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<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="publisher-id">1509409</article-id>
<article-id pub-id-type="doi">10.3389/feart.2024.1509409</article-id>
<article-categories>
<subj-group subj-group-type="heading">
<subject>Earth Science</subject>
<subj-group>
<subject>Original Research</subject>
</subj-group>
</subj-group>
</article-categories>
<title-group>
<article-title>Melt inclusion bubbles provide new insights into crystallisation depths and CO<sub>2</sub> systematics at Soufri&#xe8;re Hills Volcano, Montserrat</article-title>
<alt-title alt-title-type="left-running-head">Howe 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/feart.2024.1509409">10.3389/feart.2024.1509409</ext-link>
</alt-title>
</title-group>
<contrib-group>
<contrib contrib-type="author" corresp="yes">
<name>
<surname>Howe</surname>
<given-names>TiVonne A.</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>Christopher</surname>
<given-names>Thomas E.</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
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<contrib contrib-type="author">
<name>
<surname>Moune</surname>
<given-names>S&#xe9;verine</given-names>
</name>
<xref ref-type="aff" rid="aff4">
<sup>4</sup>
</xref>
<xref ref-type="aff" rid="aff5">
<sup>5</sup>
</xref>
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<contrib contrib-type="author">
<name>
<surname>Tuffen</surname>
<given-names>Hugh</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
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<contrib contrib-type="author">
<name>
<surname>Schiavi</surname>
<given-names>Federica</given-names>
</name>
<xref ref-type="aff" rid="aff4">
<sup>4</sup>
</xref>
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<aff id="aff1">
<sup>1</sup>
<institution>Lancaster Environment Centre</institution>, <institution>Lancaster University</institution>, <addr-line>Lancaster</addr-line>, <country>United Kingdom</country>
</aff>
<aff id="aff2">
<sup>2</sup>
<institution>Montserrat Volcano Observatory</institution>, <addr-line>Flemmings</addr-line>, <country>Montserrat</country>
</aff>
<aff id="aff3">
<sup>3</sup>
<institution>Seismic Research Centre</institution>, <institution>The University of the West Indies</institution>, <addr-line>St Augustine</addr-line>, <country>Trinidad and Tobago</country>
</aff>
<aff id="aff4">
<sup>4</sup>
<institution>Laboratoire Magmas et Volcans</institution>, <institution>Observatoire de Physique du Globe de Clermont-Ferrand</institution>, <institution>Universit&#xe9; Clermont Auvergne</institution>, <addr-line>Clermont-Ferrand</addr-line>, <country>France</country>
</aff>
<aff id="aff5">
<sup>5</sup>
<institution>Institut de Physique du Globe de Paris</institution>, <institution>Universit&#xe9; Paris Cit&#xe9;</institution>, <addr-line>Paris</addr-line>, <country>France</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/88428/overview">Marco Viccaro</ext-link>, University of Catania, Italy</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/124680/overview">David M. Pyle</ext-link>, University of Oxford, United Kingdom</p>
<p>
<ext-link ext-link-type="uri" xlink:href="https://loop.frontiersin.org/people/125470/overview">Jacob B. Lowenstern</ext-link>, United States Geological Survey (USGS), United States</p>
</fn>
<corresp id="c001">&#x2a;Correspondence: TiVonne A. Howe, <email>t.howe1@lancaster.ac.uk</email>
</corresp>
</author-notes>
<pub-date pub-type="epub">
<day>14</day>
<month>01</month>
<year>2025</year>
</pub-date>
<pub-date pub-type="collection">
<year>2024</year>
</pub-date>
<volume>12</volume>
<elocation-id>1509409</elocation-id>
<history>
<date date-type="received">
<day>10</day>
<month>10</month>
<year>2024</year>
</date>
<date date-type="accepted">
<day>16</day>
<month>12</month>
<year>2024</year>
</date>
</history>
<permissions>
<copyright-statement>Copyright &#xa9; 2025 Howe, Christopher, Moune, Tuffen and Schiavi.</copyright-statement>
<copyright-year>2025</copyright-year>
<copyright-holder>Howe, Christopher, Moune, Tuffen and Schiavi</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>Improved understanding of the magmatic system of Soufri&#xe8;re Hills Volcano, Montserrat (SHV) is needed to inform future hazard management strategy, and remaining uncertainties include the depth of magma storage and the source of ongoing gas emissions. Eruptive activity between 1995 and 2010 has been proposed to be sourced from either a dual chamber or transcrustal mush-based magmatic system, with volatile solubility models using H<sub>2</sub>O and CO<sub>2</sub> from melt inclusion (MI) glass estimating depths of 5&#x2013;6 km. To date, published SHV MI volatile data have neglected the vapour bubbles now known to sequester the bulk of MI magmatic carbon. Total CO<sub>2</sub> concentrations in SHV magma are therefore underestimated, together with volatile-derived entrapment pressures and inferred magma storage depths. Here, we present a new dataset of volatile (H<sub>2</sub>O and total CO<sub>2</sub>) and major element concentrations in plagioclase- and orthopyroxene-hosted SHV MI, that span almost all of the eruptive activity (Phases 1, 2, 4, and 5), and include the first measurement of bubble-hosted CO<sub>2</sub> for SHV and indeed the Lesser Antilles Arc. Analyses were conducted using Raman spectroscopy, ion microprobe, and electron probe analysis. Dacitic&#x2013;rhyolitic MI occur within andesitic whole rock compositions. Volatiles in MI glass are similar to published studies (H<sub>2</sub>O 2.47&#x2013;7.26 wt%; CO<sub>2</sub> 13&#x2013;1243 ppm). However, bubble-hosted CO<sub>2</sub> contributes 9&#x2013;3,145 ppm, to total inclusion CO<sub>2</sub> with 5%&#x2013;99% (median 90%) of CO<sub>2</sub> sequestered within bubbles, and total CO<sub>2</sub> concentrations (131&#x2013;3,230 ppm) are significantly higher than previously published values. Inferred entrapment depths from our dataset range from 5.7 to 17 km &#x2013; far greater than previous estimates &#x2013; and support a vertically elongated magmatic system where crystallisation spanned both upper- and mid-crustal depths. Our CO<sub>2</sub> measurements enable new estimation of CO<sub>2</sub> sources and fluxes. As a total of 4.5 Mt of CO<sub>2</sub> was held in SHV magma during the aforementioned phases, the maximum amount of CO<sub>2</sub> that can be emitted from a batch of SHV magma is &#x223c;1500&#x2013;1750 tonnes/day. Measured CO<sub>2</sub> fluxes are significantly higher, indicating additional input of CO<sub>2</sub> into the system from greater depths. Our study shows that including bubble-hosted CO<sub>2</sub> redefines understanding of the SHV plumbing system.</p>
</abstract>
<kwd-group>
<kwd>carbon dioxide</kwd>
<kwd>volatile content</kwd>
<kwd>volatile emissions</kwd>
<kwd>magma mush</kwd>
<kwd>Raman spectroscopy</kwd>
<kwd>vapour bubble</kwd>
</kwd-group>
<contract-sponsor id="cn001">Natural Environment Research Council<named-content content-type="fundref-id">10.13039/501100000270</named-content>
</contract-sponsor>
<contract-sponsor id="cn002">Lancaster University<named-content content-type="fundref-id">10.13039/100010029</named-content>
</contract-sponsor>
<custom-meta-wrap>
<custom-meta>
<meta-name>section-at-acceptance</meta-name>
<meta-value>Volcanology</meta-value>
</custom-meta>
</custom-meta-wrap>
</article-meta>
</front>
<body>
<sec id="s1">
<title>1 Introduction</title>
<p>Mitigation of risk at active island arc volcanoes is a significant challenge (<xref ref-type="bibr" rid="B62">Joseph et al., 2022</xref>) that requires detailed understanding of the nature of the magmatic plumbing system and the origin and significance of its gas emissions. Soufri&#xe8;re Hills Volcano is arguably one of the most monitored and studied arc volcanoes, with detailed datasets and models constraining the geochemical, petrological, seismological and geodetic components of the volcanic system (e.g., <xref ref-type="bibr" rid="B5">Aspinall et al., 1998</xref>; <xref ref-type="bibr" rid="B11">Barclay et al., 1998</xref>; <xref ref-type="bibr" rid="B36">Devine et al., 2003</xref>; <xref ref-type="bibr" rid="B104">Ryan et al., 2010</xref>; <xref ref-type="bibr" rid="B40">Edmonds et al., 2014</xref>; <xref ref-type="bibr" rid="B95">Plail et al., 2018</xref>). The current eruption began in 1995, and has produced both intermittent explosions and dome growth between 1995 and 2010 (<xref ref-type="bibr" rid="B117">Wadge et al., 2014</xref>). While magma extrusion has not been observed since 2010, ongoing unrest includes 1) deformation of the volcano caused by melt injection into a crustal reservoir, proposed to be dual sourced at &#x223c;5&#x2013;6 km and &#x223c;17 km depth (<xref ref-type="bibr" rid="B90">Neuberg et al., 2022</xref>) or mush based and vertically extensive, spanning the upper- and mid-crustal regions with a base at &#x223c;17 km (<xref ref-type="bibr" rid="B3">Alshembari et al., 2024</xref>), 2) seismicity mainly in the form of volcano-tectonic earthquakes that are attributed to pressurisation and fracturing related to magma injection and migration (<xref ref-type="bibr" rid="B109">Smith, 2013</xref>), and 3) emission of SO<sub>2</sub> at an average rate of 374 &#xb1; 140 tonnes/day (from February 2010 to December 2014) with occasional higher fluxes (&#x223c;10&#xd7;) accompanying volcano tectonic earthquake swarms and associated with migration of magma (<xref ref-type="bibr" rid="B30">Christopher et al., 2015</xref>).</p>
<p>During the ongoing hiatus of surface activity, some significant advances in technologies and methods are yet to be applied to the Soufri&#xe8;re Hills system. In particular, the application of Raman spectroscopy as a tool for measuring volatiles in vapour bubbles (e.g., <xref ref-type="bibr" rid="B53">Hartley et al., 2014</xref>; <xref ref-type="bibr" rid="B84">Moore et al., 2015</xref>; <xref ref-type="bibr" rid="B83">Moore and Bodnar, 2019</xref>) now permits more accurate measurement of total CO<sub>2</sub> in magmatic melt inclusions. Melt inclusions are small parcels of melt trapped during crystal growth and can represent the pre-eruptive magma, giving insight into the evolving geochemical and physical environment of subsurface magma within the plumbing system (e.g., <xref ref-type="bibr" rid="B63">Kent, 2008</xref>; <xref ref-type="bibr" rid="B84">Moore et al., 2015</xref>). The post-entrapment generation of bubble(s) allows sequestration of a proportion of the magmatic volatile species in the vapour phase&#x2013;in particular, CO<sub>2</sub>. Methodological development now allows the vapour bubble CO<sub>2</sub> to be quantified via Raman spectroscopy, revealing that in some cases more than 90% of the total CO<sub>2</sub> content of the inclusion resides in the bubble. This implies that previous measurements of melt inclusion CO<sub>2</sub>, made solely on dissolved CO<sub>2</sub> within melt inclusion glass, could have severely underestimated magmatic CO<sub>2</sub> contents (<xref ref-type="bibr" rid="B84">Moore et al., 2015</xref>; <xref ref-type="bibr" rid="B120">Wieser et al., 2021</xref>). As a consequence, constraints on magma storage depths from CO<sub>2</sub>-dependent volatile solubility models have been underestimated (e.g., <xref ref-type="bibr" rid="B53">Hartley et al., 2014</xref>; <xref ref-type="bibr" rid="B84">Moore et al., 2015</xref>; <xref ref-type="bibr" rid="B51">Hanyu et al., 2020</xref>). In this study, we use ion microprobe (SIMS) and Raman spectroscopy measurements to provide the first full CO<sub>2</sub> contents of melt inclusions from Soufri&#xe8;re Hills Volcano, using melt inclusions from four of the five phases of the 1995&#x2013;2010 eruptive activity. This leads to refined and more realistic constraints on the storage depths and volatile systematics of this important eruption.</p>
</sec>
<sec id="s2">
<title>2 Geological setting</title>
<p>The Lesser Antilles Arc trends roughly N-S, and extends &#x223c;850 km (<xref ref-type="fig" rid="F1">Figure 1</xref>). The arc is the product of subduction of the Atlantic Plate at a 67&#xb0; (ENE) vector beneath the Caribbean Plate, at an overall rate of &#x223c;2 cm/year (<xref ref-type="bibr" rid="B34">DeMets et al., 2000</xref>), erupting 5 km<sup>3</sup>Ma<sup>-1</sup>km<sup>-1</sup> of magma over a 300-year period from 1680 to 1980 (<xref ref-type="bibr" rid="B116">Wadge, 1984</xref>). The arc consists of two lines of volcanism, separated by age, marked by a central boundary at Martinique (<xref ref-type="fig" rid="F1">Figure 1</xref> inset). To the west exists the volcanic islands, where volcanism occurred during the Neogene to present (<xref ref-type="bibr" rid="B68">Macdonald et al., 2000</xref>), and to the east, islands where volcanism prevailed during the Upper Jurassic to the Lower Oligocene, with their volcanic basements now covered by sedimentary rocks (<xref ref-type="bibr" rid="B16">Bouysse et al., 1990</xref>). The arc can also be divided based on characteristics such as magma chemistry, seismicity, and overall structure (<xref ref-type="bibr" rid="B10">Balcone-Boissard et al., 2023</xref>; <xref ref-type="bibr" rid="B80">Metcalfe et al., 2023</xref>). The islands in the north, from Saba to Montserrat, can be tholeiitic (St Kitts, Redonda) and calc-alkaline (Saba, Montserrat), producing andesite (<xref ref-type="bibr" rid="B98">Rea, 1974</xref>; <xref ref-type="bibr" rid="B17">Brown et al., 1977</xref>; <xref ref-type="bibr" rid="B99">Rea and Baker, 1980</xref>; <xref ref-type="bibr" rid="B8">Baker, 1984</xref>; <xref ref-type="bibr" rid="B68">Macdonald et al., 2000</xref>). In the central and southern islands, andesites, basaltic andesites and basalts are most prevalent (<xref ref-type="bibr" rid="B17">Brown et al., 1977</xref>; <xref ref-type="bibr" rid="B68">Macdonald et al., 2000</xref>). Beneath the arc, the crust can be divided into four layers based on crustal structure, with the Mohorovi&#x10d;i&#x107; discontinuity (Moho) varying between 25&#x2013;37 km depth (<xref ref-type="bibr" rid="B77">Melekhova et al., 2019</xref>).</p>
<fig id="F1" position="float">
<label>FIGURE 1</label>
<caption>
<p>Map of Montserrat showing location of the four stratovolcanoes. Soufri&#xe8;re Hills is located in the south, denoted by the red star. Inset map illustrates the Lesser Antilles Arc and the western and eastern arcs.</p>
</caption>
<graphic xlink:href="feart-12-1509409-g001.tif"/>
</fig>
<sec id="s2-1">
<title>2.1 Soufri&#xe8;re Hills Volcano, Montserrat</title>
<p>Montserrat is the sixth island from the north of the active volcanic chain and forms part of the northerly group of islands (<xref ref-type="fig" rid="F1">Figure 1</xref>; <xref ref-type="bibr" rid="B68">Macdonald et al., 2000</xref>). It consists of four stratovolcanoes, three of which are dormant (Silver Hills, Centre Hills and South Soufri&#xe8;re Hills), last erupting 0.96 &#xb1; 0.25 million years ago (<xref ref-type="bibr" rid="B98">Rea, 1974</xref>). The active Soufri&#xe8;re Hills Volcano (SHV) is a volcanic complex located in the southern part of Montserrat, and its most recent eruption commenced on 18 July 1995, with the extrusion of crystal-rich andesitic magma (<xref ref-type="bibr" rid="B100">Robertson et al., 2000</xref>; <xref ref-type="bibr" rid="B110">Sparks and Young, 2002</xref>). This involved predominantly effusive activity, leading to the growth of lava dome complexes punctuated by dome-collapse events. Other activity involved explosive Vulcanian events of up to VEI 2&#x2013;3 (<xref ref-type="bibr" rid="B100">Robertson et al., 2000</xref>; <xref ref-type="bibr" rid="B26">Cassidy et al., 2018</xref>), and less intense ash venting (<xref ref-type="bibr" rid="B32">Cole et al., 2014</xref>).</p>
<p>A total of 988 &#xd7; 10<sup>6</sup> km<sup>3</sup> (<xref ref-type="bibr" rid="B117">Wadge et al., 2014</xref>) of material was produced over five phases of dome building activity that are interspersed with &#x201c;pauses,&#x201d; marked by a cessation in lava extrusion (<xref ref-type="table" rid="T1">Table 1</xref>). SHV has produced cycles of activity on both the sub-daily and sub-annual scale. Sub-daily cycles in Phase 1 consisted of explosions coinciding with ground deformation and seismicity (<xref ref-type="bibr" rid="B115">Voight et al., 1999</xref>), while in Phase 2, seismicity coincided with peaks in SO<sub>2</sub> flux (<xref ref-type="bibr" rid="B122">Young et al., 2003</xref>). This cyclic behavior ceased during Phase 3, and occurred again in Phases 4 and 5 in the form of seismic cycles where swarms of hybrid earthquakes merged to form continuous tremor (<xref ref-type="bibr" rid="B32">Cole et al., 2014</xref>; <xref ref-type="bibr" rid="B94">Odbert et al., 2014</xref>).</p>
<table-wrap id="T1" position="float">
<label>TABLE 1</label>
<caption>
<p>Characteristics of eruptive phases.</p>
</caption>
<table>
<thead valign="top">
<tr>
<th align="center">Phase/Pause</th>
<th align="center">Date</th>
<th align="center">Duration</th>
<th align="center">Erupted volume (x 10<sup>6</sup> m<sup>3</sup>)</th>
<th align="center">Mean effusive rate (m<sup>3</sup>s<sup>&#x2212;1</sup>)</th>
<th align="center">Eruptive characteristics</th>
</tr>
</thead>
<tbody valign="top">
<tr>
<td align="center">Phase 1</td>
<td align="center">(18/07/1995&#x2013;10/03/1998)</td>
<td align="center">846 days</td>
<td align="center">331</td>
<td align="center">4.5</td>
<td align="center">V, s-P, PDC, LDG, LDC</td>
</tr>
<tr>
<td align="center">Pause 1</td>
<td align="center">(11/03/1998&#x2013;26/11/1999)</td>
<td align="center">627 days</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="left"/>
</tr>
<tr>
<td align="center">Phase 2</td>
<td align="center">(27/11/1999&#x2013;28/07/2003)</td>
<td align="center">1339 days</td>
<td align="center">336</td>
<td align="center">2.9</td>
<td align="center">V, PDC, LDG, LDC</td>
</tr>
<tr>
<td align="center">Pause 2</td>
<td align="center">(29/07/2003&#x2013;31/07/2005)</td>
<td align="center">735 days</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="left"/>
</tr>
<tr>
<td align="center">Phase 3</td>
<td align="center">(01/08/2005&#x2013;20/04/2007)</td>
<td align="center">627 days</td>
<td align="center">282</td>
<td align="center">5.6</td>
<td align="center">LDG</td>
</tr>
<tr>
<td align="center">Pause 3</td>
