Distribution of fenvalerate and permethrin residues on cattle hair following variable application rates of impregnated ear tags

Fenvalerate and permethrin residues on hair of groups of cattle that received either two tags per adult animal or one tag for every other adult animal were determined using gas chromatography over a three-month period in 1987 and 1988. Cattle with two tags had consistently higher residues than cattle with one tag. This difference was statistically significant (P < 0.05) in the first month for residues on the head and in the first two weeks for residues from the body in 1987. Residues on cattle with one tag and without a tag in the same herd were similar (P > 0.05) on each sampling day on all regions. Residues on the hair from the head of cattle with two tags were greater than on the body and rump (P < 0.05) during the first 28 days. Residues found on hair on days 14 and 84 following tag application declined by 80–86% on the head, 73–78% on the body, and 36–86% on the rump. Isomeric compositions of fenvalerate (range 51–61% SR, RS: 39–49% SS, RR) and permethrin (range 61–67% trans: 33–39% cis) were consistent during the study. Rainfall reduced residues on hair.     

The estimation of residue levels of promacyl and its metabolites in beef tissue and fat by high-performance liquid chromatography with electrochemical detection

A method is described for the estimation of residues of the carbamate insecticide promacyl [5-methyl-m-cumenyl butyryl(methyl)carbamate] and its metabolites that are hydrolysable to isothymol (m-cymen-5-ol), using high-performance liquid chromatography with electrochemical detection to determine the isothymol. Clean-up of samples relied on the steam volatility of phenols. Recoveries at the 0.1 mg kg^?1 level varied from 72–88% for fat tissue and 81–91% for liver. The limits of detection were found to be 0.01 mg kg^?1 for and 0.02 mg kg^?1 for liver. A comparative study of the chromatography of sample extracts using both ultraviolet detection and electrochemical detection showed a substantial decrease in the level of interfering co-eluates in the latter method. A field trial, involving a single spray application of the formulated acaricide on milking cattle, revealed residues in the butter fat comparable with those found in a previous investigation.     

Residue behaviour of fenvalerate,tau-fluvalinate,lambda-cyhalothrin and monocrotophos in eggplant (Solanum melongena L.) fruits

The persistence patterns of three synthetic pyrethroids—fenvalerate, tau-fluvalinate, lambda-cyhalothrin—and an organophosphorus insecticide, monocrotophos, on eggplant (Solanum melongena L.) have been evaluated. The extractable residues ranged from 0.05 to 0.45, 0.01 to 0.40, 0.003 to 0.09 and 0.09 to 0.32 μg g^?1 for fenvalerate, tau-fluvalinate, lambda-cyhalothrin and monocrotophos, respectively. Fenvalerate was the most persistent among the four, followed by monocrotophos, lambda-cyhalothrin and tau-fluvalinate. The Maximum Residue Limit (MRL) of these pesticides on S. melongena has not yet been documented. The present data may be useful for establishing MRL and assessing the amount of pesticide residues in this vegetable.     

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.     

Disposition kinetics,cytotoxicity and residues of fenvalerate in tissues following oral administration to goats

Disposition kinetics in goats of fenvalerate [(RS)-α-cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methylbutyrate] were studied after oral administration at 5 mg kg^?1. The insecticide persisted in blood for up to 48 h. The V_d(area), t_1/2(β), and t_1/2(Ka), of fenvalerate were 12.14 (±0.39) litre kg^?1, 12.25 (±0.25) h and 0.63 (±0.11)h, while the AUC and Cl_B values were respectively 7.35 (±0.39) μg h ml^?1 and 0.68 (±0.04) litre kg^?1 h^?1. The residues in tissues reached a peak four days after insecticide administration and then started to decline. Maximum residue was found in the adrenal gland, followed by liver, kidney and intestine. Both GOT and GPT activities in kidney tissue, but only GPT activities in liver tissue had decreased significantly 4, 8 and 22 days post-administration. The fenvalerate did not produce any significant effects on serum acetylcholinesterase, cholesterol or protein levels in goats. Histopathological examination showed fatty changes in the periphery of lobule, congestion in sinusoid, haemolysis in central vein, necrosis and periportal fibrosis around the central vein of liver, and necrosis in kidney of fenvalerate-treated goats.     

