Posts Tagged 'chemistry'

The Global Ocean Data Analysis Project version 3 (GLODAPv3) – an internally consistent biogeochemical data product for the world ocean

The Global Ocean Data Analysis Project (GLODAP) is a synthesis effort providing surface-to-bottom ocean biogeochemical observations determined through chemical analysis of discrete bottle samples, with an emphasis on seawater inorganic carbon chemistry and related variables. Version 3 of GLODAP comprises data from 1181 cruises, spanning more than 50 years of observations (1972–2023). It includes all data from the previous GLODAPv2.2023 (Lauvset et al., 2024) together with newly added data from 57 cruises. For all cruises, 13 core variables (temperature, salinity, oxygen, nitrate, silicate, phosphate, dissolved inorganic carbon, total alkalinity, CFC-11, CFC-12, CFC-113, CCl₄, and SF6) have undergone extensive quality control with particular focus on the identification and removal of systematic differences between cruises. The data are available in two formats: (i) as submitted by the data originators, converted to World Ocean Circulation Experiment (WOCE) exchange format, and (ii) as a merged data product in which adjustments have been applied. These adjustments were determined using crossover analyses in combination with a newly developed global inversion method, the furthest-first routine. The applied adjustments are intended to remove systematic differences arising from differences in measurement methods, calibration, and/or data-handling practices, while preserving known or likely temporal trends and natural variability. The consistency of the adjusted data product is estimated to be 0.0013 for salinity, 0.7 % for oxygen, 0.4 % for nitrate, 0.5 % for silicate, 0.5 % for phosphate, 1.2 µmol kg⁻¹ for dissolved inorganic carbon, and 1.4 µmol kg⁻¹ for total alkalinity. Consistency estimates could not be derived for transient tracers, but they are believed to be consistent to better than 5 % (10 % for SF₆). The enhanced consistency enables different datasets to be used together with greater confidence. Newly introduced cruise-specific uncertainty estimates for all core variables provide more granular quantifications of remaining cruise-to-cruise inconsistencies. Additional variables, including pH, discrete CO₂ fugacity (fCO₂), isotopic tracers, and others, were not subjected to secondary quality control but are included in the data product.

The original data, their documentation (metadata), and DOIs are available through the Ocean Carbon and Acidification Data System (OCADS) of NOAA’s National Centers for Environmental Information (NCEI), which also hosts the merged data product. All secondary quality control decisions and supporting information can be found in the online adjustment table (https://glodapv3.geomar.de, last accesses 26.06.2026). The product is distributed as a single global file and as four regional subsets (Arctic, Atlantic, Indian, and Pacific Oceans) under https://doi.org/10.25921/m6tp-mj50 (Lange et al., 2026). These adjusted files also include ancillary and approximated data obtained through interpolation or calculation from measured data.

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Seasonal forecasts of pH and aragonite saturation for the Bering Sea shelf

The number of numerical model forecasts of ocean environmental conditions has greatly expanded in recent years, including biogeochemical variables. Forecasts can provide marine resource managers with advance warning of extreme events such as heatwaves and hypoxia, though forecast products are scarcer in high-latitude environments. The Bering Sea shelf is a large marine ecosystem that supports critical commercial, cultural, and subsistence ecosystem services that are vulnerable to extreme events and anthropogenic stressors such as ocean acidification (OA). Here, we use a regional oceanographic model of the Bering Sea to assess model forecast skill in predicting bottom water pH and aragonite saturation state (Ωarag) on lead times from 1 to 9 months. We simulate 28 years (1982–2010) of 3-member ensemble retrospective forecasts, initialized both in April and May following the retreat of winter sea ice and several months in advance of early fall when the most acidic bottom water conditions occur. The results suggest that the model is skillful (anomaly correlation coefficients > 0.5) in forecasting shelf-wide anomalies in bottom water pH and Ωarag, on lead times up to 9 months owing primarily to strong persistence. However, predictive skill for finer scale spatial anomalies is more limited and variable. Model forecast skill is also strong in Bristol Bay, home to the red king crab fishery that has faced recent closures and is threatened by OA. The model forecasts presented here can provide several months advanced notice for acidified water conditions and bolster a suite of products used to support evidence-based fisheries management.

