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  <front>
    <journal-meta><journal-id journal-id-type="publisher">OS</journal-id><journal-title-group>
    <journal-title>Ocean Science</journal-title>
    <abbrev-journal-title abbrev-type="publisher">OS</abbrev-journal-title><abbrev-journal-title abbrev-type="nlm-ta">Ocean Sci.</abbrev-journal-title>
  </journal-title-group><issn pub-type="epub">1812-0792</issn><publisher>
    <publisher-name>Copernicus Publications</publisher-name>
    <publisher-loc>Göttingen, Germany</publisher-loc>
  </publisher></journal-meta>
    <article-meta>
      <article-id pub-id-type="doi">10.5194/os-22-609-2026</article-id><title-group><article-title>Modelling seawater <inline-formula><mml:math id="M1" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2</sub> and pH in the Canary Islands region based on satellite measurements and machine learning techniques</article-title><alt-title>Modelling seawater <inline-formula><mml:math id="M3" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2</sub> and pH in the Canary Islands region</alt-title>
      </title-group>
      <contrib-group>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Sánchez-Mendoza</surname><given-names>Irene</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="yes" rid="aff1">
          <name><surname>González-Dávila</surname><given-names>Melchor</given-names></name>
          <email>melchor.gonzalez@ulpgc.es</email>
        <ext-link>https://orcid.org/0000-0003-3230-8985</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>González-Santana</surname><given-names>David</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Curbelo-Hernández</surname><given-names>David</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-9826-7437</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Estupiñán-Santana</surname><given-names>David</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>González</surname><given-names>Aridane G.</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-5637-8841</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Santana-Casiano</surname><given-names>J. Magdalena</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-7930-7683</ext-link></contrib>
        <aff id="aff1"><label>1</label><institution>Instituto de Oceanografía y Cambio Global, QUIMA, Universidad de Las Palmas de Gran Canaria, 35017 Las Palmas de Gran Canaria, Spain</institution>
        </aff>
      </contrib-group>
      <author-notes><corresp id="corr1">Melchor González-Dávila (melchor.gonzalez@ulpgc.es)</corresp></author-notes><pub-date><day>12</day><month>February</month><year>2026</year></pub-date>
      
      <volume>22</volume>
      <issue>1</issue>
      <fpage>609</fpage><lpage>628</lpage>
      <history>
        <date date-type="received"><day>30</day><month>July</month><year>2025</year></date>
           <date date-type="rev-request"><day>28</day><month>August</month><year>2025</year></date>
           <date date-type="rev-recd"><day>22</day><month>December</month><year>2025</year></date>
           <date date-type="accepted"><day>5</day><month>January</month><year>2026</year></date>
      </history>
      <permissions>
        <copyright-statement>Copyright: © 2026 Irene Sánchez-Mendoza et al.</copyright-statement>
        <copyright-year>2026</copyright-year>
      <license license-type="open-access"><license-p>This work is licensed under the Creative Commons Attribution 4.0 International License. To view a copy of this licence, visit <ext-link ext-link-type="uri" xlink:href="https://creativecommons.org/licenses/by/4.0/">https://creativecommons.org/licenses/by/4.0/</ext-link></license-p></license></permissions><self-uri xlink:href="https://os.copernicus.org/articles/os-22-609-2026.html">This article is available from https://os.copernicus.org/articles/os-22-609-2026.html</self-uri><self-uri xlink:href="https://os.copernicus.org/articles/os-22-609-2026.pdf">The full text article is available as a PDF file from https://os.copernicus.org/articles/os-22-609-2026.pdf</self-uri>
      <abstract><title>Abstract</title>

      <p id="d2e166">Recent advancements in remote sensing systems, combined with new machine-learning model-fitting algorithms, have enabled the estimation of seawater carbon dioxide partial pressure (<inline-formula><mml:math id="M5" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub>) and pH (pH<sub>T,is</sub>) in the waters around the Canary Islands (13–19° W; 27–30° N). Continuous time-series data collected from moored buoys and Voluntary Observing Ships (VOS) between 2019 and 2024 were used to train and validate the models, providing a robust observational basis for satellite-derived estimates.</p>

      <p id="d2e204">Among all models tested, bootstrap aggregation (<italic>bagging</italic>) performed best, achieving an RMSE of 2.0 <inline-formula><mml:math id="M8" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M9" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>&gt;</mml:mo><mml:mn mathvariant="normal">0.99</mml:mn></mml:mrow></mml:math></inline-formula>) for <inline-formula><mml:math id="M10" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and 0.002 for pH<sub>T,is</sub>. <italic>Multilinear regression (MLR)</italic>, <italic>neural networks (NN)</italic> and <italic>categorical boosting</italic> <italic>(CatBoost</italic>) also showed good predictive skill, with RMSE values between 5.4 and 10 <inline-formula><mml:math id="M13" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> for <inline-formula><mml:math id="M14" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> (360–481 <inline-formula><mml:math id="M16" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula>) and 0.004–0.008 for pH<sub>T,is</sub> (7.97–8.07). Using the most reliable model, we identified an increasing trend in <inline-formula><mml:math id="M18" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> of <inline-formula><mml:math id="M20" display="inline"><mml:mrow><mml:mn mathvariant="normal">3.51</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">0.31</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M21" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="normal">yr</mml:mi></mml:mrow></mml:math></inline-formula><sup>−1</sup>, exceeding the atmospheric CO<sub>2</sub> growth rate (2.3 <inline-formula><mml:math id="M24" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="normal">yr</mml:mi></mml:mrow></mml:math></inline-formula><sup>−1</sup>), alongside an acidification trend of <inline-formula><mml:math id="M26" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.003 <inline-formula><mml:math id="M27" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.001 yr<sup>−1</sup>.</p>

      <p id="d2e457">Over the 2019–2024 period, rising atmospheric CO<sub>2</sub> and increasing sea surface temperatures (reaching up to 0.2 °C yr<sup>−1</sup> during the unprecedented 2023 marine heatwave) likely contributed to these trends. The Canary Islands region shifted from a weak CO<sub>2</sub> source (0.90 Tg CO<sub>2</sub> yr<sup>−1</sup>) in 2019 to 4.5 Tg CO<sub>2</sub> yr<sup>−1</sup> in 2024. After 2022, eastern sites that previously acted as annual CO<sub>2</sub> sinks became net sources.</p>
  </abstract>
    
<funding-group>
<award-group id="gs1">
<funding-source>Consejería de Educación, Universidades, Cultura y Deportes, Gobierno de Canarias</funding-source>
<award-id>CarboCan</award-id>
</award-group>
<award-group id="gs2">
<funding-source>Loro Parque Fundación</funding-source>
<award-id>CanOA</award-id>
</award-group>
</funding-group>
</article-meta>
  </front>
<body>
      

<sec id="Ch1.S1" sec-type="intro">
  <label>1</label><title>Introduction</title>
      <p id="d2e551">Anthropogenic emissions of carbon dioxide (CO<sub>2</sub>) from fossil fuel combustion, cement production and land-use change (Doney et al., 2009; Le Quéré et al., 2009; Siegenthaler and Sarmiento, 1993; Zeebe, 2012) since the First Industrial Revolution have sharply increased atmospheric concentrations of this trace gas. This rise is partly mitigated by uptake from terrestrial vegetation and the oceans (Friedlingstein et al., 2025). The North Atlantic Ocean is reported as one of the major oceanic CO<sub>2</sub> sinks in the Northern Hemisphere, absorbing 2.6 <inline-formula><mml:math id="M39" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.4 Pg CO<sub>2</sub> yr<sup>−1</sup>. This is equivalent to <inline-formula><mml:math id="M42" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 25 % of the oceanic anthropogenic CO<sub>2</sub> sink, based on 18 years of observations (Gruber et al., 2002).</p>
      <p id="d2e617">Recent research has placed increasing emphasis on quantifying oceanic CO<sub>2</sub> uptake and its impact (e.g., Bange et al., 2024; Gregor et al., 2024). A common approach involves using regression models to estimate surface ocean CO<sub>2</sub> partial pressure (<inline-formula><mml:math id="M46" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub>) from environmental variables. However, these models often fall short in capturing the complexity of dynamic regions such as coastal zones and continental shelves (Sun et al., 2021). These areas exhibit intense physical and biogeochemical activity, driven by high rates of primary production, carbon burial, organic matter recycling, and calcium carbonate deposition (Boehme et al., 1998; Borges et al., 2005; Gattuso et al., 1998). Despite their importance, these regions remain poorly constrained in global carbon budgets and air-sea CO<sub>2</sub> flux estimates (Dai et al., 2022).</p>
      <p id="d2e668">Pioneering studies by Borges et al. (2005) and Cai et al. (2006) provided the first global assessments of coastal CO<sub>2</sub> fluxes, emphasizing strong spatial heterogeneity and functional diversity of coastal ecosystems in the global carbon cycle. More recent studies indicate that coastal regions act as significant CO<sub>2</sub> sinks, with global ingassing estimates of 0.54–1.47 Pg CO<sub>2</sub> yr<sup>−1</sup> (Cao et al., 2020; Laruelle et al., 2014), though updated assessments suggest lower rates (Dai et al., 2022; Regnier et al., 2022; Resplandy et al., 2024; Roobaert et al., 2019).</p>
      <p id="d2e710">At large latitudinal scale, sea surface temperature (SST) is a primary driver of surface ocean <inline-formula><mml:math id="M53" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub>, often expressed as CO<sub>2</sub> fugacity (<inline-formula><mml:math id="M56" display="inline"><mml:mi>f</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub>), which accounts for non-ideal gas behaviour due to molecular interactions and is typically slightly lower than <inline-formula><mml:math id="M58" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2</sub> (Wanninkhof et al., 2022). At smaller spatial scales (within latitudinal bands), additional drivers such as upwelling-driven CO<sub>2</sub> supply and biological uptake of dissolved inorganic carbon (<inline-formula><mml:math id="M61" display="inline"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mi mathvariant="normal">T</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>) become relevant (e.g., Laruelle et al., 2014).</p>
      <p id="d2e802">The <inline-formula><mml:math id="M62" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> is governed by four interconnected processes: thermodynamic forcing, biological activity, physical mixing, and air-sea CO<sub>2</sub> exchange (Fennel et al., 2008; Ikawa et al., 2013). One or two of these processes typically dominating in any given region (Bai et al., 2015). The thermodynamic component is primarily influenced by the SST and sea surface salinity (SSS), which determine CO<sub>2</sub> solubility (Weiss, 1970) and carbonic acid dissociation constants (e.g., Lueker et al., 2000). Biological effects can be approximated using satellite-derived chlorophyll <inline-formula><mml:math id="M66" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> (Chl <inline-formula><mml:math id="M67" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula>) and the diffuse attenuation coefficient of downwelling irradiance at 490 nm (Kd<sub>490</sub>) (Bai et al., 2015; Chen et al., 2019; Lohrenz et al., 2018). Vertical mixing processes, particularly those enriching surface waters with CO<sub>2</sub> from deeper layers, are commonly parameterised using mixed-layer depth (MLD) (Chen et al., 2019). Additionally, the continuous rise in <inline-formula><mml:math id="M70" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,atm</sub>, which drives the air-sea CO<sub>2</sub> gradient, must be considered in long-term assessments.</p>
      <p id="d2e907">Satellite remote sensing provides broad spatiotemporal coverage for surface <inline-formula><mml:math id="M73" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> estimation (Chen et al., 2019). In the open settings with relatively variability, satellite-based estimates achieve RMSE <inline-formula><mml:math id="M75" display="inline"><mml:mo>&lt;</mml:mo></mml:math></inline-formula> 17 <inline-formula><mml:math id="M76" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula>. Errors exceed 90 <inline-formula><mml:math id="M77" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> in coastal waters due to increased complexity in physical and biogeochemical processes (Lohrenz et al., 2018; Sun et al., 2021). Traditional empirical approaches include multilinear (MLR) and nonlinear regression (MNR). Shadwick et al. (2010) applied MLR to the Scotian Shelf (<inline-formula><mml:math id="M78" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.81</mml:mn></mml:mrow></mml:math></inline-formula>; SE <inline-formula><mml:math id="M79" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 13 <inline-formula><mml:math id="M80" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula>). Signorini et al. (2013) reported RMSE of 22.4–36.9 <inline-formula><mml:math id="M81" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> along the U.S. East Coast. Chen et al. (2016) developed a satellite-based model for the West Florida Shelf with RMSE <inline-formula><mml:math id="M82" display="inline"><mml:mo>&lt;</mml:mo></mml:math></inline-formula> 12 <inline-formula><mml:math id="M83" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula>.</p>
      <p id="d2e1018">Machine learning (ML) approaches, such as <italic>neural networks (NN)</italic>, random forests and <italic>CatBoost</italic>, have improved prediction skills. Lefèvre and Taylor (2002) reported NN residuals of 3–11 <inline-formula><mml:math id="M84" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> in the subpolar gyre. Telszewski et al. (2009) obtained RMSE of 11.6 <inline-formula><mml:math id="M85" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> in the North Atlantic. Sun et al. (2021) used  CatBoost to reach RMSE of 8.25 <inline-formula><mml:math id="M86" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M87" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.946</mml:mn></mml:mrow></mml:math></inline-formula>). Gregor et al. (2024) applied ML with target transformation at the global scale (1982–2022), resolving 15 % more CO<sub>2</sub> flux (FCO<sub>2</sub>) variance than traditional methods.</p>
      <p id="d2e1091">In coastal studies, Jo et al. (2012) used NN with SST and Chl <inline-formula><mml:math id="M90" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> in the South China Sea (RMSE <inline-formula><mml:math id="M91" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 6.9 <inline-formula><mml:math id="M92" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula>; <inline-formula><mml:math id="M93" display="inline"><mml:mrow><mml:mi>r</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.98</mml:mn></mml:mrow></mml:math></inline-formula>). Duke et al. (2024) showed that nearshore outgassing reduces net flux in the Northeast Pacific. Roobaert et al. (2024) highlighted strong seasonal FCO<sub>2</sub> variability driven by open-ocean and intracoastal exchanges. Wu et al. (2024) applied ML in the Gulf of Mexico, estimating 1.5 TgC yr<sup>−1</sup> of CO<sub>2</sub> uptake, though long-term trends remained uncertain.</p>
      <p id="d2e1161">The present study focuses on the coastal Canary Islands basin (27.0–30° N; 13.0–19° W) (Fig. 1), located in oligotrophic waters of the eastern subtropical North Atlantic gyre (Pelegrí et al., 1996). The region is influenced by the Canary Current and trade winds, which generate mesoscale eddies. Despite low surface Chl <inline-formula><mml:math id="M97" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> concentrations, primary productivity may increase due to upwelling filaments from NW Africa, eddies, and dust fertilization (Davenport et al., 1999). Marine heatwaves (MHWs) are intensifying under climate change (Frölicher and Laufkötter, 2018; Hobday et al., 2016; Holbrook et al., 2019). Varela et al. (2024) reported that 2023 was the warmest year in the Canary Upwelling System since 1982, with widespread record SST, likely affecting CO<sub>2</sub> dynamics.</p>

      <fig id="F1" specific-use="star"><label>Figure 1</label><caption><p id="d2e1183">Map of the Canary Islands showing the CanOA-VOS tracks (CanOA-VOS-1 Jona Sophie, in red; and CanOA-VOS-2 Benchijigua Express, in blue), the locations of the moored oceanographic buoys (MORGAN-1, cyan triangle; ULA-2, purple square), the ESTOC site (green star), and green circles indicate discrete sampling locations. The positions of sites A–F are also indicated, with site E corresponding to the ULA-2 buoy, site E to the MORGAN-1 buoy, and site G to the ESTOC site. The island acronyms are included (EH: El Hierro, LP: La Palma, GOM: La Gomera, TF: Tenerife, GC: Gran Canaria, FTV: Fuerteventura, LZ: Lanzarote). The figure was created with Matlab (version 2023b) software using the geoplot function with a satellite basemap. Basemap: Esri World Imagery (satellite imagery), © Esri and its data providers.</p></caption>
        <graphic xlink:href="https://os.copernicus.org/articles/22/609/2026/os-22-609-2026-f01.jpg"/>

