Kinetics of reactions between aqueous sulfates and sulfides in hydrothermal systems   总被引：1，自引：0，他引：1  

Hiroshi Ohmoto  Antonio C. Lasaga 《Geochimica et cosmochimica acta》1982,46(10):1727-1745

The rates of chemical reactions between aqueous sulfates and sulfides are essentially identical to sulfur isotopic exchange rates between them, because both the chemical and isotopic reactions involve simultaneous oxidation of sulfide-sulfur atoms and reduction of sulfate-sulfur. The rate of reaction can be expressed as a second order rate law: R = k·[∑SO₄^2?]·[∑S^2?], where R is the overall rate, k is the rate constant and [∑SO₄^2?] and [∑S^2?] are molal concentrations. We have computed the rate constants from the available experimental data on the partial exchange of sulfur isotopes between aqueous sulfates and sulfides using the rate law established by us: $\text{ln(}\text{α}{}^{\mathrm{e}}\text{? α}\text{α}{}^{\mathrm{e}}\text{? α}{}^0\text{) = ? kt([∑SO}{}_4{}^{\mathrm{2?}}\text{] + [∑S}{}^{\mathrm{2?}}\text{])}$, where t is time and α⁰, α, and α^e are, respectively, the fractionation factors at t = 0 (the initial condition), at the end of experiment, and at equilibrium. The equilibrium fractionation factor can be expressed as: $\text{1000 ln α}{}^{\mathrm{e}}\text{=}\text{6.463 × 10}{}^6\text{T}{}^2\text{+ 0.56 (±.5)}$ (T in Kelvin).The rate constants are strongly dependent on T and pH, but not in as simple a manner as suggested by Igumnov (1976). Our rate constants in Na-bearing hydrothermal solutions decrease by 1 order of magnitude with an increase in pH by 1 unit at pH's less than ~3, remain constant in the pH range of ~4 to ~7, and again decrease at pH >7. The activation energy for the reaction also depends on pH: 18.4 ± 1 kcal/mole at pH = 2, 29.6 ± 1 kcal/mole at pH = 4 to 7, and between 40 and 47 kcal/mole at pH around 9. The observed pH dependence of the rate constant and of the activation energy can be best explained by a model involving thiosulfate molecules as reaction intermediates, in which the intramolecular exchange of sulfur atoms in thiosulfates becomes the rate determining step.The rate constants obtained in this study were used to compute the changes in the isotopic fractionation factors between aqueous sulfates and sulfides during cooling of fluids. Comparisons with data of coexisting sulfate-sulfide minerals in hydrothermal deposits, suggest that simple cooling was not a likely mechanism for coprecipitation of sulfate and sulfide minerals at temperatures below 350°C. Mixing of sulfide-rich solutions with sulfate-rich solutions at or near the depositional sites is a more reasonable process for explaining the observed fractionation.The degree of attainment of chemical equilibrium between aqueous sulfates and sulfides in a hydrothermal system, and the applicability of a_O2-pH type diagrams to mineral deposits, depends on the ∑S content and the thermal history of the fluid, which in turn is controlled by the flow rate and the thermal gradient in the system.The rates of sulfate reduction by non-bacterial processes involving a variety of reductants are also dependent on T, pH, [∑SO₄^2?], and [∑S^2?], and appear to be fast enough to become geochemically important at temperatures above about 200°C.  相似文献   

∼3,850 Ma tonalites in the Nuuk region,Greenland: geochemistry and their reworking within an Eoarchaean gneiss complex     

Allen P. Nutman  Vickie C. Bennett  Clark R. L. Friend  Kenji Horie  Hiroshi Hidaka 《Contributions to Mineralogy and Petrology》2007,154(4):385-408

