Herbicide Molecules Research Articles

Potencial de lixiviação de herbicidas utilizados na cultura do algodão em colunas de solo

O intenso uso de herbicidas implica a necessidade de determinar o potencial dessas substâncias em contaminar fontes aquáticas subsuperficiais. Diante dessa preocupação, o objetivo deste trabalho foi avaliar o efeito de diferentes lâminas de água sobre o potencial de lixiviação de quatro herbicidas utilizados em pré-emergência na cultura do algodão, em dois solos provenientes de Campo Novo do Parecis-MT (RQ - textura arenosa) e Tangará da Serra-MT (LV - textura argilosa). No desenvolvimento deste trabalho utilizouse a técnica de bioensaio em colunas de solo, nas quais foram simuladas irrigações de 0, 20, 40, 60, 80 e 100 mm, após a aplicação de alachlor (RQ 2,40; LV 3,36 kg ha-1), oxyfluorfen (RQ 0,48; LV 0,72 kg ha-1), prometryne (RQ 0,75; LV 1,50 kg ha-1) e S-metolachlor (RQ 1,20; LV 1,44 kg ha-1). Nas amostras de solo com textura arenosa (RQ), evidenciou-se que lâminas de 80 e 100 mm de água proporcionaram lixiviação até a profundidade de 10-15 cm do alachlor e até 15-20 cm do S-metolachlor. Independentemente da lâmina de água aplicada, nas amostras de RQ oxyfluorfen não ultrapassou a camada de 5-10 cm, e o prometryne movimentou-se até a camada de 10-15 cm somente na lâmina de 100 mm de água. Nas amostras de solo com textura argilosa (LV), o oxyfluorfen não se movimentou além da camada superficial, mesmo sob as maiores lâminas de irrigação, e o prometryne atingiu 5-10 cm de profundidade sob lâminas de 80 e 100 mm. Os herbicidas alachlor e S-metolachlor atingiram 10-15 cm de profundidade sob lâminas de 80 e 100 mm no LV. Evidenciou-se uma maior movimentação efetiva das moléculas de herbicidas nas amostras de solo com textura arenosa (RQ), em relação às amostras de solo com textura argilosa (LV).

Remediation of Waters Contaminated with MCPA by the Yeasts Lipomyces starkeyi Entrapped in a Sol−Gel Zirconia Matrix

A single-stage sol-gel route was set to entrap yeast cells of Lipomyces starkeyi in a zirconia (ZrO(2)) matrix, and the remediation ability of the resulting catalyst toward a phenoxy acid herbicide, 4-chloro-2-methylphenoxyacetic acid (MCPA), was studied. It was found that the experimental procedure allowed a high dispersion of the microorganisms into the zirconia gel matrix; the ZrO(2) matrix exhibited a significant sorption capacity of the herbicide, and the entrapped cells showed a degradative activity toward MCPA. The combination of these effects leads to a nearly total removal efficiency (>97%) of the herbicide at 30 °C within 1 h incubation time from a solution containing a very high concentration of MCPA (200 mg L(-1)). On the basis of the experimental evidence, a removal mechanism was proposed involving in the first step the sorption of the herbicide molecules on the ZrO(2) matrix, followed by the microbial degradation operated by the entrapped yeasts, the metabolic activity of which appear enhanced under the microenvironmental conditions established within the zirconia matrix. Repeated batch tests of sorption/degradation of entrapped Lipomyces showed that the removal efficiency retained almost the same value of 97.3% after 3 batch tests, with only a subsequent slight decrease, probably due to the progressive saturation of the zirconia matrix.

