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.

Jurassic sedimentation history at DSDP Hole 76-534A

Site 534 reflects a complex interplay of global, basinal, and local influences on sedimentation during the Callovian and Late Jurassic. Rifting and rapid subsidence of the continental margins of the North Atlantic-Tethys seaway occurred during the late Early Jurassic (Sinemurian-Pliensbachian), but rapid spreading between the North American margin (Blake Spur Ridge and magnetic lineation) and the northwest African margin did not commence until the Bathonian or earliest Callovian. Site 534, drilled on marine magnetic anomaly "M-28" of Bryan et al. (1980), was initially about 150 km from either continental margin. The ?middle Callovian basal sediments are dusky red silty marl. Callovian transgression led to active carbonate platforms on the margin, recorded at Site 534 as a rise in the CCD (carbonate compensation depth), then arrival of lime-rich turbidites from the Blake Plateau platform across the Blake Spur Ridge. The host pelagic sediment is greenish black, organic-rich, radiolarian-rich, silty claystone. Hydrothermal activity on the nearby spreading ridge enriched this lower unit in metals. In the Oxfordian, the input of terrestrial silt rapidly diminished; radiolarians or other bioclasts were not preserved. The dark variegated claystone has fine-grained marl and reddish claystone turbidite beds. The late Callovian-Oxfordian Western Tethys has radiolarian chert deposition, marine hiatuses, or organic-rich sediments. The Kimmeridgian and Tithonian had a stable or receding sea level. Near the end of the Jurassic many of the carbonate platforms of the margins were buried beneath prograding fan or alluvial deposits. Carbonate deposition shifted to the deep sea. Site 534 records the deepening of the CCD and ACD (aragonite compensation depth) during the Kimmeridgian and early Tithonian, then a rise of the ACD in the middle Tithonian. Similar trends occurred throughout the Western Tethys-Atlantic. High nannofossil productivity of the seaway led to deposition of very widespread white micritic limestone in the late Tithonian-Berriasian. The underlying sediment had a slower deposition rate of carbonate, therefore its higher clay and associated Fe content produced a red marl. A short sea-level incursion occurred on the Atlantic margins during the Kimmeridgian and is reflected in the Site 534 greenish gray marl unit by numerous turbidite beds of shallow-water carbonates.

(Table 1) Chemical compositions of iron-manganese phosphate crusts, phosphorites, volcanic products, and phosphate limestones from ocean seamounts

New data on phosphorites of Atlantic seamounts are presented and used in combination with published data to analyze sources of phosphorus in them.

Contents of P2O5 and REE in phosphorites from shelves and Pacific seamounts

Recent phosphorites from the Namibian shelf are characterized by low REE contents, depletion in REE compared to host sediments and sharp deficiency of lanthanum and europium. In Late Quaternary and Pre-Quaternary phosphorites from ocean shelves REE contents and patterns in general are the same as in host sediments. Phosphorites from seamounts are enriched in REE compared to shelf phosphorites and their patterns are close to one of seawater. Behavior of REE in shelf phosphorites is determined by the fact that in early stages of phosphorite formation REE are associated not primarily with phosphate, but with organic matter and terrigenous impurities. Only in the later stages of diagenesis phosphate begins to play a leading role in concentration of REE. In metasomatic phosphorites on seamounts concentration of REE depends on age and depth of these rocks, i.e. it is determined by duration and conditions of contact with sea water.

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.