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  <front>
    <journal-meta><journal-id journal-id-type="publisher">CP</journal-id><journal-title-group>
    <journal-title>Climate of the Past</journal-title>
    <abbrev-journal-title abbrev-type="publisher">CP</abbrev-journal-title><abbrev-journal-title abbrev-type="nlm-ta">Clim. Past</abbrev-journal-title>
  </journal-title-group><issn pub-type="epub">1814-9332</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/cp-17-1627-2021</article-id><title-group><article-title>CH<inline-formula><mml:math id="M1" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M2" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O fluctuations during the penultimate deglaciation</article-title><alt-title>CH<inline-formula><mml:math id="M3" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M4" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O fluctuations during the penultimate deglaciation</alt-title>
      </title-group><?xmltex \runningtitle{CH${}_{4}$ and N${}_{2}$O fluctuations during the penultimate deglaciation}?><?xmltex \runningauthor{L. Schmidely et al.}?>
      <contrib-group>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Schmidely</surname><given-names>Loïc</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2">
          <name><surname>Nehrbass-Ahles</surname><given-names>Christoph</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-4009-4633</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Schmitt</surname><given-names>Jochen</given-names></name>
          
        <ext-link>https://orcid.org/0000-0003-4695-3029</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Han</surname><given-names>Juhyeong</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Silva</surname><given-names>Lucas</given-names></name>
          
        <ext-link>https://orcid.org/0000-0003-3623-213X</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff3 aff4">
          <name><surname>Shin</surname><given-names>Jinwha</given-names></name>
          
        <ext-link>https://orcid.org/0000-0003-4059-7748</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Joos</surname><given-names>Fortunat</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-9483-6030</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff3">
          <name><surname>Chappellaz</surname><given-names>Jérôme</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Fischer</surname><given-names>Hubertus</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-2787-4221</ext-link></contrib>
        <contrib contrib-type="author" corresp="yes" rid="aff1">
          <name><surname>Stocker</surname><given-names>Thomas F.</given-names></name>
          <email>thomas.stocker@climate.unibe.ch</email>
        </contrib>
        <aff id="aff1"><label>1</label><institution>Climate and Environmental Physics, Physics Institute and Oeschger Centre for Climate Change Research,<?xmltex \hack{\break}?> University of Bern, Bern 3012, Switzerland</institution>
        </aff>
        <aff id="aff2"><label>2</label><institution>Department of Earth Sciences, University of Cambridge, Cambridge, UK</institution>
        </aff>
        <aff id="aff3"><label>3</label><institution>Institut des Géosciences de l’Environnement (IGE), CNRS, Univ. Grenoble-Alpes, Grenoble, France</institution>
        </aff>
        <aff id="aff4"><label>a</label><institution>present address: Department of Earth and Atmospheric Sciences, University of Alberta, Edmonton, AB, T6G 2E3, Canada</institution>
        </aff>
      </contrib-group>
      <author-notes><corresp id="corr1">Thomas F. Stocker (thomas.stocker@climate.unibe.ch)</corresp></author-notes><pub-date><day>3</day><month>August</month><year>2021</year></pub-date>
      
      <volume>17</volume>
      <issue>4</issue>
      <fpage>1627</fpage><lpage>1643</lpage>
      <history>
        <date date-type="received"><day>30</day><month>September</month><year>2020</year></date>
           <date date-type="rev-request"><day>19</day><month>October</month><year>2020</year></date>
           <date date-type="rev-recd"><day>12</day><month>May</month><year>2021</year></date>
           <date date-type="accepted"><day>1</day><month>July</month><year>2021</year></date>
      </history>
      <permissions>
        <copyright-statement>Copyright: © 2021 </copyright-statement>
        <copyright-year>2021</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://cp.copernicus.org/articles/.html">This article is available from https://cp.copernicus.org/articles/.html</self-uri><self-uri xlink:href="https://cp.copernicus.org/articles/.pdf">The full text article is available as a PDF file from https://cp.copernicus.org/articles/.pdf</self-uri>
      <abstract><title>Abstract</title>
    <p id="d1e222">Deglaciations are characterized by the largest natural changes in methane (CH<inline-formula><mml:math id="M5" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>) and nitrous oxide (N<inline-formula><mml:math id="M6" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O) concentrations of the past 800 000 years. Reconstructions of millennial- to centennial-scale variability within these periods are mostly restricted to the last deglaciation. In this study, we present composite records of CH<inline-formula><mml:math id="M7" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M8" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentrations from the EPICA Dome C ice core covering the penultimate deglaciation at temporal resolutions of <inline-formula><mml:math id="M9" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">100</mml:mn></mml:mrow></mml:math></inline-formula> years. Our data permit the identification of centennial-scale fluctuations during the transition from glacial to interglacial levels. At <inline-formula><mml:math id="M10" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">134</mml:mn><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mn mathvariant="normal">000</mml:mn></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M11" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">129</mml:mn><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mn mathvariant="normal">000</mml:mn></mml:mrow></mml:math></inline-formula> years before present (hereafter ka), both CH<inline-formula><mml:math id="M12" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M13" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O increased on centennial timescales. These abrupt rises are similar to the fluctuations associated with the Dansgaard–Oeschger events identified in the last glacial period. In addition, gradually rising N<inline-formula><mml:math id="M14" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O levels at <inline-formula><mml:math id="M15" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">130</mml:mn></mml:mrow></mml:math></inline-formula> ka resemble a pattern of increasing N<inline-formula><mml:math id="M16" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentrations on millennial timescales characterizing the later part of Heinrich stadials. Overall, the events in CH<inline-formula><mml:math id="M17" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M18" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O during the penultimate deglaciation exhibit modes of variability that are also found during the last deglaciation and glacial cycle, suggesting that the processes leading to changes in emission during the transitions were similar but their timing differed.</p>
  </abstract>
    </article-meta>
  </front>
<body>
      

