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Coumaphos distribution in the hive ecosystem: case study for modeling applications.

Pesticides are currently used inside hives, against the honeybee parasite Varroa destructor, producing unwanted contamination effects. To assess the distribution and fate of one of these pesticides (coumaphos), two experimental hives were treated with Perizin (the commercial product containing the active ingredient coumaphos). Samples of honey, wax, pollen, adult bees and larvae taken before treatment and up to 104 days afterwards, showed diffuse contamination. Wood hedges and wax bridges, where the pesticide solution was applied, were analysed as well. A mass balance was calculated, yielding a recovered amount of around 60% just after treatment and 38% 1 month later. Directly contaminated surfaces and wax contained the highest amount of residues. Wax and honey contained different amounts (10, and 0.1% respectively) but both retained residues for long time. Bees ingest most of the product just after treatment, then rapidly eliminate it by metabolism, advection and deposition processes. On the basis of analytical results, a simple model (level I of the fugacity model) was applied to the hive system for different pesticides (coumaphos, malathion, fluvalinate and bromopropylate). Predicted concentrations in wax and honey were compared with those measured, indicating the good predictive capability of this approach.

Animals↗

Coumaphos intoxications mimic food poisoning.

Reports of food poisoning caused by pesticide-contaminated food are rare in the medical literature. In this paper, we report six patients who suffered food poisoning in two separate episodes in which the pesticide coumaphos was apparently misused as a food flavoring. These six patients presented not only the general manifestations of gastroenteritis, but also some unusual extraintestinal symptoms. These included cholinergic overactivity (miosis, urinary incontinence and hypersalivation) that led us to suspect organophosphate intoxication. This diagnosis was confirmed by serial changes in RBC cholinesterase and pseudocholinesterase activity, and by the presence of coumaphos in the contaminated food. Of the six patients, one was dead on arrival. Another patient developed progressive respiratory failure and required mechanical ventilation. The mortality rate among our cases was 16.7%. Since the coumaphos was apparently added to food during cooking, its toxic effects do not appear to be mitigated by heating. When food poisoning cases present with both gastroenteritis and unusual autonomic symptoms, the autonomic syndromes will aid in the diagnosis and management of these critically ill patients.

Adult↗

Repeated oral administration of coumaphos in sheep: effects on erythrocyte acetylcholinesterase and other constituents.

The effects of treating adult wethers with 2 or 4 mg of coumaphos/kg of body weight each day for 6 days were investigated. The smaller dose produced a gradual decrease of erythrocyte acetylcholinesterase (AChE) activity (to maximum average reduction of approximately 45%), but without the appearance of signs of toxicosis. The larger dose appeared to be toxic. Treatment with the drug did not seem to alter significantly the anticholinesterase effects of a 2nd treatment made 6 weeks later. Coumaphos did not significantly affect serum activities of aspartate aminotransferase (glutamic oxalacetic transaminase) or isocitrate dehydrogenase (ICD) and concentrations of serum sodium and plasma calcium. A marked decrease in blood serum potassium and an increase in plasma magnesium occurred in all wethers that died after treatment with coumaphos, whereas appreciable changes did not occur in the survivors of the treatment given 6 weeks earlier. Treatment of sheep with an intravenous injection of the organophosphorous compound trichlorfon, insufficient to produce a significant effect on erythrocyte cholinesterase activity, produced additive effects with those of coumaphos.

Acetylcholinesterase↗

[Resolution of synchronous fluorimetric spectrum for carbaryl and coumaphos and its application study].

The synchronous fluorimetric method for the simultaneous determination of carbaryl and coumaphos is described. In the Britton-Robinson buffer at pH 3.0, synchronous scanning with deltalambda= 60 nm was carried out, and the overlapped fluorimetric spectra were better separated. The two synchronous fluorimetric peaks are located at 280 and 322 nm respectively, and can be used for the determination of these two pesticides. No preliminary separation is needed. The method is simple, rapid and successfully applied to the analysis of food samples. The linear ranges of the calibration curves for carbaryl and coumaphos are 0.016-0.384 microg x mL(-1) and 0.016-0.320 microg x mL(-1), respectively. The limits of detection are 0.015 microg x mL(-1) for carbaryl, and 0.010 microg x mL(-1) for coumaphos.

