Simultaneous determination of fenitrothion and aminocarb in blueberry foliage and fruits: Application to the analysis of residues in field samples

Abstract

Samples of blueberry foliage and fruits were collected from spray blocks in Ontario after aerial application of fenitrothion and aminocarb at dosage rates of 210 g active ingredient (AI)/ha and 70 g AI/ha respectively. Residues were extracted from the samples by homogenizing with ethyl acetate, cleaned up by microcolumn chromatography using alumina as adsorbent, and analyzed by GLC‐AFID with a glass column packed with 1.5% OV‐17 and 1.95% OV‐210 on 80–100 mesh Chromosorb W‐HP. Average recoveries for fenitrothion and aminocarb from foliage at three fortification levels (1.0, 0.10 and 0.01 ppm) were respectively 99 and 96%. The corresponding values for the fruits were 99 and 95%. Foliage samples collected 1 h post‐spray contained on average 1.13 ppm of fe‐nitrothion and 1.14 ppm of aminocarb. However, residue levels reached below the detection limit (<0.01 ppm) in foliage collected 15 d after treatment. In addition, the fruit samples collected after 15 d post‐spray contained extremely low levels (0.03 ppm for fenitrothion and 0.02 ppm for aminocarb) of residues, and were barely above the detection limit.     

Persistence of deltamethrin and cypermethrin on wheat and sweetclover

Residues of cypermethrin and deltamethrin in wheat herbage and grain and deltamethrin in sweetclover herbage were determined. Cypermethrin was applied at 28 g/ha to wheat and the residues on the herbage declined exponentially from 3.74 ppm immediately after spraying to 0.20 ppm 27 days after spraying. No cypermethrin residues were detected in the grain. Deltamethrin was applied at 6 g/ha to wheat and the residues on the herbage declined exponentially from 0.70 ppm immediately after spraying to 0.05 ppm 27 days after spraying. No deltamethrin residues were detected in the grain. Deltamethrin was applied to sweetclover at 3, 4, 5, 10, and 16 g/ha. Residues on the herbage declined exponentially from 0.10, 0.16, 0.22, 0.40 and 0.70 ppm immediately after spraying to 0.02, 0.03, 0.04, 0.15 and 0.18 ppm 5 days after spraying, respectively.     

Persistence of deltamethrin and cypermethrin on wheat and sweetclover

Abstract

Residues of cypermethrin and deltamethrin in wheat herbage and grain and deltamethrin in sweetclover herbage were determined. Cypermethrin was applied at 28 g/ha to wheat and the residues on the herbage declined exponentially from 3.74 ppm immediately after spraying to 0.20 ppm 27 days after spraying. No cypermethrin residues were detected in the grain. Deltamethrin was applied at 6 g/ha to wheat and the residues on the herbage declined exponentially from 0.70 ppm immediatly after spraying to 0.05 ppm 27 days after spraying. No deltamethrin residues were detected in the grain. Deltamethrin was applied to sweetclover at 3, 4, 5, 10, and 16 g/ha. Residues on the herbage declined exponentially from 0.10, 0.16, 0.22, 0.40 and 0.70 ppm immediatly after spraying to 0.02, 0.03, 0.04, 0.15 and 0.18 ppm 5 days after spraying, respectively.     

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.     

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

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 AI/ha, fensulfothion, and 2.23 and 4.47 kg AI/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 greater than pulp greater than rutabagas root greater than peel greater than 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.     

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.     

Distribution and persistence of carbaryl in some terrestrial and aquatic components of a forest environment

Abstract

An oil‐based formulation of carbaryl (1‐naphthyl N‐methyl‐carbamate) (Sevin‐2‐Oil) was applied twice by a fixed‐wing aircraft at a dosage rate of 280 g of A.I./ha/application to a coniferous forest near Allardville, New Brunswick. The highest concentrations of the chemical in fir foliage, litter and forest soil 1 h after application were respectively 4.20, 1.21 and 0.59 ppm (fresh weight). The residues dissipated rapidly and the DT50 values obtained from the depletion curves were 2.3 d for foliage and 1.5 d for litter and soil samples. Very low levels (<0.1 ppm) of carbaryl persisted in foliage and litter beyond the 10 d sampling period. The maximum residue level found in stream water was 0.314 ppm and more than 50% of it had dissipated within 1 h. Low but detectable levels (0.001 ppm) of the chemical persisted in water until the end of the 10 d sampling period. Sediment samples contained a maximum level of 0.04 ppm, which dissipated below the detection limit within 5 h. Brook trout and slimy sculpins captured in the stream 1 d after the spray contained on average about 0.04 ppm of carbaryl and none of it was found in 3 d postspray samples.     

