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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-20-121-2024</article-id><title-group><article-title>Deglacial export of pre-aged terrigenous carbon to<?xmltex \hack{\break}?> the Bay of Biscay</article-title><alt-title>Deglacial export of pre-aged terrigenous carbon to the Bay of Biscay</alt-title>
      </title-group><?xmltex \runningtitle{Deglacial export of pre-aged terrigenous carbon to the Bay of Biscay}?><?xmltex \runningauthor{E. Queiroz Alves et al.}?>
      <contrib-group>
        <contrib contrib-type="author" corresp="yes" rid="aff1 aff5">
          <name><surname>Queiroz Alves</surname><given-names>Eduardo</given-names></name>
          <email>eduardoa@id.uff.br</email>
        <ext-link>https://orcid.org/0000-0003-0919-326X</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1 aff2 aff6">
          <name><surname>Wong</surname><given-names>Wanyee</given-names></name>
          
        <ext-link>https://orcid.org/0000-0003-1066-6829</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Hefter</surname><given-names>Jens</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-5823-1966</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1 aff4">
          <name><surname>Grotheer</surname><given-names>Hendrik</given-names></name>
          
        <ext-link>https://orcid.org/0000-0003-0207-3767</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff3">
          <name><surname>Tesi</surname><given-names>Tommaso</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Gentz</surname><given-names>Torben</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff4">
          <name><surname>Zonneveld</surname><given-names>Karin</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1 aff2 aff4">
          <name><surname>Mollenhauer</surname><given-names>Gesine</given-names></name>
          
        <ext-link>https://orcid.org/0000-0001-5138-564X</ext-link></contrib>
        <aff id="aff1"><label>1</label><institution>Alfred Wegener Institute for Polar and Marine Research, Bremerhaven, Germany</institution>
        </aff>
        <aff id="aff2"><label>2</label><institution>Department of Geosciences, University of Bremen, Bremen, Germany</institution>
        </aff>
        <aff id="aff3"><label>3</label><institution>Institute of Polar Sciences – National Research Council, Bologna, Italy</institution>
        </aff>
        <aff id="aff4"><label>4</label><institution>MARUM-Center for Marine Environmental Sciences, University of Bremen, Bremen, Germany</institution>
        </aff>
        <aff id="aff5"><label>a</label><institution>now at: Departamento de Geoquímica, Universidade Federal Fluminense, Niterói, Brazil</institution>
        </aff>
        <aff id="aff6"><label>b</label><institution>now at: NORCE Norwegian Research Centre, Bjerknes Centre for Climate Research, Bergen, Norway</institution>
        </aff>
      </contrib-group>
      <author-notes><corresp id="corr1">Eduardo Queiroz Alves (eduardoa@id.uff.br)</corresp></author-notes><pub-date><day>16</day><month>January</month><year>2024</year></pub-date>
      
      <volume>20</volume>
      <issue>1</issue>
      <fpage>121</fpage><lpage>136</lpage>
      <history>
        <date date-type="received"><day>13</day><month>February</month><year>2023</year></date>
           <date date-type="rev-request"><day>7</day><month>March</month><year>2023</year></date>
           <date date-type="rev-recd"><day>15</day><month>November</month><year>2023</year></date>
           <date date-type="accepted"><day>16</day><month>November</month><year>2023</year></date>
      </history>
      <permissions>
        <copyright-statement>Copyright: © 2024 Eduardo Queiroz Alves et al.</copyright-statement>
        <copyright-year>2024</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/cp-20-121-2024.html">This article is available from https://cp.copernicus.org/articles/cp-20-121-2024.html</self-uri><self-uri xlink:href="https://cp.copernicus.org/articles/cp-20-121-2024.pdf">The full text article is available as a PDF file from https://cp.copernicus.org/articles/cp-20-121-2024.pdf</self-uri>
      <abstract><title>Abstract</title>

      <p id="d1e181">The last deglaciation is the most recent relatively well-documented period of pronounced and fast climate warming, and, as such, it holds important information for our understanding of the climate system. Notably, while research into terrestrial organic carbon reservoirs has been instrumental in exploring the possible sources of atmospheric carbon dioxide during periods of rapid change, the underlying mechanisms are not fully understood. Here we investigate the mobilization of organic matter to the Bay of Biscay, located in the north-eastern Atlantic Ocean off the coasts of France and Spain. Specifically, we focus on the area that was the mouth of the Channel River during the last deglaciation, where an enhanced terrigenous input has been reported for the last glacial–interglacial transition. We conducted a comprehensive suite of biomarker analyses (e.g. <italic>n</italic>-alkanes, hopanes and <italic>n</italic>-alkanoic acids) and isotopic investigations (radiocarbon dating and <inline-formula><mml:math id="M1" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C measurements) on a high-resolution sedimentary archive. The present study provides the first direct evidence for the fluvial supply of immature and ancient terrestrial organic matter to the core location. Moreover, our results reveal the possibility of permafrost carbon export to the ocean, driven by processes such as deglacial warming and glacial erosion. These findings are consistent with observations from other regions characterized by present or past permafrost conditions on land, which have shown that permafrost thaw and glacial erosion can lead to carbon remobilization, potentially influencing atmospheric carbon dioxide levels.</p>
  </abstract>
    
<funding-group>
<award-group id="gs1">
<funding-source>Alexander von Humboldt-Stiftung</funding-source>
<award-id>1208249</award-id>
</award-group>
<award-group id="gs2">
<funding-source>Deutsche Forschungsgemeinschaft</funding-source>
<award-id>390741603</award-id>
</award-group>
</funding-group>
</article-meta>
  </front>
<body>
      

<sec id="Ch1.S1" sec-type="intro">
  <label>1</label><title>Introduction</title>
      <p id="d1e210">High-latitude permafrost soils hold ca. 1000 Pg of soil organic carbon (C) in the upper 3 m of the northern circumpolar region <xref ref-type="bibr" rid="bib1.bibx55" id="paren.1"/>. This immense amount of C is in the form of frozen organic matter (OM), the thawing of which releases greenhouse gases, inducing positive feedback mechanisms that have implications for the C cycle on a global scale <xref ref-type="bibr" rid="bib1.bibx151 bib1.bibx117 bib1.bibx118 bib1.bibx55 bib1.bibx119" id="paren.2"/>. While current climate change raises concerns about the stability of these massive pools of organic C <xref ref-type="bibr" rid="bib1.bibx138 bib1.bibx114" id="paren.3"/>, the dynamic character of Earth’s climate means that past trends and variability can be examined to improve future projections of this effect. The hypothesis of a combined contribution of ancient terrestrial C, potentially derived from thawing permafrost, and marine C sources to elevated atmospheric levels of carbon dioxide (<inline-formula><mml:math id="M2" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>) and methane (<inline-formula><mml:math id="M3" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CH</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>) during the last deglaciation is discussed in several studies <xref ref-type="bibr" rid="bib1.bibx25 bib1.bibx65 bib1.bibx10 bib1.bibx28 bib1.bibx122" id="paren.4"/>. Over the course of the Last Glacial Maximum (LGM), large expanses of continuous permafrost were found<?pagebreak page122?> in the Eurasian continent, covering much of central and western Europe, in areas where permafrost cover today no longer exists <xref ref-type="bibr" rid="bib1.bibx135 bib1.bibx78 bib1.bibx136 bib1.bibx147 bib1.bibx112 bib1.bibx137" id="paren.5"/> (Fig. <xref ref-type="fig" rid="Ch1.F1"/>). These regions comprise the southern edge of the LGM permafrost area and, according to <xref ref-type="bibr" rid="bib1.bibx65" id="text.6"/>, are likely to have experienced a rapid loss of massive amounts of ancient C as a result of thawing during the last deglaciation. However, while direct evidence for the deglacial remobilization of ancient C from permafrost has been reported for the Arctic <xref ref-type="bibr" rid="bib1.bibx128 bib1.bibx62 bib1.bibx84 bib1.bibx85 bib1.bibx145" id="paren.7"/> and subarctic <xref ref-type="bibr" rid="bib1.bibx143 bib1.bibx89" id="paren.8"/>, similar data are still lacking for the European realm, where the phenomenon has been suggested on the basis of enhanced terrigenous biomarker concentrations in sediment cores <xref ref-type="bibr" rid="bib1.bibx87 bib1.bibx111 bib1.bibx124" id="paren.9"/>.</p>
      <p id="d1e266">During the LGM, continental glaciers were part of the European landscape. The Fennoscandian (FIS) and the British–Irish (BIIS) ice sheets covered most of Britain, Ireland, northern Europe and the North Sea <xref ref-type="bibr" rid="bib1.bibx15 bib1.bibx127 bib1.bibx81" id="paren.10"/>, contributing to the lower eustatic sea level and altering coastlines <xref ref-type="bibr" rid="bib1.bibx35 bib1.bibx74 bib1.bibx75" id="paren.11"><named-content content-type="pre">e.g.</named-content></xref>. This sea-level lowstand, paired with the configuration of the BIIS and the FIS, led to a reorganization of major European drainage basins, with continental runoff being funnelled through the English Channel <xref ref-type="bibr" rid="bib1.bibx43" id="paren.12"/>. The so-called Fleuve Manche or Channel River received the runoff of major European rivers, carrying meltwaters from glaciers and ice sheets <xref ref-type="bibr" rid="bib1.bibx2 bib1.bibx14" id="paren.13"><named-content content-type="pre">e.g.</named-content></xref> (Fig. <xref ref-type="fig" rid="Ch1.F1"/>). As a consequence, changes in the hydrological cycle in Europe during the last glacial–interglacial transition induced a strong response from this system, resulting in increased water flow in the Channel River and its tributaries <xref ref-type="bibr" rid="bib1.bibx87 bib1.bibx129 bib1.bibx130" id="paren.14"><named-content content-type="pre">e.g.</named-content></xref>. Permafrost developed in the glacier-free areas of the continent, extending across a large portion of the Channel River (Fig. <xref ref-type="fig" rid="Ch1.F1"/>), and towards the end of the last glaciation it is likely to have reached its maximum extent, with discontinuous permafrost present in regions almost as far south as the Mediterranean Sea <xref ref-type="bibr" rid="bib1.bibx137" id="paren.15"/>.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F1"><?xmltex \currentcnt{1}?><?xmltex \def\figurename{Figure}?><label>Figure 1</label><caption><p id="d1e300">North-western Europe during the LGM. The blue arrow indicates the downstream course of the Channel River from the eastern flank of the FIS. The dashed lines show the distribution of permafrost <xref ref-type="bibr" rid="bib1.bibx108" id="paren.16"><named-content content-type="post">and references therein</named-content></xref>, and the red contours indicate the approximate limits of the ice sheets at ca. 17 ka <xref ref-type="bibr" rid="bib1.bibx98" id="paren.17"/>. The yellow dot illustrates the location where core GeoB23302-2, used in the present study, was retrieved. Map based on that in <xref ref-type="bibr" rid="bib1.bibx87" id="text.18"/>, who studied core MD95 2002 from a nearby location (red dot).</p></caption>
        <?xmltex \igopts{width=241.848425pt}?><graphic xlink:href="https://cp.copernicus.org/articles/20/121/2024/cp-20-121-2024-f01.jpg"/>

