Organic geochemical character and hydrocarbon source potential of selected black shales at DSDP Hole 93-603B

LECO analysis, pyrolysis assay, and bitumen and elemental analysis were used to characterize the organic matter of 23 black shale samples from Deep Sea Drilling Project Leg 93, Hole 603B, located in the western North Atlantic. The organic matter is dominantly gas-prone and/or refractory. Two cores within the Turonian and Cenomanian, however, contained significant quantities of well-preserved, hydrogen-enriched, organic matter. This material is thermally immature and represents a potential oil-prone source rock. These sediments do not appear to have been deposited within a stagnant, euxinic ocean as would be consistent with an "oceanic anoxic event." Their organic geochemical and sedimentary character is more consistent with deposition by turbidity currents originating on the continental shelf and slope.

Black shales from the Upper Aptian and Lower Albanian of the Volcontian Basin

Calcareous nannoplankton, palynomorph, benthic foraminifera, and oxygen isotope records from the supraregionally distributed Niveau Paquier (Early Albian age, Oceanic Anoxic Event 1b) and regionally distributed Niveau Kilian (Late Aptian age) black shales in the Vocontian Basin (SE France) exhibit variations that reflect paleoclimatic and paleoceanographic changes in the mid-Cretaceous low latitudes. To quantify surface water productivity and temperature changes, nutrient and temperature indices based on calcareous nannofossils were developed. The nutrient index strongly varies in the precessional band, whereas variations of the temperature index reflect eccentricity. Since polar ice caps were not present during the mid-Cretaceous, these variations probably result from feedback mechanisms within a monsoonal climate system of the mid-Cretaceous low latitudes involving warm/humid and cool/dry cycles. A model is proposed that explains the formation of mid-Cretaceous black shales through monsoonally driven changes in temperature and evaporation/precipitation patterns. The Lower Albian Niveau Paquier, which has a supraregional distribution, formed under extremely warm and humid conditions when monsoonal intensity was strongest. Bottom water ventilation in the Vocontian Basin was diminished, probably due to increased precipitation and reduced evaporation in regions of deep water formation at low latitudes. Surface water productivity in the Vocontian Basin was controlled by the strength of monsoonal winds. The Upper Aptian Niveau Kilian, which has a regional distribution only, formed under a less warm and humid climate than the Niveau Paquier. Low-latitude deep water formation was reduced to a lesser extent and/or on regional scale only. The threshold for the formation of a supraregional black shale was not reached. The intensity of increases in temperature and humidity controlled whether black shales developed on a regional or supraregional scale. At least in the Vocontian Basin, the increased preservation of organic matter at the sea floor was more significant in black shale formation than the role of enhanced productivity.

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.

Chemical composition of Black Sea bottom sediments

Concentrations of major-, trace- and rare earth elements in recent and Old Black Sea bottom sediments are reported in the paper. Data presented suggest that accumulation of black shale deposits was not constrained to a certain time span but proceeds in certain modern basins and generates sediments with metal contents close to those in their ancients analogues in hydrogen sulfide contaminated environments. If REE are involved in the process, their composition can vary depending on such factors as variations in redox conditions and occurrence of phosphate and barite nodules, which can induce development of either positive or negative Eu anomalies.

(Table T1) Total procaryotes, and living bacteria and archaea in black shales of ODP Leg 207 sites

Subseafloor sediments harbor over half of all prokaryotic cells on Earth (Whitman et al., 1998). This immense number is calculated from numerous microscopic acridine orange direct counts (AODCs) conducted on sediment cores drilled during the Ocean Drilling Program (ODP) (Parkes et al., 1994, doi:10.1038/371410a0, 2000, doi:10.1007/PL00010971). Because these counts cannot differentiate between living and inactive or even dead cells (Kepner and Pratt, 1994; Morita, 1997), the population size of living microorganisms has recently been enumerated for ODP Leg 201 sediment samples from the equatorial Pacific and the Peru margin using ribosomal ribonucleic acid targeting catalyzed reporter deposition-fluorescence in situ hybridization (CARD-FISH) (Schippers et al., 2005, doi:10.1038/nature03302). A large fraction of the subseafloor prokaryotes were alive, even in very old (16 Ma) and deep (>400 m) sediments. In this study, black shale samples from the Demerara Rise (Erbacher, Mosher, Malone, et al., 2004, doi:10.2973/odp.proc.ir.207.2004) were analyzed using AODC and CARD-FISH to find out if black shales also harbor microorganisms.

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.

(Table 1) Organic carbon isotopic composition in Cretaceous sediments at DSDP Hole 75-530A

Cretaceous sediments from DSDP Site 530 have been analyzed for organic carbon isotopic composition. The d13C values in the sediments decrease from -22.7 per mil to -27.5 per mil in the following order: light-olive green mudstone/claystone, dark brown-red mudstone/siltstone/claystone, and black shale. This large range is primarily the result of variation in the relative amounts of terrestrial organic carbon superimposed on that derived from marine organisms. The black shales have an average d13C value of -25.9 per mil (range is from -23.7 per mil to -27.5 per mil). These values indicate that they originated primarily in terrigenous organic materials. The average d13C value present throughout the Cretaceous suggests that a large amount of terrestrial organic matter was supplied into this paleoenvironment, except during the Campanian, when an average d13C of -23.9 per mil is found near the marine end of the range.

