Organic d13C values, kerogen atomic C/N ratios and relative weights of some kerogen pyrolysis products of ODP Hole 112-682A (Table 1)

Carbon isotopic composition of predominantly marine kerogen in latest Oligocene mudstones of the Peru Margin ODP 682A Hole shows an about 3.5? increase with decreasing age. Py-GC and elemental (C=N ratio) analysis of the kerogen plus sulphur isotopic study together with earlier knowledge on geological setting and organic geochemistry results in a better understanding of depositionary environment and allows to separation of the influence of concentration of water dissolved carbon dioxide (ce) on kerogen delta13C from that of other factors (bacterial degradation, sea surface temperature, DIC delta13C, productivity, and admixture of land plant OM). Based on this analysis, the major part of the kerogen shift is considered as a result of the latest Oligocene decrease of marine photosynthetic carbon isotopic fractionation in the Peru Margin photic zone, which in turn possibly reflects a simultaneous drop in atmospheric CO2 level. Uncertainties in the evaluation of the factors affecting the marine photosynthetic carbon isotopic fractionation and the extent of ocean-atmosphere disequilibrium do not permit calculation of the decrease of the atmospheric CO2.

(Table 1) Summary of low-molecular-weight hydrocarbon concentrations, organic carbon contents, Rock-Eval pyrolysis and lithology at DSDP Leg 79 Holes

A series of core samples taken during Cruise 79 of Glomar Challenger, drilling offshore Morocco (Mazagan Plateau), is analyzed for their low-molecular-weight hydrocarbon contents. Fifty-four samples from DSDP Holes 544A, 545, 547A, and 547B, deep frozen on board immediately after recovery, are studied by a hydrogen-stripping/thermovaporization technique combined with capillary gas chromatography. Thirty-eight compounds in the C2-C8 molecular range, including saturated, olefinic, and aromatic hydrocarbons, are identified. Because of large differences in organic carbon contents, the total C2-C8 hydrocarbon concentrations vary from about 20 to 1500 ng/g dry sediment weight in the whole sample series. Organic-carbon normalized values are about 3.2 x 10**4 ng/g Corg for Lithologic Subunits IIIA and IIIB at Site 545 (Cenomanian to Aptian) and 1.0 x 10**5 ng/g Corg for Unit V at Site 547 (Cenomanian to Albian) reflecting the slightly more advanced maturity stage at the latter site. Values exceeding 10**5 ng/g Corg (Site 545) and 2 x 10**5 ng/g Corg (Site 547) are associated with samples that are very lean in organic carbon and are generally rich in carbonate. These samples are enriched by small amounts of gaseous hydrocarbons. A detailed study of individual hydrocarbon concentrations, plotted against depth, reveal additional indications for migration phenomena. At Site 547, for instance, the most mobile hydrocarbons studied (e.g., ethane) appear to migrate by diffusion or a related process from more than 700 m depth toward the surface.

(Appendix) Total organic carbon, pyrolysis characteristics, and organic matter types at DSDP Holes 77-535 and 77-540

Lower to middle Cretaceous sediments in the eastern Gulf of Mexico are richer in organic matter and have a more marine organic facies than their counterparts in the nearby western North Atlantic, suggesting that the Gulf was the more productive of the two areas. As in the western North Atlantic, the rate of supply of terrestrial organic matter was high when the rate of supply of noncarbonate clastic materials was high (at times of low sea level) and diminished as sea level rose. The rate of supply of marine organic matter was lower in the Early Cretaceous than in the Cenomanian, perhaps in response to the global rise in sea level over this period. Where they are thermally mature, the organic matterrich units drilled at Sites 535 and 540 should be excellent sources for liquid hydrocarbons. The Pleistocene sediments of the eastern Gulf are dominated by terrestrial organic matter representing Mississippi River effluent.