Gas chromatographic method for analysis of 2,4-D in wheat: interlaboratory study

A procedure is described for the determination of 2,4-D (2,4-dichlorophenoxyacetic acid) in dried green plant material. Samples are first extracted with dilute sodium hydroxide, and then after acidification and solvent extraction, the residues are methylated using boron trifluoride-methanol reagent. The methyl ester of 2,4-D is cleaned up on a Florisil column and quantitated using a gas chromatograph equipped with an electron capture detector. Six laboratories made quadruplicate determinations on control, dried green wheat check samples, on 4 similar samples fortified at the 0.50 ppm level, and on 4 samples fortified at the 1.00 ppm level with 2,4-D. Based on the data from 5 laboratories, the plant fortifications of 0.50 and 1.00 ppm yielded average interlaboratory recoveries of 2,4-D of 83.3 and 88.2%, respectively. The procedure also has potential for the determination of 2,4-D in wheat straw and wheat grain.     

Modified method for electron capture gas-liquid chromatographic determination of diethylstilbestrol residues in urine of fattened bulls

A gas-liquid chromatographic (GLC) method with electron capture (EC) detection was developed for determining diethylstilbestrol residues in the urine of fattened bulls. Diethylstilbestrol (DES) is extracted into benzene, and then into 1N sodium hydroxide. The pH of the phenolic fraction (alkaline phase) is adjusted to 10.2 and DES is extracted again into benzene. Sample extracts are cleaned up on silica gel. Trifluoroacetic anhydride (TFAA) is used as acylation reagent, and the derivatized sample is chromatographed on a 3% OV-17 column and measured with a 63Ni EC detector. The method is suitable for determining residues at levels as low as 2 ppb.     

Relationships between microbial biomass and dissipation of 2,4-D and dicamba in soil

A study was conducted to evaluate relationships between microbial biomass and the dissipation of 2,4-D (2,4-dichlorophenoxy acetic acid) and dicamba (2-methoxy-3,6-dichlorobenzoic acid) in soil. We hypothesized that the size of the microbial biomass should be a strong predictor of the pesticide degradation capacity of a particular soil. Soils with a high microbial biomass should have relatively high levels of general microbial activity and should support a diversity of degradation pathways. In this study, we quantified the degradation of 2,4-D and dicamba in a range of soils with different concentrations of microbial biomass. The herbicides 2,4-D and dicamba were added to similar soils collected from five different land use types (home lawn, cornfield, upland hardwood forest, wetland forest, and aquifer material) and incubated for 80 days under laboratory conditions. Herbicide residue and microbial biomass (C and N) analyses were performed 5, 10, 20, 40, and 80 days following herbicide application. Microbial biomass-C and -N and soil organic matter content were positively correlated with dissipation of 2,4-D and dicamba. The results suggest that there are relationships between the size of the soil microbial biomass and the herbicide degradation capacity of an ecosystem. These relationships may be useful for developing approaches for evaluating and predicting the fate of pesticides in different ecosystems.     

Relationships between microbial biomass and dissipation of 2,4-D and dicamba in soil

A study was conducted to evaluate relationships between microbial biomass and the dissipation of 2,4-D (2,4-dichlorophenoxy acetic acid) and dicamba (2-methoxy-3,6-dichlorobenzoic acid) in soil. We hypothesized that the size of the microbial biomass should be a strong predictor of the pesticide degradation capacity of a particular soil. Soils with a high microbial biomass should have relatively high levels of general microbial activity and should support a diversity of degradation pathways. In this study, we quantified the degradation of 2,4-D and dicamba in a range of soils with different concentrations of microbial biomass. The herbicides 2,4-D and dicamba were added to similar soils collected from five different land use types (home lawn, cornfield, upland hardwood forest, wetland forest, and aquifer material) and incubated for 80 days under laboratory conditions. Herbicide residue and microbial biomass (C and N) analyses were performed 5, 10, 20, 40, and 80 days following herbicide application. Microbial biomass-C and -N and soil organic matter content were positively correlated with dissipation of 2,4-D and dicamba. The results suggest that there are relationships between the size of the soil microbial biomass and the herbicide degradation capacity of an ecosystem. These relationships may be useful for developing approaches for evaluating and predicting the fate of pesticides in different ecosystems.     

Determination of residues from the herbicide 2,4-dichloro-1-(4-nitrophenoxy)-benzene in rice and wheat by electron capture gas-liquid chromatography.

A residue method has been developed which is capable of determining not only 2,4-dichloro-1-(4-nitrophenoxy)-benzene but a majority of the known metabolites of this compound. The residues are reduced to a common amine intermediate which is further derivatized and quantitatively measured by electron capture gas-liquid chromatography. The method is sensitive to 0.01 ppm and is readily suited to routine use. The method has been used on rice and wheat samples.     

Separation of pesticide residues from lipids prior to gas-liquid chromatographic analysis.

Lipids are separated from dieldrin, endrin, and p,p'-DDE residues by saponification in ethanolic sodium hydroxide, acidification with dilute sulfuric acid, and adsorption chromatography on deactivated alumina, using petroleum ether as the eluant. Dieldrin, endrin, and p,p'-DDE are efficiently recovered (95-102%), and p,p'-DDT is converted to p,p'-DDE, which is then recovered with high yield (90-96%). Extremely low lipid carryover (less than 0.3-0.5%) is observed for 0.5-1.0 g samples of chicken fat.     

Collaborative study of a gas-liquid chromatographic method for the analysis of propazine.

