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Public health officials and leaders of 168 nations have signaled their concern regarding the health and economic impacts of smoking by becoming signatory parties to the World Health Organization Framework Convention on Tobacco Control (FCTC). One of FCTC's purposes is to help achieve meaningful regulation for tobacco products in order to decrease the exposure to harmful and potentially harmful constituents (HPHCs) delivered to users and those who are exposed to secondhand smoke. Determining baseline delivery ranges for HPHCs in modern commercial tobacco products is crucial information regulators could use to make informed decisions. Establishing mainstream smoke delivery concentration ranges for toxic metals was conducted through analyses of total particulate matter (TPM) collected with smoking machines using standard smoking regimens. We developed a rapid analytical method with microwave digestion of TPM samples obtained with smoking machines using electrostatic precipitation under the ISO and Intense smoking regimens. Digested samples are analyzed for chromium, manganese, cobalt, nickel, arsenic, cadmium and lead using inductively coupled plasma-mass spectrometry. This method provides data obtained using the ISO smoking regimen for comparability with previous studies as well as an Intense smoking regimen that represents deliveries that fall within the range of human exposure levels to toxic metals. [ABSTRACT FROM AUTHOR]

Introduction: Iq'mik, a form of smokeless tobacco (ST), is traditionally used by Cup'ik and Yup'ik Eskimo people of western Alaska. Iq'mik is sometimes incorrectly considered to be a healthier alternative to smoking because its ingredients are perceived as "natural." Our chemical characterization of iq'mik shows that iq'mik is not a safe alternative to smoking or other ST use.Methods: We measured nicotine and pH levels of tobacco and ash used to prepare iq'mik. We also characterized levels of toxins which are known to be present in ST including tobacco-specific nitrosamines (TSNAs) and polycyclic aromatic hydrocarbons (PAHs) using chromatographic separations coupled with isotope dilution mass spectrometry.Results: Nicotine content in the iq'mik tobacco was very high, ranging from 35 to 43 mg/g, with a mean of 39 mg/g. The pH of the iq'mik tobacco-ash mixture was 11, an extremely high level compared with most ST products. High levels of PAHs were seen in the fire-cured tobacco samples with a benzo[a]pyrene level of 87 ng/g. Average TSNA levels in the tobacco were 34, 2,700, and 340 ng/g for 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL), N'-nitrosonornicotine (NNN), and 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), respectively.Conclusions: Iq'mik contains high levels of the more easily absorbed unionized nicotine as well as known carcinogenic TSNAs and PAHs. The perception that iq'mik is less hazardous than other tobacco products due to the use of "natural" ingredients is not warranted. This chemical characterization of iq'mik gives a better understanding of the risk of possible adverse health effects of its use. [ABSTRACT FROM AUTHOR]

Smoking remains the leading cause of preventable death in the United States. There are numerous harmful substances in tobacco and tobacco smoke. Among the more than 4,000 identified compounds in smoke, many metals contribute to the health risks associated with tobacco use. Specific metals found in tobacco and tobacco smoke have been classified as carcinogens by the International Agency for Research on Cancer. Exposure to toxic metals can cause outcomes including inflammation, sensitization and carcinogenesis. Metals in tobacco are transported in tobacco smoke proportionally with their concentrations in tobacco filler for a given cigarette design. To quantitatively examine the metal content in numerous tobacco products, high throughput methods are desired. This study developed a simple, rapid tobacco digestion method coupled with a sensitive analytical method using inductively coupled plasma-mass spectrometry. Because of known memory effects and volatility of mercury, quantitative determinations of mercury were made with a direct combustion analyzer. The methods were utilized to examine arsenic, beryllium, cadmium, chromium, cobalt, lead, manganese, mercury and nickel contents in cigarette tobacco and to establish a reference range for the metals in 50 varieties of cigarettes available in the US. These results are comparable to the limited data sets reported by others and with available standard reference material values. [ABSTRACT FROM AUTHOR]

