sample scale carbon isotopic variability and diverse biomass in the paleoproterozoic zaonega formation russia abstract the stratigraphic record of organic matter in the c 1 97 ga zaonega formation zf onega basin northwestern russia exhibits a distinct negative 13c excursion 13corg from 25 to 40 vpdb which was previously interpreted either to reflect a disturbance in the global carbon cycle after the great oxidation event or to have been caused by an increase in basinal methanotrophic activity in order to assess the nature of primary biomass and the effects of post depositional alteration we here report the sample scale carbon isotopic characteristics of organic matter in two drill cores from the zf covering 500 m of stratigraphy by using secondary ion mass spectrometry sims the results confirm that the organic matter has to a large extent preserved the primary isotopic signatures whereas secondary effects are limited

extreme 13ccarb enrichment in ca 2 0 ga magnesite stromatolite dolomite red beds association in a global context a case for the world wide signal enhanced by a local environment abstract the palaeoproterozoic positive excursion of 13 c carb is now considered as three positive shifts of 13 c carb separated by returns to 0 which all occurred between 2 40 and 2 06 ma this isotopic event is unique in terms of both duration 300 ma and 13 c enrichment up to 18 the mechanism responsible for one of the most significant carbon isotopic shifts in earth history remains highly debatable to date 13 c of 10 to 15 cannot be balanced by organic carbon burial forg as there is no geological evidence for an enhanced corg accumulation prior to or synchronous with the excursion instead termination of these excursions is followed by formation of a vast reservoir of 13 c depleted organic material 45 at shunga and by one of the earliest known oil generation episodes at 2 0 ga none of the three positive excursions of 13 c carb is followed by a negative isotopic shift significantly below 0 as has always been observed in younger isotopic events reflecting an overturn of a major marine carbon reservoirs this may indicate that forg was constant implying that the mechanism involved in the production of corg was different onset of intensive methane cycling resulting in c change is another possibility the majority of sampled 13 c carb rich localities represents shallow water stromatolitic dolostones red beds and evaporites formed in restricted intracratonic basins and may not reflect global 13 c carb values closely spaced drill core samples n 73 of stromatolitic dolostones from the 1980 27 ma tulomozerskaya formation in the onega palaeobasin russian karelia have been analysed for 13 c carb and 18 o carb in order to demonstrate that different processes were involved in the formation of 13 c carb rich carbonates the 800 m thick magnesite stromatolite dolomite red beds succession formed in a complex combination of environments on the karelian craton peritidal shallow marine low energy protected bights barred basins evaporative ephemeral ponds coastal sabkhas and playa lakes the carbonate rocks exhibit extreme 13 c enrichment with 13 c values ranging from 5 7 to 17 2 vs v pdb mean 9 9 2 3 and 18 o from 18 6 to 26 0 vs v smow mean 22 0 1 6 the tulomozerskaya isotopic excursion is characteristic of the global 2 4 2 06 ga positive shifts of carbonate 13 c 12 c although it reveals the greatest enrichment in 13 c known from this interval an external basin s is considered to have provided an enhanced corg burial and global seawater enrichment in 13 c the global background value for the isotopic shift at tulomozero time ca 2 0 ga is roughly estimated at around 5 an explosion of stromatolite forming microbial communities in shallow water basins evaporative and partly restricted environments high bioproductivity enhanced uptake of 12 c and pene contemporaneous recycling of organic material in cyanobacterial mats with the production and consequent loss of co2 and ch4 are believed to be additional local factors which may have enhanced 13 c from 5 up to 17 such factors should be taken into account when interpreting carbon isotopic data and attempting to discriminate between the local enrichment in 13 c and globally enhanced 13 c values we propose that many previously reported 13 c values from other localities where environmental interpretations are not available or have not been taken into account may not represent the global 13 c values

multiple crust reworking in the french armorican variscan belt implication for the genesis of uranium fertile leucogranites muscovite peraluminous granites mpgs form by partial melting of the continental crust and can be related to metalliferous deposits such as tin tungsten and uranium u metal enrichment in mpgs commonly results from fractional crystallization but the metal contents of the source play a major role for their fertility between ca 320 and 300 ma late carboniferous the french armorican variscan belt was intruded by numerous u fertile mpgs that contain inherited zircon grains with a wide range of ages from archean to carboniferous u pb and hf isotopic data of zircon grains from brioverian to carboniferous sediments cambrian to early carboniferous granitoids and late carboniferous mpgs indicate that the crust of the armorican massif is made up by detritus mainly derived from the west african craton 3500 1600 ma tdm 3 8 2 3 ga grenvillian belt 1200 900 ma tdm 2 7 1 2 ga and avalonian cadomian belt 800 550 ma tdm 2 5 0 8 ga and that the crust was affected by magmatic events at 510 470 ma tdm 1 6 0 6 ga 410 330 ma tdm 1 6 1 ga and 320 300 ma furthermore they reveal that the late carboniferous mpgs were mainly formed by partial melting of brioverian sediments with cambro ordovician and devonian carboniferous granitoids which are all genetically linked with each other and characterized by th u 4 the new data suggest that the u fertile mpgs result from multiple reworking of u rich brioverian sediments deposited ca 550 ma ago on the northern margin of gondwana and partially molten during several paleozoic events causing a successive increase in u content in the middle upper crust

two step deoxygenation at the end of the paleoproterozoic lomagundi event abstract the ca 2 1 ga francevillian group of gabon was deposited in the aftermath of the great oxidation event goe and records the lomagundi event le which is the most pronounced and long lived carbon isotope excursion in the geologic record moreover the sedimentary succession contains putative evidence for the earliest appearance of macro eukaryotes an emerging paradigm is that the end of the le was accompanied by a deoxygenation event that preceded the apparent stability of environmental and redox conditions as well as the carbon cycle characteristic of the mesoproterozoic however the processes that led to deoxygenation some 300 to 200 ma after the beginning of the goe are not well understood here we present a multi proxy stable isotope 34 s 33 s 36 s 98 mo 13 c org 13 c carb and 18 o carb study of the francevillian group we suggest that sedimentation of the lower part of the francevillian group took place during the le in oxygenated shallow waters with elevated sulfate concentrations two episodes of anoxic water shoaling during deposition of the upper francevillian group correspond with broader marine deoxygenation and a contraction of the seawater sulfate reservoir this shoaling of anoxic conditions may be linked to intense submarine hydrothermal and volcanic activity that led to sedimentary manganese deposits we propose that increased concentrations of aqueous hydrothermally sourced reductants drove oxygen consumption during the first deoxygenation event and established a sulfidic oxygen minimum zone at the margin of the shallow shelf carbonates with positive 13 c carb values characteristic of the le precipitated during this first stage of deoxygenation the second deoxygenation separated from the previous event by a period of well oxygenated conditions was marked by a stronger contraction of the seawater sulfate reservoir and coincided with the end of the le during this time widespread euxinic conditions were established in shallow above storm wave base marine environments the presence of a shallow water redoxcline points to a generally low oxygen atmosphere ocean system further the negative co variation between 34 s and 13 c values in sediments of the francevillian group and other sedimentary successions of similar age worldwide suggests that the inferred two step deoxygenation corresponding to the end of the le reflects global rather than local events that likely occurred between 2 1 and 2 05 ga ago

sm nd isotopic dating of proterozoic clay material an example from the francevillian sedimentary series gabon clay fractions of 0 4 m and 0 2 m and acid leachates of these clay fractions were separated from two different kerogen rich black shale samples from the francevillian sedimentary series in gabon they yielded identical sm nd isochron ages of2099 115 ma and2036 79 ma with initial nd values of 6 5 2 0 and 9 3 1 5 respectively these ages define multi episode illitization during early diagenesis as suggested by the differentsm nd ratios of the clay fractions the sm nd isotope data of the kerogen source rock up to 13 organic carbon plot between the two isochrons but close to the clay fractions suggesting that this organic matter reached nd isotopic equilibrium with respect to the clay minerals and the diagenetic fluids analyses of fracture filling bitumen showed that it had very elevated143nd 144nd and147sm 144nd ratios these values are higher than the most elevated values of the leachates but plot on the extension of the two isochrons this indicates that the bitumen reached nd isotopic equilibrium with the kerogen source rock from which it was expelled and the authigenic clay minerals secondary migration and chemical evolution of the bitumen appear to have caused the fractionation between sm and nd with an attendant increase in thesm nd ratio the results suggest that the sm nd isotope method has potential for both dating diagenetically related illitization using leachate residue pairs of small size clay fractions and reconstructing geochemical processes during diagenesis in oil producing sedimentary basins