<sec id="Ch1.S1" sec-type="intro">
  <label>1</label><title>Introduction</title>
      <p id="d1e372">Methane (CH<inline-formula><mml:math id="M19" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>) and nitrous oxide (N<inline-formula><mml:math id="M20" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O) are currently the second- and third-most potent well-mixed anthropogenic greenhouse gases after carbon dioxide (CO<inline-formula><mml:math id="M21" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>) <xref ref-type="bibr" rid="bib1.bibx46" id="paren.1"/>. The impact of these trace gases on the Earth's radiative balance in the future depends on the sensitivity of natural sources to anthropogenic warming. Time periods of climate change in the past provide natural templates to study this coupling <xref ref-type="bibr" rid="bib1.bibx25" id="paren.2"/>. Reconstructions of greenhouse gas concentrations before the instrumental era are only enabled by analysing the composition of air trapped in tiny bubbles in polar ice cores, reflecting the atmospheric composition at the time the bubbles were formed. Ice core records of CH<inline-formula><mml:math id="M22" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M23" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentrations combined with temperature reconstructions revealed the natural variability of these gases and their coupling to climate change during the glacial cycles of the past 800 000 years. The overall increase in concentrations accompanying deglaciations represents the largest recurring changes <xref ref-type="bibr" rid="bib1.bibx63 bib1.bibx42 bib1.bibx54" id="paren.3"/>. Records spanning the last deglaciation (Termination I (TI), 18 000–11 000 years before present (hereafter ka), where present is defined as 1950 Common Era) showed that this overall increase appears as a sequence of millennial and centennial fluctuations superimposed, for CH<inline-formula><mml:math id="M24" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>, on longer-term, gradually rising concentrations <xref ref-type="bibr" rid="bib1.bibx43 bib1.bibx51" id="paren.4"/>. Records resolving short-term fluctuations within deglaciations are limited to TI, owing to the availability of multiple high-accumulation ice cores.</p>
      <?pagebreak page1628?><p id="d1e442">The aim of this study is to produce a high-resolution deglacial record for the penultimate deglaciation (Termination II (TII), 140–128 ka). We present CH<inline-formula><mml:math id="M25" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M26" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O composite datasets from the EPICA Dome C (EDC) ice core including 150 new measurements covering the time interval 145–125 ka, combined with the published data of <xref ref-type="bibr" rid="bib1.bibx42" id="text.5"/> and <xref ref-type="bibr" rid="bib1.bibx54" id="text.6"/>. We increased the sampling resolution of the aforementioned records by a factor <inline-formula><mml:math id="M27" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">3.5</mml:mn></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M28" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">5</mml:mn></mml:mrow></mml:math></inline-formula> to obtain mean resolutions of 100 and 115 years for CH<inline-formula><mml:math id="M29" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M30" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O, respectively. These values are on the order of the mean width of the gas age distribution (GAD) for the EDC ice core in the interval 145–125 ka. This width is estimated to range between <inline-formula><mml:math id="M31" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">110</mml:mn></mml:mrow></mml:math></inline-formula>–220 years using the approach of <xref ref-type="bibr" rid="bib1.bibx47" id="text.7"/>, where the width is defined as the arithmetic mean of the distribution, and <inline-formula><mml:math id="M32" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">50</mml:mn></mml:mrow></mml:math></inline-formula>–130 years using the approach of <xref ref-type="bibr" rid="bib1.bibx24" id="text.8"/>, where the width is defined as the spectral width of the distribution. In addition, we also present seven N<inline-formula><mml:math id="M33" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O isotopic measurements (<inline-formula><mml:math id="M34" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">15</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>N (N<inline-formula><mml:math id="M35" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O) and <inline-formula><mml:math id="M36" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (N<inline-formula><mml:math id="M37" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O)), used to assess the integrity of the data with respect to in situ formation of N<inline-formula><mml:math id="M38" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O.</p>
      <p id="d1e594">CH<inline-formula><mml:math id="M39" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M40" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O fluctuations observed during TI belong to recurrent modes of variability. The most studied of these modes characterizes the climate transitions from stadials to interstadials and is most notably exemplified by the transitions associated with the Dansgaard–Oeschger (DO) events of the last glacial period as well as by the transitions to the Bølling–Allerød and the Holocene during TI. This <italic>DO-type</italic> mode of variability is characterized by abrupt increases in CH<inline-formula><mml:math id="M41" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> concentrations (<inline-formula><mml:math id="M42" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">50</mml:mn></mml:mrow></mml:math></inline-formula>–260 ppb in a few centuries), approximately synchronous with the onsets of interstadial Greenland warming by a few decades <xref ref-type="bibr" rid="bib1.bibx3 bib1.bibx53" id="paren.9"/>, while N<inline-formula><mml:math id="M43" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentrations exhibit concomitant increases reaching up to <inline-formula><mml:math id="M44" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">60</mml:mn></mml:mrow></mml:math></inline-formula> ppb, taking more than a century to stabilize because of their longer atmospheric lifetime <xref ref-type="bibr" rid="bib1.bibx29 bib1.bibx54 bib1.bibx56" id="paren.10"/>. In addition, N<inline-formula><mml:math id="M45" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentrations gradually increase in the later part of Heinrich stadials (HSs), extended stadials defined by the occurrence of massive iceberg discharges through the Hudson Strait into the North Atlantic <xref ref-type="bibr" rid="bib1.bibx35" id="paren.11"/>, starting centuries to millennia before interstadial Greenland temperature and CH<inline-formula><mml:math id="M46" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> rises <xref ref-type="bibr" rid="bib1.bibx56" id="paren.12"/>. This <italic>late HS-type</italic> mode of N<inline-formula><mml:math id="M47" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O variability characterized the HS during both the last deglaciation <xref ref-type="bibr" rid="bib1.bibx26 bib1.bibx57" id="paren.13"/> as well as the last glacial period <xref ref-type="bibr" rid="bib1.bibx56" id="paren.14"/>. A second mode of CH<inline-formula><mml:math id="M48" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> variability has been identified during HSs of the last glacial and deglaciation. This <italic>HS-type</italic> mode of CH<inline-formula><mml:math id="M49" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> variability consists of intermittent CH<inline-formula><mml:math id="M50" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> peaks displaying amplitudes of 32–53 ppb and characteristic timescales of 90–190 years, sometimes followed (HS4 and HS5) by elevated background concentrations relative to before the event <xref ref-type="bibr" rid="bib1.bibx51" id="paren.15"/>.</p>
      <p id="d1e740">DO-type and HS-type CH<inline-formula><mml:math id="M51" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> fluctuations are likely driven by changes in tropical wetland emissions <xref ref-type="bibr" rid="bib1.bibx51 bib1.bibx12" id="paren.16"/>, where CH<inline-formula><mml:math id="M52" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> is produced by the decomposition of organic matter under anaerobic conditions. Changes in geologic and pyrogenic emissions as well as changes in the sink strength play only a minor role <xref ref-type="bibr" rid="bib1.bibx22 bib1.bibx11 bib1.bibx12 bib1.bibx41 bib1.bibx36" id="paren.17"/>. Wetland emissions are controlled by climate (precipitation, temperature, and atmospheric CO<inline-formula><mml:math id="M53" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> concentration), modulating wetland extent, emission rates, and ecosystem composition <xref ref-type="bibr" rid="bib1.bibx64 bib1.bibx45 bib1.bibx10" id="paren.18"/>. Changes in tropical wetland emissions during DO-type fluctuations are linked to the strengthening of monsoonal precipitation in the Northern Hemisphere (NH) tropics, enhancing wetland emission rates <xref ref-type="bibr" rid="bib1.bibx12" id="paren.19"/>. Increased NH tropical precipitation is associated with northward shifts of the Intertropical Convergence Zone (ITCZ) in response to changes in heat distribution by the Atlantic Meridional Overturning Circulation (AMOC) <xref ref-type="bibr" rid="bib1.bibx14 bib1.bibx1" id="paren.20"/>. On the other hand, HS-type CH<inline-formula><mml:math id="M54" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> fluctuations are hypothesized to result from large iceberg discharges, associated with a southward shift of the ITCZ, leading to an intensification of monsoonal precipitation in the Southern Hemisphere (SH) tropics, ultimately producing an increase in wetland emissions <xref ref-type="bibr" rid="bib1.bibx51" id="paren.21"/>.</p>
      <p id="d1e799">DO-type N<inline-formula><mml:math id="M55" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O variability is likely driven by changes in emission from the terrestrial and marine biospheres, where N<inline-formula><mml:math id="M56" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O is emitted as a by-product of nitrification and an intermediate product of denitrification <xref ref-type="bibr" rid="bib1.bibx37 bib1.bibx38 bib1.bibx26 bib1.bibx57" id="paren.22"/>. Terrestrial emissions are controlled by climate (precipitation, temperature, and atmospheric CO<inline-formula><mml:math id="M57" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> concentration) and available land area <xref ref-type="bibr" rid="bib1.bibx38 bib1.bibx64" id="paren.23"/>. During TI, the response of terrestrial N<inline-formula><mml:math id="M58" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O emissions for DO-type fluctuations is believed to result from temperature and precipitation changes <xref ref-type="bibr" rid="bib1.bibx38" id="paren.24"/> and appeared in phase with Greenland warming with the transition period lasting a maximum of <inline-formula><mml:math id="M59" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">200</mml:mn></mml:mrow></mml:math></inline-formula> years <xref ref-type="bibr" rid="bib1.bibx26" id="paren.25"/>. Marine emissions are linked to the strength of the AMOC, modulating oxygen concentrations in the upper ocean and the amount of available organic matter at depth. For DO-type fluctuations, marine emissions are believed to be stimulated mainly by deoxygenation in the upper ocean as a consequence of the reinvigoration of the AMOC <xref ref-type="bibr" rid="bib1.bibx37" id="paren.26"/>. Finally, the late HS-type N<inline-formula><mml:math id="M60" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O increase during TI is thought to be driven exclusively by marine emissions <xref ref-type="bibr" rid="bib1.bibx26 bib1.bibx57" id="paren.27"/>, possibly resulting from a long-term reorganization of the nitrate and oxygen inventories following the preceding AMOC collapse <xref ref-type="bibr" rid="bib1.bibx60" id="paren.28"/>.</p>
</sec>
<sec id="Ch1.S2">
  <label>2</label><title>Method</title>
      <p id="d1e888">The results presented in this study are derived from two different instruments. The <inline-formula><mml:math id="M61" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">15</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>N (N<inline-formula><mml:math id="M62" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O) and <inline-formula><mml:math id="M63" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (N<inline-formula><mml:math id="M64" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O) data were measured with the device described in <xref ref-type="bibr" rid="bib1.bibx59" id="text.29"/>, combining continuous extraction under vacuum with gas chromatography (GC) and isotope ratio mass spectrometry.</p>
      <?pagebreak page1629?><p id="d1e934">CH<inline-formula><mml:math id="M65" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M66" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O measurements were performed with a completely revised analytical system, firstly employed during this study (comprehensive description in Appendix A). The new apparatus uses continuous extraction under vacuum, comparable to the approach of <xref ref-type="bibr" rid="bib1.bibx59" id="text.30"/> or <xref ref-type="bibr" rid="bib1.bibx49" id="text.31"/>, combined with GC techniques to determine CH<inline-formula><mml:math id="M67" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M68" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O mole fractions in air extracted from small (<inline-formula><mml:math id="M69" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">20</mml:mn></mml:mrow></mml:math></inline-formula> g) ice samples with a sample throughput of five to six samples per day. The instrument is equipped with a thermal conductivity detector, a flame-ionization detector, and an electron-capture detector for the quantification of air, CH<inline-formula><mml:math id="M70" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>, and N<inline-formula><mml:math id="M71" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O, respectively. The results are referenced to the World Meteorological Organisation mole fraction scales: the WMOX2004A scale (CH<inline-formula><mml:math id="M72" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>) and NOAA-2006A (N<inline-formula><mml:math id="M73" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O) <xref ref-type="bibr" rid="bib1.bibx21 bib1.bibx34" id="paren.32"/> using three standard gases bracketing the glacial–interglacial range of CH<inline-formula><mml:math id="M74" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> (358.88 <inline-formula><mml:math id="M75" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.16 ppb, 838.59 <inline-formula><mml:math id="M76" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.28 ppb, and 1729.30 <inline-formula><mml:math id="M77" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.34 ppb) and N<inline-formula><mml:math id="M78" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentrations (187.10 <inline-formula><mml:math id="M79" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.12 ppb, 194.13 <inline-formula><mml:math id="M80" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.12 ppb, and 300.20 <inline-formula><mml:math id="M81" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.12 ppb). The uncertainty of the measurements derived from the revised instrument amounts to 7 (CH<inline-formula><mml:math id="M82" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>) and 6 ppb (N<inline-formula><mml:math id="M83" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O).</p>
</sec>
<sec id="Ch1.S3">
  <label>3</label><title>Results</title>
      <p id="d1e1117">Our centennial-scale records show the progressions of the overall <inline-formula><mml:math id="M84" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">390</mml:mn></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M85" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">60</mml:mn></mml:mrow></mml:math></inline-formula> ppb increase in CH<inline-formula><mml:math id="M86" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M87" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentration (Fig. <xref ref-type="fig" rid="Ch1.F1"/>), respectively, from the end of the Penultimate Glacial Maximum (PGM) to the beginning of the Last Interglacial (LIG). Our CH<inline-formula><mml:math id="M88" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> data identify an outstanding value at <inline-formula><mml:math id="M89" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">140</mml:mn></mml:mrow></mml:math></inline-formula> ka in the dataset by <xref ref-type="bibr" rid="bib1.bibx42" id="text.33"/>, <inline-formula><mml:math id="M90" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">80</mml:mn></mml:mrow></mml:math></inline-formula> ppb higher than adjacent samples (Fig. <xref ref-type="fig" rid="Ch1.F1"/>). The N<inline-formula><mml:math id="M91" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O data appear substantially more scattered in the early part of the record, especially around the PGM (<inline-formula><mml:math id="M92" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">145</mml:mn></mml:mrow></mml:math></inline-formula>–140 ka). This scatter tends to decrease with younger ages. The spikes appear in the interval where the isotopic composition of N<inline-formula><mml:math id="M93" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O becomes enriched in <inline-formula><mml:math id="M94" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">15</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>N (N<inline-formula><mml:math id="M95" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O) (up to 21 ‰) and depleted in <inline-formula><mml:math id="M96" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (N<inline-formula><mml:math id="M97" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O) (down to 41 ‰), compared to the relatively steady values in the ranges <inline-formula><mml:math id="M98" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">11</mml:mn></mml:mrow></mml:math></inline-formula>–14 ‰ and <inline-formula><mml:math id="M99" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">45</mml:mn></mml:mrow></mml:math></inline-formula>–47 ‰, respectively, observed for 125–136 ka (Fig. <xref ref-type="fig" rid="Ch1.F1"/>).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F1" specific-use="star"><?xmltex \currentcnt{1}?><?xmltex \def\figurename{Figure}?><label>Figure 1</label><caption><p id="d1e1289">CH<inline-formula><mml:math id="M100" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>, N<inline-formula><mml:math id="M101" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O, <inline-formula><mml:math id="M102" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (N<inline-formula><mml:math id="M103" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O), and <inline-formula><mml:math id="M104" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">15</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>N (N<inline-formula><mml:math id="M105" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O) records from the EDC ice core on the AICC2012 timescale <xref ref-type="bibr" rid="bib1.bibx7" id="paren.34"/>. The vertical bars represent the uncertainty of the measurements. <bold>(a)</bold> Composite CH<inline-formula><mml:math id="M106" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> record with published data (light blue, <xref ref-type="bibr" rid="bib1.bibx42" id="altparen.35"/>) and new measurements (this study, dark blue) after offset correction. The asterisk indicates the data point regarded as an outlier. <bold>(b)</bold> Composite N<inline-formula><mml:math id="M107" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O record with published data (light green, <xref ref-type="bibr" rid="bib1.bibx54" id="altparen.36"/>) and new measurements (this study, dark green) after offset correction. The empty symbols illustrate the data points considered affected by in situ production. <bold>(c)</bold> <inline-formula><mml:math id="M108" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (N<inline-formula><mml:math id="M109" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O) record. For comparison, the average (solid line) and standard deviation (dashed line, 1<inline-formula><mml:math id="M110" display="inline"><mml:mi mathvariant="italic">σ</mml:mi></mml:math></inline-formula>) of <inline-formula><mml:math id="M111" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (N<inline-formula><mml:math id="M112" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O) over TI are included <xref ref-type="bibr" rid="bib1.bibx26" id="paren.37"/>. <bold>(d)</bold> <inline-formula><mml:math id="M113" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">15</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>N (N<inline-formula><mml:math id="M114" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O) record. For comparison, the average (solid line) and standard deviation (dashed line, 1<inline-formula><mml:math id="M115" display="inline"><mml:mi mathvariant="italic">σ</mml:mi></mml:math></inline-formula>) of <inline-formula><mml:math id="M116" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">15</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>N (N<inline-formula><mml:math id="M117" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O) over TI are included <xref ref-type="bibr" rid="bib1.bibx26" id="paren.38"/>.</p></caption>
        <?xmltex \igopts{width=412.564961pt}?><graphic xlink:href="https://cp.copernicus.org/articles/17/1627/2021/cp-17-1627-2021-f01.png"/>

