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Constraining the atmospheric N2O budget from intramolecular site preference in N2O isotopomers

Nature volume 405, pages 330–334 (2000)Cite this article

Abstract

Nitrous oxide (N2O) is an important trace gas in the atmosphere. It is an active greenhouse gas in the troposphere and it also controls ozone concentration in the stratosphere through nitric oxide production1. One way to trace the geochemical cycle of N2O is by measuring the natural abundance of stable isotopes, namely 15N and 18O (refs 2,3,4,5,6,7,8,9,10,11, 12,13,14,15). Here we report the intramolecular distribution of 15N within the linear NNO molecule, determined by measuring molecular and fragment ions of N2O on a modified mass spectrometer. This revealed a preference for 15N at the central N position, or α-site, within N2O isotopomers (isotope-containing molecules). Moreover, this preference varied significantly throughout the atmosphere. In the troposphere, low α-site preference indicates local emission of N2O from soils and fossil-fuel combustion, each with distinct isotopomer signatures, which then mixes with background N2O. In the stratosphere, on the other hand, loss of N2O is observed as enhanced α-site preference for 15N, due to fractionation during ultraviolet photolysis of N2O. We have constructed an atmospheric mass balance of N2O, incorporating isotopomer abundance, which shows that the intramolecular distribution of 15N is a parameter that has the potential to increase significantly the resolution with which sources and sinks of N2O can be identified and quantified in the atmosphere.

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Figure 1: Schematic diagram of the measurement system for isotopomer ratios in N2O.
Figure 2: Site preference and nitrogen isotope ratio at the β-site in atmospheric N2O.
Figure 3: Isotopomer and isotope compositions in stratospheric N2O.

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Acknowledgements

We thank the members of the balloon launch group of The Institute of Space and Astronautical Science, and the cryogenic sampling group, for cooperation in the stratospheric sampling. We thank M. Thiemens for comments that improved an earlier version of the manuscript.

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  1. Sakae Toyoda

    Present address: Department of Environmental Chemistry and Engineering, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama, 226-8502, Japan

Authors and Affiliations

  1. Department of Environmental Science and Technology, Interdisciplinary Graduate School of Science and Engineering Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama , 226-8502, Japan

    Naohiro Yoshida

  2. CREST Project, Japan Science and Technology Corporation, Kawaguchi, 332-0012, Saitama, Japan

    Naohiro Yoshida & Sakae Toyoda

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  1. Naohiro Yoshida
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  2. Sakae Toyoda
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Correspondence to Naohiro Yoshida.

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Yoshida, N., Toyoda, S. Constraining the atmospheric N2O budget from intramolecular site preference in N2O isotopomers. Nature 405, 330–334 (2000). https://doi.org/10.1038/35012558

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