Title: Synthesis and surface spectroscopy of α-pinene isotopologues and their corresponding secondary organic material

Abstract

Atmospheric aerosol–cloud interactions remain among the least understood processes within the climate system, leaving large uncertainties in the prediction of future climates. In particular, the nature of the surfaces of aerosol particles formed from biogenic terpenes, such as α-pinene, is poorly understood despite the importance of surface phenomena in their formation, growth, radiative properties, and ultimate fate. Herein we report the coupling of a site-specific deuterium labeling strategy with vibrational sum frequency generation (SFG) spectroscopy to probe the surface C–H oscillators in α-pinene-derived secondary organic aerosol material (SOM) generated in an atmospheric flow tube reactor. Three α-pinene isotopologues with methylene bridge, bridgehead methine, allylic, and vinyl deuteration were synthesized and their vapor phase SFG spectra were compared to that of unlabeled α-pinene. Subsequent analysis of the SFG spectra of their corresponding SOM revealed that deuteration of the bridge methylene C–H oscillators present on the cyclobutane ring in α-pinene leads to a considerable signal intensity decrease (ca. 30–40%), meriting speculation that the cyclobutane moiety remains largely intact within the surface bound species present in the SOM formed upon α-pinene oxidation. These insights provide further clues as to the complexity of aerosol particle surfaces, and establish a framework for future investigations ofmore » the heterogeneous interactions between precursor terpenes and particle surfaces that lead to aerosol particle growth under dynamically changing conditions in the atmosphere.« less

Authors:

Upshur, Mary Alice ^[1]; Vega, Marvin M.  ^[1];

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• Search DOE PAGES for ORCID "0000-0002-1034-0856"

Bé, Ariana Gray  ^[1];

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• Search DOE PAGES for ORCID "0000-0002-0437-6190"

Chase, Hilary M. ^[1]; Zhang, Yue  ^[2];

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Tuladhar, Aashish  ^[3];

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• Search DOE PAGES for ORCID "0000-0003-2449-4984"

Chase, Zizwe A. ^[3]; Fu, Li  ^[3];

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• Search DOE PAGES for ORCID "0000-0003-0994-7789"

Ebben, Carlena J. ^[1]; Wang, Zheming  ^[3];

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Martin, Scot T.  ^[4];

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• Search DOE PAGES for ORCID "0000-0002-8996-7554"

Geiger, Franz M.  ^[1];

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• Search DOE PAGES for ORCID "0000-0001-8569-4045"

Thomson, Regan J.  ^[1]

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• Search DOE PAGES for ORCID "0000-0001-5546-4038"

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+ Show Author Affiliations

1. Department of Chemistry, Northwestern University, Evanston, USA
2. John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, USA
3. William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, USA
4. John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, USA, Department of Earth and Planetary Sciences

Publication Date:

Wed Sep 18 00:00:00 EDT 2019

Research Org.:

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Biological and Environmental Research (BER); National Science Foundation (NSF)

OSTI Identifier:

1545899

Alternate Identifier(s):

OSTI ID: 1577055

Report Number(s):

PNNL-SA-143837
Journal ID: ISSN 2041-6520; CSHCBM

Grant/Contract Number:  

AC05-76RL01830; CHE-1607640

Resource Type:

Published Article

Journal Name:

Chemical Science

Additional Journal Information:

Journal Name: Chemical Science Journal Volume: 10 Journal Issue: 36; Journal ID: ISSN 2041-6520

Publisher:

Royal Society of Chemistry (RSC)

Country of Publication:

United Kingdom

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY