Éditeur(s) : HAL CCSD
Résumé : The Franceville Basin (2.1 Ga) in southeastern Gabon, hosts a black shale series well preserved (FB Formation) which represents an exceptional example of unmetamorphised Paleoproterozoic sediment strata. This basin includes the protore of one of the largest Mn-oxide laterite ore worldwide, mined by Eramet-Comilog. The aim of this this work is to determine formation conditions of this protore and to characterize the global sedimentary evolution of the FB Formation which include the protore. This 75 m thick protore is constituted of Mn carbonate-rich black shales which represent a potential ore deposit for the future. It was drilled, on the Bangombé plateau, during a recent campaign of 24 boreholes with an average depth of 125 m.Through multidisciplinary study on these cores and key outcrops of the basin, this work focuses on : i) the depositional environment of the Mn-protore and FB Formation ; ii) the processes of formation of the Mn-carbonates at 2.1 Ga and iii) the architecture and distribution of Mn-rich levels of the protore on the Bangombé Plateau.A detailed sedimentological and petrological study allowed us to redefine the division of the FB into nine units, named U1 to U9 from the base to the top. These units show a fine upward cycle up to U5 and a reverse coarse loop until U9. This division leads to a new interpretation to propose an evolution from a shoreface depositional environment controlled by deltaic currents (U1) to an offshore depositional environment with anoxic conditions (U2). In this basin, a system of submarine fan is developed, feeding a network of sand injections (injectites) covering the Bangombé plateau (70 km²) and with a thickness of 150 m affecting U4 to U7, including the Mn-protore. The protore depositional environment formed below the wave base limit (U4, U5 and U6) in a starved basin, controlled by biochemical sedimentation allowed the formation of Mn-carbonates. The end of starved basin, would allow the re-opening of the detrital input into the offshore basin (U7). This basin is then filled by storm bar deposits intersected by deltaic sub-aquatic channels (U8). The U9 unit corresponds to a quiet lagoon environment, allowing the multicellular organism development for the first time on the planet.A geochemical study allowed the characterization of the depositional environment of Mn-carbonates as an anoxic to sub-oxic and alkaline environment. For the first time, we showed that the manganese carbonates, present as bacteriomorph forms, are precipitated from the seawater by the mediated photosynthetic cyanobacterial activity, which allows CO2 / HCO3 depression of the environment and a local increase of pH. The cyanobacterial activity is controlled by the absence of bottom currents, which increase the detrital input. This would stop the activity of the cyanobacteria and thus would lead to the decrease of the Mn-concentration along the protore.Finally, well-log and a sequential correlation analyses allowed us to detail spatial and timing repartition of FB Formation deposit, controlled by a tectono-sedimentary model. We propose two- tectono-sedimentary phases. A first syn-tectonic phase (U1 to U3) controls the depocentres and sedimentation gaps. Turbidite coarse deposits are located in the most subsident part, clay deposits rather on the slope and carbonates on shoals. A second post-tectonic phase (U4 to U7) allows isopach deposits. The Mn-protore formed during the post-tectonic phase. However, it shows a variable thickness due to subsidence to the north of the Bangombé plateau. So, on the Bangombé plateau, Mn-contents increase towards the south, whereas the protore thickness increases towards the NNE. Moreover sand injectites decrease Mn-content in the eastern part of the Bangombé plateau and impact on the economic evaluation of the Mn-carbonates. Currently, the protore is structured by post-sedimentary faults, which lead to a non-continuity of the high Mn levels on the Bangombé plateau.
