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<front>
<journal-meta>
<journal-id journal-id-type="publisher-id">Front. Mar. Sci.</journal-id>
<journal-title>Frontiers in Marine Science</journal-title>
<abbrev-journal-title abbrev-type="pubmed">Front. Mar. Sci.</abbrev-journal-title>
<issn pub-type="epub">2296-7745</issn>
<publisher>
<publisher-name>Frontiers Media S.A.</publisher-name>
</publisher>
</journal-meta>
<article-meta>
<article-id pub-id-type="doi">10.3389/fmars.2023.1072610</article-id>
<article-categories>
<subj-group subj-group-type="heading">
<subject>Marine Science</subject>
<subj-group>
<subject>Original Research</subject>
</subj-group>
</subj-group>
</article-categories>
<title-group>
<article-title>Differential response of chlorophyll-a concentrations to explosive volcanism in the western South Pacific</article-title>
</title-group>
<contrib-group>
<contrib contrib-type="author" corresp="yes">
<name>
<surname>Yoon</surname>
<given-names>Joo-Eun</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="author-notes" rid="fn001">
<sup>*</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/529938"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>King</surname>
<given-names>David</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Longman</surname>
<given-names>Jack</given-names>
</name>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
<xref ref-type="aff" rid="aff4">
<sup>4</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/1156877"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Cronin</surname>
<given-names>Shane J.</given-names>
</name>
<xref ref-type="aff" rid="aff5">
<sup>5</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/301743"/>
</contrib>
</contrib-group>
<aff id="aff1">
<sup>1</sup>
<institution>Centre for Climate Repair at Cambridge, Department of Applied Mathematics and Theoretical Physics, University of Cambridge</institution>, <addr-line>Cambridge</addr-line>, <country>United Kingdom</country>
</aff>
<aff id="aff2">
<sup>2</sup>
<institution>Downing College, University of Cambridge</institution>, <addr-line>Cambridge</addr-line>, <country>United Kingdom</country>
</aff>
<aff id="aff3">
<sup>3</sup>
<institution>Marine Isotope Geochemistry, Institute for Chemistry and Biology of the Marine Environment (ICBM), University of Oldenburg</institution>, <addr-line>Oldenburg</addr-line>, <country>Germany</country>
</aff>
<aff id="aff4">
<sup>4</sup>
<institution>Department of Geography and Environmental Sciences, Northumbria University</institution>, <addr-line>Newcastle upon Tyne</addr-line>, <country>United Kingdom</country>
</aff>
<aff id="aff5">
<sup>5</sup>
<institution>School of Environment, The University of Auckland</institution>, <addr-line>Auckland</addr-line>, <country>New Zealand</country>
</aff>
<author-notes>
<fn fn-type="edited-by">
<p>Edited by: Ricardo Maria Letelier, Oregon State University, United States</p>
</fn>
<fn fn-type="edited-by">
<p>Reviewed by: Sudheer A. K., Physical Research Laboratory, India; Jan-Lukas Menzel Barraqueta, European Ecological Consulting S.L., Spain</p>
</fn>
<fn fn-type="corresp" id="fn001">
<p>*Correspondence: Joo-Eun Yoon, <email xlink:href="mailto:jey28@cam.ac.uk">jey28@cam.ac.uk</email>
</p>
</fn>
<fn fn-type="other" id="fn002">
<p>This article was submitted to Marine Biogeochemistry, a section of the journal Frontiers in Marine Science</p>
</fn>
</author-notes>
<pub-date pub-type="epub">
<day>19</day>
<month>04</month>
<year>2023</year>
</pub-date>
<pub-date pub-type="collection">
<year>2023</year>
</pub-date>
<volume>10</volume>
<elocation-id>1072610</elocation-id>
<history>
<date date-type="received">
<day>17</day>
<month>10</month>
<year>2022</year>
</date>
<date date-type="accepted">
<day>31</day>
<month>03</month>
<year>2023</year>
</date>
</history>
<permissions>
<copyright-statement>Copyright &#xa9; 2023 Yoon, King, Longman and Cronin</copyright-statement>
<copyright-year>2023</copyright-year>
<copyright-holder>Yoon, King, Longman and Cronin</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>When it is deposited in the ocean, volcanic ash has the potential to release iron and other nutrients into surface water to stimulate ocean productivity. In the western South Pacific Ocean (SPO), one of the most important volcanic ash deposition regions, occasional widespread transport of volcanic ash may supply the nutrients not only locally around source islands but also within the wider the western SPO, accompanied by phytoplankton response. Through a comparative analysis of satellite and reanalysis data for the past 19 years (2004&#x2013;2022), this study reveals that four explosive volcanic eruptions, Rabaul volcano, Papua New Guinea (October, 2006), Ambae volcano, Vanuatu (July, 2018), Ulawun volcano, Papua New Guinea (June, 2019), and Hunga volcano, Tonga (January, 2022), had the most strong stratospheric injection (&gt;15&#xa0;km) and mass loading of volcanic materials over the wider the western SPO (covering an area of &gt;765,000 km<sup>2</sup>). The transport of 2006, 2018, 2019 volcanic emissions, was not likely associated with significant ash deposition over the western SPO. However, the Hunga eruption led to the deposition of ash-laden volcanic plumes over a wide area (~2,000 km from source), and was followed by the increase in chlorophyll-a concentrations (Chl-a) in the region (~70% increase). Minor changes related to other nutrient sources (e.g., hydrothermal input) suggest a link between the increase in Chl-a and 2022 Hunga ash falls over the western SPO. Our results indicate that volcanic ash deposition has implications for phytoplankton productivity in the western SPO, and highlights the need for further research into understanding how nutrient supply alleviated limitations of phytoplankton at the community level.</p>
</abstract>
<kwd-group>
<kwd>volcanic eruption</kwd>
<kwd>western South Pacific Ocean</kwd>
<kwd>satellite data</kwd>
<kwd>chlorophyll-a concentration</kwd>
<kwd>ash deposition</kwd>
</kwd-group>
<counts>
<fig-count count="4"/>
<table-count count="0"/>
<equation-count count="0"/>
<ref-count count="83"/>
<page-count count="13"/>
<word-count count="6972"/>
</counts>
</article-meta>
</front>
<body>
<sec id="s1" sec-type="intro">
<label>1</label>
<title>Introduction</title>
<p>Anthropogenic greenhouse gas release to the atmosphere since the beginning of the industrial era has caused climate change and global warming, with the oceans taking up more than 90% of the excess heat trapped in the earth system (<xref ref-type="bibr" rid="B18">Cooley et&#xa0;al., 2022</xref>). This increased ocean temperature has resulted in greater water-column stability and stronger ocean stratification, contributing to a decrease in phytoplankton biomass, due to a decrease in upward nutrient flux to the euphotic zone (<xref ref-type="bibr" rid="B4">Behrenfeld et&#xa0;al., 2006</xref>; <xref ref-type="bibr" rid="B11">Boyce et&#xa0;al., 2010</xref>; <xref ref-type="bibr" rid="B6">Bindoff et&#xa0;al., 2019</xref>; <xref ref-type="bibr" rid="B44">Li et&#xa0;al., 2020b</xref>). The external supply of nutrients to the marine environments (e.g., atmospheric deposition and riverine input) therefore is recognized to play an increasingly important role in marine biogeochemical cycles and marine ecosystems, helping to offset reduced nutrient supply <italic>via</italic> upwelling (<xref ref-type="bibr" rid="B20">Duce et&#xa0;al., 2008</xref>; <xref ref-type="bibr" rid="B77">Wang et&#xa0;al., 2015</xref>; <xref ref-type="bibr" rid="B82">Yoon et&#xa0;al., 2022</xref>).</p>
