Alkyl nitrates and secondary organic aerosol (SOA) produced during the oxidation of isoprene by nitrate radicals has been observed in the SAPHIR ( Simulation of Atmospheric PHotochemistry In a large Reaction Chamber) chamber. A 16 h dark experiment was conducted with temperatures at 289-301 K, and maximum concentrations of 11 ppb isoprene, 62.4 ppb O-3 and 31.1 ppb NOX. We find the yield of nitrates is 70 +/- 8% from the isoprene + NO3 reaction, and the yield for secondary dinitrates produced in the reaction of primary isoprene nitrates with NO3 is 40 +/- 20%. We find an effective rate constant for reaction of NO3 with the group of first generation oxidation products to be 7 x 10(-14) molecule(-1) cm(3) s(-1). At the low total organic aerosol concentration in the chamber (max=0.52 mu g m(-3)) we observed a mass yield (Delta SOA mass/Delta isoprene mass) of 2% for the entire 16 h experiment. However a comparison of the timing of the observed SOA production to a box model simulation of first and second generation oxidation products shows that the yield from the first generation products was <0.7% while the further oxidation of the initial products leads to a yield of 14% ( defined as Delta SOA/Delta isoprene(2X) where Delta isoprene(2X) is the mass of isoprene which reacted twice with NO3). The SOA yield of 14% is consistent with equilibrium partitioning of highly functionalized C-5 products of isoprene oxidation.
%0 Journal Article
%1 Rollins:2009p3596
%A Rollins, A. W
%A Kiendler-Scharr, A
%A Fry, J. L
%A Brauers, T
%A Brown, S. S
%A Dorn, H. P
%A Dube, W. P
%A Fuchs, H
%A Mensah, A
%A Mentel, T. F
%A Rohrer, F
%A Tillmann, R
%A Wegener, R
%A Wooldridge, P. J
%A Cohen, R. C
%D 2009
%J Atmospheric Chemistry and Physics
%K Chemical Chemistry, Constants Deciduous Forest, Gas-Phase Hydrocarbon Mass-Spectrometry, Mechanism, Nitrogen, No3 Peroxy-Radicals, Radicals, Rate Reactions, Reactive Ring-Down Spectroscopy,
%N 18
%P 6685--6703
%T Isoprene oxidation by nitrate radical: alkyl nitrate and secondary organic aerosol yields
%U http://apps.isiknowledge.com/InboundService.do?product=WOS&action=retrieve&SrcApp=Papers&UT=000270131400003&SID=3DBHInNJkJI5ndObejb&SrcAuth=mekentosj&mode=FullRecord&customersID=mekentosj&DestFail=http%253A%252F%252Faccess.isiproducts.com%252Fcustom_images%252Fwok_failed_auth.html
%V 9
%X Alkyl nitrates and secondary organic aerosol (SOA) produced during the oxidation of isoprene by nitrate radicals has been observed in the SAPHIR ( Simulation of Atmospheric PHotochemistry In a large Reaction Chamber) chamber. A 16 h dark experiment was conducted with temperatures at 289-301 K, and maximum concentrations of 11 ppb isoprene, 62.4 ppb O-3 and 31.1 ppb NOX. We find the yield of nitrates is 70 +/- 8% from the isoprene + NO3 reaction, and the yield for secondary dinitrates produced in the reaction of primary isoprene nitrates with NO3 is 40 +/- 20%. We find an effective rate constant for reaction of NO3 with the group of first generation oxidation products to be 7 x 10(-14) molecule(-1) cm(3) s(-1). At the low total organic aerosol concentration in the chamber (max=0.52 mu g m(-3)) we observed a mass yield (Delta SOA mass/Delta isoprene mass) of 2% for the entire 16 h experiment. However a comparison of the timing of the observed SOA production to a box model simulation of first and second generation oxidation products shows that the yield from the first generation products was <0.7% while the further oxidation of the initial products leads to a yield of 14% ( defined as Delta SOA/Delta isoprene(2X) where Delta isoprene(2X) is the mass of isoprene which reacted twice with NO3). The SOA yield of 14% is consistent with equilibrium partitioning of highly functionalized C-5 products of isoprene oxidation.
