second-year desmanthus crops from mature perennial weeds, and atrazine, terbacil and hexazinone showed some potential in this role. Overall, our results show that desmanthus tolerates herbicides which collectively control a wide range of weeds encountered in Queensland. These, in combination with cultural weed control strategies, should control most weeds in desmanthus seed crops.

Manejo de malezas bajo dos sistemas de labranza en cultivo de soya (Glycine max (L.) Merril)

El presente trabajo fue realizado en el Centro Experimental del Algodón, en el ciclo agrícola 1989-1990 con el objetivo de estudiar la influencia del control químico y la Labranza Minina y Convencional en las poblaciones de malezas, durante el primer ciclo del cultivo de soya. Se utilizó un diseño de Bloque Completos al Azar non tres tratamientos y cuatro repeticiones. Se realizaron recuentos de malezas a los 15, 30 y 45 días después de la emergencia del cultivo. Se tomaron datos de individuos/especie y biomasa seca de malezas en un metro cuadrado. Al final se midió el rendimiento del cultivo en Kg/ha Los Tratamientos fueron: Tratamiento (Lab. Min; Lab. Min; Lab. Conv.) N. Común (Paraguat; Glifosto; Imazaquin + Pendimentalin) N. Comercial (Gramoxone; Roundup; Scepter + Prowl) Dosis (1/ha) (2.13; 4.26; 0.99+1.42) En el estudio se encontró que el mejor tratamiento fue donde se utilizó Labranza Convencional y control de malezas ron Scepter y Prowl.

Influência do tipo e da quantidade de resíduos vegetais na eficácia de herbicidas aplicados em pré-emergência na cultura da soja

Com o objetivo de avaliar, em condições de campo e na região originalmente sob cerrado, os efeitos de resíduos vegetais [sorgo de cobertura (híbrido Cober Exp), milheto forrageiro (var. BN2), capim-pé-de-galinha (Eleusine coracana) e capim-braquiária (Brachiaria brizantha)] e duas quantidades de palha (3,0 e 5,5 t ha-1, no primeiro ano do estudo, e 3,5 e 5,8 t ha-1, no segundo) na eficácia de herbicidas residuais (diclosulam e imazaquin) aplicados em pré-emergência na cultura da soja, foi desenvolvido experimento, no ano agrícola 2003/2004 e repetido em 2004/2005, na fazenda Três Marcos, em Uberlândia (MG). Os herbicidas diclosulam e imazaquin não tiveram a eficácia afetada pela presença de palha na superfície do solo, independentemente da quantidade. Associados às coberturas, obteve-se melhor controle. No primeiro ano, após a instalação da cultura da soja, plantas de Eleusine coracana tornaram-se as principais infestantes na parcela de capim-pé-de-galinha.

Influência do tipo e da quantidade de resíduos vegetais associados a herbicidas residuais no desenvolvimento da cultura da soja

O objetivo do trabalho foi avaliar, em condições de campo e na região originalmente sob cerrado, os efeitos de resíduos vegetais [sorgo de cobertura (híbrido Cober Exp), milheto forrageiro (var. BN2), capim pé-de-galinha (Eleusine coracana) e capim braquiária (Brachiaria brizantha)] e duas quantidades de palha (3,0 e 5,5 t ha-1, no primeiro ano do estudo, e 3,5 e 5,8 t ha-1, no segundo), associados a herbicidas residuais (diclosulam a 35 g ha-1 e imazaquin a 140 g ha-1) aplicados em pré-emergência, no desenvolvimento da cultura da soja. Para tal, foi desenvolvido experimento no ano agrícola 2003/2004 e repetido em 2004/2005, na Fazenda Três Marcos, em Uberlândia (MG). No primeiro ano, após a instalação da cultura da soja, plantas de Eleusine coracana tornaram-se as principais infestantes na cobertura de capim pé-de-galinha. Devido à ausência de controle dessa espécie pelos herbicidas testados, a convivência entre ela e a cultura refletiu negativamente nas plantas de soja. O herbicida imazaquin afetou, indiretamente, as plantas de soja, em virtude do seu controle insatisfatório das plantas daninhas. Nas plantas de soja crescidas sobre cobertura de capim braquiária (nos dois anos) e de capim pé-de-galinha (no segundo ano) observaram-se maior produtividade de grãos, acúmulo de massa e altura de plantas. Os resíduos vegetais de sorgo influenciaram negativamente no desenvolvimento das plantas de soja, nos dois anos. Quanto aos níveis de palha, houve diferença entre eles para milheto forrageiro (no primeiro ano) e sorgo (no segundo ano). O menor nível de milheto forrageiro e o maior de sorgo ocasionaram prejuízos às plantas de soja.

