Accumulation of endosulfan residues in fish and their predators after aerial spraying for the control of tsetse fly in Botswana

Residues of endosulfan insecticide (α- and β-isomers, and ‘endosulfan sulphate’) in fish and their predators were measured during and after operations to control tsetse fly in the Okavango Delta, Botswana. Six ultra-low-volume doses of endosulfan 35% e.c. (6–12 g a.i. ha^?1) were applied from the air in a period of 12 weeks over 2500 km². The concentration of residues found in living fish was up to 0.19 mg kg^?1 wet wt in caudal muscle, and usually < 0.8 mg kg^?1 wet wt in pooled viscera (maximum 2.8 mg kg^?1). These values returned to near-normal within 3 months after cessation of spraying, but residues were still detectable after 12 months. By comparison, fish killed by spraying contained a maximum residue level (whole-body) of 1.5 mg kg^?1 wet wt. The residue level in fish was approximately proportional to their fat content. Lean fish were more susceptible to poisoning than fat fish. The proportion of the ‘endosulfan sulphate’ metabolite in fish increased at least six times with respect to the parent isomers (α+β) during the period of spraying, but more advanced stages of metabolic breakdown were not monitored. Residue levels in fish predators (fish-eating birds and crocodiles) were similar to those in their prey, and the risk to them was consequently low.     

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     

Fate of endosulfan in rats and toxicological considerations of apolar metabolites

[¹⁴C]Endosulfan, α or β isomers separately, was administered to rats as a single oral dose and as a dietary supplement for 14 days. No appreciable differences were observed in the fate of the two isomers. Five days after the single dose, 75% of the dose had been voided in the feces and 13% in the urine. Of the total radiocarbon consumed in the diet after 14 days, 56% had been eliminated in the feces and 8% in the urine. Bile collection studies showed that up to 47% of a single oral dose was eliminated from the liver via this route; enterohepatic circulation was not apparent. Maximum [¹⁴C]endosulfan equivalents in body tissue occurred in the kidney and liver, 3 and 1 ppm, respectively, after 14 days of feeding 5 ppm of endosulfan. Apolar metabolites in the excreta and/or tissues were a minor portion of the total residues and consisted of the sulfate, diol, α-hydroxy ether, lactone, and ether derivatives of endosulfan. The sulfate was slightly more toxic to mice than endosulfan, while the other products were less toxic. Neither endosulfan nor its metabolites were active in the Salmonella mutagenicity test. Endosulfan in the diet of rats for 28 days at 50 ppm did not induce liver oxidase enzymes, alter liver or kidney weights, or influence the rate of weight gain of the animals.     

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     

Residues of zeta‐cypermethrin in bovine tissues and milk following pour‐on and spray application

The depletion of zeta‐cypermethrin residues in bovine tissues and milk was studied. Beef cattle were treated three times at 3‐week intervals with 1 ml 10 kg^?1 body weight of a 25 g litre^?1 or 50 g litre^?1 pour‐on formulation (2.5 and 5.0 mg zeta‐cypermethrin kg^?1 body weight) or 100 mg kg^?1 spray to simulate a likely worst‐case treatment regime. Friesian and Jersey dairy cows were treated once with 2.5 mg zeta‐cypermethrin kg^?1 in a pour‐on formulation. Muscle, liver and kidney residue concentrations were generally less than the limit of detection (LOD = 0.01 mg kg^?1). Residues in renal‐fat and back‐fat samples from animals treated with 2.5 mg kg^?1 all exceeded the limit of quantitation (LOQ = 0.05 mg kg^?1), peaking at 10 days after treatment. Only two of five kidney fat samples were above the LOQ after 34 days, but none of the back‐fat samples exceeded the LOQ at 28 days after treatment. Following spray treatments, fat residues were detectable in some animals but were below the LOQ at all sampling intervals. Zeta‐cypermethrin was quantifiable (LOQ = 0.01 mg kg^?1) in only one whole‐milk sample from the Friesian cows (0.015 mg kg^?1, 2 days after treatment). In whole milk from Jersey cows, the mean concentration of zeta‐cypermethrin peaked 1 day after treatment, at 0.015 mg kg^?1, and the highest individual sample concentration was 0.025 mg kg^?1 at 3 days after treatment. Residues in milk were not quantifiable beginning 4 days after treatment. The mean concentrations of zeta‐cypermethrin in milk fat from Friesian and Jersey cows peaked two days after treatment at 0.197 mg kg^?1 and 0.377 mg kg^?1, respectively, and the highest individual sample concentrations were 2 days after treatment at 0.47 mg kg^?1 and 0.98 mg kg^?1, respectively. © 2001 Society of Chemical Industry     

