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

Total Alkalinity ◽

Carbonate System ◽

Coastal Acidification ◽

Autumn And Winter ◽

System Metabolism ◽

Internal Buffer ◽

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 &#215; 104 and 1.5 &#215; 105 mol d-1), suggesting the system is acidifying further. Conversely, Killary Harbour shows negative TA and DIC retention, with DIC:TA <1, suggesting an internal buffer against ocean acidification is operating.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 O2 m-2 d-1 (equivalent to 89 mol C m-2 y-1). However, Kinvara Bay shows relatively lower positive NCP in spring and summer (average of 46 mmol O2 m-2 d-1), but negative NCP in autumn and winter. Therefore, Kinvara Bay&#8217;s Total Organic Carbon (TOC) production was low, at ~21 g m-2 y-1 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.

Current estimates of K1* and K2* appear inconsistent with measured CO2 system parameters in cold oceanic regions

Ocean Science ◽

10.5194/os-16-847-2020 ◽

2020 ◽

Vol 16 (4) ◽

pp. 847-862 ◽

Cited By ~ 1

Author(s):

Olivier Sulpis ◽

Siv K. Lauvset ◽

Mathilde Hagens

Keyword(s):

Surface Water ◽

Ocean Acidification ◽

Carbonic Acid ◽

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.

CO2 perturbation experiments: similarities and differences between dissolved inorganic carbon and total alkalinity manipulations

Biogeosciences ◽

10.5194/bg-6-2145-2009 ◽

2009 ◽

Vol 6 (10) ◽

pp. 2145-2153 ◽

Cited By ~ 80

Author(s):

K. G. Schulz ◽

J. Barcelos e Ramos ◽

R. E. Zeebe ◽

U. Riebesell

Keyword(s):

Ocean Acidification ◽

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.

Norwegian Sea net community production estimated from O2 and prototype CO2 optode measurements on a Seaglider

10.5194/os-2020-72 ◽

2020 ◽

Author(s):

Luca Possenti ◽

Ingunn Skjelvan ◽

Dariia Atamanchuk ◽

Anders Tengberg ◽

Matthew P. Humphreys ◽

...

Keyword(s):

Total Alkalinity ◽

Coastal Current ◽

Norwegian Sea ◽

Chl A ◽

Summer Maximum ◽

Norwegian Coastal Current ◽

Changes Over Time ◽

Abstract. We report on a pilot study using a CO2 optode deployed on a Seaglider in the Norwegian Sea for 8 months (March to October 2014). The optode measurements required drift- and lag-correction, and in situ calibration using discrete water samples collected in the vicinity. We found the optode signal correlated better with the concentration of CO2, c(CO2), than with its partial pressure, p(CO2). Using the calibrated c(CO2) and a regional parameterisation of total alkalinity (AT) as a function of temperature and salinity, we calculated total dissolved inorganic carbon concentrations, CT, which had a standard deviation of 10 µmol kg−1 compared with direct CT measurements. The glider was also equipped with an oxygen (O2) optode. The O2 optode was drift-corrected and calibrated using a c(O2) climatology for deep samples (R2 = 0.89; RMSE = 0.009 µmol kg−1). The calibrated data enabled the calculation of CT – and oxygen-based net community production, N(CT) and N(O2). To derive N, CT and O2 inventory changes over time were combined with estimates of air-sea gas exchange and entrainment of deeper waters. Glider-based observations captured two periods of increased Chl a inventory in late spring (May) and a second one in summer (June). For the May period, we found N(CT) = (24±5) mmol m−2 d−1, N(O2) = (61±14) mmol m−2 d−1 and an (uncalibrated) Chl a peak concentration of craw(Chl a) = 3 mg m−3. During the June period, craw(Chl a) increased to a summer maximum of 4 mg m−3, which drove N(CT) to (64±67) mmol m−2 d−1 and N(O2) to (166±75) mmol m−2 d−1. The high-resolution dataset allowed for quantification of the changes in N before, during and after the periods of increased Chl a inventory. After the May period, the remineralisation of the material produced during the period of increased Chl a inventory decreased N(CT) to (−80±107) mmol m−2 d−1 and N(O2) to (−15±27) mmol m−2 d−1. The survey area was a source of O2 and a sink of CO2 for most of the summer. The deployment captured two different surface waters: the Norwegian Atlantic Current (NwAC) and the Norwegian Coastal Current (NCC). The NCC was characterised by lower c(O2) and CT than the NwAC, as well as lower N(O2), N(CT) and craw(Chl a). Our results show the potential of glider data to simultaneously capture time and depth-resolved variability in CT and O2.

Norwegian Sea net community production estimated from O2 and prototype CO2 optode measurements on a Seaglider

Ocean Science ◽

10.5194/os-17-593-2021 ◽

2021 ◽

Vol 17 (2) ◽

pp. 593-614

Author(s):

Luca Possenti ◽

Ingunn Skjelvan ◽

Dariia Atamanchuk ◽

Anders Tengberg ◽

Matthew P. Humphreys ◽

...

