Abstract

The evolution of atmospheric organic carbon as it undergoes oxidation has a controlling influence on concentrations of key atmospheric species, including particulate matter, ozone and oxidants. However, full characterization of organic carbon over hours to days of atmospheric processing has been stymied by its extreme chemical complexity. Here we study the multigenerational oxidation of α-pinene in the laboratory, characterizing products with several state-of-the-art analytical techniques. Although quantification of some early generation products remains elusive, full carbon closure is achieved (within measurement uncertainty) by the end of the experiments. These results provide new insights into the effects of oxidation on organic carbon properties (volatility, oxidation state and reactivity) and the atmospheric lifecycle of organic carbon. Following an initial period characterized by functionalization reactions and particle growth, fragmentation reactions dominate, forming smaller species. After approximately one day of atmospheric aging, most carbon is sequestered in two long-lived reservoirs—volatile oxidized gases and low-volatility particulate matter.

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References

  1. 1.

    Sillman, S. The relation between ozone, NOx and hydrocarbons in urban and polluted rural environments. Atmos. Environ. 33, 1821–1845 (1999).

  2. 2.

    Atkinson, R. Atmospheric chemistry of VOCs and NOx. Atmos. Environ. 34, 2063–2101 (2000).

  3. 3.

    Lelieveld, J., Gromov, S., Pozzer, A. & Taraborrelli, D. Global tropospheric hydroxyl distribution, budget and reactivity. Atmos. Chem. Phys. 16, 12477–12493 (2016).

  4. 4.

    Yang, Y. et al. Towards a quantitative understanding of total OH reactivity: a review. Atmos. Environ. 134, 147–161 (2016).

  5. 5.

    Zhang, Q. et al. Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically-influenced Northern Hemisphere midlatitudes. Geophys. Res. Lett. 34, L13801 (2007).

  6. 6.

    Jimenez, J.-L. et al. Evolution of organic aerosols in the atmosphere. Science 326, 1525–1529 (2009).

  7. 7.

    Aumont, B., Szopa, S. & Madronich, S. Modelling the evolution of organic carbon during its gas-phase tropospheric oxidation: development of an explicit model based on a self generating approach. Atmos. Chem. Phys. 5, 24975–2517 (2005).

  8. 8.

    Kroll, J. H. & Seinfeld, J. H. Chemistry of secondary organic aerosol: formation and evolution of low-volatility organics in the atmosphere. Atmos. Environ. 42, 3593–3624 (2008).

  9. 9.

    Cappa, C. D. & Wilson, K. R. Multi-generation gas-phase oxidation, equilibrium partitioning, and the formation and evolution of secondary organic aerosol. Atmos. Chem. Phys. 12, 9505–9528 (2012).

  10. 10.

    Donahue, N. M., Epstein, S. A., Pandis, S. N. & Robinson, A. L. A two-dimensional volatility basis set: 1. organic-aerosol mixing thermodynamics. Atmos. Chem. Phys. 11, 3303–3318 (2011).

  11. 11.

    Goldstein, A. H. & Galbally, I. Known and unexplored organic constituents in the Earth’s atmosphere. Environ. Sci. Technol. 41, 1514–1521 (2007).

  12. 12.

    Calvert, J. G., Derwent, R. G., Orlando, J. J., Tyndall, G. S. & Wallington, T. J. Mechanisms of Atmospheric Oxidation of the Alkanes (Oxford Univ. Press, Oxford, 2007).

  13. 13.

    Lee, A. et al. Gas-phase products and secondary aerosol yields from the photooxidation of 16 different terpenes. J. Geophys. Res. Atmos. 111, D17305 (2006).

  14. 14.

    Lee, A. et al. Gas-phase products and secondary aerosol yields from the ozonolysis of ten different terpenes. J. Geophys. Res. Atmos. 111, D07302 (2006).

  15. 15.

    Zhang, X. et al. Influence of vapor wall loss in laboratory chambers on yields of secondary organic aerosol. Proc. Natl Acad. Sci. USA 111, 5802–5807 (2014).

  16. 16.

    Robinson, A. L. et al. Rethinking organic aerosols: semivolatile emissions and photochemical aging. Science 315, 1259–1262 (2007).

  17. 17.

    Isaacman-VanWertz, G. et al. Using advanced mass spectrometry techniques to fully characterize atmospheric organic carbon: current capabilities and remaining gaps. Faraday Discuss. 200, 579–598 (2017).

  18. 18.

    Decarlo, P. F. et al. Field-deployable, high-resolution, time-of-flight aerosol mass spectrometer. Anal. Chem. 78, 8281–8289 (2006).

  19. 19.

