A Near‐Global Atmospheric Distribution of N2O Isotopologues

The distributions of the four most abundant isotopologues and isotopomers (N2O, 15NNO, N15NO, and NN18O) of nitrous oxide have been measured in the Earth's stratosphere by infrared remote sensing with the Atmospheric Chemistry Experiment (ACE) Fourier transform spectrometer. These satellite observations have provided a near‐global picture of N2O isotopic fractionation. The relative abundances of the heavier species increase with altitude and with latitude in the stratosphere as the air becomes older. The heavy isotopologues are enriched by 20–30% in the upper stratosphere and even more over the poles. These observations are in general agreement with model predictions made with the Whole Atmosphere Community Climate Model (WACCM). A detailed 3‐D chemical transport model is needed to account for the global isotopic distributions of N2O and to infer sources and sinks.

[1]  M. McElroy,et al.  Absorption of solar radiation by O2 - Implications for O3 and lifetimes of N2O, CFCl3, and CF2Cl2 , 1993 .

[2]  Y. Yung,et al.  Isotopic fractionation of stratospheric nitrous oxide , 1997, Science.

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

[4]  G. Toon,et al.  Vertical profiles of nitrous oxide isotopomer fractionation measured in the stratosphere , 2000 .

[5]  Peter F. Bernath,et al.  The Atmospheric Chemistry Experiment (ACE) , 2001 .

[6]  P. Crutzen,et al.  Wavelength dependence of isotope fractionation in N 2 O photolysis , 2002 .

[7]  C. Brenninkmeijer,et al.  Intramolecular 15N and 18O fractionation in the reaction of N2O with O(1D) and its implications for the stratospheric N2O isotope signature , 2002 .

[8]  D. Waugh,et al.  AGE OF STRATOSPHERIC AIR: THEORY, OBSERVATIONS, AND MODELS , 2002 .

[9]  Peter F. Bernath.  Atmospheric Chemistry Experiment (ACE): an overview , 2002, SPIE Optics + Photonics.

[10]  C. McLinden,et al.  Global modeling of the isotopic analogues of N2O: Stratospheric distributions, budgets, and the 17O–18O mass‐independent anomaly , 2003 .

[11]  Y. Yung,et al.  PRODUCTION, ISOTOPIC COMPOSITION, AND ATMOSPHERIC FATE OF BIOLOGICALLY PRODUCED NITROUS OXIDE , 2003 .

[12]  C. Brenninkmeijer,et al.  Complete and accurate mass spectrometric isotope analysis of tropospheric nitrous oxide , 2003 .

[13]  Peter F. Bernath,et al.  Atmospheric chemistry experiment (ACE): mission overview , 2004, SPIE Optics + Photonics.

[14]  J. Barnola,et al.  Constraints on N 2 O budget changes since pre-industrial time from new firn air and ice core isotope measurements , 2005 .

[15]  P. Bernath,et al.  Retrievals for the atmospheric chemistry experiment Fourier-transform spectrometer. , 2005, Applied optics.

[16]  Gang Li,et al.  The HITRAN 2008 molecular spectroscopic database , 2005 .

[17]  T. Röckmann,et al.  High‐precision determination of the changing isotopic composition of atmospheric N2O from 1990 to 2002 , 2005 .

[18]  T. Röckmann,et al.  Probing stratospheric transport and chemistry with new balloon and aircraft observations of the meridional and vertical N 2 O isotope distribution , 2006 .

[19]  K. Kawamura,et al.  Temporal variations of the atmospheric nitrous oxide concentration and its δ15N and δ18O for the latter half of the 20th century reconstructed from firn air analyses , 2007 .

[20]  M. McElroy,et al.  Absorption of Solar Radiation by 02 ' Implications for 03 and Lifetimes of N 2 O , CFC 13 , and CF 2 C 12 , 2007 .

[21]  J. C. McConnell,et al.  N2O production by high energy auroral electron precipitation , 2008 .

[22]  A. Ravishankara,et al.  Nitrous Oxide (N2O): The Dominant Ozone-Depleting Substance Emitted in the 21st Century , 2009, Science.

[23]  D. Griffith,et al.  Absolute calibration of the intramolecular site preference of 15N fractionation in tropospheric N2O by FT-IR spectroscopy. , 2009, Analytical chemistry.

[24]  M. Johnson,et al.  Isotope effects in N 2 O photolysis from first principles , 2011 .

[25]  P. Bernath,et al.  Stratospheric lifetimes of CFC-12, CCl 4 , CH 4 , CH 3 Cl and N 2 O from measurements made by the Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS) , 2013 .

[26]  Daniel R. Marsh,et al.  Climate change from 1850 to 2005 simulated in CESM1(WACCM) , 2013 .

[27]  T. Machida,et al.  Decadal time series of tropospheric abundance of N2O isotopomers and isotopologues in the Northern Hemisphere obtained by the long‐term observation at Hateruma Island, Japan , 2013 .

[28]  E. R. Polovtseva,et al.  The HITRAN2012 molecular spectroscopic database , 2013 .

[29]  J. Houghton.  Climate Change 2013 - The Physical Science Basis: Working Group I Contribution to the Fifth Assessment Report of the Intergovernmental Panel on Climate Change , 2014 .

[30]  L. Oman,et al.  Measuring and modeling the lifetime of nitrous oxide including its variability , 2015, Journal of geophysical research. Atmospheres : JGR.

[31]  S. Schiff,et al.  From the Ground Up: Global Nitrous Oxide Sources are Constrained by Stable Isotope Values , 2015, PloS one.

[32]  V. L. Orkin,et al.  Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies: Evaluation Number 18 , 2015 .

[33]  M. Johnson,et al.  Clumped isotope perturbation in tropospheric nitrous oxide from stratospheric photolysis , 2015 .

[34]  P. Bernath,et al.  Global stratospheric measurements of the isotopologues of methane from the Atmospheric Chemistry Experiment Fourier transform spectrometer , 2015 .

[35]  Jan Kaiser,et al.  Development of an atmospheric N 2 O isotopocule model and optimization procedure, and application to source estimation , 2015 .

[36]  P. Bernath,et al.  Near-global distribution of CO isotopic fractionation in the Earth's atmosphere , 2016 .

[37]  P. Bernath,et al.  Nitrous oxide in the atmosphere: First measurements of a lower thermospheric source , 2016 .

[38]  M. Uematsu,et al.  Vertical distributions of N 2 O isotopocules in the equatorial stratosphere , 2017 .