Synthesis,TEM characterization and thermal behaviour of LiNiSi<Subscript>2</Subscript>O<Subscript>6</Subscript> pyroxene     

Mario Tribaudino  Geoffrey Bromiley  Haruo Ohashi  Fabrizio Nestola 《Physics and Chemistry of Minerals》2009,36(9):527-536

A pyroxene with composition LiNiSi₂O₆ was synthesized at T = 1,473 K and P = 2.0 GPa; the cell parameters at T = 298 K are a = 9.4169(6) Å, b = 8.4465(7) Å, c = 5.2464(3) Å, β = 110.534(6)°, V = 390.78(3) Å³. TEM examination of the LiNiSi₂O₆ pyroxene showed the presence of h + k odd reflections indicative of a primitive lattice, and of antiphase domains obtained by dark field imaging of the h + k odd reflections. A HT in situ investigation was performed by examining TEM selected area diffraction patterns collected at high temperature and synchrotron radiation powder diffraction. In HTTEM the LiNiSi₂O₆ was examined together with LiCrSi₂O₆ pyroxene. In LiCrSi₂O₆ the h + k odd critical reflections disappear at about 340 K; they are sharp up to the transition temperature and do not change their shape until they disappear. In LiNiSi₂O₆ the h + k odd reflections are present up to sample deterioration at 650 K. A high temperature synchrotron radiation powder diffraction investigation was performed on LiNiSi₂O₆ between 298 and 773 K. The analysis of critical reflections and of changes in cell parameters shows that the space group is P-centred up to the highest temperature. The comparative analysis of the thermal and spontaneous strain contributions in P2₁/c and C2/c pyroxenes indicates that the high temperature strain in P-LiNiSi₂O₆ is very similar to that due to thermal strain only in C2/c spodumene and that a spontaneous strain contribution related to pre-transition features is not apparent in LiNiSi₂O₆. A different high-temperature behaviour in LiNiSi₂O₆ with respect to other pyroxenes is suggested, possibly in relation with the presence of Jahn–Teller distortion of the M1 polyhedron centred by low-spin Ni³⁺.  相似文献   

Potential of submarine-cave sediments and oxygen isotope composition of cavernicolous micro-bivalve as a late Holocene paleoenvironmental record   总被引：2，自引：1，他引：1  

Akihisa Kitamura  Nagisa Yamamoto  Tomoki Kase  Shu-ichi Ohashi  Mayumi Hiramoto  Hitoshi Fukusawa  Tsuyoshi Watanabe  Tomohisa Irino  Hiroshi Kojitani  Michiyo Shimamura  Ikuo Kawakami 《Global and Planetary Change》2007,55(4):301-316

A sediment layer (43 cm thick) and surface sediments (5 cm thick) in a submarine limestone cave (31 m water depth) on the fore-reef slope of Ie Island, off Okinawa mainland, Japan, were examined by visual, mineralogical and geochemical means. Oxygen isotope analysis was performed on the cavernicolous micro-bivalve Carditella iejimensis from both cored sediments and surface sediments, and the water temperature within the cave was recorded for nearly one year. These data show that: (1) water temperature within the cave is equal to that at 30 m deep in the open sea; (2) the biotic and non-biotic environments within the cave have persisted for the past 2000 years; (3) mud-size carbonate detritus is a major constituent of the submarine-cave deposit, and may have come mainly from the suspended carbonate mud produced on the emergent Holocene reef flat over the past two millennia; (4) the δ¹⁸O-derived temperature (T_δ18_O) of C. iejimensis suggests that the species grows between April and July; (5) the T_δ18_O of C. iejimensis from cored sediments implies that there were two warmer intervals, at AD 340 ± 40 and AD 1000 ± 40, which correspond to the Roman Warm Period and Medieval Warm Period, respectively. These suggest that submarine-cave sediments provide unique information for Holocene reef development. In addition, oxygen isotope records of cavernicolous C. iejimensis are a useful tool to reconstruct century-scale climatic variability for the Okinawa Islands during the Holocene.  相似文献   

