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<front>
<journal-meta>
<journal-id journal-id-type="publisher-id">Front. Earth Sci.</journal-id>
<journal-title>Frontiers in Earth Science</journal-title>
<abbrev-journal-title abbrev-type="pubmed">Front. Earth Sci.</abbrev-journal-title>
<issn pub-type="epub">2296-6463</issn>
<publisher>
<publisher-name>Frontiers Media S.A.</publisher-name>
</publisher>
</journal-meta>
<article-meta>
<article-id pub-id-type="doi">10.3389/feart.2016.00083</article-id>
<article-categories>
<subj-group subj-group-type="heading">
<subject>Earth Science</subject>
<subj-group>
<subject>General Commentary</subject>
</subj-group>
</subj-group>
</article-categories>
<title-group>
<article-title>Response: Commentary: Is the Neoproterozoic oxygen burst a supercontinent legacy?</article-title>
</title-group>
<contrib-group>
<contrib contrib-type="author" corresp="yes">
<name><surname>Macouin</surname> <given-names>Melina</given-names></name>
<xref ref-type="aff" rid="aff1"><sup>1</sup></xref>
<xref ref-type="author-notes" rid="fn001"><sup>&#x0002A;</sup></xref>
<uri xlink:href="http://loop.frontiersin.org/people/87851/overview"/>
</contrib>
<contrib contrib-type="author">
<name><surname>Rousse</surname> <given-names>Sonia</given-names></name>
<xref ref-type="aff" rid="aff1"><sup>1</sup></xref>
<uri xlink:href="http://loop.frontiersin.org/people/207057/overview"/>
</contrib>
<contrib contrib-type="author">
<name><surname>Ganne</surname> <given-names>J&#x000E9;r&#x000F4;me</given-names></name>
<xref ref-type="aff" rid="aff1"><sup>1</sup></xref>
</contrib>
<contrib contrib-type="author">
<name><surname>Den&#x000E8;le</surname> <given-names>Yoann</given-names></name>
<xref ref-type="aff" rid="aff1"><sup>1</sup></xref>
</contrib>
<contrib contrib-type="author">
<name><surname>Roques</surname> <given-names>Damien</given-names></name>
<xref ref-type="aff" rid="aff1"><sup>1</sup></xref>
<uri xlink:href="http://loop.frontiersin.org/people/207046/overview"/>
</contrib>
<contrib contrib-type="author">
<name><surname>Trindade</surname> <given-names>Ricardo I. F.</given-names></name>
<xref ref-type="aff" rid="aff2"><sup>2</sup></xref>
</contrib>
</contrib-group>
<aff id="aff1"><sup>1</sup><institution>G&#x000E9;osciences Environnement Toulouse, UMR 5563 Centre National de la Recherche Scientifique, UR234 IRD, Universit&#x000E9; de Toulouse</institution> <country>Toulouse, France</country></aff>
<aff id="aff2"><sup>2</sup><institution>Departamento de Geof&#x000ED;sica, Instituto de Astronomia, Geof&#x000ED;sica e Ci&#x000EA;ncias Atmosf&#x000E9;ricas, Universidade de S&#x000E3;o Paulo</institution> <country>S&#x000E3;o Paulo, Brazil</country></aff>
<author-notes>
<fn fn-type="edited-by"><p>Edited by: Eric Font, University of Lisbon, Portugal</p></fn>
<fn fn-type="edited-by"><p>Reviewed by: Dario Bilardello, University of Minnesota, USA; Nicholas L. Swanson-Hysell, University of California, Berkeley, USA; Juan Cruz Larrasoa&#x000F1;a, Instituto Geol&#x000F3;gico y Minero de Espa&#x000F1;a, Spain</p></fn>
<fn fn-type="corresp" id="fn001"><p>&#x0002A;Correspondence: Melina Macouin <email>melina.macouin&#x00040;get.omp.eu</email></p></fn>
<fn fn-type="other" id="fn002"><p>This article was submitted to Geomagnetism and Paleomagnetism, a section of the journal Frontiers in Earth Science</p></fn> 
</author-notes>
<pub-date pub-type="epub">
<day>31</day>
<month>08</month>
<year>2016</year>
</pub-date>
<pub-date pub-type="collection">
<year>2016</year>
</pub-date>
<volume>4</volume>
<elocation-id>83</elocation-id>
<history>
<date date-type="received">
<day>25</day>
<month>04</month>
<year>2016</year>
