Chemistry of Jurassic/Cretaceous black shales

Black shale samples of Jurassic to Cretaceous age recovered during the 'Norwegian Shelf Drilling Program' between 1987 and 1991 from Sites 7430/10-U-01 (Barents Sea), 6814/04-U-02 (Norwegian Shelf near the Lofoten) and 6307/07-U-02 (Norwegian Shelf near Trondheim) were analyzed for major and trace elements. These laminated black shales are characterized by high total organic carbon (TOC) and total sulfur (TS) contents as well as by significant enrichments in several redox-sensitive and/or sulfide-forming trace metals (Ag, Bi, Cd, Co, Cr, Cu, Mo, Ni, Re, Sb, Tl, U, V, and Zn). Enrichment factors relative to 'average shale' are comparable to those found in Cenomanian-Turonian boundary event (CTBE) black shales and Mediterranean sapropels. The Re content is high in the studied black shales, with maximum values up to 1221 ng/g. Re/Mo ratios averaging 2.3*10**-3 are close to the seawater value. High trace metal enrichments and Re/Mo ratios close to the seawater value point to a dominantly anoxic and sulfidic water column during black shale formation. Interbeds with higher Re/Mo ratios, especially in high-resolution sampled core sections, point to brief periods of suboxic conditions. Additionally, enhanced Zn concentrations in the black shales from the Barents Sea support the assumption that hydrothermal activity was also high during black shale deposition. Trace metal signatures of black shales at different drill sites on a transect along the Norwegian Shelf are not only influenced by water depth but also by their location in the boreal realm. Metal enrichments are higher in the northern compared to the southern sites. Volgian (=Tithonian 151-144 Ma BP) black shales exhibit elevated trace metal contents in comparison to their Berriasian (144-137 Ma BP) counterparts. This probably reflects a change in the circulation pattern during periods of black shale formation. Therefore different paleoceanographic conditions, probably controlled by climatic change linked to the transgression of the paleo-sealevel and the North Atlantic opening, may have developed from the Volgian to the Berriasian.

Physical oceanography during UPAT cruise to the Amvrakikos Gulf, August 2009

Oceanographic research in the Amvrakikos Gulf in Western Greece, a semi-enclosed embayment isolated from the Ionian Sea by a narrow, shallow sill, has shown that it is characterised by a fjord-like oceanographic regime. The Gulf is characterised by a well-stratified two layer structure in the water column made up of a surface layer and a bottom layer that are separated by a strong pycnocline. At the entrance over the sill, there is a brackish water outflow in the surface water and a saline water inflow in the near-bed region. This morphology and water circulation pattern makes the Amvrakikos Gulf the only Mediterranean Sea fjord. The investigations have also shown that the surface layer is well oxygenated, whereas in the pycnocline, the dissolved oxygen (DO) declines sharply and finally attains a value of zero, thus dividing the water column into oxic, dysoxic and anoxic environments. At the dysoxic/anoxic interface, at a depth of approximately 35 m, a sharp redox cline develops with Eh values between 0 and 120 mV occurring above and values between 0 and -250 mV occurring below, where oxic and anoxic biochemical processes prevail, respectively. On the seafloor underneath the anoxic waters, a black silt layer and a white mat cover resembling Beggiatoa-like cells are formed. The dysoxic/anoxic conditions appeared during the last 20 to 30 years and have been caused by the excessive use of fertilisers, the increase in animal stocks, intensive fish farming and domestic effluents. The inflicted dysoxia/anoxia has resulted in habitat loss on the seafloor over an area that makes up just over 50% of the total Gulf area and approximately 28% of the total water volume. Furthermore, anoxia is also considered to have been responsible for the sudden fish mortality which occurred in aquaculture rafts in the Gulf in February 2008. Therefore, anoxic conditions can be considered to be a potential hazard to the ecosystem and to the present thriving fishing and mariculture industry in the Gulf.

