Abstract. The variations of δO2/N2 and δAr/N2 in the Dome Fuji ice core were measured from 112 m (bubbly ice) to 2001 m (clathrate hydrate ice). Our method, combined with the low storage temperature of the samples (−50 ∘C), successfully excludes post-coring gas-loss fractionation signals from our data. From the bubbly ice to the middle of the bubble–clathrate transition zone (BCTZ) (112–800 m) and below the BCTZ (>1200 m), the δO2/N2 and δAr/N2 data exhibit orbital-scale variations similar to local summer insolation. The data in the lower BCTZ (800–1200 m) have large scatter, which may be caused by millimeter-scale inhomogeneity of air composition combined with finite sample lengths. The insolation signal originally recorded at the bubble close-off remains through the BCTZ, and the insolation signal may be reconstructed by analyzing long ice samples (more than 50 cm for the Dome Fuji core). In the clathrate hydrate zone, the scatter around the orbital-scale variability decreases with depth, indicating diffusive smoothing of δO2/N2 and δAr/N2. A simple gas diffusion model was used to reproduce the smoothing and thus constrain their permeation coefficients. The relationship between δAr/N2 and δO2/N2 is markedly different for the datasets representing bubble close-off (slope ∼ 0.5), bubble–clathrate hydrate transformation (∼1), and post-coring gas loss (∼0.2), suggesting that the contributions of the mass-independent and mass-dependent fractionation processes are different for those cases. The method and data presented here may be useful for improving the orbital dating of deep ice cores over the multiple glacial cycles and further studying non-insolation-driven signals (e.g., atmospheric composition) of these gases.

Abstract. Gas isotope thermometry using the isotopes of molecular nitrogen and argon has been used extensively to reconstruct past surface temperature change from Greenland ice cores. The gas isotope ratios δ15N and δ40Ar in the ice core are each set by the amount of gravitational and thermal fractionation in the firn. The gravitational component of fractionation is proportional to the firn thickness, and the thermal component is proportional to the temperature difference between the top and bottom of the firn column, which can be related to surface temperature change. Compared to Greenland, Antarctic climate change is typically more gradual and smaller in magnitude, which results in smaller thermal fractionation signals that are harder to detect. This has hampered application of gas isotope thermometry to Antarctic ice cores. Here, we present an analytical method for measuring δ15N and δ40Ar with a precision of 0.002 ‰ per atomic mass unit, a two-fold improvement on previous work. This allows us to reconstruct changes in firn thickness and temperature difference at the South Pole between 30 and 5 kyr BP. We find that variability in firn thickness is controlled in part by changes in snow accumulation rate, which is, in turn, influenced strongly by the along-flowline topography upstream of the ice core site. Variability in our firn temperature difference record cannot be explained by annual-mean processes. We therefore propose that the ice core gas isotopes contain a seasonal bias due to rectification of seasonal signals in the upper firn. The strength of the rectification also appears to be linked to fluctuations in the upstream topography. As further evidence for the existence of rectification, we present new data from the Dome Fuji ice core that are also consistent with a seasonal bias throughout the Holocene. Our findings have important implications for the interpretation of ice core gas records. For example, we show that the effects of upstream topography on ice core records can be significant at flank sites like the South Pole – they are responsible for some of the largest signals in our record. Presumably upstream signals impact other flank-flow ice cores such as EDML, Vostok, and EGRIP similarly. Additionally, future work is required to confirm the existence of seasonal rectification in polar firn, to determine how spatially and temporally widespread rectifier effects are, and to incorporate the relevant physics into firn air models.

Abstract. The variations of δO2/N2 and δAr/N2 in the Dome Fuji ice core were measured from 112 m (bubbly ice) to 2001 m (clathrate hydrate ice) at high precision. Our method, combined with the low storage temperature of the samples (−50 °C), successfully excludes post-coring gas-loss fractionation signals from our data. From the bubbly ice to the middle of the bubble-clathrate transition zone (BCTZ) (112–800 m) and below the BCTZ (> 1200 m), the δO2/N2 and δAr/N2 data exhibit orbital-scale variations similar to local summer insolation. The data in the lower BCTZ (800–1200 m) have large scatters, which may be caused by mm-scale inhomogeneity of air composition combined with finite sample lengths. The insolation signal originally recorded at the bubble close-off remains through the BCTZ, and the insolation signal may be reconstructed by analyzing long ice samples. In the clathrate hydrate zone, the scatters around the orbital-scale variability decrease with depth, indicating diffusive smoothing of δO2/N2 and δAr/N2. A simple gas diffusion model was used to reproduce the smoothing and thus constrain their permeation coefficients. The relationship between δAr/Ν2 and δO2/N2 is markedly different for the datasets representing bubble close-off (slope ~0.5), bubble-clathrate hydrate transformation (~1), and post-coring gas-loss (~0.2), suggesting that the contribution of the mass-independent and mass-dependent fractionation processes are different for those cases. The method and data presented here may be useful for improving the orbital dating of deep ice cores over the multiple glacial cycles and further studying non-insolation-driven signals (e.g., atmospheric composition) of these gases.