Le Bassin de Franceville situé au SE du Gabon présente une série de black shales (Formation FB) d'âge Paléoprotérozoïque (2,1 Ga) surmontant les grès de la Formation FA. Ce bassin peu déformé et non métamorphique représente une archive exceptionnelle des processus de dépôt de cette période de l’histoire de la Terre où la vie commence à se développer. En particulier, la Formation FB contient le protore d'un gisement mondial d'oxydes de manganèse exploité par la société Eramet-Comilog. L’objectif de ce travail est de préciser les conditions de formation de ce protore et de le replacer dans l’histoire du remplissage du bassin. Ce protore d'une épaisseur moyenne de 75 m est constitué de carbonates de manganèse ; il a fait l'objet d'une récente campagne de 24 forages carottés d'une profondeur moyenne de 125 m sur le plateau de Bangombé.A travers une approche pluridisciplinaire comprenant l'étude de ces forages et des affleurements clefs du bassin, ce travail porte sur la caractérisation i) de l'environnement de dépôt du protore et des séries qui l'encadrent (du toit du FA au toit du FB) ; ii) du mode de formation des carbonates de Mn à 2,1 Ga et iii) de l'architecture et de la répartition des hautes teneurs en Mn du protore qui représente un gisement potentiel du futur.L’étude pétro-sédimentaire détaillée a permis de distinguer neuf unités (U1 à U9) au sein de la Formation FB organisées suivant un cycle rétrogradant jusqu’à U5 puis progradant jusqu’à U9. Ce découpage montre une évolution du milieu de dépôt depuis un domaine de shoreface contrôlé par des courants deltaïques (U1) évoluant vers des dépôts d’offshore restreint (U2). Ce bassin enregistre ensuite un système de chenaux-levées turbiditiques (U3) qui alimentent un réseau d'injectites reconnu sur l’ensemble du Pl. de Bangombé et qui traverse 150 m de série (U4 à U7) en affectant le protore et ainsi les teneurs en Mn. L'environnement de dépôt du protore (U5 et U6) marque l’isolement du bassin qui devient affamé et contrôlé par une sédimentation biochimique à l’origine du dépôt des carbonates de Mn. L'Unité 7 correspond à la réouverture des apports détritiques en domaine d'offshore supérieur puis en domaine de shoreface dominé par des dépôts de tempêtes et de chenaux sous-aquatiques deltaïques (U8), et enfin lagunaire (U9) dans lequel apparaissent les premiers métazoaires de l’histoire de la planète, suivant une séquence régressive.Une étude géochimique a permis de préciser les conditions de dépôt du protore qui se forme en milieu alcalin anoxique à sub-oxique. Dans ce milieu, nous montrons pour la première fois une précipitation directe des carbonates de Mn sous forme bactériomorphe induite par l'activité photosynthétique des cyanobactéries qui consomment le CO2/HCO3 et conduisent à une augmentation du pH favorable à la formation des carbonates de Mn. L'activité cyanobactérienne est conditionnée par l’absence de courants de fond qui augmentent la turbidité du milieu et stoppent cette dernière.Les corrélations diagraphiques et séquentielles permettent de préciser la répartition spatiale et temporelle du FB permettant ainsi de replacer le protore dans l’histoire tectono-sédimentaire du bassin. Une première phase syn-tectonique (U1 à U3) contrôle l’épaisseur et la mise en place de dépôts turbiditiques dans les parties subsidentes, de dépôts argileux sur les pentes et de dépôt de carbonates sur les hauts-fonds. La seconde phase post tectonique (U4 à U7) permet la mise en place de dépôts relativement isopaques, bien que le protore enregistre une subsidence plus importante au nord du Pl. de Bangombé. On observe ainsi, sur le Plateau de Bangombé, des teneurs en Mn qui augmentent vers le sud alors que l’épaisseur du protore augmente vers le NNE. Postérieurement au dépôt du FB, le protore est structuré par des failles qui le compartimentent en touches de piano limitant ainsi sa continuité sur le Plateau de Bangombé.
https://hal.archives-ouvertes.fr/tel-01621460

