Safening activity of natural hydroxamic acids and analogous compounds against herbicide injury to maize

Abstract

Safening activities of natural compounds DIMBOA, DIBOA, and MBOA, as well as synthetic 1,4‐benzoxazin‐3‐ones were tested against acetochlor and EPTC injuries to maize. No safening activities of natural products and from low to moderate activity of synthetic benzoxazinones were observed. In order to explain inefficacy of natural compounds we studied the influence of these molecules on enzymes participating in metabolic detoxication of acetochlor and EPTC. Pretreatment with DIMBOA elevated maize cytochrome P450 levels. Pretreatments with chemicals containing 1,4‐benzoxazin‐3‐one backbone did not alter glutathione S‐transferase enzyme activities. However, all natural products inhibited glutathione S‐transferase activity of roots and shoots in vitro after addition to the enzyme. Safening ineffectiveness of natural hydroxamic acids may be explained by their inhibitory effects on GST enzymes due to their reaction with sulfhydryl groups on the enzyme.     

Liver glutathione content and glutathione‐dependent enzymes of two species of freshwater fish as bioindicators of chemical pollution

Abstract

Glutathione content and glutahione‐dependent enzymes were measured in the liver of two fish species, gudgeon (Gobio gobio) and roach (Rutilus arcasii), from the river Bernesga (Spain) caught downstream and upstream of the waste site of several chemical industries. Animals from contaminated sites display a reduced glutathione concentration and a tendency to the decrease of glutathione S‐transferase activity. Glutathione peroxidase activity was significantly elevated only in the liver of Gobio gobio and glutathione reductase activity in that of Rutilus arcasii. Our data indicate that the glutathione system constitutes a sensitive biochemical indicator of chemical pollution. Relative changes of glutathione and glutathione‐dependent enzymes in both fish species suggest a different susceptibility to toxins.     

1‐Aminobenzotriazole increases glutathione‐s‐transferase activity of maize

Abstract

Glutathione‐S‐transferase (GST) activity of maize (Zea mays L.) seedlings treated with 1‐aminobenzotriazole (ABT) derivatives and/or EPTC were measured using EPTC‐sulfoxide as substrate. Both safeners and ABT derivatives significantly elevated the GST activity in the concentrations needed for effective safening action. ABT is considered as an inhibitor of plant cytochrome P‐450 monooxygenases (P‐450) and, because of this, used to study herbicide mode of action. Our data indicate that ABT has multiple effects on plants influencing not only P‐450 but GST as well. Thus the role of ABT in herbicide metabolism needs reconsideration.     

Genotypic Differences in Effects of Cadmium Exposure on Plant Growth and Contents of Cadmium and Elements in 14 Cultivars of Bai Cai

Abstract

Fourteen cultivars of bai cai (Brassica campestris L. ssp. chinensis var. communis) were grown in the nutrient solutions containing 0–0.5 μg mL^?1 of cadmium (Cd) to investigate genotypic differences in the effects of Cd exposure on the plant growth and uptake and distribution of Cd in bai cai plants. The Cd exposure significantly reduced the dry and fresh weights of roots and shoots, the dry weight ratio of shoot/root (S/R), total biomass, and chlorophyll content (SPAD value). Cd concentrations in bai cai ranged from 13.3 to 74.9 μg g^?1 DW in shoots and from 163.1 to 574.7 μg g^?1 DW in roots under Cd exposure, respectively. The considerable genotypic differences of Cd concentrations and accumulations in both shoots and roots were observed among 14 bai cai cultivars. Moreover, Cd mainly accumulated in the roots. Cd also caused the changes of uptake and distribution of nutrients in bai cai and under the influence of cadmium, the concentration of potassium (K) decreased in shoot and increased in root. However, the concentrations of magnesium (Mg), phosphorus (P), manganese (Mn), boron (B), and iron (Fe) increased in shoots and decreased in roots. In addition, Cd exposure resulted in an increase in calcium (Ca), sulphur (S), and zinc (Zn) concentrations in both shoots and roots but had no significant effects on the whole uptake of the examined mineral nutrients except for S.     

