Posts Tagged 'chemistry'



Seawater pH fluctuations during the Ordovician to Silurian transition: insights from δ11B records in carbonates

Highlights

  • A positive δ11Bcarb excursion has been observed during the Hirnantian coinciding with Gondwana glaciation.
  • Seawater pH fluctuations during the OST are caused by declining atmospheric pCO₂, sea level fall and carbonate weathering.
  • The fluctuation of seawater pH exerted a crucial role in the climatic changes and biotic evolutions during the OST.

Abstract

Environmental changes during the Ordovician to Silurian transition (OST) and the cause of Late Ordovician Mass Extinctions (LOMEs) remain a subject of debate. This study presents the first continuous seawater pH record spanning the Late Ordovician and Early Silurian, based on carbonate boron isotope (δ11Bcarb) data obtained from a carbonate-dominated section in South China. Our results reveal predominantly stable δ11Bcarb values throughout the Late Ordovician and Early Silurian, punctuated by a positive δ11Bcarb excursion during the Hirnantian coinciding with Gondwana glaciation. The calculated seawater pH pattern indicates a generally low pH baseline across the OST, temporarily interrupted by a transient increase in surface ocean pH coinciding with the glacial episode. These pH fluctuations are interpreted to result from a combination of factors, including declining atmospheric pCO₂ levels, sea level changes, weathering of carbonate rocks, and decomposition of organic matter. This study suggests that the fluctuation of seawater pH exerted a crucial role in the climatic changes and biotic evolution during the OST. The enhanced carbonate weathering and increased seawater pH, together with sea level fall and a reduction in shelf area, likely contributed to the decreased net accumulation of carbonates and represented a negative feedback for the development of glaciation and cooling climate. Given that the living of organisms (e.g. brachiopod, conodont, sponge and radiolarian) was sensitive to the changes in seawater pH, if and how the seawater pH fluctuations affected the LOMEs still needs more detailed work in the future.

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Understanding the resilient carbon cycle response to the 2014–2015 Blob event in the Gulf of Alaska using a regional ocean biogeochemical model

Marine heatwaves (MHWs), characterized by anomalously high sea surface temperatures, are occurring with increasing frequency and intensity, profoundly impacting ocean circulation, biogeochemistry, and marine ecosystems. The MHW known as the Blob, which persisted in the subarctic NE Pacific from 2014 to 2015, significantly affected surrounding ecosystems. Warming-induced solubility reduction is expected to raise the partial pressure of carbon dioxide (pCO2) in the surface water, causing outgassing of CO2 to the atmosphere. Outgassing of CO2 is another source of atmospheric CO2 in addition to anthropogenic fossil fuel burning. However, moored observations at Ocean Station Papa (OSP; 145° W, 50° N) shows a moderate decrease in oceanic pCO2 during the Blob, resisting the warming-induced outgassing of CO2. This response is opposite of what is expected from warming alone, and instead has been attributed to reductions in dissolved inorganic carbon (DIC), although the mechanisms driving this reduction have remained unclear. We employed a regional model that accurately reproduces the temporal variability of oceanic pCO2 at OSP to investigate the cause of decrease pCO2 during the Blob. The analysis of model outputs indicates that the observed oceanic pCO2 decline resulted from the offset between warming-induced solubility reduction (increasing pCO2) and weakened physical transport of DIC (decreasing pCO2), with the latter dominating. Both horizontal and vertical transports played important roles. The near-surface carbon budget over the broad region was primarily driven by changes in the vertical transport. The decrease in DIC during the Blob resulted from the suppression of upwelling of DIC-rich subsurface waters in the winter of 2013. In this period, the horizontal transport also contributed substantially to DIC reduction. In particular, at OSP, the effect of the horizontal transport was comparable to that of the vertical transport, reflecting the northward advection of low-DIC water masses. These findings indicate that changes in physical circulation were the primary driver of the moderately enhanced CO2 uptake observed during the Blob. This study provides a critical insight into the complexity of biogeochemical response to extreme warming events and underscores the importance of resolving physical transport processes in assessing oceanic carbon uptake during MHWs.

