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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" dtd-version="3.0">
  <front>
    <journal-meta>
<journal-id journal-id-type="publisher">CP</journal-id>
<journal-title-group>
<journal-title>Climate of the Past</journal-title>
<abbrev-journal-title abbrev-type="publisher">CP</abbrev-journal-title>
<abbrev-journal-title abbrev-type="nlm-ta">Clim. Past</abbrev-journal-title>
</journal-title-group>
<issn pub-type="epub">1814-9332</issn>
<publisher><publisher-name>Copernicus GmbH</publisher-name>
<publisher-loc>Göttingen, Germany</publisher-loc>
</publisher>
</journal-meta>

    <article-meta>
      <article-id pub-id-type="doi">10.5194/cp-11-15-2015</article-id><title-group><article-title>Photic zone changes in the north-west Pacific Ocean from MIS 4–5e</article-title>
      </title-group><?xmltex \runningtitle{Photic zone changes in the north-west Pacific Ocean}?><?xmltex \runningauthor{G.~E.~A.~Swann and A.~M.~Snelling}?>
      <contrib-group>
        <contrib contrib-type="author" corresp="yes" rid="aff1">
          <name><surname>Swann</surname><given-names>G. E. A.</given-names></name>
          <email>george.swann@nottingham.ac.uk</email>
        <ext-link>https://orcid.org/0000-0002-4750-9504</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2">
          <name><surname>Snelling</surname><given-names>A. M.</given-names></name>
          
        </contrib>
        <aff id="aff1"><label>1</label><institution>School of Geography, University of Nottingham, University Park, Nottingham, NG7 2RD, UK</institution>
        </aff>
        <aff id="aff2"><label>2</label><institution>NERC Isotope Geosciences Facilities, British Geological Survey, Keyworth, Nottingham, NG12 5GG, UK</institution>
        </aff>
      </contrib-group>
      <author-notes><corresp id="corr1">G. E. A. Swann (george.swann@nottingham.ac.uk)</corresp></author-notes><pub-date><day>6</day><month>January</month><year>2015</year></pub-date>
      
      <volume>11</volume>
      <issue>1</issue>
      <fpage>15</fpage><lpage>25</lpage>
      <history>
        <date date-type="received"><day>11</day><month>August</month><year>2014</year></date>
           <date date-type="rev-request"><day>29</day><month>August</month><year>2014</year></date>
           <date date-type="rev-recd"><day>26</day><month>November</month><year>2014</year></date>
           <date date-type="accepted"><day>27</day><month>November</month><year>2014</year></date>
           
      </history>
      <permissions>
<license license-type="open-access">
<license-p>This work is licensed under a Creative Commons Attribution 3.0 Unported License. To view a copy of this license, visit <ext-link ext-link-type="uri" xlink:href="http://creativecommons.org/licenses/by/3.0/">http://creativecommons.org/licenses/by/3.0/</ext-link></license-p>
</license>
</permissions><self-uri xlink:href="https://www.clim-past.net/11/15/2015/cp-11-15-2015.html">This article is available from https://www.clim-past.net/11/15/2015/cp-11-15-2015.html</self-uri>
<self-uri xlink:href="https://www.clim-past.net/11/15/2015/cp-11-15-2015.pdf">The full text article is available as a PDF file from https://www.clim-past.net/11/15/2015/cp-11-15-2015.pdf</self-uri>


      <abstract>
    <p>In comparison to other sectors of the marine system, the palaeoceanography of the subarctic North
Pacific Ocean is poorly constrained. New diatom isotope records of <inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C,
<inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O, <inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>Si (<inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:math></inline-formula>,
<inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:math></inline-formula>, and <inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>Si<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:math></inline-formula>) are presented alongside existing
geochemical and isotope records to document changes in photic zone conditions, including nutrient
supply and the efficiency of the soft-tissue biological pump, between Marine Isotope Stage (MIS) 4
and MIS 5e. Peaks in opal productivity in MIS 5b/c and MIS 5e are both associated with the
breakdown of the regional halocline stratification and increased nutrient supply to the photic
zone. Whereas the MIS 5e peak is associated with low rates of nutrient utilisation, the MIS 5b/c
peak is associated with significantly higher rates of nutrient utilisation. Both peaks, together
with other smaller increases in productivity in MIS 4 and 5a, culminate with a significant increase
in freshwater input which strengthens/re-establishes the halocline and limits further upwelling of
sub-surface waters to the photic zone. Whilst <inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>Si<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:math></inline-formula> and previously
published records of diatom <inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>15</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>N (<inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>15</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>N<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:math></inline-formula>)
<xref ref-type="bibr" rid="bib1.bibx10 bib1.bibx11" id="paren.1"/> show similar trends until the latter half of MIS 5a, the records
become anti-correlated after this juncture and into MIS 4, suggesting a possible change in photic
zone state such as may occur with a shift to iron or silicon limitation.</p>
  </abstract>
    </article-meta>
  </front>
<body>
      

