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.

Characteristics, pyrolysis, age, lithology, sedimentation rate, organic matter, and thermal alteration index at DSDP Leg 67 Holes

Marine-derived amorphous organic matter dominates hemipelagic and trench sediments in and around the Middle America Trench. These sediments contain, on the average, 1% to 2% total organic carbon (TOC), with a maximum of 4.8%. Their organic facies and richness reflect (1) the small land area of Guatemala, which contributes small amounts of higher land plant remains, and (2) high levels of marine productivity and regionally low levels of dissolved oxygen, which encourage deposition and preservation of marine organic remains. These sediments have good potential for oil but are now immature. For this reason, gaseous hydrocarbons like the ethane identified in the deep parts of the section, as at Sites 496 and 497, are probably migrating from a mature section at depth. The pelagic sediments of the downgoing Cocos Plate are lean in organic carbon and have no petroleum potential

Organic geochemistry, visual composition, atomic ratios, and reflectance at DSDP Site 87-582, 87-583 and 87-584

Geochemical analyses of organic matter were carried out on Quaternary sediments from Sites 582 and 583 (Nankai Trough) and on Pliocene to Miocene sediments from Site 584 (Japan Trench), DSDP Leg 87, to evaluate petroleum-generating potential and to characterize the organic matter. The vitrinite-huminite reflectances of indigenous materials for these sites are less than 0.3% indicating the immature nature of the sediments. The sediments, however, contain remarkable amounts of recycled organic materials. The Quaternary sediments from Sites 582 and 583 contain small amounts of amorphous organic matter (less than 0.75 wt.% organic carbon and 66-90% amorphous debris), which is composed of predominantly recycled, oxidized, and over-matured (or matured) Type III material. The amount of hydrocarbon yield indicates that those sediments have lean-source potential for commercial hydrocarbon generation. The Pliocene to Miocene sediments from Site 584 contain organic matter (0.3-1.09 wt.% organic carbon) of predominantly amorphous debris (68-96%) that originated in two sources, an indigenous Type II material and a recycled, over-matured material. Pyrolysis shows an upward increase in the section of hydrocarbon yield and the same trend is also observed in organic-carbon content. The amount of the yield indicates that the Miocene sediments have lean-to-fair source potential and the Pliocene sediments have fair-to-good source potential.

Organic facies and hydrocarbon potential at DSDP Leg 64 Holes

The sediments from the Gulf of California are potentially good sources for oil and gas. They are rich in organic carbon (av. = 1.9%). Sediments from the margins of the Gulf are rich in oil-prone marine-amorphous organic matter. Sediments from Guaymas Basin contain the same material plus abundant subordinate amounts of gas-prone terrestrially derived organic matter. The enrichment of all of these sediments in marine-amorphous components reflects deposition in a highly productive and oxygen-poor water mass. The sediments are thermally immature, except for those altered by hydrothermal activity or by the intrusion of sills. These sediments are extensively cooked and may have lost their potential for hydrocarbon generation.

Organic geochemistry of Cretaceous black shales at DSDP Hole 75-530A

Five-hundred ten meters of Cretaceous sediments were drilled north of the Walvis escarpment in Hole 530A during Leg 75. An immature stage of evolution for organic matter can be assigned to all the samples studied. Black shales are interbedded with red and green claystone in the bottom sedimentary unit, Unit 8, which is of Coniacian to late Albian age. The richest organic carbon contents and petroleum potentials occur in the black shales. Detrital organic matter is present throughout the various members of a sequence, mixed with largely oxidized organic matter in the gray and green claystone or marlstone members on both sides. Detrital organic matter also characterizes the black streaks observed in the claystones. Vertical discontinuities in organic matter distribution are assigned to slumping. Several types of black shales can be identified, according to their content of detrital organic matter, the more detrital black levels corresponding to the Albian-Cenomanian period. Cyclic variations of organic matter observed for a sequence can occur for a set of sequences and even for some consecutive sets of sequences. Climatic factors are proposed to account for the cyclic sedimentation and distribution of organic matter for every sequence that includes a black bed.

