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The global ocean is a significant sink for anthropogenic carbon (Cant), absorbing roughly a third of human CO2 emitted over the industrial period. Robust estimates of the magnitude and variability of the storage and distribution of Cant in the ocean are therefore important for understanding the human impact on climate. In this synthesis we review observational and model-based estimates of the storage and transport of Cant in the ocean. We pay particular attention to the uncertainties and potential biases inherent in different inference schemes. On a global scale, three data-based estimates of the distribution and inventory of Cant are now available. While the inventories are found to agree within their uncertainty, there are considerable differences in the spatial distribution. We also present a review of the progress made in the application of inverse and data assimilation techniques which combine ocean interior estimates of Cant with numerical ocean circulation models. Such methods are especially useful for estimating the air–sea flux and interior transport of Cant, quantities that are otherwise difficult to observe directly. However, the results are found to be highly dependent on modeled circulation, with the spread due to different ocean models at least as large as that from the different observational methods used to estimate Cant. Our review also highlights the importance of repeat measurements of hydrographic and biogeochemical parameters to estimate the storage of Cant on decadal timescales in the presence of the variability in circulation that is neglected by other approaches. Data-based Cant estimates provide important constraints on forward ocean models, which exhibit both broad similarities and regional errors relative to the observational fields. A compilation of inventories of Cant gives us a \"best\" estimate of the global ocean inventory of anthropogenic carbon in 2010 of 155 ± 31 PgC (±20% uncertainty). This estimate includes a broad range of values, suggesting that a combination of approaches is necessary in order to achieve a robust quantification of the ocean sink of anthropogenic CO2.

The Mediterranean Sea is a semi-enclosed sea characterized by high salinities, temperatures and densities. The net evaporation exceeds the precipitation, driving an anti-estuarine circulation through the Strait of Gibraltar, contributing to very low nutrient concentrations. The Mediterranean Sea has an active overturning circulation, one shallow cell that communicates directly with the Atlantic Ocean, and two deep overturning cells, one in each of the two main basins. It is surrounded by populated areas and is thus sensitive to anthropogenic forcing. Several dramatic changes in the oceanographic and biogeochemical conditions have been observed during the past several decades, emphasizing the need to better monitor and understand the changing conditions and their drivers. During 2011 three oceanographic cruises were conducted in a coordinated fashion in order to produce baseline data of important physical and biogeochemical parameters that can be compared to historic data and be used as reference for future observational campaigns. In this article we provide information on the Mediterranean Sea oceanographic situation, and present a short review that will serve as background information for the special issue in Ocean Science on \"Physical, chemical and biological oceanography of the Mediterranean Sea\". An important contribution of this article is the set of figures showing the large-scale distributions of physical and chemical properties along the full length of the Mediterranean Sea.

Ocean observations are analysed in the framework of Collaborative Research Center 754 (SFB 754) \"Climate-Biogeochemistry Interactions in the Tropical Ocean\" to study (1) the structure of tropical oxygen minimum zones (OMZs), (2) the processes that contribute to the oxygen budget, and (3) long-term changes in the oxygen distribution. The OMZ of the eastern tropical North Atlantic (ETNA), located between the well-ventilated subtropical gyre and the equatorial oxygen maximum, is composed of a deep OMZ at about 400 m in depth with its core region centred at about 20° W, 10° N and a shallow OMZ at about 100 m in depth, with the lowest oxygen concentrations in proximity to the coastal upwelling region off Mauritania and Senegal. The oxygen budget of the deep OMZ is given by oxygen consumption mainly balanced by the oxygen supply due to meridional eddy fluxes (about 60%) and vertical mixing (about 20%, locally up to 30%). Advection by zonal jets is crucial for the establishment of the equatorial oxygen maximum. In the latitude range of the deep OMZ, it dominates the oxygen supply in the upper 300 to 400 m and generates the intermediate oxygen maximum between deep and shallow OMZs. Water mass ages from transient tracers indicate substantially older water masses in the core of the deep OMZ (about 120–180 years) compared to regions north and south of it. The deoxygenation of the ETNA OMZ during recent decades suggests a substantial imbalance in the oxygen budget: about 10% of the oxygen consumption during that period was not balanced by ventilation. Long-term oxygen observations show variability on interannual, decadal and multidecadal timescales that can partly be attributed to circulation changes. In comparison to the ETNA OMZ, the eastern tropical South Pacific OMZ shows a similar structure, including an equatorial oxygen maximum driven by zonal advection but overall much lower oxygen concentrations approaching zero in extended regions. As the shape of the OMZs is set by ocean circulation, the widespread misrepresentation of the intermediate circulation in ocean circulation models substantially contributes to their oxygen bias, which might have significant impacts on predictions of future oxygen levels.