tel-01621460
https://hal.archives-ouvertes.fr/tel-01621460
https://hal.archives-ouvertes.fr/tel-01621460/document
https://hal.archives-ouvertes.fr/tel-01621460/file/these_Dubois2017-MnGabon.pdf

Éditeur(s) : HAL CCSD
Résumé : Eight drill cores cutting through the Mn-carbonate bearing black shales from the Bangombé Plateau were studied. Mn-carbonates (up to 80 m thick) are underlain by laminated pyrite rich shales with organic carbon contents of about 4 wt. % and MnO contents of about 6 wt. %. Mn and Fe, S poor shales are intercalated. Mn-carbonate rich shales (20-29 wt. % MnO) have low contents of phyllosilicates, but are rich in organic carbon (about 7 wt. %) with moderate S contents (about 2 wt. %). All shale facies were deposited in a closed basin through suspension settling and precipitations under anoxic conditions. The Mn-carbonates, towards the top, were formed most likely under suboxic conditions. Pyrite and Mn-carbonates are characterized by bacteriomorphous structures. The latter are composed of micrometric carbonates finely intergrown with clays, quartz and organic matter. They formed around and corroded the dolomite and/or organic matter. Mn-carbonates and pyrite both form also several tenths of micrometer large agglomerates and sub-automorphous grains. The agglomerates can be attributed to evolving diagenesis. Carbonate chemistry varies mainly from rhodochrosite to dolomite. The present results point to primary microbial Mn-carbonate formation. No signs for a Mn-oxide precursor were detected. Slumping and shearing structures, distortion and disruption of thin pyrite beds indicate synsedimentary deformations.
13th Biennial SGA Meeting
Nancy, France

hal-01356155
https://hal.archives-ouvertes.fr/hal-01356155

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The Urucum region (Mato Grosso do Sul, Brazil) contains Neoproterozoic–Cambrian manganese ore in the layers Mn-1, Mn-2, and Mn-3, which are interbedded with iron formations (IFs) from the Santa Cruz Formation (Jacadigo Group) and surrounded by carbonate rocks from the Bocaina and Tamengo Formations (Corumbá Group). These rocks fill an ancient graben, with sediments from the Santa Cruz Formation overlying fluvial deposits from the Urucum Formation and limestones from the Bocaina and Tamengo Formations deposited in the shallow marginal regions. As the graben deepened, it was flooded with microbe-rich seawater and hydrothermalism began. Iron and manganese precipitated within the pores in arkosic sandstones, thereby forming the clastic Lower Mn-1 ore layer. The remaining manganese was simultaneously deposited on the basin floor with clastic clay and silt from turbidity currents, thereby forming the Upper Mn-1 clastic–chemical ore layer. The sedimentation of Mn-1 and its host IFs was controlled by seawater saturation and homogeneous oxidation, which caused manganese and iron sedimentation and the death of microorganisms, generating mangano-ferriferous sediments with high P, Co and Ni contents. Mn-2 formed during periods of tectonic quiescence through water influxes that carried abundant microbes, Fe(II), Mn(II), and SiO2. Under UV radiation, these microbes oxidized Mn(II) and Fe(II) to form hydroxides and died, thereby forming biomass that was enriched in P, Co and Ni and minor carbonate adjacent to and below the oxycline. These microbes also formed kremydilites, oblate structures that resemble manganese stromatolites, within the biomass and produced CH4 and/or H2 gas bubbles. During early diagenesis, wormlike organisms inhabited the biomass and probably separated iron from manganese to produce cryptomelane microbialites, which agglutinated to form manganese micronodules that coalesced to form the massive layer Mn-2. This process ended with the disappearance of microorganisms and the sedimentation of the IFs, and a new water influx generated layer Mn-3 via the same process. The final seawater upwelling precipitated IFs in the basin depocenter, whereas limestone from the Tamengo Formation was deposited along the basin’s edges. The diagenesis initially transformed the manganese oxides into cryptomelane and then into hollandite.
ISSN: 0169-1368

hal-01684668
https://hal.archives-ouvertes.fr/hal-01684668
DOI : 10.1016/j.oregeorev.2017.09.018

