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 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.     

Determination of residues of 1-(2-cyano-2- methoxyiminoacetyl)-3-ethylurea (DPX-3217) by gas-liquid chromatography

Residues of the fungicide 1-(2-cyano-2-methoxyiminoacetyl)-3-ethylurea (DPX-3217) in grapes, potatoes, tomatoes and wine were determined by initial extraction with ethyl acetate, clean-up by liquid-liquid partitioning and adsorption chromatography, and final determination by gas-liquid chromatography with a nitrogen-selective detector. The sensitivity of the method was 0.04 mg kg^?1 based on 50-g samples. Recoveries of the compound added to untreated substrates averaged approximately 92% in the range of 0.04-5.0 mg kg^?1.     

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.     

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 determination of the herbicide dinoseb in lentils

Residues of the herbicide dinoseb were determined gas chromatographically in lentils which had been treated at two locations in Saskatchewan with post-emergence applications of dinoseb at 1.4 and 1.7 kg ha^?1. Herbicide residues, determined at selected times after application, were not detected at the limit of detection of the analytical method (0.05 mg kg^?1) in either the seed and straw at maturity, or in the green foliage six to eight weeks after application. Recoveries of dinoseb were 76% from fortified green foliage at the 0.1 mg kg^?1 level, and 64% from fortified seed at the 0.05 mg kg^?1 level.     

Build-up and subsequent decline of residues of quintozene and hexachlorobenzene in lettuce in sequential crops

The build-up and decline of quintozene and hexachlorobenzene residues in protected lettuce, resulting from one to five treatments of the soil (each of 35 g m-2) with a quintozene formulation, have been studied. Residue levels were monitored in each experimental crop during growth until harvest. Residues in the soil at harvest were also determined. Quintozene residues in the harvested lettuce were in the range < 0.02–0.80 mg kg^?1 and those of hexachlorobenzene were in the range < 0.02–0.05 mg kg^?1 (expressed on a fresh weight basis). Residue levels in the soil were 5.4–231 mg kg^?1 for quintozene, and 0.20–5.4 mg kg^?1 for hexachlorobenzene (expressed on a dry weight basis). Under the experimental conditions of the trial there was no significant build-up of quintozene or hexachlorobenzene in harvested lettuce, even after five treatments to the same site.     

Residues of diflubenzuron and two of its metabolites in a forest ecosystem after control of the pine looper moth,Bupalus piniarius L

Diflubenzuron, 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea was used to control the pine looper population in about 1160 ha of Scots pine stand in eastern Finland in summer 1984. The control measure was effective, resulting in the collapse of the population in the treated area. Residues of diflubenzuron and two of its metabolites, 4-chloroaniline and 4-chlorophenylurea, were determined in water, pine needles, litter, humus, boleti and other wild mushrooms, bilberry (Vaccinium myrtillus L.) and cowberry (Vaccinium vitis-idaea L.) samples taken from this area. In water samples taken from the treated area diflubenzuron was still detected at concentrations of 0.1 μg litre^?1 2 months after application. No diflubenzuron was detected in this area the following year, nor outside the treated area. Neither metabolite was detected at any time. The sum of diflubenzuron and its metabolites in the litter layer was, on average, 0.7mg kg^?1 both 1 week and 1 month after the application. The next year, however, it had increased to 1.4 mg kg^?1. Diflubenzuron and its metabolites were not detected in the humus layer. The amount of diflubenzuron residues in the pine needles was, on average, 3.0 mg kg ^?1 1 day after the application, but in 2 months the level had decreased to 0.2-0.3 mg kg ^?1 or was not detectable. The following year the sum of diflubenzuron and its metabolites in two pine-needle samples was 0.3 and 1.6 mg kg ^?1. The sum of diflubenzuron and its metabolites in wild mushrooms was, on average, 0.07 mg kg ^?1 1 week after the application, but the following year no residues were detected. No residues were found in the boletus samples. The residues of diflubenzuron and its two metabolites in bilberries totalled, on average, 0.2 mg kg ^?1 1 day after the application, and 6 μg kg ^?1 the following year. The sum of diflubenzuron and metabolites in cowberries was, on average, 0.2 mg kg ^?1 1 month after application.     