Residues of chlorpyrifos-methyl in balsam fir foliage, forest litter, soil, stream water, sediment and fish tissue after double aerial applications of Reldan

Chlorpyrifos-methyl was applied twice at 70 g A.I./ha by means of a fixed-wing aircraft to a mixed coniferous forest near Allardville, New Brunswick. Residue in balsam fir foliage was highest (1 ppm wet wt) 1 hr after spraying and rapidly declined to about 30% within 1 day, but persisted at a very low level (0.03 ppm wet wt) for 125 days. Current year's foliage contained a higher level of residue than old foliage. Chlorpyrifos-methyl persisted longer in forest litter than in soil. After 125 days, trace amounts (less than 6 ppb wet wt) were still found in litter but were not detected in soil. In stream water the residue dissipated very rapidly; more than 90% disappeared 3 hours after the second application and were not detected after 4 days. Low-level residue (less than 0.1 ppm wet wt) was present in the sediment and persisted for 10 days. Although brook trout and slimy sculpin captured in the stream within 3 days of the second application contained residues (less than 0.05 ppm fresh wt) none were detected in any fish captured, 9 and 47 days later.     

Factors affecting the concentrations of lead in British wheat and barley grain

The entry of Pb into the food chain is of concern as it can cause chronic health problems. The concentration of Pb was determined in cereal grain samples collected representatively from British Cereal Quality Surveys in 1982 and 1998 (n = 176, 250 and 233 for wheat collected in 1982 and 1998, and barley in 1998, respectively). In addition, paired soil and grain samples were collected from 377 sites harvested across Britain in 1998-2000. Wheat grain Pb ranged from below the analytical detection limit (0.02 mg kg(-1) dry weight, DW) to 1.63 mg kg(-1) DW, and barley grain Pb from <0.02 to 0.48 mg kg(-1) DW. The vast majority of samples (>99% for both wheat and barley, excluding Scottish barley samples collected in 2000) were well below the newly introduced EU limit for the maximum permissible concentration of Pb in cereals (0.2 mg kg(-1) fresh weight, equivalent to 0.235 mg kg(-1) DW). There was a significant reduction in wheat grain Pb in the 1998 survey compared with the 1982 survey. However, 40 barley samples collected from Scotland in 2000 in the paired soil and crop survey showed anomalously high concentrations of Pb, with 10 samples exceeding the EU limit. Washing experiments demonstrated that surface contamination, introduced during grain harvest and/or storage, was the main reason for the high concentrations in these samples. In the paired soil and crop surveys, there were no significant correlations between grain Pb concentrations with total soil Pb and other soil properties, indicating low bioavailability of Pb in the soils and limited uptake and transport of Pb to grain. The Pb in cereal grain is likely to originate mainly from atmospheric deposition and other routes of surface contamination during harvest and storage.     

Residues of chlorpyrifos‐methyl in balsam fir foliage,forest litter,soil, stream water,sediment and fish tissue after double aerial applications of Reldan®

Abstract

Chlorpyrifos‐methyl was applied twice at 70 g A.I./ha by means of a fixed‐wing aircraft to a mixed coniferous forest near Allardville, New Brunswick. Residue in balsam fir foliage was highest (1 ppm wet wt) 1 hr after spraying and rapidly declined to about 30% within 1 day, but persisted at a very low level (0.03 ppm wet wt) for 125 days. Current year's foliage contained a higher level of residue than old foliage. Chlorpyrifos‐methyl persisted longer in forest litter than in soil. After 125 days, trace amounts (< 6 ppb wet wt) were still found in litter but were not detected in soil. In stream water the residue dissipated very rapidly; more than 90% disappeared 3 hours after the second application and were not detected after 4 days. Low‐level residue (< 0.1 ppm wet wt) was present in the sediment and persisted for 10 days. Although brook trout and slimy sculpin captured in the stream within 3 days of the second application contained residues (< 0.05 ppm fresh wt) none were detected in any fish captured, 9 and 47 days later.     

