Grain-size and bulk and clay mineralogy of ODP Leg 204 sediments

We present grain size, granulometric statistical parameters, and calcium carbonate content of sediment samples from the summit and east and west flanks of southern Hydrate Ridge (Sites 1244-1250). These data are compared with magnetic susceptibility measurements from the same intervals. Bulk and clay mineralogy from Sites 1244 (east flank), 1247 (west flank), and 1250 (summit) are also presented. The integration of these data allows us to characterize the main sedimentary facies and composition of the Quaternary age sediments from southern Hydrate Ridge.

Mineral composition and geochemistry of sediments from ODP Leg 127 sites

The lithostratigraphy of Neogene hemipelagic sediments recovered from the Japan Sea during Leg 127 was revised to improve intersite consistency and to remove confusion stemming from diagenetic modification of the lithology through the opal-A to opal-CT transformation. Special emphasis was put on the presence and nature of dark-light cycles in revising the lithostratigraphy. Mineral composition analysis was conducted for samples from Sites 794, 795, and 797. In addition, major element chemical composition analysis was conducted for these same sample sets from Site 794. The result of mineral composition analysis suggests that the detrital component, which consists of such minerals as quartz, plagioclase, illite, and kaolinite plus chlorite, is diluted to various degrees by biogenic silica (opal-A) and its diagenetic equivalents (opal-CT and quartz). Smectite, on the other hand, may be a diagenetic or hydrothermal alteration product of volcanic material, although more study is necessary to confirm its origin. As a whole, vertical variation in the sediment composition is consistent with the revised lithostratigraphy and helps to characterize the redefined lithologic units quantitatively.

