Redistribution of REE, Pb and U by supergene weathering studied from in-situ isotopic analyses of the Bangombé natural reactor, Gabon

The isotopic analyses of rare earth elements (REE), Pb and U in several kinds of minerals from the clay and black shale layers above the Bangombé natural reactor, Gabon, were performed using a sensitive high-resolution microprobe (SHRIMP) to investigate the migration and retardation processes of fission products released from the reactor. REE isotopic data of the secondary minerals found in clays and black shales show that most of fission products were effectively trapped in the clays and not distributed into the black shales over the clays, which reveals that the clays play an important role in preventing fission products from spreading.Zircon crystals in the clays heterogeneously contain high-U regions (up to 28.3 wt%) with normal ²³⁵U/²³⁸U ratios (=0.00725) and significant amounts of fissiogenic REE, which suggest the occurrence of significant chemical fractionation between REE and U during the dissolution of reactor uraninite and the recrystallization of secondary U minerals. The Pb data suggest that galena grains in the clays were also formed by the mixing of the two components during a recent alteration event, and that a significant amount of Pb was derived from 2.05-Ga-old original uraninite rather than reactor uraninite. The U-Pb systematics of zircon provide chronological information on the old igneous activity associated with the basement rock formation at 2.8 Ga and geochemical evidence of the incomplete mixing of independent Pb and U sources. This result is consistent with previous chronological results in this area.     

Formation and geochemical significance of micrometallic aggregates including fissiogenic platinum group elements in the Oklo natural reactor, Gabon

Metallic aggregates with a size of a few tens μm and consisting mainly of Ru, Rh, Pd, Te, Pb, As, Sb, S and Bi were found in the acid residue of SD37-S2/CD uraninite taken from Oklo natural reactor zone (RZ) 13. Quantitative analyses of major elements using an electron probe microanalyzer and in situ isotopic analyses of Zr, Mo, Ru, Pb and U using a sensitive high-resolution ion microprobe were performed on the metallic aggregates to determine the geochemical behaviors of fission products and actinides and to ascertain the processes of formation of the aggregates in the RZs. The chemical compositions of the aggregates investigated in this study are significantly different from those reported previously, showing lower Pb content and no correlation between the contents of Pb and S in the individual grains. The ²³⁵U/²³⁸U ratios in metallic aggregates vary significantly from 0.00478 to 0.01466, indicating chemical fractionation between U and Pu during the formation of the aggregates. The Pb isotopic data indicate that most of the Pb in the aggregates decayed from 2.05 Ga-old uraninite that existed in the RZ originally and that there was chemical fractionation between U and Pb in some aggregates. The Zr and Mo isotopic ratios, ⁹⁰Zr/⁹¹Zr and ⁹⁵Mo/⁹⁷Mo, for most of the aggregates had small variations, which can be simply explained by constant separate mixing of fissiogenic and nonfissiogenic components. On the other hand, a large variation in the ⁹⁹Ru/¹⁰¹Ru ratio (0.324-1.73) cannot be explained only by a two component mixing theory; thus, chemical fractionation between Tc and Ru during the reactor criticality is suggested. The large variations in the ²³⁵U/²³⁸U and ⁹⁹Ru/¹⁰¹Ru isotopic ratios suggest that the aggregates formed under various redox conditions owing to the radiolysis of water.     

Uraninite recrystallization and Pb loss in the Oklo and Bangombé natural fission reactors, Gabon

