Motohiro Hirabayashi

Seasonal variations of snow chemistry at NEEM, Greenland

Abstarct 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 –, SO4 2–, 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 SO4 2– peaked in winter to spring. The winter-to-spring concentrations of NO3 – and SO4 2– 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.

Sulphate–climate coupling over the past 300,000 years in inland Antarctica

Sulphate aerosols, particularly micrometre-sized particles of sulphate salt and sulphate-adhered dust, can act as cloud condensation nuclei, leading to increased solar scattering that cools Earth’s climate. Evidence for such a coupling may lie in the sulphate record from polar ice cores, but previous analyses of melted ice-core samples have provided only sulphate ion concentrations, which may be due to sulphuric acid. Here we present profiles of sulphate salt and sulphate-adhered dust fluxes over the past 300,000 years from the Dome Fuji ice core in inland Antarctica. Our results show a nearly constant flux of sulphate-adhered dust through glacial and interglacial periods despite the large increases in total dust flux during glacial maxima. The sulphate salt flux, however, correlates inversely with temperature, suggesting a climatic coupling between particulate sulphur and temperature. For example, the total sulphate salt flux during the Last Glacial Maximum averages 5.78 mg m−2 yr−1, which is almost twice the Holocene value. Although it is based on a modern analogue with considerable uncertainties when applied to the ice-core record, this analysis indicates that the glacial-to-interglacial decrease in sulphate would lessen the aerosol indirect effects on cloud lifetime and albedo, leading to an Antarctic warming of 0.1 to 5 kelvin.

Radiocarbon (14C) Diurnal Variations in Fine Particles at Sites Downwind from Tokyo, Japan in Summer

The radiocarbon ((14)C) of total carbon (TC) in atmospheric fine particles was measured at 6 h or 12 h intervals at two sites, 50 and 100 km downwind from Tokyo, Japan (Kisai and Maebashi) in summer 2007. The percent modern carbon (pMC) showed clear diurnal variations with minimums in the daytime. The mean pMC values at Maebashi were 28 ± 7 in the daytime and 45 ± 16 at night (37 ± 15 for the overall period). Those at Kisai were 26 ± 9 in the daytime and 44 ± 8 at night (37 ± 12 for the overall period). This data indicates that fossil sources were major contributors to the daytime TC, while fossil and modern sources had comparable contributions to nighttime TC in the suburban areas. At both sites, the concentration of fossil carbon as well as O(3) and the estimated secondary organic carbon increased in the daytime. These results suggest that fossil sources around Tokyo contributed significantly to the high daytime concentration of secondary organic aerosols (SOA) at the two suburban sites. A comparison of pMC and the ratio of elemental carbon/TC from our particulate samples with those from three end-member sources corroborates the dominant role of fossil SOA in the daytime.

State dependence of climatic instability over the past 720,000 years from Antarctic ice cores and climate modeling

Global cooling in intermediate glacial climate with northern ice sheets preconditions climatic instability with bipolar seesaw. Climatic variabilities on millennial and longer time scales with a bipolar seesaw pattern have been documented in paleoclimatic records, but their frequencies, relationships with mean climatic state, and mechanisms remain unclear. Understanding the processes and sensitivities that underlie these changes will underpin better understanding of the climate system and projections of its future change. We investigate the long-term characteristics of climatic variability using a new ice-core record from Dome Fuji, East Antarctica, combined with an existing long record from the Dome C ice core. Antarctic warming events over the past 720,000 years are most frequent when the Antarctic temperature is slightly below average on orbital time scales, equivalent to an intermediate climate during glacial periods, whereas interglacial and fully glaciated climates are unfavourable for a millennial-scale bipolar seesaw. Numerical experiments using a fully coupled atmosphere-ocean general circulation model with freshwater hosing in the northern North Atlantic showed that climate becomes most unstable in intermediate glacial conditions associated with large changes in sea ice and the Atlantic Meridional Overturning Circulation. Model sensitivity experiments suggest that the prerequisite for the most frequent climate instability with bipolar seesaw pattern during the late Pleistocene era is associated with reduced atmospheric CO2 concentration via global cooling and sea ice formation in the North Atlantic, in addition to extended Northern Hemisphere ice sheets.

Greenland 2012 melt event effects on CryoSat‐2 radar altimetry

CryoSat-2 data are used to study elevation changes over an area in the interior part of the Greenland Ice Sheet during the extreme melt event in July 2012. The penetration of the radar signal into dry snow depends heavily on the snow stratigraphy, and the rapid formation of refrozen ice layers can bias the surface elevations obtained from radar altimetry. We investigate the change in CryoSat-2 waveforms and elevation estimates over the melt event and interpret the findings by comparing in situ surface and snow pit observations from the North Greenland Eemian Ice Drilling Project camp. The investigation shows a major transition of scattering properties around the area, and an apparent elevation increase of 56 ± 26 cm is observed in reprocessed CryoSat-2 data. We suggest that this jump in elevation can be explained by the formation of a refrozen melt layer that raised the reflective surface, introducing a positive elevation bias.

