Effect of endosulfan in female rats growing on low- and high-protein cereal diet

Endosulfan (α,β-1,2,3,4,7,7-hexachlorobicyclo(2,2,1)-heptene-(2)-bis-hydroxymethylene(5,6)sulfite) fed daily 0.5 and 100 ppm in the diet proved significantly toxic to female rats (initial weight 40–50 g) growing on a low-protein (5%) diet as compared to those growing on a high-protein (24%) diet. The toxic symptoms which developed exclusively in low-protein-fed rats included growth retardation, low blood counts, low RNA and protein levels in liver, and high glutathione levels in liver and blood. However, no changes in the activities of liver RNase, blood glucose-6-phosphate dehydrogenase, and glutathione reductase were observed. Liver glucose-6-phosphatase activity increased significantly. Endosulfan induced an increased accumulation of perirenal adipose in rats raised both on low- and high-protein diets. Endosulfan elicited cumulative toxic manifestations as evident from the relative degree of toxicity caused by 0.5 ppm and 18 weeks feeding. α-Endosulfan, β-endosulfan, and endosulfan sulfate were recovered from adipose tissue, the recovery being higher in adipose tissue of rats raised on a low-protein diet.     

Determination of residues of endosulfan and endosulfan sulfate on eggplant,mustard and chickpea

Extractable residues of endosulfan stereoisomers and its toxic metabolite, endosulfan sulfate, on a vegetable, an oilseed and a pulse crop were determined by gas-liquid chromatography. The study revealed that the alpha isomer degraded faster than the beta isomer. Beta-endosulfan accumulated during the first three days following the treatment. Endosulfan sulfate residues appeared a few days after application and decreased with time. The total endosulfan residues in the seeds from treated mustard ranged from 0.08 to 0.12 mg kg^?1 and were at or below the limit of determination (0.02 mg kg^?1) in chickpea seeds following harvest.     

The degradation of diflubenzuron and its chief metabolites in soils. Part II: Fate of 4-chlorophenylurea

The fate of 4-chlorophenylurea in soils was studied with two preparations: one labelled with ¹⁴C in the phenyl ring and the other in the carbonyl group. The initial dose of 1 mg kg^?1 decreased to 50% in about 5 weeks in aerobic sandy clay and in about 16 weeks in anaerobic hydrosoil. Soil treatment with each of the preparations resulted in the release of [¹⁴C]carbon dioxide, pointing to decarbonylation and ring opening. The fraction of non-extractable (soil-bound) radioactivity increased during incubation. Quantities of ring-¹⁴C-labelled and carbonyl-¹⁴C-labelled bound residues differed strongly in the aerobic soil but only slightly in the anaerobic hydrosoil. It is assumed that two sorts of bound residues are formed from 4-chlorophenylurea: one is fairly stable and might consist of bound 4-chloroaniline or its transformation products, whereas the other is presumed to be a degradable derivative of 4-chlorophenylurea.     

Fate of captan and folpet in rats and their effects on isolated liver nuclei

Excretion and distribution of single and multiple intraperitoneal doses of [³⁵S]captan and [¹⁴C]folpet were similar in normal and 70% hepatectomized male rats. After receiving the single dose of captan, the rats eliminate approximately 76% of the radioactivity in the urine after 72 hr. The elimination in the feces for the same time period was 13%. Normal rats administered single or multiple doses of [¹⁴C]folpet excreted nearly 100% of the total dose in the urine within the first 24 hr. Nuclei isolated from the liver of normal and 70% hepatectomized rats receiving multiple doses of [³⁵S]captan contained 0.008–0.009 μg ³⁵S/g of tissue. Appreciable amounts of the radioactivity from [³⁵S]captan were bound by isolated nuclei from the livers of normal and partially hepatectomized rats. After a 1-hr treatment with [³⁶S]captan, the nuclei were fractionated into nuclear sap protein, deoxyribonucleoprotein (including histones), acidic ribonucleoprotein, and “residual” protein fractions. These proteins in normal nuclei bound 10, 14, 39, and 16% of the total label, respectively, with essentially the same results obtained with nuclei from regenerating rat liver. When compared by polyacrylamide gel electrophoresis, acidic nuclear proteins from treated and nontreated normal nuclei were characterized by band diffusion and the presence or absence of Amido Schwartz-staining bands. None of the abovementioned effects on histones from treated nuclei were observed. Captan treatment of isolated nuclei also altered the extraction characteristics of the nuclear protein fractions, presumably because of extensive aggregation of thiol-containing nuclear proteins.     