<sec id="Ch1.S1" sec-type="intro">
  <title>Introduction</title>
      <p>The modern-day subarctic north-west Pacific Ocean represents a major component of the
global oceanic system acting as the one of the terminuses of the deep water thermohaline
circulation. Today high precipitation and low evaporation in the region maintain a year-round halocline in the water
column (water depth <inline-formula><mml:math display="inline"><mml:mrow><mml:mo>=</mml:mo><mml:mn>100</mml:mn></mml:mrow></mml:math></inline-formula>–150 <inline-formula><mml:math display="inline"><mml:mi mathvariant="normal">m</mml:mi></mml:math></inline-formula>), reinforced in the summer/early autumn months by the
presence of a seasonal thermocline (water depth <inline-formula><mml:math display="inline"><mml:mrow><mml:mo>=</mml:mo><mml:mn>50</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mi mathvariant="normal">m</mml:mi></mml:math></inline-formula>)
<xref ref-type="bibr" rid="bib1.bibx21 bib1.bibx2 bib1.bibx50" id="paren.2"/>. This stratification exerts a major impact on the regional ocean by
limiting the mixing of surface waters with underlying nutrient- and carbon-rich deep water and by
preventing convection and formation of North Pacific Deep Water <xref ref-type="bibr" rid="bib1.bibx21 bib1.bibx56" id="paren.3"/>.</p>
      <p>The initial development of the halocline and stratified water column has been attributed to the onset of major Northern Hemisphere glaciation (NHG) at 2.73 Ma, which increased the flux of freshwater to the region, via increased monsoonal rainfall and/or glacial meltwater, and sea surface temperatures (SSTs) <xref ref-type="bibr" rid="bib1.bibx80 bib1.bibx29 bib1.bibx87 bib1.bibx62" id="paren.4"/>. The decrease of abyssal
water upwelling associated with this may have contributed to the establishment of globally cooler
conditions and the expansion of glaciers across the Northern Hemisphere from 2.73 <inline-formula><mml:math display="inline"><mml:mi mathvariant="normal">Ma</mml:mi></mml:math></inline-formula>
<xref ref-type="bibr" rid="bib1.bibx29" id="paren.5"/>. Whilst the halocline appears to have prevailed through the late Pliocene and early
Quaternary glacial–interglacial cycles <xref ref-type="bibr" rid="bib1.bibx85" id="paren.6"/>, other studies have shown that the
stratification boundary may have broken down in the late Quaternary at glacial terminations and
during the early part of interglacials <xref ref-type="bibr" rid="bib1.bibx74 bib1.bibx35 bib1.bibx36 bib1.bibx37 bib1.bibx23 bib1.bibx24 bib1.bibx25 bib1.bibx11 bib1.bibx41" id="paren.7"/>.</p>
      <p>Developing a complete understanding of the nature of regional stratification in the subarctic North
Pacific Ocean is important for a number of reasons. Firstly, the palaeoceanographic history of the
region remains poorly constrained relative to other sectors of the global ocean. Secondly, with
evidence of a pervasive link between the subarctic Pacific and Southern oceans
<xref ref-type="bibr" rid="bib1.bibx29 bib1.bibx35 bib1.bibx37" id="paren.8"/> records from the former can be used to further investigate
teleconnections between these regions <xref ref-type="bibr" rid="bib1.bibx28 bib1.bibx81" id="paren.9"/>. Thirdly, with subsurface waters in
the ocean interior rich in carbon and nutrients <xref ref-type="bibr" rid="bib1.bibx23 bib1.bibx25 bib1.bibx56" id="paren.10"/>, any
weakening/removal of the halocline has potential implications for the regional soft-tissue
biological pump and ocean–atmospheric exchanges of <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>.</p>
      <p>To further understand the subarctic north-west Pacific Ocean, diatom isotope measurements of
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:mi mathvariant="normal">Si</mml:mi></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>,
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>, and <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">Si</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>) are presented here from the open waters
of ODP Site 882 between Marine Isotope Stage (MIS) 4 and MIS 5e (Fig. <xref ref-type="fig" rid="Ch1.F1"/>). Existing research from the region has
revealed two periods of elevated opal concentration in this interval alongside large changes in
proxies relating to nutrient supply and utilisation
<xref ref-type="bibr" rid="bib1.bibx35 bib1.bibx36 bib1.bibx10 bib1.bibx11" id="paren.11"/>. The new diatom isotope data presented here will
allow the changes in photic zone conditions and the response of the soft-tissue biological pump to
be further constrained. Diatoms, unicellular siliceous algae, are ideally suited for this purpose as
they (1) occupy the uppermost sections of the water column above the halocline, (2) dominate export
production in high-latitude and upwelling zones <xref ref-type="bibr" rid="bib1.bibx60" id="paren.12"/>, and (3) represent a key component of the
soft-tissue biological pump in transferring carbon into the ocean interior by incorporating
ca. 23.5 % of all carbon produced by net primary production into their cellular organic matter
<xref ref-type="bibr" rid="bib1.bibx51" id="paren.13"/>.</p>
</sec>
<sec id="Ch1.S2">
  <title>Methods</title>
      <p>ODP Site 882 is located on the western section of the Detroit Seamounts at a water depth of
3244 <inline-formula><mml:math display="inline"><mml:mi mathvariant="normal">m</mml:mi></mml:math></inline-formula> (50<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>22<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> N, 167<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>36<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> E) (Fig. <xref ref-type="fig" rid="Ch1.F1"/>). The
age model used in this study is derived from the astronomical calibration of high-resolution GRAPE
density and magnetic susceptibility measurements with linear interpolation between selected
tie points <xref ref-type="bibr" rid="bib1.bibx36" id="paren.14"/>. Ages are constrained by two radiocarbon dates and verified by
correlating magnetic susceptibility and benthic foraminifera <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> records from ODP
Sites 882 and 883. Samples were prepared for diatom isotope analysis using techniques previously
employed at this site <xref ref-type="bibr" rid="bib1.bibx87 bib1.bibx88" id="paren.15"/> with the 75–150 <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">m</mml:mi></mml:mrow></mml:math></inline-formula> fraction
analysed. Diatom biovolumes, calculated following <xref ref-type="bibr" rid="bib1.bibx31" id="text.16"/> and <xref ref-type="bibr" rid="bib1.bibx88" id="text.17"/>, show that
samples in this fraction are dominated by a single taxa <italic>Coscinodiscus radiatus</italic> (Ehrenb.)
(Fig. <xref ref-type="fig" rid="Ch1.F2"/>) which blooms throughout the year with elevated fluxes often occurring in
autumn/early winter <xref ref-type="bibr" rid="bib1.bibx90 bib1.bibx91 bib1.bibx65" id="paren.18"/>. Consequently, the diatom isotope
measurements obtained here are interpreted as primarily reflecting annually averaged conditions with
a slight bias towards autumn/early winter months. Smaller size fractions which contain a greater
diversity of taxa were not analysed due to the potential for vital effects in
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx88" id="paren.19"/>. Sample purity was assessed for all samples using light
microscopy and SEM with unclean samples disregarded for isotope analysis. Both techniques show the
excellent preservation of diatoms in the sediment record and suggest that issues of
dissolution/diagenesis are not relevant to this study.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F1"><caption><p>Location of ODP Site 882 in the subarctic north-west Pacific Ocean.</p></caption>
        <?xmltex \igopts{width=213.395669pt}?><graphic xlink:href="https://www.clim-past.net/11/15/2015/cp-11-15-2015-f01.pdf"/>