      </fig>

      <p id="d1e1499">Our records display several fluctuations standing out in the overall evolution of the CH<inline-formula><mml:math id="M118" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M119" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentrations. For CH<inline-formula><mml:math id="M120" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>, these events are identified based on their high rates of change (<inline-formula><mml:math id="M121" display="inline"><mml:mo lspace="0mm">&gt;</mml:mo></mml:math></inline-formula>10 ppb per century, Table <xref ref-type="table" rid="Ch1.T1"/>). CH<inline-formula><mml:math id="M122" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> rises on centennial timescales at <inline-formula><mml:math id="M123" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">134</mml:mn></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M124" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">129</mml:mn></mml:mrow></mml:math></inline-formula> ka. At <inline-formula><mml:math id="M125" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">134</mml:mn></mml:mrow></mml:math></inline-formula> ka, concentrations increased by <inline-formula><mml:math id="M126" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">70</mml:mn></mml:mrow></mml:math></inline-formula> ppb in <inline-formula><mml:math id="M127" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">200</mml:mn></mml:mrow></mml:math></inline-formula> years before declining by <inline-formula><mml:math id="M128" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">60</mml:mn></mml:mrow></mml:math></inline-formula> ppb in <inline-formula><mml:math id="M129" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">400</mml:mn></mml:mrow></mml:math></inline-formula> years. The 129 ka event consists of a <inline-formula><mml:math id="M130" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">200</mml:mn></mml:mrow></mml:math></inline-formula> ppb increase proceeding in <inline-formula><mml:math id="M131" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">300</mml:mn></mml:mrow></mml:math></inline-formula> years.</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T1" specific-use="star"><?xmltex \currentcnt{1}?><label>Table 1</label><caption><p id="d1e1643">Characteristics of the events observed at <inline-formula><mml:math id="M132" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">134</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M133" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">129</mml:mn></mml:mrow></mml:math></inline-formula>, and <inline-formula><mml:math id="M134" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">130</mml:mn></mml:mrow></mml:math></inline-formula> ka. The indications “up” and “down” in the first column refer to the ascending and descending limbs of the 134 ka event, respectively. The columns “start” and “end” indicate the starting and end points of the events (rounded to the hundred). The columns <inline-formula><mml:math id="M135" display="inline"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mi mathvariant="normal">initial</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M136" display="inline"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mi mathvariant="normal">final</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> indicate the concentrations (rounded to the 10) in the years preceding and following the events, respectively. The rates of change are average values over the time period comprised between the start and end points of the events. Rates of change are calculated from spline approximations (cut-off period: 200 years) computed according to <xref ref-type="bibr" rid="bib1.bibx23" id="text.39"/> with the same routine as <xref ref-type="bibr" rid="bib1.bibx8" id="text.40"/>.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="6">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="right"/>
     <oasis:colspec colnum="3" colname="col3" align="right"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:colspec colnum="6" colname="col6" align="right"/>
     <oasis:thead>
       <oasis:row>
         <oasis:entry colname="col1">Event</oasis:entry>
         <oasis:entry colname="col2">Start</oasis:entry>
         <oasis:entry colname="col3">End</oasis:entry>
         <oasis:entry colname="col4"><inline-formula><mml:math id="M137" display="inline"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mi mathvariant="normal">initial</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col5"><inline-formula><mml:math id="M138" display="inline"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mi mathvariant="normal">final</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col6">Rate of change</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">(ka)</oasis:entry>
         <oasis:entry colname="col3">(ka)</oasis:entry>
         <oasis:entry colname="col4">(ppb)</oasis:entry>
         <oasis:entry colname="col5">(ppb)</oasis:entry>
         <oasis:entry colname="col6">(ppb per century)</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>
         <oasis:entry colname="col1">134 (CH<inline-formula><mml:math id="M139" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>, up)</oasis:entry>
         <oasis:entry colname="col2">134.0</oasis:entry>
         <oasis:entry colname="col3">133.8</oasis:entry>
         <oasis:entry colname="col4">440</oasis:entry>
         <oasis:entry colname="col5">510</oasis:entry>
         <oasis:entry colname="col6">35</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">134 (CH<inline-formula><mml:math id="M140" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>, down)</oasis:entry>
         <oasis:entry colname="col2">133.8</oasis:entry>
         <oasis:entry colname="col3">133.4</oasis:entry>
         <oasis:entry colname="col4">510</oasis:entry>
         <oasis:entry colname="col5">450</oasis:entry>
         <oasis:entry colname="col6"><inline-formula><mml:math id="M141" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">15</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">134 (N<inline-formula><mml:math id="M142" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O, up)</oasis:entry>
         <oasis:entry colname="col2">133.9</oasis:entry>
         <oasis:entry colname="col3">133.6</oasis:entry>
         <oasis:entry colname="col4">210</oasis:entry>
         <oasis:entry colname="col5">240</oasis:entry>
         <oasis:entry colname="col6">10</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">134 (N<inline-formula><mml:math id="M143" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O, down)</oasis:entry>
         <oasis:entry colname="col2">133.6</oasis:entry>
         <oasis:entry colname="col3">132.6</oasis:entry>
         <oasis:entry colname="col4">240</oasis:entry>
         <oasis:entry colname="col5">210</oasis:entry>
         <oasis:entry colname="col6"><inline-formula><mml:math id="M144" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">130 (N<inline-formula><mml:math id="M145" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O)</oasis:entry>
         <oasis:entry colname="col2">130.7</oasis:entry>
         <oasis:entry colname="col3">130</oasis:entry>
         <oasis:entry colname="col4">220</oasis:entry>
         <oasis:entry colname="col5">240</oasis:entry>
         <oasis:entry colname="col6">3</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">129 (CH<inline-formula><mml:math id="M146" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>)</oasis:entry>
         <oasis:entry colname="col2">128.9</oasis:entry>
         <oasis:entry colname="col3">128.6</oasis:entry>
         <oasis:entry colname="col4">530</oasis:entry>
         <oasis:entry colname="col5">730</oasis:entry>
         <oasis:entry colname="col6">65</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">129 (N<inline-formula><mml:math id="M147" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O)</oasis:entry>
         <oasis:entry colname="col2">129</oasis:entry>
         <oasis:entry colname="col3">128.1</oasis:entry>
         <oasis:entry colname="col4">240</oasis:entry>
         <oasis:entry colname="col5">270</oasis:entry>
         <oasis:entry colname="col6">3</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