The degradation of diflubenzuron and its chief metabolites in soils. Part III. Fate of 2,6-difluorobenzoic acid

2,6-Difluorobenzoic acid, one of the two primary diflubenzuron metabolites, is rapidly and completely degraded in soil. Times to 50% disappearance were 9 and 12 days in two agricultural soils. [¹⁴C]Carbon dioxide was an ultimate product of the ring-¹⁴C-labelled compound. A part of the radioactivity, increasing with time to one third of the applied dose of 1 mg kg^?1, could not be extracted from the soil.     

Evaluation of endosulfan residues in vegetables grown in greenhouses

The reduction in residue levels of endosulfan with time after treatment of tomatoes, green beans, peppers and cucumbers grown in different types of commercial greenhouses (flat- and asymmetric-roof greenhouses) in Almería (Spain) was investigated. A study of the major and minor degradation products of endosulfan in peppers and cucumbers (endosulfan-sulfate, -ether and -lactone) was carried out using gas chromatography-tandem mass spectrometry (GC-MS/MS). To establish the influence of environmental conditions on the degradation of endosulfan, several field trials have been carried out in which crops were sprayed at different rates (full, half- and quarter- of those rates recommended) during two seasons (spring and winter). For statistical purposes, the disappearance of endosulfan with time was considered to follow a pseudo-first-order reaction. Analysis of variance (ANOVA) has been applied to the results obtained. Half-lives of residue disappearance were 4.03-4.68 days in green beans, 4.03-4.20 days in tomatoes, 8.22 days in peppers and 7.97 days in cucumbers. Half-lives in spring were shorter than in the winter season. The application rate and the type of greenhouse did not influence the half-lives.     

Residues and fate of endosulfan on field-grown pepper and tomato

Endosulfan (Thiodan 3 EC), a mixture of α- and β-isomers, was sprayed on 92-day-old field-grown pepper and tomato at the recommended rate of 0·61 kg AI ha^-1. Plant tissue samples were collected at 1 h to 14 days after application and analysed to determine the content and dissipation rate of endosulfan isomers (α- and β-endosulfan) and the major metabolite, endosulfan sulfate. Analysis of samples was accomplished using gas chromatography-mass selective detection (GC-MSD). The results indicated the formation of endosulfan sulfate as a residue component on the plant tissues and also the relatively higher persistence of the β-isomer as compared to the α-isomer on pepper fruits. The initial total residues (α- and β-endosulfan isomers plus endosulfan sulfate) were higher on leaves than on fruits. On pepper fruits, the α-isomer, which is the more toxic to mammals, dissipated faster than the less toxic β-isomer. Total residues (α- and β-endosulfan isomers plus the sulfate metabolite) on tomato leaves revealed longer persistence (t_1/2 4·6 days) compared to the total residues detected on pepper leaves (t_1/2 2·0 days) 3–14 days following spraying. Persistence of the β-isomer on pepper fruits was high 3–14 days following spraying compared to on tomato fruits. This long persistence increases risk of exposure of the consumer. In addition, the longer persistence of the total residues on tomato foliage should be considered of importance for timing the safe entry of tomato harvesters due to the high mammalian toxicity of endosulfan. © 1998 Society of Chemical Industry     

The metabolism of the pyrethroid insecticide cypermethrin in rats; excreted metabolites

The metabolism of the pyrethroid insecticide cypermethrin has been studied in rats using three forms of ¹⁴C-labelling (benzyl-, cyclopropyl- and cyano-) and separate cis- and trans- isomers. The proportion of the dose absorbed from the intestines (50–70% at 2–3 mg kg^?1) is rapidly metabolised and eliminated. The major reaction is cleavage of the ester bond to afford the constituent cis- and trans- acids which are conjugated with glucuronic acid and eliminated in the urine. The 3-phenoxybenzyl portion of the molecule is probably released as the α-hydroxynitrile, which is converted via the aldehyde into 3-phenoxybenzoic acid. This compound is then largely hydroxylated and eliminated as a sulphate conjugate. The cyanide ion is metabolised via predictable routes, for instance, as thiocyanate. Cypermethrin is hydroxylated to some extent before hydrolysis. Most of this hydroxylation occurs at the methyl group trans to the cyclopropane carboxyl group, and at the 4-position of the phenoxy group. cis- Cypermethrin is slightly more stable than the trans-isomer.     