In situ observational research of the gap wind “Hijikawa-Arashi” in Japan     

Yukitaka Ohashi  Toru Terao  Yoshinori Shigeta  Teruo Ohsawa 《Meteorology and Atmospheric Physics》2015,127(1):33-48

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拉萨上空大气臭氧垂直分布的高空气球探测   总被引：11，自引：0，他引：11  

石广玉  白宇波  岩坂泰信  大桥铁弥 《地球科学进展》2000,15(5):522-524

用臭氧探空仪于1998年8月和10月测量了在拉萨上空的臭氧垂直分布,并与河北香河的观测资料进行了对比。结果表明,拉萨上空对流层臭氧浓度较低,在25～26 km之间臭氧分压最大,在30～34 km之间混合比最大。从典型的臭氧垂直分布廓线推算出大气臭氧总含量为261.6DU。  相似文献   

Concentrations of 222 Rn, Its Short-Lived Daughters And 212 Pb And Their Ratios Under Complex Atmospheric Conditions And Topography     

Toshio Kataoka  Eiji Yunoki  Mitsuo Shimizu  Tadashige Mori  Osamu Tsukamoto  Satoshi Takahashi  Hironori Fudeyasu  Yukitaka Ohashi  Ken Sahashi  Toshihiko Maitani  Koh'ichi Miyashita  Toru Iwata  Takayuki Sasaki  Yoko Fujikawa  Akira Kudo  Roger H. Shaw 《Boundary-Layer Meteorology》2003,107(1):219-249

Atmospheric activity concentrations of ²¹²Pb and short-lived ²²²Rndaughters, together with meteorological elements, have been observed continuously atthree sites at Kamisaibara Village in Japan. In addition, atmospheric activity concentrationof ²²²Rn, equilibrium-equivalent concentration of ²²²Rn and conditionsof the lower atmosphere were observed for three intensive observation periods at Akawase,one of the three sites in Kamisaibara Village. The equilibrium-equivalent concentration of²²²Rn is almost the same as the atmospheric activity concentration of short-lived²²²Rn daughters.The activity concentrations of ²¹²Pb and the short-lived ²²²Rn daughtersand their ratio were low in the daytime owing to convective mixing, and high at nightowing to the surface-based inversion during periods of no precipitation. Their variationshave several patterns corresponding to the scale of the drainage wind or weak mixing.Mechanical mixing due to strong winds through both day and night during the first andsecond observation periods made the atmospheric activity concentrations of ²¹²Pb and the short-lived ²²²Rn daughters continuously low. However, their ratios werecontinuously high during the first period yet continuously low during the second period.This difference can be explained by the effect ofextraction of ²²⁰Rn and ²²²Rndue to strong winds and snow cover. There were also cases in which the ratio of theatmospheric activity concentration of ²¹²Pb to that of the short-lived ²²²Rndaughters at night was equal to or less than the ratio in the daytime. Thisinverse trend, asin the periods of no precipitation mentioned above, is considered to be due to near-neutralconditions on these nights.We find a difference in the ratio of the equilibrium-equivalent concentration of²²²Rn (the activity concentration of short-lived ²²²Rn daughters) tothe activity concentration of ²²²Rn during the first observation period and thatduring the second. The difference can be explained by snow cover on the ground. Wealso find differences among the ratios of the activity concentration of the short-lived²²²Rn daughters to that of ²²²Rn during the three observation periods.These differences can be explained by the submergence of paddy fields.  相似文献   

The crystal structure of CaFe3+SiAlO6 and the crystal chemistry of Fe3+—Al3+ substitution in calcium Tschermak's pyroxene     

Subrata Ghose  Fujio P. Okamura  Haruo Ohashi 《Contributions to Mineralogy and Petrology》1986,92(4):530-535