Carbaryl↗

Bioassay of coumaphos for possible carcinogenicity.

A bioassay of coumaphos for possible carcinogenicity was conducted by administering the test chemical in feed to F344 rats and B6C3F1 mice. Groups of 50 rats of each sex and 50 mice of each sex were administered the coumaphos in the diet at one of two doses, either 10 or 20 ppm, for 103 weeks and then observed for 0-1 additional weeks. Matched controls consisted of groups of 25 untreated animals of each species and sex. All surviving animals were killed at 103-105 weeks. Mean body weights of the dosed female rats were lower than those of corresponding controls, while mean body weights of dosed male rats and of dosed male and female mice were essentially unaffected. No clinical signs that are typical of organophosphorus poisoning were reported in either rats or mice. Survival of the rats and mice was not affected by administration of the test chemical. The test animals may have been able to tolerate higher doses. Sufficient numbers of animals in all groups of the rats and mice were at risk for the development of late-appearing tumors. In both rats and mice, no tumors occurred in the dosed groups of either sex at incidences that were significantly higher than those in corresponding control groups. It is concluded that under the conditions of this bioassay, coumaphos was not carcinogenic for either F344 rats or B6C3F1 mice.

Journal Article↗

Efficacy of coumaphos applied as a dip for control of an organophosphorus-resistant strain of Boophilus microplus (Acari: Ixodidae) on cattle.

The efficacy of coumaphos, an organophosphorus acaricide, was tested on a strain of Boophilus microplus (Canestrini) that was 9.5 times more resistant to the chemical than a susceptible strain. Cattle infested with larval, nymphal, and adult ticks were dipped into a vat charged at concentrations of 0.031, 0.083, 0.160, and 0.279% (AI). Assessment of efficacy was based on surviving tick numbers, female weight, egg mass weight, egg hatchability, and index of reproduction. At 0.031% (AI), the level of control was lower than the other coumaphos treatments, and the weight, fecundity, and fertility of surviving females was similar to untreated females, indicating only minimal adverse effects on the ticks. At 0.160 and 0.279% (AI), no differences in control, female weight, egg mass weight, or percentage egg hatch were observed, but effects were greater than that of untreated ticks or ticks treated at 0.031% (AI). At 0.083% (AI), most biological parameters were intermediate, but there was no difference in control compared with the 2 higher concentrations. Thus, even with the increase in concentration of more than 3 times between treatments of 0.083 and 0.279% (AI), there was no substantial increase in control. The residual efficacy of all 4 treatments showed that none provided complete protection against larval reinfestation for even 1 wk after treatment. Therefore, the presence of organophosphorus-resistant ticks at U.S. ports-of-entry could jeopardize the success of the Boophilus eradication program.

Animals↗

Characterization of pyrethroid resistance and susceptibility to coumaphos in Mexican Boophilus microplus (Acari: Ixodidae).

Two patterns of pyrethroid resistance were characterized from Boophilus microplus (Canestrini) collected in Mexico. One was characteristic of a kdr mutation and the other involved esterase and cytochrome P450 enzyme systems. Very high resistance to permethrin, cypermethrin, and flumethrin, not synergized by TPP and PBO and high resistance to DDT, characterized the kdr-like pattern found in the Corrales and San Felipe strains. Esterase and cytochrome P450-dependent resistance was found in the Coatzacoalcos strain. It was characterized by resistance to permethrin, cypermethrin, and flumethrin, synergized by TPP and PBO, but no resistance to DDT. The Coatzacoalcos strain also showed 3.6-fold resistance to the organophosphate coumaphos. This factor appeared to be independent of pyrethroid resistance. Pyrethroid resistance patterns found in Mexico were similar to those found earlier in Australia. The significance of pyrethroid and coumaphos resistance to the U.S. cattle fever tick quarantine is discussed.

Animals↗

Determination of malathion, coumaphos, and fluvalinate residues in honey by gas chromatography with nitrogen-phosphorus or electron capture detectors.

