Calcium Carbonate Saturation State Research Articles

Effect of glacial drainage water on the CO2 system and ocean acidification state in an Arctic tidewater‐glacier fjord during two contrasting years

AbstractIn order to investigate the effect of glacial water on the CO2 system in the fjord, we studied the variability of the total alkalinity (AT), total dissolved inorganic carbon (CT), dissolved inorganic nutrients, oxygen isotopic ratio (δ18O), and freshwater fractions from the glacier front to the outer Tempelfjorden on Spitsbergen in winter 2012 (January, March, and April) and 2013 (April) and summer/fall 2013 (September). The two contrasting years clearly showed that the influence of freshwater, mixing, and haline convection affected the chemical and physical characteristics of the fjord. The seasonal variability showed the lowest calcium carbonate saturation state (Ω) and pH values in March 2012 coinciding with the highest freshwater fractions. The highest Ω and pH were found in September 2013, mostly due to CO2 uptake during primary production. Overall, we found that increased freshwater supply decreased Ω, pH, and AT. On the other hand, we observed higher AT relative to salinity in the freshwater end‐member in the mild and rainy winter of 2012 (1142 μmol kg−1) compared to AT in 2013 (526 μmol kg−1). Observations of calcite and dolomite crystals in the glacial ice suggested supply of carbonate‐rich glacial drainage water to the fjord. This implies that winters with a large amount of glacial drainage water partly provide a lessening of further ocean acidification, which will also affect the air‐sea CO2 exchange.

Seaweed fails to prevent ocean acidification impact on foraminifera along a shallow-water CO2 gradient.

Ocean acidification causes biodiversity loss, alters ecosystems, and may impact food security, as shells of small organisms dissolve easily in corrosive waters. There is a suggestion that photosynthetic organisms could mitigate ocean acidification on a local scale, through seagrass protection or seaweed cultivation, as net ecosystem organic production raises the saturation state of calcium carbonate making seawater less corrosive. Here, we used a natural gradient in calcium carbonate saturation, caused by shallow-water CO2 seeps in the Mediterranean Sea, to assess whether seaweed that is resistant to acidification (Padina pavonica) could prevent adverse effects of acidification on epiphytic foraminifera. We found a reduction in the number of species of foraminifera as calcium carbonate saturation state fell and that the assemblage shifted from one dominated by calcareous species at reference sites (pH ∼8.19) to one dominated by agglutinated foraminifera at elevated levels of CO2 (pH ∼7.71). It is expected that ocean acidification will result in changes in foraminiferal assemblage composition and agglutinated forms may become more prevalent. Although Padina did not prevent adverse effects of ocean acidification, high biomass stands of seagrass or seaweed farms might be more successful in protecting epiphytic foraminifera.

Processes determining the marine alkalinity and calcium carbonate saturation state distributions

Abstract. We introduce a composite tracer for the marine system, Alk*, that has a global distribution primarily determined by CaCO3 precipitation and dissolution. Alk* is also affected by riverine alkalinity from dissolved terrestrial carbonate minerals. We estimate that the Arctic receives approximately twice the riverine alkalinity per unit area as the Atlantic, and 8 times that of the other oceans. Riverine inputs broadly elevate Alk* in the Arctic surface and particularly near river mouths. Strong net carbonate precipitation results in low Alk* in subtropical gyres, especially in the Indian and Atlantic oceans. Upwelling of dissolved CaCO3-rich deep water elevates North Pacific and Southern Ocean Alk*. We use the Alk* distribution to estimate the variability of the calcite saturation state resulting from CaCO3 cycling and other processes. We show that regional differences in surface calcite saturation state are due primarily to the effect of temperature differences on CO2 solubility and, to a lesser extent, differences in freshwater content and air–sea disequilibria. The variations in net calcium carbonate cycling revealed by Alk* play a comparatively minor role in determining the calcium carbonate saturation state.

