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The ability to infer past temperatures from ice core records has in the past relied on the assumption that after precipitation, the stable water isotopic composition of the snow surface layer is not modified before being buried deeper into the snowpack and transformed into ice. However, in extremely dry environments, such as the East Antarctic plateau, the precipitation is so sparse that the surface is exposed to the atmosphere for significant time before burial. During that exposure, several processes have been recently identified as impacting the snow isotopic composition after snowfall: (1) exchanges with the atmosphere (i.e. sublimation/condensation cycles), (2) wind effects (i.e. redistribution and pumping) and (3) exchanges with the firn below (i.e. metamorphism and diffusion).Here we present the data over several seasons and years of the atmospheric water vapor and snow surface isotopic composition at Dome C, East Antarctica. To understand the link between these two elements, we investigate the moisture fluxes at the surface of the ice sheet, at the snow-air interface. No eddy-covariance measurements are available for the recent years, we therefore make use of the available primary meteorological parameters measured continuously on site to estimate the surface moisture fluxes using the bulk method. We estimate that the cumulative effect of the moisture fluxes is positive: about 12% of the mean annual accumulation is sublimated away. Alongside, we see an enrichment in d18O in the snow surface during the summer months, when most of the moisture fluxes are taking place. The snow d-excess is also affected and evolving in anti-phase with d18O. This indicates occurrence of fractionation during sublimation in line with previous field and laboratory studies. The moisture fluxes could be a key driver of changes in the snow isotopic composition between precipitation events influencing the climate signal stored in the isotopic record of ice cores.

The water isotope composition of snow precipitations, archived in the Antarctic ice sheet every year, is an important proxy of climatic conditions. This signal depends on several parameters such as local temperature, altitude, moisture source areas and air mass pathways.However, especially in areas where snow accumulation is very low (as on the East Antarctic Plateau), the isotopic composition is affected by additional spatial variability induced by the interactions between the atmosphere and snow surface, and the pristine signal may be modified through isotopic exchanges, sublimation processes and mechanical mixing originated from wind action.Here, we present the isotopic composition (δD and δ18O) and the second-order parameter d-excess of surface snow and snowpit samples collected during the Italian-French campaign in Antarctica (2019-2020). The sampling sites cover the area from Dumont D'Urville to Concordia Station and from Concordia Station towards the South Pole (EAIIST – East Antarctic International Ice Sheet Traverse). These data, compared with a previous dataset of Antarctic surface snow isotopic composition (Masson-Delmotte et al. 2008), are analyzed to determine the variability of the spatial relationship between precipitation isotopic composition and local temperature in relation to geographical parameters (latitude, distance from the coast and elevation). The interpretation of these factors determining the isotope signature is the base to better define the amount of the effects caused by subsequent interaction between atmosphere and surface snow, and by the wind action.Understanding the spatial variability of this proxy, which strongly decreases the signal-to-noise ratio, could permit to improve the use of the “isotopic thermometer” to quantify past changes in temperature based on the stable isotopic record of deep ice cores.

Thinning of the deep ice core layers must be considered when the water isotopic composition of the Oldest Ice Core is to be analyzed. From an experimental point of view, a novel instrument combining a micro-destructive cold femtosecond - Laser Ablation (LA) sampling system, that provides high spatial resolution together with minimal usage of ice sample, and a Cavity Ring Down Spectrometer is being built for high-quality water isotope measurements. Laser ablation results in crater formation and its morphology depends on the laser parameters used. Optical images that show crater morphology under different experimental conditions allow crater characterization towards an efficient cold LA sampling. An ablation chamber and a transfer line are both the connecting parts between the LA system and the CRDS instrument. They are to be designed and constructed in the optimal size and shape to collect the ablated mass and guarantee its smooth delivery to the CRDS analyzer with minimum disturbance. Coupling a Laser Ablation system with a CRDS analyzer has already been achieved using a laser operating at the nanosecond regime and a cryo-cell as the ablation chamber. Comparison of the two Laser Ablation systems, by the means of ice sampling and collection of the ablated material, will be of great importance to understand the ablation mechanism and post-ablation processes on ice and further develop a system dedicated to water isotope measurements.

Water isotope ratios of ice cores are a key source of information on past temperatures. Through fractionation within the hydrological cycle, temperature is imprinted in the water isotopic composition of snowfalls. However, this signal of climatic interest is modified after deposition when snow remains at the surface exposed to the atmosphere. Comparing time series of surface snow isotopic composition at Dome C with satellite observations of surface snow metamorphism, we found that long summer periods without precipitation favor surface snow metamorphism altering the surface snow isotopic composition. Using excess parameters (combining dD, d17O, and d18O fractions) allow the identification of this alteration caused by sublimation and condensation of surface hoar. The combined measurement of all three isotopic compositions could help identifying ice core sections influenced by snow metamorphism in sites with very low snow accumulation.

