Posts Tagged 'chemistry'



Contrasting effects of river and erosion-derived inputs on Arctic Ocean acidification

Although the Arctic Ocean is relatively small in volume, its extensive coastline delivers large quantities of terrigenous material from rivers and coastal erosion. As a result, the Arctic Ocean is impacted more strongly by terrigenous material than most other parts of the global ocean. Yet the effect of this material on carbon cycling and ocean acidification remains poorly quantified. In this study, we use an ocean biogeochemical model driven by observation-based estimates of terrigenous carbon, alkalinity, and nutrients to evaluate their contribution to the mean state, depth pattern, and seasonal cycle of ocean acidification, as measured by the aragonite saturation state. Riverine alkalinity generally mitigates acidification, whereas organic carbon from coastal erosion intensifies it. Nutrients from both sources mitigate ocean acidification at the surface by stimulating primary production, but intensify it at depth through subsequent remineralisation. Together, riverine and erosion-derived inputs account for about 20–40 % of the seasonal variability in the saturation state of the surface ocean. This amplification of the natural seasonal cycle is primarily caused by an increase in the summertime maximum of the saturation state. Terrigenous inputs also reduce the Arctic Ocean’s capacity to absorb atmospheric CO2 by 17–25 %. Accurately representing carbon and nutrient inputs from rivers and coastal erosion in biogeochemical models is therefore important for reliable assessments of ocean acidification, ecosystem health, and carbon budgets in the Arctic Ocean.

Continue reading ‘Contrasting effects of river and erosion-derived inputs on Arctic Ocean acidification’

Groundwater-derived carbon promotes hypoxia and acidification in a large tropical estuary

Abstract

Submarine groundwater discharge (SGD) derived nutrient inputs have been extensively documented. However, SGD-derived carbon fluxes remain largely unconstrained, representing a critical gap in most coastal carbon budgets. Here, we resolve SGD and dissolved carbon budgets in the Pearl River Estuary (PRE), the largest estuary in Southern China surrounded by the world’s largest urban conglomerate. Broadly-defined SGD contributes 89%–96% of the dissolved inorganic carbon (DIC) pool (2–4 times riverine inputs) and 20%–70% of the dissolved organic carbon (DOC) fluxes of the PRE. SGD transports DIC exceeding total alkalinity (TAlk) by 2.7–7 times, potentially driving pH decline and acidification of nearshore waters. Groundwater pCO2 values are 10–36 times higher than estuarine waters. SGD-derived DOC mineralization can decrease estuary water pH by 0.04–0.16 units and increase CO2 by 6.0–90.0 μmol L−1, affecting local coral populations and benthic organisms. SGD also reduces seawater dissolved oxygen (DO) by 12–150 μmol L−1 and fuels the development of hypoxic zones. Overall, SGD regionally intensifies seawater hypoxia and acidification, creating challenging conditions for coral reef survival in an already stressed ecosystem. Our findings demonstrate that SGD should be integrated into carbon budgets and ecological assessments of the land-ocean continuum.

Plain Language Summary

Submarine groundwater discharge can transport large amounts of dissolved carbon into the coastal ocean, but it is often overlooked due to challenges in quantification. Here, we investigate the contribution of groundwater to the dissolved carbon pool in a large tropical estuary using radium isotopes and carbon data. We found that groundwater is a significant source of estuarine dissolved carbon and has the potential to acidify seawater oxygen-depleted waters. These findings emphasize the importance of considering groundwater when evaluating carbon budgets and the ecological health of coastal ecosystems.