The effect of the annual use of pesticides on soil microorganisms,pesticide residues in the soil and barley yields

A study has been made of the influence of pesticides used annually on soil microorganisms and crop yields. The persistence of these pesticides in the soil was also investigated. The herbicides MCPA, glyphosate, maleic hydrazide and tri-allate, and the insecticide parathion, were applied on experimental plots on which barley was grown during the years 1973-1981. The fungicide 2-methoxyethylmercury chloride was used every year for dressing the seeds grown in pesticide-treated plots. The pesticide treatments did not affect significantly the numbers of several groups of soil microorganisms. A slight increase was, however, observed in the nitrification activity in the soil. The barley yields were on average higher on pesticide-treated plots than on controls because of successful weed control. Pesticide residues in the soil were generally very low; for example, for parathion they were below 0.02 mg kg^?1 within 11 days, and for MCPA 0.06 mg kg^?1 within 7 days. However, the glyphosate residue was 1.6 mg kg^?1 in the autumn 2 days after the treatment, and the residue settled to a level of 0.2 mg kg^?1 during the following summer. No clear dependence was observed between the residue level and the time between treatment and sampling.     

Residues of synthetic pyrethroid insecticides on horticultural crops

Foliar applications of synthetic pyrethroids were made to several crops to determine residue levels at various intervals after application. On onions, residues of cypermethrin, permethrin and fenvalerate were negligible > 0.1 mg kg^?1, 7 days after application. On lettuce, residues of fenvalerate and permethrin were 0.8 mg kg^?1. On celery, residues of fenvalerate did not decline and ranged from 0.12 to 0.25 mg kg^?1 during the 14-day period. On green bush-beans, residues of permethrin and cypermethrin did not decline during the 14-day period and ranged from 0.1 to 0.6 mg kg^?1. By day 7, residues of cyfluthrin, cypermethrin, deltamethrin, fenvalerate and permethrin on strawberries were less than the acceptable maximum tolerance of 0.1 mg kg^?1 with the exception of cypermethrin, applied at the rate of 0.14 kg a.i. ha^?1 which gave a residue of 0.14 mg kg^?1.     

The dietary toxicity of flocoumafen to hens: Elimination and accumulation following repeated oral administration

In a dietary toxicity study, laying hens received a diet containing the rodenticide flocoumafen at concentrations of 1.5, 5, 10 and 50 mg kg^?1 for five consecutive days. The LC₅₀ at termination following a 28-day observation period was 16.4 mg kg^?1. Livers of birds which received doses of flocoumafen between 5 and 50 mg kg^?1 had concentrations of flocoumafen (1.5 nmol g^?1) that were independent of dose. The data indicate the presence in hen liver of a saturable high-affinity flocoumafen binding site with similar characteristics and capacity to that of the quail and rat. Residues of flocoumafen in samples of breast and leg muscle were low in all exposure groups. Higher, dose-related residues were found in samples of abdominal fat and skin-associated fat and there was a clear demonstration of the transfer of dose-related residues into eggs. In a separate study in which hens were dosed with [¹⁴C]flocoumafen for five consecutive days at a daily rate of 1 and 4 mg kg^?1 body weight, the majority (68 %) of the daily radioactive dose was eliminated over the following 24 hours via excreta. Residues in liver at death or when killed accounted for < 1 % of the cumulative administered radioactivity. Residues in eggs were located primarily in the yolk with maximum concentrations 1.0 mg kg^?1 or 0.18% of the low dose; 2.1 mg kg^?1 or 0.06% of the high dose as [¹⁴C]flocoumafen equivalents were observed at 10 days after start of dosing. Some 40 % of the total activity in the yolk was unchanged flocoumafen.     