The Eoarchaean (>3,600 Ma) Itsaq Gneiss Complex of southern West Greenland is dominated by polyphase orthogneisses with a complex Archaean tectonothermal history. Some of the orthogneisses have c. 3,850 Ma zircons, and they vary from rare single phase metatonalites to more common complexly banded migmatites. This is due to heterogeneous strain, in situ anatexis and granitic veining superimposed during younger tectonothermal events. In the single-phase tonalites with c. 3,850 Ma zircon, oscillatory-zoned prismatic zircon is all 3,850 Ma old, but shows patchy ancient loss of radiogenic Pb. SHRIMP spot analyses and laser ablation ICP-MS depth profiling show that thin (usually < 10 μm) younger (3,660–3,590 Ma and Neoarchaean) shells of lower Th/U metamorphic zircon are present on these 3,850 Ma zircons. Several samples with this simple zircon population occur on islands near Akilia. In contrast, migmatites usually contain more complex zircon populations, with often more than one generation of igneous zircon present. Additional zircon dating of banded gneisses across the Complex shows that samples with c. 3,850 Ma igneous zircon are not just a phenomenon restricted to Akilia and adjacent islands. For example, migmatites from Itilleq (c. 65 km from Akilia) contain variable amounts of oscillatory-zoned 3,850 Ma and 3,650 Ma zircon, interpreted, respectively, as the rock age and the time of crustal melting under Eoarchaean metamorphism. With only 110–140 ppm Zr in the tonalites and likely magmatic temperatures of >850°C, zircon solubility–melt composition relationships show that they were only one-third saturated in zircon. Any zircon entrained in the precursor magmas would thus have been highly soluble. Combined with the cathodoluminesence imaging, this demonstrates that the c. 3,850 Ma oscillatory zoned zircon crystallised out of the melt and hence gives a magmatic age. Thus the rare well-preserved tonalites and palaeosome in migmatites testify that c. 3,850 Ma quartzo–feldspathic rocks are a widespread (but probably minor) component in the Itsaq Gneiss Complex. C. 3,850 Ma zircon with negative Eu anomalies (showing growth in felsic systems) also occurs as detrital grains in rare c. 3,800 Ma metaquartzites and as inherited grains in some 3,660 Ma granites (sensu stricto). These demonstrate that still more c. 3,850 Ma rocks were present, but were recycled into Eoarchaean sediments and crustally derived granites. The major and trace element characteristics (e.g. LREE enrichment, HREE depletion, low MgO) of the best-preserved c. 3,850 Ma rocks are typical of Archaean TTG suites, and thus argue for crust formation processes involving important contributions from melting of hydrated mafic crust to the earliest Archaean. Five c. 3,850 Ma tonalites were selected as the best preserved on the basis of field criteria and zircon petrology. Four of these samples have overlapping initial ɛ_Nd (3,850 Ma) values from +2.9 to +3.6± 0.5, with the fourth having a slightly lower value of +0.6. These data provide additional evidence for a markedly LREE-depleted early terrestrial mantle reservoir. The role of c. 3,850 Ma crust should be considered in interpreting isotope signatures of the younger (3,800–3,600 Ma) rocks of the Itsaq Gneiss Complex. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

Wave energy in surface layers for energy-based damage evaluation     

Takaji Kokusho  Ryuichi Motoyama  Hiroshi Motoyama 《Soil Dynamics and Earthquake Engineering》2007,27(4):354-366

Seismic wave energy in surface layers is calculated based on vertical array records at four sites during the 1995 Hyogo-ken Nambu earthquake by assuming vertical propagation of SH waves. The upward energy generally tends to decrease as it goes up from the base layer to the ground surface particularly in soft soil sites. Theoretical study on 1D multi-layers model to investigate the basic energy flow mechanism indicates that the energy at the ground surface can be smaller on softer soils due to high soil damping during strong shaking even if resonance effect is considered. A simple calculation for a shear-vibrating structure resting on foundation ground shows that induced strain in the structure is directly related to the energy or the energy flux of surface layers. Hence, a general perception that soft soil sites tend to suffer heavier damage than stiff sites should be explained not by greater incident energy but by other reasons such as degree of resonance. Furthermore, it is recommended that not only acceleration or velocity but also S-wave velocity should be specified at a layer where a design seismic motion is given, so that the seismic wave energy can clearly be quantified in seismic design practice.  相似文献   

ACTIVE system for monitoring volcanic activity: A case study of the Izu-Oshima Volcano,Central Japan     

