A refined TALDICE-1a age scale from 55 to 112 ka before present for the Talos Dome ice core based on high-resolution methane measurements

A precise synchronization of different climate records is indispensable for a correct dynamical interpretation of paleoclimatic data. A chronology for the TALDICE ice core from the Ross Sea sector of East Antarctica has recently been presented based on methane synchronization with Greenland and the EDC ice cores and δ18Oice synchronization with EDC in the bottom part (TALDICE-1). Using new high-resolution methane data obtained with a continuous flow analysis technique, we present a refined age scale for the age interval from 55–112 thousand years (ka) before present, where TALDICE is synchronized with EDC. New and more precise tie points reduce the uncertainties of the age scale from up to 1900 yr in TALDICE-1 to below 1100 yr over most of the refined interval and shift the Talos Dome dating to significantly younger ages during the onset of Marine Isotope Stage 3. Thus, discussions of climate dynamics at sub-millennial time scales are now possible back to 110 ka, in particular during the inception of the last ice age. Calcium data of EDC and TALDICE are compared to show the impact of the refinement to the synchronization of the two ice cores not only for the gas but also for the ice age scale.

Water isotopic ratios from a continuously melted ice core sample

A new technique for on-line high resolution isotopic analysis of liquid water, tailored for ice core studies is presented. We built an interface between a Wavelength Scanned Cavity Ring Down Spectrometer (WS-CRDS) purchased from Picarro Inc. and a Continuous Flow Analysis (CFA) system. The system offers the possibility to perform simultaneuous water isotopic analysis of δ18O and δD on a continuous stream of liquid water as generated from a continuously melted ice rod. Injection of sub μl amounts of liquid water is achieved by pumping sample through a fused silica capillary and instantaneously vaporizing it with 100% efficiency in a~home made oven at a temperature of 170 °C. A calibration procedure allows for proper reporting of the data on the VSMOW–SLAP scale. We apply the necessary corrections based on the assessed performance of the system regarding instrumental drifts and dependance on the water concentration in the optical cavity. The melt rates are monitored in order to assign a depth scale to the measured isotopic profiles. Application of spectral methods yields the combined uncertainty of the system at below 0.1‰ and 0.5‰ for δ18O and δD, respectively. This performance is comparable to that achieved with mass spectrometry. Dispersion of the sample in the transfer lines limits the temporal resolution of the technique. In this work we investigate and assess these dispersion effects. By using an optimal filtering method we show how the measured profiles can be corrected for the smoothing effects resulting from the sample dispersion. Considering the significant advantages the technique offers, i.e. simultaneuous measurement of δ18O and δD, potentially in combination with chemical components that are traditionally measured on CFA systems, notable reduction on analysis time and power consumption, we consider it as an alternative to traditional isotope ratio mass spectrometry with the possibility to be deployed for field ice core studies. We present data acquired in the field during the 2010 season as part of the NEEM deep ice core drilling project in North Greenland.

Continuous measurements of methane mixing ratios from ice cores

This work presents a new, field-deployable technique for continuous, high-resolution measurements of methane mixing ratios from ice cores. The technique is based on a continuous flow analysis system, where ice core samples cut along the long axis of an ice core are melted continuously. The past atmospheric air contained in the ice is separated from the melt water stream via a system for continuous gas extraction. The extracted gas is dehumidified and then analyzed by a Wavelength Scanned-Cavity Ring Down Spectrometer for methane mixing ratios. We assess the performance of the new measurement technique in terms of precision (±0.8 ppbv, 1σ), accuracy (±8 ppbv), temporal (ca. 100 s), and spatial resolution (ca. 5 cm). Using a firn air transport model, we compare the resolution of the measurement technique to the resolution of the atmospheric methane signal as preserved in ice cores in Greenland. We conclude that our measurement technique can resolve all climatically relevant variations as preserved in the ice down to an ice depth of at least 1980 m (66 000 yr before present) in the North Greenland Eemian Ice Drilling ice core. Furthermore, we describe the modifications, which are necessary to make a commercially available spectrometer suitable for continuous methane mixing ratio measurements from ice cores.