Dissipation rates of insecticides in six minor vegetable crops grown on organic soils in Ontario,Canada

Dissipation rates of diazinon, endosulfan, leptophos, methamidophos, methomyl, parathion and pirimicarb were studied on five minor vegetable crops, including cos and head lettuce, endive, cauliflower and Chinese cabbage. Residues from foliar treatment generally followed an exponential rate of decline. The number of days for residues to drop to below acceptable tolerances was highly dependent on the magnitude of the initial residue; large variations in initial residues were observed between years, between insecticides, and between crop types. Residues of five insecticides and two fungicides used in furrow treatments for onions intended for pickling were determined in the onions at harvest and after pickling. Fensulfothion and fonofos levels were below the accepted tolerance of 0.1 mg kg^?1 at harvest, while chlorfenvinphos, chlorpyrifos and ethion were present above this level; fungicide residues were not detected. Following pickling, only ethion residues were still present in the onions at levels greater than 0.1 mg kg^?1.     

Residues in blackcurrants,fodder peas,spinach and potatoes treated with sublethal doses of 2,4,5-T to simulate wind drift damage

Blackcurrants, treated with 0.1 kg of 2,4,5-T ha^?1 (as esters of mixed C₄–C₆ alcohols; ‘Tormona 80’), contained 0.1 mg of 2,4,5-T residues kg^?1 in the berries at ripeness 29 days after treatment. Total residues in the berries were not reduced during growth and ripening, although the residue concentrations declined in the same period due to growth dilution. In spinach leaves from old plants, treated with 0.1 kg ha^?1, 0.05 mg of 2,4,5-T kg^?1 was found 14 days after treatment. Fodder peas showed no residues (< 0.002 mg kg^?1) at harvest 62 days after treatment with 2,4,5-T esters. After application of 0.1 kg ha^?1 on potato plants, the disappearance of 2,4,5-T was rapid during the first month, but residues were translocated into the tubers and reached a constant level of 0.02 mg kg^?1 after 1 month until harvest at 108 days after treatment. In all crops, visible effects were observed after treatment with 0.1 kg ha^?1. After the application at 0.01 kg ha^?1, phytotoxic effects were observed only in blackcurrants, but negligible residues were found in all the test crops.     

Acaricides and their residues in Spanish commercial beeswax

BACKGROUND: The purpose of this work was to determine residues of acaricides in recycled Spanish beeswax. RESULTS: Chlorfenvinphos, fluvalinate, amitraz, bromopropylate, acrinathrin, flumethrin, coumaphos, chlorpyrifos, chlordimeform, endosulfan and malathion residues were determined by GC‐µECD/NPD/MS detection. Owing to the extreme instability of amitraz, this analyte was transformed into the stable end‐metabolite 2,4‐dimethylaniline, later derivatised with heptafluorobutyric anhydride and determined by GC‐µECD/MS. Recoveries from spiked samples ranged from 86 to 108%, while quantification limits varied from 0.10 to 0.30 mg kg^?1 using GC‐µECD/NPD, and from 12 to 85 µg kg^?1 by GC‐MSD. Of a total of 197 samples analysed, only eight samples (4%) were free of residues of chlorfenvinphos (0.019–10.6 mg kg^?1), fluvalinate was present in 93.6% of samples analysed (0.027 –88.7 mg kg^?1), while coumaphos was confirmed in only five of the 134 samples analysed at concentrations of less than 195 µg kg^?1. The remaining acaricides were identified with different levels of incidence at concentrations from 12 to 231 µg kg^?1. CONCLUSIONS: Residues of acaricides were found in an extensive number of beeswax samples. The contamination with chlorfenvinphos and tau‐fluvalinate was very relevant, particularly as chlorfenvinphos is not legally authorised for use in beekeeping. The possible impacts of the main acaricides detected on larval and adult honey bees are discussed. Copyright © 2010 Society of Chemical Industry     

Behaviour of trifloxystrobin and tebuconazole on grapes under semi‐arid tropical climatic conditions