multiple palaeoproterozoic carbon burial episodes and excursions organic rich rocks averaging 2 5 total organic carbon and positive carbonate carbon isotope excursions view the mathml source and locally much higher i e the lomagundi jatuli event are hallmark features of palaeoproterozoic successions and are assumed to archive a global event of unique environmental conditions following the c 2 3 ga great oxidation event here we combine new and published geochronology that shows that the main palaeoproterozoic carbon burial episodes cbes preserved in russia gabon and australia were temporally discrete depositional events between c 2 10 and 1 85 ga in northwest russia we can also show that timing of the termination of the lomagundi jatuli event may have differed by up to 50 ma between localities and that ni mineralisation occurred at c 1920 ma further cbes have traits in common with mesozoic oceanic anoxic events oaes both are exceptionally organic rich relative to encasing strata associated with contemporaneous igneous activity and marked by organic carbon isotope profiles that exhibit a stepped decrease followed by a stabilisation period and recovery although cbe strata are thicker and of greater duration than oaes 100 s of metres versus metres 106 years versus 105 years their shared characteristics hint at a commonality of cause s and feedbacks this suggests that cbes represent processes that can be either basin specific or global in nature and a combination of circumstances that are not unique to the palaeoproterozoic our findings urge circumspection and re consideration of models that assume cbes are a deep time singularity

simulation of a surface penetrating radar for mars exploration 1 in the near future several exploratory missions to mars are planned which will include orbital radar sounders capable of characterizing the planet s subsurface structure to depths of up to a few kilometers due to the limited amount of resources concerning the properties of the martian soils in particular those governing electromagnetic propagation and scattering the ability of a radar system to detect and distinguish between subsurface interfaces is difficult to predict up to this time most radar sounding simulations have been based on simplified models and do not accurately account for many of the factors that influence the response to aid in the system evaluation and data interpretation for these missions we developed a radar simulator to accurately model the response for various geological conditions the simulator uses a frequency domain algorithm and is capable of modeling the effects of dielectric layering volume debris frequency dispersion ohmic losses and interface roughness in this paper a geophysical model appropriate to the radar simulator is described and the simulation algorithms are presented in detail factors influencing wave propagation and scattering are identified including those that directly impact radar performance specifically pertaining to expected penetration depths and unambiguous detection of water or ice finally using a set of standard crustal models of different geological regions simulation results are generated and presented

alteration of monazite and zircon and lead migration as geochemical tracers of fluid paleocirculations around the oklo okelobondo and bangombe natural nuclear reaction zones franceville basin gabon abstract large scale light rare earth element lree uranium lead and phosphorus migration has been evidenced in the fa lower proterozoic sandstones of the franceville basin gabon hosting oklo natural nuclear reaction zones rz in relation with extensive accessory mineral alteration by highly saline diagenetic brines 28 7 wt nacl eq to 30 wt cacl2 eq at about 140 c and 1 kbar monazite is the most severely altered accessory mineral in the coarse grained sandstones of the basal fa formation detrital monazite crystals are altered to th oh silicate microcrystalline phase with very low concentrations of u and lree the th la ratio increase from non altered th la 0 27 to altered sandstones th la 1 14 shows that about 76 of the lree was leached this corresponds to the leaching of 2 01 109 metric tons at the scale of the fa formation in the franceville basin similarly the th u increase from monazite th u 18 6 to the th silicate phase th u 88 7 is interpreted as a result of an alteration by oxidizing brines with leaching of u together with lree and p it corresponds to the leaching of 9 06 106 metric tons of uranium this amount of uranium largely exceeds the known uranium reserves from the franceville basin in zircon crystals the cores are generally homogeneous weakly fractured and well preserved as attested by the archean ages 2867 24 and 2865 51 ma obtained by ionic microprobe analysis on zircon of the fa formation respectively from the marginal and central parts of the basin their composition corresponds to the pure end member zr hf sio4 poor in th and u th u 1 at the contrary their rims which present several growth zones with cracks fillings are enriched in ree p th and u with higher th u ratios 5 10 both altered monazite and altered zircon contain galena as numerous inclusions in the outer growth zones and as crack fillings for example in zircon the pb of galena crystals 3 23 wt largely exceeds the amount of pb maximum 0 1 wt that would have been produced in situ by radioactive decay in this mineral nearly all the lead were introduced into altered zones of accessories dissolution of accessory minerals occurred at 2000 ma producing a porous and distorted crystal structure which has allowed a later incorporation of pb galena inclusions in altered zircons located in the vicinity of reactor zones have radiogenic lead compositions altered zircon rims and galena inclusions in altered zircon located far from reactor zones have non radiogenic pb isotopic compositions confirming the external origin of lead pb isotopic evolution models indicate a crystallization age sometime after 1000 ma both for galena located close to and far from u mineralizations and reactor zones which may be synchronous with a regional extension event contemporaneous with intrusion of dolerite dyke swarms between 1000 and 750 ma at the scale of the franceville basin the present study also illustrates the different retention capacities of accessory mineral for elements representing analogs of the radiotoxic nuclides in the relatively extreme natural conditions created by the circulation of moderately hot and chloride rich fluids during the diagenesis of a sedimentary basin

depositional setting of the 2 1 ga francevillian macrobiota gabon rapid mud settling in a shallow basin swept by high density sand flows the depositional setting of the 2 1 ga fill to the franceville basin of gabon is important for understanding the habitat energy and availability of light and oxygen and taphonomy of recently discovered early macro organisms buried in black shales in unit fb the available data bearing on the stratigraphy and sedimentology of unit fb provide new insight into processes acting on the palaeo seafloor the shales are interpreted to have formed as fluid mud deposits interstratified with structureless sands the latter poubara sandstones were emplaced during a forced regression during the terminal infill of fault bounded sub basins following a stage characterised by a ferruginous to anoxic water column the structureless sandstones were deposited from high density gravity currents along with a locally strong bottom oscillation of the water column tuft structures preserved in cyanobacterial mats together with the position of the macro organisms at the top of the sandstone beds within associated black shales point to a water depth of less than 80 m the relative sea level fall that drove deposition of the poubara sandstones controlled the rise of a phototrophic ecosystem and also possibly favoured the supply of oxygen and nutrients via density flows this article is protected by copyright all rights reserved

isotopic evolution of the biogeochemical carbon cycle during the proterozoic eon abstract time related changes in the proterozoic sedimentary isotopic record of organic carbon and carbonates are consistent with the following 1 an increase in the oxidation state of the environment 2 a transition towards microbial populations dominated by producers and utilizers of o 2 and so 4 2 and 3 a relatively minor increase in organic 13 c during postdepositional thermal alteration 13 c increased 3 as h c declined from 0 8 to 0 1 the progressive oxidation of the environment was episodic for example between 2 2 and 1 9 ga crustal and atmospheric reservoirs of o 2 fe 3 and so 4 2 increased relatively rapidly and this increase was too large to be attributed solely to the declining rate of oxidant consumption by volcanic and hydrothermal fluxes of reduced species additional fundamental changes seem to be required in the tectonic style of organic sedimentation and preservation episodic changes in both the biogeochemical c cycle and atmospheric o 2 levels during the proterozoic eon likely influenced the evolution of eukarya