<p>Atmospheric deposition episodically transports macro- and micronutrients (N, P, Si, Fe, and other metals) from natural (e.g., desert dust, volcanic ash, and forest fires) and anthropogenic sources (e.g., fossil fuel combustion and biomass burning) to the surface ocean throughout the globe (<xref ref-type="bibr" rid="B28">Guieu et&#xa0;al., 2014</xref>; <xref ref-type="bibr" rid="B39">Kim et&#xa0;al., 2014</xref>; <xref ref-type="bibr" rid="B34">Jickells and Moore, 2015</xref>; <xref ref-type="bibr" rid="B74">Ventura et&#xa0;al., 2021</xref>; <xref ref-type="bibr" rid="B50">Longman et&#xa0;al., 2022</xref>). In particular, volcanic ash, which is formed during explosive volcanic eruptions, is highly reactive and can rapidly release iron and other nutrients (Si, N, Mn) into the surface water to stimulate ocean productivity (<xref ref-type="bibr" rid="B26">Frogner et&#xa0;al., 2001</xref>; <xref ref-type="bibr" rid="B21">Duggen et&#xa0;al., 2007</xref>; <xref ref-type="bibr" rid="B36">Jones and Gislason, 2008</xref>; <xref ref-type="bibr" rid="B50">Longman et&#xa0;al., 2022</xref>). This can occur on local to regional scales, with wide ranges in the nutrient supply, dependant on ash-loading, ash particle size, chemical composition, and surface salt coatings (<xref ref-type="bibr" rid="B21">Duggen et&#xa0;al., 2007</xref>; <xref ref-type="bibr" rid="B30">Hamilton et&#xa0;al., 2022</xref>). Several studies have shown that elevated fluxes of metals and nutrients following the deposition of volcanic ash stimulated primary productivity (PP) not only in high-nitrate low-chlorophyll (HNLC) regions but also in low-nitrate low-chlorophyll (LNLC) regions (<xref ref-type="bibr" rid="B31">Hamme et&#xa0;al., 2010</xref>; <xref ref-type="bibr" rid="B43">Langmann et&#xa0;al., 2010</xref>; <xref ref-type="bibr" rid="B47">Lin et&#xa0;al., 2011</xref>; <xref ref-type="bibr" rid="B1">Achterberg et&#xa0;al., 2013</xref>; <xref ref-type="bibr" rid="B62">Olgun et&#xa0;al., 2013b</xref>). Accordingly, volcanic ash has been suggested as a fertilizer material to promote ocean productivity (<xref ref-type="bibr" rid="B22">Duggen et&#xa0;al., 2010</xref>; <xref ref-type="bibr" rid="B31">Hamme et&#xa0;al., 2010</xref>; <xref ref-type="bibr" rid="B62">Olgun et&#xa0;al., 2013b</xref>; <xref ref-type="bibr" rid="B49">Longman et&#xa0;al., 2019</xref>; <xref ref-type="bibr" rid="B48">Longman et&#xa0;al., 2020</xref>).</p>
<p>The western South Pacific Ocean (SPO), a highly stratified oligotrophic system (the low-nutrient situation; <xref ref-type="bibr" rid="B7">Bock et&#xa0;al., 2018</xref>), has been recently described as a hot spot of dinitrogen (N<sub>2</sub>) fixing organisms, which contribute to the high levels of PP (<xref ref-type="bibr" rid="B9">Bonnet et&#xa0;al., 2017</xref>; <xref ref-type="bibr" rid="B15">Caffin et&#xa0;al., 2018</xref>). In this region, the west&#x2013;east gradient of N<sub>2</sub> fixation, with higher values in the western parts, has been attributed to the alleviation of iron limitation by hydrothermal submarine iron inputs, island sediment, and land runoff in the west of the Tonga arc (<xref ref-type="bibr" rid="B67">Shiozaki et&#xa0;al., 2014</xref>; <xref ref-type="bibr" rid="B8">Bonnet et&#xa0;al., 2018</xref>; <xref ref-type="bibr" rid="B29">Guieu et&#xa0;al., 2018</xref>; <xref ref-type="bibr" rid="B58">Moutin et&#xa0;al., 2018</xref>; <xref ref-type="bibr" rid="B72">Tilliette et&#xa0;al., 2022</xref>). However, the western SPO, as one of most important volcanic ash deposition regions, has the potential to be fertilized by the transport of volcanic ash from the explosive eruptions, such as the volcano from Tonga, Vanuatu, and Papua New Guinea (<xref ref-type="supplementary-material" rid="SM1">
<bold>Figure S1A</bold>
</xref>) (<xref ref-type="bibr" rid="B41">Kloss et&#xa0;al., 2020</xref>; <xref ref-type="bibr" rid="B53">McKee et&#xa0;al., 2021</xref>; <xref ref-type="bibr" rid="B24">Filho et&#xa0;al., 2022</xref>; <xref ref-type="bibr" rid="B30">Hamilton et&#xa0;al., 2022</xref>; <xref ref-type="bibr" rid="B55">Mishra et&#xa0;al., 2022</xref>). As the work of <xref ref-type="bibr" rid="B2">Barone et&#xa0;al. (2022)</xref> first detailed, the eruption of Hunga volcano on 15 January 2022, the most explosive of the 21st century, led to a massive chlorophyll-a (Chl-a) increase around Tonga island, stimulated by nutrients supplied through ash deposition. However, several studies have observed the presence of discolored water plumes at the surface around Tonga island following Hunga eruptions (2009, 2019, and 2022), and so the link between ash and Chl-a is not certain (<xref ref-type="bibr" rid="B66">Shi and Wang, 2011</xref>; <xref ref-type="bibr" rid="B79">Whiteside et&#xa0;al., 2021</xref>; <xref ref-type="bibr" rid="B78">Whiteside et&#xa0;al., 2023</xref>). Unusually sporadic and widespread transport of ash from these explosive volcanic events may supply the nutrients over the wider western SPO beyond the source region (<xref ref-type="bibr" rid="B41">Kloss et&#xa0;al., 2020</xref>; <xref ref-type="bibr" rid="B53">McKee et&#xa0;al., 2021</xref>; <xref ref-type="bibr" rid="B55">Mishra et&#xa0;al., 2022</xref>). However, little work has been dedicated to the response of phytoplankton associated with the long-distance transport of explosive ash plumes within the wider the western SPO.</p>
<p>In this study, through a comparative analysis of satellite and reanalysis data for the past 19 years (2004&#x2013;2022), we present the temporal and spatial characteristics of transport pathways of airborne volcanic ash over the western SPO during the period. We investigate changes in satellite-derived Chl-a concentrations to compare the phytoplankton responses to deposition of distally transported ash plumes.</p>
</sec>
<sec id="s2" sec-type="materials|methods">
<label>2</label>
<title>Methods &amp; materials</title>
<sec id="s2_1">
<label>2.1</label>
<title>Satellite data</title>
<p>Satellite observations of SO<sub>2</sub> have previously been used as a proxy for volcanic eruptions and volcanic ash transport (<xref ref-type="bibr" rid="B71">Thomas and Prata, 2011</xref>; <xref ref-type="bibr" rid="B65">Sears et&#xa0;al., 2013</xref>). The temporal variability of volcanic plumes produced over the western SPO (10&#xb0;N&#x2013;35&#xb0;S, 125&#xb0;E&#x2013;150&#xb0;W) during the study period of October 2004 to February 2022 was examined using daily level-3 best pixel SO<sub>2</sub> total column products with a 0.25&#xb0; regular grid, obtained from NASA&#x2019;s Aura satellite Ozone Monitoring Instrument (OMI), which is available since October 2004 (<uri xlink:href="https://disc.gsfc.nasa.gov/datasets/OMSO2e_003/summary">https://disc.gsfc.nasa.gov/datasets/OMSO2e_003/summary</uri>; <xref ref-type="bibr" rid="B45">Li et&#xa0;al., 2017</xref>; <xref ref-type="bibr" rid="B46">Li et&#xa0;al., 2020a</xref>). The background SO<sub>2</sub> loads (&lt;0.1 Dobson Units (DU); 1 DU = 2.69 &#xd7; 10<sup>16</sup> molecules cm<sup>&#x2212;2</sup>) were removed (<xref ref-type="bibr" rid="B46">Li et&#xa0;al., 2020a</xref>). To characterize the spatial distribution of volcanic plumes, we also used the level-2 PCA SO<sub>2</sub> total column products (NMSO2-PCA-L2) with a spatial resolution of 50&#xa0;km, taken from Ozone Mapping and Profiler Suite (OMPS) onboard NASA/NOAA Suomi National Polar-orbiting Partnership (SNPP) satellite, which is available since 2012 (<uri xlink:href="https://disc.gsfc.nasa.gov/datasets/OMPS_NPP_NMSO2_PCA_L2_2/summary">https://disc.gsfc.nasa.gov/datasets/OMPS_NPP_NMSO2_PCA_L2_2/summary</uri>). To ensure data quality and maintain pixel numbers, we accepted OMPS SO<sub>2</sub> values with a solar zenith angle less than 75&#xb0;, cloud cover less than 80%, and SO<sub>2</sub> values higher than 0.1 DU (<xref ref-type="bibr" rid="B81">Yang et&#xa0;al., 2013</xref>; <xref ref-type="bibr" rid="B46">Li et&#xa0;al., 2020a</xref>). We analyzed the spatial distribution of OMI level 2-PCA SO<sub>2</sub> total column products with a spatial resolution of 13 &#xd7; 24 km<sup>2</sup> for the pre-OMPS period (i.e., prior to 2012). These data were re-sampled to 0.25&#xb0; by 0.25&#xb0; using MATLAB cubic interpolation methods. The vertical and horizontal transport of ash plumes was detected using level-2 aerosol subtypes data (version 4.x) and level-1 532 nm total attenuated backscatter coefficient measurements (version 4.x) by the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) onboard the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) satellite (<ext-link ext-link-type="uri" xlink:href="https://www-calipso.larc.nasa.gov">https://www-calipso.larc.nasa.gov</ext-link>; <xref ref-type="bibr" rid="B80">Winker et&#xa0;al., 2009</xref>; <xref ref-type="bibr" rid="B76">Vernier et&#xa0;al., 2016</xref>; <xref ref-type="bibr" rid="B40">Kim et&#xa0;al., 2018</xref>). To track the vertical profile of ash particles from volcanic eruption, we further used daily level-2 aerosol extinction coefficient at 675 nm (version 2) measured by OMPS Limb Profiler sensor on the Suomi-NPP satellite (<uri xlink:href="https://disc.gsfc.nasa.gov/datasets/OMPS_NPP_LP_L2_AER_DAILY_2/summary">https://disc.gsfc.nasa.gov/datasets/OMPS_NPP_LP_L2_AER_DAILY_2/summary</uri>; <xref ref-type="bibr" rid="B42">Kramarova et&#xa0;al., 2018</xref>; <xref ref-type="bibr" rid="B51">Loughman et&#xa0;al., 2018</xref>). The aerosol extinction coefficient data have a vertical resolution of approximately 1.8&#xa0;km. To monitor atmospheric features on volcanic eruptions, the NASA WorldView images of true color corrected reflectance, derived from both SNPP-Visible Infrared Imaging Radiometer Suite (VIIRS) and Aqua-Moderate Resolution Imaging Spectroradiometer (MODIS) were also used (<ext-link ext-link-type="uri" xlink:href="https://worldview.earthdata.nasa.gov/">https://worldview.earthdata.nasa.gov/</ext-link>).</p>
