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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-2025-3108</article-id>
<title-group>
<article-title>In situ production of hybrid N&lt;sub&gt;2&lt;/sub&gt;O in dust-rich Antarctic ice</article-title>
</title-group>
<contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Soussaintjean</surname>
<given-names>Lison</given-names>
<ext-link>https://orcid.org/0000-0003-2589-8972</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>Schmitt</surname>
<given-names>Jochen</given-names>
<ext-link>https://orcid.org/0000-0003-4695-3029</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>Savarino</surname>
<given-names>Joël</given-names>
<ext-link>https://orcid.org/0000-0002-6708-9623</ext-link>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Menking</surname>
<given-names>J. Andy</given-names>
</name>
<xref ref-type="aff" rid="aff3">
<sup>3</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>Brook</surname>
<given-names>Edward J.</given-names>
<ext-link>https://orcid.org/0000-0001-5438-0115</ext-link>
</name>
<xref ref-type="aff" rid="aff5">
<sup>5</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Seth</surname>
<given-names>Barbara</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>Lipenkov</surname>
<given-names>Vladimir</given-names>
</name>
<xref ref-type="aff" rid="aff6">
<sup>6</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Röckmann</surname>
<given-names>Thomas</given-names>
<ext-link>https://orcid.org/0000-0002-6688-8968</ext-link>
</name>
<xref ref-type="aff" rid="aff7">
<sup>7</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Fischer</surname>
<given-names>Hubertus</given-names>
<ext-link>https://orcid.org/0000-0002-2787-4221</ext-link>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
</contrib-group><aff id="aff1">
<label>1</label>
<addr-line>Climate and Environmental Physics, Physics Institute and Oeschger Centre for Climate Change Research, University of  Bern, Bern, 3012, Switzerland</addr-line>
</aff>
<aff id="aff2">
<label>2</label>
<addr-line>University Grenoble Alpes, CNRS, IRD, Grenoble INP, INRAE, IGE, Grenoble, 38000, France</addr-line>
</aff>
<aff id="aff3">
<label>3</label>
<addr-line>Australian Antarctic Program Partnership, Institute for Marine and Antarctic Studies, University of Tasmania, Hobart, Australia</addr-line>
</aff>
<aff id="aff4">
<label>4</label>
<addr-line>Environmental Research Unit Commonwealth Scientific and Industrial Research Organisation Aspendale, Victoria,  Australia</addr-line>
</aff>
<aff id="aff5">
<label>5</label>
<addr-line>College of Earth, Ocean, and Atmospheric Sciences, Oregon State University, Corvallis, OR 97331, USA</addr-line>
</aff>
<aff id="aff6">
<label>6</label>
<addr-line>Climate and Environmental Research Laboratory, Arctic and Antarctic Research Institute, Saint Petersburg, 199397, Russia</addr-line>
</aff>
<aff id="aff7">
<label>7</label>
<addr-line>Institute for Marine and Atmospheric research Utrecht (IMAU), Utrecht University, 3584CC Utrecht, the Netherlands</addr-line>
</aff>
<pub-date pub-type="epub">
<day>10</day>
<month>07</month>
<year>2025</year>
</pub-date>
<volume>2025</volume>
<fpage>1</fpage>
<lpage>38</lpage>
<permissions>
<copyright-statement>Copyright: &#x000a9; 2025 Lison Soussaintjean et al.</copyright-statement>
<copyright-year>2025</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/2025/egusphere-2025-3108/">This article is available from https://egusphere.copernicus.org/preprints/2025/egusphere-2025-3108/</self-uri>
<self-uri xlink:href="https://egusphere.copernicus.org/preprints/2025/egusphere-2025-3108/egusphere-2025-3108.pdf">The full text article is available as a PDF file from https://egusphere.copernicus.org/preprints/2025/egusphere-2025-3108/egusphere-2025-3108.pdf</self-uri>
<abstract>