Molecular and stable isotope composition of headspace and total hydrogencarbon gases of ODP Leg 104 sites

Molecular and isotope compositions of headspace and total (free + sorbed) hydrocarbon gases from drilled cores of the three ODP Leg 104 Sites 642, 643, and 644 of the Voring Plateau are used to characterize the origin and distribution of these gases in Holocene to Eocene sediments. Only minor amounts of methane were found in the headspace (0.1 to < 0.001 vol%). Although methane through propane are present in all of the total gas samples, different origins account for the concentration and composition variations found. Site 643 at the foot of the outer Voring Plateau represents a geological setting with poor hydrocarbon generating potential, (sediments with low TOC and maturity overlying oceanic basement). Correspondingly, the total gas concentrations are low, typical for background gases (yield C1 - 4 = 31 to 232 ppb, C1/C2+ = 0.6 to 4; delta13C(CH4) -22 per mil to -42 per mil) probably of a diagenetic origin. Holocene to Eocene sediments, which overlie volcanic units, were drilled on the outer Vdring Plateau, at Holes 642B and D. Similar to Site 643, these sediments possess a poor hydrocarbon generating potential. The total gas character (yield C1 - 4 = 20 to 410 ppb; C1/C2+ = 1.7 to 13.3; delta13C(CH4) ca. -23 per mil to -40 per mil) again indicates a diagenetic origin, perhaps with the addition of some biogenic gas. The higher geothermal gradient and the underlying volcanics do not appear to have any influence on the gas geochemistry. The free gas (Vacutainer TM) in the sediments at Site 644 are dominated by biogenic gas (C1/C2+ > 104; delta13C(CH4) -77 per mil). Indications, in the total gas, of hydrocarbons with a thermogenic signature (yield C1 - 4 = 121 to 769 ppb, C1/ C2+ = 3 to 8; delta13C(CH4) = -39 per mil to -71 per mil), could not be unequivocally confirmed as such. Alternatively, these gases may represent mixtures of diagenetic and biogenic gases.

Geochemical characterization of black shales from the Tarfaya Basin

Organic geochemical and petrological investigations were carried out on Cenomanian/Turonian black shales from three sample sites in the Tarfaya Basin (SW Morocco) to characterize the sedimentary organic matter. These black shales have a variable bulk and molecular geochemical composition reflecting changes in the quantity and quality of the organic matter. High TOC contents (up to 18wt%) and hydrogen indices between 400 and 800 (mgHC/gTOC) indicate hydrogen-rich organic matter (Type I-II kerogen) which qualifies these laminated black shale sequences as excellent oil-prone source rocks. Low Tmax values obtained from Rock-Eval pyrolysis (404-425 MC) confirm an immature to early mature level of thermal maturation. Organic petrological studies indicate that the kerogen is almost entirely composed of bituminite particles. These unstructured organic aggregates were most probably formed by intensive restructuring of labile biopolymers (lipids and/or carbohydrates), with the incorporation of sulphur into the kerogen during early diagenesis. Total lipid analyses performed after desulphurization of the total extract shows that the biomarkers mostly comprise short-chain n-alkanes (C16-C22) and long-chain (C25-C35) n-alkanes with no obvious odd-over-even predominance, together with steranes, hopanoids and acyclic isoprenoids. The presence of isorenieratane derivatives originating from green sulphur bacteria indicates that dissolved sulphide had reached the photic zone at shallow water depths (~100m) during times of deposition. These conditions probably favoured intensive sulphurization of the organic matter. Flash pyrolysis GC-MS analysis of the kerogen indicates the aliphatic nature of the bulk organic carbon. The vast majority of pyrolysis products are sulphur-containing components such as alkylthiophenes, alkenylthiophenes and alkybenzothiophenes. Abundant sulphurization of the Tarfaya Basin kerogen resulted from excess sulphide and metabolizable organic matter combined with a limited availability of iron during early diagenesis. The observed variability in the intensity of OM sulphurization may be attributed to sea level-driven fluctuations in the palaeoenvironment during sedimentation.

Investigations of Cretaceous and Tertiary kerogens in sediments of ODP Leg 113 holes

Seventy-one samples from nine sites were analyzed for total organic carbon (TOC). Fifty-six samples, containing 0.2% or more TOC, were evaluated by Rock-Eval to assess the nature of their kerogen and its petroleum source potential. Visual kerogen studies were carried out. Petroleum potential was encountered only in Valanginian calcareous claystones at Hole 692B close to the margin of Dronning Maud Land. A section of 44.7 m was penetrated. The unit possesses a revised mean TOC of 9.8% and petroleum potential of 43.2 kg/Mg, relatively high values in comparison to other Cretaceous anoxic oceanic sections and the totality of petroleum source rocks. At Sites 689 and 690, extremely low TOC levels, mean 0.07%, preclude kerogen analysis. Kerogens in Eocene to Pliocene sediments of the central and western Weddell Sea (Sites 694, 695, 696, and 697) are similar everywhere, largely comprising brown to black, granular, amorphous material of high rank, and generally possessing several reflectance populations of vitrinite particles. The latter are interpreted as indicative of the recycling of sediments of a variety of levels of thermal maturity.

