ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Figure 1Loading Img
ADDITION / CORRECTIONThis article has been corrected. View the notice.

Conversion of Nicotine in Tobacco Smoke to Its Volatile and Available Free-Base Form through the Action of Gaseous Ammonia

View Author Information
Department of Environmental Science and Engineering, Oregon Graduate Institute, P.O. Box 91000, Portland, Oregon 97291-1000
Cite this: Environ. Sci. Technol. 1997, 31, 8, 2428–2433
Publication Date (Web):July 30, 1997
https://doi.org/10.1021/es970402f
Copyright © 1997 American Chemical Society

    Article Views

    1053

    Altmetric

    -

    Citations

    LEARN ABOUT THESE METRICS
    Other access options

    Abstract

    Ammonia-forming compounds are routinely added to cigarette tobacco. The U.S. Food and Drug Administration (FDA) has argued that this is done to promote the formation of the volatile free-base form of nicotine in mainstream smoke (MSS) particles, thus increasing its availability to the smoker. The presence of ammonia in tobacco smoke may also be expected to promote the volatilization of nicotine from environmental tobacco smoke (ETS) particles in indoor air. The gas/particle partitioning of nicotine can be parameterized in terms of the gas/particle partitioning constant Kp = cp/cg, where cp (ng/μg) is the concentration in the particle phase and cg (ng/m3) is the concentration in the gas phase. The ability of ammonia to increase the amount of nicotine in the gas phase, as compared to the particle phase, was measured and confirmed. A gas-phase am monia pressure of pNH3 of ∼100 × 10-6 atm (100 ppmV) was found to reduce the Kp value for the partitioning of nicotine to tobacco smoke particulate matter by more than 100-fold. The agreement between ETS and MSS at pNH3 ≈ 100 ppmV was excellent, suggesting that the overall physical properties (e.g., polarity and number-average molecular weight) of ETS and MSS particulate material are very similar. Because gas-phase nicotine deposits more readily in the respiratory tract than does particle-phase nicotine and because free-base nicotine is more lipid soluble than is protonated nicotine, such a reduction in Kp will increase the availability of nicotine from MSS as well as from freshly formed ETS particles. At 20 °C and a relative humidity of 60%, the partitioning constant for the free-base form of nicotine is estimated to be Kp,fb = cp,fb/cg = 10-4.94. Cor rection to a body temperature of 37 °C yields Kp,fb = 10-5.97. Calculations using this Kp,fb value indicate that about 25% of the nicotine will be in the gas phase at a temperature of 37 °C for inhaled MSS under the full ammonia effect at a total suspended smoke particulate matter level of 3 × 106 μg/m3.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    *

     To whom all correspondence should be addressed. Fax:  503-690-1556. E-mail:  [email protected].

     Abstract published in Advance ACS Abstracts, July 15, 1997.

    Cited By

    This article is cited by 61 publications.

