Seawater Carbonate Chemistry Research Articles

Decreased Diversity and Abundance of Marine Invertebrates at CO2 Seeps in Warm-Temperate Japan.

Japan has many coastal carbon dioxide seeps as it is one of the most volcanically active parts of the world. These shallow seeps do not have the spectacular aggregations of specialist fauna seen in deep-sea vent systems but they do have gradients in seawater carbonate chemistry that are useful as natural analogues of the effects of ocean acidification on marine biodiversity, ecosystem function and fisheries. Here, we compare macroinvertebrate diversity and abundance on rocky habitats at ambient (mean ≤ 410 µatm) and high (mean 971-1484 µatm) levels of seawater pCO2 in the warm-temperate region of Japan, avoiding areas with toxic sulphur or warm-water conditions. We show that although 70% of intertidal taxa and 40% of shallow subtidal taxa were able to tolerate the high CO2 conditions, there was a marked reduction in the abundance of corals, bivalves and gastropods in acidified conditions. A narrower range of filter feeders, grazers, detritivores, scavengers and carnivores were present at high CO2 resulting in a simplified coastal system that was unable to retain the high standing stocks of marine carbon biomass found in ambient conditions. It is clear that cuts in CO2 emissions would reduce the risks of climate change and ocean acidification impacts on marine biodiversity, shellfish production and biomass in the rocky coastal shores of this region.

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.

Calcification in Three Common Calcified Algae from Phuket, Thailand: Potential Relevance on Seawater Carbonate Chemistry and Link to Photosynthetic Process.

Calcifying macroalgae contribute significantly to the structure and function of tropical marine ecosystems. Their calcification and photosynthetic processes are not well understood despite their critical role in marine carbon cycles and high vulnerability to environmental changes. This study aims to provide a better understanding of the macroalgal calcification process, focusing on its relevance concerning seawater carbonate chemistry and its relationship to photosynthesis in three dominant calcified macroalgae in Thailand, Padina boryana, Halimeda macroloba and Halimeda opuntia. Morphological and microstructural attributes of the three macroalgae were analyzed and subsequently linked to their calcification rates and responses to inhibition of photosynthesis. In the first experiment, seawater pH, total alkalinity and total dissolved inorganic carbon were measured after incubation of the macroalgae in the light and after equilibration of the seawater with air. Estimations of carbon uptake into photosynthesis and calcification and carbon release into air were obtained thereafter. Our results provide evidence that calcification of the three calcified macroalgae is a potential source of CO2, where calcification by H. opuntia and H. macroloba leads to a greater release of CO2 per biomass weight than P. boryana. Nevertheless, this capacity is expected to vary on a diurnal basis, as the second experiment indicates that calcification is highly coupled to photosynthetic activity. Lower pH as a result of inhibited photosynthesis under darkness imposes more negative effects on H. opuntia and H. macroloba than on P. boryana, implying that they are more sensitive to acidification. These effects were worsened when photosynthesis was inhibited by 3-(3,4-dichlorophenyl)-1,1-dimethylurea, highlighting the significance of photosynthetic electron transport-dependent processes. Our findings suggest that estimations of the amount of carbon stored in the vegetated marine ecosystems should account for macroalgal calcification as a potential carbon source while considering diurnal variations in photosynthesis and seawater pH in a natural setting.

Responses of the marine carbonate system to a green tide: A case study of an Ulva prolifera bloom in Qingdao coastal waters