<p>Nitrous oxide (N&lt;sub&gt;2&lt;/sub&gt;O) is a potent greenhouse gas involved in the destruction of stratospheric ozone. Past atmospheric mixing ratios of N&lt;sub&gt;2&lt;/sub&gt;O are archived in ice cores; however, the presence of in situ N&lt;sub&gt;2&lt;/sub&gt;O production in dust-rich Antarctic ice complicates their accurate reconstruction, especially during glacial periods. This production occurs in extremely cold ice and without sunlight. This study aims to understand the reaction producing N&lt;sub&gt;2&lt;/sub&gt;O in Antarctic ice by identifying the precursors and the reaction pathway. We compared the oxygen and nitrogen bulk and position-specific isotope composition of in situ N&lt;sub&gt;2&lt;/sub&gt;O in ice cores to the isotopic composition of nitrate (NO&lt;sub&gt;3&lt;/sub&gt;&lt;sup&gt;-&lt;/sup&gt;), a possible precursor of N&lt;sub&gt;2&lt;/sub&gt;O. The &lt;sup&gt;15&lt;/sup&gt;N signature of NO&lt;sub&gt;3&lt;/sub&gt;&lt;sup&gt;-&lt;/sup&gt; is fully transferred into the central N atom (N&lt;sub&gt;&amp;alpha;&lt;/sub&gt;) of in situ N&lt;sub&gt;2&lt;/sub&gt;O, but it is not transferred into the terminal N atom (N&lt;sub&gt;&amp;beta;&lt;/sub&gt;), resulting in a 50 % transfer of the &lt;sup&gt;15&lt;/sup&gt;N signature of NO&lt;sub&gt;3&lt;/sub&gt;&lt;sup&gt;-&lt;/sup&gt; into the bulk &lt;sup&gt;15&lt;/sup&gt;N isotopic composition. These findings suggest that the in situ N&lt;sub&gt;2&lt;/sub&gt;O production involves two different nitrogen precursors present in ice: the central N atom (N&lt;sub&gt;&amp;alpha;&lt;/sub&gt;) originates from NO&lt;sub&gt;3&lt;/sub&gt;&lt;sup&gt;-&lt;/sup&gt; and the terminal N atom (N&lt;sub&gt;&amp;beta;&lt;/sub&gt;) from a different precursor not yet identified. Oxygen isotope analysis shows that NO&lt;sub&gt;3&lt;/sub&gt;&lt;sup&gt;-&lt;/sup&gt; cannot be the only reservoir for the O atom of in situ N&lt;sub&gt;2&lt;/sub&gt;O. Temperature, pH, and absence of sunlight in Antarctic ice point to an abiotic N-nitrosation reaction. The limiting factor of the reaction is probably associated with mineral dust and might be Fe&lt;sup&gt;2+&lt;/sup&gt;, reducing NO&lt;sub&gt;3&lt;/sub&gt;&lt;sup&gt;-&lt;/sup&gt; to NO&lt;sub&gt;2&lt;/sub&gt;&lt;sup&gt;-&lt;/sup&gt; or the precursor of the N&lt;sub&gt;&amp;beta;&lt;/sub&gt; atom. The site preference (SP) values of in situ N&lt;sub&gt;2&lt;/sub&gt;O are highly variable between different ice cores and depend on the bulk &lt;sup&gt;15&lt;/sup&gt;N isotopic composition of N&lt;sub&gt;2&lt;/sub&gt;O, itself depending on the &lt;sup&gt;15&lt;/sup&gt;N isotopic composition of the NO&lt;sub&gt;3&lt;/sub&gt;&lt;sup&gt;-&lt;/sup&gt; precursor. This finding is unexpected because SP is usually determined by the production pathway through symmetric reaction intermediates that mix the N atoms in &amp;alpha; and &amp;beta; positions and average out their isotopic difference. In contrast, our results provide the first evidence of a hybrid N&lt;sub&gt;2&lt;/sub&gt;O production pathway involving an asymmetric intermediate that preserves the distinct &lt;sup&gt;15&lt;/sup&gt;N signatures of two different precursors &amp;ndash; one contributing to the N&lt;sub&gt;&amp;alpha;&lt;/sub&gt; atom and the other to the N&lt;sub&gt;&amp;beta;&lt;/sub&gt; atom. This finding has important implications: in this pathway, SP reflects the isotopic difference between the two precursors rather than the pathway itself, challenging how SP is commonly interpreted in environmental studies.</p>
</abstract>
<counts><page-count count="38"/></counts>
<funding-group>
<award-group id="gs1">
<funding-source>Horizon 2020</funding-source>
<award-id>955750</award-id>
<award-id>955750</award-id>
</award-group>
<award-group id="gs2">
<funding-source>Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung</funding-source>
<award-id>200020_200328</award-id>
</award-group>
</funding-group>
</article-meta>
</front>
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