Shinichiro Horikawa

Molecular dynamics studies of molecular diffusion in ice Ih

We performed molecular dynamics simulations of the diffusion of interstitial He and H2O in ice Ih and found diffusion hops for these interstitial molecules from a stable site to an adjacent site. By observing the jumps of these diffusing species, we determined the jump frequencies, the crystal orientation dependence of the diffusion coefficients, and the diffusion activation energies. Most jumps are along the c axis, because the energy barrier for diffusion along the c axis is lower than that in the a–b plane. Furthermore, the diffusion mechanism for He significantly differ from that for H2O; interstitial H2O diffused by distorting the ice lattice, whereas He atom migrated by jumping from a stable interstitial site to an adjacent site without distorting the lattice. The transverse optic mode for translational lattice vibrations of the lattice surrounding the interstitial H2O shifts to high energy in comparison with that of the pure ice Ih. This upward shift is attributed to a strong coupling between local...

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.

Direct observation of salts as micro-inclusions in the Greenland GRIP ice core

We provide the first direct evidence that a number of water-soluble compounds, in particular calcium sulfate (CaSO 4 .2H 2 O) and calcium carbonate (CaCO 3 ), are present as solid, micron-sized inclusions within the Greenland GRIP ice core. The compounds are detected by two independent methods: micro-Raman spectroscopy of a solid ice sample, and energy-dispersive X-ray spectroscopy of individual inclusions remaining after sublimation. CaSO 4 .2H 2 O is found in abundance throughout the Holocene and the last glacial period, while CaCO 3 exists mainly in the glacial period ice. We also present size and spatial distributions of the micro-inclusions. These results suggest that water-soluble aerosols in the GRIP ice core are dependable proxies for past atmospheric conditions.

The chemical forms of water-soluble microparticles preserved in the Antarctic ice sheet during Termination I

This study clarifies changes in the chemical forms of microparticles during Termination I, the period of drastic climate change between the Last Glacial Maximum (LGM) and the Holocene. We determine the chemical forms of individual water-soluble microparticles through micro-Raman spectroscopy and compare the relative frequencies of different types with the ion concentrations in melted ice. Micro-Raman spectroscopy shows that Na2SO4� 10H2O and MgSO4� 11H2O are abundant in Holocene ice, while CaSO4� 2H2O and other salts are abundant in LGM ice. Further, the number of CaSO4� 2H2O particles is strongly correlated with the concentration of Ca 2+ during Termination I. Taken together, the evidence strongly suggests that most of the Ca 2+ exists as CaSO4� 2H2O. The different compositions of microparticles from the Holocene and LGM can be explained by ion balance arguments.

A Technique for Measuring Microparticles in Polar Ice Using Micro-Raman Spectroscopy

We describe in detail our method of measuring the chemical forms of microparticles in polar ice samples through micro-Raman spectroscopy. The method is intended for solid ice samples, an important point because melting the ice can result in dissociation, contamination, and chemical reactions prior to or during a measurement. We demonstrate the technique of measuring the chemical forms of these microparticles and show that the reference spectra of those salts expected to be common in polar ice are unambiguously detected. From our measurements, Raman intensity of sulfate salts is relatively higher than insoluble dust due to the specific Raman scattering cross-section of chemical forms of microparticles in ice.

Continuous long-term array analysis of seismic records observed during the 2011 Shinmoedake eruption activity of Kirishima volcano, southwest Japan

We deployed a seismic array at a site 5 km east of Shinmoedake volcano, in the Kirishima volcanic complex of southwest Japan, five days after the sub-Plinian eruption on 26 January, 2011. The array record between February and September 2011 included explosion earthquakes and episodes of weak continuous tremor during eruption periods. We estimated slownesses and back azimuths of seismic waves on a sliding 1-min window using the semblance method. The slownesses of the weak continuous tremor clustered within the range 0.2–0.8 s/km, consistent with a mix of body and surface waves. A probabilistic approach based on a grid search was used to estimate the source locations of the explosion earthquakes and weak continuous tremor. The sources of the explosion earthquakes were beneath the crater at depths of −0.5–1 km above sea level, while the source of the weak continuous tremor was beneath the northern part of Shinmoedake at depths between 1 km below sea level and 1 km above sea level. This latter region corresponds to a shallow low-resistivity layer, suggesting that hydrothermal processes are more plausible than magmatic processes as the generating mechanism of the weak continuous tremor.

Monitoring eruption activity using temporal stress changes at Mount Ontake volcano

Volcanic activity is often accompanied by many small earthquakes. Earthquake focal mechanisms represent the fault orientation and slip direction, which are influenced by the stress field. Focal mechanisms of volcano-tectonic earthquakes provide information on the state of volcanoes via stresses. Here we demonstrate that quantitative evaluation of temporal stress changes beneath Mt. Ontake, Japan, using the misfit angles of focal mechanism solutions to the regional stress field, is effective for eruption monitoring. The moving average of misfit angles indicates that during the precursory period the local stress field beneath Mt. Ontake was deviated from the regional stress field, presumably by stress perturbations caused by the inflation of magmatic/hydrothermal fluids, which was removed immediately after the expulsion of volcanic ejecta. The deviation of the local stress field can be an indicator of increases in volcanic activity. The proposed method may contribute to the mitigation of volcanic hazards.

Asynchrony between Antarctic temperature and CO 2 associated with obliquity over the past 720,000 years

The δD temperature proxy in Antarctic ice cores varies in parallel with CO2 through glacial cycles. However, these variables display a puzzling asynchrony. Well-dated records of Southern Ocean temperature will provide crucial information because the Southern Ocean is likely key in regulating CO2 variations. Here, we perform multiple isotopic analyses on an Antarctic ice core and estimate temperature variations at this site and in the oceanic moisture source over the past 720,000 years, which extend the longest records by 300,000 years. Antarctic temperature is affected by large variations in local insolation that are induced by obliquity. At the obliquity periodicity, the Antarctic and ocean temperatures lag annual mean insolation. Further, the magnitude of the phase lag is minimal during low eccentricity periods, suggesting that secular changes in the global carbon cycle and the ocean circulation modulate the phase relationship among temperatures, CO2 and insolation in the obliquity frequency band.The Antarctic temperature record displays a puzzling asynchrony with changes in CO2 through glacial cycles. Here, the authors show that a 720,000-year Antarctic temperature record is affected by variations in obliquity-induced local insolation that are associated with phase modulation of eccentricity cycle.