Insecticide residues in cotton crop soil

Dimethoate, monocrotophos, triazophos, deltamethrin, cypermethrin and endosulfan were applied to a cotton crop soil located at Nurpur village, Punjab, India. The insecticides were applied sequentially at recommended dosages in cotton fields by foliar application in 1995, 1996 and 1998. Soil samples were collected from the cotton crop farms and extracted with acetone. The extracted material was analysed by a gas liquid chromatograph (GLC) equipped with an 63Ni electron-capture detector (ECD-63Ni). Recovery data was obtained by fortifying soil with insecticide. The average recoveries from the fortified soil samples were 76-92% for organophosphorous compounds and 90-98% for synthetic pyrethroids and organochlorines. The results showed that the insecticide residues under study were present in the range of 1.16 to 41.97 ng g(-1) d.wt.soil. The pattern of dissipation of the insecticides used was similar for the duration of the crop. Half lives of the insecticides ranged from 7 to 22 days. Except endosulfan none of the other insecticides used were leached below 15 cm. Endosulfan was found to be rapidly degraded in the soil and formed a sulfate metabolite. Persistence and dissipation pattern in soils with history of exposure to the insecticide compared to non-history soils were similar.     

Dissipation of alachlor in cotton plant, soil and water and its bioaccumulation in fish

Dissipation of alachlor in soil and plant in field condition (cotton cropping system), and in soil, water and fish in simulated model ecosystem was investigated. The acetanilide herbicide, alachlor (50% w/w EC) was applied as pre-emergence at 2.5 and 5.0 kg a.i.ha(-1) three days after sowing the cotton seeds in the field. Soil and plant samples were collected at intervals and analyzed for alachlor residues. To study the fate of alachlor in water and fish, a simulated model ecosystem was constructed and fish was introduced one day after herbicide application. The dissipation of alachlor in water and soil and bioaccumulation in fish was observed in model ecosystem. At harvest, cotton lint and seed samples were found to contain alachlor well below the detectable level. However, trace amounts of residues were found in cotton oil. After harvest of cotton, coriander (Coriandrum sativum) and edible amaranth (Amaranthus mangostanus L.) were raised for herbicide bioassay. The green leafy vegetable samples did not show any toxic symptoms of alachlor residues.     

Disappearance of dimethoate,methamidophos and pirimicarb in lettuce

Abstract

Foliar sprays of dimethoate at 150 or 300 g a.i./ha, methamidophos at 450 or 900 g a.i./ha and pirimicarb at 140 or 280 g a.i./ha were applied for control of the green peach aphid, Myzus pericae (Sulzer), and the lettuce aphid, Nasonovia ribisnigri (Mosley), about 2 weeks before the lettuce started heading, and again about 1 week from harvest. In lettuce, dimethoate partially oxidized to its oxon and pirimicarb converted to its methylamino‐ and/or formyl methylamino‐analogues. Most residues were present in the outer leaves which were exposed directly to the sprays; only traces of residues were detected in samples of the inner head leaves. Total residues disappeared rapidly. Pirimicarb was the least persistent and only traces of residues (<0.01 ppm) were detected in marketable heads. Concentrations of dimethoate, including the oxon and of methamidophos were well below their respective tolerances of 2 and 1 ppra respectively.     

Terbufos residues in wheat and barley

A granular formulation of terbufos (Counter 15G) was added in-furrow at time of planting of wheat and barley. Foliage collected at several times was analyzed for total terbufos residues as terbufoxon sulfone. Maximum residues from application of 1.5 and 3.0 kg/ha were 7.4 and 10.6 ppm, respectively, in wheat foliage samples collected 10 days postseeding. Wheat foliage collected at 53 days postseeding had residues averaging 0.32 and 0.58 ppm from the 1.5 and 3.0 kg/ha applications, respectively. In 1985 residues in barley were consistently less than in wheat in 1985 with 4.4 and 7.0 ppm detected in foliage collected 10 days post application from the 1.5 and 3.0 kg/ha applications, respectively and 0.21 and 0.34 ppm detected at 53 days. Grain samples had 0.01 ppm or less residue at harvest. Straw samples had up to 0.75 ppm total terbufos residues at harvest.     

