Biodegradation of soil‐applied endosulfan in the presence of a biosurfactant

Abstract

Biodegradation of endosulfan isomers in soil‐applied and flask‐coated conditions was studied, by an isolated bacterial coculture. The degradation in soil‐applied form was 20–30% slower than in flask‐coated condition. Addition of a biosurfactant, isolated from Bacillus subtilis MTCC 1427, enhanced the rate of biodegradation by 30–45% in both the conditions. It also mobilized the residual endosulfan towards biodegradation, that otherwise remains undegraded.     

Effects of deltamethrin on hepatic microsomal cytochrome p450‐dependent monooxygenases in carp

Abstract The in vivo effects of sublethal concentrations of deltamethrin (DM), a pyrethroid insecticide, on the hepatic microsomal cytochrome P450 (Cyt P450) content and the Cyt P450‐dependent monooxygenase activities (para‐nitrophenetole‐O‐deethylase, pNPOD; aminopyrene‐N‐demethylase, APND; ethylmorphine‐N‐demethylase, EMND; 7‐ethoxycoumarin‐O‐deethylase, ECOD; and ethoxyresorufin‐O‐deethylase, EROD) were examined in adult carp (Cyprinus carpió L.).

0.2 μg/1 DM treatment resulted in significant increases in APND, EMND and ECOD activities, whereas 2 μg/1 DM resulted in significant inhibitions of all studied isoenzyme activities with the exceptions of pNPOD and APND after 72 h. EROD was the only enzyme for which a slight increase in activity was observed. On repeated treatment, Cyt P450 could not be detected after 48 h, but the Cyt P420 level increased. All tested isoenzyme activities were inhibited, with the exception ofthat of EROD, which was enhanced.

All these changes in enzyme activities and Cyt P450 content demonstrate the effects of DM on fish. DM treatment at low concentration is presumed to cause induction of the Cyt P450‐dependent monooxygenases which may lead to faster metabolization of the insecticide. In contrast, DM at higher concentration strongly inhibited the activities of the studied enzymes. This finding may be due to the damaging effect of DM on the xenobiotic metabolizing enzyme systems offish.     

Summary of efficacy evaluations using aerially applied Gypchek® against gypsy moth in the U.S.A.

Abstract

Gypchek^®, the gypsy moth (Lymantria dispar L.) nucleopolyhedrosis virus product, is manufactured by the United States Department of Agriculture (USDA) Forest Service, and Animal and Plant Health Inspection Service under controlled conditions in a laboratory strain of gypsy moth larvae. Gypchek was registered with the U.S. Environmental Protection Agency in 1978 as a general use pesticide to control gypsy moth. This product has been the subject of intense research and development targeted toward maximizing efficacy while minimizing the cost of production and application. The current Gypchek tank mix is applied at 1.25 × 10¹²occlusion bodies (OB's) per hectare for each of two applications (3‐days apart) at 18.7 litres/ha per application.     

Toxic effects of deltamethrin and λ-cyhalothrin on Xenopus laevis tadpoles

This study evaluates the toxic effects of deltamethrin and λ-cyhalothrin on Xenopus laevis tadpoles after 168 h of exposure. The LC₅₀ of deltamethrin and λ-cyhalothrin at 168 h was calculated as the μg of active ingredient per liter (μg AI/L). According to these values, the LC₅₀ was 6.26 and 3.94 μg AI/L for deltamethrin and λ-cyhalothrin, respectively. Several enzymes were studied for early signs of intoxication following exposure to the pesticides for 24 h. Glutathione-S-transferase,carboxylesterase, and lactate dehydrogenase were inhibited by λ-cyhalothrin, and both pesticides inhibited acid phosphatase and aspartate aminotransferase. In contrast, acetylcholinesterase was activated by deltamethrin. The results suggest that X. laevis is sensitive to the pyrethroids that were tested, and the enzyme responses suggest that they are potential biomarkers for evaluating the toxic effect of pyrethroids on amphibians in environmental conditions.     

Toxic effects of deltamethrin and λ-cyhalothrin on Xenopus laevis tadpoles

This study evaluates the toxic effects of deltamethrin and λ-cyhalothrin on Xenopus laevis tadpoles after 168 h of exposure. The LC(50) of deltamethrin and λ-cyhalothrin at 168 h was calculated as the μg of active ingredient per liter (μg AI/L). According to these values, the LC(50) was 6.26 and 3.94 μg AI/L for deltamethrin and λ-cyhalothrin, respectively. Several enzymes were studied for early signs of intoxication following exposure to the pesticides for 24 h. Glutathione-S-transferase,carboxylesterase, and lactate dehydrogenase were inhibited by λ-cyhalothrin, and both pesticides inhibited acid phosphatase and aspartate aminotransferase. In contrast, acetylcholinesterase was activated by deltamethrin. The results suggest that X. laevis is sensitive to the pyrethroids that were tested, and the enzyme responses suggest that they are potential biomarkers for evaluating the toxic effect of pyrethroids on amphibians in environmental conditions.     