Considerations for the measurement of spectrophotometric pH for ocean acidification and other studies

Indicator‐based spectrophotometric pH is commonly used for the analysis of seawater because of its high precision and long‐term reproducibility. Users come from an increasingly diverse range of disciplines, primarily motivated by studies focused on the causes and effects of ocean acidification. While the analysis is readily implemented and straightforward, there are many variables that must be predetermined or measured, all of which can contribute uncertainty to the measurement. The indicator equilibrium constant and molar absorption coefficient ratios are available in the literature, but for various reasons, the conditions of analysis can be different, creating errors. Most of the parameters are temperature, salinity, and pressure dependent, posing potential additional errors. Indicator impurities and indicator perturbation of the sample pH also create uncertainties. We systematically evaluate all of the sources of error and compute how the errors propagate into CO2 equilibrium calculations of the partial pressure of CO2 (pCO2) and calcium carbonate saturation states (Ω). The primary sources of uncertainty originate from wavelength and absorbance errors in low quality or poorly functioning spectrophotometers (0.007 to 0.020 pH units) and indicator impurities (0.000 to >0.040 pH units). These errors generate pCO2 and Ω uncertainties of 11‐200 µatm and 0.08‐0.38, respectively, depending upon the pH value and its uncertainty.

Pacific-wide contrast highlights resistance of reef calcifiers to ocean acidification.

Ocean acidification (OA) and its associated decline in calcium carbonate saturation states is one of the major threats that tropical coral reefs face this century. Previous studies of the effect of OA on coral reef calcifiers have described a wide variety of outcomes for studies using comparable partial pressure of CO2 (pCO2) ranges, suggesting that key questions remain unresolved. One unresolved hypothesis posits that heterogeneity in the response of reef calcifiers to high pCO2 is a result of regional-scale variation in the responses to OA. To test this hypothesis, we incubated two coral taxa (Pocillopora damicornis and massive Porites) and two calcified algae (Porolithon onkodes and Halimeda macroloba) under 400, 700 and 1000 μatm pCO2 levels in experiments in Moorea (French Polynesia), Hawaii (USA) and Okinawa (Japan), where environmental conditions differ. Both corals and H. macroloba were insensitive to OA at all three locations, while the effects of OA on P. onkodes were location-specific. In Moorea and Hawaii, calcification of P. onkodes was depressed by high pCO2, but for specimens in Okinawa, there was no effect of OA. Using a study of large geographical scale, we show that resistance to OA of some reef species is a constitutive character expressed across the Pacific.

Low calcium carbonate saturation state in an Arctic inland sea having large and varying fluvial inputs: The Hudson Bay system

AbstractThe Hudson Bay system (HBS) is a shallow inland sea in the Arctic, composed of Hudson Strait, Foxe Basin/Channel, James Bay, and Hudson Bay. Dissolved inorganic carbon (DIC) and total alkalinity (TA) measurements were used to investigate the state of ocean acidification, specifically calcium carbonate saturation states (Ω) and pH. The freshwater sources were identified from the relationship between oxygen isotope composition (δ18O) and salinity to understand the role of freshwater in ocean acidification. The saturation state of seawater with respect to calcium carbonate (Ω) in surface water (<10 m) of the HBS was strongly influenced by river runoff. Aragonite under‐saturation (Ωarg < 1) was observed in the surface water of the south‐eastern Hudson Bay, where the river runoff fraction was high (>10%). The watershed characteristics, however, influenced the alkalinity of river runoff in different parts of Hudson Bay, which contributed to Ω variation in the coastal region. In southwestern Hudson Bay where the watershed is dominated by limestone, Ω was higher compared to eastern Hudson Bay, where the watershed consists of an igneous rock formation. In deeper waters, low Ω is caused by remineralization of organic matter. The highest DIC concentrations (>2300 µmol/kg) were observed in the depths of central Hudson Bay with a pHtotal of 7.49 and Ωarg of 0.37. Over 67% and 22% of the bottom water of Hudson Bay was undersaturated with respect to aragonite and calcite respectively, despite Hudson Bay being very shallow (less than 250 m deep). The aragonite saturation horizon in the central Hudson Bay was around 50 m.

Long-term trends in alkalinity in large rivers of the conterminous US in relation to acidification, agriculture, and hydrologic modification

Long-term trends in alkalinity in large rivers of the conterminous US in relation to acidification, agriculture, and hydrologic modification

Measuring Ocean Acidification: New Technology for a New Era of Ocean Chemistry

Human additions of carbon dioxide to the atmosphere are creating a cascade of chemical consequences that will eventually extend to the bottom of all the world's oceans. Among the best-documented seawater effects are a worldwide increase in open-ocean acidity and large-scale declines in calcium carbonate saturation states. The susceptibility of some young, fast-growing calcareous organisms to adverse impacts highlights the potential for biological and economic consequences. Many important aspects of seawater CO2 chemistry can be only indirectly observed at present, and important but difficult-to-observe changes can include shifts in the speciation and possibly bioavailability of some life-essential elements. Innovation and invention are urgently needed to develop the in situ instrumentation required to document this era of rapid ocean evolution.