Continue reading ‘Groundwater-derived carbon promotes hypoxia and acidification in a large tropical estuary’

Novel in situ CO2 enrichment system reveals seagrass meadows are a refugium against coastal acidification for North Atlantic bivalves

While the accumulation of anthropogenic CO2 in the atmosphere is causing a decline in global ocean pH, many eutrophic estuaries are already experiencing acidification due to accelerated respiration driving the consumption of dissolved oxygen (DO) and production of CO2, decreasing available carbonate ions (CO32-) and threatening marine calcifiers. Here, a novel in situCO2 enrichment system was constructed to examine the effects of coastal acidification on the growth and survival of two species of North Atlantic bivalves (Argopecten irradians and Crassostrea virginica) in two distinct estuarine habitats: a seagrass meadow and an unvegetated sandy bottom in an open water estuary. The in-situ system captured natural diel dynamics as ambient chambers displayed chemistry nearly identical to the surrounding water, while CO2-enriched, acidified chambers maintained a consistent ~Δ 0.3–0.5 pH offset. At the unvegetated sandy bottom site, A. irradians and C. virginica displayed significant reductions in growth and survival in the acidified chambers (pHT = 7.3–7.5; saturation state of aragonite, ΩAr = 0.6–0.9) relative to ambient conditions (pHT = 7.6–7.9; ΩAr = 1.6–2). At the seagrass site, while growth of A. irradians and C. virginica in the acidified treatments (pHT = 7.3–7.7; ΩAr = 0.7) receiving the same delivery of CO2 was, again, significantly slowed compared to the control (pHT = 7.5–8.1; ΩAr = 2 – 2.8), the growth reduction, mortality rates, and levels of acidification were attenuated compared to the sandy bottom experiment, evidencing the ability of seagrass to buffer seawater and serve as a potential acidification refuge for bivalves. Collectively, the novel experimental CO2 enrichment system constructed for this project demonstrates that coastal acidification can have deleterious effects on marine bivalve populations, and that future conditions as well as the habitat refuge offered by seagrasses must be considered when developing management and restoration plans for temperate estuaries. 

Continue reading ‘Novel in situ CO2 enrichment system reveals seagrass meadows are a refugium against coastal acidification for North Atlantic bivalves’

Seasonal variations and key controls on seawater aragonite saturation state in the Northern Yellow Sea, China

Based on four field surveys conducted from August 2022 to May 2023, seasonal distribution and dynamics of the seawater aragonite saturation state (Ωarag) were investigated in the northern coastal zone of the Northern Yellow Sea, an important fishery region, to assess impacts of ocean acidification especially in river-dominated coastal systems. Results revealed seawater Ωarag had significant spatiotemporal variability with surface values ranging from 1.42 to 3.76 in summer, 1.22 to 2.34 in autumn, 1.71 to 2.48 in winter, and 2.03 to 3.56 in spring. Subsurface seawater Ωarag was generally lower than surface values, while seawater with Ωarag < 1.5—a critical threshold for severe biological stress—were predominantly found in the nearshore areas and in the southwestern offshore bottom waters. Persistent seasonal acidification was observed across the study area. While seawater temperature played an important role in seasonal Ωarag variation, its effect was masked in the nearshore zones by river-diluted water inputs, especially in summer, and in offshore bottom waters by community respiration during summer and autumn. These mechanistic insights clarify key drivers of coastal acidification and provide a scientific basis for developing targeted strategies to detect acidification trends and ecosystem responses in anthropogenically impacted coastal regions.

Continue reading ‘Seasonal variations and key controls on seawater aragonite saturation state in the Northern Yellow Sea, China’

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’

Environmental controls and nonlinear responses of the diatom-dinoflagellate ratio in Jiaozhou Bay

Highlights

  • Dia/dino abundance, biomass, and diversity ratios exhibited similar temporal patterns;
  • All ratios showed considerable heterogeneity without a consistent distributional trend;
  • Dia/dino ratios responded distinctly to DO, nutrients, and their interactions;
  • Shifting seawater properties exerted large influence on diatom-dinoflagellate dynamics.

