Assisted distillation cleanup of pesticide residues in animal fats: new beadless distillation tube

A new assisted distillation tube has been developed which contains no glass beads or glass wool. The sample is injected into the top of the tube, and a septum is not required. Large ground-glass joints (10/19) are used at the gas inlet and at the Florisil trap connection for maximum strength. Existing assisted distillation apparatus was easily modified to accept the new tubes. Recoveries of 9 organochlorine pesticides from butter and cattle fat ranged from 87 to 104% at a tube temperature of 230 degrees C and a nitrogen flow rate of 250 mL/min. No significant change occurred in recoveries of 8 of the 9 pesticides after 85 uses of the beadless tube. Only the recovery of HCB from butter decreased, from 95 to 80%, after 51 runs. The new tube was compared with the Unitrex glass bead-packed concentric tube at flow rates of 230, 400, and 600 mL nitrogen/min. Recoveries from the Unitrex tube were similar to those of the beadless tube for all pesticides except DDT which was significantly lower, indicating incomplete distillation at 250 mL/min and possible partial breakdown at 400 and 600 mL/min. A procedure is introduced for pressurized solvent washing of distillation tubes. This procedure is more efficient than vacuum washing.     

Determination of procaine and related local anesthetics. I. Partition chromatographic separation and assay of mixtures of procaine with tetracaine and with propoxycaine.

Determination of ionization and extraction constants for procaine, tetracaine, and propoxycaine led to selection of a simple partition chromatographic system for separation and assay of mixtures of these anesthetics. A 65% solution of chloroform in isooctane elutes tetracaine or propoxycaine from a pH 4:sodium bromide column; procaine is retained and subsequently eluted by chloroform as the bromide ion-pair. The anesthetics are then determined spectrophotometrically. Results of assay of standard and commercial formulations are presented.     

High-speed liquid chromatographic determination of phenothiazine in commercial pesticide formulations.

Phenothiazine (thiodiphenylamine) in commercial pesticide formulations is analyzed by high-speed liquid chromatography and ultraviolet absorption detection. Phenothiazine is extracted from the formulation with methanol and injected into the liquid chromatograph. Methanol-water (1+1) is the mobile phase. The amount of phenothiazine is calculated from peak height ratios. The liquid chromatographic procedure is much faster than the infrared or colorimetric method and yields values in close agreement with both of these methods.     

State programs for pesticide residues in foods

Two U.S. data collection and dissemination programs, FEEDCON and FOODCONTAM, are described. FEEDCON provides information on contamination levels in animal feeds of toxic chemical residues (pesticides, industrial chemicals, heavy metals, mycotoxins, natural plant toxins, salmonella, and therapeutic drug cross-contaminations). FEEDCON data are collected from approximately 40 state feed regulatory agencies, feed manufacturers, and related groups who subscribe ($100-$200 per year) to the program, which is sponsored by the Association of American Feed Control Officials. FOODCONTAM provides similar information, but is limited to pesticides, heavy metals and industrial chemicals (polychlorinated and polybrominated biphenyls, etc.) in human foods. Both programs have been developed and initiated under U.S. Food and Drug Administration contracts with the Mississippi State Chemical Laboratory. Program structures of both are outlined conceptually, and FOODCONTAM is described in detail. FOODCONTAM data-sharing program development is essentially complete, but expansion by incorporating FDA data with State Laboratory data is nearing reality.     

Organochlorine pesticide residues in strawberries from integrated pest management and organic farming

A rapid, specific, and sensitive method based on the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) method and a cleanup using dispersive solid-phase extraction with MgSO(4), PSA, and C18 sorbents has been developed for the routine analysis of 14 pesticides in strawberries. The analyses were performed by three different analytical methodologies: gas chromatography (GC) with electron capture detection (ECD), mass spectrometry (MS), and tandem mass spectrometry (MS/MS). The recoveries for all the pesticides studied were from 46 to 128%, with relative standard deviation of <15% in the concentration range of 0.005-0.250 mg/kg. The limit of detection (LOD) for all compounds met maximum residue limits (MRL) accepted in Portugal for organochlorine pesticides (OCP). A survey study of strawberries produced in Portugal in the years 2009-2010 obtained from organic farming (OF) and integrated pest management (IPM) was developed. Lindane and β-endosulfan were detected above the MRL in OF and IPM. Other OCP (aldrin, o,p'-DDT and their metabolites, and methoxychlor) were found below the MRL. The OCP residues detected decreased from 2009 to 2010. The QuEChERS method was successfully applied to the analysis of strawberry samples.     

Recent advances in cleanup of fats by sweep co-distillation. Part 2. Organophosphorus residues

This paper describes the isolation of 5 organophosphorus residues in beef fat by a commercial sweep co-distillation unit (Unitrex). The operating conditions specified 223 degrees C and nitrogen flow at 230 mL/min. Recoveries of chlorpyriphos, monodechlorchlorpyriphos, bromophos-ethyl, debromobromophos-ethyl, and ethion ranged from 84 to 99%, with coefficients of variation between 3 and 5%.     