</date>
<date date-type="accepted">
<day>19</day>
<month>08</month>
<year>2016</year>
</date>
</history>
<permissions>
<copyright-statement>Copyright &#x000A9; 2016 Macouin, Rousse, Ganne, Den&#x000E8;le, Roques and Trindade.</copyright-statement>
<copyright-year>2016</copyright-year>
<copyright-holder>Macouin, Rousse, Ganne, Den&#x000E8;le, Roques and Trindade</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) or licensor 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>
<related-article id="RA1" related-article-type="commentary-article" journal-id="Front Earth Sci" journal-id-type="nlm-ta" vol="3" page="80" xlink:href="10.3389/feart.2015.00080" ext-link-type="doi">A commentary on <article-title>Commentary: Is the Neoproterozoic oxygen burst a supercontinent legacy?</article-title> by N&#x000E9;d&#x000E9;lec, A., and Borisova, A.Y. (2015). Front. Earth Sci. 3:80. doi: <object-id>10.3389/feart.2015.00080</object-id></related-article> 
<kwd-group>
<kwd>rock magnetism</kwd>
<kwd>Neoproterozoic Oxygenation Event</kwd>
<kwd>hematite-magnetite buffer</kwd>
<kwd>Rodinia</kwd>
<kwd>Socotra</kwd>
<kwd>subductions</kwd>
</kwd-group>
<contract-num rid="cn001">INSU Syster, INSU PNP</contract-num>
<contract-sponsor id="cn001">Centre National de la Recherche Scientifique<named-content content-type="fundref-id">10.13039/501100004794</named-content></contract-sponsor>
<counts>
<fig-count count="1"/>
<table-count count="0"/>
<equation-count count="0"/>
<ref-count count="16"/>
<page-count count="3"/>
<word-count count="1973"/>
</counts>
</article-meta>
</front>
<body>
<p>We thank Nedelec and Borisova (<xref ref-type="bibr" rid="B12">2015</xref>) for giving us the opportunity to clarify our data and (derived) conceptual model. The purpose of Macouin et al. (<xref ref-type="bibr" rid="B10">2015</xref>) was to propose a new approach to explain the Neoproterozoic Oxygenation Event. It should be recalled that among the recent and abandoned hypotheses for the oxidation of the atmosphere, rise of less reduced gases (or more oxidized) remains one of the most frequently invoked (i.e., Kasting, <xref ref-type="bibr" rid="B8">2013</xref>).</p>
<p>We illustrate our model with data acquired on the Neoproterozoic Socotra biotite granite (SBG) thought to be related to one of the subduction zones that surrounded Rodinia around 780 Ma. The main question raised by Nedelec and Borisova (<xref ref-type="bibr" rid="B12">2015</xref>) concerns the primary origin of hematite and ilmenite in this granite and the oxidized character of the emitted gases.</p>
<p>Before discussing the oxide assemblage, we answer on the use of the hematite-magnetite buffer, for which we refer to Sun et al. (<xref ref-type="bibr" rid="B15">2015</xref>) and Botcharnikov et al. (<xref ref-type="bibr" rid="B1">2008</xref>). Indeed, the magnetite-hematite assemblage does not permit to give a precise value of &#x00394;FMQ, but as stated by these authors, the assemblage is a classical indicator of high oxygen fugacities and hence of an oxidized magma. As mentioned in the comment, it is true that, recently, fO<sub>2</sub> from gas has been shown to possibly diverge from the source magma contrary to what was commonly thought previously (i.e., Burgisser and Scaillet, <xref ref-type="bibr" rid="B3">2007</xref>). Nevertheless, these authors have estimated the deviation from the redox state of the magma source by no more than 1.5 log unit at maximum. In our case, we can still invoke oxidized gases since our estimated fO<sub>2</sub> from sources is significantly higher (&#x00394;FMQ &#x0002B; 4/5).</p>