Fenbutatin oxide,fate in soil after extensive commercial use in Italy and Spain

The long-term fate of the acaricide, fenbutatin oxide, in soil has been investigated. Residues of the compound and its two principal metabolites have been determined in soil samples obtained from citrus orchards in Italy and Spain where the product had been applied commercially over a period of 6–10 years. The average fenbutatin oxide content in the upper 0–15 cm soil layer ranged from ? 1 mg kg^?1 to 5 mg kg^?1 in sites receiving single and double applications per year. The residues were located primarily (> 95%) in the top 0–30 cm layer and there was virtually no movement of the compound through the soil to lower depths. Below 0.5 m depths, the sites contained average concentrations of ? 0.01 mg kg^?1, the limit of determination. No significant build-up of residues was observed and the data indicate an approximate half-life in soil of just less than one year. Residues of the two metabolites, dihydroxy-bis(2-methyl-2-phenylpropyl)stan-nane and 2-methyl-2-phenylpropyl stannonic acid, were on average 11% and 16% of the fenbutatin oxide concentration, respectively. As with fenbutatin oxide, there was no significant movement through the soil to lower levels.     

Pesticide residues in foodstuffs in England and Wales. Part II: Inorganic bromide ion in cucumber,tomato and self-blanching celery grown in soil fumigated with bromomethane,and the ‘natural’ bromide ion content in a range of fresh fruit and vegetables

Surveys of inorganic bromide ion residues in tomatoes, cucumbers and selfblanching celery, commercially produced in England following soil sterilisation with bromomethane, have been carried out since 1979. The mean bromide ion level in 29 late-season cucumber samples was approximately 28 mg kg⁻¹ and ranged up to 109 mg kg⁻¹. Analysis of 242 tomato samples gave estimated mean bromide ion levels per plant ranging from 6 to 187 mg kg⁻¹ in fruit picked throughout the season from seven holdings, on six of which bromomethane had been used fairly recently prior to planting. A statistically significant fall in bromide levels over the growing season was shown on four of the sites. In 38 samples of self-blanching celery, the mean bromide ion level was 104 mg kg⁻¹ even though the mean interval between fumigation and planting was in excess of 1 year. Retail surveillance indicated that a large number of crops are likely to have bromide ion levels below 10mg kg⁻¹.     

Influence of block and cell size,growing medium and insecticide dose on the behaviour and uptake of phorate by lettuce and uptake of carbofuran and chlorfenvinphos by calabrese

Phorate residues in peat blocks and lettuce were determined following incorporation of the insecticide into different block and ‘Speedling’ cell sizes. Between-block variability was influenced little by block size. Phorate oxidation was most extensive in the largest blocks containing the smallest dose. Total residue concentrations in the lettuce declined from the time of planting to harvest, although accumulation of insecticide continued and was related more to dose than to block or cell size. Residues in the lettuce at harvest exceeded the proposed maximum limit of 0.2 mg kg^?1 in some treatments. Residues at planting comprised mainly the parent sulphoxide and sulphone, but by harvest, the oxygen analogue sulphoxide and sulphone predominated. Lettuce weight was not influenced by dose but was related directly to block size. Carbofuran and chlorfenvinphos residues were determined in calabrese sown into two sizes of blocks. At planting time, carbofuran residue concentrations were 100 times greater than those of chlorfenvinphos but residues of both insecticides in the mature heads were < 0.01 mg kg^?1. Seedling weights in both sowings declined with increasing concentrations of the insecticides. It was concluded that manipulations of block size and the dose of insecticide need to be evaluated for individual insecticide/crop combinations to exploit the technique fully.     

Uptake of phorate by lettuce

Following experimental and commercial applications to soil of a granular formulalation of phorate (O,O-diethyl S-ethylthiomethyl phosphorodithioate), residues in the soil and in lettuce were determined by gas-liquid chromatography. When applied by the bow-wave method as a continuous logarithmically-changing dose ranging from approximately 0.9 to 16.0 kg a.i. ha^?1, the proportional rate of oxidation in soil of phorate sulphoxide to phorate sulphone was inversely related to dose. Ten weeks after application, total phorate residues in the soil had declined by about 35% at all dose levels. Residues in mature lettuce, from the 1-5 kg ha^?1 dose-range, comprised the parent and oxygen analogue sulphoxides and sulphones; the relative proportions of the individual metabolites were independent of dose. Over this dose-range, total residue concentrations in the crop became proportionally slightly greater with increasing dose. When single doses of 1.1, 2.0 or 2.2 kg a.i. ha^?1 were applied at drilling, the total residue concentrations in the lettuce declined from 5 mg kg^?1 in seedlings from some treatments to <0.05 mg kg^?1 at harvest. In plants raised in peat blocks containing 10 or 20 mg a.i. per block, however, residues in seedlings totalled 45-47 mg kg^?1 and declined to only 0.7 mg kg^?1 at harvest. It was concluded that bowwave applications of phorate when field-sowing lettuce were unlikely to lead to unacceptable residues in the harvested crop, but that residues in lettuce raised in phorate-treated peat blocks may be unacceptably high.     

