The present study evaluated the in vitro extraction of benzo[a]pyrene (BaP) from moist snuff into water and into artificial saliva. A similar, previous study evaluated the levels of BaP that remained in the moist snuff after the extraction but did not measure the levels of BaP in the water or saliva extract. The previous study showed that the remaining levels of BaP in the solid material were between 96.3% and 109.6% relative to the initial level of BaP, when the snuff was washed with water and between 99.4% and 108.3% from the initial level of BaP, when the snuff was washed with both saliva and water. Nine moist snuff samples (eight being the same brands as evaluated in the previous study) were analyzed in the present study. Several improvements were made compared to the previous study regarding the extraction conditions. The extraction was performed for 1 h at 37 °C, using a mechanical agitator.
The previous study used a commercially available artificial saliva which had an adjusted pH but did not contain enzymes or salts. This saliva was replaced with complete artificial saliva containing salts, mucin and enzymes. The results indicated that the level of BaP extracted in 100 mL water from 5 g of moist snuff at 37 °C ranged between 1.0% and 1.7% of the initial level present in tobacco. For artificial saliva, the extracted level of BaP was between 2% and 3.9% from the initial level, depending on the moist snuff brand. Although the BaP level extracted from the moist snuff with artificial saliva remained very low, the surfactant character of artificial saliva increased BaP extraction relative to water by a factor of approximately two. This study supports the previous reported finding that the vast majority of BaP in moist snuff is not extracted in water or artificial saliva. [Beitr. Tabakforsch. Int. 29 (2020) 21–26]
A diffusion denuder apparatus has been used to investigate the gas-particle partitioning of formaldehyde, acetaldehyde, acrolein and crotonaldehyde in cigarette mainstream smoke (MS), compounds that are of interest owing to their toxicity and near quantitative retention in the body during cigarette smoking. Formaldehyde showed the best performance in denuder experiments with simple aldehyde-air mixtures owing to the relatively fast rate of the heterogeneous reaction formaldehyde(g) + dinitrophenylhydrazine(s) 6 hydrazone(s). Analysis with the GORMLEY-KENNEDY equation revealed that formaldehyde denuder removal approached, but did not attain, complete efficiency even under optimized operational conditions. Acetaldehyde, acrolein and crotonaldehyde were trapped with considerably lower efficiency than formaldehyde under the denuder conditions used, and more effective denuder wall coatings would be required to examine gas-particle partitioning of these other carbonyls. The proportion of form-aldehyde in the smoke particulate phase initially entering the denuder was > 99%, but loss of formaldehyde from the smoke particles was relatively rapid leading to 35%–61% deposition over the denuder length. The temperature dependence of formaldehyde deposition in the denuder was well predicted using Henry’s law constant for aqueous formaldehyde solutions. These observed properties of form-aldehyde are primarily due to reversible reactions of formaldehyde with water in cigarette smoke leading to the much less volatile species methanediol, its oligomers and hydrate. These data suggest that cigarette smoke inhalation is likely to expose the deeper-lung generations of smokers to greater relative formaldehyde exposure, and greater genotoxic risk at those generations than might occur through inhalation of formaldehyde vapour alone.
Risk assessments of formaldehyde in cigarette smoke should be updated to recognise this modified risk profile. [Beitr. Tabakforsch. Int. 29 (2020) 2–20]
Background: Combustion as well as pyrolysis of tobacco greatly affect the type and levels of toxicants in cigarette smoke. We previously developed an approach to combine simultaneous temperature and pressure measurements with fast in-situ microprobe chemical sampling inside a burning cigarette, producing a series of temperature and gas-flow velocity maps that characterize this dynamic system in response to externally applied air flow.
Aim: Two cigarette types differing only in diameter were puffed under ISO 3308 and Health Canada Intense (HCI) regimes to further understand the dynamic interaction of air flow and cigarette design parameters on tobacco combustion and pyrolysis by applying the thermophysical and thermo-chemical mapping approach.
Methods: Three types of sampling probes were inserted, which are thermocouple arrays for gas-phase temperature, quartz tubes for pressure measurement, and a heated sampling microprobe coupled to a single-photon soft ionisation mass spectrometer for chemical analysis. Two kinds of similarly constructed cigarettes with the same blend were analysed: superslim (17 mm circumference) and king-size (24 mm circumference).
Synchronization among the sampled signals was achieved by mapping two probes (e.g., temperature/chemistry or temperature/pressure) at a time. The physical and chemical events were visualised and compared between the cigarettes and puffing regimes.
Results: A series of temperature, pressure, and chemical maps were obtained for the superslim and king-size cigarettes under ISO and HCI conditions. The pressure in the burning cigarette was higher in the superslim cigarette, and the temperature distribution differed between the two cigarette formats. As expected, temperatures and pressures were higher under HCI puffing than under ISO puffing for both cigarette formats. Thermochemical maps for e.g., benzene and nitric oxide formation were qualitatively similar between the superslim and king-size cigarettes. For other substances the distribution was markedly different.
