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.     

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     

Enzyme immunoassay for atrazine analysis in water and soil

Enzyme immunoassay (EIA) has been tested for the detection of atrazine in soil and water. EIA kits and atrazine-fortified samples were received from the International Atomic Energy Agency. Atrazine concentrations of about 0·01 μg litre^-1 could be detected and the central detection point was found at about 0·15 μg litre^-1 which is a reasonably sensitive region for atrazine. A validation study with spiked local water samples yielded acceptable results. No treatment was required for water samples. Extraction of atrazine from soil was done by simple shaking with methanol without any clean-up steps. Detection limits of 1×10^-2 μg litre^-1 for water and 5×10^-3 μg kg^-1 for soil were achieved. © 1998 SCI.     

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.     

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.     

Some physicochemical factors influencing foliar uptake enhancement of glyphosatemono(isopropylammonium) by polyoxyethylene surfactants

Structure-concentration–foliar uptake enhancement relationships between commercial polyoxyethylene primary aliphatic alcohol (A), nonylphenol (NP), primary aliphatic amine (AM) surfactants and the herbicide glyphosatemono(isopropylammonium) were studied in experiments with wheat (Triticum aestivum L.) and field bean (Vicia faba L.) plants growing under controlled-environment conditions. Candidate surfactants had mean molar ethylene oxide (EO) contents ranging from 5 to 20 and were added at concentrations varying from 0·2 to 10 g litre^?-1 to [¹⁴C]glyphosate formulations in acetone–water. Rates and total amounts of herbicide uptake from c. 0·2–μl droplet applications of formulations to leaves were influenced by surfactant EO content, surfactant hydrophobe composition, surfactant concentration, glyphosate concentration and plant species, in a complex manner. Surfactant effects were most pronounced at 0·5 g acid equivalent (a.e.) glyphosate litre^?-1 where, for both target species, surfactants of high EO content (15–20) were most effective at enhancing herbicide uptake: surfactants of lower EO content (5–10) frequently reduced, or failed to improve, glyphosate absorption. Whereas, at optimal EO content, AM surfactants caused greatest uptake enhancement on wheat, A surfactants gave the best overall performance on field bean; NP surfactants were generally the least efficient class of adjuvants on both species. Threshold concentrations of surfactants needed to increase glyphosate uptake were much higher in field bean than wheat (c. 2 g litre^?-1 and < 1 g litre^?-1, respectively); less herbicide was taken up by both species at high AM surfactant concentrations. At 5 and 10 g a.e. glyphosate litre^?-1, there were substantial increases in herbicide absorption and surfactant addition could cause effects on uptake that were different from those observed at lower herbicide doses. In particular, the influence of EO content on glyphosate uptake was now much less marked in both species, especially with AM surfactants. The fundamental importance of glyphosate concentration for its uptake was further emphasised by experiments using formulations with constant a.i./surfactant weight ratios. Any increased foliar penetration resulting from inclusion of surfactants in 0·5 g litre^?-1 [¹⁴C]glyphosate formulations gave concomitant increases in the amounts of radiolabel that were translocated away from the site of application. At these low herbicide doses, translocation of absorbed [¹⁴C]glyphosate in wheat was c. twice that in field bean; surfactant addition to the formulation did not increase the proportion transported in wheat but substantially enhanced it in field bean.     

A monoclonal antibody‐based ELISA for the analysis of the insecticide flucythrinate in environmental and crop samples

A competitive enzyme‐linked immunosorbent assay (ELISA) has been developed for the detection of the insecticide flucythrinate in environmental and food samples. Two types of haptens, the acid moiety that is the hydrolyzed product of flucythrinate, and the carboxylated propyl derivative of the alcohol moiety, were used to prepare monoclonal antibodies (MAbs). Five MAbs, which raised against the former hapten, were reactive with flucythrinate. Among them, MAb F1A27‐4 showed the highest activity toward flucythrinate, and did not cross‐react with other pyrethroids such as cycloprothrin, fenvalerate, fluvalinate, etofenprox and silafluofen. The assay conditions of indirect competitive ELISA with MAb F1A27‐4 were studied to optimize the detection of flucythrinate in environmental and food samples. Incubation at 4 °C in the assay buffer, pH 8, with 300 mM sodium chloride improved the sensitivity. The addition of rabbit serum albumin or rabbit antiserum and the presence of 50 ml litre^?1 of methanol reduced matrix effects of the samples. Under optimized conditions, the ELISA detected flucythrinate spiked in water, soil, and extracts of apple and tea samples down to 10 mg litre^?1, 0.2 mg litre^?1, 0.3 mg litre^?1 and 0.3 mg litre^?1, respectively. The mean recovery and CV ranged from 91% to 120% and from 5% to 12%, respectively. The ELISA results in apple samples correlated well with those from LC–MS analysis (r² = 0.99, n = 12). © 2001 Society of Chemical Industry     

