High‐accuracy spectrophotometric pH measurements were taken during a summer cruise to study the pH dynamics and its controlling mechanisms in the northern Gulf of Mexico in hypoxia season. Using the recently available dissociation constants of the purified m‐cresol purple (Douglas & Byrne, 2017,
Re-evaluation of carbonic acid dissociation constants across conditions and the implications for ocean acidification
With the increasing threat of ocean acidification and the important role of the oceans in the global carbon cycle, highly precise, accurate, and intercomparable determination of inorganic carbon system parameters is required. Thermodynamic relationships enable the system to be fully constrained using a combination of direct measurements and calculations. However, calculations are complicated by many formulations for dissociation constants (over 120 possible combinations). To address these important issues of uncertainty and comparability, we
evaluated the various combinations of constants and their (dis)agreement with direct measurements over a range of temperature (−1.9–40 ◦C), practical salinity (15–39) and pCO2 (150–1200 μatm). The results demonstrate that differences between the calculations and measurements are significantly larger than measurement uncertainties, meaning the oft-stated paradigm that one only needs to measure two parameters and the others can be calculated
does not apply for climate quality ocean acidification research. The uncertainties in calculated pHt prevent climate quality pHt from being calculated from total alkalinity (TA) and dissolved inorganic carbon (DIC) and should be directly measured instead. However, climate quality TA and DIC can often be calculated using measured pH and DIC or TA respectively. Calculations are notably biased at medium-to-high pCO2 values (~500–800 μatm) implying models underestimate future ocean acidification. Uncertainty in the dissociation constants leads to significant uncertainty in the depth of the aragonite saturation horizon (>500 m in the
Southern Ocean) and must be considered when studying calcium carbonate cycling. Significant improvements in the precision of the thermodynamic constants are required to improve pHt calculations.
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- Award ID(s):
- 1923312
- NSF-PAR ID:
- 10493887
- Publisher / Repository:
- Elsevier
- Date Published:
- Journal Name:
- Marine Chemistry
- Volume:
- 250
- Issue:
- C
- ISSN:
- 0304-4203
- Page Range / eLocation ID:
- 104247
- Subject(s) / Keyword(s):
- ["Ocean Acidification","Marine Carbon Cycle"]
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract https://doi.org/10.1016/j.marchem.2017.10.001 ; Müller & Rehder, 2018,https://doi.org/10.3389/fmars.2018.00177 ), spectrophotometrically measured pH showed excellent agreement with pH calculated from dissolved inorganic carbon (DIC) and total alkalinity over a wide salinity range of 0 to 36.9 (0.005 ± 0.016,n = 550). The coupled changes in DIC, oxygen, and nutrients suggest that biological production of organic matter in surface water and the subsequent aerobic respiration in subsurface was the dominant factor regulating pH variability in the nGOM in summer. The highest pH values were observed, together with the maximal biological uptake of DIC and nutrients, at intermediate salinities in the Mississippi and Atchafalaya plumes where light and nutrient conditions were favorable for phytoplankton growth. The lowest pH values (down to 7.59) were observed along with the highest concentrations of DIC and apparent oxygen utilization in hypoxic bottom waters. The nonconservative pH changes in both surface and bottom waters correlated well with the biologically induced changes in DIC, that is, per 100‐μmol/kg biological removal/addition of DIC resulted in 0.21 unit increase/decrease in pH. Coastal bottom water with lower pH buffering capacity is more susceptible to acidification from anthropogenic CO2invasion but reduction in eutrophication may offset some of the increased susceptibility to acidification. -
This dataset consists of the Surface Ocean CO2 Atlas Version 2022 (SOCATv2022) data product files. The ocean absorbs one quarter of the global CO2 emissions from human activity. The community-led Surface Ocean CO2 Atlas (www.socat.info) is key for the quantification of ocean CO2 uptake and its variation, now and in the future. SOCAT version 2022 has quality-controlled in situ surface ocean fCO2 (fugacity of CO2) measurements on ships, moorings, autonomous and drifting surface platforms for the global oceans and coastal seas from 1957 to 2021. The main synthesis and gridded products contain 33.7 million fCO2 values with an estimated accuracy of better than 5 μatm. A further 6.4 million fCO2 sensor data with an estimated accuracy of 5 to 10 μatm are separately available. During quality control, marine scientists assign a flag to each data set, as well as WOCE flags of 2 (good), 3 (questionable) or 4 (bad) to individual fCO2 values. Data sets are assigned flags of A and B for an estimated accuracy of better than 2 μatm, flags of C and D for an accuracy of better than 5 μatm and a flag of E for an accuracy of better than 10 μatm. Bakker et al. (2016) describe the quality control criteria used in SOCAT versions 3 to 2022. Quality control comments for individual data sets can be accessed via the SOCAT Data Set Viewer (www.socat.info). All data sets, where data quality has been deemed acceptable, have been made public. The main SOCAT synthesis files and the gridded products contain all data sets with an estimated accuracy of better than 5 µatm (data set flags of A to D) and fCO2 values with a WOCE flag of 2. Access to data sets with an estimated accuracy of 5 to 10 (flag of E) and fCO2 values with flags of 3 and 4 is via additional data products and the Data Set Viewer (Table 8 in Bakker et al., 2016). SOCAT publishes a global gridded product with a 1° longitude by 1° latitude resolution. A second product with a higher resolution of 0.25° longitude by 0.25° latitude is available for the coastal seas. The gridded products contain all data sets with an estimated accuracy of better than 5 µatm (data set flags of A