The Cenomanian/Turronian Boundary Event at ODP Hole 103-641A

Drilling at ODP Site 641 (on the western margin of Galicia Bank, off northwestern Spain) revealed a thin, but pronounced, interval of black shale and gray-green claystone. Our high-resolution study combines the sedimentology, micropaleontology (palynomorphs and others), organic and inorganic geochemistry, and isotopic values of this layer to demonstrate the distinct nature of the sediment and prove that the sequence represents the local sedimentary expression of the global Cenomanian/Turonian Oceanic Anoxic Event (OAE) of Schlanger and Jenkyns (1976), Arthur and Schlanger (1979), and Jenkyns (1980), also called the Cenomanian/Turonian Boundary Event (CTBE). The most striking evidence is that the strong positive d13C excursion characterizing the CTBE sequences in shallow areas can be traced into a pronounced deep-sea expression, thus providing a good stratigraphic marker for the CTBE in various paleosettings. The isotopic excursion at Site 641 coincides with an extremely enriched trace metal content, with values that were previously unknown for the Cretaceous Atlantic. Similar to other CTBE occurrences, the organic carbon content is high (up to 11%) and the organic matter is of dominantly marine origin (kerogen type II). The bulk mineralogy of the CTBE sediments does not differ significantly from the general trend of Cretaceous North Atlantic sediments (dominance of smectite and zeolite with minor amounts of illite and scattered palygorskite, kaolinite, and chlorite); thus, no evidence for either increased volcanic activity nor a drastic climatic change in the borderlands was found. Results from Site 641 are compared with the CTBE section found at Site 398, DSDP Leg 47B (Vigo Seamount at the southern end of the Galicia Bank).

(Table 1) Maceral composition and organic carbon chemistry of ODP Leg 104 samples

The Cenozoic sediments sampled in ODP Leg 104 on the Vøring Plateau show a distinct variability of the total organic carbon content (TOC) and the accumulation rates of TOC. Based on the geochemical and organic-petrographic characterization of the sedimentary organic matter (OM), the allochthonous and autochthonous proportion of the OM could be quantified. The results clearly demonstrate that high TOC percentages and TOC accumulation rates in Cenozoic sediment sections display a generally high input of allochthonous organic matter. Oxidized and partly well-rounded organic particles built up the main portion of OM within the Miocene, TOC-rich sediments. The most probable source of this oxidized OM are reworked sediments from the Scandinavian shelf. Changes in the input of these organic particles are to some degree correlative with sea-level changes. The Cenozoic accumulation of autochthonous OM is low and does not reveal a clear variation during the Miocene and early Pliocene. In spite of a high accumulation rate of biogenic opal during the Early Miocene, the accumulation rate of autochthonous TOC is low. The autochthonous particle assemblage is dominated by relatively inert OM, like dinoflagellate cysts. This points to an intensive biological and/or early diagenetic degradation of the marine OM under well oxidized bottom water conditions during the last 23 Myr. Nevertheless, a continuation of marine OM degradation during later stages of diagenesis cannot be excluded. A prominent dominance of allochthonous OM over autochthonous is documented with the beginning of the Pliocene. At 2.45 Ma the episodic occurrence of ice-rafted, thermally mature OM reflects the onset of the glacial erosion of Mesozoic, coal and black shale bearing sediments on the Scandinavian and Barents Sea shelves. The first occurrence of these, in view of the actual burial depth, thermally overmature OM particles is, therefore, a marker for the beginning of the strong Scandinavian glaciation and the advance of the glacial front toward the shelves.

Geochemical and nannofossil analyses of Cenomanian/Turonian sediments of DSDP Hole 75-530A

