Underground storage of carbon dioxide in depleted natural gas reservoirs and in useless aquifers

Depleted reservoirs of natural gas and petroleum can provide excellent traps for carbon dioxide. Deep aquifers, which are not used due to high salinity, can host larger amount of the carbon dioxide under their high formation pressure than natural gas and oir reservoirs. Small fraction of aquifers in sedimentary basins in the world are enough to host about 87 gigaton-C of carbon dioxide.

A preliminary technical and economical survey on the carbon dioxide injection system suggests that the energy requirement for carbon dioxide injection into subterranean aquifers is about 269 kWh/ton-C and that the investment and operation costs for system are 79 $/ton-C. By our preliminary cost estimation in Japan, the CO₂-emission-free electricity generation may become possible with a cost increase of 35% for natural-gas-fired power station, and of 60% for coal-fired-power station.     

Plutonium diffusivity in compacted bentonite

Measurements on plutonium diffusivity in water-saturated compacted bentonite were carried out. Representative specimens of sodium bentonite were taken from the Tsukinuno and Kuroishi mines situated in northeast Japan. Tsukinuno bentonite was divided into three types: raw type, purified Na-type, and H-type which was prepared by treating Na-type bentonite with hydrochloric acid. Kuroishi bentonite contained chlorite as impurity. H-type bentonite was used as reference for the convenience of profile measurement in bentonite, since plutonium diffusivity in H-type bentonite was considered to be larger than that in Na-type bentonite because of low pH and low swelling pressure of H-type bentonite.

Sampled bentonite was compacted into pellets of 20 mm in diameter and 20 mm in height. Bulk densities of these specimens were 1200–1800 kg/m³ for purified Na-type and H-type bentonite and 1600 kg/m³ for raw type bentonite.

Plutonium profiles obtained in H-type bentonite can be explained by diffusion equation with constant concentration source. Diffusivity ranges from 10^-13 to 10¹² m²/s for H-type and Kuroishi impure sodium bentonite. Diffusivity in both raw type and purified Tsukinuno bentonite was was estimated to less than 10^-14 M²/s. Diffusivity in H-type bentonite showed a tendency to decrease with increasing density. Influence of in bentonite was also studied. Quartz content up to 50% or hematite content up to 1% did not influence diffusivity significantly in H-type bentonite.

The chemical species of plutonium in pore water of Na-type and H-type were estimated Pu(OH)₃^-; and PuO₂^- , respectively.     

Measurement of elastic properties of single-crystal CaO up to 1200 K

The elastic moduli of a single-crystal calcium oxide, CaO, are measured in the temperature range from 300 to 1200 K (1.8 times of the Debye temperature) by the resonant sphere technique (RST). The lowest 18 modes are identified in the frequency range from 0.6 to 1.4 MHz for the vibrating spherical specimen, which is 5.6564 mm in diameter and 3.3493 g/cm³ in density at room temperature, and the resonant frequencies are traced as a function of temperature. The adiabatic elastic moduli are determined in the present temperature range from the observed frequencies by inversion calculations. Most of the elastic moduli, except forC ₁₂ modulus, decrease as temperature increases. The temperature curves ofC _s andC ₄₄ moduli cross at 372 K. This means that the CaO specimen has an isotropic elasticity at the temperature. The temperature derivatives (?C ₁₁/?T) _P and (?C _s/?T) _P become slightly less negative with temperature increase and (?C _s /?T) _P and (?C ₄₄/?T) _P are almost constant. Combining the present elastic data with thermal expansion and specimen heat capacity data of CaO, we present the temperature dependence of thermodynamic parameters important in the studies of earth's interior.     

Chemistry and isotope ratios of sulfur in basalts and volcanic gases at Kilauea volcano,Hawaii

Eighteen basalts and some volcanic gases from the submarine and subaerial parts of Kilauea volcano were analyzed for the concentration and isotope ratios of sulfur. By means of a newly developed technique, sulfide and sulfate sulfur in the basalts were separately but simultaneously determined. The submarine basalt has 700 ± 100 ppm total sulfur with δ³⁴S_Σs of $\text{0.7 ± 0.1 ‰}$. The sulfate/sulfide molar ratio ranges from 0.15 to 0.56 and the fractionation factor between sulfate and sulfide is $\text{+7.5 ± 1.5‰}$. On the other hand, the concentration and δ³⁴S_Σs values of the total sulfur in the subaerial basalt are reduced to 150 ± 50 ppm and $\text{?0.8 ± 0.2‰}$, respectively. The sulfate to sulfide ratio and the fractionation factor between them are also smaller, 0.01 to 0.25 and +3.0‰, respectively. Chemical and isotopic evidence strongly suggests that sulfate and sulfide in the submarine basalt are in chemical and isotopic equilibria with each other at magmatic conditions. Their relative abundance and the isotope fractionation factors may be used to estimate the $\text{?o}{}_2$ and temperature of these basalts at the time of their extrusion onto the sea floor. The observed change in sulfur chemistry and isotopic ratios from the submarine to subaerial basalts can be interpreted as degassing of the SO₂ from basalt thereby depleting sulfate and ³⁴S in basalt.The volcanic sulfur gases, predominantly SO₂, from the 1971 and 1974 fissures in Kilauea Crater have δ³⁴S values of 0.8 to 0.9%., slightly heavier than the total sulfur in the submarine basalts and definitely heavier than the subaerial basalts, in accord with the above model. However, the δ³⁴S value of sulfur gases (largely SO₂) from Sulfur Bank is 8.0%., implying a secondary origin of the sulfur. The δ³⁴S values of native sulfur deposits at various sites of Kilauea and Mauna Loa volcanos, sulfate ions of four deep wells and hydrogen sulfide from a geothermal well along the east rift zone are also reported. The high δ³⁴S values (+5 to +6%._o) found for the hydrogen sulfide might be an indication of hot basaltseawater reaction beneath the east rift zone.     

