Phthalides as promising insecticides against Tuta absoluta (Lepidoptera: Gelechiidae)

In this study, the insecticide potential of eight phthalides derived from furan-2(5H)-one was evaluated against Tuta absoluta (Meyrick) (Lepidoptera: Gelechiidae) larvae. The potency of the most active phthalides and the susceptibility of six different T. absoluta populations to these compounds were determined. The toxicity of these molecules to two non-target species (Solenopsis saevissima Smith and Tetragonisca angustula Latreille) was also evaluated. Two phthalides (3 and 4) presented insecticide potential against T. absoluta. Phthalide 4 was as toxic as piperine (positive control) and both phthalides exhibited rapid action (LT₅₀ < 2 hours). The variation in the susceptibility of T. absoluta populations to the phthalides 3 and 4 was low. Neither phthalide presented physiological selectivity for non-target species.

Therefore, the phthalides 3 and 4 are promising molecules, or at least, a starting point for a chemical optimization program leading to formulations for the management of the tomato leafminer. The application of such products should be conducted according to the principles of ecological selectivity.     

Anthropogenic and naturally-produced organobrominated compounds in bluefin tuna from the Mediterranean Sea

In the present study, bioaccumulation potential of two pyrethroid insecticides, bifenthrin and permethrin, was measured using a Lumbriculus variegatus sediment bioaccumulation test. Two sediments differing in their physical characteristics and two different aging periods were tested. Desorption rates measured by Tenax extraction suggested that pyrethroids were bioavailable to L. variegatus, however bioavailability varied among chemicals, sediments and aging time, and was greater for permethrin than bifenthrin. The relatively low biota-sediment accumulation factor (BSAF) values resulted from the extensive biotransformation of pyrethroids by L. variegatus. Biotransformation capacity of L. variegatus to permethrin was further studied with a water-only exposure, and the percentage parent compound dropped to 36.0% after 14 d. These results indicated sediment-associated pyrethroids were bioavailable to L. variegatus, however bioaccumulation was limited because L. variegatus was capable of biotransforming the pyrethroids.     

Adsorption,Desorption, and Mobility of Permethrin in Malaysian Soils

Abstract

The adsorption, desorption, and mobility of permethrin in six tropical soils was determined under laboratory and greenhouse conditions. The six soils were selected from vegetable growing areas in Malaysia. Soil organic matter (OM) was positively correlated (r ² = 0.97) with the adsorption of permethrin. The two soils, namely, Teringkap 1 and Lating series with the highest OM (3.2 and 2.9%) released 32.5 and 30.8% of the adsorbed permethrin after four consecutive repetitions of the desorption process, respectively, compared to approximately 75.4% of the Gunung Berinchang soil with the lowest OM (1.0%) under the same conditions. The mobility of permethrin down the soil column was inversely correlated to the organic matter content of the soil. Permethrin residue penetrated only to the 10–15 cm zone in the Teringkap 1 soil with 3.2% OM but penetrated to a depth of more than 20 cm in the other soils. The Berinchang series soil with the lowest OM (1.0%) yielded leachate with 14.8% permethrin, the highest level in leachates from all the soils tested. Therefore, the possibility for permethrin to contaminate underground water may be greater in the presence of low organic matter content, which subsequently allows a higher percentage of permethrin to move downwards through the soil column.     

A field study on residues of four insecticides used in strawberry protection

Abstract

In 1986 strawberry plots were treated with dimethoate, malathion, permethrin and cypermethrin at 80% bloom of primary flowers. In 1987 the plots were sprayed with dimethoate, malathion and permethrin at 30% bloom. Residue analysis of these insecticides on the flowers were analyzed using solvent extraction and gas liquid chromatography. Residue analysis at 0 to 18 days on flowers and fruit showed an exponential decrease. Organophosphates tended to degrade more quickly than synthetic pyrethroids. The results are discussed in the context of an integrated pest management program.     

