Calcium Carbonate Saturation State Research Articles

Underestimation of calcium carbonate saturation state in marginal seas due to the disregard of calcium ion addition: A case study of the Bohai sea, China

Seawater calcium ion (Ca2+) concentration was investigated based on the potentiometric titration method during the summer of 2018 in the Bohai Sea, China. The measured Ca2+ concentration ranged from 7760 to 9739 μmol kg−1 and deviated from the theoretical Ca2+ values, which were estimated from the calcium/salinity ratio. The excess calcium (Ca2+excess) ranged from 186 to 1229 μmol kg−1, showing a decreasing trend from the estuary to the nearshore, and then the offshore areas. Riverine input was an important source of seawater Ca2+excess in the Bohai Sea. Biological activity was another factor in regulating seawater Ca2+excess by precipitation in the Yellow River estuary and dissolution in other area of the Bohai Sea. Furthermore, the aragonite saturation state (Ωarag) values calculated from the measured Ca2+ concentrations showed a significant deviation from the values calculated from the theoretical Ca2+ concentrations, especially in the estuarine area with a maximum difference of 18.5%. Therefore, the disregard of the calcium addition would lead to an underestimation of the calcium carbonate saturation state and a deviation in the assessment of ocean acidification in marginal seas.

Multiple carbonate system parameters independently govern shell formation in a marine mussel

Calcification is vital to marine organisms that produce calcium carbonate shells and skeletons. However, how calcification is impacted by ongoing environmental changes, including ocean acidification, remains incompletely understood due to complex relationships among the carbonate system variables hypothesized to drive calcification. Here, we experimentally decouple these drivers in an exploration of shell formation in adult marine mussels, Mytilus californianus. In contrast to models that focus on single parameters like calcium carbonate saturation state, our results implicate two independent factors, bicarbonate concentration and seawater pH, in governing calcification. While qualitatively similar to ideas embodied in the related substrate-inhibitor ratio (bicarbonate divided by hydrogen ion concentration), our data highlight that merging bicarbonate ion and hydrogen ion concentrations into a simple quotient obscures important features of calcification. Considering a dual-parameter framework improves mechanistic understanding of how calcifiers interact with complex and changing chemical conditions.

Variability and drivers of carbonate chemistry at shellfish aquaculture sites in the Salish Sea, British Columbia

Abstract. Ocean acidification (OA) reduces seawater pH and calcium carbonate saturation states (Ω), which can have detrimental effects on calcifying organisms such as shellfish. Nearshore areas, where shellfish aquaculture typically operates, have limited data available to characterize variability in key ocean acidification parameters pH and Ω, as samples are costly to analyze and difficult to collect. This study collected samples from four nearshore locations at shellfish aquaculture sites on the Canadian Pacific coast from 2015–2018 and analyzed them for dissolved inorganic carbon (DIC) and total alkalinity (TA), enabling the calculation of pH and Ω for all seasons. The study evaluated the diel and seasonal variability in carbonate chemistry conditions at each location and estimated the contribution of drivers to seasonal and diel changes in pH and Ω. Nearshore locations experience a greater range of variability and seasonal and daily changes in pH and Ω than open waters. Biological uptake of DIC by phytoplankton is the major driver of seasonal and diel changes in pH and Ω at our nearshore sites. The study found that freshwater is not a key driver of diel variability, despite large changes over the day in some locations. We find that during summer at mid-depth (5–20 m), where it is cooler, pH, Ω, and oxygen conditions are still favourable for shellfish. These results suggest that if shellfish are hung lower in the water column, they may avoid high sea surface temperatures, without inducing OA and oxygen stress.

The additionality problem of ocean alkalinity enhancement

Abstract. Ocean alkalinity enhancement (OAE) is an emerging approach for atmospheric carbon dioxide removal (CDR). The net climatic benefit of OAE depends on how much it can increase CO2 sequestration relative to a baseline state without OAE. This so-called “additionality” can be calculated as follows: Additionality=COAE-ΔCbaseline. So far, feasibility studies on OAE have mainly focussed on enhancing alkalinity in the oceans to stimulate CO2 sequestration (COAE); however, the primary focus has not been on how such anthropogenic alkalinity would modify the natural alkalinity cycle and associated baseline CO2 sequestration (ΔCbaseline). Here, I present incubation experiments in which materials considered for OAE (sodium hydroxide, steel slag, and olivine) are exposed to beach sand to investigate the influence of anthropogenic alkalinity on natural alkalinity sources and sinks. The experiments show that anthropogenic alkalinity can strongly reduce the generation of natural alkalinity, thereby reducing additionality. This is because the anthropogenic alkalinity increases the calcium carbonate saturation state, which reduces the dissolution of calcium carbonate from sand, a natural alkalinity source. I argue that this “additionality problem” of OAE is potentially widespread and applies to many marine systems where OAE implementation is considered – far beyond the beach scenario investigated in this study. However, the problem can potentially be mitigated by dilute dosing of anthropogenic alkalinity into the ocean environment and the avoidance of OAE in natural alkalinity cycling hotspots, such as in marine sediments. Understanding a potential slowdown of the natural alkalinity cycle through the introduction of an anthropogenic alkalinity cycle will be crucial for the assessment of OAE.

