References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-12-5773-2012

Importance of biogenic precursors to the budget of organic nitrates: observations of multifunctional organic nitrates by CIMS and TD-LIF during BEARPEX 2009

Beaver

M. R.

¹ ⁴ Clair

J. M. St.

¹ Paulot

¹ Spencer

K. M.

¹ Crounse

J. D.

¹ LaFranchi

B. W.

² ⁵ Min

K. E.

² Pusede

S. E.

² Wooldridge

P. J.

² Schade

G. W.

³ Park

³ ⁶ Cohen

R. C.

² Wennberg

P. O.

California Institute of Technology, Pasadena, CA, USA

University of California, Berkeley, CA, USA

Texas A&M University, College Station, TX, USA

now at: National Exposure Research Laboratory, Environmental Protection Agency, Research Triangle Park, NC, USA

now at: Center for Accelerator Mass Spectrometry, Lawrence Livermore National Laboratory, Livermore, CA, USA

now at: University of California, Los Angeles, CA, USA

03 07 2012

12 13 5773 5785

This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

This article is available from http://www.atmos-chem-phys.net/12/5773/2012/acp-12-5773-2012.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/12/5773/2012/acp-12-5773-2012.pdf

Alkyl and multifunctional organic nitrates, molecules of the chemical form RONO2, are products of chain terminating reactions in the tropospheric HOx and NOx catalytic cycles and thereby impact ozone formation locally. Many of the molecules in the class have lifetimes that are long enough that they can be transported over large distances. If the RONO2 then decompose to deliver NOx to remote regions they affect ozone production rates in locations distant from the original NOx source. While measurements of total RONO2 (ΣANs) and small straight chain alkyl nitrates are routine, measurements of the specific multifunctional RONO2 molecules that are believed to dominate the total have rarely been reported and never reported in coincidence with ambient ΣANs measurements. Here we describe observations obtained during the BEARPEX 2009 experiment including ΣANs and a suite of multifunctional nitrates including isoprene derived hydroxynitrates, oxidation products of those nitrates, 2-methyl-3-buten-2-ol (MBO) derived hydroxynitrates, and monoterpene nitrates. At the BEARPEX field site, the sum of the individual biogenically derived nitrates account for two-thirds of the ΣANs, confirming predictions of the importance of biogenic nitrates to the NOy budget. Isoprene derived nitrates, transported to the site, are a much larger fraction of the ΣANs at the site than the nitrates derived from the locally emitted MBO. Evidence for additional nitrates, possibly from nocturnal chemistry of isoprene and α-pinene, is presented.

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