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Four species of shellfish, blue mussel (Mytilus galloprovincialis), Pacific abalone (Haliotis discus hannai), zhikong scallops (Chlamys farreri), and Pacific oyster (Crassostrea gigas), were exposed to decoupled carbonate system variables to investigate the impacts of different seawater carbonate parameters on the CO2 excretion process of mariculture shellfish. Six experimental groups with two levels of seawater pH (pH 8.1 and pH 7.7) and three levels of total alkalinity (TA = 1000, 2300, and 3600 μmol/kg, respectively) were established, while pH 8.1 and TA = 2300 μmol/kg was taken as control. Results showed that the CO2 excretion rates of these tested shellfish were significantly affected by the change in carbonate chemistry (P < 0.05). At the same TA level, animals incubated in the acidified group (pH 7.7) had a lower CO2 excretion rate than those in the control group (pH 8.1). In comparison, at the same pH level, the CO2 excretion rate increased when seawater TA level was elevated. No significant correlation between the CO2 excretion rate and seawater pCO2 levels (P > 0.05) was found; however, a significant correlation (P < 0.05) between CO2 excretion rate and TA-DIC (the difference between total alkalinity and dissolved inorganic carbon) was observed. Blue mussel has a significantly higher CO2 excretion rate than the other three species in the CO2 excretions per unit mass of soft parts, with no significant difference observed among these three species. However, in terms of CO2 excretion rate per unit mass of gills, abalone has the highest CO2 excretion rate, while significant differences were found between each species. Our studies indicate that the CO2 buffering capacity impacts the CO2 excretion rate of four shellfish species largely independent of pCO2. Since CO2 excretion is related to acid–base balancing, the results imply that the effects of other carbonate parameters, particularly the CO2 buffering capacity, should be studied to fully understand the mechanism of how acidification affects shellfish. Besides, the species difference in gill to soft parts proportion may contribute to the species difference in responding to ocean acidification. [ABSTRACT FROM AUTHOR]

The air–sea exchange of carbon dioxide (CO2) on a global scale is a key factor in understanding climate change and predicting its effects. The magnitude of sea spray's contribution to this flux is currently highly uncertain. Constraining CO2's diffusion in sea spray droplets is important for reducing error margins in global estimates of oceanic CO2 uptake and release. The timescale for CO2 gas diffusion within sea spray is known to be shorter than the timescales for the droplets' physical changes to take place while aloft. However, the rate of aqueous carbonate reactions relative to these timescales has not been assessed. This study investigates the timescales of droplet physical changes to those of chemical transformations across the H2CO3/HCO3−/CO32− sequence. We found that physical timescales are rate limiting and that evaporation drives carbonate species into gaseous CO2, promoting the production and evasion of CO2 from sea spray droplets. This has important implications for carbon cycling and feedback in the surface ocean. [ABSTRACT FROM AUTHOR]

Ocean alkalinity enhancement (OAE) via the enhanced weathering of alkaline minerals is a promising carbon dioxide removal (CDR) technology. Theoretically, these includes iron and steel slags, although their dissolution kinetics in seawater are unknown. Here, we conducted lab-scale experiments to assess the alkalinity generation potential and dissolution kinetics of various slags in seawater. We show that the alkalinity generated per mass of iron slag was logarithmic, i.e., higher amounts of iron slag added had diminishing alkalinity returns. In contrast, the relatively quick dissolution of steel slags and their linear generation of alkalinity per mass of feedstock dissolved in seawater makes them better OAE candidates. Furthermore, despite the presence of potentially toxic metals in these feedstocks, their low to non-existent presence as dissolution products suggests that harmful concentrations should not be reached, at least for the slag tested here. Finally, if all steel slag produced annually was used for OAE, between 10 and 22 gigatonnes of CO2 could be captured cumulatively by 2,100, highlighting significant CDR potential by slags. [ABSTRACT FROM AUTHOR]

To quantitatively assess seasonal variations in the partial pressure of carbon dioxide (pCO2) in the Pacific sector of the Arctic Ocean (Canada Basin and Chukchi Sea) in 2021, water temperature, salinity, chlorophyll‐a, pCO2, dissolved inorganic carbon (DIC), total alkalinity (TA), and nutrients were measured. During summer 2021, surface water pCO2 in our study area (315 ± 41 μatm) was undersaturated with respect to the atmosphere (404 ± 4 μatm), and the ocean was a sink for atmospheric CO2 (−10.5 ± 11.0 mmol C m−2 day−1). Using DIC, TA, and nutrients in the temperature minimum layer, we estimated the under‐ice pCO2 in the water during the previous winter and calculated changes in pCO2 (δpCO2) due to temperature changes, freshwater inflow, biological activity, and other factors (gas exchange and advection) from winter to summer. In the Chukchi Sea, biological activity and temperature changes had significant impacts on pCO2, whereas in the Canada Basin, the influx of freshwater caused a significant decrease in pCO2. Our results suggested that different types of freshwaters had different effects on pCO2, with sea ice meltwater having a greater effect on reducing pCO2 than river water or snowmelt water. We therefore emphasize the importance of freshwater type and proportion, as well as freshwater supply, for prediction of future pCO2 changes. Plain Language Summary: Assessment of the factors that cause ocean CO2 to vary is important in the Arctic Ocean, which acts as an atmospheric CO2 sink that will change significantly because of global warming. Seawater and sea ice samples were collected in the Pacific sector of the Arctic Ocean to investigate the carbonate chemistry. The partial pressure of carbon dioxide (pCO2) was lower on the sea surface than in the atmosphere during summer, and the ocean absorbed atmospheric CO2. The decreases of pCO2 from winter to summer were driven primarily by biological activity in the Chukchi Sea (partially offset by temperature increases) and by freshwater additions in the Canada Basin. Sea ice meltwater, snow meltwater, and river water had different effects on pCO2, even though all of them diluted the carbonate concentrations of surface water, because of differences in the alkalinity and carbonate chemistry among these freshwater sources. Key Points: The Pacific sector of the Arctic Ocean absorbed atmospheric CO2 in summerIn the Chukchi Sea, biological activity and temperature changed pCO2, while in the Canada Basin, the freshwater caused a decrease in pCO2Sea ice meltwater had a greater effect on reducing pCO2 than river water or snow meltwater [ABSTRACT FROM AUTHOR]

There is growing concern about the effects of ocean acidification (OA) on coral reefs, with many studies indicating decreasing calcium carbonate production and reef growth. However, to accurately predict how coral reefs will respond to OA, it is necessary to characterize natural carbonate chemistry conditions, including the spatiotemporal mean and variability and the physical and biogeochemical drivers across different environments. In this study, spatial and temporal physiochemical variability was characterized at two contrasting reef locations in Bocas del Toro, Panama, that differed in their benthic community composition, reef morphology, and exposure to open ocean conditions, using a combination of approaches including autonomous sensors and spatial surveys during November 2015. Mean and diurnal temporal variability in both physical and chemical seawater parameters were similar between sites and sampling depths, but with occasional differences in extreme values. The magnitude of spatial variability was different between the two sites, which reflected the cumulative effect from terrestrial runoff and benthic metabolism. Based on graphical vector analysis of TA–DIC data, reef metabolism was dominated by organic over inorganic carbon cycling at both sites, with net heterotrophy and net calcium carbonate dissolution dominating the majority of observations. The results also highlight the potentially strong influence of terrestrial freshwater runoff on surface seawater conditions, and the challenges associated with evaluating and characterizing this influence on benthic habitats. The Bocas del Toro reef is a unique system that deserves attention to better understand the mechanisms that allow corals and coral reefs to persist under increasingly challenging environmental conditions. [ABSTRACT FROM AUTHOR]

Ocean alkalinity enhancement (OAE) via the enhanced weathering of alkaline minerals is a promising carbon dioxide removal (CDR) technology. Theoretically, these includes iron and steel slags, although their dissolution kinetics in seawater are unknown. Here, we conducted lab-scale experiments to assess the alkalinity generation potential and dissolution kinetics of various slags in seawater. We show that the alkalinity generated per mass of iron slag was logarithmic, i.e., higher amounts of iron slag added had diminishing alkalinity returns. In contrast, the relatively quick dissolution of steel slags and their linear generation of alkalinity per mass of feedstock dissolved in seawater makes them better OAE candidates. Furthermore, despite the presence of potentially toxic metals in these feedstocks, their low to non-existent presence as dissolution products suggests that harmful concentrations should not be reached, at least for the slag tested here. Finally, if all steel slag produced annually was used for OAE, between 10 and 22 gigatonnes of CO2 could be captured cumulatively by 2,100, highlighting significant CDR potential by slags.