<p>Concerning the oxide assemblage found in the SBG, we first state that magmatic or late magmatic origin of (titano-poor) hematite has already been reported. For example, Carvalho and Janasi (<xref ref-type="bibr" rid="B4">2012</xref>) found hematite in the 610 Ma Pedra Branca syenite (from a magmatic arc) in Brazil. These authors described a primary assemblage of hematite, ilmenite and magnetite. They conclude that this coexistence implies oxidized conditions and probably high oxygen fugacities. One of the authors herself reports an example of magmatic hematite in the unaltered Washita granite (Nedelec et al., <xref ref-type="bibr" rid="B13">2015</xref>). In this publication, the hematite, in the unaltered granite, is interpreted as due to a change in oxygen fugacity in the magma &#x0201C;<italic>without any influence of a hydrous fluid</italic>.&#x0201D; Also, contrary to what Nedelec and Borisova (<xref ref-type="bibr" rid="B12">2015</xref>) advance in their comment, Broska and Petrik (<xref ref-type="bibr" rid="B2">2011</xref>) do not state that hematite is always post magmatic but that the reactions could begin in the magmatic stage.</p>
<p>Nedelec and Borisova (<xref ref-type="bibr" rid="B12">2015</xref>) affirm that liquidus phase hematite was uniquely found in an experimental peralkaline residual (Edgar, <xref ref-type="bibr" rid="B5">1974</xref>), and therefore not possible with natural samples. More recent literature reports formation of liquidus phase hematite on both, for example, I-type Chinese granite, remelted and recrystallized (Liaw et al., <xref ref-type="bibr" rid="B9">2006</xref>) and a synthetic analog of a ferrobasaltic melt of the Skaergaard intrusion (Botcharnikov et al., <xref ref-type="bibr" rid="B1">2008</xref>). These authors even demonstrate that they produce hematite in their experiments only at high oxygen fugacities (fO<sub>2</sub> &#x0003E; 2.5). Both these experiments involve formation of titano-poor hematite (and not of stoichiometric hematite) as it is interpreted in the SBG. This interpretation is strongly suggested by the reversible behavior of the thermomagnetic curves with N&#x000E9;el temperatures on the order of 620&#x000B0;-630&#x000B0;C (see samples CS27-CS30 from Figure 4, Macouin et al., <xref ref-type="bibr" rid="B10">2015</xref>) combined with the petrological observations.</p>
<p>We are aware that hematite can be secondary in granites due to oxygenated fluids. Such secondary hematite has been described in different forms described in Nedelec et al. (<xref ref-type="bibr" rid="B13">2015</xref>), or associated with chloritized biotite (Just and Kontny, <xref ref-type="bibr" rid="B7">2012</xref>). A typical mark of hematitization (maghemitization) of titano-magnetite is to display a progression from rims toward core center (often with the core untouched) or along the fractures (Figure 4H of Broska and Petrik, <xref ref-type="bibr" rid="B2">2011</xref>). Curved cracks are also a typical feature of maghemitization (Figure 15 of Haggerty, <xref ref-type="bibr" rid="B6">1991</xref>; Figure 3C of McEnroe and Brown, <xref ref-type="bibr" rid="B11">2000</xref>). It is worth noting that in the SBG, the hematite does not appear into any of these forms and marks of alteration are absent (Figure <xref ref-type="fig" rid="F1">1</xref>).</p>
<fig id="F1" position="float">
<label>Figure 1</label>
