Regulation of seawater dissolved carbon pools by environmental changes in Ulva prolifera originating sites: A new perspective on the contribution of U. prolifera to the seawater carbon sink function.

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 HCO3- and CO2 concentrations. Enhanced light intensity of 108 µmol m-2 s-1 could shift the carbon fixation pathway of U. prolifera towards the C4 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.

Shellfish CO2 excretion is modulated by seawater carbonate chemistry but largely independent of pCO2.

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.

Carbonate Chemistry and the Potential for Acidification in Georgia Coastal Marshes and the South Atlantic Bight, USA.

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. Supplementary Information: The online version contains supplementary material available at 10.1007/s12237-023-01261-3.

The effect of total alkalinity on growth performance and calcification in juvenile Pacific abalone Haliotis discus hannai.

A 45-day trial was conducted to study the effect of seawater total alkalinity (TA) level up- and downregulation on the growth performance and calcification of Haliotis discus hannai Ino, while seawater pH was maintained at pHNBS = 8.1. Although seawater was not acidified, the results showed that TA downregulation caused a significant reduction (P < 0.05) in the somatic tissue growth of juvenile abalone, while TA upregulation significantly increased growth performance (P < 0.05). Similar to the impacts of pH reduction, TA downregulation also induces a decline in CO2 buffering capacity, which may be the reason why somatic tissue growth was reduced, as lowered CO2 buffering capacity was reported to shift the acid-base balancing of abalone. Parts of the periostracum layer weremissing and exposed the inner shell layers of the individuals from the TA-downregulated group. Scanning electron microscopy (SEM) results showed calcium carbonate densely deposited onto the inner shell in the control and TA-upregulated groups, while sparsely deposited calcium carbonate was observed in the TA-downregulated group. The C: N ratio in the shell of individuals from the TA-downregulated group was significantly lower than that of the other two groups, indicating that less inorganic carbon was added to the shell. As a result, abalone grew lighter and thinner shells in TA-downregulated seawater. Although seawater was not acidified, TA downregulation also caused a reduction in the calcium carbonate saturation state (Ω), which induced the erosion of the surface shell and the interruption of calcium carbonate generation. In conclusion, although seawater pH remained at ambient levels, the lowered CO2 buffering capacity and Ω induced by seawater TA downregulation also showed a detrimental effect on the growth and calcification of Pacific abalone. The impact of ocean acidification on the growth of abalone should not be assessed using only seawater pH and/or pCO2 but rather taking into account all of carbonate chemistry, particularly the CO2 buffering capacity. Abalone cultivation is suggested to be carried out in seawater with a higher level of CO2 buffering capacity and Ω, which can be achieved through integrated culture with seaweed or increasing the seawater TA level.

Oyster reefs' control of carbonate chemistry-Implications for oyster reef restoration in estuaries subject to coastal ocean acidification.

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.

Imaging of CO2 and Dissolved Inorganic Carbon via Electrochemical Acidification-Optode Tandem.

Dissolved inorganic carbon (DIC) is a key component of the global carbon cycle and plays a critical role in ocean acidification and proliferation of phototrophs. Its quantification at a high spatial resolution is essential for understanding various biogeochemical processes. We present an analytical method for 2D chemical imaging of DIC by combining a conventional CO2 optode with localized electrochemical acidification from a polyaniline (PANI)-coated stainless-steel mesh electrode. Initially, the optode response is governed by local concentrations of free CO2 in the sample, corresponding to the established carbonate equilibrium at the (unmodified) sample pH. Upon applying a mild potential-based polarization to the PANI mesh, protons are released into the sample, shifting the carbonate equilibrium toward CO2 conversion (>99%), which corresponds to the sample DIC. It is herein demonstrated that the CO2 optode-PANI tandem enables the mapping of free CO2 (before PANI activation) and DIC (after PANI activation) in complex samples, providing high 2D spatial resolution (approx. 400 µm). The significance of this method was proven by inspecting the carbonate chemistry of complex environmental systems, including the freshwater plant Vallisneria spiralis and lime-amended waterlogged soil. This work is expected to pave the way for new analytical strategies that combine chemical imaging with electrochemical actuators, aiming to enhance classical sensing approaches via in situ (and reagentless) sample treatment. Such tools may provide a better understanding of environmentally relevant pH-dependent analytes related to the carbon, nitrogen, and sulfur cycles.

NaHCO3 addition enhances water permeance and Ca/haloacetic acids selectivity of nanofiltration membranes for drinking water treatment.

