Suppression of Matrix Effects in ICP-MS by High Power Operation of ICP: Application to Precise Determination of Rb, Sr, Y, Cs, Ba, REE, Pb, Th and U at ng g-1 Levels in Milligram Silicate Samples

We found that the suppression of signals for ⁸⁸Sr, ¹⁴⁰Ce and ²³⁸U in rock solution caused by rock matrix in ICP-MS (matrix effects) was reduced at high power operation (1.7 kW) of the ICP. To make the signal suppression by the matrix negligible, minimum dilution factors (DF) of the rock solution for Sr, Ce and U were 600, 400 and 113 at 1.1, 1.4 and 1.7 kW, respectively. Based on these findings, a rapid and precise determination method for Rb, Sr, Y, Cs, Ba, REE, Pb, Th and U using FI (flow injection)-ICP-MS was developed. The amount of the sample solution required for FI-ICP-MS was 0.2 ml, so that 1.8 mg sample was sufficient for analysis with a detection limit of several ng g^-1. Using this method, we determined the trace element concentrations in the USGS rock reference materials, DTS-1, PCC-1, BCR-1 and AGV-1, and the GSJ rock reference materials, JP-1, JB-1, -2, -3, JA-1, -2 and -3. The reproducibilities (RSD %) in replicate analyses (n=5) of BCR-1, AGV-1, JB-1, -2, -3, JA-1, -2, and -3 were < 6 %, and typically 2.5%. The difference between the average concentrations of this study for BCR-1 and those of the reference values were < 2%. Therefore, it was concluded that the method can give reliable data for trace elements in silicate rocks.     

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.     

Sensitivity of CFCs and Anthropogenic CO2 Uptake in a North Pacific GCM to Mixing Parameterization and Surface Forcing

Distributions and characteristics of water mass and chlorofluorocarbons (CFCs) in the North Pacific are investigated by using a General Circulation Model (GCM). The anthropogenic CO₂ uptake by the ocean is estimated with velocity fields derived from the GCM experiments. The sensitivity of the uptake to different diffusion parameterizations and different surface forcing used in the GCM is investigated by conducting the three GCM experiments; the diffusive processes are parameterized by horizontal and vertical eddy diffusion which is used in many previous models (RUN1), parameterized by isopycnal diffusion (RUN2), and isopycnal diffusion and perpetual winter forcing for surface temperature and salinity (RUN3). Realistic features for water masses and CFCs can be simulated by the isopycnal diffusion models. The horizontal and vertical diffusion model fails to simulate the salinity minimum and realistic penetration of CFCs into the ocean. The depth of the salinity minimum layer is better simulated under the winter forcing. The results suggest that both isopycnal parameterization and winter forcing are crucial for the model water masses and CFCs simulations. The oceanic uptake of anthropogenic CO₂ in RUN3 is about 19.8 GtC in 1990, which is larger by about 10% than that in RUN1 with horizontal and vertical diffusive parameterization. RUN3 well simulates the realistic water mass structure of the intermediate layer considered as a candidate of oceanic sink for anthropogenic CO₂. The results suggest that the previous models with horizontal and vertical diffusive parameterization may give the oceanic uptake of anthropogenic CO₂ underestimated. This revised version was published online in August 2006 with corrections to the Cover Date.     

Application of spectral decomposition algorithm for mapping water quality in a turbid lake (Lake Kasumigaura,Japan) from Landsat TM data

The remote sensing of Case 2 water has been far less successful than that of Case 1 water, due mainly to the complex interactions among optically active substances (e.g., phytoplankton, suspended sediments, colored dissolved organic matter, and water) in the former. To address this problem, we developed a spectral decomposition algorithm (SDA), based on a spectral linear mixture modeling approach. Through a tank experiment, we found that the SDA-based models were superior to conventional empirical models (e.g. using single band, band ratio, or arithmetic calculation of band) for accurate estimates of water quality parameters. In this paper, we develop a method for applying the SDA to Landsat-5 TM data on Lake Kasumigaura, a eutrophic lake in Japan characterized by high concentrations of suspended sediment, for mapping chlorophyll-a (Chl-a) and non-phytoplankton suspended sediment (NPSS) distributions. The results show that the SDA-based estimation model can be obtained by a tank experiment. Moreover, by combining this estimation model with satellite-SRSs (standard reflectance spectra: i.e., spectral end-members) derived from bio-optical modeling, we can directly apply the model to a satellite image. The same SDA-based estimation model for Chl-a concentration was applied to two Landsat-5 TM images, one acquired in April 1994 and the other in February 2006. The average Chl-a estimation error between the two was 9.9%, a result that indicates the potential robustness of the SDA-based estimation model. The average estimation error of NPSS concentration from the 2006 Landsat-5 TM image was 15.9%. The key point for successfully applying the SDA-based estimation model to satellite data is the method used to obtain a suitable satellite-SRS for each end-member.     