Influence of additives in the end‐use mixes of tebufenozide on deposition,adhesion and persistence in spruce foliage

Abstract

A commercial flowable formulation of tebufenozide, RH‐5992 2F [N'‐t‐butyl‐N'‐(3,5‐dimethylbenzoyl)‐N‐(4‐ethylbenzoyl) hydrazine], was diluted with water, water and canola oil, and water and the methyl ester of canola oil, to provide six end‐use mixes with concentrations of 35 and 70 g of active ingredient (Al) litre^‐1. The mixes were applied at 70 and 140 g Al ha^‐1 over white spruce [Picea glauca (Moench) Voss] seedlings in a laboratory spray chamber and foliar concentrations of tebufenozide were determined over a 60‐d period. At intervals of time post‐spray, seedlings were sprayed with monosized droplets of Sunspray®11N as rainfall, and the amount of tebufenozide knocked off from foliage was determined. The potential energy of adhesion (PEA) of the Al particles on the foliage increased with time and varied according to the type of end‐use mix, its viscosity and the dosage sprayed.

The end‐use mixes were applied over white spruce trees under field conditions and persistence of tebufenozide was investigated. DT₅₀ values were influenced by the type of mix and dosage sprayed. Oil‐containing mixes and higher dosages increased the PEA of tebufenozide particles.     

Wet deposition monitoring—Effect of sampling period

A comparison between weekly and event samples has been undertaken to assess the differences introduced by different sampling periods.The data analyzed cover the period 18 March 1981-28 June 1983.The weekly samples yielded lower concentrations and deposition values for all ions analyzed. The differences were significant at the 99.9 per cent confidence level.     

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.     

A new synthesis of tetrachlorofluorodibenzo‐p‐dioxin

Abstract

The 1,2,3,4‐tetrachloro‐7‐fluorodibenzo‐p‐dioxin has been synthesized via condensation of 4‐fluorocatechol and pentachloronitrobenzene. This compound could be used as an internal standard for the analysis of 2,3,7,8‐tetrachlorodibenzo‐p‐dioxin by Chromatographic methods.     

Volatilization of 1,2‐dibromo‐3‐chloropropane (DBCP) from soils

Abstract

The volatilization of DBCP from soils, as affected by the soil characteristics and application techniques, was studied in a laboratory experiment. The volatilization rate of DBCP applied in water was higher from sandy and silty loam soils than from clay soil. Water added after DBCP application acted as a soil cover, decreasing the volatilization rate. The results obtained with DBCP application in hexane to air‐dry soils, indicate that adsorption could be an important factor in reducing the volatilization losses.

Diffusion coefficients were calculated from the volatilization parameters, by using a simplified relationship between volatilization losses and diffusion through soil.     

Dry deposition of 4–50 μm dolomite particles on vegetation,flat surfaces and deposition gauges

Dry deposition of dolomite particles from a small plume onto various kinds of surfaces was studied. The concentration was measured in the air via isokinetic sampling on filters. The deposition and size distribution of the deposited particles were determined with a sedimentation scale. The results show significant variations in size distribution of deposited material and deposition velocity with wind velocity, particle size and type of surface. Clear indications of resuspension and ‘bounce-off’ were found.     

Transient‐phase and steady‐state kinetics of lipase‐catalyzed ester hydrolysis 1

Abstract

An experimental study has been made of both the steady‐state and the transient‐phase (presteady‐state) kinetics of the hydrolyses of several saturated aliphatic esters of p‐nitrophenol catalyzed by wheat germ lipase. The analysis of the presteady‐state part revealed two transients indicating that lipase‐catalyzed reactions proceed via a two‐intermediate mechanism suggested for other esterases. The possibility of more than one species of the enzyme engaged in catalytic activity is discussed and a reaction mechanism scheme is proposed accordingly.     

