In situ Atomic Force Microscopy study of dissolution of the barite (0 0 1) surface in water at 30 °C

The dissolution behavior of the barite (0 0 1) surface in pure water at 30 °C was investigated using in situ Atomic Force Microscopy (AFM), to better understand the dissolution mechanism and the microtopographical changes that occur during the dissolution, such as steps and etch pits. The dissolution of the barite (0 0 1) surface started with the slow retreat of steps, after which, about 60 min later, the <hk0> steps of one unit cell layer or multi-layers became two-step fronts (fast “f” and slow “s” steps) with a half-unit cell layer showing different retreat rates. The “f” step had a fast retreat rate (≈(14 ± 1) × 10⁻² nm/s) and tended to have a jagged step edge, whereas the “s” step (≈(1.8 ± 0.1) × 10⁻² nm/s) had a relatively straight front. The formation of the “f” steps led to the formation of a new one-layer step, where the front of the “s” step was overtaken by that of the immediate underlying “f” step. The “f” steps also led to the decrease of the <hk0> steps and the increase in the percentage of stable steps parallel to the [0 1 0] direction during the dissolution.Etch pits, which could be observed after about 90 min, were of three types: triangular etch pits with a depth of a half-unit cell, shallow etch pits, and deep etch pits. The triangular etch pits were bounded by the step edges parallel to [0 1 0], [1 2 0], and [] and had opposite orientations in the upper half and lower half layers. Shallow etch pits that had a depth of two or more half-unit cell layers had any two consecutive pits pointing in the opposite direction of each other. The triangular etch pit appeared to grow by simultaneously removal of a row of ions parallel to each direction from the three step edges. At first, deep etch pits were elongated in the [0 1 0] direction with a curved outline and then gradually developed to an angular form bounded by the {1 0 0}, {3 1 0}, and (0 0 1) faces. The retreat rate of the (0 0 1) face was much slower than those of the {1 0 0} and {3 1 0} and tended to separate into two rates ((0.13 ± 0.01) × 10⁻² nm/s for the deep etch pits derived from a screw dislocation and (0.07 ± 0.01) × 10⁻² nm/s for those from other line defects).The changes in the dissolution rate of a barite (0 0 1) surface during the dissolution were estimated using the retreat rates and densities of the various steps as well as the growth rates, density, and areas of the lateral faces of the deep etch pits that were obtained from this AFM analysis. Our results showed that the dissolution rate of the barite (0 0 1) surface gradually increased and approached the bulk dissolution rate because of the change in the main factor determining the dissolution rate from the density of the steps to the growth and the density of the deep etch pits on the surface.     

Comparison of sinking particles in the upper 200 m between subarctic station K2 and subtropical station S1 based on drifting sediment trap experiments

Drifting sediment trap experiments were conducted during various seasons to elucidate the characteristics of particles sinking through the upper 200 m of the water column in the western Pacific at subarctic station K2 and subtropical station S1. The sinking particle flux increased when primary productivity was high at each station, during June–July at K2 and during February at S1. Biogenic opal (Opal) and CaCO₃ were the major components of the fluxes at K2 and S1, respectively. Contrary to the expectation of a high flux at the eutrophic station K2 and low flux at the oligotrophic station S1, the annual average organic carbon fluxes at 100 m were comparable at both stations: 62.7 mg C m^?2 day^?1 at K2 and 56.1 mg C m^?2 day^?1 at S1. The similarity of the fluxes was perhaps a reflection of the unexpectedly high primary production at S1. At K2, the organic carbon export ratio (organic carbon flux/primary productivity) was significantly and negatively correlated with primary production and tended to decrease with depth. The magnitude of the rate of attenuation of the organic carbon flux with depth was larger at S1 than at K2. This rate of attenuation tended to decrease and increase with primary production at K2 and S1, respectively. The explanation for these patterns may be that the flux of labile organic carbon at relatively shallow depths decreased with increasing primary production at K2, and zooplankton grazing pressure increased with increasing primary productivity at S1.     