The Oklo and Bangombé natural fossil fission reactors formed ca. 2 Ga ago in the Franceville basin, Gabon. The response of uraninite in the natural reactors to different geological conditions has implications for the disposal of the UO₂ in spent nuclear fuel. Uraninite and galena from two reactor zones, RZ16 at Oklo and RZB at Bangombé, were studied to clarify the chronology and effect of alteration events on the reactor zones. In addition, ion microprobe U-Pb analysis of zircons from a dolerite dyke in the Oklo deposit were completed to better constrain the age of the dyke, and thereby testing the link between the dyke and an important alteration event in the reactor zones.The analyzed uraninite from RZ16 and RZB contains ca. 6 wt% PbO, indicating a substantial loss of radiogenic Pb. Transmission electron microscopy showed that microscopic uraninite grains in the reactor zones consist of mainly defect-free nanocrystalline to microcrystalline aggregates. However, the nanocrystalline regions have elevated Si contents and lower Pb contents than coarser uraninite crystallites. Single stage model ages of large, millimeter-sized galena grains at both RZ16 and RZB correlate well with the age of the Oklo dolerite dyke, 860 ± 39 Ma (2σ). Thus, the first major Pb loss from uraninite occurred at both Oklo and Bangombé during regional extension and the intrusion of a dyke swarm in the Franceville basin, ∼860-890 Ma ago. Uraninite Pb isotopes from RZ16 and RZB give lower ages of ca. 500 Ma. These ages agree with the “chemical” ages of the uraninite, and show that an ancient Pb loss occurred after the intrusion of the dolerite dykes. The presence of nanocrystallites in the reactor uraninite indicates internal recrystallization, which may have occurred around 500 Ma, resulting in the 6wt% PbO uraninite. It is suggested that leaching by fluid interaction triggered by the Pan-African orogeny was important during this second Pb-loss event. Thus, there are indications that uraninite at both the Oklo and Bangombé natural reactors has experienced at least two ancient episodes of Pb loss associated with internal recrystallization. These recrystallization events have occurred without significantly depleting the 2 Ga fission products compatible with the uraninite structure.     

SHRIMP in situ isotopic analyses of REE,Pb and U in micro-minerals bearing fission products in the Oklo and Bangombé natural reactors: A review of a natural analogue study for the migration of fission products

In the Precambrian, parts of the Oklo, Okélobondo and Bangombé uranium deposits of the Republic of Gabon, central Africa, functioned as natural fission reactors. Many elements in the Oklo and Bangombé uranium deposits show variations in isotopic composition caused by a combination of nuclear fission, neutron capture and radioactive decay. Isotopic studies provide useful information to understand the behavior of radionuclides in geological media. In our recent work, in situ REE, Pb and U isotopic analyses of individual tiny minerals in and around reactor zones have been performed using a SHRIMP (Sensitive High Resolution Ion Microprobe). The isotopic results of the SHRIMP analyses on micro-minerals found in and around the Oklo and Bangombé natural reactors are reviewed in this paper. The data suggest the selective uptake behavior of (1) Ra into illite, and (2) Pu into apatite, (3) the formation process of secondary minerals bearing fissiogenic REE and depleted U, (4) evidence of nuggets (?-particles) bearing fissiogenic platinum group elements (PGE), and (5) from the U–Pb systematics of highly altered zircons, the redistribution of U and Pb.     

Hydrothermal mobility of Ti, Zr and REE: examples from the Bergell and Adamello contact aureoles (Italy)

Contact metamorphic marbles, affected by metasomatic fluids at the contact to the Bergell and Adamello Intrusives, contain various accessory minerals (zirconolite, allanite, titanite, rutile, geikielite, hoegbomite), which provide new evidence for the hydrothermal mobility of Ti and Zr. In both examples, Ti and Zr migrated along with U, Th, Y and REE in a metasomatic fluid rich in potassium. The composition of the main minerals (fluorine-rich phlogopite, pargasite and titanian clinohumite) and the abundance of fluor-apatite demonstrate that fluorine and phosphorus were important components of the fluid. The textural relationships indicate that the formation of the accessory phases is linked to the crystallization of the hydrous minerals.     

Zircon megacrysts from basalts of the Venetian Volcanic Province (NE Italy): U–Pb ages, oxygen isotopes and REE data

Mafic alkaline lavas from the Venetian Volcanic Province (NE Italy) contain orange–brown zircon megacrysts up to 15 mm long, subhedral to subrounded and showing equant morphology, with width-to-length ratios of 1:2–1:2.5. U–Pb ages of zircon (51.1 ± 1.5 to 30.5 ± 0.51 Ma) fit the stratigraphic age of the host lava (Middle Eocene and Oligocene) and their oxygen isotope composition (δ¹⁸O = 5.31–5.51‰) is similar to that of zircon formed in the upper mantle. Cathodoluminescence images and crystal chemical features, e.g. depletion of incompatible elements such as REE, Y, U and Th at constant Hf content, indicate that centre-to-edge zircon zoning is not consistent with evolution of the melt by fractional crystallization. All the above features, together with the fact that zircon and host basalts are coeval, indicate that the studied Zr megacrysts crystallised from a primitive alkaline mafic magma, which later evolved to the less alkaline host magma.     