Mimicking direct protein–protein and solvent-mediated interactions in the CDP-methylerythritol kinase homodimer: a pharmacophore-directed virtual screening approach

The 2C-methylerythritol 4-phosphate (MEP) pathway for the biosynthesis of isopentenyl pyrophosphate and its isomer dimethylallyl pyrophosphate, which are the precursors of isoprenoids, is present in plants, in the malaria parasite Plasmodium falciparum and in most eubacteria, including pathogenic agents. However, the MEP pathway is absent from fungi and animals, which have exclusively the mevalonic acid pathway. Given the characteristics of the MEP pathway, its enzymes represent potential targets for the generation of selective antibacterial, antimalarial and herbicidal molecules. We have focussed on the enzyme 4-(cytidine 5'-diphospho)-2-C-methyl-D-erythritol kinase (CMK), which catalyses the fourth reaction step of the MEP pathway. A molecular dynamics simulation was carried out on the CMK dimer complex, and protein-protein interactions analysed, considering also water-mediated interactions between monomers. In order to find small molecules that bind to CMK and disrupt dimer formation, interactions observed in the dynamics trajectory were used to model a pharmacophore used in database searches. Using an intensity-fading matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry approach, one compound was found to interact with CMK. The data presented here indicate that a virtual screening approach can be used to identify candidate molecules that disrupt the CMK-CMK complex. This strategy can contribute to speeding up the discovery of new antimalarial, antibacterial, and herbicidal compounds.

Herbicide accumulation and evolution in reservoir sediments

The aim of the present study was to understand the effect of reservoir configurations on sediment pesticide fate. Two dams were selected on the River Garonne, in southwest France: Carbonne and Golfech, both with reservoirs subject to accumulation of herbicide-contaminated sediment. They are situated upstream and downstream respectively of an agricultural and urban area: the Mid-Garonne. The results presented include pesticide concentrations and C/N ratios in the smaller sediment particles (< 2 mm) and values of oxygenation and herbicide concentrations in the water. The dynamic behaviour of sediment in the reservoirs is discussed. The present study shows that the theoretical lifespan (weak remanence in vitro) and the results actually observed in the sediment are conflicting. Pesticide contamination in Carbonne indicates conservation, even accumulation, of herbicide molecules while in Golfech transformation processes clearly dominate. The hydromorphological position of Golfech reservoir, i.e. located at the junction of two rivers with contrasting hydrological regimes and very different oxygenation conditions, leads to accelerated pesticide desorption or degradation. Unfortunately, this configuration is rare.

Environmentally Friendly Formulations of Alachlor and Atrazine: Preparation, Characterization, and Reduced Leaching

Atrazine and alachlor formulations were designed by encapsulating the herbicide molecules into phosphatidylcholine (PC) vesicles, which subsequently were adsorbed on montmorillonite. PC and montmorillonite are classified as substances of minimal toxicological risk by the U.S. EPA. PC enhanced alachlor and atrazine solubilities by 15- and 18-fold, respectively. A 6 mM PC:5 g/L clay ratio was found as optimal for PC adsorption on the clay. Active ingredient contents of the PC-clay formulations ranged up to 8.6% for atrazine and 39.5% for alachlor. Infrared spectroscopy showed hydrophobic interactions of herbicide molecules with the alkyl chains of PC, in addition to hydrophilic interactions with the PC headgroup. Release experiments in a sandy soil showed a slower rate from the PC-clay formulations than the commercial ones. Soil column experiments under moderate irrigation and bioactivity experiments indicate that a reduction in the recommended dose of alachlor and atrazine can be accomplished by using PC-clay formulations.

Study of different herbicide molecules for the control of durum wheat weed

In order to enhance the chances to rotate the herbicide molecules, the effectiveness of a new molecule, pinoxaden, was tested, comparing it with other herbicides used in wheat weed control. The trial was carried out comparing the following herbicide mixtures: 1) no weed control treatment; 2) Tribenuron Methyl (TM); 3) Clodinafop (C); 4) Tribenuron Methyl + Clodinafop (TM+C); 5) Pinoxaden + clodinafop + propargile (PCP); 6) Pinoxaden + clodinafop + propargile + Triasulfuron (PCP+T); 7) Pinoxaden + clodinafop + propargile + absolute Ioxinil and Mecoprop (PCP+IM). The new PCP+T herbicides mixture didn&rsquo;t differ statistically from the traditional TMC treatment in terms of effectiveness, but the agronomic result of the new mixture was totally satisfactory, even taking into account that the marketing of this mixture is not aimed to compete with other existing herbicides but to widen the chance to rotate active principles in time and space, in order to control the onset of resistance phenomena.

