Oxygen isotope exchange rate between dissolved sulfate and water at hydrothermal temperatures

Oxygen isotope exchange rate between dissolved sulfate and water was experimentally determined at 100, 200 and 300°C. The isotope exchange rate is strongly dependent on temperature and pH of the solution. Combining the temperature and pH dependence of the reaction rate, the exchange reaction was estimated to be first-order with respect to sulfate. The logarithm of apparent rate constant of exchange reaction at a given temperature is a function of the pH calculated at the experimental temperatures. From the pH dependence of the apparent rate constant, it was deduced that the isotope exchange reaction between dissolved sulfate and water proceeds through collision between H₂SO⁰₄ and H₂O at low pH, and between HSO^?₄ and H₂O at intermediate pH. The isotope exchange rate obtained indicates that oxygen isotope geothermometry utilizing the studied isotope exchange is suitable for temperature estimation of geothermal reservoirs. The extrapolated half-life of this reaction to oceanic temperature is about 10⁹ years, implying that exchange between oceanic sulfate and water cannot control the oxygen isotope ratio of oceanic sulfates.     

Sulfur isotope study of Quaternary volcanic rocks from the Japanese Islands Arc

The sulfide and sulfate contents and their δ³⁴S values were determined in Quaternary volcanic rocks from the Japanese Islands Arc. The total sulfur contents are much lower (less than 40 ppm) and the δ³⁴S values are higher (+4.4 ± 2.1) than those of ocean-floor basalts (800 ± 100 ppm and +0.8 ± 0.5, respectively; Moore and Fabbi, 1971; Sakaiet al., 1982). Lateral variations of both sulfur content and δ³⁴S values were observed in the four volcanic belts in Japan. In the Northeast Japan belt, the sulfur content (30 ± 10 ppm) of the rocks in the inner zone (the Japan Sea side) is 3 to 5 times that in the outer zone (the Pacific side), although the δ³⁴S values of the two zones are almost the same (+4.3 ± 1.0). The δ³⁴S values for the two belts in West Japan are on the average 2%. higher than those of East Japan.This study suggests that the primary magmas that formed the island arc volcanic rocks are initially depleted in sulfur (<120 ppm) and enriched in ³⁴S ($\text{δ}{}^{34}\text{S: +5 ～ +7}$) compared to ocean-floor tholeiitic basalts which formed at mantle under oceanic region. This indicates that the upper-mantle is heterogeneous in sulfur content and isotope composition.     

Streaming potential observations, using geothermal wells and in situ electrokinetic coupling coefficients under high temperature

In an attempt to detect streaming potentials induced by subsurface water flows, we have observed the horizontal electric field (self-potential) variations across stationary electric dipoles near geothermal wells in the Takinoue geothermal area, Japan. We observed variations of self-potential which seem to be associated with the water flows in the aquifer, induced by turning on and off the flow of the wells. Amplitudes of the variations are 3–5 mV across 60–200 m dipoles, and can be explained well with a proposed electrokinetic model: the streaming potential coefficient of − 15 mV/bar and/or the ζ-potential of −50 to −100 mV in the aquifer are appropriate to explain the observed data by the model. The obtained electrokinetic coupling coefficients are in situ ones and determined for crustal rock-water system under high temperature (˜200°C) condition. The present results, together with a laboratory study by Ishido and Mizutani (1981), give fundamental information on electrokinetic coupling coefficients in the earth's interior, and are very important when we make quantitative interpretations of self-potentials generated by geothermal activity on the basis of electrokinetic effects.     

Zinc-rich Pyrite from the TAG Active Mound, the TAG Hydrotherma Field, Mid-Atlantic Ridge

Abstract: Pyrite rich in Zn, up to 3.1 wt%, was found in the TAG active mound of the TAG hydrothermal field, the slow-spreading Mid-Atlantic Ridge at 26°08'N and 44°49'W. The Zn-rich pyrite is characterized by an optical homogeneity, a homogeneous distribution of Zn in the back-scattered electron images, both at a magnification of about 500, a negative correlation between Fe and Zn contents of the pyrite and a rather small unit cell edge (a₀ = 5.4117 ± 0.0008Å), strongly indicating that the detected Zn is present in the pyrite in solid solution. Such Zn concentrations are observed exclusively in dendritic pyrite, suggesting that the Znrich pyrite grew from hydrothermal fluids of a high degree of supersaturation due to quenching on the seafloor.     

