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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-19-1931-2023</article-id><title-group><article-title>Late Cenozoic sea-surface-temperature evolution of the <?xmltex \hack{\break}?> South Atlantic Ocean</article-title><alt-title>Late Cenozoic sea-surface-temperature evolution of the South Atlantic Ocean</alt-title>
      </title-group><?xmltex \runningtitle{Late Cenozoic sea-surface-temperature evolution of the South Atlantic Ocean}?><?xmltex \runningauthor{F. S. Hoem et al.}?>
      <contrib-group>
        <contrib contrib-type="author" corresp="yes" rid="aff1">
          <name><surname>Hoem</surname><given-names>Frida S.</given-names></name>
          <email>frida.snho@gmail.com</email>
        <ext-link>https://orcid.org/0000-0002-8834-6799</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2 aff3">
          <name><surname>López-Quirós</surname><given-names>Adrián</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-7522-2834</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>van de Lagemaat</surname><given-names>Suzanna</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-2447-3318</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff4 aff5">
          <name><surname>Etourneau</surname><given-names>Johan</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff6">
          <name><surname>Sicre</surname><given-names>Marie-Alexandrine</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-5015-1400</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff7">
          <name><surname>Escutia</surname><given-names>Carlota</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-4932-8619</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1 aff8">
          <name><surname>Brinkhuis</surname><given-names>Henk</given-names></name>
          
        <ext-link>https://orcid.org/0000-0003-0253-6610</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Peterse</surname><given-names>Francien</given-names></name>
          
        <ext-link>https://orcid.org/0000-0001-8781-2826</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Sangiorgi</surname><given-names>Francesca</given-names></name>
          
        <ext-link>https://orcid.org/0000-0003-4233-6154</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Bijl</surname><given-names>Peter K.</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-1710-4012</ext-link></contrib>
        <aff id="aff1"><label>1</label><institution>Department of Earth Science, Utrecht University, Utrecht, the
Netherlands</institution>
        </aff>
        <aff id="aff2"><label>2</label><institution>Department of Stratigraphy and Paleontology, University of Granada,
Granada, Spain</institution>
        </aff>
        <aff id="aff3"><label>3</label><institution>Department of Geoscience, iCLIMATE Centre, Aarhus University, Aarhus C, Denmark</institution>
        </aff>
        <aff id="aff4"><label>4</label><institution>EPHE, PSL Research University, Paris, France</institution>
        </aff>
        <aff id="aff5"><label>5</label><institution>UMR 5805 EPOC, CNRS, University of Bordeaux, Bordeaux INP, EPOC, UMR 5805, Pessac, France</institution>
        </aff>
        <aff id="aff6"><label>6</label><institution>LOCEAN, CNRS, Sorbonne Université, Campus Pierre et Marie Curie, Paris, France</institution>
        </aff>
        <aff id="aff7"><label>7</label><institution>IACT, CSIC, University of Granada, Granada, Spain</institution>
        </aff>
        <aff id="aff8"><label>8</label><institution>Department of Ocean Systems Research, Royal Netherlands Institute for Sea Research (NIOZ), Texel, the Netherlands</institution>
        </aff>
      </contrib-group>
      <author-notes><corresp id="corr1">Frida S. Hoem (frida.snho@gmail.com)</corresp></author-notes><pub-date><day>13</day><month>October</month><year>2023</year></pub-date>
      
      <volume>19</volume>
      <issue>10</issue>
      <fpage>1931</fpage><lpage>1949</lpage>
      <history>
        <date date-type="received"><day>18</day><month>February</month><year>2023</year></date>
           <date date-type="rev-request"><day>1</day><month>March</month><year>2023</year></date>
           <date date-type="rev-recd"><day>17</day><month>August</month><year>2023</year></date>
           <date date-type="accepted"><day>23</day><month>August</month><year>2023</year></date>
      </history>
      <permissions>
        <copyright-statement>Copyright: © 2023 </copyright-statement>
        <copyright-year>2023</copyright-year>
      <license license-type="open-access"><license-p>This work is licensed under the Creative Commons Attribution 4.0 International License. To view a copy of this licence, visit <ext-link ext-link-type="uri" xlink:href="https://creativecommons.org/licenses/by/4.0/">https://creativecommons.org/licenses/by/4.0/</ext-link></license-p></license></permissions><self-uri xlink:href="https://cp.copernicus.org/articles/.html">This article is available from https://cp.copernicus.org/articles/.html</self-uri><self-uri xlink:href="https://cp.copernicus.org/articles/.pdf">The full text article is available as a PDF file from https://cp.copernicus.org/articles/.pdf</self-uri>
      <abstract><title>Abstract</title>

      <p id="d1e213">At present, a strong latitudinal sea-surface-temperature (SST)
gradient of <inline-formula><mml:math id="M1" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 16 <inline-formula><mml:math id="M2" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C exists across the Southern
Ocean, maintained by the Antarctic Circumpolar Current (ACC) and a set of
complex frontal systems. Together with the Antarctic ice masses, this system
has formed one of the most important global climate regulators. The timing
of the onset of the ACC system, its development towards modern-day strength
and the consequences for the latitudinal SST gradient around the southern
Atlantic Ocean are still uncertain. Here we present new TEX<inline-formula><mml:math id="M3" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula> (TetraEther indeX of tetraethers consisting of 86 carbon atoms)-derived
SST records from two sites located east of Drake Passage (south-western South
Atlantic) to assist in better understanding two critical time intervals of
prominent climate transitions during the Cenozoic: the late Eocene–early
Oligocene (Ocean Drilling Program, ODP, Site 696) and Middle–Late Miocene (IODP Site U1536)
transitions. Our results show temperate conditions (20–11 <inline-formula><mml:math id="M4" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C)
during the first time interval, with a weaker latitudinal SST gradient
(<inline-formula><mml:math id="M5" display="inline"><mml:mo lspace="0mm">∼</mml:mo></mml:math></inline-formula> 8 <inline-formula><mml:math id="M6" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C) across the Atlantic sector of the Southern
Ocean compared to present day. We ascribe the similarity in SSTs between
Sites 696 and 511 in the late Eocene–early Oligocene South Atlantic to a
persistent, strong subpolar gyre circulation connecting the sites, which
can only exist in the absence of a strong throughflow across the Drake Passage.
Surprisingly, the southern South Atlantic record Site 696 shows comparable
SSTs (<inline-formula><mml:math id="M7" display="inline"><mml:mo lspace="0mm">∼</mml:mo></mml:math></inline-formula> 12–14 <inline-formula><mml:math id="M8" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C) during both the earliest
Oligocene oxygen isotope step (EOIS, <inline-formula><mml:math id="M9" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 33.65 Ma) and the
Miocene Climatic Optimum (MCO, <inline-formula><mml:math id="M10" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 16.5 Ma). Apparently, maximum
Oligocene Antarctic ice volume could coexist with warm ice-proximal surface
ocean conditions, while at similar ocean temperatures, the Middle Miocene
Antarctic ice sheet was likely reduced. Only a few Middle–Late Miocene
(discontinuous) high-latitude records exist due to ice advances causing
unconformities. Our low-resolution Site U1536 record of southern South
Atlantic SSTs cooled to <inline-formula><mml:math id="M11" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 5 <inline-formula><mml:math id="M12" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C during the Middle
Miocene Climate Transition (MMCT, 14 Ma), making it the coldest oceanic
region in the poorly recorded Antarctic realm and likely the main location
for deep-water formation. The already-cold south-western South Atlantic
conditions at the MMCT with relatively moderate additional cooling during the
Late Miocene contrasts with the profound cooling in the lower latitudes and other
sectors of the Southern Ocean due to northward expansion of the Southern
Ocean frontal systems.</p>
  </abstract>
    
<funding-group>
<award-group id="gs1">
<funding-source>Nederlandse Organisatie voor Wetenschappelijk Onderzoek</funding-source>
<award-id>ALW.2016.001</award-id>
</award-group>
</funding-group>
</article-meta>
  </front>
<body>
      

      <?xmltex \hack{\newpage}?>
<?pagebreak page1932?><sec id="Ch1.S1" sec-type="intro">
  <label>1</label><title>Introduction</title>
      <p id="d1e325">Today, Southern Ocean surface flow is dominated by the strongest ocean
surface current on Earth, the Antarctic Circumpolar Current (ACC). This
wind-driven, eastward-flowing surface current is associated with strong
meridional gradients in sea surface temperature (SST) (<inline-formula><mml:math id="M13" display="inline"><mml:mo lspace="0mm">∼</mml:mo></mml:math></inline-formula> 16 <inline-formula><mml:math id="M14" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, <inline-formula><mml:math id="M15" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 45–60<inline-formula><mml:math id="M16" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> S) and oceanographic
conditions (Locarnini et al., 2018). Questions remain about the timing and
nature of the development of the ACC and concomitant evolution of the complex
Southern Ocean frontal systems (Fig. 1). A primary prerequisite for the
existence of a strong ACC is an unobstructed latitudinal band of (deep-ocean) water (Orsi et al., 1995; Barker and Thomas, 2004; Toggweiler et al.,
2006), which is largely determined by the tectonic evolution and opening of
the Tasmanian Gateway as well as the Drake Passage (Huber et al., 2004).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F1" specific-use="star"><?xmltex \currentcnt{1}?><?xmltex \def\figurename{Figure}?><label>Figure 1</label><caption><p id="d1e362">Present-day map of the Southern Ocean showing the location of the
drill sites used in this study. Grey areas represent present-day land
masses. The colours show average summer (January) SSTs from 1971–2000
(Reynolds et al., 2002). The white areas lack modern SST data, as they are
covered by ice shelves. The white lines represent the smoothed, simplified
position of circumpolar fronts interpreted by Orsi et al. (1995). From north
to south: the Subtropical Front (STF), the Subantarctic Front (SAF), the
Polar Front (PF), the Southern ACC Front (sACCf) and the Southern Boundary
(SBdy) Front. SI: Seymour Island; SD: SHALLDRILL; WS: Weddell Sea;
SS: Scotia Sea; SOM: South Orkney Microcontinent.</p></caption>
        <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://cp.copernicus.org/articles/19/1931/2023/cp-19-1931-2023-f01.png"/>