Effect of adjuvants on rainfastness and herbicidal activity of glyphosate deposits on trembling aspen foliage

Abstract

Radiolabelled end‐use mixtures of glyphosate with and without a cationic surfactant (Ethomeen® T/25) and an organosilicone surfactant (Silwet® L‐77) were applied onto trembling aspen (Populus tremuloids Michx.) leaves at the rate of 1.0 kg of AE (acid equivalent) in 35 L/ha area of foliage. A 5‐mm rainfall with an intensity of 10 mm/h was applied at intervals of 0.5, 8, 24, 36, 48, 72, and 96 h after treatment. Glyphosate washoff was determined by liquid scintillation counting of radioactivity in the rain‐washing. At 36 h post‐treatment, both the adjuvants significantly reduced glyphosate washoff (Ethomeen by 69.6% and Silwet by 59.7%) from foliage, compared to the washoff (82.6%) when Vision alone was applied without the adjuvants. Results on the rate of plant growth indicated that with a rain‐free period of 8 h or more, the growth of most seedlings was stunted within 1 or 2 d. Percentage of foliar browning 20 d after treatment with rain‐free period of 8 to 48 h ranged from 8 to 80% for Vision alone, 75 to 100% for Vision with Ethomeen, and 85 to 100% for Vision with Silwet, respectively. Physical properties of the end‐use mixtures were measured with and without the two adjuvants to examine droplet spreading and drying rates in relation glyphosate rainfastness. The Silwet adjuvant lowered the surface tension of the end‐use mixture, but Ethomeen did not. Droplets containing Silwet were spread more than those containing Ethomeen. However, the greater area of contact caused by Silwet did not contribute to a significant increase in the translocation rate of glyphosate into untreated parts of the seedlings, and showed no relationship with rainfastness of glyphosate deposits on trembling aspen.     

A fluorometric method to determine rainfastness,volatilization and photostability of glyphosate from glass slides,after application of vision® with two adjuvants

Abstract

A fluorometric method was developed to quantify glyphosate loss from glass surfaces after exposure to the natural forest environment. The method was based on the principle of converting glyphosate into glycine, followed by the fluorogenic labeling with o‐phthalaldehyde. A fluorometer (with λ _Ex = 360 nm / λ_Em =430 nm) was used to quantify the derivatized fluorogenic compound. Response was linear over the concentration range of 143, 286, 572, 858 and 1144 μg of glyphosate (acid equivalent, AE) per mL of the diluted Vision® formulation. Three end‐use mixtures of Vision® were prepared, each at a concentration of 28.6 g AE/L, without and with two adjuvants, Ethomeen® T/25 at 4.5 mL/L and Silwet^® L‐77 at 1.5 mL/L. Several dilutions of the end‐use mixtures were applied on glass slides without and with the coating of cuticular wax extracted from trembling aspen foliage. The slides were left for 5 days in a forest opening to determine rainfastness, volatilization and photostability of glyphosate. The residues were quantified using the method developed. Three calibration curves were required because Silwet decreased the fluorometric response of glyphosate, whereas Ethomeen increased it. The minimum detection limit was 143 μg of glyphosate/mL. Glyphosate was resistant to volatilization and sunlight‐mediated degradation, regardless of the presence of wax coating or the adjuvants. About 64% of the applied glyphosate was washed off after a 9.6 mm rainfall when no adjuvant was present. Both adjuvants provided some amount of rain‐protection to glyphosate, but Silwet reduced the washoff to a greater extent (46%) than Ethomeen (55%).     

