Comparison of gas chromatography and immunoassay methods in quantifying fenitrothion residues in grape juice processed into alcoholic drinks.

Wine and Arak, the national alcoholic drink in Lebanon, were prepared from grape juice fortified with fenitrothion to a concentration of 20ppm. Samples of the 11 fractions produced by the fermentation and distillation steps were analyzed for fenitrothion residues using gas chromatography (GC) and enzyme-linked immunosorbent assay (ELISA). Results of residue analyses showed that the two techniques were highly correlated (r = 0.978) and indicated that fenitrothion was stable during the fermentation steps but not during distillation. The clarified wine 35 days later contained about 85% (15.3 ppm) of the fenitrothion concentration found in the juice as determined by GC analysis. Arak was prepared by a two-steps distillation of the clarified wine. The alcohol distillate and undistilled fraction from the first distillation contained 2.5 ppm and 5.8 ppm of fenitrothion, respectively. No fenitrothion residues were detected by both techniques in the four fractions collected from the second distillation step.     

Fate of DDT and parathion in grapes processed into Arak,an alcoholic beverage

Abstract

Arak, the national alcoholic drink in Lebanon, was prepared from grapes to which either DDT or parathion had been added. Samples of the nine fractions produced from the fermentation and distillation steps were analyzed for DDT and parathion and their respective metabolites.

DDT degraded to DDD during the fermentation step resulting in a sharp decrease in DDT level. The two distillation steps contributed to a further decrease in the DDT level so that the final product contained less than 2% of the amount found in the fresh grape juice. Although the concentration of DDD increased sharply during fermentation, it also decreased to a negligible level during the subsequent distillation procedure.

Parathion was more stable than DDT during the fermentation and first distillation steps. However, the second distillation process caused a share decline in its level and the Arak contained only about 6% of the residues present in the fresh juice, paranitrophenol being the only metabolite detected.     

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.     

Behavior of dialifor,dimethoate, and methidathion in artificially fortified grape juice processed into wine

Abstract

Dialifor and methidathion were added to diluted “Zinfandel”; grape concentrate at 25 ppm and dimethoate at 1.0 and 25 ppm prior to fermentation with Saccharomyces cerevisiae. The finished wine 56 days later contained 10% (2.5 ppm) of the dialifor, 46% (12 ppm) of the methidathion and 85% (21 and 0.98 ppm) of the dimethoate added to the grape must. Residues in wine stored at 24°C dissipated by hydrolysis; half‐lives in wine were 7 days for dialifor and methidathion and 30 days for dimethoate. Residues were unchanged in wine in frozen storage for one year. Analysis of seven commercial wines for dimethoate indicated less than 0.03 ppm dimethoate was present; identity could not be confirmed by thin‐layer chromatography at this level.     

Persistence characteristics of operationally sprayed fenitrothion in nearby unsprayed areas of a conifer forest ecosystem in New Brunswick

Abstract

Persistence characteristics of operationally sprayed fenitrothion were investigated in various substrates sampled from neighbouring unsprayed areas in New Brunswick. Air, water, sediment, aquatic plants, fish, balsam fir [Abies balsamea (L.) Mill] foliage, forest soil and litter samples were collected from random sampling locations selected within 200 m from the operational spray blocks. The same substrates were resampled from the same plots and from the same locations about a year later just prior to the commencement of the operational spraying. Control samples were collected from an unsprayed site, near Sault Ste. Marie, Ontario. All samples were analysed for fenitrothion, by gas‐liquid chromatography. Except the fish samples all the substrates collected during the time of operational spraying contained low but detectable levels of fenitrothion. When collected a year later prior to the operational spray program, only balsam fir showed any detectable levels (detection limit, 0.01 ppm) of the chemical. All other samples showed no fenitrothion residues (detection limit for air, 10 ng/m³; for water, 0.01 ppb; and for other samples, 0.01 ppm). The findings confirmed that fenitrothion does not persist for an extended period of time in the aquatic substrates. The conifer foliage, however, showed persistent residues at a level of about 0.55 ppm even after the winter months, although there was no indication of accumulation of the chemical as a result of repeated exposure. The study demonstrated that the conifer needles acted as a micro sink for the chemical which showed a tendency to persist in the leaf tissues for a considerable length of time.     