      <p id="d1e2024">The evolution of N<inline-formula><mml:math id="M148" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentrations alternates between periods of plateaus and well-marked fluctuations. Similar to CH<inline-formula><mml:math id="M149" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>, a feature is resolved at <inline-formula><mml:math id="M150" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">134</mml:mn></mml:mrow></mml:math></inline-formula> ka where concentrations increased by <inline-formula><mml:math id="M151" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">30</mml:mn></mml:mrow></mml:math></inline-formula> ppb in <inline-formula><mml:math id="M152" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">300</mml:mn></mml:mrow></mml:math></inline-formula> years before declining to previous levels in <inline-formula><mml:math id="M153" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">1000</mml:mn></mml:mrow></mml:math></inline-formula> years. The 129 ka event is also imprinted in our N<inline-formula><mml:math id="M154" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O record and is characterized by a <inline-formula><mml:math id="M155" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">30</mml:mn></mml:mrow></mml:math></inline-formula> ppb rise in <inline-formula><mml:math id="M156" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">900</mml:mn></mml:mrow></mml:math></inline-formula> years. In addition, an increase is identified at <inline-formula><mml:math id="M157" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">130</mml:mn></mml:mrow></mml:math></inline-formula> ka, where concentrations rose by <inline-formula><mml:math id="M158" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">20</mml:mn></mml:mrow></mml:math></inline-formula> ppb in <inline-formula><mml:math id="M159" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">700</mml:mn></mml:mrow></mml:math></inline-formula> years. The 130 and 129 ka events are separated by a plateau that lasted <inline-formula><mml:math id="M160" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">1000</mml:mn></mml:mrow></mml:math></inline-formula> years.</p>
      <p id="d1e2156"><?xmltex \hack{\newpage}?>Overall, the improved resolution of our records allowed us to identify features not resolved in the previously published CH<inline-formula><mml:math id="M161" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M162" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O EDC datasets. In particular, the 134 ka event and the 130 ka event in N<inline-formula><mml:math id="M163" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O are resolved for the first time. Retrieving CH<inline-formula><mml:math id="M164" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M165" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentrations from the same samples enables us to study the relative phasing of both trace gases in the course of these events without age uncertainty. At the onset of the 134 and 129 ka events, the rise in both trace gases occurs simultaneously. In contrast, the 130 ka event in the N<inline-formula><mml:math id="M166" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O record is not accompanied by a concomitant fluctuation in CH<inline-formula><mml:math id="M167" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> concentrations.</p>
</sec>
<sec id="Ch1.S4">
  <label>4</label><title>Discussion</title>
<sec id="Ch1.S4.SS1">
  <label>4.1</label><?xmltex \opttitle{Non-atmospheric CH${}_{4}$ and N${}_{2}$O variability}?><title>Non-atmospheric CH<inline-formula><mml:math id="M168" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M169" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O variability</title>
      <p id="d1e2258">Interpreting our records in terms of atmospheric variability requires a closer inspection of the extreme values observed in the CH<inline-formula><mml:math id="M170" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M171" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O records.</p>
      <p id="d1e2279">The CH<inline-formula><mml:math id="M172" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> data point at <inline-formula><mml:math id="M173" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">140</mml:mn></mml:mrow></mml:math></inline-formula> ka, previously published by <xref ref-type="bibr" rid="bib1.bibx42" id="text.41"/>, is measured in the section characterized by the widest GAD in our record. For the time interval 141–139 ka, the width of the GAD is on the order of <inline-formula><mml:math id="M174" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">220</mml:mn></mml:mrow></mml:math></inline-formula> years, using the approach of <xref ref-type="bibr" rid="bib1.bibx47" id="text.42"/>, or <inline-formula><mml:math id="M175" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">120</mml:mn></mml:mrow></mml:math></inline-formula> years using the approach of <xref ref-type="bibr" rid="bib1.bibx24" id="text.43"/>. At <inline-formula><mml:math id="M176" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">140</mml:mn></mml:mrow></mml:math></inline-formula> ka, the adjacent data points are <inline-formula><mml:math id="M177" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">160</mml:mn></mml:mrow></mml:math></inline-formula> years older and <inline-formula><mml:math id="M178" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">170</mml:mn></mml:mrow></mml:math></inline-formula> years younger than the data point in question. Consequently, it appears unlikely that such an abrupt fluctuation in the ice core record represents an atmospheric signal. Spurious peaks could potentially result from layered bubble trapping <xref ref-type="bibr" rid="bib1.bibx52 bib1.bibx30 bib1.bibx31" id="paren.44"/>. However, this outlier is measured in a period of otherwise stable CH<inline-formula><mml:math id="M179" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> concentrations, where neither early nor late pore closures are expected to generate an anomaly <xref ref-type="bibr" rid="bib1.bibx52 bib1.bibx30" id="paren.45"/>. Secondly, similarly high concentrations are not observed in our record before the 134 ka event. Such an age anomaly (between the layers enclosing gas of abnormal age and the layers enclosing gas of the expected age) would be unrealistically high compared to the characteristic age anomalies reported by <xref ref-type="bibr" rid="bib1.bibx30" id="text.46"/> for the Vostok ice core (<inline-formula><mml:math id="M180" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">200</mml:mn></mml:mrow></mml:math></inline-formula> years). Accordingly, we regard this CH<inline-formula><mml:math id="M181" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> data point as an outlier.</p>
      <?pagebreak page1631?><p id="d1e2399">The large variability observed in adjacent data points during the early part of the N<inline-formula><mml:math id="M182" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O record (Fig. <xref ref-type="fig" rid="Ch1.F1"/>) is unlikely to reflect atmospheric fluctuations given its atmospheric lifetime of 116 <inline-formula><mml:math id="M183" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 9 years <xref ref-type="bibr" rid="bib1.bibx50" id="paren.47"/>. Elevated concentrations and disproportionately high N<inline-formula><mml:math id="M184" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O variability have been observed in many instances for ice samples rich in mineral dust in both Antarctic and Greenland ice cores and are attributed to in situ production <xref ref-type="bibr" rid="bib1.bibx27 bib1.bibx62 bib1.bibx29 bib1.bibx63 bib1.bibx54 bib1.bibx56 bib1.bibx26" id="paren.48"/>. Measurements in the Vostok ice core by <xref ref-type="bibr" rid="bib1.bibx62" id="text.49"/> demonstrated this excess N<inline-formula><mml:math id="M185" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O production to have a strong imprint in both <inline-formula><mml:math id="M186" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">15</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>N (N<inline-formula><mml:math id="M187" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O) and <inline-formula><mml:math id="M188" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (N<inline-formula><mml:math id="M189" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O) records. For some of our EDC samples we observe the same systematic isotopic deviations as for the Vostok samples of that period, with <inline-formula><mml:math id="M190" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">15</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>N (N<inline-formula><mml:math id="M191" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O) and <inline-formula><mml:math id="M192" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (N<inline-formula><mml:math id="M193" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O) values that are more enriched and depleted, respectively, than typical atmospheric values. The coupling with dust is the basis of an empirical artefact detection method applicable to EDC samples. This method considers depth intervals where dust concentrations exceed an arbitrary threshold of 300 <inline-formula><mml:math id="M194" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi></mml:mrow></mml:math></inline-formula>g kg<inline-formula><mml:math id="M195" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> as affected by in situ production <xref ref-type="bibr" rid="bib1.bibx63 bib1.bibx54" id="paren.50"/>. We follow this approach and define 134.5 ka as the boundary for the section affected by artefacts. This is a slightly younger age than the last value regarded as unbiased by <xref ref-type="bibr" rid="bib1.bibx54" id="text.51"/>. Consequently, we refrain from interpreting N<inline-formula><mml:math id="M196" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O data points older than 134.5 ka as reflecting atmospheric variability.</p>
      <p id="d1e2566">The younger part of our records are used to study CH<inline-formula><mml:math id="M197" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M198" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O fluctuations during TII. In particular, we scrutinize our record with respect to the newly resolved variations belonging to the modes of variability presented above. To achieve this, we analyse the characteristics of the individual events as well as the background climate in which they occur.</p>
</sec>
<sec id="Ch1.S4.SS2">
  <label>4.2</label><?xmltex \opttitle{The 129\,ka event}?><title>The 129 ka event</title>
      <p id="d1e2596">The 129 ka event refers to the pronounced increase in CH<inline-formula><mml:math id="M199" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M200" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentrations to interglacial levels at the end of TII (Fig. <xref ref-type="fig" rid="Ch1.F2"/>). For both gases, this event accounts for about half of the deglacial change in concentrations.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F2" specific-use="star"><?xmltex \currentcnt{2}?><?xmltex \def\figurename{Figure}?><label>Figure 2</label><caption><p id="d1e2621">Evolution of the CH<inline-formula><mml:math id="M201" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M202" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentrations combined with complementary climate proxies during TII. The boxes delineate the climate periods mentioned in the text: the Penultimate Glacial Maximum (PGM), Heinrich Stadial 11 (HS11, delineation according to <xref ref-type="bibr" rid="bib1.bibx44" id="altparen.52"/>), and the Last Interglacial (LIG). <bold>(a)</bold> Composite CH<inline-formula><mml:math id="M203" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> record. <bold>(b)</bold> Composite N<inline-formula><mml:math id="M204" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O record. <bold>(c)</bold> Speleothem <inline-formula><mml:math id="M205" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (CaCO<inline-formula><mml:math id="M206" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>) records: Sanbao SB25 (light green) <xref ref-type="bibr" rid="bib1.bibx18" id="paren.53"/>, Hulu Cave MSX (khaki) <xref ref-type="bibr" rid="bib1.bibx17" id="paren.54"/>, Hulu cave MSP (dark green) <xref ref-type="bibr" rid="bib1.bibx17" id="paren.55"/>, and Sanbao–Dongge composite (pale yellow) <xref ref-type="bibr" rid="bib1.bibx19" id="paren.56"/>. <bold>(d)</bold> <inline-formula><mml:math id="M207" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (O<inline-formula><mml:math id="M208" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>) from EDC on the AICC2012 timescale <xref ref-type="bibr" rid="bib1.bibx40" id="paren.57"/>. <bold>(e)</bold> CO<inline-formula><mml:math id="M209" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> from EDC on the AICC2012 timescale <xref ref-type="bibr" rid="bib1.bibx40" id="paren.58"/>. <bold>(f)</bold> Antarctic surface temperature (relative to the last millennium) from EDC on the AICC2012 timescale <xref ref-type="bibr" rid="bib1.bibx39" id="paren.59"/>. <bold>(g)</bold> Composite <inline-formula><mml:math id="M210" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">ε</mml:mi><mml:mi mathvariant="normal">Nd</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> from the sediment core ODP Site 1063 <xref ref-type="bibr" rid="bib1.bibx20" id="paren.60"/>, including data points from <xref ref-type="bibr" rid="bib1.bibx13" id="text.61"/> (purple) and new measurements from <xref ref-type="bibr" rid="bib1.bibx20" id="text.62"/> (pale pink), on the timescale of <xref ref-type="bibr" rid="bib1.bibx20" id="text.63"/>. <bold>(h)</bold> <inline-formula><mml:math id="M211" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">231</mml:mn></mml:msup><mml:mi mathvariant="normal">Pa</mml:mi><mml:msup><mml:mo>/</mml:mo><mml:mn mathvariant="normal">230</mml:mn></mml:msup><mml:mi mathvariant="normal">Th</mml:mi></mml:mrow></mml:math></inline-formula> record from the sediment core ODP Site 1063 <xref ref-type="bibr" rid="bib1.bibx13" id="paren.64"/>, on the timescale of <xref ref-type="bibr" rid="bib1.bibx20" id="text.65"/>. <bold>(i)</bold> Mean summer (June to August) insolation at 40<inline-formula><mml:math id="M212" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> N <xref ref-type="bibr" rid="bib1.bibx9" id="paren.66"/>. <bold>(j)</bold> Relative sea level stand from the Red Sea synchronized on a radiometric timescale, including the maximum probability curve (purple) and its 95 % confidence interval (magenta) <xref ref-type="bibr" rid="bib1.bibx32" id="paren.67"/>. <bold>(k)</bold> Ice-rafted debris (IRD) from <xref ref-type="bibr" rid="bib1.bibx61" id="text.68"/> on the radiometric timescale of <xref ref-type="bibr" rid="bib1.bibx44" id="text.69"/>.</p></caption>
          <?xmltex \igopts{width=369.885827pt}?><graphic xlink:href="https://cp.copernicus.org/articles/17/1627/2021/cp-17-1627-2021-f02.png"/>

