(Table 1) Elemental composition, pyrite-Fe and degree of pyritisation in Upper Pliensbachian and Lower Toarcian sediments from the costal section of Yorkshire

Profiles of Mo/total organic carbon (TOC) through the Lower Toarcian black shales of the Cleveland Basin, Yorkshire, United Kingdom, and the Posidonia shale of Germany and Switzerland reveal water mass restriction during the interval from late tenuicostatum Zone times to early bifrons Zone times, times which include that of the putative Early Toarcian oceanic anoxic event. The degree of restriction is revealed by crossplots of Mo and TOC concentrations for the Cleveland Basin, which define two linear arrays with regression slopes (ppm/%) of 0.5 and 17. The slope of 0.5 applies to sediment from the upper semicelatum and exaratum Subzones. This value, which is one tenth of that for modern sediments from the Black Sea (Mo/TOC regression slope 4.5), reveals that water mass restriction during this interval was around 10 times more severe than in the modern Black Sea; the renewal frequency of the water mass was between 4 and 40 ka. The Mo/TOC regression slope of 17 applies to the overlying falciferum and commune subzones: the value shows that restriction in this interval was less severe and that the renewal frequency of the water mass was between 10 and 130 years. The more restricted of the two intervals has been termed the Early Toarcian oceanic anoxic event but is shown to be an event caused by basin restriction local to NW Europe. Crossplots of Re, Os, and Mo against TOC show similar trends of increasing element concentration with increase in TOC but with differing slopes. Together with modeling of 187Os/188Os and d98Mo, the element/TOC trends show that drawdown of Re, Os, and Mo was essentially complete during upper semicelatum and exaratum Subzone times (Mo/TOC regression slope of 0.5). Drawdown sensitized the restricted water mass to isotopic change forced by freshwater mixing so that continental inputs of Re, Os, and Mo, via a low-salinity surface layer, created isotopic excursions of up to 1.3 per mil in d98Mo and up to 0.6 per mil for 187Os/188Os. Restriction thereby compromises attempts to date Toarcian black shales, and possibly all black shales, using Re-Os chronology and introduces a confounding influence in the attempts to use d98Mo and initial 187Os/188Os for palaeo-oceanographic interpretation.

Organic geochemistry of upper Jurassic-Cretaceous sediments at DSDP Hole 71-511

Cretaceous and Jurassic sediments 435 m thick were drilled at Site 511, in the basin province of the Falkland Plateau, during DSDP Leg 71. The calcareous Unit 3 and the clayey zeolitic Unit 4, both of Senonian age, revealed poorly preserved organic matter indicative of oxidized environments. The same characteristics prevailed for the clayey Unit 5 of Turonian to Albian age. Strictly reducing environments existed for black facies along Unit 6 of earliest Albian to Late Jurassic age and allowed the preservation of a rich organic material that is marine in origin. Besides the transition from reducing conditions in Unit 6 to oxidizing conditions in Unit 5, there are 20 meters of sediments in Cores 56-58 where detrital, nonmarine and then marine organic matter, both implying more or less reducing environments, are interlain by poorly preserved material. In the black shales of the bottom Cores 69 and 70, some nonmarine detritus is mixed with the predominantly marine organic material. An immature stage of evolution can be assigned to all of the samples studied. The chapter also undertakes a comparison with contemporaneous lithologies at adjacent Sites 327 and 330 and attempts some reconstruction of the geography of the eastern Falkland Plateau during the Mesozoic.

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.

Body mass, flipper length, oxidative balance indices and telomere length of king penguin chicks (A. patagonicus) on Possession Island

One of the reasons for animals not to grow as fast as they potentially could is that fast growth has been shown to be associated with reduced lifespan. However, we are still lacking a clear description of the reality of growth-dependent modulation of ageing mechanisms in wild animals. Using the particular growth trajectory of small king penguin chicks naturally exhibiting higher-than-normal growth rate to compensate for the winter break, we tested whether oxidative stress and telomere shortening are related to growth trajectories. Plasma antioxidant defences, oxidative damage levels and telomere length were measured at the beginning and at the end of the post-winter growth period in three groups of chicks (small chicks, which either passed away or survived the growth period, and large chicks). Small chicks that died early during the growth period had the highest level of oxidative damage and the shortest telomere lengths prior to death. Here, we show that small chicks that grew faster did it at the detriment of body maintenance mechanisms as shown by (i) higher oxidative damage and (ii) accelerated telomere loss. Our study provides the first evidence for a mechanistic link between growth and ageing rates under natural conditions.

