Changes In Seawater Carbonate Chemistry Research Articles

From reproductive behaviour to responses to predators: Ocean acidification does not impact the behaviour of an herbivorous marine gastropod

Ocean acidification (OA), which reduces ocean pH and leads to substantial changes in seawater carbonate chemistry, may strongly impact organisms, especially those with carbonate skeletons. In marine molluscs, while the physiological effects of OA are well known, with a reduction of growth and shell calcification, there are few studies on behavioural effects. A large marine gastropod, Haliotis tuberculata, was exposed to ambient (pHT 8.0) or low pH (pHT 7.7) during a 5-month experiment. Because animal fitness can be affected through various behavioural changes, a broad spectrum of behavioural parameters was investigated, including situations involving no stress, responses to predators, righting to evaluate indirectly the level of energy reserves, and finally, reproductive behaviour. In addition, we measured the expression profile of the GABA A-like and serotonin receptor genes, often described as central neuromodulators of sensory performance and behaviour and known to be affected by OA in molluscs. No significant effect of low pH as compared to ambient pH was observed on abalone behaviour for any of these behavioural traits or gene expressions after either one week or several months of exposure to OA. The significance tests were corroborated by estimating the size of pH effects. The behaviour of this mollusc appears not to be affected by pH decrease expected by the end of the century, suggesting some resilience of the species to OA at the adult stage. This is probably related to the ecological niche of this abalone, where important pH variations can be observed at tidal, diurnal or seasonal scales.

Influences of Atlantic Ocean thermohaline circulation and Antarctic ice-sheet expansion on Pliocene deep Pacific carbonate chemistry

Quantifying changes in seawater carbonate chemistry is crucial to deciphering of patterns and drivers of the oceanic carbon cycle and climate change. Here, we present a new deep-water carbonate ion saturation state (Δ[CO32−]) record for the Pliocene western tropical Pacific, reconstructed from the size-normalized weight of the planktonic foraminifer Trilobatus sacculifer of IODP Site U1490. A steep decline in deep-water Δ[CO32−] occurred at ∼4.6 Ma synchronous to the enhanced production of North Atlantic Deep Water (NADW) related to the closure of the Panamanian Gateway. Subsequently, at the onset of the Northern Hemisphere glaciation at ∼2.7 Ma the weakening of NADW formation resulted in a deep-water Δ[CO32−] peak. The changes in NADW production rate likely controlled a seesaw-like fluctuation in deep-water Δ[CO32−] between the Pacific and Atlantic oceans. During the late Pliocene (∼3.8–2.8 Ma), Antarctic ice-sheet/sea-ice expansions sequestered CO2 in the deep Pacific through ventilation of the deep watermass, leading to a long-term decrease in deep Pacific Δ[CO32−]. We infer that fluctuating NADW production rates at ∼4.6 Ma and ∼2.7 Ma influenced inter-basinal fractionation of deep-ocean carbon between the Atlantic and Pacific, and that deep Pacific carbon storage linked to expansions of Antarctic ice sheet/sea ice contributed to the lowering of atmospheric pCO2 and global cooling during the late Pliocene.

Molecular response of Sargassum vulgare to acidification at volcanic CO2 vents: Insights from proteomic and metabolite analyses.