Enhanced excretion of DDT and metabolites in rats treated with trans,trans-muconate

The interactions between trans,trans-muconate and p,p′-DDT were examined. Male Wistar rats were injected intraperitoneally with 6.67 mg kg^?1 [¹⁴C]p,p′-DDT. Two hours later the experimental animals received orally a solution of sodium muconate (75 mg kg^?1, 0.3 ml) in physiological saline, pH 7.2; control animals received an equal volume of physiological saline. Treatment was repeated every 12 hr for 10 days. Sodium muconate does not modify urinary excretion of labeled compounds, yet it reduces body burden by accelerating the excretion rate of these compounds in rat feces. This action was observed only during the first 24 hr after the animals were exposed to p,p′-DDT.     

Fate of fluroxypyr in soil

Batch adsorption K_oc values of fluroxypyr-methylheptyl ester (20000 1kg^?1) and fluroxypyr (74 1kg^?1) indicate increased mobility after hydrolysis of the ester to fluroxypyr. After 1 to 2 weeks incubation time in four soils, desorption K_oc values of fluroxypyr were 100-200 1kg^?1 but increased to 400-700 1kg^?1 after 8 weeks. The increase in desorption K_oc was related to incubation time and not to concentration, and it was interpreted as an entrapment of the fluroxypyr within the soil organic matter. Similar increases in desorption K_oc with incubation time were noticed for pyridinol and methoxypyridine metabolites of fluroxypyr. K_oc values also increased along the metabolic sequence fluroxypyr/pyridinol/methoxypyridine, with maximum K_oc values of 3000-4000 1 kg^?1 for the methoxypyridine metabolite. Hence mobility of the fluroxypyr aromatic ring strongly decreases with increased residence time in the soil.     

Fate of fluroxypyr in soil

Fluroxypyr-MHE (methylheptyl ester) was added to four soils and incubated at 26 ± 1°C and approximately 0.1 MPa moisture. After initial rapid hydrolysis of the ester to fluroxypyr, fluroxypyr degraded with half-lives of 12, 12, 23, and 7 days in Barnes loam, Catlin silt loam, Hanford sandy loam, and Mhoon clay soils, respectively. Two metabolites (4-amino-3,5-dichloro-6-fluoro-pyridin-2-ol and 4-amino-3, 5-dichloro - 6 - fluoro - 2 -methoxypyridine) were identified, with the pyridinol at its maximum concentration after 2 to 4 weeks of incubation, and the methoxypyridine after 8 weeks. Degradation rates of fluroxypyr and its pyridinol were not significantly altered by diurnally varying soil temperature (21°C to 32°C) or moisture, nor by the presence of growing grass. Methoxypyridine dissipation was more rapid under greenhouse conditions, suggesting that laboratory studies underestimated the dissipation rate of this metabolite.     

Fate of fluroxypyr in water

Dissipation of fluroxypyr in North Dakota lake waters was examined in three laboratory studies: photolysis, aerobic metabolism, and anaerobic metabolism. Photolysis was negligible in sterilized water, with and without natural photosensitizers. In 1:10 sediment:water systems, 50% disappearance times of 0.5–2 weeks were observed in the metabolism studies (25°C). Major metabolites (>10%) included the dichloropyridinol and 3-chloropyridinol derivatives, while the 5-chloropyridinol derivative appeared (<7%) in anaerobic systems. The pyridinols disappeared readily in aerobic but more slowly in anaerobic systems. In typical pond and lake waters, fluroxypyr and pyridinols are expected to disappear by the end of the growing season. Devenir de fluroxypyr dans l'eau La dissipation du fluroxypyr dans les eaux de lac dans le Dakota Nord a étéétudiée dans 3 études de laboratoires: photolyse, métabolisme aérobique et métabolisme anaérobique. La photolyse était négligeable dans I'eau stérilisée, avec et sans photosensibilisants naturels. Dans des systémes sédiments/eau de 1/10 des temps de disparition 50% de 0-5-2 semaines ont été observées dans les études de meéabolisme (25°C). Les principaux metabolites (>10%) comprenaient les dérivés dichloropyridinol et 3-chloropyridinol, tandis que le dérivé 5-chloro-pyridinol apparaissait (<7%) dans les systemés anaérobiques. Les pyridinols disparaissent rapidement en aérobie mais lentement dans les systémes anaerobiques. Dans les eaux typiques de mares et d'étangs, le fluroxypyr et les pyridinols sont supposés avoir disparu à la fin de la saison de croissance. Verhalten von Fluroxypyr in Wasser Der Verlust an Rückständen von Fluroxypyr im Wasser aus Seen in North Dakota wurde hinsichtlich der Photolyse sowie des aeroben und anaeroben Metabolismus untersucht. Die Photolyse war in sterilisiertem Wasser mit und ohne natürlichen Photosensitizern vernachlässigbar. Bei den Metabolismusuntersuchungen bei 25°C in l:10-Sediment:Wasser-Systemen lagen die Zeiten für 50%igen Verlust bei 0,5.2 Wochen. Zu den Hauptmetaboliten (>10%) zählten Dichlorpyridinol und 3-Chlor-pyridinol-Derivate, während 5-Chlorpyridinol-Derivate in anaeroben Systemen unter 7% blieben. Die Pyridinole verschwanden rasch in aeroben, aber viel langsamer in anaerobischen Systemen. In solchen Gewässern werden Fluroxypyr und Pyridinole erwartungsgemäß zum Ende einer Vegetationsperiode verschwunden sein.     

