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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.2022.910441</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>The Interplay Between Dimethyl Sulfide (DMS) and Methane (CH<sub>4</sub>) in a Coral Reef Ecosystem</article-title>
</title-group>
<contrib-group>
<contrib contrib-type="author" corresp="yes">
<name>
<surname>Deschaseaux</surname>
<given-names>Elisabeth S. M.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
<xref ref-type="author-notes" rid="fn001">
<sup>*</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/1506314"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Swan</surname>
<given-names>Hilton B.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/1508266"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Maher</surname>
<given-names>Damien T.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/175210"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Jones</surname>
<given-names>Graham B.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/1393542"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Schulz</surname>
<given-names>Kai G.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/140986"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Koveke</surname>
<given-names>Edwin P.</given-names>
</name>
<xref ref-type="aff" rid="aff4">
<sup>4</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/1755448"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Toda</surname>
<given-names>Kei</given-names>
</name>
<xref ref-type="aff" rid="aff4">
<sup>4</sup>
</xref>
<xref ref-type="aff" rid="aff5">
<sup>5</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/1825712"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Eyre</surname>
<given-names>Bradley D.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/312652"/>
</contrib>
</contrib-group>
<aff id="aff1">
<sup>1</sup>
<institution>Faculty of Science and Engineering, Southern Cross University</institution>, <addr-line>Lismore, NSW</addr-line>, <country>Australia</country>
</aff>
<aff id="aff2">
<sup>2</sup>
<institution>Centre for Coastal Biogeochemistry, Faculty of Science and Engineering, Southern Cross University</institution>, <addr-line>Lismore, NSW</addr-line>, <country>Australia</country>
</aff>
<aff id="aff3">
<sup>3</sup>
<institution>Southern Cross GeoScience, Faculty of Science and Engineering, Southern Cross University</institution>, <addr-line>Lismore, NSW</addr-line>, <country>Australia</country>
</aff>
<aff id="aff4">
<sup>4</sup>
<institution>Department of Chemistry, Kumamoto University</institution>, <addr-line>Kumamoto</addr-line>, <country>Japan</country>
</aff>
<aff id="aff5">
<sup>5</sup>
<institution>International Research Organization for Advanced Science and Technology (IROAST), Kumamoto University</institution>, <addr-line>Kumamoto</addr-line>, <country>Japan</country>
</aff>
<author-notes>
<fn fn-type="edited-by">
<p>Edited by: Cliff Ross, University of North Florida, United States</p>
</fn>
<fn fn-type="edited-by">
<p>Reviewed by: Gael John Lecellier, Universit&#xe9; de Versailles Saint-Quentin-en-Yvelines, France; Sohiko Kameyama, Hokkaido University, Japan</p>
</fn>
<fn fn-type="corresp" id="fn001">
<p>*Correspondence: Elisabeth S. M. Deschaseaux, <email xlink:href="mailto:elisabeth.deschaseaux@gmail.com">elisabeth.deschaseaux@gmail.com</email>
</p>
</fn>
<fn fn-type="other" id="fn002">
<p>This article was submitted to Coral Reef Research, a section of the journal Frontiers in Marine Science</p>
</fn>
</author-notes>
<pub-date pub-type="epub">
<day>20</day>
<month>06</month>
<year>2022</year>
</pub-date>
<pub-date pub-type="collection">
<year>2022</year>
</pub-date>
<volume>9</volume>
<elocation-id>910441</elocation-id>
<history>
<date date-type="received">
<day>01</day>
<month>04</month>
<year>2022</year>
</date>
<date date-type="accepted">
<day>04</day>
<month>05</month>
<year>2022</year>
</date>
</history>
<permissions>
<copyright-statement>Copyright &#xa9; 2022 Deschaseaux, Swan, Maher, Jones, Schulz, Koveke, Toda and Eyre</copyright-statement>
<copyright-year>2022</copyright-year>
<copyright-holder>Deschaseaux, Swan, Maher, Jones, Schulz, Koveke, Toda and Eyre</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>Earth&#x2019;s Radiation Budget is partly dictated by the fragile and complex balance between biogenic volatile organic compounds (BVOCs) and greenhouse gases (GHGs), which have the potential to impose cooling or warming once emitted to the atmosphere. Whilst methane (CH<sub>4</sub>) is strictly associated with global warming due to its solar-radiation absorbing properties, dimethyl sulfide (DMS) is generally considered a cooling gas through the light scattering properties of its atmospheric oxidation products. However, DMS may also partially contribute to the Earth&#x2019;s warming through a small portion of it being degraded to CH<sub>4</sub> in the water column. Coral reefs emit both DMS and CH<sub>4</sub> but they have not previously been simultaneously measured. Here, we report DMS and CH<sub>4</sub> fluxes as well as aerosol particle counts at Heron Island, southern Great Barrier Reef, during the austral summer of 2016. Sea-to-air DMS and CH<sub>4</sub> fluxes were on average 24.9 &#xb1; 1.81 and 1.36 &#xb1; 0.11 &#xb5;mol m<sup>-2</sup> d<sup>-1</sup>, whilst intermediate (&lt; 0.5-2.5 um) and large (&gt; 2.5 um) particle number concentrations averaged 5.51 x 10<sup>6</sup> &#xb1; 1.73 x 10<sup>5</sup> m<sup>-3</sup> and 1.15 x 10<sup>6</sup> &#xb1; 4.63 x 10<sup>4</sup> m<sup>-3</sup>, respectively. Positive correlations were found between DMS emissions and the abundance of intermediate (R<sup>2</sup> = 0.1669, <italic>p</italic> &lt; 0.001, <italic>n</italic> = 93) and large (R<sup>2</sup> = 0.0869, <italic>p</italic> = 0.004, <italic>n</italic> = 93) aerosol particles, suggesting that DMS sea-to-air emissions significantly contribute to the growth of existing particles to the measured size ranges at the Heron Island lagoon. Additionally, a strong positive correlation was found between DMS and CH<sub>4</sub> fluxes (R<sup>2</sup> = 0.7526, <italic>p</italic> &lt; 0.00001, <italic>n</italic> = 93), suggesting that the emission of these volatile compounds from coral reefs is closely linked. The slope of the regression between DMS and CH<sub>4</sub> suggests that CH<sub>4</sub> emissions at the Heron Island lagoon represent 5% of that of DMS, which is consistent with the average sea-to-air fluxes reported in this study (i.e. 24.9 &#xb1; 1.81 &#xb5;mol m<sup>-2</sup> d<sup>-1</sup> for DMS and 1.36 &#xb1; 0.11 for CH<sub>4</sub>). These findings provide new insights on the complexity of BVOC and GHG emissions in coral reef systems and their potential role in climate regulation.</p>
</abstract>
<kwd-group>
<kwd>fluxes</kwd>
<kwd>great barrier reef</kwd>
<kwd>biogenic volatile organic compounds (BVOCs)</kwd>
<kwd>greenhouse gases (GHGs)</kwd>
<kwd>aerosol particles</kwd>
<kwd>Heron Island</kwd>
</kwd-group>
<counts>
<fig-count count="5"/>
<table-count count="1"/>
<equation-count count="5"/>
<ref-count count="55"/>
<page-count count="12"/>
<word-count count="6471"/>
</counts>
</article-meta>
</front>
<body>
<sec id="s1" sec-type="intro">
<title>1 Introduction</title>
