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.

Migration of C1 to C8 volatile organic compounds in sediments at DSDP Hole 75-530A

The distribution of C1 to C8 hydrocarbons in sediment samples from DSDP Leg 75, Hole 530A, indicates that significant amounts of methane and ethane have migrated from organic-rich to organic-lean shales in close proximity. Most compounds larger than ethane are not migrating out of black shales, where they occur in high concentrations. These results lead to a general model for assessing migration. In addition, three shale types are identified on the basis of organic carbon and pyrolysis products and patterns.

Petrography and geochemistry of organic matter in Triassic and Cretaceous sediments from the Wombat and Exmouth Plateau

Triassic (Carnian-Rhaetian) continental margin sediments from the Wombat Plateau off northwest Australia (Sites 759, 760, 761, and 764) contain mainly detrital organic matter of terrestrial higher plant origin. Although deposited in a nearshore deltaic environment, little liptinitic material was preserved. The dominant vitrinites and inertinites are hydrogen-lean, and the small quantities of extractable bitumen contain w-alkanes and bacterial hopanoid hydrocarbons as the most dominant single gas-chromatography-amenable compounds. Lower Cretaceous sediments on the central Exmouth Plateau (Sites 762 and 763) farther south in general have an organic matter composition similar to that in the Wombat Plateau sediments with the exception of a smaller particle size of vitrinites and inertinites, indicating more distal transport and probably deposition in deeper water. Nevertheless, organic matter preservation is slightly better than in the Triassic sediments. Long-chain fatty acids, as well as aliphatic ketones and alcohols, are common constituents in the Lower Cretaceous sediments in addition to n-alkanes and hopanoid hydrocarbons. Thin, black shale layers at the Cenomanian/Turonian boundary, although present at several sites (Sites 762 and 763 on the Exmouth Plateau, Site 765 in the Argo Abyssal Plain, and Site 766 on the continental margin of the Gascoyne Abyssal Plain), are particularly enriched in organic matter only at Site 763 (up to 26%). These organic-matter-rich layers contain mainly bituminite of probable fecal-pellet origin. Considering the high organic carbon content, the moderate hydrogen indices of 350-450 milligrams of hydrocarbon-type material per gram of Corg, the maceral composition, and the low sedimentation rates in the middle Cretaceous, we suggest that these black shales were accumulated in an area of oxygen-depleted bottom-water mass (oceanwide reduced circulation?) underlying an oxygen-rich water column (in which most of the primary biomass other than fecal pellets is destroyed) and a zone of relatively high bioproductivity. Differences in organic matter accumulation at the Cenomanian/Turonian boundary at different sites off northwest Australia are ascribed to regional variations in primary bioproductivity.

Cenomanian benthic foraminifera of Demerara Rise

This study is based on Cenomanian sediments of Ocean Drilling Program (ODP) Sites 1258 and 1260 from Demerara Rise (Leg 207, western tropical Atlantic, off Suriname, ~1000 and ~500 m paleo-water depth, respectively). Studied sediments consist of laminated black shales with TOC values between 3 and 18% and include the Mid Cenomanian Event (MCE), a positive carbon isotope excursion predating the well-known Oceanic Anoxic Event 2 (OAE 2). Benthic foraminiferal assemblages of the continuously eutrophic environment at Demerara Rise are characterized by low diversities (<= 9 species per sample) and large fluctuations in abundances, indicating oxygen depletion and varying organic matter fluxes. Dominant species at both sites are Bolivina anambra, Gabonita levis, Gavelinella dakotensis, Neobulimina albertensis, Praebulimina prolixa, and Tappanina cf. laciniosa. Benthic foraminiferal assemblages across the MCE show a threefold pattern: (1) stable ecological conditions below the MCE interval indicated by relatively high oxygenation and fluctuating organic matter flux, (2) decreasing oxygenation and/or higher organic matter flux during the MCE with decreasing benthic foraminiferal numbers and diversities (Site 1258) and a dominance of opportunistic species (Site 1260), and (3) anoxic to slightly dysoxic bottom-water conditions above the MCE as indicated by very low diversities and abundances or even the absence of benthic foraminifera. Slightly dysoxic conditions prevailed until OAE 2 at Demerara Rise. A comparison with other Atlantic Ocean and Tethyan sections indicates that the MCE reflects a paleoceanographic turning point towards lower bottom-water oxygenation, at least in the proto-North Atlantic Ocean and in the Tethyan and Boreal Realms. This general trend towards lower oxygenation of bottom waters across the MCE is accompanied by ongoing climate warming in combination with rising sea-level and the development of vast shallow epicontinental seas during the Middle and Late Cenomanian. These changes are proposed to have favoured the formation of warm and saline waters that may have contributed to intermediate- and deep-water masses at least in the restricted proto-North Atlantic and Tethyan Ocean basins, poor oxygenation of the Late Cenomanian sediments, and the changes in benthic foraminiferal assemblages across the MCE.