Degradation of disulfoton,oxydemeton‐methyl,methamidophos and demeton in asparagus plant

Abstract

Disulfoton and methamidophos (both at 1.12 kg a.i./ha), oxydemeton‐methyl and demeton, (both at 0.56 kg a.i./ha) were applied as post‐harvest foliar sprays to control the European asparagus aphid, Brachycolus asparagi. Oxidation of disulfoton, oxydemeton‐methyl and demeton to their corresponding sulfoxides and sulfones occurred in asparagus foliage 2 to 5 days after application. The total residues of these three compounds, including their toxic oxidative metabolites declined to less than 0.5 ppm about 47 days after the spray application whereas methamidophos persisted longer; 0.84 ppm of its residue was found even after 85 days. No residue was found above the limit of detection of 0.002 ppm in any asparagus spears which were produced in the following spring; the four compounds were sprayed on the asparagus plants during the previous season at realistic rates for aphid control.     

The effects of the insecticide lambda-Cyhalothrin on the earthworm Eisenia fetida under experimental conditions of tropical and temperate regions

Plant Protection Products can affect soil organisms and thus might have negative impacts on soil functions. Little research has been performed on their impact on tropical soils. Therefore, the effects of the insecticide lambda-Cyhalothrin on earthworms were evaluated in acute and chronic laboratory tests modified for tropical conditions, i.e. at selected temperatures (20 and 28 °C) and with two strains (temperate and tropical) of the compost worm Eisenia fetida. The insecticide was spiked in two natural soils, in OECD artificial soil and a newly developed tropical artificial soil. The effects of lambda-Cyhalothrin did rarely vary in the same soil at tropical (LC50: 68.5-229 mg a.i./kg dry weight (DW); EC50: 54.2-60.2 mg a.i./kg DW) and temperate (LC50: 99.8-140 mg a.i./kg DW; EC50: 37.4-44.5 mg a.i./kg DW) temperatures. In tests with tropical soils and high temperature, effect values differed by up to a factor of ten.     

Studies of methamidophos-C-14 in Costa Rican vegetables and soils

In order to see the effect of time lapse between the last application of methamidophos and harvesting insecticide was applied on lettuce plants (6,84 μCi in one experiment and 4,03 μCi in the other experiment). Analysis of the crops harvested 3 days after last application showed 9,7 ppm residues on leaves, while crops harvested 1 day after application showed residues of 12,7 ppm (25% more). Treatment of tomato plants (39,65 μCi, 1,01 kg/ha) gave residues in fruits 4,92 ppm after 8 days interval between last application and harvesting. 40 days gap between the last application and harvesting leaved residues of 0,7 ppm in fruits which is much less as recommended by FAO/WHO (1 – 2 ppm).Degradation of this insecticide is dependent on the matrix of the soil, this breakdown is observed in the first ten days and than after it remains constant. C-14 radioactivity extracted from soil and plant analysis was methamidophos (92%)     

Insecticide Residues on Weathered Passerine Carcass Feet

Nine brown-headed cowbirds ( Molothrus ater ) were exposed to turf sprayed with either EarthCare® (25% diazinon; 4.77 L a.i./ha) or Ortho-Klor® (12.6% chlorpyrifos; 5.21 L a.i./ha). Birds were euthanized and one foot from each bird was weathered outdoors for up to 28 days and the other foot was kept frozen until residue analysis. When compared to the unweathered feet, feet weathered for 28 days retained 43% and 37% of the diazinon and chlorpyrifos, respectively. Insecticide residues were below the level of detection (1.0 ppm) on control feet. Weathered feet may be used for determining organophosphorus insecticide exposure to birds.     