Sunlit snow is highly photochemically active and plays a key role in the exchange of gas phase species between the cryosphere and the atmosphere. Bromine (Br), Iodine (I) and Mercury (Hg) can be photoactivated by the UV radiation and, in certain circumstances, released from the snowpack into the atmosphere. Mercury is a heavy metal with a known toxicity present in the environment in several different chemical forms. Once present in the snowpack, Hg is very labile and, thanks to the UV light, it can be reduced back to elemental Hg (Hg(0)) and undergo dynamic exchange with the atmosphere. Similar to mercury, iodine can undergo photochemical activation in surface snow resulting in its presence in the surrounding atmosphere where it plays a crucial role in new particle formation. Bromine has a central role in the mercury cycle in polar regions (through the Atmospheric mercury depletion events) as well as contributing to the tropospheric ozone cycle in the polar region causing the so-called Ozone depletion events. However, compared to Iodine and Mercury, it seems to be more stable after deposition into the snow pack. Here we present measurements of bromine, iodine and mercury performed by ICP-MS, on snow pit and shallow core samples taken over a 2100 km traverse in East Antarctica from the coast to the interior (Talos Dome – Dome C traverse 2016 and East Antarctic International Ice Sheet Traverse, EAIIST 2019). The shallow core and the snow pit samples at each site are estimated to cover about 10 to 20 years of snow accumulation, giving us a deposition record from approximately the late 90s, to around the early 21st century. The concentrations determined in different sampling sites show a rather clear decrease trend from the coast with the minima as we approach the inner part of the Antarctic plateau. In addition, the analysis of surface and bulk samples from EAIIST show a decrease of concentrations toward the inland except for the sites characterised by a strong snow metamorphosis caused mainly by the wind friction. In almost all the sampling sites of the EAIIST traverse the concentrations of Br, I and Hg increase with sample depth, possibly due to snowpack photochemical activation in the upper part of the snowpack. Future studies are planned to investigate the possible link between the determined concentration profile and the variation of the solar radiation reaching the Antarctic Plateau during spring caused by the ozone hole formation.

The growth and decay of marine ice sheets act as important controls on regional and global climate and sea level. The Wilkes Subglacial Basin ice sheet appears to have undergone thinning and ice discharge events during recent decades, but its past dynamics are still under debate. The aim of our study is to investigate ice margin retreat of the Wilkes Subglacial Basin ice sheet during late Pleistocene interglacials with the help of new high-resolution records from the TALDICE ice core. Here we present a multiproxy approach associated with modelling sensitivity experiments.The novel high-resolution δ18O signal reveals that interglacial periods MIS 7.5 and 9.3 are characterized by a unique double-peak feature, previously observed for MIS 5.5 (Masson-Delmotte et al., 2011), that is not seen in other Antarctic ice cores. A comparison with our GRISLI modelling results indicates that the Talos Dome site has probably undergone elevation variations of 100-400 m during past interglacials, with a major ice thickness variation during MIS 9.3, likely connected to a relevant margin retreat of the Wilkes Subglacial Basin ice sheet. To validate this elevation change hypothesis, the modelling outputs are compared to the ice-rafted debris record (IBRD) and the neodymium isotope signal from the U1361A sediment core (Wilson et al., 2018), which show that during MIS 5.5 and especially MIS 9.3, the Wilkes Subglacial Basin ice sheet has been subjected to ice discharge events.Overall, our results indicate that the interglacial double-peak δ18O signal could reflect decreases in Talos Dome site elevation during the late stages of interglacials due to Wilkes Subglacial Basin retreat events. These changes coincided with warmer Southern Ocean temperatures and elevated global mean sea level, confirming the sensitivity of the Wilkes Subglacial Basin ice sheet to ocean warming and its potential role in sea-level change.

The EPICA Dome C (EDC) ice core has been drilled from 1996 to 2004. Its study revealed a unique 800 ka long continuous climatic record including 9 deglaciations. Ice cores contain numerous proxies in the ice and in the air trapped in bubbles (chronological constraints, greenhouse gases concentration, local temperature proxies, mid to low latitude climate proxies).Here, we focus on the link between the high and low latitudes during the glacial/interglacial transitions provided by the isotopic composition of water and oxygen archived in both ice and gas matrix. On one hand, the water isotopic composition brings information on past temperatures and water cycle re-organizations: dD records past temperature, whereas the combination of d18O with dD or d17O provide information on the past water cycle organization through d-excess and 17O-excess linked to climatic conditions of the evaporative regions. On the other hand, the elemental composition of oxygen expressed in the O2/N2 ratio provides key information for orbital dating over the last 800 ka in complement with the isotopic composition of atmospheric oxygen (d18O of O2 or d18Oatm) which is related as well to the low latitude water cycle.In this study, we present new high resolution records of water isotopes of many proxies (d18O, d-excess and 17O-excess) as well as high resolution measurements of O2/N2 and d18Oatm over the last 9 deglaciations on the EDC ice core. We detail the coherent low to mid-latitude orbital patterns obtained using our multiproxy approach with a focus on Termination II, Termination V and the 800 – 500 ka. deglaciations. We look at the similar patterns between terminations and between the different proxies presented.