Infaunal invertebrates are affected by the overlying water and the sediment in which they live. Therefore, understanding how these environmental conditions impact infauna is critical for evaluating how they may respond to future changes in these conditions due to climate change. Here, we considered which abiotic variables, for example, salinity, sediment characteristics (i.e. mean grain size, sorting), and water column and sediment carbonate chemistry, influence infaunal invertebrate communities and juvenile bivalve abundance at intertidal sites. We used data from sites in two regions in New Brunswick, Canada with contrasting tidal regimes and oceanographic conditions, the Bay of Fundy and the Southern Gulf of St. Lawrence. We were particularly interested in bivalve recruitment due to the importance of bivalves in ecosystem services and predicted sensitivity to climate change impacts. Using data collected in 2020 and 2021, statistical modeling was done to determine which abiotic variables were potential drivers of multivariate community composition as well as species richness, total abundance, and juvenile bivalve abundance. We found that carbonate chemistry variables, both sediment and water, explained a large amount of variation (~ 7–44%) in infaunal invertebrate communities in the two regions in both our multivariate and univariate analyses. Sediment pH explained the most variation (16.9%) in the multivariate analyses for the Bay of Fundy sites. However, in the Southern Gulf of St. Lawrence, salinity explained the most variation (9.8%) in the multivariate community composition. In the univariate modeling, alkalinity, either water column or sediment, was included in all top models for all four dependent variables, suggesting the importance of this carbonate chemistry variable for bivalves and infaunal communities. Climate change is expected to have large impacts on carbonate chemistry conditions in the oceans, specifically pH, carbonate availability, and alkalinity. The influence of carbonate chemistry parameters on infaunal invertebrate communities in these regions shows the potential sensitivity these animals have to future oceanic conditions. [ABSTRACT FROM AUTHOR]

Sea‐ice dynamics can affect carbon cycling in polar oceans, with sea‐ice ikaite acting as a potentially important carbon pump. However, there is no large‐scale direct field evidence to support this. Here we used a unique data set that combined continuous measurements of atmospheric and water CO2 concentrations with water chemistry data collected over 1,200 km along the East Siberian Sea, the widest Arctic shelf sea. Our results reveal large spatial heterogeneity of sea‐ice ikaite contents, which directly interact with carbonate chemistry in the water column. Our findings demonstrate that the CO2 drawdown by sea‐ice ikaite dissolution could be as important as that by primary production. We suggest that the role of ikaite in regulating the seasonal carbon cycle on a regional scale could be more important than we previously thought. Effects of the warmer climate on sea ice loss might also play a role in the ikaite inventory. Plain Language Summary: The extent of sea ice in the Arctic Ocean has been known to be an active player in the carbon cycle. Recent studies have discovered that sea ice formation in winter leads to precipitation of calcium carbonate crystals (known as ikaite) and expels carbon dioxide (CO2) either to air or to deeper water with sinking of a heavy cold‐water mass (known as brine). In summer, ikaite in sea ice dissolves when the sea ice melts. This process takes CO2 away from air and convert it to dissolved inorganic carbon in surface ocean. Our study used non‐stop real‐time field measurements of air and water CO2 levels and water column data to investigate variability of carbonate chemistry across the East Siberian Sea. We observed that the distribution pattern of ikaite in sea ice varied largely with space. Ikaite dissolution in association with sea ice melting could take up similar amount of air CO2 as primary production does. Our findings suggest that more research efforts should be made to assess the effect of ikaite dynamics on the seasonal carbon cycle in a warmer climate. Key Points: Strong spatial heterogeneity of ikaite distribution in sea ice across East Siberian Sea is revealed via carbonate variability in water columnSea‐ice ikaite dissolution together with primary production was responsible for pCO2 drawdown in summer in the East Siberian SeaThe role of sea‐ice ikaite dynamics in the seasonal carbon cycle could be subject to change in a warmer climate [ABSTRACT FROM AUTHOR]

In coastal regions and marginal bodies of water, the increase in partial pressure of carbon dioxide (pCO2) in many instances is greater than that of the open ocean due to terrestrial (river, estuarine, and wetland) influences, decreasing buffering capacity and/or increasing water temperatures. Coastal oceans receive freshwater from rivers and groundwater as well as terrestrial-derived organic matter, both of which have a direct influence on coastal carbonate chemistry. The objective of this research is to determine if coastal marshes in Georgia, USA, may be "hot-spots" for acidification due to enhanced inorganic carbon sources and if there is terrestrial influence on offshore acidification in the South Atlantic Bight (SAB). The results of this study show that dissolved inorganic carbon (DIC) and total alkalinity (TA) are elevated in the marshes compared to predictions from conservative mixing of the freshwater and oceanic end-members, with accompanying pH around 7.2 to 7.6 within the marshes and aragonite saturation states (ΩAr) <1. In the marshes, there is a strong relationship between the terrestrial/estuarine-derived organic and inorganic carbon and acidification. Comparisons of pH, TA, and DIC to terrestrial organic material markers, however, show that there is little influence of terrestrial-derived organic matter on shelf acidification during this period in 2014. In addition, ΩAr increases rapidly offshore, especially in drier months (July). River stream flow during 2014 was anomalously low compared to climatological means; therefore, offshore influences from terrestrial carbon could also be decreased. The SAB shelf may not be strongly influenced by terrestrial inputs to acidification during drier than normal periods; conversely, shelf waters that are well-buffered against acidification may not play a significant role in mitigating acidification within the Georgia marshes. [ABSTRACT FROM AUTHOR]

The long‐term absorption by the oceans of atmospheric carbon dioxide is leading to the slow decline of ocean pH, a process termed ocean acidification (OA). The Arctic is a challenging region to gather enough data to examine the changes in carbonate chemistry over sufficient scales. However, algorithms that calculate carbonate chemistry parameters from more frequently measured parameters, such as temperature and salinity, can be used to fill in data gaps. Here, these published algorithms were evaluated against in situ measurements using different data input types (data from satellites or in situ re‐analysis climatologies) across the Arctic Ocean. With the lowest uncertainties in the Atlantic influenced Seas (AiS), where re‐analysis inputs achieved total alkalinity estimates with Root Mean Squared Deviation (RMSD) of 21 μmol kg−1 and a bias of 2 μmol kg−1 (n = 162) and dissolved inorganic carbon RMSD of 24 μmol kg−1 and bias of −14 μmol kg−1 (n = 262). AiS results using satellite observation inputs show similar bias but larger RMSD, although due to the shorter time span of available satellite observations, more contemporary in situ data would provide further assessment and improvement. Synoptic‐scale observations of surface water carbonate conditions in the Arctic are now possible to monitor OA, but targeted in situ data collection is needed to enable the full exploitation of satellite observation‐based approaches. Plain Language Summary: The long‐term absorption by the oceans of atmospheric carbon dioxide is leading to the slow decline of ocean pH, a process termed ocean acidification (OA). Sea surface salinity and temperature measurements from satellites or in situ re‐analysis products can be used as input to empirical algorithms to calculate OA parameters. This paper provides a first analysis of published Arctic Ocean empirical algorithms to estimate surface water OA parameters using observation‐based data sets. Results show promise in the Atlantic influenced Seas using both in situ re‐analysis and satellite products, but satellite salinity is relatively recent, and a paucity of in situ data in the satellite salinity era precludes a robust assessment. To fully exploit satellite‐based approaches, efforts need to focus on collecting in situ data while these satellites are overhead and operating in orbit. Key Points: Observation‐based data sets enable synoptic spatio‐temporal assessments of Arctic Ocean carbonate system parametersRe‐analysis and satellite products predict total alkalinity with accuracies of ∼21 μmol kg−1Targeted in situ data collection is needed to fully exploit satellite observations in the Arctic to enable carbonate system monitoring [ABSTRACT FROM AUTHOR]

Globally, oyster reef restoration is one of the most widely applied coastal restoration interventions. While reefs are focal points of processes tightly linked to the carbonate system such as shell formation and respiration, how these processes alter reef carbonate chemistry relative to the surrounding seawater is unclear. Moreover, coastal systems are increasingly impacted by coastal acidification, which may affect reef carbonate chemistry. Here, we characterized the growth of multiple constructed reefs as well as summer variations in pH and carbonate chemistry of reef‐influenced seawater (in the middle of reefs) and ambient seawater (at locations ~50 m outside of reefs) to determine how reef chemistry was altered by the reef community and, in turn, impacts resident oysters. High frequency monitoring across three subtidal constructed reefs revealed reductions of daily mean and minimum pH (by 0.05–0.07 and 0.07–0.12 units, respectively) in seawater overlying reefs relative to ambient seawater (p <.0001). The proportion of pH measurements below 7.5, a threshold shown to negatively impact post‐larval oysters, were 1.8×–5.2× higher in reef seawater relative to ambient seawater. Most reef seawater samples (83%) were reduced in total alkalinity relative to ambient seawater samples, suggesting community calcification was a key driver of modified carbonate chemistry. The net metabolic influence of the reef community resulted in reductions of CaCO3 saturation state in 78% of discrete samples, and juvenile oysters placed on reefs exhibited slower shell growth (p <.05) compared to oysters placed outside of reefs. While differences in survival were not detected, reef oysters may benefit from enhanced survival or recruitment at the cost of slowed growth rates. Nevertheless, subtidal restored reef communities modified seawater carbonate chemistry in ways that likely increased oyster vulnerability to acidification, suggesting that carbonate chemistry dynamics warrant consideration when determining site suitability for oyster restoration, particularly under continued climate change. [ABSTRACT FROM AUTHOR]

