O, C and Sr isotopic data for plankton and benthic foraminifera from DSDP Legs 26, 32, 36, and 71 sediments

A detailed d18O and d13C stratigraphy has been generated from analysis of well-preserved Albian - Early Maastrichtian foraminifera from Deep Sea Drilling Project (DSDP) Sites 511 and 327 (Falkland Plateau; ~58°S - 62°S paleolatitude) in the southern South Atlantic, and Cenomanian and Coniacian - Santonian foraminifera from DSDP Site 258 (Naturaliste Plateau; ~58°S paleolatitude) in the southern Indian Ocean. These results, when combined with previously published Maastrichtian stable isotope data from Ocean Drilling Program (ODP) Site 690 (Weddell Sea, ~65°S paleolatitude), provide new insight into the climatic and oceanographic history of the southern high latitudes during Middle-Late Cretaceous time. The planktonic foraminifer d18O curves reveal a gradual warming of surface waters from the Albian through the Cenomanian followed by extremely warm surface waters from the Turonian through the early Campanian. Long-term cooling of surface waters began in the late early Campanian and continued through the end of the Maastrichtian. The benthic foraminifer d18O record generally parallels changes in the oxygen isotopic curves defined by shallow-dwelling planktonic foraminifera. The vertical oxygen and carbon isotopic gradients were relatively low during the Albian - Cenomanian, high from the Turonian - Early Campanian, and then low during the late Campanian and Maastrichtian.

Cretaceous nannofossils from the Northwest African Margin

Deep Sea Drilling Project Leg 79 recovered Cretaceous nannofossils at two localities, Sites 545 and 547. Species diversity of the Cretaceous coccoliths is high, and the assemblages range in age from early Valanginian-early Hauterivian to latest Maestrichtian. Site 545 and portions of Site 547 can be combined to form a composite section ranging from the upper Aptian-lower Albian to the middle to upper Cenomanian. As defined by nannofossil events, this section represents a complete record of sedimentary deposition. The interval appears to be the most extensive and complete Cretaceous section yet drilled off the Northwest African margin. The Campanian and Maestrichtian sediments found at Site 547 (Hole 547A) are the youngest Cretaceous strata found on the Northwest African margin. Like the middle Cretaceous sections, the uppermost Maestrichtian of this interval also represents a complete record of sedimentation.

Calcium carbonate, organic carbon, sediment description and hydrogen and oxygen index at DSDP Sites 93-603, 93-605, 93-604 and 95-603

The organic matter contents of sediments and rocks sampled during DSDP Leg 93 have been characterized by CHN and Rock-Eval analyses. Most samples from Sites 604 and 605 on the New Jersey continental slope and from Site 603 on the Hatteras outer continental rise contained less than 0.5% organic carbon. Some Neogene samples from the slope contained 1 to 2% organic carbon, and Cretaceous samples from the outer rise were as rich as 13.6% organic carbon by weight. Thin layers of black claystones of Santonian, Cenomanian, and Albian age were found interbedded in organiccarbon- lean, bioturbated, turbiditic claystones. Similar layers of turbiditic black marlstones were interspersed among Neocomian limestones and sandstones. Although the organic matter in many of the samples appeared to be detrital continental material, according to Rock-Eval and C/N values, Cenomanian black shales, in particular, contained substantial proportions of marine-derived organic matter.

Total organic carbon content and redox-sensitiv trace metal concentrations of selected late Cenoman claystones from DSDP Hole 93-603B