Nicotine, the psychoactive ingredient in tobacco, is metabolically inactivated by CYP2A6 to cotinine. CYP2A6 also activates procarcinogenic tobacco-specific nitrosamines (TSNA). Genetic variation in CYP2A6 is known to alter smoking quantity and lung cancer risk in heavy smokers. Our objective was to investigate how CYP2A6 activity influences tobacco consumption and procarcinogen levels in light smokers and smokeless tobacco users. Cigarette smokers (n = 141), commercial smokeless tobacco users (n = 73) and iqmik users (n = 20) were recruited in a cross-sectional study of Alaska Native people. The participants’ CYP2A6 activity was measured by both endophenotype and genotype, and their tobacco and procarcinogen exposure biomarker levels were also measured. Smokers, smokeless tobacco users and iqmik users with lower CYP2A6 activity had lower urinary total nicotine equivalents (TNE) and (methylnitrosamino)-1-(3)pyridyl-1-butanol (NNAL) levels (a biomarker of TSNA exposure). Levels of N-nitrosonornicotine (NNN), a TSNA metabolically bioactivated by CYP2A6, were higher in smokers with lower CYP2A6 activities. Light smokers and smokeless tobacco users with lower CYP2A6 activity reduce their tobacco consumption in ways (e.g. inhaling less deeply) that are not reflected by self-report indicators. Tobacco users with lower CYP2A6 activity are exposed to lower procarcinogen levels (lower NNAL levels) and have lower procarcinogen bioactivation (as indicated by the higher urinary NNN levels suggesting reduced clearance), which is consistent with a lower risk of developing smoking-related cancers. This study demonstrates the importance of CYP2A6 in the regulation of tobacco consumption behaviors, procarcinogen exposure and metabolism in both light smokers and smokeless tobacco users. [ABSTRACT FROM PUBLISHER]

Background Modification of tobacco curing methods and other changes in cigarette manufacturing techniques could substantially reduce the levels of tobacco-specific nitrosamines (TSNA), a group of potent carcinogens, in cigarette smoke. In 1999, two major US cigarette manufacturers stated their intent to move towards using tobaccos low in TSNA. There is no information available on current TSNA levels in tobacco of various cigarettes available in the US, particularly in the newer varieties introduced over the past decade. Methods Seventeen brands of cigarettes were purchased in April of 2010 from retail stores in Minnesota. TSNA levels were measured in the tobacco filler and smoke of these cigarettes. Results In all brands, the sum of two potent carcinogenic TSNA - 4-(methylnitrosamino)-1-(3-pyridyl)- 1-butanone and N'-nitrosonornicotine--in cigarette filler averaged 2.54 (±1.05) µg/g tobacco. This value is virtually identical to the sum of these two carcinogens reported for the tobacco of a US filtered cigarette in 1979. TSNA levels in smoke positively correlated with those in tobacco filler of the same cigarettes. Conclusion We found no indication that any meaningful attempt was made to reduce or at least control TSNA levels in the new varieties of the popular brands Marlboro and Camel introduced over the last decade. In light of the recently granted regulatory authority to the FDA over tobacco products, regulation of TSNA levels in cigarette tobacco should be strongly considered to reduce the levels of these potent carcinogens in cigarette smoke. [ABSTRACT FROM AUTHOR]

Objective Oral tobacco products contain nicotine and carcinogenic tobacco-specific N-nitrosamines (TSNAs) that can be absorbed through the oral mucosa. The aim of this study was to determine typical pH ranges and concentrations of total nicotine, unionised nicotine (the most readily absorbed form) and five TSNAs in selected oral tobacco products distributed globally. Methods A total of 53 oral tobacco products from 5 World Health Organisation (WHO) regions were analysed for total nicotine and TSNAs, including 4-(methylnitrosamino)- 1-(3-pyridyl)-1-butanol (NNAL), using gas chromatography or liquid chromatography with mass spectrometric detection. Unionised nicotine concentrations were calculated using product pH and total nicotine concentrations. Fourier transform infrared spectroscopy was used to help categorise or characterise some products. Results Total nicotine content varied from 0.16 to 34.1 mg/g product, whereas, the calculated unionised nicotine ranged from 0.05 to 31.0 mg/g product; a 620-fold range of variation. Products ranged from pH 5.2 to 10.1, which translates to 0.2% to 99.1% of nicotine being in the unionised form. Some products have very high pH and correspondingly high unionised nicotine (eg, gul powder, chimo´, toombak) and/or high TSNA (eg, toombak, zarda, khaini) concentrations. The concentrations of TSNAs spanned five orders of magnitude with concentrations of 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) ranging from 4.5 to 516 000 ng/g product. Conclusions These data have important implications for risk assessment because they show that very different exposure risks may be posed through the use of these chemically diverse oral tobacco products. Because of the wide chemical variation, oral tobacco products should not be categorised together when considering the public health implications of their use. [ABSTRACT FROM AUTHOR]

