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<front>
<journal-meta>
<journal-id journal-id-type="publisher-id">Front. Mar. Sci.</journal-id>
<journal-title>Frontiers in Marine Science</journal-title>
<abbrev-journal-title abbrev-type="pubmed">Front. Mar. Sci.</abbrev-journal-title>
<issn pub-type="epub">2296-7745</issn>
<publisher>
<publisher-name>Frontiers Media S.A.</publisher-name>
</publisher>
</journal-meta>
<article-meta>
<article-id pub-id-type="doi">10.3389/fmars.2025.1595871</article-id>
<article-categories>
<subj-group subj-group-type="heading">
<subject>Marine Science</subject>
<subj-group>
<subject>Original Research</subject>
</subj-group>
</subj-group>
</article-categories>
<title-group>
<article-title>High-resolution monitoring of the pH under strong La Ni&#xf1;a conditions in Gorgona Island, Colombian Pacific, Panama Bight</article-title>
</title-group>
<contrib-group>
<contrib contrib-type="author">
<name>
<surname>Murcia</surname>
<given-names>Andrea</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
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<contrib contrib-type="author" corresp="yes">
<name>
<surname>Acosta</surname>
<given-names>Alberto</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="author-notes" rid="fn001">
<sup>*</sup>
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<contrib contrib-type="author">
<name>
<surname>Garcia</surname>
<given-names>Alejandro P.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
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<contrib contrib-type="author">
<name>
<surname>Corredor-Acosta</surname>
<given-names>Andrea</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
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<contrib contrib-type="author">
<name>
<surname>Hern&#xe1;ndez&#x2011;Ay&#xf3;n</surname>
<given-names>Jos&#xe9; Mart&#xed;n</given-names>
</name>
<xref ref-type="aff" rid="aff4">
<sup>4</sup>
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<contrib contrib-type="author">
<name>
<surname>Guiti&#xe9;rrez</surname>
<given-names>Sim&#xf3;n</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
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<contrib contrib-type="author">
<name>
<surname>Celis</surname>
<given-names>Crisp&#xed;n</given-names>
</name>
<xref ref-type="aff" rid="aff5">
<sup>5</sup>
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<contrib contrib-type="author">
<name>
<surname>Ruiz-Pino</surname>
<given-names>Diana</given-names>
</name>
<xref ref-type="aff" rid="aff6">
<sup>6</sup>
</xref>
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<aff id="aff1">
<sup>1</sup>
<institution>UNESIS (Unidad de Ecolog&#xed;a y Sistem&#xe1;tica), Departamento de Biolog&#xed;a, Facultad de Ciencias, Pontificia Universidad Javeriana</institution>, <addr-line>Bogot&#xe1;</addr-line>,&#xa0;<country>Colombia</country>
</aff>
<aff id="aff2">
<sup>2</sup>
<institution>Divisi&#xf3;n de Investigaci&#xf3;n en Acuicultura, Instituto de Fomento Pesquero (IFOP)</institution>, <addr-line>Putem&#xfa;n</addr-line>,&#xa0;<country>Chile</country>
</aff>
<aff id="aff3">
<sup>3</sup>
<institution>Centro FONDAP de Investigaci&#xf3;n en Din&#xe1;mica de Ecosistemas Marinos de Altas Latitudes (IDEAL), Instituto de Acuicultura y Ciencias Ambientales, Universidad Austral de Chile</institution>, <addr-line>Puerto Montt</addr-line>,&#xa0;<country>Chile</country>
</aff>
<aff id="aff4">
<sup>4</sup>
<institution>Instituto de Investigaciones Oceanol&#xf3;gicas, Universidad Aut&#xf3;noma de Baja California</institution>, <addr-line>Ensenada, Baja California</addr-line>,&#xa0;<country>Mexico</country>
</aff>
<aff id="aff5">
<sup>5</sup>
<institution>Laboratorio de Fitoqu&#xed;mica, L&#xed;nea de Investigaci&#xf3;n en Tecnolog&#xed;a Ambiental y de Materiales, Departamento de Qu&#xed;mica, Facultad de Ciencias, Pontificia Universidad Javeriana</institution>, <addr-line>Bogot&#xe1;</addr-line>,&#xa0;<country>Colombia</country>
</aff>
<aff id="aff6">
<sup>6</sup>
<institution>Sorbonne Universit&#xe9;s (UPMC, Univ Paris 06)-CNRS-IRD-MNHN, LOCEAN Laboratory-IPSL</institution>, <addr-line>Paris</addr-line>,&#xa0;<country>France</country>
</aff>
<author-notes>
<fn fn-type="edited-by">
<p>Edited by: Martin F. Soto-Jimenez, National Autonomous University of Mexico, Mexico</p>
</fn>
<fn fn-type="edited-by">
<p>Reviewed by: Juan Carlos Carrasco Navas-Parejo, University of C&#xe1;diz, Spain</p>
<p>Raffi Isah, University of Hawaii at Manoa, United States</p>
<p>Maria Lourdes San Diego-McGlone, University of the Philippines Diliman, Philippines</p>
</fn>
<fn fn-type="corresp" id="fn001">
<p>*Correspondence: Alberto Acosta, <email xlink:href="mailto:laacosta@javeriana.edu.co">laacosta@javeriana.edu.co</email>
</p>
</fn>
</author-notes>
<pub-date pub-type="epub">
<day>12</day>
<month>08</month>
<year>2025</year>
</pub-date>
<pub-date pub-type="collection">
<year>2025</year>
</pub-date>
<volume>12</volume>
<elocation-id>1595871</elocation-id>
<history>
<date date-type="received">
<day>18</day>
<month>03</month>
<year>2025</year>
</date>
<date date-type="accepted">
<day>22</day>
<month>07</month>
<year>2025</year>
</date>
</history>
<permissions>
<copyright-statement>Copyright &#xa9; 2025 Murcia, Acosta, Garcia, Corredor-Acosta, Hern&#xe1;ndez&#x2011;Ay&#xf3;n, Guiti&#xe9;rrez, Celis and Ruiz-Pino.</copyright-statement>
<copyright-year>2025</copyright-year>
<copyright-holder>Murcia, Acosta, Garcia, Corredor-Acosta, Hern&#xe1;ndez&#x2011;Ay&#xf3;n, Guiti&#xe9;rrez, Celis and Ruiz-Pino</copyright-holder>
<license xlink:href="http://creativecommons.org/licenses/by/4.0/">
<p>This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.</p>
</license>
</permissions>
<abstract>
<p>Few studies have investigated the potential drivers of high-resolution (daily and 24-hour scales) on ocean acidification (OA) and the carbonate system in a coastal estuary during an intense La Ni&#xf1;a event. Therefore, we conducted the first high-resolution total scale pH (pH<sub>T</sub>) monitoring every three hours for 56 days (13 September to 7 November 2021) at the Colombian Pacific in El Muelle reef, Gorgona National Natural Park. Two moored autonomous submersible instruments (iSAMI-pH and CTD-Diver) were deployed at a depth of 2 m in an area influenced by extreme precipitation, river discharge, semi-diurnal tides, and southwest winds during La Ni&#xf1;a 2020-2023. Total alkalinity was derived from salinity data and used alongside pH<sub>T</sub> to calculate sea surface seawater partial pressure of CO<sub>2</sub> (pCO<sub>2w</sub>; &#x3bc;atm), dissolved inorganic carbon (DIC; &#x3bc;mol kg<sup>-1</sup>), and omega aragonite saturation (&#x3a9;<sub>a</sub>). The findings suggest that the observed low pH (7.93) and aragonite saturation state (&#x3a9;<sub>a</sub> = 2.22) values are likely attributed to increased precipitation. This enhanced precipitation resulted in higher river discharge, transporting naturally low-pH water to the island via mixing mechanisms (RiOMar type 2). Daily, decreasing solar radiation may reduce the seawater temperature, simultaneously elevating the pCO<sub>2w</sub> levels and reducing pH<sub>T</sub>. In contrast, elevated precipitation may reduce surface seawater salinity through freshwater dilution. Throughout the diurnal cycle, peak pH<sub>T</sub> values were recorded during late afternoon hours, likely driven by photosynthetic activity, while minimum values coincided with early morning periods of maximal respiratory activity. These results underscore the dynamic nature of this area and emphasize the need for long-term evaluation.</p>
</abstract>
<kwd-group>
<kwd>ocean acidification</kwd>
<kwd>riverine input</kwd>
<kwd>ENSO</kwd>
<kwd>RioMar</kwd>
<kwd>coral reef</kwd>
</kwd-group>
<contract-sponsor id="cn001">Pontificia Universidad Javeriana<named-content content-type="fundref-id">10.13039/501100009543</named-content>
</contract-sponsor>
<counts>
<fig-count count="5"/>
<table-count count="3"/>
<equation-count count="1"/>
<ref-count count="120"/>
<page-count count="16"/>
<word-count count="8510"/>
</counts>
<custom-meta-wrap>
<custom-meta>
<meta-name>section-in-acceptance</meta-name>
<meta-value>Marine Biogeochemistry</meta-value>
</custom-meta>
</custom-meta-wrap>
</article-meta>
</front>
<body>
<sec id="s1" sec-type="intro">
<label>1</label>
<title>Introduction</title>
<p>Ocean acidification (OA) driven by human-induced increases in atmospheric carbon dioxide (CO<sub>2</sub>) (<xref ref-type="bibr" rid="B94">Sabine et&#xa0;al., 2004</xref>; <xref ref-type="bibr" rid="B38">Feely et&#xa0;al., 2009</xref>) has significantly altered carbonate chemistry, leading to increased concentration of hydrogen ions [H<sup>+</sup>] and reduced global pH levels (<xref ref-type="bibr" rid="B65">Kleypas et&#xa0;al., 1999</xref>; <xref ref-type="bibr" rid="B14">Caldeira and Wickett, 2003</xref>; <xref ref-type="bibr" rid="B43">Gattuso et&#xa0;al., 2015</xref>). The El Ni&#xf1;o&#x2013;Southern Oscillation (ENSO) modulates OA. During El Ni&#xf1;o events in the Eastern Tropical Pacific, reduced trade winds weaken equatorial upwelling, limiting the transport of cold, nutrient- and carbon-rich waters from the deep ocean to the surface (<xref ref-type="bibr" rid="B107">Vaittinada Ayar et&#xa0;al., 2022</xref>). As a result, surface dissolved inorganic carbon (DIC) concentrations decrease, leading to relatively lower seawater pCO<sub>2w</sub> and reduced CO<sub>2</sub> outgassing to the atmosphere (<xref ref-type="bibr" rid="B39">Feely et&#xa0;al., 2006</xref>; <xref ref-type="bibr" rid="B63">Ishii et&#xa0;al., 2014</xref>; <xref ref-type="bibr" rid="B34">Espinoza-Morriber&#xf3;n et&#xa0;al., 2019</xref>). In contrast, La Ni&#xf1;a events strengthen the trade winds and enhance upwelling, bringing DIC and nutrient-rich waters to the surface (<xref ref-type="bibr" rid="B107">Vaittinada Ayar et&#xa0;al., 2022</xref>). This increase in upwelling elevates pCO<sub>2w</sub> levels, thereby increasing CO<sub>2</sub> outgassing (<xref ref-type="bibr" rid="B114">Yasunaka et&#xa0;al., 2019</xref>) and can lead to lower pH levels in coastal waters, intensifying OA (<xref ref-type="bibr" rid="B80">Oliva-M&#xe9;ndez et&#xa0;al., 2018</xref>).</p>
<p>La Ni&#xf1;a event also induces increased rainfall, which enhances river discharge in coastal areas (<xref ref-type="bibr" rid="B90">Restrepo and Kjerfve, 2000</xref>; <xref ref-type="bibr" rid="B56">Hern&#xe1;ndez et&#xa0;al., 2006</xref>; <xref ref-type="bibr" rid="B11">Blanco, 2009</xref>). This influx of freshwater significantly reduces the buffering capacity of estuaries to neutralize acids and maintain stable pH levels, because freshwater lacks the carbonate buffer system found in seawater. These conditions increase the solubility of CO<sub>2</sub> and reduce the dissociation of bicarbonates (HCO<sub>3</sub>
<sup>-</sup>) into carbonate ions (CO<sub>3</sub>
<sup>-2</sup>; <xref ref-type="bibr" rid="B13">Cai et&#xa0;al., 2021</xref>). Additionally, rivers contribute to pH reduction by transporting organic matter, which releases carbon dioxide as it oxidizes upon reaching the sea (<xref ref-type="bibr" rid="B95">Salisbury et&#xa0;al., 2008</xref>; <xref ref-type="bibr" rid="B119">Zhai et&#xa0;al., 2015</xref>; <xref ref-type="bibr" rid="B109">Vargas et&#xa0;al., 2016</xref>). Moreover, nutrients from land and rivers are transported to coastal waters via runoff, forming low-salt river plumes that extend to the continental shelf, driven by winds and tides (<xref ref-type="bibr" rid="B23">Dai et&#xa0;al., 2022a</xref>). The areas influenced by these plumes, associated with the 19 largest rivers globally, cover an average of 3.7 &#xd7; 10<sup>6</sup> km<sup>2</sup> annually (<xref ref-type="bibr" rid="B64">Kang et&#xa0;al., 2013</xref>), representing approximately 14% of the total global continental shelf area (<xref ref-type="bibr" rid="B23">Dai et&#xa0;al., 2022a</xref>). Thus, salinity variations in estuary systems are determined by the mixing process influenced by tidal movements, precipitation, river discharges, and seawater influx (<xref ref-type="bibr" rid="B9">Atekwana et&#xa0;al., 2022</xref>).</p>