The Cenomanian/Turonian (C/T) intervals at DSDP Sites 105 and 603B from the northern part of the proto-North Atlantic show high amplitude, short-term cyclic variations in total organic carbon (TOC) content. The more pronounced changes in TOC are also reflected by changes in lithology from green claystones (TOC<1%) to black claystones (TOC>1%). Although their depositional history was different, the individual TOC cycles at Sites 105 and 603B can be correlated using stable carbon isotope stratigraphy. Sedimentation rates obtained from the isotope stratigraphy and spectral analyses indicate that these cycles were predominately precession controlled. The coinciding variations in HI, OI, delta13Corg and the abundance of marine relative to terrestrial biomarkers, as well as the low abundance of lignin pyrolysis products generated from the kerogen of the black claystones, indicate that these cyclic variations reflect changes in the contribution of marine organic matter (OM). The cooccurrence of lamination, enrichment of redox-sensitive trace metals and presence of molecular fossils of pigments from green sulfur bacteria indicate that the northern proto-North Atlantic Ocean water column was periodically euxinic from the bottom to at least the base of the photic zone (<150 m) during the deposition of the black claystones. In contrast, the green claystones are bioturbated, are enriched in Mn, do not show enrichments in redox-sensitive trace metals and show biomarker distributions indicative of long oxygen exposure times, indicating more oxic water conditions. At the same time, there is evidence (e.g., abundance of biogenic silica and significant 13C-enrichment for OC of phytoplanktic origin) for enhanced primary productivity during the deposition of the black claystones. We propose that increased primary productivity periodically overwhelmed the oxic OM remineralisation potential of the bottom waters resulting in the deposition of OM-rich black claystones. Because the amount of oxygen used for OM remineralisation exceeded the amount supplied by diffusion and deep-water circulation, the northern proto-North Atlantic became euxinic during these periods. Both Sites 105 and 603B show trends of continually increasing TOC contents and HI values of the black claystones up section, which most likely resulted from both enhanced preservation due to increased anoxia and increased production of marine OM during oceanic anoxic event 2 (OAE2).

Alkenon concentrations of Creatcesous sediments of DSDP Hole 76-534A (Table 1)

We here report the discovery of unusual distributions of long-chain alkenones (C37-C42) in two Cretaceous black shales from the Blake-Bahama Basin, western North Atlantic. These sediments are Cenomanian (c. 95 Ma) and mid-Albian (c. 105 Ma) in age, thus significantly extending the geological range of these compounds. The precise source of these lipids is, as yet, unknown, although they may derive from an ancient ancestor of Emiliania huxleyi.

Radiolarians of DSDP Site 136-842 and Hole 136-843C

Deep-sea cores recovered at Sites 842 and 843 on Leg 136 of the Ocean Drilling Program have yielded assemblages of Quaternary, Eocene, and Cretaceous radiolarians from the Hawaiian Arch region of the northern equatorial Pacific Ocean. Reddish-brown clays from Hole 842A (0-9.6 mbsf), Hole 842B (0-6.3 mbsf), and Hole 843C (0-4.2 mbsf) contain abundant and diverse assemblages of Quaternary radiolarians consisting of more than 80 species typical of the equatorial Pacific region. Quaternary radiolarians at these sites are assignable to the Quaternary Collosphaera tuberosa Interval Zone and Amphirhopalum ypsilon Interval Zone. The boundary between these zones cannot be determined precisely because of the rarity of zonal markers below surface sediments. Correlations have been made between radiolarian occurrences and magnetostratigraphic events elsewhere in the Pacific Ocean, but similar correlations are difficult at Sites 842 and 843 because of poor subsurface preservation. Chert samples collected from intervals in Cores 842B-10X and 842C-1W have yielded radiolarian ages of lower Cenomanian to Santonian and lower Cenomanian, respectively. Radiolarian assemblages in volcanic sand layers in Sections 6 and 7 of Core 842A-1H (7.5-9.6 mbsf) contain lower and middle Eocene radiolarians admixed with abundant Quaternary faunas. Reworked Eocene radiolarians appear to be restricted to thin layers of volcanic sands within the cores, suggesting deposition by turbidity currents.

