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Tiny samples of ancient atmosphere in air bubbles within ice cores contain argon (Ar), which can be used to reconstruct past temperature changes. At a sufficient depth, the air bubbles are compressed by the overburden pressure under low temperature and transform into air-hydrate crystals. While the oxygen (O2) and nitrogen (N2) molecules have indeed been identified in the air-hydrate crystals with Raman spectroscopy, direct observational knowledge of the distribution of Ar at depth within ice sheet and its enclathration has been lacking. In this study, we applied scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) to five air-hydrate crystals in the Greenland NEEM ice core, finding them to contain Ar and N. Given that Ar cannot be detected by Raman spectroscopy, the method commonly used for O2 and N2, the SEM-EDS measurement method may become increasingly useful for measuring inert gases in deep ice cores.
The long-term refrigerated storage of melted snow and/or ice samples for analyses of insoluble microparticles (hereafter, microparticles) may be limited by increases in the biological particle concentration caused by microbial growth after ~1–2 weeks. In this study, we examined an ultraviolet (UV) disinfection method for the storage of melted snow and/or ice samples and determined the effects of this method on microparticles. Surface snow obtained from Glacier No. 31 in the Suntar-Khayata Range, eastern Siberia, Russia was divided into two portions for UV treatment and untreated controls. Microparticle concentrations and size distributions (in the range of 0.52–12.0 μm) in the samples were measured using a Coulter counter. Whereas the microparticle concentration in untreated samples increased, no obvious increase was observed over 53 d in the samples subjected to UV treatment. Microbial growth was detected in only untreated samples using a viable particle counter. In addition, the original microparticle concentrations and size distributions were unaffected by UV treatment. Our results demonstrated that the microparticle size distribution in untreated melted water samples reflects the growth, decomposition and succession of microorganisms over time and further indicate that UV irradiation is effective for long-term storage for microparticle analysis.
We investigated the effects of microparticles and grain size on the microstructural evolutions and mechanical properties of polycrystalline ice. Uniaxial compression tests were conducted using fine-grained pure ice and silica-dispersed ice under various conditions. Deformation behavior of fine-grained ice was found to be characterized by stress exponent n ≈ 2 and activation energy Q ≈ 60 kJ mol−1. The derived strain rates of fine-grained ice were ≈ 1 order of magnitude larger than those of coarse-grained ice obtained in previous studies, and they were found to be independent of particle dispersion and dependent on the mean grain size of ice, with grain size exponent p ≈ 1.4. Work hardening was observed in dislocation creep, while the strain rate continued to decrease. These results indicate that the deformation mechanism of fine-grained ice is different from typical dislocation creep, often associated with n = 3. Although microparticles restricted grain growth, there was little direct effect on the deformation of fine-grained ice. Microstructural observations of the ice samples indicated that the grain boundaries were straight and that the subgrain boundary densities increased after deformation. Our experiments suggest that grain size and boundaries play important roles in the deformation processes of polycrystalline ice.
In order to better understand the densification of polar firn, firn cores from the three sites within ~10 km of Dome Fuji, Antarctica, were investigated using surrogates of density: dielectric permittivities εv and εh at microwave frequencies with electrical fields in the vertical and horizontal planes respectively. Dielectric anisotropy Δε (=εv − εh) was then examined as a surrogate of the anisotropic geometry of firn. We find that layered densification is explained as a result of complex effects of two phenomena that commonly occur at the three sites. Basically, layers with initially smaller density and smaller geometrical anisotropy deform preferentially throughout the densification process due to textural effects. Second, layers having a higher concentration of Cl− ions deform preferentially during a limited period from the near surface depths until smoothing out of layered Cl− ions by diffusion. We hypothesize that Cl− ions dissociated from sea salts soften firn due to modulation of dislocation movement. Moreover, firn differs markedly across the three sites in terms of strength of geometrical anisotropy, mean rate of densification and density fluctuation. We hypothesize that these differences are caused by textural effects resulting from differences in depositional conditions within various spatial scales.
Densification of firn at the North Greenland Eemian Ice Drilling (NEEM) camp is investigated using density surrogates: dielectric permittivities ∊v and ∊h at microwave frequencies with electrical fields in the vertical and horizontal planes, respectively. Dielectric anisotropy Δ∊ (= ∊v − ∊h) is then examined as a surrogate for the anisotropic geometry of firn. Its size, fluctuations and mutual correlations are investigated in samples taken at depths from the surface to ~90 m. The initial Δ∊ of ~0.06 appears within the uppermost 0.2 m. After that, Δ∊ decreases rapidly until 21–26 m depth. Below this, Δɛ decreases slowly. Layers with more ions of fluorine, chlorine and some cations deposited between the autumn and the subsequent summer deform preferentially during all these stages. This layered deformation is explained partly by the textural effects initially formed by the seasonal variation of metamorphism, and partly by ions such as fluorine, chlorine and ammonium, which are known to modulate dislocation movement in the ice crystal lattice. Insolation-sensitive microstructure appears to be preserved all the way to the pore close-off, within layers of the summer-to-autumn metamorphism. Like previous authors, we hypothesize that calcium is not the active agent in the reported deformation– calcium correlations.