      </fig>

      <p id="d1e371">The tectonic evolution of the Tasmanian Gateway is relatively well
constrained; early southern opening of the Tasmanian Gateway started around
49–50 Ma (Huber et al., 2004; Stickley et al., 2004; Bijl et al., 2013)
with a change in course of tectonic drift of Australia from the north-east to
the north (Whittaker et al., 2007). Final breakup between Australia and
Antarctica started around <inline-formula><mml:math id="M17" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 35.5 Ma, with ocean crust
formation between south-western Tasmania and Wilkes Land, Antarctica, and
onset of bottom-water currents around 35.5–33.5 Ma (Stickley et al., 2004;
Houben et al., 2019), although the strength of this so-called “proto-ACC”
during the Oligocene remains debated. New field data reconstructing SST and
water properties (Bijl et al., 2018; Hartman et al., 2018; Salabarnada et
al., 2018; Evangelinos et al., 2020, 2022; Sauermilch et al., 2021; Hoem et
al., 2021a, b, 2022; Duncan et al., 2022; Hou et al., 2023) allow tracing
of the migration of frontal systems, which may be reconducted to opening of
gateways. Furthermore, high-resolution modelling exercises (England et al.,
2017; O'Brien et al., 2020; Sauermilch et al., 2021; Nooteboom et al., 2022)
show a large effect of the opening and depth of the Southern Ocean gateways
on the Australian–Antarctic Gulf oceanographic conditions. A recent SST
compilation from around the Tasmanian Gateway (Hoem et al., 2022) shows that
the latitudinal SST gradient between the Subtropical Front and the Antarctic
Margin progressively increased from <inline-formula><mml:math id="M18" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 26 Ma onwards due to
cooling at Antarctic-proximal sites. Since the Tasmanian Gateway was already
open, wide and deep, this Antarctic cooling may have been related to the
onset of deep-ocean connections through the Drake Passage (Lyle et al.,
2007; van de Lagemaat et al., 2021). The plate tectonic configuration of the
Drake Passage–Scotia Sea region is more complex than that of the Tasmanian
Gateway, with various oceanic basins that opened at different times, and the
separation of continental fragments from southernmost South America and from
the Antarctic Peninsula (Kennett, 1977; Barker and Thomas, 2004; Maldonado
et al., 2006; Lagabrielle et al., 2009; Pérez et al., 2019, 2021). The
timing and nature of the opening, widening and deepening of the Drake
Passage have also been much debated and are placed between 50 and 16 Ma
(Barker et al., 2007; Livermore et al., 2007; Eagles and Jokat, 2014;
Maldonado et al., 2014; Pérez et al., 2021; van de Lagemaat et al.,
2021). While some deep-ocean sedimentary records suggest that oceanographic
rearrangements were possibly linked to an early Drake Passage opening
(Kennett, 1977; Scher and Martin, 2006; López-Quirós et al., 2019, 2021), we lack knowledge of the long-term
evolution of South Atlantic oceanographic conditions since the late Eocene.
By reconstructing the development of the South Atlantic SST gradient, we can
interpret phases of Antarctic cooling, strengthening of the ACC and shifts
in the frontal systems. In turn, the changes in these three processes can be
linked to the throughflow of surface and deep waters through the Drake
Passage.</p>
      <p id="d1e389">Recent drilling efforts in and around the Scotia Sea as part of
International Ocean Discovery Program (IODP) Expedition 382 (Weber et al.,
2021a) and a revisit of previously drilled records in the Weddell Sea
during Ocean Drilling Program (ODP) Leg 113 offer improved spatial coverage of sedimentary records
across two prominent climate transitions, viz. (1) the Eocene–Oligocene
transition (EOT, 33.7 Ma) and (2) the transition from the Miocene Climatic
Optimum (MCO, <inline-formula><mml:math id="M19" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 16.5 Ma) to the Middle Miocene Climate Transition
(MMCT, <inline-formula><mml:math id="M20" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 14.7–13.8 Ma) and the Late Miocene Cooling (LMC,
<inline-formula><mml:math id="M21" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 7–5.4 Ma). Both transitions are marked by increases in
benthic foraminiferal <inline-formula><mml:math id="M22" 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, suggesting cooling and expansion of
the Antarctic ice sheet (Rohling et al., 2022). Given the paucity of
carbonaceous sediments in this region, typically employed for
paleotemperature reconstructions, we choose here to generate lipid biomarker
(TetraEther indeX of tetraethers consisting of 86 carbon atoms, TEX<inline-formula><mml:math id="M23" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>)
proxy SST reconstructions, based on isoprenoid glycerol dialkyl glycerol
tetraether (isoGDGT) distributions in sediments from the northern Weddell
Sea at ODP Site 696 (late Eocene–early Oligocene) and southern Scotia Sea
IODP Site U1536 (Middle–Late Miocene) (Fig. 1). We compare our findings to
available TEX<inline-formula><mml:math id="M24" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>, alkenone unsaturation index (<inline-formula><mml:math id="M25" display="inline"><mml:mrow><mml:msubsup><mml:mi>U</mml:mi><mml:mn mathvariant="normal">37</mml:mn><mml:mrow><mml:msup><mml:mi>k</mml:mi><mml:mo>′</mml:mo></mml:msup></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>)
and clumped-isotope-derived (<inline-formula><mml:math id="M26" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="normal">Δ</mml:mi><mml:mn mathvariant="normal">47</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>) SST records from the
South Atlantic region (Fig. 1) for a reconstruction of paleoceanographic
conditions over the late Cenozoic.</p>
</sec>
<sec id="Ch1.S2">
  <label>2</label><title>Material</title>
<sec id="Ch1.S2.SS1">
  <label>2.1</label><title>Sedimentary drill cores</title>
<sec id="Ch1.S2.SS1.SSS1">
  <label>2.1.1</label><title>Site 696 lithology, age model and depositional setting</title>
      <?pagebreak page1933?><p id="d1e493">ODP Leg 113 Site 696 was drilled in the northern Weddell Sea (61<inline-formula><mml:math id="M27" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>50.959<inline-formula><mml:math id="M28" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> S, 42<inline-formula><mml:math id="M29" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>55.996<inline-formula><mml:math id="M30" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> W), on the South Orkney Microcontinent (Fig. 1), located south of the Southern Boundary (SBdy) Front. The site had a late
Eocene paleolatitude of <inline-formula><mml:math id="M31" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 67<inline-formula><mml:math id="M32" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> S (<uri>http://paleolatitude.org</uri>, last access: 1 February 2023;
Version 2.1; van Hinsbergen et al., 2015, using the paleomagnetic reference
frame of Torsvik et al., 2012, and the geological reconstruction of Seton
et al., 2012).</p>
      <p id="d1e552">Lithological descriptions and age constraints are gathered from
López-Quirós et al. (2021; Fig. 2, Table S1 in the Supplement). The age
model is based primarily on calcareous nannofossil biostratigraphy (Wei and
Wise, 1990; Villa et al., 2008) and updated age constraints from organic
walled dinoflagellate cysts (dinocysts) published previously (Houben et al.,
2013, 2019; López-Quirós et al., 2021), which places
the studied section of 607.6–548.9 m b.s.f. (metres below seafloor; Cores 59R–53R) at 36.0 to 33.2 Ma
(Houben et al., 2013; Table S1 in the Supplement). In the sediments overlying the lower Oligocene interval, 532–529.8 m b.s.f. (Cores 52R–51R), no specific age
constraint was determined, but dinocyst analysis indicates that the sediment
is of Oligocene age. Core 50R was initially dated to 14.3–14.8 Ma (Barker
et al., 1988; Gersonde and Burckle, 1990); however, the diatom
biostratigraphic scheme was adjusted, and ages were updated to 17.6–15.4 Ma
(Carter et al., 2017). More recently a thorough review of age-deterministic
diatoms (<italic>Denticulopsis maccolummii</italic> and <italic>Actinocyclus ingens</italic>) have narrowed the Carter et al. (2017) age interval of Core 50R
to 16.7–16.5 Ma (López-Quirós et al., 2018).</p>

      <?xmltex \floatpos{p}?><fig id="Ch1.F2" specific-use="star"><?xmltex \currentcnt{2}?><?xmltex \def\figurename{Figure}?><label>Figure 2</label><caption><p id="d1e563">Age–depth model of ODP Site 696 (Table S1 in the Supplement) and
lithological log modified after López-Quirós et al. (2019, 2020, 2021) and Barker et al. (1988), including new constraints of the uppermost
interval (Core 50) from López-Quirós et al. (2018).</p></caption>
            <?xmltex \igopts{width=398.338583pt}?><graphic xlink:href="https://cp.copernicus.org/articles/19/1931/2023/cp-19-1931-2023-f02.png"/>