Conclusion: The application of multi-probe in-situ chemical sampling is suitable to analyse highly dynamic combustion and pyrolysis processes occurring inside the two types of cigarettes. Ultimately, a direct comparison of cigarette circumferences on the complex combustion processes and formation of smoke constituents was achieved. [Beitr. Tabakforsch. Int. 29 (2020) 44–54]
The thermo-oxidative decomposition of lovage (Levisticum officinale) and davana (Artemisia pallens) essential oils has been studied by pyrolysis-gas chromatography/mass spectrometry in 9% oxygen and 91% nitrogen atmosphere at 300 °C to simulate low-temperature tobacco heating conditions. Both lovage and davana oils contain numerous chemical substances; the main components of both oils are various oxygen-containing compounds. Isobenzofuranones are the most important constituents of lovage oil, and their relative intensity changed significantly during oxidative pyrolysis. (Z)-ligustilide underwent two kinds of decomposition reactions: an aromatization reaction resulting in the formation of butylidenephthalide and the scission of the lactone ring with the elimination of carbon dioxide or carbon monoxide. Davanone is the main component of davana oil, which did not decompose considerably during low-temperature oxidative pyrolysis. However, the relative yield of the second most intensive component, bicyclogermacrene, reduced markedly due to bond rearrangement reactions. Davana ether underwent oxidation reactions leading to the formation of various furanic compounds. The changes in the composition of both essential oils could be interpreted in terms of bond splitting, intramolecular rearrangement mechanisms and oxidation reactions of several constituents during low-temperature oxidative pyrolysis. The applied thermo-oxidative method was found to be suitable to study the stability of the essential oils and monitor the decomposition products under simulated tobacco heating conditions. In spite of the complicated composition of the essential oils, no evidence for interaction between the oil components was found. [Beitr. Tabakforsch. Int. 29 (2020) 27–43]
The differences or equivalence of products depend on various sources of variability like analytical methods, manufacturing processes, agricultural practices and environmental conditions. In addition, the capacity to compare and discriminate accurately two products is impacted by the number of characteristics considered for the comparison. Previously, it has been shown that a comparison of two products can be performed using the critical difference (CD), because it takes into consideration both the variability of measurements and laboratories. However, some additional sources of variability need to be added in the comparison when products were not manufactured at the same period of time or in the same factory. Here, an extended critical difference is proposed including manufacturing process variability according to the number of samples and batches collected for each product. The general formula and specific cases corresponding to different situations (one vs two labs, short vs long periods of time, same vs different periods of time, one vs several batches) are given.
Although 2-nitropropane is a potentially harmful compound present in cigarette smoke, there are few fully-validated, modern methods to quantitate it in mainstream cigarette smoke. We developed an isotope dilution gas chromatography-tandem mass spectrometry (ID-GC-MS/MS) method for the detection of 2-nitropropane in mainstream cigarette smoke. The vapor fraction of mainstream cigarette smoke was collected in inert polyvinyl fluoride gas sampling bags and extracted with hexanes containing isotopically labeled internal standard, then purified and concentrated via solid-phase extraction using a normal phase silica adsorbent and a 100% dichloromethane eluant. This method is sensitive enough to measure vapor phase 2-nitro-propane concentrations in the nanogram range, with a 19 ng per cigarette method limit of detection. Product variability estimated from the analysis of 15 cigarette products yielded relative standard deviations ranging from 5.4% to 15.7%, and estimates of precision from two quality control products yielded relative standard deviations of 9.49% and 14.9%. Under the Health Canada Intense smoking regimen, 2-nitropropane in machine-generated mainstream smoke from 15 cigarette products ranged from 98.3 to 363 ng per cigarette.
Glucose and selected phosphate buffers have been reacted employing systematic variations in reaction temperature and time (150–160 °C for 60–90 min) to optimize the yield of acetol. This mixture was reacted further with NH4OH, systematically varying reaction conditions and reagent ratios to optimize pyrazine yield. The highest yield of pyrazine was obtained when 1 g of glucose was reacted with 25 mL of buffer at 150–160 °C for 60 min, which in turn was reacted with 1 mL of concentrated aqueous NH4OH at 120–130 °C for 17–18 h. Higher temperatures and higher concentrations of glucose caused a decrease in the yield of pyrazines. The addition of hydrolyzed tobacco-derived F1 protein as a secondary source of nitrogen increased the yield of pyrazines by 2–10% depending on F1 protein concentration. Furthermore, the addition of any α-hydroxyketone, similar in structure to acetol, as a pure reagent to the reaction mixture not only increased the yields of pyrazine by ranging from 25–100 % depending on the reagent concentration, but also significantly altered the qualitative and quantitative distribution of the pyrazines. With all of the reaction parameters examined (reaction time, temperature, reagent ratios, etc.) the most significant impacts on both pyrazine yield and distribution were noted when: 1) glucose was pre-reacted with buffer, 2) hydrolyzed F1 protein was added as a second nitrogen source, and 3) when pure α-hydroxyketones were employed as co-reagents. Use of these reaction parameters was found to dramatically shift the pyrazine distribution toward higher molecular weight resulting in a pyrazine array having more desirable physical and sensory attributes.