Nearshore Carbonate Dissolution in the Hawaiian Archipelago?

Inorganic carbon measurements made in the late 1980s suggest that alkalinity in the waters surrounding the Hawaiian Archipelago is elevated relative to the oligotrophic waters of the North Pacific. These observations have been interpreted as evidence for a “halo” of elevated carbonate saturation state produced by the dissolution of highly soluble magnesium calcites and aragonite on the island platform or in the water column surrounding the islands. If present, this “halo” has implications for air–sea carbon dioxide exchange in Hawaiian waters and may impact the response of coral reef communities to the acidification of the surface waters of the global ocean. The purpose of this study was to assess the magnitude and extent of the elevated calcium carbonate saturation state observed on previous expeditions to this region. Transects were conducted near several atolls in the Northwestern Hawaiian Islands from shallow water adjacent to the forereef to the open ocean 15 km from the island. Hydrographic profiles were collected at each station, and discrete water samples were collected for the measurement of carbon system parameters necessary to compute calcium carbonate saturation state. Our data were compared with observations made at the Hawaii Ocean Time-series site at Station ALOHA and with hydrographic data collected on the WOCE lines in the North Pacific around the archipelago. We did not detect a carbonate dissolution halo around the islands. We conclude that the previously observed halo was probably an analytical artifact, or possibly a result of extreme variability in carbon chemistry surrounding the islands.

Calcium carbonate corrosivity in an Alaskan inland sea

Abstract. Ocean acidification is the hydrogen ion increase caused by the oceanic uptake of anthropogenic CO2, and is a focal point in marine biogeochemistry, in part, because this chemical reaction reduces calcium carbonate (CaCO3) saturation states (Ω) to levels that are corrosive (i.e., Ω ≤ 1) to shell-forming marine organisms. However, other processes can drive CaCO3 corrosivity; specifically, the addition of tidewater glacial melt. Carbonate system data collected in May and September from 2009 through 2012 in Prince William Sound (PWS), a semienclosed inland sea located on the south-central coast of Alaska and ringed with fjords containing tidewater glaciers, reveal the unique impact of glacial melt on CaCO3 corrosivity. Initial limited sampling was expanded in September 2011 to span large portions of the western and central sound, and included two fjords proximal to tidewater glaciers: Icy Bay and Columbia Bay. The observed conditions in these fjords affected CaCO3 corrosivity in the upper water column (< 50 m) in PWS in two ways: (1) as spring-time formation sites of mode water with near-corrosive Ω levels seen below the mixed layer over a portion of the sound, and (2) as point sources for surface plumes of glacial melt with corrosive Ω levels (Ω for aragonite and calcite down to 0.60 and 1.02, respectively) and carbon dioxide partial pressures (pCO2) well below atmospheric levels. CaCO3 corrosivity in glacial melt plumes is poorly reflected by pCO2 or pHT, indicating that either one of these carbonate parameters alone would fail to track Ω in PWS. The unique Ω and pCO2 conditions in the glacial melt plumes enhances atmospheric CO2 uptake, which, if not offset by mixing or primary productivity, would rapidly exacerbate CaCO3 corrosivity in a positive feedback. The cumulative effects of glacial melt and air–sea gas exchange are likely responsible for the seasonal reduction of Ω in PWS, making PWS highly sensitive to increasing atmospheric CO2 and amplified CaCO3 corrosivity.