Keyword(s):

Total Alkalinity ◽

Coastal Current ◽

Norwegian Sea ◽

Chl A ◽

Summer Maximum ◽

Norwegian Coastal Current ◽

Abstract. We report on a pilot study using a CO2 optode deployed on a Seaglider in the Norwegian Sea from March to October 2014. The optode measurements required drift and lag correction and in situ calibration using discrete water samples collected in the vicinity. We found that the optode signal correlated better with the concentration of CO2, c(CO2), than with its partial pressure, p(CO2). Using the calibrated c(CO2) and a regional parameterisation of total alkalinity (AT) as a function of temperature and salinity, we calculated total dissolved inorganic carbon content, c(DIC), which had a standard deviation of 11 µmol kg−1 compared with in situ measurements. The glider was also equipped with an oxygen (O2) optode. The O2 optode was drift corrected and calibrated using a c(O2) climatology for deep samples. The calibrated data enabled the calculation of DIC- and O2-based net community production, N(DIC) and N(O2). To derive N, DIC and O2 inventory changes over time were combined with estimates of air–sea gas exchange, diapycnal mixing and entrainment of deeper waters. Glider-based observations captured two periods of increased Chl a inventory in late spring (May) and a second one in summer (June). For the May period, we found N(DIC) = (21±5) mmol m−2 d−1, N(O2) = (94±16) mmol m−2 d−1 and an (uncalibrated) Chl a peak concentration of craw(Chl a) = 3 mg m−3. During the June period, craw(Chl a) increased to a summer maximum of 4 mg m−3, associated with N(DIC) = (85±5) mmol m−2 d−1 and N(O2) = (126±25) mmol m−2 d−1. The high-resolution dataset allowed for quantification of the changes in N before, during and after the periods of increased Chl a inventory. After the May period, the remineralisation of the material produced during the period of increased Chl a inventory decreased N(DIC) to (-3±5) mmol m−2 d−1 and N(O2) to (0±2) mmol m−2 d−1. The survey area was a source of O2 and a sink of CO2 for most of the summer. The deployment captured two different surface waters influenced by the Norwegian Atlantic Current (NwAC) and the Norwegian Coastal Current (NCC). The NCC was characterised by lower c(O2) and c(DIC) than the NwAC, as well as lower N(O2) and craw(Chl a) but higher N(DIC). Our results show the potential of glider data to simultaneously capture time- and depth-resolved variability in DIC and O2 concentrations.

Current estimates of K1 and K2 appear inconsistent with measured CO2 system parameters in cold oceanic regions

10.5194/os-2020-19 ◽

2020 ◽

Author(s):

Olivier Sulpis ◽

Siv K. Lauvset ◽

Mathilde Hagens

Keyword(s):

Surface Water ◽

Ocean Acidification ◽

Carbonic Acid ◽

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.

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

10.5194/essd-2020-300 ◽

2020 ◽

Author(s):

Luke Gregor ◽

Nicolas Gruber

Keyword(s):

Ocean Acidification ◽

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).

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

Elem Sci Anth ◽

10.1525/elementa.151 ◽

2018 ◽

Vol 6 ◽

Cited By ~ 12

Author(s):

Laura Bianucci ◽

Wen Long ◽

Tarang Khangaonkar ◽

Gregory Pelletier ◽

Anise Ahmed ◽

...

Keyword(s):

Ocean Acidification ◽

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.

Benthic buffers and boosters of ocean acidification on coral reefs

Biogeosciences ◽

10.5194/bg-10-4897-2013 ◽

2013 ◽

Vol 10 (7) ◽

pp. 4897-4909 ◽

Cited By ~ 45

Author(s):

K. R. N. Anthony ◽

G. Diaz-Pulido ◽

N. Verlinden ◽

B. Tilbrook ◽

A. J. Andersson

Keyword(s):

Ocean Acidification ◽

Benthic Communities ◽

Time Of Day ◽

High Flow ◽

Reef Environment ◽

Saturation State ◽

Low Co2 ◽

Coral Reef Environment ◽

Abstract. Ocean acidification is a threat to marine ecosystems globally. In shallow-water systems, however, ocean acidification can be masked by benthic carbon fluxes, depending on community composition, seawater residence time, and the magnitude and balance of net community production (NCP) and calcification (NCC). Here, we examine how six benthic groups from a coral reef environment on Heron Reef (Great Barrier Reef, Australia) contribute to changes in the seawater aragonite saturation state (Ωa). Results of flume studies using intact reef habitats (1.2 m by 0.4 m), showed a hierarchy of responses across groups, depending on CO2 level, time of day and water flow. At low CO2 (350–450 μatm), macroalgae (Chnoospora implexa), turfs and sand elevated Ωa of the flume water by around 0.10 to 1.20 h−1 – normalised to contributions from 1 m2 of benthos to a 1 m deep water column. The rate of Ωa increase in these groups was doubled under acidification (560–700 μatm) and high flow (35 compared to 8 cm s−1). In contrast, branching corals (Acropora aspera) increased Ωa by 0.25 h−1 at ambient CO2 (350–450 μatm) during the day, but reduced Ωa under acidification and high flow. Nighttime changes in Ωa by corals were highly negative (0.6–0.8 h−1) and exacerbated by acidification. Calcifying macroalgae (Halimeda spp.) raised Ωa by day (by around 0.13 h−1), but lowered Ωa by a similar or higher amount at night. Analyses of carbon flux contributions from benthic communities with four different compositions to the reef water carbon chemistry across Heron Reef flat and lagoon indicated that the net lowering of Ωa by coral-dominated areas can to some extent be countered by long water-residence times in neighbouring areas dominated by turfs, macroalgae and carbonate sand.

