The GEOVIDE cruise in May-June 2014 reveals an intense Meridional Overturning Circulation over a cold and fresh subpolar North Atlantic

The GEOVIDE cruise was carried out in the subpolar North Atlantic (SPNA) along the OVIDE section and across the Labrador Sea in May-June 2014. It was planned to clarify the distribution of the trace elements and their isotopes in the SPNA as part of the GEOTRACES international program. This paper focuses on the state of the circulation and distribution of thermohaline properties during the cruise. In terms of circulation, the comparison with the 2002-2012 mean state shows a more intense Irminger Current and also a weaker North Atlantic Current, with a transfer of volume transport from its northern to its central branch. However, those anomalies are compatible with the variability already observed along the OVIDE section in the 2000s. In terms of properties, the surface waters of the eastern SPNA were much colder and fresher than the averages over 2002-2012. In spite of negative temperature anomalies in the surface waters, the heat transport across the OVIDE section estimated at 0.56±0.06PW was the largest measured since 2002. This relatively large value is related to the relatively strong Meridional Overturning Circulation measured across the OVIDE section during GEOVIDE (18.7±3.0Sv). By analyzing the air-sea heat and freshwater fluxes over the eastern SPNA in relation to the heat and freshwater content changes observed during 2013 and 2014, we concluded that on a short timescale these changes were mainly driven by air-sea heat and freshwater fluxes rather than by ocean circulation

Ocean acidification in the subpolar North Atlantic:Rates and mechanisms controlling pH changes

Repeated hydrographic sections provide critically needed data on and understanding of changes in basin-wide ocean CO2 chemistry over multi-decadal timescales. Here, high-quality measurements collected at twelve cruises carried out along the same track between 1991 and 2015 have been used to determine long-term changes in ocean CO2 chemistry and ocean acidification in the Irminger and Iceland basins of the North Atlantic Ocean. Trends were determined for each of the main water masses present and are discussed in the context of the basin-wide circulation. The pH has decreased in all water masses of the Irminger and Iceland basins over the past 25 years with the greatest changes in surface and intermediate waters (between -0.0010 ± 0.0001 and -0.0018 ± 0.0001 pH units yr-1). In order to disentangle the drivers of the pH changes, we decomposed the trends into their principal drivers: changes in temperature, salinity, total alkalinity (AT) and total dissolved inorganic carbon (both its natural and anthropogenic components). The increase in anthropogenic CO2 (Cant) was identified as the main agent of the pH decline, partially offset by AT increases. The acidification of intermediate waters caused by Cant uptake has been reinforced by the aging of the water masses over the period of our analysis. The pH decrease of the deep overflow waters in the Irminger basin was similar to that observed in the upper ocean and was mainly linked to the Cant increase, thus reflecting the recent contact of these deep waters with the atmosphere

Cold-water corals in the Subpolar North Atlantic Ocean exposed to aragonite undersaturation if the 2 °C global warming target is not met

The net uptake of carbon dioxide (CO2) from the atmosphere is changing the ocean's chemical state. Such changes, commonly known as ocean acidification, include a reduction in pH and the carbonate ion concentration ([CO32−]), which in turn lowers oceanic saturation states (Ω) for calcium carbonate (CaCO3) minerals. The Ω values for aragonite (Ωaragonite; one of the main CaCO3 minerals formed by marine calcifying organisms) influence the calcification rate and geographic distribution of cold-water corals (CWCs), important for biodiversity. Here, high-quality measurements, collected on thirteen cruises along the same track during 1991–2018, are used to determine the long-term changes in Ω aragonite in the Irminger and Iceland Basins of the North Atlantic Ocean, providing the first trends of Ωaragonite in the deep waters of these basins. The entire water column of both basins showed significant negative Ωaragonite trends between −0.0014 ± 0.0002 and −0.0052 ± 0.0007 per year. The decrease in Ω aragonite in the intermediate waters, where nearly half of the CWC reefs of the study region are located, caused the Ωaragonite isolines to rapidly migrate upwards at a rate between 6 and 34 m per year. The main driver of the decline in Ωaragonite in the Irminger and Iceland Basins was the increase in anthropogenic CO2. But this was partially offset by increases in salinity (in Subpolar Mode Water), enhanced ventilation (in upper Labrador Sea Water), and increases in alkalinity (in classical Labrador Sea Water, cLSW; and overflow waters). We also found that water mass aging reinforced the Ωaragonite decrease in cLSW. Based on these Ωaragonite trends over the last three decades, we project that the entire water column of the Irminger and Iceland Basins will likely be undersaturated for aragonite when in equilibrium with an atmospheric mole fraction of CO2 (xCO2) of ~880 ppmv, corresponding to climate model projections for the end of the century based on the highest CO2 emission scenarios. However, intermediate waters will likely be aragonite undersaturated when in equilibrium with an atmospheric xCO2 exceeding ~630 ppmv, an xCO2 level slightly above that corresponding to 2°C global warming, thus exposing CWCs inhabiting the intermediate waters to undersaturation for aragonite

