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In order to complement the picture of the atmospheric water cycle in the Southern Ocean, we have continuously monitored water vapor isotopes since January 2020 on Amsterdam Island in the Indian Ocean. We present here the first 2-year long water vapor isotopic record at this site. We show that the water vapor isotopic composition largely follows the water vapor mixing ratio, as expected in marine boundary layers. However, we detect 11 periods of a few days where there is a strong loss of correlation between water vapor δ18O and water vapor mixing ratio as well as abrupt negative excursions of water vapor δ18O. These excursions often occur toward the end of precipitation events. Six of these events show a decrease in gaseous elemental mercury, suggesting subsidence of air from a higher altitude. Our study aims to further explore the mechanism driving these negative excursions in water vapor δ18O. We used two different models to provide a data–model comparison over this 2-year period. While the European Centre Hamburg model (ECHAM6-wiso) at 0.9° was able to reproduce most of the sharp negative water vapor δ18O excursions, hence validating the physics process and isotopic implementation in this model, the Laboratoire de Météorologie Dynamique Zoom model (LMDZ-iso) at 2° (3°) resolution was only able to reproduce seven (one) of the negative excursions, highlighting the possible influence of the model resolution for the study of such abrupt isotopic events. Based on our detailed model–data comparison, we conclude that the most plausible explanations for such isotopic excursions are rain–vapor interactions associated with subsidence at the rear of a precipitation event.

In a context of global warming and sea level rise acceleration, it is key to estimate the evolution of the atmospheric hydrological cycle and temperature in polar regions, which directly influence the surface mass balance of the Arctic and Antarctic ice sheets. Direct observations are available from satellite data for the last 40 years and a few weather data since the 1950s in Antarctica. One of the best ways to access longer records is to use climate proxies in firn or ice cores. The water isotopic composition in these cores is widely used to reconstruct past temperature variations. We need to progress in our understanding of the influence of the atmospheric hydrological cycle on the water isotopic composition of ice cores. First, we present a 2-year-long time series of vapor and precipitation isotopic composition measurement at Dumont d’Urville Station, in Adélie Land. We characterize diurnal variations of meteorological parameters (temperature, atmospheric water mixing ratio (hereafter humidity) and δ18O) for the different seasons and determine the evolution of key relationships (δ18O versus temperature or humidity) throughout the year: we find that the temperature vs. δ18O relationship is dependent on synoptic events dynamics in winter contrary to summer. Then, this data set is used to evaluate the atmospheric general circulation model ECHAM6-wiso (model version with embedded water stable isotopes) in a coastal region of Adélie Land where local conditions are controlled by strong katabatic winds which directly impact the isotopic signal. We show that a combination of continental (79 %) and oceanic (21 %) grid cells leads model outputs (temperature, humidity and δ18O) to nicely fit the observations, at different timescales (i.e., seasonal to synoptic). Therefore we demonstrate the added value of long-term water vapor isotopic composition records for model evaluation. Then, as a clear link is found between the isotopic composition of water vapor and precipitation, we assess how isotopic models can help interpret short firn cores. In fact, a virtual firn core built from ECHAM-wiso outputs explains much more of the variability observed in S1C1 isotopic record than a virtual firn core built from temperature only. Yet, deposition and post-deposition effects strongly affect the firn isotopic signal and probably account for most of the remaining misfits between archived firn signal and virtual firn core based on atmospheric modeling.

