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<article xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:oasis="http://docs.oasis-open.org/ns/oasis-exchange/table" xml:lang="en" dtd-version="3.0" article-type="research-article"><?xmltex \bartext{Research article}?>
  <front>
    <journal-meta><journal-id journal-id-type="publisher">BG</journal-id><journal-title-group>
    <journal-title>Biogeosciences</journal-title>
    <abbrev-journal-title abbrev-type="publisher">BG</abbrev-journal-title><abbrev-journal-title abbrev-type="nlm-ta">Biogeosciences</abbrev-journal-title>
  </journal-title-group><issn pub-type="epub">1726-4189</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/bg-20-597-2023</article-id><title-group><article-title>Nature and origin of variations in pelagic carbonate production in the
tropical ocean since the mid-Miocene (ODP Site 927)</article-title><alt-title>Nature and origin of variations in pelagic carbonate production</alt-title>
      </title-group><?xmltex \runningtitle{Nature and origin of variations in pelagic carbonate production}?><?xmltex \runningauthor{P.~Cornuault et al.}?>
      <contrib-group>
        <contrib contrib-type="author" corresp="yes" rid="aff1">
          <name><surname>Cornuault</surname><given-names>Pauline</given-names></name>
          <email>pcornuault@marum.de</email>
        <ext-link>https://orcid.org/0000-0002-6697-4735</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Westerhold</surname><given-names>Thomas</given-names></name>
          
        <ext-link>https://orcid.org/0000-0001-8151-4684</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Pälike</surname><given-names>Heiko</given-names></name>
          
        <ext-link>https://orcid.org/0000-0003-3386-0923</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Bickert</surname><given-names>Torsten</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-5221-5922</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2">
          <name><surname>Baumann</surname><given-names>Karl-Heinz</given-names></name>
          
        <ext-link>https://orcid.org/0000-0003-2109-5179</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Kucera</surname><given-names>Michal</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-7817-9018</ext-link></contrib>
        <aff id="aff1"><label>1</label><institution>MARUM – Centre for Marine Environmental
Sciences, University of Bremen,<?xmltex \hack{\break}?> Leobener Straße 8, 28359 Bremen, Germany</institution>
        </aff>
        <aff id="aff2"><label>2</label><institution>Geoscience Department, University of Bremen, Klagenfurter Straße,
P.O. Box 330440, 28359 Bremen, Germany</institution>
        </aff>
      </contrib-group>
      <author-notes><corresp id="corr1">Pauline Cornuault (pcornuault@marum.de)</corresp></author-notes><pub-date><day>6</day><month>February</month><year>2023</year></pub-date>
      
      <volume>20</volume>
      <issue>3</issue>
      <fpage>597</fpage><lpage>618</lpage>
      <history>
        <date date-type="received"><day>24</day><month>March</month><year>2022</year></date>
           <date date-type="rev-request"><day>2</day><month>May</month><year>2022</year></date>
           <date date-type="rev-recd"><day>9</day><month>November</month><year>2022</year></date>
           <date date-type="accepted"><day>18</day><month>December</month><year>2022</year></date>
      </history>
      <permissions>
        <copyright-statement>Copyright: © 2023 Pauline Cornuault et al.</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://bg.copernicus.org/articles/20/597/2023/bg-20-597-2023.html">This article is available from https://bg.copernicus.org/articles/20/597/2023/bg-20-597-2023.html</self-uri><self-uri xlink:href="https://bg.copernicus.org/articles/20/597/2023/bg-20-597-2023.pdf">The full text article is available as a PDF file from https://bg.copernicus.org/articles/20/597/2023/bg-20-597-2023.pdf</self-uri>
      <abstract><title>Abstract</title>

      <p id="d1e136">Marine plankton is an important component of the global carbon cycle.
Whereas the production and seafloor export of organic carbon produced by the
plankton, the biological pump, has received much attention, the long-term
variability in plankton calcification, controlling the carbonate counter
pump, remains less well understood. However, it has been shown that changes in pelagic calcification (biological
compensation) could affect the ocean's buffering capacity and thus regulate
global carbon budget on
geological timescales. Here we use Neogene pelagic sediments deposited on the
Ceara Rise in the tropical Atlantic to characterize the variability in
pelagic carbonate production with a focus on warm climates. A re-evaluation of
published records of carbonate accumulation at the Ceara Rise reveals a
systematic increase in sedimentation rates since the late Miocene, but the
carbonate accumulation rate does not show a clear trend. Instead, we observe
substantial orbital timescale variability in carbonate accumulation,
combined with a trend towards less carbonate on average at sites located
below 4 km, likely due to the effect of carbonate dissolution. To evaluate
long-term changes against possible orbital-scale variability, we generated
new high-resolution records of carbonate accumulation rate at Ocean Drilling Program (ODP) Site 927
across two Quaternary interglacials (MIS 5 and MIS 9), the Pliocene warm
period (MIS KM5) and the Miocene Climatic Optimum (MCO). We observe that the
highest carbonate accumulation rates occurred during the Pliocene but that
each of the studied intervals was characterized by large-magnitude orbital
variability. Prominent variations in carbonate accumulation prior to the
Quaternary preservation cycles appear to follow Earth obliquity and
eccentricity. These results imply that pelagic carbonate accumulation in the
tropical ocean, buffered from large temperature changes, varied on orbital
timescales. The magnitude of the orbital-scale variability was similar or
even higher than the long-term mean differences among the studied intervals.
Since preservation can be excluded as a driver of these changes prior to the
Quaternary, the observed variations must reflect changes in the export flux
of pelagic biogenic carbonate. We conclude that the overall carbonate
production by pelagic calcifiers responded to local changes in light,
temperature, and nutrients delivered by upwelling, which followed long
orbital cycles, as well as to long-term shifts in climate and/or ocean
chemistry. The inferred changes on both timescales were sufficiently large
such that when extrapolated on a global scale, they could have played a role
in the regulation of the carbon cycle and global climate evolution during
the transition from the Miocene warm climates into the Quaternary icehouse.</p>
  </abstract>
    </article-meta>
  </front>
<body>
      