Abstract

Diatoms and dinoflagellates are widely recognized as key indicators of marine ecosystem status and play central roles in ecosystem functioning and biogeochemical cycling. Yet how these two major phytoplankton groups adjust to changing coastal environments, and whether such adjustments occur coherently in different ecological dimensions, remains poorly constrained. Hence, we studied the temporal and spatial dynamics of diatom-dinoflagellate (dia/dino) ratios in Jiaozhou Bay during 2021 and 2024, integrating abundance-, carbon biomass-, diversity-, and richness-based metrics. Although abundance, biomass, and diversity ratios exhibited broadly similar temporal trajectories, the richness ratio displayed an opposite pattern, highlighting a decoupling between numerical dominance and species composition. Spatially, all four ratios exhibited significant heterogeneity, without a consistent nearshore-offshore gradient, reflecting complex local regulation. Correlation analyses revealed distinct controls on dia/dino ratios. The abundance ratio increased under conditions of elevated dissolved inorganic nitrogen (DIN) and reduced dissolved oxygen (DO), whereas the diversity ratio was associated with high DIN and low dissolved inorganic phosphorus (DIP). In contrast, the carbon biomass ratio was primarily linked to reduced DO and lower pH, while the richness ratio responded most strongly to the combined influence of low DO and elevated DIP. These contrasting responses indicated that dia/dino ratios captured different facets of phytoplankton community reorganization rather than reflecting a single environmental driver. Overall, our results suggested that the balance between diatoms and dinoflagellates in Jiaozhou Bay emerged from the coupled and nonlinear interactions among nutrient availability and oxygen dynamics. This study highlighted the dia/dino balance as an integrative indicator of coastal ecosystem condition and implied the importance of considering multiple ecological dimensions when assessing phytoplankton responses to ongoing eutrophication and environmental change.

Continue reading ‘Environmental controls and nonlinear responses of the diatom-dinoflagellate ratio in Jiaozhou Bay’

Trophic status and climatic stressors in the shallow coral reefs of the Cuban marine shelf

The “Bojeo a Cuba” expedition (summer 2023) provided a synoptic, national-scale snapshot of oceanographic conditions around Cuba’s shallow coral reefs during a regional marine heatwave. At 66 sites across six regions, we evaluated key climatic stressors (sea surface temperature, pH, alkalinity) and trophic status indicators. Satellite-derived SST during each site’s sampling week revealed significantly warmer waters on the southern shelf (mean = 30.93 °C) than the northern shelf (mean = 29.21 °C, P < 0.01). In situ SST was consistently high (mean = 30.52 °C), documenting the heatwave’s intensity. pH (mean = 8.12) and total alkalinity (mean = 2343 µmol kg⁻¹) indicated a currently balanced carbonate system. Concentrations of dissolved inorganic nitrogen and phosphorus were below our methods’ quantification limits (1.61 µmol L⁻¹ for P-PO₄³⁻), while chlorophyll-a (mean = 0.04 µg L⁻¹) consistently classified waters as oligotrophic. This study establishes a critical summer baseline, confirming oligotrophic conditions while documenting the severity of thermal stress during the 2023 heatwave—the most immediate and uniform threat to Cuban reefs. Our findings underscore the vulnerability of these ecosystems to extreme warming events within the context of long-term Caribbean warming trends.

Continue reading ‘Trophic status and climatic stressors in the shallow coral reefs of the Cuban marine shelf’

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’

Two decades of skeletal density decline in Pocillopora spp. corals in the Mexican Pacific Ocean: insight into a tropical eastern Pacific acidification scenario?

Corals demonstrate vulnerability to environmental changes, exhibiting the capacity to substantially modify coral calcification. In this study, we estimated declines in the density of Pocillopora coral species in the Mexican Pacific. The samples utilized in this study encompass both recently collected corals and those stored in Mexican repositories collected in the northeastern and southern Mexican Pacific regions. Density estimates indicate a 28.6% decline in coral density over the past 23 years (−0.0227 g CaCO3 cm-3 y-1) in the southern Mexican Pacific, while at the entrance to the Gulf of California, density has decreased by 15.4% over the past 20 years (−0.017 g CaCO3 cm-3 y-1). A comprehensive evaluation of environmental data reveals that the observed decline in Pocillopora skeletal density in Mexican Pacific reefs is concomitant with decreases in Ωar and pH, and an increase in ocean temperature on a substantial regional scale. When considered in conjunction with the previously documented reductions in coral growth of Pocillopora spp. skeletons in the eastern Tropical Pacific, our findings indicate a potential decline in CaCO3 production within the region’s reef systems. The results of this study underscore the significance of generating long-term series of coral growth parameters for relevant reef-building species and the carbonate system in key and representative coastal areas, particularly those that are already challenging for coral survival and reef maintenance.