We conducted a pit study in July 2009 at the NEEM (North Greenland Eemian Ice Drilling) deep ice-coring site in northwest Greenland. To examine the seasonal variations of snow chemistry and characteristics of the drill site, we collected snow/firn samples from the wall of a 2 m deep pit at intervals of 0.03 m and analyzed them for electric conductivity, pH, Cl–, NO3–, SO42–, CH3SO3– (MSA), Na+, K+, Mg2+, Ca2+ and stable isotopes of water (δ18O and δD). Pronounced seasonal variations in the stable isotopes of water were observed, which indicated that the snow had accumulated regularly during the past 4 years. Concentrations of Na+, Cl– and Mg2+, which largely originate from sea salt, peaked in winter to early spring, while Ca2+, which mainly originates from mineral dust, peaked in late winter to spring, slightly later than Na+, Cl– and Mg2+. Concentrations of NO3– showed double peaks, one in summer and the other in winter to spring, whereas those of SO42– peaked in winter to spring. The winter-to-spring concentrations of NO3– and SO42– seem to have been strongly influenced by anthropogenic inputs. Concentrations of MSA showed double peaks, one in spring and the other in late summer to autumn. Our study confirms that the NEEM deep ice core can be absolutely dated to a certain depth by counting annual layers, using the seasonal variations of stable isotopes of water and those of ions. We calculated the annual surface mass balance for the years 2006–08. The mean annual balance was 176 mm w.e., and the balances for winter-to-summer and summer-to-winter halves of the year were 98 and 78 mm, respectively. Snow deposition during the winter-to-summer half of the year was greater than that during the summer-to-winter half by 10–20mm for all three years covered by this study.
The coherent variations of annual snow accumulation rate and dust deposition over 60 years are recorded in an ice core drilled at 6530 ma.s.l. on the Chongce ice cap, located in the west Kunlun Shan, south of the Taklimakan desert in China. These records were investigated in the context both of the dust transport pathways from the source region and of climatic changes in this arid environment. The factors relating the dust transport from the source to sink area were taken into account to ascertain the integration of these factors on the precipitation-forming process at high elevations. Results indicate that: (1) dust is predominant among aerosols in precipitation at high altitude; (2) the dust aerosol population may be more instrumental than the vapor supply in the formation of precipitation at such altitudes; (3) compared to low-elevation glaciers, snow accumulation on high mountain glaciers seems to be more sensitive to changes in the concentration of air-burden dust particulates, which are closely related to the climatic variations around the desert region; and (4) under the current climate conditions surrounding the desert region, the decreasing trend in snow accumulation, in concert with the decrease in dust deposition that has occurred over the past several decades, might continue. This effect on snow accumulation at high altitudes may explain one of the elements potentially responsible for the longer-term glacial variation, i.e. the glacial retreat that has lasted for decades in central Asia.
Three ice cores were recovered on or near Mount Logan, Yukon, Canada, at 3017, 4135 and 5340 ma.s.l. in 2002. Prior to ice-core drilling, we collected snow-pit and shallow core samples from Mount Logan in 2001 to study seasonal and spatial variations of snow chemistry. We dug snow pits at six sites between 2420 and 5340 m a.s.l. before the beginning of the melt season, with the exception of a pit at 3180 m a.s.l., where the melt season had just started but had affected only the near-surface stratigraphy. Three of the pits were extended deeper with a shallow core. The snow-pit and core samples were analyzed for ion chemistry and δ18O. A series of depth profiles of ions and δ18O shows spatial variations, though characteristic peaks can usually be traced across all the profiles. Concentrations and deposition fluxes of Na+ and Cl−, which are mainly of sea-salt origin, decrease with altitude. On the other hand, deposition fluxes of NO3−, SO42–, Ca2+ and NH4+ show a weak positive relationship with elevation below the summit plateau. Stable isotopes (δ18O) decrease with altitude, with a distinctive jump between 3200 and 4500 m a.s.l., as was reported previously. Stable isotopes (δ18O), Cl−, CH3SO3− (MSA), Na+ and Ca2+ show clear seasonal variations, which would enable us to date the cores by annual-layer counting.