Trace elements (REE) and isotopes (O,C, Sr) to characterize the metasomatic fluid sources: evidence from the skarn deposit (Fe,W, Cu) of Traversella (Ivrea,Italy)

The skarn complex of Traversella was formed at the expense of various rock types (calcic hornfels, gneiss, dolomitic marble) occurring in the contact aureole of the dioritic intrusion of Traversella (30±5 Ma). Application of phase equilibria has fixed the temperature of the primary stage of skarn formation between 550° C to 625° C. Similar applications indicate a larger range of temperature (525° C to 300° C) for the secondary stage. The different types of skarn (primary stage) are enriched in REE relative to the corresponding precursor rock (T.R.=126 ppm (protolith) to 228 ppm (inner zone) for the skarn on gneisses; T.R.=14 ppm to 71 ppm for the skarn on calcic hornfelses; T.R.=12 ppm to 200 ppm for the skarn on dolomitic marbles), but all the inner zones of these different types of skarn show a similar REE distribution with a slight LREE fractionation and no Eu anomaly. It is inferred that the primary metasomatic fluid has a parallel REE pattern. The oxygen isotope composition of water in equilibrium with the early stage of skarn at T=600° C ranges from 8.3 per mil to 8.9 per mil. At the beginning of the first hydroxylation stage (secondary stage), the fluid σ ¹⁸O remains in the range observed in the primary stage but within it, there is a sharp decrease from 8.0 per mil to 5.0 per mil. During the sulphidation stage, the fluid σ ¹⁸O decreases more gradually from 5.0 per mil to 3.0 per mil. The I _Sr of the early skarn silicates ranges from the values observed in the dolomitic marbles (0.70874 to 0.70971) to the I _Sr of the intrusion (0.70947 to 0.71064). During the secondary stage, there is a progressive increase of the minerals I _Sr up to 0.71372. The REE pattern of the primary metasomatic fluid does not put any precise constraint on the primary fluid source. On the other hand, both stable and radiogenic isotopes suggest that the early high-temperature metasomatic fluid was isotopically equilibrated with the dioritic intrusion. This implies that this early fluid is either exsolved from the crystallizing intrusion or a metamorphic water previously equilibrated with the intrusion. During the secondary stage, the replacement of the early anhydrous phases by hydrated parageneses is accompanied by the mixing with meteoric fluid as indicated by stable (σ ¹⁸O) and radiogenic (⁸⁷Sr/⁸⁶Sr) isotopes.     

Intraplate mountain building in response to continent–continent collision—the Ancestral Rocky Mountains (North America) and inferences drawn from the Tien Shan (Central Asia)

