S. Chandrasekaran

Toxicity of diafenthiuron to honey bees in laboratory, semi-field and field conditions.

BACKGROUND Cardamom, an important spice crop often attacked by many insect pests, is controlled mainly using synthetic insecticides. As honey bees play a vital role in pollination in cardamom, the impact of insecticides on honey bees needs to be explored to assess its safety. RESULTS Risk assessment based on contact toxicity revealed diafenthiuron to be a non-selective insecticide to bees with a low selectivity ratio (the ratio between the LD(50) for beneficial and pest species). A dose of diafenthiuron that killed 90% of cardamom borer, Conogethes punctiferalis Guenee, was found to kill 100% of Indian bees. Based on the hazard ratio (the ratio between the field-recommended dose and the LD(50) for the beneficial), diafenthiuron was found to be slightly to moderately toxic to bees. Diafenthiuron, even at low concentrations of LC(1) (the concentration that killed 1% of bees), was found to affect the foraging and homing behaviour of Indian bees. Of bees fed with 30 microg mL(-1) of diafenthiuron, 40% were found missing on the third day after exposure. However, diafenthiuron did not affect bee visits to the cardamom fields. CONCLUSION Diafenthiuron is more highly toxic to Apis cerana indica F. than to C. punctiferalis by contact, using selectivity ratio and probit substitution methods of risk assessment, but the hazard ratio revealed diafenthiuron to be a slightly to moderately toxic chemical. Diafenthiuron was found to affect the foraging and homing behaviour of bees at sublethal concentrations. Thus, sublethal effects are more relevant in risk assessment than lethal and acute effects.

Determination of fipronil and its major metabolites in vegetables, fruit and soil using QuEChERS and gas chromatography-mass spectrometry

A rapid, simple and selective gas chromatography with mass spectrometric detection (GC-MS) method was developed and validated for simultaneously determining fipronil and its three major metabolites in vegetables, fruit and soil. The fipronil residues were extracted using QuEChERS technique with ethyl acetate and then were purified by dispersive solid phase extraction (d-SPE) cleanup for cabbage, cauliflower, okra, tomato, grapes and soil. The linearity of the analytical response across the studied range of concentrations (0.01–0.5 µg mL−1) was excellent, obtaining correlation coefficients higher than 0.999. The average recoveries of the pesticide from all matrixes ranged from 86 to 112%, for fortification levels of 0.01, 0.05 and 0.1 µg g−1. The precision values associated with the analytical method, expressed as RSD values, were less than 10.15% for the pesticide in all matrixes. This method can be used to evaluate environmental residues and the safety of agricultural products.

Physical and biological compatibility of diafenthiuron with micro/macro nutrients fungicides and biocontrol agents used in cardamom

In the context of complex field problems, compatibility of an efficacious insecticide with other agrochemicals normally used in the field is essential. In this view diafenthiuron, a novel insecticide which inhibits ATP synthesis, used widely for pest management in cardamom, was tested for its compatibility with agrochemicals viz., fungicides and nutrients normally used in the crop. The results revealed that all the chemicals tested were physically and biologically compatible with diafenthiuron by means of physical stability and phytotoxicity ratings in the field. But the bioefficacy study on Conogethes punctiferalis in the laboratory and bioefficacy studies in the field against Sciothrips cardamomi reveal that diafenthiuron is incompatible and should not be sprayed along with fungicides like mancozeb and copper oxychloride. Another study on the compatibility of diafenthiuron with antagonistic microorganisms of plant pathogens viz., Trichoderma viride and Pseudomonas fluorescens revealed that diafenthiuron had some inhibitory effect on the mycelial growth of T. viride. Diafenthiuron did not affect the growth of P. fluorescens and thus can be used simultaneously for the control of insect pests and seed- and soil-borne diseases.