<caption><p><bold>Corrected caption of Figure 7 of Macouin et al. (<xref ref-type="bibr" rid="B10">2015</xref>)</bold>. Photomicrographs of magnetite from CS46 sample (Socotra Biotite Granite, Neoproterozoic terrains, Oman) <bold>(A)</bold> Photomicrographs of subhedral crystals of magnetite (black minerals) trapped in a poikiloblast crystal of biotite (brown mineral). <bold>(B)</bold> Recognition of treillis-like shaped hematite within the crystal of magnetite under reflected light microscopy. Note that hematite is present in the ilmenite and at the fringe of the ilmenite lamellae <bold>(C)</bold> Back-scattered electron imaging on the internal structure of oxide, using a scanning electron microscope (SEM), reveals multiple grains of magnetite-hematite separated by elongated crystals of ilmenite. <bold>(D)</bold> Oriented needles or patches of ilmenite outline the contact with biotite. <bold>(E,F)</bold> Interpreted magmatic events depicted from microscopic and SEM observations. Ilmenite and hematite lamellae developed along cleavage planes of magnetite, due to magmatic oxy-exsolution processes. Magnetite was fractured and divided.</p></caption>
<graphic xlink:href="feart-04-00083-g0001.tif"/>
</fig>
<p>In the SBG, as described by Haggerty (<xref ref-type="bibr" rid="B6">1991</xref>), the C4 stage is probably reached in the samples presenting the assemblage of magnetite-ilmenite-hematite. It is difficult to assess whether the hematite lamellae replaced previous thin ilmenite lamellae (as expected for C4 stage) or are secondary as Nedelec and Borisova (<xref ref-type="bibr" rid="B12">2015</xref>) argue. Nevertheless, in Figure <xref ref-type="fig" rid="F1">1B</xref>, thick ilmenite lamellae are seen to both contain hematite and be fringed by hematite, indicating the C4 stage. While we think that this stage was attained during the formation of the granite, late magmatic deuteric oxidation (above 600&#x000B0;C) could not completely be excluded. In this case, such a high temperature alteration would indicate high fugacity of oxygen at least in the fluids that were involved during the end or just after the crystallization as likely occured in the Malani red rhyolites described by Torsvik et al. (<xref ref-type="bibr" rid="B16">2001</xref>).</p>
<p>Furthermore, contrary to what Nedelec and Borisova (<xref ref-type="bibr" rid="B12">2015</xref>) claim, porphyries generally present hematite-magnetite assemblages and their primary origin has recently been evoked by Sun et al. (<xref ref-type="bibr" rid="B14">2013</xref>, <xref ref-type="bibr" rid="B15">2015</xref>). As stated by Sun et al. (<xref ref-type="bibr" rid="B14">2013</xref>), intergrowths of magnetite-hematite, such as the ones we exposed in our paper (Macouin et al., <xref ref-type="bibr" rid="B10">2015</xref>), are not often studied and may represent a challenge. It appears clearly that their occurrences are rare and therefore represent an unusual feature. The fact that hematite is ignored or systematically referred as secondary might be a bias in the studies.</p>
<p>Finally, the hematite in the SBG seems to be likely primary and our model remains a possible valid explanation for the NOE. This interesting discussion emphasizes the need to scrutinize this type of mineralogical assemblage in further studies. Additional methods could be used for that, such as paleomagnetic direction to decipher the synchronicity in hematite and magnetite formation or in-situ geochemistry.</p>
<sec id="s1">
<title>Author contributions</title>
<p>All authors listed, have made substantial, direct and intellectual contribution to the work, and approved it for publication.</p>
</sec>
<sec>
<title>Funding</title>
<p>The study was supported by the Tellus-Syster, PNP and Marges programs of the INSU-CNRS and by the OMP-AO1 program.</p>
<sec>
<title>Conflict of interest statement</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>
</sec>
</sec>
</body>
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