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Cold seeps, located on sea floors and frequently fueled with methane, have been much studied for the formation of carbonate nodules, crusts or masses resulting from the activity og communities of anaerobic bacteria. In this paper, we examine the impact of cold seepage on their caging sediments, as far as their geochemical composition and microfaunal content are concerned. To this end, two fossil cold seeps of the Jurassic Beauvoisin site (Vocontian Trough, SE-France) are studied, focusing on the redox-sensitive and/or sulfide-forming trace metals. We observe that: 1) the carbonate edifices of the cold seeps are enriched in specific elements, namely, Sr, Mo As and Sb, compared to their caging marlstones, and 2) the benthic foraminifer populations were present close to the edifices. The Sr enrichment is ascribed to a contamination of the seeping fluids at the contact with underlying evaporites; the Mo-As-Sb enrichment may have several, non-exclusive, origins. We retain two scenarios; in the first one, the enrichment is due to the ascending fluids that could collect these elements when passing through thick shaly formations; in the second scenario, Mo, As and Sb were supplied to the sites of carbonate precipitation together with Fe- and Mn-oxy-hydroxides (the so-called particulate shuttle process). We favor the second scenario (possibly coupled to the first one) because the rather uncommon Mo-As-Sb association is also observed for reducing sediments deposited under the influence of Fe-Mn-shuttling.
ISSN: 0009-2541

hal-00806655
https://hal.archives-ouvertes.fr/hal-00806655
DOI : 10.1016/j.chemgeo.2012.12.012

Éditeur(s) : Elsevier
Résumé : The accumulation of nine heavy metals in fine-grained sediments from the mangrove fringed coast of French Guiana is evaluated. The dynamic features of the South American tropical coastline, from the Amazon to the Orinoco Rivers, result in mangrove sediments being alternately submitted to phases of erosion and net sedimentation a few tens of years long. This process influences the distribution of the heavy metals associated with these frequently re-mobilized deposits. Sedimentary cores and mangrove plant samples were collected, at different seasons, in various swamps characterized by different properties (content of sedimentary organic matter, distance from sea water and fresh water). The ranges of measured concentrations expressed in mu mol g(-1) were the following: Cu (0.06 to 0.61), Co (0.12 to 0.68), Pb (0.08 to 0.18), Ni (0.32 to 0.76), Cr (0.61 to 1.40), Zn (1.25 to 5.94), Mn (4.36 to 45.4) and Fe (441 to 1128). No differences were found between sediments from mangroves developing upstream and downstream of urban areas, i.e. Cayenne and Kourou. This suggests that the content of mangrove sediments in heavy metals along the coastline of French Guiana is essentially the result of the continuous alternation of accumulation and transport phases occurring upstream after departing from the Amazon watershed. The sources of this heavy metals content are thus difficult to identify. However it is well known that the alluvium produced by the natural erosion of the Amazonian soils is naturally enriched in mercury. Also, the run-off from gold mining activities is known to contribute to mercury pollution. Ranges in total Hg were between 0.15 and 2.57 nmol g(-1), with mean values close to 0.41 nmol g(-1), and were clearly correlated with total organic carbon except for some outstanding high values, which may be a result of rapid geochemical changes. Heavy metal concentrations showed variations with depth. The redox conditions and the decay processes affecting the organic matter control the cycling of iron and manganese, which in turn control the concentrations and associations of heavy metals. These preliminary results suggest that the variations in heavy metal content with depth or between mangrove areas result largely from diagenetic processes rather than changes in metal input resulting from local human activities. (c) 2005 Elsevier B.V. All rights reserved.
Marine Chemistry (0304-4203) (Elsevier), 2006 , Vol. 98 , N. 1 , P. 1-17

Droits : 2005 Elsevier B.V. All rights reserved
http://archimer.ifremer.fr/doc/2006/publication-1041.pdf
DOI:10.1016/j.marchem.2005.06.001
http://archimer.ifremer.fr/doc/00000/1041/