<p>The change in phytoplankton biomass over the western SPO was evaluated using Chl-a products, derived using the OC4 blue-green band ratio algorithm, which is applicable for Case 1 waters (i.e., typically oligotrophic and open oceans) (<xref ref-type="bibr" rid="B60">O'Reilly et&#xa0;al., 2000</xref>). The Chl-a estimates are 0.25&#xb0; gridded daily merged products generated by the weighted average method from the GlobColour dataset (<ext-link ext-link-type="uri" xlink:href="https://hermes.acri.fr">https://hermes.acri.fr</ext-link>). To exclude the local impact, we removed the Chl-a values over shallow waters (bathymetry &lt;200&#xa0;m; <xref ref-type="supplementary-material" rid="SM1">
<bold>Figure S1A</bold>
</xref>). Furthermore, we estimated ocean PP, using the vertically generalized production model (VGPM) developed by <xref ref-type="bibr" rid="B3">Behrenfeld and Falkowski (1997)</xref>. The input data required for the PP estimation were obtained from GlobColour datasets for the Chl-a, photosynthetic available radiation, and euphotic depth, and the operational sea surface temperature and sea ice analysis (OSTIA) system dataset for sea surface temperature (SST) (<uri xlink:href="https://marine.copernicus.eu">https://marine.copernicus.eu</uri>; <xref ref-type="bibr" rid="B27">Good et&#xa0;al., 2020</xref>), respectively. The SST data with the spatial resolution of 0.05&#xb0; were re-sampled to 0.25&#xb0; by 0.25&#xb0; grid using MATLAB cubic interpolation methods.</p>
</sec>
<sec id="s2_2">
<label>2.2</label>
<title>Reanalysis and simulated data</title>
<p>Emitted volcanic ashes are dispersed in the atmosphere and transported by wind to the distance of ten to thousands of kilometers away from their source. The NOAA&#x2019;s hybrid single-particle Lagrangian integrated trajectory (HYSPLIT) model was applied to identify the atmospheric transport and dispersion of volcanic ash (<ext-link ext-link-type="uri" xlink:href="http://www.ready.noaa.gov">http://www.ready.noaa.gov</ext-link>) (<xref ref-type="bibr" rid="B69">Stein et&#xa0;al., 2015</xref>; <xref ref-type="bibr" rid="B64">Rolph et&#xa0;al., 2017</xref>). Global data assimilation system (GDAS) metrological data with a horizontal resolution of 1&#xb0; were used as model input to calculate the 96-hrs forward trajectories for heights in the surface layer (0.8&#xa0;km) and stratospheric layer (15 and 21&#xa0;km) from Ulawun volcano, Papua New Guinea on 7 October, 2006 (4.27&#xb0;S, 152.20&#xb0;E), Ambae volcano, Vanuatu on 27 July, 2018 (15.40&#xb0;S, 167.84&#xb0;E), Ulawun volcano, Papua New Guinea on 26 June, 2019 (5.05&#xb0;S, 151.33&#xb0;E) and Hunga volcano, Tonga on 15 January, 2022 (20.54&#xb0;S, 175.38&#xb0;W), respectively. The volcanic ash transport was also examined by using the daily zonal wind (u) and meridional wind (v) at 925 hPa from the National Centers for Environmental Prediction (NCEP)-National Center for Atmospheric Research (NCAR) Reanalysis 1 (<ext-link ext-link-type="uri" xlink:href="https://psl.noaa.gov/data/gridded/data.ncep.reanalysis.pressure.html">https://psl.noaa.gov/data/gridded/data.ncep.reanalysis.pressure.html</ext-link>).</p>
<p>To confirm the influence of the vertical mixing of the water column over the western SPO, we analyzed the weekly estimates of mixed layer depth (MLD) with a 0.25&#xb0; &#xd7; 0.25&#xb0; regular grid derived from the Multi Observation Global Ocean ARMOR3D L4 near real time weekly products and multi-year reprocessed products, for the period of 2020 to 2022 and 2004 to 2021, respectively, distributed by the Copernicus Marine Environment Monitoring Service (CMEMS) (<ext-link ext-link-type="uri" xlink:href="https://resources.marine.copernicus.eu">https://resources.marine.copernicus.eu</ext-link>). MLD data were estimated as the minimum value of a density threshold equivalent to a 0.2&#xb0;C variation of the temperature conditions from the temperature at 10&#xa0;m depth and the MLD temperature criteria with 0.2&#xb0;C threshold (<xref ref-type="bibr" rid="B19">de Boyer Mont&#xe9;gut et&#xa0;al., 2004</xref>). The weekly MLD data were re-sampled to daily data using MATLAB resample function. We also used the daily surface precipitation rate dataset derived from NCEP-NCAR reanalysis 1 to understand the nutrient supply from river flux (<xref ref-type="bibr" rid="B67">Shiozaki et&#xa0;al., 2014</xref>). To investigate the nutrient flux from the sediment arounds the islands (<xref ref-type="bibr" rid="B23">Dutheil et&#xa0;al., 2018</xref>), we analyzed surface zonal current using Ocean Surface Current Analysis Real-time (OSCAR) dataset with a 1/3 degree grid with a 5 day resolution, which was calculated from satellite datasets using a simplified physical model of an upper ocean turbulent mixed layer (<ext-link ext-link-type="uri" xlink:href="https://podaac.jpl.nasa.gov/dataset/OSCAR_L4_OC_third-deg_YEARLY">https://podaac.jpl.nasa.gov/dataset/OSCAR_L4_OC_third-deg_YEARLY</ext-link>).</p>
</sec>
<sec id="s2_3">
<label>2.3</label>
<title>Geochemical analysis of ash</title>
<p>To investigate the role that varying chemical compositions of ash may have had on phytoplankton response, the geochemical composition of volcanic ash from the studied volcanic eruptions was investigated. For the 2018 Ambae eruption, major and trace element geochemistry for the bulk ash and individual ash glasses was taken from <xref ref-type="bibr" rid="B57">Moussallam et&#xa0;al. (2019)</xref>. Comparable data for the 2009 and 2014&#x2013;2015 eruptions of Hunga were taken from <xref ref-type="bibr" rid="B12">Brenna et&#xa0;al. (2022)</xref>, supplemented by analysis of 2022 products collected on land from Tongatapu, Tonga. These samples were collected in the aftermath of the eruption, roughly 75&#xa0;km south of Hunga volcano. Bulk X-Ray Fluorescence (XRF) analysis of the whole ash sample from Nakualolofa, Tongatapu and XRF analysis of pumice separated from ash collected from Fu&#x2019;amotu airport was completed by SpectraChem Analytical Ltd. Christchurch using Li-Borate beads for major elements and pressed-powder pellets for trace elements. Individual glass shards from 2022 material deposited on Tongatapu were analyzed using a JEOL Field Emission Electron Probe Microanalyser System 8530F (Hyperprobe) at the University of Auckland. A defocussed beam of 10&#x2013;20 &#x3bc;m diameter was used with an accelerating voltage of 15 kV, with Na analyzed first and probe conditions monitored using secondary international glass standards.</p>
</sec>
</sec>
<sec id="s3" sec-type="results">
<label>3</label>
<title>Results and discussion</title>
<sec id="s3_1">
<label>3.1</label>
<title>The occurrence of four extreme volcanisms in the western SPO</title>
<p>The spatial distribution of the combined climatology of the OMI-derived mean SO<sub>2</sub> in the western SPO averaged over last 19 years (2004&#x2013;2022) is shown in <xref ref-type="supplementary-material" rid="SM1">