The intraplate Ancestral Rocky Mountains of western North America extend from British Columbia, Canada, to Chihuahua, Mexico, and formed during Early Carboniferous through Early Permian time in response to continent–continent collision of Laurentia with Gondwana—the conjoined masses of Africa and South America, including Yucatán and Florida. Uplifts and flanking basins also formed within the Laurentian Midcontinent. On the Gondwanan continent, well inboard from the marginal fold belts, a counterpart structural array developed during the same period. Intraplate deformation began when full collisional plate coupling had been achieved along the continental margin; the intervening ocean had been closed and subduction had ceased—that is, the distinction between upper versus lower plates became moot. Ancestral Rockies deformation was not accompanied by volcanism. Basement shear zones that formed during Mesoproterozoic rifting of Laurentia were reactivated and exerted significant control on the locations, orientations, and modes of displacement on late Paleozoic faults.Ancestral Rocky Mountain uplifts extend as far south as Chihuahua and west Texas (28° to 33°N, 102° to 109°W) and include the Florida-Moyotes, Placer de Guadalupe–Carrizalillo, Ojinaga–Tascotal and Hueco Mountain blocks, as well as the Diablo and Central Basin Platforms. All are cored with Laurentian Proterozoic crystalline basement rocks and host correlative Paleozoic stratigraphic successions. Pre-late Paleozoic deformational, thermal, and metamorphic histories are similar as well. Southern Ancestral Rocky Mountain structures terminate along a line that trends approximately N 40°E (present coordinates), a common orientation for Mesoproterozoic extensional structures throughout southern to central North America.Continuing Tien Shan intraplate deformation (Central Asia) has created an analogous array of uplifts and basins in response to the collision of India with Eurasia, beginning in late Miocene time when full coupling of the colliding plates had occurred. As in the Laurentia–Gondwana case, structures of similar magnitude and spacing to those in Eurasia have developed in the Indian plate. Within the present orogen two ancient suture zones have been reactivated—the early Paleozoic Terskey zone and the late Paleozoic Turkestan suture between the Siberian and East Gondwanan cratons. Inverted Proterozoic to early Paleozoic rift structures and passive-margin deposits are exposed north of the Terskey zone. In the Alay and Tarim complexes, Vendian to mid-Carboniferous passive-margin strata and the subjacent Proterozoic crystalline basement have been uplifted. Data on Tien Shan uplifts, basins, structural arrays, and deformation rates guide paleotectonic interpretations of ancient intraplate mountain belts. Similarly, exhumed deep crustal shear zones in the Ancestral Rockies offer insight into partitioning and reorientation of strain during contemporary intraplate deformation.     

Diagenesis of oxyanions (V, U, Re, and Mo) in pore waters and sediments from a continental margin

This research tests the hypothesis that trace metals respond to the extent of reducing conditions in a predictable way. We describe pore water and sediment measurements of iron (Fe), manganese (Mn), vanadium (V), uranium (U), rhenium (Re), and molybdenum (Mo) along a transect off Washington State (USA). Sediments become less reducing away from the continent, and the stations have a range of oxygen penetration depths (depth to unmeasurable O₂ concentration) varying from a few millimeters to five centimeters. When oxygen penetrates ∼1 cm or less, Fe is reduced in the pore waters but reoxidized near the sediment-water interface, preventing a flux of Fe²⁺ to overlying waters, whereas Mn oxides are reduced and Mn²⁺ diffuses to overlying waters. Both Re and U authigenically accumulate in sediments. Only at the most reducing location, where the oxygen penetrates 0.3 cm below the sediment-water interface, does the surface 30 cm of sediments become reducing enough to authigenically accumulate Mo.Stations in close proximity to the Juan de Fuca Ridge crest are enriched in Mn and Fe from hydrothermal plume processes. Both V and Mo clearly associate with Mn cycling, whereas U may be associating with either Mn oxides and/or Fe oxyhydroxides. Rhenium is uncomplicated by adsorption to Mn oxides and/or Fe oxyhydroxides, and Re accumulation in sediments appears to be due solely to the extent of reducing conditions. Therefore, authigenic sediment Re enrichment appears to be the best indicator for intermediate reducing conditions, where oxygen penetrates less than ∼1 cm below the sediment-water interface, when coupled with negligible authigenic Mo enrichment.     

Ra and Rn isotopes as natural tracers of submarine groundwater discharge in the patagonian coastal zone (Argentina): an initial assessment

Submarine groundwater discharge (SGD) is herein recognized as a significant pathway of material transport from land to the coastal SW Atlantic Ocean and thus, it can be a relevant factor affecting the marine biogeochemical cycles in the region. This paper focuses on the initial measurements of ²²⁶Ra, ²²⁸Ra and ²²²Rn made in Patagonia’s coastal zone of Chubut and Santa Cruz provinces (42°S–48°S, Argentina). ²²⁶Ra activity ranged from 2.9 to 73.5 dpm 100 L^?1, and ²²⁸Ra activity ranged from 11.9 to 311.0 dpm 100 L^?1 in groundwater wells. The radium activities found in Patagonia’s marine coastal regions and adjacent shelf indicate significant enrichment throughout the coastal waters. Groundwater samples presented the largest ²²²Rn activity and ranged from 2.66 to 1083 dpm L^?1. Conversely, in the coastal marine environment, the ²²²Rn activity ranged from 1.03 to 6.23 dpm L^?1. The Patagonian coastal aquifer showed a larger enrichment in ²²⁸Ra than in ²²⁶Ra, which is a typical feature for sites where SGD is dominant, probably playing a significant role in the biogeochemistry of these coastal waters.     

