Cipac collaborative study to test a colorimetric method for determination of the stability of dilute emulsions

A colorimetric method for the determination of the stability of dilute emulsions (down to 1 ml litre^?1) of emulsifiable concentrates (EC) has been subjected to a collaborative study with 27 participating laboratories, on behalf of the Collaborative International Pesticides Analytical Council (CIPAC). A dye is added to the emulsifiable concentrate and an aliquot is poured into standard water to obtain an aqueous emulsion. After a specified time, the absorbance of an aliquot of the dyed emulsion is measured and compared to the absorbance measured after initial formation of the emulsion. Collaborators were furnised with four emulsifiable concentrate formulations and the dye, and requested to make three replicate determinations on each dyed sample in CIPAC standard waters A and D. The repeatability and reproducibility figures obtained in these trials indicate that the method permits a good estimation of the stability of dilute emulsions when it is followed exactly.     

Uptake of aminotriazole from humectant-surfactant combinations and the influence of humidity

Uptake of aminotriazole (3-amino-1,2,4-triazole) by bean leaves (Phaseolus vulgaris var. Canadian Wonder) was not greatly influenced by the addition to the spray solution of dimethylformamide (DMF), ethylene glycol and polypropylene glycol 400 (PPG 400) over the concentration range 1.0–50.0 ml litre^?1. However, the addition of polyoxyethylene 20 sorbitan monolaurate (polysorbate 20) (0.2–1.0 g litre^?1) to spray solutions of the above additives and glycerol (5.0 ml litre^?1; except for DMF, 50.0 ml litre^?1) substantially increased uptake to 80–100% in all cases at 50 ± 10% relative humidity (r.h.). Similar penetration figures were recorded when a range of polysorbate surfactants (polysorbate 20, 40, 60, 80 and 85; 0.2 g litre^?1) were applied to spray solutions containing either dimethyl sulphoxide (DMSO) or glycerol (5.0 ml litre^?1). Humidity was found to have a critical effect upon the humectant-surfactant combinations tested, i.e. DMSO + polysorbate 20, ethylene glycol+ polysorbate 20 and PPG + 400-polysorbate 20 (5.0 ml litre^?1+0.2 g litre^?1). With DMSO + polysorbate 20 the following uptake figures were recorded: < 30% r.h., 3.1 %; 45 ± 10% r.h., 86.8%; 55–65% r.h., 48.2 % and 100% r.h., 0.3%. Similar trends were recorded with all three humectant-surfactant combinations. Further studies revealed that the adverse effect of humidity on DMSO-polysorbate mixtures could be at least overcome partially by regulating the DMSO concentration.     

Efficacies of low- to high-volume (960-10 700 litre ha− 1) citrus sprayers for applying petroleum spray oil to control chinese wax scale

Petroleum spray oil (2, 4 and 6% in water) was applied to Valencia orange, Citrus sinensis (L.) Osbeck, for the control of Chinese wax scale, Ceroplastes sinensis del Guercio, using a low-volume ( <2000 litre ha^?1)air-blast (LV AB) sprayer, a low- to high-volume (L-HV) (up to 7000 litre ha^?1) sprayer with four fan-assisted rotary atomiser (FARA) spray heads mounted on a vertical tower, and a high-volume (>7000 litre ha^?1) oscillating boom (HV OB) sprayer. The most effective sprayer was the L-HV FARA sprayer. The most cost-effective treatment was a 20 ml litre^?1 (60 litre oil ha^?1) spray applied at 3000 litre ha^?1 by the L-HV FARA sprayer. It gave mortality equivalent to a standard 20 ml litre^?1, 10 700 litre ha^?1 spray (214 litre oil ha^?1) applied by the HV OB sprayer but with 72% less spray and significantly less oil deposited per cm² of leaf area. Equivalent or significantly (P = 0·05) higher mortality than that given by the 10 700 litre ha^?1 HV OB spray was given by the 40 ml litre^?1, 3000 (120 litre oil ha^?1) and 60 ml litre^?1, 2180 and 3000 litre ha^?1 (130·8 and 180 litre oil ha^?1) L-HV FARA sprays, but the 60 ml litre^?1 sprays deposited more oil per cm² than the 20 ml litre^?1 HV OB spray and were considered to be potentially phytotoxic. The least effective sprayer was the LV AB sprayer, which applied a 60 ml litre^?1 spray (57·6 litre oil ha^?1) at 960 litre ha^?1. Linear relationships were established for Chinese wax scale mortality, transformed using an angular transformation (arcsin proportion), versus log₁₀ spray volume for the 20, 40 and 60 ml litre^?1 sprays applied by L-HV FARA at 1260,2180 and 3000 litre ha^?1, mortality versus log₁₀ μg oil cm^?2 and log₁₀ μg oil versus log₁₀ volume of oil sprayed.     