The oceanic uptake and resulting storage of the anthropogenic CO2 (Cant) that humans have emitted into the atmosphere moderates climate change. Yet our knowledge about how this uptake and storage has progressed in time remained limited. Here, we determine decadal trends in the storage of Cant by applying the eMLR(C*) regression method to ocean interior observations collected repeatedly since the 1990s. We find that the global ocean storage of Cant grew from 1994 to 2004 by 29 ± 3 Pg C dec−1 and from 2004 to 2014 by 27 ± 3 Pg C dec−1 (±1σ). The storage change in the second decade is about 15 ± 11% lower than one would expect from the first decade and assuming proportional increase with atmospheric CO2. We attribute this reduction in sensitivity to a decrease of the ocean buffer capacity and changes in ocean circulation. In the Atlantic Ocean, the maximum storage rate shifted from the Northern to the Southern Hemisphere, plausibly caused by a weaker formation rate of North Atlantic Deep Waters and an intensified ventilation of mode and intermediate waters in the Southern Hemisphere. Our estimates of the Cant accumulation differ from cumulative net air‐sea flux estimates by several Pg C dec−1, suggesting a substantial and variable, but uncertain net loss of natural carbon from the ocean. Our findings indicate a considerable vulnerability of the ocean carbon sink to climate variability and change. Plain Language Summary The ocean takes up about 30% of the anthropogenic CO2 that is emitted to the atmosphere by human activities. The removal of this anthropogenic CO2 from the atmosphere counteracts climate change. The rate at which the ocean takes up anthropogenic CO2 is controlled by its transport from the surface to the depth of the ocean, where most of it accumulates. Thus, we can quantify and understand the oceanic uptake by keeping track of the accumulation of anthropogenic CO2 in the ocean interior. In this study, we use a global collection of measurements of CO2 in seawater to infer the temporal evolution of this accumulation between 1994 and 2014. We find that the ocean continued to act as a strong sink for CO2 over this period, removing, on average, nearly 30 billion tons of carbon per decade. However, we also detect a possible weakening of this uptake, since the accumulation of anthropogenic CO2 during the second decade was not as large as expected from the increase in atmospheric CO2. Our findings suggest that the ocean sink for CO2 might further shrink as climate change progresses. Key Points The global ocean storage of anthropogenic carbon grew by 29 ± 3 and 27 ± 3 Pg C dec−1 from 1994 to 2004 and 2004 to 2014, respectively The change in oceanic storage of anthropogenic carbon relative to the atmospheric CO2 growth decreased by 15 ± 11% from the first to the second decade This reduction is attributed to a decrease of the ocean buffer capacity and changes in ocean circulation

Ventilation is the primary pathway for atmosphere–ocean boundary perturbations, such as temperature anomalies, to be relayed to the ocean interior. It is also a conduit for gas exchange between the interface of atmosphere and ocean. Thus it is a mechanism whereby, for instance, the ocean interior is oxygenated and enriched in anthropogenic carbon. The ventilation of the Mediterranean Sea is fast in comparison to the world ocean and has large temporal variability. Here we present transient tracer data from a field campaign in April 2011 that sampled a unique suite of transient tracers (SF6, CFC-12, 3H and 3He) in all major basins of the Mediterranean. We apply the transit time distribution (TTD) model to the data in order to constrain the mean age, the ratio of the advective / diffusive transport and the number of water masses significant for ventilation. We found that the eastern part of the eastern Mediterranean can be reasonably described with a one-dimensional inverse Gaussian TTD (IG-TTD), and thus constrained with two independent tracers. The ventilation of the Ionian Sea and the western Mediterranean can only be constrained by a linear combination of IG-TTDs. We approximate the ventilation with a one-dimensional, two inverse Gaussian TTD (2IG-TTD) for these areas and demonstrate a possibility of constraining a 2IG-TTD from the available transient tracer data. The deep water in the Ionian Sea has a mean age between 120 and 160 years and is therefore substantially older than the mean age of the Levantine Basin deep water (60–80 years). These results are in contrast to those expected by the higher transient tracer concentrations in the Ionian Sea deep water. This is partly due to deep water of Adriatic origin having more diffusive properties in transport and formation (i.e., a high ratio of diffusion over advection), compared to the deep water of Aegean Sea origin that still dominates the deep Levantine Basin deep water after the Eastern Mediterranean Transient (EMT) in the early 1990s. The tracer minimum zone (TMZ) in the intermediate of the Levantine Basin is the oldest water mass with a mean age up to 290 years. We also show that the deep western Mediterranean has contributed approximately 40% of recently ventilated deep water from the Western Mediterranean Transition (WMT) event of the mid-2000s. The deep water has higher transient tracer concentrations than the mid-depth water, but the mean age is similar with values between 180 and 220 years.

