Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol

Abstract

A detailed understanding of the sources, transformations and fates of organic species in the environment is crucial because of the central roles that they play in human health, biogeochemical cycles and the Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here, we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state, a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of the average carbon oxidation state, using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Figure 1: Possible combinations of average carbon oxidation state () and number of carbon atoms (nC) for stable organic molecules.
Figure 2: Location in nC space of organic aerosol, based upon measurements of organic aerosol.
Figure 3: Chemical complexity of organics as a function of oxidation state and carbon number.
Figure 4: Oxidation trajectories in nC space, as determined from laboratory studies of oxidation reactions.

References

  1. 1

    Kanakidou, M. et al. Organic aerosol and global climate modelling: a review. Atmos. Chem. Phys. 5, 1053–1123 (2005).

    CAS  Article  Google Scholar 

  2. 2

    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).

    Google Scholar 

  3. 3

    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).

    CAS  Article  Google Scholar 

  4. 4

    Logan, J. A., Prather, M. J., Wofsy, S. C. & McElroy, M. B. Tropospheric chemistry—a global perspective. J. Geophys. Res. Oceans Atmos. 86, 7210–7254 (1981).

    CAS  Article  Google Scholar 

  5. 5

    Masiello, C. A., Gallagher, M. E., Randerson, J. T., Deco, R. M. & Chadwick, O. A. Evaluating two experimental approaches for measuring ecosystem carbon oxidation state and oxidative ratio. J. Geophys. Res. Biogeosci. 113, G03010 (2008).

    Article  Google Scholar 

  6. 6

    McDermitt, D. K. & Loomis, R. Elemental composition of biomass and its relation to energy content, growth efficiency, and growth-yield. Ann. Bot. 48, 275–290 (1981).

    CAS  Article  Google Scholar 

  7. 7

    Vogel, F., Harf, J., Hug, A. & von Rohr, P. R. The mean oxidation number of carbon (MOC)—a useful concept for describing oxidation processes. Water Res. 34, 2689–2702 (2000).

    CAS  Article  Google Scholar 

  8. 8

    Jacob, D. J. Introduction to Atmospheric Chemistry (Princeton Univ. Press, 1999).

  9. 9

    Seinfeld, J. H., Erdakos, G. B., Asher, W. E. & Pankow, J. F. Modeling the formation of secondary organic aerosol (SOA). 2. The predicted effects of relative humidity on aerosol formation in the α-pinene-, β-pinene-, sabinene-, Δ3-carene-, and cyclohexene-ozone systems. Environ. Sci. Technol. 35, 1806–1817 (2001).

    CAS  Article  Google Scholar 

  10. 10

    Pankow, J. F. & Barsanti, K. C. The carbon number-polarity grid: a means to manage the complexity of the mix of organic compounds when modeling atmospheric organic particulate matter. Atmos. Environ. 43, 2829–2835 (2009).

    CAS  Article  Google Scholar 

  11. 11

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

    CAS  Article  Google Scholar 

  12. 12

    Heald, C. L. et al. A simplified description of the evolution of organic aerosol composition in the atmosphere. Geophys. Res. Lett. 37, L08803 (2010).

    Google Scholar 

  13. 13

    Carlton, A. G. et al. Atmospheric oxalic acid and SOA production from glyoxal: results of aqueous photooxidation experiments. Atmos. Environ. 41, 2588–7602 (2007).

    Article  Google Scholar 

  14. 14

    Nguyen, T. B. et al. High-resolution mass spectrometry analysis of secondary organic aerosol generated by ozonolysis of isoprene. Atmos. Environ. 44, 1032–1042 (2010).

    CAS  Article  Google Scholar 

  15. 15

    O'Brien, R. J., Holmes, J. R. & Bockian, A. H. Formation of photochemical aerosol from hydrocarbons—chemical reactivity and products. Environ. Sci. Technol. 9, 568–576 (1975).

    CAS  Article  Google Scholar 

  16. 16

    Krivacsy, Z. et al. Study on the chemical character of water soluble organic compounds in fine atmospheric aerosol at the Jungfraujoch. J. Atmos. Chem. 39, 235–259 (2001).

    CAS  Article  Google Scholar 

  17. 17

    Kiss, G., Varga, B., Galambos, I. & Ganszky, I. Characterization of water-soluble organic matter isolated from atmospheric fine aerosol. J. Geophys Res. Atmos. 107, 8339 (2002).

    Article  Google Scholar 

  18. 18

    Altieri, K. E., Turpin, B. J. & Seitzinger, S. P. Oligomers, organosulfates, and nitrooxy organosulfates in rainwater identified by ultra-high resolution electrospray ionization FT-ICR mass spectrometry. Atmos. Chem. Phys. 9, 2533–2542 (2009).