Biogeochemical Control of the Coupled CO2–O2 System of the Baltic Sea: A Review of the Results of Baltic-C

Past, present, and possible future changes in the Baltic Sea acid–base and oxygen balances were studied using different numerical experiments and a catchment–sea model system in several scenarios including business as usual, medium scenario, and the Baltic Sea Action Plan. New CO2 partial pressure data provided guidance for improving the marine biogeochemical model. Continuous CO2 and nutrient measurements with high temporal resolution helped disentangle the biogeochemical processes. These data and modeling indicate that traditional understandings of the nutrient availability–organic matter production relationship do not necessarily apply to the Baltic Sea. Modeling indicates that increased nutrient loads will not inhibit future Baltic Sea acidification; instead, increased mineralization and biological production will amplify the seasonal surface pH cycle. The direction and magnitude of future pH changes are mainly controlled by atmospheric CO2 concentration. Apart from decreasing pH, we project a decreasing calcium carbonate saturation state and increasing hypoxic area.

Ocean acidification state in western Antarctic surface waters: controls and interannual variability

Abstract. During four austral summers (December to January) from 2006 to 2010, we investigated the surface-water carbonate system and its controls in the western Antarctic Ocean. Measurements of total alkalinity (AT), pH and total inorganic carbon (CT) were investigated in combination with high-frequency measurements on sea-surface temperature (SST), salinity and Chl a. In all parameters we found large interannual variability due to differences in sea-ice concentration, physical processes and primary production. The main result from our observations suggests that primary production was the major control on the calcium carbonate saturation state (Ω) in austral summer for all years. This was mainly reflected in the covariance of pH and Chl a. In the sea-ice-covered parts of the study area, pH and Ω were generally low, coinciding with low Chl a concentrations. The lowest pH in situ and lowest aragonite saturation (ΩAr ~ 1.0) were observed in December 2007 in the coastal Amundsen and Ross seas near marine outflowing glaciers. These low Ω and high pH values were likely influenced by freshwater dilution. Comparing 2007 and 2010, the largest ΩAr difference was found in the eastern Ross Sea, where ΩAr was about 1.2 units lower in 2007 than in 2010. This was mainly explained by differences in Chl a (i.e primary production). In 2010 the surface water along the Ross Sea shelf was the warmest and most saline, indicating upwelling of nutrient and CO2-rich sub-surface water, likely promoting primary production leading to high Ω and pH. Results from multivariate analysis agree with our observations showing that changes in Chl a had the largest influence on the ΩAr variability. The future changes of ΩAr were estimated using reported rates of the oceanic uptake of anthropogenic CO2, combined with our data on total alkalinity, SST and salinity (summer situation). Our study suggests that the Amundsen Sea will become undersaturated with regard to aragonite about 40 yr sooner than predicted by models.

Future ocean acidification in the Canada Basin and surrounding Arctic Ocean from CMIP5 earth system models

Six Earth system models that include an interactive carbon cycle and have contributed results to the 5th Coupled Model Intercomparison Project (CMIP5) are evaluated with respect to Arctic Ocean acidification. Projections under Representative Concentration Pathways (RCPs) 8.5 and 4.5 consistently show reductions in the bidecadal mean surface pH from about 8.1 in 1986–2005 to 7.7/7.9 by 2066–2085 in the Canada Basin, closely linked to reductions in the calcium carbonate saturation state ΩA,C from about 1.4 (2.0) to 0.7 (1.0) for aragonite (calcite) for RCP8.5. The large but opposite effects of dilution and biological drawdown of DIC and dilution of alkalinity lead to a small seasonal amplitude change in Ω, as well as intermodel differences in the timing and sign of the summer minimum. The Canada Basin shows a characteristic layering in Ω: affected by ice melt and inflowing Pacific water, shallow undersaturated layers form at the surface and subsurface, creating a shallow saturation horizon which expands from the surface downward. This is in addition to the globally observed deep saturation horizon which is continuously expanding upward with increasing CO2 uptake. The Eurasian Basin becomes undersaturated much later than the rest of the Arctic. These CMIP5 model results strengthen earlier findings, although large intermodel differences remain: Below 200 m ΩA varies by up to 1.0 in the Canada Basin and the deep saturation horizon varies from 2000 to 4000 m among the models. Differences of projected acidification changes are primarily related to sea ice retreat and responses of wind mixing and stratification.