      </fig>

      <p><inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">Si</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> were analysed following a combined
step-wise fluorination procedure at the NERC Isotope Geoscience Laboratory (UK) <xref ref-type="bibr" rid="bib1.bibx49" id="paren.20"/> with
measurements made on a Finnigan MAT 253 and values converted to the VSMOW and NBS28 scale
respectively using the NIGL within-run laboratory diatom standard <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mtext>BFC</mml:mtext><mml:mtext>mod</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> which
has been calibrated against NBS28. A small subset of the <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> data was
previously published as part of an investigation in <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> vital effects in
<xref ref-type="bibr" rid="bib1.bibx88" id="text.21"/> (see Table S1 in the Supplement). Where sufficient material remained following
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">Si</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> analysis, samples were analysed for
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> using a Costech elemental analyser linked to an Optima mass
spectrometer via cold trapping <xref ref-type="bibr" rid="bib1.bibx34" id="paren.22"/>. Replicate analyses of sample material across the
analysed interval indicate an analytical reproducibility (1<inline-formula><mml:math display="inline"><mml:mi mathvariant="italic">σ</mml:mi></mml:math></inline-formula>) of 0.4 ‰,
0.06 ‰ and 0.3 ‰ for <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">Si</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>
and <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> respectively.</p>
</sec>
<sec id="Ch1.S3">
  <title>Results</title>
      <p>Through the analysed interval, <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> largely follows previously published
siliceous productivity (opal) records from the region in indicating two intervals of higher
productivity from 130 to 114 <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">ka</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mi mathvariant="normal">BP</mml:mi></mml:mrow></mml:math></inline-formula> (MIS 5e) and from 101 to 86 <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">ka</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="normal">BP</mml:mi></mml:mrow></mml:math></inline-formula> (MIS 5b/c)
<xref ref-type="bibr" rid="bib1.bibx35 bib1.bibx36" id="paren.23"/> (Fig. <xref ref-type="fig" rid="Ch1.F3"/>). Before/after each of these intervals
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> is lower at <inline-formula><mml:math display="inline"><mml:mrow><mml:mo>&lt;</mml:mo><mml:mo>-</mml:mo></mml:mrow></mml:math></inline-formula>18 ‰. These trends
are also largely mirrored by the <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">Si</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>15</mml:mn></mml:msup><mml:mi mathvariant="normal">N</mml:mi></mml:mrow></mml:math></inline-formula> records of
diatom-bound nitrogen (<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>15</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">N</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>) <xref ref-type="bibr" rid="bib1.bibx10 bib1.bibx11" id="paren.24"/> records of
nutrient supply/utilisation, except during MIS 5e when values for both remain low and comparable to
those in MIS 5d (Fig. <xref ref-type="fig" rid="Ch1.F3"/>). Following a return to lower values in MIS 5a, all
productivity/nutrient proxies show a series of abrupt oscillations that continue into MIS 4 with
values in this interval equivalent to the peaks and minima documented in MIS 5b–e.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F2"><caption><p>Relative diatom species biovolumes in samples analysed for <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>.</p></caption>
        <?xmltex \igopts{width=85.358268pt}?><graphic xlink:href="https://www.clim-past.net/11/15/2015/cp-11-15-2015-f02.pdf"/>

      </fig>

      <p>Measurements of <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> can be classified into three stages: (1) periods of
relative stability in MIS 5e and MIS 5b/c (124–114 and 102–87 <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">ka</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="normal">BP</mml:mi></mml:mrow></mml:math></inline-formula>), (2) periods of
significant decreases (<inline-formula><mml:math display="inline"><mml:mrow><mml:mo>≥</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:mrow></mml:math></inline-formula> ‰) in MIS 5d and MIS 5a (113–100 and 85–76 <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">ka</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="normal">BP</mml:mi></mml:mrow></mml:math></inline-formula>),
and (3) periods of increase variability in MIS 5a-4 (75–57 <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">ka</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mi mathvariant="normal">BP</mml:mi></mml:mrow></mml:math></inline-formula>) (Fig. <xref ref-type="fig" rid="Ch1.F3"/>). Intervals
of high and stable <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values in MIS 5e and MIS 5b/c coincide with peaks in
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and opal concentrations. The termination of both productivity phases,
as indicated by changes in <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>15</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">N</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>,
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">Si</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and opal concentrations, are then concordant with the large reductions
in <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> during MIS 5d and MIS 5a, suggesting a link between the processes
controlling <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and photic zone productivity/nutrient utilisation. This is
reinforced by the often synchronous changes between <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>,
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">Si</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and opal concentrations during MIS 5a and into MIS 4.</p>
</sec>
<sec id="Ch1.S4">
  <title>Discussion</title>
<sec id="Ch1.S4.SS1">
  <title>Environmental controls on diatom isotopes</title>

      <?xmltex \floatpos{t}?><fig id="Ch1.F3" specific-use="star"><caption><p>Data from ODP Site 882 showing changes in <bold>(a)</bold> productivity (<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>, BioBa; <xref ref-type="bibr" rid="bib1.bibx35" id="altparen.25"/>, and opal
concentrations; <xref ref-type="bibr" rid="bib1.bibx36" id="altparen.26"/>); <bold>(b)</bold> nutrient dynamics (<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">Si</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>
and <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>15</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">N</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>; <xref ref-type="bibr" rid="bib1.bibx11" id="altparen.27"/>); <bold>(c)</bold> modelled <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>
supply/consumption in an open system model; and <bold>(d)</bold> freshwater input
(<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>) together with EPICA Antarctic <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx39" id="paren.28"/> and
NGRIP Greenland <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">ice</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx61" id="paren.29"/>. Changes in the supply/consumption of <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> are relative to mean conditions in MIS 5e. Green/red shading indicates the increases
in productivity and decreases in <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> respectively, which are discussed in
the text.</p></caption>
          <?xmltex \igopts{width=426.791339pt}?><graphic xlink:href="https://www.clim-past.net/11/15/2015/cp-11-15-2015-f03.pdf"/>