The crystal structure of a synthetic CaFe³⁺Al-SiO₆ pyroxene (20 kb, 1,375° C) with unit cell dimensions a=9.7797(16), b=8.7819(14), c=5.3685(5) Å, =105.78(1), space group C2/c has been refined by the method of least squares to an R-factor of 0.025 based on 812 reflections measured on an automatic single crystal diffractometer. The octahedral M1 site is occupied by 0.82 Fe³⁺ and 0.18 Al³⁺. Within the tetrahedral T site, Si⁴⁺ (0.50), Al³⁺ (0.41) and Fe³⁺ (0.09) ions are completely disordered, although submicroscopic domains with short-range order are very likely. The octahedral site preference energy of the Fe³⁺ ions with respect to Al³⁺ ions in CaFe³⁺AlSiO₆ is about 10 kcal/mole, which is much higher than that found in Y₃Al _x Fe_5–2O₁₂ garnets. Topologically the structure of CaFe³⁺AlSiO₆ is intermediate between that of diopside and calcium Tschermak's pyroxene, CaAlAlSiO₆. For CaM³⁺ AlSiO₆ clinopyroxenes an increase in the size of the M1 octahedron is accompanied by an increase in the average M2-0, bridging T-0 and 03-03 distances and kinking of the tetrahedral chain.  相似文献   

57Fe mössbauer study of synthetic Fe3+-melilites     

Masahide Akasaka  Haruo Ohashi 《Physics and Chemistry of Minerals》1985,12(1):13-18

Synthetic Fe³⁺-melilites containing NaCaFe³⁺-Si₂O₇-, Ca₂Fe³⁺AlSiO₇- or Sr₂Fe³⁺AlSiO₇-components have been studied by ⁵⁷Fe Mössbauer spectroscopy. The spectrum of åkermanite containing an NaCaFe³⁺Si₂O₇-component consists of one doublet identified to belong to Fe³⁺ in T1 sites. The spectra of åkermanite and gehlenite containing Ca₂Fe³⁺ AlSiO₇- or Sr₂Fe³⁺ AlSiO₇-component consist of two doublets. The inner and outer doublets are identified to belong to Fe³⁺ in the less distorted T1 and that in the more distorted T2 sites, respectively. The area ratios of the spectra show that the site occupancy of Fe³⁺ (T1) in gehlenite is less than that in åkermanite in which the distribution of Fe³⁺ in T1 and T2 sites is apparently random. The different distributions can be explained in terms of competition between minimizing the deficiency in the electrostatic valence and the preference of Al for T1 sites which the isomer shift measurements show to be more ionic.  相似文献   

The high-pressure C2/c–P21/c phase transition along the LiAlSi2O6–LiGaSi2O6 solid solution     

Fabrizio Nestola  Tiziana Boffa Ballaran  Haruo Ohashi 《Physics and Chemistry of Minerals》2008,35(8):477-484

Two synthetic single-crystals with composition Li(Al_0.53Ga_0.47)Si₂O₆ and LiGaSi₂O₆ and space group C2/c at room conditions have been studied under pressure by means of X-ray diffraction using a diamond anvil cell. The unit-cell parameters were determined at 12 and 10 different pressures up to P = 8.849 and P = 7.320 GPa for Li(Al_0.53Ga_0.47)Si₂O₆ and LiGaSi₂O₆, respectively. The sample with mixed composition shows a C2/c to P2₁/c phase transformation between 1.814 and 2.156 GPa, first-order in character. The transition is characterised by a large and discontinuous decrease in the unit-cell volume and by the appearance of the b-type reflections (h + k = odd) typical of the primitive symmetry. The Ga end-member shows the same C2/c to P2₁/c transformation at a pressure between 0.0001 and 0.39 GPa. The low-pressure value at which the transition occurred did not allow collecting any data in the C2/c pressure stability field except that on room pressure. Our results compared with those relative to spodumene (LiAlSi₂O₆, Arlt and Angel 2000a) indicate that the substitution of Al for Ga at the M1 site of Li-clinopyroxenes strongly affects the transition pressure causing a decrease from 3.17 GPa (spodumene) to less than 0.39 GPa (LiGaSi₂O₆) and decreases the volume discontinuity at the transition. As already found for other compounds, the C2/c low-pressure phases are more rigid than the P2₁ /c high-pressure ones. Moreover, the increase of the M1 cation radius causes a decrease in the bulk modulus K _T0. The axial compressibility among the Li-bearing clinopyroxenes indicates that the c axis is the most rigid for the C2/c phases while it becomes the most compressible for the P2₁ /c phases.  相似文献   