Composition of sediments from the north-west African continental margin

Entlang dreier Profile vom NW-afrikanischen Kontinentalrand wurden Oberflächensedimente aus Wassertiefen zwischen 39m und 1514m auf ihre Zusammensetzung der Sandfraktion, auf ihre Gehalte an Karbonat und organischer Substanzen sowie auf ihre mineralogische Zusammensetzung hin untersucht. 1) Die auf dem Schelf und dem oberen Hang abgelagerten Sedimente (<500m) zeichnen sich durch hohe Sandgehalte (>70%) und durch hohe Grob/Fein-Verhältnisse aus. Unterhalb dieses Bereiches nimmt der Einfluß von Strömungen, die die Ablagerung von wesentlichen Mengen an Feinmaterial oberhalb 500m verhindern, ab, wie die starke Abnahme des Sandgehaltes, des Quarz/Glimmer und des Grob/Fein-Verhältnisses zeigen. Die Sedimente aus diesen Wassertiefen werden zum großen Teil aus Partikeln der Siltfraktion aufgebaut. Mit zunehmender Tiefe ist auch eine Zunahme der Tonfraktion zu beobachten, wobei höhere Tonanteile (>10%) erst in Tiefen unterhalb von 1200m auftreten. 2) Die quantitative Komponentenanalyse der Sandfraktion zeigt, daß der karbonatische Anteil fast ausschließlich biogener Herkunft ist. Er besteht zum wesentlichen Teil aus planktonischen Komponenten, vorwiegend Foraminiferen und mengenmäßig nur sehr untergeordnet auftretenden Pteropoden. Das opalkieselige Plankton (Diatomeen, Radiolarien) ist nur in geringen Mengen in den untersuchten Proben vorhanden. Auch das Benthos stellt nur eine untergeordnete Komponente der Sandfraktion dar. Vor allem der Anteil von Foraminiferen und Mollusken nimmt mit zunehmender Wassertiefe relativ deutlich ab. Die übrigen benthonischen Komponenten sind im Sediment nur in geringen Anteilen vertreten. 3) Hauptsedimentbildner im Profil Nouakchott sind die nichtbiogenen, terrigen-detritischen Sandkomponenten. Sie bestehen vorwiegend aus Quarz und mit zunehmender Wassertiefe aus Kotpillen bzw. Kotpillenaggregaten. Je nach Tiefe treten vor allem Glimmer (>1000m) und Glaukonit (<800m) hinzu. Die restlichen Komponenten treten nur gelegentlich und in äußerst geringen Mengen im rezenten Oberflächensediment auf. 4) Quarz wird als Windstaub mit dem NE-Passat und vor allem durch den "Harmattan" aus der Sahara heraustransportiert und vorwiegend über dem Schelfbereich sedimentiert. Windstaubmaterial besteht primär weitgehend aus Siltkorngrößen, die vor Nouakchott über die Schelfkante hinaustransportiert werden und zu einer Grobsiltanreicherung am mittleren Hang führen. 5) Das Verhältnis zwischen den karbonatischen Biogenkomponenten und den nichtbiogenen Partikeln spiegelt sich deutlich in der Karbonatverteilung sowohl des Gesamtsedimentes als auch der Sandfraktion wider. Relativ hohe Karbonatgehalte vor Cap Leven im Norden stehen sehr geringen Anteilen von Nouakchott gegenüber. Mit zunehmender Wassertiefe ist eine deutliche Abnahme des Karbonatanteils zu verfolgen. 6) Die Tatsache, daß das Profil Cap Blanc im Bereich des ganzjährigen Auftriebs liegt, spiegelt sich nicht in der Zusammensetzung der Sandfraktion wider. Südlich der Zone des ganzjährigen Auftriebs weisen verschiedene Parameter (Radiolarien, Diatomeen, Verhältnis von Radiolarien zu planktonischen Foraminiferen, Benthos/Plankton-Verhältnis der Foraminiferen) trotz abnehmender Auftriebsintensität eher steigende Werte auf. Dies ist wesentlich auf eine infolge des Nährstoffeintrages durch Flußzufuhr bedingte Verschiebung der maximalen Primärproduktion weit in südliche Richtung zurückzuführen. 7) In den aufgeführten Parametern zeigen sich von Profil zu Profil sehr deutliche fazielle Unterschiede, obwohl der großklimatische Hintergrund im gesamten Untersuchungsgebiet etwa gleich ist. Vor Cap Leven bildet sich eine Fazies, die im wesentlichen aus planktonischen Foraminiferen besteht, während das Sediment vor Nouakchott zum überwiegenden Teil aus nichtbiogenen Komponenten aufgebaut wird. Im Übergangsbereich vor Cap Blanc bildet sich eine Mischfazies, die keinerlei Prägung durch das Auftriebsgeschehen erhält. Die Ursachen dieser faziellen Unterschiede werden auf fehlenden Terrigeneinfluß vor Cap Leven einerseits und hohe Terrigenanlieferung vor Nouakchott andererseits zurückgeführt. 8) Die Zusammensetzung und Verteilung der rezenten Grobfraktionssedimente am Kontinentalrand vor Nw-Afrika wird somit im wesentlichen als Ergebnis einer Überprägung der Biogenanlieferung durch nichtbiogene Komponenten angesehen. Wesentlicher steuernder Faktor ist demnach das hier vorherrschende Windsystem.

Iron and phosphorus speciations in DSDP Leg 92 sediments

We present a detailed study of the co-diagenesis of Fe and P in hydrothermal plume fallout sediments from ~19°S on the southern East Pacific Rise. Three distal sediment cores from 340-1130 km from the ridge crest, collected during DSDP Leg 92, were analysed for solid phase Fe and P associations using sequential chemical extraction techniques. The sediments at all sites are enriched in hydrothermal Fe (oxyhydr)oxides, but during diagenesis a large proportion of the primary ferrihydrite precipitates are transformed to the more stable mineral form of goethite and to a lesser extent to clay minerals, resulting in the release to solution of scavenged P. However, a significant proportion of this P is retained within the sediment, by incorporation into secondary goethite, by precipitation as authigenic apatite, and by readsorption to Fe (oxyhydr)oxides. Molar P/Fe ratios for these sediments are significantly lower than those measured in plume particles from more northern localities along the southern East Pacific Rise, and show a distinct downcore decrease to a depth of ~12 m. Molar P/Fe ratios are then relatively constant to a depth of ~35 m. The Fe and P speciation data indicate that diagenetic modification of the sediments is largely complete by a depth of 2.5 m, and thus depth trends in molar P/Fe ratios can not solely be explained by losses of P from the sediment by diffusion to the overlying water column during early diagenesis. Instead, these sediments are likely recording changes in dissolved P concentrations off the SEPR, possibly as a result of redistribution of nutrients in response to changes in oceanic circulation over the last 10 million years. Furthermore, the relatively low molar P/Fe ratios observed throughout these sediments are not necessarily solely due to losses of scavenged P by diffusion to the overlying water column during diagenesis, but may also reflect post-depositional oxidation of pyrite originating from the volatile-rich vents of the southern East Pacific Rise. This study suggests that the molar P/Fe ratio of oxic Fe-rich sediments may serve as a proxy of relative changes in paleoseawater phosphate concentrations, particularly if Fe sulfide minerals are not an important component during transport and deposition.

