Ion Chromatographic Determination of Fluorine and Chlorine in Silicate Rocks Following Alkaline Fusion     

Kenji Shimizu  Takaaki Itai  Minoru Kusakabe 《Geostandards and Geoanalytical Research》2006,30(2):121-129

A simple and accurate method to determine fluorine and chlorine contents in small amounts (∼ 30 mg) in rock has been developed using ion chromatography after extraction by alkaline fusion. Powdered sample was mixed with sodium carbonate and zinc oxide at a mass ratio of 1:3:1, and was fused in an electric furnace at 900 °C for 30-40 minutes. An aqueous solution obtained by dissolving the fused silicate rock was diluted to the appropriate concentration of sodium carbonate (< ∼ 24 mmol l^-1) to minimise the tailing effect on F^- during ion chromatography caused by the large amount of carbonate species originating from the flux. Fluorine and chlorine contents were then determined by a standard additions method. Based on the relative standard deviation of the backgrounds, detection limits of both fluorine and chlorine were ∼ 4 μg g^-1, when 30 mg test portions were fused and diluted by a factor of 1200. We also report new fluorine and chlorine contents in nine GSJ (Geological Survey of Japan) reference materials, including peridotite (JP-1), granite (JG-1a), basalts (JB-1b, 2 and 3), andesites (JA-1 and 2) and rhyolites (JR-1 and 2). Fluorine and chlorine contents in the reference materials in this study were consistent with previously reported values. Reproducibilities were < 10 % for samples with F and Cl concentrations of > 20 μg g-1 and < 20 % with F and Cl < 20 μg g^-1.  相似文献   

Sulfur Isotope Study on Hg and Sb Deposits in Japan     

Akira Imai    Naotatsu Shikazono    Masaaki Shimizu  Hidehiko Shimazaki 《Resource Geology》2006,56(1):37-48

Abstract. Sulfur isotope ratios of cinnabar from Hg deposits and stibnite, jamesonite and berthierite from Sb deposits in Japan are examined in order to understand metallogeneses of Hg and Sb deposits in Japanese island arcs. The studied Hg and Sb deposits include the Hg deposit at Yamato‐suigin (Honshu) and the Sb deposit at Ichinokawa (Shikoku) in the Southwest Japan arc. In addition, Hg deposits including Itomuka and Ryushoden in central Hokkaido and Hg and Sb mineralizations in Northeast Japan arc are examined. The δ³⁴S values of cinnabar from the Hidaka‐Kitami district, central Hokkaido, including the Itomuka and Ryushoden deposits range widely, from ‐10 to +16 %o, the highest values encountered at the Samani deposit. The δ³⁴S values of cinnabar from other areas in Japan range from ‐12 to +5 %o, having δ³⁴S values higher than +2 %o from southwestern Hokkaido (Meiji deposit), Shikoku (Suii deposit) and Kyushu (Hasami and Yamagano deposits). On the other hand, the δ³⁴S values of stibnite from all areas in Japan range from ‐14 to +5 %o, having positive δ³⁴S values higher than +2 %o up to +5 %o from southwestern Hokkaido (Yakumo, Toyotomi and Teine deposits) and eastern‐central Honshu (Hachiman and Daikoku deposits). The variation in δ³⁴S values of Hg and Sb deposits may reflect the variation in δ³⁴S values of country rocks or variation in mixing ratio of sulfur extracted from the country rocks, sulfur derived from seawater sulfate, and sulfur derived from magmatic emanations. The relatively high δ³⁴S values of cinnabar and stibnite higher than +2 %o from southwestern Hokkaido, eastern‐central Honshu and Kyushu are probably caused by contribution of volcanic emanation from arc magmas having positive σδ³⁴S values, whereas the positive δ³⁴S values of cinnabar higher than +2 %o from Suii deposit in Shikoku may be attributed to structurally substituted sulfate in limestone country rocks and/or sulfur derived from seawater sulfate. However, the wide range of the δ³⁴S values of cinnabar from the Hidaka‐Kitami district, central Hokkaido, is difficult to explain at this moment. Other relatively low, negative δ³⁴S values of cinnabar and stibnite, berthierite from other areas in Japan may be attributed to 1) incorporation of isotopically light sedimentary sulfur or sulfur derived from ilmenite‐series silicic magma, or 2) less contribution of volcanic emanation from arc magmas having positive σδ³⁴S values.  相似文献   

Pb isotopic variability in melt inclusions from the EMI–EMII–HIMU mantle end-members and the role of the oceanic lithosphere     