Continue reading ‘Two decades of skeletal density decline in Pocillopora spp. corals in the Mexican Pacific Ocean: insight into a tropical eastern Pacific acidification scenario?’

Consequences of rising atmospheric CO₂ on ocean acidification and dissolved carbon cycling: a systematic review

Increasing atmospheric CO2 and temperature diminish ocean pH and raise the amounts of dissolved inorganic and organic carbons, causing wide-ranging shifts in marine water carbon chemistry and predicting the impacts on long-term ecosystems. This review aimed to determine the ocean chemistry and spatial variation of CO2 at a global scale, as well as to predict the influences of anthropogenic and natural changes on marine ecosystems. The literature has demonstrated that the southern polar oceans, Antarctica, and any coastal zone are predominantly susceptible to marine acidification and the dissolved carbon cycle. Based on 355 studies conducted over the last 30 years, this investigation found that marine acidification and the dissolved cycle are complex and poorly understood phenomena. These two facts and climate change are very interrelated, and the potential of these threats is very spatial, seasonal, stratified, and complex also. It was found that the atmospheric CO2 has increased by about 50% since preindustrial times and excess CO2 raise the seawater acidity through some equilibrium reactions in aqueous medium. The study observed that over the past half-century, the marine surface water acidity has risen by 30%, and predicted that by 2100, it will increase to 150. Moreover, this study critically reviewed the actual rules of marine dissolved organic and inorganic carbon on the global carbon cycle and marine acidification and vice versa. Such a major change in ocean chemistry will already have wide consequences for marine life and ocean ecosystems.

Continue reading ‘Consequences of rising atmospheric CO₂ on ocean acidification and dissolved carbon cycling: a systematic review’

Introducing the first ocean carbonate chemistry products hub

The ocean plays a critical role in stabilizing Earth’s climate. As the planet’s largest active carbon sink, it absorbs about 25% of global carbon dioxide emissions and roughly 90% of the excess heat generated by those emissions. This critical role helps regulate the planet’s climate, but comes at a cost.

“As carbon dioxide enters the ocean, some of it reacts with water to form a weak acid that increases the acidity of the ocean and alters the natural chemical balance of seawater,” said Liqing Jiang, a research scientist at Earth System Science Interdisciplinary Center and NOAA’s National Centers for Environmental Information (NCEI), “As more carbon dioxide enters the ocean, seawater becomes increasingly acidic. In fact, ocean acidity has risen by about 30% since the beginning of the Industrial Revolution.”

A more acidic ocean reduces carbonate ions, which alongside calcium, is a building block for ocean creatures that form skeletons and shells like coral reefs and oysters. Higher acidity reduces coral larval survival, weakens reef structures, and increases ecosystem vulnerability to storms and bleaching. These creatures function as key marine health indicators, and their decline threatens the entire marine ecosystem.

However, the ocean is vast, and the interconnected physical, chemical, and biological processes require scientists like Jiang to integrate many different types of data to piece together the full picture of how ocean chemistry is changing.

To support researchers navigating this complexity, Jiang led a team of international researchers to publish a comprehensive review of over 60 major ocean carbonate chemistry data products. The catalog brings together a wide range of global datasets, including historical time series, model outputs, and aggregated products spanning multiple time periods, making it one of the most comprehensive compilations of ocean carbonate chemistry data products to date.

Jiang’s goal is to present all available ocean carbonate chemistry products. He continues to collect datasets through the catalog to widen the library of data.

“My hope is that researchers will use these products to better understand changes in ocean carbonate chemistry, to improve model inputs for more accurate projections of future ocean conditions, and to support more robust assessments of marine ecosystem vulnerability,” said Jiang.

The paper detailing this work, “Synthesis of data products for ocean carbonate chemistry”, has been published in Earth System Science Data. The full data product catalog is publicly accessible at the following link.

