Organic geochemistry of DSDP Leg 41 holes

The black shale encountered in Cretaceous cores of the Cape Verde area during the DSDP Leg 41 are of marine origin and correspond to excellent potential oil source rocks. They have a low content of humic compounds. Pyrolysis assays, chloroformic extracts, and kerogen data attest to a relatively low stage of evolution for samples at Site 367 (Cape Verde Basin). The samples from Site 368 (Cape Verde Rise) are more evolved, and the deeper ones would be located at the beginning of the principal zone of oil formation.

Elemental and isotope compositions of lipids, kerogens and asphaltenes from samples of DSDP Hole 41-368

The thermal effects of three (one major and two minor) Miocene diabase intrusions on Cretaceous black shales from DSDP site 41-368 have been analyzed. A concentration gradient was observed, especially for the hydrocarbons, decreasing towards the major intrusion and between the three sills. The thermally-altered samples in the proximity of and between the sills contained elemental sulfur and an excess of thermally-derived pristane over phytane. whereas, the unaltered sediments contained no elemental sulfur, and more phytane than pristane. A maximum yield of the extractable hydrocarbons was observed at a depth of 7 m below the major sill. Two classes of molecular markers were present in this bitumen suite. The first was sesqui-, di- and triterpenoids and steranes. which could be correlated with both terrigenous and autochthonous sources. They were geologically mature and showed no significant changes due to the thermal stress. The second class was found in the altered samples, which contained only polynuclear aromatic hydrocarbons with low alkyl substitution and sulfur and oxygen heterocyclic aromatic compounds. These compounds were derived from pyrolytic reactions during the thermal event. Kerogen was isolated from all of these samples, but only traces of humic substances were present. The H/C, N/C, d13C, d34S and dD all exhibit the expected effects of thermal stress. The kerogen becomes more aromatized and richer in 13C, 34S and D in the proximity of and between the sills. Maturation trends were also measured by the vitrinite reflectance and electron spin resonance, where the thermal stress could be correlated with an elevated country rock temperature and an increased degree of aromaticity. The effects of in situ thermal stress on the organic-rich shales resulted in the generation and expulsion of petroliferous material from the vicinity of the sills.

Stable isotope (carbonates), organic carbon, calcium carbonate and occurrence of coccoliths at DSDP Hole 71-511

Thin but discrete pelagic limestone beds intercalated among the black mudstones near the top of the extensive Mesozoic black shale sequence of the Falkland Plateau are reminiscent of similar occurrences in the central and North Atlantic and may be cyclic in nature. They have been studied via carbonate, organic carbon, stable isotope, nannofloral, and ultrastructural analysis in an attempt to determine their mode of origin. Nannofossil diversity and preservation suggest that selective dissolution or diagenesis did not produce the interbedded coccolith-rich and coccolith-poor layers, nor did blooms of opportunistic species play a role. Stable isotope measurements of carbonate do not adequately constrain the origin of the cyclicity; however, the d13C data suggest that the more nannofossil-rich intervals may be due to higher nutrient supply and overturn of deeper waters at the site rather than influxes of well-oxygenated waters into an otherwise anoxic environment. Such an explanation is in accord with the nannofloral evidence

Low-molecular-weight hydrocarbon concentrations, organic carbon contents, and Rock-Eval pyrolysis hydrogen indices at DSDP Holes 75-530A and 75-532

A series of C2-C8 hydrocarbons (including saturated, aromatic, and olefinic compounds) from deep-frozen core samples taken during DSDP Leg 75 (Holes 530A and 532) were analyzed by a combined hydrogen-stripping/thermovaporization method. Concentrations representing both hydrocarbons dissolved in the pore water and adsorbed on the mineral surfaces vary in Hole 530A from about 10 to 15,000 ng/g of dry sediment weight depending on the lithology (organic-carbon-lean calcareous oozes versus "black shales"). Likewise, the organic-carbon-normalized C2-C8 hydrocarbon concentrations vary from 3,500 to 93,100 ng/g Corg, reflecting drastic differences in the hydrogen contents and hence the hydrocarbon potential of the kerogens. The highest concentrations measured of nearly 10**5 ng/g Corg are about two orders of magnitude below those usually encountered in Type-II kerogen-bearing source beds in the main phase of petroleum generation. Therefore, it was concluded that Hole 530A sediments, even at 1100 m depth, are in an early stage of evolution. The corresponding data from Hole 532 indicated lower amounts (3,000-9,000 ng/g Corg), which is in accordance with the shallow burial depth and immaturity of these Pliocene/late Miocene sediments. Significant changes in the light hydrocarbon composition with depth were attributed either to changes in kerogen type or to maturity related effects. Redistribution pheonomena, possibly the result of diffusion, were recognized only sporadically in Hole 530A, where several organic-carbon lean samples were enriched by migrated gaseous hydrocarbons. The core samples from Hole 530A were found to be severely contaminated by large quantities of acetone, which is routinely used as a solvent during sampling procedures on board Glomar Challenger.