Persistence of fensulfothion in a sandy‐loam soil and uptake by rutabagas,carrots and radishes using microplots

Abstract

Field microplots were treated with 141 and 282 ppm fensulfothion and 37.1 and 74.2 ppm fensulfothion sulfone. These concentrations are equivalent to field treatment rates of 8.48 and 16.96 kg Al/ha, fensulfothion, and 2.23 and 4.47 kg Al/ha, fensulfothion sulfone, respectively, for banded application (10 cm wide, rows 80 cm apart). The half‐lives in a sandy loam soil were 30–39 and 14–23 days, respectively. Fensulfothion sulfone and sulfide were the main derivatives found in fensulfothion treated soil.

The maximum levels of these derivatives were 21.22 and 22.95 ppm, respectively for the 8.48 kg/ha treatment and 33.90 and 42.45 ppm, respectively, for the higher treatment, which occurred between 30–60 days.

Carrots appeared to take up more fensulfothion from soil than rutabagas or radishes. The residue levels at harvest decreased in the order carrot peel > pulp > rutabagas root > peel > pulp. Residue levels of fensulfothion and sulfone in radishes were similar to those found in rutabagas. The ratio sulfoxide/sulfone in rutabagas ranged from 0.4–1.5 and in carrots from 1.7–7.6. This phenomenon is thought to be due to oxidative enzyme systems present in rutabagas. Dimethyl phosphorothioic acid, but not dimethyl phosphoric acid was detected (max. 1.33 ppm) in some rutabagas samples but not in carrots.     

Development of an analytical method for analysis of flubendiamide, des-iodo flubendiamide and study of their residue persistence in tomato and soil

Flubendiamide is a new insecticide that has been found to give excellent control of lepidopterous pests of tomato. This study has been undertaken to develop an improved method for analysis of flubendiamide and its metabolite des-iodo flubendiamide and determine residue retention in tomato and soil. The analytical method developed involved extraction of flubendiamide and its metabolite des-iodo flubendiamide with acetonitrile, liquid-liquid partitioning into hexane-ethyl acetate mixture (6:4, v v?1) and cleanup with activated neutral alumina. Finally the residues were dissolved in gradient high pressure liquid chromatography (HPLC) grade acetonitrile for analysis by HPLC. The mobile phase, acetonitrile-water at 60:40 (v v?1) proportion and the wavelength of 235 nm gave maximum peak resolution. Using the above method and HPLC parameters described, nearly 100 % recovery of both insecticides were obtained. There was no matrix interference and the limit of quantification (LOQ) of the method was 0.01 mg kg?1. Initial residue deposits of flubendiamide on field-treated tomato from treatments @ 48 and 96 g active ingredient hectare?1 were 0.83 and 1.68 mg kg?1, respectively. The residues of flubendiamide dissipated at the half-life of 3.9 and 4.4 days from treatments @ 48 and 96 g a.i. ha?1, respectively and persisted for 15 days from both the treatments. Des-iodo flubendiamide was not detected in tomato fruits at any time during the study period. Residues of flubendiamide and des-iodo flubendiamide in soil from treatment @ 48 and 96 g a.i. ha?1 were below detectable level (BDL, < 0.01 mg kg?1) after 20 days. Flubendiamide completely dissipated from tomato within 20 days when the 480 SC formulation was applied at doses recommended for protection against lepidopterous pests.     

Estimation of β-cyfluthrin and imidacloprid in okra fruits and soil by chromatography techniques