Controls on the seasonal variability of calcium carbonate saturation states in the Atlantic gateway to the Arctic Ocean

Controls on the seasonal variability of calcium carbonate saturation states in the Atlantic gateway to the Arctic Ocean

Ocean acidification in the three oceans surrounding northern North America

[1] The uptake of anthropogenic CO2 drives ocean acidification, with attendant effects on the saturation state of calcium carbonate (Ω) and marine ecosystems. Here, we examine ocean acidification within the context of large-scale water mass exchange and local physical and biogeochemical processes along a section around northern North America. Waters in the North Pacific are preconditioned by the global-scale circulation to be low Ω source waters and as they move northward across the Bering and Chukchi seas they are modified by biological activity. These waters then enter the Canada Basin and Canadian Arctic Archipelago where cooling, river discharge, sea ice formation and biological activities modify water mass characteristics further. Continuing eastward into Baffin Bay, relatively low Ω waters extend from the surface to depth due to remineralization. Changes in Ω are large along this pathway and the response of local marine ecosystems will likewise be shaped by the biogeography of species occupying a given region.

Tropical cyclones cause CaCO3undersaturation of coral reef seawater in a high-CO2world

[1] Ocean acidification is the global decline in seawater pH and calcium carbonate (CaCO3) saturation state (Ω) due to the uptake of anthropogenic CO2 by the world's oceans. Acidification impairs CaCO3 shell and skeleton construction by marine organisms. Coral reefs are particularly vulnerable, as they are constructed by the CaCO3 skeletons of corals and other calcifiers. We understand relatively little about how coral reefs will respond to ocean acidification in combination with other disturbances, such as tropical cyclones. Seawater carbonate chemistry data collected from two reefs in the Florida Keys before, during, and after Tropical Storm Isaac provide the most thorough data to-date on how tropical cyclones affect the seawater CO2 system of coral reefs. Tropical Storm Isaac caused both an immediate and prolonged decline in seawater pH. Aragonite saturation state was depressed by 1.0 for a full week after the storm impact. Based on current “business-as-usual” CO2 emissions scenarios, we show that tropical cyclones with high rainfall and runoff can cause periods of undersaturation (Ω < 1.0) for high-Mg calcite and aragonite mineral phases at acidification levels before the end of this century. Week-long periods of undersaturation occur for 18 mol % high-Mg calcite after storms by the end of the century. In a high-CO2 world, CaCO3 undersaturation of coral reef seawater will occur as a result of even modest tropical cyclones. The expected increase in the strength, frequency, and rainfall of the most severe tropical cyclones with climate change in combination with ocean acidification will negatively impact the structural persistence of coral reefs.

Spatiotemporal Variability of Dimethylsulphoniopropionate on a Fringing Coral Reef: The Role of Reefal Carbonate Chemistry and Environmental Variability

Oceanic pH is projected to decrease by up to 0.5 units by 2100 (a process known as ocean acidification, OA), reducing the calcium carbonate saturation state of the oceans. The coastal ocean is expected to experience periods of even lower carbonate saturation state because of the inherent natural variability of coastal habitats. Thus, in order to accurately project the impact of OA on the coastal ocean, we must first understand its natural variability. The production of dimethylsulphoniopropionate (DMSP) by marine algae and the release of DMSP’s breakdown product dimethylsulphide (DMS) are often related to environmental stress. This study investigated the spatiotemporal response of tropical macroalgae (Padina sp., Amphiroa sp. and Turbinaria sp.) and the overlying water column to natural changes in reefal carbonate chemistry. We compared macroalgal intracellular DMSP and water column DMSP+DMS concentrations between the environmentally stable reef crest and environmentally variable reef flat of the fringing Suleman Reef, Egypt, over 45-hour sampling periods. Similar diel patterns were observed throughout: maximum intracellular DMSP and water column DMS/P concentrations were observed at night, coinciding with the time of lowest carbonate saturation state. Spatially, water column DMS/P concentrations were highest over areas dominated by seagrass and macroalgae (dissolved DMS/P) and phytoplankton (particulate DMS/P) rather than corals. This research suggests that macroalgae may use DMSP to maintain metabolic function during periods of low carbonate saturation state. In the reef system, seagrass and macroalgae may be more important benthic producers of dissolved DMS/P than corals. An increase in DMS/P concentrations during periods of low carbonate saturation state may become ecologically important in the future under an OA regime, impacting larval settlement and increasing atmospheric emissions of DMS.