Fate of fluroxypyr in soil

Fluroxypyr-MHE (methylheptyl ester) was applied to small field plots containing Londo sandy loam soil. After 30 days, fluroxypyr had degraded to about 60% of the initial concentration, but was still the main component, while after 120 and 366 days the methoxypyridine metabolite was the main component in the soil. At 30, 120, and 366 days, lettuce, turnips, green beans, soybeans, and wheat were planted and grown with no observed injury. Residues of ¹⁴C in the edible crop fractions were indistinguishable from ¹⁴C in control plants exposed to ¹⁴CO₂, while residues in plant greens and chaff were low (0.1–0.2 mg kg^?1), with little evidence of fluroxypyr and no evidence of metabolite uptake. These results indicate that the methoxypyridine metabolite, if present in the soil, does not harm and is not taken up into the plants.     

Effect of neem cake on persistence of diazinon and endosulfan in paddy soil

Experiments were carried out to study the influence of two types of neem cake (solvent-extracted, NC-I and expeller-extracted, NC-II) on the persistence in soil of diazinon and endosulfan applied as commercial formulations. It was found that both types of neem cake applied at 10, 20 or 30 g ha^-1 prolonged the period of degradation as compared with soils without neem cake amendment, and hence increased the persistence of the insecticides. There was little difference in the effect of the two types of neem cake. Treatment of the soil with insecticide 10 days after amendment with neem cake did not lead to any increase in persistence; for a good response, treatment of soil with insecticide and with neem cake must be done at the same time. © 1998 SCI.     

Disappearance of endosulfan residues from seawater and sediment under laboratory conditions

The dissipation rate of endosulfan isomers (α and β) in seawater and sediment was studied. The disappearance rate of both isomers from seawater and pure water was compared, and the same measurements were made in both sterile and unsterile marine sediment. Flasks of water and sediment, fortified with a dispersion of a commercial endosulfan 350 g litre⁻¹ EC, Protodan 35®, were incubated under laboratory light at room temperature for 82 days. A micro on‐line extraction method and GC‐ECD was used to determine the pesticide and its metabolites. The dissipation of endosulfan (in two phases of first‐order kinetics) occurred more rapidly in seawater than in pure water. At the end of the experiment, the concentration of α‐endosulfan in sterile sediment was four times greater than in unsterile sediment, while the dissipation rate of β‐endosulfan in unsterile sediment was approximately double that observed in sterile sediment. The dissipation of both forms in sediment occurred in a single stage. Endosulfan β‐isomer was more persistent than α‐isomer in both sterile and unsterile sediment. Dissipation of endosulfan sum of α‐ and β‐isomers in sediment at the end of the experiment ranged from 80% (sterile) to 95% (unsterile). Endosulfan sulfate was detected in water and sediment as the main metabolite. © 2000 Society of Chemical Industry     

Fate of copper in ponds.

Treatments of 3 ppm copper sulfate (CuSO4-5H2O) were applied to two small aquatic systems in Michigan in 1971. To study the pathways of the added copper, samples of water, sediment, aquatic macrophytes, filamentous algae, and fish were collected and analyzed by atomic absorption. Sampling was initiated before treatment and continued up to 4 months in one of the ponds. Dissolved copper concentrations in water decreased rapidly immediately after treatment and then gradually to background levels. Reduction of dissolved copper may have involved initial precipitation of an insoluble compound, such as malachite, followed by sediment adsorption of soluble copper complexes and copper released from aquatic plants. Levels of copper in sediment increased rapidly at first and gradually later in the study. Aquatic plants and filamentous algae accumulated very high levels of copper. Uptake rates were apparently affected by water temperature and growth stages of the plants. Data indicate that aquatic macrophytes developing in one pond 10 weeks after treatment took up copper from the sediment. Although green sunfish (Lepomis cyanellus) accumulated copper soon after treatment, levels returned to background later in the study.     

