Pressure and temperature dependence of cation distribution in Mg-Mn olivine

Synthetic (Mg_0.51, Mn_0.49)₂SiO₄ olivine samples are heat-treated at three different pressures; 0, 8 and 12 GPa, all at the same temperature (～500° C). X-ray structure analyses on these single crystals are made in order to see the pressure effect on cation distribution. The intersite distribution coefficient of Mg and Mn in M1 and M2 sites, K _D = (Mn/Mg) _M1/(Mn/Mg) _M2, of these samples are 0.192 (0 GPa), 0.246 (8 GPa) and 0.281 (12 GPa), indicating cationic disordering with pressure. The small differences of cell dimensions between these samples are determined by powder X-ray diffraction. Cell dimensions b and c decrease, whereas a increases with pressure of equilibration. Cell volume decreases with pressure as a result of a large contraction of the b cell dimension. The effect of pressure on the free energy of the cation exchange reaction is evaluated by the observed relation between the cell volume and the site occupancy numbers. The magnitude of the pressure effect on cation distribution is only a fifth of that predicted from the observed change in volume combined with thermodynamic theory. This phenomenon is attributed to nonideality in this solid solution, and nonideal parameters are required to describe cation distribution determined in the present and previous experiments. We use a five-parameter equation to specify the cationic equilibrium on the basic of thermodynamic theory. It includes one energy parameter of ideal mixing, two parameters for nonideal effects, one volume parameter, and one thermal parameter originated from the lattice vibrational energy. The present data combined with some of the existing data are used to determine the five parameters, and the cation distribution in Mg-Mn olivine is described as a function of temperature, pressure, and composition. The basic framework of describing the cationic behavior in olivine-type mineral is worked out, although the result is preliminary: each of the determined parameters is not accurate enough to enable us to make a reliable prediction.     

Nuclide analyses of rare earth elements of the Oklo uranium ore samples: a new method to estimate the neutron fluence

Isotopic ratios and abundances of all REE in two Oklo ore samples have been measured. We have succeeded in developing a new method to estimate the neutron fluence, the conversion factor of uranium and the average neutron energy (or temperature) based on Gd and U isotopic ratios. This new calculation is found to be useful in evaluating those parameters for the natural nuclear reactors at Oklo. Comparison is made between the neutron fluence values evaluated by our new method employing Gd isotopes and a previous one [11] employing Sm and Nd isotopes. The relative agreement becomes better with the increase of fluence. A relationship between the abundances of fissiongenic nuclides of La, Ce, Nd, Sm, and Gd and their mass numbers is also presented.     

Classification and distribution of Oligocene Aetiocetidae (Mammalia; Cetacea; Mysticeti) from western North America and Japan

Abstract Fossil whales in the very rare, primitive, extinct cetacean family Aetiocetidae are small, relict, toothed mysticetes that persisted into Late Oligocene time after more highly derived baleen-bearing mysticetes had already evolved. No known aetiocetid could be ancestral to baleen-bearing mysticetes, but aetiocetid morphology is in many ways intermediate between archaeocetes and baleen-bearing mysticetes, demonstrating the probable transitional steps passed through in the evolution of baleen-bearing mysticetes. Their discovery indicates that mysticetes evolved from Archaeocetes, and supports theories of the monophyly of Cetacea. Late Oligocene aetiocetids have been found on both sides of the North Pacific Ocean: on Vancouver Island, British Columbia, Canada; in Oregon and Washington, USA; in Baja California Sur, México; and the islands of Kyushu and Hokkaido, Japan. The most primitive North American aetiocetid, Chonecetus sookensis Russell, 1968, is from the early Late Oligocene Hesquiat Formation on Vancouver Island, British Columbia, Canada. A more derived, Late Oligocene species, Chonecetus goedertorum Barnes and Furusawa, new species, from the Late Oligocene Pysht Formation, Olympic Peninsula, Washington, has the primitive placental mammalian tooth count of 11/11. The type genus of the family, Aetiocetus Emlong, 1966, has as its type species, A. cotylalveus Emlong, 1966, known only from the Late Oligocene Yaquina Formation on the coast of Oregon. It has 11 upper teeth on each side of the rostrum. A more derived species, Aetiocetus weltoni Barnes and Kimura, new species, from a higher stratigraphic level in the Yaquina Formation, has a more posteriorly positioned cranial vertex and a tooth count of 11/12. We describe four new species of aetiocetids in three genera from the Late Oligocene Morawan Formation near Ashoro, Hokkaido, Japan. The most primitive, Ashorocetus eguchii Barnes and Kimura, new genus and species, has a primitive stage of cranial telescoping, and is closely related to Chonecetus Russell, 1968. Another, Morawanocetus yabukii Kimura and Barnes, new genus and species, in some ways intermediate between Chonecetus and Aetiocetus, has a suite of unique derived characters, including a much foreshortened brain case. The third, Aetiocetus tomitai Kimura and Barnes, new species, is the most primitive species of Aetiocetus yet discovered. The fourth, Aetiocetus polydentatus Sawamura, new species, the most derived species of Aetiocetus known, has a highly telescoped cranium, homodonty, polydonty and a dental count of 13–14/14–15. The fossil record now indicates considerable diversity in the family, with several different contemporaneous lineages in three new subfamilies: Chonecetinae, Morawanocetinae and Aetiocetinae. Aetiocetids are not known outside the North Pacific. Many Recent mysticetes are essentially cosmopolitan, and aetiocetids might have also been relatively widely dispersed. We suspect that with time their remains will be found around other ocean basins also. If so, then they may be potentially useful in trans-oceanic geological correlations.     

