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Journal Details
Format
Journal
eISSN
2719-9509
First Published
01 Jan 1992
Publication timeframe
4 times per year
Languages
English

Search

Volume 29 (2020): Issue 1 (April 2020)

Journal Details
Format
Journal
eISSN
2719-9509
First Published
01 Jan 1992
Publication timeframe
4 times per year
Languages
English

Search

5 Articles
Open Access

Editors’ Note

Published Online: 23 May 2020
Page range: 1 - 1

Abstract

Open Access

Gas-Particle Partitioning of Formaldehyde in Mainstream Cigarette Smoke

Published Online: 23 May 2020
Page range: 2 - 20

Abstract

Summary

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) → 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 formaldehyde 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 formaldehyde 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.

Keywords

  • Mainstream cigarette smoke
  • formaldehyde
  • acetaldehyde
  • acrolein
  • crotonaldehyde
  • nicotine
  • gas-particle partitioning
  • diffusion denuder
  • 2,4-dinitrophenylhydrazine
Open Access

Extraction of Benzo[a]pyrene from Moist Snuff with Water or Artificial Saliva (Part 2)

Published Online: 23 May 2020
Page range: 21 - 26

Abstract

Summary

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.

Keywords

  • Moist snuff
  • benzo[]pyrene
  • BaP
  • extractability
  • artificial saliva
Open Access

Thermo-Oxidative Decomposition of Lovage (Levisticum officinale) and Davana (Artemisia pallens) Essential Oils under Simulated Tobacco Heating Product Conditions

Published Online: 23 May 2020
Page range: 27 - 43

Abstract

Summary

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]

Keywords

  • Flavour
  • lovage oil
  • davana oil
  • gas chromatography/mass spectrometry (GC/MS)
  • oxidative pyrolysis
Open Access

Integration of Time and Spatially Resolved In-Situ Temperature and Pressure Measurements With Soft Ionisation Mass Spectrometry Inside Burning Superslim and King-Size Cigarettes

Published Online: 23 May 2020
Page range: 44 - 54

Abstract

Summary 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]

Keywords

  • Cigarette circumference
  • puff regime
  • combustion and pyrolysis
  • microprobe analysis
  • on-line photo-ionization mass spectrometry
5 Articles
Open Access

Editors’ Note

Published Online: 23 May 2020
Page range: 1 - 1

Abstract

Open Access

Gas-Particle Partitioning of Formaldehyde in Mainstream Cigarette Smoke

Published Online: 23 May 2020
Page range: 2 - 20

Abstract

Summary

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) → 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 formaldehyde 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 formaldehyde 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.

Keywords

  • Mainstream cigarette smoke
  • formaldehyde
  • acetaldehyde
  • acrolein
  • crotonaldehyde
  • nicotine
  • gas-particle partitioning
  • diffusion denuder
  • 2,4-dinitrophenylhydrazine
Open Access

Extraction of Benzo[a]pyrene from Moist Snuff with Water or Artificial Saliva (Part 2)

Published Online: 23 May 2020
Page range: 21 - 26

Abstract

Summary

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.

Keywords

  • Moist snuff
  • benzo[]pyrene
  • BaP
  • extractability
  • artificial saliva
Open Access

Thermo-Oxidative Decomposition of Lovage (Levisticum officinale) and Davana (Artemisia pallens) Essential Oils under Simulated Tobacco Heating Product Conditions

Published Online: 23 May 2020
Page range: 27 - 43

Abstract

Summary

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]

Keywords

  • Flavour
  • lovage oil
  • davana oil
  • gas chromatography/mass spectrometry (GC/MS)
  • oxidative pyrolysis
Open Access

Integration of Time and Spatially Resolved In-Situ Temperature and Pressure Measurements With Soft Ionisation Mass Spectrometry Inside Burning Superslim and King-Size Cigarettes

Published Online: 23 May 2020
Page range: 44 - 54

Abstract

Summary 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]

Keywords

  • Cigarette circumference
  • puff regime
  • combustion and pyrolysis
  • microprobe analysis
  • on-line photo-ionization mass spectrometry

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