<p>Dimethyl sulfide (DMS) and methane (CH<sub>4</sub>) are key biogenic compounds in climate change processes (<xref ref-type="bibr" rid="B4">Carpenter et&#xa0;al., 2012</xref>). DMS is often associated with a cooling effect through contributing to aerosol formation that increase Earth&#x2019;s radiative properties (<xref ref-type="bibr" rid="B5">Charlson et&#xa0;al., 1987</xref>). In contrast, CH<sub>4</sub> is responsible for a warming effect with a short-term greenhouse potential that is 23 to 69 times greater than that of CO<sub>2</sub> (<xref ref-type="bibr" rid="B45">Shine et&#xa0;al., 2005</xref>). The bulk of DMS is produced through the algal and bacterial enzymatic cleavage of dimethylsulfoniopropionate (DMSP) (<xref ref-type="bibr" rid="B46">Sim&#xf3;, 2001</xref>), a biogenic sulfur compound that is synthesised by a wide range of marine algae (<xref ref-type="bibr" rid="B47">Stefels, 2000</xref>), bacteria (<xref ref-type="bibr" rid="B7">Curson et&#xa0;al., 2017</xref>) and invertebrate corals (<xref ref-type="bibr" rid="B41">Raina et&#xa0;al., 2013</xref>). In contrast, the bulk of biogenic CH<sub>4</sub> is mainly produced by anaerobic methanogenic bacterial activity through the reduction of either CO<sub>2</sub>, acetate or methyl-group containing compounds (<xref ref-type="bibr" rid="B29">Liu and Whitman, 2008</xref>), although recent studies show that CH<sub>4</sub> can also be produced by plants, fungi, algae and cyanobacteria from methylated nitrogen- and sulfur-containing compounds in the presence of oxygen (<xref ref-type="bibr" rid="B13">Ernst et&#xa0;al., 2022</xref>). Thus, a small portion of CH<sub>4</sub> can originate from the hydrolysis of DMS according to the following equation (<xref ref-type="bibr" rid="B22">Kiene et&#xa0;al., 1986</xref>; <xref ref-type="bibr" rid="B29">Liu and Whitman, 2008</xref>):</p>
<disp-formula>
<label>(1)</label>
<mml:math display="block" id="M1">
<mml:mrow>
<mml:mn>2</mml:mn>
<mml:msub>
<mml:mrow>
<mml:mrow>
<mml:mo>(</mml:mo>
<mml:mrow>
<mml:msub>
<mml:mrow>
<mml:mtext>CH</mml:mtext>
</mml:mrow>
<mml:mn>3</mml:mn>
</mml:msub>
</mml:mrow>
<mml:mo>)</mml:mo>
</mml:mrow>
</mml:mrow>
<mml:mn>2</mml:mn>
</mml:msub>
<mml:mtext>S</mml:mtext>
<mml:mo>+</mml:mo>
<mml:mn>2</mml:mn>
<mml:msub>
<mml:mtext>H</mml:mtext>
<mml:mn>2</mml:mn>
</mml:msub>
<mml:mtext>O</mml:mtext>
<mml:mo>&#x2192;</mml:mo>
<mml:mn>3</mml:mn>
<mml:msub>
<mml:mrow>
<mml:mtext>CH</mml:mtext>
</mml:mrow>
<mml:mn>4</mml:mn>
</mml:msub>
<mml:mo>+</mml:mo>
<mml:msub>
<mml:mrow>
<mml:mtext>CO</mml:mtext>
</mml:mrow>
<mml:mn>2</mml:mn>
</mml:msub>
<mml:mo>+</mml:mo>
<mml:mn>2</mml:mn>
<mml:msub>
<mml:mtext>H</mml:mtext>
<mml:mn>2</mml:mn>
</mml:msub>
<mml:mtext>S</mml:mtext>
</mml:mrow>
</mml:math>
</disp-formula>
<p>The link between DMS degradation and CH<sub>4</sub> production has now been reported across several studies on anoxic marine sediments (<xref ref-type="bibr" rid="B23">Kiene and Visscher, 1987</xref>; <xref ref-type="bibr" rid="B21">Kiene, 1988</xref>; <xref ref-type="bibr" rid="B51">Wang et&#xa0;al., 2009</xref>), where methanogenic bacteria are particularly abundant (<xref ref-type="bibr" rid="B33">Mechalas, 1974</xref>; <xref ref-type="bibr" rid="B1">Barnes and Goldberg, 1976</xref>). Indeed, it seems that the DMS-to-CH<sub>4</sub> conversion can also be mediated by methanogenic bacteria (<xref ref-type="bibr" rid="B23">Kiene and Visscher, 1987</xref>) but also by methylotrophic bacteria belonging to the order Methanosarcinales and Methanobacteriales (<xref ref-type="bibr" rid="B29">Liu and Whitman, 2008</xref>). More recently, the role of DMS as a precursor of CH<sub>4</sub> was clearly demonstrated in upwelling waters as addition of <sup>13</sup>C enriched-DMS led to a significant increase in <sup>13</sup>C enriched-CH<sub>4</sub> (<xref ref-type="bibr" rid="B15">Florez-Leiva et&#xa0;al., 2013</xref>). Interestingly, DMS was estimated to contribute to about 28% of CH<sub>4</sub> production in both anoxic sediments (<xref ref-type="bibr" rid="B21">Kiene, 1988</xref>) and upwelling waters (<xref ref-type="bibr" rid="B15">Florez-Leiva et&#xa0;al., 2013</xref>), although these two marine habitats are likely to host very different bacterial communities. DMS as a potential precursor of CH<sub>4</sub> across various marine ecosystems adds a level of complexity to the role of DMS as a climate cooling agent (<xref ref-type="bibr" rid="B5">Charlson et&#xa0;al., 1987</xref>; <xref ref-type="bibr" rid="B38">Quinn and Bates, 2011</xref>; <xref ref-type="bibr" rid="B19">Jones, 2013</xref>).</p>
<p>DMS is expected to be particularly concentrated in coral reef ecosystems due to the high DMSP content in corals, coral-associated symbionts and a wide range of coral reef invertebrates (<xref ref-type="bibr" rid="B11">Deschaseaux et&#xa0;al., 2016</xref>; <xref ref-type="bibr" rid="B16">Haydon et&#xa0;al., 2018</xref>). However, although coral reef sea-to-air DMS fluxes contribute to atmospheric sulfur emissions (<xref ref-type="bibr" rid="B50">Swan et&#xa0;al., 2017</xref>), a recent modelling study suggested that coral-reef-derived DMS emissions most likely have a negligible effect on the local climate of the Great Barrier Reef (<xref ref-type="bibr" rid="B14">Fiddes et&#xa0;al., 2021</xref>). Coral reef frameworks are also sites of active anoxic and suboxic organic matter oxidation, making coral reef pore waters particularly rich in CH<sub>4</sub> and coral reef ecosystems ideal platforms for the release of CH<sub>4</sub> to the water column and atmosphere (<xref ref-type="bibr" rid="B44">Sansone et&#xa0;al., 1993</xref>; <xref ref-type="bibr" rid="B36">O&#x2019;Reilly et&#xa0;al., 2015</xref>), which could be counteracting the cooling effect of DMS emissions. A recent study showed that permeable coral reef carbonate sediments were a source of DMS and CH<sub>4</sub> into the water column and that CH<sub>4</sub> production could be a sink for DMS in coral reef systems (<xref ref-type="bibr" rid="B12">Deschaseaux et&#xa0;al., 2019</xref>). Since sea-to-air DMS and CH<sub>4</sub> fluxes from coral reef systems have been independently reported by previous studies, the focus of this study was to simultaneously quantify and report sea-to-air DMS and CH<sub>4</sub> fluxes from the Heron Island reef lagoon, southern Great Barrier Reef, to assess the interplay of atmospheric DMS and CH<sub>4</sub> emissions.</p>
<p>We hypothesised that coral-reef DMS emissions would contribute to the growth of aerosol nanoparticles and that coral-reef DMS and CH<sub>4</sub> emissions are linked due to a small portion of DMS being hydrolysed to CH<sub>4</sub> in coral reef waters.</p>
</sec>
<sec id="s2">
<title>2 Material and Methods</title>
<sec id="s2_1">
<title>2.1 Study Site and Sampling</title>
<p>A field campaign was conducted on Heron Island, southern Great Barrier Reef (23.44&#xb0;S, 151.91&#xb0;E), in the austral summer of 2016 (4<sup>th</sup> to the 17<sup>th</sup> of February) where dissolved CH<sub>4</sub> and CO<sub>2</sub> were measured alongside dissolved DMS (DMS<sub>w</sub>) using a cavity-ring-down spectrometer (Picarro G2201-<italic>i</italic>) (<xref ref-type="bibr" rid="B31">Maher et&#xa0;al., 2013</xref>) and a Vapor Generation &#x2013; Chemiluminescence (VG-CL) device (<xref ref-type="bibr" rid="B34">Nagahata et&#xa0;al., 2013</xref>), respectively. A Gas Chromatograph (Varian CP3800 GC) equipped with a pulsed flame photometric detector (GC-PFPD) was used to measure atmospheric DMS (DMS<sub>a</sub>) (<xref ref-type="bibr" rid="B49">Swan et&#xa0;al., 2015</xref>; <xref ref-type="bibr" rid="B50">Swan et&#xa0;al., 2017</xref>).</p>
<p>A water pump and a 60 m suction-rated pipe were used to pump seawater from the Heron Island reef flat to the Heron Island Research Station (HIRS), where all instruments were operated. The seawater inlet was attached to a cinder block 50 cm above the sediment bed and about 50 cm below the low-tide mark. A non-return valve and a 1 mm mesh net were placed around the suction pipe inlet to prevent large pieces of sediment and seaweed getting through the suction line. The mesh was cleaned every 2-3 days to prevent biofouling. Part of the pumped seawater was diverted into a showerhead exchanger that was connected in line with the cavity-ring-down spectrometer for CH<sub>4</sub> and CO<sub>2</sub> measurements, while the remainder was diverted to the HIRS&#x2019; flow-through seawater recycling system. The recycling water outlet was used to manually sample seawater at a low flow rate using a 50 mL syringe for DMS<sub>w</sub> analysis. A HYDROLAB HL4 sonde was placed within 1 m of the water intake to record seawater temperature, salinity, dissolved oxygen (DO), and depth, every 15 min. Tide predictions were sourced from the Bureau of Meteorology (BoM) with low tide times locally adjusted +1.25 h for the Heron Island reef flat according to <xref ref-type="bibr" rid="B50">Swan et&#xa0;al. (2017)</xref>.</p>
