Strontium-isotope stratigraphy and oxygen- and carbon-isotope record of Middle Jurassic to Early Cretaceous belemnites in the South Atlantic

87Sr/86Sr data of belemnites are presented from a Middle Jurassic-Early Cretaceous succession from the Falkland Plateau (Deep Sea Drilling Project Sites 511 and 330) that was deposited in a periodically anoxic, semi-enclosed shallow water basin. Diagenetically screened strontium-isotope values of 0.706789 rise to 0.707044 before increasing sharply to 0.707428 in the uppermost part of the sampled succession. Comparison with published strontium calibration curves suggests that the oldest samples were Callovian to Oxfordian in age, whilst the remainder of the Jurassic part of the succession consisted of Kimmeridgian and Early Tithonian age sediments. The nannofossil, dinoflagellate and molluscan assemblages provide comparable age determinations. The strontium-isotope analysis of the youngest belemnites points to a Hauterivian-Barremian age, whilst age interpretations based upon the fauna provide a wide age range from the Barremian to early Albian. Strontium-isotope stratigraphy of this succession hence offers increased age resolution providing data regarding the timing of episodes of bottom water anoxia which have been recorded throughout the South Atlantic Basin. Well-preserved belemnite specimens display an oxygen-isotope range between +0.08 and -2.22? (PDB, Peedee belemnite international standard) and a carbon-isotope range from +2.35 to -1.33? (PDB). Delta13C values become increasingly negative through the Late Jurassic-Early Cretaceous and in concert with the 87Sr/86Sr data reveal a trend that could be accounted for by increasing levels of weathering and erosion. The oxygen-isotope data if interpreted in terms of palaeotemperature are consistent with warm palaeotemperatures in the Kimmeridgian and slightly cooler temperatures for the Tithonian and Early Cretaceous parts of the succession. The proposed relative Kimmeridgian warmth (based upon strontium-isotope age assignments) is thus in good agreement with other published palaeotemperature records.

Cretaceous calcareous nannofossils of ODP Leg 103 holes

Ocean Drilling Program Leg 103 recovered Lower Cretaceous sediments from the Galicia margin off the coast of Iberia. The high diversity and abundance of assemblages makes this excellent material for the study of Early Cretaceous calcareous nannofossils. With the exception of a hiatus between the upper Hauterivian and lower Barremian, nannofossil distributions form a continuous composite section from the lower Valanginian to lower Cenomanian sediments recovered at the four sites. The sedimentation history of this rifted continental margin is complex, and careful examination of the nannofossil content and lithology is necessary in order to obtain optimum biostratigraphic resolution. The Lower Cretaceous sequence consists of a lower Valanginian calpionellid marlstone overlain by terrigenous sandstone turbidites deposited in the Valanginian and Hauterivian during initial rifting of this part of the margin. Interbedded calcareous marl and claystone microturbidites overlie the sandstone turbidites. Rifting processes culminated in the late Aptian-early Albian, resulting in the deposition of a calcareous, clastic turbidite sequence. The subsequent deposition of dark carbonaceous claystones (black shales) represents the beginning of seafloor spreading, as the margin continued to subside to depths near or below the CCD. The diversity, abundance, and preservation of nannofossils within these varied lithologies differ, and an attempt to distinguish between near shore and open-marine assemblages is made. Genera used for this purpose include Nannoconus, Micrantholithus, Pickelhaube, and Lithraphidites. In this study, six new species and one new subspecies are described and documented. Ranges of other species are extended, and an attempt is made to clarify existing, yet poorly understood, taxonomic concepts. A technique in which a single specimen is viewed with both light and scanning electron microscopes was used extensively to aid in this task. In addition, further subdivisions of the Sissingh (1977) zonation are suggested in order to increase biostratigraphic resolution.

