Mechanisms and biogeochemical implications of Cenomanian/Turonian black shale formation in North Africa:An integrated geochemical, millennial-scale study from theTarfaya-LaAyoune Basin in SW Morocco

Cenomanian/Turonian (C/T; ~94 Ma ago) black shale successions from various N African basins, in particular from the Tarfaya-LaAyoune Basin (SW Morocco), have been studied in great detail using data from the field (including gamma-ray resistivity logging), sedimentology and advanced geochemical trace metal, biomarker and stable isotope methods. Deposition of these black shale units in most of the region was restricted to a short time envelope termed the C/T oceanic anoxic event (OAE2). During this short period, a favourable combination of factors existed which led to the development of exceptionally strong oxygen-deficiency in the N African Tethys and in particular in the southern proto-North Atlantic oceans. The C/T black shales in N Africa are laterally discontinuous and their distribution and thickness were controlled by the palaeorelief. The thickest and regionally most extensive C/T organic-rich shales in N Africa occur in Morocco namely in the Atlantic Tarfaya-LaAyoune Basin. The laminated biogenic sediments from this NW African shallow marine basin were deposited with very high sedimentation rates (av. 5-10 cm/ka) enabling the investigation of mid-Cretaceous paleoceanographic events at high temporal resolution with respect to rapid climate change and associated hydrocarbon source-rock formation. The low level of thermal maturity and the high degree of sulphurisation of the organic matter (kerogen) makes these black shale successions suitable for advanced inorganic and organic geochemical investigations

Steuerungsmechanismen und biogeochemische Auswirkungen von Schwarzschiefergenese an der Cenoman/Turon-Wende in Nordafrika: Ein integrierte hochauflösender geochemische Studie aus dem Tarfaya-LaAyoune Becken in SW-Marokko

Cenomanian/Turonian (C/T; ~94 Ma ago) black shale successions from various N African basins, in particular from the Tarfaya-LaAyoune Basin (SW Morocco), have been studied in great detail using data from the field (including gamma-ray resistivity logging), sedimentology and advanced geochemical trace metal, biomarker and stable isotope methods. Deposition of these black shale units in most of the region was restricted to a short time envelope termed the C/T oceanic anoxic event (OAE2). During this short period, a favourable combination of factors existed which led to the development of exceptionally strong oxygen-deficiency in the N African Tethys and in particular in the southern proto-North Atlantic oceans. The C/T black shales in N Africa are laterally discontinuous and their distribution and thickness were controlled by the palaeorelief. The thickest and regionally most extensive C/T organic-rich shales in N Africa occur in Morocco namely in the Atlantic Tarfaya-LaAyoune Basin. The laminated biogenic sediments from this NW African shallow marine basin were deposited with very high sedimentation rates (av. 5-10 cm/ka) enabling the investigation of mid-Cretaceous paleoceanographic events at high temporal resolution with respect to rapid climate change and associated hydrocarbon source-rock formation. The low level of thermal maturity and the high degree of sulphurisation of the organic matter (kerogen) makes these black shale successions suitable for advanced inorganic and organic geochemical investigations

Geochemistry of sediment cores GeoB4901-3 and GeoB4901-8 from the southern flank of the Niger Fan

Time series of terrigenous source elements (Al, K, Ti, Zr) from core GeoB4901-8 recovered from the deep-sea fan of the Niger River record variations in riverine sediment discharge over the past 245,000 yr. Although the flux rates of all the elements depend on physical erosion, which is mainly controlled by the extent of vegetation coverage in central Africa, element/Al ratios reflect conditions for chemical weathering in the river basin. Maximum sediment input to the ocean occurs during cold and arid periods, when precipitation intensity and associated freshwater runoff are reduced. High carbonate contents during the same periods indicate that the sediment supply has a positive effect on river-induced marine productivity. In general, variations in the terrestrial signals contain a strong precessional component in tune with changes in low-latitude solar radiation. However, the terrestrial signal lags the insolation signal by several thousand years. K/Al, Ti/Al, and Zr/Al records reveal that African monsoonal precipitation depends on high-latitude forcing. We attribute the shift between insolation cycle and river discharge to the frequently reported nonlinear response of African climate to primary orbital configurations, which may be caused by a complex interaction of the secondary control parameters, such as surface albedo and/or thermohaline circulation