Disposition kinetics of cypermethrin and fenvalerate in black bengal lactating goats

Disposition kinetics of cypermethrin and fenvalerate were investigated in lactating black Bengal goats following single dose intravenous administration at 57 and 45 mg kg^?1 respectively. The maximum and minimum blood concentrations of cypermethrin were 18.49 (±3.17) and 0.06 (±0.002) μg ml^?1, while the corresponding values for fenvalerate were 14.58 (±2.37) and 0.04 (±0.005) μg ml^?1 respectively. Both cypermethrin and fenvalerate remained present in blood for 36 h. The mean t1/2β) and Vd_area values were 5.56 (±0.28) h and 10.38 (±2.20) litre kg^?1 for cypermethrin and 5.66 (±0.35) h and 11.31 (±2.20) litre kg^?1 respectively for fenvalerate. Both cypermethrin and fenvalerate persisted in goat milk for 36 h. The t1/2β) and AUC values of fenvalerate were 7.37 (±1.84) h and 122.38 (±11.65) μg h ml^?1 whilst the corresponding values for cypermethrin were 6.66 (±1.54) h and 99.48 (±7.81) μg h ml^?1 in milk respectively.     

Comparative purification methods for determination of triadimenol residues in plant material

Two procedures are described for the determination of residues of triadimenol and compared on cereal material. After extraction, purification is carried out by Florisil column chromatography in method I and by semi-preparative High-Performance Liquid Chromatography in method II. Triadimenol residues are quantified by gas chromatography with a thermoionic detector. With method I, interference was observed but not with method II. This specific procedure has been tested on other plant materials. Recoveries in the range of 90–98% indicate that this procedure is suitable for residue analysis of this fungicide with detection limits of 0·008 mg kg^?1 in wheat grains, 0·03 mg kg^?1 in wheat straw and 0·004–0·008 mg kg^?1 in other plants. Maximum residue limits in France are: 0·1 mg kg^?1 in grain, 2·0 mg kg^?1 in straw and 1·0 mg kg^?1 in other vegetables and fruit.     

Development and validation of residue methods for the determination of the pyrethroids lambda-cyhalothrin and cypermethrin in natural waters

This paper describes the development of methods suitable for the sampling and analysis of the pyrethroid insecticides lambda-cyhalothrin and cypermethrin in natural waters. A solid-phase water-sampling method which avoids the requirement for transport and storage of large volumes of water is described. This method is shown to be capable of extracting trace levels (ng litre^?-1) of the title compounds from natural waters with efficiencies of at least 80%. Chromatographic analysis of processed samples by gas chromatography–electron capture detection enables determination of residues at levels of 1–2 ng litre^?-1 in water.     

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.     

Chlorpyrifos degradation in soil at termiticidal application rates

Chlorpyrifos [O,O-diethyl O-(3,5,6-trichloro-2-pyridyl) phosphorothioate] is an organophosphorus insecticide applied to soil to control pests both in agricultural and in urban developments. Typical agricultural soil applications (0.56 to 5.6 kg ha^?1) result in initial soil surface residues of 0.3 to 32 μg g^?1. In contrast, termiticidal soil barrier treatments, a common urban use pattern, often result in initial soil residues of 1000 μg g^?1 or greater. The purpose of the present investigation was to understand better the degradation of chlorpyrifos in soil at termiticidal application rates and factors affecting its behaviour. Therefore, studies with [¹⁴C]chlorpyrifos were conducted under a variety of conditions in the laboratory. Initially, the degradation of chlorpyrifos at 1000 μg g^?1 initial concentration was examined in five different soils from termite-infested regions (Arizona, Florida, Hawaii, Texas) under standard conditions (25°C, field moisture capacity, darkness). Degradation half-lives in these soils ranged from 175 to 1576 days. The major metabolite formed in chlorpyrifos-treated soils was 3,5,6-trichloro-2-pyrid-inol, which represented up to 61% of applied radiocarbon after 13 months of incubation. Minor quantities of [¹⁴C]carbon dioxide (< 5%) and soil-bound residues (? 12%) were also present at that time. Subsequently, a factorial experiment examining chlorpyrifos degradation as affected by initial concentration (10, 100, 1000 μg g^?1), soil moisture (field moisture capacity, 1.5 MPa, air dry), and temperature 15, 25, 35°C) was conducted in the two soils which had displayed the most (Texas) and least (Florida) rapid rates of degradation. Chlorpyrifos degradation was significantly retarded at the 1000 μg g^?1 rate as compared to the 10 μg g^?1 rate. Temperature also had a dramatic effect on degradation rate, which approximately doubled with each 10°C increase in temperature. Results suggest that the extended (3–24 + years) termiticidal efficacy of chlorpyrifos observed in the field may be due both to the high initial concentrations employed (termite LC ₅₀ = 0.2– 2 μg g^?1) and the extended persistence which results from employment of these rates. The study also highlights the importance of investigating the behaviour of a pesticide under the diversity of agricultural and urban use scenarios in which it is employed.     

