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<journal-meta>
<journal-id journal-id-type="publisher-id">Front. Geochem.</journal-id>
<journal-title>Frontiers in Geochemistry</journal-title>
<abbrev-journal-title abbrev-type="pubmed">Front. Geochem.</abbrev-journal-title>
<issn pub-type="epub">2813-5962</issn>
<publisher>
<publisher-name>Frontiers Media S.A.</publisher-name>
</publisher>
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<article-meta>
<article-id pub-id-type="publisher-id">1607472</article-id>
<article-id pub-id-type="doi">10.3389/fgeoc.2025.1607472</article-id>
<article-categories>
<subj-group subj-group-type="heading">
<subject>Geochemistry</subject>
<subj-group>
<subject>Original Research</subject>
</subj-group>
</subj-group>
</article-categories>
<title-group>
<article-title>Lithospheric origin of a diamond from the Rio Sorriso area, Mato Grosso State, Brazil</article-title>
<alt-title alt-title-type="left-running-head">Angellotti et al.</alt-title>
<alt-title alt-title-type="right-running-head">
<ext-link ext-link-type="uri" xlink:href="https://doi.org/10.3389/fgeoc.2025.1607472">10.3389/fgeoc.2025.1607472</ext-link>
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</title-group>
<contrib-group>
<contrib contrib-type="author">
<name>
<surname>Angellotti</surname>
<given-names>A.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
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<contrib contrib-type="author" corresp="yes">
<name>
<surname>Marras</surname>
<given-names>G.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="corresp" rid="c001">&#x2a;</xref>
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<contrib contrib-type="author">
<name>
<surname>Morana</surname>
<given-names>M.</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
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<contrib contrib-type="author">
<name>
<surname>Chariton</surname>
<given-names>S.</given-names>
</name>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
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<contrib contrib-type="author">
<name>
<surname>Stopponi</surname>
<given-names>V.</given-names>
</name>
<xref ref-type="aff" rid="aff4">
<sup>4</sup>
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<contrib contrib-type="author">
<name>
<surname>Medeghini</surname>
<given-names>L.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
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<contrib contrib-type="author">
<name>
<surname>Romano</surname>
<given-names>C.</given-names>
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<xref ref-type="aff" rid="aff5">
<sup>5</sup>
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<contrib contrib-type="author">
<name>
<surname>Correale</surname>
<given-names>A.</given-names>
</name>
<xref ref-type="aff" rid="aff6">
<sup>6</sup>
</xref>
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<contrib contrib-type="author">
<name>
<surname>Bindi</surname>
<given-names>L.</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
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<contrib contrib-type="author">
<name>
<surname>Kaminsky</surname>
<given-names>F. V.</given-names>
</name>
<xref ref-type="aff" rid="aff7">
<sup>7</sup>
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<contrib contrib-type="author" corresp="yes">
<name>
<surname>Stagno</surname>
<given-names>V.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="aff" rid="aff6">
<sup>6</sup>
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<aff id="aff1">
<sup>1</sup>
<institution>Department of Earth Sciences, Sapienza University of Rome</institution>, <addr-line>Roma</addr-line>, <country>Italy</country>
</aff>
<aff id="aff2">
<sup>2</sup>
<institution>Department of Earth Sciences, University of Florence</institution>, <addr-line>Firenze</addr-line>, <country>Italy</country>
</aff>
<aff id="aff3">
<sup>3</sup>
<institution>Center for Advanced Radiation Sources, The University of Chicago</institution>, <addr-line>Chicago</addr-line>, <addr-line>IL</addr-line>, <country>United States</country>
</aff>
<aff id="aff4">
<sup>4</sup>
<institution>CNR - Istituto Officina dei Materiali (IOM)</institution>, <addr-line>Trieste</addr-line>, <country>Italy</country>
</aff>
<aff id="aff5">
<sup>5</sup>
<institution>Department of Science, University of Roma Tre</institution>, <addr-line>Rome</addr-line>, <country>Italy</country>
</aff>
<aff id="aff6">
<sup>6</sup>
<institution>Istituto Nazionale di Geofisica e Vulcanologia</institution>, <addr-line>Palermo</addr-line>, <country>Italy</country>
</aff>
<aff id="aff7">
<sup>7</sup>
<institution>Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Science</institution>, <addr-line>Moscow</addr-line>, <country>Russia</country>
</aff>
<author-notes>
<fn fn-type="edited-by">
<p>
<bold>Edited by:</bold> <ext-link ext-link-type="uri" xlink:href="https://loop.frontiersin.org/people/2358533/overview">Michael Roden</ext-link>, University of Georgia, United States</p>
</fn>
<fn fn-type="edited-by">
<p>
<bold>Reviewed by:</bold> <ext-link ext-link-type="uri" xlink:href="https://loop.frontiersin.org/people/1876475/overview">Abdel-Aal M. Abdel-Karim</ext-link>, Zagazig University, Egypt</p>
<p>
<ext-link ext-link-type="uri" xlink:href="https://loop.frontiersin.org/people/3069859/overview">Izaac Cabral Neto</ext-link>, Geological Survey of Brazil, Brazil</p>
</fn>
<corresp id="c001">&#x2a;Correspondence: V. Stagno, <email>vincenzo.stagno@uniroma1.it</email>; G. Marras, <email>giulia.marras@uniroma1.it</email>
</corresp>
</author-notes>
<pub-date pub-type="epub">
<day>15</day>
<month>08</month>
<year>2025</year>
</pub-date>
<pub-date pub-type="collection">
<year>2025</year>
</pub-date>
<volume>3</volume>
<elocation-id>1607472</elocation-id>
<history>
<date date-type="received">
<day>07</day>
<month>04</month>
<year>2025</year>
</date>
<date date-type="accepted">
<day>17</day>
<month>07</month>
<year>2025</year>
</date>
</history>
<permissions>
<copyright-statement>Copyright &#xa9; 2025 Angellotti, Marras, Morana, Chariton, Stopponi, Medeghini, Romano, Correale, Bindi, Kaminsky and Stagno.</copyright-statement>
<copyright-year>2025</copyright-year>
<copyright-holder>Angellotti, Marras, Morana, Chariton, Stopponi, Medeghini, Romano, Correale, Bindi, Kaminsky and Stagno</copyright-holder>
<license xlink:href="http://creativecommons.org/licenses/by/4.0/">
<p>This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.</p>
</license>
</permissions>
<abstract>
<p>Diamonds are unique samples that enlarge our vision of the physical and chemical reactions occurring in Earth&#x2019;s deep, inaccessible mantle. By investigating the minerals and fluids trapped within them, it is possible to ascertain the key conditions relevant to diamond formation, such as pressure, temperature, and oxygen fugacity. In this study, we investigated a diamond from the Rio Sorriso area, Ju&#xed;na (Brazil), a site known for the high abundance of sublithospheric diamonds discovered there. The diamond contained both colorless and greenish optically visible inclusions of Na&#x2013;Cr-bearing diopside, high-Mg olivine, and enstatite. Thermobarometric estimates of the polished and entrapped inclusions suggest that the diamond likely formed at pressures between 4 and 5 GPa and temperatures of 1,050&#x2009;&#xb0;C&#x2013;1,150&#x2009;&#x2009;&#xb0;C. Major and trace elements data from one polished clinopyroxene provide evidence of interaction between the local peridotite and an oxidized Na-rich carbonated melt&#x2014;a generally proposed growth medium from which diamonds may have crystallized. Our study thus demonstrates that diamonds from underneath the Amazonian craton did not originate solely at lower mantle depths but also within a metasomatized lithospheric mantle.</p>