We present a novel application of empirical methodologies that significantly reduce the chronological uncertainty of a low latitude-high altitude Alpine ice core record obtained in 2011 from the glacier Alto dell’Ortles (3859 m, Eastern Alps, Italy). A preliminary absolute timescale based on a peak in 3H activity, and 210Pb and 14C analyses on carbonaceous particles and organic remains provided evidence of one of the oldest Alpine ice core records spanning the last ~7000 years, back to the last Northern Hemisphere Climatic Optimum. Here we combine three empirical methods that provide an additional number of time markers that corroborate the multimillennial nature of the Alto dell’Ortles ice cores while significantly decreasing the uncertainty of the chronology. First, 14C analysis of an additional organic fragment (a charred spruce needle) discovered next to the basal ice provides an age (232 ± 126 BCE) which agrees with previous 14C dates in the oldest part of the record. Second, a new millennial-scale high resolution atmospheric Pb depositional record was used to synchronize the Alto dell’Ortles cores with an accurately-dated (±5 years) Pb record from an array of Arctic ice cores during the ~200 BCE to ~1900 CE time period. This match resulted in a shift of the initial Alto dell’Ortles timescale ~200 years earlier, but still within the initial time uncertainty. Third, novel seasonally resolved pollen records from the upper firn/ice portion of the Alto dell’Ortles cores were combined with δ18O and dust annual variations to refine the dating for the 20th century by means of an automatic algorithm (Straticounter; between 2011 and 1927 CE) and visual counting (1926–1900 CE). The time markers obtained by these three methods were combined in a continuous timescale by running a Montecarlo based fit (COPRA model). This Alto dell’Ortles revised chronology shows a significantly reduced uncertainty, between ±1 and ±4 years after 1927 CE, and between a maximum of ±100 years to a minimum of ±5 years between 1927 CE and 200 BCE by conservative estimates. An investigation of the revised chronology by means of a simple 1-D flow model suggests that non-steady-state conditions (e.g., changes in past snow accumulation rate) need to be considered to provide a full physical explanation of the age-depth relationship obtained. The new revised chronology will allow the constraint of the Holocene climatic and environmental histories emerging from this high-altitude glacial archive of Central Europe. The novel methodologies may also be adopted to build or improve the chronologies of other ice cores extracted from-low latitude/high-altitude glaciers that typically suffer from larger dating uncertainties compared with well dated polar records.

The EPICA Dome C (EDC) ice core has been drilled from 1996 to 2004. Its study revealed a unique 800 ka long continuous climatic record including 9 deglaciations. Ice cores contain numerous proxies in the ice and in the air trapped in bubbles (chronological constraints, greenhouse gases concentration, local temperature proxies, mid to low latitude climate proxies). Here, we focus on information provided by the isotopic (and elemental) composition of water and oxygen archived in both ice and gas matrix. On one hand, the water isotopic composition brings information on past temperatures and water cycle re-organizations: d18O or dD records past temperature, whereas the combination of d18O with dD or d17O provide information on the past water cycle organization through d-excess and 17O-excess linked to climatic conditions of the evaporative regions. On the other hand, the elemental composition of oxygen expressed in the O2/N2 ratio provides key information for orbital dating over the last 800 ka in complement with the isotopic composition of atmospheric oxygen (d18O of O2 or d18Oatm) which is related as well to the low latitude water cycle.In this study, we present new high resolution records of water isotopes (d18O, d-excess and 17O-excess) as well as high resolution measurements of O2/N2 and d18Oatm over the last 9 deglaciations on the EDC ice core. We first use the high resolution records of O2/N2 and d18Oatm to improve absolute dating constrain over the glacial terminations and discuss the link between orbital forcing and climate variations recorded in the EDC ice core. In a second part, we use d-excess, 17O-excess and d18Oatm to constrain the relative chronology of high vs low latitude climatic events at sub-millennial scale over past deglaciations.

The growth and decay of marine ice sheets act as important controls on regional and global climate, in particular, the behavior of the ice sheets is a key uncertainty in predicting sea-level rise during and beyond this century. The East Antarctic Ice Sheet (EAIS), which contains deep subglacial basins with reverse-sloping, is considered to be susceptible to ice loss caused by marine ice sheet instability. Sediment core offshore Wilkes Subglacial Basin reveals oscillations in the provenance of detrital sediment that have been interpreted to reflect an erosion of Wilkes Basin during interglacial periods MIS 5, MIS 7, and MIS 9 greater than Holocene period (Wilson et al., 2018). The aim of our study is to investigate past climate and environmental changes in the coastal area of the East Antarctic Ice Sheet during MIS 7.5 and 9.3 with the help of a new high-resolution water isotopes record of the TALDICE ice core.Here we present new δ18O and δD high resolution (5 cm) records covering the oldest portion of the TALDICE ice core. MIS 7.5 and 9.3 isotopic signal reveals a unique feature, already observed for MIS 5.5, that has not been spotted in other Antarctic ice cores (Masson-Delmotte et al., 2011). Interglacial periods at TALDICE are characterized by a first peak, observed in correspondence to the culmination of the deglaciation event as for all Antarctic cores, followed by a less pronounced isotopic peak (for MIS 5.5 and 9.3) or a plateau (for MIS 7.5) prior to the glacial inception. Several factors might drive this peculiar behavior of the water stable isotopes record, as an increase in temperatures due to a drop in surface elevation or changes in moisture sources.The new δ18O and δD high-resolution records for the TALDICE ice core reveal a unique pattern that characterizes interglacial periods at Talos Dome. Taking into account the coastal position of the core and its vicinity to the Wilkes Subglacial Basin we intend to investigate the possible decrease in surface elevation, through the application of the GRISLI ice sheet model (Quiquet et al., 2018), and changes in moisture sources, traceable from the d-excess record.

