Geochemistry and kinetic models od Cretaceous samples

The source rock potential of Cretaceous organic rich whole rock samples from deep sea drilling project (DSDP) wells offshore southwestern Africa was investigated using bulk and quantitative pyrolysis techniques. The sample material was taken from organic rich intervals of Aptian, Albian and Turonian aged core samples from DSDP site 364 offshore Angola, DSDP well 530A north of the Walvis Ridge offshore Namibia, and DSDP well 361 offshore South Africa. The analytical program included TOC, Rock-Eval, pyrolysis GC, bulk kinetics and micro-scale sealed vessel pyrolysis (MSSV) experiments. The results were used to determine differences in the source rock petroleum type organofacies, petroleum composition, gas/oil ratio (GOR) and pressure-volume-temperature (PVT) behavior of hydrocarbons generated from these black shales for petroleum system modeling purposes. The investigated Aptian and Albian organic rich shales proved to contain excellent quality marine kerogens. The highest source rock potential was identified in sapropelic shales in DSDP well 364, containing very homogeneous Type II and organic sulfur rich Type IIS kerogen. They generate P-N-A low wax oils and low GOR sulfur rich oils, whereas Type III kerogen rich silty sandstones of DSDP well 361 show a potential for gas/condensate generation. Bulk kinetic experiments on these samples indicate that the organic sulfur contents influence kerogen transformation rates, Type IIS kerogen being the least stable. South of the Walvis Ridge, the Turonian contains predominantly a Type III kerogen. North of the Walvis Ridge, the Turonian black shales contain Type II kerogen and have the potential to generate P-N-A low and high wax oils, the latter with a high GOR at high maturity. Our results provide the first compositional kinetic description of Cretaceous organic rich black shales, and demonstrate the excellent source rock potential, especially of the Aptian-aged source rock, that has been recognized in a number of the South Atlantic offshore basins.

Geochemistry, lithology and maceral analysis at DSDP Hole 71-511

The quantity, type, and maturity of the organic matter in Recent through Upper Jurassic sediments from the Falkland Plateau, DSDP Site 511, have been determined. Sediments were investigated for their hydrocarbon potential by organic carbon and Rock-Eval pyrolysis. Kerogen concentrates were prepared and analyzed in reflected and transmitted light to determine vitrinite reflectance and maceral content. Total extractable organic compounds were analyzed for their elemental composition, and the fraction of the nonaromatic hydrocarbons was determined by capillary column gas chromatography and combined gas chromatography/mass spectrometry. Three main classes of organic matter can be determined at DSDP Site 511 by a qualitative and quantitative evaluation of microscopic and geochemical results. The Upper Jurassic to lower Albian black shales contain high amounts of organic matter of dominantly marine origin. The content of terrigenous organic matter increases at the base of the black shales, whereas the shallowest black shales near the Aptian/Albian boundary are transitional in composition, with increasing amounts of inert, partly oxidized organic matter which is the dominant component in all Albian through Tertiary sediments investigated. The organic matter in the black shales has a low level of maturity and has not yet reached the onset of thermal hydrocarbon generation. This is demonstrated by the low amounts of total extractable organic compounds, low percentages of hydrocarbons, and the pattern and composition of nonaromatic hydrocarbons. The observed reflectance of huminite and vitrinite particles (between 0.4% and 0.5% Ro at bottom-hole depth of 632 m) is consistent with this interpretation. Several geochemical parameters indicate, however, a rapid increase in the maturation of organic matter with depth of burial. This appears to result from the relatively high heat flow observed at Site 511. If we relate the level of maturation of the black shales at the bottom of Hole 511 to their present shallow depth of burial, they appear rather mature. On the basis of comparisons with other sedimentary basins of a known geothermal history, a somewhat higher paleotemperature gradient and/or additional overburden are required to give the observed maturity at shallow depth. A comparison with contemporaneous sediments of DSDP Site 361, Cape Basin, which was the basin adjacent and to the north of the Falkland Plateau during the early stages of the South Atlantic Ocean, demonstrates differences in sedimentological features and in the nature of sedimentary organic matter. We interpret these differences to be the result of the different geological settings for Sites 361 and 511.