The Fate of Paraquat in Soils

Abstract

An outstanding property of the bipyridylium herbicides is the rapidity with which they are inactivated in contact with soils. The initial inactivation is attributable to strong adsorption on soil colloids and, as may be expected, is governed by the nature of the soil. Subsequent degradation may be induced by ultraviolet radiation or, below the soil surface, by the activity of the microflora. The agronomic significance of these mechanisms is described by reference to recent work on paraquat.     

Fate of famoxadone in the environment

The fate of famoxadone [Famoxate®, 3-anilino-5-methyl-5-(4-phenoxyphenyl)-1,3-oxazolidine-2,4-dione] in the aquatic and soil environment was examined. It was found to be relatively stable at pH 5, but hydrolysed rapidly in pH 7 and 9 buffer solutions. Primary hydrolytic degradation reactions included the opening of the oxazolidinedione ring and the cleavage of the oxazolidinedione-aminophenyl linkage. The compound degraded rapidly in soil by both hydrolytic and microbial action. In addition to the generation of [¹⁴C] carbon dioxide and unextractable bound residues, hydroxylation and hydrolysis reactions occurred to yield multiple degradation products. Nitration of famoxadone at the 2- or 4-phenylamino position was observed as a novel non-biological degradation reaction of famoxadone in soil. Degradation in aqueous solution (pH 5) and on soil surfaces was accelerated under simulated sunlight irradiation. Famoxadone exhibited negligible soil mobility potential, and its primary degradation products were also shown to dissipate rapidly in the environment.     

Fate of terbutryn in macrophyte-free and macrophyte-containing farm ponds

Terbutryn (2-ethylamino-4-(tert-butylamino)-6-methylthio-s-triazine) was applied in June 1978, to two farm ponds (A and C) near Winnipeg. Canada, to give 100 μg/l water concentrations. The persistence of the herbicide and its degradation products was monitored over a 61-week period following application. The half-life of terbutryn m the water column ranged from 3 weeks in Pond C, which contained heavy growths of cattails (Typha sp.) and duckweed (Lemna sp.), to 30 days in Pond A. which was free from aquatic macrophytes, Terbutryn residues m sediment reached a maximum of 1.4 μg/g (dry wt) in Pond A and 0.5 μg/g in C. Maximum concentrations of N-deethylated terbutryn (2amino-4-(tert-butylamino)-6-methylthio-s-tria-zine)(DET) were 14.4 μg/l in Pond A water after 61 weeks and 0.14 μg/g in Pond C sediment after 30 weeks. The maximum concentration of hydroxy-terbutryn (2-hydroxy-4-ethyl-amino-6-(tert-butylamino)-s-triazine) (HT) observed in pond water was 6.4 μg/l in Pond C after 7 weeks. HT was not detected in sediment (<0.05 μg/g) during the study. After 61 weeks, about 50% of the terbutryn that was added could still be accounted for in Pond A and 35% in Pond C. Terbutryn. DET and HT represented an estimated 71, 28 and 1%, respectively, of total terbutryn remaining in Pond A and 65, 29 and 6%, respectively, of that remaining in Pond C, 61 weeks after application, Terbutryn residues in Typha ranged from 0.3 μg/g (dry wt) in the shoot to 3.3 μg/g in the roots. After 12 weeks, terbutryn residues in plants (Pond C) were estimated to account for 1 to 4% of the herbicide in the pond.     

Fate of prothiofos (O-2,4-dichlorophenyl O-ethyl S-propyl phosphorodithioate) in rats

The fate of prothiofos (O-2,4-dichlorophenyl O-ethyl S-propyl phosphorodithioate) were studied in male rats 1, 3, 8, 24, 48, and 120 hr after oral administration. In the determination of prothiofos by gas chromatography-mass spectrometry, pentadeuteroethoxy-labeled prothiofos was used as the internal standard and the carrier of residual prothiofos. Prothiofos was rapidly absorbed from the small intestine and had substantially disappeared from the gastrointestinal tract within 24 hr after dosing. The residual concentrations of prothiofos in all organs analyzed, reached a maximum at 3 hr after dosing, and then diminished exponentially. The major urinary metabolites were 2,4-dichlorophenol (21% of administered prothiofos), its conjugated substances (26%), O-2,4-dichlorophenyl O-ethyl hydrogen phosphorothioate (14%), and O-2,4-dichlorophenyl O-ethyl hydrogen phosphate (25%). While prothiofos was found in the feces (3.8%), prothiofos oxygen analog (prothiofos-oxon) was scarcely detected in any excreta. Results obtained with a single dosing of prothiofos-oxon indicated that the oxygen analog formed from prothiofos in vivo was rapidly degraded through cleavage of the PS bond and the liberation of 2,4-dichlorophenol. The low mammalian toxicity of prothiofos is probably due to depropylthiolation in the molecule.