Concentration of Gold(I) Thiosulfate Complex Ions on the Surface of Alumina Gel and their Change in Chemical State: Preliminary Experiment in the Elucidation of the Formation Mechanism of Epithermal Gold Deposits

In order to elucidate the formation mechanism of low‐sulfidation epithermal gold deposit, the adsorption of [Au(S₂O₃)₂]^3? (a model compound for gold(I) complex ion) on alumina gel (a model compound for the aluminum‐bearing minerals) and change in chemical state of [Au(S₂O₃)₂]^3? after adsorption on the surface of alumina gel were investigated as a basic model experiment. In the pH range from 4 to 6, the amount of [Au(S₂O₃)₂]^3? adsorbed on alumina gel decreased with increasing pH and decreased drastically between pH 6 and 7, and then approached zero above pH 8 at 30°C. At 60°C, the amount of gold adsorbed above pH 7 was enhanced compared with that at 30°C. This adsorption tendency indicates that [Au(S₂O₃)₂]^3? is mainly adsorbed by electrostatic interaction between negative charges of [Au(S₂O₃)₂]^3? and positive charges of alumina gel because of its isoelectric point around pH 9. The chemical state of gold after adsorption of [Au(S₂O₃)₂]^3? on alumina gel was examined using X‐ray absorption near edge structure (XANES). The result showed that [Au(S₂O₃)₂]^3? was spontaneously reduced to elemental gold even in the absence of specific reducing agents after adsorption on alumina gel. This reduction reaction might occur by two steps: (i) disproportionation of the adsorbed [Au(S₂O₃)₂]^3? at the surface of alumina gel, and (ii) spontaneous reduction of the resulting gold(III) complex ions on the surface of alumina gel. The experimental results suggest that aluminum plays an important role in the concentration of gold(I) complex ions and subsequent reduction of gold during the formation of low‐sulfidation epithermal gold deposits.     

Circulation of Intermediate and Deep Waters in the Philippine Sea

The circulation of intermediate and deep waters in the Philippine Sea west of the Izu-Ogasawara-Mariana-Yap Ridge is estimated with use of an inverse model applied to the World Ocean Circulation Experiment (WOCE) Hydrographic Program data set. Above 1500 m depth, the subtropical gyre is dominant, but the circulation is split in small cells below the thermocline, causing multiple zonal inflows of intermediate waters toward the western boundary. The inflows along 20°N and 26°N carry the North Pacific Intermediate Water (NPIW) of 11 × 10⁹ kg s⁻¹ in total, at the density range of 26.5σ_θ–36.7σ₂ (approximately 500–1500 m depths), 8 × 10⁹ kg s⁻¹ of the NPIW circulate within the subtropical gyre, whereas the rest is conveyed to the tropics and the South China Sea. The inflow south of 15°N carries the Tropical Salinity Minimum water of 35 × 10⁹ kg s⁻¹, nearly half of which return to the east through a narrow undercurrent at 15–17°N, and the rest is transported into the lower part of the North Equatorial Countercurrent. Below 1500 m depth, the deep circulation regime is anti-cyclonic. At the density range of 36.7σ₂, – 45.845σ₄ (approximately 1500–3500 m depths), deep waters of 17 × 10⁹ kg s⁻¹ flow northward, and three quarters of them return to the east at 16–24°N. The remainder flows further north of 24°N, then turns eastward out of the Philippine Sea, together with a small amount of subarctic-origin North Pacific Deep Water (NPDW) which enters the Philippine Sea through the gap between the Izu Ridge and Ogasawara Ridge. The full-depth structure and transportation of the Kuroshio in total and net are also examined. It is suggested that low potential vorticity of the Subtropical Mode Water is useful for distinguishing the net Kuroshio flow from recirculation flows. This revised version was published online in August 2006 with corrections to the Cover Date.     

Quasi-2-Day Signals Observed in the Warm Pool Region during TOGA/COARE IOP

During Tropical Ocean and Global Atmosphere (TOGA)/Coupled Ocean and Atmosphere Research Experiment (COARE) Intensive Observing Period (IOP), upward-looking acoustic Doppler current profilers (ADCP) and current meters were moored at two equatorial sites (147°E and 154°E) and two off-equatorial sites (2°N and 2°S, 156°E) in the warm pool region of the western equatorial Pacific. Using current data obtained by these moorings, we have shown that there is a dominant signal with a period of about 2 days from the end of November to the middle of December in 1992, except at the equatorial site on 147°E (Ueki et al., 1998). The energy of this quasi-2-day signal for the meridional current is larger than that for the zonal one and the signal has a high coherence between two off-equatorial sites. In this paper, using band-passed time series of the meridional curerent, we investigated characters of the quasi-2-day signal and attempted to interpret this signal as an equatorially trapped wave. Complex empirical orthogonal function (CEOF) analysis reveals two different phase propagating features between the equatorial and off-equatorial site. One is an upward propagating signal, which is dominant near the surface at two off-equatorial sites, and the other is a downward propagating signal, which is dominant near 200 m at the equatorial site. If one interprets the quasi-2-day signal as an equatorially trapped wave, it is suggested that it cannot be explained as a single wave but can be described as the superimposition of several wave signals. The main part of these signals consists of two signals, one caused by a meteorological forcing and another by another factor in the ocean field.     