<p>An air intake consisting of ~10 m Teflon&#x2122; tubing was fixed to the roof of the HIRS, within ~100 m in line of sight to the reef flat location where seawater was continuously pumped from. The air intake was shielded from rain. A wireless automated weather station (AWS, model XC0348, Electus Distribution) mounted within 1 m of the air intake provided data for wind speed (WS, &#xb1; 1 m s<sup>-1</sup> for WS &lt; 10 m s<sup>-1</sup> and &#xb1; 10% for WS &gt; 10 m s<sup>-1</sup>), wind direction (WD), rainfall, air temperature (&#xb1; 1&#xb0;C), humidity (&#xb1; 5%) and barometric pressure (&#xb1; 3hPa), at 5-min intervals. Meteorological data at 5 min intervals was used to match to the 15 min interval chemical measurements. Solar irradiance at the proximity of the air intake was recorded using a HOBO (Onset Co., USA) light logger (upper limit ~6000 &#x3bc;E m<sup>-2</sup> s<sup>-1</sup>). Light intensity HOBO Lux units were adjusted to a maximum light intensity of 2000 &#x3bc;Em<sup>&#x2212;2</sup> s<sup>&#x2212;1</sup>. First and last daytime lights were at 5:14 and 18:57 respectively on average over the sampling period. An air quality monitor laser particle counter (Dylos DC1700, Dylos Corp, CA, USA) was used to record 1-min averaged particle number concentrations at ambient humidity in the two size range fractions 0.5-2.5 &#xb5;m and &gt; 2.5 &#xb5;m every 15 min. The air quality monitor was placed in a shielded location near the air intake.</p>
</sec>
<sec id="s2_2">
<title>2.2 DMS<sub>w</sub> and DMS<sub>a</sub> Measurements</title>
<p>DMS<sub>w</sub> concentrations were determined in triplicate every 15 min by placing 10 mL of seawater into a 50 mL sample tube that was manually shaken for 1 min, then pressurised with 30 mL of air and injected onto the chemiluminescence device (VG-CL) (<xref ref-type="bibr" rid="B34">Nagahata et&#xa0;al., 2013</xref>). When DMS<sub>w</sub> mixes with ozone in the VG-CL, it generates an instant chemiluminescent emission where the light intensity is converted into a quantifiable electrical signal. The injection tube was rinsed with deionised water in between each injection to prevent analyte carry-over. A 6-point calibration was run at the beginning of the field campaign, and either a 4 nM or 10 nM DMSP standard was randomly run each day to monitor the reproducibility and stability of the system over time. Because these measurements are labour-intensive and could not be automated, sampling occurred at random times of the day and night over the 2-week field campaign.</p>
<p>DMS<sub>a</sub> concentrations were determined on the GC-PFPD using an automated cryogenic trapping system that collected ~4L of air for analysis, providing a 0.1 nmol m<sup>-3</sup> (0.002 ppb) limit of detection. The expanded relative measurement uncertainty of the automated GC-PFPD was 13% (k = 2, for a 95% CI). A complete description of the configuration, operation, calibration, and uncertainty analysis of the automated GC-PFPD is described by <xref ref-type="bibr" rid="B49">Swan et&#xa0;al. (2015)</xref>.</p>
</sec>
<sec id="s2_3">
<title>2.3 Flux Calculations</title>
<p>Sea-to-air DMS fluxes were estimated based on the different parameterisations proposed by <xref ref-type="bibr" rid="B28">Liss and Merlivat (1986)</xref> (LM86), <xref ref-type="bibr" rid="B35">Nightingale et&#xa0;al. (2000)</xref> (N00) and <xref ref-type="bibr" rid="B52">Wanninkhof (2014)</xref> (W14) and by applying the approach of <xref ref-type="bibr" rid="B27">Lana et&#xa0;al. (2011)</xref> (L11) (see details in <xref ref-type="supplementary-material" rid="SM1">
<bold>Supplementary Table&#xa0;1</bold>
</xref>). The sea-to-air DMS fluxes and uncertainties presented here correspond to the median and standard error of these combined fluxes.</p>
<p>Briefly, sea-to-air fluxes of DMS (F<sub>DMS</sub>) (in &#xb5;mol m<sup>-2</sup> d<sup>-1</sup>) were estimated based on the following equation:</p>
<disp-formula>
<label>(2)</label>
<mml:math display="block" id="M2">
<mml:mrow>
<mml:msub>
<mml:mtext>F</mml:mtext>
<mml:mrow>
<mml:mtext>DMS</mml:mtext>
</mml:mrow>
</mml:msub>
<mml:mo>=</mml:mo>
<mml:msub>
<mml:mtext>K</mml:mtext>
<mml:mtext>T</mml:mtext>
</mml:msub>
<mml:mo stretchy="false">(</mml:mo>
<mml:msub>
<mml:mtext>C</mml:mtext>
<mml:mtext>w</mml:mtext>
</mml:msub>
<mml:mo>&#x2013;</mml:mo>
<mml:mi>&#x3b1;</mml:mi>
<mml:msub>
<mml:mtext>C</mml:mtext>
<mml:mtext>g</mml:mtext>
</mml:msub>
<mml:mo stretchy="false">)</mml:mo>
</mml:mrow>
</mml:math>
</disp-formula>
<p>Where K<sub>T</sub> is the gas transfer velocity constant (in m d<sup>-1</sup>), &#x3b1; is the dimensionless Henry&#x2019;s Law constant and C<sub>w</sub> and C<sub>g</sub> are DMS concentrations (in &#xb5;mol m<sup>-3</sup>) in the water and gas phase, respectively, with each parameterisation using a different approach to estimate K<sub>T</sub>.</p>
<p>The dimensionless Henry&#x2019;s Law Constant (&#x3b1;) for DMS solubility in seawater was calculated using the following equation:</p>
<disp-formula>
<label>(3)</label>
<mml:math display="block" id="M3">
<mml:mrow>
<mml:mi>&#x3b1;</mml:mi>
<mml:mo>=</mml:mo>
<mml:mn>1</mml:mn>
<mml:mo stretchy="false">/</mml:mo>
<mml:msub>
<mml:mtext>H</mml:mtext>
<mml:mtext>K</mml:mtext>
</mml:msub>
<mml:mtext>&#xa0;x&#xa0;RT</mml:mtext>
</mml:mrow>
</mml:math>
</disp-formula>
<p>Where H<sub>K</sub> (atm L mol<sup>-1</sup>) is the Henry&#x2019;s Law Constant for DMS, R is the universal gas constant (0.082 L atm K<sup>&#x2212;1</sup> mol<sup>&#x2212;1</sup>) and T is the seawater temperature in Kelvin. H<sub>K</sub> was calculated based on the following equation by <xref ref-type="bibr" rid="B8">Dacey et&#xa0;al. (1984)</xref>:</p>
<disp-formula>
<label>(4)</label>
<mml:math display="block" id="M4">
<mml:mrow>
<mml:msub>
<mml:mtext>H</mml:mtext>
<mml:mtext>K</mml:mtext>
</mml:msub>
<mml:mo>=</mml:mo>
<mml:msup>
<mml:mtext>e</mml:mtext>
<mml:mrow>
<mml:mrow>
<mml:mo>(</mml:mo>
<mml:mrow>
<mml:mo>&#x2212;</mml:mo>
<mml:mn>3547</mml:mn>
<mml:mo stretchy="false">/</mml:mo>
<mml:mtext>T&#xa0;</mml:mtext>
<mml:mo>+</mml:mo>
<mml:mn>12.64</mml:mn>
</mml:mrow>
<mml:mo>)</mml:mo>
</mml:mrow>
</mml:mrow>
</mml:msup>
</mml:mrow>
</mml:math>
</disp-formula>
<p>Sea-to-air CH<sub>4</sub>, CO<sub>2</sub> and O<sub>2</sub> fluxes were calculated based on the parameterisation approaches proposed by <xref ref-type="bibr" rid="B18">Ho et&#xa0;al. (2006)</xref> and <xref ref-type="bibr" rid="B52">Wanninkhof (2014)</xref>. Atmospheric concentrations were assumed to be constant (CH<sub>4</sub> 1.8 ppm, CO<sub>2</sub> 400 ppm and O<sub>2</sub> 21000 ppm). Solubility coefficients for CH<sub>4</sub> (<xref ref-type="bibr" rid="B55">Wiesenburg and Guinasso Jr, 1979</xref>), CO<sub>2</sub> (<xref ref-type="bibr" rid="B54">Weiss, 1974</xref>) and O<sub>2</sub> (<xref ref-type="bibr" rid="B2">Benson and Krause Jr, 1984</xref>) were calculated based on temperature and salinity.</p>
</sec>
<sec id="s2_4">
<title>2.4 Reef Production</title>
<p>Reef DMS, CH<sub>4</sub>, CO<sub>2</sub> and O<sub>2</sub> production (RP, mol m<sup>-2</sup> h<sup>-1</sup>) were calculated around each low tide using the following equation:</p>
<disp-formula>
<label>(5)</label>
<mml:math display="block" id="M5">
<mml:mrow>
<mml:mi>R</mml:mi>
<mml:mi>P</mml:mi>
<mml:mo>=</mml:mo>
<mml:mo>&#xa0;</mml:mo>
<mml:mfrac>
<mml:mrow>
<mml:mi>&#x394;</mml:mi>
<mml:mi>C</mml:mi>
<mml:mi>w</mml:mi>
</mml:mrow>
<mml:mrow>
<mml:mi>&#x394;</mml:mi>
<mml:mi>T</mml:mi>
</mml:mrow>
</mml:mfrac>
<mml:mi>x</mml:mi>
<mml:mo>&#xa0;</mml:mo>
<mml:mi>D</mml:mi>
<mml:mo>&#xa0;</mml:mo>
<mml:mo>+</mml:mo>
<mml:mfrac>
<mml:mrow>
<mml:mi>M</mml:mi>
<mml:mi>e</mml:mi>
<mml:mi>a</mml:mi>
<mml:mi>n</mml:mi>
<mml:mi>F</mml:mi>
<mml:mi>l</mml:mi>
<mml:mi>u</mml:mi>
<mml:mi>x</mml:mi>
</mml:mrow>
<mml:mrow>
<mml:mn>24</mml:mn>
</mml:mrow>
</mml:mfrac>