    1. Leanne E. Mocniak, Neil Trushin, Zachary T. Bitzer, Prital Prabhu, John P. Richie. Tobacco Nitrate and Free Radical Levels in the Mainstream Smoke of US Cigarette Brands. Chemical Research in Toxicology 2023, 36 (4) , 653-659. https://doi.org/10.1021/acs.chemrestox.2c00355
    2. Jinlu Wu, Yihan Gao, Dian Li, Naiping Gao. Emission and Gas/Particle Partitioning Characteristics of Nicotine in Aerosols for Electronic Cigarettes. Chemical Research in Toxicology 2022, 35 (5) , 890-897. https://doi.org/10.1021/acs.chemrestox.2c00076
    3. James F. Pankow, Wentai Luo, Kevin J. McWhirter, Christopher S. Motti, Clifford H. Watson. Measurement of the Free-Base Nicotine Fraction (αfb) in Electronic Cigarette Liquids by Headspace Solid-Phase Microextraction. Chemical Research in Toxicology 2021, 34 (10) , 2227-2233. https://doi.org/10.1021/acs.chemrestox.1c00285
    4. James F. Pankow, Anna K. Duell, David H. Peyton. Free-Base Nicotine Fraction αfb in Non-Aqueous versus Aqueous Solutions: Electronic Cigarette Fluids Without versus With Dilution with Water. Chemical Research in Toxicology 2020, 33 (7) , 1729-1735. https://doi.org/10.1021/acs.chemrestox.0c00008
    5. James F. Pankow, Kilsun Kim, Wentai Luo, Kevin J. McWhirter. Gas/Particle Partitioning Constants of Nicotine, Selected Toxicants, and Flavor Chemicals in Solutions of 50/50 Propylene Glycol/Glycerol As Used in Electronic Cigarettes. Chemical Research in Toxicology 2018, 31 (9) , 985-990. https://doi.org/10.1021/acs.chemrestox.8b00178
    6. Peyton Jacob, III, Neal L. Benowitz, Hugo Destaillats, Lara Gundel, Bo Hang, Manuela Martins-Green, Georg E. Matt, Penelope J. E. Quintana, Jonathan M. Samet, Suzaynn F. Schick, Prue Talbot, Noel J. Aquilina, Melbourne F. Hovell, Jian-Hua Mao, and Todd P. Whitehead . Thirdhand Smoke: New Evidence, Challenges, and Future Directions. Chemical Research in Toxicology 2017, 30 (1) , 270-294. https://doi.org/10.1021/acs.chemrestox.6b00343
    7. Peyton Jacob, III, Maciej L. Goniewicz, Christopher M. Havel, Suzaynn F. Schick, and Neal L. Benowitz . Nicotelline: A Proposed Biomarker and Environmental Tracer for Particulate Matter Derived from Tobacco Smoke. Chemical Research in Toxicology 2013, 26 (11) , 1615-1631. https://doi.org/10.1021/tx400094y
    8. Cai Chen and James F. Pankow. Gas/Particle Partitioning of Two Acid−Base Active Compounds in Mainstream Tobacco Smoke: Nicotine and Ammonia. Journal of Agricultural and Food Chemistry 2009, 57 (7) , 2678-2690. https://doi.org/10.1021/jf803018x
    9. Maneerat Ongwandee and Glenn C. Morrison. Influence of Ammonia and Carbon Dioxide on the Sorption of a Basic Organic Pollutant to Carpet and Latex-Painted Gypsum Board. Environmental Science & Technology 2008, 42 (15) , 5415-5420. https://doi.org/10.1021/es071935j
    10. Jeffrey I. Seeman. Possible Role of Ammonia on the Deposition, Retention, and Absorption of Nicotine in Humans while Smoking†. Chemical Research in Toxicology 2007, 20 (3) , 326-343. https://doi.org/10.1021/tx600290v
    11. Clifford H. Watson,, Jenna S. Trommel, and, David L. Ashley. Solid-Phase Microextraction-Based Approach To Determine Free-Base Nicotine in Trapped Mainstream Cigarette Smoke Total Particulate Matter. Journal of Agricultural and Food Chemistry 2004, 52 (24) , 7240-7245. https://doi.org/10.1021/jf049455o