As an environmental nuisance, Ulva prolifera green tides have occurred annually in the southern Yellow Sea since 2007. While it is expected that high levels of biological activity during these blooms can alter seawater carbonate chemistry, there has been little research on the responses of marine carbonate system to green tides. Here, the effects of the bloom on the carbonate system were examined on three cruises in June, July, and September, corresponding to the early-, late-, and after-bloom periods of the U. prolifera bloom in Qingdao coastal waters in 2018. Among these three stages, the pH (National Bureau of Standards scale), dissolved inorganic carbon (DIC), total alkalinity (TA), and partial pressure of CO2 (pCO2) were all affected by bloom, with the highest pH and lowest DIC and TA concentrations of the surface seawater occurring at the late-bloom stage. While pCO2 continuously increased from the beginning to the end of the bloom. TA increased by ∼40 μmol kg−1 between the early- and after-bloom periods likely due to the shifts in the carbonate system equilibrium caused by increased CO32− concentrations and the organic matter released by U. prolifera during decomposition. Compared to nearby areas with no U. prolifera bloom, the green tide, along with increasing temperature, reduced the pH and DIC but increased the TA and pCO2. This large-scale bloom also turned the coastal waters from being an atmospheric CO2 sink to a strong source, with the estimation of air-sea CO2 fluxes about 1.69 ± 1.70, 2.28 ± 1.16, and 7.44 ± 5.84 mmol m−2 d−1 during the early-, late-, and after-bloom periods, respectively. This bloom event also promoted the formation of CaCO3 and was an important source of low molecular weight organic acids. These new findings provide nuances for the current conversations on the role of biological processes in modulating marine carbonate system and the contribution of organic matter to alkalinity.

A Unique Diel Pattern in Carbonate Chemistry in the Seagrass Meadows of Dongsha Island: The Enhancement of Metabolic Carbonate Dissolution in a Semienclosed Lagoon

In contrast to other seagrass meadows where seawater carbonate chemistry generally shows strong diel variations with higher pH but lower partial pressure of CO2 (pCO2) during the daytime and lower pH but higher pCO2 during nighttime due to the alternation in photosynthesis and respiration, the seagrass meadows of the inner lagoon (IL) on Dongsha Island had a unique diel pattern with extremely high pH and low pCO2 across a diel cycle. We suggest that this distinct diel pattern in pH and pCO2 could be associated with the enhancement of total alkalinity (TA) production coupled to carbonate sediment dissolution in a semienclosed lagoon. The confinement of the IL may hamper water exchange and seagrass detritus export to the adjacent open ocean, which may result in higher organic matter loading to the sediments, and longer residence time of the water in the IL, accompanied by microbial respiration (both aerobic and anaerobic) that may reduce carbonate saturation level to drive carbonate dissolution and thus TA elevation, thereby forming such a unique diel pattern in carbonate chemistry. This finding further highlights the importance of considering TA production through metabolic carbonate dissolution when evaluating the potential of coastal blue carbon ecosystems to buffer ocean acidification and to absorb atmospheric CO2, in particular in a semienclosed setting.

Impacts of pH on the Fitness and Immune System of Pacific White Shrimp

The atmospheric partial pressure of CO2 (pCO2) has been increasing dramatically since the beginning of the industrial revolution and about 30% of the CO2 produced by anthropogenic activities was absorbed by the ocean. This led to a perturbation of the seawater carbonate chemistry resulting in a decrease of the average surface ocean pH by 0.1 and termed ocean acidification (OA). Projections suggest that pCO2 may reach 900 μatm by the end of the twenty-first century lowering the average pH of the surface ocean by 0.4 units. The negative impacts of OA on many species of marine invertebrates such as mollusks, echinoderms, and crustaceans are well documented. However, less attention has been paid to the impacts of low pH on fitness and immune system in crustaceans. Here, we exposed Pacific white shrimps to 3 different pHs (nominal pH 8.0, 7.9, and 7.6) over a 100-days experiment. We found that, even though there were no significant effects on fitness parameters (survival, growth and allometries between length and weight), some immune markers were modified under low pH. A significant decrease in total hemocyte count and phenoloxidase activity was observed in shrimps exposed to pH 7.6 as compared to pH 8.0; and phagocytosis rate significantly decreased with decreasing pH. A significant increase in superoxide production was also observed at pH 7.6 as compared to pH 8.0. All these results suggest that a 100-days exposure to pH 7.6 did not have a direct effect on fitness but lead to a modulation of the immune response.

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.

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.