      </fig>

      <p id="d1e321">Permafrost encompasses a diverse range of organic-rich deposits, including ancient peat, organic-rich soils and potentially mineral soils, all of which can become stabilized (frozen) under permafrost conditions, preserving C within them. There is evidence for the presence of several peatlands with active peat deposition in northern latitudes (<inline-formula><mml:math id="M4" display="inline"><mml:mo lspace="0mm">&gt;</mml:mo></mml:math></inline-formula> 40<inline-formula><mml:math id="M5" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> N), including northern Europe, during the last interglacial (130–116 kyr BP; <xref ref-type="bibr" rid="bib1.bibx132" id="altparen.19"/>). Although the occurrence of permafrost during the LGM likely resulted in the long-term burial of peatland OM, deglacial permafrost thawing may have led to the fluvial export of peat-derived OM to the ocean <xref ref-type="bibr" rid="bib1.bibx113 bib1.bibx42" id="paren.20"><named-content content-type="pre">see e.g.</named-content></xref>. In addition to permafrost, petrogenic material carried by glacial meltwater may have been another source of fossil OM to the oceans during the last deglaciation. Following glacial retreat, the mechanical erosion of bedrock such as oil shales mobilizes petrogenic C, which is transported as finely ground glacial meal to the oceans <xref ref-type="bibr" rid="bib1.bibx68 bib1.bibx67" id="paren.21"/>. Therefore, if we are to accurately quantify the impact of the permafrost C feedback on Earth's climate, it is imperative to distinguish between the possible origins of the OM deposited on the continental margins over the course of the last deglaciation. Considering the presence of shale formations in Europe  <xref ref-type="bibr" rid="bib1.bibx149" id="paren.22"><named-content content-type="pre">e.g.</named-content></xref>, our study explores two primary hypotheses regarding the origin of OM: permafrost-derived OM, which includes peat preserved in past permafrost-covered European regions, and OM originating from petrogenic sources. Here, we analysed organic biomarkers and conducted compound-specific radiocarbon (<inline-formula><mml:math id="M6" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C) measurements on <italic>n</italic>-alkanoic acids isolated from a high-resolution, well-dated marine sediment core retrieved from the Channel River outflow to evaluate these hypotheses.</p>
</sec>
<sec id="Ch1.S2">
  <label>2</label><title>Materials and methods</title>
      <p id="d1e377">Herein, we provide an overview of our analytical approach; for in-depth descriptions of each method and the specific details of our analyses, please refer to the following<?pagebreak page123?> subsections. All the elemental, isotopic and biomarker analyses described in this section were conducted as part of the present study. In this research we used several analytical tools to examine core GeoB23302-2 (47<inline-formula><mml:math id="M7" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>26.61<inline-formula><mml:math id="M8" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> N, 8<inline-formula><mml:math id="M9" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>28.67<inline-formula><mml:math id="M10" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> W; 2167 m water depth) (Fig. <xref ref-type="fig" rid="Ch1.F1"/>). The chronology of the sedimentary sequence was established using an age–depth model constructed with the <inline-formula><mml:math id="M11" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C ages of planktic foraminifera with the OxCal software  (<xref ref-type="bibr" rid="bib1.bibx19 bib1.bibx21" id="altparen.23"/>). Elemental ratios were obtained through X-ray fluorescence (XRF) core scanning. The coarse fraction of sediments tends to be enriched in zirconium (Zr), while rubidium (Rb) is found in fine-grained minerals. Therefore, here we report the ratio Zr <inline-formula><mml:math id="M12" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> Rb as an elemental measure of grain size, which has been used as a proxy for river runoff <xref ref-type="bibr" rid="bib1.bibx32 bib1.bibx72 bib1.bibx141 bib1.bibx146" id="paren.24"/>. Similarly, given that iron (Fe) is normally associated with continental weathering products and that the calcium (Ca) content in the sediment primarily reflects the presence of marine carbonate, here we use the Fe <inline-formula><mml:math id="M13" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> Ca ratio as a provenance indicator, reflecting variations in terrigenous sediment delivery <xref ref-type="bibr" rid="bib1.bibx3 bib1.bibx59 bib1.bibx31 bib1.bibx99" id="paren.25"/>. We analysed lipid biomarkers using solvent extraction and gas chromatography and calculated <italic>n</italic>-alkane-derived indices, namely the carbon-number preference index (CPI<inline-formula><mml:math id="M14" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">alk</mml:mi></mml:msub></mml:math></inline-formula>) <xref ref-type="bibr" rid="bib1.bibx16 bib1.bibx86" id="paren.26"><named-content content-type="pre">e.g.</named-content></xref> and the proxy ratio <inline-formula><mml:math id="M15" display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">aq</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx39" id="paren.27"/>, which are commonly used in environmental investigations <xref ref-type="bibr" rid="bib1.bibx94 bib1.bibx110 bib1.bibx150 bib1.bibx47 bib1.bibx37" id="paren.28"><named-content content-type="pre">e.g.</named-content></xref> to assess the degree of OM degradation and reconstruct the temporal evolution of continental vegetation systems, respectively. The CPI<inline-formula><mml:math id="M16" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">alk</mml:mi></mml:msub></mml:math></inline-formula> is based on the ratio of odd to even <italic>n</italic>-alkanes, providing information about the distribution of these compounds in the samples, while the <inline-formula><mml:math id="M17" display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">aq</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> reflects the predominance of long-chain <italic>n</italic>-alkanes in terrestrial vascular plants as opposed to algae and macrophytes, which primarily synthesize short- to mid-chain <italic>n</italic>-alkanes <xref ref-type="bibr" rid="bib1.bibx11" id="paren.29"/>. The <inline-formula><mml:math id="M18" display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">aq</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> ratio indicates the relative input of aquatic macrophytes and terrestrial plants to the sediment <xref ref-type="bibr" rid="bib1.bibx39" id="paren.30"/>. The prevalence of odd-numbered <italic>n</italic>-alkanes in fresh material implies that the CPI<inline-formula><mml:math id="M19" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">alk</mml:mi></mml:msub></mml:math></inline-formula> can serve as an indicator of OM degradation <xref ref-type="bibr" rid="bib1.bibx16 bib1.bibx86 bib1.bibx88" id="paren.31"/>. To further assess the presence of petrogenic OM, we used the fractional abundance of hopanes of biological origin, e.g. bacteria-derived hopanes, in relation to their diagenetic isomers (<inline-formula><mml:math id="M20" display="inline"><mml:mrow><mml:mi>f</mml:mi><mml:mi mathvariant="italic">β</mml:mi><mml:mi mathvariant="italic">β</mml:mi></mml:mrow></mml:math></inline-formula>) <xref ref-type="bibr" rid="bib1.bibx89" id="paren.32"/>. Here, the branched and isoprenoid tetraether (BIT) index <xref ref-type="bibr" rid="bib1.bibx53" id="paren.33"/>, based on the relative abundance of branched glycerol dialkyl glycerol tetraether lipids (GDGTs) characteristic of terrestrial bacteria and the isoprenoid GDGT crenarchaeol produced by marine Thaumarchaeota, is used as a proxy for the input of terrestrially sourced OM. Carbon isotope analysis (<inline-formula><mml:math id="M21" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C) of bulk samples was conducted as part of our investigation into their origin. Finally, given that the results of bulk <inline-formula><mml:math id="M22" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C dating reflect the <inline-formula><mml:math id="M23" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C content of a heterogeneous mixture of compounds possibly derived from distinct sources, here we further address the provenance of the OM by using compound-specific <inline-formula><mml:math id="M24" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C analyses of high-molecular-weight <italic>n</italic>-alkanoic acids (C<inline-formula><mml:math id="M25" display="inline"><mml:msub><mml:mi/><mml:mrow><mml:mn mathvariant="normal">26</mml:mn><mml:mo>:</mml:mo><mml:mn mathvariant="normal">0</mml:mn></mml:mrow></mml:msub></mml:math></inline-formula>, C<inline-formula><mml:math id="M26" display="inline"><mml:msub><mml:mi/><mml:mrow><mml:mn mathvariant="normal">28</mml:mn><mml:mo>:</mml:mo><mml:mn mathvariant="normal">0</mml:mn></mml:mrow></mml:msub></mml:math></inline-formula> and C<inline-formula><mml:math id="M27" display="inline"><mml:msub><mml:mi/><mml:mrow><mml:mn mathvariant="normal">30</mml:mn><mml:mo>:</mml:mo><mml:mn mathvariant="normal">0</mml:mn></mml:mrow></mml:msub></mml:math></inline-formula>) – which are typically derived from vascular plants <xref ref-type="bibr" rid="bib1.bibx11" id="paren.34"/> – from specific depths in the core. This approach has been successfully employed for the identification of ancient terrigenous material export at other sites <xref ref-type="bibr" rid="bib1.bibx143 bib1.bibx89 bib1.bibx145" id="paren.35"><named-content content-type="pre">e.g.</named-content></xref>.</p>
<sec id="Ch1.S2.SS1">
  <label>2.1</label><title>Sampling and core chronology</title>
      <p id="d1e669">Core GeoB23302-2 was recovered from the Celtic Margin, off the English Channel (47<inline-formula><mml:math id="M28" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>26.61<inline-formula><mml:math id="M29" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> N, 8<inline-formula><mml:math id="M30" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>28.67<inline-formula><mml:math id="M31" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> W; 2167 m water depth) (Fig. <xref ref-type="fig" rid="Ch1.F1"/>), with the help of a gravity corer during cruise MSM 79 of the research vessel <italic>Maria S. Merian</italic>. The core location is in close proximity to the site where core MD95 2002, which has been studied in previous publications <xref ref-type="bibr" rid="bib1.bibx87 bib1.bibx131" id="paren.36"><named-content content-type="pre">e.g.</named-content></xref>, was retrieved (47<inline-formula><mml:math id="M32" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>27<inline-formula><mml:math id="M33" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> N, 8<inline-formula><mml:math id="M34" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>32<inline-formula><mml:math id="M35" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> W) (see Fig. <xref ref-type="fig" rid="Ch1.F1"/>). The chronology of our 700 cm core was established based on seven radiocarbon accelerator mass spectrometry (<inline-formula><mml:math id="M36" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C-AMS) measurements of planktic foraminifera (<italic>G. bulloides</italic> and <italic>N. pachyderma</italic>) picked at specific depths (Table <xref ref-type="table" rid="Ch1.T1"/>). The preparation and measurement of these samples followed well-established protocols routinely run at the MICADAS <inline-formula><mml:math id="M37" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C laboratory of the Alfred Wegener Institute (AWI) <xref ref-type="bibr" rid="bib1.bibx91" id="paren.37"/>. The <inline-formula><mml:math id="M38" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C ages were uploaded to the OxCal software version 4.4.2 (<xref ref-type="bibr" rid="bib1.bibx19 bib1.bibx21" id="altparen.38"/>), and assuming that the deposition is a Poisson process, the P Sequence model was employed for the construction of an age–depth model for core GeoB23302-2 (<xref ref-type="bibr" rid="bib1.bibx20 bib1.bibx23" id="altparen.39"/>). This deposition model (Fig. S2 in the Supplement) uses the global marine calibration curve Marine20 (<xref ref-type="bibr" rid="bib1.bibx48" id="altparen.40"/>) and a local marine reservoir correction <inline-formula><mml:math id="M39" display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:mi>R</mml:mi></mml:mrow></mml:math></inline-formula> of 94 <inline-formula><mml:math id="M40" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 45 <inline-formula><mml:math id="M41" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C yr <xref ref-type="bibr" rid="bib1.bibx73" id="paren.41"/>. It is important to note that while Marine20 incorporates larger marine reservoir age estimates for the last glacial period than Marine13, these estimates are considered more realistic due to methodological improvements in the former (<xref ref-type="bibr" rid="bib1.bibx48 bib1.bibx49" id="altparen.42"/>). A general outlier analysis was employed to account for possible outliers within the chronological model (<xref ref-type="bibr" rid="bib1.bibx22" id="altparen.43"/>). The code is available in the Supplement accompanying this paper.</p>
</sec>
<sec id="Ch1.S2.SS2">
  <label>2.2</label><title>Elemental analyses</title>
      <p id="d1e850">The XRF characterization of core GeoB23302-2 was performed using the XRF Core Scanner II (AVAATECH serial no. 2) at the Center for Marine Environmental Sciences (MARUM), University of Bremen, Germany. Measurements were performed at 1 cm intervals for the upper 3.5 m of the core and at every 2 cm for the remaining section. The scan resolution was set to 1 cm with two running rounds, during which the elements were detected with 10 and 30 kV of tube<?pagebreak page124?> voltage. In order to account for the closed sum effects of water content, grain size and OM amount (e.g. <xref ref-type="bibr" rid="bib1.bibx142" id="altparen.44"/>), we report the elemental ratios Zr <inline-formula><mml:math id="M42" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> Rb and Fe <inline-formula><mml:math id="M43" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> Ca.</p>
</sec>
<sec id="Ch1.S2.SS3">
  <label>2.3</label><title>Biomarker analyses and derived indices</title>
      <p id="d1e878">Sediment samples taken at 10 cm intervals from core GeoB23302-2 were freeze-dried and homogenized. For each depth, approximately 3 g of sediment was subsampled and underwent ultrasonic extraction with a mixture of dichloromethane : methanol <inline-formula><mml:math id="M44" display="inline"><mml:mrow><mml:mn mathvariant="normal">9</mml:mn><mml:mo>:</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M45" display="inline"><mml:mrow><mml:mi>v</mml:mi><mml:mo>:</mml:mo><mml:mi>v</mml:mi></mml:mrow></mml:math></inline-formula>). This step was repeated three times, and the total lipid extracts obtained were then saponified with 0.1 M potassium hydroxide (KOH) in methanol : water <inline-formula><mml:math id="M46" display="inline"><mml:mrow><mml:mn mathvariant="normal">9</mml:mn><mml:mo>:</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula> at 80 <inline-formula><mml:math id="M47" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C for 2 h. This procedure resulted in the separation of the neutral lipids and <italic>n</italic>-alkanoic acids fractions, which were subsequently extracted using <italic>n</italic>-hexane and dichloromethane (at pH 1), respectively. Next, silica gel chromatography was employed to further split the neutral lipids via elution with <italic>n</italic>-hexane and dichloromethane : methanol <inline-formula><mml:math id="M48" display="inline"><mml:mrow><mml:mn mathvariant="normal">1</mml:mn><mml:mo>:</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M49" display="inline"><mml:mrow><mml:mi>v</mml:mi><mml:mo>:</mml:mo><mml:mi>v</mml:mi></mml:mrow></mml:math></inline-formula>), yielding the <italic>n</italic>-alkane and GDGT subfractions, respectively. The <italic>n</italic>-alkane concentrations were measured via gas chromatography (GC) using a 7890A GC (Agilent Technologies) equipped with a flame ionization detector (FID) and DB-5MS fused silica capillary columns (60 m, ID 250 <inline-formula><mml:math id="M50" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi></mml:mrow></mml:math></inline-formula>m, 0.25 <inline-formula><mml:math id="M51" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi></mml:mrow></mml:math></inline-formula>m film coupled to a 5 m, ID 530 <inline-formula><mml:math id="M52" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi></mml:mrow></mml:math></inline-formula>m deactivated fused silica precolumn). Retention times and the comparison with an <italic>n</italic>-alkane standard were used for the identification of different compounds, whereas quantifications were achieved through the use of an internal standard (squalane) added to the sample prior to extraction. We calculated <italic>n</italic>-alkane-derived indices, namely the CPI<inline-formula><mml:math id="M53" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">alk</mml:mi></mml:msub></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx16 bib1.bibx86" id="paren.45"><named-content content-type="pre">e.g.</named-content></xref>,
