Posts Tagged 'methods'

Individual foraminiferal analysis: a promising tool for high-resolution temperature and pH reconstruction

Compared with traditional bulk foraminiferal analysis methods, in situ analysis of individual foraminiferal tests (individual foraminiferal analysis or IFA) offers several advantages over traditional bulk methods, including enhanced temporal resolution where fossiliferous sample material is limited as well as potentially resolving seasonal-scale climate variability in deep time. Despite these advantages, applications of element-to‑calcium (El/Ca) ratios and δ11B in benthic foraminifera using IFA remain limited, and the biogeochemical drivers of intra-test and inter-test geochemical variability are poorly constrained. In this study, we systematically evaluate El/Ca ratios and δ11B in individual benthic foraminifera. By analysing Holocene epifaunal benthic foraminiferal species Cibicidoides wuellerstorfi from a deep ocean core site (ODP Site 999), we conclude that intra- and inter-test variabilities are regulated by ontogenetic effects resulting in inter-test variabilities of ±0.14 mmol/mol Mg/Ca, ± 14 μmol/mol B/Ca, and ± 0.18 ‰ δ11B. Application of the IFA method to epifaunal benthic foraminifera species Cibicides lobatulus from a box core in the English Channel, UK reveals ~0.1 pH units acidification and ~ 1 °C warming since the mid-19th century. By demonstrating that individual-level variability in reconstructed temperature and pH tracks seasonal trends in the available contemporaneous water-column instrumental measurements at the same site, we provide a ground-truthing to our multi-proxy IFA methodology, and also demonstrate the potential for benthic IFA to provide seasonal-scale reconstructions of ocean climate over hundreds to millions of years.

Continue reading ‘Individual foraminiferal analysis: a promising tool for high-resolution temperature and pH reconstruction’

Experimental exposure to climate change scenarios imposed alterations on the morphological traits of sessile and low-motility marine invertebrates

Background

Over the past 50 years, the oceans have absorbed over 90% of global warming heat, leading to warming, acidification and declining oxygen levels that are disrupting marine ecosystems and altering species distributions and productivity. The vulnerability of marine organisms to these changes depends on their biological traits, habitat conditions and adaptive capacity, influencing their growth, behaviour and overall population health. Micro-computed tomography (micro-CT) has been previously used for studying the morphological traits of marine invertebrates, which provide important insights into species functionality and responses to climate change and ocean acidification. Micro-CT enables non-destructive, high-resolution 3D analysis of internal and external structures, allowing precise measurement of traits such as density, porosity and morphology that are valuable for climate change research.

New information

The present manuscript describes micro-CT imaging datasets generated to investigate the effects of climate change on the morphological structure of two benthic marine invertebrates: the low-motility gastropod Hexaplex trunculus (Linnaeus, 1758) and the sessile sponge Chondrilla nucula Schmidt, 1862. Both species are considered particularly vulnerable to environmental stressors. To date, no study has investigated the effects of ocean warming and acidification on sponges using micro-CT technology. Using a common garden experimental design, individuals from geographically distinct populations exposed to different natural environmental regimes were subjected to combined warming and acidification scenarios to assess their morphological responses and adaptive capacity.

Continue reading ‘Experimental exposure to climate change scenarios imposed alterations on the morphological traits of sessile and low-motility marine invertebrates’

Coulometric readout of ion-selective electrodes for an aquatic pH probe

Ion-selective electrodes are widely used for the detection of ions in aqueous solutions such as natural waters. Their origin traces back to 1909 with the invention of the pH glass electrode. Nowadays, routine pH measurements are still performed by potentiometric measurements with glass electrodes. The phase-boundary potential difference at the glass membrane-sample interface, measured against a reference electrode, relates to solution pH following the Nernst equation. While being user-friendly, they suffer from multiple drawbacks. Firstly, their sensitivity is intrinsically dictated by the Nernst equation and is limited to 59.2 mV/pH at 25 °C. This might not be sufficient for applications where high precision pH sensing is required, such as ocean acidification monitoring. Secondly, a Nernstian response can only be obtained if all the other potential differences in the overall electrochemical cell are constant over the whole experimental procedure. This is not the case when, for example, the temperature or the ionic strength of the sample change during the measurement routine. The former influences the glass electrode itself, while the latter rather affects the reference electrode via liquid junction potential variations.

