Cretaceous calcareous nannofossils of ODP Leg 103 holes

Ocean Drilling Program Leg 103 recovered Lower Cretaceous sediments from the Galicia margin off the coast of Iberia. The high diversity and abundance of assemblages makes this excellent material for the study of Early Cretaceous calcareous nannofossils. With the exception of a hiatus between the upper Hauterivian and lower Barremian, nannofossil distributions form a continuous composite section from the lower Valanginian to lower Cenomanian sediments recovered at the four sites. The sedimentation history of this rifted continental margin is complex, and careful examination of the nannofossil content and lithology is necessary in order to obtain optimum biostratigraphic resolution. The Lower Cretaceous sequence consists of a lower Valanginian calpionellid marlstone overlain by terrigenous sandstone turbidites deposited in the Valanginian and Hauterivian during initial rifting of this part of the margin. Interbedded calcareous marl and claystone microturbidites overlie the sandstone turbidites. Rifting processes culminated in the late Aptian-early Albian, resulting in the deposition of a calcareous, clastic turbidite sequence. The subsequent deposition of dark carbonaceous claystones (black shales) represents the beginning of seafloor spreading, as the margin continued to subside to depths near or below the CCD. The diversity, abundance, and preservation of nannofossils within these varied lithologies differ, and an attempt to distinguish between near shore and open-marine assemblages is made. Genera used for this purpose include Nannoconus, Micrantholithus, Pickelhaube, and Lithraphidites. In this study, six new species and one new subspecies are described and documented. Ranges of other species are extended, and an attempt is made to clarify existing, yet poorly understood, taxonomic concepts. A technique in which a single specimen is viewed with both light and scanning electron microscopes was used extensively to aid in this task. In addition, further subdivisions of the Sissingh (1977) zonation are suggested in order to increase biostratigraphic resolution.

Geochemistry of Albian to Santonian black shale sequences on the Demerara Rise, South American margin

Ocean Drilling Program Leg 207 recovered thick sequences of Albian to Santonian organic-carbon-rich claystones at five drill-sites on the Demerara Rise in the western equatorial Atlantic Ocean. Dark-colored, finely laminated, Cenomanian-Santonian black shale sequences contain between 2% and 15% organic carbon and encompass Oceanic Anoxic Events 2 and 3. High Rock-Eval hydrogen indices signify that the bulk of the organic matter in these sequences is marine in origin. However, d13Corg values lie mostly between -30 per mil and -27 per mil, and TOC/TN ratios range from 15 to 42, which both mimic the source signatures of modern C3 land plants. The contradictions in organic matter source indicators provide important implications about the depositional conditions leading to the black shale accumulations. The low d13Corg values, which are actually common in mid-Cretaceous marine organic matter, are consequences of the greenhouse climate prevailing at that time and an associated accelerated hydrologic cycle. The elevated C/N ratios, which are also typical of black shales, indicate depressed organic matter degradation associated with low-oxygen conditions in the water column that favored preservation of carbon-rich forms of marine organic matter over nitrogen-rich components. Underlying the laminated Cenomanian-Santonian sequences are homogeneous, dark-colored, lower to middle Albian siltstones that contain between 0.2% and 9% organic carbon. The organic matter in these rocks is mostly marine in origin, but it occasionally includes large proportions of land-derived material.

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 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.

Fossil and non-fossil source contributions to atmospheric carbonaceous aerosols during extreme spring grassland fires in Eastern Europe

In early spring the Baltic region is frequently affected by high-pollution events due to biomass burning in that area. Here we present a comprehensive study to investigate the impact of biomass/grass burning (BB) on the evolution and composition of aerosol in Preila, Lithuania, during springtime open fires. Non-refractory submicron particulate matter (NR-PM1) was measured by an Aerodyne aerosol chemical speciation monitor (ACSM) and a source apportionment with the multilinear engine (ME-2) running the positive matrix factorization (PMF) model was applied to the organic aerosol fraction to investigate the impact of biomass/grass burning. Satellite observations over regions of biomass burning activity supported the results and identification of air mass transport to the area of investigation. Sharp increases in biomass burning tracers, such as levoglucosan up to 683 ngm-3 and black carbon (BC) up to 17 μgm-3 were observed during this period. A further separation between fossil and non-fossil primary and secondary contributions was obtained by coupling ACSM PMF results and radiocarbon (14C) measurements of the elemental (EC) and organic (OC) carbon fractions. Non-fossil organic carbon (OCnf/ was the dominant fraction of PM1, with the primary (POCnf/ and secondary (SOCnf/ fractions contributing 26–44% and 13–23% to the total carbon (TC), respectively. 5–8% of the TC had a primary fossil origin (POCf/, whereas the contribution of fossil secondary organic carbon (SOCf/ was 4–13 %. Nonfossil EC (ECnf/ and fossil EC (ECf/ ranged from 13–24 and 7–13 %, respectively. Isotope ratios of stable carbon and nitrogen isotopes were used to distinguish aerosol particles associated with solid and liquid fossil fuel burning.

