Determination of Fluorine and Chlorine by Pyrohydrolysis and Ion Chromatography: Comparison with Alkaline Fusion Digestion and Ion Chromatography

A method to determine F and Cl in silicate materials by employing pyrohydrolysis and ion chromatography (IC) is described. Pyrohydrolysis involved mixing a pulverised sample (∼ 40 mg) with V₂O₅ (∼ 160 mg) and heating to 1100 °C under a wet oxygen flow in a quartz tube. Recovery yields of F and Cl were ∼ 97% using a NaF + NaCl standard solution. Detection limits of the pyrohydrolysis-IC method for silicate samples were 0.36 and 0.69 μg g^-1 for F and Cl, respectively. Fluorine and Cl concentrations were determined in the reference materials JB-2, JB-3 and JA-1 from the GSJ; BCR-2, BHVO-1, BHVO-2, AGV-1 and AGV-2 from the USGS; and NIST SRM 610, 612 and 614 glasses. Precisions (RSD) for determinations of F were 1–13% (except NIST SRM 614) and 2–19% for Cl, and were dependent on the concentration and blank correction. Most results obtained in this study were in good agreement with those of previous studies. In comparison, the Na₂CO₃ + ZnO fusion method at 900 °C showed that the yields of F and Cl by alkaline fusion systematically decreased with fusion duration time. The yields were 84% and 83% for JB-3, inferring that F and Cl were lost in this alkaline fusion.     

Measurements of air-ice drag coefficient over the ice-covered Sea of Okhotsk

The air-ice drag coefficient under neutral stratification C _DN was measured with the eddy correlation method in the southern Sea of Okhotsk. The disturbance of the wind field caused by the ship’s structure was evaluated by computational fluid dynamics (CFD), and two types of correction methods were applied to estimate the error span of C _DN : one is based on the results of CFD, and the other is based on the parameterization of C _DN over open water suggested by Taylor and Yelland (2001). The C _DN × 10³ values finally obtained ranged from 1.9 to 5.4 with a mean value of 2.7 by the CFD correction and from 1.5 to 5.0 with a mean value of 3.1 by the other method. This is somewhat larger than the value of 2.5 suggested by Shirasawa (1981), and in the same range as 2.2–4.0 over rough ice and 3.1–5.0 over very rough ice, values which were complied by Guest and Davidson (1991) for first year ice. Most of the ice conditions were characterized by broken floes with a diameter less than 100 m and raised rims, which made the surface rougher than flat, level ice. The relation between C _DN and ice concentration was not clear, mainly because the contribution of the form drag caused at the freeboard was undetectable due to the great variation of ice surface condition. The roughness length z _M was also evaluated using the model developed for snow covered ice in a previous study.     

Occurrence of coprostanol, 24-ethylcoprostanol and 5α-stanols in the marine sediments

The present study deals with the elucidation of sterol composition of the marine sediments in Kagoshima Bay. The identification of each sterol was performed by gas-liquid chromatography, Ag⁺ impregnated column chromatography, mass spectrometry, and nuclear magnetic resonance spectrometry. The sediment obtained near the estuary of River Koutsuki contained large portions of 5-stanols such as coprostanol and 24-ethylcoprostanol basides 5-stanols such as cholestanol, 24-methylcholestanol, and 24-ethylcholestanol in the sterol fraction. These 5-stanols in the marine sediment may be derived from the fecal contamination by domestic sewages.     

Temporal Variability of High Vertical Wavenumber Shear over the Izu-Ogasawara Ridge

Recent numerical studies (Hibiya et al., 1996, 1998, 2002) showed that the energy cascade across the internal wave spectrum down to small dissipation scales was under strong control of parametric subharmonic instabilities (PSI) which transfer energy from low vertical mode double-inertial frequency internal waves to high vertical mode near-inertial internal waves. To see whether or not the numerically-predicted energy cascade process is actually dominant in the real deep ocean, we examine the temporal variability of vertical profiles of horizontal velocity observed by deploying a number of expendable current profilers (XCPs) at one location near the Izu-Ogasawara Ridge. By calculating EOFs, we find the observed velocity profiles are dominated by low mode semidiurnal (∼double-inertial frequency) internal tides and high mode near-inertial internal waves. Furthermore, we find that the WKB-stretched vertical scales of the near-inertial current shear are about 250 sm and 100 sm. The observed features are reasonably explained if the energy cascade down to small dissipation scales is dominated by PSI.     