Mineralogy micromorphology, and geochemistry at DSDP Site 89-585

At Site 585 of Deep Sea Drilling Project Leg 89 more than 500 m of volcaniclastic to argillaceous middle-Late Cretaceous sediments were recovered. Analyses by X-ray diffraction (bulk sediment and clay fraction), transmission electron microscopy, molecular and atomic absorption, and electron microprobe were done on Site 585 samples. We identify four successive stages and interpret them as the expression of environments evolving under successive influences: Stage 1, late Aptian to early Albian - subaerial and proximal volcanism, chiefly expressed by the presence of augite, analcite, olivine, celadonite, small and well-shaped transparent trioctahedral saponite, Al hydroxides, Na, Fe, Mg, and various trace elements (Mn, Ni, Cr, Co, Pb, V, Zn, Ti). Stage 2, early to middle Albian - submarine and less proximal volcanic influence, characterized by dioctahedral and hairy Mg-beidellites, a paucity of analcite and pyroxenes, the presence of Mg and K, and local alteration of Mg-smectites to Mg-chlorites. Stage 3, middle Albian to middle Campanian - early marine diagenesis, marked by the development of recrystallization from fleecy smectites to lathed ones (all of alkaline Si-rich Fe-beidellite types), by the development of opal CT and clinoptilolite, and by proximal to distal volcanic influences (Na parallel to Ti, K). Local events consist of the supply of reworked palygorskite during the Albian-Cenomanian, and the recurrence of proximal volcanic activity during the early Campanian. Stage 4, late Campanian to Maestrichtian - development of terrigenous supply resulting from the submersion of topographic barriers; this terrigenous supply is associated with minor diagenetic effects and is marked by a clay diversification (beidellite, illite, kaolinite, palygorskite), the rareness of clay recrystallizations, and the disappearance of volcanic markers.

Macroturbidites of ODP Hole 103-641C

Barremian through uppermost Aptian strata from ODP Hole 641C, located upslope of a tilted fault block on the Galicia margin (northwest Spain), are syn-rift sediments deposited in the bathyal realm and are characterized by rapid sedimentation from turbidity currents and debris flows. Calcarenite and calcirudite turbidites contain shallow-water carbonate, terrigenous, and pelagic debris, in complete or partial Bouma sequences. These deposits contain abraded micritized bioclasts of reefal debris, including rudist fragments. The youngest turbidite containing shallow-water carbonate debris at Site 641 defines the boundary between syn-rift and post-rift sediments; this is also the boundary between Aptian and Albian sediments. Some Aptian turbidites are partially silicified, with pore-filling chalcedony and megaquartz. Adjacent layers of length-fast and -slow chalcedony are succeeded by megaquartz as the final pore-filling stage within carbonate reef debris. Temperatures of formation, calculated from the oxygen isotopic composition of the authigenic quartz, are relatively low for formation of quartz but are relatively warm for shallow burial depths. This quartz cement may be interpreted as a rift-associated precipitate from seawater-derived epithermal fluids that migrated along a fault associated with the tilted block and were injected into the porous turbidite beds. These warm fluids may have cooled rapidly and precipitated silica at the boundaries of the turbidite beds as a result of contact with cooler pore waters. The color pattern in the quartz cement, observed by cathodoluminescence and fluorescence techniques, and changes in the trace lement geochemistry mimic the textural change of the different quartz layers and indicates growth synchronism of the different quartz phases. Fluorescence petrography of neomorphosed low-Mg-calcite bioclasts in the silicified turbidites shows extensive zonation and details of replacive crystal growth in the bioclasts that are not observed by cathodoluminescence. Fluorescence microscopy also reveals a competitive growth history during neomorphism of the adjacent crystals in an altered carbonate bioclast. Barremian-Aptian background pelagic sediments from Hole 641C have characteristics similar to pelagic sediments from the Blake-Bahama Formation described by Jansa et al. (1979) from the western North Atlantic. Sediments at this site differ from the Blake-Bahama Formation type locality in that the Barremian-Aptian pelagic sediments have a higher percentage of dark calcareous claystone and some turbidites are silicified at Site 641. The stable isotopic composition of the pelagic marlstones from Site 641 is similar to those of other Berriasian-Aptian pelagic sediments from the Atlantic.

