The fate and insecticidal activity of pirimiphos-methyl in stored wheat grain

The degradation of [¹⁴C]pirimiphos-methyl was investigated on a 1-kg bulk of grain stored in the laboratory at 15°C for 28 weeks. Breakdown of pirimiphos-methyl was slow, leaving 77% of the applied dose unchanged at the end of the experiment. The major degradation product was the hydroxypyrimidine (up to 12.5% of the applied dose) with the remainder of the residue (up to 12.1%) remaining within the grain tissues after solvent extraction. The efficacy of the treatment was assessed in a parallel experiment by bioassay of a 5-kg bulk of grain dosed with unlabelled pirimiphos-methyl. 100% Mortality of an organophosphateresistant strain of Oryzaephilus surinamensis L. was maintained throughout the experiment whereas some survival of an organophosphate-resistant strain of Tribolium castanewm (Herbst) occurred after 12 weeks of storage. This increased to give a 20% survival rate at the end of the experiment.     

Efficacy of Surface Dust Treatments of Pirimiphos-Methyl and Etrimfos when Applied to Commercially Stored Wheat and Barley

Commercially stored wheat and barley were surface treated with dust formulations of pirimiphos-methyl and etrimfos at the manufacturer's recommended application rate. Samples were taken at four-weekly intervals for 32 and 16 weeks for wheat and barley respectively. Pesticide efficacy was determined using insect bioassays and chemical analysis of residues. There was no evidence to suggest a decline in residue levels of either pesticide over the experimental period. However, considerable variation was observed in the residue levels recorded at different sample points and also between residue levels recorded for the same point over the trial period. Control of susceptible strains of Tribolium castaneum (Herbst), Oryzaephilus surinamensis (L.) and Sitophilus granarius (L.) was achieved where recovered pesticide residues remained above 1 mg kg⁻¹ pirimiphos-methyl and 1·6 mg kg⁻¹ etrimfos.     

Combinations of pirimiphos-methyl and carbaryl for stored grain protection

In laboratory experiments, whole wheat was treated with pirimiphos-methyl or carbaryl or combinations of these two insecticides; the treated grain was then adjusted to a 12% moisture content and stored at 25°C for bioassay at various intervals over a period of 39 weeks. Pirimiphos-methyl at 5.1 mg kg^?1 effectively controlled Sitophilus granarius (L.) and Tribolium confusum Jacquelin du Val but was ineffective against Rhyzopertha dominica (F.) CRD 118, a strain showing malathion resistance. Conversely, carbaryl at 6.5 mg kg^?1 (but not at 3.1 mg kg^?1) was effective against R. dominica, but ineffective against the other two species. A combination of pirimiphosmethyl + carbaryl, at 1.8 + 5.1 mg kg^?1, controlled S. granarius and R dominica but not T. confusum, whilst a 4.2 + 3.4 mg kg^?1 combination was relatively more effective against T. confusum but less so against R. dominica. In a separate experiment, whole wheat was treated with carbaryl at 2.5, 5.0 and 7.5 mg kg^?1 (nominal rates). Samples were stored and, at various times after the treatments, were bioassayed with R. dominica CRD 2, at 20, 25, 30 and 35°C. The results were comparable with those for the CRD 118 strain, but efficacy was reduced at higher temperatures. The combination of pirimiphos-methyl at 4–5 mg kg^?1 and carbaryl at 5–6 mg kg^?1 is suggested as a potentially useful grain protectant where R. dominica is a problem and long term storage is required. These results are discussed in relation to the protection of stored grain in Australia.     