        </fig>

      <p>Given the limited number of published diatom isotope records in palaeoceanography, the section below
summarises the main controls on <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">Si</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>. Diatom isotopes act as an alternative proxy to records from planktonic
foraminifera at sites, such as ODP Site 882, depleted in carbonates. Measurements of
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> can be interpreted in the same way as those of planktonic foraminifera
(<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">foram</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>) <xref ref-type="bibr" rid="bib1.bibx86" id="paren.30"/> with variations linked to changes in temperature
(<inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.2 <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">‰</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup><mml:msup><mml:mi mathvariant="normal">C</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>) <xref ref-type="bibr" rid="bib1.bibx9 bib1.bibx58 bib1.bibx20 bib1.bibx15" id="paren.31"/> and surface water
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">water</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>). During biomineralisation diatoms uptake silicon,
in the form of silicic acid (<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">H</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub><mml:msub><mml:mi mathvariant="normal">SiO</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>), with the lighter <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn>28</mml:mn></mml:msup><mml:mi mathvariant="normal">Si</mml:mi></mml:mrow></mml:math></inline-formula> preferentially
used over <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn>29</mml:mn></mml:msup><mml:mi mathvariant="normal">Si</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn>30</mml:mn></mml:msup><mml:mi mathvariant="normal">Si</mml:mi></mml:mrow></mml:math></inline-formula>. With an enrichment factor independent of temperature,
the concentrations of <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> in the water (<inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula><inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mo>(</mml:mo><mml:mi mathvariant="normal">aq</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula>) and other vital effects
<xref ref-type="bibr" rid="bib1.bibx19 bib1.bibx57" id="paren.32"/>, <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">Si</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> reflects changes in photic zone silicic
acid utilisation which is regulated by the biological demand for silicic acid, the rate at which
nutrients are supplied to the photic zone and the <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:mi mathvariant="normal">Si</mml:mi></mml:mrow></mml:math></inline-formula> composition of the silicic
acid substrate (<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:mi mathvariant="normal">Si</mml:mi></mml:mrow></mml:math></inline-formula><inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mtext>DSi</mml:mtext></mml:msub></mml:math></inline-formula>) <xref ref-type="bibr" rid="bib1.bibx17 bib1.bibx73" id="paren.33"/>.</p>
      <p>A number of studies have examined the controls on <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> on carbon from bulk
cellular diatom organic material including the cytoplasm. Whilst palaeoenvironmental reconstructions
solely analyse the cell wall, which is preserved in the sediment and protected from dissolution by
the diatom frustule <xref ref-type="bibr" rid="bib1.bibx1" id="paren.34"/>, it is assumed that the controls on cell wall
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> are similar to those for bulk <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> as the
cell-wall organic matter forms a key template for diatom biomineralisation <xref ref-type="bibr" rid="bib1.bibx30 bib1.bibx89 bib1.bibx42 bib1.bibx83" id="paren.35"/>. During photosynthesis, organic carbon matter is formed from both
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msubsup><mml:mi mathvariant="normal">HCO</mml:mi><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mo>(</mml:mo><mml:mi mathvariant="normal">aq</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx94" id="paren.36"/> using both active and indirect
transportation mechanisms <xref ref-type="bibr" rid="bib1.bibx82" id="paren.37"/> and <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> photosynthetic
pathways <xref ref-type="bibr" rid="bib1.bibx72" id="paren.38"/>. Marine studies including those from the Bering Sea and North Pacific
Ocean have demonstrated that the majority of diatom carbon originates from <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msubsup><mml:mi mathvariant="normal">HCO</mml:mi><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> via
direct transportation <xref ref-type="bibr" rid="bib1.bibx93 bib1.bibx12 bib1.bibx53 bib1.bibx95 bib1.bibx96" id="paren.39"/>. Although
<inline-formula><mml:math display="inline"><mml:mrow><mml:mrow class="chem"><mml:msubsup><mml:mi mathvariant="normal">HCO</mml:mi><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow><mml:mo>:</mml:mo><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mo>(</mml:mo><mml:mi mathvariant="normal">aq</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:msub></mml:mrow></mml:mrow></mml:math></inline-formula> uptake ratios may alter with inter-species variations in cell
morphologies <xref ref-type="bibr" rid="bib1.bibx54" id="paren.40"/>, no link exists with changes in <inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula><inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mo>(</mml:mo><mml:mi mathvariant="normal">aq</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula>, Fe
availability, growth rates, primary productivity or frustule area : volume ratios <xref ref-type="bibr" rid="bib1.bibx12 bib1.bibx53 bib1.bibx95 bib1.bibx96" id="paren.41"/>.</p>
      <p>With <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn>12</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> preferentially fractionated over <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn>13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx45" id="paren.42"/>,
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> predominantly reflects changes in photosynthetic carbon demand driven by
variations in biological productivity or carbon cellular concentrations. Smaller magnitude
variations in <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> may then arise with changes in the composition of the
dissolved inorganic carbon substrate (<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula><inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mtext>DIC</mml:mtext></mml:msub></mml:math></inline-formula>) and through the
intracellular and extra-cellular balance of <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> with an increase in photic zone
<inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula><inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mo>(</mml:mo><mml:mi mathvariant="normal">aq</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> reducing <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx45 bib1.bibx69 bib1.bibx70" id="paren.43"/>. Whilst
questions remain over the potential for <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> to be impacted by changes in
<inline-formula><mml:math display="inline"><mml:mrow><mml:mrow class="chem"><mml:msubsup><mml:mi mathvariant="normal">HCO</mml:mi><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow><mml:mo>:</mml:mo><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:mrow></mml:math></inline-formula> uptake, growth rates, amino acid composition, cell morphology as well
as the diffusion of carbon into the cell by the enzyme RuBisCO <xref ref-type="bibr" rid="bib1.bibx45 bib1.bibx46 bib1.bibx47 bib1.bibx69 bib1.bibx70 bib1.bibx71 bib1.bibx67 bib1.bibx13" id="paren.44"/>, many of these physiological processes as well as the impact of
inter-species vital effects <xref ref-type="bibr" rid="bib1.bibx38" id="paren.45"/> can be partially circumvented by analysing samples
comprised of a single taxa. Consequently, with samples in this studies overwhelmingly dominated by
<italic>C. radiatus</italic>, changes in <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> are primarily interpreted as
reflecting changes in photic zone productivity (Fig. <xref ref-type="fig" rid="Ch1.F2"/>). We argue that the impact of a changes in <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula><inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mtext>DIC</mml:mtext></mml:msub></mml:math></inline-formula> is negligible due to the aforementioned evidence that <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula><inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mtext>DIC</mml:mtext></mml:msub></mml:math></inline-formula> exerts only a minimal impact on <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>, likely within analytical error, although the lack of carbonates in the sediments prevents an independent <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> record being established to prove this beyond doubt. Similarly we argue that higher <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values in MIS 5e, when higher <inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula><inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mo>(</mml:mo><mml:mi mathvariant="normal">aq</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> should have acted to reduce <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>, point towards <inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula><inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mo>(</mml:mo><mml:mi mathvariant="normal">aq</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> not exerting a significant control on <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>, although we are aware of the circular reasoning with this argument.</p>
</sec>
<sec id="Ch1.S4.SS2">
  <title>Changes in the regional biological pump (MIS 5e to MIS 5b)</title>