          </fig>

      <?pagebreak page1935?><p id="d1e573">The studied sediment package at Site 696 (607.6–521.08 m b.s.f.) consists of (1)
organic-rich sandy mudstone facies (607.6–606.9 m b.s.f.); (2) glaucony-bearing
packstone facies (606.9 to 569.7 m b.s.f.); (3) claystone and limestone facies
(569.7–548.9 m b.s.f.); (4) rhythmically interbedded sandy mudstone facies with
glauconite-bearing sandstone beds (548.9–529.8 m b.s.f.); and (5) pelagic
sediments, predominately biosiliceous diatom ooze (522–521 m b.s.f.)
(López-Quirós et al., 2019, 2020, 2021). The glauconitic packstone
beds of latest Eocene age (606.9–569.7 m b.s.f., <inline-formula><mml:math id="M33" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 35.5–34.1 Ma)
are attributed to a decline in terrigenous input to Site 696 and increased
winnowing (López-Quirós et al., 2019). The glauconitic packstone
beds of latest Eocene age (606.9 to 569.7 m b.s.f., <inline-formula><mml:math id="M34" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 35.5–34.1 Ma) are attributed to a decline in terrigenous input to Site 696 and
increased winnowing (López-Quirós et al., 2019) as a result of the
Powell Basin at the tip of the Antarctic Peninsula opening and incipient
South Orkney Microcontinent subsidence. However, the Antarctic-proximal
location makes the site prone to influx of terrigenous material transported
by icebergs, as shown by the unequivocal evidence of iceberg-rafted debris
(IRD) deposited across the EOT (34.1–33.6 Ma, 576–568 m b.s.f.) at Site 696
(López-Quirós et al., 2021). Across the EOT, sediments at Site 696
reflect an increasingly distal and deeper environment as the South Orkney
Microcontinent continued to deepen (López-Quirós et al., 2021).
Eutrophic surface water conditions, indicative of productive and somewhat
shallow-water and reduced-oxygen conditions, are indicated by dinocysts
(Houben et al., 2019) and sedimentary facies (López-Quirós et al.,
2019, 2021). The dominance of large-sized heterotrophic Protoperidiniacean dinocysts in the earliest Oligocene is suggested to reflect seasonal sea-ice
coverage (Houben et al., 2013). During the earliest Oligocene
(<inline-formula><mml:math id="M35" display="inline"><mml:mo lspace="0mm">∼</mml:mo></mml:math></inline-formula> 33.6–33.2 Ma), the South Orkney Microcontinent shelf
subsided, and biological production increased, partially driven by upwelling
along the shelf (López-Quirós et al., 2021). Deposition of
moderately to intensely bioturbated silty mudstones during the EOT is
attributed to the continued subsidence-related deepening at Site 696
(López-Quirós et al., 2021). Above the clayey mudstones of
the lowermost Oligocene (Core 53R; Fig. 2) we find rhythmically interbedded
sandy mudstones with glauconite-bearing sandstone beds, a result of reworked
sediments, deposited under bottom-current activity and possibly slumping
(López-Quirós et al., 2020). The nature of this sediment complicates
dating of this material. There is likely a break in the sedimentation
(hiatus) around 529 m b.s.f. (the top part of Core 51R), with a sharp contact
from glauconitic-bearing sandstone to mud-bearing diatom ooze 522–521 m b.s.f.
(Core 50R), dated to <inline-formula><mml:math id="M36" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 16.7–16.5 Ma (López-Quirós et
al., 2018).</p>
</sec>
<sec id="Ch1.S2.SS1.SSS2">
  <label>2.1.2</label><title>Site U1536: lithology, age model and depositional setting</title>
      <p id="d1e612">Site U1536 is located in the Dove Basin, in the southern Scotia Sea
(59<inline-formula><mml:math id="M37" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>26.4608<inline-formula><mml:math id="M38" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> S, 41<inline-formula><mml:math id="M39" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>3.6399<inline-formula><mml:math id="M40" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> W; 3220 m water depth). The
site was drilled to study the Neogene flux of icebergs through “Iceberg
Alley”, the main pathway along which icebergs calved from the margin of the
Antarctic ice sheet drift into the warmer waters of the ACC (Weber et al.,
2021a). Today, the site is located just south of the Southern ACC Front
(sACCf) and the Southern Boundary (SBdy) Front and is seasonally covered by
sea ice (Fig. 1). The rotary drilling at Hole U1536E penetrated down to 643 m b.s.f.. Sediments have moderate to high core disturbance and biscuiting or
brecciated core material due to the rough nature of rotary drilling and
compaction of gravel-rich material. The lithology of the studied interval
from Hole U1536E, 640–450 m b.s.f. (Cores 33R–13R), consists of silty clays
with interbedded diatom ooze (Fig. 3), with an estimated average
sedimentation rate of <inline-formula><mml:math id="M41" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 4.3 cm kyr<inline-formula><mml:math id="M42" 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> (3.9–6.4 cm kyr<inline-formula><mml:math id="M43" 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>; Pérez
et al., 2021). The shipboard bio- and magnetostratigraphic age model was
used to date the sediments (Weber et al., 2021b; Table S2 in the Supplement).
Sediments between 480–450 m b.s.f. (Cores 16R–13R) have an age of 6–5 Ma
based on bio- and magnetostratigraphy. Diatom biostratigraphy between
548–535 m b.s.f. (Cores 24R–22R) indicates ages of 7.7–6.4 Ma. The sediment
directly overlying Reflector-c (Weber et al., 2021b), at 617–570 m b.s.f.
(Cores 30R–26R), has an age of 8.4 Ma (Pérez et al., 2021). The
sediments below Reflector-c, at 622 m b.s.f. (Core 31R), are dated to
<inline-formula><mml:math id="M44" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 14.2 Ma, and as the lithologic contact is not recovered,
Reflector-c could represent a prolonged time interval of slow sedimentation
rates or non-deposition or erosion. The sparse brecciated lithology
fragments in the lower cores, below Reflector-c (566 m b.s.f.), consist of
lithified mudstone and gravel–conglomerate–breccia (Weber et al., 2021b;
Perez et al., 2021).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F3" specific-use="star"><?xmltex \currentcnt{3}?><?xmltex \def\figurename{Figure}?><label>Figure 3</label><caption><p id="d1e692">Site U1536 age model and lithology modified after the IODP
Expedition 382 shipboard report (Weber et al., 2021b). The depth and age of
the stratigraphic discontinuities (seismic reflectors) are derived from
Pérez et al. (2021) (Table S2 in the Supplement; Pérez et al., 2021). LO: last
occurrence; FO: first occurrence.</p></caption>
            <?xmltex \igopts{width=497.923228pt}?><graphic xlink:href="https://cp.copernicus.org/articles/19/1931/2023/cp-19-1931-2023-f03.png"/>

