Tracing the Origin and Fate of NOx in the Arctic Atmosphere Using Stable Isotopes in Nitrate

Atmospheric nitrogen oxides (NOx =NO+ NO2) play a pivotal role in the cycling of reactive nitrogen (ultimately deposited as nitrate) and the oxidative capacity of the atmosphere. Combined measurements of nitrogen and oxygen stable isotope ratios of nitrate collected in the Arctic atmosphere were used to infer the origin and fate of NOx and nitrate on a seasonal basis. In spring, photochemically driven emissions of reactive nitrogen from the snowpack into the atmosphere make local oxidation of NOx by bromine oxide the major contributor to the nitrate budget. The comprehensive isotopic composition of nitrate provides strong constraints on the relative importance of the key atmospheric oxidants in the present atmosphere, with the potential for extension into the past using ice cores.

[1]  J. Galloway,et al.  Transformation of the Nitrogen Cycle: Recent Trends, Questions, and Potential Solutions , 2008, Science.

[2]  S. Morin,et al.  The NO+O3 reaction: a triple oxygen isotope perspective on the reaction dynamics and atmospheric implications for the transfer of the ozone isotope anomaly. , 2008, The Journal of chemical physics.

[3]  E. Elliott,et al.  Nitrogen isotopes as indicators of NO(x) source contributions to atmospheric nitrate deposition across the midwestern and northeastern United States. , 2007, Environmental science & technology.

[4]  P. Shepson,et al.  An overview of snow photochemistry: evidence, mechanisms and impacts , 2007 .

[5]  Lars Kaleschke,et al.  Halogens and their role in polar boundary-layer ozone depletion , 2007 .

[6]  D. Shindell.  Local and remote contributions to Arctic warming , 2007 .

[7]  A. Stohl,et al.  Arctic Air Pollution: Origins and Impacts , 2007, Science.

[8]  S. Bekki,et al.  Signature of Arctic surface ozone depletion events in the isotope anomaly ( Δ 17 O) of atmospheric nitrate , 2007 .

[9]  D. Sigman,et al.  Triple oxygen isotope analysis of nitrate using the denitrifier method and thermal decomposition of N2O. , 2007, Analytical chemistry.

[10]  D. Sigman,et al.  Nitrogen and oxygen isotopic constraints on the origin of atmospheric nitrate in coastal Antarctica , 2006 .

[11]  Louisa Emmons,et al.  Ozone pollution from future ship traffic in the Arctic northern passages , 2006 .

[12]  A. Stohl.  Characteristics of atmospheric transport into the Arctic troposphere , 2006 .

[13]  M. Thiemens.  HISTORY AND APPLICATIONS OF MASS-INDEPENDENT ISOTOPE EFFECTS , 2006 .

[14]  A. Ravishankara,et al.  Variability in Nocturnal Nitrogen Oxide Processing and Its Role in Regional Air Quality , 2006, Science.

[15]  E. Quansah,et al.  Isotopic view on nitrate loss in Antarctic surface snow , 2005 .

[16]  D. Sigman,et al.  Seasonal variations in N and O isotopes of nitrate in snow at Summit, Greenland: Implications for the study of nitrate in snow and ice cores , 2004 .

[17]  A. Tye,et al.  Low 15N/14N ratios for nitrate in snow in the High Arctic (79°N) , 2004 .

[18]  C. Brenninkmeijer,et al.  Isotope effects in the chemistry of atmospheric trace compounds. , 2003, Chemical reviews.

[19]  M. Thiemens,et al.  First measurements and modeling of Δ17O in atmospheric nitrate , 2003 .

[20]  R. Hillamo,et al.  Fluxes of nitrates between snow surfaces and the atmosphere in the European high Arctic , 2003 .

[21]  Paul B. Shepson,et al.  Air-Snow Interactions and Atmospheric Chemistry , 2002, Science.

[22]  John P. Burrows,et al.  GOME MEASUREMENTS OF STRATOSPHERIC AND TROPOSPHERIC BrO , 2002 .

[23]  H. Beine,et al.  The seasonal cycle of peroxyacetyl nitrate (PAN) in the European Arctic , 2000 .

[24]  James N. Pitts,et al.  Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications , 1999 .

[25]  L. Barrie,et al.  Arctic lower tropospheric aerosol trends and composition at Alert, Canada: 1980–1995 , 1999 .

[26]  P. Shepson,et al.  Evidence of NOx production within or upon ice particles in the Greenland snowpack , 1999 .

[27]  M. Legrand,et al.  Atmospheric near‐surface nitrate at coastal Antarctic sites , 1998 .

[28]  P. Crutzen,et al.  High concentrations and photochemical fate of oxygenated hydrocarbons in the global troposphere , 1995, Nature.

[29]  R. Michener,et al.  Stable isotopes in ecology and environmental science , 1995 .

[30]  D. Kley,et al.  On the interaction of isotopic exchange processes with photochemical reactions in atmospheric oxides of nitrogen , 1993 .

[31]  P. Crutzen.  The influence of nitrogen oxides on the atmospheric ozone content , 1970 .

[32]  P. Leighton,et al.  Photochemistry of Air Pollution , 1961 .