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.     

Nuclide analyses of rare earth elements of the Oklo uranium ore samples: a new method to estimate the neutron fluence

Isotopic ratios and abundances of all REE in two Oklo ore samples have been measured. We have succeeded in developing a new method to estimate the neutron fluence, the conversion factor of uranium and the average neutron energy (or temperature) based on Gd and U isotopic ratios. This new calculation is found to be useful in evaluating those parameters for the natural nuclear reactors at Oklo. Comparison is made between the neutron fluence values evaluated by our new method employing Gd isotopes and a previous one [11] employing Sm and Nd isotopes. The relative agreement becomes better with the increase of fluence. A relationship between the abundances of fissiongenic nuclides of La, Ce, Nd, Sm, and Gd and their mass numbers is also presented.     

∼3,850 Ma tonalites in the Nuuk region,Greenland: geochemistry and their reworking within an Eoarchaean gneiss complex

The Eoarchaean (>3,600 Ma) Itsaq Gneiss Complex of southern West Greenland is dominated by polyphase orthogneisses with a complex Archaean tectonothermal history. Some of the orthogneisses have c. 3,850 Ma zircons, and they vary from rare single phase metatonalites to more common complexly banded migmatites. This is due to heterogeneous strain, in situ anatexis and granitic veining superimposed during younger tectonothermal events. In the single-phase tonalites with c. 3,850 Ma zircon, oscillatory-zoned prismatic zircon is all 3,850 Ma old, but shows patchy ancient loss of radiogenic Pb. SHRIMP spot analyses and laser ablation ICP-MS depth profiling show that thin (usually < 10 μm) younger (3,660–3,590 Ma and Neoarchaean) shells of lower Th/U metamorphic zircon are present on these 3,850 Ma zircons. Several samples with this simple zircon population occur on islands near Akilia. In contrast, migmatites usually contain more complex zircon populations, with often more than one generation of igneous zircon present. Additional zircon dating of banded gneisses across the Complex shows that samples with c. 3,850 Ma igneous zircon are not just a phenomenon restricted to Akilia and adjacent islands. For example, migmatites from Itilleq (c. 65 km from Akilia) contain variable amounts of oscillatory-zoned 3,850 Ma and 3,650 Ma zircon, interpreted, respectively, as the rock age and the time of crustal melting under Eoarchaean metamorphism. With only 110–140 ppm Zr in the tonalites and likely magmatic temperatures of >850°C, zircon solubility–melt composition relationships show that they were only one-third saturated in zircon. Any zircon entrained in the precursor magmas would thus have been highly soluble. Combined with the cathodoluminesence imaging, this demonstrates that the c. 3,850 Ma oscillatory zoned zircon crystallised out of the melt and hence gives a magmatic age. Thus the rare well-preserved tonalites and palaeosome in migmatites testify that c. 3,850 Ma quartzo–feldspathic rocks are a widespread (but probably minor) component in the Itsaq Gneiss Complex. C. 3,850 Ma zircon with negative Eu anomalies (showing growth in felsic systems) also occurs as detrital grains in rare c. 3,800 Ma metaquartzites and as inherited grains in some 3,660 Ma granites (sensu stricto). These demonstrate that still more c. 3,850 Ma rocks were present, but were recycled into Eoarchaean sediments and crustally derived granites. The major and trace element characteristics (e.g. LREE enrichment, HREE depletion, low MgO) of the best-preserved c. 3,850 Ma rocks are typical of Archaean TTG suites, and thus argue for crust formation processes involving important contributions from melting of hydrated mafic crust to the earliest Archaean. Five c. 3,850 Ma tonalites were selected as the best preserved on the basis of field criteria and zircon petrology. Four of these samples have overlapping initial ɛ_Nd (3,850 Ma) values from +2.9 to +3.6± 0.5, with the fourth having a slightly lower value of +0.6. These data provide additional evidence for a markedly LREE-depleted early terrestrial mantle reservoir. The role of c. 3,850 Ma crust should be considered in interpreting isotope signatures of the younger (3,800–3,600 Ma) rocks of the Itsaq Gneiss Complex. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Neutron capture records of mesosiderites and an iron meteorite

The Sm and Gd isotopic compositions of silicates from six mesosiderites (Dalgaranga, Estherville, Morristown, Northwest Africa (NWA) 1242, NWA 2932, and Vaca Muerta) and one iron meteorite (Udei Station) were determined to elucidate the cosmic-ray exposure records. All seven samples showed significant ¹⁵⁰Sm/¹⁴⁹Sm and ¹⁵⁸Gd/¹⁵⁷Gd isotopic shifts from neutron capture reactions corresponding to neutron fluences of (1.3-21.8) × 10¹⁵ n cm⁻². In particular, Vaca Muerta showed a significantly higher neutron fluences than the other six samples. The parameter for the degree of neutron thermalization (ε_Sm/ε_Gd) also showed a significant difference between Vaca Muerta (0.76) and the other samples (0.93-1.20). These results suggest a two-stage irradiation of the Vaca Muerta silicates in the parent body (>50 Ma) before formation of the mesosiderite and during its transit to Earth (138 Ma). This is consistent with the ⁸¹Kr-Kr cosmic-ray exposure age data of a Vaca Muerta pebble from a previous noble gas isotopic study.     