A gas-liquid chromatographic method for the determination of propazine in wettable powder formulations containing about 80% active ingredient was collaboratively studied, using a matched pair scheme. The propazine was extracted from the powder with chloroform, with dieldrin as an internal standard, and chromatographed on Carbowax 20M, using a flame ionization detector. Two samples were analyzed using peak height measurements with the following results (13 collaborators): 1.2% overall coefficient of variation and 1.2% coefficient of variation for the random error. Statistical evaluation of these factors reveals no evidence of systematic error contribution. The method has been adopted as official first action.     

Electron capture gas chromatographic determination of traces of formaldehyde in milk as the 2,4-dinitrophenylhydrazone

A quantitative method is described for the determination of formaldehyde in milk by packed-column gas chromatography and electron capture detection. Aldehyde derivatization was carried out in situ with 2,4-dinitrophenylhydrazine followed by extraction and analysis using an external standard. Average recoveries of 96.3 +/- 1.6% were characteristic of the chromatographic method with an estimated detection limit of 0.026 mg/kg. The technique was applied to determination of formaldehyde in milk from cows consuming a formalin-treated feedstuff.     

Collaborative study of a gas-liquid chromatographic method for the analysis of chlorobenzilate and chloropropylate.

A gas-liquid chromatographic method for the determination of chlorobenzilate and chloropropylate in liquid formulations containing about 46 and 26% active ingredient, respectively, was collaboratively studied, using a matched pair scheme. The samples were dissolved in acetone containing debenzyl succinate as an internal standard and chromatographed on Carbowax 20M, using a flame ionization detector. Analyses of 4 samples by 13 collaborators using peak height measurements showed the following results: chlorobenzilate-2.5% overall coefficient of variation, 1.0% coefficient of variation for the random error, and 0.7% systematic error; chloropropylate-2.0, 1.4, and 0.4%, respectively. The method has been adopted as official first action.     

Improved cleanup for gas chromatographic determination of propiconazole residues in soil, wheat grain, straw, and leaves

A simple and sensitive method is described for determination of propiconazole, a new type of broad-spectrum systemic fungicide, in soil, wheat grain, straw, and leaves. Pesticide residues in or on grain and green plant materials are extracted with methanol (or a mixture of methanol and water (4 + 1), for soil), partitioned into methylene chloride, and cleaned up on an alumina column for grain and soil or an activated charcoal column for green plant materials. The amount of residue is quantitatively measured by gas chromatography using an alkali flame ionization detector in the nitrogen-sensitive mode. Recoveries from soil, grain, and green plant materials fortified at 0.1-5 mg/kg are better than 80%. The practical detection limits of this method are 0.01 mg/kg in grain and soil and 0.02 mg/kg in green plant materials.     

Identification and gas-liquid chromatographic determination of aryl phosphate residues in environmental samples.

Aryl phosphates are widely used as flame retardant plasticizers and hydraulic fluids. Laboratory exposures of rainbow trout to a commercial phosphate hydraulic fluid in a flow-through system resulted in substantial biomagnification. Aryl phosphate residues in fish are extracted and cleaned up by the AOAC method for pesticides in fatty foods, and are detected by phosphorus-selective gas-liquid chromatography. Residues of several aryl phosphate mixtures were detected in fish near industrial sites at concentrations ranging from 0.04 to 1 ppm (edible portion basis).     

Rapid gas chromatographic method using nitrogen-phosphorus detection for N-nitrosodimethylamine in 2,4-D and MCPA herbicide formulations

A simple and rapid analytical method has been developed for the determination of N-nitrosodimethylamine (NDMA) in amine salts of phenoxy herbicide formulations of 2,4-D and MCPA, plus mixtures of these with mecoprop and dicamba amine salts. Sample preparation consists of direct extraction using pre-packed disposable extraction tubes eluted with dichloromethane followed by cleanup on a disposable silica gel mini-column using ethyl acetate as eluting solvent. Samples are injected on-column for gas chromatography with a Megabore fused silica column; the NDMA is measured by a thermionic specific detector (TSD) that is selective for nitrogen-phosphorus (NP). A detection limit of 0.1 microgram/mL was easily attainable without any concentration step because the solvent volume is minimal. TSD and thermal energy analyzer (TEA) results have been compared and confirmed by gas chromatography/mass spectrometry. Recovery studies were performed as well as a reproducibility study on one of the 2,4-D formulations.     

An analytical method for the simultaneous determination of butachlor and benoxacor in wheat and soil

Butachlor is a chloroacetanilide herbicide successfully employed in weeding some important crops, and benoxacor is a safening compound able to induce the enzymatic mechanism of chloroacetanilide detoxification in plants. A practical method for a simultaneous detection of butachlor and benoxacor residues in wheat and in soil is described. The procedure can be performed by GC and HPLC. They were extracted with methanol and cleaned up by solid phase extraction (SPE). The analytes were satisfactorily separated via both GC and HPLC techniques, and no interferences were observed coming from plant or soil matrixes or reagents. The limit of quantitation was found to be 5.0 ng by GC and 20.0 ng by HPLC for butachlor and 2.5 ng by GC and 15.0 ng by HPLC for benoxacor. Butachlor recovery tests ranged from 85.4% to 91.7% in wheat shoots and 84.0% to 93.2% in soil; benoxacor recovery tests ranged from 86.5% to 90.8% in wheat shoots and 85.7% to 90.7% in soil. The reproducibility and the accuracy make this method a selective and sensitive tool for routine analyses.