        </fig>

      <p id="d1e2847">CH<inline-formula><mml:math id="M213" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M214" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentrations rose in parallel with the main resumption of the AMOC, as indicated by the evolution of the isotopic ratio of neodymium 143 and 144 (<inline-formula><mml:math id="M215" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">ε</mml:mi><mml:mi mathvariant="normal">Nd</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>) <xref ref-type="bibr" rid="bib1.bibx20 bib1.bibx13" id="paren.70"/>. At the same time, the evolution of the isotopic composition of speleothem calcite (<inline-formula><mml:math id="M216" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (CaCO<inline-formula><mml:math id="M217" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>)) indicates a northward shift of the ITCZ <xref ref-type="bibr" rid="bib1.bibx18 bib1.bibx19" id="paren.71"/> (Fig. <xref ref-type="fig" rid="Ch1.F3"/>). These are fingerprints of DO-type variability. Accordingly, the abrupt CH<inline-formula><mml:math id="M218" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> rise likely reflects the response of terrestrial emissions from NH tropical wetlands. The simultaneous increase in both gases indicates that terrestrial emissions contributed, at least partly, to the N<inline-formula><mml:math id="M219" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O rise at <inline-formula><mml:math id="M220" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">129</mml:mn></mml:mrow></mml:math></inline-formula> ka. However, because the deglacial AMOC resumption occurred at this time, it can be assumed that marine sources also played a role. A contribution from both marine and terrestrial emissions is in agreement with the findings of <xref ref-type="bibr" rid="bib1.bibx57" id="text.72"/> and <xref ref-type="bibr" rid="bib1.bibx26" id="text.73"/> for DO-type fluctuations during TI. Higher resolution measurements of the isotopic composition of N<inline-formula><mml:math id="M221" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O combined with a deconvolution, similar to the aforementioned studies, are needed to quantitatively determine the relative contribution of the sources during the 129 ka event.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F3" specific-use="star"><?xmltex \currentcnt{3}?><?xmltex \def\figurename{Figure}?><label>Figure 3</label><caption><p id="d1e2955">Details of the 129 (left panel) and 134 ka events (right panel). <bold>(a)</bold> Composite CH<inline-formula><mml:math id="M222" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> record. <bold>(b)</bold> Composite N<inline-formula><mml:math id="M223" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O record. <bold>(c)</bold> Speleothem <inline-formula><mml:math id="M224" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (CaCO<inline-formula><mml:math id="M225" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>) records: Sanbao SB25 (light green) <xref ref-type="bibr" rid="bib1.bibx18" id="paren.74"/>, Hulu Cave MSX (khaki) <xref ref-type="bibr" rid="bib1.bibx17" id="paren.75"/>, Hulu cave MSP (dark green) <xref ref-type="bibr" rid="bib1.bibx17" id="paren.76"/>, and Sanbao–Dongge composite (pale yellow).   <bold>(d)</bold> <inline-formula><mml:math id="M226" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (O<inline-formula><mml:math id="M227" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>) from EDC on the AICC2012 timescale <xref ref-type="bibr" rid="bib1.bibx40" id="paren.77"/>. <bold>(e)</bold> Antarctic surface temperature (relative to the last millennium) from EDC on the AICC2012 timescale <xref ref-type="bibr" rid="bib1.bibx39" id="paren.78"/>. <bold>(f)</bold> Mean summer (June to August) insolation at 40<inline-formula><mml:math id="M228" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> N <xref ref-type="bibr" rid="bib1.bibx9" id="paren.79"/>. <bold>(g)</bold> Composite <inline-formula><mml:math id="M229" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">ε</mml:mi><mml:mi mathvariant="normal">Nd</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> from the sediment core ODP Site 1063 <xref ref-type="bibr" rid="bib1.bibx20" id="paren.80"/>, including data points from <xref ref-type="bibr" rid="bib1.bibx13" id="text.81"/> (purple) and new measurements from <xref ref-type="bibr" rid="bib1.bibx20" id="text.82"/> (pale pink), on the timescale of <xref ref-type="bibr" rid="bib1.bibx20" id="text.83"/>. <bold>(h)</bold> Relative sea level stand from the Red Sea synchronized on a radiometric timescale, including the maximum probability curve (purple) and its 95 % confidence interval (magenta) <xref ref-type="bibr" rid="bib1.bibx32" id="paren.84"/>.</p></caption>
          <?xmltex \igopts{width=398.338583pt}?><graphic xlink:href="https://cp.copernicus.org/articles/17/1627/2021/cp-17-1627-2021-f03.png"/>

