(Table 2) Grain composition of sediments from ODP Hole 161-974B and from beach samples

Miocene to Pleistocene sand and sandstone were recovered at Ocean Drilling Program Site 974 in the Tyrrhenian Basin and Sites 976 and 977 in the Alboran Basin. Sand detrital modes were determined for 45 samples from these sites, as well as 10 samples of Spanish beach sand. At Site 974, the Pleistocene section includes a number of volcaniclastic (vitric ash) and terrigenous sand layers; the latter are heterogeneous and contain sedimentary and metamorphic lithic fragments. Submarine canyon and onshore drainage patterns suggest that the most likely source of this sediment is the Tiber River drainage basin in central Italy, where a Pleistocene volcanic field is superimposed on Apennine orogenic rocks. In contrast, the Miocene sand in Unit III at Site 974 may have been derived from local basement highs. The quartzolithic composition and preponderance of metamorphic and sedimentary lithic debris in sand samples from Unit II at Site 976, Unit I at Sites 977 and 978, and Unit I at Site 979 are consistent with derivation from metamorphic rocks and sedimentary cover sequences that crop out in the Betic Cordillera of southern Spain (976-978) and in the Rif of Northern Africa (979). The sedimentary to metamorphic lithic fragment ratios in these samples reflect the relative proportion of metamorphic and sedimentary rocks exposed in onshore source terranes. In contrast, the source of the few quartzose Pleistocene sands at Site 976 was likely the Flysch Trough Units that crop out near Gibraltar. The significant volcanic component in certain intervals at Sites 976 (upper Miocene) and 977 (lower Pliocene to Miocene) is consistent with widespread volcanic activity during basin inception and development. Mean sand detrital modes for sand subgroups from both the Alboran and Tyrrhenian Basin sites plot in the Recycled Orogenic and Magmatic Arc compositional fields of Dickinson et al. (1983, doi:10.1130/0016-7606(1983)94<222:PONAPS>2.0.CO;2), reflecting the hybrid tectonic histories of these basins.

(Table 2) Age determination of Irminger Basin sediment cores

High-resolution records of coarse lithic content and oxygen isotope have been obtained in a piston core from the Irminger Basin. The last glacial period is characterized by numerous periods of increased iceberg discharges originating partly from Iceland and corresponding to millennial-scale instabilities of the coastal ice sheets and ice shelves in the Nordic area. A comparison with midlatitude sediment cores shows that ice-rafted material corresponding to the Heinrich events was deposited synchronously from 40° to 60°N. There are thus two oscillating systems: every 5-10 kyr massive iceberg armadas are released from large continental ice caps, whereas more frequent instabilities of the coastal ice sheets in the high latitude regions occur every 1.2-3.8 kyr. At the time of the Heinrich events the synchroneity of the response from all the northern hemisphere ice sheets attests the existence of strong interactions between the two systems.

Geochemistry of carbon at DSDP Legs 58 and 59 Holes

I obtained 68 quarter sections of cores from the JOIDES Organic Geochemistry Panel for studying type, distribution, and stages of organic diagenesis of sedimentary organic matter in the West Philippine and Parece Vela basins and Mariana Trough area (Figure 1). The present chapter compares (1) 11 geochemical parameters used to determine organic source and its stage of genesis within the 9 site locations in this study area and (2) compares these 11 with the same parameters reported from Leg 56, outer trench slope of the Japan Trench, and Leg 60, Mariana Trough and Trench (Schorno, in press a, b). Even though these sediments are considered pelagic, the organic content in most of the core sections appears to be hemipelagic. The sedimentary organic matter in these cores is believed to be in an early stage of diagenesis. Both conclusions are based primarily on the fl-alkane distribution within the organic matter. This particular parameter, I note later, has a major weakness. As Hunt (Hunt, 1979) and I (in press b) observed, marine organisms synthesize /z-alkanes with distributions containing neither odd nor even preferences. Thus those sediments that did contain w-alkane distributions with OEP near 1, suggesting a late stage of catagenesis, may in actuality be immature marine sediments.