Inactivation of fenitrothion on stored maize at different moisture contents

Biological activity of fenitrothion on stored maize at various moisture contents and at different times after application was measured by biological assay using adults of Tribolium castaneum (Herbst). Inactivation of actual residues over time was then determined after making the necessary allowance for chemical breakdown. At a given moisture content, the inactivation process was substantially completed during the first 6 weeks after application and loss of effectiveness from 6 weeks onwards resulted mainly from chemical breakdown. At a given time after application, residues were less active at higher moisture content (m.c). Differences in activity between moisture contents were apparent within a few hours of application and continued to increase for up to 3 days, with relatively little change thereafter during storage of 24 weeks. Thus after 24 weeks, residues on maize of 18% m.c. had an activity about 20% that of similarly-aged residues at 10% m.c. and 4% that of freshly-applied residues at 10% m.c. These results were in general accord with changes in the proportion of the residue which was collected from the kernels by a surface wash with methanol, this readily-extractable residue presumably representing the insecticide that may be picked up by insects.     

The analysis of crops and soils for the triazine herbicide cyanazine and some of its degradation products. II. Results

Crops and soils from field trials in 1967–1970 in several countries have been analysed for residues of the triazine herbicide cyanazine (‘BLADEX’

1 Shell Registered Trade Mark.

^a or ‘FORTROL’^a' 2-chloro-4-(1-cyano-1-methylethylamino)-6-ethylamino-1,3,5-triazine) and for its degradation products 2-chloro-4-(1-carbarmoyl-1-methylethylamino)-6-ethylamino-1,3,5-triazine ( II ), 2-chloro-4-(1-cyano-1-methylethylamino)-6-amino-1,3,5-triazine ( V ) and 2-chloro-4-(1-carbonyl-1-methylethylamino)-6-amino-1,3,5-triazine ( VI ). The time for the concentration of cyanazine in soils to fall to half the initial value was in the range 1.3 to 5 weeks with a mean value of 2.4 weeks. The rate of loss was not affected by sparse crop cover and there was some indication that the rate was greater under moist soil conditions. Residues of up to 0.5 part/million of ( II ) and up to 0.08 part/million of ( VI ) were detected in soils at 4 weeks from cyanazine application at 2 kg/ha. The residues of cyanazine and the degradation products declined rapidly and were 0.07 part/million or less at 16 weeks from treatment. Repeated annual applications did not lead to a detectable build up of residues in soil. Neither residues of cyanazine nor those of ( II ), ( V ) or ( VI ) could be detected in a wide range of crops harvested from soil treated in accordance with the likely recommendations and the limits of detectability were 0.01 to 0.04 part/million.     

A simple method for long-term cryopreservation of <Emphasis Type="Italic">Calonectria ilicicola</Emphasis> on barley grains

We developed a simple method for long-term preservation of the soybean red crown rot fungus, Calonectria ilicicola, using barley grains. Autoclaved barley grains were inoculated with the fungus, then incubated at 25°C for 1 month. After incubation, grains were dried to approximately 3% moisture content, and stored at 4, −20, or −80°C for 3 years. C. ilicicola preserved on barley grains at −80°C remained viable without any change in mycelial growth and virulence. These results showed that C. ilicicola can be successfully cryopreserved for extended periods on barley grains at −80°C. We also confirmed that cultures preserved on barley grains are suitable for direct use without further manipulation as inocula in pathogenicity tests.     

Residue levels of three organophosphorus insecticides in sweet pepper grown in commercial greenhouses

The degradation rates and residue levels of diazinon, pirimiphos-methyl and chlorpyrifos in the leaves and fruits of pepper plants grown in commercial greenhouses were studied using g.l.c. Analysis of leaves at intervals following application showed that the initial residue of diazinon was higher than that of the other two insecticides, while its dissipation rate was faster. The dissipation of chlorpyrifos in fruits was faster than diazinon. The maximum residue levels (m.r.l.) of diazinon (0.5 mg kg^?;1) and chlorpyrifos (0.1 mg kg^?;1) were reached after 13 and 8 days of application respectively. With diazinon and pirimiphos-methyl, sprayed 3 weeks before inflorescence, very low concentrations of both insecticides were found in fruits, although these compounds have no systemic behaviour. Chlorpyrifos residue level of 0-2 mg kg ^?;1 in harvested fruits did not drop below m.r.l. after 11 days holding period.     

