Description: Highlights • Biogeochemical processes create CO2 sources/sinks by altering seawater AT and CT • Source/sink strength depends on local seawater ‘isocapnic quotient’ (Q) • Q depends on seawater temperature and the state of the marine carbonate system • Spatiotemporal variability in Q drives heterogeneous CO2 source/sink magnitude • Future warming and CO2 emissions will modify Q and the size of CO2 sources/sinks Abstract The ocean holds a large reservoir of carbon dioxide (CO2), and mitigates climate change through uptake of anthropogenic CO2. Fluxes of CO2 between the atmosphere and surface ocean are regulated by a number of physical and biogeochemical processes, resulting in a spatiotemporally heterogeneous CO2 distribution. Determining the influence of each individual process is useful for interpreting marine carbonate system observations, and is also necessary to investigate how changes in these drivers could affect air-sea CO2 exchange. Biogeochemical processes exert an influence primarily through modifying seawater dissolved inorganic carbon (CT) and total alkalinity (AT), thus changing the seawater partial pressure of CO2 (psw). Here, we propose a novel conceptual framework through which the size of the CO2 source or sink generated by any biogeochemical process, denoted Φ, can be evaluated. This is based on the ‘isocapnic quotient’ (Q), which defines the trajectory through (AT,CT) phase space for which there is no change in psw. We discuss the limitations and uncertainties inherent in this technique, which are negligible for most practical purposes, and its links with existing, related approaches. We investigate the effect on Φ of spatiotemporal heterogeneity in Q in the present day surface ocean for several key biogeochemical processes. This leads the magnitude of the CO2 source or sink generated by processes that modify AT to vary spatiotemporally. Finally, we consider how the strength of each process as a CO2 source or sink may change in a warmer, higher-CO2 future ocean.

Description: The GEOTRACES Intermediate Data Product 2017 (IDP2017) is the second publicly available data product of the international GEOTRACES programme, and contains data measured and quality controlled before the end of 2016. The IDP2017 includes data from the Atlantic, Pacific, Arctic, Southern and Indian oceans, with about twice the data volume of the previous IDP2014. For the first time, the IDP2017 contains data for a large suite of biogeochemical parameters as well as aerosol and rain data characterising atmospheric trace element and isotope (TEI) sources. The TEI data in the IDP2017 are quality controlled by careful assessment of intercalibration results and multi-laboratory data comparisons at crossover stations. The IDP2017 consists of two parts: (1) a compilation of digital data for more than 450 TEIs as well as standard hydrographic parameters, and (2) the eGEOTRACES Electronic Atlas providing an on-line atlas that includes more than 590 section plots and 130 animated 3D scenes. The digital data are provided in several formats, including ASCII, Excel spreadsheet, netCDF, and Ocean Data View collection. Users can download the full data packages or make their own custom selections with a new on-line data extraction service. In addition to the actual data values, the IDP2017 also contains data quality flags and 1-σ data error values where available. Quality flags and error values are useful for data filtering and for statistical analysis. Metadata about data originators, analytical methods and original publications related to the data are linked in an easily accessible way. The eGEOTRACES Electronic Atlas is the visual representation of the IDP2017 as section plots and rotating 3D scenes. The basin-wide 3D scenes combine data from many cruises and provide quick overviews of large-scale tracer distributions. These 3D scenes provide geographical and bathymetric context that is crucial for the interpretation and assessment of tracer plumes near ocean margins or along ridges. The IDP2017 is the result of a truly international effort involving 326 researchers from 22 countries. This publication provides the critical reference for unpublished data, as well as for studies that make use of a large cross-section of data from the IDP2017.

Description: The ocean is a major sink for anthropogenic carbon dioxide (CO2), with the CO2 uptake causing changes to ocean chemistry. To monitor these changes and provide a chemical background for biological and biogeochemical studies, high quality partial pressure of CO2 (pCO2) sensors are required, with suitable accuracy and precision for ocean measurements. Optodes have the potential to measure in situ pCO2 without the need for wet chemicals or bulky gas equilibration chambers that are typically used in pCO2 systems. However, optodes are still in an early developmental stage compared to more established equilibrator-based pCO2 systems. In this study, we performed a laboratory-based characterization of a time-domain dual lifetime referencing pCO2 optode system. The pCO2 optode spot was illuminated with low intensity light (0.2 mA, 0.72 mW) to minimize spot photobleaching. The spot was calibrated using an experimental gas calibration rig prior to deployment, with a determined response time (τ63) of 50 s at 25°C. The pCO2 optode was deployed as an autonomous shipboard underway system across the high latitude North Atlantic Ocean with a resolution of ca.10 measurements per hour. The optode data was validated with a secondary shipboard equilibrator-based infrared pCO2 instrument, and pCO2 calculated from discrete samples of dissolved inorganic carbon and total alkalinity. Further verification of the pCO2 optode data was achieved using complimentary variables such as nutrients and dissolved oxygen. The shipboard precision of the pCO2 sensor was 9.5 μatm determined both from repeat measurements of certified reference materials and from the standard deviation of seawater measurements while on station. Finally, the optode deployment data was used to evaluate the physical and biogeochemical controls on pCO2.