A compilation of nitrate (NO3–) data from Greenland has shown that recent NO3– concentrations reveal a temperature dependence similar to that seen in Antarctica. Except for sites with very low accumulation rates, lower temperatures tend to lead to higher NO3– concentrations preserved in the ice. Accumulation rate, which is closely linked to temperature, might influence the concentrations preserved in snow as well, but its effect cannot be separated from the temperature imprint. Processes involved in NO3– deposition are discussed and shown to be temperature- and/or accumulation-rate-dependent. Apart from scavenging of nitric acid (HNO3) during formation of precipitation, uptake of HNO3 onto the ice crystal’s surface during and after precipitation seems to contribute further to the NO3– concentrations found in surface snow. Post-depositional loss of NO3– from the top snow layers is caused by release of HNO3 and by photolysis of NO3–. It is suggested that photolysis accounts for considerable losses at sites with very low accumulation rates. Depending on the site characteristic, and given that the temperature and accumulation-rate dependence is quantified, it should be possible to infer changes in atmospheric HNO3 concentrations.
In order to reconstruct climatic and environmental changes in the Canadian Arctic, an 85 m deep ice core drilled in 1995 on Penny Ice Cap, Baffin Island, was analyzed for ions and δ18O. In addition to the core, snow-pit samples collected in 1994 and 1995 were also analyzed. Elution of ions caused by summer melting was observed in the pits. Due to the heavy summer melting on this ice cap, seasonal variations of ion chemistry and δ18O were not always present in the core. Comparisons of this core with a previously reported core drilled 2.5 maway show that the noise contained in single annual time series is 40–50% for ions and 25% for δ18O. the ice-core data, however, provide us with a reasonable proxy record of climatic and environmental changes during the last two centuries on better than a decadal basis. Sulfate and nitrate concentrations started to increase around 1900 and 1960, respectively, due to anthropogenic influx transported from the industrialized regions in North America. Sea-salt concentrations began to increase around the mid-19th century and were elevated throughout the 20th century. This trend of sea-salt concentrations is similar to that of melt percentage, which is a measure of summer temperature. Warming after the Little Ice Age would have reduced the sea-ice extent and led to the elevated sea-salt concentrations on Penny Ice Cap.
Pit-wall samples were collected from two sites about 2 km apart on Agassiz Ice Cap, Ellesmere Island, Northwest Territories, Canada, in 1992, 1993 and 1994, and from a site a further 1 km distant, in order to study spatial and seasonal variations in snow chemistry. Two of the pits were dug in wind-scoured zones and one in an unscoured zone. Although a large part of the winter snow is removed from the scoured zones (which do not show very negative δ18O values) the winter/spring anion peaks are still evident; this may be due to the predominance of dry deposition in mid-winter. The Cl− and SO42– ions peak in late winter/early spring, while NO3− peaks both in late winter/early spring and in summer. Vertical concentration profiles of all anions did not significantly alter over a 2 year period, indicating that there are no serious post-depositional changes due to evaporation, snow melting or photochemical reactions. However, comparisons between stake/board snow-accumulation measurements and those derived from the least scoured pit indicate that a single pit will represent annual accumulation rates for a local area only.
A new flow law for anisotropic polycrystalline ice is presented. The strain-rate tensor is related by a geometrical factor tensor (G) to the stress tensor. The G factor tensor can be obtained front the c-axis fabric data and stress condition. This new flow law describes well the direction-dependent mechanical properties of anisotropic ice which cannot be demonstrated by Glen’s flow law. For example, the new flow law can explain the fact that a strong single-maximum fabric ice, such as Dye 3 Wisconsin ice, can deform several times faster than isotropic ice under horizontal shear but can hardly deform under vertical or horizontal normal stress. We also show that at a deeper part of an ice sheet, where a single-maximum fabric develops, a positive vertical strain rate can be produced with only a horizontal shear stress.
A 2.2 m deep pit and the top 42.5 m of an ice core recovered at Snøfjellafonna, northwestern Spitsbergen, were continuously analyzed for Na+, Cl−, NO3−, SO42− and pH. Seasonal variations in ionic concentrations seem to have remained in the pit and the core, in spite of the relatively severe summer melting. We dated the core by counting annual peaks of Na+ and made an adjustment with the use of a tritium peak in 1963 as a reference horizon. It turned out that the depth of 42.5 m went back to the early 1930s or late 1920s. The 60–70 year record of snow chemistry showed that the concentrations of both NO3− and SO42− had increased in the 1950s and had decreased in the late 1970s and the 1980s. The increase would be explained in terms of anthropogenic inputs from the industrial areas. The later decrease of the same ions may have been caused by a combination of the reduction of the atmospheric precursors due to pollution controls and the meltwater-associated processes.
Chemical stratigraphy in association with the texture of snow cover was studied during the period from the severe winter to the early snowmelt season. The vertical concentration profiles of N03−, SO42−, Cl− and Na+ were generally preserved until the initial stage of the snowmelt season, while there were appreciable variations in ionic concentrations. At the initial stage of the snowmelt season, redistribution of chemical constituents in the snow cover occurred in a complicated way, dependent on both the structure of internal layers and the chemical species. Major peaks, however, still remained in the profiles.
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