Plain Language Summary

Similar to weather forecasts for the atmosphere, numerical models can also be used to forecast ocean conditions. The skill of these forecasts can be high up to several months in advance because the ocean has a relatively long memory and changes occur more slowly, particularly below the surface. The Bering Sea sustains substantial marine fisheries, which are threatened by changing ocean conditions such as increasing water acidity. Here we used an ocean model to test how well the model can forecast acidified bottom water conditions several months in advance. We did this by running a suite of reforecasts (i.e., we retroactively forecast years that have already occurred) and comparing to the model simulation of the conditions that did occur. Our results suggest that the model can generate skillful forecasts with lead times of up to 9 months, mainly because the conditions that occur at the start of our forecast tend to persist through the summer and into the fall. These forecasts can provide Bering Sea resource managers with advance warnings of water conditions that are harmful to marine species, such as Bristol Bay red king crab.

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Aragonite saturation horizon variability along North Pacific seamounts and implications for deep-sea coral reefs

The 2014 discovery of living deep-sea coral reefs along the Northwest Hawaiian Islands (NWHI) and lower Emperor Seamount Chain (ESC), despite the North Pacific’s shallow aragonite saturation horizon (ASH) and high CaCO3 dissolution rates, underscores the need to understand the local seawater chemistry where these reefs persist. We investigated seawater carbonate chemistry using discrete samples along NWHI and ESC from two cruises ∼1 year apart (08/26/21–09/26/21, 09/09/22–10/24/22). Across the two cruises, ASH depth difference ranged from 15 to 77 m. Since the Pacific ASH shoals by 1–2 m yr−1, this long-term trend cannot explain the magnitude of ASH change observed. Potential contributions from anthropogenic CO2 and examining intermediate water mass changes from temperature-salinity plots did not provide an explanation for the observed changes. Instead, ASH depth variability was primarily governed by localized biogeochemical processes, namely changes in intermediate water respiration and CaCO3 dissolution. Indicators for dissolution (TA*) and respiration (AOU) suggest changes in ASH depth were driven by changes in dissolution at the northern- and southern-most sites, whereas respiration exerted stronger control at central sites. Combining 2021 and 2022 data with data from 2014 to 2019 revealed high interannual ASH variability, by as much as >200 m. Deep-sea coral reefs across the NWHI and ESC currently reside close to the ASH depth and likely experience interannual shifts between under- and supersaturation. As ocean acidification induced shoaling occurs alongside these interannual fluctuations, the frequency of undersaturation will be an important consideration for deep-sea coral reef longevity.

Plain Language Summary

In 2014, thriving deep-sea coral reefs were found in the Pacific near Hawaii and the Emperor Seamounts, where conditions were thought too acidic for reef development. To understand how these reefs persist, we studied the carbonate chemistry of this region during two research cruises (2021 and 2022). We found that the depth at which seawater becomes corrosive for coral skeletons (aragonite saturation horizon, ASH) changed far more from year to year than the gradual Pacific trend of 1–2 m yr−1. Human sourced carbon dioxide and natural shifts in ocean water masses do not explain the observed large changes. Instead, local biological and chemical processes, respiration and the dissolution of calcium carbonate, played a major role. When comparing seawater chemistry from 2014 to 2022, the ASH fluctuated even more dramatically than the predicted trend of 1–2 m yr−1. While climate change continues to drive corrosive deep waters closer to the surface, processes that occur on shorter timescales, local respiration and dissolution, can similarly expose deep sea coral reefs to corrosive conditions that can impact their longevity. Therefore, short term and local scale processes can affect long term acidification trends, making gradual shoaling harder to observe in short term data.

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Seasonal reef-scale variability in seawater CO₂ chemistry in the presence and absence of seaweed cultivation in Onna, Okinawa, Japan

