CO2 Fugacity Research Articles

Effect of a tropical cyclone on the pelagic ecosystem of a continental shelf

AbstractThis study aimed to comprehend the effects of Typhoon Maria on the pelagic ecosystem in the southern East China Sea. Shipboard measurements were conducted at eight sampling stations before (2–4 d) and after (3–6 d) the typhoon, which enabled the evaluation of the potential impacts of the typhoon on this pelagic ecosystem, with particular focus on carbon dynamics. Following the typhoon's passage, there was a slight drop in sea surface temperature. The response of the variables to the typhoon, however, exhibited variations at different sampling stations. For further analysis, t‐tests compared variables, while type II regression assessed the linear correlation between two variables. Overall, during the post‐typhoon period, concentrations of nitrate, chlorophyll a, primary production, bacterial biomass and production, plankton community respiration, and abundance of large phytoplankton (> 2 μm) and the relative abundance of picophytoplankton among larger‐sized picoeukaryotes were higher compared to the pre‐typhoon period. The mean value of fugacity of CO2 was similar to or slightly lower than pre‐typhoon period. Although the typhoon‐induced vigorous primary production might have absorbed a significant amount of CO2, the decrease in fugacity of CO2 could have been offset by the plankton community respiration. The findings suggest that the typhoon enhanced physical disturbance and increased water column mixing, which, in turn, augmented nutrient availability and promoted plankton growth in the shallow water column. Overall, this study sheds light on the complex interactions between typhoons and marine ecosystems and highlights the importance of further investigating these phenomena to better understand their ecological implications.

Spectrophotometrically derived seawater CO2‐system assessments: Parameter calculations using pH do not require measurements at standard temperatures

AbstractThe temperature range of Earth's open‐ocean waters is roughly 0–30°C, yet our understanding of the seawater carbon dioxide (CO2) system is largely derived from analyses conducted within a narrow temperature range (e.g., laboratory temperature of 20°C or 25°C). Herein, we address two aspects of open‐ocean CO2‐system measurements and modeling: (1) a highly precise spectrophotometric technique is used to determine bicarbonate dissociation constants (K2) in seawater at temperatures as low as 3°C and (2) a cruise dataset uniquely including total scale pH measurements at two temperatures is used for CO2‐system internal consistency comparisons at 12°C and 25°C. Our pK2 parameterization (where pK = −log K) is applicable for broad ranges of salinity (20 ≤ SP ≤ 40) and temperature (3°C ≤ t ≤ 35°C). Our CO2‐system internal consistency evaluation (comparison of measured and calculated CO2‐system parameters) utilized data obtained during NOAA's 2021 West Coast Ocean Acidification Cruise: total alkalinity (TA), total dissolved inorganic carbon (DIC), pH measured at 25°C, and pH measured at 12°C (n = 265). Results demonstrate that, relative to calculations utilizing the TA, DIC pair, agreement between measured and calculated parameters is improved when either TA or DIC is paired with pH measurements at either temperature. Calculations of CO2 fugacity (fCO2) and aragonite saturation state (Ωar) using pH measurements made at 25°C or 12°C (paired with either TA or DIC) are statistically indistinguishable. Results also suggest that the temperature dependence of current CO2‐system dissociation constants need further refinement.

Anthropogenic CO2, air–sea CO2 fluxes, and acidification in the Southern Ocean: results from a time-series analysis at station OISO-KERFIX (51° S–68° E)