Geochemical characterization of black shales from the Tarfaya Basin

Organic geochemical and petrological investigations were carried out on Cenomanian/Turonian black shales from three sample sites in the Tarfaya Basin (SW Morocco) to characterize the sedimentary organic matter. These black shales have a variable bulk and molecular geochemical composition reflecting changes in the quantity and quality of the organic matter. High TOC contents (up to 18wt%) and hydrogen indices between 400 and 800 (mgHC/gTOC) indicate hydrogen-rich organic matter (Type I-II kerogen) which qualifies these laminated black shale sequences as excellent oil-prone source rocks. Low Tmax values obtained from Rock-Eval pyrolysis (404-425 MC) confirm an immature to early mature level of thermal maturation. Organic petrological studies indicate that the kerogen is almost entirely composed of bituminite particles. These unstructured organic aggregates were most probably formed by intensive restructuring of labile biopolymers (lipids and/or carbohydrates), with the incorporation of sulphur into the kerogen during early diagenesis. Total lipid analyses performed after desulphurization of the total extract shows that the biomarkers mostly comprise short-chain n-alkanes (C16-C22) and long-chain (C25-C35) n-alkanes with no obvious odd-over-even predominance, together with steranes, hopanoids and acyclic isoprenoids. The presence of isorenieratane derivatives originating from green sulphur bacteria indicates that dissolved sulphide had reached the photic zone at shallow water depths (~100m) during times of deposition. These conditions probably favoured intensive sulphurization of the organic matter. Flash pyrolysis GC-MS analysis of the kerogen indicates the aliphatic nature of the bulk organic carbon. The vast majority of pyrolysis products are sulphur-containing components such as alkylthiophenes, alkenylthiophenes and alkybenzothiophenes. Abundant sulphurization of the Tarfaya Basin kerogen resulted from excess sulphide and metabolizable organic matter combined with a limited availability of iron during early diagenesis. The observed variability in the intensity of OM sulphurization may be attributed to sea level-driven fluctuations in the palaeoenvironment during sedimentation

Morocco Basin's sedimentary record may provide correlations for Cretaceous paleoceanographic events worldwide.

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Molybdenum drawdown during Cretaceous Oceanic Anoxic Event 2

During the Cretaceous greenhouse, episodes of widespread ocean deoxygenation were associated with globally occurring events of black shale deposition. Possibly the most pronounced of these oceanic anoxic events (OAE’s) was the Cenomanian-Turonian OAE2 (~94 Ma). However, although certain redox sensitive trace metals tend to be preferentially sequestered in sediments deposited under anoxic conditions, with Mo drawdown being specifically prone to euxinic settings, these elements are generally somewhat depleted in sediments deposited during OAE2. To understand the driving factors responsible for this depleted trace metal drawdown, we have studied a low latitude section from the proto-North Atlantic Ocean (Tarfaya S57), where existing biomarker and iron-sulphur data point to a dominantly euxinic water column, with periodic transitions to ferruginous (Fe-rich) water column conditions. We utilise a variety of redox proxies (Fe-speciation, redox sensitive trace metals and Mo isotopes), which, in combination, allows us to evaluate the detailed nature of ocean redox conditions and hence controls on trace metal drawdown. The results suggest that seawater δ98Mo values may have ranged between ~ 0.6 and 1.1‰ during OAE2, likely connected to changes in the local Mo reservoir as a consequence of low and probably heterogeneous concentrations of Mo in the ocean. The very low Mo/TOC ratios at Tarfaya and elsewhere in the proto-North Atlantic may support a model in which deep-water circulation was partially restricted within and between the North Atlantic and other ocean basins. We propose that the combination of a low and possibly heterogeneous δ98Mo of seawater Mo, together with low Mo/TOC ratios, points to a large decrease in the global oceanic Mo reservoir during OAE2, reflecting a major global scale increase in Mo drawdown under persistent euxinic conditions