A.E. Saal  S.R. Hart  N. Shimizu  E.H. Hauri  G.D. Layne  J.M. Eiler 《Earth and Planetary Science Letters》2005,240(3-4):605-620

Melt inclusions from four individual lava samples representing the HIMU (Mangaia Island), EMI (Pitcairn Island) and EMII (Tahaa Island) end member components, have heterogeneous Pb isotopic composition larger than that defined by the erupted lavas in each island. The broad linear trend in ²⁰⁷Pb/²⁰⁶Pb–²⁰⁸Pb/²⁰⁶Pb space produced by the melt inclusions from Mangaia, Tahaa and fPitcairn samples reproduces the entire trend defined by the Austral chain, the Society islands and the Pitcairn island and seamount groups. The inclusions preserve a record of melt composition of far greater isotopic diversity than that sampled in whole rock basalts. These results can be explained by mixing of a common depleted component with the HIMU, EMI and EMII lavas, respectively. We favor a model that considers the oceanic lithosphere to be that common component. We suggest that the Pb isotopic compositions of the melt inclusions reflect wall rock reaction of HIMU, EMI and EMII melts during their percolation through the oceanic lithosphere. Under these conditions, the localized rapid crystallization of olivine from primitive basalt near the reaction zone would allow the entrapment of melt inclusions with different isotopic composition.  相似文献   

Practical applicability of high frequency correction theories to CO<Subscript>2</Subscript> flux measured by a closed-path system     

Takanori Shimizu 《Boundary-Layer Meteorology》2007,122(2):417-438

The theoretical correction of CO₂ fluxes for high frequency attenuation in closed-path systems was re-summarized and its applicability examined using both measurements obtained at an Asiaflux forest site and empirical transfer functions used in previous studies. For our measurement system, the theoretical transfer function was applicable to high frequency correction, even when condensation occurred in the sampling line. Further, in respect to some measurement systems described in previous studies, it was found that the theoretical function was potentially applicable along with the empirical functions used. Meanwhile, in some systems significant errors could not be resolved by re-estimation of the theories. In these systems, because of undefined buffering effects, the actual response lag time decided by the maximum covariance method or by measurement of the system response time using tracer gas was significantly different from the lag time calculated from the tube dimensions and the measured flow rate. If the average flow rate calculated by the actual lag time was used to determine the theoretical function, the theoretical function became closer to, and sometimes agreed with, the empirical function. Any remaining deviation from each function might be associated with pressure fluctuations, but this problem was unable to be examined here. The results suggested that an empirical formulation for each site is considered applicable rather than a theoretical approach, although the theories are being developed to practical application.  相似文献   

Long-term variations in north-south asymmetry of solar activity   总被引：1，自引：0，他引：1  

Derek B. Swinson  Hisako Koyama  Takao Saito 《Solar physics》1986,106(1):35-42

We present a new set of data on relative sunspot number (total, northern hemisphere, and southern hemisphere), taken for the 37-yr period 1947 to 1983; this constitutes a particularly coherent and consistent set of data, taken by the same observer (Hisako Koyama) using the same observing instrument. These data are combined with earlier data (White and Trotter, 1977) on the variation of sunspot areas for both solar hemispheres from 1874 to 1971. The combined data, covering 110 years and 10 solar cycles, are examined for periodicity in solar activity north-south asymmetry. We show that, in general, northern hemisphere activity, displayed as either An/(An + As) or Rn/(Rn + Rs), peaks about two years after sunspot minimum. This peak is greater during even cycles, pointing to a 22-yr periodicity in north-south asymmetry in solar activity, suggesting that the asymmetry is related to the 22-yr solar magnetic cycle. We demonstrate that the largest and most protracted period of northern-hemisphere activity excess in the last 110 years has occurred from 1959 to 1970; we show that there is a strong correlation between northern activity excess and a cosmic-ray density gradient perpendicular to the ecliptic plane, pointing southward, which is evident in cosmic-ray diurnal variation data from the Embudo underground cosmic-ray telescope.  相似文献   

Rare earth element diffusion in diopside: influence of temperature, pressure, and ionic radius, and an elastic model for diffusion in silicates   总被引：9，自引：2，他引：9  

James A. Van Orman  Timothy L. Grove  Nobumichi Shimizu 《Contributions to Mineralogy and Petrology》2001,141(6):687-703