This thesis presents enhancements to the potentiometric experimental setup for pH sensing with glass or polymeric membrane pH electrodes, achieved through the integration of electronic components, chemical symmetry and open liquid junctions. A dynamic electrochemical readout called constant potential coulometry is explored for in situ pH sensing in coastal waters by implementation in a submersible probe deployed in the Krka River estuary in April 2025.

Continue reading ‘Coulometric readout of ion-selective electrodes for an aquatic pH probe’

Ocean acidification at the crossroads I: harmonizing unpurified and purified meta-cresol purple spectrophotometric pHT measurements based on absorbance data

Consistent monitoring of seawater spectrophotometric pH on the total hydrogen ion scale (pHT) has been questioned by an evolving method, with changes in parameterization and the purity of the meta-cresol purple (mCP). Using real seawater samples, we demonstrate that spectrophotometric pHT measurements obtained with unpurified (UNPUR) and purified (PUR) mCP can be harmonized to within 0.003 pH units, the climate-goal threshold. This agreement is only achieved when mCP impurities at 434 nm are quantified for both the UNPUR and PUR mCP, assuming no impurities affect 545 nm absorbances, and impurity-corrected absorbance data at 434 nm are used in the same parameterization to calculate pHT. We applied this approach to a ship-based pHT time series transitioning from UNPUR to PUR mCP measurements. Our results show that previous claims suggesting that UNPUR mCP underestimates pHT in the upper pH range are misleading, as they were based on the inappropriate use of absorbances obtained with UNPUR mCP with a parameterization developed for PUR mCP. In fact, our data reveal better agreement between UNPUR and PUR pHT in the upper pH range of seawater, while UNPUR mCP tends to overestimate pHT in the lower pH range. These findings highlight the urgent need for the global chemical oceanography community to establish a spectrophotometric pHT method with full traceability to the International System of Units (SI), along with affordable and distributed certified reference materials and characterized purified mCP. This work supports the need for harmonization efforts to ensure the reliability of pHT data in global synthesis products.

Continue reading ‘Ocean acidification at the crossroads I: harmonizing unpurified and purified meta-cresol purple spectrophotometric pHT measurements based on absorbance data’

High vertical resolution measurements of pH, pCO2, total alkalinity, and dissolved inorganic carbon using a new approach: the carbonate profiler

The equilibrium between the different parameters of the marine carbonate system–dissolved inorganic carbon (DIC), total alkalinity (TA), partial pressure of CO2, and pH–is the core of ocean acidification studies, evaluation of inorganic carbon inventory, and air-sea CO2 fluxes. To date, it has been challenging to simultaneously measure all those components in the water column due to different sampling methodologies, and especially in stratified waters, where sharp vertical biogeochemical gradients may occur. In this study, we designed a low-cost and easy-to-assemble pumping system, which, combined with a CTD profiler, makes a PUMP-CTD system that can efficiently serve as a precise water column sampler, allowing for simultaneous measurements and sampling of dissolved inorganic carbon, total alkalinity, partial pressure of CO2, and pH with high vertical resolution. Importantly, this water sampler (denoted as the carbonate profiler) can be easily integrated with equilibrator-based continuous pCO2 measurement systems, which are routinely used for underway data acquisition, making them suitable for water column sampling as well. We tested the carbonate profiler in the open ocean water column, where we obtained excellent consistency between measured pCO2 and calculated values based on pH and DIC. Afterwards, we tested the operability of the system by measuring the vertical variability of all the components of the marine carbonate system in the Vistula River estuarine waters (southern Baltic Sea) and within the Arctic fjords affected by continental freshwater runoff. Overall, this system performed outstandingly, with a vertical resolution of half a meter, proving its utility in accurately measuring steep biogeochemical changes in the water column regardless of the analytical method used.

Continue reading ‘High vertical resolution measurements of pH, pCO2, total alkalinity, and dissolved inorganic carbon using a new approach: the carbonate profiler’

Neglecting organic alkalinity introduces greater error than assuming boron to salinity ratios in Arctic sea ice brine carbonate system calculations

While total alkalinity (AT) is traditionally attributed to dissolved inorganic constituents, dissolved organic matter (DOM) can significantly contribute to AT as organic alkalinity (OrgAlk), introducing errors in calculated carbonate parameters, such as the CaCO3 saturation state (Ω) and partial pressure of CO2 (pCO2). This study presents measurements of OrgAlk in the Arctic Ocean sea ice system and assesses its influence on carbonate speciation, with OrgAlk contributing 0.1–1.0% to AT. Sea ice brine exhibited elevated DOM and OrgAlk, with an OrgAlk/DOC ratio of 0.13 ± 0.06 µmol kg− 1 µM− 1, consistent with global ocean values. Correcting AT for OrgAlk increased computed pCO2 up to 84 µatm and decreased Ω ≤ 0.2 for aragonite and ≤ 0.3 for calcite compared to un-adjusted values. Elevated brine pCO2 suggests that conventional estimates of Arctic sea ice CO2 uptake may be overestimated when AT is used as an input parameter, particularly in spring as OrgAlk is released. The omission of OrgAlk contributed greater errors to calculated carbonate parameters than the differences in boron from using direct measurements versus salinity based ratios, highlighting the necessity of accounting for even minor OrgAlk to refine predictions of surface pCO2, net air-sea CO2 flux, and the fate of CaCO3 minerals.

Continue reading ‘Neglecting organic alkalinity introduces greater error than assuming boron to salinity ratios in Arctic sea ice brine carbonate system calculations’

A standardised experimental setup for simulating ocean warming and acidification in benthic marine invertebrates

Recent studies identify ocean warming and acidification as major drivers of ecological change in the Eastern Mediterranean, posing serious threats to marine biodiversity, particularly for sessile or low-mobility organisms that cannot escape unfavourable conditions. At the same time, the need for standardised experimental approaches capable of generating high-quality data on organismal responses to multiple climate stressors has become increasingly evident. This manuscript presents a fully detailed and replicable experimental framework for simulating ocean warming and acidification in benthic marine invertebrates under controlled laboratory conditions. Detailed protocols include the technical set-up, experimental design, selection of climate scenarios, monitoring procedures and criteria for species selection and demonstrating its application through a validation case study from the MACCIMO project.

Continue reading ‘A standardised experimental setup for simulating ocean warming and acidification in benthic marine invertebrates’

Metrological assessment of pHT in TRIS buffers within artificial seawater: implications for high-salinity reference materials

Anthropogenic CO2 emissions drive ocean acidification through changes in the carbonate system, lowering seawater pH. In contrast, salinity variations arise from physical processes such as freshwater fluxes and circulation. This study reports the preparation and Harned cell characterization of three equimolal TRIS buffer solutions (0.01 mol·kg−1, 0.025 mol·kg−1, and 0.04 mol·kg−1) in artificial seawater (ASW) matrices with practical salinities of 35 and 50 and temperatures of 20 °C, 25 °C, and 30 °C. Determined pHT values achieved expanded uncertainties (𝑈pHT ≤ 0.006), meeting Global Ocean Acidification Observing Network (GOA-ON) “climate” quality standards. Absolute salinity (SA) was concurrently measured via density (TEOS-10), revealing systematic deviations from practical salinity due to TRIS content. A nonlinear regression model was developed to predict pHT as a function of salinity, temperature, and TRIS molality, with r2 = 0.99998. These results provide a robust dataset for developing Certified Reference Materials (CRMs) for pHT calibration under climate-relevant high-salinity environments at different temperature conditions, offering a practical tool for high-accuracy calibration in variable marine conditions.

Continue reading ‘Metrological assessment of pHT in TRIS buffers within artificial seawater: implications for high-salinity reference materials’

Experimental exposure to climate change scenarios imposed alterations on the morphological traits of sessile and low-motility marine invertebrates

Over the past 50 years, the oceans have absorbed over 90% of global warming heat, leading to warming, acidification, and declining oxygen levels that are disrupting marine ecosystems and altering species distributions and productivity. The vulnerability of marine organisms to these changes depends on their biological traits, habitat conditions, and adaptive capacity, influencing their growth, behavior, and overall population health. Micro-computed tomography (micro-CT) has been previously used for studying the morphological traits of marine invertebrates, which provide important insights into species functionality and responses to climate change and ocean acidification. Micro-CT enables non-destructive, high-resolution 3D analysis of internal and external structures, allowing precise measurement of traits such as density, porosity, and morphology that are valuable for climate change research.

