Bioavailability and toxicity to rats of bound residues of 14C-pirimiphos-methyl in stored wheat.

Wheat grains were treated with 14C-pirimiphos-methyl to generate bound residues for testing their bioavailability to rats. Bound residues accounted for 25% of the applied dose (50 ppm) at the end of one year. When the grain bound residues were fed to rats for 48 hours the animals eliminated 30 and 40% of the administered dose in urine and feces respectively, after 5 days. Radioactivity in some selected organs and blood accounted for 37% of the administered dose after 2 days, which gradually declined to 1% after 5 days. These data indicate that wheat-bound pirimiphos-methyl residues are moderately bioavailable to rats. In a 90-day feeding study, inhibition of plasma cholinesterase and brain acetylcholinesterase strongly suggest that the bound residues possess a toxicological potential.     

Bioavailability and biological activity of bound residues of radiolabelled pirimiphos-methyl in maize grains.

Using a 14C-labelled pirimiphos-methyl preparation, the percentage of pirimiphos-methyl residues bound to maize grains after 32 weeks of storage was 13% of the applied dosage, or 38% of total terminal residues. Evidence is presented to show that bound residues of pirimiphos-methyl are bioavailable to the rat: 30%, 2% and approx. 6% of radioactivity were measured in urine expired air, and some organs respectively. A major portion of radioactivity (55%) was eliminated through faeces. Grain-bound pirimiphos-methyl residues (generated after storing whole maize grains with pirimiphos-methyl at concentrations of 10 ppm and 100 ppm) were administered to albino rats for 12 weeks. Body and organ weights, enzyme activities and blood chemistry were tested. There was a significant reduction in body weight gain in female rats. Also a significant reduction in blood cholinesterase activity was observed in both male and female rats fed on grain bound pirimiphos-methyl residues at two dose levels. The white blood cell count increased significantly in male rats fed on the high dose. No significant changes were observed in the other blood chemistry parameters tested. The results indicate that maize-bound pirimiphos-methyl residues can exert adverse biological effects in the rat.     

Bioavailability to rats of bound [14C] pirimiphos-methyl in stored wheat.

Stored wheat treated with radiolabelled pirimiphos-methyl (0-2-diethyl-amino-6-methyl-pyrimidin-4-yl 0,0-dimethyl phosphorothioate) formed bound (nonextractable) 14C residues. Supercritical fluid extraction, gas chromatography and mass spectrometric techniques were used to identify and quantitate the 14C bound residues in wheat grains. The amount of bound 14C residues present after 28 weeks of storage was about 9.9% of the applied radioactivity. Pirimiphos-methyl accounted for 80% of the bound residue. Grain-bound residues were fed to rats for 5 days. After a total period of 8 days a substantially large percentage of the administered bound 14C residues (72.9%) was eliminated in urine while feces contained only 17.9%. Bound pirimiphos-methyl in wheat grain was metabolized in rats by processes involving hydrolysis, N-dealkylation and 0-demethylation. The results indicate that wheat-bound residues of pirimiphos-methyl are highly bioavailable to the rat and may possess a toxicological potential as manifested by a significant reduction in body weight gain.     

Bioavailability to rats and toxicological potential in mice of bound residues of malathion in beans.

Under conditions of local practice, the application of 2,3-succinate-14C-malathion on beans led to the formation of 17-18% of bound 14C-residues after 30 weeks. When fed to rats, 75% of these residues became bioavailable after 2 days with the major part, excreted via expired air (8%) and urine (60%). The main radioactive metabolites detected in urine were malathion monocarboxylic acid and malathion dicarboxylic acid. Feeding of bound residues to mice (1.8 ppm in feed) for 90 days resulted in a reduction in body weight gain after 60 days and inhibition of erythrocyte cholinesterase activity after 90 days. Increased levels of serum glutamic oxaloacetic transaminase and alkaline phosphatase were also observed. The results strongly suggest that bean-bound malathion residues can cause adverse biological effects in mice.     

Bioavailability and toxicological potential of lentil-bound residues of malathion in rats.