field and geochronological evidence for origin of the contendas mirante supracrustal belt sao francisco craton brazil as a paleoproterozoic foreland basin abstract the low grade contendas mirante meta volcano sedimentary belt cmb was previously interpreted as an archean greenstone belt with the uppermost formation deposited in the paleoproterozoic new zircon u pb la icp ms ages on sedimentary groups and granite sheets intrusive in the belt constrain the timing of basin development phyllites of the lower group and meta arenites of the upper group yielded similar young zircon populations at ca 2080 ma which are interpreted as the maximum deposition age for the entire sequence the unique exception is the 3273 3338 ma zircon bearing quartzite that occurs in spatial association with the 3300 ma rhyolite a granite sheet intrusive into metagraywacke of the lower group constrains the minimum deposition age of 2045 26 ma for the cmb altogether four main age clusters of detrital zircon grains were recognized namely 2075 2200 ma 2200 2440 ma 2500 2770 ma 3270 3380 ma these age intervals match the ages of igneous and metamorphic rocks in the different terranes that comprise the sao francisco craton maximum deposition age for both groups indicates that sedimentation occurred immediately prior the high grade metamorphism in the adjacent archean paleoproterozoic jequie block and itabuna salvador curaca orogen these observations along with coarsening upwards in the sediments indicate that the cmb represents a foreland basin developed along the eastern margin of the gaviao block during plate convergence paleoarchean basement rocks were reactivated and emplaced into the cmb during basin inversion and is timely correlated with the granitic intrusion recognition of older supracrustal fragments is ambiguous one main example is the 3273 3338 ma zircon bearing quartzite which correlates with the northern jacobina basin along the contendas mirante lineament e g bahia gold belt and may represent part of an archean intracontinental rift sequence

an example of lower proterozoic sediments the francevillian in gabon abstract new mineralogical and isotopic data have been obtained on diagenetic fine fractions of the francevillian sediments together with the rb sr age of a syenitic intrusive and already published isotopic ages determined by means of uranium ore and uranium fission products they allow us to present a more complete geological history of the francevillian the main steps are deposition of the fa formation before 2140 ma deposition of the fb fe formations between 2140 and 2050 ma siliceous diagenesis followed by nuclear reactions between 2050 and 1930 ma carbonate diagenesis at nearly 1870 ma end of cooling at 1700 ma and dolerite intrusion at ca 970 ma the francevillian sediments are to date the oldest true sediments known they are diagenetic lower proterozoic sediments

microfossiliferous cherty stromatolites in the 2000 ma franceville group gabon abstract cherty stromatolites reported here for the first time have been found in the palaeoproterozoic 2000 ma cover of the chaillu craton in gabon they occur in two different areas probably in the same formation fc which comprises widespread beds of black shales and silexites the buildups are 1 2 m thick biostromes comprising juxtaposed domes of pseudo columnar to columnar stromatolites the biostromes are transgressive over topographic highs marginal to the francevillian basins the environment was a protected shallow marine area with occasional inputs of small quantities of peloidal sediment deposited between the columns the high organic carbon content of francevillian formations fb fc and fd allows us to consider them as source rocks for the bitumen now found in the fa sandstones the stromatolites and their preserved microfossils support the hypothesis that microbial activity was at the origin of bitumen production

geochemistry of femn formations of the archaean sandur schist belt india mixing of clastic and chemical processes at a shallow shelf abstract the late archaean greenstone belts of karnataka are unique in having manganese formations with mineable ores an excellent example of these mn bearing greenstone belts is the sandur schist belt where fe mn formations are confined to the basin shelf clearly separated from the deeper water manganese free bif that accumulated at the basin margin and flanking the marine basin sedimentary textures and structures including stromatolites show that fe mn formations have been deposited on a shallow shelf within the photic zone and above wave base along with quartz fe mn minerals found in arenites argillites and carbonates include ripidolite mg chlorite sericite mn siderite kutnahorite dolomite ferroan dolomite psilomelane pyrolusite cryptomelane haematite and magnetite the manganese and iron contents of these rocks range up to 25 and 46 respectively al 2 o 3 tio 2 mgo cao mno 2 fe 2 o 3 t abundances and ratios show a wide variation ni cr co zr v sc rb sr u th ree lree hree la ce and eu anomalies and their binary relationships indicate that wherever the terrigenous component has increased the concentration of elements of felsic parentage such as zr and hf has gone up elevated concentrations of ni cr co and sc are contributed by chlorite and other components characteristic of basic volcanic debris the carbonates where clastic input is minimal are extremely depleted in ree and other trace elements it is proposed that feo mno and sio 2 probably were added to archaean ocean water at oceanic ridge vents the compositional data suggest that the fe mn formations of the sandur schist belt were generated by chemical and clastic sedimentary processes on a shallow shelf that led into a deeper basin open on one side in this environment chemical and clastic sediments and organic matter were mixed and buried during transgression chemical precipitation took place at the sediment water interface whereas at the time of regression these chemical sediments were buried by clastic sediments redox potential differences between the watermasses on the shallower and deeper shelf respectively fractionated fe and mn the fe mn formations were deposited within the photic zone and above wave base and in a setting where the water column was oxygenated but organic material accumulated by contrast bif was deposited below both wave base and photic zone in a relatively oxygen deficient setting where formation of stable mn oxides was not possible fe mn formation and bif provide an important constraint on greenstone tectonics a shorter distance between archaean oceanic ridge and shelf environments namely the smaller plates model appears to explain several features of fe mn formations bifs and greenstone belts

role of organic matter in the proterozoic oklo natural fission reactors gabon africa of the sixteen known oklo and the bangombe natural fission reactors hydrothermally altered elastic sedimentary rocks that contain abundant uraninite and authigenic clay minerals reactors 1 to 6 at oklo contain only traces of organic matter but the others are rich in organic substances reactors 7 to 9 are the subjects of this study these organic rich reactors may serve as time tested analogues for anthropogenic nuclear waste containment strategies organic matter helped to concentrate quantities of uranium sufficient to initiate the nuclear chain reactions liquid bitumen was generated from organic matter by hydrothermal reactions during nuclear criticality the bitumen soon became a solid consisting of polycyclic aromatic hydrocarbons and an intimate mixture of cryptocrystalline graphite which enclosed and immobilized uraninite and the fission generated isotopes entrapped in uraninite this mechanism prevented major loss of uranium and fission products from the natural nuclear reactors for 1 2 b y 24 refs 4 figs

natural nuclear fission reactors time constraints for occurrence and their relation to uranium and manganese deposits and to the evolution of the atmosphere abstract knowledge of the formation conditions of francevillian uranium and manganese ore deposits as well as natural fission reactors sheds light on the early evolution of the atmosphere between 1950 and 2150 ma ago the model explaining the formation of the oklo uranium deposits suggests that at the time of sediment deposition in the franceville basin 2150 million years ago the oxygen deficient atmosphere would have inhibited uranium dissolution dissolution of uranium was only possible during later diagenesis approximately 1950 ma reduction reactions in the presence of hydrocarbons allowed precipitation of dissolved uranium to u4 forming deposits with high enough uranium contents to trigger subsequent nuclear fission reactions such a model is in agreement with earlier suggestions that oxygen contents in atmosphere increased during a transition phase some 2450 2100 ma ago the manganese deposits were formed before the uranium deposits during the deposition of the black shales and very early diagenesis and thus at a time when oxygen content in atmosphere was very low carbon isotopes data of organic matter show decrease of 13c upward in the francevillian series 20 to 46 pdb reflecting the high ch4 and low o2 contents in the atmosphere during sediment deposition this favoured anoxic conditions during deposition of the basinal fb black shales and likewise the migration of mn over long distances the manganese precipitated first as mn oxides at the shallow edges of the franceville basin in photic zones where photosynthetic organisms flourished mn oxides were then reduced in the black shales forming mn carbonates when conditions became more reducing during transgression episodes and or the first stages of burial in the black shales reducing conditions prevailed until recent weathering allowing the good preservation of organic matter and the mn deposits the present day alteration is responsible for the dissolution of mn carbonates and precipitation of mn oxides at the water table to form the high grade mn ore 45 50 mn development of photosynthesizing organisms a volcanic source of the mn and favourable palaeogeography of the francevillian basins are all important parameters for the formation of the mn deposits for the occurrence of the natural nuclear reactors the age of 2 0 ga is the main parameter that controls the abundance of fissile 235u and the critical mass before 2 0 ga the 235u 238u ratio was sufficiently high for fission reactions to occur but conditions favourable for forming high grade uranium ores were not achieved then after 2 0 ga the increase of oxygen in the atmosphere commonly led to the formation of high grade uranium ores in which the 235u 238u ratio was too low to support criticality