<td align="center">(21/04/2007&#x2013;28/07/2008)</td>
<td align="center">466 days</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="left"/>
</tr>
<tr>
<td align="center">Phase 4</td>
<td align="center">(29/07/2008&#x2013;03/01/2009)</td>
<td align="center">158 days</td>
<td align="center">39</td>
<td align="center">2.9</td>
<td align="center">V, LDG</td>
</tr>
<tr>
<td align="center">Pause 4</td>
<td align="center">(04/01/2009&#x2013;08/10/2009)</td>
<td align="center">279 days</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="left"/>
</tr>
<tr>
<td align="center">Phase 5</td>
<td align="center">(09/10/2009&#x2013;11/02/2010)</td>
<td align="center">125 days</td>
<td align="center">70</td>
<td align="center">6.8</td>
<td align="center">LDG, LDC, V</td>
</tr>
<tr>
<td align="center">Pause 5</td>
<td align="center">(12/02/2010 - present)</td>
<td align="center">&#x223c;5,300 days as of October 2024</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="left"/>
</tr>
</tbody>
</table>
<table-wrap-foot>
<fn>
<p>V, Vulcanian; s-P, sub-Plinian; PDC, pyroclastic density current; LDG - lava dome growth; LDC, lava dome collapse. Compiled from <xref ref-type="bibr" rid="B64">Kokelaar, (2002)</xref>, <xref ref-type="bibr" rid="B41">Edmonds et al. (2016)</xref>, <xref ref-type="bibr" rid="B104">Ryan et al. (2010)</xref>, <xref ref-type="bibr" rid="B110">Sparks and Young, (2002)</xref>, <xref ref-type="bibr" rid="B32">Cole et al. (2014)</xref>, <xref ref-type="bibr" rid="B117">Wadge et al. (2014)</xref>.</p>
</fn>
</table-wrap-foot>
</table-wrap>
<p>The 15-year eruptive activity is extensively detailed in a number of studies including <xref ref-type="bibr" rid="B100">Robertson et al. (2000)</xref>; <xref ref-type="bibr" rid="B64">Kokelaar (2002)</xref>; <xref ref-type="bibr" rid="B110">Sparks and Young (2002)</xref>; <xref ref-type="bibr" rid="B52">Harford et al. (2003)</xref> for Phases 1-2 and <xref ref-type="bibr" rid="B117">Wadge et al. (2014)</xref> for Phases 15, and is summarised in <xref ref-type="table" rid="T1">Table 1</xref> below.</p>
<sec id="s2-1-1">
<title>2.1.1 Constraints on petrology and the plumbing system</title>
<p>SHV products are phenocryst-rich (30&#x2013;45 vol%), with an assemblage of plagioclase, amphibole, orthopyroxene, titanomagnetite and quartz (&#x3c;0.5%), and minor amounts of clinopyroxene occurring as microphenocrysts or as overgrowth rims on orthopyroxene, plus apatite and ilmenite (<xref ref-type="bibr" rid="B57">Humphreys et al., 2009</xref>; <xref ref-type="bibr" rid="B40">Edmonds et al., 2014</xref>). Petrological features such as mineral phases and enclave textures are similar throughout the eruptive phases, as described in <xref ref-type="bibr" rid="B31">Christopher et al. (2014)</xref>. Whole rock compositions from all phases are largely andesitic and range from 57&#x2013;64 wt% SiO<sub>2</sub> (<xref ref-type="bibr" rid="B88">Murphy et al., 2000</xref>; <xref ref-type="bibr" rid="B123">Zellmer et al., 2003</xref>; <xref ref-type="bibr" rid="B95">Plail et al., 2018</xref>), while groundmass glass compositions, published for Phases 1&#x2013;3, are 70&#x2013;80 wt% SiO<sub>2</sub> (<xref ref-type="bibr" rid="B42">Edmonds et al., 2002</xref>; <xref ref-type="bibr" rid="B52">Harford et al., 2003</xref>; <xref ref-type="bibr" rid="B18">Buckley et al., 2006</xref>; <xref ref-type="bibr" rid="B58">Humphreys et al., 2010</xref>).</p>
<p>Geochemical and geophysical studies point to both a two-tiered magma storage region (e.g., <xref ref-type="bibr" rid="B5">Aspinall et al., 1998</xref>; <xref ref-type="bibr" rid="B11">Barclay et al., 1998</xref>; <xref ref-type="bibr" rid="B36">Devine et al., 2003</xref>; <xref ref-type="bibr" rid="B103">Rutherford and Devine, 2003</xref>; <xref ref-type="bibr" rid="B45">Foroozan et al., 2010</xref>; <xref ref-type="bibr" rid="B81">Miller et al., 2010</xref>; <xref ref-type="bibr" rid="B31">Christopher et al., 2014</xref>; <xref ref-type="bibr" rid="B40">Edmonds et al., 2014</xref>) or a transcrustal mush system at Soufri&#xe8;re Hills (e.g., <xref ref-type="bibr" rid="B41">Edmonds et al., 2016</xref>; <xref ref-type="bibr" rid="B50">Gottsmann et al., 2020</xref>; <xref ref-type="bibr" rid="B3">Alshembari et al., 2024</xref>). Published measurements of dissolved H<sub>2</sub>O and CO<sub>2</sub> contents within plagioclase and quartz-hosted melt inclusion glasses are 4.07&#x2013;5.05 wt% H<sub>2</sub>O and &#x3c;60 ppm CO<sub>2</sub> for Phase 1 inclusions (<xref ref-type="bibr" rid="B11">Barclay et al., 1998</xref>), and &#x2264;6.40 wt% H<sub>2</sub>O and &#x2264;546 ppm CO<sub>2</sub> for Phase 3 inclusions (<xref ref-type="bibr" rid="B40">Edmonds et al., 2014</xref>). These translate, via the solubility-pressure model VolatileCalc (<xref ref-type="bibr" rid="B91">Newman and Lowenstern, 2002</xref>), to pressure and thus depth estimates of &#x223c;130 MPa, and 5&#x2013;6 km for Phase 1 (<xref ref-type="bibr" rid="B11">Barclay et al., 1998</xref>) and &#x2264;300 MPa for Phase 3 (<xref ref-type="bibr" rid="B40">Edmonds et al., 2014</xref>) which is equivalent to &#x223c;7&#x2013;11 km. <xref ref-type="bibr" rid="B40">Edmonds et al. (2014)</xref> attributes the higher CO<sub>2</sub> content of a few plagioclase- and orthopyroxene-hosted inclusions of 836 and 1032 ppm to CO<sub>2</sub> flushing, which occurs when CO<sub>2</sub>- rich fluids are released from deeper in the magmatic system, in shallow conduit systems, or from carbonate sources, and interact with magmas stored in the upper or mid-crust (e.g., <xref ref-type="bibr" rid="B102">Rust et al., 2004</xref>; <xref ref-type="bibr" rid="B70">Marianelli et al., 2005</xref>; <xref ref-type="bibr" rid="B111">Spilliaert et al., 2006</xref>; <xref ref-type="bibr" rid="B14">Blundy et al., 2010</xref>; <xref ref-type="bibr" rid="B21">Caricchi et al., 2018</xref>).</p>
<p>However, these CO<sub>2</sub> measurements neglect melt inclusion bubble-hosted CO<sub>2</sub> and are thus likely severely underestimated (e.g., <xref ref-type="bibr" rid="B53">Hartley et al., 2014</xref>; <xref ref-type="bibr" rid="B84">Moore et al., 2015</xref>; <xref ref-type="bibr" rid="B120">Wieser et al., 2021</xref>). The estimated magma storage depths of 5&#x2013;6 km are similar to earthquake hypocentral depths and seismic tomographic data (<xref ref-type="bibr" rid="B5">Aspinall et al., 1998</xref>; <xref ref-type="bibr" rid="B81">Miller et al., 2010</xref>). Mineral geochemistry also yields shallow storage depths (around 5&#x2013;6 km), via Al-in-hornblende geobarometry (<xref ref-type="bibr" rid="B103">Rutherford and Devine, 2003</xref>) and clinopyroxene-melt equilibria (<xref ref-type="bibr" rid="B31">Christopher et al., 2014</xref>). However, iron oxide compositions (<xref ref-type="bibr" rid="B36">Devine et al., 2003</xref>) point to deeper storage regions &#x3e;10 km, along with H<sub>2</sub>O contents of enstatites (<xref ref-type="bibr" rid="B41">Edmonds et al., 2016</xref>), which indicate a magma storage region that is vertically elongated through the crust.</p>
<p>A two-tiered model is suggested from geodesy, where best-model fits to GPS data from Phase 1 identify a source at &#x223c;6 km depth (<xref ref-type="bibr" rid="B72">Mattioli et al., 1998</xref>), seemingly switching to a deeper-fed region at 10.4 &#xb1; 2.1 km during the later phases (<xref ref-type="bibr" rid="B73">Mattioli et al., 2010</xref>). <xref ref-type="bibr" rid="B45">Foroozan et al. (2010)</xref> suggests 5 km and 17 km deep storage regions, also based on GPS data. More recently, geodetic modelling using 3D crustal mechanical and topographical data has proposed the presence of a vertically extended pressure source between &#x223c;4 and 14 km depth (<xref ref-type="bibr" rid="B50">Gottsmann et al., 2020</xref>).</p>
</sec>
</sec>
</sec>
<sec sec-type="methods" id="s3">
<title>3 Methodology</title>
<sec id="s3-1">
<title>3.1 Sample details and preparation</title>
<p>Samples from the five eruption phases were sourced from the Montserrat Volcano Observatory&#x2019;s rock catalogue and are listed in <xref ref-type="table" rid="T2">Table 2</xref>. They were crushed and separated into different sized fractions, and plagioclase and orthopyroxene phenocrysts were hand separated from the 500&#x2013;1000 &#xb5;m fraction under a binocular microscope. For this study, plagioclase and orthopyroxene were selected due to their abundance and optical properties allowing for easy preparation and analysis of melt inclusions.</p>
<table-wrap id="T2" position="float">
<label>TABLE 2</label>
<caption>
<p>List of samples used in this study along with dates of production, brief descriptions and the analytical techniques applied.</p>
</caption>
<table>
<thead valign="top">
<tr>
<th align="center">Phase</th>
<th align="center">Sample ID</th>
<th align="center">Date and Description</th>
</tr>
</thead>
<tbody valign="top">
<tr>
<td align="center">Phase 1</td>
<td align="center">MVO1085</td>
<td align="left">Glassy melt inclusions in pumice<break/>Trapped in plagioclase and orthopyroxene<break/>September/October 1997 explosion PDCs</td>
</tr>
<tr>
<td align="center">Phase 2</td>
<td align="center">MVO1243</td>
<td align="left">Glassy melt inclusions in pumice Trapped in plagioclase<break/>3 March 2004</td>
</tr>
<tr>
<td align="center">Phase 3</td>
<td align="center">MVO1524</td>
<td align="left">Crystallised melt inclusions in pumice<break/>8 January 2007 PDCs</td>
</tr>
<tr>
<td align="center">Phase 4</td>
<td align="center">MVO1531</td>
<td align="left">Glassy melt inclusions in pumice<break/>Trapped in plagioclase<break/>28 July 2008 PDCs</td>
</tr>
<tr>
<td align="center">Phase 5</td>
<td align="center">MVO1548</td>
<td align="left">Glassy melt inclusions in pumice<break/>Trapped in plagioclase and orthopyroxene<break/>11 February 2010 pumice airfall</td>
</tr>
</tbody>
</table>
</table-wrap>
<p>Individual phenocrysts were mounted on glass slides and gently polished to a flat surface using 2400 silicon carbide lapping paper and inspected under a microscope. Samples containing glassy melt inclusions were further polished with 3 and 1 &#xb5;m alumina paper until the inclusions were within &#x223c;20&#x2013;30 &#xb5;m of the surface in preparation for Raman spectroscopy. Glassy melt inclusions occurred in Phases 1, 2, 4, and 5, with Phase 3 inclusions being crystallised, likely reflecting a longer cooling history, and are therefore not considered for the analytical techniques applied in this study.</p>
<p>Inclusions analysed by Raman spectroscopy were 10&#x2013;166 &#xb5;m along their longest axis and were cuboidal (plagioclase-hosted) or ellipsoidal (orthopyroxene-hosted). All plagioclase-hosted inclusions contained at least one vapour bubble ranging from 3 to 52 &#x3bc;m, and orthopyroxene-hosted inclusions were either bubble free or contained at least one bubble, where bubble size ranged from 2 to 23 &#xb5;m.</p>
<p>Following Raman spectroscopy, inclusions &#x3e;25 &#xb5;m and therefore large enough to be analysed by SIMS were polished with 3 and 1 &#xb5;m aluminium oxide paper, (to avoid carbon contamination posed by diamond paste) until the inclusion glass was exposed at the surface. These samples were then washed in acetone to dissolve any adhesive resin, mounted in indium, and gold coated for SIMS analysis.</p>
<p>Following SIMS, samples were lightly polished with 0.25 &#xb5;m diamond paste to remove the gold coat and carbon coated for EPMA.</p>
<p>Whole rock samples from all five phases were also crushed and separated into the 100 &#xb5;m fraction in preparation for ICP-OES.</p>
</sec>
<sec id="s3-2">
<title>3.2 Analytical techniques</title>
<sec id="s3-2-1">
<title>3.2.1 Raman spectroscopy</title>
<p>Bubbles in melt inclusions were analysed at the Laboratoire Magmas et Volcans (LMV), Clermont-Ferrand, France using a Renishaw inVia confocal Raman microspectrometer. This was equipped with a 532.1 &#xb1; 0.3 nm diode-pulsed solid state laser, a Rayleigh rejection edge filter (cut-off at about 50 cm<sup>&#x2212;1</sup>), and a CCD detector of 1040 &#xd7; 256 pixels. For each analysis, a slit aperture of 20 &#xb5;m (high confocality setting) and a grating of 2400 grooves/mm was used. A Leica DM 2500 M optical microscope with a motorised XYZ stage was used to focus samples, and &#xd7;50 or &#xd7;100 microscope objectives were used, dependent on bubble size. A spectral resolution better than 0.4 cm<sup>&#x2212;1</sup>, and spatial resolutions of few &#xb5;m were achieved based on the applied conditions. To calibrate peak positions and check the linearity of the spectrometer, the 520.5 cm<sup>&#x2212;1</sup> peak of Si and the two neon emission bands (568.982 and 576.442 nm) were used, as the neon bands bracket the peaks of CO<sub>2</sub>, known as the Fermi diad (&#x394;, peaks at &#x223c;1388 and 1285 cm<sup>&#x2212;1</sup>). In order to acquire CO<sub>2</sub> spectra used for quantification of CO<sub>2</sub> concentration, spectra were collected in a single window ranging from &#x223c;725 to 1880 cm<sup>&#x2212;1</sup>, using the WiRE&#x2122; 4.4 software. Each measurement took 120 s (3 acquisitions of 40 s). Neon bands were measured before and after each analysis of CO<sub>2</sub> and the correction factor (<sup>real</sup>&#x394;<sub>Ne</sub>/<sup>measured</sup>&#x394;<sub>Ne</sub>) for each measurement lies between 0.9987 and 1.0003. In order to quantify CO<sub>2</sub> concentration in the bubbles, fluid inclusions of pure CO<sub>2</sub> with known densities were used as standards and were analysed three times during each analytical session (<xref ref-type="bibr" rid="B15">Boudoire et al., 2023</xref>). Uncertainties associated with the reproducibility of the measurement determined on standards are &#x3c;0.04 g/cc. The 60&#x2013;1320 cm<sup>&#x2212;1</sup> wavenumber range was subsequently examined for the identification of mineral phases known to occur in the bubble (sulfates, carbonates, etc.). The presence of other fluid species (i.e., liquid or vapour H<sub>2</sub>O, H<sub>2</sub>S, HS<sup>&#x2212;</sup>) was also investigated by measuring the whole spectral range up to 4,000 cm<sup>&#x2212;1</sup>.</p>
</sec>
<sec id="s3-2-2">
<title>3.2.2 Secondary ion man spectrometry (SIMS)</title>
<p>The concentration of H<sub>2</sub>O and CO<sub>2</sub> in melt inclusions glasses were measured at the Natural Environment Research Council (NERC) Ion-Probe Facility at University of Edinburgh, UK using a Cameca IMS 7f-GEO paired with a 5 nA <sup>16</sup>O<sup>&#x2212;</sup> beam.</p>
<p>Prior to analysis, each sample was pre-sputtered for 180 s <sup>24</sup>Mg<sup>2&#x2b;</sup>, <sup>26</sup>Mg, <sup>30</sup>Si (counting times &#x3d; 2s), <sup>1</sup>H (counting time &#x3d; 1s) and <sup>12</sup>C (counting time &#x3d; 10 s) were analysed over 10 cycles with an electron multiplier. In order to separate the mass interferences of <sup>24</sup>Mg<sup>2&#x2b;</sup> and <sup>12</sup>C, a mass resolving power of 2000 was applied. The curves of <sup>1</sup>H/<sup>30</sup>Si vs. H<sub>2</sub>O and (<sup>12</sup>C/<sup>30</sup>Si)&#x2a;SiO<sub>2</sub> vs. CO<sub>2</sub> for H<sub>2</sub>O and CO<sub>2</sub> respectively, were used for calibration based on a set of known glass standards (<xref ref-type="sec" rid="s13">Supplementary Figure S1</xref>; H<sub>2</sub>O &#x3d; 0.64&#x2013;7.56 wt%; CO<sub>2</sub> &#x3d; 0&#x2013;10,380 ppm). Eight of fifteen orthopyroxene-hosted, and one of sixty-one plagioclase-hosted inclusions required calculation of H<sub>2</sub>O by difference, due to high measured H<sub>2</sub>O contents which exceeded that of the standards (7.89&#x2013;8.76 wt%), leading to high total oxides of 102&#x2013;104 wt%. H<sub>2</sub>O was calculated to achieve totals of 100.44 wt%, the average total for the remaining orthopyroxene-hosted inclusions where the standard deviation is 0.54 wt%. Calculation of CO<sub>2</sub> required SiO<sub>2</sub> which was measured via EPMA. H has a matrix correction and does not require further correction. Background concentrations for H<sub>2</sub>O and CO<sub>2</sub> were measured on nominally anhydrous minerals (plagioclase and orthopyroxene) before final concentration calculations. Pressure in the sample chamber was &#x3c;6.80 &#xd7; 10<sup>&#x2212;8</sup> mbar over the analytical session. Reproducibility (2&#x3c3;) on known standards amounts to &#x3c;10% for both H<sub>2</sub>O and CO<sub>2</sub>, with a detection limit of 0.003 wt% for H<sub>2</sub>O, and 3 ppm CO<sub>2</sub>.</p>
</sec>
<sec id="s3-2-3">
<title>3.2.3 Electron probe microanalysis (EPMA)</title>
<p>Melt inclusion glass and host major elements were analysed at the University of Cambridge utilising a JEOL JXA-iHP200F HyperProbe with 15 kV accelerating voltage.</p>
<p>Major elements in the melt inclusion glasses were measured with a beam size of 5 &#xb5;m. A 5 &#xb5;m and a defocused beam were respectively applied for major element analysis of plagioclase and orthopyroxene host crystals. Beam current of 6 nA was applied across all analyses, and alkalis were measured first to mitigate for loss or migration.</p>
<p>Reproducibility (2&#x3c3;) of major elements is based on repeat measurements of known rhyolitic glass standard AthoG and are &#x3c;5% for SiO<sub>2</sub>, TiO<sub>2</sub>, Al<sub>2</sub>O<sub>3</sub>, FeO and CaO, &#x3c;10% for K<sub>2</sub>O, &#x3c;13% for MgO and Na<sub>2</sub>O.</p>
<p>Counting times for each element along with standards and associated diffraction crystals used for glass analysis are listed in <xref ref-type="sec" rid="s13">Supplementary Table S1</xref>.</p>
</sec>
<sec id="s3-2-4">
<title>3.2.4 Inductively coupled plasma optical emission spectrometry (ICP-OES)</title>
<p>Whole rock samples from Phases 1-5 were analysed for major element composition at LMV, France using an Agilent 5800 ICP-OES instrument.</p>
<p>An induction furnace was used to melt 100 mg of each sample together with 300 mg of LiBO<sub>2</sub>. The resulting product was dissolved in 1M HNO<sub>3</sub> until a final volume of 200 mL was achieved. &#x201c;GH&#x201d; and &#x2018;BR&#x2019; from Centre de Recherches P&#xe9;trographiques et G&#xe9;ochimiques (CRPG), Nancy, France were used as standards for Si, Na and K, and Al, Ti, Fe, Mn, Mg, Ca and P respectively (<xref ref-type="sec" rid="s13">Supplementary Table S2</xref>). The errors on reproducibility of the standards are &#x3c;10% (2&#x3c3;).</p>