      </fig>

      <p id="d2e1192">Long-term observations reveal a consistent rise in surface <inline-formula><mml:math id="M99" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> in this region. Takahashi et al. (2009) estimated an increase of 1.8 <inline-formula><mml:math id="M101" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.4 <inline-formula><mml:math id="M102" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> yr<sup>−1</sup> for the North Atlantic (1972–2006). Bates et al. (2014) reported 1.92 <inline-formula><mml:math id="M104" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.92 <inline-formula><mml:math id="M105" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> yr<sup>−1</sup> (1996–2012) at the ESTOC (European Station for Timeseries in the Ocean Canary Islands) site, with pH<sub>T,is</sub> (pH in total scale and at in situ temperature) decreasing by <inline-formula><mml:math id="M108" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.0018 <inline-formula><mml:math id="M109" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.0002 yr<sup>−1</sup>. More recently, González-Dávila and Santana-Casiano (2023) reported <inline-formula><mml:math id="M111" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> increasing by 2.1 <inline-formula><mml:math id="M113" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.1 <inline-formula><mml:math id="M114" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> yr<sup>−1</sup> and pH<sub>T,21</sub> decreasing by <inline-formula><mml:math id="M117" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.002 <inline-formula><mml:math id="M118" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.0001 yr<sup>−1</sup> in the upper 100 m (1995–2023), around 20 % faster than rates for 1995–2010.</p>
      <p id="d2e1407">The aim of this study was to develop and validate a machine-learning algorithm to estimate <inline-formula><mml:math id="M120" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub>, pH<sub>T,is</sub> and FCO<sub>2</sub> in the Canary Basin (NE Atlantic) using satellite-derived environmental variables and a high-resolution time series of <inline-formula><mml:math id="M124" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> observations from voluntary observing ships (VOS) and moored oceanographic buoys.</p>
</sec>
<sec id="Ch1.S2">
  <label>2</label><title>Material and methods</title>
<sec id="Ch1.S2.SS1">
  <label>2.1</label><title>Data</title>
<sec id="Ch1.S2.SS1.SSS1">
  <label>2.1.1</label><title>In situ observations</title>
      <p id="d2e1498">The observational dataset was compiled using measurements from Surface Ocean Observation Platforms (SOOPs) installed on Volunteer Observing Ships (VOS) and moored oceanographic buoys (Fig. 1; Table S1 in the Supplement). Two VOS collect continuous underway data along their routine shipping routes: <list list-type="order"><list-item>
      <p id="d2e1503">The CanOA-VOS-1 on board the <italic>Jona Sophie</italic> (formerly <italic>Renate P.</italic>) operated in Spain by Nisa Marítima and owned by Reederei Stefan Patjens GmbH &amp; Co. KG. This cargo vessel services the eastern Canary Islands between Tenerife (TF; 28.4867° N, 16.2284° W), Gran Canaria (GC; 28.1319° N, 15.4185° W) and Lanzarote (LZ; 28.9682° N, 13.5294° W) and continues northeast of Lanzarote in route to Barcelona (Spain). Seawater is sampled from a depth of 7 m. CanOA-VOS-1 contributes to the Spanish component of Integrated Carbon Observation System (ES-SOOP-CanOA, ICOS-ERIC; <uri>https://www.icos-cp.eu/</uri>,  last access: 22 January 2026) since 2021 and has been classified as an ICOS Class 1 Ocean Station.</p></list-item><list-item>
      <p id="d2e1516">The CanOA-VOS-2 on board Benchijigua Express, operated and owned by Fred Olsen Express, covering the western islands between a second port in Tenerife (TF; 28.0486° N, 16.7163° W), La Gomera (GOM; 28.0859° N, 17.1090° W) and La Palma (LP; 28.6751° N, 17.7666° W). The seawater intake is located at 5 m depth.</p></list-item></list> In addition, two coastal oceanographic buoys record surface data at 1 m depth: <list list-type="order"><list-item>
      <p id="d2e1522">MORGAN-1 (Gando, Gran Canaria, 27.9296° N, 15.3646° W; González et al., 2024).</p></list-item><list-item>
      <p id="d2e1526">ULA-2 (El Hierro, 27.6350° N, 17.9964° W).</p></list-item></list> All autonomous underway monitoring and data acquisition follows the quality-control procedures recommended by Pierrot et al. (2009). A detailed description of equipment can be found in Curbelo-Hernández et al. (2021, 2022) and in the Supplement. The number of used observations is listed in Table S1 in the Supplement.</p>
      <p id="d2e1530">Discrete samples of total alkalinity (<inline-formula><mml:math id="M126" display="inline"><mml:mrow><mml:msub><mml:mi>A</mml:mi><mml:mi mathvariant="normal">T</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>) and total inorganic carbon (<inline-formula><mml:math id="M127" display="inline"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mi mathvariant="normal">T</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>) were collected on board by a scientist on a transect every three months on the same seawater intake line used by the underway system, ensuring coverage across seasons and sampling sites (Fig. 1). Analyses were performed using a VINDTA 3C (Marianda™) following Mintrop et al. (2000). Calibration was carried out using Certified Reference Material (CRMs; provided by Andrew Dickson, Scripps Institution of Oceanography), with an accuracy of <inline-formula><mml:math id="M128" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.5 <inline-formula><mml:math id="M129" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">mol</mml:mi></mml:mrow></mml:math></inline-formula> kg<sup>−1</sup> for <inline-formula><mml:math id="M131" display="inline"><mml:mrow><mml:msub><mml:mi>A</mml:mi><mml:mi mathvariant="normal">T</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M132" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.0 <inline-formula><mml:math id="M133" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">mol</mml:mi></mml:mrow></mml:math></inline-formula> kg<sup>−1</sup> for <inline-formula><mml:math id="M135" display="inline"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mi mathvariant="normal">T</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>. Differences between <inline-formula><mml:math id="M136" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> (converted from measured xCO<sub>2,sw</sub>; for method see below) and discrete <inline-formula><mml:math id="M139" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2(AT,CT)</sub> (CO<sub>2</sub>sys.V2.1.xls, set of carbonic acid constants from Lueker et al., 2000, <inline-formula><mml:math id="M142" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">66</mml:mn></mml:mrow></mml:math></inline-formula>) were 4 <inline-formula><mml:math id="M143" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 4 <inline-formula><mml:math id="M144" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> for the GO8050 and 7 <inline-formula><mml:math id="M145" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 5 <inline-formula><mml:math id="M146" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> for the ProCV system. A correction factor was applied to account for these offsets.</p>
      <p id="d2e1755">For regional comparison, seven locations were defined across the archipelago (Fig. 1): Site A, along the LP-GOM route (17.5 <inline-formula><mml:math id="M147" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.05° W); Site B, along the GOM-TF route (16.95 <inline-formula><mml:math id="M148" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.05° W). Site C, at the intersection of multiple ship routes (14.65 <inline-formula><mml:math id="M149" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.05° W); Site D, near the NW African coast along the LZ-Iberian Peninsula route (13.2 <inline-formula><mml:math id="M150" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.05° W); Site E, at the ULA-2 buoy near El Hierro; Site F at the MORGAN-1 buoy at Gando bay (GC); and Site G at the ESTOC site.</p>
</sec>
<sec id="Ch1.S2.SS1.SSS2">
  <label>2.1.2</label><title>Satellite data</title>
      <p id="d2e1794">Satellite-derived SST, Chl <inline-formula><mml:math id="M151" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula>, Kd<sub>490</sub>, MLD data were used to develop the <inline-formula><mml:math id="M153" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and pH<sub>T,is</sub> forecast models, while wind speed was incorporated for FCO<sub>2</sub> calculation. All satellite products were obtained from the Copernicus Marine Environmental Monitoring Service (CMEMS; <uri>https://marine.copernicus.eu/access-data</uri>, last access: 27 May 2025). Wind speed data were retrieved from the Agencia Estatal de Meteorología (AEMET; AEMET Open Data, <uri>https://opendata.aemet.es/centrodedescargas/productosAEMET</uri>, last access: 8 October 2025). Wind measurements were taken La Palma Airport (33 m), La Gomera Airport (15 m), Fuerteventura Airport (25 m), Lanzarote Airport (14 m), Gran Canaria Airport (24 m), and El Hierro Airport (32 m), corresponding to sites A–F of the study area. Wind speeds were standardised to 10 m height following Allen et al. (1998). All variables were processed and matched in time and space to the observational records, and daily means were used for model calibration and validation. The full daily dataset was then applied to generate the surface marine carbonate system variables in the Canary Islands.</p>
      <p id="d2e1864">Satellite-derived products carry inherent uncertainties associated with remote sensing retrievals. For the used CMEMS products, mean uncertainties were 0.62 °C for SST and 0.485 mg m<sup>−3</sup> for Chl <inline-formula><mml:math id="M158" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula>. Their contribution to prediction error was assessed during model validation through comparison with coincident in situ measurements.</p>
</sec>
</sec>
<sec id="Ch1.S2.SS2">
  <label>2.2</label><title>Variable determination and computational methods</title>
      <p id="d2e1895">The raw data were processed using MATLAB<sup><italic>®</italic></sup> R2019b and Python 3.13.6 (2023). For the VOS dataset, <inline-formula><mml:math id="M160" display="inline"><mml:mi>x</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> measurement from the GO8050 system were calibrated using a four-standard procedure, after filtering data points collected near ports where seawater CO<sub>2</sub> concentrations may be influenced by local activities. Quality control included applying minimum flow thresholds of 2.5 L min<sup>−1</sup> for the seawater line and 50 mL min<sup>−1</sup> for the LICOR<sup><italic>©</italic></sup> gas flow.</p>
      <p id="d2e1971">The partial pressure of CO<sub>2</sub> in seawater (<inline-formula><mml:math id="M167" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,eq</sub>) was calculated from corrected dry <inline-formula><mml:math id="M169" display="inline"><mml:mi>x</mml:mi></mml:math></inline-formula>CO<sub>2</sub> (Dickson et al., 2007). Values from both VOS routes were subsequently adjusted to intake temperature to account for differences between the thermosalinograph/equilibrator temperature and SST (Takahashi et al., 1993). Fugacity (<inline-formula><mml:math id="M171" display="inline"><mml:mi>f</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub>) was then computed from <inline-formula><mml:math id="M173" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> for both VOS and buoy datasets (Dickson et al., 2007). Discrete samples analysed for <inline-formula><mml:math id="M175" display="inline"><mml:mrow><mml:msub><mml:mi>A</mml:mi><mml:mi mathvariant="normal">T</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> using the VINDTA 3C were used to determine an <inline-formula><mml:math id="M176" display="inline"><mml:mrow><mml:msub><mml:mi>A</mml:mi><mml:mi mathvariant="normal">T</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>-SSS relationship for the study region (<inline-formula><mml:math id="M177" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">66</mml:mn></mml:mrow></mml:math></inline-formula>), consistent with that previously reported for the ESTOC site (González Dávila et al., 2010). The normalised <inline-formula><mml:math id="M178" display="inline"><mml:mrow><mml:msub><mml:mi>A</mml:mi><mml:mi mathvariant="normal">T</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> (NA<inline-formula><mml:math id="M179" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mi mathvariant="normal">T</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:msub><mml:mi>A</mml:mi><mml:mi mathvariant="normal">T</mml:mi></mml:msub><mml:mo>/</mml:mo><mml:mtext>SSS</mml:mtext><mml:mo>×</mml:mo><mml:mn mathvariant="normal">35</mml:mn></mml:mrow></mml:math></inline-formula>) was <inline-formula><mml:math id="M180" display="inline"><mml:mrow><mml:mn mathvariant="normal">2290</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M181" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">mol</mml:mi></mml:mrow></mml:math></inline-formula> kg<sup>−1</sup>, significant at the 99 % confidence level (<inline-formula><mml:math id="M183" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>-value <inline-formula><mml:math id="M184" display="inline"><mml:mo>&lt;</mml:mo></mml:math></inline-formula> 0.01; <inline-formula><mml:math id="M185" display="inline"><mml:mrow><mml:msup><mml:mi>r</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.96</mml:mn></mml:mrow></mml:math></inline-formula>), with no evidence of seasonal variability, in agreement with long-term ESTOC observation (González Dávila et al., 2010). This relationship was applied to compute total scale pH<inline-formula><mml:math id="M186" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mrow><mml:mi mathvariant="normal">T</mml:mi><mml:mo>,</mml:mo><mml:mi mathvariant="normal">is</mml:mi></mml:mrow></mml:msub><mml:mo>(</mml:mo><mml:msub><mml:mi>A</mml:mi><mml:mi mathvariant="normal">T</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>(SSS), <inline-formula><mml:math id="M187" display="inline"><mml:mi>f</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub>) for the Canary Region (González Dávila et al., 2010). All process variables were averaged to a daily resolution.</p>
      <p id="d2e2241">Daily mean atmospheric <inline-formula><mml:math id="M189" display="inline"><mml:mi>x</mml:mi></mml:math></inline-formula>CO<sub>2,atm</sub> was obtained from onboard atmospheric measurements and compared with records from the World Meteorological Organisation (WMO) Izaña Atmospheric Observatory (AEMET, 2024) in Tenerife (28°18′ N, 16°29′ W), due to potential contamination by ship operations. Winter maxima were similar between datasets (<inline-formula><mml:math id="M193" display="inline"><mml:mo lspace="0mm">±</mml:mo></mml:math></inline-formula>1.5 <inline-formula><mml:math id="M194" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula>), while late summer minima at Izaña were on average 3 <inline-formula><mml:math id="M195" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> higher than values measured at the ship's 10 m inlet. As in situ coverage was limited and the Izaña record provided a longer continuous series, the Izaña <inline-formula><mml:math id="M196" display="inline"><mml:mi>x</mml:mi></mml:math></inline-formula>CO<sub>2,atm</sub> dataset was adopted for this study. Atmospheric <inline-formula><mml:math id="M198" display="inline"><mml:mi>x</mml:mi></mml:math></inline-formula>CO<sub>2,atm</sub> was converted to <inline-formula><mml:math id="M200" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,atm</sub> (Dickson et al., 2007).</p>
      <p id="d2e2387">The flux of CO<sub>2</sub>, FCO<sub>2</sub>, was determined using Eq. (1):

            <disp-formula id="Ch1.E1" content-type="numbered"><label>1</label><mml:math id="M204" display="block"><mml:mrow><mml:msub><mml:mi mathvariant="normal">FCO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.24</mml:mn><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi>k</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi>S</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="normal">Δ</mml:mi><mml:mi>p</mml:mi><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:mrow></mml:math></disp-formula>

          where 0.24 is the conversion factor to express the flux in mmol m<sup>−2</sup> d<sup>−1</sup>, <inline-formula><mml:math id="M207" display="inline"><mml:mi>S</mml:mi></mml:math></inline-formula> is the solubility of CO<sub>2</sub> in seawater (Weiss, 1970), <inline-formula><mml:math id="M209" display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:mi>p</mml:mi></mml:mrow></mml:math></inline-formula>CO<sub>2</sub> is <inline-formula><mml:math id="M211" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<inline-formula><mml:math id="M212" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>,</mml:mo><mml:mi mathvariant="normal">sw</mml:mi></mml:mrow></mml:msub><mml:mo>-</mml:mo><mml:mi>p</mml:mi></mml:mrow></mml:math></inline-formula>CO<sub>2,atm</sub> and <inline-formula><mml:math id="M214" display="inline"><mml:mi>k</mml:mi></mml:math></inline-formula> is the gas transfer rate determined using the Wanninkhof (2014) parameterization (Eq. 2):

            <disp-formula id="Ch1.E2" content-type="numbered"><label>2</label><mml:math id="M215" display="block"><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mi mathvariant="normal">Wan</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.251</mml:mn><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi>u</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mo>(</mml:mo><mml:mi>S</mml:mi><mml:mi>c</mml:mi><mml:mo>/</mml:mo><mml:mn mathvariant="normal">650</mml:mn><mml:msup><mml:mo>)</mml:mo><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.5</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></disp-formula>

          where <inline-formula><mml:math id="M216" display="inline"><mml:mi>u</mml:mi></mml:math></inline-formula> is the wind speed (m s<sup>−1</sup>) and <italic>Sc</italic> is the Schmidt number.</p>
      <p id="d2e2612">Equation (1) was applied to the daily modelled data. Daily fluxes were averaged to provide monthly fluxes, which are reported as daily average value for each month (mmol m<sup>−2</sup> d<sup>−1</sup>).</p>
      <p id="d2e2639">Each physicochemical variable <inline-formula><mml:math id="M220" display="inline"><mml:mi>y</mml:mi></mml:math></inline-formula> (including <inline-formula><mml:math id="M221" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,atm</sub> and <inline-formula><mml:math id="M223" display="inline"><mml:mi>f</mml:mi></mml:math></inline-formula>CO<sub>2,atm</sub>) was fitted to a harmonic function (Eq. 3, where <inline-formula><mml:math id="M225" display="inline"><mml:mi>t</mml:mi></mml:math></inline-formula> is the year fraction for each observation). Seasonal anomalies were obtained by adding the residuals between observed values and those predicted by Eq. (3) to the constant term <inline-formula><mml:math id="M226" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> in Eq. (3), representing the mean value of <inline-formula><mml:math id="M227" display="inline"><mml:mi>y</mml:mi></mml:math></inline-formula> for the study period. Interannual trends were then estimated using Eq. (4) applied to the deseasonalised time series. Although the length of the dataset is relatively short (5–6 years), the use of detrended seasonal anomalies minimizes end-effects and improves the robustness of the trend estimation.