Western Arctic primary productivity regulated by shelf-break warm eddies

The response of phytoplankton to the Beaufort shelf-break eddies in the western Arctic Ocean is examined using the eddy-resolving coupled sea ice–ocean model including a lower-trophic marine ecosystem formulation. The regional model driven by the reanalysis 2003 atmospheric forcing from March to November captures the major spatial and temporal features of phytoplankton bloom following summertime sea ice retreat in the shallow Chukchi shelf and Barrow Canyon. The shelf-break warm eddies spawned north of the Barrow Canyon initially transport the Chukchi shelf water with high primary productivity toward the Canada Basin interior. In the eddy-developing period, the anti-cyclonic rotational flow along the outer edge of each eddy moving offshore occasionally traps the shelf water. The primary production inside the warm eddies is maintained by internal dynamics in the eddy-maturity period. In particular, the surface central area of an anti-cyclonic eddy acquires adequate light, nutrient, and warm environment for photosynthetic activity partly attributed to turbulent mixing with underlying nutrient-rich water. The simulated biogeochemical properties with the dominance of small-size phytoplankton inside the warm eddies are consistent with the observational findings in the western Arctic Ocean. It is also suggested that the light limitation before autumn sea ice freezing shuts down the primary production in the shelf-break eddies in spite of nutrient recovery. These results indicate that the time lag between the phytoplankton bloom in the shelf region following the summertime sea ice retreat and the eddy generation along the Beaufort shelf break is an important index to determine biological regimes in the Canada Basin.     

Effects of alkali and alkaline-earth cations on the high-pressure sound velocities of aluminosilicate glasses

Physics and Chemistry of Minerals - A black tourmaline sample from Seagull batholith (Yukon Territory, Canada) was established to be a schorl with concentrations of Fe2+ among the highest currently...     

Three‐dimensional microstructure of samples recovered from asteroid 25143 Itokawa: Comparison with LL5 and LL6 chondrite particles

In this study, the three‐dimensional (3‐D) microstructure of 48 Itokawa regolith particles was examined by synchrotron microtomography at SPring‐8 during the preliminary examination of Hayabusa samples. Moreover, the 3‐D microstructure of particles collected from two LL6 chondrites (Ensisheim and Kilabo meteorites) and an LL5 chondrite (Tuxtuac meteorite) was investigated by the same method for comparison. The modal abundances of minerals, especially olivine, bulk density, porosity, and grain size are similar in all samples, including voids and cracks. These results show that the Itokawa particles, which are surface materials from the S‐type asteroid Itokawa, are consistent with the LL chondrite materials in terms of not only elemental and isotopic composition of the minerals but also 3‐D microstructure. However, we could not determine whether the Itokawa particles are purely LL5, LL6, or a mixture of the two. No difference between the particles collected from Rooms A and B of the sample chamber, corresponding to the sampling sequence of the spacecraft's second and first touchdowns, respectively, was detected because of the statistically small amount of particles from Room B.     

Crystallization temperature determination of Itokawa particles by plagioclase thermometry with X‐ray diffraction data obtained by a high‐resolution synchrotron Gandolfi camera

The crystallization temperatures of Itokawa surface particles recovered by the space probe Hayabusa were estimated by a plagioclase geothermometer using sodic plagioclase triclinicity. The Δ131‐index required for the thermometer, which is the difference in X‐ray diffraction peak positions between the 131 and 11 reflections of plagioclase, was obtained by a high‐resolution synchrotron Gandolfi camera developed for the third generation synchrotron radiation beamline, BL15XU at SPring‐8. Crystallization temperatures were successfully determined from the Δ131‐indices for four particles. The observed plagioclase crystallization temperatures were in a range from 655 to 660 °C. The temperatures indicate crystallization temperatures of plagioclases in the process of prograde metamorphism before the peak metamorphic stage.     

Summer monsoon rainfall scenario over Bangladesh using a high-resolution AGCM

Summer monsoon rainfall was simulated by a global 20 km-mesh atmospheric general circulation model (AGCM), focusing on the changes in the summer monsoon rainfall of Bangladesh. Calibration and validation of AGCM were performed over Bangladesh for generating summer monsoon rainfall scenarios. The model-produced summer monsoon rainfall was calibrated with a ground-based observational data in Bangladesh during the period 1979–2003. The TRMM 3B43 V6 data are also used for understanding the model performance. The AGCM output obtained through validation process made it confident to be used for near future and future summer monsoon rainfall projection in Bangladesh. In the present-day (1979–2003) climate simulations, the high-resolution AGCM produces the summer monsoon rainfall better as a spatial distribution over SAARC region in comparison with TRMM but magnitude may be different. Summer monsoon rainfall projection for Bangladesh was experimentally obtained for near future and future during the period 2015–2034 and 2075–2099, respectively. This work reveals that summer monsoon rainfall simulated by a high-resolution AGCM is not directly applicable to application purpose. However, acceptable performance was obtained in estimating summer monsoon rainfall over Bangladesh after calibration and validation. This study predicts that in near future, summer monsoon rainfall on an average may decrease about ?0.5 % during the period 2015–2034 and future summer monsoon rainfall may increase about 0.4 % during the period 2075–2099.