Gas-liquid chromatographic headspace method for vinyl chloride in vinegars and alcoholic beverages.

Vinyl chloride (VC) is determined in vinegars and alcoholic beverages by gas-liquid chromatographic headspace analysis. The lower limit of detection is 10 ppb and confirmation by gas chromatography-mass spectrometry, single ion monitoring at m/e 62, is possible at this level. Comparison of the headspace and the direct injection methods for the determination of VC in vinegars and alcoholic beverages showed that the results obtained by the 2 methods were not significantly different (P greater than 0.05).     

Rapid gas chromatographic method for determining ethyl carbamate in alcoholic beverages with thermal energy analyzer detection

A rapid column elution method has been developed for the determination of ethyl carbamate (EC) in alcoholic beverages. The beverage is mixed with Celite and packed in a column containing deactivated alumina capped with a layer of sodium sulfate. EC is then eluted with methylene chloride. The method, using a gas chromatograph-thermal energy analyzer with a nitrogen converter for detection and quantitation of EC, has been applied to a variety of alcoholic beverages. Recoveries +/- standard deviations of EC in wine and whisky fortified at the 20 and 133 micrograms/kg (ppb) levels averaged 87.3 +/- 5.3 and 88.7 +/- 3.6%, respectively. The method has a limit of detection of 1.5 ppb. Gas chromatography/mass spectrometry/mass spectrometry was used to confirm the identity and quantitation of EC in selected beverage extracts.     

Development of a method for the quantitation of chloro-, bromo-, and iodoacetic acids in alcoholic beverages

Chloroacetic, bromoacetic, and iodoacetic acids can be found in alcoholic beverages when they are used as preservatives/stabilizers or as disinfectants. As they are toxic components, their addition is not permitted under European Union and U.S. regulations. To date, no sensitive methods are available, and those proposed are very laborious. This paper describes a sensitive and straightforward method for the determination of the three monohalogenated acetic acids (m-HAAs) in wines and beers using static headspace extraction coupled with gas chromatography-mass spectrometry. Prior to extraction, the target analytes were esterified to increase their volatility, and all parameters related to the extraction/methylation process were optimized to achieve high efficiency (>90%). The study examined the influence both of the ethanol concentration on the headspace partitioning and of the primary acids present in wine on the derivatization reaction of the m-HAAs. The proposed method allows the determination of these compounds at microgram per liter levels in alcoholic beverages.     

Automated fluorometric determination of thiabendazole.

An automated fluorometric method is presented for the determination of thiabendazole (2-(4'-thiazolyl)benzimidazole) in 0.1N HCl solutions. Test solutions of at least 1.1 ml starting volume are sampled and pumped successively at the rate of 60/hr into a fluorometer equipped with a simple flowcell. The minimum level of detection of the fungicide is about 0.05 mu-g/ml.     

Determination of ethyl carbamate in distilled alcoholic beverages by gas chromatography with flame ionization or mass spectrometric detection

Quantitative methods are detailed for determination of ethyl carbamate in distilled alcoholic beverages by capillary gas chromatography with flame ionization detection (GC/FID) and by packed-column gas chromatography/mass spectrometry (GC/MS) using selected ion monitoring. Five g samples of distillate of known ethanol concentration are diluted with water to 25% ethanol (v/v), washed with petroleum ether, and extracted with dichloromethane prior to GC/FID or GC/MS analysis. As necessary, sample extracts that exhibit GC/FID interference are passed through alumina for additional cleanup. When internal standards (tert-butyl carbamate and n-butyl carbamate for GC/FID, or ethyl 13C-15N-carbamate for GC/MS) were used for quantitation, the limit of detection for ethyl carbamate was in the range of 5-25 ppb. Coefficients of variation ranged from 3.5 to 6.0% for GC/FID determinations, and from 1.4 to 3.2% for GC/MS. Correlation between methods for 22 random distillate samples ranging in concentration from approximately 40 to 800 ppb gave a correlation coefficient (r) of 0.996.     

