The early proterozoic Makganyene glacial event in South Africa : its implication in sequence stratigraphy interpretations, paleoenvironmental conditions and iron and manganese ore deposition

The Makganyene Formation forms the base of the Postmasburg Group in the Transvaal Supergroup in the Griqualand West Basin. It consists of diamictites, sandstones, banded iron-formations (BIFs), shales, siltstones and carbonates. It is generally accepted that the Makganyene Formation rests on an erosive regional unconformity throughout the Northern Cape Province. However this study demonstrates that this stratigraphic relationship is not universal, and conformable contacts have been observed. One of the principal aims of this study is to identify the nature of the Makganyene basal contact throughout the Griqualand West Basin. Intensive fieldwork was carried out from Prieska in the south, to Danielskuil in the north. In the Sishen and Hotazel areas, only borehole material was available to assess the stratigraphy. The Griquatown Fault Zone delimits the boundary between the deep basin and platform facies. The Koegas Subgroup is only present south of the Griquatown Fault Zone, where it pinches out. However, the transition Griquatown BIFs-Koegas Subgroup occurs in lacustrine deposits on the Ghaap platform (Beukes, 1983). The Griquatown Fault Zone represents the edge of the basin, which corresponds to a hinge rather than a fault zone. The Makganyene Formation rests with a conformable contact on the Koegas Subgroup south of the Griquatown Hinge Zone, and north of it the Makganyene Formation lies unconformably on the Asbestos Hills Subgroup. The Makganyene Formation displays lateral facies changes that reflect the paleogeography of the Griqualand West Basin, and the development of ice sheets/shelves. The Ghaap platform is characterised by coarse immature sand interbedded with the diamictites. The clasts in this area contain local Asbestos Hills material and no dropstones are present. Such settings are typical of sediments that are being deposited below a grounded ice mass. At the Griquatown Hinge Zone, the sandstone lenses are smaller, and the clasts consist of chert, of which a great number are striated and faceted. In the Matsap area, the presence of dropstones is strong evidence for the presence of a floating ice shelf that released its material by basal melting. Further south, the Makganyene Formation contains stromatolitic bioherms that only form if clastic contamination is minimal and therefore the ice that transported the detritus to the basin did not extend far into open sea conditions. The base of the Hotazel Formation also contains diamictite levels. Dropstones have been identified, implying a glacial origin. The Hotazel diamictites are interbedded with hyaloclastites and BIFs. The Makganyene glacial event, therefore, was not restricted to the Makganyene Formation, but also included the Ongeluk Formation, through to the base of the Hotazel Formation. Petrographic studies of the Makganyene Formation and the base of the Hotazel Formation reveal mineral assemblages that are diagnostic of early to late diagenetic crystallisation and of low-grade metamorphism not exceeding the very low green-schist facies. The facies identified display the same sense of basin deepening, from shallow high-energy Hotazel area on the Ghaap platform, to the deep basin in the Matsap area. Whole-rock geochemical analyses reveal that the elemental composition of the Makganyene Formation is very similar to that of the Asbestos Hills BIFs, which were the most important source of clastic detritus for the Makganyene Formation. However, minor amounts of carbonates of the Campbellrand Subgroup, as well as a felsic crustal input from the Archean granitoid basement, made contributions. On the Ghaap platform, the Makganyene diamictite is enriched in iron, calcium, and magnesium, while in the deeper parts of the basin the diamictites are enriched in detrital elements, such as titanium and aluminium, which occur in the fine clay component. The Hotazel diamictite displays a distinct mafic volcanic input, related to the extrusion of the Ongeluk basaltic andesites, which was incorporated in the glacial sediments. Sequence stratigraphy is based on the recognition of contacts separating the different systems tracts that compose a depositional sequence. However, because the basal contact of the Makganyene Formation has not been properly identified in previous work, no correct model has been proposed so far. Therefore correlations between the Griqualand West and the Transvaal basins, based on lithostratigraphic similarities and extrapolations of unconformities, have to be reviewed, especially since the publication of new radiometric ages contradict all previously proposed correlations. It is proposed here that the Transvaal Supergroup in the Griqualand West Basin represents a continuous depositional event that lasted about 200 Ma. The Makganyene glacial event occurred during changing conditions in the chemistries of the atmosphere and ocean, and in the continental configuration. A Snowball Earth event has been proposed as the causative process of such paleoenvironmental changes. However, evidence presented here of less dramatic glacial conditions, with areas of ice-free waters, implies an alternative to the Snowball Earth event. The paleoenvironmental changes are thought to represent a transition from an anaerobic to aerobic atmosphere, that was responsible for the global cooling of the surface of the Earth, Such a glacial event may have aided in the large-scale precipitation of iron and manganese in areas of intense upwellings