Abstract. The temporal variation of the carbonate system, air–sea CO2 fluxes, and pH is analyzed in the southern Indian Ocean, south of the polar front, based on in situ data obtained from 1985 to 2021 at a fixed station (50°40′ S–68°25′ E) and results from a neural network model that reconstructs the fugacity of CO2 (fCO2) and fluxes at monthly scale. Anthropogenic CO2 (Cant) is estimated in the water column and is detected down to the bottom (1600 m) in 1985, resulting in an aragonite saturation horizon at 600 m that migrated up to 400 m in 2021 due to the accumulation of Cant. At the subsurface, the trend of Cant is estimated at +0.53±0.01 µmol kg−1 yr−1 with a detectable increase in the trend in recent years. At the surface during austral winter the oceanic fCO2 increased at a rate close to or slightly lower than in the atmosphere. To the contrary, in summer, we observed contrasting fCO2 and dissolved inorganic carbon (CT) trends depending on the decade and emphasizing the role of biological drivers on air–sea CO2 fluxes and pH inter-annual variability. The regional air–sea CO2 fluxes evolved from an annual source to the atmosphere of 0.8 molC m−2 yr−1 in 1985 to a sink of −0.5 molC m−2 yr−1 in 2020. Over 1985–2020, the annual pH trend in surface waters of -0.0165±0.0040 per decade was mainly controlled by the accumulation of anthropogenic CO2, but the summer pH trends were modulated by natural processes that reduced the acidification rate in the last decade. Using historical data from November 1962, we estimated the long-term trend for fCO2, CT, and pH, confirming that the progressive acidification was driven by the atmospheric CO2 increase. In 59 years this led to a diminution of 11 % for both aragonite and calcite saturation state. As atmospheric CO2 is expected to increase in the future, the pH and carbonate saturation state will decrease at a faster rate than observed in recent years. A projection of future CT concentrations for a high emission scenario (SSP5-8.5) indicates that the surface pH in 2100 would decrease to 7.32 in winter. This is up to −0.86 lower than pre-industrial pH and −0.71 lower than pH observed in 2020. The aragonite undersaturation in surface waters would be reached as soon as 2050 (scenario SSP5-8.5) and 20 years later for a stabilization scenario (SSP2-4.5) with potential impacts on phytoplankton species and higher trophic levels in the rich ecosystems of the Kerguelen Islands area.

Regional differences in the air–sea CO2 flux between 3 and 14°S in the south-western tropical Atlantic

Context The fugacity of surface-seawater CO2 (fCO2sw) and the sea–air CO2 fluxes in the south-western tropical Atlantic (SWTA) were studied to increase the knowledge about the carbon cycle in this region. Aims This paper aims to describe the distribution of fCO2sw in SWTA. Methods The fCO2sw was measured from 2008 to 2020 by volunteer merchant ships with an onboard system that measures pCO2 while the vessels were underway. Key results Higher values occurred north of 8°S than in the region south of 8°S. The north is a strong source of CO2 for the atmosphere, with an annual mean value of 3.14 ± 0.52 mmol m−2 day−1. The south is a weaker source of CO2, with an annual average of 0.93 ± 0.90 mmol m−2 day−1. In the months of July and August, a weak sink of CO2 was observed, with a mean of −0.55 mmol m−2 day−1. Conclusions and implications The differences between these two regions are explained by the origin of the surface-water masses encountered along the ship track. The central branch of the South Equatorial Current (SEC) transports surface water, with a higher CO2 concentration and lower salinity, north of 8°S, whereas the surface waters between 8 and 14°S come from the southern branch of the SEC. The intertropical convergence zone is another physical process influencing the region north of 8°S.

The annual update GLODAPv2.2023: the global interior ocean biogeochemical data product

Abstract. The Global Ocean Data Analysis Project (GLODAP) is a synthesis effort providing regular compilations of surface to bottom ocean biogeochemical bottle data, with an emphasis on seawater inorganic carbon chemistry and related variables determined through chemical analysis of seawater samples. GLODAPv2.2023 is an update of the previous version, GLODAPv2.2022 (Lauvset et al., 2022). The major changes are as follows: data from 23 new cruises were added. In addition, a number of changes were made to the data included in GLODAPv2.2022. GLODAPv2.2023 includes measurements from more than 1.4 million water samples from the global oceans collected on 1108 cruises. The data for the now 13 GLODAP core variables (salinity, oxygen, nitrate, silicate, phosphate, dissolved inorganic carbon, total alkalinity, pH, chlorofluorocarbon-11 (CFC-11), CFC-12, CFC-113, CCl4, and SF6) have undergone extensive quality control with a focus on the systematic evaluation of bias. The data are available in two formats: (i) as submitted by the data originator but converted to World Ocean Circulation Experiment (WOCE) exchange format and (ii) as a merged data product with adjustments applied to minimize bias. For the present annual update, adjustments for the 23 new cruises were derived by comparing those data with the data from the 1085 quality-controlled cruises in the GLODAPv2.2022 data product using crossover analysis. SF6 data from all cruises were evaluated by comparison with CFC-12 data measured on the same cruises. For nutrients and ocean carbon dioxide (CO2), chemistry comparisons to estimates based on empirical algorithms provided additional context for adjustment decisions. The adjustments that we applied are intended to remove potential biases from errors related to measurement, calibration, and data-handling practices without removing known or likely time trends or variations in the variables evaluated. The compiled and adjusted data product is believed to be consistent to better than 0.005 in salinity, 1 % in oxygen, 2 % in nitrate, 2 % in silicate, 2 % in phosphate, 4 µmol kg−1 in dissolved inorganic carbon, 4 µmol kg−1 in total alkalinity, 0.01–0.02 in pH (depending on region), and 5 % in the halogenated transient tracers. The other variables included in the compilation, such as isotopic tracers and discrete CO2 fugacity (fCO2), were not subjected to bias comparison or adjustments. The original data, their documentation, and DOI codes are available at the Ocean Carbon and Acidification Data System of NOAA National Centers for Environmental Information (NCEI), which also provides access to the merged data product. This is provided as a single global file and as four regional ones – the Arctic, Atlantic, Indian, and Pacific oceans – under https://doi.org/10.25921/zyrq-ht66 (Lauvset et al., 2023). These bias-adjusted product files also include significant ancillary and approximated data, which were obtained by interpolation of, or calculation from, measured data. This living data update documents the GLODAPv2.2023 methods and provides a broad overview of the secondary quality control procedures and results.

