Rare Earth, Major and Trace Elements in the Kunimiyama Ferromanganese Deposit in the Northern Chichibu Belt, Central Shikoku, Japan

Abstract. Rare earth, major and trace element geochemistry is reported for the Kunimiyama stratiform ferromanganese deposit in the Northern Chichibu Belt, central Shikoku, Japan. The deposit immediately overlies greenstones of mid-ocean ridge basalt (MORB) origin and underlies red chert. The ferromanganese ores exhibit remarkable enrichments in Fe, Mn, P, V, Co, Ni, Zn, Y and rare earth elements (excepting Ce) relative to continental crustal abundance. These enriched elements/ Fe ratios and Post-Archean Average Australian Shale-normalized REE patterns of the ferromanganese ores are generally analogous to those of modern hydrothermal ferromanganese plume fall-out precipitates deposited on MOR flanks. However in more detail, Mn and Ti enrichments in the ferromanganese ores are more striking than the modern counterpart, suggesting a significant contribution of hydrogenetic component in the Kunimiyama ores. Our results are consistent with the interpretation that the Kunimiyama ores were umber deposits that primarily formed by hydrothermal plume fall-out precipitation in the Panthalassa Ocean during the Early Permian and then accreted onto the proto-Japanese island arc during the Middle Jurassic. The presence of strong negative Ce anomaly in the Kunimiyama ores may indicate that the Early Permian Panthalassa seawater had a more striking negative Ce anomaly due to a more oxidizing oceanic condition than today.     

Quantitative assessment on the influence of heavy rainfall on the crystalline schist landslide by monitoring system -case study on Zentoku landslide, Japan

On Shikoku Island, which is one of the four main islands of Japan, a large number of large-scale crystalline schist landslides have been revealed and are being monitored by an observation system. Seasonal heavy rainfall is the most active meteorological factor that can threaten the stability of this kind of site-specific landslide. In this paper, on the basis of the study of the rainfall-related behavior of a typical crystalline schist landslide, the Zentoku landslide, by analyzing the precisely and continuously observed piezometric and movement data, a method was developed to quantitatively assess the effect of heavy rainfall on a large-scale landslide. The results indicated that heavy rainfall-induced landslide displacement shows good correlation with the variation of groundwater levels. Variations of groundwater level have been simulated with the use of a tank model. The simulation using this model permits the change in water levels for future rainfall events to be predicted. By combining the predicted results with the empirical relation between displacements and water levels, rainfall-induced landslide movement during extreme rainfall events can be estimated in advance. The effect of heavy rainfall on sliding behavior can be quantified in terms of the change in displacement. Thus warning information or advisories for the local residents can be provided.     

Geochemical fixation of rare earth elements into secondary minerals in sandstones beneath a natural fission reactor at Bangombé, Gabon

To study geochemical processes for migration and fixation of fissiogenic rare earth elements (REE) in association with uranium dissolution, in situ isotopic analyses using an ion microprobe were performed on U- and REE-bearing secondary minerals, such as coffinite, françoisite, uraniferous goethite, and uraninite found in a sandstone layer 30 to 110 cm beneath a natural fission reactor at Bangombé, Gabon. Phosphate minerals such as phosphatian coffinite and françoisite with depleted ²³⁵U (²³⁵U/²³⁸U = 0.00609 to 0.00638) contained large amount of fissiogenic light REE, while micro-sized uraninite grains in a solid bitumen aggregate have normal U isotopic values (²³⁵U/²³⁸U = 0.00725) and small amount of fissiogenic REE components. The proportions of fissiogenic and non-fissiogenic REE components in four samples from the core of BAX03 vary in depth ranging from 30 cm to 130 cm beneath the reactor, which suggests mixing between fissiogenic isotopes from the reactor and non-fissiogenic isotopes from original minerals in the sandstone. Significant chemical fractionation was observed between Ce and the other REE in the secondary minerals, which shows evidence of an oxidizing atmosphere during their formation. Pb-isotopic analyses of individual minerals do not directly provide chronological information because of the disturbance of U-Pb decay system due to recent geologic alteration. However, systematic Pb-isotopic results from all of the minerals reveal the mobilization of fissiogenic isotopes, Pb and U from the reactor in association with dolerite dyke intrusion ∼0.798 Ga ago and the formation of the secondary minerals by mixing event between 2.05 Ga-old original minerals and reactor materials due to recent alteration.     

