Gaining insights into the seawater carbonate system using discrete fCO2 measurements

Understanding the ocean carbon sink and its future acidification-derived changes requires accurate and precise measurements with good spatiotemporal coverage. In addition, a deep knowledge of the thermodynamics of the seawater carbonate system is key to interconverting between measured and calculated variables. To gain insights into the remaining inconsistencies in the seawater carbonate system, we assess discrete water column measurements of carbon dioxide fugacity (fCO2), dissolved inorganic carbon (DIC), total alkalinity (TA), and pH measured with unpurified indicators, from hydrographic cruises in the Atlantic, Pacific, and Southern Oceans included in GLODAPv2.2020 (19,013 samples). An agreement of better than ±3% between fCO2 measured and calculated from DIC and pH is obtained for 94% of the compiled dataset, while when considering fCO2 measured and calculated from DIC and TA, the agreement is better than ±4% for 88% of the compiled dataset, with a poorer internal consistency for high-CO2 waters. Inspecting all likely sources of uncertainty from measured and calculated variables, we conclude that the seawater carbonate system community needs to (i) further refine the thermodynamic model of the seawater carbonate system, especially K2, including the impact of organic compounds and other acid-base systems on TA; (ii) update the standard operating procedures for the seawater carbonate system measurements following current technological and analytical advances, paying particular attention to the pH methodology that is the one that evolved the most; (iii) encourage measuring discrete water column fCO2 to further check the internal consistency of the seawater carbonate system, especially given the new era of sensor-based seawater measurements; and (iv) develop seawater Certified Reference Materials (CRMs) for fCO2 and pH together with seawater CRMs for TA and DIC over the range of values encountered in the global ocean. Our conclusions also suggest the need for a re-evaluation of the adjustments applied by GLODAPv2 to pH, which were based on DIC and TA consistency checks but not supported by fCO2 and DIC consistency

Ocean acidification along the 24.5°N section in the subtropical North Atlantic

9 páginas, 4 figuras.-- Proyecto CarbochangeOcean acidification is directly related to increasing atmospheric CO2 levels due to human activities and the active role of the global ocean in absorbing part of this anthropogenic CO2. Here we present an assessment of the pH changes that have occurred along 24.5°N in the subtropical North Atlantic through comparison of pH observations conducted in 1992 and 2011. It reveals an overall decline in pH values in the first 1000 dbar of the water column. The deconvolution of the temporal pH differences into anthropogenic and nonanthropogenic components reveals that natural variability, mostly owed to a decrease in oxygen levels in particular regions of the section, explains the vertical distribution of the larger pH decreases (up to −0.05 pH units), which are found within the permanent thermocline. The detection of long-term trends in dissolved oxygen in the studied region gains importance for future pH projections, as these changes modulate the anthropogenically derived acidification. The anthropogenic forcing explains significant acidification deeper than 1000 dbar in the western basin, within the Deep Western Boundary Current.We acknowledge funding from the Spanish Ministry of Economy and Competitiveness through grants CSD2008-00077 (Circumnavigation Expedition MALASPINA 2010 Project), CTM2009-08849 (ACDC Project), and CTM2012-32017 (MANIFEST Project) and from the Seventh Framework Programme FP7 CARBOCHANGE (grant agreement 264879). E.F. Guallart was funded by CSIC through a JAE-Pre grant.Peer reviewe

Ocean acidification at the crossroads: approaching unpurified and purified m-cresol spectrophotometric pH measurements

5th International Symposium on the Ocean in a High CO2 World, 13-16 September 2022, Lima, PerúThe pH spectrophotometric method is the gold standard to measure pH in the ocean and detect ocean acidification trends due to the anthropogenic carbon uptake from the atmosphere into the ocean. The pH method has an accuracy of about 0.003 and a precision of about 0.0004 pH units. The method has evolved since the 1990s when defined using manual approaches and unpurified dyes to currently automated methods using expensive and cumbersome to obtain purified dyes. From a collection of about 300 paired measurements of unpurified and purified pH measurements along with DIC and TA from natural samples in the Eastern North Atlantic and Mediterranean Sea we find that contrary to expected, unpurified and purified pH measurements calculated with the proper corresponding functions agree to within 0.003 pH units for waters with pH >7.95, while waters with lower pH, calculated unpurified pH is higher than purified pH. Applying the purposed correction from unpur to pur pH as explained in the literature is not straight forward, the community risks for an incoherence in the pH time series. Clearly, we need a definition and evaluation of the unpur to pur correction on real seawater samples by different labs, and look for a consensus agreement on seawater pH definition (scales!, ionic model), metrology, and on the Standard Operational Procedure, where loose issues are still presentN

