High vertical resolution measurements of pH, pCO2, total alkalinity, and dissolved inorganic carbon using a new approach: the carbonate profiler

The Bermuda Testbed Mooring (BTM) and Bay of Bengal Ocean Acidification (BOBOA) mooring measurements were used to identify changes in the partial pressure of CO2 at the sea surface (pCO2sea) and air-sea CO2 fluxes (FCO2) associated with passage of two tropical cyclones (TCs), Florence and Hudhud. TC Florence passed about 165 km off the BTM mooring site with strong wind speeds of 24.8 m s–1 and translation speed of 7.23 m s–1. TC Hudhud passed about 178 km off the BOBOA mooring site with wind speeds of 14.0 m s–1 and translation speed of 2.58 m s–1. The present study examined the effect of temperature, salinity, dissolved inorganic carbon (DIC), total alkalinity (TA), air-sea CO2 flux, and phytoplankton chlorophyll a change on pCO2sea as a response to TCs. Enhanced mixed layer depths were observed due to TCs-induced vertical mixing at both mooring sites. Decreased pCO2sea (–15.16±5.60 μatm) at the BTM mooring site and enhanced pCO2sea (14.81±7.03 μatm) at the BOBOA mooring site were observed after the passage of Florence and Hudhud, respectively. Both DIC and TA are strongly correlated with salinity in the upper layer of the isothermal layer depth (ILD). Strong (weak) vertical gradient in salinity is accompanied by strong (weak) vertical gradients in DIC and TA. Strong vertical salinity gradient in the upper layer of the ILD (0.031 psu m–1), that supply much salinity, dissolved inorganic carbon and total alkalinity from the thermocline was the cause of the increased pCO2sea in the BOBOA mooring water. Weak vertical salinity gradient in the upper layer of the ILD (0.003 psu m–1) was responsible for decreasing pCO2sea in the BTM mooring water. The results of this study showed that the vertical salinity gradient in the upper layer of the ILD is a good indicator of the pCO2sea variation after the passages of TCs.

To understand the effects of the glacial meltwater supply on carbonate chemistry and the air–sea CO2 flux within the fjord, water samples were collected in Bowdoin Fjord in northwestern Greenland for dissolved inorganic carbon (DIC) concentration, total alkalinity (TA), oxygen isotopic ratio (δ18O), and chlorophyll a concentration analyses in the summers of 2016 and 2017. The partial pressure of CO2 (pCO2) in surface water, calculated from DIC and TA, was less than 200 µatm, and was significantly lower than that in the atmosphere (399 ± 3 µatm). Therefore, surface water of the fjord acts as sink for CO2 in the atmosphere (–4.9 ± 0.7 mmol m–2 d–1). To evaluate the effects of freshwater and land-derived substances by glacial meltwater on pCO2 in the fjord, we calculated the changes of pCO2 in salinity and carbonate chemistry that would result from the inflow of glacial meltwater into the fjord. The calculated pCO2 was high near the calving front, where the contribution of glacier meltwater was significant. Examination of the relationship between salinity-normalized DIC and TA, which was considered DIC and TA input from the land, suggested that the land-derived high pCO2 freshwater affected mainly by the remineralization of the organic matter by bacterial activity was supplied to the Bowdoin Fjord.