Chemical composition of Fe-Mn nodules and host bottom sediments along the submeridional profile across the Brazil Basin

Sedimentation and ore formation were studied in sediments from nine stations located along the 24°W profile in the Brazil Basin of the Atlantic Ocean. Bottom sediments are represented by mio- and hemipelagic muds, which are variably enriched in hydrothermal iron and manganese oxyhydroxides. As compared to bottom sediments from other basins of the Atlantic Ocean, the sediments in study are marked by extremely high manganese contents (up to 1.33%) and maximal enrichment in Ce. It was shown that the positive Ce anomaly is related to REE accumulation on iron oxyhydroxides. Influence of hydrothermal source leads to decrease of Ce anomaly and LREE/HREE ratio. In reduced sediments preservation of positive Ce anomaly and/or its disappearance was observed after iron and manganese reduction. REE contents were determined for the first time in the Ethmodiscus oozes of the Brazil Basin. Ore deposits of the Brazil Basin are represented by ferromanganese crusts and ferromanganese nodules. Judging from contents of iron, manganese, REE, and other trace elements, these formations are ascribed to sedimentation (hydrogenic) deposits. They are characterized by a notable positive Ce anomaly in the REE pattern. Extremely high Ce content (up to 96% of total REE) was discovered for the first time in the buried nodules (Mn/Fe = 0.88).

Magnetic susceptibility stratigraphy for Pleistocene and Pliocene sediments of ODP Leg 110 samples

Whole-core magnetic susceptibility measurements define a detailed stratigraphy that enables correlation between the various Pleistocene, Pliocene, and upper Miocene sections cored on ODP Leg 110, near the Tiburon Rise. The magnetic susceptibility in these sections is primarily related to the content of volcanic ash, rich in titanomagnetite, and also inversely related to calcium carbonate content. The high resolution of the susceptibility record enables correlations with a resolution of about 0.3 m of sediment thickness, and the identification of minor faults not definable by biostratigraphic means. Reverse and normal faults identified in Hole 672A are probably a result of normal oceanic sediment dewatering and compaction processes. This work indicates some of the problems of using visible ash layers as time-stratigraphic markers.

Geochemistry of pelagic and hemipelagic sediments of ODP Leg 126 sites

Chemical analyses were performed on major, minor, and rare-earth elements of pelagic and hemipelagic sediments of the forearc, arc, and backarc sites of the Izu-Bonin Arc, Ocean Drilling Program Leg 126. Analyses of the hemipelagic and pelagic sediments of this area indicate that the chemical composition of this arc is highly affected by the chemical composition of rocks of this arc as a source of sediments. The Oligocene sediments, which are characterized by high MgO contents, reflect the chemical composition of the Paleogene volcanic rocks of the immature arc. Moreover, the late Miocene to Quaternary sediments with low MgO contents are attributed to the composition of the present arc. We also suggest that the sedimentation rates and topography of the sedimentary basin affect the MnO and SiO2 contents of pelagic and hemipelagic sediments.

Carbonate and barite content accross the Eocene/Oligocene boundary of ODP Leg 198 sites, Shatsky Rise

The barite and CaCO3 content (in weight percent) of marine sediments can be used to determine spatial and temporal changes in export production (organic and carbonate carbon flux) and/or CaCO3 preservation (inorganic carbon burial). Here we report barite and CaCO3 content in Eocene/Oligocene (E/O) boundary sediments from locations drilled on Shatsky Rise during Ocean Drilling Program Leg 198. Records of these indexes may be used along with other data to determine how the major E/O boundary climatic transition (initiation of Antarctic glaciation and resultant ocean-climate system changes) affected marine export production/preservation at Shatsky Rise. Such data are necessary to elucidate the timing and phasing of changes in the carbon cycle relative to fluctuations in oceanographic conditions across this climatically important interval.