Diatoms, total organic carbon, and total nitrogen of sediment core Dethlingen, Germany

To provide insights into the long-term evolution of aquatic ecosystems without human interference, we here evaluate a decadal- to centennial-scale-resolution diatom record spanning about 12 ka of the Holsteinian interglacial (Marine Isotope Stage 11c). Using a partially varved sediment core from the Dethlingen palaeolake (northern Germany), which has previously been studied for palynological and microfacies signals, we document the co-evolution of the aquatic and surrounding terrestrial environment. The diatom record is dominated by the genera Stephanodiscus, Aulacoseira, Ulnaria and Fragilaria. Based on the diatom assemblages and physical sediment properties, the evolution of the Dethlingen palaeolake can be subdivided into three major phases. During the oldest phase (lasting ~1900 varve years), the lake was ~10-15 m deep and characterized by anoxic bottom-water conditions and a high nutrient content. The following ~5600 years exhibited water depths >20 m, maximum diatom and Pediastrum productivity, and a peak in allochtonous nutrient input. During this phase, water-column mixing became more vigorous, resulting in a breakdown of anoxia. The youngest lake phase (~4000-5000 years) was characterized by decreasing water depth, turbulent water conditions and decreased nutrient loading. Based on our palaeolimnological data, we conclude that the evolution of the Dethlingen palaeolake during the Holsteinian interglacial responded closely to (i) changes within the catchment area (as documented by vegetation and sedimentation) related to the transition from closed forests growing on nutrient-rich soils (mesocratic forest phase) to open forests developing on poor soils (oligocratic forest phase), and (ii) short-term climate variability as reflected in centennial-scale climate perturbations.

(Table 1) Elemental composition, pyrite-Fe and degree of pyritisation in Upper Pliensbachian and Lower Toarcian sediments from the costal section of Yorkshire

Profiles of Mo/total organic carbon (TOC) through the Lower Toarcian black shales of the Cleveland Basin, Yorkshire, United Kingdom, and the Posidonia shale of Germany and Switzerland reveal water mass restriction during the interval from late tenuicostatum Zone times to early bifrons Zone times, times which include that of the putative Early Toarcian oceanic anoxic event. The degree of restriction is revealed by crossplots of Mo and TOC concentrations for the Cleveland Basin, which define two linear arrays with regression slopes (ppm/%) of 0.5 and 17. The slope of 0.5 applies to sediment from the upper semicelatum and exaratum Subzones. This value, which is one tenth of that for modern sediments from the Black Sea (Mo/TOC regression slope 4.5), reveals that water mass restriction during this interval was around 10 times more severe than in the modern Black Sea; the renewal frequency of the water mass was between 4 and 40 ka. The Mo/TOC regression slope of 17 applies to the overlying falciferum and commune subzones: the value shows that restriction in this interval was less severe and that the renewal frequency of the water mass was between 10 and 130 years. The more restricted of the two intervals has been termed the Early Toarcian oceanic anoxic event but is shown to be an event caused by basin restriction local to NW Europe. Crossplots of Re, Os, and Mo against TOC show similar trends of increasing element concentration with increase in TOC but with differing slopes. Together with modeling of 187Os/188Os and d98Mo, the element/TOC trends show that drawdown of Re, Os, and Mo was essentially complete during upper semicelatum and exaratum Subzone times (Mo/TOC regression slope of 0.5). Drawdown sensitized the restricted water mass to isotopic change forced by freshwater mixing so that continental inputs of Re, Os, and Mo, via a low-salinity surface layer, created isotopic excursions of up to 1.3 per mil in d98Mo and up to 0.6 per mil for 187Os/188Os. Restriction thereby compromises attempts to date Toarcian black shales, and possibly all black shales, using Re-Os chronology and introduces a confounding influence in the attempts to use d98Mo and initial 187Os/188Os for palaeo-oceanographic interpretation.

Turbidite sedimentology and history at DSDP Site 89-585

At Site 585 in the East Mariana Basin, a 900-m section of Aptian-Albian to Recent sediments was recovered. The upper 590 m are pelagic components (carbonate, siliceous, and clay); small-scale graded sequences and laminations are common. The underlying sediments are volcaniclastic sandstones with a large proportion of shallow-water carbonate debris; sedimentary structures including complete Bouma sequences, cross-laminae, and scouring are common. These structures indicate that the entire section was deposited by turbidity currents. The change in lithology upward in the section reflects the evolution of the surrounding seamounts, from their growth stages during the middle of the Cretaceous to the later subsidence phases. Several black layers containing pyritized organic debris and associated turbidite structures were cored near the Cenomanian/Turonian boundary; this material has been transported from the flanks of the seamounts where it was deposited within a shallow anoxic zone. Seismic data extends the stratigraphy across the entire Basin, showing the reflectors onlapping the seamounts, and indicating at least 1200 m of sediment at Site 585. The crust is placed at 6900 m after correcting for sediment loading, and the subsidence curve indicates that the Basin has been deeper than 5500 m since before the Aptian.