The present manuscript describes micro-CT imaging datasets generated to investigate the effects of climate change on the morphological structure of two low-motility benthic marine invertebrates: the gastropod Hexaplex trunculus and the sponge Chondrilla nucula. Both species are considered particularly vulnerable to environmental stressors. To date, no study has investigated the effects of ocean warming and acidification on sponges using micro-CT technology. Using a common garden experimental design, individuals from geographically distinct populations exposed to different natural environmental regimes were subjected to combined warming and acidification scenarios to assess their morphological responses and adaptive capacity.

Continue reading ‘Experimental exposure to climate change scenarios imposed alterations on the morphological traits of sessile and low-motility marine invertebrates’

Untargeted mass spectrometry to investigate ocean acidification in Cancer borealis using optimized metabolite extraction methods

Ocean acidification (OA) refers to the ongoing decline in ocean pH caused by the cascading effects of increased atmospheric CO2, which has significant negative impacts on various marine organisms, particularly crustaceans with calcified shells. However, research on the metabolic responses of crustaceans remains limited. In this study, we performed untargeted metabolomics on hemolymph samples from Cancer borealis (Jonah crab), a crustacean species well known for its tolerance to temperature and pH changes, to investigate its metabolic responses to OA. Two extraction methods—isopropanol (IPA) and acidified methanol (AcMeOH)—were employed to capture a broad range of metabolites and small peptides. Both methods enabled comprehensive detection; however, IPA yielded more consistent and extensive metabolite coverage, identifying 43 lipids compared to only 15 with AcMeOH. We identified 15 metabolites that responded significantly to OA. Several metabolites, including the potential neuropeptide cycloprolylglycine and the exogenous compound curcumin, exhibited concentration changes under OA exposure, suggesting their potential relevance in stress response pathways triggered by environmental stress. Overall, we highlight IPA as a more effective extraction method for untargeted metabolomics in crustacean hemolymph. Our study elucidates metabolic dynamics that enhance our understanding of the physiological adaptability of marine crustaceans under environmental stress and provides a comprehensive dataset that for future OA research.

Continue reading ‘Untargeted mass spectrometry to investigate ocean acidification in Cancer borealis using optimized metabolite extraction methods’

New ocean sensors could transform how scientists track the marine carbon cycle

The world’s oceans do far more than support vital marine ecosystems and provide food and recreation. They help regulate the Earth’s climate, absorbing vast amounts of heat and CO2, acting as one of the planet’s most important buffers against climate change.

Yet despite this vital role, scientists still struggle to track exactly how and where the ocean absorbs and stores CO2 – and how that process is changing.

Rintala is leading an international team that aims to extend ocean observing capacity by developing sensors for platforms that can operate beyond normal shipping routes and deep below the surface – far from ships and human intervention

At the heart of the effort is the development of the world’s first autonomous sensor capable of accurately measuring total alkalinity in the ocean – from the sea floor to the surface.

Total alkalinity is a key chemical indicator that scientists use to understand the ocean carbon system and estimate how much CO2 seawater can absorb and store.

It is also critical for tracking ocean acidification – a process driven by rising CO2 levels that lowers seawater pH and threatens marine ecosystems, particularly shell-building plankton and molluscs.

“Ocean acidification is very harmful for many marine organisms,” said Rintala. “It can cause cascading effects that ripple up the food web.”

Until now, total alkalinity has usually been measured by collecting fixed seawater samples from ships and analysing them later in onshore laboratories. That approach provides valuable data, but only at isolated points in time and space.

“If we are interested in the carbon content of the ocean as a whole, we need to measure deeper,” said ocean scientist Socratis Loucaides, based at the UK’s National Oceanography Centre (NOC).

Loucaides and his colleagues at NOC are leading the development of a radically different approach: a compact lab-on-a-chip sensor that performs a miniature chemistry experiment inside the instrument itself.

Inside the device, a small seawater sample is mixed with an acid of known strength and a dye that changes colour depending on acidity. A light-based sensor then reads those colour changes to calculate the alkalinity of the surrounding seawater.

By doing this directly in the deep ocean, the sensor can build up a far more detailed picture of how carbon is stored and transported over time – and potentially reveal early warning signs of change.