Optimizing marine macrophyte capacity to locally ameliorate ocean acidification under variable light and flow regimes: Insights from an experimental approach.

The urgent need to remediate ocean acidification has brought attention to the ability of marine macrophytes (seagrasses and seaweeds) to take up carbon dioxide (CO2) and locally raise seawater pH via primary production. This physiological process may represent a powerful ocean acidification mitigation tool in coastal areas. However, highly variable nearshore environmental conditions pose uncertainty in the extent of the amelioration effect. We developed experiments in aquaria to address two interconnected goals. First, we explored the individual capacities of four species of marine macrophytes (Ulva lactuca, Zostera marina, Fucus vesiculosus and Saccharina latissima) to ameliorate seawater acidity in experimentally elevated pCO2. Second, we used the most responsive species (i.e., S. latissima) to assess the effects of high and low water residence time on the amelioration of seawater acidity in ambient and simulated future scenarios of climate change across a gradient of irradiance. We measured changes in dissolved oxygen, pH, and total alkalinity, and derived resultant changes to dissolved inorganic carbon (DIC) and calcium carbonate saturation state (Ω). While all species increased productivity under elevated CO2, S. latissima was able to remove DIC and alter pH and Ω more substantially as CO2 increased. Additionally, the amelioration of seawater acidity by S. latissima was optimized under high irradiance and high residence time. However, the influence of water residence time was insignificant under future scenarios. Finally, we applied predictive models as a function of macrophyte biomass, irradiance, and residence time conditions in ambient and future climatic scenarios to allow projections at the ecosystem level. This research contributes to understanding the biological and physical drivers of the coastal CO2 system.

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.

High-frequency, year-round time series of the carbonate chemistry in a high-Arctic fjord (Svalbard)

Abstract. The Arctic Ocean is subject to high rates of ocean warming and acidification, with critical implications for marine organisms as well as ecosystems and the services they provide. Carbonate system data in the Arctic realm are spotty in space and time, and, until recently, there was no time-series station measuring the carbonate chemistry at high frequency in this region, particularly in coastal waters. We report here on the first high-frequency (1 h), multi-year (5 years) dataset of salinity, temperature, CO2 partial pressure (pCO2) and pH at a coastal site (bottom depth of 12 m) in a high-Arctic fjord (Kongsfjorden, Svalbard). Discrete measurements of dissolved inorganic carbon and total alkalinity were also performed. We show that (1) the choice of formulations for calculating the dissociation constants of the carbonic acid remains unsettled for polar waters, (2) the water column is generally somewhat stratified despite the shallow depth, (3) the saturation state of calcium carbonate is subject to large seasonal changes but never reaches undersaturation (Ωa ranges between 1.4 and 3.0) and (4) pCO2 is lower than atmospheric CO2 at all seasons, making this site a sink for atmospheric CO2 (−9 to −16.8 molCO2m-2yr-1, depending on the parameterisation of the gas transfer velocity). Data are available on PANGAEA: https://doi.org/10.1594/PANGAEA.960131 (Gattuso et al., 2023a).

Organic alkalinity dynamics in Irish coastal waters: Case study Rogerstown Estuary