Seaweed cultivation has been proposed as an active biogeochemical intervention to elevate seawater pH and create localized refugia from ocean acidification. To date, most studies have relied on autonomous sensors to contrast seawater pH inside and outside of seaweed cultivation plots. These studies provide important temporal observations but lack information about the spatial capacity for seaweed cultivation to provide pH refugia for surrounding habitats. This study investigated the spatiotemporal variability of seawater pH and CO₂ chemistry across the Onna-son reef, Okinawa, Japan, during the fall, winter, and spring seasons, with spring surveys coinciding with the peak extent of Mozuku (Cladosiphon okamuranus) cultivation. Relative to open-ocean conditions, seawater pH was elevated during 77–100% of afternoon observations in fall (up to + 0.10), 53% in winter (up to + 0.02), and 75–92% in spring (up to + 0.13). The greatest drawdown in dissolved inorganic carbon (DIC; − 44 µmol kg⁻1) and highest spatial pH variability (0.19) were observed during spring, the period of maximum seaweed cultivation, but coincided with reduced current velocities, small wave heights, and low mean sea level, conditions conducive to enhanced biogeochemical modification. Comparable pH elevations were observed during fall under similar temperature regimes, but higher current velocities, which suggest that seaweed cultivation may not be more effective than natural macroalgal habitats in elevating local seawater pH at this site. Future assessments of seaweed aquaculture as a mitigation strategy should explicitly incorporate local hydrodynamics and natural macroalgal influences, as these will impact the variability across both space and time.

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ISO 18191:2026 – Water quality — Determination of pHT in seawater — Method using the purple indicator of m-cresol

This document specifies a spectrophotometric determination of the pHT of seawater on the total hydrogen ion concentration pH scale. The total hydrogen ion concentration, [H+]T, is expressed as moles per kilogram of seawater. The method is suitable for assaying oceanic levels of pHT from 7.4 to 8.2 for normal seawater of practical salinity ranging from 20 to 40.

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Acidification

‘Acid rain’ changes the chemistry of soils and waters, causes damage to materials, and threatens wildlife and human health. Most important anthropogenic sources of acidifying compounds emitted to the air are fuel combustion and agriculture. Sulfur dioxide and nitrogen oxides in the atmosphere act as strong acids increasing the natural acidity of rainwater. Ammonia emissions from agriculture and the subsequent deposition of reduced nitrogen compounds trigger acidification processes in soils. Besides those external hydrogen ion (H+) sources, ecosystem internal turnover processes linked to nutrient cation uptake by vegetation, the nitrogen cycle, and biomass export from ecosystems are also of major importance. Several H+ sinks in soil, bedrock, and waters can compensate for H+ release (e.g., carbonate dissolution or silicate weathering). Land-use changes and fossil fuel use have led to dramatically increasing atmospheric carbon dioxide (CO2) concentrations worldwide. CO2 is absorbed by oceans and reacts with seawater to form carbonic acid. Acidification of oceans could have adverse effects on marine organisms using calcium carbonate in seawater to construct their shells and skeletons. Acidification is the result of a sensitive (un-)balance between ecosystem internal and external H+ sources and internal H+ sinks of different capacities and reaction rates.

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Acidification in aquatic systems

Aquatic acidification is a global change phenomenon driven by ever increasing anthropogenic carbon dioxide (CO2) emissions. This drives changes to the carbonate chemistry equilibrium in natural water, resulting in an increase in acidity, which has been shown to influence aquatic organisms. There is substantial evidence that acidification has consequences on marine, coastal, and freshwater ecosystems. The response of organisms varies among species and some biological processes are more sensitive than others, resulting in a complex biological response to acidification. Calcifying organisms, the larval and juvenile stages of many species, and coral reefs ecosystems are considered particularly vulnerable to acidification. The negative impacts of acidification may have eventual downstream consequences on species diversity and ecosystem resilience in the future if CO2 emissions continue unabated. Immediate global and local action is needed to limit the negative ecological and socioeconomic effects of this phenomenon.

The diagram illustrates the variability of p H across freshwater, coastal, and marine environments, the biological responses to acidification, and strategies for mitigation and adaptation. At the top, a landscape cross-section shows p H ranges: freshwater with less than 7.2 to 12 and high variability, multiple drivers, and uncertain responses; coastal waters with 7.5 to 8.5, high variability, multiple drivers, and complex responses; and marine waters with 7.9 to 8.1, more stable, gradual acidification, and high organism sensitivity. On the right, complex biological responses are described, including autotrophic activity raising p H, locally variable conditions, and potential refugia. Sensitive biological processes listed are behavior, calcification, metabolism and energy budgets, and larval development. Sensitive ecosystems include coral reefs, deep-sea ecosystems, and areas of high anthropogenic activity. At the bottom, two interconnected cycles are shown. The “Mitigate Impacts” cycle features reducing global emissions, carbon capture through seaweed and algae, and deacidification via calcium carbonate. The “Local Adaptation” cycle emphasizes managing multiple stressors, conserving refuge habitats with increased p H, and supporting sustainable fisheries and aquaculture.