Topical application of synthetic pyrethroids to cattle as a source of persistent environmental contamination

Abstract

Following the application of permethrin or cyhalothrin to cattle for the control of ectoparasites, the occurrence and persistence of these chemicals was assessed on the animals and in their environment. The release of permethrin from ear tags containing 1g of the drug on cattle was followed for 65 days and lead to concentrations of 5 to 35 μg of permethrin per gram of hair on the shoulders. On the flanks of the animals, the corresponding values were 10 times lower. Across the 1.5 acre pasture, high concentrations of permethiin were measured at various locations and long after treatment: 6 μg/g on bark of a birch after one week, 5 μg/g on a pole of the fence after two weeks, 1 μg/g in grass from a resting site of the animal after six weeks, and 0.5 μg/g in bark of a pine tree after three month and two weeks after the animals had left the pasture. In similar assays, cyhalothrin applied to milk cows as a pour‐on preparation was monitored. One week following treatment with 0.2 g/animal, hair cut from the shoulders contained 5 μg/g of the insecticide, which disappeared with a half‐life of 12 days. Dust collected two weeks after the pour‐on treatment from the milk barn where the cows were milked twice daily contained 47 μg/g of cyhalothrin, which disappeared with a half‐life of 44 days. These results show that synthetic pyrethroids used on farm animals can be the source of widespread and persistent contamination.     

Acute toxicity and ecotoxicological risk assessment of rice pesticides to Lithobates catesbeianus tadpoles

The objective of this study was to determine the acute toxicity of some pesticides used in irrigated rice farming to Lithobates catesbeianus tadpoles. The LC_50-96h for commercial formulations containing bentazon, penoxsulam, vegetable oil, permethrin and carbofuran, separately and their mixtures, were determined at the proportions commonly used in the field. The limits of risk concentrations of these products for the studied species were also established. The LC_50-96h for tadpoles was 4,530 mg L^?1 for bentazon; 7.52 mg L^?1 for penoxsulam + 145.66 mg L^?1 of vegetable oil; 81.57 mg L^?1 for vegetable oil; 0.10 mg L^?1 for permethrin; 29.90 mg L^?1 for carbofuran (active ingredients), and 38.79 times the dose used in the field for the mixture of these products. The environmental risk was determined only for permethrin, and care should be taken when using the vegetable oil.     

Comparative examination on synergistic toxicities of chlorpyrifos,acephate, or tetraconazole mixed with pyrethroid insecticides to honey bees (Apis mellifera L.)

Potential synergistic toxicity of pesticide mixtures has increasingly become a concern to the health of crop pollinators. The toxicities of individual and mixture of chlorpyrifos (CHL), acephate (ACE), or tetraconazole (TET) with nine pyrethroid insecticides to honey bees (Apis mellifera L.) were evaluated to reveal any aggregated interaction between pesticides. Results from feeding toxicity tests of individual pesticides indicated that organophosphate insecticides CHL and ACE had higher toxicities to honey bees compared to nine pyrethroids. Moreover, different pyrethroids exhibited considerable variation in toxicity with LC₅₀ values ranging from 10.05 (8.60–11.69) to 1125 (922.4–1442) mg a.i. L^?1 after exposure for 7 days. Among the 12 examined pesticides, a relatively low toxicity to A. mellifera was detected from the fungicide TET. All the binary mixtures of ACE or TET in combination with pyrethroids exhibited synergistic effects. However, TET in combination with pyrethroids showed greater synergistic toxicity to A. mellifera than ACE in combination with pyrethroids. Approximately 50% binary mixtures of CHL in combination with pyrethroids also showed synergistic responses in honey bees. In particular, CHL, ACE, or TET in combination with either lambda-cyhalothrin (LCY) or bifenthrin (BIF) showed the strongest synergy in A. mellifera, followed by CHL, ACE, or TET in combination with either zeta-cypermethrin (ZCY) or cypermethrin (CYP). The findings indicated that the co-exposure of various pesticides in natural settings might lead to severe injury to crop pollinators. Therefore, pesticide mixtures should be applied carefully in order to minimize negative effects on honey bees while maintaining effective management against crop pests.