Volatile halogenated organic compounds containing bromine and iodine, which are naturally produced in the ocean, are involved in ozone depletion in both the troposphere and stratosphere. Three prominent compounds transporting large amounts of marine halogens into the atmosphere are bromoform (CHBr3), dibromomethane (CH2Br2) and methyl iodide (CH3I). The input of marine halogens to the stratosphere has been estimated from observations and modelling studies using low-resolution oceanic emission scenarios derived from top-down approaches. In order to improve emission inventory estimates, we calculate data-based high resolution global sea-to-air flux estimates of these compounds from surface observations within the HalOcAt (Halocarbons in the Ocean and Atmosphere) database (https://halocat.geomar.de/). Global maps of marine and atmospheric surface concentrations are derived from the data which are divided into coastal, shelf and open ocean regions. Considering physical and biogeochemical characteristics of ocean and atmosphere, the open ocean water and atmosphere data are classified into 21 regions. The available data are interpolated onto a 1°×1° grid while missing grid values are interpolated with latitudinal and longitudinal dependent regression techniques reflecting the compounds' distributions. With the generated surface concentration climatologies for the ocean and atmosphere, global sea-to-air concentration gradients and sea-to-air fluxes are calculated. Based on these calculations we estimate a total global flux of 1.5/2.5 Gmol Br yr−1 for CHBr3, 0.78/0.98 Gmol Br yr−1 for CH2Br2 and 1.24/1.45 Gmol Br yr−1 for CH3I (robust fit/ordinary least squares regression techniques). Contrary to recent studies, negative fluxes occur in each sea-to-air flux climatology, mainly in the Arctic and Antarctic regions. \"Hot spots\" for global polybromomethane emissions are located in the equatorial region, whereas methyl iodide emissions are enhanced in the subtropical gyre regions. Inter-annual and seasonal variation is contained within our flux calculations for all three compounds. Compared to earlier studies, our global fluxes are at the lower end of estimates, especially for bromoform. An under-representation of coastal emissions and of extreme events in our estimate might explain the mismatch between our bottom-up emission estimate and top-down approaches.

The Mediterranean Sea is considered a \"hot spot\" for climate change, being characterized by oligotrophic to ultra-oligotrophic waters and rapidly increasing seasurface temperature and changing carbonate chemistry. Coccolithophores are considered a dominant phytoplankton group in these waters. As marine calcifying organisms they are expected to respond to the ongoing changes in seawater carbonate chemistry. We provide here a description of the springtime coccolithophore distribution in the Mediterranean Sea and relate this to a broad set of in situ-measured environmental variables. Samples were taken during the R/V Meteor (M84/3) oceanographic cruise in April 2011, between 0 and 100 m water depth from 28 stations. Total diatom and silicoflagellate cell concentrations are also presented. Our results highlight the importance of seawater carbonate chemistry, especially [CO32−] but also [PO43−] in unraveling the distribution of heterococcolithophores, the most abundant coccolithophore life phase. Holo- and heterococcolithophores respond differently to environmental factors. For instance, changes in heterococcolithophore assemblages were best linked to the combination of [CO32−], pH, and salinity (ρ = 0.57), although salinity might be not functionally related to coccolithophore assemblage distribution. Holococcolithophores, on the other hand, showed higher abundances and species diversity in oligotrophic areas (best fit, ρ = 0.32 for nutrients), thriving in nutrient-depleted waters. Clustering of heterococcolithophores revealed three groups of species sharing more than 65% similarities. These clusters could be assigned to the eastern and western basins and deeper layers (below 50 m), respectively. In addition, the species Gephyrocapsa oceanica, G. muellerae, and Emiliania huxleyi morphotype B/C are spatially distributed together and trace the influx of Atlantic waters into the Mediterranean Sea. The results of the present work emphasize the importance of considering holo- and heterococcolithophores separately when analyzing changes in species assemblages and diversity. Our findings suggest that coccolithophores are a main phytoplankton group in the entire Mediterranean Sea and can dominate over siliceous phytoplankton. They have life stages that are expected to respond differently to the variability in seawater carbonate chemistry and nutrient concentrations.