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Wind control of the interannual ocean‐biogeochemical variability in the South Atlantic Bight

Abstract

In the South Atlantic Bight (SAB), changes in the Gulf Stream (GS), particularly its strength and proximity to the coast, are thought to be primary factors determining the shelf-break upwelling rate. However, it is still not entirely clear if and to what extent those factors influence cross-shelf nutrient fluxes and shape the ocean biogeochemistry at interannual and longer timescales. Here, we use a high-resolution regional ocean-biogeochemical model and an ocean reanalysis product (1993–2022), along with a satellite-derived chlorophyll data set (1997–2022), to investigate the interannual ocean-biogeochemical variability in the SAB. Regional model outputs suggest that year-to-year changes in phytoplankton production are indeed largely driven by upwelling of cold and nutrient-rich water to the shelf-break. The upwelling variability, reflected in bottom temperature and vertically integrated production patterns, is strongly linked to surface velocity changes in the GS near the shelf break, but weakly related to the depth-integrated GS transport. The GS’s velocity changes, and the temperature and production anomalies, are well correlated to the alongshore wind stress, suggesting that local wind is the leading driver of the shelf-break upwelling variability at interannual timescales. Those relationships are also supported by circulation patterns from ocean reanalysis and satellite chlorophyll anomalies. Finally, examining the simulated shelf-slope interchanges in the carbonate system, we find that shelf-break upwelling significantly increases bottom acidification, a pattern linked to the low carbonate concentration in the slope waters. This study thus provides new insight for understanding and predicting GS and winds impacts on biogeochemical patterns from the SAB.

Plain Language Summary

The ocean current known as the Gulf Stream (GS) can induce upwelling of subsurface cold and nutrient-rich waters into the coastal margin of the South Atlantic Bight, influencing coastal temperature and phytoplankton growth. Previous studies suggested that the GS strength and its proximity to the coast are key factors determining the intensity of upwelling events. However, the degree to which these factors impact the year-to-year changes in phytoplankton production and other ocean properties remains unclear. Here we use numerical models of ocean currents and seawater biogeochemistry, as well as chlorophyll records derived from satellite measurements, to investigate that impact. The patterns showed that interannual changes in coastal temperature, phytoplankton production, water acidity, and dissolved oxygen are strongly modulated by upwelling changes in the outer edge of the continental margin (about 70 m depth in this region). This interannual upwelling variability is tightly coupled to variations in the surface alongshore GS velocity close to that outer edge, which is modulated by alongshore wind variability. Our study characterizes GS patterns associated with high and low productivity years, and highlights the role of surface wind as ultimate driver of the interannual upwelling variability in the South Atlantic Bight.

Key Points

  • A regional ocean model is used to investigate interannual variability of ocean-biogeochemistry in the South Atlantic Bight
  • Year-to-year changes in primary production, chlorophyll, and carbonate system patterns respond to shelf-break upwelling anomalies
  • Shelf-break upwelling is closely linked to the Gulf Stream velocity near the shelf break, modulated by alongshore wind variability
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Ocean acidification in Canada: the current state of knowledge and pathways for action

Ocean acidification (OA) generally receives far less consideration than other climate stressors and related hazards, such as global warming and extreme weather events. Canada is uniquely vulnerable to OA given its extensive coastal oceans, the oceanographic processes in its three basins, accelerated warming and sea-ice melt, and extensive coastal communities and maritime economic sectors. Canada’s coastline is also home to extensive and diverse First Nations peoples with distinct histories, rights, title, laws, governance and whose traditions and cultures are extrinsically linked to the sea. However, there are currently very limited pathways to support OA action, mitigation, and/or adaptation in Canada, particularly at the policy level. Here, we present a first synthesis of the current state of OA knowledge across Canada’s Pacific, Arctic, and Atlantic regions, including monitoring, modelling, biological responses, socioeconomic and policy perspectives, and examples of existing OA actions and efforts at local and provincial levels. We also suggest a step-wise pathway for actions to enhance the coordinated filling of OA knowledge gaps and integration of OA knowledge into decision-making frameworks. The goals of these recommendations are to improve our ability to respond to OA in Canada, and minimize risks to coastal marine environments and ecosystems, vulnerable sectors, and communities.

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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.