Constituent elements of insoluble and non-volatile particles during the Last Glacial Maximum exhibited in the Dome Fuji (Antarctica) ice core

In order to find environmental signals based on the dust and calcium-ion concentrations in ice cores, we determine the constituent elements of residue particles obtained after melting ice samples. We have designed a sublimating system that operates at -458C, below the eutectic temperatures of major salts. This system permits us to obtain a great many non-volatile particles. After studying the non- volatile particles, we immersed them in water to remove soluble particles and compounds. We thereby analyzed a total of 1272 residue particles (from the melted sample), 2418 non-volatile particles (after sublimation) and 1463 insoluble particles taken from five sections of Last Glacial Maximum ice from the Dome Fuji (Antarctica) ice core. Their constituent elements were determined by scanning electron microscopy/energy-dispersive X-ray spectrometry (SEM-EDS) and compared to the dust, calcium-ion and sodium-ion concentrations measured by ion chromatography. Our results indicate that >99.9% of the insoluble particles contain silicon but no sulfur, nitrogen or chlorine. A significant number of the non-volatile particles, however, contain sulfur and chlorine. We conclude that insoluble dust consists mostly of silicate, that almost all calcium ions originate from calcium sulfate and that almost all sodium ions originate from sodium sulfate and sodium chloride.

Chemical compositions of sulfate and chloride salts over the last termination reconstructed from the Dome Fuji ice core, inland Antarctica

The flux and chemical composition of aerosols impact the climate. Antarctic ice cores preserve the record of past atmospheric aerosols, providing useful information about past atmospheric environments. However, few studies have directly measured the chemical composition of aerosol particles preserved in ice cores. Here we present the chemical compositions of sulfate and chloride salts from aerosol particles in the Dome Fuji ice core. The analysis method involves ice sublimation, and the period covers the last termination, 25.0–11.0 thousand years before present (kyr B.P.), with a 350 year resolution. The major components of the soluble particles are CaSO4, Na2SO4, and NaCl. The dominant sulfate salt changes at 16.8 kyr B.P. from CaSO4, a glacial type, to Na2SO4, an interglacial type. The sulfate salt flux (CaSO4 plus Na2SO4) inversely correlates with δ18O in Dome Fuji over millennial timescales. This correlation is consistent with the idea that sulfate salt aerosols contributed to the last deglacial warming of inland Antarctica by reducing the aerosol indirect effect. Between 16.3 and 11.0 kyr B.P., the presence of NaCl suggests that winter atmospheric aerosols are preserved. A high NaCl/Na2SO4 fraction between 12.3 and 11.0 kyr B.P. indicates that the contribution from the transport of winter atmospheric aerosols increased during this period.

A Firn Densification Process in the High Accumulation Dome of Southeastern Greenland

ABSTRACT We examine a firn core from a dome in southeast Greenland that exhibits distinct firn densification. The ice was -20.9 °C at 20 m depth, and the core gives an average accumulation rate of 1.0 m w.e. yr-1 in water equivalent. However, the close-off density of 830 kg m-3 occurs at 83.4–86.8 m depth, which is about 20-m shallower than that obtained from two empirical models. Where the density ρ > 750 kg m-3, the densification appears faster than that from the empirical models. As a result, compared to the empirical coefficient, the actual compactive viscosity coefficient is nonlinear and decreases at ρ > 750 kg m-3, indicating that the firn with a higher density is softer than that from the empirical result. We argue here that the high accumulation rate creates a high overburden pressure in a short time. Thus, the relative softness of the firn may arise from (1) there being not enough time to form bonds between grains as strong as those in a lower accumulation-rate area, and similarly, (2) the dislocation density in the firn being relatively high.

Spatial distributions of soluble salts in surface snow of East Antarctica

To better understand how sea salt reacts in surface snow of Antarctica, we collected and identified non-volatile particles in surface snow along a traverse in East Antarctica. Samples were obtained during summer 2012/2013 from coastal to inland regions within 69°S to 80°S and 39°E to 45°E, a total distance exceeding 800 km. The spatial resolution of samples is about one sample per latitude between 1500 and 3800 m altitude. Here, we obtain the atomic ratios of Na, S and Cl, and calculate the masses of sodium sulphate and sodium chloride. The results show that, even in the coast snow sample (69°S), sea salt is highly modified by acid (HNO3 or H2SO4). The fraction of sea salt that reacts with acid increases in the region from 70°S to 74°S below 3000 m a.s.l., where some NaCl remains. At the higher altitudes (above 3300 m a.s.l.) in the inland region (74°S to 80°S), the reaction uses almost all of the available NaCl.

Frost flowers and sea-salt aerosols over seasonal sea-ice areas in north-western Greenland during winter–spring

Sea salts and halogens in aerosols, frost flowers, and brine play an important role in atmospheric chemistry in polar regions. Simultaneous sampling and observations of frost flowers, brine, and aerosol particles were conducted around Siorapaluk in northwestern Greenland during December 2013 to March 2014. Results show that watersoluble frost flower and brine components are sea-salt components (e.g., Na, Cl, Mg2+, K, Ca2+, Br, and iodine). Concentration factors of sea-salt components of frost flowers and brine relative to seawater were 1.14–3.67. Sea-salt enrichment of Mg2+, K, Ca2+, and halogens (Cl, Br, and iodine) in frost flowers is associated with sea-salt fractionation by precipitation of mirabilite and hydrohalite. High aerosol number concentrations correspond to the occurrence of higher abundance of sea-salt particles in both coarse and fine modes, and blowing snow and strong winds. Aerosol number concentrations, particularly in coarse mode, are increased considerably by release from the sea-ice surface under strong wind conditions. Sulfate depletion by sea-salt fractionation was found to be limited in sea-salt aerosols because of the presence of non-sea-salt (NSS) SO2− 4 . However, coarse and fine sea-salt particles were found to be rich in Mg. Strong Mg enrichment might be more likely to proceed in fine seasalt particles. Magnesium-rich sea-salt particles might be released from the surface of snow and slush layer (brine) on sea ice and frost flowers. Mirabilite-like and ikaite-like particles were identified only in aerosol samples collected near new sea-ice areas. From the field evidence and results from earlier studies, we propose and describe sea-salt cycles in seasonal sea-ice areas.