</abstract>
<kwd-group>
<kwd>thermobarometry</kwd>
<kwd>redox</kwd>
<kwd>synchrotron M&#xf6;ssbauer</kwd>
<kwd>metasomatism</kwd>
<kwd>Amazonian craton</kwd>
</kwd-group>
<custom-meta-wrap>
<custom-meta>
<meta-name>section-at-acceptance</meta-name>
<meta-value>Solid Earth Geochemistry</meta-value>
</custom-meta>
</custom-meta-wrap>
</article-meta>
</front>
<body>
<sec id="s1">
<title>1 Introduction</title>
<p>The investigation of mineral inclusions in diamonds, although infrequent, represents a fundamental tool for shedding light on the fluid-mediated processes that affect the deep volatile cycle at the local scale (<xref ref-type="bibr" rid="B70">Stagno and Fei, 2020</xref>). In 2008, analysis of 2,844 inclusion-bearing lithospheric diamonds revealed high affinity for peridotite (P-type)-like mineral assemblages (65%), followed by eclogite (E-type)-like inclusions (33%; <xref ref-type="bibr" rid="B67">Stachel and Harris, 2008</xref>). P-types exhibiting extensive melting, such as harzburgitic inclusions, have been frequently reported, while those recording refertilization, such as wehrlitic inclusions, are rare, representing only 0.2% of samples. In a recently updated dataset, <xref ref-type="bibr" rid="B69">Stachel et al. (2022)</xref> reported a total of 20 wehrlitic inclusions for 12 diamonds extracted from cratonic locations such as Buffalo Head (<xref ref-type="bibr" rid="B8">Banas et al., 2007</xref>), Superior (<xref ref-type="bibr" rid="B68">Stachel et al., 2018</xref>), Kalahari (<xref ref-type="bibr" rid="B17">Daniels and Gurney, 1999</xref>; <xref ref-type="bibr" rid="B77">Viljoen et al., 2014</xref>), Kimberley (<xref ref-type="bibr" rid="B30">Jaques et al., 1989</xref>), and Yakutia (<xref ref-type="bibr" rid="B62">Sobolev et al., 1977</xref>; <xref ref-type="bibr" rid="B64">2004</xref>). For these inclusions (<xref ref-type="sec" rid="s12">Supplementary Table S1</xref>), a wehrlitic (deep) origin has been proposed based on the CaO and Cr<sub>2</sub>O<sub>3</sub> content of the entrapped garnet (grt) according to the proper classification scheme (<xref ref-type="bibr" rid="B22">Gr&#xfc;tter et al., 2004</xref>). Additional inclusions are represented by olivine (ol) and clinopyroxene (cpx). Interestingly, some of the listed diamonds could be classified as type IaAB, thereby allowing nitrogen-based thermometric analyses, which resulted in residence temperatures (T) between approximately 1,070 &#x2009;&#xb0;C and 1,320 &#x2009;&#xb0;C (<xref ref-type="bibr" rid="B69">Stachel et al., 2022</xref>). On the other hand, a wehrlitic component has been proposed in the case of diamonds with a mixed paragenesis (i.e., eclogitic and wehrlitic), such as in the case of type II K14 diamond (Buffalo Head Terrane; <xref ref-type="bibr" rid="B18">Davies et al., 2004</xref>), type IaAB diamond Gahcho Kue (Slave Craton; <xref ref-type="bibr" rid="B69">Stachel et al., 2022</xref>), and type IaA Childliak (Hall Peninsula; <xref ref-type="bibr" rid="B69">Stachel et al., 2022</xref>). No lithospheric diamond inclusions have been reported from the Rio Sorriso area, Ju&#xed;na (Brazil). Diamonds from Rio Sorriso, in the Amazonian Craton, have been classified as sublithospheric, a type known for having originated at lower mantle depths (<xref ref-type="bibr" rid="B24">Hayman et al., 2005</xref>; <xref ref-type="bibr" rid="B32">Kaminsky et al., 2023</xref>). In contrast, some mantle xenoliths from the same area, transported to the surface by kimberlitic volcanism (92&#x2013;95&#xa0;Ma in age; <xref ref-type="bibr" rid="B25">Heaman et al., 1998</xref>; <xref ref-type="bibr" rid="B10">Cabral-Neto et al., 2025</xref>), present both peridotitic and eclogitic mineralogy. A recent study, based on the exceptional age of sublithospheric Ju&#xed;na diamonds, dates their formation to 610&#x2013;450&#xa0;Ma from a peri-Gondwanan subduction system, followed by their upwelling to the lithospheric keel of the Gondwana supercontinent and subsequent continental accretion and break-up (<xref ref-type="bibr" rid="B74">Timmerman et al., 2023</xref>).</p>
<p>This study reports analyses of the first lithospheric diamond from Rio Sorriso containing at least ten visible mineral inclusions (<xref ref-type="fig" rid="F1">Figure 1a</xref>), one of which polished to the surface (<xref ref-type="fig" rid="F1">Figure 1b</xref>). We employed several techniques, including <italic>in situ</italic> analyses, to investigate the chemistry (i.e., major and trace elements and the iron oxidation state) and mineralogy of the inclusions in order to determine the pressure, temperature, and redox (P-T-fo<sub>2</sub>) conditions of entrapment along with the composition of the growth medium. The combination of several techniques applied to a single diamond enables unique mineral characterization (<xref ref-type="bibr" rid="B63">Sobolev et al., 2000</xref>; <xref ref-type="bibr" rid="B51">Pearson et al., 2014</xref>; <xref ref-type="bibr" rid="B46">Nestola et al., 2017</xref>; <xref ref-type="bibr" rid="B47">Nestola et al., 2019</xref>; <xref ref-type="bibr" rid="B75">Tschauner et al., 2021</xref>; <xref ref-type="bibr" rid="B12">Carvalho et al., 2024</xref>) and a better understanding of the redox processes at the time of diamond formation (<xref ref-type="bibr" rid="B29">Jacob et al., 2016</xref>; <xref ref-type="bibr" rid="B14">Chen et al., 2018</xref>; <xref ref-type="bibr" rid="B6">Anzolini et al., 2020</xref>; <xref ref-type="bibr" rid="B48">Nestola et al., 2023</xref>). Our study not only contributes to the actual dataset but also represents the first report of the possible existence of lithospheric diamonds underneath the Amazonian craton, with evidence of metasomatic fluid&#x2013;rock interactions.</p>
<fig id="F1" position="float">
<label>FIGURE 1</label>
<caption>
<p>
<bold>(a)</bold> Optical image of COMSK3 diamond and the ten visible inclusions. <bold>(b)</bold> Detail of <italic>Inc1</italic> showing the slightly inclined orientation underneath the diamond surface.</p>
</caption>
<graphic xlink:href="fgeoc-03-1607472-g001.tif">
<alt-text content-type="machine-generated">Microscope images show mineral inclusions within a crystal. Panel a shows multiple inclusions labeled Inc1 to Inc10, with a scale of five hundred micrometers. Panel b is a close-up of a green inclusion with a scale of one hundred micrometers.</alt-text>
</graphic>
</fig>
</sec>
<sec sec-type="materials|methods" id="s2">
<title>2 Materials and methods</title>
<sec id="s2-1">
<title>2.1 Macroscopic description and major and trace element analyses of the investigated diamond</title>
<p>The lithospheric diamond (COMSK3) under investigation is octahedral, with two polished parallel surfaces cut along the [100] crystallographic face, measuring approximately 1.3 &#xd7; 1.6&#xa0;mm with a thickness of &#x223c;0.6&#xa0;mm. The diamond contains ten visible colorless and pale-green mineral inclusions (hereafter, <italic>Inc</italic>) ranging in size from 0.02 to 0.2&#xa0;mm (<xref ref-type="fig" rid="F1">Figures 1a,b</xref>). The images of the diamond and its inclusions were acquired using an AmScope stereoscope under reflected and transmitted light, while birefringence colors were observed under polarized light with a Leica DM750 microscope (<xref ref-type="sec" rid="s12">Supplementary Figure S1a-c</xref>). Both microscopes are equipped with their own high-resolution camera, and the images were collected with integrated software provided by the manufacturer.</p>