Description of manganese nodules and crust collected from the Hakurei Maru Cruise GH76-1, January-March, 1976, in the Central Pacific Basin

This report of the GH76-1 cruise mainly includes the results of the on-board observations in the survey area of the medial-eastern part of Central Pacific Basin (5 degree -10 degree N, 170 degree -175 degree W) and partly of analytical work at the on-shore laboratory. In addition, the results of some on-board optical and geophysical works along the tracks of Japan-Ogasawara-survey area-Hawaii, are described in appendices. The GH76-1 cruise of the R/V Hakurei-maru was carried out from the 10th January to the 9th March, 1976 as the second phase field work of the Geological Survey of Japan five-year research program of study on the manganese nodule deposits of the Central Pacific Basin and also as a part of the National Research Institute for Pollution and Resources research program of technological study on the exploitation of deep sea mineral resources. The GSJ research program (F.Y. 1974-F.Y. 1978) aims at providing basic information on the manganese nodule distribution and their origin on the deep sea floor of the Central Pacific Basin bounded by the Marshall Ridge to the west, the Christmas Ridge to the east, and the Mid-Pacific Mountains to the north. The first phase of investigation was carried out during the GH74-5 cruise in the eastern part of the area (6 degree -10 degree 30'W, 164 degree 30'-171 degree 30'N)(Mizuno and Chujo, eds., 1975), and the present second phase covered an areas of 5 degree square, just west of the GH74-5 area.

(Table 1) Sample description and tetrapyrrole pigment yield at DSDP Leg 60 Holes

In order to provide a better understanding of the fate of sedimentary chlorophyll and chlorophyll degradation products in all kinds of environments, we have recently expanded our studies to include examination of sediments returned from Legs which are not rich in organic matter, nor are even primarily biogenic. Eight core samples from the Mariana Basin and Trench, obtained from DSDP Leg 60, were analyzed for products of chlorophyll diagenesis. To date, the sediment samples from the South Philippine Sea have been the most organically barren examined. Through elimination of the bias of examining only sediments rich in organic matter, we hope that the fate of chlorophyllous material on a more global scale will eventually be elucidated.

(Table 1) Comparison of diatom-bound and bulk sedimentary d15N values of ODP Holes 175-1082A and 175-1084A

The Matuyama Diatom Maximum (MDM) is a time of peak opal accumulation from 2.6 to ~2.0 Ma within the Benguela Current upwelling system that was initiated by increased influence of Southern Ocean water on the eastern South Atlantic. We measured opal, total organic carbon (TOC), and CaCO3 fluxes and C and N stable isotopes in sediments deposited from 2.4 to 1.95 Ma at Sites 1082 and 1084 to explore the biogeochemical dynamics within the Benguela region. The infusion of Southern Ocean water delivered dissolved nutrients and Southern Ocean flora and fauna, resulting in local opal accumulation increasing up to 8 g/cm**2/ky and the production of diatom mats. Some d15N measurements of diatom-bound organic matter indicate that the mats grew within the Benguela region. The bulk sediment d15N records are taken to reflect changes in the d15N of nitrate in the incoming water, where lower values at 2.4 Ma reflect less nitrate utilization in the Antarctic. A long-term increase in relative nitrate uptake in the Southern Ocean is evidenced by the gradual increase in d15N toward 1.9 Ma.

Benthic foraminiferal record from Santa Barbara basin

The oxygen minimum zone (OMZ) of the late Quaternary California margin experienced abrupt and dramatic changes in strength and depth in response to changes in intermediate water ventilation, ocean productivity, and climate at orbital through millennial time scales. Expansion and contraction of the OMZ is exhibited at high temporal resolution (107-126 year) by quantitative benthic foraminiferal assemblage changes in two piston cores forming a vertical profile in Santa Barbara Basin (569 m, basin floor; 481 m, near sill depth) to 34 and 24 ka, respectively. Variation in the OMZ is quantified by new benthic foraminiferal groupings and new dissolved oxygen index based on documented relations between species and water-mass oxygen concentrations. Foraminiferal-based paleoenvironmental assessments are integrated with principal component analysis, bioturbation, grain size, CaCO3, total organic carbon, and d13C to reconstruct basin oxygenation history. Fauna responded similarly between the two sites, although with somewhat different magnitude and taxonomic expression. During cool episodes (Younger Dryas and stadials), the water column was well oxygenated, most strongly near the end of the glacial episode (17-16 ka; Heinrich 1). In contrast, the OMZ was strong during warm episodes (Bølling/Allerød, interstadials, and Pre-Boreal). During the Bølling/Allerød, the OMZ shoaled to <360 m of contemporaneous sea level, its greatest vertical expansion of the last glacial cycle. Assemblages were then dominated by Bolivina tumida, reflecting high concentrations of dissolved methane in bottom waters. Short decadal intervals were so severely oxygen-depleted that no benthic foraminifera were present. The middle to late Holocene (6-0 ka) was less dysoxic than the early Holocene.

