Tritium and helium isotope data provide key information on ocean circulation, ventilation, and mixing, as well as the rates of biogeochemical processes and deep-ocean hydrothermal processes. We present here global oceanic datasets of tritium and helium isotope measurements made by numerous researchers and laboratories over a period exceeding 60 years. The dataset's DOI is https://doi.org/10.25921/c1sn-9631, and the data are available at https://www.nodc.noaa.gov/ocads/data/0176626.xml (last access: 15 March 2019) or alternately http://odv.awi.de/data/ocean/jenkins-tritium-helium-data-compilation/ (last access: 13 March 2019) and includes approximately 60 000 valid tritium measurements, 63 000 valid helium isotope determinations, 57 000 dissolved helium concentrations, and 34 000 dissolved neon concentrations. Some quality control has been applied in that questionable data have been flagged and clearly compromised data excluded entirely. Appropriate metadata have been included, including geographic location, date, and sample depth. When available, we include water temperature, salinity, and dissolved oxygen. Data quality flags and data originator information (including methodology) are also included. This paper provides an introduction to the dataset along with some discussion of its broader qualities and graphics.

Around 1990 large volumes of Aegean Sea overflow began to be deposited in the near-bottom waters around thc Cretan Arc. The resulting. transient situation contrasts with a quasi-steady state situation prevailing previously in which the depth range below about 1200 m depth was dominated by waters of Adratic origin. In the course of the transient the distribution of ail properties changed drastically through the entire Eastern Mediterranean. The salinity of thc outflow through the Sicily Channel was lowered and nutrient concentrations in the upper waters were raised. In this communication we provide a description of the changes, address the causes and the initiation of the transient and name certain of its implications. The transient represents a unique océanographie event which warrants detailed studies also in the future. kev-words: deep waters, circulation, Eastern Mediterranean

This numerical study provides the first simulation of the anthropogenic tritium invasion and its decay product helium-3 (3He) in the Mediterranean Sea. The simulation covers the entire tritium (3H) transient generated by the atmospheric nuclear weapons tests performed in the 1950s and early 1960s and is run till 2011. Tritium, helium-3 and their derived age estimates are particularly suitable for studying intermediate and deep-water ventilation and spreading of water masses at intermediate/deep levels. The simulation is made using a high-resolution regional model NEMO (Nucleus for European Modelling of the Ocean), in a regional configuration for the Mediterranean Sea called MED12, forced at the surface with prescribed tritium evolution derived from observations. The simulation is compared to measurements of tritium and helium-3 performed along large-scale transects in the Mediterranean Sea during the last few decades on cruises of R/V Meteor: M5/6, M31/1, M44/4, M51/2, M84/3, and R/V Poseidon: 234. The results show that the input function used for the tritium generates a realistic distribution of the main hydrographic features of the Mediterranean Sea circulation. In the eastern basin, the results highlight the weak formation of Adriatic Deep Water in the model, which explains its weak contribution to the Eastern Mediterranean Deep Water (EMDW) in the Ionian sub-basin. It produces a realistic representation of the Eastern Mediterranean Transient (EMT) signal, simulating a deep-water formation in the Aegean sub-basin at the beginning of 1993, with a realistic timing of deep-water renewal in the eastern basin.

The eastern Mediterranean transient (EMT) was caused by a combination of high-salinity waters intruding into the Aegean Sea and the two particularly strong winters of 1991–1992 and 1992–1993. The approach in this chapter is to search for specific signatures in the historic hydrographic observations, which date back to 1910. To deal with the problem that up into the 1950s the data not only are of limited precision but also have gaps of about 20 years, it is advantageous to consider the fact that the evolution of the actual EMT is rather well documented over a similar time span. The chapter begins by outlining the characteristics of the current EMT. Thereafter, a selection of suitable hydrographic observations among the available historic data is provided to compare these with signatures expected from the evolution of the actual EMT.

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.

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 subsections, 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.