Carbonatation processes at the El Berrocal natural analogue granitic system (Spain): inferences from mineralogical and stable isotope studies

The El Berrocal granite/U-bearing quartz vein system has been studied as a natural analogue of a high-level radioactive waste repository. The main objective is to understand the geochemical behaviour of natural radionuclides occurring under natural conditions. In this framework, the carbonatation processes have been studied from a mineralogical and isotopic ( and ) point of view, since carbonate anions are powerful complexing agents for U(VI) under both low-temperature hydrothermal and environmental conditions. The carbonatation processes in the system are identified by the presence of secondary ankerite, with minor calcite, scattered in the hydrothermally altered granite, and Mn calcite in fracture filling materials. The isotopic signatures of these carbonates lead us to conclude that ankerite and calcite from the former were formed at the end of the same hydrothermal process that altered the granite, at a temperature range of between 72° and 61°C for ankerite, and between 52° and 35°C for calcite. The effect of edaphic CO₂ on both carbonates, greater on calcite than on ankerite, is demonstrated. Calcites from fracture fillings are, at least, binary mixtures, in different proportions, of hydrothermal calcite, formed between 25° and <100°C, and supergenic calcite, formed at ≤25°C. According to their signatures, the effect of edaphic CO₂ in both calcites is also evident. It is assumed that: (i) hydrothermal calcite from fracture fillings and ankerite from the hydrothermally altered granite are the result of the same hydrothermal process, their chemical differences being due to the intensity of the water/rock interaction which was stronger in the altered granite than in the fractures; and (ii) all of these carbonatation processes are responsible for ancient and recent migration/retention of uranium observed in the hydrothermally altered granite and fracture fillings.     

Yellow fluorescence from baghdadite and synthetic Ca3(Zr,Ti)Si2O9

Baghdadite from Fuka, Okayama Prefecture, Japan shows a bright yellow fluorescence under UV (Hg 253.7 nm) excitation. The photoluminescence (PL) spectrum at 300 K consists of one large band near 580 nm and two small UV bands at 318 and 397 nm. The optical excitation spectrum of the bright yellow fluorescence consists of two bands near 220 and 250 nm. The temperature dependence of the PL intensity exhibits linear thermal quenching. To reveal the origin of the bright yellow fluorescence from baghdadite, powder Ca₃(Zr,Ti)Si₂O₉ crystals are synthesized. Synthetic Ca₃(Zr,Ti)Si₂O₉ shows luminescence spectra similar to those of baghdadite, and the intensity of the yellow fluorescence is markedly increased by titanium addition. The origin of the bright yellow fluorescence from baghdadite is ascribed to the existence of titanium.     

Uncoupled U/Pb and REE response in zircon during the transformation of eclogite to mafic and intermediate granulite (Blanský les,Bohemian Massif)

An eclogite–mafic granulite occurs as a rare boudin within a felsic kyanite–K‐feldspar granulite in a low‐strain zone. Its boundary is marked by significant metasomatism–diffusional gain of potassium at the centimetre‐scale, and probable infiltration of felsic melt on a larger scale. This converted the eclogite–mafic granulite into an intermediate‐composition, ternary‐feldspar‐bearing granulite. Based on inclusions in garnet, the peak P–T conditions of the original eclogite are 18 kbar at 850–950 °C, with later matrix re‐equilibration at 12 kbar and 950 °C. Four samples from the transition of the eclogite–mafic granulite through to the intermediate granulite were studied. In the eclogite, REE patterns in the garnet core show no Eu anomaly, compatible with crystallization in the absence of plagioclase and consistent with eclogite facies conditions. Towards the rim of garnet, LREE decrease, and a weak negative Eu anomaly appears, reflecting passage into HP granulite facies conditions with plagioclase present. The rims of garnet next to ternary feldspar in the intermediate granulite show the lowest LREE and deepest Eu anomalies. Zircon from the four samples was analysed by LASS (laser ablation–split‐stream inductively coupled plasma–mass spectrometry). It shows U–Pb ages from 404 ± 4.0 to 331 ± 3.3 Ma, with a peak at 340 ± 4.0 Ma corresponding to the likely exhumation of the rocks to 12 kbar. Older ages from zircon with steep HREE patterns indicate the minimum age of the protolith, and ages <360 ± 4.0 Ma are interpreted to correspond to the eclogite facies metamorphism. Only some zircon grains ≤350 ± 4.0 Ma have flat HREE patterns, suggesting that these are primarily modified protolith grains, rather than new zircon crystallized in the eclogite‐ or granulite facies. The metasomatic processes that converted the eclogite–mafic granulite to an intermediate granulite may have facilitated zircon modification as zircon in the intermediate granulite has flat HREE and ages of 340 ± 4.0 Ma. The difference between the oldest and youngest ages with flat REE patterns indicates a 16 ± 5.6 Ma period of zircon modification in the presence of garnet.     