Ocean acidification is impacting marine life all over the world. Understanding how species can cope with the changes in seawater carbonate chemistry represents a challenging issue. We addressed this topic using underwater CO2 vents that naturally acidify some marine areas off the island of Ischia. In the most acidified area of the vents, having a mean pH value of 6.7, comparable to far-future predicted acidification scenarios (by 2300), the biomass is dominated by the brown alga Sargassum vulgare. The novelty of the present study is the characterization of the S. vulgare proteome together with metabolite analyses to identify the key proteins, metabolites, and pathways affected by ocean acidification. A total of 367 and 387 proteins were identified in populations grown at pH that approximates the current global average (8.1) and acidified sites, respectively. Analysis of their relative abundance revealed that 304 proteins are present in samples from both sites: 111 proteins are either higher or exclusively present under acidified conditions, whereas 120 proteins are either lower or present only under control conditions. Functionally, under acidification, a decrease in proteins related to translation and post-translational processes and an increase of proteins involved in photosynthesis, glycolysis, oxidation-reduction processes, and protein folding were observed. In addition, small-molecule metabolism was affected, leading to a decrease of some fatty acids and antioxidant compounds under acidification. Overall, the results obtained by proteins and metabolites analyses, integrated with previous transcriptomic, physiological, and biochemical studies, allowed us to delineate the molecular strategies adopted by S. vulgare to grow in future acidified environments, including an increase of proteins involved in energetic metabolism, oxidation-reduction processes, and protein folding at the expense of proteins involved in translation and post-translational processes.

Ocean acidification induced changes in Ulva fasciata biochemistry may improve Dicentrarchus labrax aquaculture via enhanced antimicrobial activity

Changes in seawater carbonate chemistry including increased seawater carbon dioxide concentrations (pCO2), commonly known as ocean acidification (OA), can impact metabolic activities and phytochemical production in marine algae. While OA impacts typically reduce animal health, this study investigated the potential of OA-induced changes in methanol bioactivity from the macroalgae Ulva fasciata, to enhance larval European sea bass (Dicentrarchus labrax) aquaculture via increasing antimicrobial activity. After exposing U. fasciata to four pCO2 levels ~280, 550, 750 and 1050 μatm, macroalgae methanol extracts at pCO2–750 exhibited the highest total phenolic content (TPC), flavonoid content (TFC) and yielded the highest antioxidant and antimicrobial activities. After using extracts as a daily water additive for sea bass larvae, U. fasciata methanolic extract at pCO2–750 yielded the greatest reduction in pathogenic bacterial community and the highest survival rate for sea bass larvae. Sea bass larvae growth was also highest after exposure to methanolic extract of U. fasciata grown at pCO2–750, potentially due to higher TPC, TFC and polyunsaturated fatty acid levels. Such nutritional benefits may have been acquired by sea bass larvae via direct uptake or via indirect transfer, by which live feed (Brachionus or Artemia) consumed by larvae accumulated more nutrients. Our results suggest that pCO2–750 has a significant physiological impact on U. fasciata, potentially allowing macroalgae under OA conditions to function as nutritional supplements to increase the performance of sea bass aquaculture

Reduced H+ channel activity disrupts pH homeostasis and calcification in coccolithophores at low ocean pH

Coccolithophores are major producers of ocean biogenic calcite, but this process is predicted to be negatively affected by future ocean acidification scenarios. Since coccolithophores calcify intracellularly, the mechanisms through which changes in seawater carbonate chemistry affect calcification remain unclear. Here we show that voltage-gated H+ channels in the plasma membrane of Coccolithus braarudii serve to regulate pH and maintain calcification under normal conditions but have greatly reduced activity in cells acclimated to low pH. This disrupts intracellular pH homeostasis and impairs the ability of C. braarudii to remove H+ generated by the calcification process, leading to specific coccolith malformations. These coccolith malformations can be reproduced by pharmacological inhibition of H+ channels. Heavily calcified coccolithophore species such as C. braarudii, which make the major contribution to carbonate export to the deep ocean, have a large intracellular H+ load and are likely to be most vulnerable to future decreases in ocean pH.

Under pressure: Nanoplastics as a further stressor for sub-Antarctic pteropods already tackling ocean acidification

In the Southern Ocean (SO), plastic debris has already been found in waters and sediments. Nanoplastics (<1 μm) are expected to be as pervasive as their larger counterparts, but more harmful to biological systems, being able to enter cells and provoke toxicity. In the SO, (nano)plastic pollution occurs concomitantly with other environmental threats such as ocean acidification (OA), but the potential cumulative impact of these two challenges on SO marine ecosystems is still overlooked. Here the single and combined effects of nanoplastics and OA on the sub-Antarctic pteropod Limacina retroversa are investigated under laboratory conditions, using two surface charged polystyrene nanoparticles (PS NPs) as a proxy for nanoplastics. Sub-Antarctic pteropods are threatened by OA due to the sensitivity of their shells to changes in seawater carbonate chemistry. Short-term exposure (48 h) to PS NPs compromised the ability of pteropods to counteract OA stress, resulting in a negative effect on their survival. Our results highlights the importance of addressing plastic pollution in the context of climate change to identify realistic critical thresholds of SO pteropods.