Continue reading ‘Introducing the first ocean carbonate chemistry products hub’

Glacial meltwater impacts marine carbonate chemistry on Iceland’s continental shelf

Increased meltwater runoff from glaciers may drive localized ocean acidification and impact carbon dioxide (CO2) uptake in the coastal ocean. However, the paucity of carbonate system observations from continental shelves receiving inputs from glaciers limits our understanding of cryosphere‐ocean connectivity. Here, we contrast meltwater impacts on seawater carbonate chemistry and stable isotopes (δ13C‐DIC) off marine‐ and land‐terminating glacier outflows off Iceland. On the shelf outside a marine‐terminating glacier, glacial meltwater reduced the seawater buffer capacity of receiving surface waters through dilution of total alkalinity, and increased CO2 uptake through salinity‐driven drawdown of pCO2. Primary production acted as a counterbalance to the lowered [TA‐DIC]. On the shelf area receiving meltwater from large glacial river deltas, CO2 uptake was almost halved and the saturation state of aragonite was 0.2 units lower than on the marine‐terminating glacier shelf. Reduced net autotrophy due to higher turbidity and upwelling of low‐pH deep waters off the delta‐dominated shelf likely explain those differences. The diverging carbonate dynamics on the two shelves build on previous observations that land‐terminating glaciers can reduce the buffer capacity as well as CO2 uptake potential of nearshore surface waters in comparison to marine‐terminating glaciers. The future retreat of many marine‐terminating glaciers onto land is likely to modify how meltwater will impact coastal seawater carbonate chemistry.

Continue reading ‘Glacial meltwater impacts marine carbonate chemistry on Iceland’s continental shelf’

Applying omics techniques to examine microscopic life fueling Gulf region ecosystems 

Scientists at NOAA’s Atlantic Oceanographic & Meteorological Lab and the Northern Gulf Institute applied omics techniques to provide the first basin-scale assessment of the microbial communities at the base of marine ecosystems across the Gulf region. The new study from Dr. Luke Thompson’s group, conducted by Dr. Sean Anderson and co-authors, is the largest environmental DNA (eDNA) or microbiome survey of the Gulf of America ever performed.

Scientists collected environmental DNA (eDNA) – genetic material from whole microbes or shed by marine life into the environment – during the 2021 Gulf and Ocean Monitoring Ecosystems and Carbon Cruise (GOMECC). These samples unlock crucial new insights into the microscopic life across an entire basin – from nearshore coastal ecosystems out to the open Gulf. By analyzing the microbial communities throughout the water column, we can better understand how they are being impacted by changing environmental conditions. 

Changes in the composition of these microbial communities in any given region has cascading effects, influencing the biodiversity and feasibility of commercially viable species to survive and flourish in a specific region. Understanding how microbial diversity throughout the water column varies with changing conditions – changes in salinity, temperature, nutrient levels – could unlock key insights and provide early indicators of how entire ecosystems will be impacted by exacerbated environmental stressors, including ocean acidification

Continue reading ‘Applying omics techniques to examine microscopic life fueling Gulf region ecosystems ‘

Synthesis of data products for ocean carbonate chemistry

As the largest active carbon reservoir on Earth, the ocean is a cornerstone of the global carbon cycle, playing a pivotal role in modulating ocean health and the Earth’s climate system. Understanding these crucial roles requires access to a broad array of data products documenting the changing chemistry of the global ocean as a vast and interconnected system. This review article provides an overview of 68 existing ocean carbonate chemistry data products and data product sets, encompassing compilations of cruise datasets, derived gap-filled data products, model simulations, and compilations thereof. It is intended to help researchers identify and access data products that best align with their research objectives, thereby advancing our understanding of the ocean’s evolving carbonate chemistry. The list will be updated periodically to incorporate new data products. The most up-to-date list is available at https://oceanco2.github.io/co2-products/ (Gregor and Jiang, 2026).

