Abiotic degradation (photodegradation and hydrolysis) of imidazolinone herbicides

The abiotic degradation of the imidazolinone herbicides imazapyr, imazethapyr and imazaquin was investigated under controlled conditions. Hydrolysis, where it occurred, and photodegradation both followed first-order kinetics for all herbicides. There was no hydrolysis of any of the herbicides in buffer solutions at pH 3 or pH 7; however, slow hydrolysis occurred at pH 9. Estimated half-lives for the three herbicides in solution in the dark were 6.5, 9.2 and 9.6 months for imazaquin, imazethapyr and imazapyr, respectively. Degradation of the herbicides in the light was considerably more rapid than in the dark with half lives for the three herbicides of 1.8, 9.8 and 9.1 days for imazaquin, imazethapyr and imazapyr, respectively. The presence of humic acids in the solution reduced the rate of photodegradation for all three herbicides, with higher concentrations of humic acids generally having greater effect. Photodegradation of imazethapyr was the least sensitive to humic acids. The enantioselectivity of photodegradation was investigated using imazaquin, with photodegradation occurring at the same rate for both enantiomers. Abiotic degradation of imidazolinone herbicides on the soil surface only occurred in the presence of light. The rate of degradation for all herbicides was slower than in solution, with half-lives of 15.3, 24.6 and 30.9 days for imazaquin, imazethapyr and imazapyr, respectively. Abiotic degradation of these herbicides is likely to be slow in the environment and is only likely to occur in clear water or on the soil surface.     

Abiotic degradation (photodegradation and hydrolysis) of imidazolinone herbicides

The abiotic degradation of the imidazolinone herbicides imazapyr, imazethapyr and imazaquin was investigated under controlled conditions. Hydrolysis, where it occurred, and photodegradation both followed first-order kinetics for all herbicides. There was no hydrolysis of any of the herbicides in buffer solutions at pH 3 or pH 7; however, slow hydrolysis occurred at pH 9. Estimated half-lives for the three herbicides in solution in the dark were 6.5, 9.2 and 9.6 months for imazaquin, imazethapyr and imazapyr, respectively. Degradation of the herbicides in the light was considerably more rapid than in the dark with half lives for the three herbicides of 1.8, 9.8 and 9.1 days for imazaquin, imazethapyr and imazapyr, respectively. The presence of humic acids in the solution reduced the rate of photodegradation for all three herbicides, with higher concentrations of humic acids generally having greater effect. Photodegradation of imazethapyr was the least sensitive to humic acids. The enantioselectivity of photodegradation was investigated using imazaquin, with photodegradation occurring at the same rate for both enantiomers. Abiotic degradation of imidazolinone herbicides on the soil surface only occurred in the presence of light. The rate of degradation for all herbicides was slower than in solution, with half-lives of 15.3, 24.6 and 30.9 days for imazaquin, imazethapyr and imazapyr, respectively. Abiotic degradation of these herbicides is likely to be slow in the environment and is only likely to occur in clear water or on the soil surface.     

Sorption of ametryn and imazethapyr in twenty-five soils from Pakistan and Australia.

Sorption of ametryn and imazethapyr in 25 soils from Pakistan and Australia was investigated using the batch method. The soils varied widely in their intrinsic capacities to sorb these herbicides as shown by the sorption coefficients, Kd, which ranged from 0.59 to 47.6 for ametryn and 0.02 to 6.94 for imazethapyr. Generally the alkaline soils of Pakistan had much lower Kd values of both herbicides than the soils of Australia. Both soil pH and soil organic carbon (SOC) were correlated significantly with the sorption of ametryn, whereas only soil pH was strongly correlated with imazethapyr sorption. No correlation was found between Kd values of the herbicides and the clay contents of the soils. Multiple regression analysis showed that Kd values were better correlated (r2=0.94 and 0.89 for ametryn and imazethapyr, respectively) if SOC and pH were simultaneously taken into account. The study indicated that sorption of these herbicides in the alkaline soils of Pakistan was low and consequently there is considerable risk of groundwater contamination.     