Global Analysis of Surface Ocean CO2 Fugacity and Air‐Sea Fluxes With Low Latency

AbstractThe Surface Ocean CO2 Atlas (SOCAT) of CO2 fugacity (fCO2) observations is a key resource supporting annual assessments of CO2 uptake by the ocean and its side effects on the marine ecosystem. SOCAT data are usually released with a lag of up to 1.5 years which hampers timely quantification of recent variations of carbon fluxes between the Earth System components, not only with the ocean. This study uses a statistical ensemble approach to analyze fCO2 with a latency of one month only based on the previous SOCAT release and a series of predictors. Results indicate a modest degradation in a retrospective prediction test for 2021–2022. The generated fCO2 and fluxes for January–August 2023 show a progressive reduction in the Equatorial Pacific source following the La Niña retreat. A breaking‐record decrease in the northeastern Atlantic CO2 sink has been diagnosed on account of the marine heatwave event in June 2023.

Deciphering carbon dioxide fluxes and interactions in the Ganga river Basin of South Asia

Anthropogenic influences significantly modify the hydrochemical properties and material flow in riverine ecosystems across Asia, potentially accounting for 40–50% of global emissions. Despite the pervasive impact on Asian rivers, there is a paucity of studies investigating their correlation with carbon dioxide (CO2) emissions. In this study, we computed the partial pressure of CO2 (pCO2) using the carbonate equilibria-based model (pCO2SYS) and examined its correlation with hydrochemical parameters from historical records at 91 stations spanning 2013–2021 in the Ganga River. The investigation unveiled substantial spatial heterogeneity in the pCO2 across the Ganga River. The pCO2 concentration varied from 1321.76 μatm, 1130.98 μatm, and 1174.33 μatm in the upper, middle, and lower stretch, respectively, with a mean of 1185.29 μatm. Interestingly, the upper stretch exhibited elevated mean pCO2 and FCO2 levels (fugacity of CO2: 3.63 gm2d−1) compared to the middle and lower stretch, underscoring the intricate interplay between hydrochemistry and CO2 dynamics. In the context of pCO2 fluctuations, nitrate concentrations in the upper segment and levels of biological oxygen demand (BOD) and dissolved oxygen (DO) in the middle and lower segments are emerging as crucial explanatory factors. Furthermore, regression tree (RT) and importance analyses pinpointed biochemical oxygen demand (BOD) as the paramount factor influencing pCO2 variations across the Ganga River (n = 91). A robust negative correlation between BOD and FCO2 was also observed. The distinct longitudinal patterns of both parameters may induce a negative correlation between BOD and pCO2. Therefore, comprehensive studies are necessitated to decipher the underlying mechanisms governing this relationship. The present insights are instrumental in comprehending the potential of CO2 emissions in the Ganga River and facilitating riverine restoration and management. Our findings underscore the significance of incorporating South Asian rivers in the evaluation of the global carbon budget.