Ocean acidification (OA) threatens coral reef persistence by decreasing calcification and accelerating the dissolution of reef frameworks. The carbonate chemistry of coastal areas where many reefs exist is strongly influenced by the metabolic activity of the underlying benthic community, contributing to high spatiotemporal variability. While characterizing this variability is difficult, it has important implications for the progression of OA and the persistence of the ecosystems. Here, we characterized the carbonate chemistry at 38 permanent stations located along 10 inshore‐offshore transects spanning 250 km of the Florida Coral Reef (FCR), which encompass four major biogeographic regions (Biscayne Bay, Upper Keys, Middle Keys, and Lower Keys) and four shelf zones (inshore, mid‐channel, offshore, and oceanic). Data have been collected since 2010, with approximately bi‐monthly periodicity starting in 2015. Increasing OA, driven by increasing DIC, was detected in the mid‐channel, offshore, and oceanic zones in every biogeographic region. In the inshore zone, however, increasing TA counteracted any measurable OA trend. Strong seasonal variability occurred at inshore sites and included periods of both exacerbated and mitigated OA. Seasonality was region‐dependent, with greater variability in the Lower and Middle Keys. Elevated pH and aragonite saturation states (ΩAr) were observed in the Upper and Middle Keys, which could favor reef habitat persistence in these regions. Offshore reefs in the FCR could be more susceptible to global OA by experiencing open‐ocean‐like water chemistry conditions. By contrast, higher seasonal variability at inshore reefs could offer a temporary OA refuge during periods of enhanced primary production. Plain Language Summary: Elevated carbon dioxide (CO2) input into the atmosphere is causing the acidification of the oceans, hindering the ability of corals to grow their hard skeleton and thus affecting coral reef habitat persistence. However, shallow ecosystems such as coral reefs can experience strong temporal and spatial variability in carbonate chemistry (such as pH and CO2), which may both mitigate or exacerbate exposure to ocean acidification (OA). From 2010 to 2021, we sampled seawater carbonate chemistry at 38 permanent stations along and across the Florida Coral Reef to assess its variability among seasons, years, and reef areas. OA was detected in most of the Florida Coral Reef, including the mid‐channel and offshore reefs. However, there were no OA trends at inshore reefs, where seasonal variability in the carbonate parameters was the greatest. Among the regions, the Upper and Middle Keys had higher pH values compared with the Lower Keys, suggesting more favorable conditions for reef persistence in the first two regions. This temporal and spatial variability may have important implications for coral reef resilience to OA. Key Points: Interannual acidification trends were detected in the mid‐channel, offshore, and oceanic zones of Florida's Coral ReefAt the inshore reefs, strong seasonal variability in carbonate chemistry and increasing TA mitigated or obscured acidification trendsHigher pH and aragonite saturation states occur in the Upper and Middle Keys, which could favor reef habitat persistence in these regions [ABSTRACT FROM AUTHOR]

The air–sea exchange of carbon dioxide (CO2) on a global scale is a key factor in understanding climate change and predicting its effects. The magnitude of sea spray’s contribution to this flux is currently highly uncertain. Constraining CO2’s diffusion in sea spray droplets is important for reducing error margins in global estimates of oceanic CO2 uptake and release. The timescale for CO2 gas diffusion within sea spray is known to be shorter than the timescales for the droplets’ physical changes to take place while aloft. However, the rate of aqueous carbonate reactions relative to these timescales has not been assessed. This study investigates the timescales of droplet physical changes to those of chemical transformations across the H2CO3/HCO3−/CO32− sequence. We found that physical timescales are rate limiting and that evaporation drives carbonate species into gaseous CO2, promoting the production and evasion of CO2 from sea spray droplets. This has important implications for carbon cycling and feedback in the surface ocean.

Abstract The long‐term absorption by the oceans of atmospheric carbon dioxide is leading to the slow decline of ocean pH, a process termed ocean acidification (OA). The Arctic is a challenging region to gather enough data to examine the changes in carbonate chemistry over sufficient scales. However, algorithms that calculate carbonate chemistry parameters from more frequently measured parameters, such as temperature and salinity, can be used to fill in data gaps. Here, these published algorithms were evaluated against in situ measurements using different data input types (data from satellites or in situ re‐analysis climatologies) across the Arctic Ocean. With the lowest uncertainties in the Atlantic influenced Seas (AiS), where re‐analysis inputs achieved total alkalinity estimates with Root Mean Squared Deviation (RMSD) of 21 μmol kg−1 and a bias of 2 μmol kg−1 (n = 162) and dissolved inorganic carbon RMSD of 24 μmol kg−1 and bias of −14 μmol kg−1 (n = 262). AiS results using satellite observation inputs show similar bias but larger RMSD, although due to the shorter time span of available satellite observations, more contemporary in situ data would provide further assessment and improvement. Synoptic‐scale observations of surface water carbonate conditions in the Arctic are now possible to monitor OA, but targeted in situ data collection is needed to enable the full exploitation of satellite observation‐based approaches.

Natural processes such as upwelling of deeper-water masses change the physical-chemical conditions of the water column creating localized ocean acidification events that can have an impact on the natural communities. This study was performed in a coral reef system of an archetypical bay within the Tayrona National Natural Park (PNNT) (Colombia), and aimed to quantify net calcification rates of a foundational coral species within a temporal context (6 months) taking into account the dynamics of seasonal upwelling that influence the study area. Net calcification rates of coral fragments were obtained in situ by the alkalinity anomaly technique in short-term incubations (~2.5 h). We found a significant effect of the upwelling on net calcification rates (Gnet) (p < 0.05) with an 42% increase in CaCO3 accretion compared to non-upwelling season. We found an increase in total alkalinity (AT) and dissolved inorganic carbon (DIC) with decreased aragonite saturation (Ωara) for the upwelling months, indicating an influence of the Subtropical Under Water mass (SAW) in the PNNT coral community. Significant negative correlations between net calcification with temperature and Ωara, which indicates a positive response of M. auretenra with the upwelling conditions, thus, acting as “enhancer” of resilience for coral calcification.

The Northwest Atlantic Shelf (NAS) region has experienced accelerated warming, heatwaves, and is susceptible to ocean acidification, yet also suffers from a paucity of carbonate chemistry observations, particularly at depth. We address this critical data gap by developing three different neural network models to predict dissolved inorganic carbon (DIC) and total alkalinity (TA) in the NAS region from more readily available hydrographic and satellite data. The models predicted DIC with r2 between 0.913–0.963 and root mean square errors (RMSE) between 15.4–23.7 (μmol kg−1) and TA with r2 between 0.986–0.983 and RMSE between 9.0–10.4 (μmol kg−1) on an unseen test data set that was not used in training the models. Cross‐validation analysis revealed that all models were insensitive to the choice of training data and had good generalization performance on unseen data. Uncertainty in DIC and TA were low (coefficients of variation 0.1%–1%). Compared with other predictive models of carbonate system variables in this region, a larger and more diverse data set with full seasonal coverage and a more sophisticated model architecture resulted in a robust predictive model with higher accuracy and precision across all seasons. We used one of the models to generate a reconstructed seasonal distribution of carbonate chemistry fields based on DIC and TA predictions that shows a clear seasonal progression and large spatial gradients consistent with observations. The distinct models will allow for a range of applications based on the predictor variables available and will be useful to understand and address ocean sustainability challenges. Plain Language Summary: The U.S. northeast coast is particularly susceptible to climate change and ocean acidification. However, the lack of observations on seawater carbonate chemistry makes it difficult to assess the impacts of ocean acidification on the region. We address this information gap by developing three different machine learning models to predict carbonate system parameters from more readily available field and satellite data. The models predicted carbonate system parameters with high accuracy and good precision. Compared with other models of carbonate chemistry variables for this region, a larger data set with full seasonal and vertical coverage of the water column and a more complex model architecture resulted in a robust model with low error and uncertainty across all four seasons as well as in surface and subsurface waters. The reconstructed distributions of carbonate chemistry fields on U.S. northeast coast based on one of the models were consistent with observations. We anticipate that the distinct versions of the model will allow for a wide range of different applications based on the predictor variables that are available. Key Points: Three neural network models were developed to predict carbonate chemistry for the Northwest Atlantic Shelf with high precision and accuracyDistinct models have increased numbers of predictors that improve model performance and allow for a wide range of different applicationsOne model was applied to modern‐day hydrographic and satellite data to generate seasonal maps of surface and bottom water conditions [ABSTRACT FROM AUTHOR]