Membrane retention of herbicides from single and multi-solute media: The effect of ionic environment

Results are reported for a systematic study on retention of three selected herbicides, in single solute or multi-solute feed-waters, by three commercial NF/ULPRO membranes, using stirred cells in the dead-end filtration mode. The effect of ionic environment on the retention of herbicides is also examined by controlling sodium and calcium concentration. The results are interpreted on the basis of the characteristic properties of herbicides and membranes used. In general, size exclusion seems to be the dominant mechanism for retention by NF/ULPRO membranes, especially in the case of membranes with a pore size similar to that of herbicide molecules. Tight and thus high-desalting membranes exhibit the best retention performance. On the other hand, the retention efficiency of relatively loose nanofiltration membranes also appears to be significantly influenced by adsorption of herbicides on the membrane. Filtration of feed-waters with more than one herbicide present results in different retentions (usually reduced) compared to those determined in single compound solutions. This is attributed to the competition between the herbicides for adsorption sites, which is directly related to membrane surface properties. Filtration experiments with saline solutions, mimicking real conditions (e.g. surface water), reveal the significant effect of divalent cations on herbicide retention, which, depending on the membrane type, can be either positive or negative. However, the effect of ionic strength, due to monovalent ions (NaCl), on herbicides retention appears to be rather minor.

Weed sustainable managment in agricultral and non-agricultural areas

Sustainable agriculture is a way to assure the availability of natural resources for future generations.Weed management in cultivated and not cultivated areas is part of sustainable agriculture as well, and has to face three important challenges: economical (to increase income and competitiveness of farm sector), social (give rural areas opportunity of economic development and improvement of living conditions), environmental (promote good agricultural practices and preserve habitats, biodiversity and landscape). The first two challenges involve the in-depth study of models, the economic threshold of intervention, the management of herbicide resistance phenomena, the study and development of new herbicide molecules, or even modern formulations, leading to the optimization of treatments with possible reduction of distributed doses per hectare. Environmental issues must be set in the studies to assess and manage the factors leading to phenomena of diffuse or point pollution (i.e. water volumes, soil, etc.). However, a sustainable agriculture production must take into account consumers’ needs and concerns, especially about food health and safety with respect to production methods (traditional, integrated and biological). In this context, the results obtained by the development of more advanced active principles, the spread of public and private Integrated Production Specifications (Disciplinari di Produzione Integrata) and the greater and greater commitment by the institutions in charge of monitoring the agro-pharmaceutical residues in agro-food products, can be set. The SIRFI SIRFI (Societa Italiana per la Ricerca sulla Flora Infestante), thanks to the multi-disciplinarity of the structures supporting it, always takes an active part into innovation especially aimed to the identification of tools implementing farm activity sustainability.

Effects of Relative Humidity on Chloroacetanilide and Dinitroaniline Herbicide Desorption from Agricultural PM2.5 on Quartz Fiber Filters

This study quantified the release of seven relatively polar preemergence herbicides to the gas phase from soil-generated PM2.5-loaded quartz fiber filters (QFFs) and bare QFF as a function of relative humidity (RH). A 48-hour desorption fraction, F48, was defined to evaluate the relative desorption behavior of herbicides from two families, chloroacetanilide (alachlor, butachlor, metolachlor, and propachlor) and dinitroaniline (pendimethalin, prodiamine, and trifluralin) using temperature- (8 degrees C) and humidity- (10-64% RH) controlled air at a flow rate of 4 L/min. With increasing RH, an increase in F48 by a factor of 2-8 was observed for all herbicides, except metolachlor and butachlor, which showed significantly strong sorption to both sorbents. The conjugate carbonyl oxygen and amide nitrogen in the chloroacetanilide structure enables stronger specific interactions with the sorbents, leading to lower desorption compared to the dinitroaniline herbicides. Desorption of chloroacetanilides decreased in the order propachlor > alachlor > metolachlor approximately butachlor, and desorption of dinitroanilines decreased in the order trifluralin > pendimethalin > prodiamine. These orders are consistent with the different substituents in the herbicide molecules for each family and their relative tendencies to coordinate with surface moieties as indicated by electron-donating capacity. Henry's law constant and Abraham's H-acceptor parameter were found to be useful empirical parameters for describing the F48 desorption behavior for all seven herbicides.