@article{Rollins:2009p3596,
abstract = {Alkyl nitrates and secondary organic aerosol (SOA) produced during the oxidation of isoprene by nitrate radicals has been observed in the SAPHIR ( Simulation of Atmospheric PHotochemistry In a large Reaction Chamber) chamber. A 16 h dark experiment was conducted with temperatures at 289-301 K, and maximum concentrations of 11 ppb isoprene, 62.4 ppb O-3 and 31.1 ppb NOX. We find the yield of nitrates is 70 +/- 8% from the isoprene + NO3 reaction, and the yield for secondary dinitrates produced in the reaction of primary isoprene nitrates with NO3 is 40 +/- 20%. We find an effective rate constant for reaction of NO3 with the group of first generation oxidation products to be 7 x 10(-14) molecule(-1) cm(3) s(-1). At the low total organic aerosol concentration in the chamber (max=0.52 mu g m(-3)) we observed a mass yield (Delta SOA mass/Delta isoprene mass) of 2% for the entire 16 h experiment. However a comparison of the timing of the observed SOA production to a box model simulation of first and second generation oxidation products shows that the yield from the first generation products was <0.7% while the further oxidation of the initial products leads to a yield of 14% ( defined as Delta SOA/Delta isoprene(2X) where Delta isoprene(2X) is the mass of isoprene which reacted twice with NO3). The SOA yield of 14% is consistent with equilibrium partitioning of highly functionalized C-5 products of isoprene oxidation.},
added-at = {2010-06-22T19:38:37.000+0200},
affiliation = {Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA},
author = {Rollins, A. W and Kiendler-Scharr, A and Fry, J. L and Brauers, T and Brown, S. S and Dorn, H. P and Dube, W. P and Fuchs, H and Mensah, A and Mentel, T. F and Rohrer, F and Tillmann, R and Wegener, R and Wooldridge, P. J and Cohen, R. C},
biburl = {https://www.bibsonomy.org/bibtex/283d69ab06c55cd727af7dafa789013ca/gsmith},
date-added = {2010-05-05 16:57:43 -0400},
date-modified = {2010-05-05 16:57:50 -0400},
interhash = {c6e382cd40c5bae0f446a6bd87770792},
intrahash = {83d69ab06c55cd727af7dafa789013ca},
journal = {Atmospheric Chemistry and Physics},
keywords = {Chemical Chemistry, Constants Deciduous Forest, Gas-Phase Hydrocarbon Mass-Spectrometry, Mechanism, Nitrogen, No3 Peroxy-Radicals, Radicals, Rate Reactions, Reactive Ring-Down Spectroscopy,},
language = {English},
local-url = {file://localhost/Users/geoffreysmith/Documents/Papers/Atmospheric%20Chemistry%20and%20Physics/2009/Atmospheric%20Chemistry%20and%20Physics,%209,%206685-6703%202009.pdf},
month = Jan,
number = 18,
pages = {6685--6703},
pmid = {000270131400003},
rating = {0},
timestamp = {2010-06-22T19:39:01.000+0200},
title = {Isoprene oxidation by nitrate radical: alkyl nitrate and secondary organic aerosol yields},
uri = {papers://E88B624E-D406-46FF-9D95-BB9C1AAE3FDC/Paper/p3596},
url = {http://apps.isiknowledge.com/InboundService.do?product=WOS&action=retrieve&SrcApp=Papers&UT=000270131400003&SID=3DBHInNJkJI5ndObejb&SrcAuth=mekentosj&mode=FullRecord&customersID=mekentosj&DestFail=http%253A%252F%252Faccess.isiproducts.com%252Fcustom_images%252Fwok_failed_auth.html},
volume = 9,
year = 2009
}