</sec>
</sec>
</sec>
<sec sec-type="results" id="s4">
<title>4 Results</title>
<sec id="s4-1">
<title>4.1 Whole rock and host compositions</title>
<p>Whole rock compositions across the five phases are andesitic, spanning 57.84&#x2013;59.97 wt% SiO<sub>2</sub> (<xref ref-type="fig" rid="F2">Figure 2</xref>; <xref ref-type="table" rid="T3">Table 3</xref>) and contain the mineral assemblage outlined in <xref ref-type="sec" rid="s2-1-1">Section 2.1.1</xref>. Samples from this study are comparable to published data across the five phases (<xref ref-type="bibr" rid="B88">Murphy et al., 2000</xref>; <xref ref-type="bibr" rid="B123">Zellmer et al., 2003</xref>; <xref ref-type="bibr" rid="B95">Plail et al., 2018</xref>), and are less evolved than groundmass glass compositions (70&#x2013;80 wt% SiO<sub>2</sub>) published for Phases 1&#x2013;3 (<xref ref-type="bibr" rid="B43">Edmonds et al., 2001</xref>; <xref ref-type="bibr" rid="B42">Edmonds et al., 2002</xref>; <xref ref-type="bibr" rid="B52">Harford et al., 2003</xref>; <xref ref-type="bibr" rid="B18">Buckley et al., 2006</xref>; <xref ref-type="bibr" rid="B58">Humphreys et al., 2010</xref>).</p>
<fig id="F2" position="float">
<label>FIGURE 2</label>
<caption>
<p>Total alkali vs. silica (TAS) plot of whole rock samples and melt inclusions from SHV. Whole rock are predominantly andesite composition except for two samples. Melt inclusions are dacitic to rhyolitic. Published data for whole rock are from <xref ref-type="bibr" rid="B88">Murphy et al., 2000</xref>, <xref ref-type="bibr" rid="B123">Zellmer et al., 2003</xref>; <xref ref-type="bibr" rid="B95">Plail et al., 2018</xref>. Published data for melt inclusions are from <xref ref-type="bibr" rid="B11">Barclay et al., 1998</xref>, <xref ref-type="bibr" rid="B35">Devine et al., 1998</xref>, <xref ref-type="bibr" rid="B43">Edmonds et al., 2001</xref>; <xref ref-type="bibr" rid="B58">Humphreys et al., 2010</xref>.</p>
</caption>
<graphic xlink:href="feart-12-1509409-g002.tif"/>
</fig>
<table-wrap id="T3" position="float">
<label>TABLE 3</label>
<caption>
<p>Whole rock compositions of samples from Phases 1-5 in wt%. Total iron is given as Fe<sub>2</sub>O<sub>3</sub> and H<sub>2</sub>O is loss on ignition.</p>
</caption>
<table>
<thead valign="top">
<tr>
<th rowspan="3" align="center"/>
<th colspan="9" align="center">Whole rock samples</th>
</tr>
<tr>
<th align="center">Phase 1</th>
<th align="center">Phase 1</th>
<th align="center">Phase 1</th>
<th align="center">Phase 2</th>
<th align="center">Phase 2</th>
<th align="center">Phase 3</th>
<th align="center">Phase 4</th>
<th align="center">Phase 4</th>
<th align="center">Phase 5</th>
</tr>
<tr>
<th align="center">MVO<break/>1085</th>
<th align="center">MVO<break/>1085</th>
<th align="center">MVO<break/>1085</th>
<th align="center">MVO<break/>1243</th>
<th align="center">MVO<break/>1243</th>
<th align="center">MVO<break/>1524</th>
<th align="center">MVO<break/>1531</th>
<th align="center">MVO<break/>1531</th>
<th align="center">MVO<break/>1548</th>
</tr>
</thead>
<tbody valign="top">
<tr>
<td align="left">SiO<sub>2</sub>
</td>
<td align="center">58.89</td>
<td align="center">59.97</td>
<td align="center">58.63</td>
<td align="center">57.84</td>
<td align="center">58.61</td>
<td align="center">59.48</td>
<td align="center">58.35</td>
<td align="center">58.01</td>
<td align="center">59.23</td>
</tr>
<tr>
<td align="left">TiO<sub>2</sub>
</td>
<td align="center">0.60</td>
<td align="center">0.56</td>
<td align="center">0.50</td>
<td align="center">0.57</td>
<td align="center">0.60</td>
<td align="center">0.59</td>
<td align="center">0.60</td>
<td align="center">0.62</td>
<td align="center">0.58</td>
</tr>
<tr>
<td align="left">Al<sub>2</sub>O<sub>3</sub>
</td>
<td align="center">17.53</td>
<td align="center">17.55</td>
<td align="center">17.52</td>
<td align="center">18.20</td>
<td align="center">18.17</td>
<td align="center">18.32</td>
<td align="center">17.94</td>
<td align="center">18.00</td>
<td align="center">18.49</td>
</tr>
<tr>
<td align="left">Fe<sub>2</sub>O<sub>3</sub>
</td>
<td align="center">7.10</td>
<td align="center">6.78</td>
<td align="center">6.56</td>
<td align="center">6.89</td>
<td align="center">7.34</td>
<td align="center">7.29</td>
<td align="center">7.09</td>
<td align="center">7.29</td>
<td align="center">6.93</td>
</tr>
<tr>
<td align="left">MnO</td>
<td align="center">0.16</td>
<td align="center">0.16</td>
<td align="center">0.18</td>
<td align="center">0.15</td>
<td align="center">0.17</td>
<td align="center">0.17</td>
<td align="center">0.15</td>
<td align="center">0.16</td>
<td align="center">0.16</td>
</tr>
<tr>
<td align="left">MgO</td>
<td align="center">2.92</td>
<td align="center">2.54</td>
<td align="center">3.05</td>
<td align="center">2.76</td>
<td align="center">3.04</td>
<td align="center">2.80</td>
<td align="center">3.04</td>
<td align="center">3.06</td>
<td align="center">2.93</td>
</tr>
<tr>
<td align="left">CaO</td>
<td align="center">7.44</td>
<td align="center">7.08</td>
<td align="center">7.35</td>
<td align="center">7.73</td>
<td align="center">7.84</td>
<td align="center">7.76</td>
<td align="center">7.73</td>
<td align="center">7.81</td>
<td align="center">7.85</td>
</tr>
<tr>
<td align="left">Na<sub>2</sub>O</td>
<td align="center">3.51</td>
<td align="center">3.59</td>
<td align="center">3.53</td>
<td align="center">3.51</td>
<td align="center">3.51</td>
<td align="center">3.41</td>
<td align="center">3.37</td>
<td align="center">3.43</td>
<td align="center">3.54</td>
</tr>
<tr>
<td align="left">K<sub>2</sub>O</td>
<td align="center">0.84</td>
<td align="center">0.85</td>
<td align="center">0.76</td>
<td align="center">0.75</td>
<td align="center">0.79</td>
<td align="center">0.80</td>
<td align="center">0.74</td>
<td align="center">0.74</td>
<td align="center">0.82</td>
</tr>
<tr>
<td align="left">P<sub>2</sub>O<sub>5</sub>
</td>
<td align="center">0.13</td>
<td align="center">0.12</td>
<td align="center">0.12</td>
<td align="center">0.12</td>
<td align="center">0.13</td>
<td align="center">0.13</td>
<td align="center">0.12</td>
<td align="center">0.13</td>
<td align="center">0.13</td>
</tr>
<tr>
<td align="left">Ba</td>
<td align="center">0.02</td>
<td align="center">0.02</td>
<td align="center">0.02</td>
<td align="center">0.02</td>
<td align="center">0.02</td>
<td align="center">0.02</td>
<td align="center">0.02</td>
<td align="center">0.02</td>
<td align="center">0.02</td>
</tr>
<tr>
<td align="left">Sr</td>
<td align="center">0.03</td>
<td align="center">0.03</td>
<td align="center">0.03</td>
<td align="center">0.03</td>
<td align="center">0.03</td>
<td align="center">0.03</td>
<td align="center">0.03</td>
<td align="center">0.03</td>
<td align="center">0.03</td>
</tr>
<tr>
<td align="left">H<sub>2</sub>O</td>
<td align="center">0.58</td>
<td align="center">0.48</td>
<td align="center">0.46</td>
<td align="center">0.36</td>
<td align="center">0.41</td>
<td align="center">0.74</td>
<td align="center">0.55</td>
<td align="center">0.26</td>
<td align="center">0.38</td>
</tr>
<tr>
<td align="left">Total</td>
<td align="center">99.74</td>
<td align="center">99.73</td>
<td align="center">98.70</td>
<td align="center">98.92</td>
<td align="center">100.65</td>
<td align="center">101.53</td>
<td align="center">99.72</td>
<td align="center">99.55</td>
<td align="center">101.09</td>
</tr>
</tbody>
</table>
</table-wrap>
<p>Fifty-eight of the melt inclusions across the four phases being studied are hosted in An<sub>48-58</sub> plagioclase, with three being hosted at An<sub>61-62</sub> and two at An<sub>68-71</sub>. Orthopyroxene data are only available for Phases 1 and 5 due to a restricted number of melt inclusions that are sufficiently large, glassy and crystal-free. Orthopyroxene phenocrysts from both phases occupy restricted compositional range of En<sub>57-59</sub>.</p>
<p>All plagioclase phenocrysts across the studied Phases are out of equilibrium with the whole rock, at a total K<sub>D</sub> range of 0.16&#x2013;0.54 (applicable K<sub>D</sub> range for equilibrium &#x3d; 0.05&#x2013;0.15; <xref ref-type="sec" rid="s4-2-1">section 4.2.1</xref>). However, equilibrium is achieved between 11 of 16 Phase 1 inclusions and the average groundmass glass composition for Phase 1 (<xref ref-type="bibr" rid="B42">Edmonds et al., 2002</xref>; <xref ref-type="bibr" rid="B52">Harford et al., 2003</xref>; <xref ref-type="bibr" rid="B18">Buckley et al., 2006</xref>). None of the fourteen Phase 2 inclusions are in equilibrium with the average groundmass glass composition for Phase 2 (<xref ref-type="bibr" rid="B42">Edmonds et al., 2002</xref>; <xref ref-type="bibr" rid="B18">Buckley et al., 2006</xref>; <xref ref-type="bibr" rid="B58">Humphreys et al., 2010</xref>). Equilibrium is unable to be calculated between inclusions and the average groundmass compositions for Phases 4 and 5 as there are no published values of Phase 4 and 5 groundmass glasses.</p>
<p>The five analysed orthopyroxene melt inclusions from Phase 1 are out of equilibrium with the average whole rock (K<sub>D</sub> &#x3d; 0.49&#x2013;0.55; <xref ref-type="sec" rid="s4-2-1">section 4.2.1</xref>), along with the groundmass glass (<xref ref-type="bibr" rid="B43">Edmonds et al., 2001</xref>; <xref ref-type="bibr" rid="B52">Harford et al., 2003</xref>; <xref ref-type="bibr" rid="B18">Buckley et al., 2006</xref>) at a K<sub>D</sub> range of 0.18&#x2013;0.19. Equilibrium is also not achieved between the nine Phase 5 inclusions and the average whole rock composition (K<sub>D</sub> &#x3d; 0.49&#x2013;0.55), and equilibrium between mineral and groundmass glass for Phase 5 cannot be calculated due to lack of measured groundmass glass compositions for Phase 5.</p>
</sec>
<sec id="s4-2">
<title>4.2 Melt inclusions</title>
<sec id="s4-2-1">
<title>4.2.1 Post-entrapment modifications</title>
<p>Post-entrapment modification of melt inclusion compositions is common, and occurs via diverse processes, resulting in compositions not representative of the parental melt. These processes include post-entrapment crystallisation that modifies both major and volatile elements (<xref ref-type="bibr" rid="B4">Anderson and Brown, 1993</xref>; <xref ref-type="bibr" rid="B33">Danyushevsky et al., 2000</xref>; <xref ref-type="bibr" rid="B63">Kent, 2008</xref>), the formation of bubbles that can be empty (<xref ref-type="bibr" rid="B106">Schipper et al., 2010</xref>; <xref ref-type="bibr" rid="B112">Steele-Macinnis et al., 2011</xref>), or contain vapour (<xref ref-type="bibr" rid="B4">Anderson and Brown, 1993</xref>; <xref ref-type="bibr" rid="B84">Moore et al., 2015</xref>; <xref ref-type="bibr" rid="B83">Moore and Bodnar, 2019</xref>), or aqueous species and solids (<xref ref-type="bibr" rid="B105">Schiavi et al., 2020</xref>). Other processes include diffusion of H<sup>&#x2b;</sup> into and out of inclusions (<xref ref-type="bibr" rid="B47">Gaetani et al., 2012</xref>), altering H<sub>2</sub>O contents, and decrepitation leading to volatile loss (<xref ref-type="bibr" rid="B89">Neave et al., 2017</xref>). As these processes allow for misrepresentation of the major element and volatile composition of the melt, it is important to assess their extent in individual inclusions, and make corrections where possible, prior to further modelling.</p>
<sec id="s4-2-1-1">
<title>4.2.1.1 Post entrapment crystallisation (PEC)</title>
<p>Assessment of PEC for plagioclase-liquid pairs was carried out by two methods. Firstly, we considered the anorthite-albite exchange between the inclusion and its host which varies with temperature, where <inline-formula id="inf1">
<mml:math id="m1">
<mml:mrow>
<mml:msub>
<mml:mi>K</mml:mi>
<mml:mi>D</mml:mi>
</mml:msub>
<mml:mo>&#x3d;</mml:mo>
<mml:mn>0.10</mml:mn>
<mml:mtext>&#x2009;</mml:mtext>
<mml:mo>&#xb1;</mml:mo>
<mml:mn>0.05</mml:mn>
</mml:mrow>
</mml:math>
</inline-formula> for inclusions trapped &#x3c;1050&#xb0;C and <inline-formula id="inf2">
<mml:math id="m2">
<mml:mrow>
<mml:msub>
<mml:mi>K</mml:mi>
<mml:mi>D</mml:mi>
</mml:msub>
<mml:mo>&#x3d;</mml:mo>
<mml:mn>0.28</mml:mn>
<mml:mtext>&#x2009;</mml:mtext>
<mml:mo>&#xb1;</mml:mo>
<mml:mn>0.11</mml:mn>
</mml:mrow>
</mml:math>
</inline-formula> for those trapped at &#x2265;1050&#xb0;C (<xref ref-type="bibr" rid="B96">Putirka, 2008</xref>). As magmatic temperature at SHV are &#x223c;850&#xb0;C based on petrological and experimental studies (<xref ref-type="bibr" rid="B110">Sparks and Young, 2002</xref>), the lower temperature K<sub>D</sub> value of 0.10 &#xb1; 0.05 was used to assess equilibrium. According to this equilibrium test, 52% of inclusions were in equilibrium with their hosts, with a total K<sub>D</sub> range of 0.02&#x2013;0.07. However, due to the hydrous nature of the inclusions, K<sub>D</sub> may not be an accurate indicator of equilibrium for SHV inclusions, as equilibrium is affected by H<sub>2</sub>O degassing (<xref ref-type="bibr" rid="B59">Humphreys et al., 2016</xref>), and a second method was employed. As an alternative test for equilibrium, the Al<sub>2</sub>O<sub>3</sub>-SiO<sub>2</sub>, Al<sub>2</sub>O<sub>3</sub>-MgO, Al<sub>2</sub>O<sub>3</sub>-K<sub>2</sub>O and MgO-K<sub>2</sub>O systematics of the melt inclusions in relation to the established liquid line of descent (LLD) for SHV whole rock and groundmass glasses were assessed, as PEC leads to a decrease in Al<sub>2</sub>O<sub>3</sub> and an increase in MgO (e.g., <xref ref-type="fig" rid="F3">Figure 3</xref>; <xref ref-type="bibr" rid="B93">Nielsen, 2011</xref>). As no deviation from any of the tested LLDs occurred, this is interpreted as an indication of no PEC occurring in the plagioclase-hosted inclusions, and therefore no correction being required.</p>
<fig id="F3" position="float">
<label>FIGURE 3</label>
<caption>
<p>Various liquid lines of descent for whole rock and groundmass glass compositions, in relation to melt inclusion compositions. Red lines indicate the amount (&#x223c;15%) and direction that compositions of plagioclase-hosted inclusions would follow as a result of post-entrapment crystallization. Therefore, SHV melt inclusions do not show any indication of post-entrapment crystallisation, as data do not follow the red lines. <bold>(A)</bold> Al<sub>2</sub>O<sub>3</sub> vs. K<sub>2</sub>O. <bold>(B)</bold> MgO vs. K<sub>2</sub>O. <bold>(C)</bold> Al<sub>2</sub>O<sub>3</sub> vs. MgO. <bold>(D)</bold> Al<sub>2</sub>O<sub>3</sub> vs. SiO<sub>2</sub>.</p>
</caption>
<graphic xlink:href="feart-12-1509409-g003.tif"/>
</fig>
<p>Orthopyroxene-liquid pairs were tested for equilibrium according to the K<sub>D</sub> threshold of <inline-formula id="inf3">
<mml:math id="m3">
<mml:mrow>
<mml:msubsup>
<mml:msub>
<mml:mi>K</mml:mi>
<mml:mi>D</mml:mi>
</mml:msub>
<mml:mrow>
<mml:mi>p</mml:mi>
<mml:mi>x</mml:mi>
<mml:mo>&#x2212;</mml:mo>
<mml:mi>l</mml:mi>
<mml:mi>i</mml:mi>
<mml:mi>q</mml:mi>
</mml:mrow>
<mml:mrow>
<mml:mi>F</mml:mi>
<mml:mi>e</mml:mi>
<mml:mo>&#x2212;</mml:mo>
<mml:mi>M</mml:mi>
<mml:mi>g</mml:mi>
</mml:mrow>
</mml:msubsup>
<mml:mo>&#x3d;</mml:mo>
<mml:mn>0.29</mml:mn>
<mml:mo>&#xb1;</mml:mo>
<mml:mn>0.06</mml:mn>
</mml:mrow>
</mml:math>
</inline-formula> (<xref ref-type="bibr" rid="B96">Putirka, 2008</xref>). All inclusions were out of equilibrium with their hosts at a K<sub>D</sub> range of 0.05&#x2013;0.22, and PEC ranges from 0.96% to 3.33%. Due to the low amount of PEC, the compositions of orthopyroxene-hosted melt inclusions do not require correcting, as this process has been shown to have negligible effects on both major and volatile elements up to 11% PEC (<xref ref-type="bibr" rid="B85">Moretti et al., 2018</xref>).</p>
<p>Melt inclusion compositions are listed in <xref ref-type="table" rid="T4">Table 4</xref>.</p>
<table-wrap id="T4" position="float">
<label>TABLE 4</label>
<caption>
<p>Compositions for seventy-eight melt inclusions across Phases 1 - 5 for Soufri&#xe8;re Hills Volcano. Major element oxides in wt% are measured via EPMA. H<sub>2</sub>O and CO<sub>2</sub> in the glass are measured by SIMS. CO<sub>2</sub> in the bubble is measured via Raman spectroscopy. PEC refers to post-entrapment crystallisation as assessed in <xref ref-type="sec" rid="s4-2-1">Section 4.2.1</xref>.</p>
</caption>
<table>
<thead valign="top">
<tr>
<th colspan="18" align="center">Melt inclusion compositions</th>
</tr>
<tr>
<th rowspan="2" align="center">Sample</th>
<th colspan="9" align="center">Major elements (wt%)</th>
<th colspan="6" align="center">Volatile elements</th>
<th colspan="2" align="center">Hosts</th>
</tr>
<tr>
<th align="center">SiO<sub>2</sub>
</th>
<th align="center">TiO<sub>2</sub>
</th>
<th align="center">Al<sub>2</sub>O<sub>3</sub>
</th>
<th align="center">FeO</th>
<th align="center">MgO</th>
<th align="center">CaO</th>
<th align="center">Na<sub>2</sub>O</th>
<th align="center">K<sub>2</sub>O</th>
<th align="center">Total</th>
<th align="center">H<sub>2</sub>O (wt%)</th>
<th align="center">Error&#xb1;</th>
<th align="center">Bubble CO<sub>2</sub> (ppm)</th>
<th align="center">Error&#xb1;</th>
<th align="center">Glass CO<sub>2</sub> (ppm)</th>
<th align="center">Error&#xb1;</th>
<th align="center">En</th>
<th align="center">An</th>
</tr>
</thead>
<tbody valign="top">
<tr>
<td colspan="18" align="left">Orthopyroxene-Hosted Melt Inclusions</td>
</tr>
<tr>
<td align="left">SHV_P1_OPX_005</td>
<td align="center">71.08</td>
<td align="center">0.16</td>
<td align="center">12.18</td>
<td align="center">2.34</td>
<td align="center">0.28</td>
<td align="center">1.64</td>
<td align="center">2.86</td>
<td align="center">2.48</td>
<td align="center">93.65</td>
<td align="center">6.67</td>
<td align="center">0.67</td>
<td align="center">n.d</td>
<td align="center">n.d</td>
<td align="center">84</td>
<td align="center">8</td>
<td align="center">58</td>
<td align="center">&#x2014;</td>
</tr>
<tr>
<td align="left">SHV_P1_OPX_008_MI1</td>
<td align="center">70.06</td>
<td align="center">0.22</td>
<td align="center">12.38</td>
<td align="center">2.42</td>
<td align="center">0.42</td>
<td align="center">1.90</td>
<td align="center">2.93</td>
<td align="center">2.23</td>
<td align="center">92.55</td>
<td align="center">6.82</td>
<td align="center">0.68</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">419</td>
<td align="center">42</td>
