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

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

First evidence for the Cenomanian-Turonian oceanic anoxic event (OAE2, Bonarelli event) from the Ionian Zone, western continental Greece

Integrated biostratigraphic (planktonic foraminifera, calcareous nannofossils), chemostratigraphic (bulk C and O isotopes) and compound-specific organic geochemical studies of a mid-Cretaceous pelagic carbonate—black shale succession of the Ionian Zone (western Greece), provide the first evidence for the Cenomanian–Turonian oceanic anoxic event (OAE2, ‘Bonarelli’ event) in mainland Greece. The event is manifested by the occurrence of a relatively thin (35 cm), yet exceptionally organic carbon-rich (44.5 wt% TOC), carbonate-free black shale, near the Cenomanian–Turonian boundary within the Vigla limestone formation (Berriasian–Turonian). Compared to the ‘Bonarelli’ black-shale interval from the type locality of OAE2 in Marche–Umbria, Italy, this black shale exhibits greatly reduced stratigraphic thickness, coupled with a considerable relative enrichment in TOC. Isotopically, enriched δ[superscript 13]C values for both bulk organic matter (−22.2‰) and specific organic compounds are up to 5‰ higher than those of underlying organic-rich strata of the Aptian-lower Albian Vigla Shale member, and thus compare very well with similar values of Cenomanian–Turonian black shale occurrences elsewhere. The relative predominance of bacterial hopanoids in the saturated, apolar lipid fraction of the OAE2 black shale of the Ionian Zone supports recent findings suggesting the abundance of N[subscript 2]-fixing cyanobacteria in Cretaceous oceans during the Cenomanian–Turonian and early Aptian oceanic anoxic events

A Holocene "frozen accident": sediments of extreme paleofloods and fires in the bedrock-confined upper Huis River, Western Cape, South Africa

Wildfires and flooding events are common and are forceful intrinsic controls over landscape evolution, biodiversity, and preserved sediment architecture in dryland environments. Charcoal-bearing Holocene flood sediments of the upper Huis River provide a rare perspective on the powerful and episodic sedimentary processes in a bedrock-confined fluvial setting in the tectonically stable SW Cape Fold Belt in South Africa. The sediments described in this paper are associated with high-magnitude, debris-flow-dominated paleofloods, and their charcoal content is linked to a series of radiocarbon-dated Holocene paleofires that occurred from ∼ 2165 ± 37 BP to ∼ 653 ± 35 BP. The five sedimentary facies associations are documented as products of: a) noncohesive pseudoplastic debris flows; b) transitional, high-matrix-strength debris flows with heterogeneous fluid content and flow behavior; c) low-cohesion debris flows; d) hyperconcentrated flows; and e) fluvial channel flow in the upper Huis River. The last is interpreted mainly from massive, subrounded to subangular boulder bars, which provide key evidence for the dramatic scouring of the upper Huis valley. The paleofloods, which not only filled the valley with debris-flow sediments up to 12 m thick, but also subsequently flushed it out nearly to the bedrock, had estimated extreme discharges of few thousands of m3/s. In summary, the upper Huis River sediments are exceptional because they preserve the geological record of recurring fires, and at least three extreme paleofloods (i.e., massive sedimentation events) over a period of ∼ 1500 years in an area typified by the fire-prone and fire-dependent Fynbos Biome. Furthermore, this study provides insights into what the gaps in the commonly fragmented bedrock-confined alluvial stratigraphic record would be like, should there be “more record than gap.