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A biogeochemical perspective on acidification and buffering capacity in the Piscataqua Estuary

Coastal acidification is influenced not only by rising atmospheric CO2 and river-ocean mixing, but also by metabolic processes that alter seawater carbonate chemistry and buffering capacity. This study examines how sedimentary biogeochemical processes contribute to carbonate system variability in the Piscataqua Estuary, a tidally dynamic channel connecting Great Bay to the Gulf of Maine. The biogeochemical processes considered include sedimentary aerobic respiration, denitrification, sulfate reduction, and carbonate dissolution or precipitation. Two incubation experiments were conducted in September and October of 2024 at the University of New Hampshire’s Coastal Marine Laboratory (CML) to quantify changes in pH, dissolved inorganic carbon (DIC), and total alkalinity (TA) in the overlying water arising from sediment-water biogeochemical exchange. Sediment cores were collected to be paired with overlying water from slack low and slack high tides during each month. Across both experiments, sediment cores consistently exhibited greater acidification and larger shifts in DIC and TA concentrations compared to water-only cores, indicating strong sedimentary biogeochemical influence. Among the processes considered, sulfate reduction is likely the most influential driver of carbonate system variability, contributing to increases in both DIC and TA. Linking experimental results to in-situ measurements at CML revealed that variability observed over individual ebb or flood tides primarily reflected processes associated with tidal advection (ie, river-ocean mixing and water-column biogeochemical activity). However, when evaluating net changes over both tidal transitions (ebb and flood), contributions from sedimentary biogeochemical processes were comparable in magnitude to those of the other processes during September and October. Sedimentary biogeochemical processes also appear to exert more consistent contributions to DIC and TA than water-column biogeochemical processes. Together, these findings demonstrate that sedimentary biogeochemical processes play a major role in regulating carbonate system variability in the Piscataqua Estuary. This study underscores the importance of examining carbonate system variability across multiple timescales to obtain a more comprehensive understanding of estuarine carbonate dynamics. Additional experimental work is needed to further resolve the influence of metabolic processes on coastal carbonate systems under changing environmental conditions.

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Shrinking shellfish? Risk of acidic water in the Indian River Lagoon

Researchers, Boat

FAU researchers measured aragonite saturation – a key indicator of water’s ability to support calcifying organisms like clams and oysters – throughout the Indian River Lagoon.

Florida’s Indian River Lagoon (IRL), one of the state’s most ecologically productive estuaries, is facing a growing but invisible threat that could reshape its marine ecosystems. Over the past decade, the lagoon has suffered severe degradation caused by nutrient pollution, excessive freshwater runoff, harmful algal blooms (HABs), and declining water quality. These changes have led to the loss of tens of thousands of acres of seagrass and have negatively impacted shellfish, fish, dolphins, manatees and other key species.

A new study from Florida Atlantic University’s Harbor Branch Oceanographic Institute now reveals that these pressures are also contributing to coastal acidification, a chemical shift in the water that threatens the ability of shell-building marine organisms to grow and thrive. 

To understand these changes, FAU Harbor Branch researchers studied the IRL from 2016 to 2017, measuring Ωarag and other water chemistry factors. They examined how nutrients, freshwater inputs, and other environmental conditions affect the lagoon’s ability to support shell-building marine life.

The study used two approaches. First, researchers conducted a broad survey across the lagoon, from nutrient-rich northern areas to southern regions affected by freshwater inflows. Second, they did weekly sampling at three central sites with different salinity and land-use conditions: an urban-influenced canal, a river mouth affected by urban and agricultural runoff, and a relatively natural reference site with strong ocean exchange.

Results of the study, published in the journal Marine Pollution Bulletin, revealed clear patterns. Northern sites with high nutrient concentrations and frequent HABs had lower aragonite saturation. Southern sites, influenced by freshwater discharges, also had lower Ωarag, primarily due to reduced salinity and dilution of aragonite. In the weekly surveys, Ωarag was positively correlated with salinity and negatively correlated with nutrient levels, confirming that both freshwater input and nutrient pollution play a role in controlling water chemistry.

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Linking surface pCO2 variability to physical processes along a continental shelf–ocean transect in the southwestern Atlantic Ocean during austral autumn and winter