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     

The behaviour of residues of flamprop-isopropyl and its breakdown products in barley

Residue data are reported for flamprop-isopropyl ( I ) in barley grain and straw samples following applications of the herbicide to crops grown in eight countries. The samples were analysed for I and its hydrolysis product N-benzoyl-N-(3-chloro-4-fluorophenyl)-DL -alanine ( II ). Following recommended applications (normally 1 kg ha^?1 at Feekes scale G-I/J), residues of I and II in the grain were low (90% were <0.02 mg kg^?1 for I , 86% were <0.06 mg kg^?1 for II , levels which were essentially the limits of determination). Residues in straw were higher and more variable, but again 63 and 77% of samples were below 1 mg kg^?1 for I and II , respectively.     

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.     

Organophosphorothioates and synergised synthetic pyrethroids as grain protectants on bulk wheat

Organophosphorothioates and synergised synthetic pyrethroids were used in duplicate field trials carried out on bulk wheat in commercial silos in Queensland and New South Wales. Laboratory bioassays using malathion-resistant strains of insects were carried out on samples of treated grain at intervals over 9 months. These established that all treatments were generally effective. Deltamethrin (2 mg kg^?1)+ piperonyl butoxide (8 mg kg^?1), fenitrothion (12 mg kg^?1)+ fenvalerate (1 mg kg^?1)+ piperonyl butoxide (8 mg kg^?1), fenitrothion (12 mg kg^?1)+ phenothrin (2 mg kg^?1)+ piperonyl butoxide (8 mg kg^?1) and pirimiphos-methyl (4 mg kg^?1)+ permethrin (1 mg kg^?1)+ piperonyl butoxide (8 mg kg^?1) controlled common field strains of Sitophilus oryzae (L.) and Rhyzopertha dominica (F.). Against a highly resistant strain of S. oryzae, deltamethrin (2 mg kg^?1)+ piperonyl butoxide (8 mg kg^?1) was superior to the remaining treatments. All treatment combinations completely prevented progeny production in Tribolium castaneum (Herbst), T. confusum Jacquelin du Val and in Ephestia cautella (Walker). Residues of deltamethrin, fenvalerate, permethrin and phenothrin were determined and shown to be highly persistent on stored wheat. During milling, residues accumulated in the bran fractions and were reduced in white flour. They were not significantly reduced during baking.     

The behaviour of residues of benzoylprop-ethyl and its breakdown products in wheat

Samples of wheat grain and straw have been analysed from trials with the wild oat herbicide benzoylprop-ethyl ( I ) in several countries. Following recommended commercial treatments (application of 1.0–1.6 kg ha^?1 at Feekes growth stage G-J), total residues of I and its hydrolysis product N-benzoyl-N-(3,4-dichlorophenyl)-DL - alanine (free and conjugated) were low and in the majority of instances they were < 0.01 mg kg^?1 in samples of grain from the UK, although rather higher residues were detected in some grain samples from other countries. Residues in straw were higher, but normally did not exceed 2 mg kg^?1, and were rather variable, possibly as a result of differences in agricultural practice.     

Herbicide residues in waste waters from ricefields

The herbicides bentazone, 2,4-D, MCPA, propanil, molinate, and tiocarbazil, and the insecticide phenthoate, were applied to ricefields in Sardinia at rates equivalent to maximum aqueous concentrations of 0.4-2.8 mg kg^?1, assuming the water to be 20 cm deep. Their concentrations in water were measured by high-performance liquid chromatography. Residues in 162 water samples, collected from 16 ricefields 1, 4, 7, 10, 12, 18, 21 and 120 days after the last spraying, were all below the limit of determination (0.03 mg kg^?1). Residues in 40 water samples taken from five drainage canals were also less than 0.03 mg kg^?1.     

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.