Description: Ocean ventilation is the integrated effect of various processes that exchange surface properties with the ocean interior and is essential for oxygen supply, storage of anthropogenic carbon and the heat budget of the ocean, for instance. Current observational methods utilise transient tracers, e.g. tritium, SF6, CFCs and 14C. However, their dating ranges are not ideal to resolve the centennial-dynamics of the deep ocean, a gap filled by the noble gas isotope 39Ar with a half-life of 269 years. Its broad application has been hindered by its very low abundance, requiring 1000 L of water for dating. Here we show successful 39Ar dating with 5 L of water based on the atom-optical technique Atom Trap Trace Analysis. Our data reveal previously not quantifiable ventilation patterns in the Tropical Atlantic, where we find that advection is more important for the ventilation of the intermediate depth range than previously assumed. Now, the demonstrated analytical capabilities allow for a global collection of 39Ar data, which will have significant impact on our ability to quantify ocean ventilation.

Description: Anthropogenic activities have resulted in enhanced lead (Pb) emissions to the environment over the past century, mainly through the combustion of leaded gasoline. Here, we present the first combined dissolved (DPb), labile (LpPb) and particulate (PPb) Pb dataset from the Northeast Atlantic (Celtic Sea) since the phasing out of leaded gasoline in Europe. Concentrations of DPb in surface waters have decreased by 4-fold over the last four decades. We demonstrate that anthropogenic Pb is transported from the Mediterranean Sea over long distances (〉2500 km). Benthic DPb fluxes exceeded the atmospheric Pb flux in the region, indicating the importance of sediments as a contemporary Pb source. A strong positive correlation between DPb, PPb and LpPb indicates a dynamic equilibrium between the phases and the potential for particles to ‘buffer’ the DPb pool. This study provides insights into Pb biogeochemical cycling and demonstrates the potential of Pb in constraining ocean circulation patterns.

Description: The South China Sea (SCS) is the largest semienclosed marginal sea in the western Pacific (WP) and connects to the west Pacific through the Luzon Strait (LU). In this study, we use the observation of transient tracer chlorofluorocarbon‐12 (CFC‐12) to calculate the ventilation time scales of the SCS, LU, and WP. The CFC‐12 and oxygen data are used together to identify the sandwiched structure vertically of the flows across the LU. The CFC‐12 and oxygen distributions reveal a pronounced decrease westward across the LU and a slight decrease southward in the transport of the SCS. The mean age gradient of the salinity minimum (Smin) water between the WP and the northern SCS could be a consequence of intensive mixing and entrainment of the inflow water from the WP. An expected difference in age between the LU and SSCS is verified to reflect the transit time for the given water layers in the SCS. Thus, a mean transit time of 77 ± 20 years is estimated for the intermediate water in the SCS interior.

Description: The Southern Ocean is the most important area of anthropogenic carbon (Cant) uptake in the world ocean, only rivalled in importance by the North Atlantic Ocean. Significant variability on decadal time-scales in the uptake of Cant in the Southern Ocean has been observed and modelled, likely with consequences for the interior ocean storage of Cant in the region, and implications for the global carbon budget. Here we use eight cruises between 1973 and 2012 to assess decadal variability in Cant storage rates in the southeast Atlantic sector of the Southern Ocean. For this we employed the extended multiple linear regression (eMLR) method. We relate variability in DIC (dissolved inorganic carbon) storage, which is assumed to equal anthropogenic carbon storage, to changes in ventilation as observed from repeat measurements of transient tracers. Within the Antarctic Intermediate Water (AAIW) layer, which is the dominant transport conduit for Cant into the interior ocean, moderate Cant storage rates were found without any clear temporal trend. In Subantarctic Mode Water (SAMW), a less dense water mass found north of the Subantarctic Front and above AAIW, high storage rates of Cant were observed up to about 2005 but lower rates in more recent times. The transient tracer data suggest a significant speed-up of ventilation in the summer warmed upper part of AAIW between 1998 and 2012, which is consistent with the high storage rate of Cant. A shift of more northern Cant storage to more southern storage in near surface waters was detected in the early 2000s. Beneath the AAIW the eMLR method as applied here did not detect significant storage of Cant. However, the presence of the transient tracer CFC-12 all through the water column suggests that some Cant should be present, but at concentrations not reliably quantifiable. The observed temporal variability in the interior ocean seems at a first glance to be out of phase with observed surface ocean Cant fluxes, but this can be explained by the time delay for the surface ocean signal to manifest itself in the interior of the ocean.