High-speed liquid chromatographic determination of o-phenylphenol residues in citrus products.

A method is presented for the quantitative analysis of o-phenylphenol residues in citrus oils, encapsulated flavors, and dried meal. The method utilizes high-speed liquid chromatography for the determination after specific sample preparations for each material. These preparations include hexane extraction of acidified basic extracts or steam distillation and extraction. The limit of the analysis is less than 1 ppm with an analysis time of less than 45 min.     

Evaluation of the studies on decline of pesticide residues

A specifically designed field trial was carried out in an apple orchard by applying Reldan 50 EC (active ingredient, chlorpyrifos-methyl) according to registered uses in Hungary to study the variability of results derived from supervised field trials. Two types of composite samples (A, size 24; and C, size 12) were taken at days 0, 3, 7, 10, and 14 after application to study the uncertainty of estimated residue values derived from supervised trials. In the case of type A the sampling officer selected the fruits from the specified quadrant of the tree, whereas for type C the fruits were taken from the vicinity of the marked position at consecutive sampling times. An evaluation model applying various formulas for the linearization of the decline curves of pesticide residues was applied, which enabled using the statistics of linear regression for calculating the best fit and confidence intervals for the experimental data. The results indicated that the uncertainty of sampling contributed approximately 84-90% of the combined uncertainty of the results (24-30%). In the decline studies performed simultaneously on the same field, the estimated time required to decrease the initial concentration to half ranged from 0.64 to 4.7 days. Despite the fact that the sample size of type C is half that of type A, both sampling methods provided similar results.     

Capillary gas chromatographic separation of various stimulants

A capillary gas chromatographic (GC) method was developed for the separation of various stimulants of forensic and pharmaceutical interest. The data consist of retention time, relative retention time, corrected retention time, and relative corrected retention time, calculated using ephedrine as reference standard.     

Organophosphorus pesticide residues in Mexican commercial pasteurized milk

A study was conducted to measure residues of 13 organophosphorus (OP) pesticides, widely used as dairy cattle ectoparasiticides or in crops used for animal feed, in homogenized and pasteurized Mexican milk samples. Four different milk brands with high distribution were collected biweekly during a 12 month period (n = 96) in supermarkets. OP pesticide residues were measured by gas chromatography with a flame photometric detector. Approximately 39.6% of the samples contained detectable levels of OP pesticide residues. Eight samples contained residues exceeding established maximum residue limits (MRL), and the OP pesticides present in these samples were dichlorvos (five samples), phorate, chlorpyrifos, and chlorfenvinphos (one sample, respectively). Average residues of 13 OP pesticides measured were below established MRLs ranging between 0.0051 and 0.0203 ppm.     

Determination of chlorinated pesticide residues in foods. II. Simultaneous analysis of chlorinated pesticide and phthalate ester residues by using AgNO3-coated Florisil column chromatography for cleanup of various samples.

A simplified method suitable for simultaneous analysis of chlorinated pesticide and phthalate ester residues in various foods was developed. Chemical residues were quantitatively extracted from fatty and vegetable samples with acetonitrile as follows: Chemical standard in 0.5 mL ethanol solution was added to 10 g homogenized sample. After 3 hr, pork and beef were extracted 3 times with 20 mL portions of acetonitrile. The acetonitrile layers were diluted with water and extracted with n-hexane. Rice samples were combined with 10 mL water, 5 mL acetonitrile and 1 mL ethanol and extracted 3 times with 20 mL portions of n-hexane. The n-hexane concentrate from each sample was submitted to AgNO3-coated Florisil column chromatography. The AgNO3 coating adequately adsorbed interfering coextractives. Extracts of fish and vegetable samples were separated into 2 fractions by the above column chromatography. Supplemental cleanup procedures were also developed to accurately determine phthalate esters eluted in the second fraction. Satisfactory gas chromatograms were obtained for most samples.     

Analysis of pesticide residues by chemical derivatization. II. N-methylcarbamates in natural water and soils.

A method for the quantitative determination of several N-methylcarbamates in natural waters and the applicability of the derivative to soil samples using a previously published extraction procedure are described. After extraction of the carbamates from the substrate, the carbamates are hydrolyzed in a 10% methanol-potassium hydroxide solution to form the phenolic hydrolysis products, which are isolated and derivatized with pentafluorobenzyl (PFB) bromide to produce the PFB ether derivatives. The PFB derivatives are cleaned up and fractionated on a silica gel microcolumn and determined by electron capture gas-liquid chromatography (GLC). Eight organophosphate pesticides and 2 phthalate acid esters that hydrolyze to phenols or phthalic acid were evaluated as potential interferences and were found not to interfere with any of the carbamates tested. Quantitative determinations of 0.1 mug carbofuran and 3-ketocarbofuran and 0.5 mug carbaryl, metmercapturon, and Mobam in a 1 L water sample are possible. Propoxur was not determined at levels less than 1 mug/L due to the short GLC retention time of the derivative and interferences from the reagents at the lower levels.     