U-Pb and Pb-Pb ages of zircons from basaltic eucrites: Implications for early basaltic volcanism on the eucrite parent body

We have undertaken petrologic and SHRIMP U-Th-Pb isotopic studies on zircons from basaltic eucrites (Yamato [Y]-75011, Y-792510, Asuka [A]-881388, A-881467 and Padvarninkai) with different thermal and shock histories. Eucritic zircons are associated with ilmenite in most cases and have subhedral shapes in unmetamorphosed and metamorphosed eucrites. Some zircons in highly metamorphosed eucrites with granulitic texture occur alone in pyroxene, and typically have rounded to subrounded shapes due to recrystallization. Superchondritic Zr/Hf ratios of eucritic zircons indicate that they crystallized from incompatible element-rich melts after crystallization of ilmenite. Concentrations of uranium and thorium in zircons in the unmetamorphosed eucrite Y-75011 are higher than those in metamorphosed eucrites.The U-Pb systems of eucritic zircons are almost concordant but some zircon grains show reverse discordance. Radiogenic lead-loss up to 48% from zircons is observed in the shock-melted eucrite Padvarninkai. The ²⁰⁷Pb-²⁰⁶Pb ages of zircon in Y-75011 (4550 ± 9 Ma, n = 5) are nearly identical, within analytical uncertainty, to the ages of zircons from the metamorphosed eucrite Y-792510 (4545 ± 15 Ma, n = 13), the highly metamorphosed eucrites A-881388 (4555 ± 54 Ma, n = 5) and A-881467 (4558 ± 13 Ma, n = 8), and the shock-melted eucrite Padvarninkai (4555 ± 13 Ma, n = 18). The averaged ²⁰⁷Pb-²⁰⁶Pb age of zircon from five eucrites analyzed in this study is 4554 ± 7 Ma (95% confidence limits, n = 49), indistinguishable from the averaged U-Pb age (4552 ± 9 Ma) of the same samples. Because of the high closure temperature of lead in zircon (T_closure = ∼1050°C with a cooling rate of 0.2°C/yr), the ²⁰⁷Pb-²⁰⁶Pb ages of eucritic zircon do not represent metamorphic ages but crystallization ages of extrusive lavas.This fact strongly suggests that volcanism of the eucrite parent body occurred at a very early stage of the Solar System history, 7-20 Ma after CAI formation (4567.2 ± 0.6 Ma), thus basaltic eucrites crystallized from parental magmas within a short interval following the differentiation of their parent body. The U-Pb ages of eucritic zircons are older than the U-Pb, Sm-Nd and Rb-Sr ages of some basaltic eucrites, which is consistent with differences in closure temperatures of each isotopic system, and suggests that thermal and shock metamorphism affected the isotopic systems of pyroxene, plagioclase and phosphates.     

Trace element distribution in mineral separates of the Allende inclusions and their genetic implications