to D) and fCO2 values with a WOCE flag of 2. Gridded products are available monthly, per year and per decade. Two powerful, interactive, online viewers, the Data Set Viewer and the Gridded Data Viewer (www.socat.info), enable investigation of the SOCAT synthesis and gridded data products. SOCAT data products can be downloaded. Matlab code is available for reading these files. Ocean Data View also provides access to the SOCAT data products (www.socat.info). SOCAT data products are discoverable, accessible and citable. The SOCAT Data Use Statement (www.socat.info) asks users to generously acknowledge the contribution of SOCAT scientists by invitation to co-authorship, especially for data providers in regional studies, and/or reference to relevant scientific articles. The SOCAT website (www.socat.info) provides a single access point for online viewers, downloadable data sets, the Data Use Statement, a list of contributors and an overview of scientific publications on and using SOCAT. Automation of data upload and initial data checks allows annual releases of SOCAT from version 4 onwards. SOCAT is used for quantification of ocean CO2 uptake and ocean acidification and for evaluation of climate models and sensor data. SOCAT products inform the annual Global Carbon Budget since 2013. The annual SOCAT releases by the SOCAT scientific community are a Voluntary Commitment for United Nations Sustainable Development Goal 14.3 (Reduce Ocean Acidification) (#OceanAction20464). More broadly the SOCAT releases contribute to UN SDG 13 (Climate Action) and SDG 14 (Life Below Water), and to the UN Decade of Ocean Science for Sustainable Development. Hundreds of peer-reviewed scientific publications and high-impact reports cite SOCAT. The SOCAT community-led synthesis product is a key step in the value chain based on in situ inorganic carbon measurements of the oceans, which provides policy makers with critical information on ocean CO2 uptake in climate negotiations. The need for accurate knowledge of global ocean CO2 uptake and its (future) variation makes sustained funding of in situ surface ocean CO2 observations imperative.more » « less
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A quantitative understanding of pH, acid-base equilibria, and chemical speciation in natural waters including seawater is needed in applications ranging from global change to environmental and water quality management. In a previous study (Humphreys et al., 2022) we implemented a model of solutions containing the ions of artificial seawater, based upon the use of the Pitzer equations for the calculation of activity coefficients and including, for the first time, the propagation of uncertainties. This was extended (Clegg et al., 2022) to include the Tris buffer solutions that are used to calibrate the seawater total pH scale. Here we apply the same methods to develop a model of solutions containing the ions of standard reference seawater, based upon studies by Millero and co-workers. We compare the predictions of the model to literature data for: the dissociation of dissolved CO2 and bicarbonate ion; boric acid dissociation; saturation with respect to calcite, the ion product of water, and osmotic coefficients of seawater. Estimates of the uncertainty contributions of all thermodynamic equilibrium constants and Pitzer parameters to the variance of the calculated quantity are used to determine which elements of the model need improvement, with the aim of agreeing with properties noted above to within their experimental uncertainty. Further studies are recommended. Comparisons made with several datasets for carbonate system dissociation in seawater suggest which are the most reliable, and identify low salinity waters (S <10) as a region for which dissociation constants of bicarbonate are not yet accurately known. At present, the model is likely to be most useful for the direct calculation of equilibria in natural waters of arbitrary composition, or for adjusting dissociation constants known for seawater media to values for natural waters in which the relative compositions of the major ions are different.more » « less
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Abstract In coastal regions and marginal bodies of water, the increase in partial pressure of carbon dioxide (
p CO2) in many instances is greater than that of the open ocean due to terrestrial (river, estuarine, and wetland) influences, decreasing buffering capacity and/or increasing water temperatures. Coastal oceans receive freshwater from rivers and groundwater as well as terrestrial-derived organic matter, both of which have a direct influence on coastal carbonate chemistry. The objective of this research is to determine if coastal marshes in Georgia, USA, may be “hot-spots” for acidification due to enhanced inorganic carbon sources and if there is terrestrial influence on offshore acidification in the South Atlantic Bight (SAB). The results of this study show that dissolved inorganic carbon (DIC) and total alkalinity (TA) are elevated in the marshes compared to predictions from conservative mixing of the freshwater and oceanic end-members, with accompanying pH around 7.2 to 7.6 within the marshes and aragonite saturation states (ΩAr) <1. In the marshes, there is a strong relationship between the terrestrial/estuarine-derived organic and inorganic carbon and acidification. Comparisons of pH, TA, and DIC to terrestrial organic material markers, however, show that there is little influence of terrestrial-derived organic matter on shelf acidification during this period in 2014. In addition, ΩArincreases rapidly offshore, especially in drier months (July). River stream flow during 2014 was anomalously low compared to climatological means; therefore, offshore influences from terrestrial carbon could also be decreased. The SAB shelf may not be strongly influenced by terrestrial inputs to acidification during drier than normal periods; conversely, shelf waters that are well-buffered against acidification may not play a significant role in mitigating acidification within the Georgia marshes.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1016/j.marchem.2023.104247