<sec id="Ch1.S1" sec-type="intro">
  <label>1</label><title>Introduction</title>
      <p id="d1e148">The ocean plays a key role in the climate system as one of the major sinks
for anthropogenic atmospheric CO<inline-formula><mml:math id="M1" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> (Landschützer et al.,
2014). Most of the excess atmospheric carbon (CO<inline-formula><mml:math id="M2" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>) is absorbed by the
ocean as dissolved CO<inline-formula><mml:math id="M3" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>, which becomes part of the seawater carbonate
system and can be sequestered by the metabolic activity of marine organisms.
A large part of the carbon sequestration is due to carbon fixation into
organic matter by photosynthesis
(Henson et al.,<?pagebreak page598?> 2012;
Passow and Carlson, 2012; Sarmiento et al., 2004). However, next to the
sequestration of CO<inline-formula><mml:math id="M4" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> by photosynthesis and export via the biological
pump, marine organisms also participate in the global carbon cycle by
carbonate biomineralization. Milliman (1993) estimated that today's
marine carbonate production by organisms amounts to 5.3 GT yr<inline-formula><mml:math id="M5" 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>, of
which about a half is accounted for by pelagic calcifiers (2.4 GT yr<inline-formula><mml:math id="M6" 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>). Since aragonite and high-Mg calcite are unstable and largely
dissolve before deposition, the geologically relevant aspect of the pelagic
biogenic carbonate production is mediated mainly by low-Mg calcite that may
be variable but is mostly dominated by both planktic foraminifera and
coccolithophores (Boudreau et al., 2018). The carbonate
biomineralization, also termed the carbonate counter pump, leads in the short
term (kyr) to the release of CO<inline-formula><mml:math id="M7" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> from seawater because it consumes
alkalinity, but on long, geological timescales (Myr) it sequesters carbon
from the dissolved volatile ocean–atmosphere reservoir into the more inert
sedimentary reservoir. Manipulative experiments, ocean chemistry profiles,
and numerical models all indicate that pelagic carbonate production is
affected by a range of environmental parameters, such as temperature,
nutrient availability or <inline-formula><mml:math id="M8" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<inline-formula><mml:math id="M9" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> (Feely, 2004;
Gehlen et al., 2007). Therefore, a change in any of these parameters could
impact the pelagic carbonate production, resulting in a process that Boudreau
et al. (2018) termed biological compensation. In contrast to
chemical compensation, where changes in ocean carbonate chemistry are
compensated by dissolution of seafloor carbonate deposits, biological
compensation refers to changes in ocean carbonate chemistry due to globally
relevant shifts in carbonate biomineralization. For example, a decrease in
global oceanic biomineralization would lead to an increase of alkalinity,
which would cause an increase CO<inline-formula><mml:math id="M10" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> solubility and therefore lead to an
increased capacity of the ocean to take up CO<inline-formula><mml:math id="M11" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> (Boudreau
et al., 2018; Sarmiento and Gruber, 2006). Using a modelling approach,
Boudreau et al. (2018) showed that a global carbonate
productivity change by only 10 % would be sufficient for the process of
biological compensation to affect the marine carbon cycle on timescales
from years to millions of years.</p>
      <p id="d1e255">For the process of biological compensation to play an important role in the
global carbon cycle, it must be demonstrated that sufficiently large changes
in global carbonate biomineralization occurred in the geological past.
However, measuring changes in global biogenic carbonate production is
difficult because productivity and biomineralization vary in space, and
changes observed in individual records could be compensated by complementary
shifts elsewhere in the ocean
(Drury
et al., 2021). In most parts of the ocean, climate change causes plankton
assemblages to migrate, with biogeographic provinces expanding and
contracting in pace with orbital cycles
(Yasuhara et al., 2020). These processes should
result mainly in the spatial reorganization of pelagic carbonate production,
and as long as the forcing is cyclic, the effects should cancel out over
time.</p>
      <p id="d1e258">Beyond orbital timescales, understanding of changes in carbonate production
are complicated by the confounding effects of biological and chemical
compensation on carbonate content of deep-sea sediments
(Boudreau et al., 2018). Nevertheless, the few existing
continuous records indicate the presence of long-term shifts in carbonate
production by a factor of 2 or more manifested, for example, as the late
Miocene carbonate maximum
(Lyle
et al., 2019; Drury et al., 2021; Liebrand et al., 2016). Although there is
abundant evidence for local changes in pelagic calcification and carbonate
production, their spatial extent remains unknown, making it difficult to
judge whether the local shifts may have resulted in globally significant
biogeochemical response
(Lyle
et al., 2019; Drury et al., 2021).</p>
      <p id="d1e261">Here we have investigated pelagic carbonate accumulation, as a proxy for
production, in an equatorial location, where the plankton could not respond
to the climate cycles by migration and where long-term changes in
temperature, a key parameter likely affecting biomineralization, were
buffered compared to higher latitudes. Low-magnitude tropical sea surface temperature (SST)
variability in the Atlantic in the Pliocene and in the Miocene was reported
by Herbert et al. (2016) and Curry et al. (1995). Since orbitally driven environmental
change still affected the tropics, the Cenozoic tropical plankton represents
a natural experiment where the tropical calcifying community responded to a
number of orbital cycles and long-term changes in ocean chemistry,
reflecting changing atmospheric CO<inline-formula><mml:math id="M12" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>. Whilst these records cannot
provide a direct answer to how much pelagic carbonate production changed
globally, they can provide a first-order constraint on the amount of change
in pelagic calcification that could occur due to changes in the constitution
and/or abundance of the calcifiers on different timescales. We specifically
decided to target intervals with warmer global climate states, providing
potential analogues to gauge the amount of change in tropical pelagic
carbonate production under a global warming scenario (Fig. 2), and the
tropical Atlantic location allows us to complement records from the Pacific
and South Atlantic
(Lyle
et al., 2019; Drury et al., 2021; Pälike et al., 2006a) to assess the
spatial coherence of long term trends and the amount and nature of
short-term variability.</p>
      <p id="d1e274">Next to analysing long-term changes in carbonate accumulation, the existence
of persistent orbital variability implies that new data will be required,
characterizing the short-term response of the tropical pelagic carbonate
production system. To this end, in the present study the changes in
carbonate production through time have been studied in four intervals,
occurring during four warm periods of the late Cenozoic: the marine isotopic
stage (MIS) 5 (87.5 to 150.2 ka), the MIS 9 (276.4 to 370.3 ka), the MIS KM5
(3095.5 to 3307 ka) and the Miocene Climatic Optimum (MCO) (15 589.3 to
15 964.3 ka).</p>
      <p id="d1e277">This approach allows us to evaluate long-term changes in pelagic carbonate
production since the Mid-Miocene and at<?pagebreak page599?> the same time to characterize the
orbital-scale variability and determine if the orbital periodicity forcing
carbonate production changed from the Miocene to present.</p>
<sec id="Ch1.S1.SSx1" specific-use="unnumbered">
  <title>Time intervals</title>
      <p id="d1e285">The MIS 5, as the last warmest and longest interglacial of the past 500 ka
(Howard, 1997), with an abrupt glacial–interglacial transition
(Howard, 1997; Müller and Kukla,
2004; Sirocko et al., 2005) is considered to be a good analogue for the
actual warm Holocene (Howard, 1997; Kukla, 1997) and
even a partial analogue for <inline-formula><mml:math id="M13" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula>1–2 <inline-formula><mml:math id="M14" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C scenarios because of
polar temperatures 3 to 5 <inline-formula><mml:math id="M15" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C warmer than today and a sea level
about 6.6 m higher than today (Clark and Huybers, 2009; Kopp
et al., 2009). During this interglacial, Chalk et al. (2019) observed a change in
the current circulation in the Atlantic Ocean, with an enhanced Antarctic
Bottom Water (AABW) below 3400 m b.s.l. and well-ventilated, high-pH, and high
[CO<inline-formula><mml:math id="M16" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>] water mass around 2200 m b.s.l. They also highlighted a
correlation between the [CO<inline-formula><mml:math id="M17" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>] and the <inline-formula><mml:math id="M18" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<inline-formula><mml:math id="M19" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> in the West
Atlantic during cold intervals, with an increase of the volume of the high
dissolved inorganic carbon (DIC), low [CO<inline-formula><mml:math id="M20" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>] deep-water masses in
the North Atlantic.</p>
      <p id="d1e375">The MIS 9 in the equatorial Atlantic presents well-preserved sediment
at a period known to be under high obliquity with a unique insolation
signal. Stable oxygen isotope values are low during this period (low ice
volume). It is one of the interglacials showing the highest <inline-formula><mml:math id="M21" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<inline-formula><mml:math id="M22" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>
(around 300 ppm) and <inline-formula><mml:math id="M23" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CH<inline-formula><mml:math id="M24" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> (around 25 ppb) conditions in the late
Pleistocene. This period is also one of the warmest, stablest and shortest
interglacials, with a weak surface water ventilation
(Past
Interglacials Working Group of PAGES, 2016; Marino et al., 2014; Voelker et
al., 2010).</p>
      <p id="d1e410">The Pliocene warm period (PWP) MIS KM5 corresponds to a period with a
similar orbital forcing to present day and an insolation distribution close
to the modern one (Haywood et al.,
2013). This interval (3.264–3.025 ka) is also described as a negative
oxygen isotope slope and a sea level 21–23 m above the present-day one
(Lunt
et al.,  2008, 2010; Naish et al., 2009; Pollard and DeConto, 2009) with a
well-ventilated deep Atlantic Ocean
(Bell et al., 2015). The
temperature is 3 <inline-formula><mml:math id="M25" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C higher than pre-industrial values
(Haywood et al., 2000; Lunt et al., 2010) and the
CO<inline-formula><mml:math id="M26" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> concentration is close to the present value, i.e. 330–425 ppmv during the
warm interglacials (Pagani et al., 2010; Seki et
al., 2010), making it a good analogue for future climate (Ravelo
and Wara, 2004) and an important period to understand the climate system
(Lunt et al., 2010). Furthermore, this period is also
described as being wetter than today
(Leroy
and Dupont, 1994; Dodson and Macphail, 2004), but the latitudinal
distribution of the rainforest was close to the present day distribution
(Salzmann et al., 2011).</p>
      <p id="d1e431">The MCO corresponds to a period with an eccentricity-modulated precession
<inline-formula><mml:math id="M27" 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 signal and low global ice volume, featuring a Northern Hemisphere that is
free of continental ice sheets, important 100 and 400 kyr orbital
variability, and an Antarctic ice sheet that is smaller but more dynamic than today
(De
Vleeschouwer et al., 2017; Holbourn et al., 2007). Haq et al. (1987) highlighted the large sea level amplitude from 16
to 14 Ma, and the annual global temperature was 3 to 8 <inline-formula><mml:math id="M28" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C higher
than today (Pound et al., 2012;
You et al., 2009). The climate during the MCO is known to be correlated with
atmospheric CO<inline-formula><mml:math id="M29" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> concentration changes
(Foster et al., 2012), with CO<inline-formula><mml:math id="M30" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>
concentration being generally lower than at present
(Foster
et al., 2012; Ruddiman, 2010; Zachos et al., 2008; Zachos, 2001a, b) but
peaking at 16 Ma between 460 and 564 ppmv (Kürschner et
al., 2008). Even if a decline in <inline-formula><mml:math id="M31" 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 and <inline-formula><mml:math id="M32" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C at 16.9 Ma was
suspected to be linked to increase of carbonate dissolution, a sign of
strong changes in the carbon cycle
(Holbourn et al., 2015), carbonate
production appears to have been the main control of the CaCO<inline-formula><mml:math id="M33" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> record
(Liebrand
et al., 2016).</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="d1e507">Location of the material of this study at the Ceara Rise, ODP Leg 154
(Ocean Data View, Schlitzer, 2018).</p></caption>
          <?xmltex \igopts{width=503.61378pt}?><graphic xlink:href="https://bg.copernicus.org/articles/20/597/2023/bg-20-597-2023-f01.png"/>