Ketones in hydrothermal petroleums and sediments from Guaymas Basin

The polar compound (NSO) fractions of seabed petroleums and sediment extracts from the Guaymas Basin hydrothermal system have been analyzed by gas chromatography and gas chromatography-mass spectrometry. The oils were collected from the interiors and exteriors of high temperature hydrothermal vents and represent hydrothermal pyrolysates that have migrated to the seafloor by hydrothermal fluid circulation. The downcore samples are representative of both thermally unaltered and thermally altered sediments. The survey has revealed the presence of oxygenated compounds correlated with samples exhibiting a high degree of thermal maturity. Several homologous series of related ketone isomers are enriched in the interiors of the hydrothermal vent samples or in hydrothermally-altered sequences of the downcore sediments (DSDP Holes 477 and 481A). The n-alkanones range in carbon number from C11 to C33 with a Cmax from 14 to 23, distributions that are similar to those of the n-alkanes. The alkan-2-ones are usually in highest concentrations, with lower amounts of 3-, 4-, 5-, 6-, 7- (and higher) alkanones, and they exhibit no carbon number preference (there is an odd carbon number preference of alkanones observed for downcore samples). The alkanones are enriched in the interiors of the hydrothermal vent spires or in downcore hydrothermally-altered sediments, indicating an origin at depth or in the hydrothermal fluids and not from an external biogenic deposition. Minor amounts of C13 and C18 isoprenoid ketones are also present. Simulation of the natural hydrothermal alternation process by laboratory hydrous pyrolysis techniques provided information regarding the mode of alkanone formation. Hydrous pyrolysis of n-C32H66 at 350°C for 72 h with water only or water with inorganic additives has been studied using a stainless steel reaction vessel. In each experiment oxygenated hydrocarbons, including alkanones, were formed from the n-alkane. The product distributions indicate a reaction pathway consisting of n-alkanes and a-olefins as primary cracking products with internal olefins and alkanones as secondary reaction products. Hydrous pyrolyses of Messel shale spiked with molecular probes have been performed under similar time and temperature constraints to produce alkanone distributions like those found in the hydrothermal vent petroleums.

Mapping of C4 plant input from North West Africa into North East Atlantic sediments

Mapping the abundance of 13C in leaf-wax components in surface sediments recovered from the seafloor off northwest Africa (0-35°N) reveals a clear pattern of delta13C distribution, indicating systematic changes in the proportions of terrestrial C3 and C4 plant input. At 20°N latitude, we find that isotopically enriched products characteristic of C4 plants account for more than 50% of the terrigenous inputs. This signal extends westward beneath the path of the dust-laden Sahara Air Layer (SAL). High C4 contributions, apparently carried by January trade winds, also extend far into the Gulf of Guinea. Similar distributions are obtained if summed pollen counts for the Chenopodiaceae-Amaranthaceae and the Poaceae are used as an independent C4 proxy. We conclude that the specificity of the latitudinal distribution of vegetation in North West Africa and the pathways of the wind systems (trade winds and SAL) are responsible for the observed isotopic patterns observed in the surface sediments. Molecular-isotopic maps on the marine-sedimentary time horizons (e.g., during the last glacial maximum) are thus a robust tool for assessing the phytogeographic changes on the tropical and sub-tropical continents, which have important implications for the changes in climatic and atmospheric conditions.