We present a comprehensive account of tritium and 3He in the Mediterranean Sea since the appearance of the tritium generated by the atmospheric nuclear-weapon testing in the 1950s and early 1960s, based on essentially all available observations. Tritium in surface waters rose to 20–30 TU in 1964 (TU = 1018 × [3H]/H]), a factor of about 100 above the natural level, and thereafter declined 30-fold up to 2011. The decline was largely due to radioactive tritium decay, which produced significant amounts of its stable daughter 3He. We present the scheme by which we separate the tritiugenic part of 3He and the part due to release from the sea floor (terrigenic part). We show that the tritiugenic component can be quantified throughout the Mediterranean waters, typically to a ± 0.15 TU equivalent, mostly because the terrigenic part is low in 3He. This fact makes the Mediterranean unique in offering a potential for the use of tritiugenic 3He as a tracer. The transient distributions of the two tracers are illustrated by a number of sections spanning the entire sea and relevant features of their distributions are noted. By 2011, the 3He concentrations in the top few hundred metres had become low, in response to the decreasing tritium concentrations combined with a flushing out by the general westward drift of these waters. Tritium-3He ages in Levantine Intermediate Water (LIW) were obtained repeated in time at different locations, defining transit times from the LIW source region east of Rhodes. The ages show an upward trend with the time elapsed since the surface-water tritium maximum, which arises because the repeated observations represent increasingly slower moving parts of the full transit time spectrum of LIW. The transit time dispersion revealed by this new application of tritium-3He dating is considerable. We find mean transit times of 12 ± 2 yr up to the Strait of Sicily, 18 ± 3 yr up to the Tyrrhenian Sea, and 22 ± 4 yr up into the Western Mediterranean. Furthermore, we present full Eastern Mediterranean sections of terrigenic 3He and tritium-3He age in 1987, the latter one similarly showing an effect of the transit time dispersion. We conclude that the available tritium and 3He data, particularly if combined with other tracer data, are useful for constraining the subsurface circulation and mixing of the Mediterranean Sea.

We present a new method to obtain samples for the measurement of helium isotopes and neon in water, to replace the classical sampling procedure using clamped-off Cu tubing containers that we have been using so far. The new method saves the gas extraction step prior to admission to the mass spectrometer, which the classical method requires. Water is drawn into evacuated glass ampoules with subsequent flame sealing. Approximately 50% headspace is left, from which admission into the mass spectrometer occurs without further treatment. Extensive testing has shown that, with due care and with small corrections applied, the samples represent the gas concentrations in the water within ±0.07% (95% confidence level; ±0.05% with special handling). Fast evacuation is achieved by pumping on a small charge of water placed in the ampoule. The new method was successfully tested at sea in comparison with Cu-tubing sampling. We found that the ampoule samples were superior in data precision and that a lower percentage of samples were lost prior to measurement. Further measurements revealed agreement between the two methods in helium, 3He and neon within ±0.1%. The new method facilitates the dealing with large sample sets and minimizes the delay between sampling and measurement. The method is applicable also for gases other than helium and neon.

The measurements reported show that movement of soil moisture is layered. A single rainfall, artificially spiked with isotope tracer, will therefore form a tagged layer of water, which, although blurred by diffusion effects, moves downward as a distinguishable boundary between the older rainwater below and the younger rainwater above. After a certain time and a corresponding displacement of the tracer peak, one can therefore draw up a balance between incoming rain (corrected for runoff) during the period in question a:nd the water still remaining in the soil and eventually yielding groundwater, the difference beIng the evaporation loss. Fine grain soils show average draining velocities below 1 meter per year, so that the method gives accurate values only for periods of at least a few months. The theoretical basis and the limitations of the method are discussed. The method should provIde detailed information on the water balance without disturbing the natural conditions and should be applicable everywhere at low cost.