<p>Textural and morphological analyses on the exposed inclusion (<xref ref-type="sec" rid="s12">Supplementary Figure S2a</xref>) were performed with a ZEISS EVO MA10 scanning electron microscope (SEM) at the CNR- Istituto di Geologia Ambientale e Geoingegneria (IGAG; Sapienza University of Rome, Italy), which is equipped with an AZTEC-integrated energy-dispersive X ray spectrometer (EDS). The analyses were performed with 20&#xa0;kV and 50&#xa0;pA, using cobalt as standard. The chemical analyses on <italic>Inc1</italic> (<xref ref-type="sec" rid="s12">Supplementary Figure S2b</xref>; <xref ref-type="sec" rid="s12">Supplementary Table S2</xref>) were performed using a JEOL JXA-8230 electron probe microanalyzer (EPMA) equipped with five spectrometers at the Department of Earth Sciences of the University of Florence (Italy). An accelerating voltage of 15&#xa0;kV and 20&#xa0;nA with a defocused electron beam of 3&#xa0;&#xb5;m diameter size were used. Oxides and silicates were employed as standards: albite for Si and Na, olivine for Mg, plagioclase and garnet for Al, bustamite for Mn, diopside for Ca, ilmenite (Smithsonian standard) for Ti and Fe, chromite for Cr, and sanidine for K. Chemical maps were also acquired (<xref ref-type="sec" rid="s12">Supplementary Figure S3</xref>). Trace element analyses of the exposed <italic>Inc1</italic> (<xref ref-type="sec" rid="s12">Supplementary Table S2</xref>) were performed by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) with an Agilent-7500 CX plasma mass spectrometer at the Istituto Nazionale di Geofisica e Vulcanologia (INGV) of Palermo (Italy). The analyses were performed with a constant laser frequency rate of 10&#xa0;Hz, fluency of 15&#xa0;J/cm<sup>2</sup>, and He flux of 0.8&#xa0;L&#xa0;min<sup>-1</sup> in the ablation cell. A diameter of 32&#xa0;&#xb5;m for the laser spot was used during the ablation. One analysis each was conducted in the core and rim of <italic>Inc1</italic>, while the background was collected from two spots on the surface of the diamond host. The accuracy of the analyses (RSD%) was calculated by repeated analysis of the USGS basaltic reference glass BCR-2G and was &#x2264; 15% for all the elements.</p>
</sec>
<sec id="s2-2">
<title>2.2 <italic>In situ</italic> synchrotron M&#xf6;ssbauer spectroscopy</title>
<p>The Fe oxidation state of three mineral inclusions, one exposed to the polished surface (<italic>Inc1)</italic> and two entrapped (<italic>Inc2</italic> and <italic>Inc5</italic>), was determined by <italic>in situ</italic> synchrotron M&#xf6;ssbauer spectroscopy at the beamline ID18 (<xref ref-type="bibr" rid="B58">R&#xfc;ffer and Chumakov, 1996</xref>) of the European Synchrotron Radiation Facility (ESRF) in Grenoble (France). The typical energy for the M&#xf6;ssbauer effect at 14.4&#xa0;keV was obtained through the (111) Bragg reflection of a <sup>57</sup>FeBO<sub>3</sub> crystal mounted on a Wissel velocity transducer driven with a sinusoidal wave form (<xref ref-type="bibr" rid="B52">Potapkin et al., 2012</xref>). The beam was focused to an area of 6 &#xd7; 15&#xa0;&#x3bc;m<sup>2</sup> using Kirkpatrick&#x2013;Baez mirrors. The velocity scale of &#xb1;6&#xa0;mm/s was calibrated using an &#x3b1;-Fe foil of 25&#xa0;&#x3bc;m of thickness. The spectra were acquired within 2.5 and 4.5&#xa0;h and fitted using a pseudo-Voigt line shape with MossA software (<xref ref-type="bibr" rid="B54">Prescher et al., 2012</xref>). <xref ref-type="bibr" rid="B45">Nestola et al. (2016)</xref> and <xref ref-type="bibr" rid="B38">Marras et al. (2023)</xref> described the advantage of this technique, which consisted of a much higher spatial resolution of the measurement (&#x223c;15&#xa0;&#x3bc;m) than the M&#xf6;ssbauer milliprobe source that, in turn, allows the acquisition of Fe<sup>3&#x2b;</sup>/&#x3a3;Fe values from multiple inclusions either entrapped or exposed. <xref ref-type="sec" rid="s12">Supplementary Figures S4a&#x2013;c</xref> show the spectra of <italic>Inc1</italic> and <italic>Inc2</italic>, collected in approximately 4.5&#xa0;h and 2.5&#xa0;h, respectively, and of <italic>Inc5</italic>, collected in 2.5&#xa0;h. The M&#xf6;ssbauer spectra of cpx inclusions were fitted with two doublets for Fe<sup>2&#x2b;</sup> and one for Fe<sup>3&#x2b;</sup>, following <xref ref-type="bibr" rid="B11">Canil and O&#x27;Neill (1996)</xref> and <xref ref-type="bibr" rid="B72">Stagno et al. (2015)</xref>. The component area ratios of the Fe<sup>2&#x2b;</sup> doublets were left unfixed but constrained to the same value to account for the preferred crystal orientation (<xref ref-type="bibr" rid="B40">McCammon et al., 2000</xref>). The spectrum of ol was also fitted with two doublets for Fe<sup>2&#x2b;</sup> and one for Fe<sup>3&#x2b;</sup>. The tiny contribution of Fe from the Be window was considered by fitting all the spectra with an extra singlet (central shift of 0.3249&#xa0;mm/s), the position of which was determined through measurements of the background performed during the analytical session. <xref ref-type="sec" rid="s12">Supplementary Table S4</xref> summarizes the hyperfine parameters for each of the three analyzed minerals and the calculated Fe<sup>3&#x2b;</sup>/&#x2211;Fe. The quadrupole splitting (QS) and center shift (CS) are reported in <xref ref-type="sec" rid="s12">Supplementary Figures S5a and b</xref> (cpx and ol, respectively) along with the known hyperfine parameter for ol (<xref ref-type="bibr" rid="B11">Canil and O&#x27;Neill, 1996</xref>; <xref ref-type="bibr" rid="B20">Ejima et al., 2018</xref>; <xref ref-type="bibr" rid="B38">Marras et al., 2023</xref>), for peridotitic cpx (<xref ref-type="bibr" rid="B11">Canil and O&#x27;Neill, 1996</xref>), for natural eclogitic cpx, and for synthetic eclogitic cpx (<xref ref-type="bibr" rid="B72">Stagno et al., 2015</xref>) (<xref ref-type="sec" rid="s12">Supplementary Table S4</xref>). Hyperfine parameters for eclogitic cpx inclusions in diamonds (<xref ref-type="bibr" rid="B39">McCammon et al., 1998</xref>) are also shown in <xref ref-type="sec" rid="s12">Supplementary Table S4</xref>.</p>
</sec>
<sec id="s2-3">
<title>2.3 Raman and &#xb5;-FTIR spectroscopy</title>
<p>The Horiba LabRam HR 800 Raman spectrometer at the University of Roma Tre (Rome, Italy) was used to identify the entrapped mineral inclusions, infer their chemical composition, and verify the presence of residual stress. A total of 57 spectra were acquired in the range of 100&#x2013;4,000&#xa0;cm<sup>&#x2212;1</sup> from eight of the ten inclusions, one of which (<italic>Inc6</italic>) appeared to consist of two smaller inclusions (<italic>Inc6a</italic> and <italic>Inc6b</italic>). The instrument is equipped with an attenuated doubled Nd<sup>3&#x2b;</sup>: YAG laser with a wavelength of 532&#xa0;nm and an optical microscope. The laser power on the sample surface was 60&#xa0;mW, and the analyses were performed with a 100&#xd7; objective and 5&#xa0;&#x3bc;m<sup>2</sup> spot size. Pure silicon was used as a standard. Instrumental settings consisted of 600 grooves/mm grating density, a confocal hole of 300&#xa0;&#x3bc;m, and a slit of 200&#xa0;&#x3bc;m, with an exposure time of 60&#xa0;s. Each collected spectrum was the average of three acquisitions to improve the signal-to-noise ratio. The acquired spectra were preliminarily compared with those available from the RUFF database (<xref ref-type="bibr" rid="B35">Lafuente et al., 2015</xref>). The precise positions of the