Resistance to metal contamination by historically-stressed populations of Ceriodaphnia pulchella: environmental influence versus genetic determination

Field populations of daphnids historically-stressed by metal contamination may show increased resistance to those contaminants. This study was undertaken aiming to confirm/infirm three main hypotheses: (1) field populations living in historically-impacted environments are more tolerant to metal stress than populations from reference sites; (2) resistance differences are genetically-determined, i.e., differences persist after controlling for environmental and maternal effects, by acclimating cloned lineages to similar conditions; and (3) resistance to stress in field populations living in historically-impacted environments is due to the disappearance of sensitive individuals rather than the appearance of highly resistant ones, i.e., the shift in the central tendency of resistance is linked to a decrease in the range of population resistance and not to an increased upper limit of the population resistance. Three populations of the cladoceran Ceriodaphnia pulchella Sars in Southern Portugal were sampled; one of which has been historically-stressed by acid mine drainage (AMD) from an abandoned cupric-pyrite mine and two from reference sites within the same watershed. To assess if resistance differences were genetically-determined, the three populations were acclimated for at least five generations under the same controlled conditions. Assays with AMD contaminated water samples were performed with both non-acclimated and acclimated individuals from all studied populations. Reproduction results in sub-lethal assays revealed significant differences between the reference and stressed populations. Significant differences in resistance to lethal levels of toxicity were observed for both non-acclimated and acclimated populations, individuals from population I being more resistant than those from reference populations. The existence of genetically-determined sensitivity differences was attested by the presence of significant differences in resistance to lethal levels of toxicity in acclimated individuals from reference and stressed populations. Results from cumulative mortality assays revealed that sensitive individuals were most probably present in the original population, but no conclusion could be draw about the presence of extreme resistant individuals in the historically-stressed population. Finally, it was shown that responses among populations converged from high to low levels of contamination.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine approximately amitrole approximately simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K(ow)) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine～ amitrole～ simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K_ow) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.     

Effect of some herbicides on activities of microorganisms and enzymes in soil

Abstract

Laboratory tests were conducted with eight herbicides, atrazine, butylate, ethalfluralin, imazethapyr, linuron, metolachlor, metribuzin and trifluralin, applied to a loamy sand at rate of 10 μg/g to determine if these materials caused any serious effects on microbial and enzymatic activities related to soil fertility. Some herbicides showed an effect on bacteria and fungi for the first week of incubation, but, subsequently, the populations returned to levels similar to those obtained in the controls. After several herbicide treatments there appeared to cause a slight depression of nitrification. Sulfur oxidation was better than that obtained with untreated soil in all treatments. Oxygen consumption was increased significantly after 96 hr incubation with atrazine. The soil dehydrogenase and amylase activities were inhibited by ethalfluralin treatment respectively for 1 wk and 1 day, and p‐nitrophenol liberation was inhibited for 2 hrs by all herbicide treatments. Results indicated that the herbicidal treatments at the level tested were not drastic enough to be considered deleterious to soil microbial and enzymatic activities which are important to soil fertility.     

Hemocyte-specific responses to the peroxidizing herbicide fomesafen in the pond snail Lymnaea stagnalis (Gastropoda, Pulmonata)

Responses of circulating hemocytes were studied in Lymnaea stagnalis exposed to 10, 30, 90, and 270 microg/L fomesafen for 24 and 504 h. Flow cytometry was used to quantify fomesafen-induced production of reactive oxygen species (ROS), phagocytic activity on Escherichia coli, and oxidative burst when hemocytes were challenged by E. coli or phorbol 12-myristate-13-acetate (PMA). Lysosomal membrane damage was assessed, using the neutral-red retention time (NRRT) assay. Exposure to fomesafen for 24 h resulted in increase in ROS levels and decreases in phagocytosis and the oxidative burst in PMA-stimulated hemocytes. After 504 h, intracellular levels of ROS returned to normal, but phagocytosis of E. coli was still inhibited and the associated oxidative burst significantly reduced. After both durations of exposure, decreases of NRRT indicated that lysosome membrane fragility increased with fomesafen concentration. Potential implications for the health and survival of the snails and consequences on populations are discussed.     