<bold>Figure S1B</bold>
</xref>. Comparatively higher SO<sub>2</sub> total column values (&gt;0.4 DU) were found in and around the land than that over ocean. The highest values of SO<sub>2</sub> are found in the regions near the volcanoes shown in <xref ref-type="supplementary-material" rid="SM1">
<bold>Figure S1</bold>
</xref>, indicating the SO<sub>2</sub> variation for the study period in the western SPO is mainly related to the state of volcanic activity. One exception is in Southeast Australia where SO<sub>2</sub> emissions are entirely anthropogenic from 19 coal-fired power stations operating in Australia (<xref ref-type="bibr" rid="B33">Hendryx et&#xa0;al., 2020</xref>).</p>
<p>To describe the explosive volcanisms that occurred in the western SPO over last 19 years, we first investigated the volcanic explosivity index (VEI; <ext-link ext-link-type="uri" xlink:href="https://volcano.si.edu/">https://volcano.si.edu/</ext-link>), which distinguishes the volcanic eruptions in the range from 0 (non-explosive eruptions) to 8 (mega-colossal explosive eruptions) on the logarithm of 10, based on volume of magma erupted during an eruption and plume height (<xref ref-type="bibr" rid="B59">Newhall and Self, 1982</xref>). During this period, twelve explosive eruptions of VEI 3 or greater have been observed (<xref ref-type="supplementary-material" rid="SM1">
<bold>Table S1</bold>
</xref>). The Hunga eruption from an andesitic submarine caldera, on 15 of January 2022, a Paroxysmal eruption, was the biggest explosion of the 21st century from with a VEI estimated at 5, which is greater by two orders of magnitude than any others in the dataset. However, there were four further events of VEI 4 from the volcanoes in Papua New Guinea, which are Ulawun, Manam, and Rabaul volcanoes. The Ambae event was the most energetic episode of a longer period of sub-Plinian/Plinian volcanism from a basaltic vent at ~1400 m elevation, with VEI of 3 (<xref ref-type="bibr" rid="B57">Moussallam et&#xa0;al., 2019</xref>).</p>
<p>
<xref ref-type="fig" rid="f1">
<bold>Figure&#xa0;1A</bold>
</xref> shows the daily variations of OMI-derived SO<sub>2</sub> total column during the study period of October 2004 to February 2022 averaged over the western SPO (10&#xb0;N&#x2013;35&#xb0;S, 125&#xb0;E&#x2013;150&#xb0;W). The daily mean SO<sub>2</sub> total column averaged over the western SPO displays generally low values (0.23 &#xb1; 0.05 DU), but episodic SO<sub>2</sub> peaks occurred for twelve explosive eruptions of VEI 3 or greater (&gt;0.9 DU) (<xref ref-type="fig" rid="f1">
<bold>Figure&#xa0;1A</bold>
</xref> and <xref ref-type="supplementary-material" rid="SM1">
<bold>Table S1</bold>
</xref>). To identify which explosive eruptions delivered the emitted substances with high intensity over the broad area of the western SPO, we extracted extremely high values fall that above 99.9<sup>th</sup> percentile of daily mean SO<sub>2</sub> total column (&gt;0.931 DU), suggestive of high volcanic ash deposition to the western SPO. There were four distinct peaks in October 2006 (maximum value: 1.63 DU), July 2018 (maximum value: 1.56 DU), June 2019 (maximum value: 0.93 DU), and January 2022 (maximum value: 1.95 DU) (<xref ref-type="fig" rid="f1">
<bold>Figure&#xa0;1B</bold>
</xref>), corresponding with timing of volcanic eruptions in the Rabaul, Papua New Guinea (October 2006), Ambae, Vanuatu (July 2018), Ulawun, Papua New Guinea (June 2019), and Hunga, Tonga (January 2022). The number of pixels (0.25&#xb0; grid) with SO<sub>2</sub> values above 99.9<sup>th</sup> percentile (0.931 DU) over the western SPO area also showed the strong peaks (&gt;1000 pixels) in the corresponding periods (<xref ref-type="supplementary-material" rid="SM1">
<bold>Figure S2</bold>
</xref>), i.e., covering an area of &gt;765,000 km<sup>2</sup>. The true color images confirm the emissions of volcanic ash from Rabaul (7 October, 2006), Ambae (especially on 20 and 27 July, 2018), Ulawun (25 June, 2019), and Hunga eruptions (14 January, 2022) (<xref ref-type="supplementary-material" rid="SM1">
<bold>Figure S3</bold>
</xref>) (<ext-link ext-link-type="uri" xlink:href="https://worldview.earthdata.nasa.gov">https://worldview.earthdata.nasa.gov</ext-link>). Combined, these data suggest the eruptions of Rabaul, Papua New Guinea (October 2006), Ambae, Vanuatu (July 2018), Ulawun, Papua New Guinea (June 2019), and Hunga, Tonga (January 2022) were the most extreme volcanic plumes produced in the western SPO over last 19 years (2004&#x2013;2022).</p>
<fig id="f1" position="float">
<label>Figure&#xa0;1</label>
<caption>
<p>The temporal variation of OMI-derived mean SO<sub>2</sub> total column averaged over the western SPO (10&#xb0;N&#x2013;35&#xb0;S, 125&#xb0;E&#x2013;150&#xb0;W) <bold>(A)</bold> for the study period of October 2004 to February 2022, enlarged figures <bold>(B)</bold> for October, 2006, July to August, 2018, June to July, 2019 and for January, 2022. The asterisk markers and blue lines in <bold>(A)</bold> (circle markers and shading in Figure&#xa0;1B) indicate the mean and one standard deviation of mean, respectively. Red dotted line indicates the threshold of SO<sub>2</sub> value that correspond to 99.9th percentile. Red circles indicate the SO<sub>2</sub> values that exceeded 99.9<sup>th</sup> percentile.</p>
</caption>
<graphic mimetype="image" mime-subtype="tiff" xlink:href="fmars-10-1072610-g001.tif"/>
</fig>
</sec>
<sec id="s3_2">
<label>3.2</label>
<title>Horizontal and vertical transport of four extreme volcanic plumes</title>
<p>During a volcanic eruption, buoyant plumes of ash and gas are produced (fragmented volcanic glass and minerals, rich in macro- and micro-nutrients; <xref ref-type="bibr" rid="B21">Duggen et&#xa0;al., 2007</xref>; <xref ref-type="bibr" rid="B50">Longman et&#xa0;al., 2022</xref>). These are rapidly transported horizontally and vertically by the wind, until deposition. Ash deposition in the western SPO may supply limiting nutrients (particularly iron for N<sub>2</sub> fixation; <xref ref-type="bibr" rid="B9">Bonnet et&#xa0;al., 2017</xref>) for phytoplankton growth (<xref ref-type="bibr" rid="B32">Heffter and Stunder, 1993</xref>; <xref ref-type="bibr" rid="B43">Langmann et&#xa0;al., 2010</xref>; <xref ref-type="bibr" rid="B61">Olgun et&#xa0;al., 2013a</xref>). To characterize the spatial pattern of the deposition of volcanic materials into the western SPO, in this section, we describe the horizontal and vertical transport and dispersion of ash plumes from Rabaul volcano in October 2006, Ambae volcano in July&#x2013;August 2018, Ulawun volcano in June&#x2013;July 2019, and Hunga volcano in January 2022.</p>
<p>
<xref ref-type="fig" rid="f2">
<bold>Figure&#xa0;2</bold>
</xref> shows the horizontal evolution of satellite-derived mean SO<sub>2</sub> total column over the western SPO averaged for the periods of the four volcanic eruptions, 2006 Rabaul eruption (7&#x2013;13 October), 2018 Ambae eruption (20&#x2013;27 July and 28 July&#x2013;4 August), 2019 Ulawun eruption (26 June&#x2013;4 July), and 2022 Hunga eruption (15&#x2013;20 January). On 7 October 2006, very high SO<sub>2</sub> columns (&gt;14 DU) were observed around Rabaul volcano (<xref ref-type="supplementary-material" rid="SM1">
<bold>Figure S4A</bold>
</xref>), and SO<sub>2</sub> plumes from this source were horizontally distributed over the western SPO, showing two pathways of westward transport and southeastern transport, respectively (<xref ref-type="fig" rid="f2">
<bold>Figures&#xa0;2A</bold>
</xref> and <xref ref-type="supplementary-material" rid="SM1">
<bold>S4A</bold>
</xref>). Highest plumes were displayed over near coastal waters with a westward relatively short distance (~700 km) around the northeastern area of Papua New Guinea after leaving the source, during southeasterly surface wind conditions. Following the continuous SO<sub>2</sub> emission from Ambae volcano (&gt;14 DU) during the period of 20&#x2013;27 July, 2018, with relatively high SO<sub>2</sub> levels around source region (Ambae) (shown in inset in <xref ref-type="fig" rid="f2">
<bold>Figure&#xa0;2B</bold>