Early Exposure of Bay Scallops (Argopecten irradians) to High CO2 Causes a Decrease in Larval Shell Growth

Ocean acidification, characterized by elevated pCO2 and the associated decreases in seawater pH and calcium carbonate saturation state (Ω), has a variable impact on the growth and survival of marine invertebrates. Larval stages are thought to be particularly vulnerable to environmental stressors, and negative impacts of ocean acidification have been seen on fertilization as well as on embryonic, larval, and juvenile development and growth of bivalve molluscs. We investigated the effects of high CO2 exposure (resulting in pH = 7.39, Ωar = 0.74) on the larvae of the bay scallop Argopecten irradians from 12 h to 7 d old, including a switch from high CO2 to ambient CO2 conditions (pH = 7.93, Ωar = 2.26) after 3 d, to assess the possibility of persistent effects of early exposure. The survival of larvae in the high CO2 treatment was consistently lower than the survival of larvae in ambient conditions, and was already significantly lower at 1 d. Likewise, the shell length of larvae in the high CO2 treatment was significantly smaller than larvae in the ambient conditions throughout the experiment and by 7 d, was reduced by 11.5%. This study also demonstrates that the size effects of short-term exposure to high CO2 are still detectable after 7 d of larval development; the shells of larvae exposed to high CO2 for the first 3 d of development and subsequently exposed to ambient CO2 were not significantly different in size at 3 and 7 d than the shells of larvae exposed to high CO2 throughout the experiment.

Spectrophotometric Measurement of Calcium Carbonate Saturation States in Seawater

Measurements of ocean pH and carbonate ion concentrations in the North Pacific and Arctic Oceans were used to determine calcium carbonate saturation states (Ω(CaCO(3))) from spectrophotometric methods alone. Total carbonate ion concentrations, [CO(3)(2-)](T), were for the first time at sea directly measured using Pb(II) UV absorbance spectra. The basis of the method is given by the following: [formula see text] where (CO(3))β(1) is the PbCO(3)(0) formation constant, e(i) are molar absorptivity ratios, and R = (250)A/(234)A (ratio of absorbances measured at 250 and 234 nm). On the basis of shipboard and laboratory Pb(II) data and complementary carbon-system measurements, the experimental parameters were determined to be (25 °C) the following: [formula see text]. The resulting mean difference between the shipboard spectrophotometric and conventional determinations of [CO(3)(2-)](T) was ±2.03 μmol kg(-1). The shipboard analytical precision of the Pb(II) method was ∼1.71 μmol kg(-1) (2.28%). Spectrophotometric [CO(3)(2-)](T) and pH(T) were then combined to calculate Ω(CaCO(3)). For the case of aragonite, 95% of the spectrophotometric aragonite saturation states (Ω(Aspec)) were within ±0.06 of the conventionally calculated values (Ω(Acalc)) when 0.5 ≤ Ω(A) ≤ 2.0. When Ω(A) > 2.0, 95% of the Ω(Aspec) values were within ±0.18 of Ω(Acalc). Our shipboard experience indicates that spectrophotometric determinations of [CO(3)(2-)](T) and Ω(CaCO(3)) are straightforward, fast, and precise. The method yields high-quality measurements of two important, rapidly changing aspects of ocean chemistry and offers capabilities suitable for long-term automated in situ monitoring.

Aragonite saturation states at cold‐water coral reefs structured by Lophelia pertusa in the northern Gulf of Mexico

Ocean acidification, the reduction in pH and calcium carbonate saturation states of seawater, is likely to exhibit its most immediate effects on cold‐water corals in deep waters with the shoaling of the aragonite saturation horizon. However, empirical data describing the carbonate chemistry at cold‐water coral reefs are very rare. Regions of the upper slope of the Northern Gulf of Mexico harbor several deep‐water reefs structured by the scleractinian Lophelia pertusa. We collected discreet water samples at a range of depths in the Gulf of Mexico, including eight Lophelia reefs, and measured total alkalinity and pH to calculate the aragonite saturation state (Ωarag). The deep waters of the Gulf of Mexico (&gt; 300 m depth) were at aragonite saturation states between 0.98 and 1.69. L. pertusa was present at sites with Ωarag between 1.25 and 1.69, and carbonate ion concentrations between 92 and 123 µmol kg−1. These data provide a critical baseline for detecting future changes in carbonate chemistry in the water column (i.e., aragonite saturation horizon shoaling), as well as at the sites of well‐developed cold‐water coral structures threatened by ongoing ocean acidification.