Numerical study of the oxidation process of dimethylsulfide in the marine atmosphere

A box model, involving simple heterogeneous reaction processes associated with the production of non-sea-salt sulfate (nss-SO ₄ ^2– ) particles, is used to investigate the oxidation processes of dimethylsulfide (DMS or CH₃SCH₃) in the marine atmosphere. The model is applied to chemical reactions in the atmospheric surface mixing layer, at intervals of 15 degrees latitude between 60° N and 60° S. Given that the addition reaction of the hydroxyl radical (OH) to the sulfur atom in the DMS molecule is faster at lower temperature than at higher temperature and that it is the predominant pathway for the production of methanesulfonic acid (MSA or CH₃SO₃H), the results can well explain both the increasing tendency of the molar ratio of MSA to nss-SO ₄ ^2– toward higher latitudes and the uniform distribution with latitude of sulfur dioxide (SO₂). The predicted production rate of MSA increases with increasing latitude due to the elevated rate constant of the addition reaction at lower temperature. Since latitudinal distributions of OH concentration and DMS reaction rate with OH are opposite, a uniform production rate of SO₂ is realized over the globe. The primary sink of DMS in unpolluted air is caused by the reaction with OH. Reaction of DMS with the nitrate radical (NO₃) also reduces DMS concentration but it is less important compared with that of OH. Concentrations of SO₂, MSA, and nss-SO ₄ ^2– are almost independent of NO _x concentration and radiation field. If dimethylsulfoxide (DMSO or CH₃S(O)CH₃) is produced by the addition reaction and further converted to sulfuric acid (H₂SO₄) in an aqueous solution of cloud droplets, the oxidation process of DMSO might be important for the production of aerosol particles containing nss-SO ₄ ^2– at high latitudes.     

Seasonal variations of spectra of wind speed and air temperature in the mesoscale frequency range

Seasonal variations of the spectra of wind speed and air temperature in the mesoscale frequency range from 1.3 × 10^-4 to 1.5 × 10^-3 Hz (10 min to 2 h periods) have been studied through observations over land for one year. Spectrographs [time series of isopleths of spectral densities, f · S(f) vs f] of wind speed and air temperature contain occasional peaks that are attributed to short-lived mesoscale atmospheric activity with narrow frequency bands. Significant spectral peaks of wind speed were found in 19% of the total observations in winter, and in 15–16% in the other seasons; for air temperature, they occured in 12% of observations in autumn, and in 16–19% in the other seasons. The peaks most often occurred in the period range from 30 min to 1 h; most had durations less than 24 h. Mesoscale fluctuations of wind speed and air temperature were highly correlated, and in most cases, phase differences were 90–180 ° with air temperature leading wind speed. Significant spectral peaks of wind speed often occurred during northerly seasonal cold winds in winter, and accompanied tropical and/or mid-latitude cyclones in the other seasons. When the peaks occurred, wind speed was usually relatively high and the atmospheric surface layer was unstable.     