Effects of certain herbicides on the oxidative decarboxylation of tryptophan by peroxidase

Non-enzymic and peroxidase-catalysed oxidative decarboxylations of tryptophan (TPP) were studied. The in-vitro rate of enzymic reaction was affected by various herbicides at low concentrations (10^?5?10^?4_M): dinoseb, 2,4-D, dichlobenil and benazolin acted as inhibitors; on the other hand, chlorpropham, bromacil, diphenamid and 4-ethylamino-6-isopropylamino-1,3,5-triazin-2-ol (hydroxyatrazine) were stimulatory. The results of in-vivo experiments showed that chlorpropham and 2,4-D changed the activity of peroxidase from Brassica germinated seeds in vivo, as they do in vttro. Determinations of consumed TPP were carried out either by spectro-photometry or by chromatography.     

An assessment of chlorpyrifos-methyl,etrimfos, fenitrothion and pirimiphos-methyl as grain protectants

Trials were carried out over two consecutive years to compare the efficacy of chlorpyrifos-methyl, etrimfos, fenitrothion and pirimiphos-methyl against susceptible and organophosphorus-resistant strains of Tribolium castaneum Herbst, Sitophilus granarius L. and Oryzaephilus surinamensis L., gamma-HCH-resistant strains of Acarus siro L. and Glycyphagus destructor Schrank, and a susceptible strain of Tyrophagus longior Ger-vais. Pirimiphos-methyl was not evaluated against the three mite species as data on the efficacy of this material had previously been published. Etrimfos and pirimiphos-methyl were also tested against a susceptible and an organophosphorus-resistant strain of Sitophilus oryzae L. Each pesticide was applied to two separate 20-tonne batches of English wheat and stored under ambient conditions for 36 weeks. The efficacy of the pesticides was assessed regularly over the storage period using established bioassay techniques. However, chlorpyrifos-methyl and fenitrothion were assessed against susceptible and resistant strains of S. granarius for 32 weeks only. Each of the four pesticides produced >95% mortality of the susceptible strain of all insect species tested for the entire duration of the trial with the exception of fenitrothion, when survival of T. castaneum increased after 32 weeks. Only fenitrothion failed to give 100% mortality of the resistant strain of S. granarius throughout the trial, but even so, the mortality was always >95%. Chlorpyrifos-methyl, etrimfos and pirimiphos-methyl gave much better control of the resistant T. castaneum than fenitrothion, and etrimfos gave slightly better control of resistant O. surinamensis than pirimiphos-methyl which was in turn better than chlorpyrifos-methyl at 36 weeks. Both etrimfos and pirimiphos-methyl gave 100% mortality of the susceptible and resistant strains of S. oryzae. None of the pesticides maintained 100% kill of A. siro throughout the trial and fenitrothion failed to achieve this level of mortality after only 4 weeks. Etrimfos produced 100% mortality of the other two mites species tested throughout the trial, whereas both chlorpyrifos-methyl and fenitrothion achieved this level of mortality for 32 weeks.     

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.     

Chlorpyrifos-methyl plus bioresmethrin; Methacrifos; Pirimiphos-methyl plus bioresmethrin; and synergised bioresmethrin as grain protectants for wheat

Field trials with various pesticide combinations were carried out on bulk wheat in commercial silos in Queensland, South Australia and Western Australia. Laboratory bioassays on samples of treated grain at intervals over 8 months using malathion-susceptible and malathion-resistant strains established the following orders of efficacy: against Sitophilus oryzae (L.), chlorpyrifos-methyl 10 mg kg^?1 + bioresmethrin 1 mg kg^?1 = methacrifos 15 mg kg^?1 in aerated storage > pirimiphos-methyl 4 or 6 mg kg^?1 + bioresmethrin 1 mg kg^?1 = bioresmethrin 4 mg kg^?1 + piperonyl butoxide 16 mg kg^?1; against Rhyzopertha dominica (F.), bioresmethrin 4 mg kg^?1 + piperonyl butoxide 16 mg kg^?1 > methacrifos 15 mg kg^?1 > chlorpyrifos-methyl 10 mg kg^?1 + bioresmethrin 1 mg kg^?1 = pirimiphos-methyl 4 or 6 mg kg^?1 + bioresmethrin 1 mg kg^?1. All treatments completely prevented production of progeny in Sitophilus granarius (L.), Tribolium castaneum (Herbst), T. confusum Jackquelin du Val and Oryzaephilus surinamensis (L.). The biological efficacy of methacrifos was greater and the rate of degradation lower in aerated than in non-aerated storage. Residue levels of all compounds were determined chemically and were below proposed international residue levels to be considered by the Codex Alimentarius Commission.     