Deconstructing the Transvaal Supergroup, South Africa: implications for Palaeoproterozoic palaeoclimate models

Current correlations between the Pretoria and Postmasburg Groups of the Transvaal Supergroup are shown to be invalid. The Postmasburg Group is also demonstrated to be broadly conformable with the underlying Ghaap Group and therefore considerably older (~2.4 Ga) than previously supposed. The new stratigraphy documents an extensive (100 Ma) and continuous cold-climate episode with a glacial maximum at the Makganyene Formation diamictite. Iron formations of the underlying Asbesheuwels and Koegas Subgroups and overlying Hotazel Formation have similar origins, related, respectively, to the onset and cessation of the glacial event. This interpretation of the Transvaal Supergroup stratigraphy has significant implications for various Palaeoproterozoic environmental models and for the timing of the development of an oxygenated atmosphere

Stratigraphy and geochemistry of the Makganyene formation, Transvaal supergroup, Northern Cape, South Africa

The Makganyene Formation forms the base of the Postmasburg Group in the Transvaal Supergroup of the Northern Cape Province. The Makganyene Formation has diamictite as the main rock type, but siltstone, sandstone, shale, and iron-formations are also present. A glacial origin has been proposed in the past due to the presence of dropstones, faceted and striated pebbles. Typically, the Makganyene Formation contains banded iron-formations interbedded with clastic rocks (shale, siltstone, sandstone and diamictites) at the contact with the underlying iron-formations. This transitional zone is generally overlain by massive or layered diamictites which contain poorly sorted clasts (mainly chert) within a shaly matrix. Striated pebbles have been found during field work, and dropstones have been observed in diamictites and banded iron-formations during the study. The top of the Makganyene Formation contains graded cycles interbedded with diamictites and thin layers of andesitic lavas from the Ongeluk Formation. The basal contact of the Makganyene Formation with the underlying Koegas Subgroup was described as unconformable by previous workers. However field work localised in the Rooinekke area shows a broadly conformable and interbedded contact with the underlying Koegas Subgroup. As described above, banded iron-formations are interbedded with the clastic rocks of the Makganyene Formation. Moreover, boreholes from the Sishen area display the same interbedding at the base of the Makganyene Formation. This suggests that no significant time gap is present in the whole succession between the Ghaap and Postmasburg Group. The Transvaal Supergroup in the Northern Cape displays the following succession : carbonates-BIFs-diamictites/ lava-BIFs-carbonates. The Makganyene Formation is thus at the centre of a symmetrical lithologic succession. Bulk rock compositions show that the diamictites have a similar composition to banded iron-formation with regard to their major element contents. Banded iron-formations acted as a source for the diamictites with carbonates and igneous rocks representing minor components. Differences in bulk composition between the Sishen and Matsap areas emphasize that the source of the diamictite was very localised. The Chemical Index of Alteration (CIA) has been calculated, but since the source dominant rock was iron-formation, this index cannot be usefully applied to the diamictites. ACN, A-CN-K, and A-CNK-FM diagrams confer a major importance in sorting processes due to the separation between the fine and coarse diamictites. The interbedded iron-formations display little clastic contamination indicating deposition in clear water conditions. However, dropstones are present in one borehole from the Matsap area, indicating that iron-formation took place under ice cover, or at least under icebergs. Stable isotope studies show that the iron-formations, interbedded towards the base of the Makganyene Formation, have similar values to the iron-formations of the Koegas Subgroup. As a result of the above observations, new correlations are proposed in this study, relating the different Transvaal Supergroup basins located on the Kaapvaal Craton. The Pretoria Group of the Transvaal Basin has no correlative in the Griqualand West Basin, and the Postmasburg Group of the Northern Cape Basin has no lateral equivalent in the Transvaal Basin. These changes have been made to overcome problems present in the current correlations between those two basins. The Makganyene Formation correlates with the Huronian glaciations which occurred between 2.4 and 2.2 Ga ago in North America. Another Precambrian glaciation is the worldwide and well-studied Neoproterozoic glaciation (640 Ma). At each of these glaciations, major banded iron-formation deposition took place with associated deposition of sedimentary manganese in post-glacial positions. The central position of the Makganyene Formation within the Transvaal Supergroup in the Northern Cape emphasizes this glacial climatic dependence of paleoproterozoic banded iron-formation and manganese deposition. However these two Precambrian glaciations are interpreted in paleomagnetic studies as having occurred near to the equator. The controversial theory of the Snowball Earth has been proposed which proposes that the Earth was entirely frozen from pole to pole. Results from field work, sedimentology, petrography and geochemistry were integrated in a proposed depositional model of the Makganyene Formation occurring at the symmetrical centre of the lithologic succession of the Transvaal Supergroup. At the beginning of the Makganyene glaciation, a regression occurred and glacial advance took place. The diamictites are mostly interpreted as being deposited from wet-based glaciers, probably tidewater glaciers, where significant slumping and debris flows occurred. Any transgression would cause a glacial retreat by rapid calving, re-establishing the chemical sedimentation of banded iron-formations. These sea-level variations are responsible for the interbedding of these different types of rocks (clastic and chemical). The end of the Makganyene glacial event is characterised by subaerial eruptions of andesitic lava of the Ongeluk Formation bringing ashes into the basin. Banded iron-formation and associated manganese accumulations are climate-dependant. Glacial events are responsible for the build up of metallic ions such as iron and manganese in solution in deep waters. A warmer climate would induce a transgression and precipitation of these metallic ions when Eh conditions are favourable. In the Transvaal Supergroup, the climatic variations from warm to cold, and cold to warm are expressed by the lithologic succession. The warm climates are represented by carbonates. Cold climates are represented by banded iron-formations and the peak in cold climate represented by the diamictites of the Makganyene Formation. These changes in climate are gradual, which contradict the dramatic Snowball Earth event: a rapid spread of glaciated areas over low-latitudes freezing the Earth from pole-to-pole. Therefore, to explain low-latitude glaciations at sea-level, a high obliquity of the ecliptic is most likely to have occurred. This high obliquity of the ecliptic was acquired at 4.5 Ga when a giant impactor collided into the Earth to form the Moon. Above the critical value of 54° of the obliquity of the ecliptic, normal climatic zonation reverts, and glaciations will take place preferentially at low-latitudes only when favourable conditions are gathered (relative position ofthe continents and PC02 in the atmosphere)