Geochemistry at DSDP Leg 75 Holes

Samples of sediments and rocks collected at DSDP Sites 530 and 532 were analyzed for 44 major, minor, and trace elements for the following purposes: (1) to document the downhole variability in geochemistry within and between lithologic units; (2) to document trace-element enrichment, if any, in Cretaceous organic-carbon-rich black shales at Site 530; (3) to document trace-element enrichment, if any, in Neogene organic-carbon-rich sediments at Site 532; (4) to document trace-element enrichment, if any, in red claystone above basalt basement at Site 530 that might be attributed to hydrothermal activity or weathering of basalt. Results of the geochemical analyses showed that there are no significant enrichments of elements in the organic-carbon-rich sediments at Site 532, but a number of elements, notably Cd, Co, Cr, Cu, Mo, Ni, Pb, V, and Zn, are enriched in the Cretaceous black shales. These elements have different concentration gradients within the black-shale section, however, which suggests that there was differential mobility of trace elements during diagenesis of interbedded more-oxidized and less-oxidized sediments. There is little or no enrichment of elements from hydrothermal activity in the red claystone immediately overlying basalt basement at Site 530, but slight enrichments of several elements in the lowest meter of sediment may be related to subsea weathering of basalt

Organic geochemical character of selected cores at DSDP Hole 75-530A

The Albian/Cenomanian strata in Hole 530A are organically richer than are the post-Cenomanian strata. Organic matter is thermally immature and appears to be of dominantly marine origin with either variable levels of oxidation or variable amounts of terrestrial input. Geochemical data alone cannot establish whether the black shales present in Hole 530A represent deposition within a stagnant basin or within an expanded oxygen-minimum layer

Micropaleontological investigation of Late Albanian Col de Palluel

The Niveau Breistroffer black shale succession in the Vocontian Basin (SE France) is the regional equivalent of the widely distributed Late Albian Oceanic Anoxic Event 1d. The studied black shale-rich interval at the Col de Palluel section is 6.28 m thick and comprises four black shale units with up to 2.5 wt% total organic carbon (TOC) intercalated with marlstones. Calcareous nannofossil, palynomorph, planktic Foraminifera and stable isotopic data from the Niveau Breistroffer succession suggest that short-term climate changes influenced its deposition, with relatively warm and humid climate during black shale formation in comparison with relatively cool and dry climatic conditions during marlstone deposition. An increase in the terrigenous/marine ratio of palynomorphs indicates enhanced humidity and higher runoff during black shale formation. A nutrient index based on calcareous nannofossils and the abundance pattern of small (63-125 µm) hedbergellid Foraminifera show short-term changes in the productivity of the surface water. Surface-water productivity was reduced during black shale formation and increased during marlstone deposition. A calcareous nannofossil temperature index and bulk-rock oxygen isotope data indicate relative temperature changes, with warmer surface waters for black shale samples. At these times, warm-humid climate and reduced surface-water productivity were accompanied by greater abundances of 'subsurface'-dwelling calcareous nannofossils (nannoconids) and planktic Foraminifera (rotaliporids). These taxa presumably indicate more stratified surface-water conditions. We suggest that the formation of the Niveau Breistroffer black shales occurred during orbitally induced increase in monsoonal activity that led to increasing humidity during periods of black shale formation. This, in turn, caused a decrease in low-latitude deep-water formation and probably an increase in surface-water stratification. The combination of these two mechanisms caused depleted O2 concentrations in the bottom water that increased the preservation potential of organic matter