Ocean acidification is likely to impact marine ecosystems and human societies adversely and is a carbon cycle issue of great concern. Projecting the degree of ocean acidification and the carbon-climate feedback will require understanding the current status, variability, and trends of ocean inorganic carbon system variables and the ocean carbon sink. With this goal in mind, we reconstructed total alkalinity (TA), dissolved inorganic carbon (DIC), CO2 partial pressure (pCO2sea), sea–air CO2 flux, pH, and aragonite saturation state (Ωarg) for the global ocean based on measurements of pCO2sea and TA. We used a multiple linear regression approach to derive relationships to explain TA and DIC and obtained monthly 1° × 1° gridded values of TA and DIC for the period 1993–2018. These data were converted to pCO2sea, pH, and Ωarg, and monthly sea-air CO2 fluxes were obtained in combination with atmospheric CO2. Mean annual sea–air CO2 flux and its rate of change were estimated to be − 2.0 ± 0.5 PgC year−1 and − 0.3 (PgC year−1) decade−1, respectively. Our analysis revealed that oceanic CO2 uptake decreased during the 1990s and has been increasing since 2000. Our estimate of the globally averaged rate of pH change, − 0.0181 ± 0.0001 decade−1, was consistent with that expected from the trend of atmospheric CO2 growth. However, rates of decline of pH were relatively slow in the Southern Ocean (− 0.0165 ± 0.0001·decade−1) and in the western equatorial Pacific (− 0.0148 ± 0.0002·decade−1). Our estimate of the globally averaged rate of pH change can be used to verify Indicator 14.3.1 of Sustainable Development Goals.

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.

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).

Shellfish and macro-algae integrated multi-trophic aquaculture (IMTA) contribute greatly to the sustainability of aquaculture. However, the effects of large-scale shellfish and macro-algae aquaculture on the functions of the ocean carbon sink are not clear. To clarify these effects, we studied the spatial and temporal changes of inorganic and organic carbon systems in seawater under different aquaculture modes (monoculture or polyculture of shellfish and macro-algae) in Sanggou Bay, together with the variation of other environmental factors. The results show that the summertime dissolved oxygen (DO) concentration in the shellfish culture zone was significantly lower than other zones (p < 0.05), with a minimum value of 7.07 ± 0.25 mg/L. The variation of pH and total alkalinity (TA) were large across different culture modes, and the seawater in the shellfish culture zone had the lowest pH and TA than the other zones. Seasonal environment and aquaculture modes significantly affected the variation of dissolved inorganic carbon (DIC), CO2 partial pressure (pCO2), dissolved organic carbon (DOC), and particulate organic carbon (POC) concentrations. The highest values of DIC, pCO2, and POC appeared in summer, and the lowest appeared in winter. For DOC concentration, the lowest value appeared in autumn. Spatially, DIC and pCO2 were highest in the shellfish culture zone and lowest in the macro-algae culture zone, DOC was highest in the macro-algae culture zone and lowest in the shellfish culture zone, and POC was lower in the shellfish culture zone and macro-algae culture zone and higher in the remaining zones. The results of sea–air CO2 fluxes showed that except for the shellfish culture zone during summertime, which released CO2 to the atmosphere, all culture zones were the sinks of atmospheric CO2 during the culture period, with the whole bay being a strong CO2 sink during autumn and winter. In summary, large-scale shellfish–macro-algae IMTA plays an important role in the local carbon cycle and contributes to mitigating ocean acidification and hypoxia.

In this study, the variations of the seawater carbonate system parameters and air-sea CO2 flux (FCO2) of Shen’ao Bay, a typical subtropical aquaculture bay located in China, were investigated in spring 2016 (March to May). Parameters related to the seawater carbonate system and FCO2 were measured monthly in 3 different aquaculture areas (fish, oyster and seaweed) and in a non-culture area near the bay mouth. The results showed that the seawater carbonate system was markedly influenced by the biological processes of the culture species. Total alkalinity was significantly lower in the oyster area compared with the fish and seaweed areas, mainly because of the calcification process of oysters. Dissolved inorganic carbon (DIC) and CO2 partial pressure (pCO2) were highest in the fish area, followed by the oyster and non-culture areas, and lowest in the seaweed area. Oysters and fish can have indirect influences on DIC and pCO2by releasing nutrients, which facilitate the growth of seaweed and phytoplankton and therefore promote photosynthetic CO2 fixation. For these reasons, Shen’ao Bay acts as a potential CO2 sink in spring, with an average FCO2 ranging from -1.2 to -4.8 mmol m-2 d-1. CO2 fixation in the seaweed area was the largest contributor to CO2 flux, accounting for ca. 58% of the total CO2 sink capacity of the entire bay. These results suggest that the carbonate system and FCO2 of Shen’ao Bay were significantly affected by large-scale mariculture activities. A higher CO2 sink capacity could be acquired by extending the culture area of seaweed.

