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<front>
<journal-meta>
<journal-id journal-id-type="doi">10.1002/(ISSN)1944-8007</journal-id>
<journal-id journal-id-type="publisher-id">GRL</journal-id>
<journal-title-group>
<journal-title xml:lang="en">Geophysical Research Letters</journal-title>
<abbrev-journal-title abbrev-type="publisher" xml:lang="en">Geophys Res Lett</abbrev-journal-title>
</journal-title-group>
<issn publication-format="ppub">0094-8276</issn>
<issn publication-format="epub">1944-8007</issn>
</journal-meta>
<article-meta>
<article-id pub-id-type="doi">10.1029/2022GL100328</article-id>
<article-id pub-id-type="publisher-id">GRL64781</article-id>
<article-id pub-id-type="society-id">2022GL100328</article-id>
<article-categories>
<subj-group subj-group-type="article-subject-classification" xml:lang="en">
<subject>Oceans</subject>
</subj-group>
<subj-group subj-group-type="article-subject-classification" xml:lang="en">
<subject>BIOGEOSCIENCES</subject>
</subj-group>
<subj-group subj-group-type="article-subject-classification" xml:lang="en">
<subject>Bioavailability: chemical speciation and complexation</subject>
</subj-group>
<subj-group subj-group-type="article-subject-classification" xml:lang="en">
<subject>Biosignatures and proxies</subject>
</subj-group>
<subj-group subj-group-type="article-subject-classification" xml:lang="en">
<subject>PLANETARY SCIENCES: ASTROBIOLOGY</subject>
</subj-group>
<subj-group subj-group-type="article-subject-classification" xml:lang="en">
<subject>Origin of life</subject>
</subj-group>
<subj-group subj-group-type="article-subject-classification" xml:lang="en">
<subject>Early environment of Earth</subject>
</subj-group>
<subj-group subj-group-type="article-subject-classification" xml:lang="en">
<subject>INFORMATION RELATED TO GEOLOGIC TIME</subject>
</subj-group>
<subj-group subj-group-type="article-subject-classification" xml:lang="en">
<subject>Precambrian</subject>
</subj-group>
<subj-group subj-group-type="overline" xml:lang="en">
<subject>Research Letter</subject>
</subj-group>
<subj-group subj-group-type="heading" xml:lang="en">
<subject>Research Letter</subject>
<subj-group subj-group-type="heading" xml:lang="en">
<subject>Oceans</subject>
</subj-group>
</subj-group>
</article-categories>
<title-group>
<article-title xml:lang="en">Characterization and Geological Implications of Precambrian Calcite‐Hosted Phosphate</article-title>
<alt-title alt-title-type="left-running-head">Richardson et al.</alt-title>
</title-group>
<contrib-group>
<contrib id="grl64781-cr-0001" contrib-type="author" corresp="yes">
<name>
<surname>Richardson</surname>
<given-names>Jocelyn A.</given-names>
</name>
<contrib-id contrib-id-type="orcid">https://orcid.org/0000-0002-0671-9265</contrib-id>
<email>jocelynr@slac.stanford.edu</email>
<xref ref-type="corresp" rid="correspondenceTo">*</xref>
<xref ref-type="aff" rid="grl64781-aff-0001">
<sup>1</sup>
</xref>
</contrib>
<contrib id="grl64781-cr-0002" contrib-type="author">
<name>
<surname>Roest‐Ellis</surname>
<given-names>Sascha</given-names>
</name>
<xref ref-type="aff" rid="grl64781-aff-0002">
<sup>2</sup>
</xref>
</contrib>
<contrib id="grl64781-cr-0003" contrib-type="author">
<name>
<surname>Phillips</surname>
<given-names>Brian L.</given-names>
</name>
<xref ref-type="aff" rid="grl64781-aff-0003">
<sup>3</sup>
</xref>
</contrib>
<contrib id="grl64781-cr-0004" contrib-type="author">
<name>
<surname>Strauss</surname>
<given-names>Justin V.</given-names>
</name>
<contrib-id contrib-id-type="orcid">https://orcid.org/0000-0003-3298-3227</contrib-id>
<xref ref-type="aff" rid="grl64781-aff-0004">
<sup>4</sup>
</xref>
</contrib>
<contrib id="grl64781-cr-0005" contrib-type="author">
<name>
<surname>Webb</surname>
<given-names>Samuel M.</given-names>
</name>
<xref ref-type="aff" rid="grl64781-aff-0001">
<sup>1</sup>
</xref>
</contrib>
<contrib id="grl64781-cr-0006" contrib-type="author" corresp="yes">
<name>
<surname>Tosca</surname>
<given-names>Nicholas J.</given-names>
</name>
<contrib-id contrib-id-type="orcid">https://orcid.org/0000-0003-4415-4231</contrib-id>
<email>njt41@cam.ac.uk</email>
<xref ref-type="corresp" rid="correspondenceTo">*</xref>
<xref ref-type="aff" rid="grl64781-aff-0005">
<sup>5</sup>
</xref>
</contrib>
</contrib-group>
<aff id="grl64781-aff-0001">
<label>
<sup>1</sup>
</label>