</mml:mrow>
</mml:math>
</disp-formula>
<p>Where &#x394;C<sub>W</sub> is the difference in dissolved concentrations between the highest point following low tide and the actual low tide, &#x394;T is the time difference between these 2 points, D is the average depth for that time period and MeanFlux is the average sea-to-air flux for that period.</p>
</sec>
<sec id="s2_5">
<title>2.5 Statistical Analysis</title>
<p>The significance of the correlations between DMS, CH<sub>4</sub>, CO<sub>2</sub> and O<sub>2</sub> were evaluated using the Pearson correlation method. Given that DMS and CH<sub>4</sub> showed the strongest correlation (R<sup>2</sup> = 0.7526, <italic>p &lt;</italic>0.00001, <italic>n</italic> = 93), we specifically assessed what drives DMS and CH<sub>4</sub> fluxes by carrying out stepwise multiple linear regressions (MLRs) against seven potential predictors and their interactions (salinity, pH, depth, wind direction, dewpoint, windchill and solar irradiance). In order to avoid over-fitting and find a balance between model complexity and explanatory power, we followed a backward elimination process based on the Akaike Information Criterion (AIC, details in <xref ref-type="supplementary-material" rid="SM1">
<bold>Supplementary Figure&#xa0;1</bold>
</xref>) starting with all seven potential measured predictors. Note that we opted not to include temperature and wind speed, which are covariates in flux calculations. Windchill and dewpoint are influenced by air temperature, which is not a covariate in flux calculations, and wind direction is not correlated to wind speed. Calculations were performed using the functions &#x201c;boxplot&#x201d;, &#x201c;stepwisefit&#x201d;, and &#x201c;plotEffects&#x201d; in MATLAB.</p>
</sec>
</sec>
<sec id="s3" sec-type="results">
<title>3 Results</title>
<sec id="s3_1">
<title>3.1 Environmental Data</title>
<p>Sea surface temperature (SST) within the Heron Island reef lagoon fluctuated between 25.0 and 29.2&#xb0;C over the course of the campaign with an average SST of 27.3 &#xb1; 0.94&#xb0;C. Salinity and pH were on average 37.0 &#xb1; 0.25 ppt and 8.18 &#xb1; 0.19, respectively. Seawater depth ranged from 0.46 to 1.38 m, 10 m wind speed from 0 to 9.20 m s<sup>-1</sup>, windchill from 21.3 to 29.9&#xb0;C, dewpoint from 20.0 to 23.4&#xb0;C and light intensity from 0 to 2000 &#xb5;E m<sup>-2</sup> s<sup>-1</sup>.</p>
</sec>
<sec id="s3_2">
<title>3.2 Sea-to-Air Fluxes and Relationships</title>
<p>Sea-to-air DMS fluxes varied from not-detectable to 69.5 &#xb5;mol m<sup>-2</sup> d<sup>-1</sup> with an average flux of 24.9 &#xb1; 1.81 &#xb5;mol m<sup>-2</sup> d<sup>-1</sup> (mean&#xb1; SE, <italic>n</italic> = 93; <xref ref-type="fig" rid="f1">
<bold>Figure&#xa0;1A</bold>
</xref>). Sea-to-air CH<sub>4</sub> fluxes varied from -0.12 to 3.91 &#xb5;mol m<sup>-2</sup> d<sup>-1</sup> with an average flux of 1.36 &#xb1; 0.11 &#xb5;mol m<sup>-2</sup> d<sup>-1</sup> (<xref ref-type="fig" rid="f1">
<bold>Figure&#xa0;1B</bold>
</xref>). Atmospheric CO<sub>2</sub> and O<sub>2</sub> fluxes varied from -15.4 to 30.7 mmol m<sup>-2</sup> d<sup>-1</sup> and from -188 to 403 mmol m<sup>-2</sup> d<sup>-1</sup>, with mean CO<sub>2</sub> and O<sub>2</sub> fluxes of 0.30 &#xb1; 0.71 and 70.5 &#xb1; 12.3 mmol m<sup>-2</sup> d<sup>-1</sup>, respectively (<xref ref-type="fig" rid="f1">
<bold>Figures&#xa0;1C, D</bold>
</xref>).</p>
<fig id="f1" position="float">
<label>Figure&#xa0;1</label>
<caption>
<p>24-h integrated DMS <bold>(A)</bold>, CH<sub>4</sub> <bold>(B)</bold>, CO<sub>2</sub> <bold>(C)</bold> and O<sub>2</sub> <bold>(D)</bold> fluxes from the Heron Island reef, southern Great Barrier Reef, for the period 4-17 February, 2016. Shaded areas represent hours of darkness.</p>
</caption>
<graphic mimetype="image" mime-subtype="tiff" xlink:href="fmars-09-910441-g001.tif"/>
</fig>
<p>All 24h-integrated sea-to-air fluxes showed a diurnal trend with DMS, CO<sub>2</sub> and CH<sub>4</sub> fluxes being generally greater at night than during the day while O<sub>2</sub> fluxes showed the opposite trend (<xref ref-type="fig" rid="f1">
<bold>Figure&#xa0;1</bold>
</xref>). Sea-to-air CO<sub>2</sub> fluxes showed the most variability during the first hours of sunlight while DMS and O<sub>2</sub> fluxes showed the most variability between dusk and midnight. CH<sub>4</sub> fluxes showed the most variability both at night and during the first hours of sunlight.</p>
<p>Sea-to-air O<sub>2</sub> fluxes negatively correlated with DMS (R<sup>2</sup> = 0.0569, <italic>n</italic> = 93, <italic>p</italic> = 0.02), CH<sub>4</sub> (R<sup>2</sup> = 0.1476, <italic>n</italic> = 93, <italic>p</italic> &lt; 0.001) and CO<sub>2</sub> (R<sup>2 =</sup> 0.346, <italic>n</italic> = 93, <italic>p &lt;</italic>0.00001), although the negative relationship between O<sub>2</sub> and CO<sub>2</sub> was clearly the strongest (<xref ref-type="fig" rid="f2">
<bold>Figure&#xa0;2</bold>
</xref>). Sea-to-air CO<sub>2</sub> and CH<sub>4</sub> fluxes were weakly positively correlated (R<sup>2 =</sup> 0.1709, <italic>n</italic> = 93, <italic>p &lt;</italic>0.001) while CO<sub>2</sub> and DMS fluxes were not significantly correlated (R<sup>2 =</sup> 0.0242, <italic>n</italic> = 93, <italic>p</italic> &gt; 0.05). Sea-to-air DMS and CH<sub>4</sub> fluxes showed the strongest positive correlation (R<sup>2</sup> = 0.7526, <italic>n</italic> = 93; p &lt; 0.00001).</p>
<fig id="f2" position="float">
<label>Figure&#xa0;2</label>
<caption>
<p>Correlations between sea-to-air fluxes of CH<sub>4</sub> and O<sub>2</sub> <bold>(A)</bold>, CO<sub>2</sub> and O<sub>2</sub> <bold>(B)</bold> and CO<sub>2</sub> and CH<sub>4</sub> <bold>(C)</bold> as well as between fluxes of DMS and CH<sub>4</sub> <bold>(D)</bold>, O<sub>2</sub> <bold>(E)</bold> and CO<sub>2</sub> <bold>(F)</bold>. Trendlines, regression equation and R<sup>2</sup> values are displayed for each correlation.</p>
</caption>
<graphic mimetype="image" mime-subtype="tiff" xlink:href="fmars-09-910441-g002.tif"/>
</fig>
<p>Dissolved DMS, CH<sub>4</sub>, CO<sub>2</sub> and O<sub>2</sub> concentrations are presented in the supplementary material (<xref ref-type="supplementary-material" rid="SM1">
<bold>Supplementary Figure&#xa0;2</bold>
</xref>). Because fluxes are calculated based on concentrations and transfer velocity, and the transfer velocity is shared across fluxes, the relationships between dissolved DMS and dissolved CH<sub>4</sub>, CO<sub>2</sub> and O<sub>2</sub> concentrations were also plotted. Dissolved DMS concentrations positively correlated with dissolved CH<sub>4</sub> (R<sup>2</sup> = 0.7706, <italic>n</italic> = 93) and CO<sub>2</sub> (R<sup>2</sup> = 0.2273, <italic>n</italic> = 93) concentrations and negatively correlated with dissolved O<sub>2</sub> concentrations (R<sup>2</sup> = 0.3847, <italic>n</italic> = 93) (<xref ref-type="supplementary-material" rid="SM1">
<bold>Supplementary Figure&#xa0;3</bold>
</xref>, p &lt; 0.00001).</p>
</sec>
<sec id="s3_3">
<title>3.3 Multiple Linear Regressions</title>
<p>The backward elimination process used in the stepwise Multiple Linear Regressions (MLRs) revealed that salinity, pH, depth, wind direction, dewpoint and wind chill were the six main drivers of sea-to-air DMS fluxes and that pH, depth, wind direction, dewpoint, wind chill and light were the six main drivers of CH<sub>4</sub> fluxes (<xref ref-type="table" rid="T1">
<bold>Table&#xa0;1</bold>
</xref>). The linear fit between measured and predicted DMS and CH<sub>4</sub> fluxes exhibited an R<sup>2</sup> of 0.717 and 0.631 (<italic>n</italic> = 93, <italic>p &lt;</italic>0.00001), respectively (<xref ref-type="fig" rid="f3">
<bold>Figures&#xa0;3A, B</bold>
</xref>). The most negative drivers of DMS emissions were wind chill and pH whereas the most positive driver was wind direction (<xref ref-type="fig" rid="f3">
<bold>Figure&#xa0;3C</bold>
</xref>). Similarly, the main negative and positive drivers of CH<sub>4</sub> emissions were pH and wind direction, respectively (<xref ref-type="fig" rid="f3">
