Matthew R. Holman

Polycyclic Aromatic Hydrocarbons in the Mainstream Smoke of Popular U.S. Cigarettes.

The mainstream smoke yields of 14 polycyclic aromatic hydrocarbons (PAHs) were determined for 50 commercial U.S. cigarettes using a validated GC/MS method with the International Organization of Standardization (ISO) and Canadian Intense (CI) smoking machine regimens. PAH mainstream smoke deliveries vary widely among the commercial cigarettes with the ISO smoking regimen primarily because of differing filter ventilation. The more abundant, lower molecular weight PAHs such as naphthalene, fluorene, and phenanthrene predominantly comprise the total PAH yields. In contrast, delivery yields of high molecular weight PAHs such as benzo[b]fluoranthene, benzo[e]pyrene, benzo[k]fluoranthene, and benzo[a]pyrene (BaP) are much lower. Comparative analysis of PAHs deliveries shows brand specific differences. Correlation analysis shows strong positive associations between BaP and most of the other PAHs as well as total PAHs. The results suggest that BaP may be a representative marker for other PAH constituents in cigarette smoke generated from similarly blended tobacco, particularly those PAHs with similar molecular weights and chemical structures.

Menthol Content in US Marketed Cigarettes.

INTRODUCTION In 2011 menthol cigarettes accounted for 32 percent of the market in the United States, but there are few literature reports that provide measured menthol data for commercial cigarettes. To assess current menthol application levels in the US cigarette market, menthol levels in cigarettes labeled or not labeled to contain menthol was determined for a variety of contemporary domestic cigarette products. METHOD We measured the menthol content of 45 whole cigarettes using a validated gas chromatography/mass spectrometry method. RESULTS In 23 cigarette brands labeled as menthol products, the menthol levels of the whole cigarette ranged from 2.9 to 19.6mg/cigarette, with three products having higher levels of menthol relative to the other menthol products. The menthol levels for 22 cigarette products not labeled to contain menthol ranged from 0.002 to 0.07mg/cigarette. The type of packaging (soft vs. hard pack) for a given cigarette product does not appear to affect menthol levels based on the current limited data. CONCLUSIONS Menthol levels in cigarette products labeled as containing menthol are approximately 50- to 5000-fold higher than those in cigarette products not labeled as containing menthol. In general, menthol content appears to occur within discrete ranges for both mentholated and nonmentholated cigarettes. IMPLICATIONS This study shows that menthol may be present in non-mentholated cigarettes and adds to the understanding of how menthol may be used in cigarette products. It is the first systematic study from the same laboratory which will readily enable comparison among menthol and non-menthol cigarettes.

Determination of Aflatoxin B1 in Smokeless Tobacco Products by Use of UHPLC-MS/MS

This work developed a UHPLC-MS/MS method for the detection and quantitation of aflatoxins in smokeless tobacco products, which was then used to determine aflatoxin B1 concentrations in 32 smokeless tobacco products commercially available in the United States. Smokeless tobacco products were dried, milled, and amended with (13)C17-labeled internal standards, extracted in water/methanol solution in the presence of a surfactant, isolated through use of immunoaffinity column chromatography, and reconstituted in mobile phase prior to UHPLC-MS/MS analysis. The method was capable of baseline separation of aflatoxins B1, B2, G1, and G2 in a 2.5 min run by use of a fused core C18 column and a water/methanol gradient. MS/MS transition (m/z) 313.3 → 241.2 was used for aflatoxin B1 quantitation, with 313.3 → 285.1 used for confirmation. The limit of detection (LOD) for aflatoxin B1 was 0.007 parts per billion (ppb). Method imprecision for aflatoxin B1 (expressed as coefficient of variation) ranged from 5.5 to 9.4%. Spike recoveries were 105-111%. Aflatoxin B1 concentrations in the smokeless tobacco products analyzed ranged from <LOD to 0.271 ppb (dry mass). Aflatoxin B1 was most frequently detected in dry snuffs and chews, whereas all moist snuff products tested were below LOD. The amounts of aflatoxin B1 detected were low relative to the 20 ppb regulatory limit established by the U.S. Food and Drug Administration for foods and feeds.