<p>In the Colombian Caribbean, La Ni&#xf1;a events have been observed to intensify precipitation, leading to increased freshwater inflow and a subsequent dilution that significantly reduces DIC and total alkalinity (TA) (<xref ref-type="bibr" rid="B91">Ricaurte-Villota et&#xa0;al., 2025</xref>). Furthermore, heavy rains in the tropical Pacific Ocean can modify salinity, with dilution effects persisting for over 10 days (<xref ref-type="bibr" rid="B55">Henocq et&#xa0;al., 2010</xref>). This phenomenon decreases two key parameters of the carbonate system: TA and DIC (<xref ref-type="bibr" rid="B105">Turk et&#xa0;al., 2010</xref>; <xref ref-type="bibr" rid="B8">Ashton et&#xa0;al., 2016</xref>; <xref ref-type="bibr" rid="B57">Ho and Schanze, 2020</xref>). The relationship between low salinity and variations in the carbonate system has also been documented in other coastal regions of the Eastern Tropical Pacific (10&#xb0;N), where precipitation influences can extend over 40,000 km<sup>2</sup>, due to surface ocean currents dispersing freshwater over larger areas (<xref ref-type="bibr" rid="B57">Ho and Schanze, 2020</xref>).</p>
<p>Estuaries and coastal waters present greater complexity compared to open ocean waters when estimating OA and the carbonate system, as they are highly variable environments due to the mixing of seawater and freshwater (<xref ref-type="bibr" rid="B111">Wang et&#xa0;al., 2019</xref>; <xref ref-type="bibr" rid="B79">Nehir et&#xa0;al., 2022</xref>). Additionally, these Tropical Pacific waters, often influenced by anthropogenic activities, are critical for acidification studies. However, their complexity and the time scales (ranging from hours to interannual changes) require high-resolution monitoring to accurately assess OA (<xref ref-type="bibr" rid="B15">Carstensen et&#xa0;al., 2018</xref>; <xref ref-type="bibr" rid="B79">Nehir et&#xa0;al., 2022</xref>). One of the key parameters to monitor in estuaries is the natural variation of water pH (<xref ref-type="bibr" rid="B79">Nehir et&#xa0;al., 2022</xref>), which is typically measured using the National Bureau of Standards scale (pH<sub>NBS</sub>) and total pH scales (pH<sub>T</sub>). The pH<sub>T</sub> is preferred in oceanography due to its accuracy. It also considers other factors that affect proton activity in complex solutions such as seawater, including the presence of salts (<xref ref-type="bibr" rid="B36">Fassbender et&#xa0;al., 2021</xref>).</p>
<p>The equatorial Pacific waters are characterized by lower pH values (8.00; <xref ref-type="bibr" rid="B120">Zhong et&#xa0;al., 2025</xref>) compared to the global average (8.05; <xref ref-type="bibr" rid="B110">von Schuckmann et&#xa0;al., 2024</xref>), making this region a key area for analyzing OA and its ecological impacts. To address this, continuous monitoring efforts using <italic>in situ</italic> submersible spectrophotometric sensors, such as Lab-on-Chip (<xref ref-type="bibr" rid="B115">Yin et&#xa0;al., 2021</xref>; <xref ref-type="bibr" rid="B79">Nehir et&#xa0;al., 2022</xref>) and the iSAMI-pH (<xref ref-type="bibr" rid="B108">Valauri-Orton et&#xa0;al., 2025</xref>), have proven effective for small-scale autonomous monitoring of the total pH scale (pH<sub>T</sub>). For example, in the Pacific Coastal Ocean, significant pH<sub>T</sub> variation (7.93 to 8.37) has been associated with upwelling events (Monterey Bay, USA) which increase pCO<sub>2w</sub> and reduce pH<sub>T</sub> (<xref ref-type="bibr" rid="B51">Gray et&#xa0;al., 2011</xref>). In contrast, during periods without upwelling and in the rainy season, a more minor pH<sub>T</sub> variation (ranging from 7.98 to 8.06) has been observed along the Pacific coast of Costa Rica (Bahia Culebra; <xref ref-type="bibr" rid="B97">S&#xe1;nchez-Noguera et&#xa0;al., 2018</xref>). In this region, a distinct 24-hour cycle was detected, with the lowest pH<sub>T</sub> occurring in the early morning hours, due to organic matter respiration at night, and the highest pH<sub>T</sub> values recorded in the late afternoon, associated with photosynthesis (<xref ref-type="bibr" rid="B97">S&#xe1;nchez-Noguera et&#xa0;al., 2018</xref>).</p>
<p>In the Colombian Pacific Ocean, high-resolution measurements of pH<sub>T</sub> have not been conducted. Instead, discrete measurements related to carbonate chemistry and pH<sub>NBS</sub> have primarily been performed in the Caribbean Sea and the Pacific Ocean, including sampling sites around Gorgona National Natural Park (GNNP) by Instituto de Investigaciones Marinas y Costeras Jos&#xe9; Benito Vives de Andr&#xe9;is (INVEMAR) as part of the program &#x201c;Red de Vigilancia para la Conservaci&#xf3;n y Protecci&#xf3;n de las Aguas Marinas y Costeras de Colombia (REDCAM)&#x201d;. In Tayrona National Natural Park, studies such as those by <xref ref-type="bibr" rid="B91">Ricaurte-Villota et&#xa0;al. (2025)</xref> have collected discrete samples of pH<sub>NBS</sub>, TA, and DIC, revealing high variability strongly influenced by coastal upwelling, precipitation, and river runoff, which are further affected by ENSO events. The high variability of oceanographic processes in coastal regions underscores the need for high-resolution monitoring, as discrete measurements are limited in their ability to capture natural variability and achieve sufficient temporal resolution (<xref ref-type="bibr" rid="B79">Nehir et&#xa0;al., 2022</xref>). Gorgona National Natural Park, located on the Colombian Pacific continental shelf, is a potential hotspot for OA due to its exposure to frequent ENSO events, which drive significant climate variability through El Ni&#xf1;o and La Ni&#xf1;a events (<xref ref-type="bibr" rid="B67">Lav&#xed;n et&#xa0;al., 2006</xref>; <xref ref-type="bibr" rid="B33">Emerton et&#xa0;al., 2017</xref>; <xref ref-type="bibr" rid="B40">Fiedler and Lav&#xed;n, 2017</xref>; <xref ref-type="bibr" rid="B10">Berri et&#xa0;al., 2019</xref>). As part of the Eastern Tropical Pacific (ETP), it is influenced by the Choco Jet, which brings intense precipitation from September to November (<xref ref-type="bibr" rid="B99">Serna et&#xa0;al., 2018</xref>; <xref ref-type="bibr" rid="B54">Guzm&#xe1;n et&#xa0;al., 2014</xref>), further increasing the already high fluvial discharge from the Patia-Sanquianga deltaic complex, the largest in Colombia (<xref ref-type="bibr" rid="B26">D&#xed;az, 2007</xref>). Additionally, the Intertropical Convergence Zone (ITCZ) intensifies cloudiness and precipitation during this period, reducing solar radiation and potentially impacting the carbonate system and OA by altering water temperature and CO<sub>2</sub> solubility, as observed in other regions (<xref ref-type="bibr" rid="B112">Webster, 2020</xref>; <xref ref-type="bibr" rid="B13">Cai et&#xa0;al., 2021</xref>).</p>
<p>Therefore, this study investigates fine-scale, high-frequency dynamics in coastal carbonate chemistry using continuous measurements of pH<sub>T</sub>, temperature, salinity, and derivation of TA, DIC, pCO<sub>2w,</sub> and omega aragonite saturation (&#x3a9;<sub>a</sub>). Focusing on Gorgona National Natural Park (GNNP) in the Colombian Pacific Ocean (Panama Bight), it examines how freshwater pulses during strong rainy season La Ni&#xf1;a events modulate coastal carbonate buffering capacity and influence pH stability and ecosystem resilience to ocean acidification under climatic stress. This study uses a fixed mooring equipped with autonomous sensors to characterize high-frequency variability (daily over 56 days and hourly over 24 hours) of pH<sub>T</sub> and other carbon chemistry variables (TA, pCO<sub>2w</sub>, and DIC). Additionally, it explores the influence of tidal dynamics (ebb vs. flood) on variations in pH<sub>T</sub>, salinity, temperature, pCO<sub>2w</sub>, DIC, and TA, synchronizing high-resolution measurements from the iSAMI-pH and CTD-Diver with tide height data to identify primary sources of pH<sub>T</sub> variation (oceanic vs. riverine influences). Furthermore, the relationships, both in magnitude and direction, between pH<sub>T</sub>, salinity, temperature, pCO<sub>2w</sub>, DIC, and TA, with external drivers such as daily solar radiation and daily precipitation (influenced by the Intertropical Convergence Zone, ITCZ) were analyzed. Daily mean values of the dependent variables were calculated to assess their response to these environmental factors under extreme climatic and hydrological dynamics. Finally, the study evaluates whether pH<sub>T</sub>, salinity, temperature, pCO<sub>2w</sub>, DIC, and TA exhibit significant differences between early morning and late afternoon within a 24-hour daily cycle, providing insights into diurnal variability in the study area. By addressing the critical role of fine-scale processes in shaping coastal carbonate chemistry, this research fills a significant gap in understanding the dynamics of coastal systems under extreme conditions.</p>
</sec>
<sec id="s2">
<label>2</label>
<title>Methods</title>
<sec id="s2_1">
<label>2.1</label>
<title>Study area</title>
<p>The Gorgona National Natural Park (GNNP; 2&#xb0; 55&#x2019;45&#x201d; - 3&#xb0; 00&#x2019; 55&#x201d; N, 78&#xb0; 09&#x2019; 00&#x2033; - 78&#xb0; 14&#x2019; 30&#x201d; W) is located on the continental shelf of the Colombian Pacific basin (<xref ref-type="fig" rid="f1">
<bold>Figure&#xa0;1</bold>
</xref>). This region is characterized by warm and low-salinity surface waters (<xref ref-type="bibr" rid="B48">Giraldo L&#xf3;pez, 2008</xref>; <xref ref-type="bibr" rid="B44">Giraldo et&#xa0;al., 2008</xref>, <xref ref-type="bibr" rid="B47">2011</xref>, <xref ref-type="bibr" rid="B46">2014</xref>), and constitutes one of the rainiest regions of the world, being also the rainiest area of Colombia with annual values ranging from 2500 mm to 8000 mm (<xref ref-type="bibr" rid="B88">Rangel and Rudas, 1990</xref>; <xref ref-type="bibr" rid="B11">Blanco, 2009</xref>). This condition is mainly associated with the latitudinal migration of the Intertropical Convergence Zone (ITCZ; <xref ref-type="bibr" rid="B28">D&#xed;az Guevara et&#xa0;al., 2008</xref>) and the Choco Jet Stream, which increases cloudiness and precipitation due to the convergence of trade winds from the northern and southern hemispheres (<xref ref-type="bibr" rid="B86">Prahl et&#xa0;al., 1990</xref>; <xref ref-type="bibr" rid="B28">D&#xed;az Guevara et&#xa0;al., 2008</xref>; <xref ref-type="bibr" rid="B54">Guzm&#xe1;n et&#xa0;al., 2014</xref>; <xref ref-type="bibr" rid="B99">Serna et&#xa0;al., 2018</xref>). During the second half of the year, the ITCZ moves north, altering the wind direction near 3&#xb0;N latitude, which becomes dominant in the southwesterlies and forms the Choco Jet off western Colombia (<xref ref-type="bibr" rid="B85">Poveda and Mesa, 2000</xref>; <xref ref-type="bibr" rid="B5">Amador et&#xa0;al., 2006</xref>; <xref ref-type="bibr" rid="B53">Guerrero Gallego et&#xa0;al., 2012</xref>). During the study period (September 13 to November 7, 2021), the area was affected by the strong La Ni&#xf1;a 2020&#x2013;2023 event (thermal anomalies of -1.4 &#xb1; 0.1&#xb0;C; <xref ref-type="supplementary-material" rid="SM1">