(Table 1) Stable isotope data of chemoherm carbonates at Hydrate Ridge on the Cascadia continental margin

Two active chemoherm build-ups growing freely up into the oceanic water column, the Pinnacle and the South East-Knoll Chemoherms, have been discovered at Hydrate Ridge on the Cascadia continental margin. These microbially-mediated carbonate formations rise above the seafloor by several tens of meters and display a pinnacle-shaped morphology with steep flanks. The recovered rocks are pure carbonates dominated by aragonite. Based on fabric and mineralogic composition different varieties of authigenic aragonite can be distinguished. Detailed visual and petrographic investigations unambiguously reveal the involvement of microbes during the formation of the carbonates. The fabric of the cryptocrystalline and fibrous aragonite can be described as thrombolitic. Fossilized microbial filaments in the microcrystalline aragonite indicate the intimate relationship between microbes and carbonates. The strongly 13C-depleted carbon isotope values of the samples (as low as -48.1 per mill PDB) are characteristic of methane as the major carbon source for the carbonate formation. The methane-rich fluids from which the carbonates are precipitated originate most probably from a gas reservoir below the bottom-simulating reflector (BSR) and rise through fault systems. The d18O values of the aragonitic chemoherm carbonates are substantially higher (as high as 5.0 per mill PDB) than the expected equilibrium value for an aragonite forming from ambient seawater (3.5 per mill PDB). As a first approximation this indicates formation from glacial ocean water but other factors are considered as well. A conceptual model is presented for the precipitation of these chemoherm carbonates based on in situ observations and the detailed petrographic investigation of the carbonates. This model explains the function of the consortium of archaea and sulfate-reducing bacteria that grows on the carbonates performing anaerobic oxidation of methane (AOM) and enabling the precipitation of the chemoherms above the seafloor surrounded by oxic seawater. Beggiatoa mats growing on the surface of the chemoherms oxidize the sulfide provided by sulfate-dependent anaerobic oxidation of methane within an oxic environment. The contact between Beggiatoa and the underlying microbial consortium represents the interface between the overlying oxic water column and an anoxic micro-environment where carbonate formation takes place.

Geochemistry of phosphatic crusts from the shelf off Peru

Authigenic phosphorite crusts from the shelf off Peru (9°40°S to 13°30°S) consist of a facies with phosphatic coated grains covered by younger phosphatic laminite. The crusts are composed of carbonate fluorapatite, which probably formed via an amorphous precursor close to the sediment water interface as indicated by low F/P2O5 ratios, Sr and Ca isotopes, as well as rare earth element patterns agreeing with seawater-dominated fluids. Small negative Ce anomalies and U enrichment in the laminite suggest suboxic conditions close to the sediment-water interface during its formation. Increased contents of chalcophilic elements and abundant sulfide minerals in the facies with phosphatic coated grains as well as in the laminite denote sulfate reduction and, consequently, point to episodical development of anoxic conditions during phosphogenesis. The Peruvian phosphorites formed episodically over an extended period of time lasting from Middle Miocene to Pleistocene. Individual phosphatic coated grains show a succession of phosphatic layers with varying contents of organic matter and sulfide-rich phosphatic layers. Coated grains supposedly formed as a result of episodic suspension caused by high turbulence and shifting redox conditions. Episodic anoxia in the pore water induced pyritization in the outermost carbonate fluorapatite layer. Phosphatic coated grains were later transported to the place of crust formation, where subsequent laminite formation was favored under lower energy conditions. A similar succession of phosphatic layers with varying contents of organic matter and sulfide-rich layers in the laminite suggests a formation mechanism analogous to that of individual coated grains.

Dinoflagellate and other palynomorph abundance in sediments from ODP Leg 189 sites