Symmetrical fft technique and its applications to earthquake engineering

The objective of this paper is to propose an FFT technique symmetrical for time and frequency, in which the symmetrization is done by introducing generating functions. By the symmetrical treatment, it becomes possible to derive several complementary relations in the time and frequency domains. Based on the idea of the symmetrical FFT technique, the phase problem of seismic waves is discussed not only in the frequency domain but also in the time domain. Furthermore, the deconvolution technique to evaluate the minimum-phase-shift and all-pass functions of seismic waves, which is not discussed sufficiently in earthquake engineering, is developed in the two domains. Numerical examples to present these basic ideas are also illustrated in the symmetrical framework.     

Fractionation of sulfur isotopes and selenium between coexisting sulfide minerals from the Besshi deposit,Central Shikoku,Japan

Fractionation of sulfur isotopes and selenium was measured between coexisting pyrite and chalcopyrite and between coexisting pyrrhotite and chalcopyrite from the Besshi deposit of Kieslager-type, Central Shikoku, Japan. In all the pyrite-chalcopyrite pairs studied, ³⁴S is enriched in pyrite relative to chalcopyrite, while selenium is enriched conversely in chalcopyrite relative to pyrite. The mean ³⁴S_py-cp value is +0.53±0.36 per mil, and the mean value of the distribution coefficient of selenium, D_cp-py, is 2.58±0.64. In all the pyrrhotite-chalcopyrite pairs studied, the two minerals are very close to each other both in sulfur isotope and Se/S ratios. The mean ³⁴S_po-cp value is –0.08±0.16 per mil and the mean D_cp-po value is 0.99±0.05. The results have been discussed in comparison with similar data obtained for the Hitachi deposits of Kieslager-type, Japan (Yamamoto et al. 1983).     

On the chondrite—achondrite transition: mineralogy and chemistry of Yamato 74160 (LL7)

We report on the petrology, mineralogic properties and contents of major elements and trace elements Ag, Au, Bi, Cd, Co, Cs, Ga, In, Rb, Se, Te, Tl, U and Zn (determined by radiochemical neutron activation analysis) in Yamato 74160, interpreted as an LL7 chondrite. All properties are consistent with this meteorite having been recrystallized and partially melted locally once at temperatures well above 1090°C under conditions such that some minerals (e.g. plagioclase, euhedral pyroxene, tetrataenite) grew from melt pockets and siderophilic and chalcophilic elements were lost by extraction into eutectic melt that drained away. Inhomogeneous plagioclase compositions and mobile element loss suggest shock as the most likely heat source. Yamato 74160, while inferentially chondritic, is a larval achondrite: even higher temperatures and longer times would have been required to cause the separations necessary to transform it to an identifiable achondrite type.     

Fine structure beneath the Tohoku district, northeastern Japan arc, as derived by an inversion of P-wave arrival times from local earthquakes

Three dimensional P-wave velocity structure beneath the Tohoku district, northeastern Japan arc, is investigated by an inversion of arrival times from local earthquakes using the method originally due to Aki and Lee (1976).In the crust (0–32 km depth) a low-velocity region is found along the volcanic front and its vicinity. Velocities at depths of 32–65 km are low beneath the regions where many Quaternary volcanoes and geothermal areas are distributed. In the region deeper than 65 km, the subduction of the Pacific plate is clearly revealed, and the mantle structure above the descending plate is rather uniform. These features suggest that volcanic activities have relation to the upper mantle structure. The results obtained in this study will be helpful in investigating the mechanism of magma generation in a subduction zone.     

Antiferromagnetic transition of fayalite under high pressure studied by Mössbauer spectroscopy

Néel temperature (Tm _N of α-Fe₂SiO₄ (fayalite) was measured as a function of pressure by means of Mössbauer spectroscopy in the pressure range 0–16 Gpa. High pressure was generated using a clamp-type miniature diamond anvil cell which was inserted into a cryostat. The Néel temperature increased linearly with increasing pressure at a rate of dT _N /dp=2.2±0.2 K/GPa. The result is discussed on the basis of the model proposed for the magnetic structure of fayalite by Santoro et al. (1966). The observed dT _N /dp suggests that the superexchange interactions vary as the ?10/3 power of the volume while the volume dependence of the direct exchange interactions is positive and small.