<td align="center">58</td>
<td align="center">&#x2014;</td>
</tr>
<tr>
<td align="left">SHV_P1_OPX_011_MI2</td>
<td align="center">71.78</td>
<td align="center">0.18</td>
<td align="center">11.85</td>
<td align="center">2.52</td>
<td align="center">0.40</td>
<td align="center">1.88</td>
<td align="center">2.64</td>
<td align="center">2.10</td>
<td align="center">93.49</td>
<td align="center">6.29</td>
<td align="center">0.62</td>
<td align="center">188</td>
<td align="center">41</td>
<td align="center">399</td>
<td align="center">40</td>
<td align="center">57</td>
<td align="center">&#x2014;</td>
</tr>
<tr>
<td align="left">SHV_P1_OPX_013_MI1</td>
<td align="center">70.21</td>
<td align="center">0.26</td>
<td align="center">12.69</td>
<td align="center">2.69</td>
<td align="center">0.35</td>
<td align="center">2.23</td>
<td align="center">2.93</td>
<td align="center">1.65</td>
<td align="center">93.42</td>
<td align="center">7.01</td>
<td align="center">0.70</td>
<td align="center">186</td>
<td align="center">54</td>
<td align="center">60</td>
<td align="center">6</td>
<td align="center">59</td>
<td align="center">&#x2014;</td>
</tr>
<tr>
<td align="left">SHV_P1_OPX_020</td>
<td align="center">71.54</td>
<td align="center">0.20</td>
<td align="center">11.79</td>
<td align="center">2.37</td>
<td align="center">0.39</td>
<td align="center">1.73</td>
<td align="center">3.00</td>
<td align="center">2.13</td>
<td align="center">94.03</td>
<td align="center">5.58</td>
<td align="center">0.56</td>
<td align="center">9</td>
<td align="center">9</td>
<td align="center">192</td>
<td align="center">19</td>
<td align="center">57</td>
<td align="center">&#x2014;</td>
</tr>
<tr>
<td align="left">SHV_P5_OPX_002_MI1</td>
<td align="center">72.49</td>
<td align="center">0.22</td>
<td align="center">11.90</td>
<td align="center">2.53</td>
<td align="center">0.11</td>
<td align="center">1.87</td>
<td align="center">3.04</td>
<td align="center">1.98</td>
<td align="center">94.68</td>
<td align="center">5.26</td>
<td align="center">0.53</td>
<td align="center">294</td>
<td align="center">41</td>
<td align="center">458</td>
<td align="center">46</td>
<td align="center">58</td>
<td align="center">&#x2014;</td>
</tr>
<tr>
<td align="left">SHV_P5_OPX_002_MI2</td>
<td align="center">70.89</td>
<td align="center">0.15</td>
<td align="center">11.88</td>
<td align="center">2.66</td>
<td align="center">0.39</td>
<td align="center">1.84</td>
<td align="center">2.91</td>
<td align="center">2.06</td>
<td align="center">92.95</td>
<td align="center">7.11</td>
<td align="center">0.71</td>
<td align="center">37</td>
<td align="center">14</td>
<td align="center">175</td>
<td align="center">18</td>
<td align="center">58</td>
<td align="center">&#x2014;</td>
</tr>
<tr>
<td align="left">SHV_P5_OPX_006_MI1</td>
<td align="center">71.14</td>
<td align="center">0.18</td>
<td align="center">11.86</td>
<td align="center">3.13</td>
<td align="center">0.46</td>
<td align="center">1.90</td>
<td align="center">2.70</td>
<td align="center">2.08</td>
<td align="center">93.78</td>
<td align="center">6.24</td>
<td align="center">0.62</td>
<td align="center">67</td>
<td align="center">33</td>
<td align="center">156</td>
<td align="center">16</td>
<td align="center">57</td>
<td align="center">&#x2014;</td>
</tr>
<tr>
<td align="left">SHV_P5_OPX_009_MI2</td>
<td align="center">70.23</td>
<td align="center">0.21</td>
<td align="center">12.34</td>
<td align="center">2.92</td>
<td align="center">0.38</td>
<td align="center">2.33</td>
<td align="center">3.06</td>
<td align="center">1.81</td>
<td align="center">93.49</td>
<td align="center">6.48</td>
<td align="center">0.65</td>
<td align="center">102</td>
<td align="center">27</td>
<td align="center">344</td>
<td align="center">34</td>
<td align="center">59</td>
<td align="center">&#x2014;</td>
</tr>
<tr>
<td align="left">SHV_P5_OPX_012_MI1</td>
<td align="center">70.69</td>
<td align="center">0.22</td>
<td align="center">12.02</td>
<td align="center">3.10</td>
<td align="center">0.36</td>
<td align="center">1.92</td>
<td align="center">3.07</td>
<td align="center">1.97</td>
<td align="center">93.47</td>
<td align="center">7.44</td>
<td align="center">0.74</td>
<td align="center">128</td>
<td align="center">38</td>
<td align="center">243</td>
<td align="center">24</td>
<td align="center">58</td>
<td align="center">&#x2014;</td>
</tr>
<tr>
<td align="left">SHV_P5_OPX_013_MI1</td>
<td align="center">70.78</td>
<td align="center">0.24</td>
<td align="center">12.12</td>
<td align="center">2.84</td>
<td align="center">0.36</td>
<td align="center">2.17</td>
<td align="center">2.93</td>
<td align="center">2.00</td>
<td align="center">93.43</td>
<td align="center">6.57</td>
<td align="center">0.66</td>
<td align="center">87</td>
<td align="center">26</td>
<td align="center">468</td>
<td align="center">47</td>
<td align="center">58</td>
<td align="center">&#x2014;</td>
</tr>
<tr>
<td align="left">SHV_P5_OPX_016</td>
<td align="center">71.07</td>
<td align="center">0.17</td>
<td align="center">11.89</td>
<td align="center">2.78</td>
<td align="center">0.48</td>
<td align="center">1.86</td>
<td align="center">2.77</td>
<td align="center">2.23</td>
<td align="center">94.25</td>
<td align="center">5.82</td>
<td align="center">0.58</td>
<td align="center">121</td>
<td align="center">23</td>
<td align="center">509</td>
<td align="center">51</td>
<td align="center">58</td>
<td align="center">&#x2014;</td>
</tr>
<tr>
<td align="left">SHV_P5_OPX_018</td>
<td align="center">69.31</td>
<td align="center">0.22</td>
<td align="center">11.99</td>
<td align="center">3.48</td>
<td align="center">0.81</td>
<td align="center">2.01</td>
<td align="center">2.53</td>
<td align="center">2.08</td>
<td align="center">92.30</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">216</td>
<td align="center">22</td>
<td align="center">58</td>
<td align="center">&#x2014;</td>
</tr>
<tr>
<td align="left">SHV_P5_OPX_020</td>
<td align="center">70.06</td>
<td align="center">0.22</td>
<td align="center">11.86</td>
<td align="center">3.61</td>
<td align="center">0.80</td>
<td align="center">1.83</td>
<td align="center">2.93</td>
<td align="center">1.92</td>
<td align="center">96.63</td>
<td align="center">6.81</td>
<td align="center">0.68</td>
<td align="center">122</td>
<td align="center">42</td>
<td align="center">422</td>
<td align="center">42</td>
<td align="center">57</td>
<td align="center">&#x2014;</td>
</tr>
<tr>
<td colspan="18" align="left">Plagioclase-Hosted Melt Inclusions</td>
</tr>
<tr>
<td align="left">SHV_P1_PLAG_014_MI1</td>
<td align="center">71.78</td>
<td align="center">0.21</td>
<td align="center">12.31</td>
<td align="center">1.84</td>
<td align="center">0.36</td>
<td align="center">1.79</td>
<td align="center">3.36</td>
<td align="center">2.38</td>
<td align="center">94.02</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">664</td>
<td align="center">251</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">52</td>
</tr>
<tr>
<td align="left">SHV_P1_PLAG_014_MI2</td>
<td align="center">71.37</td>
<td align="center">0.19</td>
<td align="center">12.94</td>
<td align="center">1.78</td>
<td align="center">0.31</td>
<td align="center">2.07</td>
<td align="center">3.23</td>
<td align="center">2.16</td>
<td align="center">94.05</td>
<td align="center">5.30</td>
<td align="center">0.53</td>
<td align="center">571</td>
<td align="center">226</td>
<td align="center">937</td>
<td align="center">94</td>
<td align="center">&#x2014;</td>
<td align="center">52</td>
</tr>
<tr>
<td align="left">SHV_P1_PLAG_015_MI1</td>
<td align="center">70.98</td>
<td align="center">0.23</td>
<td align="center">12.67</td>
<td align="center">1.48</td>
<td align="center">0.27</td>
<td align="center">1.90</td>
<td align="center">3.34</td>
<td align="center">2.04</td>
<td align="center">93.22</td>
<td align="center">5.35</td>
<td align="center">0.54</td>
<td align="center">588</td>
<td align="center">156</td>
<td align="center">385</td>
<td align="center">39</td>
<td align="center">&#x2014;</td>
<td align="center">71</td>
</tr>
<tr>
<td align="left">SHV_P1_PLAG_016_MI1</td>
<td align="center">71.70</td>
<td align="center">0.17</td>
<td align="center">12.84</td>
<td align="center">1.55</td>
<td align="center">0.27</td>
<td align="center">2.19</td>
<td align="center">3.46</td>
<td align="center">2.10</td>
<td align="center">94.46</td>
<td align="center">5.73</td>
<td align="center">0.57</td>
<td align="center">341</td>
<td align="center">131</td>
<td align="center">101</td>
<td align="center">10</td>
<td align="center">&#x2014;</td>
<td align="center">54</td>
</tr>
<tr>
<td align="left">SHV_P1_PLAG_017_MI6</td>
<td align="center">73.48</td>
<td align="center">0.17</td>
<td align="center">12.45</td>
<td align="center">1.65</td>
<td align="center">0.33</td>
<td align="center">1.66</td>
<td align="center">3.57</td>
<td align="center">2.23</td>
<td align="center">95.70</td>
<td align="center">3.71</td>
<td align="center">0.37</td>
<td align="center">439</td>
<td align="center">136</td>
<td align="center">174</td>
<td align="center">17</td>
<td align="center">&#x2014;</td>
<td align="center">51</td>
</tr>
<tr>
<td align="left">SHV_P1_PLAG_020_MI2</td>
<td align="center">72.84</td>
<td align="center">0.17</td>
<td align="center">12.40</td>
<td align="center">1.54</td>
<td align="center">0.27</td>
<td align="center">1.71</td>
<td align="center">3.29</td>
<td align="center">2.21</td>
<td align="center">95.05</td>
<td align="center">4.81</td>
<td align="center">0.48</td>
<td align="center">726</td>
<td align="center">196</td>
<td align="center">76</td>
<td align="center">8</td>
<td align="center">&#x2014;</td>
<td align="center">51</td>
</tr>
<tr>
<td align="left">SHV_P1_PLAG_024_MI2</td>
<td align="center">73.36</td>
<td align="center">0.20</td>
<td align="center">12.43</td>
<td align="center">1.58</td>
<td align="center">0.32</td>
<td align="center">1.67</td>
<td align="center">3.06</td>
<td align="center">2.20</td>
<td align="center">95.31</td>
<td align="center">5.88</td>
<td align="center">0.59</td>
<td align="center">1434</td>
<td align="center">318</td>
<td align="center">111</td>
<td align="center">11</td>
<td align="center">&#x2014;</td>
<td align="center">55</td>
</tr>
<tr>
<td align="left">SHV_P1_PLAG_024_MI3</td>
<td align="center">71.84</td>
<td align="center">0.21</td>
<td align="center">12.32</td>
<td align="center">1.59</td>
<td align="center">0.30</td>
<td align="center">1.67</td>
<td align="center">3.18</td>
<td align="center">2.29</td>
<td align="center">93.67</td>
<td align="center">5.05</td>
<td align="center">0.51</td>
<td align="center">737</td>
<td align="center">247</td>
<td align="center">59</td>
<td align="center">6</td>
<td align="center">&#x2014;</td>
<td align="center">57</td>
</tr>
<tr>
<td align="left">SHV_P1_PLAG_028_MI3</td>
<td align="center">71.54</td>
<td align="center">0.22</td>
<td align="center">12.70</td>
<td align="center">1.95</td>
<td align="center">0.38</td>
<td align="center">1.87</td>
<td align="center">3.27</td>
<td align="center">2.19</td>
<td align="center">94.13</td>
<td align="center">6.26</td>
<td align="center">0.63</td>
<td align="center">665</td>
<td align="center">200</td>
<td align="center">104</td>
<td align="center">10</td>
<td align="center">&#x2014;</td>
<td align="center">49</td>
</tr>
<tr>
<td align="left">SHV_P1_PLAG_030_MI1</td>
<td align="center">72.50</td>
<td align="center">0.17</td>
<td align="center">12.54</td>
<td align="center">1.38</td>
<td align="center">0.28</td>
<td align="center">1.91</td>
<td align="center">3.29</td>
<td align="center">2.19</td>
<td align="center">94.27</td>
<td align="center">6.06</td>
<td align="center">0.61</td>
<td align="center">440</td>
<td align="center">157</td>
<td align="center">111</td>
<td align="center">11</td>
<td align="center">&#x2014;</td>
<td align="center">52</td>
</tr>
<tr>
<td align="left">SHV_P1_PLAG_032_MI1</td>
<td align="center">72.04</td>
<td align="center">0.17</td>
<td align="center">12.91</td>
<td align="center">1.42</td>
<td align="center">0.30</td>
<td align="center">1.92</td>
<td align="center">3.92</td>
<td align="center">2.21</td>
<td align="center">95.73</td>
<td align="center">5.82</td>
<td align="center">0.58</td>
<td align="center">745</td>
<td align="center">213</td>
<td align="center">147</td>
<td align="center">15</td>
<td align="center">&#x2014;</td>
<td align="center">52</td>
</tr>
<tr>
<td align="left">SHV_P1_PLAG_032_MI2</td>
<td align="center">73.87</td>
<td align="center">0.15</td>
<td align="center">12.14</td>
<td align="center">1.41</td>
<td align="center">0.25</td>
<td align="center">1.82</td>
<td align="center">3.55</td>
<td align="center">2.19</td>
<td align="center">95.38</td>
<td align="center">4.96</td>
<td align="center">0.50</td>
<td align="center">777</td>
<td align="center">245</td>
<td align="center">69</td>
<td align="center">7</td>
<td align="center">&#x2014;</td>
<td align="center">53</td>
</tr>
<tr>
<td align="left">SHV_P1_PLAG_036_MI3</td>
<td align="center">71.37</td>
<td align="center">0.19</td>
<td align="center">12.80</td>
<td align="center">1.74</td>
<td align="center">0.31</td>
<td align="center">1.73</td>
<td align="center">3.29</td>
<td align="center">2.29</td>
<td align="center">93.86</td>
<td align="center">6.13</td>
<td align="center">0.61</td>
<td align="center">1305</td>
<td align="center">383</td>
<td align="center">102</td>
<td align="center">10</td>
<td align="center">&#x2014;</td>
<td align="center">57</td>
</tr>
<tr>
<td align="left">SHV_P1_PLAG_037_MI2</td>
<td align="center">73.08</td>
<td align="center">0.15</td>
<td align="center">12.08</td>
<td align="center">1.59</td>
<td align="center">0.30</td>
<td align="center">1.63</td>
<td align="center">3.37</td>
<td align="center">2.30</td>
<td align="center">94.50</td>
<td align="center">5.58</td>
<td align="center">0.56</td>
<td align="center">1127</td>
<td align="center">248</td>
<td align="center">230</td>
<td align="center">23</td>
<td align="center">&#x2014;</td>
<td align="center">55</td>
</tr>
<tr>
<td align="left">SHV_P1_PLAG_040</td>
<td align="center">74.04</td>
<td align="center">0.21</td>
<td align="center">11.89</td>
<td align="center">1.63</td>
<td align="center">0.29</td>
<td align="center">1.64</td>
<td align="center">3.18</td>
<td align="center">2.23</td>
<td align="center">95.10</td>
<td align="center">5.65</td>
<td align="center">0.57</td>
<td align="center">451</td>
<td align="center">204</td>
<td align="center">82</td>
<td align="center">8</td>
<td align="center">&#x2014;</td>
<td align="center">52</td>
</tr>
<tr>
<td align="left">SHV_P1_PLAG_048_MI1</td>
<td align="center">72.24</td>
<td align="center">0.18</td>
<td align="center">12.31</td>
<td align="center">1.75</td>
<td align="center">0.29</td>
<td align="center">1.88</td>
<td align="center">3.17</td>
<td align="center">2.18</td>
<td align="center">94.30</td>
<td align="center">6.25</td>
<td align="center">0.63</td>
<td align="center">567</td>
<td align="center">266</td>
<td align="center">104</td>
<td align="center">10</td>
<td align="center">&#x2014;</td>
<td align="center">51</td>
</tr>
<tr>
<td align="left">SHV_P2_PLAG_010_MI1</td>
<td align="center">74.48</td>
<td align="center">0.19</td>
<td align="center">12.06</td>
<td align="center">1.67</td>
<td align="center">0.35</td>
<td align="center">1.50</td>
<td align="center">3.70</td>
<td align="center">2.47</td>
<td align="center">96.41</td>
<td align="center">3.65</td>
<td align="center">0.37</td>
<td align="center">1339</td>
<td align="center">366</td>
<td align="center">75</td>
<td align="center">8</td>
<td align="center">&#x2014;</td>
<td align="center">61</td>
</tr>
<tr>
<td align="left">SHV_P2_PLAG_011</td>
<td align="center">70.99</td>
<td align="center">0.23</td>
<td align="center">12.83</td>
<td align="center">1.84</td>
<td align="center">0.31</td>
<td align="center">1.81</td>
<td align="center">3.72</td>
<td align="center">2.46</td>
<td align="center">94.34</td>
<td align="center">4.55</td>
<td align="center">0.46</td>
<td align="center">666</td>
<td align="center">216</td>
<td align="center">30</td>
<td align="center">3</td>
<td align="center">&#x2014;</td>
<td align="center">52</td>
</tr>
<tr>
<td align="left">SHV_P2_PLAG_013_MI1</td>
<td align="center">74.18</td>
<td align="center">0.19</td>
<td align="center">12.45</td>
<td align="center">1.30</td>
<td align="center">0.26</td>
<td align="center">1.64</td>
<td align="center">4.06</td>
<td align="center">2.34</td>
<td align="center">96.42</td>
<td align="center">3.50</td>
<td align="center">0.35</td>
<td align="center">118</td>
<td align="center">277</td>
<td align="center">13</td>
<td align="center">1</td>
<td align="center">&#x2014;</td>
<td align="center">50</td>
</tr>
<tr>
<td align="left">SHV_P2_PLAG_015_MI3</td>
<td align="center">70.74</td>
<td align="center">0.24</td>
<td align="center">12.91</td>
<td align="center">1.67</td>
<td align="center">0.27</td>
<td align="center">1.98</td>
<td align="center">3.82</td>
<td align="center">2.27</td>
<td align="center">94.38</td>
<td align="center">4.69</td>
<td align="center">0.47</td>
<td align="center">151</td>
<td align="center">364</td>
<td align="center">45</td>
<td align="center">5</td>
<td align="center">&#x2014;</td>
<td align="center">49</td>
</tr>
<tr>
<td align="left">SHV_P2_PLAG_017</td>
<td align="center">71.99</td>
<td align="center">0.16</td>
<td align="center">12.76</td>
<td align="center">1.29</td>
<td align="center">0.22</td>
<td align="center">1.93</td>
<td align="center">3.84</td>
<td align="center">2.11</td>
<td align="center">94.52</td>
<td align="center">3.88</td>
<td align="center">0.39</td>
<td align="center">467</td>
<td align="center">219</td>
<td align="center">64</td>
<td align="center">6</td>
<td align="center">&#x2014;</td>
<td align="center">53</td>
</tr>
<tr>
<td align="left">SHV_P2_PLAG_025</td>
<td align="center">71.79</td>
<td align="center">0.19</td>
<td align="center">13.23</td>
<td align="center">1.59</td>
<td align="center">0.27</td>
<td align="center">2.19</td>
<td align="center">3.86</td>
<td align="center">2.19</td>
<td align="center">95.31</td>
<td align="center">4.62</td>
<td align="center">0.46</td>
<td align="center">1451</td>
<td align="center">289</td>
<td align="center">116</td>
<td align="center">12</td>
<td align="center">&#x2014;</td>
<td align="center">50</td>
