Anthropogenic carbon pathways towards the North Atlantic interior revealed by Argo-O2, neural networks and back-calculations.

The subpolar North Atlantic (SPNA) is a region of high anthropogenic CO2 (Cant) storage per unit area. Although the average Cant distribution is well documented in this region, the Cant pathways towards the ocean interior remain largely unresolved. We used observations from three Argo-O2 floats spanning 2013-2018 within the SPNA, combined with existing neural networks and back-calculations, to determine the Cant evolution along the float pathways from a quasi-lagrangian perspective. Our results show that Cant follows a stepwise deepening along its way through the SPNA. The upper subtropical waters have a stratified Cant distribution that homogenizes within the winter mixed layer by Subpolar Mode Water formation in the Iceland Basin. In the Irminger and Labrador Basins, the high-Cant footprint (> 55 µmol kg-1) is mixed down to 1400 and 1800 dbar, respectively, by deep winter convection. As a result, the maximum Cant concentration is diluted (<45 µmol kg-1). Our study highlights the role of water mass transformation as a first-order mechanism for Cant penetration into the ocean. It also demonstrates the potential of Argo-O2 observations, combined with existing methods, to obtain reliable Cant estimates, opening ways to study the oceanic Cant content at high spatio-temporal resolution.

Nudibranch predation boosts sponge silicon cycling.

Diatoms play a key role in the marine silica cycle, but recent studies have shown that sponges can also have an important effect on this dynamic. They accumulate large stocks of biogenic silica within their bodies over long periods, which are thought to vary little on an intra-annual scale. The observation of an abrupt decline in sponge biomass in parallel with large increases in abundance of a spongivorous nudibranch (Doris verrucosa) led us to conduct a year-long study on the effect of nudibranch predation on the silicon budget of a sponge (Hymeniacidon perlevis) population. After 5 months of predation, the abundance of sponge individuals did not change but their biomass decreased by 95%, of which 48% was explained by nudibranch predation. About 97% of sponge spicules ingested by nudibranchs while feeding was excreted, most of them unbroken, implying a high rate of sponge silica deposition in the surrounding sediments. After predation, sponges partially recovered their biomass stocks within 7 months. This involved a rapid growth rate and large assimilation of dissolved silicon. Surprisingly, the highest rates of silicon absorption occurred when dissolved silicon concentration in seawater was minimal (< 1.5 µM). These findings suggest that the annual sponge predation-recovery cycle triggers unprecedented intra-annual changes in sponge silicon stocks and boosts the cycling of this nutrient. They also highlight the need for intra-annual data collection to understand the dynamics and resilience of sponge ecosystem functioning.

Spatial and temporal variation of methane emissions in the coastal Balearic Sea, Western Mediterranean.

Methane (CH4) gas is the most important GHG after carbon dioxide, with open ocean areas acting as discreet CH4 sources and coastal regions as intense but variable CH4 sources to the atmosphere. Here, we report CH4 concentrations and air-sea fluxes in the coastal area of the Balearic Islands Archipelago (Western Mediterranean Basin). CH4 levels and related biogeochemical variables were measured in three coastal sampling sites between 2018 and 2021, with two located close to the densely populated island of Mallorca and one in a pristine area in the Cabrera Archipelago National Park. CH4 concentrations in seawater during the study period ranged from 2.7 to 10.9 nM, without significant differences between the sampling sites. Averaged estimated CH4 fluxes during the sampling period for the three stations oscillated between 0.2 and 9.7 µmol m-2 d-1 according to a seasonal pattern and in general all sites behaved as weak CH4 sources throughout the sampling period.

pH trends and seasonal cycle in the coastal Balearic Sea reconstructed through machine learning.

The decreasing seawater pH trend associated with increasing atmospheric carbon dioxide levels is an issue of concern due to possible negative consequences for marine organisms, especially calcifiers. Globally, coastal areas represent important transitional land-ocean zones with complex interactions between biological, physical and chemical processes. Here, we evaluated the pH variability at two sites in the coastal area of the Balearic Sea (Western Mediterranean). High resolution pH data along with temperature, salinity, and also dissolved oxygen were obtained with autonomous sensors from 2018 to 2021 in order to determine the temporal pH variability and the principal drivers involved. By using environmental datasets of temperature, salinity and dissolved oxygen, Recurrent Neural Networks were trained to predict pH and fill data gaps. Longer environmental time series (2012-2021) were used to obtain the pH trend using reconstructed data. The best predictions show a rate of [Formula: see text] pH units year[Formula: see text], which is in good agreement with other observations of pH rates in coastal areas. The methodology presented here opens the possibility to obtain pH trends when only limited pH observations are available, if other variables are accessible. Potentially, this could be a way to reliably fill the unavoidable gaps present in time series data provided by sensors.