    12. Jeffrey I. Seeman,, Peter J. Lipowicz,, Jean-Jacques Piadé,, Laurent Poget,, Edward B. Sanders,, James P. Snyder, and, Clarence G. Trowbridge. On the Deposition of Volatiles and Semivolatiles from Cigarette Smoke Aerosols:  Relative Rates of Transfer of Nicotine and Ammonia from Particles to the Gas Phase. Chemical Research in Toxicology 2004, 17 (8) , 1020-1037. https://doi.org/10.1021/tx0300333
    13. Jeffrey I. Seeman,, Jay A Fournier,, John B. Paine III, and, Bruce E. Waymack. The Form of Nicotine in Tobacco. Thermal Transfer of Nicotine and Nicotine Acid Salts to Nicotine in the Gas Phase. Journal of Agricultural and Food Chemistry 1999, 47 (12) , 5133-5145. https://doi.org/10.1021/jf990409b
    14. Phongphot Sakulaue, Kulpavee Jitapunkul, Parinya Inthasuwan, Hiromu Takano, Takafumi Ishii, Kanokwan Kongpatpanich, Kajornsak Faungnawakij, Metta Chareonpanich, Khanin Nueangnoraj. Insight into the effects of different oxygen heteroatoms on nicotine adsorption from cigarette mainstream smoke. Scientific Reports 2023, 13 (1) https://doi.org/10.1038/s41598-023-42188-w
    15. Henry J. Colby, Erin F. Katz, Peter F. DeCarlo. Volatilization and partitioning of residual electronic cigarette emissions to particulate matter. Aerosol Science and Technology 2023, 57 (6) , 508-516. https://doi.org/10.1080/02786826.2023.2191669
    16. Takumi Yamamoto, Yoshika Sekine, Koki Sohara, Satoshi Nakai, Yukio Yanagisawa. Effect of Heating Temperature on Ammonia Emission in the Mainstream Aerosols from Heated Tobacco Products. Toxics 2022, 10 (10) , 592. https://doi.org/10.3390/toxics10100592
    17. Natalie L. Johnson, Theresa Patten, Minghong Ma, Mariella De Biasi, Daniel W. Wesson. Chemosensory Contributions of E-Cigarette Additives on Nicotine Use. Frontiers in Neuroscience 2022, 16 https://doi.org/10.3389/fnins.2022.893587
    18. Kristen Yeh, Li Li, Frank Wania, Jonathan P.D. Abbatt. Thirdhand smoke from tobacco, e-cigarettes, cannabis, methamphetamine and cocaine: Partitioning, reactive fate, and human exposure in indoor environments. Environment International 2022, 160 , 107063. https://doi.org/10.1016/j.envint.2021.107063
    19. Lehua Lu, Menghui Xiang, Haoran Lu, Zhixin Tian, Yihan Gao. Progress in quantification of nicotine content and form distribution in electronic cigarette liquids and aerosols. Analytical Methods 2022, 14 (4) , 359-377. https://doi.org/10.1039/D1AY01679B
    20. Frank T. Leone, Sarah Evers-Casey. Tobacco Use Disorder. Medical Clinics of North America 2022, 106 (1) , 99-112. https://doi.org/10.1016/j.mcna.2021.08.011
    21. Marc W. Beutel, Thomas C. Harmon, Thomas E. Novotny, Jeremiah Mock, Michelle E. Gilmore, Stephen C. Hart, Samuel Traina, Srimanti Duttagupta, Andrew Brooks, Christopher L. Jerde, Eunha Hoh, Laurie C. Van De Werfhorst, Van Butsic, Ariani C. Wartenberg, Patricia A. Holden. A Review of Environmental Pollution from the Use and Disposal of Cigarettes and Electronic Cigarettes: Contaminants, Sources, and Impacts. Sustainability 2021, 13 (23) , 12994. https://doi.org/10.3390/su132312994
    22. Ahmad Besaratinia. From Tobacco Cigarettes to Electronic Cigarettes: The Two Sides of a Nicotine Coin. Frontiers in Oral Health 2021, 2 https://doi.org/10.3389/froh.2021.790634
    23. Marija Banožić, Krunoslav Aladić, Igor Jerković, Stela Jokić. Volatile organic compounds of tobacco leaves versus waste (scrap, dust, and midrib): extraction and optimization. Journal of the Science of Food and Agriculture 2021, 101 (5) , 1822-1832. https://doi.org/10.1002/jsfa.10796
