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Atmospheric Measurement Techniques An interactive open-access journal of the European Geosciences Union
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Discussion papers
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.

Submitted as: research article 10 Jul 2019

Submitted as: research article | 10 Jul 2019

Review status
This discussion paper is a preprint. It is a manuscript under review for the journal Atmospheric Measurement Techniques (AMT).

Isotopic characterization of nitrogen oxides (NOx), nitrous acid (HONO), and nitrate (NO3(p)) from laboratory biomass burning during FIREX

Jiajue Chai1, David J. Miller1,a, Eric Scheuer2, Jack Dibb2, Vanessa Selimovic3, Robert Yokelson3, Kyle J. Zarzana4,5,b, Steven S. Brown4,6, Abigail R. Koss4,5,6,c, Carsten Warneke5,6, and Meredith Hastings1 Jiajue Chai et al.
  • 1Department of Earth, Environmental and Planetary Sciences, and Institute at Brown for Environment and Society, Brown University, Providence, RI, USA
  • 2Institute for the Study of Earth, Ocean and Space, University of New Hampshire, Durham, NH, USA
  • 3Department of Chemistry, University of Montana, Missoula, USA
  • 4Chemical Sciences Division, NOAA Earth System Research Laboratory, Boulder, CO, USA
  • 5Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA
  • 6Department of Chemistry, University of Colorado, Boulder, CO, USA
  • anow at: Environmental Defense Fund, Boston, MA, USA
  • bnow at: Department of Chemistry, University of Colorado, Boulder, CO, USA
  • cDepartment of Civil and Environmental Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA

Abstract. New techniques have recently been developed to capture reactive nitrogen species for accurate measurement of their isotopic composition. Reactive nitrogen species play important roles in atmospheric oxidation capacity (hydroxyl radical and ozone formation) and may have impacts on air quality and climate. Tracking reactive nitrogen species and their chemistry in the atmosphere based upon concentration alone is challenging. Isotopic analysis provides a potential tool for tracking the sources and chemistry of species such as nitrogen oxides (NOx = NO + NO2), nitrous acid (HONO), nitric acid (HNO3) and particulate nitrate (NO3(p)). Here we study direct biomass burning (BB) emissions during the
 Fire Influence on Regional to Global Environments Experiment (FIREX, later evolved into FIREX-AQ) laboratory experiments at the Missoula Fire Laboratory in the fall of 2016.

An annular denuder system (ADS) developed to efficiently collect HONO for isotopic composition analysis was deployed to the Fire Lab study. Concentrations of HONO recovered from the ADS collection agree well with mean concentrations averaged over each fire measured by 4 other high time resolution techniques, including mist chamber/ion chromatography (MC/IC), open-path Fourier transform infrared spectroscopy (OP-FTIR), cavity enhanced spectroscopy (CES), proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF). The concentration validation ensures complete collection of BB emitted HONO, of which the isotopic composition is preserved during the collection process. In addition, the isotopic composition of NOx and NO3(p) from direct BB emissions were also characterized.

In 20 stack fires (direct emission within ~ 5 seconds of production by the fire) that burned various biomass materials, δ15N-NOx ranges from −4.3 ‰ to +7.0 ‰, falling near the middle of the range reported in previous work. The first measurements of δ15N-HONO and δ18O-HONO in biomass burning smoke reveal a range of −5.3 – +5.8 ‰ and +5.2 – +15.2 ‰ respectively. Both HONO and NOx are sourced from N in the biomass fuel and δ15N-HONO and δ15N-NOx are strongly correlated (R2 = 0.89, p < 0.001), suggesting NOx and HONO are connected via formation pathways.

Our δ15N of NOx, HONO and NO3(p) ranges can serve as important biomass burning source signatures, useful for constraining direct emissions of these species in environmental applications. The δ18O of HONO and NO3 obtained here verify our method is capable of determining oxygen isotopic composition in BB plumes. The δ18O for both species in this study reflect the laboratory conditions (i.e. a lack of photochemistry), and would be expected to track with the influence of ozone (O3), photochemistry and nighttime chemistry in real environments. The methods used in this study will be further applied in future field studies to quantitatively track reactive nitrogen cycling in fresh and aged Western US wildfire plumes.

Jiajue Chai et al.
Interactive discussion
Status: final response (author comments only)
Status: final response (author comments only)
AC: Author comment | RC: Referee comment | SC: Short comment | EC: Editor comment
Jiajue Chai et al.
Jiajue Chai et al.
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Short summary
Isotopic analysis offers a potential tool to distinguish between sources and interpret transformation pathways of atmospheric species. We applied recently developed techniques in our lab to characterize the isotopic composition of reactive nitrogen species (NOx, HONO, HNO3, p-NO3-) in fresh biomass burning emissions. Intercomparison with other techniques confirms suitability of our methods, allowing for future applications of our techniques in a variety of environments.
Isotopic analysis offers a potential tool to distinguish between sources and interpret...