[Show abstract][Hide abstract] ABSTRACT: The Paleoproterozoic Era witnessed crucial steps in the evolution of Earth's surface environments following the first appreciable rise of free atmospheric oxygen concentrations ∼2.3 to 2.1 Ga ago, and concomitant shallow ocean oxygenation. While most sedimentary successions deposited during this time interval have experienced thermal overprinting from burial diagenesis and metamorphism, the ca. 2.1 Ga black shales of the Francevillian B Formation (FB2) cropping out in southeastern Gabon have not. The Francevillian Formation contains centimeter-sized structures interpreted as organized and spatially discrete populations of colonial organisms living in an oxygenated marine ecosystem. Here, new material from the FB2 black shales is presented and analyzed to further explore its biogenicity and taphonomy. Our extended record comprises variably sized, shaped, and structured pyritized macrofossils of lobate, elongated, and rod-shaped morphologies as well as abundant non-pyritized disk-shaped macrofossils and organic-walled acritarchs. Combined microtomography, geochemistry, and sedimentary analysis suggest a biota fossilized during early diagenesis. The emergence of this biota follows a rise in atmospheric oxygen, which is consistent with the idea that surface oxygenation allowed the evolution and ecological expansion of complex megascopic life.
[Show abstract][Hide abstract] ABSTRACT: The Archean granitoids in the Kiéné area, Gabon, are overlained by the Paleoproterozoic sediments of the Franceville basin (2.1 Ga). The basin is known for its high-grade uranium deposits among which some have been forming natural nuclear fission reactors. Most of the studies were dedicated to the FA-FB Paleoproterozoic sediments hosting these uranium deposits. Little is known on the Archean basement itself and specifically on the hydrous alteration events it experienced before and after the sediment deposition. The present work is focused on their petrographical, mineralogical and geochemical characterization. Dating the successive alteration events has been attempted on altered monazite crystals.
Rocks in different alteration states have been sampled from eight drill cores crosscutting the Archean – Paleoproterozoic unconformity. The Archean granitoids observed in the deepest levels exhibit typical petrographical features of a propylitic alteration while they are intensely illitized up to the unconformity. The propylitic alteration is mainly pervasive but the original texture of the granitoïds is conserved in spite of the formation of new minerals: Mg-chlorite, allanite and epidote forming a typical paragenesis. The illitic alteration is much more invasive near the unconformity. The illitization process leads to the replacement of feldspars and the corrosion of quartz crysals by an illitic matrix while the ferromagnesian minerals are pseudomorphosed by a Fe-chlorite + phengite + hematite assemblage. The final fluid-rock interaction step is marked by fissural deposits of calcite and anhydrite. The δ13C isotopic data show that the fissural carbonates precipitated from diagenetic fluids enriched carbon products deriving from the maturation of organic matter. The U–Pb isotopic analyzes performed on monazite crystals have dated three distinct events: 3.0–2.9 Ga (magmatic), 2.6 Ga (propylitic alteration) and 1.9 Ga (diagenetic illitization). The calculation of geochemical mass balances suggests that the water–rock ratio during the propylitic alteration event was weak. On the contrary, it was much higher during the overprinted illitization which is characterized by an intense leaching of Na, Ca, Mg, Sr, REE and an enrichment in K, Rb,Cs.
Neither the petrographic features nor the geochemical data militate for an Archean weathering event (paleosol). In the present case, diagenetic fluids have percolated from the unconformity into the basement where they overprinted the illitization processes upon the previously propylitized rocks. These fluids were probably oxidant as they are also responsible of the U mobilization which led to the formation of the ore deposits close to the FA-FB interface.
[Show abstract][Hide abstract] ABSTRACT: The Palaeoproterozoic Franceville basin, Gabon, is mainly known for its high-grade uranium deposits, which are the only ones known to act as natural nuclear fission reactors. Previous work in the Kiéné region investigated the nature of the fluids responsible for these natural nuclear reactors. The present work focuses on the top of the Archaean granitic basement, specifically, to identify and date the successive alteration events that affected this basement just below the unconformity separating it from the Palaeoproterozoic basin. Core from four drill holes crosscutting the basin–basement unconformity have been studied. Dating is based on U–Pb isotopic analyses performed on monazite. The origin of fluids is discussed from the study of fluid inclusion planes (FIP) in quartz from basement granitoids. From the deepest part of the drill holes to the unconformable boundary with the basin, propylitic alteration assemblages are progressively replaced by illite and locally by a phengite + Fe chlorite ± Fe oxide assemblage. Illitic alteration is particularly strong along the sediment–granitoid contact and is associated with quartz dissolution. It was followed by calcite and anhydrite precipitation as fracture fillings. U–Pb isotopic dating outlines three successive events: a 3.0–2.9-Ga primary magmatic event, a 2.6-Ga propylitic alteration and a late 1.9-Ga diagenetic event. Fluid inclusion microthermometry suggests the circulation of three types of fluids: (1) a Na–Ca-rich diagenetic brine, (2) a moderately saline (diagenetic + meteoric) fluid, and (3) a low-salinity fluid of probable meteoric origin. These fluids are similar to those previously identified within the overlying sedimentary rocks of the Franceville basin. Overall, the data collected in this study show that the Proterozoic–Archaean unconformity has operated as a major flow corridor for fluids circulation, around 1.9 Ga.