Honey bees of the cardamom ecosystem and the selective toxicity of diafenthiuron to four different bee species in the laboratory

Summary Bees are important pollinators necessary for fruit set in cardamom (Elettaria cardamomum). Apis cerana indica, Apis dorsata, Trigona iridipennis and Amegilla spp. were observed in cardamom plantations of south India. Since cardamom is attacked by an array of insect pests, synthetic insecticides were used in crop management. Diafenthiuron is one such insecticide found to be very effective against the cardamom borer, Conogethes punctiferalis and thrips, Sciothrips cardamomi. Most insecticides used in crop protection are reported to be hazardous to bees, so diafenthiuron was also tested for its toxicity to bees. Diafenthiuron was found to be slightly harmful to A. dorsata, A. cerana indica, A. foreaand moderately harmful to T. iridipennis. In particular, it was slightly to moderately toxic to bees on contact with treated surfaces in the laboratory. T. iridipennis and A. dorsata are found abundantly in the cardamom ecosystem and unfortunately highly susceptible to the insecticide. It was found that diafenthiuron is highly toxic when applied to the thorax of bees but it is less toxic on ingestion, i.e, contact toxicity is higher than oral toxicity. The labellum, the attractive part of the cardamom flower, where the bees land is not heavily exposed to pesticide sprays in the field because of its position and other reasons, so bees have a reduced chance of exposure to the pesticide in the field. Under critical situations, however, spraying of the chemical during peak bee activity should be avoided.

Simultaneous determination of tebuconazole, trifloxystrobin, and its metabolite trifloxystrobin acid residues in gherkin under field conditions

A rapid, simple, and selective analytical method for the simultaneous determination of tebuconazole, trifloxystrobin, and its metabolite trifloxystrobin acid residues in gherkin and soil was developed and validated by gas chromatography coupled with mass spectrometry. The samples were extracted with acetonitrile and cleaned up by dispersive solid-phase extraction with primary secondary amine sorbent. The limit of quantification of the method was 0.05 mg/kg for all three compounds. The method was validated using blank samples spiked at three levels and recoveries ranged from 83.5 to 103.8% with a relative standard deviation of 1.2 to 4.8%. The developed method was validated and applied for the analysis of a degradation study sample. The residues of trifloxystrobin and tebuconazole were found to dissipate following first-order kinetics with half-life ranging between 3.31-3.38 and 3.0-3.04 days, respectively, for two different dosages. Pesticide residues were below the European Union maximum residue level after seven days for trifloxystrobin (0.2 mg/kg) and ten days for tebuconazole (0.05 mg/kg), which suggested the use of this fungicide mixture to be safe to humans. These results can be utilized in formulating the spray schedule and safety evaluation on trifloxystrobin and tebuconazole in gherkin crop.

Efficacy of Neem Oil on Cardamom Thrips, Sciothrips cardamomi Ramk., and Organoleptic Studies

The neem tree contains promising pest control substances which are effective against many pests. Oil extracted from neem seeds was used against cardamom thrips, Sciothrips cardamomi, a severe and economic pest of cardamom. Neem oil formulations, namely, Tamil Nadu Agricultural univeristy neem oil (TNAU NO) (acetic acid & citric acid), were found effective against the pest with a overall damage reduction of 30% after 14 days of treatment. The percent damage reduction in capsules over control after three consecutive sprays of TNAU NO(C) 2% and TNAU NO(A) 2% was 78.3 and 75.2 percent, respectively. The newly extracted and unformulated neem oil, though found inferior to the formulated one, still found to cause 50% and 70% reduction in damage caused by thrips at two and three rounds of sprays, making it useful in pest management. Organoleptic tests conducted on cardamom capsules sprayed with neem oil revealed no significant difference in taste, aroma, and overall acceptability of cow milk boiled with cardamom. Thus, TNAU NO (A and C) 2% was found effective against cardamom thrips with no adverse organoleptic properties and can be recommended.