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Field-deployable full-range underwater pH sensor using a polyprotic SERS probe

Accurate measurement of pH in underwater environments is essential for oceanographic research, environmental monitoring and subsurface exploration. However, conventional electrode-based sensors are limited by drift, corrosion and narrow operational ranges, particularly under extreme pH and high-salinity conditions. Here we present a fibre-optic surface-enhanced Raman scattering platform that enables full-range (pH 0–14) underwater pH sensing using the polyprotic molecular probe 2-amino-5-mercapto-1,3,4-thiadiazole. This probe exhibits 6 pH-dependent conformations, generating distinct surface-enhanced Raman scattering fingerprints that are decoded via machine learning for accurate, drift-resistant pH prediction with errors below 0.2 pH units. The sensor demonstrates high salt tolerance (up to 1 M NaCl), rapid reversibility and robust photostability, and can be deployed remotely at depths of up to 10 m in seawater and groundwater. By establishing a versatile optical strategy based on polyprotic molecular fingerprints, this work expands the capabilities of environmental monitoring and subsurface exploration in challenging aquatic environments.

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Persistence of Arctic Ocean acidification under negative emissions

Although net negative emissions of carbon dioxide (CO2) are essential to meet climate targets, little is known about how declining atmospheric CO2 levels will affect ocean acidification. Here, by analysing the acidity ([H+]) and corrosivity to aragonite (ΩArag) in eight Earth system models that made simulations under rising then falling CO2 levels, we identify the Arctic as a hotspot for delayed reversibility of ocean acidification. Under falling CO2, Arctic surface waters remain comparatively more acidic, and aragonite-corrosive conditions (ΩArag < 1) persist until atmospheric CO2 drops ~120 ppm below the threshold at which they first appeared under rising CO2. This hysteresis arises from the erosion of the natural surface-layer deficit in dissolved inorganic carbon, initially maintained by sea ice limiting air–sea gas exchange and not fully restored as sea ice recovers during CO2 decline. Thus, the Arctic Ocean experiences not only the greatest acidification but also the most delayed benefits from negative emissions.

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Method for correcting the temperature dependence of field-type glass electrode pH sensors

Seawater pH measurement is essential for monitoring ocean acidification and its biogeochemical impacts. Glass electrode pH sensors are widely used for in situ applications due to their ease of operation, low power consumption, and no reagent requirements. However, their accuracy can be affected by temperature-dependent effects, particularly those associated with the internal reference solution. Conventional calibration methods based on the Nernst response do not explicitly account for temperature-induced variations in the internal solution, which may lead to systematic bias under conditions with large temperature gradients. In this study, a correction method is proposed to address temperature-dependent errors by modeling the internal pH (pHin). The model incorporates two primary temperature-dependent contributions: the intrinsic temperature dependence of the phosphate buffer and potential shifts caused by activity changes in saturated KCl. These effects are combined through the electrode response factor (fR), defined as the ratio of the observed electrode slope to the theoretical Nernst slope, to estimate pHin as a function of temperature and correct measured pH values to a reference temperature of 25 °C. Application of the method to vertical seawater profiles demonstrated a reduction in deviation from colorimetric reference measurements. The corrected results showed reduced temperature-dependent bias across depth. This approach provides a practical framework for improving the reliability of in situ glass electrode pH measurements under varying thermal conditions. The proposed method addresses equilibrium temperature-dependent effects of the internal solution but does not explicitly account for transient hysteresis, pressure effects, or long-term sensor drift.