The southwestern South Atlantic Ocean is an important global sink of atmospheric carbon dioxide (CO2), driven by increased primary productivity in a nearby region where oligotrophic warm currents converge with nutrient-rich cold waters. However, uncertainties remain regarding CO2 dynamics and the role of physical processes in CO2 uptake across this region. Here, we assess variations in surface partial pressure of CO2 (pCO2) and air–sea CO2 fluxes in the Southwest Atlantic, along a transect from the continental shelf to the open ocean at 34.5°S during austral autumn 2018 and winter 2019. High-resolution spatial measurements of the temperature, salinity, and molar fraction of surface CO2 were conducted. In autumn 2018, the shelf region acted as a source of CO2 to the atmosphere (median of 3.2 mmol CO2 m-2 d-1), which was partially offset by a sink (median of –2.5 mmol CO2 m-2 d-1) in the open ocean. In contrast, the entire transect in winter 2019 presented median CO2 emissions of ~1.5 mmol CO2 m-2 d-1, which differs from climatological estimates. The spatial and seasonal variations in surface ocean pCO2 were linked to variable hydrodynamic processes, including water masses and mesoscale structures. Our findings reveal that, in one of the most productive oceanic waters worldwide, pCO2 may be influenced by distinct continental inputs (e.g., rivers, runoff, and groundwater discharge) and water masses (e.g., Tropical Water, Plata Plume Water and Subtropical Shelf Water). Therefore, the local hydrodynamic processes can modulate high spatial and seasonal variability in CO2 exchange at the ocean–atmosphere interface, with potential implications for regional and global carbon budgets. General results, such as climatological, cannot fully capture the influence of regional upwelling and continental water input, which highlights the importance of high-resolution regional observations.

Continue reading ‘Linking surface pCO2 variability to physical processes along a continental shelf–ocean transect in the southwestern Atlantic Ocean during austral autumn and winter’

Seasonal air-sea CO2 flux dynamics in Colombia’s Gorgona Marine Area during La Niña 2021–2022

Air–sea CO₂ fluxes in tropical coastal zones are strongly influenced by ENSO variability, but in situ measurements in the Eastern Tropical Pacific remain scarce. We assessed seasonal CO₂ dynamics around Gorgona Island (Panama Bight, Colombian Pacific) under La Niña 2021–2022. From November 2021 to July 2022, we conducted monthly sampling at seven stations spanning the Guapi River plume to the open ocean, measuring physical (SST, SSS, thermocline depth), chemical (TA, DIC, pH, carbonate system parameters), and biological (chlorophyll-a) variables, and estimating net CO₂ fluxes (FCO₂) with the Liss and Merlivat (1986) parameterization and atmospheric CO₂ from NOAA. La Niña featured a cool-water anomaly (−0.78 °C), enhanced precipitation (+59%) and river discharge (+44%) relative to multi-year means. The nine-month mean CO₂ flux was near neutral (−0.01049 ± 0.00014 mol C m⁻²) but strongly seasonal: six post-upwelling months showed slightly positive fluxes (0.00929 ± 0.000147 mol C m⁻²) associated with high precipitation (746.4 ± 214.7 mm), warmer SST (27.5 ± 0.4 °C), elevated pCO₂w (567 ± 97.5 µatm) and lower pH (7.869 ± 0.040), whereas three upwelling months showed slightly negative fluxes (−0.00119 ± 0.00010 mol C m⁻²) with reduced precipitation (165.8 ± 82.4 mm), cooler SST (26.5 ± 0.2 °C), lower pCO₂w (461 ± 92.8 µatm) and higher pH (7.968 ± 0.048). La Niña amplified pCO₂w variability (316–839 µatm) via vertical Ekman pumping, horizontal transport (Zonal Ekman Transport, tides), and freshwater inputs, while a persistent thermocline (10–40.1 m) restricted deep CO₂-rich waters from reaching the surface. Biological uptake further modulated outgassing, as evidenced by chlorophyll-a and ΔDIC dynamics. Overall, CO₂ fluxes were relatively low compared with other tropical estuarine and oceanic sources. These results underscore the need for sustained in situ observations in estuarine–ocean systems to refine predictive models of CO₂ fluxes under ENSO conditions.

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Seaweeds (Ulva, Gracilaria) significantly increase the growth rates of North Atlantic oysters, scallops, and clams grown in an aquaculture setting

Highlights

  • Seaweeds significantly increased the growth rates of oysters by 20–70%, of clams by 60–70%, and of scallops by 130–140%.
  • Seaweeds caused significant increases in pH, DO, and the saturation state of calcium carbonate (Ω).
  • Seaweeds caused a significant increase in the concentrations of suspended chlorophyll a.
  • Co-culture of seaweeds with bivalves accelerates the growth rate of bivalves by increasing pH, DO, Ω, and food availability.