Differential enhanced degradation of cis‐ and trans‐1,3‐D in soil with a history of repeated field applications of 1,3‐D

Abstract

The fumigant 1,3‐dichloropropene (1,3‐D) is considered to be a potential alternative to methyl bromide. The degradation rates of cis‐ and trans‐l,3‐D in soil from a treated site during three successive annual applications of 1,3‐D progressively increased with an increase in the number of annual applications. The enhancement was greater for trans‐l,3‐D degradation than cis‐l,3‐D. In untreated soil, the degradation rates of the two isomers were similar. The enhancement lasted slightly longer than 2 years after annual field application of 1,3‐D had ceased. A single field reapplication of 1,3‐D to the treated site that had not been treated for 2 years resulted in resumed differential enhanced degradation of cis‐ and trans‐l,3‐D. Microorganisms were responsible for the enhanced degradation.     

Selective separation of deltamethrin by molecularly imprinted polymers using a β-cyclodextrin derivative as the functional monomer

A deltamethrin-imprinted polymer (MIP₁) was prepared using bis(-6-O-butanediacid monoester)-β-cyclodextrin (BBA-β-CD) as the functional monomer and toluene 2,4-diisocyanate (TDI) as the cross-linker. In comparison to the molecularly imprinted polymer where β-CD was applied as the functional monomer (MIP₂), MIP₁ showed a higher specific binding capacity (ΔC_P) and an improved imprinting factor (IF) for deltamethrin. The selective recognition experiments demonstrated that compared to MIP₂, MIP₁ could better recognize its template over other substrates that had similar chemical structures. The solid phase extraction (SPE) of deltamethrin using MIP₁ as the adsorbent was further investigated. The recoveries of the molecularly imprinted solid phase extraction (MISPE) column for deltamethrin were 83.2–93.4% with relative standard deviations (RSD) of 2.03–6.19%. The method has been successfully applied to the enrichment of trace deltamethrin from real water samples.     

Does nitrogen deposition increase forest production? The role of phosphorus

Effects of elevated N deposition on forest aboveground biomass were evaluated using long-term data from N addition experiments and from forest observation plots in Switzerland. N addition experiments with saplings were established both on calcareous and on acidic soils, in 3 plots with Fagus sylvatica and in 4 plots with Picea abies. The treatments were conducted during 15 years and consisted of additions of dry NH₄NO₃ at rates of 0, 10, 20, 40, 80, and 160 kg N ha⁻¹ yr⁻¹. The same tree species were observed in permanent forest observation plots covering the time span between 1984 and 2007, at modeled N deposition rates of 12-46 kg N ha⁻¹ yr⁻¹. Experimental N addition resulted in either no change or in a decreased shoot growth and in a reduced phosphorus concentration in the foliage in all experimental plots. In the forest, a decrease of foliar P concentration was observed between 1984 and 2007, resulting in insufficient concentrations in 71% and 67% of the Fagus and Picea plots, respectively, and in an increasing N:P ratio in Fagus. Stem increment decreased during the observation period even if corrected for age. Forest observations suggest an increasing P limitation in Swiss forests especially in Fagus which is accompanied by a growth decrease whereas the N addition experiments support the hypothesis that elevated N deposition is an important cause for this development.     

Metabolism of gamma‐hexachlorocyclohexah (HCH) in vivo. Metabolism of orally administered gamma‐2,3,4,5,6‐pentachlorocyclohexen (PCCH)

Abstract

Mexacarbate (4‐dimethylamino‐3,5‐xylyl N‐methylcarbamate) insecticide has potential for use in spruce budworm (Choristoneura fumiferana Clem.) control operations in Canada. Its persistence and fate in balsam fir (Abies balsamea (L.) Mill.), litter and soil samples were studied by spraying aerially oil‐based and water‐based formulations, each at 70 g A.I./ha over a coniferous forest near Bathurst, New Brunswick. The oil‐based formulation gave the maximum concentration of the chemical in the substrates studied. In fir needles, the highest concentrations observed were 0.51 ppm and 0.19 ppm (fresh weight) for the oil‐based and emulsion formulations respectively, 1 h after application. The residue levels decreased very rapidly with a half‐life of approximately 5 h. Three and eight days after the spray application of the emulsion and oil formulations respectively, the concentrations of mexacarbate in foliage decreased to trace levels ( 0.008 ppm). Only very low levels of residue were detected in litter and soil. The peak concentrations for the two formulations ranged from 0.02 to 0.11 ppm (fresh weight) in litter and from 0.01 to 0.06 ppm (fresh weight) in soil. The residue levels in both litter and soil decreased to below the detection limit (0.005 ppm) within 1 d. The ground deposit levels found on glass plates and the droplet density and size spectra measured on Kromekote® cards reflected the variations in concentrations found in fir needles, litter and soil samples and correlated with the observed maximum concentrations in them. Under the stipulated use pattern, mexacarbate concentrations found in the terrestrial components studied were low and are not likely to have any undue adverse effects on non‐target species.     