Description: Accumulation of anthropogenic CO2 is significantly altering ocean chemistry. A range of biological impacts resulting from this oceanic CO2 accumulation are emerging, however the mechanisms responsible for observed differential susceptibility between organisms and across environmental settings remain obscure. A primary consequence of increased oceanic CO2 uptake is a decrease in the carbonate system buffer capacity, which characterises the system's chemical resilience to changes in CO2, generating the potential for enhanced variability in pCO2 and the concentration of carbonate [CO32‐], bicarbonate [HCO3‐] and protons [H+] in the future ocean. We conducted a meta‐analysis of 17 shipboard manipulation experiments performed across three distinct geographical regions that encompassed a wide range of environmental conditions from European temperate seas to Arctic and Southern oceans. These data demonstrated a correlation between the magnitude of natural phytoplankton community biological responses to short‐term CO2 changes and variability in the local buffer capacity across ocean basin scales. Specifically, short‐term suppression of small phytoplankton (〈10 μm) net growth rates were consistently observed under enhanced pCO2 within experiments performed in regions with higher ambient buffer capacity. The results further highlight the relevance of phytoplankton cell size for the impacts of enhanced pCO2 in both the modern and future ocean. Specifically, cell‐size related acclimation and adaptation to regional environmental variability, as characterised by buffer capacity, likely influences interactions between primary producers and carbonate chemistry over a range of spatio‐temporal scales.

Description: Polar oceans are particularly vulnerable to ocean acidification due to their low temperatures and reduced buffering capacity, and are expected to experience extensive low pH conditions and reduced carbonate mineral saturations states (Ω) in the near future. However, the impact of anthropogenic CO2 on pH and Ω will vary regionally between and across the Arctic and Southern Oceans. Here we investigate the carbonate chemistry in the Atlantic sector of two polar oceans, the Nordic Seas and Barents Sea in the Arctic Ocean, and the Scotia and Weddell Seas in the Southern Ocean, to determine the physical and biogeochemical processes that control surface pH and Ω. High-resolution observations showed large gradients in surface pH (0.10 to 0.30) and aragonite saturation state (Ωar) (0.2 to 1.0) over small spatial scales, and these were particularly strong in sea-ice covered areas (up to 0.45 in pH and 2.0 in Ωar). In the Arctic, sea-ice melt facilitated bloom initiation in light-limited and iron replete (dFe〉0.2 nM) regions, such as the Fram Strait, resulting in high pH (8.45) and Ωar (3.0) along the sea-ice edge. In contrast, accumulation of dissolved inorganic carbon derived from organic carbon mineralisation under the ice resulted in low pH (8.05) and Ωar (1.1) in areas where thick ice persisted. In the Southern Ocean, sea-ice retreat resulted in bloom formation only where terrestrial inputs supplied sufficient iron (dFe〉0.2 nM), such as in the vicinity of the South Sandwich Islands where enhanced pH (8.3) and Ωar (2.3) were primarily due to biological production. In contrast, in the adjacent Weddell Sea, weak biological uptake of CO2 due to low iron concentrations (dFe〈0.2 nM) resulted in low pH (8.1) and Ωar (1.6). The large spatial variability in both polar oceans highlights the need for spatially resolved surface data of carbonate chemistry variables but also nutrients (including iron) in order to accurately elucidate the large gradients experienced by marine organisms and to understand their response to increased CO2 in the future.

Description: Marine carbonate chemistry measurements have been carried out annually since 2009 during UK research cruises along the Extended Ellett Line (EEL), a hydrographic transect in the northeast Atlantic Ocean. The EEL intersects several water masses that are key to the global thermohaline circulation, and therefore the cruises sample a region in which it is critical to monitor secular physical and biogeochemical changes. We have combined results from these EEL cruises with existing quality-controlled observational data syntheses to produce a hydrographic time series for the EEL from 1981 to 2013. This reveals multidecadal increases in dissolved inorganic carbon (DIC) throughout the water column, with a near-surface maximum rate of 1.800.45 mu molkg(-1)yr(-1). Anthropogenic CO2 accumulation was assessed, using simultaneous changes in apparent oxygen utilization (AOU) and total alkalinity (TA) as proxies for the biogeochemical processes that influence DIC. The stable carbon isotope composition of DIC (C-13(DIC)) was also determined and used as an independent test of our method. We calculated a volume-integrated anthropogenic CO2 accumulation rate of 2.80.4mgCm(-3)yr(-1) along the EEL, which is about double the global mean. The anthropogenic CO2 component accounts for only 316% of the total DIC increase. The remainder is derived from increased organic matter remineralization, which we attribute to the lateral redistribution of water masses that accompanies subpolar gyre contraction. Output from a general circulation ecosystem model demonstrates that spatiotemporal heterogeneity in the observations has not significantly biased our multidecadal rate of change calculations and indicates that the EEL observations have been tracking distal changes in the surrounding North Atlantic and Nordic Seas.