Fate and short-term persistence of permethrin insecticide injected in a northern Ontario (Canada) headwater stream

1·275 dm³ of a l·3g dm^?3 aqueous emulsion of permethrin (i.e. 1·658 g permethrin) was applied to the surface of a fast-flowing stream by manual injection. Water samples were collected from the top 1-cm layer at different intervals of time at various distances downstream from the site of application. Caged samples of stream detritus, crayfish, brook trout and stonefly nymphs, bottled sediment and potted aquatic plants were placed 280 m from the treatment site, and collected afterwards for residue analysis. The downstream movement of the chemical was not uniform with peak concentrations of about 12 ng ml^?1 at 30 m and 0·1 ng ml^?1 at 730 m from the treatment site. The peak concentrations (ng g^?1) in potted aquatic plants, caged detritus, crayfish and brook trout were about 18, 39, 14 and 11 respectively. The residues were higher than the ambient water concentration (1·67 ng ml^?1) and dissipated slowly. The peak concentration in the bottled sediment was 2·75 ng g^?1, and the residues were lost rapidly. In contrast, the naturally occurring sediment in a beaver pond showed high residues that persisted for a longer period of time. Permethrin concentrations in invertebrate drift ranged from 9 to 357 ng g^?1, depending on the distance from the application site. The study demonstrated that aquatic invertebrates, plants and stream detritus acted as the major sink for the chemical.     

The determination of residues of 2,4-D in post-emergence-treated triticale

A gas chromatographic method, using electrolytic conductivity detection, is presented for the determination of 2,4-0 as its methyl ester in triticale (X Triticosecale Wittmack). The method was used to monitor the dissipation of 2,4-0 residues in triticale over a growing season at two sites following post-emergence application of the dimethylamine salt of 2,4-D at 0.56 kkg ha^?1. Initial residues, in the order of30 mg kg^?1. on the day afer application (3- to 4-leaf stage of the crop), decreased to non-detectable levels in the mature straw and seed. Recoveries of 2,4-D were greater than 90% fiom green tissue fortified at 0.1 mg k^?1., and in the order of 75% from seed fortified at 0.05 mg kg^?1.     

The metabolism in the rat of the herbicidally active isomer (R)- flamprop-methyl in comparison with the racemic form

A single dose (4 mg kg^?1) of ¹⁴ C-labelled (R)-flamprop-methyl to rat was rapidly metabolised and 90% of the dose was eliminated in urine and faeces within 48 h. Four days after dosing, tissue residues were 0–1 μg equivalents g^?1 tissue or much less, with the exception of kidney (0–22 μg g^?1). There was a statistically significant sex difference in the routes of elimination; this may be attributed to differences in the biliary elimination of the major metabolite, flamprop acid, or its glucuronide conjugate. The fate of racemic flamprop-methyl was very similar to that of the (R)-isomer. The major metabolic routes were hydrolysis of the esters to the corresponding acids, hydroxylation of the benzoyl aromatic rings and conjugation. The flamprop acid derived from the (R)-flamprop-methyl was found to be partially converted to the (S)-form (R:S ratio, 87:13). This reaction is discussed in the context of other such biological racemisations recently reported.     

Protective action of fenvalerate,deltamethrin, and four stereoisomers of permethrin against black flies (Simulium spp.) attacking cattle

Fenvalerate, deltamethrin, (1R)-cis-permethrin, (1R)-trans-permethrin and (1S)-trans-permethrin, applied topically to the entire body surface of steers at a rate of 1 mg a.i. kg⁻¹, provided 70% or better protection from black flies on cattle for 16, 9, 8, 6 and 6 days, respectively. The (1S)-cis stereoisomer of permethrin was ineffective as a protectant against black flies at a rate of 1 mg a.i. kg⁻¹ when applied as a total body spray. One poly(vinyl chloride) ear tag containing 10% permethrin, in each ear of steers, provided protection from black fly attack for up to 13 days under field conditions. Poly(vinyl chloride) ear tags containing 8% fenvalerate, installed in each ear of steers, did not provide satisfactory protection from black flies under field conditions.     

Measurement of simazine residues in chickpeas,Cicer arietinum,by gas–liquid chromatography

A method is described for the measurement of simazine [2-chloro-4,6-bis(ethylamino)-1,3,5-triazine] residues in chickpeas (Cicer arietinum). Ground chickpea samples were extracted with dichloromethane, followed by clean-up on alumina. Gas-liquid chromatography using metribuzin [4-amino- 6-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one] as internal standard with thermionic detection was used to quantify simazine residues. The limit of detection was 0.02 mg kg^?1 and the recoveries of simazine from chickpea samples (0.1–4 mg kg-1) averaged 92%.     