The primary controls on U/Ca and minor element proxies in a cold-water coral cultured under decoupled carbonate chemistry conditions

Culture experiments are uniquely suited for uncovering the fundamental factors controlling skeletal geochemistry because it is possible to explore conditions beyond what is found in the modern ocean and to decouple parameters that co-vary in nature. We cultured juvenile individuals of a cold-water coral (Balanophyllia elegans) in a set of experiments that decoupled carbonate chemistry parameters over a wide range of pH, DIC, and [CO32−] values. Using a multi-element mixed spike isotope dilution method we then analyzed cultured skeletons for U/Ca, which has been proposed as a potential proxy for seawater pH and [CO32−], as well as Sr/Ca, and Mg/Ca.We find that U/Ca and Sr/Ca ratios in cultured B. elegans are most strongly correlated with solution DIC and not pH or [CO32−]. We also confirm previous observations that Metal/Calcium (Me/Ca) ratios follow the same correlated relationships between and among individuals across different experimental conditions. Interpretation of these robust Me/Ca patterns within the framework of a geochemical model of biomineralization allows us to identify two “rules” of skeletal growth for B. elegans. First, changes in seawater exchange rates can explain variability in B. elegans Me/Ca ratios, correlations between these ratios, and sensitivity of Me/Ca to changes in seawater carbonate chemistry. Second, our model best fits our data if we assume that calcifying fluid pH for B. elegans remains constant across widely varying experimental seawater compositions. Our study has implications for the recently developed Sr-U paleothermometer because it refines our understanding of the environmental parameters affecting this proxy. Our model further demonstrates that U/Ca is not a robust indicator of seawater pH or [CO32−]. Instead, U/Ca may record how calcifying fluid [CO32−] responds to changes in the environment or calcification dynamics, which may be useful in evaluating how corals respond to changes like ocean acidification. Measurements of U/Ca and additional Me/Ca ratios in other coral species, evaluated within a similar framework, may elucidate how those species respond to environmental change.

Global coral reef ecosystems exhibit declining calcification and increasing primary productivity

Long-term coral reef resilience to multiple stressors depends on their ability to maintain positive calcification rates. Estimates of coral ecosystem calcification and organic productivity provide insight into the environmental drivers and temporal changes in reef condition. Here, we analyse global spatiotemporal trends and drivers of coral reef calcification using a meta-analysis of ecosystem-scale case studies. A linear mixed effects regression model was used to test whether ecosystem-scale calcification is related to seasonality, methodology, calcifier cover, year, depth, wave action, latitude, duration of data collection, coral reef state, Ωar, temperature and organic productivity. Global ecosystem calcification estimated from changes in seawater carbonate chemistry was driven primarily by depth and benthic calcifier cover. Current and future declines in coral cover will significantly affect the global reef carbonate budget, even before considering the effects of sub-lethal stressors on calcification rates. Repeatedly studied reefs exhibited declining calcification of 4.3 ± 1.9% per year (x̄ = 1.8 ± 0.7 mmol m−2 d−1 yr−1), and increasing organic productivity at 3.0 ± 0.8 mmol m−2 d−1 per year since 1970. Therefore, coral reef ecosystems are experiencing a shift in their essential metabolic processes of calcification and photosynthesis, and could become net dissolving worldwide around 2054.