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
This study presents the geochemical composition of superficial sediment under oxic and suboxic bottom water conditions along the Chilean continental margin (SE Pacific), where evidence for benthic chemosynthetic activity associated with diffuse seeping of chemically reduced fluids has been reported. The exploration was carried out at: (1) the Chilean Triple Junction (CTJ), at a water depth of ∼2900 m, with the additional indication of hydrothermal activity near a methane-rich cold-seep area (46°S) (German et al., 2010); and (2) the El Quisco methane seep site (EQSS), at ∼340 m water depth (33°S) (Melo et al., 2007; Krylova et al., 2014). While the deeper CTJ is located within an oxic environment (dissolved oxygen in the bottom waters: 164 μM), the shallower EQSS lies within a suboxic environment (dissolved oxygen in bottom water: 23 μM), located within the lower limit of the SE Pacific oxygen minimum zone (OMZ).Pore water from short cores was analyzed for dissolved major, minor, and trace elements (Cl, Na, Mg, K, Ca, Sr, Si, B, P, Ba, Pb, Mn, Fe, Cd, U, and Mo), δ13DIC, sulfide, sulfate, and methane. The solid sediment fraction was likewise analyzed for total organic carbon (TOC), metals, and redox potential. Elevated sediment temperatures were found in superficial sediments (5–13 °C) at the CTJ site, which could be due to warm fluids associated with the proximity of the ridge, where hydrothermal vents may occur. Reduced fluids were also present here, indicated by higher Mn fluxes toward the water column even in oxidized sediments (RPD > 8 cm), which contrasted with the lower fluxes in reduced sediments of the EQSS site (RPD ∼ 2 cm). 13C-depleted DIC, anomalously low pore water Cl (∼15 ppb), and low concentrations of other major elements may be the result of dilution by fluid seeping and precipitation of major elements, producing authigenic enrichment (Ca, Mg, Sr). The fluid could also: (a) be diluted by pure water produced during methane hydrate dissociation, as observed in other cold-seep areas; and (b) correspond to clay mineral dehydration, as reported in plate subduction systems. The reducing conditions established at the CTJ conduct the Cd enrichment at a similar magnitude of that seen at the shallower suboxic site (EQSS). Evidence of chimney or vent fauna was not observed. At the EQSS, higher TOC and total sulfide contents were consistent with enhanced deposition of organic matter and reducing conditions developed in the OMZ, favoring the authigenic enrichment of Cd, U and Pb. The geochemical evidence, based only on methane concentrations and δ13DIC, is insufficient to establish the presence of methane seeps, as previously reported.
ISSN: 0079-6611

hal-01412700
https://hal.archives-ouvertes.fr/hal-01412700
DOI : 10.1016/j.pocean.2016.09.002

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Trace metals (Cd, U, Co, Ni, Cu, Ba, Fe, Mn), total organic carbon (TOC) and C and N stable isotope signatures (delta C-313 and delta N-15) were determined in short sediments cores from the inner and outer shelf off Concepcion, Chile (similar to 36 degrees S). The objectives were to establish the effect of environmental conditions on trace metal distributions at two shelf sites, one affected by seasonal oxygenation and the other by permanent low oxygen conditions due to the presence of the oxygen minimum zone (OMZ). We evaluate trace metals as proxies of past changes in primary productivity and the bottom water oxygen regime. Concentrations of pore water sulfides and NH4+ were also measured as indicators of the main diagenetic pathways at each site. Our results for the inner shelf (seasonal suboxia) suggest that the oxidative state of the sediments responds to seasonal pulses of organic matter and that seasonal oxygenation develops during high and low primary productivity in the water column. Here, positive fluxes (to the water column) estimated from pore water concentrations of several elements were observed (Ba, Co, Ni, Fe and Mn). The less reduced environment at this site produces authigenic enrichment of Cu associated with the formation of oxides in the oxic surface sediment layer, and the reduction of U within deeper sediment sections occur consistently with negative estimated pore water fluxes. In the outer shelf sediments (permanent suboxia, OMZ site), negative fluxes (to the sediment) were estimated for all elements, but these sediments showed authigenic enrichments only for Cd, Cu and U. The short oxygenation period during the winter season did not affect the accumulation of these metals on the shelf. The distribution of Cu, Cd and U have been preserved within the sediments and the authigenic accumulation rates estimated showed a decrease from the deep sections of the core to the surface sediments. This could be explained by a gradual decrease in the strength of the OMZ in the last 100 years, in combination with periods of strong oxygenations during El Nino events. (C) 2011 Elsevier Ltd. All rights reserved.
ISSN: 0278-4343