Hisashi Utada  Yuji Takahashi  Yuichi Morita  Takao Koyama  Tsuneomi Kagiyama 《Journal of Volcanology and Geothermal Research》2007

A system is proposed for the monitoring of changes in the underground structure of an active volcano over time by applying a transient electromagnetic method. The monitoring system is named ACTIVE, which stands for Array of Controlled Transient-electromagnetics for Imaging Volcano Edifice. The system consists of a transmitter dipole used to generate a controlled transient electromagnetic (EM) field and an array of receivers used to measure the vertical component of the transient magnetic field at various distances, with automatic operation of both units. In order to verify the performance of the proposed system, numerical and field experiments were carried out by application of the system to the Izu-Oshima volcano, where a remarkable change in the apparent DC resistivity over time had been detected in association with the eruption in 1986.  相似文献   

Water status in winter wheat grown under salt stress     

M Larry Lopez C~  WANG Rong~  MAO Xue-sen~  Takahashi Hidenori~ 《地理学报(英文版)》2001,11(2):202-208

1 IntroductionSalinization is one of the major problems in arid and semi-arid regions in relation to land use and in particular to agricultural production[1]. Excessive salinity leads to toxicity in crops and reduction of the availability of water to crops, by reducing the osmotic potential of the soil solution[2]. Movement of soil water induces solute transport, and solutes are transferred towards the ground surface by the upward soil-water movement caused by evaporation, resulting in an accu…  相似文献   

A New Coastal Marine Ecosystem Model Study Coupled with Hydrodynamics and Tidal Flat Ecosystem Effect   总被引：3，自引：0，他引：3  

Akio Sohma  Yasuyuki Sekiguchi  Hiroshi Yamada  Tatsuaki Sato  Kisaburo Nakata 《Marine pollution bulletin》2001,43(7-12):187-208

A new coastal marine ecosystem model was developed, which was composed of pelagic and benthic ecosystems, and was applied to Mikawa Bay, Japan. This model deals with variations of biochemical and physical interactions among dissolved oxygen and C–N–P species (composition formed out of carbon, nitrogen and phosphorus elements) so that it resolves the flux dynamics of carbon, nitrogen, phosphorus and oxygen elements. The physical and biochemical mechanism figured in this model is constructed for the purpose of simulating the estuarine lower trophic ecosystem, in areas where the sea was too deep for light to reach the sea-bottom. As a result of coupling the benthic with pelagic system, the effect of process of sedimentation and nutrient diffusion back to the pelagic system could be indicated. In addition, by implementing the tidal flat ecosystem model's calculation result, the integrated model can include the effect of water purification in tidal flats where the light can reach the sea-bottom, and where sea-weed, sea grass and benthic algae exist. In this study, the model indicates that oxygen-depleted water exists at the sea-bottom especially in summer mainly caused by an increase of oxygen consumption in the benthic system and a decrease of the vertical mixing water process. Furthermore, by comparing the case – with the tidal flat ecosystem model and the case without it, the effect of water purification of tidal flat estuaries was indicated. From the viewpoint of a short time scale, the tidal flat has the potential to restrict red tide (rapid increase of phytoplankton), and from the viewpoint of a long time scale, it restricts the sedimentation of detritus. Restricting the sedimentation prevents oxygen-depleted water occurring in the coastal marine system of Mikawa Bay.  相似文献   

Strain and tilt changes measured during a water injection experiment at the Nojima Fault zone, Japan   总被引：2，自引：0，他引：2  

Kunio Fujimori  Hiroshi Ishii  Atsushi Mukai  Shigeru Nakao  Shigeo Matsumoto  Yasuhiro Hirata 《Island Arc》2001,10(3-4):228-234