</xref>), the SO<sub>2</sub> plumes averaged during the period of 28 July to 4 August 2018 showed eastward long-distance (&gt;2000&#xa0;km) transport, showing highest plumes around the northern part of Tongatapu island (29 July 2018), but the direction of surface winds in 2018 case showed different pathways of long-distance transport of SO<sub>2</sub>, suggesting that this transport was associated with air masses at the higher altitude (<xref ref-type="fig" rid="f2">
<bold>Figures&#xa0;2B</bold>
</xref> and <xref ref-type="supplementary-material" rid="SM1">
<bold>S4B</bold>
</xref>). During 2019 Ulawun eruption event, the SO<sub>2</sub> plumes were relatively less dispersed over the western SPO, compared to those from other volcanoes studied here (<xref ref-type="fig" rid="f2">
<bold>Figures&#xa0;2C</bold>
</xref> and <xref ref-type="supplementary-material" rid="SM1">
<bold>S4C</bold>
</xref>). This event showed high plume concentrations only in the eastern area of Papua New Guinea, a short-distance (~500 km) southward from the source region as described in a recent study (<xref ref-type="bibr" rid="B53">McKee et&#xa0;al., 2021</xref>). Conversely, the SO<sub>2</sub> distribution averaged during the period of 15&#x2013;20 January illustrates that the SO<sub>2</sub> emitted from the Hunga volcano travelled a long distance (&gt;6000&#xa0;km) westward, reaching the northern part of Australia, passing over the waters around Vanuatu and Fiji (<xref ref-type="fig" rid="f2">
<bold>Figures&#xa0;2D</bold>
</xref> and <xref ref-type="supplementary-material" rid="SM1">
<bold>S4D</bold>
</xref>). The highest SO<sub>2</sub> values (&gt;14 DU) appeared in around source region (Hunga) and the water surrounded by Vanuatu, New Caledonia, and Fiji (i.e., an area of ~8.2 &#xd7; 10<sup>5</sup> km<sup>2</sup>, ~2000 km from source; blue box in <xref ref-type="fig" rid="f2">
<bold>Figure&#xa0;2D</bold>
</xref>) on 16 January 2022. The transport of volcanic plumes in the 2022 case was consistent with the easterly wind direction at the near surface.</p>
<fig id="f2" position="float">
<label>Figure&#xa0;2</label>
<caption>
<p>A spatial distribution of the SO<sub>2</sub> total column averaged over the period of <bold>(A)</bold> 7-13 October, 2006, <bold>(B)</bold> 28 July - 4 August, 2018, <bold>(C)</bold> 26 June - 4 July, 2019, and <bold>(D)</bold> 15-20 January, 2022, with surface wind (at 925 hPa). Inserted figure in <bold>(B)</bold> is the spatial distribution of SO<sub>2</sub> total column averaged over the period of 20-27 July, 2018.</p>
</caption>
<graphic mimetype="image" mime-subtype="tiff" xlink:href="fmars-10-1072610-g002.tif"/>
</fig>
<p>Based on NOAA&#x2019; HYSPLIT 96-hrs forward trajectories model, we investigated the vertical transport pathways of tropospheric (0.8&#xa0;km) and stratospheric air masses (15 and 21&#xa0;km), originating from the Rabaul, Ambae, Ulawun, and Hunga volcanoes (<xref ref-type="fig" rid="f3">
<bold>Figure&#xa0;3A</bold>
</xref>). During the Rabaul volcano event (7 October, 2006), air mass trajectories simulated by HYSPLIT showed that the air mass movement at the altitude of 15&#xa0;km captured the horizontal distribution of SO<sub>2</sub> plumes, suggesting the stratospheric injection and mass loading of volcanic materials expelled from Rabaul volcano (<xref ref-type="fig" rid="f2">
<bold>Figures&#xa0;2A</bold>
</xref>, <xref ref-type="fig" rid="f3">
<bold>3A</bold>
</xref>). The movement of air masses at the altitudes of 0.8 and 21&#xa0;km from Ambae volcano (27 July, 2018), was consistent with that of near surface wind (<xref ref-type="fig" rid="f2">
<bold>Figure&#xa0;2B</bold>
</xref>). Unlike the direction of other air masses, the air mass at an altitude of 15&#xa0;km showed a pathway consistent with the spatial distribution of SO<sub>2</sub> total column, supporting the suggestion that volcanic ash from the Ambae eruption in July 2018 was transported at an altitude of 15&#xa0;km (i.e., stratosphere aerosol level). This result is also consistent with the vertical distribution of the Ambae volcanic plume observed with a core brightness temperature (<xref ref-type="bibr" rid="B41">Kloss et&#xa0;al., 2020</xref>). The airmass at the altitude of 21&#xa0;km following the Ulawun eruption (26 June, 2019) showed a pathway eastward, which is consistent with the spatial distribution of SO<sub>2</sub> with low levels (<xref ref-type="fig" rid="f3">
<bold>Figure&#xa0;3A</bold>
</xref>). On the other hand, airmass forward trajectory, starting from altitude of 15&#xa0;km, depicted high SO<sub>2</sub> plume distribution around the eastern area of Papua New Guinea (<xref ref-type="fig" rid="f2">
<bold>Figures&#xa0;2C</bold>
</xref>, <xref ref-type="fig" rid="f3">
<bold>3A</bold>
</xref>). The pathways of air masses at the altitudes of 0.8, 15, and 21&#xa0;km, starting at the Hunga on 15 January 2022, appeared to be in the westward direction, showing consistent pathways to the region of Vanuatu, New Caledonia, and Fiji (<xref ref-type="fig" rid="f2">
<bold>Figures&#xa0;2D</bold>
</xref>, <xref ref-type="fig" rid="f3">
<bold>3A</bold>
</xref>). Dispersion of air mass at an altitude of 21&#xa0;km was nearly the same as that of the SO<sub>2</sub> distribution, indicating that volcanic ash is suspected to be more efficiently transported over a long distance to the northern part of Australia along an altitude of 21&#xa0;km, higher than the Ambae volcano. Recent studies also showed that much of the plume reached an altitude higher than 30&#xa0;km during the Hunga eruption, and it developed a massive umbrella region of ~400 km diameter (<xref ref-type="bibr" rid="B16">Carr et&#xa0;al., 2022</xref>; <xref ref-type="bibr" rid="B68">Smart, 2022</xref>), making it much more effective in dispersing ash over large areas.</p>
<fig id="f3" position="float">
<label>Figure&#xa0;3</label>
<caption>
<p>
<bold>(A)</bold> The HYSPLIT forward trajectories (96-hrs) at altitudes of 0.8&#xa0;km (green), 15&#xa0;km (red), 21&#xa0;km (blue) from Rabaul (7 October, 2018), Ambae (27 July, 2018), Ulawun (26 June, 2019), and Hunga (15 January, 2022). Grey lines indicate CALIPSO orbits. Pink lines indicate OMPS orbits. <bold>(B)</bold> The vertical distribution of CALIPSO-derived aerosol subtypes in 2006, 2018, 2019 and 2022 along the orbits shown in <bold>(A)</bold>. Colorbar indicates stratospheric aerosol subtypes (0: not determined, 1: clean marine, 2: dust, 3: polluted continental/smoke, 4: clean continental, 5: polluted dust, 6: elevated smoke, 7: dusty marine, 8: polar stratospheric clouds aerosol, 9: volcanic ash, 10: sulphate/other). <bold>(C)</bold> The vertical distribution of OMPS-derived aerosol extinction coefficient on 29 July, 2018, 27 June, 2019, 16 and 17 January, 2022 along the orbits shown in Figure&#xa0;3A.</p>
</caption>
<graphic mimetype="image" mime-subtype="tiff" xlink:href="fmars-10-1072610-g003.tif"/>
</fig>
<p>To identify whether long-range transportation of air mass in the stratosphere (usually higher than approximately 12 km above the surface) is associated with the dispersion of volcanic aerosol plumes over the western SPO, we further analyzed the CALIPSO L2 aerosol products after the 2006, 2018, 2019 and 2022 eruptions, which classify aerosols into ten subtypes for the stratospheric layer; clean marine, dust, polluted continental/smoke, clean continental, polluted dust, elevated smoke, dusty marine, polar stratospheric clouds aerosol, volcanic ash, sulphate/other (<xref ref-type="fig" rid="f3">
<bold>Figure&#xa0;3B</bold>
</xref>) (<xref ref-type="bibr" rid="B40">Kim et&#xa0;al., 2018</xref>). The stratospheric aerosols were well spread at the altitudes of around ~15 to 25&#xa0;km in 2006, 2018, and 2019 eruptions. For the 2022 eruption, relatively higher heights, at the altitudes of 18 to 30&#xa0;km, respectively, along the CALIPSO measurement orbit tracks, as shown by the HYSPLIT atmospheric long-distance trajectories (15&#xa0;km in 2006, 2018, and 2019 year and 21&#xa0;km in 2022 year) and SO<sub>2</sub> distribution (<xref ref-type="fig" rid="f2">
<bold>Figures&#xa0;2</bold>
</xref>, <xref ref-type="fig" rid="f3">
<bold>3B</bold>