            <disp-formula id="Ch1.E1" content-type="numbered"><label>1</label><mml:math id="M54" display="block"><mml:mtable class="split" rowspacing="0.2ex" displaystyle="true" columnalign="right left"><mml:mtr><mml:mtd><mml:mrow><mml:msub><mml:mi mathvariant="normal">CPI</mml:mi><mml:mi mathvariant="normal">alk</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mn mathvariant="normal">1</mml:mn><mml:mn mathvariant="normal">2</mml:mn></mml:mfrac></mml:mstyle></mml:mrow></mml:mtd><mml:mtd><mml:mrow><mml:mo>⋅</mml:mo><mml:mfenced close="" open="("><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">25</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">27</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">29</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">31</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">33</mml:mn></mml:msub></mml:mrow><mml:mrow><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">24</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">26</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">28</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">30</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">32</mml:mn></mml:msub></mml:mrow></mml:mfrac></mml:mstyle></mml:mfenced></mml:mrow></mml:mtd></mml:mtr><mml:mtr><mml:mtd/><mml:mtd><mml:mrow><mml:mfenced open="" close=")"><mml:mrow><mml:mo>+</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">25</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">27</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">29</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">31</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">33</mml:mn></mml:msub></mml:mrow><mml:mrow><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">26</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">28</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">30</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">32</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">34</mml:mn></mml:msub></mml:mrow></mml:mfrac></mml:mstyle></mml:mrow></mml:mfenced><mml:mo>,</mml:mo></mml:mrow></mml:mtd></mml:mtr></mml:mtable></mml:math></disp-formula>
          and the <inline-formula><mml:math id="M55" display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">aq</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx39" id="paren.46"/>,
            <disp-formula id="Ch1.E2" content-type="numbered"><label>2</label><mml:math id="M56" display="block"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">aq</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">23</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">25</mml:mn></mml:msub></mml:mrow><mml:mrow><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">23</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">25</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">29</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">31</mml:mn></mml:msub></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>.</mml:mo></mml:mrow></mml:math></disp-formula>
          Hopanes were analysed via GC coupled with time-of-flight mass spectrometry (GC-TOF-MS), and such a system consisted of a LECO Pegasus III (LECO Corp., St. Joseph, MI) interfaced to an Agilent 6890 GC, which was equipped with a temperature-programmable cooled injection system (CIS4, Gerstel). The measurements were performed using the instrumental set-up described in <xref ref-type="bibr" rid="bib1.bibx50" id="text.47"/>, and identification was achieved through the relative retention times and mass spectra. The sum of <inline-formula><mml:math id="M57" display="inline"><mml:mrow><mml:mi>m</mml:mi><mml:mo>/</mml:mo><mml:mi>z</mml:mi></mml:mrow></mml:math></inline-formula> 191 and 205 was used for the quantification of homohopane isomers (C<inline-formula><mml:math id="M58" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">31</mml:mn></mml:msub></mml:math></inline-formula>), namely the 17<inline-formula><mml:math id="M59" display="inline"><mml:mi mathvariant="italic">β</mml:mi></mml:math></inline-formula>,21<inline-formula><mml:math id="M60" display="inline"><mml:mi mathvariant="italic">β</mml:mi></mml:math></inline-formula> (H), 22R homohopane; the 17<inline-formula><mml:math id="M61" display="inline"><mml:mi mathvariant="italic">β</mml:mi></mml:math></inline-formula>,21<inline-formula><mml:math id="M62" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula> (H), 22R <inline-formula><mml:math id="M63" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> 17<inline-formula><mml:math id="M64" display="inline"><mml:mi mathvariant="italic">β</mml:mi></mml:math></inline-formula>,21<inline-formula><mml:math id="M65" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula> (H), 22S homohopanes; the 17<inline-formula><mml:math id="M66" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>,21<inline-formula><mml:math id="M67" display="inline"><mml:mi mathvariant="italic">β</mml:mi></mml:math></inline-formula> (H), 22R homohopane; and the 17<inline-formula><mml:math id="M68" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>,21<inline-formula><mml:math id="M69" display="inline"><mml:mi mathvariant="italic">β</mml:mi></mml:math></inline-formula> (H), 22S homohopane. Next, the <inline-formula><mml:math id="M70" display="inline"><mml:mrow><mml:mi>f</mml:mi><mml:mi mathvariant="italic">β</mml:mi><mml:mi mathvariant="italic">β</mml:mi></mml:mrow></mml:math></inline-formula> was calculated <xref ref-type="bibr" rid="bib1.bibx89" id="paren.48"/>:
            <disp-formula id="Ch1.E3" content-type="numbered"><label>3</label><mml:math id="M71" display="block"><mml:mrow><?xmltex \hack{\hbox\bgroup\fontsize{9.0}{9.0}\selectfont$\displaystyle}?><mml:mi>f</mml:mi><mml:mi mathvariant="italic">β</mml:mi><mml:mi mathvariant="italic">β</mml:mi><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">31</mml:mn></mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mi mathvariant="italic">β</mml:mi><mml:mi mathvariant="normal">R</mml:mi></mml:mrow><mml:mrow><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">31</mml:mn></mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mi mathvariant="italic">β</mml:mi><mml:mi mathvariant="normal">R</mml:mi><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">31</mml:mn></mml:msub><mml:mi mathvariant="italic">α</mml:mi><mml:mi mathvariant="italic">β</mml:mi><mml:mi mathvariant="normal">S</mml:mi><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">31</mml:mn></mml:msub><mml:mi mathvariant="italic">α</mml:mi><mml:mi mathvariant="italic">β</mml:mi><mml:mi mathvariant="normal">R</mml:mi><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">31</mml:mn></mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mi mathvariant="italic">α</mml:mi><mml:mi mathvariant="normal">S</mml:mi><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">31</mml:mn></mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mi mathvariant="italic">α</mml:mi><mml:mi mathvariant="normal">R</mml:mi></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>.</mml:mo><?xmltex \hack{$\egroup}?></mml:mrow></mml:math></disp-formula>
          The analyses of branched and isoprenoid GDGTs by high-performance liquid chromatography (HPLC) were performed on an Agilent 1200 series HPLC system coupled to an Agilent 6120 single-quadrupole MS via an atmospheric pressure chemical ionization interface (APCI), broadly following the method described in <xref ref-type="bibr" rid="bib1.bibx54" id="text.49"/>. The chromatographic separation of individual GDGTs was achieved via the use of two ultra-performance liquid chromatography (UPLC) silica columns in series (Waters Acquity BEH HILIC, 2.1 mm <inline-formula><mml:math id="M72" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 150 mm, 1.7 <inline-formula><mml:math id="M73" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi></mml:mrow></mml:math></inline-formula>m and a 2.1 mm <inline-formula><mml:math id="M74" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 5 mm pre-column of the same material) maintained at 30 <inline-formula><mml:math id="M75" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C. Positive-ion APCI-MS and selective ion monitoring (SIM) of (M <inline-formula><mml:math id="M76" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> H)<inline-formula><mml:math id="M77" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula> ions  (<xref ref-type="bibr" rid="bib1.bibx123" id="altparen.50"/>) or ion-source fragmentation products of OH-GDGTs (<xref ref-type="bibr" rid="bib1.bibx80" id="altparen.51"/>) allowed the identification of GDGTs. Quantification was performed with the use of an internal standard (C<inline-formula><mml:math id="M78" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">46</mml:mn></mml:msub></mml:math></inline-formula>-GDGT) added prior to extraction. For this research, we calculated the BIT index <xref ref-type="bibr" rid="bib1.bibx53" id="paren.52"/>:
            <disp-formula id="Ch1.E4" content-type="numbered"><label>4</label><mml:math id="M79" display="block"><mml:mrow><mml:mi mathvariant="normal">BIT</mml:mi><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:mi mathvariant="normal">I</mml:mi><mml:mo>+</mml:mo><mml:mi mathvariant="normal">II</mml:mi><mml:mo>+</mml:mo><mml:mi mathvariant="normal">III</mml:mi></mml:mrow><mml:mrow><mml:mi mathvariant="normal">I</mml:mi><mml:mo>+</mml:mo><mml:mi mathvariant="normal">II</mml:mi><mml:mo>+</mml:mo><mml:mi mathvariant="normal">III</mml:mi><mml:mo>+</mml:mo><mml:mi mathvariant="normal">cren</mml:mi></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
          where the roman numerals refer to specific GDGTs characteristic of terrestrial bacteria, and cren stands for crenarchaeol, which is derived from marine planktonic Thaumarchaeota.</p>
</sec>
<sec id="Ch1.S2.SS4">
  <label>2.4</label><title>Compound-specific radiocarbon analyses (CSRA)</title>
      <p id="d1e1596">Soxhlet extraction was employed for the compound-specific <inline-formula><mml:math id="M80" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C dating of high-molecular-weight <italic>n</italic>-alkanoic acids.  For that purpose, approximately 100 g of freeze-dried and homogenized sediment taken from selected depths in core GeoB23302-2 was extracted for 48 h using a mixture of dichloromethane : methanol <inline-formula><mml:math id="M81" display="inline"><mml:mrow><mml:mn mathvariant="normal">9</mml:mn><mml:mo>:</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M82" display="inline"><mml:mrow><mml:mi>v</mml:mi><mml:mo>:</mml:mo><mml:mi>v</mml:mi></mml:mrow></mml:math></inline-formula>). Total lipid extracts were saponified with 0.1 M KOH in methanol : water <inline-formula><mml:math id="M83" display="inline"><mml:mrow><mml:mn mathvariant="normal">9</mml:mn><mml:mo>:</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula> at 80 <inline-formula><mml:math id="M84" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C for 2 h, and the <italic>n</italic>-alkanoic acids were recovered from the saponified solution using <italic>n</italic>-hexane at pH 1. Next, <italic>n</italic>-alkanoic acids were methylated at 80 <inline-formula><mml:math id="M85" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C overnight in a nitrogen atmosphere with HCl and methanol of known <inline-formula><mml:math id="M86" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C signature to yield the fatty acid methyl esters (FAMEs) that were later extracted with <italic>n</italic>-hexane. Silica gel chromatography was employed to separate FAMEs from polar compounds. The <italic>n</italic>-C<inline-formula><mml:math id="M87" display="inline"><mml:msub><mml:mi/><mml:mrow><mml:mn mathvariant="normal">26</mml:mn><mml:mo>:</mml:mo><mml:mn mathvariant="normal">0</mml:mn></mml:mrow></mml:msub></mml:math></inline-formula>, <italic>n</italic>-C<inline-formula><mml:math id="M88" display="inline"><mml:msub><mml:mi/><mml:mrow><mml:mn mathvariant="normal">28</mml:mn><mml:mo>:</mml:mo><mml:mn mathvariant="normal">0</mml:mn></mml:mrow></mml:msub></mml:math></inline-formula> and <italic>n</italic>-C<inline-formula><mml:math id="M89" display="inline"><mml:msub><mml:mi/><mml:mrow><mml:mn mathvariant="normal">30</mml:mn><mml:mo>:</mml:mo><mml:mn mathvariant="normal">0</mml:mn></mml:mrow></mml:msub></mml:math></inline-formula> alkanoic acids underwent purification via preparative capillary GC (PC-GC; <xref ref-type="bibr" rid="bib1.bibx33" id="altparen.53"/>) on an Agilent HP6890N GC with a Gerstel cooled injection system (CIS) connected to a Gerstel preparative fraction collector <xref ref-type="bibr" rid="bib1.bibx69" id="paren.54"/>. A Restek Rxi-1ms fused silica capillary column (30 m, 0.53 mm diameter, 1.5 <inline-formula><mml:math id="M90" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi></mml:mrow></mml:math></inline-formula>m film<?pagebreak page125?> thickness) equipped the GC. Injection was performed stepwise with 5 <inline-formula><mml:math id="M91" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi></mml:mrow></mml:math></inline-formula>L per injection, and, at the end of the process, the purity of the FAMEs was checked by analysing aliquots of the samples via GC-FID. The purified FAMEs were transferred to tin capsules (25 <inline-formula><mml:math id="M92" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi></mml:mrow></mml:math></inline-formula>L volume, ELEMENTAR) using dichloromethane, dried on a hot plate at 40 <inline-formula><mml:math id="M93" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C and packed. An Elementar vario ISOTOPE EA (elemental analyser) was used for the combustion of the samples, generating <inline-formula><mml:math id="M94" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> with carbon isotopic ratios directly determined by the connected MICADAS system. Reference standards (oxalic acid II, SRM 4990C) and <inline-formula><mml:math id="M95" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C-free <inline-formula><mml:math id="M96" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> gas had their <inline-formula><mml:math id="M97" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C content measured together with the samples. The BATS software (<xref ref-type="bibr" rid="bib1.bibx139" id="altparen.55"/>) was used for blank corrections and standard normalization, and the final results are reported as fraction modern carbon (<inline-formula><mml:math id="M98" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mi mathvariant="normal">m</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>).</p>
</sec>
<sec id="Ch1.S2.SS5">
  <label>2.5</label><title>Assessment and correction of CSRA procedure blank</title>
      <p id="d1e1843">The preparation procedures for CSRA introduce exogenous C, i.e. contaminants, to samples. The degree of contamination varies according to the methods employed, and, in our case, processes such as column bleed and carryover during prep-GC compound isolation may contribute to this. For this reason, assessing the <inline-formula><mml:math id="M99" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mi mathvariant="normal">m</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and the size of the blank (<inline-formula><mml:math id="M100" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mi mathvariant="normal">mblank</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M101" display="inline"><mml:mrow><mml:msub><mml:mi>m</mml:mi><mml:mi mathvariant="normal">blank</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>, respectively) is essential for accurate results. Here, in-house reference samples of <inline-formula><mml:math id="M102" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C-free Messel shale (<inline-formula><mml:math id="M103" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mi mathvariant="normal">m</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0</mml:mn></mml:mrow></mml:math></inline-formula>) and modern apple peel (<inline-formula><mml:math id="M104" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mi mathvariant="normal">m</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mn mathvariant="normal">1.029</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">0.001</mml:mn></mml:mrow></mml:math></inline-formula>) underwent the same pre-treatment as samples of unknown age, and their results were used for blank correction following the method outlined in <xref ref-type="bibr" rid="bib1.bibx126" id="text.56"/>. Isotopic mass balance was employed in order to make a correction for the methyl group added during the derivatization of the samples. Uncertainties were fully propagated.</p>
</sec>
<sec id="Ch1.S2.SS6">
  <label>2.6</label><?xmltex \opttitle{Pre-depositional ${}^{{14}}$C ages of terrigenous compounds}?><title>Pre-depositional <inline-formula><mml:math id="M105" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C ages of terrigenous compounds</title>
      <p id="d1e1944">The <inline-formula><mml:math id="M106" display="inline"><mml:mi mathvariant="normal">Δ</mml:mi></mml:math></inline-formula><inline-formula><mml:math id="M107" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C values of the <italic>n</italic>-alkanoic acids analysed here were corrected for radioactive decay between 1950 and 2021, which is the year of measurement. These values were then used to calculate the <inline-formula><mml:math id="M108" display="inline"><mml:mi mathvariant="normal">Δ</mml:mi></mml:math></inline-formula><inline-formula><mml:math id="M109" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C values at the time of deposition:
            <disp-formula id="Ch1.E5" content-type="numbered"><label>5</label><mml:math id="M110" display="block"><mml:mrow><mml:msup><mml:mi mathvariant="normal">Δ</mml:mi><mml:mn mathvariant="normal">14</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">initial</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mfenced open="[" close="]"><mml:mrow><mml:mfenced close=")" open="("><mml:mrow><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msup><mml:mi mathvariant="normal">Δ</mml:mi><mml:mn mathvariant="normal">14</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow><mml:mn mathvariant="normal">1000</mml:mn></mml:mfrac></mml:mstyle><mml:mo>+</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:mfenced><mml:mo>⋅</mml:mo><mml:msup><mml:mi>e</mml:mi><mml:mrow><mml:mi mathvariant="italic">λ</mml:mi><mml:mi>t</mml:mi></mml:mrow></mml:msup><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:mfenced><mml:mo>⋅</mml:mo><mml:mn mathvariant="normal">1000</mml:mn><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
          where <inline-formula><mml:math id="M111" display="inline"><mml:mi mathvariant="italic">λ</mml:mi></mml:math></inline-formula> is a decay constant (<inline-formula><mml:math id="M112" display="inline"><mml:mrow><mml:mn mathvariant="normal">1</mml:mn><mml:mo>/</mml:mo><mml:mn mathvariant="normal">8267</mml:mn></mml:mrow></mml:math></inline-formula> yr<inline-formula><mml:math id="M113" 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>), and <inline-formula><mml:math id="M114" display="inline"><mml:mi>t</mml:mi></mml:math></inline-formula> is the time of deposition. The <inline-formula><mml:math id="M115" display="inline"><mml:mi mathvariant="normal">Δ</mml:mi></mml:math></inline-formula><inline-formula><mml:math id="M116" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C values of the atmosphere contemporaneous with the compounds (<inline-formula><mml:math id="M117" display="inline"><mml:mi mathvariant="normal">Δ</mml:mi></mml:math></inline-formula><inline-formula><mml:math id="M118" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C<inline-formula><mml:math id="M119" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">atm</mml:mi></mml:msub></mml:math></inline-formula>) were obtained from comparison with the IntCal20 dataset (<xref ref-type="bibr" rid="bib1.bibx107" id="altparen.57"/>) using the age ranges given by the deposition model for the respective sediment layers. Finally, pre-depositional <inline-formula><mml:math id="M120" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C ages for the <italic>n</italic>-alkanoic acids were given by
            <disp-formula id="Ch1.E6" content-type="numbered"><label>6</label><mml:math id="M121" display="block"><mml:mrow><mml:mi>A</mml:mi><mml:mo>=</mml:mo><mml:mo>-</mml:mo><mml:mn mathvariant="normal">8033</mml:mn><mml:mo>⋅</mml:mo><mml:mi>ln⁡</mml:mi><mml:mfenced close=")" open="("><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:mn mathvariant="normal">1</mml:mn><mml:mo>+</mml:mo><mml:msup><mml:mi mathvariant="normal">Δ</mml:mi><mml:mn mathvariant="normal">14</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">initial</mml:mi></mml:msub><mml:mo>/</mml:mo><mml:mn mathvariant="normal">1000</mml:mn></mml:mrow><mml:mrow><mml:mn mathvariant="normal">1</mml:mn><mml:mo>+</mml:mo><mml:msup><mml:mi mathvariant="normal">Δ</mml:mi><mml:mn mathvariant="normal">14</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:msub><mml:mo>/</mml:mo><mml:mn mathvariant="normal">1000</mml:mn></mml:mrow></mml:mfrac></mml:mstyle></mml:mfenced><mml:mo>.</mml:mo></mml:mrow></mml:math></disp-formula>
          These calculations follow the method outlined in <xref ref-type="bibr" rid="bib1.bibx113" id="text.58"/> and later in <xref ref-type="bibr" rid="bib1.bibx143" id="text.59"/>, where more details can be found.</p>
</sec>
<sec id="Ch1.S2.SS7">
  <label>2.7</label><title>Stable isotope analyses</title>
      <p id="d1e2208">Carbon stable isotope (<inline-formula><mml:math id="M122" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C) analyses were carried out on acidified samples (Ag capsules, HCl, 1.5 M) in order to remove the inorganic C (<xref ref-type="bibr" rid="bib1.bibx95" id="altparen.60"/>). Analyses were performed using a Thermo Scientific DELTA Q isotope ratio mass spectrometer coupled to a Thermo Scientific FLASH 2000 CHNS/O analyser via Conflo III at the Stable Isotope Laboratory of ISP-CNR. <inline-formula><mml:math id="M123" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C data are expressed in the conventional delta notation (‰). Isotopic data were calibrated using the IAEA reference material IAEA-CH7 polyethylene (<inline-formula><mml:math id="M124" display="inline"><mml:mo lspace="0mm">-</mml:mo></mml:math></inline-formula>32.15 ‰ vs. Vienna Pee Dee Belemnite (VPDB)). Throughout the runs, we used other standards with a sediment matrix routinely used in the laboratory to check the reproducibility of measurements. The standard deviation for <inline-formula><mml:math id="M125" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C measurements was lower than <inline-formula><mml:math id="M126" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>0.1‰ based on replicates of sediment standards.</p>
</sec>
</sec>
<sec id="Ch1.S3">
  <label>3</label><title>Results</title>
      <p id="d1e2271">The GeoB23302-2 sediment core spans a period from approximately 25 to 4 cal kyr BP (Table 1). The age–depth model for this core shows a period of enhanced deposition between approximately 20 and 15 cal kyr BP (Fig. S2). An outlier analysis shows that the model represents the foraminifera <inline-formula><mml:math id="M127" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C ages well, with an OxCal overall agreement index of 99 %. From approximately 20.6 until 15 cal kyr BP, the Zr <inline-formula><mml:math id="M128" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> Rb ratio shows a long-term increase, whereas a period of relatively high Fe <inline-formula><mml:math id="M129" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> Ca values is observed at ca. 21–16.4 cal kyr BP (Fig. <xref ref-type="fig" rid="Ch1.F2"/>c). Values for the proxy <inline-formula><mml:math id="M130" display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">aq</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> are relatively low during the LGM and show a pronounced increase at approximately 21 cal kyr BP, with higher values towards the late glacial and a sudden decrease at the onset of Heinrich event 1 (H1; iceberg discharge from the Laurentide ice sheet into the North Atlantic Ocean, ca. 17.2 cal kyr BP) (Fig. <xref ref-type="fig" rid="Ch1.F2"/>d). This is followed by a sharp increase at approximately 16.5 cal kyr BP and a drop to Holocene values around 16.3 cal kyr BP. The <inline-formula><mml:math id="M131" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CPI</mml:mi><mml:mi mathvariant="normal">alk</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and the <inline-formula><mml:math id="M132" display="inline"><mml:mrow><mml:mi>f</mml:mi><mml:mi mathvariant="italic">β</mml:mi><mml:mi mathvariant="italic">β</mml:mi></mml:mrow></mml:math></inline-formula> proxy show relatively low values in the late glacial/early deglaciation when compared to the Holocene (Fig. <xref ref-type="fig" rid="Ch1.F2"/>e). During the LGM, the <inline-formula><mml:math id="M133" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CPI</mml:mi><mml:mi mathvariant="normal">alk</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values are broadly constant, while an increase is observed at the beginning of H1 followed by a sharp drop around 16.5 cal kyr BP and a return to higher values at approximately 16.2 cal kyr BP. The <inline-formula><mml:math id="M134" display="inline"><mml:mrow><mml:mi>f</mml:mi><mml:mi mathvariant="italic">β</mml:mi><mml:mi mathvariant="italic">β</mml:mi></mml:mrow></mml:math></inline-formula> record shows fluctuations during the LGM, followed by a gradual decrease starting at approximately 18 cal kyr BP and a sharp drop around 16.5 cal kyr BP before returning to higher values at approximately 16.2 cal kyr BP (Fig. <xref ref-type="fig" rid="Ch1.F2"/>e). The <inline-formula><mml:math id="M135" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C ages of the long-chain <italic>n</italic>-alkanoic acids varied from approximately 10 to 39 <inline-formula><mml:math id="M136" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C kyr. When converted to pre-depositional age estimates, it is possible to observe that at the peak of our<?pagebreak page126?> BIT record, around 18 cal kyr BP, compounds pre-aged by up to ca. 25 000 <inline-formula><mml:math id="M137" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C yr were delivered to the continental slope (Fig. <xref ref-type="fig" rid="Ch1.F2"/>f). Pre-depositional ages broadly follow the BIT record, with younger compounds observed from the end of the BIT peak (ca. 16 cal kyr BP) towards the Holocene. The results of our bulk  <inline-formula><mml:math id="M138" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C analyses corroborate the BIT index record, showing that terrestrial C dominantly contributed to samples during the period of enhanced terrigenous deposition, while the OM in Holocene samples is mostly marine (Table 2).</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T1"><?xmltex \currentcnt{1}?><label>Table 1</label><caption><p id="d1e2411">Radiocarbon and modelled ages of planktic foraminifera picked from core GeoB23302-2.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="4">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="left"/>
     <oasis:colspec colnum="3" colname="col3" align="right"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:thead>
       <oasis:row>
         <oasis:entry colname="col1">Depth</oasis:entry>
         <oasis:entry colname="col2">Species</oasis:entry>
         <oasis:entry colname="col3"><inline-formula><mml:math id="M139" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C age</oasis:entry>
         <oasis:entry colname="col4">Modelled age</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1">(cm)</oasis:entry>
         <oasis:entry colname="col2"/>
         <oasis:entry colname="col3">(<inline-formula><mml:math id="M140" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C yr)</oasis:entry>
         <oasis:entry colname="col4">(cal BP; <inline-formula><mml:math id="M141" display="inline"><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mi mathvariant="italic">σ</mml:mi></mml:mrow></mml:math></inline-formula>)</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>
         <oasis:entry colname="col1">3–4</oasis:entry>
         <oasis:entry colname="col2"><italic>G. bulloides</italic></oasis:entry>
         <oasis:entry colname="col3">3556 <inline-formula><mml:math id="M142" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 67</oasis:entry>
         <oasis:entry colname="col4">3600–3100</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">118–119</oasis:entry>
         <oasis:entry colname="col2"><italic>G. bulloides</italic></oasis:entry>
         <oasis:entry colname="col3">9981 <inline-formula><mml:math id="M143" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 105</oasis:entry>
         <oasis:entry colname="col4">11300–10600</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">234–235</oasis:entry>
         <oasis:entry colname="col2"><italic>N. pachyderma</italic></oasis:entry>
         <oasis:entry colname="col3">14111 <inline-formula><mml:math id="M144" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 124</oasis:entry>
         <oasis:entry colname="col4">16800–15900</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">340–341</oasis:entry>
         <oasis:entry colname="col2"><italic>N. pachyderma</italic></oasis:entry>
         <oasis:entry colname="col3">15131 <inline-formula><mml:math id="M145" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 142</oasis:entry>
         <oasis:entry colname="col4">17800–17100</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">450–451</oasis:entry>
         <oasis:entry colname="col2"><italic>N. pachyderma</italic></oasis:entry>
         <oasis:entry colname="col3">15112 <inline-formula><mml:math id="M146" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 151</oasis:entry>
         <oasis:entry colname="col4">18100–17400</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">584–585</oasis:entry>
         <oasis:entry colname="col2"><italic>G. bulloides</italic></oasis:entry>
         <oasis:entry colname="col3">16893 <inline-formula><mml:math id="M147" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 203</oasis:entry>
         <oasis:entry colname="col4">20200–19100</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">686–687</oasis:entry>
         <oasis:entry colname="col2"><italic>G. bulloides</italic></oasis:entry>
         <oasis:entry colname="col3">20432 <inline-formula><mml:math id="M148" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 202</oasis:entry>
         <oasis:entry colname="col4">24200–23100</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table><?xmltex \gdef\@currentlabel{1}?></table-wrap>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T2"><?xmltex \currentcnt{2}?><label>Table 2</label><caption><p id="d1e2655">Carbon stable isotope (<inline-formula><mml:math id="M149" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C) values of bulk sediment samples from  core GeoB23302-2.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="4">
     <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:thead>
       <oasis:row>
         <oasis:entry colname="col1">Depth</oasis:entry>
         <oasis:entry colname="col2">Age</oasis:entry>
         <oasis:entry colname="col3">Uncertainty</oasis:entry>
         <oasis:entry colname="col4"><inline-formula><mml:math id="M150" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1">(cm)</oasis:entry>
         <oasis:entry colname="col2">(<inline-formula><mml:math id="M151" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C yr)</oasis:entry>
         <oasis:entry colname="col3">(<inline-formula><mml:math id="M152" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C yr)</oasis:entry>
         <oasis:entry colname="col4">(‰)</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>
         <oasis:entry colname="col1">30–33</oasis:entry>
         <oasis:entry colname="col2">4467</oasis:entry>
         <oasis:entry colname="col3">1988</oasis:entry>
         <oasis:entry colname="col4"><inline-formula><mml:math id="M153" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>22.25</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">90–93</oasis:entry>
         <oasis:entry colname="col2">9957</oasis:entry>
         <oasis:entry colname="col3">1960</oasis:entry>
         <oasis:entry colname="col4"><inline-formula><mml:math id="M154" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>22.22</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">140–143</oasis:entry>
         <oasis:entry colname="col2">11 471</oasis:entry>
         <oasis:entry colname="col3">1304</oasis:entry>
         <oasis:entry colname="col4"><inline-formula><mml:math id="M155" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>22.07</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">202–205</oasis:entry>
         <oasis:entry colname="col2">15 397</oasis:entry>
         <oasis:entry colname="col3">1456</oasis:entry>
         <oasis:entry colname="col4"><inline-formula><mml:math id="M156" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>23.37</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">247–250</oasis:entry>
         <oasis:entry colname="col2">16 441</oasis:entry>
         <oasis:entry colname="col3">301</oasis:entry>
         <oasis:entry colname="col4"><inline-formula><mml:math id="M157" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>23.88</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">302–305</oasis:entry>
         <oasis:entry colname="col2">17 108</oasis:entry>
         <oasis:entry colname="col3">373</oasis:entry>
         <oasis:entry colname="col4"><inline-formula><mml:math id="M158" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>25.72</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">350–353</oasis:entry>
         <oasis:entry colname="col2">17 482</oasis:entry>
         <oasis:entry colname="col3">194</oasis:entry>
         <oasis:entry colname="col4"><inline-formula><mml:math id="M159" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>25.93</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">451–454</oasis:entry>
         <oasis:entry colname="col2">17 778</oasis:entry>
         <oasis:entry colname="col3">236</oasis:entry>
         <oasis:entry colname="col4"><inline-formula><mml:math id="M160" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>25.83</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">510–513</oasis:entry>
         <oasis:entry colname="col2">18 585</oasis:entry>
         <oasis:entry colname="col3">591</oasis:entry>
         <oasis:entry colname="col4"><inline-formula><mml:math id="M161" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>25.09</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">590–593</oasis:entry>
         <oasis:entry colname="col2">19 761</oasis:entry>
         <oasis:entry colname="col3">699</oasis:entry>
         <oasis:entry colname="col4"><inline-formula><mml:math id="M162" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>24.44</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">680–683</oasis:entry>
         <oasis:entry colname="col2">23 604</oasis:entry>
         <oasis:entry colname="col3">576</oasis:entry>
         <oasis:entry colname="col4"><inline-formula><mml:math id="M163" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>23.23</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table><?xmltex \gdef\@currentlabel{2}?></table-wrap>