Dissipation of β-cyfluthrin and imidacloprid in okra was studied following three applications of a combination formulation of Solomon 300 OD (β-cyfluthrin 9 % + imidacloprid 21 %) @ 60 and 120 g a.i. ha(-1) at 7 days interval. Residues of β-cyfluthrin and imidacloprid in okra were estimated by gas liquid chromatography (GLC) and high performance liquid chromatography (HPLC), respectively. Residues of β-cyfluthrin were confirmed by gas chromatograph-mass spectrometry (GC-MS) and that of imidacloprid by high performance thin layer chromatography (HPTLC). Half-life periods for β-cyfluthrin were found to be 0.91 and 0.68 days whereas for imidacloprid these values were observed to be 0.85 and 0.96 days at single and double the application rates, respectively. Residues of β-cyfluthrin dissipated below its limit of quantification (LOQ) of 0.01 mg kg(-1) after 3 and 5 days at single and double the application dosage, respectively. Similarly, residues of imidacloprid took 5 and 7 days to reach LOQ of 0.01 mg kg(-1), at single and double dosages respectively. Soil samples collected after 15 days of the last application did not show the presence of β-cyfluthrin and imidacloprid at their detection limit of 0.01 mg kg(-1).     

Dissipation of chlorpyrifos in two soil environments of semi-arid India

The dissipation of chlorpyrifos (20 EC) at environment-friendly doses in the sandy loam and loamy sand soils of two semi-arid fields and the presence of pesticide residues in the harvested groundnut seeds, were monitored. The movement of chlorpyrifos through soil and its binding in the loamy sand soil was studied using 14C chlorpyrifos. Chlorpyrifos was moderately stable in both loamy sand and sandy loam soils, with half-life of 12.3 and 16.4 days, respectively. With 20 EC treatments the dissipation was slower for standing crop than seed treatment, indicative of the high degradation rates in the bioactive rhizosphere. In soil, 3,5,6-trichloro-2-pyridinol (TCP) was the principal breakdown product. Presence of 3,5,6-trichloro-2-methoxypyridine (TMP), the secondary metabolite, detected in the rhizospheric samples during this study, has not been reported earlier in field soils. The rapid dissipation of the insecticide from the soil post-application might have resulted from low sorption due to the alkalinity of the soil and its low organic matter content, fast topsoil dissipation possibly by volatilization and photochemical degradation, aided by the low water solubility, limited vertical mobility due to confinement of residues to the upper 15 cm soil layers and microbial mineralization and nucleophilic hydrolysis. Contrary to the reports of relatively greater mobility of its metabolites in temperate soils, TMP and TCP remained confined to the top 15 cm soil. The formation of bound residues (half-life 13.4 days) in the loamy sand soil was little and not "irreversible." A decline in bound residues could be correlated to decreasing TCP concentration. Higher pod yields were obtained from pesticide treated soils in comparison to controls. Post-harvest no pesticide residues were detected in the soils and groundnut seeds.     

Assessment of imidacloprid in Brassica environment

Imidacloprid was applied as seed treatment (Gaucho 70 WS, 5 and 10 g ai kg(-1) seed) and foliar spray (Confidor 200 SL, 20 and 40 g ai ha(-1)) at 50% pod formation stage on mustard (Brassica campestris Linn.) to control mustard aphid, Lipaphis erysimi Kalt. It was detectable upto 82 and 96 days in plants after sowing from lower and higher doses of seed treatment. However, it dissipated faster and became nondetectable after 7 and 15 days of foliar treatments from lower and higher rates of application, respectively. The dissipation models yielded the rate constants of 0.0209 and 0.0230 and 0.0736 and 0.0779 day(-1) from seed and foliar treatment. The corresponding half-lives of 14.40 and 13.07 and 4.09 and 3.86 days were recorded. This suggested that the dissipation was independent of initial doses and followed a first order rate kinetics. The projected TMRC of imidacloprid from seed (0.136 and 0.225 mg person(-1) day(-1)) and foliar (0.069 and 0.1497 mg person(-1) day(-1)) treatments were found lower than the MPI (3.135 mg person(-1) day(-1)). At harvest mustard grains did not contain imidacloprid residues. The absence of imidacloprid in 0-10 and 10-20 cm soil layers indicated no leaching of insecticide. Therefore, imidacloprid treatments could be taken as safe for crop protection, consumption of leaves and environmental contamination point of view.     