Alternative herbicides to manage Italian ryegrass (Lolium multiflorum lam) resistant to glyphosate at different phenological stages

During the growing season of 2002--2003, field and greenhouse experiments were conducted with the objective of evaluating the influence of Italian ryegrass phenological stages and management alternatives on the control of resistant biotypes to glyphosate. Three field experiments were conducted in Lagoa Vermelha, RS, Brazil and glyphosate was applied alone and in combinations with alternative herbicides. Two greenhouse experiments were also conducted at the Department of Crop Science, ESALQ/USP, Piracicaba, SP, Brazil. The Italian ryegrass resistant population was collected from Lagoa Vermelha, RS, Brazil. From the results it was possible to conclude that: (i) the more advanced the phenological stage of application, the more difficult the control of resistant Italian ryegrass by glyphosate, mainly by the rate of 960 g a.i. ha(-1); however, this rate applied at earlier phenological stage (five tillers), the control was higher than 90%; (ii) with the increment of glyphosate rate, it significant response was observed on the control at all stages of application; (iii) the mixture of glyphosate + clethodim (1440 + 72 g a.i. ha(-1)), paraquat + diuron (500 + 250 g a.i. ha(-1)), at all stages of application and clethodim (96 g a.i. ha(-1)) and paraquat + diuron (300 + 150 g a.i. ha(-1)) at the initial stages until pre-flowering were excellent alternatives for management of these populations; and (iv) the response of control was much faster for the mixture of glyphosate + clethodim, independently of growth stage.     

Oxidative stress and lipid peroxidation in the earthworm Eisenia fetida induced by low doses of fomesafen

Formesafen is a diphenyl ether herbicide that has adverse effects on non-target animals. However, knowledge about the effect of fomesafen on the antioxidant defense system in earthworms is vague. Thus, it is essential to investigate the effects of fomesafen on the antioxidant defense system in earthworms as a precautionary method. In the present study, earthworms (Eisenia fetida) were exposed to artificial soil treated with a range of concentrations of fomesafen (0, 10, 100, and 500 μg kg^?1) and were collected on the 3rd, 7th, 14th, 21st, and 28th days of exposure. Subsequently, the antioxidant enzyme activities (superoxide dismutase (SOD); catalase (CAT); and guaiacol peroxidase (POD)), reactive oxygen species (ROS) level, and malondialdehyde (MDA) content due to fomesafen treatment were examined in earthworms. Compared with the control, the SOD activity increased on the third and seventh days but decreased on the 14th day due to treatment with 100 and 500 μg kg^?1 of fomesafen. The activities of CAT and POD increased significantly on the third, seventh, and 14th days of exposure. In addition, the ROS level was significantly enhanced throughout the entire experimental period and showed a statistically dose-dependent relationship on the seventh and 14th days. The MDA content markedly increased on the seventh day of exposure; however, obvious changes were not detected at other exposure period. Low doses of fomesafen (≤500 μg kg^?1) may result in oxidative damage and lipid peroxidation in E. fetida by inducing the generation of ROS at short exposure periods (14 days). However, the adverse effects of fomesafen gradually disappear as the cooperation of antioxidant enzymes and exposure time are prolonged. This result may be helpful for further studies on the toxicological mechanisms of fomesafen to earthworms.     

Herbicide safeners: uses,limitations, metabolism,and mechanisms of action

Several methods were examined to minimize crops injury caused by herbicides. Thus increase their selectivity. A selective herbicide is one that controls weeds at rates that do not injure the crop. Herbicides are selective in a particular crop within certain limits imposed by the herbicide, the plant, the application rate, the method and time of application, and environment conditions. Herbicide safeners are compounds of diverse chemical families. They are applied with herbicides to protect crops against their injury. Using chemical safeners offer practical, efficient and simple method of improving herbicide selectivity. This method has been applied successfully in cereal crops such as maize, rice and sorghum, against pre-emergence thiocarbamate and chloroacetanilide herbicides. Some reports indicate promising results for the development of safeners for post-emergence herbicides in broadleaved crops. Various hypotheses were proposed explaining mechanisms of action of herbicide safeners: interference with uptake and translocation of the herbicide, alteration in herbicide metabolism, and competition at site of action of the herbicide. Even though progress was made in the development of herbicide safeners and in understanding their mechanisms of action, more research is needed to elucidate clearly how these chemicals act and why their activity is restricted to particular crops and herbicides.     