Study of poly(o-Ethoxyaniline) interactions with herbicides and evaluation of conductive polymer potential used in electrochemical sensors

Interactions of four aromatic nitrogen-heterocyclic herbicides (atrazine, imazaquin, metribuzin and paraquat) with the conductive polymer poly(o-ethoxyaniline)-POEA, were studied with atomic force microscopy (AFM), UV-visible spectrophotometry (UV-Vis) and electrochemical impedance spectroscopy. AFM profiles of self-assembled (SA) films of POEA revealed that the polymer surface became rougher (on the nanoscale) when exposed to atrazine, imazaquin and metribuzin, but slightly smoother in contact with paraquat. This suggested that specific chemical interactions, possibly electroscopic, have occurred between nitrogen atoms in the polymer chain and the dissimilar groups in the various herbicide molecules, during adsorption of the latter onto the film. The UV-Vis analyses indicated a stronger interaction of POEA in solution with imazaquin, that has a special importance for the intended application. Sensors produced by coating microelectrodes with SA films of POEA were used to perform impedance spectroscopy in aqueous solutions of each herbicide. With the resulting data, it was possible to distinguish and set detection limits for each herbicide in water, corroborating AFM and UV-Vis results.

Plasmodesmos: transporte simplástico de herbicidas na planta

Plasmodesmos são canais responsáveis pela conexão citoplasmática entre células vizinhas, possibilitando a troca de moléculas de informação, funcionais, estruturais ou ainda de xenobióticos entre as células pertencentes a um mesmo grupo. Células pertencentes ao mesmo conjunto (domínio) constituem-se numa unidade funcional, e substâncias podem se mover entre estas células com velocidade muito superior à observada no transporte através de membranas. Os plasmodesmos podem atuar ainda no transporte a longa distância, tanto pela associação com o floema como pelo intercâmbio entre domínios simplásticos. Quando a planta se encontra sob estresse e as taxas de transporte via xilema e floema são mais reduzidas, os plasmodesmos podem ser mais efetivos no transporte a longa distância, das moléculas de herbicidas sistêmicos. Falta ainda esclarecer se existe afinidade entre moléculas de determinados herbicidas com as proteínas da superfície interna dos plasmodesmos, o que poderia facilitar o transporte desses herbicidas pela manipulação do Tamanho Limite de Exclusão do plasmodesmo, independentemente do tamanho da molécula, bem como determinar se a semelhança com algum composto natural da planta promove maior taxa de transporte simplástico. Pouca importância tem sido dada à participação dos plasmodesmos no transporte de herbicidas sistêmicos. No entanto, o avanço dos trabalhos com produtos marcados e a intensificação das pesquisas em fisiologia vegetal para melhor entendimento dos processos referentes à absorção, translocação, conjugação e/ou degradação de herbicidas podem esclarecer muitos aspectos ainda não definidos do transporte de herbicidas via xilema e floema e sua associação com o apoplasto e domínios simplásticos.

Effect of Surface Chemistry, Solution pH, and Ionic Strength on the Removal of Herbicides Diuron and Amitrole from Water by an Activated Carbon Fiber

A study was conducted on the effects of carbon surface chemistry, solution pH, and ionic strength on the removal of diuron and amitrole from aqueous solutions by adsorption on an as-received and oxidized activated carbon fiber. Results obtained were explained by the surface characteristics of the adsorbents and the characteristics of the herbicide molecules. Under the experimental conditions used, diuron uptake was much higher than that of amitrole, despite its larger molecular dimensions, due to the lesser water solubility, greater hydrophobicity, and larger dipolar moment of diuron compared with amitrole. Uptake variations associated with differences in carbon surface oxidation, solution pH, and ionic strength were explained by corresponding changes in electrostatic, hydrophobic, and van der Waals interactions.