        </fig>

</sec>
</sec>
<sec id="Ch1.S2">
  <label>2</label><title>Material and methods</title>
<sec id="Ch1.S2.SS1">
  <label>2.1</label><title>Site location</title>
      <p id="d1e532">Ceara Rise, located in the equatorial Atlantic Ocean, represents an ideal
location to quantify the variability in tropical Atlantic pelagic carbonate
production since the Miocene. This aseismic ridge rises several kilometres above the
surrounding abyssal plain, well above the modern regional lysocline, located
between 4100 and 4200 m b.s.l.
(Frenz
et al., 2006; Gröger et al., 2003a, b; Curry et al., 1995; Cullen and
Curry, 1997; Bickert et al., 1997). The ridge is bathed by the shallower
North Atlantic deep water (NADW) and the deeper Antarctic bottom water
(AABW)
(Rühlemann
et al., 2001; Gröger et al., 2003b; Herrford et al., 2017), and the
interface of the two water masses corresponds to the regional lysocline
depth. Around the ridge, the average depth of the seafloor is at 4500 m b.s.l.,
but the Ceara Rise ridge rises by as much as 1900 m above the surrounding
abyssal plain, with its top reaching the depth of 2600 m b.s.l.
(Curry et al., 1995). This provides an opportunity
to sample pelagic sediments that are largely unaffected by dissolution, and
their accumulation therefore mainly reflects changes in pelagic carbonate
production as suggested by Brummer and van Eijden (1992). The Ceara Rise (Fig. 1) has been
visited by Ocean Drilling Program (ODP) Leg 154
(Curry et al., 1995), recovering a transect of
sediment sequences ranging into the Eocene that are rich in carbonate and
show prominent cycles due to variable input of clastic material from the
Amazon fan
(Shackleton
et al., 1999; Bickert et al., 1997; Shackleton and Crowhurst, 1997). The
cycles are reflected in sediment physical properties, such as colour or
magnetic susceptibility, and because of the very good recovery and repeated
coring at the same sites, continuous spliced records could be produced that
facilitated the development of orbitally tuned age models
(Shackleton
et al., 1999; Zeeden et al., 2013; Wilkens<?pagebreak page600?> et al., 2017; Shackleton and
Crowhurst, 1997), a prerequisite for the quantification of carbonate
accumulation. Since all high-resolution Neogene records of carbonate
accumulation
(Drury
et al., 2021; Lyle et al., 2019), including those from the Ceara Rise
(Curry et al., 1995; King et
al., 1997) show a large orbital-scale variability, hinting at prominent
orbital-scale variability in pelagic carbonate production, next to a
compilation and re-evaluation of existing carbonate records, the selected
time slices had to be newly sampled and analysed at higher resolution.</p>
</sec>
<sec id="Ch1.S2.SS2">
  <label>2.2</label><title>Compilation of existing carbonate data from ODP Leg 154</title>
      <p id="d1e543">The combination of the availability of high-resolution age models and good
carbonate preservation make the Ceara Rise a model region to study pelagic
carbonate production and preservation. We compiled existing data on
carbonate content (CaCO<inline-formula><mml:math id="M34" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> %) at all the Leg 154 sites since the
Miocene
(Curry
et al., 1995; Frenz et al., 2006; King et al., 1997) and used those to
calculate carbonate accumulation rates (CaCO<inline-formula><mml:math id="M35" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR). The few other
existing datasets on carbonate content from the Ceara Rise sites (e.g.
Tiedemann and Franz, 1997) could not be used because some of
the information needed to calculate accumulation rates or the original
samples ID and depths was not available.</p>
      <p id="d1e564">The carbonate content data were combined with dry bulk density (DBD) and
sedimentation rate (SR) to calculate the CaCO<inline-formula><mml:math id="M36" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR as follows.
            <disp-formula id="Ch1.Ex1"><mml:math id="M37" display="block"><mml:mrow><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CaCO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow><mml:mi mathvariant="normal">AR</mml:mi><mml:mo>=</mml:mo><mml:mo>(</mml:mo><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CaCO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="normal">%</mml:mi></mml:mrow><mml:mo>/</mml:mo><mml:mn mathvariant="normal">100</mml:mn><mml:mo>)</mml:mo><mml:mo>×</mml:mo><mml:mi mathvariant="normal">DBD</mml:mi><mml:mo>×</mml:mo><mml:mi mathvariant="normal">SR</mml:mi></mml:mrow></mml:math></disp-formula>
          Following the approach by Lyle (2003), we first derived for each
site a calibration between the gamma ray attenuation (GRA) bulk density and
DBD using data from Curry et al. (1995). The
resulting site-specific calibrations (Fig. S1) were then applied on GRA bulk
density values, which were extracted from Curry et al. (1995), and interpolated to the position of the
analysed samples using linear interpolation. This yielded DBD values between
0.40   and 1.64 g cm<inline-formula><mml:math id="M38" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>. For two samples, the calibration
returned negative DBD (at 129.62 and 135.47 mcd) due to two anomalous
GRA values below 1. In these cases, we used the DBD of the nearest point
instead.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F2" specific-use="star"><?xmltex \currentcnt{2}?><?xmltex \def\figurename{Figure}?><label>Figure 2</label><caption><p id="d1e632">Oxygen stable isotopes (<inline-formula><mml:math id="M39" 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) shown as a smoothed record (Loess)
(Westerhold et al., 2020) and <inline-formula><mml:math id="M40" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<inline-formula><mml:math id="M41" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>
(Mejía
et al., 2017; Beerling and Royer, 2011; Stap et al., 2016; Raitzsch et al.,
2021; Foster et al., 2012; Petit et al., 1999) over the last 18 000 kyr and
sampled intervals (shadows).</p></caption>
          <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://bg.copernicus.org/articles/20/597/2023/bg-20-597-2023-f02.png"/>

        </fig>

</sec>
<?pagebreak page601?><sec id="Ch1.S2.SS3">
  <label>2.3</label><title>Context and sampling plan</title>
      <p id="d1e676">We sampled the record at Site 927 at high resolution for the four periods of
interest (Fig. 2), making sure that for each interval both the interglacial
and the flanking glacial in the Quaternary and at least two full
eccentricity cycles during the Pliocene and Miocene have been covered. These
four intervals cover a large range of global temperature and CO<inline-formula><mml:math id="M42" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>
values (Fig. 2). We selected Site 927 because it is one of the two shallow
sites of Leg 154, located well above the lysocline at present
(Frenz
et al., 2005; Curry et al., 1995; Bickert et al., 1997), and because
numerous palaeoceanographic datasets and carbonate measurements exist for
this site (e.g. Pälike
et al., 2006a; Bickert et al., 1997; Frenz et al., 2006; Gröger et al.,
2003b; King et al., 1997; Curry and Cullen, 1997). The site appears
generally less affected by slumps or turbidites than the four others, which
were not observed in the four studied intervals (sampled out of the slumps
and turbidites reported lithostratigraphic units)
(Curry et al., 1995). The sampling was guided by
the Wilkens et al. (2017) age model for
the samples from 0 to 14 Ma and by the Shackleton et al. (1999) age model for the
samples from 14 to 16.5 Ma. Considering the typical mixing depth of <inline-formula><mml:math id="M43" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>10 cm in deep-sea sediments, we sampled at 5 cm in the Quaternary and 10 cm in
the Neogene, which in both cases provides sub-orbital resolution. The
resolution was higher in the Quaternary because the peak interglacial
warmth periods are short (<inline-formula><mml:math id="M44" display="inline"><mml:mrow><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">10</mml:mn></mml:mrow></mml:math></inline-formula> kyr for MIS 5e;
Stolz and Baumann, 2010;
Müller and Kukla, 2004; Sirocko et al., 2005), and we wanted to cover
these using multiple samples. In total, we collected and analysed 139 samples
for the two Quaternary intervals, 72 samples for the Pliocene and 50 samples
for the Miocene.</p><?xmltex \hack{\newpage}?>
</sec>
<sec id="Ch1.S2.SS4">
  <label>2.4</label><title>Stable isotopes analyses</title>
      <p id="d1e714">We performed stable isotopes analyses (<inline-formula><mml:math id="M45" 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 and <inline-formula><mml:math id="M46" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C) at Bremen
University, using a Thermo Fisher Scientific MAT 253plus gas isotope ratio
mass spectrometer with Kiel IV automated carbonate preparation device. This
gives <inline-formula><mml:math id="M47" 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 with a standard deviation of house standard
(Solnhofen limestone) over a measurement period of 0.07 ‰
and <inline-formula><mml:math id="M48" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C values with standard deviation of house standard (Solnhofen
limestone) over measurement period of 0.03 ‰. The
sediment samples were washed and sieved at 63 <inline-formula><mml:math id="M49" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi></mml:mrow></mml:math></inline-formula>m using tap water and
dried overnight in the oven at 50 <inline-formula><mml:math id="M50" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C. Then, they have been
dry-sieved at 150 <inline-formula><mml:math id="M51" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi></mml:mrow></mml:math></inline-formula>m for benthic foraminifera picking. All the
Miocene samples have been picked, and only three samples did not have enough
material to run the stable isotopes analyses. For some of the samples we had
enough material to analyse two or three replicates using different species
known to be relevant markers for <inline-formula><mml:math id="M52" 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 seawater: <italic>Cibicidoides mundulus</italic>, <italic>Cibicidoides wuellerstorfi</italic> and <italic>Oridorsalis umbonatus</italic>
(Katz et al., 2003; Rathmann and
Kuhnert, 2008). We did not mix the species in one single measurement. For
the species-specific <inline-formula><mml:math id="M53" 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 and <inline-formula><mml:math id="M54" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C values correction, we used the
calibration given in the Supplement Table S3 from Westerhold et al. (2020).</p>
</sec>
<sec id="Ch1.S2.SS5">
  <label>2.5</label><title>Age model</title>
<sec id="Ch1.S2.SS5.SSS1">
  <label>2.5.1</label><title>For the existing data compilation</title>
      <p id="d1e846">Because the orbitally tuned age models as well as the splices for the
individual sites have been recently revised
(Wilkens et al., 2017), we re-evaluated
the composite depth of all samples<?pagebreak page602?> and assigned new ages to them based on
Wilkens et al. (2017) and used the new
ages to derive sedimentation rates (SR).</p>
</sec>
<sec id="Ch1.S2.SS5.SSS2">
  <label>2.5.2</label><title>For the four high-resolution intervals of core 927</title>
      <p id="d1e857">The existing most recent age model for Site 927 is based on a directly tuned
age model from Site 926 that has been point-to-point correlated with the
composite record from Site 927 using core images, magnetic susceptibility,
greyscale values and stable isotopes
(Wilkens et al.,
2017; Zeeden et al., 2013). For the determination of CaCO<inline-formula><mml:math id="M55" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR during
the four target intervals, this age model requires adjustments because it
provides too low resolution and is not tuned below core 927A-30H, section
6, 70 cm (303.60 rmcd), corresponding to 926A-28H, section 3, 18 cm (277.82 rmcd). Thus, to estimate CaCO<inline-formula><mml:math id="M56" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR for the three studied intervals, we
developed modified age models, where SRs have been constrained directly by
astronomical tuning of sediment properties in the studied cores.</p>
</sec>
</sec>
<sec id="Ch1.S2.SS6">
  <label>2.6</label><title>Carbonate analyses</title>
      <p id="d1e887">To determine the CaCO<inline-formula><mml:math id="M57" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR for the newly sampled intervals, we performed
carbonate content analyses on the bulk sediment using a LECO CS744 elemental
analyser at Bremen University. The analysis was performed by heating 0.1 g
of homogenized material in a ceramic dish and measuring the resulting
CO<inline-formula><mml:math id="M58" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> in IR cells. The carbonate content has been calculated as the
difference between the total carbon content and the organic carbon content,
measured in a second sample that was pre-treated with hydrochloric acid to
remove carbonates. Both measurements have an accuracy of 0.001 mg (1 ppm) or
0.5 % relative standard deviation (RSD). The inorganic carbon was then
converted to carbonate content using the molecular mass of calcium
carbonate. Dry bulk density for all the newly analysed samples at Site 927
was determined from GRA bulk density as described above (Sect. 2.2.) and
combined with the carbonate content and SR from the modified age models to
calculate the CaCO<inline-formula><mml:math id="M59" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR.</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="d1e919"><bold>(a)</bold> Box plots of the CaCO<inline-formula><mml:math id="M60" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR for the five cores and <bold>(b)</bold>
CaCO<inline-formula><mml:math id="M61" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR and SR (grey line) through the time for the Sites 925, 926,
927, 928, and 929 (black line and dots) for the five cores of the Leg 154.
The CaCO<inline-formula><mml:math id="M62" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR are calculated from existing carbonate content data for
all Leg 154 sites
(Curry
et al., 1995; Frenz et al., 2006; King et al., 1997). The colour shade
corresponds to the values of CaCO<inline-formula><mml:math id="M63" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR.</p></caption>
          <?xmltex \igopts{width=369.885827pt}?><graphic xlink:href="https://bg.copernicus.org/articles/20/597/2023/bg-20-597-2023-f03.png"/>

