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In situ production of hybrid N2O in dust-rich Antarctic ice.

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Title: In situ production of hybrid N2O in dust-rich Antarctic ice.
Authors: Soussaintjean, Lison1 (AUTHOR) lison.soussaintjean@unibe.ch, Schmitt, Jochen1 (AUTHOR), Savarino, Joël2 (AUTHOR), Menking, J. Andy3,4 (AUTHOR), Brook, Edward J.5 (AUTHOR), Seth, Barbara1 (AUTHOR), Lipenkov, Vladimir6 (AUTHOR), Röckmann, Thomas7 (AUTHOR), Fischer, Hubertus1 (AUTHOR)
Source: Biogeosciences. 2026, Vol. 23 Issue 11, p3939-3963. 25p.
Subject Terms: *Nitrous oxide, *Antarctic ice, *Greenhouse gases, *Ice cores, *Ice, *Isotopes, *Nitrates
Geographic Terms: Antarctica
Abstract: Nitrous oxide (N2O) is a potent greenhouse gas involved in the destruction of stratospheric ozone. Past atmospheric mixing ratios of N2O are archived in ice cores; however, the presence of in situ N2O 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 N2O 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 N2O in ice cores to the isotopic composition of nitrate (NO3-), a possible precursor of N2O. The 15N signature of NO3- is fully transferred into the central N atom (Nα) of in situ N2O , but it is not transferred into the terminal N atom (Nβ), resulting in a 50 % transfer of the 15N signature of NO3- into the bulk 15N isotopic composition. These findings suggest that the in situ N2O production involves two different nitrogen precursors present in ice: the central N atom (Nα) originates from NO3- and the terminal N atom (Nβ) from a different precursor not yet identified. Oxygen isotope analysis shows that NO3- cannot be the only reservoir for the O atom of in situ N2O. 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 Fe2+ , reducing NO3- to NO2- or the precursor of the Nβ atom. The site preference (SP) values of in situ N2O are highly variable between different ice cores and depend on the bulk 15N isotopic composition of N2O , itself depending on the 15N isotopic composition of the NO3- precursor. This finding is unexpected because SP is usually determined by the production pathway through symmetric reaction intermediates that mix the N atoms in α and β positions and average out their isotopic difference. In contrast, our results provide the first evidence of a hybrid N2O production pathway involving an asymmetric intermediate that preserves the distinct 15N signatures of two different precursors – one contributing to the Nα atom and the other to the Nβ atom. [ABSTRACT FROM AUTHOR]
Database: Energy & Power Source
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  Data: In situ production of hybrid N<subscript>2</subscript>O in dust-rich Antarctic ice.
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  Data: <searchLink fieldCode="AR" term="%22Soussaintjean%2C+Lison%22">Soussaintjean, Lison</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> lison.soussaintjean@unibe.ch</i><br /><searchLink fieldCode="AR" term="%22Schmitt%2C+Jochen%22">Schmitt, Jochen</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Savarino%2C+Joël%22">Savarino, Joël</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Menking%2C+J%2E Andy%22">Menking, J. Andy</searchLink><relatesTo>3,4</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Brook%2C+Edward J%2E%22">Brook, Edward J.</searchLink><relatesTo>5</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Seth%2C+Barbara%22">Seth, Barbara</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Lipenkov%2C+Vladimir%22">Lipenkov, Vladimir</searchLink><relatesTo>6</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Röckmann%2C+Thomas%22">Röckmann, Thomas</searchLink><relatesTo>7</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Fischer%2C+Hubertus%22">Fischer, Hubertus</searchLink><relatesTo>1</relatesTo> (AUTHOR)
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  Data: <searchLink fieldCode="JN" term="%22Biogeosciences%22">Biogeosciences</searchLink>. 2026, Vol. 23 Issue 11, p3939-3963. 25p.
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  Data: *<searchLink fieldCode="DE" term="%22Nitrous+oxide%22">Nitrous oxide</searchLink><br />*<searchLink fieldCode="DE" term="%22Antarctic+ice%22">Antarctic ice</searchLink><br />*<searchLink fieldCode="DE" term="%22Greenhouse+gases%22">Greenhouse gases</searchLink><br />*<searchLink fieldCode="DE" term="%22Ice+cores%22">Ice cores</searchLink><br />*<searchLink fieldCode="DE" term="%22Ice%22">Ice</searchLink><br />*<searchLink fieldCode="DE" term="%22Isotopes%22">Isotopes</searchLink><br />*<searchLink fieldCode="DE" term="%22Nitrates%22">Nitrates</searchLink>
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  Data: <searchLink fieldCode="DE" term="%22Antarctica%22">Antarctica</searchLink>
– Name: Abstract
  Label: Abstract
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  Data: Nitrous oxide (N2O) is a potent greenhouse gas involved in the destruction of stratospheric ozone. Past atmospheric mixing ratios of N2O are archived in ice cores; however, the presence of in situ N2O 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 N2O 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 N2O in ice cores to the isotopic composition of nitrate (NO3-), a possible precursor of N2O. The 15N signature of NO3- is fully transferred into the central N atom (Nα) of in situ N2O , but it is not transferred into the terminal N atom (Nβ), resulting in a 50 % transfer of the 15N signature of NO3- into the bulk 15N isotopic composition. These findings suggest that the in situ N2O production involves two different nitrogen precursors present in ice: the central N atom (Nα) originates from NO3- and the terminal N atom (Nβ) from a different precursor not yet identified. Oxygen isotope analysis shows that NO3- cannot be the only reservoir for the O atom of in situ N2O. 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 Fe2+ , reducing NO3- to NO2- or the precursor of the Nβ atom. The site preference (SP) values of in situ N2O are highly variable between different ice cores and depend on the bulk 15N isotopic composition of N2O , itself depending on the 15N isotopic composition of the NO3- precursor. This finding is unexpected because SP is usually determined by the production pathway through symmetric reaction intermediates that mix the N atoms in α and β positions and average out their isotopic difference. In contrast, our results provide the first evidence of a hybrid N2O production pathway involving an asymmetric intermediate that preserves the distinct 15N signatures of two different precursors – one contributing to the Nα atom and the other to the Nβ atom. [ABSTRACT FROM AUTHOR]
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      – Type: doi
        Value: 10.5194/bg-23-3939-2026
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      – Code: eng
        Text: English
    PhysicalDescription:
      Pagination:
        PageCount: 25
        StartPage: 3939
    Subjects:
      – SubjectFull: Nitrous oxide
        Type: general
      – SubjectFull: Antarctic ice
        Type: general
      – SubjectFull: Greenhouse gases
        Type: general
      – SubjectFull: Ice cores
        Type: general
      – SubjectFull: Ice
        Type: general
      – SubjectFull: Isotopes
        Type: general
      – SubjectFull: Nitrates
        Type: general
      – SubjectFull: Antarctica
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      – TitleFull: In situ production of hybrid N2O in dust-rich Antarctic ice.
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              M: 06
              Text: 2026
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