      <?xmltex \floatpos{p}?><fig id="Ch1.F2"><?xmltex \currentcnt{2}?><?xmltex \def\figurename{Figure}?><label>Figure 2</label><caption><p id="d1e2982"><bold>(a)</bold> NGRIP <inline-formula><mml:math id="M164" 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 <xref ref-type="bibr" rid="bib1.bibx1" id="paren.61"/> and atmospheric CO<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> <xref ref-type="bibr" rid="bib1.bibx66" id="paren.62"/> records. <bold>(b)</bold> Sea surface temperatures in the north-eastern Atlantic Ocean <xref ref-type="bibr" rid="bib1.bibx7" id="paren.63"/> and <inline-formula><mml:math id="M166" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C values from speleothems in western Europe <xref ref-type="bibr" rid="bib1.bibx140" id="paren.64"/>. The data were smoothed to eliminate very high-frequency components. <bold>(c)</bold> Zr <inline-formula><mml:math id="M167" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> Rb and Fe <inline-formula><mml:math id="M168" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> Ca elemental ratios from XRF data. <bold>(d)</bold> Peatland area (purple) and carbon (green) in Europe as a fraction of pre-industrial (PI) values (0.231 M km<inline-formula><mml:math id="M169" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula> and 19.6 GtC) <xref ref-type="bibr" rid="bib1.bibx93" id="paren.65"/> and the <inline-formula><mml:math id="M170" display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">aq</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> index record. <bold>(e)</bold> <inline-formula><mml:math id="M171" display="inline"><mml:mrow><mml:mi>f</mml:mi><mml:mi mathvariant="italic">β</mml:mi></mml:mrow></mml:math></inline-formula><inline-formula><mml:math id="M172" display="inline"><mml:mi mathvariant="italic">β</mml:mi></mml:math></inline-formula> and CPI<inline-formula><mml:math id="M173" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">alk</mml:mi></mml:msub></mml:math></inline-formula> records. <bold>(f)</bold> Pre-depositional <inline-formula><mml:math id="M174" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C ages of <italic>n</italic>-alkanoic acids from core GeoB23302-2 and BIT index record. Yellow bands mark major flooding events of the Channel River <xref ref-type="bibr" rid="bib1.bibx131" id="paren.66"/>.</p></caption>
        <?xmltex \igopts{width=241.848425pt}?><graphic xlink:href="https://cp.copernicus.org/articles/20/121/2024/cp-20-121-2024-f02.png"/>

