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. Air in polar ice cores provides various information on past climatic and atmospheric changes. We developed a new method combining wet extraction, gas chromatography and mass spectrometry, for high-precision, simultaneous measurements of eight air components (CH4, N2O and CO2 concentrations, δ15N, δ18O, δO2/N2, δAr/N2 and total air content) from an ice core sample of ~60 g. The ice sample is evacuated for ~2 hours and melted under vacuum, and the released air is continuously transferred into a sample tube at 10 K within 10 minutes. The air is homogenized in the sample tube overnight at room temperature, and split into two aliquots for mass spectrometric and gas chromatographic measurements. Cares are taken to minimize contamination of greenhouse gases with long evacuation time, consumption of oxygen during sample storage by passivation treatment on sample tubes, and fractionation of isotopic ratios with long homogenization time for splitting. Precisions are assessed by analysing standard gases with artificial ice, and by duplicate measurements of the Dome Fuji and NEEM ice cores. The overall reproducibility (one standard deviation) from duplicate ice-core analyses are 3.2 ppb, 2.2 ppb and 3.1 ppm for CH4, N2O and CO2 concentrations, 0.006, 0.010, 0.09 and 0.12 ‰ for δ15N, δ18O, δO2/N2 and δAr/N2, and 0.67 mlSTP kg-1 for total air content, respectively. Our new method successfully combines the high-precision, small-sample and multiple-species measurements, with a wide range of applications for ice-core paleoenvironmental studies.

No abstract

Abstract. Our study is the first to demonstrate a high-temporal-resolution record of mineral composition in a Greenland ice core over the past 100 years. To reconstruct past variations in the sources and transportation processes of mineral dust in northwestern Greenland, we analysed the morphology and mineralogical composition of dust in the SIGMA-D ice core from 1915 to 2013 using scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS). The results revealed that the ice core dust consisted mainly of silicate minerals and that the composition varied substantially on multi-decadal and inter-decadal scales, suggesting that the ice core minerals originated from different geological sources in different periods during the past 100 years. The multi-decadal variation trend differed among mineral types. Kaolinite, which generally formed in warm and humid climatic zones, was abundant in colder periods (1950–2004), whereas mica, chlorite, feldspars, mafic minerals, and quartz, which formed in arid, high-latitude, and local areas, were abundant in warmer periods (1915–1949 and 2005–2013). Comparison to Greenland surface temperature records indicates that multi-decadal variation in the relative abundance of these minerals was likely affected by local temperature changes in Greenland. Trajectory analysis shows that the minerals were transported mainly from the western coast of Greenland in the two warming periods, which was likely due to an increase in dust sourced from local ice-free areas as a result of shorter snow/ice cover duration in the Greenland coastal region during the melt season caused by recent warming. Meanwhile, ancient deposits in northern Canada, which were formed in past warmer climates, seem to be the best candidate during the colder period (1950–2004). Our results suggest that SEM–EDS analysis can detect variations in ice core dust sources during recent periods of low dust concentration.

Abstract. Air in polar ice cores provides unique information on past climatic and atmospheric changes. We developed a new method combining wet extraction, gas chromatography and mass spectrometry for high-precision, simultaneous measurements of eight air components (CH4, N2O and CO2 concentrations; δ15N, δ18O, δO2∕N2 and δAr∕N2; and total air content) from an ice-core sample of ∼ 60 g. The ice sample is evacuated for ∼ 2 h and melted under vacuum, and the released air is continuously transferred into a sample tube at 10 K within 10 min. The air is homogenized in the sample tube overnight at room temperature and split into two aliquots for mass spectrometric and gas chromatographic measurements. Care is taken to minimize (1) contamination of greenhouse gases by using a long evacuation time, (2) consumption of oxygen during sample storage by a passivation treatment on sample tubes, and (3) fractionation of isotopic ratios with a long homogenization time for splitting. Precision is assessed by analyzing standard gases with artificial ice and duplicate measurements of the Dome Fuji and NEEM ice cores. The overall reproducibility (1 SD) of duplicate ice-core analyses are 3.2 ppb, 2.2 ppb and 2.9 ppm for CH4, N2O and CO2 concentrations; 0.006 ‰, 0.011 ‰, 0.09 ‰ and 0.12 ‰ for δ15N, δ18O, δO2∕N2 and δAr∕N2; and 0.63 mLSTP kg−1 for total air content, respectively. Our new method successfully combines the high-precision, small-sample and multiple-species measurements, with a wide range of applications for ice-core paleoenvironmental studies.