Rates of reaction of singlet oxygen with some systemic pyrimidine fungicides and related compounds

Rate constants have been measured for the reaction in chloroform solution of singlet oxygen with the fungicides ethirimol (5-butyl-2-ethylamino-6-methylpyrimidin-4-ol) and dimethirimol (5-butyl-2-dimethylamino-6-methylpyrimidin-4-ol), and with the compounds 2-dimethylamino-5,6-dimethylpyrimidin-4-ol, 2-dimethylamino-6-methylpyrimidin-4-ol, 4-benzyloxy-2-dimethylamino-5,6-dimethylpyrimidine and 2-diethylamino-6-methylpyrimidin-4-ol. The values obtained show that singlet oxygen reacts readily with these compounds; the differences between the rate constant values have been rationalised in terms of the different structural features of the compounds studied. The possibility that singlet oxygen may react with agricultural chemicals under natural conditions is considered.     

Stability of pyrethroids on wheat in storage

The four pyrethroids, permethrin, phenothrin, fenvalerate and deltamethrin were applied to wheat which was stored for 52 weeks at 25 or 35°C, and either 12 or 15% moisture content. Rates of loss were calculated from residue analyses of the wheat at five intervals during storage. Calculated half-lives (weeks) for the pyrethroids at 25°C (12% moisture) and 35°C (15% moisture) were: permethrin 252 and 44, phenothrin 72 and 29, fenvalerate 210 and 74, and deltamethrin 114 and 35, respectively.     

Degradation of bifenthrin,chlorpyrifos and imidacloprid in soil and bedding materials at termiticidal application rates

Organophosphorus, pyrethroid and chloronicotinyl insecticides have been used to control termites in building structures in recent years. We investigated the degradation behaviour of three insecticides (bifenthrin, chlorpyrifos and imidacloprid) at termiticidal application rates under standard laboratory conditions (25 °C, 60% field moisture capacity and darkness) for 24 months. The study was carried out on one soil and two bedding materials (sand-dolomite and quarry sand), which are commonly used under housing in Australia. Experiments were also conducted to examine the effect of soil moisture on the degradation of these insecticides. Insecticide residues in the samples collected at different days after application were measured by high performance liquid chromatography (HPLC). The rate of degradation of bifenthrin and imidacloprid insecticides was adequately described by a first-order kinetic model (r² = 0.93–0.97). However, chlorpyrifos degradation was biphasic, showing an initial faster degradation followed by a slower rate. Therefore, the degradation data during the slower phase only (after a two-month period) followed the first-order law (r² = 0.95). Soil moisture had little effect on degradation of imidacloprid and bifenthrin. Among the three insecticides, bifenthrin and imidacloprid were most stable and chlorpyrifos the least. Chlorpyrifos showed a major loss (75–90%) of residue during the 24 months incubation period. In the bedding materials, simultaneous accumulation of the primary metabolite of chlorpyrifos, TCP (3,5,6-trichloro-2-pyridinol) was observed. Hydrolysis appeared to have caused the observed rapid loss of chlorpyrifos, especially in the highly alkaline bedding materials (sand-dolomite and quarry sand). © 1999 Society of Chemical Industry     