An inter-comparison of autonomous in situ instruments for ocean CO2 measurements under laboratory-controlled conditions

Dissolved inorganic carbon dynamics in the waters surrounding forested mangroves of the Ca Mau Province (Vietnam)

The Mexican Tropical Pacific (MTP) is a key component of the Eastern Tropical North Pacific Oxygen Minimum Zone, yet its carbonate system variability remains poorly constrained. This study examines wind-driven circulation effects on dissolved oxygen (DO) and the carbonate system —dissolved inorganic carbon (DIC), total alkalinity (TA), total-scale pH (pHT), partial pressure of CO2 in seawater (pCO2w) and air–sea CO2 fluxes (FCO2)— in the Gulf of Tehuantepec (GT) and Tehuantepec Bowl (TB). Hydrographic data and discrete water samples were collected at 50 oceanographic stations during March 2020. Principal Component Analysis (PCA) identifies wind-driven circulation as the primary control of biogeochemical variability. Tehuano wind events and mesoscale eddies promoted upwelling of low-oxygen (DO < 20 µmol kg−1) and high-DIC (>2200 µmol kg−1) waters to 50 m depth in the central GT, while downwelling conditions prevailed in the TB. Stoichiometric analysis revealed DIC-DO coupling (slope = −1.39). Overall, the MTP acted as CO2 source (FCO2 ranging from −1.92 to 24.11 mmol m−2 d−1), with enhanced emissions linked to eddy-induced upwelling. This study provides the first integrated characterization of the carbonate system across both the GT and TB.

Seasonal variability in carbonate chemistry and air–sea CO2 fluxes in the southern Great Barrier Reef

The internal consistency of the North Sea carbonate system

Content and values displayed: The data is displayed in an excel file with spreadsheets representing each of the following spatial scales: -“Fjord-scale”: The data set includes information on measurements representing vertical profiles at sites distributed along a horizontal fjord gradient: Date, site (station), water depth, temperature, pH, Ωarag, oxygen concentration (O2) and fluorescence -“Small-scale/kelp-scale”: The data set includes information from 3 consecutive series of parallel deployments over 2-3 days in shallow subtidal kelp habitats (kelp) and neighboring habitats colonized by benthic microalgae and scattered filamentous algae (bare) in Kobbefjord. We provide information on date and time, deployment number (#1-3), and each of the following variables measured ca 50 cm above the seafloor in the two types of habitat (kelp and bare): temperature, pH, salinity, water depth, O2, PAR and Ωarag. In addition, we provide information on pH-variability within 1m3 of kelp forest measured by an array of 16 pH-sensors placed in 4 layers of the kelp forest: 10 cm above the seafloor, 20 cm above the seafloor, in the canopy and in the water column just above the canopy. -“Micro-scale”: The data set includes information on pH at a millimeter scale measured through the boundary layer of 6 different species of macrophytes (Ascophyllum nodosum, Fucus vesiculosus, Saccharina longicruris, Agarum clathratum, Ulva lactuca, Zostera marina) by microelectrode in a laboratory setup. For each point we provide the average and standard deviation (SD) of 3 replicate measurements of each species. -“Tidal pools”: The date set represents parallel diurnal measurements in a vegetated tidal pool and the adjacent vegetated shore in the inner part of Kobbefjord. For each site and sampling time we provide data on O2, salinity, temperature, pH, total alkalinity (AT), total inorganic carbon (CT), partial pressure of CO2 (pCO2)and Ωarag in the water.