Persistence of chlorpyrifos in a mineral and an organic soil

Chlorpyrifos (Lorsban emulsifiable concentrate) was applied at 3.4 kg AI/ha and incorporated into sand and muck soil contained in small field plots. Soil samples were taken at intervals over 2 yr. Radishes and carrots, seeded yearly, served as indicator crops for absorption of insecticide residues. Samples were extracted and analyzed, by gas-liquid chromatography, for chlorpyrifos, oxychlorpyrifos, and 3,5,6-trichloro-2-pyridinol. Chlorpyrifos residues declined rapidly, with 50% of the initial application remaining after 2 and 8 wk in sand and muck, respectively, and 4 and 9% after 1 yr. Pyridinol residues increased to 13 and 39% of the initial chlorpyrifos application in sand and muck after 1 and 8 wk, respectively, and declined thereafter. Oxychlorpyrifos was detected in the 2 soils at very low levels only in immediate posttreatment samples. In the first year of the study low levels (less than 0.1 ppm) of chlorpyrifos and the pyridinol were detected in radishes and carrots.     

Dissipation of epoxiconazole in the paddy field under subtropical conditions of Taiwan

The environmental fate and distribution of fungicide epoxiconazole were studied by a rice paddy field model ecosystem. One week before the head-sprouting stage, rice plant was treated separately once with OPUS (tradename of epoxiconazole) 12% SC 2.1 kg ha(-1) and 1.4 kg ha(-1), respectively. Soil, water and rice plant were sampled seven days intervals nine times after application. The bioconcentration factor of epoxiconazole on mosquito fish in the ecosystem was also determined, based on the amounts of epoxiconazole content both in fish and water. This was initiated one day after the fungicide treatment, and continued for four days. In addition, the residue of epoxiconazole in rice grains was analyzed after harvest. After harvest, both planted water spinach (Ipomoea aquatica Forsk) and edible amaranth (Amaranthus mangostanüs L.) were analyzed. The results showed that epoxiconazole degraded in the local environment under the experimental conditions described. The degradation equations were in accordance with the first order kinetics. The DT50 of soil, field water and rice plant were 20-69 days, 11-20 days and 14-39 days, respectively. The bioconcentration factors of epoxiconazole on mosquito fish were 12.9 and 10.6 from 2.1 kg ha(-1) and 1.4 kg ha(-1) treatment, respectively. Residues of epoxiconazole in both rice and harvest vegetables were non-detectable. This indicates that epoxiconazole applied to rice at the recommended rates and application frequencies will not accumulate on rice grain and successive cropping vegetables.     

Dissipation kinetics of spiromesifen on tea (Camellia sinensis) under tropical conditions

Spiromesifen (Oberon) is a new insecticide and miticide of chemical class ketoenol active against white flies (Bemisia spp., Trialeuroides spp.) and spider mites (Tetranychus and Panonychus spp.). Due to its potential significance in insect resistance management, it is important to establish its behaviour on crop and environment. In the present study, the degradation/dissipation of spiromesifen on tea crop under tropical environmental conditions was studied and its DT(50) (t(1/2)), and DT(90) (time to reduce to 90% of the initial value) were estimated. Spiromesifen was sprayed on tea crop after first rain flush at four different locations @ 96 and 192ga.i.ha(-1). Samples of tea leaves were drawn at 0, 1, 3, 5, 7, 10, 15, 21 and 30 days after treatment and that of soil at 10 days after treatment and at harvest from 0 to 15 and 15 to 30cm layers. After crude extraction of tea leaves for spiromesifen residues with acetone:water, the contents were partitioned with cyclohexane:ethyl acetate and cleaned up on Florosil column. Soil residues were also extracted similarly. Quantification of residues was done on GC-MS in Selected Ion Monitoring (SIM) mode in mass range 271-274m/z. The LOQ of this method was found to be 0.05microgg(-1) while LOD being 0.015microgg(-1). The DT(50) of spiromesifen when applied at recommended doses in tea leaves was found to be 5.0-8.5 days. Ninety-nine percent degradation was found to occur within 33-57 days after application. In soil, no residues of spiromesifen were detectable 10 days after treatment.     

