Organic geochemical comparison of Cretaceous green and black claystones at DSDP Hole 75-530A

Three pairs of Upper Cretaceous black shales and adjacent green claystones from Hole 530A were analyzed to compare types and amounts of organic matter and lipids and to seek information about their environments of deposition. The organic-carbon-rich black shales have C/N ratios nearly seven times those of the organic-carbon-lean green claystones. The lipid content of organic matter in the black shales is about ten times less than in adjacent green layers. Organic matter in both types of rocks is thermally immature, and distributions of alkanoic acids, alkanols, sterols, and alkanes contain large amounts of terrigenous components. Pristane/phytane ratios of less than one suggest that younger Turonian sediments were laid down under anoxic conditions, but ratios greater than one suggest that older Turonian Cenomanian deposits accumulated in a more oxic environment. Closely bedded green and black layers have very similar types of lipid distributions and differ primarily in concentrations, although black shales contain somewhat larger amounts of terrigenous lipid components. Geochemical and stratigraphic evidence suggests much of the organic matter in these samples originated on the African continental margin and was transported to the Angola Basin by turbidity flow. Rapid reburial of organic-carbon-rich sediments led to formation of the black shales.

Records of past mid-depth ventilation: Cretaceous ocean anoxic event 2 vs. recent oxygen minimum zones

Present day oceans are well ventilated, with the exception of mid-depth oxygen minimum zones (OMZs) under high surface water productivity, regions of sluggish circulation, and restricted marginal basins. In the Mesozoic, however, entire oceanic basins transiently became dysoxic or anoxic. The Cretaceous ocean anoxic events (OAEs) were characterised by laminated organic-carbon rich shales and low-oxygen indicating trace fossils preserved in the sedimentary record. Yet assessments of the intensity and extent of Cretaceous near-bottom water oxygenation have been hampered by deep or long-term diagenesis and the evolution of marine biota serving as oxygen indicators in today's ocean. Sedimentary features similar to those found in Cretaceous strata were observed in deposits underlying Recent OMZs, where bottom-water oxygen levels, the flux of organic matter, and benthic life have been studied thoroughly. Their implications for constraining past bottom-water oxygenation are addressed in this review. We compared OMZ sediments from the Peruvian upwelling with deposits of the late Cenomanian OAE 2 from the north-west African shelf. Holocene laminated sediments are encountered at bottom-water oxygen levels of < 7 µmol/kg under the Peruvian upwelling and < 5 µmol/kg in California Borderland basins and the Pakistan Margin. Seasonal to decadal changes of sediment input are necessary to create laminae of different composition. However, bottom currents may shape similar textures that are difficult to discern from primary seasonal laminae. The millimetre-sized trace fossil Chondrites was commonly found in Cretaceous strata and Recent oxygen-depleted environments where its diameter increased with oxygen levels from 5 to 45 µmol/kg. Chondrites has not been reported in Peruvian sediments but centimetre-sized crab burrows appeared around 10 µmol/kg, which may indicate a minimum oxygen value for bioturbated Cretaceous strata. Organic carbon accumulation rates ranged from 0.7 and 2.8 g C /cm2 /kyr in laminated OAE 2 sections in Tarfaya Basin, Morocco, matching late Holocene accumulation rates of laminated Peruvian sediments under Recent oxygen levels below 5 µmol/kg. Sediments deposited at > 10 µmol/kg showed an inverse exponential relationship of bottom-water oxygen levels and organic carbon accumulation depicting enhanced bioirrigation and decomposition of organic matter with increased oxygen supply. In the absence of seasonal laminations and under conditions of low burial diagenesis, this relationship may facilitate quantitative estimates of palaeo-oxygenation. Similarities and differences between Cretaceous OAEs and late Quaternary OMZs have to be further explored to improve our understanding of sedimentary systems under hypoxic conditions.

(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).