Rock eval analysis of organic matter in sediment core 159-959D

The Cretaceous Equatorial Atlantic Gateway between the Central and South Atlantic basins is of interest not only for paleoceanographic and paleoclimatic studies, but also because it provided particularly favourable conditions for the accumulation and preservation of organic-rich sediments. Deposition of carbonaceous sediments along the Côte d'Ivoire-Ghana Transform Margin (Ocean Drilling Program Leg 159) was intimately linked to the plate tectonic and paleoceanographic evolution of this gateway. Notably, the formation of a marginal basement ridge on the southeastern border of the transform margin provided an efficient shelter of the landward Deep Ivorian Basin against erosive and potentially oxidizing currents. Different subsidence histories across the transform margin were responsible for the development of distinct depositional settings on the crest and on both sides of the basement ridge. Whereas the southern, oceanward flank of the basement ridge was characterized by rapid, continuous deepening since last Albian-early Cenomanian, marine sedimentation on the northern, landward flank was interrupted by a period of uplift and erosion in the late Albian, and rapid subsidence started after the early Coniacian. Organic-rich sediments occur throughout almost the entire Cretaceous section, but hydrogen-rich marine black shales were exclusively recovered from core sections above an uplift-related unconformity. These black shales formed when separation of Africa and South America was sufficient to allow permanent oceanic midwater exchange after the late Albian. Four periods of black shale accumulation are recovered, some of them are correlated with the global oceanic anoxic events: in the last Albian-earliest Cenomanian, at the Cenomanian-Turronian boundary, during the middle Coniacian-early Campanian, and in the mid-Maastrichtian. These periods were characterized by increasing carbon flux to the seafloor, induced by enhanced palaeoproductivity and intensified supply of terrestrial organic matter. Black shale depostion appears to be intimately linked to periods of rising or maximum eustatic sea level and to the expansion of the oxygen minimum zone, as indicated by foraminiferal biofacies. Intervals between black shales units, in contrast, indicate a shrinking oxygen minimum zone and enhanced detrital flux rates, probably related to lowering sea level. Upper Cretaceous detritral limestones with high porosities may provide excellent hydrocarbon reservoirs, alsthough their areal extent appears to be limited. Palaeogene porcellanites, capped by Neogene pelagic marls and clays, extend over a wider area and max provide another target for hydrocarbon exploration.

Geochemistry and stable isotope record of black shales and inoceramids from the Demerara Rise

The bulk rock geochemistry and inoceramid isotopic composition from Cenomanian to Santonian, finely laminated, organic-rich black shales, recovered during Ocean Drilling Program Leg 207 on Demerara Rise (western tropical North Atlantic), suggest persistent anoxic (free H2S) conditions within the sediments and short-term variations within a narrow range of anoxic to episodically dysoxic bottom waters over a ~15 Ma time interval. In addition to being organic-rich, the 50-90 m thick sections examined exhibit substantial bulk rock enrichments of Si, P, Ba, Cu, Mo, Ni, and Zn relative to World Average Shale. These observations point to high organic burial fluxes, likely driven by high primary production rates, which led to the establishment of intensely sulfidic pore waters and possibly bottom waters, as well as to the enrichments of Cr, Mo, U, and V in the sediments. At the same time, the irregular presence of benthic inoceramids and foraminifera in this facies demonstrates that the benthic environment could not have been continuously anoxic. The d13C and d15N values of the inoceramid shell organics provide no evidence of chemosymbiosis and are consistent with pelagic rain as being a significant food source. Demerara Rise inoceramids also exhibit well-defined, regularly spaced growth lines that are tracked by d13C and d18O variations in shell carbonate that cannot be simply explained by diagenesis. Instead, productivity variations in surface waters may have paced the growth of the shells during brief oxygenation events suitable for benthic inoceramid settlement. These inferences imply tight benthopelagic coupling and more dynamic benthic conditions than generally portrayed during black shale deposition. By invoking different temporal scales for geochemical and paleontological data, this study resolves recent contradictory conclusions (e.g., sulfidic sedimentary conditions versus dysoxic to suboxic benthic waters) drawn from studies of either sediment geochemistry or fossil distributions alone on Demerara Rise. This variability may be relevant for discussions of black shales in general.

Organic geochemistry at DSDP Leg 80 Holes

The four sites drilled on the Irish continental margin (Goban Spur) yielded sediments ranging in age from Holocene to Barremian. Most of the sediments were deposited in well oxygenated waters, and the small amounts of organic matter they contain are highly oxidized. During a few time intervals from the Cenomanian to earliest Turonian, however, the oxygen content of the bottom waters reached very low levels, resulting in the deposition of homogeneous or laminated black sediments containing from 0.5 to 11% total organic carbon (TOC). The original organic matter was of mixed marine and terrestrial origin. The oxidizing-reducing cycles represented by interbedded black and light sediments are probably a result of changes in both circulation and productivity. The black sediments at Sites 550, 551, and 549 were probably deposited near the lower end, middle, and upper end, respectively, of an expanded oxygen-minimum layer. The oil and gas source potential of the laminated black sediments is very good to excellent. The organic-carbon-lean sediments deposited under oxidizing conditions have no oil or gas source potential. The thermal maturity of all sediments is low.