Fraction-specific controls on the trace element distribution in iron formations: Implications for trace metal stable isotope proxies

Iron formations (IFs) are important geochemical repositories that provide constraints on atmospheric and ocean chemistry, prior to and during the onset of the Great Oxidation Event. Trace metal abundances and their Mo-Cr-U isotopic ratios have been widely used for investigating ocean redox processes through the Archean and Paleoproterozoic. Mineralogically, IFs consist of three main Fe-bearing fractions: (1) Fe-Ca-Mg-Mn carbonates, (2) magnetite and/or hematite and (3) Fe-silicates. These fractions are typically fine-grained on a sub-μm scale and their co-occurrence in varying amounts means that bulk-rock or microanalytical geochemical and stable isotope data can be influenced by cryptic changes in mineralogy. Fraction specific geochemical analysis has the potential to resolve mineralogical controls and reveal diagenetic versus primary precipitative controls on IF mineralogy. Here we adapt an existing sequential extraction scheme for Fe-phases (Poulton and Canfield, 2005) to the high Fe-content in IF and the specific three-fraction mineralogy. We optimized the scheme for magnetite-dominated Archean IFs using samples from the hematite-poor Asbestos Hills Subgroup IF, Transvaal Supergroup, South Africa. Previously commonly-used hydroxylamine-HCl and dithionite leaches were omitted since ferric oxides are quantitatively insignificant in these IF samples. The acetate leach was tested at variable temperatures, reaction times and under different atmospheres in order to ensure that all micro-crystalline Fe-carbonates were effectively dissolved, resulting in an optimum extraction for 48 h at 50 °C under anoxic conditions. The dissolution of magnetite by NH4-oxalate was also tested, resulting in an optimum extraction for 24 h under an ambient atmosphere. Finally, a HF-HClO4-HNO3 leach was used to dissolve the residual silicate fraction which has to date not been considered in detail in IF. Accuracy of the extraction technique was generally excellent, as verified using 1) elemental recoveries, 2) comparison of major and trace element distributions against mineralogy and 3) comparison to results from microanalytical techniques. This study focuses on the distribution of three frequently used geochemical proxies in IF; U, Mo and Cr. Molybdenum abundances in the Kuruman and Griquatown IF are low and show an apparent correlation with mineralogical variability, as determined by the sequential extraction. This suggests that changes in bulk-rock mineralogy, rather than redox chemistry might significantly affect Mo stable isotopes. For Cr, a minor bulk-rock stratigraphic increase can be related to the oxide and silicate fraction. However, a positive relationship with Zr indicates that this was also controlled by detrital or volcanic ash input. Uranium is predominantly bound to the silicate fraction and shows clear correlations with Zr and Sc implying detrital reworking under anoxic conditions. The discrepant behaviour of these three proxies indicate that mineralogy should be taken into account when interpreting heterogeneous bulk-rock samples and that fraction specific techniques will provide new insights into the evolution of atmosphere and ocean chemistry

High-­resolution bio-­ and chemostratigraphy of an expanded record of Oceanic Anoxic Event 2 (Late Cenomanian–Early Turonian) at Clot Chevalier, near Barrême, SE France (Vocontian Basin, SE France)

A newly located exposure of the Niveau Thomel, an organic-­‐rich level at the Cenomanian–Turonian boundary, provides a highly expanded record of Oceanic Anoxic Event (OAE) 2, excepted for the lower relatively condensed glauconite-­rich part of the section. The new locality, close to Barrême in the Vocontian Basin, SE France, is developed in deep-­water hemi-­pelagic facies (shales, marls, marly limestones, variably enriched in organic matter) and provides an improved understanding of palaeoceanographic events associated with OAE 2. Investigation of the biostratigraphy (nannofossils and planktonic foramininfera), organic and inorganic geochemistry (bulk carbonate δ18O, total organic carbon (TOC), bulk organic, biomarker-specific and carbonate δ13C, major and trace elements, and Rock-­Eval data) has allowed characterization of the sediments in great detail. The combined study further constrains the detailed relationship between bio-­ and chemostratigraphy (particularly with respect to the details of the well-­displayed positive carbon-­‐isotope excursion) for this interval. The section also provides new evidence, in the form of a positive oxygen-­isotope excursion and an offset between carbonate and organic-­carbon carbon-­isotope records, which confirms the importance of cooling accompanied by a drop in dissolved CO2 in near-­surface waters during the Plenus Cold Event that characterized the early part of OAE 2. Evidence for increased oxygenation of bottom waters, together with elevated concentrations of redox-­sensitive and chalcophilic elements registered elsewhere through the level of the Plenus Cold Event, may be reflected in enhanced concentrations of iron (in glauconite) and nickel in coeval strata from the Clot Chevalier section

