scholarly journals Current estimates of K<sub>1</sub>* and K<sub>2</sub>* appear inconsistent with measured CO<sub>2</sub> system parameters in cold oceanic regions

Ocean Science ◽  
2020 ◽  
Vol 16 (4) ◽  
pp. 847-862 ◽  
Author(s):  
Olivier Sulpis ◽  
Siv K. Lauvset ◽  
Mathilde Hagens
Keyword(s):  
Surface Water ◽  
Ocean Acidification ◽  
Carbonic Acid ◽  
Dissolved Inorganic Carbon ◽  
Dissociation Constants ◽  
Total Alkalinity ◽  
Global Ocean ◽  
Polar Regions ◽  
Carbonate System ◽  
System Variables

Abstract. Seawater absorption of anthropogenic atmospheric carbon dioxide (CO2) has led to a range of changes in carbonate chemistry, collectively referred to as ocean acidification. Stoichiometric dissociation constants used to convert measured carbonate system variables (pH, pCO2, dissolved inorganic carbon, total alkalinity) into globally comparable parameters are crucial for accurately quantifying these changes. The temperature and salinity coefficients of these constants have generally been experimentally derived under controlled laboratory conditions. Here, we use field measurements of carbonate system variables taken from the Global Ocean Data Analysis Project version 2 and the Surface Ocean CO2 Atlas data products to evaluate the temperature dependence of the carbonic acid stoichiometric dissociation constants. By applying a novel iterative procedure to a large dataset of 948 surface-water, quality-controlled samples where four carbonate system variables were independently measured, we show that the set of equations published by Lueker et al. (2000), currently preferred by the ocean acidification community, overestimates the stoichiometric dissociation constants at temperatures below about 8 ∘C. We apply these newly derived temperature coefficients to high-latitude Argo float and cruise data to quantify the effects on surface-water pCO2 and calcite saturation states. These findings highlight the critical implications of uncertainty in stoichiometric dissociation constants for future projections of ocean acidification in polar regions and the need to improve knowledge of what causes the CO2 system inconsistencies in cold waters.

scholarly journals Current estimates of K<sub>1</sub><sup>*</sup> and K<sub>2</sub><sup>*</sup> appear inconsistent with measured CO<sub>2</sub> system parameters in cold oceanic regions

2020 ◽  
Author(s):  
Olivier Sulpis ◽  
Siv K. Lauvset ◽  
Mathilde Hagens
Keyword(s):  
Surface Water ◽  
Ocean Acidification ◽  
Carbonic Acid ◽  
Dissolved Inorganic Carbon ◽  
Dissociation Constants ◽  
Total Alkalinity ◽  
Global Ocean ◽  
Polar Regions ◽  
Carbonate System ◽  
System Variables

Abstract. Seawater absorption of anthropogenic atmospheric carbon dioxide (CO2) has led to a range of changes in carbonate chemistry, collectively referred to as ocean acidification. Stoichiometric dissociation constants used to convert measured carbonate system variables (pH, pCO2, dissolved inorganic carbon, total alkalinity) into globally comparable parameters are crucial for accurately quantifying these changes. The temperature and salinity coefficients of these constants have generally been experimentally derived under controlled laboratory conditions. Here, we use field measurements of carbonate system variables taken from the Global Ocean Data Analysis Project version 2 and the Surface Ocean CO2 Atlas databases to evaluate the temperature dependence of the carbonic acid stoichiometric dissociation constants. By applying a novel iterative procedure to a large dataset of 948 surface-water, quality-controlled samples where four carbonate system variables were independently measured, we show that the set of equations published by Lueker et al. (2000), currently preferred by the ocean acidification community, overestimates the stoichiometric dissociation constants at low temperatures, below ~ 8 °C. We apply these newly derived temperature coefficients to high-latitude Argo float and cruise data to quantify the effects on surface-water pCO2 and calcite saturation states. These findings highlight the critical implications of uncertainty in stoichiometric dissociation constants for future projections of ocean acidification in polar regions, and the need to improve knowledge of what causes the CO2 system inconsistencies in cold waters.

scholarly journals OceanSODA-ETHZ: A global gridded data set of the surface ocean carbonate system for seasonal to decadal studies of ocean acidification