          </fig>

</sec>
</sec>
</sec>
<sec id="Ch1.S3">
  <label>3</label><title>Methods</title>
<sec id="Ch1.S3.SS1">
  <label>3.1</label><title>Lipid extraction and glycerol dialkyl glycerol tetraether (GDGT)
analysis</title>
      <p id="d1e718">Lipid extraction of sediments from Site 696 was performed at the Laboratoire
d'Océanographie et du Climat, Expérimentations et Approches
Numériques (LOCEAN-Sorbonne Université, Paris, France). First, 71
sediment samples were freeze-dried and crushed to a fine powder. Total
lipids were extracted from <inline-formula><mml:math id="M45" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 9.5 to 15 g of homogenised
sediment using a solvent mixture of 40 mL <inline-formula><mml:math id="M46" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">dichloromethane</mml:mi><mml:mo>:</mml:mo><mml:mi mathvariant="normal">methanol</mml:mi></mml:mrow></mml:math></inline-formula>
(<inline-formula><mml:math id="M47" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">DCM</mml:mi><mml:mo>:</mml:mo><mml:mi mathvariant="normal">MeOH</mml:mi></mml:mrow></mml:math></inline-formula>; <inline-formula><mml:math id="M48" display="inline"><mml:mrow><mml:mn mathvariant="normal">3</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>). The apolar fraction was separated from the polar
lipids by passing the total lipid extract (TLE) over a silica column
using 3 mL hexane as an eluent, followed by the recovery of the polar fraction
by eluting with 3 mL <inline-formula><mml:math id="M50" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">DCM</mml:mi><mml:mo>:</mml:mo><mml:mi mathvariant="normal">MeOH</mml:mi></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M51" 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="M52" display="inline"><mml:mrow><mml:mi>v</mml:mi><mml:mo>/</mml:mo><mml:mi>v</mml:mi></mml:mrow></mml:math></inline-formula>). The polar lipid fractions were
sent to Utrecht University for GDGT analysis. Sediment samples from Site
U1536E were processed for GDGT analysis by lipid extraction at Utrecht
University from 10 g of freeze-dried and manually powdered sediments using a
Milestone Ethos X microwave system and adding <inline-formula><mml:math id="M53" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">DCM</mml:mi><mml:mo>:</mml:mo><mml:mi mathvariant="normal">MeOH</mml:mi></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M54" 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="M55" display="inline"><mml:mrow><mml:mi>v</mml:mi><mml:mo>/</mml:mo><mml:mi>v</mml:mi></mml:mrow></mml:math></inline-formula>). The TLEs
were first filtered through a NaSO<inline-formula><mml:math id="M56" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> column to remove potential
remaining water and sediments. The TLEs were then separated on an activated
Al<inline-formula><mml:math id="M57" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O<inline-formula><mml:math id="M58" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> column into apolar, ketone and polar fractions using
<inline-formula><mml:math id="M59" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">hexane</mml:mi><mml:mo>:</mml:mo><mml:mi mathvariant="normal">DCM</mml:mi></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M60" 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="M61" display="inline"><mml:mrow><mml:mi>v</mml:mi><mml:mo>/</mml:mo><mml:mi>v</mml:mi></mml:mrow></mml:math></inline-formula>), <inline-formula><mml:math id="M62" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">hexane</mml:mi><mml:mo>:</mml:mo><mml:mi mathvariant="normal">DCM</mml:mi></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M63" 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="M64" display="inline"><mml:mrow><mml:mi>v</mml:mi><mml:mo>/</mml:mo><mml:mi>v</mml:mi></mml:mrow></mml:math></inline-formula>) and <inline-formula><mml:math id="M65" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">DCM</mml:mi><mml:mo>:</mml:mo><mml:mi mathvariant="normal">MeOH</mml:mi></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M66" 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="M67" display="inline"><mml:mrow><mml:mi>v</mml:mi><mml:mo>:</mml:mo><mml:mi>v</mml:mi></mml:mrow></mml:math></inline-formula>) as
eluents, respectively. All polar fractions were dried under N<inline-formula><mml:math id="M68" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>. A known
amount of C<inline-formula><mml:math id="M69" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">46</mml:mn></mml:msub></mml:math></inline-formula> glycerol trialkyl glycerol tetraether (GTGT) standard was added to the polar fractions from Sites
696 and U1536, which were subsequently dissolved in <inline-formula><mml:math id="M70" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">hexane</mml:mi><mml:mo>:</mml:mo><mml:mi mathvariant="normal">isopropanol</mml:mi></mml:mrow></mml:math></inline-formula>
(<inline-formula><mml:math id="M71" display="inline"><mml:mrow><mml:mn mathvariant="normal">99</mml:mn><mml:mo>:</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M72" display="inline"><mml:mrow><mml:mi>v</mml:mi><mml:mo>/</mml:mo><mml:mi>v</mml:mi></mml:mrow></mml:math></inline-formula>) to a concentration of <inline-formula><mml:math id="M73" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 2 mg mL<inline-formula><mml:math id="M74" 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
filtered through a 0.45 <inline-formula><mml:math id="M75" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi></mml:mrow></mml:math></inline-formula>m polytetrafluorethylene filter. After that,
the dissolved polar fractions were injected and analysed by ultra-high-performance liquid chromatography–mass spectrometry (UHPLC–MS) according to
the method described by Hopmans et al. (2016), using an Agilent 1260
Infinity UHPLC system coupled to an Agilent 6130 single-quadrupole mass
detector at Utrecht University. Selected ion monitoring (SIM) was used to
identify the GDGTs using their [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>+<?pagebreak page1936?></mml:mo></mml:msup></mml:math></inline-formula> ions and integrated using
ChemStation software. Samples with very low concentrations (i.e. peak area
<inline-formula><mml:math id="M78" display="inline"><mml:mrow><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">3000</mml:mn></mml:mrow></mml:math></inline-formula> mV s<inline-formula><mml:math id="M79" 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/or peak height <inline-formula><mml:math id="M80" display="inline"><mml:mrow><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">3</mml:mn><mml:mo>×</mml:mo></mml:mrow></mml:math></inline-formula> background
signal) of any of the GDGTs included in the TEX<inline-formula><mml:math id="M81" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula> were excluded from
analysis.</p>
      <p id="d1e1129">Although lipid extractions of Sites 696 and U1536 were performed at
different institutions, the latest interlaboratory comparison study (Francien Peterse, personal communication, 2023) that assessed the repeatability and
reproducibility of the TEX<inline-formula><mml:math id="M82" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula> indicates that differences in sediment
extraction and workup procedures do not affect isoGDGT distributions and
thus reconstructed SSTs. Instead, variations in reported TEX<inline-formula><mml:math id="M83" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula> values
appeared to be mainly introduced by the type of mass spectrometer used for
GDGT analysis (Schouten et al., 2013). Since the polar fractions from both
sites were analysed using the same HPLC–MS instrument at Utrecht University,
the uncertainty in our TEX<inline-formula><mml:math id="M84" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>-based SSTs mostly represents the
analytical uncertainty, which is <inline-formula><mml:math id="M85" display="inline"><mml:mrow><mml:mo>±</mml:mo><mml:mn mathvariant="normal">0.3</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M86" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C based on long-term
observation of the in-house standard.</p>
</sec>
<sec id="Ch1.S3.SS2">
  <label>3.2</label><?xmltex \opttitle{GDGT indices for non-thermal overprints on TEX${}_{{86}}$}?><title>GDGT indices for non-thermal overprints on TEX<inline-formula><mml:math id="M87" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula></title>
      <?pagebreak page1937?><p id="d1e1195">The TEX<inline-formula><mml:math id="M88" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula> SST proxy is based on the temperature dependence of the
number of cyclopentane rings in GDGT membrane lipids produced by marine
Thaumarchaeota and calculated as defined by Schouten et al. (2002):
            <disp-formula id="Ch1.E1" content-type="numbered"><label>1</label><mml:math id="M89" display="block"><mml:mrow><?xmltex \hack{\hbox\bgroup\fontsize{9.5}{9.5}\selectfont$\displaystyle}?><mml:mtable rowspacing="0.2ex" class="split" displaystyle="true" columnalign="right left"><mml:mtr><mml:mtd><mml:mrow><mml:msub><mml:mi mathvariant="normal">TEX</mml:mi><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:mrow></mml:mtd><mml:mtd><mml:mrow><mml:mo>=</mml:mo><mml:mo>(</mml:mo><mml:mo>[</mml:mo><mml:mtext>GDGT-2</mml:mtext><mml:mo>]</mml:mo><mml:mo>+</mml:mo><mml:mo>[</mml:mo><mml:mtext>GDGT-3</mml:mtext><mml:mo>]</mml:mo><mml:mo>+</mml:mo><mml:mo>[</mml:mo><mml:mtext>cren'</mml:mtext><mml:mo>]</mml:mo><mml:mo>)</mml:mo><mml:mo>/</mml:mo><mml:mo>(</mml:mo><mml:mo>[</mml:mo><mml:mtext>GDGT-1</mml:mtext><mml:mo>]</mml:mo></mml:mrow></mml:mtd></mml:mtr><mml:mtr><mml:mtd/><mml:mtd><mml:mrow><mml:mo>+</mml:mo><mml:mo>[</mml:mo><mml:mtext>GDGT-2</mml:mtext><mml:mo>]</mml:mo><mml:mo>+</mml:mo><mml:mo>[</mml:mo><mml:mtext>GDGT-3</mml:mtext><mml:mo>]</mml:mo><mml:mo>+</mml:mo><mml:mo>[</mml:mo><mml:mtext>cren'</mml:mtext><mml:mo>]</mml:mo><mml:mo>.</mml:mo></mml:mrow></mml:mtd></mml:mtr></mml:mtable><?xmltex \hack{$\egroup}?></mml:mrow></mml:math></disp-formula>
          The use of TEX<inline-formula><mml:math id="M90" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula> as a proxy for SST relies upon the assumption that
isoGDGTs in marine sediments are principally derived from membrane lipids of
marine pelagic Thaumarchaeota (Schouten et al., 2013). However, in some
environments, non-thermal factors may alter the distribution of isoGDGTs
stored in the sediment and thus the temperature signal (Supplement). We assess potential non-thermal effects on isoGDGT
distributions prior to translating TEX<inline-formula><mml:math id="M91" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula> into SSTs. We use the branched and isoprenoid tetraether (BIT) index to assess possible overprints of terrestrial GDGT input (Hopmans et al., 2004) and the fractional abundance of the crenarchaeol isomer over that of crenarchaeol to explore GDGT distribution in the sediment (fcren';
O'Brien et al., 2017), the methane index to identify contributions of methanotrophic archaea
(MI; Zhang et al., 2011), the GDGT-0<inline-formula><mml:math id="M92" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula>crenarchaeol ratio to identify contributions of methanogenic archaea (Blaga et al., 2009), the GDGT-2<inline-formula><mml:math id="M93" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula>GDGT-3 ratio to assess
contributions of a deep-dwelling GDGT-producing community (Taylor et al.,
2013), and the <inline-formula><mml:math id="M94" display="inline"><mml:mi mathvariant="normal">Δ</mml:mi></mml:math></inline-formula>ring index to identify GDGT distributions that
deviate from modern analogues (<inline-formula><mml:math id="M95" display="inline"><mml:mi mathvariant="normal">Δ</mml:mi></mml:math></inline-formula>RI; Zhang et al., 2016) (Fig. S1c,
panel 2–8; Fig. S2c, panel 2–8; Tables S3 and S4 in the Supplement).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F4" specific-use="star"><?xmltex \currentcnt{4}?><?xmltex \def\figurename{Figure}?><label>Figure 4</label><caption><p id="d1e1345"><bold>(a)</bold> TEX<inline-formula><mml:math id="M96" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>-SST data (BAYSPAR calibration; Tierney and Tingley,
2015). Data points marked by a triangle represent samples (<inline-formula><mml:math id="M97" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">9</mml:mn></mml:mrow></mml:math></inline-formula>) with a
potential non-thermal overprint on the GDGT distribution (outliers;
Supplement). <bold>(b)</bold> BIT index values (Hopmans et al., 2004)
plotted next to the lithology and age constraints of Site 696, which are
modified after Lopez-Quiros et al. (2021), based on Barker et al. (1988) and
Lopez-Quiros et al. (2019, 2020), including new constraints of the uppermost
interval (Core 50) from López-Quirós et al. (2018).</p></caption>
          <?xmltex \igopts{width=497.923228pt}?><graphic xlink:href="https://cp.copernicus.org/articles/19/1931/2023/cp-19-1931-2023-f04.png"/>

        </fig>

      <?xmltex \floatpos{t}?><fig id="Ch1.F5" specific-use="star"><?xmltex \currentcnt{5}?><?xmltex \def\figurename{Figure}?><label>Figure 5</label><caption><p id="d1e1383">Biomarker indices from Site U1536. Left panel shows core recovery,
estimated age and lithological composition (Weber et al., 2021a). The
crosses (X) indicate samples with GDGT concentrations below the detection
threshold. <bold>(a)</bold> TEX<inline-formula><mml:math id="M98" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>-SST (BAYSPAR calibration; Tierney and Tingley,
2015). Triangles mark samples with a potential non-thermal overprint on the
GDGT distribution (outliers; Supplement). <bold>(b)</bold> BIT index
(Hopmans et al., 2004) values.</p></caption>
          <?xmltex \igopts{width=398.338583pt}?><graphic xlink:href="https://cp.copernicus.org/articles/19/1931/2023/cp-19-1931-2023-f05.png"/>