Natural processes such as upwelling of deeper-water masses change the physical-chemical conditions of the water column creating localized ocean acidification events that can have an impact on the natural communities. This study was performed in a coral reef system of an archetypical bay within the Tayrona National Natural Park (PNNT) (Colombia), and aimed to quantify net calcification rates of a foundational coral species within a temporal context (6 months) taking into account the dynamics of seasonal upwelling that influence the study area. Net calcification rates of coral fragments were obtained in situ by the alkalinity anomaly technique in short-term incubations (~2.5 h). We found a significant effect of the upwelling on net calcification rates (Gnet) (p < 0.05) with an 42% increase in CaCO3 accretion compared to non-upwelling season. We found an increase in total alkalinity (AT) and dissolved inorganic carbon (DIC) with decreased aragonite saturation (Ωara) for the upwelling months, indicating an influence of the Subtropical Under Water mass (SAW) in the PNNT coral community. Significant negative correlations between net calcification with temperature and Ωara, which indicates a positive response of M. auretenra with the upwelling conditions, thus, acting as "enhancer" of resilience for coral calcification. [ABSTRACT FROM AUTHOR]

To accurately predict the impacts of ocean acidification on shallow-water ecosystems, we must account for the biogeochemical impact of local benthic communities, as well as the connectivity between offshore and onshore water masses. Estimation of residence time can help quantify this connectivity and determine the degree to which the benthos can influence the chemistry of the overlying water column. We present estimates of nearshore residence time for Guam and utilize these estimates to model the effects of benthic ecosystem metabolism on the coral reef carbonate system. Control volume and particle tracking approaches were used to estimate nearshore residence time. These estimates were paired with observed patterns in the reef carbonate system around Guam using water samples collected by NOAA's National Coral Reef Monitoring Program. Model performance results suggest that when considering the effects of benthic metabolism on the carbonate system, it is paramount to represent the contact time of the water volume with the benthos. Even coarse estimates of residence time significantly increase model skill. We observed the highest predictive skill in models including control volume derived estimates of residence time, but only when those estimates were included as an interaction with benthic composition. This work shows that not only is residence time critically important to better predict biogeochemical variability in coral reef environments, but that even coarse hydrodynamic models can provide useful residence time estimates at management relevant, whole-ecosystem scales. [ABSTRACT FROM AUTHOR]

The ratio of sodium to calcium (Na/Ca) in foraminiferal calcite has been proposed as a proxy for salinity, yet relatively little is known about the incorporation of sodium into the shells of foraminifera. Ongoing debates include the location of Na in the calcite crystal lattice, the possibility that at least some Na might be complexed with organics, and the influence of spines/spine bases. We present new Na/Ca measurements, determined using both solution and laser ablation ICP-MS, of the planktonic foraminifera Globigerinoides ruber (white) from plankton tows and sediment traps spanning a wide salinity range (32.5–40.7 salinity units), laboratory cultures under varying carbonate chemistry, and globally-distributed core-top samples. Our results show that Na/Ca in recently living foraminifera measured by laser ablation ICP-MS is elevated by up to 5 mmol/mol (∼85%) relative to the same samples measured by solution ICP-MS (the same comparison for Mg/Ca shows excellent agreement between the techniques). Na/Ca in recently living foraminifera measured by laser ablation ICP-MS displays a significant relationship with salinity above ∼36 salinity units with a slope of ∼0.7 mmol/mol/salinity unit; however, only a weak relationship is observed between salinity and Na/Ca measured by solution ICP-MS. We propose that Na is incorporated in at least two discrete phases; a primary phase within the CaCO 3 mineral, and a (or likely multiple) secondary phase(s). Possibilities for these secondary phases include residual metastable CaCO 3 , fluid inclusions, high Na/Ca spine bases, and organics. These secondary phases contribute to spatially-resolved analyses (i.e. laser ablation ICP-MS) of recently living foraminifera but are removed by crushing/oxidative cleaning for solution ICP-MS, and during early diagenesis, as evidenced by the agreement between laser analysis of coretop samples and Na/Ca measured by solution. The amount of one of these secondary phases, or the amount of Na within this phase, appears to vary as a function of salinity, and is likely the principal driver of the previously observed steep Na/Ca-salinity relationship in recently living foraminifera analysed by laser ablation. Overall, we find salinity, temperature, carbonate chemistry, and bottom water saturation state (Ω calcite) all have a significant but relatively weak effect on Na/Ca in the primary calcite phase. As such, Na/Ca in planktonic foraminifera recovered from sediment cores is unlikely to find widespread utility as a salinity proxy. [ABSTRACT FROM AUTHOR]

Ocean acidification (OA) refers to a global decline in the average pH of seawater driven by the absorption of atmospheric carbon dioxide (CO2). Marine macroalgae, while affected by this pH change, are also able to modify seawater pH through their own interaction with inorganic carbon in the carbonate system. Through this action, macroalgae-dominated habitats are potential refugia from OA for associated marine species. This review summarises the most prominent literature on the role of macroalgae in OA mitigation and the potential of macroalgal habitats to serve as OA refugia. It includes a brief overview of macroalgal distribution in an effort to illustrate where such refugia might be most prevalent. Macroalgae influence seawater carbonate chemistry through the absorption of CO2 and HCO3- during photosynthesis, raising surrounding seawater pH in the process. This transient effect on seawater chemistry could provide some respite from the negative effects of OA for many marine species. This refuge role varies over a range of scales along with macroalgal architecture, which varies in size from low-growing turfs to large canopy-forming stands. The associated pH changes can range over various temporal (daily and seasonal) and spatial (from centimetre to kilometre) scales. Areas of high macroalgal biomass are likely to play an important role as significant OA refugia. Such communities are distributed widely throughout the globe. Large brown macroalgae (Laminariales) dominated communities are common in temperate regions, while members of the Fucales are responsible for substantial macroalgal stands in warmer tropical regions. These marine fields and forests have great potential to serve as localised refuges from OA. While more work needs to be done to clarify the effect of macroalgal communities on seawater pH on a large scale, such refuge areas could become important considerations for the management of marine resources and in protected area selection. [ABSTRACT FROM AUTHOR]

The ultimate fate, over the course of millennia, of nearly all of the carbon dioxide formed by humankind is for it to react with calcium carbonate in the world's oceans. Although, this reaction is of global relevance, aspects of the calcite dissolution reaction remain poorly described with apparent contradictions present throughout the expansive literature. In this perspective we aim to evidence how a lack of appreciation of the role of mass‐transport may have hampered developments in this area. These insights have important implications for both idealised experiments performed under laboratory conditions and for the measurement and modelling of oceanic calcite sediment dissolution. [ABSTRACT FROM AUTHOR]

Compared with the open ocean, knowledge of pH variability in coastal waters is rudimentary, especially in Africa. This is concerning as quantifying local pH conditions is critical when assessing the response of coastal species to future ocean acidification scenarios. The objective of this study was to capture some of the variability in pH at scales and sites relevant to coastal marine organisms in a South African temperate embayment (Algoa Bay, Indian Ocean). We used a sampling approach that captured spatial (at a resolution of ∼10 km), monthly and diel (24-hour) variability in pH and associated physical and biological parameters at offshore and shallow inshore sites in Algoa Bay. We found that pH and associated parameters (temperature, calculated pCO2, chlorophyll a) varied over space and time in Algoa Bay. The range in pH was 0.30 units at offshore sites and 0.46 at inshore sites, and the average pH was 8.10 (SD 0.06) and 8.10 (SD 0.13) at these sites, respectively, which is typical for coastal environments. Our results showed that both biological factors (at the offshore sites) and salinity (at the inshore sites) may influence temporal and spatial variability in pH. We also identified a shallow inshore site with high levels of macroalgal growth that had consistently higher average daytime pH levels (8.33 [SD 0.07]), which may serve as an ocean acidification refuge for coastal marine species. This is the first comprehensive pH-monitoring study to be implemented in a nearshore coastal area in Africa and provides recommendations for monitoring in other understudied regions. [ABSTRACT FROM AUTHOR]

