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AGU: Journal of Geophysical Research, Atmospheres

 

Keywords

  • nitrate
  • isotopes
  • Greenland

Index Terms

  • Atmospheric Composition and Structure: General or miscellaneous
  • Atmospheric Composition and Structure: Troposphere: composition and chemistry
  • Biogeosciences: Isotopic composition and chemistry
  • Cryosphere: Snow
Abstract
Cited By (0)
 

Abstract

Isotopic ratios in gas-phase HNO3 and snow nitrate at Summit, Greenland

Julia C. Jarvis

Department of Earth and Space Sciences, University of Washington, Seattle, Washington, USA

Meredith G. Hastings

Department of Geological Sciences and Environmental Change Initiative, Brown University, Providence, Rhode Island, USA

Eric J. Steig

Department of Earth and Space Sciences, University of Washington, Seattle, Washington, USA

Shelley A. Kunasek

Department of Earth and Space Sciences, University of Washington, Seattle, Washington, USA

Measurements of the isotope ratios of snow nitrate and atmospheric gas-phase HNO3 (15N/14N and 18O/16O) from Summit, Greenland provide new observational constraints on postdepositional processing of snowpack nitrate. The δ 15N of NO3 is similar in surface snow and in air sampled 1.5 m above the snow surface during Spring and Summer 2006, ranging between −15 and +6‰ versus N2. The δ 18O of NO3 , however, is ∼40‰ higher in surface snow than air samples. Photochemical box modeling of HNO3 chemistry at Summit suggests that the δ 18O of the air samples is derived predominantly from gas-phase HNO3 originating from photolyzed snow nitrate. Measurements of isotopically labeled nitrate in surface snow confirm that photolytic recycling of snowpack nitrate, in which photolyzed nitrate products recombine to form HNO3 that is subsequently redeposited to the snow surface, does occur at Summit. Calculations incorporating these measurements suggest that photolytic recycling of snow nitrate at Summit will have a maximum −7.5‰ change on the δ 18O of nitrate buried in snow, while photolytic loss of snow nitrate will decrease the δ 18O of buried nitrate by 0.9‰. Photolytic recycling and loss will increase the δ 15N of buried snow nitrate, the degree to which depends on the nitrogen isotope fractionation of nitrate photolysis. Finally, a comparison of surface snow and snowpit samples demonstrates the preservation of the seasonal cycle in isotope ratios of snow nitrate.

Received 27 March 2009; accepted 24 June 2009; published 5 September 2009.

Citation: Jarvis, J. C., M. G. Hastings, E. J. Steig, and S. A. Kunasek (2009), Isotopic ratios in gas-phase HNO3 and snow nitrate at Summit, Greenland, J. Geophys. Res., 114, D17301, doi:10.1029/2009JD012134.

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