        </fig>

</sec>
</sec>
<sec id="Ch1.S3">
  <label>3</label><title>Results</title>
<sec id="Ch1.S3.SS1">
  <label>3.1</label><title>Long-term trends in carbonate accumulation rates</title>
      <p id="d1e985">Using existing carbonate content data for all Leg 154 sites
(Curry
et al., 1995; Frenz et al., 2006; King et al., 1997), combined with new age
models (Wilkens et al., 2017), for each
site, records of CaCO<inline-formula><mml:math id="M64" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR since the mid-Miocene were calculated (Fig. 3). Curry et al. (1995) noted the occasional
presence of slumps or hiatuses in the sediment sequences, especially at Site
928 and Site 929. Here we used the age models for the entire sediment
package, ignoring the presence of these events. This is because the slumps
only represent a small fraction of the sediment sequence and therefore are
unlikely to affect the overall trends.</p>
      <p id="d1e997"><?xmltex \hack{\newpage}?>The mean CaCO<inline-formula><mml:math id="M65" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR varies considerably among the sites, reflecting their
depth and therefore likely the amount of dissolution. ODP Sites 925 and 927
(present depth 3041  and 3315 m b.s.l.) show consistently higher CaCO<inline-formula><mml:math id="M66" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>
AR (between 1.5 and 3 g cm<inline-formula><mml:math id="M67" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> ka<inline-formula><mml:math id="M68" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> than the three remaining sites,
located below 3400 m b.s.l. (around 1 g cm<inline-formula><mml:math id="M69" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> kyr<inline-formula><mml:math id="M70" 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>). Curry and Cullen (1997) show an effect of distance from
the Amazon Fan on sediment composition on Ceara Rise for the late Quaternary, but this change is
only manifested as differences in the AR of terrigenous (non-carbonate)
sediments. This is seen in patterns of carbonate content of the sediment
(their Fig. 2) but not in changes in carbonate accumulation. Also, there
is little evidence that the Amazon discharge plume reaches far enough
offshore to induce changes in productivity over the plateau. At present, the
discharge is strongly deflected northwards and stimulates productivity
mainly along a narrow coastal strip (Gouveia et
al., 2019). The same authors note that some of the Amazon discharge may be
deflected into the North Brazil Current, but this affects productivity only
little and mainly north off the Ceara Rise. To visualize long-term trends,
we subtracted at each site the mean values of CaCO<inline-formula><mml:math id="M71" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR and SR (Fig. 4).
All sites show a prominent trend of increasing SR, beginning in the late
Miocene (8 Ma ago) (Fig. 4), which is known to reflect increasing amount of
clastic material transported from the Amazon Fan
(Curry
et al., 1995; Pälike et al., 2006b; Bickert et al., 1997; Harris et al.,
1997; Shackleton and Crowhurst, 1997). The CaCO<inline-formula><mml:math id="M72" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR, on the contrary,
shows a less obvious temporal trend on a long timescale (Fig. 4),
indicating that the increase in SR is compensated by decreased carbonate
content in the sediment. Instead, the CaCO<inline-formula><mml:math id="M73" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR record at all Ceara Rise
sites show a pervasive short-term (likely orbital) variability, with
substantial magnitude (Curry et al., 1995).</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="d1e1100"><bold>(a)</bold> SR from which the average SR has been subtracted and <bold>(b)</bold>
CaCO<inline-formula><mml:math id="M74" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR from which the average CaCO<inline-formula><mml:math id="M75" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR has been subtracted, both
for the five sites of Leg 154 over the last 16 Ma.</p></caption>
          <?xmltex \igopts{width=369.885827pt}?><graphic xlink:href="https://bg.copernicus.org/articles/20/597/2023/bg-20-597-2023-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="d1e1135">Depth–age correlation for the late Pleistocene, cores 927A 1H,
927B 2H and 927A 2H (following the splice) with <bold>(a)</bold> the Lisiecki and
Raymo (2005) <inline-formula><mml:math id="M76" 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 stack; <bold>(b)</bold> the local <inline-formula><mml:math id="M77" 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 record
(Wilkens et al., 2017, modified from
Bickert et al., 2004); <bold>(c)</bold> the age–depth record with control
points; <bold>(d)</bold> the SR from Wilkens et al. (2017) (green), the SR using the LRO4
depths and ages for site 927 (blue-green), and the SR defined in this study
(blue); and <bold>(e)</bold> the core images (Wilkens et al., 2017) and grey value record for
the three cores of the splice used, the position of the switch from one
core to the other in the splice (dashed lines), and the position of the
samples used in the present study in the cores (light blue triangles).</p></caption>
          <?xmltex \igopts{width=369.885827pt}?><graphic xlink:href="https://bg.copernicus.org/articles/20/597/2023/bg-20-597-2023-f05.png"/>

        </fig>

</sec>
<sec id="Ch1.S3.SS2">
  <label>3.2</label><title>Age models for target intervals at ODP Site 927</title>
<sec id="Ch1.S3.SS2.SSS1">
  <label>3.2.1</label><title>Pleistocene</title>
      <p id="d1e1197">The Pleistocene interval in the studied core has a high-resolution age model
based on benthic oxygen isotope data (Bickert et al., 2004)
that were incorporated in the benthic stack of Lisiecki and Raymo (2005), who had added a constant 4–5 kyr lag to take into account the
delay in the <inline-formula><mml:math id="M78" 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 data (ice volume inertia) with respect to the
insolation forcing (Lisiecki and Raymo, 2005). However, Wilkens et
al. (2017) revised the splice for this
site (the way individual core segments are aligned), which means the age
model in Lisiecki and Raymo (2005) has to be validated. To this end, we
first checked the new alignment of the individual cores by generating
high-resolution sediment colour (grey value) curves from the core images
presented by Wilkens et al. (2017) (Fig. 5e). The grey value curve was
extracted using the ImageJ software and calculated from RGB images using the
NTSC formula (Rasband, 1997) with values averaged across the entire
core width perpendicular to the<?pagebreak page603?> core axis and the resulting noisy curve was
smoothed as first component of the singular spectrum analysis (SSA) obtained
with Analyseries software (Paillard et al., 1996). This curve
was used to compare the overlapping parts of the cores spanning the last 400 ka, validating the alignment by Wilkens et al. (2017), which we thus adopt
without modification. For the age model, we carried out a manual tuning of
the 927 <inline-formula><mml:math id="M79" 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 data (Bickert et al., 2004) using the new composite depth
by Wilkens et al. (2017) to the LR04 stack (Lisiecki and Raymo, 2005).
Because the benthic stable oxygen record reflects mainly global sea level
change (Bickert et al., 2004), the tuning was based on the identification of
all unambiguously recognizable <inline-formula><mml:math id="M80" 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 maxima and times of fastest
sea level change (Fig. 5a). By the fastest sea level change (coinciding with
the fastest ice volume change), we mean the inflection points of the <inline-formula><mml:math id="M81" 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
curve (327.55 mcd to 15 605 ka and 331.5 mcd to 15 930 ka). The resulting SRs
are indeed more similar to those inferred from the age model by Wilkens et
al. (2017) than those implied by the age model for the site as implemented
in the LR04 stack (Lisiecki and Raymo, 2005).</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="d1e1246">Depth–age correlation for the Pliocene interval across cores 154
927C 11H, 154 927A 12H and 154 927B 13H. <bold>(a)</bold> The daily insolation for 21 June at 65<inline-formula><mml:math id="M82" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> N record
(Laskar et al., 2004). <bold>(b)</bold> The MS
record (black) and MS smoothed record (grey) according to the splice
presented in this study. <bold>(c)</bold> The age–depth record with control points. <bold>(d)</bold>
The SR from the Wilkens et al. (2017) age model (green) and from this study
(blue). <bold>(e)</bold> The core images for the cores of the splice are from Wilkens et al. (2017) (pictures), also shown are the grey value record extracted from it (black lines), a step from one core to the other in the splice (dashed lines), and the position of the samples used in this study in the cores (light blue triangles).  <bold>(f)</bold> MS record for the individual cores (Curry et al., 1995;
Wilkens et al., 2017) and steps from one core to the other in the splice
(dashed lines).</p></caption>
            <?xmltex \igopts{width=369.885827pt}?><graphic xlink:href="https://bg.copernicus.org/articles/20/597/2023/bg-20-597-2023-f06.png"/>

