In support of the efforts to combat smuggling, as well as illegal sale and distribution of cigarettes, an analytical approach for the characterization of tobacco has been proposed and evaluated. It involves aqueous extraction of the filler tobaccos followed by direct analysis of the extracts by electrospray ionization-ion trap mass spectrometry (ESI-ITMS) in the negative mode. Typically, the deprotonated ions, [M - H](-), of organic acids (malic, citric, caffeic, quinic acid) and polyphenols (chlorogenic acid, rutin, scopoletin) were detected. MS/MS spectra of the ion at m/z 191, which is the [M - H](-) of quinic acid, citric acid, and scopoletin, and a fragment ion of chlorogenic acid were acquired. Significant differences in the MS and MS/MS spectra were observed between counterfeit samples and the corresponding authentic brand name cigarettes. Analysis of 25 commercial cigarettes showed that straight Virginia blends were readily distinguished from the blended products containing different tobacco types (Virginia, burley, and Oriental). The former exhibited consistently higher relative abundances of m/z 353 (chlorogenic acid) to m/z 133 (malic acid) in the MS spectra (0.9-1.2 vs 0.4-0.6) and higher intensity ratios of m/z 176 (scopoletin) to m/z 173 (0.4-0.8 vs 0.1-0.3) and of m/z 127 (quinic acid) to m/z 173 (0.7-1.0 vs 0.3-0.5) in the MS/MS spectra. Evidence is presented to demonstrate that the spectral differences were related not only to the tobacco type (Virginia, burley and Oriental) but also to the tobacco part (stem, lamina) used in the manufacture of the cigarettes.

A reliable method based on gas chromatographic/mass spectrometric (GC/MS) profiling of nonvolatile organic acids is described for the characterization of cigars. The method involves an aqueous extraction of ground tobacco and selective isolation of the acids by simply stirring strong anion exchange (SAX) disks in the aqueous tobacco extract. The acids are then directly silylated on the disk with N-methyl-N-trimethylsilyl-trifluroacetamide (MSTFA) in acetonitrile in an autosampler vial. Elution of the derivatized acids in situ allows the sample to be directly analyzed by GC/MS without further sample handling. Compared to the conventional disk-extraction technique using a vacuum manifold, this method is much less labor intensive, and is desirable for multiple sample analysis. Nicotinic acid, succinic acid, glyceric acid, malic acid, pyroglutamic acid, threonic acid, citric acid, uracil, and an unidentified acid were reproducibly quantified in tobacco samples. Principal component analysis (PCA) of the acid profiles of the filler tobaccos of 18 Cuban cigars and 31 non-Cuban cigars shows separation of the two groups, indicating that the acid profiles are potentially useful in the authentication of Cuban cigars.

A reliable method for measuring (15)N/(14)N and (2)H/(1)H ratios of nicotine in cigarette tobacco has been developed. It involves a simple procedure for extracting nicotine from tobacco using methanol. The extract is directly analyzed on a gas chromatography isotope ratio mass spectrometer (GC-IRMS). The method is reproducible with 4% RSD for delta(2)H and delta(15)N. Brand name cigarettes manufactured in Canada (N = 47) and in China (N = 23) have been analyzed. The results show that nicotine from Canadian cigarettes has a higher (2)H/(1)H ratio and a lower (15)N/(14)N ratio than the Chinese cigarettes. The delta(2)H values for Canadian cigarettes range from -232.7 per thousand to -203.4 per thousand with an average of -222.1 per thousand; the delta(2)H values for Chinese cigarettes range from -262.6 per thousand to -219.9 per thousand with an average of -243.8 per thousand. The delta(15)N values for Canadian cigarettes range from -7.7 per thousand to -6.3 per thousand with an average of -7.1 per thousand; the delta(15)N values for Chinese cigarettes range from -7.6 per thousand to -5.7 per thousand with an average of -6.3 per thousand. The combined measurements of (2)H/(1)H and (15)N/(14)N have been shown to be useful in identifying counterfeits of Canadian cigarettes analyzed in this study.

The use of membranes in order to lower the methanol content in a 1% methanol in pentane solution and in a mixture of 9% tertiary amyl methyl ether or methyl tertiary butyl ether, 12% methanol, 16% 2-methy1-2-butene and 62% pentane has been studied. Different commercial films were tested (Glad Wrap® , Saran Wrap®, Handi-Wrap® , Stretch'n Seal® , and No Name® brand) as well as inhouse fabricated cellulose acetate and cellulose acetate butyrate membranes. All the commercial films give a permeate depleted in methanol as opposed to the in-house ones which enrich the permeate in methanol. This work has identified the most promising membranes, however, a study using continuous flow type cells would show the real capacity of these membranes.