Oceanic response to Pliensbachian and Toarcian magmatic events: Implications from an organic-rich basinal succession in the NW Tethys

The Bächental bituminous marls (Bächentaler Bitumenmergel) belonging to the Sachrang Member of the Lower Jurassic Middle Allgäu Formation were investigated using a multidisciplinary approach to determine environmental controls on the formation of organic-rich deposits in a semi-restricted basin of the NW Tethys during the Early Jurassic. The marls are subdivided into three units on the basis of mineralogical composition, source-rock parameters, redox conditions, salinity variations, and diagenetic processes. Redox proxies (e.g., pristane/phytane ratio; aryl isoprenoids; bioturbation; ternary plot of iron, total organic carbon, and sulphur) indicate varying suboxic to euxinic conditions during deposition of the Bächental section. Redox variations were mainly controlled by sea-level fluctuations with the tectonically complex bathymetry of the Bächental basin determining watermass exchange with the Tethys Ocean. Accordingly, strongest anoxia and highest total organic carbon content (up to 13%) occur in the middle part of the profile (upper tenuicostatum and lower falciferum zones), coincident with an increase in surface-water productivity during a period of relative sea-level lowstand that induced salinity stratification in a stagnant basin setting. This level corresponds to the time interval of the lower Toarcian oceanic anoxic event (T-OAE). However, the absence of the widely observed lower Toarcian negative carbon isotope excursion in the study section questions its unrestricted use as a global chemostratigraphic marker. Stratigraphic correlation of the thermally immature Bächental bituminous marls with the Posidonia Shale of SW Germany on the basis of C27/C29 sterane ratio profiles and ammonite data suggests that deposition of organic matter-rich sediments in isolated basins in the Alpine realm commenced earlier (late Pliensbachian margaritatus Zone) than in regionally proximal epicontinental seas (early Toarcian tenuicostatum Zone). The late Pliensbachian onset of reducing conditions in the Bächental basin coincided with an influx of volcaniclastic detritus that was possibly connected to complex rifting processes of the Alpine Tethys and with a globally observed eruption-induced extinction event. The level of maximum organic matter accumulation in the Bächental basin corresponds to the main eruptive phase of the Karoo-Ferrar large igneous province (LIP), confirming its massive impact on global climate and oceanic conditions during the Early Jurassic. The Bächental marl succession is thus a record of the complex interaction of global (i.e., LIP) and local (e.g., redox and salinity variations, basin morphology) factors that caused reducing conditions and organic matter enrichment in the Bächental basin. These developments resulted in highly inhomogeneous environmental conditions in semi-restricted basins of the NW Tethyan domain during late Pliensbachian and early Toarcian time

Microbe-mineral interactions in naturally radioactive beach sands from Espirito Santo, Brazil: experiments on mutagenicity

Previous studies on naturally radioactive materials suggested that they can have a mutagenic effect on plants (growing in sands in Kerala, South West India), and on bats (dwelling in an abandoned underground mine of primary monazite ore in Namaqualand, Western Cape, South Africa). We hypothesised, based on previous theoretical work, that radioactive sands would not induce mutants in microorganisms over time scales typical of doubling times in the natural environment. The potential of exceptionally monazite (Th)-rich mineral sands collected from the coast of Espirito Santo, Brazil to induce single-point reversion in Escherichia coli cultures (both repair-competent and repair-deficient strains) was tested using the tryptophan reverse mutation assay. The results show that at least on a short-term scale (1-7 days), the monazite-rich sands did not cause an increase in reversion above background