<bold>Supplementary Table&#xa0;1</bold>
</xref>, <xref ref-type="bibr" rid="B59">IDEAM, 2021</xref>) that increased total precipitation in the Colombian Pacific.</p>
<fig id="f1" position="float">
<label>Figure&#xa0;1</label>
<caption>
<p>Location of Gorgona National Natural Park in the Colombian Pacific Ocean, Eastern Tropical Pacific (ETP). <bold>(A)</bold> iSAMI-pH and CTD-Diver measurements at El Muelle reef (black star). The colored polygons show the coral reefs (<italic>Pavona</italic> spp - <italic>Porites</italic> spp, <italic>Pavona</italic> spp, and <italic>Pocillopora</italic> spp) around Gorgona according to Colombia&#x2019;s Atlas of Coral Areas until 2020 (<xref ref-type="bibr" rid="B60">INVEMAR, 2020a</xref>). <bold>(B)</bold> The black polygon shows the protected area of Gorgona Park and its proximity to the Pacific coast (around 50 km), as well as the main rivers influencing the island (Guapi River, Patia - Sanquianga Rivers, Tapaje River, and Iscuande River). The black dot represents the &#x201c;57025020 Gorgona Guapi&#x201d; pluviometric station (<xref ref-type="bibr" rid="B25">DHIME, 2025</xref>), the orange dot represents the &#x201c;26015040 Arrayanales&#x201d; for solar radiation measurements (<xref ref-type="bibr" rid="B25">DHIME, 2025</xref>), while the red point represents the Buenaventura station for tide height measurements (<xref ref-type="bibr" rid="B41">Flanders Marine Institute [VLIZ] and Intergovernmental Oceanographic Commission [IOC], 2025</xref>). <bold>(C)</bold> Square showed the island&#x2019;s position within the ETP. The red polygon shows the Panama Bight, which includes the Panama and Colombian Pacific basins.</p>
</caption>
<graphic mimetype="image" mime-subtype="tiff" xlink:href="fmars-12-1595871-g001.tif">
<alt-text content-type="machine-generated">Map illustrating the location and type of coral reefs around Gorgona Island in the Eastern Tropical Pacific. Panel A shows detailed coral reef locations, marked by color for different species. The iSAMI-pH CTD-Diver site is indicated on the east side of the island. Panel B shows Gorgona Island's position off the Colombian coast near Pat&#xed;a-Sanquianga and other areas. Panel C places the region within the Eastern Tropical Pacific context. A legend details coral species represented by different colors.</alt-text>
</graphic>
</fig>
<p>Gorgona Park is in front of the Patia-Sanquianga delta complex (<xref ref-type="fig" rid="f1">
<bold>Figure&#xa0;1B</bold>
</xref>), the largest in the country, which contributes approximately 23% of the total freshwater discharged to the Colombian Pacific (2045 m<sup>3</sup> s<sup>-1</sup>; <xref ref-type="bibr" rid="B26">D&#xed;az, 2007</xref>). This delta comprises several rivers, including the Guapi, Patia, Iscuande, Tapaje, and Sanquianga (<xref ref-type="bibr" rid="B26">D&#xed;az, 2007</xref>, <xref ref-type="fig" rid="f1">
<bold>Figure&#xa0;1B</bold>
</xref>). Likewise, the tidal regime around GNNP is semi-diurnal, repeating twice in 24 hours, with two alternating high tides (5.82 m) and two low tides (-0.78 m; <xref ref-type="bibr" rid="B41">Flanders Marine Institute [VLIZ] and Intergovernmental Oceanographic Commission [IOC], 2025</xref>).</p>
<p>The Pacific coast has an average daily solar radiation of 3500 to 4000 Wh m<sup>-2</sup> and an annual availability of solar radiation that varies between 1,080,000 and 1,440,000 Wh m<sup>-2</sup> (<xref ref-type="bibr" rid="B106">UPME, 2005</xref>). During the year&#x2019;s second half, solar radiation decreases until it reaches its minimum in December (<xref ref-type="bibr" rid="B88">Rangel and Rudas, 1990</xref>). Regarding its biodiversity, GNNP hosts one of the most critical coral reef areas in the Eastern Tropical Pacific (ETP) region in terms of structure and species diversity (<xref ref-type="bibr" rid="B49">Glynn et&#xa0;al., 1982</xref>; <xref ref-type="bibr" rid="B116">Zapata, 2001</xref>; <xref ref-type="bibr" rid="B27">D&#xed;az et&#xa0;al., 2001</xref>) and connects the ETP with other Pacific regions (e.g., Hawaii, Polynesia) via larval potential dispersion (<xref ref-type="bibr" rid="B93">Romero-Torres et&#xa0;al., 2018</xref>). Remarkably, these reefs persist despite being regularly exposed to multiple environmental stressors. At the beginning of the year, they experience sub-aerial exposure during extreme low tides (<xref ref-type="bibr" rid="B116">Zapata, 2001</xref>; <xref ref-type="bibr" rid="B117">Zapata et&#xa0;al., 2010</xref>), low pH levels reaching as low as 7.4 (<xref ref-type="bibr" rid="B45">Giraldo and Valencia, 2013</xref>), cooler temperatures (16.69 &#xb0;C; <xref ref-type="bibr" rid="B44">Giraldo et&#xa0;al., 2008</xref>), and hypoxic conditions (&lt; 3.7 mg L<sup>-1</sup>) associated with seasonal upwelling (<xref ref-type="bibr" rid="B17">Castrill&#xf3;n-Cifuentes et&#xa0;al., 2023a</xref>, <xref ref-type="bibr" rid="B18">b</xref>). During the second half of the year, these reefs are subjected to low salinity levels during the rainy season (as low as 25; <xref ref-type="bibr" rid="B44">Giraldo et&#xa0;al., 2008</xref>), warmer temperatures (27 &#xb0;C; <xref ref-type="bibr" rid="B44">Giraldo et&#xa0;al., 2008</xref>), and increased sedimentation rates (23.30 &#xb1; 4.34 g m<sup>-2</sup> d<sup>-1</sup>; <xref ref-type="bibr" rid="B71">Lozano-Cort&#xe9;s et&#xa0;al., 2014</xref>). Coral species such as <italic>Pocillopora</italic> spp. and <italic>Pavona</italic> spp. dominate the eastern (leeward) and southern areas of Gorgona Island, while occurring more sparsely in the western and northern areas (<xref ref-type="fig" rid="f1">
<bold>Figure&#xa0;1A</bold>
</xref>, <xref ref-type="bibr" rid="B116">Zapata, 2001</xref>). The sampling point (<xref ref-type="fig" rid="f1">
<bold>Figure&#xa0;1A</bold>
</xref>) was located at the north end of El Muelle reef (northward surface current), where the genus <italic>Pocillopora</italic> spp. predominantly dominates this and the major eastern coral patch of Azufrada (<xref ref-type="bibr" rid="B116">Zapata, 2001</xref>; <xref ref-type="bibr" rid="B92">Romero-Torres and Acosta, 2010</xref>).</p>
</sec>
<sec id="s2_2">
<label>2.2</label>
<title>
<italic>In situ</italic> measurements</title>
<p>Continuous measurements of pH<sub>T</sub>, conductivity (mS cm<sup>-1</sup>), and temperature (&#xb0;C) were made at a fixed depth of around 2 meters in El Muelle reef, GNNP (2&#xb0; 57&#x2019; 39&#x201d; N, 78&#xb0; 10&#x2019; 25&#x201d; W; <xref ref-type="fig" rid="f1">
<bold>Figure&#xa0;1A</bold>
</xref>) from 13 September to 07 November 2021, every three hours, using a buoy anchoring system designed to compensate the tidal changes and to keep the equipment at a similar depth. The iSAMI-pH equipment (programmed with SAMI Client v2.5 software) was used to record pH<sub>T</sub> (accuracy: 0.0004 and precision: &#xb1; 0.0024) and temperature (accuracy: &#xb1; 0.14&#xb0;C; at 24.55 &#xb0;C Tris bottle number 10 Sunburst Sensors). The CTD Diver equipment (programmed with Diver Field software, Van Essen Instruments) was used to take conductivity measurements (accuracy: &#xb1; 1% mS cm<sup>-1</sup>). Conductivity data were also downloaded using Diver Field software. The salinity was calculated using the practical scaling relationship proposed by <xref ref-type="bibr" rid="B6">Aminot and K&#xe9;rouel (2004)</xref>. The iSAMI-pH data were downloaded with the SAMI program (QC pH v4.4). Because the QC pH v4.4 program handles a constant salinity of 35 units by default, the pH<sub>T</sub> data were corrected for salinity. To do the correction, the program was set to the corresponding average salinity (29.74 &#xb1; 0.94, 31.29; mean &#xb1; SD, maximum, n = 403) of the sampling point (2&#xb0; 57&#x2019; 39&#x201d; N, 78&#xb0; 10&#x2019; 25&#x201d; W). With the correction, differences in pH<sub>T</sub> of &#xb1; 0.01 units were observed. We used the average salinity value to ensure consistency in salinity correction, as the CTD Diver recorded salinity 30 minutes after iSAMI-pH measurements from October 10 to November 7. When both devices recorded simultaneously between September 13 and October 10, the difference between pH corrected with average and measured salinity was insignificant (&#xb1; 0.0001). iSAMI recorded 49 outliers out of 441 data points, which were excluded from the analysis as iSAMI-pH identified them as measurement anomalies (error codes 100, 1001, 1010, and 1000) associated with issues related to pumping, dye supply, or blank measurement. Additionally, 19 temperature and 38 salinity data points were identified as outliers when plotting variables and their relationship to total pH<sub>T</sub>. These points were excluded from the analysis after applying a criterion based on standard deviation to consecutive measurements. Any change greater than 0.030 in pH, 0.30&#xb0;C in temperature, or 0.94&#xb0;C in salinity between measurements was considered a potential outlier. Flagged data points underwent contextual evaluation, considering environmental consistency (e.g., salinity-TA relationships, diel cycles, water mass characteristics), sensor artifacts, and physical plausibility. Only measurements inconsistent both statistically and contextually were excluded.</p>
</sec>
<sec id="s2_3">
<label>2.3</label>
<title>Carbonate system derivation</title>
<p>Total alkalinity (TA; &#x3bc;mol kg<sup>-1</sup>) was calculated using a regression line between salinity (<italic>in situ</italic> data taken with CastAway-CTD equipment) and TA. <xref ref-type="bibr" rid="B87">Preciado (2023)</xref> built the regression (y = 57.479x+249.08; R2 = 0.94; n=268) using measured local discrete TA data obtained from 8 sampling stations around Gorgona, one of which included the iSAMI-pH deployment site. The data were collected over 13 sampling months, from September 2021 to October 2022, at depths ranging from 2 to 80 meters, following the SOP-3b protocol (<xref ref-type="bibr" rid="B30">Dickson et&#xa0;al., 2007</xref>). Discrete samples of TA (&#xb1; 13 &#x3bc;mol kg<sup>-1</sup>, Batch #182 2230.91&#x3bc;mol kg<sup>-1</sup>) were collected monthly at the iSAMI-pH site from November 2021 to July 2022. Comparing the measured TA values &#x200b;&#x200b;with those estimated from salinity, a mean difference of 11 &#xb1; 5 &#x3bc;mol kg<sup>-1</sup> and a regression coefficient of R&#xb2; = 0.91 were observed (<xref ref-type="supplementary-material" rid="SM1">
<bold>Supplementary Figure&#xa0;1</bold>
</xref>). Specifically, in November 2021, the difference was 10 &#xb1; 3 &#x3bc;mol kg<sup>-1</sup>. This regression approach for estimating TA through salinity has been validated in previous studies (<xref ref-type="bibr" rid="B69">Lee et&#xa0;al., 2006</xref>; <xref ref-type="bibr" rid="B101">Takatani et&#xa0;al., 2014</xref>; <xref ref-type="bibr" rid="B16">Carter et&#xa0;al., 2016</xref>; <xref ref-type="bibr" rid="B35">Fassbender et&#xa0;al., 2017</xref>; <xref ref-type="bibr" rid="B74">Metzl et&#xa0;al., 2024</xref>).</p>