Abstract In order to make geophysical and geological investigations of the Nojima Fault on Awaji Island, Japan, three boreholes measuring 1800 m, 800 m and 500 m deep were drilled into the fault zone. The fault is one of the seismic source faults of the 1995 Hyogo-ken Nanbu earthquake of M 7.2. A new multicomponent borehole instrument was installed at the bottom of the 800 m borehole and continuous observations of crustal strain and tilt have been made using this instrument since May 1996. A high-pressure water injection experiment within the 1800 m borehole was done in February and March 1997 to study the geophysical response, behavior, permeability, and other aspects of the fault zone. The injection site was located approximately 140 m horizontally and 800 m vertically from the instrument. Associated with the water injection, contraction of approximately 0.7 × 10⁻⁷ str (almost parallel to the fault) and tilt of approximately 1 × 10^-7 rad in the sense of upheaval toward the injection site were observed. In addition to these controlled experiments, the strainmeter and tiltmeter also recorded daily variations. We interpret strain and tilt changes to be related to groundwater discharge and increased ultra-micro seismicity induced by the injected water.  相似文献   

Assessment of Debris-Flow Hazards of Alluvial Fans   总被引：1，自引：0，他引：1  

Okunishi  Kazuo  Suwa  Hiroshi 《Natural Hazards》2001,23(2-3):259-269

A strategy is presented for the assessment ofdebris-flow hazards on alluvial fans on the basis ofa case study carried out on the southern foot of astratovolcano named Mt. Yatsugatake. Transformation ofcommercial forests into a golf course was planned ata corner of the Kikkakezawa fan. The case studyinvolves an assessment of hazards due to debris flowsof different magnitudes and their recurrenceintervals. The environmental conditions for therecurrence of these debris flows are discussed as wellas the extent of the areas affected by them. In orderto generalize the case study, concepts of hazardpotential, hazard and risk for debris flows onalluvial fans are established. Accordingly, the hazardpotential is the possible hazards at any location onan alluvial fan in an indefinitely long time period,which can be assessed on the basis of hydrological andother geoscientific investigations. Hazards associatedwith a particular land use can be evaluated on thebasis of the hazard potential considering the locationand the time period associated with the land use. Riskcan be further assessed considering the life styles inthis land and the social conditions.  相似文献   

Simulations of seasonal variations of sulfur compounds in the remote marine atmosphere   总被引：1，自引：0，他引：1  

Seizi Koga  Hiroshi Tanaka 《Journal of Atmospheric Chemistry》1996,23(2):163-192

A photochemical box model is used to simulate seasonal variations in concentrations of sulfur compounds at latitude 40° S. It is assumed that the hydroxyl radical (OH) addition reaction to sulfur in the dimethyl sulfide (DMS) molecule is the predominant pathway for methanesulfonic acid (MSA) production, and that the rate constant increases as the air temperature decreases. Concentration of the nitrate radical (NO₃) is a function of the DMS flux, because the reaction of DMS with NO₃ is the most important loss mechanism of NO₃. While the diurnally averaged concentration of OH in winter is a factor of about 8 smaller than in summer, due to the weak photolysis process, the diurnally averaged concentration of NO₃ in winter is a factor of about 4–5 larger than in summer, due to the decrease of DMS flux. Therefore, at middle and high latitudes in winter, atmospheric DMS is mainly oxidized by the reaction with NO₃. The calculated ratio of the MSA to SO₂ production rates is smaller in winter than in summer, and the MSA to non-sea-salt sulfate (nssSO₄ ^2-) molar ratio varies seasonally. This result agrees with data on the seasonal variation of the MSA/nssSO₄ ^2- molar ratio obtained at middle and high latitudes. The calculations indicate that during winter the reaction of DMS with NO₃ is likely to be a more important sink of NO_x (NO+NO₂) than the reaction of NO₂ with OH, and to serve as a significant pathway of the HNO₃ production. If dimethyl sulfoxide (DMSO) is produced through the OH addition reaction and is heterogeneously oxidized in aqueous solutions, half of the nssSO₄ ^2- produced in summer may be through the oxidation process of DMSO. It is necessary to further investigate the oxidation products by the reaction of DMS with OH, and the possibility of the reaction of DMS with NO₃ during winter.  相似文献   

Observation　and　research　on　ULF　and　VLF　seismo－electromagnetic　radiation     

袁家治  钱书清  赵华兴  任克新 《地震学报(英文版)》1996,9(2):351-355

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