Contrasting drivers and trends of ocean acidification in the subarctic Atlantic.

The processes of warming, anthropogenic CO2 (Canth) accumulation, decreasing pHT (increasing [H+]T; concentration in total scale) and calcium carbonate saturation in the subarctic zone of the North Atlantic are unequivocal in the time-series measurements of the Iceland (IS-TS, 1985-2003) and Irminger Sea (IRM-TS, 1983-2013) stations. Both stations show high rates of Canth accumulation with different rates of warming, salinification and stratification linked to regional circulation and dynamics. At the IS-TS, advected and stratified waters of Arctic origin drive a strong increase in [H+]T, in the surface layer, which is nearly halved in the deep layer (44.7 ± 3.6 and 25.5 ± 1.0 pmol kg-1 yr-1, respectively). In contrast, the weak stratification at the IRM-TS allows warming, salinification and Canth uptake to reach the deep layer. The acidification trends are even stronger in the deep layer than in the surface layer (44.2 ± 1.0 pmol kg-1 yr-1 and 32.6 ± 3.4 pmol kg-1 yr-1 of [H+]T, respectively). The driver analysis detects that warming contributes up to 50% to the increase in [H+]T at the IRM-TS but has a small positive effect on calcium carbonate saturation. The Canth increase is the main driver of the observed acidification, but it is partially dampened by the northward advection of water with a relatively low natural CO2 content.

Anthropogenic CO2 and ocean acidification in Argentine Basin Water Masses over almost five decades of observations.

The chemical conditions of the Argentine Basin (western South Atlantic Ocean) water masses are evaluated with measurements from eleven hydrographic cruises to detect and quantify anthropogenic and natural stressors in the ocean carbon system. The database covers almost half-century (1972-2019), a time-span where the mean annual atmospheric carbon dioxide concentration (CO2atm) increased from 325 to 408 ppm of volume (ppm). This increase of atmospheric CO2 (83 ppm, the 64% of the total anthropogenic signal in the atmosphere) leads to an increase in anthropogenic carbon (Cant) across all the water column and the consequent ocean acidification: a decrease in excess carbonate that is unequivocal in the upper (South Atlantic Central Water, SACW) and intermediate water masses (Sub Antarctic Mode Water, SAMW and Antarctic Intermediate Water, AAIW). For each additional ppm in CO2atm the water masses SACW, SAMW and AAIW lose excess carbonate at a rate of 0.39 ± 0.04, 0.47 ± 0.05 and 0.23 ± 0.03 µmol·kg-1·ppm-1 respectively. Modal and intermediate water masses in the Argentine Basin are very sensitive to carbon increases due low buffering capacity. The large rate of AAIW acidification is the synergic effect of carbon uptake combined with deoxygenation and increased remineralization of organic matter. If CO2 emissions follows the path of business-as-usual emissions (SSP 5.85), SACW would become undersaturated with respect to aragonite at the end of the century. The undersaturation in AAIW is virtually unavoidable.

The Mediterranean mussel Mytilus galloprovincialis: responses to climate change scenarios as a function of the original habitat.

The impact of simulated seawater acidification and warming conditions on specimens of the mussel Mytilus galloprovincialis locally adapted to very distinct, widely separated sites in the Mediterranean Sea (Tunisia) and Atlantic Sea (Galicia, NW Spain) was evaluated in relation to key behavioural and eco-physiological parameters. Over the 2-month exposure to the experimental conditions, mussels were fed optimally to ensure that there are no synergistic interactions between climate change drivers and energetic status of the individuals. In general, regardless of origin (Atlantic or Mediterranean), the mussels were rather resilient to acidification for most of the parameters considered and they were able to grow in strongly acidified seawater through an increased feeding activity. However, shell strength decreased (40%) consistently in both mussel populations held in moderately and highly acidified seawater. The observed reduction in shell strength was not explained by slight alterations in organic matter, shell thickness or aragonite:calcite ratio. The combined effects of high acidification and warming on the key response of byssus strength caused a strong decline in mussel performance, although only in Galician mussels, in which the valve opening time decreased sharply as well as condition index (soft tissue state) and shell growth. By contrast, the observed negative effect of highly acidified scenario on the strength of Tunisian mussel shells was (partly but not totally) counterbalanced by the higher seawater temperature. Eco-physiological and behavioural interactions in mussels in relation to climate change are complex, and future scenarios for the ecology of the species and also the feasibility of cultivating them in Atlantic and Mediterranean zones are discussed.

Behavioural responses to predators in Mediterranean mussels (Mytilus galloprovincialis) are unaffected by elevated pCO2.