          </fig>

</sec>
<sec id="Ch1.S3.SS2.SSS2">
  <label>3.2.2</label><title>Pliocene</title>
      <p id="d1e1291">For the Pliocene interval, the first step has been to validate the core
alignment. First, we generated a grey value curve (Sect. 3.2.1) but noted
that this signal is weaker and shows many idiosyncratic features among the
overlapping parts of the cores from the individual holes. Therefore, we
decided to carry out the tuning on the magnetic susceptibility (MS) signal
as done by Shackleton et al. (1999), which was also measured
in all cores (Curry et al., 1995). MS shows a distinct signal in this part
of the sediment sequence, which can be<?pagebreak page604?> used for tuning (like it has been
used at Site 926), but for this it must be in alignment across the
individual core segments. The alignment revealed that the existing splice by
Wilkens et al. (2017) has to be adjusted for the purpose of tuning in this
interval (Fig. S2) by a shift of the core 927C 11H by 2 cm shallower, a
shift of the core A 12H by 15 cm deeper and a shift of the core B 13H  9 cm deeper in the splice compared to the spliced MS record of Wilkens et al. (2017). Otherwise, the construction of the spliced record remained the same,
retaining the same depths where the signal from one core switches to a
signal from the adjacent core. These depths are indicated by dashed lines
across the overlapping sections of the cores (Fig. 6d). The spliced MS
signal (Fig. 6b) has then been tuned to the daily insolation on 21 June
at 65<inline-formula><mml:math id="M83" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> N. This is because this representation of orbital forcing
of global climate shows the best pattern of influence from both obliquity
and precession (Laskar et al., 2004) (Fig. 6a) and has been used for tuning
at the studied location in previous studies (e.g.
Zeeden et al., 2013), who also provide arguments
for why the MS and insolation are co-varying without lag. The tuning of the
MS signal to an orbital target is possible because the existing age model of
Wilkens et al. (2017) is sufficiently precise to provide a specific tuning
target age interval, as confirmed by similar modulation of the insolation
target and of the spliced MS record. The tuning has been done by correlating
recognizable 23 MS minima to insolation maxima for this interval, using the
Analyseries software (Paillard et al., 1996), assuming the
signals are in antiphase without lag
(Wilkens
et al., 2017; Zeeden et al., 2013, 2015). As MS minima are easier to
identify than the MS maxima, we prefer here to work with MS minima and
insolation maxima instead of MS maxima and insolation minima as in Zeeden et
al. (2013).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F7" specific-use="star"><?xmltex \currentcnt{7}?><?xmltex \def\figurename{Figure}?><label>Figure 7</label><caption><p id="d1e1305">Depth–age correlation for the Mid-Miocene, core 154 927 A33H. <bold>(a)</bold> The
<inline-formula><mml:math id="M84" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C loess smooth composite record (from sites U1337 and U1338,
Westerhold et al., 2020) and corrected <inline-formula><mml:math id="M85" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C measured in Miocene samples
from this study (<italic>O.umbonatus</italic> in pink, <italic>C. mundulus</italic> in green, and <italic>C. wuellerstorfi</italic> in blue; the line corresponds to
the average value). <bold>(b)</bold> The <inline-formula><mml:math id="M86" 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 loess smoothed composite record (from sites
U1337 and U1338, Westerhold et al., 2020) and corrected <inline-formula><mml:math id="M87" 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 measured
in Miocene samples from this study (<italic>O.umbonatus</italic> in pink, <italic>C. mundulus</italic> in green, and <italic>C. wuellerstorfi</italic> in blue; the
line corresponds to the average value). <bold>(c)</bold> The obliquity (grey) and <inline-formula><mml:math id="M88" display="inline"><mml:mrow><mml:mi>E</mml:mi><mml:mo>+</mml:mo><mml:mi>T</mml:mi><mml:mo>-</mml:mo><mml:mi>P</mml:mi></mml:mrow></mml:math></inline-formula>
(black) records (Laskar et al., 2004). <bold>(d)</bold> The SSA of the grey value record
extracted from the core image and corrected from the light bias. <bold>(e)</bold> The age–depth relationship
and control points. <bold>(f)</bold> SR from the Shackleton et al. (1999) age model (green),
from nannofossil events
(Curry
et al., 1995; Pälike et al., 2010; Wilkens et al., 2017) (dark blue) and
from this study (blue). <bold>(g)</bold> The corrected <inline-formula><mml:math id="M89" 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 measured on Miocene samples
from this study against depth (<italic>O.umbonatus</italic> in pink, <italic>C. mundulus</italic> in green and <italic>C. wuellerstorfi</italic> in blue; the line
corresponds to the average value). <bold>(h)</bold> The core image (Wilkens et al., 2017),
smoothed grey value record and position of the samples for this study in the
core (light blue triangles).</p></caption>
            <?xmltex \igopts{width=369.885827pt}?><graphic xlink:href="https://bg.copernicus.org/articles/20/597/2023/bg-20-597-2023-f07.png"/>

          </fig>

</sec>
<sec id="Ch1.S3.SS2.SSS3">
  <label>3.2.3</label><title>Miocene</title>
      <p id="d1e1447">The existing age model for the Miocene interval by Shackleton et al. (1999)
is based on a combination of orbital tuning and biostratigraphy. It presents
a distinct shift in the SR around 330 mcd (Fig. 7c), dominating the
CaCO<inline-formula><mml:math id="M90" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR record for the studied period. There does not seem to be any
distinct shift in the physical properties at that depth (Curry et al.,
1995), and we therefore felt compelled to test the possibility that the
singular change in SR does not correctly represent the changes in the
sedimentation at this site. Since the studied interval is within one core
segment, we tested whether a “nested” tuned age model can be developed,
allowing a more precise estimation of the variability in the SR. As in this
part of the sediment sequence the MS was not the dominant signal, we have
made the choice to work with both the sediment colour and the stable
isotopes to have two independent markers for this age model (analyses run
for the purpose of this study; see Sects. 3.2.1. and 2.4.).</p>
      <?pagebreak page605?><p id="d1e1459">To have an independent estimation of the SR, we also evaluated the
biostratigraphy from the shipboard data (Curry et al., 1995) with revised metre composite depth
(Wilkens et al., 2017) and revised biomarker ages GTS 2020
(Raffi et al., 2020). Three biostratigraphic
markers have been evaluated: last appearance datum (LAD) of <italic>Sphenolithus heteromorphus</italic>, LAD
<italic>Helicosphaera ampliaperta </italic> and LAD abundant <italic>Discoaster deflandrei</italic>. The combination of these markers gives us two SR options.
Using LAD <italic>H. ampliaperta</italic> (the less reliable marker according to Raffi et al., 2020), in
combination with LAD <italic>D. deflandrei</italic>, gives an SR of 1.65 cm kyr<inline-formula><mml:math id="M91" 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>. Alternatively,
considering LAD <italic>S. heteromorphus</italic>, which is recorded in the core further from the studied
interval but is considered more reliable according to Raffi et al. (2020),
in combination with LAD <italic>D. deflandrei</italic>, gives an SR of 1.11 cm kyr<inline-formula><mml:math id="M92" 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>.</p>
      <?pagebreak page607?><p id="d1e1508">A sediment colour proxy was generated for the studied core (Sect. 3.2.1)
(Fig. 7d). Due to the light appearance of the sediment composing this core
and the way the pictures have been taken onboard (1.5 m sections with a centred camera and centred white source of
light), there is a strong 1.5 m induced light cyclicity in the original
light images (Curry et al., 1995; Wilkens et al., 2017). To reduce this
bias, the core images were adjusted for the edge effect using the lighting
correction function inside the Code for Ocean Drilling Data (CODD, Wilkens
et al., 2017) (Fig. 7d). For the identification of the cyclicity in the
core, we carried out spectral analyses on the corrected grey value curve
using the multitaper method (MTM) (carried out using astrochron package on
R, Meyers, 2014; R 4.1.2., R Core Team, 2021)
(Fig. S6). This revealed three broad but distinct peaks for the frequencies
0.48 (period: 2.08 m), 0.7 (period: 1.43 m) and 1.4 (period: 0.71 m).
Applying the two alternatives, biostratigraphy-derived SR reveals that the
most distinct 71 cm cycles could represent obliquity when the SR of 1.65 cm kyr<inline-formula><mml:math id="M93" 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> is applied. Finally, we used the <inline-formula><mml:math id="M94" 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 record to define the
exact temporal window of the sampled interval and confirm the assumed
cyclicity by matching the isotopic signal to the Westerhold et al. (2020) stable isotope loess smoothed record
<inline-formula><mml:math id="M95" 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  curve as a target. The new isotopic curve reveals a prominent
minimum, which corresponds to the 15.6 Ma event, but the older 16.0 Ma
isotopic minimum (also seen in carbon isotopic record of the target) is not
recorded, indicating that the sampled interval spans less than 400 kyr and
confirming that the average SR must be <inline-formula><mml:math id="M96" display="inline"><mml:mrow><mml:mi mathvariant="italic">&gt;</mml:mi><mml:mn mathvariant="normal">1.2</mml:mn></mml:mrow></mml:math></inline-formula> cm kyr<inline-formula><mml:math id="M97" 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>.
Overall, the new oxygen and carbon stable isotope signals show similar
trends and absolute values as the global stack and representative individual
records (Fig. S3), but the resolution of the new record is slightly lower. It
does seem to record stable oxygen isotopic maxima at 15 720 and 15 900 ka that
are also seen in the other records, but the absolute values appear lighter
by about 0.5 ‰, and the shape of the corrected average
record between these maxima appears to display a stronger eccentricity
component. The new stable carbon isotope record also shows similar absolute
values and an overall decreasing trend as seen in the global stack (Fig. S3), but our corrected average signal is hard to compare to the stack in
detail, and the representative records both show substantial divergence at
orbital timescales. The new record does not show the stable carbon isotopic
minimum at 15 980 ka nor the increasing trend afterwards, indicating that it
must have started later. The divergence at the beginning of our record by
almost 1 ‰ from the stack has to be seen in the context
of a similar departure seen in the record from Site U1338. Because the new
isotopic curve does not allow sufficiently robust tuning within the target
interval, after the alignment with the younger isotopic maximum we used the
<inline-formula><mml:math id="M98" display="inline"><mml:mrow><mml:mi>E</mml:mi><mml:mo>+</mml:mo><mml:mi>T</mml:mi><mml:mo>-</mml:mo><mml:mi>P</mml:mi></mml:mrow></mml:math></inline-formula> signal as a target curve (taking in account the eccentricity, the
obliquity and the precession) (Fig. 7a) (Laskar et al., 2004) to tune
prominent light minima with <inline-formula><mml:math id="M99" display="inline"><mml:mrow><mml:mi>E</mml:mi><mml:mo>+</mml:mo><mml:mi>T</mml:mi><mml:mo>-</mml:mo><mml:mi>P</mml:mi></mml:mrow></mml:math></inline-formula> minima (and obliquity minima)
(Shackleton et al., 1999; Zeeden et al., 2013) (Fig. 7a and b). This tuning
has then been verified by plotting the stable isotope (both <inline-formula><mml:math id="M100" 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 and
<inline-formula><mml:math id="M101" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C) record using the new given ages and comparing it to the existing
stable isotopes loess smooth records from Westerhold et al. (2020) (Fig. S3.).</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="d1e1625"><bold>(a)</bold> Quaternary and Pliocene benthic stable oxygen records from Site
927 and a global stack for the Miocene (Bickert et al., 2004; Westerhold et
al., 2020). <bold>(b)</bold> Orbital parameters: eccentricity and daily summer insolation for
21 June at 65<inline-formula><mml:math id="M102" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> N (Laskar et al., 2004). <bold>(c)</bold> CaCO<inline-formula><mml:math id="M103" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR
and boxplot for each interval. <bold>(d)</bold> SR and <bold>(e)</bold> CaCO<inline-formula><mml:math id="M104" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> % in the dried
bulk sediment and a boxplot for each interval.</p></caption>
            <?xmltex \igopts{width=369.885827pt}?><graphic xlink:href="https://bg.copernicus.org/articles/20/597/2023/bg-20-597-2023-f08.png"/>