     

Fate of permethrin in model outdoor ponds

Abstract

In 1979 and 1980, outdoor artificial ponds were treated with ¹⁴C‐pennethrin (labelled at either the cyclopropyl or methylene position) at 0.028 kg/ha (15 ug/L). Uptake of permethrin by duckweed and hydrosoil was monitored by direct combustion, TLC‐autoradiography, HPLC, and liquid scintillation counting. Rapid loss of permethrin from the waiter coincided with the detection of five degradation products in the water at concentrations below 2.0 ug/L. The products were cis‐ and trans‐cyclopropyl acid, phenoxybenzoic acid, and phenoxybenzyl alcohol, and an unknown non‐cleaved product of permethrin. Permethrin was readily sorbed by duckweed but was not persistent. Permethrin residues in the hydrosoil, which was the major sink for permethrin added to the ponds, were persistent and were detected at 420 days post‐treatment. Cis‐permethrin was more persistent in the hydrosoil than the trans‐permethrin. The results indicated that permethrin in water was short‐lived at an application rate of 15 ug/L because of the rapid degradation of permethrin in the water and sorption of permethrin by the hydrosoil and vegetation. However, at one year post‐treatment, permethrin residues were still detected in the hydrosoil at 1.0 ug/kg.     

Comparative study on the environmental risk induced by several pyrethroids in estuarine and freshwater invertebrate organisms

The acute toxicity of permethrin, resmethrin, and cypermethrin to four species of aquatic non-target invertebrate organisms, found in estuarine and freshwater ecosystems, was evaluated. Artemia franciscana and Brachionus plicatilis larvae, as estuarine organisms, and Brachionus calyciflorus and Thamnocephalus platyurus larvae, as freshwater organisms, were exposed for 24 h to concentrations of these pyrethroids, and the LC(50) values were compared. The freshwater organisms were more sensitive to these pyrethroids than estuarine organisms tested. A. franciscana larvae were more tolerant organisms than B. plicatilis larvae. The freshwater organisms tested have demonstrated to be a good alternative to the standard acute toxicity assays using Daphnia, although Brachionus plycatilis larvae were more sensitive to these pyrethroid insecticides than T. platyurus. Analysis of 24 h LC(50) values of these pyrethroids, determined by static bioassays, revealed that the rank order of toxicity was: permethrin相似文献   

The response of Chenopodium album L. and Abutilon theophrasti Medik. to reduced doses of mesotrione

Limited toxicity data are available for estuarine and marine species and the widely used pyrethroid insecticide, permethrin. This study determined acute effects of permethrin on survival, lipid peroxidation, acetylcholinesterase activity, and splenocyte proliferation for two fish species found in South Carolina estuaries; juvenile red drum (Sciaenops ocellatus) and adult mummichog (Fundulus heteroclitus). Juvenile S. ocellatus were significantly more sensitive than adult F. heteroclitus to permethrin exposure, with a 96-h LC50 value of 8 μg/L determined for red drum compared to 23 μg/L for mummichog. Lipid peroxidation activity of the liver increased in permethrin-treated fish compared to control animals after 24 h and decreased after 96 h. Permethrin had no effect on acetylcholinesterase activity of the brain at the concentrations tested. Permethrin exposure significantly inhibited splenocyte proliferation, indicating an immunosuppressive effect. Most of the effects of permethrin on fish cellular stress enzymes and survival occurred at concentrations much higher than those typically measured in the environment. However, inhibition of splenocyte proliferation in juvenile red drum occurred at approximately twice that of measured permethrin concentrations in surface water. These findings may prove useful to the future management and regulation of pyrethroid insecticide use near estuarine habitats.     

Atmospheric polycyclic aromatic hydrocarbons and isomer ratios as tracers of biomass burning emissions in Northern India

Emission from large-scale post-harvest agricultural-waste burning (paddy-residue burning during October–November and wheat-residue burning in April–May) is a conspicuous feature in northern India. The poor and open burning of agricultural residue result in massive emission of carbonaceous aerosols and organic pollutants to the atmosphere. In this context, concentrations of atmospheric polycyclic aromatic hydrocarbons (PAHs) and their isomer ratios have been studied for a 2-year period from a source region (Patiala: 30.2°N; 76.3°E) of two distinct biomass burning emissions. The concentrations of 4—6 ring PAHs are considerably higher compared to 2–3 ring PAHs in the ambient particulate matter (PM_2.5). The crossplots of PAH isomer ratios, fluoranthene?/?(fluoranthene?+?pyrene) and indeno[1,2,3-cd]pyrene/(indeno[1,2,3-cd]pyrene?+?benzo[g,h,i]perylene) for two biomass burning emissions, exhibit distinctly different source characteristics compared to those for fossil-fuel combustion sources in south and south-east Asia. The PAH isomer ratios studied from different geographical locations in northern India also exhibit similar characteristics on the crossplot, suggesting their usefulness as diagnostic tracers of biomass burning emissions.     