Ocean acidification (OA) is expected to modify the structure and function of coral reef ecosystems by reducing calcification, increasing bioerosion, and altering the physiology of many marine organisms. Much of our understanding of these relationships is based on experiments with static OA treatments, although evidence suggests that the magnitude of diurnal fluctuations in carbonate chemistry may modulate the calcification response to OA. These light‐mediated swings in seawater pH are projected to become more extreme with OA, yet their impact on bioerosion remains unknown. We evaluated the influence of diurnal carbonate chemistry variability on the bioerosion rates of two Caribbean sponges: the zooxanthellate Cliona varians and azooxanthellate Cliothosa delitrix. Replicate fragments from multiple colonies of each species were exposed to four precisely controlled pH treatments: contemporary static (8.05 ± 0.00; mean pH ± diurnal pH oscillation), contemporary variable (8.05 ± 0.10), future OA static (7.80 ± 0.00), and future OA variable (7.80 ± 0.10). Significantly enhanced bioerosion rates, determined using buoyant weight measurements, were observed under more variable conditions in both the contemporary and future OA scenarios for C. varians, whereas the same effect was only apparent under contemporary pH conditions for C. delitrix. These results indicate that variable carbonate chemistry has a stimulating influence on sponge bioerosion, and we hypothesize that bioerosion rates evolve non‐linearly as a function of pCO2 resulting in different magnitudes and directions of rate enhancement/reduction between day and night, even with an equal fluctuation around the mean. This response appeared to be intensified by photosymbionts, evident by the consistently higher percent increase in bioerosion rates for photosynthetic C. varians across all treatments. These findings further suggest that more variable natural ecosystems may presently experience elevated sponge bioerosion rates and that the heightened impact of OA enhanced bioerosion on reef habitat could occur sooner than prior predictions. [ABSTRACT FROM AUTHOR]

The Ulva prolifera bloom is considered one of the most serious ecological disasters in the Yellow Sea in the past decade, forming a carbon sink in its source area within a short period but becoming a carbon source at its destination. To explore the effects of different environmental changes on seawater dissolved carbon pools faced by living U. prolifera in its originating area, U. prolifera were cultured in three sets with different light intensity (54, 108, and 162 μmol m−2 s−1), temperature (12, 20, and 28 °C) and nitrate concentration gradients (25, 50, and 100 μmol L−1). The results showed that moderate light (108 μmol m−2 s−1), temperature (20 °C), and continuous addition of exogenous nitrate significantly enhanced the absorption of dissolved inorganic carbon (DIC) in seawater by U. prolifera and most promoted its growth. Under the most suitable environment, the changes in the seawater carbonate system were mainly dominated by biological production and denitrification, with less influence from aerobic respiration. Facing different environmental changes, U. prolifera continuously changed its carbon fixation mode according to tissue δ13C results, with the changes in the concentrations of various components of DIC in seawater, especially the fluctuation of HCO 3 − and CO 2 concentrations. Enhanced light intensity of 108 μmol m−2 s−1 could shift the carbon fixation pathway of U. prolifera towards the C 4 pathway compared to temperature and nitrate stimulation. Environmental conditions at the origin determined the amount of dissolved carbon fixed by U. prolifera. Therefore, more attention should be paid to the changes in marine environmental conditions at the origin of U. prolifera , providing a basis for scientific management of U. prolifera. [Display omitted] • Moderate light, temperature and nitrate addition boost U. prolifera DIC absorption. • U. prolifera adapts carbon fixation modes to environmental changes. • Origin environmental conditions determine U. prolifera's carbon sink contribution. [ABSTRACT FROM AUTHOR]

Ocean acidification (OA) refers to a global decline in the average pH of seawater driven by the absorption of atmospheric carbon dioxide (CO2). Marine macroalgae, while affected by this pH change, are also able to modify seawater pH through their own interaction with inorganic carbon in the carbonate system. Through this action, macroalgae-dominated habitats are potential refugia from OA for associated marine species. This review summarises the most prominent literature on the role of macroalgae in OA mitigation and the potential of macroalgal habitats to serve as OA refugia. It includes a brief overview of macroalgal distribution in an effort to illustrate where such refugia might be most prevalent. Macroalgae influence seawater carbonate chemistry through the absorption of CO2 and HCO3− during photosynthesis, raising surrounding seawater pH in the process. This transient effect on seawater chemistry could provide some respite from the negative effects of OA for many marine species. This refuge role varies over a range of scales along with macroalgal architecture, which varies in size from low-growing turfs to large canopy-forming stands. The associated pH changes can range over various temporal (daily and seasonal) and spatial (from centimetre to kilometre) scales. Areas of high macroalgal biomass are likely to play an important role as significant OA refugia. Such communities are distributed widely throughout the globe. Large brown macroalgae (Laminariales) dominated communities are common in temperate regions, while members of the Fucales are responsible for substantial macroalgal stands in warmer tropical regions. These marine fields and forests have great potential to serve as localised refuges from OA. While more work needs to be done to clarify the effect of macroalgal communities on seawater pH on a large scale, such refuge areas could become important considerations for the management of marine resources and in protected area selection.

The interplay between ocean circulation and coral metabolism creates highly variable biogeochemical conditions in space and time across tropical coral reefs. Yet, relatively little is known quantitatively about the spatiotemporal structure of these variations. To address this gap, we use the Coupled Ocean Atmosphere Wave and Sediment Transport (COAWST) model, to which we added the Biogeochemical Elemental Cycling (BEC) model computing the biogeochemical processes in the water column, and a coral polyp physiology module that interactively simulates coral photosynthesis, respiration and calcification. The coupled model, configured for the north-shore of Moorea Island, successfully simulates the observed (i) circulation across the wave regimes, (ii) magnitude of the metabolic rates, and (iii) large gradients in biogeochemical conditions across the reef. Owing to the interaction between coral net community production (NCP) and coral calcification, the model simulates distinct day versus night gradients, especially for pH and the saturation state of seawater with respect to aragonite (Ωα). The strength of the gradients depends non-linearly on the wave regime and the resulting residence time of water over the reef with the low wave regime creating conditions that are considered as “extremely marginal” for corals. With the average water parcel passing more than twice over the reef, recirculation contributes further to the accumulation of these metabolic signals. We find diverging temporal and spatial relationships between total alkalinity (TA) and dissolved inorganic carbon (DIC) (≈ 0.16 for the temporal vs. ≈ 1.8 for the spatial relationship), indicating the importance of scale of analysis for this metric. Distinct biogeochemical niches emerge from the simulated variability, i.e., regions where the mean and variance of the conditions are considerably different from each other. Such biogeochemical niches might cause large differences in the exposure of individual corals to the stresses associated with e.g., ocean acidification. At the same time, corals living in the different biogeochemical niches might have adapted to the differing conditions, making the reef, perhaps, more resilient to change. Thus, a better understanding of the mosaic of conditions in a coral reef might be useful to assess the health of a coral reef and to develop improved management strategies.

Seawater carbonate chemistry links Earth's climate and carbon cycle through the production and preservation of carbonate sediments. Models and carbonate facies abundance records have generated hypotheses about trajectories of seawater carbonate chemistry, including responses to key events in the evolutionary history of carbonate biomineralizers. However, tests of these hypotheses have remained elusive. We applied a novel proxy for the carbonate mineral saturation state (Ω) of seawater based on the diameters of ooids—concentrically‐coated carbonate sand grains—to estimate Ω, dissolved inorganic carbon, alkalinity, and pH of seawater spanning Phanerozoic time. Reconstructed Ω values decreased sharply around ∼120 Ma, which we interpret as the fingerprint of the Mid‐Mesozoic Revolution of planktic calcifiers. Shifts in Ω across Ordovician time also suggest a possible causal relationship with the Great Ordovician Biodiversification Event. Our results demonstrate that ooid sizes are a useful tool for reconstructing Earth's ancient carbon cycle. Plain Language Summary: Earth's oceans play an important role in removing carbon from Earth's surface environments. One of the ways this happens is through the production and burial of calcium carbonate sediments, which include shells and calcium carbonate minerals formed in other ways. The chemistry of the oceans, including pH and the concentrations of carbonate ions, affect how easy it is for carbonate minerals to form, and whether they can survive long enough to be permanently buried on the seafloor. Tracking these aspects of the chemistry of ancient oceans can enable scientists to better understand the balance of carbon entering and exiting Earth's surface environments in the past. Until recently, we have not had the right tools to extract this information from sedimentary rocks. Here, we used a recently developed method that uses the sizes of ooids—sand grains that grow by accumulating concentric layers of calcium carbonate—to track ancient ocean carbonate chemistry. We compared the results of our new approach with previous efforts and found that our approach works well. Our work demonstrates that ooid size measurements can improve our understanding of ancient oceans. Key Points: We estimated seawater calcite saturation states spanning Phanerozoic time using a proxy based on ooid sizeWe combined our calcite saturation state values with pCO2 and seawater chemistry proxy data to calculate seawater carbonate chemistryDissolved inorganic carbon, alkalinity, and pH estimates based on the ooid size proxy agree with predictions from carbon cycle models and carbonate facies records [ABSTRACT FROM AUTHOR]