Seasonal variability of coastal pH and CO2 using an oceanographic buoy in the Canary Islands

Ocean acidification, caused by the absorption of carbon dioxide (CO2) from the atmosphere into the ocean, ranks among the most critical consequences of climate change for marine ecosystems. Most studies have examined pH and CO2 trends in the open ocean through oceanic time-series research. The analysis in coastal waters, particularly in island environments, remains relatively underexplored. This gap in our understanding is particularly important given the profound implications of these changes for coastal ecosystems and the blue economy. The present study focuses on the ongoing monitoring effort that started in March 2020 along the east coast of Gran Canaria, within the Gando Bay, by the CanOA-1 buoy. This monitoring initiative focuses on the systematic collection of multiple variables within the CO2 system, such as CO2 fugacity (fCO2), pH (in total scale, pHT), total inorganic carbon (CT), and other hydrographic variables including sea surface salinity (SSS), sea surface temperature (SST) and wind intensity and direction. Accordingly, the study allows the computation of the CO2 flux (FCO2) between the surface waters and the atmosphere. During the study period, stational (warm and cold periods) behavior was found for all the variables. The lowest SST values were recorded in March, with a range of 18.8-19.3°C, while the highest SST were observed in September and October, ranging from 24.5-24.8°C. SST exhibited an annual increase with a rate of 0.007°C yr-1. Warmer months increased SSS, while colder periods, influenced by extreme events like tropical storms, led to lower salinity (SSS=34.02). The predominant Trade Winds facilitated the arrival of deeper water, replenishing seawater. The study provided insights into atmospheric CO2. Atmospheric fCO2 averaged 415 ± 4 µatm (2020-2023). Surface water fCO2sw presented variability, with the highest values recorded in September and October, peaking at 437 µatm in September 2021. The lowest values for fCO2sw were found in February 2021 (368 µatm). From 2020 to 2023, surface water fCO2sw values displayed an increasing rate of 1.9 µatm yr-1 in the study area. The assessment of fCO2sw decomposition into thermal and non-thermal processes revealed the importance of SST on the fCO2sw. Nevertheless, in the present study, it is crucial to remark the impact of non-thermal factors on near-shallow coastal regions. Our findings highlight the influence of physical factors such as tides, and wind effect to horizontal mixing in these areas. The CT showed a mean concentration of 2113 ± 8 μmol kg-1 and pH at in-situ temperature (pHT,IS) has a mean value of 8.05 ± 0.02. The mean FCO2 from 2020 to 2023 was 0.34 ± 0.04 mmol m-2 d-1 (126 ± 13 mmol m-2 yr-1) acting as a slight CO2 source. In general, between May and December were the months when the area was a source of CO2. Extrapolating to the entire 6 km2 of Gando Bay, the region sourced 33 ± 4 Tons of CO2 yr-1.

Trends and drivers of CO2 parameters, from 2006 to 2021, at a time-series station in the Eastern Tropical Atlantic (6°S, 10°W)

The seawater fugacity of CO2 (fCO2) has been monitored hourly at an instrumented mooring at 6°S, 10°W since 2006. The mooring is located in the South Equatorial Current and is affected by the equatorial Atlantic cold tongue. This site is characterized by large seasonal sea surface temperature variations (>4°C). The fCO2 is measured by a spectrophotometric sensor deployed at about 1.5 meters deep. Measurements of seawater fCO2, sea surface temperature (SST) and sea surface salinity (SSS) are used to calculate total dissolved inorganic carbon (TCO2) and pH. Total alkalinity (TA) is calculated using an empirical relationship with SSS determined for this region. Satellite chlorophyll-a concentrations at 6°S, 10°W are low (<0.2 mg m-3) but some peaks over 0.8 mg m-3 are sometimes detected in August. Nevertheless, the site is a permanent source of CO2 to the atmosphere, averaging 4.7 ± 2.4 mmol m-2d-1 over 2006-2021. Despite the weakening of the wind, the CO2 flux increases significantly by 0.20 ± 0.05 mmol m-2d-1 yr-1. This suggests that the source of CO2 is increasing in this region. This is explained by seawater fCO2 increasing faster than the atmospheric increase during 2006-2021. Most of the seawater fCO2 increase is driven by the increase of TCO2, followed by SST. The fCO2 increase leads to a pH decrease of -0.0030 ± 0.0004 yr-1. The SST anomalies (SSTA) at 6°S, 10°W are correlated to the Tropical Southern Atlantic (TSA) index and to the Atlantic 3 region (ATL3) index with a correlation coefficient higher than 0.75. The strong positive phase of both ATL3 and TSA, observed towards the end of the time-series, is likely contributing to the strong increase of seawater fCO2.