Research on the seismotectonics of the Jan－uary 17，1995 Hanshin M7．2 earthquake

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Nutrients adsorption from seawater by new porous carrier made from zeolitized fly ash and slag

This study investigated the adsorption and precipitation of phosphate by blast furnace slag (BFS) separately.

In order to evaluate the adsorption capacity of BFS, BFS was treated before its use by acid. The authors aim to develop a new porous carrier to adsorb simultaneously ammonium and phosphate from seawater under eutrophic conditions. The current paper deals with a promising new approach to improve the utilization of some industrial solid wastes such as BFS and zeolite synthesized from fly ash [ZFA(Fe)] by their solidification to cylindrical porous carriers using a hydrothermal hot-pressing (HHP) method.

Attempts to produce porous carriers using an arranged HHP method with different porosities (24%, 40% and 52% (v/v)) were carried out. Physical properties of carriers such as porosity, compressive strength and height have been investigated. Laboratory studies showed strong evidence that the porous carrier was very selective towards phosphate and ammonium. The results demonstrated the role of porosity in enhancing phosphate and ammonium adsorption by the increase of the surface area per weight. The estimates of the parameters and the correlation coefficients according to the Freundlich equations revealed that adsorption was related to the porosity of carriers and phosphate and ammonium were adsorbed well on the carriers having large porosity.

The results suggested that developing carrier with high porosity was a promising way to enhance nutrients adsorption.     

A Shock-Wave Heating Model for Chondrule Formation: Effects of Evaporation and Gas Flows on Silicate Particles

A shock-wave heating model is one of the possible models for chondrule formation. We examine, within the framework of a shock-wave heating model, the effects of evaporation on the heating of chondrule precursor particles and the stability of their molten state in the postshock flow. We numerically simulate the heating process in the flow taking into account evaporation. We find that the melting criterion and the minimum radius criterion do not change significantly. However, if the latent heat cooling due to the evaporation dominates the radiative cooling from the precursor particle, the peak temperature of the precursor particle is suppressed by a few hundred Kelvins. We also find that the total gas pressure (ram plus static) acting on the precursor particle exceeds the vapor pressure of the molten precursor particle. Therefore, it is possible to form chondrules in the shock-wave heating model if the precursor temperature increases up to the melting point.     

Oxygen isotope fractionation factors between anhydrite and water from 100 to 550°C

Oxygen isotope exchange between anhydrite and water was studied from 100 to 550°C, using the partial equilibrium method. The exchange rate was extremely low in NaCl solution. In the lower-temperature range, acid solutions were used to produce sufficient reaction to determine the oxygen isotope fractionation factors. The fractionation factors obtained in the present study are definitely different from those given by Lloyd [8]. They are similar to those for the HSO₄^?-water system studied by Mizutani and Rafter [19], and are consistently 2‰ higher than those of the barite-water system by Kusakabe and Robinson [5]. The temperature dependence of the oxygen isotope fractionation factors was calculated by the least squares method in which the weight was taken to be inversely proportional to the experimental error. The fractionation is given by:10³lnαanhydrite-water=3.21×(10³/T)²?4.72Available δ¹⁸O values of natural anhydrite were used to test the validity of this expression. It is shown that this newly revised geothermometer can be successfully applied to natural hydrothermal anhydrite.     

Molecular and isotopic characteristics of gas hydrate-bound hydrocarbons in southern and central Lake Baikal

We investigated the molecular composition (methane, ethane, and propane) and stable isotope composition (methane and ethane) of hydrate-bound gas in sediments of Lake Baikal. Hydrate-bearing sediment cores were retrieved from eight gas seep sites, located in the southern and central Baikal basins. Empirical classification of the methane stable isotopes (δ¹³C and δD) for all the seep sites indicated the dominant microbial origin of methane via methyl-type fermentation; however, a mixture of thermogenic and microbial gases resulted in relatively high methane δ¹³C signatures at two sites where ethane δ¹³C indicated a typical thermogenic origin. At one of the sites in the southern Baikal basin, we found gas hydrates of enclathrated microbial ethane in which ¹³C and deuterium were both highly depleted (mean δ¹³C and δD of –61.6‰ V-PDB and –285.4‰ V-SMOW, respectively). To the best of our knowledge, this is the first report of C₂ δ¹³C–δD classification for hydrate-bound gas in either freshwater or marine environments.