Formation of carcinogens indoors by surface-mediated reactions of nicotine with nitrous acid, leading to potential thirdhand smoke hazards

Edited by Barbara J. Finlayson-Pitts, University of California, Irvine, Irvine, CA, and approved January 6, 2010 (received for review November 7, 2009)
February 8, 2010
107 (15) 6576-6581

Abstract

This study shows that residual nicotine from tobacco smoke sorbed to indoor surfaces reacts with ambient nitrous acid (HONO) to form carcinogenic tobacco-specific nitrosamines (TSNAs). Substantial levels of TSNAs were measured on surfaces inside a smoker’s vehicle. Laboratory experiments using cellulose as a model indoor material yielded a > 10-fold increase of surface-bound TSNAs when sorbed secondhand smoke was exposed to 60 ppbv HONO for 3 hours. In both cases we identified 1-(N-methyl-N-nitrosamino)-1-(3-pyridinyl)-4-butanal, a TSNA absent in freshly emitted tobacco smoke, as the major product. The potent carcinogens 4-(methylnitrosamino)-1-(3-pyridinyl)-1-butanone and N-nitroso nornicotine were also detected. Time-course measurements revealed fast TSNA formation, with up to 0.4% conversion of nicotine. Given the rapid sorption and persistence of high levels of nicotine on indoor surfaces—including clothing and human skin—this recently identified process represents an unappreciated health hazard through dermal exposure, dust inhalation, and ingestion. These findings raise concerns about exposures to the tobacco smoke residue that has been recently dubbed “thirdhand smoke.” Our work highlights the importance of reactions at indoor interfaces, particularly those involving amines and NOx/HONO cycling, with potential health impacts.

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Acknowledgments.

We express our gratitude to S. Schick (University of California San Francisco), C.J. Weschler (Environmental & Occupational Health Science Institute, Rutgers University, and Technical University of Denmark), K. Asotra (University of California Tobacco-Related Diseases Research Program), and W.J. Fisk (LBNL) for helpful suggestions and to R. Maddalena, M. Russell, R. Dod, F. Mizbani, E. Smith (LBNL), W. Luo, C. Chen, W. Ascher (Portland State University), C. Havel, and M. Goniewicz (University of California San Francisco) for their assistance. We also thank the journal editor and reviewers for their helpful suggestions. This work was supported by the University of California Tobacco-Related Diseases Research Program (Project 16RT-0158). Experimental work was carried out at LBNL under US Department of Energy Contract DE-AC02-05CH11231. Laboratory resources at University of California San Francisco were supported by the Flight Attendant Medical Research Institute and by National Institutes of Health Grant DA012393.

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Published in

Go to Proceedings of the National Academy of Sciences
Go to Proceedings of the National Academy of Sciences
Proceedings of the National Academy of Sciences
Vol. 107 | No. 15
April 13, 2010
PubMed: 20142504

Classifications

Submission history

Published online: February 8, 2010
Published in issue: April 13, 2010

Keywords

  1. exposure
  2. indoor environment
  3. nitrosamine
  4. nitrogen oxides
  5. heterogeneous chemistry

Acknowledgments

We express our gratitude to S. Schick (University of California San Francisco), C.J. Weschler (Environmental & Occupational Health Science Institute, Rutgers University, and Technical University of Denmark), K. Asotra (University of California Tobacco-Related Diseases Research Program), and W.J. Fisk (LBNL) for helpful suggestions and to R. Maddalena, M. Russell, R. Dod, F. Mizbani, E. Smith (LBNL), W. Luo, C. Chen, W. Ascher (Portland State University), C. Havel, and M. Goniewicz (University of California San Francisco) for their assistance. We also thank the journal editor and reviewers for their helpful suggestions. This work was supported by the University of California Tobacco-Related Diseases Research Program (Project 16RT-0158). Experimental work was carried out at LBNL under US Department of Energy Contract DE-AC02-05CH11231. Laboratory resources at University of California San Francisco were supported by the Flight Attendant Medical Research Institute and by National Institutes of Health Grant DA012393.

Notes

This article is a PNAS Direct Submission.

Authors

Affiliations

Mohamad Sleiman
Indoor Environment Department, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, MS 70-108B, Berkeley, CA 94720;
Lara A. Gundel
Indoor Environment Department, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, MS 70-108B, Berkeley, CA 94720;
James F. Pankow
Department of Chemistry, Portland State University, Portland, OR 97201;
Peyton Jacob, III
Departments of Medicine and Psychiatry, University of California San Francisco, CA 94143; and
Brett C. Singer
Indoor Environment Department, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, MS 70-108B, Berkeley, CA 94720;
Hugo Destaillats1 [email protected]
Indoor Environment Department, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, MS 70-108B, Berkeley, CA 94720;
School of Sustainable Engineering and the Built Environment, Arizona State University, Tempe, AZ 85287

Notes

1
To whom correspondence should be addressed. E-mail: [email protected].
Author contributions: M.S., L.A.G., J.F.P., P.J., B.C.S., and H.D. designed research; M.S., L.A.G., and H.D. performed research; P.J. contributed new reagents/analytic tools; M.S., L.A.G., J.F.P., P.J., B.C.S., and H.D. analyzed data; and M.S., L.A.G., J.F.P., P.J., B.C.S., and H.D. wrote the paper.

Competing Interests

The authors declare no conflict of interest.

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    Formation of carcinogens indoors by surface-mediated reactions of nicotine with nitrous acid, leading to potential thirdhand smoke hazards
    Proceedings of the National Academy of Sciences
    • Vol. 107
    • No. 15
    • pp. 6553-7113

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