Fate of parathion in artificially fortified grape juice processed into wine

"Semellon" grape juice fortified with a high level of 25 ppm parathion was fermented using Saccharomyces cerevisiae var. ellipsoideus. After 12 days inte parathion levels in the wine and lees were 10.3 and 156 ppm, respectively; the paraoxon, aminoparathion, and p-nitrophenol levels in the wine were 0.16, 0.20, and 4.5 ppm, respectively, and in the lees were 0.04, 3.1 and 10 ppm, respectively. Thus, hydrolysis of parathion to p-nitrophenol and parathion sorption to sedimented particulate matter were important pathways for parathion residue reduction in the wine. The 56-day-old finished wine just prior to bottling contained 8.8 ppm parathion, 0.04 ppm paraoxon, 0.21 ppm aminoparathion, and 3.0 ppm p-nitrophenol. Two months storage at 24 degrees, 12 degrees, 4 degrees, and -20 degrees C had no effect on paraoxon and aminoparathion residue levels in the wine; parathion residues in wine decreased at all storage temperatures.     

Behavior of dialifor, dimethoate, and methidathion in artificially fortified grape juice processed into wine.

Dialifor and methidathion were added to diluted "Zinfandel" grape concentrate at 25 ppm and dimethoate at 1.0 and 25 ppm prior to fermentation with Saccharomyces cerevisiae. The finished wine 56 days later contained 10% (2.5 ppm) of the dialifor, 46% (12 ppm) of the methidathion and 85% (21 and 0.98 ppm) of the dimethoate added to the grape must. Residues in wine stored at 24 degrees C dissipated by hydrolysis; half-lives in wine were 7 days for dialifor and methidathion and 30 days for dimethoate. Residues were unchanged in wine in frozen storage for one year. Analysis of seven commercial wines for dimethoate indicated less than 0.03 ppm dimethoate was present; identity could not be confirmed by thin-layer chromatography at this level.     

Analysis and fate of acephate and its metabolite,methamidophos, in pepper and cucumber

Abstract

Levels of acephate (Orthene^R) and its principle metabolite, methamidophos, in/on greenhouse‐grown pepper and cucumber fruits and leaves in relation to the applied methamidophos were monitored. Dislodgeable and total residues of acephate and methamidophos were determined by gas‐liquid chromatography equipped with a flame ionization detector (GC‐FID) and were confirmed by nitrogen phosphorus detector (GC‐NPD). The dissipation curves of the residues followed first‐order kinetics (R²> 0.96). Initial residues of acephate on fruits varied between pepper (15.12 ppm) and cucumber (2.16 ppm) . Total residues in fruits and leaves determined at intervals following application revealed the greater persistence of acephate on pepper fruits (half‐life [t_1/2] of 6 d) than on cucumber fruits (t_1/2 was 3.7 d) . T_1/2 values for the applied methamidophos were 4.7 and 5.3 d on pepper and cucumber fruits, respectively. Deacety‐lation of acephate (formation of its metabolite) was detectable 1 d following acephate treatment and reached a maximum of 2.05% of initial acephate residues 3 d after application on pepper fruits. On cucumber fruits, acephate metabolite reached a maximum of 2.12% one wk following application. No acephate residues were detected above the limit of detection of 0.001 ppm in pepper fruits 50 d following acephate application while its metabolite was detectable at that time (detectability limit was 0.0001 ppm).     

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.     

Herbicide residues in grapes and wine

Abstract

The persistence of several common herbicides from grapes to wine has been studied. Shiraz, Tarrango and Doradillo grapes were separately sprayed with either norflurazon, oxyfluorfen, oxadiazon or trifluralin ‐ persistent herbicides commonly used for weed control in vineyards. The dissipation of the herbicides from the grapes was followed for 28 days following treatment. Results showed that norflurazon was the most persist herbicide although there were detectable residues of all the herbicides on both red and white grapes at the end of the study period. The penetration of herbicides into the flesh of the grapes was found to be significantly greater for white grapes than for red grapes. Small‐lot winemaking experiments showed that norflurazon persisted at levels close to the initial concentration through vinification and into the finished wine. The other herbicides degraded, essentially via first‐order kinetics, within the period of “ first fermentation”; and had largely disappeared after 28 days. The use of charcoal together with filter pads, or with diatomaceous earth was shown to be very effective in removing herbicide residues from the wine. A 5% charcoal filter removed more than 96% of the norflurazon persisting in the treated wine.     