Meteoric hydrothermal origin of calcites in “Green Tuff” formations,Miocene age,Japan

Oxygen and carbon isotope compositions were determined for calcites from the Green Tuff formations of Miocene age in Japan. Values of ¹⁸O from 24 calcites in altered rocks from 5 districts range from –2 to +16_SMOW, in most cases from 0 to +8_SMOW. The low ¹⁸O values rule out the possibility of their low-temperature origin or any significant contribution of magmatic fluid in the calcite precipitation. These values, coupled with their mineral assemblages, suggest that the calcites formed from meteoric hydrothermal solutions which caused propylitic alteration after the submarine strata became emergent.Values of ¹³C from the calcites show a wide variation from –17 to 0_PDB. Calcites from different districts have different ranges of ¹³C values, indicating that there was no homogeneous reservoir of carbon at the time the calcite formed, and that the carbon had local sources. Carbon isotopic compositions of calcite within ore deposits in the Green Tuff formations range from –19 to 0_PDB, similar to those of calcite in the altered rocks in the same district, suggesting that the carbon in ore calcites was likely supplied from the surrounding rocks through activity of meteoric hydrothermal solutions.     

Seasonal variation of bromocarbons at Hateruma Island,Japan: implications for global sources

High-frequency measurements of dibromomethane (CH₂Br₂) and bromoform (CHBr₃) at Hateruma Island, in the subtropical East China Sea, were performed using automated preconcentration gas chromatography/mass spectrometry. Their baseline concentrations, found in air masses from the Pacific Ocean, were 0.65 and 0.26 ppt, respectively, in summer and 1.08 and 0.87 ppt, respectively, in winter. Air masses transported from Southeast Asia were rich in bromocarbons, suggesting strong emissions in this area. The passage of cold fronts from the Asian continent was associated with sharp increases in observed concentrations of bromocarbons derived from coastal regions of the continent. Comparison of the relationships between [CH₂Br₂]/[CHBr₃] and [CHBr₃] in the Hateruma Island data with those in monthly mean data from 14 globally distributed U.S. National Oceanic and Atmospheric Administration ground stations suggested that these gases are produced primarily from a common process on a global scale.     

Frequency-dependence of velocity and attenuation of elastic waves in granite under uniaxial compression

Velocity as well as attenuation factorQ ^–1 ofP-wave in a dry granitic rock sample under uniaxial compressions were measured in the range of frequency between 100 kHz and 710 kHz by using the pulse transmission technique. Above the stress of 0.5 _f , where _f is the fracture stress, theP-wave velocity decreases with increasing axial stress, whereasQ ^–1 increases. Particularly, the change ofQ ^–1 is greater for high frequency than for low frequency. At a given stress level, the higher the frequency, the higher theP-wave velocity and the largerQ ^–1. This result means that the velocity decrease with increasing stress is smaller for higher frequency. Because of this frequency-dependence of velocity decrease, theP-wave in the rock under dilatant state shows dispersion. The body wave dispersion is more remarkable at higher stress, and is not found in a homogeneous material with no cracks. Thus the disperison is attributed to the generation of cracks. When the frequency-dependence ofQ ^–1 is approximated asf ⁿ in the present frequency range, the exponentn takes a value from 0.63 to 0.77.     

The ZnSiO3 clinopyroxene-ilmenite transition: Heat capacity,enthalpy of transition,and phase equilibria

ZnSiO₃ clinopyroxene stable above 3 GPa transforms to ilmenite at 10–12 GPa, which further decomposes into ZnO (rock salt) plus stishovite at 20–30 GPa. The enthalpy of the clinopyroxene-ilmenite transition was measured by high-temperature solution calorimetry, giving ΔH⁰=51.71 ±3.18 kJ/mol at 298 K. The heat capacities of clinopyroxene and ilmenite were measured by differential scanning calorimetry at 343–733 and 343–633 K, respectively. The C _p of ilmenite is 3–5% smaller than that of clinopyroxene. The entropy of transition was calculated using the measured enthalpy and the free energy calculated from the phase equilibrium data. The enthalpy, entropy and volume changes of the pyroxene-ilmenite transition in ZnSiO₃ are similar in magnitude to those in MgSiO₃. The present thermochemical data are used to calculate the phase boundary of the ZnSiO₃ clinopyroxene-ilmenite transition. The calculated boundary,

Wind-dependent formation of phytoplankton spring bloom in Otsuchi Bay,a ria in Sanriku,Japan

Spring blooms of phytoplankton composed of centric diatoms developed in late February, March, and April in Otsuchi Bay on Sanriku ria coast, Japan. During this period, associated with prolonged seasonal west wind (>1 day), intense exchange of waters occurred between inside and outside the bay: outflow of nearsurface brackish water over inflow of oceanic water at depth. This circulation interrupted formation of the blooms, and transported phytoplankton populations seaward. By such water movements, a significant amount of nutrients in the bay was carried out, otherwise replenished into the bay, depending on water masses located outside the bay. Owing to irregular features of wind events, a bloom lasted from several days to a week. From February to April, supply of nutrients seemed to be replete except for the latter half of the bloom period, and estimates of the critical depth exceeded the depth of the bottom consistently. Thus, net growth of phytoplankton was expected throughout the observation period, and potentially blooms could be formed. However, the blooms were only formed under calm weather. We hypothesize that the exchange of waters dilutes populations in the bay, and that formation of the bloom, that is, accumulation of biomass depends on a balance between the growth of phytoplankton and the dilution of bay water.