The EPICA (European Project for Ice Coring in Antarctica) Dome C (EDC) ice core drilling in East Antarctica reaches a depth of 3260 m. The reference EDC chronology, the AICC2012 (Antarctic Ice Core Chronology 2012), provides an age vs. depth relationship covering the last 800 kyr (thousands of years), with an absolute uncertainty rising up to 8000 years at the bottom of the ice core. The origins of this relatively large uncertainty are twofold: (1) the δ18Oatm, δO2/N2 and total air content (TAC) records are poorly resolved and show large gaps over the last 800 kyr, and (2) large uncertainties are associated with their orbital targets. Here, we present new highly resolved δ18Oatm, δO2/N2 and δ15N measurements for the EDC ice core covering the last five glacial–interglacial transitions; a new low-resolution TAC record over the period 440–800 ka BP (ka: 1000 years before 1950); and novel absolute 81Kr ages. We have compiled chronological and glaciological information including novel orbital age markers from new data on the EDC ice core as well as accurate firn modeling estimates in a Bayesian dating tool to construct the new AICC2023 chronology. For the first time, three orbital tools are used simultaneously. Hence, it is possible to observe that they are consistent with each other and with the other age markers over most of the last 800 kyr (70 %). This, in turn, gives us confidence in the new AICC2023 chronology. The average uncertainty in the ice chronology is reduced from 1700 to 900 years in AICC2023 over the last 800 kyr (1σ). The new timescale diverges from AICC2012 and suggests age shifts reaching 3800 years towards older ages over marine isotope stages (MISs) 5, 11 and 19. But the coherency between the new AICC2023 timescale and independent chronologies of other archives (Italian Lacustrine succession from Sulmona Basin, Dome Fuji ice core and northern Alpine speleothems) is improved by 1000 to 2000 years over these time intervals.

The EPICA Dome C (EDC) ice core provides the longest continuous climatic record, covering the last 800 000 years (800 kyr). A unique opportunity to investigate decadal to millennial variability during past glacial and interglacial periods is provided by the high-resolution water isotopic record (δ18O and δD) available for the EDC ice core. We present here a continuous compilation of the EDC water isotopic record at a sample resolution of 11 cm, which consists of 27 000 δ18O measurements and 7920 δD measurements (covering, respectively, 94 % and 27 % of the whole EDC record), including published and new measurements (2900 for both δ18O and δD) for the last 800 kyr. Here, we demonstrate that repeated water isotope measurements of the same EDC samples from different depth intervals obtained using different analytical methods are comparable within analytical uncertainty. We thus combine all available EDC water isotope measurements to generate a high-resolution (11 cm) dataset for the past 800 kyr. A frequency decomposition of the most complete δ18O record and a simple assessment of the possible influence of diffusion on the measured profile shows that the variability at the multi-decadal to multi-centennial timescale is higher during glacial than during interglacial periods and higher during early interglacial isotopic maxima than during the Holocene. This analysis shows as well that during interglacial periods characterized by a temperature optimum at the beginning, the multi-centennial variability is strongest over this temperature optimum.

Obtaining precise continuous measurements of water vapor isotopic composition in dry places (polar or high-altitude regions) is an important challenge. The current limitation is the strong influence of humidity on the measured water isotopic composition by laser spectroscopy instruments for low humidity levels (below 3000 ppmv). This problem is addressed by determining the relationships between humidity and measured δ18O and δD of known water standards. Here, we present the development of a robust field instrument able to generate water vapor, down to 70 ppmv, at very stable humidity levels (average 1σ lower than 10 ppmv). This instrument, operated by a Raspberry interface, can be coupled to a commercial laser spectroscopy instrument. We checked the stability of the system as well as its accuracy when expressing the measured isotopic composition of water vapor on the VSMOW–SLAP (Vienna Standard Mean Ocean Water – Standard Light Antarctic Precipitation) scale. It proved to be highly stable during autonomous operation over more than 1 year at the East Antarctic Concordia and Dumont d'Urville stations.