spectral bands were determined through deconvolution using PeakFit software. <xref ref-type="sec" rid="s12">Supplementary Figures S6a&#x2013;h</xref> show the collected spectra along with the zoomed image of the analyzed inclusions. Spectra for <italic>Inc8</italic> and <italic>Inc9</italic> are not shown due to their low-quality signal caused by the small sizes (less than 20&#xa0;&#xb5;m) of the inclusions. To account for the temporal drift in the Raman band position, the collected spectra were corrected with respect to the peak at 1,330.4 cm<sup>&#x2212;1</sup> measured on the diamond surface. In each of the collected spectra, a broad band appears at &#x223c;1,150&#xa0;cm<sup>&#x2212;1</sup>, which we attribute to a residual solvent (i.e., ethanol) used to clean the diamond prior to the Raman analyses. The occurrence of hydroxyl groups could be investigated only in <italic>Inc1</italic> by reflectance micro-Fourier-transform infrared spectroscopy (&#xb5;-FTIR) using an IR Nicolet iS50 spectrometer coupled with the Nicolet Continuum IR microscope, available at the Department of Earth Sciences, Sapienza University of Rome, Italy. The spectra were collected in the range of 4,000-650&#xa0;cm<sup>&#x2212;1</sup> with a spatial resolution of 4&#xa0;cm<sup>&#x2212;1</sup> averaged from 300 scans and a 50 &#xd7; 50-&#x3bc;m spot size. Additional measurements were conducted by transmission &#xb5;-FTIR spectroscopy at the Material Science branch of SISSI beamline of CNR-IOM at Elettra Sincrotrone Trieste (Italy) to characterize the host diamond for possible thermometric applications; a smaller and circular detectable area avoids the inference of small inclusions when collecting transmission-mode spectra. The analyses were carried out between 6,000 and 600&#xa0;cm<sup>&#x2212;1</sup> using a Vertex 70 v interferometer coupled with a Hyperion2000 microscope (Bruker Optics), liquid N<sub>2</sub>-cooled HgCdTe (MCT) detector, and a KBr beam splitter. Measurements were conducted using the synchrotron source with a resolution of 2&#xa0;cm<sup>&#x2212;1</sup> and an aperture of 30&#x2013;60&#xa0;&#x3bc;m by collecting five to ten acquisitions per area of 128 scans each. The &#xb5;-FTIR spectra were elaborated using OPUS and Spectragryph (<xref ref-type="bibr" rid="B42">Menges, 2020</xref>) software programs.</p>
</sec>
<sec id="s2-4">
<title>2.4 X-ray diffraction and tomographic analyses</title>
<p>Structural information on the entrapped mineral inclusions was acquired by <italic>in situ</italic> synchrotron single-crystal X-ray diffraction (SCXRD) at the GSECARS 13BM-D beamline of the Argonne National Laboratory (Chicago, USA). Prior to the SCXRD measurements, the diamond was scanned, and its inclusions were localized with the help of X-ray computed microtomography (CMT; <xref ref-type="sec" rid="s12">Supplementary Figure S7</xref>) in conjunction with the SCXRD setup at beamline 13BM-D (<xref ref-type="bibr" rid="B73">Sutton et al., 2022</xref>). For the CMT measurements, a monochromatic beam at 30&#xa0;keV was defocused to provide a large field of view on a scintillator plate. A Mitutoyo 5&#xd7; objective attached to a 75-mm tube allowed a pixel resolution of 2.08&#xa0;&#xb5;m. A total of 900 frames with 0.2&#xb0; step and 2-s exposure was collected as the diamond rotated. Tomographic reconstruction of the projections was carried out with the help of IDL-based software available at the beamline. The reconstructed images were used to accurately place the inclusion of interest in the center of the X-ray rotation. Subsequently, the same monochromatic beam was focused on a 20 &#xd7; 20&#xa0;&#x3bc;m beam, and the diffraction setup was automatically railed in. The X-ray diffraction system was equipped with a Pilatus 1M CdTe detector. The sample&#x2013;detector distance was set to 227.91&#xa0;mm and the energy at 30&#xa0;keV (&#x3bb; &#x3d; 0.4133&#xa0;&#xc5;). SCXRD data collection was performed as a series of &#x3c9; scans with a step of 0.5&#xb0; and 10&#xa0;s exposure/step over a &#xb1;35&#xb0; range. Single-crystal X-ray diffraction data were collected on <italic>Inc1</italic>, <italic>Inc4</italic>, <italic>Inc5</italic>, <italic>Inc6a</italic>, and <italic>Inc6b</italic>; the unit-cell parameters are reported in <xref ref-type="sec" rid="s12">Supplementary Figure S5</xref>. The crystallinity of the targeted inclusion was initially verified using Dioptas (<xref ref-type="bibr" rid="B53">Prescher and Prakapenka, 2015</xref>), followed by further analysis of the unit-cell determination, integration of the reflection intensities, and empirical absorption correction using the CrysAlisPro software package. The refinements were performed using SHELXL (<xref ref-type="bibr" rid="B60">Sheldrick, 2015</xref>). Charged scattering curves (<xref ref-type="bibr" rid="B55">Prince, 2004</xref>) were employed in the refinement of the olivine crystal structures. EosFit-Pinc software (<xref ref-type="bibr" rid="B3">Angel et al., 2017</xref>) was employed to determine the final pressure of the inclusion at ambient conditions (P<sub>inc</sub>) and pressure of entrapment (P<sub>trap</sub>).</p>
</sec>
</sec>
<sec sec-type="results" id="s3">
<title>3 Results</title>
<sec id="s3-1">
<title>3.1 Optical, textural, and chemical analyses of the inclusions</title>
<p>The diamond examined under polarized transmitted light revealed a typical birefringence (<xref ref-type="bibr" rid="B36">Lang, 1967</xref>; <xref ref-type="bibr" rid="B26">Howell et al., 2012</xref>) which consisted of the formation of strain-nodules caused by the stressed <italic>Inc4</italic> and <italic>Inc5</italic> (<xref ref-type="sec" rid="s12">Supplementary Figure S1a</xref>). <xref ref-type="sec" rid="s12">Supplementary Figures S1b and c</xref> show the (sub)euhedral shape of the inclusions varying from rounded (<italic>Inc5</italic>; <xref ref-type="sec" rid="s12">Supplementary Figure S1b</xref>) to prismatic (<italic>Inc6</italic>; <xref ref-type="sec" rid="s12">Supplementary Figure S1c</xref>). These images highlight both the presence of composite inclusions (e.g., <italic>Inc6</italic> is composed of two tiny inclusions, <italic>Inc6a</italic> and <italic>Inc6b</italic>, positioned &#x223c;120&#xb0; from each other) and the occurrence of tiny radial fractures departing from the inclusions, which are generally much shorter than the inclusion size, along with a dark brownish and wavy rim. Some inclusions are rimmed by dark halos, interpreted by <xref ref-type="bibr" rid="B1">Agros&#xec; et al. (2019)</xref> as the residue of carbonate-bearing fluids from which the diamond might have formed. Striations, commonly referred to as stepped-face growth, are visible on the external surface of the diamond (<xref ref-type="sec" rid="s12">Supplementary Figure S8</xref>) and represent resorption features formed during transport by oxidized ascending magma (<xref ref-type="bibr" rid="B21">Fedortchouk et al., 2019</xref>). The textural analysis of the exposed polished inclusion <italic>Inc1</italic> shows the presence of radial fractures and a (sub)euhedral shape (<xref ref-type="fig" rid="F1">Figure 1b</xref>). The chemical analysis of the polished inclusion (<xref ref-type="sec" rid="s12">Supplementary Table S2</xref>) appears homogeneous, which is also confirmed by compositional maps (<xref ref-type="sec" rid="s12">Supplementary Figure S3</xref>). The core-to-rim chemical composition of <italic>Inc1</italic> shows a slight decrease of MgO (from 14.00 to 13.47&#xa0;wt%), CaO (from 14.30 to 13.98&#xa0;wt%), and Na<sub>2</sub>O (from 3.79 to 3.68&#xa0;wt%), while the other oxides remain constant within the uncertainty of the measurement. The obtained average composition calculated from the four analyses, with totals close to 100&#xa0;wt%, is 54.82 (&#xb1;0.63) wt% SiO<sub>2</sub>, 0.04 (&#xb1;0.01) wt% TiO<sub>2</sub>, 2.57 (&#xb1;0.05) wt% Al<sub>2</sub>O<sub>3</sub>, 6.33 (&#xb1;0.08) wt% Cr<sub>2</sub>O<sub>3</sub>, 1.82 (&#xb1;0.06) wt% FeO, 0.05 (&#xb1;0.01) wt% MnO, 13.61 (&#xb1;0.32) wt% MgO, 14.11 (&#xb1;0.23) wt% CaO, 3.73 (&#xb1;0.07) wt% Na<sub>2</sub>O, and 0.50 (&#xb1;0.01) wt% K<sub>2</sub>O. On the basis of six oxygen atoms, the chemical formula of the polished inclusion can be written as<disp-formula id="equ1">