(Appendix) Late Cretaceous calcareous nannofossils of DSDP Holes 80-549 and 80-551

he early late Cretaceous (Cenomanian-early Turonian) is thought to have been one of the warmest periods of the Phanerozoic. This period was characterised by tropical sea surface temperatures of up to 36 °C and a pole-to-equator-gradient of less than 10 °C. The subsequent Turonian-Maastrichtian was characterised by a continuous climatic cooling, peaking in the Maastrichtian. This climatic cooling and the resulting palaeoceanographic changes had an impact on planktic primary producer communities including calcareous nannofossils. In order to gain a better understanding of these Cenomanian-Maastrichtian palaeoceanographic changes, calcareous nannofossils have been studied from the proto North Atlantic (Goban Spur, DSDP Sites 549, 551). In order to see potential differences between open oceanic and shelf dwelling nannofossils, the data from Goban Spur have been compared to findings from the European shelf (northern Germany). A total of 77 samples from Goban Spur were studied for calcareous nannofossils revealing abundant (mean 6.2 billion specimens/g sediment) and highly diverse (mean 63 species/sample) nannofossil assemblages. The dominant taxa are Watznaueria spp. (mean 30.7%), Prediscosphaera spp. (mean 18.3%), Zeugrhabdotus spp. (mean 8.3%), Retecapsa spp. (mean 7.2%) and Biscutum spp. (mean 6.6%). The Cenomanian assemblages of both Goban Spur (open ocean) and Wunstorf (shelf) are characterised by elevated abundances of high fertility taxa like Biscutum spp., Zeugrhabdotus spp. and Tranolithus orionatus. Early Turonian to Maastrichtian calcareous nannofossil assemblages of Goban Spur are, however, quite different to those described from European sections. Oceanic taxa like Watznaueria spp., Retecapsa spp. and Cribrosphearella ehrenbergii dominate in Goban Spur whereas the fertility indicators Biscutum spp. and T. orionatus are more abundant in the European shelf assemblages. This shift from a homogeneous distribution of calcareous nannofossils in the Cenomanian towards a heterogeneous one in the Turonian-Maastrichtian implies a change of the ocean circulation. The "eddy ocean" system of the Cenomanian was replaced by an oceanic circulation similar to the modern one in the Turonian-Maastrichtian, caused by the cooling. The increased pole-to-equator-gradients resulted in an oceanic circulation similar to the modern one.

Magnetic suceptibility, carbon and oxygen stable isotope ratios and reflectance from the Bottaccione Gorge and Furlo section, Italy

The oceans at the time of the Cenomanian-Turonian transition were abruptly perturbed by a period of bottom-water anoxia. This led to the brief but widespread deposition of black organic-rich shales, such as the Livello Bonarelli in the Umbria-Marche Basin (Italy). Despite intensive studies, the origin and exact timing of this event are still debated. In this study, we assess leading hypotheses about the inception of oceanic anoxia in the Late Cretaceous greenhouse world, by providing a 6-Myr-long astronomically-tuned timescale across the Cenomanian-Turonian boundary. We procure insights in the relationship between orbital forcing and the Late Cretaceous carbon cycle by deciphering the imprint of astronomical cycles on lithologic, geophysical, and stable isotope records, obtained from the Bottaccione, Contessa and Furlo sections in the Umbria-Marche Basin. The deposition of black shales and cherts, as well as the onset of oceanic anoxia, is related to maxima in the 405-kyr cycle of eccentricity-modulated precession. Correlation to radioisotopic ages from the Western Interior (USA) provides unprecedented age control for the studied Italian successions. The most likely tuned age for the Livello Bonarelli base is 94.17 ± 0.15 Ma (tuning #1); however, a 405-kyr older age cannot be excluded (tuning #2) due to uncertainties in stratigraphic correlation, radioisotopic dating, and orbital configuration. Our cyclostratigraphic framework suggests that the exact timing of major carbon cycle perturbations during the Cretaceous may be linked to increased variability in seasonality (i.e. a 405-kyr eccentricity maximum) after the prolonged avoidance of seasonal extremes (i.e. a 2.4-Myr eccentricity minimum). Volcanism is probably the ultimate driver of oceanic anoxia, but orbital periodicities determine the exact timing of carbon cycle perturbations in the Late Cretaceous. This unites two leading hypotheses about the inception of oceanic anoxia in the Late Cretaceous greenhouse world.