Acid–base balance in the hæmolymph of European abalone (Haliotis tuberculata) exposed to CO2-induced ocean acidification

Ocean acidification (OA) and the associated changes in seawater carbonate chemistry pose a threat to calcifying organisms. This is particularly serious for shelled molluscs, in which shell growth and microstructure has been shown to be highly sensitive to OA. To improve our understanding of the responses of abalone to OA, this study investigated the effects of CO2-induced ocean acidification on extra-cellular acid–base parameters in the European abalone Haliotis tuberculata. Three-year-old adult abalone were exposed for 15 days to three different pH levels (7.9, 7.7, 7.4) representing current and predicted near-future conditions. Hæmolymph pH and total alkalinity were measured at different time points during exposure and used to calculate the carbonate parameters of the extracellular fluid. Total protein content was also measured to determine whether seawater acidification influences the composition and buffer capacity of hæmolymph. Extracellular pH was maintained at seawater pH 7.7 indicating that abalones are able to buffer moderate acidification (−0.2 pH units). This was not due to an accumulation of HCO3− ions but rather to a high hæmolymph protein concentration. By contrast, hæmolymph pH was significantly decreased after 5 days of exposure to pH 7.4, indicating that abalone do not compensate for higher decreases in seawater pH. Total alkalinity and dissolved inorganic carbon were also significantly decreased after 15 days of low pH exposure. It is concluded that changes in the acid–base balance of the hæmolymph might be involved in deleterious effects recorded in adult H. tuberculata facing severe OA stress. This would impact both the ecology and aquaculture of this commercially important species.

Patterns of Element Incorporation in Calcium Carbonate Biominerals Recapitulate Phylogeny for a Diverse Range of Marine Calcifiers.

Elemental ratios in biogenic marine calcium carbonates are widely used in geobiology, environmental science, and paleoenvironmental reconstructions. It is generally accepted that the elemental abundance of biogenic marine carbonates reflects a combination of the abundance of that ion in seawater, the physical properties of seawater, the mineralogy of the biomineral, and the pathways and mechanisms of biomineralization. Here we report measurements of a suite of nine elemental ratios (Li/Ca, B/Ca, Na/Ca, Mg/Ca, Zn/Ca, Sr/Ca, Cd/Ca, Ba/Ca, and U/Ca) in 18 species of benthic marine invertebrates spanning a range of biogenic carbonate polymorph mineralogies (low-Mg calcite, high-Mg calcite, aragonite, mixed mineralogy) and of phyla (including Mollusca, Echinodermata, Arthropoda, Annelida, Cnidaria, Chlorophyta, and Rhodophyta) cultured at a single temperature (25°C) and a range of pCO2 treatments (ca. 409, 606, 903, and 2856 ppm). This dataset was used to explore various controls over elemental partitioning in biogenic marine carbonates, including species-level and biomineralization-pathway-level controls, the influence of internal pH regulation compared to external pH changes, and biocalcification responses to changes in seawater carbonate chemistry. The dataset also enables exploration of broad scale phylogenetic patterns of elemental partitioning across calcifying species, exhibiting high phylogenetic signals estimated from both uni- and multivariate analyses of the elemental ratio data (univariate: λ = 0-0.889; multivariate: λ = 0.895-0.99). Comparing partial R 2 values returned from non-phylogenetic and phylogenetic regression analyses echo the importance of and show that phylogeny explains the elemental ratio data 1.4-59 times better than mineralogy in five out of nine of the elements analyzed. Therefore, the strong associations between biomineral elemental chemistry and species relatedness suggests mechanistic controls over element incorporation rooted in the evolution of biomineralization mechanisms.

Viral-Mediated Microbe Mortality Modulated by Ocean Acidification and Eutrophication: Consequences for the Carbon Fluxes Through the Microbial Food Web.