<p>For the derivation of the carbonate system pCO<sub>2w</sub> (&#x3bc;atm), dissolved inorganic carbon (DIC; &#x3bc;mol kg<sup>-1</sup>), and omega aragonite (&#x3a9;<sub>a</sub>), we used the Carbonate System equation solution (CO2sys v3.0, <xref ref-type="bibr" rid="B84">Pierrot et&#xa0;al., 2021</xref>), with the pair pH<sub>T</sub> (n = 392) from iSAMI-pH and TA derived from the former regression, as well as salinity from CTD (<xref ref-type="bibr" rid="B6">Aminot and K&#xe9;rouel, 2004</xref>) and temperature (iSAMI-pH). Propagation error analysis using CO2sys v3.0 estimated uncertainties of &#xb1;52 &#xb5;mol&#xb7;kg<sup>-1</sup> for DIC, &#xb1; 33 &#x3bc;atm for pCO<sub>2</sub>, and &#xb1;0.16 for &#x3a9;<sub>a</sub>. In the carbonate system equation solution, the following constants were used: (i) Dissociation constants for K<sub>1</sub> and K<sub>2</sub> from <xref ref-type="bibr" rid="B76">Millero, 2010</xref>) for waters ranging from 0 to 40, given that the study area the salinities variation are between 27.03 to 31.29, (ii) KHSO<sub>4</sub> dissociation constant from <xref ref-type="bibr" rid="B29">Dickson (1990)</xref>, (iii) KHF from <xref ref-type="bibr" rid="B83">Perez and Fraga (1987)</xref>, (iv) Total pH scale (mol-kg SW), (v) [B]T value from <xref ref-type="bibr" rid="B68">Lee et&#xa0;al. (2010)</xref>, and (vi) EOS-80 standard.</p>
<p>To evaluate the influence of temperature and salinity, pH<sub>T</sub> was normalized using the mean temperature (27.39&#xb0;C) and salinity (29.74), as recommended by <xref ref-type="bibr" rid="B102">Terlouw et&#xa0;al. (2019)</xref>. Additionally, normalization was performed using constant values representing the minimum observed temperature (26.72&#xb0;C) and salinity (27.03), to account for the most extreme conditions in the dataset (<xref ref-type="supplementary-material" rid="SM1">
<bold>Supplementary Figure&#xa0;2</bold>
</xref>). This normalization process isolates the potential effect of temperature and salinity on pH<sub>T</sub>, following the methodology outlined by <xref ref-type="bibr" rid="B98">Sarmiento and Gruber (2006)</xref>. The influence of temperature and salinity corresponds to the difference between the normalized pH<sub>T</sub> and the <italic>in situ</italic> measured pH<sub>T</sub>.</p>
</sec>
<sec id="s2_4">
<label>2.4</label>
<title>Statistical analysis: evaluation of external forcing on carbon chemistry</title>
<sec id="s2_4_1">
<label>2.4.1</label>
<title>Tidal movement data</title>
<p>Daily tide measurements (m) between 13 September and 07 November 2021 were obtained from the UNESCO Sea Level Monitoring Facility database (<xref ref-type="bibr" rid="B41">Flanders Marine Institute [VLIZ] and Intergovernmental Oceanographic Commission [IOC], 2025</xref>), specifically from the Buenaventura station (3&#xb0; 53&#x2019; 26&#x201d; N, 77&#xb0; 4&#x2019; 51&#x201d; W), which measures the tide using a radar sensor. These tide measurements were temporally synchronized with iSAMI-pH and CTD-Diver data and subsequently labeled according to the water movement (ebb or flood; <xref ref-type="supplementary-material" rid="SM1">
<bold>Supplementary Figure&#xa0;3</bold>
</xref>). The dependent variables do not meet the assumptions of normality, so non-parametric tests were chosen (<xref ref-type="supplementary-material" rid="SM1">
<bold>Supplementary Table&#xa0;2</bold>
</xref>). The Kruskal-Wallis nonparametric test was used to determine if there were significant differences (p &lt; 0.05) in the dependent variables (pH<sub>T</sub>, salinity, temperature, pCO<sub>2W</sub>, DIC, and TA) when comparing tidal movements (ebb and flood tides).</p>
</sec>
<sec id="s2_4_2">
<label>2.4.2</label>
<title>Atmospheric variables, solar radiation, and precipitation, and correlation with carbon chemistry</title>
<p>For the study period, 56 days, daily solar radiation (Wh m<sup>-2</sup>) was obtained from the &#x201c;26015040 Arrayanales&#x201d; fixed station (2&#xb0; 26&#x2019; 53&#x201d; N, 76&#xb0; 26&#x2019; 9&#x201d; W; <xref ref-type="bibr" rid="B25">DHIME, 2025</xref>), and daily total precipitation (mm) from the &#x201c;57025020 Gorgona Guapi&#x201d; fixed station (2&#xb0; 57&#x2019; 47&#x201d; N, 78&#xb0; 10&#x2019; 28&#x201d; W; <xref ref-type="bibr" rid="B25">DHIME, 2025</xref>).</p>
<p>Daily means of the dependent variables (pH<sub>T</sub>, salinity, temperature, pCO<sub>2W</sub>, DIC, and TA) were calculated. A Spearman correlation analysis was performed between the dependent physical and chemical parameters and atmospheric variables (solar radiation and total precipitation) to evaluate the importance and direction of their relationship (rho value).</p>
</sec>
<sec id="s2_4_3">
<label>2.4.3</label>
<title>Hour carbon chemistry cycle analysis</title>
<p>The hourly cycle analysis was performed by calculating the average of the variables (pH<sub>T</sub>, salinity, temperature, pCO<sub>2W</sub>, DIC, and TA) taken at the same hour every three hours between 13 September and 7 November 2021. Carbonate alkalinity was also calculated following the equation proposed by <xref ref-type="bibr" rid="B78">Munhoven, 2013</xref>:</p>
<disp-formula>
<mml:math display="block" id="M1">
<mml:mrow>
<mml:msub>
<mml:mrow>
<mml:mtext>Alk</mml:mtext>
</mml:mrow>
<mml:mtext>C</mml:mtext>
</mml:msub>
<mml:mo>=</mml:mo>
<mml:mo stretchy="false">[</mml:mo>
<mml:msubsup>
<mml:mrow>
<mml:mtext>HCO</mml:mtext>
</mml:mrow>
<mml:mn>3</mml:mn>
<mml:mo>&#x2212;</mml:mo>
</mml:msubsup>
<mml:mo stretchy="false">]</mml:mo>
<mml:mo>+</mml:mo>
<mml:mn>2</mml:mn>
<mml:mo stretchy="false">[</mml:mo>
<mml:msubsup>
<mml:mrow>
<mml:mtext>CO</mml:mtext>
</mml:mrow>
<mml:mn>3</mml:mn>
<mml:mrow>
<mml:mn>2</mml:mn>
<mml:mo>&#x2212;</mml:mo>
</mml:mrow>
</mml:msubsup>
<mml:mo stretchy="false">]</mml:mo>
</mml:mrow>
</mml:math>
</disp-formula>
<p>The Kruskal-Wallis test executed in RStudio was used to determine if there were significant differences (p-value &lt; 0.05) in the dependent variables (pH<sub>T</sub>, salinity, temperature, pCO<sub>2W</sub>, DIC, TA, and carbonate alkalinity) when comparing the early morning hours (5:00 - 6:00) with the late afternoon hours (17:00 - 18:00).</p>
</sec>
</sec>
</sec>
<sec id="s3" sec-type="results">
<label>3</label>
<title>Results</title>
<p>The sampling period took place during a year with strong La Ni&#xf1;a conditions displaying atmospheric thermal anomalies of -1.4 &#xb1; 0.1&#xb0;C (<xref ref-type="supplementary-material" rid="SM1">
<bold>Supplementary Table&#xa0;1</bold>
</xref>; <xref ref-type="bibr" rid="B59">IDEAM, 2021</xref>) and extreme precipitation values (959 &#xb1; 316 mm/monthly; <xref ref-type="bibr" rid="B25">DHIME, 2025</xref>). Throughout the study period, pH<sub>T</sub> decreased from September until October 25 (<xref ref-type="fig" rid="f2">
<bold>Figure&#xa0;2</bold>
</xref>), after which it increased until November 7, while pCO<sub>2w</sub>, DIC, and salinity increased until October 25 and then decreased until November 7. Throughout the study period, pH<sub>T</sub> and pCO<sub>2w</sub> exhibited opposite trends (<xref ref-type="fig" rid="f2">
<bold>Figure&#xa0;2</bold>
</xref>), with lower pH<sub>T</sub> values corresponding to higher pCO<sub>2w</sub> levels and vice versa (<xref ref-type="table" rid="T1">
<bold>Table&#xa0;1</bold>
</xref>). pH<sub>T</sub> averaged 8.01 &#xb1; 0.03, peaking on September 15 (8.09), then decreasing until October 25, reaching a minimum on October 16 (7.93), before increasing again until November 7. In contrast, pCO<sub>2w</sub> averaged 397 &#xb1; 36 &#x3bc;atm, reaching its minimum on September 15 (302 &#x3bc;atm), increasing until October 25, reaching a maximum on October 16 (499 &#x3bc;atm), and then decreasing until November 7. Salinity averaged 29.74 &#xb1; 0.94, increasing until October 25, with a peak on October 20 (31.29), then decreasing until November 7, reaching its minimum on that date (27.03). Similarly, TA averaged 1959 &#xb1; 54 &#x3bc;mol kg<sup>-1</sup>, increasing until October 25, with a maximum on October 20 (2048 &#x3bc;mol kg<sup>-1</sup>), then decreasing until November 7, when it reached its minimum (1803 &#x3bc;mol kg<sup>-1</sup>). DIC followed a similar pattern, averaging 1728 &#xb1; 49 &#x3bc;mol kg<sup>-1</sup>, increasing until October 25, with a maximum on October 11 (1807 &#x3bc;mol kg<sup>-1</sup>), and decreasing until November 7, with a minimum on November 5 (1574 &#x3bc;mol kg<sup>-1</sup>). The temperature averaged 27.39 &#xb1; 0.30&#xb0;C, with a peak on September 20 (28.50&#xb0;C), decreasing until October 9 and remaining stable until October 25 (27.25 &#xb1; 0.16&#xb0;C), before oscillating until November 7, when it reached a minimum on November 4 (26.72&#xb0;C).</p>
<fig id="f2" position="float">
<label>Figure&#xa0;2</label>
<caption>
<p>High-frequency measurements of <bold>(A)</bold> pH<sub>T</sub> (green), <bold>(B)</bold> salinity (blue), <bold>(C)</bold> temperature (brown), <bold>(D)</bold> pCO<sub>2w</sub> (orange), <bold>(E)</bold> dissolved inorganic carbon (DIC; red), and <bold>(F)</bold> total alkalinity (TA; black) every three hours between September 13 and November 07, 2021. The black circles highlight each variable&#x2019;s highest and lowest values, while the red dot marks October 25, when pH<sub>T</sub> began to increase and pCO<sub>2w</sub>, salinity, TA, and DIC began to decrease.</p>
</caption>
<graphic mimetype="image" mime-subtype="tiff" xlink:href="fmars-12-1595871-g002.tif">
<alt-text content-type="machine-generated">Six time-series graphs (A-F) showing trends from September 13 to November 7. Graph A plots pH levels in green, B shows salinity in blue, and C depicts temperature in brown. Graph D presents pCO2 in yellow, E displays DIC in red, and F illustrates TA in black. Each graph uses a red dot to mark a specific data point.</alt-text>
</graphic>
</fig>
<table-wrap id="T1" position="float">
<label>Table&#xa0;1</label>
<caption>
<p>Descriptive statistics of the measured and derived variables (*) from September 13 to November 07, 2021, in El Muelle reef, GNNP, Colombian Pacific.</p>
</caption>
<table frame="hsides">
<thead>
<tr>
<th valign="middle" rowspan="2" align="right">Statistics</th>
<th valign="top" align="right">pH</th>
<th valign="top" rowspan="2" align="right">Salinity</th>
<th valign="top" align="right">Temperature</th>
<th valign="top" align="right">pCO<sub>2w</sub>*</th>
<th valign="top" align="right">DIC *</th>
<th valign="top" align="right">TA *</th>
<th valign="top" rowspan="2" align="right">&#x2126;<sub>a</sub>*</th>
</tr>
<tr>
<th valign="top" align="right">(total scale)</th>
<th valign="top" align="right">(&#xb0;C)</th>
<th valign="top" align="right">(&#x3bc;atm)</th>
<th valign="top" align="right">(&#x3bc;mol kg<sup>-1</sup>)</th>
<th valign="top" align="right">(&#x3bc;mol kg<sup>-1</sup>)</th>
</tr>
</thead>
<tbody>
<tr>
<td valign="top" align="left">Mean<break/>&#xb1; SD</td>
<td valign="top" align="right">8.01&#x202f;&#xb1;&#x202f;0.03</td>
<td valign="top" align="right">29.74&#x202f;&#xb1;&#x202f;0.94</td>
<td valign="top" align="right">27.39&#x202f;&#xb1;&#x202f;0.30</td>
<td valign="top" align="right">396.78&#x202f;&#xb1;&#x202f;36.25</td>
<td valign="top" align="right">1728.10&#x202f;&#xb1;&#x202f;49.06</td>
<td valign="top" align="right">1959.42&#x202f;&#xb1;&#x202f;54.14</td>
<td valign="top" align="right">2.71&#x202f;&#xb1;&#x202f;0.17</td>
</tr>
<tr>
<td valign="top" align="left">Maximum</td>
<td valign="top" align="right">8.09</td>
<td valign="top" align="right">31.29</td>
<td valign="top" align="right">28.50</td>
<td valign="top" align="right">498.94</td>
<td valign="top" align="right">1806.97</td>
<td valign="top" align="right">2047.60</td>
<td valign="top" align="right">3.09</td>
</tr>
<tr>
<td valign="top" align="left">Minimum</td>
<td valign="top" align="right">7.93</td>
<td valign="top" align="right">27.03</td>
<td valign="top" align="right">26.72</td>
<td valign="top" align="right">302.29</td>
<td valign="top" align="right">1574.23</td>
<td valign="top" align="right">1802.74</td>
<td valign="top" align="right">2.22</td>
</tr>
<tr>
<td valign="top" align="left">N</td>
<td valign="top" align="right">392</td>
<td valign="top" align="right">403</td>
<td valign="top" align="right">422</td>
<td valign="top" align="right">354</td>
<td valign="top" align="right">355</td>
<td valign="top" align="right">391</td>
<td valign="top" align="right">355</td>
</tr>
</tbody>
</table>
<table-wrap-foot>
<fn>
<p>The mean value, standard deviation (SD), maximum, minimum, and sample size of the measured variables pH<sub>T</sub>, salinity, temperature, and derived variables pCO<sub>2w</sub>, DIC, TA, and &#x3a9;<sub>a</sub> are described.</p>
</fn>
</table-wrap-foot>
</table-wrap>
<p>When pH<sub>T</sub> was normalized using salinity and temperature, the variation attributed to mean salinity reached up to 0.001 pH units, and up to 0.047 pH units when using the minimum salinity. In contrast, minor temperature-related variations reached only 0.000028 pH units with the mean temperature and 0.017 pH units with the minimum temperature. These results suggest that salinity plays a more significant role than temperature in driving pH<sub>T</sub> variability (<xref ref-type="supplementary-material" rid="SM1">
<bold>Supplementary Figure&#xa0;2</bold>
</xref>).</p>
<sec id="s3_1">
<label>3.1</label>
<title>Tidal movement</title>
<p>No significant differences were found between high and low tides for the dependent variables of pH<sub>T</sub>, salinity, temperature, pCO<sub>2w</sub>, DIC, and TA (<xref ref-type="supplementary-material" rid="SM1">
<bold>Supplementary Table&#xa0;3</bold>
</xref>). However, pH<sub>T</sub> during flood tide (8.010 &#xb1; 0.031) was slightly higher than during ebb tide (8.008 &#xb1; 0.029), with a lower positive slope on the regression line (<xref ref-type="fig" rid="f3">
<bold>Figure&#xa0;3A</bold>
</xref>). pCO<sub>2w</sub> and DIC showed similar values during the flood tide (396 &#xb1; 38 &#x3bc;atm and 1726 &#xb1; 52 &#xb5;mol kg<sup>-</sup>&#xb9;, respectively) and the ebb tide (397 &#xb1; 35 &#x3bc;atm and 1730 &#xb1; 46 &#xb5;mol kg<sup>-</sup>&#xb9;, respectively), with a slight negative slope observed in the regression trend (<xref ref-type="fig" rid="f3">
<bold>Figures&#xa0;3D, E</bold>
</xref>, respectively). Variables such as temperature, salinity, and TA exhibited slopes close to zero, indicating that this area&#x2019;s seawater and river water are well-mixed.</p>
<fig id="f3" position="float">
<label>Figure&#xa0;3</label>
<caption>
<p>Normalized water level (0.00&#x2013;1.00) plotted against the dependent variables: <bold>(A)</bold> pH<sub>T</sub>, <bold>(B)</bold> salinity, <bold>(C)</bold> temperature, <bold>(D)</bold> pCO<sub>2W</sub>, <bold>(E)</bold> dissolved inorganic carbon (DIC), and <bold>(F)</bold> total alkalinity (TA). The blue regression line and dots represent flood, while the red regression line and triangles represent ebb. A normalized tide value of 0.00 corresponds to a minimum low tide, and 1.00 corresponds to a maximum high tide.</p>
</caption>
<graphic mimetype="image" mime-subtype="tiff" xlink:href="fmars-12-1595871-g003.tif">
<alt-text content-type="machine-generated">Six scatter plots labeled A to F show relationships between normalized water level and various parameters. A: pH (total scale) ranges around 8.00. B: Salinity varies near 29 to 31. C: Temperature fluctuates between 26.5 to 28.5 degrees Celsius. D: pCO2, measured in microatmospheres, spans 300 to 500. E: DIC, in micromoles per kilogram, is between 1690 to 1810. F: TA, also in micromoles per kilogram, ranges from 1800 to 2050. Each plot includes trend lines with scatter points.</alt-text>
</graphic>
</fig>
</sec>
<sec id="s3_2">
<label>3.2</label>
<title>Physico-chemical seawater parameters and atmospheric variables (56 days&#x2019; time scale)</title>
<p>The independent atmospheric variables (solar radiation and total precipitation) were correlated with water type (sea surface temperature and salinity) and carbon chemistry data (pH<sub>T</sub>, pCO<sub>2w</sub>, DIC, and TA). Total daily solar radiation showed the strongest correlations with all dependent variables; suggesting that average radiation values of 3078 &#xb1; 1098 Wh m<sup>-</sup>&#xb2; (n= 56), as well as radiation values in a range of 1378 to 5968 Wh m<sup>-</sup>&#xb2; displayed positively correlations with mean daily temperature and pH<sub>T</sub>, and negative correlations with salinity, pCO<sub>2w</sub>, DIC, and TA (<xref ref-type="table" rid="T2">
<bold>Table&#xa0;2</bold>
</xref>). In contrast, total daily precipitation (mean average of 31 &#xb1; 27 mm; n= 56) within the 0 to 115 mm range only correlated negatively with mean daily salinity (<xref ref-type="table" rid="T2">
<bold>Table&#xa0;2</bold>
</xref>). No significant correlation was observed between daily precipitation and pH<sub>T</sub>, temperature, pCO<sub>2W</sub>, DIC, and TA (<xref ref-type="table" rid="T2">
<bold>Table&#xa0;2</bold>
</xref>). In addition, rainwater samples collected during the high rainfall season (May 2022) in GNNP showed the lowest salinity values (0.26).</p>
<table-wrap id="T2" position="float">
<label>Table&#xa0;2</label>
<caption>
<p>Spearman correlation between the dependent variables (daily average) pH<sub>T</sub>, salinity, temperature, pCO<sub>2W</sub>, dissolved inorganic carbon (DIC), total alkalinity (TA), and the independent variables (daily total) solar radiation and precipitation.</p>
</caption>
<table frame="hsides">
<thead>
<tr>
<th valign="top" align="left">Variables</th>
<th valign="bottom" colspan="1" align="left">Statistics</th>
<th valign="top" align="right">pH<sub>T</sub>
</th>
<th valign="top" align="right">Salinity</th>
<th valign="top" align="right">T</th>
<th valign="top" align="right">pCO<sub>2w</sub>*</th>
<th valign="top" align="right">DIC *</th>
<th valign="top" align="right">TA*</th>
</tr>
</thead>
<tbody>
<tr>
<td valign="bottom" align="left">Radiation</td>
<td valign="bottom" align="left">p value</td>
<td valign="top" align="right">
<bold>0.01</bold>
</td>
<td valign="top" align="right">
<bold>0.00</bold>
</td>
<td valign="top" align="right">
<bold>0.00</bold>
</td>
<td valign="top" align="right">
<bold>0.00</bold>
</td>
<td valign="top" align="right">
<bold>0.00</bold>
</td>
<td valign="top" align="right">
<bold>0.00</bold>
</td>
</tr>
<tr>
<td valign="bottom" align="left">
</td>
<td valign="bottom" align="left">rho</td>
<td valign="top" align="right">0.37</td>
<td valign="top" align="right">-0.41</td>
<td valign="top" align="right">0.51</td>
<td valign="top" align="right">-0.46</td>
<td valign="top" align="right">-0.42</td>
<td valign="top" align="right">-0.41</td>
</tr>
<tr>
<td valign="bottom" align="left">Precipitation</td>
<td valign="bottom" align="left">p value</td>
<td valign="top" align="right">0.22</td>
<td valign="top" align="right">
<bold>0.04</bold>
</td>
<td valign="top" align="right">0.85</td>
<td valign="top" align="right">0.13</td>
<td valign="top" align="right">0.06</td>
<td valign="top" align="right">0.06</td>
</tr>
<tr>
<td valign="bottom" align="left">
</td>
<td valign="bottom" align="left">rho</td>
<td valign="top" align="right">0.17</td>
<td valign="top" align="right">-0.28</td>
<td valign="top" align="right">0.03</td>
<td valign="top" align="right">-0.21</td>
<td valign="top" align="right">-0.26</td>
<td valign="top" align="right">-0.26</td>
</tr>
<tr>
<td valign="bottom" align="left">pH</td>
<td valign="bottom" align="left">p value</td>
<td valign="top" align="right"/>
<td valign="top" align="right">
<bold>0.00</bold>
</td>
<td valign="top" align="right">
<bold>0.03</bold>
</td>
<td valign="top" align="right">
<bold>0.00</bold>
</td>
<td valign="top" align="right">
<bold>0.00</bold>
</td>
<td valign="top" align="right">
<bold>0.00</bold>
</td>
</tr>
<tr>
<td valign="bottom" align="left">
</td>
<td valign="bottom" align="left">rho</td>
<td valign="top" align="right"/>
<td valign="top" align="right">-0.54</td>
<td valign="top" align="right">0.29</td>
<td valign="top" align="right">-0.95</td>
<td valign="top" align="right">-0.63</td>
<td valign="top" align="right">-0.53</td>
</tr>
<tr>
<td valign="bottom" align="left">N</td>
<td valign="bottom" align="left">
</td>
<td valign="top" align="right">56</td>
<td valign="top" align="right">56</td>
<td valign="top" align="right">56</td>
<td valign="top" align="right">56</td>
<td valign="top" align="right">56</td>
<td valign="top" align="right">56</td>
</tr>
</tbody>
</table>
<table-wrap-foot>
<fn>
<p>In bold, the variables that were significantly correlated (p &lt; 0.05). Dependent variables marked with an asterisk (*) indicate values derived either from a regression with salinity (e.g., TA) or calculated using CO2sys (e.g., pCO<sub>2W</sub> and DIC). In contrast, unmarked variables were directly measured in the field.</p>
</fn>
</table-wrap-foot>
</table-wrap>
</sec>
<sec id="s3_3">
<label>3.3</label>
<title>Diurnal, 24-hour cycle of the carbonate system</title>
<p>pH<sub>T</sub>, temperature, pCO<sub>2W,</sub> and DIC followed a pronounced diurnal cycle with significant differences (p &lt; 0.05; <xref ref-type="supplementary-material" rid="SM1">
<bold>Supplementary Table&#xa0;4</bold>
</xref>) between early morning and late evening hours (<xref ref-type="fig" rid="f4">
<bold>Figure&#xa0;4</bold>
</xref>). During early morning hours, after sunrise (5:00 - 6:00), at 8:00 the lowest values of pH<sub>T</sub> (7.993 &#xb1; 0.040; <xref ref-type="fig" rid="f4">
<bold>Figure&#xa0;4A</bold>
</xref>) and temperature (27.23 &#xb1; 0.18; <xref ref-type="fig" rid="f4">
<bold>Figure&#xa0;4B</bold>
</xref>) were recorded, as well as the highest values of pCO<sub>2W</sub> (413 &#xb1; 40 &#x3bc;atm; <xref ref-type="fig" rid="f4">
<bold>Figure&#xa0;4C</bold>
</xref>) and DIC (1739 &#xb1; 46 &#x3bc;mol kg<sup>-</sup>&#xb9;; Figure D). In the late afternoon (17:00 - 18:00), during sunset, the highest values of pH<sub>T</sub> (8.030 &#xb1; 0.025; <xref ref-type="fig" rid="f4">
<bold>Figure&#xa0;4A</bold>
</xref>) and temperature (27.61 &#xb1; 0.36; <xref ref-type="fig" rid="f4">
<bold>Figure&#xa0;4B</bold>
</xref>) were found, together with the lowest pCO<sub>2W</sub> (374 &#xb1; 25 &#x3bc;atm; <xref ref-type="fig" rid="f4">
<bold>Figure&#xa0;4C</bold>
</xref>) and DIC (1718 &#xb1; 50 &#x3bc;mol kg<sup>-</sup>&#xb9;; <xref ref-type="fig" rid="f4">
<bold>Figure&#xa0;4D</bold>
</xref>). In contrast, salinity (<xref ref-type="fig" rid="f4">
<bold>Figure&#xa0;4E</bold>
</xref>), TA (<xref ref-type="fig" rid="f4">
<bold>Figure&#xa0;4F</bold>
</xref>), and carbonate alkalinity did not show significant differences (p &gt; 0.05, <xref ref-type="supplementary-material" rid="SM1">
<bold>Supplementary Table&#xa0;4</bold>
</xref>) between early morning and late evening hours.</p>
<fig id="f4" position="float">
<label>Figure&#xa0;4</label>
<caption>
<p>The diurnal scale (24 hours) of <bold>(A)</bold> pH<sub>T,</sub> <bold>(B)</bold> temperature, <bold>(C)</bold> pCO<sub>2W</sub>, <bold>(D)</bold> dissolved inorganic carbon (DIC), <bold>(E)</bold> salinity, and <bold>(F)</bold> total alkalinity (TA). The points represent the daily averages of measurements recorded every 3 hours over 56 consecutive days, with the red lines indicating the standard deviation of the daily averages. The shaded area highlights the daylight hours.</p>
</caption>
<graphic mimetype="image" mime-subtype="tiff" xlink:href="fmars-12-1595871-g004.tif">
<alt-text content-type="machine-generated">Six line graphs labeled A to F, each depicting different parameters over time (2:00 to 23:00). Graph A shows pH on a total scale, B shows temperature in Celsius, C displays partial pressure of CO2, D shows DIC (dissolved inorganic carbon) in micromoles per kilogram, E displays salinity, and F shows TA (total alkalinity) in micromoles per kilogram. Yellow shading indicates a specific time period shared across graphs. Data points have error bars, showing variations and trends throughout the day.</alt-text>
</graphic>
</fig>
</sec>
</sec>
<sec id="s4" sec-type="discussion">
<label>4</label>
<title>Discussion</title>
<sec id="s4_1">
<label>4.1</label>
<title>Freshwater input, precipitation, and river discharges play a key role in the Pacific Colombian GNNP region</title>
<p>The high variability found in variables pH<sub>T</sub>, salinity, temperature, pCO<sub>2w</sub>, DIC, and TA at El Muelle reef highlights the influence of La Ni&#xf1;a 2020&#x2013;2023 event. La Ni&#xf1;a event strengthened the Choco Jet (<xref ref-type="bibr" rid="B58">Hoyos et&#xa0;al., 2013</xref>; <xref ref-type="bibr" rid="B7">Arias et&#xa0;al., 2015</xref>; <xref ref-type="bibr" rid="B99">Serna et&#xa0;al., 2018</xref>), which caused an increase in precipitation in the Colombian Pacific basin and, consequently, an increase in the river flow into the sea (<xref ref-type="bibr" rid="B90">Restrepo and Kjerfve, 2000</xref>; <xref ref-type="bibr" rid="B11">Blanco, 2009</xref>; <xref ref-type="bibr" rid="B99">Serna et&#xa0;al., 2018</xref>). During the sampling period from September to November 2021, the station &#x201c;57025020 Gorgona Guapi&#x201d; recorded a total precipitation of 2878 mm, exceeding the total multiannual monthly average by more than 59% to 1815 mm.</p>
<p>Likewise, the station &#x201c;53047010 Sangaral&#x201d; recorded a monthly average flow of the Guapi River of 447 m&#xb3; s<sup>-1</sup>, exceeding by 44% the total multiannual monthly average of 309 m&#xb3; s<sup>-1</sup>. Thus, the sampling period was characterized by a considerable inflow of freshwater from river discharges and high rainfall that explained the reduced recorded salinity values and part of the pH<sub>T</sub> variability (<xref ref-type="fig" rid="f2">
<bold>Figure&#xa0;2</bold>
</xref>). The salinity normalization and correlation (<xref ref-type="table" rid="T2">
<bold>Table&#xa0;2</bold>
</xref>) suggest that salinity plays a significant role in pH<sub>T</sub> variability. The interplay between low salinity and reduced alkalinity (directly correlated) and pH variability underscores its critical role in coastal biogeochemical cycles. Reduced salinity not only dilutes carbonate and bicarbonate ions but also disrupts the equilibrium of the CO<sub>2</sub> system, as observed in estuarine zones by <xref ref-type="bibr" rid="B37">Feely et&#xa0;al. (2010)</xref> and <xref ref-type="bibr" rid="B13">Cai et&#xa0;al. (2021)</xref>, where freshwater influx exacerbates anthropogenic CO<sub>2</sub> uptake. These dynamics challenge the buffering capacity and resilience, particularly in reefs, where a range of water pH is essential for calcification.</p>
<p>Additionally, high rainfall and the consequent excess of freshwater (characteristic of a RioMar system) acted as a surface layer dilution factor (<xref ref-type="bibr" rid="B118">Zeebe and Wolf-Gladrow, 2001</xref>; <xref ref-type="bibr" rid="B105">Turk et&#xa0;al., 2010</xref>; <xref ref-type="bibr" rid="B104">Trujillo and Thurman, 2016</xref>; <xref ref-type="bibr" rid="B57">Ho and Schanze, 2020</xref>), contributing to reducing, even more, the salinity over time. For example, <xref ref-type="bibr" rid="B57">Ho and Schanze (2020)</xref> reported a rapid decrease in salinity of 4.4 at depths of 2 to 3 cm in response to heavy rainfall in the Eastern Equatorial Pacific, highlighting the impact of precipitation on coastal salinity dynamics. Salinity gradients and alkalinity depletion may act as synergistic stressors, which align with broader concerns about coastal acidification (<xref ref-type="bibr" rid="B31">Doney et&#xa0;al., 2009</xref>) and the ecological risks associated with climate change scenarios.</p>
<p>The tides exert a continuous physical influence, due considerable tidal variation, having maximum amplitudes of 5.82 m and minimum of -0.78 m in 2021 (3.39 &#xb1; 1.20 m; <xref ref-type="bibr" rid="B41">Flanders Marine Institute [VLIZ] and Intergovernmental Oceanographic Commission [IOC], 2025</xref>), implying millions of cubic meters of freshwater entering and leaving the coastal system, mixing oceanic water with freshwater coming from the Patia-Sanquianga complex plus the rainfall. The well-mixed RioMar water has minimal salinity variations throughout a full ebb and flow cycle (<xref ref-type="fig" rid="f3">
<bold>Figure&#xa0;3</bold>
</xref>). This high mixing condition persists up to 55 km downstream of the river mouth. As indicated by <xref ref-type="bibr" rid="B82">Palacios Moreno and Pinto Tovar (1992)</xref>, due to the high tide, mixing begins at the river mouth, where seawater enters through the bottom of the Guapi River, resulting in waters with a salinity of 25.60 at 10 m, compared to 17 at 1 m. Furthermore, tides and the southern trade winds during La Ni&#xf1;a events generate coastal currents and a strong swell (<xref ref-type="bibr" rid="B81">Osorio et&#xa0;al., 2014</xref>) that contribute to mixing these two water types, creating an estuary environment. Consequently, this coastal zone can be classified as a Type 2 RiOMar regime (<xref ref-type="bibr" rid="B23">Dai et&#xa0;al., 2022a</xref>), characterized by a high-energy tidal system and significant mixing near the river mouths (<xref ref-type="bibr" rid="B66">Lamarque et&#xa0;al., 2022</xref>).</p>
<p>In this scenario, the riverine influence reaching GNNP may explain the observed decrease in pH<sub>T</sub> over the study period. This trend is likely driven by the input of CO<sub>2</sub> derived from riverine DIC, potentially due to the input and decomposition of organic matter, which increases H<sup>+</sup> ion concentrations, as observed in other coastal regions (<xref ref-type="bibr" rid="B109">Vargas et&#xa0;al., 2016</xref>; <xref ref-type="bibr" rid="B13">Cai et&#xa0;al., 2021</xref>). In fact, in the Eastern Colombian Pacific, the observed decrease and low values of pH<sub>T</sub> were strongly correlated with salinity, pCO<sub>2w</sub>, and DIC (<xref ref-type="table" rid="T2">
<bold>Table&#xa0;2</bold>
</xref>). Between 2018 and 2021, data collected at 13 river stations near the GNNP showed pH<sub>NBS</sub> values ranging from 6.3 to 8.3. Suspended solids ranged from 11 to 407 mg L<sup>-1</sup>, while nitrate (NO<sub>3</sub>
<sup>-</sup>) concentrations ranged from 2 to 90.9 &#xb5;g L<sup>-1</sup>. Phosphate (P-PO<sub>4</sub>
<sup>3-</sup>) levels fluctuated between 2 and 3.3 &#xb5;g L<sup>-1</sup>, and chlorophyll-a concentrations ranged from 0.07 to 9.8 &#xb5;g L<sup>-1</sup>. The highest values &#x200b;&#x200b;for these parameters were recorded during the year&#x2019;s second half, coinciding with the rainy season (<xref ref-type="bibr" rid="B61">INVEMAR, 2020b</xref>; <xref ref-type="bibr" rid="B62">INVEMAR, 2022</xref>), which could contribute to acidification. This phenomenon aligns with RiOMar systems, where high DIC and nutrient inputs from rivers reach nearshore waters, and organic matter is subsequently exported to the continental shelf (<xref ref-type="bibr" rid="B42">Gan et&#xa0;al., 2009</xref>; <xref ref-type="bibr" rid="B23">Dai et&#xa0;al., 2022a</xref>). Decreases in pH<sub>T</sub> in other estuaries have been indirectly linked to fluvial discharges. For example, along the central-southern Chilean Pacific coast (Biob&#xed;o River basin), the expansion of the river plume seaward led to reduced pH<sub>T</sub> conditions (7.6) during periods of maximum higher river discharge, compared to more oceanic stations where pH<sub>T</sub> ranged from 7.95 to 8.15 (<xref ref-type="bibr" rid="B109">Vargas et&#xa0;al., 2016</xref>). Likewise, in the South Pacific Ocean, in Coral Bay, fluvial discharges from low-pH rivers (7.739 &#xb1; 0.022) cause coastal areas with low pH<sub>T</sub> (8.014 &#xb1; 0.015) (<xref ref-type="bibr" rid="B2">Aguilera et&#xa0;al., 2013</xref>), similar to low pH observed across the GNNP Colombian Pacific Region. Indeed, the surface values (2m) of pH<sub>T</sub> (8.01 &#xb1; 0.03), salinity (29.74 &#xb1; 0.94), TA (1959 &#xb1; 54 &#xb5;mol kg<sup>-1</sup>), DIC (1728 &#xb1; 49 &#xb5;mol kg<sup>-1</sup>) and &#x3a9;<sub>a</sub> (2.71 &#xb1; 0.17) at El Muelle reef (GNNP) are below the surface averages reported for the North Pacific (8. 105 &#xb1; 0.06, 34.05 &#xb1; 0.86, 2255 &#xb1; 34 &#xb5;mol kg<sup>-1</sup>, 1959 &#xb1; 42 &#xb5;mol kg<sup>-1</sup> and 3.30 &#xb1; 0.7; respectively) and the South Pacific (8.079 &#xb1; 0.03, 35.29 &#xb1; 0.55, 2319 &#xb1; 35 &#xb5;mol kg<sup>-1</sup>, 2003 &#xb1; 39 &#xb5;mol kg<sup>-1</sup> and 3.52 &#xb1; 0.4) (<xref ref-type="bibr" rid="B38">Feely et&#xa0;al., 2009</xref>).</p>
<p>On the contrary, oceanic areas without river input, such as North Pacific Monterey Bay, have recorded relatively high pH<sub>T</sub> (<xref ref-type="bibr" rid="B51">Gray et&#xa0;al., 2011</xref>). However, at higher latitudes on the Pacific coast of Costa Rica, low pH<sub>T</sub> levels were associated with the rainy season (<xref ref-type="bibr" rid="B97">S&#xe1;nchez-Noguera et&#xa0;al., 2018</xref>). A drop in pH<sub>T</sub> is also known to occur in the estuaries of Swartkops and Sundays in South Africa, where, due to strong inflows of freshwater, a high pH<sub>T</sub> decrease of 0,46 pH units was produced (<xref ref-type="bibr" rid="B32">Edworthy et&#xa0;al., 2022</xref>). The relatively low pH<sub>T</sub> of the Pacific Colombian Coast (El Muelle, GNNP, <xref ref-type="table" rid="T3">
<bold>Table&#xa0;3</bold>
</xref>) is similar to studies in the East River China Sea, where the low pH<sub>T</sub> (7.98 to 8.07) was attributed to the high river inputs from the Changjiang plume, known to carry organic carbon, nutrients, and CO<sub>2</sub> supersaturated water (<xref ref-type="bibr" rid="B113">Wu et&#xa0;al., 2021</xref>). We already know that freshwater inputs from rivers play a critical role in shaping carbonate chemistry in coastal systems, particularly in the continental shelf. As well as in our study site, <xref ref-type="bibr" rid="B89">R&#xe9;rolle et&#xa0;al. (2018)</xref> have identified riverine discharges, characterized by high DIC and TA, as key drivers of reduced pH<sub>T</sub> in the Irish Sea, southern North Sea, and Skagerrak region. Further studies on carbon chemistry in the region are needed, including direct measurements of DIC and dissolved organic matter in the Patia-Sanquianga complex during wet and dry seasons. These and other chemical parameters, such as nutrients, are crucial to evaluating rivers&#x2019; contribution to coastal carbonate chemistry, particularly near reef systems, and the impact on ocean acidification (<xref ref-type="bibr" rid="B12">Borges et&#xa0;al., 2005</xref>; <xref ref-type="bibr" rid="B13">Cai et&#xa0;al., 2021</xref>). The main knowledge gaps include the effects of remineralization on pH in tropical estuaries (<xref ref-type="bibr" rid="B24">Dai et&#xa0;al., 2022b</xref>; <xref ref-type="bibr" rid="B109">Vargas et&#xa0;al., 2016</xref>) to understand the vulnerability of ecosystems to OA.</p>
<table-wrap id="T3" position="float">
<label>Table&#xa0;3</label>
<caption>
<p>Comparison between autonomous sensors recorded total scale pH (pH<sub>T</sub>) across various geographical zones.</p>
</caption>
<table frame="hsides">
<thead>
<tr>
<th valign="top" align="left">Location</th>
<th valign="top" align="left">Long.</th>
<th valign="top" align="left">Lat.</th>
<th valign="top" align="left">Ocean</th>
<th valign="top" align="left">Instrument</th>
<th valign="top" align="left">pH<sub>T</sub> range</th>
<th valign="top" align="left">Reference</th>
</tr>
</thead>
<tbody>
<tr>
<td valign="top" align="left">Bahia Monterrey, <break/>EEUU</td>
<td valign="top" align="left">121&#xb0; 54&#x2032; 0&#x2033; W</td>
<td valign="top" align="left">36&#xb0; 49&#x2032; 48&#x2033; N</td>
<td valign="top" align="left">Pacific Ocean</td>
<td valign="top" align="left">iSAMI-pH</td>
<td valign="top" align="right">7.93 - 8.37</td>
<td valign="top" align="left">
<xref ref-type="bibr" rid="B51">Gray et&#xa0;al., 2011</xref>
</td>
</tr>
<tr>
<td valign="top" align="left">Bahia Culebra, Costa Rica</td>
<td valign="top" align="left">85&#xb0; 36&#x2032; 0&#x2033; W</td>
<td valign="top" align="left">10&#xb0; 30&#x2032; 0&#x2033; N</td>
<td valign="top" align="left">Pacific Ocean</td>
<td valign="top" align="left">iSAMI-pH</td>
<td valign="top" align="right">7.98 - 8.06</td>
<td valign="top" align="left">
<xref ref-type="bibr" rid="B97">S&#xe1;nchez-Noguera et&#xa0;al., 2018</xref>
</td>
</tr>
<tr>
<td valign="top" align="left">East China Sea</td>
<td valign="top" align="left">128&#xb0; 30&#x2032; 0&#x2033; E</td>
<td valign="top" align="left">30&#xb0; 0&#x2032; 0&#x2033; N</td>
<td valign="top" align="left">Pacific Ocean</td>
<td valign="top" align="left">SeaFET Ocean pH sensor</td>
<td valign="top" align="right">7.98 - 8.07</td>
<td valign="top" align="left">
<xref ref-type="bibr" rid="B113">Wu et&#xa0;al., 2021</xref>
</td>
</tr>
<tr>
<td valign="top" align="left">Northwest European Shelf Seas</td>
<td valign="top" align="left">10&#xb0; 0&#x2032; 0&#x2033; W to 10&#xb0; 0&#x2032; 0&#x2033; E</td>
<td valign="top" align="left">45&#xb0; 0&#x2032; 0&#x2033; N to 60&#xb0; 0&#x2032; 0&#x2033; N</td>
<td valign="top" align="left">Atlantic Ocean</td>
<td valign="top" align="left">Lab-on-Chip</td>
<td valign="top" align="right">7.99 - 8.21</td>
<td valign="top" align="left">
<xref ref-type="bibr" rid="B89">R&#xe9;rolle et&#xa0;al., 2018</xref>
</td>
</tr>
<tr>
<td valign="top" align="left">Algoa Bay, South Africa</td>
<td valign="top" align="left">25&#xb0; 48&#x2032; 0&#x2033; E</td>
<td valign="top" align="left">33&#xb0; 48&#x2032; 0&#x2033; S</td>
<td valign="top" align="left">Atlantic Ocean</td>
<td valign="top" align="left">iSAMI-pH</td>
<td valign="top" align="right">7.98 - 8.44</td>
<td valign="top" align="left">
<xref ref-type="bibr" rid="B32">Edworthy et&#xa0;al., 2022</xref>
</td>
</tr>
<tr>
<td valign="top" align="left">Gorgona, Colombia</td>
<td valign="top" align="left">78&#xb0; 6&#x2032; 0&#x2033; W</td>
<td valign="top" align="left">2&#xb0; 54&#x2032; 0&#x2033; N</td>
<td valign="top" align="left">Pacific Ocean</td>
<td valign="top" align="left">iSAMI-pH</td>
<td valign="top" align="right">7.93 - 8.09</td>
<td valign="top" align="left">This study (2021)</td>
</tr>
</tbody>
</table>
<table-wrap-foot>
<fn>
<p>Note that the minimum pH<sub>T</sub> recorded at Gorgona Island, Colombia, is lower than in other regions.</p>
</fn>
</table-wrap-foot>
</table-wrap>
</sec>
<sec id="s4_2">
<label>4.2</label>
<title>Daily scale of carbon and physical seawater variability and atmospheric variables, solar radiation, and precipitation</title>
<p>During the study period, the ITCZ was located close to the equator in the Colombian Pacific Ocean (<xref ref-type="bibr" rid="B28">D&#xed;az Guevara et&#xa0;al., 2008</xref>), which intensified cloudiness and precipitation due to the convergence of trade winds from the northern and southern hemispheres (<xref ref-type="bibr" rid="B28">D&#xed;az Guevara et&#xa0;al., 2008</xref>). The increase in cloudiness likely contributed to the decline in solar radiation, which diminished from 3,709 &#xb1; 1,205 Wh m<sup>-2</sup> in September to 2,501 &#xb1; 789 Wh m<sup>-2</sup> in November, with a marked reduction between October 1 and 25 (2,488 &#xb1; 590 Wh m<sup>-2</sup>; <xref ref-type="fig" rid="f5">
<bold>Figure&#xa0;5A</bold>
</xref>). Given the positive correlation between solar radiation and temperature (<xref ref-type="bibr" rid="B104">Trujillo and Thurman, 2016</xref>; <xref ref-type="bibr" rid="B112">Webster, 2020</xref>), the decrease in solar radiation may explain the low SST observed from September 13 to November 7. According to <xref ref-type="bibr" rid="B75">Millero (2007</xref>, <xref ref-type="bibr" rid="B77">2013)</xref> lower temperatures increase CO<sub>2</sub> solubility in seawater, suggesting that the temperature decline likely improved oceanic CO<sub>2</sub> uptake by enabling its transfer from the atmosphere to the ocean during the study period. The resulting CO<sub>2</sub> increase could explain pCO<sub>2w</sub> and DIC&#x2019;s highest values (<xref ref-type="fig" rid="f2">
<bold>Figure&#xa0;2</bold>
</xref>), particularly between October 1 and 25, when solar radiation was at its lowest (<xref ref-type="fig" rid="f5">
<bold>Figure&#xa0;5</bold>
</xref>). Thus, the solar radiation and temperature reduction may partially explain the observed decline in pH<sub>T</sub> during this period. The inverse correlation between pH<sub>T</sub> and pCO<sub>2w</sub> also suggests that fluctuations in pCO<sub>2w</sub> (indirectly DIC) could help explain pH<sub>T</sub> variations over September-November (<xref ref-type="table" rid="T2">
<bold>Table&#xa0;2</bold>
</xref>; <xref ref-type="bibr" rid="B118">Zeebe and Wolf-Gladrow, 2001</xref>; <xref ref-type="bibr" rid="B77">Millero, 2013</xref>; <xref ref-type="bibr" rid="B13">Cai et&#xa0;al., 2021</xref>). After October 25, the rise in solar radiation and temperature may have led to a pH<sub>T</sub> increment by approximately 0.028 units, along with a decrease in pCO<sub>2w</sub> by 41 &#x3bc;atm and DIC by 100 &#x3bc;mol kg<sup>-1</sup> (<xref ref-type="fig" rid="f2">
<bold>Figures&#xa0;2D, E</bold>
</xref>).</p>
<fig id="f5" position="float">
<label>Figure&#xa0;5</label>
<caption>
<p>Atmospheric variables in the study area from September 13 to November 7, 2021. <bold>(A)</bold> Solar radiation was recorded at station 26015040 (Arrayanales). The black line indicates the daily (September to 7 November 2021) for solar radiation (3078 Wh m<sup>-2</sup>) and precipitation (31 mm), and <bold>(B)</bold> Total precipitation was recorded at station 57025020 (Gorgona). Periods above the daily average are highlighted in blue, while periods below the daily average are shown in red.</p>
</caption>
<graphic mimetype="image" mime-subtype="tiff" xlink:href="fmars-12-1595871-g005.tif">
<alt-text content-type="machine-generated">Two bar charts compare solar radiation and precipitation over time. Chart A shows solar radiation in watt-hours per square meter, with blue and red bars, fluctuating around the 3000 level from September 13 to November 7. Chart B displays precipitation in millimeters, using similar color coding, varying around the 60 mark for the same period. Data points indicate differences in measurements over time.</alt-text>
</graphic>
</fig>
<p>Between October 3 and 16, total precipitation amounted to 22 mm (<xref ref-type="fig" rid="f5">
<bold>Figure&#xa0;5B</bold>
</xref>), with most days recording values below the mean daily precipitation of 31 mm. The observed reduction in precipitation likely diminished freshwater inflow relative to seawater, thereby enhancing salinity levels and elevating TA and DIC concentrations during this period. During the sampling period (September 13 to November 7), evaporation (<xref ref-type="bibr" rid="B20">Copernicus Climate Change Service, 2024</xref>) was highest in October (-62 mm), followed by September (-36 mm) and November (-15 mm). However, in all cases, the monthly accumulated evaporation remained well below the corresponding monthly precipitation totals of 680 mm, 727 mm, and 261 mm, respectively (<xref ref-type="bibr" rid="B25">DHIME, 2025</xref>).</p>
<p>In addition to previously discussed mechanisms, the elevated levels of pCO<sub>2w</sub>, DIC, and salinity observed between October 1 and 25 may also be influenced by a coastal upwelling event. This hypothesis is supported by the positive values of zonal Ekman transport (ZET) during this period, which indicates eastward surface water movement, given the regional coastline orientation and prevailing wind patterns (<xref ref-type="bibr" rid="B21">Corredor-Acosta et&#xa0;al., 2020</xref>). The eastward Ekman transport suggests offshore water displacement and the potential for deeper, carbon- and nutrient-rich water upwelling (<xref ref-type="supplementary-material" rid="SM1">
<bold>Supplementary Figure&#xa0;4</bold>
</xref>).</p>
</sec>
<sec id="s4_3">
<label>4.3</label>
<title>24-hour cycle of the carbonate system</title>
<p>During early morning hours (5:00 - 6:00 am), we registered the lowest pH<sub>T</sub> and temperature values, along with the highest concentration of pCO<sub>2w</sub> and DIC, suggesting the influence of night-time respiration processes before daylight (<xref ref-type="bibr" rid="B77">Millero, 2013</xref>; <xref ref-type="bibr" rid="B3">Albright et&#xa0;al., 2013</xref>; <xref ref-type="bibr" rid="B97">S&#xe1;nchez-Noguera et&#xa0;al., 2018</xref>). On the other hand, the highest values of pH<sub>T</sub> and temperature and the lowest values of pCO<sub>2w</sub> and DIC recorded during the late afternoon (17:00 - 18:00) suggest photosynthetic processes during daylight driven by increased solar radiation (<xref ref-type="bibr" rid="B22">Cyronak et&#xa0;al., 2013</xref>). The mean diel change of 0.037 units in pH<sub>T</sub> and 0.38 &#xb0;C in temperature between early morning and afternoon hours fall within the expected diel variability for shallow environments (0.7&#x2013;17 m), where biological and physical processes significantly influence pH and temperature dynamics (<xref ref-type="bibr" rid="B22">Cyronak et&#xa0;al., 2013</xref>).</p>
<p>The absence of a significant difference in TA and carbonate alkalinity between early morning and late afternoon hours may be due to the derivation of TA using a TA-salinity relationship, which primarily accounts for processes such as evaporation, precipitation, and mixing tides (<xref ref-type="bibr" rid="B100">Spaulding et&#xa0;al., 2014</xref>). In contrast, calcification and dissolution, more likely to exhibit variations over a 24-hour cycle, may not be adequately reflected (<xref ref-type="bibr" rid="B118">Zeebe and Wolf-Gladrow, 2001</xref>; <xref ref-type="bibr" rid="B77">Millero, 2013</xref>; <xref ref-type="bibr" rid="B13">Cai et&#xa0;al., 2021</xref>). However, the data indicate that the El Muelle reef, close to the sampling point, is composed predominantly of <italic>Pocillopora</italic> spp. (<xref ref-type="fig" rid="f1">
<bold>Figure&#xa0;1</bold>
</xref>; <xref ref-type="bibr" rid="B116">Zapata, 2001</xref>; <xref ref-type="bibr" rid="B1">Acosta et&#xa0;al., 2007</xref>), was exposed during the sampling period to low pH<sub>T</sub> (8.01 &#xb1; 0.03), salinity (29.32 &#xb1; 1.01), and &#x3a9;<sub>a</sub> (2.71 &#xb1; 0.17). These environmental conditions are considered challenging for <italic>Pocillopora</italic> spp., which are known to be highly sensitive to reduced pH and lowered salinity associated with river discharge (<xref ref-type="bibr" rid="B4">Alvarado et&#xa0;al., 2005</xref>; <xref ref-type="bibr" rid="B70">Lizcano-Sandoval et&#xa0;al., 2018</xref>; <xref ref-type="bibr" rid="B96">S&#xe1;nchez-Noguera, 2019</xref>). Notably, the global, annually averaged tolerance limit for coral reefs is an &#x3a9;<sub>a</sub> of 2.82, indicating that corals at this site live below the threshold commonly reported in the literature (<xref ref-type="bibr" rid="B52">Guan et&#xa0;al., 2015</xref>).</p>