      <p>Previously published opal concentration data <xref ref-type="bibr" rid="bib1.bibx36" id="paren.46"/> together with
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> data from this study indicates two intervals of high siliceous
productivity at ODP Site 882 through the analysed interval: the first from 130 to 114 <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">ka</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="normal">BP</mml:mi></mml:mrow></mml:math></inline-formula>
corresponding to the last interglacial (MIS 5e: 130–116 <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">ka</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mi mathvariant="normal">BP</mml:mi></mml:mrow></mml:math></inline-formula>), the second from
101 to 86 <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">ka</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="normal">BP</mml:mi></mml:mrow></mml:math></inline-formula> covering the latter half of MIS 5c (105–93 <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">ka</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="normal">BP</mml:mi></mml:mrow></mml:math></inline-formula>) and most of MIS
5b (93–86 <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">ka</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="normal">BP</mml:mi></mml:mrow></mml:math></inline-formula>) <xref ref-type="bibr" rid="bib1.bibx36" id="paren.47"/> (Fig. <xref ref-type="fig" rid="Ch1.F3"/>, green shading). Whilst records of
biogenic barium (BioBa) capture the MIS 5e peak <xref ref-type="bibr" rid="bib1.bibx36" id="paren.48"/>, they fail to do so with the
second flux event. Modern day calibrations have noted the lack of a relationship between BioBa and export production in the region <xref ref-type="bibr" rid="bib1.bibx76" id="paren.49"/> and speculated that the mismatch can be attributed to early diagenetic remobilisation of barium following a change in redox state <xref ref-type="bibr" rid="bib1.bibx25" id="paren.50"/>. On the other hand, all evidence points against an actual preservation/dissolution issue in this BioBa record <xref ref-type="bibr" rid="bib1.bibx36" id="paren.51"><named-content content-type="pre">see</named-content></xref> and so, in line with <xref ref-type="bibr" rid="bib1.bibx36" id="text.52"/>, we interpret BioBa as a measure of organic carbon export rather than siliceous productivity. With the isotope records reported here derived from diatoms and the siliceous fraction of the sediment record, we focus our discussion on the opal siliceous productivity record and only used BioBa as a proxy of organic carbon export.</p>
      <p>Similar to the Southern Ocean, the modern-day subarctic north-west Pacific Ocean photic zone is
largely limited by iron availability <xref ref-type="bibr" rid="bib1.bibx27 bib1.bibx97" id="paren.53"/>. Accordingly, increases in bioavailable
iron represent a plausible mechanism for explaining the two main (opal inferred) productivity peaks
during MIS 5. Today iron supply is thought to primarily occur via aeolian dust deposition
originating from East Asia and the Badain Juran Desert <xref ref-type="bibr" rid="bib1.bibx99" id="paren.54"/> and other global regions
<xref ref-type="bibr" rid="bib1.bibx33" id="paren.55"/>. Additional iron is then derived from volcanic activity <xref ref-type="bibr" rid="bib1.bibx4" id="paren.56"/>, continental
margins <xref ref-type="bibr" rid="bib1.bibx43" id="paren.57"/>, advection of waters from the Okhotsk Sea <xref ref-type="bibr" rid="bib1.bibx63" id="paren.58"/> and winter mixing
of surface/sub-surface water <xref ref-type="bibr" rid="bib1.bibx79" id="paren.59"/>. Both productivity peaks occur without
a corresponding increase in aeolian dust at “Station 3” (close to ODP Site 882 at
50<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>00<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> N, 164<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>59<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> E) <xref ref-type="bibr" rid="bib1.bibx77" id="paren.60"/> or in East Asian
winter monsoon records from the Chinese Loess Plateau and other marine sites <xref ref-type="bibr" rid="bib1.bibx84 bib1.bibx100" id="paren.61"/>. Whilst a doubling in aeolian dust does occur at “Station 3” during
the early stages of MIS 5c, this ceases before any increase in <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>, opal or
other proxy at ODP Site 882 <xref ref-type="bibr" rid="bib1.bibx77" id="paren.62"/>. The absence of a significant increase in
bioavailable iron would appear to rule out a major role for iron in driving the two productivity
peaks in MIS 5e and MIS 5b/c. This would be in line with evidence indicating that productivity peaks
during the last deglaciation across the North Pacific Ocean also occur without a corresponding
increase in aeolian dust or other iron source input <xref ref-type="bibr" rid="bib1.bibx41" id="paren.63"/>. Others have also argued that
iron only exerts a secondary or minor control on regional water column productivity in the palaeo-record <xref ref-type="bibr" rid="bib1.bibx40 bib1.bibx44" id="paren.64"/> whilst we are unable to account for possible changes in the flux of bioavailable iron from the Okhotsk Sea, winter mixing and other sources identified above.</p>
<sec id="Ch1.S4.SS2.SSS1">
  <title>Nutrient utilisation and supply</title>
      <p>The deep and intermediate waters of the subarctic North Pacific Ocean contain some of the highest
nutrient levels in the world <xref ref-type="bibr" rid="bib1.bibx98" id="paren.65"/>. Accordingly productivity peaks over
glacial–interglacial cycles, including those covered in this study, have been linked to changes in
the regional halocline and water column stratification which would alter the advection of
nutrient- and carbon-rich sub-surface waters into the photic zone <xref ref-type="bibr" rid="bib1.bibx35 bib1.bibx25" id="paren.66"/>. A key
difference between the two productivity events in MIS 5e and MIS 5b/c is the response of the
biological community to raised photic zone nutrient availability. Although productivity is high
during MIS 5e, values are low for <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">Si</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> at ODP Site 882 (<inline-formula><mml:math display="inline"><mml:mrow><mml:mo>&lt;</mml:mo><mml:mn>1.0</mml:mn></mml:mrow></mml:math></inline-formula> ‰,
<inline-formula><mml:math display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:math></inline-formula>) and for <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>15</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">N</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math display="inline"><mml:mrow><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">6</mml:mn></mml:mrow></mml:math></inline-formula> ‰) at a nearby site
(49<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>72<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> N, 168<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>30<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> E) <xref ref-type="bibr" rid="bib1.bibx11" id="paren.67"/> (Fig. 3). In contrast
during MIS 5b/c the productivity peak is concordant with an increase in
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">Si</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>15</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">N</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> to ca. 1.2–1.3 ‰ and
<inline-formula><mml:math display="inline"><mml:mrow><mml:mo>&gt;</mml:mo><mml:mn mathvariant="normal">6</mml:mn></mml:mrow></mml:math></inline-formula> ‰ respectively (Fig. <xref ref-type="fig" rid="Ch1.F3"/>).</p>
      <p>Changes in <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">Si</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> may reflect either increased biological uptake of silicic
acid (consumption) and/or changes in the supply of silicic acid to the photic zone. The modern-day
regional stratified water column is best represented by a closed system model in which a finite
amount of silicic acid exists for biomineralisation <xref ref-type="bibr" rid="bib1.bibx73" id="paren.68"/>. In contrast an unstratified
water column would be reflected by an open system model with continual supply of silicic acid. By
assuming that the two productivity peaks reflect a weakening in the stratification, an open system
model can be used to investigate the controls on <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">Si</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>:
              <disp-formula id="Ch1.E1" content-type="numbered"><mml:math display="block"><mml:mrow><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">Si</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow><mml:mo>=</mml:mo><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow><mml:mo>+</mml:mo><mml:mi mathvariant="italic">ϵ</mml:mi><mml:mo>⋅</mml:mo><mml:mi>f</mml:mi><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
            where <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> is the isotopic composition of dissolved silicic acid supplied to the photic zone, <inline-formula><mml:math display="inline"><mml:mi mathvariant="italic">ϵ</mml:mi></mml:math></inline-formula>
is the enrichment factor between diatoms and dissolved silicic acid and <inline-formula><mml:math display="inline"><mml:mi>f</mml:mi></mml:math></inline-formula> is the fraction of
utilised <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> remaining in the water. Existing work from the North Pacific Ocean has estimated
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> at 1.23 ‰ and <inline-formula><mml:math display="inline"><mml:mi mathvariant="italic">ϵ</mml:mi></mml:math></inline-formula> as 1.0 <xref ref-type="bibr" rid="bib1.bibx73" id="paren.69"/>. Using changes
in <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> consumption (Eq. <xref ref-type="disp-formula" rid="Ch1.E1"/>) and siliceous productivity (opal), the supply
of <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> into the photic zone can be constrained relative to mean conditions during MIS 5e
as