Abstract

While bivalve populations are threatened by climate change stressors including ocean acidification and hypoxia, the photosynthetic activity of seaweeds can raise the pH and dissolved oxygen (DO) of seawater, combatting these stressors. Here, three commercially important North Atlantic bivalves (Eastern oysters, Crassostrea virginica; hard clams, Mercenaria mercenaria; bay scallops, Argopecten irradians) were grown in the presence and absence of two common seaweeds (Ulva sp. and Gracilaria sp.) in replicated 300 L outdoor aquaculture tables with flow-through seawater. Environmental conditions including pH, DO, and chlorophyll a were continuously monitored and levels of dissolved inorganic carbon and the complete carbonate chemistry of seawater were quantified. The presence of seaweeds significantly increased shell- and tissue-based growth rates of oysters by 20–70%, of clams by 60–70%, and of scallops by 130–140% (p < 0.05) with both seaweeds being similarly effective. Both seaweed species caused significant increases in pH, DO, and the saturation state of calcium carbonate (Ω) during the day (p < 0.05) whereas differences at night were muted with night-time Ωaragonite levels being at or below saturation in all treatments. In some experiments, the presence of seaweeds caused a significant increase in the concentrations of suspended chlorophyll a, suggesting that seaweeds increased the total amount and diversity of food available to bivalves. Collectively, this study demonstrates that the co-culture of seaweeds with bivalves in a land-based aquaculture setting can significantly accelerate the growth rate of bivalves by increasing pH, DO, Ω, and food availability.

Continue reading ‘Seaweeds (Ulva, Gracilaria) significantly increase the growth rates of North Atlantic oysters, scallops, and clams grown in an aquaculture setting’

Summary of ocean acidification data collected by the National Coral Reef Monitoring Program in the U.S. Pacific Islands, 2021—2023

Coral reefs are among the most biologically diverse and economically valuable ecosystems on earth. They provide billions of dollars annually in food, jobs, recreation, coastal protection, and other critical ecosystem services (Brander & van Beukering, 2013; Costanza et al., 2014). However, these ecosystems are also among the most vulnerable to ocean acidification (OA). Even under the most optimistic model projections, increasing atmospheric and seawater carbon dioxide concentrations are likely to occur over the next few decades, decreasing seawater pH and reducing the availability of the carbonate ion (CO32-) building blocks that corals and other marine calcifiers use to construct reef habitat (Chan & Connolly, 2013; Jiang et al., 2023). OA threatens the persistence of coral reefs by reducing rates of coral and crustose coralline algae (CCA) calcification and accelerating rates of bioerosion, thereby lowering net production of calcium carbonate (CaCO3) and compromising the structural complexity and integrity of three-dimensional reef habitat (Cornwall et al., 2021; Hill & Hoogenboom, 2022). As a result, many of the ecological, economic, and cultural values offered by coral reefs could be significantly impacted by OA over the next century.

NOAA’s National Coral Reef Monitoring Program (NCRMP) provides a framework for long-term, national-level monitoring of the U.S.-affiliated coral reef areas. Funded jointly by the NOAA Coral Reef Conservation Program and Ocean Acidification Program, NCRMP assesses the status and trends of U.S. coral reef ecosystems and supports the management of the nation’s reefs (NOAA Coral Program, 2021). NCRMP’s long-term monitoring of OA and related coral reef ecosystem responses (NCRMP-OA) evaluates patterns and trends in carbonate chemistry and key ecosystem indicators across gradients of biogeography, oceanographic conditions, habitat types, and human impacts. These data sets are used to inform the efficacy of place-based coral reef management in close collaboration with federal, state, and jurisdictional partners.

To assess the progression of OA and impacts on coral reef ecosystems in the U.S. Pacific Islands, NCRMP-OA monitoring includes the following objectives:

  • Conduct carbonate chemistry sampling to monitor spatial variability and temporal change in pH, aragonite saturation state (Ωar), and other carbon system parameters;
  • Conduct diel carbonate chemistry water sampling and oceanographic instrument deployments at select sites;
  • Conduct census-based carbonate budget assessments to estimate rates of coral reef biological carbonate production and erosion.

This report summarizes the monitoring effort and results from 2021–2023 NCRMP-OA sampling and surveys. Additional NCRMP environmental, benthic, and fish data are not included in this report, but they can be accessed at the links provided in the Data Availability section.

