Dorcas Weber

Analysis of Canadian and imported beers for Fusarium mycotoxins by gas chromatography—mass spectrometry

A sensitive method was developed for the determination of deoxynivalenol (DON), nivalenol (NIV), alpha-zearalenol (alpha-ZEL), beta-zearalenol (beta-ZEL) and zearalenone (ZEN) in beer by capillary gas chromatography-mass spectrometry (GC-MS) of their heptafluorobutyrate (HFB) derivatives. Recoveries averaging 90-103% were obtained from beers spiked with each mycotoxin in the 5-20 ng/ml concentration range. Limits of detection were 0.1-1.5 ng DON/ml, 0.01-0.3 ng NIV/ml, 2.5-3 ng alpha- and beta-ZEL/ml, and 1.5-2 ng ZEN/ml. Twenty-nine of 50 samples of Canadian and imported beer surveyed were found to contain DON; of these nine contained greater than 5 ng/ml (up to 50 ng/ml). The identity of DON was confirmed by response ratios at m/z 670 and m/z 884 for the HFB derivative and m/z 497 and m/z 512 for the trimethylsilyl (TMS) derivative. NIV was also detected in three beer samples (0.1-0.84 ng/ml) but no alpha-ZEL, beta-ZEL or ZEN was found.

Levels of chlorinated hydrocarbon residues in Canadian human breast milk and their relationship to some characteristics of the donors

A total of 412 breast milk samples from women in all provinces of Canada were analysed for polychlorinated biphenyls, eight chlorinated benzenes, 2,3-dichloronaphthalene, Mirex, alpha, beta, gamma and delta hexachlorocyclohexane, alpha and gamma chlordane, oxychlordane, transnonachlor, p,p-DDT and some analogues, heptachlor epoxide, dieldrin and octachlorostyrene. No delta-hexachlorocyclohexane, heptachlor or aldrin were found in any of the samples, while median levels of the 1,2,4- and 1,3,5-trichlorobenzene, 1,2,3,4- and 1,2,3,5-tetrachlorobenzenes, gamma chlordane, o,p-DDT and octachlorostyrene were all less than the minimum detectable level (MDL). All other compounds were present at median levels ranging from < 0.1 to 7.2 ng/g whole milk, but did not occur in all samples. Di to tetrachlorobenzenes, except 1,2,4-trichlorobenzene, 2,3-dichloronaphthalene and alpha-chlordane were observed in < 50% of the samples. From 1967 to 1986 a steady decline of hexachlorobenzene, gamma-hexachlorocyclohexane, DDTs, heptachlor epoxide and dieldrin was observed in Canadian breast milk. In addition, a decrease in some chlorinated benzenes, gamma-hexachlorocyclohexane and PCBs was also observed between 1982 and 1986. Levels of oxychlordane and trans-nonachlor remained constant. Canadian breast milk contamination appears to be one of the lowest among the industrialized nations. Regional and provincial differences in residue levels appeared minimal, although more often samples from Quebec and British Columbia had higher levels of some contaminants, such as oxychlordane, than samples from other provinces. No relationship was found between maternal age and residue levels, but some contaminants, such as PCBs, were significantly higher in the milk of mothers who breastfed their first child as compared to multiparous mothers. Breast milk residue levels were not related to fish consumption.

Determination of butyltin, cyclohexyltin and phenyltin compounds in beers and wines

Butyl- cyclohexyl- and phenyltin compounds were extracted from enzymically-hydrolysed wine and beer samples with 0.05% tropolone in pentane. Methyl derivatives were made by Grignard reaction for determination by gas chromatography-atomic absorption spectrometry. Wine and beer samples contained less than 0.1 to 160 nl/ml of butyltins from an undetermined source of contamination. GC-MS confirmation of butyltins also detected phenyltin, and di- and tricyclohexyltin compounds at levels less than the GC-AAS based method detection limits of 0.05-0.13 ng Sn/mL.

Application of capillary gas chromatography to a survey of wheat for five trichothecenes

A previously published method for the determination of deoxynivalenol (DON) and nivalenol (NIV) in grains by capillary gas chromatography (GC) with electron-capture detection (ECD) has been modified to include HT-2 toxin (HT-2), T-2 toxin (T-2) and diacetoxyscirpenol (DAS). Recoveries of the five trichothecenes from wheat averaged 71-92% in the range 0.8-4 micrograms/g. Detection or quantitation limits found in two laboratories were from 0.02 to 0.4 micrograms/g, with those for T-2 and DAS at the high end of this range. The method proved of practical use in survey work for the screening and determination of these trichothecenes in wheat from the 1987 western Canadian crop. There were no false positives for HT-2, T-2 and DON in durum and HY-320 wheat. However, interferences precluded the determination of 4- and 15-monoacetoxyscirpenol (MAS) by GC-ECD. The natural occurrence of HT-2 toxin (0.06-0.59 micrograms/g) was demonstrated by GC-ECD and confirmed by GC-mass spectrometry (MS) in 23 samples of durum and HY-320 wheats (1986 and 1987 crops); it was almost always accompanied by DON and in one sample a low concentration of NIV (0-05 micrograms/g). False positives for HT-2 and DAS in red spring wheat detected in 1987 by GC-ECD were 6% (nearly all identified as variety Katepwa) and 8%, respectively. Hence confirmation of suspected HT-2 and DAS by GC-MS is necessary, particularly with red spring wheat.