<bold>Figure&#xa0;3D</bold>
</xref>). When plotting wind direction (in azimuth degrees) against DMS and CH<sub>4</sub> fluxes (<xref ref-type="supplementary-material" rid="SM1">
<bold>Supplementary Figure&#xa0;4</bold>
</xref>), it appeared that the wind direction leading to the greatest DMS and CH<sub>4</sub> emissions was predominantly at 180&#xb0;, which corresponds to the direction of the dominant southerly trade winds at Heron Island.</p>
<table-wrap id="T1" position="float">
<label>Table&#xa0;1</label>
<caption>
<p>Multiple Linear Regression (MLR) statistics (estimated coefficient, standard error &#x2013; SE; <italic>t</italic> and <italic>p</italic> values), describing sea-to-air DMS and CH<sub>4</sub> fluxes in response to various environmental variables (salinity, pH, depth, wind direction &#x2013; WD, dewpoint &#x2013; DP, windchill &#x2013; WC and light) with interactions, for the best six-variable model using the Akaike Information Criterion (AIC, Supp. Mat.), i.e. lowest number (compare to <xref ref-type="fig" rid="f3">
<bold>Figure&#xa0;3</bold>
</xref>).</p>
</caption>
<table frame="hsides">
<thead>
<tr>
<th valign="top" align="left">DMS</th>
<th valign="top" align="center">Estimate</th>
<th valign="top" align="center">SE </th>
<th valign="top" align="center">t</th>
<th valign="top" align="center">p </th>
<th valign="top" align="center">CH<sub>4</sub>
</th>
<th valign="top" align="center">Estimate</th>
<th valign="top" align="center">SE </th>
<th valign="top" align="center">t</th>
<th valign="top" align="center">p </th>
</tr>
</thead>
<tbody>
<tr>
<td valign="top" align="left">(Intercept)</td>
<td valign="top" align="center">19054</td>
<td valign="top" align="center">2785</td>
<td valign="top" align="center">6.841</td>
<td valign="top" align="center">
<bold>&lt;0.001</bold>
</td>
<td valign="top" align="left">(Intercept)</td>
<td valign="top" align="center">999.7</td>
<td valign="top" align="center">174.9</td>
<td valign="top" align="center">5.717</td>
<td valign="top" align="center">
<bold>&lt;0.001</bold>
</td>
</tr>
<tr>
<td valign="top" align="left">salinity</td>
<td valign="top" align="center">22.42</td>
<td valign="top" align="center">5.333</td>
<td valign="top" align="center">4.203</td>
<td valign="top" align="center">
<bold>&lt;0.001</bold>
</td>
<td valign="top" align="left">pH</td>
<td valign="top" align="center">-122.9</td>
<td valign="top" align="center">21.27</td>
<td valign="top" align="center">-5.778</td>
<td valign="top" align="center">
<bold>&lt;0.001</bold>
</td>
</tr>
<tr>
<td valign="top" align="left">pH</td>
<td valign="top" align="center">-2419</td>
<td valign="top" align="center">348.3</td>
<td valign="top" align="center">-6.944</td>
<td valign="top" align="center">
<bold>&lt;0.001</bold>
</td>
<td valign="top" align="left">depth</td>
<td valign="top" align="center">19.07</td>
<td valign="top" align="center">5.476</td>
<td valign="top" align="center">3.483</td>
<td valign="top" align="center">
<bold>0.001</bold>
</td>
</tr>
<tr>
<td valign="top" align="left">depth</td>
<td valign="top" align="center">211.4</td>
<td valign="top" align="center">88.35</td>
<td valign="top" align="center">2.393</td>
<td valign="top" align="center">
<bold>0.019</bold>
</td>
<td valign="top" align="left">WD</td>
<td valign="top" align="center">0.025</td>
<td valign="top" align="center">0.005</td>
<td valign="top" align="center">4.679</td>
<td valign="top" align="center">
<bold>&lt;0.001</bold>
</td>
</tr>
<tr>
<td valign="top" align="left">WD</td>
<td valign="top" align="center">0.321</td>
<td valign="top" align="center">0.078</td>
<td valign="top" align="center">4.132</td>
<td valign="top" align="center">
<bold>&lt;0.001</bold>
</td>
<td valign="top" align="left">DP</td>
<td valign="top" align="center">-44.22</td>
<td valign="top" align="center">7.805</td>
<td valign="top" align="center">-5.666</td>
<td valign="top" align="center">
<bold>&lt;0.001</bold>
</td>
</tr>
<tr>
<td valign="top" align="left">DP</td>
<td valign="top" align="center">-651.5</td>
<td valign="top" align="center">121.1</td>
<td valign="top" align="center">-5.382</td>
<td valign="top" align="center">
<bold>&lt;0.001</bold>
</td>
<td valign="top" align="left">WC</td>
<td valign="top" align="center">0.371</td>
<td valign="top" align="center">0.199</td>
<td valign="top" align="center">1.868</td>
<td valign="top" align="center">0.065</td>
</tr>
<tr>
<td valign="top" align="left">WC</td>
<td valign="top" align="center">-203.1</td>
<td valign="top" align="center">56.71</td>
<td valign="top" align="center">-3.581</td>
<td valign="top" align="center">
<bold>0.001</bold>
</td>
<td valign="top" align="left">light</td>
<td valign="top" align="center">-0.024</td>
<td valign="top" align="center">0.010</td>
<td valign="top" align="center">-2.476</td>
<td valign="top" align="center">
<bold>0.015</bold>
</td>
</tr>
<tr>
<td valign="top" align="left">pH:DP</td>
<td valign="top" align="center">79.02</td>
<td valign="top" align="center">14.73</td>
<td valign="top" align="center">5.366</td>
<td valign="top" align="center">
<bold>&lt;0.001</bold>
</td>
<td valign="top" align="left">pH:DP</td>
<td valign="top" align="center">5.371</td>
<td valign="top" align="center">0.948</td>
<td valign="top" align="center">5.664</td>
<td valign="top" align="center">
<bold>&lt;0.001</bold>
</td>
</tr>
<tr>
<td valign="top" align="left">pH:WC</td>
<td valign="top" align="center">24.78</td>
<td valign="top" align="center">7.047</td>
<td valign="top" align="center">3.517</td>
<td valign="top" align="center">
<bold>0.001</bold>
</td>
<td valign="top" align="left">pH:light</td>
<td valign="top" align="center">0.003</td>
<td valign="top" align="center">0.001</td>
<td valign="top" align="center">2.462</td>
<td valign="top" align="center">
<bold>0.016</bold>
</td>
</tr>
<tr>
<td valign="top" align="left">depth:WD</td>
<td valign="top" align="center">-0.312</td>
<td valign="top" align="center">0.090</td>
<td valign="top" align="center">-3.474</td>
<td valign="top" align="center">
<bold>0.001</bold>
</td>
<td valign="top" align="left">depth:WD</td>
<td valign="top" align="center">-0.027</td>
<td valign="top" align="center">0.006</td>
<td valign="top" align="center">-4.507</td>
<td valign="top" align="center">
<bold>&lt;0.001</bold>
</td>
</tr>
<tr>
<td valign="top" align="left">depth:WC</td>
<td valign="top" align="center">-6.458</td>
<td valign="top" align="center">3.482</td>
<td valign="top" align="center">-1.854</td>
<td valign="top" align="center">0.067</td>
<td valign="top" align="left">depth:WC</td>
<td valign="top" align="center">-0.579</td>
<td valign="top" align="center">0.212</td>
<td valign="top" align="center">-2.734</td>
<td valign="top" align="center">
<bold>0.008</bold>
</td>
</tr>
</tbody>
</table>
<table-wrap-foot>
<p>Significant <italic>p</italic> values appear in bold for a level of significance of &#x2264; 0.05.</p>
</table-wrap-foot>
</table-wrap>
<fig id="f3" position="float">
<label>Figure&#xa0;3</label>
<caption>
<p>Linear fits through <italic>in situ</italic> and predicted sea-to-air DMS (<bold>A</bold>, R<sup>2</sup> = 0.717) and CH<sub>4</sub> (<bold>B</bold>, R<sup>2</sup> = 0.631) fluxes by the stepwise Multiple Linear Regression (MLR) model with the lowest Akaike Information Criterion (AIC) with six main variables, and resulting main effect sizes of salinity, pH, depth, wind direction (WD), Dewpoint (DP) and Wind Chill (WC) for DMS fluxes <bold>(C)</bold> and of pH, depth, WD, DP and WC and light for CH<sub>4</sub> fluxes <bold>(D)</bold> (compare to <xref ref-type="table" rid="T1">
<bold>Table&#xa0;1</bold>
</xref>).</p>
</caption>
<graphic mimetype="image" mime-subtype="tiff" xlink:href="fmars-09-910441-g003.tif"/>
</fig>
</sec>
<sec id="s3_4">
<title>3.4 Reef Production</title>
<p>The DMS reef production exhibited positive values at all times, with a few sporadic spikes around peak hours of sunlight (~ 11:00) and in the middle of the night (~23:00) (<xref ref-type="fig" rid="f4">
<bold>Figure&#xa0;4A</bold>