    CAS  Article  Google Scholar 

  19. 19

    Bateman, A. P., Nizkorodov, S. A., Laskin, J. & Laskin, A. Time-resolved molecular characterization of limonene/ozone aerosol using high-resolution electrospray ionization mass spectrometry. Phys. Chem. Chem. Phys. 11, 7931–7942 (2009).

    CAS  Article  Google Scholar 

  20. 20

    Wozniak, A. S., Bauer, J. E., Sleighter, R. L., Dickhut, R. M. & Hatcher, P. G. Technical note: molecular characterization of aerosol-derived water soluble organic carbon using ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Atmos. Chem. Phys. 8, 5099–5111 (2008).

    CAS  Article  Google Scholar 

  21. 21

    Mazzoleni, L. R., Ehrmann, B. M., Shen, X. H., Marshall, A. G. & Collett, J. L. Water-soluble atmospheric organic matter in fog: exact masses and chemical formula identification by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry. Environ. Sci. Technol. 44, 3690–3697 (2010).

    CAS  Article  Google Scholar 

  22. 22

    Fuzzi, S. et al. A simplified model of the water soluble organic component of atmospheric aerosols. Geophys. Res. Lett. 28, 4079–4082 (2001).

    CAS  Article  Google Scholar 

  23. 23

    Gilardoni, S. et al. Characterization of organic ambient aerosol during MIRAGE 2006 on three platforms. Atmos. Chem. Phys. 9, 5417–5432 (2009).

    CAS  Article  Google Scholar 

  24. 24

    Aiken, A. C. et al. O/C and OM/OC ratios of primary, secondary, and ambient organic aerosols with high-resolution time-of-flight aerosol mass spectrometry. Environ. Sci. Technol. 42, 4478–4485 (2008).

    CAS  Article  Google Scholar 

  25. 25

    Shilling, J. E. et al. Loading-dependent elemental composition of alpha-pinene SOA particles. Atmos. Chem. Phys. 9, 771–782 (2009).

    CAS  Article  Google Scholar 

  26. 26

    Presto, A. A. et al. Intermediate-volatility organic compounds: a potential source of ambient oxidized organic aerosol. Environ. Sci. Technol. 43, 4744–4749 (2009).

    CAS  Article  Google Scholar 

  27. 27

    Chhabra, P., Flagan, R. C. & Seinfeld, J. H. Elemental analysis of chamber organic aerosol using the aerodyne high resolution mass spectrometer. Atmos. Chem. Phys. 10, 4111–4131 (2010).

    CAS  Article  Google Scholar 

  28. 28

    Sun, Y. et al. Size-resolved aerosol chemistry on Whistler Mountain, Canada with a high-resolution aerosol mass spectrometer during INTEX-B. Atmos. Chem. Phys. 9, 3095–3111 (2009).

    CAS  Article  Google Scholar 

  29. 29

    Chen, Q. et al. Mass spectral characterization of submicron biogenic organic particles in the Amazon Basin. Geophys. Res. Lett. 36, L20806 (2009).

    Article  Google Scholar 

  30. 30

    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. Discuss. 10, 24091–24133 (2010).

    Article  Google Scholar 

  31. 31

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

    CAS  Article  Google Scholar 

  32. 32

    Atkinson, R. Rate constants for the atmospheric reactions of alkoxy radicals: an updated estimation method. Atmos. Environ. 41, 8468–8485 (2007).

    CAS  Article  Google Scholar 

  33. 33

    Lambe, A. T., Miracolo, M. A., Hennigan, C. J., Robinson, A. L. & Donahue, N. M. Effective rate constants and uptake coefficients for the reactions of organic molecular markers (n-alkanes, hopanes, and steranes) in motor oil and diesel primary organic aerosols with hydroxyl radicals. Environ. Sci. Technol. 43, 8794–8800 (2009).

    CAS  Article  Google Scholar 

  34. 34

    MacCarthy, P. The principles of humic substances. Soil Sci. 166, 738–751 (2001).

    CAS  Article  Google Scholar 

  35. 35

    Reemtsma, T., These, A., Springer, A. & Linscheid, M. Fulvic acids as transition state of organic matter: indications from high resolution mass spectrometry. Environ. Sci. Technol. 40, 5839–5845 (2006).

    CAS  Article  Google Scholar 

  36. 36

    Graber, E. R. & Rudich, Y. Atmospheric HULIS: how humic-like are they? A comprehensive and critical review. Atmos. Chem. Phys. 6, 729–753 (2006).

    CAS  Article  Google Scholar 

  37. 37

    Trainer, M. G. et al. Organic haze on Titan and the early Earth. Proc. Natl Acad. Sci. USA 103, 18035–18042 (2006).

    CAS  Article  Google Scholar 

  38. 38

    Kroll, J. H. et al. Measurement of fragmentation and functionalization pathways in the heterogeneous oxidation of oxidized organic aerosol. Phys. Chem. Chem. Phys. 11, 8005–8014 (2009).

