Total Peroxy Nitrates (ΣPNs) in the atmosphere: the Thermal Dissociation-Laser Induced Fluorescence (TD-LIF) technique and comparisons to speciated PAN measurements

Author:

Wooldridge P. J.,Perring A. E.,Bertram T. H.,Flocke F. M.,Roberts J. M.,Singh H. B.,Huey L. G.,Thornton J. A.,Wolfe G. M.,Murphy J. G.,Fry J. L.,Rollins A. W.,LaFranchi B. W.,Cohen R. C.

Abstract

Abstract. Peroxyacetyl nitrate (PAN) and its chemical analogues are increasingly being quantified in the ambient atmosphere by thermal dissociation (TD) followed by detection of either the peroxyacyl radical or the NO2 product. Here we present details of the technique developed at University of California, Berkeley which detects the sum of all peroxynitrates (ΣPNs) via laser-induced fluorescence (LIF) of the NO2 product. We review the various deployments and compare the Berkeley ΣPNs measurements with the sums of PAN and its homologue species detected individually by other instruments. The observed TD-LIF ΣPNs usually agree to within 10% with the summed individual species, thus arguing against the presence of significant concentrations of unmeasured PAN-type compounds in the atmosphere, as suggested by some photochemical mechanisms. Examples of poorer agreement are attributed to a sampling inlet design that is shown to be inappropriate for high NOx conditions. Interferences to the TD-LIF measurements are described along with strategies to minimize their effects.

Publisher

Copernicus GmbH

Subject

Atmospheric Science

Reference82 articles.

1. Alaghmand, M., Slade, N. J., Mielke, L., Starn, T., Carroll, M., Bertman, S. B., Stevens, P.S., and Shepson, P.B., Determination of reactive nitrogen species (NOx, NOy-HNO3, Peroxyacetyl Nitrates, Total Organic Nitrates) during PROPHET summer 2008 intensive, Eos Trans. AGU, 89(53), Fall Meet. Suppl., Abstract A31A-0069, 2008.

2. Anderson, L. C. and Fahey, D. W.: Studies with ClONO2: thermal dissociation rate and catalytic conversion to nitric oxide using an NO/O3 chemiluminescence detector, J. Phys. Chem., 94, 644–652, 1990.

3. Apodaca, R. L., Simpson, W. R., Ball, S. M., Bauers, T., Brown, S. S., Cohen, R. C., Crowley, J., Dorn, H.-P., Dube, W. P., Fry, J. L., Fuchs, H., Haseler, R., Heitnam, U., Kato, S., Kajii, Y., Kiendler-Scharr, A., Kleffmann, J., Labazan, I., Matsumoto, J., Nishada, S., Rollins, A. W., Tillmann, R., Wahner, A., Wegener, R., and Wooldridge, P. J.: Intercomparison of N2O5 sensors using the SAPHIR reaction chamber, Atmos. Chem. and Phys. Discuss., in preparation, 2010.

4. Atlas, E. L., Ridley, B. A., and Cantrell, C.: The Tropospheric Ozone Production about the Spring Equinox (TOPSE) experiment: Introduction, J. Geophys. Res., 108, 8353, https://doi.org/10.1029/2002JD003172, 2003.

5. Baulch, D. L., Duxbury, J., Grant, S. J., and Montague, D. C.: Evaluated kinetic data for high temperature reactions. Volume 4 Homogeneous gas phase reactions of halogen- and cyanide- containing species, J. Phys. Chem. Ref. Data, Supplement No. 1 to vol. 10, 1981.

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