Lentil grains treated with malathion and stored under laboratory conditions for 12 months formed bound residues. Bioavailability and the effects of lentil-bound residues of malathion in rats were studied. The amount of bound residues in lentils treated with 14C-malathion at 10 ppm and 50 ppm gradually increased to 9.52% and 13.01% of the initially applied doses after 12 months. When rats were fed these 14C-bound residues, radioactivity excreted in urine accounted for 34.49% of the administered dose. In feces, 26.15% of given dose was methanol-extractable while 18.67% was determined as nonextractable. Various tissues including liver, kidney, fat and lungs contained 8.93% while radioactivity in expired air (14CO2) was low (1.51%). The results indicate that lentil-bound malathion residues are highly bioavailable to rats. Analysis of the lentil material containing bound residues indicated that the main compound was malathion. Lentil-bound malathion residues were administered to albino rats at 0.95 and 6.51 ppm in the feed for 3 months. Body weights were determined during and at the end of the experiment. Terminal organ weights were also determined and a number of blood chemistry parameters were examined. A significant reduction in serum cholinesterase activity and an increase in blood urea nitrogen and in white cell count suggest a toxocological potential of the bound residues.     

Biological activity and bioavailability of grain bound 14C-malathion residues in rats.

Paddy (unmilled rice), milled rice and maize-bound 14C residues were prepared using 14C-succinate-labelled malathion at 10 and 152 ppm. After 3 months, the bound residues accounted for 12%, 6.5% and 17.7% of the applied dose in paddy, milled rice and maize respectively in the grains treated at 10 ppm. The corresponding values for the 152 ppm were 16.6%, 8.5% and 18.8%. Rats fed milled rice - bound 14C-residues eliminated 61% of the 14C in the faeces and 28% in the urine. The corresponding percentages for paddy and maize were 72%, 9% and 53%, 41% respectively; indicating that bound residues from milled rice and maize were moderately bioavailable. When rice-bound malathion residues (0.65 ppm in feed) were administered to rats in a 5 week feeding study, no signs of toxicity were observed. Plasma and RBC cholinesterase activities were slightly inhibited: blood urea nitrogen was significantly elevated in the test animals. Other parameters examined showed no or marginal changes.     

Biological activity and bioavailability of grain bound 14C‐malathion residues in rats

Abstract

Paddy (unmilled rice), milled rice and maize‐bound ¹⁴C residues were prepared using ¹⁴C‐succinate‐labelled malathion at 10 and 152 ppm. After 3 months, the bound residues accounted for 12%, 6.5% and 17.7% of the applied dose in paddy, milled rice and maize respectively in the grains treated at 10 ppm. The corresponding values for the 152 ppm were 16.6%, 8.5% and 18.8%. Rats fed milled rice ‐ bound ¹⁴C‐residues eliminated 61% of the ¹⁴C in the faeces and 28% in the urine. The corresponding percentages for paddy and maize were 72%, 9% and 53%, 41% respectively; indicating that bound residues from milled rice and maize were moderately bioavailable. When rice‐bound malathion residues (0.65 ppm in feed) were administered to rats in a 5 week feeding study, no signs of toxicity were observed. Plasma and RBC cholinesterase activities were slightly inhibited: blood urea nitrogen was significantly elevated in the test animals. Other parameters examined showed no or marginal changes.     

Bioavailability and toxicological potential of sunflower-bound residues of (14)C-chlorpyrifos insecticide in rats

Sunflower plants were treated with (14)C-chlorpyrifos under conditions simulating local agricultural practice. Residues present in the oil, methanol extract and cake of the treated sunflower seeds were 7.2, 2.8, and 12 ppm, respectively. When rats fed on sunflower cake containing bound residues for three days, the animals eliminated 46 % of the radioactivity in urine, 25 % in feces and 10 % in the expired air. A further bioavailable amount of 8 % was found in selected organs indicating that the bound residues were highly bioavailable. Chromatographic analysis of urine extract revealed the presence of the parent compound, its oxon, desethyl chlorpyrifos and desethyl chlorpyrifos oxon as free metabolites in addition to a conjugated metabolite. It was liberated by acid hydrolysis and identified as 3,5,6-trichloro-2-hydroxypyridine. Bound residues were found to have biological effects such as inhibition of rat plasma ChE, elevations of liver parameters (ALT, AST, and ALP), decrease in total protein and albumin content suggesting a hepatotoxic potential. A significant increase in the values of creatinine, urea, cholesterol, triglycerides and significant decrease in Catalase and Glutathion-S-Transfrase were observed in treated rats.     

