Dissolution mechanisms of water in depolymerized silicate melts: Constraints from H and Si NMR spectroscopy and ab initio calculations

Dissolution of water in magmas significantly affects phase relations and physical properties. To shed new light on the this issue, we have applied ¹H and ²⁹Si nuclear magnetic resonance (NMR) spectroscopic techniques to hydrous silicate glasses (quenched melts) in the CaO-MgO-SiO₂ (CMS), Na₂O-SiO₂, Na₂O-CaO-SiO₂ and Li₂O-SiO₂ systems. We have also carried out ab initio molecular orbital calculations on representative clusters to gain insight into the experimental results.The most prominent result is the identification of a major peak at ∼1.1 to 1.7 ppm in the ¹H MAS NMR spectra for all the hydrous CMS glasses. On the basis of experimental NMR data for crystalline phases and ab initio calculation results, this peak can be unambiguously attributed to (Ca,Mg)OH groups. Such OH groups, like free oxygens, are only linked to metal cations, but not part of the silicate network, and are thus referred to as free hydroxyls in the paper. This represents the first direct evidence for a substantial proportion (∼13∼29%) of the dissolved water as free hydroxyl groups in quenched hydrous silicate melts. We have found that free hydroxyls are favored by (1) more depolymerized melts and (2) network-modifying cations of higher field strength (Z/R²: Z: charge, R: cation-oxygen bond length) in the order Mg > Ca > Na. Their formation is expected to cause an increase in the melt polymerization, contrary to the effect of SiOH formation. The ²⁹Si MAS NMR results are consistent with such an interpretation. This water dissolution mechanism could be particularly important for ultramafic and mafic magmas.The ¹H MAS NMR spectra for glasses of all the studied compositions contain peaks in the 4 to 17 ppm region, attributable to SiOH of a range of strength of hydrogen bonding and molecular H₂O. The relative population of SiOH with strong hydrogen bonding grows with decreasing field strength of the network-modifying cations. Ab initio calculations confirmed that this trend largely reflects hydrogen bonding with nonbridging oxygens.     

Application of AVO Analysis to Seismic Data for Detection of Gas below Methane Hydrate Stability Zone in Nankai Trough Area

Abstract. For the purpose of development of methane hydrate, occurring in the deep marine subsurface, as a resource, the most important issue is to understand the methane hydrate system (generation, migration and accumulation) as well as to delineate the methane hydrate reservoir properties. We have applied the Amplitude Versus Offset (AVO) analysis to the seismic data acquired in the Nankai Trough, offshore Japan, in order to confirm the occurrence of gas just below the methane hydrate-bearing zone, assuming that gas will show a so-called Class-3 AVO response. Knowledge of the amount and occurrence of gas in the sediment below methane hydrate-bearing zone is one of the keys to understand the methane hydrate system.
We have utilized the qualitative analysis of AVO methodology to delineate how gas is located below the BSR, which is thought to be the reflection event from the interface between the methane hydrate-bearing zone and the underlying gas-bearing zone. In the region of MITI Nankai Trough Well PSW-3, we observe two BSRs separated by 25 ms. After AVO modeling using well data, we applied AVO attribute analysis and attribute crossplot analysis to the seismic data. Finally we applied an offset-amplitude analysis to CMP gather data at specific locations to confirm the results of AVO attribute analysis. The AVO analysis shows that there is very little gas located in the underlying sediment below methane hydrate-bearing zone. This result supports the fact that we could not obtain any clear evidence of gas occurrence just below the methane hydrate-bearing zone in the Nankai Trough well drilling.     

Phytoplankton dynamics in Lake Biwa during the 20th century: complex responses to climate variation and changes in nutrient status

We examined algal remains and fossil pigments in ²¹⁰Pb-dated sediment cores from Lake Biwa to explore historical changes in the phytoplankton community of the lake over the past 100 years and to identify environmental factors that caused those changes. Fluxes of fossil pigments and algal remains were very low before the 1960s, but increased through the 1960s and 1970s, indicating that the lake had eutrophied in the 20 years since 1960. After 1980, however, fluxes of all fossil pigments and algal remains decreased or stabilized. Redundancy analysis with meteorological and limnological variables explained more than 70% of the variation of these fluxes and showed that the decrease in fluxes of most algal taxa that occurred in the 1980s was related to changes in meteorological variables such as wind velocity, rather than changes in the lake’s trophic state. Sedimentary records of algal remains also revealed that Aulacoseira nipponica, an endemic diatom species that grows in winter, decreased dramatically after 1980, while Fragilaria crotonensis, a cosmopolitan spring diatom species, became dominant. Replacement of one dominant diatom species by another could not be explained simply by changes in the lake trophic state, but was reasonably strongly related with an increase in winter water temperature. These results suggest that the phytoplankton community in Lake Biwa was influenced by changes in local environmental conditions (nutrient loading) through the 1960s and 1970s, but more so by regional (meteorological) and global (climate warming) factors since 1980.     