Anthropogenic carbon emissions are causing changes in seawater carbonate chemistry including a decline in the pH of the oceans. While its aftermath for calcifying microbes has been widely studied, the effect of ocean acidification (OA) on marine viruses and their microbial hosts is controversial, and even more in combination with another anthropogenic stressor, i.e., human-induced nutrient loads. In this study, two mesocosm acidification experiments with Mediterranean waters from different seasons revealed distinct effects of OA on viruses and viral-mediated prokaryotic mortality depending on the trophic state and the successional stage of the plankton community. In the winter bloom situation, low fluorescence viruses, the most abundant virus-like particle (VLP) subpopulation comprising mostly bacteriophages, were negatively affected by lowered pH with nutrient addition, while the bacterial host abundance was stimulated. High fluorescence viruses, containing cyanophages, were stimulated by OA regardless of the nutrient conditions, while cyanobacteria of the genus Synechococcus were negatively affected by OA. Moreover, the abundance of very high fluorescence viruses infecting small haptophytes tended to be lower under acidification while their putative hosts' abundance was enhanced, suggesting a direct and negative effect of OA on viral–host interactions. In the oligotrophic summer situation, we found a stimulating effect of OA on total viral abundance and the viral populations, suggesting a cascading effect of the elevated pCO2 stimulating autotrophic and heterotrophic production. In winter, viral lysis accounted for 30 ± 16% of the loss of bacterial standing stock per day (VMMBSS) under increased pCO2 compared to 53 ± 35% in the control treatments, without effects of nutrient additions while in summer, OA had no significant effects on VMMBSS (35 ± 20% and 38 ± 5% per day in the OA and control treatments, respectively). We found that phage production and resulting organic carbon release rates significantly reduced under OA in the nutrient replete winter situation, but it was also observed that high nutrient loads lowered the negative effect of OA on viral lysis, suggesting an antagonistic interplay between these two major global ocean stressors in the Anthropocene. In summer, however, viral-mediated carbon release rates were lower and not affected by lowered pH. Eutrophication consistently stimulated viral production regardless of the season or initial conditions. Given the relevant role of viruses for marine carbon cycling and the biological carbon pump, these two anthropogenic stressors may modulate carbon fluxes through their effect on viruses at the base of the pelagic food web in a future global change scenario.

Air-sea CO2 flux in an equatorial continental shelf dominated by coral reefs (Southwestern Atlantic Ocean)

Coral reefs are ecosystems highly vulnerable to changes in seawater carbonate chemistry, including those related to the ocean acidification and global warming. Brazilian coral reefs contains the major area of reefs coverage in the Southwestern (SW) Atlantic Ocean, however, studies aimed at investigating the controls of seawater carbonate chemistry in coral reefs are still overlooked in Brazil. This study comprehends the first investigation of complete seawater carbonate chemistry parameters in a section of the equatorial continental shelf dominated by coral reefs in the SW Atlantic Ocean. The sampling included spatial continuous underway measurements of sea surface CO2 fugacity (fCO2sw), temperature (SST), salinity (SSS), and discrete investigations of total alkalinity (TA), dissolved inorganic carbon (DIC), bicarbonate (HCO3-), carbonate (CO32−), and saturation state of aragonite (Ωara). The study was conducted during a dry period (July-2019) in the Marine State Park of Pedra da Risca do Meio (PRM), a marine protected area dominated by coral reef communities. Overall, the coral-reef dominated waters presented higher values of fCO2sw (475 ± 28 μatm), and lower values of pHT (7.98 ± 0.008), CO32− (217 ± 5 μmol kg-1) and Ωara (3.49 ± 0.07), compared to nearshore regions without the influence of coral reef waters, where the averages of fCO2sw, pHT, CO32−, and Ωarawere, respectively, 458 ± 21 μatm, 8.00 ± 0.007, 224 ± 4 μmol kg-1, and 3.58 ± 0.05. The relationship between salinity-normalized TA (nTA) and salinity-normalized DIC (nDIC) showed a slope higher than 1 (1.26) in the coral reef, evidencing the occurrence of calcium carbonate (CaCO3) precipitation and prevalence of inorganic carbon metabolism. The CaCO3 precipitation involves the consumption of TA and DIC in a ratio 2:1, with production of CO2. This mechanism explains the higher values of fCO2sw in the coral reef-dominated waters. The values of fCO2sw were always higher than the atmospheric values (fCO2air), indicating a permanent source of CO2 in the study area during the sampled period. The calculated fluxes of CO2 at the air-sea interface averaged 8.4 ± 6.5 mmolC m-2 d-1 in the coral reef-dominated waters, and these data are higher than those verified in nearshore and offshore locations. These higher emissions of CO2 in coral reef-dominated waters evidence that the carbon budgets calculated for North and Northeastern continental shelf of Brazil must include these environments taking into account the widespread coral reef coverage in the region. This study also confirms that biogeochemical processes occurring in coral reefs are modifying the seawater carbonate chemistry, with implication in the context of the current process of ocean acidification.