Evolution of Air-Sea CO2 Flux during ARAMIS, EGEE and ROAM

The aim of this study is to compare evolution of the CO2 in two different areas of the tropical Atlantic Ocean. We investigate the spatial and temporal variability of CO2 fluxes, Total Alkalinity (TA), Dissolved Inorganic Carbon (DIC) and hydrological parameters (Salinity and Temperature) in the western and eastern tropical Atlantic for three years (2005-2006-2007), using the data collected during the ARAMIS 7, 8 and 10, EGEE and ROAM cruises (2019-2020). Our results showed that Sea Surface Salinity (SSS), Sea Surface Temperature (SST), TA and DIC are higher on average in the western area than in the eastern tropical Atlantic, except the oceanic CO2 fugacity (fCO2sw). A north-south gradient is observed with high values in the south of the Equator and low values in the north. This gradient is due to the Equatorial upwelling, which upwelled CO2-rich deep water to the surface; in addition, the Guinea current (GC) transports low salinity and parameters of carbon in the eastern area and Amazon outflow at West decreases the concentration of these parameters. On average, the western area was a sink of 0.34 mmol.m-2.d-1 and the eastern basin a source of 1.15 mmol.m-2.d-1. During ROAM cruises, air-sea CO2 flux was ten times higher than during all the EGEE cruises and more for all ARAMIS cruises.

A synthesis of ocean total alkalinity and dissolved inorganic carbon measurements from 1993 to 2022: the SNAPO-CO2-v1 dataset

Abstract. Total alkalinity (AT) and dissolved inorganic carbon (CT) in the oceans are important properties with respect to understanding the ocean carbon cycle and its link to global change (ocean carbon sinks and sources, ocean acidification) and ultimately finding carbon-based solutions or mitigation procedures (marine carbon removal). We present a database of more than 44 400 AT and CT observations along with basic ancillary data (spatiotemporal location, depth, temperature and salinity) from various ocean regions obtained, mainly in the framework of French projects, since 1993. This includes both surface and water column data acquired in the open ocean, coastal zones and in the Mediterranean Sea and either from time series or dedicated one-off cruises. Most AT and CT data in this synthesis were measured from discrete samples using the same closed-cell potentiometric titration calibrated with Certified Reference Material, with an overall accuracy of ±4 µmol kg−1 for both AT and CT. The data are provided in two separate datasets – for the Global Ocean and the Mediterranean Sea (https://doi.org/10.17882/95414, Metzl et al., 2023), respectively – that offer a direct use for regional or global purposes, e.g., AT–salinity relationships, long-term CT estimates, and constraint and validation of diagnostic CT and AT reconstructed fields or ocean carbon and coupled climate–carbon models simulations as well as data derived from Biogeochemical-Argo (BGC-Argo) floats. When associated with other properties, these data can also be used to calculate pH, the fugacity of CO2 (fCO2) and other carbon system properties to derive ocean acidification rates or air–sea CO2 fluxes.

Machine learning-based prediction of CO2 fugacity coefficients: Application to estimation of CO2 solubility in aqueous brines as a function of pressure, temperature, and salinity

Fugacity is a fundamental thermodynamical property of gas and gas mixtures to determine their behavior and dynamics in complex systems. Fugacity can be deduced experimentally from the measurements of volume as a function of pressure at constant temperature or calculated iteratively using analytical equations of states (EOS). Experimental measurement is time-consuming, and analytical models based on EOS are computationally demanding, especially when an approximate but quick estimation is desired. In this work, machine learning (ML) is employed as a viable alternative to analytical EOSs for quick and accurate approximation of CO2 fugacity coefficients. Five different ML algorithms are used to estimate the fugacity coefficients of pure CO2 as a function of pressure (≤ 2000 bar) and temperature (≤ 1000 °C). A combination of experimental and pseudo-experimental (obtained from an analytical EOS) data of CO2 fugacity coefficients is used to train, validate, and test the models. The best results were found using the Extreme Gradient Boosting algorithm, which showed a mean square error of only 0.0002 in the validation data and an average deviation of only 1.3% in the test data (pure prediction). To quantify the effectiveness of the machine learning techniques, results from the best-performing model are compared with two state-of-the-art analytical models. The ML model with significantly less computational complexity showed similar accuracy to the analytical models. The estimated fugacity data are then used to compute the CO2 solubility in aqueous NaCl solution of different concentrations, and a maximum deviation of only 3.2% from the experimental data is observed.