The aerobic soil degradation of spinosad ‐ a novel natural insect control agent

Abstract

Spinosad is a natural product with biological activity against a range of insects including lepidoptera. It is comprised of two major components namely spinosyns A and D. The degradation of spinosad in soil under aerobic conditions was investigated using two U.S. soils (a silt loam and a sandy loam) which were treated with either ¹⁴C‐spinosyn A or ‐spinosyn D at a 2X use rate of 0.4mg/kg soil for spinosyn A and 0.1mg/kg for spinosyn D. Further samples of soil were pre‐sterilised prior to treatment in order to establish whether spinosyns A and D degrade abiotically. Flasks of treated soil were incubated in the dark at 25°C for up to one year after treatment.

HPLC and LC‐MS of soil extracts confirmed that the major degradation product of spinosyn A was spinosyn B, resulting from demethylation on the forosamine sugar. Other dégradâtes were hydroxylation products of spinosyns A and B, with hydroxylation probably taking place on the aglycone portion of the molecule. Half lives were similar for both spinosyns and were in the range 9–17 days, with longer half lives in the pre‐sterilised soils (128–240 days) suggesting that degradation was largely microbial.     

Behavior of the organophosphorus insecticide fenitrothion in stored faba beans and its biological effects towards experimental animals

Sound whole-seed faba beans were treated with (methyl-¹⁴C) fenitrothion [O, O-dimethyl-O-(3-methyl-4-nitrophenyl) phosphorothioate] at 5 and 10 mg insecticide/kg seeds, a dose normally used in practice. During the 30 weeks of storage period, the penetration and distribution of insecticide residues were studied. The amount of surface residues, internal residues and bound insecticide residues was estimated. Surface residues were found to decrease with the increase in time of storage, whereas internal residues showed a gradual increase with time apparently not dose dependent. Grain-bound residues increased with time and reached to its maximum (14–18%) after 24 weeks of storage. Chromatographic analysis of the internal extracts revealed the presence of the parent compound together with three main metabolites which were found in both free and conjugated form. Feeding mice for 90 days with a diet mixed with total internal fenitrothion residues in stored faba beans led to a reduction in body weight gain, and an appreciable decrease in cholinesterase activity of 32% for plasma and 15% for red blood cells (RBC_S) after two months of experiment. Also, a significant decrease was showed in both total protein and albumin concentration at the end of feeding period (90 days). Liver and kidney function, as well as lipid profile of treated mice significantly increased at the end of feeding period. After a one-month recovery period, all the examined blood parameters returned to about the control values except blood urea and serum triglyceride.     

Behavior of the organophosphorus insecticide fenitrothion in stored faba beans and its biological effects towards experimental animals

Sound whole-seed faba beans were treated with (methyl-(14)C) fenitrothion [O, O-dimethyl-O-(3-methyl-4-nitrophenyl) phosphorothioate] at 5 and 10 mg insecticide/kg seeds, a dose normally used in practice. During the 30 weeks of storage period, the penetration and distribution of insecticide residues were studied. The amount of surface residues, internal residues and bound insecticide residues was estimated. Surface residues were found to decrease with the increase in time of storage, whereas internal residues showed a gradual increase with time apparently not dose dependent. Grain-bound residues increased with time and reached to its maximum (14-18%) after 24 weeks of storage. Chromatographic analysis of the internal extracts revealed the presence of the parent compound together with three main metabolites which were found in both free and conjugated form. Feeding mice for 90 days with a diet mixed with total internal fenitrothion residues in stored faba beans led to a reduction in body weight gain, and an appreciable decrease in cholinesterase activity of 32% for plasma and 15% for red blood cells (RBC(S)) after two months of experiment. Also, a significant decrease was showed in both total protein and albumin concentration at the end of feeding period (90 days). Liver and kidney function, as well as lipid profile of treated mice significantly increased at the end of feeding period. After a one-month recovery period, all the examined blood parameters returned to about the control values except blood urea and serum triglyceride.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.