Carbon chemistry of cretaceous marine organic matter

Geochemical studies of Cretaceous strata rich in organic carbon (OC) from Deep Sea Drilling Project (DSDP) sites and several land sections reveal several consistent relationships among amount of OC, hydrocarbon generating potential of kerogen (measured by pyrolysis as the hydrogen index, HI), and the isotopic composition of the OC. First, there is a positive correlation between HI and OC in strata that contain more than about 1% OC. Second, percent OC and HI often are negatively correlated with carbon isotopic composition (delta13C) of kerogen. The relationship between HI and OC indicates that as the amount of organic matter increases, this organic matter tends to be more lipid rich reflecting the marine source of the organic matter. Cretaceous samples that contain predominantly marine organic matter tend to be isotopically lighter than those that contain predominantly terrestrial organic matter. Average delta13C values for organic matter from most Cretaceous sites are between -26 and -28 per mil, and values heavier than about -25 per mil occur at very few sites. Most of the delta13C values of Miocene to Holocene OC-rich strata and modern marine plankton are between -16 to -23 per mil. Values of delta13C of modern terrestrial organic matter are mostly between -23 and -33 per mil. The depletion of terrestial OC in 13C relative to marine planktonic OC is the basis for numerous statements in the literature that isotopically light Cretaceous organic matter is of terrestrial origin, even though other organic geochemical and(or) optical indicators show that the organic matter is mainly of marine origin. A difference of about 5 per mil in delta13C between modern and Cretaceous OC-rich marine strata suggests either that Cretaceous marine planktonic organic matter had the same isotopic signature as modern marine plankton and that signature has been changed by diagenesis, or that OC derived from Cretaceous marine plankton was isotopically lighter by about 5 per mil relative to modern plankton OC. Diagenesis does not produce a significant shift in delta13C in Miocene to Holocene sediments, and therefore probably did not produce the isotopically light Cretaceous OC. This means that Cretaceous marine plankton must have had delta13C values that were about 5 per mil lighter than modern marine plankton, and at least several per mil lighter than Cretaceous terrestrial vegetation. The reason for these lighter values, however, is not obvious. It has been proposed that concentrations of CO2 were higher during the middle Cretaceous, and this more available CO2 may be responsible for the lighter delta13C values of Cretaceous marine organic matter.

Organic geochemistry and sedimentology of lower to mid-Cretaceous at DSDP Leg 77 Holes

Analyses of 40 carbonate core samples - 27 from Site 535, 12 from Site 540, and 1 from Site 538A - have confirmed many of the findings of the Shipboard Scientific Party. The samples, all but one Early to mid-Cretaceous in age (Berriasian to Cenomanian), reflect sequences of cyclically anoxic and oxic depositional environments. They are moderately to very dark colored, dominantly planar-parallel, laminated lime mudstones. Most show the effects of intense mechanical compaction. Visual kerogen characteristics and conventional Rock-Eval parameters indicate that these deep basinal carbonates contain varying mixtures of thermally immature kerogen derived from both marine and terrigenous precursors. However, variations in kerogen chemistry are evident upon analysis of the pyrolysis mass spectral data in conjunction with the other geochemical analyses. Particularly diagnostic is the reduction index, Rl, a measure of H2S produced during pyrolysis. Total organic carbon, TOC, ranges from 0.6 to 6.6%, with an overall average of 2.4%. Average TOCs for these fine-grained mudstones are: late Eocene 2.5% (1 sample), Cenomanian 2.2% (6), Albian 2.0% (10), Aptian 1.3% (1), Barremian-Hauterivian 2.8% (11), late Valanginian 4.8% (3), Berriasian-early Valanginian 1.6% (7). Most of the carbonates have source-potential ratings of fair to very good of predominantly oil-prone to mixed kerogen, with only a few gas-prone samples. The ratings correlate well with the inferred depositional environments, i.e., whether oxic or anoxic. Several new organic-geochemical parameters, especially Rl, based on pyrolysis mass spectrometry of powdered whole-rock samples, support this view. Tar from fractures in laminated to bioturbated limestones of Unit IV (late Valanginian) at 535-58-4, 19-20 cm (530 m sub-bottom) appears to be mature, biodegraded, and of migrated rather than on site indigenous origin.

Inorganic and organic geochemistry and sediment descriptions at DSDP Hole 93-603B