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.4,84

Decadal acidification in the water masses of the Atlantic Ocean

Global ocean acidification is caused primarily by the ocean's uptake of CO2 as a consequence of increasing atmospheric CO2 levels. We present observations of the oceanic decrease in pH at the basin scale (50°S-36°N) for the Atlantic Ocean over two decades (1993-2013). Changes in pH associated with the uptake of anthropogenic CO2 (ΔpHCant) and with variations caused by biological activity and ocean circulation (ΔpHNat) are evaluated for different water masses. Output from an Institut Pierre Simon Laplace climate model is used to place the results into a longer-term perspective and to elucidate the mechanisms responsible for pH change. The largest decreases in pH (ΔpH) were observed in central, mode, and intermediate waters, with a maximum ΔpH value in South Atlantic Central Waters of -0.042 ± 0.003. The ΔpH trended toward zero in deep and bottom waters. Observations and model results show that pH changes generally are dominated by the anthropogenic component, which accounts for rates between -0.0015 and -0.0020/y in the central waters. The anthropogenic and natural components are of the same order of magnitude and reinforce one another in mode and intermediate waters over the time period. Large negative ΔpHNat values observed in mode and intermediate waters are driven primarily by changes in CO2 content and are consistent with (i) a poleward shift of the formation region during the positive phase of the Southern Annular Mode in the South Atlantic and (ii) an increase in the rate of the water mass formation in the North Atlantic

Detection and quantification of CO2 seepage in seawater using the stoichiometric Cseep method:Results from a recent subsea CO2 release experiment in the North Sea

Carbon Capture and Storage (CCS) is a potential significant mitigation strategy to combat climate change and ocean acidification. The technology is well understood but its current implementation must be scaled up nearly by a hundredfold to become an effective tool that helps meet mitigation targets. Regulations require monitoring and verification at storage sites, and reliable monitoring strategies for detection and quantification of seepage of the stored carbon need to be developed. The Cseep method was developed for reliable determination of CO2 seepage signal in seawater by estimating and filtering out natural variations in dissolved inorganic carbon (C). In this work, we analysed data from the first-ever subsea CO2 release experiment performed in the north-western North Sea by the EU STEMM−CCS project. We successfully demonstrated the ability of the Cseep method to (i) predict natural C variations around the Goldeneye site over seasonal to interannual time scales; (ii) establish a process-based baseline C concentration with minimal variability; (iii) determine CO2 seepage detection threshold (DT) to reliably differentiate released−CO2 signal from natural variability and quantify released−CO2 dissolved in the sampled seawater. DT values were around 20 % of the natural C variations indicating high sensitivity of the method. Moreover, with the availability of DT value, the identification of released−CO2 required no pre-knowledge of seepage occurrence, but we used additional available information to assess the confidence of the results. Overall, the Cseep method features high sensitivity, automation suitability, and represents a powerful future monitoring tool both for large and confined marine areas

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

North Atlantic CO2 sink variability revealed by the Go-Ship A25-OVIDE section

EGU General Assembly 2022, Vienna, Austria, 23–27 May 2022.-- This work is distributed under the Creative Commons Attribution 4.0 LicenseAbout 30% of the carbon dioxide derived from human activities (CANTH) has been absorbed by the ocean (DeVries, 2014; Gruber et al., 2019; Friedlingstein et al., 2021), with the North Atlantic (NA) being one of the largest CANTH sinks per unit area (Khatiwala et al., 2013; Sabine et al., 2004). In the NA, oceanic CANTH uptake strongly relies on the meridional overturning circulation and the associated regional winter deep convection. In fact, the formation and deep spreading of Labrador Sea Water stands as a critical CANTH gateway to intermediate and abyssal depths. The NA CANTH uptake has fluctuated over the years according to changes in the North Atlantic Oscillation. Biennial observation of the marine carbonate system along the Go-Ship A25-OVIDE section has allowed us assessing the decadal and interannual variability of the CANTH storage in the subpolarNA from 2002 to 2021. In this study, we investigate 1) the trend of CANTH and 2) the relationship between the CANTH saturation, the apparent oxygen utilization, and the ventilation of the water masses between the A25-OVIDE section and the Greenland-Iceland-Scotland sills during 2002-2021. We divided the A25-OVIDE section into three main basins (Irminger, Iceland, and Eastern NA). Our results show that the Irminger Basin presents a more homogenous CANTH profile and higher CANTH saturation values at depth than the other two basins, which is related to the pronounced convective activity in the Irminger Basin. In contrast, the Eastern NA Basin has higher CANTH values at the surface due to its higher surface temperature, but its deep water masses show the lowest CANTH values since they are the less ventilated in the section. Our analysis also reveals that, overall, the NA CANTH storage has increased during 2002-2021, but varied according to the ventilation changes. While the Eastern NA water masses experienced a relatively constant, although shallower, average ventilation, the Irminger and Iceland Basins underwent a less steady CANTH uptake pattern characterized by alternating periods of strong and weak CANTH storageN

Ventilation versus biology:What is the controlling mechanism of nitrous oxide distribution in the North Atlantic?