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Deep dive: evaluating students’ use of Toulmin’s argumentation pattern in chemistry classrooms for constructing scientific arguments about ocean acidification

Science education plays a key role in helping students to become responsible citizens, capable of making appropriate decisions based on scientific information, participating in discussions on socio-scientific issues (SSIs), and taking action in the context of climate change. Thus, achieving scientific literacy in general and practising scientific argumentation skills – as part of scientific literacy – in particular, are essential. Therefore, the pilot study presented here focusses on improving upper secondary students’ (ISCED 3) scientific argumentation skills by implementing Toulmin’s Argumentation Pattern (TAP) in the chemistry classroom. We focus on chemistry education to better understand subject-specific argumentation in chemistry classrooms. This pilot study is part of an interventional study that aims to implement TAP as a construction mechanism to improve students’ scientific argumentation skills. Our study is embedded in the SSI of human-induced ocean acidification. In order to gain insight into students’ scientific argumentation patterns and develop adequate teaching materials, we asked 29 upper secondary students to write well-founded arguments to confirm a claim about calcification of coral skeletons made in a newspaper headline. Students’ arguments were constructed prior to and following the provision of support material based on TAP. These arguments were analysed with regards to their formal quality using qualitative content analysis. Our findings indicate that TAP aligned well with our participants’ intuitive arguments. We discuss our findings and propose how using TAP can contribute to teaching and learning chemistry-specific argumentation skills.

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Giant kelp-associated variation in coastal seawater chemistry across contrasting sites in Chile and Tasmania

Background and Aims

Widespread shifts in seawater chemistry are occurring across spatial and temporal scales, with important consequences for coastal ecosystems. Giant kelp (Macrocystis pyrifera) forests elevate seawater pH and dissolved oxygen (DO) through photosynthesis, potentially providing short-term refugia from ocean acidification and deoxygenation. However, whether these effects persist across contrasting environmental settings remains unclear. Here, we assess how biological and oceanographic conditions regulate giant kelp-mediated modification of seawater chemistry across multiple sites.

Methodology

Hourly measurements of seawater pH, DO and temperature were collected during spring–summer 2022–23 using paired deployments inside and outside giant kelp forests at one site in central Chile and four sites in Tasmania, Australia. The influence of giant kelp density was also evaluated at two sites in southern Chile and three sites in Tasmania. An upwelling index was calculated for the central Chile site to assess the influence of regional oceanographic forcing on kelp-associated seawater chemistry patterns.

Key Results

Hourly pH and DO were higher inside giant kelp forests than outside at the central Chile site and at one Tasmanian site. At these locations, stronger daytime pH–DO relationships indicated that photosynthetic carbon uptake exceeded night-time respiration, generating a net positive metabolic signal. In Tasmania, giant kelp density was positively associated with hourly pH and DO, whereas no such relationship was detected in southern Chile. At the central Chile site, kelp-associated effects intensified during a strong upwelling event, reducing the severity of low pH and DO conditions.

Conclusions

Giant kelp forests can locally buffer short-term fluctuations in seawater pH and DO, but this capacity is highly site-dependent and influenced by giant kelp density and environmental conditions. Overall, our findings suggest that continued loss of giant kelp forests in Tasmania may reduce their potential to provide short-term refugia, while in Chile the strength of kelp-mediated seawater chemistry modification is likely to remain strongly influenced by variability in upwelling and freshwater inputs.

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CARIMED (CARbon, tracers, and ancillary data In the MEDiterranean Sea): a ship-based data synthesis product – overview and quality control procedures

The Mediterranean Sea (MedSea) is highly sensitive to climate-driven changes in temperature, oxygen, and pH, among other variables. To better assess these long-term trends, we developed CARIMED (CARbon, tracers, and ancillary data In the MEDiterranean Sea), the first comprehensive, harmonised data synthesis product for the MedSea. CARIMED integrates hydrographic, inorganic carbon, transient tracer, and ancillary measurements from 46 research cruises spanning the period from 1976 to 2018, containing observations for the entire water column across all MedSea sub-basins. A substantial component of the data was retrieved from fragmented or locally archived historical records, thus consolidating previously inaccessible measurements. Following global synthesis approaches, CARIMED applies a quality-controlled, and bias-adjusted framework. A key adaptation was the secondary quality control (2QC) procedure, specifically tailored to the MedSea’s unique hydrography, utilising sub-basin divisions and supplementary checks (including statistical consistency assessments) to resolve complex, often contradictory, inter-cruise offsets. This rigorous process minimised systematic biases, yielding a dataset with improved consistency, and highlights the urgent need for adapted standard operating procedures and reference materials to address the MedSea biogeochemical particularities. CARIMED delivers two complementary, freely available products: the aggregated original cruise data product (https://doi.org/10.20350/digitalCSIC/17785, García-Ibáñez et al., 2025) and the final bias-adjusted data synthesis product (https://doi.org/10.25921/cp5b-zq67, Álvarez et al., 2025; hosted at https://www.ncei.noaa.gov/access/ocean-carbon-acidification-data-system/oceans/CARIMED/, last access: 26 June 2026). This essential resource establishes a new benchmark for assessing long-term biogeochemical trends, validating regional ocean models, and supporting climate-change mitigation and adaptation strategies in this rapidly changing semi-enclosed basin.

