Chemical evolution of atmospheric organic carbon over multiple generations of oxidation

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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Fig. 1: Measured carbon in the photooxidation of α-pinene, characterized by molecular formula.
Fig. 2: Chemical characterization of carbon measured in the photooxidation of α-pinene in terms of \(\bar{{{\bf{O}}{\bf{S}}}_{{\bf{C}}}}\) and c*, commonly used for simplified representation of atmospheric organic carbon.
Fig. 3
Fig. 4: Changes in atmospheric lifetime and reactivity through multigenerational oxidation of α-pinene.

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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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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.

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

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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.

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Supplementary experimental details and results

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*

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

Supplementary Data 1

A list of all ions measured in this work

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Isaacman-VanWertz, G., Massoli, P., O’Brien, R. et al. Chemical evolution of atmospheric organic carbon over multiple generations of oxidation. Nature Chem 10, 462–468 (2018). https://doi.org/10.1038/s41557-018-0002-2

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