[Show abstract][Hide abstract] ABSTRACT: Clay minerals are exceptionally well preserved in marine black shale of the ca. 2.1 Ga Francevillian Group in southeastern Gabon. The FB Formation of the Francevillian Group is characterized by smectite-rich clay minerals including randomly ordered (R0-type) and ordered (R1-type) mixed layer illite/smectite (I/S). The preservation of R0-type clay minerals suggests unexpectedly slow mineral transformation and a moderate degree of diagenesis, which is unique, considering the Paleoproterozoic age of the sedimentary rocks. R0- and R1-type, smectite-rich particles occur in stratigraphic intervals with high organic carbon content and are associated with carbonaceous filamentous structures, suggesting formation of clay–organic matter complexes. Our data suggests that clay minerals may have enhanced organic matter preservation, providing the oldest example where a link between clay minerals and organic matter sequestration can be established. Our findings are consistent with the hypothesis that clay minerals enhanced organic carbon burial and aided in atmospheric oxygen accumulation through time.
Chemical Geology 12/2013; 362:181-192. · 3.15 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The oxygen content of Earth's atmosphere has varied greatly through time, progressing from exceptionally low levels before about 2.3 billion years ago, to much higher levels afterward. In the absence of better information, we usually view the progress in Earth's oxygenation as a series of steps followed by periods of relative stasis. In contrast to this view, and as reported here, a dynamic evolution of Earth's oxygenation is recorded in ancient sediments from the Republic of Gabon from between about 2,150 and 2,080 million years ago. The oldest sediments in this sequence were deposited in well-oxygenated deep waters whereas the youngest were deposited in euxinic waters, which were globally extensive. These fluctuations in oxygenation were likely driven by the comings and goings of the Lomagundi carbon isotope excursion, the longest-lived positive δ(13)C excursion in Earth history, generating a huge oxygen source to the atmosphere. As the Lomagundi event waned, the oxygen source became a net oxygen sink as Lomagundi organic matter became oxidized, driving oxygen to low levels; this state may have persisted for 200 million years.
Proceedings of the National Academy of Sciences 09/2013; · 9.74 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Explanation of the so-called Oklo phenomenon can only be found by associating neutron physics and geological observations. The framework of Reactor Zone #9 (RZ9) from the Oklo uranium deposit in Gabon is discussed. A realistic model of RZ9 is proposed and studied with present-day numerical tools. Anchor points for this model are set by means of a selection of relevant parameters acting on geological conditions and neutron-transport physics, including ore homogeneity, initial reactor thickness, reflector effect and initial neutron poison content. Based on Monte Carlo simulations, the present modeling enables discussion of start-up conditions of the RZ9 reactor at optimal overlap of two opposing long-term processes: geochemical enrichment of the uranium content of the ore and its progressive impoverishment in 235U. On the basis of the present work, the inception and operation of Oklo natural reactors can be discussed from the largest to smallest initial core size, whereas before, only the largest ones had found some explanation.
[Show abstract][Hide abstract] ABSTRACT: Highly depleted C isotope composition of organic matters from the Onega (Fennoscandian shield) and Francevillian (Gabon) basins are differently interpreted. Kump et al. (2011) suggested the occurrence of a massive and global oxidation event during the period of 1980–2090 Ma, which follows the Great Oxidation Event (2450–2320 Ma) (Bekker et al., 2004). Inversely, Gauthier-Lafaye and Weber (2003) invoke the possible action of methanotrophic microorganisms to explain the δ13C values as low as –46‰ measured in the Franceville basin. Here we present the isotope data available in the Franceville basin in order to discuss these two interpretations. The lack of any δ13C correlation between organic matter and carbonate in the Franceville basin does not allow the consideration of a massive and global oxidation event.RésuméLes mesures de la composition isotopique du carbone des matières organiques des bassins d’Onéga (Bouclier fennoscandinave) et de Franceville (Gabon) ont révélé des valeurs très basses qui ont été différemment interprétées. Kump et al. (2011) suggèrent l’existence d’une oxydation globale et massive pendant la période 1980 à 2090 Ma, qui suit le Grand Évènement oxydant (GOE) (2450–2320 Ma) (Bekker et al., 2004). Inversement, Gauthier-Lafaye et Weber (2003) invoquent l’action possible de microorganismes méthanotrophes pour expliquer des valeurs de δ13C aussi basses que –46 ‰, mesurées dans le bassin de Franceville. Nous présentons ici les mesures isotopiques effectuées dans le bassin de Franceville pour discuter ces deux hypothèses. L’absence de corrélation entre les valeurs de δ13C des matières organiques et des carbonates ne permet pas d’envisager une période d’oxydation massive et globale dans le bassin de Franceville.