Effect of temperature on the toxicity of low concentrations of methyl bromide to diapausing larvae of the warehouse moth Ephestia elutella (Hübner)

The performance of low concentrations of methyl bromide against diapausing larvae of Ephestia elutella at 15 and 25°C was assessed in extended exposure periods. At concentrations of 1.9 mg litre^?1 and below, test batches required higher concentration-time (ct) products for 100% kill at 25°C than at 15°C. The minimum concentration at which the concentration: time relationship still applied was between 1.3 and 1.9 mg litre^?1 at 15°C, whereas at 25°C it was between 2.7 and 4.0 mg litre^?1. For many individuals within each population sample, however, lower concentrations at moderate dosage levels remained lethal. At 25°C, a ct product of about 90 mg litre^?1 h gave between 53 and 77% kill at 6.1, 4.0, 2.7 and 1.9 mg litre^?1. The trends observed suggest that the most tolerant members of the population have an enhanced ability to detoxify methyl bromide at the higher temperature. The implications of the results for the build-up of resistance and for practical control measures are discussed.     

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.     

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).     

Effect of short exposures to a high concentration on the subsequent toxicity of low concentrations of methyl bromide to diapausing larvae of the warehouse moth,Ephestia elutella (Hübner)

Ephestia elutella larvae in diapause were exposed at 25°C to methyl bromide at 12 mg litre^?1 for 3.5 or 7.5 h and then immediately exposed to a lower concentration. The minimum effective concentration (that at which Haber's rule, concentration × time = k, a constant for mortality, still applied) was about 3 mg litre^?1 in tests with no previous exposure toa high concentration, but it was about 2.5 mg litre^?1 for individuals surviving a 3.5 h exposure to 12 mg litre^?1, and was about 1.6 mg litre^?1 for those surviving a 7.5 h exposure to 12 mg litre^?1. These exposures to 12 mg litre^?1, respectively, killed 2–20% and 50–75% of larvae exposed, and hence the smaller the proportion of survivors of exposure to a high concentration, the lower the minimum effective concentration needed against them. Thus the low concentration persisting at the end of a practical fumigation should contribute significantly to the success of the treatment and be much more effective than any similar low concentration present soon after the introduction of gas.     

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.     

The response of three soil fungi to dalapon and diuron treatments

Dalapon and diuron are two common herbicides used for the control of weeds. A study of the response of Gliocladium virens, Trichoderma hamatum and T. koningii in cultures to the herbicides was carried out. Changes in fungal colony morphology and growth and sporulation rates in the presence of up to 10⁵ mg herbicide litre^?1 were monitored. The three fungi were not adversely affected at a concentration of 10³ mg litre^?1. Changes in colony morphology and decreases in growth and sporulation rates were evident at the maximum test concentration (10⁵ mg litre^?1) of both herbicides. These generally recovered when the fungi were replated in the absence of the herbicides.     

Relation between volatility rating and composition of phenoxy herbicide ester formulations

A CIPAC/AOAC test with tomato plants is used to specify the volatility ratings of herbicide ester formulations. This work compares the tomato plant test with an alternative chemical one. The concentrations of esters and the effective molecular weight and density of each formulation were used with the ester vapour pressures to calculate its herbicide vapour pressure as complete, and evaporated formulations. The range was from 28.8 mPa (at 257deg;C) for a mixture of 2,4–D esters to 0–07 mPa (at 25°C) for a 2,4,5–T-(iso-octyl) formulation, as complete formulations, and 35-5 and 0–16 mPa (at 25°C) as evaporated ones. A value of 0–6 mPa (at 25°C) was selected on the basis of the tomato plant test as the cut-off area for low-volatile esters and is recommended to be included in specifications for herbicide esters. Formulations with a herbicide vapour pressure above 3.3 mPa (at 25°C) are high-volatile ones according to the tomato plant test, while between 0–6–3.3 mPa (at 25°C) is a borderline region where the test gives mixed results. Levels of 2,4–D-ethyl and methyl were added to pure 2–ethylhexyl esters of 2,4–D and a 2,4,5–T-(iso-octyl) formulation to find what level of contamination would change the rating of these esters from low to high volatile. Formulations of 2,4–D-(iso-octyl) should not contain more than 11 g litre^?1 2,4–D as methyl ester or 2.0 g litre^?1 2,4–D as ethyl ester. Formulations of 2,4,5–T-(iso-octyl) should not contain more than 26 g litre^?1 2,4–D as methyl ester or 4.7g litre^?1 2,4–D as ethyl ester.     