Ba isotopic signature for early differentiation between Cs and Ba in natural fission reactors

Ba isotopic studies of the Oklo and Bangombé natural fission reactors in east Gabon provide information on the geochemical behavior of radioactive Cs (¹³⁵Cs and ¹³⁷Cs) in a geological medium. Large isotopic deviations derived from fissiogenic Ba were found in chemical leachates of the reactor uraninites. The fissiogenic Ba isotopic patterns calculated by subtracting the non-fissiogenic component are classified into three types that show different magnifications of chemical fractionation between Cs and Ba. In addition, the isotopic signatures of fissiogenic ¹³⁵Ba, ¹³⁷Ba and ¹³⁸Ba suggest an early differentiation between Cs and Ba of less than 20 years after the production of fissiogenic Cs and Ba. On the other hand, only small excesses of ¹³⁵Ba (ε < +1.8) and/or ¹³⁷Ba (ε < +1.3) were identified in some clay samples, which might have resulted from selective adsorption of ¹³⁵Cs and ¹³⁷Cs that migrated from the reactors by differentiation.     

Global distribution and atmospheric transport of chlorinated hydrocarbons: HCH (BHC) isomers and DDT compounds in the Western Pacific,Eastern Indian and Antarctic Oceans

Concentrations of chlorinated hydrocarbons such as HCH isomers and DDT compounds were determined in air and surface water samples taken from the Western Pacific, Eastern Indian and Antarctic Oceans. The most interesting finding was their presence in measurable concentrations in the Antarctic Ocean. Chlorinated hydrocarbon pesticides are widely distributed in the open ocean environment over both the northern and southern hemispheres, and some characteristic distribution patterns of pesticide species in different oceanic regions were observed both in air and water samples. HCH residues found in the northern hemisphere were much higher in concentration than those in the southern hemisphere. On the other hand, higher concentrations of DDT residues were found in the tropical regions, but their levels were not so different between both the northern and southern hemispheres. HCH isomers found in the northern hemisphere had the following order of concentrations:-HCH> HCH>-HCH, while in the southern hemisphere-HCH was apparently dominant. DDT compound compositions were rather uniform in all the oceans surveyed, and more than 50% wasp,p-DDT. These facts can be explained by the world wide situation regarding pesticide use and the physicochemical properties of the pesticides such as their vapor pressures and water solubilities. In addition, the meridional circulation of the atmosphere, particularly the mass flows of the Hadley and Ferrel cells in the troposphere, also contributes to the atmospheric transport and global distribution of these pesticides.     

A highly sensitive and large concentration range colorimetric continuous flow analysis for ammonium concentration

A continuous flow method for the determination of ammonium concentration in seawater from a nanomolar to a micromolar level is described. To prevent spurious peaks derived from salinity difference, a gas-permeable hydrophobic membrane filter was used to separate the manifold into an outgassing section and an indophenol blue reaction section. The indophenol blue reaction section was adopted for colorimetric analysis and is equipped with a 1-m path length liquid capillary cell and a fiber-optic spectrometer, which is able to record the absorbance at multiple wavelengths. The minimum detection limit at wavelength 630 nm is 5.5 ± 1.8 nM, and the calibration curves are linear to at least 2,000 nM. In addition, the minimum detection limit at wavelength 530 nm was 13 ± 5.3 nM, and linear calibration curves were observed until at least 10,000 nM. The slopes of the calibration curves were similar for standards prepared using filtered seawater and ultrapure water. The ammonium concentration of the ultrapure water was similar to those of ion-exchanged water and unfiltered low-nutrient seawater, but was significantly lower than those of filtered seawater and solutions that contained sodium hydroxide. Therefore, ultrapure water is optimal for both blank and standard preparations because of its stable quality and availability. Given its large concentration range and the use of readily available blanks, this method is suitable for the determination of ammonium concentration and helps our understanding of ammonium dynamics in the ocean.     

Siderophile element characteristics of acapulcoite–lodranites and winonaites: Implications for the early differentiation processes of their parent bodies

We have studied magnetic fractions of five acapulcoites, three lodranites, and two winonaites to investigate chemical compositions of their precursor materials and metallic partial melting processes occurring on their parent bodies. One winonaite metal is similar in composition to low Au, low Ni IAB iron subgroup, indicating genetic relationship between them. Magnetic fractions of chondrule‐bearing acapulcoite and winonaite have intermediate chemical compositions of metals between H chondrites and EL chondrites. This fact indicates that the precursor materials of acapulcoite–lodranites and winonaites were similar to H and/or EL chondrites in chemical compositions. Magnetic fractions in acapulcoite–lodranites have a large variety of chemical compositions. Most of them show enrichments of W, Re, Ir, Pt, Mo, and Rh, and one of them shows clear depletion in Re and Ir relative to those of chondrule‐bearing acapulcoite. Chemical compositional variations among acapulcoite–lodranite metals cannot be explained by a single Fe‐Ni‐S partial melting event, but a two‐step partial melting model can explain it.