Chemical composition of Black Sea bottom sediments

Concentrations of major-, trace- and rare earth elements in recent and Old Black Sea bottom sediments are reported in the paper. Data presented suggest that accumulation of black shale deposits was not constrained to a certain time span but proceeds in certain modern basins and generates sediments with metal contents close to those in their ancients analogues in hydrogen sulfide contaminated environments. If REE are involved in the process, their composition can vary depending on such factors as variations in redox conditions and occurrence of phosphate and barite nodules, which can induce development of either positive or negative Eu anomalies.

Chemical profiles in sediment and basalt at DSDP Hole 74-525A

Forty sediment and four basement basalt samples from DSDP Hole 525A, Leg 74, as well as nine basalt samples from southern and offshore Brazil, were subjected to instrumental neutron activation analysis. Thirty-two major, minor, and trace elements were determined. The downcore element concentration profiles and regression analyses show that the rare earth elements (REE) are present in significant amounts in both the carbonate and noncarbonate phases in sediments; Sr is concentrated in the carbonate phase, and most of the other elements determined exist mainly in the noncarbonate phase. The calculated partition coefficients of the REE between the carbonate phase and the free ion concentrations in seawater are high and increase with decreasing REE ionic radii from 3.9 x 10**6 for La to 15 x 10**6 for Lu. Calculations show that the lanthanide concentrations in South Atlantic seawater have not been changed significantly over the past 70 Ma. The Ce anomaly observed in the carbonate phase is a redox indicator of ancient seawater. Study of the Ce anomaly reveals that seawater was anoxic over the Walvis Ridge during the late Campanian. As the gap between South America and West Africa widened and the Walvis Ridge subsided from late Campanian to late Paleocene times, the water circulation of the South Atlantic improved and achieved oxidation conditions about 54 Ma that are similar to present seawater redox conditions in the world oceans. The chemical compositions of the basement rocks correspond to alkalic basalts, not mid-ocean ridge basalts (MORBs). The results add more evidence to support the hypothesis that the Walvis Ridge was formed by a series of volcanos moving over a "hot spot" near the Mid-Atlantic Ridge. From the chemical composition and REE pattern, one 112 Ma old basalt on the Brazilian continental shelf has been identified as an early stage MORB. To date, this is the oldest oceanic tholeiite recovered from the South Atlantic. This direct evidence indicates that the continental split between South America and Africa commenced > 112 Ma.

Chemistry of hydrothermal clasy and sulfides of ODP Site 106-649

Several meters of unconsolidated hydrothermal sediment were recovered from the Snake Pit hydrothermal field during ODP Leg 106. Polymetallic sulfides comprise most of the sediment with minor fragments of massive sulfide, organic debris, clay minerals, and fresh glass shards. Trace element and Sr-isotope contents of hydrothermal clays and sulfides from Holes 649B and 649G indicate that these minerals precipitated from a mixed hydrothermal fluid-seawater solution. Evaluation of the REE mineral data and the Snake Pit hydrothermal fluids shows that the REE distribution coefficients between the hydrothermal fluids and clay-sulfide mixes range from 100-500. This indicates that hydrothermal fluids originating in the root-zone of the Snake Pit hydrothermal system may be modified by the precipitation of hydrothermal minerals, either in the shallow subsurface or within chimney structures. Contrasting REE profiles of clay-sulfide aggregates and massive sulfides from Holes 649B and 649G may be accounted for by spatial and/or temporal variations in redox conditions in the plumbing system.