Arid Coastal Carbonates and the Phanerozoic Record of Carbonate Chemistry

AbstractOcean chemistry and carbonate sedimentation link Earth's climate, carbon cycle, and marine pH. The carbonate system in seawater is complex and there are large uncertainties in key parameters in deep time. Here, we link sedimentary textures formed in arid coastal environments and preserved in the rock record to past seawater carbonate chemistry. Prior to the mid‐Mesozoic, tepee structures and pisoids – features associated with peritidal environments – co‐vary with available shelf area during cycles of supercontinent formation and rifting. In contrast, tepees and pisoids are consistently scarce after the mid‐Mesozoic, which coincides with a radiation in pelagic calcifiers as well as the breakup of Pangea. Numerical models suggest that the global and temporal abundances of tepee structures and pisoids are correlated with secular shifts in seawater chemistry, and that trends likely reflect the underlying influence of tectonics and biotic innovation on marine alkalinity and the saturation states of carbonate minerals. As independent sedimentary proxies, tepees and pisoids serve as benchmarks for global carbon cycle models and provide a new proxy record of seawater chemistry that can help discern links among tectonics, biotic innovation, and seawater chemistry.

Major loss of coralline algal diversity in response to ocean acidification.

Calcified coralline algae are ecologically important in rocky habitats in the marine photic zone worldwide and there is growing concern that ocean acidification will severely impact them. Laboratory studies of these algae in simulated ocean acidification conditions have revealed wide variability in growth, photosynthesis and calcification responses, making it difficult to assess their future biodiversity, abundance and contribution to ecosystem function. Here, we apply molecular systematic tools to assess the impact of natural gradients in seawater carbonate chemistry on the biodiversity of coralline algae in the Mediterranean and the NW Pacific, link this to their evolutionary history and evaluate their potential future biodiversity and abundance. We found a decrease in the taxonomic diversity of coralline algae with increasing acidification with more than half of the species lost in high pCO2 conditions. Sporolithales is the oldest order (Lower Cretaceous) and diversified when ocean chemistry favoured low Mg calcite deposition; it is less diverse today and was the most sensitive to ocean acidification. Corallinales were also reduced in cover and diversity but several species survived at high pCO2 ; it is the most recent order of coralline algae and originated when ocean chemistry favoured aragonite and high Mg calcite deposition. The sharp decline in cover and thickness of coralline algal carbonate deposits at high pCO2 highlighted their lower fitness in response to ocean acidification. Reductions in CO2 emissions are needed to limit the risk of losing coralline algal diversity.

Long-term effects of high CO2 on growth and survival of juveniles of the striped venus clam Chamelea gallina: implications of seawater carbonate chemistry

Long-term effects of high CO2 on growth and survival of juveniles of the striped venus clam Chamelea gallina: implications of seawater carbonate chemistry

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.

Morphological Properties of Gastropod Shells in a Warmer and More Acidic Future Ocean Using 3D Micro-Computed Tomography

The increased absorption of atmospheric CO2 by the ocean reduces pH and affects the carbonate chemistry of seawater, thus interfering with the shell formation processes of marine calcifiers. The present study aims to examine the effects of ocean acidification and warming on the shell morphological properties of two intertidal gastropod species, Nassarius nitidus and Columbella rustica. The experimental treatments lasted for 3 months and combined a temperature increase of 3°C and a pH reduction of 0.3 units. The selected treatments reflected the high emissions (RCP 8.5) “business as usual” scenario of the Intergovernmental Panel on Climate Change models for eastern Mediterranean. The morphological and architectural properties of the shell, such as density, thickness and porosity were examined using 3D micro-computed tomography, which is a technique giving the advantage of calculating values for the total shell (not only at specific points) and at the same time leaving the shells intact. Nassarius nitidus had a lower shell density and thickness and a higher porosity when the pH was reduced at ambient temperature, but the combination of reduced pH and increased temperature did not have a noticeable effect in comparison to the control. The shell of Columbella rustica was less dense, thinner and more porous under acidic and warm conditions, but when the temperature was increased under ambient pH the shells were thicker and denser than the control. Under low pH and ambient temperature, shells showed no differences compared to the control. The vulnerability of calcareous shells to ocean acidification and warming appears to be variable among species. Plasticity of shell building organisms as an acclimation action toward a continuously changing marine environment needs to be further investigated focusing on species or shell region specific adaptation 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.