Fate of terbutryn in macrophyte-free and macrophyte-containing farm ponds

Terbutryn (2-ethylamino-4-(tert-butylamino)-6-methylthio-s-triazine) was applied in June 1978, to two farm ponds (A and C) near Winnipeg. Canada, to give 100 μg/l water concentrations. The persistence of the herbicide and its degradation products was monitored over a 61-week period following application. The half-life of terbutryn m the water column ranged from 3 weeks in Pond C, which contained heavy growths of cattails (Typha sp.) and duckweed (Lemna sp.), to 30 days in Pond A. which was free from aquatic macrophytes, Terbutryn residues m sediment reached a maximum of 1.4 μg/g (dry wt) in Pond A and 0.5 μg/g in C. Maximum concentrations of N-deethylated terbutryn (2amino-4-(tert-butylamino)-6-methylthio-s-tria-zine)(DET) were 14.4 μg/l in Pond A water after 61 weeks and 0.14 μg/g in Pond C sediment after 30 weeks. The maximum concentration of hydroxy-terbutryn (2-hydroxy-4-ethyl-amino-6-(tert-butylamino)-s-triazine) (HT) observed in pond water was 6.4 μg/l in Pond C after 7 weeks. HT was not detected in sediment (<0.05 μg/g) during the study. After 61 weeks, about 50% of the terbutryn that was added could still be accounted for in Pond A and 35% in Pond C. Terbutryn. DET and HT represented an estimated 71, 28 and 1%, respectively, of total terbutryn remaining in Pond A and 65, 29 and 6%, respectively, of that remaining in Pond C, 61 weeks after application, Terbutryn residues in Typha ranged from 0.3 μg/g (dry wt) in the shoot to 3.3 μg/g in the roots. After 12 weeks, terbutryn residues in plants (Pond C) were estimated to account for 1 to 4% of the herbicide in the pond.     

The uptake,excretion and metabolism of the acylurea insecticide,flufenoxuron in spodoptera littoralis larvae,by feeding and topical application

Flufenoxuron is an acylurea insecticide which inhibits chitin synthesis. Its uptake, excretion and metabolism in larvae of Spodoptera littoralis have been measured. Larvae fed on a leaf disc sprayed at an application rate equivalent to 50 g ha^?1rapidly absorbed a maximum of 20% of ingested flufenoxuron, the remainder being voided in the frass. Excretion of absorbed compound was slow, with a 50% excretion time of approximately 20 h. Flufenoxuron was equally effective as an insecticide by topical application or ingestion. Following topical application, a total of 11% of the dose had penetrated into the body within 24 h. Of this 11%, half had travelled to the gut so that the rest of the body tissues contained no more than 6% of the toxicant dose. The concentration of flufenoxuron in the body tissues was maintained for at least 24 h, the surface residue probably acting as a reservoir. The compound was metabolically quite stable. Following topical application the 6 % of the applied dose which was absorbed into the body was still 92% as unchanged flufenoxuron 24 h after application. The enhanced toxicity of flufenoxuron to S. littoralis compared with earlier acylureas can probably be attributed to its slower metabolism and reduced excretion.     

Pirimiphos-methyl applied to spanish citrus trees: Residue decay and final residue levels at harvest time in precocious fruits

Pirimiphos-methyl [O-(2-diethylamino-6-methylpyrimidin-4-yl) O,O-dimethyl phosphorothioate], the active ingredient in ‘Actellic 50E’ (ICI PLC, Plant Protection Division) insecticide formulation, was field-applied at a rate of 7.5 kg a.i. 6000 litres^?1 ha^?1 to Spanish mandarin, orange and lemon trees growing in the main production areas (provinces of Castellón, Valencia, Alicante and Murcia). Dissipation curves over a 28-day post-application period, as well as the final residue levels at the harvest-time in precocious fruits, were determined in order to assist in the setting of legal fruit tolerances and harvest withholding periods. In all cases, residue decay could be fitted to two consecutive first-order processes. Final residue levels at harvest-time (the first fortnight of October) in precocious fruits, as a result of one, two or three sprays at the usual application dates (the first fortnight of June and/or September) were, respectively: for Clementina mandarins 0.05, 0.57 and 0.72; for Satsuma mandarins 0.09, 0.55 and 0.73; and for Navelina oranges 0.08, 0.25 and 0.46 mg of pirimiphos-methyl kg^?1. The data indicated that starting from the seventh post-application day, pirimiphos-methyl degraded much more slowly in lemons growing in Alicante than in those growing in Murcia. It was speculated that this difference could be due to variations between the local field climates, or to a severe water stress, suffered by the orchard in Murcia as the result of a lack of irrigation water.     