Hydrocarbon analyses of submarine mud volcanoes (MV) in the Kumano forearc basin

Twelve submarine mud volcanoes (MV) in the Kumano forearc basin within the Nankai Trough subduction zone were investigated for hydrocarbon origins and fluid dynamics. Gas hydrates diagnostic for methane concentrations exceeding solubilities were recovered from MVs 2, 4, 5, and 10. Molecular ratios (C1/C2<250) and stable carbon isotopic compositions (d13C-CH4 >-40 per mil V-PDB) indicate that hydrate-bound hydrocarbons (HCs) at MVs 2, 4, and 10 are derived from thermal cracking of organic matter. Considering thermal gradients at the nearby IODP Sites C0009 and C0002, the likely formation depth of such HCs ranges between 2300 and 4300 m below seafloor (mbsf). With respect to basin sediment thickness and the minimum distance to the top of the plate boundary thrust we propose that the majority of HCs fueling the MVs is derived from sediments of the Cretaceous to Tertiary Shimanto belt below Pliocene/Pleistocene to recent basin sediments. Considering their sizes and appearances hydrates are suggested to be relicts of higher MV activity in the past, although the sporadic presence of vesicomyid clams at MV 2 showed that fluid migration is sufficient to nourish chemosynthesis-based organisms in places. Distributions of dissolved methane at MVs 3, 4, 5, and 8 pointed at fluid supply through one or few MV conduits and effective methane oxidation in the immediate subsurface. The aged nature of the hydrates suggests that the major portion of methane immediately below the top of the methane-containing sediment interval is fueled by current hydrate dissolution rather than active migration from greater depth.

Standing stocks and carbon isotopes of live benthic foraminifera from the South Atlantic

Live (Rose Bengal stained) and dead benthic foraminifera of surface and subsurface sediments from 25 stations in the eastern South Atlantic Ocean and the Atlantic sector of the Southern Ocean were analyzed to decipher a potential influence of seasonally and spatially varying high primary productivity on the stable carbon isotopic composition of foraminiferal tests. Therefore, stations were chosen so that productivity strongly varied, whereas conservative water mass properties changed only little. To define the stable carbon isotopic composition of dissolved inorganic carbon (d13CDIC) in ambient water masses, we compiled new and previously published d13CDIC data in a section running from Antarctica through Agulhas, Cape and Angola Basins, via the Guinea Abyssal Plain to the Equator. We found that intraspecific d13C variability of all species at a single site is constantly low throughout their distribution within the sediments, i.e. species specific and site dependent mean values calculated from all subbottom depths on average only varied by +/-0.09 per mil. This is important because it makes the stable carbon isotopic signal of species independent of the particular microhabitat of each single specimen measured and thus more constant and reliable than has been previously assumed. So-called vital and/or microhabitat effects were further quantified: (1) d13C values of endobenthic Globobulimina affinis, Fursenkoina mexicana, and Bulimina mexicana consistently are by between -1.5 and -1.0 per mil VPDB more depleted than d13C values of preferentially epibenthic Fontbotia wuellerstorfi, Cibicidoides pachyderma, and Lobatula lobatula. (2) In contrast to the Antarctic Polar Front region, at all stations except one on the African continental slope Fontbotia wuellerstorfi records bottom water d13CDIC values without significant offset, whereas L. lobatula and C. pachyderma values deviate from bottom water values by about -0.4 per mil and -0.6 per mil, respectively. This adds to the growing amount of data on contrasting cibicid d13C values which on the one hand support the original 1:1-calibration of F. wuellerstorfi and bottom water d13CDIC, and on the other hand document severe depletions of taxonomically close relatives such as L. lobatula and C. pachyderma. At one station close to Bouvet Island at the western rim of Agulhas Basin, we interpret the offset of -1.5 per mil between bottom water d13CDIC and d13C values of infaunal living Bulimina aculeata in contrast to about -0.6 +/- 0.1 per mil measured at eight stations close-by, as a direct reflection of locally increased organic matter fluxes and sedimentation rates. Alternatively, we speculate that methane locally released from gas vents and related to hydrothermal venting at the mid-ocean ridge might have caused this strong depletion of 13C in the benthic foraminiferal carbon isotopic composition. Along the African continental margin, offsets between deep infaunal Globobulimina affinis and epibenthic Fontbotia wuellerstorfi as well as between shallow infaunal Uvigerina peregrina and F. wuellerstorfi, d13C values tend to increase with generally increasing organic matter decomposition rates. Although clearly more data are needed, these offsets between species might be used for quantification of biogeochemical paleogradients within the sediment and thus paleocarbon flux estimates. Furthermore, our data suggest that in high-productivity areas where sedimentary carbonate contents are lower than 15 weight %, epibenthic and endobenthic foraminiferal d13C values are strongly influenced by 13C enrichment probably due to carbonate-ion undersaturation, whereas above this sedimentary carbonate threshold endobenthic d13C values reflect depleted pore water d13CDIC values.