Ocean acidification is expected to affect marine organisms in the near future. Furthermore, abrupt short-term fluctuations in seawater pCO2 characteristic of near-shore coastal regions and high-density aquaculture sites currently have the potential to influence organismal and community functioning by altering animal behaviour. While anti-predator responses in fishes exposed to elevated pCO2 are well documented, such responses in benthic marine invertebrates are poorly studied. We used high frequency, non-invasive biosensors to test whether or not short term (3-week) exposure to elevated pCO2 could impact behavioural responses to the threat of predation in adult Mediterranean mussels from Galicia on the northwestern coast of Spain. Predator alarm cues (crushed conspecifics) resulted in a prolonged (1 h) reduction in the degree of valve opening (-20%) but had no clear effect on overall valve movement activity, while elevated pCO2 did not affect either response. Our results add to the increasing body of evidence suggesting that the effects of end-of-century pCO2 levels on marine animal behaviour are likely weak. Nonetheless, longer-term exposures spanning multiple generations are needed to better understand how ocean acidification might impact behavioural responses to predation in marine bivalves.

The Northeast Atlantic is running out of excess carbonate in the horizon of cold-water corals communities.

The oceanic uptake of atmospheric carbon dioxide (CO2) emitted by human activities alters the seawater carbonate system. Here, the chemical status of the Northeast Atlantic is examined by means of a high-quality database of carbon variables based on the GO-SHIP A25 section (1997-2018). The increase of atmospheric CO2 leads to an increase in ocean anthropogenic carbon (Cant) and a decrease in carbonate that is unequivocal in the upper and mid-layers (0-2,500 m depth). In the mid-layer, the carbonate content in the Northeast Atlantic is maintained by the interplay between the northward spreading of recently conveyed Mediterranean Water with excess of carbonate and the arrival of subpolar-origin waters close to carbonate undersaturation. In this study we show a progression to undersaturation with respect to aragonite that could compromise the conservation of the habitats and ecosystem services developed by benthic marine calcifiers inhabiting that depth-range, such as the cold-water corals (CWC) communities. For each additional ppm in atmospheric pCO2 the waters surrounding CWC communities lose carbonate at a rate of - 0.17 ± 0.02 µmol kg-1 ppm-1. The accomplishment of global climate policies to limit global warming below 1.5-2 â„ƒ will avoid the exhaustion of excess carbonate in the Northeast Atlantic.

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 needed.

Decadal acidification in Atlantic and Mediterranean water masses exchanging at the Strait of Gibraltar.

Seawater pH is undergoing a decreasing trend due to the absorption of atmospheric CO2, a phenomenon known as ocean acidification (OA). Biogeochemical processes occurring naturally in the ocean also change pH and hence, for an accurate assessment of OA, the contribution of the natural component to the total pH variation must be quantified. In this work, we used 11 years (2005-2015) of biogeochemical measurements collected at the Strait of Gibraltar to estimate decadal trends of pH in two major Mediterranean water masses, the Western Mediterranean Deep Water (WMDW) and the Levantine Intermediate Water (LIW) and assess the magnitude of natural and anthropogenic components on the total pH change. The assessment was also performed in the North Atlantic Central Water (NACW) feeding the Mediterranean Sea. Our analysis revealed a significant human impact on all water masses in terms of accumulation of anthropogenic CO2. However, the decadal pH decline found in the WMDW and the NACW was markedly affected by natural processes, which accounted for by nearly 60% and 40% of the total pH decrease, respectively. The LIW did not exhibit a significant pH temporal trend although data indicated natural and anthropogenic perturbations on its biogeochemical signatures.

The oceanic sink for anthropogenic CO2 from 1994 to 2007.

We quantify the oceanic sink for anthropogenic carbon dioxide (CO2) over the period 1994 to 2007 by using observations from the global repeat hydrography program and contrasting them to observations from the 1990s. Using a linear regression-based method, we find a global increase in the anthropogenic CO2 inventory of 34 ± 4 petagrams of carbon (Pg C) between 1994 and 2007. This is equivalent to an average uptake rate of 2.6 ± 0.3 Pg C year-1 and represents 31 ± 4% of the global anthropogenic CO2 emissions over this period. Although this global ocean sink estimate is consistent with the expectation of the ocean uptake having increased in proportion to the rise in atmospheric CO2, substantial regional differences in storage rate are found, likely owing to climate variability-driven changes in ocean circulation.

Meridional overturning circulation conveys fast acidification to the deep Atlantic Ocean.

