High temperature infrared spectra of hydrous microcrystalline quartz

A series of in-situ high temperature infrared (IR) measurements of water in an agate sample and in a milky quartz has been conducted in order to understand the nature of water in silica at high temperatures (50–700?°C) and the dehydration behavior. IR absorption bands of water molecules trapped in the milky quartz showed a systematic decrease in intensities and a shift from 3425?cm^?1 at 50?°C toward 3590?cm^?1 at 700?°C without any loss of water. This indicates a change in IR absorption coefficients corresponding to different polymeric states of water at different temperatures. The broad 3430?cm^?1 band in the agate sample also showed a systematic decrease in IR intensity and a band shift toward higher frequency with increasing temperature (～700?°C). This indicates that the agate sample also contains fluid inclusion-like water. For this agate sample, a dehydration of loosely hydrogen-bonded molecular water occurred at lower temperatures (<200?°C). At higher temperatures (>400?°C), sharp bands around 3660 and 3725?cm^?1 (3740?cm^?1 at 50?°C) due to surface silanols, appeared. This indicates dehydration of H₂O molecules that are hydrogen bonded to surface silanols. SiOH species in the agate are divided into three groups, namely SiOH group located at structural defects, surface silanols hydrogen bonded to each other and free surface silanols. Former two dehydrate below 700?°C and the dehydration rate of the SiOH at structural defects is faster than the other. IR spectra show that SiOH species decrease continuously even after the dehydration of most of H₂O molecules. All these results provide realistic bases for the change in physicochemical states of different OH species in silica at high temperatures.     

High temperature X-ray study of single crystal stishovite synthesized with Li2WO4 as flux

Single crystal stishovite with a square prismatic habit and maximum length 0.8 mm was grown from α-quartz at 120 kbar and ～1,300° C. Li₂WO₄, chosen as a result of a previous experiment in growing coesite, was also successful as flux for stishovite. Single crystal X-ray structure analysis of the crystals thus obtained has been carried out at high temperatures under ambient pressure. Lattice constant measurements give a larger thermal expansion coefficient along the a-axis than along the c-axis. The bond distances and bond angles show a decreasing distortion of the SiO₆ octahedron with increasing temperature. The increasing amplitude of thermal vibrations of oxygen atoms with increasing temperature results in increasing O-O repulsion in the basal plane, which explains the observed crystallographic changes.     

Holocene Climate in the Northern Great Plains Inferred from Sediment Stratigraphy, Stable Isotopes, Carbonate Geochemistry, Diatoms, and Pollen at Moon Lake, North Dakota

Seismic stratigraphy, sedimentary facies, pollen stratigraphy, diatom-inferred salinity, stable isotope (δ¹⁸O and δ¹³C), and chemical composition (Sr/Ca and Mg/Ca) of authigenic carbonates from Moon Lake cores provide a congruent Holocene record of effective moisture for the eastern Northern Great Plains. Between 11,700 and 9500¹⁴C yr B.P., the climate was cool and moist. A gradual decrease in effective moisture occurred between 9500 and 7100¹⁴C yr B.P. A change at about 7100¹⁴C yr B.P. inaugurated the most arid period during the Holocene. Between 7100 and 4000¹⁴C yr B.P., three arid phases occurred at 6600–6200¹⁴C yr B.P., 5400–5200¹⁴C yr B.P., and 4800–4600¹⁴C yr B.P. Effective moisture generally increased after 4000¹⁴C yr B.P., but periods of low effective moisture occurred between 2900–2800¹⁴C yr B.P. and 1200–800¹⁴C yr B.P. The data also suggest high climatic variability during the last few centuries. Despite the overall congruence, the biological (diatom), sedimentological, isotopic, and chemical proxies were occassionally out of phase. At these times the evaporative process was not the only control of lake-water chemical and isotopic composition.     