Envelhecimento de resíduos vegetais sobre o solo e os reflexos na eficácia de herbicidas aplicados em pré-emergência

Com o objetivo de avaliar os efeitos do envelhecimento dos resíduos vegetais de diferentes espécies [sorgo de cobertura (Sorghum bicolor x S. sudanensis 'Cober Exp'), milheto forrageiro (Pennisetum americanum 'BN2'), capim-pé-de-galinha (Eleusine coracana) e capim-braquiária (Brachiaria brizantha)], no controle de Ipomoea grandifolia, pelos herbicidas diclosulam e imazaquin, aplicados em pré-emergência, foi desenvolvido experimento em casa de vegetação, no período de agosto a dezembro de 2004. Foram realizadas determinações químicas nos materiais vegetais em decomposição. A eficácia do herbicida diclosulam não foi afetada pelo envelhecimento da palha de nenhuma das coberturas estudadas. Pelo contrário, a associação desse herbicida a qualquer dos resíduos vegetais estudados, principalmente o de capim-braquiária, favoreceu o controle da planta daninha. O imazaquin teve o potencial de controle influenciado pelas coberturas de milheto forrageiro e capim-braquiária, aos 90 dias após a deposição dos resíduos vegetais sobre o solo. Tal comportamento pode ser atribuído ao enriquecimento de celulose e lignina nos materiais vegetais de milheto forrageiro e capim braquiária.

Seletividade de herbicidas pré-emergentes para gramíneas forrageiras tropicais

Este trabalho constou de quatro estudos que foram realizados em casa de vegetação, nos quais se avaliou a seletividade de diferentes herbicidas, aplicados em pré-emergência, sobre algumas gramíneas forrageiras tropicais: Brachiaria decumbens, Brachiaria brizantha cv. Marandu e Panicum maximum cultivares Tanzânia e Mombaça. Os herbicidas e as doses utilizadas, em g ha-1, para cada estudo foram: alachlor - 1.680 e 3.360, metolachlor - 1.200 e 2.400, diuron - 800 e 1.600, imazaquin - 75 e 150, imazapyr - 250 e 500, imazethapyr - 50 e 100, clomazone - 450 e 900, flumetsulam - 70 e 140, ametryn - 625 e 1.250, metribuzin - 525 e 1.050 e trifluralin - 900 e 1.800, além de uma testemunha sem aplicação de herbicidas. Utilizou-se o delineamento experimental inteiramente casualizado, com seis repetições. O consumo de calda de aplicação foi de 180 L ha-1,e a barra de aplicação continha quatro bicos de jato plano tipo 'Teejet' 110.02, espaçados de 0,50 m. Avaliou-se visualmente a intoxicação das plantas através de uma escala percentual de notas e, no final dos estudos, a altura e o peso de matéria seca de plantas. Para P. maximum cv. Mombaça, apenas os herbicidas imazaquin (75 g ha-1), imazethapyr e flumetsulam, em ambas as doses testadas, foram seletivos. Para P. maximum cv. Tanzânia, nenhum dos herbicidas testados foi totalmente seletivo. em relação a B. decumbens, os herbicidas imazaquin e imazethapyr, em ambas as doses, e ametryn (625 g ha¹) foram seletivos. No caso de B. brizantha, os herbicidas diuron (800 g ha¹), ametryn, imazaquin, imazethapyr e flumetsulam, em ambas as doses, apresentaram-se seletivos.

Segurança das condições de trabalho de tratorista em aplicações de herbicidas em soja e amendoim e eficiência de equipamentos de proteção individual

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

Seletividade de herbicidas aplicados em pré-emergência em gramíneas forrageiras

O presente trabalho teve o objetivo de avaliar a seletividade de herbicidas aplicados em pré-emergência sobre a produção e a qualidade de sementes de Brachiaria brizantha cv. Marandu e Brachiaria decumbens cv. Basilisk. Os herbicidas avaliados foram: diuron (800 e 1.600 g ha-1), ametryn (625 e 1.250 g ha-1), imazaquin (75 e 150 g ha-1), imazethapyr (50 e 100 g ha-1) e flumetsulam (70 e 140 g ha-1), além de uma testemunha sem aplicação de herbicidas. As espécies foram avaliadas separadamente no campo. Os experimentos foram instalados no delineamento em blocos casualizados com quatro repetições. Os herbicidas ametryn (625 g ha-1), imazaquin (75 e 150 g ha-1), imazethapyr (50 e 100 g ha-1) e flumetsulam (70 e 140 g ha-1) foram os que proporcionaram maior seletividade às plantas de B. brizantha, enquanto para B. decumbens o diuron (800 e 1.600 g ha-1), o ametryn (625 e 1.250 g ha-1) e o imazethapyr (50 e 100 g ha-1) foram mais seletivos, destacando-se o diuron na menor dose. Contudo, os herbicidas avaliados não alteram a produção e a qualidade das sementes das forrageiras estudadas.

Seletividade de herbicidas para gramíneas forrageiras tropicais aplicados em pré e pós-emergência

Pós-graduação em Agronomia (Agricultura) - FCA

Adubação nitrogenada e aplicação de herbicidas como reguladores de crescimento em grama esmeralda

Pós-graduação em Agronomia - FEIS