Herbicide application timing in preharvest desiccation of soybean cultivars with different growth habits

In order to evaluate the ideal time of herbicide applications to desiccate soybean cultivars with determinate and indeterminate growth habits in preharvest, an experiment was carried out at the University of Ponta Grossa (PR), during 2002--2003. The experimental design used was a randomized blocks arranged in a factorial scheme 4 x 5 (herbicides and time of application), with three replications, using four soybean cultivars: Spring, V-Max, BR-16, and BRS-133. The herbicides glufosinate, diquat, and paraquat were used at the rate of 400 g ha(-1), when soybean was at stage of R6.0, R6.5, R7.0, R7.5, and R8.0. The assessments included yield, as well as yield components, considering each cultivar separately. The results show that desiccation should be done on cultivars with determinate growth habit at stages between R7.0 and R7.5, independent of herbicide used. For indeterminate growth habit cultivars, desiccation should be done later, because those pods formed after R6.5 stage are important to define yield; although herbicides have different mode of action, yield results were similar. In cultivars, desiccation should start when all pods in the middle of plants become yellow and grains are not held by fibers.     

MSMA resistance studies

Monosodium methanearsonate (MSMA)-resistant and -susceptible common cocklebur (Xanthium strumarium L.) and cotton (Gossypium hirsutum L.) were treated with MSMA. Plant parameters analyzed were: glutathione synthetase activity, selected amino acid (arginine, glutamic acid, alanine, citrulline, glutamine, and glutathione) content and arsenic content (MSMA, total arsenic, and arsonate). No reduction of arsenic from the parent pentavalent form present in MSMA to the trivalent form was detected. Arginine, glutamic acid, and glutamine content increased in tissue three days after MSMA treatment. Glutathione content decreased during the first three days after treatment; however, five days after treatment the resistant biotype of cocklebur and cotton had elevated glutathione levels (8-20 times greater, respectively). Glutathione Synthetase activity was higher in cotton than in either of the cocklebur biotypes; MSMA did not affect its activity in cotton or either cocklebur biotype. Resistant biotypes have a slightly higher activity than the susceptible biotype. Tolerance of cotton to MSMA may be related to glutathione synthetase activity and possibly to the presence of phytochelatins. Also, increased glutathione levels in the resistant biotype may implicate phytochelatin involvement in the resistance mechanism.     

Effects of spraying the herbicides 2,4-D and 2,4,5-T on a population of the tortoise Testudo hermanni in southern Greece

A population of the tortoise Testudo hermanni near Olympia in southern Greece was studied by mark-recapture from 1975 to 1984. Part of the site was sprayed with the herbicides 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) each year from 1980, producing symptoms of poisoning (swollen eyes, fluid discharge from the nose and immobility) in tortoises. Survival rates of tortoises 10 cm or larger were significantly lower in the affected areas, with extra mortality of about 34% year-1, against an annual survival rate of 0.85-0.90 in unaffected areas. Changing population structures showed that juveniles were even more strongly affected, with the proportion of juveniles in samples decreased by half. The population in the sprayed area declined to near zero by 1984, due to mortality rather than to emigration, since more movements were recorded into than out of the affected area. There was no difference in body mass condition between sprayed and unsprayed areas, showing that effects were acute; mortality was not due to starvation from loss of food plants. The scale and pattern of mortality was similar to that from a severe scrub fire; spraying is potentially more catastrophic since often repeated at shorter intervals than burning. Possible physiological mechanisms of death are discussed. The susceptibility of tortoises to 2,4-D and 2,4,5-T (or to associated dioxin impurities) presents a warning for conservation of these late-maturing animals.     