uranium deposits of franceville basin gabon role of organic matter and oil cracking on uranium mineralization abstract the lower proterozoic uranium deposits in the franceville basin gabon are mainly known to have hosted natural nuclear reactors however this basin also witnessed a former petroleum system which shows major occurrences of uranium ores associated with organic matter the uranium mineralization is the result of several episodes of oil generation and migration fluid mixing and hydrofracturing during burial at around 2 0 ga black shales were heated and expelled hydrocarbons which migrated in underlying sandstones the first episode of oil migration was synchronous with a silicification event produced by a hot low salinity fluid as shown by fluid inclusions trapped in quartz overgrowths the second episode was contemporaneous with quartz dissolution and is characterized by the mixing of hydrocarbons and oxidizing u bearing brine which resulted in the precipitation of uo2 inclusions in oil then oil to gas conversion generated overpressured gas trapped in pores with uraniferous bitumen nodules changes in the stress regime probably favored radial hydrofracturing around bitumen nodules and subsequently the development of a pervasive micro fracture network there uo2 precipitated together with cu fe sulfides through thermochemical sulfate reduction favored by the presence of hydrocarbons and methane

oxygen dynamics in the aftermath of the great oxidation of earth s atmosphere 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 13c 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

pbpe systematics on diagenetic clays an example from proterozoic black shales of the franceville basin gabon this study presents the first dating attempt of diagenetic clay material by the pb cpb isotope method pb pb isotopic measurements were performed on authigenic 0 4 m clay fractions illite 1m fe mg chlorite extracted from black shales highly enriched in organic matter of the francevillian lower proterozoic sedimentary series in gabon the clay residues and acid leachates 1 n hcl yield a pb pb isochron age of 2328 130 ma mswd 1 24 even if this age is within error limits identical with two sm nd isochron ages previously reported for the same material it is not considered as a true isochron age the pb isotopic data of the residues indicate that the clay minerals are not in isotopic equilibrium however the isotope data of the leachates separately define an isochron age of 2265 150 ma mswd 0 36 which is closer to the sm nd age it is suggested that the leachates are the most appropriate phases for dating diagenetic processes with pb isotopes the u th pb fractionation in the clay fractions is related to the occurrence of organic matter in the sediments the upb and uth ratios of the clays correlate with their organic carbon contents this fractionation is probably due to differential complexation of u th and pb by organic ligands during the dissolution of detrital mineral phases and clay mineral authigenesis

natural fission reactors of oklo fourteen natural fission reactors are known to date in three different ore deposits located in the franceville basin the most famous and the first discovered are those in the oklo uranium ore deposit petrographic geochemical and oxygen isotope studies have been performed in an attempt to answer these questions 1 what are the main characteristics of the uranium ores in which fission reactions took place 2 what are the processes that created such exceptionally high grade ores and 3 what are the effects of such fission reactions on the host rocks the ore which hosts the fission reactions at oklo is characterized by a gangue of clay minerals whereas the normal ore of oklo consists of sandstones these clay minerals are the result of hydrothermal alteration of sandstone hydrothermal circulation was induced by the heat produced by fission reactions the reactor ores are further characterized by very high uranium contents 20 60 and high uranium accumulation by means of silica depletion and by uranium enrichment of the normal ore without uranium depletion hydrothermal convective circulation induced by the fission reactions created very high grade ore next to the reactors hydrothermal processes are thus critical to the propagation of the fission reactions

textural and paleo fluid flow control on diagenesis in the paleoproterozoic franceville basin south eastern gabon abstract the paleoproterozoic 2 15 ga franceville basin south eastern gabon is a continental sedimentary basin that host unmetamorphosed sediments this study involve detailed mineralogy sedimentology and petrography of the basal sedimentary units of fa and lower fb fb1 formations from the basin margin to centre in relation to mineral paragenesis and fluid flow the fa formation conglomerate sandstone and mudstone consists lithofacies of mixed fluvial and fluvio deltaic transitional origin while the overlying fb1 formation includes alternating organic rich black shale and sandstone of marine deposit the medium to coarse grained fluvio deltaic quartz arenite in upper part of fa formation is characterized by pervasive authigenic quartz cementation that reduced the porosity and permeability in the early stage of burial history this provides a resistant framework for subsequent diagenetic modification and also inhibits fluid flow during burial diagenesis in contrast the clay and unstable detrital grains rich fluvial arkosic to sub arkosic sandstones that escaped early quartz cementation show considerable pressure solution at grain contacts these arkosics were less porous and permeable when deposited but transformed to diagenetic aquifers as a result of dissolution of detrital grains during diagenesis and subsequent precipitation of authigenic mineral cements in the resulting secondary porosities from the proximal to distal basin and within sample suites there is no considerable chemical variation in the petrographic distinct generations of the precipitated illite and chlorite suggesting their precipitation from a near equilibrium homogenous pore fluid the predominance of 1mt illite polytype in most lithologies reflects precipitation of the clay minerals and probably other cements in an environment with high fluid rock ratio dolomite anhydrite barite and fe oxides are the main crystallized authigenic minerals aside illite and fe rich chlorite clay minerals the mineralogical assemblages and textural occurrences of the rocks suggest that diagenesis and fluid flow in the fa formation in the franceville basin are mainly controlled by depositional facies

petrography and paragenesis of organic matter associated with the natural fission reactors at oklo republic of gabon a preliminary report sixteen known uranium rich pockets in the sediment hosted uranium ore deposits in the oklo area became nuclear fission reactors 1968 50 ma ago and operated as such for up to 1 ma nuclear criticality was caused by unique and fortuitous geological environments and events these included the localized high concentrations of uranium in small pockets in the ore bodies the fact that the relative abundance of the fissile 235u isotope was five times greater in uranium 2 ga ago than present the presence of water which acted as a moderator in the natural reactors and the absence of neutron poisons which are elements that can prevent nuclear chain reactions organic matter is present in all of the oklo natural reactors but it is abundant only in reactors 7 to 16 organic matter has been studied in natural reactors 7 to 9 and at locations at various distances from these reactors bitumen in the oklo reactors is the predominant organic phase it is now solid bitumen containing dispersed cryptocrystalline graphite in crystal domains smaller than optical microscopic size its immediate precursor was liquid bitumen generated from syngenetic kerogen in organic rich sedimentary rocks in the francevillian basin of gabon and in the natural reactors themselves by hydrous reaction mechanisms prior to during and after nuclear criticality a preliminary paragenesis of organic matter at oklo may be defined through the following sequence of events a protokerogen and kerogen evolve from abundant cyanobacteria in the tidal and deltaic sediments in the basal fa formation of the francevillian series during sedimentation and burial respectively b during subsequent subsidence of the basin the first generation of bitumen and petroleum occurred c during uplift the sedimentary strata were fractured and bitumen and petroleum migrated through fractures following this oxidizing aqueous solutions carrying uranyl ions migrated through the highly fractured rocks met and were reduced by organic matter and precipitated pitchblende or uraninite at the present sites of the oklo uranium ore deposits and natural reactors the natural reactors reached nuclear criticality they were heated and produced the second generation of bitumen through hydrous reactions from the by now solid first generation bitumen and remaining kerogen finally hydrothermal effects associated with the dolerite dike swarm intrusion 750 150 ma ago produced yet another localized generation of liquid bitumen from solid organic matter possibly other bitumen generations also occurred during and following this time interval the organic matter in the natural reactors soon became a solid and was able to prevent the loss of uraninite grains enclosed in it these uraninite grains trapped and then immobilized fission products until and to an extent even after a major tectonic igneous event the intrusion of the dolerite dike swarm