Total alkalinity (TA) is a popularly measured carbonate system parameter and is widely used in calculations of key carbonate system descriptors such as the calcium carbonate saturation state, an important indicator of ocean acidification. Organic alkalinity (OrgAlk) is recognised as a contributor to TA in coastal waters, with this having implications on the use of TA to calculate key carbonate chemistry descriptors. As titratable charge groups of OrgAlk can act as unknown acid-base species, the inclusion of the total concentration and apparent dissociation constants of OrgAlk in carbonate calculations involving TA is required to minimise uncertainty in computed speciation. Here we present an investigation of the prevalence and properties of OrgAlk as well as the impact of OrgAlk on carbonate chemistry calculations in a transitional waterbody. Water samples were collected during low and high tide over a 5-week period in Rogerstown Estuary, Dublin Ireland. TA and OrgAlk were measured using modified Global Ocean Acidification Observing Network (GOA-ON) titration apparatus in conjunction with OrgAlkCalc, an open-source Python based computational programme. pH was measured on the total scale using meta-cresol purple (mCP) as the indicator dye. Dissolved inorganic carbon (DIC), the partial pressure of CO2 (pCO2), in situ pH on the total scale (pHT) and the saturation state of aragonite (∆ΩA) were calculated using pH and both OrgAlk adjusted TA and measured TA as the input parameters. Optical analysis of DOM was conducted to compliment OrgAlk characterisations and to further elucidate OrgAlk sources and dynamics. OrgAlk charge groups concentrations ranged from 35,198 μmol·kg−1, with the highest concentrations observed in more marine waters. Two apparent charge groups were associated with OrgAlk, with pK values of 4.38 ± 0.27 and 6.95 ± 0.43. Differences between calculated carbonate system parameters when using OrgAlk adjusted TA and non-OrgAlk adjusted TA ranged from 88 to 254 μmol·kg−1 DIC, −98–67 μatm pCO2, −0.02–0.12 pHT and 0.02–0.64 ∆ΩA. Variability in the differences in calculated carbonate systems was largely a factor of OrgAlk charge group concentration and pK. This work highlights the importance of considering OrgAlk if using TA as an input parameter in carbonate system investigations of coastal waters.

The role of irradiance in controlling coralline algal calcification

AbstractCoralline algae are an essential element of benthic ecosystems throughout the ocean's photic zone. Yet, the role of light in shaping the physiology of coralline algae from cold‐water, low‐light habitats is poorly understood. Here, we assess the calcification physiology of five cool temperate coralline algae in response to different irradiance levels over 3 months. We show that in contrast to current models focused on warmer water species, previously observed enhancement of calcification rates by photosynthesis is largely limited to lower irradiances, and that the removal of CO2 from the calcifying fluid is not the underlying mechanism of this enhancement. Instead, this most likely occurs via two processes: (1) increased ion pumping rates to elevate the calcium carbonate saturation state in the calcifying fluid; and (2) a higher daytime pH in the diffusion boundary layer that raises calcifying fluid pH. However, as irradiance increases, ion pumping becomes increasingly saturated limiting further enhancements. Our results also suggest the existence of two calcification strategies in coralline algae and indicate that magnesium incorporation is determined by the magnesium to calcium ratio in the calcifying fluid ([Mg]CF/[Ca]CF). This study adds to our mechanistic understanding of calcification in coralline algae and fills in much needed knowledge about the role of light in controlling their physiology.

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.

Evaluating the Evolving Ocean Acidification Risk to Dungeness Crab: Time-Series Observations and Modeling on the Olympic Coast, Washington, USA

The state of Washington’s Olympic coast is home to four US coastal treaty tribes who have relied on the region’s rich marine resources since time immemorial. The region is characterized by large dynamic ranges of physical and biogeochemical oceanographic parameters, particularly during the upwelling season (April–September). Here, we present novel estimates of ocean acidification metrics—pH and calcium carbonate saturation states (Ω)—representing pre-industrial, present-day (using 2010 as the index year), and near-future (2030) conditions. We compare these new estimates of past, present, and near-future ocean acidification status and seasonality to published end-of-century (2100) ocean acidification projections under a high CO2 emissions scenario, and also to sensitivity information for Dungeness crab, a regionally important subsistence and commercial fishery species projected to show strong declines in fisheries yields and revenues later this century.

Carbonate system data tracing freshwater inflow into the Ross Sea through the eastern gate and along the Ross Ice Shelf (Antarctica)

The eastern Ross Sea is a key area to understand the role of the Amundsen Sea inflow of freshwater that can influence the Ross Sea water properties and salt budget. A survey was carried out in the eastern Ross Sea during the austral summer 2019–20 to evaluate the contribution of the Amundsen Sea Water (ASW) to the salinity variability. A total of 248 seawater samples were collected f\or the analysis of total alkalinity (AT) and pH. The data collected were used together with temperature and salinity to obtain a full description of the carbonate system properties including total inorganic carbon (CT), CO2 partial pressure (pCO2), calcium carbonate saturation state of aragonite and calcite (Ω), and Revelle factor. Moreover, we estimated the anthropogenic carbon (Cant) throughout the TrOCA method to better understand the carbon cycle, also considering the effect of atmospheric CO2 uptake on ocean acidification. We used principal component analysis (PCA) to investigate the major controls on the carbonate system parameters with the aim of defining their sensitivity as chemical tracers. The changes in carbonate chemistry in surface waters were mainly due to the physical properties. AT and pH traced the entry of the ASW showing limited mixing between water masses on the shelf area. Shelf waters were enriched in Cant, which resulted lower than the estimated value for shelf waters produced in western Ross Sea.