                <disp-formula specific-use="gather" content-type="numbered"><mml:math id="M228" display="block"><mml:mtable displaystyle="true"><mml:mlabeledtr id="Ch1.E3"><mml:mtd><mml:mtext>3</mml:mtext></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:mtable class="split" rowspacing="0.2ex" displaystyle="true" columnalign="right left"><mml:mtr><mml:mtd><mml:mrow><mml:mi>y</mml:mi></mml:mrow></mml:mtd><mml:mtd><mml:mrow><mml:mo>=</mml:mo><mml:mi>a</mml:mi><mml:mo>+</mml:mo><mml:mi>c</mml:mi><mml:mo>⋅</mml:mo><mml:mi>sin⁡</mml:mi><mml:mfenced close=")" open="("><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mi mathvariant="italic">π</mml:mi><mml:mi>t</mml:mi></mml:mrow></mml:mfenced><mml:mo>+</mml:mo><mml:mi>d</mml:mi><mml:mo>⋅</mml:mo><mml:mi>cos⁡</mml:mi><mml:mfenced close=")" open="("><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mi mathvariant="italic">π</mml:mi><mml:mi>t</mml:mi></mml:mrow></mml:mfenced><mml:mo>+</mml:mo><mml:mi>e</mml:mi><mml:mo>⋅</mml:mo><mml:mi>sin⁡</mml:mi><mml:mfenced close=")" open="("><mml:mrow><mml:mn mathvariant="normal">4</mml:mn><mml:mi mathvariant="italic">π</mml:mi><mml:mi>t</mml:mi></mml:mrow></mml:mfenced></mml:mrow></mml:mtd></mml:mtr><mml:mtr><mml:mtd/><mml:mtd><mml:mrow><mml:mo>+</mml:mo><mml:mi mathvariant="normal">cos</mml:mi><mml:mo>(</mml:mo><mml:mn mathvariant="normal">4</mml:mn><mml:mi mathvariant="italic">π</mml:mi><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:mtd></mml:mtr></mml:mtable></mml:mrow></mml:mtd></mml:mlabeledtr><mml:mlabeledtr id="Ch1.E4"><mml:mtd><mml:mtext>4</mml:mtext></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:mtable class="split" rowspacing="0.2ex" displaystyle="true" columnalign="right left"><mml:mtr><mml:mtd><mml:mrow><mml:mi>y</mml:mi></mml:mrow></mml:mtd><mml:mtd><mml:mrow><mml:mo>=</mml:mo><mml:mi>a</mml:mi><mml:mo>+</mml:mo><mml:mi>b</mml:mi><mml:mo>⋅</mml:mo><mml:mfenced open="(" close=")"><mml:mrow><mml:mi>t</mml:mi><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2019</mml:mn></mml:mrow></mml:mfenced><mml:mo>+</mml:mo><mml:mi>c</mml:mi><mml:mo>⋅</mml:mo><mml:mi>sin⁡</mml:mi><mml:mfenced open="(" close=")"><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mi mathvariant="italic">π</mml:mi><mml:mi>t</mml:mi></mml:mrow></mml:mfenced><mml:mo>+</mml:mo><mml:mi>d</mml:mi><mml:mo>⋅</mml:mo><mml:mi>cos⁡</mml:mi><mml:mfenced open="(" close=")"><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mi mathvariant="italic">π</mml:mi><mml:mi>t</mml:mi></mml:mrow></mml:mfenced></mml:mrow></mml:mtd></mml:mtr><mml:mtr><mml:mtd/><mml:mtd><mml:mrow><mml:mo>+</mml:mo><mml:mi>e</mml:mi><mml:mo>⋅</mml:mo><mml:mi>sin⁡</mml:mi><mml:mfenced close=")" open="("><mml:mrow><mml:mn mathvariant="normal">4</mml:mn><mml:mi mathvariant="italic">π</mml:mi><mml:mi>t</mml:mi></mml:mrow></mml:mfenced><mml:mo>+</mml:mo><mml:mi mathvariant="normal">cos</mml:mi><mml:mo>(</mml:mo><mml:mn mathvariant="normal">4</mml:mn><mml:mi mathvariant="italic">π</mml:mi><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:mtd></mml:mtr></mml:mtable></mml:mrow></mml:mtd></mml:mlabeledtr></mml:mtable></mml:math></disp-formula></p>
</sec>
<sec id="Ch1.S2.SS3">
  <label>2.3</label><title>Model fitting and statistical treatment</title>
      <p id="d2e2913">Statistical analyses were conducted using R (R Core Team, 2019). Machine-learning methods were used to fit the different models. The dataset was initially partitioned into training (80 %) and validation (20 %) subsets, with allocation performed randomly at the cruise level to avoid temporal bias. This random split was repeated for each model run to ensure representative sampling. Once model performance had been evaluated, the complete dataset was used to provide the optimal model parameters.</p>
      <p id="d2e2916">The simplest fitted model was a multiple linear regression (MLR), defined analytically in Eq. (5):

            <disp-formula id="Ch1.E5" content-type="numbered"><label>5</label><mml:math id="M229" display="block"><mml:mtable rowspacing="0.2ex" class="split" displaystyle="true" columnalign="right left"><mml:mtr><mml:mtd><mml:mrow><mml:mi>p</mml:mi><mml:msub><mml:mrow class="chem"><mml:mi mathvariant="normal">CO</mml:mi></mml:mrow><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>,</mml:mo><mml:mi mathvariant="normal">sw</mml:mi></mml:mrow></mml:msub></mml:mrow></mml:mtd><mml:mtd><mml:mrow><mml:mo>=</mml:mo><mml:msub><mml:mi>p</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:mover accent="true"><mml:mi mathvariant="italic">α</mml:mi><mml:mo stretchy="true" mathvariant="normal">^</mml:mo></mml:mover><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi>p</mml:mi><mml:msub><mml:mrow class="chem"><mml:mi mathvariant="normal">CO</mml:mi></mml:mrow><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>,</mml:mo><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:msub><mml:mo>(</mml:mo><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow><mml:mo>)</mml:mo><mml:mo>+</mml:mo><mml:mover accent="true"><mml:mi mathvariant="italic">β</mml:mi><mml:mo mathvariant="normal" stretchy="true">^</mml:mo></mml:mover><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mi mathvariant="normal">SST</mml:mi><mml:mfenced open="(" close=")"><mml:mrow class="unit"><mml:mi mathvariant="normal">°</mml:mi><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:mfenced></mml:mrow></mml:mtd></mml:mtr><mml:mtr><mml:mtd/><mml:mtd><mml:mrow><mml:mo>+</mml:mo><mml:mover accent="true"><mml:mi mathvariant="italic">γ</mml:mi><mml:mo mathvariant="normal" stretchy="true">^</mml:mo></mml:mover><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mi mathvariant="normal">Chl</mml:mi><mml:mfenced open="(" close=")"><mml:mrow class="unit"><mml:mi mathvariant="normal">mg</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:mfenced><mml:mo>+</mml:mo><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mover accent="true"><mml:mi mathvariant="italic">δ</mml:mi><mml:mo mathvariant="normal" stretchy="true">^</mml:mo></mml:mover><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msub><mml:mi>K</mml:mi><mml:mrow><mml:mi mathvariant="normal">d</mml:mi><mml:mo>,</mml:mo><mml:mn mathvariant="normal">490</mml:mn></mml:mrow></mml:msub><mml:mfenced close=")" open="("><mml:mrow class="unit"><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:mfenced></mml:mrow></mml:mtd></mml:mtr><mml:mtr><mml:mtd/><mml:mtd><mml:mrow><mml:mo>+</mml:mo><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mover accent="true"><mml:mi mathvariant="italic">ε</mml:mi><mml:mo stretchy="true" mathvariant="normal">^</mml:mo></mml:mover><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="normal">MLD</mml:mi><mml:mfenced open="(" close=")"><mml:mrow class="unit"><mml:mi mathvariant="normal">m</mml:mi></mml:mrow></mml:mfenced><mml:mo>+</mml:mo><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="italic">ϑ</mml:mi></mml:mrow></mml:mtd></mml:mtr></mml:mtable></mml:math></disp-formula>

          where <inline-formula><mml:math id="M230" display="inline"><mml:mrow><mml:mover accent="true"><mml:mrow><mml:mi mathvariant="italic">α</mml:mi><mml:mo>,</mml:mo></mml:mrow><mml:mo mathvariant="normal" stretchy="true">^</mml:mo></mml:mover><mml:mover accent="true"><mml:mi mathvariant="italic">β</mml:mi><mml:mo stretchy="true" mathvariant="normal">^</mml:mo></mml:mover><mml:mo>,</mml:mo><mml:mover accent="true"><mml:mi mathvariant="italic">γ</mml:mi><mml:mo mathvariant="normal" stretchy="true">^</mml:mo></mml:mover><mml:mo>,</mml:mo><mml:mover accent="true"><mml:mi mathvariant="italic">δ</mml:mi><mml:mo stretchy="true" mathvariant="normal">^</mml:mo></mml:mover></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M231" display="inline"><mml:mover accent="true"><mml:mi mathvariant="italic">ε</mml:mi><mml:mo stretchy="true" mathvariant="normal">^</mml:mo></mml:mover></mml:math></inline-formula> are the estimated coefficients for each predictor and <inline-formula><mml:math id="M232" display="inline"><mml:mi mathvariant="italic">ϑ</mml:mi></mml:math></inline-formula> the residuals. The same equation (without the <inline-formula><mml:math id="M233" display="inline"><mml:mover accent="true"><mml:mi mathvariant="italic">α</mml:mi><mml:mo mathvariant="normal" stretchy="true">^</mml:mo></mml:mover></mml:math></inline-formula> term) was used to model pH<sub>T,is</sub> dependence.</p>
      <p id="d2e3152">Three machine-learning techniques were used: <italic>neural network</italic> (NN; Wang, 2003), <italic>categorical boosting</italic> (CatBoost; Dorogush et al., 2018; Prokhorenkova et al., 2018; Qian et al., 2023) and bootstrap aggregation (<italic>bagging</italic>; Breiman, 1996).</p>
      <p id="d2e3164">These approaches are widely employed in environmental modelling and provide complementary approaches for improving predictive accuracy by reducing variance and capturing nonlinear relationships.</p>
      <p id="d2e3168">CatBoost is a gradient-boosting algorithm that constructs decision trees sequentially and efficiently handles categorical features, minimising information loss. Its ordered-boosting framework reduces prediction shift associated with gradient bias (Dorogush et al., 2018; Prokhorenkova et al., 2018; Qian et al., 2023; Sun et al., 2021).</p>
      <p id="d2e3171">Neural Networks (NN) are flexible nonlinear models inspired by the human brain, capable of capturing complex relationships between inputs and outputs (Wang, 2003). These methods are composed of interconnected neurons arranged in layers: an input layer representing predictors, one or more hidden layers, and an output layer producing the final prediction.</p>
      <p id="d2e3174">Bootstrap aggregation (bagging) is an ensemble technique that improves predictive robustness by generating multiple versions of a model trained on different bootstrap samples of the dataset (Breiman, 1996). Predictions are then averaged to reduce variance and prevent overfitting, making the overall model more stable and reliable.</p>
      <p id="d2e3177">Model performance was assessed using the validation dataset through the coefficient of determination (<inline-formula><mml:math id="M235" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>), root mean square error (RMSE; Eq. 6), mean absolute error (MAE; Eq. 7), and daily sum of squared errors (SSE; Eq. 8).

                <disp-formula specific-use="gather" content-type="numbered"><mml:math id="M236" display="block"><mml:mtable displaystyle="true"><mml:mlabeledtr id="Ch1.E6"><mml:mtd><mml:mtext>6</mml:mtext></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:mi mathvariant="normal">RMSE</mml:mi><mml:mo>=</mml:mo><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msqrt><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msubsup><mml:mo>∑</mml:mo><mml:mrow><mml:mi>i</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow><mml:mi>N</mml:mi></mml:msubsup><mml:msup><mml:mfenced close=")" open="("><mml:mrow><mml:mi>p</mml:mi><mml:msub><mml:mrow class="chem"><mml:mi mathvariant="normal">CO</mml:mi></mml:mrow><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>,</mml:mo><mml:mi>i</mml:mi></mml:mrow></mml:msub><mml:mo>-</mml:mo><mml:mover accent="true"><mml:mrow><mml:mi>p</mml:mi><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>,</mml:mo><mml:mi>i</mml:mi></mml:mrow></mml:msub></mml:mrow><mml:mo mathvariant="normal" stretchy="true">^</mml:mo></mml:mover></mml:mrow></mml:mfenced><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow><mml:mi>N</mml:mi></mml:mfrac></mml:mstyle></mml:msqrt></mml:mrow></mml:mtd></mml:mlabeledtr><mml:mlabeledtr id="Ch1.E7"><mml:mtd><mml:mtext>7</mml:mtext></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:mi mathvariant="normal">MAE</mml:mi><mml:mo>=</mml:mo><mml:msubsup><mml:mo>∑</mml:mo><mml:mrow><mml:mi>i</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow><mml:mi>N</mml:mi></mml:msubsup><mml:mfenced close="|" open="|"><mml:mrow><mml:mi>p</mml:mi><mml:msub><mml:mrow class="chem"><mml:mi mathvariant="normal">CO</mml:mi></mml:mrow><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>,</mml:mo><mml:mi>I</mml:mi></mml:mrow></mml:msub><mml:mo>-</mml:mo><mml:mover accent="true"><mml:mrow><mml:mi>p</mml:mi><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>,</mml:mo><mml:mi>i</mml:mi></mml:mrow></mml:msub></mml:mrow><mml:mo stretchy="true" mathvariant="normal">^</mml:mo></mml:mover></mml:mrow></mml:mfenced><mml:mo>/</mml:mo><mml:mi>d</mml:mi></mml:mrow></mml:mtd></mml:mlabeledtr><mml:mlabeledtr id="Ch1.E8"><mml:mtd><mml:mtext>8</mml:mtext></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:mi mathvariant="normal">SSE</mml:mi><mml:mo>=</mml:mo><mml:msubsup><mml:mo>∑</mml:mo><mml:mrow><mml:mi>i</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow><mml:mi>N</mml:mi></mml:msubsup><mml:msup><mml:mfenced close=")" open="("><mml:mrow><mml:mi>p</mml:mi><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>,</mml:mo><mml:mi>I</mml:mi></mml:mrow></mml:msub><mml:mo>-</mml:mo><mml:mover accent="true"><mml:mrow><mml:mi>p</mml:mi><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>,</mml:mo><mml:mi>i</mml:mi></mml:mrow></mml:msub></mml:mrow><mml:mo stretchy="true" mathvariant="normal">^</mml:mo></mml:mover></mml:mrow></mml:mfenced><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>/</mml:mo><mml:mi>d</mml:mi></mml:mrow></mml:mtd></mml:mlabeledtr></mml:mtable></mml:math></disp-formula>

          where <inline-formula><mml:math id="M237" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:msub><mml:mrow class="chem"><mml:mi mathvariant="normal">CO</mml:mi></mml:mrow><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>,</mml:mo><mml:mi>i</mml:mi></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M238" display="inline"><mml:mover accent="true"><mml:mrow><mml:mi>p</mml:mi><mml:msub><mml:mrow class="chem"><mml:mi mathvariant="normal">CO</mml:mi></mml:mrow><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>,</mml:mo><mml:mi>i</mml:mi></mml:mrow></mml:msub></mml:mrow><mml:mo mathvariant="normal" stretchy="true">^</mml:mo></mml:mover></mml:math></inline-formula> are the observed and modelled <inline-formula><mml:math id="M239" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2</sub>, <inline-formula><mml:math id="M241" display="inline"><mml:mi>N</mml:mi></mml:math></inline-formula> is the number of observations and <inline-formula><mml:math id="M242" display="inline"><mml:mi>d</mml:mi></mml:math></inline-formula> is the number of days in the dataset.</p>
      <p id="d2e3457">The Akaike information criterion corrected for a finite dataset (AIC<sub>c</sub>) was determined using Eq. (9). It evaluates the balance between goodness-of-fit and model complexity (i.e., number of predictors). Among competing models, the one with the lowest AIC<sub>c</sub> is considered the most appropriate.

            <disp-formula id="Ch1.E9" content-type="numbered"><label>9</label><mml:math id="M245" display="block"><mml:mrow><mml:msub><mml:mi mathvariant="normal">AIC</mml:mi><mml:mi mathvariant="normal">c</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mn mathvariant="normal">2</mml:mn><mml:mi>k</mml:mi><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn><mml:mi>ln⁡</mml:mi><mml:mfenced close=")" open="("><mml:mi>L</mml:mi></mml:mfenced><mml:mo>+</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:msup><mml:mi>k</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>+</mml:mo><mml:mn mathvariant="normal">2</mml:mn><mml:mi>k</mml:mi></mml:mrow><mml:mrow><mml:mi>n</mml:mi><mml:mo>-</mml:mo><mml:mi>k</mml:mi><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:mfrac></mml:mstyle></mml:mrow></mml:math></disp-formula>

          where <inline-formula><mml:math id="M246" display="inline"><mml:mi>k</mml:mi></mml:math></inline-formula> is the number of parameters involved in the model, <inline-formula><mml:math id="M247" display="inline"><mml:mrow><mml:mi>ln⁡</mml:mi><mml:mo>(</mml:mo><mml:mi>L</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> is the log-likelihood for the predicted model and <inline-formula><mml:math id="M248" display="inline"><mml:mi>n</mml:mi></mml:math></inline-formula> is the number of observations.</p>
      <p id="d2e3562">To estimate the coefficients of each seasonal model and determine confidence intervals, two assumptions were tested: (1) normality of residuals, assessed using the two-Welch Shapiro-Wilk test (<inline-formula><mml:math id="M249" display="inline"><mml:mrow><mml:mi mathvariant="italic">α</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.05</mml:mn></mml:mrow></mml:math></inline-formula>) and quantile-quantile plots, and (2) homogeneity of residual variance (homoscedasticity), assessed graphically. When the normality assumption was not met, bootstrapping was used to determine confidence intervals. Model comparisons were performed using analysis of covariance (ANCOVA) and analysis of variance (ANOVA) to detect significant differences at <inline-formula><mml:math id="M250" display="inline"><mml:mrow><mml:mi mathvariant="italic">α</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.05</mml:mn></mml:mrow></mml:math></inline-formula>.</p>
</sec>
</sec>
<sec id="Ch1.S3">
  <label>3</label><title>Results</title>
      <p id="d2e3598">The observational data enabled the construction of a database for modelling the behaviour of <inline-formula><mml:math id="M251" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and pH<sub>T,is</sub> in the Canary Basin. To characterise the measured and satellite-derived parameters used in this study, Table 1 summarises their seasonal mean and standard deviations for each observation system. In situ SST (Fig. 2) showed a clear seasonal cycle, with maximum temperatures in summer (July–September) and minima in winter (January–March). The highest SST occurred in the westernmost sector of the archipelago (between La Palma and Tenerife), averaging <inline-formula><mml:math id="M254" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 1 °C warmer than the eastern sector (between Gran Canaria and Lanzarote). A similar seasonal and longitudinal pattern was observed for <inline-formula><mml:math id="M255" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and pH<sub>T,is</sub> (Table 1). Seasonal and annual SST means derived from in situ and satellite observations differed by <inline-formula><mml:math id="M258" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 0.15 °C on average.</p>