Volume diffusion rates for five rare earth elements (La, Ce, Nd, Dy, and Yb) have been measured in single crystals of natural diopside at pressures of 0.1 MPa to 2.5 GPa and temperatures of 1,050 to1,450 °C. Polished, pre-annealed crystals were coated with a thin film of rare earth element oxides, then held at constant temperature and pressure for times ranging from 20 to 882 h. Diffusion profiles in quenched samples were measured by SIMS (secondary ion mass spectrometry) depth profiling. At 1 atm pressure, with the oxygen fugacity controlled near the quartz-fayalite-magnetite buffer, the following Arrhenius relations were obtained for diffusion normal to (001) (diffusion coefficient D in m²/s): log₁₀D_Yb=(-4.64ǂ.42)-(411ᆠ kJ/mol/2.303RT); log₁₀D_Dy=(-3.31ǃ.44)-(461ᆽ kJ/mol/2.303RT); log₁₀D_Nd=(-2.95DŽ.64)-(496ᇡ kJ/mol/2.303RT); log₁₀D_Ce=(-4.10ǃ.08)-(463ᆳ kJ/mol/2.303RT); log₁₀D_Lu=(-4.22DŽ.66)-(466ᇢ kJ/mol/2.303RT). Diffusion rates decrease significantly with increasing ionic radius, with La a factor of ~35 slower than Yb. The relationship between diffusivity and ionic radius is consistent with a model in which elastic strain plays a critical role in governing the motion of an ion through the crystal lattice. Activation volumes for Yb and Ce diffusion, at constant temperature and oxygen fugacity, are 9.0DŽ.0 cm³/mol and 8.9Dž.2 cm³/mol, respectively, corresponding to an order of magnitude decrease in diffusivity as pressure is increased from 0 to 3 GPa at 1,200 °C. Diffusion of Nd is such that grain-scale isotopic equilibrium in the mantle can be achieved in ~1 My under conditions near the peridotite solidus (~1,450 °C at 2.5 GPa). The equilibration time is much longer under P, T conditions of the lithospheric mantle or at the eclogite solidus (~1 Gy at 1.5 GPa and 1,150 °C). Because of the relatively strong decrease in diffusivity with pressure (two orders of magnitude between 2.5 and 15 GPa along an adiabatic temperature gradient), Nd transport in clinopyroxene will be effectively frozen at pressures approaching the transition zone, on time scales less than 100 My. Rare earth element diffusion rates are slow enough that significant disequilibrium uptake of REE by growing clinopyroxene phenocrysts may be preserved under natural conditions of basalt crystallization. The relative abundances and spatial distributions of REE in such crystals may provide a sensitive record of the cooling and crystallization history of the host lava.  相似文献   

Geochemistry of transition elements in garnet lherzolite nodules in kimberlites     

N. Shimizu  C. J. Allègre 《Contributions to Mineralogy and Petrology》1978,67(1):41-50

The clinopyroxenes and garnets from garnet lherzolite nodules in kimberlites were analyzed for the major and trace elements (Sc, Ti, V, Cr, Mn, Co, Sr, and Zr) with the secondary ion mass spectrometry (SIMS) techniques using an ion-microprobe. The concentration ranges for clinopyroxenes are: 12–90 ppm Sc, 60–2540 ppm Ti, 110–350 ppm V, 2400 ppm-1.68% Cr, 470–1100 ppm Mn, 18–70 ppm Co, 85–710 ppm Sr, and 6.3–120 ppm Zr. Those for garnets are: 71–180 ppm Sc, 140–6200 ppm Ti, 220–450 ppm V, 1.05–6.24% Cr, 1600–5220 ppm Mn, 33–92 ppm Co, and 66–250 ppm Zr.These data were used to assess a possible use of distribution of transition elements between clinopyroxene and garnet for geothermometry/geobarometry. The distribution coefficients of V and Mn show good correlations with (Ca/Ca+Mg+Fe)_CPX, suggesting their potential usefulness.The abundances of these elements in minerals (and estimated whole-rocks) suggest that garnet lherzolite nodules in kimberlites can be classified into three groups. It is suggested that one of the groups (Group I) could be close to the pristine mantle on the basis of Ti and Zr abundances as well as REE systematics. Arguments on Ti/Zr ratios among different nodule types suggest that abundant granular garnet lherzolites could be cumulates crystallized from a residual liquid after ilmenite was extracted.IPG Contribution No. 281  相似文献   