The toxicity of cyromazine to Chironomus zealandicus (chironomidae) and Deleatidium sp. (leptophlebiidae)

The toxicity of cyromazine and a commercial formulation, ‘Vetrazin’®, to Chironomus zealandicus (thummi) Hudson and Deleatidium sp. was investigated. Under acute test conditions, the LC₅₀ values for each species were quite comparable. For C. zealandicus, the value varied according to instar, 100–400 mg litre^?1 for second- and third-instar to 1000–10000 mg litre^?1 for older fourth-instars. For the one size class of Deleatidium tested (c.10 mm long), the value was 300–400 mg litre^?1. High control mortalities of C. zealandicus limit that species' usefulness as an acute bioassay candidate. Under chronic test conditions, cyromazine showed a high toxicity to eggs or early-instar larvae of C. zealandicus. The maximum acceptable toxicant concentration for cyromazine against C. zealandicus was approximately 17.5 μg litre^?1. The possibility of water contamination at this level is discussed. Whole-of-life chronic tests with C. zealandicus indicated that the most susceptible stage was in the egg or soon after larval emergence. These results highlight the dangers of using short-term acute toxicity results to formulate environmental exposure limits for modern pesticides that do not have dysfunction of the nervous system as their mode of action.     

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     

Depression of the minimum concentration of methyl bromide effective against diapausing warehouse moth larvae at 15°c by prior exposure at a moderate concentration

Warehouse moth (Ephestia elutella) larvae in diapause were exposed at 15°C to methyl bromide at 8 mg litre^?1 for 14.5 h and then immediately exposed at a lower concentration. The exposure at 8 mg litre^?1 killed 44–69% of the larvae treated. Subsequent concentrations down to 1.1 mg litre^?1 obeyed Haber's rule (concentration × time= k, a constant for mortality), but a higher concentration-time product (ct) was required for over 90% kill at 0.8 mg litre^?1. Only concentrations down to 1.9 mg litre^?1 obey Haber's rule if there is no prior exposure at a higher concentration. Although minimum effective concentrations are lower at 15°C than at 25°C, exposure at a higher concentration depresses the subsequent level to a similar extent at each temperature. The contribution to the efficacy of a treatment, of low concentrations persisting at the end of fumigation, is thus likely to be even greater at moderate to low temperatures than at 25°C. The implications for the development of resistance to methyl bromide are discussed.     

The algaecidal activity of some substituted 1,3-diphenylureas, 1-phenyl-3-(2-pyridyl)ureas and the corresponding thioureas

Twelve ureas and thioureas with 1,3-diphenyl- and 1-phenyl-3-(2-pyridyl) were tested as potential herbicides in a simple screen against two species of algae Chlorella fusca and Anabaena variabilis. Several were shown to inhibit growth at 100 mg litre^?1 but only 1-[2,4-bis(azidosulphonyl)phenyl]-3-(2-pyridyl)urea and 1,3-bis(4-isopropyl- idenehydrazinosulphonylphenyl)thiourea showed any activity at 1 mg litre^?1. This compares with the well-established urea herbicide diuron which, in identical tests, gives similar inhibition of growth at concentrations as low as 0.01 mg litre^?1.     

Effects of some foliar fungicides on the chrysomelid beetle Gastrophysa polygoni (L.)

The effects of the fungicides benomyl, thiophanate-methyl and triadimefon on the chrysomelid beetle Gastrophysa polygoni were investigated in the laboratory. Contact with a suspension of benomyl (1.5 g a. i. litre^?1 did not affect the hatchability of the eggs. Larvae were reared on shoots of knotgrass (Polygonum aviculare) that had been sprayed with suspensions of benomyl, ranging in concentration from 0.1 to 5.0 g a. i. litre^?1. The mortality to the adult stage, of larvae reared on shoots treated with concentrations of benomyl of 0.5 g a. i. litre^?1 and above, was significantly higher than that of control larvae. At concentrations of 2.0 g a. i. litre^?1 and above, no larvae survived to the adult stage. The LD₅₀ was 0.78 g a. i. benomyl litre^?1. The LT₅₀ values at concentrations of 1.0, 2.0 and 5.0 g a. i. benomyl litre^?1 were 22.6, 12.6 and 5.3 days, respectively. The mean weights of adults bred from larvae that had been reared on shoots treated with benomyl (0.5 and 1.0 g a. i. litre^?1) were significantly less than those of adults bred from control larvae. The mortality of larvae, reared on shoots of P. aviculare treated with triadimefon (0.5 g a. i. litre^?1) or thiophanate-methyl (1.0 g a. i. litre^?1), was also significantly higher than that of control larvae. Females kept on plants of P. aviculare treated with benomyl (1.5 g a. i. litre^?1) laid similar numbers of eggs to those kept on untreated plants, and the hatchability of the eggs was not affected.     