</tr>
<tr>
<td align="left">SHV_P2_PLAG_029</td>
<td align="center">70.57</td>
<td align="center">0.17</td>
<td align="center">13.41</td>
<td align="center">1.36</td>
<td align="center">0.18</td>
<td align="center">1.89</td>
<td align="center">3.89</td>
<td align="center">2.68</td>
<td align="center">94.15</td>
<td align="center">4.78</td>
<td align="center">0.48</td>
<td align="center">3145</td>
<td align="center">733</td>
<td align="center">84</td>
<td align="center">8</td>
<td align="center">&#x2014;</td>
<td align="center">52</td>
</tr>
<tr>
<td align="left">SHV_P2_PLAG_030_MI1</td>
<td align="center">74.15</td>
<td align="center">0.20</td>
<td align="center">12.70</td>
<td align="center">1.52</td>
<td align="center">0.28</td>
<td align="center">1.74</td>
<td align="center">4.06</td>
<td align="center">2.24</td>
<td align="center">96.91</td>
<td align="center">3.85</td>
<td align="center">0.39</td>
<td align="center">829</td>
<td align="center">327</td>
<td align="center">71</td>
<td align="center">7</td>
<td align="center">&#x2014;</td>
<td align="center">54</td>
</tr>
<tr>
<td align="left">SHV_P2_PLAG_031_MI1</td>
<td align="center">71.23</td>
<td align="center">0.23</td>
<td align="center">13.34</td>
<td align="center">1.44</td>
<td align="center">0.24</td>
<td align="center">2.24</td>
<td align="center">3.95</td>
<td align="center">2.12</td>
<td align="center">94.79</td>
<td align="center">4.88</td>
<td align="center">0.49</td>
<td align="center">1149</td>
<td align="center">296</td>
<td align="center">57</td>
<td align="center">6</td>
<td align="center">&#x2014;</td>
<td align="center">50</td>
</tr>
<tr>
<td align="left">SHV_P2_PLAG_031_MI2</td>
<td align="center">70.83</td>
<td align="center">0.22</td>
<td align="center">13.40</td>
<td align="center">1.44</td>
<td align="center">0.27</td>
<td align="center">2.20</td>
<td align="center">3.85</td>
<td align="center">2.13</td>
<td align="center">94.34</td>
<td align="center">4.94</td>
<td align="center">0.49</td>
<td align="center">1249</td>
<td align="center">353</td>
<td align="center">81</td>
<td align="center">8</td>
<td align="center">&#x2014;</td>
<td align="center">56</td>
</tr>
<tr>
<td align="left">SHV_P2_PLAG_032_MI1</td>
<td align="center">72.44</td>
<td align="center">0.22</td>
<td align="center">12.68</td>
<td align="center">1.87</td>
<td align="center">0.38</td>
<td align="center">1.66</td>
<td align="center">3.87</td>
<td align="center">2.32</td>
<td align="center">95.74</td>
<td align="center">3.98</td>
<td align="center">0.40</td>
<td align="center">977</td>
<td align="center">357</td>
<td align="center">40</td>
<td align="center">4</td>
<td align="center">&#x2014;</td>
<td align="center">55</td>
</tr>
<tr>
<td align="left">SHV_P2_PLAG_038_MI2</td>
<td align="center">75.37</td>
<td align="center">0.23</td>
<td align="center">11.95</td>
<td align="center">1.70</td>
<td align="center">0.31</td>
<td align="center">1.45</td>
<td align="center">3.94</td>
<td align="center">2.50</td>
<td align="center">98.08</td>
<td align="center">3.24</td>
<td align="center">0.32</td>
<td align="center">2016</td>
<td align="center">557</td>
<td align="center">34</td>
<td align="center">3</td>
<td align="center">&#x2014;</td>
<td align="center">50</td>
</tr>
<tr>
<td align="left">SHV_P2_PLAG_039</td>
<td align="center">70.36</td>
<td align="center">0.46</td>
<td align="center">13.51</td>
<td align="center">1.55</td>
<td align="center">0.22</td>
<td align="center">2.32</td>
<td align="center">4.09</td>
<td align="center">2.38</td>
<td align="center">95.05</td>
<td align="center">5.26</td>
<td align="center">0.53</td>
<td align="center">328</td>
<td align="center">191</td>
<td align="center">43</td>
<td align="center">4</td>
<td align="center">&#x2014;</td>
<td align="center">52</td>
</tr>
<tr>
<td align="left">SHV_P2_PLAG_049</td>
<td align="center">74.06</td>
<td align="center">0.21</td>
<td align="center">12.78</td>
<td align="center">1.52</td>
<td align="center">0.28</td>
<td align="center">1.60</td>
<td align="center">4.18</td>
<td align="center">2.49</td>
<td align="center">97.85</td>
<td align="center">3.07</td>
<td align="center">0.31</td>
<td align="center">1795</td>
<td align="center">557</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">53</td>
</tr>
<tr>
<td align="left">SHV_P4_PLAG_002_MI2</td>
<td align="center">75.15</td>
<td align="center">0.17</td>
<td align="center">11.68</td>
<td align="center">1.48</td>
<td align="center">0.29</td>
<td align="center">1.19</td>
<td align="center">3.65</td>
<td align="center">2.32</td>
<td align="center">96.26</td>
<td align="center">3.40</td>
<td align="center">0.34</td>
<td align="center">1152</td>
<td align="center">770</td>
<td align="center">32</td>
<td align="center">3</td>
<td align="center">&#x2014;</td>
<td align="center">49</td>
</tr>
<tr>
<td align="left">SHV_P4_PLAG_004</td>
<td align="center">74.51</td>
<td align="center">0.21</td>
<td align="center">12.55</td>
<td align="center">1.62</td>
<td align="center">0.23</td>
<td align="center">1.45</td>
<td align="center">4.30</td>
<td align="center">2.38</td>
<td align="center">97.25</td>
<td align="center">2.85</td>
<td align="center">0.29</td>
<td align="center">415</td>
<td align="center">258</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">51</td>
</tr>
<tr>
<td align="left">SHV_P4_PLAG_006_MI1</td>
<td align="center">76.48</td>
<td align="center">0.25</td>
<td align="center">11.51</td>
<td align="center">1.48</td>
<td align="center">0.23</td>
<td align="center">1.15</td>
<td align="center">3.73</td>
<td align="center">2.42</td>
<td align="center">97.26</td>
<td align="center">3.38</td>
<td align="center">0.34</td>
<td align="center">412</td>
<td align="center">151</td>
<td align="center">32</td>
<td align="center">3</td>
<td align="center">&#x2014;</td>
<td align="center">55</td>
</tr>
<tr>
<td align="left">SHV_P4_PLAG_008</td>
<td align="center">73.66</td>
<td align="center">0.21</td>
<td align="center">11.63</td>
<td align="center">1.65</td>
<td align="center">0.35</td>
<td align="center">1.29</td>
<td align="center">3.36</td>
<td align="center">2.26</td>
<td align="center">94.54</td>
<td align="center">4.58</td>
<td align="center">0.46</td>
<td align="center">3767</td>
<td align="center">1372</td>
<td align="center">30</td>
<td align="center">3</td>
<td align="center">&#x2014;</td>
<td align="center">57</td>
</tr>
<tr>
<td align="left">SHV_P4_PLAG_009</td>
<td align="center">75.31</td>
<td align="center">0.24</td>
<td align="center">12.06</td>
<td align="center">1.87</td>
<td align="center">0.35</td>
<td align="center">1.40</td>
<td align="center">4.35</td>
<td align="center">2.52</td>
<td align="center">98.30</td>
<td align="center">2.89</td>
<td align="center">0.29</td>
<td align="center">1026</td>
<td align="center">503</td>
<td align="center">37</td>
<td align="center">4</td>
<td align="center">&#x2014;</td>
<td align="center">52</td>
</tr>
<tr>
<td align="left">SHV_P4_PLAG_018_MI1</td>
<td align="center">72.14</td>
<td align="center">0.24</td>
<td align="center">12.78</td>
<td align="center">1.83</td>
<td align="center">0.33</td>
<td align="center">1.32</td>
<td align="center">4.00</td>
<td align="center">2.44</td>
<td align="center">95.54</td>
<td align="center">3.82</td>
<td align="center">0.38</td>
<td align="center">567</td>
<td align="center">291</td>
<td align="center">25</td>
<td align="center">3</td>
<td align="center">&#x2014;</td>
<td align="center">52</td>
</tr>
<tr>
<td align="left">SHV_P4_PLAG_019_MI2</td>
<td align="center">-</td>
<td align="center">-</td>
<td align="center">-</td>
<td align="center">-</td>
<td align="center">-</td>
<td align="center">-</td>
<td align="center">-</td>
<td align="center">-</td>
<td align="center">-</td>
<td align="center">2.48</td>
<td align="center">0.25</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
</tr>
<tr>
<td align="left">SHV_P4_PLAG_024_MI1</td>
<td align="center">74.39</td>
<td align="center">0.18</td>
<td align="center">12.29</td>
<td align="center">1.37</td>
<td align="center">0.18</td>
<td align="center">1.13</td>
<td align="center">4.26</td>
<td align="center">2.84</td>
<td align="center">97.37</td>
<td align="center">2.47</td>
<td align="center">0.25</td>
<td align="center">2136</td>
<td align="center">541</td>
<td align="center">29</td>
<td align="center">3</td>
<td align="center">&#x2014;</td>
<td align="center">46</td>
</tr>
<tr>
<td align="left">SHV_P4_PLAG_024_MI2</td>
<td align="center">74.07</td>
<td align="center">0.20</td>
<td align="center">12.78</td>
<td align="center">1.27</td>
<td align="center">0.21</td>
<td align="center">1.34</td>
<td align="center">4.71</td>
<td align="center">2.80</td>
<td align="center">97.38</td>
<td align="center">2.97</td>
<td align="center">0.30</td>
<td align="center">3313</td>
<td align="center">691</td>
<td align="center">31</td>
<td align="center">3</td>
<td align="center">&#x2014;</td>
<td align="center">50</td>
</tr>
<tr>
<td align="left">SHV_P4_PLAG_026_MI2</td>
<td align="center">76.21</td>
<td align="center">0.18</td>
<td align="center">11.51</td>
<td align="center">1.42</td>
<td align="center">0.30</td>
<td align="center">1.21</td>
<td align="center">3.89</td>
<td align="center">2.45</td>
<td align="center">97.39</td>
<td align="center">3.26</td>
<td align="center">0.33</td>
<td align="center">647</td>
<td align="center">197</td>
<td align="center">31</td>
<td align="center">3</td>
<td align="center">&#x2014;</td>
<td align="center">49</td>
</tr>
<tr>
<td align="left">SHV_P4_PLAG_026_MI3</td>
<td align="center">76.59</td>
<td align="center">0.15</td>
<td align="center">11.24</td>
<td align="center">1.38</td>
<td align="center">0.25</td>
<td align="center">1.04</td>
<td align="center">3.59</td>
<td align="center">2.50</td>
<td align="center">97.02</td>
<td align="center">2.93</td>
<td align="center">0.29</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">49</td>
</tr>
<tr>
<td align="left">SHV_P4_PLAG_028_MI1</td>
<td align="center">78.15</td>
<td align="center">0.20</td>
<td align="center">11.04</td>
<td align="center">1.38</td>
<td align="center">0.22</td>
<td align="center">1.15</td>
<td align="center">4.04</td>
<td align="center">2.50</td>
<td align="center">98.68</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">1456</td>
<td align="center">421</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">48</td>
</tr>
<tr>
<td align="left">SHV_P4_PLAG_035_MI1</td>
<td align="center">75.66</td>
<td align="center">0.19</td>
<td align="center">11.99</td>
<td align="center">1.46</td>
<td align="center">0.31</td>
<td align="center">1.30</td>
<td align="center">4.46</td>
<td align="center">2.43</td>
<td align="center">97.79</td>
<td align="center">2.81</td>
<td align="center">0.28</td>
<td align="center">2139</td>
<td align="center">468</td>
<td align="center">63</td>
<td align="center">6</td>
<td align="center">&#x2014;</td>
<td align="center">50</td>
</tr>
<tr>
<td align="left">SHV_P4_PLAG_035_MI4</td>
<td align="center">75.16</td>
<td align="center">0.21</td>
<td align="center">12.16</td>
<td align="center">1.54</td>
<td align="center">0.27</td>
<td align="center">1.39</td>
<td align="center">4.06</td>
<td align="center">2.40</td>
<td align="center">97.19</td>
<td align="center">3.10</td>
<td align="center">0.31</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">47</td>
<td align="center">5</td>
<td align="center">&#x2014;</td>
<td align="center">52</td>
</tr>
<tr>
<td align="left">SHV_P4_PLAG_035_MI5</td>
<td align="center">75.50</td>
<td align="center">0.19</td>
<td align="center">12.07</td>
<td align="center">1.71</td>
<td align="center">0.30</td>
<td align="center">1.40</td>
<td align="center">4.14</td>
<td align="center">2.34</td>
<td align="center">97.64</td>
<td align="center">3.24</td>
<td align="center">0.32</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">37</td>
<td align="center">4</td>
<td align="center">&#x2014;</td>
<td align="center">51</td>
</tr>
<tr>
<td align="left">SHV_P4_PLAG_038_MI1</td>
<td align="center">74.49</td>
<td align="center">0.26</td>
<td align="center">11.84</td>
<td align="center">1.94</td>
<td align="center">0.36</td>
<td align="center">1.46</td>
<td align="center">4.25</td>
<td align="center">2.45</td>
<td align="center">97.86</td>
<td align="center">2.96</td>
<td align="center">0.30</td>
<td align="center">2653</td>
<td align="center">519</td>
<td align="center">32</td>
<td align="center">3</td>
<td align="center">&#x2014;</td>
<td align="center">53</td>
</tr>
<tr>
<td align="left">SHV_P4_PLAG_040</td>
<td align="center">73.38</td>
<td align="center">0.24</td>
<td align="center">12.23</td>
<td align="center">1.91</td>
<td align="center">0.36</td>
<td align="center">1.55</td>
<td align="center">3.99</td>
<td align="center">2.28</td>
<td align="center">95.95</td>
<td align="center">3.46</td>
<td align="center">0.35</td>
<td align="center">1465</td>
<td align="center">312</td>
<td align="center">44</td>
<td align="center">4</td>
<td align="center">&#x2014;</td>
<td align="center">53</td>
</tr>
<tr>
<td align="left">SHV_P4_PLAG_041_MI1</td>
<td align="center">76.00</td>
<td align="center">0.23</td>
<td align="center">11.49</td>
<td align="center">1.25</td>
<td align="center">0.15</td>
<td align="center">1.21</td>
<td align="center">3.51</td>
<td align="center">2.63</td>
<td align="center">96.96</td>
<td align="center">3.51</td>
<td align="center">0.35</td>
<td align="center">641</td>
<td align="center">305</td>
<td align="center">19</td>
<td align="center">2</td>
<td align="center">&#x2014;</td>
<td align="center">55</td>
</tr>
<tr>
<td align="left">SHV_P4_PLAG_043_MI1</td>
<td align="center">75.30</td>
<td align="center">0.28</td>
<td align="center">12.19</td>
<td align="center">2.03</td>
<td align="center">0.41</td>
<td align="center">1.40</td>
<td align="center">4.35</td>
<td align="center">2.58</td>
<td align="center">99.47</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">881</td>
<td align="center">304</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">61</td>
</tr>
<tr>
<td align="left">SHV_P4_PLAG_044_MI2</td>
<td align="center">74.93</td>
<td align="center">0.29</td>
<td align="center">11.91</td>
<td align="center">1.75</td>
<td align="center">0.34</td>
<td align="center">1.23</td>
<td align="center">3.60</td>
<td align="center">2.52</td>
<td align="center">97.02</td>
<td align="center">3.69</td>
<td align="center">0.37</td>
<td align="center">670</td>
<td align="center">247</td>
<td align="center">28</td>
<td align="center">3</td>
<td align="center">&#x2014;</td>
<td align="center">62</td>
</tr>
<tr>
<td align="left">SHV_P4_PLAG_045_MI1</td>
<td align="center">76.39</td>
<td align="center">0.10</td>
<td align="center">11.74</td>
<td align="center">1.45</td>
<td align="center">0.28</td>
<td align="center">1.06</td>
<td align="center">3.99</td>
<td align="center">2.72</td>
<td align="center">97.72</td>
<td align="center">2.75</td>
<td align="center">0.28</td>
<td align="center">545</td>
<td align="center">279</td>
<td align="center">30</td>
<td align="center">3</td>
<td align="center">&#x2014;</td>
<td align="center">49</td>
</tr>
<tr>
<td align="left">SHV_P4_PLAG_047_MI2</td>
<td align="center">75.63</td>
<td align="center">0.20</td>
<td align="center">11.77</td>
<td align="center">1.47</td>
<td align="center">0.24</td>
<td align="center">1.45</td>
<td align="center">3.70</td>
<td align="center">2.37</td>
<td align="center">96.83</td>
<td align="center">4.20</td>
<td align="center">0.42</td>
<td align="center">1517</td>
<td align="center">363</td>
<td align="center">40</td>
<td align="center">4</td>
<td align="center">&#x2014;</td>
<td align="center">49</td>
</tr>
<tr>
<td align="left">SHV_P5_PLAG_002_MI4</td>
<td align="center">70.71</td>
<td align="center">0.24</td>
<td align="center">13.07</td>
<td align="center">1.81</td>
<td align="center">0.34</td>
<td align="center">2.26</td>
<td align="center">3.32</td>
<td align="center">2.19</td>
<td align="center">93.94</td>
<td align="center">6.39</td>
<td align="center">0.64</td>
<td align="center">884</td>
<td align="center">257</td>
<td align="center">1126</td>
<td align="center">113</td>
<td align="center">&#x2014;</td>
<td align="center">54</td>
</tr>
<tr>
<td align="left">SHV_P5_PLAG_008_MI1</td>
<td align="center">73.25</td>
<td align="center">0.17</td>
<td align="center">12.53</td>
<td align="center">1.43</td>
<td align="center">0.29</td>
<td align="center">2.07</td>
<td align="center">3.35</td>
<td align="center">2.13</td>
<td align="center">95.53</td>
<td align="center">5.66</td>
<td align="center">0.57</td>
<td align="center">804</td>
<td align="center">219</td>
<td align="center">95</td>
<td align="center">10</td>
<td align="center">&#x2014;</td>
<td align="center">55</td>
</tr>
<tr>
<td align="left">SHV_P5_PLAG_009_MI2</td>
<td align="center">72.20</td>
<td align="center">0.16</td>
<td align="center">12.87</td>
<td align="center">1.37</td>
<td align="center">0.28</td>
<td align="center">2.01</td>
<td align="center">3.53</td>
<td align="center">2.11</td>
<td align="center">94.52</td>
<td align="center">6.18</td>
<td align="center">0.62</td>
<td align="center">487</td>
<td align="center">200</td>
<td align="center">835</td>
<td align="center">84</td>
<td align="center">&#x2014;</td>
<td align="center">55</td>
</tr>
<tr>
<td align="left">SHV_P5_PLAG_016_MI1</td>
<td align="center">71.96</td>
<td align="center">0.15</td>
<td align="center">12.68</td>
<td align="center">1.57</td>
<td align="center">0.28</td>
<td align="center">1.92</td>
<td align="center">3.35</td>
<td align="center">2.17</td>
<td align="center">95.10</td>
<td align="center">6.18</td>
<td align="center">0.62</td>
<td align="center">268</td>
<td align="center">97</td>
<td align="center">128</td>
<td align="center">13</td>
<td align="center">&#x2014;</td>
<td align="center">52</td>
</tr>
<tr>
<td align="left">SHV_P5_PLAG_016_MI3</td>
<td align="center">72.71</td>
<td align="center">0.10</td>
<td align="center">12.66</td>
<td align="center">1.48</td>
<td align="center">0.28</td>
<td align="center">1.86</td>
<td align="center">3.51</td>
<td align="center">2.14</td>
<td align="center">95.06</td>
<td align="center">5.87</td>
<td align="center">0.59</td>
<td align="center">467</td>
<td align="center">163</td>
<td align="center">147</td>
<td align="center">15</td>
<td align="center">&#x2014;</td>