Control of blueberry thrips,frankliniella vaccinii morgan,with permethrin and effect on yield and residue in fruit

Abstract

Permethrin at 0.4 kg a.i./ha controlled blueberry thrips Frankliniella vaccinii Morgan. There was no plant damage and crop yield was notably increased. Permethrin was extracted from berries with acetone, partitioned in hexane, cleaned‐up on Florisil column and analysed by the electron capture gas chromatography using a 3% OV‐210 column. No permethrin residues were found in the berries. The relative retention times of cis‐, and trans‐permethrins to aldrin were 10.3 and 12.1, respectively. The absence of permethrin from berries was further confirmed by TLC.     

Herbicide toxicity,selectivity and hormesis of nicosulfuron on 10 Trichogrammatidae (Hymenoptera) species parasitizing Anagasta ( = Ephestia) kuehniella (Lepidoptera: Pyralidae) eggs

Selective agrochemicals including herbicides that do not affect non-target organisms such as natural enemies are important in the integrated pest management (IPM) programs. The aim of this study was to evaluate the herbicide toxicity, selectivity and hormesis of nicosulfuron, recommended for the corn Zea mays L. (Poaceae) crop, on 10 Trichogrammatidae (Hymenoptera) species. A female of each Trichogramma spp. or Trichogrammatoidea annulata De Santis, 1972 was individually placed in plastic test tubes (no choice) with a cardboard containing 45 flour moth Anagasta ( = Ephestia) kuehniella Zeller, 1879 (Lepidoptera: Pyralidae) eggs. Parasitism by these natural enemies was allowed for 48 h and the cardboards were sprayed with the herbicide nicosulfuron at 1.50 L.ha^?1, along with the control (only distilled water). Nicosulfuron reduced the emergence rate of Trichogramma bruni Nagaraja, 1983 females, but increased that of Trichogramma pretiosum Riley, 1879, Trichogramma acacioi Brun, Moraes and Smith, 1984 and T. annulata females. Conversely, this herbicide increased the emergence rate of Trichogramma brasiliensis Ashmead, 1904, T. bruni, Trichogramma galloi Zucchi, 1988 and Trichogramma soaresi Nagaraja, 1983 males and decreased those of T. acacioi, Trichogramma atopovilia Oatman and Platner, 1983 and T. pretiosum males. In addition, nicosulfuron reduced the sex ratio of T. galloi, Trichogramma bennetti Nagaraja and Nagarkatti, 1973 and T. pretiosum and increased that of T. acacioi, T. bruni, T. annulata, Trichogramma demoraesi Nagaraja, 1983, T. soaresi and T. brasiliensis. The herbicide nicosulfuron was “harmless” (class 1, <30% reduction) for females and the sex ratio of all Trichogrammatidae species based on the International Organization for Biological Control (IOBC) classification. The possible hormesis effect of nicosulfuron on Trichogrammatidae species and on the bacterium Wolbachia sp. (Rickettsiales: Rickettsiaceae) was also discussed.     

The synthetic pyrethroid isomers II. Biological activity

Abstract

Pure optical isomers of phenothrin, permethin and cypermethrin were synthesised and tested on a wide spectrum of insects (Blattella germanica, Leptinotarsa decemlineata, Tribolium confusum, Oncopeltus fasciatus, Musca domestica, Aedes aegypti). Our results suggest that in the structurally related series phenothrin, permethrin and cypermethrin the chemical modifications had only a small influence on intrinsic activity of the compounds at the target site. The activity of piperonylbutoxide synergised 1Rtrans phenothrin and 1Rcis permethrin (LD₅₀=1.2 ng/fly in both cases) is in a similar range to the most active 1RcisS cypermethrin isomer alone or with PB (LD₅₀=0.9 and 0.4 ng/fly, respectively). Some cypermethrin isomers considered previously to be totally inactive show significant activity depending on the tested insect species. The 1ReisR and 1RtransR isomers proved to be as active as the most potent isomers on mosquito. A similarly unexpected result was that in the case of mosquito all four trans isomers were significantly more active than the corresponding eis isomers.