Phosalone applied to cotton (Gossypium hirsutum L.): its deposition and persistence on foliages, soils and final residues in seeds

Phosalone, O,O-diethyl-S-(6-chloro-1,3-benzoxazol-2(3H)-onyl)methyl phosphorodithioate, was field-applied by ground equipment to cotton (Gossypium hirsutum L.) at the rates of 1050 and 2100 g a.i./ha, respectively, to determine its dissipation on leaves and soils and the residues in seeds at harvest. The insecticide concentrations on cotton leaves and soils were measured periodically for 14 days following its application. It was found that the half lives of the insecticide on cotton leaves at the dosages of 1050 and 2100 g a.i./ha were 6.8 and 6.3 days, respectively. And the half lives on soils for the 2 dosages were 7 and 5.8 days, respectively. The residues remaining in soils at harvest time were 0.072 and 0.121 mg/kg 14 days post-application and the residues in cotton seeds were relatively low (less than 0.02-0.12 mg/kg).     

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.     

The effect of aldicarb on nematode population and its persistence in carrots, soil and hydroponic solution

Aldicarb, Temik 15 G, was incorporated in furrows at 3.37 and 6.73 kg ai (active ingredient)/ha and carrots (Daucus carota L.) were directly seeded on the same day. The numbers of nematode larvae were significantly suppressed in the treated plots; averages were 249, 74, and 51/50 cc soil samples for control (0), 3.37 and 6.73 kg ai/ha, respectively. Aldicarb treatment resulted in a 28% yield increase as compared to the untreated. Aldicarb residue in carrots was 28 ppb for the low treatment and 46 ppb for the high. Residual levels in soil of high treatment declined from 61 to 31 ppb during two weeks prior to harvest, meanwhile, those in the low decreased slightly from 13 to 12 ppb. Carrots placed in hydroponic solution containing aldicarb 14.5 ppm for 6 days, had an aldicarb residue of 10.26 ppb and the hydroponic solution, 2.7 ppb. Persistence of aldicarb residue was in carrot greater than in soil greater than in hydroponic solution.     

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.     

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.     

The persistence of insecticidal chemicals in soils treated with granular formulations of aldicarb and their uptake by potato plants

Abstract

Potatoes were grown in Plainfield sand and muck treated, in furrow, with aldicarb (Temik 15G, 3.36 kg Al/ha). .Soils were contained in 2 m^z field plots and had not been treated previously with pesticides. Soil, seed pieces, foliage and tubers were analyzed for the insecticide and its sulfoxide and sulfone metabolites during the 12 wk following planting. The disappearance of aldicarb from the soil was accompanied by partial conversion to the sulfoxide and sulfone. After increasing rapidly during the first 2 wk, the aldicarb concentration in the seed piece declined and a similar concentration of aldicarb sulfoxide accumulated which subsequently slowly disappeared. Aldicarb sulfoxide was the major insecticidal material in the new foliage. High initial concentrations, observed at 3–4 wk, declined by about 90% after 6 wk. Aldicarb sulfoxide residues of 2–4 ppm in the first new tubers at 6 wk declined by 90% by 12 wk. Potatoes were also grown under greenhouse conditions in Plainfield sand treated with Temik 10G at rates equivalent to 1.68, 3.36 and 6.72 kg Al/ha. Maximum aldicarb sulfoxide concentrations in soil, seed piece and foliage increased with application rate. The sulfoxide was much more persistent in the soil and foliage than in the field experiment indicating the importance of environmental factors to its behaviour in both soil and potato plants.     

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).     