</xref>). Although an order of magnitude lower, the CH<sub>4</sub> reef production was also positive at all times but with greater values recorded at night (<xref ref-type="fig" rid="f4">
<bold>Figure&#xa0;4B</bold>
</xref>). The CO<sub>2</sub> reef production was positive at night and for the first half of the day but negative from about 12:00 to 20:00 (<xref ref-type="fig" rid="f4">
<bold>Figure&#xa0;4C</bold>
</xref>). As expected, the O<sub>2</sub> reef production was essentially positive during the day until dusk, and negative at night (<xref ref-type="fig" rid="f4">
<bold>Figure&#xa0;4D</bold>
</xref>).</p>
<fig id="f4" position="float">
<label>Figure&#xa0;4</label>
<caption>
<p>24h-integrated reef production (RP) for DMS <bold>(A)</bold>, CH<sub>4</sub> <bold>(B)</bold>, CO<sub>2</sub> <bold>(C)</bold> and O<sub>2</sub> <bold>(D)</bold> calculated around each low-tide period. Shaded areas represent hours of darkness.</p>
</caption>
<graphic mimetype="image" mime-subtype="tiff" xlink:href="fmars-09-910441-g004.tif"/>
</fig>
</sec>
<sec id="s3_5">
<title>3.5 Particle Number Concentrations and Their Relationship With Wind Speed and DMS Exchange</title>
<p>Over the course of the study, intermediate (&lt; 0.5-2.5 &#xb5;m) and large (&gt; 2.5 &#xb5;m) aerosol particle number concentrations averaged 5.51 x 10<sup>6</sup> &#xb1; 1.73 x 10<sup>5</sup> m<sup>-3</sup> and 1.15 x 10<sup>6</sup> &#xb1; 4.63 x 10<sup>4</sup> m<sup>-3</sup>, respectively (<xref ref-type="fig" rid="f5">
<bold>Figures&#xa0;5A, B</bold>
</xref>). Particle numbers in the 0.5&#xb5;m-2.5 &#xb5;m portion size fraction were highest in the early morning (7:00 and 11:00) and again at the end of the day around and following sunset (from 18:30 to 20:00). Particle numbers in the &gt; 2.5 &#xb5;m size fraction occurred slightly later in the morning (~11:00), early afternoon (11:00 to 15:00) and in the evening between 18:30 and 20:00.</p>
<fig id="f5" position="float">
<label>Figure&#xa0;5</label>
<caption>
<p>24h-integrated abundance of intermediate (0.5-2.5 &#xb5;m) <bold>(A)</bold> and large (&gt;2.5 &#xb5;m) <bold>(B)</bold> aerosol particles and their relationships with wind speed <bold>(C, D)</bold> and sea-to-air DMS fluxes <bold>(E, F)</bold>, respectively. Shaded areas represent hours of darkness.</p>
</caption>
<graphic mimetype="image" mime-subtype="tiff" xlink:href="fmars-09-910441-g005.tif"/>
</fig>
<p>Wind speed positively correlated with the abundance of intermediate (R<sup>2</sup> = 0.3337, <italic>n</italic> = 93, <italic>p</italic> &lt; 0.0001) and large (R<sup>2</sup> = 0.1424, <italic>n</italic> = 93, <italic>p</italic> = 0.0002) aerosol particles (<xref ref-type="fig" rid="f5">
<bold>Figures&#xa0;5C, D</bold>
</xref>). Sea-to-air DMS fluxes also positively correlated with the abundance of intermediate (R<sup>2</sup> = 0.1669, <italic>n</italic> = 93, <italic>p</italic> = 0.0001) and large (R<sup>2</sup> = 0.0869, <italic>n</italic> = 93, <italic>p</italic> = 0.004) aerosol particles (<xref ref-type="fig" rid="f5">
<bold>Figures&#xa0;5E, F</bold>
</xref>).</p>
</sec>
</sec>
<sec id="s4" sec-type="discussion">
<title>4 Discussion</title>
<sec id="s4_1">
<title>4.1 Flux Estimations</title>
<p>DMS fluxes reported in this study (Min = not-detectable, Max = 69.5 &#xb5;mol m<sup>-2</sup> d<sup>-1</sup>, Mean = 24.9 &#xb1; 1.81 &#xb5;mol m<sup>-2</sup> d<sup>-1</sup>, <italic>n</italic> = 93) fell within the range of previously reported sea-to-air DMS fluxes for 5 coral reef systems across the Great Barrier Reef, which varied from not-detectable to 153 &#xb5;mol m<sup>-2</sup> d<sup>-1</sup> in the austral summer wet season (<xref ref-type="bibr" rid="B20">Jones et&#xa0;al., 2018</xref>). However, seasonal DMS fluxes recorded in the current study were about five and four times greater on average than the 2012 summer wet season study conducted on Heron Island (5.0 &#xb5;mol m<sup>-2</sup> d<sup>-1</sup>
<italic>, n</italic> = 651) (<xref ref-type="bibr" rid="B50">Swan et&#xa0;al., 2017</xref>) and the average DMS fluxes reported by <xref ref-type="bibr" rid="B20">Jones et&#xa0;al. (2018)</xref> (6.4 &#xb5;mol m<sup>-2</sup> d<sup>-1</sup>, <italic>n</italic> = 237), respectively. Since DMS<sub>a</sub> (mean &#xb1; SD) at Heron Island in the 2012 and 2016 summers were similar (i.e. 3.9 &#xb1; 1.5, <italic>n</italic> = 651, and 3.7 &#xb1; 0.8, <italic>n</italic> = 761 nmol m<sup>-3</sup>, respectively, data not shown), the high fluxes in this study most likely result from temporally elevated DMS production in the Heron Island reef lagoon in the year 2016 or on the section of the Heron Island reef flat where seawater samples were collected. The significant differences in the average DMS fluxes for the summers of 2012 and 2016 at Heron Island might also reflect differences in the employed flux calculation (photochemical ambient mass balance approach used by <xref ref-type="bibr" rid="B50">Swan et&#xa0;al. (2017)</xref> as opposed to the gradient method flux calculation used in this study). Similarly, <xref ref-type="bibr" rid="B20">Jones et&#xa0;al. (2018)</xref> used the LM86 gradient method flux parameterisation, which was shown to give much lower flux estimates than the other gradient method flux parameterisations used in the current study (see <xref ref-type="supplementary-material" rid="SM1">
<bold>Supplementary Table 1</bold>
</xref>), hence indicating that the approach employed can lead to significantly different values. The estimated flux difference might also reflect the limitations of the non-automated VG-CL instrument used in this study, which ultimately led to preferential DMS<sub>w</sub> sampling during the day and evenings, with a lack of night-time measurements to match with the continuous DMS<sub>a</sub> measurements.</p>
<p>Sea-to-air fluxes for CH<sub>4</sub> (Min = &#x2212;0.12 &#xb5;mol m<sup>-2</sup> d<sup>-1</sup>, Max = 3.91 &#xb5;mol m<sup>-2</sup> d<sup>-1</sup>, mean = 1.36 &#xb1; 1.03 mmol m<sup>-2</sup> d<sup>-1</sup>) and CO<sub>2</sub> (Min = &#x2212;15.4, Max = 30.7 mmol m<sup>-2</sup> d<sup>-1</sup>, mean = 0.30 mmol m<sup>-2</sup> d<sup>-1</sup>) were consistent with previously reported water-air fluxes for the Great Barrier Reef (3.4 &#xb1; 0.1 &#xb5;mol m<sup>-2</sup> d<sup>-1</sup> (<xref ref-type="bibr" rid="B36">O&#x2019;Reilly et&#xa0;al., 2015</xref>) and 2.2 &#xb1; 0.5 &#xb5;mol m<sup>-2</sup> d<sup>-1</sup> (<xref ref-type="bibr" rid="B43">Reading et&#xa0;al., 2021</xref>) for CH<sub>4</sub>; &#x2212;5.4 &#xb1; 0.8 mmol m<sup>-2</sup> d<sup>-1</sup> (<xref ref-type="bibr" rid="B36">O&#x2019;Reilly et&#xa0;al., 2015</xref>), 1.44 &#xb1; 0.15 mmol m<sup>&#x2212;2</sup> d<sup>&#x2212;1</sup> (<xref ref-type="bibr" rid="B26">L&#xf8;nborg et&#xa0;al., 2019</xref>) and 1.9 &#xb1; 0.4 mmol m<sup>-2</sup> d<sup>-1</sup> (<xref ref-type="bibr" rid="B43">Reading et&#xa0;al., 2021</xref>) for CO<sub>2</sub>).</p>
<p>Sea-to-air O<sub>2</sub> fluxes in this study (Min = &#x2212;188 mmol m<sup>-2</sup> d<sup>-1</sup>, Max = 403 mmol m<sup>-2</sup> d<sup>-1</sup>, mean = 70 &#xb1; 12 mmol m<sup>-2</sup> d<sup>-1</sup>) were similar to water-air fluxes reported for a Puerto Rican coral reef, with rates varying between &#x2212;285 and 329 mmol m<sup>-2</sup> d<sup>-1</sup> (<xref ref-type="bibr" rid="B32">McGillis et&#xa0;al., 2011</xref>). However, they were rather low compared to O<sub>2</sub> fluxes reported for another coral reef system in the Florida Keys, (Min = &#x2212;450 mmol m<sup>-2</sup> d<sup>-1</sup>, Max = 4500 mmol m<sup>-2</sup> d<sup>-1</sup>) (<xref ref-type="bibr" rid="B30">Long et&#xa0;al., 2013</xref>), which most likely reflects differences between the phototrophic communities of different reef systems (e.g. algal versus coral cover, phytoplankton composition).</p>
</sec>
<sec id="s4_2">
<title>4.2 The Interplay Between DMS and CH<sub>4</sub>
</title>