Adsorption of imidazolinone herbicides on ferrihydrite-humic acid associations.

Adsorption of the imidazolinone herbicides imazapyr, imazethapyr and imazaquin was studied on two binary systems (ferrihydrite-humic acid) prepared by treating ferrihydrite (Fh) immediately after its precipitation with a soil humic acid (HA) at different loadings (4% and 8% HA content), and on a blank ferrihydrite sample prepared in the same way, but without HA addition. Imidazolinone adsorption on pure Fh and on the 4% Fh-HA decreased with increasing of the herbicide hydrophobicity (imazaquin相似文献   

MSMA Resistance Studies

Abstract

Monosodium methanearsonate (MSMA)-resistant and -susceptible common cocklebur (Xanthium strumarium L.) and cotton (Gossypium hirsutum L.) were treated with MSMA. Plant parameters analyzed were: glutathione synthetase activity, selected amino acid (arginine, glutamic acid, alanine, citrulline, glutamine, and glutathione) content and arsenic content (MSMA, total arsenic, and arsonate). No reduction of arsenic from the parent pentavalent form present in MSMA to the trivalent form was detected. Arginine, glutamic acid, and glutamine content increased in tissue three days after MSMA treatment. Glutathione content decreased during the first three days after treatment; however, five days after treatment the resistant biotype of cocklebur and cotton had elevated glutathione levels (8–20 times greater, respectively). Glutathione Synthetase activity was higher in cotton than in either of the cocklebur biotypes; MSMA did not affect its activity in cotton or either cocklebur biotype. Resistant biotypes have a slightly higher activity than the susceptible biotype. Tolerance of cotton to MSMA may be related to glutathione synthetase activity and possibly to the presence of phytochelatins. Also, increased glutathione levels in the resistant biotype may implicate phytochelatin involvement in the resistance mechanism.     

Herbicide residues in grapes and wine

The persistence of several common herbicides from grapes to wine has been studied. Shiraz, Tarrango and Doradillo grapes were separately sprayed with either norflurazon, oxyfluorfen, oxadiazon or trifluralin-persistent herbicides commonly used for weed control in vineyards. The dissipation of the herbicides from the grapes was followed for 28 days following treatment. Results showed that norflurazon was the most persist herbicide although there were detectable residues of all the herbicides on both red and white grapes at the end of the study period. The penetration of herbicides into the flesh of the grapes was found to be significantly greater for white grapes than for red grapes. Small-lot winemaking experiments showed that norflurazon persisted at levels close to the initial concentration through vinification and into the finished wine. The other herbicides degraded, essentially via first-order kinetics, within the period of "first fermentation" and had largely disappeared after 28 days. The use of charcoal together with filter pads, or with diatomaceous earth was shown to be very effective in removing herbicide residues from the wine. A 5% charcoal filter removed more than 96% of the norflurazon persisting in the treated wine.     

Herbicide residues in grapes and wine

Abstract

The persistence of several common herbicides from grapes to wine has been studied. Shiraz, Tarrango and Doradillo grapes were separately sprayed with either norflurazon, oxyfluorfen, oxadiazon or trifluralin ‐ persistent herbicides commonly used for weed control in vineyards. The dissipation of the herbicides from the grapes was followed for 28 days following treatment. Results showed that norflurazon was the most persist herbicide although there were detectable residues of all the herbicides on both red and white grapes at the end of the study period. The penetration of herbicides into the flesh of the grapes was found to be significantly greater for white grapes than for red grapes. Small‐lot winemaking experiments showed that norflurazon persisted at levels close to the initial concentration through vinification and into the finished wine. The other herbicides degraded, essentially via first‐order kinetics, within the period of “ first fermentation”; and had largely disappeared after 28 days. The use of charcoal together with filter pads, or with diatomaceous earth was shown to be very effective in removing herbicide residues from the wine. A 5% charcoal filter removed more than 96% of the norflurazon persisting in the treated wine.