Multivariate Statistical Analysis of Cigarette Design Feature Influence on ISO TNCO Yields

The aim of this study is to explore how differences in cigarette physical design parameters influence tar, nicotine, and carbon monoxide (TNCO) yields in mainstream smoke (MSS) using the International Organization of Standardization (ISO) smoking regimen. Standardized smoking methods were used to evaluate 50 U.S. domestic brand cigarettes and a reference cigarette representing a range of TNCO yields in MSS collected from linear smoking machines using a nonintense smoking regimen. Multivariate statistical methods were used to form clusters of cigarettes based on their ISO TNCO yields and then to explore the relationship between the ISO generated TNCO yields and the nine cigarette physical design parameters between and within each cluster simultaneously. The ISO generated TNCO yields in MSS are 1.1-17.0 mg tar/cigarette, 0.1-2.2 mg nicotine/cigarette, and 1.6-17.3 mg CO/cigarette. Cluster analysis divided the 51 cigarettes into five discrete clusters based on their ISO TNCO yields. No one physical parameter dominated across all clusters. Predicting ISO machine generated TNCO yields based on these nine physical design parameters is complex due to the correlation among and between the nine physical design parameters and TNCO yields. From these analyses, it is estimated that approximately 20% of the variability in the ISO generated TNCO yields comes from other parameters (e.g., filter material, filter type, inclusion of expanded or reconstituted tobacco, and tobacco blend composition, along with differences in tobacco leaf origin and stalk positions and added ingredients). A future article will examine the influence of these physical design parameters on TNCO yields under a Canadian Intense (CI) smoking regimen. Together, these papers will provide a more robust picture of the design features that contribute to TNCO exposure across the range of real world smoking patterns.

The use of charcoal in modified cigarette filters for mainstream smoke carbonyl reduction

&NA; Carbonyls are harmful and potentially harmful constituents (HPHCs) in mainstream cigarette smoke (MSS). Carbonyls, including formaldehyde and acrolein, are carcinogenic or mutagenic in a dose‐dependent manner. Past studies demonstrate significant reduction of HPHCs by charcoal filtration. However, limits of charcoal filtration and cigarette design have not yet been investigated in a systematic manner. Objective data is needed concerning the feasibility of HPHC reduction in combustible filtered cigarettes. This systematic study evaluates the effect of charcoal filtration on carbonyl reduction in MSS. We modified filters of ten popular cigarette products with predetermined quantities (100–400 mg) of charcoal in a plug‐space‐plug configuration. MSS carbonyls, as well as total particulate matter, tar, nicotine, carbon monoxide (TNCO), and draw resistance were quantified. Significant carbonyl reductions were observed across all cigarette products as charcoal loading increased. At the highest charcoal loadings, carbonyls were reduced by nearly 99%. Tar and nicotine decreased modestly (<20%) compared to reductions in carbonyls. Increased draw resistance was significant at only the highest charcoal loadings. This work addresses information gaps in the science base that can inform the evaluation of charcoal filtration as an available technological adaptation to cigarette design which reduces levels of carbonyls in MSS. HighlightsEffect of charcoal load on carbonyl removal from smoke was systematically assessed.100 mg charcoal reduced most carbonyls investigated by between 48% and 95%.300 mg and 400 mg charcoal reduced most carbonyls studied by at least 90%.Modest changes to tar, nicotine, and draw resistance occurred with charcoal filters.Data gathered may inform strategies for exposure reduction.

Development of a Cigarette Tobacco Filler Standard Reference Material

A new tobacco filler Standard Reference Material (SRM) has been issued by the National Institute of Standards and Technology (NIST) in September 2016 with certified and reference mass fraction values for nicotine, N-nitrosonornicotine, 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone, and volatiles. The constituents have been determined by multiple analytical methods with measurements at NIST and at the Centers for Disease Control and Prevention, and with confirmatory measurements by commercial laboratories. This effort highlights the development of the first SRM for reduced nicotine and reduced tobacco-specific nitrosamines with certified values for composition.