      </fig>

</sec>
<sec id="Ch1.S4">
  <label>4</label><title>Discussion</title>
<sec id="Ch1.S4.SS1">
  <label>4.1</label><title>Source of the OM in the sedimentary record</title>
      <?pagebreak page127?><p id="d1e3146">Our results corroborate the previous findings of <xref ref-type="bibr" rid="bib1.bibx87" id="text.67"/>, showing a notable increase in the influx of terrigenous OM in the Bay of Biscay during the last deglacial period. Between ca. 20.6 and 15 cal kyr BP, the values of the Zr <inline-formula><mml:math id="M175" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> Rb ratio reflect the deposition of coarse-grained sediments at the core location, which may be associated with enhanced fluvial activity <xref ref-type="bibr" rid="bib1.bibx141" id="paren.68"/>. A period of relatively high Fe <inline-formula><mml:math id="M176" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> Ca values (ca. 21–16.4 cal kyr BP) is indicative of a greater influx of sediment from land (Fig. <xref ref-type="fig" rid="Ch1.F2"/>c). This is consistent with a period of elevated terrestrial contribution to the bulk OM present in the sediment, from approximately 20.5 to 16.5 cal kyr BP, except for a sudden decrease at approximately 19 cal kyr BP, as revealed by the BIT index <xref ref-type="bibr" rid="bib1.bibx53 bib1.bibx51 bib1.bibx63 bib1.bibx116 bib1.bibx44" id="paren.69"><named-content content-type="pre">see e.g.</named-content></xref> (Fig. <xref ref-type="fig" rid="Ch1.F2"/>f). These Fe <inline-formula><mml:math id="M177" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> Ca and BIT patterns are also recorded in core MD95 2002 <xref ref-type="bibr" rid="bib1.bibx131 bib1.bibx87" id="paren.70"><named-content content-type="pre">see Figs. S3 and S4;</named-content></xref> and a similar pattern of marked Fe <inline-formula><mml:math id="M178" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> Ca peaks, sometimes associated with peaks in OM content, during Heinrich events and much lower values throughout the Holocene has been observed at other sites <xref ref-type="bibr" rid="bib1.bibx61 bib1.bibx76 bib1.bibx148 bib1.bibx29" id="paren.71"/>.</p>
      <p id="d1e3201">Beyond identifying the presence of terrestrial OM transported to the Bay of Biscay via the Channel River during the LGM–Holocene transition, the comprehensive analysis of elemental, geochemical, and isotopic proxies presented here provides insights into the potential sources of this terrigenous OM. Values for the <inline-formula><mml:math id="M179" display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">aq</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> proxy point to a major contribution of OM from aquatic plants between approximately 20.2 and 17.2 cal kyr BP, suggesting the presence of OM sourced from wetland vegetation (Fig. <xref ref-type="fig" rid="Ch1.F2"/>d). Our CPI<inline-formula><mml:math id="M180" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">alk</mml:mi></mml:msub></mml:math></inline-formula> record reflects the degree of degradation the sedimentary OM has undergone in its previous terrestrial reservoir or during transportation <xref ref-type="bibr" rid="bib1.bibx17" id="paren.72"><named-content content-type="pre">cf.</named-content></xref>. During the peak of terrigenous deposition, the signal of more mature OM fluvially transported to the continental slope is detected in our <inline-formula><mml:math id="M181" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CPI</mml:mi><mml:mi mathvariant="normal">alk</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M182" display="inline"><mml:mrow><mml:mi>f</mml:mi><mml:mi mathvariant="italic">β</mml:mi><mml:mi mathvariant="italic">β</mml:mi></mml:mrow></mml:math></inline-formula> records, which reach relatively low values when compared to the Holocene (Fig. <xref ref-type="fig" rid="Ch1.F2"/>e). The presence of petrogenic, i.e. thermally mature, material <xref ref-type="bibr" rid="bib1.bibx36 bib1.bibx60" id="paren.73"/> is another factor to consider when interpreting these records. Nonetheless, throughout the archive, the <inline-formula><mml:math id="M183" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CPI</mml:mi><mml:mi mathvariant="normal">alk</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values remain above the diagnostic value of petrogenic material (ca. 1) reported by <xref ref-type="bibr" rid="bib1.bibx16" id="text.74"/>. Additionally, in contrast with the results of <xref ref-type="bibr" rid="bib1.bibx89" id="text.75"/> for the Bering Sea, in the present study the <inline-formula><mml:math id="M184" display="inline"><mml:mrow><mml:mi>f</mml:mi><mml:mi mathvariant="italic">β</mml:mi><mml:mi mathvariant="italic">β</mml:mi></mml:mrow></mml:math></inline-formula> proxy is not indicative of petrogenic material in the sediment (see the Supplement). This is because the values do not decrease in response to diagenetic transformations but rather due to enhanced inputs of the C31<inline-formula><mml:math id="M185" display="inline"><mml:mrow><mml:mi mathvariant="italic">α</mml:mi><mml:mi mathvariant="italic">β</mml:mi></mml:mrow></mml:math></inline-formula>R hopane, which is abundant in peat <xref ref-type="bibr" rid="bib1.bibx57" id="paren.76"/>.</p>
      <p id="d1e3303">The compound-specific <inline-formula><mml:math id="M186" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C results disclose that the analysed terrigenous biomarkers are ancient and pre-aged, indicating that they are not contemporaneous with sediment deposition but rather older  (Fig. <xref ref-type="fig" rid="Ch1.F2"/>f). Despite the large variability in OM residence time in permafrost soils, the pre-depositional ages of some of the compounds present in core GeoB23302-2 (up to 25 000 <inline-formula><mml:math id="M187" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C yr) are considerably greater than those previously attributed to permafrost-derived OM at other sites and at different timescales <xref ref-type="bibr" rid="bib1.bibx46 bib1.bibx143" id="paren.77"><named-content content-type="pre">e.g. up to ca. 10 000 <inline-formula><mml:math id="M188" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C yr;</named-content></xref>. Although petrogenic contributions are commonly thought to be devoid of <italic>n</italic>-alkanoic acids, this assumption does not always hold <xref ref-type="bibr" rid="bib1.bibx71" id="paren.78"/>, and the erosion of organic-rich sedimentary rocks can supply fossil OM to the ocean, thereby depleting the <inline-formula><mml:math id="M189" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C compound-specific signal in the sediment <xref ref-type="bibr" rid="bib1.bibx106 bib1.bibx27 bib1.bibx145" id="paren.79"><named-content content-type="pre">e.g.</named-content><named-content content-type="post">and references therein</named-content></xref>. However, the OM present in core GeoB23302-2 presents <inline-formula><mml:math id="M190" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C values in the range from <inline-formula><mml:math id="M191" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>25.9 ‰ to <inline-formula><mml:math id="M192" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>22.3 ‰, heavier than the average value of <inline-formula><mml:math id="M193" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C <inline-formula><mml:math id="M194" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> <inline-formula><mml:math id="M195" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>29.4 ‰ displayed by organic-rich rocks in the region <xref ref-type="bibr" rid="bib1.bibx149" id="paren.80"><named-content content-type="pre">e.g.</named-content></xref>. These values are rather comparable to those observed in peat, corroborating the results of the CPI<inline-formula><mml:math id="M196" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">alk</mml:mi></mml:msub></mml:math></inline-formula> and <inline-formula><mml:math id="M197" display="inline"><mml:mrow><mml:mi>f</mml:mi><mml:mi mathvariant="italic">β</mml:mi><mml:mi mathvariant="italic">β</mml:mi></mml:mrow></mml:math></inline-formula> proxies and pointing to a pre-aged immature source such as ancient peat. The pre-depositional ages observed during the peak of OM deposition likely result from a <inline-formula><mml:math id="M198" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C reservoir effect, which is caused by radioactive decay and a lack of exchange with the atmosphere <xref ref-type="bibr" rid="bib1.bibx125" id="paren.81"/>. This effect occurs as the OM is stored in its source reservoir before eventual erosion and transportation to the core location. Mechanisms such as deposition–resuspension loops on the continental slope could be invoked to explain pre-aged <italic>n</italic>-alkanoic acids during the most recent part of our record <xref ref-type="bibr" rid="bib1.bibx70" id="paren.82"><named-content content-type="post">and references therein</named-content></xref>. To summarize, our results strongly support previous findings describing a massive remobilization of terrestrial C from the European continent to the North Atlantic Ocean during the last deglaciation, with notable peaks at ca. 19.5 and between approximately 19 and 17 cal kyr BP <xref ref-type="bibr" rid="bib1.bibx87" id="paren.83"/>. In addition, the set of proxies applied in the present study allows us to go further and suggest peat-derived material as a major source of OM to the Bay of Biscay during the last deglaciation.</p>
</sec>
<sec id="Ch1.S4.SS2">
  <label>4.2</label><title>Landscape development and OM remobilization mechanisms</title>
      <?pagebreak page128?><p id="d1e3472">Wetlands are dynamic ecosystems that fix <inline-formula><mml:math id="M199" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> from the atmosphere, store C and contribute to the C cycle through various processes, including the decomposition of OM that releases <inline-formula><mml:math id="M200" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx90" id="paren.84"/>. Therefore, the establishment of wetlands in the study region towards the end of the LGM and during the last deglaciation (Fig. <xref ref-type="fig" rid="Ch1.F2"/>d), combined with permafrost distribution data that imply gradual permafrost decomposition <xref ref-type="bibr" rid="bib1.bibx135 bib1.bibx78 bib1.bibx136 bib1.bibx112 bib1.bibx137" id="paren.85"><named-content content-type="pre">e.g.</named-content></xref> and records of atmospheric <inline-formula><mml:math id="M201" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> concentration <xref ref-type="bibr" rid="bib1.bibx66" id="paren.86"/>, suggests the need to investigate thawing permafrost as a possible source of OM to the deposition site. Although some of the peatlands formed during the Eemian period were buried by glaciers and mineral sediments, Weichselian ice sheets were not as extensive as the ones from the Saalian, and some deposits remained uncovered <xref ref-type="bibr" rid="bib1.bibx34" id="paren.87"><named-content content-type="pre">e.g. in northern Germany, on the cliff of the Elbe river;</named-content></xref>. Peat deposits formed during the last interglacial occur widely across the studied region <xref ref-type="bibr" rid="bib1.bibx133" id="paren.88"/>, from Belgium <xref ref-type="bibr" rid="bib1.bibx30" id="paren.89"><named-content content-type="pre">e.g.</named-content></xref> and the Netherlands <xref ref-type="bibr" rid="bib1.bibx115" id="paren.90"><named-content content-type="pre">e.g.</named-content></xref> to Poland <xref ref-type="bibr" rid="bib1.bibx144" id="paren.91"><named-content content-type="pre">e.g.</named-content></xref>, through Germany <xref ref-type="bibr" rid="bib1.bibx13 bib1.bibx45" id="paren.92"><named-content content-type="pre">e.g.</named-content></xref> and Denmark <xref ref-type="bibr" rid="bib1.bibx24" id="paren.93"><named-content content-type="pre">e.g.</named-content></xref>. Although the environmental conditions of the last glaciation were unfavourable for the development of peatlands, factors such as the formation of permafrost in Europe resulted in the long-term preservation of OM from older periods (e.g. frozen peat OM) (<xref ref-type="bibr" rid="bib1.bibx132" id="altparen.94"/>). However, during the last deglaciation, the thawing of permafrost and the presence of meltwater streams may have contributed to the erosion of these peats. We propose that Eemian peatlands represent the primary source of fossil biomarkers transported to the Bay of Biscay, with processes such as thermal and physical erosion of these deposits <xref ref-type="bibr" rid="bib1.bibx120 bib1.bibx121" id="paren.95"><named-content content-type="pre">see e.g.</named-content></xref> leading to pre-aged material reaching the final burial site. At this point, it is crucial to emphasize that, in the context of this study, permafrost plays a more significant role as a storage mechanism for peatland OM rather than serving as a unique source of OM by itself.</p>
      <p id="d1e3564">In north-western and central Europe, continuous permafrost prevailed at approximately 27–17 cal kyr BP <xref ref-type="bibr" rid="bib1.bibx135" id="paren.96"/>, with the deposits likely degrading and shrinking due to the warming observed at the end of the LGM. For instance, in the Netherlands, there has been evidence of widespread permafrost degradation between 22 and 21 cal kyr BP <xref ref-type="bibr" rid="bib1.bibx134" id="paren.97"/>, with continuous permafrost in the Dutch coversand region completely disappearing after 20 cal kyr BP <xref ref-type="bibr" rid="bib1.bibx8" id="paren.98"/>. This episode is an example of permafrost thawing that may have contributed to wetland development between ca. 21 and 16 cal kyr BP as recorded in our <inline-formula><mml:math id="M202" display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">aq</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> record (Fig. <xref ref-type="fig" rid="Ch1.F2"/>d). Between 17 and 15 cal kyr BP, permafrost zones in the study region were restricted to areas near the retreating ice sheets <xref ref-type="bibr" rid="bib1.bibx108" id="paren.99"><named-content content-type="post">and references therein</named-content></xref>. Afterwards, apart from a short later period of discontinuous permafrost (ca. 10.9–10.5 cal kyr BP) that has also been reported for north-western and central Europe <xref ref-type="bibr" rid="bib1.bibx135" id="paren.100"/>, there is evidence of the presence of permafrost in this region during the Younger Dryas <xref ref-type="bibr" rid="bib1.bibx58 bib1.bibx100" id="paren.101"><named-content content-type="pre">e.g.</named-content></xref>.</p>