2020 ◽  
Author(s):  
Luke Gregor ◽  
Nicolas Gruber
Keyword(s):  
Ocean Acidification ◽  
Dissolved Inorganic Carbon ◽  
Total Error ◽  
Total Alkalinity ◽  
Global Ocean ◽  
Carbonate System ◽  
Data Set ◽  
Saturation State ◽  
Mean Squared Errors ◽  
Surface Ocean

Abstract. Ocean acidification has altered the ocean's carbonate chemistry profoundly since preindustrial times, with potentially serious consequences for marine life. Yet, no long-term global observation-based data set exists that permits to study changes in ocean acidification for all carbonate system parameters over the last few decades. Here, we fill this gap and present a methodologically consistent global data set of all relevant surface ocean parameters, i.e., dissolved inorganic carbon (DIC), total alkalinity (TA), partial pressure of CO2 (pCO2), pH, and the saturation state with respect to mineral CaCO3 (Ω) at monthly resolution over the period 1985 through 2018 at a spatial resolution of 1 × 1°. This data set, named OceanSODA-ETHZ, was created by extrapolating in time and space the surface ocean observations of pCO2 (from the Surface Ocean CO2 ATlas (SOCAT)) and total alkalinity (TA, from the Global Ocean Data Analysis Project (GLODAP)) using the newly developed Geospatial Random Cluster Ensemble Regression (GRaCER) method. This method is based on a two-step (cluster-regression) approach, but extends it by considering an ensemble of such cluster-regressions, leading to higher robustness. Surface ocean DIC, pH, and Ω were then computed from the globally mapped pCO2 and TA using the thermodynamic equations of the carbonate system. For the open ocean, the cluster regression method estimates pCO2 and TA with global near-zero biases and root mean squared errors of 12 µatm and 13 µmol kg−1, respectively. Taking into account also the measurement and representation errors, the total error increases to 14 µatm and 21 µmol kg−1, respectively. We assess the fidelity of the computed parameters by comparing them to direct observations from GLODAP, finding surface ocean pH and DIC global biases of near zero, and root mean squared errors of 0.023 and 16 µmol kg−1, respectively. These errors are very comparable to those expected by propagating the total errors from pCO2 and TA through the thermodynamic computations, indicating a robust and conservative assessment of the errors. We illustrate the potential of this new dataset by analyzing the climatological mean seasonal cycles of the different parameters of the surface ocean carbonate system, highlighting their commonalities and differences. The OceanSODA-ETHZ data can be downloaded from https://doi.org/10.25921/m5wx-ja34 (Gregor and Gruber, 2020).

Organic and inorganic whole system metabolism in two acidified coastal systems in Ireland

2020 ◽  
Author(s):  
Maria Teresa Guerra ◽  
Carlos Rocha
Keyword(s):  
Ocean Acidification ◽  
Dissolved Inorganic Carbon ◽  
Total Alkalinity ◽  
Carbonate System ◽  
Net Community Production ◽  
Coastal Acidification ◽  
Autumn And Winter ◽  
System Metabolism ◽  
Internal Buffer ◽  
Community Production