Rare earth elements in alpine peridotites     

M. Loubet  N. Shimizu  C. J. Allègre 《Contributions to Mineralogy and Petrology》1975,53(1):1-12

The samples from alpine peridotite massifs (Beni Bouchera, Lherz and the Alps) have been analyzed for rare earth elements. The peridotites as a whole are characterized by various degrees of light REE depletion (Ce varies from 1.2 to 0.02 times chondrite) and a small variation in heavy REE (Yb varies about a factor of 2, from 1.3 to 2.2 times chondrite). They show a restricted and regular distribution in a Ce-Yb diagram, giving two types of linear trends for individual massifs (trend A for the Alps and Lizard; trend B for Beni Bouchera and Lherz, branching from trend A). The model calculations of partial melting based on the partition relations of REE among silicate minerals and melts suggest that trend A could represent a series of residua left after partial melting of garnet peridotite despite the fact that there is no garnet observed in the peridotites studied here. It is suggested that trend A would represent a melting event which predated the emplacement of the massifs and occurred at higher pressure (in the presence of garnet) than expected from the present mineralogy. The calculations also suggest that trend B could represent a partial melting event at lower pressures than trend A after the massifs uplifted into spinel peridotite field. It is also suggested that the REE concentrations of the mantle could be estimated as 2–2.5 times chondrite.  相似文献   

Strontium and samarium diffusion in diopside   总被引：1，自引：0，他引：1  

Mark Sneeringer  Stanley R. Hart  Nobumichi Shimizu 《Geochimica et cosmochimica acta》1984,48(8):1589-1608

The volume chemical diffusion of trace amounts of Sr in diopside has been measured as a function of temperature (1100–1300°C), pressure (1 bar–20 kbar), crystallographic direction, and composition. Three experimental/analytical techniques were employed: radiotracer and sectioning; stable tracer and ion microprobe; and Rutherford back-scattering spectroscopy. Comparison of the three yielded excellent agreement. Both natural and synthetic single crystal samples were used with results in the natural diopside giving diffusivities approximately two orders of magnitude greater than those in the man-made crystals. Samarium diffusion in the synthetic crystals was also examined with the ion probe technique with results similar to Sr.Arrhenius relations for diffusion (D = D₀exp[?ΔH_a/RT]) were calculated for different pressures and analytical techniques, and activation volumes (gDV_a) were derived from the equation D = D' exp[?PΔV_a/ RT]. Values of ΔV_a were negative for Sr diffusion. An empirical relation describing the temperature and pressure dependence of D for Sr in the c direction of the synthetic samples is: D(P, T) = 1200 (cm²/sec) exp[?122 (Kcal/mol)/RT (°K)]exp[?P (bar)/(2.94T ? 4640)R]. The expression for D_Sr in the natural samples (c direction) at one atmosphere is: D(0, T) = 54 (cm²/sec) exp[?97 (Kcal/mol)/RT (°K)]. A single compensation trend for all the data was evident for all values of D₀ and ΔH_a in the synthetic crystals.A number of models of geologic processes were investigated in light of the present data. Closure temperatures (T_c) were calculated for examples of mineral-mineral age-dating and trace element geothermometry. High values of T_c indicate that pyroxenes record emplacement events and are generally not disturbed unless a fluid enters the system. Isotopic equilibration times were examined for lower crustal xenoliths and the mantle source region for MORB using the formula of Hofmann and Hart (1978). Equilibration was shown to be too fast for production of isotopic anomalies in MORB via disequilibrium melting. Also. reasonable residence times at lower crustal temperatures were shown to produce the mineralogical-scale isotopic homogeneity observed in a crustal xenolith from Kilbourne Hole, New Mexico.  相似文献   

Diarrhetic shellfish poisoning in Narragansett Bay     

Lucie Maranda  Yuzuru Shimizu 《Estuaries and Coasts》1987,10(4):298-302

A two-year survey for diarrhetic shellfish poisoning (DSP) was conducted in Narragansett Bay using the mouse assay method. The suspected causative organisms,Dinophysis spp., were monitored at the same time. Only one shellfish sample, in September 1984, yielded an unequivocal positive result at a time when the dinoflagellate population was dominated byD. acuminata. False positive results were suspected in May, when the mussels appeared sexually matured, and in, the summer of 1985, at the time of an unusual massive picoplanktonic bloom. Evidence of toxin production byD. acuminata was obtained from an almost monospecific sample; we calculated that over 5.4×10⁵ cells would be necessary to produce one mouse unit. The specificity and sensitivity of the assay method are questioned and improvements for DSP detection are suggested.  相似文献