Continue reading ‘Synthesis of data products for ocean carbonate chemistry’

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’

Modelling seawater pCO2 and pH in the Canary Islands region based on satellite measurements and machine learning techniques

Recent advancements in remote sensing systems, combined with new machine-learning model-fitting algorithms, have enabled the estimation of seawater carbon dioxide partial pressure (pCO2,sw) and pH (pHT,is) in the waters around the Canary Islands (13–19° W; 27–30° N). Continuous time-series data collected from moored buoys and Voluntary Observing Ships (VOS) between 2019 and 2024 were used to train and validate the models, providing a robust observational basis for satellite-derived estimates.

Among all models tested, bootstrap aggregation (bagging) performed best, achieving an RMSE of 2.0 µatm (R2>0.99) for pCO2,sw and 0.002 for pHT,isMultilinear regression (MLR)neural networks (NN) and categorical boosting (CatBoost) also showed good predictive skill, with RMSE values between 5.4 and 10 µatm for pCO2,sw (360–481 µatm) and 0.004–0.008 for pHT,is (7.97–8.07). Using the most reliable model, we identified an increasing trend in pCO2,sw of 3.51±0.31 µatm yr−1, exceeding the atmospheric CO2 growth rate (2.3 µatm yr−1), alongside an acidification trend of −0.003 ± 0.001 yr−1.

Over the 2019–2024 period, rising atmospheric CO2 and increasing sea surface temperatures (reaching up to 0.2 °C yr−1 during the unprecedented 2023 marine heatwave) likely contributed to these trends. The Canary Islands region shifted from a weak CO2 source (0.90 Tg CO2 yr−1) in 2019 to 4.5 Tg CO2 yr−1 in 2024. After 2022, eastern sites that previously acted as annual CO2 sinks became net sources.

Continue reading ‘Modelling seawater pCO2 and pH in the Canary Islands region based on satellite measurements and machine learning techniques’

Physics-guided machine-learning forecasting and analysis of carbonate changes in the surface Western Mediterranean

Highlights

  • Physics-guided ML forecasts surface pCO2 and pH along a Western Mediterranean VOS line.
  • Day-ahead pCO2 is predicted with μatm-level RMSE; pH behaves nearly deterministically.
  • Boosted trees and sequence models retain skill under strict, deployable forecast conditions.
  • Explainable AI recovers dominant thermal control and air–sea CO2 gradient drivers.
  • Improved pCO2 forecasts directly reduce uncertainty in air–sea CO2 flux estimates.

Abstract

We introduce a hybrid, physics-guided machine-learning system for forecasting and explaining surface marine carbonate changes along a fixed Volunteer Observing Ship route between Gibraltar and Barcelona from 2019 to 2024. The dataset includes more than 90 high-frequency transects collected under ICOS/SOOP standards, containing underway pCO2/fCO2, pH (measured and derived), sea-surface temperature, and salinity. After applying consistent quality control and harmonizing the data in time and space, we combine physics-based carbonate diagnostics—such as the thermal/non-thermal decomposition (FASS) and first-order Taylor attribution of temperature, salinity, total alkalinity, and dissolved inorganic carbon sensitivities—with time-aware models including linear regressions, boosted trees, and sequence networks (1-D CNNs and LSTMs) trained on historical windows. We evaluate generalization and uncertainty through chronological splits, leave-one-year-out tests, and year-wise bootstrap sampling. With all current predictors available, day-ahead pH and pCO2 predictions reach near-optimal skill; pH behaves almost deterministically, while pCO2 achieves RMSE on the order of a few μatm. Even under stricter forecast conditions without real-time carbonate chemistry, boosted trees and sequence models maintain strong performance by exploiting persistence and seasonal timing. Model-explanation tools (SHAP, partial dependence) recover the expected carbonate drivers, highlighting dominant thermal effects and key roles of seawater CO2 state and air–sea gradients. Spatial–temporal diagnostics reveal amplified summer pCO2 peaks in the Alboran/northern Morocco region and out-of-phase pH patterns. Predicted fields are converted to air–sea CO2 flux using standard solubility and gas-transfer formulations, and propagated uncertainties show that improving pCO2 accuracy directly reduces flux uncertainty. The resulting air–sea CO2 fluxes exhibit a pronounced seasonal cycle, with summer outgassing reaching several mmol m-2 d-1 and winter uptake of comparable magnitude along the transect, while interannual variability dominates over 2019–2024 and no statistically robust long-term trend is detected; typical flux uncertainties are on the order of 0.1–0.2 mmol m-2 d-1. Altogether, this delivers an explainable, uncertainty-aware system ready for deployment, linking forecast skill to process understanding and CO2 exchange in a climate-sensitive corridor.