    CAS  Article  Google Scholar 

  39. 39

    Kessler, S. H. et al. Chemical sinks of organic aerosol: kinetics and products of the heterogeneous oxidation of erythritol and levoglucosan. Environ. Sci. Technol. 44, 7005–7010 (2010).

    CAS  Article  Google Scholar 

  40. 40

    Pankow, J. & Asher, W. SIMPOL.1: a simple group contribution method for predicting vapor pressures and enthalpies of vaporization of multifunctional organic compounds. Atmos. Chem. Phys. 8, 2773–2796 (2008).

    CAS  Article  Google Scholar 

  41. 41

    Cappa, C. D. & Jimenez, J. L. Quantitative estimates of the volatility of ambient organic aerosol. Atmos. Chem. Phys. 10, 5409–5424 (2010).

    CAS  Article  Google Scholar 

  42. 42

    Aschmann, S. M., Atkinson, R. & Arey, J. Products of reaction of OH radicals with α-pinene. J. Geophys Res. Atmos. 107, 4191 (2002).

  43. 43

    Edney, E. O. et al. Polar organic oxygenates in PM2.5 at a southeastern site in the United States. Atmos. Environ. 37, 3947–3965 (2003).

    CAS  Article  Google Scholar 

  44. 44

    Surratt, J. D. et al. Chemical composition of secondary organic aerosol formed from the photooxidation of isoprene. J. Phys. Chem. A 110, 9665–9690 (2006).

    CAS  Article  Google Scholar 

  45. 45

    Kleindienst, T. E. et al. Estimates of the contributions of biogenic and anthropogenic hydrocarbons to secondary organic aerosol at a southeastern U.S. location. Atmos. Environ. 41, 8288–8300 (2007).

    CAS  Article  Google Scholar 

  46. 46

    Szmigielski, R. et al. 3-Methyl-1,2,3-butanetricarboxylic acid: an atmospheric tracer for terpene secondary organic aerosol. Geophys. Res. Lett. 34, L24811 (2007).

    Article  Google Scholar 

  47. 47

    Paulot, F. et al. Isoprene photooxidation: new insights into the production of acids and organic nitrates. Atmos. Chem. Phys. 9, 1479–1501 (2009).

    CAS  Article  Google Scholar 

  48. 48

    Claeys, M. et al. Terpenylic acid and related compounds from the oxidation of α-pinene: implications for new particle formation and growth above forests. Environ. Sci. Technol. 43, 6976–6982 (2009).

    CAS  Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the US Environmental Protection Agency (EPA) Science To Achieve Results (STAR) program (grant R833746 to J.H.K., N.M.D., D.R.W.), the US Department of Energy (DOE: grant DE-FG02-05ER63995), the National Science Foundation (NSF: grant ATM-0904292 to C.E.K., D.R.W. and M.R.C.; grants ATM-0449815 and ATM-0919189 to J.L.J.) and the National Oceanic and Atmospheric Administration (NOAA: grant NA08OAR4310565). K.R.W., H.B., E.R.M. and J.D.S are supported by the Director, Office of Energy Research, Office of Basic Energy Sciences, and Chemical Sciences Division of the US DOE (contract no. DE-AC02-05CH11231), with additional support from the Laboratory Directed Research and Development Program at the Lawrence Berkeley National Laboratory (LBNL). J.D.S. was also supported by the Camille and Henry Dreyfus foundation postdoctoral program in environmental chemistry. This paper has not been subject to peer and policy review by the above agencies, and therefore does not necessarily reflect their views; no official endorsement should be inferred.

Author information

Affiliations

Authors

Contributions

The present work was originally conceived by J.H.K. with C.E.K. and D.R.W., with substantial input by N.M.D., J.L.J., M.R.C., S.H.K. and K.R.W. The ESI data were provided by K.E.A., L.R.M. and A.S.W. (Table 1 and Fig. 2). S.H.K. carried out the combinatorial calculations to produce Fig. 3. Data on the aging of organics (Fig. 4) were collected by J.D.S., S.H.K., J.H.K. and K.R.W. (squalane, triacontane and levoglucosan) and E.R.M., J.D.S., K.R.W. and H.B. (coronene). J.H.K. wrote the paper with input from all co-authors, especially N.M.D., J.L.J., M.R.C. and C.E.K. The Supplementary Information was written by J.H.K., N.M.D., H.B. and E.R.M.

Corresponding authors

Correspondence to Jesse H. Kroll or Erin R. Mysak or Jared D. Smith.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 890 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Kroll, J., Donahue, N., Jimenez, J. et al. Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol. Nature Chem 3, 133–139 (2011). https://doi.org/10.1038/nchem.948

Download citation

Further reading