Helium isotopes (3He, 4He) are useful tracers for investigating the deep ocean circulation and for evaluating ocean general circulation models, because helium is a stable and conservative nuclide that does not take part in any chemical or biological process. Helium in the ocean originates from three different sources, namely, (i) gas dissolution in equilibrium with atmospheric helium, (ii) helium-3 addition by radioactive decay of tritium (called tritiugenic helium), and (iii) injection of terrigenic helium-3 and helium-4 by the submarine volcanic activity which occurs mainly at plate boundaries, and also addition of (mainly) helium-4 from the crust and sedimentary cover by α-decay of uranium and thorium contained in various minerals. We present the first simulation of the terrigenic helium isotope distribution in the whole Mediterranean Sea using a high-resolution model (NEMO-MED12). For this simulation we build a simple source function for terrigenic helium isotopes based on published estimates of terrestrial helium fluxes. We estimate a hydrothermal flux of 3.5 mol3 He yr−1 and a lower limit for the crustal flux at 1.6 × 10−7 4He mol m−2 yr−1. In addition to providing constraints on helium isotope degassing fluxes in the Mediterranean, our simulations provide information on the ventilation of the deep Mediterranean waters which is useful for assessing NEMO-MED12 performance. This study is part of the work carried out to assess the robustness of the NEMO-MED12 model, which will be used to study the evolution of the climate and its effect on the biogeochemical cycles in the Mediterranean Sea, and to improve our ability to predict the future evolution of the Mediterranean Sea under the increasing anthropogenic pressure.

Two newly discovered hydrothermal vent fields of the Wallis and Futuna region, Kulo Lasi and Fatu Kapa, were sampled for fluid geochemistry. A great geochemical diversity was observed and assigned to the diversity of lithologies as well as the occurrence of various processes. Kulo Lasi fluids likely formed by interaction with fresh volcanic rocks, phase separation, and mixing with magmatic fluid. Conversely, the geochemistry of the Fatu Kapa fluids would be mostly due to water/felsic lavas reactions. In terms of organic geochemistry, fluids from both fields were found to be enriched in formate, acetate, and semivolatile organic compounds (SVOCs): n-alkanes, n-fatty acids, and polyaromatic hydrocarbons (PAHs). Concentrations of SVOCs reached a few ppb at most. The distribution patterns of SVOCs indicated that several processes and sources, at once of biogenic, thermogenic, and abiogenic types, likely controlled organic geochemistry. Although the contribution of each process remains unknown, the mere presence of organics at the μM level has strong implications for metal dispersion (cycles), deposition (ore-forming), and bioavailability (ecosystems), especially as our fluxes estimations suggest that back-arc hosted vent fields could contribute as much as MOR to the global ocean heat and mass budget.

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 report the complete conversion of inulin in gas/liquid media by a dielectric barrier discharge plasma at atmospheric pressure. Depending on the plasma treatment time (from 1 to 30 min) and the chemical nature of the gases (air, oxygen, nitrogen), it was possible to depolymerize inulin into fructo-oligosaccharides with a degree of polymerization under 5 or to achieve a total conversion of inulin into its two monomeric constituents, fructose and glucose in 20 min, without any degradation products. Combined results from liquid chromatography (HPLC), solid state Nuclear Magnetic Resonance (ssNMR) and mass spectroscopy revealed that the breakage of the β 1-4-bridged oxygen occurs by an acidic attack, following the oxidation of the polymer. Infrared spectroscopy revealed the oxidation and breakage of the polymer and also adsorption of nitrate species. Non thermal plasma treatment appears as a promising technology for the efficient production of mono and oligosaccharides from various sources for the added value molecules in food and pharmaceutical application domains., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The Rhône is characterised by a heavy concentration of nuclear-based industries including nuclear power stations and nuclear sites housing civilian and military facilities. Here, we report the results of a four-year survey (2010-2013) of tritium and radiocarbon levels in a variety of matrices within the Rhône delta and along the French Mediterranean coastline. The aim of the study is to create a spatial reference framework of environmental levels of these two radionuclides, which are the most prevalent in radioactive effluents from nuclear power stations. Although both tritium and radiocarbon levels in the samples analysed are very low and can only be detected using ultra-sensitive analytical techniques, they clearly show the influence of the tritium and radiocarbon discharges carried by the Rhône plume along the Mediterranean coast. The tritium content of suspended matter and sediments of the Rhône is a special case, which shows elevated tritium values not seen in other French rivers with similar nuclear facilities. The north-south spatial distribution of this tritium anomaly shows that these trace values are at their highest in the upper Rhône, close to the Swiss border and upstream of Creys Malville, the northernmost nuclear power station on the Rhône. This points to a legacy of past tritium releases by the watchmaking industry. A dedicated study would be needed to clearly identify the source and the exact nature of this contamination., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