        </fig>

</sec>
<sec id="Ch1.S3.SS3">
  <label>3.3</label><?xmltex \opttitle{TEX${}_{{86}}$ calibration}?><title>TEX<inline-formula><mml:math id="M99" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula> calibration</title>
      <p id="d1e1425">The empirical relationship between TEX<inline-formula><mml:math id="M100" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula> values and SST has appeared to
not always be straightforward, as reflected by continued revisions of the
approach of TEX<inline-formula><mml:math id="M101" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>-SST calibrations (Kim et al., 2010; Tierney and
Tingley, 2015; Ho and Laepple, 2016; O'Brien et al., 2017; Dunkley Jones et
al., 2020). Particularly, the relationship between TEX<inline-formula><mml:math id="M102" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula> and SST seems
to become obscured at both extreme ends of the core-top calibration: at or
above modern SSTs and in cold polar regions. However, for the time
intervals (late Eocene–early Oligocene and Middle–Late Miocene) and
locations we are targeting, we expect SSTs within the intermediate
temperature range. In this study, we used the regionally varying BAYSPAR SST
calibration of Tierney and Tingley (2015) to reconstruct SST (<inline-formula><mml:math id="M103" display="inline"><mml:mrow><mml:mo>±</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M104" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C standard calibration error) from TEX<inline-formula><mml:math id="M105" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula> values. BAYSPAR
compares measured TEX<inline-formula><mml:math id="M106" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula> values to modern TEX<inline-formula><mml:math id="M107" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula> values obtained
from surface sediments to derive linear regression parameters and
propagates uncertainties in the surface sediment data into resulting
temperature predictions (Tierney and Tingley, 2015). Even when GDGT-2<inline-formula><mml:math id="M108" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula>GDGT-3
ratios indicate that deeper-dwelling GDGT producers do not contribute to the
sedimentary signal, the GDGTs could still originate from the subsurface
(50–200 m water depth) rather than the sea surface (Schouten et al., 2013).
However, since the BAYSPAR calibration translates TEX<inline-formula><mml:math id="M109" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula> values to SSTs,
we refer to the proxy results as SSTs in the remainder of
this work. For all new and existing TEX<inline-formula><mml:math id="M110" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula> records discussed in this
study, we applied a standard deviation of <inline-formula><mml:math id="M111" display="inline"><mml:mrow><mml:mo>±</mml:mo><mml:mn mathvariant="normal">20</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M112" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C and a
prior mean of 20 <inline-formula><mml:math id="M113" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C for the late Eocene–early Oligocene interval
and 15 <inline-formula><mml:math id="M114" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C for the Miocene. We also compare the BAYSPAR-derived SST
estimates with those based on the exponential function (GDGT index-2) from
Kim et al. (2010) and the linear function by O'Brien et al. (2017). The SST
records all show similar trends, but BAYSPAR-derived SSTs are usually cooler
compared to those obtained from the functions of Kim et al. (2010) and
O'Brien et al. (2017) and can thus be considered conservative estimates
(Tables S3 and S4 and Figs. S3 and S4 in the Supplement).</p>
</sec>
</sec>
<sec id="Ch1.S4">
  <label>4</label><title>Results</title>
<sec id="Ch1.S4.SS1">
  <label>4.1</label><?xmltex \opttitle{Site 696 GDGT distributions and TEX${}_{{86}}$-SST trends}?><title>Site 696 GDGT distributions and TEX<inline-formula><mml:math id="M115" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>-SST trends</title>
      <p id="d1e1592">A total of 71 samples from ODP Site 696 were analysed for TEX<inline-formula><mml:math id="M116" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>
paleothermometry (Table S3 in the Supplement). The GDGT pool consists of <inline-formula><mml:math id="M117" display="inline"><mml:mrow><mml:mn mathvariant="normal">90</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">5</mml:mn></mml:mrow></mml:math></inline-formula> % isoGDGTs and <inline-formula><mml:math id="M118" display="inline"><mml:mrow><mml:mn mathvariant="normal">10</mml:mn><mml:mo>±</mml:mo></mml:mrow></mml:math></inline-formula>5 % branched GDGTs (brGDGTs), resulting in BIT index
values <inline-formula><mml:math id="M119" display="inline"><mml:mrow><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.2</mml:mn></mml:mrow></mml:math></inline-formula> (Fig. 5b). The isoGDGT distributions indicate that
GDGTs are primarily derived from surface-dwelling Thaumarchaeota
(Fig. S1 in the Supplement). In total, nine samples had higher <inline-formula><mml:math id="M120" display="inline"><mml:mi mathvariant="normal">Δ</mml:mi></mml:math></inline-formula>RI values than the cutoff of 0.3 (Fig. S1b), indicating a potential
non-thermal overprint on the GDGT distribution, and are excluded from SST
analysis (triangles in Fig. 4). The TEX<inline-formula><mml:math id="M121" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>-based SST record from Site
696 (607–521 m b.s.f., 36–33 Ma and <inline-formula><mml:math id="M122" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 16.5 Ma; Fig. 4) thus
consists of 62 data points and predominantly ranges between 12
and 18 <inline-formula><mml:math id="M123" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, although the total temperature range is from
4 to 25 <inline-formula><mml:math id="M124" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C (<inline-formula><mml:math id="M125" display="inline"><mml:mrow><mml:mo>±</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M126" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C standard
calibration error). There is a general cooling trend of <inline-formula><mml:math id="M127" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 8 <inline-formula><mml:math id="M128" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C between the upper Eocene and the lower Oligocene (from
20 to 12 <inline-formula><mml:math id="M129" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C between 610 and 558 m b.s.f.). This
is followed by an average <inline-formula><mml:math id="M130" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 5 <inline-formula><mml:math id="M131" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C increase in
temperature between <inline-formula><mml:math id="M132" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 558 and <inline-formula><mml:math id="M133" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 552 m b.s.f.. In the
organic-rich interval at <inline-formula><mml:math id="M134" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 555 m b.s.f. (Core 53R, 33.5–33.2 Ma), 35 sediment samples were analysed, with 1 sample every 3 cm (<inline-formula><mml:math id="M135" display="inline"><mml:mo lspace="0mm">∼</mml:mo></mml:math></inline-formula> 15 kyr resolution). In this interval, the high-resolution TEX<inline-formula><mml:math id="M136" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>-SST record shows high-amplitude variability (total
range of 4–21 <inline-formula><mml:math id="M137" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, with most data points falling within the range
of 8–17 <inline-formula><mml:math id="M138" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C). At <inline-formula><mml:math id="M139" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 550 m b.s.f. (lower Oligocene)
SSTs rapidly decrease to 10 <inline-formula><mml:math id="M140" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C. In the Middle Miocene
(<inline-formula><mml:math id="M141" display="inline"><mml:mo lspace="0mm">∼</mml:mo></mml:math></inline-formula> 520 m b.s.f., <inline-formula><mml:math id="M142" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:math></inline-formula>) SST values are <inline-formula><mml:math id="M143" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 14 <inline-formula><mml:math id="M144" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C.</p>
</sec>
<sec id="Ch1.S4.SS2">
  <label>4.2</label><?xmltex \opttitle{Site U1536 GDGT distributions and TEX${}_{{86}}$-SST trends}?><title>Site U1536 GDGT distributions and TEX<inline-formula><mml:math id="M145" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>-SST trends</title>
      <p id="d1e1865">A total of 40 sediment samples from IODP Hole U1536E were processed for GDGT
analysis (Table S4 in the Supplement), of which 14 had GDGT concentrations below
the detection limit (Fig. 5). The Site U1536 GDGT pool consists of variable
quantities of both isoGDGTs and brGDGTs, where brGDGTs are relatively more
abundant in the middle (500–560 m b.s.f.) and top parts of the record (450 m b.s.f.) (Fig. S2a), resulting in high BIT index values in these intervals of
the record (Fig. 5b). GDGT distributions in 12 sediment samples were outside
the range of what is considered reliable for multiple indicator proxies
(triangles in Figs. 5a and S2). For the
remaining 14 samples TEX<inline-formula><mml:math id="M146" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula> values were translated into SSTs using the
BAYSPAR calibration (Fig. 5a). The obtained record shows temperatures of
5–11 <inline-formula><mml:math id="M147" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C for the Middle Miocene (619–640 m b.s.f.) and
1.5–5 <inline-formula><mml:math id="M148" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C for the Upper Miocene (570–450 m b.s.f.).</p>
</sec>
</sec>
<sec id="Ch1.S5">
  <label>5</label><title>Discussion</title>
<sec id="Ch1.S5.SS1">
  <label>5.1</label><title>Late Eocene–early Oligocene South Atlantic SST conditions</title>
      <p id="d1e1911">We have compiled available South Atlantic SST records from Site 1090 (Liu et
al., 2009), Site 511 (Houben et al., 2019) and Seymour Island (Douglas et
al., 2014), in addition to our new SST record from Site 696 (Fig. 6), to put
the SST records into a broader regional context and discuss the surface
oceanographic development during the late Eocene–early Oligocene. Our SST
record from Site 696 (yellow in Fig. 6a) shows warm–temperate conditions
(SST range: 22–14 <inline-formula><mml:math id="M149" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C) during the latest Eocene (<inline-formula><mml:math id="M150" display="inline"><mml:mo lspace="0mm">∼</mml:mo></mml:math></inline-formula> 36.5–33.6 Ma) and on average decreasing SSTs (<inline-formula><mml:math id="M151" display="inline"><mml:mo lspace="0mm">∼</mml:mo></mml:math></inline-formula> 15–9 <inline-formula><mml:math id="M152" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C) in the earliest Oligocene (33.6–33.2 Ma). The cooling
of South Atlantic surface waters across the EOT is in broad agreement with the
average Southern Ocean-wide temperature drop (Kennedy-Asser et al., 2020;
Tibbett et al., 2023), the increase in benthic foraminifer <inline-formula><mml:math id="M153" 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
values as a result of deep-sea cooling, a drop in atmospheric <inline-formula><mml:math id="M154" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<inline-formula><mml:math id="M155" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>
levels (<uri>https://www.paleo-co2.org</uri>, last access: 1 August 2023; Pearson et al., 2009; Steinthorsdottir et
al., 2016; Hoenisch, 2021; Rae et al., 2021) and the growth of a
continent-wide Antarctic ice sheet across the EOT (e.g. Bohaty et al.,
2012). Sites 511 and 1090 also show a stepwise cooling across the EOT
(Hutchinson et al., 2021), where the first step occurs around 34.1 Ma and
coincides with common IRDs at Site 696, indicating the onset of
marine-terminating<?pagebreak page1939?> glaciers in the region (López-Quirós et al.,
2021), and the second step coincides with the earliest Oligocene oxygen
isotope step (EOIS, 33.65 Ma; Hutchinson et al., 2021). Miospores at Site 696, believed to be of local origin from the South Orkney Microcontinent, changed
concomitantly from southern beech, <italic>Nothofagus</italic>-dominated
vegetation to a more abundant gymnosperm and cryptogam vegetation, accompanied by a rapid rise in taxon diversity after the EOIS (<inline-formula><mml:math id="M156" display="inline"><mml:mo lspace="0mm">∼</mml:mo></mml:math></inline-formula> 33.65 Ma, 568.82 m b.s.f.; Thompson et
al., 2022). This shift in vegetation to a cooler and drier climate occurred
after the onset of the earliest glacial expansions (<inline-formula><mml:math id="M157" display="inline"><mml:mo lspace="0mm">∼</mml:mo></mml:math></inline-formula> 34.1 Ma).
Sedimentological investigations by López-Quirós et al. (2021) for
the same interval showed deepening of the South Orkney Microcontinent shelf
and enhancement of biological production, possibly due to upwelling along
the shelf, leading to low-oxygen conditions at the seafloor.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F6" specific-use="star"><?xmltex \currentcnt{6}?><?xmltex \def\figurename{Figure}?><label>Figure 6</label><caption><p id="d1e1996"><bold>(a)</bold> The upper panel shows biomarker-based SST trends from this
study (Site 696) compared with data from Site 1090 (Liu et al., 2009) and
Site 511 (Houben et al., 2019) and clumped-isotope-based SST from Seymour
Island (Douglas et al., 2014). The bars to the left indicate the standard
calibration error in the SST proxies. The arrows indicate the temperature
gradient between the TEX<inline-formula><mml:math id="M158" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>-SST records of Site 511 (green) and Site 696
(yellow). The lower record represents the global benthic foraminiferal
<inline-formula><mml:math id="M159" 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 compilation, smoothed by a locally weighted function over
20 kyr (black curve) (CENOGRID; Westerhold et al., 2020). The black curve is
the smoothed LOESS (span <inline-formula><mml:math id="M160" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 0.2). <bold>(b)</bold> Reconstructed paleogeographic map at
34 Ma, based on the GPlates reconstruction of van de Lagemaat et al. (2021)
in the paleomagnetic reference frame of Torsvik et al. (2012). All sites
from the data compilation in <bold>(a)</bold> are shown as stars. Arrows show the ocean
circulation derived from the general circulation model (GCM) by Goldner et al. (2014).</p></caption>
          <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://cp.copernicus.org/articles/19/1931/2023/cp-19-1931-2023-f06.png"/>