<table-wrap id="T1" specific-use="star"><label>Table 1</label><caption><p id="d2e3689">Seasonal mean and standard deviations of observational data (pCO<sub>2,sw</sub> and SST) and satellite-derived data (SST, Chl <inline-formula><mml:math id="M260" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula>, Kd<sub>490</sub> and MLD) used in this study. The locations listed in the first column correspond to the two ship routes (CanOA-VOS-1 Jona Sophie and CanOA-VOS-2 Benchijigua Express) and the two moored buoys (MORGAN-1 and ULA-2).</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="8">
     <oasis:colspec colnum="1" colname="col1" align="justify" colwidth="2cm"/>
     <oasis:colspec colnum="2" colname="col2" align="left"/>
     <oasis:colspec colnum="3" colname="col3" align="right"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:colspec colnum="6" colname="col6" align="right"/>
     <oasis:colspec colnum="7" colname="col7" align="right"/>
     <oasis:colspec colnum="8" colname="col8" align="right"/>
     <oasis:thead>
       <oasis:row>

         <oasis:entry colname="col1"/>

         <oasis:entry colname="col2"/>

         <oasis:entry colname="col3">SST</oasis:entry>

         <oasis:entry colname="col4">SST Satellite</oasis:entry>

         <oasis:entry colname="col5">Chl <inline-formula><mml:math id="M262" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> Satellite</oasis:entry>

         <oasis:entry colname="col6">Kd<sub>490</sub> Satellite</oasis:entry>

         <oasis:entry colname="col7">MLD Satellite</oasis:entry>

         <oasis:entry colname="col8"><inline-formula><mml:math id="M264" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub></oasis:entry>

       </oasis:row>
       <oasis:row rowsep="1">

         <oasis:entry colname="col1"/>

         <oasis:entry colname="col2"/>

         <oasis:entry colname="col3">(°C)</oasis:entry>

         <oasis:entry colname="col4">(°C)</oasis:entry>

         <oasis:entry colname="col5">(mg m<sup>−3</sup>)</oasis:entry>

         <oasis:entry colname="col6">(m<sup>−1</sup>)</oasis:entry>

         <oasis:entry colname="col7">(m)</oasis:entry>

         <oasis:entry colname="col8">(<inline-formula><mml:math id="M268" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula>)</oasis:entry>

       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>

         <oasis:entry rowsep="1" colname="col1" morerows="4">CanOA-VOS-2 (Bechinjigua  Express  LP-TNF)</oasis:entry>

         <oasis:entry colname="col2">Winter</oasis:entry>

         <oasis:entry colname="col3">20.05 <inline-formula><mml:math id="M269" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.34</oasis:entry>

         <oasis:entry colname="col4">20.03 <inline-formula><mml:math id="M270" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.25</oasis:entry>

         <oasis:entry colname="col5">0.172 <inline-formula><mml:math id="M271" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.041</oasis:entry>

         <oasis:entry colname="col6">0.041 <inline-formula><mml:math id="M272" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.003</oasis:entry>

         <oasis:entry colname="col7">43.6 <inline-formula><mml:math id="M273" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 17.6</oasis:entry>

         <oasis:entry colname="col8">402.0 <inline-formula><mml:math id="M274" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 6.6</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry colname="col2">Spring</oasis:entry>

         <oasis:entry colname="col3">21.39 <inline-formula><mml:math id="M275" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.47</oasis:entry>

         <oasis:entry colname="col4">21.08 <inline-formula><mml:math id="M276" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.37</oasis:entry>

         <oasis:entry colname="col5">0.115 <inline-formula><mml:math id="M277" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.0217</oasis:entry>

         <oasis:entry colname="col6">0.035 <inline-formula><mml:math id="M278" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.002</oasis:entry>

         <oasis:entry colname="col7">18.4 <inline-formula><mml:math id="M279" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 6.5</oasis:entry>

         <oasis:entry colname="col8">419.8 <inline-formula><mml:math id="M280" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 8.3</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry colname="col2">Summer</oasis:entry>

         <oasis:entry colname="col3">23.40 <inline-formula><mml:math id="M281" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.51</oasis:entry>

         <oasis:entry colname="col4">23.31 <inline-formula><mml:math id="M282" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.56</oasis:entry>

         <oasis:entry colname="col5">0.12 <inline-formula><mml:math id="M283" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.0214</oasis:entry>

         <oasis:entry colname="col6">0.036 <inline-formula><mml:math id="M284" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.003</oasis:entry>

         <oasis:entry colname="col7">18.5 <inline-formula><mml:math id="M285" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 6.3</oasis:entry>

         <oasis:entry colname="col8">440.3 <inline-formula><mml:math id="M286" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 8.1</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry colname="col2">Autumn</oasis:entry>

         <oasis:entry colname="col3">22.80 <inline-formula><mml:math id="M287" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.38</oasis:entry>

         <oasis:entry colname="col4">22.61 <inline-formula><mml:math id="M288" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.33</oasis:entry>

         <oasis:entry colname="col5">0.115 <inline-formula><mml:math id="M289" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.0124</oasis:entry>

         <oasis:entry colname="col6">0.037 <inline-formula><mml:math id="M290" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.002</oasis:entry>

         <oasis:entry colname="col7">39.4 <inline-formula><mml:math id="M291" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 11.4</oasis:entry>

         <oasis:entry colname="col8">428.8 <inline-formula><mml:math id="M292" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 7.3</oasis:entry>

       </oasis:row>
       <oasis:row rowsep="1">

         <oasis:entry colname="col2">Annual</oasis:entry>

         <oasis:entry colname="col3">21.91 <inline-formula><mml:math id="M293" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.43</oasis:entry>

         <oasis:entry colname="col4">21.76 <inline-formula><mml:math id="M294" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.38</oasis:entry>

         <oasis:entry colname="col5">0.131 <inline-formula><mml:math id="M295" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.024</oasis:entry>

         <oasis:entry colname="col6">0.037 <inline-formula><mml:math id="M296" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.003</oasis:entry>

         <oasis:entry colname="col7">29.9 <inline-formula><mml:math id="M297" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 10.4</oasis:entry>

         <oasis:entry colname="col8">422.7 <inline-formula><mml:math id="M298" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 7.6</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry rowsep="1" colname="col1" morerows="4">CanOA-VOS-1 (<italic>Jona Sophie</italic>;  GC-LNZ)</oasis:entry>

         <oasis:entry colname="col2">Winter</oasis:entry>

         <oasis:entry colname="col3">19.39 <inline-formula><mml:math id="M299" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.53</oasis:entry>

         <oasis:entry colname="col4">19.41 <inline-formula><mml:math id="M300" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.36</oasis:entry>

         <oasis:entry colname="col5">0.172 <inline-formula><mml:math id="M301" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.029</oasis:entry>

         <oasis:entry colname="col6">0.034 <inline-formula><mml:math id="M302" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.002</oasis:entry>

         <oasis:entry colname="col7">52.4 <inline-formula><mml:math id="M303" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 13.7</oasis:entry>

         <oasis:entry colname="col8">395.1 <inline-formula><mml:math id="M304" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 5.9</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry colname="col2">Spring</oasis:entry>

         <oasis:entry colname="col3">20.64 <inline-formula><mml:math id="M305" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.46</oasis:entry>

         <oasis:entry colname="col4">20.44 <inline-formula><mml:math id="M306" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.35</oasis:entry>

         <oasis:entry colname="col5">0.146 <inline-formula><mml:math id="M307" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.024</oasis:entry>

         <oasis:entry colname="col6">0.034 <inline-formula><mml:math id="M308" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.002</oasis:entry>

         <oasis:entry colname="col7">40.8 <inline-formula><mml:math id="M309" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 12.0</oasis:entry>

         <oasis:entry colname="col8">408.2 <inline-formula><mml:math id="M310" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 8.6</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry colname="col2">Summer</oasis:entry>

         <oasis:entry colname="col3">22.87 <inline-formula><mml:math id="M311" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.43</oasis:entry>

         <oasis:entry colname="col4">22.73 <inline-formula><mml:math id="M312" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.39</oasis:entry>

         <oasis:entry colname="col5">0.122 <inline-formula><mml:math id="M313" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.018</oasis:entry>

         <oasis:entry colname="col6">0.036 <inline-formula><mml:math id="M314" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.002</oasis:entry>

         <oasis:entry colname="col7">41.3 <inline-formula><mml:math id="M315" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 8.9</oasis:entry>

         <oasis:entry colname="col8">432.8 <inline-formula><mml:math id="M316" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 6.8</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry colname="col2">Autumn</oasis:entry>

         <oasis:entry colname="col3">22.09 <inline-formula><mml:math id="M317" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.45</oasis:entry>

         <oasis:entry colname="col4">21.98 <inline-formula><mml:math id="M318" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.37</oasis:entry>

         <oasis:entry colname="col5">0.106 <inline-formula><mml:math id="M319" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.022</oasis:entry>

         <oasis:entry colname="col6">0.034 <inline-formula><mml:math id="M320" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.002</oasis:entry>

         <oasis:entry colname="col7">32.2 <inline-formula><mml:math id="M321" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 5.6</oasis:entry>

         <oasis:entry colname="col8">415.3 <inline-formula><mml:math id="M322" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 5.8</oasis:entry>

       </oasis:row>
       <oasis:row rowsep="1">

         <oasis:entry colname="col2">Annual</oasis:entry>

         <oasis:entry colname="col3">21.25 <inline-formula><mml:math id="M323" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.47</oasis:entry>

         <oasis:entry colname="col4">21.32 <inline-formula><mml:math id="M324" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.37</oasis:entry>

         <oasis:entry colname="col5">0.136 <inline-formula><mml:math id="M325" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.023</oasis:entry>

         <oasis:entry colname="col6">0.034 <inline-formula><mml:math id="M326" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.002</oasis:entry>

         <oasis:entry colname="col7">41.7 <inline-formula><mml:math id="M327" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 10.0</oasis:entry>

         <oasis:entry colname="col8">412.8 <inline-formula><mml:math id="M328" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 4.3</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry rowsep="1" colname="col1" morerows="4">MORGAN-1  (GC)</oasis:entry>

         <oasis:entry colname="col2">Winter</oasis:entry>

         <oasis:entry colname="col3">21.07 <inline-formula><mml:math id="M329" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.30</oasis:entry>

         <oasis:entry colname="col4">20.99 <inline-formula><mml:math id="M330" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.23</oasis:entry>

         <oasis:entry colname="col5">0.193 <inline-formula><mml:math id="M331" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.045</oasis:entry>

         <oasis:entry colname="col6">0.043 <inline-formula><mml:math id="M332" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.004</oasis:entry>

         <oasis:entry colname="col7">57.0 <inline-formula><mml:math id="M333" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 11.3</oasis:entry>

         <oasis:entry colname="col8">393.4 <inline-formula><mml:math id="M334" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.9</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry colname="col2">Spring</oasis:entry>

         <oasis:entry colname="col3">21.49 <inline-formula><mml:math id="M335" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.31</oasis:entry>

         <oasis:entry colname="col4">20.66 <inline-formula><mml:math id="M336" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.25</oasis:entry>

         <oasis:entry colname="col5">0.129 <inline-formula><mml:math id="M337" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.021</oasis:entry>

         <oasis:entry colname="col6">0.039 <inline-formula><mml:math id="M338" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.004</oasis:entry>

         <oasis:entry colname="col7">25.3 <inline-formula><mml:math id="M339" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 9.4</oasis:entry>

         <oasis:entry colname="col8">405.1 <inline-formula><mml:math id="M340" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 2.0</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry colname="col2">Summer</oasis:entry>

         <oasis:entry colname="col3">21.50 <inline-formula><mml:math id="M341" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.34</oasis:entry>

         <oasis:entry colname="col4">22.97 <inline-formula><mml:math id="M342" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.24</oasis:entry>

         <oasis:entry colname="col5">0.11 <inline-formula><mml:math id="M343" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.016</oasis:entry>

         <oasis:entry colname="col6">0.04 <inline-formula><mml:math id="M344" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.004</oasis:entry>

         <oasis:entry colname="col7">23.1 <inline-formula><mml:math id="M345" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 5.9</oasis:entry>

         <oasis:entry colname="col8">431.7 <inline-formula><mml:math id="M346" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 2.8</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry colname="col2">Autumn</oasis:entry>

         <oasis:entry colname="col3">21.53 <inline-formula><mml:math id="M347" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.66</oasis:entry>

         <oasis:entry colname="col4">22.48 <inline-formula><mml:math id="M348" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.25</oasis:entry>

         <oasis:entry colname="col5">0.126 <inline-formula><mml:math id="M349" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.019</oasis:entry>

         <oasis:entry colname="col6">0.042 <inline-formula><mml:math id="M350" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.004</oasis:entry>

         <oasis:entry colname="col7">41.2 <inline-formula><mml:math id="M351" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 10.3</oasis:entry>

         <oasis:entry colname="col8">423.4 <inline-formula><mml:math id="M352" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 5.9</oasis:entry>

       </oasis:row>
       <oasis:row rowsep="1">

         <oasis:entry colname="col2">Annual</oasis:entry>

         <oasis:entry colname="col3">21.39 <inline-formula><mml:math id="M353" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.40</oasis:entry>

         <oasis:entry colname="col4">21.78 <inline-formula><mml:math id="M354" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.24</oasis:entry>

         <oasis:entry colname="col5">0.139 <inline-formula><mml:math id="M355" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.025</oasis:entry>

         <oasis:entry colname="col6">0.041 <inline-formula><mml:math id="M356" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.004</oasis:entry>

         <oasis:entry colname="col7">36.7 <inline-formula><mml:math id="M357" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 9.2</oasis:entry>

         <oasis:entry colname="col8">413.9 <inline-formula><mml:math id="M358" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 3.2</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry colname="col1" morerows="4">ULA-2  (EH)</oasis:entry>

         <oasis:entry colname="col2">Winter</oasis:entry>

         <oasis:entry colname="col3">19.76 <inline-formula><mml:math id="M359" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.38</oasis:entry>

         <oasis:entry colname="col4">19.73 <inline-formula><mml:math id="M360" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.39</oasis:entry>

         <oasis:entry colname="col5">0.193 <inline-formula><mml:math id="M361" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.033</oasis:entry>

         <oasis:entry colname="col6">0.042 <inline-formula><mml:math id="M362" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.003</oasis:entry>

         <oasis:entry colname="col7">47.7 <inline-formula><mml:math id="M363" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 19.0</oasis:entry>

         <oasis:entry colname="col8">385.6 <inline-formula><mml:math id="M364" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 3.3</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry colname="col2">Spring</oasis:entry>

         <oasis:entry colname="col3">20.52 <inline-formula><mml:math id="M365" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.56</oasis:entry>

         <oasis:entry colname="col4">20.48 <inline-formula><mml:math id="M366" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.52</oasis:entry>

         <oasis:entry colname="col5">0.155 <inline-formula><mml:math id="M367" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.037</oasis:entry>

         <oasis:entry colname="col6">0.037 <inline-formula><mml:math id="M368" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.003</oasis:entry>

         <oasis:entry colname="col7">24.5 <inline-formula><mml:math id="M369" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 7.9</oasis:entry>

         <oasis:entry colname="col8">397.9 <inline-formula><mml:math id="M370" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 5.0</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry colname="col2">Summer</oasis:entry>

         <oasis:entry colname="col3">21.92 <inline-formula><mml:math id="M371" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.38</oasis:entry>

         <oasis:entry colname="col4">21.83 <inline-formula><mml:math id="M372" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.33</oasis:entry>

         <oasis:entry colname="col5">0.159 <inline-formula><mml:math id="M373" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.039</oasis:entry>

         <oasis:entry colname="col6">0.041 <inline-formula><mml:math id="M374" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.006</oasis:entry>

         <oasis:entry colname="col7">25.2 <inline-formula><mml:math id="M375" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 8.0</oasis:entry>

         <oasis:entry colname="col8">429.3 <inline-formula><mml:math id="M376" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 4.6</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry colname="col2">Autumn</oasis:entry>

         <oasis:entry colname="col3">23.29 <inline-formula><mml:math id="M377" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.33</oasis:entry>

         <oasis:entry colname="col4">23.20 <inline-formula><mml:math id="M378" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.30</oasis:entry>

         <oasis:entry colname="col5">0.171 <inline-formula><mml:math id="M379" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.035</oasis:entry>

         <oasis:entry colname="col6">0.042 <inline-formula><mml:math id="M380" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.004</oasis:entry>

         <oasis:entry colname="col7">24.0 <inline-formula><mml:math id="M381" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 6.9</oasis:entry>

         <oasis:entry colname="col8">409.4 <inline-formula><mml:math id="M382" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 5.9</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry colname="col2">Annual</oasis:entry>

         <oasis:entry colname="col3">21.65 <inline-formula><mml:math id="M383" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.36</oasis:entry>

         <oasis:entry colname="col4">21.59 <inline-formula><mml:math id="M384" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.34</oasis:entry>

         <oasis:entry colname="col5">0.174 <inline-formula><mml:math id="M385" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.035</oasis:entry>

         <oasis:entry colname="col6">0.041 <inline-formula><mml:math id="M386" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.004</oasis:entry>

         <oasis:entry colname="col7">32.3 <inline-formula><mml:math id="M387" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 11.3</oasis:entry>

         <oasis:entry colname="col8">405.6 <inline-formula><mml:math id="M388" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 4.7</oasis:entry>

       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

      <fig id="F2" specific-use="star"><label>Figure 2</label><caption><p id="d2e5241">Monthly mean in situ SST (black) obtained from ship-based observations and moored buoys, and satellite-based SST (red) at locations <bold>(A)</bold>–<bold>(F)</bold>. Harmonic fittings (Eq. 4) of the data are shown together with the linear fitting for the seasonally detrended data. Error bars represent the standard deviation of the measurements.</p></caption>
        <graphic xlink:href="https://os.copernicus.org/articles/22/609/2026/os-22-609-2026-f02.png"/>