<td align="center">48</td>
</tr>
<tr>
<td align="left">SHV_P5_PLAG_016_MI6</td>
<td align="center">73.16</td>
<td align="center">0.14</td>
<td align="center">12.68</td>
<td align="center">1.49</td>
<td align="center">0.32</td>
<td align="center">1.64</td>
<td align="center">3.52</td>
<td align="center">2.22</td>
<td align="center">95.17</td>
<td align="center">4.87</td>
<td align="center">0.49</td>
<td align="center">&#x2014;</td>
<td align="center">&#x2014;</td>
<td align="center">211</td>
<td align="center">21</td>
<td align="center">&#x2014;</td>
<td align="center">50</td>
</tr>
<tr>
<td align="left">SHV_P5_PLAG_024_MI2</td>
<td align="center">74.54</td>
<td align="center">0.20</td>
<td align="center">11.77</td>
<td align="center">1.57</td>
<td align="center">0.30</td>
<td align="center">1.69</td>
<td align="center">3.27</td>
<td align="center">2.20</td>
<td align="center">95.75</td>
<td align="center">4.97</td>
<td align="center">0.50</td>
<td align="center">2347</td>
<td align="center">691</td>
<td align="center">206</td>
<td align="center">21</td>
<td align="center">&#x2014;</td>
<td align="center">48</td>
</tr>
<tr>
<td align="left">SHV_P5_PLAG_025_MI1</td>
<td align="center">72.45</td>
<td align="center">0.21</td>
<td align="center">12.27</td>
<td align="center">1.69</td>
<td align="center">0.32</td>
<td align="center">1.66</td>
<td align="center">3.37</td>
<td align="center">2.28</td>
<td align="center">94.25</td>
<td align="center">5.80</td>
<td align="center">0.58</td>
<td align="center">720</td>
<td align="center">241</td>
<td align="center">96</td>
<td align="center">10</td>
<td align="center">&#x2014;</td>
<td align="center">55</td>
</tr>
<tr>
<td align="left">SHV_P5_PLAG_034_MI2</td>
<td align="center">71.58</td>
<td align="center">0.18</td>
<td align="center">12.83</td>
<td align="center">1.61</td>
<td align="center">0.31</td>
<td align="center">2.16</td>
<td align="center">3.37</td>
<td align="center">2.23</td>
<td align="center">94.28</td>
<td align="center">5.98</td>
<td align="center">0.60</td>
<td align="center">1421</td>
<td align="center">260</td>
<td align="center">152</td>
<td align="center">15</td>
<td align="center">&#x2014;</td>
<td align="center">51</td>
</tr>
<tr>
<td align="left">SHV_P5_PLAG_037_MI1</td>
<td align="center">73.25</td>
<td align="center">0.15</td>
<td align="center">12.63</td>
<td align="center">1.55</td>
<td align="center">0.30</td>
<td align="center">1.65</td>
<td align="center">3.51</td>
<td align="center">2.27</td>
<td align="center">95.30</td>
<td align="center">5.33</td>
<td align="center">0.53</td>
<td align="center">381</td>
<td align="center">178</td>
<td align="center">442</td>
<td align="center">44</td>
<td align="center">&#x2014;</td>
<td align="center">51</td>
</tr>
<tr>
<td align="left">SHV_P5_PLAG_042_MI2</td>
<td align="center">72.48</td>
<td align="center">0.24</td>
<td align="center">12.91</td>
<td align="center">1.71</td>
<td align="center">0.31</td>
<td align="center">1.90</td>
<td align="center">3.55</td>
<td align="center">2.18</td>
<td align="center">95.29</td>
<td align="center">5.82</td>
<td align="center">0.58</td>
<td align="center">1384</td>
<td align="center">417</td>
<td align="center">1243</td>
<td align="center">124</td>
<td align="center">&#x2014;</td>
<td align="center">53</td>
</tr>
<tr>
<td align="left">SHV_P5_PLAG_043_MI3</td>
<td align="center">74.89</td>
<td align="center">0.28</td>
<td align="center">11.76</td>
<td align="center">1.72</td>
<td align="center">0.34</td>
<td align="center">1.64</td>
<td align="center">3.35</td>
<td align="center">2.31</td>
<td align="center">96.28</td>
<td align="center">4.55</td>
<td align="center">0.46</td>
<td align="center">800</td>
<td align="center">304</td>
<td align="center">233</td>
<td align="center">23</td>
<td align="center">&#x2014;</td>
<td align="center">68</td>
</tr>
</tbody>
</table>
</table-wrap>
</sec>
<sec id="s4-2-1-2">
<title>4.2.1.2 Bubble growth</title>
<p>After entrapment of melt, bubbles can be formed in response to the pressure-volume-temperature relationship between host mineral and melt. Based on this relationship, bubbles can grow via 1) post-entrapment crystallization, 2) diffusive H<sup>&#x2b;</sup> loss and 3) differential thermal contraction (<xref ref-type="bibr" rid="B101">Roedder, 1979</xref>; <xref ref-type="bibr" rid="B4">Anderson and Brown, 1993</xref>; <xref ref-type="bibr" rid="B67">Lowenstern, 1995</xref>; <xref ref-type="bibr" rid="B63">Kent, 2008</xref>; <xref ref-type="bibr" rid="B53">Hartley et al., 2014</xref>; <xref ref-type="bibr" rid="B118">Wallace et al., 2015</xref>; <xref ref-type="bibr" rid="B6">Aster et al., 2016</xref>; <xref ref-type="bibr" rid="B51">Hanyu et al., 2020</xref>; <xref ref-type="bibr" rid="B120">Wieser et al., 2021</xref>). The process with the largest effect occurs due to differing thermal expansivities between host mineral and melt during cooling from high trapping temperatures to the glass transition temperature, after which bubble growth is suppressed (<xref ref-type="bibr" rid="B84">Moore et al., 2015</xref>). However, bubbles are also known to nucleate in the melt prior to entrapment, and can grow by diffusion of volatiles from the inclusion glass into the bubble, coalescence, decompression during ascent or Ostwald ripening (<xref ref-type="bibr" rid="B23">Cashman and Mangan, 1994</xref>; <xref ref-type="bibr" rid="B12">Best, 2013</xref>). It is therefore necessary to identify bubbles that have grown homogenously post-entrapment, in order to prevent overestimation of the bubble volatile content caused by volatile-bearing bubbles being trapped at the time of melt inclusion formation. Homogenous bubble growth has been reported to be 5%&#x2013;12% for a range of volcanic systems (e.g., <xref ref-type="bibr" rid="B53">Hartley et al., 2014</xref>; <xref ref-type="bibr" rid="B6">Aster et al., 2016</xref>; <xref ref-type="bibr" rid="B51">Hanyu et al., 2020</xref>), and we adopt the lower end of 5% bubble volume to distinguish bubbles that nucleated and grew post-entrapment, in comparison to those trapped with the melt.</p>
<p>Previous studies combining CO<sub>2</sub> analysis in vapour bubbles and their host melt inclusions have shown that up to 90% of CO<sub>2</sub> can be sequestered to bubbles in the form of vapour (<xref ref-type="bibr" rid="B53">Hartley et al., 2014</xref>; <xref ref-type="bibr" rid="B84">Moore et al., 2015</xref>; <xref ref-type="bibr" rid="B114">Venugopal et al., 2020</xref>). However, CO<sub>2</sub> can exist in its liquid form and also as carbonates that can store up to 50% of CO<sub>2</sub> in the bubble. This is also true for sulphur-bearing minerals precipitated on bubble walls, which can store up to 60% of sulphur originally trapped in an inclusion (<xref ref-type="bibr" rid="B44">Esposito et al., 2016</xref>; <xref ref-type="bibr" rid="B105">Schiavi et al., 2020</xref>), and H<sub>2</sub>O of which up to 16% can be sequestered (<xref ref-type="bibr" rid="B44">Esposito et al., 2016</xref>). Overall, melt inclusion bubbles have the ability to not only store large amount of CO<sub>2</sub> and S, but also H<sub>2</sub>O and major and minor elements that constitute carbonates, sulphates, sulphides, halides and other minerals such as Na, Ca, Mg, Fe or Cu (<xref ref-type="bibr" rid="B105">Schiavi et al., 2020</xref>; <xref ref-type="bibr" rid="B114">Venugopal et al., 2020</xref>).</p>
<p>The concentration of CO<sub>2</sub> sequestered to bubbles post-entrapment is calculated by mass-balance equations (<xref ref-type="bibr" rid="B83">Moore and Bodnar, 2019</xref>), taking into consideration: 1) the volume fraction of the melt inclusion that is constituted by the bubble, and 2) the density of CO<sub>2</sub> measured by Raman spectroscopy (<xref ref-type="sec" rid="s13">Supplementary Data Sheet</xref>). Total inclusion and bubble volumes were estimated from photomicrographs, assuming a spherical shape for bubbles, an ellipsoid shape for orthopyroxene hosted inclusions and cuboidal shapes for inclusions hosted in plagioclase, based on their 2D appearances from a polished surface (<xref ref-type="fig" rid="F4">Figure 4</xref>). The two perpendicular axes were measured using a Leica DM4500 P LED microscope on the Leica Application Suite software, and the third unseen axis was calculated using the arithmetic mean of the measured axes. This method is associated with an average 5% error, but a 1&#x3c3; error of &#x2212;48% to 37% (<xref ref-type="bibr" rid="B113">Tucker et al., 2019</xref>). Uncertainty in bubble sizes was &#xb1;2 &#xb5;m,w which yielded bubble volume uncertainties of 6%&#x2013;24%. (Mean 11%; <xref ref-type="sec" rid="s13">Supplementary Data Sheet</xref>). Density calculations were undertaken by firstly processing the Raman spectra of individual bubbles using the WiRE&#x2122; 4.4 spectral analysis software. After baselines were applied to each spectrum with &#x3e;500 counts using a polynomial curve, the Fermi diad was truncated at 1200 and 1500 cm<sup>&#x2212;1</sup>. Each peak was fitted with a mixed Gaussian-Lorentzian curve, and the Fermi diad split was calculated as the difference between the centres (in wave number) of the two peaks. In the absence of a CO<sub>2</sub> densimetry curve specifically calibrated for the instrument used, the experimental equation of <xref ref-type="bibr" rid="B65">Lamadrid et al. (2017)</xref> was adopted to calculate CO<sub>2</sub> density. Fermi diad peaks with counts &#x3c;500 or asymmetrical peaks to which curves could not be readily fitted were not used to quantify CO<sub>2</sub>.</p>
<fig id="F4" position="float">
<label>FIGURE 4</label>
<caption>
<p>Examples of melt inclusions adopting different shapes. <bold>(A)</bold> SHV_P1_PLAG_010 is a plagioclase hosted inclusion taking the 2D shape of a rectangle, assumed to be cuboidal in 3D. <bold>(B)</bold> SHV_P5_OPX_006_MI1 is an orthopyroxene hosted inclusion taking the 2D shape of an oval, assumed to be ellipsoidal in 3D.</p>
</caption>
<graphic xlink:href="feart-12-1509409-g004.tif"/>
</fig>
</sec>
<sec id="s4-2-1-3">
<title>4.2.1.3 H<sub>2</sub>O loss</title>
<p>Loss of H<sub>2</sub>O in melt inclusions was assessed from H<sub>2</sub>O vs. K<sub>2</sub>O, which shows no significant variation of H<sub>2</sub>O at a given K<sub>2</sub>O (<xref ref-type="fig" rid="F7">Figure 7</xref>), and thereby indicates no significant H<sub>2</sub>O loss in SHV melt inclusions.</p>
</sec>
</sec>
<sec id="s4-2-2">
<title>4.2.2 Major element compositions</title>
<p>The major element composition of seventy-seven SHV melt inclusions across phases 1, 2, 4, and 5 is plotted against K<sub>2</sub>O as a representation of magma differentiation (<xref ref-type="fig" rid="F5">Figure 5</xref>). There are trends in the overall dataset, and the dataset can also be divided into distinct groups, where the compositions differ based on Phase and host mineral. Overall, SiO<sub>2</sub> ranges from 69.63&#x2013;78.15 wt% with total alkalis of 4.48&#x2013;7.51 wt% across K<sub>2</sub>O 1.61&#x2013;2.84 wt%, classifying the inclusions as dacite and rhyolite based on total alkali vs. silica (<xref ref-type="fig" rid="F2">Figure 2</xref>; <xref ref-type="bibr" rid="B66">Le Bas et al., 1986</xref>). Inclusions hosted in orthopyroxene are less evolved than those hosted in plagioclase, and inclusions are all more evolved than whole rock compositions. However, they overlap with groundmass glass compositions of 69.85&#x2013;80.03 wt% for Phases 1&#x2013;3 (<xref ref-type="bibr" rid="B42">Edmonds et al., 2002</xref>; <xref ref-type="bibr" rid="B52">Harford et al., 2003</xref>; <xref ref-type="bibr" rid="B18">Buckley et al., 2006</xref>; <xref ref-type="bibr" rid="B58">Humphreys et al., 2010</xref>). Increasing trends with differentiation are seen in SiO<sub>2</sub> and Na<sub>2</sub>O vs. K<sub>2</sub>O, while decreasing trends occur in CaO vs. K<sub>2</sub>O. Trends remain relatively constant for TiO<sub>2</sub>, Al<sub>2</sub>O<sub>3</sub>, FeO and MgO vs. K<sub>2</sub>O.</p>
<fig id="F5" position="float">
<label>FIGURE 5</label>
<caption>
<p>Harker diagram showing major elements plotted against K<sub>2</sub>O for assessment of variation with magma differentiation. The composition of inclusions differs with phase, where there is an increase in evolution through Phases 1 to 4, followed by less evolved inclusions at Phase 5. Grey zones are data reported in the literature for Phases 1-3 from <xref ref-type="bibr" rid="B42">Edmonds et al. (2002)</xref>, <xref ref-type="bibr" rid="B18">Buckley et al. (2006)</xref>, <xref ref-type="bibr" rid="B58">Humphreys et al. (2010)</xref>, <xref ref-type="bibr" rid="B69">Mann et al. (2013)</xref>. <bold>(A)</bold> SiO<sub>2</sub> vs K<sub>2</sub>O, <bold>(B)</bold> MgO vs K<sub>2</sub>O, <bold>(C)</bold> TiO<sub>2</sub> vs K<sub>2</sub>O, <bold>(D)</bold> CaO vs K<sub>2</sub>O, <bold>(E)</bold> Al<sub>2</sub>O<sub>3</sub> vs K<sub>2</sub>O, <bold>(F)</bold> Na<sub>2</sub>O vs K<sub>2</sub>O, <bold>(G)</bold> FeO vs K<sub>2</sub>O.</p>
</caption>
<graphic xlink:href="feart-12-1509409-g005.tif"/>
</fig>
<p>In Phase 1, SiO<sub>2</sub> ranges from 70.06&#x2013;74.04 wt%, and is one of the least evolved Phases. Major element data exist only for plagioclase hosted inclusions in Phase 2. This group generally overlaps with Phases 1 and 5 with SiO<sub>2</sub> of 70.36&#x2013;75.37 wt%. Phase 4 stands out as the most evolved group, with SiO<sub>2</sub> ranging from 72.14&#x2013;78.15 wt% in plagioclase hosted inclusions. Inclusions in Phase 5 are similar to those of Phase 1, with 69.63&#x2013;74.89 wt% SiO<sub>2</sub>. Overall, there is a trend of increasingly evolved melt compositions through Phases 1&#x2013;4, before compositions revert to lower SiO<sub>2</sub> contents during Phase 5. Similar temporal evolution&#x2013;with a distinction between the Phase 1-4 trend and Phase 5 &#x2013; is also identified in CaO and Na<sub>2</sub>O (<xref ref-type="fig" rid="F5">Figure 5</xref>).</p>
</sec>
</sec>
<sec id="s4-3">
<title>4.3 Volatile element compositions</title>
<sec id="s4-3-1">
<title>4.3.1 Melt inclusion glass</title>
<p>SHV melt inclusions are rich in volatiles, with H<sub>2</sub>O in the glass of seventy-five orthopyroxene-hosted inclusions ranging from 5.38&#x2013;7.74 wt%, and 2.47&#x2013;6.40 wt% in plagioclase-hosted inclusions (<xref ref-type="fig" rid="F7">Figure 7A</xref>) throughout the eruption. Melt inclusion H<sub>2</sub>O values across all Phases are similar to those recorded for Phase 1 and 2 plagioclase- and quartz-hosted inclusions (1.20&#x2013;6.86 wt%, reported by <xref ref-type="bibr" rid="B11">Barclay et al., 1998</xref>; <xref ref-type="bibr" rid="B69">Mann et al., 2013</xref>), and are also similar to values reported by <xref ref-type="bibr" rid="B57">Humphreys et al. (2009)</xref> and <xref ref-type="bibr" rid="B40">Edmonds et al. (2014)</xref> where H<sub>2</sub>O in plagioclase- and orthopyroxene-hosted inclusions measured 0.03&#x2013;6.40 wt% for Phase 3 samples. Values from this study are also roughly similar to H<sub>2</sub>O measured in orthopyroxene cores (6-9 wt%) for Phase 3 data of <xref ref-type="bibr" rid="B41">Edmonds et al., 2016</xref>.</p>
<p>H<sub>2</sub>O across the eruption exhibits a decreasing trend with K<sub>2</sub>O. This trend is also apparent in individual Phase groups, where plagioclase-hosted inclusions indicate degassing associated with crystallisation, except in Phase 1, where most of the data fall between a very restricted K<sub>2</sub>O range, but are consistent with the overall degassing trend. Separating the dataset into Phase groups illustrates not only the degassing trend in the Phases, but also the difference in H<sub>2</sub>O content as the eruption progresses. Similar to major elements, there is a decrease in H<sub>2</sub>O contents from Phase 1, at the beginning of the eruption, to Phase 4, with a return to high H<sub>2</sub>O in Phase 5 (<xref ref-type="fig" rid="F7">Figure 7A</xref>). Based on their relationship with K<sub>2</sub>O, the conclusion is made that SHV inclusions experienced at most negligible H<sub>2</sub>O loss, as inclusions do not fall out of trend at a given K<sub>2</sub>O.</p>
<p>This distinction in Phase groups is however not seen with melt inclusion glass CO<sub>2</sub> concentrations, where CO<sub>2</sub> across the eruption does not trend with K<sub>2</sub>O except for Phase 2, and are typically &#x3c;1000 ppm, with 67 of 69 inclusions containing 13&#x2013;937 ppm, while two inclusions which contain 1126 (SHV_P5_PLAG_002_MI4) and 1243 (SHV_P5_PLAG_042_MI2) ppm.</p>
</sec>
<sec id="s4-3-2">
<title>4.3.2 Melt inclusion bubble</title>
<p>Bubbles at SHV contain CO<sub>2</sub> vapour along with solid phases crystallised on the bubble wall, identified via their main and other vibrations (<xref ref-type="bibr" rid="B46">Frezzotti et al., 2012</xref>; <xref ref-type="fig" rid="F6">Figure 6</xref>). Solids are in the form of sulphates and are normally anhydrite and gypsum. No carbonates were observed.</p>
<fig id="F6" position="float">
<label>FIGURE 6</label>
<caption>
<p>Raman spectra of gaseous and solid phases found in Soufri&#xe8;re Hills bubbles. <bold>(A)</bold> Raman spectra of bubble from SHV_P2_OPX_001_MI1 displaying Fermi diad indicating the presence of CO<sub>2</sub>. <bold>(B)</bold> Raman spectra of the bubble of plagioclase-hosted inclusion &#x2018;SHV_P1_PLAG_030_MI1&#x2019; showing Fermi diad. <bold>(C)</bold> Raman spectra of bubble in SHV_P5_OPX_002_MI1 showing presence of sulphate (anhydrite) crystals on bubble wall with peaks at 430, 500, 611, 629, 676, 1018, and 1131 cm<sup>&#x2212;1</sup>.</p>
</caption>
<graphic xlink:href="feart-12-1509409-g006.tif"/>
</fig>