Bioavailability to rats and toxicity in mice of carbofuran residues bound to faba beans.

14C-carbofuran penetrated readily into seeds of Vicia faba and the rate of penetration was found to be dose dependent. The percentage of bound residues was generally low and did not exceed 3% of the applied dose. When the bound residues were fed to rats 46% of the radioactivity was eliminated via CO2 and urine, while tissues contained 25%. Carbofuran phenol and 3-hydroxy carbofuran represented the main metabolites in the urine. These data indicate that bean-bound carbofuran residues are highly bioavailable to rats. Feeding mice with bound carbofuran residues for 90 days led to inhibition of erythrocyte cholinesterase activity after 30 days (35-40%) while the plasma enzyme remained unaffected. Serum transaminases and blood urea nitrogen were significantly elevated, indicating injury to hepatic and renal structures. The results strongly suggest that the bound residues can induce adverse biological effects in mice.     

Bioavailability and toxicological potential of sunflower-bound residues of 14C-chlorpyrifos insecticide in rats

Sunflower plants were treated with ¹⁴C-chlorpyrifos under conditions simulating local agricultural practice. Residues present in the oil, methanol extract and cake of the treated sunflower seeds were 7.2, 2.8, and 12 ppm, respectively. When rats fed on sunflower cake containing bound residues for three days, the animals eliminated 46 % of the radioactivity in urine, 25 % in feces and 10 % in the expired air. A further bioavailable amount of 8 % was found in selected organs indicating that the bound residues were highly bioavailable. Chromatographic analysis of urine extract revealed the presence of the parent compound, its oxon, desethyl chlorpyrifos and desethyl chlorpyrifos oxon as free metabolites in addition to a conjugated metabolite. It was liberated by acid hydrolysis and identified as 3,5,6-trichloro-2-hydroxypyridine. Bound residues were found to have biological effects such as inhibition of rat plasma ChE, elevations of liver parameters (ALT, AST, and ALP), decrease in total protein and albumin content suggesting a hepatotoxic potential. A significant increase in the values of creatinine, urea, cholesterol, triglycerides and significant decrease in Catalase and Glutathion-S-Transfrase were observed in treated rats.     

Bioavailability of bound 14C residues in rats from bean plants treated with 14C-deltamethrin

Bean plants were treated with deltamethrin labeled with ¹⁴C at the methyl or benzylic position. The aerial portion of the plants was exhaustively extracted with solvents and the extracted material containing bound ¹⁴C residues was fed to rats. After 4 days 60% and 53% of the dose was excreted in feces and 31% and 20% in the urine from rats fed extracted bean plants treated with deltamethrin labeled at the methyl and benzylic position, respectively. The data demonstrated that bound residues in bean plants treated with deltamethrin may be bioavailable in rats.     

Bioavailability, biological activity and characterization of bound residues of diflubenzuron in wheat.

Wheat grain was treated with radiolabeled diflubenzuron at 100 ppm and stored for various periods; up to 6 months. The grain was surface washed, Soxhlet-extracted with methanol, and the residues determined. A relative constant amount of bound residues (4%), i.e., non-extractable radioactivity, was found 4 months after application and remained constant. More than 97% of the extractable radioactivity in the grain after 6 months was identified as diflubenzuron. When the bound residues were fed to rats, 47% of the administered dose was eliminated via the urine and the remainder via feces within 96 h. Diflubenzuron was the major component in the urine. Adding bound residues to housefly media resulted in a dose-dependent mortality of housefly pupae. Bound residues were biologically active, preventing the emergence of adult houseflies. Supercritical fluid extraction of the bound residues extracted 92% and 96% of the radioactivity associated with grain and feces, respectively. Only diflubenzuron was present in these extracts. The bioavailability and biological activity of bound residues of diflubenzuron have been demonstrated and the identity of the radioactivity was shown to be parent compound. Based on these findings, bound pesticide residues can no longer be ignored or overlooked in the evaluation of pesticide residues and their possible toxicological implications.     