Enantioselective aptameric molecular recognition material: Design of a novel chiral stationary phase for enantioseparation of a series of chiral herbicides by capillary electrochromatography

A chiral stationary phase derived from an L-RNA aptamer is evaluated for the enantiomer separation of a series of herbicide molecules (aryloxypropionic, aryloxyphenoxypropionic, and aminopropionic acid) by CEC after binding to biotin and grafting upon streptavidin-modified porous glass beads. We demonstrated that the aptamer capillary was stable in term of efficiency and retention during a long period. The influences of the mobile phase constitution and its flow-velocity on the enantioseparation were also investigated. The results suggest that the interactions of the enantiomer during CEC are solely based on chromatographic mechanisms and that the electrophoresis plays only a minor role. The separation efficiency and peak shape could be improved by Mg2+ divalent cation that stabilized the aptamer secondary structure and thus enhanced the mass transfer kinetics during the ligand-aptamer binding process. In addition, it was demonstrated that the determination of the enantiomerization barrier of flamprop was possible using this chiral stationary phase.

Detection and analysis of nitrogen‐containing pesticides in environment by surface‐ionization methods

AbstractThe results of a study of the possibilities of surface‐ionization mass spectrometry (SI/MS) and atmospheric‐pressure thermodesorption surface‐ionization spectroscopy (APTDSIS) for high‐sensitivity and selective detection and identification of nitrogen‐containing pesticides are presented for some trisubstituted 1,3,5‐triazines (prometryne, atrazine) and aromatic amines (trifluralin). An oxidized W band in vacuum (SI/MS) and oxidized Mo crystals doped with Ir in air (APTDSIS) were used as ion emitters. The SI mass spectra of pesticides have a small number of lines and consist of the ion lines (M + H)+, M+, (M − H)+ and (M − R)+, being the products of chemical reactions in the adlayer (M is the molecule; H is the hydrogen atom; R is the radical). The herbicide molecules are ionized by SI with high efficiency. The APTDSIS spectra of pesticides have two characteristic maxima connected with energy of sublimation and desorption. The SI efficiency increases in the order 2.5, 35 and 72 C/mol for trifluralin, atrazine, prometryne, respectively, and is within the linear range of the concentration dependence of 2–4 orders of magnitude. The results obtained by the SI/MS and APTDSIS methods have been compared with those obtained by GC/MS with electron ionization. Copyright © 2006 John Wiley &amp; Sons, Ltd.

Effect of ionic strength and pH on the adsorption of selected herbicides on Amberlite

The effect of ionic strength on the adsorption of alachlor, trifluralin, and prometryn on Amberlite XAD-4 polymeric resin is studied. Static adsorption experiments are carried out at pH 3–6.5 and ionic strength 0.01–2 M at 20°C. By increasing the ionic strength, the adsorption of herbicides can be significantly increased. The electrolyte addition affects both the effectiveness and efficiency of adsorption, leading eventually to a saturation of the resin surface. An explanation of the alteration of adsorption mechanisms, caused by ionic strength, is given, based mainly on the reduction in repulsive forces at the resin–herbicide interface and between adsorbing herbicide molecules, since both resin and herbicides have a polar ring as part of their structure.

Biotechnology approaches to developing herbicide tolerance/selectivity in crops

The use of herbicides has revolutionized weed control in many crop production systems. However, with the increasing development of weed resistances to many popular selective herbicides, the need has arisen to rethink the application of chemical weed control. Approaches to maintain the efficiency of chemical weed control include the discovery of new herbicide target sites in plants and the discovery/ synthesis of new, more potent herbicidal molecules. However, these approaches are expensive to execute, take considerably long times to succeed and may lead to increased chemical loads in the environment. Since many existing broad-spectrum herbicides are still effective, an alternative strategy adopted to ensure the safe use of broad-spectrum herbicides in a wide range of crops is the application of biotechnological techniques to engineer crop selectivity to these herbicides. In this review we summarize efforts being made to develop crop herbicide selectivity using biotechnology. Keywords: Biotechnology, herbicide resistance, cell culture, mutagenesis, genetic transformation

Biotechnology approaches to developing herbicide tolerance/selectivity in crops

The use of herbicides has revolutionized weed control in many crop production systems. However, with the increasing development of weed resistances to many popular selective herbicides, the need has arisen to rethink the application of chemical weed control. Approaches to maintain the efficiency of chemical weed control include the discovery of new herbicide target sites in plants and the discovery/ synthesis of new, more potent herbicidal molecules. However, these approaches are expensive to execute, take considerably long times to succeed and may lead to increased chemical loads in the environment. Since many existing broad-spectrum herbicides are still effective, an alternative strategy adopted to ensure the safe use of broad-spectrum herbicides in a wide range of crops is the application of biotechnological techniques to engineer crop selectivity to these herbicides. In this review we summarize efforts being made to develop crop herbicide selectivity using biotechnology. Keywords: Biotechnology, herbicide resistance, cell culture, mutagenesis, genetic transformation