Evaluation of genotoxicity and coumarin production in conventional and organic cultivation systems of Mikania glomerata Spreng

Abstract

Mikania glomerata Sprengel, popularly known as “guaco,” is used in Brazilian folk medicine for several inflammatory and allergic conditions. Besides, the popular use “guaco” is indicated by the Brazilian Ministry of Health as a safe and effective herbal medicine. The biological activity of M. glomerata extracts is due to the presence of the coumarins, a large family of phenolic substances found in plants and is made of fused benzene and α-pyrone rings. Considering that there are few data on the biological effects of the extracts of M. glomerata, mainly in genetic level, this work aims to evaluate, in vitro, the genotoxicity and coumarin production in M. glomerata in conventional and organic growing. The data showed that the organic culture system showed double the concentration of coumarin being significantly more productive than the conventional system. Besides, the results of comet assay suggest that extracts of M. glomerata cultivated in a conventional system was genotoxic, increased DNA damage levels while the organic extracts seem to have antigenotoxic effect possibly due to the concentration of coumarins. Additional biochemical investigations are necessary to elucidate the mechanisms of action of M. glomerata extracts, which were found to have a role in protection against DNA damage.     

Pesticides impact on Clavibacter michiganensis ssp. sepedonicus biofilm formation

The effect of various pesticides on the biofilm formation by the phytopathogenic bacterium Clavibacter michiganensis ssp. sepedonicus (Cms), the potato ring rot causative agent, was explored for the first time. Systemic herbicides: 2,4-D, diuron, glyphosate, clopyralid, fluorodifen, as well as the commercial preparations “Lazurite,” “Ridomil Gold,” and the mitochondria inhibiting pesticides analog, sodium monoiodoacetate, were studied. These pesticides' effect on the Cms biofilm formation was shown to be distinct and dependent on the agent under question. Cms biofilm formation was reduced when exposed to sodium monoiodoacetate, as well as “Lazurite” preparation, that could be due to the bactericidal effect of these agents. 2,4-D and “Ridomil Gold” preparation stimulated the biofilm formation. Systemic herbicides diuron, glyphosate, clopyralid, fluorodifen did not exert appreciable influence on the process of bacterial biofilm formation.     

Scientific Basis of an Improved EPA Policy on Control of Organic Emissions for Ambient Ozone Reduction

ABSTRACT

This article describes an effort to re-examine the scientific bases of the existing, more than two decades-old U.S. Environmental Protection Agency (EPA) policy on volatile organic compound reactivity in light of recent scientific knowledge and understanding. The existing policy allows “negligibly reactive” organic emissions, that is, emissions with ambient ozone production potential lower than that of ethane, to be exempted from all ozone regulations. It relies on use of k_OH and incremental reactivity data for determining whether an organic compound is negligibly reactive. Recent scientific evidence suggests that (1) exempting the negligibly reactive organic emissions from all regulations is unjustifiable, (2) the choice of ethane as the benchmark organic species for distinguishing reactive from negligibly reactive organics may be inappropriate, (3) the assumptions and methods used for classifying organic compounds as “reactive” and “negligibly reactive” should be reconsidered, and (4) the volatility factor should be considered, more appropriately, in much the same way as the reactivity factor.     

Festuca arundinacea,glutathione S-transferase and herbicide safeners: A preliminary case study to reduce herbicidal pollution

The expression of glutathione S-transferase (GST) activity in Festuca arundinacea was investigated in response to the following herbicide safeners: benoxacor, cloquintocet-mexyl, fenchlorazol-ethyl, fenclorim, fluxofenim and oxabetrinil. All the above compounds enhanced the GST activity tested towards the “model” substrate 1-chloro-2,4-dinitrobenzene (CDNB). Assays of GST activity towards the herbicides terbuthylazine (N ²-tert-butyl-6-chloro-N ⁴-ethyl-1,3,5-triazine-2,4-diamine) and butachlor (N-butoxymethyl-2-chloro-2′,6′-diethylacetanilide) as substrates also showed the ability of the safeners to enhance the enzyme activity towards both these herbicides, with the exception of cloquintocet-mexyl for the enzyme activity towards butachlor. As a consequence of the above effects at a macro-scale level, decreased herbicide accumulation and persistence were ascertained in response to the addition of the safener benoxacor to both terbuthylazine and butachlor treatments. These results are discussed in terms of capacity of benoxacor to induce herbicide detoxification in Festuca arundinacea with a view to utilizing them in reducing herbicide pollution.     