Introduction: Heterocyclic aromatic amines (HAAs) represent an important class of carcinogens in mainstream cigarette smoke. Accurate HAA quantification is challenging because of their relative low abundances and numerous chemical interferences that arise naturally from thousands of the constituents present in cigarette smoke. We have developed and validated a straightforward high-throughput method to quantify HAA levels in mainstream cigarette smoke and demonstrated the applicability by analyzing select research and domestic cigarette brands. Methods: Machine-smoked cigarette condensate collected under both standard and intensive smoking regimens was examined. Mainstream smoke particulate from individual cigarettes trapped on a glass fiber filter pad was spiked with an appropriate internal standard solution and subsequently solvent extracted. The extract was quantitatively analyzed by high-performance liquid chromatography and tandem mass spectrometry. Results: Method validation data showed excellent accuracy, reproducibility and high throughput; it is suitable for the routine analysis of HAAs in cigarette smoke condensate delivered under a wide of differing smoking conditions. The smoking machine deliveries of HAAs are strongly influenced by cigarettes’ physical design, filler blend, and smoking regimen. Conclusions: A quick and accurate method has been developed for the analysis of 6 HAAs in mainstream cigarette smoke condensate. Results provided a good mean to access the ranges of HAAs in commercial products and evaluate the relative contribution of cigarette design, filler blend, and smoking regimen on delivery. Such data are vital in helping provide exposure ranges for potential human exposure estimates. [ABSTRACT FROM AUTHOR]

Objectives To investigate how the tobacco industry is adapting to regulatory action in accordance with provisions of the Framework Convention on Tobacco Control that targets misleading packaging and labelling. To relate the packaging and labelling of new cigarette varieties to their construction and performance. Methods The principal design features and tar, nicotine and carbon monoxide yields of the Marlboro 'brand family' in Australia were measured and compared with those of the US equivalents. Results Marlboro Red and Blue/Medium, could not be differentiated in preliminary tests in Australia, but were different in the USA. However, yield testing showed Marlboro Blue/Medium did not have lower tar and nicotine yields in either country, indeed being higher in Australia. Conclusions Colour can be used to market cigarettes as 'milder', independently of ISO yields and 'Light'/'Mild' descriptors. Banning of 'Light' and 'Mild' brand descriptors may be inadequate to end belief in less harmful cigarettes so long as the tobacco industry remains free to engineer 'mildness' and to use colours, other descriptors and design features to characterise varieties it wants to market as 'milder'. [ABSTRACT FROM AUTHOR]

Introduction:: Standardized machine smoking measurements are poor predictors of exposure. We have refined a method using the solanesol deposited in discarded cigarette butts as a marker for estimating deliveries of mainstream smoke constituents. Developing a fast and accurate method for measuring solanesol in cigarette filters to assess tobacco smoke intake could provide a way to assess how people smoke under natural conditions. We have developed and validated a new, lower-cost, high-throughput method to measure the solanesol content in discarded cigarette filter butts and correlated these measurements with mainstream smoke deliveries of nicotine and tobacco-specific nitrosamines (TSNAs). [ABSTRACT FROM PUBLISHER]

In 2005, approximately 2.3% of U.S. adults used smokeless tobacco. Moist snuff leads all types of smokeless tobacco in revenues and marketing expenditures. The U.S. Surgeon General has concluded that smokeless tobacco use can lead to nicotine addiction. The National Toxicology Program of the National Institutes of Health has classified smokeless tobacco as a human carcinogen. Tobacco-specific nitrosamines (TSNAs) are potent carcinogens in smokeless tobacco products, and the pH of the product influences the content of un-ionized nicotine which is the form of nicotine most rapidly absorbed in the mouth. The Centers for Disease Control and Prevention analyzed 40 top-selling brands of moist snuff to measure nicotine, moisture, pH, un-ionized nicotine, and TSNAs, including 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL). The study findings indicate that moist snuff brands varied widely in content of rapidly absorbed, addictive un-ionized nicotine (500-fold range) and of carcinogenic TSNAs (18-fold range). Product characteristics such as packaging and moisture content appeared to be correlated with concentrations of un-ionized nicotine, and flavor characteristics of low-priced brands may correlate with TSNA concentrations. These findings warrant further study in light of (a) the marketing of smokeless tobacco for use in places where smoking is prohibited, (b) the promotion of smokeless tobacco as a harm-reduction product, and (c) the ever-expanding number of highly flavored smokeless varieties brought to the market. [ABSTRACT FROM AUTHOR]