An original methodology to quantitatively explore exchangeability of hydrogen isotopes in carbohydrate molecules is proposed. To access the speciation of organically bound hydrogen isotopes, isotopic exchanges were carried out under a soft path regime in the vapor phase at 20 °C with set (D,T/H) vapor pressure ratios. When steady states were reached, the fraction of exchangeable hydrogen of microcrystalline cellulose, alpha-cellulose and wheat grains were obtained and ranged from 13 to 31% (versus a theoretical value of 30%). In cellulose, and more specifically in microcrystalline cellulose, the molecular hydrogen bonds as well as the different conformations of the network seemed to decrease the hydroxyl groups of glucose units available for isotopic exchange. On the contrary, the assumed enzymatic hydrolysis of the constitutive molecules of wheat starch into low-molecular weight carbohydrate molecules enhanced the exchangeable pool. An average value of the activity between non-exchangeable organically bound tritium (NE-OBT) and non-exchangeable organically bound hydrogen was calculated for wheat grains, (TH) NE  = 0.55 ± 0.03 Bq.g -1 of hydrogen atoms., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

We have investigated the effect of non-thermal atmospheric plasma (NTAP) on the structure of microcrystalline cellulose. In particular, by means of different characterization methods, we demonstrate that NTAP promotes the partial cleavage of the β-1,4 glycosidic bond of cellulose leading to the release of short-chain cellodextrins that are reassembled in situ, preferentially at the C6 position, to form branched glucans with either a glucosyl or anhydroglucosyl terminal residue. The ramification of cellulosic chain induced by NTAP yields branched glucans that are soluble in DMSO or in water, thus opening a straightforward access to processable glucans from cellulose. Importantly, the absence of solvent and catalyst considerably facilitates downstream processing as compared to (bio)catalytic processes which typically occur in diluted conditions., (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The (3)He ingrowth technique is based on the detection of the tritium radioactive daughter, (3)He, by mass spectrometry. Over the last three decades it has been used extensively in oceanography and groundwater studies for measurements of very low to ultra-low levels of tritium. To compare it with the best available methods of radioactive counting, we applied this method to measure the massic activity of a tritiated-water primary standard prepared by the French Laboratoire National Henri Becquerel (LNHB). One liter of a low-level tritium solution was prepared from a small aliquot of the LNHB standard by two-step gravimetric dilution with tritium-free groundwater. Sixteen samples of this solution were analyzed at the LSCE-Saclay noble gas facility, using the (3)He ingrowth method. The massic activity of the prepared solution was also measured by Liquid Scintillation Counting using the Quantulus LNHB counter and an internal calibration method with the LNHB tritiated water standard. All results agree within their standard uncertainty., (© 2013 Published by Elsevier Ltd.)

Following recent suggestions regarding the strong affinity of tritiated water for organic matter in suspended particulates and sediments, two equilibration experiments between sediment organic matter (dry and fresh) and tritiated water were performed to look for potential tritium bio-concentration. The T/H ratios measured at the end of both experiments are lower in the sediment organic matter than in the water, indicating that only a fraction of the hydrogen pool (between 14% and 20%) within the sediment equilibrated with the tritiated water. These results are consistent with the widely used concept of exchangeable and non-exchangeable tritium pools in organic matter and show no sign of tritium bio-accumulation in the sediment relative to water., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Tritium (³H or T) is one of the major radionuclides released by nuclear power plants (NPP) into rivers. However, tritiated water (HTO) flux from water to air is seldom considered when assessing health effects of such releases. The aim of this paper is to present the result of a research program, called LORA, conducted on the Loire River (France). To improve our understanding of HTO flux from surface water to air, three field campaigns were organised during the NPP's radioactive releases to measure simultaneously the activity concentrations in air on the riverbank, using an innovative system, and in river water. The measurements showed that during radioactive releases, water vapour was enriched in ³H. These results were used to calibrate exchange velocities. The average of these estimated exchange velocities was more than one order of magnitude higher than those calculated in the literature from indoor experiments. The variability of these values was also larger, showing that outdoor studies cover a wide range of conditions influencing HTO flux. No correlation was observed between exchanges velocities and meteorological conditions. However, there was a significant difference between day and night with a higher value observed during the day. Two approaches used to calculate HTO evaporation from water (i.e. the approach based on water evaporation and the approach considering that HTO follows its own concentration gradient) were included in a hydrodynamic model, which was used to evaluate HTO air activity along the Loire River. In conclusion, only the approach considering that HTO follows its own gradient led to a good agreement between measurements and predictions. A one-year simulation was done to estimate the contribution of this process to the dose. Its contribution can be considered as negligible in this case compared to the other pathways such as ingestion of water or foodstuffs., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