Growth as a function of sea ice cover, light and temperature in the arctic/subarctic coralline C. compactum: A year-long in situ experiment in the high arctic

Long-term, high-resolution measurements of environmental variability are sparse in the High Arctic. In the absence of such data, we turn to proxies recorded in the layered skeletons of the long-lived crustose coralline algae Clathromorphum compactum. Annual growth banding in this alga is dependent on several factors that include temperature, light availability, nutrients, salinity, and calcium carbonate saturation state. It has been observed that growth slows during winter as sunlight reaching the seafloor diminishes due to decreased insolation and the build-up of sea-ice, such that the relationship between sea-ice cover extent and algal growth has allowed for reconstructions of relative sea-ice variability through time. However, recent laboratory work has shown that C. compactum continue growing in complete darkness (sea-ice cover). Therefore, a more complete understanding of algal growth is necessary for the refinement of the sea-ice proxy. Here, we present the results of a ~year-long in-situ growth and environmental monitoring experiment in Arctic Bay, Nunavut, Canada (~73°N) which addresses, for the first time in situ, the gaps in our understanding of growth over an annual cycle in the High Arctic. Algal growth was assessed on a quasi-monthly basis, where specimens were subsampled to quantify monthly extension in the context of ocean temperature and light availability. By measuring extension rate through time, we observed that the algae grew on average 72 µm yr-1, with ~54% of annual growth occurring during the sea-ice free summer months (June-September), ~25% during the winter months (November-April), and ~21% occurring during the transition months of May and October. Although winter growth slowed, we did not observe a consistent cessation of linear extension during low-or no-light months. We posit that substantial growth during the winter months at this latitude is most likely a consequence of the mobilization of stored energy (photosynthate) produced during the photosynthetically active summer months. However, we also discuss the possibility of low light-photosynthetic activity and/or dark carbon fixation, which could also facilitate extension through time. Overall, the novel growth model presented here has implications for the use of C. compactum growth for reconstructing the environment as well as for trace-element-based (typically Mg/Ca) algal chronologies.

COASTAL OCEAN ACIDIFICATION IN BRAZIL: A BRIEF OVERVIEW AND PERSPECTIVES

This perspective paper aims at presenting the current knowledge on the processes of ocean acidification (OA) and coastal acidification (CA) in the Brazilian coastal ocean. We define and differentiate the processes of OA and CA: the first driven by the actual global increase of atmospheric carbon dioxide (CO2); the second driven by a combination of ocean uptake of atmospheric CO2 and other local/regional chemical additions or subtractions in aquatic ecosystems at the land-ocean interface. Regarding OA, we have centered our analysis on the data available for the main water masses along the Brazilian coast: South Atlantic Central Water (SACW), Tropical Water (TW), and Coastal Water (CW). The few data available for the shallow coastal waters (&lt; 200 m depth) of the continental shelf reveal an increase in the anthropogenic component of the total dissolved inorganic carbon (DIC) pool in the SACW, with a decline in the ocean pH (over two decades; 1993-2013), and in the saturation state of calcium carbonate (CaCO3) minerals. We could not find OA trends for TW and CW because no data was available. Overall, the colder water masses (SACW, Plata Plume) have lower buffering capacity and simulations show that will potentially experience earlier negative OA impacts than the warmer waters masses (TW, Amazon Plume). Regarding CA, we have identified some local/regional studies investigating the carbonate chemistry in nearshore/estuarine ecosystems, particularly on the quantification of sources and sinks of CO2 , and determining short-term variabilities. Apparently, spreading coastal eutrophication in Brazil can enhances or reduces the process of OA, depending on the net ecosystem metabolism in combination with other chemical alterations. However, we could not find medium-long term acidification trends due to the limited data. There is a limited capacity to produce long time-series of carbonate chemistry parameters in key ecosystems and regions along the Brazilian coast. This lack of past information hinders and impairs the scientific community for identifying potential patterns of acidification along the Brazilian coast. We call for an urgent action in Brazil, with emphasis on the establishment of moored buoys/stations and/or scientific programs in the long term with continuous, real-time measurements of the main carbonate chemistry parameters.&#x0D; Keywords: ocean acidification, coastal acidification, coastal eutrophication, continental shelf, Southwestern Atlantic Ocean