A comparison of the persistence in a clay loam of single and repeated annual applications of seven granular insecticides used for corn rootworm control

In May 1983, granular formulations of carbofuran, chlorpyrifos, disulfoton, fonofos, isofenphos, phorate, and terbufos were applied in incorporated bands to duplicate 2 m2 field plots of clay loam. Insecticide concentrations were determined in the bands at 0,1,2,3,4,6,8,10,12,16, and 20 wk. Following spring cultivation, the insecticides were applied to the same plots in 1984 and 1985. In addition, carbofuran was applied to previously untreated plots in 1984 and all 7 materials were applied to previously untreated plots in 1985. Sampling and analysis were carried out as in 1983. Persistence was assessed on the basis of the disappearance rates measured for the 1st 8 wk and of a calculated Effectiveness Potential (the ratio of the average residue in the upper 5 cm of the band at 8, 10 and 12 wk and the published LC95 for western corn rootworm in clay loam soil). Soils treated with carbofuran and isofenphos in 1984 and all soils treated in 1985 were tested for anti-insecticide activity. Soil cores from some carbofuran, chlorpyrifos and terbufos treated plots were sectioned vertically to establish the distribution of the insecticides during 1985. In addition, granular and pure chemical forms of isofenphos and carbofuran were applied at 10 ppm to anti-isofenphos and anti-carbofuran active and control soils (from field plots) maintained at 10 and 20% moisture in the laboratory to assess the effect of formulation and moisture on persistence in active soils. Insecticide concentrations were determined at 0,1,3,7, 10,14,21,28, and 35 days. The persistence of chlorpyrifos, terbufos and phorate was relatively constant over the 3 years and between plots receiving single and multiple treatments. Disulfoton and fonofos behavior was more variable and that of carbofuran and isofenphos was extremely variable. Anti-insecticide activity against carbofuran and isofenphos was detectable 2 wk after an initial application and was still present the following spring. Anti-insecticide activity against fonofos, terbufos sulfoxide, phorate sulfone and disulfoton sulfone was also generated in this soil. Anti-insecticide activity against chlorpyrifos, disulfoton, terbufos and phorate was not present. Carbofuran, chlorpyrifos and terbufos (+ metabolites) present in the upper 5 cm of soil averaged 93, 94 and 94%, respectively, of the total core contents over 12 wk. Significant moisture dependent differences were observed between the behavior of granular carbofuran and granular isofenphos in anti-insecticide active soils.(ABSTRACT TRUNCATED AT 400 WORDS)     

The effect of aldicarb on nematode population and its persistence in carrots,soil and hydroponic solution

Abstract

Aldicarb, Temik^® 15 G, was incorporated in furrows at 3.37 and 6.73 kg ai (active ingredent)/ha and carrots (Caucus carota L.) were directly seeded on the same day. The numbers of nematode larvae were significantly suppressed in the treated plots; averages were 249, 74, and 51/ 50 cc soil samples for control (0), 3.37 and 6.73 kg ai/ha, respectively. Aldicarb treatment resulted in a 28% yield increase as compared to the untreated. Aldicarb residue in carrots was 28 ppb for the low treatment and 46 ppb for the high. Residual levels in soil of high treatment declined from 6l to 31 ppb during two weeks prior to harvest, meanwhile, those in the low decreased slightly from 13 to 12 ppb. Carrots placed in hydroponic solution containing aldicarb 14.5 ppm for 6 days, had an aldicarb residue of 10.26 ppb and the hydroponic solution, 2.7 ppb. Persistence of aldicarb residue was in carrot > in soil > in hydroponic solution.     

Preliminary study on persistence in soil and residues in maize of imidacloprid

The aim of this work was to study the distribution of imidacloprid in soil and its translocation to roots and aerial parts of maize plant. The main objective was to assess imidacloprid residues in field environment, in order to provide data on honeybees exposure level to such an active substance. Imidacloprid has been detected and quantified by Triple Quadrupole HPLC-MS-MS. Pesticide persistence in the soil and its residues in pollen and in maize plants have been evaluated during the growing of maize plants developed from seeds dressed with Gaucho 350 FS (imidacloprid: 1.0 mg/seed). The sowing has been performed by means of a pneumatic precision drill. Samples have been collected at 30, 45, 60, 80, 130 days after the sowing, as pollen samples have been collected at the tasseling. Imidacloprid presence in aerial part of maize plant declined to 2-3 μg/kg 80 days after the sowing, while concentration in kernel at harvest was <1 μg/kg. Maize pollen represents an important part of protein supply of beehives, and it is of critical importance to bee foraging. The values detected (imidacloprid residues <1 μg/kg) showed that maize pollen source should not be relevant for acute toxicity impact on honey bees.