Kinetics of reactions between aqueous sulfates and sulfides in hydrothermal systems

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.     

Wave energy in surface layers for energy-based damage evaluation

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.     

A New Coastal Marine Ecosystem Model Study Coupled with Hydrodynamics and Tidal Flat Ecosystem Effect

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.     

Mesozoic radiolarians and radiolarian-bearing sequences in the circum-Pacific regions: A report of the symposium-'Radiolarians and Orogenic Belts'

Abstract This paper contains extended abstracts of the seven papers presented at the symposium 'Radiolarians and Orogenic Belts' held at the seventh meeting of the International Association of Radiolarian Paleontologists (INTERRAD). Important results of the symposium include the following: (1) Upper Paleozoic and Mesozoic cherts are widely distributed within accretionary complexes in the circum-Pacific orogenic belt. Radiolarian dating reveals that long durations of chert sedimentation in a pelagic environment are recorded on both sides of Pacific-rim accretionary complexes (e.g. New Zealand, Japan, Russian Far East, Canadian Cordillera). (2) Triassic radiolarian faunas from New Zealand and the Omolon Massif, northeast Siberia are similar in composition and are characterized by the absence of typical Tethyan elements. This suggests that radiolarian faunal provincialism may have been established as early as the Triassic. High-latitude radiolarian taxa exhibit a bi-polar distribution pattern. (3) The Lower Triassic interval in chert dominant pelagic sequences is mechanically weaker than other levels and acted as a décollement in accretionary events. This lithologic. contrast in physical property is considered to reflect radiolarian evolution, such as the end-Permian mass extinction.     

Age model, physical properties and paleoceanographic implications of the middle Pleistocene core sediments in the Choshi area, central Japan

Abstract   A continuous, well-preserved core was obtained from the Choshi area, on the Pacific side of Japan, to investigate paleoceanographic and paleoclimatic changes around the northwestern Pacific region during the middle Pleistocene. Siliciclastic sequences in the core are divided into five formations – the Obama, Yokone, Kurahashi and Toyosato Formations in the Inubo Group and the Katori Formation, in ascending order. Examination of calcareous nannofossils and magnetic polarities detected four datums in the core sediments of the Inubo Group: the top of Reticulofenestra asanoi , the base of Helicosphaera inversa , the top of Pseudoemiliania lacunosa and the Brunhes–Matuyama boundary. Fourteen marine isotope stages (MIS24–MIS11) were identified in the δ¹⁸O and δ¹³C records based on detected datums and the graphic correlation with the standard stack oxygen isotope curve. Magnetic susceptibility and gamma-ray attenuation porosity evaluator density were also measured and low values characterize the glacial intervals. Biogenic sedimentation by primary production may be larger during the glacial periods because of invasions of nutrient-rich northern surface-waters related to the southward shift of the Kuroshio front in the Choshi area.     

Pressure dependence on partition coefficients for trace elements between olivine and the coexisting melts

Partition coefficients between olivine and melt at upper mantle conditions, 3 to 14 GPa, have been determined for 27 trace elements (Li, Be, B, Na, Mg, Al, Si, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Rb, Sr, Y, Zr, Cs, Ba, La and Ce) using secondary-ion mass-spectrometry (SIMS) and electron-probe microanalysis (EPMA). The general pattern of olivine/melt partitioning on Onuma diagrams resembles those reported previously for natural systems. This agreement strongly supports the argument that partitioning is under structural control of olivine even at high pressure. The partition coefficients for mono- and tri-valent cations show significant pressure dependence, both becoming larger with pressure, and are strongly correlated with coupled substitution into cation sites in the olivine structure. The dominant type of trace element substitution for mono- and tri-valent cations into olivine changes gradually from (Si, Mg)↔(Al, Cr) at low pressure to (Si, Mg)↔(Al, Al) and (Mg, Mg)↔(Na, Al) at high pressure. The change in substitution type results in an increase in partition coefficients of Al and Na with pressure. An inverse correlation between the partition coefficients for divalent cations and pressure has been observed, especially for Ni, Co and Fe. The order of decreasing rate of partition coefficient with pressure correlates to strength of crystal field effect of the cation. The pressure dependence of olivine/melt partitioning can be attributed to the compression of cation polyhedra induced by pressure and the compensation of electrostatic valence by cation substitution. Received: March 6, 1997 / Revised, accepted: March 12, 1998     

Fast Oxidation Reaction of Nitrite by Dissolved Oxygen in the Freezing Process in the Tropospheric Aqueous Phase

Nitrite oxidation in the tropospheric aqueous phase by freezing was evaluated by freezing a field sample. Nitrite oxidation by dissolved oxygen in the freezing process is much faster than by other oxidation processes, such as reactions with ozone, hydrogen peroxide or dissolved oxygen in an aqueous solution at pHs 3 to –6. At pH 4.5 and 25°C, the lifetime of nitrite in the aqueous phase is ca. 1 hr in oxidation by ozone (6×10^-10 mol dm^-3), ca. 10 hr in oxidation by H₂O₂ (2×10^-4 mol dm^-3), and 7.5 hr (Fischer and Warneck, 1996) in photodissociation at midday in summer. Under the same conditions at a temperature below 0°C, the lifetime of nitrite in the freezing process is estimated as ca. 2 sec when the droplets are frozen within a second. The reaction by freezing is affected by the presence of salts, such as NaCl or KCl, or orgnaic compounds, such as methanol or acetone. The results of freezing a field rain or fog sample showed that nitrite oxidation proceeds below pH 6, and the conversion ratio of nitrate from nitrite increases with decreasing pH. The oxidation of nitrite by freezing was also observed in freezing fog particles generated by an ultrasonic humidifier. The ratios of the concentrations of ions in the winter sample to those in the summer sample (or those in the fog sample) were almost the same values. However, the concentration of nitrite in the winter sample was lower than that estimated by the ratios of other ions. From the present study, it seems that the freezing process plays an important role in the nitrite sink process in the tropospheric aqueous phase.     

MOS-1/1b MESSR Observations of the Antarctic Sea Ice: Ice Bands and Ice Streamers

Meso- or submeso-scale features of the Antarctic sea ice are investigated using the MOS-1/1b MESSR Images (spatial resolution of approximately 50 m) received at Syowa Station. Particular attention is paid to the ice bands and ice streamers in coastal polynyas. In the Antarctic Ocean, ice bands can be often seen not only at the ice edge but also in the ice interior zone throughout the year and they extend for hundreds of kilometers in the latitudinal direction. It is found that the width and spacing of ice bands tend to decrease from winter to summer. The width of ice band is about 2–6 km in August and September, and 0.1–0.7 km in December. The spacing of ice bands is about 3–10 km in August and September, and 0.1–2 km in December. In coastal polynyas, ice streamers, which are composed of new ice, are sometimes observed. In general, the row of the streamers is spaced at 0.5–2 km with a width of 0.1–1.0 km.