The design, setup and performance of a mass spectrometric system for the analysis of low to very low-level tritium in environmental samples are described. The tritium concentration is measured indirectly by the (3)He ingrowth from radioactive decay after complete initial degassing of the sample. The analytical system is fully computer-controlled and consists in a commercial helium isotope mass spectrometer coupled with a high vacuum inlet system. A detection limit of 0.15 Bq/kg is routinely obtainable for sample sizes of 20g of water equivalent and an accumulation time of three months. Larger samples (and/or longer accumulation time) can be used to obtain lower detection limits. In addition to the benefit of a lower detection limit, another advantage of this non-destructive method lies in the simplicity of the analytical procedure which strongly limits the risk of contamination. An inter-comparison was successfully performed with the conventional beta counting technique on lyophilized grass samples, in a range of tritium concentrations of environmental interest. It shows that the (3)He mass spectrometry method yields results that are fully consistent with the conventional liquid scintillation technique over a wide range of tritium concentrations., (Copyright 2009 Elsevier Ltd. All rights reserved.)

The Creys-Malville nuclear plant, located on the left bank of the Rhône, was shut down in 1998. The facilities are currently in their initial stage of dismantling. In order to establish a baseline for tritium in the vicinity of the site prior to the main dismantling phase, we carried out a monitoring program between 2002 and 2005 in the main terrestrial and aquatic compartments of the local environment. Tritium levels in the groundwaters and in the Rhône waters correspond to the regional tritium concentration in precipitation. The data obtained for the terrestrial environment are also in good agreement with the regional background and do not show any specific signature linked to the nuclear plant. The various aquatic compartments of the Rhône (fish, plant, sediment) are significantly enriched in tritium both upstream and downstream of the power plant: although Tissue-Free Water Tritium concentrations are in equilibrium with the river water, the non-exchangeable fraction of organic bound tritium in plants and fishes shows values which outpace the river water background by one to two orders of magnitude, and up to four to five orders of magnitude in the sediments. This tritium anomaly is not related to the nuclear plant, as it is already present at the Swiss border 100km upstream of the site. Although fine particles of tritiated polystyrene entering the composition of the luminous paints used by the clock industry have been suspected on several occasions, the exact nature and the origin of this tritium source remain unknown and require further investigations.

In the hydrothermal circulation at mid-ocean ridges, sea water penetrates the fractured crust, becomes heated by its proximity to the hot magma, and returns to the sea floor as hot fluids enriched in various chemical elements. In contradiction to earlier results that predict diminishing hydrothermal activity with decreasing spreading rate, a survey of the ultra-slowly spreading Gakkel Ridge (Arctic Ocean) by Edmonds et al. and Michael et al. suggests that, instead of being rare, the hydrothermal activity is abundant--exceeding by at least a factor of two to three what would be expected by extrapolation from observation on faster spreading ridges. Here we use helium-3 (3He), a hydrothermal tracer, to show that this abundance of venting sites does not translate, as would be expected, into an anomalous hydrothermal 3He output from the ridge. Because of the wide implications of the submarine hydrothermal processes for mantle heat and mass fluxes to the ocean, these conflicting results call for clarification of the link between hydrothermal activity and crustal production at mid-ocean ridges.