Concentrations of the REE, Sc, Co, Fe, Zn, Ir, Na and Cr were determined by instrumental neutron activation and mass spectrometric isotope dilution analysis for mineral separates of the coarseand fine-grained types (group I and II of Martin and Mason's classification) of the Allende inclusions.These data, combined with data on mineral/liquid partition coefficients, oxygen isotope distributions and diffusion calculations, suggest the following: (1) Minerals in the coarse-grained inclusions (group I) crystallized in a closed system with respect to refractory elements. On the other hand, differences in oxygen isotope distributions among minerals preclude a totally molten stage in the history of the inclusion. Group I inclusions were formed by rapid condensation (either to liquid or solid) in a supercooled solar nebula; extrasolar pyroxene and spinel dust were included but not melted in the condensing inclusions, thus preserving their extrasolar oxygen isotope composition. REE were distributed by diffusion during the subsequent heating at subsolidus temperatures; because oxygen diffuses much more slowly at these temperatures, the oxygen isotope anomalies were preserved. (2) The fine-grained (group II) inclusions were also formed by condensation from a super-cooled nebular gas; however, REE-rich clinopyroxene and spinel were formed early and REE-poor sodalite and nepheline were formed later and mechanically mixed with clinopyroxene and spinel to form the inclusions. The REE patterns of the bulk inclusions and the mineral separates are fractionated, indicating that REE abundances in the gaseous phase were already fractionated at the time of condensation of the minerals. (3) Pre-existing Mg isotope anomalies in the coarse-grained inclusions must have been erased during the heating stage thus resetting the ²⁶Al-²⁶Mg chronometer.     

Seasonal variations of spectra of wind speed and air temperature in the mesoscale frequency range

Seasonal variations of the spectra of wind speed and air temperature in the mesoscale frequency range from 1.3 × 10^-4 to 1.5 × 10^-3 Hz (10 min to 2 h periods) have been studied through observations over land for one year. Spectrographs [time series of isopleths of spectral densities, f · S(f) vs f] of wind speed and air temperature contain occasional peaks that are attributed to short-lived mesoscale atmospheric activity with narrow frequency bands. Significant spectral peaks of wind speed were found in 19% of the total observations in winter, and in 15–16% in the other seasons; for air temperature, they occured in 12% of observations in autumn, and in 16–19% in the other seasons. The peaks most often occurred in the period range from 30 min to 1 h; most had durations less than 24 h. Mesoscale fluctuations of wind speed and air temperature were highly correlated, and in most cases, phase differences were 90–180 ° with air temperature leading wind speed. Significant spectral peaks of wind speed often occurred during northerly seasonal cold winds in winter, and accompanied tropical and/or mid-latitude cyclones in the other seasons. When the peaks occurred, wind speed was usually relatively high and the atmospheric surface layer was unstable.     

Characteristics of rainfall systems accompanied with Changma front at Chujado in Korea

The rainy season from June to July in the East Asia is called the Changma in Korea, the Meiyu in China, or the Baiu in Japan. The mesoscale convective systems which occur near a front frequently lead to severe weather phenomenon such as localized gust and heavy rainfall. An intensive field experiment was conducted at Chujado (33.95°N, 126.28°E) to find out the characteristics of the precipitating system using information such as the raindrop size distribution, kinematic features during a Changma period between June 21 2007 and July 11 2007. Different characteristics of three identified rainfall cases in a Changma frontal precipitation system occurred from 5 to 6 July in 2007 at Chujado area have been identified. Based on the radar reflectivity and raingage at Chujado, each rainfall system maintained for 7 hours, 4 hours, and 9 hours, respectively. According to the analysis of a total vertical wind shear (TVWS) and a directional vertical wind shear (DVWS), the temperature gradient was the strongest near the surface and both warm and cold advections were occurred in all cases but at different levels. The deep warm advection was related to the longer rainfall lifetime and stronger rainrate, but smaller raindrop size. The unstable atmospheric condition, which has cold advection at the surface and warm advection in higher level, caused the larger size diameter of raindrop. The echo top height of 30 dBZ was around 6 km in the two rainfall systems and around 4 km in the other one. The number concentrations of raindrop has turning point at the drop size of 2 mm in diameter. The stronger (weaker) updraft and downdraft were also related to the decreased number concentration of smaller (larger) size drops and increased that of the larger (smaller) drops.     