Residues of lindane and its metabolites in eggs, chicks, and body tissues of hen pheasants after ingestion of lindane-14C via treated wheat seed or gelatin capsules.

Studies were carried out to investigate possible contamination of pheasants with residues of lindane used as seed dressings for the control of wireworms in cereal crops. One group of laying hen pheasants was fed 20 mg of lindane-14C in gelatin capsules while another group was fed wheat seed treated with 100 ppm of lindane-14C for 15 days. Residues in eggs were monitored for about 70 days. Residues in chicks hatched from the eggs were also measured. Concentrations of residues in muscle, liver, brain, and fatty tissues were determined at various times. 14C-labeled residues in eggs increased sharply in the capsule treated group and reached an average maximum of about 19 ppm in 8 days. This level decreased to less than 0.5 ppm in about 50 days. Residues in eggs from the pheasants fed treated seed increased gradually to an average maximum of 17 ppm 22 days after commencement of the feeding program. This level decreased to less than 0.5 ppm 50 days later. Residues in hatched chicks were significantly lower than those in the eggs. Highest concentrations of residues were found in fatty tissues which decreased to non-detectable level in 6 months. Several chlorobenzene metabolites were identified in egg yolk and chick tissues. Chlorophenolic metabolites were indicated only in chicks.     

Persistence of deltamethrin and cypermethrin on wheat and sweetclover

Residues of cypermethrin and deltamethrin in wheat herbage and grain and deltamethrin in sweetclover herbage were determined. Cypermethrin was applied at 28 g/ha to wheat and the residues on the herbage declined exponentially from 3.74 ppm immediately after spraying to 0.20 ppm 27 days after spraying. No cypermethrin residues were detected in the grain. Deltamethrin was applied at 6 g/ha to wheat and the residues on the herbage declined exponentially from 0.70 ppm immediately after spraying to 0.05 ppm 27 days after spraying. No deltamethrin residues were detected in the grain. Deltamethrin was applied to sweetclover at 3, 4, 5, 10, and 16 g/ha. Residues on the herbage declined exponentially from 0.10, 0.16, 0.22, 0.40 and 0.70 ppm immediately after spraying to 0.02, 0.03, 0.04, 0.15 and 0.18 ppm 5 days after spraying, respectively.     

Disappearance of bromopropylate residues in artichokes, strawberries and beans

Residues of Bromopropylate were determine in artichokes, strawberries and beans after foliar spray of acaricide at two rates. The rates used were 1 g/l formulated product (normal recommended) and 1.5 g/l. The residue levels of bromopropylate in the three crops after 14 days were lower than 0.7 ppm and did not exceed the Maximum Residual Level (MRL) recommended by FAO. In the artichokes and strawberries, the total concentration of residues decreased by 50% of the initial level after 2-3 days. Only trace levels of the bromopropylate residues (less than 0.01 ppm) were detected in the "hearts" of the artichokes. Bromopropylate residues in the green beans were also less than 0.8 ppm after the first day of foliar spraying. The kinetic of degradation occurred in two different steps. In the first step (4-6 days) the dissipation of bromopropylate was faster whereas in the second step (7-14 days) the loss of residues was much slower.     

Persistence of deltamethrin and cypermethrin on wheat and sweetclover

Abstract

Residues of cypermethrin and deltamethrin in wheat herbage and grain and deltamethrin in sweetclover herbage were determined. Cypermethrin was applied at 28 g/ha to wheat and the residues on the herbage declined exponentially from 3.74 ppm immediately after spraying to 0.20 ppm 27 days after spraying. No cypermethrin residues were detected in the grain. Deltamethrin was applied at 6 g/ha to wheat and the residues on the herbage declined exponentially from 0.70 ppm immediatly after spraying to 0.05 ppm 27 days after spraying. No deltamethrin residues were detected in the grain. Deltamethrin was applied to sweetclover at 3, 4, 5, 10, and 16 g/ha. Residues on the herbage declined exponentially from 0.10, 0.16, 0.22, 0.40 and 0.70 ppm immediatly after spraying to 0.02, 0.03, 0.04, 0.15 and 0.18 ppm 5 days after spraying, respectively.     