Optical spectroscopic study of synthetic NaScSi<Subscript>2</Subscript>O<Subscript>6</Subscript>–CaNiSi<Subscript>2</Subscript>O<Subscript>6</Subscript> pyroxenes at normal and high pressures     

Michail N. Taran  Haruo Ohashi  Monika Koch-Müller 《Physics and Chemistry of Minerals》2008,35(3):117-127

Six synthetic NaScSi₂O₆–CaNiSi₂O₆ pyroxenes were studied by optical absorption spectroscopy. Five of them of intermediate (Na_1−x , Ca _x )(Sc_1−x , Ni _x )Si₂O₆ compositions show spectra typical of Ni²⁺ in octahedral coordination, more precise Ni²⁺ at the M1 site of the pyroxene structure. The common feature of all spectra is three broad absorption bands with maxima around 8,000, 13,000 and 24,000 cm⁻¹ assigned to ³ A _2g → ³ T _2g, ³ A _2g → ³ T _1g and →³ T _1g (³ P) electronic spin-allowed transitions of ^VINi²⁺. A weak narrow peak at ∼14,400 cm⁻¹ is assigned to the spin-forbidden ³ A _2g → ¹ T _2g (¹ D) transition of Ni²⁺. Under pressure the spin-allowed bands shift to higher energies and change in intensity. The octahedral compression modulus, calculated from the shift of the ³ A _2g → ³ T _2g band in the (Na_0.7Ca_0.3)(Sc_0.7Ni_0.3)Si₂O₆ pyroxene is evaluated as 85±20 GPa. The Racah parameter B of Ni²⁺(M1) is found gradually changing from ∼919 cm⁻¹ at ambient pressure to ∼890 cm⁻¹ at 6.18 GPa. The Ni end-member pyroxene [(Ca_0.93 Ni_0.07)NiSi₂O₆] has a spectrum different from all others. In addition to the above mentioned bands of Ni²⁺(M1) it displays several new relatively intense and broad extra bands, which were attributed to electronic transitions of Ni²⁺ at the M2 site. In difference to CaO₈ polyhedron geometry of an eightfold coordination, Ni²⁺(M2)O₈ polyhedra are assumed to be relatively large distorted octahedra. Due to different distortions and different compressibilities of the M1 and M2 sites the Ni²⁺(M1)- and Ni²⁺(M2)-bands display rather different pressure-induced behaviors, becoming more resolved in the high-pressure spectra than in that measured at atmospheric pressure. The octahedral compression modulus of Ni²⁺(M1) in this end-member pyroxene is evaluated as 150 ± 25 GPa, which is noticeably larger than in Ni_0.3 pyroxene. This is due to a smaller size and, thus, a stiffer character of Ni²⁺(M1)O₆ octahedron in the (Ca_0.93Ni_0.07)NiSi₂O₆ pyroxene compared to (Na_0.7Ca_0.3)(Sc_0.7Ni_0.3)Si₂O₆.

Monika Koch-MüllerEmail:

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Reconstruction of paleotemperatures in the Northwest Pacific over the past 3000 years from δO values of the micro-bivalvia Carditella iejimensis found in a submarine cave     

Nagisa Yamamoto  Akihisa Kitamura  Tomohisa Irino  Tomoki Kase  Syu-ichi Ohashi 《Global and Planetary Change》2008,62(1-2):97-106

We measured the δ¹⁸O values of the whole shells of the cavernicolous micro-bivalvia Carditella iejimensis obtained from sediments within a submarine cave (31 m water depth) at Ie Island (Okinawa Island, Japan) in the subtropical Northwest Pacific. Our results show no significant millennial-scale trend in the δ¹⁸O record, implying that both springtime temperature and the δ¹⁸O of sea water at 30 m depth around the Okinawa Islands have been stable for the past 3000 years at values similar to those of today. Moreover, we found one exceptionally light δ¹⁸O value from specimens spanning the past 250 years. The δ¹⁸O-derived temperature represents a departure of 2.1 °C from the average value for the past 250 years, being equal to the departure recorded during unusually high temperatures in the spring of 1998. This finding may imply that such high springtime sea surface temperature has been a rare event over the past 3000 years.  相似文献