<p>The strong positive correlation between water-air DMS and CH<sub>4</sub> fluxes (R<sup>2</sup> = 0.7526) suggests that DMS and CH<sub>4</sub> emissions from the Heron Island reef lagoon are closely linked. Further to this observation, the MLR analysis revealed that sea-to-air DMS and CH<sub>4</sub> fluxes were both driven by pH, depth, wind direction, dewpoint and wind chill. This indicates that DMS and CH<sub>4</sub> fluxes are driven by very similar environmental factors, thus potentially explaining part of the correlation between DMS and CH<sub>4</sub> emissions at the Heron Island reef lagoon. Dissolved concentrations of DMS and CH<sub>4</sub> were also strongly correlated (<bold>Supplementary Figure 3</bold>), which indicates that the production of DMS and CH<sub>4</sub> in this reef system is also intimately linked. In contrast there was no clear correlation between the RPs of DMS and CH<sub>4</sub>, which suggests that DMS and CH<sub>4</sub> were subject to different accumulation rates and thus to different production and/or degradation processes.</p>
<p>DMS production mainly relies on the enzymatic cleavage of DMSP in the water column (<xref ref-type="bibr" rid="B46">Sim&#xf3;, 2001</xref>) while methanogenesis mainly depends on the conversion of CO<sub>2</sub> and acetate into CH<sub>4</sub> under anaerobic conditions (<xref ref-type="bibr" rid="B29">Liu and Whitman, 2008</xref>), which most likely occurs in marine sediments in coral reef ecosystems (<xref ref-type="bibr" rid="B12">Deschaseaux et&#xa0;al., 2019</xref>; <xref ref-type="bibr" rid="B43">Reading et&#xa0;al., 2021</xref>). The main sinks of dissolved DMS are expected to be biological and photochemical oxidation (<xref ref-type="bibr" rid="B9">del Valle et&#xa0;al., 2009</xref>) as well as emission fluxes from the water column to the atmosphere (<xref ref-type="bibr" rid="B27">Lana et&#xa0;al., 2011</xref>). Similarly, oceanic emissions (<xref ref-type="bibr" rid="B53">Weber et&#xa0;al., 2019</xref>) and microbial oxidation to CO<sub>2</sub> through both aerobic and anaerobic pathways (<xref ref-type="bibr" rid="B37">Pain et&#xa0;al., 2019</xref>) are considered the main sinks of dissolved CH<sub>4</sub> in marine systems. However, the rate and magnitude of DMS and CH<sub>4</sub> sinks rely on different degradation processes (e.g. microbial communities, vertical distribution in the water column). For instance, the magnitude of the aerobic and anaerobic CH<sub>4</sub> oxidation sinks is dictated by oxygen gradients and groundwater residence time, respectively (<xref ref-type="bibr" rid="B37">Pain et&#xa0;al., 2019</xref>). The different sources and sinks of DMS and CH<sub>4</sub> in coral reef systems thus most likely explain the divergence in correlation between DMS and CH<sub>4</sub> sea-to-air emissions on one hand and the RPs of DMS and CH<sub>4</sub> on the other hand.</p>
<p>At the Heron Island reef lagoon, negative correlations were found between dark DMS and CH<sub>4</sub> fluxes from permeable carbonate coral reef sediments to the water column (<xref ref-type="bibr" rid="B12">Deschaseaux et&#xa0;al., 2019</xref>), suggesting that part of the DMS produced in coral reef sediments was degraded to CH<sub>4</sub> under dark anoxic conditions, most likely by anaerobic methanogens (<xref ref-type="bibr" rid="B23">Kiene and Visscher, 1987</xref>). However, CH<sub>4</sub> production can also occur under aerobic conditions and across all living organisms, including marine phytoplankton (<xref ref-type="bibr" rid="B24">Klintzsch et&#xa0;al., 2019</xref>; <xref ref-type="bibr" rid="B13">Ernst et&#xa0;al., 2022</xref>). As such, DMS-to-CH<sub>4</sub> hydrolysis may not only occurs in permeable carbonate coral reef sediments, but also in reef waters through phytoplankton activity and possibly within the coral tissue, where DMS plays a major role in structuring coral-associated bacterial communities (<xref ref-type="bibr" rid="B40">Raina et&#xa0;al., 2010</xref>).</p>
<p>Growing evidence shows that organic compounds containing sulfur- bonded methyl groups such as DMS are a source of CH<sub>4</sub> under both anaerobic and aerobic conditions (<xref ref-type="bibr" rid="B29">Liu and Whitman, 2008</xref>; <xref ref-type="bibr" rid="B13">Ernst et&#xa0;al., 2022</xref>), with CH<sub>4</sub> production by certain bacteria being enhanced in the presence of reactive oxygen species under oxidative stress (<xref ref-type="bibr" rid="B13">Ernst et&#xa0;al., 2022</xref>). DMS concentrations in marine algae and corals also increase under oxidative stress due to DMS being used as an antioxidant (<xref ref-type="bibr" rid="B48">Sunda et&#xa0;al., 2002</xref>; <xref ref-type="bibr" rid="B10">Deschaseaux et&#xa0;al., 2014</xref>). This suggests that the increase in CH<sub>4</sub> production might be due to more sulfur-methylated compounds made readily available to methylotrophs in various types of organisms.</p>
<p>It was estimated that DMS contributes up to 28% of CH<sub>4</sub> production in various marine systems (<xref ref-type="bibr" rid="B21">Kiene, 1988</xref>; <xref ref-type="bibr" rid="B15">Florez-Leiva et&#xa0;al., 2013</xref>), which could well be the case for coral reef ecosystems. At the Heron Island reef lagoon, it was estimated that a small portion (~6.5%) of the CH<sub>4</sub> produced in coral reef sediments under dark anoxic conditions might originate from DMS (<xref ref-type="bibr" rid="B12">Deschaseaux et&#xa0;al., 2019</xref>). Here, the slope of the regression between DMS and CH<sub>4</sub> indicates that 0.05 mole of CH<sub>4</sub> is emitted for each mole of DMS being emitted to the atmosphere. This shows that sea-to-air CH<sub>4</sub> emissions from the Heron Island reef lagoon represents 5% of that of DMS, which is consistent with the average sea-to-air DMS (24.9 &#xb1; 1.81 &#xb5;mol m<sup>-2</sup> d<sup>-1</sup>) and CH<sub>4</sub> (1.36 &#xb1; 0.11 &#xb5;mol m<sup>-2</sup> d<sup>-1</sup>) fluxes reported in this study. However, without using isotopic tracers, we cannot draw conclusions on the actual portion of CH<sub>4</sub> emissions from coral reef systems that actually originate from DMS hydrolysis.</p>
</sec>
<sec id="s4_3">
<title>4.3 Drivers of DMS and CH<sub>4</sub> in Coral Reef Systems</title>
<p>In addition to pH, depth, wind direction, dewpoint and wind chill, DMS emissions were also positively driven by salinity. These findings could be counter intuitive given that the most intense plume of DMS measured over the Heron Island reef occurred in the winter of 2013 at low tide when rainfall on the aerially exposed reef apparently caused a combined hypo-salinity osmotic and hypo-thermic temperature shock to the coral (<xref ref-type="bibr" rid="B50">Swan et&#xa0;al., 2017</xref>). However, salinity in this study only ranged from 36.4 to 37.4 ppt, and thus DMS emissions under rainfall at low tide was not captured. Nevertheless, it could also be that it was not only low salinity that led to high DMS emissions reported by <xref ref-type="bibr" rid="B50">Swan et&#xa0;al. (2017)</xref>, but also temperature stress and/or other rain-induced environmental conditions. For instance, rain increases transfer velocity (<xref ref-type="bibr" rid="B17">Ho et&#xa0;al., 1997</xref>), which could explain the higher emissions in <xref ref-type="bibr" rid="B50">Swan et&#xa0;al. (2017)</xref> under rainfall at low tide.</p>
<p>Similarly, in addition to pH, depth, wind direction, dewpoint and wind chill, CH<sub>4</sub> emissions were also negatively affected by light whereas previous studies show that CH<sub>4</sub> production by phytoplankton was accentuated under increased light conditions (<xref ref-type="bibr" rid="B25">Klintzsch et&#xa0;al., 2020</xref>). Given that light mainly influences photosynthesis and O<sub>2</sub> production in biological systems, this data suggests that light-driven O<sub>2</sub> production might negatively impact CH<sub>4</sub> production or lead to enhanced CH<sub>4</sub> oxidation in coral reefs. This is consistent with sea-to-air O<sub>2</sub> fluxes being negatively correlated with both CH<sub>4</sub> and CO<sub>2</sub> in this study, with CO<sub>2</sub> being a precursor of CH<sub>4</sub> production (<xref ref-type="bibr" rid="B29">Liu and Whitman, 2008</xref>). Although CH<sub>4</sub> can originate from various biogenic sources in the presence of oxygen (<xref ref-type="bibr" rid="B13">Ernst et&#xa0;al., 2022</xref>), it could be that the main source of CH<sub>4</sub> in coral reef systems are methanogen-rich permeable carbonate sediments (<xref ref-type="bibr" rid="B12">Deschaseaux et&#xa0;al., 2019</xref>), which are productive under dark anoxic conditions.</p>