At Ocean Drilling Program (ODP) Leg 189 Sites 1170-1172, the climatologically critical Eocene-Oligocene (E-O) transition is barren of any calcareous microfossils but contains rich marine organic walled dinoflagellate cyst (dinocyst) and diatom assemblages, suitable for detailed biostratigraphic and paleoenvironmental analysis. The resulting first-ever integrated dinocyst/diatom magnetostratigraphy allows confident correlation of the E-O interval between all Leg 189 sites, including Site 1168. Our correlations indicate that the (deep) opening of the Tasmanian Gateway occurred quasi-synchronously throughout the Tasmanian region, starting at ~35.5 Ma. At Sites 1170-1172, quantitatively, three distinct dinocyst assemblages may be distinguished that reflect the relatively rapid and pronounced stepwise environmental changes associated with the E-O transition in the Tasmanian region, from a pro-deltaic setting to a deep marine pelagic setting. Moreover, synchronous with the deepening of the gateway, at the southern and eastern Sites 1170-1172, typical endemic Antarctic assemblages were replaced by more cosmopolitan dinocyst communities. In marked contrast, at Site 1168 off western Tasmania, endemic Antarctic taxa are virtually absent during the E-O transition. At Sites 1170-1172, the endemic Antarctic dinocyst assemblage (Transantarctic Flora) drastically changes into a more cosmopolitan assemblage at ~35.5 Ma, with a more offshore character, reflecting the arrival of different oceanographic and environmental conditions associated with the deepening of the Tasmanian Gateway. In turn, this assemblage grades at ~34 Ma into one more typical for even more offshore and/or upwelling conditions at Site 1172. In slightly younger deposits at all sites, organic microfossils are virtually absent, reflecting winnowing and oxidation, indicative of a next step of oceanographic development. This phase may be dated as close to the Oceanic Anoxic (Oi)-1 18O (Antarctic glaciation) event (~33.3 Ma). In a single productive sample from the earliest Oligocene the northern Site 1172, a relatively warm-water cosmopolitan assemblage has been recovered. This aspect contrasts findings from coeval deposits from the Ross Sea, where endemic Antarctic species remain dominant. Somewhere between the paleogeographic positions of Site 1172 and the Ross Sea, a strong differentiation of surface waters occurred in the earliest Oligocene, possibly reflecting the onset of the Antarctic Circumpolar Current.

Geochemistry of sediments and kerogenes of ODP Hole

The organic matter contained within a series of Albian to Cenomanian, dark gray to black marls was characterized using pyrolysis techniques and analysis (elemental and carbon isotopes) of isolated kerogens. It was concluded that this material had a marine affinity. Variations in geochemical characteristics reflect differences in the extent of preservation, rather than changes in organic provenance. These changes appear to reflect differences in water depth and the position of the depositional site relative to the oxygen-minimum zone. Sediments displaying the most elevated levels of organiccarbon and hydrogen enrichment probably reflect sedimentation within the oxygen-minimum zone. Waters within the oxygen-minimum zone were probably dysaerobic, rather than anoxic. The presence of at least trace quantities of oxygen at the depositional site explains the poor degree of organic preservation and the material's largely gas-prone characteristics.

Cenomanian/Turonian sea surface temperatures of the equatorial Atlantic reconstructed from geochemical data

Oceanic anoxic event 2 (OAE-2) occurring during the Cenomanian/Turonian (C/T) transition is evident from a globally recognized positive stable carbon isotopic excursion and is thought to represent one of the most extreme carbon cycle perturbations of the last 100 Myr. However, the impact of this major perturbation on and interaction with global climate remains unclear. Here we report new high-resolution records of sea surface temperature (SST) based on TEX86 and d 18O of excellently preserved planktic foraminifera and stable organic carbon isotopes across the C/T transition from black shales located offshore Suriname/French Guiana (Demerara Rise, Ocean Drilling Program Leg 207 Site 1260) and offshore Senegal (Cape Verde Basin, Deep Sea Drilling Project Leg 41 Site 367). At Site 1260, where both SST proxy records can be determined, a good match between conservative SST estimates from TEX86 and d 18O is observed. We find that late Cenomanian SSTs in the equatorial Atlantic Ocean (33°C) were substantially warmer than today (27°-29°C) and that the onset of OAE-2 coincided with a rapid shift to an even warmer (35°-36°C) regime. Within the early stages of the OAE a marked (4°C) cooling to temperatures lower than pre-OAE conditions is observed. However, well before the termination of OAE-2 the warm regime was reestablished and persisted into the Turonian. Our findings corroborate the view that the C/T transition represents the onset of the interval of peak Cretaceous warmth. More importantly, they are consistent with the hypotheses that mid-Cretaceous warmth can be attributed to high levels of atmospheric carbon dioxide (CO2) and that major OAEs were capable of triggering global cooling through the negative feedback effect of organic carbon-burial-led CO2 sequestration. Evidently, however, the factors that gave rise to the observed shift to a warmer climate regime at the onset of OAE-2 were sufficiently powerful that they were only briefly counterbalanced by the high rates of carbon burial attained during even the most extreme interval of organic carbon burial in the last 100 Myr.