&lt;p&gt;Organic and inorganic whole system metabolism for two Irish coastal areas were compared to evaluate carbonate system resilience to acidification. The two systems are characterized by contrasting watershed input types and composition. Kinvara Bay is fed by Submarine Groundwater Discharge (SGD) derived from a karstic catchment while Killary Harbour is fed by river discharge draining a siliciclastic catchment. Freshwater sources to sea have distinct Total Alkalinity (TA) and Dissolved Inorganic Carbon (DIC) concentrations, higher and lower than the open ocean, respectively, but both evidence seasonally variable low pH, ranging from 6.20 to 7.50. Retention of TA and DIC was calculated for the two areas using LOICZ methodology. In Kinvara bay, annually averaged retention of DIC was greater than for TA (5 &amp;#215; 10&lt;sup&gt;4&lt;/sup&gt; and 1.5 &amp;#215; 10&lt;sup&gt;5&lt;/sup&gt; mol d&lt;sup&gt;-1&lt;/sup&gt;), suggesting the system is acidifying further. Conversely, Killary Harbour shows negative TA and DIC retention, with DIC:TA &lt;1, suggesting an internal buffer against ocean acidification is operating.&lt;/p&gt;&lt;p&gt;Net Community Production (NCP) was calculated for both systems using Dissolved Oxygen data. Subsequently, we estimated Net Community Calcification (NCC) from the ratio between TA and DIC. NCP was always positive in Killary Harbour with an average of 318 mmol O&lt;sub&gt;2&lt;/sub&gt; m&lt;sup&gt;-2 &lt;/sup&gt;d&lt;sup&gt;-1&lt;/sup&gt; (equivalent to 89 mol C m&lt;sup&gt;-2&lt;/sup&gt; y&lt;sup&gt;-1&lt;/sup&gt;). However, Kinvara Bay shows relatively lower positive NCP in spring and summer (average of 46 mmol O&lt;sub&gt;2&lt;/sub&gt; m&lt;sup&gt;-2&lt;/sup&gt; d&lt;sup&gt;-1&lt;/sup&gt;), but negative NCP in autumn and winter. Therefore, Kinvara Bay&amp;#8217;s Total Organic Carbon (TOC) production was low, at ~21 g m&lt;sup&gt;-2&lt;/sup&gt; y&lt;sup&gt;-1&lt;/sup&gt; and not enough to overcome acidification driven by the SGD source composition. These results emphasize the complexity of interactions between the drivers of coastal acidification rate, affecting our ability to accurately assess the resilience of the carbonate system in these areas to ocean acidification pressure in the future.&lt;/p&gt;

scholarly journals OceanSODA-ETHZ: a global gridded data set of the surface ocean carbonate system for seasonal to decadal studies of ocean acidification

2021 ◽  
Vol 13 (2) ◽  
pp. 777-808
Author(s):  
Luke Gregor ◽  
Nicolas Gruber
Keyword(s):  
Ocean Acidification ◽  
Total Alkalinity ◽  
Global Ocean ◽  
Carbonate System ◽  
Data Set ◽  
Saturation State ◽  
Total Uncertainty ◽  
Mean Squared Errors ◽  
Surface Ocean ◽  
Basin Scale

Abstract. Ocean acidification has profoundly altered the ocean's carbonate chemistry since preindustrial times, with potentially serious consequences for marine life. Yet, no long-term, global observation-based data set exists that allows us to study changes in ocean acidification for all carbonate system parameters over the last few decades. Here, we fill this gap and present a methodologically consistent global data set of all relevant surface ocean parameters, i.e., dissolved inorganic carbon (DIC), total alkalinity (TA), partial pressure of CO2 (pCO2), pH, and the saturation state with respect to mineral CaCO3 (Ω) at a monthly resolution over the period 1985 through 2018 at a spatial resolution of 1∘×1∘. This data set, named OceanSODA-ETHZ, was created by extrapolating in time and space the surface ocean observations of pCO2 (from the Surface Ocean CO2 Atlas, SOCAT) and total alkalinity (TA; from the Global Ocean Data Analysis Project, GLODAP) using the newly developed Geospatial Random Cluster Ensemble Regression (GRaCER) method (code available at https://doi.org/10.5281/zenodo.4455354, Gregor, 2021). This method is based on a two-step (cluster-regression) approach but extends it by considering an ensemble of such cluster regressions, leading to improved robustness. Surface ocean DIC, pH, and Ω were then computed from the globally mapped pCO2 and TA using the thermodynamic equations of the carbonate system. For the open ocean, the cluster-regression method estimates pCO2 and TA with global near-zero biases and root mean squared errors of 12 µatm and 13 µmol kg−1, respectively. Taking into account also the measurement and representation errors, the total uncertainty increases to 14 µatm and 21 µmol kg−1, respectively. We assess the fidelity of the computed parameters by comparing them to direct observations from GLODAP, finding surface ocean pH and DIC global biases of near zero, as well as root mean squared errors of 0.023 and 16 µmol kg−1, respectively. These uncertainties are very comparable to those expected by propagating the total uncertainty from pCO2 and TA through the thermodynamic computations, indicating a robust and conservative assessment of the uncertainties. We illustrate the potential of this new data set by analyzing the climatological mean seasonal cycles of the different parameters of the surface ocean carbonate system, highlighting their commonalities and differences. Further, this data set provides a novel constraint on the global- and basin-scale trends in ocean acidification for all parameters. Concretely, we find for the period 1990 through 2018 global mean trends of 8.6 ± 0.1 µmol kg−1 per decade for DIC, −0.016 ± 0.000 per decade for pH, 16.5 ± 0.1 µatm per decade for pCO2, and −0.07 ± 0.00 per decade for Ω. The OceanSODA-ETHZ data can be downloaded from https://doi.org/10.25921/m5wx-ja34 (Gregor and Gruber, 2020).