Stable water isotopes are widely-used tracers to investigate hydrological processes occurring in the atmosphere and to determine the geospatial origin of water, i.e. to acquire useful information about the hydrological cycles over catchment basins and to find the origin of water recharging rivers, aquifers, and springs. Mapping the isotopic composition of precipitation provides hydrological and climate information at regional and global scales. However, the isotopic composition of precipitation is usually analyzed at large scales with a limited spatial resolution. In Italy, a few studies mapped the oxygen stable isotopes using annually-averaged data, not accounting for the strong seasonality of the isotopic composition linked to climatic and weather factors. To partially fill this gap, the present study proposes a detailed analysis of more than 2250 isotope data (δ18O, δ2H, and deuterium excess) related to precipitations collected in the Friuli Venezia Giulia (FVG) region (Italy) with monthly or seasonal frequency in 36 sites between 1984 and 2015.The FVG region lies at the north-eastern end of Italy, bordering Austria in the North and Slovenia in the East, and extends over ~7.9·103 km2. From a hydrogeological point of view, FVG is an interesting case study. Large highly-permeable carbonate aquifers are present in the Alps and Prealps, while the southern part of the region is characterized by an alluvial plain, split by the spring belt into two sectors: the High Plain in the North, characterized by an highly-permeable unconfined aquifer, and the Low Plain in the South, characterized by a system of confined and artesian aquifers. All the aquifers are recharged by the effective precipitations which in the FVG exhibits among the highest annual precipitation rates in Italy (with peaks >3000 mm/year).For the present research, the isotopic data were used: (i) to analyze the spatial and seasonal variability of isotopic composition; (ii) to relate water isotopes with orography and weather parameters collected from meteorological stations as well as using ECMWF ERA5 reanalysis; (iii) to reconstruct the local meteoric water lines across the FVG at annual and seasonal bases; (iv) to quantify interannual trends and analyze their spatial distribution; and (iv) to model the spatial distribution of isotope content in precipitation and create annual and seasonal maps.

The iconic curve of D in water showing the 8 glacial/interglacial cycles from the EPICA Dome C icecore is now a reference in paleoclimate. It shows past temperature variability back to 800 ka over the3200 m deep ice core with a 55 cm resolution. However, the millennial and centennial scalevariability gets more challenging to observe in the deepest part of the core. Indeed, the timeresolution worsens when going deeper in the ice because of the ice thinning: it is larger than 200years at 2500 m depth. Furthermore, isotopic diffusion affects the signal at the bottom of the icecore. Pol et al., (2010) have thus shown that the sub-millennial MIS (Marine Isotopic Stage) 19 signal(3157-3181 m deep) is erased because of diffusion and high resolution doesn’t add any furtherinformation at this depth. In this study we want to better characterize the increase of the isotopicdiffusion with depth by providing new high resolution water isotopes at several intervals over theEPICA ice core (EDC).We present here published high resolution (11 cm) d18O measurements over the EDC ice core aswell as new records of high resolution (11 cm) D over MIS 7;13 and 14). We use spectral analyses todetermine at which depth the isotopic diffusion erases the sub-millennial variability. We also showthat cold periods exhibit a larger variability of water isotopes than interglacial periods.The information obtained here is crucial for the new project Beyond EPICA oldest ice core, which hasthe goal of analyzing a 1.5 Ma old ice core. In the deepest part, 1 m of ice core could represent10 000 years of climate archive.

The study of the deep portions of ice cores still represents a poorly explored field due to the presence of processes acting in the lowermost layers and possibly affecting the preservation of the original climatic signal. For the 1620 m TALDICE ice core, drilled at Talos Dome (East Antarctica), the high-resolution climate reconstruction and chronology definition are available only until the depth of ~1450 m (150 kyr BP) (Stenni et al., 2011, Bazin et al., 2013). Our aim is to investigate the portion below 1460 m depth to the bottom of the core, where radargrams show the presence of an unconformity in the ice sheet, to define a preliminary chronology and identify a discernible climatic signal.Here we present the new TALDICE δ18Oatm record in the air bubbles, in association with the new high-resolution δ18Oice and δDice profiles and an 81Kr radiometric date. New 46 measurements of δ18Oatm allowed to increase the resolution of the available profile from 1357 to 1553.95 m depth and to extend the record till the bottom of the core at 1617 m depth. The comparison between the δ18Oatm profile of TALDICE and the one of EPICA Dome C (EDC) ice core (Extier et al., 2018) allows to solidly define a preliminary age-depth relationship for the TALDICE core until 1500 m depth, where the gas age is estimated to be ~200 kyr BP. Below 1500 m, supplementary δ18Oatm measurements will be needed to identify older precession cycles and to extend the age-depth relationship further back in time. On the other hand, the high-resolution isotopic profiles in the ice (18O/16O and D/H ratios) obtained below the depth of 1528 m and compared with the EDC ones suggest that the climatic signal in the ice is preserved until to the lower level of 1547.8 m, which is dated back to 343 kyr BP. However, the lack of similarities with the EDC water isotopes record below this depth, in spite of the 81 Kr radiometric age 459 ± 50 kyr BP at the depth of 1574-1578 m, indicates the missing of the MIS 11 in the isotopic profiles. Moreover, the increase of high-frequency variability in the δ18Oice and δDice below 1547.8 m depth implies that this part of the core lays in an area of the ice sheet characterized by different properties in comparison to the ice above.Additional δ18Oatm, 40Ar, δ18Oice, and δDice measurements will be performed in the lowermost portion of the core and the results will be compared with the new 81Kr radiometric dating at the depth of 1560-1564 m and 1614-1619 m to better constrain the chronology and to investigate the ice properties in the deeper portion of the core.