      </fig>

<sec id="Ch1.S3.SS1">
  <label>3.1</label><title>Variability of the SST data</title>
      <p id="d2e5264">Figure 2 shows the monthly mean SST derived from observations and satellite products at sites A–F. A clear seasonal cycle is evident across sites, with maximum SST in September (24.20 <inline-formula><mml:math id="M389" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.76 °C in the western sites at A–B and 23.70 <inline-formula><mml:math id="M390" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.68 °C in the eastern sites C–D) and minima in March (19.47 <inline-formula><mml:math id="M391" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.24 and 18.97 <inline-formula><mml:math id="M392" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.31 °C, respectively). Anomalous high SST were recorded during summer 2023, exceeding 25 °C at sites A–C and 24 °C at site D. The seasonal amplitude was 4.2 <inline-formula><mml:math id="M393" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.4 °C along CanOA-VOS-1 and 4.5 <inline-formula><mml:math id="M394" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.5 °C along the CanOA-VOS-2. Although no significant differences were found between sections within the same region (A vs B and C vs D), the mean SST at site D (20.59 <inline-formula><mml:math id="M395" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.09 °C) was slightly lower than at site C (21.00 <inline-formula><mml:math id="M396" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.09 °C). The covariance analysis between observational and satellite SST shows no significant differences between datasets (<inline-formula><mml:math id="M397" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">0.05</mml:mn></mml:mrow></mml:math></inline-formula>). The mean daily residuals were 0.16 °C (SE <inline-formula><mml:math id="M398" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 0.12 °C) in the western region and 0.12 °C (SE <inline-formula><mml:math id="M399" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 0.10 °C) in the eastern region.</p>
      <p id="d2e5350">A seasonal SST cycle was evident at site E, despite the scarcity and temporal gaps of the ULA-2 buoy (Fig. 2E). Using the year with the most continuous data (2021), the seasonal amplitude was 5.10 <inline-formula><mml:math id="M400" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.18 °C, with maximum SST in September (24.70 <inline-formula><mml:math id="M401" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.26 °C) and minimum values in March (19.60 <inline-formula><mml:math id="M402" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.40 °C). A comparable pattern was observed at site F from the MORGAN-1 buoy record (Fig. 2F), with SST peaking in September (23.71 <inline-formula><mml:math id="M403" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.47 °C) and reaching its lowest in March (19.46 <inline-formula><mml:math id="M404" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.52 °C), corresponding to a seasonal amplitude of 4.22 <inline-formula><mml:math id="M405" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.51 °C.</p>
      <p id="d2e5396">Longitudinal variability in SST from both CanOA-VOS and satellite records is shown in Figs. 2 and  S1 in the Supplement. In the western region, observed SST ranged from 20.59 <inline-formula><mml:math id="M406" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.09 °C in winter to 24.04 <inline-formula><mml:math id="M407" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.13 °C in summer, with an annual mean of 22.45 <inline-formula><mml:math id="M408" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.11 °C. Seasonal averages matched those calculated from the satellite-derived data (0.1–0.2 °C), with the largest differences occurring in summer (0.26 °C). Although SST in the eastern region were lower throughout the year (annual mean 21.02 <inline-formula><mml:math id="M409" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.27 °C), influenced by the Northwest African upwelling, similar seasonal variations were found (from 19.19 <inline-formula><mml:math id="M410" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.24 °C in winter to 22.82 <inline-formula><mml:math id="M411" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.25 °C in summer). Differences between in situ and satellite SST were smaller than those in the western region (0.05–0.2 °C). The west-east SST decrease persisted consistently along the longitudinally monitored span of the Canary archipelago, except for a slight warming associated with the island wake effect south of Tenerife captured along the CanOA-VOS-2 route (Fig. S1).</p>
</sec>
<sec id="Ch1.S3.SS2">
  <label>3.2</label><title>Predictive models of <inline-formula><mml:math id="M412" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub></title>
      <p id="d2e5471">Daily averaged <inline-formula><mml:math id="M414" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and SST from all observational platforms, together with coincident satellite-derived chlorophyll <inline-formula><mml:math id="M416" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> and MLD data at the same location, were used to train the four predictive models.</p>
<sec id="Ch1.S3.SS2.SSS1">
  <label>3.2.1</label><title>Multiple linear regression (MLR)</title>
      <p id="d2e5509">The first set of models used traditional multiple linear regression (<italic>MLR</italic>) to provide an initial, simple approximation of <inline-formula><mml:math id="M417" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> prediction. Five model configurations were tested, using different combinations of the available predictors: <inline-formula><mml:math id="M419" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,atm</sub>, SST, Chl <inline-formula><mml:math id="M421" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula>, Kd<sub>490</sub> and MLD, following the analytical form in Eq. (5). Considering the strong correlation between Chl <inline-formula><mml:math id="M423" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> and Kd<sub>490</sub> (<inline-formula><mml:math id="M425" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.96</mml:mn></mml:mrow></mml:math></inline-formula>), Kd<sub>490</sub> was deemed non-significant and excluded from further analysis. The coefficients obtained for each configuration are listed in Table 2.</p>

<table-wrap id="T2" specific-use="star"><label>Table 2</label><caption><p id="d2e5617">Regression coefficients obtained from the multiple linear regression models for pCO<sub>2,sw</sub> (top) and pH<sub>T,is</sub> (bottom), applied to the different predictor combinations according to Eq. (5), using the full dataset.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="6">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="right"/>
     <oasis:colspec colnum="3" colname="col3" align="right"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:colspec colnum="6" colname="col6" align="right"/>
     <oasis:thead>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1">Variables</oasis:entry>
         <oasis:entry colname="col2"><inline-formula><mml:math id="M429" display="inline"><mml:mrow><mml:msub><mml:mi>p</mml:mi><mml:mi mathvariant="normal">o</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M430" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula>)</oasis:entry>
         <oasis:entry colname="col3"><inline-formula><mml:math id="M431" display="inline"><mml:mover accent="true"><mml:mi mathvariant="italic">α</mml:mi><mml:mo stretchy="true" mathvariant="normal">^</mml:mo></mml:mover></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col4"><inline-formula><mml:math id="M432" display="inline"><mml:mover accent="true"><mml:mi mathvariant="italic">β</mml:mi><mml:mo stretchy="true" mathvariant="normal">^</mml:mo></mml:mover></mml:math></inline-formula>  (<inline-formula><mml:math id="M433" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> ° C<sup>−1</sup>)</oasis:entry>
         <oasis:entry colname="col5"><inline-formula><mml:math id="M435" display="inline"><mml:mover accent="true"><mml:mi mathvariant="italic">δ</mml:mi><mml:mo stretchy="true" mathvariant="normal">^</mml:mo></mml:mover></mml:math></inline-formula>  (<inline-formula><mml:math id="M436" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> mg<sup>−1</sup> m<sup>3</sup>)</oasis:entry>
         <oasis:entry colname="col6"><inline-formula><mml:math id="M439" display="inline"><mml:mover accent="true"><mml:mi mathvariant="italic">ε</mml:mi><mml:mo mathvariant="normal" stretchy="true">^</mml:mo></mml:mover></mml:math></inline-formula>  (<inline-formula><mml:math id="M440" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> m<sup>−1</sup>)</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>
         <oasis:entry colname="col1">SST</oasis:entry>
         <oasis:entry colname="col2">198.5</oasis:entry>
         <oasis:entry colname="col3">–</oasis:entry>
         <oasis:entry colname="col4">10.40</oasis:entry>
         <oasis:entry colname="col5">–</oasis:entry>
         <oasis:entry colname="col6">–</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">SST <inline-formula><mml:math id="M442" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M443" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col2">257.0</oasis:entry>
         <oasis:entry colname="col3">–</oasis:entry>
         <oasis:entry colname="col4">9.54</oasis:entry>
         <oasis:entry colname="col5"><inline-formula><mml:math id="M444" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>10.89</oasis:entry>
         <oasis:entry colname="col6">–</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">SST <inline-formula><mml:math id="M445" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col2">262.3</oasis:entry>
         <oasis:entry colname="col3">–</oasis:entry>
         <oasis:entry colname="col4">7.72</oasis:entry>
         <oasis:entry colname="col5">–</oasis:entry>
         <oasis:entry colname="col6"><inline-formula><mml:math id="M446" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.17</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">SST <inline-formula><mml:math id="M447" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M448" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M449" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col2">313.3</oasis:entry>
         <oasis:entry colname="col3">–</oasis:entry>
         <oasis:entry colname="col4">7.99</oasis:entry>
         <oasis:entry colname="col5"><inline-formula><mml:math id="M450" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.31</oasis:entry>
         <oasis:entry colname="col6"><inline-formula><mml:math id="M451" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.15</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"><inline-formula><mml:math id="M452" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,atm</sub> <inline-formula><mml:math id="M454" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> SST <inline-formula><mml:math id="M455" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M456" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M457" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col2">141.3</oasis:entry>
         <oasis:entry colname="col3">0.19</oasis:entry>
         <oasis:entry colname="col4">9.08</oasis:entry>
         <oasis:entry colname="col5"><inline-formula><mml:math id="M458" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>1.79</oasis:entry>
         <oasis:entry colname="col6"><inline-formula><mml:math id="M459" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.003</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1">Variables</oasis:entry>
         <oasis:entry colname="col2">pH<sub>o</sub></oasis:entry>
         <oasis:entry colname="col3"><inline-formula><mml:math id="M461" display="inline"><mml:mover accent="true"><mml:mi mathvariant="italic">α</mml:mi><mml:mo stretchy="true" mathvariant="normal">^</mml:mo></mml:mover></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col4"><inline-formula><mml:math id="M462" display="inline"><mml:mover accent="true"><mml:mi mathvariant="italic">β</mml:mi><mml:mo stretchy="true" mathvariant="normal">^</mml:mo></mml:mover></mml:math></inline-formula> (°C<sup>−1</sup>)</oasis:entry>
         <oasis:entry colname="col5"><inline-formula><mml:math id="M464" display="inline"><mml:mover accent="true"><mml:mi mathvariant="italic">δ</mml:mi><mml:mo mathvariant="normal" stretchy="true">^</mml:mo></mml:mover></mml:math></inline-formula> (mg<sup>−1</sup> m<sup>3</sup>)</oasis:entry>
         <oasis:entry colname="col6"><inline-formula><mml:math id="M467" display="inline"><mml:mover accent="true"><mml:mi mathvariant="italic">ε</mml:mi><mml:mo stretchy="true" mathvariant="normal">^</mml:mo></mml:mover></mml:math></inline-formula> (m<sup>−1</sup>)</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">SST</oasis:entry>
         <oasis:entry colname="col2">8.225</oasis:entry>
         <oasis:entry colname="col3">–</oasis:entry>
         <oasis:entry colname="col4"><inline-formula><mml:math id="M469" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.009</oasis:entry>
         <oasis:entry colname="col5">–</oasis:entry>
         <oasis:entry colname="col6">–</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">SST <inline-formula><mml:math id="M470" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M471" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col2">8.201</oasis:entry>
         <oasis:entry colname="col3">–</oasis:entry>
         <oasis:entry colname="col4"><inline-formula><mml:math id="M472" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.008</oasis:entry>
         <oasis:entry colname="col5">0.069</oasis:entry>
         <oasis:entry colname="col6">–</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">SST <inline-formula><mml:math id="M473" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col2">8.193</oasis:entry>
         <oasis:entry colname="col3">–</oasis:entry>
         <oasis:entry colname="col4"><inline-formula><mml:math id="M474" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.008</oasis:entry>
         <oasis:entry colname="col5">–</oasis:entry>
         <oasis:entry colname="col6">0.0002</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">SST <inline-formula><mml:math id="M475" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M476" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M477" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col2">8.185</oasis:entry>
         <oasis:entry colname="col3">–</oasis:entry>
         <oasis:entry colname="col4"><inline-formula><mml:math id="M478" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.007</oasis:entry>
         <oasis:entry colname="col5">0.001</oasis:entry>
         <oasis:entry colname="col6">0.008</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

      <p id="d2e6323">Model selection based on the Akaike Information Criterion (AIC<inline-formula><mml:math id="M479" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mi mathvariant="normal">c</mml:mi></mml:msub><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:math></inline-formula>) together with performance statistics (Table 3) suggest that the best-performing MLR included the atmospheric CO<sub>2</sub>, thermal, physical and biological drivers (<inline-formula><mml:math id="M481" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<inline-formula><mml:math id="M482" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>,</mml:mo><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:msub><mml:mo>+</mml:mo></mml:mrow></mml:math></inline-formula> SST <inline-formula><mml:math id="M483" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD <inline-formula><mml:math id="M484" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M485" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula>). However, a two-variable model (SST and <inline-formula><mml:math id="M486" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,atm</sub>) produced comparable accuracy. Figure S2 shows measured versus predicted values for the training and validation datasets using four variables, <inline-formula><mml:math id="M488" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<inline-formula><mml:math id="M489" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>,</mml:mo><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:msub><mml:mo>+</mml:mo></mml:mrow></mml:math></inline-formula> SST <inline-formula><mml:math id="M490" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD <inline-formula><mml:math id="M491" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M492" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula>. Although many measured and predicted <inline-formula><mml:math id="M493" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> showed small differences, considerable scatter was observed, reflected in the performance metrics (Table 3). Validation results (Table S2) were consistent with training performance.</p>

<table-wrap id="T3" specific-use="star"><label>Table 3</label><caption><p id="d2e6487">Performance metrics for the comparison between predicted and measured pCO<sub>2,sw</sub> (<inline-formula><mml:math id="M496" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula>) for each model using the training dataset.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="6">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="left"/>
     <oasis:colspec colnum="3" colname="col3" align="right"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:colspec colnum="6" colname="col6" align="right"/>
     <oasis:thead>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1">Algorithm</oasis:entry>
         <oasis:entry colname="col2">Variables</oasis:entry>
         <oasis:entry colname="col3"><inline-formula><mml:math id="M497" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col4">RMSE (<inline-formula><mml:math id="M498" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula>)</oasis:entry>
         <oasis:entry colname="col5">MAE (<inline-formula><mml:math id="M499" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> d<sup>−1</sup>)</oasis:entry>
         <oasis:entry colname="col6">SSE (<inline-formula><mml:math id="M501" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> d<sup>−1</sup>)</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>
         <oasis:entry colname="col1">MLR</oasis:entry>
         <oasis:entry colname="col2">SST</oasis:entry>
         <oasis:entry colname="col3">0.651</oasis:entry>
         <oasis:entry colname="col4">11.6</oasis:entry>
         <oasis:entry colname="col5">9.1</oasis:entry>
         <oasis:entry colname="col6">23.5</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M503" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M504" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col3">0.689</oasis:entry>
         <oasis:entry colname="col4">11.1</oasis:entry>
         <oasis:entry colname="col5">8.5</oasis:entry>
         <oasis:entry colname="col6">21.6</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M505" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col3">0.710</oasis:entry>
         <oasis:entry colname="col4">10.6</oasis:entry>
         <oasis:entry colname="col5">8.2</oasis:entry>
         <oasis:entry colname="col6">19.9</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M506" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M507" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M508" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col3">0.738</oasis:entry>
         <oasis:entry colname="col4">10.6</oasis:entry>
         <oasis:entry colname="col5">8.0</oasis:entry>
         <oasis:entry colname="col6">18.5</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M509" display="inline"><mml:mrow><mml:mo>+</mml:mo><mml:mi>p</mml:mi></mml:mrow></mml:math></inline-formula>CO<sub>2,atm</sub></oasis:entry>
         <oasis:entry colname="col3">0.865</oasis:entry>
         <oasis:entry colname="col4">6.7</oasis:entry>
         <oasis:entry colname="col5">5.0</oasis:entry>
         <oasis:entry colname="col6">15.3</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2"><inline-formula><mml:math id="M511" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,atm</sub> <inline-formula><mml:math id="M513" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> SST <inline-formula><mml:math id="M514" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M515" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M516" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col3">0.904</oasis:entry>
         <oasis:entry colname="col4">4.9</oasis:entry>
         <oasis:entry colname="col5">3.5</oasis:entry>
         <oasis:entry colname="col6">10.3</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">Neural Network (NN)</oasis:entry>
         <oasis:entry colname="col2">SST</oasis:entry>
         <oasis:entry colname="col3">0.740</oasis:entry>
         <oasis:entry colname="col4">10.4</oasis:entry>
         <oasis:entry colname="col5">7.7</oasis:entry>
         <oasis:entry colname="col6">25.6</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M517" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M518" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col3">0.778</oasis:entry>
         <oasis:entry colname="col4">9.4</oasis:entry>
         <oasis:entry colname="col5">6.7</oasis:entry>
         <oasis:entry colname="col6">19.5</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M519" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col3">0.842</oasis:entry>
         <oasis:entry colname="col4">8.1</oasis:entry>
         <oasis:entry colname="col5">5.7</oasis:entry>
         <oasis:entry colname="col6">18.2</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M520" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M521" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M522" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col3">0.881</oasis:entry>
         <oasis:entry colname="col4">7.2</oasis:entry>
         <oasis:entry colname="col5">5.0</oasis:entry>
         <oasis:entry colname="col6">17.2</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M523" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> <inline-formula><mml:math id="M524" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,atm</sub></oasis:entry>
         <oasis:entry colname="col3">0.877</oasis:entry>
         <oasis:entry colname="col4">7.8</oasis:entry>
         <oasis:entry colname="col5">5.1</oasis:entry>
         <oasis:entry colname="col6">17.8</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2"><inline-formula><mml:math id="M526" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<inline-formula><mml:math id="M527" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>,</mml:mo><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:msub><mml:mo>+</mml:mo></mml:mrow></mml:math></inline-formula> SST <inline-formula><mml:math id="M528" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M529" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M530" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col3">0.896</oasis:entry>
         <oasis:entry colname="col4">7.1</oasis:entry>
         <oasis:entry colname="col5">5.0</oasis:entry>
         <oasis:entry colname="col6">16.2</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">CatBoost</oasis:entry>
         <oasis:entry colname="col2">SST</oasis:entry>
         <oasis:entry colname="col3">0.737</oasis:entry>
         <oasis:entry colname="col4">10.1</oasis:entry>
         <oasis:entry colname="col5">7.4</oasis:entry>
         <oasis:entry colname="col6">16.2</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M531" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M532" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col3">0.848</oasis:entry>
         <oasis:entry colname="col4">7.7</oasis:entry>
         <oasis:entry colname="col5">5.5</oasis:entry>
         <oasis:entry colname="col6">9.3</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M533" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col3">0.877</oasis:entry>
         <oasis:entry colname="col4">6.9</oasis:entry>
         <oasis:entry colname="col5">5.0</oasis:entry>
         <oasis:entry colname="col6">7.5</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M534" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M535" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M536" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col3">0.935</oasis:entry>
         <oasis:entry colname="col4">5.4</oasis:entry>
         <oasis:entry colname="col5">3.9</oasis:entry>
         <oasis:entry colname="col6">4.7</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M537" display="inline"><mml:mrow><mml:mo>+</mml:mo><mml:mi>p</mml:mi></mml:mrow></mml:math></inline-formula>CO<sub>2,atm</sub></oasis:entry>
         <oasis:entry colname="col3">0.933</oasis:entry>
         <oasis:entry colname="col4">4.2</oasis:entry>
         <oasis:entry colname="col5">4.0</oasis:entry>
         <oasis:entry colname="col6">5.4</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2"><inline-formula><mml:math id="M539" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<inline-formula><mml:math id="M540" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>,</mml:mo><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:msub><mml:mo>+</mml:mo></mml:mrow></mml:math></inline-formula> SST <inline-formula><mml:math id="M541" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M542" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M543" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col3">0.956</oasis:entry>
         <oasis:entry colname="col4">3.6</oasis:entry>
         <oasis:entry colname="col5">2.4</oasis:entry>
         <oasis:entry colname="col6">3.0</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">Bagging</oasis:entry>
         <oasis:entry colname="col2">SST</oasis:entry>
         <oasis:entry colname="col3">0.946</oasis:entry>
         <oasis:entry colname="col4">4.7</oasis:entry>
         <oasis:entry colname="col5">3.4</oasis:entry>
         <oasis:entry colname="col6">3.5</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M544" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M545" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col3">0.972</oasis:entry>
         <oasis:entry colname="col4">3.4</oasis:entry>
         <oasis:entry colname="col5">2.3</oasis:entry>
         <oasis:entry colname="col6">1.9</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M546" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col3">0.975</oasis:entry>
         <oasis:entry colname="col4">3.0</oasis:entry>
         <oasis:entry colname="col5">2.1</oasis:entry>
         <oasis:entry colname="col6">1.5</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M547" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M548" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M549" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col3">0.991</oasis:entry>
         <oasis:entry colname="col4">2.5</oasis:entry>
         <oasis:entry colname="col5">1.6</oasis:entry>
         <oasis:entry colname="col6">0.9</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M550" display="inline"><mml:mrow><mml:mo>+</mml:mo><mml:mspace width="1em" linebreak="nobreak"/><mml:mi>p</mml:mi></mml:mrow></mml:math></inline-formula>CO<sub>2,atm</sub></oasis:entry>
         <oasis:entry colname="col3">0.982</oasis:entry>
         <oasis:entry colname="col4">2.6</oasis:entry>
         <oasis:entry colname="col5">2.085</oasis:entry>
         <oasis:entry colname="col6">1.1</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2"><inline-formula><mml:math id="M552" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<inline-formula><mml:math id="M553" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>,</mml:mo><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:msub><mml:mo>+</mml:mo></mml:mrow></mml:math></inline-formula> SST <inline-formula><mml:math id="M554" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M555" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M556" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col3">0.991</oasis:entry>
         <oasis:entry colname="col4">2.0</oasis:entry>
         <oasis:entry colname="col5">1.6</oasis:entry>
         <oasis:entry colname="col6">0.8</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