Continue reading ‘New ocean sensors could transform how scientists track the marine carbon cycle’

Y/Ho ratios in marine sediments unveil Neoproterozoic ocean acidification

Understanding Precambrian seawater pH is critical for unraveling Earth’s early marine environments and biospheric evolution. Yet, quantitative constraints remain elusive due to the lack of robust proxies. Here, we demonstrate that yttrium/holmium (Y/Ho) fractionation during adsorption onto marine sediments serves as a novel and reliable pH proxy. Experimental results reveal that Y/Ho fractionation in ferruginous sediments follows a pH-dependent power-law relationship, while in argillaceous sediments, it is jointly controlled by pH and salinity at low salinities (< 29‰) but stabilizes (KdY/Ho ≈ 0.4) at higher salinities (≥ 29‰). Temperature exerts a negligible influence, ensuring broad applicability across geological timescales. Leveraging these relationships, we develop a quantitative method to reconstruct paleo-seawater pH using Y/Ho ratios from coexisting ferruginous and argillaceous sediments. Validation against modern and Phanerozoic records confirms the proxy’s accuracy (e.g., pH 8.21 ± 0.22 for modern Pacific sediments). Application to Neoproterozoic meta-pelites and iron formations reveals prolonged oceanic acidification (pH 5.9–6.4), deviating from previous model-based neutral-to-alkaline estimates. This acidic state, likely sustained by CO2 outgassing from carbonatite-alkaline volcanism during Rodinia’s breakup, challenges conventional views of Precambrian ocean chemistry. Our findings provide a transformative tool for probing early Earth’s environmental dynamics and highlight the interplay between tectonics, magmatism, and marine pH evolution.

Continue reading ‘Y/Ho ratios in marine sediments unveil Neoproterozoic ocean acidification’

An experimental approach to study climate change stress in benthic marine invertebrates

Climate change is altering ocean temperature and chemistry, with ocean warming and acidification posing serious threats to marine biodiversity, particularly for sessile or low-mobility organisms that cannot escape unfavorable conditions. The MACCIMO project investigated the effects of these stressors on the sponge Chondrilla nucula and the gastropod Hexaplex trunculus using an integrative approach that examined molecular, physiological, morphological, and symbiotic responses. By applying a common garden experiment to populations from different Mediterranean regions, the study aimed to distinguish genetic and environmental influences on stress tolerance and assess intraspecific variability. Three experimental scenarios were simulated, including a control treatment and two climate change treatments based on the “high GHG emissions” RCP 8.5 scenario. A semi-enclosed experimental system with precise control of temperature and pH was designed which can be easily replicated to support laboratory studies on the effects of climate change and ocean acidification on small marine invertebrates across multiple biological levels.

Continue reading ‘An experimental approach to study climate change stress in benthic marine invertebrates’

Detecting the acidity of the ocean with sound, the role of lead in human evolution, and how the universe ends (podcast)

First up on the podcast, increased carbon dioxide emissions sink more acidity into the ocean, but checking pH all over the world, up and down the water column, is incredibly challenging. Staff Writer Paul Voosen joins host Sarah Crespi to discuss a technique that takes advantage of how sound moves through the water to detect ocean acidification.

This week’s episode was produced with help from Podigy.

Continue reading ‘Detecting the acidity of the ocean with sound, the role of lead in human evolution, and how the universe ends (podcast)’

The internal consistency between calculated and measured variables of the marine carbonate system in Arctic open and coastal waters, case study: Atlantic Arctic

Highlights

  • Good consistency between calculated and measured variables of the marine carbonate system in Oceanic waters.
  • Only pH and pCO2 can be calculated with good accuracy in coastal waters.
  • The nutrient data are not required to calculate accurate marine carbonate system data in this region.
  • Total Alkalinity and pH (or pCO2) can be used to obtain good quality pCO2 (or pH) data.