Concentrations and isotopic ratios of thorium and uranium in pelagic sediments

The predictable in situ production of 230Th from the decay of uranium in seawater, and its subsequent removal by scavenging onto falling particles, provides a valuable tool for normalizing fluxes to the seafloor. We describe a new application, determination of the 232Th that dissolves in the water column and is removed to the seafloor. 232Th is supplied to the ocean in continental minerals, dissolution of which leads to a measurable standing stock in the water column. Sedimentary adsorbed 232Th/230Th ratios have the potential to provide a proxy for estimating the amount of dissolved material that enters the ocean, both today and in the past. Ten core top samples were treated with up to eight different leaching techniques in order to determine the best method for the separating adsorbed from lattice bound thorium. In addition, separate components of the sediments were analyzed to test whether clay dissolution was an important contribution to the final measurement. There was no systematic correlation between the strength of acid used in the leach and the measured 232Th/230Th ratios. In all cases clean foraminifera produced the same ratio as leaches on bulk sediment. In three out of five samples leaches performed on non-carbonate detritus in the <63 µm size fraction were also identical. Without additional water column data it is not yet clear whether there is a simple one to one correlation between the expected deep-water 232Th/230Th and that produced by leaching, especially in carbonate-rich sediments. However, higher ratios, and associated high 232Th adsorbed fluxes, were observed in areas with high expected detrital inputs. The adsorbed fraction was ~35-50% of the total 232Th in seven out of ten samples. Our 230Th normalized 232Th fluxes are reasonable by comparison to global estimates of detrital inputs to the ocean. In nine cases out of ten, the total 230Th-normalized 232Th flux is greater than predicted from the annual dust fall at each specific location, but lower than the average global detrital input from all sources.

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.

Chemistry of siliciclastic and volcanoclastic sediments of DSDP Site 47-397

The Lower Cretaceous and Miocene sequences of the NW African passive continental margin consist of siliciclastic, volcaniclastic and hybrid sediments. These sediments contain a variety of diagenetic carbonates associated with zeolites, smectite clays and pyrite, reflecting the detrital mineralogical composition and conditions which prevailed during opening of the North Atlantic. In the Lower Cretaceous siliciclastic sediments, siderite (-6 per mil to +0.7per mil d18O PDB, -19.6 per mil to +0.6 per mil d13C PDB) was precipitated as thin layers and nodules from modified marine porewaters with input of dissolved carbon from the alteration of organic matter. Microcrystalline dolomite layers, lenses, nodules and disseminated crystals (-3.0 per mil to +2.5 per mil d18O PDB, -7.2 per mil to +4.9 per mil d13C PDB) predominate in slump and debris-flow deposits within the Lower Miocene sequence. During the opening of the Atlantic, volcanic activity in the Canary Islands area resulted in input of volcaniclastic sediments to the Middle and Upper Miocene sequences. Calcite is the dominant diagenetic carbonate in the siliciclastic-bioclastic-volcaniclastic hybrid and in the volcaniclastic sediments, which commonly contain pore-rimming smectite. Diagenetic calcite (-22 per mil to +1.6 per mil d18O PDB, -35.7 per mil to +0.8 per mil d13C PDB) was precipitated due to the interaction of volcaniclastic and bioclastic grains with marine porewaters. Phillipsite is confined to the alteration of volcaniclastic sediments, whereas clinoptilolite is widely disseminated, occurring essentially within foraminiferal chambers, and formed due to the dissolution of biogenic silica.