        </fig>

      <p id="d1e2040">The high-amplitude SST variability (<inline-formula><mml:math id="M161" display="inline"><mml:mo lspace="0mm">∼</mml:mo></mml:math></inline-formula> 4–8 <inline-formula><mml:math id="M162" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C) in
our TEX<inline-formula><mml:math id="M163" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>-SST record would suggest that this upwelling regime was
strongly variable. The variability in upwelling conditions could be induced
by strong fluctuating ice sheet expansion and retreat and shifts in wind
patterns and ocean frontal systems. Low-resolution palynological
investigations on late Eocene–early Oligocene sediments from the southern
South Atlantic (Houben et al., 2019; Hoem, 2022) show a highly
diverse and variable dinocyst assemblage, which includes indicative Antarctic-derived,
open-ocean, temperate and high-nutrient species, respectively,
and indeed infers a fluctuation in surface ocean conditions, potentially
related to shifts in frontal systems and upwelling regions. Alternatively,
the high variability in the TEX<inline-formula><mml:math id="M164" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula> signal could be introduced by the
input of reworked isoGDGTs. Such inputs were previously found to be high at
ice-proximal sites where the onset of large-scale Antarctic glaciation
across the EOT caused reworking of pre-Eocene deposits, such as, for example, Prydz
Bay (Tibbett et al., 2021). However, Tibbett et al. (2021) found that this
had little impact on the overall TEX<inline-formula><mml:math id="M165" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>-SST trend. Furthermore, we
record very low BIT index values (<inline-formula><mml:math id="M166" display="inline"><mml:mrow><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.2</mml:mn></mml:mrow></mml:math></inline-formula>; Table S3 in the Supplement, Fig. 4b) throughout the record, whereas Eocene sediments around Antarctica are
commonly high in brGDGTs (e.g. Bijl et al., 2013) because<?pagebreak page1940?> of the
well-developed soils on Antarctica at the time (Inglis et al., 2022). The
lack of brGDGTs in our record thus suggests little influence of reworked
Eocene GDGTs. We therefore assume that the TEX<inline-formula><mml:math id="M167" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula> record from Site 696
represents an in situ pelagic signal and that the variability in the SST
record is introduced by upwelling.</p>
      <p id="d1e2107">The clumped-isotope-based (<inline-formula><mml:math id="M168" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="normal">Δ</mml:mi><mml:mn mathvariant="normal">47</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>) SST data point from Seymour
Island (34 Ma; purple star in Fig. 6b) shows a similar temperature
(13 <inline-formula><mml:math id="M169" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C) to that derived from the TEX<inline-formula><mml:math id="M170" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula> proxy at the same site
(Douglas et al., 2014), as well as from nearby Site 696. The correspondence
of the biomarker-derived SSTs with that from <italic>Eurhomalea</italic> (bivalve) <inline-formula><mml:math id="M171" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="normal">Δ</mml:mi><mml:mn mathvariant="normal">47</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> (mean annual temperature) adds reliability to the temperature proxies
accurately reflecting SST in this region. Interestingly, the SSTs from
Seymour Island and Site 696 are very similar to Site 511, even though there
was a paleolatitudinal difference of <inline-formula><mml:math id="M172" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 12<inline-formula><mml:math id="M173" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> between
Site 511 and Seymour Island (Fig. 6). The subtropical Site 1090 is the
warmest site (<inline-formula><mml:math id="M174" display="inline"><mml:mo lspace="0mm">∼</mml:mo></mml:math></inline-formula> 19–27 <inline-formula><mml:math id="M175" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C) in our compilation, which
is expected given its lower paleolatitude. However, the absolute SSTs of
Sites 696 and 511 are strikingly similar across the EOT (Fig. 6a). The
south-western South Atlantic temperature gradient (between Sites 511 and 696)
decreased from <inline-formula><mml:math id="M176" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 1.8 <inline-formula><mml:math id="M177" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C in the late Eocene to
<inline-formula><mml:math id="M178" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 0 <inline-formula><mml:math id="M179" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C in the early Oligocene. A larger throughflow
through Drake Passage would increase the temperature gradient between Sites
696 and 511. Today both sites are separated by the strong ACC and an SST
gradient of <inline-formula><mml:math id="M180" display="inline"><mml:mrow><mml:mi mathvariant="italic">&gt;</mml:mi><mml:mn mathvariant="normal">7</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M181" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C (Locarnini et al., 2018). We
therefore imply that the throughflow changes induced by the opening of Drake
Passage did not change the South Atlantic Ocean circulation across the EOT.
Tectonic evidence suggests that the Drake Passage was narrow, with little
deep-water connection from the Pacific to the Atlantic around the EOT
(Livermore et al., 2007; Eagles and Jokat, 2014; van de Lagemaat et al.,
2021), which may explain the lack of regional oceanographic response. Model
experiments (Huber et al., 2004; Hill et al., 2013; England et al., 2017;
Sauermilch et al., 2021) show that a Southern Ocean without deep gateways
featured wind-driven clockwise gyres in the<?pagebreak page1941?> South Pacific and South
Indian Ocean/Atlantic Ocean basins (Fig. 6b) that would advect warm surface waters
toward the Antarctic coast. Specifically, eddy-resolving ocean model
simulations by Sauermilch et al. (2021) for the Eocene show that a
restricted (depths <inline-formula><mml:math id="M182" display="inline"><mml:mrow><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">600</mml:mn></mml:mrow></mml:math></inline-formula> m) Drake Passage throughflow would sustain
the subpolar gyre and lead to SSTs reaching 19 <inline-formula><mml:math id="M183" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C in the
Australian–Antarctic Basin and 15–17 <inline-formula><mml:math id="M184" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C in the subpolar Pacific
and Atlantic. This is very similar to our Site 696 TEX<inline-formula><mml:math id="M185" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>-SST EOT record
(<inline-formula><mml:math id="M186" display="inline"><mml:mo lspace="0mm">∼</mml:mo></mml:math></inline-formula> 11–18 <inline-formula><mml:math id="M187" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C). We thus propose that the small
differences in SSTs between Sites 511 and 696 are the result of a restricted
Drake Passage during the latest Eocene–earliest Oligocene, facilitating a
persistent wind-driven gyral circulation that connected the southern South
Atlantic sites in our compilation.</p>
</sec>
<sec id="Ch1.S5.SS2">
  <label>5.2</label><title>Middle to Late Miocene</title>
      <p id="d1e2300">To investigate the cooling step in the Middle to Late Miocene, the new
Miocene SST records from the Antarctic-proximal south-western South Atlantic
Sites 696 and U1536 are compared to records from the Antarctic Peninsula
(SHALDRILL II, Core 5D; Tibbett et al., 2022) and Wilkes Land (Site U1356;
Sangiorgi et al., 2018). However, there is still a lack of well-constrained
and overlapping records form the Southern Ocean Middle to Late Miocene due
to glacial expansions and erosion causing discontinuous records. Due to the
large age uncertainties and gaps in the sedimentary records of these
sites (Weber et al., 2021a; Pérez et al., 2021; Bohaty et al., 2011), we
present the TEX<inline-formula><mml:math id="M188" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>-derived SSTs as average temperatures within two broad
time intervals corresponding to the age uncertainty. We also compare SST
trends from the above-mentioned sites to those from the subantarctic zone:
ODP Site 1171 from the south-western Pacific Ocean (Leutert et al., 2020) and
Subtropical Front, ODP Site 1088 (Herbert et al., 2016) in the south-eastern
Atlantic, and Site ODP 1168 west of Tasmania (Hou et al., 2023). Further, we
compare our new Site U1536 SST record to clumped-isotope bottom-water
temperatures (BWTs) from South Indian Ocean ODP Site 747 (Leutert et al.,
2021) (Fig. 7).</p>

      <?xmltex \floatpos{p}?><fig id="Ch1.F7" specific-use="star"><?xmltex \currentcnt{7}?><?xmltex \def\figurename{Figure}?><label>Figure 7</label><caption><p id="d1e2314"><bold>(a)</bold> TEX<inline-formula><mml:math id="M189" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>-based SST data from Site 696 and U1536 (this study)
compared to Southern Ocean-wide SST and BWT records. The bars on the left
indicate the standard calibration error in the SST proxies. Data of Site
U1536 are displayed as two bar plots (red) showing the temperature ranges for
the Middle Miocene (16–14 Ma) and Late Miocene (7–5.3 Ma); individual data
points are shown as red dots. We compare our data to SST records from Wilkes
Land Site U1356 (Sangiorgi et al., 2018), SHALDRIL II Core 5D (Tibbett et
al., 2022; grey bars indicate the age uncertainty), Site 1168 (west of
Tasmania; Hou et al., 2023), Site 1171 (south-western Pacific Ocean; Leutert et
al., 2020), <inline-formula><mml:math id="M190" display="inline"><mml:mrow><mml:msubsup><mml:mi>U</mml:mi><mml:mn mathvariant="normal">37</mml:mn><mml:mrow><mml:msup><mml:mi>k</mml:mi><mml:mo>′</mml:mo></mml:msup></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>-SST data from Site 1088 (Herbert et al.,
2016) and clumped-isotope bottom-water temperature (BWT) data from Leutert
et al. (2021) (Site 747). The arrows indicate the temperature gradient
between the TEX<inline-formula><mml:math id="M191" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>-SST record from the south-western South Atlantic and the
Subtropical Front Site 1168. The black line is the benthic foraminiferal
<inline-formula><mml:math id="M192" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O compilation, smoothed by a locally weighted function over
20 kyr (thin blue curve) (CENOGRID; Westerhold et al., 2020). The thick black curve is the smoothed LOESS (span <inline-formula><mml:math id="M193" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 0.2). The stippled vertical line
indicates the age for the paleogeographic map below. <bold>(b)</bold> Paleogeographic
reconstruction at 16 Ma, based on the GPlates reconstruction of van de
Lagemaat et al. (2021) in the paleomagnetic reference frame of Torsvik et
al. (2012). All sites from data compilation in <bold>(a)</bold> are shown as stars. The dashed
black line represents the Miocene surface ocean currents derived from Herold
et al. (2012).</p></caption>
          <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://cp.copernicus.org/articles/19/1931/2023/cp-19-1931-2023-f07.png"/>

