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

Environmental Science & Technology
Andrew T LambeNeil M Donahue

Abstract

Hydroxyl radical (OH) uptake by organic aerosols, followed by heterogeneous oxidation, happens nearly at the collision frequency. Oxidation complicates the use of organic molecular markers such as hopanes for source apportionment, since receptor models assume markers are stable during transport. We report the oxidation kinetics of organic molecular markers (C(25)-C(32) n-alkanes, hopanes and steranes) in motor oil and primary organic aerosol emitted from a diesel engine at atmospherically relevant conditions inside a smog chamber. A thermal desorption aerosol gas chromatograph/mass spectrometer (TAG) and Aerodyne high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) were used to measure the changes in molecular comosition and bulk primary organic aerosol. From the measured changes in molecular composition, we calculated effective OH rate constants, effective relative rate constants, and effective uptake coefficients for molecular markers. Oxidation rates varied with marker volatility, with more volatile markers being oxidized at rates much faster than could be explained from heterogeneous oxidation. This rapid oxidation can be explained by significant gas-phase OH oxidation that dominates heterogeneous oxidation...Continue Reading

References

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Citations

Jul 26, 2011·Environmental Science & Technology·Akihiro FushimiKiyoshi Tanabe
Nov 24, 2011·Environmental Science & Technology·Heather Simon, Prakash V Bhave
Jul 4, 2012·Environmental Science & Technology·Changgeng LiuJinian Shu
Sep 6, 2012·Environmental Science & Technology·Gabriel IsaacmanAllen H Goldstein
Nov 23, 2012·Environmental Science & Technology·Changgeng LiuJinian Shu
Jul 24, 2013·Environmental Science & Technology·Lauren M PetrickYael Dubowski
Mar 24, 2012·The Journal of Physical Chemistry. a·Kaytlin M Henry, Neil M Donahue
Aug 24, 2010·Nature Chemistry·I J George, J P D Abbatt
Aug 8, 2012·Proceedings of the National Academy of Sciences of the United States of America·Neil M DonahueUrs Baltensperger
Feb 22, 2014·Environmental Science & Technology·Katheryn R KolesarChristopher D Cappa
Aug 30, 2014·Critical Reviews in Environmental Science and Technology·David A Morgott
Dec 15, 2016·Environmental Science & Technology·Houssni LamkaddamJean-François Doussin
Oct 11, 2014·Environmental Science. Processes & Impacts·Chang-Geng LiuPeng Zhang
Apr 1, 2015·Physical Chemistry Chemical Physics : PCCP·Chengyue LaiHong He
Jun 5, 2012·Chemical Society Reviews·J P D AbbattJ A Thornton
Apr 12, 2019·The Science of the Total Environment·Yee Ka WongJian Zhen Yu
Jul 7, 2018·The Journal of Physical Chemistry Letters·Yosuke SakamotoYoshizumi Kajii

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