    24. Theresa Patten, Mariella De Biasi. History repeats itself: Role of characterizing flavors on nicotine use and abuse. Neuropharmacology 2020, 177 , 108162. https://doi.org/10.1016/j.neuropharm.2020.108162
    25. William W Nazaroff, Charles J. Weschler. Indoor acids and bases. Indoor Air 2020, 30 (4) , 559-644. https://doi.org/10.1111/ina.12670
    26. Rola Salman, Soha Talih, Rachel El-Hage, Christina Haddad, Nareg Karaoghlanian, Ahmad El-Hellani, Najat A Saliba, Alan Shihadeh. Free-Base and Total Nicotine, Reactive Oxygen Species, and Carbonyl Emissions From IQOS, a Heated Tobacco Product. Nicotine & Tobacco Research 2019, 21 (9) , 1285-1288. https://doi.org/10.1093/ntr/nty235
    27. Gideon St.Helen, Marian Shahid, Sherman Chu, Neal L. Benowitz. Impact of e-liquid flavors on e-cigarette vaping behavior. Drug and Alcohol Dependence 2018, 189 , 42-48. https://doi.org/10.1016/j.drugalcdep.2018.04.032
    28. Gideon St.Helen, Delia A. Dempsey, Christopher M. Havel, Peyton Jacob, Neal L. Benowitz. Impact of e-liquid flavors on nicotine intake and pharmacology of e-cigarettes. Drug and Alcohol Dependence 2017, 178 , 391-398. https://doi.org/10.1016/j.drugalcdep.2017.05.042
    29. Todd Pagano, A. Gary DiFrancesco, Susan B. Smith, Jerrin George, Gloria Wink, Irfan Rahman, Risa J. Robinson. Determination of Nicotine Content and Delivery in Disposable Electronic Cigarettes Available in the United States by Gas Chromatography-Mass Spectrometry. Nicotine & Tobacco Research 2016, 18 (5) , 700-707. https://doi.org/10.1093/ntr/ntv120
    30. Alena Celsie, J. Mark Parnis, Donald Mackay. Impact of temperature, pH, and salinity changes on the physico-chemical properties of model naphthenic acids. Chemosphere 2016, 146 , 40-50. https://doi.org/10.1016/j.chemosphere.2015.11.122
    31. Donald Mackay, Alena K.D. Celsie, J. Mark Parnis. The evolution and future of environmental partition coefficients. Environmental Reviews 2016, 24 (1) , 101-113. https://doi.org/10.1139/er-2015-0059
    32. James F. Pankow. Phase considerations in the gas/particle partitioning of organic amines in the atmosphere. Atmospheric Environment 2015, 122 , 448-453. https://doi.org/10.1016/j.atmosenv.2015.09.056
    33. Angelo Cecinato, Paola Romagnoli, Mattia Perilli, Claudia Patriarca, Catia Balducci. Psychotropic substances in indoor environments. Environment International 2014, 71 , 88-93. https://doi.org/10.1016/j.envint.2014.06.008
    34. Rina Kuswahyuning, Michael S. Roberts. Concentration Dependency in Nicotine Skin Penetration Flux from Aqueous Solutions Reflects Vehicle Induced Changes in Nicotine Stratum Corneum Retention. Pharmaceutical Research 2014, 31 (6) , 1501-1511. https://doi.org/10.1007/s11095-013-1256-4
    35. Arian Saffari, Nancy Daher, Ario Ruprecht, Cinzia De Marco, Paolo Pozzi, Roberto Boffi, Samera H. Hamad, Martin M. Shafer, James J. Schauer, Dane Westerdahl, Constantinos Sioutas. Particulate metals and organic compounds from electronic and tobacco-containing cigarettes: comparison of emission rates and secondhand exposure. Environ. Sci.: Processes Impacts 2014, 16 (10) , 2259-2267. https://doi.org/10.1039/C4EM00415A
    36. Ivan L Gee, Sean Semple, Adrian Watson, Andrea Crossfield. Nearly 85% of tobacco smoke is invisible—a confirmation of previous claims: Table 1. Tobacco Control 2013, 22 (6) , 429-429. https://doi.org/10.1136/tobaccocontrol-2012-050475
    37. Angelo Cecinato, Catia Balducci, Paola Romagnoli, Mattia Perilli. Airborne psychotropic substances in eight Italian big cities: Burdens and behaviours. Environmental Pollution 2012, 171 , 140-147. https://doi.org/10.1016/j.envpol.2012.07.033
    38. D. L. McKinney, M. Gogova, B. D. Davies, V. Ramakrishnan, K. Fisher, W. H. Carter, H. T. Karnes, W. R. Garnett, S. S. Iyer, A. A. Somani, G. Kobal, W. H. Barr. Evaluation of the Effect of Ammonia on Nicotine Pharmacokinetics Using Rapid Arterial Sampling. Nicotine & Tobacco Research 2012, 14 (5) , 586-595. https://doi.org/10.1093/ntr/ntr257
    39. M. Viana, C. Postigo, C. Balducci, A. Cecinato, M. J. López de Alda, D. Barceló, B. Artíñano, P. López-Mahía, A. Alastuey, X. Querol. Psychoactive Substances in Airborne Particles in the Urban Environment. 2012, 435-460. https://doi.org/10.1007/698_2011_135
    40. Jan van Amsterdam, Annemarie Sleijffers, Paul van Spiegel, Roos Blom, Maarten Witte, Jan van de Kassteele, Marco Blokland, Peter Steerenberg, Antoon Opperhuizen. Effect of ammonia in cigarette tobacco on nicotine absorption in human smokers. Food and Chemical Toxicology 2011, 49 (12) , 3025-3030. https://doi.org/10.1016/j.fct.2011.09.037
    41. J.H. Lauterbach, M. Bao, P.J. Joza, W.S. Rickert. Free-base nicotine in tobacco products. Part I. Determination of free-base nicotine in the particulate phase of mainstream cigarette smoke and the relevance of these findings to product design parameters. Regulatory Toxicology and Pharmacology 2010, 58 (1) , 45-63. https://doi.org/10.1016/j.yrtph.2010.05.007
    42. Dorothy K Hatsukami, Kenneth A Perkins, Mark G LeSage, David L Ashley, Jack E Henningfield, Neal L Benowitz, Cathy L Backinger, Mitch Zeller. Nicotine reduction revisited: science and future directions. Tobacco Control 2010, 19 (5) , e1-e1. https://doi.org/10.1136/tc.2009.035584
    43. Neha Gowadia, Derek Dunn-Rankin. A transport model for nicotine in the tracheobronchial and pulmonary region of the lung. Inhalation Toxicology 2010, 22 (1) , 42-48. https://doi.org/10.3109/08958370902862442
    44. Jeffrey Wigand. Smoking and Mental Illness: A Commentary and Counterpoint. Journal of Dual Diagnosis 2009, 5 (2) , 219-223. https://doi.org/10.1080/15504260902869931
    45. Terrell Stevenson, Robert N. Proctor. The SECRET and SOUL of Marlboro. American Journal of Public Health 2008, 98 (7) , 1184-1194. https://doi.org/10.2105/AJPH.2007.121657
    46. Jeffrey I. Seeman, Richard A. Carchman. The possible role of ammonia toxicity on the exposure, deposition, retention, and the bioavailability of nicotine during smoking. Food and Chemical Toxicology 2008, 46 (6) , 1863-1881. https://doi.org/10.1016/j.fct.2008.02.021
    47. Maneerat Ongwandee, Glenn C. Morrison, Xiaowen Guo, Charles C. Chusuei. Adsorption of trimethylamine on zirconium silicate and polyethylene powder surfaces. Colloids and Surfaces A: Physicochemical and Engineering Aspects 2007, 310 (1-3) , 62-67. https://doi.org/10.1016/j.colsurfa.2007.05.076
    48. W E Stephens. Dependence of tar, nicotine and carbon monoxide yields on physical parameters: implications for exposure, emissions control and monitoring. Tobacco Control 2007, 16 (3) , 170-176. https://doi.org/10.1136/tc.2006.017491