Leaching potential and decomposition of fluroxypyr in Swedish soils under field conditions

The mobility and decomposition of the herbicide fluroxypyr (4-amino-3,5-dichloro-6-fluoro-2-pyridyloxyacetic acid) was studied under field conditions in a sandy soil and a clay soil. Leachate was collected in lysimeters with undisturbed soil (sand) and in tile-drained plots (clay). Soil samples to a depth of one metre were also collected in both soils to characterize the temporal depth distribution of fluroxypyr in the profiles. The herbicide was applied as the I-methylheptyl ester of fluroxypyr at two rates, 187.5 and 375.0 g a.e. ha^?1, representing the normal and double the dose of the compound used for spring cereals. Some lysimeters received supplementary watering. Only two leachate samples (one from each soil) had concentrations of fluroxypyr above the detection limit (1 μg litre^?1), i.e. 2 and 5 μg litre^?1. Both samples were collected within two months after application, when less than 2 mm of drainage had been collected. The methylheptyl ester of fluroxypyr was not found in any of the samples. Fluroxypyr levels above the detection limit in soil (5 μg kg^?1 dry soil), were never found below the topsoil (0.2 m) in the clay profile, while, in the sandy profile, levels just above the detection limit were found occasionally in deeper soil layers. Concentrations were reduced to undetectable or very low levels within three months after spraying.     

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.     

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.     

Effects of some nonionic polyoxyethylene surfactants on uptake of ethirimol and diclobutrazol from suspension formulations applied to wheat leaves

The influence of a number of commercial nonionic polyoxyethylene surfactants on the foliar penetration and movement of two systemic fungicides, ethirimol and diclobutrazol, was studied in outdoor-grown wheat plants at different growth stages and post-treatment temperatures in two consecutive growing seasons. Both fungicides were applied as ca 0·2 μl droplets of aqueous suspension formulations containing 0·5 g litre^?1 of ¹⁴C-labelled active ingredient; surfactants were added to these suspensions at concentrations ranging from 0·2-10 g litre^?1. To achieve optimum uptake of each fungicide the use of surfactants with different physicochemical properties was required. For diclobutrazol, a lipophilic compound, uptake of radiolabel was best with surfactants of low mean molar ethylene oxide (E) content (5-6) but it was necessary to use concentrations of ca 5 g litre^?1 to attain this. The surfactant threshold concentration for uptake enhancement of radiolabel from ethirimol formulations (< 2 g litre^?1) was much lower than that for diclobutrazol but surfactants with E contents > 10 induced the greatest amount of uptake. For both fungicides, surfactants with an aliphatic alcohol hydrophobe were generally more efficient in promoting their uptake than those with a nonylphenol moiety. The sorbitan-based surfactant ‘Tween 20’ proved to be an effective adjuvant only for the ethirimol formulation; the uptake enhancing properties of the block copolymer ‘Synperonic PE/F68’ were weak. Uptake performance could not be related to the spreading properties of the respective formulations on the wheat leaf surface or to differences in solubilisation of the two fungicides by the surfactants. Although surfactants could substantially increase the amount of acropetal transport of radiolabel from both fungicides, none of those tested specifically promoted it; a constant proportion of the radioactive dose absorbed by a treated leaf was usually exported away from the site of application. The results are discussed in the light of current theories about the mode of action of surfactants as spray adjuvants.     

A rapid high-pressure liquid chromatographic method for the determination of carbaryl residues in wheat grain

Carbaryl residues in wheat grain have been determined in methanol extracts using normal-phase high-pressure liquid chromatography (h. p. l. c.) with ultraviolet detection. A single-injection, clean-up and analysis technique was used to allow more rapid analysis of samples after extraction. A detection limit of 0.1 mg kg^?1 in a 50 g sample of wheat was achieved. Recoveries of 86% at the 1 mg kg^?1 level and 90-99% at the 5 mg kg^?1 level were obtained for fortified grain samples. Methanol was found to be a superior extractant for carbaryl from wheat when compared with hexane, acetone and dichloromethane. Twelve samples containing aged carbaryl residues were analysed by the h. p. l. c. technique and by a colorimetric procedure which allowed statistical analysis of errors. For the h. p. l. c. method (excluding sampling error), a relative standard deviation of 4.4% was obtained.     