Combining Trichoderma virens-inoculated compost and a rye cover crop for weed control in transplanted vegetables

A number of techniques exist that have potential to be integrated into low-external-input weed management systems but it is not the norm for these different techniques to be investigated in combination. Here, we evaluate the weed management potential of two cultural weed management techniques, cover cropping and fertility management, with two allelochemical-releasing organisms compared to herbicides. Trichoderma virens (= Gliocladium virens ), which releases the herbicidal molecule viridiol, is applied incorporated in composted chicken manure (CCM), and rye, which is known to release the herbicidal molecules (3 H )-benzoxazolinone (BOA) and 2,4-dihydroxy-1,4-(2 H )benzoxazine-3-one (DIBOA), is used as the cover crop. Both T. virens -inoculated CCM and rye cover crops provided significant weed control in some experiments without a significant loss of crop vigor and yield. Yield was comparable to those obtained with chemical herbicides, although the results were not consistent. Clear weed suppressive activity exists with these nonherbicidal treatments, and effective weed management in transplanted vegetables seems feasible with these approaches. However, further refinements in these treatments is needed to ensure reliable performance prior to grower acceptance.

Germ line genetic transformation in cotton ( Gossypium hirsutum L.) by selection of transgenic meristematic cells with a herbicide molecule

Imazapyr is a herbicide molecule that when applied, concentrates in the apical meristematic region of plants. It inhibits the activity of acetohydroxyacid synthase, the enzyme that catalyzes the initial step in biosynthesis of isoleucine, leucine and valine. Previously isolated from Arabidopsis thaliana, the selectable marker gene, ahas, contains a mutation at position 653. Using a combination of imazapyr, the ahas gene, and a multiple shoot induction protocol, we have developed a novel system to select transgenic cotton meristematic cells after the physical introduction of foreign genes. In the present study, we describe the protocol for obtaining germ line transformation of Brazilian cotton varieties (var. 7MH: 0.49%; var. Antares: 0.62%; var. CD-401: 0.71% and var. ITA94: 0.47%).

Sorption–desorption behavior of triazine and phenylurea herbicides in Kishon river sediments

Sorption and desorption hysteresis of widely applied triazine and phenylurea herbicides were studied for river sediments. Organic carbon normalized sorption coefficient (K(OC)) values for all herbicides were significantly higher for the sediment from the downstream region of the river vs. the upstream sediment. On the basis of the measured K(OC) values, the triazine herbicides can be arranged in the following order: terbutryn > terbuthylazine > ametryn > atrazine. Among the phenylurea herbicides, chlorotoluron exhibited higher sorption than isoproturon (K(OC) values of 137 vs. 60 and 228 vs. 125 L/kg for the upstream and downstream sediments, respectively). Moreover, chlorotoluron exhibited lower desorption potential as compared with isoproturon (apparent hysteresis index values were 0.2-0.3 for chlorotoluron vs. 0.6-0.9 for isoproturon, measured with the upstream sediment). High sorption affinity of chlorotoluron to the sediments is probably due to stronger H-bonding interactions of the herbicide molecules with the sorbents. For both phenylurea herbicides, desorption hysteresis increased with decrease in sorbed amount. This behavior was opposite to the hysteresis trend observed for the triazines. The Cl-triazines (atrazine and terbuthylazine) exhibited higher desorption hysteresis than the S-triazines (ametryn and terbutryn). Therefore, the apparent hysteresis index values calculated for the Cl-triazines were lower than the values of S-triazines (about 0.4 and 0.7, respectively). Based on the relative strength of H-bonding interactions of Cl- and S-triazines with formate anion and on the desorption hysteresis data we suggest a gradient-derived hole-filling sorption mechanism for the triazine herbicides with the river sediments.