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).     

Gas chromatographic determination of fenpropimorph residues in citrus fruit

A rapid gas chromatographic method for determining fenpropimorph residues in citrus fruit is reported. The fungicide is extracted with hexane after pH adjustment of the fruit homogenate. A short liquid-liquid partitioning process is performed before gas chromatography on an OV-17 column with nitrogen-phosphorus specific detection. The limit of detection of the method was 0.01 mg/kg, based on a 25 g sample. Recovery was always higher than 70%. Fenpropimorph residues in "Washington Navel" oranges and "Hernandina" clementine fruits dipped in a 1500 mg/L fungicide solution were determined. The fungicide remains mainly in the peel, with levels less than 0.1 mg/kg in the pulp. Fungicide residues in the peel decrease during storage, mainly in Washington Navel peel, where values decreased from 5.2 to 2.8 mg/kg.     

Liquid chromatographic determination of tetracycline residues in animal feeds

A liquid chromatographic method for the multiresidue determination of tetracyclines (TCs) in feeds is described. The levels of quantitation were 10 ppm each for tetracycline-HCl (TC), oxytetracycline (OTC), and chlortetracycline-HCl (CTC); the detection limit was 40 ppb for each. The calibration curves were linear between 2.5 and 100 ppm. The procedure involved double extraction with pH 2.0 and pH 4.5 McIlvain buffers, cleanup on a Sephadex LH-20 column, separation on a Nova-Pak C18 column, and detection at 370 nm. Recoveries of 10 micrograms/g of each TC in multiresidue feed samples ranged from 55.8 to 75.5% for OTC, 71.6 to 100% for TC, and 22.4 to 60.6% for CTC. The identities of the TCs were confirmed by thin layer chromatography.     

State findings on pesticide residues in food--1988 and 1989

Findings of pesticide and related chemical residues are presented for 27,065 samples of foods collected and analyzed in 10 state food laboratories over 1988 and 1989 (fiscal years (FY) 88 and 89). These laboratories conduct food regulatory programs compatible with national programs of the U.S. Food and Drug Administration. Of the findings, 6325 samples contained detectable levels of 1 or more pesticide analytes and 418 (or 1.5%) of the total number of samples were deemed to be of regulatory significance.     

Gas-liquid chromatographic determination of kepone residues in finfish, shellfish, and crustaceans.

Finfish, shellfish, and crustacean samples are extracted with isopropanol and benzene; the extract is filtered and then concentrated. The extract, dissolved in hexane, is treated with oleum and extracted with aqueous alkali. The aqueous phase is acidified and extracted with petroleum ether-ethyl ether (1 + 1). The Kepone residue is determined by electron capture gas-liquid chromatography (GLC). Recoveries obtained by 8 laboratories from 15 species of finfish fortified at 0.02-0.23 ppm ranged from 37 to 107% with a mean +/- relative standard deviation of 79.4 +/- 14.5%. For oysters fortified at 0.01-0.10 ppm, recoveries range from 63 to 129% with a mean of 78.8 +/- 20.8%. For crustaceans fortified at 0.05-0.26 ppm, recoveries ranged from 52 to 110% with a mean of 78 +/- 16.4%. The approximate limits of quantitation for finfish and for shellfish and crustaceans are 0.02 and 0.05 ppm, respectively, under the GLC conditions used in this study.     

Disappearance of organochlorine residues from abdominal and egg fats of chickens, Ontario, Canada, 1969-1982

Abdominal fats were collected from 8-week old broilers slaughtered at provincially inspected abattoirs across Ontario between 1969 and 1982. Domestically produced hen eggs were collected from either egg grading stations or producers over the same period. Composite samples were analyzed for organochlorine insecticides and industrial chemicals. Between 1979 and 1982, organophosphorus insecticides were routinely included in these analyses. Sigma DDT and PCB residues declined rapidly between 1969 and 1982 in extractable lipids of both abdominal and egg fats, while dieldrin declined less markedly over the same period. Declines in residues followed first order logarithmic regression equations. Chlordane and heptachlor epoxide were rarely observed above the detection limit of 1 microgram/kg in egg fat; however, the incidence of these residues in abdominal fat increased after 1973 following the removal of aldrin, dieldrin, and heptachlor in 1969 and the subsequent increased use of chlordane for soil insect control until 1977. Lindane residues were rarely observed above the detection limit. In 1979, when the detection limit was reduced, both alpha-BHC and lindane were identified, but at levels below 1 microgram/kg. Endosulfan, methoxychlor, and fenthion were identified on one or 2 occasions over the 13-year period.     

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.