The Mediterranean Sea (MedSea) is considered a \"laboratory basin\" being an ocean in miniature, suffering dramatic changes in its oceanographic and biogeochemical conditions derived from natural and anthropogenic forces. Moreover, the MedSea is prone to absorb and store anthropogenic carbon due to the particular CO2 chemistry and the active overturning circulation. Despite this, water column CO2 measurements covering the whole basin are scarce. This work aims to be a base-line for future studies about the CO2 system space-time variability in the MedSea combining historic and modern CO2 cruises in the whole area. Here we provide an extensive vertical and longitudinal description of the CO2 system variables (total alkalinity - TA, dissolved inorganic carbon - DIC and pH) along an East-West transect and across the Sardinia-Sicily passage in the MedSea from two oceanographic cruises conducted in 2011 measuring CO2 variables in a coordinated fashion, the RV Meteor M84/3 and the RV Urania EuroFleets 11, respectively. In this sense, we provide full-depth and length CO2 distributions across the MedSea, and property-property plots showing in each sub-basin post-Eastern Mediterranean Transient (EMT) situation with regard to TA, DIC and pH. The over-determined CO2 system in 2011 allowed performing the first internal consistency analysis for the particularly warm, high salinity and alkalinity MedSea waters. The CO2 constants by Mehrbach et al. (1973) refitted by Dickson and Millero (1987) are recommended. The sensitivity of the CO2 system to the atmospheric CO2 increase, DIC and/or TA changes is evaluated by means of the Revelle and buffer factors.

This work presents data of dichlorodifluoromethane (CFC‐12), dissolved inorganic carbon and total alkalinity from a cruise to the Mediterranean Sea during October–November 2001, with the main focus on the CFC‐12 data and on the eastern basin. Using the transit time distribution method, the anthropogenic carbon concentrations in the basin were estimated. Results were cross‐checked with a back‐calculation technique. The entire water column of the Mediterranean Sea contains anthropogenic CO2, with minimum concentrations of 20.5 μmol kg−1 (error range: 16.9–27.1 μmol kg−1) in the most eastern part of the basin at intermediate depths, where the waters' mean age is >130 yr. Column inventories of up to 154 mol m−2 (132–179 mol m−2) are found and a total inventory of 1.7 Pg (1.3–2.1 Pg) of anthropogenic carbon in the Mediterranean Sea was estimated. There is a net flux of 38 Tg yr−1 (30–47 Tg yr−1) of dissolved inorganic carbon through the Strait of Gibraltar into the Atlantic Ocean and an opposite net flux of 3.5 Tg yr−1 (−1.8–9.2 Tg yr−1) of anthropogenic carbon into the Mediterranean Sea.

Significant changes in the overturning circulation of the Mediterranean Sea has been observed during the last few decades, the most prominent phenomena being the Eastern Mediterranean Transient (EMT) in the early 1990s and the Western Mediterranean Transition (WMT) during the mid-2000s. During both of these events unusually large amounts of deep water were formed, and in the case of the EMT, the deep water formation area shifted from the Adriatic to the Aegean Sea. Here we synthesize a unique collection of transient tracer (CFC-12, SF6 and tritium) data from nine cruises conducted between 1987 and 2011 and use these data to determine temporal variability of Mediterranean ventilation. We also discuss biases and technical problems with transient tracer-based ages arising from their different input histories over time; particularly in the case of time-dependent ventilation. We observe a period of low ventilation in the deep eastern (Levantine) basin after it was ventilated by the EMT so that the age of the deep water is increasing with time. In the Ionian Sea, on the other hand, we see evidence of increased ventilation after year 2001, indicating the restarted deep water formation in the Adriatic Sea. This is also reflected in the increasing age of the Cretan Sea deep water and decreasing age of Adriatic Sea deep water since the end of the 1980s. In the western Mediterranean deep basin we see the massive input of recently ventilated waters during the WMT. This signal is not yet apparent in the Tyrrhenian Sea, where the ventilation seems to be fairly constant since the EMT. Also the western Alboran Sea does not show any temporal trends in ventilation.