Mineralogy and geochemistry of laterites from the Morro dos Seis Lagos Nb (Ti,REE) deposit (Amazonas,Brazil)

The Morro dos Seis Lagos niobium deposit (2897.9 Mt at 2.81 wt% Nb₂O₅) is associated with laterites formed by the weathering of siderite carbonatite. This iron-rich lateritic profile (>100 m in thickness) is divided into six textural and compositional types, which from the top to the base of the sequence is: (1) pisolitic laterite, (2) fragmented laterite, (3) mottled laterite, (4) purple laterite, (5) manganiferous laterite, and (6) brown laterite. All the laterites are composed mainly of goethite (predominant in the lower and upper varieties) and hematite (predominant in the intermediate types, formed from goethite dehydroxylation). The upper laterites were reworked, resulting in goethite formation. In the manganiferous laterite (10 m thick), the manganese oxides (mainly hollandite, with associated cerianite) occur as veins or irregular masses, formed in a late event during the development of the lateritic profile, precipitated from a solution with higher oxidation potential than that for Fe oxides, closer to the water table. Siderite is the source for the Mn. The main Nb ore mineral is Nb-rich rutile (with 11.26–22.23 wt% Nb₂O₅), which occurs in all of the laterites and formed at expense of a former secondary pyrochlore, together with Ce-pyrochlore (last pyrochore before final breakdown), Nb-rich goethite and minor cerianite. The paragenesis results of lateritization have been extremely intense. Minor Nb-rich brookite formed from Nb-rich rutile occurs as broken spherules with an “oolitic” (or Liesegang ring structure). Nb-rich rutile and Nb-rich brookite incorporate Nb following the [Fe³⁺ + (Nb, Ta) for 2Ti] substitution and both contain up to 2 wt% WO₃. The laterites have an average Nb₂O₅ content of 2.91 wt% and average TiO₂ 5.00 wt% in the upper parts of the sequence. Average CeO₂ concentration increases with increasing depth, from 0.12 wt% in the pisolitic type to 3.50 wt% in the brown laterite. HREE concentration is very low.     

Stable isotopes (2H, 18O and 13C) in groundwaters from the northwestern portion of the Guarani Aquifer System (Brazil)

The groundwater flow pattern of the western part of the Guarani Aquifer System (GAS), Brazil, is characterized by three regional recharge areas in the north, and a potentiometric divide in the south, which trends north–south approximately. Groundwater flow is radial from these regional recharge areas toward the center of Paraná Sedimentary Basin and toward the western outcrop areas at the border of the Pantanal Matogrossense, because of the potentiometric divide. The isotopic composition of GAS groundwater leads to understanding the paleoclimatic conditions in the regional recharge areas. The δ¹⁸O and δ²H isotopic ratios of GAS groundwaters vary, respectively, from –9.1 to –4.8‰ V-SMOW and –58.4 to –21.7‰ V-SMOW. In the recharge zones, enriched δ¹⁸O values are observed, while in the confined zone lighter δ¹⁸O values are observed. These suggest that climatic conditions were 10°C cooler than the present during the recharge of these waters. The δ¹³C ratios in groundwater of GAS, in the study area, vary from –19.5 to –6.5‰ VPDB, increasing along the regional flow lines toward the confined zone. This variation is related to dissolution of carbonate cement in the sandstones.