<mml:math id="m1">
<mml:mrow>
<mml:mrow>
<mml:mrow>
<mml:mfenced open="(" close=")" separators="|">
<mml:mrow>
<mml:msub>
<mml:mtext>Ca</mml:mtext>
<mml:mn>0.56</mml:mn>
</mml:msub>
<mml:msub>
<mml:mtext>Na</mml:mtext>
<mml:mn>0.27</mml:mn>
</mml:msub>
<mml:msub>
<mml:mi mathvariant="normal">K</mml:mi>
<mml:mn>0.02</mml:mn>
</mml:msub>
<mml:msubsup>
<mml:mtext>Fe</mml:mtext>
<mml:mn>0.05</mml:mn>
<mml:mrow>
<mml:mn>2</mml:mn>
<mml:mo>&#x2b;</mml:mo>
</mml:mrow>
</mml:msubsup>
<mml:msub>
<mml:mtext>Mg</mml:mtext>
<mml:mn>0.10</mml:mn>
</mml:msub>
</mml:mrow>
</mml:mfenced>
</mml:mrow>
<mml:mrow>
<mml:mfenced open="(" close=")" separators="|">
<mml:mrow>
<mml:msub>
<mml:mtext>Mg</mml:mtext>
<mml:mn>0.69</mml:mn>
</mml:msub>
<mml:msubsup>
<mml:mtext>Cr</mml:mtext>
<mml:mn>0.19</mml:mn>
<mml:mrow>
<mml:mn>3</mml:mn>
<mml:mo>&#x2b;</mml:mo>
</mml:mrow>
</mml:msubsup>
<mml:msub>
<mml:mtext>Al</mml:mtext>
<mml:mn>0.11</mml:mn>
</mml:msub>
<mml:msubsup>
<mml:mtext>Fe</mml:mtext>
<mml:mn>0.01</mml:mn>
<mml:mrow>
<mml:mn>3</mml:mn>
<mml:mo>&#x2b;</mml:mo>
</mml:mrow>
</mml:msubsup>
</mml:mrow>
</mml:mfenced>
</mml:mrow>
</mml:mrow>
<mml:msub>
<mml:mtext>Si</mml:mtext>
<mml:mn>2.00</mml:mn>
</mml:msub>
<mml:msub>
<mml:mi mathvariant="normal">O</mml:mi>
<mml:mn>6</mml:mn>
</mml:msub>
<mml:mo>,</mml:mo>
</mml:mrow>
</mml:math>
</disp-formula>identified as a diopside with &#x223c;20% of kosmochlor (NaCrSi<sub>2</sub>O<sub>6</sub>) component and ratios of Cr/(Cr &#x2b; Al) (Cr) of 0.63 and Mg/(Mg &#x2b; Fe) (Mg&#x23;) of 0.93.</p>
</sec>
<sec id="s3-2">
<title>3.2 Spectroscopic identification of the inclusions and diamond classification</title>
<p>
<italic>Inc1</italic>, <italic>Inc2</italic>, and <italic>Inc4</italic> (<xref ref-type="sec" rid="s12">Supplementary Figures S6a,b,d</xref>) exhibit the characteristic vibrational features of a diopside with major peaks at 333&#x2013;341, 403&#x2013;407, and 558&#x2013;564&#xa0;cm<sup>&#x2212;1</sup> related to metal-oxygen translation, 672&#x2013;678 cm<sup>&#x2212;1</sup> (&#x3bd;11) caused by stretching vibrations of bridging O&#x2013;Si&#x2013;O atoms, and 1,014&#x2013;1,021 cm<sup>&#x2212;1</sup> (&#x3bd;16) caused by stretching vibrations of non-bridging O&#x2013;Si&#x2013;O atoms (<xref ref-type="bibr" rid="B16">Chopelas, 1999</xref>; <xref ref-type="bibr" rid="B27">Huang et al., 2000</xref>; <xref ref-type="bibr" rid="B79">Wang and Gasparik, 2001</xref>). The consistency of the vibrational modes, especially for &#x3bd;11, between <italic>Inc1, Inc2, and Inc4</italic> (<xref ref-type="sec" rid="s12">Supplementary Table S6</xref>) might indicate that they all have the same chemical composition. According to the parametrization of the Raman shift of &#x3bd;11 as a function of CaO, MgO, Na<sub>2</sub>O, Al<sub>2</sub>O<sub>3</sub>, and Cr&#x23; (<xref ref-type="bibr" rid="B31">Kalugina and Zedgenizov, 2020</xref>), these Cr-clinopyroxene inclusions have compositions between peridotitic and eclogitic, with low Al<sub>2</sub>O<sub>3</sub> content of approximately 3&#xa0;wt% calculated as<disp-formula id="e1">
<mml:math id="m2">
<mml:mrow>
<mml:msub>
<mml:mtext>Al</mml:mtext>
<mml:mn>2</mml:mn>
</mml:msub>
<mml:msub>
<mml:mi mathvariant="normal">O</mml:mi>
<mml:mn>3</mml:mn>
</mml:msub>
<mml:mtext>&#x2009;</mml:mtext>
<mml:mrow>
<mml:mfenced open="(" close=")" separators="|">
<mml:mrow>
<mml:mtext>wt</mml:mtext>
<mml:mo>%</mml:mo>
</mml:mrow>
</mml:mfenced>
</mml:mrow>
<mml:mo>&#x3d;</mml:mo>
<mml:mn>0.81</mml:mn>
<mml:mtext>&#x2009;</mml:mtext>
<mml:mrow>
<mml:mfenced open="(" close=")" separators="|">
<mml:mrow>
<mml:mo>&#xb1;</mml:mo>
<mml:mtext>&#x2009;</mml:mtext>
<mml:mn>0.05</mml:mn>
</mml:mrow>
</mml:mfenced>
</mml:mrow>
<mml:mo>&#xb7;</mml:mo>
<mml:mi mathvariant="normal">&#x3bd;</mml:mi>
<mml:mn>11</mml:mn>
<mml:mtext>&#x2009;</mml:mtext>
<mml:mo>&#x2010;</mml:mo>
<mml:mtext>&#x2009;</mml:mtext>
<mml:mn>545.2</mml:mn>
<mml:mtext>&#x2009;</mml:mtext>
<mml:mrow>
<mml:mfenced open="(" close=")" separators="|">
<mml:mrow>
<mml:mo>&#xb1;</mml:mo>
<mml:mtext>&#x2009;</mml:mtext>
<mml:mn>37.2</mml:mn>
</mml:mrow>
</mml:mfenced>
</mml:mrow>
<mml:mo>.</mml:mo>
</mml:mrow>
</mml:math>
<label>(1)</label>
</disp-formula>
</p>
<p>The spectra collected from <italic>Inc5</italic>, <italic>Inc6a</italic>, and <italic>Inc6b</italic> (<xref ref-type="sec" rid="s12">Supplementary Figures S6e&#x2013;f</xref>) are consistent with olivine (<xref ref-type="bibr" rid="B15">Chopelas, 1991</xref>). The position of bands at 826&#xa0;cm<sup>&#x2212;1</sup> and 857&#xa0;cm<sup>&#x2212;1</sup> correlate with the Mg&#x23; (but also with P). According to the available parameterizations (<xref ref-type="bibr" rid="B34">Kuebler et al., 2006</xref>; <xref ref-type="bibr" rid="B85">Yasuzuka et al., 2009</xref>), these three inclusions have Mg&#x23; &#x3e; 90, which is further supported by the appearance of a band at &#x223c;610&#xa0;cm<sup>&#x2212;1</sup>, typical of forsteritic olivine. The Raman spectra of <italic>Inc3</italic>, <italic>Inc7</italic>, and <italic>Inc10</italic> (<xref ref-type="sec" rid="s12">Supplementary Figures S6c, g, h</xref>; <xref ref-type="sec" rid="s12">Supplementary Table S6</xref>) are representative of (ortho)enstatite with Mg&#x23; of 90 (<xref ref-type="bibr" rid="B27">Huang et al., 2000</xref>). The presence of additional bands at 368&#xa0;cm<sup>&#x2212;1</sup> (<italic>Inc3</italic>) and 367&#xa0;cm<sup>&#x2212;1</sup> (<italic>Inc10</italic>), identifiable only by peak deconvolution, can however be interpreted as characteristic of clinoenstatite (Cen; <xref ref-type="bibr" rid="B76">Ulmer and Stader, 2001</xref>). In conclusion, few variations of the main bands in some inclusions are observed with respect to those from the literature; these can be explained as the effect of either the chemical composition or some possible residual stress of those inclusions entrapped in the diamond. The infrared (IR) spectrum (<xref ref-type="sec" rid="s12">Supplementary Figure S9a</xref>) shows no defect-induced absorption in the 1,500-500&#xa0;cm<sup>&#x2212;1</sup> region, which excludes the presence of N and H in the diamond with the two-phonon absorption characteristic of type II diamonds in the 2,800-1,500 cm<sup>&#x2212;1</sup> spectrum. No evidence of molecular H<sub>2</sub>O was found in <italic>Inc1</italic> (<xref ref-type="sec" rid="s12">Supplementary Figure S9b</xref>).</p>
</sec>
<sec id="s3-3">
<title>3.3 Trace element composition of polished <italic>Inc1</italic>
</title>
