Solid phase phosphorus geochemistry in surface sediments of sediment cores GeoB3718-4, GeoB3702-2 and GeoB3707-4

In this study we investigate benthic phosphorus cycling in recent continental margin sediments at three sites off the Namibian coastal upwelling area. Examination of the sediments reveals that organic and biogenic phosphorus are the major P-containing phases preserved. High Corg/Porg ratios just at the sediment surface suggest that the preferential regeneration of phosphorus relative to that of organic carbon has either already occurred on the suspension load or that the organic matter deposited at these sites is already rather refractory. Release of phosphate in the course of benthic microbial organic matter degradation cannot be identified as the dominating process within the observed internal benthic phosphorus cycle. Dissolved phosphate and iron in the pore water are closely coupled, showing high concentrations below the oxygenated surface layer of the sediments and low concentrations at the sediment-water interface. The abundant presence of Fe(III)-bound phosphorus in the sediments document the co-precipitation of both constituents as P-containing iron (oxyhydr)oxides. However, highly dissolved phosphate concentrations in pore waters cannot be explained, neither by simple mass balance calculations nor by the application of an established computer model. Under the assumption of steady state conditions, phosphate release rates are too high as to be balanced with a solid phase reservoir. This discrepancy points to an apparent lack of solid phase phosphorus at sediment depth were suboxic conditions prevail. We assume that the known, active, fast and episodic particle mixing by burrowing macrobenthic organisms could repeatedly provide the microbially catalyzed processes of iron reduction with authigenic iron (oxyhydro)oxides from the oxic surface sediments. Accordingly, a multiple internal cycling of phosphate and iron would result before both elements are buried below the iron reduction zone.

Geochemistry of continental slope and deep sea basin sediments off Uruguay

Pore water and solid phase from surface sediments of the continental slope off Uruguay and from the Argentine Basin (southwestern Atlantic) were investigated geochemically to ascribe characteristic early diagenetic reactions of iron and manganese. Solid-phase iron speciation was determined by extractions as well as by Mössbauer spectroscopy. Both methods showed good agreement (<6% deviation) for total-Fe speciation. The proportion of easy reducible iron oxyhydroxide relative to total-Fe oxides decreased from the continental slope to the deep sea which is attributed to an increase in crystallinity during transport as well as to a general decrease of iron mobilization. The product of iron reoxidation is Fe oxyhydroxide which made up less than 5% of total Fe. In addition to this fraction, a proportion of smectite bound iron was found to be redox reactive. This fraction made up to 10% of total Fe in sediments of the Argentine Basin and was quantitatively extracted by 1 N HCl. The redox reactive Fe(+II) fraction of smectite was almost completely reoxidized within 24 h under air atmosphere and may therefore considerably contribute to iron redox cycling if bioturbation occurs. In the case of the slope sediments we found concurrent iron and manganese release to pore water. It is not clear whether this is caused by dissimilatory iron and manganese reduction at the same depth or dissimilatory iron reduction alone inducing Mn(+IV) reduction by (abiotic) reaction with released Fe2+. The Argentine Basin sediment showed a significant manganese solid-phase enrichment above the denitrification depth despite the absence of a distinct pore-water gradient of Mn. This implies a recent termination of manganese mobilization and thus a non-steady-state situation with respect to sedimentation or to organic carbon burial rate.

Geochemistry from the S1 tephra of core GeoTü SL112 and samples from Erciyes Dag eruptions Dikkartin, Karagüllü and Perikartin

A hitherto unknown distal volcanic ash layer has been detected in a sediment core recovered from the southeastern Levantine Sea (Eastern Mediterranean Sea). Radiometric, stratigraphical and sedimentological data show that the tephra, here termed as S1 tephra, was deposited between 8,970 and 8,690 cal yr BP. The high-silica rhyolitic composition excludes an origin from any known eruptions of the Italian, Aegean or Arabian volcanic provinces but suggests a prevailing Central Anatolian provenance. We compare the S1 tephra with proximal to medial-distal tephra deposits from well-known Mediterranean ash layers and ash fall deposits from the Central Anatolian volcanic field using electron probe microanalyses on volcanic glass shards and morphological analyses on ash particles. We postulate a correlation with the Early Holocene 'Dikkartin' dome eruption of Erciyes Dag volcano (Cappadocia, Turkey). So far, no tephra of the Central Anatolian volcanic province has been detected in marine sediment archives in the Eastern Mediterranean region. The occurrence of the S1 tephra in the south-eastern part of the Levantine Sea indicates a wide dispersal of pyroclastic material from Erciyes Dag more than 600 km to the south and is therefore an important tephrostratigraphical marker in sediments of the easternmost Mediterranean Sea and the adjacent hinterland.