</sec>
<sec id="Ch1.S3.SS2.SSS2">
  <label>3.2.2</label><title>Machine learning techniques</title>
      <p id="d2e7584">Table 3 compares the performance of the machine-learning approaches trained using observational <inline-formula><mml:math id="M557" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> data. All models were developed using the same dataset and input variables.</p>
</sec>
<sec id="Ch1.S3.SS2.SSSx1" specific-use="unnumbered">
  <title>Neural Network (NN)</title>
      <p id="d2e7615">The first machine-learning method applied to predict <inline-formula><mml:math id="M559" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> was a neural network (NN). The performance metrics are presented in Table 3.</p>
      <p id="d2e7639">No analytical expression is provided, as the learned relationships are embedded within the synoptic weights of its neurons. Statistics indicate similar performances between the three-variable models (SST <inline-formula><mml:math id="M561" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD <inline-formula><mml:math id="M562" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M563" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula>) and the four-variable model, including <inline-formula><mml:math id="M564" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,atm</sub>, where two-variable models performed only slightly less effectively. Scatter plots of measured versus predicted <inline-formula><mml:math id="M566" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> for both training and validation datasets using the best NN model are shown in Fig. S2. Overall agreement was good, although prediction dispersion increased at higher <inline-formula><mml:math id="M568" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub>, suggesting slightly poorer fitness in this range. For the training dataset, RMSE, MAE, SSE, and <inline-formula><mml:math id="M570" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> were 7.1 <inline-formula><mml:math id="M571" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula>, 5.0 <inline-formula><mml:math id="M572" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> d<sup>−1</sup>, 16.2 <inline-formula><mml:math id="M574" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula><sup>2</sup> d<sup>−1</sup>, and 0.891, respectively.</p>
</sec>
<sec id="Ch1.S3.SS2.SSSx2" specific-use="unnumbered">
  <title>Categorical boosting (CatBoost) regression</title>
      <p id="d2e7807">The second machine-learning method applied to predict the <inline-formula><mml:math id="M577" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> in the Canary Archipelago was CatBoost. A total of 500 iterations were used to generate the prediction model. The performance statistics for all model configurations are summarised in Table 3. The <inline-formula><mml:math id="M579" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<inline-formula><mml:math id="M580" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>,</mml:mo><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:msub><mml:mo>+</mml:mo></mml:mrow></mml:math></inline-formula> SST <inline-formula><mml:math id="M581" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M582" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M583" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD configuration yielded the best results, achieving the lowest RMSE, MAE and SSE, and the highest <inline-formula><mml:math id="M584" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>. The performance of this model (Fig. S2), applied to both the training and validation datasets, yielded an <inline-formula><mml:math id="M585" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> greater than 0.95 with an RSME of only 3.6 <inline-formula><mml:math id="M586" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula>. The training dataset provided the most accurate results, with an MAE of 2.4 <inline-formula><mml:math id="M587" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> d<sup>−1</sup> and an SSE of 3.0 <inline-formula><mml:math id="M589" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula><sup>2</sup> d<sup>−1</sup>. The validation statistics were consistent with those obtained during the training phase (Table S2).</p>
</sec>
<sec id="Ch1.S3.SS2.SSSx3" specific-use="unnumbered">
  <title>Bootstrap aggregating (bagging) regression</title>
      <p id="d2e7968">A bagging algorithm was applied to predict <inline-formula><mml:math id="M592" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> using 200 bootstrap replicates. The computed statistics for the training set, combining the different parameters controlling the <inline-formula><mml:math id="M594" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> are summarised in Table 3.</p>
      <p id="d2e8013">Based on the statistical analysis, the models with the best predictive capacity were those that considered three or four parameters, as they yielded lower RMSE, MAE, and SSE. As observed in the previously fitted models, those including SST <inline-formula><mml:math id="M596" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD or SST <inline-formula><mml:math id="M597" display="inline"><mml:mrow><mml:mo>+</mml:mo><mml:mi>p</mml:mi></mml:mrow></mml:math></inline-formula>CO<sub>2,atm</sub> also performed well (Table 3). The bagging algorithm provided the highest <inline-formula><mml:math id="M599" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>, lowest RMSE, MAE and SSE (0.991, 2.0, 1.6, 0.8, respectively) for any combination of variables, even when only SST was considered. The plot of measured versus predicted <inline-formula><mml:math id="M600" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> for both the training and validation sets using a four-variable model is shown in Fig. S2. This model presented low RMSE, MAE, and SSE (2.0 <inline-formula><mml:math id="M602" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula>, 1.6 <inline-formula><mml:math id="M603" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> d<sup>−1</sup>, and 0.8 <inline-formula><mml:math id="M605" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula><sup>2</sup> d<sup>−1</sup>, respectively). In this scenario, the application of the model to the validation set showed greater data dispersion than the training set (Table S2), due to the smaller sample size (Fig. S2).</p>
</sec>
</sec>
<sec id="Ch1.S3.SS3">
  <label>3.3</label><title>Predictive models for pH<sub>T,is</sub></title>
      <p id="d2e8166">pH<sub>T,is</sub> predictions were generated from the computed pH<inline-formula><mml:math id="M610" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mi mathvariant="normal">T</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:msub><mml:mi>A</mml:mi><mml:mi mathvariant="normal">T</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>(SSS), <inline-formula><mml:math id="M611" display="inline"><mml:mi>f</mml:mi></mml:math></inline-formula>CO<sub>2</sub>), using observations and satellite data (interpolated to the time and location of each observation) as input variables. In this case, <inline-formula><mml:math id="M613" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,atm</sub> was excluded from the predictive variables to avoid redundancy. Table 4 shows a comparison of the models employed in the machine-learning-based approaches. It is important to note that all models were developed using the same dataset and input variable.</p>

<table-wrap id="T4" specific-use="star"><label>Table 4</label><caption><p id="d2e8241">Performance metrics for the comparison between predicted and measured pH<sub>T,is</sub> for each model using the training dataset.        </p></caption><oasis:table frame="topbot"><oasis:tgroup cols="6">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="left"/>
     <oasis:colspec colnum="3" colname="col3" align="right"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:colspec colnum="6" colname="col6" align="right"/>
     <oasis:thead>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1">Algorithm</oasis:entry>
         <oasis:entry colname="col2">Variables</oasis:entry>
         <oasis:entry colname="col3"><inline-formula><mml:math id="M616" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col4">RMSE (<inline-formula><mml:math id="M617" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula>)</oasis:entry>
         <oasis:entry colname="col5">MAE (<inline-formula><mml:math id="M618" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> d<sup>−1</sup>)</oasis:entry>
         <oasis:entry colname="col6">SSE (<inline-formula><mml:math id="M620" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> d<sup>−1</sup>)</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>
         <oasis:entry colname="col1">MLR</oasis:entry>
         <oasis:entry colname="col2">SST</oasis:entry>
         <oasis:entry colname="col3">0.678</oasis:entry>
         <oasis:entry colname="col4">0.009</oasis:entry>
         <oasis:entry colname="col5">0.008</oasis:entry>
         <oasis:entry colname="col6">0.056</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M622" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M623" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col3">0.713</oasis:entry>
         <oasis:entry colname="col4">0.009</oasis:entry>
         <oasis:entry colname="col5">0.007</oasis:entry>
         <oasis:entry colname="col6">0.040</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M624" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col3">0.733</oasis:entry>
         <oasis:entry colname="col4">0.009</oasis:entry>
         <oasis:entry colname="col5">0.007</oasis:entry>
         <oasis:entry colname="col6">0.028</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M625" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M626" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M627" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col3">0.745</oasis:entry>
         <oasis:entry colname="col4">0.006</oasis:entry>
         <oasis:entry colname="col5">0.005</oasis:entry>
         <oasis:entry colname="col6">0.013</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">Neural Network (NN)</oasis:entry>
         <oasis:entry colname="col2">SST</oasis:entry>
         <oasis:entry colname="col3">0.751</oasis:entry>
         <oasis:entry colname="col4">0.009</oasis:entry>
         <oasis:entry colname="col5">0.007</oasis:entry>
         <oasis:entry colname="col6">0.050</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M628" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M629" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col3">0.805</oasis:entry>
         <oasis:entry colname="col4">0.009</oasis:entry>
         <oasis:entry colname="col5">0.006</oasis:entry>
         <oasis:entry colname="col6">0.027</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M630" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col3">0.819</oasis:entry>
         <oasis:entry colname="col4">0.008</oasis:entry>
         <oasis:entry colname="col5">0.005</oasis:entry>
         <oasis:entry colname="col6">0.013</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M631" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M632" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M633" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col3">0.853</oasis:entry>
         <oasis:entry colname="col4">0.008</oasis:entry>
         <oasis:entry colname="col5">0.009</oasis:entry>
         <oasis:entry colname="col6">0.009</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">CatBoost</oasis:entry>
         <oasis:entry colname="col2">SST</oasis:entry>
         <oasis:entry colname="col3">0.756</oasis:entry>
         <oasis:entry colname="col4">0.008</oasis:entry>
         <oasis:entry colname="col5">0.008</oasis:entry>
         <oasis:entry colname="col6">0.041</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M634" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M635" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col3">0.866</oasis:entry>
         <oasis:entry colname="col4">0.006</oasis:entry>
         <oasis:entry colname="col5">0.004</oasis:entry>
         <oasis:entry colname="col6">0.006</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M636" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col3">0.898</oasis:entry>
         <oasis:entry colname="col4">0.005</oasis:entry>
         <oasis:entry colname="col5">0.004</oasis:entry>
         <oasis:entry colname="col6">0.009</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M637" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M638" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M639" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col3">0.934</oasis:entry>
         <oasis:entry colname="col4">0.004</oasis:entry>
         <oasis:entry colname="col5">0.003</oasis:entry>
         <oasis:entry colname="col6">0.002</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">Bagging</oasis:entry>
         <oasis:entry colname="col2">SST</oasis:entry>
         <oasis:entry colname="col3">0.954</oasis:entry>
         <oasis:entry colname="col4">0.004</oasis:entry>
         <oasis:entry colname="col5">0.002</oasis:entry>
         <oasis:entry colname="col6">0.015</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M640" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M641" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col3">0.982</oasis:entry>
         <oasis:entry colname="col4">0.003</oasis:entry>
         <oasis:entry colname="col5">0.002</oasis:entry>
         <oasis:entry colname="col6">0.002</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M642" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col3">0.983</oasis:entry>
         <oasis:entry colname="col4">0.002</oasis:entry>
         <oasis:entry colname="col5">0.002</oasis:entry>
         <oasis:entry colname="col6">0.005</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">SST <inline-formula><mml:math id="M643" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M644" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M645" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD</oasis:entry>
         <oasis:entry colname="col3">0.991</oasis:entry>
         <oasis:entry colname="col4">0.002</oasis:entry>
         <oasis:entry colname="col5">0.001</oasis:entry>
         <oasis:entry colname="col6">0.001</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

<sec id="Ch1.S3.SS3.SSS1">
  <label>3.3.1</label><title>Multiple linear regression (MLR)</title>
      <p id="d2e8880">The coefficients obtained for each of the four combination models are shown in Table 2. The statistical performance of these models is presented in Table 4. As observed for the <inline-formula><mml:math id="M646" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> fitting, the model including SST <inline-formula><mml:math id="M648" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M649" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M650" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD provided the best performance for pH<sub>T,is</sub>, with an <inline-formula><mml:math id="M652" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> of 0.745 and an RMSE of 0.006. The plot of measured versus predicted pH<sub>T,is</sub> for model training (Fig. S3) shows a distribution similar to that of the validation dataset. This indicates that the number of data points used for validation was not a limiting factor for the model.</p>
</sec>
<sec id="Ch1.S3.SS3.SSS2">
  <label>3.3.2</label><title>Machine learning techniques</title>
      <p id="d2e8974">All three techniques yielded higher correlation coefficients than those obtained using MLR (Table 4). The performance of the NN was lower than that of CatBoost, while bagging showed the best performance across all models. The model including three variables (SST <inline-formula><mml:math id="M654" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Chl <inline-formula><mml:math id="M655" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M656" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> MLD) was the most accurate for predicting pH<sub>T,is</sub> in all cases (Table 4), with an <inline-formula><mml:math id="M658" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> of up to 0.99 and an RMSE as low as 0.002 when applying the bagging technique. Every combination of satellite data, even when considering only the SST, resulted in an <inline-formula><mml:math id="M659" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> greater than 0.95 with bagging. For CatBoost, the three-variable model was required to achieve an <inline-formula><mml:math id="M660" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> above 0.93.</p>
      <p id="d2e9046">We compared the accuracy indicators for the training and validation datasets for the three-variable models (Tables 4 and S3, Fig. S3) within the pH<sub>T,is</sub> range of this study (7.97–8.07). When applying machine learning techniques, bagging consistently provided the best fit, ad increasing the data volume improved determination. RMSE, MAE, and SSE for both training and validation datasets remained below 0.01 in pH, reaching 0.002 and 0.003, respectively, when using bagging.</p>
</sec>
</sec>
<sec id="Ch1.S3.SS4">
  <label>3.4</label><title>Validation of the results</title>
      <p id="d2e9072">The best prediction models for each class, based on the evaluated statistical parameters, were used to reconstruct the monthly mean <inline-formula><mml:math id="M662" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and pH<sub>T,is</sub> at sites A–D, and the results were compared. The temporal variability of observed and predicted values is presented in Fig. 3. All models successfully reproduced the seasonal cycle: <inline-formula><mml:math id="M665" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> reached its maximum in March and its minimum in August-September, while pH<sub>T,is</sub> exhibited the opposite pattern. The predictions showed minor but statistically non-significant differences relative to the observations (<inline-formula><mml:math id="M668" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>&gt;</mml:mo><mml:mn mathvariant="normal">0.05</mml:mn></mml:mrow></mml:math></inline-formula>). No significant differences were detected among the linear, NN, CatBoost models (<inline-formula><mml:math id="M669" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">0.05</mml:mn></mml:mrow></mml:math></inline-formula>). When comparing bagging predictions with observational data, no significant differences were found, confirming that boostrap aggregation yielded the most accurate representation of the measured values. Overall, observed <inline-formula><mml:math id="M670" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> were slightly higher than predicted ones, with mean differences of 1.7 <inline-formula><mml:math id="M672" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.8 <inline-formula><mml:math id="M673" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> for <inline-formula><mml:math id="M674" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and 0.002 <inline-formula><mml:math id="M676" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.001 for pH<sub>T,is</sub>.</p>