HPLC separation and subsequent detection of aromatic heptaene polyenes in peat after treatment with Streptomyces griseoviridis

Aromatic heptaene polyenes (AHPs), the largest group of antifungal polyene antibiotics, were detected in steam-sterilized Sphagnum peat after treatment with a new biofungicide containing fermenter-cultivated Streptomyces griseoviridis Anderson K61, a bacterium capable of producing AHPs in vitro. Three concentrations (0.05 g litre^?1, 0-2 g litre^?1 and 2.0 g litre^?1) of the biofungicide were used and compared to untreated controls. The substrates were incubated for seven weeks under greenhouse conditions, with and without cucumber seedlings, and samples were analysed for heptaene polyenes by HPLC using a photodiode array detector. Changes in AHP concentrations indicated that the fermenter-cultivated mycelium was a partial source of extractable heptaenes in peat. The identification of p-aminoacetophenone (PAAP) by HPLC-MS in peat hydrolysates verified the presence of AHPs.     

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     

Spectrophotometric determination of ferric dimethyldithiocarbamate (ferbam) in formulations,grain and apples using 1, 10-phenanthroline

A procedure has been developed for the determination of ferbam (ferric dimethyldithiocarbamate) by converting it into ferbam-phenanthroline complex, which is dissolved in acetone + water (1 + 1 by volume), and the absorbance measured at 490 nm against a reagent blank. Beer's law is obeyed over the concentration range 0–8–20-0 mg litre^?1 in the final solution. The method is sensitive, selective and can be used for the direct determination of ferbam in commercial samples, in mixtures with various other dithiocarbamates (ziram, zineb, maneb, etc.) and from grains (rice and wheat) and apples. The limit of determination from foodstuffs is 0–4 mg kg^?1.     

Determination of carbofuran in pesticide formulations by flow injection spectrophotometry

A flow injection spectrophotometric method for the determination of carbofuran in commercial pesticide formulations was developed. The determination involves on‐line hydrolysis of the extracted carbofuran at room temperature with sodium hydroxide. The resulting carbofuran‐phenol is coupled with diazotized 4‐aminobenzoic acid in order to achieve an appropriate selectivity and sensitivity for the spectrophotometric measurements. The calibration curve is linear over the range 1–10 mg litre⁻¹ of carbofuran. The proposed method has a detection limit of 0.15 mg litre⁻¹ of carbofuran and a sample frequency of 120 injections per hour. The relative standard deviation of six independent determinations of a sample containing 1 mg litre⁻¹ carbofuran was 0.6%. The suitability of the proposed procedure for the determination of carbofuran in commercial pesticide formulations was studied. The procedure provides results comparable to those obtained by liquid chromatographic analysis. © 2000 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.     

Influence of different field sites on pesticide movement into subsurface drains

Pesticide movement to subsurface drains was monitored in two typical crop production areas in Germany. Field trials were conducted on two subsurfacedrained soils, a silt loam and a poorly structured sandy soil, under different climatic conditions. Over a period of one year, the drainflow was measured and the drain water was analysed for all applied herbicides. Different leaching behaviour was observed at the two field sites. Following autumn application of pendimethalin and isoproturon to the Soester Börde soil, maximum concentrations of about 62 μg litre^?1 for isoproturon and 0.7 μg litre^?1 for pendimethalin were observed in drainflow from this silt loam. The early occurrence of both herbicides in the drain water only two days after application is consistent with fast flow through macropores. In contrast, on the subsurfacedrained sandy soil in Brandenburg, isoproturon did not reach the drains until two months after autumn application and was found at maximum concentrations of only 1.4 μg litre^?1; pendimethalin was not detected in the drain water. Pesticide movement after spring application seemed to be of minor importance. At both locations, spring application led to low concentrations of pesticides in the drainflow (pendimethalin < 0.01 μ litre^?1; metolachlor ? 0.05 μ litre^?1; chloridazon ? 0.15 μ litre^?1; metamitron ? 0.02 μg litre^?1; terbuthylazine ? 1.4 μ litre^?1).     

The determination of imazalil on potatoes and its use in controlling potato storage diseases

Methods are described for the extraction and analysis by gas-liquid and high-pressure liquid chromatography of the fungicide imazalil, 1-(β-allyloxy-2, 4-dishlorophenethyl) imidazole, on potatoes. Before storage, over 80% was recovered from potatoes treated with 0.01–3.0 mg imazalil kg^?1, with a detection limit of 2 μg kg^?1. Imazalil applied to potatoes at 10 g t^?1 before storage decreased the incidence of gangrene (Phoma exigua), silver scurf (Helminthosporium solani), skin spot (Polyscytalum pustulans) and black scurf (Rhizoctonia solani), and was at least as effective as thiabendazole applied at 40 g t^?1. At 1 g t^?1 it also decreased skin spot and silver scurf. Incidence of black dot (Colletotrichum coccodes) was unaffected by these fungicide treatments.     

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.