          </fig>

</sec>
<sec id="Ch1.S3.SS2.SSS4">
  <label>3.2.4</label><title>High-resolution records of carbonate content and carbonate accumulation
rates at ODP Site 927</title>
      <p id="d1e1684">The new carbonate content analyses are based on 261 measurements, yielding
values comparable to existing low-resolution measurements, confirming
decreasing carbonate content throughout the Neogene due to dilution by
clastic sediments from Amazon fan
(Curry et al., 1995;<?pagebreak page608?> Bickert
et al., 1997; Harris et al., 1997) and indicating particularly strong
variations in the Quaternary (Fig. 8). In combination with the new
high-resolution SR data (Fig. 8), these measurements provide records of
sub-orbital variability in CaCO<inline-formula><mml:math id="M105" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR across the four intervals, showing
orbital-scale variability exceeding the differences in mean CaCO<inline-formula><mml:math id="M106" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR
among the intervals (Fig. 8).</p>
      <p id="d1e1705">The comparison between the highly resolved record for the four intervals of
interest (Fig. 8c, d, and e) and the environmental parameters (Fig. 8a and
b) highlights the good correlation – in terms of phase and amplitude –
between the CaCO<inline-formula><mml:math id="M107" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR (reflecting the pelagic carbonate production) and
the insolation at 65<inline-formula><mml:math id="M108" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> N signal for the two warm interglacials
observed. For the MIS 5 and the MIS 9 warm interglacials, there is a strong
correlation between the CaCO<inline-formula><mml:math id="M109" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> % and CaCO<inline-formula><mml:math id="M110" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR (<inline-formula><mml:math id="M111" display="inline"><mml:mrow><mml:msup><mml:mi>r</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> of 0.86
and 0.93) (Figs. 8 and  9). At the same time, the SR is reaching high
values (3 to 5 cm kyr<inline-formula><mml:math id="M112" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, independently of CaCO<inline-formula><mml:math id="M113" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR changes,
indicating the role of another component than the pelagic carbonate
production influencing the SR. In contrast, during the MIS KM5, the
CaCO<inline-formula><mml:math id="M114" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR is driven by both the carbonate content and the SR, and in the
Miocene, the CaCO<inline-formula><mml:math id="M115" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR appears to be dominantly driven by SR only (Fig. 9). Furthermore, the slope of the relationship between carbonate content and
CaCO<inline-formula><mml:math id="M116" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR appears to decrease with increasing age, indicating that the
earlier in the record, the less the carbonate content is influencing the
CaCO<inline-formula><mml:math id="M117" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F9" specific-use="star"><?xmltex \currentcnt{9}?><?xmltex \def\figurename{Figure}?><label>Figure 9</label><caption><p id="d1e1818"><bold>(a)</bold> Relationship between the CaCO<inline-formula><mml:math id="M118" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR and the SR and <bold>(b)</bold>
relationship between the CaCO<inline-formula><mml:math id="M119" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR and the CaCO<inline-formula><mml:math id="M120" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> % for the four
periods of interest.</p></caption>
            <?xmltex \igopts{width=369.885827pt}?><graphic xlink:href="https://bg.copernicus.org/articles/20/597/2023/bg-20-597-2023-f09.png"/>

          </fig>

      <?pagebreak page609?><p id="d1e1860">The presence of multiple CaCO<inline-formula><mml:math id="M121" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR values for the same SR values,
especially for the Quaternary intervals, is due to the few available values
of SR, because the studied intervals are short and the tuning cannot be
carried out on much higher resolution than orbital. This pattern likely
affects the correlation analysis and in such a situation, it would have been
appropriate to treat the CaCO<inline-formula><mml:math id="M122" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR data as groups of observations, each
representing a different mean SR, and test for differences using ANOVA.
However, the number of observations for some of the intervals is too low, to
run the test effectively. However, this limitation may have caused the
apparently significant relationship between CaCO<inline-formula><mml:math id="M123" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR and SR for MIS9,
which we indeed consider likely to be an artefact.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F10" specific-use="star"><?xmltex \currentcnt{10}?><?xmltex \def\figurename{Figure}?><label>Figure 10</label><caption><p id="d1e1892">CaCO<inline-formula><mml:math id="M124" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR for each period of interest, average value between
two maxima per period (for Quaternary and Pliocene), average value taking into
account maxima and minima for the Pliocene and the Miocene, and
quantification of change within (amplitude) or between each of the periods of
interest. The shaded areas are underlying the maxima values of CaCO<inline-formula><mml:math id="M125" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR
used for the quantification of change between the time intervals
calculation.</p></caption>
            <?xmltex \igopts{width=369.885827pt}?><graphic xlink:href="https://bg.copernicus.org/articles/20/597/2023/bg-20-597-2023-f10.png"/>

          </fig>

      <p id="d1e1919">When we look at the trend of the highest values reached on long geological
timescale from the mid-Miocene to MIS 5 (Fig. 10), we observe a 31 %
decrease in CaCO<inline-formula><mml:math id="M126" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR from the Pliocene (highest value) to the
Pleistocene MIS 5 (lowest value), excluding dissolution intervals in the
Pleistocene. Taking into account the average value of the MCO and MIS KM5, we
found an increase in the pelagic carbonate production of 59 % from
Miocene to Pliocene MIS KM5. If we now take into account the maxima values for
the Quaternary and Pliocene MIS KM5, we observe a decrease of 12 % from
the Pliocene MIS KM5 to Pleistocene and a decrease of 22 % from
Pleistocene MIS 9 to Pleistocene MIS 5.</p>
      <p id="d1e1931">Looking at the amplitude of the variability within the Pliocene and Miocene
interval, we found higher values in the Pliocene (65 %) compared to the
average of the period (1.98 g cm<inline-formula><mml:math id="M127" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> kyr<inline-formula><mml:math id="M128" 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>) than in the Miocene (42 %) compared to the average (1.24 g cm<inline-formula><mml:math id="M129" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> kyr<inline-formula><mml:math id="M130" 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>).</p>
</sec>
</sec>
</sec>
<sec id="Ch1.S4">
  <label>4</label><title>Discussion</title>
<sec id="Ch1.S4.SS1">
  <label>4.1</label><title>Carbonate preservation during the Quaternary</title>
      <p id="d1e1999">During the Pleistocene, the CaCO<inline-formula><mml:math id="M131" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR at Site 927 was driven only by the
carbonate content, indicating that the signal is affected by dissolution.
This is confirmed by the presence of very low values of carbonate content
and CaCO<inline-formula><mml:math id="M132" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR during the cold intervals in the Pleistocene, in phase
with the <inline-formula><mml:math id="M133" 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 and insolation signal, indicating a relationship to
changes in deep-water circulation, confirming the conclusions by Bickert et
al. (1997). As expected from the overall stratigraphy and palaeoceanography
of the Ceara Rise sites
(Curry
et al., 1995; Frenz et al., 2006; King et al., 1997), the new carbonate
content (Fig. 8e) and CaCO<inline-formula><mml:math id="M134" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR (Fig. 8c) records from Site 927 show
strong minima during cold intervals of the Quaternary (indicated by
<inline-formula><mml:math id="M135" 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 record), which is consistent with the shoaling of the corrosive
AABW (Miller et al., 2012; Harris et
al., 1997), causing dissolution at shallower depth (Gröger et al.,
2003a, b). In contrast, the maxima in CaCO<inline-formula><mml:math id="M136" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR and carbonate content in
the sediment during the Quaternary do not appear to be affected by
dissolution. Therefore, whilst we cannot use the Quaternary variability in
the CaCO<inline-formula><mml:math id="M137" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR to estimate the orbital-scale variability in pelagic
carbonate production, we can use the interglacial maxima (Fig. 10) to
estimate pelagic carbonate production during the Quaternary, assuming that
during the studied Pleistocene interglacials Site 927 was positioned
above the lysocline, as is the case during the Holocene.</p><?xmltex \hack{\newpage}?>
</sec>
<?pagebreak page610?><sec id="Ch1.S4.SS2">
  <label>4.2</label><title>Carbonate preservation during the Pliocene and Miocene</title>
      <p id="d1e2079">Because the Ceara Rise sites became periodically affected by the more
corrosive Antarctic bottom water only after the initiation of the North
Hemisphere glaciation
(Liebrand
et al., 2016; Harris et al., 1997; Pälike et al., 2006a), the studied
Pliocene and Miocene intervals should not be affected by dissolution. Paul
et al. (2000) note that the exact subsidence history of the
Ceara Rise is unknown but assume minimal subsidence since the early Miocene.
Similarly, sea level differences among Quaternary interglacials and the Pliocene
and Miocene were likely on the order of tens of metres. Therefore, the
largest changes in palaeodepth would have been due to sediment cover, which
would make the studied mid-Miocene interval about 300 m deeper compared to
the present one (this depth is still above the present day lysocline depth
of 4200 m b.s.l.). Throughout the entire studied interval since the Miocene
(Fig. 3), the shallowest cores (925 and 927) record higher CaCO<inline-formula><mml:math id="M138" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR
values than the deeper ones. This also indicates that these sites likely
remained above the lysocline (Curry et al., 1995; Bickert et al., 1997;
Frenz et al., 2006; Gröger et al., 2003a, b) and that the CaCO<inline-formula><mml:math id="M139" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR
signals recorded at these sites primarily record changes in pelagic
carbonate production. To provide further support for the lack of dissolution
control on the pre-Quaternary variation in CaCO<inline-formula><mml:math id="M140" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR, for
the Pliocene and Miocene interval we generated new data on the degree of fragmentation of
planktonic foraminifera shells, a commonly accepted proxy for the extent of
carbonate dissolution
(Berger et
al., 1982; Preiss-Daimler et al., 2013). The fragmentation data (Fig. S4)
reveal good preservation (see also Fig. S7) of foraminiferal shells
throughout the Pliocene and Miocene intervals, showing no correlation with
CaCO<inline-formula><mml:math id="M141" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR (Fig. S5), confirming that the CaCO<inline-formula><mml:math id="M142" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR was not driven by
dissolution at that time and therefore must reflect pelagic carbonate
production changes.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F11" specific-use="star"><?xmltex \currentcnt{11}?><?xmltex \def\figurename{Figure}?><label>Figure 11</label><caption><p id="d1e2129">MTM spectral analysis of the CaCO<inline-formula><mml:math id="M143" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR record through time
(Meyers, 2014; R Core Team, 2021). The dashed lines represent the 95 %
significance level. The pink shadows correspond to the orbital periodicities
(eccentricity at 404 and 100 ka, obliquity at 54 and 41 ka, and precession at 21 ka).</p></caption>
          <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://bg.copernicus.org/articles/20/597/2023/bg-20-597-2023-f11.png"/>