Acidification of the Nordic Seas

Abstract. Due to low calcium carbonate saturation states, and winter mixing that brings anthropogenic carbon to the deep ocean, the Nordic Seas and their cold-water corals are vulnerable to ocean acidification. Here, we present a detailed investigation of the changes in pH and aragonite saturation in the Nordic Seas from preindustrial times to 2100, by using in situ observations, gridded climatological data, and projections for three different future scenarios with the Norwegian Earth System Model (NorESM1-ME). During the period of regular ocean biogeochemistry observations from 1981–2019, the pH decreased with rates of 2–3 × 10−3 yr−1 in the upper 200 m of the Nordic Seas. In some regions, the pH decrease can be detected down to 2000 m depth. This resulted in a decrease in the aragonite saturation state, which is now close to undersaturation in the depth layer of 1000–2000 m. The model simulations suggest that the pH of the Nordic Seas will decrease at an overall faster rate than the global ocean from the preindustrial era to 2100, bringing the Nordic Seas' pH closer to the global average. In the esmRCP8.5 scenario, the whole water column is projected to be undersaturated with respect to aragonite at the end of the 21st century, thereby endangering all cold-water corals of the Nordic Seas. In the esmRCP4.5 scenario, the deepest cold-water coral reefs are projected to be exposed to undersaturation. Exposure of all cold-water corals to corrosive waters can only be avoided with marginal under the esmRCP2.6 scenario. Over all timescales, the main driver of the pH drop is the increase in dissolved inorganic carbon (CT) caused by the raising anthropogenic CO2, followed by the temperature increase. Thermodynamic salinity effects are of secondary importance. We find substantial changes in total alkalinity (AT) and CT as a result of the salinification, or decreased freshwater content, of the Atlantic water during all time periods, and as a result of an increased freshwater export in polar waters in past and future scenarios. However, the net impact of this decrease (increase) in freshwater content on pH is negligible, as the effects of a concentration (dilution) of CT and AT are canceling.

Seagrass meadows mixed with calcareous algae have higher plant productivity and sedimentary blue carbon storage.

Seagrass meadows capture and store large amounts of carbon in the sediment beneath, thereby serving as efficient sinks of atmospheric CO2. Carbon sequestration levels may however differ greatly among meadows depending on, among other factors, the plant community composition. Tropical seagrass meadows are often intermixed with macroalgae, many of which are calcareous, which may compete with seagrass for nutrients, light, and space. While the photosynthetic CO2 uptake by both seagrasses and calcareous algae may increase the overall calcification in the system (by increasing the calcium carbonate saturation state, Ω), the calcification process of calcareous algae may lead to a release of CO2, thereby affecting both productivity and calcification, and eventually also the meadows’ carbon storage. This study estimated how plant productivity, CaCO3 production, and sediment carbon levels were affected by plant community composition (seagrass and calcareous algae) in a tropical seagrass‐dominated embayment (Zanzibar, Tanzania). Overall, the patterns of variability in productivity differed between the plant types, with net areal biomass productivity being highest in meadows containing both seagrass and calcareous algae. Low and moderate densities of calcareous algae enhanced seagrass biomass growth, while the presence of seagrass reduced the productivity of calcareous algae but increased their CaCO3 content. Sedimentary carbon levels were highest when seagrasses were mixed with low or moderate cover of calcareous algae. The findings show that plant community composition can be an important driver for ecosystem productivity and blue carbon sequestration.

Calcium carbonate saturation states along the West Antarctic Peninsula

AbstractThe waters along the West Antarctic Peninsula (WAP) have experienced warming and increased freshwater inputs from melting sea ice and glaciers in recent decades. Challenges exist in understanding the consequences of these changes on the inorganic carbon system in this ecologically important and highly productive ecosystem. Distributions of dissolved inorganic carbon (CT), total alkalinity (AT) and nutrients revealed key physical, biological and biogeochemical controls of the calcium carbonate saturation state (Ωaragonite) in different water masses across the WAP shelf during the summer. Biological production in spring and summer dominated changes in surface water Ωaragonite (ΔΩaragonite up to +1.39; ~90%) relative to underlying Winter Water. Sea-ice and glacial meltwater constituted a minor source of AT that increased surface water Ωaragonite (ΔΩaragonite up to +0.07; ~13%). Remineralization of organic matter and an influx of carbon-rich brines led to cross-shelf decreases in Ωaragonite in Winter Water and Circumpolar Deep Water. A strong biological carbon pump over the shelf created Ωaragonite oversaturation in surface waters and suppression of Ωaragonite in subsurface waters. Undersaturation of aragonite occurred at &lt; ~1000 m. Ongoing changes along the WAP will impact the biologically driven and meltwater-driven processes that influence the vulnerability of shelf waters to calcium carbonate undersaturation in the future.