<named-content content-type="organisation-division">SLAC National Accelerator Laboratory</named-content>

<institution>Stanford Synchrotron Radiation Lightsource</institution>

<city>Menlo Park</city>
 <named-content content-type="country-part">CA</named-content>
 <country country="US">USA</country>

</aff>
<aff id="grl64781-aff-0002">
<label>
<sup>2</sup>
</label>

<named-content content-type="organisation-division">Department of Earth Science</named-content>

<institution>University of Oxford</institution>

<city>Oxford</city>
 <country country="GB">UK</country>

</aff>
<aff id="grl64781-aff-0003">
<label>
<sup>3</sup>
</label>

<named-content content-type="organisation-division">Department of Geosciences</named-content>

<institution>Stony Brook University</institution>

<city>Stony Brook</city>
 <named-content content-type="country-part">NY</named-content>
 <country country="US">USA</country>

</aff>
<aff id="grl64781-aff-0004">
<label>
<sup>4</sup>
</label>

<named-content content-type="organisation-division">Department of Earth Sciences</named-content>

<institution>Dartmouth College</institution>

<city>Hanover</city>
 <named-content content-type="country-part">NH</named-content>
 <country country="US">USA</country>

</aff>
<aff id="grl64781-aff-0005">
<label>
<sup>5</sup>
</label>

<named-content content-type="organisation-division">Department of Earth Sciences</named-content>

<institution>University of Cambridge</institution>

<city>Cambridge</city>
 <country country="GB">UK</country>

</aff>
<author-notes>
<corresp id="correspondenceTo"><label>*</label>

<bold>Correspondence to:</bold><break/>
J. A. Richardson and N. J. Tosca,<break/>
<email>jocelynr@slac.stanford.edu</email>;<break/>
<email>njt41@cam.ac.uk</email><break/>

</corresp>
</author-notes>
<pub-date date-type="pub" publication-format="electronic"><day>10</day>
<month>09</month>
<year>2022</year>
</pub-date><pub-date date-type="pub" publication-format="print"><day>16</day>
<month>09</month>
<year>2022</year>
</pub-date><volume>49</volume>
<issue seq="20">17</issue>
<issue-id pub-id-type="doi">10.1002/grl.v49.17</issue-id>
<elocation-id>e2022GL100328</elocation-id>
<history>

<date date-type="rev-recd">
<day>31</day>
<month>08</month>
<year>2022</year>
</date>

<date date-type="received">
<day>07</day>
<month>07</month>
<year>2022</year>
</date>

<date date-type="accepted">
<day>01</day>
<month>09</month>
<year>2022</year>
</date>

