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.

Geochemistry of dark-light rhythm sediments of the Japan Sea

Ocean Drilling Program Legs 127 and 128 in the Japan Sea have revealed the existence of numerous dark-light rhythms of remarkable consistency in sediments of late Miocene, latest Pliocene, and especially Pleistocene age. Light-colored units within these rhythms are massive or bioturbated, consist of diatomaceous clays, silty clays, or nannofossil-rich clays, and are generally poor in organic matter. Dark-colored units are homogeneous, laminated, or thinly bedded and include substantial amounts of biogenic material such as well-preserved diatoms, planktonic foraminifers, calcareous nannofossils, and organic matter (maximum 7.4 wt%). The dark-light rhythms show a similar geometrical pattern on three different scales: First-order rhythms consist of a cluster dominated by dark-colored units followed by a cluster dominated by light-colored units (3-5 m). Spectral analysis of a gray-value time series suggests that the frequencies of the first-order rhythms in sediments of latest Pliocene and Pleistocene age correlate to the obliquity and the eccentricity cycles. The second-order dark-light rhythms include a light and a dark-colored unit (10-160 cm). They were formed in time spans of several hundred to several ten thousand years, with variance centering around 10,500 yr. This frequency may correspond to half the precessional cycle. Third-order rhythms appear as laminated or thinly bedded dark-light couplets (2-15 mm) within the dark-colored units of the second-order rhythms and may represent annual frequencies. In interpreting the rhythms, we have to take into account that (1) the occurrence of the first- and second-order rhythms is not necessarily restricted to glacial or interglacial periods as is shown by preliminary stable-isotope analysis and comparison with the published d18O record; (2) they appear to be Milankovitch-controlled; and (3) a significant number of the rhythms are sharply bounded. The origin of the dark-light rhythms is probably related to variations in monsoonal activity in the Japan Sea, which show annual frequencies, but also operates in phase with the orbital cycles.

Mineral composition, rare earth elements, and trace elements from samples of the northern Congo deep-sea fan

Authigenic carbonates were collected from methane seeps at Hydrate Hole at 3113 m water depth and Diapir Field at 2417 m water depth on the northern Congo deep-sea fan during RV Meteor cruise M56. The carbonate samples analyzed here are nodules, mainly composed of aragonite and high-Mg calcite. Abundant putative microbial carbonate rods and associated pyrite framboids were recognized within the carbonate matrix. The d13C values of the Hydrate Hole carbonates range from -62.5 permil to -46.3 permil PDB, while the d13C values of the Diapir Field carbonate are somewhat higher, ranging from -40.7 permil to -30.7 permil PDB, indicating that methane is the predominant carbon source at both locations. Relative enrichment of 18O (d18O values as high as 5.2 permil PDB) are probably related to localized destabilization of gas hydrate. The total content of rare earth elements (REE) of 5% HNO3-treated solutions derived from carbonate samples varies from 1.6 ppm to 42.5 ppm. The shale-normalized REE patterns all display positive Ce anomalies (Ce/Ce* > 1.3), revealing that the carbonates precipitated under anoxic conditions. A sample from Hydrate Hole shows a concentric lamination, corresponding to fluctuations in d13C values as well as trace elements contents. These fluctuations are presumed to reflect changes of seepage flux.

Chemical and isotopic compositions of sediments and some minerals from the Derugin Basin, Sea of Okhotsk

The paper reports specific mineralogical and geochemical characteristics of deposits from local depressions of the Derugin Basin. They were formed in an environment with periodic changes from oxic to anoxic conditions and show evidence for presence of hydrogen sulfide in bottom waters. Deposits of this type can be considered as a modern model for ancient ore-bearing black shale associations. Compared with typical metalliferous black shale sequences, which are characterized by high contents of organic matter, the sediments described here are depleted in elements of the organophilic association (Mo, Ni, Cu, Zn, V, and U), but have higher Mn contents.

Geochemistry on water profiles from the Kara Sea

As a part of the Russian-German project "Siberian River-Runoff (SIRRO)" the major element composition of the dissolved load and the major and trace element composition of particulate load and bottom sediment of the Yenisei River and Estuary were analyzed and examined in context of the basin lithology and climate. In addition, the processes controlling the transformation of the river load in the estuarine mixing zone were investigated. The chemical composition of the dissolved and particulate load of the Yenisei fluvial endmember is generally comparable to that of other major world rivers. The dissolved load is chiefly controlled by carbonate weathering and the chemical composition of the river suspended particulate matter (SPM) is similar to that of the North American Shale Composite (NASC), which represents the weathering product of the upper continental crust. The Chemical Index of Alteration (CIA) of the Yenisei SPM amounts to 71, which indicates moderate chemical weathering. With regard to the SPM geochemistry, the Yenisei occupies an intermediate position between the adjacent rivers Khatanga and the Lena. Drastic changes in the composition of the river load are seen in the mixing zone between fresh and salt water. While dissolved Na, Ca, Mg, K, CI, S04, F, Br, Sr and HC03 behave conservatively, dissolved Fe is completely removed from solution at very low salinities. Particulate Mn exhibits a pronounced mid-salinity minimum concomitant with a maximum of dissolved Mn, which is probably related to suboxic conditions in the area of the so-called "marginal filter", where highest turbidities are found. The Mn-minimum in SPM is paralleled by depletions of the elements Ba, Zn, Cd, Ni, Cu and V, which can be associated with manganese particles. The estuarine bottom sediments are composed of mud and sand and the sedimentological parameters of the bottom sediments have to be considered for the interpretation of the bulk geochemical data. The chemical composition of the mud is comparable to the SPM, whereas the sand is relatively enriched in Si/Al, Ba/Al, Zr/Al and Sr/Al ratios and depleted in transition metals.

Geochemistry of Mid-Atlantic Ridge sediments

Geochemical compositions and Sr and Nd isotopes were measured in two cores collected ~2 and 5 km from the Rainbow hydrothermal vent site on the Mid-Atlantic Ridge. Overall, the cores record enrichments in Fe and other metals from hydrothermal fallout, but sequential dissolution of the sediments allows discrimination between a leach phase (easily leachable) and a residue phase (refractory). The oxy-anion and transition metal distribution combined with rare earth element (REE) patterns suggest that (1) the leach fraction is a mixture of biogenic carbonate and hydrothermal Fe-Mn oxy-hydroxide with no significant contribution from detrital material and (2) >99.5% of the REE content of the leach fraction is of seawater origin. In addition, the leach fraction has an average 87Sr/86Sr ratio indistinguishable from modern seawater at 0.70916. Although we lack the epsilon-Nd value of present-day deep water at the Rainbow vent site, we believe that the REE budget of the leach fraction is predominantly of seawater origin. We suggest therefore that the leach fraction provides a record of local seawater epsilon-Nd values. Nd isotope data from these cores span the period of 4-14 ka (14C ages) and yield epsilon-Nd values for North East Atlantic Deep Water (NEADW) that are higher (-9.3 to -11.1) than those observed in the nearby Madeira Abyssal Plain from the same depth (-12.4 ± 0.9). This observation suggests that either the Iceland-Scotland Overflow Water (ISOW) and Lower Deep Water contributions to the formation of NEADW are higher along the Mid-Atlantic Ridge than in the surrounding basins or that the relative proportion of ISOW was higher during this period than is observed today. This study indicates that hydrothermal sediments have the potential to provide a higher-resolution record of deep water epsilon-Nd values, and hence deepwater circulation patterns in the oceans, than is possible from other types of sediments.