Abstract. Information on changes in the oceanic carbon dioxide (CO2) concentration and air–sea CO2 flux as well as on ocean acidification in the Indian Ocean is very limited. In this study, temporal changes of the inorganic carbon system in the eastern equatorial Indian Ocean (EIO, 5° N–5° S, 90–95° E) are examined using partial pressure of carbon dioxide (pCO2) data collected in May 2012, historical pCO2 data since 1962, and total alkalinity (TA) data calculated from salinity. Results show that sea surface pCO2 in the equatorial belt (2° N–2° S, 90–95° E) increased from ∼307 μatm in April 1963 to ∼373 μatm in May 1999, ∼381 μatm in April 2007, and ∼385 μatm in May 2012. The mean rate of pCO2 increase in this area (∼1.56 μatm yr−1) was close to that in the atmosphere (∼1.46 μatm yr−1). Despite the steady pCO2 increase in this region, no significant change in air–sea CO2 fluxes was detected during this period. Ocean acidification as indicated by pH and saturation states for carbonate minerals has indeed taken place in this region. Surface water pH (total hydrogen scale) and saturation state for aragonite (Ωarag), calculated from pCO2 and TA, decreased significantly at rates of −0.0016 ± 0.0001 and −0.0095 ± 0.0005 yr−1, respectively. The respective contributions of temperature, salinity, TA, and dissolved inorganic carbon (DIC) to the increase in surface pCO2 and the decreases in pH and Ωarag are quantified. We find that the increase in DIC dominated these changes, while contributions from temperature, salinity, and TA were insignificant. The increase in DIC was most likely associated with the increasing atmospheric CO2 concentration, and the transport of accumulated anthropogenic CO2 from a CO2 sink region via basin-scale ocean circulations. These two processes may combine to drive oceanic DIC to follow atmospheric CO2 increase.

Gradual increase of anthropogenic CO2 concentration in the Earth's atmosphere changes the CO2 uptake capacity by seawater, leading to alteration of ocean carbon chemistry and therefore resulting in ‘Ocean Acidification’. Dissolved Inorganic Carbon (DIC) is one of the key parameters among the four primary variables (i.e., pH, partial pressure of CO2 (pCO2), Total Alkalinity (TA), and DIC) along with temperature, salinity, and macronutrients to fully characterize the seawater carbonate system. To improve our quantitative and mechanistic understanding of the marine carbonate system, high-quality and high spatial-temporal resolution observations of DIC are required. To meet these expectations, an autonomous DIC analyzer is needed which is cost-effective, offers high sampling frequency, low reagent as well power consumption. Here we present the development and validation of a novel analyzer for autonomous measurements of DIC in seawater using conductometric detection technique. The presented DIC analyzer employs a gas diffusion flow injection approach in a “Tube In A Tube” configuration that facilitates diffusion of gaseous CO2 from an acidified sample through a gas permeable membrane (Teflon AF2400) into a stream of alkaline solution (NaOH). The change in conductivity in the alkaline medium is measured using a detection cell with 4-hollow brass electrodes and the change in conductivity is directly proportional to the DIC concentration of the sample. Physical and chemical optimizations of the analyzer yielded sample acidification to pH < 4, a NaOH concentration of 7 mM with a flowrate of 300 µL min-1, and an inner diameter of the gas permeable tube of 0.6 mm, allowing DIC measurements in both freshwater and marine systems between 500 and 3000 µmol kg-1. The analyzer can measure 4 samples hour-1 and it requires 0.2 mL of H3PO4, 0.75 mL of NaOH, and 2 mL of sample for each measurement. Temperature and salinity effects were characterized over the ranges 5-35°C and 0-35 in the laboratory, respectively, with the formulation of a mathematical T-S correction for accurate DIC determination. Measurements of a DIC reference material (RM) over four days yielded an analytical precision of ±4.89 µmol kg-1 (n=6) and an accuracy of +1 µmol kg-1. The operational robustness of the system has been demonstrated through a field deployment in the southwest Baltic Sea, yielding an analytical precision of ±9.69 µmol kg-1 (n=6). This study describes an autonomous, on-site, cost-effective DIC analyzer capable of measuring DIC in seawater at a high temporal resolution with an ultimate aim to develop an underwater DIC sensor. The achieved accuracy and precision offer an excellent opportunity to employ the analyzer in CO2 leakage monitoring and detection in the context of Carbon Capture and Storage.