              <disp-formula id="Ch1.E2" content-type="numbered"><mml:math display="block"><mml:mrow><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mrow><mml:mn mathvariant="normal">4</mml:mn><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mi mathvariant="normal">supply</mml:mi></mml:mrow></mml:msub></mml:mrow><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msub><mml:mtext>Opal</mml:mtext><mml:mtext>sample</mml:mtext></mml:msub><mml:mo>/</mml:mo><mml:msub><mml:mtext>Opal</mml:mtext><mml:mtext>MIS 5e</mml:mtext></mml:msub></mml:mrow><mml:mrow><mml:mfenced open="(" close=")"><mml:mn mathvariant="normal">1</mml:mn><mml:mo>-</mml:mo><mml:msubsup><mml:mi>f</mml:mi><mml:mtext>consumed</mml:mtext><mml:mtext>sample</mml:mtext></mml:msubsup></mml:mfenced><mml:mfenced close="" open="/"><mml:mfenced open="(" close=")"><mml:mn mathvariant="normal">1</mml:mn><mml:mo>-</mml:mo><mml:msubsup><mml:mi>f</mml:mi><mml:mtext>consumed</mml:mtext><mml:mtext>MIS 5e</mml:mtext></mml:msubsup></mml:mfenced></mml:mfenced></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>.</mml:mo></mml:mrow></mml:math></disp-formula>
            Estimates of <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> consumption and supply from Eqs. (<xref ref-type="disp-formula" rid="Ch1.E1"/>) and
(<xref ref-type="disp-formula" rid="Ch1.E2"/>) are only applicable for intervals when the water column represents an open system
(e.g. the productivity peaks in MIS 5e and MIS 5b/c) and are dependant on modern-day estimates of
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> being representative of past conditions. This assumption is based on evidence that <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> is relatively resilient to change, outside of seasonal biological fluxes, over
timescales similar to this study except in extreme circumstances linked to major reductions in the flux of riverine silicon into the ocean <xref ref-type="bibr" rid="bib1.bibx18" id="paren.70"/>. The results show that the
productivity peaks in MIS 5e and MIS 5b/c are both closely correlated with elevated levels of
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> being supplied to the photic zone (Fig. <xref ref-type="fig" rid="Ch1.F3"/>), supporting the
suggestion that these intervals are linked to a reduction in water column stratification and an increase in the
vertical flux of nutrients bearing sub-surface waters into the photic zone <xref ref-type="bibr" rid="bib1.bibx35 bib1.bibx25" id="paren.71"/>. However, whilst the increase in <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> supply in MIS 5b/c is matched by
a corresponding increase in biological consumption of <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, increasing the ratio of
regenerated to preformed nutrients in the ocean interior, the opposite occurs during MIS 5e when the
rates of <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> consumption are at their lowest over the analysed
interval. (Fig. <xref ref-type="fig" rid="Ch1.F3"/>). Whilst reduced <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> consumption during MIS 5e could be
linked to iron limitation, records indicate that aeolian dust deposition was equally low during both
the MIS 5e and the MIS 5b/c productivity peaks. However, as before we are unable to account for changes in iron supply from non-aeolian sources.</p>
</sec>
<sec id="Ch1.S4.SS2.SSS2">
  <?xmltex \opttitle{Implications for $p${$\chem{CO_{2}}$}}?><title>Implications for <inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula><inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula></title>
      <p>Understanding the mechanisms that regulate changes in atmospheric concentrations of <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>
(<inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula><inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>) remains a key objective in palaeoclimatology. Previous research has demonstrated
that the Southern Ocean and low-latitude oceans act as the dominant source/sink of atmospheric <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>
over glacial–interglacial cycles <xref ref-type="bibr" rid="bib1.bibx66 bib1.bibx22 bib1.bibx81" id="paren.72"/>. Whilst the North Pacific
Ocean does not need to be invoked to explain the full amplitude of glacial–interglacial changes,
recent work has advocated a potential role for the region in regulating atmospheric <inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula><inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>
over the last termination <xref ref-type="bibr" rid="bib1.bibx68" id="paren.73"/>.</p>
      <p>Today the net annual ocean–atmosphere exchange of <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> in the subarctic north-west Pacific
Ocean is close to zero, but alters from being a sink of atmosphere <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> in spring to a source
in winter <xref ref-type="bibr" rid="bib1.bibx92 bib1.bibx3" id="paren.74"/> (Fig. <xref ref-type="fig" rid="Ch1.F4"/>a). This seasonal variability can be attributed
to changes in the biological pump and in SST which affects the solubility of <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>
<xref ref-type="bibr" rid="bib1.bibx32 bib1.bibx14 bib1.bibx3" id="paren.75"/>. A weakening of the halocline stratification in MIS 5e and MIS 5b/c
would have increased the advection of nutrient- and carbon-rich waters from the ocean interior,
raising photic zone <inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula><inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mo>(</mml:mo><mml:mi mathvariant="normal">aq</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> and the potential for <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> to be ventilated into
the atmosphere due to an air–sea disequilibrium in <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>. This, however, is dependant on the
response and relative efficiency of the biological pump in taking advantage of the increased
nutrient supply and altering the ratio of regenerated : performed nutrients to re-export carbon
into the deep ocean <xref ref-type="bibr" rid="bib1.bibx80 bib1.bibx81 bib1.bibx52" id="paren.76"/>. Whilst changes in the temperature/thermocline may also have been important, the only SST record for the region <xref ref-type="bibr" rid="bib1.bibx55" id="paren.77"/> does not contain the temporal resolution to investigate this further and does not provide a surface–subsurface depth temperature transect.</p>
      <p>During MIS 5e a scenario of both higher <inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula><inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mo>(</mml:mo><mml:mi mathvariant="normal">aq</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> and incomplete/low rates of nutrient
utilisation suggests the regional ocean could have ventilated <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> into the atmosphere faster
than the soft-tissue biological pump reabsorbed and sequestered <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> into the deep ocean
(Fig. <xref ref-type="fig" rid="Ch1.F4"/>b) despite evidence for higher organic carbon export (BioBa) in this period (Fig. <xref ref-type="fig" rid="Ch1.F3"/>). The culmination of this interval at the end of MIS 5e would have resulted in the
system returning to a stratified state, perhaps similar to the modern-day water column
(Fig. <xref ref-type="fig" rid="Ch1.F4"/>a) with minimal air–sea fluxes of <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>. In contrast the opal productivity peak in
MIS 5b/c is marked by similar levels of photic zone <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> supply as in MIS 5e but with
ca. 20 % higher rates of <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> consumption (Figs. <xref ref-type="fig" rid="Ch1.F3"/> and <xref ref-type="fig" rid="Ch1.F4"/>c). The
combination of high siliceous productivity (opal/<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>) and a highly
efficient biological pump (<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">Si</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>/<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>15</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">N</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>) during this
interval suggests that the net flux of ocean–atmosphere <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> exchanges arising from the
sea–air disequilibrium could have remained close to zero if photosynthetic carbon demand
were similar to the rate of sub-surface carbon flux to the photic zone. Whilst a highly efficient
soft-tissue biological pump raises the possibility for the region to have acted as a net sink of
atmospheric <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, the potential and significance for this is limited by the relatively low
proportion of surface waters which reach the deep ocean interior <xref ref-type="bibr" rid="bib1.bibx26" id="paren.78"/> and low BioBa in this interval (Fig. <xref ref-type="fig" rid="Ch1.F3"/>).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F4"><caption><p>Schematic models showing subarctic north-west Pacific Ocean conditions for <bold>(a)</bold>
modern day: halocline water column with nutrient poor surface waters limiting biological export;
<bold>(b)</bold> MIS 5e: no halocline and enhanced upwelling of nutrient- and carbon-rich sub-surface
waters leading to increased productivity. Low rates of nutrient utilisation suggest a possible
increase in <inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula><inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> and release of <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> to the atmosphere; <bold>(c)</bold> MIS 5b/c:
conditions similar to MIS 5e but with higher rates of nutrient consumption and a more efficient
soft-tissue biological pump limiting/preventing ventilation of <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>.</p></caption>
            <?xmltex \igopts{width=170.716535pt}?><graphic xlink:href="https://www.clim-past.net/11/15/2015/cp-11-15-2015-f04.pdf"/>

