CO<Subscript>2</Subscript> Flux Measurements over the Sea Surface by Eddy Correlation and Aerodynamic Techniques

The measurements of the vertical transport of CO₂ were carried out over the Sea of Japan using the specially designed pier of Kyoto University on September 20 to 22, 2000. CO₂ fluxes were measured by the eddy correlation and aerodynamic techniques. Both techniques showed comparable CO₂ fluxes during sea breeze conditions: −0.001 to −0.08 mg m⁻²s⁻¹ with the mean of −0.05 mg m⁻²s⁻¹. This means that the measuring site satisfies the fetch requirement for meteorological observations under sea breeze conditions. Moreover, the eddy diffusivity coefficient used in the aerodynamic technique is found to be consistent with the coefficient used in the eddy correlation technique. The present result leads us to conclude that the aerodynamic technique may be applicable to underway CO₂ flux measurements over the ocean and may be used in place of the bulk technique. The important point is the need to maintain a measuring accuracy of CO₂ concentration difference of the order of 0.1 ppmv on the research vessels or the buoys.     

Fluid–Sediment Interaction in a Marine Shallow-Water Hydrothermal System in the Wakamiko Submarine Crater, South Kyushu, Japan

The Wakamiko submarine crater is a small depression located in Kagoshima Bay, southwest Japan. Marine shallow‐water hydrothermal activity associated with fumarolic gas emissions at the crater sea floor (water depth 200 m) is considered to be related with magmatic activity of the Aira Caldera. During the NT05‐13 dive expedition conducted in August 2005 using remotely operated vehicle Hyper‐Dolphine (Japan Agency for Marine‐Earth Science and Technology), an active shimmering site was discovered (tentatively named the North site) at approximately 1 km from the previously known site (tentatively named the South site). Surface sediment (up to 30 cm) was cored from six localities including these active sites, and the alteration minerals and pore fluid chemistry were studied. The pore fluids of these sites showed a drastic change in chemical profile from that of seawater, even at 30 cm below the surface, which is attributed to mixing of the ascending hydrothermal component and seawater. The hydrothermal component of the North site is estimated to be derived from a hydrothermal aquifer at 230°C based on the hydrothermal end‐member composition. Occurrence of illite/smectite interstratified minerals in the North site sediment is attributed to in situ fluid–sediment interaction at a temperature around 150°C, which is in accordance with the pore fluid chemistry. In contrast, montmorillonite was identified as the dominant alteration mineral in the South site sediment. Together with the significant low potassium concentration of the hydrothermal end‐member, the abundant occurrence of low‐temperature alteration mineral suggests that the hydrothermal aquifer in the South site is not as high as 200°C. Moreover, the montmorillonite is likely to be unstable with the present pore fluid chemistry at the measured temperature (117°C). This disagreement implies unstable hydrothermal activity at the South site, in contrast to the equilibrium between the pore fluid and alteration minerals in the North site sediment. This difference may reflect the thermal and/or hydrological structure of the Wakamiko Crater hydrothermal system.     

Decarbonation reaction of magnesite in subducting slabs at the lower mantle

High-pressure and temperature experiments (28–62 GPa, and 1,490–2,000 K, corresponding to approximately 770–1,500 km depth in the mantle) have been conducted on a MgCO₃ + SiO₂ mixture using a laser-heated diamond anvil cell combined with analytical transmission electron microscope observation of the product phases to constrain the fate of carbonates carried on the subducting basalt into the lower mantle. At these conditions, the decarbonation reaction MgCO₃ (magnesite) + SiO₂ (stishovite) → MgSiO₃ (perovskite) + CO₂ (solid) has been recognized. This indicates that above reaction takes place as a candidate for decarbonation of the carbonated subducting mid ocean ridge basalts in the Earth’s lower mantle.     

Strain field measurements of rubber by image analysis and design criteria for laminated rubber bearings (LRB)

Although seismic isolation rubber bearings in bridges and buildings have proven to be a very effective passive method for reducing earthquake‐induced forces, a detailed mechanical modeling of the rubber that is used in bearings under large strains has not been established. Therefore, a 3D model of failure behavior and the design criteria for the safety evaluation of seismic isolation bearings have not yet been developed. This paper presents: (1) correlation‐based template‐matching algorithms to measure large strain fields of continua; (2) a failure criterion for rubber; and (3) the design criteria for the safety evaluation of laminated algorithms, data‐validation algorithms were developed and implemented to eliminate possible unrealistic displacement vectors present in the measured displacement field. The algorithms were successfully employed in the strain field measurement of LRB and rubber materials that are subjected to failure. The measured local strains for rubber material at failure were used to develop a failure criterion for rubber. The validity of the proposed criterion was evaluated by applying it to the LRB; the criterion was introduced into a 3D finite element model of LRB, compared with the experimental results of bearings failure, and verified. Finally, design criteria are proposed for LRB for the safety evaluation. Copyright © 2003 John Wiley & Sons, Ltd.     

