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.

Tie points and goechemical analysis from different Holes of ODP Site 165-1002

The fine-grained sediments of the Cariaco Basin, Venezuela, of the last 130 ky, whose deposition history is well characterized, were analyzed geochemically in order to test the validity of sediment bulk geochemistry as an indicator of detrital provenance. Several binary and ternary diagrams as well as the chemical index of alteration (CIA) were tested for their capacity to discriminate the poorly contrasted detrital sources to the Cariaco Basin, and to describe the temporal evolution of the contributions of these different sources. Most of the diagrams tested did not allow a good discrimination of sources or, when sources were well discriminated, did not allow an interpretation of the temporal variations consistent with the known history. A relatively good discrimination of sources and a consistent interpretation of temporal variations were however obtained using Hf vs. Th and La/Yb vs. Gd/Yb binary diagrams, as well as Ti-Zr-Th, Ti-Zr-La, and Lu-Hf-Th ternary diagrams. Compared to the previous studies of the detrital content of the Cariaco Basin sediments, the geochemical approach permitted the recognition of a sediment contribution eroded from the Unare platform and Gulf of Cariaco during rapid sea level oscillations, and the contribution of Saharan eolian particles during the Younger Dryas-Preboreal and MIS6-5 transition. The choice of plotted elements was determined after considering carrier minerals, so that different elements may be informative in different sedimentary contexts. Overall, mineral sorting during transport appears as a major limit to quantitative estimation of the different contributions. In particular mineral sorting leads to the selective enrichment of elements associated with clays (Al, Rb, Th and LREE) in sediments deposited in the basin. Unless the geochemical effect of mineral sorting can be measured, it appears that quantitative provenance analysis should be performed on fractions of similar grain size instead of bulk sediment.

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 tephra from the Taupo Volcanic Zone

The Taupo Volcanic Zone (TVZ), central North Island, New Zealand, is the most frequently active Quaternary rhyolitic system in the world. Silicic tephras recovered from Ocean Drilling Programme Site 1123 (41°47.16'S, 171°29.94'W; 3290 m water depth) in the southwest Pacific Ocean provide a well-dated record of explosive TVZ volcanism since ~1.65 Ma. We present major, minor and trace element data for 70 Quaternary tephra layers from Site 1123 determined by electron probe microanalysis (1314 analyses) and laser ablation inductively coupled plasma mass spectrometry (654 analyses). Trace element data allow for the discrimination of different tephras with similar major element chemistries and the establishment of isochronous tie-lines between three sediment cores (1123A, 1123B and 1123C) recovered from Site 1123. These tephra tie-lines are used to evaluate the stratigraphy and orbitally tuned stable isotope age model of the Site 1123 composite record. Trace element fingerprinting of tephras identifies ~4.5 m and ~7.9 m thick sections of repeated sediments in 1123A (49.0-53.5 mbsf [metres below seafloor]) and 1123C (48.1-56.0 mbsf), respectively. These previously unrecognised repeated sections have resulted in significant errors in the Site 1123 composite stratigraphy and age model for the interval 1.15-1.38 Ma and can explain the poor correspondence between d18O profiles for Site 1123 and Site 849 (equatorial Pacific) during this interval. The revised composite stratigraphy for Site 1123 shows that the 70 tephra layers, when correlated between cores, correspond to ~37-38 individual eruptive events (tephras), 7 of which can be correlated to onshore TVZ deposits. The frequency of large-volume TVZ-derived silicic eruptions, as recorded by the deposition of tephras at Site 1123, has not been uniform through time. Rather it has been typified by short periods (25-50 ka) of intense activity bracketed by longer periods (100-130 ka) of quiescence. The most active period (at least 1 event per 7 ka) occurred between ~1.53 and 1.66 Ma, corresponding to the first ~130 ka of TVZ rhyolitic magmatism. Since 1.2 Ma, ~80% of tephras preserved at Site 1123 and the more proximal Site 1124 were erupted and deposited during glacial periods. This feature may reflect either enhanced atmospheric transport of volcanic ash to these sites (up to 1000 km from source) during glacial conditions or, more speculatively, that these events are triggered by changes in crustal stress accumulation associated with large amplitude sea-level changes. Only 8 of the ~37-38 Site 1123 tephra units (~20%) can be found in all three cores, and 22 tephra units (~60%) are only present in one of the three cores. Whether a tephra is preserved in all three cores does not have any direct relationship to eruptive volume. Instead it is postulated that tephra preservation at Site 1123 is 'patchy' and influenced by the vigorous nature of their deposition to the deep ocean floor as vertical density currents. At this site, at least 5 cores would need to have been drilled within a proximity of 10's to 100's of metres of each other to yield a >99% chance of recovering all the silicic tephras deposited on the ocean surface above it in the past 1.65 Ma.

(Table 1) Redox potential and chemical element contents in CaCO3 and amorphous silica free matter in surface layer bottom sediments of the Pacific Ocean from Hawaiian Islands to Mexico coast

Distribution of Fe, Mn, P, Ti, Cu, Ni, Co, V, Cr, W, Mo, and As in the surface sediment layer on the section from the Hawaiian Islands to the coast of Mexico (Mexico section) is studied. Contents of all studied elements increase from biogenic-terrigenous sediments off the coast of Mexico to pelagic red clays of the Northeast Basin, and more sharply for mobile elements - Mn, Mo, Cu, Ni, Co, and As. In near Hawaii sediments rich in coarsely fragmented volcanic-terrigenous and pyroclastic material of basaltic composition with high contents of Ti, Fe, V, Cr, W, and P, contents of these elements increase sharply, and contents of Mn, Mo, Ni, Co, and Cu for the same reason decrease sharply in comparison with red clay. Abnormally high contents of Mn, Mo, Cu, Ni, Co, and As in the upper layer of hemipelagic and transition sediments of the Mexico section result from diagenetic redistribution and their accumulation on the surface. Processes of diagenetic redistribution in hemipelagic and transition sediment mass of the Mexico section are more rapid than in similar sediments of the Japan section due lower sedimentation rates and higher initial concentrations of Mn. Basic similarity of element distribution regularities in sediments of Japan and Mexico sections is shown.

Geochemistry of bulk sediment from the Cape Basin

A technique for onsite application of X-ray fluorescence (XRF) spectrometry to samples from sediment cores aboard a research vessel was developed and tested. The method is sufficiently simple, precise, and fast to be used routinely for high-resolution analyses of depth profiles as well as surface samples. Analyses were performed with the compact high-performance energy-dispersive polarisation X-ray fluorescence (EDPXRF) analyser Spectro Xepos. Contents of the elements Si, Ti, Al, Fe, Mn, Mg, Ca, K, Sr, Ba, Rb, Cu, Ni, Zn, P, S, Cl and Br were simultaneously determined on 200-225 samples of each core within 24 h of recovery. This study presents a description of the employed shipboard preparation and analysis technique, along with some example data. We show land-based datasets that support our decisions to use powder samples and to reduce the original measuring time for onboard analyses. We demonstrate how well the results from shipboard measurements for the various elements compare with the land-based findings. The onboard geochemical data enabled us to establish an element stratigraphy already during the cruise. Correlation of iron, calcium and silicon enrichment trends with an older reference core provided an age model for the newly retrieved cores. The Spectro Xepos instrument performed without any analytical and technical difficulties which could have been caused by rougher weather conditions or continuous movement and vibration of the research vessel. By now, this XRF technique has been applied during three RV Meteor cruises to approximately 5,000 Late Quaternary sediment samples from altogether 23 gravity cores, 25 multicorer cores and two box cores from the eastern South Atlantic off South Africa/Namibia and the eastern Atlantic off NW Africa.