The U.S. Pacific Islands span a dramatic natural gradient in climate and oceanographic conditions, and benthic community states vary significantly across the region’s coral reefs. Here we leverage a decade of integrated ecosystem monitoring data from American Samoa, the Mariana Archipelago, the main and Northwestern Hawaiian Islands, and the U.S. Pacific Remote Island Areas to evaluate coral reef community structure and reef processes across a strong natural gradient in pH and aragonite saturation state (Ωar). We assess spatial patterns and temporal trends in carbonate chemistry measured in situ at 37 islands and atolls between 2010 and 2019, and evaluate the relationship between long-term mean Ωar and benthic community cover and composition (benthic cover, coral genera, coral morphology) and reef process (net calcium carbonate accretion rates). We find that net carbonate accretion rates demonstrate significant sensitivity to declining Ωar, while most benthic ecological metrics show fewer direct responses to lower-Ωar conditions. These results indicate that metrics of coral reef net carbonate accretion provide a critical tool for monitoring the long-term impacts of ocean acidification that may not be visible by assessing benthic cover and composition alone. The perspectives gained from our long-term, in situ, and co-located coral reef environmental and ecological data sets provide unique insights into effective monitoring practices to identify potential for reef resilience to future ocean acidification and inform effective ecosystem-based management strategies under 21st century global change.

To understand the effects of the glacial meltwater supply on carbonate chemistry and the air–sea CO2 flux within the fjord, water samples were collected in Bowdoin Fjord in northwestern Greenland for dissolved inorganic carbon (DIC) concentration, total alkalinity (TA), oxygen isotopic ratio (δ18O), and chlorophyll a concentration analyses in the summers of 2016 and 2017. The partial pressure of CO2 (pCO2) in surface water, calculated from DIC and TA, was less than 200 µatm, and was significantly lower than that in the atmosphere (399 ± 3 µatm). Therefore, surface water of the fjord acts as sink for CO2 in the atmosphere (–4.9 ± 0.7 mmol m–2 d–1). To evaluate the effects of freshwater and land-derived substances by glacial meltwater on pCO2 in the fjord, we calculated the changes of pCO2 in salinity and carbonate chemistry that would result from the inflow of glacial meltwater into the fjord. The calculated pCO2 was high near the calving front, where the contribution of glacier meltwater was significant. Examination of the relationship between salinity-normalized DIC and TA, which was considered DIC and TA input from the land, suggested that the land-derived high pCO2 freshwater affected mainly by the remineralization of the organic matter by bacterial activity was supplied to the Bowdoin Fjord.

As concerns about ocean acidification continue to grow, the importance of macroalgal communities in buffering coastal seawater biogeochemistry through their metabolisms is gaining more attention. However, studies on diel and seasonal fluctuations in seawater chemistry within these communities are still rare. Here, we characterized the spatial and temporal heterogeneity in diel and seasonal dynamics of seawater carbonate chemistry and dissolved oxygen (DO) in three types of macroalgal habitats (UAM: ulvoid algal mat dominated, TAM: turf algal mat dominated, and SC: Sargassum horneri and coralline algae dominated). Our results show that diel fluctuations in carbonate parameters and DO varied significantly among habitat types and seasons due to differences in their biological metabolisms (photosynthesis and calcification) and each site’s hydrological characteristics. Specifically, carbonate parameters were most affected by biological metabolisms at the SC site, and by environmental variables at the UAM site. Also, we demonstrate that macroalgal communities reduced ocean acidification conditions when ocean temperatures supported photosynthesis and thereby the absorption of dissolved inorganic carbon. However, once temperatures exceeded the optimum ranges for macroalgae, respiration within these communities exceeded photosynthesis and increased CO2 concentrations, thereby exacerbating ocean acidification conditions. We conclude that the seawater carbonate chemistry is strongly influenced by the metabolisms of the dominant macroalgae within these different habitat types, which may, in turn, alter their buffering capacity against ocean acidification.

A four-decade dataset that spans seven estuaries along a latitudinal gradient in the northwestern Gulf of Mexico and includes measurements of pH and total alkalinity was used to calculate partial pressure of CO2 (pCO2), dissolved inorganic carbon (DIC), saturation state of aragonite (ΩAr), and a buffer factor (βDIC, which measures the response of proton concentration or pH to DIC concentration change) and examine long-term trends and spatial patterns in these parameters. With the notable exception of the northernmost and southernmost estuaries (and selected stations near freshwater input), these estuaries have generally experienced long-term increases in pCO2 and decreases in DIC, ΩAr, and βDIC, with the magnitude of change generally increasing from north to south. At all stations with increasing pCO2, the rate of increase exceeded the rate of increase in atmospheric pCO2, indicating that these estuaries have become a greater source of CO2 to the atmosphere over the last few decades. The decreases in ΩAr have yet to cause ΩAr to near undersaturation, but even the observed decreases may have the potential to decrease calcification rates in important estuarine calcifiers like oysters. The decreases in βDIC directly indicate that these estuaries have experienced continually greater change in pH in the context of ocean acidification.

Carbonate minerals are ubiquitous in most sediment-hosted mineral deposits. These deposits can contain a variety of carbonate types with complex paragenetic relationships. When normalized to chondritic values (CN), rare-earth elements and yttrium (REE+YCN) can be used to constrain fluid chemistry and fluid-rock interaction processes in both low- and high-temperature settings. Unlike other phases (e.g., pyrite), the application of in situ laser ablation-inductively coupled plasma-mass spectroscopy (LA-ICP-MS) data to the differentiation of pre-ore and hydrothermal carbonates remains relatively untested. To assess the potential applicability of carbonate in situ REE+Y data, we combined transmitted light and cathodoluminescence (CL) petrography with LA-ICP-MS analysis of carbonate mineral phases from (1) the Proterozoic George Fisher clastic dominated (CD-type) massive sulfide deposit and from (2) correlative, barren host rock lithologies (Urquhart Shale Formation). The REE+YCN composition of pre-ore calcite suggests it formed during diagenesis from diagenetic pore fluids derived from ferruginous, anoxic seawater. Hydrothermal and hydrothermally altered calcite and dolomite from George Fisher is generally more LREE depleted than the pre-ore calcite, whole-rock REE concentrations, and shale reference values. We suggest this is the result of hydrothermal alteration by saline Cl--rich mineralizing fluids. Furthermore, the presence of both positive and negative Eu/Eu* values in calcite and dolomite indicates that the mineralizing fluids were relatively hot (>250°C) and cooled below 200–250°C during ore formation. This study confirms the hypothesis that in situ REE+Y data can be used to differentiate between pre-ore and hydrothermal carbonate and provide important constraints on the conditions of ore formation. [ABSTRACT FROM AUTHOR]

In order to evaluate the spatiotemporal distribution of the carbonate system in the northern East China Sea (ECS), we first measured the seasonal dissolved inorganic carbon (DIC) and total alkalinity (TA), from which the aragonite saturation state (Ωarag) was calculated for the years 2015–2017. The DIC, TA, and Ωarag were 1,680.9–2,211.4 μmol kg−1, 2,145.1–2,312.8 μmol kg−1, and 1.2–6.0, respectively. The spatiotemporal variability of Ωarag in the northern ECS was mainly controlled by seasonal water mass, such as Yellow Sea Surface Water, Changjiang Dilute Water, and Yellow Sea Bottom Water (YSBW). The lowest Ωarag (∼1.4) in bottom layer was observed in high primary production areas caused by the extension of the Changjiang River plume with the higher Ωarag (up to 6) and was closely linked to the YSBW with low Ωarag expanded southward from Yellow Sea near bottom. Although this area was not a hypoxia zone unlike western shelf region (Chinese region) of the northern ECS, YSBW near bottom could enhance the suppression of bottom aragonite without hypoxia. In eastern region of northern ECS, higher production at surface, YSBW with lower Ωarag extension, and longer respiration product accumulations near bottom tend to lower Ωarag, as compared with western region where the summer hypoxia led to lower Ωarag. Therefore, this result indicates that the eastern region of the northern ECS is also susceptible to ocean acidification, along with the summer hypoxic zone of the western region. Plain Language Summary: Excess carbon dioxide from fossil fuel burning enters the ocean and reacts with seawater decreasing ocean pH, and lowering carbonate ion concentrations. These chemical reactions are known as ocean acidification (OA). Aragonite saturation state (Ωarag) is generally used to trace OA because it measures carbonate ion concentration. A decrease in Ωarag affects marine calcifying organisms and marine ecosystem. In previous studies on OA in East China Sea (ECS), most data were confined to the western shelf region (Chinese region), and this has limited our knowledge about the state of OA for the entire ECS. This study is the first to explore spatiotemporal variability of Ωarag in the northern ECS (Korean region). We found that the spatiotemporal variability of Ωarag in the northern ECS was mainly controlled by seasonal water mass, such as Yellow Sea Surface Water, Changjiang Dilution Water, and Yellow Sea Bottom Water (YSBW). The lowest Ωarag (∼1.4) at the bottom layer was found in areas of surficial high primary production (Ωarag = 6.0), where the Changjiang River plume with nutrient‐rich water discharged and the YSBW with lower Ωarag expanded southward from Yellow Sea near bottom. This value was almost the same as that in areas of hypoxia in Chinese region. Compared with Chinese region, higher production at surface, YSBW with lower Ωarag extension, and long‐term respiration product accumulations near bottom tend to lower Ωarag. This result shows that the Korean region of ECS also could be also vulnerable to OA. Key Points: Dissolved inorganic carbon concentration was main driver of the seasonal variability of aragonite saturation state (Ωarag) in the northern East China Sea (ECS)Spatial variability of Ωarag was mainly controlled by seasonal water massThe northern ECS could be vulnerable to acidification due to high production, Yellow Sea Bottom Water expansion with low Ωarag, and long‐term remineralization [ABSTRACT FROM AUTHOR]