Exposure to hydroxyl-substituted arenes, commonly referred to as phenols or phenolic compounds, can have serious health consequences. Select phenols present in tobacco smoke are cardiovascular toxins, act as tumor copromoters and show genotoxic activity. To examine the mainstream smoke levels of these compounds, we developed and applied a method for quantitative analysis of seven phenols (phenol, o-cresol, m-cresol, p-cresol, catechol, resorcinol, and hydroquinone) in mainstream smoke. Total mainstream smoke particulate matter was collected on a Cambridge filter pad and spiked with an isotopically labeled internal standard solution. This pad underwent an automated phenol derivatization procedure to increase analyte volatility and enhance detection. Following the derivatization step, phenols from the particulate matter were sampled using solid-phase microextraction with subsequent gas chromatography/mass spectrometric detection. Sensitivity, selectivity, accuracy, and reproducibility were more than adequate for routine detection of phenols in mainstream smoke. Detection limits ranged from 0.04-0.57 μg, with a quantification range of 0.1-710 μg. Higher sensitivity and sample throughput were achieved compared with previously described methods. Mainstream smoke from 28 brands of domestic commercial cigarettes was evaluated to assess typical levels, and reference cigarettes containing single tobacco blends were examined to ascertain the phenolic profile from different types of tobaccos. As expected under machine smoking conditions using the Federal Trade Commission parameters, full-flavored cigarettes deliver more phenols than the light varieties, followed by the ultra light varieties. Differences were seen in relative levels of phenolic compounds in the mainstream smoke from unfiltered cigarettes made with a single type of tobacco. [ABSTRACT FROM AUTHOR]

Tobacco‐specific nitrosamines (TSNAs) comprise one of the major classes of carcinogenic compounds in mainstream cigarette smoke. As part of collaborative efforts between the World Health Organization and the U.S. Centers for Disease Control and Prevention (CDC) to reduce tobacco use and resulting disease, the CDC examined carcinogenic TSNA levels from cigarettes obtained from selected countries around the world. Using a modern, high‐throughput liquid chromatography/mass spectrometry/mass spectrometry method under stringent quality control protocols, we determined the carcinogenic TSNA levels in mainstream smoke from a globally marketed brand, Marlboro, and from local top‐selling cigarette brands from 14 countries. The levels of carcinogenic TSNAs in mainstream smoke collected using a 35‐ml puff volume, 60‐s puff interval, and 2‐s puff duration correlated well ( R = 0.79, p <.0001) with previously reported levels in the corresponding tobacco filler. Marlboro cigarettes purchased in 10 countries had significantly higher carcinogenic TSNA levels in mainstream smoke than did local‐brand cigarettes from the same country. In only one country, Brazil, were the carcinogenic TSNA levels in mainstream smoke from Marlboro cigarettes significantly lower than in the locally popular brand. However, carcinogenic TSNA levels in mainstream smoke from Brazilian Marlboro cigarettes were usually lower than those in mainstream smoke from the Marlboros purchased in the other 13 countries, suggesting a reason for the difference. The wide range of mainstream smoke carcinogenic TSNA levels measured in the present study (8.7–312&ThickSpace;ng/cigarette) suggest that manufacturers can lower the carcinogenic TSNA levels and that, for similar filter ventilation, carcinogenic TSNA levels in the tobacco filler of a cigarette are a useful indicator of the corresponding levels in mainstream smoke. [ABSTRACT FROM AUTHOR]