Root uptake,translocation, accumulation and dissipation of the botanical insecticide,azadirachtin, in young spruce trees

Abstract

A formulation containing the biopesticide azadirachtin‐A (AZ‐A), extracted from the seeds of neem tree, Azadirachta indica A. Juss, was applied (10 μg/mL) in a nutrient solution (200 mL) to the roots of young spruce trees [Picea glauca (Moench) Voss]. The uptake, translocation, persistence and dissipation of AZ‐A in spruce were studied. The insecticide was taken up by the root system, translocated via xylem vessels and accumulated in the photosynthate sinks (areas of new growth, especially shoots), confirming that AZ‐A is systemic. The peak AZ‐A concentrations (μg/g, fresh weight) in the shoots (5.16 ± 0.73) and needles (2.56 ± 0.31) occurred at 8 and 15 d after treatment, respectively. The AZ‐A concentrations in bark and wood during this period were very low, however they were high in the root samples. The dissipation of AZ‐A from the shoots was rapid compared to other matrices. The initial (0‐d) and final (20‐d) AZ‐A concentrations (μg/mL) in the nutrient solution were 8.99 ± 1.24 and 3.24 + 0.55, respectively. The dissipation of AZ‐A in the nutrient solution followed first‐order kinetics. Dissipation half‐life (DT₅₀) and rate constant (C), calculated from the nonlinear regression equation (Y = 8.400 e^‐00544t), were 12.74 d and 0.0544, respectively. Usefulness of AZ‐A as a systemic insecticide in forest insect control programs is discussed.     

Bioaccumulation of glyphosate and its formulation Roundup Ultra in Lumbriculus variegatus and its effects on biotransformation and antioxidant enzymes

The bioaccumulation potential of glyphosate and the formulation Roundup Ultra, as well as possible effects on biotransformation and antioxidant enzymes in Lumbriculus variegatus were compared by four days exposure to concentrations between 0.05 and 5 mg L⁻¹ pure glyphosate and its formulation. Bioaccumulation was determined using ¹⁴C labeled glyphosate. The bioaccumulation factor (BCF) varied between 1.4 and 5.9 for the different concentrations, and was higher than estimated from log P_ow. Glyphosate and its surfactant POEA caused elevation of biotransformation enzyme soluble glutathione S-transferase at non-toxic concentrations. Membrane bound glutathione S-transferase activity was significantly elevated in Roundup Ultra exposed worms, compared to treatment with equal glyphosate concentrations, but did not significantly differ from the control. Antioxidant enzyme superoxide dismutase was significantly increased by glyphosate but in particular by Roundup Ultra exposure indicating oxidative stress. The results show that the formulation Roundup Ultra is of more ecotoxicological relevance than the glyphosate itself.     

Effect of external iron and arsenic species on chelant-enhanced iron bioavailability and arsenic uptake in rice (Oryza sativa L.)

This study was conducted to investigate the effect of external iron status and arsenic species on chelant-enhanced iron bioavailability and arsenic uptake. Rice seedlings (Oryza sativa L.) were used as model plant, and were grown in artificially contaminated sandy soils irrigated with Murashige and Skoog (MS) culture solution. Arsenate uptake in roots and shoots of rice seedlings were affected significantly (p > 0.05) while dimethylarsinic acid (DMAA) was not by the additional iron and chelating ligand treatments. Regardless of iron concentrations in the soil solution, HIDS increased arsenic uptake for roots more than EDTA and EDDS. Chelating ligands and arsenic species also influenced iron uptake in rice roots. Irrespective of arsenic species, HIDS was found to be more effective in the increase of iron bioavailability and uptake in rice roots compared to other chelants. There was a significant positive correlation (r = 0.78, p < 0.05) between arsenate and iron concentrations in the roots of rice seedlings grown with or without additional iron indicating that arsenate inhibit iron uptake. In contrast, there was no correlation between iron and DMAA uptake in roots. Poor correlation between iron and arsenic in shoots indicated that iron uptake in shoots was neither affected by additional iron nor by arsenic species. Compared to the control, chelating ligands increased iron uptake in shoots of rice seedlings significantly (p < 0.05). Regardless of additional iron and arsenic species, iron uptake in rice shoots did not differed among EDTA, EDDS, and HIDS treatments.     

