ALBERT

Description: Since a pH sensor has become available that is principally suitable for use on demanding autonomous measurement platforms, the marine CO2 system can be observed independently and continuously by Biogeochemical Argo floats. This opens the potential to detect variability and long-term changes in interior ocean inorganic carbon storage and quantify the ocean sink for atmospheric CO2. In combination with a second parameter of the marine CO2 system, pH can be a useful tool to derive the surface ocean CO2 partial pressure (pCO2). The large spatiotemporal variability in the marine CO2 system requires sustained observations to decipher trends and study the impacts of short-term events (e.g., eddies, storms, phytoplankton blooms) but also puts a high emphasis on the quality control of float-based pH measurements. In consequence, a consistent and rigorous quality control procedure is being established to correct sensor offsets or drifts as the interpretation of changes depends on accurate data. By applying current standardized routines of the Argo data management to pH measurements from a pH / O2 float pilot array in the subpolar North Atlantic Ocean, we assess the uncertainties and lack of objective criteria associated with the standardized routines, notably the choice of the reference method for the pH correction (CANYON-B, LIR-pH, ESPER-NN, and ESPER-LIR) and the reference depth for this adjustment. For the studied float array, significant differences ranging between ca. 0.003 pH units and ca. 0.04 pH units are observed between the four reference methods which have been proposed to correct float pH data. Through comparison against discrete and underway pH data from other platforms, an assessment of the adjusted float pH data quality is presented. The results point out noticeable discrepancies near the surface of 〉 0.004 pH units. In the context of converting surface ocean pH measurements into pCO2 data for the purpose of deriving air–sea CO2 fluxes, we conclude that an accuracy requirement of 0.01 pH units (equivalent to a pCO2 accuracy of 10 µatm as a minimum requirement for potential future inclusion in the Surface Ocean CO2 Atlas, SOCAT, database) is not systematically achieved in the upper ocean. While the limited dataset and regional focus of our study do not allow for firm conclusions, the evidence presented still calls for the inclusion of an additional independent pH reference in the surface ocean in the quality control routines. We therefore propose a way forward to enhance the float pH quality control procedure. In our analysis, the current philosophy of pH data correction against climatological reference data at one single depth in the deep ocean appears insufficient to assure adequate data quality in the surface ocean. Ideally, an additional reference point should be taken at or near the surface where the resulting pCO2 data are of the highest importance to monitor the air–sea exchange of CO2 and would have the potential to very significantly augment the impact of the current observation network.

Description: The presented pilot for the Synthesis Product for Ocean Time Series (SPOTS) includes data from 12 fixed ship-based time-series programs. The related stations represent unique open-ocean and coastal marine environments within the Atlantic Ocean, Pacific Ocean, Mediterranean Sea, Nordic Seas, and Caribbean Sea. The focus of the pilot has been placed on biogeochemical essential ocean variables: dissolved oxygen, dissolved inorganic nutrients, inorganic carbon (pH, total alkalinity, dissolved inorganic carbon, and partial pressure of CO2), particulate matter, and dissolved organic carbon. The time series used include a variety of temporal res- olutions (monthly, seasonal, or irregular), time ranges (10–36 years), and bottom depths (80–6000 m), with the oldest samples dating back to 1983 and the most recent one corresponding to 2021. Besides having been harmo- nized into the same format (semantics, ancillary data, units), the data were subjected to a qualitative assessment in which the applied methods were evaluated and categorized. The most recently applied methods of the time- series programs usually follow the recommendations outlined by the Bermuda Time Series Workshop report (Lorenzoni and Benway, 2013), which is used as the main reference for “method recommendations by prevalent initiatives in the field”. However, measurements of dissolved oxygen and pH, in particular, still show room for improvement. Additional data quality descriptors include precision and accuracy estimates, indicators for data variability, and offsets compared to a reference and widely recognized data product for the global ocean: the GLobal Ocean Data Analysis Project (GLODAP). Generally, these descriptors indicate a high level of continuity in measurement quality within time-series programs and a good consistency with the GLODAP data product, even though robust comparisons to the latter are limited. The data are available as (i) a merged comma-separated file that is compliant with the World Ocean Circulation Experiment (WOCE) exchange format and (ii) a format dependent on user queries via the Environmental Research Division’s Data Access Program (ERDDAP) server of the Global Ocean Observing System (GOOS). The pilot increases the data utility, findability, accessibility, interoperability, and reusability following the FAIR philosophy, enhancing the readiness of biogeochemical time series. It facilitates a variety of applications that benefit from the collective value of biogeochemical time-series observations and forms the basis for a sustained time-series living data product, SPOTS, complementing relevant products for the global interior ocean carbon data (GLobal Ocean Data Analysis Project), global surface ocean carbon data (Surface Ocean CO2 Atlas; SOCAT), and global interior and surface methane and nitrous oxide data (MarinE MethanE and NiTrous Oxide product). Aside from the actual data compilation, the pilot project produced suggestions for reporting metadata, im- plementing quality control measures, and making estimations about uncertainty. These recommendations aim to encourage the community to adopt more consistent and uniform practices for analysis and reporting and to update these practices regularly. The detailed recommendations, links to the original time-series programs, the original data, their documentation, and related efforts are available on the SPOTS website. This site also pro- vides access to the data product (DOI: https://doi.org/10.26008/1912/bco-dmo.896862.2, Lange et al., 2024) and ancillary data.