To quantitatively assess the inorganic carbon cycle in the eastern Indian sector of the Southern Ocean (80–150°E, south of 60°S), we measured ocean surface temperature, salinity, total alkalinity (TA), the partial pressure of carbon dioxide (pCO2), and concentrations of chlorophyll‐a (chl a), dissolved inorganic carbon (DIC), and nutrients during the KY18 survey (December 2018–January 2019). The sea–air CO2 flux in this region was −8.3 ± 12.7 mmol m−2 day−1 (−92.1 to +10.6 mmol m−2 day−1). The ocean was therefore a weak CO2 sink. Based on the DIC and TA in the temperature minimum layer, we estimated the change of pCO2 from winter to summer (δpCO2) due to changes in water temperature, salinity, and biological activity (photosynthesis). The spatial distribution of pCO2 in the western part (80–110°E) of the study area was mainly driven by biological activity, which decreased pCO2 from December to early January, and in the eastern part (110–150°E) by temperature, which increased pCO2 from January to February. We also examined the changes in the CO2 concentrations (xCO2) over time by comparing data from 1996 with our data (2018–2019). The oceanic and atmospheric xCO2 increased by 23 and 45 ppm in 23 years, respectively. These changes of ocean xCO2 were mainly driven by an increase in CO2 uptake from the atmosphere as a result of the rise in atmospheric xCO2 and increase in biological activity associated with the change in the water‐mass distribution. Plain Language Summary: Determining the drivers of seasonal changes in ocean CO2 is important for estimating the global carbon cycle. Seawater samples were collected in the eastern Indian sector of the Southern Ocean to investigate the carbonate chemistry of the ocean surface water. During winter and summer, the partial pressure of carbon dioxide (pCO2) at the ocean surface decreased and increased due to photosynthesis and temperature changes, respectively. Surface water pCO2 was lower than the pCO2 of the atmosphere in summer: the result was CO2 uptake by the ocean. A comparison of data from 1996 with our data (2018–2019) indicated that the CO2 concentration (xCO2) of the seawater had increased by 23 ppm. This increase was due primarily to an increase in uptake of CO2 from the atmosphere as a result of the rise of atmospheric xCO2. Key Points: The eastern Indian sector of the Southern Ocean absorbs atmospheric CO2 weakly in summerBiological activity and increases in water temperature change the pCO2 from winter to summerChanges in atmospheric pCO2 and water masses explained the interannual variations of dissolved CO2 in the ocean [ABSTRACT FROM AUTHOR]

Globally, coral reefs are threatened by ocean warming and acidification. The degree to which acidification will impact reefs is dependent on the local hydrodynamics, benthic community composition, and biogeochemical processes, all of which vary on different temporal and spatial scales. Characterizing the natural spatiotemporal variability of seawater carbonate chemistry across different reefs is critical for elucidating future impacts on coral reefs. To date, most studies have focused on select habitats, whereas fewer studies have focused on reef scale variability. Here, we investigate the temporal and spatial seawater physicochemical variability across the entire Heron Island coral reef platform, Great Barrier Reef, Australia, for a limited duration of six days. Autonomous sensor measurements at three sites across the platform were complemented by reef-wide boat surveys and discrete sampling of seawater carbonate chemistry during the morning and evening. Variability in both temporal and spatial physicochemical properties were predominantly driven by solar irradiance (and its effect on biological activity) and the semidiurnal tidal cycles but were influenced by the local geomorphology resulting in isolation of the platform during low tide and rapid flooding during rising tides. As a result, seawater from previous tidal cycles was sometimes trapped in different parts of the reef leading to unexpected biogeochemical trends in space and time. This study illustrates the differences and limitations of data obtained from high-frequency measurements in a few locations compared to low-frequency measurements at high spatial resolution and coverage, showing the need for a combined approach to develop predictive capability of seawater physicochemical properties on coral reefs. [ABSTRACT FROM AUTHOR]

The carbonate chemistry was investigated in the semiarid eutrophic Araruama Lagoon (Brazil), one of the largest hypersaline coastal lagoons in the world. Spatial surveys during winter and summer periods were performed, in addition to a diurnal sampling in summer. The hypersaline waters have higher concentrations of total alkalinity (TA) and dissolved inorganic carbon (DIC) than the seawater that feed the lagoon, due to evaporation. However, TA and DIC concentrations were lower than those expected from evaporation. Calcium carbonate (CaCO3) precipitation partially explained these deficits. The negative correlation between the partial pressure of CO2 (pCO2) and chlorophyll a (Chl a) indicated that DIC was also consumed by primary producers. The uptake by photosynthesis contributes to 57–63% of DIC deviation from evaporation, the remaining credited to CaCO3 precipitation. Marked pCO2 undersaturation was prevalent at the innermost region with shallow, confined, and phytoplankton-dominated waters, with a strong enrichment of heavier carbon isotope (δ13C-DIC up to 5.55‰), and highest pH (locally counter-acting the process of ocean acidification). Oversaturation was restricted to an urbanized region, and during night-time. The lagoon behaved as a marked CO2 sink during winter (− 15.32 to − 10.15 mmolC m−2 day−1), a moderate sink during summer (− 5.50 to − 4.67 mmolC m−2 day−1), with a net community production (NCP) of 93.7 mmolC m−2 day−1 and prevalence of net autotrophic metabolism. A decoupling between CO2 and O2 exchange rate at the air–water interface was attributed to differences in gas solubility, and high buffering capacity. The carbonate chemistry reveals simultaneous and antagonistic actions of CaCO3 precipitation and autotrophic metabolism on CO2 fluxes, and could reflect future conditions in populated and semiarid coastal ecosystems worldwide. [ABSTRACT FROM AUTHOR]

The aragonite saturation state (Ωarag) was determined for the surface waters of the western Arctic Ocean over 3 years, from 2016 to 2018, in an investigation of the present state of acidification of its waters and the main factors controlling the spatial and temporal variations in the surface Ωarag. The study area was divided into the Chukchi marginal area (CMA) and the East Siberian marginal area (ESMA) along a longitude of 180°E. In the CMA, the surface Ωarag during the study period ranged from 0.86 to 1.77, with an average of 1.16, indicating near saturation with respect to aragonite. In the ESMA, the surface Ωarag during the study period ranged from 1.01 to 2.21, with a higher average (1.59) than the CMA. Aragonite undersaturation in the ESMA was not observed during any of the measurement periods, so ocean acidification was less serious there than in the CMA. The surface Ωarag of the CMA was mainly determined by the mixing of seawater and freshwater introduced from rivers and/or sea ice, whereas in the ESMA it was influenced by the mixing of seawater and freshwater but also biological production and lateral mixing. Plain Language Summary: The study was conducted in the western Arctic Ocean and included the Northwind Ridge, Chukchi Plateau, Chukchi Abyssal Plain, Chukchi Sea Slope, East Siberian Sea Slope, and Mendeleyev Ridge. The waters encompassed by these sites are highly vulnerable to acidification because of the inflow of lower‐pH water from the Pacific Ocean through the Bering Sea and the current rapid reduction in the amount of sea ice. The study area was divided into the Chukchi marginal area (CMA) and the East Siberian marginal area (ESMA) along a longitude of 180°E. In the CMA, the surface waters were almost saturated with respect to aragonite but in the ESMA they were undersaturated, indicating that oceanic acidification was more serious in the CMA than in the ESMA. In the near future, the aragonite undersaturation in the most of the surface waters of the CMA will prohibit the survival of calcareous organisms and may lead to their extinction from this area. However, a similar short‐term scenario is not expected in the ESMA, due to its relatively high biological production, which favors aragonite saturation and will thus delay aragonite undersaturation of the surface water. Key Points: In the Chukchi marginal area (CMA), aragonite saturation state (Ωarag) at the surface was determined mainly by the mixing of seawater and fresh waterIn the East Siberian marginal area, Ωarag was affected by freshwater mixing, biological production, and lateral mixingIn the near future, most of surface waters in the CMA will be undersaturated with respect to aragonite [ABSTRACT FROM AUTHOR]