<p>Maximum dissolved DMS and DMSP concentrations in coral reef systems coincide with low pH, especially over areas dominated by seagrass and macroalgae (<xref ref-type="bibr" rid="B3">Burdett et&#xa0;al., 2013</xref>), which is consistent with pH negatively affecting DMS emissions in the current study. Coral-reef DMS emissions are thus expected to increase under low pH conditions, possibly due to macroalgae using DMSP to maintain metabolic functions during periods of low carbonate saturation state (<xref ref-type="bibr" rid="B3">Burdett et&#xa0;al., 2013</xref>). Sea-to-air CH<sub>4</sub> fluxes at Heron Island were also negatively correlated with pH, which suggests that ocean acidification may increase CH<sub>4</sub> emissions in coral reef systems, possibly due to low pH enhancing organic matter degradation in coral reefs like it is the case in seagrass sediments (<xref ref-type="bibr" rid="B42">Ravaglioli et&#xa0;al., 2020</xref>).</p>
<p>Spikes in DMS emissions at the Heron Island reef lagoon were previously detected at low tide generally under low wind speeds &lt; 2 m s<sup>-1</sup> (<xref ref-type="bibr" rid="B50">Swan et&#xa0;al., 2017</xref>), which agrees with depth being a negative driver of DMS emissions in this study. On the other hand, it is unknown whether dewpoint and windchill have ever been considered as environmental factors driving DMS and CH<sub>4</sub> emissions in marine systems, although it seems that low dewpoint and air temperatures coincided with high DMS and CH<sub>4</sub> emissions at the Heron Island reef system. This suggests that air temperature also plays a role in the gas transfer velocity of DMS and CH<sub>4</sub>, most likely as it influences water temperature and thus the temperature-dependent gas solubility of these two compounds.</p>
<p>DMS and CH<sub>4</sub> emissions were highest under southerly winds, which travelled over the Heron Island&#x2019;s reef and the adjacent large Wistari reef, directly south of our sampling site. This indicates that Wistari reef is possibly the major source of coral-reef-derived DMS<sub>a</sub> measured at Heron Island and that coral reefs are a more predominant source of DMS and CH<sub>4</sub> than the surrounding ocean.</p>
</sec>
<sec id="s4_4">
<title>4.4 DMS and Climate in Coral Reef Systems</title>
<p>Although there is insufficient information to attribute the particle counts in this study to new particle formation, because the measured size ranges are far above that of new nanoparticles (<xref ref-type="bibr" rid="B6">Clarke et&#xa0;al., 2006</xref>), it was interesting to see that sea-to-air DMS fluxes positively correlated with intermediate (0.5-2.5 &#xb5;m) and large (&gt; 2.5 &#xb5;m) particles, and that a stronger correlation occurred between DMS emissions and the abundance of particles in the intermediate size range. This likely indicates that DMS oxidation products possibly contributed to the growth of existing particles within the 0.5-2.5 &#xb5;m measured size range, which are suspected to be predominantly sea spray aerosols (SSA) (<xref ref-type="bibr" rid="B39">Quinn et&#xa0;al., 2015</xref>). Given that number concentrations of intermediate size particles were correlated with wind speed (R<sup>2</sup> = 0.3337, <xref ref-type="fig" rid="f5">
<bold>Figure&#xa0;5C</bold>
</xref>) and that wind speed is a covariate in DMS flux, the observed correlation is expected to be linked to wind speed, which exchanges more DMS and SSA from the ocean. Given that coral-reef derived DMS and CH<sub>4</sub> emissions could be linked, with a small portion of DMS being hydrolysed to CH<sub>4</sub> in the water column, and that CH<sub>4</sub> is a GHG with a stronger greenhouse potential than that of CO<sub>2</sub> (<xref ref-type="bibr" rid="B45">Shine et&#xa0;al., 2005</xref>), it is important to consider both dissolved DMS and CH<sub>4</sub> when predicting BVOC and GHG emissions from marine systems.</p>
</sec>
</sec>
<sec id="s5">
<title>5 Conclusion</title>
<p>To our knowledge, this study is the first to simultaneously measure and report sea-to-air DMS fluxes alongside sea-to-air CH<sub>4</sub> fluxes in a coral reef ecosystem. Depth, pH, wind direction, dewpoint and wind chill were common drivers of DMS and CH<sub>4</sub> emissions at Heron Island, a coral reef system on the southern Great Barrier Reef. Additionally, salinity was a positive driver of DMS emissions while light negatively affected sea-to-air CH<sub>4</sub> fluxes. This research also showed the strong correlation that exists between DMS and CH<sub>4</sub> emissions at Heron Island. Although it is not possible at this stage to estimate the portion of CH<sub>4</sub> that derives from DMS hydrolysis, it is clear that DMS and CH<sub>4</sub> emissions from the Heron Island reef are intimately linked, with potential consequences on ocean warming. DMS emissions were well correlated with the abundance of intermediate size particles (0.5-2.5 &#xb5;m), which indicates that DMS contributes to the growth of existing aerosol particles, which could eventually form cloud condensation nuclei and induce cloud-mediated cooling on a local scale. This study highlights the complexity of BVOC and GHG co-emissions and the potential impact they may have on the regional climate of the Great Barrier Reef.</p>
</sec>
<sec id="s6" sec-type="data-availability">
<title>Data Availability Statement</title>
<p>The data collected for this study has been made publicly available from the Southern Cross University online repository at: <uri xlink:href="https://doi.org/https://doi.org/10.4226/47/59c460fbe8322">https://doi.org/https://doi.org/10.4226/47/59c460fbe8322</uri> and <uri xlink:href="https://doi.org/10.25918/data.193">https://doi.org/10.25918/data.193</uri>.</p>
</sec>
<sec id="s7" sec-type="author-contributions">
<title>Author Contributions</title>
<p>ED, BE, GJ, HS and DM conceptualised the experimental design. ED conducted the DMS<sub>w</sub> analysis, DMS<sub>w</sub> data processing, all data compiling, and manuscript writing. HS conducted the analysis and processing of DMS<sub>a</sub> and particle number concentrations. DM conducted the analysis and processing of CH<sub>4</sub> and CO<sub>2</sub> data. ED and DM conducted the flux calculations for DMS and CH<sub>4</sub>, CO<sub>2</sub> and O<sub>2</sub>, respectively. KS conducted the MLR analysis and data processing on MATLAB. EK and KT designed the VG-CL and provided analytical support in the field. BE and GJ funded this research. All authors contributed to the article and approved the submitted version.</p>
</sec>
<sec id="s8" sec-type="funding-information">
<title>Funding</title>
<p>This research was funded by the ARC Discovery Project grants DP150102092 (recipient BE), &#x201c;Dissolution of calcium carbonate in sediments in an acidifying ocean&#x201d; and DP150101649 (recipient GJ), &#x201c;The Great Barrier Reef as a significant source of climatically relevant aerosol particles&#x201d;.</p>
</sec>
<sec id="s9" 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="s10" 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>
</body>
<back>
<ack>
<title>Acknowledgments</title>
<p>We would like to thank the staff at the Heron Island Research Station for their assistance.</p>
</ack>
<sec id="s11" 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.2022.910441/full#supplementary-material">https://www.frontiersin.org/articles/10.3389/fmars.2022.910441/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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