Behaviour of pendimethalin in tropical and mediterranean plain field condition

Abstract

Behaviour of the herbicide pendimethalin [N‐(l‐ethylpropyl)‐3,4‐dimethyl‐2,6‐dinitrobenzenamine] was evaluated in plain field under wet tropical conditions (Martinique, FWI) and in the Mediterranean area (Languedoc, South of France). Simultaneously, adsorption parameters were discussed with Freundlich equation, and desorption evaluated using a model with two compartments corresponding to two different energy levels. Pendimethalin showed a strong adsorption in all three soils and was very difficult to desorb. Higher clay content in tropical vertisol and ferrisol involved adsorption parameters (Kfa) higher than the one found in the Mediterranean fluvisol. Although heavy rainfalls in the tropics intervene on migration, pendimethalin propensity to leaching is levelled by its strong adsorption potential and appears very limited under the conditions chosen during this work. Half‐life of the compound (in the 0–25 cm soil layer) varied from 13 to 17 days. Pendimethalin was also classified as a “non‐leacher” compound using the “Gustafson model”.     

Antioxidant responses to simulated acid rain and heavy metal deposition in birch seedlings

This study measured the responses of different anti-oxidants in 2-year-old birch (Betula pendula Roth) seedlings subjected to simulated acid rain (pH 4.0) and heavy metals (Cu/Ni), applied alone or in combination for 2 months. The applied concentrations of pollutants did not significantly affect seedling biomass or total glutathione levels. Acid rain alone increased superoxide dismutase (SOD) activity both in leaves and roots, while heavy metals alone inhibited SOD activity in roots. Both acid rain and heavy metals applied singly increased ascorbate peroxidase (APX) and guaiacol peroxidase (GPX) activities in leaves but decreased activities in roots. In contrast, acid rain and heavy metal treatments increased glutathione reductase (GR) activity in roots but not in leaves. Spraying birch seedlings with a mixture of acid rain and heavy metals increased SOD, APX and GPX activities in leaves and GR activity in roots. However, the effects of mixed pollutants on enzyme activities usually were less than the summed effects of individual pollutants. Enzyme responses also depended on where pollutants were applied: spraying pollutants onto the shoots initiated higher responses in SOD, APX and GPX than did application to the soil surface, while the opposite was true for GR.     

Effects of DDT and piperonyl butoxide on the metabolic alterations in pigeon (columba livia)

Abstract

Effect of acute doses of technical grade of dichloro diphenyl trichloro ethane (DDT) and piperonyl butoxide (PB) on hepatic micro‐somal cytochrome P₄₅₀ (Cyt. P450) and cytosolic glutathione‐S‐transferase (GST) activity in pigeon were studied after 24 hours of treatment. A completely reverse trend of changes in Cyt. P450 and GST activity were found as increase in Cyt. ?450 paralleled with decrease in GST activity following exposure to DDT. However, intensity of changes in Cyt. P450 was greater than that of GST. A dose dependent decrease in Cyt. ?450 and GST activity was observed after PB treatment. The study may, therefore, throw some light on metabolic alterations in wild birds resulting from environmental pollution by DDT and allied chemicals.     

New bacterial strain of the genus Ochrobactrum with glyphosate-degrading activity

Thirty bacterial strains with various abilities to utilize glyphosate as the sole phosphorus source were isolated from farm soils using the glyphosate enrichment cultivation technique. Among them, a strain showing a remarkable glyphosate-degrading activity was identified by biochemical features and 16S rRNA sequence analysis as Ochrobactrum sp. (GDOS). Herbicide (3 mM) degradation was induced by phosphate starvation, and was completed within 60 h. Aminomethylphosphonic acid was detected in the exhausted medium, suggesting glyphosate oxidoreductase as the enzyme responsible for herbicide breakdown. As it grew even in the presence of glyphosate concentrations as high as 200 mM, Ochrobactrum sp. could be used for bioremediation purposes and treatment of heavily contaminated soils.     