Sable isotope record and sediment composition of Cretaceous samples of Deremara Rise

We estimate tropical Atlantic upper ocean temperatures using oxygen isotope and Mg/Ca ratios in well-preserved planktonic foraminifera extracted from Albian through Santonian black shales recovered during Ocean Drilling Program Leg 207 (North Atlantic Demerara Rise). On the basis of a range of plausible assumptions regarding seawater composition at the time the data support temperatures between 33° and 42°C. In our low-resolution data set spanning ~84-100 Ma a local temperature maximum occurs in the late Turonian, and a possible minimum occurs in the mid to early late Cenomanian. The relation between single species foraminiferal d18O and Mg/Ca suggests that the ratio of magnesium to calcium in the Turonian-Coniacian ocean may have been lower than in the Albian-Cenomanian ocean, perhaps coincident with an ocean 87Sr/86Sr minimum. The carbon isotopic compositions of distinct marine algal biomarkers were measured in the same sediment samples. The d13C values of phytane, combined with foraminiferal d13C and inferred temperatures, were used to estimate atmospheric carbon dioxide concentrations through this interval. Estimates of atmospheric CO2 concentrations range between 600 and 2400 ppmv. Within the uncertainty in the various proxies, there is only a weak overall correspondence between higher (lower) tropical temperatures and more (less) atmospheric CO2. The GENESIS climate model underpredicts tropical Atlantic temperatures inferred from ODP Leg 207 foraminiferal d18O and Mg/Ca when we specify approximate CO2 concentrations estimated from the biomarker isotopes in the same samples. Possible errors in the temperature and CO2 estimates and possible deficiencies in the model are discussed. The potential for and effects of substantially higher atmospheric methane during Cretaceous anoxic events, perhaps derived from high fluxes from the oxygen minimum zone, are considered in light of recent work that shows a quadratic relation between increased methane flux and atmospheric CH4 concentrations. With 50 ppm CH4, GENESIS sea surface temperatures approximate the minimum upper ocean temperatures inferred from proxy data when CO2 concentrations specified to the model are near those inferred using the phytane d13C proxy. However, atmospheric CO2 concentrations of 3500 ppm or more are still required in the model in order to reproduce inferred maximum temperatures.

Organic geochemistry of Cretaceous black shales

Organic-carbon-rich 'black shales' and adjacent organic-carbon-poor rocks from three different Cretaceous settings encountered during ODP Leg 103 have been studied by organic geochemical methods. Rock-Eval analysis, carbon isotope data, and lipid biomarkers show organic matter to contain varying proportions of marine and continental materials. In Hauterivian-Barremian organic-carbon-rich marlstone turbidites, large amounts of land-derived organic matter are found. Aptian-Albian black-colored shales are interspersed within green claystones, from which they differ by containing more marine organic matter. An abbreviated layer of black shale from the Cenomanian/Turonian boundary is dominated by well-preserved marine organic matter. Downslope transport and rapid reburial within a predominantly oxygenated deep-water setting created most of these examples of black shales, except for the Cenomanian-Turonian deposits in which deep-water anoxia may have been involved.

(Appendix) Bulk inorganic chemistry at DSDP Leg 77 Holes

Clay mineralogic and inorganic geochemical investigations of Cretaceous and Cenozoic sediments of the western Gulf of Mexico lead to the following main conclusions. (1) Transition of lowermost Cretaceous continental to marine sedimentation is marked by a clay evaporitic stage, north of the Campeche Escarpment. (2) Existence of combined mineralogic and geochemical stratigraphy allows us to propose correlations between Sites 535 and 540, especially for the Albian. (3) Predominance of detrital clay assemblages is indicative of hot and variably humid continental climate until the early late Cenozoic. (4) Tectonic destabilization of the margins of Gulf of Mexico occurred at different periods, especially until the middle Cretaceous, with a mixed erosion of rocks and soils and temporary oxidized conditions of deposition. (5) Successive developments of confined perimarine basins occurred from the earliest Cretaceous until the Miocene, chiefly in the Florida area. The sources of inorganic materials were chiefly situated on the east of the studied area until the late Tertiary and after that in the Mississippi River basin. (6) Occasionally, volcanic activity influenced the clay mineralogy and mainly the geochemistry, and possibly contributed to the rather strong magnesian character of the deposition until the late Paleogene. (7) The argillaceous diagenesis is weak; variability of the carbonate diagenesis is marked by the relation Sr = f(CaO) and chiefly depends on the depth of burial, the clay content, the porosity, and the geologic age.