The geology and geochemistry of the Palaeoproterozoic Makganyene diamictite

The Palaeoproterozoic Earth experienced a global glacial event at 2400 Ma that occurred during the transitional period from anoxic to aerobic conditions in the atmosphere and oceans. The Transvaal Supergroup in the Griqualand West Basin, South Africa, hosts glacial deposits and associated major iron and manganese deposits that are apparently related to these global changes. The focus of this study is to assess the stratigraphy and geochemistry of the glaciogenic Makganyene Formation, in order to constrain its palaeoenvironmental settings. The Makganyene Formation forms the base of the Postmasburg Group and has been regarded as resting on an erosive regional unconformity throughout the Northern Cape Province. Systematic regional field observations and regional mapping carried out during this study demonstrate that this stratigraphic relationship is not universal. The Makganyene Formation is, in fact, conformable with underlying formations of the Koegas Subgroup in the deep southern Prieska basin and rests on an unconformity only on the shallow Ghaap platform to the north-east. The Makganyene Formation displays lateral facies changes that reflect the palaeogeography of the study area, and the advance and retreat of ice sheets/shelves. Geochemical investigations of glacial strata of the Makganyene Formation demonstrate that underlying banded iron formations of the Transvaal Supergroup acted as the main clastic source for the diamictite detritus. Geographic variations in bulk composition of the diamictites correlate well with field observations, and show that sorting processes were controlled largely by the morphology of the palaeobasin. Carbon isotope results emphasize the transitional nature of the Makganyene Formation in terms of the environmental conditions that resulted in widespread global glaciation in the Palaeoproterozoic. On the basis of the above geological evidence, it is proposed that the Transvaal Supergroup in the Northern Cape Province represents a continuous depositional event that lasted approximately 250 Ma and hence provides a unique opportunity for assessing the transitional changes experienced by the Palaeoproterozoic Earth

Synthesis of Ni-poor NiO nanoparticles for p-DSSC applications

International audienceTo improve the performances of p-Dye Sensitized Solar Cell (p-DSSC) for the future, the synthesis of modified p-type nickel oxide semiconductor, commonly used as photocathode in such devices, was initiated with Ni3O2(OH)4 as precursor. This specific nickel oxyhydroxide was first characterized by X-ray photo-electron spectroscopy and magnetic susceptibility measurements. Then its thermal decomposition was thoroughly studied in order to control the particles size of the as-prepared NiO nanopowders. Low temperature decomposition in air of this precursor allows the formation of Ni1-xO nanoparticles with a large amount of Ni vacancies and specific surface areas up to 250 m2.g-1. Its ammonolysis at 250°C leads to nanostructured N-doped NiO (NiO:N) materials

