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<front>
<journal-meta>
<journal-id journal-id-type="publisher">EGUsphere</journal-id>
<journal-title-group>
<journal-title>EGUsphere</journal-title>
<abbrev-journal-title abbrev-type="publisher">EGUsphere</abbrev-journal-title>
<abbrev-journal-title abbrev-type="nlm-ta">EGUsphere</abbrev-journal-title>
</journal-title-group>
<issn pub-type="epub"></issn>
<publisher><publisher-name>Copernicus Publications</publisher-name>
<publisher-loc>Göttingen, Germany</publisher-loc>
</publisher>
</journal-meta>
<article-meta>
<article-id pub-id-type="doi">10.5194/egusphere-2026-874</article-id>
<title-group>
<article-title>An absolute reference frame for nitrous oxide clumped and position-specific isotopes provided by thermal equilibration</article-title>
</title-group>
<contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Magyar</surname>
<given-names>Paul M.</given-names>
<ext-link>https://orcid.org/0000-0003-0234-247X</ext-link>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Kueter</surname>
<given-names>Nico</given-names>
<ext-link>https://orcid.org/0000-0003-3620-5414</ext-link>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Brunamonti</surname>
<given-names>Simone</given-names>
<ext-link>https://orcid.org/0000-0001-7667-443X</ext-link>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Zhang</surname>
<given-names>Naizhong</given-names>
<ext-link>https://orcid.org/0000-0002-0065-8641</ext-link>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Prokhorov</surname>
<given-names>Ivan</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Chénier</surname>
<given-names>Noémy</given-names>
<ext-link>https://orcid.org/0000-0001-8854-7294</ext-link>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="aff" rid="aff4">
<sup>4</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Emmenegger</surname>
<given-names>Lukas</given-names>
<ext-link>https://orcid.org/0000-0002-9812-3986</ext-link>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Tuzson</surname>
<given-names>Béla</given-names>
<ext-link>https://orcid.org/0000-0001-7442-5405</ext-link>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Mohn</surname>
<given-names>Joachim</given-names>
<ext-link>https://orcid.org/0000-0002-9799-1001</ext-link>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
</contrib-group><aff id="aff1">
<label>1</label>
<addr-line>Empa, Laboratory for Air Pollution / Environmental Technology, 8600 Dübendorf, Switzerland</addr-line>
</aff>
<aff id="aff2">
<label>2</label>
<addr-line>Department of Earth and Planetary Sciences, ETH Zürich, 8092 Zurich, Switzerland</addr-line>
</aff>
<aff id="aff3">
<label>3</label>
<addr-line>Geological Institute, RWTH Aachen University, 52062 Aachen, Germany</addr-line>
</aff>
<aff id="aff4">
<label>4</label>
<addr-line>Department of Environmental Science, University of Basel, 4056 Basel, Swizterland</addr-line>
</aff>
<pub-date pub-type="epub">
<day>31</day>
<month>03</month>
<year>2026</year>
</pub-date>
<volume>2026</volume>
<fpage>1</fpage>
<lpage>25</lpage>
<permissions>
<copyright-statement>Copyright: &#x000a9; 2026 Paul M. Magyar et al.</copyright-statement>
<copyright-year>2026</copyright-year>
<license license-type="open-access">
<license-p>This work is licensed under the Creative Commons Attribution 4.0 International License. To view a copy of this licence, visit <ext-link ext-link-type="uri"  xlink:href="https://creativecommons.org/licenses/by/4.0/">https://creativecommons.org/licenses/by/4.0/</ext-link></license-p>
</license>
</permissions>
<self-uri xlink:href="https://egusphere.copernicus.org/preprints/2026/egusphere-2026-874/">This article is available from https://egusphere.copernicus.org/preprints/2026/egusphere-2026-874/</self-uri>
<self-uri xlink:href="https://egusphere.copernicus.org/preprints/2026/egusphere-2026-874/egusphere-2026-874.pdf">The full text article is available as a PDF file from https://egusphere.copernicus.org/preprints/2026/egusphere-2026-874/egusphere-2026-874.pdf</self-uri>
<abstract>
<p>Clumped isotopic measurements of nitrous oxide (N₂O) have the potential to offer unique constraints on the processes governing N₂O production and destruction, building on the information provided by &amp;delta;&lt;sup&gt;15&lt;/sup&gt;N, &amp;delta;&lt;sup&gt;18&lt;/sup&gt;O and &lt;sup&gt;15&lt;/sup&gt;N site preference (SP). Extending their application requires a robust absolute reference frame. Here we show that thermal equilibration of N₂O over &amp;gamma;-Al₂O₃ provides such a reference frame for measurements of the isotopologues &lt;sup&gt;14&lt;/sup&gt;N&lt;sup&gt;15&lt;/sup&gt;N&lt;sup&gt;18&lt;/sup&gt;O and &lt;sup&gt;15&lt;/sup&gt;N&lt;sup&gt;14&lt;/sup&gt;N&lt;sup&gt;18&lt;/sup&gt;O, as well as for SP. Using a quantum cascade laser absorption spectroscopy (QCLAS) platform, we simultaneously quantify seven isotopologues of N₂O, including &lt;sup&gt;14&lt;/sup&gt;N&lt;sup&gt;15&lt;/sup&gt;N&lt;sup&gt;18&lt;/sup&gt;O, &lt;sup&gt;15&lt;/sup&gt;N&lt;sup&gt;14&lt;/sup&gt;N&lt;sup&gt;18&lt;/sup&gt;O, and &lt;sup&gt;15&lt;/sup&gt;N&lt;sup&gt;15&lt;/sup&gt;N&lt;sup&gt;16&lt;/sup&gt;O. Experiments starting from isotopically-distinct starting materials show convergence to time-invariant compositions that are in agreement with theoretically predicted temperature dependencies. These results demonstrate that &amp;gamma;-Al₂O₃ activated at &amp;ge; 550 &amp;deg;C catalyzes isotope exchange among isotopologues of N₂O at equilibration temperatures between 153 &amp;deg;C and 218 &amp;deg;C and thereby define an absolute stochastic reference frame for &amp;Delta;&lt;sup&gt;14&lt;/sup&gt;N&lt;sup&gt;15&lt;/sup&gt;N&lt;sup&gt;18&lt;/sup&gt;O and &amp;Delta;&lt;sup&gt;15&lt;/sup&gt;N&lt;sup&gt;14&lt;/sup&gt;N&lt;sup&gt;18&lt;/sup&gt;O. In contrast, &lt;sup&gt;15&lt;/sup&gt;N&lt;sup&gt;15&lt;/sup&gt;N&lt;sup&gt;16&lt;/sup&gt;O does not equilibrate under these conditions, suggesting selective activation of N&amp;ndash;O but not N&amp;ndash;N bonds. Comparison of equilibrium SP values with theoretical predictions reveals a systematic offset relative to the current reference scale, which will require future work to reconcile.</p>
</abstract>
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<funding-group>
<award-group id="gs1">
<funding-source>Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung</funding-source>
<award-id>200020_204907</award-id>
<award-id>CRSK-2_228699</award-id>
</award-group>
<award-group id="gs2">
<funding-source>European Partnership on Metrology</funding-source>
<award-id>24GRD03 MetHIR</award-id>
</award-group>
</funding-group>
</article-meta>
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