A rapid, reliable, and inexpensive extraction method was developed to determine acaricide residues in honey by gas chromatography (GC) with nitrogen-phosphorus (NP) or electron capture (EC) detectors. Because of the high selectivity of the NP detector, no interfering peaks were present and no cleanup was necessary. A simple cleanup step is proposed for the GC-ECD analysis. Recoveries from spiked honey samples ranged from 79 to 94.4%, with coefficients of variation of 0.3-18.5%. The quantitation limit obtained was 0.015 mg/kg for malathion, 0.020 mg/kg for coumaphos, and 0.005 mg/kg for fluvalinate. The method was used to determine the disappearance of malathion and coumaphos residues from honey samples collected from beehives treated with these acaricides. The disappearance of both acaricides was rapid and followed a first-order model for the duration of the experiment.

Chromatography, Gas↗

Optimization of sweep codistillation apparatus for determination of coumaphos and other organophosphorus pesticide residues in animal fat.

Optimum conditions have been developed for the quantitative recovery of coumaphos from animal fat by using a commercial sweep codistillation unit. Under the conditions specified (255 degrees C distillation temperature, 250 mL/min of nitrogen, 60 min sweep time) and using Florisil trapping, the mean recovery of coumaphos was 91% with a coefficient of variation of 6%. Other organophosphorus pesticides recovered include diazinon, chlorpyrifos, ethion, and bromophos-ethyl with recoveries ranging from 90 to 96% and coefficients of variation ranging between 4 and 6%.

Animals↗

Efficacy of coumaphos crumbles and naftalofos boluses against nematodes of cattle.

Coumaphos crumbles (0.32%) administered to cattle at the dose level of 2 mg of active ingredient per kilogram of body weight each day for 6 days reduced fecal egg counts by 98.4%. The compound was highly efficacious in removing adult worms of the genera Haemonchus, Ostertagia, Trichostrongylus, Cooperia, Oesophagostomum, and Trichuris, removing 99.8, 86.7, 95.9, 99.8, 74.8, and 90.9% of the worms, respectively. The overall efficacy of coumaphos crumbles against the adult forms of the 6 genera was 91.3%. Naftalofos boluses administered to cattle at the dose level of 50 mg of active ingredient per kilogram of body weight reduced fecal egg counts by 83.5%. The efficacies against adult nematodes were as follows: Haemonchus, 99.8%; Ostertagia, 86.9%; Trichostrongylus, 74.0%; Cooperia, 71.9%; Oesophagostomum, 40.1%; and Trichuris, 87.9%. The overall efficacy of naftalofos boluses against the nematodes was 76.8%.

Animals↗

Determination of residual bromopropylate and coumaphos in honey and honeycomb by capillary gas chromatography.

This study describes a method for the quantitative determination of residual bromopropylate (BP) and coumaphos (Cph) in honey and honeycomb. It is based on a reversed phase extraction technique on sorbent octadecyl. Both phyto-pharmaceuticals are determined by electron-capture using a fused silica capillary column CP Sil 5 CB. The absolute detection limit for BP and Cph is 2.5 and 5 pg, respectively. Recoveries of 99.6% and 94.4% are obtained for samples fortified at levels of 400 micrograms BP/kg and 1,000 micrograms Cph/kg. Twelve samples of honey and 8 samples of honey-honeycomb have been analysed using this method. BP and Cph could not be detected in the honey samples. Samples of honey-honeycomb recently treated with Perizin (Cph) and Folbex VA (BP) contained different amounts of BP and Cph.

Animals↗

Synthesis of (Diethyl-d(10)) coumaphos and related compounds.

Two deuterated insecticides were prepared for use as internal standards for gas-liquid chromatographic-mass spectrometric analyses. Diethyl chlorothiophosphate-d(10) was prepared by reaction of ethanol-d(6) with P(2)S(5) to give labeled diethyldithiophosphoric acid, followed by chlorination. Treatment of the acid chloride with 3-chloro-4-methyl-7-hydroxycoumarin and potassium carbonate in acetone at reflux gave labeled coumaphos. An analogous reaction with 4-methyl-7-hydroxycoumarin gave labeled potasan, and the technique should be usable for synthesis of labeled forms of other dialkyl thiophosphate insecticides.

Coumaphos↗

Systemic activity of coumaphos, famphur, crufomate, ronnel, and phosmet given orally to hens for control of the northern fowl mite, Ornitbonyssus sulviarum (Canestrini and Fanzago).