      <fig id="F3" specific-use="star"><label>Figure 3</label><caption><p id="d2e9253">Monthly means of observational-based and model-predicted pCO<sub>2,sw</sub>(pCO<sub>2,atm</sub>, SST, Chl <inline-formula><mml:math id="M680" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula>, MLD) and pH<sub>T</sub>(SST, Chl <inline-formula><mml:math id="M682" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula>, MLD) at the locations A–D (Fig. 1). MLR (red) means multilinear regression, NN (green) means neural network, CBo (blue) means CatBoost and Bag (purple) means bagging. Linear fittings for the seasonally detrended data are plotted.</p></caption>
          <graphic xlink:href="https://os.copernicus.org/articles/22/609/2026/os-22-609-2026-f03.png"/>

        </fig>

      <p id="d2e9313">Statistical differences (<inline-formula><mml:math id="M683" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>&gt;</mml:mo><mml:mn mathvariant="normal">0.05</mml:mn></mml:mrow></mml:math></inline-formula>) were detected when comparing the western and eastern sectors by ANCOVA. At sites A and B (Fig. 3), <inline-formula><mml:math id="M684" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> (and pH<sub>T,is</sub>) varied seasonally between 404 <inline-formula><mml:math id="M687" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 18 <inline-formula><mml:math id="M688" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> (8.045 <inline-formula><mml:math id="M689" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.012) and 449 <inline-formula><mml:math id="M690" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 19 <inline-formula><mml:math id="M691" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> (8.004 <inline-formula><mml:math id="M692" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.010), with seasonal amplitudes of 47 <inline-formula><mml:math id="M693" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 8 <inline-formula><mml:math id="M694" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> (0.049 <inline-formula><mml:math id="M695" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.005). At sites C and D (Fig. 3), seasonal values ranged between 390 <inline-formula><mml:math id="M696" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 15 <inline-formula><mml:math id="M697" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> (8.069 <inline-formula><mml:math id="M698" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.008) and 440 <inline-formula><mml:math id="M699" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 16 <inline-formula><mml:math id="M700" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> (8.028 <inline-formula><mml:math id="M701" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.012), with amplitudes of 52 <inline-formula><mml:math id="M702" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 7 <inline-formula><mml:math id="M703" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> (0.038 <inline-formula><mml:math id="M704" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.006).</p>
</sec>
</sec>
<sec id="Ch1.S4">
  <label>4</label><title>Discussion</title>
      <p id="d2e9519">Three oceanographic variables (SST, Chl <inline-formula><mml:math id="M705" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> and MLD) with high-resolution satellite coverage for oceanic surface seawater, together with atmospheric CO<sub>2</sub> partial pressure, were used to model <inline-formula><mml:math id="M707" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and pH<sub>T,is</sub> in the Canary Archipelago. Salinity was excluded from the fitted models due to its negligible influence on <inline-formula><mml:math id="M710" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> variability (Sarmiento et al., 2007; Shadwick et al., 2010). Furthermore, satellite-derived salinity has been shown to differ considerably from in situ measurements, exhibiting elevated variability and uncertainty (Yu, 2020). Although Kd<sub>490</sub> was included in the initial model tests, its lack of statistical significance is likely due to its strong correlation with Chl <inline-formula><mml:math id="M713" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> (<inline-formula><mml:math id="M714" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.96</mml:mn></mml:mrow></mml:math></inline-formula>), making it redundant and therefore not retained as a predictor.</p>
<sec id="Ch1.S4.SS1">
  <label>4.1</label><title>The Canary Region during 2019–2024: Observational and modelling data</title>
      <p id="d2e9633">In the Canary Islands, the highest temperatures (Fig. 2) were recorded in late summer (September), driven by enhanced stratification of the water column and increased solar radiation. The lowest temperatures were measured in winter (February–March) due to convective mixing induced by surface cooling of the water column. This seasonal behaviour is consistent with the hydrographic conditions described at the ESTOC site, where surface waters exhibit a seasonal temperature amplitude of 4–6 °C, with minimum and maximum temperatures of 18 and 24 °C, respectively, recorded before 2023 (González-Dávila and Santana-Casiano, 2023). This range is also comparable to the SST observed in the easternmost region covered by the CanOA VOS-1 during 2019–2020 (Curbelo-Hernández et al., 2021).</p>
      <p id="d2e9636">The statistically significant differences (<inline-formula><mml:math id="M715" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">0.05</mml:mn></mml:mrow></mml:math></inline-formula>) observed between the western and eastern sections are related to their distance from the African continent. The easternmost part of the archipelago is more exposed to upwelling filaments (Davenport et al., 1999), whereas the westernmost part is partially sheltered by the islands themselves. This spatial pattern, clearly visible in Figs. 2 and S1 as a progressive decrease in SST towards the African coast, is well captured by satellite observations. Their validation showed no significant differences (<inline-formula><mml:math id="M716" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">0.05</mml:mn></mml:mrow></mml:math></inline-formula>), even near the islands. Therefore, satellite data were deemed suitable for model fitting and subsequent parameter estimation.</p>
      <p id="d2e9663">MORGAN-1 data (site F) show anomalously high SST during the summer of 2023, consistent with the occurrence of extreme SST conditions in the Canary Upwelling System in 2023 (Varela et al., 2024). Satellite data at the coastal buoy locations also showed anomalously high summer values, although these were on average 0.3 °C lower than those measured by the buoy sensors. In situ temperatures from June to October 2023 were more than 1 °C higher than those recorded in previous years. These elevated temperatures were not observed in 2024, indicating that 2023 should be considered an anomalous year in this region.</p>
      <p id="d2e9666">It is noteworthy that SST during February–March 2024 remained high. Winter SST (JFM) increased in 2024 and was, on average, 1 °C warmer than in the previous years (average for 2020–2022 was 19.09 <inline-formula><mml:math id="M717" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.20 °C; average for 2023–2024 was 20.01 <inline-formula><mml:math id="M718" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.25 °C). These anomalies strongly influence the trends observed in both satellite and observational datasets.</p>
      <p id="d2e9684">Harmonic fitting of temperature (Eq. 4) for the period March 2020 to March 2023, despite the limitation of only three years of data, indicates a warming trend of 0.03 °C yr<sup>−1</sup> in the seasonally detrended Gando Bay dataset (González et al., 2024). This rate is comparable to warming rates trends reported at the ESTOC site for the period October 1995 to March 2023 (González-Dávila and Santana-Casiano, 2023) and for the full Canary Upwelling System over 1982–2023 (Varela et al., 2024).</p>
      <p id="d2e9699">When considering the full five-year seasonally detrended in situ dataset from Gando Bay (March 2020 to October 2024), the warming rate increases to 0.19 <inline-formula><mml:math id="M720" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.06 °C yr<sup>−1</sup> (0.14 <inline-formula><mml:math id="M722" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.06 °C yr<sup>−1</sup> when derived from monthly mean satellite data). This SST increase was also observed at sites A–D (Fig. 2), where warming rates over the six years from February 2019 to October 2024 ranged from 0.29 <inline-formula><mml:math id="M724" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.03 °C yr<sup>−1</sup> at sites A–C to 0.21 °C r<sup>−1</sup> at site D. The mean temperature at the western station (ULA-2) was <inline-formula><mml:math id="M727" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 1 °C higher (22.12 <inline-formula><mml:math id="M728" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.16 °C) than at the eastern station F (MORGAN-1; 21.13 <inline-formula><mml:math id="M729" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.12 °C), reflecting the influence of Northwest African upwelling and island coastal upwelling. ANCOVA applied to both buoy datasets showed no significant differences between in situ and the satellite-derived SST, with mean differences below 0.19 °C, comparable to the regional mean difference of 0.15 °C for the full Canary dataset.</p>
      <p id="d2e9793">Satellite-derived data were used to predict <inline-formula><mml:math id="M730" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and pH<sub>T,is</sub>. The neural network model exhibited the highest prediction error (RMSE <inline-formula><mml:math id="M733" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 7.1 <inline-formula><mml:math id="M734" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M735" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.896</mml:mn></mml:mrow></mml:math></inline-formula>), whereas the MLR model performed slightly better (RMSE <inline-formula><mml:math id="M736" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 4.9 <inline-formula><mml:math id="M737" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M738" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.904</mml:mn></mml:mrow></mml:math></inline-formula> for <inline-formula><mml:math id="M739" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub>). Previous studies applying MLR along the US coasts reported RMSE values ranging from 22.4 to 36.9 <inline-formula><mml:math id="M741" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> (Signorini et al., 2013), while NN-based approaches in the North and South Atlantic Ocean yielded RMSE values exceeding 19 <inline-formula><mml:math id="M742" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> (Ford et al., 2022) and 21.68 <inline-formula><mml:math id="M743" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> (Friedrich and Oschlies, 2009), respectively. In comparison, both MLR and NN models applied in the present study perform favourably, likely due to the limited spatial domain and the extensive observational dataset. For pH<sub>T,is</sub> estimation, RMSE as low as 0.006 and 0.008 were obtained for MLR and NN, respectively, which fall within the typical analytical uncertainty.</p>
      <p id="d2e9962">The CatBoost empirical algorithm estimated <inline-formula><mml:math id="M745" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and pH<sub>T,is</sub> with uncertainties below 4 <inline-formula><mml:math id="M748" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> and 0.004 pH, respectively, and <inline-formula><mml:math id="M749" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>&gt;</mml:mo><mml:mn mathvariant="normal">0.93</mml:mn></mml:mrow></mml:math></inline-formula> for both variables. This demonstrates robustness to uncertainty in satellite-derived variables influenced by different processes and coastal proximity, supporting its applicability in the region. However, the bagging approach exhibited exceptional performance, yielding uncertainties of 2.0 <inline-formula><mml:math id="M750" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> for <inline-formula><mml:math id="M751" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and 0.002 pH for pH<sub>T,is</sub> over the period 2019–2024.</p>
      <p id="d2e10071">These particularly favourable results, and the comparatively low errors relative to ocean-scale models, likely arise because variability in <inline-formula><mml:math id="M754" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and pH<sub>T,is</sub> in the Canary Island waters is largely dominated by thermal effects (González-Dávila and Santana-Casiano, 2023; Takahashi et al., 2002). In this region, thermal control of surface carbonate chemistry is effectively captured by satellite-derived SST. In all cases, models using SST alone showed high correlation coefficients (<inline-formula><mml:math id="M757" display="inline"><mml:mrow><mml:mn mathvariant="normal">0.65</mml:mn><mml:mo>&lt;</mml:mo><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">0.94</mml:mn></mml:mrow></mml:math></inline-formula>). Although not the best-performing configurations, these single-variable models provide a reasonable representation of observed variability. The coefficient estimated from annual linear regression (10.40 <inline-formula><mml:math id="M758" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> °C<sup>−1</sup>, Table 2) deviates from the theoretical regional rate for 2019–2024 (16 <inline-formula><mml:math id="M760" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> °C<sup>−1</sup>; Takahashi et al., 2002), likely reflecting the influence of biological and physical processes (i.e., primary production, remineralisation and water mass mixing). Nevertheless, this rate remains consistent with those reported for ESTOC (Santana-Casiano et al., 2007).</p>
      <p id="d2e10173">Across all four sites and in Gando Bay, both observational data and model predictions indicate that <inline-formula><mml:math id="M762" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> increased between 2019 and 2024 at a rate of 3.8 <inline-formula><mml:math id="M764" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.6 <inline-formula><mml:math id="M765" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> yr<sup>−1</sup>. The pH<sub>T,is</sub> decreased at a rate of <inline-formula><mml:math id="M768" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.004 <inline-formula><mml:math id="M769" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.001 yr<sup>−1</sup> over the same period. Previous analyses at ESTOC for 1995–2023 (González-Dávila and Santana-Casiano, 2023) and at Gando Bay (site F) for 2020–2023 (González et al., 2024) reported a <inline-formula><mml:math id="M771" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> increase of 2.1 <inline-formula><mml:math id="M773" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.1 <inline-formula><mml:math id="M774" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> yr<sup>−1</sup> and a pH<sub>T,is</sub> decrease of <inline-formula><mml:math id="M777" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.002 <inline-formula><mml:math id="M778" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.001 yr<sup>−1</sup>. Comparable rates are observed across all selected sites when restricting analysis to March 2019–March 2023, excluding the anomalous conditions observed in late 2023, consistent with González et al. (2024).</p>
</sec>
<sec id="Ch1.S4.SS2">
  <label>4.2</label><title>Monthly <inline-formula><mml:math id="M780" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and pH<sub>T,is</sub> gridded maps</title>
      <p id="d2e10403">The bagging technique was used to construct gridded monthly maps of <inline-formula><mml:math id="M783" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and pH<sub>T,is</sub> for the Canary region (13–19° W, 27–30° N) over the study period. Results for the year 2023 are presented in Fig. 4. Monthly experimental averages are shown alongside the model predictions to illustrate the accuracy of the estimates. The expected seasonal pattern was reproduced, with higher <inline-formula><mml:math id="M786" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> in September and lower in March, and the opposite behaviour for pH<sub>T,is</sub>. A clear longitudinal gradient was observed, with higher <inline-formula><mml:math id="M789" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and lower pH<sub>T,is</sub> toward the eastern sector, primarily driven by the thermal effect. Cooler seawater in the east, together with the influence of nutrient-rich, lower-pH Northeast African upwelled seawater (Pelegrí et al., 2005), counteract each other, increasing mean values while reducing seasonal amplitude.</p>

      <fig id="F4" specific-use="star"><label>Figure 4</label><caption><p id="d2e10514">Gridded maps for pCO<sub>2,sw</sub> (left) and pH<sub>T,sw</sub> (right) predicted with bagging for the full March (Mar), June (Jun), September (Sep) and December (Dec) 2023 using pCO<sub>2,atm</sub> and satellite conditions of SST, Chl <inline-formula><mml:math id="M795" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula>, and MLD together with observational data available for that month (the same colour code was used). Figure produced with Ocean Data View (Schlitzer, 2021; <uri>https://odv.awi.de</uri>, last access: 10 July 2025).</p></caption>
          <graphic xlink:href="https://os.copernicus.org/articles/22/609/2026/os-22-609-2026-f04.jpg"/>

        </fig>

      <p id="d2e10575">Several oceanographic features are apparent. Upwelling filaments, characterised by lower temperatures, locally reduce <inline-formula><mml:math id="M796" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub>. In contrast, leeward island wake zones exhibit warmer waters, leading to increased <inline-formula><mml:math id="M798" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and decreased pH<sub>T,is</sub>. The African coastal upwelling signal is particularly evident in June and September, when lower <inline-formula><mml:math id="M801" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and higher pH<sub>T,is</sub> are observed as a result of enhanced biological activity that partially offsets the CO<sub>2</sub>-rich upwelled waters.</p>
      <p id="d2e10680">Monthly mean <inline-formula><mml:math id="M805" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and pH<sub>T,is</sub> for the Canary Basin, predicted using the bagging approach for the period 2019–2024, are shown in Fig. 5. Monthly means were computed by applying the bagging model to daily satellite-derived SST, Chl <inline-formula><mml:math id="M808" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula>, and MLD, together with <inline-formula><mml:math id="M809" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,atm</sub>, and subsequently averaging the results spatially and temporally. Over these six years, mean <inline-formula><mml:math id="M811" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> was 419.7 <inline-formula><mml:math id="M813" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 16 <inline-formula><mml:math id="M814" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula>, with a seasonal amplitude of 55 <inline-formula><mml:math id="M815" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula>. Harmonic fitting (Eq. 4) of the predicted time series indicates an increasing trend of 3.51 <inline-formula><mml:math id="M816" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.31 <inline-formula><mml:math id="M817" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> yr<sup>−1</sup> for 2019–2024, exceeding the contemporaneous increase in <inline-formula><mml:math id="M819" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,atm</sub> (2.3 <inline-formula><mml:math id="M821" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> yr<sup>−1</sup>).</p>

      <fig id="F5"><label>Figure 5</label><caption><p id="d2e10871">Monthly means of pCO<sub>2,sw</sub> (<inline-formula><mml:math id="M824" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula>) and pH<sub>T,sw</sub> predicted with bagging for 2019–2024 for the entire Canary region (27–30° N, 13–19° W). Linear fittings for the seasonally detrended data are also plotted.</p></caption>
          <graphic xlink:href="https://os.copernicus.org/articles/22/609/2026/os-22-609-2026-f05.png"/>