        </fig>

</sec>
<sec id="Ch1.S4.SS3">
  <label>4.3</label><?xmltex \opttitle{The 130\,ka event}?><title>The 130 ka event</title>
      <p id="d1e3112">The 129 ka event is preceded by a phase of rising N<inline-formula><mml:math id="M230" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentrations in the interval from 130.7 to 130 ka at the end of HS11 (Fig. <xref ref-type="fig" rid="Ch1.F2"/>). This is reminiscent of the pattern of late HS-type increase, where N<inline-formula><mml:math id="M231" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentrations rose before the rapid DO-type Greenland temperature and CH<inline-formula><mml:math id="M232" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> increases <xref ref-type="bibr" rid="bib1.bibx56" id="paren.85"/>. The timescale of the 130 ka event is in the range of the duration typically observed for these episodes (<inline-formula><mml:math id="M233" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">0.5</mml:mn></mml:mrow></mml:math></inline-formula>–2 millennia) <xref ref-type="bibr" rid="bib1.bibx56" id="paren.86"/>, while the N<inline-formula><mml:math id="M234" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O growth rate appears slightly larger (<inline-formula><mml:math id="M235" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:math></inline-formula> ppb compared to typically <inline-formula><mml:math id="M236" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula> ppb per century). The lack of a concomitant CH<inline-formula><mml:math id="M237" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> fluctuation suggests that only the marine source contributed to the N<inline-formula><mml:math id="M238" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O increase, in agreement with the findings of <xref ref-type="bibr" rid="bib1.bibx57" id="text.87"/> and <xref ref-type="bibr" rid="bib1.bibx26" id="text.88"/> for the late HS1 rise. The change in marine emissions may be linked to a long-term adjustment of the nitrate and oxygen inventories in the upper ocean after a period of AMOC interruption <xref ref-type="bibr" rid="bib1.bibx60" id="paren.89"/>. Overall, despite the somewhat different rates of change, the 130 ka event likely constitutes an instance of a late-HS N<inline-formula><mml:math id="M239" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O fluctuation during TII. The attribution of the 130 ka feature to the pattern of late HS increase would be strengthened by additional measurements of <inline-formula><mml:math id="M240" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">15</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>N (N<inline-formula><mml:math id="M241" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O) and <inline-formula><mml:math id="M242" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (N<inline-formula><mml:math id="M243" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O), allowing the unambiguous identification of the source contributing to this event.</p>
</sec>
<?pagebreak page1634?><sec id="Ch1.S4.SS4">
  <label>4.4</label><?xmltex \opttitle{The 134\,ka event}?><title>The 134 ka event</title>
      <p id="d1e3277">Turning to the 134 ka event, its occurrence within HS11 and the properties of the CH<inline-formula><mml:math id="M244" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> increase (duration and amplitude) are reminiscent of the HS-type pattern of variability evidenced by <xref ref-type="bibr" rid="bib1.bibx51" id="text.90"/>. HS-type fluctuations resolved in the WAIS Divide (WD) ice core fully developed within 90–190 years <xref ref-type="bibr" rid="bib1.bibx51" id="paren.91"/>. The broader GAD of the EDC ice core implies that any such features would appear strongly dampened in our data. This is supported by continuous CH<inline-formula><mml:math id="M245" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> measurements in the Vostok ice core, demonstrating the absence of the characteristic overshoot resolved in the WD ice core during HS4 <xref ref-type="bibr" rid="bib1.bibx31 bib1.bibx51" id="paren.92"/>. Therefore, the sharpness and amplitude of the 134 ka event is not consistent with the picture of a substantially smoothed version of an HS-type fluctuation. The <inline-formula><mml:math id="M246" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">70</mml:mn></mml:mrow></mml:math></inline-formula> ppb rise observed in the EDC record would translate into a WD signal exceeding by far the amplitude range of the HS1, HS2, HS4, and HS5 fluctuations (32–53 ppb) <xref ref-type="bibr" rid="bib1.bibx51" id="paren.93"/>. Secondly, HS-type CH<inline-formula><mml:math id="M247" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> variability is also characterized by abrupt CO<inline-formula><mml:math id="M248" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> jumps, millennial-scale increases in <inline-formula><mml:math id="M249" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (O<inline-formula><mml:math id="M250" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>), enrichment in speleothem <inline-formula><mml:math id="M251" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (CaCO<inline-formula><mml:math id="M252" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>), and the absence of concomitant N<inline-formula><mml:math id="M253" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O variability <xref ref-type="bibr" rid="bib1.bibx4 bib1.bibx5 bib1.bibx6 bib1.bibx43 bib1.bibx26 bib1.bibx56 bib1.bibx54 bib1.bibx33" id="paren.94"/>. The simultaneous occurrence of the CH<inline-formula><mml:math id="M254" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M255" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O pulses at <inline-formula><mml:math id="M256" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">134</mml:mn></mml:mrow></mml:math></inline-formula> ka, the depletion in speleothem <inline-formula><mml:math id="M257" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (CaCO<inline-formula><mml:math id="M258" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>), and the lack of any fluctuation in the <inline-formula><mml:math id="M259" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (O<inline-formula><mml:math id="M260" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>) record <xref ref-type="bibr" rid="bib1.bibx40" id="paren.95"/> contradict these observations (Fig. <xref ref-type="fig" rid="Ch1.F3"/>). The 134 ka event is therefore likely to have resulted from different mechanisms and does not constitute an instance of an HS-type CH<inline-formula><mml:math id="M261" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> fluctuation during TII. On the other hand, simultaneous rises of atmospheric CH<inline-formula><mml:math id="M262" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M263" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentrations are observed during DO-type fluctuations. During the last glacial cycle, the amplitude of DO-type CH<inline-formula><mml:math id="M264" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> increases ranges from <inline-formula><mml:math id="M265" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">50</mml:mn></mml:mrow></mml:math></inline-formula> to 220 ppb in Greenland ice cores and elevated concentrations lasted for centuries to millennia <xref ref-type="bibr" rid="bib1.bibx3 bib1.bibx29" id="paren.96"/>. Accordingly, the magnitude of the 134 ka event fits well within the amplitude range observed for the well-resolved DO-type fluctuations in the EDC record of <xref ref-type="bibr" rid="bib1.bibx42" id="text.97"/> (<inline-formula><mml:math id="M266" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">50</mml:mn></mml:mrow></mml:math></inline-formula>–185 ppb). Going further, results from Greenland ice cores have shown that the amplitude of DO-type CH<inline-formula><mml:math id="M267" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> rises tracks the variations in low- to mid-latitude NH summer insolation, where the most substantial changes in concentration are associated with higher insolation. This indicates that the amount or seasonal distribution of solar radiation has modulated the response of CH<inline-formula><mml:math id="M268" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> sources during interstadials <xref ref-type="bibr" rid="bib1.bibx15 bib1.bibx29" id="paren.98"/>. The 134 ka event occurs during a time period of low NH summer insolation (Fig. <xref ref-type="fig" rid="Ch1.F2"/>), comparable to this at DO2. Yet, the magnitude of the 134 ka event appears larger (<inline-formula><mml:math id="M269" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">70</mml:mn></mml:mrow></mml:math></inline-formula> ppb compared to <inline-formula><mml:math id="M270" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">50</mml:mn></mml:mrow></mml:math></inline-formula> ppb for DO2 in the EDC record).</p>
      <p id="d1e3574">Associating our event with a DO-type pattern of variability requires evidence for a northward shift of the ITCZ and reinvigoration of the AMOC. Synchronous with the 134 ka event, within dating uncertainty, we observe a short-lived negative excursion in speleothem <inline-formula><mml:math id="M271" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (CaCO<inline-formula><mml:math id="M272" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>) records <xref ref-type="bibr" rid="bib1.bibx17" id="paren.99"/> (Fig. <xref ref-type="fig" rid="Ch1.F3"/>) as well as fluctuations in proxies reflecting salinity and runoff intensity in the Bay of Bengal <xref ref-type="bibr" rid="bib1.bibx48" id="paren.100"/>. These data indicate a transient strengthening of the NH tropical monsoon systems consistent with a northward shift of the ITCZ. Concerning the behaviour of the AMOC, we are not aware of studies reporting on a potential reinvigoration at this time. Nevertheless, oceanic tracers exhibit a small and short-lived fluctuation in the time interval 133–132 ka (on the timescale of <xref ref-type="bibr" rid="bib1.bibx13" id="altparen.101"/>) before reaching their maximum HS11 values <xref ref-type="bibr" rid="bib1.bibx13" id="paren.102"/>. On the updated chronology of the sediment core ODP Site 1063 <xref ref-type="bibr" rid="bib1.bibx20" id="paren.103"/>, the negative excursion in the <inline-formula><mml:math id="M273" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">ε</mml:mi><mml:mi mathvariant="normal">Nd</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> record of <xref ref-type="bibr" rid="bib1.bibx13" id="text.104"/> coincides with a comparably small value in the data of <xref ref-type="bibr" rid="bib1.bibx20" id="text.105"/> (Fig. <xref ref-type="fig" rid="Ch1.F2"/>). However, the revised chronology places the excursion in <inline-formula><mml:math id="M274" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">ε</mml:mi><mml:mi mathvariant="normal">Nd</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M275" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">231</mml:mn></mml:msup><mml:mi mathvariant="normal">Pa</mml:mi><mml:msup><mml:mo>/</mml:mo><mml:mn mathvariant="normal">230</mml:mn></mml:msup><mml:mi mathvariant="normal">Th</mml:mi></mml:mrow></mml:math></inline-formula> substantially earlier than the 134 ka event (Fig. <xref ref-type="fig" rid="Ch1.F3"/>). The onset of this excursion is at <inline-formula><mml:math id="M276" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">137.4</mml:mn></mml:mrow></mml:math></inline-formula> ka, corresponding to a shift by <inline-formula><mml:math id="M277" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">4900</mml:mn></mml:mrow></mml:math></inline-formula> years with respect to the timescale of <xref ref-type="bibr" rid="bib1.bibx13" id="text.106"/>. Since the timescale of the sediment core is tuned to the Antarctic Ice Core Chronology (AICC2012) <xref ref-type="bibr" rid="bib1.bibx7 bib1.bibx65" id="paren.107"/> within an estimated uncertainty of 400 years, the fluctuations resolved in the ice and marine cores should, in principle, not be regarded as synchronous. However, the alignment with the AICC2012 is performed using only one tie point between CH<inline-formula><mml:math id="M278" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and the isotopic composition of planktonic foraminifera (at <inline-formula><mml:math id="M279" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">128.7</mml:mn></mml:mrow></mml:math></inline-formula> ka, corresponding to the abrupt CH<inline-formula><mml:math id="M280" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> increase into the LIG) <xref ref-type="bibr" rid="bib1.bibx20" id="paren.108"/>. Therefore, it may be possible that the two timescales are less tightly aligned away from this tie point. If this would be the case, it could be hypothesized that the excursions in oceanic proxies are synchronous with the fluctuations of  <inline-formula><mml:math id="M281" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (CaCO<inline-formula><mml:math id="M282" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>), CH<inline-formula><mml:math id="M283" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>, and N<inline-formula><mml:math id="M284" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O.</p>
      <p id="d1e3764">DO-type variability is typically also imprinted in the temperature record from Antarctic ice cores as well as in the <inline-formula><mml:math id="M285" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (O<inline-formula><mml:math id="M286" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>) record. However, the responses of these proxies are generally attenuated or occur on longer timescales compared to those of CH<inline-formula><mml:math id="M287" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and <inline-formula><mml:math id="M288" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (CaCO<inline-formula><mml:math id="M289" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>). Accordingly, a short and small-amplitude interstadial at <inline-formula><mml:math id="M290" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">134</mml:mn></mml:mrow></mml:math></inline-formula> ka might not have left discernible imprints in the respective records of <xref ref-type="bibr" rid="bib1.bibx40" id="text.109"/> and <xref ref-type="bibr" rid="bib1.bibx39" id="text.110"/> (Figs. <xref ref-type="fig" rid="Ch1.F2"/> and <xref ref-type="fig" rid="Ch1.F3"/>).</p>
      <?pagebreak page1635?><p id="d1e3838">Taking the proxy evidences together, we speculate that a brief and small-scale resumption of the AMOC might have occurred within HS11, accounting for the northward ITCZ shift and the rise in atmospheric CH<inline-formula><mml:math id="M291" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M292" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentrations. We acknowledge that our interpretation is limited by the relatively coarse resolution of <inline-formula><mml:math id="M293" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">ε</mml:mi><mml:mi mathvariant="normal">Nd</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M294" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">231</mml:mn></mml:msup><mml:mi mathvariant="normal">Pa</mml:mi><mml:msup><mml:mo>/</mml:mo><mml:mn mathvariant="normal">230</mml:mn></mml:msup><mml:mi mathvariant="normal">Th</mml:mi></mml:mrow></mml:math></inline-formula> as well as by the uncertainty arising from cross-dating sediment and ice core records. Concerning N<inline-formula><mml:math id="M295" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O, we finally note that the duration of the rise and the simultaneity with the excursion in CH<inline-formula><mml:math id="M296" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> suggest that terrestrial N<inline-formula><mml:math id="M297" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O emissions contributed by far the most to the 134 ka event <xref ref-type="bibr" rid="bib1.bibx26" id="paren.111"/>.</p>
      <p id="d1e3920">Should our interpretation hold, the 134 ka event can be regarded as a short DO-type fluctuation. We speculate that the hypothesized AMOC reinvigoration might have been perturbed by Meltwater Pulse 2B (MWP-2B). MWP-2B represents <inline-formula><mml:math id="M298" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">70</mml:mn></mml:mrow></mml:math></inline-formula> % of the deglacial sea level change and coincides with the 134 ka event within dating uncertainty (Fig. <xref ref-type="fig" rid="Ch1.F2"/>) <xref ref-type="bibr" rid="bib1.bibx44" id="paren.112"/>. The disruption of the oceanic circulation by freshwater forcing might have been enabled by the high susceptibility of the AMOC to perturbations at a time when the high-latitude SH was particularly cold <xref ref-type="bibr" rid="bib1.bibx16" id="paren.113"/>, as was the case during HS11 (Fig. <xref ref-type="fig" rid="Ch1.F2"/>). This situation favours the occurrence of relatively short, centennial, interstadials such as those appearing near the Last Glacial Maximum in Greenland ice cores.</p>
</sec>
</sec>
<sec id="Ch1.S5" sec-type="conclusions">
  <label>5</label><title>Conclusions</title>
      <p id="d1e3953">In the present study, we increased the resolution of the deglacial CH<inline-formula><mml:math id="M299" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M300" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O records, allowing us to derive composite datasets covering TII (140–128 ka) at average resolutions of <inline-formula><mml:math id="M301" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">100</mml:mn></mml:mrow></mml:math></inline-formula> years. Our results display pronounced fluctuations standing out of the overall transition of CH<inline-formula><mml:math id="M302" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M303" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentrations to interglacial conditions. The most prominent one is placed at <inline-formula><mml:math id="M304" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">129</mml:mn></mml:mrow></mml:math></inline-formula> ka and delineates the transition into the LIG. We assume that terrestrial and marine sources contributed to the N<inline-formula><mml:math id="M305" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O increase at this time. Additionally, we unequivocally identify a 134 and 130 ka event. We link the latter to the pattern of late HS-type N<inline-formula><mml:math id="M306" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O increase, where changes in marine emissions are likely to be the only contributor. The former is regarded as a short DO-type fluctuation, whose timescale indicates that only terrestrial N<inline-formula><mml:math id="M307" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O sources likely contributed to the increase. We note that these fluctuations in CH<inline-formula><mml:math id="M308" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M309" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentrations during the penultimate deglaciation are all instances of recurrent modes of variability, also evidenced during the last deglaciation as well as during the last glacial period.</p><?xmltex \hack{\clearpage}?>
</sec>

