Capillary gas chromatographic-mass spectrometric determination of fluoroacetate residues in animal tissues

A method for the quantitative determination of fluoroacetate (FAC) residues in animal tissues is described. The procedure involves tungstic acid extraction, partitioning into ethyl acetate, evaporation of ethyl acetate, derivatization with pentafluorobenzyl bromide (PFB), and analysis of the resulting derivative (PFB-FAC) by capillary gas chromatography-mass spectrometry (CGC-MS) with specific ion monitoring (SIM). The tungstic acid system extracted 96.8 +/- 4.2% of the endogenous 14C-1080 residues in rat tissues. Recovery of FAC during the extraction, purification, and derivatization procedures is established by use of a 14C-FAC spike. 1,2-Dibromobenzene is used as an internal standard for the CGC-MS analysis. PFB-FAC is identified on the basis of comparative retention times and the relative intensities of m/z 257.9 and 181.0. PFB-FAC is quantitated by comparing the response at m/z 257.9 to a PFB-FAC standard curve. Routine sensitivity of the method allows determination of 10 ppb fluoroacetate in tissue.     

Quantitative gas chromatographic-mass spectrometric assay of five sulfonamide residues in animal tissue

A gas chromatographic-mass spectrometric procedure using isotopically labeled internal standards and the technique of selective-ion monitoring was used to assay sulfamethazine, sulfadimethoxine, sulfabromethazine, sulfathiazole, and sulfaquinoxaline in liver and muscle tissue of swine, poultry, and cattle. The data presented clearly demonstrate the applicability of this procedure for confirmation of sulfonamide residues in animal tissue.     

Gas chromatographic-mass spectrometric detection and quantitation of lincomycin in animal feedingstuffs

A substantially improved assay was developed for lincomycin A in animal feedingstuffs. The assay allows unambiguous quantitation of at least 0.1 ppm in feed. Lincomycin B did not interfere because of differences in both retention time and mass of the main fragment ion in electron impact (EI) spectra. The assay using single ion monitoring with EI detection would not discriminate between lincomycin A and clindamycin. The presence of the latter was easily confirmed by using gas chromatography-mass spectrometry in the chemical ionization mode. The assay for lincomycin A was linear in the range 0-40 ng applied to the gas chromatographic column. The recovery was 93.4 +/- 4.2% at 1 and 5 ppm and 86.2 +/- 5.5% at 0.1 ppm in feed. The coefficient of variation of the assay was 4.8% at both 1 and 5 ppm, and was 6.43% at 0.1 ppm.     

Gas chromatographic-mass spectrometric determination of adipate-based polymeric plasticizers in foods

A method for the quantitative determination of adipate-based polymeric plasticizers in foods is described. The procedure involves extraction from the food and transmethylation of the polymeric plasticizer to form dimethyladipate (DMA). The derivative is cleaned up by size-exclusion chromatography and determined by capillary gas chromatography-mass spectrometry with selected ion monitoring. The use of a deuterated internal standard at the extraction stage enables quantitation by stable isotope dilution. A detection limit of 0.1 mg/kg of the polymeric plasticizer in foods and a relative standard deviation of 4% have been achieved routinely. The method has been applied successfully to the analysis of cheese, sandwiches, meat, biscuits, and cake that have been in contact with polymeric plasticized poly(vinyl chloride) films.     

Methods for determination of ionophore-type antibiotic residues in animal tissues

Methods for the analysis of polyether antibiotics in animal tissues and fluids are described. For monensin and nigericin, only methods based on bioautography are available. For lasalocid, in addition to TLC bioautography for quantitation in chicken skin and fat, LC methods based on fluorescence detection have been developed for quantitation in animal blood, milk, liver, skin, and fat. In addition, a confirmatory method for lasalocid is described; this is based on purification by LC followed by silylation and pyrolysis gas chromatography-positive chemical ionization mass spectrometry.     