<p>The concentration of trace elements in <italic>Inc1</italic> (<xref ref-type="sec" rid="s12">Supplementary Table S3</xref>) between core and rim is within uncertainty, such as Sr with 939&#xa0;ppm (942&#xa0;ppm at the rim), Ti with 104&#xa0;ppm (109&#xa0;ppm at the rim), Mn with 663&#xa0;ppm, V with 543&#xa0;ppm (539&#xa0;ppm at the rim), Ni with 338&#xa0;ppm (331&#xa0;ppm at the rim), Ce with 37&#xa0;ppm, and Sc with 31&#xa0;ppm. Hence, no significant variations occur between the rim and core of <italic>Inc1</italic>. <xref ref-type="fig" rid="F2">Figure 2a</xref> shows the abundance of seven analyzed trace elements at the core and rim of <italic>Inc1</italic>, normalized to the carbonaceous Ivuna chondrite used as reference (<xref ref-type="bibr" rid="B69">Stachel et al., 2022</xref>; <xref ref-type="bibr" rid="B41">McDonough and Sun, 1995</xref>) and plotted along with those from 30 lherzolitic inclusions with the aim of reconstructing the possible petrological history of the inclusions and, hence, of the diamond. The trace element distribution is consistent with published data for lherzolitic P-type inclusions (<xref ref-type="bibr" rid="B69">Stachel et al., 2022</xref>). The (CI chondrite-) normalized rare earth elements (REE) are shown in <xref ref-type="fig" rid="F2">Figure 2b</xref>, where the typical steep trend for light rare earth elements (LREE) agrees with that reported for lherzolitic cpx inclusions and would indicate coexistence with garnet in the diamond-forming mineral assemblage (<xref ref-type="bibr" rid="B69">Stachel et al., 2022</xref>).</p>
<fig id="F2" position="float">
<label>FIGURE 2</label>
<caption>
<p>
<bold>(a)</bold> Concentration of selected trace elements in the <italic>Inc1</italic> cpx from the core (dashed line) and rim (dotted line) normalized to the CI chondrite (<xref ref-type="bibr" rid="B41">McDonough and Sun, 1995</xref>) and compared with concentrations of P-type (orange) cpx inclusions available in the dataset (<xref ref-type="bibr" rid="B69">Stachel et al., 2022</xref>). <bold>(b)</bold> REE concentrations in <italic>Inc1</italic> cpx (core, dashed line and rim, dotted line) normalized to the CI chondrite and compared with P-type (orange).</p>
</caption>
<graphic xlink:href="fgeoc-03-1607472-g002.tif">
<alt-text content-type="machine-generated">Graph a shows the clinopyroxene to CI chondrite ratios for elements Ba, Nb, Sr, Zr, Hf, Ti, and Y. Graph b shows the same ratios for elements La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Both graphs compare the COMK3 core and rim, using dashed and dotted lines, among multiple P-type CPX inclusions represented by orange dots. The y-axis is logarithmic, ranging from 0.01 to 1000.</alt-text>
</graphic>
</fig>
</sec>
<sec id="s3-4">
<title>3.4 Iron oxidation state of trapped clinopyroxene and olivine inclusions</title>
<p>Very few Fe<sup>3&#x2b;</sup>/&#x2211;Fe data exist for the tiny minerals entrapped in diamonds that might shed light the redox environment where diamonds grew. Here, <italic>in situ</italic> synchrotron M&#xf6;ssbauer analyses were performed to determine the Fe<sup>3&#x2b;</sup>/&#x2211;Fe ratio of two cpx crystals (<italic>Inc1</italic> polished to the surface, <italic>Inc2</italic> entrapped) and one entrapped ol (<italic>Inc5</italic>). The calculated Fe<sup>3&#x2b;</sup>/&#x2211;Fe ratio in <italic>Inc1</italic> is 0.16 (&#xb1;0.03), 0.14 (&#xb1;0.02) in <italic>Inc2</italic>, but 0.02 (&#xb1;0.01) in <italic>Inc5</italic> (<xref ref-type="sec" rid="s12">Supplementary Figure S4</xref>). These data agree with the only available data for Fe<sup>3&#x2b;</sup>/&#x2211;Fe, varying from 0.08 to 0.14, in cpx diamond inclusions from George Creek (<xref ref-type="bibr" rid="B39">McCammon et al., 1998</xref>). When compared with Fe<sup>3&#x2b;</sup>/&#x2211;Fe ratio of cpx from mantle rocks (<xref ref-type="sec" rid="s12">Supplementary Table S7</xref>), we notice that spinel (spl)-peridotites (95 samples; <xref ref-type="bibr" rid="B37">Luth and Canil, 1993</xref>) have cpx with Fe<sup>3&#x2b;</sup>/&#x2211;Fe that ranges between 0.03 and 0.35 (0.24&#x2013;0.29 is the most frequent interval); cpx crystals in grt-peridotites (22 samples; <xref ref-type="bibr" rid="B37">Luth and Canil, 1993</xref>; <xref ref-type="bibr" rid="B83">Woodland et al., 2006</xref>) have Fe<sup>3&#x2b;</sup>/&#x2211;Fe between 0.09 and 0.44 (0.24&#x2013;0.29 is the most frequent interval), while cpx crystals from eclogites (63 samples <xref ref-type="bibr" rid="B43">Mikhailenko et al., 2020</xref>) have Fe<sup>3&#x2b;</sup>/&#x2211;Fe varying between 0.05 and 0.63 (0.15&#x2013;0.24 being the most frequent interval). Finally, Fe<sup>3&#x2b;</sup>/&#x2211;Fe of wehrlitic cpx crystals (3 samples) vary from 0.16 to 0.21. Our measured Fe<sup>3&#x2b;</sup>/&#x2211;Fe in cpx is also compared with that of synthetic cpx equilibrated at high P, T, and fo<sub>2</sub> of dry eclogitic assemblages. The Fe<sup>3&#x2b;</sup>/&#x2211;Fe of eclogitic cpx varies between 0.13 and 0.24 under the carbon&#x2013;carbon dioxide (CCO) buffer (<xref ref-type="bibr" rid="B56">Purwin et al., 2013</xref>) and 0.04 to 0.19 under the carbon&#x2013;carbonate buffer (<xref ref-type="bibr" rid="B72">Stagno et al., 2015</xref>), respectively. It is, therefore, difficult to infer a possible interaction between cpx and oxidized fluid just by looking at the Fe<sup>3&#x2b;</sup>/&#x2211;Fe. The Fe<sup>3&#x2b;</sup>/&#x2211;Fe measured on the ol of <italic>Inc5</italic> is consistent with the literature (<xref ref-type="bibr" rid="B20">Ejima et al., 2018</xref>; <xref ref-type="bibr" rid="B38">Marras et al., 2023</xref>).</p>
</sec>
<sec id="s3-5">
<title>3.5 Thermobarometric determinations</title>
<p>Elastic geobarometry allows the calculation of the conditions of entrapment, exploiting the difference in elastic properties between the host and the inclusion starting from the residual pressure on the latter&#x2014;<italic>Pinc</italic> (<xref ref-type="bibr" rid="B5">Angel et al., 2022</xref>). Olivine inclusions in diamonds have been employed as geobarometers to infer the growth conditions of the diamond host (<xref ref-type="bibr" rid="B44">Nestola et al., 2011</xref>). The unit-cell volume that the ol inclusion would have at room pressure <italic>V<sub>0</sub>
</italic> is needed to determine <italic>P<sub>inc</sub>
</italic>, and it depends on the Mg&#x23; (0.93 for <italic>Inc5</italic> and <italic>Inc6b</italic>, and 0.92 for <italic>Inc6a</italic>, all obtained here by <italic>in situ</italic> structure refinement and Raman spectroscopy). For <italic>Inc6a</italic>, isotropic approximation was employed due to the lower number of available reflections (<xref ref-type="sec" rid="s12">Supplementary Table S8</xref>). We calculated <italic>V<sub>0</sub>
</italic> using two different equations: a linear regression (<xref ref-type="bibr" rid="B82">Wang et al., 2023</xref>) and the equation proposed by <xref ref-type="bibr" rid="B59">Schwab and K&#xfc;stner (1977)</xref>. The resulting <italic>P<sub>inc</sub>
</italic> of 0.4&#x2013;1.1&#xa0;GPa was calculated using the third-order Birch&#x2013;Murnaghan equation of states (EoS) isothermal model for olivine (<xref ref-type="bibr" rid="B4">Angel et al., 2018</xref>), taken as minimum and maximum values by combining the two models in <xref ref-type="sec" rid="s12">Supplementary Table S9</xref>. From <italic>P<sub>inc</sub>
</italic>, a pressure of entrapment, <italic>P<sub>trap</sub>
</italic>, was calculated using the EoS for diamond (<xref ref-type="bibr" rid="B2">Angel et al., 2015</xref>). From the three ol inclusions, applying a temperature of entrapment, <italic>T<sub>trap</sub>