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Crustose coralline algae buffer shallow reef environments from dissolution

Ocean acidification threatens coral reefs by reducing seawater pH and carbonate saturation state. Crustose coralline algae are particularly vulnerable because their high-magnesium calcite skeletons dissolve more readily than coral aragonite skeletons. However, this dissolution may increase alkalinity and buffer reef-water chemistry. Here we show, using repeated low-tide observations and in situ incubations in a shallow reef system in the southern Great Barrier Reef, that reef-water pH varies by more than one unit over the day (7.47 – 8.61), reaching levels comparable to those projected for the end of this century. Nighttime respiration promotes dissolution of high-magnesium calcite produced by crustose coralline algae, increasing alkalinity and helping maintain seawater supersaturated with respect to aragonite. At the same time, isolated coral incubations experience a greater decline in pH and aragonite saturation state in the absence of this buffering effect. These findings suggest that high-magnesium calcite-producing communities may help partially buffer reefs against future acidification.

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Annual variations of seawater carbonate system in the surface layer of the South-Eastern Mediterranean Sea

Seawater carbonate system measurements in the Mediterranean Sea are relatively scarce, especially in its eastern basin. This study describes the monthly variations of carbonate system parameters in the open sea and coastal water column of the eastern Mediterranean Sea during the period February 2018 to January 2019. Water samples were collected for analysis of Total Alkalinity and pHT at the shallow coastal THEMO1 and the deeper open-water THEMO2 (1,500 m bottom depth) stations off the Mediterranean coast of Israel. In the surface layer (<25 m), TA increased with salinity at a rate of +72 μmol·kg−1 and the pCO2(SW) was strongly and positively correlated with temperature. During summertime, surface waters were highly super-saturated with respect to atmospheric pCO2 (pCO2(SW) ∼ 600 μatm), while during winter they were only slightly super-saturated. The estimated net annual CO2 flux from the surface of the eastern Mediterranean Sea to the atmosphere during the study period was +2.8 Tg C·y−1, which is three times greater than a previous estimate made for this region (0.9 Tg C·y−1), and is attributed to the smaller volume of Atlantic water input in the present study compared to the previous one as well as the substantially shallower total dissolved inorganic carbon enriched core of the Levantine Intermediate Water in this study. Based on these results, it is still expected that future warming and salinization, reduced Atlantic Water influx to the eastern Mediterranean Sea, and increased stratification will increase the flux of CO2 to the atmosphere in this region.

Plain Language Summary

This study investigated annual variations in atmospheric CO2 flux from the surface of the eastern Mediterranean Sea based on monthly seawater sampling and carbon chemistry analyses conducted at two locations off the Mediterranean coast of Israel from February 2018 to January 2019. The results indicate that the southeastern Mediterranean Sea was a net source of CO2 to the atmosphere. This behavior was largely driven by seasonal changes in seawater temperature, which controls the saturation concentration of dissolved CO2 in seawater. During summer months, warm surface waters were a strong source of CO2 to the atmosphere, while during winter they were a weak sink. The study estimates that approximately 2.8 million tons of carbon were released annually from the sea to the atmosphere during the study period. This revised and more comprehensive estimate is ∼3 times higher than previous estimates reported for the same region. The increase is suggested to result from recent changes in regional circulation, particularly a reduced inflow of Atlantic Ocean waters into the eastern Mediterranean Sea. Based on these findings, continued warming, increasing salinity, and enhanced stratification of the eastern Mediterranean Sea are expected to further intensify CO2 release to the atmosphere in the future.