(Table 3) Geochemistry at DSDP Leg 79 Holes

Detailed mineralogical and geochemical studies were performed on samples from selected time intervals recovered during Leg 79 on the Mazagan Plateau. The uppermost Albian and Cenomanian sediments of Sites 545 and 547 can be correlated on the basis of mineralogy and geochemistry; these sediments illustrate differential settling processes and the existence of hot climates with alternating humid and dry seasons in the African coastal zone. The upper Aptian to Albian black shales of Site 545 point to an irregular alternation of tectonic activity and relaxation stages, allowing different behaviors in the reworking of soils, crystalline rocks, and sediments born in peri-marine basins. The barren lower Mesozoic reddish sediments and evaporitic series of Sites 546 and 547 are characterized by a strong physical erosion of sialic landscapes, without clear evidence of post-depositional metamorphic events. At Site 546 strong early diagenetic processes in a confined evaporitic environment affect both the mineralogy and the geochemistry of pre-Miocene rocks.

Trace and rare elements and factors at DSDP Hole 71-511

The distribution of paragenetic assemblages of trace and rare elements, as revealed by factor analysis (R-mode, Q-mode), the ratios of elements to Zr and the interpretation of these data in the context of the known mineralogy, lithology, and geology of the region, provide the bases for the outline of the geochemical history of sedimentation in the study area that forms the subject of this chapter. Two stages may be discerned. 1. Late-Middle Jurassic-Early Cretaceous (160-106? Ma). The sediments that accumulated in relatively shallow water (shelf) were predominantly clay, with dispersed sapropelic organic matter, plant fragments, pyrite, admixtures of acid-medium volcanic glass, and epigenetic crystals of gypsum. The bottom water layers of the basin are notably stagnant. The sediments are characterized by higher amounts of V, Zn, Cu, Cr, Rb, and Be associated with organic matter. Lower Cretaceous sediments, separated from those of the Upper Jurassic by a hiatus, accumulated in a deepened and enlarging basin. These Lower Cretaceous deposits are chemically similar to those of the Upper Jurassic, but contain diagenetic concentrations of Zn, Ni, and La. 2. Early-middle Albian (Unit 5)-middle Maestrichtian (1067-66.6Ma). The prevailing regime was that of an open ocean basin that tended to expand and deepen. During the second half of the early-middle Albian, the biogenic components Ba, Sr, and CaCO3 accumulated. By the end of this interval, Ti/Zr values had increased. In conjunction data on mineral composition, they testify to an outburst of basaltoid volcanism related to tectonic activity before an erosional hiatus (late Albian-Cenomanian). At the end of the Cenomanian-Turonian, residual deposits of predominantly clay sediments with relatively high amounts of Ti and Zr and associated rare alkalis (Li, Rb) accumulated. Clay sediments deposited during the Coniacian-Santonian were characterized by higher concentrations of Ti, Zr, Li, and Rb, by diagenetic carbonate phases of Ni, Zn, and La, and by sulphides and Fe-oxides with an admixture of Ni and Co. The latter half of the interval saw the deposition of fine basaltoid volcanoclastic material, diagenetically altered by zeolitization and carbonatization and enriched with Se, Pb, Ti, Sr, Ba, Y, and Yb. Sediments with a similar chemistry accumulated in the Campanian-middle Maestrichtian. Strong current activity preceding a global hiatus at the Mesozoic/Cenozoic boundary is reflected in both lower sedimentation rates and the presence of higher residual concentrations of Ti, Zr, Ba, Sr, and other elements studied in this chapter.