        </fig>

      <p id="d1e2385">The data compilation of South Atlantic SSTs (Fig. 7a) shows a 7 <inline-formula><mml:math id="M194" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C
cooling between Site 696 (yellow dots, <inline-formula><mml:math id="M195" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">14</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M196" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C standard calibration error, <inline-formula><mml:math id="M197" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:math></inline-formula>) during the Miocene Climatic
Optimum (MCO, <inline-formula><mml:math id="M198" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 16.5 Ma) and Site U1536 (red, <inline-formula><mml:math id="M199" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">7</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M200" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, <inline-formula><mml:math id="M201" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">5</mml:mn></mml:mrow></mml:math></inline-formula>) in the Middle Miocene Climate Transition
(MMCT, <inline-formula><mml:math id="M202" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 14.7–13.8 Ma). Both sites were located at comparable
paleolatitudes (albeit with a 2.5<inline-formula><mml:math id="M203" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> latitudinal difference; Fig. 8a)
during the Miocene (Fig. 7b). SSTs at Wilkes Land Site U1356 were warmer
(17 <inline-formula><mml:math id="M204" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C around 17 Ma) than at Site 696 (<inline-formula><mml:math id="M205" display="inline"><mml:mo lspace="0mm">∼</mml:mo></mml:math></inline-formula> 14 <inline-formula><mml:math id="M206" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C), even though Site U1356 was situated closer to the cooler
East Antarctic ice sheet. Additionally, a less pronounced cooling (SST
<inline-formula><mml:math id="M207" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 16–12 <inline-formula><mml:math id="M208" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C) occurred across the MMCT at Site U1356
(Sangiorgi et al., 2018) than the <inline-formula><mml:math id="M209" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 7 <inline-formula><mml:math id="M210" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C cooling
shown in the South Atlantic low-resolution dataset. Thus, the South Atlantic
sector was colder, with a likely more proximal ice mass at the onset of MMCT
than the Wilkes Land Antarctic margin. There was a <inline-formula><mml:math id="M211" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 6–10 <inline-formula><mml:math id="M212" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C temperature difference between the south-western South
Atlantic Antarctic-proximal Sites 696 and U1536 and the subantarctic Site 1171
(south-western Pacific Ocean), with Site 1171 clumped-isotope (<inline-formula><mml:math id="M213" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="normal">Δ</mml:mi><mml:mn mathvariant="normal">47</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>)
SSTs of 14–12 <inline-formula><mml:math id="M214" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C and TEX<inline-formula><mml:math id="M215" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula> SSTs of 18–13 <inline-formula><mml:math id="M216" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C
during MMCT (Leutert et al., 2020). This suggests a relatively strong SST
gradient between the coldest Antarctic-proximal regions and the subantarctic
zone in the Middle Miocene, even though the subantarctic zone was likely
situated at lower paleolatitudes in the Australian–Antarctic Gulf than in
the South Atlantic due to the more southerly position of Australia. The
increase in the temperature gradient in the complied SST records (Fig. 7a)
during the Middle Miocene indicates breakdown of the dominant gyral
circulation at the early Oligocene and a subsequent strengthening of the ACC
during the Middle–Late Miocene. The alkenone-based SST reconstructions for
Site 1088 and TEX<inline-formula><mml:math id="M217" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>-based SST reconstructions for Site 1168, together
representing Subtropical Front conditions, show MCO temperatures between
32–27 <inline-formula><mml:math id="M218" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C that progressively cooled during the MMCT
(<inline-formula><mml:math id="M219" display="inline"><mml:mo lspace="0mm">∼</mml:mo></mml:math></inline-formula> 24–14 <inline-formula><mml:math id="M220" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C) (Hou et al., 2023). This subtropical
cooling is weaker than at the Antarctic-proximal sites, which indicates that
the cooling was amplified at high latitudes. The clumped-isotope (<inline-formula><mml:math id="M221" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="normal">Δ</mml:mi><mml:mn mathvariant="normal">47</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>) BWT record from Site 747 in the South Indian Ocean (Leutert et
al., 2021) shows strikingly similar temperatures to the reconstructed SSTs
at Site U1536, which may suggest that the Weddell Gyre in the south-western
South Atlantic was an important region of deep-water formation in the
Miocene, like today (e.g. Orsi et al., 1999), which furthermore is in line
with what modelling studies suggest for the Miocene (e.g. Herold et al.,
2012). The 7 <inline-formula><mml:math id="M222" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C cooling of the south-western South Atlantic between
the MCO and MMCT occurs during a time of declining <inline-formula><mml:math id="M223" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<inline-formula><mml:math id="M224" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> (Foster et al.,
2012; Greenop et al., 2014) (Fig. 8d) and increasing benthic foraminiferal
<inline-formula><mml:math id="M225" 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 (Figs. 7a and 8c), reflecting an increasingly colder climate
with larger (in area) ice sheets on the Antarctic continent with oceanward
expansion (Lewis et al., 2008; Shevenell et al., 2008; Holbourn et al.,
2018; Levy et al., 2019; Leutert et al., 2020). Given estimates of
<inline-formula><mml:math id="M226" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<inline-formula><mml:math id="M227" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> decline (by 100–300 ppm; Sosdian et al., 2018; Super et al.,
2018), paleoclimate sensitivity (1.5–4.5 <inline-formula><mml:math id="M228" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C per <inline-formula><mml:math id="M229" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<inline-formula><mml:math id="M230" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>
doubling; Martínez-Botí et al., 2015) and polar amplification
factors (2–3; Holland and Bitz, 2003), the 7 <inline-formula><mml:math id="M231" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C cooling in the
south-western South Atlantic records (Sites 696 and U1536) could have been
completely induced by <inline-formula><mml:math id="M232" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<inline-formula><mml:math id="M233" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> decline in the Middle Miocene. This also
means that regional cooling was not amplified through strengthening of the
ACC and destruction of the subpolar gyre, which occurred later in the
Miocene (Evangelinos et al., 2022).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F8" specific-use="star"><?xmltex \currentcnt{8}?><?xmltex \def\figurename{Figure}?><label>Figure 8</label><caption><p id="d1e2757">South Atlantic SST compilation. <bold>(a)</bold> Paleolatitude evolution of sites
presented in this study (see legend; <uri>http://www.paleolatitude.org</uri>, last access: 1 February 2023; version 2
by van Hinsbergen et al., 2015). Stippled lines indicate hiatuses. <bold>(b)</bold> The
coloured points and lines indicate the biomarker-based SSTs (see legend),
excluding all samples with potential GDGT overprints (see Sect. 3.2). The
bars on the left indicate the standard calibration error in the SST proxies.
TEX<inline-formula><mml:math id="M234" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>-SST data from Site 696 (yellow; this study). TEX<inline-formula><mml:math id="M235" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>-SST data
from Site 1090 (dark pink; Liu et al., 2009). <inline-formula><mml:math id="M236" display="inline"><mml:mrow><mml:msubsup><mml:mi>U</mml:mi><mml:mn mathvariant="normal">37</mml:mn><mml:mrow><mml:msup><mml:mi>k</mml:mi><mml:mo>′</mml:mo></mml:msup></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>-SST and
TEX<inline-formula><mml:math id="M237" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>-SST from Site 511 (green; Houben et al., 2019).
<inline-formula><mml:math id="M238" display="inline"><mml:mrow><mml:msubsup><mml:mi>U</mml:mi><mml:mn mathvariant="normal">37</mml:mn><mml:mrow><mml:msup><mml:mi>k</mml:mi><mml:mo>′</mml:mo></mml:msup></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>-SST from 1088 (pink; Herbert et al., 2016).
TEX<inline-formula><mml:math id="M239" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">86</mml:mn></mml:msub></mml:math></inline-formula>-SST from Site U1536 (red; this study). Clumped-isotope (<inline-formula><mml:math id="M240" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="normal">Δ</mml:mi><mml:mn mathvariant="normal">47</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>) SST estimates from La Meseta Fm., Seymour Island (purple; Douglas
et al., 2014). <bold>(c)</bold> Benthic foraminiferal <inline-formula><mml:math id="M241" 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 compilation, with
a locally weighted smooth over 20 kyr (black curve) (CENOGRID; Westerhold et
al., 2020) and a LOESS smooth (black; span <inline-formula><mml:math id="M242" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 0.2). <bold>(d)</bold> Published
paleo-CO<inline-formula><mml:math id="M243" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> data from selected proxies named in the legend
(<uri>https://www.paleo-co2.org</uri>, last access: 1 August 2023), with LOESS smooth (red; span <inline-formula><mml:math id="M244" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 0.3).
LMC: Late Miocene Cooling; MCO: Miocene Climatic Optimum; EOIS: early
Oligocene oxygen isotope step; EOT: Eocene–Oligocene transition. The shaded grey areas indicate the time intervals discussed in Sect. 5.1 and 5.2
as indicated above the figure.</p></caption>
          <?xmltex \igopts{width=398.338583pt}?><graphic xlink:href="https://cp.copernicus.org/articles/19/1931/2023/cp-19-1931-2023-f08.png"/>