Geochemistry of Lesser Antilles forearc sediments

Oceanic sediments contain the products of erosion of continental crust, biologic activity and chemical precipitation. These processes create a large diversity of their chemical and isotopic compositions. Here we focus on the influence of the distance from a continental platform on the trace element and isotopic compositions of sediments deposited on the ocean floor and highlight the role of zircons in decoupling high-field strength elements and Hf isotopic compositions from other trace elements and Nd isotopic compositions. We report major and trace element concentrations as well as Sr and Hf isotopic data for 80 sediments from the Lesser Antilles forearc region. The trace-element characteristics and the Sr and Hf isotopic compositions are generally dominated by detrital material from the continental crust but are also variably influenced by chemical or biogenic carbonate and pure biogenic silica. Next to the South American continent, at DSDP Site 144 and on Barbados Island, sediments, coarse quartz arenites, exhibit marked Zr and Hf excesses that we attribute to the presence of zircon. In contrast, the sediments from DSDP Site 543, which were deposited farther away from the continental platform, consist of fine clay and they show strong deficiencies in Zr and Hf. The enrichment or depletion of Zr-Hf is coupled to large changes in Hf isotopic compositions (-30 < epsilon-Hf < +4) that vary independently from the Nd isotopes. We interpret this feature as a clear expression of the "zircon effect" suggested by Patchett and coauthors in 1984. Zircon-rich sediments deposited next to the South American continent have very low epsilon-Hf values inherited from old zircons. In contrast, in detrital clay-rich sediments deposited a few hundred kilometers farther north, the mineral fraction is devoid of zircon and they have drastically higher epsilon-Hf values inherited from finer, clay-rich continental material. In the two DSDP sites, average Hf isotopes are very unradiogenic relative to other oceanic sediments worldwide (epsilon-Hf = -14.4 and -7.4) and they define the low Hf end member of the sedimentary field in Hf-Nd space. Their compositions correspond to end members that, when mixed with mantle, are able to reproduce the pattern of volcanic rocks from the Lesser Antilles. More generally, we find a relationship between Nb/Zr ratios and the vertical deviation of Hf isotope ratios from the Nd-Hf terrestrial array and we suggest that this relationship can be used as a tool to distinguish sediment input from fractionation during melting during the formation of arc lavas.

Mg/Ca and Sr/Ca ratios of Hoeglundina elegans from surface sediments

Core top samples from Atlantic (Little Bahama Banks (LBB)) and Pacific (Hawaii and Indonesia) depth transects have been analyzed in order to assess the influence of bottom water temperature (BWT) and aragonite saturation levels on Mg/Ca and Sr/Ca ratios in the aragonitic benthic foraminifer Hoeglundina elegans. Both the Mg/Ca and Sr/Ca ratios in H. elegans tests show a general decrease with increasing water depth. Although at each site the decreasing trends are consistent with the in situ temperature profile, Mg/Ca and Sr/Ca ratios in LBB are substantially higher than in Indonesia and Hawaii at comparable water depths with a greater difference observed with increasing water depth. Because we find no significant difference between results obtained on "live" and "dead" specimens, we propose that these differences are due to primary effects on the metal uptake during test formation. Evaluation of the water column properties at each site suggests that in situ CO3 ion concentrations play an important role in determining the H. elegans Mg/Ca and Sr/Ca ratios. The CO3 ion effect is limited, however, only to aragonite saturation levels ([DeltaCO3]aragonite) below 15 µmol/kg. Above this level, temperature exerts a dominant effect. Accordingly, we propose that Mg/Ca and Sr/Ca in H. elegans tests can be used to reconstruct thermocline temperatures only in waters oversaturated with respect to the mineral aragonite using the following relationships: Mg/Ca = (0.034 ± 0.002)BWT + (0.96 ± 0.03) and Sr/Ca = (0.060 ± 0.002)BWT + (1.53 ± 0.03) (for [DeltaCO3]aragonite > 15 µmol/kg). The standard error associated with these equations is about ±1.1°C. Reconstruction of deeper water temperatures is complicated because in undersaturated waters, changes in Mg/Ca and Sr/Ca ratios reflect a combination of changes in [CO3] and BWT. Overall, we find that Sr/Ca, rather than Mg/Ca, in H. elegans may be a more accurate proxy for reconstructing paleotemperatures.

Chemical and amino acid compositions of bottom sediments from the Canary upwelling

Amino acid composition of bottom sediments on the northwestern continental slope of Africa is determined. Correlation similar to that found earlier in Caspian sediments between type of amino acid spectra of Atlantic sediments and distribution of reduced forms of sulfur in them is found. These correlations result from geochemical activity of benthic biocoenosis, which transforms sulfur compounds.