Anthropogenic carbon estimation in the surface ocean from atmospheric CO2 fugacity at the BATS (Bermuda Atlantic Time-series Study) station

In surface seawater, it is usually very difficult to quantify anthropogenic carbon concentrations. Many processes (such as air-sea exchanges of gases and heat, biological activity, and mixing of water masses), are at play and often on different timescales. Thus, various hypotheses are used to estimate the anthropogenic concentrations in surface waters. Here, using the relatively long (1980s to present) time series data sets from the Bermuda Atlantic Time-series Study site (BATS; 31°40′N, 64°10′W) in the North Atlantic Ocean, we evaluate results based upon two different hypotheses. The results clearly confirm that it is very difficult to assess anthropogenic carbon concentrations in surface waters from sole oceanic properties. However, this study further indicates that at this ocean site, they can be appropriately determined from low-frequency variations of atmospheric CO2 concentrations. Consequently, the impact of anthropogenic carbon penetration in surface waters on their acidification could be predicted.

Long-term trends of pH and inorganic carbon in the Eastern North Atlantic: the ESTOC site

Using 25 years of data from the North-East Atlantic Ocean at the ESTOC site, we confirm the surface ocean is actively absorbing carbon emissions caused by human activities and undergoing ocean acidification. The carbon dioxide is also increasing in the subsurface and deepest waters. Seawater salinity normalized inorganic carbon (NCT), fugacity of CO2 (fCO2) and anthropogenic CO2 increase at a rate of 1.17 ± 0.07 µmol kg−1, 2.1 ± 0.1 µatm yr−1 and 1.06 ± 0.11 μmol kg−1 yr−1, respectively, while the ocean pHT fixed to the average temperature of 21°C, declines at a rate of 0.002 ± 0.0001 pH yr−1 in the first 100 m. These rates are 20% higher than values determined for the period 1995–2010. Over the 25 years, the average surface fCO2 increased by 52.5 µatm while the pHT declined by 0.051 pH units (~13% increase in acidity), like the observed seasonal signal. After 2020, seawater conditions are outside the range of surface fCO2 and pHT seasonal amplitude observed in the 1990s. It was also predicted by the year 2040, fCO2 seawater data will be smaller than atmospheric one and the area will be acting as a sink the full year around. Parameterizations of AT, CT, pHT and fCO2 using observations of water temperature, salinity and dissolved oxygen were determined for the ESTOC site with standard error of estimation of 6.5 µmol kg−1, 6.8 µmol kg−1, 0.010 pH and 9.6 µatm, respectively, and were applied to the North-East Atlantic Ocean. The observations and the parameterizations showed that the trends of the carbonate variables along the water column in the eastern subtropical ESTOC region are dominated by anthropogenically induced changes, observed in the whole water profile.

Rapid fCO2 rise in the northern Barents Sea and Nansen Basin

Maps of surface water fugacity of CO2 (fCO2) over eastern Fram Strait, south-western Nansen Basin, and the north-western Barents Sea (73–84°N, 5–46°E) from September 1997 to December 2020 were made and used to investigate seasonal and temporal trends. The mapping utilized a neural network technique, the self-organizing map (SOM), that was trained with different combinations of satellite/observational/model data of sea surface temperature (SST), sea surface salinity (SSS), mixed layer depth (MLD), chlorophyll a (Chl a), sea ice concentration, and atmospheric mole fraction of CO2 (xCO2). The trained SOM was labelled with available surface ocean fCO2 data, and the labelled SOM was subsequently used to map the fCO2. The produced maps reveal that fCO2 in northern Barents Sea, at the border of the Nansen Basin, has increased significantly over the last decades by between 4.2 and 5.5 ± 0.6–1.1 µatm yr−1 over the winter to summer seasons. These rates are twice the rate of atmospheric CO2 increase, which was about 2 µatm yr−1. The spatial pattern coincides with the strongest decreases in sea ice concentration as well as with a salinification of the surface water. The former allows for a prolongation of the air-sea CO2 flux with resultant oceanic CO2 uptake in previously ice-covered waters, and the latter is caused by a shift from Arctic Water dominance to more saline waters containing more dissolved inorganic carbon, most likely of Atlantic Water origin although brine-release influenced deep water may also contribute.