About one hundred samples of sediments and rocks recovered in Hole 603B were analyzed for type, abundance, and isotopic composition of organic matter, using a combination of Rock-Eval pyrolysis, C-H-N-S elemental analysis, and isotope-ratio mass spectrometry. Concentrations of major, minor, and trace inorganic elements were determined with a combination of X-ray fluorescence and induction-coupled plasma spectrometry. The oldest strata recovered in Hole 603B (lithologic Unit V) consist of interbedded light-colored limestones and marlstones, and black calcareous claystones of Neocomian age. The inorganic and organic geochemical results suggest a very terrigenous aspect to the black claystones. The organic geochemical results indicate that the limestones and marlstones contain a mixture of highly degraded marine and terrestrial organic matter. Comparison of the Neocomian carbonates at Site 603 with those on the other side of the North Atlantic, off Northwest Africa at Site 367, shows that the organic matter at Site 367 contains more marine organic matter, as indicated by higher pyrolysis hydrogen indices and lighter values of d13C. Comparison of inorganic geochemical results for the carbonate lithologies at Site 603 with those for carbonate lithologies at Site 367 suggests that the Site 603 carbonates may contain clastic material from both North American and African sources. The black claystones at Site 603, on the other hand, probably were derived almost entirely from North American clastic sources. Lithologic Unit IV overlying the Neocomian carbonates, consists of interbedded red, green, and black claystones. The black claystones at Site 603 contain more than ten times the organic carbon concentration of the interbedded green claystones. The average concentration of organic carbon in the black claystones (2.8%), however, is low relative to most mid-Cretaceous black claystones and shales in the Atlantic, particularly those found off Northwest Africa. The geochemical data all suggest that the organic matter in the black claystones is more abundant but generally more degraded than the organic matter in the green claystones, and that it was derived mainly from terrestrial sources and deposited in oxygenated bottom waters. The increased percentage of black claystone beds in the upper Cenomanian section, and the presence of more hydrogen-rich organic matter in this part of the section, probably resulted from the increased production and accumulation of marine organic matter that is represented worldwide near the Cenomanian/Turonian boundary in deep-sea and land sections. A few upper Cenomanian black claystone samples that have hydrogen indices > 150 also contain particularly high concentrations of V and Zn. Most samples of black claystone, however, are not particularly metal-rich compared with other black claystones and shales. Compared with red claystones from lithologic Unit IV, the green and black claystones are enriched in many trace transition elements, especially V, Zn, Cu, Co, and Pb. The main difference between the "carbonaceous" claystones of lithologic Unit IV and "variegated" or "multicolored" claystones of the overlying Upper Cretaceous to lower Tertiary Unit III is the absence of black claystone beds. As observed at several other sites (105 and 386), the multicolored claystones at Site 603 are somewhat enriched in several trace transition elements-especially Cu, Ni, and Cr-relative to most deep-sea clays. The multicolored claystones are not enriched in Fe and Mn, and therefore are not "metalliferous" sediments in the sense of those found at several locations in the eastern Pacific. The source of the slightly elevated concentrations of transition metals in the multicolored claystones probably is upward advection and diffusion of metals from the black claystones of the underlying Hatteras Formation. The red, orange, and green claystone beds of lithologic Unit II (Eocene), like those of Unit III, really represent a continuation of deposition of multicolored claystone that began after the deposition of the Neocomian carbonates. The color of the few black beds that occur within this unit results from high concentrations of manganese oxide rather than high concentrations of organic matter.

Organic geochemistry of ODP Leg 107 sediments

The Rock-Eval pyrolysis of rock samples and the elemental analysis of kerogens show clear differences between Messinian black shales and Pliocene-Pleistocene sapropels recovered during ODP Leg 107. The Messinian black shales are characterized by a large variety of compositions which probably reflects a great diversity of depositional and diagenetic paleoenvironments. In contrast, the Pliocene-Pleistocene sapropels, occurring as discrete layers in nannofossil oozes barren of organic carbon, constitute a rather homogeneous group in terms of organic content. A considerable contribution of terrestrial organic matter in the sapropels could mean that an identical phenomenon of terrestrial input has been periodically reproduced in the basin. The maturity and the nature of the organic matter are discussed with respect to anomalous values recorded for Tmax parameter.

Epoch, organic carbon and compounds at DSDP Holes 93-605 and 95-613

Twenty-four sediment samples from DSDP Holes 605 (Leg 93) and 613 (Leg 95) on the New Jersey continental rise were analyzed by pyrolysis-gas chromatography. Twelve of these samples were also analyzed by pyrolysis-gas chromatography/mass spectrometry. The degree of preservation of sediment organic matter, as determined by these techniques, helped to distinguish slumped sediments from sediments that have not moved from their original place of deposition. Total levels of pyrolyzable organic material, as determined from pyrolysis-gas chromatography, were low in sediments that were not slumped, indicating that the organic material is highly degraded. Nitrogen- and oxygen-containing compounds were the primary compounds detected by gas chromatography/mass spectrometry (GCMS) analysis of the pyrolyzate of non-slumped sediments. Smaller amounts of aromatic compounds and branched alkanes were also present in some of these samples. In contrast, slumped sediments showed larger amounts of pyrolyzable organic matter, as determined from pyrolysis-gas chromatography, and better preservation of alkyl chains in the sediment organic matter, as suggested by the presence of n-alkanes in GCMS analysis of the pyrolyzate. Better preservation of the organic matter in slumped sediments can be attributed to more moderate bioturbation by bottom-dwelling organisms at the original deposition site.