      <p id="d1e3603">The erosion of European permafrost and peatland deposits by glacial meltwater is a mechanism likely to have exported OM to the ocean. The decay of the European ice sheets and glaciers at the onset of the last deglaciation <xref ref-type="bibr" rid="bib1.bibx83 bib1.bibx109 bib1.bibx96 bib1.bibx6 bib1.bibx98" id="paren.102"><named-content content-type="pre">e.g.</named-content></xref> contributed to strengthening the Channel River discharge into the Bay of Biscay <xref ref-type="bibr" rid="bib1.bibx2 bib1.bibx14" id="paren.103"/>, and it has been proposed that this was the main mechanism controlling the river activity during this time period <xref ref-type="bibr" rid="bib1.bibx129" id="paren.104"/>. Deglacial pulses of meltwater emanating from the BIIS (at 22 and 18.6 cal kyr BP) and the FIS (starting around 19 cal kyr BP) <xref ref-type="bibr" rid="bib1.bibx15 bib1.bibx109" id="paren.105"/> were routed to the North Atlantic via the Channel River. In this way, the activity of the river responded to changes in the European ice masses, being particularly influenced by the dynamics of the FIS <xref ref-type="bibr" rid="bib1.bibx130" id="paren.106"/>.</p>
      <p id="d1e3623">Although subglacial meltwater can flow through permeable sediments as groundwater, the presence of frozen ground with reduced hydraulic transmissivity, i.e. permafrost, hinders this process <xref ref-type="bibr" rid="bib1.bibx102" id="paren.107"/>. This leads to trapped pressurized water accumulating underneath ice sheets and eventually draining during catastrophic events. As the climate warmed, and the ice sheets retreated, and/or permafrost decayed, bursts of subglacial meltwater were released, carving glacial features known as tunnel valleys in the ground and discharging large amounts of eroded material into rivers (<xref ref-type="bibr" rid="bib1.bibx101 bib1.bibx103 bib1.bibx64" id="altparen.108"/>; and references therein). Subglacial channels from major Pleistocene glaciations are still present today in Europe and serve as evidence of this phenomenon <xref ref-type="bibr" rid="bib1.bibx103 bib1.bibx104" id="paren.109"><named-content content-type="pre">e.g.</named-content></xref>. Meltwater streams from the FIS discharged through the Elbe river and provoked several flooding events of the Channel River <xref ref-type="bibr" rid="bib1.bibx81 bib1.bibx131" id="paren.110"/>, with remarkable episodes (R2–R5) recorded as peaks in the ratios Ti <inline-formula><mml:math id="M203" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> Ca and Fe <inline-formula><mml:math id="M204" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> Ca of both the GeoB23302-2 and the MD95 2002 archives (Fig. S3). Floods R2–R5 were most likely associated with enhanced processes of erosion and sediment export in the catchment <xref ref-type="bibr" rid="bib1.bibx12" id="paren.111"><named-content content-type="pre">see e.g.</named-content></xref>, and the intensified freshwater influx, resulting from riverine discharge due to a mixture of precipitation and glacial meltwaters, is reflected in the terrestrially sourced OM signal shown by our BIT index record, which corroborates that reported for core MD95 2002 <xref ref-type="bibr" rid="bib1.bibx87" id="paren.112"/> (Fig. S4). Furthermore, the process of post-glacial sea-level rise may have played a role in the erosion of coastal permafrost deposits, potentially serving as an additional pathway for the transport of OM to the ocean <xref ref-type="bibr" rid="bib1.bibx89" id="paren.113"><named-content content-type="pre">e.g.</named-content></xref>.</p>
      <?pagebreak page129?><p id="d1e3669">The remobilization of OM from land to ocean is largely mediated by rivers, with factors such as precipitation and temperature being major regulators of fluvial C fluxes <xref ref-type="bibr" rid="bib1.bibx9" id="paren.114"><named-content content-type="post">and references therein</named-content></xref>. Between 21 and 17 cal kyr BP, a temperature rise (Fig. <xref ref-type="fig" rid="Ch1.F2"/>a) observed in various Atlantic environmental records <xref ref-type="bibr" rid="bib1.bibx3 bib1.bibx7 bib1.bibx26 bib1.bibx97" id="paren.115"><named-content content-type="pre">e.g.</named-content></xref> marked a transition from cold and dry to warm and wet conditions in continental Europe. For example, a gradual increase in the north-eastern Atlantic sea surface temperature (SST) starting at about 25 cal kyr BP and preceding the peak of terrigenous deposition is recorded in core SU8118 (37<inline-formula><mml:math id="M205" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>46<inline-formula><mml:math id="M206" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> N, 10<inline-formula><mml:math id="M207" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>11<inline-formula><mml:math id="M208" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> W) <xref ref-type="bibr" rid="bib1.bibx7" id="paren.116"/>. This same warming trend can be observed on land, reflected in the <inline-formula><mml:math id="M209" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C signature of a speleothem record from western Europe (45<inline-formula><mml:math id="M210" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>30<inline-formula><mml:math id="M211" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> N, 0<inline-formula><mml:math id="M212" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>50<inline-formula><mml:math id="M213" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> E) <xref ref-type="bibr" rid="bib1.bibx140" id="paren.117"/> and starting roughly at the same time (Fig. <xref ref-type="fig" rid="Ch1.F2"/>). The speleothem time series is not high-resolution, and long-term trends may be in fact punctuated with short-term oscillations. In any case, it is important to acknowledge that, although speleothem <inline-formula><mml:math id="M214" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C values can potentially serve as a proxy for temperature <xref ref-type="bibr" rid="bib1.bibx77" id="paren.118"><named-content content-type="pre">see e.g.</named-content><named-content content-type="post">and references therein</named-content></xref>, the correlation must be interpreted with caution due to several other factors influencing C isotopic ratios in these archives <xref ref-type="bibr" rid="bib1.bibx40" id="paren.119"/>. Enhanced precipitation in response to warming led to increases in fluvial runoff and, due to widespread permafrost, increased erosion and transport of sediment from land to the Channel River outlet <xref ref-type="bibr" rid="bib1.bibx87" id="paren.120"/>. After approximately 18 cal kyr BP, as the climate warmed, the area occupied by peatlands in Europe increased <xref ref-type="bibr" rid="bib1.bibx93" id="paren.121"/>. This is in agreement with our <inline-formula><mml:math id="M215" display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">aq</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> index record, which indicates the re-establishment of formerly frozen wetlands, potentially including peat-rich environments (Fig. <xref ref-type="fig" rid="Ch1.F2"/>d).</p>
      <p id="d1e3818">Considering that the OM buried in marine sediment is only a relatively small part of the total OM entering rivers, which is predominantly returned to the atmosphere as <inline-formula><mml:math id="M216" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx4" id="paren.122"><named-content content-type="pre">e.g.</named-content></xref>, the OM export to the Bay of Biscay via the Channel River is likely to have been accompanied by the transfer of <inline-formula><mml:math id="M217" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M218" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CH</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> to the atmosphere <xref ref-type="bibr" rid="bib1.bibx114 bib1.bibx119 bib1.bibx17" id="paren.123"><named-content content-type="pre">e.g.</named-content></xref>. It follows that our comprehensive analysis, encompassing biomarkers, elemental proxies and radiocarbon dating, consistently corroborates the hypothesis of permafrost thawing in the Northern Hemisphere contributing to the observed perturbations in the atmospheric C reservoir <xref ref-type="bibr" rid="bib1.bibx65" id="paren.124"/>. This essentially means that north-western and central Europe too, similar to other permafrost sites <xref ref-type="bibr" rid="bib1.bibx143 bib1.bibx89" id="paren.125"/>, may have contributed to the deglacial rise in atmospheric <inline-formula><mml:math id="M219" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx65 bib1.bibx82" id="paren.126"/>. However, it is likely that the deglacial loss of European permafrost was offset by the subsequent accumulation of significant amounts of C in permafrost-free soils and peatlands (<xref ref-type="bibr" rid="bib1.bibx79" id="altparen.127"/>). Our elevated pre-depositional ages at ca. 17.5 cal kyr BP (up to ca. 15 <inline-formula><mml:math id="M220" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C kyr) may partly explain the steep drop in the <inline-formula><mml:math id="M221" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C signature of atmospheric <inline-formula><mml:math id="M222" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> during the period known as the Mystery Interval (17.5–14.5 kyr BP) <xref ref-type="bibr" rid="bib1.bibx18" id="paren.128"><named-content content-type="pre">see e.g.</named-content></xref>. In other words, this result implies that thawing European permafrost combined with the deep-ocean reservoir contributed <inline-formula><mml:math id="M223" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C-depleted <inline-formula><mml:math id="M224" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> to the atmosphere during this period. However, our results show that the remobilization of C from this terrestrial pool started as early as ca. 20.2 cal kyr BP, which considerably precedes estimates of large permafrost contributions to atmospheric <inline-formula><mml:math id="M225" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> between 17.5 and 15 kyr BP <xref ref-type="bibr" rid="bib1.bibx28" id="paren.129"/>. This suggests the need to investigate leads and lags in the permafrost carbon feedback.</p>
      <p id="d1e3958">After approximately 18 cal kyr BP, a rerouting of the Elbe–Weser system meant that FIS meltwater carrying ancient C was being delivered to the Norwegian Channel <xref ref-type="bibr" rid="bib1.bibx130" id="paren.130"><named-content content-type="post">and references therein</named-content></xref>. After 17 cal kyr BP, sea-level rise caused a shift in the shoreline, with the Bay of Biscay no longer being suitable to record terrestrial runoff during the Holocene <xref ref-type="bibr" rid="bib1.bibx74" id="paren.131"/>. This is reflected in the sudden drop observed in the BIT index record (Fig. <xref ref-type="fig" rid="Ch1.F2"/>f). Notably, although our data support what has been previously inferred for the study region <xref ref-type="bibr" rid="bib1.bibx87 bib1.bibx111 bib1.bibx124" id="paren.132"/>, the distinct timing for the discharge peak observed in this study compared to other sites may imply different mechanisms of C remobilization, and these need to be further investigated. Indeed, factors such as the local hydrology and vegetation have been shown to play a role in the accumulation and degradation pathways of permafrost-influenced peatlands <xref ref-type="bibr" rid="bib1.bibx56" id="paren.133"><named-content content-type="post">and references therein</named-content></xref>.</p>
      <p id="d1e3979">Peat-forming wetlands remain an important source of terrestrial OM to the ocean and of <inline-formula><mml:math id="M226" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CH</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M227" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> to the atmosphere, with flux rates likely increasing due to current warming <xref ref-type="bibr" rid="bib1.bibx41 bib1.bibx52" id="paren.134"/>. In high-northern-latitude wetlands, it has been shown that permafrost degradation leads to wetland shrinkage <xref ref-type="bibr" rid="bib1.bibx5" id="paren.135"/>. In the tropics the situation is also critical, with anthropogenic <xref ref-type="bibr" rid="bib1.bibx92" id="paren.136"/> and natural <xref ref-type="bibr" rid="bib1.bibx113 bib1.bibx42" id="paren.137"/> factors contributing to the remobilization of pre-aged C from peatlands. Therefore, the release of large amounts of peat-derived OM described here for deglacial Europe has analogues in the present day and may be useful to inform future projections of permafrost peatland loss <xref ref-type="bibr" rid="bib1.bibx38" id="paren.138"><named-content content-type="pre">e.g.</named-content></xref>, with our results advocating for the importance of better constraining the C cycle in wetlands.</p>
</sec>
</sec>
<sec id="Ch1.S5" sec-type="conclusions">
  <label>5</label><title>Conclusions</title>
      <p id="d1e4032">To reconcile the great pre-depositional ages observed here with geochemical data that do not hint towards highly degraded petrogenic material, we argue that the OM in core GeoB23302-2 is mostly derived from ancient continental peat deposits. During the last interglacial, peatlands were established in the European landscape. These deposits were widely distributed and were preserved in a frozen state throughout the last glaciation due to the widespread presence of permafrost. Over the course of the last deglaciation, warming and episodes of ice-sheet retreat and associated flooding through the Channel River resulted in the erosion of these permafrost deposits, enhancing the downstream transport of sediment and mobilizing ancient C to the core site. Our results indicate that during the period between 20.2 and 15.8 cal kyr BP, a substantial portion of the OM transported to the Bay of Biscay originated from ancient European peatlands. After approximately 17 cal kyr BP, our core location was not suitable for recording terrigenous inputs via the Channel River. Instead, the Norwegian Channel may have become the primary recipient of fluvially discharged permafrost-derived C. It is possible that the emission of greenhouse gases resulting from the degradation of formerly frozen OM in European permafrost contributed to the rapid rise of approximately 30 ppm in the atmospheric <inline-formula><mml:math id="M228" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> concentration between 17.5 and 16 cal kyr BP. However, further investigation is needed to accurately quantify the rates<?pagebreak page130?> and magnitudes of the processes responsible for this contribution. This study provides empirical evidence of a cycle of peat formation during warm periods and long-term storage under colder conditions. Owing to the size of the C pool involved, such a mechanism is likely to increase atmospheric greenhouse gas concentrations, with important implications for Earth’s climate. In this context, our results will be useful to better constrain the role of ancient C mobilization and the permafrost carbon feedback in climate models.</p>
</sec>