Benthic buffers and boosters of ocean acidification on coral reefs

Biogeosciences Discussions ◽

10.5194/bgd-10-1831-2013 ◽

2013 ◽

Vol 10 (2) ◽

pp. 1831-1865 ◽

Cited By ~ 6

Author(s):

K. R. N. Anthony ◽

G. Diaz-Pulido ◽

N. Verlinden ◽

B. Tilbrook ◽

A. J. Andersson

Keyword(s):

Ocean Acidification ◽

Time Of Day ◽

High Flow ◽

Reef Environment ◽

Saturation State ◽

Low Co2 ◽

Coral Reef Environment ◽

Co2 Level ◽

Abstract. Ocean acidification is a threat to marine ecosystems globally. In shallow-water systems, however, ocean acidification can be masked by benthic carbon fluxes, depending on community composition, seawater residence time, and the magnitude and balance of net community production (pn) and calcification (gn). Here, we examine how six benthic groups from a coral reef environment on Heron Reef (Great Barrier Reef, Australia) contribute to changes in seawater aragonite saturation state (Ωa). Results of flume studies showed a hierarchy of responses across groups, depending on CO2 level, time of day and water flow. At low CO2 (350–450 μatm), macroalgae (Chnoospora implexa), turfs and sand elevated Ωa of the flume water by around 0.10 to 1.20 h−1 – normalised to contributions from 1 m2 of benthos to a 1 m deep water column. The rate of Ωa increase in these groups was doubled under acidification (560–700 μatm) and high flow (35 compared to 8 cm s−1). In contrast, branching corals (Acropora aspera) increased Ωa by 0.25 h−1 at ambient CO2 (350–450 μatm) during the day, but reduced Ωa under acidification and high flow. Nighttime changes in Ωa by corals were highly negative (0.6–0.8 h−1) and exacerbated by acidification. Calcifying macroalgae (Halimeda spp.) raised Ωa by day (by around 0.13 h−1), but lowered Ωa by a similar or higher amount at night. Analyses of carbon flux contributions from four different benthic compositions to the reef water carbon chemistry across Heron Reef flat and lagoon indicated that the net lowering of Ωa by coral-dominated areas can to some extent be countered by long water residence times in neighbouring areas dominated by turfs, macroalgae and potentially sand.

Ocean acidification from 1997 to 2011 in the subarctic western North Pacific Ocean

Biogeosciences Discussions ◽

10.5194/bgd-10-8283-2013 ◽

2013 ◽

Vol 10 (5) ◽

pp. 8283-8311 ◽

Cited By ~ 1

Author(s):

M. Wakita ◽

S. Watanabe ◽

M. Honda ◽

A. Nagano ◽

K. Kimoto ◽

...

Keyword(s):

Ocean Acidification ◽

Mixed Layer ◽

North Pacific ◽

North Pacific Ocean ◽

Total Alkalinity ◽

Co2 Uptake ◽

The North ◽

Western Subarctic Gyre ◽

Calcite Saturation

Abstract. Rising atmospheric CO2 contents have led to greater CO2 uptake by the oceans, lowering both pH due to increasing hydrogen ions and CaCO3 saturation states due to declining carbonate ion (CO32−). Here, we used previously compiled data sets and new data collected in 2010 and 2011 to investigate ocean acidification of the North Pacific western subarctic gyre. In winter, the western subarctic gyre is a source of CO2 to the atmosphere because of convective mixing of deep waters rich in dissolved inorganic carbon (DIC). We calculated pH in winter mixed layer from DIC and total alkalinity (TA), and found that it decreased at the rate of −0.001 ± 0.0004 yr−1 from 1997 to 2011. This decrease rate is slower than that expected under condition of seawater/atmosphere equilibration, and it is also slower than the rate in the subtropical regions (−0.002 yr−1). The slow rate is caused by a reduction of CO2 emission in winter due to an increase in TA. Below the mixed layer, the calcite saturation horizon (~185 m depth) shoaled at the rate of 2.9 ± 0.9 m yr−1 as the result of the declining CO32− concentration (−0.03 ± 0.01 μmol k−1yr−1). Between 200 m and 300 m depth, pH decline during the study period (−0.0051 ± 0.0010 yr−1) was larger than ever reported in the open North Pacific. This enhanced acidification rate below the calcite saturation horizon reflected not only the uptake of anthropogenic CO2 but also the increase in the decomposition of organic matter evaluated from the increase in AOU, which suggests that the dissolution of CaCO3 particles increased.