Appendix

Abstract

The interaction of glyphosate [N‐(phosphonomethyl)‐glycine] with four typical European soils is reported. Results of adsorption and desorption isotherms show that the interaction of glyphosate with these soils was mainly related to content of iron and aluminium amorphus hydroxides. Moreover, it was found that the presence of divalent cations in 2: 1 clay minerals also contribute to glyphosate adsorption. The S‐type form of the adsorption isotherms revealed the existence of two different binding sites. These were exchangeable cations at low herbicide concentration and Fe and Al at higher glyphosate concentrations. The K maximum values of adsorption provided by the linear form of the Langmuir equation were found to be more consistent with soil parameters than those calculated by the Freundlich equation. The order of desorption from the soils was the reverse of that found for adsorption. Moreover, desorption varied from around 15 to 80% of the adsorbed herbicide according to the soil characteristics. This indicated that glyphosate adsorption on soils is far from being permanent and leaching to lower soil horizons with limited biological activity may occur.     

A Reexamination of the Ozone Limiting Approach to Estimating Short-Term NO2 Concentrations

The partition and effective diffusion coefficients of formaldehyde were measured for three materials (conventional gypsum wallboard, “green” gypsum wallboard, and “green” carpet) under three relative humidity (RH) conditions (20%, 50%, and 70% RH). The “green” materials contained recycled materials and were friendly to environment. A dynamic dual-chamber test method was used. Results showed that a higher relative humidity led to a larger effective diffusion coefficient for two kinds of wallboards and carpet. The carpet was also found to be very permeable resulting in an effective diffusion coefficient at the same order of magnitude with the formaldehyde diffusion coefficient in air. The partition coefficient (K _ma) of formaldehyde in conventional wallboard was 1.52 times larger at 50% RH than at 20% RH, whereas it decreased slightly from 50% to 70% RH, presumably due to the combined effects of water solubility of formaldehyde and micro-pore blocking by condensed moisture at the high RH level. The partition coefficient of formaldehyde increased slightly with the increase of relative humidity in “green” wallboard and “green” carpet. At the same relative humidity level, the “green” wallboard had larger partition coefficient and effective diffusion coefficient than the conventional wallboard, presumably due to the micro-pore structure differences between the two materials. The data generated could be used to assess the sorption effects of formaldehyde on building materials and to evaluate its impact on the formaldehyde concentration in buildings.

Implications: Based on the results of this study, the sink effects of these commonly used materials (conventional and “green” gypsum wallboards, “green” carpet) on indoor formaldehyde concentration could be estimated. The effects of relative humidity on the diffusion and partition coefficients of formaldehyde were found to differ for materials and for different humidity levels, indicating the need for further investigation of the mechanisms through which humidity effects take place.     

Hormetic effect of glyphosate on Urochloa decumbens plants

Abstract

Urochloa decumbens plants may be reached by herbicide drift from applications of glyphosate from neighboring areas or by variations during applications. Considering the different phenological stages and size of plants in these areas, the amount of active ingredient that reaches the plants probably varies. The objective of this study was to evaluate the effects of the application of different doses of glyphosate on U. decumbens plants. Two greenhouse experiments were conducted with two replications at different times. The first experiment evaluated the biological response of U. decumbens plants to glyphosate doses (0, 2.81, 5.63, 11.25, 22.5, 45, 90, 180, 360, 720, and 1,440?g a.e. ha^?1), with six replications. The second experiment evaluated the response of U. decumbens plants to the application of a selected low dose of 11.25?g a.e. ha^?1. Evaluations of injury were performed at 0, 7, 14, and 21?days after application, and dry weight of plants was determined for each evaluation period. U. decumbens plants increased in dry weight when using the glyphosate dose of 11.25?g a.e. ha^?1. However, plants had different responses to the application of this low dose. It can promote both stimulation and inhibition of plant growth.