Description: The replenishment of consumed oxygen in the open ocean oxygen minimum zone (OMZ) off northwest Africa is accomplished by oxygen transport across and along density surfaces, i.e. diapycnal and isopycnal oxygen supply. Here the diapycnal oxygen supply is investigated using a large observational set of oxygen profiles and diapycnal mixing data from years 2008 to 2010. Diapycnal mixing is inferred from different sources: (i) a large-scale tracer release experiment, (ii) microstructure profiles, and (iii) shipboard acoustic current measurements plus density profiles. From these measurements, the average diapycnal diffusivity in the studied depth interval from 150 to 500m is estimated to be 1×10−5 m2 s−1, with lower and upper 95%confidence limits of 0.8×10−5 m2 s−1 and 1.4×10−5 m2 s−1. Diapycnal diffusivity in this depth range is predominantly caused by turbulence, and shows no significant vertical gradient. Diapycnal mixing is found to contribute substantially to the oxygen supply of the OMZ. Within the OMZ core, 1.5 μmol kg−1 yr−1 of oxygen is supplied via diapycnal mixing, contributing about one-third of the total demand. This oxygen which is supplied via diapycnal mixing originates from oxygen that has been laterally supplied within the upper CentralWater layer above the OMZ, and within the Antarctic Intermediate Water layer below the OMZ. Due to the existence of a separate shallow oxygen minimum at about 100m depth throughout most of the study area, there is no net vertical oxygen flux from the surface layer into the Central Water layer. Thus all oxygen supply of the OMZ is associated with remote pathways.

Description: 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

Description: 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.

Description: 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.

Description: Ocean observations carried out in the framework of the Collaborative Research Center 754 (SFB 754) "Climate-Biogeochemistry Interactions in the Tropical Ocean" are used 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 depth with its core region centred at about 20° W, 10° N and a shallow OMZ at about 100 m depth with 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 time scales 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.

Description: This paper is the outcome of a workshop held in Rome in November 2011 on the occasion of the 25th anniversary of the POEM (Physical Oceanography of the Eastern Mediterranean) program. In the workshop discussions, a number of unresolved issues were identified for the physical and biogeochemical properties of the Mediterranean Sea as a whole, i.e., comprising the Western and Eastern sub-basins. Over the successive two years, the related ideas were discussed among the group of scientists who participated in the workshop and who have contributed to the writing of this paper. Three major topics were identified, each of them being the object of a section divided into a number of different sub-sections, each addressing a specific physical, chemical or biological issue: 1. Assessment of basin-wide physical/biochemical properties, of their variability and interactions. 2. Relative importance of external forcing functions (wind stress, heat/moisture fluxes, forcing through straits) vs. internal variability. 3. Shelf/deep sea interactions and exchanges of physical/biogeochemical properties and how they affect the sub-basin circulation and property distribution. Furthermore, a number of unresolved scientific/methodological issues were also identified and are reported in each sub-section after a short discussion of the present knowledge. They represent the collegial consensus of the scientists contributing to the paper. Naturally, the unresolved issues presented here constitute the choice of the authors and therefore they may not be exhaustive and/or complete. The overall goal is to stimulate a broader interdisciplinary discussion among the scientists of the Mediterranean oceanographic community, leading to enhanced collaborative efforts and exciting future discoveries.