The existence of disinfection by-products such as haloacetic acids (HAAs) in drinking water severely threatens water safety and public health. Nanofiltration (NF) is a promising strategy to remove HAAs for clean water production. However, NF often possesses overhigh rejection of essential minerals such as calcium. Herein, we developed highly selective NF membranes with tailored surface charge and pore size for efficient rejection of HAAs and high passage of minerals. The NF membranes were fabricated through interfacial polymerization (IP) with NaHCO3 as an additive. The NaHCO3-tailored NF membranes exhibited high water permeance up to ∼24.0 L m - 2 h - 1 bar-1 (more than doubled compared with the control membrane) thanks to the formation of stripe-like features and enlarged pore size. Meanwhile, the tailored membranes showed enhanced negative charge, which benefitted their rejection of HAAs and passage of Ca and Mg. The higher rejection of HAAs (e.g., > 90%) with the lower rejection of minerals (e.g., < 30% for Ca) allowed the NF membranes to achieve higher minerals/HAAs selectivity, which was significantly higher than those of commercially available NF membranes. The simultaneously enhanced membrane performance and higher minerals/HAAs selectivity would greatly boost water production efficiency and water quality. Our findings provide a novel insight to tailor the minerals/micropollutants selectivity of NF membranes for highly selective separation in membrane-based water treatment.

Seawater carbonate parameters function differently in affecting embryonic development and calcification in Pacific abalone (Haliotis discus hannai).

pH or pCO2 are usually taken to study the impact of ocean acidification on molluscs. Here we studied the different impact of seawater carbonate parameters on embryonic development and calcification of the Pacific abalone (Haliotis discus hannai). Early embryonic development was susceptible to elevated pCO2 level. Larvae hatching duration was positively and hatching rate was negatively correlated with the pCO2 level, respectively. Calcium carbonate (CaCO3) deposition of larval shell was found to be susceptible to calcium carbonate saturation state (Ω) rather than pCO2 or pH. Most larvae incubated in seawater with Ωarag = 1.5 succeeded in shell formation, even when seawater pCO2 level was higher than 3700 µatm and pHT was close to 7.4. Nevertheless, larvae failed to generate CaCO3 in seawater with Ωarag ≤ 0.52 and control level of pCO2, while seawater DIC level was lowered (≤ 852 µmol/kg). Surprisingly, some larvae completed CaCO3 deposition in seawater with Ωarag = 0.6 and slightly elevated DIC (2266 µmol/kg), while seawater pCO2 level was higher than 2700 µatm and pHT was lower than 7.3. This indicates that abalone may be capable of regulating carbonate chemistry to support shell formation, however, the capability was limited as surging pCO2 level lowered growth rate and jeopardized the integrity of larval shells. Larvae generated thicker shell in seawater with Ωarag = 5.6, while adult abalone could not deposit CaCO3 in seawater with Ωarag = 0.29 and DIC = 321 µmol/kg. This indicates that abalone may lack the ability to directly remove or add inorganic carbon at the calcifying sites. In conclusion, different seawater carbonate parameters play different roles in affecting early embryonic development and shell formation of the Pacific abalone, which may exhibit limited capacity to regulate carbonate chemistry.

Decoupling of Estuarine Hypoxia and Acidification as Revealed by Historical Water Quality Data.

Hypoxia and acidification are commonly coupled in eutrophic aquatic environments because aerobic respiration is usually dominant in bottom waters and can lower dissolved oxygen (DO) and pH simultaneously. However, the degree of coupling, which can be weakened by non-aerobic respiration and CaCO3 cycling, has not been adequately assessed. In this study, we applied a box model to 20 years of water quality monitoring data to explore the relationship between hypoxia and acidification along the mainstem of Chesapeake Bay. In the early summer, dissolved inorganic carbon (DIC) production in mid-bay bottom waters was dominated by aerobic respiration, contributing to DO and pH declines. In contrast, late-summer DIC production was higher than that expected from aerobic respiration, suggesting potential buffering processes, such as calcium carbonate dissolution, which would elevate pH in hypoxic waters. These findings are consistent with contrasting seasonal relationships between riverine nitrogen (N) loads and hypoxic and acidified volumes. The N loads were associated with increased hypoxic and acidified volumes in June, but only increased hypoxic volumes in August, when acidified volume declines instead. Our study reveals that the magnitude of this decoupling varies interannually with watershed nutrient inputs, which has implications for the management of co-stressors in estuarine systems.

Modified future diurnal variability of the global surface ocean CO2 system.