oil and its biomarkers associated with the palaeoproterozoic oklo natural fission reactors gabon abstract the 2 1 ga fa formation sandstone of the franceville basin in gabon that hosts the oklo natural fission reactors has been discovered to contain abundant palaeoproterozoic oil bearing fluid inclusions inside which syngenetic biomarkers are preserved the oil occurs within h2o and co2 dominated inclusions trapped in syntaxial quartz overgrowths and intragranular and transgranular microfractures in detrital quartz homogeneous fluid inclusion assemblages with oil inside a brine and carbonic fluid indicate that there was intermixing of brines and co2 with liquid hydrocarbons prior to trapping textural relationships and microthermometry suggest that entrapment of oil occurred first during diagenesis of the sandstone at ca 115 to 200 c soon after deposition of the sequence at ca 2 1 ga and secondly during a hydrothermal event at 200 to 285 c linked to the operation of the reactors ca 1 98 ga a series of sequential outside rinse blanks of framework grains analysed by gas chromatography mass spectrometry gc ms prior to fluid inclusion crushing shows a first solvent rinse dominated by hydrocarbons derived from co occurring solid bitumens which have a different geochemical distribution compared to the fluid inclusion oil the crush leach extract containing oil from fluid inclusions is markedly richer than the final outside rinse blank displays significant geochemical differences in compound distribution and is interpreted to include only a very small contribution from solid bitumen the fluid inclusion oil has a high maturity is non biodegraded and lacks clear effects of radiolysis it is therefore likely that the oil that migrated at temperatures higher than those of diagenesis was generated by hydrothermal alteration caused by reactor heated fluids rather than by the criticality event itself biomarkers include hopanes 2 methylhopanes terpanes and steranes indicative of bacteria including cyanobacteria and of eukaryotes the relatively high concentration of regular steranes suggests that the source rock had a substantial eukaryotic contribution trace amounts of c30n propylcholestanes indicate a contribution from marine algae the oil was likely derived from conformably overlying marine black shales that were deposited during the great oxidation event during which the earth s atmosphere became oxygenated the biomarker content of the oil is remarkably similar to that of other oils formed in sedimentary basins between 2 7 and 1 4 ga it is thus suggested that hydrocarbons were derived from a uniform range of organisms in this time period despite apparent fluctuations of atmospheric o2

late archean initiation of manganese metallogenesis its significance and environmental controls abstract manganese metallogenesis was initiated in a modest scale during the late archean time selectively in india and brazil sedimentary deposits occur in both greenstone belts and high grade granulite terranes in shallow water shelf regimes only and are often intimately associated with stromatolites the changes in the rates of continental crustal growth mantle heat flux and outgassing along with the evolution of tectonic regimes sedimentary environments the state of the biosphere and finally the compositions of interacting atmosphere hydrosphere system from the early to the late archean time have been traced as interdependent parameters and interpreted to explain the first appearance of sedimentary manganese deposits promoted by possibly localized oxygenated environments compared to the spectacular manganese event represented by the giant paleoproterozoic kalahari deposit south africa which is interpreted to have been formed as a consequence of the rapid increase in atmospheric oxygen level ca 2 5 2 4 ga ago the modest initiation of the late archean manganese depositions was triggered by localized photosynthetic oxygen supply forming basin margin oxygen oases as a prologue for the succeeding stratified ocean system the dissolved manganese in the basin water that was oxidized to form shelf type shallow water deposits is suspected by analogy with contemporary banded iron formations bifs but not proved to be of hydrothermal ancestry the initiation of concentrated manganese sedimentation during the late archean by itself provides an evidence for an increase in the oxygen content in the contemporary atmosphere hydrosphere system compared to that in the earlier period supporting the geochemical indications from paleoweathering profiles

kolosjoki sedimentary formation a record in the aftermath of the paleoproterozoic global positive δ13c excursion in sedimentary carbonates abstract the kolosjoki sedimentary formation of the pechenga greenstone belt north eastern fennoscandia records the aftermath of the paleoproterozoic global positive 13 c excursion in sedimentary carbonates the lomagundi jatuli isotope excursion the goals of this research were to provide detailed new data on the 13 c trend in the kolosjoki sedimentary formation and generate a secular 13 c curve for the time period immediately succeeding the lomagundi jatuli isotope excursion for these purposes sedimentary carbonate samples from two new drillcores representing the kolosjoki sedimentary formation were collected in total 88 whole rock samples and 67 micro drilled subsamples ca 1 3 mg were analyzed for the isotope composition of c and o the whole rock elemental abundances and for the composition of the acid soluble fraction the kolosjoki carbonate rocks are dolostone or calcitic dolostone mg ca 0 50 0 67 with minor limestone mg ca 0 04 0 06 only weak correlation was observed between the mn sr ratios and the 13 c and 18 o values and the carbonate samples have likely retained their near primary 13 c values the sedimentary carbonate rocks show first low 13 c values at 2 to 1 and then a subtle upward increasing 13 c trend from ca 1 to 3 the increasing 13 c trend is interpreted to record a recovery from a 13 c minimum following the lomagundi jatuli isotope excursion

hydrothermal and supergene clays of the oklo natural reactors conditions of radionuclide release migration and retention abstract mineralogical chemical and o isotopic analyses were performed on the clay matrices surrounding two natural fission reactors of the oklo deposit in the deeply preserved reactor 10 450 m clays are composed of hydrothermal mg chlorites and sudoites al chlorites the wide range of their o isotopic compositions from 0 0 to 15 1 smow is consistent with crystallisation during conditions of criticality when the reactors created a thermal gradient of 100 c m the temperature in the core of reactor is calculated to have been approximately 400 c in contrast in the shallow reactor 9 120 m deep vermiculitized al chlorites are the products of the weathering of the hydrothermal chlorites these vermiculitized al chlorites are 18 o enriched 18 o 18 smow and underwent interaction with surface fluids 2 to 5 149 sm 147 sm isotopic ratios of the clays of reactor 9 show a wide dispersion 2 3 m of the fissiogenic sm around the reactor the migration of the fissiogenic sm which is usually retained in the deep reactors is here related to the circulation of meteoric water under oxidising conditions

isotopic evidence for massive oxidation of organic matter following the great oxidation event the stable isotope record of marine carbon indicates that the proterozoic eon began and ended with extreme fluctuations in the carbon cycle in both the paleoproterozoic 2500 to 1600 million years ago ma and neoproterozoic 1000 to 542 ma extended intervals of anomalously high carbon isotope ratios 13c indicate high rates of organic matter burial and release of oxygen to the atmosphere in the neoproterozoic the high 13c interval was punctuated by abrupt swings to low 13c indicating massive oxidation of organic matter we report a paleoproterozoic negative 13c excursion that is similar in magnitude and apparent duration to the neoproterozoic anomaly this shunga francevillian anomaly may reflect intense oxidative weathering of rocks as the result of the initial establishment of an oxygen rich atmosphere

structural and metamorphic evolution of the gabon orogenic belt collision tectonics in the lower proterozoic abstract the archaean granite gneiss terrain of central gabon comprises medium to high grade gneisses metamorphosed at 3 15 ga forming the monts cristal and underlying the mitzic region intruded by and enclosed as enclaves in granitoids 3 0 2 6 ga old that form the extensive chaillu and north gabon blocks these rocks are unconformably overlain in the east of gabon by early proterozoic francevillian sedimentary rocks between 2 3 and 2 0 ga old forming the franceville and booue basins the francevillian is overthrust on its west side by the ogooue metamorphics themselves considered to be of early proterozoic age these rocks crop out in a broad synclinorium consisting essentially of paragneisses with orthogneisses appearing locally at the base the overall tectonic setting is discussed in terms of the evolution of the various domains from west to east 1 1 on the west flank of the synclinorium is a migmatitic granulitic dome the abamie dome in which structures diverge away from the core metamorphism is of high temperature intermediate to low pressure type 2 2 on the east flank of the ogooue synclinorium the medium grade ogooue metamorphics sillimanite biotite kyanite staurolite staurolite muscovite biotite have been thrust eastwards on to the low grade kyanite sericite francevillian 3 3 the francevillian is parautochthonous being widely detached from its archaean basement owing to the effects of the same eastward directed tangential tectonics 4 4 locally slices of archaean basement have been tectonically incorporated the structural cross section illustrates a history of diapiric uprise passing eastward into tangential tectonics that is typical of classical collision belts the suture marking the collision is interpreted to be located in the abamie migmatite dome where the nappes are rooted the gabon orogenic belt is correlated with the collision belts of about the same age on the eastern margin of the congo craton and with the trans amazonian orogenic belt of the guyana shield

