Organic geochemistry of Upper Albian sediments from the Kirchrode I borehole

In the framework of a multidisciplinary research program, an organic geochemical study was carried out on a drill core which comprises a 245 m thick sequence of light-colored, Upper Albian marlstones that were deposited in the central part of the Lower Saxony basin (northern Germany). For part of the Upper Albian sequence, high-resolution measurements of carbonate contents reveal cycles which can be related to earth orbital forcing. Based on these data, sediment accumulation rates were calculated to be in the order of 15 g/m**2/yr. These high accumulation rates contrast with very low organic carbon contents and an extremely poor preservation of the autochthonous organic matter. Most of the sedimentary organic matter is of terrigenous origin and mainly derived from the erosion of older sedimentary rocks. Organic petrography reveals only a very small fraction of marine organic particles. Carbon/sulphur ratios, pristane/phytane ratios as well as the predominance of resedimented organic particles over autochthonous organic particles suggest that aerobic degradation processes rather than anaerobic processes (sulphate reduction) were responsible for the degradation of the organic matter. Furthermore, the scarcity of terrigenous organic particles (vitrinite) indicates that there was little vegetation on nearby land areas. To explain these analytical results, a depositional model was developed which could explain the scarcity of organic matter in the Upper Albian sediments. This model is based on downwelling of oxygen-rich, saline waters of Tethyan origin, which reduces the nutrient content of surface waters and thus primary bioproductivity while degradation of primary organic matter in the water column is enhanced at the same time. These conditions contrast to those which existed in Barremian and early Aptian times in this basin, when limited water exchange with adjacent oceans caused oxygen deficiency and the deposition of numerous organic carbon-rich black shales. The thick, organic matter-poor Upper Albian sequence of northern Germany also contrasts with comparatively thin, time-equivalent, deep-sea black shales from Italy. This discrepancy indicates that local and regional oceanographic factors (at least in this case) have a greater influence on organic matter deposition than global events.

Facies and diagenesis of organic matter in sediments at DSDP Leg 87

A series of upper Pliocene to Pleistocene sediment samples from DSDP Sites 582 and 583 (Nankai Trough, active margin off Japan) were investigated by organic geochemical methods including organic carbon determination, Rock- Eval pyrolysis, gas chromatography of extractable hydrocarbons, and kerogen microscopy. The organic carbon content is fairly uniform and moderately low (0.35 to 0.77%) at both sites, although accompanied by high sedimentation rates. The low organic matter concentrations are the result of the combined effect of several factors: low bioproductivity, oxic depositional environment, and dilution with lithogenic material. Organic petrography revealed a mixture of three maceral types: (1) fresh, green fluorescent alginites of aquatic origin probably transported by turbidites from the shelf edge, (2) gelified huminites and paniculate liptinites derived from the erosion of unconsolidated peat, and (3) highly reflecting inertinites derived from continental erosion. By a combination of organic petrography and Rock-Eval pyrolysis results, the organic matter is characterized as mainly type III kerogen with a slight tendency to a mixed type II-III. During Rock-Eval pyrolysis, a mineral matrix effect on the generated hydrocarbons was observed. The organic matter in all sediments has a low level of maturity (below 0.45% Rm) and has not yet reached the onset of thermal hydrocarbon generation according to several geochemical maturation parameters. This low maturity is in contrast to anomalously high extract yields at both sites and large hydrocarbon proportions in the extracts at Site 583. This contrast may be due to early generation of polar compounds and perhaps redistribution of hydrocarbons caused by subduction tectonics. Carbon isotope data of the interstitial hydrocarbon gases indicate their origin from bacterial degradation of organic matter, although only very few bacterially degraded maceral components were detected.

Terrestrial organic matter in marine sediments of the Central Equatorial Atlantic

Terrestrial organic matter (OM) in pelagic sediments is discussed with regard to depositional processes and land-sea interactions in the modern and past glacial/interglacial Equatorial Atlantic. Special emphasis is placed on a critical evaluation of different analytical approaches (C/N, Rock-Eval Pyrolysis, stable carbon isotopes, palynology, organic petrology, and selected biomarkers) which are currently used for the qualitative and quantitative assessment of terrigenous organic carbon. If binary mixing equations are used to calculate terrestrial and marine proportions of organic carbon, we consider the definition of endmember values to be most critical since these values may be biased by a great number of independent controls. A combination of geochemical methods including optical studies (organic petrology and palynology) is therefore suggested to evaluate each individual proxy. Organic geochemical analyses performed on sediments from the modern and Late Quaternary Equatorial Atlantic evidence fluctuations in eolian supply of terrigenous OM related to changes in intensity of the trade winds. Quantification of this organic fraction leads to differing proportions depending on the approach applied, i.e. the organic carbon isotopic composition or maceral analyses. Modern distribution of terrigenous OM reveals a decrease in supply towards the basin contributing less than a fifth of the total OM in pelagic areas. Organic geochemical data indicate that sedimentation in the modern northeastern Brasil Basin is affected by lateral advection of reworked OM probably from southern source areas. Glacial/interglacial deposits from the pelagic Equatorial Atlantic (ODP Site 663), covering isotopic stages 12 and 11, reveal that deposition of terrigenous OM was higher under past glacial conditions, in correspondence to generally enhanced dust fluxes. Proportions of terrigenous OM, however, never exceed 50% of the total OM according to maceral analyses. Other estimates, recently proposed by Verardo and Ruddiman (1996), are considered to be too high probably for analytical reasons. Palynological records in the Equatorial Atlantic parallel dust records. Increased portions of grass pollen suggest the admixture of C4-plant material under modern and past glacial conditions. It is therefore assumed, as one possible interpetation, that C4-plant debris has an effect on sedimentary d13Corg and might explain differences between isotopic and microscopic quantitative estimates. Using the difference between these two records, we calculate that maximum supply of C4-material remains below 20% of the total OM for the deep modern and past glacial/interglacial Equatorial Atlantic.