Description: The stable carbon isotope composition of dissolved inorganic carbon (δ13C-DIC) can be used to quantify fluxes within the carbon system. For example, knowing the δ13C signature of the inorganic carbon pool can help in describing the amount of anthropogenic carbon in the water column. The measurements can also be used for evaluating modeled carbon fluxes, for making basin-wide estimates of anthropogenic carbon, and for studying seasonal and interannual variability or decadal trends in interior ocean biogeochemistry. For all these purposes, it is not only important to have a sufficient amount of data, but these data must also be internally consistent and of high quality. In this study, we present a δ13C-DIC dataset for the North Atlantic which has undergone secondary quality control. The data originate from oceanographic research cruises between 1981 and 2014. During a primary quality control step based on simple range tests, obviously bad data were flagged. In a second quality control step, biases between measurements from different cruises were quantified through a crossover analysis using nearby data of the respective cruises, and values of biased cruises were adjusted in the data product. The crossover analysis was possible for 24 of the 32 cruises in our dataset, and adjustments were applied to 11 cruises. The internal accuracy of this dataset is 0.017 ‰.

Description: The stable carbon isotope composition of dissolved inorganic carbon (δ13CDIC) in seawater was measured in samples collected during June—July 2014 in the subpolar North Atlantic. Sample collection was carried out on the RRS James Clark Ross cruise JR302, part of the "Radiatively Active Gases from the North Atlantic Region and Climate Change" (RAGNARoCC) research programme. The observed δ13CDIC values for cruise JR302 fall in a range from 0.07 ‰ to +1.95 ‰, relative to the Vienna Peedee Belemnite standard. From duplicate samples collected during the cruise, the 1σ precision for the 341 results is 0.08 ‰, which is similar to our previous work and other studies of this kind. We also performed a cross-over analysis using nearby historical δ13CDIC data, which indicated that there were no significant systematic offsets between our measurements and previously published results. We also included seawater reference material (RM) produced by A. G. Dickson (Scripps Institution of Oceanography, USA) in every batch of analysis, enabling us to improve upon the calibration and quality-control procedures from a previous study. The δ13CDIC is consistent within each RM batch, although its value is not certified. We report δ13CDIC values of 1.15 ± 0.03 ‰ and 1.27 ± 0.05 ‰ for batches 141 and 144 respectively. Our JR302 δ13CDIC data can be used – along with measurements of other biogeochemical variables – to constrain the processes that control DIC in the interior ocean, in particular the oceanic uptake of anthropogenic carbon dioxide and the biological carbon pump. Our δ13CDIC results are available from the British Oceanographic Data Centre – doi:10.5285/22235f1a-b7f3-687f-e053-6c86abc0c8a6.

Description: The Surface Ocean CO2 Atlas (SOCAT) is a synthesis of quality-controlled fCO2 (fugacity of carbon dioxide) values for the global surface oceans and coastal seas with regular updates. Version 3 of SOCAT has 14.7 million fCO2 values from 3646 data sets covering the years 1957 to 2014. This latest version has an additional 4.6 million fCO2 values relative to version 2 and extends the record from 2011 to 2014. Version 3 also significantly increases the data availability for 2005 to 2013. SOCAT has an average of approximately 1.2 million surface water fCO2 values per year for the years 2006 to 2012. Quality and documentation of the data has improved. A new feature is the data set quality control (QC) flag of E for data from alternative sensors and platforms. The accuracy of surface water fCO2 has been defined for all data set QC flags. Automated range checking has been carried out for all data sets during their upload into SOCAT. The upgrade of the interactive Data Set Viewer (previously known as the Cruise Data Viewer) allows better interrogation of the SOCAT data collection and rapid creation of high-quality figures for scientific presentations. Automated data upload has been launched for version 4 and will enable more frequent SOCAT releases in the future. High-profile scientific applications of SOCAT include quantification of the ocean sink for atmospheric carbon dioxide and its long-term variation, detection of ocean acidification, as well as evaluation of coupled-climate and ocean-only biogeochemical models. Users of SOCAT data products are urged to acknowledge the contribution of data providers, as stated in the SOCAT Fair Data Use Statement. This ESSD (Earth System Science Data) "living data" publication documents the methods and data sets used for the assembly of this new version of the SOCAT data collection and compares these with those used for earlier versions of the data collection (Pfeil et al., 2013; Sabine et al., 2013; Bakker et al., 2014). Individual data set files, included in the synthesis product, can be downloaded here: doi:10.1594/PANGAEA.849770. The gridded products are available here: doi:10.3334/CDIAC/OTG.SOCAT_V3_GRID.

Description: 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 sulphur 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 onboard the RV Knorr in the Indian Ocean in 1994–1995 which are now adjusted using 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, 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.