Biological activity and bioavailability of grain bound 14C‐malathion residues in rats

Abstract

Paddy (unmilled rice), milled rice and maize‐bound ¹⁴C residues were prepared using ¹⁴C‐succinate‐labelled malathion at 10 and 152 ppm. After 3 months, the bound residues accounted for 12%, 6.5% and 17.7% of the applied dose in paddy, milled rice and maize respectively in the grains treated at 10 ppm. The corresponding values for the 152 ppm were 16.6%, 8.5% and 18.8%. Rats fed milled rice ‐ bound ¹⁴C‐residues eliminated 61% of the ¹⁴C in the faeces and 28% in the urine. The corresponding percentages for paddy and maize were 72%, 9% and 53%, 41% respectively; indicating that bound residues from milled rice and maize were moderately bioavailable. When rice‐bound malathion residues (0.65 ppm in feed) were administered to rats in a 5 week feeding study, no signs of toxicity were observed. Plasma and RBC cholinesterase activities were slightly inhibited: blood urea nitrogen was significantly elevated in the test animals. Other parameters examined showed no or marginal changes.     

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.     

Residues of carbofuran and its two carbamate metabolites in field‐treated rutabaga 1

Abstract

Carbofuran was applied over seeded rutabaga cv. York and residues (corrected for recovery) of carbofuran, 3‐hydroxy‐ and 3‐ketocarbofuran in the harvested roots averaged 0.15, 0.23 and 0.07 ppm in peel and 0.09, 0.14 and 0.05 ppm in pulp, respectively. Samples were extracted by hot acid digestion, partitioned in methylene chloride and cleaned up on Florisil. The 3‐hydroxy‐carbofuran was ethoxylated and the compounds were converted into their dinitrophenyl ethers and analysed by electron capture gas chromatography using 3% OV‐3 column.     

Residue levels of fenitrothion and aminocarb in the air samples collected from experimental spray blocks in New Brunswick in 1982

Abstract

Fenitrothion and aminocarb formulations were aerially sprayed over mixed coniferous forests near Fredericton and Bathurst, New Brunswick, Canada. Insecticide concentrations inside the spray blocks were measured at intervals of time by trapping the airborne toxicants in a fritted‐glass bubbler containing dimethylformamide (DMF). The residues in DMF were analysed by gas chromatography. Concentrations of the insecticides in the air sampled decreased rapidly with time from peak levels of 1997 ng/m³ (fenitrothion) and 1201 ng/m³ (aminocarb). Concentrations of the two insecticides in the air samplers were dependent upon the nature of the chemicals, type of formulation used, spray timings and other environmental factors.     

Improved Gas Chromatographic method for analysis of trichlorfon insecticide in soil and turfgrass thatch

Abstract

An improved Gas Chromatographic method utilizing simple extraction and one‐step purification on solid phase extraction tubes was developed for analysis of trichlorfon as an intact insecticide compound in turfgrass thatch and soil. A Gas Chromatograph/Mass Spectrum (GC/MS) was used for confirmation of trichlorfon structure. The method readily determines trichlorfon in the presence of dichlorvos. Using an electron capture (EC) detector, the detection limits were 0.02 ppm in soil, 0.04 ppm in turfgrass thatch, and 0.09 ppm in soil, and 0.2 ppm in turfgrass thatch using an nitrogen phosphorus (NP) detector.     

Influence of surfactant concentration on foliar retention of pesticides used in forestry

Abstract

Aqueous tank mixes of permethrin, fenitrothion, Bacillus thuringiensis (B.t.), diflubenzuron (DFB), and glyphosate containing different amounts of Triton® X‐114, a nonionic surfactant, were prepared. Glyphosate formed clear solutions, permethrin and fenitrothion formed emulsions, DFB and B.t provided suspensions. Emulsion stability of permethrin and fenitrothion increased with increasing surfactant level, while the emulsion drop size decreased.

Foliage of white oak, trembling aspen, white spruce and balsam fir were dipped in tank mixes of pesticides (except B.t.) labelled with ¹⁴carbon. The amount of pesticide retained on foliage was determined by liquid scintillation counting. Foliage was also dipped in non‐radioactive B.t. tank mixes, and the protein retained was determined colorimetrically. With all tank mixes, a direct relationship was observed between the mass of liquids retained on foliage and liquid viscosity. In contrast, the amount of pesticide retained was unaffected by viscosity, but was influenced by emulsion drop size. Initially, the amount of pesticide retained on foliage increased with increasing surfactant concentration. Beyond an optimum surfactant level, the emulsion drop sizes were too small and the emulsions became too stable to allow maximum retention of pesticides on foliage. With the glyphosate solutions, however, no optimum surfactant level was indicated because foliar concentrations continued to increase with increasing surfactant levels.     