    Graus, M., Müller, M. & Hansel, A. High resolution PTR-TOF: quantification and formula confirmation of VOC in real time. J. Am. Soc. Mass Spectrom. 21, 1037–1044 (2010).

  20. 20.

    Jordan, A. et al. A high resolution and high sensitivity proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS). Int. J. Mass Spectrom. 286, 122–128 (2009).

  21. 21.

    Aljawhary, D., Lee, A. K. Y. & Abbatt, J. P. D. High-resolution chemical ionization mass spectrometry (ToF-CIMS): application to study SOA composition and processing. Atmos. Meas. Tech. 6, 3211–3224 (2013).

  22. 22.

    Jokinen, T. et al. Atmospheric sulphuric acid and neutral cluster measurements using CI-APi-TOF. Atmos. Chem. Phys. 12, 4117–4125 (2012).

  23. 23.

    Krechmer, J. E. et al. Formation of low volatility organic compounds and secondary organic aerosol from isoprene hydroxyhydroperoxide low-NO oxidation. Environ. Sci. Technol. 49, 10330–10339 (2015).

  24. 24.

    Lee, B. H. et al. An iodide-adduct high-resolution time-of-flight chemical-ionization mass spectrometer: application to atmospheric inorganic and organic compounds. Environ. Sci. Technol. 48, 6309–6317 (2014).

  25. 25.

    Lopez-Hilfiker, F. D. et al. Constraining the sensitivity of iodide adduct chemical ionization mass spectrometry to multifunctional organic molecules using the collision limit and thermodynamic stability of iodide ion adducts. Atmos. Meas. Tech. 9, 1505–1512 (2016).

  26. 26.

    Eddingsaas, N. C. et al. α-Pinene photooxidation under controlled chemical conditions—Part 1: gas-phase composition in low-and high-NOx environments. Atmos. Chem. Phys. 12, 6489–6504 (2012).

  27. 27.

    Capouet, M., Peeters, J., Nozière, B. & Müller, J.-F. Alpha-pinene oxidation by OH: simulations of laboratory experiments. Atmos. Chem. Phys. Discuss 4, 4039–4103 (2004).

  28. 28.

    Pathak, R. K., Stanier, C. O., Donahue, N. M. & Pandis, S. N. Ozonolysis of α-pinene at atmospherically relevant concentrations: temperature dependence of aerosol mass fractions (yields). J. Geophys. Res. Atmos. 112, D03201 (2007).

  29. 29.

    Donahue, N. M. et al. Aging of biogenic secondary organic aerosol via gas-phase OH radical reactions. Proc. Natl Acad. Sci. USA 109, 13503–13508 (2012).

  30. 30.

    Hatakeyama, S., Ohno, M., Weng, J., Takagi, H. & Akimoto, H. Mechanism for the formation of gaseous and particulate products from ozone-cycloalkene reactions in air. Environ. Sci. Technol. 21, 52–57 (1987).

  31. 31.

    Daumit, K. E., Kessler, S. H. & Kroll, J. H. Average chemical properties and potential formation pathways of highly oxidized organic aerosol. Faraday Discuss. 165, 181–202 (2013).

  32. 32.

    Ehn, M. et al. A large source of low-volatility secondary organic aerosol. Nature 506, 476–479 (2014).

  33. 33.

    Ehn, M. et al. Composition and temporal behavior of ambient ions in the boreal forest. Atmos. Chem. Phys. 10, 8513–8530 (2010).

  34. 34.

    Saunders, S. M., Jenkin, M. E., Derwent, R. G. & Pilling, M. J. Protocol for the development of the Master Chemical Mechanism, MCMv3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds. Atmos. Chem. Phys. 3, 161–180 (2003).

  35. 35.

    Worton, D. R., Gentner, D. R., Isaacman, G. & Goldstein, A. H. Embracing complexity: deciphering origins and transformations of atmospheric organics through speciated measurements. Environ. Sci. Technol. 46, 5265–5266 (2012).

  36. 36.

    Nah, T. et al. Influence of seed aerosol surface area and oxidation rate on vapor wall deposition and SOA mass yields: a case study with α-pinene ozonolysis. Atmos. Chem. Phys. 16, 9361–9379 (2016).

  37. 37.

    Trump, E. R., Epstein, S. A., Riipinen, I. & Donahue, N. M. Wall effects in smog chamber experiments: a model study. Aerosol Sci. Technol. 50, 1180–1200 (2016).

  38. 38.

    Ye, P. et al. Vapor wall loss of semi-volatile organic compounds in a Teflon chamber. Aerosol Sci. Technol. 50, 822–834 (2016).

  39. 39.