Geochemistry of ODP Site 125-786 volcanic rocks

Eocene-Oligocene volcanic rocks drilled at Site 786 in the Izu-Bonin forearc cover a wide range of compositions from primitive boninites to highly evolved rhyolites. K-Ar dating reveals at least two distinct episodes of magmatism; one at 41 Ma and a later one at 35 Ma. The early episode produced low-Ca boninites and bronzite andesites that form an oceanic basement of pillow lavas and composite intrusive sheets, overlain by flows and intrusive sheets of intermediate-Ca boninites and bronzite-andesites and a fractionated series of andesites, dacites, and rhyolites. The later episode produced high-Ca boninites and intermediate-Ca boninites, exclusively as intrusive sheets.

Mineralogy and geochemistry at DSDP Leg 80 Holes

Cenozoic sediments recovered from Sites 548, 549, and 550 were the objects of mineralogical (bulk sample and <2 - µm fraction) and geochemical (HCl extract) studies. Thin sections of rock pebbles embedded in sediments (upper levels at Site 548, particularly) were examined on a polarizing microscope. This study outlines the vertical and lateral variation and evolution of the sedimentation. In the Paleocene and lower Eocene, the clay fraction is abundant and smectite is practically the sole existing clay mineral. High Mn, Al, Fe, Mg, and K contents were measured in HCl extracts. Through the middle Eocene, carbonates become more abundant - highly dominant at Site 548. Metal contents in HCl extracts are very low. The clay fraction, although dominated at all sites by smectites, becomes richer in illite and poorly crystallized chlorite. At the middle/upper Miocene boundary, a significant decrease in the smectite/(illite + chlorite) ratio occurs at all sites, and this decrease continues into the middle Pliocene. This decrease is marked by an abrupt increase of quartz at Site 548. At the two other sites, carbonates remain highly predominant; HCl extracts reflect the relative abundance of the clay and carbonate fractions. After a brief recurrence of smectite in a high-metal-content interval, illite and chlorite become the dominant clay minerals in the upper Pliocene and the Pleistocene, where numerous variations in mineralogical composition occur in the clay fraction (Sites 548 and 549) or in non-clay components (Site 548). Several pebbles of various nature and origin, encountered in different levels of this interval at Site 548, appear to have an ice-rafting origin. This study points out three main breaks in the general evolution of the sedimentation: the first, corresponding to the lower/middle Eocene boundary, is marked by the increase of carbonates and associated elements; the second, corresponding to the middle/upper Miocene boundary, is marked by a major decrease of the smectite/(illite + chlorite) ratio at all sites and by a massive appearance of quartz at Site 548; and the third, which occurred toward the late Pliocene, is marked by the dominance of primary clay minerals and the arrival of ice-rafted pebbles. Our interpretation of results considers paleohydrological and paleoclimatic phenomena. It is suggested that the major middle/late Miocene break was associated with an increase of the deep bottom-water circulation between the Norwegian Sea and the North Atlantic Ocean, and/or a climatic evolution: humidification and cooling of climate. The changes toward the late Pliocene appear to have been the first effects of the glaciations at the end of Cenozoic.