      
      </body>
    <back><app-group>

<?pagebreak page1636?><app id="App1.Ch1.S1">
  <?xmltex \currentcnt{A}?><label>Appendix A</label><?xmltex \opttitle{New measurement system for CH${}_{4}$ and N${}_{2}$O}?><title>New measurement system for CH<inline-formula><mml:math id="M310" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M311" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O</title>
      <p id="d1e4089">Although gas chromatography (GC) has been used extensively to measure CH<inline-formula><mml:math id="M312" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M313" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O at the University of Bern <xref ref-type="bibr" rid="bib1.bibx27 bib1.bibx28 bib1.bibx29 bib1.bibx2 bib1.bibx3 bib1.bibx42 bib1.bibx54 bib1.bibx55 bib1.bibx56 bib1.bibx63" id="paren.114"><named-content content-type="pre">e.g.</named-content></xref>, the totally revised extraction and GC setup presented here has not been described before. The device is composed of different functional units, enabling the different actions of the system (standard injection, extraction, separation, and detection) (coloured boxes in Fig. <xref ref-type="fig" rid="App1.Ch1.S1.F4"/>). The measurements are carried out using three distinct lines. The ice line (IL, under vacuum, red path in Fig. <xref ref-type="fig" rid="App1.Ch1.S1.F4"/>) is used to extract air from ice core samples. The continuous-flow line (CFL, flushed with He, green path in Fig. <xref ref-type="fig" rid="App1.Ch1.S1.F4"/>) is used to measure standards to calibrate ice core measurements. Standards and samples are introduced differently into the separation unit to gain time during daily operation. Therefore, following the identical treatment principle, we also employ the standard over ice line (SOIL, blue line in Fig. <xref ref-type="fig" rid="App1.Ch1.S1.F4"/>) to periodically inject standards for comparison with similar measurements performed with the CFL in order to account for contamination stemming from the IL. The mean offset between the lines is used to correct IL data.</p>
      <p id="d1e4124">To extract gas from ice core samples, we use continuous extraction under vacuum. Air is released from the ice during the melting (immersing the bottom of the vessel in a <inline-formula><mml:math id="M314" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">20</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M315" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C water bath) and is simultaneously adsorbed on an activated charcoal trap held at <inline-formula><mml:math id="M316" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">196</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M317" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C using liquid nitrogen (T2 in Fig. <xref ref-type="fig" rid="App1.Ch1.S1.F4"/>). Water vapour is condensed beforehand using another cold trap held at <inline-formula><mml:math id="M318" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">80</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M319" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C (T1 in Fig. <xref ref-type="fig" rid="App1.Ch1.S1.F4"/>). The progression of the extraction is monitored with a pressure gauge (P5 in Fig. <xref ref-type="fig" rid="App1.Ch1.S1.F4"/>). The completion of the extraction is indicated by a P5 pressure value <inline-formula><mml:math id="M320" display="inline"><mml:mrow><mml:mi mathvariant="italic">⩽</mml:mi><mml:mn mathvariant="normal">0.25</mml:mn></mml:mrow></mml:math></inline-formula> mbar. When this value is reached, T2 is isolated from the vessel and heated to facilitate CH<inline-formula><mml:math id="M321" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M322" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O desorption from the charcoal bed. The duration and final temperature of the heating (5 min, 130 <inline-formula><mml:math id="M323" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C) ensure full recovery of the adsorbed gas. At the end of this phase, He flushes the content of T2 into the separation unit. Overall, the advantage of our procedure is the permanently low CH<inline-formula><mml:math id="M324" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M325" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O partial pressure, as well as total air pressure, prevailing in the vessel during the extraction. Accordingly, equilibrium conditions with respect to solubility are never reached, precluding the need of a solubility correction. This type of correction was required in traditional analyses using a melt–refreeze method, where the air sample is enclosed in the vessel head space during the extraction.</p>
      <p id="d1e4247">CH<inline-formula><mml:math id="M326" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M327" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O are separated from the bulk air in the separation unit before reaching the detection unit equipped with a thermal conductivity detector (TCD), a flame-ionization detector (FID), and an electron-capture detector (ECD) to quantify the amount of air, CH<inline-formula><mml:math id="M328" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>, and N<inline-formula><mml:math id="M329" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O, respectively. The separation unit is composed of a succession of GC columns. CH<inline-formula><mml:math id="M330" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M331" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O are separated from the bulk air in the precolumn and analytical column (Fig. <xref ref-type="fig" rid="App1.Ch1.S1.F4"/>). After detection of the air peak by the TCD, V8 allows us to route CH<inline-formula><mml:math id="M332" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> towards the FID (via T5 and T7) and N<inline-formula><mml:math id="M333" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O towards the ECD (via T4 and T6) (Fig. <xref ref-type="fig" rid="App1.Ch1.S1.F4"/>). T5 and T4 are used to separate CH<inline-formula><mml:math id="M334" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M335" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O, respectively, from species having almost similar retention times. T7 and T6 are used to focus the gas to obtain sharp peaks in the chromatograph.</p>
      <p id="d1e4347">The amount of air, CH<inline-formula><mml:math id="M336" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>, and N<inline-formula><mml:math id="M337" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O is quantified by integrating the area below the corresponding GC peaks. For each species, calibration curves are established between areas and the number of moles calculated using the volume, temperature, and pressure of the sample loop as well as the known CH<inline-formula><mml:math id="M338" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M339" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O mole fractions of the standard gases. We use a set of primary standards provided by the National Oceanic and Atmospheric Administration and referenced to the World Meteorological Organisation mole fraction scales: the WMOX2004A scale (CH<inline-formula><mml:math id="M340" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>) and NOAA-2006A (N<inline-formula><mml:math id="M341" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O) <xref ref-type="bibr" rid="bib1.bibx21 bib1.bibx34" id="paren.115"/>. This set of standards brackets the glacial–interglacial range of CH<inline-formula><mml:math id="M342" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> (358.88 <inline-formula><mml:math id="M343" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.16 ppb, 838.59 <inline-formula><mml:math id="M344" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.28 ppb, and 1729.30 <inline-formula><mml:math id="M345" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.34 ppb) and N<inline-formula><mml:math id="M346" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentrations (187.10 <inline-formula><mml:math id="M347" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.12 ppb, 194.13 <inline-formula><mml:math id="M348" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.12 ppb, and 300.20 <inline-formula><mml:math id="M349" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.12 ppb). CH<inline-formula><mml:math id="M350" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M351" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O mole fractions are calculated by dividing the number of CH<inline-formula><mml:math id="M352" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M353" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O moles by the number moles of air. In addition, total air content can also be quantified using the TCD area as well as the volume, temperature, and pressure of the sample loop.</p>
      <p id="d1e4506">After calibration, the results are corrected for the line offset between CFL and SOIL. This offset accounts for the blank introduced in the IL and is averaged over, at least, a measurement campaign. The CH<inline-formula><mml:math id="M354" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M355" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O line offsets appear to be linearly dependent on the concentration enabling the use of linear interpolations to correct ice core results.</p>
      <p id="d1e4527">The uncertainty of the CH<inline-formula><mml:math id="M356" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M357" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O data derived with our instrument amounts to 7 and 6 ppb, respectively. It is calculated as the sum of the individual uncertainty, associated with the overall analytical procedure (1<inline-formula><mml:math id="M358" display="inline"><mml:mi mathvariant="italic">σ</mml:mi></mml:math></inline-formula> standard deviation of SOIL measurements) and with the line offset correction, in quadrature.</p>