(Table 1) Summary of low-molecular-weight hydrocarbon concentrations, organic carbon contents, Rock-Eval pyrolysis and lithology at DSDP Leg 79 Holes

A series of core samples taken during Cruise 79 of Glomar Challenger, drilling offshore Morocco (Mazagan Plateau), is analyzed for their low-molecular-weight hydrocarbon contents. Fifty-four samples from DSDP Holes 544A, 545, 547A, and 547B, deep frozen on board immediately after recovery, are studied by a hydrogen-stripping/thermovaporization technique combined with capillary gas chromatography. Thirty-eight compounds in the C2-C8 molecular range, including saturated, olefinic, and aromatic hydrocarbons, are identified. Because of large differences in organic carbon contents, the total C2-C8 hydrocarbon concentrations vary from about 20 to 1500 ng/g dry sediment weight in the whole sample series. Organic-carbon normalized values are about 3.2 x 10**4 ng/g Corg for Lithologic Subunits IIIA and IIIB at Site 545 (Cenomanian to Aptian) and 1.0 x 10**5 ng/g Corg for Unit V at Site 547 (Cenomanian to Albian) reflecting the slightly more advanced maturity stage at the latter site. Values exceeding 10**5 ng/g Corg (Site 545) and 2 x 10**5 ng/g Corg (Site 547) are associated with samples that are very lean in organic carbon and are generally rich in carbonate. These samples are enriched by small amounts of gaseous hydrocarbons. A detailed study of individual hydrocarbon concentrations, plotted against depth, reveal additional indications for migration phenomena. At Site 547, for instance, the most mobile hydrocarbons studied (e.g., ethane) appear to migrate by diffusion or a related process from more than 700 m depth toward the surface.

(Appendix) Total organic carbon, pyrolysis characteristics, and organic matter types at DSDP Holes 77-535 and 77-540

Lower to middle Cretaceous sediments in the eastern Gulf of Mexico are richer in organic matter and have a more marine organic facies than their counterparts in the nearby western North Atlantic, suggesting that the Gulf was the more productive of the two areas. As in the western North Atlantic, the rate of supply of terrestrial organic matter was high when the rate of supply of noncarbonate clastic materials was high (at times of low sea level) and diminished as sea level rose. The rate of supply of marine organic matter was lower in the Early Cretaceous than in the Cenomanian, perhaps in response to the global rise in sea level over this period. Where they are thermally mature, the organic matterrich units drilled at Sites 535 and 540 should be excellent sources for liquid hydrocarbons. The Pleistocene sediments of the eastern Gulf are dominated by terrestrial organic matter representing Mississippi River effluent.

Geochemical composition of ODP Site 210-1276 shales

During Ocean Drilling Program Leg 210, a greatly expanded sedimentary sequence of continuous Cretaceous black shales was recovered at Site 1276. This section corresponds to the Hatteras Formation, which has been documented widely in the North Atlantic Ocean. The cored sequence extends from the lowermost Albian, or possibly uppermost Aptian, to the Cenomanian/Turonian boundary and is characterized by numerous gravity-flow deposits and sporadic, finely laminated black shales. The sequence also includes several sedimentary intervals with high total organic carbon (TOC) contents, in several instances of probable marine origin that may record oceanic anoxic events (OAE). These layers might correspond to the Cenomanian-Turonian OAE 2; the mid-Cenomanian event; and OAE 1b, 1c, and 1d in the Albian. In addition, another interval with geochemical characteristics similar to OAE-type layers was recognized in the Albian, although it does not correspond to any of the known OAEs. This study investigates the origin of the organic matter contained within these black shale intervals using TOC and CaCO3 contents, Corg/Ntot ratios, organic carbon and nitrogen isotopes, trace metal composition, and rock-eval analyses. Most of these black shale intervals, especially OAE 2 and 1b, are characterized by low 15N values (<0) commonly observed in mid-Cretaceous black shales, which seem to reflect the presence of an altered nitrogen cycle with rates of nitrogen fixation significantly higher than in the modern ocean.