Geochemistry of ODP Sites 121-758 and 121-757

Nd isotopes are useful tracers for paleoceanography due to the short Nd residence time in seawater and the large differences between the isotopic signatures of various geological reservoirs. Therefore, ?Nd variations reflect the geological history of individual oceanic basins. Using a differential dissolution technique, which extracts Nd isotopes of seawater trapped in MnO2 coatings and carbonates in marine sediment, we measured almost two hundred samples from ODP Sites 758 and 757 in the Northern Bay of Bengal covering the last 4 Ma. For the first time, we have shown a covariation between epsilon-Nd and d18O over at least the last 800 ka. We also show that from 4 Ma to 2.6 Ma, epsilon-Nd is almost constant and starts to fluctuate at 2.6 Ma when northern glaciations increased. From 2.6 Ma to 1 Ma the fluctuation period is close to 40 ka while from 1 Ma to present it is dominantly 100 ka. We attribute these findings to mixing between Himalayan river water (that ultimately originates as Indian summer monsoon rain) and normal Bay of Bengal seawater. Previous studies on seawater, using epsilon-Nd, d18O analyzed on planktonic foraminifera and sedimentary data, can be integrated into this model. A simple quantitative binary mixing model suggests that the summer monsoon rain was more intense during interglacial than glacial periods. During last glacial episode, the monsoon trajectory was deviated to the east. At a large scale, the Indian monsoon is fully controlled by the variations in Northern Hemisphere climate but with a complex response function to this forcing. Our study clearly establishes the large potential of Nd isotope data to evaluate the hydrological river regime during the Quaternary and its relationship with climate fluctuations, particularly when the sediment archive is sampled close to sediment sources.

Mineralogy and geochemistry of alteration products in DSDP Leg 81 Holes

Alteration products of basalts from the four holes drilled during Leg 81 were studied and found to be characterized by the widespread occurrence of trioctahedral clay minerals (Mg smectite to chlorite). In some cases zeolites (analcite, chabazite) are associated with the saponite. A more oxidizing stage is marked by a saponite-celadonite association, presenting the geochemical characteristics of hydrothermal processes. Later stages of alteration are represented by palagonitization and subaerial weathering at two sites. These different alteration processes of basalts from Leg 81 record the paleoenvironment during the first opening stages of the Northeast Atlantic Ocean in the Paleocene-Eocene periods.

Correlation of Bolboforma zonation and nannoplankton stratigraphy in the Neogene of the North Atlantic

The Neogene Bolboforma zones established in the North Atlantic have been correlated with the calcareous nannoplankton stratigraphy obtained by investigation of the same samples from DSDP Sites 12-116 (44 samples), 49-408 (76 samples), 81-555 (43 samples) and 94-608 (103 samples). The absolute ages for the zonal boundaries were determined by the paleomagnetic record of Site 94-608. This correlation and the age determinations are additional useful tools to develop a precise biostratigraphy of Neogene sediments in the Northern Atlantic.

Geochemistry of FeMn oxyhydroxides of IODP Site 303-U1302 and 303-1303

Regional weathering intensity must have changed dramatically at high latitudes during the Quaternary as a consequence of repeated continental glaciation. Investigation of these glacial/interglacial changes at high temporal resolution is possible with the recent development of Pb isotopes in FeMn oxyhydroxide phases as a proxy for region-specific weathering intensity, where increases in the radiogenic component are thought to correspond to increased continental weathering fluxes. Here we present a Pb isotope record sourced from the FeMn oxyhydroxide fraction in marine sediments from IODP Sites U1302/3 on Orphan Knoll (~3500 mbsl, NW Atlantic), spanning the last 37 ka. Located at the eastern edge of the Laurentide Ice Sheet (LIS), Site U1302/3 is well-placed to monitor changes in weathering intensity associated with LIS glacial history. Overall, the data show a close correspondence to local surface water d18O, with least radiogenic values during times of heavy d18O (glacial maximum) and most radiogenic values during times of light d18O (Holocene). This supports the prediction that weathering intensity in glaciated regions of the North Atlantic correlates with the exposure age of glacial debris. Superimposed on these background trends are extreme radiogenic excursions (e.g. variation in 206Pb/204Pb from ~19.2-21.0) contemporaneous with Heinrich events and the Younger Dryas. These data are substantially more radiogenic than existing records from the NW Atlantic, and most likely represent episodes of exceptionally high inputs of pre-formed FeMn oxyhydroxides during drainage of the LIS. Due to its extreme isotope composition, at least in the NW Atlantic region, Pb would appear to be a good proxy for the fluxes of weathered continental material and perhaps, by inference, nutrients to the surface ocean