The extent to which water mass mixing and ocean ventilation contribute to nitrous oxide (N2O) distribution at the scale of oceanic basins is poorly constrained. We used novel N2O and chlorofluorocarbon measurements along with multiparameter water mass analysis to evaluate the impact of water mass mixing and Atlantic Meridional Overturning Circulation (AMOC) on N2O distribution along the Observatoire de la variabilité interannuelle et décennale en Atlantique Nord (OVIDE) section, extending from Portugal to Greenland. The biological N2O production has a stronger impact on the observed N2O concentrations in the water masses traveling northward in the upper limb of the AMOC than those in recently ventilated cold water masses in the lower limb, where N2O concentrations reflect the colder temperatures. The high N2O tongue, with concentrations as high as 16 nmol kg−1, propagates above the isopycnal surface delimiting the upper and lower AMOC limbs, which extends from the eastern North Atlantic Basin to the Iceland Basin and coincides with the maximum N2O production rates. Water mixing and basin-scale remineralization account for 72% of variation in the observed distribution of N2O. The mixing-corrected stoichiometric ratio N2O:O2 for the North Atlantic Basin of 0.06 nmol/μmol is in agreement with ratios of N2O:O2 for local N2O anomalies, suggesting than up to 28% of N2O production occurs in the temperate and subpolar Atlantic, an overlooked region for N2O cycling. Overall, our results highlight the importance of taking into account mixing, O2 undersaturation when water masses are formed and the increasing atmospheric N2O concentrations when parameterizing N2O:O2 and biological N2O production in the global oceans

FICARAM-15 Cruise Report 20th March – 22nd May 2013 on board BIO Hespérides by the Group FICARAM

54 páginas, 19 figuras, 3 anexosThe FICARAM-15 is the fifteenth repetition of a section conducted in 1994. This section is part of the international program GOSHIP (http://www.go-ship.org/CruisePlans.html) to develop a globally coordinated network of sustained hydrographic sections as part of the global ocean/climate observing system. The objective of the FICARAM-15 cruise is to investigate the temporal evolution of the anthropogenic carbon and evaluate the CO2 absorption capacity of the South Atlantic region, the Equatorial zone, and the subtropical region of Azores-Gibraltar in the North Atlantic. This cruise is supported by the CATARINA project funded by the Ministry of Economy and Competitiveness (CTM2010-17141) and is part of the European Union FP7 project CARBOCHANGE (http://carbochange.b.uib.no/). The objective of FICARAM-15 cruise is framed in the CATARINA project conducted by the tasks I.2.1 (air-sea CO2 exchange) I.3 (ventilation of water masses), I.4.1 (zonal variability of N2O and CH4), I.4.2 (anthropogenic carbon storage), I.4.4 (saturation horizon of calcium carbonate along the section) and I.5.4 (evolution of the acidification rates). Another component of the FICARAM-15 cruise aims to examine the biological and biogeochemical mechanisms that hinder total dissolved organic carbon (DOC) remineralisation in marine systems, taking a multidisciplinary perspective and applying many different approaches. This is the global objective of the Spanish project DOREMI (CTM2012-34294) that joins this FICARAM-15 cruise.During the FICARAM cruise the physical oceanography group was responsible for collecting the following data sets: CTD and XBT data; vessel-mounted ADCP and lowered ADCP; continuous thermosalinograph. Physical oceanographers participated in the cruise financed through Project “Tipping Corners in the Meridional Overturning Circulation” (TIC-MOC), CTM2011-28867. The FICARAM-15 cruise was organized in two phases with a common sampling. LEG 1: From Punta Arenas (Chile) to Recife (Brazil): 62 stations. Chief Scientist: Aida F. Ríos, PI of CATARINA project LEG 2: From Recife (Brazil) to Cartagena (Spain): 46 stations Chief Scientist: Celia Marrasé, PI of DOREMI project This report contains the sampling of all the variables at each station along the FICARAM section, as well as the analysis of the biogeochemical variables and the preliminary results. The principal investigator of the DOREMI project produced another report with the common sampling section, showing the analysis and results of the experiments on dissolved organic matter carried out on board.This cruise is supported by the CATARINA project funded by the Ministry of Economy and Competitiveness (CTM2010-17141) and is part of the European Union FP7 project CARBOCHANGE (http://carbochange.b.uib.no/)Peer reviewe