redistribution of fissiogenic and non fissiogenic ree th and u in and around natural fission reactors at oklo and bangombe gabon abstract elemental abundances and isotopic compositions of rare earth elements ree th and u of twenty eight samples from four kinds of natural fission reactors at the oklo and bangombe uranium ores were determined by mass spectrometry fissiogenic and non fissiogenic ree components of each sample were calculated from the isotopic compositions the geochemical distribution of both fissiogenic and non fissiogenic ree differs among the four reactors each reactor shows the following features possibly associated with the local geochemical conditions 1 reactor 9 at the shallow depth of the oklo deposit contains higher amounts of non fissiogenic ree than the other reactors the distribution of non fissiogenic ree does not reflect the primordial ree abundance patterns and might have been disturbed in and around the reactor due to supergene alteration our results suggest that significant amounts of fissiogenic lighter ree lree such as la ce and pr were mobile in the reactor 2 reactors 10 and 13 located deep underground have much lower contents of non fissiogenic ree than reactor 9 all fissiogenic ree show high retention in the reactors non fissiogenic ree of reactor 10 inform of the primordial ore formation without any geochemical disturbance little redistribution of both fissiogenic and non fissiogenic ree in the reactor 10 was observed and 3 the bangombe reactor located at shallow depth has apparently well preserved fissiogenic ree non fissiogenic ree in the bangombe reactor might have been disturbed possibly by hydrothermal processes the distribution behavior of fissiogenic ree is considered to be related with physico chemical reactor conditions such as nuclear reaction temperature and chemical compositions of each reactor but clear relationship between nuclear parameters and the ree distribution could not be obtained in this study

precambrian superplumes and supercontinents a record in black shales carbon isotopes and paleoclimates prominent maxima in black shale abundance and in black shale total shale ratio occur at 2 0 1 7 ga with less prominent peaks in the late neoproterozoic 800 600 ma and in the late archean 2 7 2 5 ga peaks in chemical index of alteration cia of shales at the same times suggest corresponding warm paleoclimates the peaks in cia and black shale abundance are correlated in time at a 94 confidence level the black shale and cia peaks may reflect the combined effects of mantle superplume events and supercontinent formation at 2 7 and 1 9 ga mantle superplume events may have introduced large amounts of co2 into the atmosphere ocean system increasing depositional rates of carbon and increasing global warming increased black shale deposition may reflect some combination of 1 increased oceanic hydrothermal fluxes introducing nutrients 2 anoxia on continental shelves and 3 disrupted ocean currents the apparent absence of carbon isotope anomalies at these times reflects an increase in the deposition and burial rate of both reduced and oxidized carbon peaks in black shale abundance at 2 1 ga and 800 600 ma correlate with peaks in 13 c in marine carbonates increases in atmospheric oxygen and with high cia values in shales these are all consistent with higher rates of organic carbon burial in black shales at these times these peaks may record the breakup of supercontinents at 2 2 2 0 ga and again at 800 600 ma which resulted in increased numbers of partially closed marine basins disruption of ocean currents and increased hydrothermal vents at ocean ridges all of which led to widespread anoxia 2001 elsevier science b v all rights reserved

origin and environment of manganese rich sediments within black shale basins abstract sediments with unusually high manganese contents occur in anoxic basins of the central baltic sea we present a new model for the enrichment of manganese which is based on sedimentological and geochemical analyses of holocene sediments from the gotland deep and on published hydrographic data due to salinity stratification and high primary production bottom waters of the central baltic sea are anoxic and rich in dissolved mn 2 episodically bottom waters become oxygenated by inflows of denser water from the north sea mixing results in oxidation of mn 2 to fine grained particulate oxides which accumulate in the deepest parts of the basins where currents are mostly absent here anoxic conditions are re established within a few months or years and manganese oxides are again dissolved causing high concentrations of mn 2 in the near bottom layer alkalinity is high as a consequence of bacterial reduction of manganese oxides and sulphate under these conditions manganese is reprecipitated and forms a layer of ca rich rhodochrosite on the top of laminated sapropels occasionally periods of such extremely and rapidly changing redox conditions are followed by long term oxygenation of bottom waters in that case a layer rich in manganese oxides forms on the top of a bioturbated layer due to dissolution of rhodochrosite and oxidation of manganese in the near surface sediment return of anoxic conditions results again in the transformation of manganese oxides into rhodochrosite varying rhodochrosite contents in the basinal sediments therefore record a detailed history of redox conditions in bottom waters the manganese rich sediments of the baltic sea share many features with some occurrences of lower jurassic and lower carboniferous manganese ores in western and central europe we therefore suggest that these manganese enrichments were formed by similar processes

organism motility in an oxygenated shallow marine environment 2 1 billion years ago evidence for macroscopic life in the paleoproterozoic era comes from 1 8 billion year old ga compression fossils han tm runnegar b 1992 science 257 232 235 knoll et al 2006 philos trans r soc lond b 361 1023 1038 stirling biota bengtson s et al 2007 paleobiology 33 351 381 and large colonial organisms exhibiting signs of coordinated growth from the 2 1 ga francevillian series gabon here we report on pyritized string shaped structures from the francevillian basin combined microscopic microtomographic geochemical and sedimentologic analyses provide evidence for biogenicity and syngenicity and suggest that the structures underwent fossilization during early diagenesis close to the sediment water interface the string shaped structures are up to 6 mm across and extend up to 170 mm through the strata morphological and 3d tomographic reconstructions suggest that the producer may have been a multicellular or syncytial organism able to migrate laterally and vertically to reach food resources a possible modern analog is the aggregation of amoeboid cells into a migratory slug phase in cellular slime molds at times of starvation this unique ecologic window established in an oxygenated shallow marine environment represents an exceptional record of the biosphere following the crucial changes that occurred in the atmosphere and ocean in the aftermath of the great oxidation event goe

pyrite multiple sulfur isotope evidence for rapid expansion and contraction of the early paleoproterozoic seawater sulfate reservoir abstract earth s oxygenation is often described in terms of two unidirectional steps at the beginning and end of the proterozoic eon separated by a long lived intermediate redox state recent work defines a more complicated path to oxygenation exemplified by an apparent drop in oxidation state following the early paleoproterozoic lomagundi carbon isotope excursion the timing of this proposed drop in oxidation state is not well constrained and it is not clear how it relates to redox conditions during the remainder of the proterozoic here we present a study of pyrite multiple sulfur isotopes supported by fe speciation and organic carbon isotopes from early paleoproterozoic black shales we find evidence for the rapid expansion of the seawater sulfate reservoir during the great oxidation event at ca 2 3 ga followed by a subsequent contraction in the size of the seawater sulfate reservoir at ca 2 05 ga this scenario is consistent with the emerging view of a rise and fall in surface oxidation state during the early paleoproterozoic comparison of our new data to other records of the seawater sulfate reservoir suggests that the elevated sulfate concentrations that characterize the early paleoproterozoic did not return until the late neoproterozoic

links between palaeoproterozoic palaeogeography and rise and decline of stromatolites fennoscandian shield through a review of literature and new data we have documented two major events in the palaeoproterozoic history of stromatolites as indicated by palaeontological and palaeoenvironmental studies with a time resolution of between 40 and 200 ma we confirm semikhatov and raaben s and awramik s albeit approximately maximum in diversity and abundance of stromatolites between 2330 and 2060 ma ago jatulian diversification we suggest that this taxonomic diversity was driven by a major phase of cratonisation formation of the karelian carbonate platform and numerous rift related shallow water carbonate basins supersaturated with ca 2 mg 2 and co2 the jatulian stromatolite explosion is synchronised with a positive 13ccarb shift of jatulian age carbonates we also document stromatolite decline which occurred on the fennoscandian shield somewhere between 2060 and 1900 ma ago this decline both in abundance and in taxonomic diversity is interpreted as having been caused by the first phase of oceanisation the oceanisation led to the considerable reduction in ecological niches that could be utilised by cyanobacteria the post jatulian decline of stromatolites coincides with an abrupt downward 13corg shift from 19 to 38 and is roughly coeval with the appearance of the first eukaryotic algae documented elsewhere the systematics of the fennoscandian diversity of palaeoproterozoic stromatolites is identical to that reported from india and china and reveals a dissimilarity with abundance and diversity patterns in australia and northern america