Geochemical analysis of nine sections from the Nama Group, Namibia

The first appearance of skeletal metazoans in the late Ediacaran (~550 million years ago; Ma) has been linked to the widespread development of oxygenated oceanic conditions, but a precise spatial and temporal reconstruction of their evolution has not been resolved. Here we consider the evolution of ocean chemistry from ~550 to ~541 Ma across shelf-to-basin transects in the Zaris and Witputs Sub-Basins of the Nama Group, Namibia. New carbon isotope data capture the final stages of the Shuram/Wonoka deep negative C-isotope excursion, and these are complemented with a reconstruction of water column redox dynamics utilising Fe-S-C systematics and the distribution of skeletal and soft-bodied metazoans. Combined, these inter-basinal datasets provide insight into the potential role of ocean redox chemistry during this pivotal interval of major biological innovation. The strongly negative d13C values in the lower parts of the sections reflect both a secular, global change in the C-isotopic composition of Ediacaran seawater, as well as the influence of 'local' basinal effects as shown by the most negative d13C values occurring in the transition from distal to proximal ramp settings. Critical, though, is that the transition to positive d13C values postdates the appearance of calcified metazoans, indicating that the onset of biomineralization did not occur under post-excursion conditions. Significantly, we find that anoxic and ferruginous deeper water column conditions were prevalent during and after the transition to positive d13C that marks the end of the Shuram/Wonoka excursion. Thus, if the C isotope trend reflects the transition to global-scale oxygenation in the aftermath of the oxidation of a large-scale, isotopically light organic carbon pool, it was not sufficient to fully oxygenate the deep ocean. Both sub-basins reveal highly dynamic redox structures, where shallow, inner ramp settings experienced transient oxygenation. Anoxic conditions were caused either by episodic upwelling of deeper anoxic waters or higher rates of productivity. These settings supported short-lived and monospecific skeletal metazoan communities. By contrast, microbial (thrombolite) reefs, found in deeper inner- and mid-ramp settings, supported more biodiverse communities with complex ecologies and large skeletal metazoans. These long-lived reef communities, as well as Ediacaran soft-bodied biotas, are found particularly within transgressive systems, where oxygenation was persistent. We suggest that a mid-ramp position enabled physical ventilation mechanisms for shallow water column oxygenation to operate during flooding and transgressive sea-level rise. Our data support a prominent role for oxygen, and for stable oxygenated conditions in particular, in controlling both the distribution and ecology of Ediacaran skeletal metazoan communities.

Foraminiferal trace element ratios from South Atlantic sediments

The rate of uranium accumulation in oceanic sediments from seawater is controlled by bottom water oxygen concentrations and organic carbon fluxes-two parameters that are linked to deep ocean storage of CO2. To investigate glacial-interglacial changes in what is known as authigenic U, we have developed a rapid method for its determination as a simple addition to a procedure for foraminiferal trace element analysis. Foraminiferal calcite acts as a low U substrate (U/Ca < 15 nmol/mol) upon which authigenic U accumulates in reducing sediments. We measured a downcore record of foraminiferal U/Ca from ODP Site 1090 in the South Atlantic and found that U/Ca ratios increase by 70-320 nmol/mol during glacial intervals. There is a significant correlation between U/Ca records of benthic and planktonic foraminiferal species and between U/Ca and bulk sediment authigenic U. These results indicate that elevated U/Ca ratios are attributable to the accumulation of authigenic U coatings in sediments. Foraminiferal Mn/Ca ratios were lower during the glacial intervals, suggesting that the observed U accumulation on the shells is not directly linked to U incorporation into secondary manganese phases. Thus, foraminiferal U/Ca ratios may provide useful information on past changes in sediment redox conditions.

Chemistry of bulk-rocks and minerals of ODP Hole 120-748C

Five hundred meters of a unique Upper Cretaceous Cr-rich glauconitic sequence (Unit III) that overlies a 3-m-thick alkali-basalt flow with underlying epiclastic volcanogenic sediments was drilled at ODP Leg 120 Site 748. The Cr-rich glauconitic sequence is lithostratigraphically and biostratigraphically divided into three subunits (IIIA, IIIB, IIIC) that can also be recognized by the Cr concentration of the bulk sediment, which is low (<200 ppm) in Subunits IIIC and IIIA and high (400-800 ppm) in Subunit IIIB. The Cr enrichment is caused by Cr-spinel, which is the only significant heavy mineral component beside Fe-Ti ores. Other Cr-bearing components are glauconite pellets and possibly some other clay minerals. The glauconitic sequence of Subunit IIIB was formed by reworking of glauconite and volcanogenic components that were transported restricted distances and redeposited downslope by mass-transportation processes. The site of formation was a nearshore, shallow inner shelf environment, and final deposition may have been on the outer part of a narrow shelf, at the slope toward the restricted, probably synsedimentary, faulted Raggatt Basin. The volcanic edifices uncovered on land were tholeiitic basalts (T-MORB), alkali-basaltic (OIB) and (?)silicic volcanic complexes, and ultramafic rocks. The latter were the ultimate source for the Cr-spinel contribution. Terrestrial aqueous solutions carried Fe, K, Cr, Si, and probably Al into the marine environment, where, depending on the redox conditions of microenvironments in the sediment, green (Fe- and K-rich) or brown (Al-rich) glauconite pellets formed. The Upper Cretaceous glauconitic sequence at Site 748 on the Southern Kerguelen Plateau constitutes the transition in space and time from terrestrial to marine, from magmatically active subaerial to magmatically passive submarine conditions, and from a tranquil platform to active rifting conditions.

Palynofacies investigation of Callovian sediments of DSDP Hole 79-534A

During the extension of Deep Sea Drilling Project (DSDP) Leg 76 a new and previously unpenetrated lithological unit composed mainly of claystones was cored above basalt basement at Site 534 in the Blake-Bahama Basin. The Callovian part of the new unit contains interbedded 'black shales' which were hitherto unexpected in this part of the section. This Paper presents a brief palynological examination of lithofacies-kerogen relationships in these sediments and shows that their organic content is almost entirely a function of the re-deposition of terrestial and marine organic matter versus the ambient redox conditions of the depositional environment. Allochthonous organic matter inputs are highest in the interbedded turbidites and decline progressively toward the pelagic black shales in which marine organic matter is comparatively well preserved. The significance of various kerogen and palynomorph indices are discussed. The study emphasizes the absolute necessity for sedimentologically-aware sampling in all palynological and geochemical work on lithologically heterogeneous sequences.

Geochemistry of the Kimmeridge Clay Formation, Dorset Coast

The Kimmeridge Clay Formation (KCF) and its equivalents worldwide represent one of the most prolonged periods of organic carbon accumulation of the Mesozoic. In this study, we use the molybdenum (Mo) stable isotope system in conjunction with a range of trace metal paleoredox proxies to assess how seawater redox varied both locally and globally during the deposition of the KCF. Facies with lower organic carbon contents (TOC 1-7 wt %) were deposited under mildly reducing (suboxic) conditions, while organic-rich facies (TOC >7 wt %) accumulated under more strongly reducing (anoxic or euxinic) local conditions. Trace metal abundances are closely linked to TOC content, suggesting that the intensity of reducing conditions varied repeatedly during the deposition of the KCF and may have been related to orbitally controlled climate changes. Long-term variations in d98/95Mo are associated with the formation of organic-rich intervals and are related to third-order fluctuations in relative sea level. Differences in the mean d98/95Mo composition of the organic-rich intervals suggest that the global distribution of reducing conditions was more extensive during the deposition of the Pectinatites wheatleyensis and lower Pectinatites hudlestoni zones than during the deposition of the upper Pectinatites hudlestoni and Pectinatites pectinatus zones. The global extent of reducing conditions during the Kimmerigidan was greater than today but was less widespread than during the Toarcian (Early Jurassic) oceanic anoxic event. This study also demonstrates that the Mo isotope system in Jurassic seawater responded to changes in redox conditions in a manner consistent with its behavior in present-day sedimentary environments.