The influence of CO2 partial pressure on the stability of dawsonite-based on water-rock physical experiment and numerical simulation

Dawsonite has the potential to serve as a significant mineral for carbon sequestration in geological storage, and its stability in the reservoir is determined by intricate fluid-rock interactions. Thus, it is crucial to elucidate the mechanism that influences the stability of dawsonite. In this study, a natural dawsonite-bearing sandstone in Dongying Sag was utilized for CO2–H2O-Rock interaction experiments and TOUGHREACT numerical simulations at varying CO2 pressures. Additionally, the CO2 fugacity value acting on the sandstone in the reactor experiment was corrected using thermodynamic analysis. By systematically analyzing the dissolution response and elemental composition evolution of dawsonite through techniques such as scanning electron microscopy observation and energy spectrum analysis, X-ray diffraction analysis, hydrochemical analysis, and dawsonite stability indicator parameters, the influence mode on the stability of dawsonite was clarified. The atomic ratio of dawsonite in each experimental group (between Al:O = 1:3 and Al:O = 1:2) suggested that gibbsite and boehmite were formed after the dissolution of dawsonite under high CO2 pressure. When pCO2≤7.3 MPa or pCO2＞8.3 MPa, increasing the CO2 pressure could enhance the thermal stability of dawsonite and inhibit its decomposition. However, when pCO2 was between 7.3 MPa and 8.3 MPa, the reaction equilibrium was disrupted, and a considerable amount of dawsonite was dissolved and transformed into new minerals. Both physical experimentation and numerical simulation indicated that dawsonite achieved a stable state at pCO2 = 7.3 MPa and 120 °C.

Low‐pressure plasticization of PEBAX 2533 membrane by carbon dioxide

AbstractPEBAX 2533 membrane is used to investigate plasticization by carbon dioxide (CO2) at low pressure. To reduce complex interaction caused by hydrostatic pressure and competitive sorption, a new experimental technique named the “Rest test” is presented. In the Rest test, the membrane is exposed to permeation of CO2 at 4 bar for 30 min and then put to rest for up to 12 h with residual CO2 after ventilation. When the membrane rests more than 9 h with residual CO2 after the permeation, the permeability increases by, at least, 50%. Permeation of CO2 is the prerequisite condition of permeability increase during the rest. Permeability increase in the Rest test is improved by permeate side purge and prolonged rest period. Fugacity and sorption of leftover CO2 during the rest are the main factors inducing the permeability increase, whereas the permeability increase is suppressed by higher feed pressure and longer CO2 permeation time, indicating the influence of hydrostatic pressure. The Rest test cannot increase the permeability of glassier PEBAX 1657. The findings and relevant factors suggest that low‐pressure plasticization during the rest is a potential source of the permeability increase.

Determination of discrete sampling locations minimizing both the number of samples and the maximum interpolation error: Application to measurements of carbonate chemistry in surface ocean

Over the past three decades, a variety of programs have conducted extensive measurements of ocean properties at fixed stations throughout the water column, as well as in the surface ocean via oceanographic ships and ships of opportunity. Ships of opportunity were particularly used to determine the air-sea CO2 fluxes from automated measurements of sea-surface temperature, salinity, and CO2 fugacity. These underway measurements, often recorded at a frequency of every minute, generate large data files that need to be quality controlled, stored and analyzed. For practical use these data are often binned by 1° latitude x 1° longitude. Unfortunately, by doing so, there is a consequential loss of accuracy for these data sets.Here, using the original 2010 underway data sets of sea-surface temperature, sea-surface salinity, total alkalinity and total inorganic carbon, along the cruise track from Hobart (Tasmania) to Dumont D'Urville (Antarctica), we show what would had been a more appropriate sampling strategy for each of these properties, maintaining their full measurement accuracy, while improving their interpolation accuracy. Furthermore, this analysis illustrates a general methodology for objectively determining, under suitable conditions, the appropriate locations for each property measurement according to a required accuracy. These results should greatly facilitate future cruise preparation and reduce the cost of measurements, while improving their scientific value.