    Nozière, B., Barnes, I. & Becker, K.-H. Product study and mechanisms of the reactions of α-pinene and of pinonaldehyde with OH radicals. J. Geophys. Res. Atmos. 104, 23645–23656 (1999).

  40. 40.

    Iyer, S., Lopez-Hilfiker, F. D., Lee, B. H., Thornton, J. A. & Kurtén, T. Modeling the detection of organic and inorganic compounds using iodide-based chemical ionization. J. Phys. Chem. A 120, 576–587 (2016).

  41. 41.

    Pagonis, D., Krechmer, J. E., Gouw, J. De, Jimenez, J. L.& Ziemann, P. J. Effects of gas–wall partitioning in Teflon tubing and instrumentation on time-resolved measurements of gas-phase organic compounds. Atmos. Meas. Tech. 10, 4687–4696 (2017).

  42. 42.

    Kroll, J. H. et al. Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol. Nat. Chem. 3, 133–139 (2011).

  43. 43.

    Lee, B. H. et al. Highly functionalized organic nitrates in the southeast United States: contribution to secondary organic aerosol and reactive nitrogen budgets. Proc. Natl Acad. Sci. USA 113, 1516–1521 (2016).

  44. 44.

    Manion, J. A. et al. NIST Chemical KineticsDatabase, NIST Standard Reference Database 17 v.7.0 (web version), data v.2015.12 (National Institute of Standards and Technology, 2015); http://kinetics.nist.gov/kinetics/

  45. 45.

    Donahue, N. M. et al. Why do organic aerosols exist? Understanding aerosol lifetimes using the two-dimensional volatility basis set. Environ. Chem. 10, 151–157 (2013).

  46. 46.

    Kroll, J. H., Lim, C. Y., Kessler, S. H. & Wilson, K. R. Heterogeneous oxidation of atmospheric organic aerosol: kinetics of changes to the amount and oxidation state of particle-phase organic carbon. J. Phys. Chem. A 119, 10767–10783 (2015).

  47. 47.

    Dixon-Lewis, G. Flames structure and flame reaction kinetics VII. Reactions of traces of heavy water, deuterium and carbon dioxide added to rich hydrogen + nitrogen + oxygen flames. Proc. R. Soc. London A 330, 219–245 (1972).

  48. 48.

    Raff, J. D., Stevens, P. S. & Hites, R. A. Relative rate and product studies of the OH–acetone reaction. J. Phys. Chem. A 108, 4728–4735 (2005).

  49. 49.

    Richards-Henderson, N. K., Goldstein, A. H. & Wilson, K. R. Large enhancement in the heterogeneous oxidation rate of organic aerosols by hydroxyl radicals in the presence of nitric oxide. J. Phys. Chem. Lett. 6, 4451–4455 (2015).

  50. 50.

    Paulot, F. et al. Unexpected epoxide formation in the gas-phase photooxidation of isoprene. Science 325, 730–733 (2013).

  51. 51.

    Surratt, J. D. et al. Reactive intermediates revealed in secondary organic aerosol formation from isoprene. Proc. Natl Acad. Sci. USA 107, 6640–6645 (2010).

  52. 52.

    Palm, B. B. et al. In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor. Atmos. Chem. Phys. 16, 2943–2970 (2016).

  53. 53.

    Chan, A. W. H. et al. Speciated measurements of semivolatile and intermediate volatility organic compounds (S/IVOCs) in a pine forest during BEACHON-RoMBAS 2011. Atmos. Chem. Phys. 16, 1187–1205 (2016).

  54. 54.

    Tkacik, D. S., Presto, A. A., Donahue, N. M. & Robinson, A. L. Secondary organic aerosol formation from intermediate-volatility organic compounds: cyclic, linear, and branched alkanes. Environ. Sci. Technol. 46, 8773–8781 (2012).

  55. 55.

    Park, J.-H. et al. Active atmosphere–ecosystem exchange of the vast majority of detected volatile organic compounds. Science 341, 643–648 (2013).

  56. 56.

    Nguyen, T. B. et al. Rapid deposition of oxidized biogenic compounds to a temperate forest. Proc. Natl Acad. Sci. USA 112, E392–E401 (2015).

  57. 57.

    Wolfe, G. M. et al. Formaldehyde production from isoprene oxidation across NOx regimes. Atmos. Chem. Phys. 16, 2597–2610 (2016).

  58. 58.

    Warneke, C. et al. Photochemical aging of volatile organic compounds in the Los Angeles basin: weekday–weekend effect. J. Geophys. Res. Atmos. 118, 5018–5028 (2013).

  59. 59.

    Faulhaber, A. E. et al. Characterization of a thermodenuder-particle beam mass spectrometer system for the study of organic aerosol volatility and composition. Atmos. Meas. Tech. 2, 15–31 (2009).