A survey of the nicotine, tar, and carbon monoxide (CO) levels in mainstream smoke from 21 brands of bidi cigarettes and five brands of traditional cigarettes was conducted using a variation of the Federal Trade Commission (FTC) standardized cigarette smoking machine method. The primary difference between this method and the FTC method was a reduction of the 60-s puff interval to 15 s. The shorter puff interval was required to prevent the bidi cigarettes from self-extinguishing and may represent a closer approximation to human usage. The goal of this study was to evaluate the smoke-delivery potential for tar, nicotine, and CO in mainstream smoke from bidi cigarettes compared with traditional domestic cigarettes smoked under identical conditions. Approximately half of the bidi brands examined were marketed as filtered varieties. Unlike traditional cigarettes, the filtered and unfiltered bidi brands yielded comparable smoke deliveries. Thus, a filtered bidi cigarette brand does not provide any harm-reduction benefit that might result from a reduction in levels of tar, nicotine, and CO compared with an unfiltered variety. Our findings indicate that bidi cigarettes can deliver high levels of tar (77.9+/-9.5 mg/bidi), nicotine (2.7+/-.4 mg/bidi), and CO (39.2+/-5.7 mg/bidi). In comparison, traditional cigarettes smoked using the bidi cigarette protocol have lower tar and CO yields, but have nicotine deliveries comparable with bidi cigarettes. [ABSTRACT FROM AUTHOR]

Research gaps exist in toxic metals characterization in e-cigarette, or vaping, products (EVPs) as these analytes typically have low concentrations and most standard aerosol trapping techniques have high metals background. An additional complication arises from differences in the EVP liquid formulations with nicotine products having polar properties and non-nicotine products often being non-polar. Differences in polar and non-polar matrices and the subsequent aerosol chemistries from various EVPs required modifications of our previously reported nicotine-based EVP aerosol method. Validation and application of the expanded method, suitable for both hydrophobic and hydrophilic aerosols, are reported here. The metals analyzed for this study were Al, Cr, Fe, Co, Ni, Cu, Cd, Sn, Ba, and Pb. The method limits of detection for the modified method ranged from 0.120 ng/10 puffs for Cd to 29.3 ng/10 puffs for Al and were higher than reported for the previous method. Results of the analyses for metals in aerosols obtained from 50 EVP products are reported. Cannabinoid based EVP aerosols were below reportable levels, except for one sample with 16.08 ng/10 puffs for Cu. Nicotine-based EVP results ranged from 6.72 ng/10 puffs for Pb to 203 ng/10 puffs for Sn. Results of the analyses for these metals showed that aerosols from only 5 of the 50 devices tested had detectable metal concentrations. Concentrations of toxic elements in the aerosols for nicotine-based EVP aerosol metal concentration ranges were consistent with previously published results of aerosol analyses from this class of devices. [ABSTRACT FROM AUTHOR]

Three novel collisionally induced dissociation pathways, additional to the usual formation of pyridine or pyridinium cation, are described for laser-desorbed N-substituted pyridinium cations. Particularly prevalent is the formation of an ion of m/ z 94, corresponding to [PyCH3]+. Doubly charged pyridiniums tend to lose H+, and one example of the apparent formation of the neutral radical C5H6N˙ is reported. [ABSTRACT FROM AUTHOR]

Solanesol, a naturally occurring constituent of tobacco, has been utilized as a good marker for environmental tobacco smoke particulate and as a noninvasive predictor of mainstream cigarette smoke tar and nicotine intake under naturalistic smoking conditions. A fast and accurate method for measuring free solanesol to assess tobacco smoke exposure is highly desirable. We have developed and validated a new environmentally friendly, high-throughput method for measuring solanesol content in discarded cigarette filter butts. The solanesol deposited in the used filters can be correlated with mainstream smoke deliveries of nicotine and total particle matter to estimate constituent delivery to smokers. A portion of filter material is removed from cigarette butts after machine smoking, spiked with internal standard solution, extracted and quantitatively analyzed using reverse-phase liquid chromatography coupled to a triple-quadrupole mass spectrometer. The new method incorporates a 48-well plate format for automated sample preparation that reduces sample preparation time and solvent use and increases sample throughput 10-fold compared to our previous method. Accuracy and precision were evaluated by spiking known amounts of solanesol on both clean and smoked cigarette butts. Recoveries exceeded 93% at both low and high spiking levels. Linear solanesol calibration curves ranged from 1.9 to 367 µg/butt with a 0.05 µg/butt limit of detection. [ABSTRACT FROM AUTHOR]