<p>Two groups can be identified from a total of 577 bubbles analysed by Raman spectroscopy. Group A consists of 91% of the bubble population, and are described as displaying a Fermi diad. Group B accounts for 9% of the bubble population, and their Raman spectra lack observable Fermi diads, indicating no CO<sub>2</sub> or CO<sub>2</sub> with very low densities. The 523 bubbles displaying Fermi diads have a CO<sub>2</sub> density range from 0.001 to 0.22 g cm<sup>&#x2212;3</sup>, with an upper limit of 0.13 (<xref ref-type="fig" rid="F8">Figure 8B</xref>) for those with glass analysed via SIMS. Overall, bubble CO<sub>2</sub> density exists below the critical density of CO<sub>2</sub> (0.468 g cm<sup>&#x2212;3</sup>; <xref ref-type="bibr" rid="B82">Moldover, 1974</xref>), therefore, CO<sub>2</sub> exists solely as vapour and is not underestimated due to the presence of aqueous CO<sub>2</sub>. In order to correct the total melt inclusion CO<sub>2</sub> to account for the bubble-hosted component, we take the mass of CO<sub>2</sub> in the bubble and add it back into the entire mass of glass in the MI and must thus account for their relative volumes. The contribution of the bubble-hosted CO<sub>2</sub> to the total inclusion CO<sub>2</sub> is based on the mass ratio between the bubble and the glass, and is therefore given by <xref ref-type="disp-formula" rid="e1">Equation 1</xref>:<disp-formula id="e1">
<mml:math id="m4">
<mml:mrow>
<mml:msub>
<mml:mrow>
<mml:mfenced open="[" close="]" separators="|">
<mml:mrow>
<mml:msub>
<mml:mrow>
<mml:mi>C</mml:mi>
<mml:mi>O</mml:mi>
</mml:mrow>
<mml:mn>2</mml:mn>
</mml:msub>
</mml:mrow>
</mml:mfenced>
</mml:mrow>
<mml:mrow>
<mml:mi>b</mml:mi>
<mml:mi>u</mml:mi>
<mml:mi>b</mml:mi>
<mml:mi>b</mml:mi>
<mml:mi>l</mml:mi>
<mml:mi>e</mml:mi>
</mml:mrow>
</mml:msub>
<mml:mo>&#x3d;</mml:mo>
<mml:mfrac>
<mml:mrow>
<mml:msub>
<mml:mi>&#x3c1;</mml:mi>
<mml:mrow>
<mml:mi>C</mml:mi>
<mml:msub>
<mml:mi>O</mml:mi>
<mml:mn>2</mml:mn>
</mml:msub>
</mml:mrow>
</mml:msub>
<mml:msub>
<mml:mi>V</mml:mi>
<mml:mrow>
<mml:mi>b</mml:mi>
<mml:mi>u</mml:mi>
<mml:mi>b</mml:mi>
<mml:mi>b</mml:mi>
<mml:mi>l</mml:mi>
<mml:mi>e</mml:mi>
</mml:mrow>
</mml:msub>
</mml:mrow>
<mml:mrow>
<mml:msub>
<mml:mi>&#x3c1;</mml:mi>
<mml:mrow>
<mml:mi>g</mml:mi>
<mml:mi>l</mml:mi>
<mml:mi>a</mml:mi>
<mml:mi>s</mml:mi>
<mml:mi>s</mml:mi>
</mml:mrow>
</mml:msub>
<mml:msub>
<mml:mi>V</mml:mi>
<mml:mrow>
<mml:mi>g</mml:mi>
<mml:mi>l</mml:mi>
<mml:mi>a</mml:mi>
<mml:mi>s</mml:mi>
<mml:mi>s</mml:mi>
</mml:mrow>
</mml:msub>
</mml:mrow>
</mml:mfrac>
<mml:mi>x</mml:mi>
<mml:mtext>&#x2009;</mml:mtext>
<mml:msup>
<mml:mn>10</mml:mn>
<mml:mn>6</mml:mn>
</mml:msup>
</mml:mrow>
</mml:math>
<label>(1)</label>
</disp-formula>where [CO<sub>2</sub>]<sub>bubble</sub> is the amount that the concentration of CO2 in the entire inclusion will be corrected when CO<sub>2</sub> in the bubble is accounted for. CO<sub>2</sub> density, volume of the bubble(s) and volume of the total inclusion are calculated according to <xref ref-type="sec" rid="s4-2-1">Section 4.2.1</xref>, and glass density is calculated for individual inclusions using DensityX (<xref ref-type="bibr" rid="B61">Iacovino and Till, 2019</xref>). Important sources of errors in calculating the amount of CO<sub>2</sub> that is contributed from the bubble are the estimation of bubble and inclusion volumes. For bubbles in the range 3&#x2013;6 &#xb5;m (majority orthopyroxene-hosted inclusions), volume errors are as large as 24%. However, the contribution of CO<sub>2</sub> from the bubble to total CO<sub>2</sub> in these inclusions are small in comparison to the concentration of CO<sub>2</sub> in the glass, and therefore the total error is small (&#x223c;11%). For bubbles over 6 &#x3bc;m, errors on volume calculations are 5%&#x2013;10%. Additionally, large errors are introduced in calculation of the CO<sub>2</sub> density, especially at low densities (<xref ref-type="sec" rid="s13">Supplementary Data Sheet</xref>), calculated using the densimeter equation of <xref ref-type="bibr" rid="B65">Lamadrid et al. (2017)</xref> in the absence of a calibration curve specific to the Raman spectrometer used. Overall, errors on the calculation of total CO<sub>2</sub> amount to &#x223c;22%. Based on (i) CO<sub>2</sub> existing solely as vapour in the bubble(s), and (ii) carbonates being absent in the bubble, the contribution of CO<sub>2</sub> from the bubble of seventy-two inclusions for which there are SIMS and EPMA data ranges from 9 to 3767 ppm. However, for further calculations and models, we use bubbles that do not show signs of heterogeneous entrapment (bubbles &#x3c;5% of total inclusion volume). The contribution of CO<sub>2</sub> from these bubbles to the total inclusion is 9&#x2013;3145 ppm.</p>
</sec>
<sec id="s4-3-3">
<title>4.3.3 Total CO<sub>2</sub>
</title>
<p>The summation of CO<sub>2</sub> in the glass and CO<sub>2</sub> in the bubble (5% threshold applied) gives a total CO<sub>2</sub> budget of melt inclusions of 131&#x2013;3230 ppm, with an average of 1006 &#xb1; 684 ppm at SHV (<xref ref-type="fig" rid="F7">Figure 7C</xref>), the highest for the Northern Group islands where maximum CO<sub>2</sub> is 720 ppm for St Kitts (<xref ref-type="bibr" rid="B76">Melekhova et al., 2017</xref>), and is most comparable with islands in the Central Group where CO<sub>2</sub> values extend up to 1507 and 4012 ppm for bubble-free melt inclusions from Guadeloupe and Dominica respectively (<xref ref-type="bibr" rid="B9">Balcone-Boissard et al., 2018</xref>; <xref ref-type="bibr" rid="B7">d&#x2019;Augustin et al., 2020</xref>; <xref ref-type="bibr" rid="B79">Metcalfe et al., 2022</xref>).</p>
<fig id="F7" position="float">
<label>FIGURE 7</label>
<caption>
<p>
<bold>(A)</bold> H<sub>2</sub>O vs. K<sub>2</sub>O in the glass shows degassing within Phases and an overall decrease of H2O with time, reverting to high H2O during the last Phase of eruption. <bold>(B)</bold> Total CO<sub>2</sub> vs. H<sub>2</sub>O does not follow simple open or closed degassing trends. <bold>(C)</bold> Concentration of CO<sub>2</sub> in the glass, bubble and total CO<sub>2</sub> of the MI. Grey areas are values reported in the literature. H<sub>2</sub>O and CO<sub>2</sub> data from <xref ref-type="bibr" rid="B11">Barclay et al. (1998)</xref>; <xref ref-type="bibr" rid="B69">Mann et al. (2013)</xref> &#x26; <xref ref-type="bibr" rid="B40">Edmonds et al. (2014)</xref>. Error bars show 10% errors on H<sub>2</sub>O, and are calculated individually for CO<sub>2</sub> based on the contribution from both the bubble and the glass. Where error bars are not shown, the error is smaller than the symbol size.</p>
</caption>
<graphic xlink:href="feart-12-1509409-g007.tif"/>
</fig>
<p>While the bubble comprised &#x2264;5% of total inclusion volume, the percentage of CO<sub>2</sub> sequestered to the bubble amount to 5%&#x2013;76% for inclusions hosted in orthopyroxene, and 37%&#x2013;99% for those hosted in plagioclase (<xref ref-type="fig" rid="F8">Figure 8A</xref>), in agreement with published data on CO<sub>2</sub> loss to the bubble (e.g., <xref ref-type="bibr" rid="B53">Hartley et al., 2014</xref>; <xref ref-type="bibr" rid="B118">Wallace et al., 2015</xref>; <xref ref-type="bibr" rid="B83">Moore and Bodnar, 2019</xref>; <xref ref-type="bibr" rid="B114">Venugopal et al., 2020</xref>). It is noted that orthopyroxene-hosted melt inclusions trapped less evolved and less differentiated magma and therefore contain more H<sub>2</sub>O than the plagioclase-hosted melt inclusions. Following this trend, it is expected that these inclusions should also contain higher CO<sub>2</sub> contents, but this is not the case, and we are unable to adequately explain this phenomenon.</p>
<fig id="F8" position="float">
<label>FIGURE 8</label>
<caption>
<p>
<bold>(A)</bold> Percentage of CO<sub>2</sub> contributed by the bubble vs. bubble to inclusion ratio. In orthopyroxene-hosted inclusions, 5%&#x2013;76% of CO<sub>2</sub> in the total melt inclusion is contributed by the bubble. In plagioclase-hosted inclusions, this value is 37%&#x2013;99%. Overall, there is a median of 90% contribution from the bubble to the total inclusion CO<sub>2</sub> <bold>(B)</bold> There is no correlation with CO<sub>2</sub> density as a function of bubble volume percentage. The red line on both plots denote the 5% bubble threshold of homogenous vs. heterogeneous bubble growth.</p>
</caption>
<graphic xlink:href="feart-12-1509409-g008.tif"/>
</fig>
<p>H<sub>2</sub>O and total CO<sub>2</sub> do not show simple open- or closed-system degassing trends overall or when separated by Phases (<xref ref-type="fig" rid="F7">Figure 7B</xref>). However, CO<sub>2</sub> during Phase 1 appears 1082&#x2013;1685 ppm lower than Phases 2, 4, and 5. The case can be made for CO<sub>2</sub> degassing in each Phase as large variations in CO<sub>2</sub> exist at relatively constant H<sub>2</sub>O while being hosted in phenocrysts with similar enstatite and anorthite contents. Due to its low solubility, CO<sub>2</sub> begins to exsolve at high pressures and is the first volatile species to be degassed (<xref ref-type="bibr" rid="B12">Best, 2013</xref>).</p>
</sec>
</sec>
</sec>
<sec sec-type="discussion" id="s5">
<title>5 Discussion</title>
<sec id="s5-1">
<title>5.1 Magma storage conditions</title>
<p>The compositions (corrected for PEC) of major and volatile elements are applied to models to facilitate connection between melt inclusion data and crystallisation temperatures, magma storage depths, degassing systematics and magmatic CO<sub>2</sub> budgets.</p>
<sec id="s5-1-1">
<title>5.1.1 Geothermometry</title>
<p>The temperatures calculated represent magmatic temperatures at the time of melt inclusion trapping, and account for PEC. For orthopyroxene-hosted inclusions from Phase 1 and Phase 5, the temperature calculation was based on orthopyroxene-liquid equilibria using Equation 28a of <xref ref-type="bibr" rid="B96">Putirka, (2008)</xref>. Temperatures from the two Phases are not highly varied, with a total range of 880&#xb0;C&#x2013;916&#xb0;C, and a standard error of estimate (SEE) of 28&#xb0;C. Phase 1 and 5 results are not significantly different, being 880&#xb0;C&#x2013;898&#xb0;C for Phase 1 (three melt inclusions) and 884&#xb0;C&#x2013;916&#xb0;C for eight Phase 5 inclusions. Plagioclase-liquid equilibria are applied to fifty-two plagioclase-hosted inclusions where H<sub>2</sub>O was measured via SIMS, to reduce overestimation of temperature due to its strong dependence on H<sub>2</sub>O. Applying Equation 24a of <xref ref-type="bibr" rid="B96">Putirka, (2008)</xref> yields a narrow temperature range across Phases, with temperatures ranging from 828&#xb0;C to 893&#xb0;C and SEE of 36&#xb0;C. However, the plagioclase melt inclusion data do reveal a significant difference in temperature between Phases, where Phase 2 inclusions yield the hottest temperatures from 875&#xb0;C to 893&#xb0;C along with Phase 4 (849&#x2013;891). Phases 1 and 5 are cooler, with temperatures of 828&#xb0;C&#x2013;881&#xb0;C and 836&#xb0;C&#x2013;864&#xb0;C respectively (<xref ref-type="fig" rid="F9">Figure 9</xref>). While Phase 5 inclusions are more primitive than Phase 2 and 4, based on SiO<sub>2</sub>, FeO and MgO contents (<xref ref-type="fig" rid="F5">Figure 5</xref>), their temperatures are lower. This may indicate a lack of hotter, more mafic magma input, correlating with evidence from uranium-series disequilibria in mafic enclaves and their hosts that suggest the intrusion of mafic magma had halted by Pause 2 (<xref ref-type="bibr" rid="B75">McGee et al., 2019</xref>).</p>
<fig id="F9" position="float">
<label>FIGURE 9</label>
<caption>
<p>Pressurevs temperature graph for inclusions at SHV showing the magmatic conditions at the time of plagioclase and orthopyroxene crystal growth. Grey horizontal dashes represent the depths of magma storage based on deformation modelling (<xref ref-type="bibr" rid="B45">Foroozan et al., 2010</xref>). Error bars represent the uncertainty in depths based on uncertainties in total CO<sub>2</sub>. Error bars for orthopyroxene-hosted melt inclusions are not shown as the uncertainty is smaller than the size of the symbol.</p>
</caption>
<graphic xlink:href="feart-12-1509409-g009.tif"/>
</fig>
<p>Temperatures calculated in this study are the first temperature estimates for Phases 2, 4 and 5 using melt inclusion data and are similar to those of Phase 1 (812&#xb0;C&#x2013;891&#xb0;C) obtained via geothermometry and experimental phase equilibria (e.g., <xref ref-type="bibr" rid="B11">Barclay et al., 1998</xref>; <xref ref-type="bibr" rid="B35">Devine et al., 1998</xref>; <xref ref-type="bibr" rid="B88">Murphy et al., 2000</xref>).</p>
<p>Constraints on hornblende stability have been used to infer that the andesitic magma was originally cooler (&#x2264;840&#xb0;C), before being reheated by injection of deeper basalt, which elevated the andesite temperature to &#x223c;880&#xb0;C (<xref ref-type="bibr" rid="B11">Barclay et al., 1998</xref>; <xref ref-type="bibr" rid="B35">Devine et al., 1998</xref>).</p>
</sec>
<sec id="s5-1-2">
<title>5.1.2 Saturated pressures and associated depths</title>
<p>The crustal depth and thus pressure at which magma accumulates is a key influence on volcanic system behaviour, including exsolution of volatiles, crystallisation, and mineral growth (<xref ref-type="bibr" rid="B56">Huber et al., 2019</xref>). The mush model, whereby melt exists within a continuous crystalline framework (<xref ref-type="bibr" rid="B71">Marsh, 2004</xref>; <xref ref-type="bibr" rid="B24">Cashman et al., 2017</xref>) has been proposed for arc volcanoes including those of the Lesser Antilles, with storage regions being continuous (Dominica and Kick &#x2018;em Jenny) or multi-leveled (Guadeloupe, Martinique and St Lucia; <xref ref-type="bibr" rid="B80">Metcalfe et al., 2023</xref>). Storage depths at SHV, Montserrat have been previously estimated using volatiles in melt inclusion glasses alone (e.g., <xref ref-type="bibr" rid="B40">Edmonds et al., 2014</xref>; <xref ref-type="bibr" rid="B41">Edmonds et al., 2016</xref>) and are clearly underestimated as bubble-hosted CO<sub>2</sub> was neglected. Recalculation is now possible with the new whole melt inclusion glass &#x2b; bubble CO<sub>2</sub> results provided here, providing a better understanding of the plumbing system.</p>
<p>After accounting for PEC and bubble growth, the values of total CO<sub>2</sub>, H<sub>2</sub>O, melt inclusion composition, and temperature were input into the H<sub>2</sub>O-CO<sub>2</sub> solubility model MagmaSat (<xref ref-type="bibr" rid="B49">Ghiorso and Gualda, 2015</xref>), hosted in VESIcal (<xref ref-type="bibr" rid="B60">Iacovino et al., 2021</xref>). MagmaSat permits calculation of saturation pressures for each melt inclusion based on specific composition-relevant pressure-solubility relations, and its usefulness is underpinned by the assumption that the melt trapped within inclusions is representative of the magma storage regions from which the crystals are derived (<xref ref-type="bibr" rid="B20">Cannatelli et al., 2016</xref>). Model results indicate that melt inclusion saturation pressures over the duration of eruptions at SHV are highly variable, with plagioclase-hosted inclusions yielding entrapment pressures spanning 1000&#x2013;6800 bars (100&#x2013;680 MPa). Pressures for orthopyroxene-hosted inclusions are more restricted in range, between 1900&#x2013;3200 bars (190&#x2013;320 MPa).</p>
<p>To correlate entrapment pressures to depths (MI<sub>depth</sub>), <xref ref-type="disp-formula" rid="e2">Equation 2</xref> is applied:<disp-formula id="e2">
<mml:math id="m5">
<mml:mrow>
<mml:msub>
<mml:mrow>
<mml:mi>M</mml:mi>
<mml:mi>I</mml:mi>
</mml:mrow>
<mml:mrow>
<mml:mi>d</mml:mi>
<mml:mi>e</mml:mi>
<mml:mi>p</mml:mi>
<mml:mi>t</mml:mi>
<mml:mi>h</mml:mi>
</mml:mrow>
</mml:msub>
<mml:mo>&#x3d;</mml:mo>
<mml:mfrac>
<mml:mi>p</mml:mi>
<mml:mrow>
<mml:mi>&#x3c1;</mml:mi>
<mml:mi>g</mml:mi>
</mml:mrow>
</mml:mfrac>
</mml:mrow>
</mml:math>
<label>(2)</label>
</disp-formula>where MI<sub>depth</sub> (m), is based on pressure <italic>&#x201c;p&#x201d;</italic> (in Pascals) calculated above, Lesser Antilles crustal density <italic>&#x201c;</italic>&#x3c1;<italic>&#x201d;</italic> of 2660 kgm<sup>&#x2212;3</sup> (<xref ref-type="bibr" rid="B29">Christeson et al., 2008</xref>) and g &#x3d; 9.81 m<sup>&#x2212;2</sup>.</p>
<p>Therefore, the pressures derived here indicate that SHV melt inclusions were trapped in orthopyroxenes and plagioclases at upper to mid crustal depths (5.7 &#xb1; 0.8 to 17 &#xb1; 2.5 km), with four plagioclase-hosted inclusions in the lower crust (20 &#xb1; 2.8 to 23 &#xb1; 1.3 km), and one deeper inclusion plotting at 26 &#xb1; 4.0 km. While plagioclase-hosted inclusions span the entire calculated range, orthopyroxene-hosted inclusions are restricted to 7.4 &#xb1; 0.1 to 12 &#xb1; 0.3 km, similar to depth estimates from the H<sub>2</sub>O content of enstatites (mean of 10 km, over a total range of 4&#x2013;16 km; <xref ref-type="bibr" rid="B41">Edmonds et al., 2016</xref>).</p>
<p>The depth of magma storage has been linked to 1) the depth of neutral buoyancy where the density of magma and country rock are similar (<xref ref-type="bibr" rid="B55">Hooft and Detrick, 1993</xref>), 2) rheological conditions of the crust (<xref ref-type="bibr" rid="B74">Mazzarini et al., 2010</xref>), and 3) to the location of pre-existing zones of crust weakness (<xref ref-type="bibr" rid="B28">Chaussard and Amelung, 2014</xref>). Alternatively, inferred magma storage depths may instead merely reflect the magmatic water concentrations (<xref ref-type="bibr" rid="B97">Rasmussen et al., 2022</xref>), where the maximum H<sub>2</sub>O content of SHV magmas correlates to &#x223c;13 km depth. However, melt inclusion data at SHV resolve depths greater than 13 km for 20% of inclusions, and are outside of the mafic-intermediate dataset range used in the study. This H<sub>2</sub>O limit does not appear to apply to this volcanic system - perhaps due to the higher silica content of the SHV magma.</p>
<p>Our new melt inclusion H<sub>2</sub>O and CO<sub>2</sub> data support a vertically extensive transcrustal magmatic system (<xref ref-type="fig" rid="F9">Figure 9</xref>; <xref ref-type="fig" rid="F10">Figure 10</xref>; e.g;, <xref ref-type="bibr" rid="B24">Cashman et al., 2017</xref>). The wide range of pressures and depths relate to inclusion trapping during crystal growth within a vertically extensive magma storage system that spans 5&#x2013;17 km, with no distinct gaps in crystallisation depths. The transcrustal model can also explain the wide range of entrapment pressures inferred from H<sub>2</sub>O and Al<sub>2</sub>O<sub>3</sub> contents of Phase 3 orthopyroxenes (<xref ref-type="bibr" rid="B41">Edmonds et al., 2016</xref>), and 3D modelling of the ground deformation during Pause 5, where best solutions require melt injection into the base of a mush-based reservoir at &#x223c;17 km depth (<xref ref-type="bibr" rid="B50">Gottsmann et al., 2020</xref>; <xref ref-type="bibr" rid="B3">Alshembari et al., 2024</xref>). Vertically extensive mush systems are the proposed magma storage types in arc environments, including the Lesser Antilles (<xref ref-type="bibr" rid="B80">Metcalfe et al., 2023</xref>), and are more importantly not uncommon to Montserrat, where melt inclusions from South Soufri&#xe8;re Hills reveal trapping pressures equivalent to 3&#x2013;17 km depth using vapour-bubble-free melt inclusions hosted in olivine and clinopyroxene (<xref ref-type="bibr" rid="B25">Cassidy et al., 2015a</xref>; <xref ref-type="bibr" rid="B27">Cassidy et al., 2015b</xref>).</p>