An integrated investigation of the effects of ocean acidification on adult abalone (Haliotis tuberculata)

Abstract Ocean acidification (OA) and its subsequent changes in seawater carbonate chemistry are threatening the survival of calcifying organisms. Due to their use of calcium carbonate to build their shells, marine molluscs are particularly vulnerable. This study investigated the effect of CO2-induced OA on adult European abalone (Haliotis tuberculata) using a multi-parameter approach. Biological (survival, growth), physiological (pHT of haemolymph, phagocytosis, metabolism, gene expression), and structural responses (shell strength, nano-indentation measurements, Scanning electron microscopy imaging of microstructure) were evaluated throughout a 5-month exposure to ambient (8.0) and low (7.7) pH conditions. During the first 2 months, the haemolymph pH was reduced, indicating that abalone do not compensate for the pH decrease of their internal fluid. Overall metabolism and immune status were not affected, suggesting that abalone maintain their vital functions when facing OA. However, after 4 months of exposure, adverse effects on shell growth, calcification, microstructure, and resistance were highlighted, whereas the haemolymph pH was compensated. Significant reduction in shell mechanical properties was revealed at pH 7.7, suggesting that OA altered the biomineral architecture leading to a more fragile shell. It is concluded that under lower pH, abalone metabolism is maintained at a cost to growth and shell integrity. This may impact both abalone ecology and aquaculture.

Ocean acidification impacts growth and shell mineralization in juvenile abalone (Haliotis tuberculata)

Ocean acidification (OA) is a major global driver that leads to substantial changes in seawater carbonate chemistry, with potentially serious consequences for calcifying organisms. Marine shelled molluscs are ecologically and economically important species, providing essential ecosystem services and food sources for other species. Due to their physiological characteristics and their use of calcium carbonate (CaCO3) to build their shells, molluscs are among the most vulnerable invertebrates with regard to OA, with early developmental stages being particularly sensitive to pH changes. This study investigated the effects of CO2-induced OA on juveniles of the European abalone Haliotis tuberculata, a commercially important gastropod species. Six-month-old juvenile abalones were cultured for 3 months at four pH levels (8.1, 7.8, 7.7, 7.6) representing current and predicted near-future conditions. Survival, growth, shell microstructure, thickness, and strength were compared across the four pH treatments. After 3 months of exposure, significant reductions in juvenile shell length, weight, and strength were revealed in the pH 7.6 treatment. Scanning electron microscopy observations also revealed modified texture and porosity of the shell mineral layers as well as alterations of the periostracum at pH 7.6 which was the only treatment with an aragonite saturation state below 1. It is concluded that low pH induces both general effects on growth mechanisms and corrosion of deposited shell in H. tuberculata. This will impact both the ecological role of this species and the costs of its aquaculture.

