Statistically designed survey of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and co-planar polychlorinated biphenyls in U. S. meat and poultry, 2002-2003: results, trends, and implications.

To obtain information on dioxin levels in the human diet, the Food Safety and Inspection Service of the United States Department of Agriculture recently determined levels of dioxin-like compounds (dioxins/dibenzofurans/PCBs) in four major slaughter classes (steers and heifers, market hogs, young chickens, and young turkeys) that comprise over 90% of the meat and poultry production in the United States. The data were analyzed and compared to data from smaller surveys carried out from 1994 to 1996. These surveys were conducted by different laboratories nearly 10 years apart, so a direct comparison of the data was not straightforward.

Levels of polychlorinated dibenzo-p-dioxins and dibenzofurans in cattle raised at agricultural research facilities across the USA and the influence of pentachlorophenol-treated wood.

Adipose tissue samples from 158 cattle raised locally at experiment stations across the USA were analysed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F). While 80% of the samples had PCDD/F concentrations that fell within the range of a previous US survey of beef animals (not detected -4.1 ppt toxic equivalency), several animals had exceptionally high concentrations (8-54 ppt toxic equivalency).

Treated wood in livestock facilities: relationships among residues of pentachlorophenol, dioxins, and furans in wood and beef.

Wood and other environmental samples were collected from sites that produced beef with higher than average residues of dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF). Analyses of these samples for PCDD/Fs and pentachlorophenol (PCP) indicated that the high beef residues were associated with PCP-treated wood in the animal facilities. Concentrations of PCDD/Fs in wood as toxic equivalents ranged from 10 to 320,000 pg/g.

Chlorinated dibenzo-p-dioxin and dibenzofuran concentrations in beef animals from a feeding study.

Four calves were fed polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans for 120 days at levels somewhat higher than what may be found in forage near some waste incinerators and manufacturing plants. Four calves were fed identical diets but without the chemicals. Using bioelectrical impedance measurements of total body fat, 30-50% of the dosed 2,3,7,8-TCDD, 1,2,3,7,8-PeCDD, and 2,3,4,7,8-PeCDF was estimated to be retained by the animals.

An investigation of the in vivo formation of octachlorodibenzo-p-dioxin.

The in vivo formation of dioxins from chemical precursors was investigated in rats. Sprague-Dawley rats were fed pentachlorophenol or a predioxin in peanut oil for 14 days. Mass balance calculations indicated that pentachlorophenol was not converted to dioxins; however, the predioxin, nonachloro-2-phenoxyphenol, was converted to OCDD.

Depletion of residues from milk and blood of cows dosed orally and intravenously with sulfamethazine.

Cows were dosed orally (n = 4) or intravenously (n = 4) with sulfamethazine [sulmet; 4-amino-N-(4,6-dimethyl-2-pyrimidinyl)benzenesulfonamide] for 5 consecutive days (220 mg/kg of body weight on day 1 and 110 mg/kg on days 2-5). The concentrations of sulmet, N4-acetylsulfamethazine (Ac-sulmet), and the N4-lactose conjugate of sulfamethazine (lac-sulmet) were measured in milk and blood collected at 24 h intervals after the last doses of sulmet were given. The method of analysis included (1) spiking of samples with known amounts of 13C6-labeled reference compounds, (2) resolution of the 3 compounds by reversed-phase chromatography, (3) hydrolysis of lacsulmet, (4) treatment with diazomethane to yield N1-methyl derivatives, and (5) gas chromatography/mass spectrometry.

Isotope dilution assay for urinary methanesulfinic and methanesulfonic acids: application to detection of methylthio turnover.

Methanesulfinic and methanesulfonic acids were shown to be present in urine from rats fed laboratory rat diet. The daily excretions of each acid were equivalent at 0.47 mumol day-1.

Steady state kinetics of 14C-sulfamethazine [4-amino-N-(4,6-dimethyl-2-pyrimidinyl)benzene[U-14C]sulfonamide] metabolism in swine.