Paleoclimate reconstructions from ice core records can be hampered due to the lack of a reliable chronology, especially when the stratigraphy is disturbed and conventional dating methods are not readily applied. The noble gas radioisotopes 81Kr and 39Ar can in these cases provide robust constraints as they yield absolute, radiometric ages. 81Kr (half-life 229 ka) covers the time span from 50-1300 ka, which is particularly relevant for polar ice cores, whereas 39Ar (half-life 269 a) with a dating range of 50-1400 a is suitable for high mountain glaciers. For a long time the use of 81Kr and 39Ar for dating of ice samples was hampered by the lack of a detection technique that can meet its extremely small abundance at a reasonable sample size. Here, we report on 81Kr and 39Ar dating of Antarctic and Tibetan ice cores with the detection method Atom Trap Trace Analysis (ATTA), using 5-10 kg of ice for 81Kr and 2-5 kg for 39Ar. Among others, we measured 81Kr in the lower section of Taldice ice core, which is difficult to date by conventional methods, and in the meteoric bottom of the Vostok ice core in comparison with an age scale derived from hydrate growth. Moreover, we have obtained an 39Ar profile for an ice core from central Tibet in combination with a timescale constructed by layer counting. The presented studies demonstrate how the obtained 81Kr and 39Ar ages can complement other methods in developing an ice core chronology, especially for the bottom part.[1] Z.-T. Lu, Tracer applications of noble gas radionuclides in the geosciences, Earth-Science Reviews 138, 196-214, (2014)[2] C. Buizert, Radiometric 81Kr dating identifies 120,000-year-old ice at Taylor Glacier, Antarctica, Proceedings of the National Academy of Sciences, 111, 6876, (2014)[3] L. Tian, 81Kr Dating at the Guliya Ice Cap, Tibetan Plateau, Geophysical Research Letters, (2019)[4] http://atta.ustc.edu.cn

The Antarctic temperature changes over the past millennia remain more uncertain than in many other continental regions. This has several origins: 1) the number of high resolution ice cores is small, in particular on the Antarctic Plateau and in some coastal areas in East Antarctica; 2) the short instrumental records limit the calibration period for reconstructions and the assessment of the methodologies; 3) the link between isotope records from ice cores and local climate is usually complex and dependent on the spatial and time scales investigated. Here, we use climate model results, pseudoproxy and data assimilation experiments to assess the potential of reconstructing the Antarctic temperature over the last two millennia based on a new database of stable oxygen isotopes in ice cores compiled in the framework of Antarctica2k (Stenni et al., 2017). The well-known covariance between δ18O and temperature is reproduced in the two isotope-enabled models used (ECHAM5/MPI-OM and ECHAM5-wiso), but is generally weak over the different Antarctic regions, limiting the skill of the reconstructions. Furthermore, the strength of the link displays large variations over the past millennium, further affecting the potential skill of temperature reconstructions based on statistical methods which rely on the assumption that the last decades are a good estimate for longer temperature reconstructions. Using a data assimilation technique allows in theory taking into account changes in the δ18O-temperature link through time and space. Pseudoproxy experiments confirm the benefits of using data assimilation methods instead of statistical ones that provide reconstructions with unrealistic variances in some Antarctic subregions. They also confirm that the relatively weak link between both variables leads to a limited potential for reconstructing temperature based on δ18O. The reconstruction skill is however higher and more uniform among reconstruction methods when the reconstruction target is the Antarctic as a whole rather than smaller Antarctic subregions. This consistency between the methods at the large scale is also observed when reconstructing temperature based on the real δ18O regional composites of Stenni et al. (2017). In this case, temperature reconstructions based on data assimilation confirm the long term cooling over Antarctica during the last millennium, and the later onset of anthropogenic warming compared to the simulations without data assimilation, especially visible in West Antarctica. Data assimilation also allows reconciling models and direct observations by reconstructing the East-West contrast regarding the recent temperature trends, indicating that internal variability likely plays a major role in driving this heterogeneous recent warming. This is further supported by the large spread of individual PMIP/CMIP model realizations regarding the recent warming pattern. As in the pseudoproxy framework, the reconstruction methods perform differently at the subregional scale, especially in terms of the variance of the produced time series. While the potential benefits of using a data assimilation method instead of a statistical one have been highlighted in a pseudoproxy framework, the instrumental series are too short to confirm it in a realistic setup.