A technique for continuous detection of drill liquid in ice cores

When drilling ice cores deeper than ∼100 m, drill liquid is required to maintain ice-core quality and to limit borehole closure. Due to high-pressure air bubbles in the ice, the ice core can crack during drilling and core retrieval, typically at 600–1200 m depth in Greenland. Ice from this 'brittle zone' can be contaminated by drill liquid as it seeps through cracks into the core. Continuous flow analysis (CFA) systems are routinely used to analyse ice for chemical impurities, so the detection of drill liquid is important for validating accurate measurements and avoiding potential instrument damage. An optical detector was constructed to identify drill liquid in CFA tubing by ultraviolet absorption spectroscopy at a wavelength of 290 nm. The set-up was successfully field-tested in the frame of the NEEM ice-core drilling project in Greenland. A total of 27 cases of drill liquid contamination were identified during the analysis of 175 m of brittle zone ice. The analyses most strongly affected by drill liquid contamination include insoluble dust particles, electrolytic conductivity, ammonium, hydrogen peroxide and sulphate. This method may also be applied to other types of drill liquid used at other drill sites.

Aeolian dust and chemistry records from the EDML and EDC ice cores

To improve quantitative interpretation of ice core aeolian dust records a systematic methodical comparison has been made involving methods of water-insoluble particle counting (Coulter Counter and laser-sensing particle detector), soluble ions (ion chromatography, IC, and continuous flow analysis, CFA), elemental analysis (inductively coupled plasma mass spectroscopy, ICP-MS, at pH 1 and after full acid digestion), and water-insoluble elemental analysis (proton induced X-ray emission, PIXE). Ice core samples covering the last deglaciation have been used from the EPICA Dome C (EDC) and the EPICA Dronning Maud Land (EDML) ice cores. All methods correlate very well amongst each other. The ratios of glacial age concentrations to Holocene concentrations, which are typically a factor ~100, differ significantly between the methods, but differences are limited to a factor < 2 for most methods with insoluble particles showing the largest change. The recovery of ICP-MS measurements depends on the digestion method and is different for different elements and during different climatic periods. EDC and EDML samples have similar dust composition, which suggests a common dust source or a common mixture of sources for the two sites. The analysed samples further reveal a change of dust composition during the last deglaciation.

Chemistry record of icecore BER11C95_25

A 181 m deep ice core drilled in 1994/95 on the south dome of Berkner Island, Antarctica, was analyzed for stable isotopes, major ions and microparticle concentrations. Samples for ion chromatography were prepared by using a novel technique of filling decontaminated sample from a device for continuous ice-core melting directly into the sample vials. The core was dated through identification of volcanic horizons and interpolative layer counting. The core, together with a similar core from the north dome, reveals a 1000 year history of relatively stable climate. Temporal variations in the two cores deviate from each other owing to changing patterns of regional-scale circulation; the best correspondence between them is found for MSA-. delta18O, accumulation rate and a sea-salt proxy show only negligible correlation, which suggests a complex meteorological setting. Increasing annual accumulation is observed for the last 100 years. A period of increased sea-salt concentrations started around AD 1405, as has also been observed in other cores. Microparticle concentrations are on average 1220 particles (>=1.0 ?m diameter)/mL; they are enhanced from AD 1200 to 1350, possibly because of a higher atmospheric mineral dust load or because local volcanic activity was stronger than previously thought. Microparticles and NH4+show marked but multiple and very irregular sub-annual peaks; long-term stacking of 1 year data intervals yields seasonal maxima in austral spring or mid-summer, respectively. Post-depositional redistribution was observed for MSA, NO3- and F- at volcanic horizons.