          </fig>

      <p>Although the data suggest that changes in the regional photic zone may have contributed to variations
in atmospheric <inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula><inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> during MIS 5, both via the soft-tissue biological pump and associated
changes in ocean alkalinity, it is not possible to quantify the magnitude of any fluxes or access
whether they were accompanied by a change in diatom silicification and cellular Si : C
ratios. Firstly, insufficient purified diatom material remains to measure diatom silicon
concentrations. Secondly, although diatom elemental carbon measurements obtained during the analysis
of <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> increase from <inline-formula><mml:math display="inline"><mml:mrow><mml:mo>&lt;</mml:mo><mml:mn>0.3</mml:mn></mml:mrow></mml:math></inline-formula> wt% in MIS 5e to ca. 0.4 wt% in MIS
5b–d (see Supplement Table S1), the analytical reproducibility for <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> is relatively
high at 0.1 % (1<inline-formula><mml:math display="inline"><mml:mi mathvariant="italic">σ</mml:mi></mml:math></inline-formula>) <xref ref-type="bibr" rid="bib1.bibx34" id="paren.79"/> and measurements are derived from the cell wall
material and not the bulk cellular matter formed <?xmltex \hack{\mbox\bgroup}?>during<?xmltex \hack{\egroup}?><?xmltex \hack{\mbox\bgroup}?>photosynthesis<?xmltex \hack{\egroup}?>. Furthermore, whilst other
cores from the region show a similar double peak in opal productivity during MIS 5 <xref ref-type="bibr" rid="bib1.bibx59" id="paren.80"/>
records at other sites suggest that the second peak is restricted to MIS 5b with no increase in MIS
5c <xref ref-type="bibr" rid="bib1.bibx77" id="paren.81"/>. Such discrepancies either suggest poor stratigraphic controls on the age model for either core, or the potential for significant spatial
variability across the region and reiterates that the magnitude of any ocean–atmosphere fluxes of
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> would be low compared to those occurring elsewhere in the marine system such as the
Southern Ocean and low-latitude oceans.</p>
</sec>
<sec id="Ch1.S4.SS2.SSS3">
  <title>Freshwater controls on siliceous productivity</title>
      <p>Records show that the decline in siliceous productivity for both intervals culminates with large decreases in
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> of ca. 3–5 ‰ from ca. 113 <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">ka</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mi mathvariant="normal">BP</mml:mi></mml:mrow></mml:math></inline-formula> and
85 <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">ka</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="normal">BP</mml:mi></mml:mrow></mml:math></inline-formula> (Fig. <xref ref-type="fig" rid="Ch1.F3"/>, red shading). The magnitude of change is too large to be driven
by reductions in deep water upwelling or shifts in ocean water masses from both higher and lower
latitudes, which would only alter <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">water</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> by ca. 1 ‰
<xref ref-type="bibr" rid="bib1.bibx48" id="paren.82"/>. Instead the drop in <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> suggests an input of isotopically
depleted freshwater that may be similar in origin to events documented at the same site during the
late Pliocene/early Quaternary <xref ref-type="bibr" rid="bib1.bibx85" id="paren.83"/>.</p>
      <p>Although the modern-day regional halocline is maintained by high precipitation and low evaporation <xref ref-type="bibr" rid="bib1.bibx21" id="paren.84"/>, it is difficult to envisage a sufficient increase in precipitation to initiate
a 3–5 ‰ decrease in <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>. This is reiterated by evidence that
monsoonal activity was largely stable during MIS 5b–e <xref ref-type="bibr" rid="bib1.bibx84 bib1.bibx100" id="paren.85"/>. At the same time the
potential for a glacial source is questioned by evidence indicating a restricted glaciation in north-east Russia, closest to ODP Site 882, at the Last Glacial Maximum (LGM) <xref ref-type="bibr" rid="bib1.bibx5 bib1.bibx6" id="paren.86"/>,
although other work suggests these ice sheets may have been considerably larger prior to the LGM
<xref ref-type="bibr" rid="bib1.bibx8 bib1.bibx7" id="paren.87"/>. Recent work has shown that both of the major decreases in
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> coincide with increases in IRD accumulation in some, but not all, cores
from the Okhotsk Sea <xref ref-type="bibr" rid="bib1.bibx64" id="paren.88"/>. It has also been argued that the regional water column was
regulated by significant inputs of meltwater from the North American ice sheets during the last
deglaciation <xref ref-type="bibr" rid="bib1.bibx44" id="paren.89"/>. In either case, the decrease in <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> at the end
of each siliceous productivity peak suggests that inputs of freshwater helped re-establish/strengthen the
halocline, limiting the upwelling of nutrient-/<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>-rich sub-surface waters and biological
activity. However, with the decrease in <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> only occurring after the
initial decline in productivity, freshwater can only be acting as a secondary control in
re-establishing the halocline.</p>
      <p>Previous work has suggested a link between changes in the subarctic north-west Pacific Ocean and the
Southern Ocean <xref ref-type="bibr" rid="bib1.bibx35 bib1.bibx37 bib1.bibx10 bib1.bibx77 bib1.bibx24 bib1.bibx81" id="paren.90"/>. The
most viable mechanisms for synchronous changes between polar regions are temperature- and salinity-driven variations in water column density <xref ref-type="bibr" rid="bib1.bibx10" id="paren.91"/>. For example a cooling of polar SST
would reduce the rate of sub-surface upwelling into the photic zone <xref ref-type="bibr" rid="bib1.bibx16" id="paren.92"/>, lowering nutrient
availability and potentially triggering the initial decline in siliceous productivity. At the same time,
a decrease in SST would increase the sensitivity of the water column to subsequent changes in
salinity, making the region highly vulnerable to inputs of freshwater which would strengthen the
water column and inhibit productivity <xref ref-type="bibr" rid="bib1.bibx80" id="paren.93"/>. Additional reductions in siliceous productivity may
then arise from lower North Atlantic overturning and associated deep-water incursions and upwelling
in the North Pacific <xref ref-type="bibr" rid="bib1.bibx75" id="paren.94"/>. Support for a series of events similar to this at ODP Site
882 lies with the concordant decreases at ODP Site 882 between supplied
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>/<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">Si</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>/opal and Antarctic (<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula>)/NGRIP
(<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">ice</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>) ice-core records <xref ref-type="bibr" rid="bib1.bibx61 bib1.bibx39" id="paren.95"/> at the start of each productivity
decline from ca. 118 and 89 <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">ka</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="normal">BP</mml:mi></mml:mrow></mml:math></inline-formula> respectively (Fig. <xref ref-type="fig" rid="Ch1.F3"/>). The final switch to a low
productivity system then coincides with the later decreases in <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> at 113
and 85 <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">ka</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="normal">BP</mml:mi></mml:mrow></mml:math></inline-formula>, suggesting that the climatic deterioration associated with lower <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula>/<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">ice</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> may have fuelled the increase in precipitation and/or an advancement