Simulations of seasonal variations of sulfur compounds in the remote marine atmosphere

A photochemical box model is used to simulate seasonal variations in concentrations of sulfur compounds at latitude 40° S. It is assumed that the hydroxyl radical (OH) addition reaction to sulfur in the dimethyl sulfide (DMS) molecule is the predominant pathway for methanesulfonic acid (MSA) production, and that the rate constant increases as the air temperature decreases. Concentration of the nitrate radical (NO₃) is a function of the DMS flux, because the reaction of DMS with NO₃ is the most important loss mechanism of NO₃. While the diurnally averaged concentration of OH in winter is a factor of about 8 smaller than in summer, due to the weak photolysis process, the diurnally averaged concentration of NO₃ in winter is a factor of about 4–5 larger than in summer, due to the decrease of DMS flux. Therefore, at middle and high latitudes in winter, atmospheric DMS is mainly oxidized by the reaction with NO₃. The calculated ratio of the MSA to SO₂ production rates is smaller in winter than in summer, and the MSA to non-sea-salt sulfate (nssSO₄ ^2-) molar ratio varies seasonally. This result agrees with data on the seasonal variation of the MSA/nssSO₄ ^2- molar ratio obtained at middle and high latitudes. The calculations indicate that during winter the reaction of DMS with NO₃ is likely to be a more important sink of NO_x (NO+NO₂) than the reaction of NO₂ with OH, and to serve as a significant pathway of the HNO₃ production. If dimethyl sulfoxide (DMSO) is produced through the OH addition reaction and is heterogeneously oxidized in aqueous solutions, half of the nssSO₄ ^2- produced in summer may be through the oxidation process of DMSO. It is necessary to further investigate the oxidation products by the reaction of DMS with OH, and the possibility of the reaction of DMS with NO₃ during winter.     

An Improved Mellor–Yamada Level-3 Model: Its Numerical Stability and Application to a Regional Prediction of Advection Fog

This note describes a numerically stable version of the improved Mellor–Yamada (M–Y) Level-3 model proposed by Nakanishi and Niino [Nakanishi, M. and Niino, H.: 2004, Boundary-Layer Meteorol. 112, 1–31] and demonstrates its application to a regional prediction of advection fog. In order to ensure the realizability for the improved M–Y Level-3 model and its numerical stability, restrictions are imposed on computing stability functions, on L/q, the temperature and water-content variances, and their covariance, where L is the master length scale and q ²/2 the turbulent kinetic energy per unit mass. The model with these restrictions predicts vertical profiles of mean quantities such as temperature that are in good agreement with those obtained from large-eddy simulation of a radiation fog. In a regional prediction, it also reasonably reproduces the satellite-observed horizontal distribution of an advection fog.     

Numerical study of the oxidation process of dimethylsulfide in the marine atmosphere

A box model, involving simple heterogeneous reaction processes associated with the production of non-sea-salt sulfate (nss-SO ₄ ^2– ) particles, is used to investigate the oxidation processes of dimethylsulfide (DMS or CH₃SCH₃) in the marine atmosphere. The model is applied to chemical reactions in the atmospheric surface mixing layer, at intervals of 15 degrees latitude between 60° N and 60° S. Given that the addition reaction of the hydroxyl radical (OH) to the sulfur atom in the DMS molecule is faster at lower temperature than at higher temperature and that it is the predominant pathway for the production of methanesulfonic acid (MSA or CH₃SO₃H), the results can well explain both the increasing tendency of the molar ratio of MSA to nss-SO ₄ ^2– toward higher latitudes and the uniform distribution with latitude of sulfur dioxide (SO₂). The predicted production rate of MSA increases with increasing latitude due to the elevated rate constant of the addition reaction at lower temperature. Since latitudinal distributions of OH concentration and DMS reaction rate with OH are opposite, a uniform production rate of SO₂ is realized over the globe. The primary sink of DMS in unpolluted air is caused by the reaction with OH. Reaction of DMS with the nitrate radical (NO₃) also reduces DMS concentration but it is less important compared with that of OH. Concentrations of SO₂, MSA, and nss-SO ₄ ^2– are almost independent of NO _x concentration and radiation field. If dimethylsulfoxide (DMSO or CH₃S(O)CH₃) is produced by the addition reaction and further converted to sulfuric acid (H₂SO₄) in an aqueous solution of cloud droplets, the oxidation process of DMSO might be important for the production of aerosol particles containing nss-SO ₄ ^2– at high latitudes.