Sulphur and iron species in Dvurechenskii mud volcano sediments

The deep Black Sea is known to be depleted in electron-acceptors for sulphide oxidation. This study on depth distributions of sulphur species (S(II), S(0),S(n)**2-,S2O3**2-,SO3**2-,SO4**2-) in the Dvurechenskii mud volcano, a cold seep situated in the permanently anoxic eastern Black Sea basin (Sorokin Trough, 2060 m water depth), showed remarkable concentrations of sulphide oxidation products. Sulphite concentrations of up to 11 µmol L**1-, thiosulphate concentrations of up to 22 µmol L**1-, zero-valent sulphur concentrations of up to 150 µmol L**1- and up to five polysulphide species were measured in the upper 20 cm of the sediment. Electron-acceptors found to be available in the Dvurechenskii mud volcano (DMV) for the oxidation of hydrogen sulphide to sulphide oxidation intermediates are iron-minerals, and probably also reactive manganese phases. Up to 60 µmol g**1- of reactive iron-minerals and up to 170 µmol L**1- dissolved iron was present in the central summit with the highest fluid upflow and fresh mud outflow. Thus, the source for the oxidative power in the DMV are reactive iron phases extruded with the mud from an ancient source in the deeply buried sediments, leading to the formation of various sulphur intermediates in comparably high concentrations. Another possible source of sulphide oxidation intermediates in DMV sediments could be the formation of zero-valent sulphur by sulphate dependent anaerobic microbial oxidation of methane followed by disproportionation of zero-valent sulphur. Sulphide oxidation intermediates, which are produced by these processes, do not reach thermodynamic equilibrium with rhombic sulphur, especially close to the active center of the DMV due to a short equilibration time. Thus, mud volcano sediments, such as in the DMV, can provide oxidizing niches even in a highly reduced environment like the abyssal part of the Black Sea.

Cretaceous planktonic foraminifera of DSDP Hole 71-511

Lower and Upper Cretaceous sediments of the Maurice Ewing Bank, Site 511 (black shales, mudstones, zeolitic clays, and nannofossil chalk and ooze, 361 m thick) are characterized by an assemblage of planktonic foraminifers of low systematic diversity, including over 50 species. Representatives of Hedbergella, Globigerinelloides, Archaeoglobigerina, Whiteinella, Rugoglobigerina, and Heterohelix are predominant; species of Ticinella, Praeglobotruncana, Globotruncana, Schackoina, and Planoglobulina associated with some interbeds occur in smaller numbers. Planktonic foraminifers enable us to subdivide the Cretaceous sediments into Barremian-Aptian, Albian, upper Cenomanian, Turonian, Coniacian-Santonian, Santonian, Campanian, and upper Campanian-Maestrichtian intervals. The Lower Cretaceous (Albian) and Upper Cretaceous (upper Cenomanian-Turonian) are separated by a distinct hiatus and unconformity. In the Upper Cretaceous section, a hiatus may be present at the top of the Campanian. The upper Cenomanian-Santonian sediments are reduced in thickness, whereas the Campanian-Maestrichtian interval is expanded. In the Barremian-Aptian black shales, planktonic foraminifers are very rare: they were deposited in shallow water under anoxic conditions. In the Albian, when sedimentation conditions became oxidizing and the depth increased to 200-400 meters, they became more common. By the end of the Upper Cretaceous, depths appear to increase to 2000 meters. In the interbeds of calcareous sediments, planktonic foraminifers are common; in interbeds of zeolitic clays they are rare or absent (dissolution facies). Alternation of these types of sediments is especially characteristic of the Coniacian-lower Campanian, testifying to abrupt CCD fluctuations. The planktonic foraminifers of the Falkland Plateau belong to the Austral Province of the Southern Hemisphere. In their systematic composition they are extremely similar to microfauna of the Boreal Province of the Northern Hemisphere.

Composition of sedimentary rocks from the Mountainous Crimea and the Northwestern Caucasus

Detailed data obtained on chemistry of sedimentary rocks from the Mountainous Crimea and the Northwestern Caucasus that were dated at the Cenomanian/Turonian boundary and formed during Oceanic Anoxic Event 2 make it possible to calculate dissolved oxygen concentration in bottom waters of the sedimentation basin. Enrichment factors of trace elements in black shales are revised and an explanation is suggested for genesis of the rocks with regard for unusual climatic changes.