</italic>, of both 1,100&#xa0;&#x2009;&#xb0;C and 1,200&#xa0;&#x2009;&#xb0;C results in <italic>Ptrap</italic> of 5.2 and 5.5 GPa, respectively, using the linear regression, and 4.5 and 4.7 GPa, respectively (<xref ref-type="bibr" rid="B59">Schwab and K&#xfc;stner, 1977</xref>). The available dataset of inclusions in diamond (<xref ref-type="bibr" rid="B69">Stachel et al., 2022</xref>) reports 14 diamond samples with only cpx crystals found as inclusion. Among these diamonds, one is type II and four have no analyses of N aggregation. Temperature estimates vary from 1,116&#xa0;&#x2009;&#xb0;C to approximately 1,370&#xa0;&#x2009;&#xb0;C using the available geothermobarometer of <xref ref-type="bibr" rid="B49">Nimis and Taylor (2000)</xref> and <xref ref-type="bibr" rid="B50">Nimis et al. (2020)</xref>. In this study, thermobarometry on <italic>Inc1</italic> gives T of 1,060&#xa0;&#x2009;&#xb0;C and P of 4.3 GPa, the latter being consistent with a P range of 4.5 and 5.5&#xa0;GPa obtained by elastic barometry on <italic>Inc5</italic>, <italic>Inc6a</italic>, and <italic>Inc6b</italic>. By projecting the mid-pressure value of 5&#xa0;GPa on the 40&#xa0;mW/m<sup>2</sup> geotherm of the Amazonian craton, we obtained an independent T of 1,155&#xa0;&#x2009;&#xb0;C, which is consistent with a T range of 1,170 &#x2009;&#xb0;C&#x2013;1,300&#xa0;&#x2009;&#xb0;C proposed for the Ju&#xed;na area aged approximately 2&#xa0;Ga (<xref ref-type="bibr" rid="B9">Bulanova et al., 2010</xref>). These thermobarometric estimates are reported in <xref ref-type="fig" rid="F3">Figure 3</xref> along with the P-T conditions equally determined for those diamonds where only cpx inclusions have been reported. The P-T conditions for COMSK3 fall below the graphite&#x2013;diamond transition line (<xref ref-type="bibr" rid="B19">Day, 2012</xref>).</p>
<fig id="F3" position="float">
<label>FIGURE 3</label>
<caption>
<p>P-T conditions determined for inclusions of cpx from <xref ref-type="bibr" rid="B69">Stachel et al. (2022)</xref> and for the COMSK3 diamond using the cpx-thermobarometer (see text) plotted along with three geotherms taken as reference including the 40&#xa0;mW/m<sup>2</sup> for the Amazonian craton (<xref ref-type="bibr" rid="B13">Chagas de Melo et al., 2025</xref>). The graphite&#x2013;diamond boundary is also shown.</p>
</caption>
<graphic xlink:href="fgeoc-03-1607472-g003.tif">
<alt-text content-type="machine-generated">Scatter plot showing pressure in gigapascals versus temperature in degrees Celsius, with data points represented by various colored diamonds. Solid and dashed lines represent different data sets and models, including Ptrap XRD data, G/D Transition (Day 2012), and varying milliwatt per square meter values. The legend identifies markers and lines by color and type.</alt-text>
</graphic>
</fig>
</sec>
</sec>
<sec sec-type="discussion" id="s4">
<title>4 Discussion</title>
<sec id="s4-1">
<title>4.1 Na-rich, CO<sub>2</sub>-rich melt as a diamond-forming medium?</title>
<p>Typical diagrams have been used to distinguish peridotitic from eclogitic cpx inclusions in lithospheric diamonds on the basis of their major elements, such as Cr, Ti, Ca, Na, Al, Mg, Fe, and Cr (<xref ref-type="fig" rid="F4">Figures 4a&#x2013;c</xref>). The deviation from the proposed P- and E-type fields as well as differences with respect to the composition of cpx from mantle peridotites are evidence of metasomatic reactions (<xref ref-type="bibr" rid="B87">Mikhail et al., 2021</xref>; <xref ref-type="bibr" rid="B69">Stachel et al., 2022</xref>). The concentration of trace elements in diamond inclusions (LREE/HREE, Ce/Nb, Nd/Dy, Zr/Hf, and Ti/Eu) is also indicative of metasomatism, with a strong dependence on the chemical composition of the reactive fluid (<xref ref-type="bibr" rid="B66">Stachel and Harris, 1997</xref>; <xref ref-type="bibr" rid="B69">Stachel et al., 2022</xref>). The major elements for the exposed <italic>Inc1</italic> were compared with the available chemical dataset for cpx inclusions in lithospheric diamonds. While the Mg&#x23; and Cr&#x23; of <italic>Inc1</italic> cpx falls within the characteristic range of the peridotitic suite (<xref ref-type="fig" rid="F4">Figure 4a</xref>), the Na and Al contents (expressed in atoms per formula units, apfu) lie in between peridotitic and eclogitic compositions (<xref ref-type="fig" rid="F4">Figure 4b</xref>; <xref ref-type="disp-formula" rid="e1">Equation 1</xref>). The average values of Cr<sub>2</sub>O<sub>3</sub> (6.3&#xa0;wt%) along with the high CaO content (14.11&#xa0;wt%) of <italic>Inc1</italic> are typical concentrations of some wehrlitic garnets (<xref ref-type="bibr" rid="B61">Sobolev et al., 1973</xref>). These values deviate from the typical values found in cpx inclusions in peridotitic and eclogitic suite (<xref ref-type="fig" rid="F4">Figure 4c</xref>), with the exception of few cpx, such as D1364A (<xref ref-type="bibr" rid="B17">Daniels and Gurney, 1999</xref>) and Kmsm-6 and Kmsm-7 from Yakutian wehrlitic diamonds (<xref ref-type="bibr" rid="B62">Sobolev et al., 1977</xref>; <xref ref-type="bibr" rid="B64">2004</xref>). Both the major (e.g., Na, Cr, and Al) and trace (e.g., V and Sc) element composition of the entrapped cpx suggest a refertilization process similar to that recorded by cpx formed by (re-)fertilization of spl-bearing peridotite (<xref ref-type="bibr" rid="B7">Aulbach et al., 2020</xref>). Wehrlitization processes thus occur through the interaction of a mantle grt harzburgite with a metasomatic CO<sub>2</sub>-bearing melt at 1.5&#x2013;2&#xa0;GPa, leading to the formation of opx poor/free, cpx-rich rocks through the equilibrium reaction (<xref ref-type="bibr" rid="B78">Wallace and Green, 1988</xref>; <xref ref-type="bibr" rid="B86">Yaxley et al., 1998</xref>):<disp-formula id="e2">
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</disp-formula>
</p>
<fig id="F4" position="float">
<label>FIGURE 4</label>
<caption>
<p>
<bold>(a)</bold> Mg&#x23; plotted against Cr&#x23;, <bold>(b)</bold> Na (apfu) against Al (apfu), and <bold>(c)</bold> Cr<sub>2</sub>O<sub>3</sub> (wt%) against TiO<sub>2</sub> (wt%) of <italic>Inc1</italic> cpx (black circle) compared with the composition of cpx diamond inclusions available in the literature.</p>
</caption>
<graphic xlink:href="fgeoc-03-1607472-g004.tif">
<alt-text content-type="machine-generated">Three scatter plots labeled a, b, and c. Plot a shows Mg# versus Cr#, plot b displays Na (apfu) versus Al (apfu), and plot c presents Cr&#x2082;O&#x2083; (wt%) versus TiO&#x2082; (wt%). Data points are categorized by color and shape, representing eclogitic, peridotitic, websteritic, wehrlitic, and COMSK inclusion types, with a legend provided.</alt-text>
</graphic>
</fig>
<p>An analog reaction occurring more in-depth is<disp-formula id="e3">
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<label>(3)</label>