The superiority of the (S)‐α configuration over (R)‐α was found. It does not result from a higher intrinsic activity at the target site, but rather from the enhanced metabolic resistance of (S)‐α‐esters to ester cleavage as confirmed by Synergist studies. The activity of the two most potent stereoisomers, 1ReisS and 1RtransS, could not be elevated by quinalphos, while the inactive 1ScisR and 1StransR isomers showed significant activity with the esterase inhibitor quinalphos administered sublethally.

In contrast with the antagonism between (S)‐ and (R)‐α‐epimers of cypermethrin reported earlier a considerable synergism was observed between 1RtransS and 1StransR enantiomer pair on flour beetle and housefly in tarsal contact tests.

The results with stereoisomers and their mixtures were utilised in the development of two new products, Chinmix (beta‐cypermetrhin) and Transmix (theta‐cypermetrhin).     

A simple HPLC method for determination of permethrin residues in wine

An isocratic High Performance Liquid Chromatographic (HPLC) method was optimized for 3-phenoxybenzyl (1RS)-cis-trans-3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate (permethrin) residues identification and quantification in wine matrix. Analytical reverse phase (RP) C-18 column was used (25 cm × 4 mm i.d., 5 μ m) with mobile phase consisting of acetonitrile and water in ratio 70 %/30 % (v v^?1), flow-rate 2.0 mL min^?1, UV-detection at 215 nm and controlled oven temperature at 25°C. The peaks of isomers were identified with the retention times as compared to standard cis-/trans- mixture and confirmed with characteristic spectra using photodiode array detector. Under these conditions, permethrin isomers were well separated with resolution 2.8 and no interference with the naturally present wine compounds was observed. The method was validated for linearity, precision, accuracy, limit of detection (LOD) and limit of quantification (LOQ). Linear regression analysis data proved a good linear relationship (correlation coefficients, r², for cis- and trans-isomer are: 0.9995 and 0.9997, respectively) between response of the detector and concentration of permethrin isomers over a wide concentration range for both isomers (0.55 mg L^?1 ?4.40 mg L^?1). Experimental data showed mean recoveries between 93.95% and 96.58% with RSD values in range: 0.89% ?3.69%. The effect of ethanol content in the solvent on permethrin isomers peak areas was also studied and 60% v v^?1 ethanol was found to be optimal for sample preparation. The method was successfully tested on 20 commercial wine samples from the market in which no permethrin was detected. Thus, it was proved that it is suitable for routine permethrin residues analysis. The proposed method is suitable for routine analysis because of the simple sample preparation, acceptable run-time, low cost and its applicability with conventional instruments.     

Pyrolysis of permethrin and formation of precursors of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) under non-oxidative conditions