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Trends and persistence in ocean acidification as measured by station ALOHA

Ocean acidification, largely driven by the uptake of anthropogenic carbon dioxide, is reflected in a sustained decline in seawater pH. This paper examines the dynamics of surface-ocean pH at Station ALOHA over the period 1985–2024 using fractional integration methods, which allow for a flexible characterisation of persistence and trend behaviour. The differencing parameter is estimated under alternative assumptions concerning the error term, namely white-noise and autocorrelated Bloomfield disturbances, and recursive estimation is used to assess the evolution of the relevant parameters over time. The results show a negative and statistically significant time trend in both the original and logged pH series. The estimates of the differencing parameter are positive and significantly different from zero in all cases, providing evidence of long-memory behaviour. Under white-noise errors, the estimate of the differencing parameter is 0.89 and the unit-root hypothesis cannot be rejected, whereas allowing for autocorrelation yields an estimate of approximately 0.55, implying mean reversion with long-lasting but transitory effects of shocks. Recursive estimates further indicate that both persistence and the magnitude of the negative pH trend have increased over time. These findings suggest that pH dynamics at Station ALOHA are characterised by a persistent decline and slow adjustment following disturbances, highlighting the importance of long-term ocean monitoring and modelling approaches that account for fractional dependence. Nevertheless, the results should be interpreted with caution because the analysis is based on a single long-term record combining observational and reconstructed data.

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Ocean acidification as a planetary signal linking Earth system memory to deep-time lithosphere–ocean geochemical interactions

Highlights

  • First ever reinterpretation of ocean acidification as a planetary-scale signal encoding Earth system disequilibrium.
  • Links rapid surface pH decline to deep-ocean, sedimentary, and lithospheric memory.
  • Reveals a rate mismatch that overwhelms geological buffering despite modest pH magnitude.
  • Identifies CCD shoaling as the key integrator of short-term forcing and deep-time response.
  • Synthesis elevates ocean acidification to a diagnostic of long-term carbon cycle stability.

Abstract

Ocean acidification (OA) is widely recognized as a defining chemical signature of the Anthropocene ocean, yet it is still predominantly framed as a near-surface ecological stressor. Here, we advance a planetary-scale reinterpretation of OA as an information-bearing signal that links rapid anthropogenic carbon forcing to deep-time lithosphere–ocean geochemical interactions and long-lived Earth system memory. Observations since the late 20th century document a persistent, spatially heterogeneous decline in global surface-ocean pH, corresponding to a ∼30–35% increase in hydrogen ion concentration, driven by sustained air–sea CO2 uptake. Projected pH declines of 0.3–0.4 units by 2100 under high-emission scenarios imply rates of change at least an order of magnitude faster than most natural variations recorded in the geological archive. We synthesize carbonate system thermodynamics, carbonate compensation depth dynamics, sedimentary proxy evidence, and Earth system modeling to demonstrate how small, rapid surface perturbations propagate vertically, trigger widespread carbonate undersaturation, and imprint durable stratigraphic and geochemical signatures through sediment dissolution, altered burial fluxes, and delayed alkalinity restoration. Comparison with hyperthermal events, particularly the Paleocene–Eocene Thermal Maximum, reveals that the uniqueness of modern OA lies not in magnitude alone but in an unprecedented rate mismatch that overwhelms geological buffering mechanisms. Furthermore, we identify critical knowledge gaps regarding irreversibility, sedimentary signal emergence, and threshold behavior under rapid forcing. Overall, this study reframes OA as a planetary-scale diagnostic of whole-Earth system disequilibrium, revealing its fundamental significance for evaluating long-term carbon cycle stability, Earth system resilience, and the enduring geological legacy of anthropogenic emissions beyond human timescales.