Abstract

The Arctic Ocean plays a crucial role in anthropogenic carbon sequestration, while also being among the regions most susceptible to Ocean Acidification (OA). To understand, quantify, and monitor the rapid biogeochemical changes in the Arctic shelves and coastal waters, it is necessary to accurately determine the complete marine carbonate system. However, the uncertainty range in the calculated values is still unclear, fogging our ability to properly estimate carbon inventory and OA. In this study, we collected samples in the Arctic open and coastal waters to estimate the internal consistency of total alkalinity (TA), pH, partial pressure of CO2 (pCO2) and dissolved inorganic carbon (DIC) when only two of them are measured and the other two calculated. In open ocean waters, calculated values generally show good consistency with observations, whereas in coastal areas, it was only possible to accurately calculate two variables: 1) pH using as input parameters pCO2 together with either TA or DIC, and 2) pCO2 using DIC and pH. Furthermore, we found that, in this dataset, using the TA estimated from its correlation with salinity together with pCO2 also allowed obtaining accurate pH values in both coastal and ocean waters. This opens a new possibility of monitoring changes in the carbon cycle by measuring only salinity and pCO2 in areas where its consistency has been evaluated. Finally, in this study, we provide guidelines for obtaining and reporting good-quality carbonate system data in Arctic coastal areas.

Continue reading ‘The internal consistency between calculated and measured variables of the marine carbonate system in Arctic open and coastal waters, case study: Atlantic Arctic’

Metrological concepts applied to Total Alkalinity measurements in seawater: reference materials, inter-laboratory comparison and uncertainty budget

Total alkalinity (TA) measurements in seawater are crucial for characterizing and monitoring the oceanic carbonate system. While international best practices and guidelines exist, the field still lacks widely available traceable reference materials and a well-established uncertainty budget of the measurement method. In this study, we applied key metrological principles – development of reference materials, inter-laboratory comparison and uncertainty quantification – to TA measurements. We developed two reference materials, including an artificial material with a rigorously characterized reference value and an associated uncertainty budget, being traceable to the International System of units (SI). These materials were tested in an inter-laboratory comparison involving five laboratories and demonstrated the applicability of the reference materials developed for quality control. Additionally, we established an uncertainty budget for the TA measurement method using two metrological approaches. The resulting expanded uncertainty was 5 µmol kg−1 (with a coverage factor k=2) in TA, approaching the 4 µmol kg−1 target set by the Global Ocean Acidification Observing Network for climate monitoring. These findings mark a significant step toward improving the quality and comparability of TA measurements, thereby strengthening long-term ocean carbonate system monitoring.

Continue reading ‘Metrological concepts applied to Total Alkalinity measurements in seawater: reference materials, inter-laboratory comparison and uncertainty budget’

An indoor mesocosm system for cost-effective simulation of multiple ocean stressors affecting marine organisms

Global climate change is exacerbating multiple ocean stressors, including ocean acidification (OA), ocean warming (OW), and deoxygenation (deOxy), which collectively threaten marine ecosystems and fisheries. Understanding how these stressors interact to shape organismal and ecosystem responses is increasingly critical, yet it remains technically challenging and expensive to simulate them concurrently under controlled indoor conditions. To address this limitation, we developed a closed indoor mesocosm system that enables stable and long-term simulation of these three stressors for biological and aquaculture research. The system maintains consistent levels of CO2, temperature, and dissolved oxygen (DO) over multi-month experiments without automated control units, relying instead on robust initial settings. High-purity CO2 and N2 gases are blended with ambient air in controlled ratios to regulate carbonate chemistry and oxygen levels, while chillers and heaters ensure precise temperature control. Validation experiments demonstrated that the system can (1) increase pCO2 to approximately twice the present-day level with a pH reduction of ~ 0.22 units, (2) elevate temperature by + 3 °C above ambient temperature, and (3) reduce DO by up to 40% relative to ambient concentration, reflecting projected climate scenarios. This simple and versatile mesocosm provides a practical platform for investigating the ecophysiological responses of marine organisms under multi-stressor environments, supporting research on climate adaptation and aquaculture resilience.