GLODAPv2.2022: the latest version of the global interior ocean biogeochemical data product

Abstract. The Global Ocean Data Analysis Project (GLODAP) is a synthesis effort providing regular compilations of surface-to-bottom ocean biogeochemical bottle data, with an emphasis on seawater inorganic carbon chemistry and related variables determined through chemical analysis of seawater samples. GLODAPv2.2022 is an update of the previous version, GLODAPv2.2021 (Lauvset et al., 2021). The major changes are as follows: data from 96 new cruises were added, data coverage was extended until 2021, and for the first time we performed secondary quality control on all sulfur hexafluoride (SF6) data. In addition, a number of changes were made to data included in GLODAPv2.2021. These changes affect specifically the SF6 data, which are now subjected to secondary quality control, and carbon data measured on board the RV Knorr in the Indian Ocean in 1994–1995 which are now adjusted using certified reference material (CRM) measurements made at the time. GLODAPv2.2022 includes measurements from almost 1.4 million water samples from the global oceans collected on 1085 cruises. The data for the now 13 GLODAP core variables (salinity, oxygen, nitrate, silicate, phosphate, dissolved inorganic carbon, total alkalinity, pH, chlorofluorocarbon-11 (CFC-11), CFC-12, CFC-113, CCl4, and SF6) have undergone extensive quality control with a focus on systematic evaluation of bias. The data are available in two formats: (i) as submitted by the data originator but converted to World Ocean Circulation Experiment (WOCE) exchange format and (ii) as a merged data product with adjustments applied to minimize bias. For the present annual update, adjustments for the 96 new cruises were derived by comparing those data with the data from the 989 quality-controlled cruises in the GLODAPv2.2021 data product using crossover analysis. SF6 data from all cruises were evaluated by comparison with CFC-12 data measured on the same cruises. For nutrients and ocean carbon dioxide (CO2) chemistry comparisons to estimates based on empirical algorithms provided additional context for adjustment decisions. The adjustments that we applied are intended to remove potential biases from errors related to measurement, calibration, and data handling practices without removing known or likely time trends or variations in the variables evaluated. The compiled and adjusted data product is believed to be consistent to better than 0.005 in salinity, 1 % in oxygen, 2 % in nitrate, 2 % in silicate, 2 % in phosphate, 4 µmol kg−1 in dissolved inorganic carbon, 4 µmol kg−1 in total alkalinity, 0.01–0.02 in pH (depending on region), and 5 % in the halogenated transient tracers. The other variables included in the compilation, such as isotopic tracers and discrete CO2 fugacity (fCO2), were not subjected to bias comparison or adjustments. The original data, their documentation, and DOI codes are available at the Ocean Carbon and Acidification Data System of NOAA NCEI (https://www.ncei.noaa.gov/access/ocean-carbon-acidification-data-system/oceans/GLODAPv2_2022/, last access: 15 August 2022). This site also provides access to the merged data product, which is provided as a single global file and as four regional ones – the Arctic, Atlantic, Indian, and Pacific oceans – under https://doi.org/10.25921/1f4w-0t92 (Lauvset et al., 2022). These bias-adjusted product files also include significant ancillary and approximated data, which were obtained by interpolation of, or calculation from, measured data. This living data update documents the GLODAPv2.2022 methods and provides a broad overview of the secondary quality control procedures and results.

Comparison of discrete and underway CO2 measurements: Inferences on the temperature dependence of the fugacity of CO2 in seawater

The fugacity or partial pressure of CO2 in surface water (fCO2w) is a key parameter to determine air-sea CO2 fluxes and the evolution of ocean acidification. Despite its importance some key physical chemical characteristics are not fully resolved, notably its dependence on temperature. The fCO2w is mostly measured by autonomous underway systems near in situ sea surface temperature (SST). Subsurface measurements are commonly carried out on individual (discrete) samples at a fixed temperature, normally 20 °C. Here, the underway system observations are compared with co-located discrete observations to determine the consistency of these types of measurements. The co-located discrete fCO2w at 20 °C and underway fCO2w measurements at SST are used to infer the temperature dependence of CO2. In addition, calculated fCO2w from total alkalinity (TA) and total dissolved inorganic carbon (DIC) are compared with the underway and discrete fCO2w measurements. For 21 cruises spanning the major ocean basins from 1992 to 2020 a temperature dependence of 4.13 ± 0.01% °C−1 is determined in close agreement with a widely used previous empirical estimate of 4.23 ± 0.02% °C−1 for North Atlantic surface water. The temperature dependency of calculated fCO2w from TA and DIC using recommended constants is 4.10% °C−1 for 17 cruises where there are co-located measurements of fCO2w, TA and DIC.