Continue reading ‘Physics-guided machine-learning forecasting and analysis of carbonate changes in the surface Western Mediterranean’

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’

Ocean acidification and changes in biological production in the western subarctic region of the North Pacific over the quarter century, 1999–2023

Changes in the physical and biogeochemical conditions of the ocean over time can affect marine ecosystems. In this study, we use biogeochemical observational data for the past 25 years (1999–2023) to investigate ocean acidification and changes in biological production at site K2 (47˚ N, 160˚ E) in the western subarctic region of the North Pacific Ocean. During this period, satellite-derived sea surface temperatures increased at a rate of 0.056 °C yr–1, while the surface mixed-layer salinity decreased by 0.004 yr−1. As a result of the oceanic uptake of anthropogenic CO2 from the atmosphere, the deseasonalized annual mean surface mixed-layer pH and saturation states of calcium carbonate minerals of calcite and aragonite decreased at rates of 0.0013 ± 0.0004, 0.007 ± 0.003, and 0.004 ± 0.002 yr−1, respectively. These rates are consistent with those calculated for winter. Under these acidification conditions, no significant trends were observed in either the annual mean or winter concentrations of nutrients (phosphate, nitrate, and silicate), or in total alkalinity in the surface mixed layer. However, the decadal trends in nutrient concentrations show a significant increase in May and decrease in July. Net community production (NCP), which is an index of biological production, was estimated from differences in nutrient concentrations between winter and May or July. This analysis revealed significant decreasing trends in NCP from winter to May, followed by increasing trends from winter to July. The stoichiometric molar ratio of Si associated with the July NCP increase (P:N:Si = 1:15:55) is higher than the previously reported ratio (1:16:40). A significant decreasing trend in satellite-derived photosynthetically active radiation (PAR) was observed in May (0.20 ± 0.08 yr−1), which may be linked to reduced biological production during that month. This decrease may be offset by increased production in summer that is likely due to a shift in the timing of the diatom bloom. These findings highlight the effects of long-term changes of potential drivers of both atmospheric and deep oceanic origin on oceanic biological production.

Continue reading ‘Ocean acidification and changes in biological production in the western subarctic region of the North Pacific over the quarter century, 1999–2023’

Decadal biogeochemical predictions for the bottom marine environment of the Northeast U.S. Continental Shelf

The Gulf of Maine and the surrounding Northeast U.S. Continental Shelf are experiencing rapid marine environmental change arising from complex regional dynamics that challenge near-term (1–10 years) predictive capabilities for valuable living marine resources. Here, using a high-resolution regional ocean model, we demonstrate skilful decadal forecasts of ocean bottom habitat characteristics including bottom temperature, dissolved oxygen (O2), pH and aragonite saturation state (Ωar). Bottom temperature and pH predictions show substantial skill driven primarily by radiatively forced warming and carbon uptake trends, while bottom O2 and Ωar predictions benefit more from initialization due to stronger internal variability. Retrospective forecasts successfully predicted observed historical changes in water masses and environmental properties, including recent cooling/freshening transitions driven by replacement of Warm Slope Water with Labrador Slope Water. This water mass variability also modulates biogeochemical conditions and ocean acidification buffering capacity, with our recent forecasts indicating that benefits from the expected respite from rapid warming might be tempered by challenges posed by rapid acidification. The demonstrated predictability of coupled physical-biogeochemical processes supports developing integrated prediction systems for climate-informed marine resource management.

Continue reading ‘Decadal biogeochemical predictions for the bottom marine environment of the Northeast U.S. Continental Shelf’

Subscribe

Search

  • Reset

OA-ICC Highlights

Resources