Calcareous nannofossils of ODP Sites 149-897 and 149-901

Mesozoic calcareous nannofossil assemblages recovered during Ocean Drilling Program Leg 149 from the Iberia Abyssal Plain off the coast of Portugal were examined to determine the age of the rifting processes that affected the western Iberia Margin. Dark carbonaceous claystones (black shales) recovered from Site 901 contain highly diverse and abundant Tithonian calcareous nannofossil assemblages. Careful examination and documentation of this material has extended the ranges of numerous Jurassic and Cretaceous species and detailed a significant Late Jurassic assemblage turnover observed in the calcareous nannofossil record. The Lower Cretaceous sequence consists of intervals of serpentinized peridotite intercalated between various breccias and dark claystones. With the exception of a few samples, calcareous nannofossils are few and moderately preserved. The age of nannofossils within these varied sedimentary lithologies ranges from the late Barremian to the late Aptian. Eight new species are described: Ansulasphaera covingtonii, Clepsilithus meniscus, Conusphaera sinespina, Crepidolithus parvulus, Diazomatholithus galicianus, Percivalia arata, Rotelapillus pleoseptatus, and Tranolithus incus. Also proposed are five new combinations.

Rock eval analysis of organic matter in sediment core 159-959D

The Cretaceous Equatorial Atlantic Gateway between the Central and South Atlantic basins is of interest not only for paleoceanographic and paleoclimatic studies, but also because it provided particularly favourable conditions for the accumulation and preservation of organic-rich sediments. Deposition of carbonaceous sediments along the Côte d'Ivoire-Ghana Transform Margin (Ocean Drilling Program Leg 159) was intimately linked to the plate tectonic and paleoceanographic evolution of this gateway. Notably, the formation of a marginal basement ridge on the southeastern border of the transform margin provided an efficient shelter of the landward Deep Ivorian Basin against erosive and potentially oxidizing currents. Different subsidence histories across the transform margin were responsible for the development of distinct depositional settings on the crest and on both sides of the basement ridge. Whereas the southern, oceanward flank of the basement ridge was characterized by rapid, continuous deepening since last Albian-early Cenomanian, marine sedimentation on the northern, landward flank was interrupted by a period of uplift and erosion in the late Albian, and rapid subsidence started after the early Coniacian. Organic-rich sediments occur throughout almost the entire Cretaceous section, but hydrogen-rich marine black shales were exclusively recovered from core sections above an uplift-related unconformity. These black shales formed when separation of Africa and South America was sufficient to allow permanent oceanic midwater exchange after the late Albian. Four periods of black shale accumulation are recovered, some of them are correlated with the global oceanic anoxic events: in the last Albian-earliest Cenomanian, at the Cenomanian-Turronian boundary, during the middle Coniacian-early Campanian, and in the mid-Maastrichtian. These periods were characterized by increasing carbon flux to the seafloor, induced by enhanced palaeoproductivity and intensified supply of terrestrial organic matter. Black shale depostion appears to be intimately linked to periods of rising or maximum eustatic sea level and to the expansion of the oxygen minimum zone, as indicated by foraminiferal biofacies. Intervals between black shales units, in contrast, indicate a shrinking oxygen minimum zone and enhanced detrital flux rates, probably related to lowering sea level. Upper Cretaceous detritral limestones with high porosities may provide excellent hydrocarbon reservoirs, alsthough their areal extent appears to be limited. Palaeogene porcellanites, capped by Neogene pelagic marls and clays, extend over a wider area and max provide another target for hydrocarbon exploration.

An investigation of the Chattanooga black shale of Tennessee as a source of Uranium.

"U.S. AEC Contract No. AT-(40-1)-1337".

Geochemical composition of ODP Site 210-1276 shales

During Ocean Drilling Program Leg 210, a greatly expanded sedimentary sequence of continuous Cretaceous black shales was recovered at Site 1276. This section corresponds to the Hatteras Formation, which has been documented widely in the North Atlantic Ocean. The cored sequence extends from the lowermost Albian, or possibly uppermost Aptian, to the Cenomanian/Turonian boundary and is characterized by numerous gravity-flow deposits and sporadic, finely laminated black shales. The sequence also includes several sedimentary intervals with high total organic carbon (TOC) contents, in several instances of probable marine origin that may record oceanic anoxic events (OAE). These layers might correspond to the Cenomanian-Turonian OAE 2; the mid-Cenomanian event; and OAE 1b, 1c, and 1d in the Albian. In addition, another interval with geochemical characteristics similar to OAE-type layers was recognized in the Albian, although it does not correspond to any of the known OAEs. This study investigates the origin of the organic matter contained within these black shale intervals using TOC and CaCO3 contents, Corg/Ntot ratios, organic carbon and nitrogen isotopes, trace metal composition, and rock-eval analyses. Most of these black shale intervals, especially OAE 2 and 1b, are characterized by low 15N values (<0) commonly observed in mid-Cretaceous black shales, which seem to reflect the presence of an altered nitrogen cycle with rates of nitrogen fixation significantly higher than in the modern ocean.

Organic carbon and nitrogen, sediment composition, and clay mineralogy of Deep Sea Drilling Project Site 603, western Atlantic Ocean

Sediment and interstitial water samples recovered during DSDP Leg 93 at Site 603 (lower continental rise off Cape Hatteras) were analyzed for a series of geochemical facies indicators to elucidate the nature and origin of the sedimentary material. Special emphasis was given to middle Cretaceous organic-matter-rich turbidite sequences of Aptian to Turanian age. Organic carbon content ranges from nil in pelagic claystone samples to 4.2% (total rock) in middle Cretaceous carbonaceous mudstones of turbiditic origin. The organic matter is of marine algal origin with significant contributions of terrigenous matter via turbidites. Maturation indices (vitrinite reflectance) reveal that the terrestrial humic material is reworked. Maturity of autochthonous material (i.e., primary vitrinite) falls in the range of 0.3 to 0.6% Carbohydrate, hydrocarbon, and microscopic investigations reveal moderate to high microbial degradation. Unlike deep-basin black shales of the South and North Atlantic, organic-carbon-rich members of the Hatteras Formation lack trace metal enrichment. Dissolved organic carbon (DOC) in interstitial water samples ranges from 34.4 ppm in a sandstone sample to 126.2 ppm in an organic-matter-rich carbonaceous claystone sample. One to two percent of DOC is carbohydratecarbon.

(Table 1) Organic and inorganic geochemical analysis of Late Jurassic to Early Cretaceous black shale sediments from the Norwegian-Greenland Seaway

The Late Jurassic to Early Cretaceous (Volgian-Ryazanian) was a period of a second-order sea-level low stand, and it provided excellent conditions for the formation of shallow marine black shales in the Norwegian-Greenland Seaway (NGS). IKU Petroleum Research drilling cores taken offshore along the Norwegian shelf were investigated with geochemical and microscopic approaches to (1) determine the composition of the organic matter, (2) characterize the depositional environments, and (3) discuss the mechanisms which may have controlled production, accumulation, and preservation of the organic matter. The black shale sequences show a wide range of organic carbon contents (0.5-7.0 wt %) and consist of thermally immature organic matter of type II to II/III kerogen. Rock-Eval pyrolysis revealed fair to very good petroleum source rock potential, suggesting a deposition in restricted shallow marine basins. Well-developed lamination and the formation of autochthonous pyrite framboids further indicate suboxic to anoxic bottom water conditions. In combination with very low sedimentation rates it seems likely that preservation was the principal control on organic matter accumulation. However, a decrease of organic carbon preservation and an increase of refractory organic matter from the Volgian to the Hauterivian are superimposed on short-term variations (probably reflecting Milankovitch cycles). Various parameters indicate that black shale formation in the NGS was gradually terminated by increased oxidative conditions in the course of a sea-level rise.