scholarly journals Intercomparison of carbonate chemistry measurements on a cruise in northwestern European shelf seas

2014 ◽  
Vol 11 (2) ◽  
pp. 2793-2822 ◽  
Author(s):  
M. Ribas-Ribas ◽  
V. M. C. Rérolle ◽  
D. C. E. Bakker ◽  
V. Kitidis ◽  
G. A. Lee ◽  
...  
Keyword(s):  
Degrees Of Freedom ◽  
Dissolved Inorganic Carbon ◽  
Maximum Amplitude ◽  
Total Alkalinity ◽  
Carbonate Chemistry ◽  
Carbonate System ◽  
European Shelf ◽  
Shelf Seas ◽  
The Difference ◽  
System Variables

Abstract. Four carbonate system variables were measured in surface waters during a cruise traversing northwestern European shelf seas in the summer of 2011. High resolution surface water data were collected for partial pressure of carbon dioxide (pCO2; using two independent instruments) and pHT, in addition to discrete measurements of total alkalinity and dissolved inorganic carbon. We thus overdetermined the carbonate system (four measured variables, two degrees of freedom) which allowed us to evaluate the level of agreement between the variables. Calculations of carbonate system variables from other measurements generally compared well (Pearson's correlation coefficient always &amp;geq; 0.94; mean residuals similar to the respective uncertainties of the calculations) with direct observations of the same variables. We therefore conclude that the four independent datasets of carbonate chemistry variables were all of high quality, and as a result that this dataset is suitable to be used for the evaluation of ocean acidification impacts and for carbon cycle studies. A diurnal cycle with maximum amplitude of 41 μatm was observed in the difference between the pCO2; values obtained by the two independent analytical pCO2; systems, and this was partly attributed to irregular seawater flows to the equilibrator and partly to biological activity inside the seawater supply and one of the equilibrators. We discuss how these issues can be addressed to improve carbonate chemistry data quality on research cruises.

scholarly journals CO<sub>2</sub> perturbation experiments: similarities and differences between dissolved inorganic carbon and total alkalinity manipulations

2009 ◽  
Vol 6 (10) ◽  
pp. 2145-2153 ◽  
Author(s):  
K. G. Schulz ◽  
J. Barcelos e Ramos ◽  
R. E. Zeebe ◽  
U. Riebesell
Keyword(s):  
Ocean Acidification ◽  
Inorganic Carbon ◽  
Dissolved Inorganic Carbon ◽  
Total Alkalinity ◽  
Calcium Carbonate Precipitation ◽  
Carbonate Chemistry ◽  
Carbonate System ◽  
Experimental Conditions ◽  
Saturation State ◽  
Basic Approaches

Abstract. Increasing atmospheric carbon dioxide (CO2) through human activities and invasion of anthropogenic CO2 into the surface ocean alters the seawater carbonate chemistry, increasing CO2 and bicarbonate (HCO3−) at the expense of carbonate ion (CO32−) concentrations. This redistribution in the dissolved inorganic carbon (DIC) pool decreases pH and carbonate saturation state (Ω). Several components of the carbonate system are considered potential key variables influencing for instance calcium carbonate precipitation in marine calcifiers such as coccolithophores, foraminifera, corals, mollusks and echinoderms. Unravelling the sensitivities of marine organisms and ecosystems to CO2 induced ocean acidification (OA) requires well-controlled experimental setups and accurate carbonate system manipulations. Here we describe and analyse the chemical changes involved in the two basic approaches for carbonate chemistry manipulation, i.e. changing DIC at constant total alkalinity (TA) and changing TA at constant DIC. Furthermore, we briefly introduce several methods to experimentally manipulate DIC and TA. Finally, we examine responses obtained with both approaches using published results for the coccolithophore Emiliania huxleyi. We conclude that under most experimental conditions in the context of ocean acidification DIC and TA manipulations yield similar changes in all parameters of the carbonate system, which implies direct comparability of data obtained with the two basic approaches for CO2 perturbation.