Cretaceous calcareous nannofossils from Exmouth and Wombat Plateau, Northwest Australia

Three sites drilled during Leg 122, Site 761 on the Wombat Plateau and Sites 762 and 763 on the Exmouth Plateau, provide a composite Cretaceous section ranging in age from Berriasian to Maestrichtian. Together, these sites contain an apparently complete, expanded Aptian-Maestrichtian record. Consistently occurring and moderately well-preserved nannofossil assemblages allow reasonably high biostratigraphic resolution. Our data indicate that traditional middle and Upper Cretaceous nannofossil biozonations are not entirely applicable in this region. In this investigation, we compare in detail the relative ranges of key Cretaceous nannofossil markers in the eastern Indian Ocean and in sections from Europe and North Africa. We have determined which previously used events are applicable, and which additional markers have biostratigraphic utility in this region. Significant differences in Campanian-Maestrichtian assemblages exist between the more northern Site 761 and Sites 762 and 763. Such differences are surprising, considering that these sites are only separated by 3° of latitude. We interpret them as marking a strong thermal gradient over the Exmouth Plateau region. Other results include the recovery of an expanded Albian-Cenomanian sequence containing a mixture of Austral and Tethyan floras, which will enable correlation of biozonations established for these two realms; the recovery of two condensed but apparently complete Cenomanian-Turonian boundary sections; correlation of Upper Cretaceous calcareous nannofossil biostratigraphy with magneto- and foraminifer stratigraphy; and correlation of portions of the Barrow Group equivalents to the Berriasian and Valanginian stages.

Lithology, stratigraphy, organic carbon content, extract and liquid chromatography yields, and Rock-Eval pyrolysis at DSDP Holes 75-530A and 75-532

Seventeen sediment samples of Albian-Cenomanian to early Pliocene age from DSDP Hole 530A in the Angola Basin and six sediment samples of early Pliocene to late Pleistocene age from the Walvis Ridge were investigated by organic geochemical methods, including organic carbon determination, Rock-Eval pyrolysis, gas chromatography and combined gas chromatography/mass spectrometry of extractable hydrocarbons, and kerogen microscopy. The organic matter in all samples is strongly influenced by a terrigenous component from the nearby continent. The amount of marine organic matter present usually increases with the total organic carbon content, which reaches an extreme value of more than 10% in a Cenomanian black shale from Hole 530A. At Site 530 the extent of preservation of organic matter in the deep sea sediments is related to mass transport down the continental slope, whereas the high organic carbon contents in the sediments from Site 532 reflect both high bioproductivity in the Benguela upwelling regime and considerable supply of terrigenous organic matter. The maturation level of the organic matter is low in all samples.

Foraminiferal oxygen and carbon isotope data for DSDP Sites 32-305 and 62-463 and ODP Sites 171-1049 and 171-1050

Oxygen isotope analyses of well-preserved foraminifera from Blake Nose (30°N paleolatitude, North Atlantic) and globally distributed deep-sea sites provide a long-term paleotemperature record for the late Albian-Maastrichtian interval that is difficult to reconcile with the existence of significant Cretaceous ice sheets. Given reasonable assumptions about the isotopic composition of Cretaceous seawater, our results suggest that middle bathyal water temperatures at Blake Nose increased from ~12°C in the late Albian through middle Cenomanian to a maximum of 20°C during the latest Cenomanian and earliest Turonian. Bottom waters were again ~12°C during the middle Campanian and cooled to a minimum of 9°C during the Maastrichtian. Correlative middle bathyal foraminifera from other ocean basins yield paleotemperature estimates that are very similar to those from Blake Nose. Comparison of global bottom-water temperatures and latitudinal thermal gradients suggests that global climate changed from a warm greenhouse state during the late Albian through late Cenomanian to a hot greenhouse phase during the latest Cenomanian through early Campanian, then to cool greenhouse conditions during the mid-Campanian through Maastrichtian.