of regional glaciers around the North Pacific Basin that triggered the increase in freshwater
input. Whilst it remains unclear what initiated either siliceous productivity peak, it can be speculated that
reductions in freshwater after 100 <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">ka</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="normal">BP</mml:mi></mml:mrow></mml:math></inline-formula> could have weakened the halocline and created the
conditions for the second productivity bloom to eventually develop later in MIS 5b/c.</p>
</sec>
</sec>
<sec id="Ch1.S4.SS3">
  <title>Photic zone changes from MIS 4-5a</title>
      <p>Previous research has documented reduced levels of productivity in the north-west Pacific Ocean
during the last glacial in response to surface water stratification <xref ref-type="bibr" rid="bib1.bibx59 bib1.bibx35 bib1.bibx37 bib1.bibx10 bib1.bibx11 bib1.bibx77 bib1.bibx24 bib1.bibx25" id="paren.96"/>. From the latter half of
MIS 5a onwards records of <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>15</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">N</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">Si</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>/<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> consumption become anti-correlated
(Fig. 3). Combined with a long-term shift to lower rates of <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> supply and higher
rates of <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> consumption, this supports suggestions that changes in dust/iron inputs
in the last glacial may have helped regulate the biological pump by altering the biological demand
for individual nutrients <xref ref-type="bibr" rid="bib1.bibx10 bib1.bibx11 bib1.bibx24 bib1.bibx78" id="paren.97"/>, in this case by
increasing biological uptake of silicon over nitrogen to the extent that <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>
consumption in MIS 4 was up to 40 % higher than during MIS 5e. Elevated <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>
consumption may also indicate that the availability of <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> rather than iron may
have ultimately limited siliceous productivity over this interval, in line with a previous suggestion by
<xref ref-type="bibr" rid="bib1.bibx40" id="text.98"/>.</p>
      <p>Superimposed on a trend of low siliceous productivity during MIS 5a and MIS 4 are two small–moderate
increases in opal at ca. 76–74 <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">ka</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mi mathvariant="normal">BP</mml:mi></mml:mrow></mml:math></inline-formula> and ca. 70 <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">ka</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mi mathvariant="normal">BP</mml:mi></mml:mrow></mml:math></inline-formula> (Fig. <xref ref-type="fig" rid="Ch1.F3"/>, green shading). The
increase at 70 <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">ka</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mi mathvariant="normal">BP</mml:mi></mml:mrow></mml:math></inline-formula> does not coincide with any samples analysed in this study, but the
increase at 76–74 <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">ka</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="normal">BP</mml:mi></mml:mrow></mml:math></inline-formula> coincides with higher <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>,
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>30</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">Si</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> supply/consumption (open model). Similar to
before, both opal peaks culminate with a 2–3 ‰ reduction in <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>
(Fig. <xref ref-type="fig" rid="Ch1.F3"/>, red shading), reiterating the role of freshwater in controlling photic zone
dynamics in an era that coincides with increased monsoonal and thus precipitation variability
<xref ref-type="bibr" rid="bib1.bibx84 bib1.bibx77 bib1.bibx100" id="paren.99"/>. However, whereas the earlier declines in siliceous productivity during MIS
5e and MIS 5b/c are accompanied by reductions in both <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> supply and consumption, here
the declines initially occur with reduced <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> supply and higher rates of
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> consumption. This advocates the aforementioned suggestion that the photic zone
shifted to a new state from the end of MIS 5a, highlighted by further large changes in
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> consumption in MIS 4 that do not coincide with a changes in siliceous productivity or
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">diatom</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> (Fig. 3).</p>
</sec>
</sec>
<sec id="Ch1.S5" sec-type="conclusions">
  <title>Conclusions</title>
      <p>Results here provide evidence for significant temporal changes in the strength and efficiency of the
regional soft-tissue biological pump from MIS 4–5e, altering the ratio of regenerated to preformed
nutrients in the water column. In particular the results show evidence of an inefficient soft-tissue
biological pump from 124 to 114 <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">ka</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mi mathvariant="normal">BP</mml:mi></mml:mrow></mml:math></inline-formula>, creating the potential for the region to have played
a role in maintaining the warm climate of the last interglacial through the ventilation of oceanic
<inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> to the atmosphere. In addition to highlighting temporal changes in the biological pump,
the data also reveal that the end of both these and other siliceous productivity fluxes over the analysed
interval are linked to significant increases in freshwater input to the region,
re-establishing/strengthening the halocline and limiting the sub-surface supply of nutrient- and
carbon-rich waters to the photic zone. However, further work is needed to resolve the source of
these freshwater inputs and the mechanisms responsible for initiating the increase in
siliceous productivity and <inline-formula><mml:math display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Si</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>)</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> supply to the photic zone. Finally, whilst these findings
reiterate earlier work in indicating a highly dynamic and changing water column in the subarctic
North Pacific Ocean during the last glacial–interglacial cycle, further work is needed to assess
the spatial representativeness of these results in other sectors of the subarctic North Pacific
Ocean.</p>
</sec>

      
      </body>
    <back><app-group>
        <supplementary-material position="anchor"><p><bold>The Supplement related to this article is available online at <inline-supplementary-material xlink:href="http://dx.doi.org/10.5194/cp-11-15-2015-supplement" xlink:title="pdf">doi:10.5194/cp-11-15-2015-supplement</inline-supplementary-material>.</bold></p></supplementary-material>
        </app-group><ack><title>Acknowledgements</title><p>Thanks are owed to Eric Galbraith and Sam Jaccard for providing information on the ODP Site 882
age model and previously published BioBa and Opal data. Funding for GEAS was provided in part by
a Natural Environment Research Council (NERC) postdoctoral fellowship award (NE/F012969/1). Finally we thank two anonymous reviewers whose comments helped to improve this manuscript.
<?xmltex \hack{\newline}?><?xmltex \hack{\newline}?>
Edited by: E. McClymont</p></ack><ref-list>
    <title>References</title>

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