The influence of organic alkalinity on the carbonate system in coastal waters

Total alkalinity (TA) is one of the four main carbonate system variables and is a conventionally measured parameter used to characterise marine water carbonate chemistry. It is an important indicator of a waterbody's buffering capacity and a measure of its ability to resist acidification, a matter of growing concern in the marine environment. Although TA is primarily associated with the inorganic components of seawater such as bicarbonate, there is a growing consensus that dissolved organic matter (DOM) can significantly contribute to TA in coastal waters. This organic fraction of TA (OrgAlk) is typically deemed negligible and is not accounted for in conventional TA expressions. However, omission of OrgAlk can lead to the propagation of errors in subsequent carbonate system calculations and to misinterpretation of key carbonate chemistry descriptors such as calcium carbonate saturation states. Here we provide an overview of OrgAlk contributions to TA and investigate the implications of its omission in carbonate system studies conducted in coastal waters. We examine the prevalence of OrgAlk across both coastal and pelagic waters using publicly available carbonate system data products, such as GLODAP and GOMECC. Current measures to account for, incorporate and characterise the contribution of OrgAlk to TA are also critically examined.

The Gulf of St. Lawrence Biogeochemical Model: A Modelling Tool for Fisheries and Ocean Management

The goal of this paper is to give a detailed description of the coupled physical-biogeochemical model of the Gulf of St. Lawrence that includes dissolved oxygen and carbonate system components, as well as a detailed analysis of the riverine contribution for different nitrogen and carbonate system components. A particular attention was paid to the representation of the microbial loop in order to maintain the appropriate level of the different biogeochemical components within the system over long term simulations. The skill of the model is demonstrated using in situ data, satellite data and estimated fluxes from different studies based on observational data. The model reproduces the main features of the system such as the phytoplankton bloom, hypoxic areas, pH and calcium carbonate saturation states. The model also reproduces well the estimated transport of nitrate from one region to the other. We revisited previous estimates of the riverine nutrient contribution to surface nitrate in the Lower St. Lawrence Estuary using the model. We also explain the mechanisms that lead to high ammonium concentrations, low dissolved oxygen, and undersaturated calcium carbonate conditions on the Magdalen Shallows.

Continuous Monitoring and Future Projection of Ocean Warming, Acidification, and Deoxygenation on the Subarctic Coast of Hokkaido, Japan

As the ocean absorbs excessive anthropogenic CO2 and ocean acidification proceeds, it is thought to be harder for marine calcifying organisms, such as shellfish, to form their skeletons and shells made of calcium carbonate. Recent studies have suggested that various marine organisms, both calcifiers and non-calcifiers, will be affected adversely by ocean warming and deoxygenation. However, regardless of their effects on calcifiers, the spatiotemporal variability of parameters affecting ocean acidification and deoxygenation has not been elucidated in the subarctic coasts of Japan. This study conducted the first continuous monitoring and future projection of physical and biogeochemical parameters of the subarctic coast of Hokkaido, Japan. Our results show that the seasonal change in biogeochemical parameters, with higher pH and dissolved oxygen (DO) concentration in winter than in summer, was primarily regulated by water temperature. The daily fluctuations, which were higher in the daytime than at night, were mainly affected by daytime photosynthesis by primary producers and respiration by marine organisms at night. Our projected results suggest that, without ambitious commitment to reducing CO2 and other greenhouse gas emissions, such as by following the Paris Agreement, the impact of ocean warming and acidification on calcifiers along subarctic coasts will become serious, exceeding the critical level of high temperature for 3 months in summer and being close to the critical level of low saturation state of calcium carbonate for 2 months in mid-winter, respectively, by the end of this century. The impact of deoxygenation might often be prominent assuming that the daily fluctuation in DO concentration in the future is similar to that at present. The results also suggest the importance of adaptation strategies by local coastal industries, especially fisheries, such as modifying aquaculture styles.