Relationship between shell integrity of pelagic gastropods and carbonate chemistry parameters at a Scottish Coastal Observatory monitoring site

AbstractOcean acidification (OA), the anthropogenic carbon dioxide-induced changes in seawater carbonate chemistry, is likely to have a significant impact on calcifying plankton. Most planktonic studies on OA are based on “one-off” cruises focused on offshore areas while observations from inshore waters are scarce. This study presents the first analysis on the shell integrity of pelagic gastropods (holoplanktonic pteropods and planktonic larvae of otherwise benthic species) at the Scottish Coastal Observatory monitoring site at Stonehaven on the east coast of Scotland. The shell integrity of archived pelagic gastropods specimens from 2011 to 2013 was examined using Scanning Electron Microscopy and the relationship with OA (pH and aragonite saturation, Ωarg) and other environmental parameters was investigated. Evidence of shell dissolution was detected in all analysed taxa even though the seawater was supersaturated with respect to aragonite. The shell condition matched the temporal pattern observed in Ωarg, with higher proportion of dissolution associated with decreasing Ωarg, suggesting that the seasonality component of carbonate chemistry might affect the shell integrity of pelagic gastropods. The proportion of shell dissolution differed significantly between larvae and adult stages of pteropods, supporting the hypothesis that early-life stages would be more vulnerable to OA-induced changes. Our data also suggest that sensitivity to OA may differ even between closely related taxonomic groups. The strong interannual variability revealed by the year-to-year shell dissolution and Ωarg illustrates the difficulty in assessing the plankton response to OA in the field and the value of time series studies.

Effects of long-term exposure to reduced pH conditions on the shell and survival of an intertidal gastropod

Volcanic CO2 vents are useful environments for investigating the biological responses of marine organisms to changing ocean conditions (Ocean acidification, OA). Marine shelled molluscs are highly sensitive to changes in seawater carbonate chemistry. In this study, we investigated the effects of reduced pH on the intertidal gastropod, Phorcus sauciatus, in a volcanic CO2 vent off La Palma Island (Canary Islands, North East Atlantic Ocean), a location with a natural pH gradient ranging from 7.0 to 8.2 over the tidal cycles. Density and size-frequency distribution, shell morphology, shell integrity, fracture resistance, and desiccation tolerance were evaluated between populations from control and CO2 vent sites. We found no effects of reduced pH on population parameters or desiccation tolerance across the pH gradient, but significant differences in shell morphology, shell integrity, and fracture resistance were detected. Individuals from the CO2 vent site exhibited a higher shell aspect ratio, greater percentages of shell dissolution and break, and compromised shell strength than those from the control site. Our results highlight that long-term exposure to high pCO2 can negatively affect the shell features of P. sauciatus but may not have a significant effect on population performance. Moreover, we suggest that loss of shell properties could lead to changes in predator-prey interactions.

Responses of carbonic anhydrases and Rubisco to abrupt CO2 changes of seawater in two marine diatoms.

Diatoms are experiencing striking fluctuations in seawater carbonate chemistry in the natural marine environment, especially in coastal seawaters. Here, we show that the diatoms Thalassiosira weissflogii and Phaeodactylum tricornutum, which utilize different carbon acquisition mechanisms, respond differently to short-term changes in seawater carbonate chemistry. Our results showed that T. weissflogii showed significantly higher photosynthetic oxygen evolution rates than that of P. tricornutum at low levels of CO2 or HCO3-. This suggests that T. weissflogii had higher affinities for CO2 or HCO3- when their concentrations were not sufficient to support saturated growth and photosynthesis. While the activity of Rubisco in P. tricornutum positively correlated with carbonic anhydrases (CA), we observed negative relationship between Rubisco and CA activity in the diatom T. weissflogii. These contrasting physiological responses of diatoms with varied carbon acquisition mechanisms indicate different abilities to cope up with abrupt changes in seawater carbonate chemistry. We propose that the ability to respond to varying carbonate chemistry may act as one determinant of the diatom distributions and phytoplankton community structures.

