ALBERT

Description: Because the total air content (TAC) of polar ice is directly affected by the atmospheric pressure, its record in polar ice cores was considered as a proxy for past ice sheet elevation changes. However the Antarctic ice core TAC record is known to also contain an insolation signature, although the underlying physical mechanisms are still a matter of debate. Here we present a high-resolution TAC record over the whole North Greenland Ice Core Project ice core, covering the last 120 000 years, which independently supports an insolation signature in Greenland. Wavelet analysis reveals a clear precession and obliquity signal similar to previous findings on Antarctic TAC, with different insolation history. In our high-resolution record we also find a decrease of 3–5 % (3–4.2 mL kg−1) in TAC as a response to Dansgaard-Oeschger-Events (DO-events). TAC starts to decrease in parallel to increasing Greenland surface temperature and slightly before CH4 reacts to the warming, but also shows a two-step decline that lasts for several centuries into the warm phase/interstadial. The TAC response is larger than expected considering only local temperature and atmospheric pressure as a driver, pointing to transient firnification response caused by the accumulation-induced increase in the load on the firn at bubble close-off, while temperature changes deeper in the firn are still small.

Description: Gases in ice cores are invaluable archives of past environmental changes (e.g., the past atmosphere). However, gas fractionation processes after bubble closure in the firn are poorly understood, although increasing evidence indicates preferential leakages of smaller molecules (e.g., neon, oxygen, and argon) from the closed bubbles through ice crystals. These fractionation processes are believed to be responsible for the observed millennial δO2/N2 variations in ice cores, linking ice core chronologies with orbital parameters. Herein, we found that δAr/N2 at decadal resolution on the gas age scale in the GISP2 ice core has a significant negative correlation with accumulation rate over the past 6000 years. Furthermore, the precise temperature and accumulation rate records over the past 4000 years are found to have nearly equal effects on δAr/N2 with sensitivities of 0.72 ± 0.1 ‰ °C−1 and −0.58 ± 0.09 ‰ (0.01 m ice yr−1)−1, respectively. To understand the fractionation processes, we applied a permeation model to "microbubbles (〈 1 % of air content in the Vostok ice core)" and "normal bubbles" in the firn. The model indicates that δAr/N2 in the microbubbles is negatively correlated with the accumulation rate as found in the observation, due to changes in overloading pressure. Colder (warmer) temperatures in the firn induce more (less) depletions in δAr/N2. The microbubbles are so depleted in δAr/N2 at the bubble closeoff depth that they dominate the total δAr/N2 changes in spite of their smaller volumes. The model also indicates that δAr/N2 of GISP2 and NGRIP should have experienced several permil of depletion during the storage 14 years after coring. Further understanding of the δAr/N2 and δO2/N2 fractionation processes in the firn may lead to a new proxy for the past temperature and accumulation rate.

Description: Gases in ice cores are invaluable archives of past environmental changes (e.g., the past atmosphere). However, gas fractionation processes after bubble closure in the firn are poorly understood, although increasing evidence indicates preferential leakages of smaller molecules (e.g., neon, oxygen, and argon) from the closed bubbles through the ice matrix. These fractionation processes are believed to be responsible for the observed millennial δO2/N2 variations in ice cores, linking ice core chronologies with orbital parameters. In this study, we investigated high-resolution δAr/N2 of the GISP2 (Greenland Ice Sheet Project 2), NGRIP (North Greenland Ice Core Project), and Dome Fuji ice cores for the past few thousand years. We find that δAr/N2 at multidecadal resolution on the "gas-age scale" in the GISP2 ice core has a significant negative correlation with accumulation rate and a positive correlation with air contents over the past 6000 years, indicating that changes in overloading pressure induced δAr/N2 fractionation in the firn. Furthermore, the GISP2 temperature and accumulation rate for the last 4000 years have nearly equal effects on δAr/N2 with sensitivities of 0.72 ± 0.1 ‰ °C−1 and −0.58 ± 0.09 ‰ (0.01 m ice year−1)−1, respectively. To understand the fractionation processes, we applied a permeation model for two different processes of bubble pressure build-up in the firn, "pressure sensitive process" (e.g., microbubbles: 0.3–3 % of air contents) with a greater sensitivity to overloading pressures and "normal bubble process". The model indicates that δAr/N2 in the bubbles under the pressure sensitive process are negatively correlated with the accumulation rate due to changes in overloading pressure. On the other hand, the normal bubbles experience only limited depletion (〈 0.5 ‰) in the firn. Colder temperatures in the firn induce more depletion in δAr/N2 through thicker firn. The pressure sensitive bubbles are so depleted in δAr/N2 at the bubble close-off depth that they dominate the total δAr/N2 changes in spite of their smaller air contents. The model also indicates that δAr/N2 of ice cores should have experienced several per mil of depletion during the storage 14–18 years after coring. Further understanding of the δAr/N2 fractionation processes in the firn, combined with nitrogen and argon isotope data, may lead to a new proxy for the past temperature and accumulation rate.

