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.     

Structural change of GeO2 under pressure

Pressure-induced amorphization of α-quartz type GeO₂ was studied with a newly developed X-ray diffraction system which consists of a 4-circle goniometer and a curved position sensitive detector. Single-crystal diffraction was measured under pressurs up to 7.3 GPa at room temperature in order to investigate pretransitional phenomena. Diffraction intensity and line width of the diffraction profiles showed no remarkable change up to 5.9 GPa. However, no sharp diffraction line was observed at pressures over 6.5 GPa. The bulk modulus at 0.1 MPa and its pressure derivative of α-quartz type GeO₂ were determined to be K _T =32.8(3.3) GPa and K′ _T =6.0(2.0), respectively. In situ microscopic observations of the amorphization transformation was also performed. The large volume change due to amorphization was observed and estimated to be about 10%.     

Characteristics of ionic components in precipitation in Kitakyushu City,Japan

Precipitation samples were collected by filtrating bulk sampler in Kitakyushu City, Japan, from January 1988 to December 1990. Volume weighted annual mean of pH was 4.93, but the pH distribution indicated that most probable value lay in the range pH 6.0–6.4. Volume weighted annual mean concentrations of major ionic components were as follows; SO ₄ ^2– : 84.2, NO ₃ ^– : 28.1, Cl^–: 86.3, NH ₄ ⁺ : 45.5, Ca²⁺: 63.3, Mg²⁺: 27.0, K⁺: 3.4, Na⁺: 69.0 µ eq l^–1. The highest concentrations of these ionic components were observed in winter and the lowest occurred in the rainy season. The ratio of ex-SO ₄ ^2– /NO ₃ ^– exhibited the lowest ratio in summer, and the highest ratio in winter. Good correlations were obtained between Cl^– and Na⁺, ex-SO ₄ ²⁺ and ex-Ca²⁺, NO ₃ ^– and ex-Ca²⁺, and NH ₄ ⁺ and ex-SO ₄ ^2– , respectively. However, no correlation between Cl^– and Na⁺ with Ca²⁺ was observed. The relationship of H⁺ with (ex-SO ₄ ^2– + NO ₃ ^– ) - (ex-Ca²⁺ + NH ₄ ⁺ ) indicated positive correlation.     

Depositional mechanics of turbulent nuées ardentes (surges) from their grain sizes

The ability of turbulent nuées ardentes (surges) to transport coarse pyroclasts has been questioned on the basis that settling velocities of coarse fragments in the deposits are much too high for them to have been supported by turbulence in a dilute gas suspension. A computer model is used to evaluate the settling velocity of pyroclasts in suspensions of varying concentration and temperature. Since suspension of grains in low-concentration surges occurs if the shear velocity exceeds the settling velocity, the shear velocities related to the 16th and 84th percentiles, and the mean of the grain-size distribution are compared in surge deposits of the Vulsini, with the shear velocity necessary to move the coarsest grain on the bed surface (the Shields criterion). The results show that the settling velocities do not vary significantly in gaseous suspensions having volume concentrations lower than 15%, and that an increase in concentration to 25% is not sufficient to decrease the settling velocity of the coarser fraction, if it represents flow shear velocity. It is shown that the settling velocity of the mean grain size (M _z ) best depicts the shear velocity of a dilute turbulent suspension. Applying the results to the May 1902 paroxysmal nuées ardentes of Mount Pelée shows that the estimated mean velocities are well within the observed velocities, and sufficient to support all the clasts in dilute, turbulent suspensions.     

Isotopic geochemistry of acid thermal waters and volcanic gases from Zaō volcano in Japan

The chemical composition and D/H, and ratios have been determined for the acid hot waters and volcanic gases discharging from Zaō volcano in Japan. The thermal springs in Zaō volcano issue acid sulfate-chloride type waters (Zaō) and acid sulfate type waters (Kamoshika). Gases emitted at Kamoshika fumaroles are rich in CO₂, SO₂ and N₂, exclusive of H₂O. Chloride concentrations and oxygen isotope data indicate that the Zaō thermal waters issue a fluid mixture from an acid thermal reservoir and meteoric waters from shallow aquifers. The waters in the Zaō volcanic system have slight isotopic shifts from the respective local meteoric values. The isotopic evidence indicates that most of the water in the system is meteoric in origin. Sulfates in Zaō acid sulfate-chloride waters with δ³⁴S values of around +15‰, are enriched in ³⁴S compared to Zaō H₂S, while the acid sulfate waters at Kamoshika contain supergene light sulfate (δ³⁴S = + 4‰) derived from volcanic sulfur dioxide from the volcanic exhalations. The sulfur species in Zaō acid waters are lighter in δ³⁴S than those of other volcanic areas, reflecting the difference in total pressure.     