Pharmacokinetics of Intravenous Fenvalerate in Cattle Treated Topically with a Low Dose of Piperonyl Butoxide

Experiments were conducted to identify pharmacokinetic interactions between topically applied piperonyl butoxide and intravenous fenvalerate in cattle (Angus steers). Intact fenvalerate in plasma was derivatized by condensation with acetone and measured by negative chemical ionization gas chromatography/mass spectrometry. Noncompartmental pharmacokinetic analyses indicated that the elimination-phase rate constant (β, 0·00069 (±0·00006) min^-1), mean residence time (172 (±14) min), systemic clearance (10·4 (±0·7) ml min^-1 kg^-1) or volume at steady state (1800 (±230) ml kg^-1) were not changed (P>0·05) after topical application of a low dose of piperonyl butoxide. These data indicate that topical application of a low dose of the metabolic synergist piperonyl butoxide would not be expected to modify the in-vivo disposition of fenvalerate in cattle. © of SCI.     

Utilisation des chlorelles pour le dosage biologique de l'atrazine dans le sol

The use of Chlorella for biological estimation of atrazine in soil The use of a Chlorella culture in well-defined experimental conditions permits the estimation of atrazine bioactivity in soil without preliminary extraction. The determination was made with a non-absorbant material (sand). In this way, atrazine concentrations of 0.10 μg g^?1 of sand could be detected and from 0.45 μg g^?1 of sand determined accurately. Examples of applications are given for soils of very different composition. Comparison with the oat-seedling method shows that the method proposed gives results of similar magnitude.     

Toxicity of 1,2-dibromoethane and 1,3-dichloropropene to microsclerotia of Verticillium dahliae

The toxicity of two fumigants to microsclerotia (MS) of Verticillium dahliae in air and in soil was determined in sealed containers. 1, 2-Dibromoethane (DBE, ethylene dibromide) at 470 μ ml^?1 of air, or at 12.5 μ g^?1 of soil, killed 97% of the MS, both after incubation for 16 days. 1, 3-Dichloropropene (1, 3-D) at 20 μ ml^?1 of air, however, killed 100% of the MS after incubation for 30 h, and at 100 μ g^?1 of soil after incubation for 3 days. Higher temperatures increased the toxicity of both DBE and 1, 3-D to the MS. The toxicity of DBE increased with increase in soil moisture between 0–80% of field capacity while the toxicity of 1, 3-D increased between 0–20% of field capacity and was constant between 20–80% of field capacity.     

A rapid bioassay for the detection of photosynthesis inhibitors in water

A modified leaf disc buoyancy procedure for the detection of photosynthesis-inhibiting residues in water is described. The modifications proposed, mainly the presence of sodium hydrogen carbonate in the infiltration solution, increased the sensitivity of the method and reduced the time required. The substituted urea and 1,3,5-triazine herbicides diuron, linuron, monuron, atrazine, ametryn and atraton were detected below 0.7 mg litre^?1 using cucumber (Cucumis sativus L., cv. ‘Dalia’) leaf discs. A concentration as low as 0.09 mg diuron litre^?1 could be detected. Although bean (Phaseolus vulgaris L., cv. ‘Bulgarian’) leaf tissue was less sensitive in this bioassay than cucumber, 0.3 mg diuron litre^?1 could still be detected. The test, being very rapid (less than 30 min per determination) and relatively sensitive, could be used for the detection of photosynthesis inhibitors in recycled water used for irrigation.     

The persistence and activity of insecticide spary deposits on woven polypropylene fabric

Wettable powder formulations of the organophosphorus insecticides, fenitrothion and pirimiphos-methyl, and the pyrethroids, permethrin and deltamethrin, have been compared for persistence and activity on woven polypropylene fabric; the residues produced in maize kept under the test sheets have also been measured. The test insects were Sitophilus oryzue (L.) and Tribolium custuneum (Herbst). Permethrin at 41 and 83 mg m^?2 was completely effective for the full 12 weeks of the experiment. Deltamethrin at 6.2 and 12.5 mg m^?2 was almost equally effective but after 4 weeks the deposit was slower acting against S. oryzae. The organophosphorus compounds were effective only up to 2 weeks at 250 mg m^?2 and up to 4 weeks at 500 mg m^?2. No residues could be detected under the pyrethroids but the organophosphorus insecticides gave residues of 2–4 mg kg^?1 on a thin layer of grain. This residue was biologically effective against the test insects.