        </fig>

      <?pagebreak page1943?><p id="d1e2901">By the latest Miocene (<inline-formula><mml:math id="M245" display="inline"><mml:mo lspace="0mm">∼</mml:mo></mml:math></inline-formula> 6.4–5.2 Ma), temperatures at Site
U1536 cooled to an average SST of 3.4 <inline-formula><mml:math id="M246" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C (<inline-formula><mml:math id="M247" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">8</mml:mn></mml:mrow></mml:math></inline-formula>), which matches those
at SHALLDRILL II for the earliest Pliocene (5.1–4.3 Ma, average
2.8 <inline-formula><mml:math id="M248" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, <inline-formula><mml:math id="M249" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:math></inline-formula>). The 2–5 <inline-formula><mml:math id="M250" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C SST decrease at Site U1536
between the MMCT (<inline-formula><mml:math id="M251" display="inline"><mml:mo lspace="0mm">∼</mml:mo></mml:math></inline-formula> 14 Ma) and the latest Miocene
(<inline-formula><mml:math id="M252" display="inline"><mml:mo lspace="0mm">∼</mml:mo></mml:math></inline-formula> 6.4–5.2 Ma) is relatively small compared to the
<inline-formula><mml:math id="M253" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 10 <inline-formula><mml:math id="M254" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C cooling at the Subtropical Front Sites 1168
and 1088 at the same time. We surmise that high-latitude cooling was subdued
during this time interval because south-western South Atlantic surface waters
(Site U1536) were already cold (5–7 <inline-formula><mml:math id="M255" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C) at the end of the MMCT
(Fig. 7a) and thus could not cool as much as the subtropics. Instead, the
remaining warmer part of the Southern Ocean experienced pronounced cooling
during this time interval. Based on the Southern Ocean SST records (Fig. 7a), the south-western South Atlantic was already possibly the coldest region of the
Southern Ocean since at least the Middle Miocene. However, there is
a strong lack of Antarctic-proximal records (e.g. no records from the Ross
Sea; Levy et al., 2019) that cover the MMCT to Late Miocene, partly due to
glacial advances, to paint a full picture of circum-Antarctic cooling since
the MMCT.</p>
      <p id="d1e3002">Site U1536 SSTs and Site 747 BWTs were low during the MMCT (Leutert et al.,
2021), with minor cooling thereafter. Leutert et al. (2021) attributed the
subdued post-MMCT cooling to the growing Antarctic ice sheet, which could
have led to increased stratification and shielding of deeper waters in the
Southern Ocean. We conclude here that the<?pagebreak page1944?> south-western South Atlantic
regions already reached cold conditions during the MMCT because of the
proximity to ice sheets and, as a result, could not cool much more given
the global cold climate of the Late Miocene. The cooling of the subtropics
(Sites 1088 and 1168) is much more pronounced than the south-western South
Atlantic because of the gradual northward expansion of the westerly winds,
ACC and cold subantarctic waters (Leutert et al., 2020) in response to the
expansion of the Antarctic ice sheet in the Late Miocene. This process
likely also further promoted cooling in other sectors of the
Antarctic-proximal Southern Ocean.</p>
</sec>
<sec id="Ch1.S5.SS3">
  <label>5.3</label><title>South Atlantic SST gradient evolution</title>
      <p id="d1e3013">Compiling all available SST records for the two time slices discussed above
(Sect. 5.2 and 5.3) yields a unique insight into the long-term temperature
trends in the South Atlantic Ocean (Fig. 8). The SST records from the South
Atlantic region show unidirectional temperature drops across the EOT, with a
small degree of polar amplification where Antarctic-proximal records (Site 696 and
511) cooled by <inline-formula><mml:math id="M256" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 8 <inline-formula><mml:math id="M257" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C and subtropical records (Site
1090) cooled by <inline-formula><mml:math id="M258" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 5 <inline-formula><mml:math id="M259" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C. The strong, large and
persistent South Atlantic subpolar gyre kept the latitudinal SST gradient
low in the southernmost part of the South Atlantic across the EOT (Huber et
al., 2004; Houben et al., 2019). The latitudinal temperature gradient in the
South Atlantic increased during the MMCT (Figs. 7 and 8) due to the largest
cooling at high latitudes, almost reaching modern temperatures, followed by
a subdued cooling during the Late Miocene. Meanwhile the SSTs at the
Subtropical Front (Sites 1090 and 1088) remained relatively stable from the
earliest Oligocene (Site 1090, 33 Ma) until the Late Miocene (Site 1088)
(Fig. 8), with minimal cooling until the latest Miocene.</p>
      <p id="d1e3048">The cooling phases in the South Atlantic across the EOT and from the MCO to
the MMCT represent two climatic transitional phases, both characterised by
declining atmospheric <inline-formula><mml:math id="M260" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<inline-formula><mml:math id="M261" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> concentrations (Pearson et al., 2009; Foster
et al., 2012; Greenop et al., 2014; Steinthorsdottir et al., 2016) and
increasing benthic foraminiferal <inline-formula><mml:math id="M262" 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 values (Westerhold et
al., 2020), indicating deep-sea cooling and/or ice sheet expansion (Flower
and Kennett, 1993; Zachos et al., 1996) (Fig. 8). The EOT marks the first
installation of a continent-wide Antarctic ice sheet (Deconto and Pollard,
2003; Coxall et al., 2005), with a volume between 60 % and 130 % of that of
the present-day ice sheet (Bohaty et al., 2012). The MCO is considered to be a
global warm phase, with warm–temperate ice-proximal conditions (Sangiorgi et
al., 2018) and a profoundly reduced Antarctic ice volume (Shevenell et al.,
2008; Foster et al., 2012), and the MMCT is a strong and stepwise transition
towards a larger Antarctic ice sheet (Rohling et al., 2022). Surprisingly,
although south-western South Atlantic records (Sites 696 and U1536) are of
low resolution with notable age uncertainties, they do suggest similar
Antarctic-proximal SSTs (<inline-formula><mml:math id="M263" display="inline"><mml:mo lspace="0mm">∼</mml:mo></mml:math></inline-formula> 12–14 <inline-formula><mml:math id="M264" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C) for the early
Oligocene, when a large, predominately terrestrial ice sheet with marine-terminating glaciers was installed, to those for the MCO, when ice sheets were
profoundly reduced. Keeping in mind the higher-than-modern Antarctic
paleotopography in the Oligocene (Wilson and Luyendyk, 2009; Duncan et al., 2022),
with a gradual subsidence during the Miocene (Paxman et al., 2019), this
still puts both climate phases into perspective: apparently the Oligocene
Antarctic ice sheet could coexist with warm ice-proximal surface ocean
conditions, while the Middle Miocene Antarctic ice sheet could be strongly
reduced despite a relatively cold ice-proximal South Atlantic Ocean.</p>
</sec>
</sec>
<sec id="Ch1.S6" sec-type="conclusions">
  <label>6</label><title>Conclusions</title>
      <p id="d1e3103">Our lipid biomarker records from IODP Site U1536 and ODP Site 696 have
generated new insights for the understanding of the SST evolution of the
South Atlantic Ocean, as follows:
<list list-type="bullet"><list-item>
      <p id="d1e3108">The EOT in the South Atlantic is characterised by a relatively small
latitudinal SST gradient of <inline-formula><mml:math id="M265" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 5 <inline-formula><mml:math id="M266" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C between the
Subtropical Front and the western Weddell Sea and a regional decrease in SST
(4–6 <inline-formula><mml:math id="M267" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C) as global <inline-formula><mml:math id="M268" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<inline-formula><mml:math id="M269" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> declined.</p></list-item><list-item>
      <p id="d1e3153">The South Atlantic latitudinal SST gradient remains constant across the EOT,
which we ascribe to a gyral circulation that connects all South Atlantic
sites and can persist in the absence of a strong throughflow through Drake
Passage.</p></list-item><list-item>
      <p id="d1e3157">South-western South Atlantic SSTs at the earliest Oligocene glaciation were
similar to those of the warm MCO, implying that Antarctic-proximal SSTs are
not the only determining factor for the extent of the Antarctic ice sheet.</p></list-item><list-item>
      <p id="d1e3161">The south-western South Atlantic experienced cold polar climate conditions
(SSTs of <inline-formula><mml:math id="M270" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 5 <inline-formula><mml:math id="M271" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C) during the MMCT. This made it the
coldest oceanic region around Antarctica and the likely region of deep-water
formation.</p></list-item><list-item>
      <p id="d1e3181">Due to the already relatively cold conditions in the south-western South
Atlantic in the Middle Miocene, it experienced little further cooling during
the Late Miocene. This is in contrast to subtropical sites and other sectors
of the Southern Ocean which experienced profound cooling due to northward
expansion of the Southern Ocean frontal systems as the Antarctic ice sheet
expanded in the Late Miocene.</p></list-item></list></p>
</sec>

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

      <p id="d1e3188">The data are available for download from the Zenodo data archive at <ext-link xlink:href="https://doi.org/10.5281/zenodo.8279466" ext-link-type="DOI">10.5281/zenodo.8279466</ext-link> (Hoem et al., 2023).</p>
  </notes><app-group>
        <supplementary-material position="anchor"><p id="d1e3194">The supplement related to this article is available online at: <inline-supplementary-material xlink:href="https://doi.org/10.5194/cp-19-1931-2023-supplement" xlink:title="zip">https://doi.org/10.5194/cp-19-1931-2023-supplement</inline-supplementary-material>.</p></supplementary-material>
        </app-group><notes notes-type="authorcontribution"><title>Author contributions</title>

      <p id="d1e3203">FSH, PKB and FS designed the research. FSH, PKB, CE, ALQ and JE collected
the samples. ALQ and CE provided depositional information, core description,
facies analyses and age constraint for ODP Site 696. SvdL advised on the
Drake Passage tectonic evolution and provided (paleo)geographic maps for
Figs. 1, 6 and 7. JE, MAS and FSH processed samples for organic
geochemistry. FSH, PKB, FP and FS interpreted the data. FSH wrote the paper
with input from all authors.</p>
  </notes><notes notes-type="competinginterests"><title>Competing interests</title>

      <p id="d1e3209">The contact author has declared that none of the authors has any competing interests.</p>
  </notes><notes notes-type="disclaimer"><title>Disclaimer</title>

      <p id="d1e3215">Publisher’s note: Copernicus Publications remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.</p>
  </notes><ack><title>Acknowledgements</title><p id="d1e3222">This work used International Ocean Discovery Program (IODP) archived samples
and data. We thank the great scientists and crew on Expedition 382, who also
helped with data interpretation and discussions of results from Site U1536.
We thank Mariska Hoorweg for technical support at the Utrecht University
GeoLab. Frida S. Hoem and Peter K. Bijl acknowledge funding from the ERC starting grant 802835 “OceanNice”. Carlota Escutia and Adrián López-Quirós
acknowledge funding provided by the Spanish Ministry of Science and
Innovation (grants CTM2014-60451-C2-1/2-P and CTM2017-89711-C2-1/2-P,
co-funded by the European Union through FEDER funds) and JUAN DE LA CIERVA-TRAINING AID 2021 (FJC2021-047046-I, MCIN/AEI/10.13039/501100011033 and NextGenerationEU/PRTR). Suzanna van de Lagemaat
acknowledges funding by NWO Vici (grant no. 865.17.001) awarded to Douwe van Hinsbergen.</p></ack><notes notes-type="financialsupport"><title>Financial support</title>

      <p id="d1e3227">This research has been supported by the
Dutch Research Council (NWO) Polar Programme  (grant no. ALW.2016.001).</p>
  </notes><notes notes-type="reviewstatement"><title>Review statement</title>

      <p id="d1e3233">This paper was edited by Ran Feng and reviewed by Xiaoqing Liu and one anonymous referee.</p>
  </notes><ref-list>
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