Our understanding of how increasing atmospheric CO2 and climate change influences the marine CO2 system and in turn ecosystems has increasingly focused on perturbations to carbonate chemistry variability. This variability can affect ocean-climate feedbacks and has been shown to influence marine ecosystems. The seasonal variability of the ocean CO2 system has already changed, with enhanced seasonal variations in the surface ocean pCO2 over recent decades and further amplification projected by models over the 21st century. Mesocosm studies and CO2 vent sites indicate that diurnal variability of the CO2 system, the amplitude of which in extreme events can exceed that of mean seasonal variability, is also likely to be altered by climate change. Here, we modified a global ocean biogeochemical model to resolve physically and biologically driven diurnal variability of the ocean CO2 system. Forcing the model with 3-h atmospheric outputs derived from an Earth system model, we explore how surface ocean diurnal variability responds to historical changes and project how it changes under two contrasting 21st-century emission scenarios. Compared to preindustrial values, the global mean diurnal amplitude of pCO2 increases by 4.8 µatm (+226%) in the high-emission scenario but only 1.2 µatm (+55%) in the high-mitigation scenario. The probability of extreme diurnal amplitudes of pCO2 and [H+ ] is also affected, with 30- to 60-fold increases relative to the preindustrial under high 21st-century emissions. The main driver of heightened pCO2 diurnal variability is the enhanced sensitivity of pCO2 to changes in temperature as the ocean absorbs atmospheric CO2 . Our projections suggest that organisms in the future ocean will be exposed to enhanced diurnal variability in pCO2 and [H+ ], with likely increases in the associated metabolic cost that such variability imposes.

The influences of diurnal variability and ocean acidification on the bioerosion rates of two reef-dwelling Caribbean sponges.

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.

Calcium Carbonate Dissolution from the Laboratory to the Ocean: Kinetics and Mechanism.

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.

Contrasting land-uses in two small river basins impact the colored dissolved organic matter concentration and carbonate system along a river-coastal ocean continuum.

Human activities have led to an increase in land use change, with effects on the structure and functioning of ecosystems. The impact of contrasting land uses along river basins on the concentration of colored dissolved organic matter (CDOM) reaching the coastal zone, and its relationship with the carbonate system of the adjacent coastal ocean, is poorly known. To understand the relationship between land use change, CDOM and its influence on the carbonate system, two watersheds with contrasting land uses in southern Chile were studied. The samples were collected at eight stations between river and adjacent coastal areas, during three sampling campaigns in the austral summer and spring. Chemical and biological samples were analyzed in the laboratory according to standard protocols. Landsat 8 satellite images of the study area were used for identification and supervised classification using remote sensing tools. The Yaldad River basin showed 82% of native forest and the Colu River basin around 38% of grassland (agriculture). Low total alkalinity (AT) and Dissolved Inorganic Carbon (DIC), but high CDOM proportions were typically observed in freshwater. A higher CDOM and humic-like compounds concentration was observed along the river-coastal ocean continuum in the Yaldad basin, characterized by a predominance of native forests. In contrast, nutrient concentrations, AT and DIC, were higher in the Colu area. Low CaCO3 saturation state (ΩAr < 2) and even undersaturation conditions were observed at the coastal ocean at Yaldad. A strong negative correlation between AT, DIC and ΩAr with CDOM/fDOM, suggested the influence of terrestrial material on the seawater carbon chemistry. Our results provide robust evidence that land uses in river basins can influence CDOM/fDOM proportion and its influence on the carbonate chemistry of the adjacent coastal, with potential implications for the shellfish farming activity in this region.

Disentangling the Effects of Ocean Carbonation and Acidification on Elemental Contents and Macromolecules of the Coccolithophore Emiliania huxleyi.

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.

Coast-wide evidence of low pH amelioration by seagrass ecosystems.

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.

Greenhouse gas emissions (CO2 and CH4) and inorganic carbon behavior in an urban highly polluted tropical coastal lagoon (SE, Brazil).

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.

Seaweed farms provide refugia from ocean acidification.