        </fig>

</sec>
<sec id="Ch1.S4.SS3">
  <label>4.3</label><title>Orbital variability in the Pliocene and Miocene</title>
      <p id="d1e2155">Assuming dissolution did not play a significant role in the observed
variations in CaCO<inline-formula><mml:math id="M144" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR in Pleistocene interglacials and prior to the
Quaternary and that pelagic carbonate is the main component of the carbonate
fraction of the sediment (Curry et al., 1995), we here observe the changes
in the export flux of pelagic biogenic carbonate. Under the same assumption,
the new record from Site 927 reveals that pelagic carbonate production
(assessed by the pelagic CaCO<inline-formula><mml:math id="M145" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR) in the equatorial ocean (avoiding
large-amplitude temperature changes) has changed on a geological timescale by
a factor of 2 and on orbital timescales by up to 50 %. The presence of
orbital-scale variability in pelagic carbonate production is an interesting
phenomenon that requires further analysis. First, we tested whether or not
this variability is periodic, i.e. whether the underlying changes in pelagic
carbonate production responded to orbital forcing. Such analysis is
possible because the studied intervals have been tuned to the orbital
target using parameters other than carbonate content (Figs. 6 and 7).
Multitaper method (MTM) spectra derived with the astrochron package in R
(Meyers, 2014, using R 4.1.2., R Core Team, 2021) (Fig. 11) highlight
significant periodicity close to the precession band for the MIS KM5 and
periodicities in the obliquity and 100 ka eccentricity bands for the MCO.
This implies that during both intervals, the pelagic production likely
varied in response to orbitally driven environmental factors, such as
insolation (light intensity for phytoplankton,
Cavaleiro et al., 2018) or
nutrient availability due to changes in upwelling
(Cavaleiro et al.,<?pagebreak page611?> 2020).
Interestingly, the dominant periodicities appear different between the
Pliocene and Miocene. Next, we asked whether or not the observed
periodicities in CaCO<inline-formula><mml:math id="M146" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR are coherent with the actual insolation,
obliquity and eccentricity signals. This is possible because the underlying
age models have been tuned such that they should preserve the correct phase
relationship with the orbital forcing (Figs. 6 and 7). To this end, we
carried out cross Blackman–Tukey (BT) analyses using the Analyseries
software 2.0 (Paillard et al., 1996). The results (Fig. 12) indicate a
coherence with insolation in the precession band and with the 41 ka
obliquity for the MIS KM5. In both cases, the coherence occurs in phase. In
contrast, for the MCO we observe a coherence at 41 ka with the obliquity
periodicity and at 100 ka with eccentricity, but in both cases the
coherence is anti-phased. That the pelagic carbonate production is
responding to an eccentricity-paced periodicity (Figs. 11 and 12) is
interesting, as eccentricity was not the main driver of the Earth climate
signal (Westerhold et
al., 2020; De Vleeschouwer et al., 2020). The carbon cycle in the Miocene
appears to show eccentricity pacing
(Holbourn
et al., 2007, 2018; De Vleeschouwer et al., 2020; Raitzsch et al., 2021),
and our results indicate that pelagic carbonate productivity may play a role
in modulation of this cyclicity. We also note that the discovery of
eccentricity forcing pelagic carbonate production in the Miocene and a shift
towards obliquity and precession forcing in the Pliocene is consistent with
the observations from mid-latitudes by Drury et al. (2021),
and the modelling study by Vervoort et al. (2021) provides potential mechanisms on how
the eccentricity and obliquity frequencies in carbonate production may arise
despite the dominance of the precession frequencies in the forcing.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F12" specific-use="star"><?xmltex \currentcnt{12}?><?xmltex \def\figurename{Figure}?><label>Figure 12</label><caption><p id="d1e2187">Coherence diagram BT cross correlation (Paillard et al., 1996)
between the CaCO<inline-formula><mml:math id="M147" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR and the orbital parameters (Laskar et al., 2004).
The dashed curves show the 90 % confidence intervals. The horizontal red
line corresponds to the non-zero coherence at a significance level of 90 %. The vertical pink lines correspond to the orbital periodicities
(eccentricity at 404 and 100 ka, obliquity at 54 and 41 ka, and precession at 21 ka).</p></caption>
          <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://bg.copernicus.org/articles/20/597/2023/bg-20-597-2023-f12.png"/>

        </fig>

      <?xmltex \floatpos{t}?><fig id="Ch1.F13" specific-use="star"><?xmltex \currentcnt{13}?><?xmltex \def\figurename{Figure}?><label>Figure 13</label><caption><p id="d1e2207">Comparison of the CaCO<inline-formula><mml:math id="M148" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR (black) with both the obliquity
(grey) and the <inline-formula><mml:math id="M149" display="inline"><mml:mrow><mml:mi>E</mml:mi><mml:mo>+</mml:mo><mml:mi>T</mml:mi><mml:mo>-</mml:mo><mml:mi>P</mml:mi></mml:mrow></mml:math></inline-formula> orbital records (blue) (Laskar et al., 2004) for <bold>(a)</bold>
MIS KM5 and <bold>(b)</bold> the MCO.</p></caption>
          <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://bg.copernicus.org/articles/20/597/2023/bg-20-597-2023-f13.png"/>

        </fig>

      <?xmltex \floatpos{t}?><fig id="Ch1.F14" specific-use="star"><?xmltex \currentcnt{14}?><?xmltex \def\figurename{Figure}?><label>Figure 14</label><caption><p id="d1e2250">Comparison of the CaCO<inline-formula><mml:math id="M150" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR at <bold>(a)</bold> the five Ceara Rise sites
(Sect. 3.1., in grey) and CaCO<inline-formula><mml:math id="M151" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR at high resolution (this study; in
colours) and <bold>(b)</bold> the CaCO<inline-formula><mml:math id="M152" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR record in the equatorial Pacific (colours)
(Lyle et al., 2019) and
South Atlantic Ocean (black) (Site 1264, Drury et al., 2021).</p></caption>
          <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://bg.copernicus.org/articles/20/597/2023/bg-20-597-2023-f14.png"/>