BACKGROUND: A mixture of trifloxystrobin and tebuconazole is excellent in controlling both powdery and downy mildew of grapes. The objective of the present work was to study the behaviour of trifloxystrobin and tebuconazole on grape berries and soil following treatment with Nativo 75 WG, a formulation containing both fungicides (trifloxystrobin 250 + tebuconazole 500 g kg^?1). This study was carried out for planned registration of this mixture for use on grapes in India. RESULTS: Initial residue deposits of trifloxystrobin and tebuconazole on grapes were below their maximum residue limit (MRL) of 0.5 and 2 mg kg^?1, respectively, when Nativo 75 WG was applied at the recommended dose of 175 g product ha^?1. The residues dissipated gradually to 0.02 and 0.05 mg kg^?1 by 30 days, and were below the quantifiable limit of 0.01 mg kg^?1 at the time of harvest (60 days after the last treatment). Trifloxystrobin and tebuconazole dissipated at a pre‐harvest interval (PHI) of 36 and 34 days, respectively, from the recommended treatment dose. The acid metabolite of trifloxystrobin, CGA 321 113, was not detected in grape berries at any point in time. Soil at harvest was free of any pesticide residues. CONCLUSION: Residue levels of both trifloxystrobin and tebuconazole were below MRLs when grapes were harvested 30 days after the last of four applications of 175 g product ha^?1 (trifloxystrobin 44 g AI ha^?1, tebuconazole 88 g AI ha^?1) under the semi‐arid tropical climatic conditions of India. Copyright © 2010 Society of Chemical Industry     

Dissipation of cyproconazole and quinalphos on/in grapes

The persistence of cyproconazole and quinalphos on/in grapes was investigated when both compounds were applied to vines at the locally recommended application frequencies and rates and at double these rates, using commercially available formulations. Residues of cyproconazole applied at recommended and double the recommended rates of application in/on grapes immediately after the last application were 0-049 (±0.034) and 0.077 (±0.008) mg kg^?1, respectively, reduced to 0.011 (±0.003) and 0.018 (±0.010) mg kg^?1 respectively seven days after the last application. The corresponding residue levels of quinalphos immediately following the last application were 1.42 (±0.10) and 3.36 (±0.07) mg kg^?1, reduced to 0.043 (±0.002) and 0.072 (±0.028) mg kg^?1 respectively 21 days after the last application. Cyproconazole, being systemic, is rapidly absorbed by the grape tissues and its residues dissipate with a half-life of three to four days, while quinalphos, being non-systemic, dissipates faster with a half-life of two or three days. The residues of both pesticides were analysed by a GLC-NPD system.     

Gamma-HCH in rape seedlings grown from treated seeds

Rape seedlings grown from seeds treated with a gamma-HCH seed dressing at a dose rate of 15.7 g kg^?1 had a maximum gamma-HCH concentration of 380 mg kg^?1 in seedlings collected 1 day after emergence. The mean gamma-HCH concentration in the seedlings decreased to 2.6 and to 0.9 mg kg^?1 by 7 and 15 days after emergence, respectively. Gamma-HCH was chemically detected in true leaves, at concentrations up to 1.9 mg kg^?1, indicating translocation of gamma-HCH in young plants.     

The HPLC determination of residues of maleic hydrazide in cloves of garlic bulbs following foliar application

A method was developed for the extraction and HPLC analysis of the plant growth regulator maleic hydrazide (MH) from garlic bulbs. Recovery of MH from fortified garlic tissue was 75.8(±6.1)% at the 1 and 2 mg kg^?1 fortification levels. MH residues were determined by HPLC in cloves of garlic bulbs following treatment at three sites in southern Ontario with foliar applications at 3.75 kg ha^?1. MH residues in the cloves were in the order of 3 mg kg^?1 at two sites, and 11 mg kg^?1 at the third side.     

The effect of the annual use of some pesticides on soil microorganisms,pesticide residues in soil and carrot yields

The study deals with the effect of common, annually-used pesticides on soil microorganisms, pesticide residues in soil, and carrot (Daucus carota) yields in Central Finland. Linuron residues in carrot roots were also analysed. Thiram+lindane and dimethoate were applied from 1973–1981 at the commercially recommended doses on experimental plots of carrots, linuron was applied at twice the recommended rate from 1973–1979 and at the normal rate thereafter and in addition TCA was applied in 1978. Maleic hydrazide was used in the years 1973–1976, and glyphosate after 1977. The numbers of different soil microorganisms, their activities and the pesticide residues were studied from autumn 1978 to 1981. The pesticide treatments reduced the growth of soil algae but increased the total number of microorganisms and the number of aerobic spore-forming bacteria. Linuron residues in the soil were 0.9–2.8 mg kg^?1 in the growing season and 1.2–1.7 mg kg^?1 in the autumn, 3 months after application. The residues of glyphosate in the soil were 0.7 mg kg^?1 in the autumn, 41 days after the treatment, and had declined to a level of about 0.2 mg kg^?1 by the following summer. In the pesticide-treated plots the carrot yield was only 20–60% of the yield in the hand-weeded plots. The herbicide programme controlled most of the annual weeds but not couchgrass Elymus repens and milk sow-thistle Sonchus arvensis.     