Geochemistry and Nd-Pb isotope ratios of sediments from the Lesser Antilles arc

The Lesser Antilles arc is a particularly interesting island arc because it is presently very active, it is located perpendicular to the South American continent and its chemical and isotopic compositions display a strong north-south gradient. While the presence in the south of a thick pile of sedimentary material coming from the old South American continent has long been suspected to explain the geochemical gradient, previous studies failed to demonstrate unambiguously a direct link between the arc lava compositions and the subducted sediment compositions. Here, we present new Nd, Sm, Th, U and Pb concentrations and Nd-Pb isotopic data for over 60 sediments from three sites located in the fore arc region of the Lesser Antilles arc. New data for DSDP Site 543 drill core located east of Dominica Island complement the data published by White et al. (1985, doi:10.1016/0016-7037(85)90082-1) and confirm their relatively uniform isotopic compositions (i.e., 206Pb/204Pb between 19.13 and 19.53). In contrast, data obtained on DSDP Site 144 located further south, on the edge of the South American Rise and on sediments from Barbados Island are much more variable (206Pb/204Pb ranges from 18.81 to 27.69). The very radiogenic Pb isotopic compositions are found in a 60 m thick black shale unit, which has no age equivalent in the Site 543 drill core. We interpret the peculiar composition of the southern sediments as being due to two factors, (a) the proximity of the South American craton, which contributes coarse grain old detrital material that does not travel far from the continental shelf, and (b) the presence of older sediments including the thick black shale unit formed during Oceanic Anoxic events 2 and 3. The north-south isotopic change known along the Lesser Antilles arc can be explained by the observed geographical changes in the composition of the subducted sediments. About 1% contamination of the mantle wedge by Site 543 sediments explains the composition of the northern islands while up to 10% sediments like those of Site 144 is required in the source of the southern island lavas. The presence of black shales in the subducted pile provides a satisfactory explanation for the very low Delta8/4 values that characterize the Lesser Antilles arc.

Composition of sediments and cores from DSDP Legs 54 and 61-63

The monograph gives results of studies of sediments and rocks collected from D/S Glomar Challenger in the Pacific Ocean. These studies have been based on the lithological facial analysis applied for the first time for identificating genesis of ocean sediments. These results include new ideas on formation of the Earth's sedimentary cover and can be used for constructing regional and global schemes of ocean paleogeography, reconstructing some structures, correlating sedimentation on continents and in oceans, estimating perspectives of oil- and gas-bearing deposits and ore formation. The monograph also gives the first petrographic classification of organic matter in black shales.

Lower Cretaceous nannofossils of ODP Holes 113-682B and 113-693A

Organic-rich, moderately to sparsely nannofossiliferous Lower Cretaceous claystones ("black shales") were cored at two Ocean Drilling Program Leg 113 sites on the continental slope of East Antarctica off Dronning Maud Land. A 39 m section at Site 692 yielded a Neocomian assemblage of limited diversity with rare Cyclagelosphaera deflandrei, Diadorhombus rectus, and Cruciellipsis cuvillieri, and is probably Valanginian in age. A 70-m section at Site 693 is assigned to the Rhagodiscus angustus Zone (late Aptian-early Albian in age). The latter zone is represented at DSDP sites on the Falkland Plateau, but equivalents to the Neocomian section are absent there, probably due to a disconformity. Watznaueria barnesae is the dominant species at both ODP sites, but it shares dominance with Repagulum parvidentatum at Site 693, where they total 70%-90% of the assemblage; their dominance is attributed to a paleogeographic setting within a restricted basin rather than to postdepositional dissolution of other species. The evolutionary development of this restricted basin and its eventual ventilation in early Albian times is discussed in terms of the regional stratigraphy and the breakup and dispersal of southwestern Gondwanaland. One new species, Corollithion covingtonii, is described.

Late Albian foraminiferal carbon and oxygen isotope data and biostratigraphic datums from ODP holes 171-1050C and 171-1052E

A late Albian-early Cenomanian record (~103.3 to 99.0 Ma), including organic-rich deposits and a d13C increase associated with oceanic anoxic event 1d (OAE 1d), is described from Ocean Drilling Program sites 1050 and 1052 in the subtropical Atlantic. Foraminifera are well preserved at these sites. Paleotemperatures estimated from benthic d18O values average ~14°C for middle bathyal Site 1050 and ~17°C for upper bathyal Site 1052, whereas surface temperatures are estimated to have ranged from 26°C to 31°C at both sites. Among planktonic foraminifera, there is a steady balance of speciation and extinction with no discrete time of major faunal turnover. OAE 1d is recognized on the basis of a 1.2 per mill d13C increase (~100.0-99.6 Ma), which is similar in age and magnitude to d13C excursions documented in the North Atlantic and western Tethys. Organic-rich "black shales" are present throughout the studied interval at both sites. However, deposition of individual black shale beds was not synchronous between sites, and most of the black shale was deposited before the OAE 1d d13C increase. A similar pattern is observed at the other sites where OAE 1d has been recognized indicating that the site(s) of excess organic carbon burial that could have caused the d13C increase has (have) yet to be found. Our findings add weight to the view that OAEs should be chemostratigraphically (d13C) rather than lithostratigraphically defined.