Since the Industrial Revolution, the North Atlantic Ocean has been accumulating anthropogenic carbon dioxide (CO2) and experiencing ocean acidification, that is, an increase in the concentration of hydrogen ions (a reduction in pH) and a reduction in the concentration of carbonate ions. The latter causes the 'aragonite saturation horizon'-below which waters are undersaturated with respect to a particular calcium carbonate, aragonite-to move to shallower depths (to shoal), exposing corals to corrosive waters. Here we use a database analysis to show that the present rate of supply of acidified waters to the deep Atlantic could cause the aragonite saturation horizon to shoal by 1,000-1,700 metres in the subpolar North Atlantic within the next three decades. We find that, during 1991-2016, a decrease in the concentration of carbonate ions in the Irminger Sea caused the aragonite saturation horizon to shoal by about 10-15 metres per year, and the volume of aragonite-saturated waters to reduce concomitantly. Our determination of the transport of the excess of carbonate over aragonite saturation (xc[CO32-])-an indicator of the availability of aragonite to organisms-by the Atlantic meridional overturning circulation shows that the present-day transport of carbonate ions towards the deep ocean is about 44 per cent lower than it was in preindustrial times. We infer that a doubling of atmospheric anthropogenic CO2 levels-which could occur within three decades according to a 'business-as-usual scenario' for climate change-could reduce the transport of xc[CO32-] by 64-79 per cent of that in preindustrial times, which could severely endanger cold-water coral habitats. The Atlantic meridional overturning circulation would also export this acidified deep water southwards, spreading corrosive waters to the world ocean.

Dissolved Organic Carbon in the North Atlantic Meridional Overturning Circulation.

The quantitative role of the Atlantic Meridional Overturning Circulation (AMOC) in dissolved organic carbon (DOC) export is evaluated by combining DOC measurements with observed water mass transports. In the eastern subpolar North Atlantic, both upper and lower limbs of the AMOC transport high-DOC waters. Deep water formation that connects the two limbs of the AMOC results in a high downward export of non-refractory DOC (197 Tg-C·yr(-1)). Subsequent remineralization in the lower limb of the AMOC, between subpolar and subtropical latitudes, consumes 72% of the DOC exported by the whole Atlantic Ocean. The contribution of DOC to the carbon sequestration in the North Atlantic Ocean (62 Tg-C·yr(-1)) is considerable and represents almost a third of the atmospheric CO2 uptake in the region.

Trends of pH decrease in the Mediterranean Sea through high frequency observational data: indication of ocean acidification in the basin.

A significant fraction of anthropogenic carbon dioxide (CO2) released to the atmosphere is absorbed by the oceans, leading to a range of chemical changes and causing ocean acidification (OA). Assessing the impact of OA on marine ecosystems requires the accurate detection of the rate of seawater pH change. This work reports the results of nearly 3 years of continuous pH measurements in the Mediterranean Sea at the Strait of Gibraltar GIFT time series station. We document a remarkable decreasing annual trend of -0.0044 ± 0.00006 in the Mediterranean pH, which can be interpreted as an indicator of acidification in the basin based on high frequency records. Modeling pH data of the Mediterranean outflow allowed to discriminate between the pH values of its two main constituent water masses, the Levantine Intermediate Water (LIW) and the Western Mediterranean Deep Water (WMDW). Both water masses also exhibited a decline in pH with time, particularly the WMDW, which can be related to their different biogeochemical nature and processes occurring during transit time from formation sites to the Strait of Gibraltar.

Spectrophotometric Measurements of the Carbonate Ion Concentration: Aragonite Saturation States in the Mediterranean Sea and Atlantic Ocean.

Measurements of ocean pH, alkalinity, and carbonate ion concentrations ([CO3(2-)]) during three cruises in the Atlantic Ocean and one in the Mediterranean Sea were used to assess the reliability of the recent spectrophotometric [CO3(2-)] methodology and to determine aragonite saturation states. Measurements of [CO3(2-)] along the Atlantic Ocean showed high consistency with the [CO3(2-)] values calculated from pH and alkalinity, with negligible biases (0.4 ± 3.4 µmol·kg(-1)). In the warm, salty, high alkalinity and high pH Mediterranean waters, the spectrophotometric [CO3(2-)] methodology underestimates the measured [CO3(2-)] (4.0 ± 5.0 µmol·kg(-1)), with anomalies positively correlated to salinity. These waters also exhibited high in situ [CO3(2-)] compared to the expected aragonite saturation. The very high buffering capacity allows the Mediterranean Sea waters to remain over the saturation level of aragonite for long periods of time. Conversely, the relatively thick layer of undersaturated waters between 500 and 1000 m depths in the Tropical Atlantic is expected to progress to even more negative undersaturation values. Moreover, the northern North Atlantic presents [CO3(2-)] slightly above the level of aragonite saturation, and the expected anthropogenic acidification could result in reductions of the aragonite saturation levels during future decades, acting as a stressor for the large population of cold-water-coral communities.

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 (∆pH) 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.