Effects of scattering and dust grain size on the temperature structure of protoplanetary discs: a three-layer approach

The temperature in the optically thick interior of protoplanetary discs is essential for the interpretation of millimetre observations of the discs, for the vertical structure of the discs, for models of the disc evolution and the planet formation, and for the chemistry in the discs. Since large icy grains have a large albedo even in the infrared, the effect of scattering of the diffuse radiation in the discs on the interior temperature should be examined. We have performed a series of numerical radiation transfer simulations, including isotropic scattering by grains with various typical sizes for the diffuse radiation as well as for the incident stellar radiation. We also have developed an analytic model including isotropic scattering to understand the physics concealed in the numerical results. With the analytic model, we have shown that the standard two-layer approach is valid only for grey opacity (i.e. grain size ≳10 μm) even without scattering. A three-layer interpretation is required for grain size ≲10 μm. When the grain size is 0.1–10 μm, the numerical simulations show that the isotropic scattering reduces the temperature of the disc interior. This reduction is nicely explained by the analytic three-layer model as a result of the energy loss by scatterings of the incident stellar radiation and of the warm diffuse radiation in the disc atmosphere. For grain size ≳10 μm (i.e. grey scattering), the numerical simulations show that the isotropic scattering does not affect the interior temperature. This is nicely explained by the analytic two-layer model; the energy loss by scattering in the disc atmosphere is exactly offset by the 'green-house effect' due to the scattering of the cold diffuse radiation in the interior.     

Transformation textures,mechanisms of formation of high‐pressure minerals in shock melt veins of L6 chondrites,and pressure‐temperature conditions of the shock events

Abstract— The high‐pressure polymorphs of olivine, pyroxene, and plagioclase in or adjacent to shock melt veins (SMVs) in two L6 chondrites (Sahara 98222 and Yamato 74445) were investigated to clarify the related transformation mechanisms and to estimate the pressure‐temperature conditions of the shock events. Wadsleyite and jadeite were identified in Sahara 98222. Wadsleyite, ringwoodite, majorite, akimotoite, jadeite, and lingunite (NaAlSi₃O₈‐hollandite) were identified in Yamato 74445. Wadsleyite nucleated along the grain boundaries and fractures of original olivine. The nucleation and growth of ringwoodite occurred along the grain boundaries of original olivine, and as intracrystalline ringwoodite lamellae within original olivine. The nucleation and growth of majorite took place along the grain boundaries or fractures in original enstatite. Jadeite‐containing assemblages have complicated textures containing “particle‐like,” “stringer‐like,” and “polycrystalline‐like” phases. Coexistence of lingunite and jadeite‐containing assemblages shows a vein‐like texture. We discuss these transformation mechanisms based on our textural observations and chemical composition analyses. The shock pressure and temperature conditions in the SMVs of these meteorites were also estimated based on the mineral assemblages in the SMVs and in comparison with static high‐pressure experimental results as follows: 13–16 GPa, >1900 °C for Sahara 98222 and 17–24 GPa, >2100 °C for Yamato 74445.     

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.     

Intercomparison and analyses of the climatology of the West African Monsoon in the West African Monsoon Modeling and Evaluation project (WAMME) first model intercomparison experiment

This paper briefly presents the West African Monsoon (WAM) Modeling and Evaluation Project (WAMME) and evaluates WAMME general circulation models’ (GCM) performances in simulating variability of WAM precipitation, surface temperature, and major circulation features at seasonal and intraseasonal scales in the first WAMME experiment. The analyses indicate that models with specified sea surface temperature generally have reasonable simulations of the pattern of spatial distribution of WAM seasonal mean precipitation and surface temperature as well as the averaged zonal wind in latitude-height cross-section and low level circulation. But there are large differences among models in simulating spatial correlation, intensity, and variance of precipitation compared with observations. Furthermore, the majority of models fail to produce proper intensities of the African Easterly Jet (AEJ) and the tropical easterly jet. AMMA Land Surface Model Intercomparison Project (ALMIP) data are used to analyze the association between simulated surface processes and the WAM and to investigate the WAM mechanism. It has been identified that the spatial distributions of surface sensible heat flux, surface temperature, and moisture convergence are closely associated with the simulated spatial distribution of precipitation; while surface latent heat flux is closely associated with the AEJ and contributes to divergence in AEJ simulation. Common empirical orthogonal functions (CEOF) analysis is applied to characterize the WAM precipitation evolution and has identified a major WAM precipitation mode and two temperature modes (Sahara mode and Sahel mode). Results indicate that the WAMME models produce reasonable temporal evolutions of major CEOF modes but have deficiencies/uncertainties in producing variances explained by major modes. Furthermore, the CEOF analysis shows that WAM precipitation evolution is closely related to the enhanced Sahara mode and the weakened Sahel mode, supporting the evidence revealed in the analysis using ALMIP data. An analysis of variability of CEOF modes suggests that the Sahara mode leads the WAM evolution, and divergence in simulating this mode contributes to discrepancies in the precipitation simulation.     

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.