Gas chromatographic determination of incurred dimetridazole residues in swine tissues

A gas chromatographic method for determination of 2-hydroxymethyl-1-methyl-5-nitroimidazole (DMZOH), the hydroxy metabolite of dimetridazole, in swime muscle has been developed. The method uses cleanup steps similar to those of an earlier polarographic method. The present method is capable of quantitating levels as low as 2 ppb and detecting less than 1 ppb. Recoveries from 30 control tissues spiked at 1, 2, or 4 ppb averaged 80.4%. Performance of the method in incurred tissue was documented and limited data on the depletion of the metabolite in muscle were generated. The muscle of swine given 150 ppm dimetridazole in feed for 14 days contained less than 1 ppb DMZOH at 12 h withdrawal time.     

Gas chromatographic-mass spectrometric determination of epoxidized soybean oil contamination of foods by migration from plastic packaging

A method for the quantitative determination of epoxidized soybean oil (ESBO) in foods is described. The procedure involves addition of a diepoxidized fatty acid ester internal standard, followed by lipid extraction from the food and transmethylation under basic conditions. Without further cleanup, the methylated fatty acid epoxides are derivatized to form 1,3-dioxolanes, which are then determined by capillary gas chromatography-mass spectrometry with selected ion monitoring. A detection limit of 2.0 mg/kg of epoxidized soybean oil in foods and a relative standard deviation of 7% have been achieved routinely. The method has been applied successfully to the analysis of cheeses, sandwiches, cakes, and microwave-cooked meals which have been contaminated with ESBO by migration from PVC film.     

Gas chromatographic-mass spectrometric method for the analysis of dimethomorph fungicide in dried hops

An analytical method for the determination of dimethomorph [(E,Z)-4-[3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)acryloyl]morpholine] residues in dried hops was developed utilizing liquid-liquid partitioning, automated gel permeation chromatography (GPC), Florisil and aminopropyl solid phase extraction (SPE) column cleanups, and gas chromatography (GC) with mass selective detection (MSD). Method validation recoveries from dried hops ranged from 79 to 103% over four levels of fortification (0.1, 1.0, 5.0, and 20 ppm). Control and dimethomorph-treated hop samples collected from three field sites had residue levels of <0.10 and 4.06-17.32 ppm, respectively. The method was validated to the limit of quantitation at 0.10 ppm. The limit of detection for this method was 0.045 ppm.     

Liquid chromatographic determination of multiple sulfonamide residues in bovine milk

A liquid chromatographic method has been developed for simultaneous determination of residues of 10 sulfonamide drugs at 10 ppb and above in raw bovine milk. The method is based on a chloroform-acetone extraction, evaporation of organic phase, dissolution of residues in an aqueous potassium phosphate solution, and extraction of fatty residue into hexane. The aqueous layer is collected, filtered, injected onto an LC system, and detected by ultraviolet absorption at 265 nm. To elute all 10 sulfonamides isocratically, 2 chromatographic conditions are required. Seven sulfonamides can be quantitated with 12% methanol in the mobile phase; 4 sulfonamides can be quantitated with 30% methanol. Sulfamethazine, the most widely used sulfonamide, is detected on both systems. Recoveries are 44-87% for individual sulfonamides, with only 2 below 60%. Coefficients of variation are 3-13% at 10 ppb.     

Gas chromatographic determination of cholesterol in egg products

A method has been developed for quantification of cholesterol in fresh egg yolks, spray-dried egg yolks, fresh whole eggs, and spray-dried whole eggs. The method uses saponification followed by petroleum ether extraction of cholesterol. Separation of organic and aqueous layers is enhanced by sodium chloride. Petroleum ether extracts are dried under nitrogen and redissolved in chloroform-methanol (2 + 1) for injection into a gas chromatograph. Cholesterol is separated and quantitated on a high temperature capillary column coated with 5% diphenyl and 95% dimethyl polysilicone crosslinked gum. The method was compared with the current AOAC method 17.017-17.022, and results indicated no significant difference (alpha = 0.05). However, the proposed method allowed separation and analysis of 16 samples in 7 h while the current AOAC method allowed separation and analysis of only 4 samples in 9 h.     