Simultaneous spaced direction-finding measurements of medium-latitude VLF/ELF emissions

Simultaneous spaced measurements of medium-latitude VLF/ELF emissions were carried out during the three northern winters from 1976 to 1979. The experiment was making use of two different kinds of direction-finding systems (a field-analysis method and a goniometer network) at two stations in Europe, namely Brorfelde in Denmark (L = 2.9) and Chambron-la-Foret in France (L = 1.9); this enabled us to locate the ionospheric exit regions of emissions over a wide range of L-values up to and beyond 4.0, the average plasmapause location. In order to study the time delay in the temporal evolution of VLF emissions or the longitudinal drift of the emissions, observations from the Moshiri Observatory in Japan, widely separated in longitude, are also used. The overall system of the VLF equipment installed at the three stations is described. Then we present the VLF/ELF data of good quality obtained during the final year's campaign (Nov. 1978–Feb. 1979). By making use of the direction-finding data, we were able to classify the observed emissions into several categories, and some early results for some of the emissions are presented.     

Relation between chemical composition and particle-size distribution of ores in the profile of nickeliferous laterite deposits of the Rio Tuba Mine, Philippines

Lateritic Ni ore mined in the Rio Tuba Mine, Philippines, derived from ultramafic rock by tropical intense weathering, is generally composed of two accumulated zones, an upper laterite zone and a lower saprolite zone. These two zones are very different in appearance, mineral assemblage, chemical composition, and in other ways. A transitional zone may be seen between the upper and lower zones, but it does not develop to any appreciable thickness. Although serpentine and goethite are still predominant in the constituent minerals, other clay minerals are increasing.

The transitional zone may be subdivided into three groups based on chemical composition. The behaviour of the chemical composition in this horizon indicates a complicated process of component transportation under the weathering process.

In the ore, chemical components are closely related in particle size of constituent minerals. In the laterite - transitional - saprolite sequence, a common variation range and tendency in chemical composition for each particle size can be seen. However, taking samples with the same particle size the chemical composition obviously differed, representing the characteristics of the components for each zone.

Concerning the correlation coefficient of the chemical components of each zone, a somewhat different inter-component relationship can be seen in these zones. These differences of correlation suggest the different complicated lateritized conditions under which they are formed.     

Detection of Methane Hydrate-Bearing Zones from Seismic Data

Abstract. The MITI Nankai Trough wells were drilled offshore Japan in the Tokai area in 1999 and 2000. The occurrence of methane hydrate was confirmed by various indicators in the borehole logs and from core data. These findings have a large impact on potential future Japanese energy resources and other related-scientific interests.
We first tried to find the methane hydrate-bearing zones using interval velocities derived from NMO velocity analysis. However, this analysis produced poor resolution. To achieve a more detailed delineation of the gas hydrate- and gas-bearing zones, we executed a seismic impedance inversion calibrated by the logs from two of the MITI Nankai Trough wells. Although these two wells are only about 90 m apart, we were able to produce an impedance section with fine detail by adopting a simple initial model and incorporating physical properties of the methane hydrate-bearing zones. The locations of the methane hydrate-bearing zones are readily apparent in the final section.     

IPRT/AMATERAS: A New Metric Spectrum Observation System for Solar Radio Bursts

A new radio spectropolarimeter for solar radio observation has been developed at Tohoku University and installed on the Iitate Planetary Radio Telescope (IPRT) at the Iitate observatory in Fukushima prefecture, Japan. This system, named AMATERAS (the Assembly of Metric-band Aperture TElescope and Real-time Analysis System), enables us to observe solar radio bursts in the frequency range between 150 and 500 MHz. The minimum detectable flux in the observation frequency range is less than 0.7 SFU with an integration time of 10 ms and a bandwidth of 61 kHz. Both left and right polarization components are simultaneously observed in this system. These specifications are accomplished by combining the large aperture of IPRT with a high-speed digital receiver. Observational data are calibrated and archived soon after the daily observation. The database is available online. The high-sensitivity observational data with the high time and frequency resolutions from AMATERAS will be used to analyze spectral fine structures of solar radio bursts.     

Investigation on piezoelectric lead zirconate titanate detector bombarded obliquely with hypervelocity iron particles

A cosmic dust detector for use onboard a satellite is currently being constructed from piezoelectric lead zirconate titanate (PZT). The characteristics of the PZT detector were studied by bombarding it with hypervelocity iron particles, which were supplied by a Van de Graaff accelerator. There was a linear relationship between the rise time of the signal observed from the detector and the particle's velocity, which was above 10 km/s on impact. It was also found that the rise time was almost independent of the collisional angle between the particles and the PZT surface within the limits of the particle's parameters used in this experiment.