Swine were dosed orally with 14C-sulfamethazine [4-amino-N-(4, 6-dimethyl-2-pyrimidinyl)benzene[U-14C]sulfonamide] for 3, 5, or 7 days (two 165-mg doses/day; 0.46 muCi/mg) and killed 8 hr after the last dose. The concentration of carbon-14 in the tissues increased by an average of 21% from day 3 to day 5 of dosing.

Identification and quantitation of sulfamethazine metabolites by liquid chromatography and gas chromatography-mass spectrometry.

Methods for the identification and quantitation of carbon-14 labeled sulfamethazine [4-amino-N-(4,6-dimethyl-2-pyrimidinyl)benzenesulfonamide], N4-acetylsulfamethazine, the N4-glucose conjugate of sulfamethazine, and desaminosulfamethazine in swine tissue are described. Tissues are ground and extracted with methanol, and the 14C-labeled compounds are purified by XAD-2 column chromatography and C-18 reverse phase liquid chromatography (LC) and the 14C-labeled compounds are then methylated and identified by gas chromatography-mass spectrometry analysis. Quantitation is accomplished by measuring the amount of 14C-activity that cochromatographs (C-18 reverse phase LC) with reference compounds.

Mass spectra of aniline glucuronides.

Mass spectra of TMS derivatives of aniline glucuronide and pentachloroaniline glucuronide are presented, and the fragmentation of these derivatives is compared with that of TMS aryl-O-glucuronides. Fragmentation yielding ions entirely from the glycone moiety was sufficiently similar to establish these N-glucuronides as TMS glucuronides in the same manner used for TMS-O-glucuronides; however, differences observed may be diagnostic for TMS-N-glucuronides.

Mass spectral characterization of the glucuronide conjugates of crufomate (4-t-butyl-2-chlorophenyl methyl methylphosphoramidate) metabolites.

Seven sheep metabolites of crufomate (4-t-butyl-2-chlorophenyl methyl methylphosphoramidate) were characterized as glucuronide conjugates by interpretation of mass spectral data obtained from ths of the methyl esters.

Synthesis and mass spectrometry of crufomate metabolites and related compounds.

Phosphates and phosphoramidates related to 2-chloro-4-t-butylphenyl methyl methylphosphoramidate (crufomate) were synthesized to aid in the identification of crufomate metabolites. Deuterium labeling metastable determinations and precise mass measurements were used to establish fragmentation pathways. Evidence was obtained for the rearrangement of an N-formyl phosphoramidate (the expected result of oxidative metabolism of N-methyl phosphoramidates) to an iminomethyl phosphate.

Metabolism of [4C]crufomate (4-t-butyl-2-chlorophenyl methyl methylphosphoramidate) by the sheep.

Twenty-five metabolites were isolated from the urine, feces or plasma of sheep given single oral doses of [14C]crufomate (4-t-butyl-2-chlorophenyl methyl methylphosphoramidate). These metabolites resulted from one or more of the following transformations: oxidatin of a methyl group in the t-butyl moiety to yield either an alcohol or a carboxylic acid; hydrolysis of the phosphate and phosphate and phosphoramidate bonds; oxidatin of the N-methyl group to yield N-formyl phosphoramidates; methylation of the N-formyl group to yield N-methyl-N-formyl phosphoramidates; oxidative N-demethylation; conjugation with glucuronic acid. No ring-hydroxylation of dechlorination was observed, and no crufonate was isolated from the urine, feces or plasma.

Mirex in the environment: its degradation to kepone and related compounds.

The chlorocarbon mirex undergoes slow, successive loss of chlorine in the field to a series of related compounds that had lost one or more chlorine atoms. Soil samples were recovered 12 years after treatment at 1 part per million (ppm), and ant bait was recovered 5 years after an aircraft crash. As much as 50 percent of the original mirex was recovered at levels of about 0.

Mass spectra of methyl-branched hydrocarbons from eggs of the tobacco hornworm.

Hydrocarbons from three homologous series of branched alkanes from the eggs of the tobacco hornworm, Manduca sexta (L.), were identified by mass spectrometry. Gas-liquid chromatography (GLC) peaks 37-A (equivalent chain length of 37.