Non-orthochlorine substituted coplanar polychlorinated biphenyl congeners in canadian adipose tissue, breast milk and fatty foods

Abstract Nine fatty food composites together with one human milk and one human adipose tissue sample were analyzed for the 3,4,3′,4′-tetrachloro-, 3,4,5,3′,4′-pentachloro-, and 3,4,5,3′,4′,5′-hexachlorobiphenyl congeners. Levels of these non-orthochlorine substituted coplanar polychlorinated biphenyls ranged from

The Routine Analysis of Some Specific Isomers of Polychlorinated Biphenyl Congeners in Human Milk

A mixture of 14 polychlorinated biphenyl (PCB) isomers of various congeners, representing approximately 70% of all human milk PCBs reported in the literature, was made up to identify and approximate their residues in human milk. Individual isomer levels varied from 5 to 103 nanograms per gram of milkfat with the 2,2,4,4,5,5-hexachlorobiphenyl isomer as the major PCB contaminant of human milk. PCB isomer numbers 74, 118, 153, 138 and 180 made up approximately 75% of all PCBs as measured by this mixture. There was close agreement of total PCB isomer content in breast milk between electron capture gas chromatography and gas chromatographic mass spectrometry determinations. A major interference was encountered however for PCB isomer no. 52, whose residue level in the breast milk was approximately 3 X higher by gas liquid chromatography than by mass spectrometry.

Gas chromatographic—mass spectrometric determination of ethyl carbamate in alcoholic beverages

A sensitive and specific method based on gas chromatography-mass spectrometry for the quantitative determination of ethyl carbamate in table wines, fortified wines (such as ports and sherries), distilled spirits, brandies and liqueurs has been developed. Three characteristic ions from ethyl carbamate [m/z 89 (molecular ion), 74 and 62] were monitored in the selected-ion monitoring (SIM) mode. The lowest detection limit (based on the response on the m/z 62 ion) was estimated to be 0.5 ng/g (ppb). Additional confirmation techniques, including high-resolution SIM, and methane or isobutane chemical ionization are described.

Specimc polychlorinated biphenyl congener distribution in breast milk of Canadian women

Abstract A total of 412 breast milk samples from across Canada were analyzed for selected polychlorinated biphenyl congeners. The median level for those congeners present in more than 80% of the samples ranged from 0.11–0.87 ng/g whole milk. Of these the most predominant (>5% of total polychlorinated biphenyls) congeners were: the 2,4,4’,5‐tetra‐, 2,2’,4,4’,5‐ and 2,3’,4,45‐penta‐, 2,2’,3,4,4’,5‐ and 2,2’,4,4’,5,5‐ hexa‐ and 2,2’,3,4,4’,5,5‐ heptachlorobiphenyls. Two percent of the congeners were non‐ortho‐, 33% mono‐ortho‐ and 66% di‐orthochlorine substituted biphenyls. Compared to the 14 congeners measured in a 1982 study, all but one (2,3’,4,4‐tetra‐chlorobiphenyl) showed a decrease in residue level, with a more than‐ 50% decline for most of the predominant congeners. In addition the polychlorinated biphenyl congeners levels in this study were comparable to or lower than those reported in breast milk studies from other countries. Regional and/or provincial differences in residue levels for polychl...

A method for the determination of methyl carbamate and ethyl carbamate in wines

A method is described for the simultaneous determination of methyl carbamate (MC) and ethyl carbamate (EC) in wines that is based on: (a) extraction of the sample with dichloromethane using an extraction tube or an alumina-Celite column, (b) concentration of the extract to a small volume, and (c) determination by gas-liquid chromatography-thermal energy analyser (N-mode). The method is highly sensitive (1-2 ng/ml), accurate (recoveries greater than 80%), and precise (CV, 5-10%). Nineteen of 27 samples of wines analysed contained traces (up to 2.7 ng/ml) of MC, and most contained EC (up to 70 ng/ml). Wines treated in the laboratory with 200 ppm dimethyl pyrocarbonate (DMPC)-a cold sterilant recently approved for use in wines-indicated that such a treatment may increase the MC contents of the wines to 10 ng/ml. Additional studies suggested that formation of MC in DMPC-treated wines is dependent on both pH and ammonia content of the wines. The identity of MC in a few selected samples was confirmed by gas-liquid chromatography-high resolution (10 K) mass spectrometry. The natural low levels of MC found in these wines are not considered to pose a risk to human health.

Analytical methods for the determination and mass spectrometric confirmation of 1‐methyl‐2‐nitroso‐1,2,3,4‐tetrahydro‐β‐carboline‐3‐carboxylic acid and 2‐nitroso‐1,2,3,4‐tetrahydro‐β‐carboline‐3‐carboxylic acid in foods

A method is described for the determination of the two title compounds that is based on: (a) extraction of the acidified sample with methanol, (b) removal of fats and lipids by partitioning of the extract with n-hexane, (c) clean-up on acidic alumina extraction cartridge, and (d) determination by a post-HPLC column chemical denitrosation-thermal energy analyser (TEA) technique or by conventional HPLC-TEA analysis after derivatization of the compounds with diazomethane. Confirmation was carried out by HPLC-mass spectrometry of the free acids and also by gas chromatography-mass spectrometry of the methyl esters. The formation of both 1-methyl-2-nitroso-1,2,3,4-tetrahydro-beta-carboline-3-carboxylic acid and 2-nitroso-1,2,3,4-tetrahydro-beta-carboline-3-carboxylic acid in nitrosated samples of several Japanese and Chinese pickled vegetables, one soy sauce, and two cheeses was demonstrated.