Landsat infrared analysis of fumarole activity at Unzen Volcano: time-series comparison with gas and magma fluxes

We analyse shortwave infrared thermal data of the phase 1 eruption of Unzen Volcano (Japan) extracted from eight nighttime Thematic Mapper (TM) images taken from the Landsat 5 satellite between October 1991 and November 1992. We identify two discrete regions of the dome that were heated to high temperature by the ongoing eruptive activity; a fumarolically heated region and an area associated with the effusion of new lava. We concentrate analysis on the fumarolically heated region and investigate the relationships between parameters derived from the infrared radiance data and the nature of the fumarolic gas and magma fluxes. Temporal variations in the parameters derived from the radiance data closely follow those observed in the measured rate of magma effusion. The positive correlation observed between the fumarolically driven shortwave infrared flux and the magma discharge rate (r²=0.64) indicates that degassing occurred efficiently and in proportion to the amount of magma supplied. Over our monitoring period, the data suggest that gas accumulation within the edifice did not occur, this conclusion agreeing with a previous finding obtained using correlation spectrometer (COSPEC) analysis of SO₂ flux rates. A positive correlation (r²=0.56) was also found between the mean radiance of the pixels in the fumarolically heated region and the overall size of that region. This suggests a potential mechanism whereby, when gas pressure within the edifice increased, excess gas escaped through additional pathways to the surface as well through an increased flux at the main fumarolic vents.     

Petrological variation of large-volume felsic magmas from Hakkoda-Towada caldera cluster: Implications for the origin of high-K felsic magmas in the Northeast Japan Arc

Abstract The Hakkoda‐Towada caldera cluster (HTCC) is a typical Late Cenozoic caldera cluster located in the northern part of the Northeast Japan Arc. The HTCC consists of five caldera volcanoes, active between 3.5 Ma and present time. The felsic magmas can be classified into high‐K (HK‐) type and medium‐ to low‐K (MLK‐) type based on their whole‐rock chemistry. The HK‐type magmas are characterized by higher K₂O and Rb contents and higher ⁸⁷Sr/⁸⁶Sr ratios than MLK‐type magmas. Both magmas cannot be derived from fractional crystallization of any basaltic magma in the HTCC. Assimilation‐fractional crystallization model calculations show that crustal assimilation is necessary for producing the felsic magmas, and HK‐type magmas are produced by higher degree of crustal assimilation with fractional crystallization than MLK‐type magmas. Although MLK‐type magmas were erupted throughout HTCC activity, HK‐type magmas were erupted only during the initial stage. The temporal variations of magma types suggest the large contribution of crustal components in the initial stage. A major volcanic hiatus of 3 my before the HTCC activity suggests a relatively cold crust in the initial stage. The cold crust probably promoted crustal assimilation and fractional crystallization, and caused the initial generation of HK‐type magmas. Subsequently, the repeated supply of mantle‐derived magmas raised temperature in the crust and formed relatively stable magma pathways. Such a later system produced MLK‐type magmas with lesser crustal components. The MLK‐type magmas are common and HK‐type magmas are exceptional during the Pliocene–Quaternary volcanism in the Northeast Japan Arc. This fact suggests that exceptional conditions are necessary for the production of HK‐type magmas. A relatively cold crust caused by a long volcanic hiatus (several million years) is considered as one of the probable conditions. Intensive crustal assimilation and fractional crystallization promoted by the cold crust may be necessary for the generation of highly evolved HK‐type felsic magmas.     