(Figure 1 and 2) Phosphorus pools in the investigated sediments quantified by SEDEX sequential extraction and distribution of recovered 33P spike between sedimentary P pools after incubation

Phosphorus is an essential nutrient for life. In the ocean, phosphorus burial regulates marine primary production**1, 2. Phosphorus is removed from the ocean by sedimentation of organic matter, and the subsequent conversion of organic phosphorus to phosphate minerals such as apatite, and ultimately phosphorite deposits**3, 4. Bacteria are thought to mediate these processes**5, but the mechanism of sequestration has remained unclear. Here, we present results from laboratory incubations in which we labelled organic-rich sediments from the Benguela upwelling system, Namibia, with a 33P-radiotracer, and tracked the fate of the phosphorus. We show that under both anoxic and oxic conditions, large sulphide-oxidizing bacteria accumulate 33P in their cells, and catalyse the nearly instantaneous conversion of phosphate to apatite. Apatite formation was greatest under anoxic conditions. Nutrient analyses of Namibian upwelling waters and sediments suggest that the rate of phosphate-to-apatite conversion beneath anoxic bottom waters exceeds the rate of phosphorus release during organic matter mineralization in the upper sediment layers. We suggest that bacterial apatite formation is a significant phosphorus sink under anoxic bottom-water conditions. Expanding oxygen minimum zones are projected in simulations of future climate change**6, potentially increasing sequestration of marine phosphate, and restricting marine productivity.

Seafloor spreading magnetic anomaly isochron map compilation for the Weddell Sea and Scotia Sea

The deep sea sedimentary record is an archive of the pre-glacial to glacial development of Antarctica and changes in climate, tectonics and ocean circulation. Identification of the pre-glacial, transitional and full glacial components in the sedimentary record is necessary for ice sheet reconstruction and to build circum-Antarctic sediment thickness grids for past topography and bathymetry reconstructions, which constrain paleoclimate models. A ~3300 km long Weddell Sea to Scotia Sea transect consisting of multichannel seismic reflection data from various organisations, were used to interpret new horizons to define the initial basin-wide seismostratigraphy and to identify the pre-glacial to glacial components. We mapped seven main units of which three are in the inferred Cretaceous-Paleocene pre-glacial regime, one in the Eocene-Oligocene transitional regime and three units in the Miocene-Pleistocene full glacial climate regime. Sparse borehole data from ODP leg 113 and SHALDRIL constrain the ages of the upper three units. Compiled seafloor spreading magnetic anomalies constrain the basement ages and the hypothetical age model. In many cases, the new horizons and stratigraphy contradict the interpretations in local studies. Each seismic sedimentary unit and its associated base horizon are continuous and traceable for the entire transect length, but reflect a lateral change in age whilst representing the same deposition process. The up to 1240 m thick pre-glacial seismic units form a mound in the central Weddell Sea basin and, in conjunction with the eroded flank geometry, support the interpretation of a Cretaceous proto-Weddell Gyre. The base reflector of the transitional seismic unit, which marks the initial ice sheet advances to the outer shelf, has a lateral model age of 26.6-15.5 Ma from southeast to northwest. The Pliocene-Pleistocene glacial deposits reveals lower sedimentations rates, indicating a reduced sediment supply. Sedimentation rates for the pre-glacial, transitional and full glacial components are highest around the Antarctic Peninsula, indicating higher erosion and sediment supply of a younger basement. We interpret an Eocene East Antarctic Ice Sheet expansion, Oligocene grounding of the West Antarctic Ice Sheet and Early Miocene grounding of the Antarctic Peninsula Ice Sheet.

Alkenones in the Mediterranean Sea

Time-series of downward alkenone fluxes have been investigated at 200 m depth over a one year sediment trap experiment, in the Northwestern Mediterranean Sea. Alkenone flux maxima occurred in autumn and to a lesser extent in May, during the spring bloom. Temperature estimates calculated from the UK'37 index revealed that alkenone producers preferentially develop in subsurface waters (at about 50 m) in spring, whereas the autumn alkenone production occurred upper in the water column (around 30 m). Examination of the core-top UK'37 index values at various sites of the Northwestern Mediterranean basin, suggested that the spring bloom period do not significantly imprint the temperatures recorded in the sediments. The sedimentary temperature estimates would rather reflect annually integrated SST, with a major influence of the autumnal post-bloom development of the coccolithophores in the euphotic zone.