</xref>). The presence of volcanic ash plumes was also characterized by CALIPSO L1B total attenuated backscattering coefficient at 532 nm (~0.002 km<sup>-1</sup> sr<sup>-1</sup>; yellow in the figure) (<xref ref-type="supplementary-material" rid="SM1">
<bold>Figure S5</bold>
</xref>). Most importantly, the CALIPSO measurements show that the composition of the 2006, 2018, and 2019 plumes was primarily sulphate aerosols (grey in the figures), while the 2022 Hunga eruption was a mixture of volcanic ash and sulphate aerosols (red and grey in the figure), indicating the persistence of ash-laden plumes over the western SPO after the eruption (<xref ref-type="fig" rid="f3">
<bold>Figure&#xa0;3B</bold>
</xref>). Furthermore, we investigated the vertical distribution of OMPS L2 aerosol extinction to understand the quantitative retrievals of volcanic ash transported and deposited to the western SPO following 2018, 2019, and 2022 eruptions (<xref ref-type="fig" rid="f3">
<bold>Figure&#xa0;3C</bold>
</xref>). There was no available data in 2006. The vertical distribution of aerosol extinction along the OMPS orbit track on 29 July 2018, confirmed a slight increase (~0.02 km<sup>-1</sup>) at altitudes of ~15 to 20&#xa0;km in the northern area of Tongatapu island where the highest levels in SO<sub>2</sub> were shown, indicating relatively potential low deposition (<xref ref-type="fig" rid="f2">
<bold>Figures&#xa0;2B</bold>
</xref>, <xref ref-type="fig" rid="f3">
<bold>3C</bold>
</xref>). After the 2019 volcanic eruption, aerosol extinction coefficients on 27 June 2019 also showed a slight increase (&gt;0.02 km<sup>-1</sup>) at altitudes of ~15 to 20&#xa0;km around Papua New Guinea. However, unlike these events, the vertical distribution of aerosol extinction coefficients on 16 January 2022 showed relatively higher values with levels of &gt;~0.05 km<sup>-1</sup> at all observed altitudes (&lt;30&#xa0;km) in the water surrounded by Vanuatu, New Caledonia, and Fiji (<xref ref-type="fig" rid="f3">
<bold>Figure&#xa0;3C</bold>
</xref>), where ash-laden plumes and high levels in SO<sub>2</sub> were mainly observed, but relatively low aerosol extinction coefficients in the western part of Vanuatu on 17 January 2022 (<xref ref-type="fig" rid="f2">
<bold>Figures&#xa0;2D</bold>
</xref>, <xref ref-type="fig" rid="f3">
<bold>3A, C</bold>
</xref>). <xref ref-type="bibr" rid="B55">Mishra et&#xa0;al. (2022)</xref> showed that on 16 January the maximum SO<sub>2</sub> value in the region occurred when the spread speed of atmospheric westward plume was lowest as &lt;1000&#xa0;km day<sup>-1</sup>, but &gt;2500&#xa0;km day<sup>-1</sup> after 17 January. Ash deposition maxima can result from the trapping of ash related to relatively low wind speed, as shown in a numerical modeling study (<xref ref-type="bibr" rid="B63">Poulidis et&#xa0;al., 2018</xref>). Therefore, these results suggest 2022 Hunga eruption was accompanied by high deposition of ash-rich aerosols over the water surrounded by Vanuatu, New Caledonia, and Fiji on 16 January 2022, probably by relatively weak winds.</p>
</sec>
<sec id="s3_3">
<label>3.3</label>
<title>The volcanic ash composition</title>
<p>The composition of the deposited volcanic ash has the potential to control the phytoplankton response, with differing levels of nutrient release from different ash compositions already noted (<xref ref-type="bibr" rid="B36">Jones and Gislason, 2008</xref>; <xref ref-type="bibr" rid="B50">Longman et&#xa0;al., 2022</xref>). Our ash classification showed that in October 2006, the large sub-Plinian eruption from Rabaul volcano, with a whole-rock composition of Trachydacite (<xref ref-type="supplementary-material" rid="SM1">
<bold>Figure S6</bold>
</xref>) (<xref ref-type="bibr" rid="B10">Bouvet de Maisonneuve et&#xa0;al., 2015</xref>; <xref ref-type="bibr" rid="B5">Bernard and Bouvet de Maisonneuve, 2020</xref>). The 2018 Amabe volcano, which is a basaltic shield volcano, produced basaltic andesite to trachy-basalt ash (<xref ref-type="bibr" rid="B57">Moussallam et&#xa0;al., 2019</xref>). The 2022 Hunga eruption produced andesitic to basaltic andesite ash, similar to earlier eruptions of this volcano (<xref ref-type="bibr" rid="B12">Brenna et&#xa0;al., 2022</xref>). <xref ref-type="supplementary-material" rid="SM1">
<bold>Figure S7</bold>
</xref> shows that both Ambae and Vanuatu ash contain high iron contents in their total glass and bulk analyses (often &gt;10 wt%), which is a common nutrient deficiency in the ocean, but Rabaul ash contains relatively low iron contents (&lt;10 wt%) (<xref ref-type="supplementary-material" rid="SM1">
<bold>Table S2 and S3</bold>
</xref>) (<xref ref-type="bibr" rid="B56">Moore et&#xa0;al., 2013</xref>). This may explain the lack of phytoplankton response to Rabaul, but our data do not contain information on bioavailability of the Fe contained within the ash. As such, further research is necessary to confirm the hypothesis that changing ash composition leads to different phytoplankton response.</p>
</sec>
<sec id="s3_4">
<label>3.4</label>
<title>The response of chlorophyll-a concentrations to distal plumes transport</title>
<p>To understand the response of phytoplankton subsequent to distal ash transport from four extreme eruptions (2006 Rabaul, 2018 Ambae, 2019 Ulawun, and 2022 Hunga eruptions) in the western SPO, we carried out an inspection of area-averaged time series of GlobColour-merged Chl-a concentrations in the distal region (<xref ref-type="fig" rid="f4">
<bold>Figures&#xa0;4A&#x2013;D</bold>
</xref>), i.e., regions having highest atmospheric SO<sub>2</sub> loading (&gt;14 DU) extending toward the western SPO (blue box; 2006: 0&#x2013;4&#xb0;S, 145&#x2013;150&#xb0;E, 2018: 12&#x2013;18&#xb0;S, 178&#xb0;E&#x2013;169&#xb0;W; 2019: 6.5&#x2013;10&#xb0;S, 147&#x2013;157&#xb0;E; 2022: 15&#x2013;23&#xb0;S, 165&#x2013;174&#xb0;E) (<xref ref-type="fig" rid="f2">
<bold>Figure&#xa0;2</bold>
</xref>). A time series of Chl-a estimates in the distal region, which is affected regions by long-range transport of volcanic plumes (&gt;500&#xa0;km), showed profoundly different response to 2022 Hunga events when compared to all other volcanic events (2006, 2018, 2019 events; <xref ref-type="fig" rid="f4">
<bold>Figures&#xa0;4A&#x2013;D</bold>
</xref>). Following long-range transport of the 2006, 2018, 2019 volcanic emissions (<xref ref-type="fig" rid="f2">
<bold>Figures&#xa0;2A&#x2013;C</bold>
</xref>), Chl-a concentrations did not show any noticeable increases (<xref ref-type="fig" rid="f4">
<bold>Figures&#xa0;4A&#x2013;C</bold>
</xref>), suggesting limited nutrient supply (particularly iron) probably due to low volumes of ash deposition. However, in regions affected by likely high deposition of long-distance transported Hunga ash on 16 January 2022 (<xref ref-type="fig" rid="f2">
<bold>Figures&#xa0;2D</bold>
</xref>, <xref ref-type="fig" rid="f3">
<bold>3C</bold>
</xref>), Chl-a estimates were two times higher than that of climatological mean and one standard deviation for approximately 10 days after a lag period of 6 days (<xref ref-type="fig" rid="f4">
<bold>Figure&#xa0;4D</bold>