Global ocean spectrophotometric pH assessment: consistent inconsistencies

Ocean acidification (OA)—or the decrease in seawater pH resulting from ocean uptake of CO2 released by human activities—stresses ocean ecosystems and is recognized as a Climate and Sustainable Development Goal Indicator that needs to be evaluated and monitored. Monitoring OA-related pH changes requires a high level of precision and accuracy. The two most common ways to quantify seawater pH are to measure it spectrophotometrically or to calculate it from total alkalinity (TA) and dissolved inorganic carbon (DIC). However, despite decades of research, small but important inconsistencies remain between measured and calculated pH. To date, this issue has been circumvented by examining changes only in consistently measured properties. Currently, the oceanographic community is defining new observational strategies for OA and other key aspects of the ocean carbon cycle based on novel sensors and technologies that rely on validation against data records and/or synthesis products. Comparison of measured spectrophotometric pH to calculated pH from TA and DIC measured during the 2000s and 2010s eras reveals that (1) there is an evolution toward a better agreement between measured and calculated pH over time from 0.02 pH units in the 2000s to 0.01 pH units in the 2010s at pH > 7.6; (2) a disagreement greater than 0.01 pH units persists in waters with pH < 7.6, and (3) inconsistencies likely stem from variations in the spectrophotometric pH standard operating procedure (SOP). A reassessment of pH measurement and calculation SOPs and metrology is urgently neede

Two new coastal time-series of seawater carbonate system variables in the NW Mediterranean Sea : rates and mechanisms controlling pH changes

Arturo Lucas present address: Universitat Autònoma de Barcelona. Institut de Ciència i Tecnologia AmbientalsIn this work, we present, for the first time, the seawater carbonate system measurements of two coastal time-series in the NW Mediterranean Sea, L'Estartit Oceanographic Station (EOS; 42.05°N 3.2542°E) and the Blanes Bay Microbial Observatory (BBMO; 41.665°N 2.805°E). At these two time-series, measurements of total alkalinity (TA), pH, and associated variables, such as dissolved inorganic nutrients, temperature, and salinity, have been performed monthly since 2010 in surface seawater. Seasonality and seasonal amplitude are analogous in both time-series, with seasonality in pHTin situ (pH at in situ seawater conditions on the total hydrogen ion scale) primarily determined by seasonality in sea surface temperature. The evaluated pHTin situ trends at BBMO (-0.0021 ± 0.0003 yr-1) and EOS (-0.0028 ± 0.0005 yr-1) agree with those reported for coastal and open ocean surface waters in the Mediterranean Sea and open ocean surface waters of the global ocean, therefore indicating that these time-series are representative of global ocean acidification signals despite being coastal. The decreases in pHTin situ can be attributed to increases in total dissolved inorganic carbon (DIC; 1.5 ± 0.4 µmol kg-1 yr-1 at BBMO and 1.6 ± 0.6 µmolESkg-1 yr-1 at EOS) and sea surface temperature (0.08 ± 0.02 °C yr-1 at BBMO and 0.08 ± 0.04 °C yr-1 at EOS). The increases in carbon dioxide fugacity (fCO2; 2.4 ± 0.3 µmol kg-1 yr-1 at BBMO and 2.9 ± 0.6 µmol kg-1 yr-1 at EOS) follow the atmospheric CO2 forcing, thus indicating the observed DIC increase is related to anthropogenic CO2 uptake. The increasing trends in TA (1.2 ± 0.3 µmol kg-1 yr-1 at BBMO and 1.0 ± 0.5 µmol kg-1 yr-1 at EOS) buffered the acidification rates, counteracting 60% and 72% of the pHTin situ decrease caused by increasing DIC at EOS and BBMO, respectively. Once accounted for the neutralizing effect of TA increase, the rapid sea surface warming plays a larger role in the observed pH decreases (43% at EOS and 62% at BBMO) than the DIC increase (36% at EOS and 33% at BBMO)

Spectrophotometric Measurement of Carbonate Ion in Seawater over a Decade: Dealing with Inconsistencies

The spectrophotometric methodology for carbonate ion determination in seawater was first published in 2008 and has been continuously evolving in terms of reagents and formulations. Although being fast, relatively simple, affordable, and potentially easy to implement in different platforms and facilities for discrete and autonomous observations, its use is not widespread in the ocean acidification community. This study uses a merged overdetermined CO2 system data set (carbonate ion, pH, and alkalinity) obtained from 2009 to 2020 to assess the differences among the five current approaches of the methodology through an internal consistency analysis and discussing the sources of uncertainty. Overall, the results show that none of the approaches meet the climate goal (+/- 1 % standard uncertainty) for ocean acidification studies for the whole carbonate ion content range in this study but usually fulfill the weather goal (+/- 10 % standard uncertainty). The inconsistencies observed among approaches compromise the consistency of data sets among regions and through time, highlighting the need for a validated standard operating procedure for spectrophotometric carbonate ion measurements as already available for the other measurable CO2 variables