Baseline toxicity of emamectin and spinosad to Helicoverpa armigera (Lepidoptera: Noctuidae) for resistance monitoring

Acute toxicity studies of emamectin and spinosad against Helicoverpa armigera revealed that the pest is highly susceptible to both the insecticides. The median lethal dose (LD50) of emamectin is 3.86 × 10−3 µg per larva. The median lethal concentrations (LC50) of emamectin and spinosad were found to be 0.09 and 2.94 ppm, respectively. The discriminating doses were fixed based on the LC95 of the susceptible population of H. armigera as 0.80 ppm for emamectin and 10 ppm for spinosad. Resistance was not observed when the discriminating doses of emamectin and spinosad were applied on field‐collected populations of H. armigera from two intensive cotton growing areas, Coimbatore and Madurai, India.

Estimation of Diafenthiuron Residues in Cardamom (Elettaria cardamomum (L.) Maton) Using Normal Phase HPLC: Dissipation Pattern and Safe Waiting Period in Green and Cured Cardamom Capsules

Diafenthiuron is an effective insecticide used for pest management in cardamom. Residues of diafenthiuron and its degradation/dissipation pattern in cardamom were determined to work out safe waiting period. Samples were collected after three sprays of diafenthiuron @ 400 and 800 g a.i ha−1 and the residues extracted in acetonitrile and quantified in normal phase HPLC in UV detector. Diafenthiuron was detected in min. The limits of detection (LOD) and limits of quantification (LOQ) were determined to be 0.01 and 0.05 μgmL−1. The initial deposits were found to be 3.82 and 4.10 μg g−1 after sprays of diafenthiuron @ 400 g a.i ha−1 in the first and second experiments, respectively. Nearly cent percent of residues dissipated at 10 days after treatment in the recommended dose of diafenthiuron 400 g a.i ha−1 and the half life varied from 2.0 to 2.8 days with a waiting period of 5.5 to 6.7 days in green capsules of cardamom. The waiting period was 5.4 to 7.0 days in cured capsules of cardamom. With harvest being the focal point for enforcement of residue tolerances, the suggested waiting period of seven days is safe without the problem of pesticide residues in harvestable produce.

Determination of fluopicolide in grapes and soil using an easy sample preparation method and gas chromatography-mass spectrometry

A simple analytical method was developed and validated to determine fluopicolide residues in grapes and soil using the “Quick, Easy, Cheap, Effective, Rugged and Safe” approach followed by gas chromatography-mass spectrometry in the selected ion monitoring mode. Fluopicolide residues were extracted from grape and soil samples with acetonitrile, and the extracts were cleaned up by dispersive solid-phase extraction with primary secondary amine sorbent. The limit of quantification was 0.02 mg kg−1 with grape and soil samples spiked at three levels, and recoveries were from 95% to 101% and 94% to 101% with relative standard deviations from 0.2% to 4.4%. The method is less expensive and safer than existing analytical methods for grapes and soil.

Dislodgeable residues of profenofos on jasmine and risk assessment of post application exposure to flower bud pickers

A field study was conducted to measure the dislodgeable residues of profenofos applied to jasmine (Jasminum sambac) and risk assessment was done for laborers engaged in picking of flower buds. Profenofos was applied at 0.10, 0.15, and 0.20% concentration and the jasmine bud samples were analysed for residues using GC. The initial deposit of 1.6–3.8, 3.8–7.1, and 5.2–7.6 µg cm−2 was detected on jasmine buds at 0.10, 0.15, and 0.20% concentration, respectively. At the recommended dose of 0.10%, the half-life was 1–2 days and the dislodgeable residues disappeared within 7 days. The results indicate faster disappearance of dislodgeable residues on jasmine buds. Risk assessment was done based on dislodgeable foliar residues and exposure estimates based on surrogate data and expressed as Margin of Exposure (MOE). The entry restrictions for exposure of jasmine flower pickers to profenofos, would be at least, 1 day following application, for the recommended concentration of 0.10% (MOE = 106) and 3 days, at higher concentrations of 0.15% (MOE = 156) and 0.20% (MOE = 115).