Physical properties and accumulation rates in Dronning Maud Land, Antarctica

The European Programme for Ice Coring in Antarctica includes a comprehensive pre-site survey on the inland ice plateau of Dronning Maud Land, Antarctica. The German glaciological programme during the 1997/98 field season was carried out along a 1200 km traverse on Amundsenisen and involved sampling the snow cover in pits and by shallow firn cores. This paper focuses on the accumulation studies. The cores were dated by dielectric-profiling and continuous-flow analysis. Distinct volcanogenic peaks and seasonal signals in the profiles served to establish a depth time-scale. The eruptions of Krakatoa, Tambora, an unknown volcano, Kuwae and El Chichon are well-documented in the ice. Variations of the accumulation rates over different times were inferred from the depth time-scales. A composite record of accumulation rates for the last 200 years was produced by stacking 12 annually resolved records. According to this, accumulation rates decreased in the 19th century and increased in the 20th century. The recent values are by no means extraordinary, as they do not exceed the values at the beginning of the 19th century. Variations in accumulation rates are most probably linked to temperature variations indicated in d18O records from Amundsenisen.

Seasonally resolved chemical records of six ice cores from the Dronning Maud Land, Antarctica

The ammonium, calcium, and sodium concentrations from three intermediate depth ice cores drilled in the area of Dronning Maud Land, East Antarctica, have been investigated. Since all measurements were performed by a high-resolution Continuous Flow Analysis system, for the first time seasonal signals of chemical trace species could be obtained from the interior of central Antarctica over a period of approximately 2 millennia. Although the elevation as well as the accumulation rate differ between the drilling sites, similar values were obtained by comparing mean concentrations spanning the last 900 years. However, a distinct lack of intersite correlation was found on decadal timescales. Despite a noticeable accumulation change, apparent in one core, no significant concentration change of all three species has occurred. All the measured ions show clear seasonal signals over the whole records. While the sea-salt-related component sodium peaks simultaneously with calcium, the maximum ammonium concentration occurs in the snow with a time lag of 2 months after the sea-salt peak. More than 60% of the calcium concentration can be attributed to an ocean source. Elevated sodium concentrations were found within this millennium compared to mean values of the whole records, but the spatially varying shape of the increase suggests that a possible climatic signal is biased by local deposition effects.

Stable-isotope records from Dronning Maud Land, Antarctica

The European Project for Ice Coring in Antarctica (EPICA) includes a comprehensive pre-site survey on the inland ice plateau of Dronning Maud Land. This paper focuses on the investigation of the 18O content of shallow firn and ice cores. These cores were dated by profiles derived from dielectric-profiling and continuous flow analysis measurements. The individual records were stacked in order to obtain composite chronologies of 18O contents and accumulation rates with enhanced signal-to-noise variance ratios.These chronologies document variations in the last 200 and 1000 years.The 18O contents and accumulation rates decreased in the 19th century and increased during the 20th century.Using the empirical relationships between stable isotopes, accumulation rates and the 10m firn temperature, the variation of both parameters can be explained by the same temperature history.But other causes for these variations, such as the build-up of the snow cover, cannot be excluded. A marked feature of the 1000 year chronology occurs during the period AD 1180-1530 when the 18O contents remains below the long-term mean. Cross-correlation analyses between five cores from the Weddell Sea region and Dronning Maud Land show that 18O records can in some periods be positively correlated and in others negatively correlated, indicating a complex climatic history in time and space.