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Microbial community dynamics over large spatial and environmental gradients in a subtropical ocean basin

Microbes are fundamental to ocean ecosystem function, yet they remain understudied across broad spatial and environmental scales in dynamic regions like the Gulf of America/Gulf of Mexico (GOM). We employed DNA metabarcoding to characterize prokaryotes (16S V4–V5) and protists (18S V9) across 51 stations, spanning 16 inshore–offshore transects and three depths. Cluster analysis revealed three clusters corresponding to depth zones that integrated vertical and horizontal sampling: photic zone (inshore near surface–bottom and offshore surface), deep chlorophyll maximum (offshore), and aphotic zone (offshore near bottom). We applied group-specific generalized additive models (GAMs) to log-transformed abundance data of major taxa in the photic zone, identifying key environmental factors that explained 42%–82% of the variation in abundance. SAR11 and SAR86 were positively associated with temperature and dissolved inorganic carbon, while cyanobacterial genera (Prochlorococcus and Synechococcus) were differently impacted by nutrients, salinity, and pH in ways that often followed their expected ecological niches. Representatives of protist parasites (Syndiniales) and grazers (Sagenista) showed group-specific nonlinear associations with salinity, oxygen, nutrients, and temperature. Using GAMs, we expanded the spatial resolution of DNA sampling and predicted surface log abundances at 84 cruise sites lacking amplicon data. Indicator analysis was performed with sequence-level data, revealing several protists that were indicative of more acidic waters and the absence of any significant prokaryote indicators. Our results provide the first basin-scale survey of microbes in the GOM and highlight the need for coordinated omics and environmental sampling to improve predictions of microbial responses to changing conditions.

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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.

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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.

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Flow as a mediator of ecosystem engineering: hydrodynamics shape chemical modification by kelp and mussel beds

Ecosystem engineers are organisms that modify their physical and chemical surroundings in ways that shape the structure and function of ecological communities. Physically, they build biogenic structures that modify flow, light, and habitat complexity. Chemically, they change oxygen and pH levels through metabolic processes such as photosynthesis and respiration. These modifications can either facilitate the presence of associated species by creating favorable microhabitats or inhibit them by amplifying environmental stress. Understanding the circumstances under which and how these shifts occur has become increasingly important as climate change intensifies environmental variability in coastal ecosystems. Advancing our understanding of how ecosystem engineers shape their communities requires considering how external factors, particularly flow, mediate their influence on the surrounding environment. Driven by tides, waves, and currents, flow regulates water residence time and thus the accumulation or dispersion of biologically modified water. Yet despite its central importance, the role of flow in controlling the strength and direction of ecosystem engineering remains poorly understood.

This dissertation examines how local hydrodynamics influences the capacity of marine ecosystem engineers to modify their surrounding chemical environments. It focuses on two contrasting but complementary systems: an autotroph, bull kelp (Nereocystis luetkeana), and a heterotroph, mussels (Mytilus spp.). Looking across these systems provides a broader view of how different types of engineers—those that produce oxygen through photosynthesis and those that consume it through respiration—shape their local chemical environments. By studying both systems, this work links two aspects of ecosystem engineering: 1) oxygen production and depletion, and 2) explores how flow determines when these species have the potential to act as facilitators or inhibitors within their communities. I combined field observations with laboratory and field experiments to explore how flow dynamics interact with biological traits, such as canopy structure, density, and behavior, to determine when these engineers act as facilitators or inhibitors within their communities. Across chapters, the work progresses from identifying environmental controls on kelp-driven chemical modification (Chapter 1) to isolating mechanistic feedbacks between flow, mussel behavior, and chemistry (Chapter 2), and then investigating density effects on chemistry and behavior by out-planting manipulated mussel aggregations in natural conditions (Chapter 3).

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Persistence of extreme low pH in a coralline algae habitat

Abstract

The extent of projected ocean acidification is partly dependent on the natural variability of marine carbonate chemistry—which is higher in coastal systems than in the open ocean. However, there are limited empirical studies quantifying the rate, magnitude and drivers of coastal environmental variability, preventing accurate assessments for how species and their associated communities may respond to projected climate change. Here, we quantified the annual variability of pH, temperature and dissolved oxygen in a coralline algae reef, a globally distributed biodiverse habitat that may be one of the most sensitive to projected climate change. We found that coralline algae and their communities are exposed to pH values as low as those projected for 2100 (even under a low emission scenario) for 63% of the year, including most of autumn and all of winter. Annual fluctuations in pH ranged by 0.46 units, with identifiable patterns at diel to seasonal timescales driven by various biogeochemical factors. Biologically driven patterns in dissolved oxygen and pH were coupled at multiple periodicities, and temperature was coupled to pH during the winter. Tidal cycling additionally modulated biological forcing of pH, increasing the complexity of intra-seasonal pH variability. Forecasting this environmental variability to the future led to projections of new pH extremes well beyond all IPCC emission scenarios. However, persistent long-term exposure to low pH may increase the acclimation and adaptation potential of coralline algae and their associated communities, providing a level of optimism for the continued survival of this habitat despite sensitivity to projected climate change.