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.

Carbonate, organic carbon, pyrolysis and composition of the extracts at DSDP Holes 76-534A and 44-391

The geochemical studies of Sites 534 and 391 and their comparison allow us to improve the chemical characterization of different geological formations dating from the early Callovian to the Maestrichtian along the continental margin of eastern North America. Three of the formations are favorable for the preservation of organic matter: (1) the unnamed formation (middle Callovian to Oxfordian), (2) the Blake-Bahama Formation (Berriasian to Barremian), and (3) the Hatteras Formation (Aptian to Cenomanian). The organic matter is mainly detrital, except for a few organic-rich layers where a contribution of aquatic material occurs. In these organic-rich layers, the petroleum potential is medium to good. Maturation has not quite reached the beginning of the oil window even for the deepest organic material.

Lithology and organic geochemistry at DSDP Hole 77-535

Analyses of extractable organic matter from selected core samples obtained at DSDP Site 535 in the eastern Gulf of Mexico show that the asphalt (or tar) and adjacent oil stains in Lower Cretaceous fractured limestones have a common origin and are not derived from the surrounding organic-matter-rich limestones. Organic matter indigenous to those surrounding limestones was shown to be thermally immature and incapable of yielding the hydrocarbon mixture discovered. In contrast, the oil-stained and asphaltic material appears to be a post-migration alteration product of a mature oil that has migrated from source rocks deeper in the section, or from stratigraphically equivalent but compositionally different source-facies down-dip from the drill site. Further, hydrocarbons of the altered petroleum residues were shown to be similar to Sunniland-type oils found in Lower Cretaceous rocks of South Florida. The results suggest that shallowwater, platform-type source-rock facies similar to those that generated Sunniland-type oils, or deeper-water facies having comparable oil-generating material, are present in this deep-water (> 3000 m) environment. These findings have important implications for the petroleum potential in the eastern Gulf of Mexico and for certain types of deep-sea sediments.

Distribution, origin, and hydrocarbon-potential of organic matter in sediments from DSDP Leg 66 Holes

As part of an ongoing program of organic geochemical studies of sediments recovered by the Deep Sea Drilling Project, we have analyzed the types, amounts, and thermal alteration indices of organic matter collected from the Pacific continental margin of southern Mexico on Leg 66. The samples were pieces of core frozen aboard ship. Some of them were analyzed by pyrolysis, heavy C15+ hydrocarbons, and nonhydrocarbons to help determine their origin and hydrocarbon potential. Our main objectives were to find out how much organic matter was being deposited; to establish whether it derived from marine or terrestrial sources; to determine the controls of deposition of organic matter; to estimate the hydrocarbon potential of the drilled section; and to compare and contrast organic sedimentation here with that on other margins.

Geochemical analyses at DSDP Holes 72-515B and 72-516F

The petroleum-generating potential of five samples from Hole 515B, Vema Channel, and of 23 samples from Hole 516F, Rio Grande Rise, was analyzed. Organic carbon and pyrolysis data indicated that source rocks of good quality are not present. Microscopic examination showed predominance of woody organic matter, which is more favorable for the generation of gas in a mature stage; all samples, however, are still thermally immature.

Organic geochemistry of sediment samples from Prydz Bay

High molecular weight aliphatic hydrocarbons were extracted from sediments at two sites (741 and 742) drilled during Ocean Drilling Program Leg 119 in Prydz Bay, a major embayment on the continental shelf of East Antarctica. The distributions of n-alkanes and triterpenoid and steroid hydrocarbons suggest that the n-alkanes and steranes are mainly of terrestrial origin and that the hydrocarbons are immature to slightly mature in the Lower Cretaceous sediments and immature to mature in the Tertiary sediments. At Site 741, the Lower Cretaceous depositional sequence, which is generally characterized by immature hydrocarbons, is interrupted by sediment having more mature components, suggesting a change of source during part of Early Cretaceous time. At Site 742, the mature geochemical parameters of a Pliocene sample correlate with results reported elsewhere for Site 739. In all but one of the other Tertiary samples, the geochemical parameters indicate intermediate maturity. The Lower Cretaceous and Pliocene sediments average about 1.9% organic carbon, a value of interest from the point of view of potential sources of petroleum offshore from Antarctica.