[Show abstract][Hide abstract] ABSTRACT: The activity concentrations of radionuclides within the uranium and thorium series were determined in wheat and lettuce at five sites in France, and in their respective potential sources: crop soils of wheat and crop soils and irrigation waters of lettuce. These data were used to calculate concentration ratios and to enrich the database supported by the technical report series N°472 of the IAEA (2010). For wheat and lettuce, the activity concentrations were in the same range for all radionuclides studied, except for 210Pb, which had higher activity concentrations in wheat, ranging between 1.3 and 11 Bq kg−1 (fresh weight) as compared to 0.4 and 0.7 Bq kg−1 (fresh weight) for lettuce. For wheat, the range of activity concentrations (mBq kg−1; fresh weight) decreased as 210Pb > 226Ra (56–1511) ≈ 228Ra (86–769) > 228Th (19–176) ≈ 238U (11–169) ≈ 234U (12–150) ≈ 230Th (9.08–197.18) ≈ 232Th (8.61–121.45) > 235U (0.53–7.9). For lettuce, it decreased as 228Ra (<320–1221) > 210Pb (409–746) > 226Ra (30–599) ≈ 228Th (<29–347) > 238U (8–120) ≈ 234U (8–121) ≈ 230Th (5.21–134.63) ≈ 232Th (5.25–156.99) > 235U (0.35–5.63). The species differences may reflect different plant physiologies. Through the study of activity ratios of wheat and lettuce in relation with those of the various radionuclide sources it has been possible to highlight the contribution of the main sources of natural radionuclides. Indeed, irrigation water when the uranium concentration is enhanced (>30 mBq L−1) contributed significantly to the activity concentration of uranium in lettuces. Concerning the high activity concentrations of 210Pb, it could be explained by atmospheric particle deposition. The effect of soil particles resuspension and their adhesion to the plant surface seemed to be important in some cases. The soil-to-plant transfer factors were calculated for lettuce and wheat. The values were lower in wheat than in lettuce except for 210Pb which had similar values in the two species (0.11–0.13 respectively). For both species, 210Pb followed by 228Ra (0.015–0.10) and 226Ra (0.010–0.051) displayed the highest transfer factor, whereas 238U had intermediate values (0.0015–0.030) and 232Th exhibited the lowest (0.0014–0.013).
Journal of Environmental Monitoring 10/2012; 14(11):2902-2912. · 2.09 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Activity concentrations of the uranium and thorium series radionuclides were determined in chicken meat and eggs as well as in soil, water and other dietary intakes of poultry at five sites of the French territory. These data allow the calculation of transfer coefficients which enrich the database given by the technical report series no. 472 of the IAEA. In egg contents, the highest activity concentrations (in mBq kg(-1) fresh weight) are for (226)Ra, ranging between 136 and 190 and are much lower for uranium (between 0.51 and 1.30 for (238)U). In chicken meat, (238)U activity concentration is higher than in egg contents and ranges between 1.7 and 9.7. Concerning (232)Th, its activity concentration is lower than uranium and ranges between 0.5 and 4.9. Daily ingested activity concentration by the animals was assessed taking into account the activity concentrations measured in the grains, in the soil and in the drinking water. The activity concentration in grains and the daily intakes allow the calculation of concentration ratios and transfer coefficients for chicken meat and egg contents. In chicken meat the transfer coefficients (d kg(-1)) range between 0.0018 and 0.0073 for (238)U and between 0.0008 and 0.0028 for (232)Th. In egg contents they range from 0.00018 to 0.0018 for (238)U and are much higher for radium isotopes (0.10-0.23 for (226)Ra and 0.07-0.11 for (228)Ra).
Journal of Environmental Monitoring 06/2012; 14(8):2170-80. · 2.09 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The occurrence of more than 15 natural nuclear Reactor Zones (RZ) in a geological environment remains a mystery even 40 years after their discovery. The present work gives for the first time an explanation of the chemical and physical processes that caused the start-up of the fission reactions with two opposite processes, uranium enrichments and progressive impoverishment in 235U. Based on Monte-Carlo neutronics simulations, a solution space was defined taking into account realistic combinations of relevant parameters acting on geological conditions and neutron transport physics. This study explains criticality occurrence, operation, expansion and end of life conditions of Oklo natural nuclear reactors, from the smallest to the biggest ones.