hal-00745672
https://hal.archives-ouvertes.fr/hal-00745672
DOI : 10.1016/j.csr.2011.11.006

Éditeur(s) : HAL CCSD Elsevier
Résumé : Iron content of the bulk marine sediment from the Chilean continental margin has been used to infer millenial-scale climate changes in southeast Pacific [Lamy, F., Klump, J., Hebbeln, D., Wefer, G., 2000. Rapid climate change in northern Chile over the last 80 ka recorded in a marine sediment core. Terra Nova 12: 8–13]. Changes of iron contents have been related to a varying contribution of Andean (Fe-rich) versus Coastal Range (Fe-poor) source rocks ultimately controlled by continental rainfall changes. However, variations observed could also be produced by changes in the proportions of two components in the sediment — a detrital component with low and constant Fe content and an authigenic phase (Fe oxide, pyrite, apatite, etc.) with high Fe content. A sequential extraction has been used to partition the total iron content in the sediment of core GeoB 7101 at the continental margin of Chile. The extraction steps included five fractions: exchangeable, bound to carbonates, bound to Fe–Mn oxides, bound to organic matter, and residual. Iron appeared to be mainly present in the residual fraction, i.e. in the detrital component. Our study indicates that total Fe or Fe/Al may be used to infer millenial-scales climate changes in the southeastern Pacific.
ISSN: 0025-3227

hal-00407253
https://hal.archives-ouvertes.fr/hal-00407253
DOI : 10.1016/j.margeo.2007.03.006

Éditeur(s) : HAL CCSD Elsevier
Résumé : Detailed sedimentological investigations on numerous outcrops and drill-core sections in the 2.1-Ga-old Franceville basin, Gabon, provide evidence for a large-scale injectite network. The injectites were formed by the injection of sands through a thickness of about 150 m of the FB1 Member, and now cover a minimum area of 70 km2 corresponding to the Bangombé plateau, but are also recognized close to Franceville 35 km farther south-east. The injectite lithology corresponds to a mud- or carbonate-supported sandstone characterized by a loose and uncompacted fabric contrasting with the host-rock. Because the injectites are often parallel to subparallel to the stratification, they were misinterpreted as depositional beds by previous authors. At outcrop, the injectite bodies exhibit sill, dyke, wing and protrusive geometries emplaced during early burial within poorly compacted material, with partial wall erosion and dissociation. The source of the sand material is attributed to a channel-levee turbidite depositional system located in the lower part of the FB1 Member. These deposits were buried by a thick biochemical muddy cap deposited during a starvation phase, which increased the seal capacity of the system. This type of architecture has a high potential to develop compaction disequilibrium during burial. Moreover, in the case of the Francevillian injectites, the abundance of microbial organic matter favoured early methane degassing and lateral charging of the sand reservoir. The overpressure in the channels was periodically released during early burial, through the effect of rapid sedimentary and tectonic loading, and possible seismic activity. The fluidized sand was injected according to a symmetrical wing pattern. Thus, the injected masses caused a local decrease in the grade of the lateritic manganese ore deposit of the Bangombé plateau.
ISSN: 0301-9268

hal-01667217
https://hal.archives-ouvertes.fr/hal-01667217
DOI : 10.1016/j.precamres.2017.09.022