Sedimentology and origin of lower Cretaceous pelagic carbonates and redeposited clastics at DSDP Hole 76-534A

Drilling at Site 534 in the Blake-Bahama Basin recovered 268 m of Lower Cretaceous, Berriasian to Hauterivian, pelagic carbonates, together with volumetrically minor intercalations of claystone, black shales, and terrigenous and calcareous elastics. Radiolarian nannofossil pelagic carbonates accumulated in water depths of about 3300 to 3650 m, below the ACD (aragonite compensation depth) but close to the CCD (calcite compensation depth). Radiolarian abundance points to a relatively fertile ocean. In the Hauterivian and Barremian, during times of warm, humid climate and rising sea level, turbiditic influxes of both terrigenous and calcareous sediments, and minor debris flows were derived from the adjacent Blake Plateau. The claystones and black shales accumulated on the continental rise, then were redeposited onto the abyssal plain by turbidity currents. Dark organic-rich and pale organic-poor couplets are attributed to climatic variations on land, which controlled the input of terrigenous organic matter. Highly persistent, fine, parallel lamination in the pelagic chalks is explained by repeated algal "blooms." During early diagenesis, organic-poor carbonates remained oxygenated and were cemented early, whereas organic-rich intervals, devoid of burrowing organisms, continued to compact later in diagenesis. Interstitial dissolved-oxygen levels fluctuated repeatedly, but bottom waters were never static nor anoxic. The central western Atlantic in the Lower Cretaceous was thus a relatively fertile and wellmixed ocean basin.

Stable oxygen and carbon isotope ratios of foraminifera and test results after different sample cleaning procedures from ODP Leg 207 sediments

We report oxygen and carbon stable isotope analyses of foraminifers, primarily planktonic, sampled at low resolution in the Cretaceous and Paleogene sections from Sites 1257, 1258, and 1260. Data from two samples from Site 1259 are also reported. The very low resolution of the data only allows us to detect climate-driven isotopic events on the timescale of more than 500 k.y. A several million-year-long interval of overall increase in planktonic 18O is seen in the Cenomanian at Site 1260. Before and after this interval, foraminifers from Cenomanian and Turonian black shales have d18O values in the range -4.2 per mil to -5.0 per mil, suggestive of upper ocean temperatures higher than modern tropical values. The d18O values of upper ocean dwelling Paleogene planktonics exhibit a long-term increase from the early Eocene to the middle Eocene. During shipboard and postcruise processing, it proved difficult to extract well-preserved foraminifer tests from black shales by conventional techniques. Here, we report results of a test of procedures for cleaning foraminifers in Cretaceous organic-rich mudstone sediments using various combinations of soaking in bleach, Calgon/hydrogen peroxide, or Cascade, accompanied by drying, repeat soaking, or sonication. A procedure that used 100% bleach, no detergent, and no sonication yielded the largest number of clean, whole individual foraminifers with the shortest preparation time. We found no significant difference in d18O or d13C values among sets of multiple samples of the planktonic foraminifer Whiteinella baltica extracted following each cleaning procedure.

Organic geochemistry of upper Jurassic-Cretaceous sediments at DSDP Hole 71-511

Cretaceous and Jurassic sediments 435 m thick were drilled at Site 511, in the basin province of the Falkland Plateau, during DSDP Leg 71. The calcareous Unit 3 and the clayey zeolitic Unit 4, both of Senonian age, revealed poorly preserved organic matter indicative of oxidized environments. The same characteristics prevailed for the clayey Unit 5 of Turonian to Albian age. Strictly reducing environments existed for black facies along Unit 6 of earliest Albian to Late Jurassic age and allowed the preservation of a rich organic material that is marine in origin. Besides the transition from reducing conditions in Unit 6 to oxidizing conditions in Unit 5, there are 20 meters of sediments in Cores 56-58 where detrital, nonmarine and then marine organic matter, both implying more or less reducing environments, are interlain by poorly preserved material. In the black shales of the bottom Cores 69 and 70, some nonmarine detritus is mixed with the predominantly marine organic material. An immature stage of evolution can be assigned to all of the samples studied. The chapter also undertakes a comparison with contemporaneous lithologies at adjacent Sites 327 and 330 and attempts some reconstruction of the geography of the eastern Falkland Plateau during the Mesozoic.