One of the key objectives of Deep Sea Drilling Project (DSDP) Leg 75 was to shed light on the underlying causes of Cretaceous oceanic anoxia in the South Atlantic by addressing two major hypotheses: productivity productivity-driven anoxia vs. enhanced ocean stratification leading to preservation of organic matter and black shale deposition. Here we present a detailed geochemical dataset from sediments deposited during the Cenomanian/Turonian (C/T) transition and the global oceanic anoxic event 2 (OAE 2) at DSDP Site 530A, located off-shore Namibia (southeast Angola Basin, north of Walvis Ridge). To characterise the succession of alternating black and green shales at this site and to reconstruct the evolution of their paleoenvironmental setting, we have combined data derived from investigations on bulk organic matter, biomarkers and the inorganic fraction. The location of the C/T boundary itself is biostratigraphically not well constrained due to the carbonate-poor (but organic matter-rich) facies of these sediments. The bulk d13Corg record and compound-specific d13C data, in combination with published as well as new biostratigraphic data, enabled us to locate more precisely the C/T boundary at DSDP Site 530A. The compound-specific d13C record is the first of this kind reported from C/T black shales in the South Atlantic. It is employed for paleoenvironmental reconstructions and chemostratigraphic correlation to other C/T sections in order to discuss the paleoceanographic aspects and implications of the observations at DSDP Site 530A in a broader context, e.g., with regard to the potential trigger mechanisms of OAE 2, global changes in black shale deposition and climate. On a stratigraphic level, an approximation and monitoring of the syndepositional degree of oxygen depletion within the sediments/bottom waters in comparison to the upper water column is achieved by comparing normalised concentrations of redox-sensitive trace elements with the abundance of highly source specific molecular compounds. These biomarkers are derived from photoautotrophic and simultaneously anoxygenic green sulphur bacteria (Chlorobiacea) and are interpreted as paleoindicators for events of photic zone euxinia. In contrast to a number of other OAE 2 sections that are characterised by continuous black shale sequences, DSDP Site 530A represents a highly dynamic setting where newly deposited black shales were repeatedly exposed to conditions of subtle bottom water re-oxidation, presumably leading to their progressive alteration into green shales. The frequent alternation between both facies and the related anoxic to slight oxygenated conditions can be best explained by variations in vertical extent of an oxygen minimum zone in response to changes in a highly productive western continental margin setting driven by upwelling.

Detailed analysis of the organic carbon content in sediment cores M0002 and M0004

During IODP Expedition 302 (Arctic Coring Expedition-ACEX), the first scientific drilling campaign in the permantly ice-covered central Arctic Ocean, a 430 m thick sequence of upper Cretaceaous to Quaternary sediments has been drilled. The lower half of this sequence is composed of organic-carbon-rich (black shale-type) sediments with total organic carbon contents of about 1-14%. Significant amounts of the organic matter preserved in these sediments is of algae-type origin and accumulated under anoxic/euxinic conditions. Here, for the first time detailed data on the source-rock potential of these black shales are presented, indicating that most of the Eocene sediments have a (fair to) good source-rock potential, prone to generate a gas/oil mixture. The source-rock potential of the Campanian and upper Paleocene sediments, on the other hand, is rather low. The presence of oil or gas already generated in situ, however, can be ruled out due to the immaturity of the ACEX sediments.

(Table 1) Planktonic foraminifer abundance and stable isotope ratios of a sediment core near Baddeckenstedt, north Germany

A refined sample processing technique using glacial acetic acid has been applied to Upper Cenomanian and Lower Turonian limestones from Baddeckenstedt (Lower Saxony) enabeling the first quantitative analysis of planktonic foraminiferal populations through the Stage boundary succession in northwestern Germany. Measurements of carbonate contents, organic carbon and stable carbon and oxygen isotopes were also reported. These data allow a correlation to be made of the Baddeckenstedt section with those at Misburg (basinal facies, northwestern Germany) and Dover (Plenus Marls, southern England). Significant maxima of the organic carbon content at Baddeckenstedt correspond to prominent black shale couplets at Misburg. The planktonic foraminiferal generic groups show at Baddeckenstedt similar fluctuations as reported from Dover. Their correlation reveals details of a complex paleoceanographic regime in the NW-German Basin during the Cenomanian/Turonian Oceanic Anoxic Event.

Low-molecular-weight hydrocarbons in sediments at DSDP Sites 89-585 and 89-586

C2-C8 hydrocarbon concentrations (about 35 compounds identified, including saturated, aromatic, and olefinic compounds) from 38 shipboard sealed, deep-frozen core samples of Deep Sea Drilling Project Sites 585 (East Mariana Basin) and 586 (Ontong-Java Plateau) were determined by a gas stripping-thermovaporization method. Total concentrations, which represent the hydrocarbons dissolved in the pore water and adsorbed on the mineral surfaces of the sediment, vary from 20 to 630 ng/g of rock at Site 585 (sub-bottom depth range 332-868 m). Likewise, organic-carbon normalized yields range from 3*10**4 to 9*10**5 ng/g Corg, indicating that the organic matter is still in the initial, diagenetic evolutionary stage. The highest value (based on both rock weight and organic carbon) is measured in an extremely organic-carbon-poor sample of Lithologic Subunit VB (Core 585-30). In this unit (504-550 m) several samples with elevated organic-carbon contents and favorable kerogen quality including two thin "black-shale" layers deposited at the Cenomanian/Turonian boundary (not sampled for this study) were encountered. We conclude from a detailed comparison of light hydrocarbon compositions that the Core 585-30 sample is enriched in hydrocarbons of the C2-C8 molecular range, particularly in gas compounds, which probably migrated from nearby black-shale source layers. C2-C8 hydrocarbon yields in Site 586 samples (sub-bottom depth range 27-298 m) did not exceed 118 ng/g of dry sediment weight (average 56 ng/g), indicating the immaturity of these samples.