Calibration: The classical calibration of mass spectrometric helium and neon measurements uses aliquots of atmospheric air, which is convenient but limited in accuracy and long-term stability. Our alternative is to use water samples equilibrated with undisturbed air, so that their mass can be converted into equivalent volumes of air using a solubility function. In this way, the samples allow a precise recalibration of the air aliquots. A bias relative to regular samples is excluded because the equilibrated water is subjected to exactly the same treatment. The equilibration unit has a water capacity of 4.5 liters. The water is circulated over exchange mats, yielding full air-water equilibrium within two hours, and temperature, pressure, and humidity are precisely controlled. In consequence, we achieve solubility equilibrium within 0.03%, so that high accuracy and long-term stability of the calibration are guaranteed. The solubility equilibrium values are more uncertain, but a biased value will only introduce a common shift to the data, i.e. it will not affect the internal consistency of the calibration. The new calibration mode will also enable efficient intercalibration between laboratories. Solubility determination and sampling procedures: We shall use the equilibration unit to obtain solubility functions of helium and neon in distilled water and seawater with a projected accuracy of 0.2%. One measure to achieve this is to compare the mass spectrometric signals of the water and the air phase directly. In this context, we developed a procedure to sample water into glass ampoules to be flame-sealed. They are filled about half, which means that the gas in the head space can directly be admitted into the mass spectrometer, because only about 1% of the helium and neon remains in solution. The uncertainty of the helium and neon concentrations introduced by the procedure does not exceed 0.05% and blanks are about negligible. The device is simple and handling fast. Experience on a cruise into the tropical Atlantic has proven that the sampling procedure can be applied reliably in the field. We also devised a way to transfer air samples into identical ampoules.

The observed small excesses of helium and neon over solubility-equilibrium concentrations in the ocean mixed layer serve as a tool to study the physics of the atmosphere-ocean exchange of gases in general. Currently this application is limited by the fact that published solubilities differ by 1% or more, compared to excesses of mostly about 4% and to measurement precisions of 0.4% or better. To resolve that discrepancy, we have developed a procedure capable of solubility measurement accurate to 0.2%. Water and clean atmospheric air are equilibrated in a container under precise temperature control and at exact laboratory pressure. The solubility equilibrium is reached within about 1 hour. Samples of both the water and air phases are analyzed for helium and neon using the Bremen mass spectrometric facility. To minimize systematic errors, we rely on direct comparison for the samples of the two phases (alternate measurement). Sample treatment and transfer into the mass spectrometer is much the same for the two phases, and we made sure that remaining differences between the phases are small (< 0.1%). First results are presented, in comparison with literature data.

Observations of tritium and 3He in the Tyrrhenian Sea, 1987–2009, confirm the enhanced vertical mixing of intermediate waters into the deep waters that has been noted and associated with the Eastern Mediterranean Transient in previous studies. Our evidence for the mixing rests on increasing tracer concentrations in the Tyrrhenian deep waters, accompanied by decreases in the upper waters, which are supplied from the Eastern Mediterranean. The downward transfer is particularly evident between 1987 and 1997. Later on, information partly rests on increasing tritium-3He ages; here we correct the observed 3He for contributions released from the ocean floor. The Tyrrhenian tracer distributions are fully compatible with data upstream of the Sicily Strait and in the Western Mediterranean. The tracer data show that mixing reached to the bottom and confirm a cyclonic nature of the deep water circulation in the Tyrrhenian. They furthermore indicate that horizontal homogenization of the deep waters occurs on a time scale of roughly 5 years. Various features point to a reduced impact of Western Mediterranean Deep Water (WMDW) in the Tyrrhenian during the enhanced-mixing period. This is an important finding because it implies less upward mixing of WMDW, which has been named a major process to enable the WMDW to leave the Mediterranean via the Gibraltar Strait. On the other hand, the TDW outflow for several years represented a major influx of enhanced salinity and density waters into the deep-water range of the Western Mediterranean.

The paper presents interesting observations of tritium and 3He in the Tyrrhenian Sea. The work addresses key questions for the Mediterranean oceanographic community such as the deep water formation in the Thyrrenian Sea and the role of the Eastern Mediterranean Transient. The results presented here are a substantial contribution since they provide evidence of a convective mixing of intermediate waters into deep waters associated to Eastern Mediterranean Transient. Moreover, they provide confirmation of the cyclonic nature of