Element Mobility During Incipient Granulite Formation at Kabbaldurga, Southern India

At Kabbaldurga, infiltration of carbonic fluids along a systemof ductile shears and foliation planes has led to partial transformationof Archaean grey biotite–hornblende gneiss to coarse-grainedmassive charnockite at about 2.5 b.y. ago. The dehydration ofthe gneiss assemblage was induced by a marked metasomatic changeof the reacting system from granodioritic to granitic, and obviouslytook place under conditions of an open system at 700–750?C and 5–7 kb. Extensive replacement of plagioclase (An_16–30)by K-feldspar through Na, Ca–K exchange reactions withthe ascending carbonic fluids led to strong enrichment in K,Rb, Ba, and SiO₂, and to a depletion in Ca. Progressive dissolutionof hornblende, biotite, magnetite, and the accessory mineralsapatite and zircon resulted in a marked depletion in Fe, Mg,Ti, Zn, V, P, and Zr. Most important is the recognition of REEmobility: with advancing charnockitization, the moderately fractionatedREE distribution patterns of the grey gneisses (La_N270; La_N/Yb_N= 5–20; Eu_N27; Eu/Eu^* = 0.6–0.3) give way to stronglyfractionated REE patterns with a positive Eu-anomaly (La_N200;La_N/Yb_N = 20–80; Eu_N22; Eu/Eu^* = 0.6–1.8). The systematicdepletion especially in the HREE is due to the progressive dissolutionof zircon, apatite (and monazite), which strongly concentratethe REE. Stable isotope data (¹⁸O of 6.9–8.0 per mille for gneissesand charnockites; ¹³C of –8.5 and –6.5 per millefor late carbonate) indicate a magmatogenic source for the carbonicfluids. In contrast to the currently favoured derivation ofcarbonic fluids by decarbonation of the upper mantle or degassingof underplated basaltic intrusions, it is discussed here thatabundant fluid inclusions in lower crustal charnockites providedan extensive reservoir of ‘fossil’ carbonic fluids.Shear deformation has tapped this reservoir and generated thechannel-ways for fluid ascent. Charnockitization of the Kabbaldurgatypethus appears to be a metasomatic process which is tectonicallycontrolled and restricted to the crustal level of the amphiboliteto granulite transition.     

Tectono-thermal modeling of the Yinggehai Basin,South China Sea

Based on the observed data, the average value of surface heat flow in the Yinggehai Basin is calculated and it turns out to be 84.1 mW/m². The thermal evolution of the basin since the Cenozoic era has been attempted by tectono-thermal modeling. Three-phase extension made the basin become hotter and hotter, reaching its climax in paleo-temperature history since 5.2 Ma. And nowadays, the basin is in the heat flow decreasing period. During the Cenozoic era, the basement heat flow remained at 50–70 mW/m² all the time. This is related to the degree of each extension phase, stretching rate mode and also the limited basin scale. Modeling results also show that, the surface heat flow is controlled mainly by the basement heat flow, and less than 20% comes from radiogenic heat production in the sediments of the basin     

Iodine concentrations of soils near Trabzon, Turkey: a region of endemic goiter

Iodine contents of soils developed over the major rock formations of the northern zone of the Eastern Pontide Tectonic Belt (Northeastern Turkey) have been investigated with respect to soil-parent rock relationship, effect of topography, elevation, and climate to construe its effect on the health of the local population. Samples were collected from the A and B horizons of the soils developed over the major stratigraphic units constituting the eastern Pontides, including the Lower Basic Complex of Jurassic-Lower Cretaceous age, the Berdiga limestone (Jurassic-lower Cretaceous), the Dagbasi granitoid (Upper Cretaceous), volcano-sedimentary sequence of Upper Cretaceous age, ore-bearing and barren dacites of Upper Cretaceous age, and Neogene alkaline basalts. Chemical analyses of soil samples indicate significantly lower iodine abundances for all the soils studied (5–28 ppm) in comparison to the average abundance of iodine in analogous soils of other parts of the world (22–93 ppm). The concentration of iodine in soils developed over the same geologic formation decrease with increasing elevation. In certain cases, this decrease may reach up to 70%. Goiter is highly common throughout this region in Turkey. The results of this study suggest that the iodine deficiency of region’s soils may be a principal underlying cause for this area of Turkey being an endemic goiter region.