  60. 60.

    McManus, J. B. et al. Pulsed quantum cascade laser instrument with compact design for rapid, high sensitivity measurements of trace gases in air. Appl. Phys. B Lasers Opt. 92, 387–392 (2008).

  61. 61.

    Canagaratna, M. R. et al. Elemental ratio measurements of organic compounds using aerosol mass spectrometry: characterization, improved calibration, and implications. Atmos. Chem. Phys. 15, 253–272 (2015).

  62. 62.

    Lopez-Hilfiker, F. D. et al. A novel method for online analysis of gas and particle composition: description and evaluation of a filter inlet for gases and AEROsols (FIGAERO). Atmos. Meas. Tech. 7, 983–1001 (2014).

  63. 63.

    La, Y. S. et al. Impact of chamber wall loss of gaseous organic compounds on secondary organic aerosol formation: explicit modeling of SOA formation from alkane and alkene oxidation. Atmos. Chem. Phys. 16, 1417–1431 (2016).

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Acknowledgements

We thank H. Stark for insights into correcting for mass-dependent transmission in the I CIMS calibration, J.-L. Jimenez for valuable discussions regarding vapour wall loss, C. Heald for valuable discussions of overall chemical trends and L. Wattenberg for the inspiration for the stacked plot approach to visualizing these data. This work was supported in part by the National Science Foundation (NSF) Postdoctoral Research Fellowship programme (AGS-PRF 1433432), as well as grants AGS-1536939, AGS-1537446 and AGS-1536551. D.A.K. acknowledges support from NSF grant AGS-1446286.

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Affiliations

  1. Department of Civil and Environmental Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA

    • Gabriel Isaacman-VanWertz
    • , Rachel O’Brien
    • , Christopher Lim
    • , Jonathan P. Franklin
    • , Joshua A. Moss
    • , James F. Hunter
    •  & Jesse H. Kroll
  2. Department of Civil and Environmental Engineering, Virginia Tech, Blacksburg, VA, USA

    • Gabriel Isaacman-VanWertz
  3. Aerodyne Research Inc., Billerica, MA, USA

    • Paola Massoli
    • , John B. Nowak
    • , Manjula R. Canagaratna
    • , Joseph R. Roscioli
    • , Scott T. Herndon
    • , Timothy B. Onasch
    • , Andrew T. Lambe
    • , John T. Jayne
    •  & Douglas R. Worsnop
  4. NASA Langley Research Center, Hampton, VA, USA

    • John B. Nowak
  5. Department of Environmental Science, Policy, and Management, University of California, Berkeley, Berkeley, CA, USA

    • Pawel K. Misztal
    • , Caleb Arata
    •  & Allen H. Goldstein
  6. School of Marine and Atmospheric Sciences, Stony Brook University, Stony Brook, NY, USA

    • Luping Su
    •  & Daniel A. Knopf
  7. Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA

    • Jesse H. Kroll

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Contributions

Experiments were conducted by G.I.-V.W., P.M., R.O’B., C.L., J.B.N., J.P.F., P.K.M., C.A., L.S., D.A.K., A.T.L., J.R.R. and S.T.H., with data analysis by these researchers with significant contributions by J.A.M., J.F.H., A.H.G., T.B.O., M.R.C., J.H.K., J.T.J. and D.R.W. G.I.-V.W. and J.H.K. interpreted the results. The manuscript was prepared by G.I.-V.W. and J.H.K., with contributions and editing by all listed authors.

Competing interests

P.M., J.B.N., J.R.R., S.T.H., T.B.O., M.R.C., J.T.J. and D.R.W. are (or were during this work) employees of Aerodyne Research, Inc. (ARI), which developed and commercialized several of the advanced mass spectrometric instruments utilized in this study.

Corresponding authors

Correspondence to Gabriel Isaacman-VanWertz or Jesse H. Kroll.

Supplementary information

  1. Supplementary Information

    Supplementary experimental details and results

  2. Supplementary Video 1

    Chemical characterization of carbon measured in the photooxidation of α-pinene in terms of two parameters commonly used for simplified representations of atmospheric organic carbon: \(\bar{{{\bf{OS}}}_{{\bf{C}}}}\) and c*

  3. Supplementary Video 2

    Chemical characterization of carbon measured in the photooxidation of α-pinene in terms of two parameters commonly used for simplified representations of atmospheric organic carbon: \(\bar{{{\bf{OS}}}_{{\bf{C}}}}\) and nC

  4. Supplementary Data 1

    A list of all ions measured in this work

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https://doi.org/10.1038/s41557-018-0002-2