        </fig>

      <p id="d1e2292">Finally, we consider the apparent shift in the phase in the relationship
between orbital forcing and the CaCO<inline-formula><mml:math id="M153" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR record between the Pliocene
and Miocene. This relationship implied by the cross-spectral analysis is
clearly visible in the raw data (Fig. 13), and we consider it unlikely that
it is due to tuning artefacts. We note that the Miocene record ends with a
strong and distinct minimum in the oxygen isotope record, which provides a
strong constraint on the phase relationship between the youngest CaCO<inline-formula><mml:math id="M154" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>
AR and obliquity cycle. These show an opposite phase relationship to that
observed during the Pliocene. This could be explained by a change in the
carbonate production response to the insolation changes between the Pliocene
and the Miocene. Indeed, the production of different pelagic calcifiers
could be promoted by a decreased mean annual insolation at equatorial
latitude (with high <inline-formula><mml:math id="M155" display="inline"><mml:mrow><mml:mi>E</mml:mi><mml:mo>+</mml:mo><mml:mi>T</mml:mi><mml:mo>-</mml:mo><mml:mi>P</mml:mi></mml:mrow></mml:math></inline-formula> and high obliquity) during the Pliocene compared
to the Miocene, when the pelagic carbonate calcifiers appears to be promoted
by a higher mean annual insolation at equatorial latitude (with low <inline-formula><mml:math id="M156" display="inline"><mml:mrow><mml:mi>E</mml:mi><mml:mo>+</mml:mo><mml:mi>T</mml:mi><mml:mo>-</mml:mo><mml:mi>P</mml:mi></mml:mrow></mml:math></inline-formula>
and low obliquity). We can then expect a higher weight of the foraminifera
(non-photosynthetic) in the carbonate production balance during the Pliocene
and a higher weight of the coccolithophores (doing photosynthesis) in the
carbonate production balance during the Miocene. This is coherent with the
climate–carbon cycle changes occurring between the Miocene and the Pliocene,
highlighted by De Vleeschouwer et al. (2020), who found changes in the phase
relationship of <inline-formula><mml:math id="M157" 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 and <inline-formula><mml:math id="M158" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C before and after 6 Ma.</p>
</sec>
<sec id="Ch1.S4.SS4">
  <label>4.4</label><title>Long-term trend (differences between periods)</title>
      <p id="d1e2376">Because of the observed changes in what appears to be carbonate production
among the studied intervals and especially within the studied intervals, we
conclude that tropical pelagic calcifiers responded to environmental or
biotic forcing on orbital cycles, as well as to long-term shifts in<?pagebreak page612?> climate
and/or ocean chemistry. In other words, either the production, the community
composition or the biomineralization of the tropical pelagic calcifiers may
respond to local changes in light, temperature and nutrients delivered by
upwelling, which followed orbital cycles, as well as to long-term shifts in
climate and/or ocean chemistry. The inferred changes in pelagic carbonate
production on both timescales are sufficiently large that when extrapolated
on a global scale, they could have played a role in the regulation of the
carbon cycle. For example, Boudreau et al. (2018) estimated that
changes in global pelagic carbonate production on the order of 10 % would
be sufficient to affect the marine carbon cycle on timescales from years to
millions of years. Whereas the drivers of the orbital-scale variability could be
plausibly attributed to changes in local oceanic parameters affecting
primary production, the causes of the long-term shifts require another
explanation.</p>
      <p id="d1e2379">There are two studies presenting long continuous CaCO<inline-formula><mml:math id="M159" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR records from
the Miocene to the present (Fig. 14). Both records show an increasing
CaCO<inline-formula><mml:math id="M160" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR from the early Miocene to Pliocene and a decreasing CaCO<inline-formula><mml:math id="M161" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR
from the Pliocene to Quaternary and both records indicate the<?pagebreak page613?> presence of
high-amplitude variability on orbital scales throughout the last 16 Myr
(Drury et al., 2021; Lyle et al., 2019). The observed CaCO<inline-formula><mml:math id="M162" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR at the
Ceara Rise appears coherent with both records (Fig. 14), as well as with the
recent results by Sutherland et al. (2022) from the
South Pacific. Our record shows similar absolute values to Lyle et al. (2019) and Drury et al. (2021) (a CaCO<inline-formula><mml:math id="M163" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR between 0 and 5 g cm<inline-formula><mml:math id="M164" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> ka<inline-formula><mml:math id="M165" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> and a similar overall trend, with its highest values being in the late
Miocene–early Pliocene. Clearly, the overall trend of CaCO<inline-formula><mml:math id="M166" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR at the
Ceara Rise supports the existence of a late Miocene carbonate maximum also
under tropical conditions. Interestingly, our observations from the Ceara
Rise also support the conclusion from Sutherland et al. (2022) that there
does not appear to be any strong relationship between pelagic carbonate
production and global CO<inline-formula><mml:math id="M167" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>, other than the fact that the lowest
CaCO<inline-formula><mml:math id="M168" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR in both their and our records are observed during the MCO with
presumably highest CO<inline-formula><mml:math id="M169" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>.</p>
</sec>
</sec>
<sec id="Ch1.S5" sec-type="conclusions">
  <label>5</label><title>Conclusions</title>
      <p id="d1e2501">A compilation of CaCO<inline-formula><mml:math id="M170" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR for the five sites of Leg 154 in the
western equatorial Atlantic Ocean documents a distinct increase in SR from
Miocene to Quaternary, but the CaCO<inline-formula><mml:math id="M171" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR remained relatively stable. The
two shallowest sites at the Ceara Rise (925 and 927) consistently record
higher CaCO<inline-formula><mml:math id="M172" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR, confirming observations of good carbonate preservation
during Quaternary interglacials and throughout the Pliocene and Miocene.
This means that the observed changes in CaCO<inline-formula><mml:math id="M173" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR at these sites should
reflect changes in pelagic carbonate production.</p>
      <p id="d1e2540">To analyse long-term and orbital-scale patterns of pelagic carbonate
production variability, we generated new data for four periods at Site 927.</p>
      <p id="d1e2543">We found that CaCO<inline-formula><mml:math id="M174" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR, as a proxy for pelagic carbonate production in
the tropical Atlantic, exhibited both long-term changes and a pervasive
orbital-scale variability. We observe a 31 % decrease in CaCO<inline-formula><mml:math id="M175" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR
from the Pliocene MIS KM5 to the Pleistocene interglacial MIS 5, but 59 %
higher values for the Pliocene warm period than for the Miocene climatic
optimum. On the orbital timescale, the Quaternary signals are overprinted
by precession and insolation forcing on deep-water circulation, causing
dissolution. However, concerning the Pliocene Warm Period and the Miocene
Climatic Optimum, we observe a persistent variability in CaCO<inline-formula><mml:math id="M176" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR with
an amplitude exceeding that of the long-term mean shifts. We show that the
CaCO<inline-formula><mml:math id="M177" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> AR at low latitude varied in phase with insolation (precession)
cycles during the Pliocene, whereas the Miocene signal is dominated by 100 kyr eccentricity cycles, which are exactly anti-phased with the carbonate
signal.</p>
      <p id="d1e2582">We conclude that the low-latitude pelagic carbonate production responded
strongly to orbital-driven local tropical processes, rather than to secular
changes in the global climate or ocean chemistry (like global CO<inline-formula><mml:math id="M178" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>). The
Ceara Rise records are consistent with the existence of a late Miocene<?pagebreak page614?> to
Pliocene global carbonate production optimum, but the magnitude of the
long-term change appears smaller than outside the tropics. Instead,
orbital-scale variability dominates the record and the inferred magnitude of
production changes are potentially sufficient to affect the global carbon
cycle through the process of biological compensation (Boudreau et al.,
2018).</p>
      <p id="d1e2595">Our results imply that in the context of the ongoing and projected global
change, pelagic carbonate production may be an important variable in the
parameterization of the global marine carbon cycle, especially with regard to
the long-term (millennial-scale) fate of anthropogenic carbon injection. To
parameterize the pelagic carbonate production, it remains to be shown whether
it changes due to changes in production (population sizes),
biomineralization (amount of carbonate produced per individual) or community
composition (shift to more or less calcified taxa).</p>
</sec>

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

      <p id="d1e2602">All data sets are available on Pangaea (<ext-link xlink:href="https://doi.org/10.1594/PANGAEA.945848" ext-link-type="DOI">10.1594/PANGAEA.945848</ext-link>, Cornuault  et al., 2022a, <ext-link xlink:href="https://doi.org/10.1594/PANGAEA.945773" ext-link-type="DOI">10.1594/PANGAEA.945773</ext-link>, Cornuault  et al., 2022b, <ext-link xlink:href="https://doi.org/10.1594/PANGAEA.945812" ext-link-type="DOI">10.1594/PANGAEA.945812</ext-link>, Cornuault  et al., 2022c, <ext-link xlink:href="https://doi.org/10.1594/PANGAEA.945789" ext-link-type="DOI">10.1594/PANGAEA.945789</ext-link>, Cornuault  et al., 2022d, <ext-link xlink:href="https://doi.org/10.1594/PANGAEA.945707" ext-link-type="DOI">10.1594/PANGAEA.945707</ext-link>, Cornuault  et al., 2022e).</p>
  </notes><app-group>
        <supplementary-material position="anchor"><p id="d1e2620">The supplement related to this article is available online at: <inline-supplementary-material xlink:href="https://doi.org/10.5194/bg-20-597-2023-supplement" xlink:title="pdf">https://doi.org/10.5194/bg-20-597-2023-supplement</inline-supplementary-material>.</p></supplementary-material>
        </app-group><notes notes-type="authorcontribution"><title>Author contributions</title>

      <p id="d1e2629">The conceptualisation, as well as samples selection, was carried out by all the co-authors. PC compiled all the existing carbonate data for he five sites of Leg 154 and calculated carbonate accumulation rates from it. PC analysed all of the newly generated carbon content from the samples of this study, calculated the carbonate content and accumulation rates from it, and revised the tuned age models for the three periods of interest in this study (with the help of TW and MK). PC ran the spectral analysis and prepared all the figures presented in this paper. PC wrote the manuscript, and all co-authors contributed to the manuscript.</p>
  </notes><notes notes-type="competinginterests"><title>Competing interests</title>

      <p id="d1e2635">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="d1e2641">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="d1e2647">We
thank Brit Kockisch for assistance with carbonate content analyses and
Anna-Joy Drury for providing South Atlantic carbonate data and discussing
the results.</p></ack><notes notes-type="financialsupport"><title>Financial support</title>

      <p id="d1e2652">This research used samples and data provided by the Ocean Drilling Program
(ODP), which is sponsored by the US National Science 15 Foundation (NSF) and
participating countries. This research was supported by the DFG through
Germany's Excellence Strategy, Cluster of Excellence “The Ocean
Floor – Earth's Uncharted Interface” (EXC-2077, Project 390741603).
<?xmltex \hack{\newline}?><?xmltex \hack{\newline}?>
The article processing charges for this open-access<?xmltex \notforhtml{\newline}?>  publication were covered by the University of Bremen.</p>
  </notes><notes notes-type="reviewstatement"><title>Review statement</title>

      <p id="d1e2663">This paper was edited by Caroline P. Slomp and reviewed by two anonymous referees.</p>
  </notes><ref-list>
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