</history>
<permissions>
<copyright-statement content-type="issue-copyright">© 2022. The Authors.</copyright-statement>
<copyright-statement content-type="article-copyright">© 2022. The Authors.</copyright-statement>
<copyright-year>2022</copyright-year>
<copyright-holder>© 2022. The Authors.</copyright-holder>
<license>
<ali:license_ref>http://creativecommons.org/licenses/by/4.0/</ali:license_ref>
<license-p>This is an open access article under the terms of the <ext-link ext-link-type="uri" xlink:href="http://creativecommons.org/licenses/by/4.0/">Creative Commons Attribution</ext-link> License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.</license-p>
</license>
</permissions>
<abstract xml:lang="en" abstract-type="main">
<title>Abstract</title>
<p xml:lang="en">Constraints on marine phosphate availability and cycling directly inform our understanding of long‐term biological evolution. However, early Earth phosphate records are sparse, biased toward siliciclastic samples, and susceptible to post‐depositional modification. Well‐preserved shallow marine inorganic carbonate precipitates provide a complementary yet understudied record of phosphate cycling. We combined micro‐X‐ray fluorescence mapping, X‐ray absorption, and Nuclear Magnetic Resonance spectroscopy on samples of Precambrian syndepositional herringbone calcite (HBC) and microspar to characterize phosphorus speciation and distribution in these carbonate fabrics. Phosphorus spectroscopy from synthetic calcite, HBC, and microspar, is qualitatively consistent with a disordered distribution of phosphate. These characteristics are diagnostic of calcite‐hosted phosphate, which is pervasive at low concentrations in HBC and microspar. This study provides evidence that ancient, well‐preserved carbonate fabrics retain phosphate sourced from seawater and highlights the potential for an unaltered archive of marine phosphate concentration over geologic time.</p>
</abstract>
<abstract xml:lang="en" abstract-type="synopsis">
<title>Plain Language Summary</title>
<p xml:lang="en">Phosphorus is a critical nutrient to sustain life on Earth as we know it. Understanding the form and source of phosphorus on the early Earth will enhance our knowledge of the origins and early evolution of life. However, there is no way to directly measure the source, form and abundance of phosphorus in the environment when life was evolving over 2.5 billion years ago. The rock record provides a potential archive to indirectly measure phosphorus from ancient marine environments, yet there are a number of considerations, for example; (a) which minerals are able to record information about marine phosphorus? (b) How do we know those minerals have not been altered over time? In this work, we have identified well‐preserved, unaltered carbonate minerals from ∼2.5 billion and 800 million years ago, that preserve marine phosphate within their mineral structure using micron‐scale techniques. The characterization of this form of phosphorus is important to our understanding of the evolution of the phosphorus cycle over Earth's history.</p>
</abstract>
<abstract xml:lang="en" abstract-type="short">
<title>Key Points</title>
<p xml:lang="en">

<list list-type="bullet">
<list-item>
<p xml:lang="en">Synchrotron analyses identify calcite‐hosted phosphate in well‐preserved Precambrian carbonate fabrics</p>
</list-item>
<list-item>
<p xml:lang="en">Herringbone calcite and synsedimentary microspar serve as an unaltered archive for ancient marine dissolved inorganic phosphate</p>
</list-item>
<list-item>
<p xml:lang="en">Micrite retains abundant apatite mineral micro‐inclusions that may bias bulk calcite‐hosted phosphate or P/Ca records</p>
</list-item>
</list>

</p>
</abstract>
<kwd-group xml:lang="en">
<kwd id="grl64781-kwd-0001">Precambrian</kwd>
<kwd id="grl64781-kwd-0002">phosphorus</kwd>
<kwd id="grl64781-kwd-0003">synchrotron‐XRF</kwd>
<kwd id="grl64781-kwd-0004">NMR spectroscopy</kwd>
<kwd id="grl64781-kwd-0005">XANES spectroscopy</kwd>
<kwd id="grl64781-kwd-0006">carbonate</kwd>
</kwd-group>
<funding-group>
<award-group id="funding-0001">
<funding-source>

<institution-wrap>
<institution>Leverhulme Trust</institution>
<institution-id>http://dx.doi.org/10.13039/501100000275</institution-id>
</institution-wrap>

</funding-source>
<award-id>PLP‐2015‐286</award-id>
</award-group>
</funding-group>
<funding-group>
<award-group id="funding-0002">
<funding-source>

<institution-wrap>
<institution>National Geographic Society</institution>
<institution-id>http://dx.doi.org/10.13039/100006363</institution-id>
</institution-wrap>

</funding-source>
<award-id>CP‐129R‐17</award-id>
</award-group>
</funding-group>
<counts>
<fig-count count="3"/>
<table-count count="0"/>
<page-count count="11"/>
<word-count count="7015"/>
</counts>
</article-meta>
</front>
</article>