The degradation of (Z)- and (E)-1,3-dichloropropenes and 1,2-dichloropropane in soil

The degradation in soil of the major constituents of a 1,3-dichloropropene-1,2-dich-loropropane nematicide has been studied under laboratory and outdoor conditions. In sealed glass containers, ( Z)- and ( E)-1,3-dichloropene- 2-¹⁴C were converted in soil into the corresponding 3-chloroallyl alcohols and these alcohols were in part strongly bound to the soil. The ( Z)- and ( E)-3-chloroacrylic acids were also found as minor products. More polar products were detected and these released the chloroacrylic acids in 20–30% yield upon hydrolysis. Although the 1,3-dichloropropenes were lost by volatilisation from soil stored in open glass jars outdoors, they also underwent degradation to the same products that were detected in sealed containers. There was evidence of only slight degradation of 1,2-dichloropropane- 2-¹⁴C (4 % or less of the applied radioactivity remained unextracted from a loam soil after 5 months). When soil treated with the 1,2-dichloropropane was stored outdoors in an open glass container, less than 1 % of the original radiolabel remained in the soil after 10 days under these conditions due to volatilisation of the applied material. In a separate experiment potatoes were grown in soil 6 months after treatment with a mixture of both ( Z)- and ( E)-1,3-dichloropropene- 2-¹⁴C and 1,2-dichloropropane- 2-¹⁴C. Although 5 % of the applied radiolabel remained in the soil at potato harvest the potato tubers contained only a very small residue (0.007 mg/kg).     

DIFFERENTIAL PHYTOTOXICITY OF ATRAZINE AND AMETRYNE TO BANANAS*

Summary. In field screening trials for bananas (Musa acuminata var. Dwarf Cavendish) in Hawaii, ametryne (2-methylthio-4-ethylamino-6-isopropylamino-s-triazine) was less phytotoxic to bananas than atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine). Sand culture experiments showed that both herbicides were equally injurious to banana plants. Differential degradation of the herbicides by the plants did not account for the phytotoxicity observed. Both herbicides were partly metabolized by the plant to their common hydroxyl derivative (hydroxyatrazine) and two other unidentified metabolites after 3 and 7 days of exposure to nutrient solution containing ¹⁴C-labelled ametryne and atrazine. Phytotoxicity was directly related to leachability of the herbicides and negatively related to adsorption capacity of each soil for the herbicides. Organic matter content seemed to be correlated to the response observed. It was postulated that phytotoxicity in the field may have been attributed to differential location of the herbicide in relation to the roots.     

Adsorption of transformation products of atrazine by soil

The adsorption of atrazine and its transformation products, desisopropylatrazine (2-chloro-4-ethylamino-6-amino-l,3,5-triazine), desethyl-atrazine (2-chloro-4-amino-6-isopropylamino-l,3,5-triazine) and hydroxyatrazine (2-hydroxy-4-ethylamino-6-isopropylamino-l,3,5-triazine) to four top-soils was measured. Adsorption coefficients decreased in the order hydroxy atrazine, atrazine, desisopropylatrazine, and desethyl-atrazine: the distribution coefficient between organic matter and water (K_OM) ranged from 40 to 100 dm³ kg^?1 for atrazine, from 30 to 60 dm³ kg^?1 for desisopropylatrazine, from 20 to 50 dm³ kg^?1 for desethylatrazine and from 100 to 590 dm³ kg^?1 for hydroxy atrazine. Data are discussed in the context of earlier literature.