Organic geochemistry of ODP Leg 104 holes

The Leg 104 organic geochemistry program consisted of monitoring (a) hydrocarbon gases, (b) organic and inorganic carbon, and (c) parameters resulting from Rock-Eval pyrolysis at three sites on the Voring Plateau. The results amplify some of those obtained earlier on Deep Sea Drilling Project (DSDP) Leg 38. In a regional sense there is an inverse correlation between amounts of hydrocarbon gas and organic carbon. For example, significant concentrations of methane are present only at Site 644 in the inner part of the plateau where organic carbon contents are always less than 1%; in contrast, at Site 642 on the outer plateau, methane concentrations are very low (ppm range) whereas amounts of organic carbon approach 2%. Only at Site 644 are the environmental conditions such that methanogenesis is an active diagenetic process. Because of the importance of routine gas analyses to the Ocean Drilling Program (ODP), a procedure was devised to improve the use of Vacutainers for collection of gas samples. Comparison of methods for determining organic carbon showed that at Sites 643 and 644 Rock-Eval TOC could be used as a measure of organic carbon, but not at Site 642. Although no liquid or solid hydrocarbons were encountered at any of the sites, a catalog of potential organic geochemical contaminants was developed in anticipation of such a discovery.

Geochemistry, trace elements and minerals at DSDP Holes 80-550B and 80-551

The Leg 80 basalts drilled on the Porcupine Abyssal Plain 10 km southwest of Goban Spur (Hole 550B) and on the western edge of Goban Spur (Hole 551), respectively, are typical light-rare-earth-element- (LREE-) depleted oceanic tholeiites. The basalts from the two holes are almost identical; most of their primary geochemical and mineralogical characteristics have been preserved, but they have undergone some low-temperature alteration by seawater, such as enrichment in K, Rb, and Cs and development of secondary potassic minerals of the "brownstone facies." K/Ar dating fail to give realistic emplacement ages; the apparent ages obtained become younger with alteration (causing an increase in K2O). Hole 551 basalts are clearly different from the continental tholeiites emplaced on the margins of oceanizing domains during the prerift and synrift stages.

Composition of carbonaceous sediments from the Late Jurassic Volgian Basin of the East European Platform (Kostroma Region, Russia)

Lithological, geochemical, stratigraphic, and paleoecological features of carbonaceous sediments in the Late Jurassic Volgian Basin of the East European Platform (Kostroma Region) are considered. The shale-bearing sequence studied is characterized by greater sedimentological completeness as compared with its stratotype sections in the Middle Volga region (Gorodishche, Kashpir). Stratigraphic position and stratigraphy of the shale-bearing sequence, as well as distribution of biota in different sedimentation settings are specified. It is shown that Volgian sediments show distinct cyclic structure. The lower and upper elements of cyclites consist of high-carbonaceous shales and clayey-calcareous sediments, respectively, separated by transitional varieties. Bioturbation structures in different rocks are discussed. Microcomponent composition and pyrolytic parameters of organic matter, as well as distribution of chemical elements in lithologically variable sediments are analyzed. Possible reasons responsible for appearance of cyclicity and accumulation of organic-rich sediments are discussed.

Geochemistry and trace elements at DSDP Hole 78-543A

The upper part of the basaltic substratum of the Atlantic abyssal plain, approaching subduction beneath the Barbados Ridge and thus presumably beneath the Lesser Antilles island arc, is made of typical LREE-depleted oceanic tholeiites. Mineralogical (microprobe) and geochemical (X-ray fluorescence, neutron activation analyses) data are given for 12 samples from the bottom of Hole 543A, which is 3.5 km seaward of the deformation front of the Barbados Ridge complex. These basalts are overlain by a Quaternary to Maestrichtian-Campanian sedimentary sequence. Most of the basalts are relatively fresh (in spite of the alteration of olivine and development of some celadonite, clays, and chlorite in their groundmass), and their mineralogical and geochemical compositions are similar to those of LREE-depleted recent basalts from the Mid-Atlantic Ridge. The most altered samples occur at the top of the basaltic sequence, and show trends of enrichment in alkali metals typical of altered oceanic tholeiites.