Boric acid and borate incorporation in inorganic calcite inferred from B/Ca, boron isotopes and surface kinetic modeling

The boron concentration (B/Ca ratio) and isotopic composition (δ11B) of biogenic calcite are widely applied to reconstruct past changes in seawater carbonate chemistry. Knowledge of B incorporation pathways into calcite is critical for these applications and for improving the theoretical basis of B proxies. While the canonical interpretation of δ11B holds that B in calcite predominantly derives from dissolved borate anion in seawater, recent studies of the B content, coordination, and isotopic composition in calcite suggest more complex B incorporation pathways. To provide new insights into these pathways, here we present δ11B of inorganic calcite precipitated from saline solutions of varying pH, calcium and dissolved inorganic carbon (DIC) concentration for which B/Ca data were previously reported by Uchikawa et al. (2015). Results show that calcite δ11B significantly increases with increasing pH and decreases with increasing [Ca2+] and [DIC]. In combination, these experiments show that the difference in δ11B between solid calcite and aqueous borate linearly decreases with increasing calcite precipitation rate. To interpret these data, we present the first application of surface kinetic modeling (SKM) to boron incorporation. The SKM can simultaneously explain rate-dependent B/Ca and δ11B patterns observed in our and previously published inorganic calcite precipitation experiments when both aqueous borate and boric acid contribute to boron in inorganic calcite. If the B incorporation mechanism shown here for inorganic calcite is applicable to biogenic calcite, precipitation rate variations could modify δ11B patterns by changing the contributions of aqueous boric acid and borate to boron in calcite. However, better knowledge of biogenic calcite precipitation mechanisms and rates is needed to assess the importance of this effect for applications of B proxies in biogenic carbonates.

Effect of CO2–induced ocean acidification on the early development and shell mineralization of the European abalone (Haliotis tuberculata)

Ocean acidification is a major global stressor that leads to substantial changes in seawater carbonate chemistry, with potentially significant consequences for calcifying organisms. Marine shelled mollusks are ecologically and economically important species providing essential ecosystem services and food sources for other species. Because they use calcium carbonate (CaCO3) to produce their shells, mollusks are among the most vulnerable invertebrates to ocean acidification, with early developmental stages being particularly sensitive to pH changes. This study investigated the effects of CO2-induced ocean acidification on larval development of the European abalone Haliotis tuberculata, a commercially important gastropod species. Abalone larvae were exposed to a range of reduced pHs (8.0, 7.7 and 7.6) over the course of their development cycle, from early-hatched trochophore to pre-metamorphic veliger. Biological responses were evaluated by measuring the survival rate, morphology and development, growth rate and shell calcification. Larval survival was significantly lower in acidified conditions than in control conditions. Similarly, larval size was consistently smaller under low pH conditions. Larval development was also affected, with evidence of a developmental delay and an increase in the proportion of malformed or unshelled larvae. In shelled larvae, the intensity of birefringence decreased under low pH conditions, suggesting a reduction in shell mineralization. Since these biological effects were observed for pH values expected by 2100, ocean acidification may have potentially negative consequences for larval recruitment and persistence of abalone populations in the near future.

Interactive network configuration maintains bacterioplankton community structure under elevated CO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; in a eutrophic coastal mesocosm experiment

Abstract. There is increasing concern about the effects of ocean acidification on marine biogeochemical and ecological processes and the organisms that drive them, including marine bacteria. Here, we examine the effects of elevated CO2 on the bacterioplankton community during a mesocosm experiment using an artificial phytoplankton community in subtropical, eutrophic coastal waters of Xiamen, southern China. Through sequencing the bacterial 16S rRNA gene V3-V4 region, we found that the bacterioplankton community in this high-nutrient coastal environment was relatively resilient to changes in seawater carbonate chemistry. Based on comparative ecological network analysis, we found that elevated CO2 hardly altered the network structure of high-abundance bacterioplankton taxa but appeared to reassemble the community network of low abundance taxa. This led to relatively high resilience of the whole bacterioplankton community to the elevated CO2 level and associated chemical changes. We also observed that the Flavobacteria group, which plays an important role in the microbial carbon pump, showed higher relative abundance under the elevated CO2 condition during the early stage of the phytoplankton bloom in the mesocosms. Our results provide new insights into how elevated CO2 may influence bacterioplankton community structure.