scholarly journals Intercomparison of carbonate chemistry measurements on a cruise in northwestern European shelf seas

2014 ◽  
Vol 11 (16) ◽  
pp. 4339-4355 ◽  
Author(s):  
M. Ribas-Ribas ◽  
V. M. C. Rérolle ◽  
D. C. E. Bakker ◽  
V. Kitidis ◽  
G. A. Lee ◽  
...  
Keyword(s):  
Degrees Of Freedom ◽  
Dissolved Inorganic Carbon ◽  
Maximum Amplitude ◽  
Total Alkalinity ◽  
Future Research ◽  
Carbonate Chemistry ◽  
Carbonate System ◽  
European Shelf ◽  
Shelf Seas ◽  
System Variables

Abstract. Four carbonate system variables were measured in surface waters during a cruise aimed at investigating ocean acidification impacts traversing northwestern European shelf seas in the summer of 2011. High-resolution surface water data were collected for partial pressure of carbon dioxide (pCO2; using two independent instruments) and pH using the total pH scale (pHT), in addition to discrete measurements of total alkalinity and dissolved inorganic carbon. We thus overdetermined the carbonate system (four measured variables, two degrees of freedom), which allowed us to evaluate the level of agreement between the variables on a cruise whose main aim was not intercomparison, and thus where conditions were more representative of normal working conditions. Calculations of carbonate system variables from other measurements generally compared well with direct observations of the same variables (Pearson's correlation coefficient always greater than or equal to 0.94; mean residuals were similar to the respective accuracies of the measurements). We therefore conclude that four of the independent data sets of carbonate chemistry variables were of high quality. A diurnal cycle with a maximum amplitude of 41 μatm was observed in the difference between the pCO2 values obtained by the two independent analytical pCO2 systems, and this was partly attributed to irregular seawater flows to the equilibrator and partly to biological activity inside the seawater supply and one of the equilibrators. We discuss how these issues can be addressed to improve carbonate chemistry data quality on future research cruises.

scholarly journals Concomitant ocean acidification and increasing total alkalinity at a coastal site in the NW Mediterranean Sea (2007-2015)

2016 ◽  
Author(s):  
Lydia Kapsenberg ◽  
Samir Alliouane ◽  
Frédéric Gazeau ◽  
Laure Mousseau ◽  
Jean-Pierre Gattuso
Keyword(s):  
Ocean Acidification ◽  
Mediterranean Sea ◽  
Dissolved Inorganic Carbon ◽  
Coastal Ocean ◽  
Total Alkalinity ◽  
Global Ocean ◽  
Coastal Zones ◽  
Carbonate Chemistry ◽  
Nw Mediterranean ◽  
Nw Mediterranean Sea

Abstract. Monitoring of global ocean change is necessary in coastal zones due to their physical and biological complexity. Here, we document changes in coastal carbonate chemistry at the coastal time-series station, Point B, in the NW Mediterranean Sea from 2007 through 2015 at 1 and 50 m. The rate of surface ocean acidification (−0.0028 ± 0.0003 units pHT yr−1) was faster-than-expected based on atmospheric carbon dioxide forcing alone. Changes in carbonate chemistry were predominantly driven by an increase in total dissolved inorganic carbon (CT, +2.97 ± 0.20 μmol kg−1 yr−1), > 50 % of which was buffered by a synchronous increase in total alkalinity (AT, +2.08 ± 0.19 μmol kg−1 yr−1). The increase in AT was unrelated to salinity and its cause remains to be identified. Interestingly, concurrent increases in AT and CT were most rapid from May to July. Changes at 50 m were slower compared to 1 m. It seems therefore likely that changes in coastal AT cycling via a shallow coastal process gave rise to these observations. This study exemplifies the importance of understanding coastal ocean acidification through localized biogeochemical cycling that extends beyond simple air-sea gas exchange dynamics, in order to make relevant predictions about future coastal ocean change and ecosystem function.