Synthesis of Ni-poor NiO nanoparticles for DSSC-p applications

International audienceOver the last decade, p-type semiconductors (SC) have known a renewed interest. Indeed these materials may have potentialapplications for light-emitting diodes, transistors, solar cells, etc. Since the achievement of the first Dye Sensitized Solar Cells (DSSC) by Grätzel in 1991 a new generation of solar cells has been developed where the n-type SC is replaced by a p-type one. This leads to the photo-injection of holes instead of electrons in the circuit. To date nickel oxide (NiO) is the reference p-type semiconductor.However yields are still far from those of n-DSSC and many studies aim to replace NiO by other systems such as CuAlO2 , CuGaO2,CuCrO2 or NiCo2O4 nanoparticles. Following our recent synthesis of N doped ZnO with stabilization of p-type charge carriers, wefocus now on the preparation of N doped NiO nanoparticles to improve the p-type conductivity of NiO. We study here the chemicalreactivity of a nickel oxyhydroxide precursor under air and ammonia that conducts to nanostructured Ni-poor NiO

Focused fluid-flow structures potentially caused by solitary porosity waves

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The pre-breakup stratigraphy and petroleum system of the Southern Jan Mayen Ridge revealed by seafloor sampling

The authors would like to acknowledge the contribution from the vessel’s crew (captain I. Rasmussen) and operator (Thor Ltd), the two surveyors (K. Høysæth and H.B. Bortne), and two sampling assistants (F. Gausepohl and A.-M. Voelsch). Sverre Planke and Dougal Jerram are partly funded through a Norwegian Research Council Centers of Excellence project (project number 223272, CEED). Adriano Mazzini is funded by the European Research Council under the European Union's Seventh Framework Programme Grant agreement n° 308126 (LUSI LAB project, PI A. Mazzini). TGS and VBPR funded the cruise and allowed the publication of the data and interpretation. Steve Killops from APT refined our interpretation of the biomarker data. The reviewers and the editor are also thanked for their constructive comments. Finally, this article is dedicated to the biostratigrapher Haavard Selnes who sadly passed away in 2015.Peer reviewedPostprin

Quantification and restoration of the pre‐drift extension across the NE Atlantic conjugate margins during the mid‐Permian‐early Cenozoic multi‐rifting phases

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Structural and fluid-migration control on hill-hole pair formation: Evidence from high-resolution 3D seismic data from the SW Barents Sea

Hill-hole pairs are subglacial landforms consisting of thrust-block hills and associated source depressions. Formed by evacuation of material where ice sheets have been locally frozen to the substrate, they give insights into paleo-ice-sheet dynamics. The aim of this study was to document the relationships between ancient hill-hole pairs identified on a buried glacial unconformity with the structure of the underlying sedimentary deposits, and then to determine if the basin geology and glacial fluid migration pathways promoted local subglacial freeze-on during the hill-hole pair formation. The study is based on seismic geomorphological interpretation of four high-resolution 3D seismic cubes covering an area of 800 km2 in the SW Barents Sea, and fluid seepage data from 37 gravity cores. The seismic datasets allowed the identification of 55 hill-hole pairs along the buried unconformity. The hills are characterized by chaotic to homogenous seismic facies forming up to 19 m high mounds, each covering areas of 2000–644,000 m2. The holes form depressions between 1 and 44 m deep and 2000–704,000 m2 in areal extent, which cut into preglacial Mesozoic bedrock and later infilled by glacial till. The holes are often found above fault terminations. High-amplitude reflections identified along the faults and in the strata below the holes are interpreted as shallow gas migrating upward towards the glacial unconformity. Geochemical data of the seabed sediment cores further indicates an association between hill-hole pair occurrence and present-day thermogenic hydrocarbon seepage. The hill-hole pairs geometries were also used to identify five paleo-ice-flow directions along the glacial unconformity. These ice flows exhibit polythermal regimes, and four of them are parallel to ice-stream flow sets interpreted from glacial lineations. The integrated interpretation supports localized fault-related basal freezing of the Barents Sea Ice Sheet which resulted in the formation of hill-hole pairs when the ice sheet moved. In this context, the faults functioned as migration pathways for deep thermogenic fluids, possibly sourced from leaking Jurassic reservoirs.>p> This study highlights the importance of the underlying geology for ice-sheet dynamics: While hill-hole pairs above glacial till appear to be commonly associated with dispersed gas hydrates, hill-hole pairs above bedrock additionally indicate a link to underlying fault systems and hydrocarbon reservoirs. Freeze-on of underlying bedrock to the basal ice along the strike of faults in sedimentary bedrock explains deeper hill-hole pairs with smaller extents along the glacial unconformity compared to areally larger but shallow hill-hole pairs detected above glacial till on modern seabeds. Such close association between paleo-thermogenic gas seepage and the location of hill-hole pairs strongly support that hill-hole pairs are excellent markers revealing exit points of fluid migration pathways in petroleum system models