Here we review Antarctic snow accumulation variability, at the regional scale, over the past 1000 years. A total of 80 ice core snow accumulation records were gathered, as part of a community led project coordinated by the PAGES Antarctica 2k working group. The ice cores were assigned to seven geographical regions, separating the high accumulation coastal zones below 2000 m elevation from the dry central Antarctic Plateau. The regional composites of annual snow accumulation were evaluated against modelled surface mass balance (SMB) from RACMO2.4 and precipitation from ERA-interim reanalysis. With the exception of the Weddell Sea coast, the low-elevation composites capture the regional precipitation and SMB variability. The central Antarctic sites lack coherency and are either not representing regional precipitation or indicate the models inability to capture relevant precipitation processes in the cold, dry central plateau. The drivers of precipitation are reviewed for each region and the temporal variability and trends evaluated over the past 100, 200 and 1000 years. Our study suggests an overall increase in SMB across the grounded Antarctic ice sheet of ~ 44 GT since 1800 AD, with the largest (area-weighted) contribution from the Antarctic Peninsula (AP). Only four ice core records cover the full 1000 years and suggest a decrease in snow accumulation during this period. However, our study emphasizes the importance of low elevation coastal zones (especially AP and DML), which have been underrepresented in previous investigations of temporal snow accumulation.

Climate trends in the Antarctic region remain poorly characterised, owing to the brevity and scarcity of direct climate observations and the large magnitude of interannual to decadal-scale climate variability. Here, within the framework of the PAGES Antarctica 2k working group, we build an enlarged database of ice core water stable isotope records from Antarctica, consisting of 112 records. We produce both unweighted and weighted isotopic (δ18O) composites and temperature reconstructions since 0 CE, binned at 5 and 10-year resolution, for 7 climatically-distinct regions covering the Antarctic continent. Following earlier work of the Antarctica 2k working group, we also produce composites and reconstructions for the broader regions of East Antarctica, West Antarctica, and the whole continent. We use three methods for our temperature reconstructions: i) a temperature scaling based on the δ18O-temperature relationship output from an ECHAM5-wiso model simulation nudged to ERA-interim atmospheric reanalyses from 1979 to 2013, and adjusted for the West Antarctic Ice Sheet region to borehole temperature data; ii) a temperature scaling of the isotopic normalized anomalies to the variance of the regional reanalysis temperature and iii) a composite-plus-scaling approach used in a previous continental scale reconstruction of Antarctic temperature since 1 CE but applied to the new Antarctic ice core database. Our new reconstructions confirm a significant cooling trend from 0 to 1900 CE across all Antarctic regions where records extend back into the 1st millennium, with the exception of the Wilkes Land coast and Weddell Sea coast regions. Within this long-term cooling trend from 0–1900 CE we find that the warmest period occurs between 300 and 1000 CE, and the coldest interval from 1200 to 1900 CE. Since 1900 CE, significant warming trends are identified for the West Antarctic Ice Sheet, the Dronning Maud Land coast and the Antarctic Peninsula regions, and these trends are robust across the distribution of records that contribute to the unweighted isotopic composites and also significant in the weighted temperature reconstructions. Only for the Antarctic Peninsula is this most recent century-scale trend unusual in the context of natural variability over the last 2000-years. However, projected warming of the Antarctic continent during the 21st Century may soon see significant and unusual warming develop across other parts of the Antarctic continent. The extended Antarctica 2k ice core isotope database developed by this working group opens up many avenues for developing a deeper understanding of the response of Antarctic climate to natural and anthropogenic climate forcings. The first long-term quantification of regional climate in Antarctica presented herein is a basis for data-model comparison and assessments of past, present and future driving factors of Antarctic climate.

Stable water isotopes (δ18O) obtained from snow and ice samples of polar regions are used to reconstruct past climate variability, but heat and mass transport processes can affect the isotopic composition. Here we present an experimental study on the effect on the snow isotopic composition by airflow through a snow pack in controlled laboratory conditions. The influence of isothermal and controlled temperature gradient conditions on the δ18O content in the snow and interstitial water vapor is elucidated. The observed disequilibrium between snow and vapor isotopes led to exchange of isotopes between snow and vapor under non-equilibrium processes, significantly changing the δ18O content of the snow. The type of metamorphism of the snow had a significant influence on this process. These findings are pertinent to the interpretation of the records of stable isotopes of water from ice cores. These laboratory measurements suggest that a highly resolved history is relevant for the interpretation of the snow isotopic composition in the field.

Water stable isotopes in Greenland ice core data provide key paleoclimatic information, and have been compared with precipitation isotopic composition simulated by isotopically enabled atmospheric models. However, post-depositional processes linked with snow metamorphism remain poorly documented. For this purpose, monitoring of the isotopic composition (δ18O, δD) of near-surface water vapor, precipitation and samples of the top (0.5 cm) snow surface has been conducted during two summers (2011–2012) at NEEM, NW Greenland. The samples also include a subset of 17O-excess measurements over 4 days, and the measurements span the 2012 Greenland heat wave. Our observations are consistent with calculations assuming isotopic equilibrium between surface snow and water vapor. We observe a strong correlation between near-surface vapor δ18O and air temperature (0.85 ± 0.11‰ °C−1 (R = 0.76) for 2012). The correlation with air temperature is not observed in precipitation data or surface snow data. Deuterium excess (d-excess) is strongly anti-correlated with δ18O with a stronger slope for vapor than for precipitation and snow surface data. During nine 1–5-day periods between precipitation events, our data demonstrate parallel changes of δ18O and d-excess in surface snow and near-surface vapor. The changes in δ18O of the vapor are similar or larger than those of the snow δ18O. It is estimated using the CROCUS snow model that 6 to 20% of the surface snow mass is exchanged with the atmosphere. In our data, the sign of surface snow isotopic changes is not related to the sign or magnitude of sublimation or deposition. Comparisons with atmospheric models show that day-to-day variations in near-surface vapor isotopic composition are driven by synoptic variations and changes in air mass trajectories and distillation histories. We suggest that, in between precipitation events, changes in the surface snow isotopic composition are driven by these changes in near-surface vapor isotopic composition. This is consistent with an estimated 60% mass turnover of surface snow per day driven by snow recrystallization processes under NEEM summer surface snow temperature gradients. Our findings have implications for ice core data interpretation and model–data comparisons, and call for further process studies.