Electrical resistivity, formation factors, and sound velocity at DSDP Holes 75-530A and 75-530B

From 0 to 277 m at Site 530 are found Holocene to Miocene diatom ooze, nannofossil ooze, marl, clay, and debrisflow deposits; from 277 to 467 m are Miocene to Oligocene mud; from 467 to 1103 m are Eocene to late Albian Cenomanian interbedded mudstone, marlstone, chalk, clastic limestone, sandstone, and black shale in the lower portion; from 1103 to 1121 m are basalts. In the interval from 0 to 467 m, in Holocene to Oligocene pelagic oozes, marl, clay, debris flows, and mud, velocities are 1.5 to 1.8 km/s; below 200 m velocities increase irregularly with increasing depth. From 0 to 100 m, in Holocene to Pleistocene diatom and nannofossil oozes (excluding debris flows), velocities are approximately equivalent to that of the interstitial seawater, and thus acoustic reflections in the upper 100 m are primarily caused by variations in density and porosity. Below 100 or 200 m, acoustic reflections are caused by variations in both velocity and density. From 100 to 467 m, in Miocene-Oligocene nannofossil ooze, clay, marl, debris flows, and mud, acoustic anisotropy irregularly increases to 10%, with 2 to 5% being typical. From 467 to 1103 m in Paleocene to late Albian Cenomanian interbedded mudstone, marlstone, chalk, clastic limestone, and black shale in the lower portion of the hole, velocities range from 1.6 to 5.48 km/s, and acoustic anisotropies are as great as 47% (1.0 km/s) faster horizontally. Mudstone and uncemented sandstone have anisotropies which irregularly increase with increasing depth from 5 to 10% (0.2 km/s). Calcareous mudstones have the greatest anisotropies, typically 35% (0.6 km/s). Below 1103 m, basalt velocities ranged from 4.68 to 4.98 km/s. A typical value is about 4.8 km/s. In situ velocities are calculated from velocity data obtained in the laboratory. These are corrected for in situ temperature, hydrostatic pressure, and porosity rebound (expansion when the overburden pressure is released). These corrections do not include rigidity variations caused by overburden pressures. These corrections affect semiconsolidated sedimentary rocks the most (up to 0.25 km/s faster). These laboratory velocities appear to be greater than the velocities from the sonic log. Reflection coefficients derived from the laboratory data, in general, agree with the major features on the seismic profiles. These indicate more potential reflectors than indicated from the reflection coefficients derived using the Gearhart-Owen Sonic Log from 625 to 940 m, because the Sonic Log data average thin beds. Porosity-density data versus depth for mud, mudstone, and pelagic oozes agree with data for similar sediments as summarized in Hamilton (1976). At depths of about 400 m and about 850 m are zones of relatively higher porosity mudstones, which may suggest anomalously high pore pressure; however, they are more probably caused by variations in grain-size distribution and lithology. Electrical resistivity (horizontal) from 625 to 950 m ranged from about 1.0 to 4.0 ohm-m, in Maestrichtian to Santonian- Coniacian mudstone, marlstone, chalk, clastic limestone, and sandstone. An interstitial-water resistivity curve did not indicate any unexpected lithology or unusual fluid or gas in the pores of the rock. These logs were above the black shale beds. From 0 to 100 m at Sites 530 and 532, the vane shear strength on undisturbed samples of Holocene-Pleistocene diatom and nannofossil ooze uniformly increases from about 80 g/cm**2 to about 800 g/cm**2. From 100 to 300 m, vane shear strength of Pleistocene-Miocene nannofossil ooze, clay, and marl are irregular versus depth with a range of 500 to 2300 g/cm**2; and at Site 532 the vane shear strength appears to decrease irregularly and slightly with increasing depth (gassy zone). Vane shear strength values of gassy samples may not be valid, for the samples may be disturbed as gas evolves, and the sediments may not be gassy at in situ depths.