Plain Language Summary

Here, we studied how the underwater environment naturally changes during the year on a coastal reef made of coralline algae, a type of red seaweed that builds reef habitats and supports diverse marine life. These reefs are thought to be especially vulnerable to climate change, particularly ocean acidification, which lowers the pH of seawater. Unlike the open ocean, coastal areas naturally experience more variability in pH, temperature, and oxygen. Monitoring these throughout the year, we found that the coralline algae reef already experiences pH levels as low as those expected for the year 2100. In fact, for about two-thirds of the year, including all of winter, the reef was exposed to these low pH conditions. We found that pH levels also varied a lot throughout the day and between seasons, influenced by biological activity of the algae and animals living in the reef, the ebb and flow of the tide, and water temperature. With some optimism, since long-term exposure to low pH is already experienced, these algae and their ecosystems may already be somewhat adapted to future conditions. This gives hope that they will be more resilient to future climate change than previously thought.

Key Points

  • Coralline algae are naturally exposed to pH at or below future climate projections, especially during autumn and winter
  • This is driven by an interaction between physical factors (temperature, tidal cycling) and biological processes (community metabolism)
  • Given future climate projections, these pH lows may become more extreme, but prolonged exposure may increase coralline algae resilience
Continue reading ‘Persistence of extreme low pH in a coralline algae habitat’

Climate change and ocean acidification pose a risk to underwater cultural heritage

Ocean acidification caused by climate change drives a spectrum of ecological impacts on the marine environment, while also posing a lurking threat to the traces of human history lying on seabeds. We present a quantitative assessment of the climate change risk to underwater cultural heritage, focusing on the vulnerability of historical stone materials to shifting ocean pH levels. We monitored the amount and rate of stone surface material loss and textural alteration triggered by natural processes of mineral dissolution and biodeterioration in submarine settings, combining field and laboratory experimentations with climate models. Stone deterioration has been minimal in pre-industrial and present times; however, escalating anthropogenic emissions might lead to an exponential surge in vulnerability, with irreversible decay processes accelerating in the next decades and centuries, constrained by material properties and shifting biofouling dynamics. Ocean acidification will dramatically challenge the protection of underwater cultural heritage, demanding urgent preservation and adaptation policies.

Continue reading ‘Climate change and ocean acidification pose a risk to underwater cultural heritage’

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)’

Coastal eutrophication and freshwater inputs drive acidification in the Indian River Lagoon, Florida

Highlights

  • First quantification of acidification throughout the IRL using Ωarag.
  • A positive relationship was found between Ωarag and salinity.
  • Ωarag had a negative relationship with dissolved nutrients.
  • Nutrients, algal blooms, and freshwater are drivers of acidification in the IRL.
  • Ωarag is important to understand eutrophication in estuaries.

Abstract

The additive effects of eutrophication and acidification in coastal environments have a wide range of implications for the health of organisms and ecosystems. In the eutrophic waters of the Indian River Lagoon (IRL), FL, USA, decreases in overall shellfish size have been reported, which may be related to coastal acidification. To better understand the relationship between acidification and eutrophication in the IRL, environmental parameters, dissolved nutrients, and aragonite saturation state (Ωarag) were monitored along the entire IRL in the 2016–2017 wet and dry seasons. Additionally, three sites in the central IRL were sampled approximately weekly from June 2016–June 2017 to observe temporal variability. For the IRL-wide survey, northern sites with higher dissolved nutrient concentrations had lower Ωarag due to nutrient pollution and harmful algal blooms, while southern sites with lower salinity had lower Ωarag related to freshwater inputs (i.e., discharges and rainfall). In the time series sampling, there was a positive correlation between Ωarag with salinity and negative correlations with dissolved nutrient concentrations. This work suggests that freshwater inputs and associated dissolved nutrients and organics have implications for acidification in the IRL, which will be important considerations for restoration efforts in the IRL and beyond.

Continue reading ‘Coastal eutrophication and freshwater inputs drive acidification in the Indian River Lagoon, Florida’

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’

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