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Observations of total RONO_2 over the boreal forest: NO_x sinks and HNO_3 sources

Browne, E. C. and Min, K.-E. and Wooldridge, P. J. and Apel, E. and Blake, D. R. and Brune, W. H. and Cantrell, C. A. and Cubison, M. J. and Diskin, G. S. and Jimenez, J. L. and Weinheimer, A. J. and Wennberg, P. O. and Wisthaler, A. and Cohen, R. C. (2013) Observations of total RONO_2 over the boreal forest: NO_x sinks and HNO_3 sources. Atmospheric Chemistry and Physics, 13 (9). pp. 4543-4562. ISSN 1680-7316.

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In contrast with the textbook view of remote chemistry where HNO_3 formation is the primary sink of nitrogen oxides, recent theoretical analyses show that formation of RONO_2 (ΣANs) from isoprene and other terpene precursors is the primary net chemical loss of nitrogen oxides over the remote continents where the concentration of nitrogen oxides is low. This then increases the prominence of questions concerning the chemical lifetime and ultimate fate of ΣANs. We present observations of nitrogen oxides and organic molecules collected over the Canadian boreal forest during the summer which show that ΣANs account for ~20% of total oxidized nitrogen and that their instantaneous production rate is larger than that of HNO3. This confirms the primary role of reactions producing ΣANs as a control over the lifetime of NO_x (NO_x = NO + NO_2) in remote, continental environments. However, HNO_3 is generally present in larger concentrations than ΣANs indicating that the atmospheric lifetime of ΣANs is shorter than the HNO_3 lifetime. We investigate a range of proposed loss mechanisms that would explain the inferred lifetime of ΣANs finding that in combination with deposition, two processes are consistent with the observations: (1) rapid ozonolysis of isoprene nitrates where at least ~40% of the ozonolysis products release NO_x from the carbon backbone and/or (2) hydrolysis of particulate organic nitrates with HNO_3 as a product. Implications of these ideas for our understanding of NO_x and NO_y budget in remote and rural locations are discussed.

Item Type:Article
Related URLs:
URLURL TypeDescription
Brune, W. H.0000-0002-1609-4051
Diskin, G. S.0000-0002-3617-0269
Jimenez, J. L.0000-0001-6203-1847
Weinheimer, A. J.0000-0001-6175-8286
Wennberg, P. O.0000-0002-6126-3854
Cohen, R. C.0000-0001-6617-7691
Additional Information:© 2013 the Author(s). This work is distributed under the Creative Commons Attribution 3.0 License. Published by Copernicus Publications on behalf of the European Geosciences Union. Received: 11 December 2012; Published in Atmos. Chem. Phys. Discuss.: 4 January 2013 Revised: 8 April 2013; Accepted: 12 April 2013; Published: 2 May 2013. The analysis described here was supported by NASA grant NNX08AR13G and a NASA Earth Systems Science Fellowship to ECB. MJC and JLJ were supported by NASA NNX08AD39G and NNX12AC03G. PTR-MS measurements were supported by the Austrian Research Promotion Agency (FFG-ALR) and the Tiroler Zukunftstiftung, and were carried out with the help/support of T. Mikoviny, M. Graus, A. Hansel and T. D. Maerk. We thank the NASA ground and flight crews for their hard work during ARCTAS. Edited by: F. Keutsch
Funding AgencyGrant Number
NASA Earth Systems Science FellowshipUNSPECIFIED
FWF Der WissenschaftsfondsUNSPECIFIED
Issue or Number:9
Record Number:CaltechAUTHORS:20130709-103850684
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Official Citation:Browne, E. C., Min, K.-E., Wooldridge, P. J., Apel, E., Blake, D. R., Brune, W. H., Cantrell, C. A., Cubison, M. J., Diskin, G. S., Jimenez, J. L., Weinheimer, A. J., Wennberg, P. O., Wisthaler, A., and Cohen, R. C.: Observations of total RONO2 over the boreal forest: NOx sinks and HNO3 sources, Atmos. Chem. Phys., 13, 4543-4562, doi:10.5194/acp-13-4543-2013, 2013.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:39268
Deposited By: Jason Perez
Deposited On:10 Jul 2013 21:32
Last Modified:09 Mar 2020 13:19

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