Bioavailability to rats of 14C‐lindane residues in stored potato tubers

Abstract

Potato tubers were applied with radiolabelled lindane (U‐¹⁴C γ‐ 1,2,3,4,5,6 hexachlorocyclohexane) at three dose levels 30, 150, and 300 ppm and stored for 30, 60 and 90 days at room temperature. The data revealed that lindane penetrated into the pulp tissues through the epidermal layer. The amounts recovered in the peel were found to increase with a greater storage period up to 60 days followed by a drop at 90 days. On the other hand, there was a slight increase in radioactivity in the pulp tissue from 30 to 60 days followed by significant increase after 90 days. The incorporation of the compound in the tubers was dose independent. Methanol extraction showed binding of about 8.1% and 5.8% ofthe applied dose in peel and pulp tissues, respectively. The insecticide was found to be bioavailable when rats health hazard. It is therefore, desirable to demonstrate that the quantity of the terminal residues may be safe for the consumer. In the present investigation an attempt was made to determine the fate and bioavailability of lindane when applied to stored potato tubers.     

Persistence, degradation and leaching of coumaphos in soil

Dissipation, degradation and leaching of fresh 14C coumaphos, alkylated 14C coumaphos and aged residues of 14C coumaphos from vats were studied in alkaline sandy loam soil in soil columns in the field under subtropical conditions in Delhi for a year. Dissipation, degradation and bound residue formation was more in case of alkali treated coumaphos than fresh coumaphos. After 365 days total residues of fresh coumaphos accounted for 33.25% while that of alkali treated coumaphos was 19.12%. Bound residue formation was almost double in case of alkali treated coumaphos (18.95%) than fresh coumaphos (9.53%) after 150 days followed by release of bound residue in both the cases. The proportion of metabolites 4-methylumbelliferone, chlorferon and potasan collectively was 86.05% in fresh coumaphos extractable residues while the same was 91.74% in alkali treated coumaphos after 365 days. Aged residues from vats containing copper sulphate and buffer were found to be more persistent in soil as total residues remained were 95.58% in comparison with 83.09% total residues of aged residues from vats containing only buffer after 150 days of treatment. Copper sulphate seems to inhibit the degradatiion of coumaphos in soil by microorganisms. Chlorferon was the major metabolite in generally all the samples. Coumaphos did not leach below 10 cm in all the cases.     

Deltamethrin residues in milk and tissues of lactating dairy cows.

Lactating dairy cows were fed deltamethrin (2 or 10 mg kg-1 feed) for 28 consecutive days and deltamethrin residues measured in milk and tissues. Deltamethrin residues were higher relative to dose administered. The order of relative concentrations of deltamethrin in tissues, measured 1, 4, and 9 days after the last dose was: renal fat greater than subcutaneous fat greater than forequarter muscle greater than hindquarter muscle greater than liver greater than kidney. Depletion of deltamethrin residues in milk was very rapid indicating the half-life of the insectide of about 1 day. Trace amounts of deltamethrin metabolites 3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane carboxylic acid (less than 0.0235 ppm) and 3-phenoxybenzoic acid (less than 0.034 ppm) were also detected in milk and tissues of treated cows.     

Studies of methamidophos-C-14 in Costa Rican vegetables and soils

In order to see the effect of time lapse between the last application of methamidophos and harvesting insecticide was applied on lettuce plants (6,84 μCi in one experiment and 4,03 μCi in the other experiment). Analysis of the crops harvested 3 days after last application showed 9,7 ppm residues on leaves, while crops harvested 1 day after application showed residues of 12,7 ppm (25% more). Treatment of tomato plants (39,65 μCi, 1,01 kg/ha) gave residues in fruits 4,92 ppm after 8 days interval between last application and harvesting. 40 days gap between the last application and harvesting leaved residues of 0,7 ppm in fruits which is much less as recommended by FAO/WHO (1 – 2 ppm).Degradation of this insecticide is dependent on the matrix of the soil, this breakdown is observed in the first ten days and than after it remains constant. C-14 radioactivity extracted from soil and plant analysis was methamidophos (92%)