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.     

贵阳地表水-地下水的硫和氯同位素组成特征及其污染物示踪意义

喀斯特地表水和地下水的交换活跃,地下水系统容易受到地表污染物的污染。为了解喀斯特城市地表水—地下水系统污染特征和污染物质来源,对贵阳市地表水、地下水、雨水和城市排污污水的硫同位素和氯同位素组成变化进行了研究。贵阳市不同类型水体的δ³⁷Cl值在-4.07‰～+2.03‰之间变化,δ34SSO4值变化为-20.4‰～+20.9‰。大气输入物质和城市排污污水的δ³⁷Cl、δ³⁴S及Cl^-/SO₄^2-比值与地表水和地下水的不同,稳定硫和氯同位素的结合研究为示踪地下水污染物来源提供了有效研究手段。贵阳市地下水中的Cl^-和SO^₄2-至少有4种来源,人为活动通过城市排污和大气输入向地下水系统大量输入了硫酸盐和氯离子。      

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.     

Hydrogeochemical Characterization and Groundwater Quality of Jamshedpur Urban Agglomeration in Precambrian Terrain,Eastern India

This paper reports petrography, geochemistry and Rb-Sr age data on the rare metal bearing Neoarchean fertile (Nb-Ta) granite at Allapatna and elucidates its petrogenesis and role in Nb-Ta-Li-Be mineralization. The Allapatna granite (AG) intrudes the Tonalitic-Trondhjemitic - Granodioritic (TTG) Peninsular Gneiss and analysed SiO₂ (72.3-75.6 wt%), K₂O (4.0-5.7wt%), Na2O (3.0-4.4wt%), CaO (0.7-1wt%), MgO (0.13-0.25wt%) and K₂O/Na₂O (>1) indicating evolved nature. The presence of muscovite, biotite and garnet in the mode, peraluminous nature and high initial ⁸⁷Sr/⁸⁶Sr ratio (0.7284±0.0083) attest to their S-type characteristics. Varying Nb/Ta ratio and high Li with moderate abundance of Cs further indicate affinity to Li-Cs-Ta (LCT) type granite-pegmatite system. TheAG showing whole rock Rb-Sr isochron age of 2803± 68 Ma, is the oldest reported fertile granite in India parental to rare metal pegmatites hosting Nb-Ta, Be, and Li resources. Partial melting of a mixed source consisting of both basement TTG rocks and metapelites has generated such type of granitic magma. Fractionation of such granitic magma possibly has given rise to the rare metal (Ta-Nb-Li-Be) bearing pegmatites intruding the nearby schist belt.     

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.     

Carbon and Noble Gas Isotopes in the Tengchong Volcanic Geothermal Area, Yunnan, Southwestern China

Carbon and noble gas isotope analyses are reported for bubbling gas samples from the Tengchong volcanic geothermal area near the Indo-Eurasian suture zone. All samples contain a resolvable component of mantle-derived 3He. Occurrence of mantle-derived 3He coincides with surface volcanism. However, 3He occurs over a larger geographic areathan do surface volcanics. δ13C values for CO2 and CH4 vary from -33.4‰ to 1.6 ‰ and from -52.8‰ to -2.8‰, respectively. He and C isotope systematics indicate that CO2 and CH4 in the CO2-rich gases originated predominantly from magmatic component mixed with crustal CO2 produced from carbonate. However, breakdown of organic matter and near-surface processes accounts for the CH4 and CO2 in N2-rich gases. 3He/4He ratio distribution pattern suggests that mantle-derived He and heat sources of high-temperature system in central Tengchong originate from a hidden magma reservoir at subsurface. CO2-rich gases with the highest 3He/4He ratio (5.2 Ra) may be representative of the     

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.     

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.     

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.