scholarly journals EPOCA/EUR-OCEANS data-mining compilation on the impacts of ocean acidification

2010 ◽  
Vol 3 (1) ◽  
pp. 109-130 ◽  
Author(s):  
A.-M. Nisumaa ◽  
S. Pesant ◽  
R. G. J. Bellerby ◽  
B. Delille ◽  
J. Middelburg ◽  
...  
Keyword(s):  
Ocean Acidification ◽  
Dissociation Constants ◽  
Data Access ◽  
Environmental Data ◽  
Ion Concentration ◽  
Carbonate Chemistry ◽  
Ancillary Data ◽  
Carbonate System ◽  
Common Framework ◽  
System Variables

Abstract. The uptake of anthropogenic CO2 by the oceans has led to a rise in the oceanic partial pressure of CO2, and to a decrease in pH and carbonate ion concentration. This modification of the marine carbonate system is referred to as ocean acidification. Numerous papers report the effects of ocean acidification on marine organisms and communities but few have provided details concerning full carbonate chemistry and complementary observations. Additionally, carbonate system variables are often reported in different units, calculated using different sets of dissociation constants and on different pH scales. Hence the direct comparison of experimental results has been problematic and often misleading. The need was identified to (1) gather data on carbonate chemistry, biological and biogeochemical properties, and other ancillary data from published experimental data, (2) transform the information into common framework, and (3) make data freely available. The present paper is the outcome of an effort to integrate ocean carbonate chemistry data from the literature which has been supported by the European Network of Excellence for Ocean Ecosystems Analysis (EUR-OCEANS) and the European Project on Ocean Acidification (EPOCA). A total of 166 papers were identified, 86 contained enough information to readily compute carbonate chemistry variables, and 67 datasets were archived at PANGAEA – The Publishing Network for Geoscientific &amp; Environmental Data. This data compilation is regularly updated as an ongoing mission of EPOCA. Data access: http://doi.pangaea.de/10.1594/PANGAEA.735138

scholarly journals Sensitivity of the regional ocean acidification and carbonate system in Puget Sound to ocean and freshwater inputs

Elem Sci Anth ◽  
2018 ◽  
Vol 6 ◽  
Author(s):  
Laura Bianucci ◽  
Wen Long ◽  
Tarang Khangaonkar ◽  
Gregory Pelletier ◽  
Anise Ahmed ◽  
...  
Keyword(s):  
Ocean Acidification ◽  
Dissolved Inorganic Carbon ◽  
Puget Sound ◽  
Ocean Model ◽  
Total Alkalinity ◽  
Salish Sea ◽  
Carbonate System ◽  
Saturation State ◽  
Juan De Fuca ◽  
Freshwater Inputs

While ocean acidification was first investigated as a global phenomenon, coastal acidification has received significant attention in recent years, as its impacts have been felt by different socio-economic sectors (e.g., high mortality of shellfish larvae in aquaculture farms). As a region that connects land and ocean, the Salish Sea (consisting of Puget Sound and the Straits of Juan de Fuca and Georgia) receives inputs from many different sources (rivers, wastewater treatment plants, industrial waste treatment facilities, etc.), making these coastal waters vulnerable to acidification. Moreover, the lowering of pH in the Northeast Pacific Ocean also affects the Salish Sea, as more acidic waters get transported into the bottom waters of the straits and estuaries. Here, we use a numerical ocean model of the Salish Sea to improve our understanding of the carbonate system in Puget Sound; in particular, we studied the sensitivity of carbonate variables (e.g., dissolved inorganic carbon, total alkalinity, pH, saturation state of aragonite) to ocean and freshwater inputs. The model is an updated version of our FVCOM-ICM framework, with new carbonate-system and sediment modules. Sensitivity experiments altering concentrations at the open boundaries and freshwater sources indicate that not only ocean conditions entering the Strait of Juan de Fuca, but also the dilution of carbonate variables by freshwater sources, are key drivers of the carbonate system in Puget Sound.

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