Capillary column gas chromatographic determination of ethyl carbamate in alcoholic beverages with confirmation by gas chromatography/mass spectrometry

A method is described for determining ethyl carbamate at low microgram/kg levels in several types of alcoholic beverages by capillary column gas chromatography with Hall electrolytic conductivity detection and confirmation by mass spectrometry. Samples are diluted to obtain a uniform concentration of ethanol (ca 10%) then saturated with NaCl and extracted with methylene chloride. Extracts are evaporated to a small volume and injected in ethyl acetate solution for chromatographic analysis. The method was evaluated by 5 laboratories, 4 employing the Hall detector and one using mass spectrometric detection. Overall between-laboratory mean percent recoveries were: wine, 85.3 +/- 21.0% coefficient of variation (CV) (spiking level 20-45 micrograms/kg); sherry, 83.8 +/- 16.1% CV (spiking level, 81-142 micrograms/kg); whiskey, 79.5 +/- 13.9% CV (spiking level 127-190 micrograms/kg); and brandy, 85.0 +/- 12.5% CV (spiking level 297-446 micrograms/kg). Mass spectrometric results agreed well with the Hall results for all commodities. Detection limits were about 5 micrograms/kg for the Hall detector and about 0.5 microgram/kg for mass spectrometric detection.     

Gas-liquid chromatographic-mass fragmentographic determination of low levels of diethylcarbonate in beverages.

Sodium chloride and ethanol (omitted for samples with greater than 10% alcohol) are added to the beverage sample and the sample is allowed to equilibrate in a 30 degrees C water bath. An aliquot of the headspace is injected into a gas chromatography containing a column packed with 0.2% Carbowax 1500 on 80--100 mesh Carbopack C. During the elution of diethylcarbonate (DEC), an impurity that is present in diethylpyrocarbonate, the column effluent is vented to a mass spectrometer with a multiple ion detection system and operated in the electron impact mode. The ions at m/e 63 and 91 are monitored. Lemonade, fruit drinks, wine, and beer samples (138 total) were analyzed for DEC. Sixteen samples had greater than 30 ppb DEC. Eight analyses of a lemonade sample gave a mean of 88 ppb with a coefficient of variation of 11%.     

Liquid chromatography analysis of erythromycin A in salmon tissue by electrochemical detection with confirmation by electrospray ionization mass spectrometry

A rapid and sensitive method is described for the quantitation of erythromycin A (EA) in edible salmon tissue by liquid chromatography (LC) analysis using either electrochemical detection (ED) or electrospray ionization mass spectrometric (ESI/MS) detection. The salmon tissue is extracted with 10 mM ammonium formate. The extract is then purified by solid phase extraction using a hydrophilic-lipophilic balanced (HLB) polymeric-based C18 packing, followed by partitioning of EA into methylene chloride at alkaline pH, evaporation, and final dilution. The mean recoveries of EA at 50, 100, 200, and 400 ppb levels in fortified salmon tissue were 63.8 +/- 6.0 and 75.5 +/- 5.4% by LC-ED and LC-ESI/MS, respectively. There was no evidence of formation of the anhydro-EA (m/z 716) decomposition product of EA (m/z 734) that was reported to occur by other published methods.     

Analysis of vinyl chloride by mass fragmentography.

Vinyl chloride is analyzed by mass fragmentography by simultaneously recording its m/e 62 and 64 ions. The minimum quantity necessary for detection is 8.7 X 10(-12) g/10 ml injection. At this level the coefficient of variation is 8.51%.     

Determination of cadmium, copper, and lead in sodium chloride food salts by flame atomic absorption spectroscopy

A method for determination of Cd, Cu, and Pb in sodium chloride food salt samples has been developed. It consists of extraction in 4-methyl-2-pentanone of the complexes formed with ammonium pyrrolidine dithiocarbamate and further analysis of the extracts by flame atomic absorption spectroscopy. Detection limits in ng/g salt were 0.2 for Cd, 0.7 for Cu, and 10.0 for Pb. The coefficients of variation of 12 independent analyses were 13% for Cd (at a level of 0.4 ppb), 18% for Cu (1.6 ppb), and 5% for Pb (40 ppb). The recoveries were 100 +/- 0% for Cd, 115 +/- 14% for Cu, and 100 +/- 13% for Pb.     