</xref>). The difference between Chl-a values from the 2022 Hunga event with the climatological values were statistically significant (p &lt;0.05; t-test analysis). The response of Chl-a values to 2022 Hunga eruptions (0.15 mg m<sup>-3</sup>) showed a 67% increase in average compared to climatological values (0.09 &#xb1; 0.03 mg m<sup>-3</sup>) (red shading in figure). Oceanic PP estimates subsequent to 2022 Hunga eruptions (383 mg C m<sup>-2</sup> d<sup>-1</sup>) also showed a 43% increase compared to climatological value (268 &#xb1; 74 mg C m<sup>-2</sup> d<sup>-1</sup>). This conclusion is echoed by the findings of a recent study, which showed increasing Chl-a in close proximity to Hunga volcano, but with a higher magnitude in Chl-a values (&gt;10-fold than before eruption) immediately after the eruption (<xref ref-type="bibr" rid="B2">Barone et&#xa0;al., 2022</xref>). However, as the presence of ash particles can directly influence the satellite ocean color signatures, in turn biasing the appraised Chl-a estimates, monitoring of the phytoplankton response to the ash deposition using satellite-derived optical datasets should be interpreted with caution (<xref ref-type="bibr" rid="B35">Johnson et&#xa0;al., 2011</xref>; <xref ref-type="bibr" rid="B14">Browning et&#xa0;al., 2015</xref>). The ash particles have residence times of up to 2 days in the euphotic zone depending on the particle sizes (<xref ref-type="bibr" rid="B21">Duggen et&#xa0;al., 2007</xref>). <xref ref-type="bibr" rid="B78">Whiteside et&#xa0;al. (2023)</xref> revealed that there were extremely high amounts of suspended ash particles in the surface waters around the Hunga volcano 2 days after 2022 eruption, which probably led to ash-contaminated Chl-a estimates but 9 days after the eruption the ash-related values recovered to normal, suggesting the removal of ash signal in the surface with time. In addition, previous studies have shown that the phytoplankton began to respond five to six days after deposition of volcanic ash, as shown in mesoscale iron-fertilization experiments (<xref ref-type="bibr" rid="B17">Coale et&#xa0;al., 2004</xref>; <xref ref-type="bibr" rid="B21">Duggen et&#xa0;al., 2007</xref>; <xref ref-type="bibr" rid="B43">Langmann et&#xa0;al., 2010</xref>; <xref ref-type="bibr" rid="B47">Lin et&#xa0;al., 2011</xref>; <xref ref-type="bibr" rid="B83">Yoon et&#xa0;al., 2018</xref>). Therefore, in the context of this study, the increase in Chl-a at a time period &#x223c;6 days after 2022 Hunga eruption, potentially after sinking of ash particles below surface waters, would exclude the misinterpretation of Chl-a estimates by ash particles itself in the surface water (<xref ref-type="bibr" rid="B43">Langmann et&#xa0;al., 2010</xref>).</p>
<fig id="f4" position="float">
<label>Figure&#xa0;4</label>
<caption>
<p>The area-averaged time series of Chl-a (red markers) over the distal region in <bold>(A)</bold> 2006 (0&#x2013;4&#xb0;S, 145&#x2013;150&#xb0;E), <bold>(B)</bold> 2018 (12&#x2013;18&#xb0;S, 178&#xb0;E&#x2013;169&#xb0;W), <bold>(C)</bold> 2019 (6.5&#x2013;10&#xb0;S, 147&#x2013;157&#xb0;E), and <bold>(D)</bold> 2022 (15&#x2013;23&#xb0;S, 165&#x2013;174&#xb0;E). Each region is shown as blue box in <xref ref-type="fig" rid="f2">
<bold>Figure&#xa0;2</bold>
</xref>. The blue dotted line indicates the area-averaged climatological mean and blue shading indicates one standard deviation of climatological mean. Star markers indicate main volcanic eruptions. The red shading indicates a Chl-a response subsequent to 2022 Hunga event. The spatial distribution of &#x394;Chl-a for the period of <bold>(E)</bold> 13-22 October, 2006, <bold>(F)</bold> 2-11 August, <bold>(G)</bold> 2-11 July, 2019 and <bold>(H)</bold> 21-30 January, 2022. &#x394;Chl-a is difference of Chl-a<sub>year</sub> and Chl-a<sub>climatology except year</sub> for corresponding each period, respectively.</p>
</caption>
<graphic mimetype="image" mime-subtype="tiff" xlink:href="fmars-10-1072610-g004.tif"/>
</fig>
<p>Furthermore, we analyzed the spatial distribution of the difference of 10-days mean Chl-a concentrations 6 days after volcanic eruption (2006: Chl-a<sub>2006 (13&#x2013;22 October)</sub>; 2018: Chl-a<sub>2018 (2-11 August)</sub>; 2019: Chl-a<sub>2019 (2&#x2013;11 July)</sub>; 2022: Chl-a<sub>2022 (21&#x2013;30 January)</sub>) and 10-days mean climatological Chl-a concentrations (2006: Chl-a<sub>2006clim (13&#x2013;22 October)</sub>; 2018: Chl-a<sub>2018clim (2-11 August)</sub>; 2019: Chl-a<sub>2019clim (2&#x2013;11 July)</sub>; 2022: Chl-a<sub>2022clim (21&#x2013;30 January)</sub>) averaged for corresponding periods for 19 years (2004&#x2013;2022) except corresponding year, respectively (e.g., &#x394;Chl-a <sub>2006 (13&#x2013;22 October)</sub> = Chl-a<sub>2006 (13&#x2013;22 October)</sub> &#x2013; Chl-a<sub>clim (13&#x2013;22 October) except 2006</sub>) (<xref ref-type="fig" rid="f4">
<bold>Figures&#xa0;4E&#x2013;H</bold>
</xref>). As shown in the temporal analysis, the long-distance transport of 2006, 2018, 2019 volcanic plumes over western SPO was not followed by any apparent response in Chl-a over regions that have high levels in SO<sub>2</sub> (<xref ref-type="fig" rid="f2">
<bold>Figures&#xa0;2A&#x2013;C</bold>
</xref>, <xref ref-type="fig" rid="f3">
<bold>3C</bold>
</xref>, <xref ref-type="fig" rid="f4">
<bold>4E&#x2013;G</bold>
</xref>). However, in 2022, considerable positive anomalies of Chl-a values (<xref ref-type="fig" rid="f4">
<bold>Figure&#xa0;4H</bold>
</xref>) were also distinctively visible over the water surrounded by Vanuatu, New Caledonia, and Fiji which showed potential high deposition following the long-range transport of ash released from Hunga (<xref ref-type="fig" rid="f2">
<bold>Figures&#xa0;2D</bold>
</xref>, <xref ref-type="fig" rid="f3">
<bold>3C</bold>
</xref>). Furthermore, an anomalously high phytoplankton stock was detected in waters in close proximity to Hunga volcano at a time period 6 days after the 2022 eruption (<xref ref-type="fig" rid="f4">
<bold>Figure&#xa0;4H</bold>
</xref>), as shown in <xref ref-type="bibr" rid="B2">Barone et&#xa0;al. (2022)</xref>, indicating a continued response in Chl-a even under a substantial sinking of ash particles (<xref ref-type="bibr" rid="B21">Duggen et&#xa0;al., 2007</xref>; <xref ref-type="bibr" rid="B78">Whiteside et&#xa0;al., 2023</xref>). These results suggest that volcanic ash deposition is considered the likely explanation for the enhancements in phytoplankton response in the western SPO.</p>
</sec>
<sec id="s3_5">
<label>3.5</label>
<title>Other possible drivers of 2022 chlorophyll-a response</title>
<p>In the western SPO, PP has been linked to the occurrence of N<sub>2</sub> fixing organisms, and high N<sub>2</sub> fixation rates have been recently assumed to be due to the alleviation of iron limitation, driven by multiple potential iron inputs, such as shallow hydrothermal plumes, island sediment, and river runoff (<xref ref-type="bibr" rid="B67">Shiozaki et&#xa0;al., 2014</xref>; <xref ref-type="bibr" rid="B15">Caffin et&#xa0;al., 2018</xref>; <xref ref-type="bibr" rid="B23">Dutheil et&#xa0;al., 2018</xref>; <xref ref-type="bibr" rid="B29">Guieu et&#xa0;al., 2018</xref>; <xref ref-type="bibr" rid="B72">Tilliette et&#xa0;al., 2022</xref>). Therefore, to investigate the hypothesis that significant ash deposition on the western SPO led to the Chl-a increase following the 2022 Hunga eruption, we investigated the possibility of Chl-a response to nutrient supply from other sources.</p>
<p>First, the shallow hydrothermal sources along Tonga-Kermadec arc have the potential to fertilise the western SPO with iron (<xref ref-type="bibr" rid="B29">Guieu et&#xa0;al., 2018</xref>; <xref ref-type="bibr" rid="B72">Tilliette et&#xa0;al., 2022</xref>). However, as <xref ref-type="bibr" rid="B72">Tilliette et&#xa0;al. (2022)</xref> say, shallow hydrothermal plumes release high levels of iron only around the shallow hydrothermal sources on the Tonga-Kermadec arc, and to lesser extent, into the water surrounded by Vanuatu, New Caledonia, and Fiji. This indicates the Chl-a increase following the 2022 Hunga eruption was not driven by a shallow hydrothermal source of iron.</p>
<p>
<xref ref-type="bibr" rid="B23">Dutheil et&#xa0;al. (2018)</xref> showed that the spatial distribution of Chl-a estimates is tightly controlled by iron release from the sediment flux, which are related to the zonal (eastward) advection of iron downstream of the islands, a second potential iron source. <xref ref-type="supplementary-material" rid="SM1">
<bold>Figure S8A</bold>
</xref> shows the spatial distribution of the 5-day mean surface zonal current anomalies for January 2022 against 2004&#x2013;2021 climatology. Positive (negative) values of surface zonal currents imply eastward (westward) anomalies. However, the surface zonal current dataset showed the insignificant changes in this region between pre- and post-eruption of Hung volcano in January 2022, when compared to other years.</p>