</disp-formula>that is, equivalent to the fo<sub>2</sub> buffering equilibrium (the acronym is <italic>EDDOD</italic>; <xref ref-type="bibr" rid="B71">Stagno and Frost, 2010</xref>) and describes the coexistence of carbonate (either liquid or solid) with diamond in the upper mantle. At the P and T determined from <italic>Inc1</italic>, this equilibrium reaction locally buffers the &#x394;logfo<sub>2</sub> at values between &#x2212;1.3 and &#x2212;1.6, assuming a reacting (metasomatic) melt varying from Na-bearing dolomitic to carbonate&#x2013;silicate in composition. The lack of a chemical zonation between rim and core in <italic>Inc1</italic> would support the cpx origin by direct transformation of a preexisting opx rather than by metasomatic contamination of a lherzolitic cpx. Indeed, a recent experimental study (<xref ref-type="bibr" rid="B81">Wang et al., 2022</xref>) helps distinguish peridotitic cpx from cpx formed by wehrlitization (<xref ref-type="disp-formula" rid="e2">Equation 2</xref>) on the basis of the variation of the major element composition, which is affected by the nature of the interacting melt, whether carbonatitic or silicic. In the case of <italic>Inc1</italic>, the simultaneous increase of the Ca/Al ratio with Mg&#x23; opposite the decreasing trend of Al<sub>2</sub>O<sub>3</sub> and TiO<sub>2</sub> are proposed evidence of the formation by interaction with coexisting carbonatitic melts (<xref ref-type="disp-formula" rid="e3">Equation 3</xref>). The high kosmochlor component has been classically considered a marker of <italic>groups 6</italic> and <italic>7</italic> cpx used as mineral indicators for diamond exploration (<xref ref-type="bibr" rid="B57">Quirt, 2004</xref>) and related to lithospheric refertilization by Na-rich carbonatite metasomatism of either Cr-rich, grt-bearing peridotites (<xref ref-type="bibr" rid="B23">Gr&#xfc;tter et al., 2024</xref>) or Cr-rich, spl-bearing peridotites (<xref ref-type="bibr" rid="B28">Ikehata and Arai, 2004</xref>). Notably, the V content is much greater than that reported in P-type inclusions (542&#xa0;ppm; <xref ref-type="fig" rid="F5">Figure 5</xref>). Such enrichment would require crystallization from (or equilibration with) a parental melt with 100&#x2013;300&#xa0;ppm of V (<xref ref-type="bibr" rid="B80">Wang et al., 2019</xref>) that, in the absence of data for carbonatites, is consistent with 100&#x2013;300&#xa0;ppm measured in natural kimberlitic rocks (<xref ref-type="bibr" rid="B33">Kostrovitsky et al., 2023</xref>). Thus, the minerals found entrapped in COMSK3 diamonds are representative of a lherzolitic environment, then P-type; however, the enrichment in kosmochlor is possible evidence of fluid&#x2013;rock interaction as described by reaction (3). The proposed presence of carbonate halos, by analogy with the literature, might be further evidence of CO<sub>2</sub>-rich fluids from which diamonds might have formed.</p>
<fig id="F5" position="float">
<label>FIGURE 5</label>
<caption>
<p>Concentration of V (ppm) plotted against Sc (ppm) in COMSK3 cpx and in cpx inclusions in diamonds along with in peridotitic and eclogitic cpx in mantle xenoliths (GEOROC Database updated at 03/01/2024).</p>
</caption>
<graphic xlink:href="fgeoc-03-1607472-g005.tif">
<alt-text content-type="machine-generated">Scatter plot showing Vanadium (V) versus Scandium (Sc) concentrations in parts per million (ppm). Data points are categorized into groups: Peridotite xenoliths (light green), Eclogite xenoliths (light pink), E-type inclusions in diamonds (orange), Deep eclogitic/lower mantle inclusions (blue), and COMSK (this study in yellow). A legend in the top right identifies each group.</alt-text>
</graphic>
</fig>
</sec>
</sec>
<sec sec-type="conclusion" id="s5">
<title>5 Conclusion</title>
<p>
<list list-type="simple">
<list-item>
<p>- The investigated COMSK3 is a type II lithospheric diamond with P-type lherzolitic inclusions that record (redox) interaction with a Na-rich carbonatitic (or carbonate-silicate) melt within a young lithospheric mantle accreted beneath the Amazonian craton.</p>
</list-item>
<list-item>
<p>- Major and trace elements from protogenetic <italic>Inc1</italic> support the interaction between Na-rich, CO<sub>2</sub>-rich melts.</p>
</list-item>
<list-item>
<p>- The Fe<sup>3&#x2b;</sup>/&#x2211;Fe ratio in cpx ranges between 0.13 and 0.16, which is higher than expected for cpx that did not undergo oxidation.</p>
</list-item>
<list-item>
<p>- A single diamond might not provide all the answers about lithospheric diamond formation at Ju&#xed;na, but the unique characteristics of this diamond provide insights into such a process when compared with the characteristics of the local lithosphere, which is given by available studies of mantle xenoliths and xenocrysts.</p>
</list-item>
</list>
</p>
</sec>
</body>
<back>
<sec sec-type="data-availability" id="s6">
<title>Data availability statement</title>
<p>The original contributions presented in the study are included in the article/<xref ref-type="sec" rid="s12">Supplementary Material</xref>; further inquiries can be directed to the corresponding author.</p>
</sec>
<sec sec-type="author-contributions" id="s7">
<title>Author contributions</title>
<p>AA: Formal Analysis, Writing &#x2013; original draft, Visualization, Methodology, Data curation, Investigation. GM: Investigation, Data curation, Validation, Formal Analysis, Visualization, Writing &#x2013; original draft, Funding acquisition, Methodology. MM: Methodology, Formal Analysis, Writing &#x2013; original draft, Investigation. SC: Writing &#x2013; original draft, Formal Analysis, Visualization, Investigation, Software. VSo: Data curation, Formal Analysis, Software, Writing &#x2013; original draft. LM: Formal Analysis, Data curation, Writing &#x2013; original draft. CR: Formal Analysis, Data curation, Writing &#x2013; original draft. AC: Writing &#x2013; original draft, Formal Analysis, Data curation. LB: Writing &#x2013; original draft, Data curation, Validation, Formal Analysis. FK: Data curation, Resources, Writing &#x2013; original draft, Conceptualization. VSa: Writing &#x2013; original draft, Project administration, Visualization, Supervision, Validation, Funding acquisition, Conceptualization, Data curation.</p>
</sec>
<sec sec-type="funding-information" id="s8">
<title>Funding</title>
<p>The author(s) declare that financial support was received for the research and/or publication of this article. This work was funded by the Dr. Eduard G&#xfc;belin Association for Research and Identification of Precious Stones through the &#x201c;Dr. Eduard G&#xfc;belin Research Scholarship&#x201d; (GM) and by PRIN MUR HERMES project no. 2022R35X8Z (VS).</p>
</sec>
<ack>
<p>We thank Eleonora Braschi and Andrea Orlando for their help with EPMA analyses and Matteo Paciucci for his technical assistance with the SEM. We thank Alessandro Frontoni for his technical support during the Raman measurements. We are grateful to Sonja Aulbach for sharing the dataset on the trace elements of diamond inclusions. We are thankful to the beamline staff of ex ID18 of ESRF (Grenoble, France; beamtime ES-1489) for assistance during the experimental session. Part of this work was also performed at SISSI beamline (Elettra Sincrotrone Trieste, Italy) and at GeoSoilEnviroCARS (The University of Chicago, Sector 13), Advanced Photon Source (APS), Argonne National Laboratory. GeoSoilEnviroCARS was supported by the National Science Foundation&#x2013;Earth Sciences (EAR &#x2013; 1634415).</p>
</ack>
<sec sec-type="COI-statement" id="s9">
<title>Conflict of interest</title>
<p>The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.</p>
<p>The author(s) declared that they were an editorial board member of Frontiers, at the time of submission. This had no impact on the peer review process and the final decision.</p>
</sec>
<sec sec-type="ai-statement" id="s10">
<title>Generative AI statement</title>
<p>The author(s) declare that no Generative AI was used in the creation of this manuscript.</p>
</sec>
<sec sec-type="disclaimer" id="s11">
<title>Publisher&#x2019;s note</title>
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<title>Supplementary material</title>
<p>The Supplementary Material for this article can be found online at: <ext-link ext-link-type="uri" xlink:href="https://www.frontiersin.org/articles/10.3389/fgeoc.2025.1607472/full#supplementary-material">https://www.frontiersin.org/articles/10.3389/fgeoc.2025.1607472/full&#x23;supplementary-material</ext-link>
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