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.     

The microimmersion bioassay: A novel method for the topical application of pesticides to spider mites

A novel and versatile method is described for measuring the contact activity of acaricides against spider mites. The microimmersion (MI) bioassay involves drawing batches of 25 mites into small pipette tips under vacuum, immersing them for 30 s in 35 μ1 of a test solution, and then confining the treated subjects on clean foliage in holding cells. Evaluations of amitraz, bifenthrin, chlorpyrifos and dicofol against susceptible strains of Tetranychus urticae Koch showed the MI bioassay to be equally applicable to formulated and technical acaricides (the latter dissolved in acetone + distilled water; 20 + 80 by volume), and to give LC₅₀ values that corresponded well with those from a conventional residual bioassay. The most important difference between bioassay methods was the consistently greater slope of probit lines from MI tests. Results were not highly sensitive to varying the immersion period between 15 and 60 s, and low control mortality was observed with ethanol or acetone concentrations of up to 500 ml litre^?1, and surfactant concentrations of up to 10 g litre^?1. The potential of this method for assessing the relative toxicity of both fast- and slow-acting acaricides, screening small quantities of experimental compounds for acaricidal activity, and improving the laboratory procedure for selection and characterization of acaricide resistance is discussed.     

A field unit for determining dimethoate in fruit and vegetable dips

The concentration of dimethoate in post-harvest dips needs to be maintained at 400 or 500 mg litre^?1 to ensure that fruit fly are killed and also to keep residue levels below the MRL. A field unit which contains a colorimeter, a heating block and cooling positions has been evaluated. The diluted dip sample produces a colour with 4-(p-nitrobenzyl)pyridine after heating and the addition of tetraethylenepentamine. Precision of the unit was acceptable for a field test (repeatability of ± 10.1%) and there was reasonable agreement between determinations made on the unit and by an HPLC method for a range of dimethoate concentrations from 300 to 700 mg litre^?1. The unit can be used at the dip site and the analysis is completed in 30 minutes.     

Leaching of atrazine and hexazinone from Abies nordmanniana (Steven) spach plantations

The content of the herbicides atrazine and hexazinone was measured in drainage water from seven to ten-year-old plantations grown with Abies nordmanniana (Steven) Spach on two clayey soils in Denmark. The concentrations of atrazine varied between 0.06 and 7.79 μg litre^?1. The concentrations of hexazinone were different at the two locations, ranging from 0.07 to 2.09 μg litre^?1 at Bremersvold and from 3.47 to 42.66 μg litre^?1 at Koege. Metabolites of both herbicides were identified.     

Non-target effect of herbicides: I. effect of glyphosate and hexazinone on soil microbial activity. Microbial population,and in-vitro growth of ectomycorrhizal fungi

The effects of two herbicides, glyphosate (as a 359 g litre^?1 SL) and hexazinone (as a 50gkg^?1 granule) on soil microbial population, carbon dioxide evolution, and in-vitro growth of five species of ectomycorrhizal fungi were investigated. Glyphosate at 0–54 and 3.23 kg a.i. ha^?1 and hexazinone at 1. 2 and 8 kg a.i. ha^?1 did not reduce soil microbial population or carbon dioxide evolution in the long term (6 months). However, there was a significant short-term (2 months) effect of glyphosate on both fungal and bacterial counts at the 0.54 kg ha^?1 treatment. In in-vitro tests, Cenococcum graniforme. Hebeloma crustuliniforme and Laccaria laccata were more susceptible to both herbicides than was Suillus tomentosus. which was, in turn, more susceptible than Paxillus involutus. The growth of all five ectomycorrhizal fungi was significantly reduced when subjected to concentrations above 50 μl formulation litre^?1 (glyphosate) or 50 μg formulation litre^?1 (hexazinone).