Continue reading ‘An indoor mesocosm system for cost-effective simulation of multiple ocean stressors affecting marine organisms’

Ventilation and buffering capacity effects on ocean acidification in low oxygen environments

Ocean acidification results from oceanic uptake of anthropogenic CO2 (ΔCant). Weak carbonate buffering capacity (high Revelle factor, RF) amplifies acidification, but its role in persistently low-oxygen, poorly ventilated regions is unclear. Here we compare preindustrial to present changes in partial pressure of CO2 (pCO2), hydrogen ion concentration ([H+]), pH, aragonite saturation state (Ωara), and RF within permanent oxygen minimum zones (OMZs) versus well-ventilated regions. We find that acidification is negligible in the least-ventilated, poorly buffered lower OMZs, but detectable in moderately ventilated upper OMZs. In upper OMZs, pCO2 and [H+] increase faster while Ωara, pH, and RF change more slowly than in adjacent well-ventilated regions. Our analysis reveals that limited ΔCant delivery by ventilation ultimately constrain acidification in low-oxygen regions. Accordingly, low-oxygen regions with poor ventilation will experience less acidification than well-ventilated regions, and different metrics (notably [H+] versus Ωara) respond distinctly due to their different definitions and sensitivities.

Continue reading ‘Ventilation and buffering capacity effects on ocean acidification in low oxygen environments’

An autonomous pH sensor for real-time high-frequency monitoring of ocean acidification in estuarine and coastal areas

In situ pH sensing is crucial for the real-time monitoring of ocean acidification and investigations into the marine carbon cycle. Although ion sensitive field-effect transistor (ISFET) has been proven suitable for marine pH monitoring, its supply and implementation remain challenging. An underwater pH sensor for environmental analysis (uSEA-pH) based on ISFET was developed herein, incorporating a modified commercial laboratory pH probe through engineering design. Laboratory characterization demonstrated that uSEA-pH exhibited a Nernstian response (slope −57.60 ± 1.05 mV/pH, R2 > 0.999), rapid response time (∼7 s), and low measurement uncertainty (<0.01 pH). The sensor supports a sampling frequency of 1 Hz with an average power consumption of only 0.72 W. Its compact design (self-contained with battery: Φ15 × 45 cm; miniaturized version: Φ6.4 × 21 cm) facilitates deployment on various observational platforms. During high-frequency underway monitoring in the Pearl River Estuary and Dongshan Bay, uSEA-pH successfully detected subtle pH variations (<0.05 pH). In extended in situ deployments, buoy-mounted uSEA-pH reliably recorded tidal-driven pH fluctuations in Dapeng Bay (27 days) and Xiamen Bay (7 days), generating over 2.3 million field measurements. This study presents a viable, robust, and high-resolution approach for continuous pH monitoring in estuarine and coastal areas.

Continue reading ‘An autonomous pH sensor for real-time high-frequency monitoring of ocean acidification in estuarine and coastal areas’

Symmetrical pH electrochemical cell coupled to constant potential coulometry for improved sensitivity and precision: part 2. Submersible probe for in situ measurements

Seawater pH is a critical parameter influencing many processes in the ocean. Today it is mainly measured by indicator- based spectrophotometry to allow for high precision. This, however, is at the expense of traceability and systematic errors originating from changes in temperature, salinity and other matrix effects. Moreover, in routine practice this approach is not performed in situ and requires sampling and manual manipulations, which is prone to introduce additional errors including gas exchange with the atmosphere. Unfortunately, in the last few decades the electrochemical sensing community has failed to make efforts to improve the performance of the gold standard method, which is potentiometric detection with pH glass electrodes. To address this, we aim here to improve the sensitivity and precision of submersible pH probes on the basis of pH glass electrodes by minimizing systematic errors from temperature changes and by implementing a recently described coulometric method. The electrodes are mounted in a symmet- rical cell reported in part 1 of this work to reduce sensor drift and minimize inaccuracies due to liquid junction potential variations and pH changes of the inner solution from temperature fluctuations. The development and construction of the probe is explained. The circuit is evaluated and the sensors are calibrated over a range of temperatures, approaching ideal behavior. The submersible probe was deployed in situ in April 2025 in the vertically stratified Krka River Estuary in Croatia. The precision of the probe were evaluated in situ by stability experiments in the seawater layer. The determined precision is 0.001 pH unit, which is significantly better than reported earlier for routine pH probes. A recalibration procedure with synthetic seawater is also evaluated for minimizing drift. A depth profile with changing salinity was performed and compared with CTD probes.

Continue reading ‘Symmetrical pH electrochemical cell coupled to constant potential coulometry for improved sensitivity and precision: part 2. Submersible probe for in situ measurements’

Subscribe

Search

  • Reset

OA-ICC Highlights

Resources