    49. Rob Crane. The Most Addictive Drug, the Most Deadly Substance: Smoking Cessation Tactics for the Busy Clinician. Primary Care: Clinics in Office Practice 2007, 34 (1) , 117-135. https://doi.org/10.1016/j.pop.2007.02.003
    50. Charlene H. Callicutt, Richard H. Cox, Frank Hsu, Robin D. Kinser, Susan W. Laffoon, Peter N. Lee, Kenneth F. Podraza, Edward B. Sanders, Jeffrey I. Seeman. The role of ammonia in the transfer of nicotine from tobacco to mainstream smoke. Regulatory Toxicology and Pharmacology 2006, 46 (1) , 1-17. https://doi.org/10.1016/j.yrtph.2006.05.008
    51. G Ferris Wayne, G N Connolly, J E Henningfield. Brand differences of free-base nicotine delivery in cigarette smoke: the view of the tobacco industry documents. Tobacco Control 2006, 15 (3) , 189-198. https://doi.org/10.1136/tc.2005.013805
    52. M. Ongwandee, S. S. Bettinger, G. C. Morrison. The influence of ammonia and carbon dioxide on the sorption of a basic organic pollutant to a mineral surface. Indoor Air 2005, 15 (6) , 408-419. https://doi.org/10.1111/j.1600-0668.2005.00380.x
    53. T. Heitzer, T. Meinertz. Rauchen und koronare Herzkrankheit. Zeitschrift für Kardiologie 2005, 94 (S3) , iii30-iii42. https://doi.org/10.1007/s00392-005-1306-y
    54. Geoffrey Ferris Wayne, Gregory Connolly, Jack Henningfield. Assessing internal tobacco industry knowledge of the neurobiology of tobacco dependence. Nicotine & Tobacco Research 2004, 6 (6) , 927-940. https://doi.org/10.1080/14622200412331324839
    55. P.J. Lipowicz, J.J. Piadé. Evaporation and subsequent deposition of nicotine from mainstream cigarette smoke in a denuder tube. Journal of Aerosol Science 2004, 35 (1) , 33-45. https://doi.org/10.1016/S0021-8502(03)00385-9
    56. S Chapman. “Keep a low profile”: pesticide residue, additives, and freon use in Australian tobacco manufacturing. Tobacco Control 2003, 12 (suppl 3) , iii45-iii53. https://doi.org/10.1136/tc.12.suppl_3.iii45
    57. James F. Pankow. Gas/particle partitioning of neutral and ionizing compounds to single and multi-phase aerosol particles. 1. Unified modeling framework. Atmospheric Environment 2003, 37 (24) , 3323-3333. https://doi.org/10.1016/S1352-2310(03)00346-7
    58. Bradley J. Ingebrethsen, Cynthia S. Lyman, Charles H. Risner, Patricia Martin, Bert M. Gordon. Particle-Gas Equilibria of Ammonia and Nicotine in Mainstream Cigarette Smoke. Aerosol Science and Technology 2001, 35 (5) , 874-886. https://doi.org/10.1080/02786820126850
    59. E Luque-Pérez, A Rı́os, M Valcárcel, L.-G Danielsson, F Ingman. Analysis of solid samples using supported liquid membranes: a method for the evaluation of the release of nicotine from Swedish snuff. Analytica Chimica Acta 1999, 387 (2) , 155-164. https://doi.org/10.1016/S0003-2670(99)00077-X
    60. Harmanjatinder S. Sekhon, Yibing Jia, Renee Raab, Alexander Kuryatov, James F. Pankow, Jeffrey A. Whitsett, Jon Lindstrom, Eliot R. Spindel. Prenatal nicotine increases pulmonary α7 nicotinic receptor expression and alters fetal lung development in monkeys. Journal of Clinical Investigation 1999, 103 (5) , 637-647. https://doi.org/10.1172/JCI5232
    61. David L. Ashley, James F. Pankow, Ameer D. Tavakoli, Clifford H. Watson. Approaches, Challenges, and Experience in Assessing Free Nicotine. , 437-456. https://doi.org/10.1007/978-3-540-69248-5_15

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect