Geochemistry and petrography of organic matter at DSDP Hole 77-535

Organic geochemical and organic petrographic methods were used to study three Lower to middle Cretaceous sediment samples from Hole 535 in the southeastern Gulf of Mexico for organic matter contents and origin and level of maturation. All three samples contain mixed kerogen Type II/III organic matter with a maturity corresponding to about 0.4% vitrinite reflectance. The marine component increases with stratigraphic age, and microbial reworking of the organic matter is significant in each age. The lower two samples of Hauterivian to Valanginian age appear to be impregnated (or contaminated) with soluble polar organic compounds, but there is only a weak indication for the presence of more mature, nonindigenous hydrocarbons.

Organofacies reconstruction and lipid geochemistry of sediments from the Galicia margin

Samples of Lower to middle Cretaceous rocks from ODP Sites 638, 640, and 641, drilled on the Galicia continental margin in the northeast Atlantic, have been investigated by organic geochemical methods (i.e., organic carbon determination, Rock-Eval pyrolysis, kerogen microscopy, gas chromatography, and gas chromatography/mass spectrometry) to define the Organofacies types and the depositional environments of these sediments. The results of this study fit well into the general picture drawn for the depositional history of the organic matter in Cretaceous organic-carbon-rich sediments in the North Atlantic from previous DSDP investigations. During the Valanginian to Albian, terrigenous organic carbon dominated the organic matter deposited on the Galicia continental margin. Cyclic changes in total organic carbon content were probably controlled by climatic-triggered changes in the supply of terrigenous organic matter from the nearby continent. A drastic change in depositional environment must have occurred near the Cenomanian/Turonian boundary. The preservation of large amounts of marine organic carbon in these sediments was probably caused by anoxic deep-water conditions during that time, rather than high productivity. All of the primary organic matter of the sediment samples investigated is thermally immature, as indicated by very low vitrinite reflectance values.

Organic matter in sediments of ODP Site 131-808

Microscopic studies reveal a predominance of terrestrial organic matter in sediments of Site 808. Terrestrial vitrinite and inertinite are more abundant (73% to 100%) than marine organic matter (alginite, 0% to 27%), which increases from open oceanic deposits of the Shikoku Basin sediments to sediments of the outer trench wedge. The abundance of terrestrial organic matter is also reflected through carbon isotope values of -23 per mil to -25.9 per mil. Mass accumulation rates of organic carbon are low in hemipelagic sediments of the Shikoku Basin (<0.2 g/cm**2/k.y.) but increase significantly in sediments of the Nankai Trench (0.2 to 1.7 g/cm**2/k.y.). Although the organic mass accumulation is high in sediments of the Nankai Trench, a comparison of sedimentation rates and total organic carbon suggests relative dilution of organic carbon through turbidite flows. Calculated marine paleoproductivity of organic carbon is low in sediments of the open ocean (Shikoku Basin) and increases closer to the shore (Nankai Trench). Thermal evolution of organic matter is obtained from vitrinite reflectance measurements. Two populations of vitrinites have been observed between 600 and 1234 mbsf. Reflectance values change with increasing depth and temperature in both groups of vitrinite (0.3% to 0.68% in group 1; 0.6% to 1% in group 2).

Analysis of organic matter from DSDP Leg 81 Holes

Organic geochemical and visual kerogen analyses were carried out on approximately 50 samples from Leg 81 (Rockall Plateau, North Atlantic). The sediments are from four sites (Sites 552-555), Pleistocene to Paleocene in age, and represent significantly different depositional environments and sources of organic matter. The Pleistocene glacial-interglacial cycles show differences in sedimentary organic matter based on Rock-Eval pyrolysis, organic phosphorus, and pyrolysis/mass-spectrometry analyses. Glacial samples contain more organic carbon, with a larger proportion of reworked organic matter. This probably reflects increased erosion of continental and shelf areas as a result of low sea level stands. Inter glacial samples contain a larger proportion of marine organic matter as determined by organic phosphorus and pyrolysis analyses. This immature, highly oxidized marine organic matter may be associated with the skeletal organic matrix of calcareous organisms. In addition, Rock-Eval data indicate no significant inorganic-carbonate contribution to the S3 pyrolysis peak. The Pliocene-Miocene sediments consist of pelagic, biogenic carbonates. The organic matter is similar to that of the Pleistocene interglacial periods; a mixture of oxidized marine organic matter and reworked, terrestrial detritus. The Paleocene-Oligocene organic matter reflects variations in source and depositional factors associated with the isolation of Rockall from Greenland. Paleocene sediments contain primarily terrestrial organic matter with evidence of in situ thermal stress resulting from interbedded lava flows. Late Paleocene and early Eocene organic matter suggests a highly oxidized marine environment, with major periods of deposition of terrestrially derived organic matter. These fluctuations in organic-matter type are probably the result of episodic shallowing and deepening of Rockall Basins. The final stage of Eocene/Oligocene sedimentation records the accelerating subsidence of Rockall and its isolation from terrestrial sources (Rockall and Greenland). This is shown by the increasingly marine character of the organic matter. The petroleum potential of sediments containing more than 0.5% organic carbon is poor because of their thermal immaturity and their highly oxidized and terrestrial organic-matter composition.

Organic- and carbonate-carbon values and extract data for DSDP Holes 63-467 and 63-471

Quantity, type, and maturity of the organic matter of middle Miocene to Quaternary sediments from the eastern North Pacific (Deep Sea Drilling Project Leg 63) were determined. Hydrocarbons and fatty acids in lipid extracts were analyzed by capillary column gas chromatography and combined gas chromatography/mass spectrometry. Kerogens were investigated by Rock-Eval pyrolysis and microscopy, and vitrinite reflectance values were determined. At Site 467, in the San Miguel Gap of the outer California Continental Borderland, organic carbon contents range from 1.46% to 5.40%. Normalized to organic carbon, total extracts increase from about 10 to 36 mg/g Corg with depth. The organic matter is a mixture of both marine and terrestrial origin, with the marine organic matter representing a high proportion in some of the samples. Steroid hydrocarbons - sterenes and steradienes in the upper part of the section and steranes in the deepest sample - are the most abundant compounds in the nonaromatic hydrocarbon fractions. Perylene, alkylated thiophenes, and aromatic steroid hydrocarbons dominate in the aromatic hydrocarbon fractions of the shallower samples; increasing maturation is indicated by a more petroleumlike aromatic hydrocarbon distribution. Microscopy revealed a high amount of liptinitic organic matter and confirmed the maturation trend as observed from analysis of the extracts. The vitrinite reflectance may be extrapolated to a bottom-hole value of nearly 0.5% Ro. The liquid hydrocarbon potential of the sediments at higher maturity levels is rated to be good to excellent. At Site 471, off Baja California, organic carbon values are between 0.70% and 1.12%. Extract values increase with depth, as at Site 467. The investigation of the soluble and insoluble organic matter, despite some compositional similarities, consistently revealed a more terrigenous influx compared with Site 467. Thus the potential for liquid hydrocarbon generation is lower, the organic matter being more gas-prone. The deepest sample analyzed indicates the onset of hydrocarbon generation. At this site, frequent sand intercalations offer pathways for migration and possibly reservoir formation.

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.

Hydrous and anhydrous pyrolysis of DSDP Leg 75 kerogens

The aliphatic hydrocarbon distributions obtained from the natural bitumens of three Leg 75 sediments were compared using computerised gas chromatography-mass spectrometry (C-GC-MS). The kerogens isolated from these sediments were heated in sealed tubes at 330°C using the techniques of hydrous (i.e. heating kerogen in the presence of water) and anhydrous pyrolysis (i.e. heating dry kerogen alone). These experiments were then repeated at a lower temperature (280°C). At 330°C, under anhydrous conditions, considerable destruction of biomarkers in the ancient kerogens (i.e. pre-Tertiary) occurred, whereas with water present significant amounts of hopanes were obtained. However, with more recent kerogens (which contain larger amounts of chemically bound water), both anhydrous and hydrous pyrolysis gave a similar suite of biological markers, in which long chain acyclic isoprenoids (C40) are significant components. Lowering the temperature of pyrolysis to 280°C yielded biological markers under both hydrous and anhydrous conditions for all kerogens. n-Alkenes were not detected in any of the pyrolysates; however, a single unknown triterpene was discovered in several of the hydrous and anhydrous pyrolysates. The results tentatively indicate that the chief value to petroleum research of kerogen hydrous pyrolysis lies in its ability to increase the yield of pyrolysate. High temperature hydrous pyrolysis (280-330°C), under high pressure (2000 psi), does not appear to mimic natural conditions of oil generation. However, this study does not take into account whole rock pyrolysis.

Organic matter from black shales collected in DSDP Holes 41-367 and 41-368

It is shown that microscopic algae dominate in source material of organic matter of black shales, and admixture of residues of organisms and terrestrial humic material is contained. The main direction of source material transformation during syngenesis and sedimentogenesis is associated with jellofication resulting to formation of organic matter of significantly sapropelic type. Low reflectance of vitrinite and alginite from organic matter refer to the primary and secondary lignite stages of its carbonification. Significantly sapropel type of organic matter and low stage of carbonification are reliable criteria for assigning black shales to the category of potential oil source strata.

(Table 1) Comparison of adjacent Cenomanian black shales with green claystones from DSDP Hole 75-530A

Black shales possessing high concentrations of organic carbon (Foresman, 1978, doi:10.2973/dsdp.proc.40.111.1978) were deposited in many parts of the proto South Atlantic Ocean during the Cretaceous period (Bolli et al., 1978, doi:10.2973/dsdp.proc.40.104.1978). The way such sediments accumulated is not fully understood, but is likely to have occurred through a combination of low oxygen availability and abundant supply of organic matter. Thin, centimetre-thick layers of black shales are commonly interbedded with thicker layers of organic carbon-deficient, green claystones, as found in strata of Aptian to Coniacian age, at Deep Sea Drilling Project (DSDP) Site 530, in the southern Angola Basin (Hay et al., 1982, doi:10.1130/0016-7606(1982)93<1038:SAAOOC>2.0.CO;2) and elsewhere. These differences in carbon content and colour reflect the conditions of deposition, and possibly variations in the supply of organic matter (Summerhayes and Masran, 1983, doi:10.2973/dsdp.proc.76.116.1983; Dean and Gardner, 1982). We have compared, using organic geochemical methods the compositions of organic matter in three pairs of closely-bedded black and green Cenomanian claystones obtained from Site 530. Kerogen analyses and distributions of biological markers show that the organic matter of the black shales is more marine and better preserved than that of the green claystones.

Organic sedimentation of ODP Sites 124-767 and 124-768

This study relates the organic sedimentation characteristics to the lithostratigraphic successionsthat were observed at Site 767 (Celebes Sea) and Site 768 (Sulu Sea) during ODP Leg 124. It is based on the total organic carbon content (TOC) of the sediments, on the petrographictype and maturity of the organic matter, and on the TOC accumulation rates calculated for the lithostratigraphic units. In the Celebes and Sulu Seas sediments, the organic matter is mainly of terrestrial origin with the highest concentrations and TOC accumulation rates occurring in the middle Miocene turbiditic sequences that correspond to a major compressive event between the Philippine Mobile Belt and the Palawan, Cagayan, and Sulu Ridges. Petrographic analysis of the Eocene and lower Miocene organic matter in the Celebes Sea shows that it consists only of highly degraded terrestrial particles. This observation and the very low TOC accumulation rates indicate poor conditions for organic carbon preservation during this open-ocean phase of the Celebes Basin formation. The organic matter, either of marine or terrestrial origin, is much better preserved in the younger sediments, suggesting physico-chemical changes in the depositional environment. Because of the dilution phenomena by turbidites, it is difficult to observe the progressive improvement of the organic matter preservation throughout the turbiditic series. The same change in preservation is broadly observed in the Sulu Sea from the early Miocene (rapid opening phase of the basin with massive pyroclastic deposits) to the present.

Organic chemistry of sediments from the Tyrrhenian Sea

Thirty sediment samples from Tortonian to Pleistocene age of five ODP locations (Holes 650A, 651A, and 652A, and Sites 654 and 655) in the Marsili Basin, Vavilov Basin, and Sardinia Margin (Tyrrhenian Sea) were studied by organic geochemical methods including total organic carbon determination, Rock-Eval pyrolysis, bitumen extraction, pyrolysis-gas chromatography, and organic petrography. Six organic facies, including open ocean anoxia with variable terrestrial input, oxic open ocean, oxic tidal flat, mildly oxic lagoon, and anoxic lacustrine algal-bacterial mat environments, have been recognized in these sediments. The sediments below 500 m in Sardinia Margin are mature for significant hydrocarbon generation. Possible mature source-rock (Type I and IIB/III kerogen) and migrated bitumen occur in the deeper part of the section in Vavilov Basin and Sardinia Margin sediments. Sporadic sapropel formation observed in the studied Pliocene-Pleistocene sediment section is probably controlled by organic productivity due to nutrient supply by the rivers and terrestrial input associated with open ocean anoxia or anoxia caused by the material balance between rate of organic matter supplied by turbidites and organic matter consumption. Pliocene and Pleistocene sapropels are mostly immature and lie within Type II-III (precisely as IIA-IIB and IIB source rocks) kerogen maturation path.

Organic geochemistry of Lower Cretaceous sediments from the northwetsern Pacific guyits

Organic geochemical data of Lower Cretaceous shallow water sediments from two sites (865 and 866) drilled during ODP leg 143 are presented. The organic matter is mainly terrestrial at the bottom of the sedimentary column at site 865, whereas algal and/or bacterial organic matter is dominant at site 866. This is the first evidence of shallow water deposition of organic matter during the Early Cretaceous in the Northwestern Pacific. The lower Aptian organic carbon-rich layers from the shallow water sediments of site 866 are geochemically similar to coeval mid-water sediments of site 463.

Chemistry of organic matter of glacial and Cretaceous sediments from the Prydz Bay

Organic matter in Miocene glacial sediments in Hole 739C on the Antarctic Shelf represents erosional recycled continental material. Various indications of maturity in bulk organic matter, kerogens, and extracts imply that an exposed section of mature organic carbon-rich material was present during the Miocene. Based on biomarker, n-alkane, and kerogen analysis, a massive diamictite of early Eocene/Oligocene age at Hole 739C contains immature organic matter. Visual and pyrolysis analyses of the kerogens suggest a predominance of terrestrial organic matter in all samples from Hole 739C. A reversal of thermal maturities, i.e., more-mature overlying less-mature sections, may be related to redeposition generated from glacial erosion. Siliciclastic fluviatile sediments of Lower Cretaceous age from Hole 741A were analyzed. The organic matter from this hole contains immature aliphatic and aromatic biomarkers as well as a suite of odd carbon number-dominated nalkanes. Visual examination and pyrolysis analysis of the kerogen suggests that predominantly immature terrestrial organic matter is present at Hole 741A. The similarities between Hole 739C Unit V and Hole 741A suggest that the source of the organic matter in the glacial sediments in Unit V at Hole 739C could be Cretaceous in age and similar to sediments sampled at Hole 741A in Prydz Bay.