References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-11-6529-2011

Characterization of a thermal decomposition chemical ionization mass spectrometer for the measurement of peroxy acyl nitrates (PANs) in the atmosphere

Zheng

¹ ² Flocke

F. M.

¹ Tyndall

G. S.

¹ Swanson

¹ ² ⁵ Orlando

J. J.

¹ Roberts

J. M.

³ Huey

L. G.

⁴ Tanner

D. J.

⁴

Atmospheric Chemistry Division, National Center for Atmospheric Research, Boulder, Colorado, USA

Coorperative Institute for Research in Environmental Science, University of Colorado, Boulder, Colorado, USA

Chemical Sciences Division, Earth System Research Lab, National Oceanic and Atmospheric Administration, Boulder, Colorado, USA

School of Earth and Atmospheric Science, Georgia Institute of Technology, Atlanta, Georgia, USA

now at: Northrop Grumman Aerospace Systems, Redondo Beach, California, USA

08 07 2011

11 13 6529 6547

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.

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This paper presents a detailed laboratory characterization of a thermal dissociation chemical ionization mass spectrometer (TD-CIMS) for the atmospheric measurement of Peroxyacetyl nitrate (PAN) and its homologues (PANs). PANs are efficiently dissociated in a heated inlet and the resulting peroxy acyl radicals are reacted with I− ions in a flow tube. The mass spectrometer detects the corresponding carboxylate ions. PAN, peroxypropionyl nitrate (PPN), peroxyisobutyryl nitrate (PiBN), peroxy-n-butyryl nitrate (PnBN), peroxyacryloyl nitrate (APAN), peroxycrotonyl nitrates (CPAN) and peroxymethacryloyl nitrate (MPAN) were cross-calibrated with both a dual channel GC/ECD and a total odd-nitrogen (NOy) instrument for the NCAR TD-CIMS' typical aircraft operation conditions. In addition, the instrument sensitivity to a number of more exotic PANs (peroxyhydroxyacetyl nitrate, methoxyformyl peroxynitrate, and peroxybenzoyl nitrate) was evaluated qualitatively by comparisons with a long-path FTIR instrument. The sensitivity for PPN is slightly higher than that of PAN. Larger aliphatic and olefinic PAN compounds generally showed lower sensitivities. We postulate that these differences are owing to secondary reactions in the thermal decomposition region, which either reduce the yield of peroxy acyl radicals or cause losses of these radicals through intramolecular decomposition. The relative importance of these secondary reactions varies considerably between different PAN species. Results also indicate that the reaction of the larger peroxy acyl radicals with the ion-water cluster, I−(H2O)n proceeds about an order of magnitude faster than with I− alone, as has been observed for peroxy acetyl radicals. Sensitivity variations among the individual PAN species at very low water vapor were observed. The results call for careful evaluation of each PAN species to be measured and for each desired operating condition of a TD-CIMS instrument.

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