<p>Many islands could also deliver terrigenous nutrients through runoff to the western SPO. A large amount of runoff from land is expected to be triggered by high precipitation, which causes the water column stratification and land drainage required for N<sub>2</sub> fixation (<xref ref-type="bibr" rid="B67">Shiozaki et&#xa0;al., 2014</xref>). <xref ref-type="supplementary-material" rid="SM1">
<bold>Figure S8B</bold>
</xref> shows the daily variation of precipitation rates averaged over the western SPO for 2022 vs. climatological mean with one standard deviation of the mean (2004 to 2021). However, there was no significant increase in precipitation over the waters of Vanuatu, New Caledonia, and Fiji during 2022 volcanic episodes compared to climatological values, indicating a likely minor impact of river runoff on nutrient supply.</p>
<p>A final alternative explanation for the changes in phytoplankton biomass in the western SPO may be the changes in MLD, related to the supply of nutrients from below the thermocline to the euphotic zone (<xref ref-type="bibr" rid="B73">Vaughan et&#xa0;al., 2007</xref>; <xref ref-type="bibr" rid="B11">Boyce et&#xa0;al., 2010</xref>; <xref ref-type="bibr" rid="B52">Mantas et&#xa0;al., 2011</xref>; <xref ref-type="bibr" rid="B37">Jutzeler et&#xa0;al., 2014</xref>; <xref ref-type="bibr" rid="B38">Jutzeler et&#xa0;al., 2020</xref>). Indeed, <xref ref-type="bibr" rid="B70">Terry et&#xa0;al. (2022)</xref> reported the tsunamis produced by the 2022 Hunga eruption, were up to 15&#xa0;m on the islands near to the source volcano. However, there was no significant change in the area-averaged MLDs in 2022 year with time, relative to climatological area-averaged MLDs (<xref ref-type="supplementary-material" rid="SM1">
<bold>Figure S8C</bold>
</xref>). Therefore, in summary, the lack of alternative plausible hypotheses supports our conclusion that the increase in Chl-a is linked to the 2022 Hunga ash fall over the western SPO.</p>
</sec>
</sec>
<sec id="s4">
<label>4</label>
<title>Summary and conclusion</title>
<p>Using multiple satellite and reanalysis data sets during the past 19 years (2004&#x2013;2022), we analyzed the transport pathways of extreme explosive volcanic plumes and their impacts on phytoplankton biomass in the western SPO. Our study revealed that there were four extreme volcanic events, which have a VEI above 3 and exceeded 99.9th percentile of daily SO<sub>2</sub> values averaged over the western SPO over last 19 years, from Rabaul volcano (October 2006), Ambae volcano (July 2018), Ulawun volcano (June 2019), and Hunga volcano (January 2022). Four extreme volcanic eruptions produced sporadic SO<sub>2</sub> plumes which have the long-distance transport (covering an area of &gt;765,000 km<sup>2</sup>) over the western SPO and injection into the stratosphere (&gt;15&#xa0;km). The 2006 Rabaul and 2019 Ulawun eruptions showed relatively high volcanic plumes over coastal waters around the source volcano. In July 2018, Ambae eruption showed eastward long-distance (&gt;2000&#xa0;km) transport, reaching the northern part of the Tongan archipelago. On the other hand, the SO<sub>2</sub> emitted from the 2022 Hunga volcano travelled a long distance (&gt;6000&#xa0;km) westward, reaching the northern part of Australia, passing over Vanuatu and Fiji. In particular, there was likely high deposition of ash-laden plumes transported long-distance over the waters surrounded by Vanuatu, New Caledonia, and Fiji (~2000 km from source). In addition, this study showed that the high positive Chl-a anomaly to the 2022 Hunga volcanic eruption was spatially distributed in the water surrounded by Vanuatu, New Caledonia, and Fiji. The phytoplankton response to 2022 Hunga eruptions was associated with a ~70% increase in Chl-a (~40% increase in PP), compared to climatological changes. However, the other three events studied here (2006 Rabaul, 2018 Ambae, and 2019 Ulawun eruptions) were not associated with a Chl-a response over the regions with the high volcanic plumes, likely a result of low ash deposition. Minor changes in nutrient supply from other sources for 2022 vs. climatological means suggest a link between the increase in Chl-a and the 2022 Hunga ash fall. These results indicate that the phytoplankton response to the long-distance transport of the explosive volcanic plumes is not ubiquitous. Only volcanic events accompanied by high ash deposition strongly impact ocean productivity over the western SPO, supporting the hypothesis that volcanic ash fertilization has a potential to alleviate the limited nutrients of phytoplankton growth (particularly iron for N<sub>2</sub> fixation) in the western SPO. Assuming that an increase of surface ocean iron concentrations by 2 nM (usually with surface condition of ~0.5 nM Fe in the waters around Vanuatu and Fiji; <xref ref-type="bibr" rid="B72">Tilliette et&#xa0;al., 2022</xref>) is needed to induce the optimal phytoplankton growth condition (<xref ref-type="bibr" rid="B25">Fitzwater et&#xa0;al., 1996</xref>), observed phytoplankton response for the distal ash deposits over the area of ~8.2 &#xd7; 10<sup>5</sup> km<sup>2</sup> with MLD of ~20 m (<xref ref-type="fig" rid="f2">
<bold>Figures&#xa0;2D</bold>
</xref>, <xref ref-type="fig" rid="f4">
<bold>4H</bold>
</xref>, <xref ref-type="supplementary-material" rid="SM1">
<bold>S8C</bold>
</xref>) might be supported by the supply of a total amount of ~2.5 &#xd7; 10<sup>16</sup> nmol Fe following 2022 Hunga eruption. Our findings underline the importance of further studies based on geochemical experiments and shipboard bioassay experiments, to improve our understanding of which nutrients alleviate nutrient limitation of phytoplankton at community level following volcanic ash deposition in the western SPO (<xref ref-type="bibr" rid="B21">Duggen et&#xa0;al., 2007</xref>; <xref ref-type="bibr" rid="B13">Browning et&#xa0;al., 2014</xref>; <xref ref-type="bibr" rid="B54">M&#xe9;lan&#xe7;on et&#xa0;al., 2014</xref>; <xref ref-type="bibr" rid="B75">Vergara-Jara et&#xa0;al., 2021</xref>).</p>
</sec>
<sec id="s5" sec-type="data-availability">
<title>Data availability statement</title>
<p>The original contributions presented in the study are included in the article/<xref ref-type="supplementary-material" rid="SM1">
<bold>Supplementary Material</bold>
</xref>. Further inquiries can be directed to the corresponding author.</p>
</sec>
<sec id="s6" sec-type="author-contributions">
<title>Author contributions</title>
<p>J-EY and DK proposed the motivation of this work. J-EY designed the research. J-EY obtained, analyzed, and interpreted the satellite and reanalysis data. JL and SC provided, analyzed, and interpreted the geochemical data. J-EY wrote the manuscript with inputs from DK, JL, and SC. All authors contributed to the article and approved the submitted version.</p>
</sec>
</body>
<back>
<sec id="s7" sec-type="funding-information">
<title>Funding</title>
<p>SC was supported by the Ministry of Business, Innovation and Employment (MBIE) Endeavour Research Program (UOAX1913) and Ministry of Lands of the Kingdom of Tonga and the University of Auckland for support for the sampling and analysis of 2022 Hunga tephra.</p>
</sec>
<ack>
<title>Acknowledgments</title>
<p>This work was conducted as a part of the Marine Biomass Regeneration project in the Centre for Climate Repair at Cambridge. We thank the editor and four reviewers for helpful feedback. We acknowledge NASA for providing CALIPSO, OMI, and OMPS data, European Space Agency for providing GlobColour datasets, Copernicus for providing MLD and SST data, and NOAA for providing precipitation rate and wind datasets.</p>
</ack>
<sec id="s8" sec-type="COI-statement">
<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 id="s9" sec-type="disclaimer">
<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="s10" sec-type="supplementary-material">
<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/fmars.2023.1072610/full#supplementary-material">https://www.frontiersin.org/articles/10.3389/fmars.2023.1072610/full#supplementary-material</ext-link>
</p>
<supplementary-material xlink:href="DataSheet_1.docx" id="SM1" mimetype="application/vnd.openxmlformats-officedocument.wordprocessingml.document"/>
</sec>
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