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.

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.

Organic carbon analyses of ODP Site 160-971 in the Mediterranean Sea

Mud volcanism on the Mediterranean Ridge is caused by extrusion of overpressured sediments, with consequent formation of spectacular dome-shaped features composed of mud breccias at the seafloor. The organic material in the mud breccia of the Napoli mud volcano is a mixture of different facies, stratigraphic origin and thermal maturities. One portion is synsedimentary organic material with only minor diagenetic alterations and represents sedimenting material that was embedded into the mud volcano during its extrusion. The mud breccia also contains thermally mature organic material of mainly terrestrial provenance with algae of fresh- and brackish-water origin. Vitrinite reflectance data of this maturity generation range from 0.65 to 0.90% R(oil) and thus characterize thermally mature source rocks, a rank which is corroborated by fluorescence and molecular characteristics. The predominance of vitrinite in the maceral assemblages and the occurrence of biomarkers of terrigenous origin suggest that the major part of the mud matrix derives from a lacustrine or riverine sedimentary unit in the subsurface, possibly from the Messinian stage. A third generation of organic material includes inertinites and vitrinites of high reflectance, which represent recycled organic matter present in any marine sediment. By use of the Lopatin method for modelling the thermal maturation of hydrocarbon source rocks from the vitrinite reflectance data, we calculated that the depth of mobilization ranges from 4900 m to 7500 m, depending upon the temperature gradient used.

Total organic carbon content and maceral composition of sediment at DSDP Holes 72-515B and 72-516F

The amount, type, and thermal maturation of organic matter in sediments from two DSDP holes in the South Atlantic (Leg 72) were investigated. Isolated kerogens were studied by microscopy, and nonaromatic hydrocarbons were characterized by capillary gas chromatography. Organic carbon values are low in all samples and range between 0.05 and 0.21% in Hole 515B (Brazil Basin) and only between 0.02 and 0.10% in Hole 516F (Rio Grande Rise). The organic matter is predominantly terrigenous, mixed with some unicellular marine algae; it is severely oxidized in most samples. N-alkane distributions are usually dominated by long-chain wax alkanes with odd-over-even carbon number predominance; when the marine organic matter is relatively more abundant, however, significant amounts of n-alkanes are centered upon n-C17. The organic matter is not mature enough in any sample to generate appreciable amounts of hydrocarbons.

Fossil plant remains in DSDP Leg 80 holes

The lower part of the syn-rift Barremian-?Hauterivian section at Site 549 contains a large amount of acid-resistant land-derived organic matter that, as elsewhere in the Cretaceous sediments of the IPOD Leg 80 sites, is thermally immature. This plant debris was derived from a vegetation made up of many species of pteridophytes and gymnosperms. The palynofacies indicate that the sediments were deposited in shallow marginal and nonmarine environments and that the climate was probably warm temperate and fairly moist at the time. Source potential for gas is suggested at some horizons. Most of the younger Lower Cretaceous sediments at this and the other sites were deposited in more open marine conditions. Although they generally contain less organic matter, land plant remains continue to comprise a major part of the palynofacies. The Upper Cretaceous sediments were mainly deposited in well oxygenated conditions and are organically lean. However, stratigraphically restricted dark-colored shales at Sites 549 to 551 contain relatively large quantities of amorphous detritus of at least partly marine origin. These characteristics are suggestive of deposition during periods of restricted circulation and also of source potential for oil and gas if maturation levels had been higher.

(Table 1) Experimental data for kerogens from DSDP Hole 41-368

Potassium permanganate oxidative degradations were conducted for kerogens isolated from Cretaceous black shales (DSDP Leg 41, Site 368), thermally altered during the Miocene by diabase intrusions and from unaltered samples heated under laboratory conditions (250-500°C). Degradation products of less altered kerogens are dominated by normal C4-C15 alpha,omega-dicarboxylic acids, with lesser amounts of n-C16 and n-C18 monocarboxylic acids, and benzene mono-to-tetracarboxylic acids. On the other hand, thermally altered kerogens show benzene di-to-tetracarboxylic acids as dominant degradation products, with lesser or no amounts (variable depending on the degree of thermal alteration) of alpha,omega-dicarboxylic acids. Essentially no differences between the oxidative degradation products of naturally- and artificially-altered kerogens are observed. As a result of this study, five indices of aromatization (total aromatic acids/kerogen; apparent aromaticity; benzenetetracarboxylic acids/total aromatic acids; benzene-1,2-dicarboxylic acid/benzenedicarboxylic acids; benzene-1,2,3-tricarboxylic acid/benzenetricarboxylic acids) and two indices of aliphatic character (Total aliphatic acids/kerogen; Aliphaticity) are proposed to characterize the degree of thermal alteration of kerogens. Furthermore, a good correlation is observed between apparent aromaticity estimated by the present KMnO4 oxidation method and that from the 13C NMR method (Dennis et al., 1982; doi:10.1016/0016-7037(82)90046-1).