Calcium and sodium concentrations of the Talos Dome ice core, Antarctica

In this study we report on new non-sea salt calcium (nssCa2+, mineral dust proxy) and sea salt sodium (ssNa+, sea ice proxy) records along the East Antarctic Talos Dome deep ice core in centennial resolution reaching back 150 thousand years (ka) before present. During glacial conditions nssCa2+ fluxes in Talos Dome are strongly related to temperature as has been observed before in other deep Antarctic ice core records, and has been associated with synchronous changes in the main source region (southern South America) during climate variations in the last glacial. However, during warmer climate conditions Talos Dome mineral dust input is clearly elevated compared to other records mainly due to the contribution of additional local dust sources in the Ross Sea area. Based on a simple transport model, we compare nssCa2+ fluxes of different East Antarctic ice cores. From this multi-site comparison we conclude that changes in transport efficiency or atmospheric lifetime of dust particles do have a minor effect compared to source strength changes on the large-scale concentration changes observed in Antarctic ice cores during climate variations of the past 150 ka. Our transport model applied on ice core data is further validated by climate model data. The availability of multiple East Antarctic nssCa2+ records also allows for a revision of a former estimate on the atmospheric CO2 sensitivity to reduced dust induced iron fertilisation in the Southern Ocean during the transition from the Last Glacial Maximum to the Holocene (T1). While a former estimate based on the EPICA Dome C (EDC) record only suggested 20 ppm, we find that reduced dust induced iron fertilisation in the Southern Ocean may be responsible for up to 40 ppm of the total atmospheric CO2 increase during T1. During the last interglacial, ssNa+ levels of EDC and EPICA Dronning Maud Land (EDML) are only half of the Holocene levels, in line with higher temperatures during that period, indicating much reduced sea ice extent in the Atlantic as well as the Indian Ocean sector of the Southern Ocean. In contrast, Holocene ssNa+ flux in Talos Dome is about the same as during the last interglacial, indicating that there was similar ice cover present in the Ross Sea area during MIS 5.5 as during the Holocene.

Chemical measurements from the EPICA Dome C core

Sea ice and dust flux increased greatly in the Southern Ocean during the last glacial period. Palaeorecords provide contradictory evidence about marine productivity in this region, but beyond one glacial cycle, data were sparse. Here we present continuous chemical proxy data spanning the last eight glacial cycles (740,000 years) from the Dome C Antarctic ice core. These data constrain winter sea-ice extent in the Indian Ocean, Southern Ocean biogenic productivity and Patagonian climatic conditions. We found that maximum sea-ice extent is closely tied to Antarctic temperature on multi-millennial timescales, but less so on shorter timescales. Biological dimethylsulphide emissions south of the polar front seem to have changed little with climate, suggesting that sulphur compounds were not active in climate regulation. We observe large glacial-interglacial contrasts in iron deposition, which we infer reflects strongly changing Patagonian conditions. During glacial terminations, changes in Patagonia apparently preceded sea-ice reduction, indicating that multiple mechanisms may be responsible for different phases of CO2 increase during glacial terminations. We observe no changes in internal climatic feedbacks that could have caused the change in amplitude of Antarctic temperature variations observed 440,000 years ago.

Chemical concentrations and fluxes from EPICA ice cores EDML and EDC

Continuous sea salt and mineral dust aerosol records have been studied on the two EPICA (European Project for Ice Coring in Antarctica) deep ice cores. The joint use of these records from opposite sides of the East Antarctic plateau allows for an estimate of changes in dust transport and emission intensity as well as for the identification of regional differences in the sea salt aerosol source. The mineral dust flux records at both sites show a strong coherency over the last 150 kyr related to dust emission changes in the glacial Patagonian dust source with three times higher dust fluxes in the Atlantic compared to the Indian Ocean sector of the Southern Ocean (SO). Using a simple conceptual transport model this indicates that transport can explain only 40% of the atmospheric dust concentration changes in Antarctica, while factor 5-10 changes occurred. Accordingly, the main cause for the strong glacial dust flux changes in Antarctica must lie in environmental changes in Patagonia. Dust emissions, hence environmental conditions in Patagonia, were very similar during the last two glacials and interglacials, respectively, despite 2-4 °C warmer temperatures recorded in Antarctica during the penultimate interglacial than today. 2-3 times higher sea salt fluxes found in both ice cores in the glacial compared to the Holocene are difficult to reconcile with a largely unchanged transport intensity and the distant open ocean source. The substantial glacial enhancements in sea salt aerosol fluxes can be readily explained assuming sea ice formation as the main sea salt aerosol source with a significantly larger expansion of (summer) sea ice in the Weddell Sea than in the Indian Ocean sector. During the penultimate interglacial, our sea salt records point to a 50% reduction of winter sea ice coverage compared to the Holocene both in the Indian and Atlantic Ocean sector of the SO. However, from 20 to 80 ka before present sea salt fluxes show only very subdued millennial changes despite pronounced temperature fluctuations, likely due to the large distance of the sea ice salt source to our drill sites.