      
      </body>
    <back><notes notes-type="dataavailability"><title>Data availability</title>

      <p id="d1e4050">Data generated in this study are freely available at <uri>https://doi.pangaea.de/10.1594/PANGAEA.954937</uri> <xref ref-type="bibr" rid="bib1.bibx105" id="paren.139"/>.</p>
  </notes><app-group>
        <supplementary-material position="anchor"><p id="d1e4059">The supplement related to this article is available online at: <inline-supplementary-material xlink:href="https://doi.org/10.5194/cp-20-121-2024-supplement" xlink:title="pdf">https://doi.org/10.5194/cp-20-121-2024-supplement</inline-supplementary-material>.</p></supplementary-material>
        </app-group><notes notes-type="authorcontribution"><title>Author contributions</title>

      <p id="d1e4068">GM designed the study. GM, KZ and HG collected the sediment core. Funding for the project was acquired by GM and EQA. EQA and WW conducted the laboratory analyses with the support of JH, HG, TG and TT. EQA, GM, JH, HG and WW analysed the data. EQA wrote the paper and generated the figures. All authors provided feedback on the paper.</p>
  </notes><notes notes-type="competinginterests"><title>Competing interests</title>

      <p id="d1e4074">One of the co-authors is an employee of EGU. This has not influenced the decision of the independent journal editor.</p>
  </notes><notes notes-type="disclaimer"><title>Disclaimer</title>

      <p id="d1e4080">Publisher’s note: Copernicus Publications remains neutral with regard to jurisdictional claims made in the text, published maps, institutional affiliations, or any other geographical representation in this paper. While Copernicus Publications makes every effort to include appropriate place names, the final responsibility lies with the authors.</p>
  </notes><ack><title>Acknowledgements</title><p id="d1e4086">This research was funded by the Alexander von Humboldt Foundation via a post-doctoral fellowship granted to Eduardo Queiroz Alves. Thanks are also due to the Brazilian National Council for Scientific and Technological Development (CNPq) for the support provided to Eduardo Queiroz Alves. Hendrik Grotheer was funded by the German Science Foundation within the Cluster of Excellence EXC 2077 “The Oceans Floor – Earth’s Uncharted Interface” (project no. 390741603). We thank  Enno Schefuß,   Kita Macario and Fernanda Matos for helpful discussions that benefited this research. We are also grateful for the data provided by Samuel Toucanne and  Fortunat Joos and for the technical laboratory support offered by Elizabeth Bonk and Lea Phillips. Finally, we are grateful to Alberto Reyes, Benjamin Gagliotti, and two anonymous referees for their constructive comments and valuable suggestions.</p></ack><notes notes-type="financialsupport"><title>Financial support</title>

      <p id="d1e4091">This research has been supported by the Alexander von Humboldt-Stiftung (grant no. 1208249) and the German Science Foundation within the Cluster of Excellence EXC 2077 “The Oceans Floor – Earth’s Uncharted Interface” (project no. 390741603).</p>
  </notes><notes notes-type="reviewstatement"><title>Review statement</title>

      <p id="d1e4097">This paper was edited by Alberto Reyes and reviewed by Benjamin Gaglioti and two anonymous referees.</p>
  </notes><ref-list>
    <title>References</title>

      <ref id="bib1.bibx1"><?xmltex \def\ref@label{{Andersen et~al.(2004)Andersen, Azuma, Barnola, Bigler, Biscaye,
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