        </fig>

      <p id="d2e10918">Predicted pH<sub>T,is</sub> (Fig. 5) ranged from 8.015 <inline-formula><mml:math id="M827" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.049 in February–March to 7.980 <inline-formula><mml:math id="M828" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.058 in September–October, reflecting a seasonal decrease of <inline-formula><mml:math id="M829" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 0.04 pH from winter to summer. Elevated winter values reflect lower temperatures and enhanced convective mixing, whereas lower summer values are attributed to biological activity and water-column stratification (Santana-Casiano et al., 2001, 2007). This seasonal pH decrease is partially offset by the thermal effect, which compensates for approximately 33 % of the total decline. The thermal contribution corresponds to a pH decrease of 0.06 associated with a temperature increase of 4.1 °C. This compensating effect is evident near the African coast (Fig. 5), where upwelling of deep, cold, CO<sub>2</sub>-rich waters reduces both SST and pH, generating a pronounced longitudinal gradient across the Canary region.</p>
      <p id="d2e10965">Figure 5 further shows that pH<sub>T,is</sub> declined throughout the study period due to increasing ocean acidity, with a rate of <inline-formula><mml:math id="M832" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.003 <inline-formula><mml:math id="M833" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.001 yr<sup>−1</sup> derived from seasonally detrended data. The strong influence of MHW events, particularly during summer 2023 and winter 2023–2024, on the interannual trends of both variables is evident. The rise in <inline-formula><mml:math id="M835" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,atm</sub> is accompanied by an increase in SST of 0.2 °C yr<sup>−1</sup> over the six years, equivalent to a cumulative warming of 1.2 °C between 2019 and 2024. This increase is largely driven by the anomalously warm conditions in 2023, higher SST in winter 2020 compared to 2019, and elevated winter SST in 2023 and 2024 relative to 2022, when winter temperatures dropped below 18 °C and have since remained near 19 °C. These conditions have contributed to higher recent trends in <inline-formula><mml:math id="M838" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and ocean acidification relative to long-term estimates at ESTOC, which were 2.1 <inline-formula><mml:math id="M840" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> yr<sup>−1</sup> and <inline-formula><mml:math id="M842" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.002 yr<sup>−1</sup>, respectively, for the period 1995 to early 2023 (González-Dávila and  Santana-Casiano, 2023). The limited six-year time series may also contribute to the magnitude of the observed rates. Notably, winters with SST exceeding 19 °C and summers with SST above 25 °C had not been recorded at the ESTOC site before 2023.</p>
</sec>
<sec id="Ch1.S4.SS3">
  <label>4.3</label><title>Long-term model prediction at ESTOC site</title>
      <p id="d2e11113">The bagging predictive model developed using data from the period 2019–2024 was applied to the ESTOC site for the period 2004–2024. Earlier years were not considered because the monthly satellite data before this period had lower spatial resolution. Satellite-derived SST, Chl <inline-formula><mml:math id="M844" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula>, and MLD, together with atmospheric <inline-formula><mml:math id="M845" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2</sub> computed from <inline-formula><mml:math id="M847" display="inline"><mml:mi>x</mml:mi></mml:math></inline-formula>CO<sub>2</sub> measurements at the Izaña (IZO) station, were used as model inputs (<uri>https://gml.noaa.gov/aftp/data/trace_gases/co2/flask/surface/txt/co2_izo_surface-flask_1_ccgg_event.txt</uri>, last access: 26 May 2025). Estimated values at 29°10′ N and 15°30′ W were compared with in situ observations from ESTOC (González-Dávila and Santana Casiano, 2023), updated to 2024, and are shown in Fig. 6. The model reproduced the ESTOC observations with mean residuals of 1.3 <inline-formula><mml:math id="M851" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 3.1 <inline-formula><mml:math id="M852" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> and yielded consistent trends of 1.9 <inline-formula><mml:math id="M853" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.1 <inline-formula><mml:math id="M854" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> yr<sup>−1</sup> over the study period, as determined from both model output and the seasonally detrended observational data.</p>

      <fig id="F6"><label>Figure 6</label><caption><p id="d2e11238">Monthly means of pCO<sub>2,sw</sub> (<inline-formula><mml:math id="M857" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula>) predicted with bagging considering pCO<sub>2,atm</sub>, SST, Chl <inline-formula><mml:math id="M859" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula>, MLD for the period 2004–2024 at the location of the ESTOC site (G in Fig. 1) and measured ESTOC pCO<sub>2,sw</sub>.</p></caption>
          <graphic xlink:href="https://os.copernicus.org/articles/22/609/2026/os-22-609-2026-f06.png"/>

        </fig>

      <p id="d2e11306">When models excluding <inline-formula><mml:math id="M861" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,atm</sub> were applied, residuals increased to values exceeding 2 <inline-formula><mml:math id="M863" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula>, particularly during the early part of the record (2004–2010), when residuals approached 4 <inline-formula><mml:math id="M864" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula>. This behaviour reflects the increased weighting assigned to SST in the absence of atmospheric forcing, especially during periods characterised by strong thermal anomalies such as the 2023 marine heatwave in the Canary Upwelling System. Analysis of satellite-derived SST at the ESTOC site for 2004–2024 shows minimal temperature variability during 2004–2019 (0.0012 <inline-formula><mml:math id="M865" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.002 °C yr<sup>−1</sup>), followed by a marked warming trend during 2019–2024 (0.21 <inline-formula><mml:math id="M867" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.01 °C yr<sup>−1</sup>), consistent with the behaviour observed at sites A–F (Fig. 1). Consequently, when models based solely on SST, Chl <inline-formula><mml:math id="M869" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> and MLD were applied to earlier periods, lower <inline-formula><mml:math id="M870" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> trends were predicted. In contrast, inclusion of <inline-formula><mml:math id="M872" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,atm</sub> in the model allows both thermal and atmospheric contributions to <inline-formula><mml:math id="M874" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> to be accounted for, ensuring that periods with weak SST trends still reflect the concurrent rise in atmospheric CO<sub>2</sub> and its influence on surface seawater <inline-formula><mml:math id="M877" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2</sub>.</p>
</sec>
<sec id="Ch1.S4.SS4">
  <label>4.4</label><title>Air-sea CO<sub>2</sub> exchange in the Canary Archipelago</title>
      <p id="d2e11505">The predicted <inline-formula><mml:math id="M880" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> is highly useful for estimating FCO<sub>2</sub> with improved spatial and temporal resolution. Figure 7 shows FCO<sub>2</sub> calculated using the parametrisation proposed by Wanninkhof (2014) under monthly mean conditions for the period 2019–2024. The seasonal cycle of FCO<sub>2</sub> is primarily controlled by the large seasonal variability in <inline-formula><mml:math id="M885" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub>, which governs <inline-formula><mml:math id="M887" display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:mi>p</mml:mi></mml:mrow></mml:math></inline-formula>CO<sub>2</sub>, as <inline-formula><mml:math id="M889" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,atm</sub> exhibits a much smaller seasonal amplitude. In contrast, the effect of wind speed and gas solubility exhibits a smaller seasonal amplitude (Landschützer et al., 2014).</p>

      <fig id="F7"><label>Figure 7</label><caption><p id="d2e11620"><bold>(A)</bold> Monthly means of FCO<sub>2</sub> (mmol m<sup>−2</sup> d<sup>−1</sup>) in the Canary archipelagic waters predicted with bagging from 2019 to 2024 and <bold>(B)</bold> net annual FCO<sub>2</sub> (mol m<sup>−2</sup> yr<sup>−1</sup>). In both plots, FCO<sub>2</sub> was represented at locations A–F and for the entire Canary Region (CR). Linear fittings for the seasonally detrended data are also plotted.</p></caption>
          <graphic xlink:href="https://os.copernicus.org/articles/22/609/2026/os-22-609-2026-f07.png"/>

        </fig>

      <p id="d2e11710">The region acts as a strong CO<sub>2</sub> sink during winter and spring, whereas during the warm season it behaves as a source. During the warm period from late May to early September (González-Dávila et al., 2003), when the dominant trade winds impact the Canary Islands, <inline-formula><mml:math id="M899" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> exceeds <inline-formula><mml:math id="M901" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,atm</sub>. This leads to higher wind speeds and reinforces the role of CO<sub>2</sub> supersaturation in the total flux estimation, favouring the region's role as a CO<sub>2</sub> source.</p>
      <p id="d2e11784">Sites located closer to the African continent (C and D) and the coastal waters (F in the Gando Bay, also in the eastern part of the Canary Islands) are more likely to act as a CO<sub>2</sub> sink than the westernmost region (Curbelo-Hernández et al., 2021). This behaviour is primarily associated with the thermal gradient, with temperatures more than 1 °C lower than in the western sector, as well as with higher biological productivity. However, Fig. 7B shows that, due to the increase in SST across the Canary Islands during the study period, all locations that previously acted as an annual CO<sub>2</sub> sink shifted to behaving as a source after 2022.</p>
      <p id="d2e11805">For the period 2019–2024, the Canary region acted as a weak CO<sub>2</sub> source, with a mean flux of 0.39 <inline-formula><mml:math id="M908" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.17 mol m<sup>−2</sup> yr<sup>−1</sup>. Increasing flux trends were observed across all sub-regions, ranging from 0.18 to 0.37 mmol m<sup>−2</sup> d<sup>−1</sup>, with an average rate of 0.25 <inline-formula><mml:math id="M913" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.02 mmol m<sup>−2</sup> d<sup>−1</sup>. When considering the entire Canary region (13–19° W, 27–30° N), covering an area of 185 000 km<sup>2</sup> after excluding the island land masses, the system transitioned from a weak source of 0.9 Tg CO<sup>2</sup> in 2019 to a source of 4.5 Tg CO<sub>2</sub> in 2024, with a maximum of 4.8 Tg CO<sub>2</sub> in 2023. This peak coincided with the highest SST recorded during the study period (Fig. 2), favouring the largest increase in <inline-formula><mml:math id="M920" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub>.</p>
      <p id="d2e11962">These estimates are primarily based on surface water measurements, particularly those derived from satellite data. Although such datasets provide high spatial resolution and robust representation of surface trends, they do not capture subsurface processes or vertical gradients in CO<sub>2</sub> and temperature.</p>
</sec>
</sec>
<sec id="Ch1.S5" sec-type="conclusions">
  <label>5</label><title>Conclusions</title>
      <p id="d2e11984">This study presents the first predictive modelling framework for surface seawater <inline-formula><mml:math id="M923" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and pH<sub>T,is</sub> in the Canary Islands basin. The results demonstrate the value of satellite observations as a complement to in situ platforms such as voluntary observing ships and moored buoys. By combining satellite products from the Copernicus Marine Environmental Monitoring Service with in situ observations, it was possible to characterise the variability of <inline-formula><mml:math id="M926" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and pH<sub>T,is</sub> in the waters surrounding the Canary Islands and to quantify the regional air-sea CO<sub>2</sub> flux.</p>
      <p id="d2e12067">Four modelling approaches, ranging from classical multivariate statistics to more sophisticated machine-learning techniques, were applied using atmospheric <inline-formula><mml:math id="M930" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2</sub>, SST, Chl <inline-formula><mml:math id="M932" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula>, and MLD as controlling variables. Multiple linear regression, neural network, and categorical boosting models yielded comparable results, with RMSE, MAE, and <inline-formula><mml:math id="M933" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> values similar to those reported for oceanic-scale applications. Among all approaches, the bagging model provided the best performance, with RMSE values below 2.5 <inline-formula><mml:math id="M934" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">atm</mml:mi></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M935" display="inline"><mml:mo lspace="0mm">&lt;</mml:mo></mml:math></inline-formula> 0.7 %) for <inline-formula><mml:math id="M936" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and 0.002 for pH<sub>T,is</sub>, <inline-formula><mml:math id="M939" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> exceeding 0.99, and no significant differences relative to monthly mean observations.</p>
      <p id="d2e12168">Application of the bagging approach enabled a detailed description of the seasonal and longitudinal variability of <inline-formula><mml:math id="M940" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and pH<sub>T,is</sub> across the Canary region. After confirming agreement between in situ and satellite-derived SST within <inline-formula><mml:math id="M943" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>0.15 °C, the model was trained using measured <inline-formula><mml:math id="M944" display="inline"><mml:mi>x</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> (converted to <inline-formula><mml:math id="M946" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub>) together with satellite SST, chlorophyll <inline-formula><mml:math id="M948" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> and MLD, providing high-resolution spatial and temporal coverage. A persistent longitudinal SST gradient of <inline-formula><mml:math id="M949" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 1 °C, driven by African coastal upwelling and offshore transport of upwelling filaments, resulted in systematically higher <inline-formula><mml:math id="M950" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and lower pH<sub>T,is</sub> values in the western sector (between El Hierro and Tenerife) compared with the eastern sector (between Tenerife and Lanzarote). In terms of air-sea CO<sub>2</sub> exchange, the western region acted as a source throughout the study period, whereas the eastern region transitioned from a weak sink to a source after 2022. The increasing trend in SST across the Canary region, particularly during the anomalous warm year 2023 and during warmer winters in 2020, 2023 and 2024, is identified as the main driver of enhanced CO<sub>2</sub> outgassing. Overall, the Canary region acted as a net CO<sub>2</sub> source of 0.39 <inline-formula><mml:math id="M956" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.17 mol m<sup>−2</sup> yr<sup>−1</sup> between 2019 and 2024, increasing from 0.9 Tg CO<sub>2</sub> in 2019 to 4.5 Tg CO<sub>2</sub> in 2024, with a maximum of 4.8 Tg CO<sub>2</sub> in 2023.  These results highlight the complexity of modelling <inline-formula><mml:math id="M962" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and pH<sub>T,is</sub> in coastal and island-influenced environments, where physical and biological is greater than in the open ocean. The pronounced influence of the 2023 marine heatwave, which persisted for more than one year, underscores the sensitivity of short time series to extreme events and reinforces the need for long-term observations when assessing interannual trends. Although model performance is robust, longer time series are required to better constrain long-term changes in <inline-formula><mml:math id="M965" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2,sw</sub> and pH<sub>T,is</sub> in the Canary Islands waters. Nevertheless, this study demonstrates that the integration of sustained observations, satellite data and machine-learning techniques provides a powerful framework for characterising regional air-sea CO<sub>2</sub> exchange.</p>
</sec>

      
      </body>
    <back><notes notes-type="codedataavailability"><title>Code and data availability</title>

      <p id="d2e12479">Underway observations from the SOOP CanOA-VOS programme in the Canary region, including buoys data for the period February 2019 to December 2024, used in this study, are openly available via Zenodo (<ext-link xlink:href="https://doi.org/10.5281/zenodo.16780085" ext-link-type="DOI">10.5281/zenodo.16780085</ext-link>, Gonzalez-Davila and Santana-Casiano, 2025) and have been accessible since September 2023 through the ICOS Data Portal (<uri>https://www.icos-cp.eu/data-products/ocean-release</uri>, last access: 22 January 2026) under the CanOA-VOS-1 product. The model codes used to implement the different machine-learning approaches are also available in open access via Zenodo (<ext-link xlink:href="https://doi.org/10.5281/zenodo.16780313" ext-link-type="DOI">10.5281/zenodo.16780313</ext-link>, Irene et al., 2025). All satellite datasets are available from the Copernicus Climate Data Store (<uri>https://cds.climate.copernicus.eu/</uri>,  last access: 22 January 2026). Atmospheric <inline-formula><mml:math id="M969" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>CO<sub>2</sub> data from the IZAÑA (IZO) station are available from the NOAA's Global Monitoring Laboratory at <ext-link xlink:href="https://doi.org/10.15138/wkgj-f215" ext-link-type="DOI">10.15138/wkgj-f215</ext-link> (Lan et al., 2025).</p>
  </notes><app-group>
        <supplementary-material position="anchor"><p id="d2e12514">The supplement related to this article is available online at <inline-supplementary-material xlink:href="https://doi.org/10.5194/os-22-609-2026-supplement" xlink:title="pdf">https://doi.org/10.5194/os-22-609-2026-supplement</inline-supplementary-material>.</p></supplementary-material>
        </app-group><notes notes-type="authorcontribution"><title>Author contributions</title>

      <p id="d2e12523">All authors made significant contributions to this research. MGD, JMSC, AGG and DGS installed and maintained the VOS and buoy instrumentation and led the study conceptualisation. Together with ISM and DCH, carried out data curation and formal analysis. ISM and DE developed analytical routines and applied machine-learning techniques to data processing. All authors contributed to the writing of the manuscript, review, editing and approved its submission.</p>
  </notes><notes notes-type="competinginterests"><title>Competing interests</title>

      <p id="d2e12529">The contact author has declared that none of the authors has any competing interests.</p>
  </notes><notes notes-type="disclaimer"><title>Disclaimer</title>

      <p id="d2e12535">Publisher's note: Copernicus Publications remains neutral with regard to jurisdictional claims made in the text, published maps, institutional affiliations, or any other geographical representation in this paper. The authors bear the ultimate responsibility for providing appropriate place names. Views expressed in the text are those of the authors and do not necessarily reflect the views of the publisher.</p>
  </notes><ack><title>Acknowledgements</title><p id="d2e12541">We thank the owner of the <italic>JONA SOPHIE</italic>, Reederei Stefan Patjens GmbH &amp; Co. KG, as well as NISA-Marítima, the captains, and crew members for their support during this collaboration. We also thank the FRED OLSEN EXPRESS shipping company and its captains and crews for their assistance with all operations. Special thanks are extended to the technician Adrián Castro-Álamo for biweekly equipment maintenance and discrete sampling of total alkalinity aboard the vessel.</p><p id="d2e12546">The SOOP CanOA-VOS line has been part of the Spanish contribution to the Integrated Carbon Observation System (ICOS-ERIC; <uri>https://www.icos-cp.eu/</uri>, last access: 22 January 2026) since 2021 and has been recognised as an ICOS Class 1 Ocean Station. D. C.-H. was supported by the PhD grant PIFULPGC-2020-2 ARTHUM-2. This work also received funding from the PLANCLIMAC2 project (1/MAC/2/2.4/0006) under the Interreg VI Madeira–Azores–Canarias (MAC) 2021–2027 Territorial Cooperation Programme, co-funded by the European Regional Development Fund (ERDF).</p></ack><notes notes-type="financialsupport"><title>Financial support</title>

      <p id="d2e12554">This research was supported by the Canary Is20 lands Government and the Loro Parque Foundation through the CanBIO project, CanOA subproject (2019–2024), and the CARBOCAN agreement (Consejería de Transición Ecológica y Energía, Gobierno de Canarias). This work also received funding from the PLANCLIMAC2 project (1/MAC/2/2.4/0006) under the Interreg VI 25 Madeira–Azores–Canarias (MAC) 2021–2027 Territorial Cooperation Programme, co-funded by the European Regional Development Fund (ERDF).</p>
  </notes><notes notes-type="reviewstatement"><title>Review statement</title>

      <p id="d2e12560">This paper was edited by Matthew P. Humphreys and reviewed by two anonymous referees.</p>
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