[Show abstract][Hide abstract] ABSTRACT: The evidence for macroscopic life during the Palaeoproterozoic era (2.5-1.6 Gyr ago) is controversial. Except for the nearly 2-Gyr-old coil-shaped fossil Grypania spiralis, which may have been eukaryotic, evidence for morphological and taxonomic biodiversification of macroorganisms only occurs towards the beginning of the Mesoproterozoic era (1.6-1.0 Gyr). Here we report the discovery of centimetre-sized structures from the 2.1-Gyr-old black shales of the Palaeoproterozoic Francevillian B Formation in Gabon, which we interpret as highly organized and spatially discrete populations of colonial organisms. The structures are up to 12 cm in size and have characteristic shapes, with a simple but distinct ground pattern of flexible sheets and, usually, a permeating radial fabric. Geochemical analyses suggest that the sediments were deposited under an oxygenated water column. Carbon and sulphur isotopic data indicate that the structures were distinct biogenic objects, fossilized by pyritization early in the formation of the rock. The growth patterns deduced from the fossil morphologies suggest that the organisms showed cell-to-cell signalling and coordinated responses, as is commonly associated with multicellular organization. The Gabon fossils, occurring after the 2.45-2.32-Gyr increase in atmospheric oxygen concentration, may be seen as ancient representatives of multicellular life, which expanded so rapidly 1.5 Gyr later, in the Cambrian explosion.
[Show abstract][Hide abstract] ABSTRACT: 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.
Geochimica et Cosmochimica Acta 01/2010; 74(16):4709-4722. · 3.88 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: We have carried out a comparative Rb–Sr, Sm–Nd and Lu–Hf isotopic study of a progressively deformed hercynian leucogranite from the French Massif Central, belonging to the La Marche ductile shear zone, in order to investigate the respective perturbation of these geochronometers with fluid induced deformation. The one-meter wide outcrop presents a strongly deformed and mylonitized zone at the center, and an asymmetric deformation pattern with a higher deformation gradient on the northern side of the zone. Ten samples have been carefully collected every 10 cm North and South away from the strongest deformed mylonitic zone. They have been analyzed for a complete major, trace element data set, oxygen isotopes, Rb–Sr, Sm–Nd and Lu–Hf isotopic systematics.We show that most of major and trace elements except SiO2, alkaline elements (K2O, Rb), and some metal transition elements (Cu), are progressively depleted with increasing deformation. This depletion includes REE + Y, but also HFS elements (Ti, Hf, Zr, Nb) which are commonly considered as immobile elements during upper level processes. Variations in elemental ratios with deformation, e.g. decrease in LREE/MREE- HREE, Nd/Hf, Th/Sr, increase in Rb/Sr, U/Th and constant Sr/Nd, lead to propose the following order of element mobility: U ≫ Th > Sr = Nd ≫ Hf + HREE. We conclude in agreement with previous tectonic and metallogenic studies that trace element patterns across the shear zone result from circulation of oxidizing F-rich hydrothermal fluids associated with deformation. A temperature of the fluid of 470–480 °C can be deduced from the δ18O equilibrium between quartz–muscovite pairs.Elemental fractionation induces perturbation of the Rb–Sr geochronometer. The well-defined 87Rb/86Sr–87Sr/86Sr correlation gives an apparent age of 294 ± 19 Ma, slightly younger than the 323 ± 4 Ma age of leucogranites in this area. This apparent age is interpreted as dating event of intense deformation and fluid circulation associated with mass transfer, and exhumation of the ductile crust shortly after the leucogranite emplacement. Sm–Nd and Lu–Hf isochron-type diagrams do not define any correlation, because of the low fractionated Sm/Nd and Lu/Hf ratios. Isotopic data demonstrate that only the Lu–Hf geochronometer system is not affected by fluid circulation and gives reliable TDM age (1.29 ± 0.03 Ga) and εHf signatures. By contrast, the Sm–Nd geochronometer system gives erroneous old TDM ages of 2.84–4 Ga. There is no positive εNd–εHf correlation, because of decreasing εNd values with deformation at constant εHf values. However, εNd–εHf values remain in the broad εNd–εHf terrestrial array, which strongly indicates that fluid-induced fractionation can contribute to the width of the terrestrial array. The strong εHf negative values of the leucogranite are similar to metasedimentary granulitic xenoliths from the French Massif Central and confirm the generation of the leucogranite by several episodes of reworking of the lower crust.
Geochimica et Cosmochimica Acta 01/2009; 73(10):2961-2977. · 3.88 Impact Factor