This study evaluated between-sample memory in isotopic measurements of δ2H and δ18O in water samples by laser spectroscopy. Ten isotopically depleted water samples spanning a broad range of oxygen and hydrogen isotopic compositions were measured by three generations of off-axis integrated cavity output spectroscopy and cavity ring-down spectroscopy instruments. The analysis procedure encompassed small (less than 2‰ for δ2H and 1‰ for δ18O) and large (up to 201‰ for δ2H and 25‰ for δ18O) differences in isotopic compositions between adjacent sample vials. Samples were injected 18 times each, and the between-sample memory effect was quantified for each analysis run. Results showed that samples adversely affected by between-sample isotopic differences stabilised after seven–eight injections. The between-sample memory effect ranged from 14% and 9% for δ2H and δ18O measurements, respectively, but declined to negligible carryover (between 0.1% and 0.3% for both isotopes) when the first ten injections of each sample were discarded. The measurement variability (range and standard deviation) was strongly dependent on the isotopic difference between adjacent vials. Standard deviations were up to 7.5‰ for δ2H and 0.54‰ for δ18O when all injections were retained in the computation of the reportable δ-value, but a significant increase in measurement precision (standard deviation in the range 0.1‰–1.0‰ for δ2H and 0.05‰–0.17‰ for δ18O) was obtained when the first eight injections were discarded. In conclusion, this study provided a practical solution to mitigate between-sample memory effects in the isotopic analysis of water samples by laser spectroscopy.

We measured δ17O and δ18O in two Antarctic ice cores at EPICA Dome C (EDC) and TALDICE (TD), respectively, and computed 17O-excess with respect to VSMOW. The comparison of our 17O-excess data with the previous record obtained at Vostok (Landais et al., 2008a) revealed differences up to 35 ppm in 17O-excess mean level and evolution for the three sites. Our data show that the large increase depicted at Vostok (20 ppm) during the last deglaciation is a regional and not a general pattern in the temporal distribution of 17O-excess in East Antarctica. The EDC data display an increase of 12 ppm, whereas the TD data show no significant variation from the Last Glacial Maximum (LGM) to the Early Holocene (EH). A Lagrangian moisture source diagnostic revealed very different source regions for Vostok and EDC compared to TD. These findings combined with the results of a sensitivity analysis, using a Rayleigh-type isotopic model, suggest that normalized relative humidity (RHn) at the oceanic source region (OSR) is a determining factor for the spatial differences of 17O-excess in East Antarctica. However, 17O-excess in remote sites of continental Antarctica (e.g. Vostok) may be highly sensitive to local effects. Hence, we consider 17O-excess in coastal East Antarctic ice cores (TD) to be more reliable as a proxy for RHn at the OSR.

Documenting past changes in the East Antarctic surface mass balance is important to improve ice core chronologies and to constrain the ice sheet contribution to global mean sea level. Here we reconstruct the past changes in the ratio of surface mass balance (SMB ratio) between the EPICA Dome C (EDC) and Dome Fuji (DF) East Antarctica ice core sites, based on a precise volcanic synchronisation of the two ice cores and on corrections for the vertical thinning of layers. During the past 216 000 years, this SMB ratio, denoted SMBEDC/SMBDF, varied between 0.7 and 1.1, decreasing during cold periods and increasing during warm periods. While past climatic changes have been depicted as homogeneous along the East Antarctic Plateau, our results reveal larger amplitudes of changes in SMB at EDC compared to DF, consistent with previous results showing larger amplitudes of changes in water stable isotopes and estimated surface temperature at EDC compared to DF. Within interglacial periods and during the last glacial inception (Marine Isotope Stages, MIS-5c and MIS-5d), the SMB ratio deviates by up to 30% from what is expected based on differences in water stable isotope records. Moreover, the SMB ratio is constant throughout the late parts of the current and last interglacial periods, despite contrasting isotopic trends. These SMB ratio changes not closely related to isotopic changes are one of the possible causes of the observed gaps between the ice core chronologies at DF and EDC. Such changes in SMB ratio may have been caused by (i) climatic processes related to changes in air mass trajectories and local climate, (ii) glaciological processes associated with relative elevation changes, or (iii) a combination of climatic and glaciological processes, such as the interaction between changes in accumulation and in the position of the domes. Our inferred SMB ratio history has important implications for ice sheet modeling (for which SMB is a boundary condition) or atmospheric modeling (our inferred SMB ratio could serve as a test).