Coumaphos (O-(3-chloro-4-methyl-2-oxo-2H-1-benzopyran-7-yl)O,O-diethyl phosphorothioate), famphur (O-[p-(dimethylsulfamoyl)phenyl] O,O-dimethyl phosphorothioate). crufomate (4-tert-butyl-2-chlorophenyl methyl methylphosphoramidate), ronnel (O,O-dimethyl O-(2,4,5-trichlorophenyl) phosphorothioate) and phosmet (O,O-dimethyl phosphorodithioate S-ester with N-(mercaptomethyl) phthalimide) were administered as systemic acaricides (either single or multiple oral doses or as feed additives) for control of the nortnern fowl mite, Ornithonyssus sylviarum (Canestrini and Fanzago), on caged White Leghorn hens. None of the treatments controlled the mites, but some hens were poisoned.

Animals↗

Determination of coumaphos and its oxygen analog in eggs by in situ fluorometry.

A method is reported for the simultaneous determination of coumaphos (o,o-diethyl o(3-chloro-4-methyl-2-oxo-2H-1-benzopyran-7-yl)phosphorothioate) and its oxygen analog, Coroxon, in eggs in the ppb range. The residues are extracted with acetone and chloroform. The extract is purified by liquid-liquid partition followed by column chromatography and then by 2-dimensional thin layer chromatography. The fluorescence is measured directly on the chromatogram.

Animals↗

Acute oral median lethal dose of haloxon and coumaphos in sheep as influenced by plasma A esterase.

Determination of the acute oral medial lethal dose (LD50) of haloxon for lambs classified as to the presence or absence of plasma esterases (A esterase; EsA) rapidly hydrolyzing haloxon revealed markedly different values for the 2 phenotypes of sheep. The LD50 for EsA- lambs was 763 mg/kg of body weight with 95% confidence limits of 543 to 1,072 mg/kg. The acute oral LD50 for EsA+ lambs remains undetermined but was demonstrated to be in excess of 11,392 mg/kg. The acute oral LD50 for a closely related organophosphate (coumaphos) was not different in the 2 phenotypes of sheep.

Administration, Oral↗

Influence of dietary protein on the effect of coumaphos and triflupromazine interaction in sheep.

Coumaphos (8 or 15 mg/kg of body weight), triflupromazine HCl (1.1 mg/kg of body weight), or isotonic saline solution were given to 8 groups of sheep (5 per group) fed a low-or normal-dietary protein ration. One set of clinical signs, mortality rate, mean survival time, necropsy lesions, and plasma and erythrocyte cholinesterase (ChE) activity were monitored for each group. Observations suggested potentiation effect between the administered compounds. Inhibition of ChE activity was enhanced in groups given both drugs. Feeding of low-dietary protein ration adversely affected the development of clinical signs, mortality rate, mean survival time, and ChE activity. Recovery of ChE activity of triflupromazine HCl-treated animals was faster than in their respective controls, and sheep fed normal-dietary protein ration had faster ChE recovery than those fed the low-dietary protein ration. Inhibition of erythrocyte ChE found was a better index of organophosphorus toxicosis than that of plasma ChE.

Animals↗

Biotransformation and disposition of the coumaphos metabolite 3-chloro-4-methyl-(4-14C)-7-hydroxycoumarin in rats.

The biotransformation and disposition of 3-chloro-4-methyl-(4-14C)-7-hydroxycoumarin [(14C) chlorferron] were investigated in rats after single oral administration. Following administration of (14C) chlorferron at 0.5 and 20 mg/kg body weight to male rats, greater than 90% of the given dose was eliminated in the urine (77-84%) and faeces (7-15%) within 24 h. Low levels of (14C) chlorferron derived residues were detected in different organs of rats 7 days after dosing. Administration of (14C) chlorferron at 20 mg/kg allowed the isolation of three metabolites in the 24-h urine of male and female rats. Compounds tentatively identified were dechlorinated metabolites of chlorferron besides unchanged chlorferron. The majority of the metabolites were excreted in conjugated forms. The pattern of biotransformation of chlorferron was qualitatively similar in male and female rats. Comparative studies on the elimination and biodistribution of (14C) chlorferron and its parent compound (14C) coumaphos in male rats indicated rapid metabolism and faster elimination of chlorferron and its metabolites from the body than that of the parent compound.

Animals↗