chronology and geodynamic setting of cretaceous cenozoic rifting in west and central africa abstract the development of the early cretaceous to palaeogene west and central african rift system which extends from nigeria benue trough to kenya anza trough can be related to the build up of intraplate tensional stresses during the break up of gondwana which caused reactivation of pre existing zones of lithospheric weakness repeated changes in the intraplate stress regime of africa are reflected by phases of crustal extension alternating with episodes of compression many of these events can be correlated with changes in rates of seafloor spreading in the central and south atlantic oceans as reflected in flowline patterns the west and central african rifts can be considered as typical passive rifts which evolved in response to the build up of intraplate stresses however the st helena hot spot appears to have been located beneath the equatorial plate boundary at approximately 120 ma and may have played an important role in weakening the lithosphere during extension

natural fission reactors in the franceville basin gabon a review of the conditions and results of a critical event in a geologic system abstract natural nuclear fission reactors are only known in two uranium deposits in the world the oklo and bangombedeposits of the franceville basin gabon since 1982 five new reactor zones have been discovered in these deposits and studied since 1989 in a cooperative european program new geological mineralogical and geochemical studies have been carried out in order to understand the behavior of the actinides and fission products which have been stored in a geological environment for more than 2 0 ga years the franceville basin and the uranium deposits remained geologically stable over a long period of time therefore the sites of oklo and bangombeare well preserved for the reactors two main periods of actinide and radionuclides migration have been observed during the criticality under p t conditions of 300 bars and 400 500 c respectively and during a distention event which affected the franceville basin 800 to 900 ma ago and which was responsible for the intrusion of dolerite dikes close to the reactors new isotopic analyses on uranium dioxides clays and phosphates allow us to determine their respective importance for the retention of fission products the uo 2 matrix appears to be efficient at retaining most actinides and fission products such as rees y and zr but not the volatile fission products cd cs xe and kr nor rb sr and ba some fissiogenic elements such as mo tc ru rh pd and te could have formed metallic and oxide inclusion in the uo 2 matrix which are similar to those observed in artificial spent fuel clays and phosphate minerals also appear to have played a role in the retention of fissiogenic rees and also of pu

environments and processes of manganese deposition concentration of manganese in solution and its deposition takes place by redox controlled processes in a variety of modern and ancient geologic and geochemical environments modern mn deposition occurs predominantly in deep sea areas rather than shallow water domains although deep sea sedimentary deposits dominate hydrothermal contribution of mn to the ocean system may be substantial mn deposition from hydrothermal solutions at or near sea floor spreading centers and less commonly in island arc areas is known in addition near and far field dispersion of mn from vent sites is also substantial such distributions are controlled by the flow rate and egress temperature of the solution and the residence time of mn in seawater thus even in sedimentary deposit domains at least partial derivation of mn from a hydrothermal source is possible sedimentary fe mn crusts on older volcanic substrates on seamounts form by hydrogenous deposition of metal concentrated from terrigenous sources in the mid water column oxygen minimum zones thus the presence or absence of volcanic rocks is not a clear indication of whether sedimentary mn deposits particularly in the ancient geologic record are the result of a totally terrigenous or a totally volcanogenic source abyssal fe mn nodules are considered to form from a basin water hydrogenous and or pore water early diagenetic supply of metals but in most cases the extent of supply from either of the sources is unknown the metal incorporation mechanisms of free moving nodules is little understood and it is possible that in most cases both sources contribute to the nodule composition therefore no nodule should be considered as totally hydrogenous or totally early diagenetic based only on its bulk composition the determined growth rate giving only an average value cannot by itself reveal the growth history of the nodules biological participation directly or indirectly controls mn deposition the stratified black sea demonstrates the concentration of mn in solution in an anoxic zone its advection toward the redox interface and its precipitation in an oxygenated condition similar stratified basins are contemplated for ancient mn deposition in shallow water basin margin areas geologic and geochemical signatures indicate that during sea level highstands stratified basins formed in which mn was concentrated in solution in the anoxic part corresponding transgression led to the impingement of the redox interface on the continental shelf and precipitation of mn oxides could take place across the interface during transgression regression cycles offshore in anoxic or dysaerobic conditions mn carbonate could form by early diagenetic reaction of mn super 2 with co 2 or hco 3 super produced by organic carbon oxidation critical mn deposits occurring in transgressive glaciogenic and black shale bearing ancient sequences support this paleoenvironmental model for mn deposition

fractionation between inorganic and organic carbon during the lomagundi 2 22 2 1 ga carbon isotope excursion article i nfo the lomagundi 2 22 2 1 ga positive carbon isotope excursion in shallow marine sedimentary carbonates has been associated with the rise in atmospheric oxygen but subsequent studies have demonstrated that the carbon isotope excursion was preceded by the rise in atmospheric oxygen the amount of oxygen released to the exosphere during the lomagundi excursion is constrained by the average global fractionation between inorganic and organic carbon which is poorly characterized because dissolved inorganic and organic carbon reservoirs were arguably larger in the paleoproterozoic ocean at a time of lower solar luminosity and lower ocean redox state decoupling between these two variables might be expected we determined carbon isotope values of carbonate and organic matter in carbonates and shales of the silverton formation south africa and in the correlative sengoma argillite formation near the border in botswana these units were deposited between 2 22 and 2 06 ga along the margin of the kaapvaal craton in an open marine deltaic setting and experienced lower greenschist facies metamorphism the prodelta to offshore marine shales are overlain by a subtidal carbonate sequence carbonates exhibit elevated 13 c values ranging from 8 3 to 11 2 vs vpdb consistent with deposition during the lomagundi positive excursion the total organic carbon toc contents range from 0 01 to 0 6 and 13 c values range from 24 8 to 13 9 thus the isotopic fractionation between organic and carbonate carbon was on average 30 3 2 8 n 32 in the shallow marine environment the underlying sengoma shales have highly variable toc contents 0 14 to 21 94 and 13 c values 33 7 to 20 8 with an average of 27 0 3 0 n 50 considering that the shales were also deposited during the lomagundi excursion and taking 13 c values of the overlying carbonates as representative of the 13 c value of dissolved inorganic carbon during shale deposition a carbon isotope fractionation as large as 37 appears to characterize the production of bulk organic matter in the deeper part of the pretoria basin at that time this enhanced fractionation relative to that observed in shallow water environments likely reflects heterotrophic secondary and chemotrophic productivity at and below a pronounced redoxcline consistent with the euxinic conditions inferred from independent evidence for the deeper part of the pretoria basin greater variability in organic carbon vs carbonate carbon isotopic values on the shallow marine carbonate platform suggests that the carbon cycling was dominated by a large dissolved inorganic carbon reservoir during the lomagundi excursion our study suggests that in contrast to the late neoproterozoic and phanerozoic when carbon isotope fractionation between carbonate and organic carbon in the open ocean was mostly controlled by primary producers in the paleoproterozoic redox stratified ocean heterotrophic and chemotrophic productivity overprinted a signal of primary productivity below the redoxcline this strong imprint of heterotrophic and chemotrophic productivity on organic carbon isotope records complicates the reconstruction of spatial patterns and secular trends in the 13 c values of dissolved inorganic carbon in the paleoproterozoic seawater

exceptional preservation of expandable clay minerals in the ca 2 1 ga black shales of the francevillian basin gabon and its implication for atmospheric oxygen accumulation 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