<fig id="F10" position="float">
<label>FIGURE 10</label>
<caption>
<p>Schematic of the plumbing system beneath Soufriere Hills Volcano, exhibiting mush properties similar to other arc volcanoes. This is a vertically extensive transcrustal magmatic system consists of a melt-rich zone with high H<sub>2</sub>O and CO<sub>2</sub> contents and a crystal rich zone dominated by calcic plagioclase and orthopyroxene spanning &#x223c;5&#x2013;17 km, and is periodically flushed with CO<sub>2</sub> from deeper in the system. Melt inclusions from Phases 1 and 5 plot in the mid crustal region whereas Phases 2 and 4 span the upper to mid crustal regions.</p>
</caption>
<graphic xlink:href="feart-12-1509409-g010.tif"/>
</fig>
<p>Phase 1 inclusions are evenly spread at 9.7 &#xb1; 0.7 to 16 &#xb1; 1.3 km, with one outlier at 7.3 &#xb1; 0.5 km. In Phase 2, depths span 7.2 &#xb1; 1.3 to 16 &#xb1; 2.7 km, with one outlier at 26 &#xb1; 4.0 km. Phases 4 and 5 also have similar depths to the first two phases at 5.7 &#xb1; 0.8 to 17 &#xb1; 2.5 and 9.9 &#xb1; 0.4 to 17 &#xb1; 1.3 km respectively, however, with outliers at 20 &#xb1; 1.2 to 23 &#xb1; 1.3 km.</p>
<p>Geochemical, geodetic and Fe-oxide data place a lower limit of &#x223c;17 km for the SHV magma storage region in both dual and mush reservoir scenarios (<xref ref-type="bibr" rid="B45">Foroozan et al., 2010</xref>; <xref ref-type="bibr" rid="B41">Edmonds et al., 2016</xref>; <xref ref-type="bibr" rid="B3">Alshembari et al., 2024</xref>), consistent with the inferred entrapment pressure of 58 of the 63 melt inclusions characterised in this study. Thus, the overwhelming majority of the inclusions, which resolve depths &#x3c;17 km, are taken as representative of a melt undergoing crystallization, degassing, and thus differentiation.</p>
</sec>
</sec>
<sec id="s5-2">
<title>5.2 CO<sub>2</sub> budget</title>
<p>The maximum measured CO<sub>2</sub> concentration in melt inclusions glass and bubble, representing the least degassed CO<sub>2</sub> trapped in melt inclusions is compared to estimates of CO<sub>2</sub> degassed through the plume using the petrological method (<xref ref-type="bibr" rid="B37">Devine, et al., 1984</xref>), assuming that the concentration of volatiles in melt inclusions represents the concentration of volatiles dissolved in the magma at depth. A total of 4.5 Mt of CO<sub>2</sub> (M<sub>dv</sub>) is calculated to have been contained in SHV magma during Phases 1, 2, 4, and 5 based on <xref ref-type="disp-formula" rid="e3">Equation 3</xref>:<disp-formula id="e3">
<mml:math id="m6">
<mml:mrow>
<mml:msub>
<mml:mi>M</mml:mi>
<mml:mrow>
<mml:mi>d</mml:mi>
<mml:mi>v</mml:mi>
</mml:mrow>
</mml:msub>
<mml:mo>&#x3d;</mml:mo>
<mml:msub>
<mml:mi>X</mml:mi>
<mml:mrow>
<mml:mi>M</mml:mi>
<mml:mi>I</mml:mi>
</mml:mrow>
</mml:msub>
<mml:mi>V</mml:mi>
<mml:mi>&#x3c1;</mml:mi>
</mml:mrow>
</mml:math>
<label>(3)</label>
</disp-formula>where X<sub>MI</sub> is the maximum concentration of CO<sub>2</sub> measured in melt inclusions (3230 ppm) in the studied Phases, V is the volume of erupted magma (<xref ref-type="bibr" rid="B117">Wadge et al., 2014</xref>), and &#x3c1; refers to the magma density of 2400 kg m<sup>&#x2212;3</sup> Dense Rock Equivalent (<xref ref-type="bibr" rid="B78">Melnik and Sparks, 2002</xref>). Phases 1 and 2 held more dissolved CO<sub>2</sub> in their magmas with maxima of 1.2 and 2.6 Mt respectively, exceeding the corresponding figures for Phases 4 and 5 (0.25 and 0.44 Mt respectively). This total of 4.5 Mt of CO<sub>2</sub> dissolved in the magma is however much less than the 7.7&#x2013;12 Mt total plume-emitted CO<sub>2</sub> estimated by <xref ref-type="bibr" rid="B40">Edmonds et al. (2014)</xref> during the period 1995&#x2013;2009, using an average molar CO<sub>2</sub>/SO<sub>2</sub> ratio of 5.1. However, the ratio of 5.1 used in their estimation introduces a large error, as it is derived from 5 days of measurements during Pause 3, and assumes a constant ratio over 14 years of activity. This mismatch of petrological estimates in comparison to direct measurements is often seen in SO<sub>2</sub> fluxes, and is a feature common to arc settings where magmas are more oxidized, and is not generally observed in non-arc magmas (e.g., <xref ref-type="bibr" rid="B108">Sigurdsson, et al., 1990</xref>; <xref ref-type="bibr" rid="B119">Westrich and Gerlach, 1992</xref>; <xref ref-type="bibr" rid="B48">Gerlach et al., 1994</xref>; <xref ref-type="bibr" rid="B13">Blake, 2003</xref>; <xref ref-type="bibr" rid="B107">Sharma et al., 2004</xref>).</p>
<p>Applying the 5 days of CO<sub>2</sub> measurements (<xref ref-type="bibr" rid="B40">Edmonds et al., 2014</xref>) in the plume taken during July 2008 to a shorter time period of Phase 4 (July 2008-January 2009), we calculate that 0.24 Mt was released in the plume over 158 days. Therefore 96% of the CO<sub>2</sub> dissolved in Phase 4 magma was emitted during the eruption. Applying the calculations to Phase 5 (October 2009-January 2010), an average of 2297 tonnes/day of CO<sub>2</sub> emitted from June-November 2010 (<xref ref-type="bibr" rid="B40">Edmonds et al., 2014</xref>) amounts to 0.29 Mt or 66% of the CO<sub>2</sub> dissolved in the magma being released over 125 days. While these estimates are termed &#x2018;maxima&#x2019; based on the maximum CO<sub>2</sub> considered for each Phase, it is noted that masses calculated can be underestimated due to 1) unerupted volumes of magma which are not taken into account, and 2) entrapment of already degassed melt (<xref ref-type="bibr" rid="B86">Moune et al., 2007</xref>). The percentage of CO<sub>2</sub> released during Phases 1 and 2 is unable to be estimated due to lack of published CO<sub>2</sub> fluxes.</p>
<p>Original magmatic CO<sub>2</sub> contents can also be estimated using the CO<sub>2</sub> flux derived by combining SO<sub>2</sub> fluxes measured using UV spectrometer and CO<sub>2</sub>/SO<sub>2</sub> ratio acquired via Multisensor Gas Analyser System (MultiGAS) over the 5 days in July 2008 and 15 days during June to October 2009. The highest CO<sub>2</sub> flux reported (<xref ref-type="bibr" rid="B40">Edmonds et al., 2014</xref>) of 5494 tonnes/day measured on 1 October 2010 is used to calculate a maximum mass of CO<sub>2</sub> for a period of 125 days during Phase 5, amounting to 0.69 Mt, and magma masses are calculated from reported magma volume estimates and magmatic density of 2400 kgm<sup>&#x2212;3</sup>. We can therefore use <xref ref-type="disp-formula" rid="e3">Equation 3</xref> to estimate the required melt inclusion CO<sub>2</sub> concentration to match the measured CO<sub>2</sub> emissions. This value of 4107 ppm is 877 higher than the initial CO<sub>2</sub> from the least degassed melt inclusions measured across the eruption. This value correlates to a pressure of 8090 bars or 31.0 km depth assuming a H<sub>2</sub>O content of 6.39 wt%, the highest of the Phase 5 inclusions. As a result, we attribute this high CO<sub>2</sub> flux to CO<sub>2</sub> flushing (e.g., <xref ref-type="bibr" rid="B14">Blundy et al., 2010</xref>; <xref ref-type="bibr" rid="B21">Caricchi et al., 2018</xref>) from degassing deeper in the system, a process that is commonplace in the arc, and occurs in all island groups (<xref ref-type="bibr" rid="B80">Metcalfe et al., 2023</xref>). The related depth would extend into the Moho situated &#x223c;30 km under Montserrat, based on crustal xenolith petrology and seismic data (<xref ref-type="bibr" rid="B77">Melekhova et al., 2019</xref>). Based on fluxes generated during June to October, and compared to Phase 5, a CO<sub>2</sub> flux greater than &#x223c;1500&#x2013;1750 tonnes/day cannot be accounted for by the dissolved CO<sub>2</sub> in this batch of magma, and therefore relate to CO<sub>2</sub> flushing from mantle depths.</p>
</sec>
<sec id="s5-3">
<title>5.3 CO<sub>2</sub> controls on explosivity and implications for the future</title>
<p>Quantification of dissolved magmatic gases as well as their emissions is essential for understanding the influence of volatiles on volcanic system dynamics and the related hazards. The dissolved magmatic CO<sub>2</sub> concentration can, alongside more abundant H<sub>2</sub>O, drive eruptions, dictate eruptive style or impact both in volcanic settings (e.g., <xref ref-type="bibr" rid="B19">Burton et al., 2007</xref>; <xref ref-type="bibr" rid="B1">Allard, 2010</xref>; <xref ref-type="bibr" rid="B2">Allison et al., 2021</xref>). The eruptive style at SHV can be described as transitioning, with both effusive and explosive eruptions occurring during each Phase, producing lava domes and explosions (e.g., <xref ref-type="bibr" rid="B38">Druitt et al., 2002</xref>; <xref ref-type="bibr" rid="B39">Edmonds and Herd, 2007</xref>; <xref ref-type="bibr" rid="B104">Ryan et al., 2010</xref>). However, at SHV, microlite petrology from Phase 3 samples has demonstrated that shallow conduit processes determine eruptive style, with similar decompression pathways within the deeper magmatic system resulting in both lava dome growth and explosions (<xref ref-type="bibr" rid="B87">Murch and Cole, 2019</xref>). Nevertheless, melt inclusion analysis conducted in this study shows that while each Phase produced VEI 2-3 events, their SiO<sub>2</sub> content, H<sub>2</sub>O content, CO<sub>2</sub> content, duration, and the number of explosions differ. Particularly, Phase 1 and 5 are similar in silica content, H<sub>2</sub>O and also have similar pressures and depths based on solubility modeling of melt inclusion H<sub>2</sub>O and CO<sub>2</sub> concentrations. While these Phases exhibit similar chemistry, their explosive behaviours have differed, with Phase 5 producing more Vulcanian explosions within a shorter timeframe (125 days) than Phase 1 (846 days). This is likely due to the amount of CO<sub>2</sub> in the system during these Phases as Phase 1 had &#x223c;1,000 ppm less CO<sub>2</sub> dissolved within its melt and Phase 5 was influenced by CO<sub>2</sub> flushing. However, due to the limited availability of CO<sub>2</sub> flux data at SHV, it is unclear if CO<sub>2</sub> flushing occurred during either Phases.</p>
<p>The monitoring of volatile release at SHV has primarily focused on SO<sub>2</sub> flux (e.g., <xref ref-type="bibr" rid="B121">Young et al., 1998</xref>; <xref ref-type="bibr" rid="B22">Carn and Prata, 2010</xref>; <xref ref-type="bibr" rid="B92">Nicholson et al., 2013</xref>; <xref ref-type="bibr" rid="B30">Christopher et al., 2015</xref>), however trends in SO<sub>2</sub> have not correlated with the eruptive Phases, but instead occur on multi-year (&#x223c;2 years) and multi-week cycles (&#x223c;50 days and &#x223c;5 months), independent of lava extrusion and dome building (<xref ref-type="bibr" rid="B92">Nicholson et al., 2013</xref>; <xref ref-type="bibr" rid="B30">Christopher et al., 2015</xref>), upon which Phases are determined. We recommend that CO<sub>2</sub> should also be routinely monitored as it provides insight into movement of magma in the deep system, and also has the ability to drive eruptions through processes such as CO<sub>2</sub> flushing, which can alter the physical properties of the magma - increasing magma volume, leading to overpressure and potentially eruptions (<xref ref-type="bibr" rid="B21">Caricchi et al., 2018</xref>). While data are severely limited, instances of CO<sub>2</sub> flushing at SHV are evident at the transition between Pause 3 and Phase 4, and &#x223c;6 months after the cessation of Phase 5. As the crystallinity of SHV magma, at 30%&#x2013;45%, is at or beneath the threshold at which magmas reach their rheological locking point (40%&#x2013;50%), flushing at SHV can potentially trigger eruptions. This further highlights the importance of monitoring of CO<sub>2</sub> flux at SHV, especially during the current period of unrest.</p>
</sec>
</sec>
<sec sec-type="conclusion" id="s6">
<title>6 Conclusion</title>
<p>We have provided the most comprehensive study published to date of magmatic carbon in the Soufri&#xe8;re Hills Volcano magmatic system, providing the first measurements to include bubble-hosted CO<sub>2</sub> in melt inclusions and the first pre-eruptive CO<sub>2</sub> measurements for the most recent eruptive phases. H<sub>2</sub>O and total CO<sub>2</sub> contents for melt inclusions hosted in plagioclase from pumice erupted during four phases of eruption are 2.47&#x2013;6.40 wt% H<sub>2</sub>O and 131&#x2013;3230 ppm CO<sub>2</sub>. Those hosted in orthopyroxene are 5.15&#x2013;7.26 wt% and 199&#x2013;736 ppm CO<sub>2</sub>. The sequestration of CO<sub>2</sub> to the bubble has proven to be an important post-entrapment modification at SHV, with 5%&#x2013;99% (median 90%) of CO<sub>2</sub> contained in bubbles and thus excluded in earlier analyses. Our measurements therefore provide unprecedented insight into the magmatic CO<sub>2</sub> concentrations within the SHV system and indicate higher concentrations than previous studies. Our volatile solubility-based estimates of magma storage depths (5.7&#x2013;17 km) indicate that a transcrustal magmatic system was persistent throughout the eruption, consistent with geodetic modelling (<xref ref-type="bibr" rid="B3">Alshembari et al., 2024</xref>).</p>
<p>We use melt inclusion compositions to estimate magmatic temperatures at entrapment, based on liquid-mineral pairs. Temperature results (828&#xb0;C&#x2013;916&#xb0;C) are similar to published estimates for Phase 1 (812&#xb0;C&#x2013;891&#xb0;C) and are the first temperature estimates for Phases 2, 4, and 5.</p>
<p>The total amount of CO<sub>2</sub> contained in magma from Phases 1, 2, 4, and 5 is &#x223c;4.5 Mt, using the petrological method. We calculate that 96% of the dissolved CO<sub>2</sub> in Phase 4 magma was released to the atmosphere during Phase 4, and 66% of the dissolved CO<sub>2</sub> in Phase 5 was released. Our results indicate that &#x223c;1500&#x2013;1750 tonnes/day CO<sub>2</sub> can be emitted from the magma, and thus any CO<sub>2</sub> fluxes higher than 1750 tonnes/day are likely the result of CO<sub>2</sub> flushing from deeper in the magmatic system. Pauses 4 and 5 therefore experienced CO<sub>2</sub> flushing, with up to 5494 tonnes/day being released (<xref ref-type="bibr" rid="B40">Edmonds et al., 2014</xref>), and are the only Phases with reported CO<sub>2</sub> fluxes.</p>
<p>Our new melt inclusions dataset covers four of five Phases of eruptive activity at SHV, and provides the first account of total (glass &#x2b; bubble hosted) CO<sub>2</sub>. Our data indicates that the magmatic system feeding SHV is a vertically elongated mush system, as corroborated by geophysics and geochemistry.</p>
</sec>
</body>
<back>
<sec sec-type="data-availability" id="s7">
<title>Data availability statement</title>
<p>The original contributions presented in the study are included in the article/<xref ref-type="sec" rid="s13">Supplementary Material</xref>, further inquiries can be directed to the corresponding author.</p>
</sec>
<sec sec-type="author-contributions" id="s8">
<title>Author contributions</title>
<p>TH: conceptualization, writing&#x2013;original draft, writing&#x2013;review and editing, investigation, methodology, formal analysis, visualization, funding acquisition. TC: conceptualization, writing&#x2013;review and editing, formal analysis, supervision. SM: conceptualization, writing&#x2013;review and editing, formal analysis, supervision. HT: conceptualization, writing&#x2013;review and editing, formal analysis, supervision, funding acquisition. FS: investigation, methodology, formal analysis, writing&#x2013;review and editing.</p>
</sec>
<sec sec-type="funding-information" id="s9">
<title>Funding</title>
<p>The author(s) declare that financial support was received for the research, authorship, and/or publication of this article. This study was supported by a Government of Montserrat PhD scholarship awarded to TH. Funding for ionprobe analysis was provided by NERC IMF grant IMF746/1122 awarded to HT and TH. Raman and whole rock analyses were graciously covered by the Volcanology team at Laboratoire Magmas et Volcans. Article Processing Fees were provided by Lancaster University.</p>
</sec>
<ack>
<p>We thank the Montserrat Volcano Observatory for granting use of samples. Many thanks to Cees-Jan de Hoog for assistance with SIMS, Iris Buisman for EPMA assistance and Claire Fonquernie for whole rock analysis. We are grateful to David Neave and Margaret Hartley for discussions on melt inclusions and in particular their reconstruction.</p>
</ack>
<sec sec-type="COI-statement" id="s10">
<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>
</sec>
<sec sec-type="ai-statement" id="s11">
<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="s12">
<title>Publisher&#x2019;s note</title>
<p>All claims expressed in this article are solely those of the authors and do not necessarily represent those of their affiliated organizations, or those of the publisher, the editors and the reviewers. Any product that may be evaluated in this article, or claim that may be made by its manufacturer, is not guaranteed or endorsed by the publisher.</p>
</sec>
<sec id="s13">
<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/feart.2024.1509409/full#supplementary-material">https://www.frontiersin.org/articles/10.3389/feart.2024.1509409/full&#x23;supplementary-material</ext-link>
</p>
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<supplementary-material xlink:href="DataSheet2.xlsx" id="SM2" mimetype="application/xlsx" xmlns:xlink="http://www.w3.org/1999/xlink"/>
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