From 10 to 8 ka BP (thousand years before present), paleoclimate records show an atmospheric and oceanic cooling in the high latitudes of the Southern Hemisphere. During this interval, temperatures estimated from proxy data decrease by 0.8 °C over Antarctica and 1.2 °C over the Southern Ocean. In order to study the causes of this cooling, simulations covering the early Holocene have been performed with the climate model of intermediate complexity LOVECLIM constrained to follow the signal recorded in climate proxies using a data assimilation method based on a particle filtering approach. The selected proxies represent oceanic and atmospheric surface temperature in the Southern Hemisphere derived from terrestrial, marine and glaciological records. Two mechanisms previously suggested to explain the 10–8 ka BP cooling pattern are investigated using the data assimilation approach in our model. The first hypothesis is a change in atmospheric circulation, and the second one is a cooling of the sea surface temperature in the Southern Ocean, driven in our experimental setup by the impact of an increased West Antarctic melting rate on ocean circulation. For the atmosphere hypothesis, the climate state obtained by data assimilation produces a modification of the meridional atmospheric circulation leading to a 0.5 °C Antarctic cooling from 10 to 8 ka BP compared to the simulation without data assimilation, without congruent cooling of the atmospheric and sea surface temperature in the Southern Ocean. For the ocean hypothesis, the increased West Antarctic freshwater flux constrainted by data assimilation (+100 mSv from 10 to 8 ka BP) leads to an oceanic cooling of 0.7 °C and a strengthening of Southern Hemisphere westerlies (+6%). Thus, according to our experiments, the observed cooling in Antarctic and the Southern Ocean proxy records can only be reconciled with the reconstructions by the combination of a modified atmospheric circulation and an enhanced freshwater flux.

A single isotope ratio (δD or δ18O) of water is widely used as an air-temperature proxy in Antarctic ice cores. These isotope ratios, however, do not solely depend on air-temperature but also on the extent of distillation of heavy isotopes out of atmospheric water vapor from an oceanic moisture source to a precipitation site. The temperature changes at the oceanic moisture source (ΔTsource) and at the precipitation site (ΔTsite) can be retrieved by using deuterium-excess (d) data. A new d record from Dome Fuji, Antarctica is produced spanning the past 360 000 yr and compared with records from Vostok and EPICA Dome C ice cores. To retrieve ΔTsource and ΔTsite information, different linear regression equations have been proposed using theoretical isotope distillation models. A major source of uncertainty lies in the coefficient of regression, βsite which is related to the sensitivity of d to ΔTsite. We show that different ranges of temperature and selections of isotopic model outputs may increase the value of βsite by a factor of two. To explore the impacts of this coefficient on the reconstructed temperatures, we apply for the first time the exact same methodology to the isotope records from the three Antarctica ice cores. We show that uncertainties in the βsite coefficient strongly affect (i) the glacial-interglacial magnitude of ΔTsource; (ii) the imprint of obliquity in ΔTsource and in the site-source temperature gradient. By contrast, we highlight the robustness of ΔTsite reconstruction using water isotopes records.

We expand here the description of the Antarctic temperature variability during the long interglacial period occurring ~400 thousand years before present (Marine Isotopic Stage, MIS 11). This is achieved thanks to new detailed deuterium measurements conducted on the EPICA Dome C ice core, Antarctica, with a ~50 year temporal resolution. Despite an ice diffusion length reaching ~8 cm at MIS 11 depth, the data allow to highlight a variability at multi-centennial scale for MIS 11, as it has already been observed for the Holocene (MIS 1). Differences between MIS 1 and MIS 11 are analysed regarding the links between multi-millennial trends and sub-millennial variability. The EPICA Dome C deuterium record shows an increased variability and a shift in the observed periodicities at the onset of the final cooling phase of MIS 11, with stronger millennial to multi-millennial variability. Our findings are robust with respect to sensitivity tests on the somewhat uncertain MIS 11 duration.

The aim of this study was to analyse the reproducibility of off-axis integrated cavity output spectroscopy (OA-ICOS)-derived δ2H and δ18O measurements on a set of 35 water samples by comparing the performance of four laser spectroscopes with the performance of a conventional mass spectrometer under typical laboratory conditions. All samples were analysed using three different schemes of standard/sample combinations and related data processing to assess the improvement of results compared with mass spectrometry. The repeatability of the four OA-ICOS instruments was further investigated by multiple analyses of a sample subset to evaluate the stability of δ2H and δ18O measurements. Results demonstrated an overall agreement between OA-ICOS-based and mass spectrometry-based measurements for the entire dataset. However, a certain degree of variability existed in precision and accuracy between the four instruments. There was no evident bias or systematic deviations from the mass spectrometer values, but random errors, which were apparently not related to external factors, significantly affected the final results. Our investigation revealed that analytical precision ranged from ±0.56‰ to 1.80‰ for δ2H and from ±0.10‰ to 0.27‰ for δ18O measurements, with a marked variability among the four instruments. The overall capability of laser instruments to reproduce stable results with repeated measurements of the same sample was acceptable, and there were general differences within the range of the analytical precision for each spectroscope. Hence, averaging the measurements of three identical samples led to a higher degree of accuracy and eliminated the potential for random deviations.