Determination of benzene in polypropylene food-packaging materials and food-contact paraffin waxes

An analytical procedure was developed for determination of benzene in polypropylene food packaging and was adapted for determination of benzene in commercial paraffin waxes intended for food-contact use. The polymer was dissolved in hexadecane at 150 degrees C. The wax was melted in an 80 degrees C oven. A simple helium-sparging apparatus was used to remove the volatile chemical from the polymer or wax. The contaminant was collected in methanol, distilled water was added, and the resulting solution was analyzed by headspace gas chromatography. The instrument was equipped with a 30 m fused silica open tubular capillary column and a photoionization detector. Average recoveries of benzene from polymer and paraffin wax at low parts-per-billion concentrations were 63 and 70%, respectively. Limits of detection and quantitation for analysis of polypropylene were 8 and 17 ppb, respectively; the limit of quantitation for analysis of paraffin wax was 2 ppb. In several commercial polypropylene products examined, benzene levels ranged from none detected to 426 ppb. In 3 commercial waxes examined, concentrations of 16-73 ppb benzene were determined. The presence of benzene was confirmed by gas chromatography/mass spectrometry.     

Survey results of benzene in soft drinks and other beverages by headspace gas chromatography/mass spectrometry

Benzene, a carcinogen that can cause cancer in humans, may form at nanogram per gram levels in some beverages containing both benzoate salts and ascorbic or erythorbic acids. Through a series of reactions, a hydroxyl radical forms that can decarboxylate benzoate to form benzene. Elevated temperatures and light stimulate these reactions, while sugar and ethylenediaminetetraacetic acid (EDTA) can inhibit them. A headspace gas chromatography/mass spectrometry method for the determination of benzene in beverages was developed and validated. The method was used to conduct a survey of 199 soft drinks and other beverages. The vast majority of beverages sampled contained either no detectable benzene or levels below the U.S. Environmental Protection Agency's drinking water limit of 5 ng/g. Beverages found to contain 5 ng/g benzene or more were reformulated by the manufacturers. The amount of benzene found in the reformulated beverages ranged from none detected to 1.1 ng/g.     

Quantitative fluorodensitometric determination and survey of aflatoxins in nutmeg.

A study is presented for the quantitative fluorodensitometric analysis of aflatoxins in spices, in particular nutmeg (Semen myristicae). Samples were extracted with chloroform, followed by silica gel column cleanup according to the AOAC officail first action method, 26.019(a), and by 2-dimensional thin layer chromatography according to the antidiagonal technique. The method includes a confirmatory test for aflatoxins by hemiacetal formation. The concentrations of aflatoxins in samples were determined by measurement of the fluorescent intensities of the separated aflatoxin spots from sample and standards on the same chromato-plate with a reflectance flying-spot sensitometer. With such a technique, a coefficient of variation value of 5.22 plus or minus 1.24% (P = 99%) was calculated for a series of 5 standard B-1 spots and averaged for 13 TLC plates, demonstrating the precision of the chromatographic and densitometric procedures. An average recovery of 108.4 plus or minus 5.8% (P = 95%) was obtained for 11 spiked nutmeg extracts (5.0-20.0 mu-g B-1 added/kg), whereas an average recovery of 92.6 plus or minus 4.9 (P = 95%) was established for 13 spiked nutmeg samples (5.0-20.0 mu-g B-1 added/kg). The coefficient of variation of the complete analytical procedure for ground nutmeg was 8.80%. In a survey on the occurrence of aflatoxins in 40 commercial nutmeg samples (covering 12 different brands) in The Netherlands, aflatoxins were detected in 30 ground samples (32 ground samples analyzed) in concentrations ranging from 1.0 to 23.2 mu-g B-1/kg or 2.7 to 36.5 mu-g B-1 + B-2 + G-1 + G-2/kg, whereas no aflatoxins were present in whole nutmeg kernels (8 samples analyzed). The lowest level of detection was 1.0 mu-g B-1/kg. In addition, 50 commercial spices consisting of 19 different types of commodities other than nutmeg wer assayed for aflatoxins according to the same procedure. No aflatoxins were detected in these samples, with the exception of 1 sample of bay leaf which contained 5.1 mu-g B-1/kg.     