Behavior of parathion in tomatoes processed into juice and ketchup

Fresh tomatoes were cut, fortified with 25 ppm (micrograms/g) of parathion (0,0-diethyl 0-4-nitrophenylphosphorothioate) and processed into either juice or ketchup. Tomato juice was canned, while ketchup was placed in bottles. All samples were stored at room temperature for analysis at two-monthly intervals. Parathion residues were measured quantitatively by GLC, while the two metabolites, aminoparathion (0,0-diethyl 0-4-aminophenylphosphorothioate) and 4-nitrophenol, were determined colorimetrically. The presence of the three compounds was confirmed qualitatively by TLC. Blanching of tomatoes resulted in about 50% reduction of parathion level. Pulping of fruits caused a further decrease in parathion residues in juice as a result of its sorption and concentration in the semi-solid pulp. About 85% of parathion added to tomatoes was lost during the processing steps. Storage of juice resulted in a gradual decrease in parathion levels, whereby only 1.7% of the original amount was detected after six months of storage. The compound was stable in ketchup for the first four months of storage but decreased thereafter to almost 7% of the original quantity added to fruits. Aminoparathion and 4-nitrophenol were detected in low levels.     

Residues of EBDC fungicides and ETU in experimental and commercial beverages (beer and wine)

Residues of EBDC (ethylenebisdithiocarbamate) fungicides and ETU (ethylenethiourea; 2-imidazolidinethione) were monitored in beers and wines from different locations. No EBDC residues were detected in any of the samples examined. Concerning the ETU residues, the residue levels higher than the limit of method detection (0.01 ppm) were 22.6% and 7.3% in the commercial beer and wine samples respectively, but the number of samples containing more than 0.1 ppm of ETU was practically negligeable.     

Determination of organochlorine and organophosphorus pesticide residues in low moisture,nonfatty products using a solid phase extraction cleanup and gas chromatography

Abstract

A multiresidue solid‐phase extraction (SPE) method for the isolation and subsequent gas Chromatographie determination of organochlorine and organophosphorus pesticide residues in low‐moisture, nonfatty products is described. Residues are extracted from samples with an acetonitrile/water mixture. Cleanup of the extract is performed using graphitized carbon black and anion exchange SPE columns, and analysis is performed by gas chromatography with Hall electrolytic conductivity and flame photometric detection. Recovery data was obtained by fortifying corn, oats and wheat with pesticides. The average recoveries were 79–123% for eight organochlorine and 51–122% for 28 organophosphorus pesticide residues. The limit of quantitation for chlorpyriphos was 0.05 ppm using the Hall electrolytic conductivity detector and <0.005 ppm using the flame photometric detector.     

Bioconcentration and metabolism of DDT, fenitrothion and chlorpyrifos by the blue-green algae Anabaena sp. and Aulosira fertilissima

Anabaena and Aulosira fertilissima showed a marked ability to accumulate DDT, fenitrothion and chlorpyrifos. Although the maximum accumulation of DDT was almost the same in both organisms, there were significant differences in their abilities to accumulate fenitrothion and chlorpyrifos. Patterns of uptake of DDT under different treatments were also similar in both Anabaena and Aulosira, but there were significant differences in the patterns of accumulation of fenitrothion between these two organisms. In Aulosira the maximum accumulation of fenitrothion was observed on the second day, whereas, in Anabaena, maximum accumulation was noticed on the first day. A completely different pattern of accumulation of chlorpyrifos was observed in Aulosira, which continued to accumulate chlorpyrifos throughout the experimental period. Bioconcentration of DDT in Anabaena and Aulosira ranged from 3 to 1568 ppm (microg g(-1)) and 6 to 1429 ppm, respectively. Bioconcentration of fenitrothion and chlorpyrifos in Anabaena varied from 53 to 3467 ppm and 7 to 6779 ppm, respectively. In Aulosira the bioconcentration varied from 100 to 6651 ppm and 53 to 3971 ppm for fenitrothion and chlorpyrifos, respectively. Anabaena and Aulosira metabolised DDT to DDD and DDE. Amounts of these DDT metabolites detected in the organisms were dependent on the concentration of treatment. DDD was the major, and DDE the minor, metabolite. These organisms were not able to metabolise the organophosphorus insecticides, fenitrothion and chlorpyrifos.