Major, trace and rare earth element concentrations of sediments from ODP Leg 207 sites

The Cretaceous and Paleogene sediments recovered during Ocean Drilling Program Leg 207 can be divided into three broad modes of deposition: synrift clastics (lithologic Unit V), organic matter-rich, laminated black shales (Unit IV), and open-marine chalk and calcareous claystones (Units III-I). The aim of this study is to provide a quantitative geochemical characterization of sediments representing these five lithologic units. For this work we used the residues (squeeze cakes) obtained from pore water sampling. Samples were analyzed for bulk parameters (total inorganic carbon, total organic carbon, and S) and by X-ray fluorescence for major (Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, and P) and selected minor (As, Ba, Co, Cr, Cu, Mo, Ni, Pb, Rb, Sr, U, V, Y, Zn, and Zr) elements. Inductively coupled plasma-mass spectrometry analyses for rare earth elements (REEs) were performed on acid digestions of the squeeze cake samples from Site 1258. The major element composition is governed by the mixture of a terrigenous detrital component of roughly average shale (AS) composition with biogenous carbonate and silica. The composition of the terrigenous detritus is close to AS in Units II-IV. For Unit I, a more weathered terrigenous source is suggested. Carbonate contents reach >60 wt% on average in chalks and calcareous claystones of Units II-IV. The SiO2 contribution in excess of the normal terrigenous-detrital background indicates the presence of biogenous silica, with highest amounts in Units II and III. The contents of coarse-grained material (quartz) are enhanced in Unit V, where Ti and Zr contents are also high. This indicates a high-energy depositional environment. REE patterns are generally similar to AS. A more pronounced negative Ce anomaly in Unit IV may indicate low-oxygen conditions in the water column. The Cretaceous black shales of Unit IV are clearly enriched in redox-sensitive and stable sulfide-forming elements (Mo, V, Zn, and As). High phosphate contents point toward enhanced nutrient supply and high bioproductivity. Ba/Al ratios are rather high throughout Unit IV despite the absence of sulfate in the pore water, indicating elevated primary production. Manganese contents are extremely low for most of the interval studied. Such an Mn depletion is only possible in an environment where Mn was mobilized and transported into an expanded oxygen minimum zone ("open system"). The sulfur contents show a complete sulfidation of the reactive iron of Unit IV and a significant excess of sulfur relative to that of iron, which indicates that part of the sulfur was incorporated into organic matter. We suppose extreme paleoenvironmental conditions during black shale deposition: high bioproductivity like in recent coastal upwelling settings together with severe oxygen depletion if not presence of hydrogen sulfide in the water column.

Palynofacies analysis of sediments in the eastern Equatorial Atlantic

Analyses of the palynofacies and sporomorph thermal alteration indices (TAI) of sediments from Ocean Drilling Program (ODP) Sites 959 to 962 in the Cote d'Ivoire-Ghana Transform Margin, West Africa were undertaken to (1) determine the source and depositional conditions of the organic matter in the sediments, (2) refine a paleobathymetric curve derived from other data for Site 959, which drilled the most continuous sedimentary sequence from Pleistocene to Albian and (3) interpret the paleothermal history of the area. Twelve types of dispersed organic matter were identified: amorphous organic matter (AOM), marine palynomorphs, algae, resins, black debris, yellow-brown fragments, black-brown fragments, cuticles, plant tissue, wood, sporomorphs and fungi, The relative abundances of these organic matter components at each site were analyzed using cluster analysis, resulting in the identification of seven palynofacies assemblages at Site 959, five each at sites 960 and 961, and four at Site 962. Amorphous organic matter (which is chiefly marine derived), black debris and wood have played the most significant role in defining palynofacies assemblages. The palynofacies assemblages show some correlation with lithologic units, sediment sources and depositional environments. Previous palynofacies studies in passive margins have demonstrated that changes in the ratio of AOM to terrestrial organic matter are related primarily to proximal-distal positions of depositional environments relative to the shoreline. However, this assumption does not always hold true for a transform margin where tectonic factors play an important role in the organic matter distribution, at least in the early stages of evolution. Lithofacies, CCD paleodepths for the North Atlantic, trace fossil association, benthic foraminifera and palynofacies data were the criteria used for reconstructing a paleobathymetric curve for Site 959. A cyclicity in the organic matter distribution of the Upper Miocene to Lower Pliocene pelagic sediments could be related to fluctuations in productivity of biosiliceous and calcareous organisms, and sedimentation rates. A drastic increase in the amount of AOM and a decrease in black debris and wood in the carbonate and clastic rocks (Lithologic Unit IV) overlying the tectonized Albian sediments (Lithologic Unit V) at Sites 959 and 960 coincide with the presence of an unconformity. Qualitative color analysis of palynomorphs was undertaken for all sites, although the main focus was on Site 959 where detailed organic geochemical data were available. At Site 959, TAI values indicate an immature stage of organic maturation (<2) down to the black claystones of Lithologic Unit III at about 918.47 mbsf. Below this, samples show an increase with depth to a moderately mature stage (>2 except for the claystone samples between 1012.52 and 1036.5 mbsf, and one limestone sample at 1043.4 mbsf), reaching peak levels of 2.58 to 3.0 in the tectonized Albian sediments below the unconformity. These TAI values show a positive correlation with the Tma x values derived from Rock-Eval pyrolysis data. The highest values recorded in the basal tectonized units at all the sites (Sites 960-962 have mean values between 2.25 and 3.13) may be related to high heat flow during the intracontinental to syntransform basin stage in the region.

Description of the fossil manganese nodules found in the Oligocene clay deposits of Moravia, Brno area, Czech Republic

In the green Oligocene clay of Krizanovice (former Krzyzanowicz) the author found numerous black nodules. In the 3-4 centimeter thick black crust of a particular specimen the concentration in MnO2 is evaluated at 46.6% MnO2. The determination was done using the Volhard's method (precipitation of Fe by ZnO and titration with KMnO4). Only the dissoleved part in HCL was analysed. The non soluble residue was essentially a silica precipitate in the form of many gray flakes. The specific gravity of the crust was evaluated at 3.8. In the internal yellow core the amount of manganese is about 2.39% MnO2. Due to the light color it is judged to probably be in the form of Mn2O3.

Chemical composition of the chalcophanite rich surface of an encrusted rock ashore Lake Macquarie, Australia

Mineralogical interest in the nature of manganese oxide particulates in natural marine water (Suess, 1979), natural lake water (Klaveness, 1977), and simulated lake water (Giovanoli, 1980), prompted a search for such particulates in a large New South Wales coastal lake. The investigated waters did show the existence of manganese oxide replacement phenomena in fragmentary sedimentary rocks near the south margin of Lake Macquarie. The black crusts of manganese oxide discovered on rocks close to the waterline have revealed a three layers structure. Layer A (0-35 micron), adjacent to the rock, is composed essentially of kaolinite of weathering origin, together with low levels of manganese oxide without detectable Zn. Layer B (35-80 micron) follows as a manganese oxide layer containing admixed kaolinite and low amounts of Zn. Layer C (80-130 micron) is the closest to the surface and is made of Chalcophanite containing 10-15% of ZnO.

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 2) Organic residue at DSDP Hole 76-534A

The kind, sedimentation rate, and diagenesis of organic particles delivered to the North Atlantic seafloor during the Middle Jurassic-Early Cretaceous were responsible for the presence of carbonaceous sediments in Hole 534A. Organic-rich black clays formed from the rapid supply of organic matter; this organic matter was composed of either abundant, well-preserved, and poorly sorted particles of land plants deposited in clays and silty clays within terrigenous turbiditic sequences (tracheal facies) or abundant amorphous debris (xenomorphic facies) generated through the digestive tracts of marine zooplankton and sedimented as fecal pellets. Evidence for the fecal-pellet origin of xenomorphic debris is illustrated. Black clays were also produced in sediments containing less organic matter as a result of the black color of carbonized particles composing all or most of the residues (micrinitic facies). Slowly sedimented hematitic Aptian clays contain very little carbonized, organic debris that survived diagenetic oxidation. In the red calcareous clay sequence of the Late Jurassic, larger amounts of this oxidized debris turned several clay layers black or blackish red. Carbonized debris also dominates the residues recovered in interbedded black and green Albian clays. Carbonization of organic matter in these sediments either turned them black or provided the diagenetic environment for reduced iron. Carbonized debris is also appreciable in burrow-mottled black-green Kimmeridgian clay. The study of Hole 534A organic matter indicates that during the middle Callovian there was a rapid supply of terrigenous organic matter, followed by a late Callovian episode of rapidly supplied xenomorphic debris deposited as fecal pellets. The Late Jurassic-Berriasian was a time of slower sedimentation of organic matter, primarily of a marine dinoflagellate flora in a poorly preserved xenomorphic facies variously affected by diagenetic oxidation. Several intervals of carbonized tracheal tissue in the Oxfordian and Kimmeridgian suggest episodes of oxidized terrigenous matter. The same sequence of Callovian organic events is evident in much of the Early Cretaceous

Chert petrology and geochemistry at DSDP Leg 62 Holes

Sixty-five chert, porcellanite, and siliceous-chalk samples from Deep Sea Drilling Project Leg 62 were analyzed by petrography, scanning electron microscopy, analysis by energy-dispersive X-rays, X-ray diffraction, X-ray spectroscopy, and semiquantitative emission spectroscopy. Siliceous rocks occur mainly in chalks, but also in pelagic clay and marlstone at Site 464. Overall, chert probably constitutes less than 5% of the sections and occurs in deposits of Eocene to Barremian ages at sub-bottom depths of 10 to 820 meters. Chert nodules and beds are commonly rimmed by quartz porcellanite; opal-CT-rich rocks are minor in Leg 62 sediments 65 to 108 m.y. old and at sub-bottom depths of 65 to 520 meters. Chert ranges from white to black, shades of gray and brown being most common; yellow-brown and red-brown jaspers occur at Site 464. Seventy-eight percent of the studied cherts contain easily recognizable burrow structures. The youngest chert at Site 463 is a quartz cast of a burrow. Burrow silica maturation is always one step ahead of host-rock silicification. Burrows are commonly loci for initial silicification of the host carbonate. Silicification takes place by volume-f or-volume replacement of carbonate sediment, and more-clay-rich sediment at Site 464. Nannofossils are commonly pseudomorphically replaced by quartz near the edges of chert beds and nodules. Other microfossils, mostly radiolarians and foraminifers, whether in chalk or chert, can be either filled with or replaced by calcite, opal-CT, and (or) quartz. Chemical micro-environments ultimately control the removal, transport, and precipitation of calcite and silica. Two cherts from Site 465 contain sulfate minerals replaced by quartz. Site 465 was never subaerially exposed after sedimentation began, and the formation of the sulfate minerals and their subsequent replacement probably occurred in the marine environment. Several other cherts with odd textures are described in this paper, including (1) a chert breccia cemented by colloform opal-CT and chalcedony, (2) a transition zone between white porcellanite containing opal-CT and quartz and a burrowed brown chert, consisting of radial aggregates of opal-CT with hollow centers, and (3) a chert that consists of silica-replaced calcite pseudospherules interspersed with streaks and circular masses of dense quartz. X-ray-diffraction analyses show that when data from all sites are considered there are poorly defined trends indicating that older cherts have better quartz crystallinity than younger ones, and that opal-CT crystallite size increases and opal-CT cf-spacings decrease with depth of occurrence in the sections. In a general way, depth of burial and the presence of calcite promote the ordering in the opal-CT crystal structure which allows its eventual conversion to quartz. Opal-CT in porcellanites converts to quartz after reaching a minimum d-spacing of 4.07 Å. Quartz/opal-CT ratios and quartz crystallinity vary randomly on a fine scale across four chert beds, but quartz crystallinity increases from the edge to the center of a fifth chert bed; this may indicate maturation of the silica. Twenty-four rocks were analyzed for their major- and minor-element compositions. Many elements in cherts are closely related to major mineral components. The carbonate component is distinguished by high values of CaO, MgO, Mn, Ba, Sr, and (for unknown reasons) Zr. Tuffaceous cherts have high values of K and Al, and commonly Zn, Mo, and Cr. Pure cherts are characterized by high SiO2 and B. High B may be a good indicator of formation of chert in an open marine environment, isolated from volcanic and terrigenous materials.

(Table 3) Geochemistry at DSDP Leg 79 Holes

Detailed mineralogical and geochemical studies were performed on samples from selected time intervals recovered during Leg 79 on the Mazagan Plateau. The uppermost Albian and Cenomanian sediments of Sites 545 and 547 can be correlated on the basis of mineralogy and geochemistry; these sediments illustrate differential settling processes and the existence of hot climates with alternating humid and dry seasons in the African coastal zone. The upper Aptian to Albian black shales of Site 545 point to an irregular alternation of tectonic activity and relaxation stages, allowing different behaviors in the reworking of soils, crystalline rocks, and sediments born in peri-marine basins. The barren lower Mesozoic reddish sediments and evaporitic series of Sites 546 and 547 are characterized by a strong physical erosion of sialic landscapes, without clear evidence of post-depositional metamorphic events. At Site 546 strong early diagenetic processes in a confined evaporitic environment affect both the mineralogy and the geochemistry of pre-Miocene rocks.

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.