Graphitization of carbonaceous matter during metamorphism with references to carbonate and pelitic rocks of contact and regional metamorphisms,Japan

This study is an attempt to correlate the graphitization process of carbonaceous matter during metamorphism with metamorphic grade. Graphitization can be parameterized using crystal structure and chemical and isotopic compositions. The extent of graphitization could be characterized mainly by temperature, duration of metamorphism and rock composition. We compared the graphitization trends for two metamorphic terrains, a contact aureole of the Kasuga area and a regional metamorphic terrain of high-temperature/low pressure type of the Ryoke metamorphic terrain in Northern Kiso area, Central Japan, and for two different lithologies (carbonate and pelite), using X-ray diffractogram, DTA-TG analysis, and chemical and stable isotope analyses. During contact metamorphism, graphitization and carbon isotopic exchange reactions proceeded simultaneously in pelitic and carbonate rocks. The decreases in basal spacing d(002) of the carbonaceous matter in carbonate rocks is greatly accelerated at temperatures higher than about 400° C. Furthermore, carbon isotopic ratios of graphite in carbonate rocks also change to ¹³C-enriched values implying exchange with carbonates. The beginning of this enrichment of ¹³C in the carbonaceous matter coincides with an abrupt increase of the graphitization processes. Carbon isotopic shifting up to 5 in pelites could be observed as metamorphic temperature increased probably by about 400° C. Carbonaceous matter in pelitic rocks is sometimes a mixture of poorly crystallized organic matter and well-crystallized graphite detritus. DTA-TG analysis is an effective tool for the distinction of detrital graphitic material. Two sources for the original carbon isotopic composition of carbonaceous matter in pelites in the Kasuga contact aureole can be distinguished, about-28 and-24 regardless of the presence of detrital graphite, and were mainly controlled by depositional environment of the sediments. Graphitization in limestones and pelitic rocks in regional metamorphism proceeds further than in a contact aureole. In the low-temperature range, the differences in extent of graphitization between the two metamorphic regions is large. However, at temperatures higher than 600° C, the extent of graphitization in both regions is indistinguishable. The degree of graphitization is different in limestones and pelitic rocks from the Ryoke metamorphic terrain. We demonstrate that the graphitization involves a progressive re-construction process of the crystal structure. The sequence of the first appearance of crystal inter planar spacing correlates with the metamorphic grade and indicates the crystal growth of three-dimensional structured graphite.     

Characteristics of SSH Anomaly Based on TOPEX/POSEIDON Altimetry and in situ Measured Velocity and Transport of Oyashio on OICE

An observation line along the TOPEX/POSEIDON (T/P) ground track 060 was set to estimate the Oyashio transport. We call this line the OICE (Oyashio Intensive observation line off-Cape Erimo) along which we have been conducting repeated hydrographic observations and maintaining mooring systems. T/P derived sea surface height anomaly (SSHA) was compared with velocity and transport on OICE. Although the decorrelation scale of SSHA was estimated at about 80–110 km in the Oyashio region, the SSHA also contains horizontal, small-scale noise, which was eliminated using a Gaussian filter. In the comparison between the SSHA difference across two selected points and the subsurface velocity measured by a moored Acoustic Doppler Current Profiler (ADCP), the highest correlation (0.92) appeared when the smoothing scale was set at 30 km with the two points as near as possible. For the transport in the Oyashio region, the geostrophic transport between 39°30′ N and 42°N was compared with the SSHA difference across the same two points. In this case the highest correlations (0.79, 0.88 and 0.93) occurred when the smoothing scale was set at 38, 6 and 9 km for reference levels of 1000, 2000 and 3000 db, respectively. The annual mean transport was estimated as 9.46 Sv in the 3000 db reference case. The Oyashio transport time series was derived from the T/P SSHA data, and the transports are smaller than that estimated from the Sverdrup balance in 1994–1996 and larger than that in 1997–2000. This difference is consistent with baroclinic response to wind stress field. This revised version was published online in July 2006 with corrections to the Cover Date.     

Stress Concentration at the Bottom of a Borehole and its Effect on Borehole Breakout Formation

Summary Stress concentration at the bottom of a borehole due to the corners with small radius of curvature in an axial section and its effect on the azimuth of breakout was studied. To this end, a 3-D finite element analysis was conducted and the stress around the borehole was examined for boreholes arbitrarily oriented to three principal axes of remote stress. Results show that, in the case of high strength rock, compressive failure resulting in spalling of a borehole may occur only at the bottom of the borehole. The spalling can occur continuously with drilling, and results in continuous spalling with depth, i.e., a breakout. This type of breakout tends to form on one side of the borehole and its orientation is approximately perpendicular to the orientation of standard breakouts, inferred from the stress concentration due to the cylindrical shape of the borehole.