nanoscale analysis of preservation of ca 2 1 ga old francevillian microfossils gabon abstract the fc formation of the francevillian of gabon displays the oldest gunflint type assemblage of microfossils that is hosted in shallow water stromatolites the fc formation was deposited between 2 14 and 2 08 billion years ago ga after the great oxygenation event 2 4 2 3 ga and near the end of the lomagundi event 2 3 2 06 ga although they have been used as a benchmark for the search for older microfossils the nature of gunflint type microfossils has remained elusive due to their simple shapes their small sizes and their alteration here we report the first nanoscale study of francevillian gunflint type microfossils we used a combination of raman spectroscopy palynology in situ focused ion beam sectioning and analytical electron microscopy in spite of the relatively high thermal maturity of organic matter inferred peak burial temperature 296 30 c spherical cell walls huroniospora and filamentous sheaths gunflintia minuta 3 m in diameter and broader filaments are preserved organic matter in on cell walls and sheaths is associated with nanocrystalline quartz whereas coarser quartz crystals fill and surround the microfossils this pattern likely inherited from recrystallization of texturally heterogenous opal generations could have allowed the observed preservation of organic structures and limited migrations of organic matter moreover we demonstrate the preservation of thick sheathed broad 3 m filaments for the first time in a stromatolitic gunflint type assemblage such thick sheaths are common in cyanobacteria but not in other filamentous bacteria we distinguished two types of star shaped organic microstructures eoastrion but found no diagnostic evidence for against a microfossil nature at the nanoscale furthermore we show that titanium is commonly associated with organic structures of microfossils likely as a result of diagenetic mineralization in contrast iron rich nanocrystals associated with microfossils occur in quartz not in organic matter and could possibly represent recrystallized biominerals

characterization of organic matter associated with uranium deposits in the francevillian formation of gabon lower proterozoic abstract elemental analysis organic petrography and high resolution transmission electron microscopy were used to study organic matter in lower proterozoic rocks of the francevillian series in africa results show a convincing relationship between solid bitumens derived from thermal alteration of crude oil and deposition of uraninite ores evidence is presented that suggests the presence of migration paths for crude oil in associated sandstones moreover the solid bitumens appear to have been further altered by radiation damage as a consequence of oxidation and uranium mineralization

microboudin structure of piedmontite in quartz schists a proposal for a new indicator of relative palaeodifferential stress abstract this paper proposes a new method to infer the relative differential stress for the rock body bulk differential stress from microboundinage the method is applied to four piedmontite bearing quartz schists collected from the high pressure low temperature metamorphic belts in japan nuporomaporo yamagami asemi and matsunosako in the samples brittle piedmontite grains are broken and subsequently pulled apart within the flowing quartz matrix the method consists of 1 statistical measurement of the fraction of microboudinaged grains 2 theoretical prediction of this fraction as a function of bulk differential stress and 3 inference of bulk differential stress by comparing the measured with the theoretical fraction the theoretical prediction has two aspects one is the model connecting bulk differential stress acting on a whole rock quartz schist with the tensile stress generated in the competent material piedmontite and the other is the model for the fracture strength of the competent material we use a fibre loading theory for the stress and a weakest link theory for the fracture strength the theoretical analysis is found to explain successfully the measured data by a chi squared test and we can obtain relative estimates of bulk differential stress the b value they are 1 0 0 7 0 4 and 0 2 for nuporomaporo yamagami matsunosako and asemi respectively

iron and sulphur isotopes from the carajas mining province para brazil implications for the oxidation of the ocean and the atmosphere across the archaean proterozoic transition abstract mineralogical analyses and major and trace element geochemistry combined with iron and sulfur isotopes were applied to banded iron formations bifs and pyrite bearing sandstones from the carajas mineral province brazil the bifs belong to the 2 7 ga old grao para group and show a rather simple mineralogy hematite and quartz or cryptocrystalline silica their ree y patterns suggest deposition under marine sub oxic conditions fe isotopes show highly positive values 57 fe irmm 14 2 06 0 34 in average which can be explained by the partial oxidation of fe 2 aq in the surface ocean subsequent to the upwelling of deep anoxic seawater the resulting iron oxy hydroxides likely formed in the shallow photic zone as a seasonal process and acquired highly positive iron isotope signature values consistent with a rayleigh distillation model the pyrite bearing sandstones belong to the aguas claras formation of palaeoproterozoic younger age and were cored at the base of the giant azul manganese deposit diagenetic pyrite is characterized by positive 57 fe irmm 14 1 02 0 2 and 34 s vctd 11 97 0 12 average values that are different from values of modern marine biogenic pyrite results likely indicate that dissolved sulfate was the limiting factor controlling biogenic pyrite formation at that time near zero 33 s values 0 013 0 003 indicate minimal mass independent sulfur isotope fractionation mif s consistent with the 2 1 ga age previously obtained from the aguas claras pyrites this result suggests deposition at a time when the oxygen partial pressure in the atmosphere was already high enough 10 5 to 10 2 pal or present atmospheric level to hinder mif s by photochemical reactions incidentally this also confirms that the giant mn deposit of carajas is in the same age range 2 1 0 2 ga as other mn ores in gabon and south africa pointing to the importance of mn precipitation in paleoproterozoic times

the neodymium isotope system as a tool for petroleum exploration abstract mineralogical petrological geochemical and neodymium isotopic investigations strongly suggest isotopic and chemical exchange between authigenic silicate phases and petroleum alteration of organic matter sulfur reduction generation of aqueous acidic solutions with the resultant dissolution of k feldspar leads to in situ crystallization of illite and chlorite as well as neodymium isotopic equilibration between the silicate phases and petroleum these findings are of significance not only to understand the mechanisms leading to neodymium isotopic equilibration between authigenic clay minerals in detrital sediments but also to source rock petroleum in reservoir correlations in particularly when biomarker molecules i e isoprenoid hydrocarbons have been obliterated by prolonged severe diagenesis

carbon isotopes as biogeochemical recorders of life over 3 8 ga of earth history evolution of a concept ever since pioneering studies in the late 1930s had shown that the conversion of inorganic carbon into biogenic substances entails sizeable redistributions of the stable carbon isotopes biologically mediated 13c 12c fractionations have come to be recognized as a common corollary of biochemical reactions meanwhile it is firmly established that the universal bias in favour of 12c characterizing biological materials primarily derives from a kinetic isotope effect that is imposed on the first carbon fixing enzymatic carboxylation reaction in the primary metabolism of co2 fixing autotrophic organisms this preference for 12c has turned out to be one of the most enduring relics of the ordered state of the biological precursor substances that may be preserved in fossil organics over billions of years with the currently known sedimentary record at hand it can be stated with confidence that biological carbon isotope fractionations have persisted throughout 3 8 ga of recorded earth history indicating that microbial prokaryotic and archaeoprokaryotic ecosystems had been prolific already on the archean earth while for the time span 3 5 ga the isotopic evidence is unequivocal the information encoded in the preceding record is commonly blurred by a metamorphic overprint this holds particularly for the metasediments of the 3 8 ga old isua supracrustal belt of west greenland which apart from widespread metasomatism have suffered amphibolite grade metamorphism it is known that 13c 12c exchange occurs in organic kerogenous rock constituents during both amphibolite and granulite facies metamorphism if a second carbon partner is available as either fluids or carbonate with isotopic re equilibration often only partially achieved due to the sluggish kinetics of the exchange reaction thermodynamic equilibria predict however that 13c 12c ratios in kerogen and graphite increase during this process hence high t exchange equilibria are always bound to drive 13c values in positive direction the lowermost values encountered being consequently the least exchanged and most pristine with the lowest values of reduced graphitic carbon obtained in early isua studies falling into the range 22 to 28 pdb we had straightforward evidence since the late 1970s that carbon constituents with the isotopic composition of biogenic matter were indeed present in the pre metamorphic isua suite it was therefore by no means surprising that the results of recent isotope work performed on apatite hosted carbonaceous microdomains in isua banded iron formation utilizing advanced techniques of instrumental microanalysis had prompted similar conclusions hence the mainstream of the sedimentary carbon isotope record can be best interpreted as the geochemical manifestation of the isotope discriminating properties of the principal co2 fixing reactions s in biological carbon assimilation suggesting an extreme degree of evolutionary conservatism in the biochemistry of autotrophic carbon fixation as a consequence biological modulation of the geochemical carbon cycle had been established at least 3 8 ga ago having been fully operative by the time of formation of the earth s oldest sediments