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Localized biogeochemistry and seasonality govern carbonate chemistry in estuarine mangrove ecosystems

Sundarbans, the world’s largest contiguous mangrove ecosystem and representing shallow coastal Bay of Bengal of the Northern Ocean, faces dynamic climate variations, including ocean acidification. To delineate ocean acidification from natural pH variations, it is crucial to perform long-term measurements of multiple carbonate chemistry parameters such as pH, total alkalinity (TA), and dissolved nutrients, among others. In the present study, surface water carbonate chemistry parameters, including TA, pH, and dissolved nutrients (o-phosphate and silicate), were analysed monthly between 2014 and 2022 in three pre-defined stations, namely Stn1, Stn2, and Stn3, part of Sundarbans Biological Observatory Time Series (SBOTS) located in Sagar Island, the largest island of the Indian Sundarbans. The observed deviation from the linear TA-Salinity curve in the studied sites of SBOTS showed the influence of freshwater in modulating TA. Generalized Additive Model (GAM) revealed substantial seasonal variability in the controls on TA. During monsoon, salinity was a dominant driver of carbonate chemistry, consistent with enhanced freshwater discharge. In contrast, during the post-monsoon season, primary productivity as indicated by the relationship with Chla, dissolved silicate, was found to exert a stronger influence on TA variability. Multilinear regression (MLR) analysis of calculated pCO2 further supported these seasonal trends. Overall, the findings highlight the importance of season-specific assessments, highlighting the critical role of freshwater discharge in shaping estuarine carbonate dynamics. These insights are vital for predicting the vulnerability and response of mangrove estuaries under future climate change scenarios.

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Seasonal variations in the bulk density of planktic foraminiferal tests in response to oceanographic changes in the western North Pacific

Ocean acidification (OA) is a major component of ongoing global environmental change, yet its biological impacts on open-ocean calcifiers remain insufficiently quantified. Here, we investigate seasonal variability in the individual test density of the planktic foraminifer Globigerina bulloides in the western North Pacific. Test density was determined using high-resolution microfocus X-ray computed tomography, enabling micron-scale structural assessment. Time-series samples collected by sediment traps moored at 150 m and 540 m at station K2 (2008–2009) reveal pronounced seasonal variability, with test density reduced by ~ 20% during winter relative to other seasons. Seasonal reductions were associated with enhanced vertical mixing and positively correlated with mixed-layer pH, carbonate-ion concentration, and temperature. Additional plankton-tow samples collected between 2010 and 2016 further support a strong linkage between carbonate chemistry and calcification intensity. Multiple regression analysis shows that carbonate-ion concentration independently explains 46.6% of the variance in test density, whereas temperature accounts for only 0.25%, indicating that carbonate-ion availability exerts a dominant control on test density. Given the ongoing decline in carbonate-ion concentration in the North Pacific (~ 0.77 µmol kg−1 yr−1), our results imply an annual decrease of ~ 2 µg mm−3 in foraminiferal test density. Continued OA may therefore reduce biogenic CaCO3 shell density, potentially weakening the efficiency of the carbonate-based biological carbon pump. This study provides quantitative field-based evidence linking seasonal carbonate chemistry to shell density variability in open-ocean calcifiers.

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Variation and influencing factors of water alkalinity in estuary-bay waters of Zhanjiang Bay, China

This study investigated the spatial distribution, seasonal variation, and drivers of surface seawater alkalinity (Alk) in Zhanjiang Bay (ZJB) using high-frequency seasonal sampling in the summers and winters of 2023. Surface Alk ranged from 525.3 to 2213.3 μmol·L−1, with mean values of 1373.1 ± 420.9 μmol·L−1 (summer, n = 28) and 1612.3 ± 343.7 μmol·L−1 (winter, n = 20). Spatially, Alk increased progressively from the estuary to the inner bay and further to the bay mouth, reflecting a typical dilution gradient. Correlation analyses showed that summer Alk was positively correlated with salinity (ρ = 0.706, p < 0.001), indicating that salinity changes associated with conservative mixing were a dominant control, whereas the weaker winter correlation (ρ = 0.473, p < 0.001) suggested that biological processes may play a more important role. Tidal forcing was significantly associated with diurnal Alk variations, particularly in the estuary and inner bay. In the estuary, high Alk occurred during high tide, consistent with tidal mixing; in the inner bay, elevated Alk was observed during low tide, suggesting a possible tidal pumping effect. These findings provide baseline data on Alk dynamics in a subtropical estuarine bay and contribute to understanding the carbonate system and buffering capacity in similar coastal systems. However, because measurements of dissolved inorganic carbon and pCO2 were unavailable, a quantitative assessment of carbon sink capacity requires further investigation.

Continue reading ‘Variation and influencing factors of water alkalinity in estuary-bay waters of Zhanjiang Bay, China’

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