Effects of sub‐chronic low‐level dietary intake of chlordane on rats with cirrhosis of the liver.

Abstract

Male rats, 60 days old, were treated with chlordane during or after induction of liver cirrhosis with carbon tetrachloride to determine the effect of treatment with chlordane on the response of the rats to the disease. When liver cirrhosis was induced simultaneously with chlordane treatment the disease symptoms were aggravated; the lipid content of the tissue was lowered significantly, growth rate was significantly lower than controls and there was no apparent replacement of damaged liver tissue by liver growth. The cytochrome P₄₅₀ content of the liver was similar after both treatments. Continuation of the chlordane treatment after termination of the carbon tetrachloride treatment brought about a more rapid recovery from the induced cirrhotic condition. All these responses were to a dose range one tenth the recommended “no effect”; level for healthy animals.     

Degradation of chlorpyrifos and its hydrolysis product, 3,5,6‐trichloro‐2‐pyridinol,in soil

Abstract

The degradation of ¹⁴C‐chlorpyrifos and its hydrolysis product, 3,5,6‐trichloro‐2‐pyridinol (TCP), was investigated in soil in laboratory experiments. Between 12 and 57% of the applied chlorpyrifos persisted in a variety of agricultural soils after a 4‐week incubation. Concentrations of TCP present in these soils ranged from 1 to 34% of the applied dose. Two patterns of persistence were observed. In some soils, significant quantities of TCP and soil‐bound residues were produced, but little ¹⁴CO₂. In other soils, neither TCP nor soil‐bound residues accumulated, but large quantities of ¹⁴CO₂ were evolved. Direct treatment of fresh samples of each of these soils with ¹⁴C‐TCP resulted in rapid mineralization of TCP to ¹⁴CO₂ only in those soils in which TCP had not accumulated after chlorpyrifos treatment. The rapid mineralization of TCP in these soils was microbially mediated, but populations of soil microorganisms capable of using TCP as a sole carbon‐energy source were not detected.     

Metabolism of 14C‐carbaryl and 14C‐1‐naphthol in moist and flooded soils

Abstract

The metabolism of ¹⁴C‐carbaryl and ¹⁴C‐1‐naphthol in moist and flooded soils was studied in a continuous flow‐through system over a period of 28 days permitting ¹⁴C‐mass balance. The percent distribution of radiocarbon in organic volatiles, carbon dioxide, extractable and non‐extractable (bound) fractions of soils were determined. Organic volatiles could not be detected in both carbaryl and 1‐naphthol treated soils. More of ¹⁴CO₂ (25.6%) was evolved from moist than flooded soil (15.1%) treated with carbaryl. However, the mineralization of ¹⁴C‐1‐naphthol was negligible. The extractable radiocarbon was more in flooded soil (28.9%) than moist soil (5.5%) from carbaryl treatment. Less than one percent was present as parent compound, whereas carbaryl was mainly metabolized to 5‐hydroxy carbaryl in moist soil and to 4‐ and 5‐hydroxy carbaryl in flooded soil. The extractable radiocarbon amounted to 18.2 and 24.3% in moist and flooded soils respectively and the parent compound was less than one percent with 1‐naphthol treatment. Most of the radiocarbon was found as soil bound residues; the formation being more with 1‐naphthol than carbaryl. Humin fraction of the soil organic matter contributed most to soil bound residues of both carbaryl and 1‐naphthol.     

Metabolism of 2‐chloro‐N‐isopropylacetanilide (propachlor) in the sheep and milk goat

Abstract

Sheep metabolized a single oral dose of 2‐chloro‐N‐isopro‐pylacetanilide (propachlor) to four urinary metabolites. These were 2‐(S‐cysteinyl)‐N‐isopropylacetanilide and 2‐[S‐(N‐acetyl) cysteinyl]‐N‐isopropylacetanilide and the glucuronide conjugates of 4'‐hydroxy‐N‐isopropyl‐2‐methylsulfonylacetanilide and N‐(1‐hydroxyisopropyl)‐2‐methylsulfonylacetanilide. Residues (ppb equivalents of propachlor) from [¹⁴C]‐propachlor in the milk from a goat given daily oral doses (1.3 mg of propachlor three times daily for 15 days) plateaued at about 2 to 4 ppb equivalents of propachlor. In goat tissue, residues ranged from 1 ppb (fat) to 20 ppb (liver). Fecal and tissue metabolites were not identified.