Lateral, Vertical, and Temporal Variability of Seawater Carbonate Chemistry at Hog Reef, Bermuda

Spatial and temporal carbonate chemistry variability on coral reefs is influenced by a combination of seawater hydrodynamics, geomorphology, and biogeochemical processes, though their relative influence varies by site. It is often assumed that the water column above most reefs is well-mixed with small to no gradients outside of the benthic boundary layer. However, few studies to date have explored the processes and properties controlling these multi-dimensional gradients. Here, we investigated the lateral, vertical, and temporal variability of seawater carbonate chemistry on a Bermudan rim reef using a combination of spatial seawater chemistry surveys and autonomous in situ sensors. Instruments were deployed at Hog Reef measuring current flow, seawater temperature, salinity, pHT, pCO2, dissolved oxygen (DO), and total alkalinity (TA) on the benthos, and temperature, salinity, DO, and pCO2 at the surface. Water samples from spatial surveys were collected from surface and bottom depths at 13 stations covering ∼3 km2 across 4 days. High frequency temporal variability in carbonate chemistry was driven by a combination of diel light and mixed semi-diurnal tidal cycles on the reef. Daytime gradients in DO between the surface and the benthos suggested significant water column production contributing to distinct diel trends in pHT, pCO2, and DO, but not TA. We hypothesize these differences reflect the differential effect of biogeochemical processes important in both the water column and benthos (organic carbon production/respiration) vs. processes mainly occurring on the benthos (calcium carbonate production/dissolution). Locally at Hog Reef, the relative magnitude of the diel variability of organic carbon production/respiration was 1.4–4.6 times larger than that of calcium carbonate production/dissolution, though estimates of net organic carbon production and calcification based on inshore-offshore chemical gradients revealed net heterotrophy (−118 ± 51 mmol m–2 day–1) and net calcification (150 ± 37 mmol CaCO3 m–2 day–1). These results reflect the important roles of time and space in assessing reef biogeochemical processes. The spatial variability in carbonate chemistry parameters was larger laterally than vertically and was generally observed in conjunction with depth gradients, but varied between sampling events, depending on time of day and modifications due to current flow.

Implications of giant ooids for the carbonate chemistry of Early Triassic seawater

Abstract Lower Triassic limestones contain giant ooids (&amp;gt;2 mm) along with other precipitated carbonate textures more typical of Precambrian strata. These features appear to have resulted from changes in seawater chemistry associated with the end-Permian mass extinction, but quantifying the carbonate chemistry of Early Triassic seawater has remained challenging. To constrain seawater carbonate saturation state, dissolved inorganic carbon, alkalinity, and pH, we applied a physicochemical model of ooid formation constrained by new size data on Lower Triassic ooids from south China, finding that the Triassic giant ooids require a higher carbonate saturation state than typifies modern sites of ooid formation. Model calculations indicate that Early Triassic oceans were at least seven times supersaturated with respect to aragonite and calcite. When combined with independent constraints on atmospheric pCO2 and oceanic [Ca2+], these findings require that Early Triassic oceans had more than twice the modern levels of dissolved inorganic carbon and alkalinity and a pH near 7.6. Such conditions may have played a role in inhibiting the recovery of skeletal animals and algae during Early Triassic time.

Ghost Factors of Laboratory Carbonate Chemistry Are Haunting Our Experiments.

AbstractFor many historical and contemporary experimental studies in marine biology, seawater carbonate chemistry remains a ghost factor, an uncontrolled, unmeasured, and often dynamic variable affecting experimental organisms or the treatments to which investigators subject them. We highlight how environmental variability, such as seasonal upwelling and biological respiration, drive variation in seawater carbonate chemistry that can influence laboratory experiments in unintended ways and introduce a signal consistent with ocean acidification. As the impacts of carbonate chemistry on biochemical pathways that underlie growth, development, reproduction, and behavior become better understood, the hidden effects of this previously overlooked variable need to be acknowledged. Here we bring this emerging challenge to the attention of the wider community of experimental biologists who rely on access to organisms and water from marine and estuarine laboratories and who may benefit from explicit considerations of a growing literature on the pervasive effects of aquatic carbonate chemistry changes.

Aqueous Uranium Speciation on U/Ca in Foraminiferal Calcite: The Importance of Minor Species—UO2(CO3)22–

The decrease of uranium to calcium ratios (U/Ca) in biogenic CaCO3 with increasing pH and/or [CO32–] is being explored as a proxy to reconstruct past seawater carbonate chemistry. This inverse rela...