Organic carbon geochemistry of ODP Leg 121 samples

Organic petrological and geochemical analyses were performed on samples cored on Broken Ridge and Ninetyeast Ridge in the Central Indian Ocean during Leg 121. Organic carbon (Corg) contents are less than 1% in each individual sample and average Corg values calculated for larger stratigraphic units are less than 0.2%. Generally, there is more organic matter in Cretaceous sediments than in Tertiary. In the Cretaceous, the bulk of the organic matter consists of terrigenous debris, but a significant contribution of marine-derived organic matter was found in some samples, especially in the early Maestrichtian on Broken Ridge (Site 754). The youngest Pliocene-Pleistocene sediments at Site 758 (northern part of Ninetyeast Ridge) contain a significant amount of clastic material transported to the site by the (distal) Bengal Fan. In these sediments, Corg contents of up to 0.9% were measured and are due to the inflow of terrigenous organic debris. Corg values are positively correlated with bulk sediment accumulation rates (i.e., sediments contain more organic matter at times of faster deposition). The size of terrigenous organic particles is generally small in all sediments. The extremely small number of particles in the Cretaceous sediments at Site 758 and their smaller grain size, compared to the Cretaceous sediments on Broken Ridge, indicate that Cretaceous surface water paleocurrents flowed from southeast to northwest in the Proto-Indian Ocean. In the central Indian Ocean, sediments deposited above the carbonate compensation depth consist of nannofossil and foraminiferal oozes. In contrast to Corg values, calcite contents in the sediments are negatively correlated with bulk sediment accumulation rates (i.e., carbonate oozes were deposited only during times of extremely slow sedimentation). Therefore, older sediments deposited in the young and still narrow Indian Ocean accumulated faster and are less carbonate-rich than Neogene sediments, although carbonate accumulation rates were higher.

Palynofacies analysis of sediments in the eastern Equatorial Atlantic

Analyses of the palynofacies and sporomorph thermal alteration indices (TAI) of sediments from Ocean Drilling Program (ODP) Sites 959 to 962 in the Cote d'Ivoire-Ghana Transform Margin, West Africa were undertaken to (1) determine the source and depositional conditions of the organic matter in the sediments, (2) refine a paleobathymetric curve derived from other data for Site 959, which drilled the most continuous sedimentary sequence from Pleistocene to Albian and (3) interpret the paleothermal history of the area. Twelve types of dispersed organic matter were identified: amorphous organic matter (AOM), marine palynomorphs, algae, resins, black debris, yellow-brown fragments, black-brown fragments, cuticles, plant tissue, wood, sporomorphs and fungi, The relative abundances of these organic matter components at each site were analyzed using cluster analysis, resulting in the identification of seven palynofacies assemblages at Site 959, five each at sites 960 and 961, and four at Site 962. Amorphous organic matter (which is chiefly marine derived), black debris and wood have played the most significant role in defining palynofacies assemblages. The palynofacies assemblages show some correlation with lithologic units, sediment sources and depositional environments. Previous palynofacies studies in passive margins have demonstrated that changes in the ratio of AOM to terrestrial organic matter are related primarily to proximal-distal positions of depositional environments relative to the shoreline. However, this assumption does not always hold true for a transform margin where tectonic factors play an important role in the organic matter distribution, at least in the early stages of evolution. Lithofacies, CCD paleodepths for the North Atlantic, trace fossil association, benthic foraminifera and palynofacies data were the criteria used for reconstructing a paleobathymetric curve for Site 959. A cyclicity in the organic matter distribution of the Upper Miocene to Lower Pliocene pelagic sediments could be related to fluctuations in productivity of biosiliceous and calcareous organisms, and sedimentation rates. A drastic increase in the amount of AOM and a decrease in black debris and wood in the carbonate and clastic rocks (Lithologic Unit IV) overlying the tectonized Albian sediments (Lithologic Unit V) at Sites 959 and 960 coincide with the presence of an unconformity. Qualitative color analysis of palynomorphs was undertaken for all sites, although the main focus was on Site 959 where detailed organic geochemical data were available. At Site 959, TAI values indicate an immature stage of organic maturation (<2) down to the black claystones of Lithologic Unit III at about 918.47 mbsf. Below this, samples show an increase with depth to a moderately mature stage (>2 except for the claystone samples between 1012.52 and 1036.5 mbsf, and one limestone sample at 1043.4 mbsf), reaching peak levels of 2.58 to 3.0 in the tectonized Albian sediments below the unconformity. These TAI values show a positive correlation with the Tma x values derived from Rock-Eval pyrolysis data. The highest values recorded in the basal tectonized units at all the sites (Sites 960-962 have mean values between 2.25 and 3.13) may be related to high heat flow during the intracontinental to syntransform basin stage in the region.