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Atmospheric Measurement Techniques An interactive open-access journal of the European Geosciences Union
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© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.
© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.

  20 Jul 2020

20 Jul 2020

Review status
This preprint is currently under review for the journal AMT.

Thermal dissociation cavity ring-down spectrometer (TD-CRDS) for detection of organic nitrates in gas and particle phase

Natalie I. Keehan1, Bellamy Brownwood1, Andrey Marsavin1, Douglas A. Day2, and Juliane L. Fry1 Natalie I. Keehan et al.
  • 1Chemistry Department and Environmental Studies Program, Reed College, Portland, OR 97205, USA
  • 2Cooperative Institute for Research in Environmental Sciences (CIRES) and Department of Chemistry, University of Colorado, Boulder, CO 80303, USA

Abstract. A thermal dissociation – cavity ring-down spectrometer (TD-CRDS) was built to measure NO2, peroxy nitrates (PNs), alkyl nitrates (ANs), and HNO3 in the gas and particle phase. The detection limit of the TD-CRDS is 0.66 ppb for ANs, PNs, and HNO3 and 0.48 ppb for NO2. For all four classes of NOy, the time resolution for separate gas and particle measurements is 8 minutes and for total gas + particle measurements is 3 minutes. The accuracy of the TD-CRDS was tested by comparison of NO2 measurements with a chemiluminescent NOx monitor, and aerosol-phase ANs with an Aerosol Mass Spectrometer (AMS). N2O5 causes significant interference in the PNs and ANs channel under high oxidant concentration chamber conditions, and ozone pyrolysis causes a negative interference in the HNO3 channel. Both interferences can be quantified and corrected for, but must be considered when using TD techniques for measurements of organic nitrates. This instrument has been successfully deployed for chamber measurements at widely varying concentrations, as well as ambient measurements of NOy.

Natalie I. Keehan et al.

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Natalie I. Keehan et al.

Natalie I. Keehan et al.


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Publications Copernicus
Short summary
This paper describes a new instrument (a thermal dissociation cavity ringdown spectrometer, TD-CRDS) for the measurements of key atmospheric gaseous and particle-phase molecules containing the nitrate functional group. Several operational considerations that affect the measurements are described, as well as several characterization experiments comparing the TD-CRDS measurements to analogous measurements from other instruments. Examples are given using TD-CRDS for ambient and laboratory studies.
This paper describes a new instrument (a thermal dissociation cavity ringdown spectrometer,...