<p>Despite these adverse conditions and frequent riverine influence, especially during the rainy season in the latter half of the year (<xref ref-type="bibr" rid="B44">Giraldo et&#xa0;al., 2008</xref>, <xref ref-type="bibr" rid="B47">2011</xref>), <italic>Pocillopora</italic> spp. persist and even dominate the area (<xref ref-type="bibr" rid="B116">Zapata, 2001</xref>; <xref ref-type="bibr" rid="B1">Acosta et&#xa0;al., 2007</xref>; <xref ref-type="bibr" rid="B70">Lizcano-Sandoval et&#xa0;al., 2018</xref>). Previous studies have shown that <italic>Pocillopora</italic> spp. in GNNP can maintain growth rates (<xref ref-type="bibr" rid="B70">Lizcano-Sandoval et&#xa0;al., 2018</xref>) and tolerate hypoxia, low salinity, and temperature fluctuations by reducing reproductive output rather than growth (<xref ref-type="bibr" rid="B17">Castrill&#xf3;n-Cifuentes et&#xa0;al., 2023a</xref>, <xref ref-type="bibr" rid="B18">2023</xref>). This suggests that these corals are either locally adapted or possess a degree of physiological tolerance to low pH, salinity, and &#x3a9;<sub>a</sub>. Similar findings from the Pearl River Estuary in Southeast China indicate that long-term hypo-salinity acclimation can enhance the tolerance of <italic>Pocillopora</italic> spp. to low salinity by reducing energy consumption, slowing metabolism, improving the energy metabolism of their symbiotic algae (Symbiodiniaceae), and altering their symbiotic bacterial communities to avoid bleaching (<xref ref-type="bibr" rid="B19">Chen et&#xa0;al., 2024</xref>). Nevertheless, <italic>Pocillopora</italic> spp. corals at Gorgona Island exhibit lower calcification rates (3.16 g CaCO<sub>3</sub> cm<sup>-2</sup> yr<sup>-1</sup>; <xref ref-type="bibr" rid="B70">Lizcano-Sandoval et&#xa0;al., 2018</xref>) compared to those reported in other reef systems, such as Panama (5&#x2013;6 g CaCO<sub>3</sub> cm<sup>-2</sup> yr<sup>-1</sup>; <xref ref-type="bibr" rid="B72">Manzello, 2010</xref>) and Mexico (2.99&#x2013;6.02 g CaCO<sub>3</sub> cm<sup>-2</sup> yr<sup>-1</sup>; <xref ref-type="bibr" rid="B73">Medell&#xed;n-Maldonado et&#xa0;al., 2016</xref>; <xref ref-type="bibr" rid="B50">Gonz&#xe1;lez-Pab&#xf3;n et&#xa0;al., 2021</xref>; <xref ref-type="bibr" rid="B103">Tortolero-Langarica et&#xa0;al., 2022</xref>). To establish a more robust correlation between the carbonate system and calcification rates in <italic>Pocillopora</italic> spp. at GNNP, future research efforts should prioritize <italic>in situ</italic> measurements of TA, dissolved oxygen, and direct calcification assessments (e.g., via buoyant weight or alkalinity anomaly techniques) on a 24-h scale during both rainy and dry seasons, to better quantify metabolic dynamics and clarify the adaptive capacity of this species under adverse environmental conditions.</p>
<p>In addition, future research should prioritize high-frequency measurements of pH, nutrient concentrations, and stable isotopes across diurnal, seasonal, and interannual timescales. These efforts should encompass both rainy and dry seasons and different ENSO phases, such as El Ni&#xf1;o and neutral conditions, to better distinguish water sources in the region and assess the influence of these temporal scales on carbonate chemistry variability.</p>
</sec>
</sec>
<sec id="s5" sec-type="conclusions">
<label>5</label>
<title>Conclusions</title>
<p>The natural variability of the Ocean Acidification on 24-hour and daily scales and during 56 days at El Muelle reef, Colombian Pacific, Gorgona Island, was assessed in a fixed station using high-resolution measurements of seawater pH<sub>T</sub>, salinity, and temperature taken every three hours during a year with a strong La Ni&#xf1;a event and extreme precipitation months. The prolonged 2020&#x2013;2023 La Ni&#xf1;a event amplified rainfall and freshwater discharges from the Guapi River, establishing a Type 2 RIOMar (river-marine) system dominated by high-energy tidal dynamics and intense river-sea mixing. This freshwater influx likely contributed to localized declines in seawater pH<sub>T</sub>. Concurrently, the southward migration of the ITCZ triggered persistent cloud cover and strong southwesterly winds, attenuating solar radiation and lowering both sea surface temperatures and pH<sub>T</sub>. Enhanced rainfall within the RIOMar system further diluted the surface layer, progressively reducing salinity and TA, thereby diminishing the system&#x2019;s buffering capacity against carbonate chemistry fluctuations. Biological processes such as photosynthesis and respiration shaped pronounced diurnal patterns within the 24-hour cycles, driving decreased and increased pH, pCO<sub>2w,</sub> and DIC. These results highlight the substantial and high-frequency variability of pH and acidification conditions formed by the heavy rainfall and runoff that characterize this Pacific Colombian region. Therefore, we strongly recommend implementing long-term monitoring programs (COCAS Ocean Decade Project) to support acidification impact studies and adaptive management and conservation efforts within this National Natural Park.</p>
</sec>
</body>
<back>
<sec id="s6" sec-type="data-availability">
<title>Data availability statement</title>
<p>The datasets generated for this study can be found in the NOAA - National Centers for Environmental Information (NCEI; Accession Number 0300707). <uri xlink:href="https://www.ncei.noaa.gov/data/oceans/ncei/ocads/metadata/0300707.html">https://www.ncei.noaa.gov/data/oceans/ncei/ocads/metadata/0300707.html</uri>).</p>
</sec>
<sec id="s7" sec-type="author-contributions">
<title>Author contributions</title>
<p>AM: Conceptualization, Investigation, Methodology, Supervision, Validation, Visualization, Writing &#x2013; original draft, Writing &#x2013; review &amp; editing, Data curation, Formal Analysis. AA: Conceptualization, Formal Analysis, Funding acquisition, Investigation, Methodology, Project administration, Resources, Supervision, Validation, Visualization, Writing &#x2013; original draft, Writing &#x2013; review &amp; editing. AG: Conceptualization, Investigation, Methodology, Writing &#x2013; review &amp; editing. AC: Formal Analysis, Investigation, Supervision, Validation, Visualization, Writing &#x2013; review &amp; editing. JH: Conceptualization, Formal Analysis, Supervision, Validation, Visualization, Writing &#x2013; review &amp; editing. SG: Investigation, Methodology, Validation, Visualization, Writing &#x2013; review &amp; editing. CC: Methodology, Validation, Writing &#x2013; review &amp; editing. DR: Conceptualization, Supervision, Validation, Visualization, Writing &#x2013; review &amp; editing.</p>
</sec>
<sec id="s8" sec-type="funding-information">
<title>Funding</title>
<p>The author(s) declare financial support was received for the research and/or publication of this article. The Principal Investigator (PI), AA, acknowledges receiving financial support for various research activities, including purchasing equipment, acquiring laboratory and field materials, and funding field trips. Additionally, these funds were used to establish and equip a laboratory at the Pontificia Universidad Javeriana. Partial resources from the same fund were also allocated to cover the publication costs of this article (ID 21346). The National Geographic Explorer program funded this research through the project titled <italic>&#x201c;Ocean Acidification Vulnerability in Colombia: First Monitoring Program in the Tropical Pacific&#x201d;</italic> (Grant No. NGS-64756R-19), with additional COVID-19 grant support (Grant No. NGS-81727R-20). The Pontificia Universidad Javeriana provided further funding under the project <italic>&#x201c;Monitoreo de acidificaci&#xf3;n marina en el Pac&#xed;fico colombiano&#x201d;</italic> (Project ID: 120132C0401200, No. 20019).</p>
</sec>
<ack>
<title>Acknowledgments</title>
<p>Dr. Cristian Vargas of the Laboratory of Aquatic Ecosystems Performance (LAFE) at the University of Concepci&#xf3;n (EULA Chile) supported getting the iSAMI-pH equipment. The Ocean Foundation donated the GOA-ON in a Box kit, OA training, and grant support for equipment maintenance under the Memorandum of Understanding between Pontificia Universidad Javeriana and The Ocean Foundation (&#x201c;TOF&#x201d;). Dra. Andrea Corredor-Acosta thanks FONDECYT Postdoctoral Project No. 3230740, granted by the Chilean Agency for Research and Development (ANID). This research is part of the collaboration with the International COCAS project (2021-2030), Ocean Decade-United Nations (Leader Diana Ruiz Pino and Alban Lazar) <ext-link ext-link-type="uri" xlink:href="https://oceandecade.org/fr/actions/coastal-observatory-for-climate-co2-and-acidification-for-theglobal-south-society-cocas/">https://oceandecade.org/fr/actions/coastal-observatory-for-climate-co2-and-acidification-for-theglobal-south-society-cocas/</ext-link>. We also thank Parques Nacionales Naturales de Colombia - Gorgona for their logistical support at Gorgona (Christian D&#xed;az &#x2013; research head &amp; Monitoring of the Gorgona park), accommodation, boat, and the research permit No. 004 de 2020 - file number: OTRP 004-2020. To Dra. Reggie Spaulding, James Beck, and Dr. Christopher Sabine for their technical support with the iSAMI-pH equipment. To Camilo, Freddy, and Jaime for their help in the Ocean Acidification laboratory. To Juan Felipe Cifuentes for his assistance deploying the iSAMI-pH at El Muelle Reef. Thanks to Dr. Alan Giraldo of Universidad del Valle for funding research interns Cristian Claros, Sebasti&#xe1;n Ortiz, and Natalia Londo&#xf1;o, who collaborated with us in the field sampling. We thank Camilo Rodr&#xed;guez and Enrique Herman for their help during the long days of boat sampling and for hosting us in their home during our stay at Guapi.</p>
</ack>
<sec id="s9" sec-type="COI-statement">
<title>Conflict of interest</title>
<p>The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.</p>
<p>The author(s) declared that they were an editorial board member of Frontiers, at the time of submission. This had no impact on the peer review process and the final decision.</p>
</sec>
<sec id="s10" sec-type="ai-statement">
<title>Generative AI statement</title>
<p>The author(s) declare that no Generative AI was used in the creation of this manuscript.</p>
</sec>
<sec id="s11" sec-type="disclaimer">
<title>Publisher&#x2019;s note</title>
<p>All claims expressed in this article are solely those of the authors and do not necessarily represent those of their affiliated organizations, or those of the publisher, the editors and the reviewers. Any product that may be evaluated in this article, or claim that may be made by its manufacturer, is not guaranteed or endorsed by the publisher.</p>
</sec>
<sec id="s12" sec-type="supplementary-material">
<title>Supplementary material</title>
<p>The Supplementary Material for this article can be found online at: <ext-link ext-link-type="uri" xlink:href="https://www.frontiersin.org/articles/10.3389/fmars.2025.1595871/full#supplementary-material">https://www.frontiersin.org/articles/10.3389/fmars.2025.1595871/full#supplementary-material</ext-link>
</p>
<supplementary-material xlink:href="DataSheet1.pdf" id="SM1" mimetype="application/pdf"/>
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