Geochemistry and accumulation rates of the early Paleogene in the Weddel Sea, Maud Rise and Kerguelen Plateau

Marine biological productivity has been invoked as a possible climate driver during the early Paleogene through its potential influence on atmospheric carbon dioxide concentrations. However, the relationship of export productivity (the flux of organic carbon (C) from the surface ocean to the deep ocean) to organic C burial flux (the flux of organic C from the deep ocean that is buried in marine sediments) is not well understood. We examine the various components involved with atmosphere-to-ocean C transfer by reconstructing early Paleogene carbonate and silica production (using carbonate and silica mass accumulation rates (MARs)); export productivity (using biogenic barium (bio-Ba) MARs); organic C burial flux (using reactive phosphorus (P) MARs); redox conditions (using uranium and manganese contents); and the fraction of organic C buried relative to export productivity (using reactive P to bio-Ba ratios). Our investigations concentrate on Paleocene/Eocene sections of Sites 689/690 from Maud Rise and Site 738 from Kerguelen Plateau. In both regions, export productivity, organic C burial flux, and the fraction of organic C buried relative to export productivity decreased from the Paleocene/early Eocene to the middle Eocene. A shift is indicated from an early Paleogene two-gyre circulation in which nutrients were not efficiently recycled to the surface via upwelling in these regions, to a circulation more like the present day with efficient recycling of nutrients to the surface ocean. Export productivity was enhanced for Kerguelen Plateau relative to Maud Rise throughout the early Paleogene, possibly due to internal waves generated by the plateau regardless of gyre circulation.

Geochemistry and stable isotope record of carbonate oozes and chalks of ODP Hole 130-807B

Light greenish gray and pale purple color bands are common in the ooze and chalk of the Ontong Java Plateau. Analyses of Pleistocene and Pliocene ooze samples that contain abundant bands indicate that the purple bands are colored by finely disseminated iron sulfide, whereas the green bands are colored by finely disseminated Fe- and Al-bearing silicates (probably clays). No local contrasts in the total organic carbon contents, carbon and oxygen isotopic compositions, and grain sizes were found. Band abundances, counted from core photographs of all Leg 130 holes, can be correlated from hole to hole on the basis of age rather than depth. The temporal distribution of these color bands is also comparable with that of the green bands described from the Lord Howe Rise, which were previously interpreted as products of altered volcanic glass. This may indicate that the green and purple bands on the Ontong Java Plateau originate from the early alteration of volcanic ash. The crosscutting relationships between the green and purple bands and original structures in the host sediment indicate that the bands have been locally altered by redox conditions in the sediments after the bands were formed.

Ba, Mn, and Mg record derived from Hoeglundina elegans of sediment core SLA-9

The evolution of productivity, redox conditions, temperature, and ventilation during the deposition of an Aegean sapropel (S1) is independently constrained using bulk sediment composition and high-resolution single specimen benthic foraminiferal trace metal and stable isotope data. The occurrence of benthic foraminifer, Hoeglundina elegans (H. elegans), through a shallow water (260 m) sapropel, permits for the first time a comparison between dissolved and particulate concentrations of Ba and Mn and the construction of a Mg/Ca-based temperature record through sapropel S1. The simultaneous increase in sedimentary Ba and incorporated Ba in foraminiferal test carbonate, (Ba/Ca)H. elegans, points to a close coupling between Ba cycling and export productivity. During sapropel deposition, sedimentary Mn content ((Mn/Al)sed) is reduced, corresponding to enhanced Mn2+ mobilization from sedimentary Mn oxides under suboxic conditions. The consequently elevated dissolved Mn2+ concentrations are reflected in enhanced (Mn/Ca)H. elegans levels. The magnitude and duration of the sapropel interruption and other short-term cooling events are constrained using Mg/Ca thermometry. Based on integrating productivity and ventilation records with the temperature record, we propose a two-mode hysteresis model for sapropel formation.