Multiresidue pesticide analysis of agricultural commodities using acetonitrile salt-out extraction, dispersive solid-phase sample clean-up, and high-performance liquid chromatography-tandem mass spectrometry

A multiresidue method analyzing 209 pesticides in 24 agricultural commodities has been developed and validated using the original Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) procedure and high performance liquid chromatography-positive electrospray ionization-tandem mass spectrometry (LC-MS/MS) analysis. Using solvent-only calibration standards (SOCSs) and matrix-matched calibration standards (MMCSs), it was demonstrated that a minimal concentration of 5-10 μg/kg (part per billion, ppb) of analytes in matrix is required for the consistent identification of targeted pesticides with two MRM transitions. Method performance was validated by the precision and accuracy results obtained from fortification studies at 10, 25, 100, and 500 ppb and MMCSs. The method was demonstrated to achieve an average recovery of 100 ± 20% (n = 4) for >75% of evaluated pesticides at the low fortification level (10 ppb) and improved to >84% at the higher fortification concentrations in all 24 matrices. Matrix effects in LC-MS/MS analysis were studied by evaluating the slope ratios of calibration curves (1.0-100 ng/mL) obtained from the SOCSs and MMCSs. Principal component analysis (PCA) of LC-MS/MS and method validation data confirmed that each matrix exerts its specific effect during the sample preparation and LC-MS/MS analysis. The matrix effect is primarily dependent on the matrix type, pesticide type and concentration. Some caution is warranted when using matrix matched calibration curves for the quantitation of pesticides to alleviate concerns on matrix effects. The QuEChERS method with LC-MS/MS was used to identify and quantitate pesticides residues, with concentrations ranging from 2.5 to >1000 ppb in a variety of agricultural samples, demonstrating fitness for screening and surveillance applications.     

Determining multifumigants in whole grains and legumes, milled and low-fat grain products, spices, citrus fruit, and beverages

Whole grain and legumes, milled and low-fat products, spices, citrus fruit, and dry beverage ingredients are leached with purified, acidified acetone-water solutions. Portions of these leachates are then back-extracted with purified isooctane. Liquid beverages are directly extracted with the isooctane. Six to 10 microL of each isooctane extract is then screened for 11 fumigant residues by gas chromatography (GC) using electron-capture and Hall electroconductivity detectors, and dual 20% OV-101 columns. Further confirmation of residue identity is done on 20% OV-225/20% OV-17 (2.5 + 1 mixed-bed) and 10% SP-1000 columns. The analytes determined include methyl bromide, methylene chloride, carbon disulfide, chloroform, ethylene dichloride, methyl chloroform, carbon tetrachloride, trichloroethylene, chloropicrin, ethylene dibromide, and tetrachloroethylene, using mixed-component reference solutions. Average recoveries from fortified grain range from 25 to 85%; methyl bromide and chloropicrin were recovered the least. Recoveries from the other kinds of food samples range from 43 to 111%. Advantages of this procedure are (1) clean sample extracts, (2) ppb detection limits, (3) residue stability, (4) relative speed, quality control, and safety of the analysis, and (5) results which gave an accurate picture of residual fumigants in grain and food products.     

Chemometric characterization of the cypriot spirit "zivania"

In 42 alcoholic beverages produced in Cyprus and other countries, 26 chemical and physical-chemical variables were determined by HPLC and GC chromatography, (1)H NMR and ICP spectroscopy, and other techniques. Data were processed using multivariate chemometric techniques, involving principal component analysis, cluster analysis, regularized discriminant analysis, and classification and regression trees. Zivania can be differentiated from beverages from other countries. Using 2- and 3-methyl-butanol, 2-methyl-propanol, furfural, methanol, and the alcoholic grade and the chemical shift of -CH(3) in (1)H NMR spectra as features, a nearly correct classification for zivania was achieved. The reasons for diversions are given.     