Elemental contents change with shifts in macromolecular composition of marine phytoplankton. Recent studies focus on the responses of elemental contents of coccolithophores, a major calcifying phytoplankton group, to changing carbonate chemistry, caused by the dissolution of anthropogenically derived CO2 into the surface ocean. However, the effects of changing carbonate chemistry on biomacromolecules, such as protein and carbohydrate of coccolithophores, are less documented. Here, we disentangled the effects of elevated dissolved inorganic carbon (DIC) concentration (900 to 4,930μmolkg−1) and reduced pH value (8.04 to 7.70) on physiological rates, elemental contents, and macromolecules of the coccolithophore Emiliania huxleyi. Compared to present DIC concentration and pH value, combinations of high DIC concentration and low pH value (ocean acidification) significantly increased pigments content, particulate organic carbon (POC), and carbohydrate content and had less impact on growth rate, maximal relative electron transport rate (rETR max), particulate organic nitrogen (PON), and protein content. In high pH treatments, elevated DIC concentration significantly increased growth rate, pigments content, rETR max, POC, particulate inorganic carbon (PIC), protein, and carbohydrate contents. In low pH treatments, the extents of the increase in growth rate, pigments and carbohydrate content were reduced. Compared to high pH value, under low DIC concentration, low pH value significantly increased POC and PON contents and showed less impact on protein and carbohydrate contents; however, under high DIC concentration, low pH value significantly reduced POC, PON, protein, and carbohydrate contents. These results showed that reduced pH counteracted the positive effects of elevated DIC concentration on growth rate, rETR max, POC, PON, carbohydrate, and protein contents. Elevated DIC concentration and reduced pH acted synergistically to increase the contribution of carbohydrate–carbon to POC, and antagonistically to affect the contribution of protein–nitrogen to PON, which further shifted the carbon/nitrogen ratio of E. huxleyi. [ABSTRACT FROM AUTHOR]

Elemental contents change with shifts in macromolecular composition of marine phytoplankton. Recent studies focus on the responses of elemental contents of coccolithophores, a major calcifying phytoplankton group, to changing carbonate chemistry, caused by the dissolution of anthropogenically derived CO2 into the surface ocean. However, the effects of changing carbonate chemistry on biomacromolecules, such as protein and carbohydrate of coccolithophores, are less documented. Here, we disentangled the effects of elevated dissolved inorganic carbon (DIC) concentration (900 to 4,930μmolkg−1) and reduced pH value (8.04 to 7.70) on physiological rates, elemental contents, and macromolecules of the coccolithophore Emiliania huxleyi. Compared to present DIC concentration and pH value, combinations of high DIC concentration and low pH value (ocean acidification) significantly increased pigments content, particulate organic carbon (POC), and carbohydrate content and had less impact on growth rate, maximal relative electron transport rate (rETRmax), particulate organic nitrogen (PON), and protein content. In high pH treatments, elevated DIC concentration significantly increased growth rate, pigments content, rETRmax, POC, particulate inorganic carbon (PIC), protein, and carbohydrate contents. In low pH treatments, the extents of the increase in growth rate, pigments and carbohydrate content were reduced. Compared to high pH value, under low DIC concentration, low pH value significantly increased POC and PON contents and showed less impact on protein and carbohydrate contents; however, under high DIC concentration, low pH value significantly reduced POC, PON, protein, and carbohydrate contents. These results showed that reduced pH counteracted the positive effects of elevated DIC concentration on growth rate, rETRmax, POC, PON, carbohydrate, and protein contents. Elevated DIC concentration and reduced pH acted synergistically to increase the contribution of carbohydrate–carbon to POC, and antagonistically to affect the contribution of protein–nitrogen to PON, which further shifted the carbon/nitrogen ratio of E. huxleyi.

Increasing eutrophication of coastal waters generates disturbances in greenhouse gas (GHG) concentrations and emissions to the atmosphere that are still poorly documented, particularly in the tropics. Here, we investigated the concentrations and diffusive fluxes of carbon dioxide (CO2) and methane (CH4) in the urban-dominated Jacarepagua Lagoon Complex (JLC) in Southeastern Brazil. This lagoonal complex receives highly polluted freshwater and shows frequent occurrences of anoxia and hypoxia and dense phytoplankton blooms. Between 2017 and 2018, four spatial surveys were performed (dry and wet conditions), with sampling in the river waters that drain the urban watershed and in the lagoon waters with increasing salinities. Strong oxygen depletion was found in the rivers, associated with extremely high values of partial pressure of CO2 (pCO2; up to 20,417 ppmv) and CH4 concentrations (up to 288,572 nmol L−1). These high GHG concentrations are attributed to organic matter degradation from untreated domestic effluents mediated by aerobic and anaerobic processes, with concomitant production of total alkalinity (TA) and dissolved inorganic carbon (DIC). In the lagoon, GHG concentrations decreased mainly due to dilution with seawater and degassing. In addition, the phytoplankton growth and CH4 oxidation apparently consumed some CO2 and CH4, respectively. TA concentrations showed a marked minimum at salinity of ~20 compared to the two freshwater and marine end members, indicating processes of re-oxidation of inorganic reduced species from the low-salinity region, such as ammonia, iron, and/or sulfides. Diffusive emissions of gases from the entire lagoon ranged from 22 to 48 mmol C m−2 d−1 for CO2 and from 2.2 to 16.5 mmol C m−2 d−1 for CH4. This later value is among the highest documented in coastal waters. In terms of global warming potential (GWP) and CO2 equivalent emissions (CO2-eq), the diffusive emissions of CH4 were higher than those of CO2. These results highlight that highly polluted coastal ecosystems are hotspots of GHG emissions to the atmosphere, which may become increasingly significant in future global carbon budgets. [ABSTRACT FROM AUTHOR]

In this study, we investigated the seawater carbonate chemistry in the Dongsha Atoll Lagoon (DAL) in summer 2015, summer 2016, and autumn 2016. According to the calculation of the total alkalinity anomaly (ΔTA), the DAL is currently maintaining a net calcification status, with higher calcification potential in summer and lower calcification potential in autumn. The calculation of the partial pressure of CO2 anomaly (ΔpCO2) shows that the DAL acts as a CO2 source for the atmosphere, with higher ΔpCO2 values in summer and lower values in autumn. In addition to seasonal variation, ΔpCO2 also exhibits a clear variation between two summer investigations, with higher values in summer 2016 than in summer 2015, which could be associated with the different weather conditions during the sampling periods (2015 vs. 2016: sunny vs. stormy). Moreover, analyzing the salinity-normalized total alkalinity vs. dissolved inorganic carbon relationship reveals that calcification was the dominant process controlling the CO2 dynamics in summer 2015, while those in summer 2016 were regulated mainly by the combination of calcification and organic respiration. This result further suggests that the change in the organic carbon metabolism induced by the different weather conditions could be the driving force behind the observed variation in pCO2 between summer 2015 and 2016. [ABSTRACT FROM AUTHOR]

Global‐scale ocean acidification has spurred interest in the capacity of seagrass ecosystems to increase seawater pH within crucial shoreline habitats through photosynthetic activity. However, the dynamic variability of the coastal carbonate system has impeded generalization into whether seagrass aerobic metabolism ameliorates low pH on physiologically and ecologically relevant timescales. Here we present results of the most extensive study to date of pH modulation by seagrasses, spanning seven meadows (Zostera marina) and 1000 km of U.S. west coast over 6 years. Amelioration by seagrass ecosystems compared to non‐vegetated areas occurred 65% of the time (mean increase 0.07 ± 0.008 SE). Events of continuous elevation in pH within seagrass ecosystems, indicating amelioration of low pH, were longer and of greater magnitude than opposing cases of reduced pH or exacerbation. Sustained elevations in pH of >0.1, comparable to a 30% decrease in [H+], were not restricted only to daylight hours but instead persisted for up to 21 days. Maximal pH elevations occurred in spring and summer during the seagrass growth season, with a tendency for stronger effects in higher latitude meadows. These results indicate that seagrass meadows can locally alleviate low pH conditions for extended periods of time with important implications for the conservation and management of coastal ecosystems. [ABSTRACT FROM AUTHOR]