Metal binding to dissolved organic matter and adsorption to ferrihydrite in shallow peat groundwaters: Application to diamond exploration in the James Bay Lowlands,Canada

The speciation and solubility of kimberlite pathfinder metals (Ni, Nd, Ba and K) in shallow peat groundwaters is investigated over the Yankee, Zulu and Golf kimberlites in the Attawapiskat region, James Bay Lowlands, Canada. The purpose of this study is to examine the relationship between dissolved organic matter (DOM) complexation with kimberlite pathfinder metals and determine the spatial distribution of those metals in shallow peat groundwaters along sampling transects over subcropping kimberlites. Nickel, Nd, Ba and K complexation with DOM and the adsorption of these metals onto ferrihydrite were calculated using Visual MINTEQ 3.0 and the NICA-Donnan database. Calculations predict almost 100% of soluble Nd, Ni and Ba form complexes with DOM at sampling sites with little to no contribution from upwelling groundwater (i.e., dissolved organic C (DOC) concentrations = 40–132 mg/L, pH = 3.9–5.5, and log ionic strength ??3). In only the most ombrotrophic peat groundwater conditions does a majority fraction of K bind to DOM. By contrast, under conditions with large contributions from upwelling groundwaters (i.e., DOC concentrations ?40 mg/L, pH = 5.5–6.5, and log ionic strength = ?3 to ?2), as little as 10% of Nd and Ni, and 0% K and Ba are predicted to complex with DOM. The modeling calculations suggest the dominant control on metal–DOM complexation, particularly with respect to Ni and Nd, is competitive effects for DOM binding sites due to elevated ionic strength where there is evidence of strong groundwater upwelling. Visual MINTEQ modeling of metal adsorption on ferrihydrite surfaces predicts that under strong upwelling conditions, Ni and Nd are scavenged from solution due to increased ferrihydrite precipitation and decreased fractions of metals complexed with DOM. Analytical geochemical data are consistent with model predictions of metal adsorption on ferrihydrite. Total dissolved Ni and Nd concentrations at sites of strong upwelling are up to five times lower than waters with little to no upwelling and log ferrihydrite saturation indices (logSI_ferr) indicate precipitation (values up to 5) at sites of strong groundwater upwelling. Where the majority of Ni and Nd complex with DOM and ferrihydrite is highly under saturated (logSI_ferr = ?18 to ?5), the concentrations of total Ni and Nd are elevated compared to other sites along sampling transects. Metal complexation with DOM effectively inhibits metal scavenging from solution via adsorption and/or from forming secondary mineral precipitates. Also, because alkaline earth metals do not compete strongly with Ni and Nd for adsorption sites on ferrihydrite surfaces, but do compete strongly for insoluble organic sites, Ni and Nd are more likely to adsorb onto ferrihydrite.     

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.     

Preferred orientation of antiphase boundaries in pigeonite as a cooling ratemeter

Antiphase domains (APD's) of pigeonite lamellae in natural and heated augite crystals from the Hakonetoge andesite have been examined by a transmission electron microscope (TEM). Antiphase boundaries (APB's) of the pigeonite lamellae in natural specimens have a sigmoidal shape cutting the c axis in (010) sections. APB's in specimens heated at temperatures above the high-low inversion and then quenched are nearly parallel to the c axis with almost straight boundaries. These observations indicate that the preferred orientation of APB's in (010) sections depends on cooling rate; at fast colling rates the APB's are nearly parallel to the c axis, whereas at slower cooling rates they are inclined to the c axis. The cooling rate of the natural augite specimen from Hakonetoge is estimated to be about 0.01 °C/h from the experimentally determined time-temperature-transformation (TTT) diagram for the APB orientations. APD sizes are large in specimens quenched from above the inversion temperature; they are at a minimum after cooling rates of around 1–0.1 °C/h, and then become larger with slower cooling rates.     

Electron microscopy studies of akermanites (Ca1−xSrx)2CoSi2O7 with modulated structure

Single crystals of akermanite (Ca_1–x Sr _x )₂Co-Si₂O₇ solid solution were grown in nitrogen by the floating zone method using a lamp-image furnace. The grown crystals were 6 mm in diameter by 50 mm in length. Microprobe analyses indicate uniform strontium content x except in the initially crystallized part. Synthetic crystals with x from 0.0 to 0.3 give, at room temperature, satellite reflections and circular diffuse scatterings in the electron diffraction pattern, which are related to an incommensurate phase and microdomains, respectively. With increasing Sr content the wavelength of a modulation increases and the intensity of satellites decreases, but the intensity of circular diffuse scattering increases up to x=0.15 and then decreases until eventually the satellites and the circular diffuse scatterings disappear at x = 0.3. The circular diffuse scattering is explained by the cluster model for the transition state, proposed by De Ridder et al. (1976).