X-ray CT based numerical analysis of fracture flow for core samples under various confining pressures

The X-ray CT based numerical analysis of fracture flow for core samples, recently developed by the authors, was applied to two granite core samples having either a mated artificial or a mated natural fracture at confining pressures of 5 to 50 MPa. A third-generation medical X-ray CT scanner was used to image the samples within a core holder consisting of an aluminum liner and a carbon fiber overwrap. Fracture models (i.e., aperture distributions) were obtained by the CT images, the resolution of which was coarser than the apertures, and a single-phase flow simulation was performed using a local cubic law-based fracture flow model. Numerical results were evaluated by a fracture porosity measurement and a solution displacement experiment using NaCl and NaI aqueous solutions. These numerical results coincided only qualitatively with the experimental results, primarily due to image noise from the aluminum liner of the core holder. Nevertheless, the numerical results revealed flow paths within the fractures and their changes with confining pressure, whereas the experimental results did not provide such results. Different stress-dependencies in the flow paths were observed between the two samples despite the similar stress-dependency in fracture porosity and permeability. The changes in total area of the flow paths with confining pressure coincided qualitatively with changes in breakthrough points in the solution displacement experiment. Although the data is limited, the results of the present study suggest the importance of analyzing fluid flows within naturally fractured core samples under in situ conditions in order to better understand the fracture flow characteristics in a specific field. As demonstrated herein, X-ray CT-based numerical analysis is effective for addressing this concern. Using a multi-phase flow model, as well as a core holder constructed of an engineered plastic, should provide a useful, non-destructive, and non-contaminative X-ray CT-based fracture flow analysis for core samples under in situ conditions in future studies.     

Complex vertical migration of larvae of the ghost shrimp, Nihonotrypaea harmandi, in inner shelf waters of western Kyushu,Japan

The position of meroplanktonic larvae in the water column with depth-dependent current velocities determines horizontal transport trajectories. For those larvae occurring in inner shelf waters, little is known about how combined diel and tidally-synchronized vertical migration patterns shift ontogenetically. The vertical migration of larvae of Nihonotrypaea harmandi (Decapoda: Thalassinidea: Callianassidae) was investigated in mesotidal, inner shelf waters of western Kyushu, Japan in July–August 2006. The larval sampling at seven depth layers down to 60 m was conducted every 3 h for 36 h in a 68.5-m deep area 10 km off a major coastal adult habitat. Within a 61–65-m deep area 5–7.5 km off the adult habitat, water temperature, salinity, chlorophyll a concentration, and photon flux density were measured, and water currents there were characterized from harmonic analysis of current meter data collected in 2008. The water column was stratified, with pycnocline, chlorophyll a concentration maximum, and 2% of photon flux density at 2 m, recorded at around 22–24 m. The stratified residual currents were detected in their north component, directed offshore and onshore in the upper and lower mixed layers, respectively. More than 87% of larvae occurred between 20 m and 60 m, producing a net onshore transport of approximately 1.3 km d⁻¹. At the sunset flooding tide, all zoeal-stage larvae ascended, which could further promote retention (1.4-km potential onshore transport in 3 h). The actual onshore transport of larvae was detected by observing their occurrence pattern in a shallow embayment area with the adult habitat for 24 h in October 1994. However, ontogenetic differences in the vertical migration pattern in inner shelf waters were also apparent, with the maximum mean positions of zoeae deepening with increasing stages. Zoeae I and II performed a reverse diel migration, with their minimum and maximum depths being reached around noon and midnight, respectively. Zoeae IV and V descended continuously. Zoeae III had behaviors that were intermediate to those of the earlier- and later-stage zoeae. Postlarvae underwent a normal diel migration (nocturnal ascent) regardless of tides, with the deepest position (below 60 m and/or on the bottom) during the day. These findings give a new perspective towards how complex vertical migration patterns in meroplanktonic larvae enable their retention in inner shelf waters before the final entry of postlarvae into their natal populations.     

A structure of the Kuroshio and its related upwelling on the East China Sea shelf slope

The ADCP on an advanced towed fish with controllable main and tail wings, called DRAKE measured a detailed sectional structure of the Kuroshio flowing to the NE along the East China Sea shelf slope west of Okinawa. At the observation period, a countercurrent directed to the SW formed in near-bottom water on the shelf slope. The horizontal flow perpendicular to the stream axis of the Kuroshio constructed a convergence zone around the boundary between the Kuroshio and the countercurrent. An intensive upwelling with the maximum velocity of 2.8 cm s^–1 was found to distribute on the shelf slope around the convergence zone. A dynamic cause of this intensive upwelling is discussed carefully.