Description: The stratospheric degradation of chlorofluorocarbons (CFCs) releases chlorine, which is a major contributor to the destruction of stratospheric ozone (O3). A recent study reported strong chlorine isotope fractionation during the breakdown of the most abundant CFC (CFC-12, CCl2F2, Laube et al., 2010a), similar to effects seen in nitrous oxide (N2O). Using air archives to obtain a long-term record of chlorine isotope ratios in CFCs could help to identify and quantify their sources and sinks. We analyse the three most abundant CFCs and show that CFC-11 (CCl3F) and CFC-113 (CClF2CCl2F) exhibit significant stratospheric chlorine isotope fractionation, in common with CFC-12. The apparent isotope fractionation (ϵapp) for mid- and high-latitude stratospheric samples are respectively −2.4 (0.5) and −2.3 (0.4) ‰ for CFC-11, −12.2 (1.6) and −6.8 (0.8) ‰ for CFC-12 and −3.5 (1.5) and −3.3 (1.2) ‰ for CFC-113, where the number in parentheses is the numerical value of the standard uncertainty expressed in per mil. Assuming a constant isotope composition of emissions, we calculate the expected trends in the tropospheric isotope signature of these gases based on their stratospheric 37Cl enrichment and stratosphere–troposphere exchange. We compare these projections to the long-term δ (37Cl) trends of all three CFCs, measured on background tropospheric samples from the Cape Grim air archive (Tasmania, 1978–2010) and tropospheric firn air samples from Greenland (North Greenland Eemian Ice Drilling (NEEM) site) and Antarctica (Fletcher Promontory site). From 1970 to the present day, projected trends agree with tropospheric measurements, suggesting that within analytical uncertainties, a constant average emission isotope delta (δ) is a compatible scenario. The measurement uncertainty is too high to determine whether the average emission isotope δ has been affected by changes in CFC manufacturing processes or not. Our study increases the suite of trace gases amenable to direct isotope ratio measurements in small air volumes (approximately 200 mL), using a single-detector gas chromatography–mass spectrometry (GC–MS) system.

Description: The Toba eruption that occurred some 74 ka ago in Sumatra, Indonesia, is among the largest volcanic events on Earth over the last 2 million years. Tephra from this eruption has been spread over vast areas in Asia, where it constitutes a major time marker close to the Marine Isotope Stage 4/5 boundary. As yet, no tephra associated with Toba has been identified in Greenland or Antarctic ice cores. Based on new accurate dating of Toba tephra and on accurately dated European stalagmites, the Toba event is known to occur between the onsets of Greenland interstadials (GI) 19 and 20. Furthermore, the existing linking of Greenland and Antarctic ice cores by gas records and by the bipolar seesaw hypothesis suggests that the Antarctic counterpart is situated between Antarctic Isotope Maxima (AIM) 19 and 20. In this work we suggest a direct synchronization of Greenland (NGRIP) and Antarctic (EDML) ice cores at the Toba eruption based on matching of a pattern of bipolar volcanic spikes. Annual layer counting between volcanic spikes in both cores allows for a unique match. We first demonstrate this bipolar matching technique at the already synchronized Laschamp geomagnetic excursion (41 ka BP) before we apply it to the suggested Toba interval. The Toba synchronization pattern covers some 2000 yr in GI-20 and AIM- 19/20 and includes nine acidity peaks that are recognized in both ice cores. The suggested bipolar Toba synchronization has decadal precision. It thus allows a determination of the exact phasing of inter-hemispheric climate in a time interval of poorly constrained ice core records, and it allows for a discussion of the climatic impact of the Toba eruption in a global perspective. The bipolar linking gives no support for a long-term global cooling caused by the Toba eruption as Antarctica experiences a major warming shortly after the event. Furthermore, our bipolar match provides a way to place palaeoenvironmental records other than ice cores into a precise climatic context.