      <?xmltex \floatpos{h!}?><fig id="App1.Ch1.S1.F4"><?xmltex \currentcnt{A1}?><?xmltex \def\figurename{Figure}?><label>Figure A1</label><caption><p id="d1e4557">Flow scheme of the CH<inline-formula><mml:math id="M359" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M360" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O measurement system. The red, green, and blue paths highlight the ice line (IL), continuous-flow line (CFL), and standard over ice line (SOIL), respectively. Coloured boxes display the different functional units of the system discussed in Appendix A.</p></caption>
        <?xmltex \hack{\hsize\textwidth}?>
        <?xmltex \igopts{width=497.923228pt}?><graphic xlink:href="https://cp.copernicus.org/articles/17/1627/2021/cp-17-1627-2021-f04.png"/>

      </fig>

<?xmltex \hack{\clearpage}?>
</app>

<?pagebreak page1638?><app id="App1.Ch1.S2">
  <?xmltex \currentcnt{B}?><label>Appendix B</label><?xmltex \opttitle{Construction of composite CH${}_{4}$ and N${}_{2}$O records}?><title>Construction of composite CH<inline-formula><mml:math id="M361" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M362" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O records</title>
      <p id="d1e4615">The construction of the composite records presented in this study is complicated by offsets between the datasets, where our results appear on average 18 <inline-formula><mml:math id="M363" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 10 ppb (CH<inline-formula><mml:math id="M364" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>) and 21 <inline-formula><mml:math id="M365" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 3 ppb (N<inline-formula><mml:math id="M366" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O) higher than previous data, although all datasets show the same relative changes (Fig. <xref ref-type="fig" rid="App1.Ch1.S2.F5"/>). The offsets are calculated as the mean of the residuals between splines with cut-off periods of 10 000 years fitted through the datasets. We computed splines according to <xref ref-type="bibr" rid="bib1.bibx23" id="text.116"/>, using the same routine as <xref ref-type="bibr" rid="bib1.bibx8" id="text.117"/>, where each spline is the average of 1000 iterations with data points varied within a normal distribution inside their uncertainty range.</p>
      <p id="d1e4659">It seems likely that the offsets are linked to the different extraction techniques employed. In fact, the published EDC data were measured at the University of Bern and Grenoble with instruments using melt–refreeze extraction <xref ref-type="bibr" rid="bib1.bibx42 bib1.bibx54" id="paren.118"/>. Melt–refreeze extraction is prone to underestimate CH<inline-formula><mml:math id="M367" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M368" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentrations if the refreezing is not perfectly efficient, while in our method air is quantitatively extracted from the ice samples. We note that also the values presented in previous publications had to be aligned for interlaboratory offsets on the order of 10 ppb for CH<inline-formula><mml:math id="M369" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx42" id="paren.119"/>, which may also reflect differences in the extraction efficiency of previously used melt–refreeze methods in different labs. Because melt–refreeze extraction has been the standard procedure for decades, the EDC records have been measured exclusively using this technique. We therefore think that additional overlapping measurements with an independent extraction technique (e.g. sublimation) are needed to resolve the dispute. Without further evidence, we prefer striving for consistency by correcting our data to the EDC benchmark records of <xref ref-type="bibr" rid="bib1.bibx42" id="text.120"/> and <xref ref-type="bibr" rid="bib1.bibx54" id="text.121"/>. To achieve this, we subtract the mean offsets of 18 (CH<inline-formula><mml:math id="M370" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>) and 21 ppb (N<inline-formula><mml:math id="M371" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O) from our results. This approach is facilitated by the high degree of co-variation between the datasets (Fig. <xref ref-type="fig" rid="App1.Ch1.S2.F5"/>).</p>
      <p id="d1e4722">The merging procedure described above adds an additional source of uncertainty to our results. Accounting for the uncertainty of the mean offset, taken as the standard deviation (1<inline-formula><mml:math id="M372" display="inline"><mml:mi mathvariant="italic">σ</mml:mi></mml:math></inline-formula>) of the residuals between the splines, increases the total uncertainty of the new data included in the composite records to 12 (CH<inline-formula><mml:math id="M373" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>) and 8 ppb (N<inline-formula><mml:math id="M374" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O). For the published EDC values and the isotopic measurements, the uncertainties amount to 10 ppb (CH<inline-formula><mml:math id="M375" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>), 4 ppb (N<inline-formula><mml:math id="M376" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O), 0.22 ‰ (<inline-formula><mml:math id="M377" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">15</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>N (N<inline-formula><mml:math id="M378" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O)), and 0.34 ‰ (<inline-formula><mml:math id="M379" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O (N<inline-formula><mml:math id="M380" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O)), as reported in <xref ref-type="bibr" rid="bib1.bibx42" id="text.122"/>, <xref ref-type="bibr" rid="bib1.bibx54" id="text.123"/>, and <xref ref-type="bibr" rid="bib1.bibx59" id="text.124"/>.</p><?xmltex \hack{\clearpage}?><?xmltex \floatpos{h!}?><fig id="App1.Ch1.S2.F5"><?xmltex \currentcnt{B1}?><?xmltex \def\figurename{Figure}?><label>Figure B1</label><caption><p id="d1e4822">Offsets between new and published CH<inline-formula><mml:math id="M381" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M382" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O EDC records. Dashed lines show the new measurements plotted against the published ones (data are from the spline approximations introduced in Appendix B). Solid lines are linear fits through these data.</p></caption>
        <?xmltex \hack{\hsize\textwidth}?>
        <?xmltex \igopts{width=497.923228pt}?><graphic xlink:href="https://cp.copernicus.org/articles/17/1627/2021/cp-17-1627-2021-f05.png"/>

      </fig>

<?xmltex \hack{\clearpage}?>
</app>
  </app-group><notes notes-type="dataavailability"><title>Data availability</title>

      <p id="d1e4857">The new CH<inline-formula><mml:math id="M383" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M384" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O data are available at the World Data Center for Paleoclimatology under the following link: <uri>https://www.ncdc.noaa.gov/paleo/study/33673</uri> <xref ref-type="bibr" rid="bib1.bibx58" id="paren.125"/>.</p>
  </notes><notes notes-type="authorcontribution"><title>Author contributions</title>

      <p id="d1e4887">The present study was designed by TFS, HF, and LoS. LoS and JH performed the methane and nitrous oxide measurements. JoS provided the isotopic data. LoS wrote the text with inputs from CNA, JoS, JH, LuS, JiS, FJ, JC, HF, and TFS.</p>
  </notes><notes notes-type="competinginterests"><title>Competing interests</title>

      <p id="d1e4893">The authors declare that they have no conflict of interest.</p>
  </notes><notes notes-type="disclaimer"><title>Disclaimer</title>

      <p id="d1e4899">Publisher’s note: Copernicus Publications remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.</p>
  </notes><ack><title>Acknowledgements</title><p id="d1e4905">The authors would like to thank Barbara Seth for the measurements of the isotopic composition of N<inline-formula><mml:math id="M385" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O, Gregory Teste for assistance in cutting ice samples, and Michael Bock and Jan Strähl for the construction of the new CH<inline-formula><mml:math id="M386" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and N<inline-formula><mml:math id="M387" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O measurement system. We thank the reviewers and the editor for detailed and constructive comments that improved this paper. We acknowledge financial support by the Swiss National Science Foundation (SNF project numbers 200020_172745, 200020_200492, 200020_172506, 200020_200511, and 200020_159563). This work is a contribution to the European Project for Ice Coring in Antarctica (EPICA), a joint European Science Foundation/European Commission scientific programme, funded by the European Union and by national contributions from Belgium, Denmark, France, Germany, Italy, The Netherlands, Norway, Sweden, Switzerland, and the United Kingdom. The main logistic support was provided by IPEV and PNRA (at Dome C) and AWI (at Dronning Maud Land). This is EPICA publication no. 319. This project is TiPES (Tipping Points in the Earth System) contribution no. 125. This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant 820970.</p></ack><notes notes-type="financialsupport"><title>Financial support</title>

      <p id="d1e4937">This research has been supported by the Swiss National Science Foundation (SNF project numbers 200020_172745, 200020_172506, 200020_159563,  200020_200492 and 200020_200511) and by the European Union's Horizon 2020 research and innovation programme (grant no. 820970).</p>
  </notes><notes notes-type="reviewstatement"><title>Review statement</title>

      <p id="d1e4943">This paper was edited by Luke Skinner and reviewed by two anonymous referees.</p>
  </notes><ref-list>
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    <!--<article-title-html>CH<sub>4</sub> and N<sub>2</sub>O fluctuations during the penultimate deglaciation</article-title-html>
<abstract-html><p>Deglaciations are characterized by the largest natural changes in methane (CH<sub>4</sub>) and nitrous oxide (N<sub>2</sub>O) concentrations of the past 800&thinsp;000 years. Reconstructions of millennial- to centennial-scale variability within these periods are mostly restricted to the last deglaciation. In this study, we present composite records of CH<sub>4</sub> and N<sub>2</sub>O concentrations from the EPICA Dome C ice core covering the penultimate deglaciation at temporal resolutions of  ∼ 100 years. Our data permit the identification of centennial-scale fluctuations during the transition from glacial to interglacial levels. At  ∼ 134 000 and  ∼ 129 000 years before present (hereafter ka), both CH<sub>4</sub> and N<sub>2</sub>O increased on centennial timescales. These abrupt rises are similar to the fluctuations associated with the Dansgaard–Oeschger events identified in the last glacial period. In addition, gradually rising N<sub>2</sub>O levels at  ∼ 130&thinsp;ka resemble a pattern of increasing N<sub>2</sub>O concentrations on millennial timescales characterizing the later part of Heinrich stadials. Overall, the events in CH<sub>4</sub> and N<sub>2</sub>O during the penultimate deglaciation exhibit modes of variability that are also found during the last deglaciation and glacial cycle, suggesting that the processes leading to changes in emission during the transitions were similar but their timing differed.</p></abstract-html>
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