Seaweed farming has been proposed as a strategy for adaptation to ocean acidification, but evidence is largely lacking. Changes of pH and carbon system parameters in surface waters of three seaweed farms along a latitudinal range in China were compared, on the weeks preceding harvesting, with those of the surrounding seawaters. Results confirmed that seaweed farming is efficient in buffering acidification, with Saccharina japonica showing the highest capacity of 0.10 pH increase within the aquaculture area, followed by Gracilariopsis lemaneiformis (ΔpH = 0.04) and Porphyra haitanensis (ΔpH = 0.03). The ranges of pH variability within seaweed farms spanned 0.14-0.30 unit during the monitoring, showing intense fluctuations which may also help marine organisms adapt to enhanced pH temporal variations in the future ocean. Deficit in pCO2 in waters in seaweed farms relative to control waters averaged 58.7 ± 15.9 µatm, ranging from 27.3 to 113.9 µatm across farms. However, ΔpH did not significantly differ between day and night. Dissolved oxygen and Ωarag were also elevated in surface waters at all seaweed farms, which are benefit for the survival of calcifying organisms. Seaweed farming, which unlike natural seaweed forests, is scalable and is not dependent on suitable substrate or light availability, could serve as a low-cost adaptation strategy to ocean acidification and deoxygenation and provide important refugia from ocean acidification.

Coccolith volume of the Southern Ocean coccolithophore Emiliania huxleyi as a possible indicator for palaeo-cell volume.

Coccolithophores are a key functional phytoplankton group and produce minute calcite plates (coccoliths) in the sunlit layer of the pelagic ocean. Coccoliths significantly contribute to the sediment record since the Triassic and their geometry have been subject to palaeoceanographic and biological studies to retrieve information on past environmental conditions. Here, we present a comprehensive analysis of coccolith, coccosphere and cell volume data of the Southern Ocean Emiliania huxleyi ecotype A, subject to gradients of temperature, irradiance, carbonate chemistry and macronutrient limitation. All tested environmental drivers significantly affect coccosphere, coccolith and cell volume with driver-specific sensitivities. However, a highly significant correlation emerged between cell and coccolith volume with Vcoccolith  = 0.012 ± 0.001 * Vcell  + 0.234 ± 0.066 (n = 23, r2  = .85, p < .0001, σest  = 0.127), indicating a primary control of coccolith volume by physiological modulated changes in cell volume. We discuss the possible application of fossil coccolith volume as an indicator for cell volume/size and growth rate and, additionally, illustrate that macronutrient limitation of phosphorus and nitrogen has the predominant influence on coccolith volume in respect to other environmental drivers. Our results provide a solid basis for the application of coccolith volume and geometry as a palaeo-proxy and shed light on the underlying physiological reasons, offering a valuable tool to investigate the fossil record of the coccolithophore E. huxleyi.

Ervilia castanea (Mollusca, Bivalvia) populations adversely affected at CO2 seeps in the North Atlantic.

Sites with naturally high CO2 conditions provide unique opportunities to forecast the vulnerability of coastal ecosystems to ocean acidification, by studying the biological responses and potential adaptations to this increased environmental variability. In this study, we investigated the bivalve Ervilia castanea in coastal sandy sediments at reference sites and at volcanic CO2 seeps off the Azores, where the pH of bottom waters ranged from average oceanic levels of 8.2, along gradients, down to 6.81, in carbonated seawater at the seeps. The bivalve population structure changed markedly at the seeps. Large individuals became less abundant as seawater CO2 levels rose and were completely absent from the most acidified sites. In contrast, small bivalves were most abundant at the CO2 seeps. We propose that larvae can settle and initially live in high abundances under elevated CO2 levels, but that high rates of post-settlement dispersal and/or mortality occur. Ervilia castanea were susceptible to elevated CO2 levels and these effects were consistently associated with lower food supplies. This raises concerns about the effects of ocean acidification on the brood stock of this species and other bivalve molluscs with similar life history traits.

Natural and Anthropogenic Drivers of Acidification in Large Estuaries.

Oceanic uptake of anthropogenic carbon dioxide (CO2) from the atmosphere has changed ocean biogeochemistry and threatened the health of organisms through a process known as ocean acidification (OA). Such large-scale changes affect ecosystem functions and can have impacts on societal uses, fisheries resources, and economies. In many large estuaries, anthropogenic CO2-induced acidification is enhanced by strong stratification, long water residence times, eutrophication, and a weak acid-base buffer capacity. In this article, we review how a variety of processes influence aquatic acid-base properties in estuarine waters, including coastal upwelling, river-ocean mixing, air-water gas exchange, biological production and subsequent aerobic and anaerobic respiration, calcium carbonate (CaCO3) dissolution, and benthic inputs. We emphasize the spatial and temporal dynamics of partial pressure of CO2 (pCO2), pH, and calcium carbonate mineral saturation states. Examples from three large estuaries-Chesapeake Bay, the Salish Sea, and Prince William Sound-are used to illustrate how natural and anthropogenic processes and climate change may manifest differently across estuaries, as well as the biological implications of OA on coastal calcifiers.