Ethyl carbamate levels in selected fermented foods and beverages

Ethyl carbamate (EC), also known as urethane, is an animal carcinogen and a by-product of fermentation. Because EC has been found in distilled spirits and wines, a variety of fermented foods and beverages were analyzed to assess its occurrence in other products. Previously described methods using a gas chromatograph-thermal energy analyzer with a nitrogen converter were modified for each matrix and gave recoveries of greater than 80%, with a limit of detection in the 1-2 micrograms/kg (ppb) range. A total of 152 test samples were analyzed; EC levels ranged from none found to 3 ppb in 15 cheeses, 6 teas, 12 yogurts, and 8 ciders; from none found to 13 ppb in 30 breads and 69 malt beverages; and from none found to 84 ppb in 12 soy sauces. Gas chromatography/mass spectrometry/mass spectrometry was used to confirm EC identity and to quantitate EC in selected food extracts.     

Determination of Ni (II) in beverages without any sample pretreatment by adsorptive stripping chronopotentiometry (AdSCP)

The purpose of this paper was to use adsorptive stripping chronopotentiometry for the determination of Ni (II) in worldwide consumed beverages without any sample pretreatment, using dimethilglyoxime (DMG) as complexing agent and a glassy carbon mercury film electrode as the working electrode. Ni (DMG)2 complex is adsorbed onto the mercury film at an electrolysis potential of -500 mV for 60 s and then reduced by a -5 microA constant cathodic current. The sensitivity of the method was studied for certified reference water and black tea in the pH range 6.5-11. At pH 9.5 in ammonia buffer, a detection limit of 0.2 microg L(-1) was achieved; the instrumental precision (expressed as rsd %) was 1.5%, and the accuracy, expressed as obtained recoveries both from certified and not certified matrixes, ranged from 93.0 to 95.5 %. The chronopotentiometric analysis executed on commercial beverages provided evidence that black tea samples were the richest source of Ni (II) (1500-3700 microg L(-1)), followed by coffee (100.0-300.5 microg L(-1)); bottled mineral water showed a Ni (II) concentration lower than 4.6 microg L(-1). Among alcoholic beverages, red wines presented the highest content of Ni (II) (55.5-105.0 microg L(-1)). Significant differences were noticed between Ni (II) levels of fermented and distillated alcoholic beverages; moreover, canned cola and beer did not show higher Ni (II) levels with respect to the glass-bottled products.     

Aloe exudate: characterization by reversed phase HPLC and headspace GC-MS

From the leaves of aloe, a succulent plant, a dried exudate commonly called aloe can be obtained, which is used as a natural drug for its cathartic effect and is widely employed as a bittering agent in alcoholic beverages. This investigation provides a tentative characterization of several commercial aloe exudates carried out both by reversed phase HPLC and by headspace GC-MS analysis. By means of HPLC the derivatives were evaluated, and by GC-MS the volatile fraction was investigated. Qualitative and quantitative differences among the constituents in various samples of different origins were found. In particular, these were evident in the HPLC profile of Kenya aloe and an Aloe barbadensis sample, which exuded a high content of isoaloeresin D and aloins, whereas GC-MS analysis showed the presence of anisole exclusively in Kenya aloe samples. Moreover, the results obtained by means of the latter technique suggested a reason for the prevailing use of Mosselbay and Port Elizabeth aloes in bitter spirits formulation.     

Enzyme-linked immunosorbent assay for deoxynivalenol in corn and wheat

The availability of antibody against deoxynivalenol (DON) triacetate (Tri-Ac-DON) has enabled development of a direct enzyme-linked immunosorbent assay (ELISA) and an indirect ELISA for DON in corn and wheat. In both assays, DON is extracted from the sample with acetonitrile-water, reacted with acetic anhydride to form Tri-Ac-DON, and diluted in phosphate buffer for analysis. Direct ELISA was found to be the more sensitive procedure. Fewer interferences are evidenced, and the assay is less time consuming than is indirect ELISA. For direct ELISA, recovery of 10-1000 ppb DON added to corn and wheat was 100% (SD 15, CV 15%) and 102.1% (SD 12.2, CV 11.9%), respectively. For indirect ELISA, overall recovery of 10-1000 ppb DON added to wheat was 121.5% (SD 39.5, CV 32.5%); in the higher concentration range (500-1000 ppb), recovery was 105% (SD 18, CV 17%). The minimal detection level for DON was around 10 ppb. Analysis of 7 naturally contaminated samples for DON showed that the ELISA results agreed well with those obtained by radioimmunoassay and thin-layer chromatography.