Liquid chromatographic determination and gas chromatographic-mass spectrometric confirmation of lasalocid sodium in bovine liver: interlaboratory study

An analytical method has been developed that can reliably measure the metabolic marker residue of lasalocid. The method monitors this marker residue in food samples to ensure that the total residue of toxicological concern is not being exceeded. Interlaboratory studies of the liquid chromatographic determinative procedure and the gas chromatographic/mass spectrometric confirmatory procedure for lasalocid sodium at the 0.7 ppm level and higher were successful.     

Gas-liquid chromatographic-mass spectrometric determination of alpha- and beta-naphthylamines in FD&C Red No. 2 (amaranth)

A method is described for the simultaneous quantitation of trace amounts of alpha- (alpha-NA) and beta-naphthylamines (beta-NA) with detectability in the 0.1 ppb range and sensitivity of 50 picomoles in certified food grade amaranth (FD&C Red No. 2; C.I. Food Red 9; CI 16185). The amaranth sample is extracted with benzene, and the evoporated residue is derivatized with perfluorooctanoic anhydride. The resulting derivatives are separated by gas-liquid chromatography and identified and quantitated by mass spectrometric monitoring of the m/e at 539.04. The method was used for quantitation of alpha-NA and beta-NA in randomly chosen samples of amaranth. Of 11 samples from different manufacturers, 5 were free of the beta-isomer; the remaining samples contained up to 1.2 ppb beta-NA. The concentration of alpha-NA ranged from no detectable amount to 970 ppb; the majority of the samples contained less than 7 ppb.     

Identification of nosiheptide in feeds and detection of residues in animal tissues

Nosiheptic is determined in fermentation broths of Streptomyces actuosus either by a microbiological method using Staphylococcus aureus or, more easily, by an automated colorimetric method. The results obtained with both methods correspond well for concentrations greater than 100 microgram/mL with a standard deviation of 1-3%. For determination of nosiheptide as a feed additive, the microbiological assay is made more specific by pretreatment with petroleum ether and 1N HCl. Standard deviation is less than 4%, and the assay is sensitive to 1 ppm. Nosiheptide is identified in feed containing other frequently used antibiotics by thin layer chromatography with bioautography; sensitivity is 1 ppm. The absence of traces of nosiheptide in tissues of treated swine and broiler is confirmed by microbiological diffusion, sensitive to 0.025 ppm.     

Liquid chromatographic determination of three sulfonamides in animal tissue and egg

Sulfonamides are widely used as a feed additive in animal production in Japan. The present paper is a determination of 3 sulfonamides: sulfamethazine (SMZ), sulfamonomethoxine [SMX, 4-amino-N-(3-methoxypyrazinyl)-benzenesulfonamide], and sulfadimethoxine (SDX) in animal tissue and egg by liquid chromatography (LC). Tissues were extracted with acetonitrile and fat was removed by liquid/liquid partition. The sulfonamides were purified by an ODS cartridge column; then each compound was separated by an ODS LC column and detected at 268 nm. Quantification levels were 0.02 ppm for SMZ and SMX, and 0.04 ppm for SDX; detection limits were 0.01 ppm for SMZ and SMX, and 0.02 ppm for SDX. Calibration curves were linear between 2 and 40 ng for SMZ and SMX, and between 4 and 80 ng for SDX. Recoveries from muscle and egg samples spiked with 1-2 micrograms/10 g were 81-98%.     

Liquid chromatographic determination of carbadox residues in animal feed

A liquid chromatographic (LC) method for determining residues of carbadox in the 0.01-10 ppm range in swine feed is described. Carbadox is extracted from ground feed with 25% acidified methanol-CHCl3, removed from emulsion-forming coextractables via an alumina column, separated from highly colored pigments by acid-base liquid-liquid partitioning, and finally isolated from interferences on a second alumina column. Isocratic reverse phase LC at 305 nm is used for quantitation. The average overall recovery at the 0.1, 0.5, and 1.0 ppm spike levels was 83.0% with a standard deviation of 2.04% and a coefficient of variation of 2.46%.