This article reports the computational and experimental results of the thermal decomposition of permethrin, a potential source of dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). We have performed a quantum chemical analysis by applying density functional theory to obtain the decomposition pathways of permethrin and the formation mechanism of dibenzofuran. We have conducted the pyrolysis experiments in a tubular reactor and identified the pyrolysis products to demonstrate the agreement between the experimental measurements and quantum chemical calculations. The initiation of the decomposition of permethrin involves principally the aromatisation of permethrin into 3-phenoxyphenylacetic acid, 2-methylphenyl ester (J) and concomitant loss of 2HCl. This rearrangement is followed by the rupture of the O–CH₂ linkage in J, with a rate constant derived from the quantum chemical results of 1 × 10¹⁵ exp(−68 kcal/mol/RT) s⁻¹ for temperatures between 700 and 1300 K. This is confirmed by finding that the rate constant for unimolecular rearrangement of permethrin into J is 1.2 × 10¹² exp(−53 kcal/mol/RT) s⁻¹ over the same range of temperatures and exceeds the direct fission rate constant at all temperatures up to 850 ± 120 °C as well as by the experimental detection of J prior to the detection of the initial products incorporating diphenyl ether, 1-methyl-3-phenoxybenzene, 3-phenoxybenzaldehyde and 1-chloromethyl-3-phenoxybenzene. As the temperature increases, we observe a rise in secondary products formed directly or indirectly (via phenol/phenoxy) including aromatics (naphthalene), biphenyls (biphenyl, 4-methyl-1,1′-biphenyl) and dibenzofuran (DF). In particular, we discover by means of quantum chemistry a direct route from 2-phenoxyphenoxy to naphthalene. We detect no polychlorinated dibenzo-p-dioxins and dibenzofurans. Unlike the case of oxidative pyrolysis [Tame, N.W., Dlugogorski, B.Z., Kennedy, E.M., 2007b. Formation of dioxins in fires of arsenic-free treated wood: Role of organic preservatives. Environ. Sci. Technol. 41, 6425–6432] where significant yields of both PCDD and PCDF were obtained, under non-oxidative conditions the thermal decomposition of permethrin does not form appreciable amounts of PCDD or PCDF and the presence of oxygen (and/or a sizable radical pool) appears necessary for the formation of dibenzo-p-dioxin itself or PCDD/F from phenol/phenoxy.     

Interconversions and toxicity changes in hexachlorocyclohexane isomers on dispersion in water

Abstract

Studies on the transformations of hexachlorocyclohexane isomers, α‐, β‐, γ‐ and δ‐, in aqueous solution were carried out at 25 ± 1°C over a period of four weeks. Gas liquid chromatographic technique was used for analysis. The results indicated a loss as well as interconversion of all the four isomers with time. The resulting changes in toxicity of the aqueous solution were studied against Drosophila using topical application. Toxicity studies with aqueous solution of technical hexachlorocyclohexane were simultaneously carried out for comparison. Toxicity of the aqueous solutions of α‐, β‐, and δ ‐isomers showed an increase while that of the γ‐isomer decreased significantly during the four week experimental period. Aqueous solution of technical HCH was equally toxic as that of the γ‐isomer initially and did not show much decrease in its toxicity at the end. Changes in toxicity of the individual isomer solutions were considered to be due, in part, to interconversions of HCH isomers.     

The synaptosomal membrane bound ATPase as a target for the neurotoxic effects of pyrethroids,permethrin and cypermethrin

Pyrethroids are used widely as insecticides both in agriculture and in households. A cellular target of pyrethroids is the sodium channel in the membrane. In the present study, the activity of the membrane bound integral protein ATPase was studied as a biomarker for the membrane effect of the pyrethroids permethrin and cypermethrin. Male Sprague-Dawley rats were used for cerebral synaptosome preparation. The isolation of synaptosomes was performed with the Percoll gradient method. Both total ATPase and Mg(2+) activated ATPase were studied by determining inorganic phosphate liberated from the substrate ATP. One hour exposure to permethrin (Biokill) and cypermethrin (Ripcord) insecticide products affected ATPase activities. The activity of Na(+), K(+) ATPase decreased dose-dependently in 10-50 microM concentrations of permethrin, and Mg(2+) activated ATPase increased over twofold in the same concentrations of the active components. The effect of the cypermethrin compound Ripcord was not clearly dose-dependent. The activity of total ATPase was almost entirely lost in the concentrations of 100 microM of permethrin and cypermethrin. The results support the idea that membrane ATPases are one target of the neurotoxic effect of pyrethroid compounds.     

Effects of pyrethroid insecticide seed treatments on Rhizobium japonicum and its symbiotic relationship with,and growth of soybean

Abstract

Two pyrethroid insecticides were compared with two fungicides for their effects on the rhizobial and seedling components of the N₂‐fixing symbiosis in soybeans (Glycine max Merr. variety Olinda). In vitro growth of Rhizobium japonicum RI16, was inhibited in the order of HgCl₂ > thiram > cypermethrin > permethrin. The emergence of the seedlings was stimulated by all chemicals tested. Also, none of the pesticides studied had any significant effect on N₂ fixation (acetylene reduction), at the dosages used. Consequently, yields of the various organs were also not significantly influenced by the chemicals.