Disappearance of carbosulfan residues in peaches

The disappearance kinetics of the carbamate insecticide, carbosulfan, applied at 2 kg AI ha^?1 (‘Marshal’ 250 g litre^?1 EC) in peaches was studied. Degradation took place in two consecutive stages (0–28 and 28–57 days), with half-lives of 7.4 and 17.5 days, respectively. The residues obtained 57 days after treatment did not exceed 0.2 mg kg^?1. When treatments were carried out 30, 21 and 14 days before the probable date of harvest (date of fruit maturation) with two doses (1.0 and 2.0 g formulated product litre^?1) and two volumes applied (750 and 1500 litre ha^?1), the residual levels detected were between 0.122 mg kg^?1 (30 days before harvest) and 0.4 mg kg^?1 (14 days before harvest). The major metabolite, carbofuran, was never detected above its determination limit of 0.004 mg kg^?1 throughout the whole study.     

Residues of the algicide endothal in water,soil and rice,after paddy field applications

In order to obtain residue data from the application of the algicide endothal in Italian rice paddy fields, two experiments were carried out using a 50 g kg^?1 granular formulation in a small pond and the same granular and two liquid formulations in actual paddy fields of the Italian rice growing area. Endothal decay in the pond water was very rapid, reaching residue levels of 0·01-1·02 mg litre^?1 in two days and 0·004-0·01 mg litre^?1 at the third day. The muddy soil of the pond was free from measurable endothal residues( <0·02 mg kg^?1). In the paddy-field waters, the endothal decay was slower, with an average half-life time of 3·3 days, independently of the type of formulation. The actual residues in water after 6 days ranged from 0·3 to 1·3 mg litre^?1 according to the initial amount of product applied, and, consequently, to the initial concentration in water. Rice samples collected at the normal harvest time from the two paddy fields, treated with three different formulations, showed no endothal residue at the minimum detectable level of 0·01 mg kg^?1.     

The metabolism of tefluthrin in the goat

A goat was dosed orally with [¹⁴C]tefluthrin, twice daily for 4 days, at a rate equivalent to 10.9 mg kg^?1 in its diet. Within 16 h of the final dose, 70.1% of the dose had been excreted (urine 41.4%, faeces 28.7%). Extensive metabolism occurred in the goat by ester cleavage and oxidation at a variety of positions on the molecule. Low radioactive residues were detected in the milk (0.076 mg kg^?1), fat (0.076 mg kg^?1) and muscle (0.016 mg kg^?1), with tefluthrin as the largest individual component of the residue (milk 66.5%, fat 76.7%, muscle 34.2%). Higher residues were present in the kidney (0.3 mg kg^?1) and liver (1.0 mg kg^?1) and only a small percentage of this residue was due to tefluthrin (kidney 3.4%, liver 6.1%). The remainder of the residue in the kidney and liver was a complex mixture of metabolites. Most of the kidney metabolites were identified, but a high proportion of the liver residue was due to six unidentified polar compounds.     

Residues of Mecoprop in Post-emergence-Treated Wheat and Oat

The dissipation of mecoprop in wheat (Triticum aestivum L.) and oat (Avena sativa L.) was monitored over a growing season following post-emergence application of the dimethylamine salt of mecoprop to each crop at 1·1 kg ha^?1. Residues of mecoprop, as its methyl ester, were determined gas chromatographically using electrolytic conductivity detection. Initial residues in wheat (119 (±20) mg kg^?1) and oat (95·3 (± 10·0) mg kg^?1) on the day of application (four-leaf stage of wheat and four- to five-leaf stage of oat) decreased to 0·1 to 0·2 mg kg^?1, respectively, within six weeks. Residues were non-detectable in the mature seed of both crops. Recoveries of mecoprop were in the order of 90% from the green tissue and seed of both crops fortified at 0·05 mg kg^?1.